CS267459B1 - Method of polyhalogen compounds production by means of addition reaction catalyzed by immobilized catalysts - Google Patents

Abstract

Process for the production of polyhalogen compounds of formula R-CHClCHR CCl. addition 10 to 20 times molar excess carbon tetrachloride to alkenes of formula R-CH = CHR, wherein R is aliphatic, an alicyclic or aromatic chain three to six carbons and R is H or R at 50 to 80 ° C under an inert atmosphere pressure of 0.1 to 0.3 MPa, resting in that the addition catalysts are complexes copper bound to polymeric organic a matrix formed from styrene copolymers or methacrylic or acrylic esters with 1 to 40 wt. "-I crosslinkers through primary and secondary amino groups incorporated in the polymer. As a catalyst it can be reused once immobilized copper complex used isolated from the reaction mixture reaction.

Description

The invention relates to a process for the preparation of polyhalo compounds by the addition of carbon tetrachloride to unsaturated hydrocarbons catalyzed by immobilized copper complexes on polymeric organic supports according to the reaction:

R-CH = CHR '+ CCl ₄ --------------- ý R-CHCl-CHR -CCl-j (I) (II) wherein R is alkyl and chain or aryl: R = H or R.

The use of addition products, of which mainly 1,1,1,3-tetrachloro-3-phenylpropane is an important intermediate in the production of cinnamic acid, is possible in the pharmaceutical and food industries.

The current preparation of type II polyhalohydrocarbons is based on the radical addition of carbon tetrachloride to alkenes in the presence of homogeneous catalysts. .A complex formed from ferric or copper chloride and amine hydrochlorides in the presence of acetonitrile at 110 ° C (Israel Pat. No. 16,079 (1963)), (Chem. Abstr. 59, 9591 (1963)) or by treatment with the complex (triphenylphosphine) can be used. ruthenium at 80 ° C (Tetrahedron Lett. 1973, 5147). Also in the presence of metal oxides in combination with secondary or tertiary amines, 1,1,1,3-tetrachloro-3-phenylpropane is obtained at 120 DEG C. in a yield of 85 DEG C. (Cf. A. O. 209 347, 1982). Another method uses as a catalyst the addition of a complex formed in situ from copper compounds and primary or secondary amines (Čs. A. 0. 241 686, 1984; Hájek M., Šilhavý P., Málek J .: New synthesis of cinnamon aldehyde: Chem. Industry 35, 423 (1985)).

A disadvantage of the current state of preparation of polyhalo compounds formed by the addition of carbon tetrachloride to alkenes and especially alkenyl aromatics in the presence of homogeneous catalysts is the difficulty of removing the catalysts from the reaction mixture.

This disadvantage is overcome by a heterogeneous catalyst for the preparation of type II polyhalohydrocarbons by the addition of carbon tetrachloride to the type I alkenes according to the invention, which uses a copper-based catalyst complexed on a polymeric organic support containing primary or secondary amino groups.

The described process for the preparation of type II polyhalo compounds by the addition reaction of carbon tetrachloride to C 1 -C 0 alkenes or alkenyl aromatics is characterized in that the addition is catalyzed by a preformed immobilized catalyst where the copper compounds are complexed on the polymer matrix via incorporated amino groups. A macroporous or gel copolymer can be used in the form of a polymeric carrier. based on styrene or methacrylic or acrylic acid esters containing 1 to 40 wt. % of crosslinker. The addition is carried out in 10 to 20-fold mol. excess of carbon tetrachloride at catalyst concentrations corresponding to 0.03 to 0.08 geq. Cu / 1. The reaction temperature is in the range of 50 to 80 ° C and the overpressure of the inert atmosphere is 0 to 0.2 MPa.

The activity of heterogeneous catalysts depends on the chemical structure of the organic polymer, the type of modifying agent containing the amino group-containing polymer and the type of crosslinking. Macroporous types of polymers are more preferred than gels. The activity of the catalysts also depends on the ratio of amino groups and Cu bound complexly to the polymer. The most preferred such ratio is in the range of 1.3 to 3.0.

The advantages of using immobilized catalyst complexes for the above addition reactions are the low cost of the catalyst and the relatively simple preparation of the catalyst complex and the reaction under mild conditions, mainly in the ease of removal from the reaction mixture after the reaction.

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The following examples characterize the subject matter of the invention without limiting its scope in any way.

Example 1

A solution of 0.469 parts was added to 0.501 parts by weight of a copolymer of glycidyl methacrylate with 40% by weight of diethylene dimethacrylate modified with diethylenetriamine with a primary amino group concentration of 1.30 mmol / g, a specific surface area of 54.1 m 2 and a pore volume of 1.091 ml / g and a particle size of 400-500. copper chloride dissolved in 15 parts of acetonitrile. After stirring with a vibrating stirrer at 20 DEG C. for 4 hours, the polymer was filtered off on a frit under a nitrogen atmosphere, washed five times with 5 parts of acetonitrile. After vacuum drying, it contained 0.736 mg eq. Cu / g, wherein the molar ratio of NH 4 - groups / Cu in the resulting polymer is 1.76.

Example 2

From 0.331 part of a copolymer of carbohydrate methacrylate with 20 '·; of ammonia-modified ethylene dimethacrylate having 2.53 mmol amino groups / g and a specific surface area of 30.2 m 2 / g, a pore volume of 0.833 ml / g and a particle size of 125 to 180 μm together with 0.472 part of CuCl. polymeric carrier containing 1.46 mg eq. Cu / g. By performing the standard addition described in Example 1 while maintaining the same Cu concentration relative to the other reactants, the yield of 1,1,1,3-tetrachloro-3-phenylpropane after 25 hours of reaction at 25 mol was determined by GLC. 'í teorie.

Example 3

From 0.65 part of a polystyrene-divinylbenzene copolymer with about 20% crosslinking, which contained 5.5 mmol of amino groups / g and a density of 650 g / l and a granulation of 300 to 1000 .mu.m, and from 0.826 part of CuCl, a catalyst containing 1 78 mgeq. Cu / g. Using a catalyst for the addition of carbon tetrachloride to styrene according to the procedure described in Example 1, it was found that after 2 hours of reaction, 1,1,1,3-carbon tetrachloride-3-phenylpropane was formed in a yield of 15.5%.

Example 4

Of the 1.31 parts of polystyrene-divinylbenzene copolymer which contained 7.0 mmol NH 2 groups / g with a grain size of 0.3 to 0.55 mm and a density of 650 g / l and 1.64 parts of CuCl, a catalyst containing 2.83 mg eq. Cu / g polymer carrier. 0.22 part of such a catalyst was used for the addition of CCl 2 to styrene according to the procedure described in Example 1 and a 6.5% GLC yield of 1,1,1,3-tetrachloro-3-phenylpropane was obtained in 8 hours. After the reaction, the immobilized polymer catalyst was filtered off from the reaction mixture under an inert atmosphere, washed with CCl 2 and vacuum dried. 0.3% of the copper originally present in the catalyst complex was found in the filtered reaction mixture. 0.21 part of the catalyst thus regenerated was reused for a fresh reaction mixture of the same addition. After 8 hours, a 2% yield of 1,1,1,3-tetrachloro-3-phenylpropane was obtained, even with a decrease in reactivity.

Example 5

To 0.248 parts of the polymer-supported catalyst prepared from styrene-divinylbenzene according to Example 5 were added 16.8 parts of CCl 2 and 0.89 parts of 1-heptene. The addition reaction was carried out at 75 ° C and 75 kPa overpressure. After 5 h of reaction, 3.1% of 1,1,1,3-tetrachlorooctane product was determined in the reaction mixture by GLC.

Example 6

From 0.70 part of a polystyrene-divinylbenzene copolymer with a grain size of 0.3 to 0.5 mm and a density

CS 267 459 Bl

650 g / l, which contained 2.5 mmol of amino groups / g and from 0.19 part of CuCl, an anchored catalyst with a content of 1.82 mg eq. Cu / g polymer carrier.

0.20 part of this catalyst was used to add 8.23 parts of carbon tetrachloride to 0.46 parts of styrene according to the procedure of Example 1. The reaction was carried out at 70 DEG C., yielding 6% in 4 hours and 20% in 14 hours. yield of 1,1,1,3-tetrachloro-3-phenylpropane without the catalyst losing activity.

Example 7

From 0.81 part of polystyrene-divinylbenzene copolymer containing 0.16 mmol amino groups / g and 0.29 part of CuCl, an immobilized catalyst containing 0.56 mg eq. Cu / g, of which 0.13 parts together with 5.2 parts of CCl ₄ and 0.20 parts of 3-methyl-1-butene were added at 65 ^U C at a pressure of 137 kPa. After 10 hours, it was chromatographed to give 1,1,1,3-tetrachloro-4-methylpentane in 2.5% yield.

Example 8

With 0.34 parts of the immobilized catalyst prepared in Example 7 and containing 0.56 mgeq. Cu / g was added by adding 9.0 parts of carbon tetrachloride to 0.54 parts of 1-octene. The reaction temperature was 74 ° C and the pressure above the reaction mixture was 139 kPa. After 10 hours of reaction, 19.8 "of the theoretically possible amount of 1,1,1,3-tetrachlorononane was formed.

Claims (2)

A process for the preparation of polyhalo compounds of the general formula R-CHClCHCH CCLj by an addition reaction 10 to 20-fold molar excess of carbon tetrachloride to alkenes of the general formula R-CH = CHR ', where R is an aliphatic, alicyclic or aromatic chain of three to six carbons and R is H or R at a temperature of 50 to 80 ° C in an inert atmosphere under pressure 0.1 to 0.3 MPa, characterized in that the addition catalysts are copper complexes bound to a polymeric organic matrix formed from copolymers of styrene or esters of methacrylic or acrylic acid with 1 to 40 wt. ¾ crosslinkers via primary and secondary amino groups incorporated in the polymer. 2. The process according to item 1, characterized in that the once used immobilized copper complex isolated from the reaction mixture after the previous reaction is reused as the catalyst.