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Organic microsynthesis
254
ABSTRACTS
Progress in organic and inorganic microsynthesis: 1968, A. R. Ronzio, Microchem. J., 3,459-65 (1959). Those problems of microchemists engaged in microsynthesis
which will continue as no systematic attempts are made for collection and systematization of this information are discussed. On the new substitution product of Cr( CO)6 with aromatic amines, H. Behrens and J. Kiihler, 2. anorg. u. allgem. them., 300,51-60 (1959). Synthesis of decigram quan-
tities of pentacarbonyl amine chromium(O) compounds from alkali pentacarbonyl chromates(I1) and aromatic amines are described. Hydroxy-cobalt(IIZ)-amides, 0. Schmitz-Du Mont and W. Hilger, 2. anorg. u. allgem. Chem., 300, 174-93 (1959). Preparation of isomeric hydroxy-cobalt(II)amides by interaction of KNH, (from decigram quantities of K) with [CO(NHB)~OH] (NO& and [Co2(NH&(OH)2] (where X may be NOa- or SCN-), respectively, in liquid ammonia is described. On the iron carbonyl compounds with the elements of the third to thzfifth main groups, W. Heiber, J. Gruber, and F. Lux, 2. anorg. u. allgem. Chem., 300,275-87 (1959).
Decigram quantities of iron carbonyls were treated with compounds of As, Sb, and Bi, producing non-ionogenic iron carbonyl compounds, such as AsnFea(CO),,, SbFer( CO)*, and B12Fes(CO)20. On the basic reactions of molybdenum hexacarbonyls, W. Hieber, K. Englert, and K. Rieger, 2. anorg. u. allgem. them., 300, 295-303 (1959). Decigram quantities of
[Mo~(CO)G(OH)~H~] were used to prepare secondary salts with potassium and tetramethylammonium hydroxide.
Organic Microsynthesis The structure of jfuorocurarin, W. Philipsborn, K. Bernauer, H. Schmid, and P. Karrer, Helv. Chim. Acta, 42,461-63 (1959). A proof of fluorocurarin structure is given.
Caratinoid syntheses. XXVI. Introduction of mercapto and anilido groups into @carotene, C. Martin and P. Karrer, Helv. Chim. Acta, 42,46466 (1959). The use of N-bromosuccinimide in the presence of appropriate mercaptan or aniline derivatives is detailed. of retiodehydro-kryptoxanthin, and on conversion products of @-carotenone, R. Eutschel and P. Karrer, Helv. Chim. Acta, 42,466-72 (1959). Dehydrogenation of zeaxanthin to rhodoxanthin via MnOs, and a parallel reaction of kryptoxanthin are detailed. Reduction of @-carotenone to a tetraol and dehydrogenation to a dioldione or a triolone are also described.
Synthesis of rhodoxanthin,
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Dehydrogenation of sarcostene with selenium, J. M. Nascimento, H. J&ger, C. The dehydrogenTamm, and T. Reichstein, Helv. Chim. Acta, 42,661-64 (1959). ation of sarcostene gives Jacobs’ compound and a ketone whose spectrum resembles that of a fluorene derivative. Ozonolysis of bufadienolides, 664-69 (1959). Ozonolysis acids.
H. SchrGter and K. Meyer, Helv. Chim. Acta, 42, of bufadienolides gives only 20-keto-21-norcholanic
Contribution to the constitution of antiarigenin, Antiarigenin Chim. Acta, 42, 696-712 (1959). thidin.
R. P. Martin and C. Tamm, Helv. is probably la@-hydroxystrophan-
New alkaloids from Peumus boldus (Molina), A. Riiegger, Helv. Chim. Acta, 42, 7.54-62 (1959). Isolation of three alkaloids and proof of structure of norisocorydine are detailed. Constitution 26 (1959).
of resibufogenin, H. Linde and K. Meyer, Helv. Chim. Acta, 42, 807Proof of structure of resibufogenin is detailed.
E’artial synthesis of hellebrigenin B-D-glucoside-(1,6) and hellebrigenol p-D-glucoside(1,5) as well as the identijication of these two glycosides in the bulbs of UrgineL depressa (Baker), R. Rees, 0. Schindler, and T. Reichstein, Helv. Chim. Acta, 42, 1052-65 (1959). The partial synthesis of hellebrigenin @-D-glucoside (1,5) and hellebrigenol fl-n-glucoside (1,5) are described. and ISol, l?‘~l, Steroids and sex hormones. CCX. Synthesis of 18-noTpTogesteTone 18-nOTpTOgeSteTOne, R. Auliker, M. Miiller, M. Perelman, J. Wohlfahrt, and H. The synthesis of these l&norHeusser, Helv. Chim. Acta, 42, 1071-85 (1959). progesterones is described. Steroids and sex hormones. CCXZ. Direct introduction of an oxygen function in the C-18 methyll group in the intact steroid skeleton, G. Cainelli, M. L. Mihailovir, D. Lead tetraacetate is Arigoni, and 0. Jego, Helv. Chim. Acta, 42, 1124-27 (1959). used to introduce the oxygen function. Toward the structure of erythrophleum alkaloids. XV. Conversion of cassaidin into cassain, B. G. Engel, Helv. Chim. Acta, 42, 1127-31 (1959). Interconversions within the cassain group are described. On the two isomers of 4,&dehydromuscarine, R. Deuss, E. Girod, E. Hiifliger, and Both compounds were preC. H. Engster, Helv. Chim. Acta, 42,1191-93 (1959). pared and isolated from 2-methyl-5-dimethylaminomethyl-2,3-dihydrofuran-3one. &‘tructure of a plant quinone with isoprenoid side chains, M. Kofler, A. Langemann, R. Rtiegg, L. H. Chopard-dit-Jean, A. Rayround, and 0. Isler, Helv. Chim. Acta,
256 42, 1283-92 (1959). 50-carbon isoprenoid
ABSTRACTS The structure side chain.
is that, of an o-dimethylbenaoquinone
with
a
Synthesis of pyrimidines. Study of the condensation of methylethoxy-carbonyldithioacetate with amidines, D. Isbecque, R. Rromel, R. C. Quinaux, and R. H. Martin, Helv. Chim. Acta, 42, 1317-23 (1959). A synthesis and structure proof of 2-amino-4-hydroxy-6-mercaptopyrimidine are given. On the constitution of marinobufagin. ZZZ. H. Schroter, R. Rees, and K. Meyer, Helv. Chim. Acta, 42, 1385-94 (1959). The structure of marinobufagin and of its degradation products is reported. Conversion of marinobufagin to telocinobufagin, M. Bharucha, H. Jiiger, K. Meyer, T. Reichstein, and 0. Schindler, Helv. Chim. Actu, 42, 1395-98 (1959). Reduction via NaBH4 in aqueous EtOH is the key reaction in conversion of marinobufagin to kelocinobufagin. .4 further degradation of onabagenin. L., G. Volpp and C. Tamm, Helv. C’him. Acta: 42,140&18 (1959). Degradation to two known, nonaromatic steroids is described. .4 further degradation of onabagenin. II., Helv. Chim. Acta, 42, 7418-32 (1959). described.
G. Volpp, G. Baumgartner, and C. Tamm, Degradation to etianic acid derivatives is
Constitution of xysmalogenin, J. Polonia, A. Kuritakes, H. Jager, and T. Reichstein, Helv. Chim. Acta, 42, 1437-47 (1959). A proof of structure of xysmalogenin is given. Further partial structure proofs for the glycosides of the sarmentoside A and tholloside series, B. Fechtig, 0. Schindler, and T. Reichstein, Helv. Chim. Acta, 42, 1448-57 ‘1959). Interrelationships between the two glucoside series are reported. 15-keto- and 16-hydroxyaetianic acids, A. Lardon, H. P. Sigg, and T. Reichstein, Helv. Chim. Acta, 42, 1457 (1959). The reaction at Cl4 to furnish a series of Ifioxygenated steroids is reported. Psilocybin and psilocin, two psychotropic agents of Mexican hallucinogenic fungi, H. Hoffmann, R. Hein, A. Brack, H. Kobel, A. Frey, H. Ott, T. Petrzilka, and F. Troxler, Helv. Chim. Acta, 42, 1551-71 (1959). Isolation and synthesis of psilorybin and psilocin are described. .4 new total synthesis of dl-aldosterone, K. Hensler, P. Wieland, and A. Wettstein, Helv. Chim. Acta, 42, 1586-93 (1959). The starting point is a total synthesis of dZ-aldosterone is a duodecahydrophenanthrone derivative. l’he chemistry of rosewood. ZZZ. Isolation of 5,6-dehydrokavain and J-methoxyparacotoin from Aniba firmula Mez, 0. R. Gottlieb and W. B. Mars, J. Org. Chem., 24, .MICROCHEMICAL
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1i-18 i 1959). Extraction of pulverized wood with benzene and chromatographyof the extract on alumina gave 5,6-dehydrokavain and 4-methoxyparacot’oin. Oxidation of 123 mg. 5,6-dehydrokavain with potassium permanganate gave benxnic acid. Alkaline oxidation of 200 mg. 5,6-dehydrokavain gave cinnamic acid or cinnamolyacetone, depending on the conditions.
12earmngement of methyl-3-aza-benzocycloheptene-4,7-dione-6-carboxylate to 2,.&dihydroxyquinoline-S-acetic acid in acid and base, T. A. Geissman and A. K. Cho, J. OrFg. Chem., 24, 41-43 (1959). Preparation of 0.1 g. dehydrodictamine by the reaction of sodium hydride with 0.2 g. 4-methoxy-2-hydroxy-3(2’-hydroxyethyl) quinoline followed by reaction with p-toluenesulfonyl chloride (all in t,etrahydrofuran) is given. (See specifically p. 43). :I new synthesis of 3-phenanthrol; absorption spectra of the quinhydrone-type molecular compound between Y-phenanthrol and phenanthreneguinone, E. J. Moriconi et al., J. Org. Chem., 24, 86-90 (1959). Synthesis starting with 750 mg. phenanthrene with a novel quantitative pinacol rearrangement of cis- or trans-9,10-dihydra-9,10-phenanthrenediol is described. The Diels-Alder reaction ojsteroidal I-methylene-A”-pregnene derivatives with maleic anhydride, F. Sondeimer and R. Mechoulan, J. Org. Chem., 24, 106-10 (1959). Details of the preparation of 20-methylene-A 5y16-pregnadien-3@-01 acetate and liisopropenvl-A1~a~s~(10)1e-estratetraen-3-ol acetate maleic adducts from 60-100 mg. of steroid are given. tiynlhesis of r-methyl steroid hormones. II. 7B-Methylcortisone acetate and 7p-methyl hydrocortisone acetate, C. H. Robinson, 0. Gnoj, and E. P. Oliveto, J. Org. Chem., 24, 121-123 (1959). Experimental data are given for the preparation of 7& methylcortisone acetate from 620 mg. 7-methyl-4,6-pregnadiene-17a-21-diol-3,11,20-trione-21-acetate and for the preparation of the semicarbazones of 7p-methylcortisone acetate and 7/%methyl hgdrocortisone acetate. Ring I) steroid oximes and the Beckman rearrangement, R. D. H. Heard, M. T. Ryan, and H. I. Bolker, J. Org. Chem., 24,172-75 (1959). Instead of behaving as a Ring D or Ring A steroid oxime, upon mild acetylation 3-hydroxyandrostan-16. J7-dione 16oxime (100 mg.) yields a pure crystalline compound, 3&hydroxy-16. 17-seco-androstan-16.17-dioic acid. Oxidation of methyl-8-nitrodehydro-abietate, W. J. Considine and H. H. Zeiss, J. Org. Chem., 24, 253-55 (1959). Oxidation of methyl-S-nitrodehydroabietate wit.h chromic acid and reactions of the resultant methyl-9-oxo-%nitrodehydroabietate and methyl-9-oxo-lO-oxa-ll-hydroxy-S-nitrodehydroabietate are rcported, samples of 24-1000 mg. being used. Heterocyclic vinyl ethers. XIV. Photochemical dimerization of 2-nitrobenzo-1,4-dithiadiene and reactions of benzodithiadiene with mercuric salts, W. E. Parham, P. L. Rtright, and W. R. Hasek, J. Ore. Chem., 24, 262-64 (1959). Photodimerization
258
ABSTRACTS
of 2-nitrobenzo-1,4-dithiadiene gives a product further reacted to yield pure benzene-e-disulfonyl
which is oxidized chloride.
(129 mg.)
and
Morphine-N-methyl-U4, K. S. Andersen and L. A. Woods, J. Org. Chem., 24,27475 (1959). Preparation of morphine-N-methyl-C4 from 195 mg. normorphine and paraformaldehyde-C14 is given. Techniques of purification, chromatography, and autoradiography are also described. Compounds related to 22-ketocholesterol, F. S. Prout and Z. F. Chmielewicz, J. Org. Chem., 24, 308-l 1 (1959). The rearrangement of 6+methoxy-3,BcyclocholeStan-22-one by hydrogen chloride in acetone, the reaction of thionyl chloride on 22ketocholesterol, and the preparation of the 1-dione from 3,5-cyclocholestane-6,22dione are all studied on semimicro size samples. .$-0xo-6,6-dihydro-4H-pyrido[3,2,1-jk]carbazole and its aralkylene derivatives, H. Rapaport and D. M. Bowman, J. Org. Chem., 24, 324-27 (1959). The procedure is given for the preparation of 4oxo-5-p-dimethylaminophenylimino-5,6-dihydro4H-pyrido[3,2,1-jklcarbazole from 300 mg. Foxo-5,6-dihydro[3,2,1-jklcarbazole and p-dimethylaminonitrosobenzene (See specifically p. 327). of nitration products of ester-blocked 2-hydroxybiphenyl, Chromatographic separation J. C. Colbert and D. P. Denny, J. Org. Chem., 24,348-52 (1959). The procedure is given for nitration of 0.5 g. 4’-nitro-2-hydroxybiphenyl to 3,4’- and 5,4’-dinitro2-hydroxybiphenyl and further nitration of these and 2’-nitro-2-hydroxybiphenyl (See specifically pp. 351-52). Acenaphthene chemistry. V. f,2-Diketopyracene, H. J. Richter and F. Stocker, J. Org. Chem., 24,366-67 (1959). The chromic acid oxidation of 0.42 g. 1,2-diketopyracene to 4,5-dibenzoylnaphthalic anhydride and the preparation of 5,6-dibenzoylacenaphthene from 0.12 g. 1,2-diphenyl-1,2-pyracenediol are described. coprostane-Sff,7~,12~-triol-2.&one Synthesis of coprostane-3~,7a,lZ~-triol-27-C~4, 27-Cl4 and coprostane-Sa,7~,12~,2&-tetrol-27-C~4, E. Staple and M. W. Whitehouse, The series of reactions starting with 1.50 g. J. Org. Chem., 24, 433-34 (1959). triformylcholyl chloride and a Grignard reagent made from 2.40 g. 2-bromopropane-1,3-Cl4 is given in detail. Some compounds derived from lanosterol, J. W. Huffman, J. Org. Chem., 24,447-51 (1959). The selenium dioxide oxidation of A7~s-lanostadiene to a-lanostatriene, the preparation of A*-lanostene, hydrogenation of isolanostadiene, preparation of As-lanosten-3ru-01, and its reaction with phosphorus oxychloride are reported. Synthesis of tetrahydrocarbazole and carbazoles by the Bischler reaction, E. Campaigne and R. D. Lake, J. Org. Chem., 24,47887 (1959). Preparation of 5-methyl1,2,3,4-tetrahydrocarbazole from 0.5 g. 8-chloro-5-methyltetrahydrocarbazole and of ll-hydroperoxy-5-methyl-1,2,3,4-tetrahydrocarbazolenine from 182 mg. of 5-methyl-1,2,3,4tetrahydrocarbazole are described (See specifically p. 486). MICROCHEMICAL
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Psoralene. II. Certain reactions of xanthotoxin, M. E. Brokke and B. E. Christensen, J. Org. Chem., 24, 523-26 (1959). Oxidation, chlorination, sulfonation, and ether cleavage of 9-methoxy psoralene in less than 500 mg. quantities are described. Chemistry of ethyleneimine. VI. Pyrolysis of 7-acetyl-7-azaspiro[6,6]octane, P. B. Talukdar and P. E. Fanta, J. Org. Chem., 24, 526-28 (1959). Hydrolysis of 0.5 g. 7-azaspiro[5,2]octane with aqueous sulfuric acid is reported (See specifically p. 528). III. Catalytic Degradation of corticosteroids. J. Org. Chem., 24,669-73 (1959). Catalytic plicated mixtures instead of the equatorial allo was used for partial separation of lo-635 mg. cation and further reaction.
hydrogenation of co&sol, E. Caspi, hydrogenation of cortisol gave comisomer expected. Chromatography fractions of the steroids for identifi-
( +)-2,3-Diaminosuccinic acid, F. A. Hochstein, J. Org. Chem., 24, 679-80 (1959). (+)-2,3-Diaminosuccinic acid is the first acid of its kind to be isolated from natural sources. Identification of it was done with 200-500 mg. samples. Polyphosphoric acid-catalyzed reaction of anisole with y-butyrolactone, H. 0. House and R. J. McCaully, J. Org. Chem., 24,725-26 (1959). The preparation of 32 mg. p-(p-methoxybenzoyl)propionic acid by the chromic acid oxidation of the keto alcohol is given (See specifically p. 726). Steroidal sapogenins. LZII. Permanganate-periodate oxidation ojpseudosapogenins M. E. Wall and S. Serota, J. Org. Chem., 24,741-43 (1959). A smooth oxidation procedure for 0.4 g. 12-methylenetigogenin and 0.42 g. 3&acetoxy-16-pregnen-20one is completely described. Reaction of cystine with sodium sulfide in sodium hydroxide solution, G. S. Rao and G. Gorin, J. Org. Chem. 24,749-55 (1959). Reaction of 100 mg. or more cystine with sodium sulfide under varying acidic conditions and at various concentrations The products are identified by spectrophotometric and polarimetric are given. study. III. Studies on the synthesis and partial Synthetic approaches to ipecac alkaloids. reduction of pyridones, J. A. Berson and J. S. Walla, J. Org. Chem., 24, 756-60 (1959). Preparation of N+(3,4aimethoxyphenylethyl)-5-ethyl-2-pyridione and N-@-(3,Pdimethoxyphenylethyl)-2-pyridone, their reduction with lithium aluminum hydride or lithium, sodium, or calcium in liquid ammonia, and the products obtained are described. XIX. Some transformation reactions of SbrcnnoSantonin and related compounds. cr-tetrahydrosantonin, K. Yamakawa, J. Org. Chem., 24, 897-902 (1959). Preparation and reactions of (Y- and -,+tetrahydrosantonins and of 2-bromo-ol-tetrahydrosantonins are studied on 20-200 mg. samples.
‘60
ABSTRACTS
and related compounds. XX. Some transformation reactions of Z-bromo+y-tetrahydrosantonin, M. Yanagita and K. Yamakawa, J. Org. Chem., 24,90X-909 (1959). Additional preparations and reactions of a- and r-tetrahydrosantonins are given. Santcmin
Steroids. CXZX. The preparation of some vicinal glycols in the cortical hormone series, J. A. Zderic, H. Carpio, and C. Djerassi, J. Org. Chem., 24,909-11 (1959). Reaction of 150 mg. 6a,7a-dihydroxycortisone acetate with perchloric acid and pyridine yields 6a,7a-dihydroxycortisone acetate 6,7-acetonide (See specifically p. 910). The reaction of cis- and trans-stilbene-2-carboxylic acids with peroxy acids, G. Berti, Stereochemistry of the reaction of derivatives J. Org. Chem., 24,934-38 (1959). of o-vinylbenzoic acid with organic peroxy acids to produce predominantly hydroxylactones are studied on samples of 500 mg. or less. Some urea and picrate derivatives of pyridoxamine, G. E. McCasland, E. Blanz, Jr., Pyridoxurea hydrochloride and A. Furst, J. Org. Chem., 24, 1000-1001 (1959). and its mono- and dipicrates, and pyridoxurea 5-o-acetate monohydrochloride are prepared in 25-1400 mg. quantities. Synthesis of dihydrosphingosine-i$cyclophosphate, B. Weiss, J. Org. Chem., 24, 1026-27 (1959). Experimental data are given for the conversion of 151 mg. dihydrosphingosine-1,3-cyclophosphate to 142 mg. dihydrosphingosine-I ,3-phosphate and oxidation of the latter with periodate. Pyridoxine N-oxide, T. Sakuragi and F. Kummerow, J. Org. Chem., 24, 1032-33 (1959). Pyridoxine hydrochloride (45 mg.) free of pyridoxine N-oxide is prepared from 120 mg. pyridoxine N-oxide hydrochloride by action of zinc dust in ethanol. Cortical steroid analogs. ZZZ. Further synthetic and structure studies on acylcic dihydroxyacetones derived from 8,S-butanedione. 1 ,S-Dihydroxy-S-phenyl-8-butanone, G. W. Stacy et al., J. Org. Chem., 24, 1099-1103 (1959). Ester intermediates of various types are studied for synthesis of 1,3-dihydroxy-3-phenyl-2-butanonr in less than 500-mg. quantities. Steroidal aldosterone blockers. ZZ. J. A. Cella and R. C. Tweit, J. Org. Chem., 24, 1109-10 (1959). Synthesis of 50-500 mg. quantities of 17-spirolactones are reported and their biological activities described. Preparation of pregnane-Sor,i6a,ZOc-trio1 and of two of its stereoisomers, H. Hirschmann and M. A. Daus, J. Org. Chem., 24, 1114-19 (1959). Preparations of l&537 mg. pregnane-3cy,16a,20a-triol, pregnane-3ay,1601,20@-triol, and 38, 160l, 2Op-trio1 are described. Preparation of other 16a-acetoxy steroids in less t,han 100-mg. amounts are also given. MICROCHEMIC$L
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Dienone-phenol rearrangement of%phenyl-oquinol acetate, H. Buclzikiewicz and W. Metlisics, J. Org. Chem., 24, 1125-26 (1959). Rearrangement of 2-phenyl-oquinol acetate (0.2 g.) with acetic anhydride and perchloric acid results in 2,6diacetoxybiphenyl. Synthesis of 2,6-hydroxybiphenyl from B-hydroxybiphenyl%e:trboxylic acid is also reported. tetroxide-catalyzed oxidations of pyrene, F. G. Oberender and J. A. Dixon, J. Org. Chem., 24, 1226-29 (1959). Reaction of 17 mg. pyrene4,5--quinone with o-phenylenediamine and glacial acetic acid yields 19 mg. pyrene+I‘,5, ‘2,3-quinoxaline.
Osmium and ruthenium
Reaction of the enot form of 1,2-cyclohexanedione
with the phenyl Grignard reagent, P. Tomboulian and C. A. A. Bloomquist, J. Org. Chem., 24, 1239-44 (1959). Oxidation of about 500 mg. 2-hydroxy-3-phenylcyclohexanone with chromic acid, periodic acid, and lead tetraacetate was studied. Also studied were the reactions of 5-benzoyl-2-phenylpentanal and 1,3-diphenyl-1,2-cyclohexanediol. The structure of C,rH,nOa, G. R. Oxidation of 2,6-di-tert-butyl-.&methylphenol. Yohe et al., J. Org. Chem., 24, 1251-56 (1959). The structure of C,aH,Z03 previously reported as the oxidation product of 2,6-di-tertbutyl-4-methylphenol is now believed to be nL-trans-5,6-di-tert-butyl-2-hydroxy-l,4-diketo-2-cyclohexene as a result of a series of reactions on samples of less than 500-mg. size. The solvolysis of &$-dimethylcholesteryl-p-toluenesulfonate, R. W. Moriarty and E. S. Wallis, J. Org. Chem., 24,1274-78 (1959). Solvolysis in 60% aqueous acetone in the presence of potassium acetate is conducted in less than 500 mg. quantities, and the identification of the products is reported.
Synthesis in the cardiac aglycone field. I. The condensation of or-ketol tetrahydropyranyl ethers with acetylene and with propiolic esters, F. Sondheimer, N. StjernStrom, and D. Rosenthal, J. Org. Chem., 24, 1280-84 (1959). Unsuccessful at-
tempts to synthesize a steroidal lactone containing a 5’-cu-pyrone grouping at the 17&position are reported. Reactions of the mono-p-toluenesulfonic acid ester of yohimbyl alcohol, R. C. Elderfield et al., J. Org. Chem., 24,1296-1301 (1959). Hydrolysis of less than 500 mg.
of the mono-p-toluenesulfonic acid ester of yohimbyl alcohol under acid conditions gives yohimbyl alcohol and under basic conditions results in the formation of an oxetane. of glycineamidine, A. K. Bose et al., J. Org. Chem., 24, 1309-13 (1959). The reactions of phthalimidoacetonitrile and ethyl phthalimidoacetate with ammonia under varying conditions are reported.
Some derivatives
Chlorination o,f1,8diacetylurea and of barbituric Elrovy, Jr., J. Org. Chem., 24,1383-84 (1959).
acid, F. B. Slezak and H. A. McThe procedure for chlorination of
262
ABSTRACTS
acetylurea is described, and the warning given that overchlorination resulted in an explosive oil. sulfonium salts with sulfur at a bridgehead, R. H. Eastman and G. Kritchevsky, J. Org. Chem., 24, 1428-32 (1959). Preparation of 150 mg. bicyclo[4..3.0]nonane-1-thianium picrate from 100 mg. crude 4(2-tetrahydrothienyl)butanol is given (See specifically p. 1430).
Bicyclic
A. J. Castro et al., J. Org. Chem., 24, 1437-40 (1959). Potassium permanganate oxidation of 2,2’-2,“-tripyrrylmethanes (300-900 mg.) gives varying yields of the corresponding methenes.
,9,.%“,B”-Tripyrrylmethenes,
p-Phenylazobenzenesulfonyl chloride-a new reagent for identification and separation of amines, E. 0. Woolfolk, W. E. Reynolds, and J. L. Mason, J. Org. Chem., 24,
1445-50 (1959). N-substituted p-phenylazobenzenesulfonamides are prepared from 100 mg. of the p-phenylazobenzenesulfonyl chloride and the amines, and the Tswett absorption method is used for separation and identification of the derivatives. Some nitrogen-containing ferrocene derivatives, E. M. Acton and R. M. Silverstein, J. Org. Chem., 24, 1487-90 (1959). The preparation of derivatives of ferrocenyl-
amine and of N-substituted are given.
ferrocene-carboxamides in amounts of 80-1000 mg.
experiments with i,3-oxathiolan-5-ones, A. Romo de Vivar and J. Romo, J. Org. Chem., 24, 1490-93 (1959). The preparation of 2-hydroxycyclohexanone diphenylacetate from 100 mg. cyclohexane-1,2-diol-diphenylacetate and from 80 mg. hydroxycyclohexanone are described. Desulfuration of oxathiolanone in amounts of 50-850 mg. is also given (See specifically p. 1493).
Desulfuration
Nitration of i- and Q-jluorojfuorene, K. Suzuki, E. K. Weisburger, and J. H. Weisburger, J. Org. Chem., 24, 1511-17 (1959). Oxidation of 42 mg. 1-fluoro-7-nitrofluorenone with chromium trioxide is given along the ultraviolet data on the fluorenone product. Also described are the catalytic reductions of I-fluoro-Bnitrofluorene, 1-fluoro-4-nitrofluorene, and 1-fluoro-7-nitrofluorene, and the preparation of the acetamide derivatives of the resulting amines (See specifically p. 1515). Characterization of cupressaceae tropolones as dicyclohexylamine salts, E. Zavarin, R. B. Smith, and A. B. Anderson, J. Org. Chem., 24,1584-85 (1959). The preparation of derivatives of tropolones (about 250 mg.) with dicyclohexylamine is described as is the recovery of the tropolone from the resulting salts. of S-phenyl-3-acetoxypropanyl chloride with ethyl sodioacetoacetote, E. M. Smissman and F. B. Block, J. Org. Chem., 24, 1593-95 (1959). Alkali hydrolysis of 123 mg. 4-phenyl-5-carboethoxy-6-methyl-3,4dihydro-2-p~one to give 95 mg. 3-phenyl-5-ketocaproic acid and also the identification of the acid are reported.
Reaction
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11-Alkylated steroids. III. Two syntheses of Ii-methylhydrocortisone, G. S. Fonken, J. A. Hogg, and A. V. McIntosh, Jr., J. Org. Chem., 24,1600-1604 (1959). Much of the work of the syntheses starting with lip-hydroxy-11-methyl-5&pregnenedione was done with 200-500 mg. samples. Syntheses of hormonesfrom 5,6-dichloro-steroids. I. Addition of chlorine to pregnenolone acetate, F. A. Cutler, Jr., et al., J. Org. Chem., 24,1621-25 (1959). Reactions of 50-500 mg. 5cu-6fl-dichloro-3fl-acetoxy-pregnan-20-one and 5a,6or-dichloro3@-acetoxy-pregnane-20-one with zinc, potassium hydroxide, or chromous chloride are reported (See specifically p. 1625). Oxygen heterocycles. A new isojlavanone from Sophora japonica, L., H. Suginome, J. Org. Chem., 24,1655-62 (1959). Degradation studies on 200 mg. or more of an optically active isoflavanone from Sophora japonica, L., called sophorol, shows it to be 2’,7-dihydroxy-4’,5’-methylenedioxyisoflavanone or 2’,7-dihydroxy-5’,6’isoflavanone. (See specifically p. 1661). Synthesis of some heterocyclic derivatives of a-keto acids, J. D. Fissekis, C. G. Skinner, and W. Shive, J. Org. Chem., 24,1722-25 (1959). Preparation of 2cyclopentyl-3hydroxyquinoxaline, 2-cyclohexyl-3-hydroxyquinoxaline, and Pamino-6-cyclohexyl-7-hydroxypteridine from about 150 mg. of appropriately substituted glyoxylic acid is given. A new technique for preparing 8,4-dinitrophenylhydrazones. III. Two examples of diacetone alcohol and methyl vinyl ketone, H. hitherto unobtainable simple derivatives: J. Shine, J. Org. Chem., 24,1790-91(1959). Diglyme is used as the solvent in preparing the 2,4-dinitrophenylhydrazone derivatives of sensitive compounds. Th,e synthesis of nitroestradiols, T. L. Patton, J. Org. Chem., 24, 1795-96 (1959). Preparation of nitroestradiols by sodium borohydride reduction of 500 mg. 2- or Pnitroestrone or 2,4dinitroestrone is given. Ntm-lability of the a-hydrogen during ninhydrin oxidation of alanine, J. G. Kay and F. S. Rowland, J. Org. Chem., 24,1800-1807 (1959). Oxidation of tritium-labeled and nonlabeled alanine is studied with 50-290 mg. samples. In vivo hydroxylation of I-ethynyl-cyclohexyl carbamate. II. The orientation on hydroxylation, R. E. McMahon, J. Org. Chem., 24,1834-36 (1959). Various isomers of I-ethynyl-cyclohexane-1,4-diol (500-mg. samples) are catalytically hydrogenated to the corresponding saturated acids. Basic hydrolysis of 10 mg. l-ethyl cylohexane-1,4diol is also described. Micro
Apparatus
and Miscellaneous
A modijed chromatographic microapplicator, D. Kirman, 410-11 (1959). The apparatus is described.
Tools Am. J. Clin. Pathol.,
31,
ABSTRACTS
Progress in organic and inorganic microsynthesis: 1968, A. R. Ronzio, Microchem. J., 3,459-65 (1959). Those problems of microchemists engaged in microsynthesis
which will continue as no systematic attempts are made for collection and systematization of this information are discussed. On the new substitution product of Cr( CO)6 with aromatic amines, H. Behrens and J. Kiihler, 2. anorg. u. allgem. them., 300,51-60 (1959). Synthesis of decigram quan-
tities of pentacarbonyl amine chromium(O) compounds from alkali pentacarbonyl chromates(I1) and aromatic amines are described. Hydroxy-cobalt(IIZ)-amides, 0. Schmitz-Du Mont and W. Hilger, 2. anorg. u. allgem. Chem., 300, 174-93 (1959). Preparation of isomeric hydroxy-cobalt(II)amides by interaction of KNH, (from decigram quantities of K) with [CO(NHB)~OH] (NO& and [Co2(NH&(OH)2] (where X may be NOa- or SCN-), respectively, in liquid ammonia is described. On the iron carbonyl compounds with the elements of the third to thzfifth main groups, W. Heiber, J. Gruber, and F. Lux, 2. anorg. u. allgem. Chem., 300,275-87 (1959).
Decigram quantities of iron carbonyls were treated with compounds of As, Sb, and Bi, producing non-ionogenic iron carbonyl compounds, such as AsnFea(CO),,, SbFer( CO)*, and B12Fes(CO)20. On the basic reactions of molybdenum hexacarbonyls, W. Hieber, K. Englert, and K. Rieger, 2. anorg. u. allgem. them., 300, 295-303 (1959). Decigram quantities of
[Mo~(CO)G(OH)~H~] were used to prepare secondary salts with potassium and tetramethylammonium hydroxide.
Organic Microsynthesis The structure of jfuorocurarin, W. Philipsborn, K. Bernauer, H. Schmid, and P. Karrer, Helv. Chim. Acta, 42,461-63 (1959). A proof of fluorocurarin structure is given.
Caratinoid syntheses. XXVI. Introduction of mercapto and anilido groups into @carotene, C. Martin and P. Karrer, Helv. Chim. Acta, 42,46466 (1959). The use of N-bromosuccinimide in the presence of appropriate mercaptan or aniline derivatives is detailed. of retiodehydro-kryptoxanthin, and on conversion products of @-carotenone, R. Eutschel and P. Karrer, Helv. Chim. Acta, 42,466-72 (1959). Dehydrogenation of zeaxanthin to rhodoxanthin via MnOs, and a parallel reaction of kryptoxanthin are detailed. Reduction of @-carotenone to a tetraol and dehydrogenation to a dioldione or a triolone are also described.
Synthesis of rhodoxanthin,
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Dehydrogenation of sarcostene with selenium, J. M. Nascimento, H. J&ger, C. The dehydrogenTamm, and T. Reichstein, Helv. Chim. Acta, 42,661-64 (1959). ation of sarcostene gives Jacobs’ compound and a ketone whose spectrum resembles that of a fluorene derivative. Ozonolysis of bufadienolides, 664-69 (1959). Ozonolysis acids.
H. SchrGter and K. Meyer, Helv. Chim. Acta, 42, of bufadienolides gives only 20-keto-21-norcholanic
Contribution to the constitution of antiarigenin, Antiarigenin Chim. Acta, 42, 696-712 (1959). thidin.
R. P. Martin and C. Tamm, Helv. is probably la@-hydroxystrophan-
New alkaloids from Peumus boldus (Molina), A. Riiegger, Helv. Chim. Acta, 42, 7.54-62 (1959). Isolation of three alkaloids and proof of structure of norisocorydine are detailed. Constitution 26 (1959).
of resibufogenin, H. Linde and K. Meyer, Helv. Chim. Acta, 42, 807Proof of structure of resibufogenin is detailed.
E’artial synthesis of hellebrigenin B-D-glucoside-(1,6) and hellebrigenol p-D-glucoside(1,5) as well as the identijication of these two glycosides in the bulbs of UrgineL depressa (Baker), R. Rees, 0. Schindler, and T. Reichstein, Helv. Chim. Acta, 42, 1052-65 (1959). The partial synthesis of hellebrigenin @-D-glucoside (1,5) and hellebrigenol fl-n-glucoside (1,5) are described. and ISol, l?‘~l, Steroids and sex hormones. CCX. Synthesis of 18-noTpTogesteTone 18-nOTpTOgeSteTOne, R. Auliker, M. Miiller, M. Perelman, J. Wohlfahrt, and H. The synthesis of these l&norHeusser, Helv. Chim. Acta, 42, 1071-85 (1959). progesterones is described. Steroids and sex hormones. CCXZ. Direct introduction of an oxygen function in the C-18 methyll group in the intact steroid skeleton, G. Cainelli, M. L. Mihailovir, D. Lead tetraacetate is Arigoni, and 0. Jego, Helv. Chim. Acta, 42, 1124-27 (1959). used to introduce the oxygen function. Toward the structure of erythrophleum alkaloids. XV. Conversion of cassaidin into cassain, B. G. Engel, Helv. Chim. Acta, 42, 1127-31 (1959). Interconversions within the cassain group are described. On the two isomers of 4,&dehydromuscarine, R. Deuss, E. Girod, E. Hiifliger, and Both compounds were preC. H. Engster, Helv. Chim. Acta, 42,1191-93 (1959). pared and isolated from 2-methyl-5-dimethylaminomethyl-2,3-dihydrofuran-3one. &‘tructure of a plant quinone with isoprenoid side chains, M. Kofler, A. Langemann, R. Rtiegg, L. H. Chopard-dit-Jean, A. Rayround, and 0. Isler, Helv. Chim. Acta,
256 42, 1283-92 (1959). 50-carbon isoprenoid
ABSTRACTS The structure side chain.
is that, of an o-dimethylbenaoquinone
with
a
Synthesis of pyrimidines. Study of the condensation of methylethoxy-carbonyldithioacetate with amidines, D. Isbecque, R. Rromel, R. C. Quinaux, and R. H. Martin, Helv. Chim. Acta, 42, 1317-23 (1959). A synthesis and structure proof of 2-amino-4-hydroxy-6-mercaptopyrimidine are given. On the constitution of marinobufagin. ZZZ. H. Schroter, R. Rees, and K. Meyer, Helv. Chim. Acta, 42, 1385-94 (1959). The structure of marinobufagin and of its degradation products is reported. Conversion of marinobufagin to telocinobufagin, M. Bharucha, H. Jiiger, K. Meyer, T. Reichstein, and 0. Schindler, Helv. Chim. Actu, 42, 1395-98 (1959). Reduction via NaBH4 in aqueous EtOH is the key reaction in conversion of marinobufagin to kelocinobufagin. .4 further degradation of onabagenin. L., G. Volpp and C. Tamm, Helv. C’him. Acta: 42,140&18 (1959). Degradation to two known, nonaromatic steroids is described. .4 further degradation of onabagenin. II., Helv. Chim. Acta, 42, 7418-32 (1959). described.
G. Volpp, G. Baumgartner, and C. Tamm, Degradation to etianic acid derivatives is
Constitution of xysmalogenin, J. Polonia, A. Kuritakes, H. Jager, and T. Reichstein, Helv. Chim. Acta, 42, 1437-47 (1959). A proof of structure of xysmalogenin is given. Further partial structure proofs for the glycosides of the sarmentoside A and tholloside series, B. Fechtig, 0. Schindler, and T. Reichstein, Helv. Chim. Acta, 42, 1448-57 ‘1959). Interrelationships between the two glucoside series are reported. 15-keto- and 16-hydroxyaetianic acids, A. Lardon, H. P. Sigg, and T. Reichstein, Helv. Chim. Acta, 42, 1457 (1959). The reaction at Cl4 to furnish a series of Ifioxygenated steroids is reported. Psilocybin and psilocin, two psychotropic agents of Mexican hallucinogenic fungi, H. Hoffmann, R. Hein, A. Brack, H. Kobel, A. Frey, H. Ott, T. Petrzilka, and F. Troxler, Helv. Chim. Acta, 42, 1551-71 (1959). Isolation and synthesis of psilorybin and psilocin are described. .4 new total synthesis of dl-aldosterone, K. Hensler, P. Wieland, and A. Wettstein, Helv. Chim. Acta, 42, 1586-93 (1959). The starting point is a total synthesis of dZ-aldosterone is a duodecahydrophenanthrone derivative. l’he chemistry of rosewood. ZZZ. Isolation of 5,6-dehydrokavain and J-methoxyparacotoin from Aniba firmula Mez, 0. R. Gottlieb and W. B. Mars, J. Org. Chem., 24, .MICROCHEMICAL
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25;
1i-18 i 1959). Extraction of pulverized wood with benzene and chromatographyof the extract on alumina gave 5,6-dehydrokavain and 4-methoxyparacot’oin. Oxidation of 123 mg. 5,6-dehydrokavain with potassium permanganate gave benxnic acid. Alkaline oxidation of 200 mg. 5,6-dehydrokavain gave cinnamic acid or cinnamolyacetone, depending on the conditions.
12earmngement of methyl-3-aza-benzocycloheptene-4,7-dione-6-carboxylate to 2,.&dihydroxyquinoline-S-acetic acid in acid and base, T. A. Geissman and A. K. Cho, J. OrFg. Chem., 24, 41-43 (1959). Preparation of 0.1 g. dehydrodictamine by the reaction of sodium hydride with 0.2 g. 4-methoxy-2-hydroxy-3(2’-hydroxyethyl) quinoline followed by reaction with p-toluenesulfonyl chloride (all in t,etrahydrofuran) is given. (See specifically p. 43). :I new synthesis of 3-phenanthrol; absorption spectra of the quinhydrone-type molecular compound between Y-phenanthrol and phenanthreneguinone, E. J. Moriconi et al., J. Org. Chem., 24, 86-90 (1959). Synthesis starting with 750 mg. phenanthrene with a novel quantitative pinacol rearrangement of cis- or trans-9,10-dihydra-9,10-phenanthrenediol is described. The Diels-Alder reaction ojsteroidal I-methylene-A”-pregnene derivatives with maleic anhydride, F. Sondeimer and R. Mechoulan, J. Org. Chem., 24, 106-10 (1959). Details of the preparation of 20-methylene-A 5y16-pregnadien-3@-01 acetate and liisopropenvl-A1~a~s~(10)1e-estratetraen-3-ol acetate maleic adducts from 60-100 mg. of steroid are given. tiynlhesis of r-methyl steroid hormones. II. 7B-Methylcortisone acetate and 7p-methyl hydrocortisone acetate, C. H. Robinson, 0. Gnoj, and E. P. Oliveto, J. Org. Chem., 24, 121-123 (1959). Experimental data are given for the preparation of 7& methylcortisone acetate from 620 mg. 7-methyl-4,6-pregnadiene-17a-21-diol-3,11,20-trione-21-acetate and for the preparation of the semicarbazones of 7p-methylcortisone acetate and 7/%methyl hgdrocortisone acetate. Ring I) steroid oximes and the Beckman rearrangement, R. D. H. Heard, M. T. Ryan, and H. I. Bolker, J. Org. Chem., 24,172-75 (1959). Instead of behaving as a Ring D or Ring A steroid oxime, upon mild acetylation 3-hydroxyandrostan-16. J7-dione 16oxime (100 mg.) yields a pure crystalline compound, 3&hydroxy-16. 17-seco-androstan-16.17-dioic acid. Oxidation of methyl-8-nitrodehydro-abietate, W. J. Considine and H. H. Zeiss, J. Org. Chem., 24, 253-55 (1959). Oxidation of methyl-S-nitrodehydroabietate wit.h chromic acid and reactions of the resultant methyl-9-oxo-%nitrodehydroabietate and methyl-9-oxo-lO-oxa-ll-hydroxy-S-nitrodehydroabietate are rcported, samples of 24-1000 mg. being used. Heterocyclic vinyl ethers. XIV. Photochemical dimerization of 2-nitrobenzo-1,4-dithiadiene and reactions of benzodithiadiene with mercuric salts, W. E. Parham, P. L. Rtright, and W. R. Hasek, J. Ore. Chem., 24, 262-64 (1959). Photodimerization
258
ABSTRACTS
of 2-nitrobenzo-1,4-dithiadiene gives a product further reacted to yield pure benzene-e-disulfonyl
which is oxidized chloride.
(129 mg.)
and
Morphine-N-methyl-U4, K. S. Andersen and L. A. Woods, J. Org. Chem., 24,27475 (1959). Preparation of morphine-N-methyl-C4 from 195 mg. normorphine and paraformaldehyde-C14 is given. Techniques of purification, chromatography, and autoradiography are also described. Compounds related to 22-ketocholesterol, F. S. Prout and Z. F. Chmielewicz, J. Org. Chem., 24, 308-l 1 (1959). The rearrangement of 6+methoxy-3,BcyclocholeStan-22-one by hydrogen chloride in acetone, the reaction of thionyl chloride on 22ketocholesterol, and the preparation of the 1-dione from 3,5-cyclocholestane-6,22dione are all studied on semimicro size samples. .$-0xo-6,6-dihydro-4H-pyrido[3,2,1-jk]carbazole and its aralkylene derivatives, H. Rapaport and D. M. Bowman, J. Org. Chem., 24, 324-27 (1959). The procedure is given for the preparation of 4oxo-5-p-dimethylaminophenylimino-5,6-dihydro4H-pyrido[3,2,1-jklcarbazole from 300 mg. Foxo-5,6-dihydro[3,2,1-jklcarbazole and p-dimethylaminonitrosobenzene (See specifically p. 327). of nitration products of ester-blocked 2-hydroxybiphenyl, Chromatographic separation J. C. Colbert and D. P. Denny, J. Org. Chem., 24,348-52 (1959). The procedure is given for nitration of 0.5 g. 4’-nitro-2-hydroxybiphenyl to 3,4’- and 5,4’-dinitro2-hydroxybiphenyl and further nitration of these and 2’-nitro-2-hydroxybiphenyl (See specifically pp. 351-52). Acenaphthene chemistry. V. f,2-Diketopyracene, H. J. Richter and F. Stocker, J. Org. Chem., 24,366-67 (1959). The chromic acid oxidation of 0.42 g. 1,2-diketopyracene to 4,5-dibenzoylnaphthalic anhydride and the preparation of 5,6-dibenzoylacenaphthene from 0.12 g. 1,2-diphenyl-1,2-pyracenediol are described. coprostane-Sff,7~,12~-triol-2.&one Synthesis of coprostane-3~,7a,lZ~-triol-27-C~4, 27-Cl4 and coprostane-Sa,7~,12~,2&-tetrol-27-C~4, E. Staple and M. W. Whitehouse, The series of reactions starting with 1.50 g. J. Org. Chem., 24, 433-34 (1959). triformylcholyl chloride and a Grignard reagent made from 2.40 g. 2-bromopropane-1,3-Cl4 is given in detail. Some compounds derived from lanosterol, J. W. Huffman, J. Org. Chem., 24,447-51 (1959). The selenium dioxide oxidation of A7~s-lanostadiene to a-lanostatriene, the preparation of A*-lanostene, hydrogenation of isolanostadiene, preparation of As-lanosten-3ru-01, and its reaction with phosphorus oxychloride are reported. Synthesis of tetrahydrocarbazole and carbazoles by the Bischler reaction, E. Campaigne and R. D. Lake, J. Org. Chem., 24,47887 (1959). Preparation of 5-methyl1,2,3,4-tetrahydrocarbazole from 0.5 g. 8-chloro-5-methyltetrahydrocarbazole and of ll-hydroperoxy-5-methyl-1,2,3,4-tetrahydrocarbazolenine from 182 mg. of 5-methyl-1,2,3,4tetrahydrocarbazole are described (See specifically p. 486). MICROCHEMICAL
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Psoralene. II. Certain reactions of xanthotoxin, M. E. Brokke and B. E. Christensen, J. Org. Chem., 24, 523-26 (1959). Oxidation, chlorination, sulfonation, and ether cleavage of 9-methoxy psoralene in less than 500 mg. quantities are described. Chemistry of ethyleneimine. VI. Pyrolysis of 7-acetyl-7-azaspiro[6,6]octane, P. B. Talukdar and P. E. Fanta, J. Org. Chem., 24, 526-28 (1959). Hydrolysis of 0.5 g. 7-azaspiro[5,2]octane with aqueous sulfuric acid is reported (See specifically p. 528). III. Catalytic Degradation of corticosteroids. J. Org. Chem., 24,669-73 (1959). Catalytic plicated mixtures instead of the equatorial allo was used for partial separation of lo-635 mg. cation and further reaction.
hydrogenation of co&sol, E. Caspi, hydrogenation of cortisol gave comisomer expected. Chromatography fractions of the steroids for identifi-
( +)-2,3-Diaminosuccinic acid, F. A. Hochstein, J. Org. Chem., 24, 679-80 (1959). (+)-2,3-Diaminosuccinic acid is the first acid of its kind to be isolated from natural sources. Identification of it was done with 200-500 mg. samples. Polyphosphoric acid-catalyzed reaction of anisole with y-butyrolactone, H. 0. House and R. J. McCaully, J. Org. Chem., 24,725-26 (1959). The preparation of 32 mg. p-(p-methoxybenzoyl)propionic acid by the chromic acid oxidation of the keto alcohol is given (See specifically p. 726). Steroidal sapogenins. LZII. Permanganate-periodate oxidation ojpseudosapogenins M. E. Wall and S. Serota, J. Org. Chem., 24,741-43 (1959). A smooth oxidation procedure for 0.4 g. 12-methylenetigogenin and 0.42 g. 3&acetoxy-16-pregnen-20one is completely described. Reaction of cystine with sodium sulfide in sodium hydroxide solution, G. S. Rao and G. Gorin, J. Org. Chem. 24,749-55 (1959). Reaction of 100 mg. or more cystine with sodium sulfide under varying acidic conditions and at various concentrations The products are identified by spectrophotometric and polarimetric are given. study. III. Studies on the synthesis and partial Synthetic approaches to ipecac alkaloids. reduction of pyridones, J. A. Berson and J. S. Walla, J. Org. Chem., 24, 756-60 (1959). Preparation of N+(3,4aimethoxyphenylethyl)-5-ethyl-2-pyridione and N-@-(3,Pdimethoxyphenylethyl)-2-pyridone, their reduction with lithium aluminum hydride or lithium, sodium, or calcium in liquid ammonia, and the products obtained are described. XIX. Some transformation reactions of SbrcnnoSantonin and related compounds. cr-tetrahydrosantonin, K. Yamakawa, J. Org. Chem., 24, 897-902 (1959). Preparation and reactions of (Y- and -,+tetrahydrosantonins and of 2-bromo-ol-tetrahydrosantonins are studied on 20-200 mg. samples.
‘60
ABSTRACTS
and related compounds. XX. Some transformation reactions of Z-bromo+y-tetrahydrosantonin, M. Yanagita and K. Yamakawa, J. Org. Chem., 24,90X-909 (1959). Additional preparations and reactions of a- and r-tetrahydrosantonins are given. Santcmin
Steroids. CXZX. The preparation of some vicinal glycols in the cortical hormone series, J. A. Zderic, H. Carpio, and C. Djerassi, J. Org. Chem., 24,909-11 (1959). Reaction of 150 mg. 6a,7a-dihydroxycortisone acetate with perchloric acid and pyridine yields 6a,7a-dihydroxycortisone acetate 6,7-acetonide (See specifically p. 910). The reaction of cis- and trans-stilbene-2-carboxylic acids with peroxy acids, G. Berti, Stereochemistry of the reaction of derivatives J. Org. Chem., 24,934-38 (1959). of o-vinylbenzoic acid with organic peroxy acids to produce predominantly hydroxylactones are studied on samples of 500 mg. or less. Some urea and picrate derivatives of pyridoxamine, G. E. McCasland, E. Blanz, Jr., Pyridoxurea hydrochloride and A. Furst, J. Org. Chem., 24, 1000-1001 (1959). and its mono- and dipicrates, and pyridoxurea 5-o-acetate monohydrochloride are prepared in 25-1400 mg. quantities. Synthesis of dihydrosphingosine-i$cyclophosphate, B. Weiss, J. Org. Chem., 24, 1026-27 (1959). Experimental data are given for the conversion of 151 mg. dihydrosphingosine-1,3-cyclophosphate to 142 mg. dihydrosphingosine-I ,3-phosphate and oxidation of the latter with periodate. Pyridoxine N-oxide, T. Sakuragi and F. Kummerow, J. Org. Chem., 24, 1032-33 (1959). Pyridoxine hydrochloride (45 mg.) free of pyridoxine N-oxide is prepared from 120 mg. pyridoxine N-oxide hydrochloride by action of zinc dust in ethanol. Cortical steroid analogs. ZZZ. Further synthetic and structure studies on acylcic dihydroxyacetones derived from 8,S-butanedione. 1 ,S-Dihydroxy-S-phenyl-8-butanone, G. W. Stacy et al., J. Org. Chem., 24, 1099-1103 (1959). Ester intermediates of various types are studied for synthesis of 1,3-dihydroxy-3-phenyl-2-butanonr in less than 500-mg. quantities. Steroidal aldosterone blockers. ZZ. J. A. Cella and R. C. Tweit, J. Org. Chem., 24, 1109-10 (1959). Synthesis of 50-500 mg. quantities of 17-spirolactones are reported and their biological activities described. Preparation of pregnane-Sor,i6a,ZOc-trio1 and of two of its stereoisomers, H. Hirschmann and M. A. Daus, J. Org. Chem., 24, 1114-19 (1959). Preparations of l&537 mg. pregnane-3cy,16a,20a-triol, pregnane-3ay,1601,20@-triol, and 38, 160l, 2Op-trio1 are described. Preparation of other 16a-acetoxy steroids in less t,han 100-mg. amounts are also given. MICROCHEMIC$L
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Dienone-phenol rearrangement of%phenyl-oquinol acetate, H. Buclzikiewicz and W. Metlisics, J. Org. Chem., 24, 1125-26 (1959). Rearrangement of 2-phenyl-oquinol acetate (0.2 g.) with acetic anhydride and perchloric acid results in 2,6diacetoxybiphenyl. Synthesis of 2,6-hydroxybiphenyl from B-hydroxybiphenyl%e:trboxylic acid is also reported. tetroxide-catalyzed oxidations of pyrene, F. G. Oberender and J. A. Dixon, J. Org. Chem., 24, 1226-29 (1959). Reaction of 17 mg. pyrene4,5--quinone with o-phenylenediamine and glacial acetic acid yields 19 mg. pyrene+I‘,5, ‘2,3-quinoxaline.
Osmium and ruthenium
Reaction of the enot form of 1,2-cyclohexanedione
with the phenyl Grignard reagent, P. Tomboulian and C. A. A. Bloomquist, J. Org. Chem., 24, 1239-44 (1959). Oxidation of about 500 mg. 2-hydroxy-3-phenylcyclohexanone with chromic acid, periodic acid, and lead tetraacetate was studied. Also studied were the reactions of 5-benzoyl-2-phenylpentanal and 1,3-diphenyl-1,2-cyclohexanediol. The structure of C,rH,nOa, G. R. Oxidation of 2,6-di-tert-butyl-.&methylphenol. Yohe et al., J. Org. Chem., 24, 1251-56 (1959). The structure of C,aH,Z03 previously reported as the oxidation product of 2,6-di-tertbutyl-4-methylphenol is now believed to be nL-trans-5,6-di-tert-butyl-2-hydroxy-l,4-diketo-2-cyclohexene as a result of a series of reactions on samples of less than 500-mg. size. The solvolysis of &$-dimethylcholesteryl-p-toluenesulfonate, R. W. Moriarty and E. S. Wallis, J. Org. Chem., 24,1274-78 (1959). Solvolysis in 60% aqueous acetone in the presence of potassium acetate is conducted in less than 500 mg. quantities, and the identification of the products is reported.
Synthesis in the cardiac aglycone field. I. The condensation of or-ketol tetrahydropyranyl ethers with acetylene and with propiolic esters, F. Sondheimer, N. StjernStrom, and D. Rosenthal, J. Org. Chem., 24, 1280-84 (1959). Unsuccessful at-
tempts to synthesize a steroidal lactone containing a 5’-cu-pyrone grouping at the 17&position are reported. Reactions of the mono-p-toluenesulfonic acid ester of yohimbyl alcohol, R. C. Elderfield et al., J. Org. Chem., 24,1296-1301 (1959). Hydrolysis of less than 500 mg.
of the mono-p-toluenesulfonic acid ester of yohimbyl alcohol under acid conditions gives yohimbyl alcohol and under basic conditions results in the formation of an oxetane. of glycineamidine, A. K. Bose et al., J. Org. Chem., 24, 1309-13 (1959). The reactions of phthalimidoacetonitrile and ethyl phthalimidoacetate with ammonia under varying conditions are reported.
Some derivatives
Chlorination o,f1,8diacetylurea and of barbituric Elrovy, Jr., J. Org. Chem., 24,1383-84 (1959).
acid, F. B. Slezak and H. A. McThe procedure for chlorination of
262
ABSTRACTS
acetylurea is described, and the warning given that overchlorination resulted in an explosive oil. sulfonium salts with sulfur at a bridgehead, R. H. Eastman and G. Kritchevsky, J. Org. Chem., 24, 1428-32 (1959). Preparation of 150 mg. bicyclo[4..3.0]nonane-1-thianium picrate from 100 mg. crude 4(2-tetrahydrothienyl)butanol is given (See specifically p. 1430).
Bicyclic
A. J. Castro et al., J. Org. Chem., 24, 1437-40 (1959). Potassium permanganate oxidation of 2,2’-2,“-tripyrrylmethanes (300-900 mg.) gives varying yields of the corresponding methenes.
,9,.%“,B”-Tripyrrylmethenes,
p-Phenylazobenzenesulfonyl chloride-a new reagent for identification and separation of amines, E. 0. Woolfolk, W. E. Reynolds, and J. L. Mason, J. Org. Chem., 24,
1445-50 (1959). N-substituted p-phenylazobenzenesulfonamides are prepared from 100 mg. of the p-phenylazobenzenesulfonyl chloride and the amines, and the Tswett absorption method is used for separation and identification of the derivatives. Some nitrogen-containing ferrocene derivatives, E. M. Acton and R. M. Silverstein, J. Org. Chem., 24, 1487-90 (1959). The preparation of derivatives of ferrocenyl-
amine and of N-substituted are given.
ferrocene-carboxamides in amounts of 80-1000 mg.
experiments with i,3-oxathiolan-5-ones, A. Romo de Vivar and J. Romo, J. Org. Chem., 24, 1490-93 (1959). The preparation of 2-hydroxycyclohexanone diphenylacetate from 100 mg. cyclohexane-1,2-diol-diphenylacetate and from 80 mg. hydroxycyclohexanone are described. Desulfuration of oxathiolanone in amounts of 50-850 mg. is also given (See specifically p. 1493).
Desulfuration
Nitration of i- and Q-jluorojfuorene, K. Suzuki, E. K. Weisburger, and J. H. Weisburger, J. Org. Chem., 24, 1511-17 (1959). Oxidation of 42 mg. 1-fluoro-7-nitrofluorenone with chromium trioxide is given along the ultraviolet data on the fluorenone product. Also described are the catalytic reductions of I-fluoro-Bnitrofluorene, 1-fluoro-4-nitrofluorene, and 1-fluoro-7-nitrofluorene, and the preparation of the acetamide derivatives of the resulting amines (See specifically p. 1515). Characterization of cupressaceae tropolones as dicyclohexylamine salts, E. Zavarin, R. B. Smith, and A. B. Anderson, J. Org. Chem., 24,1584-85 (1959). The preparation of derivatives of tropolones (about 250 mg.) with dicyclohexylamine is described as is the recovery of the tropolone from the resulting salts. of S-phenyl-3-acetoxypropanyl chloride with ethyl sodioacetoacetote, E. M. Smissman and F. B. Block, J. Org. Chem., 24, 1593-95 (1959). Alkali hydrolysis of 123 mg. 4-phenyl-5-carboethoxy-6-methyl-3,4dihydro-2-p~one to give 95 mg. 3-phenyl-5-ketocaproic acid and also the identification of the acid are reported.
Reaction
MICROCHEMICAL
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ABSTRACTS
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11-Alkylated steroids. III. Two syntheses of Ii-methylhydrocortisone, G. S. Fonken, J. A. Hogg, and A. V. McIntosh, Jr., J. Org. Chem., 24,1600-1604 (1959). Much of the work of the syntheses starting with lip-hydroxy-11-methyl-5&pregnenedione was done with 200-500 mg. samples. Syntheses of hormonesfrom 5,6-dichloro-steroids. I. Addition of chlorine to pregnenolone acetate, F. A. Cutler, Jr., et al., J. Org. Chem., 24,1621-25 (1959). Reactions of 50-500 mg. 5cu-6fl-dichloro-3fl-acetoxy-pregnan-20-one and 5a,6or-dichloro3@-acetoxy-pregnane-20-one with zinc, potassium hydroxide, or chromous chloride are reported (See specifically p. 1625). Oxygen heterocycles. A new isojlavanone from Sophora japonica, L., H. Suginome, J. Org. Chem., 24,1655-62 (1959). Degradation studies on 200 mg. or more of an optically active isoflavanone from Sophora japonica, L., called sophorol, shows it to be 2’,7-dihydroxy-4’,5’-methylenedioxyisoflavanone or 2’,7-dihydroxy-5’,6’isoflavanone. (See specifically p. 1661). Synthesis of some heterocyclic derivatives of a-keto acids, J. D. Fissekis, C. G. Skinner, and W. Shive, J. Org. Chem., 24,1722-25 (1959). Preparation of 2cyclopentyl-3hydroxyquinoxaline, 2-cyclohexyl-3-hydroxyquinoxaline, and Pamino-6-cyclohexyl-7-hydroxypteridine from about 150 mg. of appropriately substituted glyoxylic acid is given. A new technique for preparing 8,4-dinitrophenylhydrazones. III. Two examples of diacetone alcohol and methyl vinyl ketone, H. hitherto unobtainable simple derivatives: J. Shine, J. Org. Chem., 24,1790-91(1959). Diglyme is used as the solvent in preparing the 2,4-dinitrophenylhydrazone derivatives of sensitive compounds. Th,e synthesis of nitroestradiols, T. L. Patton, J. Org. Chem., 24, 1795-96 (1959). Preparation of nitroestradiols by sodium borohydride reduction of 500 mg. 2- or Pnitroestrone or 2,4dinitroestrone is given. Ntm-lability of the a-hydrogen during ninhydrin oxidation of alanine, J. G. Kay and F. S. Rowland, J. Org. Chem., 24,1800-1807 (1959). Oxidation of tritium-labeled and nonlabeled alanine is studied with 50-290 mg. samples. In vivo hydroxylation of I-ethynyl-cyclohexyl carbamate. II. The orientation on hydroxylation, R. E. McMahon, J. Org. Chem., 24,1834-36 (1959). Various isomers of I-ethynyl-cyclohexane-1,4-diol (500-mg. samples) are catalytically hydrogenated to the corresponding saturated acids. Basic hydrolysis of 10 mg. l-ethyl cylohexane-1,4diol is also described. Micro
Apparatus
and Miscellaneous
A modijed chromatographic microapplicator, D. Kirman, 410-11 (1959). The apparatus is described.
Tools Am. J. Clin. Pathol.,
31,