JPS62242635A - Manufacture of halogenated organic compound - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a halogenated organic compound used in the production of birethroid.

[Conventional technology]

Several types of halogenated compounds are very useful intermediates for the production of highly effective insecticides called synthetic birethroids. These halogenated compounds are advantageously prepared by radical addition reactions of halogenalkanes to appropriate unsaturated hydrocarbons. Initiators and catalysts hitherto known in the art for that addition reaction are rarely active and selective, require high temperatures and pressures, or are expensive;
And you can barely get it. For example, halogen alkanes, such as tetrachloromethane.

1,1,1-)lichlorotrifluoroethane, Freon and the like and unsaturated compounds such as 3-methyl-1-butene, alkyl acrylates, alkyl 3,
The addition reaction with 3-dimethyl-4-pentenoate is carried out using ethanolamine or diethylamine hydrochloride (Ger, Offen) as a catalyst.

2920536 (1979), Bull, Chem.
Soc, Jpn 52.1511 (1979)), cuprous chloride (Ger.

Offen, 3045768 (1979), European Patent No. 50777 (1981), He1v, Ch
im, Acta 63.1947 (1980)) and pentacarbonyl iron [UK Patent No. 2092578 (1980)
1)) together with peroxide [US Pat. No. 407]
No. 0404 (197B), Ger, Offen, 2
802962 (1978)).

Ruthenium complex (Ger, Offen, 275143
5 (1977)).

brought about by iron chloride and copper chloride. The product was obtained in maximum yield of 60-85%. Low reactivity 1
, 1, 1-) In the reaction of dichlorotrifluoroethane with ethyl acrylate, the product is 140
It was obtained in a yield of only 40% at . Similarly, recent catalytic reactions based on metal oxides in combination with organic bases have been carried out at high temperatures (12o-140'C).

Czechoslovakia Patent No. 209347).

[Means for solving problems]

The aim of the invention is to eliminate or alleviate these disadvantages.

The present invention relates to the following general formula (I): R'HX'' [wherein R1 is hydrogen or a methyl group, and R2 is a methyl group, 2-propyl group, or carboxyl (COOR) group (where R is 01 to C3 alkyl group or C(C1,I)
zcHzcOZ (cocote Z is a methyl group) or OR group (where R is the same as above), X is chlorine or bromine, Xl and X2 are fluorine, chlorine or bromine Yes, and Y is fluorine, chlorine, bromine or c(
x') s group (where Xl is as described above)]
The present invention relates to a method for producing a halogenated organic compound comprising: Compound (1) is produced by combining an unsaturated compound represented by the following general formula (II): [wherein R1 and R2 are the same as above] and the following general formula (■): X- in the presence of a catalyst. C-Y
(1) Produced by reaction with a halogenated compound represented by [wherein x, x', or 0.001 to 0.15 mol part of a copper component selected from a copper salt of an organic acid, a copper complex, or a mixture of the copper compounds and the following general formula (■): R'-NH-R' (
rV) [wherein R3 is hydrogen or R4 group, and R
4 is a linear or branched C2-C1□ alkyl group, preferably an ethyl group, 2-propyl group, n-butyl group, n
-didecyl group or cycloalkyl group.

In particular cyclohexyl or aryl, particularly preferably phenyl or arylalkyl, most preferably benzyl, or R3 and R4 are both -(c
ut), -alkylene group (n is 2 to 5) or -(
0.01-1.0 amine component of the amine or mixture of these amines
1 molar part of an unsaturated compound of general formula (■) and a halogenated compound of general formula (III) 1 to 1 in the presence of molar parts of
It comprises stirring a reaction mixture containing 20 mol at a temperature of 20-120<0>C.

According to the invention, the catalyst system is formed by a copper component and an amine that forms a copper complex. The copper component of the present invention is preferably copper chloride (II) or copper chloride (■).

Selected from copper bromide (■) and copper bromide (1).

Instead of the copper halides, other types of copper compounds may also be used, such as nitrates, sulfates, acetates, ethylhexanoates, acetylacetonates, naphthinates, and the like. However, due to their low activity and low selectivity, their application offers few identified advantages.

According to the invention, the amine of formula -a R'NHR' can be ethylamine, 2-propylamine, n-butylamine, t
selected from the group consisting of ert, -butylamine, n-decylamine, cyclohexylamine, benzylamine, diethylamine, piperidine, pyrrolidine or morpholine, in which case the catalyst system contacts the copper component with the amine prior to the addition reaction. or prepared in situ in the reaction mixture. During the exothermic reaction, the unsaturated compound or amine is preferably added dropwise to the reaction mixture.

The addition reaction of the invention is preferably carried out in the absence of a solvent. Nevertheless, inert solvents can be effectively used for dilution of the more expensive halogenated starting compounds. Preferably used solvents are chlorinated compounds of low reactivity, such as dichloromethane, 1,
1.2.2-Tetrachloroethane, chlorobenzene, dichlorobenzene or non-halogenated compounds such as acetonitrile, dioxane, tetrahydrofuran and the like.

Compared to catalyst systems hitherto known in the art for radical addition reactions, the distinguishing features of the catalyst systems described in this invention are their high efficiency and selectivity under mild reaction conditions. It is low cost, and easily available.

The reaction is carried out under almost normal pressure and preferably at a temperature of 60-90°C, and this means that tetrachloromethane and a low-boiling alkene, such as 3-methyl-1-butene (b
, p, 20° C.) was shown to yield a 91.1% yield of product. Yields of the desired product are generally very high, and in most reactions 85-97% (100%) conversion.
(up to). The addition reactions of the invention proceeded easily even with low reactivity, halogenated compounds such as freons. For example, 1,1,1-)lichlorotrifluoroethane reacts readily at 80-90°C under mild conditions with high selectivity of over 90%.

The high selectivity of these reactions catalyzed by the catalysts described in this invention results in a small amount of waste in the form of polymeric distillation residues of 1-10% by weight with respect to the product and even higher conversions (90-10% by weight). 100%).

The high efficiency and selectivity of the novel catalyst systems of the invention is based on the high yet undiscovered ability of these catalysts to activate halogenated compounds even under mild conditions. Furthermore, the special characteristics of these catalysts are that they are non-conductive, leading to an almost complete suppression of the polymerization reaction (the effect of which is limited only to the extension of the radical chain) compared to catalysts hitherto known in the art. Their ability to orchestrate radical addition reactions as they proceed through chain mechanisms.

The radical addition reactions of the present invention can be easily carried out on an industrial scale, with low requirements for equipment, raw materials and energy, and with small amounts of waste.

The following examples more clearly illustrate the implementation of the preparation of halogenated compounds of the present invention.

14.1 g of 5-3-methyl-1-butene, 307.6 g of tetrachloromethane, 0.398 g of copper(I) chloride, and 2
- A mixture of 4.14 g of propylamine was added to 63-75.
The mixture was refluxed at 5° C. for 6 hours, at which time the conversion rate of 3-methyl-1-butene was 89%. The reaction mixture was then cooled, washed with 7% hydrochloric acid and then water, excess tetrachloromethane and unreacted 3-methyl-1-butene removed by evaporation, followed by vacuum 1.1,1.3-tetrachloro-4-methylpentane (h, p, 90-91') with a yield of 81.1%.
C/1.6 and Pa) 36.3 g were obtained.

91.1 for reacted 3-methyl-1-butene
% yield. The distillation residue weighed 1.0 g.

■-1 A mixture of 3.5 g of 3-methyl-1-butene, 38.5 g of tetrachloromethane, 0.1 g of copper chloride (1), and 1.7 g of chlorohexylamine was sealed while shaking under a nitrogen atmosphere. Heated to 80°C in an ampoule for 5 hours.

By using the method described in Example 1, 1,
1,1.3-tetrachloro-4-methylpentane 9.6
g (85.7%).

This corresponds to 92.3% with respect to the reacted 3-methyl-1-butene. The distillation residue weighed 0.10 g.

Examples 3 to 19 carried out as described in Kanshu Nijo Work Example 2
exemplify different reaction conditions and different types of catalyst systems of the present invention for the reaction of 3-methyl-1-butene (A) and tetrachloromethane (B). The yields of 1.1.1.3-tetrachloro-4-methylpentane shown in the table were determined by chromatography and calculated on the charged 3-methyl-1-butene.

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-propylamine was refluxed at 78 to 88°C for 5 hours. do. By the method described in Example 1, ethyl 2,4.4.4-tetrachlorobutyrate (b, p,
109-110°C/2 KPa) was obtained (88.7% yield). The distillation residue weighed 2.56 g.

±1 ethyl acrylate 0.3229 g, tetrachlorometha 79.92 g, chloride w4(I) 0.0095 g
and 0.0685 g of 2-propylamine,
6 in a sealed ampoule with shaking under nitrogen atmosphere.
．． Heated to 80°C for 5 hours. Ethyl 2.4.4.4-
The yield of tetrachlorobutyrate by chromatography was 97%.

A mixture of 0.4578 g of ethyl acrylate, 8.65 g of tetrachloromethane, 0.055 g of copper(1) chloride and 0.189 g of 2-propylamine was placed in a sealed ampoule with shaking under a nitrogen atmosphere. 3 hours inside
Heated to 80°C. The yield of ethyl 2,4,4,4-tetrachlorobutyrate by chromatography is 9
It was 4.3%.

A mixture of 34.4 g of Okushimoto methyl acrylate, 123.0 g of tetrachloromethane, 0.4 g of copper chloride (1) and 4.73 g of 2-propylamine was refluxed for 7 hours.

By the method described in Example 1, methyl 2°4.4
．． 4-Tetrachlorobutyrate (b, p, 101-b) The distillation residue weighed 3.2 g.

A mixture of 1.756 g of charcoal ↓ 2-methylpropane, 19.26 g of tetrachloromethane, 0.063 g of copper chloride (T) and 0.83 g of 2-propylamine was sealed with shaking under a nitrogen atmosphere. 8 hours in ampoule, 80
heated to ℃. By the method described in Example 1, 1
．． 1.1.3-Tetrachloro-3-methylbutane (b,
p, 70-b (90.1% yield). The distillation residue weighs 0.0
It was 42g. 3-Methyl-1-butene 1.42g, 1 , 1 , 1
- 9.45 g of trichlorotrifluoroethane, copper chloride (
1) A mixture of 0.06 g, 2-propylamine, 0.30 g and dichloromethane 6- was heated to 80<0>C in a sealed ampoule for 6 hours with shaking under nitrogen atmosphere. By the method described in Example 1, 1 , 1
, 1-) refluoro-2,2,4-trichloro-5-methylhexane (b, ρ, 65°C/1,6 KPa)3.
92 g were obtained (75% yield). The distillation residue is
It weighed 0.32g.

Base 26 Ethyl acrylate 1-2.02g, 1, 1, 1
-) 9.5 g of dichlorotrifluoroethane, 1 m of chloride
(1) 0.06g, cyclohexylamine 0.66
A mixture of g and dichloromethane 6- was heated at 90°C for 5 hours in a sealed ampoule with shaking under a nitrogen atmosphere.
heated to. By the method described in Example 1, ethyl 2,4.4-)lichloro5.5.5-1-lifluoropentanoate (b, p, sa ~ 60 °C/133 Pa
) Obtained 4.15 g (71.5% yield).

Charcoal 11 Ethyl 3.3-dimethyl-4-pentenoate 15.6
g, 1 , 1 , 1-) A mixture of 37.5 g dichlorotrifluoroethane, 0.1 g copper chloride (r) and 0.24 g 2-propylamine in a sealed ampoule with shaking under nitrogen atmosphere. Heated to 80°C for 4 hours. By the method described in Example 1, ethyl 3.3-
dimethyl-4,6,6-t-lichloro7.7.7-)
Lifluoroheptanoate (b, p, 86-b yield).

■1.29 g of 3-methyl-1-butene, 18.66 g of 1,2-difluorotetrachloroethane, AM chloride (
I) 0.073 g and 2-propylamine 0.163
The mixture of g was heated to 80° C. for 7 hours in a sealed ampoule with shaking. By the method described in Example 1, 1,2-difluoro-1,1,2°4-tetrachloro-5-methylhexane (b, p, 84~b) was prepared by reacting 3-methyl-1 - corresponds to a yield of 86.7% with respect to butene, the distillation residue weighing 0.
It was 067 g.

1.22 g of 3-methyl-1-butene, 1, 1, 2
-trifluoro-2-chloro-1,2-dibromoethane 23.95 g, copper chloride (1) 0.068 g and 2
- A mixture of 0.82 g of propylamine was added for 8 hours in a sealed ampoule with shaking under a nitrogen atmosphere for 6.5 hours.
Heated to 0°C. By the method described in Example 1,
1,1.2-)lifluoro-2-chloro-1,4-dibromo-5-methylhexane (b, 9°88-b) which is 85.6% with respect to the reacted 3-methyl-1-butene Corresponds to the yield.The distillation residue weighs 0.
It was 094 g. 'C of a mixture of diastereomers
Nl'lR (CDCJ! 3, TMS) analysis: C8
, δ= 16.26; 17.69; 20.5
8; 21.85C11, δ= 43.08 (J
(CF)=19.2Hz) :42.7(J(CF)
-19,5Hz) CHδ= 32.96: 35.36CHRr
δ= 53.92; 56.20CF δ=
110.6: 110.8 ('J(CF)=2
44H2) CF2 δ-120,1; 120.3
('J(CP)=353Hz)''- 1.29 g of 3-methyl-1-butene, 12.2 g of tetrabromomethane, 0.037 g of copper chloride (1), and 0.81 g of 2-propylamine. The mixture was incubated for 7 hours in a sealed ampoule with shaking under a nitrogen atmosphere for 80
heated to ℃. By the method described in Example 1, 1
．． 1,1,3-tetrabromo-4-methylpentane (b
, p, = 99°C/160Pa) 4.45 g was obtained (
50.2% yield). This is the reacted 3-methyl-
For 1-butene, this corresponds to a yield of 85.2%.

”CNMR (C[)CP, , T?lS) analysis: CH
, l δ= 17.46; 21.22CH δ=
34.99

Claims (1)

[Claims] 1. General formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [In the formula, R^1 is hydrogen or a methyl group, and R^
2 is a methyl group, 2-propyl group, COOR group {here R
is an alkyl group of C_1 to C_3 or a group of the formula C(CH_3)_2CH_2COZ (where Z is a methyl group)} or an OR group (where R is a C_1
~C_3 is an alkyl group)] and the following general formula (III): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) [In the formula, X is chlorine or bromine , X^1 and X^2 are fluorine, chlorine, or bromine, and Y is fluorine, chlorine, bromine, or a C(X^1)_3 group, where X^1 is as defined above. ] By reacting with a halogenated compound represented by the following in the presence of a catalyst system, the following general formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^1 , R^2, X, X^1, X^2 and Y are as defined above], the method comprises: metallic copper, copper oxide, copper halide or Copper component selected from the class comprising mixtures of said copper compounds from 0.001 to 0.
15 mole parts and the following general formula (IV): R^3-NH-R^
4(IV) [In the formula, R^3 is hydrogen or R^4 group, R^4 is a straight chain or branched chain C_1 to C_1_2 alkyl group, C
_5 to C_8 cycloalkyl group, or aryl C_1
~C_3 is an alkyl group, or R^3 and R^4 are both -(CH_2)_2O(CH_2)_2- or -(
in the presence of 0.01 to 1.0 mole parts of an amine component of CH_2)_n- group (where n is 2 to 5);
1 mole part of unsaturated compound of general formula (II) and general formula (III)
1 to 20 mole parts of a halogenated compound of
A method comprising reacting at a temperature of 120° C. with stirring. 2. The method according to claim 1, wherein the reaction is carried out in the presence of a copper-amine complex prepared from a copper component and an amine component before the addition reaction. 3. The claim 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 which amounts to up to 90% by volume of the reaction mixture. The method according to item 1 or 2. 4. The method according to claims 1 to 3, wherein the reaction mixture is heated to a temperature of 60 to 100°C.