CA1120048A - Process for the preparation of halogenoalkyl- substituted oxiranes - Google Patents
Process for the preparation of halogenoalkyl- substituted oxiranesInfo
- Publication number
- CA1120048A CA1120048A CA000308194A CA308194A CA1120048A CA 1120048 A CA1120048 A CA 1120048A CA 000308194 A CA000308194 A CA 000308194A CA 308194 A CA308194 A CA 308194A CA 1120048 A CA1120048 A CA 1120048A
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- Prior art keywords
- alkyl
- substituted
- dichloro
- dibromo
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Classifications
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
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 an aromatic hydrocarbon solvent.
Description
0~
The present invention relates to an improved process for the preparation of halogenoalkyl-substituted oxiranes from halogenoalkyl-substituted olefins and percarboxylic acids~
Halogenoalkyl-~ubstituted oxiranes are used in the field of lacquers and plastics and as organic intermediate products.
It is known to prepare chloroalkyl-3ubstituted oxi-ranes from the corresponding olefins by the chlorohydrin process. Thi~ process has the disadvantage that undesired chlorinated by-product~ 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 ~eq., in p~rticular 3. 13-15; and DAS (German Published Specification~
19543,174, column 2, line 15 et ~eq., in particular 3. 32-35).
It i8 al80 frequentl~ icult definitively -to pre-pare a single reaction prod,~ct by the,chlorohydrin method.
Thu~, th~ reaction o~ 4-chlorobut-2-ene,wi,th hypochlorous acid zo l~ads to a mixture of two products, which may be characterised by the follcwing formulao:
OH Cl Cl Cl 0~ Cl CH3-CH-CH CH2 and CH3-CH-CH-CH2 ',' ~ Accordingly, subsequent dehydrohalogenation o~ thi~
mixture u~ing a',bas~ gives a mixture of two i~omeric oxiranes, as the ~ormulae below illustrate (DAS (German Published Specification) 19056,596, column 1, line 53 to column 2, 3-43):
~ ~1 Cl O - - ' / \
CH~-C~CH-~, and CH3-CH-SH-CH2 Furthermore, it ls known to convert olefins into the corresp~nding oxlr~n~ with the aid of a percarboxylic acid.
.
~213~
(N. Prile3chajew, Ber. dt3ch. Chem. Ges. 42, 4,811 (1909)) This reaction is an electrophilic attack of the oxi-dislng 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 o~ the ole~in decreases with decr~a~lng nucleophilicity of the double bond. Electro-negative ~ubstituents in the a~position relative to the C=C double bond thus impede the epoxidation. (S. N. Lewis in R. Lo Augu~tin, "Oxidation", volume I, page 227, in par--ticular page 227, 3. 9-13, Marcel Dekker, New York (1969).) Halo~enoalkyl-substituted ole~ins there~ore 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 gives ris~ to the formation of unde~ired by-products, such as dihydroxy and hydroxyacyloxy derlvat~ve~ of the starting mat-erials. (S. N. Lewis in R. L. Augu~tln, "Oxidat1on'1, volume I, page 233, in particular 3. 6-11, Marcel Dekker, New York 1969). .,:
.
The ~tructure and method of preparat1on of the percarb-oxylic aci~ usedis thusof great importance, in p~rticular with re~ard to the nature and procedure o~ the reac~ion between a halogenoalkyl-aub~t1tuted olefin and a percar~oxylic acid.
~ A~ n~wn, lower ~liphatic percarbo~ylic acids can .
be prcpar~d from a carboxylic acid and hydrogen peroxide in an equill~rium ~e~ction according to equation (1). tD. Swern, in nOrgenla Peroxid~s1', volume 1, page 619 Wiley Interscie~se 1971) RCOON + N22 ~ RCOOOH ~ H20 (1~
~xcept ~o~ when relatively strong carboxylic acids are u~ed, ~uch as formic acid and trifluroacetic acid, strong ~ . .
~ - 3 -~ 2~ ~ ~ 8 acids, ~uch a~ sulphuric acid, p-toluenesulphonic acid and others, are required as a catalyst for rapid e~tablishment of the equilibrium (S. N. Lewis in R. L. Augustin "Oxidation", volume I, pRge 216 ("C. Peracids"), Marcel Dekker, New York 1969). However, the reaction of olefins with, for example, peracetic acid prepared by thi~ method did not lead to oxi-rane_ but to ~-glycols and hydroxyacetate~ (J. Boseken, W. C. 5mit and Gaster, Proc. Acad. Sci. A~sterdam, 32 377-383 (1~29)-) The mineral acid present in the reaction mixture catalyse~ the splitting-open of the oxirane pri-marily formed tD. Swern "Organic Peroxide~", Wiley Interscien~e 1971, volume 2, page 436), which can lead to oxi-rane losse~Q, especlally in the case o~ ole~ins which are 9ioW to react, quch as halogenoalkyl-substituted olefins, for the reaction of which high temperatures and long reaction times are nece~sary.
Per~ormic acid can ~e prepared from hydrogen per-oxide and ~ormic acid without an additional catalyst (S. N.
Lewi~ in R. L~ Augustin, "Oxidation", volume I, page 217, ~irst~paragraph, Marcel Dekker, New York 1969). - However, th~ reaction of a-chloroalkyl-~ubstituted olefins with thi~
mineral acid-~ree percarbo~ylic acid al~o gave the correspon-ding epoxide onlr in low yialds. A performic acid prepared ~rom 9~% ~tr~ngth formic acid and 85% strength hydro-gen peroxide ~a8 thus uQed for the epoxidation of 3,4-di- -chlorobut-l-ene. A~ter a reaction time of five hours at 60&, 2~(1,2-dichloroethyl-)oxirane was obtained in ~0~ yield (E. G. E~ Hawkln~, J. ~hem. Soc., 1959 pages 248 to 256, in par*icular page 250, li~e 19).
~ A proce~ ~or the preparation of aliphatic chloro-epoxides by reacting an allylchloro~ydrocarbon, which has a ~_L~ 4 ~
:
, 0~8 chlorine atom in the ad~acent position to the double bond, with an organic per-compound which i3 free from inorganic impurities has been disclosed recently (DAS (German Published Speci~ication) 1,056,596). The per-compounds usedin this proces3 are ~'pure peracetic 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 Specification) 1,056,596, of olefins, which are chloro-substituted in the allyl position, using acetaldehyde monoperacetate gives the corresponding oxi ranes in yield~ of between 17% and 56%, relative to the per-compound, depending on the olefin. (DAS (German Published Spocification) 1,056,596, colu~n 5 to 7, line 35 et seq~, Example 1, 3, 4 and 6).
The peracetic acid and perpropionic acid used in this proces$ for the epoxidation is employed in solution in an in~rt organic solventO As described at another point, typi-cal 1nert solvents which can be employed in this process are, inter alla, acetone, ethyl acetate, butyl acetate and dibutyl ether (U.S. P~tent 3,150,154, column 3, line 1~-3)~
Al~ylchlorohydrocarbons can be epoxidised with the per-acid~ prep~r~d according to th~ process of DAS (German Publish~d ~pecification) 1,056,596; however, the yields of oxir~n~ ~r~ low; the peracid con~ersion is incomplete. In ~he ~ les 1ndicated it is only about 90% and the purity of tho oxira~e~ isolated i8 inadequate for industrial use.
- ~ .
Thu8g ~h~ o~ida~ion of 3-chloro-1-butene with a solution of .. ..
pera~t~c~-a~d in acaton~ is described in DAS ~German Pub-li~he~ ~peG~ atlon) 1,056,596 in Example 5, column 7, line 5 at 8~q. ~.: A~ter a reaction time of ten hours, the peracid ~ - 5 -:
' " .
conversion is 91%. The oxirane i9 isolated in 68% yield with a purlty of 90.5~0 The pr~paration of 3,4-dichloro-1,2-epoxybutane by reacting 3,4-dichloro-1-butene with peracetic acid in acetone is described in British Patent Specification 784l620, in Example VII, page 7, line 5 et seq. According to this pre-paration, the peracid conversion i8 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 perproplonic acid is also given in British Patent Speci~ica-tion 784,620, in Example IX, page 7, line 85 et seq.
According to this epoxidation, after reacting crotyl chloride with a solution of perpropionic acid in ethyl propionate7 l-chloro-2,3-epoxybut~ne was obtained in 56% yield. The peracid conver~ion was 90~.
In contrast, it has now been found that halogenoalkyl-sub~tituted oxirane~ can be prepared in high yields and high purity from halogenoalkyl-substituted olefins and percarboxylic acids in organic 301ution by a procb~s in. which a chloroalkyl-&ubstituted or bromoalkyl-~ubstituted monoole~in of the general ~o~mula - ' whereln Rl and R4 independently o~ onq another denote hydrogen, Cl~ to C~ alkyl, C5 to ! C7~cycloalky1, monochloro-Cl to C5_a1ky1, monobromo-Cl- to C5~alkyl, dichloro-Cl- to C5-a~lkyl~ dibromo-Cl- to C5-alkyl, monochloro-C~- to C7-cyeloal~rl, monobromo-C5- to C7-cycloalkyl, dichloro-~5- ~o C7 Gyc10alkyl or dibromo-C5- to C7-cycloalkyl ~nd , ~ . , I A . . ~ , , R2 and R3 independently of one another represent hydrogen, Cl- to C5-alkyl, monochloro-Cl- to C5-al-kyl, monobro~o-Cl- to C5-alkyl, dichloro-Cl- to C5-alkyl and dibromo-Cl- to C5-alkyl, it being pos-sible ~or 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 Rl to R4 being an al~yl or cycloalkyl radical of the type mentioned con-taining chlorine or bromine, is reacted with a 301ution of a percarboxylic acid containing 3 to 4 carbon atom3 in an aromatic hydrocarbon containing 6 to 12 carbon atoms at a molar ratio of monoolefin to per-cabo~ylic acid of 1.1 to 10 : 1 and at R temperature of ~0C
to 100C~ .
W1thin the scope of the co~pounds of the formula (I), ~xample9 0~ possible compound~ are, in particular, tho~e of the following ~ormulae: .
R5-C~`CH-R6 (II) wherein .
R5 and R6 independently o~ bne another denote Cl- to C5-alkyl, monochloro~Cl- to C5-alkyl, monobromo-Cl- -to C5-al ~l, dichIoro~el~ tb C5-alkyl or dibromo-Cl-to C5 alkyl, 1 . ~ .
~5 ~ ~ it being po~ible ~or theradicals R5 and R6 to be linked to form a ring, together with the group CH=CH, and at loa~t one of ~he radicals R5and R6 denoting monochlorQ~ to C5-alkyl~ monobromo-Cl- to C5-alkyl, dlchloro~Cl- to C5-alk~l or dibromo~Cl- to C5 alkyl;
..
'.
, .
.
.
4~3 ~C=C ~
Rg~''' \ ~10, (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, dichloro-Cl- to C5-alkyl or dlbromo-Cl- to C5-alkyl, Rg and Rlo independently of one another repre~ent a methylene, chloromethylene, bromomethylene, l,2-di-chloroethylene or 1,2-di~romomethylene radical and . n represent~ an integer from 1 to 6, at lea~t one of the radicals R7 - Rlo repre~enting an alkyl, cyclo-alkyl or alkylene radical Qf the type mentioned containing chlorine or bromine.
In detail, halogenoal~ ubstituted ~onoolefin~ which may be mentioned are: allyl chloride, 2-chloromethyl-propene, 3-chloro-2-chloromethyl-propene, 3-chloro-1-butene:? l-chloro-
The present invention relates to an improved process for the preparation of halogenoalkyl-substituted oxiranes from halogenoalkyl-substituted olefins and percarboxylic acids~
Halogenoalkyl-~ubstituted oxiranes are used in the field of lacquers and plastics and as organic intermediate products.
It is known to prepare chloroalkyl-3ubstituted oxi-ranes from the corresponding olefins by the chlorohydrin process. Thi~ process has the disadvantage that undesired chlorinated by-product~ 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 ~eq., in p~rticular 3. 13-15; and DAS (German Published Specification~
19543,174, column 2, line 15 et ~eq., in particular 3. 32-35).
It i8 al80 frequentl~ icult definitively -to pre-pare a single reaction prod,~ct by the,chlorohydrin method.
Thu~, th~ reaction o~ 4-chlorobut-2-ene,wi,th hypochlorous acid zo l~ads to a mixture of two products, which may be characterised by the follcwing formulao:
OH Cl Cl Cl 0~ Cl CH3-CH-CH CH2 and CH3-CH-CH-CH2 ',' ~ Accordingly, subsequent dehydrohalogenation o~ thi~
mixture u~ing a',bas~ gives a mixture of two i~omeric oxiranes, as the ~ormulae below illustrate (DAS (German Published Specification) 19056,596, column 1, line 53 to column 2, 3-43):
~ ~1 Cl O - - ' / \
CH~-C~CH-~, and CH3-CH-SH-CH2 Furthermore, it ls known to convert olefins into the corresp~nding oxlr~n~ with the aid of a percarboxylic acid.
.
~213~
(N. Prile3chajew, Ber. dt3ch. Chem. Ges. 42, 4,811 (1909)) This reaction is an electrophilic attack of the oxi-dislng 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 o~ the ole~in decreases with decr~a~lng nucleophilicity of the double bond. Electro-negative ~ubstituents in the a~position relative to the C=C double bond thus impede the epoxidation. (S. N. Lewis in R. Lo Augu~tin, "Oxidation", volume I, page 227, in par--ticular page 227, 3. 9-13, Marcel Dekker, New York (1969).) Halo~enoalkyl-substituted ole~ins there~ore 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 gives ris~ to the formation of unde~ired by-products, such as dihydroxy and hydroxyacyloxy derlvat~ve~ of the starting mat-erials. (S. N. Lewis in R. L. Augu~tln, "Oxidat1on'1, volume I, page 233, in particular 3. 6-11, Marcel Dekker, New York 1969). .,:
.
The ~tructure and method of preparat1on of the percarb-oxylic aci~ usedis thusof great importance, in p~rticular with re~ard to the nature and procedure o~ the reac~ion between a halogenoalkyl-aub~t1tuted olefin and a percar~oxylic acid.
~ A~ n~wn, lower ~liphatic percarbo~ylic acids can .
be prcpar~d from a carboxylic acid and hydrogen peroxide in an equill~rium ~e~ction according to equation (1). tD. Swern, in nOrgenla Peroxid~s1', volume 1, page 619 Wiley Interscie~se 1971) RCOON + N22 ~ RCOOOH ~ H20 (1~
~xcept ~o~ when relatively strong carboxylic acids are u~ed, ~uch as formic acid and trifluroacetic acid, strong ~ . .
~ - 3 -~ 2~ ~ ~ 8 acids, ~uch a~ sulphuric acid, p-toluenesulphonic acid and others, are required as a catalyst for rapid e~tablishment of the equilibrium (S. N. Lewis in R. L. Augustin "Oxidation", volume I, pRge 216 ("C. Peracids"), Marcel Dekker, New York 1969). However, the reaction of olefins with, for example, peracetic acid prepared by thi~ method did not lead to oxi-rane_ but to ~-glycols and hydroxyacetate~ (J. Boseken, W. C. 5mit and Gaster, Proc. Acad. Sci. A~sterdam, 32 377-383 (1~29)-) The mineral acid present in the reaction mixture catalyse~ the splitting-open of the oxirane pri-marily formed tD. Swern "Organic Peroxide~", Wiley Interscien~e 1971, volume 2, page 436), which can lead to oxi-rane losse~Q, especlally in the case o~ ole~ins which are 9ioW to react, quch as halogenoalkyl-substituted olefins, for the reaction of which high temperatures and long reaction times are nece~sary.
Per~ormic acid can ~e prepared from hydrogen per-oxide and ~ormic acid without an additional catalyst (S. N.
Lewi~ in R. L~ Augustin, "Oxidation", volume I, page 217, ~irst~paragraph, Marcel Dekker, New York 1969). - However, th~ reaction of a-chloroalkyl-~ubstituted olefins with thi~
mineral acid-~ree percarbo~ylic acid al~o gave the correspon-ding epoxide onlr in low yialds. A performic acid prepared ~rom 9~% ~tr~ngth formic acid and 85% strength hydro-gen peroxide ~a8 thus uQed for the epoxidation of 3,4-di- -chlorobut-l-ene. A~ter a reaction time of five hours at 60&, 2~(1,2-dichloroethyl-)oxirane was obtained in ~0~ yield (E. G. E~ Hawkln~, J. ~hem. Soc., 1959 pages 248 to 256, in par*icular page 250, li~e 19).
~ A proce~ ~or the preparation of aliphatic chloro-epoxides by reacting an allylchloro~ydrocarbon, which has a ~_L~ 4 ~
:
, 0~8 chlorine atom in the ad~acent position to the double bond, with an organic per-compound which i3 free from inorganic impurities has been disclosed recently (DAS (German Published Speci~ication) 1,056,596). The per-compounds usedin this proces3 are ~'pure peracetic 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 Specification) 1,056,596, of olefins, which are chloro-substituted in the allyl position, using acetaldehyde monoperacetate gives the corresponding oxi ranes in yield~ of between 17% and 56%, relative to the per-compound, depending on the olefin. (DAS (German Published Spocification) 1,056,596, colu~n 5 to 7, line 35 et seq~, Example 1, 3, 4 and 6).
The peracetic acid and perpropionic acid used in this proces$ for the epoxidation is employed in solution in an in~rt organic solventO As described at another point, typi-cal 1nert solvents which can be employed in this process are, inter alla, acetone, ethyl acetate, butyl acetate and dibutyl ether (U.S. P~tent 3,150,154, column 3, line 1~-3)~
Al~ylchlorohydrocarbons can be epoxidised with the per-acid~ prep~r~d according to th~ process of DAS (German Publish~d ~pecification) 1,056,596; however, the yields of oxir~n~ ~r~ low; the peracid con~ersion is incomplete. In ~he ~ les 1ndicated it is only about 90% and the purity of tho oxira~e~ isolated i8 inadequate for industrial use.
- ~ .
Thu8g ~h~ o~ida~ion of 3-chloro-1-butene with a solution of .. ..
pera~t~c~-a~d in acaton~ is described in DAS ~German Pub-li~he~ ~peG~ atlon) 1,056,596 in Example 5, column 7, line 5 at 8~q. ~.: A~ter a reaction time of ten hours, the peracid ~ - 5 -:
' " .
conversion is 91%. The oxirane i9 isolated in 68% yield with a purlty of 90.5~0 The pr~paration of 3,4-dichloro-1,2-epoxybutane by reacting 3,4-dichloro-1-butene with peracetic acid in acetone is described in British Patent Specification 784l620, in Example VII, page 7, line 5 et seq. According to this pre-paration, the peracid conversion i8 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 perproplonic acid is also given in British Patent Speci~ica-tion 784,620, in Example IX, page 7, line 85 et seq.
According to this epoxidation, after reacting crotyl chloride with a solution of perpropionic acid in ethyl propionate7 l-chloro-2,3-epoxybut~ne was obtained in 56% yield. The peracid conver~ion was 90~.
In contrast, it has now been found that halogenoalkyl-sub~tituted oxirane~ can be prepared in high yields and high purity from halogenoalkyl-substituted olefins and percarboxylic acids in organic 301ution by a procb~s in. which a chloroalkyl-&ubstituted or bromoalkyl-~ubstituted monoole~in of the general ~o~mula - ' whereln Rl and R4 independently o~ onq another denote hydrogen, Cl~ to C~ alkyl, C5 to ! C7~cycloalky1, monochloro-Cl to C5_a1ky1, monobromo-Cl- to C5~alkyl, dichloro-Cl- to C5-a~lkyl~ dibromo-Cl- to C5-alkyl, monochloro-C~- to C7-cyeloal~rl, monobromo-C5- to C7-cycloalkyl, dichloro-~5- ~o C7 Gyc10alkyl or dibromo-C5- to C7-cycloalkyl ~nd , ~ . , I A . . ~ , , R2 and R3 independently of one another represent hydrogen, Cl- to C5-alkyl, monochloro-Cl- to C5-al-kyl, monobro~o-Cl- to C5-alkyl, dichloro-Cl- to C5-alkyl and dibromo-Cl- to C5-alkyl, it being pos-sible ~or 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 Rl to R4 being an al~yl or cycloalkyl radical of the type mentioned con-taining chlorine or bromine, is reacted with a 301ution of a percarboxylic acid containing 3 to 4 carbon atom3 in an aromatic hydrocarbon containing 6 to 12 carbon atoms at a molar ratio of monoolefin to per-cabo~ylic acid of 1.1 to 10 : 1 and at R temperature of ~0C
to 100C~ .
W1thin the scope of the co~pounds of the formula (I), ~xample9 0~ possible compound~ are, in particular, tho~e of the following ~ormulae: .
R5-C~`CH-R6 (II) wherein .
R5 and R6 independently o~ bne another denote Cl- to C5-alkyl, monochloro~Cl- to C5-alkyl, monobromo-Cl- -to C5-al ~l, dichIoro~el~ tb C5-alkyl or dibromo-Cl-to C5 alkyl, 1 . ~ .
~5 ~ ~ it being po~ible ~or theradicals R5 and R6 to be linked to form a ring, together with the group CH=CH, and at loa~t one of ~he radicals R5and R6 denoting monochlorQ~ to C5-alkyl~ monobromo-Cl- to C5-alkyl, dlchloro~Cl- to C5-alk~l or dibromo~Cl- to C5 alkyl;
..
'.
, .
.
.
4~3 ~C=C ~
Rg~''' \ ~10, (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, dichloro-Cl- to C5-alkyl or dlbromo-Cl- to C5-alkyl, Rg and Rlo independently of one another repre~ent a methylene, chloromethylene, bromomethylene, l,2-di-chloroethylene or 1,2-di~romomethylene radical and . n represent~ an integer from 1 to 6, at lea~t one of the radicals R7 - Rlo repre~enting an alkyl, cyclo-alkyl or alkylene radical Qf the type mentioned containing chlorine or bromine.
In detail, halogenoal~ ubstituted ~onoolefin~ which may be mentioned are: allyl chloride, 2-chloromethyl-propene, 3-chloro-2-chloromethyl-propene, 3-chloro-1-butene:? l-chloro-
2-butene, 1,4-dichloro-2 butene~ 3,4~dichlo~o-1-butenP, ~-chlo-ro-l-pentene, 4-chloro-2-pentene, l chloro-2-~ente~e, 1,4-di-chloro-2-pente~e, 3,4-dichloro-1-pentene, 1,2-dichloro 3-pen- -tene, ~-chloro~1-cyclopéntene, 1,4-dich10ro-2-cyclopentene,
3-chloro-1-hsx~né, 1-chloro-2-hexene, 1~4-dichloro-2-hexene, 3,4-dichloro-1-ho~ene, 2~chloro-3-hexene, 2,5-dichloro~3-hex-ene, 3-chloro-1-cyclohexene, 1,4-dlchloro-2-cyclohexene, l-chloro-2 h~ptone, 3-chloro-1-heptene, 3,4-dichloro-1-heptene, 1,4-diohloro-2-heptene~ 2-chloro-3-heptene, 2,5-dichloro-3-heptene, 3-ohloro~l-cycloheptene, 1,4-dichloro-2-cycloheptene, l-chloro-2-octene, 3-chloro-1-octene, 1,4-dichloro-2-octene, 2,5-dichloro-3-octene, 2-chloro-3-octeneS 3-chloro-4-octene) 3,6_dlchloro-4-octene, 3-chloro-1-cyclooctene, 1,4-dichloro-2-cyclooctene, l-(l-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-l-decene, 4-chloro-2-decene, 194-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-di-chloro-5-decene, 1-chloro-3-undecene, 3-chloro-1-undecene, 1,4-dichloro-2-undecene~ 2-chloro-3-undecene, 4-chloro-2-unde-cene, 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-dode-cene, 3-chloro-1-dodecene, 1,4-dichloro-2-dodecene, 2-chloro-3-dodecene, 4-chloro-2-dodec;ene, 2,5-dichloro-3-dodecene, 5-chloro-3-dodecene, 6-chloro-4-dodecene, 4-chloro-5-dodecene, 4,7-d$chloro-5-dodec;ene9 5-chloro-6-dodecene, 5,8-dichloro-
6-dodecene, 5,7-dichloro 6-dod:ecene and 7-chloro-5-dodecene;
allyl bromid~, 2-bromometh~l-propene, 3-bromo-2-bromomethyl-propene, 3~bromo-1-butene, 1-bromo-2-butene, 1,4-dibromo-2-butene, 314-dibromo-l-butene, 3-bromo-1-pentene, 4-bromo-2-pentene, 1-bromo-2-pentene, 1,4-dlbromo-2-pentene, 3,4-di-bromo-l-p~ntene, 1,2-dibromo-3-pentene, 3-bromo-1-cyclopentene, 1,4-dibromo-~-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, 19 4-dibromo-2-cyclohexene, l-bromo-2-heptene, 3-bromo-1-heptene, 3,4-dibromo-l-hept~ne, 1,4-dibromo-2-heptene, 2 bromo-3-heptene, ~,5~di-bromo-3-heptene, 3-bromo-1-cycloheptene, 1,4-dibromo-2-cyclo-heptene, l-bromo-2-octene, 3-bromo-1-octene, 1,4-dibromo-_ g _ ..
2-octene, 2,5-dibromo-3-octene, 2-bromo-3-octene, 3-bromo-4-octene, 3,6-dibromo-4-octene, 3-bromo-l-cyclooctene, 1,4-dibromo-2-cyclooctene, l-(l-bromo-cyclohexyl)-ethene, l-bro-mo-2-nonene, 3-bromo~l-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, l-bromo-3-decene, 3-bromo-l-decene, 4-bromo-2-decene, 1,4-dibromo-2-decene, 2,bromo-3-decene, 295-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, l-bromo-3-undecene, 3-bromo-l-undecene, 1,4-dibromo-2-undecene, 2-bromo-3-undecene, 4-bromo-2-undecene, 2,5-di-bromo-3-undecene, 5-bromo-3-lmdecene, 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-dodecene9 5-bromo-6-dodecene, 5,8-dibromo-6-dodecene, 5,7-dibromo-5-dodecene and 7-bromo-5 dodecene.
Chloroalkyl-sub~tituted or bromoalkyl-Yub~tituted monoole~in~ which are particularly suitable ~or ~e~ction with percarboxylic acids by the process according to the invention ~re those o~ ~he ~ormula Rll-CH=CH-Rl2 (IV) wherein Rll and R12 independently o~ one another denote hydrogen, ~ to C ~ lkyl,mono~oro-~- to C5-alkyl, monobromo-~-to C5-al~yl,dlchloro ~- to C5-alkyl or dibromo-Cl- to C5-alkyl, at least one o~ the radicals Rll and Rl2 representing monochloro~Cl- to C5-alkyl, monobromo-Cl- ~o C5-alkyl, d~chloro-Cl~ to C5-alkyl or dibromo-Cl- to C5-alkyl.
, .
~ Q ~ 8 In detail, examples which may be mentioned are:
allyl chloride, 2-chloromethyl-propene, 3-chloro-2-chloro-methyl-propene, 3;chloro-1-butene, 1-chloro-2-butene, 1,4-di-chloro-2-butene, 3,4-dichloro-1-butene, 3-chloro-1-pentene, 4-chloro-2-pentene, 1-chloro-2-pentene, 1,4-dlchloro-2-pen-tene, 3,4-dichloro-1-pentene, 1,2-dichloro-3-pentene~ 3-chloro-l-hexene, l-chloro-2~hexene, 1,4-dichloro-2-hexene, 3,4-di-chloro-l-hexene, 2-chloro-2-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 J 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-dibro-1-hexene, 2-bromo-~-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 suitable for reac-tion wlth peroarbo~ylic acids by the process according to the ~o invention.
Th~ most diverse aromatic hydrocarbons with 6 to 12 .
carbon atom~, which can also be substituted, can be used as solYent~. Po3~1ble examples arebenzene, nitrobenzene, tolu-ene, xylene, ethylbenzene, diethylbenzene, cumene, diisopro-pylhenzene and chlorobenzene.
Aromatic hydrocarbons with 6 to 8 carbon atoms, such as benzene, ni~robenzene~ chlorobenzene, toluene, xylene and ethyl-benzene, are particul rly ~uitable.
P~eferred solv~nts are benzene and toluene. A par-ticularly pre~erred solvent is benzene. Mixtures of different aromatic 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 prepara-tion of the mineral acid-free peracids in one of the organic solvents mentioned can be carried out, for example, by the pro-cess descrlbed 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 ~rom 30-100C. It is pre~erably carried out at 60~80C and particularly preferably at 65-75C. In special 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 reac-tion with the setting up of a so-called temperature gradient, which in general increases as the reaction progresses~ How-ever, lt 1s also pos~ible to carry out the reaction in a manner ~uch that a decreasing temperature gradient is set up as~the~reaction progre~es.
According to the invention, the molar ratio o~ olefin to p~racid is 1.1 : 1 to 10 : 1. A molar ratio of 1.25 : 1 to 5 : 1 is pre~erably used. It is very particularly advan-tageous to use a molar ratio of 105 to 3.0 mols of olefin per mol o~ peracidO
The process according to the invention can be carried out under the most d.~er~e pressures~ In general9 it is carried out under normal pressure; however, the process can al80 be carried out under reduced pressure or excess pressure.
.
., . ,.,~ , .: . . .
0~8 In ganeral, 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 percaboxyllc acid with a water content of up to 2% by weight, for ex~mple, is suitable. A percar-boxylic acid solution w~lich contains less than 1% by weight of water is pre~erably uqed. A water content of less than 0.1~ by weight is particularly preferred.
In general, the h~drogen peroxide content of the per-carbo~ylic acid used should be as low as possible. It can be up to Z~ by weigh~. The reaction is advantageou~ly car-ried out with a hydrogen peroxide content of less than 1% by weight. It is particularly advantageous to car~y out the reaction with a percarboxyl~c acid solution which has a hydro-gen peroxide content below 0.3%.
The mineral acid content of the percarboxylic acid solutlon used ~or the reaction should be as low as possible.
It is advantageou~ to carry out the reaction with a percar-boxylic acid ~olution which ha~ a mineral acid content below 50 ppm. A miner~l acid content o~ less than 10 ppm is par-ticularlr ad~antageous.
Th~ reaction can be carried out discontinuously or con-tinuou~ly in the customary devices for reactions of this type, such as atirred kettles, boiling reactors, tube reactors, loop reactors or circulatory reactors~
~la~, st~inless steels or enamelled material can be us~d a~mat@~ia~ o~ construction for carrying out theprocesses.
Heavy metal ions in the reaction mixture catalyse the decompositlon o~ the percarboxylic acid. Substances which lnactiv~te the heavy metal ions by means of complex formation ~re therefQ~e gen~rally added to the percarboxylic acid solution~ Known substances of this type are gluoonic acid, ethylenediaminetetraacetic acid9 sodium silicate, sodium pyrophosphate, sodium hexametaphosphate, disodium dimethyl pyrophosphate or Na2(2-ethYl-heXYl)s(P30lo)2 (DAS (German Published Specification) 1,056,596, column 4, line 60 et seq).
The halogenoalkyl-~ubstituted 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 in separately from one another. Furthermore, it is possible to intro-duce the olefin and the percarboxylic acid solution into the reactor unit at different points. If several reactors con-nected in a cascade are used, it can be appropriate to introduce all the olefin into the first reactor. However, it iq also possible to distribute the olefin among the vari-ous reactors.
The heat of reaction is removed by internal or exter-nal cooler~. In order to remo~e the heat of reaction, it is also po~sible to carry out the reaction under reflux (boil-in~ reactQrs).
The reaction is appropriately carried out with as com-plete a~ pos~ible converslon of the percarboxylic acid. In gcneral, more than 95 mol % o~ the percarboxylic acid are reac-ted. It is appropriate to react more than 98 mol % of the peracid.
When the reaction between the halogenoalkyl-sub~tituted ole~in and the peracid is carried out according to the invsntion, it i8 possible to achieve oxirane yields of 90%
of theory and more, relative to percarboxylic acid employed.
Th~ reaction mixture is wor~ed up in a manner which is in itsel~ kno~n, ~or example by distillation. It is - ~2~
particularly advantageous to extract the reaction mixture with water, before working up by dlstillation, in order to separate off the carboxylic acid, corresponding to the per-carboxylic acid, which is formed during the reaction. The extraction can be carried out in the customary extractors, such as mixertseparators,perforated tray extractors, pulsating per~orated tray columns, rotatlng disc extractors or extrac-tion centrifuges.
In a preferred manner of carrying out the process, an approximately 20% strength by weight solution of perpropionic acid in benzene is added to three times the molar amount of halogenoalkyl-substituted ole~ln~ 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 0.1% 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 perpropionic acid in order -to complex heavy metal ions. The proKress and the end of the reaction are monitored by removing samp` e9 from the reaction solution at intervals of time and determining tritrimetrically the content of percarboxylic acid still present. A~ter the reaction has ended, the reaction mixture is cooled and washed three times with the same amount by weight o~ water in order to remove the propionic acid.
The propionic acid-free reaction mixture is then fractionated.
The example~ which ~ollow illu~trate the invention, Unle~s indicated otherwise, all the percentage data represent per cent by weight.
Preparation of epichlorohydrin from allyl chloride and per-propionic acid.
~ - 15 -, ~%~
45 g o~ 20% strength perpropionic acid in benzene (0.1 mol) were initially introduced into a 200 ml three-necked double-walled ~lask with a magnetic stirrer, internal thermometer, dropping funnel and re~lux condenser and were thermostatically controlled at 70C. Thereafter, 22.96 g (0.3 mol) of allyl chloride are added dropwise such that the temperature could be kep-t at 70C. After stirring under reflux ~or a further 6 hours, tritrimetric analysis gave a perpropionic acid conversion of 98.5%. Analysis of the reaction mixture by gas chromatography showed that epichloro-hydrin was formed with a selectivity of 97.5%, relative to perpropionic acid employed. After cooling, the reaction mlxture was washed several times with water in order to remove the propionic acid and was then fractionated. 8.73 g of epichlorohydrin resulted, xample 2 Preparation o~ 2-(1,2~dichloroethyl-)oxirane from 3,4-di-chloro-l-buten~ and perpropionic acid.
62.9~ g (0.147 mol~ of perpropionic acid, as a 21%
~treng~h svlution in benzene, were added dropwise to 55.87 g (0.447 molj of 3,4-dichloro-1-butene at 70C, whilst stirring.
After the dropwise addition, the mixture was stirred at this temperature ~or a ~urther 6 hours, and tritrimetric analysis then ~howed a perpropionic acid conversion o~ 97%. Ths reaction solut{on was cooled to room temperature and analysed by gas chromatography. As the analysis showed, 2-(1,2-di-chloroethyl-)-oxirane was ~ormed with a selectivity of 94.Z%, relat~ve to perpropionic acid employed.
The reaction mi~ture was washed several times with water in order to remo~e the propionic acid, benzene was dis-till~d o~ and the re~ction product was then ~ractionated in ., -a 40 cm packed column, packed with 4 mm glass Raschig ring~.
18.9 g of 2-(1,2-dichloroethyl-)-oxirane were isolated with a purity of 99.4%.
Ex~mple ~
Preparation o~ 2,3-bis-(chloro~ethyl)-oxirane from 1,4-di-chloro-2-butene and perpropionic acid.
63.97 g (0.147 mol) o~ perpropionic acid, as a 20.68%
strength solution in benzene, were added dropwise to 55.2 g (0.4416 mol) of 1,4-dichloro-2-butene at 70C and the mixture was then further stirred at this temperature. A~ter a reaction time of 4 hours, the peracid conversion was 96%, and a~ter 6 hours it was over 99%. 2,3 Bis(chloromethyl)-oxi-rane was formed with a selectivity of 96.5%, relative to per-propionic acid employed. After removing the propionic acid by extracting the reaction mixture by shaking several time~
with water and subsequently ssparating o~f -the benzene by dis-tillation, and after fractionation of the reaction product over a ~0 cm packed column, filled with 4 mm glass Raschig rings, 19.6 g of 2,3-bis-(chloromethyl)-oxirane were obtained with a purity of 99.g%~
~cntinuou~ preparation o~ 2,3-bis-(chloromethyl)-oxirane from 1,4-diohloro-2-butene and perpropionic acid.
A solution of perpropionic acid in benzene, to which a ~tabili~er o~ the type9 which is commercially available, con-sisting o~ sodium salts of polyphosphoric acids partially esterified with loffg-chain alcohols has been added, was reac-ted with 1,4~dichloro-2 butene in a reaction system in the ~orm of a t~ ee-stage ca~cade o~ stirred kettles. Each o~ the throe ~stirred ~ettles had a volume of 10 1. The kettles were heated via heating coil~ located in the kettle. All Le A 17 776 - 17 -4~3 three kettles were the~no tatically controlled at 70C.
2,137.5 g (4.75 mols) of perpropionic acid, as a 20%
strength solution in benzene, and 1,781.25 g (14.25 molsj of ~ 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 per-propionic acid was converted ~o the exten~ o~ 96.~%. The selectivity of the 2,~-bis-(chloromethyl)-oxirane formed was 96%, relative to perpropionic acid amployed.
The reaction mixture obtained after the third reactor had the following average composition: 35.6% of benzene, 30.8% of 1,4-dichloro-2-butene, 16.24~ of 2,3-bis-(chloro-methyl)-oxirane and 17% of propionic acid. This mixture was extracted in a pulsating per~orated tray column with twice the amount of water in order to separate off the propionic acid. Therea~ter, the residual content of propionic acid was 0.04%. The reaction mixture obtained after this opera-tion wa~ fractionated in a distillation line. Benzene was di~tilled in a fir~t column in an amount o~ 1,395 g per hour.
The bot~om product o~ this column, which essentially consisted of star~ing materlal and oxirane~ waq ~ractionated in a second column under reduced pressure. 1,206.5 g o~ 1,4-dichloro-2-butene per hour were obtained a~ the head product. The bottom pr~duct o~ thi~ column waq freed from high-boiling constituents i~ a third column under reduced pressure.
629.5 g of 2,3-bis-(chloromet~yl) oxirane per hour were obtained as the head product with a purity of over 99.~.
Thi3 correspond~ to a yleld o~ 94%~ relative to the perpro-pio~ic acid employed in the reastion ystem~
.. ,~.
L~ a~ 18 -:. ~
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 ~or a further 2 hour~. 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 1,4-di-bromo-2-butene to 3,4-dibromo-1-butene being about 2 : 1.
The 1,4-dibromo-2-butene was isolated by distillation.
b) Reactlon of 1,4~dibromo-2-butene with perpropionic acid 45 g of 20% strength perpropionic acid in benzene (Ool mol) were added dropwise to 64.2 g (0.3 mol) of 1,4-di-bromo-2-butene at 70C, whilst stirring, and the mixture was stirred at this temperature for a further 4 hours. After this time, the peracld conversion was 95%. Analysis by ga3 chromatography ~howed that the epoxide was ~ormed with a selec-tivity o~ 92.6%, relative to perpropionic acid employed.
After cooling, the reaction mixture was washed several times with water in order to remove the propionic acid and the reac-tion product was fractionated. 20~7 g o~ epoxide were obtained.
~La~ - 19 --~ .
allyl bromid~, 2-bromometh~l-propene, 3-bromo-2-bromomethyl-propene, 3~bromo-1-butene, 1-bromo-2-butene, 1,4-dibromo-2-butene, 314-dibromo-l-butene, 3-bromo-1-pentene, 4-bromo-2-pentene, 1-bromo-2-pentene, 1,4-dlbromo-2-pentene, 3,4-di-bromo-l-p~ntene, 1,2-dibromo-3-pentene, 3-bromo-1-cyclopentene, 1,4-dibromo-~-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, 19 4-dibromo-2-cyclohexene, l-bromo-2-heptene, 3-bromo-1-heptene, 3,4-dibromo-l-hept~ne, 1,4-dibromo-2-heptene, 2 bromo-3-heptene, ~,5~di-bromo-3-heptene, 3-bromo-1-cycloheptene, 1,4-dibromo-2-cyclo-heptene, l-bromo-2-octene, 3-bromo-1-octene, 1,4-dibromo-_ g _ ..
2-octene, 2,5-dibromo-3-octene, 2-bromo-3-octene, 3-bromo-4-octene, 3,6-dibromo-4-octene, 3-bromo-l-cyclooctene, 1,4-dibromo-2-cyclooctene, l-(l-bromo-cyclohexyl)-ethene, l-bro-mo-2-nonene, 3-bromo~l-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, l-bromo-3-decene, 3-bromo-l-decene, 4-bromo-2-decene, 1,4-dibromo-2-decene, 2,bromo-3-decene, 295-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, l-bromo-3-undecene, 3-bromo-l-undecene, 1,4-dibromo-2-undecene, 2-bromo-3-undecene, 4-bromo-2-undecene, 2,5-di-bromo-3-undecene, 5-bromo-3-lmdecene, 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-dodecene9 5-bromo-6-dodecene, 5,8-dibromo-6-dodecene, 5,7-dibromo-5-dodecene and 7-bromo-5 dodecene.
Chloroalkyl-sub~tituted or bromoalkyl-Yub~tituted monoole~in~ which are particularly suitable ~or ~e~ction with percarboxylic acids by the process according to the invention ~re those o~ ~he ~ormula Rll-CH=CH-Rl2 (IV) wherein Rll and R12 independently o~ one another denote hydrogen, ~ to C ~ lkyl,mono~oro-~- to C5-alkyl, monobromo-~-to C5-al~yl,dlchloro ~- to C5-alkyl or dibromo-Cl- to C5-alkyl, at least one o~ the radicals Rll and Rl2 representing monochloro~Cl- to C5-alkyl, monobromo-Cl- ~o C5-alkyl, d~chloro-Cl~ to C5-alkyl or dibromo-Cl- to C5-alkyl.
, .
~ Q ~ 8 In detail, examples which may be mentioned are:
allyl chloride, 2-chloromethyl-propene, 3-chloro-2-chloro-methyl-propene, 3;chloro-1-butene, 1-chloro-2-butene, 1,4-di-chloro-2-butene, 3,4-dichloro-1-butene, 3-chloro-1-pentene, 4-chloro-2-pentene, 1-chloro-2-pentene, 1,4-dlchloro-2-pen-tene, 3,4-dichloro-1-pentene, 1,2-dichloro-3-pentene~ 3-chloro-l-hexene, l-chloro-2~hexene, 1,4-dichloro-2-hexene, 3,4-di-chloro-l-hexene, 2-chloro-2-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 J 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-dibro-1-hexene, 2-bromo-~-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 suitable for reac-tion wlth peroarbo~ylic acids by the process according to the ~o invention.
Th~ most diverse aromatic hydrocarbons with 6 to 12 .
carbon atom~, which can also be substituted, can be used as solYent~. Po3~1ble examples arebenzene, nitrobenzene, tolu-ene, xylene, ethylbenzene, diethylbenzene, cumene, diisopro-pylhenzene and chlorobenzene.
Aromatic hydrocarbons with 6 to 8 carbon atoms, such as benzene, ni~robenzene~ chlorobenzene, toluene, xylene and ethyl-benzene, are particul rly ~uitable.
P~eferred solv~nts are benzene and toluene. A par-ticularly pre~erred solvent is benzene. Mixtures of different aromatic 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 prepara-tion of the mineral acid-free peracids in one of the organic solvents mentioned can be carried out, for example, by the pro-cess descrlbed 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 ~rom 30-100C. It is pre~erably carried out at 60~80C and particularly preferably at 65-75C. In special 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 reac-tion with the setting up of a so-called temperature gradient, which in general increases as the reaction progresses~ How-ever, lt 1s also pos~ible to carry out the reaction in a manner ~uch that a decreasing temperature gradient is set up as~the~reaction progre~es.
According to the invention, the molar ratio o~ olefin to p~racid is 1.1 : 1 to 10 : 1. A molar ratio of 1.25 : 1 to 5 : 1 is pre~erably used. It is very particularly advan-tageous to use a molar ratio of 105 to 3.0 mols of olefin per mol o~ peracidO
The process according to the invention can be carried out under the most d.~er~e pressures~ In general9 it is carried out under normal pressure; however, the process can al80 be carried out under reduced pressure or excess pressure.
.
., . ,.,~ , .: . . .
0~8 In ganeral, 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 percaboxyllc acid with a water content of up to 2% by weight, for ex~mple, is suitable. A percar-boxylic acid solution w~lich contains less than 1% by weight of water is pre~erably uqed. A water content of less than 0.1~ by weight is particularly preferred.
In general, the h~drogen peroxide content of the per-carbo~ylic acid used should be as low as possible. It can be up to Z~ by weigh~. The reaction is advantageou~ly car-ried out with a hydrogen peroxide content of less than 1% by weight. It is particularly advantageous to car~y out the reaction with a percarboxyl~c acid solution which has a hydro-gen peroxide content below 0.3%.
The mineral acid content of the percarboxylic acid solutlon used ~or the reaction should be as low as possible.
It is advantageou~ to carry out the reaction with a percar-boxylic acid ~olution which ha~ a mineral acid content below 50 ppm. A miner~l acid content o~ less than 10 ppm is par-ticularlr ad~antageous.
Th~ reaction can be carried out discontinuously or con-tinuou~ly in the customary devices for reactions of this type, such as atirred kettles, boiling reactors, tube reactors, loop reactors or circulatory reactors~
~la~, st~inless steels or enamelled material can be us~d a~mat@~ia~ o~ construction for carrying out theprocesses.
Heavy metal ions in the reaction mixture catalyse the decompositlon o~ the percarboxylic acid. Substances which lnactiv~te the heavy metal ions by means of complex formation ~re therefQ~e gen~rally added to the percarboxylic acid solution~ Known substances of this type are gluoonic acid, ethylenediaminetetraacetic acid9 sodium silicate, sodium pyrophosphate, sodium hexametaphosphate, disodium dimethyl pyrophosphate or Na2(2-ethYl-heXYl)s(P30lo)2 (DAS (German Published Specification) 1,056,596, column 4, line 60 et seq).
The halogenoalkyl-~ubstituted 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 in separately from one another. Furthermore, it is possible to intro-duce the olefin and the percarboxylic acid solution into the reactor unit at different points. If several reactors con-nected in a cascade are used, it can be appropriate to introduce all the olefin into the first reactor. However, it iq also possible to distribute the olefin among the vari-ous reactors.
The heat of reaction is removed by internal or exter-nal cooler~. In order to remo~e the heat of reaction, it is also po~sible to carry out the reaction under reflux (boil-in~ reactQrs).
The reaction is appropriately carried out with as com-plete a~ pos~ible converslon of the percarboxylic acid. In gcneral, more than 95 mol % o~ the percarboxylic acid are reac-ted. It is appropriate to react more than 98 mol % of the peracid.
When the reaction between the halogenoalkyl-sub~tituted ole~in and the peracid is carried out according to the invsntion, it i8 possible to achieve oxirane yields of 90%
of theory and more, relative to percarboxylic acid employed.
Th~ reaction mixture is wor~ed up in a manner which is in itsel~ kno~n, ~or example by distillation. It is - ~2~
particularly advantageous to extract the reaction mixture with water, before working up by dlstillation, in order to separate off the carboxylic acid, corresponding to the per-carboxylic acid, which is formed during the reaction. The extraction can be carried out in the customary extractors, such as mixertseparators,perforated tray extractors, pulsating per~orated tray columns, rotatlng disc extractors or extrac-tion centrifuges.
In a preferred manner of carrying out the process, an approximately 20% strength by weight solution of perpropionic acid in benzene is added to three times the molar amount of halogenoalkyl-substituted ole~ln~ 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 0.1% 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 perpropionic acid in order -to complex heavy metal ions. The proKress and the end of the reaction are monitored by removing samp` e9 from the reaction solution at intervals of time and determining tritrimetrically the content of percarboxylic acid still present. A~ter the reaction has ended, the reaction mixture is cooled and washed three times with the same amount by weight o~ water in order to remove the propionic acid.
The propionic acid-free reaction mixture is then fractionated.
The example~ which ~ollow illu~trate the invention, Unle~s indicated otherwise, all the percentage data represent per cent by weight.
Preparation of epichlorohydrin from allyl chloride and per-propionic acid.
~ - 15 -, ~%~
45 g o~ 20% strength perpropionic acid in benzene (0.1 mol) were initially introduced into a 200 ml three-necked double-walled ~lask with a magnetic stirrer, internal thermometer, dropping funnel and re~lux condenser and were thermostatically controlled at 70C. Thereafter, 22.96 g (0.3 mol) of allyl chloride are added dropwise such that the temperature could be kep-t at 70C. After stirring under reflux ~or a further 6 hours, tritrimetric analysis gave a perpropionic acid conversion of 98.5%. Analysis of the reaction mixture by gas chromatography showed that epichloro-hydrin was formed with a selectivity of 97.5%, relative to perpropionic acid employed. After cooling, the reaction mlxture was washed several times with water in order to remove the propionic acid and was then fractionated. 8.73 g of epichlorohydrin resulted, xample 2 Preparation o~ 2-(1,2~dichloroethyl-)oxirane from 3,4-di-chloro-l-buten~ and perpropionic acid.
62.9~ g (0.147 mol~ of perpropionic acid, as a 21%
~treng~h svlution in benzene, were added dropwise to 55.87 g (0.447 molj of 3,4-dichloro-1-butene at 70C, whilst stirring.
After the dropwise addition, the mixture was stirred at this temperature ~or a ~urther 6 hours, and tritrimetric analysis then ~howed a perpropionic acid conversion o~ 97%. Ths reaction solut{on was cooled to room temperature and analysed by gas chromatography. As the analysis showed, 2-(1,2-di-chloroethyl-)-oxirane was ~ormed with a selectivity of 94.Z%, relat~ve to perpropionic acid employed.
The reaction mi~ture was washed several times with water in order to remo~e the propionic acid, benzene was dis-till~d o~ and the re~ction product was then ~ractionated in ., -a 40 cm packed column, packed with 4 mm glass Raschig ring~.
18.9 g of 2-(1,2-dichloroethyl-)-oxirane were isolated with a purity of 99.4%.
Ex~mple ~
Preparation o~ 2,3-bis-(chloro~ethyl)-oxirane from 1,4-di-chloro-2-butene and perpropionic acid.
63.97 g (0.147 mol) o~ perpropionic acid, as a 20.68%
strength solution in benzene, were added dropwise to 55.2 g (0.4416 mol) of 1,4-dichloro-2-butene at 70C and the mixture was then further stirred at this temperature. A~ter a reaction time of 4 hours, the peracid conversion was 96%, and a~ter 6 hours it was over 99%. 2,3 Bis(chloromethyl)-oxi-rane was formed with a selectivity of 96.5%, relative to per-propionic acid employed. After removing the propionic acid by extracting the reaction mixture by shaking several time~
with water and subsequently ssparating o~f -the benzene by dis-tillation, and after fractionation of the reaction product over a ~0 cm packed column, filled with 4 mm glass Raschig rings, 19.6 g of 2,3-bis-(chloromethyl)-oxirane were obtained with a purity of 99.g%~
~cntinuou~ preparation o~ 2,3-bis-(chloromethyl)-oxirane from 1,4-diohloro-2-butene and perpropionic acid.
A solution of perpropionic acid in benzene, to which a ~tabili~er o~ the type9 which is commercially available, con-sisting o~ sodium salts of polyphosphoric acids partially esterified with loffg-chain alcohols has been added, was reac-ted with 1,4~dichloro-2 butene in a reaction system in the ~orm of a t~ ee-stage ca~cade o~ stirred kettles. Each o~ the throe ~stirred ~ettles had a volume of 10 1. The kettles were heated via heating coil~ located in the kettle. All Le A 17 776 - 17 -4~3 three kettles were the~no tatically controlled at 70C.
2,137.5 g (4.75 mols) of perpropionic acid, as a 20%
strength solution in benzene, and 1,781.25 g (14.25 molsj of ~ 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 per-propionic acid was converted ~o the exten~ o~ 96.~%. The selectivity of the 2,~-bis-(chloromethyl)-oxirane formed was 96%, relative to perpropionic acid amployed.
The reaction mixture obtained after the third reactor had the following average composition: 35.6% of benzene, 30.8% of 1,4-dichloro-2-butene, 16.24~ of 2,3-bis-(chloro-methyl)-oxirane and 17% of propionic acid. This mixture was extracted in a pulsating per~orated tray column with twice the amount of water in order to separate off the propionic acid. Therea~ter, the residual content of propionic acid was 0.04%. The reaction mixture obtained after this opera-tion wa~ fractionated in a distillation line. Benzene was di~tilled in a fir~t column in an amount o~ 1,395 g per hour.
The bot~om product o~ this column, which essentially consisted of star~ing materlal and oxirane~ waq ~ractionated in a second column under reduced pressure. 1,206.5 g o~ 1,4-dichloro-2-butene per hour were obtained a~ the head product. The bottom pr~duct o~ thi~ column waq freed from high-boiling constituents i~ a third column under reduced pressure.
629.5 g of 2,3-bis-(chloromet~yl) oxirane per hour were obtained as the head product with a purity of over 99.~.
Thi3 correspond~ to a yleld o~ 94%~ relative to the perpro-pio~ic acid employed in the reastion ystem~
.. ,~.
L~ a~ 18 -:. ~
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 ~or a further 2 hour~. 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 1,4-di-bromo-2-butene to 3,4-dibromo-1-butene being about 2 : 1.
The 1,4-dibromo-2-butene was isolated by distillation.
b) Reactlon of 1,4~dibromo-2-butene with perpropionic acid 45 g of 20% strength perpropionic acid in benzene (Ool mol) were added dropwise to 64.2 g (0.3 mol) of 1,4-di-bromo-2-butene at 70C, whilst stirring, and the mixture was stirred at this temperature for a further 4 hours. After this time, the peracld conversion was 95%. Analysis by ga3 chromatography ~howed that the epoxide was ~ormed with a selec-tivity o~ 92.6%, relative to perpropionic acid employed.
After cooling, the reaction mixture was washed several times with water in order to remove the propionic acid and the reac-tion product was fractionated. 20~7 g o~ epoxide were obtained.
~La~ - 19 --~ .
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 bromo-alkyl-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-cycloalkyl, 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 an aromatic hydrocarbon containing 6 to 12 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.
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 an aromatic hydrocarbon containing 6 to 12 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 possible for the radicals R5 to R6 to be linked to form a ring, together with the group CH=CH, 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, monobromo-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-dichloroethylene or 1,2-dibromomethylene radical and n represents an integer from 1 to 6, at least one of the radicals R7 - R10 representing an alkyl, cycloalkyl or alkylene radical of the type mentioned containing chlorine or bromine, is employed as the chloroalkyl-substituted or bromoalkyl suhstituted monoolefin.
4. Process according to claims 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 to 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 allyl chloride is employed as the chloroalkyl-substituted or bromoalkyl-substituted olefin.
6. Process according to claim 1, characterised in that 1,4-dichloro-2-butene is employed as the chloroalkyl-substituted or bromoalkyl-substituted olefin.
7. Process according to claim 1, characterised in that 3,4-dichloro-1-butene is employed as the chloroalkyl-substituted or bromoalkyl-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 perpropionic acid is employed as the percarboxylic acid.
10. Process according to claim 1, characterised in that perisobutyric acid is employed as the percarboxylic acid.
11. Process according to claim 1, characterised in that benzene is used as the aromatic 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 |
|---|---|---|---|
| DE19772734086 DE2734086A1 (en) | 1977-07-28 | 1977-07-28 | PROCESS FOR THE PREPARATION OF HALOGENALKYL SUBSTITUTED OXIRANS |
| DEP2734086.9 | 1977-07-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1120048A true CA1120048A (en) | 1982-03-16 |
Family
ID=6015053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000308194A Expired CA1120048A (en) | 1977-07-28 | 1978-07-26 | Process for the preparation of halogenoalkyl- substituted oxiranes |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0000555B1 (en) |
| JP (1) | JPS5427514A (en) |
| AT (1) | AT358058B (en) |
| CA (1) | CA1120048A (en) |
| DD (1) | DD138066A5 (en) |
| DE (2) | DE2734086A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2456096A1 (en) * | 1979-05-10 | 1980-12-05 | Solvay | PROCESS FOR THE MANUFACTURE OF OLEFIN OXIDES |
Family Cites Families (2)
| 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 |
| DE2519297B2 (en) * | 1975-04-30 | 1981-05-14 | Bayer Ag, 5090 Leverkusen | Process for the continuous production of propylene oxide |
-
1977
- 1977-07-28 DE DE19772734086 patent/DE2734086A1/en not_active Withdrawn
-
1978
- 1978-07-20 EP EP19780100457 patent/EP0000555B1/en not_active Expired
- 1978-07-20 DE DE7878100457T patent/DE2861620D1/en not_active Expired
- 1978-07-26 JP JP9056878A patent/JPS5427514A/en active Granted
- 1978-07-26 DD DD20695678A patent/DD138066A5/en unknown
- 1978-07-26 CA CA000308194A patent/CA1120048A/en not_active Expired
- 1978-07-26 AT AT544678A patent/AT358058B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DE2734086A1 (en) | 1979-02-22 |
| JPS6236030B2 (en) | 1987-08-05 |
| DE2861620D1 (en) | 1982-03-18 |
| AT358058B (en) | 1980-08-25 |
| EP0000555A1 (en) | 1979-02-07 |
| DD138066A5 (en) | 1979-10-10 |
| JPS5427514A (en) | 1979-03-01 |
| ATA544678A (en) | 1980-01-15 |
| EP0000555B1 (en) | 1982-02-10 |
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