DE2734085A1 - PROCESS FOR THE PREPARATION OF HALOGENALKYL SUBSTITUTED OXIRANS - Google Patents

Description

SILBERBAYER AG · GERMAN GOLD AND

5090 Leverkusen SCHEIDEANSTALT formerly ROESSLER

6000 Frankfurt / M.

Leverkusen / Frankfurt, the

Dz / AD

Process for the production of halogenated alkyl is substituted oxiranes

The prior invention relates to an improved method oxiranes are used to produce ha lcxjena lky lsubs halogenated alkyl-substituted olefins and percarboxylic acids.

Halogena 1 ky lsubs tied oxiranes are used in the field of paints and plastics and as organic intermediates.

It is known to produce chlorohydrin-substituted oxiranes from the corresponding olefins by the chlorohydrin process. This process has the disadvantage that undesired chlorinated by-products and environmentally harmful salt waste are formed (Ulimanns Encyklopadie d. Techn. Chemie, Hd. 10, p. 565, left column, Ze i Ie 1 £ f., In particular 5.11- 15; DAS 1 51J 174, column 2, lines 15 ff., In particular \. J2-J5).

It is also often difficult to produce a single reaction product in a defined manner using the chlorohydrin method. The reaction of 4-chlorobutene- (2) with hypochlorous Le A 17 775 /
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Acid to a mixture of two products, which are characterized by the following formulas:

OH Cl Cl Cl OH Cl

CH ₃ -CH-CH-CH ₂ and CH ₃ -CH-CH-CH ₂

Accordingly, subsequent dehydrohalogenation of this mixture with a base provides a mixture of two isomers Oxiranes, as illustrated by the following formulas (DAS 1 056 596, column 1, line 53 to column 2, 3-43):

0 Cl Cl 0

CH ₃ -CH-CH-CH ₂ and CH ₃ -CH-CH-CH ₂

It is also known to convert olefins into the corresponding oxiranes with the aid of a percarboxylic acid. (N. Prileschajew, Ber. German Chem. Ges. 42, 4811 (1909)).

This reaction is an electrophilic attack by the oxidizing agent on the olefin. (K.D. Bingham, G.D. Meakins, G.H. Whitham, Chem. Commun. (1966, p and 446).) For this reason, the reactivity of the olefin decreases with decreasing nucleophilicity of the double bond. That's why complicate electronegative substituents in the A position to C = C double bond epoxidation. (S.N. Lewis in R.L. Augustin, "Oxidation", Vol. I, p. 227, in particular S. 227, 3. 9-13, Marcel Dekker, New York (1969).) Haloalkyl-substituted olefins can therefore be combined with percarboxylic acids do not simply epoxidize. As a result of the low reactivity of their double bond, temperatures are high and long reaction times are required, which leads to the formation of undesired by-products such as dihydroxy and hydroxyacyloxy derivatives of the starting materials

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gives. (S. N. Lewis in R. L. Augustin, "Oxidation", Vol. I, page 233, especially 3. 6-11, Marcel Dekker, New York 1969).

This is particularly the case with regard to the type and implementation of the reaction between a haloalkyl-substituted Olefin and a percarboxylic acid, the structure and method of preparation of the percarboxylic acid used is of great importance.

It is known that lower aliphatic percarboxylic acids can be obtained from carboxylic acid in an equilibrium reaction and produce hydrogen peroxide according to equation (1). (D. Swern, in "Organic Peroxides", Vol. 1, p. 61, Wiley Intersciense 1971)

RCOOH + H ₂ O ₂ <« RCOOOH + H ₃ O (1)

With the exception of stronger carboxylic acids such as formic acid and trifluoroacetic acid, this is required for quick adjustment strong acids, such as sulfuric acid, p-toluenesulfonic acid and others, act as catalysts (S.N. Lewis in R.L. Augustin "Oxidation", Vol. I, p. 216 ("C. Peracids"), Marcel Dekker, New York 1969). The implementation of olefins with z. B. peracetic acid produced by this method did not lead to oxiranes, but to dL glycols and hydroxyacetates (J. Böseken, W. C. Smit and Gaster, Proc. Acad. May be. Amsterdam, 3_2 377-38 3 (1929).) The mineral acid present in the reaction mixture catalyzes the splitting of the primarily formed oxirane (D. Swern "Organic Peroxides", Wiley Intersciense 1971, Vol. 2, p. 4 36), which is particularly important in the case of poorly reactive olefins, such as Haloalkyl-substituted olefins, whose conversion requires high temperatures and long reaction times, lead to oxirane losses can lead.

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Performic acid can be prepared from hydrogen peroxide and formic acid without an additional catalyst (S.N. Lewis in R. L. Augustin, "Oxidation", Vol. I, p. 217, first paragraph, Marcel Dekker, New York 1969). The implementation of «T-chloroalkyl-substituted olefins with this mineral acid-free However, percarboxylic acid only gave the corresponding epoxide in low yields. So became epoxidation of 3,4-dichlorobutene- (1) one of 90% formic acid Performic acid made from 85% hydrogen peroxide is used. After a reaction time of five hours at 60 ° C was 2- (1,2-dichloroethyl) oxirane in 30% strength Yield obtained (E. G. E. Hawkins, J. Chem. Soc., 1959 pp. 248 to 256, especially p. 250, line 19).

More recently there is a method of making aliphatic Chlorine epoxides by reaction of an allyl chlorohydrocarbon, which has a chlorine atom in the vicinity to the double bond, with an organic per-compound that is free of inorganic impurities, became known (DAS 1 056 596). The per compounds used are "pure peracetic acid, perpropionic acid or acetaldehyde monoperacetate mixed with acetaldehyde and / or acetone ". (DAS 1 O56 596, column 10, lines 32-35.) The epoxidation according to the method of DAS 1 056 596 of allyl-substituted olefins with acetaldehyde monoperacetate provides the corresponding oxiranes in yields based on the per compound between 17% depending on the olefin and 56%. (DAS 1 056 596, columns 5 to 7, lines 35 ff., Examples 1, 3, 4 and 6).

The peracetic acid and perpropionic acid used for epoxidation in this process are dissolved in an inert one

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organic solvents are used. As described elsewhere, this process can be considered to be typical inert Solvents including acetone, ethyl acetate, butyl acetate and dibutyl ether can be used (US-P. 3,150,154, Column 3, lines 1-3).

With the peracids prepared according to the method of DAS 1 056 596, allylchlorohydrocarbons can be epoxidized; however, the yields of oxiranes are low; the peracid conversion is incomplete. It amounts to in the specified Examples only about 90% and the purity of the isolated oxiranes is insufficient for industrial use. Thus, in DAS 1 056 596 in Example 5, column 7, line 5 ff., The epoxidation of 3-chloro-1-butene with a solution of peracetic acid in acetone. The peracid conversion after a reaction time of ten hours is 91%. The oxirane is isolated with a purity of 90.5% in 68% yield.

In the Brit. PS 784 620 is described in Example VII, page 7, line 5 ff., The preparation of 3,4-dichloro-1,2-epoxybutane by reacting 3,4-dichloro-1-butene with peracetic acid in acetone. Thereafter, the peracid conversion is 89 % and the epoxide yield is 7.5%. The purity of the epoxy is given as 93.3%. In the Brit. PS 784 620 is also reported in Example IX, page 7, line 85 ff. On the epoxidation of an olefin with perpropionic acid. Thereafter, after the reaction of crotyl chloride with a solution of perpropionic acid in ethyl propionate, 1-chloro-2,3-epoxybutane was obtained in 56% yield. The peracid conversion was 90%.

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In contrast, it has now been found that haloalkyl-substituted oxiranes can be used from haloalkyl-substituted olefins and percarboxylic acids in organic solution in high yields and high purity can produce if you have a chloroalkyl or bromoalkyl-substituted monoolefin of the general formula

R ₂ ^R 3
R ₁ -C = CR _{4 t} (I)

R ₁ and R ₄ independently of one another are hydrogen,

C ₁ - to C ₅ -alkyl, C ₅ - to Cj-cycloalkyl, MOnOChIOr-C ₁ to C, - alkyl, monobromo-C ₅ ~ Cjbis alkyl, dichloro-C ₁ - to Cj-alkyl, dibromo-C ..- to Cc-alkyl, monochloro-C, .- to Cy-cycloalkyl, monobromo-Cg- to C ₇ -cycloalkyl, dichloro-Cg- to C ₇ -cycloalkyl, dibromo-C ₅ ~ to C ₇ -cycloalkyl
mean,

R- and R, independently of one another, represent hydrogen, C ₁ - to Cc-alkyl, monochloro-Cj- to C ₅ -alkyl, monobromo-C ^ to Cg-alkyl, dichloro-C ₁ -to Cc-alkyl and dibromo-C ^ to C ₅ alkyl, the radicals

R5 and R ₃ together with the carbon atoms of the C = C double bond form a ring with up to 12 carbon atoms
can,

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and where at least one of the radicals R- to R _- J is an alkyl or cycloalkyl radical of the type mentioned containing chlorine or bromine,

reacting 1 and at a temperature of 30 ⁰ C to 100 ⁰ C with a solution of 3 percarboxylic to 4 carbon atoms containing in a chlorinated, from 1 to carbon atoms-containing hydrocarbon at a molar ratio of monoolefin to Percabonsäure such as 1,1 to 10th

A chloroalkyl- or bromoalkyl-substituted monoolefin with at least 4 carbon atoms is preferably used.

In the context of the compounds of the formula (I), for example, compounds of the following formulas are particularly useful into consideration:

R ₅ -CH = CH-R ₆ , ^(II)

wherein

R and R ₆ independently of one another Cj to C ₅ ~ alkyl,

MOnOChIOr-C ₁ - to C ₅ -alkyl, monobromo-C, - to C ₅ -alkyl, DiChIOr-C ₁ - to C ₅ ~ alkyl or dibromo-C, - to C ₅ ~ alkyl,

where the radicals R ₅ and R _g can be linked together with the group CH = CH to form a ring,

and where at least one of the radicals R ₅ and R ₆ MOnOChIOr-C ₁ - to C ₅ ~ alkyl, monobromo

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C ₁ - to C ₅ -alkyl, dichloro-C, - to C ₅ -alkyl or dibromo-Cj- to C ₅ -alkyl;

(III)

R ₇ and Rq independently of one another are hydrogen / C ..- to C ₅ ~ alkyl, MOnOChIOr-C ₁ - to Cg-alkyl, monobromo-C ^ to C ₅ -alkyl, DiChIOr-C ₁ - to C ₅ -alkyl or dibromo -C ..- to C ^ -alkyl,
Rq and R ₁₀ independently of one another are a methylene,

Chloromethylene, bromomethylene, 1,2-dichloro

ethylene or 1,2-dibromomethylene radical

represent,

stands for an integer from 1 to 6,

and where at least one of the radicals R ₇ R _{10 is} a chlorine or bromine-containing alkyl, cycloalkyl or alkylene radical of the type mentioned.

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The following are specifically mentioned as haloalkyl-substituted monoolefins:

2-chloromethyl-propene, S-chloro - ^ - chloromethyl-propene, 3-chloro-1-butene, i-chloro-2-butene, 1,4-dichloro-2-butene, 3,4-dichloro-1-butene, 3-chloro-i-pentene, 4-chloro-2-pentene, 1-chloro-2-pentene, 1,4-dichloro-2-pentene, 3,4-dichloro-1-pentene, 1,2-dichloro-3-pentene, 3-chloro-1-cyclopentene, 1,4-dichloro-2-cyclopentene, 3-chloro-1-hexene, 1-chloro-2-hexene, 1,4-dichloro-2-hexene, 3,4-dichloro-1-hexene, 2-chloro-3-hexene, 2,5-dichloro-3-hexene, 3-chloro-i-cyclohexene, 1,4-dichloro-2-cyclohexene, 1-chloro-2-hepten, 3-chloro-1-hepten, 3,4-dichloro-1-hepten, 1,4-dichloro-2-hepten, 2-chloro-3-hepten, 2,5-dichloro-3-hepten, 3-chloro-1-cycloheptene, 1,4-dichloro-2-cycloheptene, 1-chloro-2-octene, 3-chloro-1-octene, 1,4-dichloro-2-octene, 2,5-dichloro-3-octene, 2-chloro-3-octene, 3-chloro-4-octene, 3,6-dichloro-4-octene, 3-chloro-1-cyclooctene, 1,4-dichloro-2-cyclooctene, 1- (1-chloro-cyclohexyl) -ethene, 1-chloro-2-nonene, 3-chloro-1-nonene, 1,4-dichloro-2-nonene, 2-chloro-3-nonene, 2,5-dichloro-3-nonene, 3-chloro-4-nonene, 6-chloro-4-nonene, 3,6-dichloro-4-nonene, 1-chloro-3-decene, 3-chloro-1-decene, 4-chloro-2-decene, 1,4-dichloro-2-decene, 2-chloro-3-decene, 2,5-dichloro-3-decene, 5-chloro-3-decene, 6-chloro-4-decene, 3,6-dichloro-4-decene, 4-chloro-5-decene, 4,7-dichloro-5-decene, 1-chloro-3-undecene, 3-chloro-1-undecene, 1,4-dichloro-2-undecene, 2-chloro-3-undecene, 4-chloro-2-undecene, 2,5-dichloro-3-undecene, 5-chloro-3-undecene, 6-chloro-4-undecene, 4-chloro-5-undecene, 4,7-dichloro-5-undecene, 5-chloro-6-undecene, 5,8-dichloro-6-undecene, 1-chloro-3- dodecen, 3-chloro-1-dodecene, 1,4-dichloro-2-dodecene, 2-chloro-3-dodecene, 4-chloro-2-dodecene, 2,5-dichloro-3-dodecene, 5-chloro-3-dodecene, 6-chloro-4-dodecene, 4-chloro-5-dodecene, 4,7-dichloro-5- dodecen, 5-chloro-6-dodecene, 5,8-dichloro-6-dodecene, 5,7-dichloro-6-dodecene, 7-chloro-5-dodecene; 2-bromomethyl-propene, 3-bromo-2-

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bronunethyl propene, 3-bromo-1-butene, 1-bromo-2-butene, 1,4-dibromo-2-butene, 3,4-dibromo-1-butene, 3-bromo-i-pentene, 4-bromo-2-pentene, 1-bromo-2-pentene, 1,4-dibromo-2-pentene, 3,4-dibromo 1-penten, 1,2-dibromo-3-pentene, 3-bran-i-cyclopentene, 1,4-dibromo-2-cyclopentene, 3-bromo-1-hexene, 1-bromo-2-hexene, 1,4-dibromo-2-hexene, 3,4-dibromo-1-hexene, 2-bromo-3-hexene, 2,5-dibromo-3-hexene, 3-bromo-i-cyclohexene, 1,4-dibromo-2-cyclohexene, i-bromo-2-hepten, 3-bromo-1-hepten, 3,4-dibromo-1-hepten, 1,4-dibromo-2-hepten, 2-bromo-3-hepten, 2,5-dibromo-3-hepten, S-bromo-i-cycloheptene, 1,4-dibromo-2-cycloheptene, 1-bran-2-octene, 3-bromo-1-octene, 1,4-dibromo-2-octene, 2,5-dibromo-3-octene, 2-bromo-3-octene, 3-bromo-4-octene, 3,6-dibromo-4-octene, S-bromo-i-cyclooctene, 1,4-dibromo-2-cyclooctene, 1- (1-bromo -cyclohexyl) -ethene, 1-bromo-2-nonene, 3-bromo-1-nonene, 1,4-dibromo-2-nonene, 2-bromo-3-nonene, 2,5-dibromo-3-nonene, 3-bromo-4- nuns, 6-bromo-4-nonene, 3,6-dibromo-4-nonene, 1-bromo-3-decene, 3-bromo-1-decene, 4-bromo-2-decene, 1,4-dibromo-2- decen, 2-bran-3-decen, 2, S-dibromo-S-decene, 5-bromo-3-decene, 6-bromo-4-decene, 3,6-dibromo-4-decene, 4-bromo-5-decene, 4,7-dibromo-5-decene, 1-bromo-3-undecene, 3-bromo-1-undecene, 1,4-dibromo-2-undecene, 2-bromo-3-undecene, 4-brcin-2-undecene, 2,5-dibromo-3-undecene, 5-brcin-3-undecene, 6-bromo-4-undecene, 4-bromo-5-undecene, 4,7-dibromo-5-undecene, S-Brcxn-G-undecene, 5,8-dibromo-6-undecene, 1-bromo-3- dodecen, 3-bromo-i-dodecene, 1,4-dibromo-2-dodecene, 2-bromo-3-dodecene, 4-bromo-2-dodecene, 2, S-dibromo-S-dodecene, 5-bromo-3-dodecene, 6-bromo-4-dodecene, 4-bran-5-dodecene, 4,7-dibromo-5-dodecene, S-Brcan-6-dodecen, S ^ -dibrom-e-dodecen, 5,7-dibromo-6-dcx3ecene, 7-bromo-5-dodecene.

Particularly suitable for the reaction with percarboxylic acids according to the process according to the invention are chloroalkyl- or bromoalkyl-substituted Monoolefins of the formula

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R ₁₁ -CH = CH-R ₁₂ , (IV)

R ₁₁ and R ₁₂ independently of one another are hydrogen, C ₁ - to C ₅ -alkyl, MOnOChIOr-C ₁ -bis Cc-alkyl, monobromo-Cj- to C ₅ -alkyl, DiChIOr-C ₁ - bis or dibromo-C .. - to Cc mean

where at least one of the radicals R ₁ . and R _{12 stands} for MOnOChIor-C ₁ - to Cc-alkyl, monobromo-C- to Cc-alkyl, DiChIor-C ₁ - to C ₅ -alkyl or dibromo-Cj- to Cg-alkyl.

Examples include: 2-chloromethyl-propene, 3-chloro-2-chloromethyl-propene, 3-chloro-1-butene, 1-chloro-2-butene, 1,4-dichloro-2-butene, 3,4-dichloro-1-butene, 3-chloro-i-pentene, 4-chloro-2-pentene, 1-chloro-2-pentene, 1,4-dichloro-2-pentene, 3,4-dichloro-i-pentene, 1,2-dichloro-3-pentene, 3-chloro-1-hexene, 1-chloro-2-hexene, 1,4-dichloro-2-hexene, 3,4-dichloro-1-hexene, 2-chloro-3-hexene,

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2,5-dichloro-3-hexene, S-chloro-i-cyclohexene, 1,4-dichloro-2-cyclohexene; Allyl bromide, 2-bromoethyl-propene, 3-bromo-2-bromomethyl-propene, 3-bromo-1-butene, 1-bromo-2-butene, 1,4-dibromo-2-butene, 3,4-dibromo-1-butene, 3-bromo-1-pentene, 4-bromo-2-pentene, 1,4-dibromo-2-pentene, 3,4-dibromo-1-pentene, 1 ^ -dibromo-S-pentene, 3-bromo-1-hexene, 1-bromo-2-hexene, 1,4-dibromo-2-hexene, 3,4-dibromo-1-hexene, 2-bromo-3-hexene, 2,5-dibromo-3-hexene, 3-bromo-1-cyclohexene, 1,4-dibromo-2-cyclohexene.

Reacting with percarboxylic acids according to the process according to the invention are very particular 1,4-dichloro-2-butene, 1,4-dibromo-2-butene and 3,4-dichloro-1-butene is suitable.

A wide variety of chlorinated hydrocarbons can be used as solvents, such as methylene chloride, chloroform, carbon tetrachloride, 1-chloroethane, 1,2-dichloroethane, 1,1-dichloroethane, 1,1,2,2-tetrachloroethane, 1-chloropropane, 2-chloropropane, 1,2-dichloropropane, 1,3-dichloropropane, 2,3-dichloropropane, 1,2,3-trichloropropane, 1,1,2,3-tetrachloro

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propane, butyl chloride, 1,2-dichlorobutane, 1,4-dichlorobutane, 2,3-dichlorobutane, 1,3-dichlorobutane, 1, 2,3,4-tetrachlorobutane, tert. Butyl chloride, amyl chloride, 1,2-dichloropentane, 1,5-dichloropentane, 1,2,3,4-tetrachloropentane, cyclopentyl chloride, 1,2-dichlorocyclopentyl chloride, hexyl chloride, 1,2-dichlorohexane, 1,6-dichlorohexane, 1,2,3,4-tetrachlorohexane, 1,2,5,6-tetrachlorohexane, Cyclohexyl chloride, 1,2-dichlorohexane, chlorobenzene, Heptyl chloride, 1,2-dichloroheptane, 1,2,3,4-tetrachloroheptane, Cycloheptyl chloride, 1,2-dichlorheptane, octyl chloride, 1,2-dichloroctane, 1,2,3,4-tetrachloroctane, cyclooctyl chloride, and 1,2-dichloroctane.

Preferred solvents are methylene chloride, chloroform, carbon tetrachloride and 1,2-dichloropropane. Particularly the preferred solvent is 1,2-dichloropropane. Solvent mixtures of chlorinated hydrocarbons can also be used .

Peracids which can be used according to the invention are perpropionic acid, Perbutyric acid and perisobutyric acid. Used with preference become perpropionic acid and perisobutyric acid. Perpropionic acid is particularly preferred. The production of the mineral acid-free Peracids in one of the organic solvents mentioned can, for. B. after that described in DOS 2,262,970 Procedure.

In general, the process according to the invention is carried out in practice in a temperature range from 30-100 ° C. It is preferred to work at 60-80 ° C., especially preferably at 65-75 ° C. In special cases, the specified temperatures can also be exceeded or not reached.

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In addition to working under isothermal conditions, i. H. Maintaining a uniform temperature throughout Reaction mixture, the reaction can also be carried out with the formation of a so-called temperature gradient, which generally increases as the reaction proceeds. But one can also lead the reaction in such a way that it deals with the As the reaction progresses, a gradient of falling temperature forms.

According to the invention, the molar ratio of olefin to peracid is 1.1: 1 to 10: 1. A molar ratio is preferred from 1.25: 1 to 5: 1 applied. It is particularly advantageous to have a molar ratio of 1.5 to 3.0 mol of olefin each McI peracid to apply.

The process according to the invention can be carried out at a wide variety of pressures. Generally one works at Normal pressure; however, the process can also be carried out under negative or positive pressure.

The water content of the percarboxylic acid used for the epoxidation should generally be as low as possible. Low Amounts of water up to 5% by weight are generally not troublesome. For example, a percabonic acid with a is suitable Water content of up to 2% by weight. A percarboxylic acid solution is preferably used which contains less than 1% by weight of water contains. A water content of less than 0.1% by weight is particularly preferred.

The hydrogen peroxide content of the percarboxylic acid used should generally be as low as possible. He can go up to

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2% by weight. It is advantageous to work with a salary less than 1% by weight. It is particularly advantageous that the Carry out reaction with a percarboxylic acid solution which has a hydrogen peroxide content below 0.3%.

The mineral acid content of the percarboxylic acid solution used for conversion should be as low as possible. It is advantageous to carry out the reaction with a percarboxylic acid solution, which has a mineral acid content below 50 ppm. A mineral acid content is particularly advantageous less than 10 ppm.

The reaction can be carried out batchwise or continuously in the manner customary for reactions of this type Of ichtuiigen such as agitator vessels, boiler reactors, tube reactors, Loop reactors or loop reactors take place.

Glass, stainless steel or enamelled material can be used as materials for carrying out the process.

Heavy metal ions in the reaction mixture catalyze the decomposition of the percarboxylic acid. Substances are therefore generally added to the percarboxylic acid solution which inactivate the heavy metal ions by forming complexes. Known substances of this type are gluconic acid, ethylenediaminetetraacetic acid, sodium silicate, sodium pyrophosphate, sodium hexametaphosphate, disodium dimethyl pyrophosphate or Na ~ (2-ethylhexyl) ₅ (P ₃ 0 ₁₀ ) ₂ (DAS 1 056 596, column 4, line 60 ff.).

The haloalkyl-substituted olefin can be various Kind introduced into the device used for the implementation

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will. It can be used together with the percarboxylic acid solution give into the reactor or the two components are fed to the reactor separately from one another. It is also possible to pass the olefin and the percarboxylic acid solution into the reactor unit at different points. When using multiple For reactors connected in cascade, it may be advisable to introduce all of the olefin into the first reactor. However, the olefin can also be divided between the various reactors.

The heat of reaction is dissipated through internal or external coolers. To dissipate the heat of reaction, the Implementation can also be carried out under reflux (boiler reactors).

The reaction is expediently as complete as possible Implementation of the percarboxylic acid made. In general, more than 95 mol% of the percarboxylic acid is converted. It is expedient to convert more than 98 mol% of peracid.

When carrying out the reaction according to the invention between the haloalkyl-substituted olefin and the peracid succeed in oxirane yields of 90% of theory and above, based on on the percarboxylic acid used.

The reaction mixture is worked up in a manner known per se, for. B. by distillation. Particularly beneficial is to the reaction mixture before the distillative work-up to separate the formed in the reaction, to extract the carboxylic acid corresponding to the percarboxylic acid with water. The extraction can be carried out in the

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common extractors, such as mixer-separators, sieve floor extractors, pulsating sieve tray columns, rotary disk extractors or extraction centrifuges are carried out.

In a preferred implementation of the process, an approximately 20% strength by weight perpropionic acid solution in 1,2-dichloropropane is added with stirring to the three-fold molar amount of haloalkyl-substituted olefin which is thermostatted to 70.degree. The perpropionic acid solution contains less than 10 ppm mineral acid; it has a water content below 0.1% and a hydrogen peroxide content of less than 0.3%. To complex heavy metal ions, about 0.05% by weight of Na ₅ (2-ethylhexyl) "( ^P 3 ° i ₀ ) 2 was added to the perpropionic acid before the reaction. The progress and the end of the reaction are monitored by taking samples from the reaction solution at regular intervals and titrimetrically determining the amount of percarboxylic acid that is still present. After the reaction has ended, the co-action rubber is cooled and washed three times with the same amount by weight of water to remove the propionic acid. The propionic acid-free reaction mixture is then fractionated.

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The following examples illustrate the invention. All Unless otherwise stated, percentages represent percentages by weight.

example

Production of 2- (1,2-dichloroethyl) oxirane from 3,4-dichloro-1-butene and perpropionic acid.

62.96 g (0.147 mol) of perpropionic acid were added dropwise to 55.87 g (0.447 mol) of 3,4-dichloro-1-butene at 70 ° C. while stirring
21% solution in 1,2-dichloropropane. After being added dropwise
Stirred for a further 6 hours at this temperature, then the titrimetric analysis showed a perpropionic acid conversion of 95%. The reaction solution was cooled to room temperature and analyzed by gas chromatography. As the analysis showed, 2- (1,2-dichloroethyl) oxirane was formed with a selectivity, based on the perpropionic acid used, of 92.6%.

The reaction mixture was washed several times with water to remove the propionic acid, 1,2-dichloropropane was distilled off and then in a 40 cm packed column,
filled with 4 mm glass Rasching rings, fractionated. There were 18.5 g of 2- (1,2-dichloroethyl) - oxirane with a purity
of 99.4% isolated.

Example 2

Production of 2,3-bis (chloromethyl) oxirane from 1,4-dichloro-2-butene and perpropionic acid.

To 55.2 g (0.4416 mole) of 1,4-dichloro-2-Buton were incubated at 70 ⁰ C

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63.97 g (0.147 mol) of perpropionic acid were added dropwise as an approx. 20% solution in 1,2-dichloropropane and then with this Temperature continued to stir. After a reaction time of 4 hours, the peracid conversion was 94%, after 6 hours it was over 97%. 2,3-bis (chloromethyl) oxirane was produced with a selectivity based on perpropionic acid used, formed by 94%. After removing the propionic acid by shaking it out several times the reaction mixture with water and then separating off 1,2-dichloropropane by distillation After fractionation through a 30 cm packed column filled with 4 mm glass Raschig rings, 19.0 g of 2,3-bis (chloromethyl) oxirane were obtained obtained with a purity of 99.9%.

Example 3

Continuous production of 2,3-bis (chloromethyl) oxirane from 1,4-dichloro-2-butene and perpropionic acid.

A solution of perpropionic acid in 1,2-dichloropropane, the with a stabilizer of the type of the commercially available sodium salts of partially esterified with long-chain alcohols Polyphosphoric acids are mixed with 1,4-dichloro-2-butene in a three-stage stirred tank cascade trained reaction system implemented. Each of the three stirred kettles had a volume of 9.4 1. The heating of the The boiler took place via heating coils installed in the boiler. All three kettles were thermostatted to 70 ° C.

To this reaction system, 2,137.5 g of perpropionic acid was added per hour as a 20% solution in 1,2-dichloropropane (4.75 mol)

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and 1,781.25 g (14.25 mol) 1,4-dichloro-2-butene fed, which corresponded to an average residence time of about 8 hours. Under these reaction conditions, the perpropionic acid 94.2% implemented. The selectivity of the 2,3-bis (chloromethyl) oxirane formed was 92%, based on the amount used Perpropionic acid.

The reaction mixture obtained after the third reactor had the following composition on average: 35.6% 1,2-dichloropropane, 31.4% 1,4-dichloro-2-butene, 15.7% 2,3-bis (chloromethyl) -oxirane and 17% propionic acid. This mixture was used to separate off the propionic acid in a pulsating sieve tray column extracted with twice the amount of water. Thereafter, the residual propionic acid content was less than 0.1%. The reaction mixture obtained after this operation was separated in a distillation line. In a first Column was 1,2-dichloropropane in an amount of 1,395 g distilled off per hour. The bottom product of this column, which essentially consisted of starting product and oxirane, was separated in a second column under reduced pressure. The top product was 1,235 g of 1,4-dichloro-2-butene per hour obtain. The bottom product of this column was in a third column under reduced pressure of high boilers freed. The top product per hour was 606 g of 2,3-bis (chloromethyl) oxirane with a purity of over 99.9% obtain. This corresponds to a yield of 90.5%, based on the perpropionic acid used in the reaction system.

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Example 4

Production of 2,3-bis (bromomethyl) oxirane from 1,4-dibromo-2-butene and perpropionic acid.

a) Bromination of butadiene

171.4 g (3.17 mol) of butadiene were dissolved in 400 ml of η-hexane. At -20 ° C., 314 g (1.964 mol) of bromine were added dropwise with stirring. After the end of the dropping, 2 hours were left stirred at this temperature. The mixture was then allowed to warm to room temperature and the solvent was removed in a vacuum. This gave 380.4 g of crude dibromobutene, the ratio of 1,4-dibromo-2-butene to 3,4-dibromo-1-butene was about 2: 1. The 1,4-dibromo-2-butene was isolated by distillation.

b) Reaction of 1,4-dibromo-2-butene with perpropionic acid

-Dibromo-1,4 butene-2 to 64.2 g (0.3 mol) was added at 70 ⁰ C with stirring, 45 g 20% perpropionic acid in 1,2-dichloropropane (0.1 mol) was dropped and further 4 Stirred for hours at this temperature. After this time, the peracid conversion was 93%. The gas chromatographic analysis showed that 2,3-bis (bromomethyl) oxirane were formed with a selectivity of 90.8%, based on the perpropionic acid used. After cooling, the reaction mixture was washed several times with water and fractionated to remove the propionic acid. 20.3 g of 2,3-bis (bromomethyl) oxirane were obtained.

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Claims (1)

Claims 1J Process for the preparation of haloalkyl-substituted Oxiranes from haloalkyl-substituted olefins and percarboxylic acids, characterized in that a chloroalkyl or bromoalkyl-substituted monoolefin of the general formula ? 3 R ₁ -C = CR ₄ wherein R ₁ and R ₄ independently of one another are hydrogen, C ₁ - to Cg-alkyl, C ₅ - to ^ -cycloalkyl, monochloro-Cj- to Cc-alkyl, monobromo-C ..- to C ₅ -alkyl, DiChIOr-C ₁ - to C ₅ ~ alkyl, dibromo- Cj- to Cj-alkyl, monochloro-C ₅ ~ to C ^ -cycloalkyl, monobromo-C ^ - to C ₇ -cycloalkyl, dichloro-Cj- to ^ -cycloalkyl, dibromo-Cg- to C ^ -cycloalkyl, R2 and R ₃ independently of one another for hydrogen, C ₁ - to Cj-alkyl, MOnOChIOr-C ₁ - to C ₅ -alkyl, monobromo-C ₁ - to Cc-alkyl, dichloro-C ₁ - to Cj-alkyl and dibromo C ^ to C ₅ -alkyl, the radicals R2 and R, together with the carbon atoms of the C * C double bond, form a ring with up to 12 carbon atoms can. Le A 17 775 - 22 - 009808 / $ 002 and where at least one of the radicals R ₁ to R4 is a chlorine or bromine- containing alkyl or cycloalkyl radical of the type mentioned , with a solution of a percarboxylic acid containing 3 to 4 carbon atoms in a chlorinated hydrocarbon containing 1 to 8 carbon atoms at a molar ratio of monoolefin to percarboxylic acid of 1.1 : 1 to 10 : 1 and at a temperature of 30 ° C to 100 ° C . 2. The method according to claim 1, characterized in that there is used as a chloroalkyl or bromoalkyl-substituted monoolefin an olefin of the formula R _C -CH = CH-R, D D wherein
R5 and independently of one another C ₁ - to C ₁ -MonOChIor-C ₁ -to C ₅ -alkyl, monobromo-C ..- to C ₅ -alkyl, DiChIor-C ₁ - to C ₅ -alkyl or dibromo-C ..- to Mean C ^ -alkyl, where the radicals R ₅ and R _g can be linked together with the group CH = CH to form a ring, and where at least one of the radicals R ₁ . and Rg is MOnOChIOr-C ₁ - to C ₅ -alkyl, monobromo-C ^ to C ^ -alkyl, dichloro-C ..- to C ₅ -alkyl or dibromo-C ..- to C ₅ -alkyl, begins Le A 17 775 - 23 - 909808/0025 3. The method according to claim 1 and 2, characterized in that there is substituted as chloroalkyl or bromoalkyl Monoolefin is an olefin of the formula wherein R ₇ and Rg independently of one another hydrogen, Cj- to Cc-alkyl, MOnOChIOr-C ₁ - to C ₅ ~ alkyl, Monobromo-Cj- to C ₅ ~ alkyl, DiChIOr-C ₁ - to Cg-alkyl or dibromo-Cj- to C ^ -alkyl,
R _g and R ₁₀ independently of one another are a methylene, Chloromethylene, bromomethylene, 1,2-dichloroethylene or represent 1,2-dibromomethylene radical, represents an integer from 1 to 6, and where at least one of the radicals R ₇ R _{10 represents} an alkyl, cycloalkyl or alkylene radical of the type mentioned containing chlorine or bromine. Process according to Claims 1 and 2, characterized in that the chloroalkyl or bromoalkyl-substituted Monoolefin is an olefin of the formula R- λ -CH ⁼ Cxi-R- ^ Le A 17 775 - 24 - 909808/0021 wherein and R.J2 independently of one another hydrogen, C ₁ - to C ₅ -alkyl, monochloro-C, - bis ₅ I, monobromo-C ..- to C ₅ -alkyl, DiChIOr-C ₁ - to C ₅ ~ alkyl or dibromo-C ^ to C ₅ ~ alkyl, where at least one of the radicals R ₁₁ and R _{12 is} MOnOChIOr-C ₁ - to C ^ -alkyl, monobromo-C ^ to C ₅ -alkyl, dichloro-C-j to C ₅ -alkyl or dibromo-Cj- to C ₅ - Alkyl stands,
begins. 5. The method according to claim 1 to 4, characterized in that there is a chloroalkyl or bromoalkyl-substituted monoolefin with at least 4 carbon atoms. 6. The method according to claim 1 to 5, characterized in that that 1,4-dichloro-2-butene is used as the chloroalkyl- or bromoalkyl-substituted olefin. 7. The method according to claim 1 to 5, characterized in that that 3,4-dichloro-1-butene is used as the chloroalkyl- or bromoalkyl-substituted olefin. 8. The method according to claim 1 to 5, characterized in that that 1,4-dibromo-2-butene is used as the chloroalkyl- or bromoalkyl-substituted olefin. 9. The method according to claim 1 to 8, characterized in that the percarboxylic acid used is perpropionic acid. 10. The method according to claim 1 to 8, characterized in that that the percarboxylic acid used is perisobutyric acid. Le A 17 775 - 25 - 909808/0025 11. The method according to claim 1 to 10, characterized in that that dichloropropane is used as the chlorinated hydrocarbon. 12. '' experience according to claim 1 to 11, characterized in that that the reaction is carried out at a molar ratio of olefin to peracid such as 1.5 to 3: 1. 13. The method according to claim 1 to 12, characterized in that the
performs. that the reaction is carried out at a temperature of 60 to 80.degree 14. The method according to claim 1 to 13, characterized in that that the reaction product is used to separate the corresponding percarboxylic acid formed during the reaction Carboxylic acid by extracting the reaction mixture with water. Le A 17 775 - 26 - 909808/0025