CA1120047A - Process for the preparation of halogenoalkyl- substituted oxiranes - Google Patents
Process for the preparation of halogenoalkyl- substituted oxiranesInfo
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- CA1120047A CA1120047A CA000308193A CA308193A CA1120047A CA 1120047 A CA1120047 A CA 1120047A CA 000308193 A CA000308193 A CA 000308193A CA 308193 A CA308193 A CA 308193A CA 1120047 A CA1120047 A CA 1120047A
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- dibromo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
- C07C17/02—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
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- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Bayer 3493-JGK
PROCESS FOR THE PREPARATION OF HALOGENOALKYL-SUBSTITUTED OXIRANES
Abstract of the Disclosure A process has been invented for the preparation of halogenoalkyl-substituted oxiranes by reaction between certain halogenoalkyl-substituted olefins and percarboxylic acids in the presence of a halogenoated hydrocarbon solvent.
Le A 17 775
PROCESS FOR THE PREPARATION OF HALOGENOALKYL-SUBSTITUTED OXIRANES
Abstract of the Disclosure A process has been invented for the preparation of halogenoalkyl-substituted oxiranes by reaction between certain halogenoalkyl-substituted olefins and percarboxylic acids in the presence of a halogenoated hydrocarbon solvent.
Le A 17 775
Description
~lZ~ 7 The present invention relates to an improved process for the preparation of halogenoalkyl-substituted oxiranes from halogenoalkyl-substituted ole~ins and percarboxylic acids.
'~ Halogenoalkyl-substituted oxiranes are used in the field o~ lacquers and plastics and as organic intermediate products.
It is known to prepare chloroalkyl-substituted oxi-ranes from the corresponding olefins by the chlorohydrin 1() process. This process has the disadvantage that undesired chlorinated by-products and waste salts which pollute the environment are formed (Ullmanns Encyklopadie der technischen Chemie (Ullmanns Encyclopaedia of Industrial Chemistry), vol-ume 10, page 565, left-hand column, line 1 et seq., in l'i particular 3. 13-15; and DAS (German Published Specification) 1,543,174, column 2, line l'j et seq., in particular 3. 32-35~.
It is also frequently di~ficult de~initively to pre-pare a single reaction product by the ~hlorohydrin method.
Thus, the reaction of 4-chlorobut-2-ene with hypochlorous acid leads to a mixture of two products, which may be characterised by the following formulae:
OH Cl Cl Cl OH Cl CH3-CH-CH-~H2 and CH3-CH-CH-CH2 Accordingly, subsequent dehydrohalogenation o~ this mixture using a base gives a mixture of two isomeric oxiranes,
'~ Halogenoalkyl-substituted oxiranes are used in the field o~ lacquers and plastics and as organic intermediate products.
It is known to prepare chloroalkyl-substituted oxi-ranes from the corresponding olefins by the chlorohydrin 1() process. This process has the disadvantage that undesired chlorinated by-products and waste salts which pollute the environment are formed (Ullmanns Encyklopadie der technischen Chemie (Ullmanns Encyclopaedia of Industrial Chemistry), vol-ume 10, page 565, left-hand column, line 1 et seq., in l'i particular 3. 13-15; and DAS (German Published Specification) 1,543,174, column 2, line l'j et seq., in particular 3. 32-35~.
It is also frequently di~ficult de~initively to pre-pare a single reaction product by the ~hlorohydrin method.
Thus, the reaction of 4-chlorobut-2-ene with hypochlorous acid leads to a mixture of two products, which may be characterised by the following formulae:
OH Cl Cl Cl OH Cl CH3-CH-CH-~H2 and CH3-CH-CH-CH2 Accordingly, subsequent dehydrohalogenation o~ this mixture using a base gives a mixture of two isomeric oxiranes,
2'j as the formulae below illustrate (DAS (German Published Speci~ication) 1,056,596~ column 1, line 53 to column 2, 3-43):
/0\ C1 ll / \
CH3-CH-CH-CH2 and CH~-CH-CH-CH2 Furthermore, it ls known to convert ole~ins into -the corresponding oxiranes with -the aid of a percarboxylic acid.
.' ~
~ ' :
l~Z~
(N. Prileschajew, Ber. dtsch. Chem. Ges~ 42, 4,811 ~1909)).
This reaction is an electrophilic attack of the oxi-dising agent on -the olefin. (K.D. Bingham, G.D. Meakins and G.H. Whitham, Chem. Commun. (1966, pages 445 and 446).) For this reason, the reactivity of the olefin decreases with decreasing nucleophilicity of the double bond. Electro-negative substituents in the a-position relative to the C=C double b~nd thus impede -the epoxidation. (S. N. Lewis in R. L. Augustln, "Oxidation", volume I, page 227, in par- -ticular page 227, 3. 9-13, Marcel Dekker~ New York (1969).) Halogenoalkyl-substituted olefins therefore cannot be epoxi-dised with percarboxylic acids without problems. As a result of the low reactivity of their double bond, high temperatures and long reaction times are necessary, which give~ rise to the formation of undesired by-products, such as dihydroxy and hydroxyacyloxy d~xi~atives of the starting mat-erials. (S. N. Lewis in R~ L. Augustin, "Oxidation", volume I, page 233, in particular 3. 6-11, Marcel Dekker, New York 1969).
The structure and method o~ preparation of the per-carboxylic acid used is thus of great importance, in parti-cular with regard to the nature and p~ocedure of the reaction between a halogenoalkyl-substituted olefin and a percarboxylic ,.. . . . . .
acid.
As is known, lower aliphatic percarboxylic acids can be prepared ~rom a carboxylic acid and hydrogen peroxide in an equilibrium reaction according to equation (1). (D. Swern, in "Organic Peroxidesl', volume 1, page 619 Wiley Intersciense 1971) RCOOH + H22 ~ RCOOOH ~ H20 (1) Except ~or when relatively strong carboxylic acids are
/0\ C1 ll / \
CH3-CH-CH-CH2 and CH~-CH-CH-CH2 Furthermore, it ls known to convert ole~ins into -the corresponding oxiranes with -the aid of a percarboxylic acid.
.' ~
~ ' :
l~Z~
(N. Prileschajew, Ber. dtsch. Chem. Ges~ 42, 4,811 ~1909)).
This reaction is an electrophilic attack of the oxi-dising agent on -the olefin. (K.D. Bingham, G.D. Meakins and G.H. Whitham, Chem. Commun. (1966, pages 445 and 446).) For this reason, the reactivity of the olefin decreases with decreasing nucleophilicity of the double bond. Electro-negative substituents in the a-position relative to the C=C double b~nd thus impede -the epoxidation. (S. N. Lewis in R. L. Augustln, "Oxidation", volume I, page 227, in par- -ticular page 227, 3. 9-13, Marcel Dekker~ New York (1969).) Halogenoalkyl-substituted olefins therefore cannot be epoxi-dised with percarboxylic acids without problems. As a result of the low reactivity of their double bond, high temperatures and long reaction times are necessary, which give~ rise to the formation of undesired by-products, such as dihydroxy and hydroxyacyloxy d~xi~atives of the starting mat-erials. (S. N. Lewis in R~ L. Augustin, "Oxidation", volume I, page 233, in particular 3. 6-11, Marcel Dekker, New York 1969).
The structure and method o~ preparation of the per-carboxylic acid used is thus of great importance, in parti-cular with regard to the nature and p~ocedure of the reaction between a halogenoalkyl-substituted olefin and a percarboxylic ,.. . . . . .
acid.
As is known, lower aliphatic percarboxylic acids can be prepared ~rom a carboxylic acid and hydrogen peroxide in an equilibrium reaction according to equation (1). (D. Swern, in "Organic Peroxidesl', volume 1, page 619 Wiley Intersciense 1971) RCOOH + H22 ~ RCOOOH ~ H20 (1) Except ~or when relatively strong carboxylic acids are
3 -0~7 used, such as formic acid and trifluroacetic acid, strong acids, such as sulphuric acid, p-toluenesulphonic acid and others, a~e required as a catalyst for rapid establishment of the equilibri~ (S. N. Lewis in R. L. Augustin "Oxidation", volume I, page 216 ("C. Peracids"), Marcel Dekker, New York 1969). However, the reac-tion of olefins with, for example, peracetic acid prepared by this method did not lead to oxi-ranes but to a-glycols and hydroxyacetates (J. Boseken, W. C. Smit and Gaster, Proc. Acad. Sci. Amsterdam, 32 377-383 (1929).) The mineral acid present in the reaction mixture catalyses the splitting-open of the oxirane pri-marily formed (D. Swern l'Organic Peroxides"~Wiley Intersciense 1971, volume 2, page 436), which can lead to oxi-rane losses, especially in the case of olefins which are slow to react, such as halogenoalkyl-substituted olefins, ~or the reaction of which high temperatures and long reaction times are necessary.
Per~ormic acid can be prepared from hydrogen per-oxide and ~ormic acid without an additional catalyst (S. N.
Lewi~ in R.L. Augustin, "Oxidation", volume I, page 217, first paragraph, Marcel Dekker~ New York 1969). However, the reactio~ o~ ~-chloroalkyl-substituted ole~ins with this mineral acid-~ree percarboxylic acid also gave the correspon-ding epoxide only in low yields. A perfo~mic acid prepared from 90% streng-th formic acid and 85% strength hydro-gen peroxide was thus used ~or the epoxidation of 3,4-di-chlorobut~l ene. After a reaction time o~ ~ive hours at 60C, 2-~192~dichloroethyl-)oxirane was obtained in 30% yield (E. G. E. Hawkins, J. Chem. Soc., 1959 pages 248 to 256, in particular page 250, line 19).
A process for the preparation of aliphatic chloro-
Per~ormic acid can be prepared from hydrogen per-oxide and ~ormic acid without an additional catalyst (S. N.
Lewi~ in R.L. Augustin, "Oxidation", volume I, page 217, first paragraph, Marcel Dekker~ New York 1969). However, the reactio~ o~ ~-chloroalkyl-substituted ole~ins with this mineral acid-~ree percarboxylic acid also gave the correspon-ding epoxide only in low yields. A perfo~mic acid prepared from 90% streng-th formic acid and 85% strength hydro-gen peroxide was thus used ~or the epoxidation of 3,4-di-chlorobut~l ene. After a reaction time o~ ~ive hours at 60C, 2-~192~dichloroethyl-)oxirane was obtained in 30% yield (E. G. E. Hawkins, J. Chem. Soc., 1959 pages 248 to 256, in particular page 250, line 19).
A process for the preparation of aliphatic chloro-
4 -~Z~ L7 epoxides by reacting an allylchlorohydrocarbon, which has a chlorine atom in the adjacent position to the double bond, with an or~anic per-compound which is free from inorganic impurities has been disclosed recently (DAS (German Published Specification) 1,056,596). The per-compounds used in this process are "pure peracetlc acid, perpropionic acid or acet-aldehyde monoperacetate mixed with acetaldehyde and/or acetone". (DAS (German Published Specification) 1,056,596, column 10, lines 32-35.) The epoxidation, according to the process of DAS (German Published Speci~ication) 1,056,596, of ole~in$, which are chloro-substituted in the allyl position, using acetaldehyde monoperacetate gives the corresponding oxi-ranes in yields of between 17% and 56%, relative to the per-compound, depending on the olefin. (DAS (German Published Specification) 1,056,596, column 5 to 7, line 35 et seq., Example 1, 3, 4 and 6).`;
~he peracetic acid and perpropionic acid used in this process for the epoxidation is employed in solution in an inert organic solvent. As described at another point, typi-cal inert solvents which can be employed in this process are, inter alla, acetone9 ethyl acetate, butyl acetate and dibutyl ether ~U~S. Patent 3,150,154, col D 3, line 1-3).
Allylchlorohydrocarbons can be epoxidised with the per-acids prepared according to the process o~ DAS (German Publi~hed Specification) 1,056,596; however, the yields of oxiranes are low; the peracid conversion is incomplete. In the examples indicated it is only about 90% and the purity o~
the oxiranes isolated is inadequate for industrial use.
Thus, the epoxidation of 3-chloro-1-butene with a solution of peracetic acid in acetone is described in DAS (German Pub-lished Specification) 1,056,596 in Example 55 column 7, line
~he peracetic acid and perpropionic acid used in this process for the epoxidation is employed in solution in an inert organic solvent. As described at another point, typi-cal inert solvents which can be employed in this process are, inter alla, acetone9 ethyl acetate, butyl acetate and dibutyl ether ~U~S. Patent 3,150,154, col D 3, line 1-3).
Allylchlorohydrocarbons can be epoxidised with the per-acids prepared according to the process o~ DAS (German Publi~hed Specification) 1,056,596; however, the yields of oxiranes are low; the peracid conversion is incomplete. In the examples indicated it is only about 90% and the purity o~
the oxiranes isolated is inadequate for industrial use.
Thus, the epoxidation of 3-chloro-1-butene with a solution of peracetic acid in acetone is described in DAS (German Pub-lished Specification) 1,056,596 in Example 55 column 7, line
5 -: ' :
5 et seq.. After a reaction time o~ ten hours, the peracid conversion is 91~. The oxirane is isolated in 68Q~ yield with a purity of 90.5%.
The preparation o~ 3,4-dichloro-1,2-epoxybutane by reacting 3,4-dichloro-1-butene with peracetic acid in acetone is described in British Patent Specification 784,620, in Example VII, page 7, line 5 et seq.. According to this pre-paration, the peracid conversion is 89% and the yield of epoxide is 75%. The purity of the epoxide is given as 93.3%. An account of the epoxidation of an olefin with perpropionic acid is also given in British Patent Specification 784,620, in Example IX, page 7, line 85 et seq. According to this epoxida-tion, after reacting crotyl chloride with a solutisn of perpropionic acid in ethyl propionate, l-chloro-2,3-epoxybutane was obtained in 56% yield. The peracid conversion was 90~.
In contrast, it has now been found that halogenoalkyl-substituted oxiranes can be prepared in high yields and high purity from halogenoalkyl-substituted olefins and percarboxylic acids in organic solution by a process in which a chloroalkyl-sub&titute~l or bromoalkyl-substituted monoole~in of the general formula Rl-C = C-R4 (I) wherein Rl and R4 independently of one another denote hydrogen, Cl- to C5-alkyl, C5- to C7~cycloalkyl, monochloro-Cl- to C5-alkyl, monobromo-Cl- to C5-alkyl, dichloro-Cl- to C5~alkyl, dibrsmo-Cl- to C5-alkyl, monochloro-C5 to C7-cycloalkyl, monsbromo-C5- to C7-cycloalkyl, 3C dichloro~C5~ to C7 cycloalkyl or dibromo-C5- to C7-~@_~_a~ 6 -cycloalkyl and R2 and R3 independently of one another represent hydrogen, Cl- to C5-alkyl, monochloro-Cl- to C5-al-kyl, monobromo-Cl- to C5-alkyl, dichloro-Cl- to C5-alkyl and dibromo-Cl- to C5-alkyl, it being pos-sible for the radicals R2 and R3, together with the carbon atoms of the C=C
double bond, to form a ring with up to 12 carbon atoms, and at least one o~ the radicals Rl ~o R4 being an alkyl or cycloalkyl radical of the type mentioned con-taining chlorine or bromine, is reacted with a solution of a percarboxylic acid containing ~ to 4 carbon atoms in a chlorinated hydrocarbon containing 1 to 8 carbon atoms at a molar ratio o~ monoolefin to per-caboxylic acid o~ 1.1 to 10 : 1 and at.a temperature of 30C
to 100C, A chloroalkyl-substituted or bromoalkyl-substituted monoole~in with at least 4 carbon atoms is preferably employed.
Within the scope of the compounds of the formula (I), exampl~s of possible compounds are, in particular, those o~
th~ following formulae:
R5-~H=CH-R6 (II) wherein R5 and R6 independently o~ one another denote Cl- to C5-alkyl, monochloro-Cl- to C5-alkyl, monobromo-Cl-to C5~alkyl, dichloro-Cl to C5-alkyl or dibromo-Cl-to C5-alkyl, it being possible for the radicals R5 and R6 to be li~ked to form a ring, together with the group CH=CH, and at least one o~ -the radicals R5 and R6 denoting monochloro Cl- to C5-alkyl, monobromo~Cl- to C5-alkyl, , ~219~
dichl~ro-Cl- to C5-alkyl or dibromo-Cl- to C5 alkyl;
--C=C ~
R9 ~ ~ R10, (III) (CH2)n wherein R7 and R8 independently of one another denote hydrogen, Cl- to C5-alkyl, monochloro-Cl- to C5-alkyl, monobro-mo-Cl- to C5-alkyl, di¢hloro-Cl- to C5-alkyl or dibromo~Cl- to C5_Q1kY1, R9 and Rlo independently o~ one another represent a methylene, chloromethylene, bromomethylene, 1,2 di-chloroethylene or 1,2 dibromomethylene radical and n represents an integer from 1 to 6, at least one of the radicals R7 - Rlo representing an alkyl, cyclo-alkyl or alkylene radical o~ the type mentioned containing chlorine or:bromine.
In detail, halogenoalkyl-substituted monoolefins which may be mentioned are: 2-c~loromethyl-propene, 3-chloro 2-chloromethyl-propene, 3-chloro-l butene, 1-chloro-2-butene f 1,4-dichloro-2-butene, 3,4-dichloro~l-butene, 3-chloro-1-pentene, 4-chloro-2-pentene, 1-chloro-2-pentene, 1,4-dichloro-2-pentene9 3,4-dichloro-1-pentene, 1,2-dichloro-3-pentene, 3~chloro-1-cyclopentene, 1,4-dichloro-2-cyclopentene, 3-chlo- -ro-l-hexene, l--chloro-2-hexene, 1,4-dichloro--2-hexene, 3,4-dichloro-l-hexene, 2-chloro-~-hexene, 2,5~dichloro-3-hexene, 3~chloro-1-cyclohexene, 19 4-dichloro-2-cyclohexene, l-chloro-2-heptene, 3-chloro-1-h~ptene, 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, l-chlo-ro-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, l-(l-chloro-cyclohexyl)-ethene, l-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-~.ecene, 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-dichlo-ro-2-undecene, 2-chloro-3-undecene, 4-chloro-2-undecene, 2,5-dichloro-3-undecene, 5-chloro-3-u~decene, 6-chloro-4-undecene, 4-chloro-5-undecene, 4,7-dichloro-5-undecene, 5-chloro~6-undecene, 5,8-dichloro-6-undeoene, 1-chloro-3-dodecene, 3-chloro-1-dodecene, 1,4-dichioro-2-dodecene, 2-chloro-3-dode-cene, 4-chloro-2-dodecene,.2,5-dichloro-3-dodecene, 5-chloro-3-dodecene, 6-chloro-4-dodecene, 4-chloro-5-dodecene, 4,7-dlchloro-5-dodecene, 5-chloro-6 dodecene, 5,8-dichloro-6-dodeoene, 5?7-dichloro-6-dodecene and 7 chloro-5-dodecene;
ZO 2-bromomethyl-propene, 3-bromo-2-bromomethyl-propene, 3-bromo-l-butene, l-bromo-2-butene, 1,4-dibromo-2-butene, 3,4-di-bromo-l-butene, 3-~romo~l-pentene, 4-bromo-2-pentene, l-bromo-2-pentene~ 1,4-dibromo~2-pentene, 3,4-dibromo-1-pentene; 1,2-dibro~o~3 pentene, 3-bromo-1-cyclopentene, 1,4-dibromo-2-cyclo-pentene, 3-bromo-1-hexene~ 1-bromo-2-hexene, 1,4-dibromo-2-hexene, 3 9 4-dibromo-1-hexene, 2-bromo 3-hexene, 2,5-dibromo-3-hexene/ ~-bromo-1-cyclohexene, 1,4-dibromo-2-cyclohexene, l-bromo-2-haptene, 3-bromo-l-hepten0, 3,4 dibromo-l-heptene, 1,4-di~romo-2-heptene ! 2-bromo 3-heptene 9 2,5 dibromo-3-31 heptene, 3-bromo-1-cycloheptene, 1,4-dibromo-Z-cycloheptene, l-bromo-2-octene, 3-bromo-1-octene, 1,4-dibromo-2-octene, 2 ~ 9 ~
.
3~ 7 2,5-dibromo-3-octene, 2-bromo-3-octene, 3-bromo-4-octene, 3,6~dibromo-4-octene, ~-bromo~l-cyclooctene, 1,4-dibromo-2-cyclooctene, l-(l-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, ~-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, Z,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-undeoene, 3-bromo-1-undecene, 1,4-dibro-mo-2-undecene, 2-bromo-3-undecene, 4-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-dodecenel 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 by the process according to the invention are tho~e of the formula R11-CH=cH-Rl~ (IV) wherein Rll and R12 independently o~ one another denote hydro-gen, Cl- to C~-alkyl, monochloro-Cl- to C5-alkyl, monobromo-Cl- to C5-alkyl, dichloro-Cl- to C5-alkyl or dibromo-Cl- to C5-alkyl, at least one of the radicals Rll and R12 representing monochloro-Cl to C5-alkyl, mon~bromo~Cl- to C5-alkyl, dichloro-Cl- to C5-alkyl or dibromo-Cl- to C5-alkyl.
In detail, examples which may be mentioned are: 2-chloromethyl-propene, 3-chloro-2-chloromethyl-propene, 3-chloro-l-butene, l-chloro-2-butene, 1,4 dichloro-2-butene~
394-dichloro-l-butene, ~chloro-l-pentene, 4-chloro-2-pentene, l-chloro-2-pentene, 1,4-dichloro-2-pentene, 3,4-dichloro-1-pentene; 1,2-dichloro-3-pentene, 3-chloro-1-hexene, l-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-l-pentene, 4-bromo-2-pentene, 1,4-dibromo-2-pentene, 3,4~dibromo-1-pentene, 1,2-dibromo-3-pentene, ~-bromo-l-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-l-butene are very particularly Ruitable ~or reaction with percarboxylic acids by the process according to the invention.
The most diverse chlorinated hydrocarbons can be used as sol~nts~ ~uch as methylene chloride, chloroform, carbon tetrachlorlde~ 1 chloroethane, ],2-dichloroethane, l,l-dichloro-eth~ne, 1,1,2,2-tetrachloroethane, l-chloroporpane, 2-chloro-propane, lf2-dichloropropane, 1,3-dichloropropane7 273-dichloro-propane, 1,2,3-trichloropropane, 1,1,2,3-tetrachloropropane9 butyl chlorid , 1,2-dichlorobutane, 1,4-dichlorobutane~
2,3-dichlorobutane, 1,3-dichlorobutane, 1,2,3,4-tetrachlorobutane, tertS butyl chloride, amyl chloride, ~0 1,2-dichloropentane 9 1,5-dichloropentane, 192,374-tetrachloro-pentane, cyclopentyl chloride, 192-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-dichloroheptane, octyl chloride, 1,2-dichlorooctane, 1,2,3,4-tetrachlorooctane, cyclooctyl chloride, and 1,2-dichlorooctane.
Preferred solvents are methylene chloride, chloroform, carbon tetrachloride and 1,2-dichloropropane. A particularly 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. Perpropionic acid and perisobutyric acid are preferably used. Perpropionic acid is particularly preferred. The preparation of the mineral acid-free peracids in one of the organic solvents mentioned can be carried out, for example, by the process described in DOS ~German Published Specification) 2,262,970.
In general, when carrying out the process according to the invention in practice, it is carried out in a temperature range from 30-100C. It is preferably carried out at 60-80C and particularly pre-ferably at 65-75C. In particular cases, the process can also be carried out below or above the temperatures indicated.
Besides the procedure under isothermal conditions, that is to say maintaining a uniform temperature in the entire reaction mixture, it is also possible to carry out the reaction with the setting up of a so-called temperature gradient, which in general increases as the reaction progresses. However, it is also possible to carry out the reaction in a manner such that a decreasing temperature gradient is set up as the reaction progresses.
According to the invention, the molar ratio of olefin to peracid is 1.1: 1 to 10:1. A molar ratio of 1.25:1 to 5:1 is preferably used. It is very particularly advantageous to use a molar ratio of 1.5 to 3.0 mols of olefin per mol of peracid.
The process according to the invention can be carried out under the most diverse pressures. In general, it is carried out under normal pressure; however, the process can also be carried out under reduced pressure or excess pressure.
rn general, the water content of the percarboxylic acid used for the epoxidation should be as low as possible. Low amounts of water of up to 5% by weight are generally not troublesome. A percaboxylic acid with a water content o up to 2% by weight, for example, is suitable.
la A percarboxylic acid solution which contains less than 1% by weight of water is preferably used. A water content of less than 0.1% by weight is particularly preferred.
In general, the hydrogen peroxide content of the percarboxylic acid used should be as low as possible. It 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 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 the reaction 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 of less than 10 ppm is particularl~ advantageous.
The reaction can be carried out discontinuously or contin-uously in the customary devices for reactions of this type, such as stirred kettles, boiling reactors, tube reactors, loop-reactors or cir-culatory reactors.
Glass, stainless steels or enamelled material can be used as materials of construction for carrying out the processes.
Heavy metal ions in the reaction mixture catalyse the decomposition of the percarboxylic acid. Substances which inactivate the ~ea~y~metal ions by means of complex formation are therefore generally ~z~
added to the percarboxylic ac;d solution. Kno~n substances of this type are gluconic acid, ethylenediaminetetraacetic acid, sodium silicate, sodium pyrophosphate, sodium hexametaphosphate, disodium dimethyl pyrophosphate or Na2(2-ethyl-hexyl)5(P3010)2 (DAS (German Published Specification) 1,056,596, column 4, line 60 et seq.).
The halogenoalkyl-substituted olefin can be introduced in various ways into the device used for the reaction. It can be put into the reactor together with the percarboxylic acid solution, or the two components are fed into the reactor separately from one another. Further-lQ more, it is possible to introduce the olefin and the percarboxylic acid solution into the reactor unit at different points. If several reactors connected in a cascade are used, it can be appropriate to introduce all the olefin into the first reactor. ~lowever, it is also possible to distribute the olefin among the various reactors.
The heat of reaction is remo~ed by internal or external coolers. In order to remove the heat of reaction, it is also possible to carry out the reaction under reflux (boiling reactors).
The reaction is appropriately carried out with as complete as possible conversion of the percarboxylic acid. In general, more than 95 mol % of the percarboxylic acid are reacted. It~is appropriate to react more than 98 mol % of the peracid.
When the reaction between the halogenoalkyl-substituted olefin and the peracid is carried out according to the invention, it is possible to achieve oxirane yields of 90% of theory and more, relative to percarbox~llc acid employed.
The reaction mixture is worked up ln a manner which is in itsel known, for example by distillation. It is particularly advantageous to extract the reaction mixture with water, before working up by distil-lation, in order to separate off the carboxylic acid, corresponding to the percarboxylic acid, which is formed during the reaction. The extraction can be carried out in the customary extractors, such as mixer/separators, perforated tray extractors, pulsating perforaced tray columns, rotating disc extractors or extraction centrifuges.
In a preferred manner of carrying out the process, an approximately 20% strength by weight solution of perpropionic acid in 1,2-dichloropropane is added to three times the molar amount of halogeno-alkyl-substituted olefin, which is thermostatically controlled at 70C, whilst stirring. The perpropionic acid solution contains less than 10 ppm of mineral acid; it has a water content which is below o.l% and has a hydrogen peroxide content of less than 0.3%. Before the reaction, about 0.05% by weight of Na5~2-ethylhexyl)5(P3010)2 was added to the perpropionic acid in order to complex heavy metal ions. The progress and the end of the reaction are monitored by removing samples from the reaction solution at intervals of time and determining tritrimetrically the content of percarboxylic acid still present. After the reaction has ended, the reaction mixture is cooled and washed three times with the same amount by weight of water in order to remove the propionic acid. The propionic acid-free reaction mixture is then fractionated.
The examples which follow illustrate the invention. Unless indicated otherwise, all the percentage data represent per cent by weight.
Example 1 -Preparation of 2-(1,2-dichloroethyl-)oxirane from 3,4-dichloro-1-butene and perpropionic acid.
62,96 g ~0.147 mol) of perpropionic acid, as a 21% strength solution in 1,2-dichloropropane, were added dropwise to 55.87 g ~0.447 mol) of 3,4-dichloro-1-butene at 70C, whilst stirring. After the dropwise addition, the mixture was stirred at this temperature for a further 6 hours, and the tritrimetric analysis then showed a perpropionic acid conversion of 95%. The reaction solution was cooled to room temperature and analysed by gas chromatography. As the analysis showed, 2-~1,2-dichloroethyl-)-oxirane was formed with a selectivity of 92.6%, 3Q rela~ive to perpropionic acid employed.
The reaction mixture was washed several times with water in order to remove the propionic acid, 1,2-dichloropropana was distilled - ~26~7 off and the reaction product was then fractionated in a 40 cm packed column, packed with 4 mm glass Raschig rings. 18.5 g of 2-(1,2-dichloroethyl-)-oxirane were isolated with a purity oE 99.4%.
F~xample 2 Preparation of 2,3-bis-(chloromethyl)-oxirane from 1,4-dichloro-2-butene and p~rpropionic acid.
66,15 g (0.147 mol) o perpropionic acid, as an approximately 20% strength solution in 1,2-dichloropropane, were added dropwise to 55.2 g (0.4416 mol) o 1,4-dichloro-2-butene at 70C and the mixture was then further stirred at this temperature. After a reaction time of 4 hours, the peracid conversion was 94%, and after 6 hours it was over 97%. 2,3-Bis~chloromethyl)-oxirane was formed with a selectivity of 94%, relative to perpropionic acid employed. After removing the propionic acid by extracting the reaction mixture by shaking several times with water and subsequently separating off the 1,2-dichloropropane by distillation, and after fractionation of the reac~ion product over a 30 cm packed column, ~11ed with 4 mm glass Raschig rings, 19.0 g of 2,3-bis-(chloromethyl)- ;
oxirane were obtained with a purity of 99.9%.
Example 3 Continuous preparation of 2,3-bis-~chloromethyl)-oxirane from 1,4-dichloro-2-butene and perpropionic acid.
A solution of perpropionic acid ln 1,2-dichloropropane, to wh~ch a stabiliser o the type, which is commercially available, consisting of sodium salts of polyphosphorlc acids partially esterified with long-chain alcohols has been added, was reacted with 1,4-dichloro-2-butene in a reactlon system in the form of a three-stage cascade of stirred kettles.
~ach of the three stirred kettles had a volume of 9.41. The kettles were heated via heating coils located in the kettle. All three kettles were thermostatically controlled at 70C.
3Q 2,137.5 g ~4.75 mols) of perpropionic acid, as a 20% strength solution in 1,2-dichloropropane, and 1,781.25 g (14.25 mols) of 1,4-l6-dichloro-2-butene per hour were fed into this reaction system, which corresponded to an average residence time of about 8 hours. Under these reaction conditions, the perpropionic acid was converted to the extent Oe 94.2%. The selectivity of the 2,3-bis-(chloromethyl)-oxirane formed was 92%, relative to perpropionic acid employed.
The reaction mixture obtained after the third reactor had the following average composition: 35.6% of 1,2-dichloropropane, 31.4%
of 1,4-dichloro-2-butene, 15.7% of 2,3-bis-~chloromethyl)-oxirane and 17% of propionic acid. This mixture was extracted in a pulsating per-forated tray column with twice the amount of water in order to separate off the propionic acid. Thereafter, the residual content of propionic acid was less than 0.1%. The reaction mixture obtained after this operation was fractionated in a distillation line. 1,2-dichloropropane ~as distilled off in a first column in an amount of 1,395 g per hour.
~he bottom product of this column, which essentially consisted of starting m~terial and oxirane, was fractionated in a second column under reduced pressure. 1,235 g of 1,4-dichloro-2-butene per hour were obtained as the head product. The bottom product of this column was freed from high-boiling constituents in a third column under reduced pressure. 606 g of 2,3-bis-(chloromethyl)-oxirane per hour were obtained as the head product with a purity of over 99.9%. This corresponds to a yield of 90.5%, relative to the perpropionic acid employed in the reaction system.
Example 4 Epoxidation of 1,4-dibromo-2-butene with perpropionic acid.
a) Bromination of butadiene 171.4 g (3.17 mols) of butadiene were dissolved in 400 ml of n-hexane. 314 g (1.964 mols) of bromine were added dropwise at -20C, whilst stirring. After the end of the dropwise addition, the mixture was stirred at this temperature for a further 2 hours. It was then allowed to warm to room temperature and the solvent was removed in vacuo. 380.4 g of crude dibromobutene resulted, the ratio of l,4-dibromo-2-butene to 3,4-dibromo-l~butene being about 2:1. The 1,4-dibromo-2-butene was . .
isolated b~ dist~llation.
b~ Reaction of 1,4-dibromo-2-butene with perpropionic acid 45 g of 20% strength perproplonic acid in 1,2-dichloropropane ~0.1 mol) were added dropwise to 64.2 g ~0.3 mol~ of 1,4-dibromo-2-butene at 70C, whilst stirring, and the mixture was stirred at this temperature for a further 4 hours. After this time, the peracid con-~ersion was 93%. Analysls by gas chromatography showed that the epoxide was formed with a selectivity of 90.8%, relative to perpropionic acid employed. After cooling, the reaction mixture was washed several times w~th water in order to remove the propionic acid and the reaction product was fractlonated. 20.3 g of epoxide were obtained.
,~
5 et seq.. After a reaction time o~ ten hours, the peracid conversion is 91~. The oxirane is isolated in 68Q~ yield with a purity of 90.5%.
The preparation o~ 3,4-dichloro-1,2-epoxybutane by reacting 3,4-dichloro-1-butene with peracetic acid in acetone is described in British Patent Specification 784,620, in Example VII, page 7, line 5 et seq.. According to this pre-paration, the peracid conversion is 89% and the yield of epoxide is 75%. The purity of the epoxide is given as 93.3%. An account of the epoxidation of an olefin with perpropionic acid is also given in British Patent Specification 784,620, in Example IX, page 7, line 85 et seq. According to this epoxida-tion, after reacting crotyl chloride with a solutisn of perpropionic acid in ethyl propionate, l-chloro-2,3-epoxybutane was obtained in 56% yield. The peracid conversion was 90~.
In contrast, it has now been found that halogenoalkyl-substituted oxiranes can be prepared in high yields and high purity from halogenoalkyl-substituted olefins and percarboxylic acids in organic solution by a process in which a chloroalkyl-sub&titute~l or bromoalkyl-substituted monoole~in of the general formula Rl-C = C-R4 (I) wherein Rl and R4 independently of one another denote hydrogen, Cl- to C5-alkyl, C5- to C7~cycloalkyl, monochloro-Cl- to C5-alkyl, monobromo-Cl- to C5-alkyl, dichloro-Cl- to C5~alkyl, dibrsmo-Cl- to C5-alkyl, monochloro-C5 to C7-cycloalkyl, monsbromo-C5- to C7-cycloalkyl, 3C dichloro~C5~ to C7 cycloalkyl or dibromo-C5- to C7-~@_~_a~ 6 -cycloalkyl and R2 and R3 independently of one another represent hydrogen, Cl- to C5-alkyl, monochloro-Cl- to C5-al-kyl, monobromo-Cl- to C5-alkyl, dichloro-Cl- to C5-alkyl and dibromo-Cl- to C5-alkyl, it being pos-sible for the radicals R2 and R3, together with the carbon atoms of the C=C
double bond, to form a ring with up to 12 carbon atoms, and at least one o~ the radicals Rl ~o R4 being an alkyl or cycloalkyl radical of the type mentioned con-taining chlorine or bromine, is reacted with a solution of a percarboxylic acid containing ~ to 4 carbon atoms in a chlorinated hydrocarbon containing 1 to 8 carbon atoms at a molar ratio o~ monoolefin to per-caboxylic acid o~ 1.1 to 10 : 1 and at.a temperature of 30C
to 100C, A chloroalkyl-substituted or bromoalkyl-substituted monoole~in with at least 4 carbon atoms is preferably employed.
Within the scope of the compounds of the formula (I), exampl~s of possible compounds are, in particular, those o~
th~ following formulae:
R5-~H=CH-R6 (II) wherein R5 and R6 independently o~ one another denote Cl- to C5-alkyl, monochloro-Cl- to C5-alkyl, monobromo-Cl-to C5~alkyl, dichloro-Cl to C5-alkyl or dibromo-Cl-to C5-alkyl, it being possible for the radicals R5 and R6 to be li~ked to form a ring, together with the group CH=CH, and at least one o~ -the radicals R5 and R6 denoting monochloro Cl- to C5-alkyl, monobromo~Cl- to C5-alkyl, , ~219~
dichl~ro-Cl- to C5-alkyl or dibromo-Cl- to C5 alkyl;
--C=C ~
R9 ~ ~ R10, (III) (CH2)n wherein R7 and R8 independently of one another denote hydrogen, Cl- to C5-alkyl, monochloro-Cl- to C5-alkyl, monobro-mo-Cl- to C5-alkyl, di¢hloro-Cl- to C5-alkyl or dibromo~Cl- to C5_Q1kY1, R9 and Rlo independently o~ one another represent a methylene, chloromethylene, bromomethylene, 1,2 di-chloroethylene or 1,2 dibromomethylene radical and n represents an integer from 1 to 6, at least one of the radicals R7 - Rlo representing an alkyl, cyclo-alkyl or alkylene radical o~ the type mentioned containing chlorine or:bromine.
In detail, halogenoalkyl-substituted monoolefins which may be mentioned are: 2-c~loromethyl-propene, 3-chloro 2-chloromethyl-propene, 3-chloro-l butene, 1-chloro-2-butene f 1,4-dichloro-2-butene, 3,4-dichloro~l-butene, 3-chloro-1-pentene, 4-chloro-2-pentene, 1-chloro-2-pentene, 1,4-dichloro-2-pentene9 3,4-dichloro-1-pentene, 1,2-dichloro-3-pentene, 3~chloro-1-cyclopentene, 1,4-dichloro-2-cyclopentene, 3-chlo- -ro-l-hexene, l--chloro-2-hexene, 1,4-dichloro--2-hexene, 3,4-dichloro-l-hexene, 2-chloro-~-hexene, 2,5~dichloro-3-hexene, 3~chloro-1-cyclohexene, 19 4-dichloro-2-cyclohexene, l-chloro-2-heptene, 3-chloro-1-h~ptene, 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, l-chlo-ro-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, l-(l-chloro-cyclohexyl)-ethene, l-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-~.ecene, 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-dichlo-ro-2-undecene, 2-chloro-3-undecene, 4-chloro-2-undecene, 2,5-dichloro-3-undecene, 5-chloro-3-u~decene, 6-chloro-4-undecene, 4-chloro-5-undecene, 4,7-dichloro-5-undecene, 5-chloro~6-undecene, 5,8-dichloro-6-undeoene, 1-chloro-3-dodecene, 3-chloro-1-dodecene, 1,4-dichioro-2-dodecene, 2-chloro-3-dode-cene, 4-chloro-2-dodecene,.2,5-dichloro-3-dodecene, 5-chloro-3-dodecene, 6-chloro-4-dodecene, 4-chloro-5-dodecene, 4,7-dlchloro-5-dodecene, 5-chloro-6 dodecene, 5,8-dichloro-6-dodeoene, 5?7-dichloro-6-dodecene and 7 chloro-5-dodecene;
ZO 2-bromomethyl-propene, 3-bromo-2-bromomethyl-propene, 3-bromo-l-butene, l-bromo-2-butene, 1,4-dibromo-2-butene, 3,4-di-bromo-l-butene, 3-~romo~l-pentene, 4-bromo-2-pentene, l-bromo-2-pentene~ 1,4-dibromo~2-pentene, 3,4-dibromo-1-pentene; 1,2-dibro~o~3 pentene, 3-bromo-1-cyclopentene, 1,4-dibromo-2-cyclo-pentene, 3-bromo-1-hexene~ 1-bromo-2-hexene, 1,4-dibromo-2-hexene, 3 9 4-dibromo-1-hexene, 2-bromo 3-hexene, 2,5-dibromo-3-hexene/ ~-bromo-1-cyclohexene, 1,4-dibromo-2-cyclohexene, l-bromo-2-haptene, 3-bromo-l-hepten0, 3,4 dibromo-l-heptene, 1,4-di~romo-2-heptene ! 2-bromo 3-heptene 9 2,5 dibromo-3-31 heptene, 3-bromo-1-cycloheptene, 1,4-dibromo-Z-cycloheptene, l-bromo-2-octene, 3-bromo-1-octene, 1,4-dibromo-2-octene, 2 ~ 9 ~
.
3~ 7 2,5-dibromo-3-octene, 2-bromo-3-octene, 3-bromo-4-octene, 3,6~dibromo-4-octene, ~-bromo~l-cyclooctene, 1,4-dibromo-2-cyclooctene, l-(l-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, ~-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, Z,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-undeoene, 3-bromo-1-undecene, 1,4-dibro-mo-2-undecene, 2-bromo-3-undecene, 4-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-dodecenel 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 by the process according to the invention are tho~e of the formula R11-CH=cH-Rl~ (IV) wherein Rll and R12 independently o~ one another denote hydro-gen, Cl- to C~-alkyl, monochloro-Cl- to C5-alkyl, monobromo-Cl- to C5-alkyl, dichloro-Cl- to C5-alkyl or dibromo-Cl- to C5-alkyl, at least one of the radicals Rll and R12 representing monochloro-Cl to C5-alkyl, mon~bromo~Cl- to C5-alkyl, dichloro-Cl- to C5-alkyl or dibromo-Cl- to C5-alkyl.
In detail, examples which may be mentioned are: 2-chloromethyl-propene, 3-chloro-2-chloromethyl-propene, 3-chloro-l-butene, l-chloro-2-butene, 1,4 dichloro-2-butene~
394-dichloro-l-butene, ~chloro-l-pentene, 4-chloro-2-pentene, l-chloro-2-pentene, 1,4-dichloro-2-pentene, 3,4-dichloro-1-pentene; 1,2-dichloro-3-pentene, 3-chloro-1-hexene, l-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-l-pentene, 4-bromo-2-pentene, 1,4-dibromo-2-pentene, 3,4~dibromo-1-pentene, 1,2-dibromo-3-pentene, ~-bromo-l-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-l-butene are very particularly Ruitable ~or reaction with percarboxylic acids by the process according to the invention.
The most diverse chlorinated hydrocarbons can be used as sol~nts~ ~uch as methylene chloride, chloroform, carbon tetrachlorlde~ 1 chloroethane, ],2-dichloroethane, l,l-dichloro-eth~ne, 1,1,2,2-tetrachloroethane, l-chloroporpane, 2-chloro-propane, lf2-dichloropropane, 1,3-dichloropropane7 273-dichloro-propane, 1,2,3-trichloropropane, 1,1,2,3-tetrachloropropane9 butyl chlorid , 1,2-dichlorobutane, 1,4-dichlorobutane~
2,3-dichlorobutane, 1,3-dichlorobutane, 1,2,3,4-tetrachlorobutane, tertS butyl chloride, amyl chloride, ~0 1,2-dichloropentane 9 1,5-dichloropentane, 192,374-tetrachloro-pentane, cyclopentyl chloride, 192-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-dichloroheptane, octyl chloride, 1,2-dichlorooctane, 1,2,3,4-tetrachlorooctane, cyclooctyl chloride, and 1,2-dichlorooctane.
Preferred solvents are methylene chloride, chloroform, carbon tetrachloride and 1,2-dichloropropane. A particularly 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. Perpropionic acid and perisobutyric acid are preferably used. Perpropionic acid is particularly preferred. The preparation of the mineral acid-free peracids in one of the organic solvents mentioned can be carried out, for example, by the process described in DOS ~German Published Specification) 2,262,970.
In general, when carrying out the process according to the invention in practice, it is carried out in a temperature range from 30-100C. It is preferably carried out at 60-80C and particularly pre-ferably at 65-75C. In particular cases, the process can also be carried out below or above the temperatures indicated.
Besides the procedure under isothermal conditions, that is to say maintaining a uniform temperature in the entire reaction mixture, it is also possible to carry out the reaction with the setting up of a so-called temperature gradient, which in general increases as the reaction progresses. However, it is also possible to carry out the reaction in a manner such that a decreasing temperature gradient is set up as the reaction progresses.
According to the invention, the molar ratio of olefin to peracid is 1.1: 1 to 10:1. A molar ratio of 1.25:1 to 5:1 is preferably used. It is very particularly advantageous to use a molar ratio of 1.5 to 3.0 mols of olefin per mol of peracid.
The process according to the invention can be carried out under the most diverse pressures. In general, it is carried out under normal pressure; however, the process can also be carried out under reduced pressure or excess pressure.
rn general, the water content of the percarboxylic acid used for the epoxidation should be as low as possible. Low amounts of water of up to 5% by weight are generally not troublesome. A percaboxylic acid with a water content o up to 2% by weight, for example, is suitable.
la A percarboxylic acid solution which contains less than 1% by weight of water is preferably used. A water content of less than 0.1% by weight is particularly preferred.
In general, the hydrogen peroxide content of the percarboxylic acid used should be as low as possible. It 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 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 the reaction 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 of less than 10 ppm is particularl~ advantageous.
The reaction can be carried out discontinuously or contin-uously in the customary devices for reactions of this type, such as stirred kettles, boiling reactors, tube reactors, loop-reactors or cir-culatory reactors.
Glass, stainless steels or enamelled material can be used as materials of construction for carrying out the processes.
Heavy metal ions in the reaction mixture catalyse the decomposition of the percarboxylic acid. Substances which inactivate the ~ea~y~metal ions by means of complex formation are therefore generally ~z~
added to the percarboxylic ac;d solution. Kno~n substances of this type are gluconic acid, ethylenediaminetetraacetic acid, sodium silicate, sodium pyrophosphate, sodium hexametaphosphate, disodium dimethyl pyrophosphate or Na2(2-ethyl-hexyl)5(P3010)2 (DAS (German Published Specification) 1,056,596, column 4, line 60 et seq.).
The halogenoalkyl-substituted olefin can be introduced in various ways into the device used for the reaction. It can be put into the reactor together with the percarboxylic acid solution, or the two components are fed into the reactor separately from one another. Further-lQ more, it is possible to introduce the olefin and the percarboxylic acid solution into the reactor unit at different points. If several reactors connected in a cascade are used, it can be appropriate to introduce all the olefin into the first reactor. ~lowever, it is also possible to distribute the olefin among the various reactors.
The heat of reaction is remo~ed by internal or external coolers. In order to remove the heat of reaction, it is also possible to carry out the reaction under reflux (boiling reactors).
The reaction is appropriately carried out with as complete as possible conversion of the percarboxylic acid. In general, more than 95 mol % of the percarboxylic acid are reacted. It~is appropriate to react more than 98 mol % of the peracid.
When the reaction between the halogenoalkyl-substituted olefin and the peracid is carried out according to the invention, it is possible to achieve oxirane yields of 90% of theory and more, relative to percarbox~llc acid employed.
The reaction mixture is worked up ln a manner which is in itsel known, for example by distillation. It is particularly advantageous to extract the reaction mixture with water, before working up by distil-lation, in order to separate off the carboxylic acid, corresponding to the percarboxylic acid, which is formed during the reaction. The extraction can be carried out in the customary extractors, such as mixer/separators, perforated tray extractors, pulsating perforaced tray columns, rotating disc extractors or extraction centrifuges.
In a preferred manner of carrying out the process, an approximately 20% strength by weight solution of perpropionic acid in 1,2-dichloropropane is added to three times the molar amount of halogeno-alkyl-substituted olefin, which is thermostatically controlled at 70C, whilst stirring. The perpropionic acid solution contains less than 10 ppm of mineral acid; it has a water content which is below o.l% and has a hydrogen peroxide content of less than 0.3%. Before the reaction, about 0.05% by weight of Na5~2-ethylhexyl)5(P3010)2 was added to the perpropionic acid in order to complex heavy metal ions. The progress and the end of the reaction are monitored by removing samples from the reaction solution at intervals of time and determining tritrimetrically the content of percarboxylic acid still present. After the reaction has ended, the reaction mixture is cooled and washed three times with the same amount by weight of water in order to remove the propionic acid. The propionic acid-free reaction mixture is then fractionated.
The examples which follow illustrate the invention. Unless indicated otherwise, all the percentage data represent per cent by weight.
Example 1 -Preparation of 2-(1,2-dichloroethyl-)oxirane from 3,4-dichloro-1-butene and perpropionic acid.
62,96 g ~0.147 mol) of perpropionic acid, as a 21% strength solution in 1,2-dichloropropane, were added dropwise to 55.87 g ~0.447 mol) of 3,4-dichloro-1-butene at 70C, whilst stirring. After the dropwise addition, the mixture was stirred at this temperature for a further 6 hours, and the tritrimetric analysis then showed a perpropionic acid conversion of 95%. The reaction solution was cooled to room temperature and analysed by gas chromatography. As the analysis showed, 2-~1,2-dichloroethyl-)-oxirane was formed with a selectivity of 92.6%, 3Q rela~ive to perpropionic acid employed.
The reaction mixture was washed several times with water in order to remove the propionic acid, 1,2-dichloropropana was distilled - ~26~7 off and the reaction product was then fractionated in a 40 cm packed column, packed with 4 mm glass Raschig rings. 18.5 g of 2-(1,2-dichloroethyl-)-oxirane were isolated with a purity oE 99.4%.
F~xample 2 Preparation of 2,3-bis-(chloromethyl)-oxirane from 1,4-dichloro-2-butene and p~rpropionic acid.
66,15 g (0.147 mol) o perpropionic acid, as an approximately 20% strength solution in 1,2-dichloropropane, were added dropwise to 55.2 g (0.4416 mol) o 1,4-dichloro-2-butene at 70C and the mixture was then further stirred at this temperature. After a reaction time of 4 hours, the peracid conversion was 94%, and after 6 hours it was over 97%. 2,3-Bis~chloromethyl)-oxirane was formed with a selectivity of 94%, relative to perpropionic acid employed. After removing the propionic acid by extracting the reaction mixture by shaking several times with water and subsequently separating off the 1,2-dichloropropane by distillation, and after fractionation of the reac~ion product over a 30 cm packed column, ~11ed with 4 mm glass Raschig rings, 19.0 g of 2,3-bis-(chloromethyl)- ;
oxirane were obtained with a purity of 99.9%.
Example 3 Continuous preparation of 2,3-bis-~chloromethyl)-oxirane from 1,4-dichloro-2-butene and perpropionic acid.
A solution of perpropionic acid ln 1,2-dichloropropane, to wh~ch a stabiliser o the type, which is commercially available, consisting of sodium salts of polyphosphorlc acids partially esterified with long-chain alcohols has been added, was reacted with 1,4-dichloro-2-butene in a reactlon system in the form of a three-stage cascade of stirred kettles.
~ach of the three stirred kettles had a volume of 9.41. The kettles were heated via heating coils located in the kettle. All three kettles were thermostatically controlled at 70C.
3Q 2,137.5 g ~4.75 mols) of perpropionic acid, as a 20% strength solution in 1,2-dichloropropane, and 1,781.25 g (14.25 mols) of 1,4-l6-dichloro-2-butene per hour were fed into this reaction system, which corresponded to an average residence time of about 8 hours. Under these reaction conditions, the perpropionic acid was converted to the extent Oe 94.2%. The selectivity of the 2,3-bis-(chloromethyl)-oxirane formed was 92%, relative to perpropionic acid employed.
The reaction mixture obtained after the third reactor had the following average composition: 35.6% of 1,2-dichloropropane, 31.4%
of 1,4-dichloro-2-butene, 15.7% of 2,3-bis-~chloromethyl)-oxirane and 17% of propionic acid. This mixture was extracted in a pulsating per-forated tray column with twice the amount of water in order to separate off the propionic acid. Thereafter, the residual content of propionic acid was less than 0.1%. The reaction mixture obtained after this operation was fractionated in a distillation line. 1,2-dichloropropane ~as distilled off in a first column in an amount of 1,395 g per hour.
~he bottom product of this column, which essentially consisted of starting m~terial and oxirane, was fractionated in a second column under reduced pressure. 1,235 g of 1,4-dichloro-2-butene per hour were obtained as the head product. The bottom product of this column was freed from high-boiling constituents in a third column under reduced pressure. 606 g of 2,3-bis-(chloromethyl)-oxirane per hour were obtained as the head product with a purity of over 99.9%. This corresponds to a yield of 90.5%, relative to the perpropionic acid employed in the reaction system.
Example 4 Epoxidation of 1,4-dibromo-2-butene with perpropionic acid.
a) Bromination of butadiene 171.4 g (3.17 mols) of butadiene were dissolved in 400 ml of n-hexane. 314 g (1.964 mols) of bromine were added dropwise at -20C, whilst stirring. After the end of the dropwise addition, the mixture was stirred at this temperature for a further 2 hours. It was then allowed to warm to room temperature and the solvent was removed in vacuo. 380.4 g of crude dibromobutene resulted, the ratio of l,4-dibromo-2-butene to 3,4-dibromo-l~butene being about 2:1. The 1,4-dibromo-2-butene was . .
isolated b~ dist~llation.
b~ Reaction of 1,4-dibromo-2-butene with perpropionic acid 45 g of 20% strength perproplonic acid in 1,2-dichloropropane ~0.1 mol) were added dropwise to 64.2 g ~0.3 mol~ of 1,4-dibromo-2-butene at 70C, whilst stirring, and the mixture was stirred at this temperature for a further 4 hours. After this time, the peracid con-~ersion was 93%. Analysls by gas chromatography showed that the epoxide was formed with a selectivity of 90.8%, relative to perpropionic acid employed. After cooling, the reaction mixture was washed several times w~th water in order to remove the propionic acid and the reaction product was fractlonated. 20.3 g of epoxide were obtained.
,~
Claims (14)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Process for the preparation of halogenoalkyl-substituted oxiranes from halogenoalkyl-substituted olefins and percarboxylic acids, characterised in that a chloroalkyl-substituted or bromoalkyl-substituted monoolefin of the general formula wherein R1 and R4 independently of one another denote hydrogen, C1- to C5-alkyl, C5- to C7-cycloalkyl, monochloro-C1-to C5-alkyl, monobromo-C1- to C5-alkyl,dichloro-C1-to C5-alkyl, dibromo-C1- to C5-alkyl, monochloro-C5-to C7-cycloalkyl, monobromo-C5- to C7-cylcoalkyl, dichloro-C5- to C7-cycloalkyl or dibromo-C5- to C7-cycloalkyl and R2 and R3 independently of one another represent hydrogen, C1- to C5-alkyl, monochloro-C1- to C5-alkyl, monobromo-C1-to C5-alkyl, dichloro-C1- to C5-alkyl and dibromo-C1- to C5-alkyl, it being possible for the radicals R2 and R3, together with the carbon atoms of the C=C double bond, to form a ring with up to 12 carbon atoms, and at least one of the radicals R1 to R4 being an alkyl or cycloalkyl radical of the type mentioned containing chlorine or bromine, is reacted 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 Process according to Claim 1, characterised in that an olefin of the formula R5-CH=CH-R6 wherein R5 and R6 independently of one another denote C1- to C5-alkyl, monochloro-C1- to C5-alkyl, monobromo-C1-to C5-alkyl, dichloro-C1- to C5-alkyl or dibromo-C1-to C5-alkyl, it being posslble for the radicals R5 and R6 to be linked to form a ring, together with the group CH=CH, and at least one of the radicals R5 and R6 denoting monochloro-C1- to C5-alkyl, monobromo-C1 to C5-alkyl, dichloro-C1- to C5-alkyl or dibromo-C1- to C5 alkyl, is employed as the chloroalkyl-substituted or bromoalkyl-substituted monoolefin.
3. Process according to Claim 1 and 2, characterised in that an olefin of the formula , wherein R7 and R8 independently of one another denote hydrogen, C1- to C5-alkyl, monochloro-C1- to C5-alkyl, monobro-mo-C1- to C5-alkyl, dichloro-C1- to C5-alkyl or dibromo-C1- to C5-alkyl, R9 and R10 independently of one another represent a methylene, chloromethylene, bromomethylene, 1,2-di-chloroethylene or l,2-dibromomethylene radical and n represents an integer from 1 to 6, at least one of the radicals R7 - R10 representing an alkyl, cyclo-alkyl or alkylene radical of the type mentioned containing chlorine or bromine, is employed as the chloroalkyl-substituted or bromoalkyl-substituted monoolefin.
4. Process according to Claim 1 and 2, characterised in that an olefin of the formula R11-CH=CH-R12 wherein R11 and R12 independently of one another denote hydrogen, C1- to C5-alkyl, monochloro-C1- to C5-alkyl, monobromo-C1- to C5-alkyl, dichloro-C1- to C5-alkyl or dibromo-C1- to C5-alkyl, at least one of the radicals R11 and R12 representing monochloro-C1- to C5-alkyl, monobromo-C1- to C5-alkyl, dichloro-C1- to C5-alkyl or dibromo-C1- to C5-alkyl, is employed as the chloroalkyl-substituted or bromoalkyl-substituted monoolefin.
5. Process according to Claim 1, characterised in that a chloro-alkyl-substituted or bromoalkyl-substituted monoolefin with at least 4 carbon atoms is employed.
6. Process according to Claim 1, characterised in that 1,4-dichloro-2-butene is employed as the chloroalkyl-substituted or bromo-alkyl-substituted olefin.
7. Process according to Claim 1, characterised in that 3,4-dichloro-l-butene is employed as the chloroalkyl-substituted or bromo-alkyl-substituted olefin.
8. Process according to Claim 1, characterised in that 1,4-dibromo-2-butene is employed as the chloroalkyl-substituted or bromoalkyl-substituted olefin.
9. Process according to Claim 1, characterised in that per-propionic acid is employed as the percarboxylic acid.
10. Process according to Claim 1, characterised in that per-isobutyric acid is employed as the percarboxylic acid.
11. Process according to Claim 1, characterised in that dichloro-propane is used as the chlorinated hydrocarbon.
12. Process according to Claim 1, characterised in that the reaction is carried out at a molar ratio of olefin to peracid of 1.5 to 3:1.
13. Process according to Claim 1, characterised in that the reaction is carried out at a temperature from 60 to 80°C.
14. Process according to Claim 1, characterised in that the reaction product is carried out by extraction of the reaction mixture with water in order to separate off the carboxylic acid, corresponding to the percarboxylic acid, formed during the reaction.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19772734085 DE2734085A1 (en) | 1977-07-28 | 1977-07-28 | PROCESS FOR THE PREPARATION OF HALOGENALKYL SUBSTITUTED OXIRANS |
| DEP2734085.8 | 1977-07-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1120047A true CA1120047A (en) | 1982-03-16 |
Family
ID=6015052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000308193A Expired CA1120047A (en) | 1977-07-28 | 1978-07-26 | Process for the preparation of halogenoalkyl- substituted oxiranes |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0000554B1 (en) |
| JP (1) | JPS5424806A (en) |
| AT (1) | AT358057B (en) |
| CA (1) | CA1120047A (en) |
| DD (1) | DD138067A5 (en) |
| DE (2) | DE2734085A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2456096A1 (en) * | 1979-05-10 | 1980-12-05 | Solvay | PROCESS FOR THE MANUFACTURE OF OLEFIN OXIDES |
| DE102005019296A1 (en) | 2005-04-26 | 2006-11-09 | Deutsche Exide Gmbh | Degassing valve for acid batteries |
| DE102021123420A1 (en) | 2020-09-11 | 2022-03-17 | Illinois Tool Works Inc. | emergency degassing valve |
| DE102023106792A1 (en) | 2022-04-11 | 2023-10-12 | Illinois Tool Works Inc. | Emergency degassing valve device |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1535313A (en) * | 1975-02-04 | 1978-12-13 | Interox Chemicals Ltd | Production of peracids and of epoxides |
| GB1584355A (en) * | 1976-10-26 | 1981-02-11 | Propylox Sa | Epoxidation |
| BE860029A (en) * | 1976-10-26 | 1978-04-24 | Propylox Sa | PROCESS FOR THE EPOXIDATION OF OLEFINS |
-
1977
- 1977-07-28 DE DE19772734085 patent/DE2734085A1/en not_active Withdrawn
-
1978
- 1978-07-20 EP EP78100456A patent/EP0000554B1/en not_active Expired
- 1978-07-20 DE DE7878100456T patent/DE2861619D1/en not_active Expired
- 1978-07-26 CA CA000308193A patent/CA1120047A/en not_active Expired
- 1978-07-26 AT AT544578A patent/AT358057B/en not_active IP Right Cessation
- 1978-07-26 JP JP9056778A patent/JPS5424806A/en active Pending
- 1978-07-26 DD DD78206957A patent/DD138067A5/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE2734085A1 (en) | 1979-02-22 |
| AT358057B (en) | 1980-08-25 |
| ATA544578A (en) | 1980-01-15 |
| DD138067A5 (en) | 1979-10-10 |
| EP0000554B1 (en) | 1982-02-10 |
| DE2861619D1 (en) | 1982-03-18 |
| JPS5424806A (en) | 1979-02-24 |
| EP0000554A1 (en) | 1979-02-07 |
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