Organic Compounds Containing Fluorine

CHAPTER 4

Organic Compounds Containing Fluorine BY PAUL T A R R A N T Department of Chemistry, University of Florida, Gainsville, Introduction Hydrofluorocarbons Aliphatic Hydrofluorocarbons Aromatic Compounds with an Aliphatic Side Chain Compounds with Fluorine in an Aromatic Nucleus Unsaturated Hydrofluorocarbons Cyclobutane Derivatives Alcohols Ethers Aldehydes and Ketones Acids and Their Derivatives Amines Heterocyclic Compounds Amino Acids Dyes Drugs Pesticides Polymers Containing Fluorine Styrene Derivatives Acrylic Acid and Its Derivatives Vinyl Fluoride 1-Chloro-l-fluoroethylene Vinylidene Fluoride Trifluoroethylene Chlorotrifluoroethylene Fluoroprene 2,3-Difluoro- and 2-Chloro-3-fluorobutadiene Bibliography

Florida Page 213 214 214 220 223 224 226 229 232 235 238 242 243 246 248 253 258 260 261 264 265 266 267 267 267 269 2708

Introduction Organic compounds containing fluorine have held the attention of chemists for a long time because of the unusual and often unexpected properties which the fluorine atom gives to the molecule. For example, monofluoro compounds are sometimes very unstable, and certain com­ pounds such as the fluoroacetates are quite reactive physiologically; on the other hand, other compounds such as CF 3CH 2C1 are quite unreactive both chemically and physiologically. 213

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PAUL TARRANT

The introduction of fluorine atoms into an organic molecule makes pronounced changes in the physical properties of the compounds as well. Many chemists have been surprised to find the index of refraction of many fairly common fluorine compounds to be less than 1.3000, the lowest reading on the ordinary refractometer. Although the replacement of hydrogen by fluorine in a hydrocarbon usually gives a negligible change in boiling point, marked changes often occur in molecules containing functional groups. The following data show the change in boiling points as fluorine atoms are progressively introduced into ethyl acetate : CH3CO2C2H6

C H 2F C 0 2C 2H 6 C H F 2C 0 2C 2H 6 CF 3C0 2C>H 5

77°C 116° 99° 62°

The organic chemists arc continuously striving to tailor-make new molecules with unusual properties, and fluorine compounds are being used in increasingly large amounts in synthetic work. It may be a while before the chemist can obtain a wide variety of compounds with func­ tional groups, but there are available today certain reactive fluorine compounds which can be used in synthetic processes. For example, a number of olefins such as C F 2= C H 2, C F 2= C F C 1 , and C F 2= C C 1 2 can be obtained in pound batches; these molecules react readily with alcohols, amines, mercaptans, and with themselves to give other compounds con­ taining the ordinary functional groups such as ether, amide, sulfide, etc. A vast number of compounds can also be obtained from the fluorocarbon derivatives such as the acids, aldehydes, etc., as discussed in Volume I. It is hoped that the following pages will reveal to the reader the variety of interests which has led a great many investigators to contribute so much to our knowledge of the chemistry of fluorine compounds; the workers in this field may feel justly proud of their accomplishments. It is also hoped that the uninitiated may see the need for additional research in this area and accept*the challenge it offers. Hydrofluorocarbons ALIPHATIC HYDROFLUOROCARBONS

In general, the methods most frequently employed for the preparation of aliphatic hydrofluorocarbons are: (a) the addition of hydrogen fluoride to an unsaturated compound, or (6) the replacement of other halogens by the use of a suitable fluorinating agent such as antimony trifluoride, mercuric fluoride, hydrogen fluoride, or even potassium fluoride.

ORGANIC COMPOUNDS CONTAINING FLUORINE

215

The preparation of ethyl fluoride can be carried out conveniently and in good yields simply by heating ethylene and hydrogen fluoride for several hours in an autoclave (156). Other olefins such as propylene and cyclohexene react readily to give the corresponding alkyl fluoride. How­ ever, it should be pointed out that alkyl fluorides are generally quite difficult to purify sufficiently to prevent their decomposition except for the low boiling compounds. Traces of water or acids or even the use of temperatures of 60 to 75° during a distillation will often cause the molecule to lose hydrogen fluoride and form olefins which may undergo polymeriza­ tion. This possibility is particularly noticeable in the case of secondary or tertiary fluorides. CH3

CH3

I

I

CH 3—C—CH 3

> C H 2= C — C H 3 + H F

I

F CH3

I

HF

n C H 2= C — C H 3 > [—CH 2—C(CH 3) 2—] n The preparation of alkyl fluorides by the reaction of alcohols and hydrogen fluoride appears attractive but such is actually not the case. In the first place, any water formed in the reaction will remove hydrogen fluoride from the alkyl fluoride formed to give the olefin. Even if the olefin did not polymerize in the presence of the acid, it is possible that a new alkyl fluoride will be formed by the reaction of hydrogen fluoride with the olefin. Since hydrogen fluoride adds to olefins in the normal manner, secondary or tertiary fluorides are formed. Therefore, it can readily be seen that the reaction of primary alcohols may give rise to a mixture of primary and secondary alkyl fluorides. 1. R C H 2C H 2O H + H F - > R C H 2C H 2F + H 20 H 20 2. R C H 2C H 2F > R C H = C H 2 + HF 3. R C H = C H 2 + H F - + R C H F C H 3 Because of the unavoidable difficulties in the preparation of monofluorides in addition to their limited usefulness due to their instability, the litera­ ture contains few references to them. Certain difluoroalkanes can be made in excellent yields by adding hydrogen fluoride to an olefin containing a chlorine atom on one of the carbon atoms of the unsaturated bond. The reaction proceeds so readily to give the difluoro compound that care must be exercised to prevent an excess of hydrogen fluoride in reactions in which the chlorofluoro deriva­ tive is desired. For example, in the reaction between 2-chloro-2-butene and

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PAUL TARRANT

hydrogen fluoride, even a slight excess of the latter gives a considerable amount of 2,2-difluorobutane together with some 2,2-dichlorobutane. The reactions with chloroolefins in many cases take place at room tem­ perature or below and thus the tar usually formed in many fluorination reactions is absent; furthermore, since a large excess of hydrogen fluoride is unnecessary for the reaction, elaborate equipment for separating the unreacted fluorinating agent is not required. Renoll has reported the addition of hydrogen fluoride to several 2-chloro-2-alkene compounds to give 2,2-difluoroalkanes in yields from 60 to 70% (393). Under the conditions employed, with an excess of hydrogen fluoride, only the substitution product was ever isolated. Henne and Pleuddeman made an extensive study of the addition of hydrogen fluoride to haloolefins (201). Olefins of the type R H C = C H X did not react well to yield one or two simple products. For example, C H 3C H = C H C 1 gave traces of C 2H 5C H F 2, 5 % of unreacted olefin, 10% of the addition product, 20% of CH 3CHC1CH 2C1, and the rest tar. On the other hand, monochloroolefins of the type R R ' C = C H C 1 reacted smoothly with hydrogen fluoride at low temperature to give excellent yields of the simple addition product. From ( C H 3) 2C = C H C 1 at —23°, there was obtained a 6 5 % yield of (CH 3) 2CHCHFC1; tar formation was negligible at this temperature. As might be expected, compounds of the type R R O = C C 1 2 also reacted smoothly at 65° to give both the addition product and more highly fluorinated compounds. Dihaloolefins of the type R C X = C R ' X varied considerably in their reactivity toward hydrogen fluoride. Neither CHC1=CHC1 nor CHC1=CC1 2 was found to react with hydrogen fluoride even under drastic conditions. Although CH 3CC1=CHC1 reacted smoothly at 120° with hydrogen fluoride, low yields of fluoro compounds were obtained. However, in the presence of boron trifluoride, even perhaloethylenes can be made to accept hydrogen fluoride (183). Tetra-, tri-, and 1,2-dichloroethylene gave the corresponding addition products in yields of 30, 60, and 26%, respectively; even the very unreactive C F C l ^ C F C l gave a 4 3 % yield of CHFC1CF 2C1. The addition of hydrogen fluoride to acetylenic hydrocarbons has received a great deal of attention. This reaction is of interest in the preparation of compounds on an industrial scale because of its simplicity and its complete utilization of the fluorinating agent. It is possible to add a single molecule of hydrogen fluoride to the triple bond to give vinyl fluoride, and, in certain cases, fluoroprene is obtained as a by-product. If two molecules of hydrogen fluoride add, then the saturated 1,1-difluoroethane results. It is believed that this is the initial step in the process

ORGANIC COMPOUNDS CONTAINING FLUORINE

217

used by a leading American industrial concern for the preparation of a variety of 1,1-difluoroethanes such as CH 2C1CHF 2, CH 3CF 2C1, and more highly chlorinated products. The addition of hydrogen fluoride to acetylene was apparently first carried out in the middle 1930's in Germany (243, 248). In recent years, in the United States and in England, the reaction has been studied as a method of preparation of vinyl fluoride, 1,1-difluoroethane, and 2-fluorobutadiene-1,3. In some cases mercury salts are listed as catalysts, whereas in others fluorosulfonic acid, boron fluoride, and hydrogen chloride are claimed to have catalytic properties. Calfee and Bratton claim the complete conversion of acetylene to C H 3C H F 2 by passing C 2H 2 and hydrogen fluoride in a molar ratio of 1:2 into a mixture of fluorosulfonic acid and hydrogen fluoride maintained at 0°. At higher temperatures both vinyl fluoride and the saturated difluoride are obtained (57). Hillyea claims that good yields of vinyl fluoride are obtained by pass­ ing acetylene, hydrogen chloride, and hydrogen fluoride over mercuric chloride maintained at 100 to 315°; in the absence of hydrogen chloride, the yields of vinyl fluoride were low (219). Aluminum oxide or fluoride is used as the catalyst in a process de­ scribed by Hillyea and Wilson for the production of vinyl fluoride or difluoroalkanes (220). Acetylene and hydrogen fluoride in a molar ratio of 1:2.24 at 315° give vinyl fluoride and C H 2F C H 2F . 1-Hexyne gives an 85% yield of C H 3( C H 2) 3C F 2C H 3, and 1-pentyne gives an 84% yield of C H 3( C H 2) 2C F 2C H 3 under similar conditions. The catalytic activity of the aluminum compounds did not decrease over periods as long as 32 hours. Mercuric acetate or oxides as well as zinc- or nickel-mercury chromite have been impregnated on charcoal for use as catalysts in the reaction (254, 255). It has been claimed that mercury compounds deposited on alkaline earth metal salts serve as better catalysts because charcoal reduces and deactivates the mercuric salts at elevated temperatures. In the past several years some interest has been shown in elastomers made from fluoroprene, C H 2= C F C H = = C H 2, because of their oil and sunlight resistance, high resilience, and other desirable qualities. The monomer can be made by several methods, but a number of patents have been issued to cover the reaction of vinylacetylene with hydrogen fluoride (72, 418, 419). In a typical example, hydrogen fluoride, vinylacetylene, and nitrogen are passed over a charcoal-supported mercuric salt catalyst at 40° with a contact time of about 40 seconds. The conversion to fluoroprene was about 40%; in addition, some 3,3-difluoro-l-butene was obtained.

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Aliphatic hydrofluorocarbons are frequently obtained by replacing another halogen atom with fluorine by the use of a suitable fluorinating agent. In most cases, organic chlorine compounds are generally used as starting materials and very often products containing both fluorine and chlorine are obtained. Since the methods of replacement of chlorine in such aliphatic compounds has been discussed quite adequately by Park (Chapter 15, Volume I), only a very brief account will be given here. Actually, the number of saturated aliphatic compounds containing only hydrogen and fluorine which have been obtained by this method is limited. Probably the best known is 1,1,1-trifluoroethane, C H 3 C F 3 , which can be prepared in excellent yield by heating methyl chloroform with anhydrous hydrogen fluoride (425). Sometimes antimony trifluoride with a pentavalent antimony salt as catalyst is used; C H 3 C H 2 C C I 3 has been converted to C H 3C H 2C F 3 by such a mixture. A somewhat more convenient procedure is to carry out a simultaneous addition across a double bond and replacement of chlorine atoms in the molecule; for example, by such a reaction C H 3C F 3 can be obtained readily from C H 2= C C 1 2 and C 2H 5C F 3 from C H 3C H = C C 1 2. It is also reasonably easy to effect the replacement of both chlorine atoms in compounds of the type RCC1 2R/ by refluxing such compounds with antimony trifluoride and a suitable catalyst. Whalley has reported that stannic chloride is superior to antimony pentachloride as a catalyst in such reactions since the formation of tars is greatly reduced (545, 546). Although detailed directions for fluorination reactions are often found in the literature, quite frequently the experimenter meets with little success in carrying out the same or similar reactions for the first several trials until certain details such as rate of heating, amount of catalyst, and speed of stirring, which may seem insignificant, are worked out properly. Mercuric fluoride has been found to be an effective reagent for replac­ ing other halogen atoms to yield aliphatic fluoro compounds (193). How­ ever, it is expensive and its preparation requires the use of elemental fluorine. In 1938, Henne reported that excellent results could be obtained by employing a mixture of mercuric oxide and hydrogen fluoride as the active fluorinating agent (179). By the use of such a reagent, the replace­ ment of chlorine can be carried out at low temperatures where the forma­ tion of by-products and tars are minimized and, consequently, good yields of the desired product are often obtained. For example, 70 to 80% yields of compounds such as C H 2F 2 and C H 3C H F 2 have been obtained. In some cases, mercurous fluoride, which is easily prepared, is treated with a second halogen to give a mixture of mercuric fluoride and mercuric halide which then converts organic halogen compounds to fluorides. For

ORGANIC COMPOUNDS CONTAINING FLUORINE

219

instance, methylene fluoride has been obtained from methylene iodide, mercurous fluoride, and iodine (38). In recent years, potassium fluoride has been used to replace other halogen atoms for the preparation of alkyl fluorides. For example, Gryskiewicz-Trochimowski has reported that C 6H i 3F and C 1 1 H 2 3 F have been obtained in 20% yields from the corresponding chlorine analogs (159). Hoffmann (231) has improved the process for preparing aliphatic fluorides by carrying out the reaction with solvents such as the simple glycols; for example, by using this technique the yield of hexyl fluoride has been increased to 54%. Although this method is inferior in some respects to those using antimony or mercury fluorides, the availability of potassium fluoride and the ease with which the reaction can be carried out in conventional equipment make it a convenient method in certain instances. Surprisingly enough, sodium fluoride does not participate in exchange reactions of this type. Alkyl fluorides are reported to lose hydrogen fluoride readily. How­ ever, compounds containing two fluorine atoms on a single carbon are remarkably stable. For instance, McBee and Hausch were unable to effect the removal of hydrogen fluoride from C H 3C F 2C H = C H 2 even on heating with potassium hydroxide at 200° (326). It is well recognized that the presence of two or more fluorine atoms on a terminal carbon with a second halogen reduces the reactivity of the halogen. Numerous instances have also shown that the — C F 2— or the CF 3— group also greatly retards the reactivity of a halogen atom on an adjacent carbon. For example, CF 3CH 2Br has not as yet been made into a Grignard reagent and does not substitute readily with bases to give either an alcohol or an ether. The —CF 2— group likewise stabilizes a chlorine atom next to it since the dehydrochlorination of C H 3C F 2CHC1CH 3 occurs only slowly with alcoholic potassium hydroxide even at 150° (326). In contrast, Henne and Hinkamp have shown that C H 3C F 2CH 2CH 2C1 gives the olefin readily at a much lower temperature (188). It is postulated in the latter case that the hydrogen atom alpha to the — C F 2— group is more acidic and is therefore removed by alkali, following which the chloride ion is eliminated and the olefin formed. In some cases, the reactivity of a chlorine atom is so greatly reduced that it seems that a fluorine atom from a methforyl group is displaced. For example, McBee and Bolt have shown that CF 3CHC1CF 3reacts with sodium aryl oxides to give compounds of the type CF 3CHC1CF 20R rather than the expected CF 3CH(CF 3)OR (316). However, in this case, the hydrogen atom is probably very susceptible to attack and, when removed, causes a fluoride

220

PAUL TARRANT

ion to be eliminated to form the olefin CF 3CC1=CF2, which accepts the phenol to form the ether CF 3CHC1CF 20R. The chlorination of hydrofluorocarbons has been the subject of several investigations. Henne has amply demonstrated that the chlorination of compounds containing two or three fluorine atoms per carbon follows certain definite patterns. For instance, the chlorination of C F 3C H 2C H 3 in sunlight gave successively CF 3CH 2CH 2C1, CF 3CH 2CHC1 2, C F 3C H 2C C 1 3 and then proceeded directly to CF 3CC1 2CC1 3 without any tetrachloride being found (213). Again the resistance to substitution of hydrogen atoms alpha to a methforyl group was demonstrated in the chlorination of C F 3C H 2C H 2C H 3, which gave only CF 3CH 2CH 2CH 2C1 and C F 3C H 2CHC1CH 3 (189). Chlorine more often will accumulate on a carbon atom already holding chlorine as shown when CF 3CH 2CHC1CH 3 gave 4 parts of CF 3CH 2CC1 2CH 3 to 3 of CF 3CH 2CHC1CH 2C1 and when C F 3C H 2C H 2CH 2C1 gave twice as much C F 3C H 2C H 2C H C 1 2 as CF 3CH 2CHC1CH 2C1. In sunlight and in the presence of water C H 3C F 2C H 2C H 3 upon chlorination gave 2 parts of CH 3CF 2CHC1CH 3 and 3 parts of C H 3C F 2CH 2CH 2C1 but no CH 2C1CF 2CH 2CH 3 (188). The methyl group adjacent to the C F 2 was not attacked even when three chlorine atoms entered the butane molecule, again indicating the reluctance of certain hydrogen atoms to take part in substitution reactions with chlorine. Quite probably higher chlorination temperatures give a more random distribution of chlorine atom since McBee and Hausch found a consider­ ably greater amount of CH 3CF 2CHC1CH 3 than was previously reported when C H 3C F 2C H 2C H 3 was chlorinated (326). A — CC1F— group is much less effective in directing substitutive chlorination away from the alpha position than — C F 2— or — C F 3 groups. For example, the chlorination of CH 3CFC1CH 2CH 3 yielded 4 5 % CH 3CFC1CHC1CH 3 as against 2 1 % CH 3CFC1CH 2CH 2C1. McBee and his coworkers have reported that the bromination of alkanes containing fluorine occurs only at elevated temperatures. Methyl fluoroform, when reacted at 500° at a contact time of 25 seconds, gave about 50% of CF 3CH 2Br, 7 % of CF 3CHBr 2, and traces of C F 2BrCH 2Br and CF 3CBr 3. Ethyl fluoroform, C F 3C H 2C H 3, at 450° yielded about 4 parts of C F 3C H B r C H 3 and 7 parts of C F 3C H 2C H 2B r along with C F 3C H 2C H B r 2 (324). AROMATIC COMPOUNDS WITH AN ALIPHATIC SIDE CHAIN

Aromatic compounds containing fluorine in a side chain have been known for many years. S warts first prepared benzotrifluoride by reacting benzotrichloride with antimony trifluoride (473). In 1933 a patent was

ORGANIC COMPOUNDS CONTAINING FLUORINE

221

issued for the use of hydrogen fluoride in preparing C eH6CF 3 (266), and it is now made on a commercial scale by this process. = Henne has pointed out the similarity of this easily fluorinated molecule to that of CC12 CC1CC1 3, which will also react with hydrogen fluoride or S b F 3without catalyst, and has concluded that chlorine atoms adjacent to an olefinic bond are replaced more readily than in other positions. In an attempt to correlate the reactivity of some metal fluorides with other properties, Tewksbury and Haendler made a study of the vapor phase fluorination of benzotrichloride at 225° (514). The fluorides of lithium, potassium, calcium, magnesium, aluminum, and manganese gave no benzotrifluoride. With the other agents, the percentage yields were: NaF, 15; ZnF 2, 70; CdF 2, CoF 2, 18; P b F 2, 45; SbF 3, 60-65; BiF 3, 29; CuF 2, 44. The results show that the reactive fluorides are those of metals, except sodium, with oxidation-reduction potentials below manganese, but there is no parallelism between yield and potential. There appears to be no correlation between activity of the fluorides with the crystal structures of the fluorides or chlorides nor with their solubili­ ties in organic solvents. Compounds containing more than one methforyl group are readily prepared. In the 1930's, German chemists had prepared the three isomeric bis (methforyl) benzenes, and the preparation of tris (methforyl) benzenes has also been reported (239, 241). It is of interest to note that a somewhat involved procedure is used for the preparation of l,2-bis(methforyl)benzene. CH3

CC1 3

CF3

Since the chlorination of o-xylene does not proceed beyond the pentachloro stage, it is necessary to replace the bulky chlorine atoms by smaller fluorine atoms before the last hydrogen atom can be removed. Certain ring-substituted derivatives of benzotrifluoride may be made easily. By nitration, chlorination, or bromination, the corresponding meta-substituted compound may be obtained from which a wide variety of other substances may be made by the usual synthetic methods. For instance, ra-bromobenzotrifluoride has been converted to th^ Grignard

222

PAUL TARRANT

reagent from which alcohols, olefins, etc., containing the 3-methforylphenyl group have been obtained (4). In cases where the methforyl group is desired ortho or para to some other group, a different approach must be used, since ordinary substitu­ tion reactions such as nitration and halogenation take place exclusively in the meta position of benzotrifluoride. In some instances, the group desired may be introduced in the ortho or para position of toluene which may then be chlorinated and treated with antimony trifluoride or hydro­ gen fluoride to give the substituted benzotrifluoride. In such a manner, the ring-substituted nitro and chloro compounds have been made. fhe preparation of the o- and p-bromobenzotrifluoride has not been carried out by this procedure because no satisfactory method has been found to chlorinate the bromotoluenes without removing the nuclear-bound bromine; instead, Jones made a number of phenols, fluorides, chlorides, bromides, and iodides by the diazonium transformation of o- and paminobenzotrifluoride (261). The amino compounds were made by rather lengthy syntheses; the synthesis for the p-compound is shown. C B R 3 0 2N — f ~ \ — C H 3^ 0 2N — ^ y > — SbF

3 0 N—(/jf~\ 2

>

Y-CF

SnCl 3

2• H N—(/ / - \> - C F 2

C NaNOi; F HBr B r — ^ ~ y ~

'<

A somewhat more convenient synthesis of p-bromobenzotrifluoride has been carried out by the bromination of ra-aminobenzotrifluoride, which is commercially available, followed by the deamination by hypophosphorous acid of the amino group ; in this synthesis, some o-bromobenzotrifluoride is also obtained (287). Recently Benkeser and Severson have found that o-bromobenzotrifluoride may be made in 28% over-ail yield by the metallation of benzotrifluoride with n-butyllithium followed by a reaction with bromine (23). Under most circumstances compounds containing methforyl groups on an aromatic nucleus are remarkably stable. For many years, the pro­ cedure used for making trifluoroacetic acid consisted of the oxidation of ra-aminobenzotrifluoride with dichromate, whereby the aromatic ring was destroyed. However, under the influence of concentrated acid, the — C F 3 group can be converted to the carboxylic acid group, and such a reaction has been used to advantage in proving the structures of many such compounds (282). In compounds containing both the methforyl and

ORGANIC COMPOUNDS CONTAINING FLUORINE

223

the difluoromethyl groups, the difluoromethyl group can be hydrolyzed and, as a result, trifluoromethylbenzaldehyde is formed. McBee and coworkers report that chlorination of the bis(methforyl)benzenes in the presence of conventional catalysts and at temperatures approaching the boiling point of the fluorides does not occur (325). Bradsher and Kittila have shown that 1,3-bis (methforyl) benzene can be made to react with chlorine to yield the 5-chloro derivative at tempera­ tures of 150 to 170° and a chlorine pressure of 20 atmospheres (48). McBee and Pierce have reported that l-ethforyl-4-(methforyl)benzene may be obtained from the corresponding chloro compound by fluorination with a mixture of antimony trifluoride and antimony pentachloride for 7 hours at 165°. However, the octachloroethyltoluene must be highly purified if the fluorination is to be successful (333). An attempt to introduce the pentafluoroethyl group into benzene was made earlier by Simons and Ramier, who made use of the FriedelCrafts reaction between trifluoroacetyl chloride and benzene to yield trifluoroacetophenone (451). The ketone was then treated with PC1 5 to give C 6 H 5 C C I 2 C F 3 in yields of about 45%. The latter compound failed to react with antimony trifluoride to give pentafluoroethylbenzene as had been expected to occur rather readily. Cohen et al. succeeded in preparing C 6H 5CFC1CF 3 in 3 5 % yield from C 6 H 5 C C I 2 C F 3 at elevated temperatures with antimony trifluoride and bromine (73). Simons and Herman showed that it was not possible to replace all five atoms of chlorine in CeH 5CCl 2CCl3 with the more usual fluorinating agents. They were successful in preparing a small sample of the pentafluoride with active silver fluoride made by using elemental fluorine (449). COMPOUNDS WITH FLUORINE IN AN AROMATIC NUCLEUS

Although aromatic fluorine compounds may be prepared by the decomposition of diazonium salts in hydrofluoric acid or by the decom­ position of diazonium piperides with concentrated hydrofluoric acid, the most widely used method is that of Balz and Schiemann (11). In this procedure, the amine is diazotized by the usual agent such as nitrous acid, amyl nitrite, or nitrosylsulfuric acid, followed by the addition of fluoroboric acid or one of its salts, with the insoluble diazonium fluoro­ borate being precipitated. The solid is filtered, washed, and dried. The dried salt is then decomposed by gentle heating to yield the fluoro deriva­ tive. An alternate method consists in carrying out the diazotization in the presence of a fluoroborate so that the diazonium fluoroborate precipitates continuously as it forms; in this manner, very good yields of pure fluoro­ borates have been obtained.

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PAUL TARRANT

Roe, in his excellent review of the Schiemann reaction, suggests that variations in the yield of fluoroborates are due to differences in solubility of the various compounds used (404). For example, the carboxyl and hydroxyl groups cause increased solubility of the fluoroborate, and when these groups are converted to esters and ethers, the yields are improved. The highest yield of the diazonium fluoroborate from o-aminobenzoic acid has been reported to be 46%, whereas the ethyl o-aminobenzoate gives a yield of 90%. The anisidines gave o-, m-, and p-fluoroanisole in yields of 91, 82, and 85%, respectively, whereas m-aminophenol gave only a 50% yield of m-fluorophenol and o- and p-aminophenol gave none of the corresponding fluorophenols. The decomposition of the diazonium fluoroborate generally takes place smoothly by heating the dry salt gently with a burner until a reaction is noted; frequently no additional heat is necessary to continue the decomposition. For the most part, yields in this step are good. Benzene diazonium fluoroborate has been converted to fluorobenzene quantita­ tively, while yields with alkyl groups or the halogens are 80% or greater. Nitrodiazonium fluoroborates are troublesome to work with since they do not decompose evenly and low yields of the fluoride are obtained. For the decomposition of such compounds, it is advisable to dilute the fluoro­ borate with several times their weight of some inert material such as sand and to carry out the reaction with small quantities of compound at a time. Most of the fluoroborates decompose at temperatures of 80° or more, but the diazonium fluoroborates of a number of heterocylic com­ pounds decompose at room temperature or below. In recent years, there has been renewed interest in the preparation of aromatic fluorine compounds by diazotization of the amine in hydrogen fluoride. Ferm and Vanderwerf have made a study of this reaction and report that in many cases yields are as good or better than those reported for the Schiemann reaction (135). The following compounds were pre­ pared successfully by Ferm and Vanderwerf in the percentage yields indicated: fluorobenzene, 87; o-fluorotoluene, 73; m-fluorotoluene, 82; p-fluorotoluene, 78; 4-fluoro-l,3-dimethylbenzene, 57 ; 2-fluoro-l,4-dimethylbenzene, 43; ra-chlorofluorobenzene, 81; p-chlorofluorobenzene, 74; m-nitrofluorobenzene, 39; p-nitrofluorobenzene, 62; o-fluorobenzoic acid, 57; and p-fluorobenzoic acid, 98. UNSATURATED HYDROFLUOROCARBONS

Although a large number of aliphatic olefins containing fluorine have been prepared and studied, most of such compounds also contain chlorine and have thus been treated earlier (Volume I, Chapter 15). The olefins containing only carbon and fluorine will also be described elsewhere.

225

ORGANIC COMPOUNDS CONTAINING FLUORINE

Vinyl fluoride, as previously noted, has been prepared from acetylene. Interest in this material and in vinylidene fluoride, C H 2= C F 2 has been largely confined to their use in polymers. Park (336) has recently reported an interesting synthesis of trifluoroethylene : Zn

HBr

Zn

C F 2C l C F C l 2- » C F 2= C F C 1 • CF 2BrCHFCl -> C F 2= C H F This material is more convenient to handle than the low-boiling (ca. —80°) vinyl fluoride, and, consequently, its reactions have been studied more extensively (363). For example, the olefin accepts bromine and chlorine readily across the double bond; methanol adds to give methyl trifluoroethyl ether, C H 3O C F 2C H 2F . The majority of the other aliphatic olefins containing only carbon, hydrogen, and fluorine which have been reported have a trifluoromethyl group. The simplest of these, C F 3C H = C H 2, has been prepared by Henne as follows (212): == ==: HF CI base CC12 CHCH3 • C F 3C H 2C H 3 —• CF 3CH 2CH 2C1 • C F 3C H C H 2 Henne and coworkers have shown that this olefin is rather unreactive owing to the effect of the — C F 3 group (190). In contrast to the hydro­ carbon, C H 3C H = C H 2, the electronic displacement of the double bond is toward the — C F 3 group so that hydro acids add, but with difficulty, to yield compounds of the type C F 3C H 2C H 2X . Water could not be added and polyacrylates were formed in concentrated sulfuric acid. Addition reactions of CHC1 3 and CCI4 catalyzed by peroxides and polymerization in the presence of a peroxide did not take place. More readily decomposed compounds, such as C F 3I and CCl 3Br, have been found to add to C F 3C H = C H 2 under the influence of ultraviolet light (195). Iodotrifluoromethane gave C F 3C H I C H 2C F 3 whose structure was shown by dehydrohalogenation to the known C F 3C H = C H C F 3. Goldschmidt has reported that both C F 3C H = C H 2 and C H 2= C ( C F 3) C H 3 can be made to undergo polymerization in the presence of a free radical initiator and a co-solvent for the monomer and the initiator (153) ; however, Friedel-Crafts reagents were unsuccessful as polymerization catalysts. Trifluoropropyne, C F 3C = C H , has recently been prepared and its properties studied (194). The most successful synthesis was carried out as follows: SbFa

CC1 3CH 2CH 2C1

KOH

> CF 3CH 2CH 2C1

CF 3CHBrCH 2Br

KOH

Br

• C F 3C H = C H 2- + Br

• C F 3C B r = C H 2- > C F 3C B r 2C H 2B r

KOH

>

Zn

C F 3C B r = C H B r - > C F 3C = C H

226

PAUL TARRANT

The propyne forms a white silver acetylide which darkens on standing but explodes on heating. Chlorine reacts with CF 3Cs=CH in sunlight to

yield CF3CCI2CCI3.

An interesting property of C F 3C = C C F 3 is its ability to accept acetic : The addition of one molecule of acid gives an enolacetate, acid (208). CF 3CH= C(CF3)02CCH3, while two, molecules give the diacetate CF 3CH 2C(CF3)(OCOCH3)2; some trifluoroacetone, CF 3COCH 3, and acetyl fluoride are also formed. The monoacetate can be converted in excellent yields to C F 3C O C H 2C F 3 by reflux with butanol treated with a few drops of sulfuric acid. Cyclobutane Derivatives Generally, there is not a great tendency toward the formation of the cyclobutane ring in reactions of organic compounds. However, it has been found that C F 2= C F 2, C F 2= C F C 1 , and C F 2= C C 1 2, in contrast to the other haloolefins, will very easily dimerize to give the cyclo compounds and will even react with a vast number of other unsaturated compounds to give a variety of derivatives containing the cyclobutane ring. Investigations of the formation of CF 2—CF 2—CFC1CFC1 and I

I

CF 2CF 2CCl 2CCl2 apparently were being conducted simultaneously in 1

1

Germany and the United States during the early 1940's. Henne and Ruh reported the synthesis and properties of these compounds and identified them by the following reactions (206) : COOH C F 2C F 2C C 1 2C C 1 2^ C F 2C F 2C C 1 = C C 1 ^ ( C F 2) 2

I

I

I

J

I

COOH These reactions offer a good method for preparing tetrafluorosuccinic acid and its derivatives. Chemists of the duPont Company have been most active in studying the reactions of C F 2= C F C 1 , and C F 2= C F 2, in particular, with olefins containing a functional group to give aldehydes, ketones, acids, nitriles, and many other classes of organic compounds (17, 21). In an excellent research study, Coffman et al. found that the synthesis of many such compounds containing the 4-membered ring occurs more readily than the dimerization of the fluoroolefin so that the yields are generally good (68). The reaction with ethylene is illustrated below: C F 2 C H 2 C F 2— C H 2

II

CF2

+ II

-

CH2

I

I

C F 2— C H 2

ORGANIC COMPOUND S CONTAININ G FLUORIN E

227

The eas e o f reactio n varie s wit h th e unsaturate d reactant . Compound s containing th e C H 2= g r o u p combin e mor e readil y tha n d o 1,2-disubsti tuted compound s suc h a s 2-buten e o r trichloroethylene , whil e reactant s having conjugate d unsaturate d linkages , suc h a s occur s i n 1,3-butadiene , acrylonitrile, an d stryene , ar e eve n mor e reactive . Tetrafluoroethylene react s wit h monoolefins , viny l chloride , viny l acetate, an d ally l alcoho l t o giv e compound s o f th e typ e: CF 2—CHX

I

I

C F 2— C H 2 With propylene , a 72 % yiel d o f methy l tetrafluorocyclobutan e wa s ob tained; viny l chlorid e an d vinyliden e chlorid e gav e yield s o f 2 3 % an d 46%, respectively . Tetrafluoroethylene an d acrylonitril e combin e t o for m i n 84 % yiel d cyanotetrafluorocyclobutane CF 2—CHCN

I

I

C F 2— C H 2 which ca n b e hydrolyze d t o th e cyclobutan e carboxyli c acid . Methy l methacrylate likewis e give s excellen t yield s o f methy l l-methyl-2,2,3,3, tetrafluorocyclobutanecarboxylate. A wid e variet y o f ethylenicall y unsaturate d oxygen-containin g com pounds includin g acrolein , methacrolein , viny l acetate , methy l viny l ketone, methy l viny l ether , 2-vinylfuran , an d butadien e monoxid e hav e been treate d wit h tetrafluoroethylen e t o giv e th e cyclobutan e derivativ e in yield s rangin g fro m 9 t o 77% . Very interestin g product s ar e obtaine d fro m th e reactio n o f 1,3-diene s and tetrafluoroethylene . Th e simples t compoun d forme d i s th e 1-vinyl 2,2,3,3-tetrafluorocyclobutane an d no t th e tetrafluorocyclohexen e whic h would b e forme d b y a Diels-Alde r reaction . Thi s compoun d ca n reac t with a secon d tetrafluoroethylen e molecul e t o giv e a produc t containin g two 4-membere d rings . C F 2— C H 2 C H 2— C F 2

I

I

I

I

C F 2— C H — C H — C F 2 Aliène react s t o giv e methylen e tetrafluorocyclobutane , CF2CF2CH2C—CH

I

I

228

PAUL TARRANT

and 1,1,2,2,5,5,6,6-octafluorospiro[3,3]heptane, CH2

/

CF2

\ /

\

C

CF2

\

CF2

/ \ CF2

/ CH2

Two isomeric 1:1 adducts are obtained from 2-halo-l,3-butadienes. For example, the following are obtained from 2-fluoro-1,3-butadiene: CF2—CH2

I

CF2—CH2

I

I

I

C F 2— C — C H = C H 2

C F 2— C — C F = C H 2

I

I

F H A variety of products is also obtained from compounds containing both a double bond and a triple bond. Vinylacetylene cah form simple addition products in which either the ethylene or the acetylene bonds are involved, such as CF2—CH2

CF2—CH

I

II

II

C F 2— C H — C = C H C F 2— C — C H = C H 2 I II The compound represented by structure II can then react with a second tetrafluoroethylene to give a bicyclic compound, CF 2—CH

C H 2— C F 2

CF 2—C

CH—CF2

I

A fourth product,

I!

CF2

I

I

I

CH2

I

CF2—CH—CeH 5 can be accounted for by assuming that the vinylacetylene dimerized to give stryene, which then reacted with the fluoroolefin. In general, the fluorocyclobutane ring retains its structure during a number of reactions. For example, 2,2,3,3,-tetrafluorocyclobutane carboxylic acid is readily obtained either by the acid hydrolysis of the nitrile or by oxidation of the 1-vinyl derivative. Recently, however, Barney, and Cairns reported (14) that the basic hydrolysis of the nitrile splits the ring to give á,á-difluoroglutaric acid. They showed, furthermore, that trifluorochloroethylene, water, and acrylonitrile also gave the same compound. For these unusual reactions, the following mechanism was proposed :

ORGANIC COMPOUNDS CONTAINING FLUORINE

C H 2= C H C N

C F 2= CFC1

• CF 2—CFC1

H 20

> CF 2—CFC1

I

CH 2—CH—CN

I

H 20

I

CH 2—CH—COOH

C F 2— C = 0

I

229

I

H 20

> CF 2—COOH

I

CH 2—CHCOOH CH 2CH 2COOH Alcohols The method of preparing an alcohol containing fluorine generally depends upon the number of atoms of fluorine desired in the molecule. If a single fluorine atom is needed, the preparation may be carried out from a halohydrin or epoxy compound by reaction with hydrogen fluoride or potassium fluoride ; the preparation of alcohols containing the trifluoromethyl group generally begins with trifluoroacetic acid. Knunyants and his colleagues have been able to form fluoroalkanols from the epoxy compounds and hydrogen fluoride by using diethyl ether as the diluent (272). In this manner, they obtained a 40% yield of fluoroethanol and a 56% yield of C H 2F C H O H C H 3; epifluorohydrin gave a 40% yield of C H 2F C H O H C H 2F . These investigators claim that the reaction of ethylene chlorohydrin with potassium fluoride is in reality a. reaction of this type since it proceeds in two stages as shown: CH 2C1CH 20H + K F —* C H 2C H 2 + KC1 + H F \ / Ď C H 2— C H 2 + H F -> C H 2F C H 2O H / \ Ď They base their ideas on the fact that CH 2C1CH 20H when refluxed with potassium fluoride gave a 90% yield of ethylene oxide. Saunders et al. used the chlorohydrin to give a 42% yield of fluoroethanol, but Gryszkiewicz-Trochimowski preferred to react the acetates (159, 423). It should be noted that fluoroethanol is quite toxic and, in its action, comparable to a-fluoroacetates. Difluoroethanol was obtained first by Swarts by the reaction of 2,2-difluoro-l-bromoethane with mercuric oxide and water (480). More recent practice is to reduce ethyl difluoroacetate with lithium aluminum hydride. Trifluoroethanol has been prepared by the reaction of 1,1,1-trifluoro2-chloroethane with potassium acetate and hydrolysis of the resulting ester; the use of potassium hydroxide in this reaction gives much lower yields due, undoubtedly, to the formation of C F 2= C H C 1 as a by-product. Most investigators, however, prefer to reduce a derivative of trifluoro-

230

PAUL TARRANT

acetic acid. Campbell et al. found the most convenient method of prepara­ tion of trifluoroethanol to consist of the reduction of butyl trifluoroacetate with lithium aluminum hydride; using this procedure, they obtained a 76% yield of alcohol (58). Trifluoroethanol is much more acidic than ethanol, as might be expected, and does not undergo many of the characteristic alcohol reac­ tions (58). It does not react with concentrated sulfuric acid at 200° nor does p-toluenesulfonyl chloride convert it to the ether. Campbell et al. were not able to convert the alcohol to trifluoroethyl bromide by treat­ ment with phosphorus pentabromide. The Grignard reaction is useful in the preparation of a number of compounds containing the trifluoromethyl group. Ethyl trifluoroacetate CH3 and methylmagnesium bromide give good yields of CH 3—C—CF 3,

Τ

H although some investigators have preferred to use higher esters. Unfor­ tunately, this method is not applicable to the preparation of long-chain tertiary alcohols because the use of larger Grignard reagents lead to the formation of secondary alcohols. Thus, n-propylmagnesium bromide gave a 74% yield of C F 3C H O H C H 2C H 3; n-hexylmagnesium bromide gave similar results, and in neither case could any tertiary alcohol be found. Campbell et al. have shown that the secondary carbinol is formed by the reduction of the intermediate ketone CF 3COR which is formed when one molecule of Grignard reagent reacts with ethyl trifluoroacetate : MgBr Ď

Ď II

CF3C—C3H7

η—C3H7MgBr

|

> CH3—C—C3H7 -f- C 3He 1

H They were able to isolate the ketone and to convert it to the alcohol by treatment with an excess of Grignard reagent (58). R 1 I Although dehydration of alcohols of the type CF 3—C—R is generι ο

Ç CH3

I

ally difficult, Swarts treated CF 3—C—CH 3 with phosphorus pentaOH

ORGANIC COMPOUNDS CONTAINING

231

FLUORINE

bromide and obtained some of the olefin, while Henne obtained a good yield using phosphorus pentoxide at 130° with careful heating (209). The secondary alcohols l,l,l-trifluoro-2-octanol was found to be more resistant since it was not dehydrated when heated with potassium acid sulfate, concentrated sulfuric acid, 8 5 % phosphoric acid, or phosphorus pentoxide at 235° (58). Vapor phase dehydration over activated alumi­ num at 350° gave only lower molecular weight decomposition products; the methyl xanthate derivative could be distilled at atmospheric pressure with but slight decomposition. Finally, the carbinol was converted to the olefin in 6 5 % yield by pyrolysis of the acetate over glass wool at 500°; at temperatures sufficient to crack other molecules, the trifluoromethyl carbinol was recovered. McBee and Truchan made use of the Grignard reagents from 1,1,1trifluoro-3-chloropropane for the preparation of the primary alcohol 3,3,3-trifluoropropanol, while the secondary alcohol 1,1,1-trifluoropropanol-2 has been made in very good yield by the catalytic reduction of trifluoroacetone (338). A number of papers have appeared describing the use of ra-trifluoromethylphenylmagnesium bromide in preparing alcohols containing the m-trifluoromethylphenyl group. In some cases, these compounds were prepared for conversion to trifluoromethylstyrene (4). Szmont, Anzenberger, and Hartle added the Grignard reagent to formaldehyde, ethylene oxide, propylene oxide, and epichlorohydrin to give the expected alcohols (511). With propylene oxide, however, there was formed a mixture of the secondary and primary alcohols: CF3

CF3

C H 2C H O H C H 3

CH

\ CH2OH

-7Swarts has reported the ionization constant of C H C H O H C F to be 3 3 1 0 which indicates this alcohol is more acidic than phenol21(509). Recent data by Henne and Pelley (198) give a value of 6 X 10 for this com­ pound with similar values for C F 3C H 2O H and C F 3C ( C H 3) 2 0 H , thus 4 a trifluoromethyl group adjacent to the indicating compounds containing carbinDl group are about 10 times more acidic than ethanol. McBee, Marzluff, and Pierce prepared a number of diols of the type H O C H 2 ( C F 2) nC H 2O H by reduction of the ethyl esters of perfluoro acids with lithium aluminum hydride and determined their ionization constants (332). They, too, found that these compounds were not as acidic as might

232

PAUL TARRANT

1 3 values for the ionization constant for tri­ have been anticipated. Their fluoroethanol was 5 X 10~ . The values for the first and second ioniza­ tion constants for two diols are: 13 14 HOCH CF CF CH OH 7.9 X 10" 13 2 Χ 10" 13 2 2 2 2 HOCH CF CF CF CF CH OH 7 . 9 Χ 10" 5 X 10~ 2 2 2 2 2 2 Ethers The study of ethers containing fluorine has received a great deal of attention, especially in the last several years. There are probably two reasons for this interest in fluoro ethers: first, many can be conveniently prepared from simple fluorine compounds commonly available; second, the products formed in these reactions are sometimes quite reactive and may lead to other classes of compounds of interest in synthetic chemistry. The fluoro ethers are generally made by the reaction of a saturated fluorohalo compound or by the addition of an alcohol to a fluoroolefin. The latter method has been extensively investigated in the past five years. Swarts in 1899 first prepared an ether containing fluorine by the reac­ tion of l,l,2-trifluoro-l,2-dibromoethane with potassium ethylate; he continued his studies of the reaction of other fluorohaloethanes and reported the formation of â,â-difluoro ethers from the reaction of CHF 2— CH 2Br and sodium ethylate in 1901, and later made C H 2B r C F 2O C 2H 6 and C H B r 2C F 2O C 2H 5 (475). In 1940 Gowland extended this method to include fluorochloro compounds by preparing ethers of the type CHC1 2CF2OR from CHC1 2CF 2C1 (155). McBee and Bolt later used sodium aryloxides to react with CHC1 2CF 2C1, CH 2C1CF 2C1, and CF3CHCICF3 to yield aromatic ethers in good yields (316, 317, 318). They noted that the chlorine of the —CF 2C1 group was apparently displaced in preference to the supposedly more reactive chlorine of the —CH 2C1 or —CHC1 2 groups. The olefin-alcohol addition method was first employed in 1946 by Hanford and Rigby, who added a number of alcohols to C F 2= C F 2 to give tetrafluoroethyl alkyl ethers; C F 2= C F C 1 and C F 2= C H C 1 were reacted with ethanol to give the α,α-difluoro ethers in good yield (170). Miller et al.y in reporting the addition of methanol to several fluoroolefins, postulated the following mechanism for the base catalyzed addi­ tion of alcohols to fluoroolefins (346) : F

F \

/

C=C

F \

/

-» ( + ) C—C ( - )

RO-

\

• ROC—C

/

F ROH

\

/

> ROC—CH

ORGANIC COMPOUNDS CONTAINING FLUORINE

233

Somewhat later Park and others showed that C F 2= C F C 1 reacted with a series of alcohols to give the corresponding ethers, CHFC1CF 20R, in good yield by simply passing the fluoroolefin through a solution of alcoholic potassium hydroxide in glass equipment (369). Since then, many alcohols have been added to C F 2= C F 2, C F 2= C C 1 2, C F 2= C H F , and C F 2= C H C 1 , and in all cases, the alkoxide group has added to the carbon atom having the greater number of fluorine atoms (367). It has also been reported that phenols add readily to fluoroolefins, and a number of phenyl and cresyl ethers have been made by this method (513). Although the saturated ethers are generally formed in greatest yield by the reaction of a fluoroolefin and alcohol, in some cases vinyl ethers, ortho esters, and even acids result. For example, when Ł-butyl alcohol adds to C F 2= C C 1 2 at 100°, the principal product is ( C H 3) 3C 0 C F = C C 1 2 (512). Hexafluorocyclobutene does not give the saturated cyclobutyl ether as expected (365). Instead, there was formed a diether of the type: CF 2—C—OR

I II

CF 2—C—OR Later, Barr et al. reported that the monoalkoxycyclobutene, CF 2—CF

I II

CF 2—C—OR could be obtained by reacting the butene with alcohols in the presence of a quaternary ammonium base (15). Park et al. showed that CF 2CF 2CC1=CC1 reacted to give the monoether, CF 2—CCI

I

, with a number of alcohols. There was also obtained

II

CF 2—C—OR a triether having the empirical formula C4F 2C1(0R) 3. Although definite proof of structure of the triethers is lacking, it is believed that the formula RO \

c—C—CI /

RO F 2C—C—OR may account satisfactorily for its properties (368). Ordinarily, it has been assumed that compounds containing the — C F 2— group are stable and unreactive. This has not been found to be

234

PAUL TARRANT

the case always with the fluoro ethers. For example, ethers such as CHF2CF2OR and CHFCICF2OR are readily attacked by concentrated sulfuric acid and the á-fluorine atoms replaced by oxygen to yield difluoroand fluorochloroacetates; this reaction has become a convenient method for the synthesis of derivatives of haloacetic acids (554, 555). Ethers containing more than one hydrogen atom in the beta position are even more reactive; C H 2C 1 C F 2 0 C 2H 5 hydrolyzes even in water and C H 3C F 2OC2HB is apparently too reactive for isolation under ordinary circum­ stances, since attempts to prepare it from CH 3CF 2C1 and sodium ethoxide gave only ethyl acetate (556). The thermal stability of fluoro ethers depends a great deal on the alkyl group containing no halogen. Methyl, ethyl, and propyl difluoroethyl ethers can be readily distilled without decomposing, but branched chain alkyl ethers are not so stable. For example, isopropyl a-difluoroâ-dichloroethyl ether gives both isopropyl fluoride and dichloroacetyl fluoride upon distillation at atmospheric pressure; the ß-butyl ether from C F 2= C F C 1 gives ß-butyl fluoride, isobutylene, and chlorofluoroacetic acid (512). Polyfluoroalkyl ethers of the type formed by the addition of alcohols to trifluorochloroethylene are generally more stable than the chloroalkyl ethers (385). These fluoro compounds do not react with Grignard re­ agents, nor could they be converted to Grignard reagents themselves. However, they react with aluminum chloride to give alkyl and acyl halides. Chlorination of such ethers occurs in the presence of ultraviolet light, and the chlorine enters the alkyl chain which contains no fluorine. The chlorinated compounds are very stable both chemically and ther­ mally. They are not soluble in concentrated sulfuric acid, and thus do not hydrolyze in the normal manner to the halo esters. Park, Sharrah, and Lâcher have shown that the fluorocyclobutene diethers react with alkaline permanganate to yield diethyl tetrafluorosuccinate in 80% yield. The monoalkoxypentafluorocyclobutenes can be oxidized by the same reagent, but the resulting compound is generally tetrafluorosuccinic acid rather than the ester. Recently the idea has been presented that the reactions of saturated fluorochloro compounds with alkoxides to yield fluoro ethers is not a simple displacement reaction of the Williamson type, but that fluoroolefins are first formed which then add a molecule of alcohol to yield the ether (556). For example, it has been found that CHF 2CC1 3and C H F 2CHFC1 give C H C 1 2C F 20 C 2H 5 and C H 2C 1 C F 20 C 2H 5 when treated with sodium ethoxide and alcohol. It is difficult to account for their formation by any mechanism except that involving olefin intermediates,

ORGANIC COMPOUNDS CONTAINING FLUORINE -OR

CHF 2CC1 3

235

HOR

> C F 2= C C 1 2 -OR

> CHC1 2CF 20R HOR

CHF 2CHFC1

> C F 2= C H C 1 > CH 2C1CF 20R It is known, of course, that saturated compounds of this type can give olefins readily and such products are quite reactive under dehydrohalogenation conditions. Even with CF 3CH 2Br it is difficult to replace the bromine to yield C F 3C H 2O C 2H 5; in spite of the inertness of the methforyl group, a fluorine is eliminated to yield C F 2= C H B r which reacts normally to give CH 2BrCF 2OC 2H 5. In these cases, the base attacks a hydrogen atom adjacent to the cluster of fluorine atoms to form HX, leaving the reactive olefins. It has recently been shown that alcohols will add to hexafluoro2-butyne (63). For example, ethanol gave both C F 3C ( O C 2H 5) = C H C F 3 and C F 3C ( O C 2H 5) 2C H 2C F 3 while CH 2OHCH 2OH gave C F 3C H = CF3

I

C(CF 3)OC 2H 4OH and CF 3CH 2C—OCH 2.

I

I

Ď CH2 Fluoroacrylonitriles and acrylates have also been shown to form ethers with alcohols (60). Ethanol adds to CF 2=CC1CN and to C F 2= CFCN to give C 2H 50CF 2CHC1CN and C 2H 5O C F 2C H F C N , respectively; the acrylates react in an analogous manner. Aldehydes and Ketones The literature dealing with aliphatic aldehydes containing fluorine is relatively meager. The preparation of aromatic aldehydes is a rather simple task, since it is only necessary to introduce the fluorine atom into the nucleus of a ring containing a methyl side chain and subsequently to convert it to the aldehyde group, or to begin with an amino aldehyde and replace the — N H 2 by a diazotization in hydrofluoric acid or by the Schiemann reaction. The number of times these operations have been carried out may be determined by an inspection of the table at the end of the chapter. In the aliphatic series, however, these simple synthetic methods are not applicable and, as a result, research on this class of compounds has been neglected until recently. As late as 1944 it was stated that "fluorinated aldehydes are unknown" (180). In 1950, Henne and coworkers prepared CF 3CHO by the reduction of trifluoroacetonitrile with lithium aluminum hydride, while Skechter and Conrad obtained the aldehyde by the reaction of C F 3C H 2C H 3 with nitric acid and oxygen at about 450°.

236

PAUL TARRANT

Fluoral boils at about —18°, dissolves slowly in water, and forms a hydrate. Fluoral forms a polymer which, upon heating, decomposes readily into the aldehyde. It is oxidized by Tollens reagent and gives fluoroform when treated with a strong base. Phenylmagnesium bromide reacted with it to give a compound which was oxidized to trifluoroacetophenone. Aldehydes containing a methforyl group not adjacent to the carbonyl group may be made by conventional means when the proper starting materials are available. For example, CF 3CH 2CHO has been made by the dichromate oxidation of CF 3CH 2CH 2OH, while C F ?C H 2C H 2C H O was prepared by reacting CF 3CH 2CH 2MgCl with ethyl orthoformate (199, 330). Ketones containing fluorine have received somewhat more attention than aldehydes, quite possibly because of the ease with which trifluoro­ methyl ketones can be made from the commercially available trifluoroacetic acid. S warts in 1926 showed that ethyl acetate could be made to undergo the Claisen condensation with ethyl trifluoroacetate to yield C F 3C O C H 2C 0 2C 2H 5, which gave CF 3COCH 3 by decomposition with sulfuric acid. In 1947, Henne and coworkers obtained CF 3COCH 2COC 2H 6 by the Claisen reaction in improved yields by making use of the insoluble copper chelate to isolate the product (197). The reaction was extended to include the condensation of ketones with ethyl trifluoroacetate, with CF 3COCH 2COCH 3 and CF 3COCH 2COCF 3 being obtained from acetone and trifluoroacetone, respectively. Ethyl difluoroacetate condensed with ethyl acetate to give C H F 2C O C H 2C 0 2C 2H 5; the difluoroacetate would not condense with itself nor with ethyl trifluoroacetate when sodium ethoxide was employed as the condensing agent. Although trifluoroacetone has thus been available in reasonable amounts only since 1948 or 1949, it has been used in several interesting syntheses. For example, a recent patent claims that trifluoromethylbutadiene may be synthesized by the following reactions (218). CF3 MgS0

I

C H = C M g B r + CF3COCH3-» C H = C — C — C H 3

I

4 >

ο

Ç CF3

I

[H]

CF3

I

C H = C — C = C H 2— * C H 2= C H — C = C H 2 Trifluoroacetone readily forms a cyanohydrin when treated with sodium cyanide-and sulfuric acid (81). Treatment of the cyanohydrin

ORGANIC COMPOUNDS CONTAINING FLUORINE

237

with alcoholic ammonium sulfide gives a-hydroxy-a-trifluoromethylthiopropionamide which can be hydrolyzed with dilute acid to give a-hydroxyá-trifluoromethylpropionic acid. Although the patent literature (100) claims that the cyanohydrin can be dehydrated with thionyl chloride and pyridine, Darrall et al. reported no evidence of unsaturated products with acetic anhydride, sulfuric acid, or phosphorus pentoxide (81). Since then, a number of 0-diketones have been prepared by condensing various methyl ketones with ethyl trifluoroacetate (392). Such compounds are of great interest because of the fact that they form insoluble chelates with a number of the heavier metal ions. Thenoyltrifluoroacetone

has been investigated as a complexing agent for the separation and puri­ fication of various metallic ions such as aluminum, beryllium, cobalt, copper, iron, zinc, yttrium, zirconium, and hafnium. It has certain ad­ vantages, such as stability at lower pH's and the formation of chelates which may be sublimed under vacuum yet are not too volatile at atmos­ pheric pressures (39). Ketones containing two trifluoromethyl groups have been reported (330). Ethyl carbonate gave an 18% yield of l,l,l,7,7,7-hexafluoro-4heptanone with CF3CH 2CH 2MgCl; l,l,l,5,5,5-hexafluoro-2-pentanone re­ sulted when this Grignard reagent reacted with trifluoroacetonitrile. A halogen exchange reaction is rarely used for the preparation of fluoro ketones although monofluoroacetone has been prepared by the reaction of bromoacetone with thallium fluoride (387). The preparation of aromatic ketones containing fluorine has been confined chiefly to those prepared by the reaction of benzene and a suit­ able acid chloride in the presence of aluminum chloride. Simons and Ramier were the first to prepare trifluoroacetophenone, using this method. This ketone undergoes the haloform reaction with strong bases, forms an insoluble sodium bisulfite addition product, and reacts with PCU to form the dichloride, but fails to form a cyanohydrin. Cohen et al. prepared trifluoro-, difluorochloro-, and difluoroacetophenone as intermediates for the preparation of substituted styrenes; trifluoroacetyl chloride gave a 6 1 % yield of ketone with diphenylcadmium (73). Jones has made use of organometallic derivatives of benzyl chloride to react with CF 3CN and CF 3COCl to give trifluoromethyl ketones (262). I t was first thought that benzyl trifluoromethyl ketones had been pro­ duced, but later work by Nes and Burger showed that the benzylmetallic derivatives rearranged and that o-methylphenyl trifluoromethyl ketone

238

PAUL TARRANT

resulted. The benzyl ketone was obtained by Nes and Burger by the following sequence: H +

C 6H 6C H 2C N + C F 3C 0 2C 2H 6^ C eH 6CH(CN)COCF 3 —• H-h

C 6H 6C H ( C O C F 3) C O N H 2^ C 6H 6C H 2C O C F 3 Its structure was established unequivocably by alkaline cleavage to phenylacetic acid (354). Acids and Their Derivatives The preparation of acids containing fluorine has been accomplished by perhaps the most varied procedures of any class of organic compounds. In most cases, however, carboxylic acids themselves have not been used as the starting point. The simplest organic acid containing fluorine, CH 2FCOOH, was prepared by Swarts in 1896 by reacting methyl iodoacetate with silver fluoride at 170° in a platinum vessel and saponifying the fluoroester with barium hydroxide. Since that time, numerous methods of preparing the acid or one of its derivatives have been described. For example, the ethyl ester has been prepared by heating the haloacetate with thallous fluoride (388) or with potassium fluoride (421); the amide resulted when chloroacetamide was heated with K F under reduced pressure (7) ; and oxidation of fluoroethanol gave the acid (491). Considerable interest has been shown in the preparation of derivatives of fluoroacetic acid because of their physiological properties, and, as a result, the literature since World War II contains many references to these compounds. The ethyl ester of á-fluoropropionic acid has been prepared by heating the á-chloropropionate with anhydrous potassium fluoride while â-fluoropropionic acid has been made by the oxidation of C H 2F C H 2C H 2O H with potassium dichromate and sulfuric acid (160). 4-Fluorobutanol gave 7-fluorobutyric acid which decomposed to butyrolactone unless distilled under reduced pressure. The reaction of the esters of halo acids with silver fluoride has been used to prepare a number of carboxylic acids or their derivatives contain­ ing a,fluoromethyl group at the end of a long aliphatic chain (54). For example, C H 2I C H 2C H 2C H 2C 0 2C 2H 6 and AgF gave a small amount of 5-fluorohexanoic acid; in a similar manner, acids containing from 6 to 12 carbon atoms were prepared. Interestingly enough, in compounds of the type F ( C H 2) nC 0 2R , it has been demonstrated that if η is odd, the compound is toxic and causes fluoroacetate symptoms in animals; when η is even, the compounds exhibit no such toxic properties.

ORGANIC COMPOUNDS CONTAINING FLUORINE

239

Difluoroacetic acid is not nearly so readily available as trifluoroacetic acid and, consequently, has not been studied to the same extent. How­ ever, some interesting syntheses have been developed : difluoroacetic acid or derivatives have been prepared by the oxidation of C H F 2C H = C C 1 2, by the hydrolysis of 2,4,6-tris(difluoromethyl)-triazine (67), or from CHF 2CF 2C1 (Fréon 124A) by the following synthesis (555) : Ď H S0

Na

CHF 2CF 2C1 + ROH —> R O C F 2C F 2H

II

2 4 > ROC—CHF 2

α,α-Difluoropropionic acid, C H 3C F 2C 0 2H , has been made by alkaline oxidation of C H 3C F 2C C 1 = C H 2 and α,α-difluorobutyric acid from C H 3C H 2C F 2C H = C H 2 (215). 0-Fluoro acids could not be made by the same procedure because the basic solution caused the loss of hydrogen fluoride to give C F 2= C H C 0 2H and C H 3C F = C H C 0 2H instead of C F 3C H 2C 0 2H and C H 3C F 2C H 2C 0 2H , respectively. 0-Difluoro esters such as C H 3C F 2C H 2C 0 2C 2H 6 could be made by adding hydrogen fluoride to C H 3C = C C 0 2C 2H 6, but saponification gave the unsaturated acid. Attempts to prepare CHF 2CH 2COOH by adding hydrogen fluoride to CH==CC0 2H or its ester led only to resin formation. I t should be noted the â-fluoro acids resemble â-hydroxy acids in the ease in which unsaturates are formed. In â-difluoro acids, this activity should be increased because of the additional inductive effect of the — C F 2— which makes the α-hydrogen more mobile: F

I

H

O

I I

R—C<-C -> C—OR'

II

F

I ·

Ď

Ď

Il

II

R—C—C—C—OR -> R—C=C—C—OR

I I

I

F H F H F H Kharasch has recently reported the preparation of difluorosuccinic acid, HOOCCHFCHFCOOH, by thé decomposition of peroxides influoroacetic acid (264). It is interesting to observe that the acid, containing two â-fluorine atoms, is extremely reactive even with water and imme­ diately forms the acetylenic dicarboxylic acid. The preparation of acids containing a difluoro group in the gamma position proved difficult. Henne and Zimmerschied attempted to prepare C H 3C F 2C H 2C H 2C N from CH 3CF 2CH 2CH 2C1 and sodium cyanide, but this combination led only to C H 3C F 2C H = C H 2. 5-Chloro-2,2-difluoropentane, CH 3CF 2CH 2CH 2CH 2C1, was next prepared for conversion to C H 3C F 2C H 2C H 2C H 2O H which would presumably give a gamma acid on oxidation; however, reaction with the solvent led to the formation of ethers, C H ?C F 2C H 2C H 2C H 2O C 4H 9, rather than the alcohol.

240

paul

tarrant

The reaction of the chlorodifluoropentane took place with sodium cyanide to give CH3CF2CH2CH2CH2CN, from which the ä-difluoro acid was obtained. Acids containing the two fluorine atoms on the same carbon further removed from the carboxyl group have also been prepared. For example, hydrogen fluoride may be added to an acetylenic compound containing either the nitrile group or a chlorine atom in a suitable position to react with sodium cyanide. Of the two routes, the former proved better for the preparation of 5,5- and 6,6-difluorodecanenitriles (358). The nitriles were then converted to the acids by hydrolysis. Acids containing the trifluoromethyl group have been made by the Grignard reaction. McBee and Truchan prepared CF3CH2CH2CO2H and CF3CH2CH2CO2C2H5 by the reaction of CF,CH 2CH 2MgCl with C 0 2and ethyl chlorocarbonate (338). Since the Grignard reagent has not been made from CF 3CH 2Br, this method is only useful for the preparation of 7-fluoro acids or those in which the fluorine is further from the carboxyl group. Potassium fluoride has proved effective in replacing the halogen atoms in various esters (162). The reaction must be carried out with finely powdered, anhydrous K F at 150-250° and with good agitation; under these conditions, yields of 20-50% are usually obtained. The esters of á-chloropropionic and chloromalonic acid give the fluoro derivative but in poorer yield than ethyl chloroacetate. Compounds such as methyl dichloroacetate which have two halogen atoms on the same carbon react to give difluoroesters. Special syntheses have been worked out for the preparation of specific derivatives. For instance, the reactivity of fluorine atoms alpha to an ether linkage is made use of to prepare esters of fluorochloroacetic acid from the easily obtainable C F 2= C F C 1 : C F C 1 = C F 2 + ROH -> CHFCICF2OR

H 2S O . > CHFCICO2R

Amides may be prepared in a one-step reaction from fluoroolefins in good yields (119, 399): H 0 2 C F 2= C F 2 + H 2N R > CHF2CONHR The use of chlorotrifluoroethylene gives a mixture of amides, as amines will add to either carbon of the double bond : C F C 1 = C F 2 + H 2N R -> CHF 2CONHR + CHFC1CONHR In the absence of water, reactive intermediates have been isolated by Pruett et al. For example, they were able to isolate and characterize

ORGANIC COMPOUNDS CONTAINING

241

FLUORINE

N-n-butyl-a-chloro-a-fluoroacetimidyl fluoride (I) and Í,Í'-di-n-butylá-chloro-a-fluoroacetamidine (II) and propose the following mechanism for the addition of amines to olefins (377a).

n-CH,NH + CFC1=CF2-+ 4

NC H 4

2

9

S

II

CHFC1C

[CHFC1CF2NHC4H9] I

n-C HtNH,

4

\rHC H 4

<

1

CHFC1CF=NC4H9

|H,0 Ď CHFClè—NHCH

9

4

I

9

In al l case s excep t wit h amines , th e additio n o f anioni c reagent s t o unsymmetrical fluoroolefins suc h a s C F 2= C F C 1 give s a singl e product . With amines , onl y on eproduc t i sobtaine d i f th ereactio n i scarrie d ou t a t room temperatur e ; however , a t highe r temperatures , a mixtur e o f difluor o and fluorochloro product s ar e obtained . Acid chloride s hav e bee n mad e b yoxidizin g a halocarbo n olefin . Whe n CF 2C1CC1=CC1 2 wa s irradiate d wit h a mercur y vapo r lam p whil e oxygen an d chlorin e i n a ratio n o f 10: 1wer epasse d i nfo r2 0hours , a con siderable amoun t o f CF 2C1CC1 2C0C1 resulted . Thi s reactio n i sth e start ing poin t fo r th e preparatio n o f fluoroacrylonitriles (59 ,61 ,62 , 64) .

Ď

CF 2C1CC1=CC1 2-> CF 2C1CC1 2C0C1

NH3

> CF 2C1CC1 2C0NH 2

P 20 6 >

Zn

CF 2C1CC1 2CN -» C F 2= C C 1 C N If CF 2C1CF=CC1 2 is thus oxidized, both CF 2C1CFC1C0C1 and CF 2C1CC1 2C0F are formed. Fluoroacetonitrile has been obtained from the corresponding chloro compound by treatment with AgF, H g F 2, or C d F 2; however, yields were low. Because of the ease with which one acid derivative may be converted to another, fluoroacetonitrile may be made from the amide in good over-all yield from chloroacetamide in a two-step reaction (7).

KF

PO 2

e

CH 2C1CC0NH 2 —> C H 2F C O N H 2 • C H 2F C N The reaction between hydrocyanic acid and trifluoroacetone has CF3 produced á-trifluoromethyl-a-hydroxypropionic acid, C H 3— C — C 0 2H ,

i

Ç which has unusual properties. I t differs from ordinary á-hydroxy acids in its reluctance to form the lactide, and it is difficult to dehydrate

242

PAUL TARRANT

(81). A recent patent claims that the nitrile can be dehydrated to yield CF3

I

C H 2= C — C N , which should be of real interest to the polymer chemist (100). The preparation of fluorocarbon acids by the oxidation of olefinic compounds has been reported by numerous investigators. Tetrafluorosuccinic acid can be made conveniently from available starting materials as follows: Zn

KMnO<

C F 2= C C 1 2 -* CF 2—CC1 2 -> CF 2—CCI

I

I

I

CF 2—CC1 2

II

CF 2—CCI

> C 0 2H

I

CF2

I

CF2

I

C 0 2H Recently, an unusual reaction has led to the formation of á,á-difluoroglutaric acid (14). H 20 C H 2= C H C N + C F 2= C F C l > H 0 2C C H 2C H 2C F 2C 0 2H 150°

The suggested mechanism for this reaction has been shown in the section on cyclobutane derivatives. Amines â-Fluoroethylamine has been prepared by adding â-aminoethylsulfonitrosaminic acid, H 2N C H 2C H 2N ( N O ) S 0 2H , to cold 40% hydrofluoric acid (521). In 1904, Swarts prepared 0,0-difluoroethylamines by heating l,l-difluoro-2-bromoethane with alcoholic ammonia. The primary amine, C H F 2C H 2N H 2, is miscible with water and absorbs carbon dioxide (481). The secondary amine, ( C H F 2C H 2) 2N H , reacts with nitrous acid to give the nitrosoamine. Some tertiary amine, ( C H F 2C H 2) 2N C 2H 5, was also formed, presumably by some alcohol taking part in the reaction; it was reported to be insoluble in water and only slightly basic (482). Gilman and Jones prepared trifluoroe thy lamine, C F 3C H 2N H 2, by hydrogenating the nitrile (149). As a general rule, trifluoromethyl com­ pounds have a lower boiling point than the nonfluorinated analogs, as is illustrated in the extreme case by the trifluoroacetonitrile, which boils 145° lower than acetonitrile ; however, trifluoroethylamine boils at 47° or

ORGANIC COMPOUNDS CONTAINING FLUORINE

243

21° higher than its hydrocarbon analog. Trifluoroisopropylamine also boils higher than isopropylamine. Trifluoroethylamine is a very weak base. It reacts with nitrous acid to yield the diazo compound, C F 3C H N 2, which is rapidly decomposed by acids and reacts with iodine to yield diiodotrifluoroethane, C F 3C H I 2. The reaction with nitrous acid is another example of the similarity of the — C F 3 group to the carbonyl since the only aliphatic amines previously reported to give diazo compounds are of the type RCHNH 2COX. Amines containing fluorine next to the primary amine group have not been reported. It is to be expected that such compounds would give nitriles: X C F 2C F 2N H 2 -> X C F 2C N + 2HF. A closely related compound, CHFC1CF 2N(C 2H 5) 2, has been obtained from the reaction of C F 2= C F C 1 and ethyl amine (377a). This tertiary amine reacted vigorously with water, alcohols, and other amines; the reaction with water was quantitative, producing two moles of hydrogen fluoride and one mole of N,N-diethyl-a-fluoro-a-chloroacetamide for each mole of amine hydrolyzed. A wide variety of aromatic amines which contain fluorine have been reported; however, they have been made by the usual methods of syn­ thesis and need not be discussed here. I t should be noted that the basicity of heterocyclic compounds is reduced by the introduction of fluorine into the molecule. For instance, McBee, Pierce, and Bolt have reported 2,4,6-tris(methforyl)triazine to be devoid of basic properties (333a). Heterocyclic Compounds As might be expected, heterocyclic compounds containing fluorine have been made by a variety of methods such as the Schiemann reaction, replacement of another halogen with a fluorinating agent, or synthetic methods using a compound already containing fluorine. Perhaps more research has been conducted on pyridine derivatives than on the other heterocyclic compounds. 2-Fluoropyridine has been prepared by the Schiemann method in 34% yield and by diazotization in concentrated hydrofluoric acid in 25% yield; 3-aminopyridine gives the corresponding fluorine compounds in 50% and 22% yields, respectively, by the two methods (33, 65, 408). These compounds were the first pre­ pared by the Schiemann method, and modified techniques were necessary as these fluoroborates decompose spontaneously and with violence at room temperature. Roe et al. (409) were unable to prepare 4-fluoropyridine because of its instability.

244

PAUL TARRANT

Several methylpyridines containing a fluorine atom have been pre­ pared; the corresponding carboxylic acids and amides were prepared since these are related to nicotinic acid and nicotinamide. The modified Schiemann reaction was used to prepare 2-fluoro-3-methylpyridine, 2-fluoro-5-methylpyridine, and 5-fluoro-3-methylpyridine (177, 348). Several derivatives of 2-fluoro-4-methyl- and 2-fluoro-6-methylpyridine have also been recently reported (406). McBee, Hass, and Hodnett prepared a number of pyridine derivatives containing one or two methforyl groups by heating the corresponding trichloromethylpyridines with anhydrous hydrogen fluoride at elevated temperatures. These compounds do not form an insoluble hydrochloride when hydrogen chloride is bubbled through a benzene solution, indicating their lack of basic properties (321). Tris(trichloromethyl)triazine, prepared from trichloroacetonitrile, can be fluorinated about as readily as the corresponding benzene derivative to the tris(methforyl)triazine (333a). These compounds are not basic and appear to affect the upper respiratory system of persons inhaling the compound. Roe and Hawkins have reported the preparation of all the monofluoroquinolines (409). It was found that the 5-, 6-, 7-, and 8-quinolinediazonium fluoroborates, in which the diazonium group is located on the benzene ring, are stable compounds which may be decomposed in the normal manner. Several fluoroisoquinolines have been prepared (410). The 1- and 5-isoquinolinediazonium fluoroborates were stable, whereas the 3- and 4-isomers decomposed at room temperature. The Skraup synthesis has been used to prepare methforylquinolines (152):

Since the yield of the 5-methforyl derivative is greater than 5-methyiquinoline when m-toluidine is used, Pouterman and Girardet interpret this to indicate that the steric hindrance of the methforyl group is much less than for the methyl group (374). A number of 4-amino-, 4-chloro-, and 4-hydroxyquinolines having a fluorine atom or the methforyl group in the 5- and 7-positions have

245

ORGANIC COMPOUNDS CONTAINING FLUORINE

been prepared from either ra-fluoroaniline or ra-aminobenzotrifluoride (352, 453). Wilkinson and Finar have begun a study of fluorine-substituted 5-aminoacridines and related compounds (544). The general method of synthesis which they employed for a number of monofluoro- and trimethforyl-5-aminoacridines is illustrated by the following: NH2

COOH

H

NH2 The monofluoro bases resembled the 5-aminoacridines in physical prop­ erties; the 2-methforyl-5-aminoacridine resembled the corresponding methyl derivative. However, the 4-methforyl compound was highly soluble in most organic solvents and no diacetyl derivative could be obtained. It is postulated that the difficulty may be due to hydrogen bonding between the — N H 2 and — C F 3 (I). H...F AcN CF2

I

H...F O CF2

II

Ď

II

CF3

Ç III

It was hoped that this idea could be substantiated by the behavior of 5-hydroxy-4-methforylacridine (II) ; however, the properties of this sub­ stance so closely resembled that of acridone that it must be formulated as 4-methforylacridone (III). Several 6-fluoroacridines have been pre­ pared by a synthesis somewhat similar to that shown above. Schiemann and Winkelmuller have used p-fluorophenylhydrazine with acetone to give 2-methyl-5-fluoroindole ; with acetoacetic ester, pyrazolones were obtained (439). Activity in preparing thiazole derivatives has been confined chiefly to p-fluorophenyl derivatives. Wetherill and Hann prepared substituted thiazoles as shown

246

PAUL TARRANT

HC— S

\ HS

C 0 C H 2C 1

C—Ν

\

+ F

CR

ΗΝ

and made several derivatives (543). 6',4'-Difluoro-2-anilinobenzothiazole has been prepared by treating bis(4-fluorophenyl)thiourea with bromine followed by the reduction of the hydrotribromide which formed to the thiazole with sulfur dioxide (128). Farooq and Hunter prepared a number of 4'-fluoro-2-anilinobenzothiazole derivatives containing chlorine, bromine, methyl, and nitro substituents in various positions (134). The preparation of 2-fluorothiophene has been reported by Van Fleck by the reaction of 2-iodothiophene with antimony trifluoride (531). Attempts to prepare fluorothiophene from 2-aminothiophene through the fluoroborate were unsuccessful. Stover and Sachanan were successful by the reaction of CF2C1CFC12, 2-chlorol^gJOFClCF^l thiophene and sodium amalgam (459). Amino Acids Research in this field has been confined principally to tyrosine and thyronine derivatives. It is interesting to note that these amino acids are the only ones found in nature with halogen atoms in the aromatic nucleus. The synthesis of 3-fluorotyrosine was accomplished by Schiemann and Winkelmuller (439) in 1932. This compound was the subject of study by Litzka (292a) who reported that it prevented, or greatly inhibited, the depletion of liver and muscle glycogen by thyroxine. It was also reported that daily doses of 1 mg. would slowly lower the blood sugar in chronic cases of hyperthyroidism and diabetes over a long period of time. This compound was also reported to inhibit tumor formation or growth in animals in which carcinoma was induced experimentally (306a). ΐhese reports increased interest in fluorine-containing amino acids and led Niemann and Phillips to begin a study of the synthesis and pharmacological activity of compounds containing fluorine in the aromatic ring. English, Mead, and Niemann (133) reported an improved synthesis of 3-fluorotyrosine by the following reactions:

ORGANIC COMPOUNDS CONTAINING FLUORINE

OCH,

OCH3

OCH,

ç Í Ç 2 _^ N02

247

OCH,

Ď

NH2

OCH,

OCH3

OCH,

CN

CHO

CH=C

Ç Ď

CO

C H 2C H N H 2C 0 2H

CeHô

Iodination of 3-fluoro-DL-tyrosine gave 3-fluoro-5-iodo-DL-tyrosine. 3,5-Difluoro-DL-tyrosine was obtained in a 0.73% over-all yield from o-anisidine in an eight-step process. Several compounds containing fluorine in the benzene nucleus containing the hydroxy group have been described (360). The prepara­ tion of the monofluoro derivatives was accomplished by condensing 4-methoxy-2-fluorophenol with triiodonitrobenzene from which the amino acid was prepared in several steps. The following compounds were prepared:

A later paper (359) gives the procedure for preparing 3',5'-difluoroand 3',5'-diiodothyronine. In 1947 Mitchell and Niemann (349) presented data on inhibition of growth of Neurospora crassa by 3-fluoro-DL-phenylalanine and the 3-fluorotyrosines.

PAUL TARRANT

248

In 1950 Rinderknecht and Niemann (399a) outlined a synthesis for 5-fluoro-DL-tryptophan, which is a particularly interesting compound as a possible metabolic antagonist. Dyes The use of dyes containing fluorine was begun in the 1930's in Ger­ many, and by 1939 more than 100 tons of Naphtol-AS bases were sold. Some typical examples of these bases are :

Fast Orange GGD Fast Golden Orange GR

SO2C2H5

NH2

Fast Scarlet VD

These bases were generally coupled with Naphtol AS to give a molecule such as

fA

CF3 O

C O N H ^

Such dyes gave vivid hues which were resistant to fading by light; the red coloration of the Nazi flag was due to a dye of this type, presumably that shown above. There was considerable activity in preparing acylaminoanthraquinones and acridones with methforyl groups. Indanthrenblue CLB was marketed during the war for use by the Luftwaffe; its formula is:

249

ORGANIC COMPOUNDS CONTAINING FLUORINE

The synthesis of anthraquinones containing methforyl groups is illustrated by the following reactions:

CCI; HF

CI

Ď

I^JCF, Ď Ď CF 3 2

· I

CI +

II

c

FeCl, CF

.COF

CI CI

H3Cl CH 3

H sO

Ď C

CF |T T 3

Y

^ 1 C 1 _ C F 3|

I0 2Cl

Three dyes containing the trifluoroethoxy group showed interesting possibilities when investigated by the Germans; they are: H

1

i

0

0

1

II n

C F 3C H 20 ^ ~ ^ >CONH

1

J I

Ď

NHCO

ll

1 0

0

H

250

PAUL TARRANT

C F 3C H 20

II

0

O C H 2C F 3 Ď

I

C

c

C F 3C H 20 |

IOCH 2CF;3 III

In general, it was found that the exchange of a trifluoroethoxy group for the alkoxy caused the colors to assume a lighter hue. This is particularly noticeable with the dihydroxy dibenzanthrone derivative (II) in which the green color turns blue. The exception is the thioindigo (III) whose color deepens even when changing from orange to scarlet. Several dyestuff bases containing the trifluoroethoxy group for coupling with Napthol OS were prepared ; a typical example is

Beautiful tints were obtained but the resistance of such dyes to the action of soaps was poor. In the United States, the literature on dyes containing fluorine is meager except for patent references (97-106). It was assumed that the introduction of fluorine in the molecule of a dye would invariably induce resistance to oxidation and give a light fast dye. This has not always been the case, as is illustrated by the following examples (107) :

CF;3

ORGANIC COMPOUNDS CONTAINING FLUORINE

251

R

R'

C F 3 or N 0 2 C F 3 II X

R

Y

N02

R'

III

wherein R and R' are alkyl or substituted alkyl groups and X and Y are selected from hydrogen, alkyl, alkoxy, or chlorine. The light fastness properties of dyes from (I) and (II) are no better and in many cases poorer than those from (III). The position of a methforyl group in a particular type of compound has an important effect on the fastness of the molecule as illustrated by the following: X N

°' V7

N=N

I

f c ,

v/\

Y

CF3

_

R

IV

n = n

R' X

_

R

n

O O( I

Y

R'

NOt

V The light fastness properties of dyes from (IV) are invariably markedly superior to those from (V). However, there are other examples in which the position of methforyl and the nitro group must be reversed to give better properties. H /=\ F3Ci

/>N<; s . r x . j

N02 VI

252

PAUL TARRANT

CF3 VII

F3c/\NHN=C

W

0 2N<(

I N02

COCH 2 \

\

/

H

C

/

COCH 2

\R

COCH 2

Ç

VIII

>NHN=C'

\

/

V

COCH 2

\

R

IX

Dyes from both (VI) and (VIII) have very good light fastness, whereas those from (VII) and (IX) are very poor. A scarlet dye of superior quality for use with cellulose acetate has been recently described; it has the formula

CH 2CH 2OH F 3Q C H 2C H 2C N N02 Fluoroethylaminoanthraquinone dyes have been claimed to give light and gas-fast orange to violet shades on Nylon and cellulose acetate (98, 99). For example, l-(2,2,2-trifluoroethylamino)-4-hydroxyanthraquinone has been used to dye cellulose pinkish red. Acetate rayon was dyed a violet-pink with l,4-bis(2,2,2-trifluoroethylamino)anthraquinone. l-(2,2,2-Trifluoroethylamino)-4-bromoanthraquinone gives an orange color on Nylon. The use of the difiuoroethylamino group in the first two examples above gave reddish violet and reddish blue shades, respectively, on Nylon. Azo dyes of the type X R 0 2N ( V / ) N = N i >N C \ /J F \ // \ 3

C 2H 6

R'

ORGANIC COMPOUNDS CONTAINING FLUORINE

253

where R is alkyl, hydroxyalkyl, alkoxyalkyl, cyanoalkyl, or carboalkoxyalkyl, R' is hydroxyalkyl, and X is halogen, hydrogen, or methforyl group, are claimed to have excellent fastness to light, gas fumes, perspira­ tion, and washing. Rubine shades are produced on acetate rayon by the molecule where X is hydrogen, R is ethyl, and R' is 2,3-dihydroxypropyl. Reddish-brown dyes were obtained from diazotized l-amino-2-methforyl-4-nitro-6chlorobenzene and N-substituted 3-ethylanilines. Water-insoluble azo dyes for numerous textile materials have been prepared by coupling a diazotized arylamine with a methforyl-1,2,3,4tetrahydroquinoline or a methforylbenzomorpholine joined to the azo group in the 6-position (109). Unsulfonated material is valuable for cellulose derivatives, whereas the sulfonated dyes are suitable for wool, silk, and rayon. For example, a blue dye, CH 2CHOHCH 2OH

I

Í

is prepared by coupling the diazotized dinitroethylsulfonamide with the hydroquinoline derivative in glacial acetic acid. The corresponding morpholine dye (CH 2 in the 4-position = O) is also blue. Replacement of the methforyl group by hydrogen and the methyl group by methforyl gives a violet color. Drugs Although organic fluorine compounds for use in chemotherapy have not reached the prominence of the other halogen compounds, increasing interest has been shown in the synthesis and testing of such compounds for potential use as antimalarials, anesthetics, antimetabolites, bacteriacides, and other specialized uses. During the years of World War II, an extensive program was under­ taken to find antimalarial drugs to replace quinine which was made unavailable to the Allies by the Japanese invasion of Java. Relatively few compounds containing fluorine were synthesized and screened for anti­ malarial activity; none showed any particular promise (549). Snyder et al. (453) made a number of compounds related to plasmochin, 8-(4-diethylamino-l-methylbutylamino)-6-methoxyquinoline, which

254

PAUL TARRANT

is an antimalarial comparable to quinine in activity. These compounds, 4-(3-diethylaminopropylamino)-6-fluoroquinoline (SN 14884), 4-(4-diethylamino-l-methylacetylamino)-7-fluoro- (SN 13986), and -7-methforyl quinoline (SN 11524) were made by condensing a primary aromatic amine with ethoxymethylenemalonic ester to give a-carbethoxy-0-arylaminoacrylates of the type H C ( C 0 2C 2H 6) 2

Ď

| C 0 2C 2H 6

which were converted to the 4-hydroxyquinolines. These were treated with phosphorus pentachloride and then with the proper amine to give the desired product; somewhat later, Mooradian and Suter (352) used essentially the same reactions to prepare several 3-methyl-4-alkylaminoquinolines with a methforyl group in the 5- and in the 7-positions. The corresponding 5- and 7-fluoroquinolines were also tested. Gilman and his colleagues (152) prepared some heterocyclic compounds, including several quinolines, containing the methforyl group and reported them to be devoid of activity toward ovian malaria. Fluoroacridines are the subject of investigations by Wilkinson and Finar who prepared monofluoro-5-aminoacridines and 4-methforyl-5aminoacridine (544). NH2

NH2

These compounds were examined for antibacterial activity against Staph, aureus, B. coli, and Ps pyocyanea. The only compound which com­ pared favorably with 5-aminoacridine was 2-fluoro-5-amino-10-methylacridinium bromide, which exhibited higher activity against B. coli. Apparently, these compounds were not tested as antimalarials. In 1941, Magidson and Travin (298) prepared several methoxyfluoroacridines including 2-methoxy-6-fluoro-9-(4-diethylaminobutylamino) acridine, which is quite closely related to atabrine, which has a chlorine atom in the 6-position. It was reported that this compound had no therapeutic value. VanderWerf has prepared a potential antimalarial related to atabrine in which the methoxy group of the known drug has been replaced by a

ORGANIC COMPOUNDS CONTAINING FLUORINE

255

fluorine atom. Its activity has apparently not been reported. In another study, the hydroxy group of the antimalarial drug Camoquin was replaced by fluorine to give 2-diethylaminomethyl-4-(7-chloro-4-quinolylamino)fluorobenzene

CI the activity of which was considerably less than that of Camoquin (465). / claimed (22) that compounds such as 4-acetylamino- and It has /been 4-amino-3 ,5 -bis(methforyl)benzenesulfonanilide were suitable for the treatment or prophylaxis of malaria. Fosdick and his collaborators have been interested in the synthesis and pharmacological properties of fluorine compounds related to procaine, diethylaminoethyl p-aminobenzoate, for use in producing anesthesia. In 1941, a study was begun of several alkylaminoalkyl esters of p-fluorobenzoic acid. The anesthetic efficiency of these compounds was equal to, or slightly greater than, that of procaine and all possessed a low toxicity. Unfortunately, tissue irritation was so pronounced that they could not be used for clinical work (142). As it had been shown that the anesthetic efficiency of procaine analogs could be increased from four to six times by the substitution of sulfur for oxygen, Fosdick and Barnes (140) prepared a series of alkyl and alkyl­ aminoalkyl esters of p-fluorothiobenzoic acid. Pharmacological data indicate that these compounds have greater toxicity and no greater anesthetic activity than the compounds which have no sulfur. In a further effort to reduce the irritating effect of fluoroprocaines by introducing the amino group into the benzene ring, Fosdick and Dobbs then made a number of esters of 3-amino-4-fluorobenzoic acid. All the hydrochloride salts were potent topical anesthetics with the exception of the dimethylaminoethyl derivative. The toxicity of the diethylamino­ ethyl compound was approximately one-half that of procaine itself. These compounds produced more irritation than those without fluorine but less than that of the p-fluorobenzoates (143). The esters of 2-nitro- and 2-amino-5-fluorobenzoic acid (141) produced profound anesthesia, lasting in some cases as long as twenty-four hours. All compounds of this type caused considerable irritation and, in some cases, tissue necrosis. In 1939, Suter, Lawson, and Smith (460) made and determined the phenol coefficients of a series of 2-n-alkyl-4-fluorophenols. The values

256

PAUL TARRANT

against B. typhosus reached the maximum with the amyl derivative. The fluorine compounds were more effective than the unsubstituted alkylphenols but were inferior to the chloro and bromo analogs. Mercury compounds were the subject of an investigation by Dunker and colleagues. By replacing the diazonium borofluoride group with freshly reduced mercury, the three isomeric fluorophenyl mercuric chlorides were obtained (117). The synthesis of 4-fluoro-3-chloromercuribenzoic acid and 4-fluoro-2-acetoxymercuriphenol were also reported. The mercuribenzoic acid was the most active compound of the group; in serum dilutions, the presence of fluorine in the benzene ring gave decidedly more antibacterial activity than chlorine in a similar position, but this was not the case for tests with aqueous solutions (116). A series of sulfa drugs containing fluorine were prepared and tested in vitro as antagonists of the, growth of Staphylococcus aureus and Escher­ ichia coli (464). The p-fluorobenzamido and p-fluorobenzenesulfamido derivatives of pyrimidine, pyridine, and thiazole were not so effective as the corresponding amino analogs. N-Sulfanilyl-4-fluoroaniline has been found to be much less effective than sulfanilamide against streptococcus infections in white mice (462). Roe and Fleishmann (407) prepared several isomeric fluorohydroxybiphenyls as potential bacteriacides, but their activity was not indicated. VanderWerf and his coworkers have been active in preparing com­ pounds in which the amino or hydroxy group of a substance of established medicinal value has been replaced by a fluorine atom or the methforyl group. In their first reported work (46), the synthesis of medicinals of the following general types were described: (a) antimalarials; (b) arsenicals; (c) diphenyl sulfones; (d) antiseptics derived from resorcinol; and (e) sulfonanilides. Data were reported for the preparation of an analog of atabrine ; 3,3 -diamino-4,4'-difluoroarsenobenzene, 3-amino- and 3-acetylamino-4-fluorophenylarsonic acids; several 4-fluorophenyl sulfones; 2-acetoxymercuri-5-fluorophenol and two isomeric s-amyl-5-fluorophenols 4 as resorcinol derivatives; 3,3 -bis(4-fluorophenyl)phthalide as an isosteric phenolphthalein; and p-fluoro derivatives of N -succinylsulfanilanilide and 4-succinimidobenzenesulfonanilide. Another study (288) was made of compounds in which the methforyl group and the fluorine atom, substituted at the various positions in the phenyl group, replace the methyl group in the central depressant 3-(2methylphenoxy)propane-l,2-diol(Myanesin). These 2-fluoro-, 3-fluoro-, and 4-fluorophenyl compounds were less effective than Myanesin; how­ ever, the analogous methforyl compounds were extremely effective, par­ ticularly when the CF 3— group was in the 3-position. The a,7-disubsti-

ORGANIC COMPOUNDS CONTAINING FLUORINE

257

tuted ethers showed insignificant paralyzing action. The toxicity of these compounds was comparable to the corresponding chloro or bromo derivatives. Pressor amines containing fluorine have been investigated to some extent. In 1937, Hansen prepared 3-fluoro-4-hydroxy-
1+

, ci-

have been synthesized (289). Of the compounds tested, the 4-fluorophenyl derivative was the most active when injected intraveneously; it was moderately active when administered orally. Antibiotics containing fluorine have been reported by Rebstock (390), who prepared a number of compounds related to chloroamphenicol (Chloromycetin) which has the structure

258

PAUL TARRANT

Ď NHCCHCU

•

n

<

0:

Ç I C—C—CH 2OH Ď Ç Ç

For example, the mono-, di-, trifluoro-, fluorochloro- and difluorochloroacetamides were prepared and tested for antibacterial, antiviral, and antifungal properties, but they were inferior to the chloro derivative. In 1939, Suter and Weston (461) prepared 5-fluorosalicylic acid and its acetyl derivative which they called fluoroaspirin ; these compounds were found to be more toxic than the unsubstituted substances. A patent has been issued (405) for the use of 5-fluoronicotinic acid and the amide as antimetabolite against streptococcic and staphylococcic infections. Before the war, fluorotyrosine Ç

NH2 achieved some importance in Germany as a pharmaceutical for the treat­ ment of hyperthyroidism; it was known as Pardinon (136). Later work, reported more fully under the section on amino acids, indicates that this compound was not as effective as had been earlier claimed. Mitchell and Nieman (349) report that 3-fluoro-DL-phenylalanine is far more effective than sulfathiazole for inhibition of growth of certain airborne yeasts, molds and bacteria. The fluorotyrosines also possess outstanding effectiveness as competitive inhibitors for their parent amino acids. VanderWerf has reported the synthesis of 2-methforyl-l,4-napthoquinone, a trifluoromethyl derivative of menadione of interest as a possi­ ble vitamin Ę antagonist (178). Pesticides Bradlow and VanderWerf made a study of the preparation and chemi­ cal composition of bis(p-fluorophenyl)trichloroethane (DFDT), which has been claimed to be superior to DDT as an insecticide (45). Various modifications of the general method used for preparing D D T proved satisfactory for making DFDT, but the optimum yield for the condensa­ tion of chloral with fluorobenzene was obtained at a maximum of 25 to

ORGANIC COMPOUNDS CONTAINING FLUORINE

259

30°, using a 3:1 mixture of sulfuric acid and oleum. The principal product was the ń,ń'-compound, 1, l-bis(p-fluorophenyl)-2,2,2-trichloroethane. Although isolatable amounts of the ď,ń'-isomer were obtained, the per­ centage of this compound was in most cases considerably less than that of its chlorine analog found in DDT. No ď,ď'-isomer was isolated from the reaction mixture. Some other compounds containing fluorine which are related to D D T and which have been prepared by condensing a suitable phenyltrichloroethanol with a second aromatic compound are l-(p-methoxyphenyl)-l(p-fluorophenyl)-, l-(p-chlorphenyl)-l-(p-fluorophenyl)-, l-phenyl-l-(p)fluorophenyl)-, and l-(p-tolyl)-l-(p-fluorophenyl)-2,2,2-trichloroethane. In addition, certain bis(chlorofluorophenyl)trichloroethanes have been synthesized. The tribromoethane and dichloroethane analogs of D F D T have also been prepared. Kirkwood and Dacey prepared the compounds l,l-bis(p-fluorophenyl)trichloroethane (I), l,l-bis(p-chlorophenyl)- (II), and l,l-bis(p-fluorophenyl)-2,2,2-trifluoroethane (III), which are analogs of D D T (267a). CC1 3

CF3

CF3

The pentafluoro derivative (III) was made by treating bis(p-fluorophenyl)trichloroethane with hydrogen fluoride. When tested against Drosophila melanogoster, I had two-fifths the potency of pure DDT, while the other two compounds had potencies one-hundredth that of DDT. Derivatives of fluoroacetic acids seemed promising as insecticides until it was found that such compounds containing the CH 2FCO— group were extremely toxic, both orally and by skin absorption, to warm blooded animals. A convenient method of preparing such derivatives was de­ veloped from the reaction of chloroacetamide and potassium fluoride to give fluoroacetamide, which served as the starting point for the prepara­ tion of other carbonyl compounds (7). A considerable amount of research and developmental work was carried out in England, Canada, and the United States during World War II for the production of methyl fluoroacetate for use in chemical warfare.

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The toxicity of á-fluoroacetic acid derivatives to insects is remarkable, as the following report by David will show (84). When plants were dipped into a 0.001% solution of sodium fluoroacetate, a complete kill of Aphis labial resulted in two days. Tests made on plants growing in soil showed that as little as 1 mg. of the salt added to a pot 3.5 inches in diameter containing approximately 400 g. of soil freed the plant from aphids in 5 days. Toxicity was also imparted by allowing the solution to drip on one pair of leaves; in favorable cases the entire plant was freed from aphids in 4 to 5 days. Sodium fluoroacetate, "1080," is a useful rodenticide, but must be used under careful control by experienced pest control operators owing to its toxicity to human beings. However, this rodenticide has been spectacularly successful in the ridding of pests in commercial buildings, such as warehouses and barns, where there is no danger of children or domestic animals coming in contact with the material. It has been claimed (381) that fluorohydracrylic acid, CH 2OHCHFCO2H, is useful as a rodenticide, but little or no information is available concerning its activity. Polymers Containing Fluorine Perhaps the most widely used organic fluorine compounds are the polymers of tetrafluoro- and chlorotrifluoroethylene, produced commer­ cially under the trade name Teflon and Kel-F, respectively. Although these materials have been available for use only since World War II, they have many useful applications where other plastics would be worthless, and, as new techniques for their handling and fabrication are being developed, there is no doubt but they are to be used in ever increasing quantities because of their amazing properties. Teflon, for example, resists attack by all corrosive agents except the molten alkali metals and fluorine, and, at the same time, can withstand exposure of from —100° to +500°F. The fluoroplastics have been extensively used as coatings for magnet wire, insulation for coaxial cable, and supports for radar and FM antennas because of their excellent electrical properties. Such polymers are also being used on conveyor belts to handle sticky materials and on breadmaking machinery because practically nothing will stick to them. Teflon is being used for gaskets and for pump parts as well as for stockcocks which will not stick. Other uses of these remarkable fluoroplastics are being developed so rapidly that they are classed among the "glamour babies of the American plastic industry" (453a). There can be no question of the effect of these two materials in stimulating research and develop­ ment of other polymers containing fluorine.

261

ORGANIC COMPOUNDS CONTAINING FLUORINE

Because of military needs for rubber and rubber products with im­ proved properties over the natural and synthetic rubber being used, con­ siderable interest has been shown in organic fluorine compounds for applications where elastomers are needed. Because of the immiscibility of fluorocarbons and hydrocarbons, it is believed that oil resistance can be built into an elastomer if sufficient fluorine is present in the molecule. Although the Armed Services have placed contracts for research and development work directed toward finding fluoroine compounds which will be new members of the rubber family suitable for use under extreme conditions, it appears that no polymer as yet has been produced which can be expected to fulfill future requirements. There is a real need for new elastomers with high resistance to fuel, oil, oxygen, and fire and which at the same time will be serviceable at high and low temperatures and have strength, elasticity, and resistance to permanent deformation. Since the introduction of fluorine atoms into molecules exerts such pronounced effects on their physical and chemical properties, the use of fluorine compounds as substitutes for styrene, butadiene, or such monomers offers hope for some solution of the problem. However, the literature contains few references to the preparation of monomers containing fluorine useful in elastomers and progress in this field is likely to be slow. STYRENE DERIVATIVES

Considerable activity has been directed toward the preparation of styrene derivatives containing fluorine. A number of investigators have prepared derivatives containing fluorine atoms or methforyl groups attached to the aromatic nucleus; others have studied styrene derivatives containing fluorine atoms in the ethylene side chain. The method generally used for the preparation of styrene derivatives containing the methforyl group involves the use of the Grignard reagent. For example, ra-methforylstyrene has been prepared as follows (4, 302, 396): CF3

CF3

CF3

CF3

CH3CHO

MgBr

CHOHCH3

CH=CH2

The monomer has been illuminated with ultraviolet radiation for 24 hours to give a polymer with a softening point of 130 to 155° and an approximate molecular weight of 7350. It has been claimed that m-methforylstyrene, when heated at 105° without a catalyst, gives a hard colorless polymer. Films of this material are flexible and resistant to sunlight and heat (397).

262

PAUL TARRANT

The methforylstyrenes have been shown to give interesting copoly­ mers with butadiene. Renoll has reported that the substitution in part or altogether of methforylstyrene for styrene in a GR—S type polymeriza­ tion gives an elastomer with greater tensile strength and improved plasticity (398). Marvel and his colleagues have evaluated o-, m-, p-fluorostyrene, and m-methforylstyrene in the course of their study of copolymers containing butadiene (303, 304). The elastomers, which were formed by the usual methods employed to yield GR—S, were compounded, vulcanized, and tested by the standard procedures. Their properties were approximately equal to GR—S. Bachman and Lewis have reported the preparation of a number of styrene derivatives containing fluorine (4). CH=CH2 CH=CH2 CH=CH2 CH=CH3

CF3 C H 3C = C H 2

F

CF3 CH=CHCH3

C H 3C = C H 2

In general, the syntheses involved the conversion of fluorobromides, via the Grignard reagent, to primary, secondary, or tertiary alcohols which were dehydrated to the olefins. m-Methforylstyrene was prepared by alternate procedures: MgBr

CH 2CH 2OH

ORGANIC COMPOUNDS CONTAINING FLUORINE

263

The styrene derivatives containing no a- or 0-methyl group polymerized readily with peroxide catalysts to give brilliantly clear, hard polymers. Copolymers of the styrenes were prepared with vinyl acetate, methyl methacrylate, styrene, and maleic anhydride at 70°. Hard, transparent or translucent polymers similar to styrene were formed except with the a- or 0-methylstyrenes and vinyl acetate. Elastic copolymers with butadiene were prepared using the usual GR—S emulsion technique with the fluorostyrenes. A number of styrene derivatives containing one or more methforyl groups and chlorine in the benzene nucleus have been prepared by the general procedure discussed above (334). The monomers were polymerized in emulsion at 50° in the presence of Tergitol No. 4. Although styrenes containing two methforyl groups on the ring can be prepared satisfactorily from the corresponding bromine compounds, the use of lithium butyl is required in the synthesis of 2,4,6-tris(methforyl)styrene (335). F 3C ^ > C F 3

CH3CHO CHOHCH3 LiBu > F 3C f ^ , C F 3 > F^ff^CF,

F 3Ci

Attempts to polymerize trismethforylstyrene in the presence of benzoyl peroxide or with ultraviolet radiation were unsuccessful. McBee and Sanford have suggested that polymerization was prevented by the steric effects of the two o-methforyl groups. Styrene derivatives containing fluorine on the ethylenic carbon atoms have not been studied so extensively as those containing aromatically bound fluorine. The method employed to prepare several compounds is illustrated by the preparation of á,â,â-trifluorostyrene (73). C O C CC 1C Fl l2 C ^ Q + C C l F 2C O C . - . Q z ,CF=CFS n

1 j ^ j C F C l C F 2C I

Using this procedure, Cohen et al. have also prepared a-chloro-^,|8difluorostyrene and /3-chloro-a,/3-difluorostyrene (74).

F

2

C

264

PAUL TARRANT

More recently it has been shown that a,/3,0-trifluorostyrene could be made directly from benzene and chlorotrifluoroethylene (376) :

by passing the reactants in the gas phase through a hot tube. This derivative has also been made by the dehydrohalogenation of a-chloroa,0,0-trifluoroethylbenzene. á,/3-Difluorostyrene, C eH 5CF=CH*F, and a-chloro-0-fluorostyrene, C 6H 5CC1=CHF, have been prepared by the removal with zinc of fluorine and chlorine atoms from C eH 5C F C l C H F 2 and C6H5CCI2CHF2, respectively. â,â-Difluorostyrene was formed by the thermal decomposition of the benzoate of 2,2-difluoro-l-phenylethanol, CeH 5CHOHCHF 2. The bulk polymerization of trifluorostyrene gave some high melting polymers but a significant side reaction was a dimerization to a cyclobutane derivative. The polymer formed by emulsion polymerization had a higher softening point than polychlorotrifluoroethylene and possessed good electrical properties. The yields of polymer from â,â-difluorostyrene were low, whereas a-chloro-Ł-fluorostyrene did not polymerize to any great extent. Polymers from á,â-difluorostyrene were unstable. ACRYLIC ACID AND ITS DERIVATIVES

As might be expected, fluoroacrylic acid derivatives and acrylic acid derivatives containing fluorine atoms as part of an ester or substi­ tuted amide group have been reported. The patent literature contains references to polymers of low refractive indices and high relative disper­ sions obtained from esters of acrylic acid and alcohols containing fluorine. For example, Ł,/3,0-trifluoroethyl acrylate, made from acryl chloride and trifluoroethanol, has been polymerized with benzoyl peroxide (80). Acryl chloride has been treated with fluoro amines to give N-fluoroalkyl acrylamides (75). The following acrylamides have been reported: N-(2,2,2-trifluoroethyl) (I) ; N-(3,3,3-trifluoropropyl) ; N-(2,2-difluoroethyl) (II) ; N-(3,3-difluorobutyl) ; N,N-bis(2,2-difluoroethyl) ; and N,Nbis(2,2,2-trifluoroethyl). Analogous derivatives of methacrylic acid were also prepared. Homopolymers were made of I and II. In addition, copoly­ mers with acrylonitrile and methyl methacrylate were prepared. Methyl á-fluoroacrylate has been converted to the â-fluoroethyl ester, which could be polymerized readily to a transparent solid of low index of refraction (79). McGinty has reported a novel method of synthesis of esters of á-fluoroacrylic acid (342). These compounds were made by treating α-β-dihalo-a-fluoropropionic esters, obtained from the trihalide

265

ORGANIC COMPOUNDS CONTAINING FLUORINE

and mercuric fluoride, with hydrogen whereby the chlorine or bromine atoms on adjacent carbon atoms were removed. Polyfluoroacry lie acid derivatives have been made from polyfluoropropylenes (59, 61, 62, 64). For example, Chaney has shown that com­ pounds of the type C F 2X C X = C C 1 2, where X is chlorine or fluorine, react with a mixture of oxygen and chlorine under ultraviolet irradiation to give propionyl chlorides. In this manner, CF 2C1CC1 2C0C1 and CF 2C1CFC1COC1 were obtained. The acryl chlorides react with alcohols to give esters which have been converted by standard methods to the porresponding amides and nitriles; the acid chloride has also been treated with ammonia to yield the amide. The fluoroacrylonitriles were prepared by treating the corresponding á,â-dichloro derivative with zinc; for instance C F 2C 1 C F C 1 C N and CF 2C1CC1 2CN gave C F 2= C F C N and C F 2= C C 1 C N , respectively. á-Methforylacrylate esters can be polymerized or copolymerized with other vinyl-type monomers by the use of peroxide catalysts (100). Methylacrylonitriles containing fluorine on the branched chain also form homopolymers or can be copolymerized with styrene, butadiene, or other acrylic acid derivatives (105). Such nitriles have been prepared by the method illustrated below for the preparation of a-methforylacrylonitrile according to Dickey (100).

CF3 I

CF3COCH3 + HCN

CH 3—C—CN I

CF3 soci2

I

• C H 2= C — C N C*H*N

Ď Ç Apparently the dehydration step is difficult to carry out properly since other investigators were unable to effect the transformation with phosphoric oxide (81). VINYL FLUORIDE

Newkirk has made an extensive study of the polymerization of vinyl fluoride (357). Previous investigators had reported considerable difficulty in obtaining polymers. Newkirk found that the conversion of monomer to polymer could be increased from 2 % to 40% by the addition of a cosolvent for the monomer and catalyst. Reproducible results were obtained only from carefully purified monomer. Light of wave length below 2800 A as well as benzoyl peroxide, lauryl peroxide, and acetyl peroxide catalyzed the polymerization. The material polymerized by ultraviolet radiation remained white indefinitely whereas samples polymerized with benzoyl peroxide became brown on standing. Extrac­ tion of lower molecular polymeric material by ethanol gave a product

266

PAUL TARRANT

which did not darken on storage. Calcium stéarate and magnesium oxide, when used in an amount equal to 2 % of the weight of the polymer, increased the color stability of the polymer. A brief study made of the thermal stability of polyvinyl fluoride indicated that it decomposes more slowly than polyvinylchloride except for an initial rapid decomposition in tests in air at 175°. The polymer was not appreciably soluble in a number of common solvents but could be dissolved in hot dioxane, cyclohexanone, and certain chloroethanes. Copolymers of vinyl fluoride have been copolymerized with vinyl esters of the lower fatty acids from which films can be cast which are tougher and more resistant to discoloration by sunlight than those from similar vinyl chloride-vinyl acetate copolymers (514a). Polyvinyl fluoride may be stabilized from decomposition by heat by the addition of primary and secondary amines or amides (258). For example, it has been claimed that 2 % of urea gives a mixture which can be molded at 250° for 5 minutes with no sign of discolorization; under the same conditions, unstabilized polymer decomposed violently. The use of three different monomers gives products with interesting properties (301). For instance, a polymer containing tetrafluoroethylene, vinyl fluoride, and vinyl chloride in the ratio 1:5.4:1 gives films with tensile strength of 4850 lb. per square inch at an elongation of 460% with tack temperature of 115 to 120°. Such films are nonflammable. Vinylidene fluoride, 1-chloro-l-fluoroethylene, or similar materials may replace the vinyl chloride. The properties of these polymers make them suitable for use as a base for film or in coating compositions for wrapping or insulation. Films made from polyvinyl fluoride with a thin layer of vinyl acetate under the emulsion are permanently clear, have excellent dimensional stability even in the presence of water and possess a low degree of flammability (3). Copolymers of vinyl fluoride and vinyl acetate are claimed to be useful for yarns, bristles, brushes and as leather and rubber substitutes because of their resistance to hydrolysis (253). Acetylene-free vinyl fluoride can be polymerized in the presence of an organic peroxide. Films cast from a 10% solution in cyclohexanone on a plate at 135° are continuous and clear. Copolymers of vinyl fluoride and a terminally unsaturated monoolefin can be readily made (69). 1-CHLORO-1-FLUOROETHYLENE

1-Chloro-l-fluoroethylene has been polymerized to a white, rubbery solid; films made from the polymer have good resistance to ultraviolet rays (394). It has been claimed that polymers useful for the production of

ORGANIC COMPOUNDS CONTAINING FLUORINE

267

films, filaments, or coatings may be made by polymerizing vinylidene chlorofluoride in the presence of ultraviolet light, benzoyl peroxide, and lead tetraethyl. Polymers thus formed were low melting and softened at 60 to 70° (371). Copolymers may be made with acrylonitrile. For example, the product containing five parts of acrylonitrile and two of vinylidene chlorofluoride softens at 170° (372). VINYLIDENE FLUORIDE

The polymerization of vinylidene fluoride has been carried out in the presence of acetyl peroxide in a stainless steel autoclave (327). The polymer, of softening point of 132°, was obtained in 19% conversion at 100° for 48 hours. Bis(methforyl)benzenes and carbon tetrachloride were successfully used as solvents but the polymerizations were reported to occur in the gas phase since the polymer was always found on the walls of the reactor. Films showing no discoloration when heated to 300° for 5 minutes have been obtained from a copolymer of tetrafluoroethylene and vinyli­ dene fluoride. Copolymers of vinylidene fluoride may also be made from ethylene or vinyl fluoride in the presence of peroxide catalysts (138). Ford and Hanford have polymerized vinylidene fluoride under care­ fully controlled conditions to yield a tough, transparent or translucent, material which softens at 145 to 160° and can be cold drawn to a perma­ nent increase in length of 100% with molecular orientation in the direc­ tion of elongation (139). Poly vinylidene fluoride films have tensile strengths of about 4500 lb. per square inch, density of 1.74 g. per cubic centimeter, and were not discolored or embrittled when exposed outdoors for 6 months. TRIFLUOROETHYLENE

Copolymers of tetrafluoroethylene and trifluoroethylene can be processed into films or filaments. The film has a tensile strength of 1600 lb. per square inch and an elongation of 204%. The polymer has a power factor loss of 0.0036 and a dielectric constant of 3.42 (125). Trifluoroethylene either alone or with vinyl fluoride or other vinyltype monomers can be polymerized in bulk or in emulsions in the presence of a peroxide catalyst (170). CHLOROTRIFLUOROETHYLENE

Polymers from chlorotrifluoroethylene are now being produced on a commercial scale. Such polymers are finding wide use as gaskets, as

268

PAUL TARRANT

insulation for electrical and radio wires, and in molded articles where inertness is a factor. Although polychlorotrifluoroethylene does not possess the inertness of polytetrafluoroethylene, it is preferred in many cases because the polymer can be processed by standard plastic fabricat­ ing techniques. Copolymers of chlorotrifluoroethylene are reported to have interesting properties. Resins useful as films, fibers, adhesives, or molding compounds have been made by copolymerizing chlorotrifluorcethylene and a vinyl ester of a fatty acid; the copolymer may be hydrolyzed to give a product which contains alcohol groups. Copolymers of chlorotrifluoroethylene and vinyl fluoride can be made which are claimed to adhere to polished metal surfaces at 60 to 65°; such materials can be molded at 150°. Other comonomers which may be used in such applications are tetrafluoro­ ethylene, vinylidene fluoride, trifluoroethylene, and dichlorodifluoroethylene (124). Copolymers of chlorotrifluoroethylene and ethylene in the molar ratio of 1:1 have higher melting points than polymers of either substance when polymerized alone (120). Copolymers give films with tensile strengths of 2700 lb. per square inch; these films can be cold drawn to 400% elonga­ tion. Higher molecular weight polymers generally result when the poly­ merizations are carried out at higher pressures (168). Low molecular polymers derived from chlorotrifluoroethylene have been found to have unusual chemical stability. Miller et al. in their work on the preparation of lubricants for the Manhattan Project, were able to prepare oils, waxes, and greases by the polymerization of the monomer in the presence of chain transfer agents such as chloroform or carbon tetrachloride (345). Such polymers, however, were somewhat reactive because of terminal —CHCU or — C C I 3 groups but this difficulty was overcome by a fluorination step in which fluorine was introduced into these terminal groups. The overall reactions for the production of the inert polymer are given below. Zn

CF 2C1CFC1 2-> C F 2= C F C 1 (Freon 113) Peroxides

C F 2= C F C 1

CHCI3

> R(CF 2CFCl) nR'

R(CF 2CFCl) nR' -+ R"(CF 2CFCl) nR"' Oils satisfactory for use as lubricants were prepared by separating the low polymer oil (b. 100 to 240° at 0.3 mm.) and subjecting it to fluorination. Such oils were found to be free from breakdown and to have

ORGANIC COMPOUNDS CONTAINING FLUORINE

269

provided adequate lubrication for test machines operated continuously for 6 months. Waste sheets of polychlorotrifluoroethylene have been pyrolyzed at 400 to 475° to form lower molecular weight products useful as lubricants. A waxy residue, melting from 110 to 250°, can form chemical resistant coatings on filaments and fabrics (267). FLUOROPRENE

The usefulness of chloroprene as a synthetic rubber suggests the possi­ bilities of fluoroprene in applications where the chloro compound has advantages. Fluoroprene has been prepared by the addition of hydrogen fluoride to vinylacetylene ; it has been polymerized to give a rubber with interesting properties. Mochel et al. report that fluoroprene occupies a position between butadiene and chloroprene in its properties; it polymer­ izes twenty-five times faster than butadiene but slower than chloroprene (351). Polymers of fluoroprene resemble butadiene in being amorphous in the stretched state and require the use of fillers for high tensile strengths. Fluoroprene will copolymerize with a wide range of dienes and vinyl compounds whereas chloroprene copolymerizes only partially with many monomers. The polymerization of fluoroprene may be carried out by the pro­ cedures common to chloroprene but is greatly affected by the presence of certain impurities such as vinylacetylene or peroxides. Polyfluoroprenes have shown tensile strengths of 2800 to 3200 lb. per square inch in typical tire tread stocks but only 800 to 900 lb. per square inch at 1000% break elongation in pure gum stocks. The tensile strength and resilience of fluoroprene vulcanizates are equal to or superior to GR—S but inferior to GR—M. Polyfluoroprene is more resistant to stiffening and embrittlement at low temperature than the most freezeresistant polychloroprene and is much superior to the commercial oil resistant rubbers in freeze resistance. The oil resistance of polyfluoroprene compares favorably with that of Neoprene Type GN. Polyfluoroprene can be made as resistant to sunchecking as neoprene by the addition of certain inhibitors. Fluoroprene-dimethyl(vinylethinyl)carbinol copolymers are superior to polyfluoroprene in milling properties and tensile strength; they have comparable freeze, sunlight, and oil resistance. Fluoroprene-styrene copolymers have been prepared and found to be highly freeze resistant, with good mill behavior; however, they are some­ what poor in oil resistance.

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PAUL TARRANT

Copolymers of fluoroprene and acrylonitrile have been found to be highly resistant to oil. Rubber vulcanizate of fluoroprene and' 15% acrylonitrile have exhibited tensile strengths of 3800 to 4800 lb. per square inch with 500% break elongation. The solvent resistance of such copoly­ mers is markedly superior to that of Neoprene Type GN and is at least equivalent to that of a butadiene-acrylonitrile (75/25) copolymer: a batch having an original tensile strength of 4860 lb. per square inch retain a strength of 4000 lb. at 520% elongation after immersion in kerosene at 100° for 2 days. 2 , 3 - D l F L U O R O - AND 2-CHLORO-3-FLUOROBUTADIENE

Wakefield has made a study of the properties of 2,3-difluoro- and 2-chloro-3-fluorobutadiene and reached the conclusion that the use of fluorine-substituted dienes would not lead to superiority in either cold resistance or general physical properties (534). It should be noted that the monomers were available on a limited scale, and it was thus impossible to adjust the polymerization details and processing techniques to opti­ mum conditions. Polymerizations of 2,3-difluorobutadiene were carried out initially by an anionic (GR—S) recipe. The homopolymer was rubbery although harder and tougher than GR—S; the copolymer with styrene was highly thermoplastic, being stiff at room temperature but pliable when warm. The copolymer with butadiene was the softest and most rubbery but was similar to polybutadiene, being weak and short. The milling characteris­ tics of the copolymer with butadiene were normal, but the styrene copoly­ mer became hard and brittle when the carbon black was added, while the homopolymer stiffened and became leathery at that point. The tensile strength of a GR—S black recipe containing a ratio of butadiene to the difluorobutadiene of 75:25 averaged 2200 lb. per square inch and swelled 360% in 24 hours in ASTM standard fuel No. 2. The polymerization of the difluorobutadiene under cationic conditions gave a product which was compounded and vulcanized using a tire tread recipe. Tests showed a reduction in tensile strength. Since the lowtemperature bending modulus values showed that the polymer stiffens at a much higher temperature than would be expected, Wakefield concluded that the fluorine atoms caused a greater chain interaction than had been expected. Polymers of 2-chloro-3-fluorobutadiene were found to be quite similar to polychloroprene in having a high ozone resistance. In neoprene-type recipes, the homopolymer had equal solvent resistance and tensile strengths. It is inferior in rebound, being almost dead at 25°.

TABLE I Properties Formula

Structure

M.p., °C

CBrF CBr F

Compounds t. ° C

l

n

l d

FCONF CF NO

3

-138 -42 Sublimes at - 7 2 -114 -83.1 -22.5

2

CF OF

3

-152.2 -152

<-215 -115

-35 HCOF

2

3 2 3 3 2 2 2 3 3 2 2 2 2 2 2 2 2 2 2 2 2

-72.9 32.8 45.5 122.5

-112

124.2 92 49-50 51 93-94 -2.5 1 -23to-21 114 93.1 140 139

70.5 75.4 46.4 147.2

2 3

25 18 18.5

1.97 1.55 2.4256

-30

20 16

1.195

1.3596 1.427

-18

1.89

20

1.4278

2.2478

20

1.4535

2.3121

15

2.6699

2

2

3 2 2 3 3 3

3 3 3 2 3 3 2 2 3 3 3 2 2 3 2 2 2 32 3 65 3 2 3 2 CF =CC1 + Br 2 2 CFC1=CC1 + Br 2 CF BrCHBr + KC H 0 + K C0 2 2 2 32 2 3 CFBr CHFBr + NaOC H 2 25 CBr COCl + SbF 3 3 C H B r F + KOH/alcohol 2 4

Ref. 50 12 386 450 78 416 12 187 415 414 237 263 31 486 487 413 355 413 290 86 313 516 468 516 474 516 50 469 207 214 214 294 488 471 472 294 470

271

H NCOF CH S0 F CH S0 F CF ClCOBr CFClBrCOF CCl FCOBr CF =CBrF CF COBr CF CF Br CBr ClCOF CBrF CBrClF CBrClFCBrCIF CBrF CBrCl CBrClFCBrCl CF =CBr CFBr=CFBr CBr FCOF CF BrCF Br CFBr=CBr

-122 46-47

-82.4 -84

-95 36.1 -14.5 65 100 -26 21,6

C H F + B r , 600° C B r + A g F (60%) CBr + BrF3 CBr + BrF CBr + SbF COCl + HF, 80° A g F + ICN A g F + CO CI + IF CF C0 Ag + I AgCN + Ο + F AgCN + F CF BrN0 + C 1 F CF NO + Pb0 CH3OH o r C O + F / A g F CHClBr + SbF CHBr + SbF CHBr + SbF CHI + HgF HC0 H + K F CHI + HgF Cyanic acid + HF CH S0 C1 + ZnF C H O C H + HS0 F CF ClCOOH + CeHsCOBr CClBr COCl + SbF CCl FCOOH + CeHsCOBr C F B r C H B r F + K C H 0 + alcohol CF COOH + C H COBr CHF + Br CClBr COCl + SbF CF =CFC1 + Br

3 4 4 4 3 4 3 2 2 4 5 3 2

107 C1COF FCN FCOF

Preparation

ORGANIC COMPOUNDS CONTAINING FLUORINE

2 3 CF NO 3 CF N0 3 2 CF 0 4 CHBrCIF CHBrF 2 CHBr F 2 CHFI 2 CHFO CHF I 2 CH FNO 2 CH F0 S 3 2 CH F0 S 3 3 C BrClF 0 2 2 C BrCl FO 2 2 C BrF 2 3 C BrF 0 2 3 C BrF 2 5 C Br ClFO 2 2 C Br ClF 2 2 3 C Br Cl F 2 2 22 C Br Cl F 2 2 3 C Br F 2 22 C Br F 0 2 22 C Br F 2 24 C Br F 2 3

Fluorine

B.p.,°C -59 24.5

3 22 CBr F 3

CC1FO CFN CF 0 CF I

of Organic

272

T A B L E I (Continued) Structure

Formula C Br F C Br F

2 2 2 2 3 2 CC1FN0 CF N0 2 2 2 CF COCl 3 CFC1N0 CFC1N0 2 2 CF ClCOCl 2 CFCl COF 2 CCI3COF CCI2FCOCI (COF) CF CN CF ICF I CF N0 CF N0 CF COF CF CF I CF N=NCF Dicyanohexafluoride CF NFCF Dicyanooctailuoride CHBrFCOCl CBrClFCOOH CBrF CHClF CBrF CHCl CHF=CBrF CHBr=CF CF BrCCOH CHF CF Br CF BrCHClBr CBrCl CHBrF CHBrClCBrCIF CBr =CHF CHBr=CBrF CHBrFCOBr

2 3 2 2 2 2 2 2 3 3 2 3 3 3 3 2 2

2 2 2 2 2 2

M.p., °C

62.5 99 176 (dec.)

12-18

-41.5

-133 -130

-5

2

2

CBr FC0 H CBrF CHBrF CBrF CHBr CHBrFCBr CHBr CBr F CHC1FCN

2 2 2 2 2 3 2 2

40

26.5

B.p., °C 117 187 185 98-99 - 1 9 to - 1 8 5 5 - 5 6 at 35 m m . 134 31 66.8 75 26 -61.5 112-113 57-58 -59 13 -32 -40 -37 -2.2 98 181 46 at 620 m m . 88.5 at 621 m m . 19.6 6.2 145-160 - 3 at 626 m m . 118.7 163.5 163.5 90.3 at 748 m m . 88.8 112.5 198 69 at 630 m m . 144 104 at 23 m m . 106 at 24 m m . 66

t. ° C 7

20

1.4666

2.56656

25 1.37482 5 1.674

20

1.4116

1.646

25 20

1.4895 1.34825

2.6293 1.695

-32.7

1.487

-2.2 14.5

1.608 1.879

25 25 0 0

23 23 17.5 17.5 10 0 17.5 16 17.5 25

1.3685 1.4349 1.3846

1.5160 1.4954

1.41924 1.5022 1.5971 1.3627

1.8636 1.9043 1.8434 1.82

2.1301 2.2833 2.2908 2.289 2.3314 2.274 2.6077 1.9387 2.909 1.267

Preparation

Ref.

CF =CFBr + Br CFBr=CFBr + Br CF =CBr + Br CFBr=CBr + Br CF =CFC1 + N 0 CF COOH + C H COCl CFC1=CFC1 + N 0 C H F C H O H + CI CCl COOH + SbF CCl COOH + C H C O F (CCl3CO) 0 + SbF + Br CH COCH + F CF CONH + P 0 CF =CF + I CF =CF + N 0

474 471 488 470 176 516 176 483 467 306 467 147 502 379 176 147 12 417 414 515 414 478 468 366 366 471 488 479 366 191 478 191 470 488 478

2 2 2 2 2 24 3 65 24 2 2 3 3 3 65 2 3 3 3 3 2 25 2 2 2 2 24 CH COCH + F 1F ( C H3I ) + 3 2 2 5 ICN + P F 5 AgCN + F (CH ) N + CoF (or CoF ) 33 3 2 AgCN + F CHFBrCOOH + P C 1 3 CBrClFC0 C H 2 2 5 + KOH CF =CFC1 + HBr 2 CF =CC1 + HBr 2 2 C B r F C H F B r + Zn 2 CF BrCH Br + KC H 0 2 2 2 3 2+ CHF COOH + Br 2 CF =CF 2 2 + HBr CF =CHC1 + Br 2 CHF=CC1 + Br 2 C H B r F + KOH 2 2 3 C B r F C H B r + KOH 2 2 C H B r F + [O] 2 2 CFBr=CFBr + air CF =CHF + Br 2 CHBr=CF + Br 2 CHF=CBr 2 + Br CFBr=CHBr + Br CHFClCONH + P 0 2 25

K C0

2 3

472 363 488 470 488 554

PAUL TARRANT

2 33 2 42 C Br F 2 5 C C1F N 0 2 3 24 C C1F 0 2 3 C C1 F N 0 2 2 2 24 C C1 F 0 2 22 C Cl FO 2 3 C F 0 222 C F N 23 C F I 2 42 C F N 0 24 24 C F 0 24 C F I 2 C F e5N 2 2 C F N 27 C F N 282 C HBrClFO 2 C HBrClFΤ 2 2 C HBrClF 2 3 C HBrCl F 2 22 C HBrF 2 2 C HBrF 0 2 22 C HBrF 2 4 C HBr ClF 2 2 2 C HBr Cl F 2 2 2 C HBr F 2 2 C HBr FO 2 2 C HBr F0 2 2 2 C HBr F 2 23 C HBr F 2 32 C HBr F 2 4 C HC1FN 2

CFBr CF Br CBr FCBr F CBr CBrF

C C C C

C H Br FNO C H Br F

2 2 2 2 2 2 CHC1FCOC1 CCl FCOOH 2 CHF CN 2 CHF=CF 2 CF CHI 3 2 CF CHNN 3 CF CHO 3 CF3COOH CF CHF 3 2 CF NHCF 3 3 CBrClFCONH 2 CH BrCF Cl 2 2 CHBrClCHCIF CH =CBrF 2 CH FCOBr 2 CHBrFCOOH CF CH Br 3 2 CBrF CH F 2 2 CHBrFCHF 2 CBr FCONH 2 2 CH BrCBrF 2 2 CHBr CHF 2 2 CHBrFCHBr 2 CBr FCH Br 2 2 CH FCOCl 2 CH ClCOF 2 CHC1FCOOH CF ClCONH 2 2 CCl FCONH 2 2 CH FCN 2 CH =CF 2 2 CH FCOF 2 CHF COOH 2 CF CH I 3 2 CF CONH 3 2 CHF CHF 2 2 CHF CF S0 H 2 2 3 CH BrCHClF 2 CHBrFCONH 2 CHF CH Br 2 2

22.9

-20

-15to-13.5

-15.3 -103 -130 131.5 —75.8

49 -93.9

136 -56

78 126.5

75

-67 44 -74.5

25 121.5 90 70.5

17

1.3961

1.4802

69.5

25

1.3992

1.468

162.5 23 - 5 6 at 628 m m . 54 at 39 m m . 13-13.5 at 752 m m . -20

15 27.4 22

1.113 1.265 2.595

72.4 -48.5 6.3

-194

68.4 125 6.8 95-96 183 26.3 25 41 at 735 m m .

20 20

93 107 178 163 71 73-76 162 9 3 a t 18 m m . 215 80 -82 51 134.2 55 at 730 m m . 162.5 -23 59.5 96.6 57.3

2.21 1.4018 1.4776

1.8300 1.932

CHF COOH CHF C0 H CHF CF S0 CHCl COCl

+ PC1 2 5 2 2 +H C+I PCI5 2 2 3+ S b F 2 3 CHC1FCOOH + P C 1 5 CCl FCOF + H 0 2 2 CHF CONH + P 0 2 2 25 C F B r C H F C l + Zn 2 CF CHN + I 3 2 C F C H N H + HN0 3 2 2 2 C F C N + L1AIH4 3 C H + F 26 . ICN + P F 5 CBrClFC0 C H + N H 22 5 3 C F B r C H B r + Zn CHF COOH + P B r CHBrFCOBr + H 0

2 2 2

20

1.3331

1.7881

10

1.3618

1.874

12.2 20 18 17.5 27

1.4525 1.4622 1.5638 1.5022 1.3835

2.2423 2.312 2.6737 2.6054

25

1.4085

1.532

1.5359 1.989

10 23

20

1.4546

10.5 1 . 3 9 4 0

10

1.8291 1.8368

3 2

CH BrCBrF + AgF CHBr CHBr + AgF CBr FC0 C H + NH CH =CF + Br CHBr CHBr + SbF CHBr CHBr + SbF CBrF=CH + Br CH FC0 Na + PC1

2 2 2 2 2 2 2

2 2 2 225 3 2 2 3 2 3 2 2 5 CHFC1C0 C H + H P0 2 2 5 3 4 CF C1C0 C H + NH 2 225 3 CC1 FC0 C H + NH 2 225 3 CH FCONH + P 0 2 2 25 CHF CH Br + NaOC Hn 2 2 5 CH FCOCl + SbF 2 3 CHF CH OH + Cr 0 2 2 23 C F C H N + HI 3 2 + NH CF C0 C H 3 225 3 CHF CHBr + HgF 2 2 2 CF =CF + Na S0 2 2 2 3 CHBrClCH Br + HgF 2 2 CHBrFC0 C H + NH 225 3 CH BrCHBr + SbF 2 2 3

*

479 483 126 478

554 467 503 363 149 149 199

502 552 417 468 207 202 488 163 478 207 488 202 472 477 470 470 488 522 520 554 483 467 53 477, 207 421 479 150 502 202 16 202 478 477

273

22 2 2 2 22 C H Br F 22 3 C H C1F0 22 C H C1F0 22 2 C H ClF NO 22 2 C H Cl FNO 22 2 C H FN 22 C H F 2 22 C H F 0 2 22 C H F 0 2 2 22 C H F I 2 23 C H F NO 2 23 C H F 2 24 C H F 0 S 2 2 43 C H BrClF 2 3 C H BrFNO 23 C H BrF 23 2

CHF COCl CClF COOH CHF CF S0 C1 CHC1 C0F

ORGANIC COMPOUNDS CONTAINING FLUORINE

2HH CC 11 FF 200 2 22 2HH CCl1 FF O40 2S 2 2 C HC1 F0 2 2 2 C HF N 2 2 C HF 2 3 C HF I 2 32 C HF N 2 32 C HF 0 2 3 C HF 0 2 32 C HF 2 5 C HF N 2 6 C H BrClFNO 22 C H BrClF 22 2 C H BrCl F 22 2 C H BrF 22 C H BrFO 22 C H BrF0 22 2 C H BrF 22 3

274

T A B L E I (Continued) Structure

Formula

C2H3CIFNO C2H3F

CHBrFCH Br CHClFCONH CH =CHF

C H FO C H F0

CH FCOOH

C2H3Br F

2

23 23 2 C H F I 2 32 C2H F NO 32 C H3F N0 2 2 3 C H F 2 33 C2H3F3O

2

-54

2

2 2 CH3OCOF CH ICHF 2 2 CHF CONH2 2 CHF2CH N03 CH CF 2 3 3 CH FCHF 2 2 CF3OCH3 o r

-160.5

CH3COF

31-32

51.2

CHF2OCH2F

CF3CH2OH

24 C H C1F0 S 24 2 C H C1F0 S C H FI C H FNO

24 3 24 24 C H FN0 24 2 C H F 2 42 C H F N 0 2 42 22 C2H F20 4 C H F N 2 43 C H F 2 5 C H FO 25 C H F0 S 25 2 C H F0 S 25 3 C H FS 2 5 C H F N 2 52 C H C1FN 26 2 C BrF7 3 C Br Cl F 3 2 24 C3Br F6 C C 1 F2N 3 2

-107 -84 -96.2 -43.5

CH FCH Br

2 2 CH FCH S0 C1 2 2 2 CH CHC1S0 F 3 2 CH FCH S0 C1 2 2 3 CH FCH I 2 2 CH FCONH 2 2 CH FCH N0 2 2 2 CH FCH F 2 2 CH CHF 3 2 CHF CH NHN0 2 2 2 CHF2CH2OH CF CH NH 3 2 2 CH CH F 3 2 CH FCH OH 2 2 CH3CH S0 F 2 2 CH3CH2SO3F CH FCH SH 2 2 CHF CH NH 2 2 2 CH FC(NH )=NHHC1 2 2 CCl BrCFBrCF 2 3 C3Br F6 C F = C2C 1 C N 2

B.p., °C 121.5 72 at 1 m m . -72.2 21-22 168 40 89.5 109 at 3 5 m m .

t.

°c

10.5 25 -149 0 33 2.2

nt

d<

1.5178 1.4535

7

2.25701 1.510 0.998 1.032

1.06 1.468112 2 2 . 2 4 3 3

-47 3 30.1 74

25 20

1.290722

1.328 1.3842

71.7

25

1.4226

1.7044

138 8 0 a t 18 m m . 98-102

20

1.4070

65-66 10-11 -26 111 at 12 m m . 96 37 at 737 m m . -37.7 103.5

20

1.3572

107-108

-143.2 -43

134 113 38.5 at 225 m m . 67.7

-26 11.8 25 -40 20

36

1.1409 1.03

1.3345

1.3647

1.308417 1.2452 1.3057 1.040

15 20 25 11.9

1.4288 1.347

1.310 1.082 1.1758

24

1.3793

1.3560

161-162(d) 11-12 154 71 63

CHBr CH Br + SbF

2 2 2

CHFC1C0 C2H C2H2 + H F CH3COOH +

5+

3

NH

Ref. 477 554 245 306 421 154 477 479 484 202 552 40 58, 510 202 423 423

3

C6H5COF

CICO2CH3 + T I F CHF CH Br + Cal

2 2 2 3 2 2 3 3 26 4 4 CH BrCH Br + HgF 2 2 2 CH FCH OH + PBr 2 2 3 CH FCH OH + S0 C1 2 2 2 2 CH FCH CNS + C1 /H 0 2 2 2 2 CH CHC1S0 C1 + KF 3 2 CH FCH OH + S0 C1 2 2 2 2 CH ICH I + HgF 2 2 2 CH FC02C H + NH3 2 25 CH FCH OH + HN0 2 2 2 CH2BrCH2Br + HgF2 C H + HF 22

CHF2CO2C2H5 + N H

84 at 13 m m .

-117 22.4 -28.2

Preparation

1.3757

a

C H F C H O H + HNO3. CH CCl3 + SbF C H + F C2H3CI3O + S b F 3 CF3C02C H9 + LiAlH

CHF2CH2Br + HgO/H20 CF CN + H C H + HF CH ClCH OH + KF

86 423 202 53, 469 273 202 248 481 480 149 156 491,

'

3 24 2 2 CH CH S0 C1 + KF 3 2 2 C H O H + HSO3F 25 C H F C H S C O C H + HC1 2 2 3 CHF CH Br + NH 2 2 3 CH FC(OC H )=NHHCl + NH 2 25 3 C3HF7 + B r , 600° CC1 =CFCF + Br 2 3 C H F 7 + Br, 600° 3 C F C 1 C C 1 C N + Zn 2 2

#

423 86 313 131 481 53 50 204 50 59

PAUL TARRANT

C H BrF

M.p., °C

C C C C

3CF 1N3F 2N 33 3FF 60 36 C F 8 C3 3H B r F 6 C HBr F5 3 2 C HF 3 5 C HF C3 H F7 3 2NOS C H F 3 24 C H F 3 26 C H BrClF 33 3 C H Br F 3 3 23 C H C1 F0 33 2 2 C H F 3 33 C H F 0 3 33 C H F 0 3 332 C H BrClF 34 2 C H BrF 3 4 3 C H Br F 3 4 22 C3H4CIFO C H C1F0 34 2 C H C1F 0 34 3 C H C1 F 0 3 4 22 C H FNS 34 C H F N 0 3 42 22 C H F20 34 C H F 0 3 422 C H F 0 3 423 C H F I 3 43 C H F 0 3 44 C H BrClF 35 C H BrF 35 2

CC1F CC1 CN CF2=CFCN CF CF=CF CF COCF

2 2 3 2 3 3 CF CF CF 3 2 3 CBrF CHFCF 2 3 CBrF CHBrCF 2 3 CF CH=CF2 3 CF CF=CH

3

2

-32.5 -156.2 -129 -183

-153.11

-152.24

95 18 -29.3 -28 -38 30 at 624 m m . 88 -21 -18.5 t o - 1 7 76 at 50 m m . -28.3

CHF CF CHF

2 2

10-11

CF CBrClCH CF CHBrCH2Br CF CH CHBr CC1 FC0 CH CF CH=CH2

69 115.8 111 116 -18

2 3 3 3 3 2 2 2 2 3 3 CF COCH 3 3 CF C02CH 3 3 CF ClCHBrCH 2 3 CF ClCH CH Br 2 2 2 CF CH CH Br 3 2 2 CH BrCF CH Br 2 2 2 CH ClCOCH F 2 2 CHC1FC0 CH 2 3 C1C0 CH CH F 2 2 2 CH OF CHClF 3 2 CH 0CF CHC1 3 2 2 CH FCH CNS 2 2 H NOCCF CONH 2 2 2 CHF COCH 2 3 CHF C0 CH 2 2 3 CH CF C0 H 3 2 2 CH OHCF C0 H 2 2 2 CF CH CH I 3 2 2 CH OCF CHF 3 2 2 CH BrCClFCH 2 3 CH CHBrCHClF 3 CHF CHBrCH 2 3 CH BrCF CH 2 2 3

-92 -35

21.9 43 90 101 62-62.5 136 141.5-143.5 116 130 70.6

1.5171 1.312

1.3990 1.3162

1.3031 1.3780

1.8016 2.163723

1.5327

1.3527

1 (

1.3790 1.4281 > 1.4242

-107

2 3

2

3

C + F CF =CFCF + CF =CHCF + CF CH CF2C1 CF CF=CF +

2 3 HB Br r 2 3 + KOH 3 2 3 2 HF CH =CFCF C1 + SbF 2 2 3 CHF Br ^ 2 CF CHC1CH + Br 3 3 CF CH=CH + Br 3 CF CH2CH + Br 3 3 CC1 C0 CH 3 2 3 + SbF3 C F C H C H C 1 + KOH 3 2 2 CF C0CH C0 C H 3 2 2 2 5 + H 2S 0 4 CF C1C H + Br 2 25 CF C1C H + Br 2 25 CF C H5 + Br 32 CH BrCBr CH Br + SbF 2 2 2 3 CH ClCHOHCH F + K C r 0 2 2 2 27 CHFClCF OCH + H S0 2 3 2 4 COCl + CH FCH OH 2 2 2 C H 0 H + CF =CFC1 3 2

61 59 553 147, 209 448 366 339 212 174 391 212 115

1.1644

CF =CC1 CH FCH2Br + KCNS Methyl ester + N H CHF2COCH2CO2C2H5 + H S 0

334 324 324 163 212, 403 507 163 324 324 324 323 272 554 273 346, 369 346 423 184 94

1.2939 1.6475 1.626 1.601 1.6102

CH CF CF CH CH CH CH CH

162 215 381 330 346 203 323 323 203

1.708 2.121 2.086

1.282 1.4045 1.4140 1.3572 1.4586 1.4235 1.3903 1.4020 1.3340

1.662 1.726 1.653 2.132 1.296 1.323 1.3620 1.3636

105 78 a t 19 m m .

1.3861

1.4262

4 6 . 5 - 4 6 . 7 at 757 m m . 85-86 140-141

1.3280

88 36.5 110-112 112.5 72.6 76.2

1.4175 <1.3 1.4550 1.4460 1.3890 1.3886

CH3OH +

2

206.4

38-41 49-53

Amide + P O s CF C1CFC1CN + Z n CF3CFCICF2CI + Z n CH COCH + F

2

2 3

2 4

3C F 2C C 1 = C H 2 + K M n 0 4 2C= HC FC2H+B rC H+20N a l 3O H 2+ C2F = C F 3C C l B r C H 2B r + 2H g O + H F 3 2 3CC HH BB rr CC HH BB rr CC ll ++ HH gg OO ++ HH FF 3C C l B r C H B r + H g O + H F 3 2

T A B L E I (Continued)

2

C3H5FOS C H F0

35 2

C3H5F3 C H F 0

3 53

36 36

C3H6FNO C H F

3 62 C H F 0 3 62 C3H7F •

C3H7FO C H7F0 C4Br F6

3

2

2 C C1 F S 4 28 C C1 F8S 4 2 2 C C1 F S 4 283 C C1 F 0 4 37 C F 46 C F C F 0

48 463

M.p.,°C

162 -3 44 72 85-86.4

2 2 2 2 3 2 2 3 2 2

2 3 2 2 3 CH2 FCH2COOH FCO2C2H5 CH CH CF 3 2 3 CF CH(CH )OH 3 3 CH OCF2CH2F 3 CH3OCH2CF3 CH BrCH2CH2F 2 CH C10CH CH F 2 2 2 CH ClCHOHCH F 2 2 CH FCONHCH 2 3 CH CH CHF 3 2 2 CH CF CH 3 2 3 CH FCHOHCH F 2 2 CH OCH CHF 3 2 2 C H F O C H 5 (impure) 2 2 CH CH CH F 3 2 2 CH3CHFCH3 CH CHOHCH F 3 2 CH FCHOHCH OH 2 2 CF -CF2-CFBrCFBr 1 2 1 (CF C1CF ) S 2 2 2 (CF C1CF ) S 2 22 2 (CF C1CF ) S 2 22 3 CF CCl OCF CF Cl 3 2 2 2 CF C=CCF 3 3 CF CF CF=ÇF 2 2 CF CF=CFCF 3 3 (CF CO) 0 3 2

B.p.,°C

-32

-149 -52

t.

°c

d*

25

1.5093

10 21 20

1.3693 1.373

Preparation

2.089

1.090

CH =CHCH F + Br CH =CHCH I + AgF (CH CH CO) 0 + HF CH BrCOCH + T1F C H F C H O H C H F + KOH

2 2 2 2 3 2 2 2 3 2 2

0.974 0.96724

-159 -133.4

20

1.3679

1.1744

CH C1C0 CH

15 25 3 25 20 20

1.3172 1.2997 1.2942 1.429523 1.4120 1.4360

1.2799 1.1820 1.1661 1.542 1.190 1.300

CCl2=CHCH + HF CF3COCH3 + H CH3OH + C F = C H F C F C H O N a + CH3Br Br(CH ) Br + KF FCH CH OH + (CH 0) CH C1CHCH + HF

7-8 -0.1 59 at 4 0 m m .

0 20

1.2904 1.380

0.9204 1.2443

22 20 -20 20

1.304 1.3326 1.3240 1.3822

1.0214

20

1.3889

2.1981

47 24 -3.2 -10.1 107-108

232 310 76 389 272

3

142-143 104.5 51-52 at 2 m m . 55.5 -13 77.4 45.2 31.2 101.4 4 2 - 4 3 at 60 m m . 153-156

163 421 160 421 213 509 363 210 232 273 271

2 2 3 + KF C H 2 FCH2CH2OH + K 2C r 20 7 CICO2C2H5 + K F 3

2 3 2 23 2 2 2 3 + HC1 2 2 C H 2 F C 0 C H + H2NCH3 2 3 CH3CHCICH2CI + H g F 2 C H 3 C = C H + H F , CH3CCI2CH3 +

64 -105

Ref.

CH2FCHCH2 + HF CHF CH Br + CH ONa CHBrF + KOC H (CH ) + HF CH3CH=CH + H F CH CHCH + HF

2 2 3 2 25 23 2 3 2

SbF

3

53 205 157 272 477 210 156 156 272

Ο

103 at 13 m m . 96

-117.4 -60.4 - 1 2 9 to - 1 3 9 -65

68-72 141-142 84-88 at 40 m m . 89.6 -24.6 1.1 0.4-3.0 40

CF2CF2CF=CF + B r I 1

159 174

-

20

1.3303

1.6486

CF =CF

380

C F C H O C F C F H + CI C F C C 1 = C C 1 C F + Zn C F C F C F C 1 C F C 1 + Zn 1 1

210 185 206

CF3CFCICFCICF3 + Z n

196 502

2 2 + S 2C 1 2 3 2 2 2 3 3 2 2

CF3COOH

+ p 2o 5

PAUL TARRANT

C H BrF C H ClFO

Structure CH BrCHBrCH F CH =CHCH F CH CH COF CH FCOCH CH CH-CH F \ i Ο CH FCOSCH CH FC0 CH

276

Formula C3H5Br F C3H5F C3H5FO

CF CF CF CF CF CF CFBrCHF 1 1

4 4 6 C HF 4 7 C H F N 4 23 C H F 0 4 244 C H F 4 26 C H F 0 4 262 C H F0 S 4 3 22 C H F N 0 4 332

3 2 2 3 2 2 CF -CF -CF-CHF 21 2 1 2 CH =C(CF )CN 2 3 (CF COOH) 2 2 CF CH=CHCF 3 3 CF C0 CH CF 3 2 2 3 2-Thiophenesulfonyl fluoride

C H F 0

CF C0 CH=CH CF COCH COOH CF COCFs-semi-carbazone CHF CF OCH CF

C Fio C HBr

4 332 4H 3F 30 3 4HH 3FF 6N0 30 4 37 4HH 4FF 20 4 4 44 C H F 4 46 C H Br F 4 5 23 C H C1F 0 4 5 22 C H F 4 5 C H FO 45 C H F0 45 2 C H F N02 4 52 C H F 4 53 C H F N 0 4 532 C H F 0 4 532 C C C C C

C C C C C C C C

4HH 5FF 300 3 4 55 4HH 66BB rr FF 0 2 4H B r F 30 46 3 4H e B r 2F 2 4HH 6CC l1FFO0 S 46 2

C H C1F 0

46

3

s-Pyrazolone,

3-methforyl-

3 2 2 3 2 3 2 2 2 3 (CHFCOOH)2 CF CF CH CH 21 2 1 2 2 CF CH CH CF 3 2 2 3 CF CH(CF )CH 3 3 3 CF CBr(CH )CH2Br 3 3 CF C1C0 C H5 2 22 CH =CFCH=CH 2 2 CH =C(CH )COF 2 3 CH CH=CFCOOH 3 CH CF=CHCOOH 3 (CH2FNHCO)NH CF C(CH )=CH 3 3 2 CF C(=NH)CH CONH 3 2 2 CF C0 C H 3 225 CF CH CH CCX)H 3 2 2 CH C0 CH CF 3 2 2 3 CF CHOHCH COOH 3 2 CH CF OCH CF 3 2 2 3 CH BrC0 CH2CH F 2 2 2 CF CBr(CH ) 3 32 C H OCF CHFBr 25 2 CH BrCHBrCF CH 2 2 3 CH FCOSCH CH Cl 2 2 2 CH FC0 CH CH C1 2 2 2 2 CH C1C0 CH CH F 2 2 2 2 CHC1FC0 C H 225 C H OCF CHClF 25 2

-84.5

4 56 at 632 m m .

25

1.3402

1.8504

16

87 -90.5 -65.5

17-18 1 5 0 a t 15 m m . 33.2 55 95 at 20 m m .

2.2 18

1.2825 1.2812

1.4128° 1.4725

-53.7 -106.7 -54

112 83 84

3 2

25

1.3151

1.2031

56.7

20

1.2728

1.4870

50.5

25

1.3046

3

1.2752

0 0 14.5 23 0 25

1.2732 1.2712.9

1.3702 1.3725 1.9825 1.252 0.951

39.5-40.5 79

24.6 21.5 131 97 11.8-12 56.6

1.4410 1.330 1.3703

109 at 8.5 m m . 6.4

1.056

0

137 62

16.7

1.30783«

1.1953

78

16

1.3219

1.2595

20 17 10.5 27

1.4530

1.659 1.550 1.6121 1.933

33 69.5-70

-12 -8.7

2 2 1 + HBr I CHC1F + heat 2 CH COH(CF )CN + SOCl 3 3 2 CF CF CC1=CC1 + Ο 2 2 C F C C 1 = C C 1 C F + Zn + C H O H 3 3 25 CF CH COCH C0 C H

209

72.8 153

C + F CF CF CF=CF

37.8 8 7 - 9 0 a t 12 m m . 80 106 157 105 at 33 m m . 178-179 178 128 82 at 630 m m .

1.3794 1.4594

20 25 20

1.3230 1.3927 1.3479

1.225 1.2726

?

2 2 2 5+

C H + CF C-OH CF COCH C0 C H + HC1 CF COCF + H NNHCONH + HOCH CF CF =CF CH FCOOH + peroxide CF =CF + CH =CH

NH

22 3 3 2 225 3 3 2 2 2 2 2 3 2 2 2 2 2 + Η CF C=CCF 3 3 CH C(CF )=CC1 + HF/SbF 3 3 2 3 CF C(OH)(CH )2 + P B r 3 3 5 CF ClCOCl + C H OH 2 25 C H = C H - C = C H + HF 2 Acid chloride + S b F 3 C H C H F C H F C O O H + NaOH 3 CH CF CH C0 C H 3 2 2 2 2 5 + NaOH C H 2 F C O N H + B r + KOH 2 CF C(OH)(CH ) + PBr 3 32 5 CF C0CH C0 C H 3 2 2 2 5 + NH3 CF C0 H + C H OH 3 2 25 CF CH CH MgCl + C 0 3 2 2 2 CH COCl + CF CH OH 3 3 2 + HC1 CF CH0HCH C0 C H 3 2 225 CF CH ONa + CF C1CH 3 2 2 3 Acid halide + C H F C H O H 2 2 Alcohol + HBr C HF Br 2 3 2 + N a O C 2H 5 C H C F C H = C H + Br 3 2 2 CH FCOCl + HSCH CH C1 2 2 2 Acid chloride + CH ClCH OH 2 2 Acid chloride + C H F C H O H 2 2 CHFClCF OC H 2 2 5 + H 2S 0 4 C H QH + CF =CFC1 25 2

3

448 336

361 105 215 185 510 457 152

gQ > 2

122 506 147 210 264 68

5

° Ο 2 * Ď d S

209 508 483 351 123 37 215 53 508 506 502 338 510 262 210 272 508 475 326 422 422 422 554 369

g § H > 3 g Q S § Ď g 5} W

K> ^

T A B L E I (Continued)

H Cl2F 0 H FI0 H FN H F HeF 0

46 2 46 2 46 4 62 4 22

C C C C

Structure

M.p., °C

CHCI2CF2OC2H5 CH2lC0 CH CH F CH FCH CH CN CH2=CHCF2CH3 CH2FC0 CH2CH2F CHF2C02C H CH CH CF COOH CH3CHFCHFCOOH

2 2 2 2 2 2 2 25 3 2 2

-25.4 8.1

CF3CHOHCH2CONH2 CF COCH -semicarbazone (CHF CH )NNO CHF2CF2OC2H5

C H C1FN 0 C H C1F 0 C H Cl FO

CH C1C(CH F)=NHC0NH CH2CICF2OC2H5 CHCI2CHFOC2H5 CCl FC(OH)(CH ) CH CH CF=CH CH CF=CHCH C H COF CH COSCH CH F

3

3 2 2

CHF CF20CH CH OH CHF2CF2SC2H5 CH2FCONHCH2CH2CI

2

120.5 9 9 - 1 0 5 a t 15 m m . 98 at 100 m m . 24.5 91 99.2 100-101 at85 mm. f 811 s t e r e o 1< 0J i s o m e r s

t. ° C

20 20 0 20 17.5 25

n<

1.5080 1.330

1.3618

1.991 1.0034 0.951 1.2906 1.1800 1.2201

124-125 127 179 57.5

2 2

65

94 at 100 m m . 86-88 77 at 0.3 m m .

Preparation

d

16.5 25

1.1978

1.4490 1.294

25

1.3418

1.4159

Ref.

C H C 1 C F C 1 + C H O H + KOH Acid chloride + alcohol

2 2

25

CH3CF2CH2CH2CI + K O H Acid chloride + alcohol C H F C O O H + C2H5OH C H CF CH=CH + KMn0 CH CH=CHC0 H + F

2 25 2 3

2

2

4

CF3CHOHCO2C2H5 + NH3 CF3COCH3 + H N H N C O N H (CHF CH )2NH + HN0 CF =CF + C H OH

2 2 2 2 2 2 2 25 CF =CF 2 2 ++ C( C HH 2SOHH ) 2 CF =CF 2 2 25 CH FCONHCH CH OH + SOCl 2 2Ο 2 2

155 272 391 351 422 479 215 37 262 507 481 170, 364 170 121 53

II

47 3 47 2 47 2 C H F 47 C H FO 47 C H FOS 47 C H F0 47 2

2

2

2 3 2 3 37 3 2

2

111-112 91-93 121 4 1 at 13 m m . 23.5 26 67 87 at 100 m m .

32 2 3 2

CH3CO2CH2CH2F CH3CH2CHFCOOH CH2FCH(CH3)COOH CH3CHFCO2CH3 CH FCH C0 CH CH2FCH2CO2CH3 CH2FC0 C H CH FCH CH COOH CH CH CH CF CF CH OCH CH CF CH CH OCH CF C(OH)(CH ) (CHF CH ) NH CH ClCH OCH CH F

2

C H F C H F 0

4 73 4 73

C H F N C H C1F0

4 74 48

2 2 3 225 2 2 2 3 2 2 3 3 2 2 3 3 2 2 3 3 32 2 22 2 2 2 2

-115

20.7

119.3 90 at 13 m m . 8 0 - 8 2 a t 13 m m . 107-108 117 117 120 61 at 2 m m . 16.7 49.8 54.9 81.6 124 144

25

1.214 1.3492

0.824

15.5 25

1.3487 1.4525

0.944 1.4041

20

1.377910

1.0982

20

1.3767

1.093

20 20 20 22.6 16.5 20

1.0144 1.3042 1.3114 1.3324 1.3490 1.4170

1.2921 1.0910 1.1129 1.1903 1.3041 1.137

0

Ketone + H N H - C - N H CF =CHC1 + C H O H CHFC1CHC1 + N a O C H CFC1 C0 CH + CH MgBr

2 2 2 25 2 25 2 2 3 3

C H COF + C H C0 H CH3COSH + C H = C H F

65

37 2 2 CH C0 CH2CH Br + AgF or HgF 3 2 2 2 H y d r o l y s i s of e t h y l e s t e r CH3CH(CH )COOH + F 3 CH CHBrCOOCH + KF 3 3 A c i d + CH3OH A c i d + CH3OH CH BrC0 C H5 + TIF CH F(CH ) OH + H Cr 0 C C 1 = C H C H + HF CF CH ONa + C H C1 CF CH CH ONa + CH Br C F C 0 C H n + CH MgI CHF CH Br + NH H O ( C H ) 0 ( C H ) 2 F + SOCI2

2 22 2 23 2 27 2 25 3 2 25 3 2 2 3 3 25 3 2 2 3 22 2

272 170 478 159 326 326 306 131, 159 498 37 37 421, 162 160 388 160 189 210 210 508 481 272

PAUL TARRANT

4H 6F 3N 0 2 4HH 6FF 3NN 300 4H 6F 40 2 4 64 C H F 0 4 6 42 C H F S 4 64 C H C1FN0 47

B.p., °C

278

Formula C C C C C

l

C H ClF NO

48 2

CH FC(=NHHC1)

161 ( d e c o m p . )

2

CH FCN

2

+ HOCH CH F

+ HC1

2 2

53

OCH CH F

C C C C

4H 8F N 0 2 4HH e8FF N 30 4H F 20 4 82

4 8 24 49 49 C H FO 49

(CH FCH ) S0 CH FC(=NH-HCl)OC H CH CH CH CH F CH CF(CH ) C2H5OCH2CH2F CH2FCH2CH2CH2OH CH FC(OH)(CH )

2 22 4 2 3 2 2 2 3 32

2

C F N C F

21 131.5 -117

-77

32

NCCF CF CF CN CF CF CF=CFCF

C H F 0

5 2 64 C H F 0 5 2 82 C H C1F 0 53 4

CF (CF COOH)

C H F N OS C H F N

Uracil, 2-thio-6-trifluoromethylCF CF CH CHCN

2 2 2 2 2 I 2 (CF ) 2 5 CF COCH CCF 3 2II 3

30.5

20

66.5

15

1.3133

0.9016 1.039

1 4 5 a t 18 m m .

25

562 58 C F 5 10 C H F 0 5 2 62

114 at 0.1 m m .

32 12.1 75 5 2 - 5 3 a t 11 m m . 58 at 8 2 m m .

15 12

1.3419 1.3241

0.7824 0.7527

20

1.3913

0.9610

37-38 33-35

I

10

21-22 63-65

20

78-88

134-138 at 3 m m .

1.648

CH FC0 CH CH FCOCH CH C = CCH (CH C1CH ) CHF CH Br

H NCH CH OH 2 2 3+ + H2NNHCONH2 2 2 2 2 3 + HF 3 30 +• H g F 2 22 2 2 2 +- N a O C 2H 5

CH FCH OH + SOCl C H F C N + C H O H + HC1 » - C H I + HgF

2 2 2 49

2

25

C2H5OCH2CH2CI + K F CH FCH CH2CH202CCH ( C H ) Η C H Q + HF

2 2 3+ NaOH 32 2 (CF ) (CONH ) + P 0 23 22 2 5 CHC1F , 650° 2 C + F/HgF 2 CF C0 C H 3 2 2 5 + C F 3C O C H 3

53 387 157 343 210, 477, 403 423 53 93 158 162 159 272 341 361 446 197

ο

5 332 5 34 C H FN 54

2 2

2

CHF2CF2CF2CF2COOH CF CF CH -CHCOCl

I I

2 2 2

C H F N C H F

CF CF CH C=CH

C H F 0

CF CF CH CHCHO

5 44 5 44 5 4 42

2 2 2 2 2 2I

2 2 2

4 6 22

1

(CF ) (CONH )

23

22

2

1.3909

25

1.3568

125

20

1.4674

2-Aminopyridine

+ HBF

20

1.4700

3-Aminopyridine

+

53-54

61.5-63.0

CF =CF

2

2+

341 21

344 68

148

105-107

2

CF CF CH CHCOOH

I C5H F N 0

2I

1

181

4

CH =CHCN

2

4+ HBF + 4

NaNO

z NaN0 2

65, 408 33, 408

CF CF CH CHCN + NH

3

18 68

I

2 2 2I

65

25

1.3318

1.2288

CF =CF

25

1.3768

1.5089

CF =CF

2 2

2

117-117.5

100 at 24 m m .

25

1.3684

1.5103

CF CF CH CHCN

+ H S0

2 2

2+ 2+

CH =C=CH

CH =CHCHO

2 2 2

I

1

2 4

(CF ) (COC H )2 + NH

23

25

3

68

21, 68 341_

279

C H F 0

I

1.4915

+ KMn0

248

2 2 2I

2

1.3782

2 2 2 24 2 2 2 2

HOOC(CF ) COOH, 280° CF CF CF CH CHCOOH + SOCl

I

Pyridine, 2-fluoro-

I

25

CF CF CF CC1=CC1

I

Pyridine, 3-fluoroNH II CF CCH CHCN

5 422

155-160 70 at 124 m m .

ORGANIC COMPOUNDS CONTAINING FLUORINE

C H F 0 S C H C1FN0 C H F

2 2 2 2 2 3 2 2 3 2 22 2 2 2

CH FCONHCH CH OH 2-Propanone, fluorosemicarbazone CH CF CH CH (CH FCH ) 0 CHF CH OC H5

280

T A B L E I (Continued) Structure

Formula C H F 0 C H F 0

C5H5CI2F3O2

CF CH CH COCF H(CF ) CH OH CF2CICFCICO2C2H5

5 532

CF2C1CC1 C0 C H5 CF3COCH2COCH3 CF CF CH CHCONH

5 46 5 48

C5H5CI3F2O2 C H F 0 C5H5F4NO

C5H ClF NO

6 2 5 62 5 22 5 62

C H F C H6F 0 C H F 03 C5H6F2O4

5 63 5 64 C H F 0 5 64

C5H6F4O2 C5H6F6O2

C5H7F

C5H7FO2 C5H7FO4 C5H7F3O2 C5H8CIFO2 C5H8CIF3O C H F C5H8F2O2 C5H8F2O3

5 82

C H F 0 C5H9FOS C5H9FO2

5 84

3

2 22 2 2 21 1 C H OCF CHClCN 2 5 2 CH =CHCF CH=CH 2 2 2 CH =CFC0 CH CH F 2 2 2 2 CH FCOCHFC0 CH 2 2 3 CH FC0 CH 0 CCH F 2 2 22 2 CH 0 CCF C0 CH 3 2 2 2 3 C H OCF CHFCN 25 2 CF CF CH CHCH 2 2 21 3 1 CF CF CH CHCH OH 2 2 21 2 1 1,3-Dioxolane,

3 2 2 2 2 3 2 2 2 3 2 3 2 3 2 2 3 2 CHC1FCF OC H7(0 2 C 3H CH =CHCF 2 225 CH FC0 CH(CH )CH F 2 2 3 2 CH FCH OC0 CH CH F 2 2 2 2 2 CH OHCF C0 C H 2 2 2 25 CHF CF OC H (n) 2 2 37 CH FCH CH COSCH 2 2 2 3 CH FCH CH C0 CH 2 2 2 2 3

-135.3

57 -35

5 92

C5H9F3I

3 2 2 2 22 3 2 2 3

82 170-171 142 172 107

25

1.3020

23 23

1.3830 1.418

d<

93 at 100 m m . 46.8 142 97 a t 14 m m .

37.6

3 2 2 CH3OH+ 2 2

1.3552 1.3981

0.9368

58-59 120-122 68.5

20

1.3721

1.3059

25

1.3193

1.1961

155-157

25

1.3670

1.3998

25 20

1.397 1.3759

0.847 1.0826

15 25 20 20 20 25 20 20 25 25 20

1.3314 1.3994 1.4227 1.3575 1.3521 1.3438 1.398 1.3940 1.3830 1.3141 1.4587

1.1823 1.170 1.2365 1.2173 1.2010 0.921 1.202 1.2552

25

1.4165

1.207920

25

1.4335

1.1541 1.1135

CF3CN

Ref.

CF =CF + A c i d c h l o r i d e +- a l c o h o l Acid chloride + alcohol C F C 0 C 2 H + CH3COCH3 Acid chloride + NH3

330 121 60 60 197 21

C H OH + CF =CC1CN ( C H C 1 C H ) C F + KOH CH =CFC0 CH + CH FCH OH CH FC0 CH + NaOCH C H F C O F + (HCHO) Acid + alcohol CF =CFCN + C H OH CF =CF + CH =CHCH

60 184 79 421 421 184 60 68

3 2

20 20

47.4 65 at 50 m m . 8 0 - 8 2 a t 12 m m . 86 147 92 at 4 0 m m . 102 at 6 3 0 m m . 94 at 630 m m . 54-55 167 9 5 - 9 8 a t 16 m m . 181 71.7 at 630 m m . 54 at 6 m m . 135-137 122.5-123.0 108-109 98 at 19 m m . 184-185 137

Preparation CF CH CH MgBr

1.405 1.460

64.5

CH CF(CH3)C0 CH3 CH2FCHOHCH2CO2CH3 CHF CH NHC0 C H5 CF CH CH CHICH

n<

128-137

CH3CHFCO2C2H5

C5H9FO3 C H F N02

t. ° C

126-127

tetrafluoroethyl-

CF CH CH C(OH) CF3 CH =CF-C(CH )=CH CH2FC02CH CH=CH CH3O2CCHFCO2CH3 CF CH(0 CCH )CH3 CHClFC0 C3H7(n) CH CHFCH CHC1C0 CH CHClFCF OC3H7(n)

B.p., °C

5

25 2 2 22 2 2 2 3 2 2 2 2 3 3 2 3 2 25 2 2 2 3 CF =CF + CH =CHCH OH 2 2 2 2 1,3-Dioxolane + C F = C F 2 2 C F C H C H M g B r + CF3CN + H 0 3 2 2 2 CHnC-C(CH )=CH + HF 3 2 CH FCOCl + CH =CHCH OH 2 2 2 CH 0 CCHC1C0 CH + KF A c i d3 c2h l o r i d e + 2 a l c o3 hol CHC1FC0 CH + C3H7OH 2 3 CFC1=CF + n-C3H OH 2 7 CFC1=CF + t - C H O H 2 37 C H C F C H C H C 1 + KOH 2 5 2 2 2 CH IC0 CH(CH3)CH F + HgF /KF 2 2 2 2 CH FCH OCOCl + CH FCH OH 2 2 2 2 CH OHCF COOH + C H OH 2 2 25 C F = C F + C3H7OH 2 2 CH FCH CH COOH + CH OH 2 2 2 3 Chloro compound + K F + AgF CH CBr(CH )C0 CH 3 3 2 3 CHF CH NH + C1C0 C H 2 2 2 225 CF3CH2CH2CHOHCH3 F Ρ + I

68 169 330 72 391 162 509 554 391 369 369 215 272 272 381 364 391 159 162 421 391 481 330

PAUL TARRANT

C H F NO C H F

3 2 2 24 2

M.p., °C

c H F o

5 93

CSHIOFNO

C5H10F2 C5H10F2O C5H10F2O2 C5H11F

C5H11F2N C C1F N

6 83

C6CI2F7N3 C6CI3F6N3 C6CI4F5N3 C6CI5F4N3 C6CI6F3N3 C6Cl7F N C F C F CEFEN C F N C F C FI4 C6HBr F0 C HBr FO C6HC1 F0 C6HCI3F2O4S2

66 68

23

69 3 6 12 6 2 2 6 4 22

C6HFI2O2 CEHFN C6H Br FN0 C H Br FO C6H2CIF3O6S3 C6H2C1 F 04S C H CL2F N C H C1 F

2 2 3 62 3 22 2 62 3 62 3

CF CH CH20C H5 C3H7OCH2CF3 CF CH CH CHOHCH (C H ) NCOF C H CF2C2H5 CH CF C H7

3 2 2 3 2 2 2 52 25 3 23

3 -94.0

CHF2CH2OC3H7 (CH2FCH20)2CH2 CH3CH2CH2CH2CH2F C3H7CHFCH3 CH3CH2CH(CH3)CH2F (CH )2CHCH CH F (CH FCH ) NCH

3 2

2 2 22 3

s-Triazine, 2-(chlorodifluoromethyl)-51.6 4,6-bis(trif luoromethyl) s-Triazine, 2,4,6-trimethyl-, -36.2 dichlor oheptaf luoro s-Triazine, trichlorotrimethylhexa-21.1 fluoros-Triazine, trimethyl, tetrachloropentafluoro- - 9 . 4 s-Triazine, trimethyl, pentachlorotetrafluoro—10.2 s-Triazine,trimethyl, hexachlorotrifluoro9.6 s-Triazine,trimethyl, heptachlorodifluoro14 Hexafluorobenzene -14 Cyclohexadiene, octafluoro6 NC(CF2)4CN s-Triazine, 2,4,6-tris(trifluoromethyl)-24.8 Cyclohexane, dodecafluoro48-49 Hexane, tetradecafluoro- 4 3-F-2,6-Br-benzoquinone 150 2,4,5,6-Br-3-F-C6HOH 114 3-F-2,6-Cl-/>-benzoquinone 145 2,4,6-Cl-l,3-S0 F-C H 110 3-F-2,6-I-benzoquinone 195 Cyclohexane, hendecafluoro41-43, -16 to-l< 3-F-4,6-Br-2-N0 -C HOH 76 3-F-2,4,6-Br-C HOH 152 3-Cl-l,2,4-S0 F-C H 180 4,6-Cl-l,3-S0 F-C6H 141-143 15 2-Picoline, 3 , 5 - C l - a , a , a - F 2,4,5-Cl-C H F 62 2,4,6-Cl-C H F 11.2

72.3 at 746 m m .

20

1.3258

126 154 60.2 59

25

1.330

20 20

1.3370 1.3352

0.9023 0.8904

20 20 20 20

1.3860 1.3562a

1.1302 0.7880 0.7788 0.7906

20

1.3540

145

20

1.3827

167

20

1.4129

194 217 248 274 81-82 57 62 99 50 60

20 20 20 20 20 20 20 20

1.4420 1.4611 1.4920 1.5009 1.3760 1.3149 1.2770 1.3231

89 162-164 62.8

53.2 123-124 at 762 m m . 119

1.0593

3 2 2 25 37 3 2 3 2 2 3 (C H )2NH + C O F 25 C H CC1 C H + H2F 25 225 C H C=CH + HF 37

CH BrCHF

1.3520 1.3576

2 2 + N a O C 3H 7 3 5 3 7 3 CH CH2CH(CH )CH2BR + A g F 3 3 (CH ) CHCH CH2L + HgF 26 / > - C3H23C 6H 4S20 3C H 2C H 2F + C H 3N H 2 1.6090 CeCl9N + H F / S b F 3 5 1 . 6 2 3 4 2 6 CECL9N + H F / S b F 3 5 1 . 6 4 5 8 2 6 CECL9N + H F / S b F 3 5 1 . 6 6 5 6 2 6 C6CL9N + H F / S b F 3 5 1 . 6 8 6 0 2 6 C6CI9N3 + H F / S b F 1 . 7 1 3 4 2 6 C6CI9N3 + H F / S b F 5 1 . 7 4 0 0 2 6 C6CI9N3 + H F / S b F 5 5 1.612 C6C16 + S b F 5 ; then Z n 1.601 C6C16 + S b F ; then Z n 5 1.430429 A m i d e + dehydrating agent 1.585726 C C 1 N 6 9+3F+ H F / S b F 5 C H 66 C + F CH2FCH2OH + (CH20) + HC1

n - C H u B r + HgF C H CHBrCH +AgF

3-Fluoro-2,4,6-tribromophenol 3 - F - 2 , 4 , 6 - C l - C H O H + HNO3 Sulfonyl chloride + K F 3 - F - 2 , 4 , 6 - I - C e H O H + HNO3 C H + F

6

2 6

2 6 6 2 62 2 2 62 62

CF CH CH ONa + C H Br. C H ONa + CF CH C1 CF CH CH MgBr + CH CHO

62

66

3-F-2,4,6-Br-CeHOH + NaN0 3-F-C H OH + Br Sulfonyl chloride + K F Sulfonyl chloride + K F Chloro compound + H F

64

178 208.4

1.4780

1.5122

D i a z o t i z a t i o n of a m i n e

210 26 330 132 200 157, 395 210 273 500 49 49 500 66 333a 333a 333a

333a 333a 333a 333a 286 331 340 333a 148 448 + HNO3 2 2 8 383 228 85 228 148

3

382 383 85 85 321 87 41

Ο W

©

> 2

ο ο d CD Ο Ο

55 > Ο

d

ο w

ΗΊ Μ

Κ)

00

282

T A B L E I (Continued) Formula C H Cl FO C6H2CI3F2N C H C1 FN C H FI 0

62 3 62 4 62 3 C H FN 0 6 2 36 C H FN 0 6 2 37 C6H2F8O4 C H BrFN0 63 3

Structure 3-F-2,4,6-Cl-C HOH 2-Picoline, 3,5,a-Cl-of,a-F

6

2-Picoline, 3 , 5 , a , a - C l - a - F 3-F-2,4,6-I-C HOH Picryl fluoride P i c r i c acid, 3-fluoroAdipic acid, octofluoro2-Br-4-F-6-N0 -C H OH 4-Br-2-F-6-N0 -C6H OH 6-Br-2-F-4-N0 -C H OH 3-Br-4-N0 -l-S0 F-C H 2,4-Br-C H F 3,5-Br-C H F 3,4-Br-C H F

6

B.p., °C

55 8 9 - 9 3 a t 10 m m . 1 0 6 - 1 0 8 at 10 m m . 138-139 150-160 173

85 59 89 38 2

230 199 237 178 140 at 5 m m . 152 168

42 7 1 - 7 5 a t 10 m m . 9 5 - 9 6 at 3 m m .

102

228 321 321 228 542 225 340 382 382 382 457

64

2 4

3 3 3 3

64

171

67 132 24.3 34 43 50.2

Ref.

62 62 62

216 205

10.2

Preparation 3 - F - C H O H + CI Chloro compound + HF Chloro compound + HF 3-F-C H OH + I Picryl chloride + NaF 3-F-C H OH + H S0 /HN0 Octafluorodichlorocyclopentene + K M n 0 4-F-2,6-Br-C H OH + NaN0 2-F-4,6-Br-C H OH + NaN0 2-F-4,6-Br-C H OH + NaN0 B r o m o s u l f o n y l f l u o r i d e + HNO3 Schiemann reaction Schiemann reaction 4-Br-C H F + Br Amine + Br Nitrophenol + B r 2-F-C H OH + Br 4-F-C H OH + Br F l u o r o n i t r o b e n z e n e + CI Schiemann reaction

64 64

67 62 101 104

69 119 45 35 56 41

t. ° C

64 64

4-Cl-C H F + HN0 Schiemann reaction Chlorosulfonyl fluoride + HNO3 Sulfonyl chloride + K F Sulfonyl chloride + K F Chloro compound + HF 3 - F - 4 - C l - C 6 H N H + Sandmeyer r e ­ action Amine + N a N 0 +- H F Schiemann reaction 4 - F - C H O H + NaCIO Chloro compound + HF

64

3

3 2 2

64

4-F-C H OH

64 + 64 2

NalO

4-F-C H N0 + HN0 Schiemann reaction Schiemann reaction 4-F-C H OH

64

+ HNO3

H y d r o l y s i s of a n i s o l e

3

4

463 89 523 34 230 383 383 401 92 495 495 457 283 85 321 87 275 92 228 321 127 228 456 234 89 88 432, 490 432

PAUL TARRANT

2 62 2 2 2 62 C H BrFN0 S 63 4 2 2 63 C H Br F 63 2 63 63 63 C H Br FN 0 6 3 2 2 2 23 -- FF -- 44 ,, 66 -- BB rr -- C3 - HN 0O2-HC 6H N H 2 C H Br FO 63 2 62 2-F-4,6-Br-C H OH 62 4-F-2,6-Br-C H OH 62 2-Cl-4-N0 -C H F C H C1FN0 63 2 2 63 3-Cl-5-N0 -C H F 2 63 4-Cl-2-N0 -C H F 2 63 4-Cl-3-N0 -C H F 2 63 C H C1FN0 S 63 4 43 -- CC ll -- 34 -- NN 00 2-- CC e6HH 3SS 00 2FF 2 3 2 C H C1F 0 S 6 3 2 4 2 42 -- PCi lc-oll,i 3n -e S, 0 25F- C- Cl -6aH, c3r , o r - F C H C1F N 6 3 3 C H C1 F 2,5-Cl-C H F 63 2 63 3,4-Cl-C H F 63 3,5-Cl-C H F 63 C H Cl FO 4-F-2,6-Cl-C H OH 6 3 2 62 C H C1 F N 2-Picoline, a , 5 - C l - a , a - F 6 3 22 C H C1 F N s-Triazine, 2,4,6-trischlorofluoromethyl 6 3 3 3 3 4-F-2,6-I-C H OH C H FI 0 63 2 62 C H FI 0 S 2,6-I-4-S0 F-C H OH 6 3 23 2 62 C H FN 0 2,4-N0 -C H F 6 3 24 2 6 3 3,4-N0 -C H F 2 63 3,5-N0 -C H F 2 63 4-F-2,6-N0 -C H OH C H FN 0 2 62 6 3 25 2-F-4,6-N0 -C H OH 2 62

M.p., °C

C H FN205

63

C H F0 C6H3F2NO2 C H F N07S2 C H F

C H C1F0 S

64

2

C H C1F0 S

64

3

C H C1F0 S C H C1F N

6 4 52 64 2 C H C1 FI0 S 64 2 2 C H C1 FN 64 2 C H FI 64 C H FNO 64 C H FN0 64 2

2 2 l,4-F-2-N0 -C H 2 63 6-N0 -2.4-S0 F-C H OH 2 2 62 2,4-F-C H F 63 1,3,5-S0 F-C H 2 63 4-Bromobenzeneiododifluoride 4-Bromobenzeneiodoxydifluoride 4-Br-C H F 3-F-2-Br-C H OH 3-Br-C H S0 F

64 63 64 2 4-F-2,6-Br-C H NH 62 2 3-F-2-NH -4,6-Br-C HOH 2 6 3-F-6-NH -2,4-Br-C HOH 2 6 2-Cl-C H F 65 3-Cl-C H F 65 4-Cl-C H F 65 4-Cl-C H S0 F 64 2 3-Cl-C H S0 F 64 2 4-F-C H S0 Cl 64 2 2-Cl-C H S0 F 64 3 3-Cl-C H S0 F 64 3 4-Cl-C H S0 F 64 3 2-SO2CI-4-SO2F-C6H3OH 2-Picoline, a-Cl-a,a,F Benzenesulfonyl fluoride, dichloride 5-F-2,4-Cl-C H NH 2-I-C H F 4-I-C H F 4-F-C H NO Nicotinic acid, 2-fluoroNicotinic acid, 6-fluoro2-F-4-NO-C H OH 3-F-4-NO-C H OH 2-F-C H N0 3-F-C H N0

64 64 64

62 2

103 at 2 5 m m . 88

166-167 110 225(d) -8 <-20

152 123 at 8 0 m m . 122 at 23 m m .

63-64 143(d) 148 -42.5 <-78 -27 47-48

4 4 + HNO3 6 4 3-F-4-NH -C H OH + FeCl 2 6 3 3 4-F-C H F + HN0 64 3 N i t r a t i o n of s u l f o n y l f l u o r i d e Schiemann reaction Sulfonyl chloride + KF

C H F + Br 3 - F - C 6 H O H disulfonate + Br 3-NH -C H S0 F + Cu Br + HBr

65 4 2 64 2 2 2+ 2-F-5-NH2-C H3S0 H + Br 6 3

138

4-F-3-Cl-C H NHNH

128

Schiemann

130

Schiemann reaction Sulfonyl chloride + KF

63

2+

NaN0

CH3COOH + CuS0

reaction

90 at 22 m m .

3-NH -C H S0 F

152 at 26 m m . 154 at 2 2 m m . 208-211

Acid + chlorinating agent Sandmeyer reaction Sandmeyer reaction Sandmeyer reaction

36

2 64 2

+ Cu Cl

2 2++

105 at 100 m m .

NaN0

Chloro compound + HF

98-99

3-I-C H S0 F

67 -14.5

C h l o r i n a t i o n of 3 - f l u o r o a c e t a n i l i d e Schiemann reaction D i a z o p i p e r i d i d e + HI

64 2

219 189 183

35 164

+ Cl

2

+ (NH ) S 0 4-F-C H NH O x i d a t i o n of p i c o l i n e O x i d a t i o n of p i c o l i n e 2-F-C H OH + HN0 From the anisole

64 2

146 144 161 -5.9 36

214 86 at 19 m m .

C H F + HNO3 Schiemann reaction

26.5

96 at 22 m m .

Schiemann

64

42 2 8

2

65

reaction

2

4

HC1

75-76 3-iodo,

225 225 225 224 490 456 428 85 539 539 434 226 457a

3 - F - C e H O H + HNO3 3 - F - C e H O H + HNO3 3 - F - C H O H disulfonate

2

462 384 148 401 41, 293 495 85 457 284 281 281 281 456 321 456 87 402 536 401 348 348 222 223 493 433, 489 433

283

63 63 64 2 64 2 4-F-C H N0 64 2

80 69 138 80 -11.7 99

ORGANIC COMPOUNDS CONTAINING FLUORINE

63 2 6 32 6 33 C6H3F3O6S3 C H BrF I 6 4 2 C H BrF IO 64 2 C H BrF 64 C H BrFO 64 C H BrF0 S 64 2 C H Br FN 64 2 C H Br FNO 64 2 C H C1F 64

3-F-4,6-N02-C6H OH 3-F-2.6-N02-C6H20H 3-F-2,4-N02-C6H OH Quinone, fluoro-

to

T A B L E I (Continued)

00 Structure

Formula C H FN0

64

3

C H FN0 S

64 5 6 42

C H F

C C C C

6H 4F 20 6HH 4FF 200 4SS 2 6H 4F 2 5 2 6 44

C H F N 0 C H Br F C H C1FN

6 4 8 22 65 6 65

C H C1F 0

6 5 42 C H F 65 C H FN 0 65 2 C H FN 0 6 5 22 C H FO

65

C H F0 S

65 2

C6H5FO3S C6H5FS C6H F IO C H F N

52 6 52

2-F-6-N0 -C H OH 3-F-5-N0 -C H OH 3-F-4-N0 -C H OH 3-F-6-N0 -C H OH 3-F-2-N0 -C H OH 4-F-2-N0 -C H OH 4-N02-C H S0 F 2-N0 -4-S0 F-C H OH 2-F-C H F 3-F-C H F 4-F-C H F 2,4-F-C H OH 3-S0 F-C H S0 F 4-HO-3S0 F-C H S0 F CF CF CH CH-C=CH 1 1

2 63 2 63 2 63 2 63 2 63 2 63 64 3 2 2 63 64 64 64 63 2 64 2 2 63 2 2 2 2 CF CF CH=C-CH=CH 2 1 2 2 1 Adipamide, octofluoroHexabromofluorocyclohexane 2-Cl-5-F-C H NH 3-Cl-4-F-C H NH 4-Cl-3-F-C H NH CF CF CH CC1C0 CH 1 1

63 63 63 2 2 2

2 2 2 2 3

M.p.,

B.p., °C

°C

2 63 2 2 3 2 2 3 2 2 63 2 3-F-C H OH 6 4 4-F-C H OH 64 C6H S0 F 5 2 4-HO-C6H4S0 F 2 4-F-C6H4SH Benzeneiodoxydifluoride 2,5-F-C H NH

63 2

η'

d*

25

1.3553

1.2498

98-99

25

1.3742

1.2588

Vinyl acetylene +

156 a t 19 m m . 66-67 91-92 82-83 88.5

121 1 4 6 (d) 102 115 92 98 16.1 13.7 46.5

C H F

m.p.

65

NH +

53 at 14 m m . 77 at 14 m m . 74 at 12 m m . 203-204 9 0 - 9 1 at 14 m m . 162 85 at 30 m m .

3

25

1.3850

1.4478

3

2 2 2 CF =CF 2 2

359 90 225 225 225 221 281 456 433 433 433 438 456 456 68 68

>

d

341

3

Br

Nitro compound +

77 120 13.5

64 2

Ester + and / 3 - i s o m e r s have s a m e 211

57 at 36 m m .

3 3 3

64 2 64 2

38-39 120-121

a-

Ref.

82-84

64 3 2 63 64 64 64

-34 -59 -13

237 154-156 26 44 61

Preparation + HN0 2-F-C H OCH 3 - F - 5 - N 0 - C H O C H + HC1 3-F-C H OH + HN0 3-F-C H OH + HN0 3 - F - C H O H d i s u l f o n a t e + HNO3 From acetoxy mercuri derivative F r o m diazonium fluorosulfonic acid 4-HO-C H S0 F + HN0 From 2-F-C H NH From m-phenylenediamine F r o m />-phenylenediamine H y d r o l y s i s of a n i s o l e Sulfonyl chloride + KF 4-HO-C H S0 F + HOS0 F Vinyl acetylene + C F = C F

90-91 112 42 32 39 195

85 2-Fluoronicotamide 3-Fluoronicotamide 2-F-5-N0 -C H NH 3-F-5-N0 -C6H NH 4-F-2-N0 -C6H NH 4-F-3-N0 -C H NH 2-F-C6H4OH

t. ° C

Sn/HCl

CF =CF

2 2 + C H 2= C C 1 C 0 2C H 3 C H NH 6 5 2+ N a N 0 2+ HF Acid chloride + N H 3 Acid chloride + N H 3 2 , 4 - N 0 - C H F + SnCl 2 6 3 2 3 , 5 - N 0 - C H F + NH4HS 2 63 H y d r o l y s i s of a c e t a n i l i d e

526 87 401 87 68

C H

536 348 348 495 91 495 234 427 427 427 456

C H OH + HOS0 F 4-F-C H MgBr + S

456 441

+ HN0 4-F-C H NH F r o m a n i s o l e + HI F r o m a n i s o l e + HI F r o m a n i s o l e + HI

64 2

3

6 6 + H O S 0 2F 65 2 64 3 - F - C H F + H N 0 , then 64 3

[H]

539 492

w

C6H5F2N05S2 C6H5F4N C H F

6 55

CeH FN

6

C C C C

6HH 6FFNNO0 S 6H 6F N 0 2S 6 6 52 6H 6F 4 C H F 0 6 64

2,4-S0 F-6-HO-C6H NH2

2 CF CF2 CH2-C(CH3)CN

120

2 2

CF2CF CH CF-CH=CH2

2 2I CF CF CH CH-CF=CH 2 2 2I 2 I 2-F-CeH NH 4 2 3-F-C H NH 64 2 4-F-C H NH 6 4 2 P y r i d i n e , 2 - F - 3 -- C H P y r i d i n e , 2 - F - 5 -- C H 3 3 4-F-C H NHOH 64 F-C H S0 NH 6 4 2 2 2-HO-5-SO2F-C6H3SO2NH2 CF CF CH CH- CH=CH 2 I 2 2 2I I

2 2 2 2 2I I

C6HeF 02

4 68 67 2

CF CF CH CFCH CH

[CHF CF OCH ]2 3,5-NH -C H F 4-F-C H NHNH

2 2 2I I

1.3193

25

1.3489

1.1866

25

1.3625

1.3113

25

1.3582

1.3114

25

1.3730

2 2 3 2 3 3 2 3 24 CF2 CF2CH2CHC2H5 tetrafluoroethyl-

1.3660

1.3310

25

1.3690

1.3409

25

1.3202

1.4726

37 at 11 m m .

42

-39.1

129 a t 12 m m . 115 132

25

72 at 30 m m . 140 a t 11 m m . 69 at 0.7 m m . 157 a t 145 m m . 82 at 3 m m . 90 155

68 433 489 433 348 348 401 238 456 68

2

Sulfonyl chloride + N H CF =CF + CH =CHCH=CH

3 2 2 2 2 CF =CF 2 2 + C H 2= C ( C H 3) C H O CF =CF 2 2 + C H 2= C H C O C H 3 CF =CF 2 2 + C H 2= C H CΟH C H 2 CF =CF 2 2 + C H 2= C H O C O C H 3 C F C F C F = C F + CH3OH 2 2

CF =CF

90

2 3

fCH FC0 CH2]2 CH OCOCHFCHFC0 CH CF C(=NH)CH2C0 C2H5 CF (CH ) SCN

25 139

39

2 2 + C H 3= C ( C H 3) C N CF =CF + CH =CFCH=CH 2 2 2 2 CF =CF + CH =CFCH=CH 2 2 2 2 2-F-C6H N0 + SnCl /HCl 4 2 2 3-F-C H N0 6 4 2 ++ SS nn CC ll 2// HH CC ll 4-F-C H N0 6 4 2 2 Schiemann reaction 64 2

86 at 100 m m .

456 21, 68 68

CF =CF

Schiemann reaction 4-F-C H N0 + H S

75 at 67 m m .

CHF2COCH2C02C2H5

1,3-Dioxane,

1.3458

134

-5.3

GF2-C-OCH3 CF2CF CH2CH(CH )C0 H

C H F

6 83 2 6 83 6 84 C H F 0 6 842

25

84

CF2CF2CH2CH-OCOCH3

C6H7F3O2 C6H7F3O3

C H F N0 C H F NS C H F

1.2941

90 124-125 175

1 "o

2 3 2 2 2 2 2 63 64 2 CH =C(CH3)C0 2 2CH2CF3 CF3COCH2CO2C2H5

6 75 C6H F 0 8 23 C H F 0 6 824

1.3405

95

3

CF2-C-OCH3

C6H F 02 C H FN

25

5 8 a t 11 m m . 186 181 151 155-156

CF2CF2CH2CHCHCH2

42

1.3459

121

CF CF CH CHCOCH

C6H6F 0

1.3748

85

CF CF CH2C(CH3)CHO

ι

25 192-195

25

1.3295

20

1.4018

1.2570

2 + CH2=C(CH3)C0 2CH 3+ 2 2 2 2 63 2 2 3 3 225 3 225 CF CF CH CF-CH=CH 2 2 2I 2+ H I 2 2

CF =CF + HOCH CH OH 3 , 5 - N 0 - C H F + SnCl Diazonium chloride + N a S 0 / H C l A c i d c h l o r i d e + HOCH2CF3 CF C0 C H + CH C0 C H

25

1.3370

25

1.3677

1.1506

Ο d

68 68 365

Η+

21, 68 121 92 439 80 506, 197 68

169

2

2

ο 00

Dioxane + C F = C F

3 225 2 2 3 22 3

Ο

68

197 421 265 52 420 68

2 225 2 3

Ο

68

CHF C0 C H + CH C0 C H CH FCOCl + HOCH CH OH CH FC0 CH + (CH C0 ) Acetoacetic ester + N H Chloride + KSCN Vinyl compound + [H]

2 2

Ο ο

ο Ο 55 g

g Ł3 Ο g

3 W

C7i

286

T A B L E I (Continued) Formula

C H F8N

68 2 6 92 C6H F 0 9 32 C H F N

C6H9F3O3

C H C H C H

ClFO ClF O C1 FNO

61 0 2 6 1 03 6 1 02 C H Cl F O 6 1 20 2 C Hi F O 6 02 2

C H

F O

6 1 40

C6H F O C HnClFNO C H F

1 402 6 6 n

C H F0

6 U 2 C H F0 S 6 n 2 C H F NO 6 n2 C H F N 6 n4 C H C1F N 6 1 22 C H C1 FN 61 2 C H F 6 1 22 C H

6 1F 220 2 2 22 6 1 32 61 3

C6Hj F S C H F N C H F

C H F0

C 6 6H 1LF N342

C7CIF7

2 2 2 22 3 2 23 CF C0 C H 3 249 CF CH CH C0 C H 3 2 2 225 CF CHOHCH C0 C H 3 2 225 CH FCH CH C0 CH CH C1 2 2 2 2 2 2 CHC1FCF 0C H 9 C H F C O N (2 CH 4 2 2C H 2C l ) 2 CHCl CF OC H -s 2 2 49 CH CH CF C0 C H 3 2 2 225 CH CF (CH ) COOH 3 2 23 CF CHOHCH CONHCH CH OH 3 2 2 2 C H CF CHF 49 2 2 CH C(CH ) CF CHF 3 32 2 2 C Hi F O 6 04 C H OCF CHF 49 2 2

M.p., °C 44-45 -38

27

34 59-60

CHC1FC0NHC4H9

CH =CH(CH ) F Cyclohexyl fluoride CH CH CHFC0 C H CH C0 (CH ) F C H S0 F CHF CONHC H (CHF CH ) NC H (CH FCH ) NCH CH C1 CH FCH N(CH CH C1) 2,2-Difluorohexane 3,3-Difluorohexane 4,4-Difluoro-2-methylpentane CH CH(OCH CH F) (CH FCH SCH ) (CH FCH ) N 1-Fluorohexane 2-Fluorohexane Butane, l - f l u o r o - 3 , 3 - d i m e t h y l -

2 24 3 2 225 3 2 24 6n 2 2 49 2 22 2 5 2 22 2 2 2 2 2 2 2 3 2 2

-82.5 -89.3 -113

2 2 2 2 22 23

CH FCH(OC H )2 (C H ) NCH CH F Toluene, chloroheptafluoro-

2 2 52

13

25 2 2

<-70

B.p.,

°C

65 at 5.5 m m . 198 103 127 181 80 at 5.5 m m . 125 at 6 3 0 m m . 102 at 0.04 m m . 154 128 8 5 a t 15 m m . 187 at 2 m m . 83-84 83-85 98-104 22 at 23 m m . 141-151 90 at 0.5 m m . 91 71 140 138 218 113 at 3 0 m m . 137 96 at 19 m m . 1 1 5 a t 13 m m . 86 87 78 80 at 30 m m . 1 3 8 a t 17 m m . 74 at 25 m m . 93 86 76 60 at 125 m m . 107-113 136

t. ° C

20 20 25 30 20 20

Preparation

1.3848 1.3391 1.3620 1.3707 1.4283 1.3680

1.0559 1.1016

Ref.

Nitrile + [H] Chloride + KCN Acid + alcohol

C F C H C H M g B r + C1C0 C H 1.275 1.2005 1.1779

3 2 2

225

CF =CFC1+

C HgOH (HOCH CH ) NH

A c e t o a c e t a t e + [H]

2 2

CH FC0 CH

2 3+

4

2 22

+ SOCI2

CHC1 CF C1 + s - C H O H

20

1.3665

1.082

25

1.3354

1.1110

25

1.3480

1.0726

25 26 20

1.4431 1.3869 1.4147

1.1376

25 16

1.4112

1.1029 1.4941

2 2

49 Ethyl e s t e r + H P0 4 E s t e r + H O C H C3H N 2 2 H2 C Hi + CF =CF 4 0 2 2 Isobutane + C F = C F 2 2 C F = C F + (C H ) 0 2 52 C F 2= C F 2 + C H 2 2 4 9O H (CH OCH ) + C F = C F 3 22 2 2 CF =CFC1 + C H NH 2 49 2 Acid + alcohol

Cyclohexene + HF Bromide + AgF Chloride + KF Cyclohexyl sulfonyl chloride + KF CF =CF + C H NH CHF CH Br + C H OH/NH

2 2 2 H e x2 yne

2 49 2 2 25 3 22 22 22 +2 H F2

( C H F C H ) N H + ( C H ) 0 + HC1 C H F C H N H + ( C H ) 0 + HC1 20 20

1.3535 1.3546

0.8923 0.9024

20

1.3936

1.0914

20 20 20 34 20 20

1.3748 1.3693 1.3721 1.4363 1.400 1.4043

0.8002 0.7918 0.780 1.447 0.8775 1.70024

Hexyne-3 + HF Chloropentene + HF CH3CHO + H O C H C H F CHF CH Br + Na (SCH )

2 2 2 2

2 2 2 22 2 2

(CH FCH )2NH +- C H F C H B r HgF + bromide CH =CH + (CH ) CF Bromo compound + TIF

2

2

341 215 58 330 262 391 369 53

33

155 215 215 262 19 19 169 364, 170 169 399 232 156 37 162 86 399 482 66 66 200 200 393 273 422 66 93 93 291 387

( C H ) N H + 4-CH3-C H S0 CH CH F 273 C C 1 F C F 3 + Zn 285

2 52 6 47

64 3 2 2

PAUL TARRANT

C6H10F3NO3 C6H10F4

Structure (H NCH CF CF ) CH CF (CH ) CN

90-92

c ciFii

7 C C1F 7 13 C C1F C C1 F

C H C1F N

72 6 72 7 2 23 2 C H C1 F N0 S 7 2 23 3 C H ClFn C H C1 F N0

6 1 03 6U 2

Heptane, chloropentadecafluoroC C1 F CF Cyclohexene, trifluoromethyl-, dichloroheptafluoroHeptane, dichlorotetradecafluoroC C1 F CF Cyclohexene, trifluoromethyl, trichlorohexafluoroC C1 F CF C F CF Norcamphane, dodecafluoroC HC1 CF C HFioCF 5-Br-2,4-Cl-C H CF 5-Br-3,4-Cl-C H CF 5-Br-2,3-Cl-C H CF Chloro-2,4-(trifluoromethyl)-pyridine Chloro-2,6-(trifluoromethyl)-pyridine Heptene, chlorohendecafluoro2,4-Cl-5-N0 -C H CF 2,3-Cl-5-N0 -C H CF 2,4-Cl-6-N0 -C H SOCF 2,5-Cl-4-N0 -C H SOCF

6 23 3

-59

6 32 3

-27 <-70

6 47 3 65 3 6 4 3 6 3

62 3 62 3 62 3

1.3104 1.3122 1.3073

1.822 1.824 1.7999

107 171 116

20 20 20

1.295 1.4445 1.3842

1.756 1.71524

132 207 160

20 25 20

1.3188 1.4840 1.3930

1.792 1.721 1.79225

104 70 248

20 20

1.3664 1.283

1.660 1.76730

10 86, 95 8-9 -22 10

225 220 110 at 20 m m . 145 165 95

20 20 25 25 25 20

1.525 1.519 1.5259 1.4113 1.4140 1.313

1.836 1.741 1.8365 1.5426 1.5644 1.5925

2 53-54 17 100 100

116 a t 10 m m .

25

1.5237

1.6454

1.7174

100 76 60

-21 -25 -22 17 151 115

O c t a c h l o r o - 1 - vinyl

cyclopentadiene + SbF + CI + C o F C H C1CF C H C F C 1 + CI + C o F Octachloro-1-vinyl cyclopentadiene + SbF C H Cl3F9 + C0F3 C C1 F CF + Zn Octachloro-1-vinyl cyclopentadiene + SbF C H C1 F + CoF C e C l F C F 3 + Zn C C1 CF + BrF /SbF

64 3 65 2

3 3

72 6 47 3

7 2 39 3 47 6 5 3 3 5 C C1 CF + BrF /SbF 6 5 3 3 5 C C1 CF 6 5 3 + B r F 3/ S b F 5 Bicyclo-[2-21]-2-heptene + C H CF 6 5 3 ++ CF I C H CF 65 3 C H C1 CF 6 3 2 3 ++ BB rr C H C1 CF 6 3 2 3 Sandmeyer reaction

AgF

2

Trichloromethyl compound + HF Trichloromethyl compound + HF Polychloroheptane + HF/SbCls + HNO3 C H C1 CF 2-Cl-5-N0 -C H CF + CI Sulfide + HNO3 Sulfide + HNO3

63 2 3 2 63 3

Sulfide + H N 0 S u l f o x i d e + [O] Sulfoxide + [O] Sulfoxide + [O] Polychloroheptane Polychloroheptane Polychloroheptane n-C H + C0F3 2-Cl-C6H CF3 + 3-Cl-C6H CF + + 4-Cl-C H CF 3-Cl-C6H CF + 3-Br-4-F-2-HO-C 3-Br-4-F-6-HO-C 3-Br-C H CF +

3

118 140-145 70-71 96 198 194 192 195

98 at 5 m m .

25 20 20

1.345 1.362 1.282

25 25 25 25

1.505 1.500 1.496 1.504

25

1.5180

1.65 1.6725 1.5325

7 16

4 4 3 64 3 4 3

1.799

64 3

+ + +

HF/SbCl HF/SbCl HF/SbCl

Br Br Br Br H2CHO H CHO HN0

6 62

3

5 5 5

+ HNO3 + HNO3

356

5329 329 356

5329 285 356

5329 285 331 285 331 314 235 519 336 336 335 321 321 337 239 335 440 440, 251 440 440 440 440 337 337 337 24 336 336 336 336 226 226 4

287

2 62 3 2 62 3 2 62 3 2 62 3 3,4-Cl-6-N0 -C H SOCF 2 6 2 3 C H C1 F N0 S 7 2 2 3 4 22 ,, 45 -- CC ll -- 64 -- NN 00 2-- CC 6HH 2SS 00 2CC FF 3 2 62 2 3 3,4-Cl-6-N0 -C H S0 CF 2 62 2 3 Heptene, dichlorodecaf luoroC H Cl F o 7 2 21 Heptene, trichlorononafluoroC H C1 F 7 2 39 Heptene, dodecafluoroC H F 7 2 1 2 Heptane, tetradecafluoroC H F 7 2 1 4 5-Br-2-Cl-C H CF C H BrClF 63 3 73 3 4-Br-3-Cl-C H CF 63 3 3-Br-4-Cl-C H CF 63 3 2-Br-5-Cl-C H CF 63 3 3-Br-4-F-2-HO-5-N0 -C6HCHO C H BrFN0 73 4 3 - B r - 4 - F - 6 - H O - 5 - N 02- C H C H O 2 6 C H BrF N0 7 3 3 2 5 - B r - 2 - N 0 2- C 6H 3C F 3

<-70

1.7009

20 20 20

102-103 102-103 102

chlorotridecafluoro-

1.3210

ORGANIC COMPOUNDS CONTAINING FLUORINE

7 15 7 26 C C1 F 7 2 10 C Cl Fi4 7 2 C C1 F 7 35 C Cl3Fg 7 C Cl Fio 7 4 C F 78 C F 7 12 C HC1 F 7 43 C HF 7 13 C H BrF Cl 72 3 2

C C1F CF C F CF C1 Ethyl cyclopentane,

20

T A B L E I (Continued)

C7H BrF C H Br F3

3 4 73 2 C7H Br F 0 3 23 C7H Br FN0 3 3 3 C7H C1F N0 3 3 2 C7H3CIF3NO2S C H C1F N0 S

C H FN 0

7 3 26 7 33 2 7 34 2 C H F N 7 36 C H BrF0 74 2 C H Br F 7 4 22 C H ClFO 74 C H F IN0 C H F N0

C H C1F0

74

2

5-Br-2-F—C6H3CF3 2,5-Br-C H CF 3,4-Br-C H CF 3,5-Br-4-HO-C H CF 2,4-Br-6-HO-C6H CF 2,4,6-ΒΓ-3-Γ-5-Ν0^ ΟΰΗ 4-Cl-3-N0 -C H -CF 5-Cl-2-N0 -C H CF

63 3 63 3 62 3 2 3 6 3 2 63 3 2 63 3 2-Cl-4-N0 -C H SCF 2 63 3 4-Cl-3-N0 -C H SCF 2 63 3 2-Cl-4-N0 -C H3SOCF 2 6 3 2-Cl-4-N0 -C6H S0 CF3 2 3 2 2,4-Cl-C H CF 6 3 3 3,4-Cl-C H CF 63 3 2,5-Cl-C H S0 CF 63 2 3 2,4-Cl-C H S0 CF 63 2 3 2,5-Cl-C H SCF 6 3 3 2,4-Cl-C H SCF 63 3 3,4-Cl-C H3SCF 6 3 2-F-4-HO-3,5-N0 -C HCHO 2 6 4-F-2-HO-3,5-N0 -C HCHO 2 6 5-I-2-N0 -C6H CF 2 3 3 2-N0 -5-F-C H CF3 2 63 2,4-Bis(trifluoromethyl)pyridine 2,6-Bis(trifluoromethyl)pyridine 3-Br-2-F-4-HO-C H CHO 3-Br-4-F-2-HO-C H CHO 2,6-F-C H CHBr 2-F-C H COCl

62 62 2

63 64 3-F-C H COCl 64 4-F-C H COCl 64 2-Cl-4-F-C H CHO 63 2-Cl-6-F-C H CHO 63 2-Cl-4-F-C H COOH 63 2-Cl-6-F-C H COOH 63

M.p., °C

t

B.p., °C

t. ° C

8 0 at 50 m m .

25

n' 1.4580

Preparation

d 1.720

49-50

65 3

8 5 at 10 m m . 50 58 87

'

6

9 5 at 10 m m . 21

3-Cl-C H CF

64 3

12 50

Trichloromethyl sulfide + HF Trichloromethyl sulfide + H F Sulfide + [O]

1 7 1 a t 17 m m .

Sulfide + [O]

117 173

3,4-Cl-C H CCl + SbF Sulfide + [O] Sulfide + [O] Trichloromethyl sulfide + H F

63 3

129 at 12 m m . 84 at 10 m m . 8 5 at 10 m m . 8 3 a t 10 m m . 138 165 61-62

127 150

57 106 <-20 45 4

204

-30

189

9

192

38.5 105 at 20 m m .

3

2 - F - 4 - H O - C H C H O + HNO3 4 - F - 2 - H O - C 6 H C H O + HNO3 Sandmeyer reaction 3-F-C H CF + HNO3

63 3 64 3

88 a t 12 m m .

181 159

3

+ HNO3

131 at 17 m m . 1 3 2 a t 17 m m . 51 46

Ref.

Schiemann reaction + Br C H CF C6H5CF3 + B r Trifluoromethyl phenol + B r Trifluoromethyl phenol + B r 3-F-2,4,6-Br-C HOCH + HNO3

25

1.3833

1.4701

Chloro compound + HF Chloro compound + H F P h e n o l + CHCI3 P h e n o l + CHCI3 2,6-F-C H CH + Br Acid + SOCl

63 3 2 Acid + SOCl 2 Acid + SOCl 2 2-Cl-4-F-C H CH 6 3 3 ++ B[ Or ] + H 2S 0 4 2-Cl-6-F-C H CH 6 3 3 2-Cl-4-F-C H CH 6 3 3 + K 2C r 20 7 2-Cl-6-F-C H CHO + Ag 0 63 2

4 4 4 261 261 228 239 217, 210 247 247 440, 251 251, 247 239 42 247 247 247 247 247 226 226 261 216, 217 321 321 226 226 293 312, 452 312, 452 312, 452 293 547 298 293

PAUL TARRANT

73 3 3 73 3 4 C H C1 F 7 3 23 C H C1 F 0 S 7 3 2 32 C H C1 F S 7 3 23

C H C1F N0 S

Structure

288

Formula

C H C1F0 S C H C1F I

74 3 74 2 C7H4CIF2NO2

C7H4CIF3

C7H4CIF3O2S

2 64 6 2 2 64 3 4 3 4 - d - C 6 H 4C F 3 2-Cl-C6H 4S0 2CF3 4-CI-C6H4SO2CF3

109

3 -55 -34

64 64

C7H 4C1 2FN0 2 C7H4CI2F3N

4-NH -2,5-Cl-C6H2CF3

C7H4CI3F

5-NH -2,3-Cl-C6H CF 2-F-C H CCl 4-F-C H CCl

70 a t 15 m m . 60 at 12 m m . 173 260 97 a t 0.8 m m .

2-NO2-C6H4CCI2F

2

5-NH2-2,4-Cl-C 6H 2CF3

C7H4FIO2 C7H4FI2NO3 C7H4FI3O C7H4FN C7H4FNO

C7H4FNO3S C7H4FNO4

56

2 3

2-I-3-F-C6H3COOH 3-F-2,4-I-6-N02-C6HOCH 3-F-2,4,6-CH 0-C H 2-F-C H CN 3-F-C H CN 4-F-C H CN 3-F-4-HO-C H CN 3-Fluorosaccharin 2-F-6-N02-C6H COOH

64 64 64

3 6

3

63 3 2-F-5-NO2-C6H3COOH 3 - F - 6 - N 0 - C H COOH 2 63 4-F-3-NO2-C6H3COOH

4-F-2-NO2-C6H3COOH

C7H 4FN 30 7 C7H4F2O C7H4F2O2 C7H4F3I C7H4F3NO2

2-F-4-HO-5-N0 -C6H CHO 4-F-^-HO-5-N0 -C6H CHO 3-F-2,4,6-N02-C6HOCH 2,6-F-C H CHO 2,6-F-C H COOH 2-l-C H CF3 3-t-C H CF

2 2

63 63 64 64 3

3-NO2-C6H4CF3 3-NO2-C6H4CF3

2 2

3

65

109 at 7 m m . 132 at 10 m m . 95 at 12 m m . 212

90 at 21 m m . 183 188

64

134 201 127 138 134 121 130

83 at 15 m m .

63

157 198 186 a t 475 m m . 216 201

41.5

2

2

3 3

126 120 180

17 32

2

64 3 64 3

152 102 107 -16

3

3 3

197

25 25

1.5258 1.5158

1.896 1.851

6

2

3

2 4

3

65 3

289

4-NO2-C6H4CF3

64

1 2 2 a t 17 m m .

3 3

2 64 3 64 3

65 2

55

2-CI-C6H4SCF3

3-Cl-C H SCF 4-Cl-C H SCF

456 270 476 42 42 42 4-Cl-C H CCl + SbF 247 Sulfide + [O] 247 Sulfide + [O] 247 Trichloromethyl compound + HF 247 Trichloromethyl compound + H F 247 Trichloromethyl compound + HF 476 C H C C 1 F + HNO3 242, Hydrolysis + phthalimide 244 239 H y d r o l y s i s of p h t h a l i m i d e 335 Nitro compound + SnCl2 429 2-F-C H CH + CI 42 4-F-C H CH + CI 454 Schiemann reaction 3 - F - 6 - N O 2 - C 6 H 3 O H + I + methylation 228 228 43 2-C H CONH + SOCl 505 Sandmeyer reaction 401 Sandmeyer reaction 27 Sandmeyer reaction 96 O x i d a t i o n of 3 - F - 6 - C H 3 C 6 H 3 S O 2 N H 2 530 452 Acid + H N 0 452 A c i d + HN0 452 A c i d + HNO3 528, 4-F-2-NO2-C6H3C6H5 + [ O ] 529 226 Aldehyde + HNO3 226 Aldehyde + HNO3 228 3-F-2,4,6-Cl-C HOCH + HN0 293 2,6-F-C H CHBr + H S0 293 Aldehyde + A g 2 0 261 261 411, 216 216, C H CF + HNO3 473, 411 411

Schiemann reaction C H C F C 1 + HNO3 2-CI-C6H4CCI3 + SbF Schiemann reaction

245 230 148 138 139

ORGANIC COMPOUNDS CONTAINING FLUORINE

C7H4CIF3S

F0 SC H COCl 2,4-F-3-I-5-Cl-C HCH 3-N0 -C6H4CF Cl 2-Cl-C H CF 3-Cl-C6H CF

Structure

Formula

C7H4F3NO2S C7H4F3NO4S C7H4F4 C7H4F4N2O2 C H F C H BrFN0 C H BrF N

7 48 75 2 75 3 C7H Br F 2 C H 5 7 5B r 2F O

C7H5CIFNO

64

B.p., °C

4-N0 -C H4S0 CF3

2 6 2 3-NO2-C6H4SO2CF3

-41 68

64 3

5-F-2-NH2-3NO2-C6H2CF3 Spiro[3-3]heptane, 1,1,2,2,6,6,7,7-octafluoro3-Br-2-F-4-HO-C H CH=NOH 148

62 4-Br-2-NH2-C H CF3 3 - F - C H C H B r6 3 64 2 2,6-Br-4-F-C H OCH 62 3 4-F-2-Cl-C H CH=NOH 63 2-F-C H CONHCl 64 2-F-5-CI-4-NO2-C6H2CH3

55 134 88 18-19 84-85

2-CI-4-CH3-5-NO2-C6H2SO2F C H CF C1

108

6-CI-2-NH2-C6H3CF3

57 at 0.5 m m .

5-CI-2-NH2-C6H3CF3

67 at 3 m m .

3-CI-2-NH2-C6H3CF3

40 at 0.1 m m .

2-CI-4-NH2-C6H3CF3

97 a t 10 m m .

4-CI-3-NH2-C6H3CF3

82 at 10 m m .

C7H5CI2F

C H CC1 F

179 72 at 13 m m .

C7H5CI2FO C7H5CI6F3

2-F-C H CHCl 2,6-Cl-4-F-C H OCH Cyclohexane, 1,2,3,4,5,6-hexachlorotrifluoromethyl-

C7H5FINO3 C7H5FI2O C7H5FNO3 C7H5FN2O3 C7H5FN2O4 C7H5FN2O5 C7H5FN4O5

3

2 2 62 3

4-F-3-NO2-C6H3CONH2 4-F-C H NHCOF 2-F-4-HO-5-N0 -C H CH=NOH 4-F-2,6-N02-C H OCH 2-F-4,6-N0 -C6H20CH 4-F-3,5-N0 -2-HO-C HCH=NNH

64

2 62 62 3 2 3 2 6

144 at 4 m m .

1.5137

1.5281

1.712

221

64 2 2

3+ SbF3 2 2

5 - F - 2 - N H 2 - C 6 H 3 C F 3 + HNO3 CF =CF + CH =C=CH Schiemann reaction 3-F-C H CH +Br Phenol + methylating agent Aldehyde + HONH From o-fluorobenzamide Schiemann reaction

64 3

C6H5CCI3 +

SbF F l u o r i n a t i o n a n d h y d r o l y s i s of t r i chloromethylphenylphthalimide F l u o r i n a t i o n a n d h y d r o l y s i s of t r i chloromethylphenylphthalimide F l u o r i n a t i o n a n d h y d r o l y s i s of t r i chloromethylphenylphthalimide F l u o r i n a t i o n a n d h y d r o l y s i s of t r i chloromethylphenylphthalimide F l u o r i n a t i o n a n d h y d r o l y s i s of t r i chloromethylphenylphthalimide F l u o r i n a t i o n a n d h y d r o l y s i s of t r i chloromethylphenylphthalimide C H CC1 + SbF 2-F-C H CH + CI Phenol + ( C H ) S 0 C H CF + CI

3

65

25

1.846

3 3 64 3 32 4 65 3

6 2 3 + HNO3 32 3

4-F-2,6-I-C H OCH Phenol + ( C H ) S 0 4 Acid chloride + N H 4 - F - C H N C O +HF

64

164 a t 10 m m .

2

1.3325

25

36

53 61 153 141 132 83

4-F-5-I-2-N0 C6H OCH3 4-F-2,6-P-C H OCH

Ref.

2

142.5 83 at 4 m m .

2 62

25

247

4-CI-2-NH2-C6H3CF3

65 2

Sulfide + [O] Sulfide + [O] 4-F-C H CCl

147 a t 11 m m . 103

85 at 5 m m . 109 at 8 m m .

Preparation Trichloromethyl sulfide + H F

85

4-F-C H CF

2 64

d

115 at 20 m m . 104 a t 10 m m .

3

3-NO2-C6H4SCF3

65

t. ° C

4-F-C H OCH + HNO3 2-F-4-N0 -C H OCH3 + Aldehyde + H N N H

64 3 2 63 2 2

HNO3

247 247 247 247 42 137 68 226 4 523 227 293 429 270 85 476 242, 244 244 244 244 242, 244 239 476 429 228 315 228 228 412 56 226 432 432 226

PAUL TARRANT

C7H5CIFNO2 C7H5CIFNO4S C7H5CIF2 C7H5CIF3N

4-N02-C H SCF

M.p., ° C

290

l

T A B L E I (Continued)

C H FO

C H COF 2-F-C6H4CHO 3-F-C6H4CHO 4-F-C H CHO 4-F-C H COSH 2-F-C H C0 H

75

C7H5FOS C7H5FO2

75 3 7 52 2 7 52 3 53 C H F N 0 7 53 22

C H F N0 C H F N0 C7H F

C H F 0

7 53 C H BrF 76 C H BrF0 S C H C1F

7HH 6CC11FFI0N S 7H 6F I 0 S2 76 2 7H 6F N O

36 168

153

133 71 at 0.6 m m . 102

109 129 64 46 47 8 4 a t 15 m m . 7 7 a t 12 m m . 8 5 a t 15 m m . 75

76

67 44 35 116 130 154 63 63 8 1 , 116

3

64

124 182 171 69 186 179 -13.5 37-38 -29

65

2

T o l u e n e + [O] T o l u e n e + [O] C H OH + COF Phenol + CHC1 Phenol + CHCl A n i s o l e + HI P h e n e t o l e + HI S-NOz-Ce^CHC^ Anisole + H N 0 C H CC1 + SbF

65

2 3 3

+ SbF

3

3

65 3 3 3 6 4 3 + HN03 3-CH CONHC H CF 3 6 4 3 ++ HH NN 00 3 3-CH CONHC H CF 3 64 3 3 Diazonium chloride + H 0 2 2-F-C H CH 6 4 3 ++ BB rr 3-F-C H CH 6 4 3 4-F-C H CH 6 4 3 +* B r 2-F-C H CH 6 4 3 ++ CC II 3-F-C H CH 6 4 3 4-F-C H CH 6 4 3 + CI Schiemann reaction 3-CH CONHC H CF

147 72 at 8 m m .

78 a t 16 m m . 68 a t 15 m m . 76 at 20 m m . 152 154

Schiemann reaction 3-Iodomercuri compound + I Sandmeyer reaction Acid chloride + N H Acid chloride + N H Acid chloride + N H Aldehyde + HONH Aldehyde + HONH Aldehyde + HONH

2 2 2

3 3 3

533 427 427 427 140 452, 428 452 452 132 226 226 226 461 527 359 473, 42 239, 374 411 374 261 261 445 445 445 456 25 25 25 298 547 270 85 458 452 452 452 444 444 402, 444

FLUORINE

C C C C

3

64 64 64 2 3-F-C H C0 H 6 4 2 4-F-C H C0 H 64 2 C H OCOF 65 2-F-4-HO-C H CHO 63 4-F-2-HO-C H CHO 63 4-F-2-HO-C6H C0 H 3 2 5-F-2-HO-C H C0 H 63 2 3-N0 -C H CHF 2 64 2 4-N0 -2,6-F-C H OCH 2 62 3 C H CF 65 3 3-NH -4-N0 -C H CF 2 2 63 3 3-NH -6-N0 -C H CF 2 2 63 3 3-NH -2-N0 -C H CF 2 2 63 3 2-HO-C H CF 6 4 3 4-HO-C H CF 6 4 3 2-F-C H CH Br 64 2 3-F-C H CH Br 64 2 4-F-C H CH Br 64 2 5-Br-4-HO-3-S0 F-C H CH 2 62 3 2-F-C H CH Cl 64 2 3-F-C H CH Cl 64 2 4-F-C H CH Cl 64 2 2-Cl-4-F-CeH CH 3 3 2-C1-6-F—C6H CH 3 3 2-F-3-I-4-NH -5-Cl-C HCH 2 6 3 6-Cl-2-CH -C H S0 F 3 63 2 3-I-4-CH -C H S0 F 3 63 2 2-F-C H CONH 64 2 3-F-C H CONH 6 4 2 4-F—C6H CONH 4 2 2-F-C H CH=NOH 64 3-F-C H CH=NOH 64 4-F-C H CH=NOH 64

C H COCl + SbF T o l u e n e + [O) T o l u e n e + [O) Toluene + fO| 4-F-C H COCl + H S Toluene + [ 0 |

ORGANIC COMPOUNDS CONTAINING

C H F0

76 76

136 87 at 3 6 m m . 76 at 26 m m . 175

65

291

292

T A B L E I (Continued) Formula C H FN0

76 2

Structure 2-F-3-N0 -C H CH

2 63 3 2 3 3 2 63 3 3 3 3 3 2 6 3 3 4-F-3-N02-C6HSCH3 2-F-6-N0 —C6H CH 3-F-2-N0 -C H CH S-F-4-NO^C6H CH 3-F-6-N02-C6H CH 4-F-2-N0 -C H CH

4-Fluoroanthranilic acid 2-Fluorobenzoquinone, methyl ether oxime 2-F-4-HO-C H CH=NOH 4- F - 2 - H O - C H C H = N O H C H FN0

76 3

H F HeF H F H F

0 0 0 S N

7 62 7 22 7 6 242 7 63

C H F 0

7 6 82 77 77

C H C1FN C H F

C H FN 0

7 7 23 77 2

C H FN S

2,5-F-C H CH 2,6-F-C H CH 2,6-F-C H OCH 2,6-F-4-HO-C H OCH

63 3 63 3 63 3 62 3 2,4-S0 F-C H CH 63 3 2 - N H -2 2 C 6H 4C F 3 3-NH2-C H CF 64 3 4-NH2-C H CF 64 3 CHF CF CF CF C0 C H 2 2 2 2 225 2-F-4-NH -5-Clr-C6H CH 2 2 3 2-F-C H C 6 4 H3 3-F-C H CH 6 4 3 4-F-C H CH 64 3 2-F-4-N0 -6-NH -C H OCH 2 2 62 3 2-F-5-N0 -4-NH2-C H OCH 62 3 4 - F - C H N2 6 4 HCSNH2

t. °C

nt

d*

110 a t 12 m m . 97 a t 11 m m . 92 a t 11 m m .

38

3-F-C 3-F-C 3-F-C 4-F-C 4-F-C Methyl

97 a t 10 m m . 213 241

HN03 6HH 4CC HH 3 ++ HN0 6H 4C H 3 + HN0 3 6H 4C H3 + HN03 6H 4C H 3 + HN03 6f l u4o r o a3c e t a m e n o3b e n z e n e

+ [O]

Aldehyde + HONH Aldehyde + HONH Schiemann reaction Sodium phenolat£ + methylation

2 2

93 a t 3 m m .

Schiemann reaction

2-CH C H S0 F

364 2

C H CHC1

65

117 112 62 a t 40 m m . 71 a t 0.2 m m .

141 30 a t 26 m m . 114 116

+

HN03

2 + S b F 3; C 6H 5C F 2C 1

+ [H]

Schiemann reaction Schiemann reaction Schiemann reaction 2-CH -C H S0 Nitro compound Nitro compound Nitro compound

3 6 4 2F+

55 a t 9 m m . 187 73 a t 5 m m .

55

108 143 163

Ref.

Schiemann reaction Schiemann reaction

133

69-70 87-88

Preparation

20

1.3261

1.4528

+ HOS0 F SnCl + SnCl + SnCl

2 2 2

2

Acid + alcohol Nitro compound + [H] Schiemann reaction Schiemann reaction D e c o m p . of diazopiperidide R e d u c t i o n of d i n i t r o c o m p o u n d

HN03 4 2+ m e t a l

Anisole + 4-F—C6H NH

thiocyanate

532 293 426 426 426 95 95 455 222 226 226 360 359 225 225 90 225 456 456 456 456 527, 476 426 293 359 359 456 216 473 216, 374 341 270 426 426 535 432 130 295

TARRANT

C C C C

S 7H 6FF NN 00 3 S 7H 6 4 S 7H 6FF NN 00 5 7H 5S H6 F 7 62

63 63 2-F-4-N02-C6H OCH 3 3 2- F - 6 - N 0 2 - C H O C H 63 3 3-F-2-N02-C6H80CHS 3-F-4-N0 -C H OCH 2 63 3 3-F-5-N0 -C H OCH 2 63 3 3-F-6-N0 -C H OCH 2 63 3 3-S0 F-C H CONH 2 64 2 2-CH -5-N02-C6H S0 F 3 32 4-CH 0-3-N02-C H S0 F 3 63 2 2-HO-4-N0 -5-CH -C H S0 F 3 62 2 C6H5CHF2 2

7 18 53 27 -9 26 193 89 151 125 104 9 43.5 56.5 150(ti) 52 109 57 78 87

B.p., °C

PAUL

C C C C C

M.p., ° C

C7H7FO

C H7F02

7

C7H7FO2S C7H7FO3S

C7H7F2N C H F NO

7 72

C7H7F3N2 C H8Br F3 C H FN

77 8 3

C H FNO

78

64 64

3 3 63 3 2-CH3-C6H4SO2F 4-CH -C H S0 F 3 6 4 2 4-CH 0-C H S0 F 3 64 2 5-CH -2-HO-C6H S0 F 3 3 2 2-CH -C H S0 F 3 64 3 4-CH -C H IF 0 - T o l u3e n e6 i o d4o x y2d i f l u o r i d e m -Tolueneiodoxydif luor ide />-Tolueneiodoxydifluoride 3-NH2-C6H4CHF2 2,6-F-4-NH2-C6H OCH Cyclobutenecarbonitrile, 2-ethoxy3,3-difluoro-

2

-35 -45

3

112 170(d) 178, 180(d) 207(d) -20

2-F-4-NH2-C6H3CH3

3-F-4-NH2-C6H3OCH3 3 - F - 6-NH2-C 6 H 3 O C H 3 C H FN0 S C H F 0

78 2 7 842 C H F 0 7 86 C7HgBr F 23 C7H9F3 C7HioBrF3

C7H10F3NO2 C7H10F4

3-F-6-CH3-C6H3SO2NH2 CF CF2CH2C(CH3)C0 CH3

2 2 1 1 CF (CH ) CO(CH2)2CF3 3 2 2 Cyclohexane, trifluoromethyl-, dibromoCyclohexene, trifluoromethylCyclohexane, trifluoromethyl-, b r o m o Cyclohexane, trifluoromethyl-, nitroCF CF2CH2-C(CH3)C H5 1

12

2

CF2CF2CH2CHC3H7

C7H11F3

7 n3

C7H12F2

2

122 at 33 m m .

2 64 2 2 2 21 1

Aminonitro compound + [H] C H CF + Br Nitro compound +[H] Nitro compound + [H] Nitro compound +[H] Nitro compound +[H] Nitro compound +[H] Nitro compound +[H] Nitro compound + [H] Nitro compound + [H] Nitro compound + [H] Sulfonyl chloride + N H

262 86 at 12 m m . 203 90 at 15 m m . 94 a t 16 m m . 94 at 10 m m . 208

50 215 155 1.3656

1.2890

1.3435

164 219 105 177 225 108

1.3529

1.912 1.127 1.561 1.3154 1.1285

113

1.3516

1.1190

1

Cyclohexane, trifluoromethylCF C H OH Isoamyl trifluoroacetate Cyclohexane, difluoromethyl-

361 0

107 182 119 125.2

CF =CF

411 501 532 51 293 426 360 359 229 229 229 96 68

C 6 H 1 1 C F 3 + HNO3 CF2=CF2 + isoprene

330 501 501 501 501 68

6 1 33

83

70 at 56 m m .

5

1.3530

1.087 1.2611 1.0834 1.017

3 2 2 + C H 2 = C ( C H 3) C 0 2C H 3 CF CH CH MgBr + (CH 0) CO 3 2 2'+ B r 32 C HnCF 6 3 CF C H OH + P 0 361 0 25 C6H11CF3 + B r CF =CF

+ pentadiene-1,3 2 C H CF 6 5 3 +[H] + [H] 3-HO-C H CF 64 3 Acid + alcohol C H C H F + [H] 65 2

68 499 504 508 499

293

C H F 0 C7H11F3O2

1

175 136 at 2 0 m m . 192

58

3-F-2-NH2-C6H3OCH3

2

2

83 at 31 m m .

32 7

reaction reaction reaction reaction

427 427 427 51 2-F-4-NH2-C6H3OCH3 + H N 0 + H 0 3 6 0 85 85 456 />-Cresol + H O S 0 F 456 281 539 538 539 539 527 + Zn/HCl 3-N0 -C H CHF R e d u c t i o n of n i t r o a n i s o l e 359 18 C F - C F - C H C H C N + NaOC2H

224

2-F-3-NH2-C6H3CH3 2-F-6-NH2-C6H3CH3 5-F-2-NH2-C6H3CH3 2-F-4-NH2-C6H3OCH3 2-F-6-NH2-C6H3OCH3

Schiemann Schiemann Schiemann Schiemann

54-55 41-42 13 58

3

2,5-NH2-C6H CF3 Cyclohexane, trifluoromethyl-, tribromo-

59 at 12 m m . 51 at 15 m m . 51 a t 13 m m . 195

ORGANIC COMPOUNDS CONTAINING FLUORINE

C7H7F2I C7H7F2IO

2-F-c H OCH 3-F-C6H40CH3 4-F-C H OCH 2-F-4-HO-C6H3CH3 3-F-4-HO-C H OCH

T A B L E I (Continued)

n-C H iOCF CF H

C H

F(CH2)4C0 C H5 1,1-Difluoroheptane 2,2-Dif luoroheptane -73 1-Fluor oheptane 65-66 C Cl5C2Cl F 120-121 C6C1 C C1 F2 40-41 Tricyclo[4.2 0 0 - ]octane, dodecafluoro(C F ) 0 40.0-40.5 2-Br-3,4-Cl-l,5-bis(CF )C H C H C1 F(CF )2 45.0-45.3 5-Br-2-Cl-l,4-bis(CF )C H 20.4-20.9 5-Br-2-Cl-l,3-bis(CF )C H 1 1 .5to-11.0 3-Br-2-Cl-l,5-bis(CF )C6H 72.0-72.5 2,5-Br- l,4-bis(C F ) C H 91 2-Cl-5-F-C H -NHCOCH 34.6-34.9 2,5-Cl-l,4-bis(CF )C H 4.5-5.0 2-Br-l,4-bis(CF )C H -16.0to-15.5 5-Br-l,3-bis(CF )C6H -48 to-47 4-Br-l,2-bis(CF )C H 3-Cl-4-CF -C H COF 5-Cl-l,3-bis(CF )C H Cyclohexadiene, chlorodifluoro-bis(C F ) Cyclohexene, chlorotetrafluoro-bis(C F ) 5-Cl-2-CF -C H COCl

51

7 1 F 0 23 C7H14F2 C7H15F C C1 F

8 73 2 C8F12 C Fi 0 8 8 CeHBrCl2F6 C8Cl8F

C8HCI2F7 C8H BrClF

2

6

C8H C H C H C H

2B r 2F 6 8 2CC l1F NF O 8 2B r F26 6 83

C H C H C H C8H C H

8 3C 1 F 40 8 3CC 11 FF 6 8 3C l F 8i 3 0 8 3C 1 2F 30 C H C1 F 8 3 43 C H C1 F 83 6 C H F0 83 3 C8H F N 0 3 3 22 C H F N0 8 36 2 C H BrF0 84 4 C H BrF 0 8 4 32 C H C1F 0 84 3 C H C1F

84 5 C8H C1 F N02 32 C H 4 8 4C 1 3F 3

2 2 22

2 3 25 52 3 4 92 62 2 3

t. ° C

31 at 20 m m . 58 a t 16 m m . 120 112 120

25

1.3480

1.0726

20 20 21

1.3710 1.3659

0.8959 0.8889 0.8027

6

3 6 3 62 3 62 3 2 3 62 63 3 3 62 3 63 3 3 3 63 3 63 3 63

3 63 3,4-d-C H -CCl CF 63 2 3 4-F-l,3-bis(CCl )C H 3 63 4-F-phthalic anhydride 2_N0 -4-CF -C H CN

2 3 63 5-N0 -l,3-bis(CF )C H 2 3 63 4 - B r - l - F - p h t h a l i c acid 2-Br-4-CF -C H C0 H 3 6 3 2 5-Cl-2-CF -C H CHO 3 63 2-CF -C H COCl 3 64 3-d-C H COCF 64 3 5-Cl-2-CF -C H CHF 3 63 2 3-N02-C H4C Cl F2 6 2 3 d-C6H C Cl F 42 23 3-d-C6H CCl CF 4 2 3

3 3

76-78 47-48

80 100.4 84.5 at 1 m m . 170-171 189.5 at 750 m m . 192.1 at 748 m m . 186.3 at 7 4 5 m m . 112.0 at 4 0 m m .

20 25

e

174.4-177.6 161.8 at 751 m m . 151.3 at 751 m m . 87.0 at 40 m m . 138-139 147 143 214-217 187.5 at 172 m m . 157.5-159.5 at 112 m m . 260 at 746 m m . 156-158 at 1ft- 1 m

1.2619 1.465

1.7288 1.70723

1.460 1.455

1.815 1.825

25 25 25

1.431 1.425 1.440

30 32 32

1.4023 1.3922 1.3607

20

1.5221

1.741 1.715 1.759

1.624425

C H -CC1 CF + CI 4-F-l,3-CH -C H + CI

364 54 200 200 498 322 322 377 210 336 325 336 336 336 336 87 320 336 336 336 276 48 519 519 252, 425 362 47

4-F-phthalic acid - H 0 2 - N 0 - 4 - C F C H X + CuCN

36 249

n-C HnOH + CF =CF Iodo compound + A g F Dichloro compound + HgO/HF Heptyne + H F Bromide + AgF + CI C H C1C2C1 F C H C 1 C 2 C 1 F 2 + CI ( C F = C F - C F = C F ) 2 at 500° (C Hg) 0 + HF + electrolysis C H C 1 F 6 + B r + CI C6H C1 (CC1 )2 + HF + SbF C H C1F + Br

5

64 64 2 4 82 2 83

2

23 3

2 2 2 3 6

2

2

5

8 4 6+ Br C H F 8 4 6 ++ CB Ir C H F 8 4 6 + Br C H F 8 4 6+ Br C H F 8 46 4-CCl C H COCl + HF + 364 C H F 8 4 6 + CI 4-Cl-l,3-bis(CF )C H 3 63+ 4-Cl-l,3-bis(CF )C H 3 63+ 65

173-177

20

1.4800

1.421125

25 25

1.4818 1.4970

1.498 1.5173

83-84

SbF

3

F F

2 3 3 63

2 363 C H F + HN0 8 46 3 4-Br-l-F-naphthalene

Ι "Ο7Q ±Ξ M

213 at 745 m m . 201 at 632 m m .

Ref.

C H F

155 182-183 8 2 - 8 6 a t 18 m m . 90 a t 15 m m . 93 at 3 6 . 5 m m . 164-167

Preparation

2

+ Ο

5-Cl-2-CF C H CHF + 2 - C F C H C H O + CI C H COCF + Cl/FeCl

3 6 3 2 H 2S 0 4 364 65 3 3 C H C C1 F2 + HN0 6 5 2 3 3 C H C 1 C C 1 + HF + S b F 6 4 2 5 + CI 5 C H CC1 CF 65 2 3

239 431 4 246 246 362 246 540 322 362

PAUL TARRANT

C7H12F4O

d*

B.p., °C

294

M.p., °C

Structure

Formula

C8H C H C H C H

C C C C

8HH 5FF NN 200 3 8H 5F 0 2 4 85 4 8H 5F 30

C H C1CC1 F 3-CF -C H CN 3-CF -C H COF l,4-bis(CF )C H l,3-bis(CF )C H CH -CF -CF -CH-C=CH-CF -CF

64

32 3 64 3 64 3 64 3 64 2 2 I I 2I 2 I 2 2-F-C H CH=CBrN0 64 2 3-Br-2-F-5-CH -4-N0 -C HC0 H 3 2 6 2 4-Cl-2-CH -6-N02-C6H SOCF 3 2 3 2-Cl-5-CH -4-N0 -C H SOCF 3 2 62 3 2-Cl-5-CH -4-N0 -C H S0 CF 3 2 62 2 3 4-Cl-2-CH -6-N02-C H S0 CF 3 6 2 2 3 C H C C1 F 652 2 C H 0CF=CC1 65 2 4-d-C H CHFCCl 64 3 4-F-C H CHClCCl 6 4 3 3-N0 -4-F-C H NHCOCH 2 63 3 2-F-5-N0 -C H CH=CHN0 2 63 2 4-F-l,2-di(C0 H)C H 2 63 3-CF^CeH^HO 3-CF3-C6H4CO2H

C C C C

2,4-bis(CF )C H NH 2,6-bis(CF )C H NH 2,5-bis(CF )C H NH 3,5-bis(CF )C H NH 2-F-3,5-CH -4,6-N02-C Br 4-F-C H COCH Br 3,5-Br-2-F-6-OH-C HNHCOCH C H -OCF=CHCl

H H H H

BrFN 0 BrFO Br FN0 ClFO

86 24 86 86 2 2 86

C H C1F0

25

1.5140

1.537

4 9 - 5 0 a t 13 m m .

25

1.3596

1.5147

89-90

- 4 2 to-44.5

75 at 0.7 m m . 210.0 at 740 m m . 9 4 . 5 - 9 6 . 5 at 1 mm. 94-96 at 2 m m .

20 25

1.5162 1.5463

1.336427

138.9 142-143 147-148 8 3 - 8 6 at 30 m m . 70 at 16 m m . 103-104

238.2

2-CF -C H CHF

3 64 2 3 63 2 3 63 2 3 63 2 3 63 2 3 6 64 2 6 65 4-F-C H COCH Cl 64 2 3-F-4-OH-C H COCH Cl 63 2 2-F-C H OCOCH Cl 6 4 2 2,4-Cl-5-F-C H NHCOCH 62 3 C6H OCF CHCi2 5 2

50 at 0.4 m m . 37 at 0.2 m m . 173-177 8 0 - 8 1 a t 12 m m .

3

86-87 48-49 190 -50to-51 48 101-102 36-38 126 - 2 3 . 5to -24.0

189.5 at 740 m m . 4 9 . 7 - 4 9 . 8 at 4 m m .

64

2 5 5 64 3 2 3 64 3 84 6 CH =CH-C=CH + CF =CF 2 2 2 2-F-C H CH=CHN0 64 2 + Br; then C H O H + KOH 25 3-Br-2-F-l,5-CH -4-N0 -C6H + Ο 3 2 C H C1(CH )(N0 )SCF + Ο 62 3 2 3 C6H C1(CH )(N0 )S0CF + Ο 2 3 2 3 C H C1(CH )(N0 )S0CF + Ο 62 3 2 3 C H C C 1 C C 1 + HF 65 2 3 4-Cl-C6H CH(OH)CCl 4 3 + HF 4-F-C H CH(OH)CCl + PC1 64 3 5 3-N0 -4-F-C H NH 2 6 3 2 + ( C H 3C O ) 20 2 - F - C e H C H = C H N 0 + fuming H N 0 4 2 3 4-F-l,2-di(C0 C>>H )C H 2 5 6 3 + H 20 3-CF -CeH CN 4 SnCl + H C l / E t 0 3 4 2 2 2-CF -C H CHF 3 6 4 2 + c o n e . H 2S 0 4 a t 9 0 ° 3-CF -C6H CHO + air or 3 4 3-CF -CeH CN + H 0 3 4 2 F l u o r i n a t i o n of C H C 1 85 5

20

1.5049

1.227127

322 473 276 241 241 68 551 269 251 251 251 251 541 316 447

8 489 551 36 51 252, 425 473 51 252, 425 H y d r o l y s i s of p h t h a l i m i d e 242 H y d r o l y s i s of p h t h a l i m i d e 242 + Η 239 2,5-bis(CF )C H N0 3,5-bis(CF )C H N0 + Η 239 2 , 4 - D i ( C H ) - 5 - N 0 - 6 - B r - C H F + H N 0 268 + Br 297 4-F-C H COCH 384 316

3 63 2 3 63 2 3 2 64 3

6

3

C H F + CH ClCOCl 2 - F - C 6 H O C O C H 2 C l + A1C1 CH C1C0 H + 2-FC H OH + SOCl 3-F-C H NHCOCH + CI

90-94 at 4 m m .

216.0 at 740 m m . 67.9 at 4 m m .

C H C1C C1 + SbF + HF 3-NH2-C H CF + H N 0 + CuCN 3 - C C l - C H C O C l + HF + SbF C H C 1 + HF

20

1.4789

1.370627

172 65 2 173 4 3 173 2 2 64 2 87, 64 3 256 C e H O N a + CF C1CHC1 in CH COCH 3 1 6 5 2 2 3 3

295

86 2 C H Cl FNO 86 2 C H C1 F 0 8 6 22

245 at 7 4 5 m m . 189 159-163 116-118

249-251 114 105 69 59

2-CFs-CeH^HO

C H F 0

8 532 C H F 8 55 C H F N 8 56

14.5

* ORGANIC COMPOUNDS CONTAINING FLUORINE

4C 1 4F 2 8 4FF 3N0 8 4F 4 8 46 C H F 8 48 C H BrFN0 85 2 C H BrFN0 8 5 4 C H C1F N0 S 85 3 3 C H C1F N0 S 85 3 4 C H C1 F 85 2 C H Cl FO 85 2 C H C1 F 85 4

Formula C8H6CI3F2N C H FI0 C H FN C H FNO C H FN0 C H FN0 C H FN0 C H F 03 C H F NO

86 2 86 86 86 2 86 4 86 5 8 62 8 63

C H F N0

C H F N C H F

8 65 8 68 C H BrFN0 87 2 C H BrFN 0 87 32 C H Br F 87 2 C H C1FN0 87 C H C1F 0

87 2 87 8 7 23 C H FN 0 8 7 24 C H FN 87 4 C H FN 0 8 7 44 C H FO 87 C H F C H FN 0

M.p., °C

3-NH2-C6H4C2CI3F2 3-F-2-I-C6H3CO2CH3 4-F-C H CH CN 4-CH3O-3-F-C6H3CN 2-F-C H CH=CHN0 3-F-4-CH 0-5-N02-C6H CHO 3-F-4-CH3O-5-NO2-C6H2CO2H 3,5-F-4-CH 0-C6H2C0 H C6H5NHCOCF3 3-CF -C H CH=NOH 4-CF3-C6H4CONH2 4-CH30-3-N02-C6H3CF3 5-CH3O-2-NO2-C6H3CF3 4-CH3-2-NO2-C6H3SOCF3

64 2 64 3 3 3 64

2

96.5 56.5-57.6 57-58 166

2 2

2

I

2

I 1

2

2

20

1.5128

1.30529

86.5 at 80 m m .

25

1.4073

1.3341

1

6

4-F-C H CHBrCH Br 2-Cl-5-F-C H NHCOCH 4-Cl-3-F-C H NHCOCH

2 63 3 63 3 C H OCF CH Cl 65 2 2 4-F-C H CH=CH 64 2 4-F-2-N0 -C H3NHCOCH 2 6 3 4-F-3-N02-C H NHCOCH3 63 3-F-4-CH 0-5-N02-C6H CH=NOH 3 2 Guanidine, l-cyano-3-(/>-fluorophenyl)-

- 5 0 . 0 to -52.5 -34.5 71.5 138.5 138-139 204-205

2

Ref.

3-NO2C6H4C2CI3F2 + H Acid + Alcohol 4 - F C H C H C l + NaCN 4-CH30-3-FC H N X + Cu CN 2 - F C H C H O + CH3ONO + ( C H ) N 3 - F - 4 - C H O C H C H O + HNO3 3 - F - 4 - C H 3 0 C H C 0 H + HNO3 Schiemann reaction CF C0 H + C H NH at 120° 3 - C F C H C H O + H NOH 4-CF3-C H COCl + NH 4 - F - 3 - N O 2 - C 6 H 3 C F 3 + CH3OH/KOH 5 - F - 2 - N 0 2 - C 6 H C F 3 + CH3OH/KOH From 4 - C H - C H S C F or F r o m 4-CH3-2-NO2-C6H3SCF3 4-CH3-2-N02-C6H3SOCF3 + Ο

540 454 463 133 551 133 133 133 502 152 261 51 51 440 440 440 240 4,6-N02-2-CF -C6H Cl+ CH NH 83 0-CH=CH-CH=C-CH=CH + C F = C F 68

64 2 632 2 2 64 33 3 63 63 2 3 2 65 2 364 2 64 3 3 3 64 3 3 I

2

2

3 2 2 2

83 150-158

CJÎ2-CF^-CF^^H-CH==CH From borofluoride 3-Br-2-F-4-OH-C H CHO

75 143 115

64

2-F-4-OH-5-N0 -C H CH=NNHCOCH C H CH COF

Preparation

I

49-51 210

2 62

1 0 2 - 1 0 4 a t 12 m m .

36 150-151 67-68

6-Br-2,4-CH3-5-N02-C HF 3-Br-2-F-4-OH-C6H CH=N-NHCONH2

65 2

127-128 at4 m m . 122-123 at 21 m m . 96.8 at 2 m m .

159 48 39 84

2 2 2

l d

162

68-69 49-50

2 2

n

87.6 subl.

3,5-F-2-CH NH-C6H CF3 (CH -CF -CF2-ÇH)

3

t. ° C

55

4-CH3-2-NO2-C6H3SO2CF3 2-NO2-4-CF3-C6H3SO2CH3 4,6-N0 -2-CF3-C6H NHCH3 0-CH=CR-CH=C-CH-CH -CF -CF

2

B.p., °C

196.0 at 740 m m . 55.8 at 4 m m . 67.4 at 50 m m .

258(d) 8 8 - 8 9 a t 17 m m .

20

1.4777

1.270427

25

1.5130

1.0178

2+ C F 2= C F 26 8 268

6 2+ H N - N H C O N H 2 2 6 2 21 4 4 4-F-C H CH=CH 64 2 + Br 256 3-F-C H NHCOCH 64 3+ C a ( O C l ) / K H C 0 2 5867, 2 3316 C H ONa + CF C1CH C1 65 2 2 4-F-C H CHOHCH 396 64 3 - H 20 4 - F - C 6 H N H C O C H + HNO3 495 4 3 4-F-C H NHCOCH 495 64 3 + HNO3 Aldehyde + NH OH 133 2 4-F—C6H4NH2 + N a N O 175 z + H NC(=NH)NHCN 2 Aldehyde + H N N H C O N H 226 2 2 C H C H C 0 N a + KSO3F 520 65 2 2

PAUL TARRANT

8 63 3 8 63 3 C H F N0 S 8 63 4 C H F N 04 8 633 C H F 0 8 64 C H F N0 S

Structure

296

t

T A B L E I (Continued)

C H FO

87

C H FOS C H F0

87 87 2

8H 7F 0 3 8HH 7FF 00 4SS 87 5 8H 7F 2N O

C H F N0 C H F N 0 C H F 0

8 72 2 8 723 8 73 C H BrF 88 C H BrFO 88 C H FNO 88

C H FN0

88 2 C H FN0 88 3 C H FN0

2

265 3 63 64 2 2 64 3 64 2 3 6 2 3 64 2 3 63 3 63 2 3 63 2 3 63 2 64 2 2 2 2 3 3 2 65 2 63 3 6 3 3 62 2 63 2

4-F-C H CH CH Br 2-F-3,5-CH C6H Br 2-Br-4-F-C H OC H 2-F-C H NHCOCH 3-F-C H NHCOCH 4-F-C H NHCOCH

64 2 2 ^ 3 2 63 25 64 3 64 3 64 3 C H N(CH )COF 65 3 2-F-4-CH 0-C6H CH=NOH 3 3 4-F-2-CH 0-C6H CH=NOH 3 3 3-F-5-N0 -C H OC H 2 6 3 25 4-F-2-N0 -C H OC H 2 63 25 4-F-3-N0 -C H OC H 2 63 25 2-F-4-N0 -C H OC H 2 63 25 3-F-4-CH 0-5-N0 -C H CH OH 3 2 62 2 4-C H -3-N0 -C H S0 F 25 2 63 2 2-F-5-N0 -C H NHCOCH 2 63 3

36.5-37.5 63.5-64 29-30 86 -20 -10 4.5 114 56 165 160-161 208-210 110-111 183 52.4 120.9 122.5 158-160 226 - 1 4 . 1 to -14.3

7 9 . 0 a t 10 m m .

1.5081

1.1382

8 0 - 8 5 a t 16 m m . 1 3 2 a t 18 m m .

8 5 - 8 7 a t 16 m m . 207 194-195 197

C H F

65

+ (CH CO) 0/AlCl3

3 2

2-F-C H4CN + CH MgI CH FCOCl + C H SH C H F C O C l + C H O H + C5H5N 4-CN-2-F-C H OCH + SnCl /HCl 4 - F - C H C H C l + NaCN then H 0

2 2

93 at 4 m m . 25

1.4830

1.170

6

3 65 65 63 3 64 2

Acid chloride + Acid chloride + Acid chloride + 4-F-C H COCH

64

9 4 - 9 9 a t 12 m m .

CH3OH CH3OH CH3OH OCOCH

2

2

3+

259.8

80 84 152

BaC0

65 2

2 2

3

20

1.4525

3

2

1.2616

4

2 2

A c e t y l a t i o n of a m i n e Acid chloride + N H Aldehyde + H N N H C O N H 173.7 at 754 m m .

2

Diazonium chloride + HF 3-F-4-CH 0-C H COCH3 + KMn0 Na-4-F-sulfinate + C1CH C0 H . C H N H + C H F C 0 H at 170°

3 63

1 0 1 - 1 0 2 a t 17 m m . 8 7 - 8 9 at 11 m m . 1 0 8 - 1 1 1 at 24 m m .

2

4-F-C H CH CH OH + PBr /C H F r o m borofluoride 4-F-C H OC H + Br From 2-F-C H CONHCl

64 2 2 64 25 64

3 66

A c y l a t i o n of a m i n e 1 0 9 a t 14 m m .

95 128 63.5-64.0 33.7 33.5 77 155-159 at 3 m m . 179 at 15 m m . 178.4

25

C H NHCH

65

3+

COF

2

F r o m borofluoride 4-F-C H OC H + CH3CONO3 2,5-F-C H N0 + C H ONa C H F O + HNO3 o r f r o m b o r o f l u o r i d e Aldehyde + [ ( C H ) C H O ] A l / (CH ) CHOH Nitration

65 25 63 2 25 89 32 3

32

142, 396, 434 43 53 421 133 114 460 312 312 312 172 460 437 370 133 171 456 485 496 492 359 293 319 463 268 460 429 87 490, 536 132 226 226 90 489 490 432 133 457a 495

297

88 4 C H FN0 S 88 4 C H FN 0 8 8 23

2-F-C6H4COCH3 C6H5S-COCH2F CH FC0 C H 3-F-4-CH 0-C H CHO 4-F-C H CH C0 H 4-F-C H OCOCH 2-F-C6H4CO2CH3 3-F-C H C0 CH 4-F-C H4C0 CH 4-F-C H COCH OH 2-CH CO-4-F-C H OH 4-F-3-CH -C H C0 H 2-F-4-CH -C H C0 H 3-F-4-CH 0-C H C0 H 4-F-C H S0 CH C0 H 5-(S0 F)-2-CH 0-C6H C0 H C H NHCOCHF 2,4-F-C H NHCOCH 2,5-F-C H3NHCOCH 3,5-F-4-CH O-C H C0NH 2,6-F-C H CH=N-NHCONH 2-CF3-C6H4OCH3

-2.7

ORGANIC COMPOUNDS CONTAINING FLUORINE

C C C C

4-F-C6H4COCH3

298

T A B L E I (Continued) Structure C H8FN 02

8

3 C8H8F N 0 2 22 C H F 0 8 82 C H F 0 S2 8 824 C H F NO 8 83 C H F N0 S 8 83 2 C H F 8 84 C H F 0 8 882 C H F 89

89

C H F0 S

89 2

C H F0 S C H F0

89 3 89 4 C H FN 81 0 C H FNO C Hi FNO

81 0 8 0 2

63 2 63 2 3 62 2 63 25 3 6 2 2 3 3 63 2 3 3 63 2 3 3 2 3

3 63 6425 4-F-C H C H 6425 3-CH C H CH F 3 64 2 4-CH C H CH F 364 2 3-F-4-CH OC H CONHNH 3 63 2 2-F-C H OC H 64 25 3-F-C H OC H 64 25 4-F-C H OC H 64 25 2-CH 0-5-CH -C H F 3 3 63 2-C H -4-F-C H OH 25 63 4-F-C H CH(OH)CH 6 4 3 4-F-C H CH CH OH 64 2 2 CH FCH20C H 2 65 2,4-CH -C H S0 F 3 63 2 4-C H C H S0 F 2564 2 4-C2H OC6H S0 F 5 4 2 CF=CH-CH2CH(C0 H)CH(C0 H)CH2 2 2 _l 4-F-C6H CH CH NH2 4 2 2 2-F-C H N(CH ) 64 32 4-F-C H N(CH ) 64 32 4-NH2-2-F-C H OC H 63 25 3-F-4-CH 0-5-NH2-C H CH OH 3 62 2

B.p., °C

Preparation

t. ° C

2 2

72 a t 18 m m .

147-149 83-90 at 5 m m . 143-144 136-137

25 25

1.4019 1.3484

19.5-20 178-179(d)

2564 4-C H C6H NH 2 5 4 2+

20 20

1.4952 1.4919

1.0089 1.0032

64 a t 11 m m . 65 a t 15 m m . -8.5

9.3

41-41.5

7 1 a t 18 m m . 7 2 a t 12 m m . 64-65 at 3 m m . 9 0 . 5 a t 10 m m . 117-118 at 20 m m . 9 2 . 5 - 9 3 . 0 a t 17 m m . 246 238 1 2 4 . 5 a t 14 m m .

108-109.5 163

25

9 9 - 1 0 0 at 24 m m . 6 4 - 6 5 a t 13 m m . 7 8 - 7 9 . 5 at 16 m m .

55

141 a t 2 m m .

2 2 63 2

Dihydrazobenzene + CF2=CF2 />-Dioxane + C F 2 = C F 2 m-Xylyldiazonium borofluoride 2-C H C H NH2 + NaN0 + HF

141 48.5 at 8.5 m m . 46.5-47 at 8 m m .

Ref.

Aldehyde + H N - N H C O N H Aldehyde + H N - N H C O N H From methyl ester From 2-F-4-NH2-C H OC H5

1.061

25 25

1.5056 1.4980

1.124 1.1108

2 NaN0 + HF 2 Benzyl bromide + H g F 2 Benzyl bromide + H g F 2 From methyl ester F r o m ethoxy benzene diazonium boro­ fluoride F r o m ethoxy benzene diazonium boro­ fluoride F r o m ethoxy benzene diazonium boro­ fluoride F r o m diazonium borofluoride Phenetole + H I / C H C 0 H

3 2

4-F-C H MgBr + O-CH2-CH2

64

I

C6H5C2H5 +

11, 378 378, 434 32 32 359 427 427 427, 460 427 460 4 463

I

FCH CH C1 + C H ONa

2 2

226 226 359 442 85 239 239 240 68 169 517

65 HOS0 F 2

423 85 457a

CH ==CFCH=CH

456 72

F r o m borofluoride Nitro compound Fe/HCl Nitro compound H

463 532 439 442 133

2 2 + C O C H = C H C O_JO F C H C H B r +• N H 6424 3

PAUL TARRANT

C 8 H 9 F N 22O C H FO

M.p., °C

238 2- F - 4 - O H - C H CH=N-NHCONH 236 4-F-2-OH-C H CH=N-NHCONH 189-190(d) 3,5-F-4-CH OC H CONHNH 2,4-F-C H OC H 116-118 l,3-CH -4,6-C H2(S0 F) 57-58 2-CH 0-5-CF -C H NH 58-60 4-CH 0-5-CF -C H NH 94-95 2-NH2-4-CF -C6H S0 CH Bicyclo[4-2-0]-2-octene, 7,7,8,8-tetrafluoro p - D i o x a n e - ( 1 , 1 , 2 , 2 , 3 , 3 , 4 , 4 - o c t a f l u o r o b u t y 1) 2,4-CH -C H F 2-F-C H C H

C H

8 1FF NO0O22S 1 40

C8H

C8H10F4O4 C H F O

C H F 0 CsHi F0

8 1 42 3 2 C H BrF0 81 42 C H FNO 81 4 CeHi F N 0 42 22 C H F 0 8 1 242 C H F0 8 1 25 C H FN0 8 1 62 C Hi F 8 62 C H F 81 7 C HC1 F C H C1F N C H C1F 0

C H C1F 0

CH FCOSCH CH SCOCH F CH (CH ) CHCF CHF 1 1

2 2 2 2 2 24 2 2 C HnCF CHF 6 2 2 C HnOCF CHF 6 2 2 CH (CH ) -CHF-CH-OCOCH 2 2 3 3 1 1 Br(CH ) C0 CH CH F 25 2 2 2 CH FCONHC Hn 2 6 (CH CH CH NHCOF) 2 2 2 2 CH CF (CH ) C0 C H 3 2 2 3 225 F(CH ) C0 CH CH F 2 5 2 2 2 F(CH ) C0 C H 25 2 2 5 CH FC0 CH CH N(C H ) 2 2 2 2 2 52 CH CF (CH ) CH 3 2 25 3 CH CH CH CF (CH ) CH 3 2 2 2 23 3 CH CHF(CH ) CH 3 25 3 CH F(CH ) CH 2 26 3 C HC1 CF 6 4 3 4-Cl-3,5-CN-C H CF 62 3 2,5-CF -C H COCl 3 63 3,5-COF-C H CF 63 3 3,5-CF -C H COF 3 63 2,5-CF -C H CHO 3 63 3,5-CF -C H CHO 3 63 C H 0CF=CC1CF 65 3 3-CF -C H OCF=CHCl 3 64 3-CF -C H OCF CHCl 3 6 4 2 2 4-CF -2-Br-C H CH=CH 3 63 2 2-Cl-6-F-C H CH=CHC0 H 63 2 C H OCF CHClCF 65 2 3 3-CF -C H OCF CH Cl 3 64 2 2 1- Fluor oisoquinoline 3 - Fluoroisoquinoline 4- Fluoroisoquinoline 5- Fluoroisoquinoline

52.8 at 10.3 m m .

25

1.3790

1.2123

89 a t 15 m m . 158-158.5 180-190 161.0-162.0 at 3m m . 141.5-142.0

20

1.369

1.264

25

1.3841

75-77 at 21 m m . 86 at 100 m m . 7 5 - 7 8 at 12 m m .

25 25

1.3626 1.3848

-50 -45.9

10

102 at 4 0 m m . 1 0 3 - 1 0 5 a t 14 m m . 8 2 - 8 4 a t 14 m m . 9 6 . 5 - 9 7 . 0 at 16 m m . 136.3-136.6 137.3 139.3 60 at 4 0 m m . 142-142.5 at 754 m m . 248 210 70 at 10 m m .

456 365

Acid + alcohol (C H )20 + CF =CF (-CH OCH ) + CF =CF Dithioglycol + acid Cyclohexane + CF2=CF2

215 169 169 163 20

C H + CF =CF C HnOH + CF =CF Chloro compound + K F

19 170 162

Acid + a l c o h o l / H S 0 Cyclohexylamine + ethyl e s t e r

54 7 56 215 54 54 163 200 200 500

2 2

25 2

1.1526

142 a t 18 m m . 99-100 75 -50.2

F r o m nitro compound CF=CF-CF CF + C H OH/KOH 1 1

32

6 12 6

2

25

2

2

2 2 2

2

2

2 4

1.0548

20 20

1.3901

20 20

1.3763 1.378

0.8854 0.8919

14

1.3970

0.8036

(CH CH2CH NCO)2 + HF Acid + alcohol Br(CH )5C0 C2H F + AgF B r compound + A g F Acid + alcohol Octene-2 + HF Octene-4 + HF Octyl iodide + A g F

2

2

2 2

4

Octyl iodide + A g F + CI C H CF Halo compound + CuCN 2 , 5 - C F - C H C H O + CI

65 3 3 63

Chloro compound + H F or S b F Chloro compound + H F or S b F

88 at 15 m m . 160 170-172

Benzylidene fluoride +

H2SO4

3 3

B e n z y l i d e n e f l u o r i d e + H SC«4 -54 -64

212 -33 -42

43

185 189 211 72 at 5 m m .

20 20 20 25

1.4513 1.4454 1.437 1.5228

1.367327 1.390927 1.48527

188 197 208 251 236 145 at 6 2 m m .

20 20 30 30 30

1.4215 1.4255 1.5861 1.5875 1.594

1.411227 1.417727

S a t u r a t e d e t h e r 4- b a s e

2

CHCI2CF2CI + aryl oxide

1.558 2-C1-6-F— CeH CHO + malonic acid CF CHC1CF + C H ONa CH2CICF2CI + aryl oxide Schiemann reaction Schiemann reaction Schiemann reaction Schiemann reaction

3

3

3

65

498, 500 235 249 252, 425 276 276 246, 425 246 316 316 316 4 547 316 316 410 410 410 410

299

95 4 C H C1 F 0 9 5 25 C H BrF 96 3 C H C1F0 96 2 C H C1F 0 96 5 C H FN 96

55-56 -50.9

FLUORINE

9 43 92 32 93 6 C H F 0 9 352 C H F 0 9 37 C H F 0 9 46

2 3 62 2 25 25 2 2 (CF C0 C H ) 2 2 2 52

ORGANIC COMPOUNDS CONTAINING

8 1 80 C8Hi F O 08 2 C Hi F 04S 8 22 C H F 8 1 42

5-NH -2,4-CH -C H S0 F

C(OC H )=C(OC H >-C F C F 1 1

300

T A B L E I (Continued)

C H F C H BrFN0 C H7Br F02

9 64 97 4 9 2

M.p., °C

Structure

Formula

3-CF -4-F-C H CH=CH 3-Br-2-F-5-CH -4-N0 -C HC0 CH 3-(2-F-C H )-2,3-Br-C H C0 H

3

63 3 64

2 2 6 2 3 22 2

B.p., °C

t. ° C

77 at 40 m m .

25

n< 1.4522

d<

Ref.

Preparation

4

1.263 Acid + alcohol

88 183

269 547

<^^CHBrCHBrC0 H

2

C H7FU3

9 F3 97

C H

9 73 98 3 98

C H C1F 0 C H C1 F 0

98 3 9 8 22

C H FI0 C H FN0

98 2 98 3

C H FN0 C C C C C C C

C C C C

98 4 9HH 8FF N00 5 9 823 9HH 8FF 3NN O0 S 9H 8F 30 4 9 84 9H 9B r 2F 9H 9C 1 F 20 9H 9C 1 2F 9HH 9FFINN 00 3 9 9 24 9H 9F N 20 6S

3 64 3 64

6 32 2 2

3

4-CF -C H CH=CH 4-CH -C H COCF 4-CF -2-Br-C H CHOHCH 2-CH -C H OCF=CHCl 3-CH -C H OCF=CHCl 4-CH -C H OCF=CHCl 3-CF -4-d-C H CHOHCH 2-CH -C6H OCF CHCl 3-CH -C H OCF CHCl 4-CH -C H OCF CHCl 2-I-3-F-C H C0 C H 2-F-C H CONHCH C02H

3 64 2 3 64 3 3 63 3 3 64 3 64 3 64 3 63 3 3 4 2 2 3 64 2 2 3 64 2 2 63 225 64 2 3- F-C H CONHCH C0 H 6 4 2 2 4-F-C H CONHCH C0 H 64 2 2 4-F-3-N0 -C H C0 C H 2 63 225 3-F-4-CH 0-5-N0 -C H COCH 3 2 62 3 3-F-4-CH 0-5-N0 -C H C0 CH 3 2 62 2 3 3,5-F-4-CH 0-C H C0 CH 3 6 2 2 3 3-CH CONH-C H CF 3 64 3 4-CF -2-N0 -C H SO C H5 3 22 3-CF 3 - 4 - F - C2H 6 3 6 3C H O H C H 3 2,4,5-CH -3,6-Br-C F 3 6 2-CH -C H OCF CH Cl 3 64 2 2 3-CH -C H OCF CH Cl 3 64 2 2 4-CH -C H OCF CH Cl 3 64 2 2 2,4,5-CH -3,6-Cl-C F 3 6 4-HO-3-F-5-I-C H CH CHNH C0 H 62 2 2 2 2,4,5-CH -3,6-N0 -C F 3 2 6 2,4,6-CH -3,5-N02-C S0 F 3 6 2

130

-39

-15 -19 -15

61 at 40 m m . 64.5 at 40 m m .

25 25

1.4677 1.4632

1.1749 1.1588

66 at 40 m m . 131 at 173 m m . 104 at 3 m m . 59 a t 4 m m . 64 a t 4 m m . 64 at 4 m m . 109 at 6 m m . 230 230 234 149 at 6 m m .

25 20 25 20 20 20 25 20 20 20

1.4648 1.4693 1.5060 1.5057 1.5031 1.5032 1.4853 1.485 1.482 1.481

1.1653 1.2304 1.601 1.1903 1.1880 1.1854 1.3672 1.33427 1.32227 1.32027

121 152 161 45 50 37 103 117 144 -33

150 192 75 157

145 at 4 m m . 130 at 3 m m . 55 a t 0.2 m m . 287

461 277 4, 277, 396 277 362 C H CH + CF COCl 4 4 - C F - 2 - B r - C H M g B r + CH3CHO 316 Saturated ether + base Saturated ether + base 316 Saturated ether + base 316 3 _ C F - 4 - d - C H M g B r + CH CHO 335 316 Sodium cresolate + CHC1 CF C1 316 Sodium cresolate + CHC1 CF C1 316 Sodium cresolate + CHC1 CF C1 Acid + alcohol 454 77 I s o l a t e d f r o m u r i n e of d o g s f e d t h e c o r ­ responding fluorobenzoic acids 77 77 412 133 Acetophenone + H N 0 133 Acid + alcohol 359 Acid + alcohol 473 Amine + ( C H C O ) 0 240 4 Grignard reagent + CH CHO 518 Trimethylfluorobenzene + B r 316 Sodium cresolate + C H C 1 C F C 1 316 316 518 T r i m e t h y l f l u o r o b e n z e n e + CI 133 3-Fluorotyrosine + I 518 Trimethylfluorobenzene + H N 0 458 Mesityl sulfonyl fluoride + H N Q

5-F-2-HO-C H COOH + Alcohol + P 0

63 25

65 3 3

3 63

3

63

(CH C0 )

3 22

3 2 2 2 2 2 2

3

3

86 at 5 m m .

25

1.4461

1.332

66 at 4 m m . 70 at 4 m m . 70 a t 4 m m .

20 20 20

1.4758 1.4731 1.4732

1.2388 1.2325 1.2222

2

3 2

2

3 3

PAUL TARRANT

C H F 0 C H BrF 0 C H ClFO

F 4-F-2-CCOH-C H 0 CCH 2-CF -C H CH=CH 3-CF -C H CH=CH

C6H5CH2CH2COF

C9H9FO

2-F-C6H4COC2H5 4-F-C6H4CH2COCH3

2-F-C6H4CO2C2H5 3-F-C6H4CO2C2H5 4-F-C6H4CO2C2H5

C9H9FO2

- 2 1 -33

2-HO-5-F-C6H3COC2H5

30

4-F-C6H4O2CC2H5

3

C H F0

99 3

C9H9FO3S C9H9F2NO C9H9F2NO3

5

3

3

3

2

C9H9F3O

92 66 70 66

25

1.4623

1.2608

520 43 463 505 505 452 460 460 2-F-C H OCH + ( C H C O ) 0 + AICI3 1 3 3 Grignard reagent + C 0 461 Schiemann reaction 359 4-F-C H4S0 Na + CH ClCOCH 171 Amine + (CH CO) 0 547 H y d r o l y s i s a n d r e d u c t i o n of b e n z o y l 133, aminocinnamic acid 359 Grignard reagent + C H C H 0 4

25

1.4560

1.2369

G r i g n a r d r e a g e n t + CH3CHO

2-F-C6H CN + C H MgBr 4-F-C H MgBr + CH ClCOCH Acid + alcohol Acid + alcohol Acid + alcohol

4 64

25

1.4768

1.128

64

116 at 5 m m .

6

280(d)

3-CF3-C6H4CH2CH2OH

25

87 at 4 m m .

2

3

2 3

3 2 2 2 3

2

I 3-CF3-C6H4CHOHCH3 C9H10FNO

9 9 at 15 m m .

3-F-2-CH3-C H NHCOCH

132

C9H10FNO2

63 3 4-CH3O-3-F-5-NH2-C6H2COCH3

C9H10FNO3

4-CH3O-3-F-5-NH2-C6H2CO2CH3

55

4-HO-3-F— C 6 H 3 - C H C H N H C 0 H

277(d)

2

C9H10F3NO2S C9H11F

91 2 C Hi FN0 S 9 2 2 C9H13FN2O2S CioHτBrF CioH BrF0 S Ci H ClF

6 06

2

Ci H ClFO S

l,3,5-CH -2-F-C H 4-F-C6H CH(CH )2 5-F-2-HO-C6H3C3H7 4-F-C6H4CH2CH2NHCH3 4-F-C6H4CH CH(CH )NH2 2,4,6-CH -3-NH2-C6HS0 F 2,4,6-CH -3,5-NH2-C6S0 F l-Br-2-F-naphthalene l-Br-4-F-naphthalene l-F-5-S0 Br-naphthalene l-Cl-4-F-naphthalene l-Cl-5-F-naphthalene l-Cl-8-F-naphthalene 2-F-6-S0 Cl-naphthalene 4-F-l-S0 Cl-naphthalene l-F-4-N0 -naphthalene l-N02-2-F-naphthalene

2 2

3 3

2

2 2 2

42-43 26-27

2

3

2 2

62 142-143 49 37 145 85 32 44 97 86 80 49

Amine + (CH CO) 0 Nitro compound + [H] Nitro compound + [H]

3

138 at 2 m m . 117 at 0.1 m m .

2

H y d r o l y s i s a n d r e d u c t i o n of b e n z o y l aminocinnamic acid 172-175

Pseudocumenediazopiperidide

171-172 164 68 at 2.5 m m . 106 at 26 m m . 9 6 at 17 m m .

62 3

2 2I

' 130 at 12 m m .

25

1.5000

1.088

4 - F - C H B r + C H B r + Na P h e n e t o l e + HI 4-F-C H4CH CH Br + CH NH 4-F-C6H4CH2COCH3 + H C O N H Nitro compound + Sn/HCl Nitro compound + Sn/HCl Schiemann reaction Schiemann reaction Acid + P B r Sulfonyl chloride + P C l / h e a t Sulfonyl chloride + P C l / h e a t Schiemann reaction Acid + P C 1 A c i d + PCI5 + HNO3 Schiemann reaction

64 37 6 2 2

5

5

C10H7F

120 at 12 m m .

+ HF

3 2 2

5 5

4, 396 293 133 133, 359 359 240 517, 536 517 434 460 463 463 458 458 353 431 307 307 307 30 431 308 431 548

301

06 06

Ci H FNO

4-CF3-2-NH2-C6H3SO2C2H5 l,2,4-CH3-5-F—C6H2

3 4

C9H11FO C H FN

2 2

3

ORGANIC COMPOUNDS CONTAINING FLUORINE

3-F-4-CH 0-C6H COCH 5-F-2-C2H 0-C6H C02H 3-F-4-CH3O-C6H3CO2CH3 4-F-C6H4SO2CH2COCH3 3-CH3CONHC6H4CHF2 3,5-F-4-HO-C6H2-CH CHNH2C02H

9 6 a t 17 m m . 97 at 19 m m . 108 at 18 m m . 221 209 210 120 at 22 m m . 1 0 2 a t 19 m m .

Formula

C10H6F2 C10H7F C10H7FSO3 CioHsFN CioHeFN0 S

2

0 82 2 0 84 9 4 2

04 2 CioHuF0 2 CioHiiF0 3 Ci HiiF O 0 3 CioHi FO 3 Ci Hi FO 0 3 2 Ci Hi FN 0 4 CioH FI0 1 82 CioHi F 0 8 22 Ci Hi FO 0 9 2 C10H19F2NO 0

Ci H iF C11H9F CnH F0 S CnH FN 0

02 9 3 1 23 6 C11H13FO CnHi F0 3 2

C11H13FO3 CnH

1

F

5

2 6 2 2 0 2 2 06 2 2

65 3 2 3 2 6 225 5 2 3 64 22 3 3 6 32 6 42 3 7 63 37 65 225 25 63 2 2 364 32 3 4 25 34 25 6325 25 63 3 6 4 2 52 27 2 2 2 27 2 2 2 27 2 2 5 2 8 17 2 4 92 3 28 2 3 1 60 06 3 3 2 36 33 25 63 3 63 49 64 49 3763 2 363 33

M.p., °C

B . p . , °C

31.5 70.5 - 9 59 100 105 48 104-205 196-197 133 120

98 at 34 m m .

39

n

d

2 2

Ref.

2

Nitro compound + [H] S u l f o n y l c h l o r i d e + NH3 Sulfonyl chloride + N H Sulfonyl chloride + N H

3 3

25

1.4530

1.230

138 at 23 m m .

Carbinol -

H 0

2

Benzaldehyde + C H F C 0 C H Phenacyl chloride + C H C 0 N a Carbinol - H 0

2

84 at 40 m m . 8 2 at 5 m m . 124 at 36 m m . 117 a t 14 m m . 108 at 11 m m .

25 25

1.4625 1.4475

1.1358 1.285

9 1 a t 10 m m . 88 at 5 m m . 91 at 4 m m . 68 at 2.5 m m . 111 at 6 m m . 93 at 12 m m . 123 at 0.8 m m . 1 2 9 at 13 m m . 191

25 25 25 25 25

1.4572 1.4562 1.4964 1.4801 1.4985

1.2039 1.197 1.061 1.027 1.127

96-97

2 3 3 2

2

Fluorophenol + C H C l C 0 N a

184 260

0.792

10

118 95 8

Preparation Schiemann reaction Schiemann reaction Amine + H N 0 + HF Amine + H N 0 + HF Sulfonyl chloride + H 0

212 212

90 at 4 0 m m . 65-66 25 49

t. ° C

93 at 0 m m . 133 1 2 2 at 16 m m .

74 97 at 25 m m .

25

1.5246

1.037

25

1.4832

1.094

2

2

P h e n e t o l e + HI Ethylene + [H] Schiemann reaction Acid + alcohol I(CH ) C0 CH CH F + AgF Iodide + A g F CF =CF + C Hi NH C F = C F + (C H ) NH Decyi bromide + HgF Schiemann reaction Silver salt + CH I 3-F-5-CH -C H C(CH ) + HN0 Carbinol + H P 0 , 200°

2 2

27 2 2 2 2 8 7 2 2 4 92 3 3 63 3 4

33

Phenol + C H C l C 0 N a 3-F-C H CH + (CH ) CC1

2 64 3

2

33

3

431 431 129 129 431 431 431 308 307 431 497 4 269 497 172 4 4 460 460 145 460 4 4 460 460 460 439 54 54 54 399 399 500 548 307 82 460 460 460 460 82

PAUL TARRANT

Ci H F O Ci H F CioH BrFN0 CioH9F0 C10H9FO3 C10H9F3 CioHi F 0 Ci HnFO

Structure 1,4-F-naphthalene 1,5-F-naphthalene 1-F-naphthalene 2-F-naphthalene I-F-C10H6-4-SO3H 2-F-C10H6-6-SO3H 4-F-l-NH -naphthalene 4-F-CioH S0 NH 5-F-Ci H6SO NH 2-F-Ci H -6-SO NH C H CHFCHFCOOH 3-CF -4-F-C6H3C(CH3)=CH 3-Br-2-F-5-CH -4-N0 -C HC0 C H C6H CH=CFC0 CH 4-F-C H COCH 0 CCH Z-Η.YZQ$&IQ{ΗMS)=QK>L 3-CF -4-F-C H3COH(CH ) 4-F—C H 0 CC H 5-F-2-HO-C H COC H C H CHFC0 C H 2-C H -4-F-C H OCH C0 H 3-CF C H COH(CH ) 3-CF C6H CHOHC H 5-F-2-HO-C6H C H9 5-F-2-C H OC H C H 5-F-2-C H OC H CHOHCH 4-F-C H N(C H ) I(CH ) C0 CH CH F F(CH ) C0 CH CH F F(CH ) C0 C H CHF CONHC H CHF CON(C H ) CH (CH ) CH F l-F-2-CH C H 5-F-Ci H SO CH 3-F-2,4,6-N0 -5-CH C C(CH ) 5-F-2-C H OC H CH=CHCH 3-F-2-HOC H COC H 4-F-C H OCOC H 4-F-2-C H C H OCH2C0 H 3-F-5-CH C H C(CH )

l

302

l

T A B L E I (Continued)

CnHi FO

5

C12H6F3NO2 C12H6F4 C12H7F2NO2

C12H7F3

28 28

2

104 139 93 95 83 100 123 60 54 75 72 81 118 8 88

2 6 4 63 263 6 4 4 2 4

2 64 6 2 6 4 4

Ci2H F2

8

Ci H F N Ci H F 0 S Ci H F 0 S Ci H F 0 S Ci H F3N C12H9F

2 822 2 822 2 823 2 8242 28

C12H9F2N C12H9F3N2 Ci H FN

21 0

Ci HiiFN 0 S C12H11FN2O5S2

2

105 at 4 m m . 1 0 1 a t 16 m m .

22

C12H11FO3S C12H15FN2O4 C12H15FO C12H15FO2

21 7

64 6 2 64 3 2 4 4

,

2 2

2 2

4

6 2

6 6 4 6 2 4 2 2

5

4

2

63 3 62 2

3 3

6

3

3 3

3

1.4782

1.000

t

49 73

636 64 64 6 64

6465 64 6 646 6 65 64 65 64 65

254

101 98 95 133 72 71 24 74 100 120 42 36 91 166 260(d) 285(d) 79 93 54 89

P h e n e t o l e + HI Propenyl compound + H 3 , 4 , 4 ' - F - C H C H 4 + HNO3 Schiemann reaction 4,4'-F-C H -C H + HNO3 4 4 ' - F - C H 4 - C H + HNO3 Schiemann reaction Schiemann reaction 4-F-C H C H + HNO3 4 - F - C H - C H 5 + HNO3 4 - F - C H C H 5 + HNO3 2-F-C H4-C H + HNO3 2-F-C H -C H + HNO3 2-F-C H -C H + HNO3 Schiemann reaction Schiemann reaction F r o m diazopiperidide

401 238 281 458 435 435 435 435 430 437 Nitro compound + Sn/HCl 528 Nitro compound + Sn/HCl 528 Nitro compound + Sn/HCl 528 Nitro compound + Sn/HCl 528 A c e t a n i l i d e , 4 - F - C 6 H N H + HOSO2CI 1 6 5 462 Sulfonyl chloride + a m i n e Sulfonyl chloride + a m i n e 462 Salt + C H I 307 Salt + C H I 308 F l u o r o c o m p o u n d + HNO3 82 F l u o r o c o m p o u n d + HNO3 82 C a r b i n o l + H3PO4, 2 0 0 ° 460 460 460 Phenol + C H C l C 0 N a 460 4-F-3-CH C H CH3 + (CH ) CC1 82 4-F-3-CH3C6H3CH3 + ( C H ) C C 1 82 C H F + HOS0 Cl C H F + HOS0 Cl 3-I-C6H4SO2F + C u Nitro compound + Zn/HCl Schiemann reaction Schiemann reaction Schiemann reaction Nitro compound + Sn/HCl

65 65

186 at 4 0 m m . 200 at 25 m m .

2 2

4 2

25 25

122 a t 13 m m . 1 3 4 - 1 5 0 at 16 m m . 147 at 12 m m . 97 at 21 m m . 100 at 2 2 m m .

25 25

1.5145 1.4719

1.023 1.046

460 460 435 435 435 436 435 300 528 528 528 528 528 528 437 437 430, 536

2 2 363

33 33

303

C12H15FO3 Ci H F

4,4'-F-(C H )2N2 (4-F-C H4) S02 (4-F-C H )2S0 3,3'-S0 F-C6H C6H4 3,3,4'-F-5-NH2-C6H -C6H4 2-F—C6H4C6H5 3-F—C6H4C6H5 4-F—C6H -C6H5 4,4'-F-3-NH2-C H3-C6H4 2,4,4'-F-2',5-NH -C6H2-C H3 4-F-4'-NH -C6H4'C H4 4-F-2'-NH -C6H4-C H4 2-F-4 -NH2-C6H4-C6H 2-F-2'-NH2-C6H4-C H4 4-F-C6H NHS0 C6H NH2 4-NH -C6H4S0 NH(4-F-3-S03H-C6H3) 4-NH -C6H4S0 NH(4-F-2-S0 H-C6H3) 5-F-C10H6SO3C2H5 4-F-C10H6SO3C2H5 2-F-4,6-N02-3,5-CH C6C(CH )3 4-F-2,6-N02-3,5-CH C6C(CH )3 5-F-2-C2H 0-C6H3CH=CH(C2H5) 4-F-C6H4OCOC5HH 5-F-2-HO-C6H3COC5H11 4-F-2-C H9C H OCH2COOH 2-F-3,5-CH -C H C(CH3)3 4-F-3,5-CH3-C6H C(CH )3

25

ORGANIC COMPOUNDS CONTAINING FLUORINE

Ci H BrF Ci H FN0

5-F-2-HOC6H3C5H11 5-F-2-C2H6OC6H3C3H7 3,4,4'-F-5-N02C6H C6H4 3,4,4',5-F-C H2C6H 4,4'-F-3-N02-C H C6H4 4,4'-F-2-N0 C H -C6H4 3,4,4'-F-CeH3-C6H4 4-Br-4'-F-C6H4-C H4 4-F-4'-N02-C6H C6H 4-F-2'-N0 -C6H4C6H 4-F-2-NO2-C6H3C6H5 2-F-4'-N02-C6H4'C6H4 2-F-2'-N0 -C H -C H4 2-F-4-N0 -C6H3-C H5 2,2'-F—C6H4C6H4 3,3'-F—C6H4-CeH 4,4'-F-C6H4-C6H

304

T A B L E I (Continued ) Formula C12H17FO

Structure

M.p., ° C

5.F-2-C H OC H C4H9

t. ° C

112 a t 1 4 m m . 106 a t2. 4 m m . 165 a t 1 5 m m . 186 a t 1 1 m m . 147 a t 1 2 m m . 136 a t 1 0 m m .

25 25 25

d* 1.4780 1.4956 1.4909

0.988 1.032 1.053

127 1 0 5 a t4 m m .

29 2 2 2 29 2 2 2

20

1.5071

1.42227

3

3

6 5 4 - F C 6H 4C O C l C H COCl+ C H F 65 65 Ketone + HONH 2 Oxime + H +

48 137 184 60

Fluorobenzyl chlorid e + chloropheno l Fluorobenzyl chlorid e + chloropheno l Fluorobenzyl chlorid e + chloropheno l Phenol + CH OH Sulfinate + benzoy l chlorid e (C6H ) CC1 + SbF

224 a t 1 2m m . 170 a t 1 2 m m .

3

260

52

Thiourea +

110 a t4 m m . 136 a t7 m m . 125 a t 1 1 m m . 140 a t 1 1 m m . 297 182 197

Nitrile + hydrolysi s Triiodonitrobenzene + fluoropheno l Naphthol + C F C H C 1 C F Triiodonitrobenzene + fluoropheno l

C H F +

150 a t 1 6 m m .

35 84 185 -2 226 188 47 90 114 147 175 48

Butène + H Phenetole + H I Br(CH ) C0 H + HOCH CH F Br(CH ) C0 CH CH F + Ag F Bromoester + Ag F

233 237 -11 128 110 118 114 108

Preparation

25

1.5128

1.008

25

1.4797

0.982

2

3

4 2

4-F—C6H NH

64 2 65

Thiocyanate + 4 - F — C H N H 4-F-C H MgBr + C H CHO Dehydration o f carbino l Benzoyl chlorid e + alcoho l Pentene + [H ]

64

Oxidation o fdimethy l compoun d Chloro compoun d + H F Chloro compoun d + H F

Réf. 460 460 460 54 54 54 359 360 359 316 360 225 225 225 118 29 118 118 118 259 259 259 430 171 192 429 295 164 444 444 444 295 434 460 142 460 54 270 242 242, 244

PAU L TARRAN T

25 63 636 3 C12H17FO2 25 63 9 Ci H 2BrF0 2 9 2 2 2 2 2 2 Ci H F 0 2 2 2 2 2 2 2 2 2 Ci H F0 F ( C H ) 9 C 0, C H 5 2 2 23 2 22 C13H6F2I2O4 3,5-1-4-0,5-F-4'-HO-C H 0)-C H C0 H 62 2 C13H7FI2O4 3 , 5 - I - 4 - ( 3 - F - 4 ' - H O - C H60 2 6 3 ) - C 6 H 2C 0 2H C13H7F2I2NO4 3,5-I-4-(3',5'-F-4'-CH OC H 0)-C6H N0 3 6 2 2 2 C13H8CIF5O l-(CF CHClCF O)Ci H C H8FI N04 3 , 5 - I - 43- ( 3 ' - F - 4 '2- C H 0O7 C H 0)-C6H N0 1 3 2 3 63 2 2 Ci H FN0 3-F-6-N0 -C H 0 CC H 38 4 2 6 32 6 5 3-F-4-N0 -C H 0 CC H5 2 6 32 6 3-F-2-N0 -C H 0 CC H 2 6 32 6 5 C H F 0 4,4'-(C H ) CO 1 8 3 2 6 4 2 Ci H FO 2-F-C H COC H5 39 64 6 4 - F,- C H C O C 6 H 5 Ci H F NO 4 , 4 ' - F6 - ( C4 H ) C = N O H 3 92 64 4,4 -F-C H4NHCOC H4 6 6 Ci Hi ClFO 4-F-C CH 0(4-Clr-C6H4) 3 0 6 2 3-F-C CH 0(4-Cl-C6H4) 6 2 4-F-C CH 0(2-Cl-C6H4) 6 2 4' - F - 4 - C H 0 - 3 - N 0 - < : H 4 C 6 H 3 Ci Hi FNO 3 2 6 3 0 3 Ci Hi FNO S 4-F-C6H S0 -CH C6H4-4-N0 3 0 4 2 2 Ci Hi F ( C H ) C F4 2 3 0 2 6 5 2 2 Ci Hi F N O (2-F-C H NH) CO 3 0 2 2 6 4 2 Ci Hi F N S (2-F-C H NH) CS 3 022 64 2 (4-F-C H ) CHOH Ci Hi F O 3 02 6 42 2-F-C6H CH=NNHC H C13H11FN2 4 65 3-F-C H4CH=NNHC H5 6 6 4-F-C H CH=NNHC H 64 65 Ci HnFN S 4-F-C6H4NHCSNHC6H5 3 2 C13H11FO 4-F-C H CHOHC6H 64 5 Ci Hi FO 5-F-2-C H 0-C H CH=CHC H7 3 7 C H FN0 4 - F - C H 2C 5 0 ( C6 H 3 ) N ( C H )3 1 1 3 8 2 6 4 2 2 2 2 52 C H FO 5-F-2-C H 0-C6H C H i i 13 9 25 351 C H F0 F(CH )ioC0 C2H5 1 23 25 2 2 C14H4CI2F4 2,2\6,6'-F-3,3'-C0 H-5,5'-Cl-biphenyl 2 Phthalimide, 4 - C F - 2 , 5 - C l - p h e n y l Ci4H Cl F N0 3 6 23 2 Ci H ClF N0 4 7 3 2 P h t h a l i m i d e , 2 - C F 3- 5 - C l - p h e n y l 5-F-2-HO-C H C Hi 5-F-2-C H OC H CHOHC4H Br(CH ) C0 CH CH F F(CH )9C0 CH CH F

B.p., ° C

C14H7CIF3NO2

C14H7FO2

2 8 2 2 8 22 Ci4H F N0 83 2 Ci H8F6N 4 2 C14H9CIFNO C14H9FO C14H9FI2O3

C14H9FO3 C14H10FNO4 Ci Hi F

4 02

C14H10F2N2O4 C14H10F6N2O2S

C14H11F C H FN 0 C14HHFO C14H11FO2 C14H11FO3

1 14 12 4

C14H11FO3S Ci4HnF N0 Ci Hi BrFO

4 2

,

2

>

62

2

2 2

C14H12FNO3 Ci4Hi F

22

3

3

3

5

C14H9F5

197 200 at 1 m m . 183 at 0.2 m m .

3

6

6

2

6 2 3 3-F—C6H4CH 02CC6H4-4-N0 2 2 4-F—C6H4CH20 CC6H4-4-N0 2 2 C6H CF=CFC H 5 65 4,4'-F-stilbene 4,4'-F-6,6'-N0 -3,3'-CH -biphenyl 2 3 3,5-F-4-CH30C6H NHCOC H4-4-N02 2 6 4-NH2-C6H4S0 NHC6H3-3,5-CF 2 3 2-F-4'-CH=CH-biphenyl (C H ) C=CHF 6 5 2 2-CH 0-3-F-C H3NHCOC H4-4-N0 3 6 6 2 2-F-4'-CH CO-biphenyl 3 2-(4'-F-C6H4CH )-C6H4C02H 2 2-(4'-F-C H4CH 0>-C6H4C02H 6 2 4-(2'-F-C H4CH 0)-C H4C02H 6 2 6 4 - ( 3 ',- F - C 6 H C H 0 ) - C 6 H 4 C 0 H 4 2 2 4-(4'-F-C6H4CH 0)-C6H4C0 H 2 2 2 - ( 4 - C H - 2 - F - C, H C O ) - € 6 H 4 C 0 H 63 2 4-F—C6H3S0 CH COC6H 42 2 5 4,4'-F-6-N0 -3,3 -CH -biphenyl 2 3 3-(2-CH -5-Br-C H OCH )-C6H4F 3 63 2 3-(4-CH -3-Br-C6H30CH )-C6H4F 3 2 N-(4-CH OC6H )-4-F-anthranilic acid 3 4 4,4'-F-3,3'-CH3-biphenyl 52 (C6H5CHF)

2

2

130 148 82 167

D e c a r b o x y l a t i o n of a c i d D e c a r b o x y l a t i o n of a c i d A m i n e + H N 0 + CuCN Iodotoluene + Cu A m i n e + C4H9NO2 + C u C N F r o m nitrile

2

283

107 137 63 86 98 122-123 106 143-144 207 166 37 93 148 85 148 87 181 194 213 129 151 89 73 41 188 59 38 66 129

Chloro compound + HF Chloro compound + HF Trifluorotoluidine + N a C r 0 7 A n t h r a n i l i c a c i d + POCI3

2 2

From nitrile Phthalic anhydride + C H F Phenol + C H C O C l

65

Benzyl Benzyl Chloro 4-F-C

65

chloride + sodium benzoate chloride + sodium benzoate compound + HF H CH /heat

65 3

Amine + benzoyl chloride N i t r o compound + [H] 106 at 1 m m . ( C H 5 ) C F C H F + KOH Amine + benzoyl chloride

6 2

2

R e d u c t i o n of b e n z o y l b e n z o i c a c i d Benzyl chloride + phenol Benzyl chloride + phenol Benzyl chloride + phenol Benzyl chloride + phenol Phthalic anhydride + 3 - F - C H C H Sulfinate + bromoacetophenone Schiemann reaction Benzyl chloride + phenol Benzyl chloride + phenol Chlorobenzoic acid + anisidine Schiemann reaction 3-F-C6H4CH3 + h e a t (C H ) C=CH + PbF Chloro compound + HF

64 3

1 4 0 a t 14 m m .

6 52

2

244 244 244 244 166 166 359 270 360 359 242 242 502 298 296 360 166 226 267a 25 25 10 311 437 359 22 396 113 359 396 166 259 259 259 259 378 171 436 260 260 298 436 311 113 10

305

3,3'-F-bibenzyl (C6H ) CFCH F

200-202 128 203 129-134 137-138 116 125

·

ORGANIC COMPOUNDS CONTAINING FLUORINE

C!4H7F2l2N0 C14H8CI2F4 Ci4H FI N0 Ci4H F I 03

Phthalimide, 2 - C F - 3 - C l - p h e n y l Phthalimide, 2-CF3-4-Cl-phenylPhthalimide, 2-CF3-6-Cl-phenylPhthalimide, 4-CF3-3-Cl-phenyl1-F-anthraquinone 2-F-anthraquinone 3,5-I-4-(3 ,5'-F-4'-CH30C6H 0)-C6H2CN 2 2',6,6'-F-3,3'-CH3-5,5'-Cl-biphenyl 3,5-I-4-(3'-F-4'-CH3O-C6H 0>-C6H2CN 3,5-I-4-(3',5'-F-4'-CH 0C H 0)C6H CHO Phthalimide, N-2-trifluoromethylphenylPhthalimide, N-3-trifluoromethylphenylAzobenzene, 4,4'-trifluoromethyl2-CH 0-6-F-9-Cl-acridine 3-F-benzanthrone 3,5-I-4-(3'-F-4'-CH30-C H30)-C6H2CHO 2-(4'-F-C H4CO>-C6H4C0 H 4-(C6H C02)-2-F-C H3CHO (4-F-C6H4) CHCF

306

T A B L E I (Continued) Structure

Formula

M.p., °C

C14H12F2O4S2 C14H12F2O6S2 C14H13FN2O3S

2,2'-CH -5,5'-S0 F-biphenyl 2,2'-CH 0-5,5'-S02F-biphenyl 4-F-C6H4NHSO2C6H4-4-NHCOCH3

2

146 205 163

Ci Hi FN 0 S

3-F-4-CH3O-C6H3CONHNHSO2C6H5 3-F-4'-CH CO-biphenyl 4,4'-F-6-NH -3,3'-CH3-biphenyl

176 88 210

4 3 24 C14H13FO C14H13F2N Ci H FO C14H21FO C15H7FO4

41 9

C15H7F6NO2

C15H11FI3NO4 C15H11FO3 C15H11F2I2NO3 C15H11F2I2NO4 C15H12FI2NO3 Ci Hi FI N0

5 2 2 4

C15H13CI2FO Ci Hi F0 C15H13F2NO4 Ci Hi FN0

5 3 2 5 4 4

C15H14F2 C15H19FO2 C15H22FNO2 Ci6HioF N 08

22

C16H11FO2

3 2 5-F-2-C2H 0-C6H CH=CHC4H9 5 3 5-F-2-C2H5O-C6H3C6H13

3-F-2-COOH-anthraquinone 4 - F - 1-COOH-anthraquinone Phthalimide, N - 2 , 4 - C F - p h e n y l Phthalimide, N - 2 , 6 - C F 3 -phenyl 4-CH3-2-F-anthraquinone 2_(3' - F - 4 ' - C 0 H - C 6 H 3 C O ) C 6 H 4 C 0 H 4-F-C6H COCH 0 CC6H4-2'-N02 4-F-C6H4COCH 0 CC6H4-3'-N02 4-F-C6H4COCH 02CC H4-4'-N02 (3,5-I-4-[3'-F-5'-I-4'-HO-C H 0]C H )-CH2CHNH2C0 H 2'-(5-F-2-CH3-C H CO>-C6H4C02H 2'-(3-F-4-CH3-C H CO)-C6H4C0 H 3,5-I-4-(3',5'-F-4'-CH 0-C6H 0)C H NHCOCH 3,5-I-3',5'-F-thyronine 3,5-I-4-(3'-F-4'-CH30-C6H 0)C H NHCOCH3 (3,5-I-4-[3'-F-4'-HO-C H30]-C6H )CH CHNH C0 H 3-(2',4'-Cl-3 ,5'-CH3-C HOCH )-C6H4F

2

4

62 62

22 22 2 6 2 63 63 3 3

62 , 6 2 2 2 6 4-F-C H4CH2CH 0 CC6H5 6 22 3', 5'-F-thyronine 4-(3'-F-4'-HO-C H30)6 C6H4CH2CHNH2CO2H (C H ) CFCHFCH 6 52 3 4-F-l-CH3-anthraquinone

2

62 2

2

2

2

2

3-F-2-CH3-anthraquinone 4-F-C6H4C0 CH CH N(C3H7)2 2,2'-F-3,3'-C0 H-5,5'-CH3-6,6'-N02biphenyl 4-F-l,3-CH -anthraquinone

2 2 2 2

3

Preparation

Ref.

Iodotoluene + Cu Iodoanisole + Cu Aniline + sulfonyl chloride Hydrazide + sulfonyl chloride 176 at 44 m m . 135 at 9 m m . 107 a t 3 m m .

183

25 25

1.5030 1.4820

0.996 0.982

Carbinol + H3PO4 R e d u c t i o n of h e x e n e c o m p o u n d Methyl anthraquinone + H N 0 Methyl anthraquinone + HNO3 Chloro compound + H F

3

185-190 160-163atO 2 m m .

3

t. ° C

458 458 165, 462 359 396 437 460 460 166 166 242 242 378 166 172 172 172 360

136 183 75 105 134 201(d)

F r o m benzoylbenzoic acid O x i d a t i o n of m e t h y l c o m p o u n d Phenacyl chloride + sodium benzoate Phenacyl chloride + sodium benzoate Phenacyl chloride + sodium benzoate

150 154 219

4-F-C H CH + phthalic acid 3-F-C H CH + phthalic acid A c y l a t i o n of a m i n e

166 166 359

248(d) 199

A c y l a t i o n of a m i n e

359 360

64 3 64 3

248(d)

360

88

55 242 238(d) 117 at 2 m m . 155 172 150 at 7 m m . 318-320 178

Phenol + benzyl chloride Alcohol + acid T r e a t m e n t of 3 , 5 - d i o d i d e w i t h [ H ]

260 463 359 360

(C6H ) C=CHCH3 + F F r o m benzoylbenzoic acid From benzoylbenzoic acid A c i d c h l o r i d e 4- e t h a n o l a m i n e Bromobenzene derivative + Cu

113 166 166 142 269

From benzoylbenzoic acid

166

52

PAUL TARRANT

C15H9FO2 C15H9FO5 C15H10FNO5

3 3

B.p., °C

6

Ci HiiF0

2

C16H12FNO C16H12F2N4O8

224 C16H12F6N2O3S Ci6Hi F 0

C16H13FO3

C16H18F2N2

2 24

Ci6H oF N

C17H11F2NO3 C17H12FNO3

7 32 4 C Hi FN0 1 47 4 Ci Hi F N0

C17H15FO3 C18H16F2O4

1 19 2 3 C19H13CIF2

C

H

C1F

9 4

Ci Hi ClF

C

1 49 2 Hi F

C19H15F

9 1F O5

Ci H

C20H12F2S2

3-F-2-C2H5-anthraquinone 4 - F - 1 - C2 H5-anthraquinon e 4-F-C6H COCH CHCNC6H 3,3',5,5'-CH -2,2'-F-4,4',6,6'-N0 biphenyl 2,2' - F - 6 , 6 ' -CO2CH 3- b i p h e n y1 3,5-CF3-C6H NHS0 C6H -4'-NHCOCH 2.(3-F-4-C H5-C6H3CO)-C6H C0 H 2-(5-F-2-C H5-C6H3CO)-C6H C0 H 2-(5-F-2,4-CH -C H CO>-C6H C02H 2-(3-F-2,6-CH -C H CO)-C6H C02H 3,3',5,5'-CH -2,2'-F-6,6'-NH -biphenyl 3,3',5,5'-CH -2,2'-F-4,4',6,6'-NH biphenyl 4-(3,5-F-4'-CH 0-C6H CH=)-2-C6H5-5oxazolone 4-(3'-F-4'-CH30-C H CH=)-2-C6H5-5oxazolone a-N-benzoylamino-3,5-F-4-CH30cinnamic aci d a-N-benzoylamino-3-F-4-CH30cinnamic aci d Methyl a-phenyl-/3-(4-F-benzoyl) propionate 2,2'- F - 6 , 6 ' - C 0 C H - b i p h e n y l (4-F-C H )3CCl (4-F-C6H ) CClC H5 (4-F-C H CCl(C6H )2 (2-F-C H CCl(C H )2 C H5-C6H CHCl-4-F-C H ) (4-F-C6H ) CHC H5 (C H ) CF

4

3

2 2

2

3

3 3

5

2

4

3 62 3 62 3

2

4 2 4 2 4 4 2 2

3

2 63

225 64 42 6 64 5 64 65 6 5 64 42 6 6 53 C H5-C6H CH2-(4-F-C6H ) 6 5 4 (C H ) CH(2-F-C H ) 6 52 64 C H5-C6H CHOH-(4-F-C H ) 6 5 6 4 (C H5) COH-(2-F-C6H4) 6 2

CÔJÏO

Phenyl bromid e + C u

37 8 37 8 1 26 8

126 154-155 250-253

Iodo c o m p o u n d + C u Amine + acetylatin g agen t Phthalic anhydrid e + ethylfluorobenzen e Phthalic anhydrid e + ethylfluorobenzen e 4 - F - l , 3 - C H - C H +phthali c anhydrid e 4 - F - l , 3 - C H - C H +phthali c anhydrid e Nitro compoun d + [H ] N i t r o compoun d + [H ]

45 4 2 2 37 8 37 8 16 6 16 6 26 8 26 8

165-169

From anisaldehyde

110 80-82 102 202-204 116-117 211 120 210-220

F r o m benzoylbenzoi c aci d F r o m benzoylbenzoi c aci d

3 63 3 63

Ο 133

200-201

From anisaldehyde

359

g

H y d r o l y s i s of 5 - o x a z o l o n e

133

Ο d

H y d r o l y s i s of 5 - o x a z o l o n e

359

221-222

2 42 2 4

C26H20F2O2

6 52

3 5

3

3

3

Ο

QQ Acid + alcohol 105-107 81-82 56-57 90-91 110-111 91-92 55-56 102-104 115-124 85-87 121-122 116

2

130 180-190 176 188-195

ο

Ο Iodobenzene + Cu 4-F-C H MgBr + 4-F-C H C0 CH3

64

64 2

4-Fluorophenone + CeHsMgBr

Carbinol + acetylfluoride

454 6

6

g ^

S 6 28 44 5 35 44

3 2

Ο §

r-»

w

173-174

(C H ) COH-<2-CH 0-5-F-C6H ) 4-(3',5'-I-4'-[3"-F-4"-CH 0-C6H 0-]C6H2CH=)-2-C6H -5-oxazolone 4,4'-Dif luorobenzopinaco l 2 , 2 '- D i f l u o r o b e n z o p i n a c o l

^

Ο

s

C20H17FO2 C Hi FI N0

2 Q •> 2

550 Hydrazone and hippuric acid

360

B e n z o p h e n o n e + Zn B e n z o p h e n o n e + Zn

274 28

308

P A U L TARRANT

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