CH671220A5 - - Google Patents

Description

DESCRIPTION

The invention relates to a process for the preparation of halogenated organic compounds which are used for the preparation of pyrethroids.

Certain types of halogenated compounds are very important intermediates in the production of insecticidal active ingredients, which are also known as synthetic pyrethroids. In the majority of cases, these halogenated compounds are prepared by radical addition reactions of haloalkanes to corresponding unsaturated compounds. The previously known initiators and catalysts used in these addition reactions are not very active and are selective to a limited extent, they either require elevated reaction temperatures or higher pressures, and moreover they are often difficult to obtain and expensive. So z. B. for the addition reactions of haloalkanes, such as carbon tetrachloride, 1,1,1-trichlorotrifluoroethane, freons and the like. are with unsaturated compounds, such as with 3-methyl-1-butene, alkyl acrylates, alkyl-3,3-dimethyl-4-pentenoates and the like. Ä., as catalysts, organic peroxides (US Patent 4,070,404 [1978], FRG Patent 2,802,962 [1978]), ruthenium complexes (FRG Patent 2751435 [1977]), iron and copper chlorides in combinations with ethanolamine or diethylamine hydrochloride (FRG patent 2,920,536 [1979], "Bull. Chem. Soc. Japan" 52,1511 [1979]), copper (I) chloride in acetonitrile (FRG patent 3,045 7 [1979], " European patent "50, III [1981]," Helv. Chim. Acta "63, 1947 [1980]) and iron pentacarbonyls (GB patent 2 092 578 [1981]). The maximum yields of products reached values between 60 and 85%. In the case of the less reactive 1,1,1-trichlorotrifluoroethane in reaction with ethyl acrylate, the yield of the product at 140 ° C was only 40%. The newer catalysts, which are based on the combination of metal oxides with organic bases, also required higher (120 to 140 ° C) temperatures (Czechoslovak author certificate 209 347). This invention overcomes the disadvantages listed above.

The subject matter of the invention is a method according to claim L Advantageous further developments of the method result from the dependent claims.

The catalytic system according to the invention is composed of a copper component and an amine, which form an amine-copper complex. As the copper component of the catalyst according to the invention, copper halides, such as copper (I) cMoride, copper (II) chloride, copper (I) bromide and copper (II) bromide, have proven to be the most suitable. Instead of the copper halides mentioned, other types of copper compounds, such as nitrates, sulfates, acetates, ethylhexanoates, acetylacetonates, naphthenates and the like, can also be used. Ä., are used; However, their use does not bring the advantages outlined above, since they are much less active and, above all, are not very selective.

According to the invention, amine of the general formula R3NHR4 can be ethylamine, 2-propylamine, n-butylamine, tert-butylamine, n-decylamine, cyclohexylamine, benzylamine, diethylamine, piperidine or pyrrolidine, the catalytic system being mixed with the amine the copper component is prepared in advance or in situ in the reaction mixture. In view of the exothermic course of the reaction, it is advantageous to gradually add the unsaturated compound, possibly the amine, to the reaction mixture.

The addition reactions according to the invention are advantageously carried out without the presence of a solvent, but inert solvents can be used for the dilution of the more expensive halogenated starting compounds. Suitable solvents are non-reactive chlorinated substances such as dichloromethane, 1,1,2,2-tetrachloroethane, chlorobenzene, dichlorobenzene or non-chlorinated substances such as acetonitrile, dioxane, tetrahydrofuran and the like. Ä.

The greatest advantage of the catalytic systems according to the invention compared to the catalysts of radical addition reactions known hitherto results from their high effectiveness and their selectivity even under mild reaction conditions, from their low price and their easy accessibility. The reaction can easily be carried out generally without pressure and advantageously at temperatures between 60 and 90 ° C., which is clearly illustrated by the pressure-free reaction of carbon tetrachloride with low-boiling alkenes, such as with 3-methyl-1-butene (boiling point 20 ° C.) , can be proven with a yield of 91.1%. The yields of the desired products are usually very high and in the majority of cases reach values between 85 and 97% with high sales (up to 100%). Addition reactions according to the invention proceed easily even in the case of less reactive halogenated ones

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671220

Connections like freons; for example, 1,1,1-trichlorotrifluoroethane without any problems under mild conditions at 80 to 90 ° C with a high selectivity above 90%. The high selectivity of the reactions which are catalyzed by the systems according to the invention is further documented by a low proportion of waste in the form of polymeric distillation residues, which in amounts of between 1 and 10% by weight (based on the product), even at high levels Sales (90 to 100%) accrue.

The high effectiveness and selectivity of the new catalytic systems according to the invention is based on their hitherto not described high ability to activate halogenated compounds even under mild reaction conditions. These catalysts are further distinguished by the specific property of influencing radical addition reactions in such a way that they take place via a non-chain-like mechanism, which results in a virtually complete suppression of polymerization reactions, in contrast to the catalysts known hitherto, the mode of action of which is only limited to the extension of the radical chain.

The implementation of the radical addition reactions 20

According to the invention, it is also easy to implement on an industrial scale, and this with small demands on apparatus, raw materials and energy and with small amounts of waste.

The examples given describe in more detail the process for the preparation of halogenated organic compounds according to the invention, without restricting or limiting the scope of their validity.

example 1

A mixture of 14.1 g of 3-methyl-1-butene, 307.6 g of tetrachloromethane, 0.398 g of copper (II) chloride and 4.14 g of 2-propylamine is 6 at 63 to 75.5 ° C. 6 Heated to the boiling point for hours, after which the conversion of the 3-methyl-1-butene reached 89%. The reaction mixture is cooled, washed with dilute 7% hydrochloric acid and water; the excess carbon tetrachloride and the 35% converted 3-methyl-1-butene are removed by evaporation. Subsequent distillation at reduced pressure gives 36.3 g of l, l, l, 3-tetrachloro-4-methylpentane with a boiling point (Sdt.) 90 to 91 ° C / 1.6 kPa, in a yield of

Example 22

A mixture of 0.4578 g of ethyl acrylate, 8.65 g of carbon tetrachloride, 0.055 g of copper (I) chloride and 0.189 g of 2-propylamine is heated in a sealed ampoule with vibration stirring in a nitrogen atmosphere at 80 ° C. for 3 hours. The chroma81.1%, d. H. 91.1% on the converted 3-methyl-1-butene. The distillation residue is 1.0 g.

Example 2

A mixture of 3.5 g of 3-methyl-1-butene, 38.5 g of carbon tetrachloride, 0.1 g of copper (I) chloride and 1.7 g of cyclohexylamine is in a sealed ampoule with vibration stirring in a nitrogen atmosphere at 80 ° C heated for 5 hours. The process described in Example 1 gives 9.6 g of 1,1,1,3-tetra-chloro-4-methylpentane in a yield of 85.7%, which is a yield of 92.3%, calculated on that converted 3-methyl-1-butene, corresponds.

Examples 3 to 19

Examples 3 to 19, which were carried out according to the process described in Example 2, document the variability of the reaction conditions and the different types of catalyst systems according to the invention in the reaction of 3-methyl-1-butene (A) with carbon tetrachloride (B) . The indicated yields of l, l, l, 3-tetrachloro-4-methylpentane were determined by chromatography and relate to the 3-methyl-l-butene used.

Example 20

A mixture of 40.0 g of ethyl acrylate, 184.6 g of carbon tetrachloride, 1.1 g of copper (I) chloride and 5.9 g of 2-propylamine was heated to the boiling point at 78 to 88 ° C for 5 hours. The process described in Example 1 gives 90.1 g of ethyl 2,4,4,4-tetrachlorobutyrate, Sdt. 109 to 110 ° C / 2 kPa, in a yield of 88.7%. The distillation residue is 2.56 g.

Example 21

A mixture of 0.3329 g of ethyl acrylate, 9.92 g of carbon tetrachloride, 0.0095 g of copper (I) chloride and 0.0685 g of 2-propylamine is 6.5 in a sealed ampoule with vibration stirring in a nitrogen atmosphere at 80 ° C. Heated for hours. The chromatographically determined yield of ethyl 2,4,4,4-tetrachlorobutylate is 97%.

example

Copper component

Amine

Molar ratio

temperature

Response time

yield

(C)

(D)

A: B: C: D

(° C)

(H)

(%)

3rd

CuCl

2-propylamine

1

5: 0.02: 0.40

80

8th

94

4th

CuCl

Cyclohexylamine

1

20: 0.02: 0.35

80

6

90.5

5

CuCl

Cyclohexylamine

1

1: 0.02: 0.35

80

6

77

6

Cu

Cyclohexylamine

1

5: 0.10: 0.35

80

6

85

7

Cu20

Cyclohexylamine

1

5: 0.02: 0.35

80

6

91

8th

CuCl2 • 2H20

Cyclohexylamine

1

5: 0.02: 1.0

80

6

90

9

CuO

Cyclohexylamine

1

5: 0.005: 0.25

80

4th

51

10th

CuCl

Diethylamine

1

5: 0.02: 0.35

80

6

67

11

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

60

14

CuCl

Morpholine

1

5: 0.02: 0.40

80

7

82

15

CuCl

Ethylamine

1

5: 0.02: 0.40

80

6.5

82

16

CuCl

Cyclohexylamine

1

5: 0.02: 0.50

110

6

78

17th

CuCl

Cyclohexylamine

1

5: 0.02: 0.45

50

19th

89

18th

CuCl

Cyclohexylamine

1

5: 0.02: 0.23

23

86

57

19th

CuCl

Cyclohexylamine

1

5: 0.02: 0.35

80

6

94

The graphically determined yield of 2,4,4,4-tetrachlorobutyrate 65 is 94.3%.

Example 23

A mixture of 34.4 g methyl acrylate, 123.0 g tetrachloromethane

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than, 0.014 g of copper (I) chloride and 4.73 g of 2-propylamine is heated to the boiling point for 7 hours. The process described in Example 1 gives 87.3 g of methyl 2,4,4,4-tetrachlorobutyrate with a Sdt. 101 to 102 ° C / 2.1 kPa, in a yield of 91%. The distillation residue is 3.2 g.

Example 24

A mixture of 1.756 g of 2-methyl propene, 19.26 g of carbon tetrachloride, 0.063 g of copper (I) chloride and 0.83 g of 2-propylamine is heated in a sealed ampoule with vibration stirring in a nitrogen atmosphere at 80 ° C. for 8 hours. The process described in Example 1 gives 5.92 g of 1,1,1,3-tetra-chloro-3-methylbutane with a Sdt. 70 to 71 ° C / 1.6 kPa, in a yield of 90.1%. The distillation residue is 0.042 g.

Example 25

A mixture of 1.42 g of 3-methyl-1-butene, 9.45 g of trichlorotrifluoroethane, 0.06 g of copper (I) chloride, 0.30 g of 2-propylamine and 6 ml of dichloroethane is sealed in a sealed ampoule Heated under vibration stirring in a nitrogen atmosphere at 80 ° C for 6 hours. By the method described in Example 1, 3.92 g of l, l, l-trifluoro-2,2,4-trichloro-5-methylhexane with a Sdt is obtained. 65 ° C / 1.6 kPa, in a yield of 75%. The distillation residue is 0.32 g.

Example 26

A mixture of 2.02 g of ethyl acrylate, 9.5 g of 1,1,1-trichlorotrifluoroethylene, 0.06 g of copper Ω-chloride, 0.66 g of cyclohexylamine and 6 ml of dichloromethane is in a sealed ampoule with vibration stirring in a nitrogen atmosphere heated at 90 ° C for 5 hours. 4.15 g of ethyl 2,4,4-trichloro-5,5,5-trifluoropentauoate with a Sdt is obtained by the process described in Example 1. 58 to 60 ° C / 133 Pa, in a yield of 71.5%.

Example 27

A mixture of 15.6 g of ethyl 3,3-dimethyl-4-pentenoate, 37.5 g of 1,1,1-trichlorotrifluoroethane, 0.1 g of copper (I) chloride and 0.24 g of 2-propylamine heated in a sealed ampoule with vibration stirring in a nitrogen atmosphere at 80 ° C for 4 hours. The process described in Example 1 gives 31.3 g of ethyl 3,3-dimethyl-4,6,6-trichloro-7,7,7-trifluoro-heptanoate with a Sdt. 86 to 87 ° C / 20 Pa, in a yield of 91%.

Example 28

A mixture of 1.29 g of 3-methyl-1-butene, 18.66 g of 1,2-difluoro

Tetrachloroethane, 0.073 g copper (I) chloride and 0.163 g 2-propylamine are heated in a sealed ampoule with vibration stirring at 80 ° C for 7 hours. The process described in Example 1 gives 1.54 g of 1,2-difluoro-1,1,4,4-tetrachloro-5-methylhexane with a Sdt. 84 to 86 ° C / 1.2 kPa, in a yield of 30.7%, which corresponds to a yield based on the converted 3-methyl-1-butene of 86.7%. The distillation residue is 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-dibromomethane, 0.068 g of copper (I) chloride and 0.82 g 2-Propylamine is heated in a sealed ampoule with vibration stirring in a nitrogen atmosphere at 80 ° C for 6.5 hours. The process described in Example 1 gives 2.13 g of l, l, 2-trifluoro-2-chloro-l, 4-dibromo-5-methyl-hexane with a Sdt. 88 to 92 ° C / 1.6 kPa, in a yield of 35.4%, which corresponds to a yield based on the converted 3-methyl-1-butene of 85.6%. The distillation residue is 0.094 g.

13C-NMR (CDC13j TMS) analysis of the mixture of the diastereoisomers:

CH3 8 = 16.26; 17.69; 20.58; 21.85

CH2 5 = 43.08 (J (CF) = 19.2Hz); 42.7 (J (CF) = 19.5Hz)

CH 5 = 32.96; 35.36

CHBr 5 = 53.96; 56.20

CF 8 = 110.6; 110.8 (lJ (CF) = 244Hz)

CF2 8 = 120.1; 120.3 (^ (CF) = 353Hz)

Example 30

A mixture of 1.29 g of 3-methyl-1-butene, 12.2 g of tetrabromomethane, 0.037 g of copper (I) chloride and 0.81 g of 2-propylamine is in a sealed ampoule with vibration stirring in a nitrogen atmosphere at 80 ° C heated for 7 hours. The process described in Example 1 gives 4.45 g of 1,1,1,3-tetra-bromo-4-methylpentane with a Sdt. 99 ° C / 160 Pa, in a yield of 50.2%, which corresponds to a yield based on the converted 3-methyl-1-butene of 85.2%. The distillation residue is 0.32 g.

13C-NMR (CDCI3, TMS) analysis:

CH3 8 = 17.46; 21.22

CH S = 34.99

CHBr 5 = '60, 10

CH2 8 = 64.90

CBr3 8 = 36.93

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Claims (3)

671220 1. Process for the preparation of halogenated organic compounds of the general formula (I): R1 H X1 I I I X-C-C-C-Y (I), I I I R2 H X2 in which R1 is hydrogen or methyl, R2 is methyl or a COOR group or 2-propylene or the group C (CH3) 2 - CH2 - COOR, where R is Cr to C3-alkyl, X is chlorine or bromine, X1 and X2 Fluorine, chlorine or bromine and Y are fluorine, chlorine, bromine or emeC (X1) 3 group, in which X1 has the meaning given above, by reaction of unsaturated compounds of the general formula (II): "> C = CH2 (II), R2 in which R1 and R2 have the meaning given above, with halogenated compounds of the general formula (III): X1 X-C-Y (III), X2 in which X, X1, X2 and Y have the meaning given above, in the presence of a catalytic system, characterized in that 1 molar part of an unsaturated compound of the general formula (II) is reacted with 1 to 20 molar parts of a halogenated compound of the general Formula (III) in the presence of 0.001 to 0.15 molar parts of a copper component selected from the group consisting of metallic copper, copper oxide, a copper halide and mixtures thereof, and from 0.01 to 1.0 molar files of an amine component of the general Formula (IV): R3-NH-R4 (IV), in which R3 is hydrogen or an R4 group and R4 is normal or branched Ci to C12 alkyl, Cs to C8 cycloalkyl or aryl with Cj to C3 alkyl or where R3 and R4 together form a group of the formula - (CH2 ) 20 (CH2) 2 - or - (CH2) „-, in which is equal to 2 to 5, with stirring at temperatures between 20 and 120 ° C. 2. The method according to claim 1, characterized in that the reaction is carried out in the presence of an amine-copper complex prepared from the outset, which was prepared from a copper component and an amine component. 2nd PATENT CLAIMS 3. The method according to claims 1 and 2, characterized in that the reaction is carried out in the presence of a solvent selected from the group containing dichloromethane, dichloroethane, 1,1,2,2-tetrachloroethane and chlorobenzene and in amounts up to 90 vol .-% of the reaction mixture is used.