JPS6236030B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to an improved process for the preparation of halogenoalkyl-substituted oxiranes from halogenoalkyl-substituted olefins and percarboxylic acids. Halogenoalkyl-substituted oxiranes are used in the lacquer and plastics fields and as organic intermediates. The preparation of chloroalkyl-substituted oxiranes from the corresponding olefins by the chlorohydrin method is known. This process has the disadvantage of producing undesirable chlorinated by-products and unnecessary salts that pollute the environment [Ullmanns,
Encyklop¨adie der technischen Chemie
(Ullmanns, Encyclopaedia of Industrial
Chemistry), Volume 10, Page 565, left column, line 1, especially 3.13-15; and German Patent Application Publication No.
1543174, column 2.13 et seq. 3.32-35]. Furthermore, it is often difficult to produce a single reaction product in a limited manner by the chlorohydrin method. The reaction of 4-chlorobut-2-ene with hypochlorous acid thus leads to a mixture of two products characterized by the following formula:

[Formula] and

[Formula] Subsequent dehydrohalogenation of this mixture using a base therefore yields two isomeric oxiranes of the formula shown below (German Patent Application No. 1056596, columns 1.53 to 1). Column 2.3-43
reference):

[Formula] and

[Formula] Furthermore, it is known to convert olefins to the corresponding oxiranes by means of percarboxylic acids [N. Prileschajew, Ber.dtsch.Chem.Ges. 42 ,
4811 (1909)]. This reaction is an electrophilic attack of the oxidizing agent onto the olefin. [KDBingham, GDMeakins and
GHWhitham, Chem.Commun (1966), pp. 445 and 446]. For this reason, the reactivity of olefins decreases as the nucleophilicity of the double bond decreases. Thus, electronegative substituents in the α-position relative to the C═C double bond hinder epoxidation [SN・
Lewis in RLAugustin, “Oxidation”, vol. 227, especially p. 227, 3.9-13, Marcel
Dekker, New York (1969)]. Halogenoalkyl-substituted olefins therefore cannot be epoxidized with percarboxylic acids without problems. As a result of the low reactivity of the double bond, high temperatures and long reaction times are required, leading to the formation of undesirable by-products, such as dihydroxy and hydroxyacyloxy derivatives of the starting materials [SN Lewis in RLAugustin, "Oxidation", Volume 233, especially 3.6-11, Marcel Dekker,
New York (1966)]. The structure and method of preparation of the percarboxylic acid thus used are of great importance, especially with regard to the nature and method of the reaction between the halogenoalkyl-substituted olefin and the percarboxylic acid. As is known, lower aliphatic percarboxylic acids have the reaction formula
(1) can be produced from carboxylic acid and hydrogen peroxide in an equilibrium reaction (D. Swern,
“Organic Peroxides”, Volume 1, page 61, Wiley
Intersciense 1971): RCOH+H ₂ O ₂ 〓RCOOOH+H ₂ O (1) Strong acids such as sulfuric acid, p-toluenesulfonic acid, etc. undergo rapid equilibrium, except when relatively strong carboxylic acids such as formic acid and trifluoroacetic acid are used. necessary as a catalyst to reach
in RLAugustin “Oxidation”, Vol. 216 (“C.Peracids”), Marcel Dekker, New York
1969]. However, reaction of olefins with, for example, peracids prepared in this way does not lead to oxiranes, but to α-glycols and hydroxyacetates [JB¨oseken, WCSmit
and Gaster, Proc.Acad.Sci.Amsterdam, 32 ,
377-383 (1929)]. The inorganic acid present in the reaction mixture catalyzes the ring-splitting ring-opening of the initially formed oxirane (D. Swern “Organic Peroxides”, Wiley
Intersciense 1971, Vol. 2, p. 436), which results in loss of oxirane in the case of slow-reacting olefins, such as halogenoalkyl-substituted olefins, where the reaction requires high temperatures and long reaction times. . Performic acid can be produced from hydrogen peroxide and formic acid without the addition of a catalyst (SNLewis in R.
L. Augustin, “Oxidation”, Vol. 217, Section 1, Marcel Dekker, New York 1969). However, the reaction of α-chloroalkyl-substituted olefins with this inorganic acid-free percarboxylic acid gives the corresponding epoxides only in low yields. Performic acid, thus prepared from 90% formic acid and 85% hydrogen peroxide, was converted into 3,4-dichlorobut-1-
Used in epoxidation of ene. After a reaction time of 5 hours at 60 °C, 2-(1,2-dichloroethyl)-oxirane is obtained with a yield of 30% (EGE
Hawkins, J, Chem.Soc., 1959, pp. 248-256.
Especially page 250, line 19). A method for producing aliphatic chloroepoxides by the reaction of an allylchlorohydrocarbon having a chlorine atom adjacent to the double bond with an organic percompound free of inorganic impurities was recently revealed (German Patent Application Publication No. No. 1056596). The per-compound used in this method is "pure peracetic acid, perpropionic acid or acetaldehyde monoperacetate mixed with acetaldehyde and/or acetone". (German Patent Application Publication No. 1056596, columns 10.32-35
line). Epoxidation of olefins substituted with chloro in the allylic position using acetaldehyde monoperacetate according to the method of German Patent Application No. 1056596 gives yields of between 17% and 56% based on the per-compound depending on the olefin. to give the corresponding oxirane. (German Patent Application Publication No.
No. 1056596, columns 5 to 7, lines 35 and below, Example 1,
3, 4 and 6). The peracetic acid and perpropionic acid used in this method for epoxidation are used as solutions in inert organic solvents. As mentioned elsewhere, typical inert solvents that can be used in this process are acetone, ethyl acetate, butyl acetate and dibutyl ether, among others (US Pat. No. 3,150,154).
No., column 3.1 to line 3). Allylchlorohydrocarbons can be epoxidized with peracids prepared according to the method of DE 10 56 596; however, the yield of oxirane is low; the peracid conversion is incomplete. In the example shown, the yield is only about 90% and the purity of the isolated oxirane is unsuitable for industrial use. Thus, the epoxidation of 3-chloro-1-butene with a solution of peracetic acid in acetone is described in DE 105 6 596, Example 5, column 7, lines 5 et seq. After a reaction time of 10 hours, the peroxide conversion rate is 91%. Oxirane is isolated in 68% yield with 90.5% purity. 3,4-dichloro-1,2 by reaction of 3,4-dichloro-1-butene with peracetic acid in acetone
- The production of epoxybutane is patented in the UK.
No. 784620, Examples, page 7, lines 5 and below. According to this production method, the peroxide conversion rate is 89% and the epoxide yield is 75%. The purity of the epoxide is shown as 93.3%. Regarding the epoxidation of olefin and perpropionic acid, see British Patent No. 784620, Examples, page 7.
Shown below line 85. According to this epoxidation, 1-chloro-2,3-epoxybutane is obtained in a yield of 56% after reaction of crotyl chloride with a solution of perpropionic acid in ethyl propionate. Peroxide conversion rate is 90%. On the other hand, in aromatic hydrocarbons containing 6 to 12 carbon atoms, the general formula In the formula, R ₁ and R ₄ are each independently hydrogen, C ₁ to C ₅ −
Alkyl, _C5 - _C7 -cycloalkyl, monochloro- _C1 - _C5 -alkyl, monobromo- _C1 - _C5-
Alkyl, dichloro- _C1 - _C5 -alkyl, dibromo- _C1 - _C5 -alkyl, monochloro- _C5 - _C7
-cycloalkyl, monobromo- _C5 - _C7 -cycloalkyl, dichloro- _C5 - _C7 -cycloalkyl or dibromo- _C5 - _C7 -cycloalkyl, R2 _{and R3} each independently represent hydrogen; , _C1 ~ _C5
-alkyl, monochloro- _C1 - _C5 -alkyl,
Monobromo- _C1 - _C5 -alkyl, dichloro- _C1
~C ₅ -alkyl and dibromo-C ₁ -C ₅ -alkyl, for the radicals R ₂ and R ₃ together with the carbon atoms of the C═C double bond form a ring of up to 12 carbon atoms; is possible to form, and the group R ₁
chloroalkyl-substituted or bromoalkyl-, wherein at least one of ~R ₄ is an alkyl or cycloalkyl group of the above type containing chlorine or bromine
A solution of a substituted monoolefin and a percarboxylic acid containing 3 to 4 carbon atoms is prepared at a molar ratio of monoolefin to percarboxylic acid of 1.1:10:1 and at 30°C to
It has been found that a halogenoalkyl-substituted oxirane can be produced in high yield and purity from a halogenoalkyl-substituted olefin and percarboxylic acid in an organic solvent by a reaction method at a temperature of 100°C. Within the scope of the compounds of formula (), examples of possible compounds are in particular those of the following formula: R ₅ -CH=CH-R ₆ in which R ₅ and R ₆ are independently of each other C ₁ ~ _C5 -alkyl, monochloro- _C1 - _C5 -alkyl, monobromo- _C1 -C5-alkyl, dichloro- _C1 - _C5 -alkyl or dibromo- _{C1 -C5 -} alkyl, and the group R ₅ and R ₆ can be taken together with the group CH=CH to form a ring, and the group R ₅
and at least one of R ₆ is monochloro-C ₁ to _{C 5}
-alkyl, monobromo- _C1 - _C5 -alkyl,
dichloro- _C1 - _C5 -alkyl or dibromo-
Represents _C1 - _C5 -alkyl; In the formula, R ₇ and R ₈ are each independently hydrogen, C ₁ to C ₅ −
Alkyl, monochloro- _C1 - _C5 -alkyl, monobromo- _C1 - _C5 -alkyl, dichloro- _C1-
represents _C5 -alkyl or dibromo- _C1 - _C5 -alkyl, _R9 and _R10 are each independently methylene,
represents a chloromethylene, bromomethylene, 1,2-dichloroethylene or 1,2-dibromomethylene group, n represents an integer of 1 to 6, and the group R ₇ to
At least one of R ₁₀ represents an alkyl, dichloroalkyl or alkylene group of the above type containing chlorine or bromine. More specifically, the halogenoalkyl-substituted monoolefins that may be mentioned are: allyl chloride, 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-1-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-1-cyclohexene, 1,4-dichloro-
2-cyclohexene, 1-chloro-2-heptene, 3-chloro-1-heptene, 3,4-dichloro-1-heptene, 1,4-dichloro-2-heptene, 2-chloro-3-heptene, 2, 5-dichloro-3-heptene, 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
-dodecene, 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-dodecene,
5-chloro-6-dodecene, 5,8-dichloro-
6-dodecene, 5,7-dichloro-6-dodecene and 7-chloro-5-dodecene; allyl bromide, 2-bromomethyl-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-bromo-2-pentene, 1,4
-dibromo-2-pentene, 3,4-dibromo-
1-pentene, 1,2-dibromo-3-pentene, 3-bromo-1-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-1-
Cyclohexene, 1,4-dibromo-2-cyclohexene, 1-bromo-2-heptene, 3-bromo-1-heptene, 3,4-dibromo-1-heptene, 1,4-dibromo-2-heptene, 2- Bromo-3-heptene, 2,5-dibromo-3-heptene, 3-bromo-1-cycloheptene, 1,
4-dibromo-2-cycloheptene, 1-bromo-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, 3-bromo- 1-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-nonene, 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-decene, 2-bromo-3-decene, 2,5-dibromo-3-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,
-bromo-2-undecene, 2,5-dibromo-
3-undecene, 5-bromo-3-undecene,
6-bromo-4-undecene, 4-bromo-5-
Undecene, 4,7-dibromo-5-undecene, 5-bromo-6-undecene, 5,8-dibromo-6-undecene, 1-bromo-3-dodecene, 3-bromo-1-dodecene, 1,4- dibromo-2-dodecene, 2-bromo-3-dodecene,
4-bromo-2-dodecene, 2,5-dibromo-
3-dodecene, 5-bromo-3-dodecene, 6-
Bromo-4-dodecene, 4-bromo-5-dodecene, 4,7-dibromo-5-dodecene, 5-bromo-6-dodecene, 5,8-dibromo-6-dodecene, 5,7-dibromo-6- Dodecene and 7-
Bromo-5-dodecene. Chloroalkyl-substituted or bromoalkyl-substituted monoolefins which are particularly suitable for reaction with percarboxylic acids according to the process of the invention have the formula R ₁₁ -CH=CH-R ₁₂ () where R ₁₁ and R ₁₂ are independently hydrogen, C ₁ ~
_C5 -alkyl, monochloro- _C1 - _C5 -alkyl, monobromo- _C1 - _C5 -alkyl, dichloro- _C1 - _C5 -alkyl or dibromo- _C1 - _C5-
represents alkyl, at least one of the groups R ₁₁ and R ₁₂
represents monochloro- _C1 - _C5 -alkyl, monobromo- _C1 - _C5 -alkyl, dichloro- _C1 - _C5 -alkyl or dibromo- _C1 - _C5 -alkyl. In particular, examples that may be mentioned are: allyl chloride, 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-1-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-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-1-cyclohexene and 1,4-dichloro-2-cyclohexene; allyl bromide, 2-bromomethyl-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,
1,2-dibromo-3-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 and 1,4-dibromo-2-
Cyclohexene. 1,4-dichloro-2-butene, 1,4-dibromo-2-butene and 3,4-dichloro-1-butene are particularly highly suitable for the reaction with percarboxylic acids according to the process according to the invention. ing. Optionally substituted carbon atom 6 as a solvent
~12 A wide variety of aromatic hydrocarbons can be used. Possible examples are benzene, nitrobenzene, toluene, xylene, ethylbenzene, diethylbenzene, cumene, diisopropylbenzene and chlorobenzene. Aromatic hydrocarbons having 6 to 8 carbon atoms, such as benzene, nitrobenzene, chlorobenzene, toluene, xylene and ethylenebenzene, are particularly suitable. Preferred solvents are benzene and toluene. A particularly preferred solvent is benzene. It is also possible to use mixtures of different aromatic hydrocarbons. Peracids that can be used according to the invention are perpropionic acid, perbutyric acid and perisobutyric acid. Preferably, perpropionic acid and perisobutyric acid are used. Particular preference is given to perpropionic acid. A process for producing inorganic acid-free peracids in one of the above-mentioned organic solvents can be made, for example, by the method described in DE-A-2262970. Generally, when the method of the present invention is actually carried out, the reaction is carried out at a temperature range of 30 to 100°C. Preferably the reaction is carried out at 60-80°C, particularly preferably 65-75°C. In special cases, the process can also be carried out at temperatures below or above the abovementioned temperatures. With the exception of isothermal conditions, i.e. with the entire reaction mixture being kept at a uniform temperature, the reaction can be carried out in a so-called temperature gradient, in which case:
Generally the temperature increases as the reaction progresses. However, it is also possible to carry out the reaction in a temperature gradient that decreases as the reaction progresses. According to the invention, the molar ratio of olefin to peracid is
The ratio is 1.1:1 to 10:1. Preferably 1.25:1~
A molar ratio of 5:1 is used. Very particular preference is given to using molar ratios of 1.5 to 3.0 mol of olefin per mol of peracid. The process according to the invention can be carried out under a wide variety of pressures. Generally, the process is carried out under normal pressure; however, the process can also be carried out under reduced or elevated pressure. Generally, the water content of the percarboxylic acid used for epoxidation should be as low as possible. Small amounts, usually up to 5% by weight, are not a problem. For example, percarboxylic acids with a water content of up to 2% by weight are suitable. Preference is given to using percarboxylic acid solutions containing less than 1% by weight of water. Water contents of less than 0.1% by weight are particularly preferred. In general, the hydrogen peroxide content of the percarboxylic acids used should be as low as possible. This content can be up to 2% by weight. The reaction is advantageously carried out with a hydrogen peroxide content of less than 1% by weight. It is particularly advantageous to carry out the reaction in percarboxylic acid solutions with a hydrogen peroxide content of 0.3% or less. The inorganic acid content of the percarboxylic acid solution used in the reaction should be as low as possible. Inorganic acid content
It is advantageous to carry out the reaction with less than 50 ppm percarboxylic acid solution. Particularly advantageous are inorganic acid contents of less than 10 ppm. The reaction can be carried out batchwise or continuously in the equipment customary for reactions of this type, such as stirred kettles, boiling reactors, tube reactors, loop reactors or circulation reactors. Glass, stainless steel or enameled materials can be used as the structural material for carrying out the method. Heavy metal ions in the reaction mixture catalyze the decomposition of the percarboxylic acid. Therefore, substances which render the heavy metal ions inactive by complexation are generally added to the percarboxylic acid solution. Known substances of this type are gluconic acid, ethylenediaminetetraacetic acid, sodium silicate, sodium pyrophosphate, sodium hexametaphosphate, disodium dimethylpyrophosphate or Na ₂ (2-ethyl-hexyl) ₅
(P ₃ O ₁₀ ) ₂ (German patent application publication no.
No. 1056596, column 4, 60 lines or less). The halogenoalkyl-substituted olefin can be introduced into the equipment used in the reaction in a variety of ways. Either the olefin is placed in the reactor together with the percarboxylic acid solution, or the two components are fed separately to the reactor. Furthermore, the olefin and percarboxylic acid solutions can be introduced at different locations in the reactor. When using several reactors connected in a cascade process, it is appropriate to introduce all the olefins into the first reactor. However, it is also possible to distribute the olefin in various reactors. The heat of reaction is removed by an internal or external cooler. In order to remove the heat of reaction, the reaction can be carried out under reflux (boiling reaction). The reaction is carried out until as complete as possible the addition of percarboxylic acid. Generally more than 95 mole percent of the percarboxylic acid is reacted. Suitably, more than 98 mole % of peracid is reacted. When the reaction between a halogenoalkyl-substituted olefin and a peracid is carried out according to the invention, oxirane yields of 90% or more of theory can be obtained based on the percarboxylic acid used. The reaction mixture is worked up in a manner known per se, for example by distillation. In order to separate the carboxylic acid corresponding to the percarboxylic acid formed during the reaction, it is particularly advantageous to extract the reaction mixture with water before working up by distillation. Extraction can be carried out in conventional extractors, such as mixers/separators, perforated dish extractors, shaken perforated dish extraction columns, rotating disk extractors or centrifugal extractors. In a preferred method of carrying out the process, a molar amount of halogenoalkyl-substituted olefin thermostatted at 70 DEG C. is added in three portions to a stirred approximately 20% by weight solution of perpropionic acid in benzene. The perpropionic acid solution contains less than 10 ppm of inorganic acid; the water content is less than 0.1% and the hydrogen peroxide content is less than 0.3%. Approximately 0.05 to complex the heavy metal ions before the reaction.
wt% Na ₂ (2-ethylhexyl) ₅
(P ₃ O ₁₀ ) ₂ can be added to perpropionic acid. The progress and completion of the reaction are monitored by removing samples from the reaction solution from time to time and measuring the content of percarboxylic acid present by titration. After the reaction is complete, the reaction mixture is cooled and washed three times with equal weight parts of water to remove propionic acid. The reaction mixture free of propionic acid is then fractionated. The following examples illustrate the invention. All percentages are by weight unless otherwise specified. Example 1 Preparation of epichlorohydrin from allyl chloride and perpropionic acid A three-necked, double-walled flask with a capacity of 200 ml, equipped with a magnetic stirrer, an internal thermometer, a dropping funnel and a reflux condenser, was first charged with benzene. 45 g (0.1 mol) of 20% perpropionic acid were introduced and the thermostat was adjusted to 70°C. Thereafter, 22.96 g (0.3 mol) of allyl chloride was added dropwise while maintaining the temperature at 70° C. After further stirring for 6 hours under reflux, titration analysis showed a perpropionic acid conversion of 98.5%. Gas chromatographic analysis of the reaction mixture revealed that it was 97.5% based on the perpropionic acid used.
It was found that epichlorohydrin was produced with a selectivity of . After cooling, the reaction mixture was washed several times with water to remove propionic acid and then fractionated. 8.73 g of epichlorohydrin was obtained. Example 2 Preparation of 2-(1,2-dichloroethyl)-oxirane from 3.4-dichloro-1-butene and perpropionic acid Perpropionic acid as a 21% solution in benzene
While stirring 62.96g (0.147mol) at 70℃,
It was added dropwise to 55.87 g (0.447 mol) of 3,4-dichloro-1-butene. After the addition was complete, the mixture was stirred at this temperature for a further 6 hours and titrimetric analysis showed a perpropionic acid conversion of 97%. This reaction solution was cooled to room temperature and analyzed by gas chromatography. As a result of analysis, it was 94.2% based on the perpropionic acid used.
2-(1,2-dichloroethyl)-oxirane was produced with a selectivity of . The reaction mixture was washed several times with water to remove the propionic acid, the benzene was distilled off, and the reaction product was then washed with water several times to remove the propionic acid.
Fractional distillation was carried out in a 40 cm column packed with a mm glass Ratschig ring. 2-(1,
18.9 g of 2-dichloroethyl)-oxirane were isolated. Example 3 Preparation of 2,3-bis-(chloromethyl)-oxirane from 1,4-dichloro-2-butene and perpropionic acid 63.97 g (0.147 mol) of perpropionic acid as a 20.68% solution in benzene at 70°C was added dropwise to 55.2 g (0.4416 mol) of 1,4-dichloro-2-butene,
The mixture was then further stirred at this temperature. After a reaction time of 4 hours, the conversion of peracid was 96% and 6
After hours, it was over 99%. 2,3-bis-(chloromethyl)-oxirane was produced with a selectivity of 96.5% relative to the perpropionic acid used. The reaction mixture is shaken several times with water to remove the propionic acid by extraction and the benzene is separated by distillation;
The reaction product was then fractionated using a 30cm column packed with a 4mm glass Ratschig ring, resulting in a purity of 99.9%.
19.6 g of 2,3-bis-(chloromethyl)-oxirane were obtained. Example 4 Continuous production of 2,3-bis-(chloromethyl)-oxirane from 1,4-dichloro-2-butene and perpropionic acid A commercially available product consisting of the sodium salt of polyphosphoric acid partially esterified with a long-chain alcohol A solution of perpropionic acid in benzene with the addition of a stabilizer of 1.
Reacted with 4-dichloro-2-butene. Each of the three stirrers had a capacity of 10. The kettle was heated by a heating coil placed inside the kettle. All three kettles were thermostatted at 70°C. Perpropionic acid as a 20% solution in benzene
2137.5g (4.75mol), and 1,4-dichloro-
1781.25 g (14.25 moles) of 2-butene were fed to the reaction system per hour, corresponding to an average residence time of about 8 hours. Under these reaction conditions, perpropionic acid was converted to about 96.8%. The selectivity of the resulting 2,3-bis-(chloromethyl)-oxirane relative to the perpropionic acid used was 96%. The reaction mixture obtained from the third reactor had the following average composition: 35.6% benzene, 1,4-
Dichloro-2-butene 30.8%, 2,3-bis-
(chloromethyl)-oxirane 16.24% and propionic acid 17%. This mixture was extracted with twice the volume of water in a shaking perforated dish extraction column to separate the propionic acid. Afterwards, the residual content of propionic acid was 0.04%. The reaction mixture obtained after this operation was fractionated using a distillation system. Benzene 1395
g/h in the first column. The product at the bottom of this column, consisting essentially of starting material and oxirane, was fractionated in a second column under reduced pressure. 1206.5 g of 1,4-dichloro-2-butene were obtained per hour as head product. From the product at the bottom of this second column, high boiling components were removed under reduced pressure in a third column. 629.5 g of 2,3-bis-(chloromethyl)oxirane was obtained per hour as a head product with a purity of over 99.9%, which was a yield of 94% based on the perpropionic acid used in the reaction system. It was equivalent to Example 5 1,4-dibromo-2- with perpropionic acid
Epoxidation of butene a Bromination of butadiene 171.4 g (3.17 mol) of butadiene was dissolved in 400 ml of n-hexane. To this was added dropwise 314 g (1.964 mol) of bromine while stirring at -20°C. After the addition was complete, the mixture was stirred at this temperature for a further 2 hours.
It was then warmed to room temperature and the solvent was removed under vacuum.
380.4 g of crude dibromobutene was obtained, 1,4
-dibromo-2-butene vs. 3,4-dibromo-1
-butene ratio was approximately 2:1. 1,4-dibromo-2-butene was isolated by distillation. b Reaction of 1,4-dibromo-2-butene with perpropionic acid 45 g (0.1 mol) of 20% perpropionic acid in benzene was reacted with 1,4-dibromo-2-butene while stirring at 70°C.
64.2 g (0.3 mol) of 2-butene were added dropwise and the mixture was stirred for a further 4 hours at this temperature. At this point, the conversion rate of peracid was 95%. . Gas chromatographic analysis revealed that epoxide was produced with a selectivity of 92.6% relative to the perpropionic acid used. After cooling, the reaction mixture was washed several times with water to remove propionic acid, and the reaction product was fractionated. 20.7 g of epoxide was obtained.

Claims (1)

[Scope of Claims] 1 In an aromatic hydrocarbon containing 6 to 12 carbon atoms, the general formula In the formula, R ₁ and R ₄ are each independently hydrogen, C ₁ to C ₅ −
Alkyl, _C5 - _C7 -cycloalkyl, monochloro- _C1 - _C5 -alkyl, monobromo- _C1 - _C5-
Alkyl, dichloro- _C1 - _C5 -alkyl, dibromo- _C1 - _C5 -alkyl, monochloro- _C5 - _C7
-cycloalkyl, monobromo- _C5 - _C7 -cycloalkyl, dichloro- _C5 - _C7 -cycloalkyl or dibromo- _C5 - _C7 -cycloalkyl, R2 _{and R3} each independently represent hydrogen; , C ₁ ~C ₅ −
Alkyl, monochloro- _C1 - _C5 -alkyl, monobromo- _C1 - _C5 -alkyl, dichloroC1 _{- C5}
-alkyl and dibromo-C ₁ -C ₅ -alkyl, which together with the carbon atoms of the C═C double bond form rings of up to 12 carbon atoms for the radicals R ₂ and R ₃ ; is possible, and the groups R ₁ to _{R 4}
chloroalkyl-substituted or bromoalkyl- of , at least one of which is an alkyl or cycloalkyl group of the above type containing chlorine or bromine
A solution of a substituted monoolefin and a percarboxylic acid containing 3 to 4 carbon atoms is prepared in a molar ratio of monoolefin to percarboxylic acid of 1.1:1 to 10:1 and 30
A method for producing a halogenoalkyl-substituted oxirane from a halogenoalkyl-substituted olefin and a percarboxylic acid, characterized in that the reaction is carried out at a temperature of 100°C to 100°C. 2 as a chloroalkyl-substituted or bromoalkyl-substituted monoolefin with the formula R ₅ -CH=CH-R ₆ in which R ₅ and R ₆ are independently of each other C ₁ -C ₅ -alkyl, monochloroC ₁ - C ₅ -alkyl, monobromo
represents _C1 - _C5 -alkyl, dichloro- _C1 - _C5 -alkyl or _dibromoC1 - _C5 -alkyl;
For the radicals R ₅ and R ₆ they can be taken together with the radical CH=CH to form a ring, and for the radicals R ₅ and R ₆
at least one of monochloro- _C1 - _C5 -alkyl, monobromo- _C1 - _C5 -alkyl, dichloro- _C1 - _C5 -alkyl or dibromo- _C1 - _C5-
2. A method according to claim 1, using an olefin represented by the following: alkyl. 3 as a chloroalkyl-substituted or bromoalkyl-substituted monoolefin of the formula In the formula, R ₇ and R ₈ are each independently hydrogen C ₁ -C ₅ -alkyl, monochloroC ₁ -C ₅ -alkyl, monobromo-C ₁ -C ₅ -alkyl, dichloro-C ₁ -C ₅ -
represents alkyl or dibromo- _C1 - _C5 -alkyl, _R9 and _R10 each independently represent methylene, chloromethylene, bromomethylene, 1,2-dichloroethylene or 1,2-dibromomethylene group, and n is represents an integer from 1 to 6 and at least one of the radicals R ₇ to _{R 10} represents an alkyl, cycloalkyl or alkylene group of the above type containing chlorine or bromine. The method described in Section 2. 4 as a chloroalkyl-substituted or bromoalkyl-substituted monoolefin with the formula R ₁₁ -CH=CH-R ₁₂ where R ₁₁ and R ₁₂ are each independently hydrogen, C ₁ -C ₅
-alkyl, monochloro- _C1 - _C5 -alkyl,
Monobromo- _C1 - _C5 -alkyl, dichloro- _C1
~ _C5 -alkyl or dibromo- _C1 - _C5 -alkyl, and at least one of _R11 and _R12 is monochloro- _C1 - _C5 -alkyl, monobromo- _C1
3. Process according to claims 1 and 2, using an olefin of _-C5 -alkyl, dichloro- _C1 - _C5 -alkyl or dibromo- _C1 - _C5 -alkyl. 5. The method according to claims 1 to 4, in which allyl chloride is used as the chloroalkyl-substituted or bromoalkyl-substituted monoolefin. 6. The method according to claims 1 to 5, wherein 1,4-dichloro-2-butene is used as the chloroalkyl-substituted or bromoalkyl-substituted olefin. 7. Process according to claims 1 to 6, in which 3,4-dichloro-1-butene is used as the chloroalkyl-substituted or bromoalkyl-substituted olefin. 8. Process according to claims 1 to 7, in which 1,4-dibromo-2-butene is used as the chloroalkyl-substituted or bromoalkyl-substituted olefin. 9. The method according to claims 1 to 8, in which perpropionic acid is used as the percarboxylic acid. 10. The method according to claims 1 to 9, in which perisobutyric acid is used as the percarboxylic acid. 11. The method according to claims 1 to 10, wherein benzene is used as the aromatic hydrocarbon. 12 The reaction is carried out at a molar ratio of olefin to peracid of 1.5 to
12. The method according to claims 1 to 11, which is carried out at a ratio of 3:1. 13. The method according to claims 1 to 12, wherein the reaction is carried out at a temperature of 60 to 80°C. 14. Process according to claims 1 to 13, characterized in that the reaction product is treated by extraction of the reaction mixture with water in order to separate the carboxylic acid corresponding to the percarboxylic acid produced during the reaction.