DE2734086A1 - PROCESS FOR THE PREPARATION OF HALOGENALKYL SUBSTITUTED OXIRANS - Google Patents

Description

t 2734081

BAYER AG GERMAN GOLD AND SILVER

5090 Leverkusen SCHEIDEANSTALT formerly ROESSLER

6000 Frankfurt / M.

Leverkusen / Frankfurt, the

Dz / AB

Process for the preparation of haloalkyl-substituted oxiranes

The present invention relates to an improved process for the preparation of haloalkyl-substituted oxiranes from haloalkyl-substituted olefins and percarboxylic acids.

Haloalkyl-substituted oxiranes are used in the field of paints and plastics and as organic Intermediates.

It is known to produce chloroalkyl-substituted oxiranes from the corresponding olefins by the chlorohydrin process. This process has the disadvantage that undesirable chlorinated by-products and polluting Salt waste are formed (Ulimanns Encyklopadie d. Techn. Chemistry, Vol. 10, p. 565, left column, line 1 ff., especially 3. 13-15; DAS 1 543 174, column 2, line 15 ff. » especially 3. 32-35).

It is also often difficult to produce a single reaction product in a defined manner using the chlorohydrin method. So leads to the reaction of 4-chlorobutene- (2) with hypochlorous Le A 17 776 7103 PV

509808/002 «

Acid to a mixture of two products, which are characterized by the following formulas:

OH Cl Cl Cl OH Cl

t I I III

CH ₃ -CH-CH-CH ₂ and CH ₃ -CH-CH-CH ₂

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

0 Cl Cl 0

/ \ 1 / V

CH ₃ -CH-CH-CH ₂ and CH ₃ -CH-CH-CH ₂

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

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

Le A 17 776 - 2 -

909808/0026

gives. (SN Lewis in RL Augustin, "Oxidation", Vol. I, St? Ite 233, in particular 3. 6-11, Marcel Dekker, New York 1969).

In particular, with regard to the type and implementation of the reaction between a haloalkyl-substituted olefin and a percarboxylic acid, the structure and manufacturing prices of the percarboxylic acid used are of great importance.

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

RCOOH 4 H ₂ O ₂ ^ - RCOOOH + H ₃ O (1)

With the exception of stronger carboxylic acids such as formic acid and trifluoroacetic acid, strong acids such as sulfuric acid, p-toluenesulionic acid and others are required as a catalyst to quickly establish the equilibrium (SN Lewis in RL Augustin "Oxidation", Vol. I, p. 216 ("C. . Peracids "), Marcel Dekker, New York 1969). The implementation of olefins with z. B. peracetic acid produced by this method did not lead to oxiranes, but to d-glycols and hydroxyacetates (J. Böseken, WC Smit and Gaster, Proc. Acad. Sci. Amsterdam, _32. 377-383 (1929).) The im Mineral acid present in the reaction mixture catalyzes the splitting of the primarily formed oxirane (D. Swern "Organic Peroxides", Wiley Intersciense 1971, Vol. 2, p. 436), which is particularly important in the case of slow-reacting olefins, such as haloalkyl-substituted olefins, with high temperatures and long reaction times when they are converted are necessary, can lead to oxirane losses.

Lo Λ 17 77 (»- 3 -

909808/0026

Peramic acid can be prepared from hydrogen peroxide and formic acid without an additional catalyst (SN Lewis in RL Auqustin, "Oxidation", Vol. I, p. 217, first paragraph, Marcel Dekker, New York 1 'J69). The reaction of "k-chloroalkyl-substituted olefins" with this mineral-acid-free percarboxylic acid, however, only gave the corresponding epoxide in low yields. For example, for the epoxidation of 3,4-dichlorobutene- (1), a 1 st periodic acid was used which was obtained from 0 i-lqer formic acid and 5-icjem hydrogen peroxide. After five hours of reaction at 6 ° C., I- (I, 2-Dlchloräthy1-) oxirane was obtained in 30% yield (EGE Hawkins, J. Chem. Soc., 1959 p. 248 bis 256, especially page 25O, line) ¹ )).

More recently, a process for the preparation of aliphatic chloroepoxides by reacting an allylchlorocarbon5, which has a chlorine atom in the vicinity of the double bond, with an organic per compound which is free of inorganic impurities, has become known (DAS 1 056 5 ') 6). The Perverb indunqen used here are "pure Peric acid, Perproplcms.iure oil acetaldehyde monoperacetate in a mixture with acetaldehyde and / or acetone". (DAS 1 O56 ^r >') 6, Column K), Z. M-Vi.) The Epox idlerumj qem.iß the procedure of DAS 1 O><>">U> of in All / Istel lunq chlorsubi; 11 tu ated olefins with Acet.ilc.hyiimonoperacetat provides the corresponding oxiranes in yields based on the per compound depending on the olefin between 17 * and 56 i. (DAS 1 056 596, column i bL; 1, line J5 ff., Example 1, J , 4 and 6).

The p <; resslgic acid used in this process for epoxidation and perpropionic acid is dissolved in an inert

_Le a 17 776 - 4 -

9 8 η!) / Η ο 2 6

BATH ORIGINAL

orq. mixed solvents are used. As elsewhere can be described as typical inert in this process Solvents including acetone, ethyl acetate, butyl acetate and DLbutylether are wounded (US-P. 3,150,154, Column 3, lines 1-3).

With the according to the procedure of the DA ;; 1,056,596 produced peracids can be epoxidized A LIy I solder hydrocarbons; the; However, triggers at oxiranes are low; the Persäare turnover is incomplete. In the specified Ue i.spie Len it is only about ¹ JO & and the purity of the insulated oxide is insufficient for technical use. For example, DAS 1 () 56 5) 6 in Example 5, column 7, line 5 ff. Describes the epoxidation of I-chloro-1-butene with a solution of l'eracetic acid in acetone. The Persäire-Um:; atz is after ten hours of reaction time Ί 1 i. The oxirane is isolated with a purity of 90.5 % in 68% yield.

In the Hrit. PS / 81 6JO is in DeispieL VII, page 7, line 5 ff., The her; te L Lung of), l-DichLoro-1,2-epoxybutane by unsettling of}, 1 -Dich Lor- 1 -butene with Peres : "I" js iure described in acetone. According to this, the peracid conversion is 3) * iin 1 ili-j Fpoxide yield / 5 * · The purity of the epoxide is given as 3%. In the third ΡΓ> 78 1 62Ο winl in the story I <, page /, line (J '> ff. Inch about the epoxidation of a ;; olefins not with Perpr opionsäute reported. After that η i was: 1 answer by Croty I lor id with a solution From Perprcpion: Acid in A ^- tliy iptopionate 1-chloro-2,} -epoxybutane obtained in 56% yield. The peracid conversion was 10%.

I.ti A 17 776 - 5 -

9803 / D026

It is now possible to produce halojiaialkylisubijtituiertu oxiano from halon "'''ialkylsubst ituioil en olefins and] ercai ixjiisäui'tai in organic solution in high yields and great purity , if one can produce a chloroalkyl- or bromoalkyl- substituted monoolefin of the general formula

R ₁ -C - CH _{4 f} (I)

R ₁ and H- independently of one another hydrogen,

C ₁ - to C ₅ -AlKyI, C ₅ - to C ^ cycloalkyl, monochloro-C.- to Cr-alkyl, monobromo-C ^ to C ^ -alkyl, dichloro-Cj- to C ₅ ~ alkyl, DiI) TOm-C ₁ - to Cr-alkyl, monochlor-Cc to C ₇ -cycloalkyl, monobromo-C ₅ - to C, -cycloalkyl, dichloro-Cc "to C, -cycloalkyl, dibromo-C 1- _{to C 7 -cycloalkyl}
mean,

R _? and R ^ independently of one another for hydrogen, C ₁ - to C ₅ -alkyl, monochloro-C ..- to C ₅ -alkyl, monobromo-C ..- to Cr-alkyl, dichloro-C ₁ -to C ₅ -alkyl and dibromo-C 1 to C ₅ alkyl, the grates

R2 and R, together with the carbon atoms of the C = C double bond, form a ring with up to 12 carbon atoms
can,

Le A 17 77Γ> - 6 -

9098Ö8 / 002C

41

and where at least one of the radicals R ₁ to R4 is a chlorine or bromine-containing alkyl or cycloalkyl radical of the type mentioned,

with a solution of a percarboxylic acid containing 3 to 4 carbon atoms in an aromatic hydrocarbon containing 6 to carbon atoms at a molar ratio of monoolefin to percarboxylic acid such as 1.1 to 10: 1 and at a temperature of 30 ⁰ C to 100 ° C.

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

R ₅ -CH = CH-Rg, ^(II)

Rc and R _c are independently C ₁ - to Cc-alkyl, MOnOChIOr-C ₁ - to Cc-alkyl, monobromo-C ..- to C ₅ alkyl, dichloro-C ₁ - to C ₅ -alkyl or DIbTOm-C ₁ - to Cg-alkyl,

where the radicals Rc and Rg together with the group CH = CH can be linked to form a ring,

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

Le A 17 776 - 7 -

909808/0026

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

(III)

R ₇ and Rq independently of one another hydrogen, C.- to C ₅ -alkyl, MOnOChIOr-C ₁ - to Cj ^ -alkyl, monobromo-C.- to Cc-alkyl, DiChIOr-C ₁ - to C ₅ - alkyl or dibromo -Cj- to C ₅ -alkyl,
Rg and Rj ₀ independently of one another a methylene,

Chloromethylene, bromomethylene, 1,2-dichloro

ethylene or 1,2-dibromomethylene radical

represent,

stands for a whole number from 1 to 6,

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

Le A 17 77f> - 8 -

909808/0026

In particular, monoolefins are isubstituted as ha locjena Iky named:

AL lyLchlorid, 2-Ch LoimüthyL-prorxn,] -Chlor-2-chlonifthyL-prc - {<. ΐ ·, 3-Ctilor-1-butene, 1-chloro-2-butene, 1,4-dichloro-2-butene, 3,4-dichloro-1-butene, 3-chloro-1-pentene, 4-chloro-2-pentene, 1-chloro-2-pentene, 1,4-dichloro-2-pentene, 3,4-dichloro-1-pentene, 1,2-dichloro-3-pentene, 3-chloro -1-cyclopentene, 1,4-dichloro-2-cyclopentene, J-chloro-1-hexene, 1-chloro-2-hexene, 1,4-dichloro-2-hexene, 3,4-dichloro-1-hexene , 2-chloro-3-hexene, 2,5-chloro-3-hexene, 3-chloro-1-cyclohexene, 1,4-dichloro-2-cyclohexene, 1-chloro-2-heptene, 3-chloro-1 -hepten, 3,4-dichloro-1-hepten, 1,4-dichloro-2-hepten, 2-chloro-J-hepten, 2,5-dichloro-3-hepten, 3-chloro-1-eyelohepten, 1,4-dichloro-2-cycloheptene, 1-chloro-2-octene, 3-chloro-1-octene, 1,4-dichloro-2-octene, 2,5-dichloro-3-octene, 2-chloro -3-octene, 3-chloro-4-octene, 3,6-dichloro-4-octene, J-chloro-J-cyclooctene, 1,4-dichloro-2-eyelooctene, 1- (1-chior-cyclohexy1 ) ethene, 1-chloro-2-nonene, 3-chloro-1-monene, 1,4-dichloro-2-ion, 2-chloro-3-nonene, 2,5-dichloro-noiieti, 3-Ch 4-chloro ions, 6-chloro-4-nonene, 3,6-dichloro-4-nonene, 1-chloro-1-ducene, 3-chloro-1-decene, 4-C Chlor-2-decene, 1,4-dichloro-2-ilucene, 2-chloro-3-decene, 2,5-dichloro-3-decene, 5-chloro-3-decene, 6-chloro-1 -decene, i , 6-dichloro-4-decene, 4-Clilor- ^r > -decene, 4, / -Dichlor-'j-deceii, 1-chloro-3-undecene, 3-chloro-1-undecene, 1 , 4-dichloro-2-undecene, 2-chloro-3-undecene, 4-chloro-2-unducene, 2,5-Uich lor-3-umlecen, 5-chloro-3-undecene, 6-chloro-4- undecene, l-chloro-5-unducene, 4, 7-dichloro-5-undecene, 5-chloro-6-undecene, ^r >, B-dichloro-o-undecene, 1 -chloro-3-dodecene, 3- Chlor-1-dodecene, 1,4-dichloro-2-dodecene, 2-chloro-3-dodecene, 4-chloro-2-dodecene, I, S-Diehlor-3-dodecene, 5-chloro-3-dodecene , 6-chloro-4-dodecene, 4-chloro-5-dodecene, 4, T-dichloro-S-dodecene, 5- ^{chloro-6-dodecene, r} >, 8-dichloro-6-dodecene, 5, 7-DI chloro-6-do- (It) Ct-Ii, V-Ch lnr-'i-clodt'ct'M; Λ1 Iy I brom id, 2-Hrmnmt'thy LJ-Urom-2-

Le Λ M 776 - 0 -

9Q9S08 / 0026

BATH ORIGINAL

bromomethyl propene, 3-bromo-1-butene, 1-bromo-2-butene, 1,4-dibromo-2-butene, 3,4-dibromo-1-butene, 3-bromo-i-pentene, 4- Bran-2-pentene, 1-bromo-2-pentene, 1,4-dibromo-2-pentene, 3,4-dibromo-1-pentene, 1,2-dibromo-3-pentene, 3-bromo-1- cyclopentene, 1,4-dibromo-2-cyclopentene, 3-bromo-1-hexene, i-bromo-2-hexene, 1,4-dibromo-2-hexene, 3,4-dibromo-1-hexene, 2- Bromo-3-hexene, 2,5-dibromo-3-hexene, 3-bromo-1-cyclohexene, 1,4-dibromo-2-cyclohexene, 1-bromo-2-heptene, 3-bromo-1-heptene, 3,4-dibromo-iheptene, 1,4-dibromo-2-heptene, 2-bromo-3-heptene, 2,5-dibromo-3-heptene, 3-bromo-1-cycloheptene, 1,4-dibromo- 2-cycloheptene, 1-bromo-2-octene, 3-bromo-1-octene, 1,4-dibromo-2-octene, 2,5-dibromo-3-octene, 2-bromo-3-octene, 3- Bromo-4-octene, 3,6-dibromo-4-octene, 3-bromo-i-cyclooctene, 1,4-dibromo-2-cyclooctene, 1- (1-bromo-cyclohexyl) -ethene, 1-bromo 2-nonene, 3-bromo-1-nonene, 1,4-dibromo-2-nonene, 2-bromo-3-nonene, 2,5-dibromo-3-nonene, 3-bromo-4-nonene, 6- 4-bromo-nonene, 3,6-dibromo-4-nonene, 1-bromo-3-decene _f 3-bromo-1-decene, 4-bromo-2-decene, 1,4-dibromo-2-decene, 2-bran-3-decene, 2,5-dib rom-3-decene, 5-bromo-3-decene, 6-bromo-4-decene, 3,6-dibromo-4-decene, 4-bromo-5-decene, 4,7-dibromo-5-decene, 1-bromo-3-undecene, 3-bromo-1-undecene, 1,4-dibromo-2-undecene, 2-bromo-3-undecene, 4-bromo-2-undecene, 2,5-dibromo-3- undecene, 5-bran-3-undecene, 6-bromo-4-undecene, 4-bromo-5-undecene, 4,7-dibromo-5-undecene, S-bromo-o-undecene, S ^ -dibromo-ö -undecene, 1-bromo-3-dodecene, 3-bromo-1-dodecene, 1,4-dibromo-2-dodecene _/ 2-bromo-3-dodecene, 4-bromo-2-dodecene, 2, S-dibromo -S-dodecene, 5-bromo-3-dodecene, 6-bromo-4-dodecene, 4-bromo-5-dodecene _/ 4,7-dibromo-5-dodecene, S-bromo-e-dodecene, S ^ - Dibromo-6-dodecene, 5,7-dibromo-6-dodecene, 7-bromo-5-dodecene.

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

_Le Λ 17 77 6 - 10 -

909808/0026

JAlIiGiHO CAH

(IV)

R ₁₁ and R ₁₂ independently of one another hydrogen, C ₁ - to Cc-alkyl, monochloro-C ^ to Cc-alkyl, monobromo-C ^ to C ^ - alkyl, DiChIOr-C ₁ - to C ₅ ~ alkyl or dibromo-Cj - to mean C ^ -alkyl,

where at least one of the radicals R ₁ and R _{12 is} MOnOChIOr-C ₁ - to C ₅ -alkyl, MOnObTOm-C ₁ -to Cg DiChIOr-C ₁ - to C ₅ -alkyl or DIbTOm-C ₁ - to C ₅ -alkyl stands.

Examples include:

Allyl chloride, 2-chloromothyl propene, 3-chloro-2-chloromethyl propene, 3-chloro-1-butene, i-chloro-2-butene, 1,4-dichloro-2-

butene, 3,4-dichloro-i-butene, 3-chloro-i-pentene, 4-chloro-2-pentene, 1-chloro-2-pentene, 1,4-dichloro-2-pentene, 3,4-dichloro-i-pentene, 1 ^ -dichloro-S-pentene, 3-chloro-1-hexene, 1-chloro-2-hexene, 1,4-dichloro-2-hexene, 3,4-dichloro-1-hexene, 2-chloro-3-hexene,

Lp h. 17 7 7 fj - 11 -

QAfi

2734Ü86

2, 5-dichloro-1-hexene, J-Ch lor-1-cyclühexen, 1, l-dichloro-2-cyclohexene; Allyl bromide, 2-bromomethyl-propon, 3-bromo-2-bromomethyl-propene, 3-bromo-1-butene, 1-urom-2-butene, 1,4-dibromo-2-butt'n, J, 1- Πibromo-1-butene, J-bromo-1-pentune, 4-bromo-2-penton, 1, 1 -di bromo- λ -penten, ), 4-1) i bromo- 1 -penten, 1, 2-dibromo-3-pentene, 1-uroni- I -hexene, I -bromo-2-hexene, 1,1-dibromo-2-hexene, 3, 4-1) ibro-1-hexene, 2-bromo- 3-hexene, 2, ¹ S-dibromo-3-hoxone, 3-bromo-1-cyclohexene, 1, 1-1) ibromo-2-cyc lohexone.

Very special:; .are to be added with i'crcatbons.iuren after which he completed procedure 1, 4 -I) chloro-2-butene, 1,1-dibromo-2-butene and 3, 1-I) i lor- 1 -but en qeeiqnet.

As Lcisunqsmi t te 1 dit: vet:; ch iedt-nsten aromatic ι Kohlenwii.'5S (! R:; t () ft (! With fi l) i: j 1.! K <> li It nst ■ > tt 1 1 <mu η vetwtn.li ^ t been, the; also r.ubst i tu iei t: u; in kcimn-n. IJe is [) ie Iswe i :; ) benzene, nitrobenzene, I'oluene, xylene, ethylbenzene, I) i'it hy 1 bt'ii.'o 1, (Ίπι 1, I) ii s <ipr opy 1 benzene and C 'come into consideration hlorbtMizol.

Particularly "jeeiqnet are ai ciiiat i:; che K" h lenwasKt; r stot f e with 6 to H carbon f atciiit ι /.ic lien / .ol, nitrobenzoL, chlorobeiizol. Toluene, xylene and eth, Ihii'nl.

Preferred solution t t; l ·; i η I Ιίίι.'οΙ and l'oluoL. Particularly Preferred solvent in the form of benzene. V «r« / ends will be possible also mixtures of different donors with i scher Kc h lenw i:; ser stof f «·

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. Perpropions.i-ire is particularly preferred. Dio production of the mineral acid-free peracids in one of those back or janischen solvents can z. B. be carried out according to the method described in DOS λ 262 970.

Le Λ 1/7 7t I >

BATH ORIGINAL

Generally ⁰ C. preferably carried out in the practice of the erfindumjs <jemäßen process in a temperature range from 30 K) O is carried out at 60-8O ⁰ C, particularly preferably at 65-75 ° C. In special cases, the specified temperatures can also be exceeded or not reached.

In addition to the procedure under isothermal conditions, ie K inhu 11uiKj a uniform temperature in the entire reaction mixture, the reaction can also be carried out with the formation of a so-called temperature gradient, which generally increases as the reaction proceeds. However, M.in can also lead the reaction in such a way that as the reaction progresses, a gradient of falling temperature may arise

According to the invention, the molar ratio of olefin to peracid is 1.1: 1 to K): 1. A molar ratio of V (1H 1.2: 1: 1 to 1: 1 is particularly advantageous. Lit. ;, a molar ratio of 1.5 to 1.0 mol of olefin per molar ionic acid.

The development-related author can be with the most varied of people

Print dont be clocked. Generally one works at

Nor in ι ldr uc k; di; However, the procedure can also be used in the case of under or Put the clock back to ground.

The Via i ier Jt h 111 1er zui tpoxilition used Percarbonsä πe s.) Ll never be low to any extent. Little knowledge is that bi>><)t> v /. -4 iinl ii.i generally not disturbing. (jt> ei jiif.'t IJt at ipit; l ^ weisi> a perc lboxylic acid with a W ι ·> er jc.h ι It / r>nt>L; to 2 i! ew. i. Preferably one uses a P-rcnb ns iiol.isung, which contains less than 1 (each contains water. He Minier j levoiz produces a water content of less than 1), 1 <; ew. - *.

I. λ I _ / M-

Ή) 9 8 0 β Ι ϋ 0 2 S BAD ORIGINAL

The hydrogen peroxide content of the percarboxylic acid used should generally be as low as possible. i: r can be up to 2% by weight. It is advantageous to work with a salary less than 1% by weight. It is particularly advantageous that the Carry out reaction with a percarboxylic acid solution which has a hydrogen peroxide content below 0.3%.

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

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

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

Heavy metal ions in the reaction mixture catalyze the decomposition of the percarboxylic acid. Therefore, substances are generally added to the percarboxylic acid solution which; inactivate the heavy metal ions by forming complexes. Known substances of this type are gluconic acid, ethylenediaminetetraacetic acid, sodium silicate, sodium pyrophosphate, sodium hexametaphosphate, disodium dimethyl pyrophosphate or Na ₂ (2-ethylhexyl) ^ (P ₃ O _1o ) ₂ (DAS 1 O56 l> 96,! Column? 4, line 60 ff .).

The haloalkyl-substituted olefin can be different Kind introduced into the direction used for the implementation

Lv Λ 17 7 7 (. 14 -

B 0 9 8 0 8 / η 0 2 f.

lo 2734085

will. It can be added to the reactor together with the percarboxylic acid solution , or the two components can be fed to the reactor separately from one another . It is also possible to feed the olefin and the percarboxylic acid solution into the reactor unit at different points. When using several reactors connected in cascade, it can be advantageous to introduce all of the olefin into the first reactor . However, the olefin can also be divided between the various reactors .

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

The reaction is expediently carried out with as complete conversion of the percarboxylic acid as possible. In general , more than 95 mol% of the percarboxylic acid are converted. It is expedient to convert more than 98 mol% of peracid.

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

The reaction mixture is worked up in a manner known per se, for. B. by distillation. It is particularly advantageous to use the reaction mixture before the distillative Working up to separate off the carboxylic acid formed during the reaction and corresponding to the percarboxylic acid with water extract. The extraction can be carried out in the

Le A 17 776 - 15 -

909808/0026

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

In a preferred implementation of the method, about 20 wt .-% is added strength perpropionic acid in benzene with stirring to the triple-molar quantity halogenalkylsubstituiertem olefin which is thermostated at 70 ⁰ C. The perpropionic acid solution contains less than 10 ppm mineral acid; it has a water content below 0.1% and a hydrogen peroxide content of less than 0.3%. To complex heavy metal ions, about 0.05% by weight of Na ₅ (2-ethylhexyl) ₅ (Ρ, Ο.-) _{2 was} added to the perpropionic acid before the reaction. The progress and the end of the reaction are monitored by taking samples of the reaction solution at intervals and titrimetrically determining the remaining percarboxylic acid content. After the reaction has ended, the reaction mixture is cooled and washed three times with the same amount by weight of water to remove the propionic acid. The propionic acid-free reaction mixture is then fractionated.

Le A 17 776 - £ 1 -

909808/0026

$ 273,408

The following examples illustrate the invention. Unless otherwise stated, all percentages are Percent by weight.

example 1

Production of epichlorohydrin from allyl chloride and perpropionic acid.

In a 200 ml three-necked jacketed flask equipped with a magnetic stirrer, internal thermometer, dropping funnel and reflux condenser, 45 g of 20% perpropionic acid in benzene (0.1 mol) were charged and thermostatted at 70 ⁰ C. 22.96 g (0.3 mol) of allyl chloride are then added dropwise in such a way that the temperature could be kept at 70.degree. After stirring under reflux for a further 6 hours, the titrimetric analysis showed a perpropionic acid conversion of 98.5%. Gas chromatographic analysis of the reaction mixture showed that epichlorohydrin was formed with a selectivity of 97.5%, based on the perpropionic acid used. After cooling, the reaction mixture was washed several times with water to remove the propionic acid and then fractionated. 8.73 g of epichlorohydrin resulted.

Example 2

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

In 55.87 g (0.447 mol) of 3,4-dichloro-1-butene were added dropwise at 70 ⁰ C with stirring, 62.96 g (0.147 mol) of perpropionic acid as 21% solution in benzene. After dropping, more was added

Le-A 17 776 - 17 -

909808/0028

Stirred for 6 hours at this temperature, then the titrimetric analysis showed a perpropionic acid conversion of 97% The reaction solution was cooled to room temperature and analyzed by gas chromatography. As the analysis showed was 2- (1,2-dichloroethyl) - oxirane with a selectivity based on the perpropionic acid used, formed by 94.2%

The reaction mixture was washed several times with water to remove the propionic acid, benzene was distilled off and then fractionated in a 40 cm packed column filled with 4 mm glass Rasching rings. It was 18.9 g 2- (1,2-dichloroethyl) - oxirane isolated with a purity of 99.4%.

Example 3

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

63.97 g (0.147 mol) of perpropionic acid as a 20.68% solution in benzene were added dropwise to 55.2 g (0.4416 mol) of 1,4-dichloro-2-butene at 70 ° C. and stirring was then continued at this temperature . After a reaction time of 4 hours the peracid conversion was 96%, after 6 hours it was over 99%. 2,3-Bis (chloromethyl-oxirane was formed with a selectivity, based on the perpropionic acid used, of 96.5%. After removal of the propionic acid by shaking out the reaction mixture several times with water and then separating off benzene by distillation, after fractionation via a 30 cm packed column, filled with 4 mm glass raschig rings, 19.6 g of 2,3-bis (chloromethyl) oxirane with a purity of 99.9% were obtained.

Le A 17 776 - 18 -

909808/0026

$ 273,403

Sh

Example 4 ^{m /} i

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

A solution of perpropionic acid in benzene, to which a stabilizer of the type of commercially available sodium salts of polyphosphoric acids partially esterified with long-chain alcohols, was reacted with 1,4-dichloro-2-butene in a reaction system designed as a three-stage stirred tank cascade. Each of the three stirred kettles had a volume of 10 liters. The kettles were heated using heating coils installed in the kettle. All three boilers were thermostatically controlled at 70 ⁰ C.

To this reaction system, 2,137.5 g of perpropionic acid was added per hour fed as a 20% solution in benzene (4.75 mol) and 1,781.25 g (14.25 mol) of 1,4-dichloro-2-butene, which corresponded to an average residence time of about 8 hours. Under these reaction conditions, the perpropionic acid 96.8% implemented. The selectivity of the 2,3-bis (chloromethyl) oxirane formed was 96%, based on the amount used Perpropionic acid.

The reaction mixture obtained after the third reactor had the following composition on average: 35.6% benzene, 30.8% 1,4-dichloro-2-butene, 16.24% 2,3-bis (chloromethyl) oxirane and 17% propionic acid. This mixture was used to separate off the propionic acid in a pulsating sieve tray column extracted with twice the amount of water. The residual propionic acid content was then 0.04%. That after this The reaction mixture obtained from the operation was separated in a distillation line. In a first column was benzene distilled in an amount of 1,395 g per hour. The bottom product of this column, which consists essentially of starting material

Le A 17 776 - 19 -

909808/0025

The product and oxirane were separated in a second column under reduced pressure. The top product was pro 1 hour 1206.5 g of 1,4-dichloro-2-butene were obtained. The bottom product of this column was in a third column under freed from high boilers under reduced pressure. As a top product 629.5 g of 2,3-bis (chloromethyl) oxirane were added per hour obtained with a purity of over 99.9%. This corresponds to a yield of 94% based on that in the reaction system used perpropionic acid.

Example 5

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

a) Bromination of butadiene

171.4 g (3.17 mol) of butadiene were dissolved in 400 ml of η-hexane. At -20 ° C. , 314 g (1.964 mol) of bromine were added dropwise with stirring. After the dropwise addition, the mixture was stirred at this temperature for a further 2 hours. The mixture 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-dibromo-2-butene to 3,4-dibromo-1-butene being about 2: 1. The 1,4-dibromo-2-butene was isolated by distillation.

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

Le A 17 776 - 20 -

909808/0026

$ 273,408

To 64.2 g (0.3 mol) of 1,4-dibromo-2-butene was added at 70 ° C under Stirring 45 g of 20% perpropionic acid in benzene (0.1 mol) added dropwise and a further 4 hours at this temperature touched. After this time, the peracid conversion was 95%. The gas chromatographic analysis showed that 2,3-bis (bromomethyl) oxirane with a selectivity of 92.6%, based on the perpropionic acid used. That After cooling, the reaction mixture was washed several times with water and fractionated to remove the propionic acid. 20.7 g of 2,3-bis (bromomethyl) oxirane were obtained.

Le A 17 776

- 21 -

$ 909808/002

Claims (14)

Claims Ί. ' Process for the preparation of haloalkyl-substituted oxiranes from haloalkyl-substituted olefins and percarboxylic acids, characterized in that a chloroalkyl- or bromo-alkyl-substituted ilonoolefin of the general formula ? 3 R ₁ -C = CR.
ι 4 wherein R ₁ and R ₄ independently of one another are hydrogen, C ₁ - to C ₅ -alkyl, C ₅ - to ^ -cycloalkyl, monochloro-Cj- to C ₅ -alkyl, monobromo-C, -to C ₅ -alkyl, DiChIOr-C ₁ - to Cj-alkyl, dibromo- C ..- to C, - alkyl, monochloro-C ^ - to Cj -cycloalkyl, monobromo-C ^ - to C ₇ -cycloalkyl, dichloro-Cc "to C ₇ -CyClO-alkyl, dibromo-Cc" to C ^ -Cycloalkyl mean R ₂ and R ₃ independently of one another for hydrogen / C ₁ - to Cc-alkyl, monochloro-Cj- to Cg-alkyl, monobromo-C ₁ - to C ^ -alkyl, dichloro-C ₁ - to C ₅ -alkyl and dibromine -C ^ to C ^ - alkyl, where the radicals R ₂ and R ₃ together with the carbon atoms of the C »C double bond can form a ring with up to 12 carbon atoms, Le A 17 776 - 22 - $ 909808/002 and where at least one of the radicals R ₁ to R _{4 is} a chlorine or bromine-containing alkyl or cycloalkyl radical of the type mentioned, with a solution of one containing 3 to 4 carbon atoms Percarboxylic acid in an aromatic, 6 to 12 carbon atoms containing hydrocarbon at a molar ratio of monoolefin to percarboxylic acid of 1.1: 1 to 10: 1 and at a temperature of 30 ° C to 100 ° C. 2. The method according to claim 1, characterized in that one dafl as a chloroalkyl- or bromoalkyl-substituted monoolefin, an olefin of the formula R ₅ -CH = CH-R ₆ , wherein R ₅ and R ₆ independently of one another C ₁ - to C MOnOChIOr-C ₁ - to Cg-alkyl, monobromo _{-C 1 -C 5} -alkyl, DiChIOr-C 1 - to C ₅ "alkyl or dibromo-Cj- to Cg-alkyl, where the radicals R ₅ and R _g can be linked together with the group CH = CH to form a ring, begins. and where at least one of the radicals R _{1 and R 6 is} MOnOChIOr-C 1 - to Cg-alkyl, monobromo _{-C 1 - to Cg-alkyl, dichloro-C 1 to C 5} -alkyl or dibromo-C 1 to C ₅ Alkyl means Le A 17 776 - 23 - 909808/002 « 3. The method according to claim 1 and 2, characterized in that there is substituted as chloroalkyl or bromoalkyl Monoolefin is an olefin of the formula wherein R ₇ and Rg independently of one another are hydrogen, C ₁ - to C ₅ -alkyl, MOnOChIOr-C ₁ - to Cg-alkyl, Monobromo-Cj- to Cg-alkyl, DiChIOr-C ₁ - to C ₅ -alkyl or dibromo-C, - to Cj-alkyl, Rg and R _{10 are} independently a methylene, Represent chloromethylene, bromomethylene, 1,2-dichloroethylene or 1,2-dibromomethylene radical, _{n stands} for an integer from 1 to 6, and where at least one of the radicals R ₇ -R _{10 is} an alkyl, cycloalkyl or alkylene radical of the type mentioned containing chlorine or bromine. 4. The method according to claim 1 and 2, characterized in that there is an olefin of the formula as the chloroalkyl or bromoalkyl-substituted monoolefin R ₁₁ -CH = CH-R ₁₂ , Le A 17 776 - 24 - §09800 / 002 « V 273408 © RiI and R-- independently of one another hydrogen, C ₁ - to Cc-alkyl, monochloro-C ..- to C, - alkyl, monobromo-C ..- to Cc-alkyl, DiChIOr-C ₁ - to C ₅ - Alkyl or dibromo-Cj- to Cg-alkyl , wherein at least one of R _{1 1} and R ₁₂ is MOnOChIOr-C ₁ - to C _{# c} alkyl monobromo-C .j- to Cc-alkyl, dichloro-C ..- to C ₅ alkyl or dibromo-CJ to C ₅ alkyl,
begins. 5. The method according to claim 1 to 4, characterized in that there is used as the chloroalkyl or bromoalkyl-substituted olefin Allyl chloride is used. 6. The method according to claim 1 to 5, characterized in that there is substituted as chloroalkyl or bromoalkyl Olefin 1,4-dichloro-2-butene is used. 7. The method according to claim 1 to 6, characterized in that there is substituted as chloroalkyl or bromoalkyl Olefin 3,4-dichloro-i-butene is used. 8. The method according to claim 1 to 7, characterized in that there is substituted as chloroalkyl or bromoalkyl Olefin 1,4-dibromo-2-butene is used. 9. The method according to claim 1 to 8, characterized in that the percarboxylic acid used is perpropionic acid. 10. The method according to claim 1 to 9, characterized in that the percarboxylic acid used is perisobutyric acid. Le A 17 776 - 25 - 909808/0021 11. The method according to claim 1 to 10, characterized in that the aromatic hydrocarbon is benzene used. 12. The method according to claim 1 to 11, characterized in that that the reaction is carried out at a molar ratio of olefin to peracid such as 1.5 to 3: 1. 13. The method according to claim 1 to 12, characterized in that that one performs. that the reaction is carried out at a temperature of 60 to 80.degree 14. The method according to claim 1 to 13, characterized in that the reaction product for the separation of the Reaction formed, the percarboxylic acid corresponding carboxylic acid by extraction of the reaction mixture with Water makes. Le A 17 776 - 26 - 909808/0021