FR2597093A1 - PROCESS FOR THE PREPARATION OF HALOGENIC ORGANIC COMPOUNDS - Google Patents

Abstract

THE INVENTION CONCERNS A PROCESS FOR THE PREPARATION OF HALOGENOUS ORGANIC COMPOUNDS RESPONDING TO GENERAL FORMULA I (CF DRAWING IN BOPI) IN WHICH R IS H OR CH, R IS CH, (CH) CH OR A COOR GROUP IN WHICH R IS AN ALKYL IN CC OR A GROUP C (CH) CHCOZ IN WHICH Z IS CH OR A GOLD GROUP IN WHICH R IS AN ALKYL IN CC, X IS CL OR BR, X AND X ARE F, CL, BR OR A GROUP C (X) IN WHICH X IS AS DEFINED ABOVE, BY REACTION OF UNSATURE COMPOUNDS WITH HALOGEN COMPOUNDS IN THE PRESENCE OF A CATALYTIC SYSTEM CONSTITUTED BY A COPPER CONSTITUENT CHOSEN FROM METAL COPPER, OXIDES OR HALOGENIDES OF COPPER AND BY AMINE PRIMARY AND SECONDARY AMINES CONTAINING CC ALKYL, CC CYCLOALKYL, CC ARYL-ALKYL, - (CH) O (CH) - OR - (CH) - OR N IS 2 TO 5, WITH AGITATION OF THE MIXTURE REACTIONAL, AT A TEMPERATURE OF 20 TO 120 C. HALOGENOUS ORGANIC COMPOUNDS ARE INTERMEDIARIES FOR THE PREPARATION OF ACID DERIVATIVES DIMETHYLCYCLOPROPANECARBOXYL CALLED SYNTHETIC PYRETHROIDS. THESE COMPOUNDS ARE EFFECTIVE INSECTICIDES FOR THE PROTECTION OF PLANTS.

Description

The present invention relates to a process for preparing compounds

  halogenated organic compounds for the preparation of pyrethroids.

  Halogenated compounds of certain types are very useful intermediates for the preparation of highly effective insecticides called synthetic pyrethroids. These halogenated compounds are advantageously prepared by radical addition reactions of haloalkanes to suitable unsaturated hydrocarbons. The initiators and catalysts known hitherto in the art for reactions

  additives are not very active and not very selective, and require both high temperatures and high pressures or they are expensive and they are obtained with difficulty.

  For example, the addition reactions of haloalkanes such as tetrachloromethane, 1,1,1-trichlorotrifluoroethane, Freons and the like with unsaturated compounds, among others 3-methyl-1-butene, alkyl acrylates, 3,3 Alkyl dimethyl-4-pentenoates were made using organic peroxides as catalysts (U.S. Patent 4,070,404 (1978), DE.A 2,802,962 (1978)), ruthenium complexes (DE.A 2,751 435 (1977)), iron and copper chlorides in combination with ethanolamine or diethylamine hydrochloride (DE.A 2,920,536 (1979) Bull., Joc., 52, 1511 (1979)), cuprous chloride in acetonitrile (DE.A. 3,045,768 (1979), EP 50,777 (198), Helv Chim Acta 63, 1947).

  (1980)) and iron-pentacarbonyl (GB 2 092 578 (1981)). The products were obtained with maximum yields of 60 to 85%.

  In the reaction of 1,1,1-trichlorotrifluoroethane with low reactivity with ethyl acrylate the product was obtained in only 40% yield at 140 ° C. Similarly, even newer catalysts based on combined metal oxides with organic bases require higher temperatures

(120 to 140 C, CS 209 347)

  An object of the present invention is to avoid or mitigate these disadvantages.

  The invention relates to a process for the preparation of halogenated organic compounds of the following general formula I:

R1 H X

I

X-C-C-C-Y

  Wherein R is hydrogen or methyl, R 2 is methyl, 2-propyl or carboxyl COOR, wherein R is C 1 -C 3 alkyl or C (CH 3) 2 CH 2 COZ wherein Z is methyl or a group OR in which R has the above definition, X is chlorine or bromine, X1 and X2 are each fluorine, chlorine or bromine and Y is fluorine, chlorine, bromine or a group C (X1 ) In which X is as defined above, by reaction of unsaturated compounds of general formula II: R1

RC = CH2

R2

  in which R 1 and R are as defined above, with halogenated compounds of general formula III xl

X-C-Y

X

  wherein X, X1, x2 and Y are as defined above, in the presence of a catalyst system, comprising stirring the reaction mixture containing 1 molar portion of unsaturated compound of the general formula II, 1 to 20 molar parts halogenated compound of general formula III, 0.001 to 0.15 molar part of copper metal or copper oxide, copper salt of inorganic or organic acids or a copper complex or a mixture above-mentioned copper compounds and 0.01 to 1.0 molar part of amine of general formula IV

R3 - NH - R4

  in which R 3 is a hydrogen or a group R and R is a straight or branched chain C1-C12 alkyl group, preferably ethyl, 2-propyl, n-butyl, n-dodecyl or cycloalkyl, especially cyclohexyl or aryl, in particular phenyl or arylalkyl, preferably benzyl, or in which R3 and R4 together represent an alkylene group - (CH2) n- is 2 to 5 or a group - (CH2) 20 (CH2) 2 or a mixture of above-mentioned amines at a temperature of 20

at 120 ° C.

  According to the present invention, the catalyst system is formed by the copper component and the amine which give a copper complex. The copper component according to the invention is preferably selected from cupric chloride, cuprous chloride, cupric bromide and cuprous bromide. Instead of the aforementioned copper halides, other types of copper compounds such as nitrates, sulphates, acetates, ethylhexanoates, acetylacetonates, naphthenates and the like can also be used. However, because of their lower activity and selectivity, their implementation does not

  not the benefits just mentioned.

  According to the invention, the amine of general formula R3NHR4 is chosen from ethylamine, 2-propylamine, n-butylamine, tert-butylamine, necylamine, cyclohexylamine, benzylamine, diethylamine and piperidine. the

  pyrrolidine or morpholine, in which case the catalyst system is prepared by contacting the amine with the copper component before the addition reaction or is produced in situ in the reaction mixture. In view of the exothermicity of the reaction, the unsaturated compound or amine is preferably added in portions to the reaction mixture.

  The addition reactions according to the invention are preferably carried out in the absence of solvents. Nevertheless, inert solvents can advantageously be used to disperse the most expensive starting halogenated compounds. The solvents employed are preferably chlorinated compounds of very low reactivity such as dichloromethane,

  1,1,2,2-tetrachloroethane, chlorobenzene, dichlorobenzene or non-halogenated compounds such as acetonitrile, dioxane, tetrahydrofuran and the like.

  The remarkable character of the catalyst systems according to the invention with respect to the systems known until now in the state of the art for the addition reactions

  radicals is their high efficiency and selectivity under moderate reaction conditions, their

  low price and the ease with which one gets them.

  The reactions can be carried out for the most part under normal pressure and preferably at temperatures of 60 to C, as evidenced by the reaction under low pressure of tetrachloromethane with low-boiling alkenes such as 3-methyl-1-butene. (boiling point 20 C), providing the product with a yield of 91.1%. The desired product yields are generally very high and for most reactions reach 85 to 97% at high conversions (up to 100%). The addition reactions according to the present invention proceed easily even in the case of low reactive halogen compounds such as Freons. For example, 1,1,1-trichlorotrifluoroethane readily reacts under mild conditions at 80-90 C with high selectivity exceeding 90%. The high selectivity of these reactions catalyzed by the systems according to the invention is further attested by the small percentage of waste in the form of 80 distillation polymer residues representing 1 to 10% by weight of the product, even at high conversion rates.

(from 90 to 100%).

  The high efficiency and selectivity of the new catalyst systems according to the present invention results from the great ability, not found so far, of these catalysts to activate halogenated compounds even under mild reaction conditions. In addition, the particular characteristic of these catalysts is their ability to control radical addition reactions so that they take place by a non-chain mechanism, which causes the almost total suppression of the polymerization reactions, unlike the catalysts known until now in the state of the art, the effect of which is limited to

  simple extension of the radical chain.

  The radical addition reactions according to the present invention can be carried out easily on an industrial scale with moderate costs of material, raw materials and energy, and with amounts of

weak waste.

  The examples below are given to better illustrate

  the implementation of the process for the preparation of halogenated organic compounds according to the present invention.

EXAMPLE 1

  A mixture of 14.1 g of 3-methyl-1-butene, 307.6 g of tetrachloromethane, 0.398 g of cuprous chloride and 4.14 g of 2-propylamine is refluxed at 63-75.5 ° C. for 6 hours. during which the conversion of 3-methyl-1-butene is 89%. The reaction mixture is then cooled, washed with 7% hydrochloric acid and then with water, the excess tetrachloromethane and unreacted 3-methyl-1-butene are removed by evaporation and further distillation under reduced pressure gave 36.3 g of 1,1,1,315 tetrachloro-4-methylpentane (PE: 90-91 ° C. at 1.6 kPa) in a yield of 81.1%, a yield of 91, 1% calculated on 3-methyl-1-butene reacted. The weight of

  distillation residue is 1.0 g.

EXAMPLE 2

  A mixture of 3.5 g of 3-methyl-1-butene, 38.5 g of tetrachloromethane, 0.1 g of cuprous chloride and 1.7 g of cyclohexylamine under a nitrogen atmosphere in an ampoule is heated to 80 ° C. sealed by shaking for 5 hours. By proceeding as described in Example 1, 9.6 g of 1,1,1,325 tetrachloro-4-methylpentane is obtained, ie a yield of 85.7% which corresponds to 92.3% calculated relative to 3-methyl- l-butene

  having reacted. The weight of the distillation residue is 0.10 g.

EXAMPLES 3 TO 19

  Examples 3 to 19 in which the procedure described in Example 2 illustrates the possibilities of variations of the reaction conditions and of the types of catalyst systems according to the invention for the reaction of 3-methyl-butene (A) with tetrachloromethane (B). The yields of 1,1,1,3-tetrachloro-4-methylpentane presented in

  Table are determined chromatographically and reported to the load of 3-methyl-1-butene.

EXAMPLE 20

  The mixture is refluxed at 78.degree.-8.degree.

  40.0 g of ethyl acrylate, 184.6 g of tetrachloromethane, 1.1 g of cuprous chloride and 5.9 g of 2-propylamine. By proceeding as described in Example 1, a total of 90.1 g of ethyl 2,4,4,4tetrachlorobutyrate boiling at 109 ° -110 ° C. at 2 kPa was obtained with a yield of 88.7%. The distillation residue weighs 2.56 g.

EXAMPLE 21

  A mixture of 0.3229 g of ethyl acrylate, 9.92 g of tetrachloromethane, 0.0095 g of cuprous chloride and 0.0685 g of 2-propylamine under nitrogen atmosphere is placed at 80 ° C. in a sealed ampoule with vibration shaking

  for 6.5 hours. The yield determined chromatographically in 2,44,4% -tetrachlorobutyrate is 97%.

SEE TABLE NEXT PAGE

I -

  Table relating to Examples 3 to 19 Example Cu Amine Constituent (D) Mol. Temp. Time Yield (C) A / B / C / D oC h% 3 CuCl 2propylamine 1/5 / 0.02 / 0.4 80 8 94 4 CuCi cyclohexylamine 1/20 / 0.02 / 0.35 80 6 90, CuCl cyclohexylamine 1/1 / 0.02 / 0.35 80 6 77 6 Cu cyclohexylamine 1/5 / 0.1 / 0.35 8o 6 85 7 Cu 2 O cyclohexylamine 1/5 / 0.02 / 0.35 80 6 91 8 CuCI2. 2H20 cyclohexylamine 1/5 / 0.02 / 1.0 80 6 90 9 CuO cyclohexylamine 1/5/0, 005 / 0.25 80 4 51 CuCl diethylamine 1/5 / 0.02 / 0.35 80 6 67 i CuCl benzylamine 1/5 / 0.02 / 0.35 80 6 65 12 CuCl n-butylamine 1/5 / 0.02 / 0.40 80 7 83.5 13 CuCl piperidine 1/5 / 0.02 / 0, 40 80 7 6o 14 CuCl morpholine 1/5/0, 02 / 0.40 80 7 82 CuCl ethylamine 1/5 / 0.02 / 0.40 80 6.5 82 16 CuCl cyclohexylamine 1/5 / 0.02 / 0.50 110 6 78 17 CuC1 cyclohexylamine 1/5 / 0.02 / 0, 45 50 19 89 18 CuCi cyclohexylamine 1/5 / 0.02 / 0.23 23 86 57 19 CuCl cyclohexylamine 1/5 / 0.02 / 0.35 80 6 94 -4 c> O

EXAMPLE 22

  A mixture of 0.4578 g of ethyl acrylate, 8.65 g of tetrachloromethane, 0.055 g of cuprous chloride and 0.189 g of 2-propylamine under a nitrogen atmosphere is heated to 80 ° C. in a sealed ampoule with vibration shaking for one hour. 3 hours. The yield determined by chromatographic method in ethyl 2,4,4,4-tetrachlorobutyrate is 94.3%.

EXAMPLE 23

  A mixture of 34.4 g of methyl acrylate, 123.0 g of tetrachloromethane, 0.4 g of cuprous chloride and 4.73 g of propylamine is refluxed for 7 hours. By proceeding as described in Example 1, 87.3 g of

  Methyl 2,4,1,4-tetrachlorobutyrate boiling at 101-102 ° C at 2.1 kPa with a yield of 91%. The distillation residue weighs 3.2 g.

EXAMPLE 2%

  A mixture of 1.756 g of 2-methylpropene, 19.26 g of tetrachloromethane, 0.063 g of cuprous chloride and 0.83 g of propylamine under a nitrogen atmosphere in a sealed ampoule with vibration shaking for 8 hours is heated to 80.degree. Using the procedure described in Example 1, 5.92 g of 1,1,1,3-tetrachloro-3-methylbutane, boiling 70-7 ° C., are obtained under 1.6 kPa with a yield of 90.1%. The residue

of distillation weighs 0.042 g.

EXAMPLE 25

  A mixture of 1.42 g of 3-methyl-1-butane, 9.45 g of 1,1,1-trichlorotrifluoroethane, 0.06 g of cuprous chloride, 0.30 g of 2-propylamine and 6 g is added at 80 ° C. ml of dichloromethane under a nitrogen atmosphere in a sealed ampoule with vibration stirring for 6 hours. The procedure described in Example 1 gives 3.92 g of 1,1,1-trifluoro-2,2,4-trichloro-5-methylhexane boiling at 65 ° C. at 1.6 kPa with a yield of 75%. The distillation residue

weighs 0.32 g.

EXAMPLE 26

  A mixture of 2.02 g of ethyl acrylate, 9.5 g of 1,1,1-trichloro-trifluoroethane and 0.06 g of chloride is heated to 90 ° C.

  copper, 600 g of cyclohexylamine and 6 ml of dichlorometha-

  under a nitrogen atmosphere in a sealed ampoule with shaking for 5 hours. By proceeding as in Example 1, 4.15 g of ethyl 2,4,4-trichloro5,5,5-trifluoropentanoate boiling at 58 ° -60 ° C. under 133 Pa is obtained with a yield of 71.5%.

EXAMPLE 27

  A mixture of 15.6 g of 3,3-dimethyl-4-pentenoate, 37.5 g of 1,1,1-trichlorotrifluoroethane, 0.1 g of cuprous chloride and 0.24 g of 2 is heated to 800 ° C. propylamine under a nitrogen atmosphere in a sealed ampoule with shaking for 4 hours. Using the procedure described in Example 1, 31.3 g of ethyl 3,3-dimethyl-4,6,6-trichloro-7,7,7-trifluoroheptanoate, boiling at 86 ° -87 ° C. at 20 Pa, are obtained in a yield of 91%. EXAMPLE 28 A mixture of 1.29 g of 3-methyl-1-butene, 18.66 g of 1,2-difluorotetrachloroethane, 0.073 g of cuprous chloride and 0.163 g of 2-propylamine in a blister is heated to 80 ° C. sealed with vibration shaking for 7 hours. 1.54 g of 1,2-difluoro-1,1,1,4-tetrachloro-5-methylhexane boiling at 84-86 ° C. at 1.6 kPa in a yield of 30 are obtained in the manner described in Example 1; 7%, corresponding to a yield of 86.7%, based on the 3-methyl-butene reacted. The distillation residue weighs 0.067 g. EXAMPLE 29 A mixture of 1.22 g of 3-methyl-1-butene, 23.95 g of 1,1,2-trifluoro-2-chloro-1, 2-dibromoethane and o, o68 g of cuprous chloride and 0.82 g of 2-propylamine under a nitrogen atmosphere in a sealed vial with vibration shaking for 6.5 hours. By proceeding as in Example 1, 2.13 g of 1,1,2-trifluoro-2chloro-1,4-dibromo-5-methylhexane boiling at 88-92 ° C. at 1.6 kPa with a yield of 35.4 are obtained. % corresponding to a yield of 85.6% calculated relative to the 3-methyl-1-butene reacted. The distillation residue weighs 0.094 g. 13 C NMR analysis (CDCl3, TMS) of the mixture of diastereoisomers: CH3 g = 16.26; 17.69; 20.58; 21.85 CH 2 = 43.08 (J (CF) = 19.2 Hz); 42.7 (J (CF) = 19.5 Hz)

CH 0 = 32.96; 35.36

  CHBr / = 53.92; 56.20 CF i = 110.6; 110.8 (1 J (CF) = 244 Hz) CF 2 = 120.1; 120.3 (1J (CF) = 353 Hz)

EXAMPLE 30

  A mixture of 1.29 g of 3-methyl-1-butene, 12.2 g of tetrabromomethane, 0.037 g of cuprous chloride and 0.81 g of 2-propylamine under a nitrogen atmosphere in a sealed ampoule is heated to 80 ° C. with vibration stirring for 7 hours. By proceeding as described in Example 1, 4.45 g of 1,1,1,3-tetrabromo-4-methylpentane boiling at 99 ° C. in Pa are obtained with a yield of 50.2%, corresponding to 85.degree. , 2% based on reacted 3-methyl-1-butene. The distillation residue weighs 0.32 g. 13 C NMR analysis (CDCl 3, TMS):

CH3 = 17.46; 21.22

CH S = 34.99

CHBr δ '= 60, o10

CH2 '= 64.90

CBr3 δ = 36.93

Claims (4)

  A process for the preparation of halogenated organic compounds corresponding to the general formula I: R 1 H X 1 I I J X - 2- C - y - Y R H X   wherein R is hydrogen or methyl, R2 is methyl or 2-propyl or COOR wherein R is C1-C3 alkyl or the group of formula C (CH3) 2COZ wherein Z is methyl or OR wherein R is C 1 -C 3 alkyl, X is chloro or bromo, X 1 and X are fluorine, chlorine or bromine and Y is fluorine, chlorine, bromine or C (X 1) Wherein X is as defined above, by reaction of unsaturated compounds of general formula II: R1 C = CH2 (II) R2 1 2 "-2   wherein R 1 and R are as defined above, with a halogenated compound of the general formula III X 1 X - C - Y (III)   Wherein X, X1, x2 and Y are as defined above in the presence of a catalyst system, comprising reacting 1 molar portion of the unsaturated compound of the general formula II with 1 to 20 molar parts of the halogenated compound of general formula III in the presence of 0.001 to 0.15 molar part of a copper component selected from copper metal or a copper oxide or copper halide or a mixture of the above-mentioned copper compounds and from 0.01 to 1 0 molar portion of an amine component of the general formula IV R3 _ NH - R4 (IV)   (iv) daslqule 3 est4 4 in which. R is hydrogen or RR is straight or branched chain C 1 -C alkyl, cycloalkyl, C 5 -C 8, aryl-C 1 -C 3 alkyl or R 3 and R represent together a group - (CH 2) 20 (CH 2) 2 = or - (CH 2) n- is equal to 2 to 5, with stirring of the mixture, at a temperature of 20 to 1200C. 2. Process according to claim 1, characterized in that the reaction is carried out in the presence of the copper-amine complex prepared before the addition reaction from the constituent copper and amine component.   3. Process according to claim 1 or 2, characterized in that the reaction is carried out in the presence of a chosen solvent.   from dichloromethane, 1,1,2,2-tetrachloroethane and chlorobenzene, the amount of solvent up to 90% by volume of the reaction mixture.   4. Process according to claims 1 to 3, characterized   in that the reaction mixture is heated to a temperature from 60 to 100 ° C. NOT