Reaction of olefin α-oxides with boric anhydride

]Petrol. Chem. U.S.S.R. ¥oL 20, No. 2, pp. 10~-108, 1 9 ~ 0 Printed in Poland

00~l-.64f~81M/0e010~06507.80,t0 C 1981 l~rgamon ~ Ltd.

REACTION OF OLEFIN ¢~-OXl~ES WITH BORIC ANHYDRIDE* K. M. Soxov~, G. A. Z~m~AYA, V. F. Cnu~KOVA and A. N. BAsm~mov A. V. Topchiyev Institute of Petrochemical Synthesis, U.S.S.R. Academy of Sciences (Rece/ved 13 .March 1979) DURn~G oxidation of unsaturated hydrocarbons in the presence of boric acid and its derivatives olefin oxides and unsaturated alcohols are the main reaction products [1, 2]. Polyfunctional compounds containing oxygen--diols, ketoalcohols, polyesters, etc. of high boiling point are formed as reaction byproducts. Interaction of olefin oxides with boron-containing compounds m a y be a possible method of forming these compounds. It was shown previously [3] that epoxycyclododecane reacts with boric acid and boric anhydride. Polyfunctional hydroxyl-containing compounds and cyclododecen01 are the main reaction products, obtained by a number of conversions of the primary complex formed as a result of the electron pair of the donor molecule of oxide and the vacant p-orbit of the boron atom. Results are given in this study obtained in the course of chemical conversions of ~-oxides of aliphatic olefins during their reaction with compounds containing boron. Dodecene ~-oxide and heptene ~-oxide were used for the investigation. EXPERIMENTAL

Dodecene ~-oxide was obtained by the reaction of dodec-l-ene with 30% hydrogen peroxide in the presence of acetic acid and small amounts of cationexchange resin as catalyst [3]. The dodecene ~-oxide synthesized had b.p. 95-96°/3 mmHg, n~° 1.4351 and an 0 content of 8.3°/o. Results in the litera, ture were as follows [4]: 1,2-epoxydodecane, b.p. 97-98°/3.5 mmHg, noBO 1.4356. Calculated: 0 8-70/o. The reaction of dodecane oxide with boric anhydride was carried out in a four-necked flask provided with a stirrer, thermometer, inlet for boron compounds and a Dean trap. Dodecene oxide was placed in a reaction vessel, heated to given temperature and a boron-containing compound added while stirring vigorously. Samples were taken during the reaction, and were then treated with hot water, dried and analysed by well-known methods. Kinetics of dodecene oxide consumption and of the formation of main functional groups during reaction with boric anhydride at a temperature of 150 °. and a varying ratio of reacting masses are shown in Fig. 1. For c o r n *

Neftekhimiya 20, No. 3, 430-435, 1980. 103

104

K . M. S o K o v A

~ ~.

parison, data derived from epoxycyclododecane under similar conditions are given. Experimental results prove t h a t dodecene oxide has a higher reactivity in relation to boric anhydride than epoxycyclododecane. With dodecene oxide the reaction ends basically in 10-15 min. Further increase in reaction time produces some consumption of oxide, however, functional group content in reaction products remains practically unchanged. As with epoxycyelododecane [3], the main factor influencing the degree of conversion of dodecene oxide is the ratio between reacting components. An increase in the concentramequiv/s

mequiv/$

91/1009 producf

5~

h

Q'

a _

.40

C

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! zol I

2

i0

3 i

I

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q5 rain

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30

45 rain

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ourvee of the consumption of dodecene oxide (a), the formation of c a r b o n y l (4, 5), hydroxyl (1"5") groupe (b) and unsaturated bonds (e) in the reaction of dodeoene oxide (1, 1"-4, 4') and epoxycyelododecane (5, 5") with boric anhydride a~ a temperature of 150°C. [B=O=], % wt.: ], 1'--3.5; 2, 2", 5, 5'--6; 3, 3"-- 10; 4, 4"--20. l ~ o . I. ~ i n e t i c

",~

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~ 60

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20 I

I

I

0 3.5 5

I

I0

2O

[B:03], % wt. FIG. 2. Dependence of the degree of eonvorsion of dodeoeno oxide on the amount Of BIO, at & tempersture

o f 150°C a n d a r e a o t i o n t i m e o f 15 m i ~

Reaction of olefin g-oxides with boric anhydride

I05

tion of boric anhydrid~ in the reaction medium increases the degree of conversion of oxide (Fig. 2). Reaction products are characterized in every case by a high hydroxyl group content, while acid, ester and carbonyl numbers vary withi~ the range of 2-6 units, iodine number during t h e reaction remaiuing unchanged. For epoxycyclododeeane the iodine number increases continuously (Fig. 1). ~ U I ~ C T I O N A L A N A L Y S I S O F ]~,EACTIOlq P R O D U C T S O F O L E F I N O X I D E S W I T H B O R I C A.NHYDRID]m

T 98°C; reaction time 180 rain

No. of 1 exp. 1

Reaction product of

O~ide Hydro- I Carbo- Ester Acid Conversion xyl

I

nyl

of oxide, mol.%

number mgKOH/g Heptene ~-oxide with BIOa Hydrolysis of heptene g-oxide with water Heptene g-oxide with BsO~ in the pnesenee of water Hydrolysis of dodeee~e a-oxide with water Dodecene ~ x i d e with BiOa in the presenoe of water

22

311

211 17

2 m

765

3

95 54 96

302

o

281 ]

7

To determine the chemical composition of oxygen compounds formed during the reaction of dodecene oxide with 10~/o B208 (temperature 150°; duration 30 rain, Fig. 1, curves 3), reaction products after saponification with water were separated into monofunctional and polyfunctional compounds by distillation in vacuum. The yield of monofunctional compounds was 17.3°/o wt. of the reaction mass. Gas chromatographic analysis using a "Khrom-31" chromatograph indicates that monofunctional compounds are basically represented by dodecene oxide. No dodecen-3-ol was found in reaction products. Consequently, in contrast with epoxycyclododecane, no unsaturated alcohols were formed during the reaction of dodecene oxide w i t h Bt0s under the conditions studied. The yield of polyfunctional high-boiling oxygen compounds was 82.7~/0 wt. The compounds isolated had a hydroxyl number of 19g, an acid number of 3 and an ester number of 7. The product was free from carbonyl and oxide groups. Elementary analysis of high-boiling oxygen-containing compounds showed the following: "

106

K. M. S o x o v A ~ ~ .

Found, %: C 76.34, H 12.43, O 11.23 (from the difference). Molecular weight 558 (obullioscopieally) C86H7,O4. Calculated, %: C 75"78, H 12.98, O 11.24. Molecular weight 570; hydroxyl number 197. Results suggest that the compounds examined correspond to the following structure: CH3--(CH2)g--CH--CH~--O--CH--CH~--O--CH--(CH2)9--CH3. I OH

I (CH2)9 I

I CHzOH

CH8

Consequently, during the reaction of dodecene oxide with B203 as main reaction product boric acid esters of 13, 16-dioxa-14-decyl-17-oxymethylh e p t a c o ~ n o l - l l are formed. Product yield under the conditions studied is about 95o/0 in terms of the oxide converted with a degree of conversion of To elucidate the problem concerning the effect of molecular weight of olefin oxides on their reactivity in relation to compounds containing boron and to examine in more detail the composition of reaction products formed, a study was made of the reaction of heptene oxide with BzOs. Heptene oxide obtained by oxidation of hept-l-ene under pressure had b.p. 143-144 °, oxide oxygen content of 13.2~/o, n~° of 1,4150. Results in the literature [5] were: ~-oxide ofhept-!-ene had b.p. 143-145 °, n~ of 1.4164. C~H140. Calculated, ~o: 014.0. The reaction of hept-l-ene oxide with B~O.~ was carried out in a roundbottomed flask provided with a reflux condenser over a boiling water bath while stirring vigorously with a stirrer. Reaction products were treated t h e same way as in previous experiments using dodecene oxide. Results are tabu° lated. For comparison, data are given derived using dodecene oxide under similar conditions. Experimental results prove that with a reduction in the molecular weight of olefin oxide, reactivity increases both in relation to HsO and in relation to B~Os. If dodecene oxide cannot be hydrolysed in practice on being heated with H20 for 3 hr, the degree of conversion of heptene oxide is 54 m o l . ~ under these conditions. The addition of B20 s has a catalytic action on the reaction. In the presence of B20 s the degree of conversion of dodecene oxide and heptene oxide is 7 and 96 mol.~/o, respectively. The product obtained with heptene oxide has a high hydroxyl number (765, exp. 3), typical ofheptane diols (calculated for C~Hle02:

848). A molecular spectroscopic study of the reaction product o f exp. 3 using a UR-20 device shows t h a t an intense broad band with m aYima at 1050 and 1080 cm -1 is observed in the spectrum, due to vibrations v(CO) and 6(OH) in primary and secondary alcohol groups, respectively and a band at 3400 cm -1 caused by bond-stretching vibrations of OH groups combined with i n t r a - a n d intermolecular hydrogen bonds. Bands at 1380, 1460 and 1475 cm -1 are due

Reaction of olefm ~xides with boric anhydride

107

to deformation vibrations of methyl and m e t h y l e n e groups. Bond-stretching vibrations of these groups are observed at 2930, 2870 and 2975 cm -I. Ronki,g vibrations of methylene groups (CHub are observed at 735 cm -1. The spectrum contains a band at 1720 cm -1, which corresponds to bond-stretching vibrations of the carbonyl group. From the results it may. therefore be stated t h a t d~ring the reaction of heptene oxide with B20 8 in the l~resence of H20 ~-heptane diol is formed as main p r o d u c t , o f which the yield is 90 mol.~/o in terms of the oxide converted, with a degree of conversion of 96 mol.°/o. The product formed during the reaction of heptene oxide with BzO 3 in the absence of H20 (exp.1), contrast with the product of exp: 3, had a comparatively low hydroxyl number (311). Elementary analysis of the reaction product of exp. 1 shows: Found, ~/o:C 69.51, H 12.15, O (from the difforonoo) 18.34. Molecular weight 390; ~0 1-4510. CmlH~404. Calculated, %: C 7(>00, H 12.22, O 17.78. Molecular weight 360: hydroxyl number 311. The moleeular-spectroscopic study of the product of exp. 1 shows t h a t the spectrum contains a broad band with maxima at 1050,1110 and 1140 cm -1, which is evidence of the presence in the molecule of a C-O group in primary and secondary alcohol groups and in the ether group. Methyl and methylene groups are represented by bands at 1380, 1460, 1470, 2930, 2870 and 2970 cm-L The presence in the spectrum of a band at 735 cm -1 confirms the existence in the molecule of a (CH2)4 group. I t m a y be concluded from experimental results that the reaction product of experiment I (after saponification with water) is 8,11-dioxao9-amyl-12oxymethylhepta-6-decanol CH3~(CH~)4_CH__CHs_0--CH--CH~.--0--CH--(CH~h--CH3 I

I

1

()H C~Hn CH20H The reaction mechanism m a y be ]presented in the following way: CHa--(CH.~),C H - - C H ~ + H 0--B--0---~CHt--(CH,h--CH--CH,°Xid--,eCHs--(CH~),--CH ,, NO/ ( + I I 0 0 I

I

HO--B--O

CH2

I

I

+CH

C H 0r~_xid_~ e i 0 I --B--O-I OH

(CHub CH~

--,CH3--(CHD4--CH O

I

~H,O

. CPI, O

I

~CHs--(CH~--CH--CH~--O--CH--CH~--0--CH--CH~OH (CH,h

\

CH, H0-~B--0 ÷ t 1 (IHr-(CH2)4--CH--CHr-O--CH l (CH,), CH*

"

OH I

I

CH,

(CH~)4

I

CHs

108

K.M. SoxovA ~ ~. In the presence of HsO the reaction goes in another direction CHs--(CHz)4--CH--CH2-~HO--B--O-- --' CH3(CH2)4--CH--CH2~ ~.HOFI ",0/. I + I 0

I HO--B--O-a

-~CHs--(CHt)4--CH--CH2OH~HsBO3 OH SUMMARY

1. A s t u d y was made of the reaction of aliphatic olefin oxides of different molecular weights with compounds containing boron. Boric acid esters of high molecular weight alcoholic esters are the main reaction products, their yield varying within 95-98 reel. ~/o in terms of the oxide converted with a degree of conversion of 85-97 mol. % 2. During the reaction of heptene oxide with boric anhydride in the presence of water as main reaction product ~-heptane diol is formed, of which the yield is 9 0 ~ of the oxide converted. 3. The reaction of olefm oxides with compounds containing boron m a y be • egarded as one of the methods of forming polyfmlctional hydroxyl-containing compounds obtained b y oxidation of aliphatic olefins in the presence of boric acid. REFERENCES

t. A. N. BAk~iHKIP-0V,Ye. V. ~ 0 L ' K I N A , S. A. LODZTK and V. V. K.AMZOT.'KTN', Dokl. AN SSSR 184, 597, 1969 2. K. M. SOKOVA, G. A. ZELENAYA and A. N. B ~ O V , l~Teftelrhlmiya 16, ~ 5 , 1976 3. K. M. SOKOVA, G. A. Z~.~IAYA, Yo. V. KAMZOT.lgr~A and A. N. BASHWrgOV, l~eftekl~imlya 18, 793, 1978 4. D. SWERN, G. N. BIT.T.~ and J. T. S4~ANLAN,J. Amer. Chem. See. 68, 1504, 1946 3. F. Ya. PERVEYEV, Zh. obahoh. Irhlmll ~.~, 1673, 1953