CA1064045A - Process for preparing oxirane compounds - Google Patents

Abstract

PROCESS FOR PREPARING OXIRANE COMPOUNDS

Ethylenically unsaturated hydrocarbons having form 8 to 60 carbon atoms may be epoxidized with high yields by reaction with mixtures of acetic acid and hydrogen peroxide in the pre-sence of liquid, inert, aliphatic chlorinated hydrocarbons ha ving from 1 to 3 carbon atoms, whereof at least one is present in the form of a -CCl3, -CHCl2 or C=Cl2 group.

Description

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I-t has been known for a long time -to convert ethylenically unsaturated compounds into their epoxides by reacting them ~ith c)rganic peracids. As peracids there have been used ori-ginally perbenzoic acid as well as monoperphthalic acid, where-as peracetic acid prepared and used in acetic acid was consi-dered to be unsuitable since the reaction products of olefins and such peracetic acid solutions exclusively contained ~-gly-cols or their monoacetates.
Swern and his collaborators~however~demons-trated that mix-tures of perace-tic acid and acetic acid are quite suitable for epoxidi~ing long chain unsaturated fat alcohols 9 fatty acids and fatty acids esters when maintaining low temperatures and short reactio~ times and when avoiding the use o~ strong acids which would ca-talyse the ope~ing of the oxirane ring by acetic acid CJ.Am.Chem. SOCD 67 (1945), pages 412 and 1786;
68 (1946)9 page 1504 7. This process9 however, is less conven-ier~t for epoxidizing 1-alkenes such as octene-1, decene 1 te~
ra~ecene-19 hexadecene~1 and octadecene-1 ? as reaction times of 24 to 30 hours are required compared to 3 hours when using oleic aci~ and from 40 to 56 % of epoxides are only obtained ~.
-~ besides 5 to 25 ~ of unreacted olefin and 15 to 40 % hydro-xyacstate. The C~6 to C18 epoxides may onl~ be isolated more-over in a purity of 80 to 90 ~ by ~orking them up by distil-lation~
.

; 25 The aforesaid method may be simplified and improved by : the so-called "process in situ" w~erein hydrogen peroxide is allowed to act on a mixture of olefinic compound, acetic acid and s~lfuric acid (or an acidic ion exchanger), optionally in 29 the presence of a saturated aliphatic or aroma~ic hydrocarbon : ., . , . .. . , .: . . . . . .
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HOE 74/F 80~ K
L~
as solvent ~ cf. US Patent Specifications Nos. 29801,253 and

2~692,271; Fall and Greenspan9 Ind. Eng. Chem. 47 (1955), page 1~7; J.Am.Oil Chemist's Soc. 34 (1957), page 161 J.
The peracetic acid process performed in situ is especial-ly convenient for reacting compounds to be epoxidized rapidly and easily~ According to a reactivity scale published in "Che-mical Week Magazine" (April 6th3 1963) the natural fats and oils which may be reacted in an especially simple manner with all usual epoxidation agents to the corresponding oxiranes may be numbered in the first place among these compounds. ~-Olefi~
on the contrary belong to the olefins to be epoxidized ~ith difficulty which pratically may not be epoxidized with perace-tic acid prepared in situ according to "Chemical Week Magazi-ne" r Houben-Weyl, ~ethoden der Organischen Chemie~ volume VI/

3, 392 (1965)also points to the fact -that the epoxidation of ter!ninal ethylenic double bonds is rendereddifficult and reco~
~ends to carry out epoxidation in these cases with peracetic acid previously prepared for this purpose.
The present invention is based on the problem to find a way for modifying the peracetic acid process ~ ob~ious-ly haYing a series of advantages compared to other known epo-xidation processes~ and being distinguished especially by its easy handling, its low technical expenditure, the use of aque-ous hydrogen peroxide instead of peracids pre~iously prepar~, ; the low consumptlon of acetic acid9 an easy isola-tion of the reaction products and high yields of epoxides such that it ., .
may be used successfully and with high yields even in the case 29 of olefins 9 especially of long chain 1-alkenes, which may on-`~ ~ 3 ~

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ly be oxidized with difEiculty~
The problem may be solved surprisingly by performing the peracetic acid process in situ in the presence of a solvent, the type and the quantity of the solvent being of decisive S importance.
The present invention consequently provides a process for preparing oxiranes of straight chain or little branched mainly terminal ethylenically unsaturated aliphatic hydrocarbons ha-ving from 8 to 60 carbon atoms in the molecule by epoxidizing said hydrocarbons with an oxidation comprising acetic acid and aqueous hydrogen peroxide in the presence of an acidic catalyst, which comprises carrying out the expoxidation in an inert, chlor-inated aliphatic hydrocarbon being liquid under the reaction con-ditions of ~rom 1 to 3 carbon atoms, whereof at least one is pre-sent in the form of a -CCL3, -C~IC12, or =CC12 group, the pro-portion by weight of ethylenically Imsaturated hydrocarbons and ~` solvent being from 1 : 1 to 1 : 50. The acetic acid in the oxi-dation mixture may be completely or partly replaced optionally by acetic acid anhydride.
According to the proess o the invention even the unbran-ched or little branched mainly terminal ethylenically unsatura-ted hydrocarbons of from 8 to 60 carbon atoms, which are consi-dered to be epoxidlzable with special difficulties may be con-verted into the corresponding oxiranes smoothl;y and with con-uersions oE from 95 to 100%. This could not be expected as in , the epoxidation in situ o other long chain olefins, for examp-., le, oleic acid butyl ester yielding 9.10 epoxystearic acid butyl ester the addition of 20~ by weight of hexane or ben~
. zene-(calculated on oleic acid ester used) only has an insigni-- - . ~ . :
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ficant i-nfluence on the course of the reaction and the yield.
The desired epoxystearic acid butyl es-ter could be obtained in the presence of benzene wi-th a yield of 80 ~)whereas a yield of 76 ~ was obtained without an addition of benzene ~ cf~ Gall and Greenspan, Ind. Eng. Chem. ~ ~1955)~ page 148 ~.
Among the straight chain or little branched mainly termi-nal ethylenically unsaturated alipha-tic hydrocarbons of from 8 to 60 carbo~ atoms in the molecule -there may be mentioned especially 1-alkenes .such as 1-octene, 1---nonene, 1-decene 9 1-undecene? 1-dodecene, 1-tetradecene, 1-hexadecene, 1~octadecene, long c~in l~alkenes of from 20 to 60 carbonn atoms as well as mixtures of the afore~aid 1-all~enes, for examp]el technical ol~
~in fractions of ~rom 20 to 24 carbon atoms or of from 26 to 52 carbon atoms and more~y~r branched 1-alkenes~mixtures of branched 1~alkenes, mixtures of bra~ched and unbr~nched 1-al kenes, mixtures of unbranched 1-alkenes, branched 1 alkenes and unbranched or branched alkenes haYingcen-tral ethylenic double bo~ds. The bra~ched hydrocarbons should contain per mo~
leculeat most two branching points with side`chains o~ from 1 to 4 carbon atoms. Hydrocarbons ha~ing central double bonds considered to be easily epox~di~ed may o~ course be epoxidized smoothly according to the proGess o~ -the invention Suitable organic solvents which must be liquid and stable under the reaction conditions and mu~t neither react with the starting materials or with the final products ~re chlorinated - aliphatic hydrocarbons of from 1 to 3 carbon atoms in the mole-cule. At least one of the carbon atoms should be present in the ~orm o~ a ~CCl~-~ -C~Cl2-or-CCl2 group. There may be mentio-~9 ned for example chloroform, 1.1.2-trichloroethan~ tri~
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chloroethane, 1.i.1.2-tetrachloroethane, 1q102.2.~tetrachloro-ethaIle 9 tetrachlnroe-thylene and pentachloroethylene RS well as mixtures of these hydrocarbons.Chloroform is preferably used.
The quantity of the solvent plays an essential par~. in the success o~ the process besides the nature of the solvent, The process is carried out with a weight ra-tio of olefin to be epoxidized and solvent of from 1 : 1 to 1 : 50, preferably of from 1 : 1 to 1 : 20, especially o~ from 1 : 2 to 1 : 6, where by epoxide yields of up to 100 ~ are obtained. It may be sup-posed, consequently, that the solvents used according to the inve~tion are especially capable owing to their chemical struc-ture of protecting the oxirane groups formed a~ainst the clea-vage of the epoxide ri~g by acetic acid and/or water cataly~ed by hydrogen ions. The reac-tion temperature generally is Prom 30 to 800C preferably from 50 to 800C
The reaction pressure is not critical, the reac-tion is usually carried out at atmospheric pressure, higher or lower pressures bei~g likewise suitable, however.
As acidic catalysts generally are used mineral acids~
ethanesulfonic acid or cation exchanger resins in the H~ formg generally ln an amount of 1 to 3 ~ by weight calculated on the mixture of oxidants.
The epoxidation generally is carried out in the ~ollowing . manner: An oxidation mlxture of acetic acid and hydrogen pero-xide in the prese~ce of catalytical quantities of -the acidic catalyst (sulf'uric acid~ ethanesulfonic acid, acidic cation ex-changer resi~) is allowed to act on -the olefill dissolved in the solvent or-in the case of liquid olefins-mlxed with -the solvent 29 Or the mixture of solven~, ~ olefin, ace~ic acid and catalyst ls ~, .

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H~C

introduced in-to the reacti.on vessel and reac-ted ;i~ t~L .,-~drogen peroxide. ~ preferred method consi.sts in in-troducing into -the reaction vessel a m:ix-ture of ~ne part b~ weight of olefin and

4 parts by weight of solvent and in addi.~g subequently per mole of olefi~ an oxidation mixture of 0.5 to 1.5 moles (preferably of 0.5 to 1.1 moles) of concentrated acetic acid, 1.05 to 1 t 5 moles) (preYerably 1.05 to 103 moles) oX a 25 to 30 ~ hydrogen peroxide solution and 1 to 3 % by weight (calculated on the to-tal weight of acetic acid and hydrogen peroxide solution) of concentrated sulfuric acid and in ~aintaining the mix-ture for about 6 to 20 hours a-t a temperature of 50 to 80C~ preferably o~ 60 to 65C.
A slightly modifie~ method having the ad~antage that epo-sidatioll times are required which rarge at the lower limit of the aoresaid consits in replacing in the oxida-tion mix-ture the acetic acid completely or party by acetic acid anhydride, In this case one proceeds in the following manner: A mixture of acetic acid anhydride,. hydrogen peroxide and optionally acetic acid is prepared~ which is allowed to stand for 0~5 to 10 hours, pre~erably for 1 to 4 hours at a temperature of 10 to 60Qc,pre-ferably o~ 30 to 50C. The acidic ca-talyst~ the sol~ent and the olefin are then added and the mixture is allowed to react as ~ mentioned above while stirring. From 1.05 to 1.5 mol.es of H202 - (in the form vf an aqueous solution of 25 to 50 % by weight) and from 0.25 to 0.75 moles preferably of from 0.25 to 0.50 mo - les of acetic acid anhydride ge~erally are used per mole of ol~
fin. When using mixtures of acetic acid a~ydride and acetic .~ acid it is recommended to choose a molar ratio of 0.1 to 0.6 29 mole of acetic acid anhydride and of 0.3 -to 1~3 moles of acetic ., .
: - 7 ~

~ 7~h~ ~K

acid.
For isolat-.ing the reaction products from -the reaction mlx~
ture obtained by one of the aforesaid me-thods the aqueous phase is separated from the organic phase, the lat-ter i5 washed with ~ untilit is ~ree orm acidic components and the solvent is distilled of~, optionally in vacuo.
The epoxides obtained o~ an oxirane content of 90 -to 100 a~
are valuable intermediates for syntheses7~or example~o.~ alcoh~
esters or amides because of their high reactivity. They are distinguished by an unusually high puri.ty, cortaln only traces of unreacted ole~in~ and secondary productsa~d may be direc-tly used for practically all applications or further reactions wit~
out additional puri~ication. Higher members o~ -the homologous series may be used as lubricants and costabilizers in the processing of plastics . The extremely high ~egree of purity is especially important in the case o~ epoxides having a chain length of from 20 or more carbon atoms 7 as purification pro-cesses may only be carried out with a grea-t exp~nditure or not -- at~l with epoxides of these chain lengths.
The ~ollowing examples illustrate the invention. The ~ndi-cated iodine numbers ha~e been determined according to Eauf-~ann, the oxygen content o~ -the oxiranes according to AOJ.Durb~
taki, Anal.Chem~28 (1956~9 pages 2000 to 2021y by means of HBr in glacial acetic acid.

A 4 liter ~our neck flask provided with an agitator, a re-flux cooler, a proportioning funnel and an inn~r -thermome-ter was charged with 504 g o~ dodecene-1 (iodine number 149~) 29 and 2020 g o~ chlorQform. A mixture o~ 90 g of glacial acetic ".
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acid, 390 g of a 34 % hydrogen peroxide and 9 g of 50 ~ sulfu ric acid was added thereoto within about 5 miml-tes while stir-ring. The two phase mixture was heated -to an inner temperature of 60 -to 62C9 s-~irred for 12 hours at I,his temperature and coo~
led to room tempera-ture~ The aqueous phase was separated, the chloroform solution was liberated ~rom acidic components by washing it wi-th water and the chloroform was then distilled off with the residual ~later. 550 g of orude 1.2-epoxydodecane rema~
ned in the distillation flask in the form of a clear, transpa-rent liquid. The oxygen content of oxirane was 8~3 % (theory 8~7 ~), the iodine number 4.9.
The reaction product consequently contained about 95 ~ of 1.2-epoxydodecane besides about 3 ~ of unreacted olefln; the yield of epox.ide consequently was about 89 %7 the con~ersion being about 97 %.
E X A M P ~ E 2-In an analogous ma~ner to example 1 a ~olu-tion o~ 588 g of tetradecane-1 (iodine number 128.1) in 2355 g of chloroform was reacted with a mixture of 90 g of glacial acetic acid, 360 g - 20 of 34 % hydrogen pervxide and 9 g of 50 % sulfuric acid. 63~ g of crude 1.2-epoxytetradecane wsre obtained in the form o~ a clear9 colorless liquid~oxygen content o~ oxira~e: 7.1 ~ (cal-culated 7.6 %)~iodine number, 5D8 The reaction product consequently consisted o~ about 93 %
f 1.2-epoxytetradecane and of ab4ut 5 ~ of unreacted olefin;
the yield conse~uently was about 98 % for a co~version of abou-t . ~5 %-~, ~
29 A 150 liter enamelled ~essel pro~ided with a~ ag~tator 9 a ., .... . ..

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~a~L~f~I~I HOE 74/F 805K

reflux cooler, a dosage vessel and a thermostate was charged with a solu~ion of 25.76 kg of hexadecene-1 (iodine number 1]1.
8) in 51.5 kg of chloroform. A mixture of 3.45 kg of glacial acetic acid, 14.g5 kg of 34% hydrogen peroxide and 0.345 kg of 50% sulfuric acid was added while stirring over a period of 2 hours into a olefin solution heated to 50C. The inner tempera-ture which had raised during the time of addition to 56 - 59C
was now adjusted to 61 to 63C and the reaction mixture was stirred at this temperature for 14 hours. After cooling the aqueous phase was separated and the chloroform solution was was-hed with water until it was free from acid. After having distil-led off chloroform and residues of water 27.0 ky of crude 1.2-epoxyhexadecane were obtained in the form of a clear, colorless liquid which gradually crystallized when kept at room tempera-ture for a certain time.
oxygen con-tent of oxirane: 6.4% (calculated 6.7%) ; iodine number: 4~6 The reaction product consisted of about 95% of 1.2-epoxy-hexadecane and of about 4% of unreacted olefin. The conversion - 20 was about 96% and the yield consequently about 99%.
;~ E X A M P L E 4:
A solution of 24.2 kg o-f octadecene-l (iodine number 99.6) in 50.4 kg of chloroform was reacted with a mixture of 6.0 kg of glacial acetic acid, 13~0 kg of 34~ hydrogen peroxide and 600 g o 50~ sulfuric acid in the apparatus described in ; example 3. After a reaction time of 10 hours the reaction pro-duct was worked up. 26.7 kg of crude 1.2-epoxyoctadecane were obtained as a clear, colorless liquid crystallizing when coo-ling to room temperature.

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oxygen content of oxira~ 5.5 % (calculated: 6.0 %) iodine nl~her: 2,2 The reaction product consequently contained about 92 ~ of 1.2-epoxyoctadecane besides about 2 ~0 of unreacted ole~in; the conversion was about ~8 ~ and -the yield consequen-tly about 94~.
E X A M P ~
A solution o~ 840 g of eicosene-1 (iodine number 89.9) in 2520 g o~ chloroform was reacted wi-th a mixture of 270 g of gla-cial acetic acid, 450 g of 34 ~0 hydrogen peroxide and 27 g o~
~0 50 ~0 sulfur.ic acid for 16 hours at a temperature of ~rom 60 to 63C in the apparatus and in the manner of example l.885 g o~
crude ~.2-epoxyeicosane were obtai~ed as colorless liquid ~ry~
stallizing at room temperature.
oxygen content o~ oxirane: 5.2 % (calculated 504 %~
iodine number~
The reaction product contained about 96 ~ of 1.2-e~oxyei-cos,:ne besides 1 ~ of unreacted olefin. The conversioll was 99 ~: the yield consequently about 97 %0 E X ~ M P ~ E 6:
A solution of 616 g of docosene-1 (iodine number 7g.8 in 2460 g of chloro~orm was reacted with a mixture of 180 g gla-cial acetic acid~ 300 g of 34 ~0 hydrogen peroxide and 18 g of 50 % sulfuric acid ~or 16 hours at a temperature of from 60 to 63C in an analogous manner to example 1. After working up 664 g of crude 1.2-epoxydocosane were obtai~ed in the ~orm of a ~ colorless liquid crystallizing at room ~emperature~
; oxygen content of oxirane: 4~5 ~ (calculated L~95 %) iodine number: 1.4 29 The reaction product consequently consisted of about 91 , .

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L,~, o~ 1.2~epoxydQcosane and of about 2 o~O of unreacted ole.~in;
the con~ersion ~as about 98 ~0 and the yield about 93 ~.
E X A M P I, E 7-In an analogous ma~ler -to example 1 a solu-tion of 882 g of ~l~kene~ a~ having of ~rom 2.0 to 24 carbon atoms and an a~erage molecular weight of 294 (iodine number 86.9~ in 1765 g of chloroform was reacted with a mix-ture of 180 g of glacial ace-tic acid, 390 g of 34 % hydrogen peroxide and 18 g of 50 ~0 sulfuric acid for 18 hours at a temperature of from 60 to 61C.
After working up 928 g of an epoxide mixture having of from 20 to 24 carbon a-toms were obtained as a white, soft-wax -like product .
oxygen content of oxirane: 4.9 ~0 ~calcula-ted 5.2 %~
iodine number: 2.5 t5 The reaction product consequently consisted of about 94 ~o of epoxides and of about 3 ~ unreacted olefins; the co~ersion was .~bout 97 ~0 and the yield of epoxide about 97 %.
_A M P ~ E 8:
A solution of 1008 g ofan alkene-1frac-t1On ~la~ing of from 24 to 28 carbon atoms and an average molecular weight of 364 (iodine number 66,4) in 2020 g of chlorofor.~ was reacted with a mixture of 180 g of glacial acetic acid 3 450 g of 34 ~0 hydro gen peroxide and 18 g of 50 ~0 sulfuric acid f or 18 hours at a ; temperature of from 60 to 62C. After working up 11~6 g of 25. epoxide mixture of from 24 to 28 carbon atoms were obtained as . a white sof~ wax~
oxygen co~tent o~ oxirane: 4.0 ~ (calsulated 4,2 %) lodine number: 1.4 . 29 The reaction prcduct co~sisted of about 95 % of the desi ~2 -. .. ~ : ,-. . , ~

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red eposide and of about 2% of unreacted olefin; the conver-sion was about 98% and the yield about 97%.
E X A M P L E 9:
According to example 1 a solution of 940 g of an alkene-fract.ion of from 26 to 52 carbon atoms whereo about 67% oE
the olefinic double bonds had a vinyl structure, about 30~
a vinylidene structure and about 3% a transvinylidene struc-ture (average molecular weight 470; iodine number 44), in 3760 g of chloroform was reacted with a m.ixture of 120 g of glacial acetic acid, 260 g of 34% hydrogen peroxide and 12 g of 50%
sulfuric acid for 16 hours at a temperature of from 60 to 65~C~
After working up 966 g of epoxide mixture of from 26 to 52 car-bon atoms were obtained in the form of a white wax.
oxygen content of oxirane; 3.0% (calculated 3.3~) iodine number: 0.5 It may be calculated therefrom that the reaction product consisted of about 91% of epoxide mixture of from 26 to 52 carbon atoms and of about 1% of unreacted olefins. The conver-sion was about 99% and the yield about 92%.
i~ 20 ~ X A M P L E 10:
:
As solution of 949 g of an alkene fraction having of from ;~ 25 to 52 carbon atoms,- whereof about 67% of the olefinic doub-le bonds had a vinyl structure, about 30% a vinylidene struc-ture and about 3% a trans-vinylidene structure (average mole-cular weight 470; iodine n.umber 44) in 2000 g of 1Ol.2.2 tetra-~ chloroethane was reacted with a mixture of 120 g of glacial `' acetic acid and 12 g of 50% sulfuric acid for 16 hours at a temperature of from 60 to 65C in an analogous manner to examp-- le 1. 965 g of epoxide mixture of from 26 to 52 carbon atoms -~ 30 were obtained in the ~form of a white wax-like product~

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oxygen content of oxirane: 2.9 % ~calculated 3.~ ~) iodine n1lmber: 1~8 The reaction product contained abou-t 88 % o:E epoxlde mix-ture of from 26 to 52 carbon atoms besides abou-t 4 ~0 of unreac ted olefin; conversion about 96 %, yield about 92 ~0.
E X A M P ~ E 11:
In the manner of example 1 a solu-tion of 940 g of an alkene ~raction Of fro~26to 52 carbon a-tom~, whereof about g2 $ of the olefinic double bonds had a vinyl structure 9 about 4 % a ~inylidene structure and about 4 ~0 a trans-~inylidene structu~
re (average molecular weight 470; iodine number 46~:in 5640 g of tetrachloroethylene ~as reacted with a mixture o:E 120 g of glac~al acid~ 260 g of 34 ~ hydrogen peroxide and 12 g of 50 ~0 sulfuric acid for 16 hours at a tempera-ture of from 60 to 65C 1.965 g of epoxide mixture ha~ing from 26 -to 52 carbon atoms were obtained in the f orm of a white waxy product.
oxygen con-tent of oxirane: 3.1 (calculated 3.3 %) iodine number: O
The reaction product consequently cons:Lsted o f about - 20 94 ~0 o~ epoxides. The conversion was 100 ~0 and the yield. of epoxide conse~uently about 94 ~o, E X A M P ~ E 12:
.~
In the manner of example 1 a solution of 940 g of an alkene ~raction having of from 26 to 52 carbon atoms 7 the olefinic double bonds whereof exGlusively had a tra~s-vinyl-ene structure (a~erage molecular weight 4709 iodins number 45) i~ 3760 g of chloroform was reacted with a mix~ure o f 120 g of glacial ac~ti~ acid9 260 g of 34 ~0 hydrogen peroxide and 12 g 29 of 50 G~o sulfuric acid for 16 hours at a temperature of :fro~
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60 to 65C, 9~4 g of epoxide mix-ture having from 26 to 52 car-bon atoms were obtclined in the forrn of a wilite waxy product~
oxygen con-ten-t of oxlrane: 300 ~ (salculated 3.3 %) iodine number: 1.2 The react.ion product consequently consisted of about 91 %
of epoxides o~ the olefln mixture haviIlg from 26 to 52 carbon atoms and o~ about 3 ~0 o~ unreacted olefins; conversion about 9'7 ~ and yield about 94 %.
X A M P L E 13:
The apparatus described in example 1 was charged with 700 g of decene~1(iodine number 177~1) 9 2100 g of chloroform and 70 g of a catio~ exch-anger resln based on styrene divinyl ben~
æene activated with a 6 ~ hydrochloric acid.Thereaf-ter a mix~
ture o~ 150 g of glacial acetic acid and 600 g of ~4 ~ H202 was added within 5 mi~utes and the reaction mixture was heated to 60 to 62~C and stirred at this temperature for 18 hoursO
A~ter cooling the exchanger resin was filtered off~ the aqueous layer was seParated from the chloroform layer and the crude 102 -epoxydodeoane was isolated.
`~ 20 yleld: 772 g o~ liquid clear product oxygen content of oxirane: 9.9 % (theory 10.3 %) iodine number: 8.9 The reaction product co~sequently consisted of 96 % of the desired epoxide and of 5 % unreacted olefin; conversion 95 %9 ; 25 yleld~about 99 %~
I' X ,~
As described in example 13~ 940 g o~ the alkene frac-tion used in example 9, 3760 g of chloro~orm a~d 94 g of activated : .
;` 29 excha~ger resin were reacted with a mix-~ure of 120 g of gla-~
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cial acetic acid and 260 g of 34 ~ H202 for 2U hours at a tem-perature of fro~ 60 to 65C. 962 g of epoxide mixture were ob tained in the form of a white wa~.
oxygen conten-t of oxirane: 3.0 ~0 calcula-ted 3~3 ~) iodine number: 0 It may be calcula-ted therefrom -tha-t -the epoxide content 9 the conversion an~ the yield respective:ly were 91 ~.
E X A M P L E 15:
102 g of ace-tic acid anhydride were introduced into the apparatus described i~ example 1.440 g of 34 ~ H~02 were added within 30 minutes while stirring~the reaction mixture was hea-ted to 40C and again stirred a-t this tempera-ture for 1.5 hou~0 After having added 12 g of 50 % sulfuric acid~ 1800 g of chlo~
ro~orm and 672 g of dodecene-1 (iodine ~ber 149.6)~ stir-ring was carried our for 6 hours at a tempera-ture of from 60 to 62C, the reaction mixture was then cooled ~nd worked up as de~
cribed in example 1.
yield: 730 g of crude 1.2-epoxydodecane - oxygen content of oxirane: 8.0 _20 lodine number: 7.5 epoxide conte~t about 92 %9 conversion about 95 %3yield of epo-xide about 97 ~.
E_X A M P ~ E 16:
900 g of the mixture of alkenes having from 26 to 52 carbon -2~ atoms as used in example 9 were dissolved ln 2100 g of chloro~
form and epoxidation was then carried out with a mixture of 22Q g of 34 % ~22s 51 g of ac~tic acid anhydride and 60 g of acetic acid whi~h had been kept ~or 1 hour at 40C, i~ t~e pre-29 sence of 12 g o~ 50 ~ su1furic ac.id ~or 4 hours a-t a tempera-~: . ' . -~ - . . . . .

: . . . . . . . ......... . . . . .

J~
ture of from 60 to 63C. A~ter working up 930 g o:~ epoxide mixture were obtained having an oxygen conten-t of o~irane of 20 9 ~ and a iodine number of 1.8.
epoxide content about 88 ~ con~ersion abo-l~ 96 %, yield about 92 %.

Claims (4)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for the preparation of an oxirane of a straight chain or little branched mainly terminal ethylenically unsaturated hydrocarbon having from 8 to 60 carbon atoms in the molecule, in which the hydrocarbon is epoxidized at a temperature in the range of from 50 to 80°C with an oxidation mixture con-sisting of (a) acetic acid, acetic acid anhydride or a mixture thereof and (b) aqueous hydrogen peroxide, in the presence of an acidic catalyst selected from the group consisting of mineral acids, ethane sulfonic acid and cationic exchanger resins in the H+ form and the catalyst is present in an amount of from 1 to 3% by weight calculated on the oxidation mixture, and in an inert chlorinated hydrocarbon solvent, which is liquid under the reaction conditions, having 1 to 3 carbon atoms and at least one of the carbon atoms is present in the form of a -CCl3-, -CHCl2 or =CCl2 group, the proportion by weight of ethylenically unsaturated hydrocarbons to solvent being from 1:1 to 1:50.

2. A process as claimed in claim 1 in which the sol-vent is selected from the group consisting of chloroform, 1,1,2-trichloroethane, 1,1,1-trichloroethane , 1,1,1,2-tetra-chloroethane, 1,1,2,2-tetrachloroethane, tetrachloroethylene, pentachlorethylene and mixtures thereof.

3. A process as claimed in claim 1 in which the sol-vent is chloroform.

4. A process as claimed in claim 1, claim 2 or claim 3 in which the proportion of hydrocarbon to solvent is in the range of from 1:2 to 1-6.