NL8700852A - METHOD FOR PREPARING HALOGENATED ORGANIC COMPOUNDS. - Google Patents

Description

NO 34430 1

Process for the preparation of halogenated organic compounds.

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

Halogenated compounds of some types are very suitable intermediates for the preparation of highly effective insecticides, called synthetic pyrethroids. These halogenated compounds are advantageously prepared by reactions adding radicals of haloalkanes to suitable unsaturated hydrocarbons. The initiators and catalysts hitherto known in the art for the addition reactions are little active and selective, require elevated temperatures and higher pressures, or they are expensive and difficult to obtain. For example, the addition reactions of haloalkanes such as tetrachloromethane, 1,1,1-trichlorotrifluoroethane, freons and the like with unsaturated compounds, including 3-methyl-1-15-butene, alkyl acrylic atoms, alkyl-3,3-dimethyl-4- pentenoates performed with organic peroxides (U.S. Patent 4,070,404 (1978), German Offenlegungsschrift 2,802,962 (1978)), Ruthenium complexes (German Offenlegungsschrift 2,751,435 (1977)), iron and copper chlorides in combination with ethanolamine or diethylamine hydrochloride (German Offenlegungsschrift 2,920,536 (1979)), Bull. Chem. Soc. Jpn. 52, (1979) 1511), copper (I) chloride in acetonitrile (German Offenlegungsschrift 3,045,768 (1979), European Patent 50,777 (1981), Helv. Chim. Acta 63, (1980) 1947) and iron pentacarbonyl ( British Patent 2,092,578 (1981)) as catalysts. The products were obtained in maximum 25 yields from 6Q to 85¾. With the little reactive 1,1,1-trichlorotrifluoroethane in the reaction with ethyl acrylate, the product was obtained in a yield of only 40% at 140 ° C. Similarly, even the more recent catalysts based on metal oxides combined with organic bases require higher temperatures (120-140 ° C, Czech Patent 209,347).

An object of the present invention is to overcome or alleviate these drawbacks.

The present invention relates to a process for preparing halogenated organic compounds of the general formula 1, wherein R 1 is hydrogen or methyl, R 2 is methyl or 2-propyl or the carboxyl group COOR, wherein R (4 to C3 alkyl or the C (CH 3) 2 CH 2 CO 2 group, where Z is methyl or the OR group, is 8700852 I * * 2 wherein R is as defined above, X is chlorine or bromine, X1 and χ2 are fluorine, chlorine or bromine and Y is fluorine, chlorine, bromine or the group C (X ^) 3, wherein X1 is as defined above, by the reaction of unsaturated compounds of the general formula 2.5 wherein R1 and r2 are as defined above, with halogenated compounds having the general formula 3, wherein X, χΐ, χ2 and Y are as defined above, in the presence of a catalytic system, which involves stirring the reaction mixture containing 1 mole part of the unsaturated compound of the general formula 2, from 1 to 20 moles and halogenated connection to the general formula 3, 0.001 to 0.15 mol parts and metallic copper or copper oxide, a copper salt of inorganic or organic acids or a copper complex or the mixture of the aforementioned compounds and 0.01 to 1.0 mol parts of amine of the general formula 4 wherein R3 is hydrogen or the group R4 and R4 is a normal branched alkyl group having 1 to 12 carbon atoms, preferably ethyl, 2-propyl, n-butyl, n-dodecyl or cycloalkyl, especially cyclohexyl or aryl, in in particular phenyl or arylalkyl, preferably benzyl, or wherein R 3 and R 4 together represent the - (CH 2) r-alkylene group, with n equal to 2 to 5 or the - (CH 2) 20 (CH 2) 2 -9 R or the mixture 20 of the aforementioned amines at a temperature of from 20 to 120 ° C.

According to the present invention, the catalytic system is formed by the copper component and the amine, which produces a copper complex. The copper component of the present invention is preferably selected from copper (II) chloride, copper (I) chloride, copper (II) bromide and copper (I) bromide. Instead of the aforementioned copper halides, other types of copper compounds may also be used, such as nitrates, sulfates, acetates, ethyl hexanoates, acetylacetonates, naphthenates, etc. However, because of their lower activity and selectivity, their application does not provide the benefits just specified.

According to the invention, the amine of the general formula R3NHR4 is selected from the group consisting of ethyl amine, 2-propylamine, n-butylamine, tert-butyl amine, n-decylamine, cyclohexylamine, benzyl-35 amine, diethylamine, piperidine, pyrrolidine or morpholine, in which case the catalytic system is prepared by contacting the amine with the copper component before the addition reaction or being generated in situ in the reaction mixture. With respect to the exothermic course of the reaction, the unsaturated compound 40 or the amine is preferably added portionwise to the reaction mixture. 8700852 3.

The addition reactions of the present invention are preferably conducted in the absence of solvents. Nevertheless, inert solvents can advantageously be used for the dilution of the more expensive halogenated starting compounds. The solvents used are preferably chlorinated compounds with a very low activity such as dichloromethane, 1,1,2,2-tetrachloroethane, chlorobenzene, dichlorobenzene or non-halogenated compounds such as acetonitrile, dioxane, tetrahydrofuran and the like.

The peculiar feature of the catalytic systems described in the present invention as compared to the hitherto known radicals for addition reaction radicals is their high efficiency and selectivity under mild reaction conditions, low cost, and ease of availability . The reactions can usually be carried out under normal pressure and preferably at temperatures from 60 to 90 ° C, which is substantiated by the low pressure reaction of tetrachloromethane with low boiling olefins such as 3-methyl-1-butene (boiling point 20 ° C C), forming the product at a yield of 91.1¾. The yields of desired products are generally very high, reaching 85 to 97% in most reactions at high conversions (up to 100%). The addition reactions of the present invention proceed easily even in the case of low reactive halogenated compounds, such as freons. For example, 1,1,1-trichlorotrifluoroethane readily reacts under mild conditions at 80 to 90 ° C with a high selectivity exceeding 90%. The high selectivity of these reactions, catalyzed by the systems described in the present invention, is further substantiated by the small amount of waste products in the form of polymer distillation residues, which are 1 to 10 wt% with respect to the product, even at high conversions (90 to 100%).

The high efficiency and high selectivity of the novel catalytic systems of the present invention is based on the previously undiscovered high ability of these catalysts to activate halogenated compounds even under mild reaction conditions. Furthermore, the specific feature of these catalysts is their ability to control free radical reactions so that they proceed via the non-chain mechanism, resulting in the almost complete suppression of polymerization reactions, unlike any hitherto in the art known catalysts, 8700352 v4, the effect of which is limited only to the extension of the radical chain.

The radical addition reactions of the present invention can be easily conducted on an industrial scale with low equipment, raw material and energy needs along with small amounts of waste products.

The following examples are set forth to clearly illustrate the practice of preparing halogenated organic compounds of the invention.

10

EXAMPLE I

A mixture of 14.1 g of 3-methyl-1-butene, 307.6 g of tetrachloromethane, 0.398 g of copper (I) chloride and 14.4 g of 2-propylamine is stirred at 63 to 75.5 ° C for 6 hours. heated under reflux, where the conversion percentage of 3-methyl-1-butene is 89¾. The reaction mixture is then cooled, washed with dilute 1% hydrochloric acid and then with water, the excess tetrachloromethane and the unreacted 3-methyl-1-butene are removed by evaporation and then distillation under reduced pressure yields 36.3 g of 1 1,1,3-tetrachloro-20 4-methylpentane (boiling point 90 to 91 ° C / 1.6 kPa) with an efficiency of 81 W, i.e. with an efficiency of 91.1 91 with respect to converted 3- methyl 1-butene. The distillation residue weighed 1.0 g.

EXAMPLE Een 25 A mixture of 3.5 g of 3-methyl-1-butene, 38.5 g of tetrachloromethane, 0.1 g of copper (I) chloride and 1.7 g of cyclohexylamine was placed in a sealed ampoule with shaking in a nitrogen atmosphere heated to 80 ° C for 5 hours. Using the method described in Example I, 9.6 µl, 1,1,3-tetrachloro-4-methylpentane was obtained (yield 85.7¾) corresponding to 92.3¾ with respect to converted 3-methyl-1 -butene. The distillation residue weighed 0.10 g.

EXAMPLES III to XIX

Examples III to XIX, as described in Example 35 II, illustrate the variability of reaction conditions and types of catalytic systems of the invention for the reaction of 3-methyl-1-butene (A) with tetrachloromethane (B). The yields of 1,1,1,3-tetrachloro-4-methylpentane presented in the table are determined chromatographically and calculated with respect to the added 40 3-methyl-1-butene.

87 0 08 5 2 'Λ, δ

EXAMPLE XX

A mixture of 40.0 g of ethyl acrylate, 184.6 g of tetrachloromethane, 1.1 g of copper (I) chloride and 5.9 g of 2-propyl amine is refluxed at 78 to 88 ° C for 5 hours. According to the method described in Example I, a total of 90.1 g of ethyl 2,4,4,4-tetrachlorobutoxide boiling at 109 to 110 ° C / 2 kPa was obtained in a yield of 88.7% . The distillation residue weighed 2.56 g.

EXAMPLE XXI

A mixture of 0.3229 g of ethyl acrylate, 9.92 g of tetrachloromethane, 0.0095 g of copper (I) chloride and 0.0685 g of 2-propyl amine is placed in a sealed ampoule with shaking in a nitrogen atmosphere for 6.5 heated to 80 ° C for hours. The chromatographic yield of ethyl 2,4,4,4-tetrachlorobutoxide was 97%.

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EXAMPLE XXII

A mixture of 0.4578 g ethyl acrylate, 8.65 g tetrachloromethane, 0.055 g copper (I) chloride and 0.189 g 2-propyl amine is placed in a sealed ampoule with shaking in a nitrogen atmosphere for 5 hours at 80 ° C C heated. The chromatographic yield of ethyl 2,4,4,4-tetrachlorobutoxide was 94.3%.

EXAMPLE XXIII

A mixture of 34.4 g of methyl acrylate, 123.0 g of tetrachloromethane, 0.4 g of copper (I) chloride and 4.73 g of 2-propylamine is refluxed for 7 hours. The method described in Example I provided 87.3 g of methyl 2,4,4,4-tetrachlorobutoxide which boils at 100-102 ° C / 2.1 kPa at 91% yield. The distillation residue weighed 3.2 g.

15

EXAMPLE XXIV

A mixture of 1.756 g of 2-methylpropene, 19.26 g of tetrachloromethane, 0.063 g of copper (I) chloride and 0.83 g of 2-propylamine is placed in a sealed ampoule with shaking in a nitrogen atmosphere for 8 hours at 80 ° C. C heated. The method described in Example I provided 5.92 g of 1,1,1,3-tetrachloro-3-methylbutane, which boils at 70 to 71 ° C / 1.6 kPa at 90.1% yield. The distillation residue weighed 0.042 g.

25 EXAMPLE XXV

A mixture of 1.42 g of 3-methyl-1-butene, 9.45 g of 1,1,1-trichlorotrifluoroethane, 0.06 g of copper (I) chloride, 0.30 g of 2-propyl amine and 6 ml dichloromethane was heated in a sealed ampoule to 80 ° C for 6 hours with stirring in a nitrogen atmosphere. The method described in Example I provided 3.92 µl, 1,1-trifluor-2,2,4-tri-chloro-5-methylhexane, which at 65 ° C / 1.6 kPa, at an efficiency of 75%, boiled. The distillation residue weighed 0.32 g.

EXAMPLE XXVI

A mixture of 2.02 g of ethyl acrylate, 9.5 g of 1,1,1-trichlorotrifluoroethane, 0.06 g of copper (I) chloride, 0.66 g of cyclohexylamine and 6 ml of dichloromethane is placed in a sealed ampoule under stirring in a nitrogen atmosphere heated to 90 ° C for 5 hours. The method as in Example 1 gave 4.15 g of ethyl 2,4,4-trichloro-5,5,5-trifluoropentanoate, which boiled at 58.5% / 133 kPa at 71.5% reduction .

8 700 852 8

EXAMPLE XXVII

A mixture of 15.6 g of ethyl 3,3-dimethyl-4-pentanoate, 37.5 g of 1,1,1-trichlorotrifluoroethane, 0.1 g of copper (I) chloride and 0.24 g of 2-propylamine is placed in a Sealed ampoule heated to 80 ° C for 4 hours with a vigorous stirring in a nitrogen atmosphere. The method described in Example I gave 31.3 g of ethyl 3,3-dimethyl-4,6,6-trichloro-7,7,7-trifluorheptanoate, which was obtained at 86 to 87 ° C / 20 Pa with an efficiency of 91¾ boiled.

Example XXVIII

A mixture of 1.29 g of 3-methyl-1-butene, 18.66 g of 1,2-difluorotetrachloroethane, 0.073 g of copper (I) chloride and 0.163 g of 2-propylamine is placed in a sealed ampoule with shaking for 7 heated to 80 ° C for hours. The method described in Example I gave 1.54 g of 15 1,2-difluoro-1,2,4-tetrachloro-5-methylhexane, which boiled at 84 to 86 ° C / 1.6 kPa in a yield of 30 .7%, which corresponds to an efficiency of 86.7% with respect to converted 3-methyl-1-butene. The distillation residue weighed 0.067 g.

EXAMPLE XXIX

a

A mixture of 1.22 g 3-methyl-L-butene, 23.95 g 1,1,2-trifluoro-2-chloro-1,2-dibromoethane, 0.068 g copper (I) chloride and 0.82 g 2 propylamine is heated in a sealed ampoule to 80 ° C for 6.5 hours with stirring in a nitrogen atmosphere. The method described in Example I provided 2.13 µl, 1,2-trifluoro-2-chloro-1,4-dibromo-5-methylhexane, which boiled at 88 to 92 ° C / 1.6 kPa in a efficiency of 35.4%, which corresponds to an efficiency of 86.6% with respect to converted 3-methyl-1-butene. The distillation residue weighed 0.094 g. 13 C NMR (CDCl 3, TMS) analysis of the mixture of 30 distereoisomers: CH 3 J = 16.26; 17.69; 20.58; 21.85 CH2 J = 43.08 (J (CF) = 19.2 Hz); 42.7 (J (CF) = 19.5 Hz) CH v / = 32.96; 35.36 CHBr = 53.92; 56.20 CF S = 110.6; 110.8 (1J (CF) = 244 Hz) CF2 J = 120.1; 120.3 (XJ (CF) = 353 Hz) 8700852% 9

EXAMPLE XXX

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 placed in a sealed ampoule under a nitrogen atmosphere with stirring. -5 heated to 80 ° C for 7 hours. The method described in Example I gave 4.45 µl, 1,1,3-tetrabromo-4-methylpentane, which boiled at 99 ° C / 160 Pa in an efficiency of 50.2%, corresponding to an efficiency of 85, 2% with respect to converted 3-methyl-1-butene. The distillation residue weighed 0.32 g.

13 C NMR (CDCl 3, TMS) analysis: CH 3 J = 17.46; 21.22 CH cf = 34.99 CHBrc / = 60.10 15 CHz «/ = 64.90 CBr * 3 * 36.93 8700852

Claims (4)

1. Process for the preparation of halogenated organic compounds, characterized in that compounds of the general formula 15 are prepared in which R * is hydrogen or methyl, R2 is methyl or 2-propyl or the group COOR, wherein R is alkyl with 1 up to 3 carbon atoms or the group of the formula C (CH 3) 2 CH 2 CO 2, wherein Z is methyl or the group OR, wherein R is alkyl of 1 to 3 carbon atoms, X is chlorine or bromine, χΐ and X 2 is fluorine, chlorine or bromine and Y is fluorine, chlorine, bromine or the group C (X ^ -) 3, wherein heeft has the aforementioned meaning, by reacting unsaturated compounds of the general formula 2, wherein R1 and R2 are as defined above, with a halogenated compound of the general formula 3, wherein X, χΐ, X2 and Y are as defined above, in the presence of a catalytic system, which reacts 1 mol part of the unsaturated compound of the general formula 2 with 1 to 20 mol del and of the halogenated compound with the general ne formula 3 in the presence of 0.001 to 0.15 moldings of a copper component selected from the group consisting of metallic copper, a copper oxide or a copper halide or the mixture of the aforementioned copper compounds and 0.01 to 1.0 mol part of an amine component of the general formula 4, wherein R 2 is hydrogen or the group R 4, R 4 straight or branched chain alkyl with 1 to 12 carbon atoms, cycloalkyl with 5 to 8 carbon atoms, aryl alkyl with 1 to 3 carbon atoms alkyl part or R3 and R4 together represent the 25 - (CH2) 20 (CH2) 2 ~ or “(CH2) n-9 rOp, where n equals 2 to 5, while stirring the mixture at a temperature of 20 to 120 ° C. 2. Process according to claim 1, characterized in that the reaction is carried out in the presence of the copper amine complex, which has been prepared from the copper component and the amine component before the addition reaction. 3. Process according to claim 1 or 2, characterized in that the reaction is carried out in the presence of a solvent selected from dichloromethane, 1,1,2,2-tetrachloroethane and chlorobenzene, the amount of solvents being up to 90% by volume, % of the reaction mixture. Process according to claims 1 to 3, characterized in that the reaction mixture is heated to a temperature of 60 to 100 ° C. 87 0 08 5 2 '_L R1 Η X1 X - C - C - C - Y I o I 12 ir h x * 2. rI 7 = ch2 R 3_ X1 X - C-Y X2 g-3- »NH — R ^ 1 8700852