JPS60149540A - Production of 2-(4-alkoxyphenyl)-2-methylpropyl chloride - Google Patents

Abstract

PURPOSE:2-(3-Halogeno-4-alkoxyphenyl)-2-methylpropyl chloride, as a starting material, is subjected to catalytic hydrogenation to produce the titled compound used as a synthetic intermediate of insecticides in high yield with industrial advantage. CONSTITUTION:The catalytic hydrogenation of 2-(3-halogeno-4-alkoxyphenyl)-2- methylpropyl chloride is carried out at -20-100 deg.C, preferably 10-60 deg.C under normal pressure to 150kg/cm<2>, when necessary, in the presence of a base to give the objective compound. In the above reaction it is preferred to use palladium as a catalyst. The base used is an acetate salt and the solvent is an acetate ester. The amounts are 0.01-0.2pt. in the catalyst, 1.0-2.0pts. in the base and 1.0-10pts. in the solvent per 1pt. of the starting substance of formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 2-(4-alkoxyphenyl)-2-methylpropyl chlorides.

More specifically, 2-(3-halogeno-4-alkoxyphenyl)- represented by the general formula ([); (in formula (I), R represents a lower alkyl group and X represents a chlorine atom or a bromine atom) Catalytic reduction of 2-methylpropyl chlorides, if necessary in the presence of a base,
Production of 2-(4-alkoxyphenyl)-2-methylpropyl chloride represented by the general formula σ); (in formula (n), R represents the above meaning) characterized by dehalogenation. Regarding the law. 2-(4-Alkoxyphenyl)-2-methylpropyl chlorides are useful compounds in various industrial fields, and are useful as intermediates for agricultural chemicals, especially insecticides.

2-(4-alkoxyphenyl)-2-methylpropyl chlorides are novel insecticides that have high insecticidal and acaricidal activity, and are excellent in fast-acting, residual-acting, and low toxicity to fish. 3-noenoxybenzyl 2-(4-alkoxyphenyl)-2-methylpropyl ethers (JP-A-57-72921'1, JP-A-57-72921'1, JP-A-F+7-646)
As a method for producing 2-(4-alkoxyphenyl)-2-methylpropyl chloride, which is an important intermediate of 2-(32), alkoxybenzenes and 3-chloro-2
-Methyl-1-propene.

For example, in the presence of concentrated sulfuric acid, anisole and 3-chloro-
A method for synthesizing 2-(4-methoxyphenyl)-2-methylpropyl chloride by reacting 2-methyl-1-propene has been reported (C4am, B<a, 94.2
609 (1961)). In the Kono method, the objective 2-(4
-Methoxyphenyl)-2-methylpropyl chloride is simultaneously generated isomer 2-(2-methoxyphenyl)-
Since only about 30% to 50% of 2-methylpropyl chloride is produced, precise distillation operations are required. Furthermore, it is expected that other alkoxybenzenes other than anisole will give similar results.

Therefore, using the alkoxybenzene 3-chloro-2-methyl-1-propene as a starting material, the purpose +17) 2-
The industrial production of (4-alkoxyphenyl)-2-methylpropyl chloride is very disadvantageous.

As another method, JP-A-58-81"t336 discloses that 2-(4-acyloxyphenyl)-2-methylpropyl chloride is treated with a base and an alkylating agent, and 2-(4-alkoxy A method for producing phenyl)-2-methylpropyl chlorides has been reported.

However, the starting material 2-(
The production of 4-acyloxyphenyl)-2-methylpropyl chloride requires two steps: acylation of 4-t-butylphenol and further photochlorination (JP-A-58-83'650). In addition, it is very disadvantageous industrially, as it requires complex purification steps such as precise distillation operations to separate raw materials from the reaction mixture in the photochlorination step and to separate generated by-products.

Because of this, 2-(4-alkoxyphenyl)-2
- Easy production of methylpropyl chlorides l-b) An industrial method was desired.

Book'4 Intermediate 2-(4-alkoxyphenyl)-2
- As a result of intensive electrical testing on an industrially advantageous production method for methylpropyl chlorides, a surprising finding was found 1C2-(3-
By catalytically reducing halogen-4-alkoxyphenyl)-2-methylpropyl chloride in the presence of a base if necessary, 2-(4-alkoxyphenyl)-2-methylpropyl chloride is selectively produced in high yield. The present invention has been completed based on the discovery that this can be obtained.

The 2-(4-alkoxyphenyl)-2-methylpropyl chloride produced by the present invention has the general formula (II)
; Represented by ;

In formula (11), (■) represents a lower alkyl group, specifically methyl group, ethyl group, 11-propyl group, isopropyl group, 1]-butyl group, isobutyl group, t-butyl group, 11-pentyl group. 2-(4-alkoxyphenyl)-2-methylpropyl chloride. 4
-methoxyphenyl)-2-methylpropyl chloride,
2-(4--f-)xyphenyl)-2-methylpropyl chloride, 2-(4-n-fluorokidiphenyl)-2
-Methylpropyl chloride, 2-(4-impropoxyphenyl)-2-methylpropyl chloride, 2-(4-
n-butoxyphenyl)-2-methylpropyl chloride, 2-(4-1-butoxyphenyl)-2-methylpropyl chloride, 2-(4-n-pentyloxyphenyl)-2-methylpropyl chloride, 2-( The above-mentioned alkyl group-substituted oxyphenyl derivatives such as 4-isopentyloxyphenyl)-2-methylpropyl chloride and 2-(4-n-hexyloxyphenyl)-2-methylpropyl chloride can be mentioned.

2-(3-halogen-4-alkoxyphenyl)-2-methylpropyl chloride used as a raw material in the present invention is represented by the formula (■); In formula (I), R represents the above-mentioned lower alkyl group, and X represents a chlorine atom or a bromine atom.

Examples of these 2-(3-halogeno-4-alkoxyphenyl)-2-methylpropyl chlorides include the following compounds.

2-(3-chloro-4-methoxyphenyl)-2-methylpropyl chloride, 2-(3-bromo-4-methoxyphenyl)-2-methyl-propyl chloride, 2-(
3-chloro-4-ethoxyphenyl)-2-methylpropyl chloride, 2-(3-bromo-4-ethoxyphenyl)-2-methylpropyl chloride, 2-(3-chloro-4-11-fluorokidiphenyl) ) -2-methyl-
Propyl chloride, 2-(3-bromo-4-inpropoxyphenyl)-2-methyl-propyl chloride, 2
-(3-chloro-4-n-butoxyphenyl)-2-methyl-propyl chloride, 2-(3-bromo-4-inftoxyphenyl)-2-merIF-propyl chloride, 2-(3-chloro- 4-1-butoxyphenyl)-
2-methylpropyl chloride, 2-(3-bromo-4-
n-butoxyphenyl)-2-methylpropyl chloride, 2-(3-chloro-4-isopentyloxyphenyl)-2-methylpropyl chloride, 2-(3-bromo-
Examples include 4-n-hexyloxyphenyl)-2-methylpropyl chloride.

The starting material 2-(3-halogeno-4-alkoxyphenyl)-2-methylpropyl chloride is 2-halokene-
Alkoxybenzenes and 3-chloro0-2-mef-1-
When propene is reacted in the presence of an acid catalyst, it is easy to react, and
Can be manufactured selectively.

Catalytic reduction catalysts such as rhodium, ruthenium, rhenium, palladium, platinum, Raney nickel, reduced nickel, nickel formate, urushihara nickel, nickel-copper, and copper chromium oxide are suitable as catalysts used in the production method of the present invention, and preferably It is palladium, and bases include alkali metal and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide, carbonates such as sodium carbonate, sodium bicarbonate, and potassium carbonate, and triphosphates. Phosphates such as sodium, organic acid salts such as sodium formate, sodium acetate, potassium acetate, magnesium acetate, sodium propionate, alkaline earth metal oxides such as magnesium oxide and calcium oxide, organic acids such as pyridine and triethylamine. There are bases, etc., and acetates are preferred.

Although not essential, it is desirable to use a solvent to improve yield. As a solvent, water, alcohols such as methanol, ethanol, and isopropyl alcohol, organic acids such as acetic acid and propionic acid, esters such as methyl formate, methyl acetate, ethyl acetate, isopropyl acetate, and butyl acetate, diethyl ether, tetrahydrofuran, 1. Ethers such as 4-dioxane,
Ketones such as acetone and methyl ethyl ketone; aliphatic hydrocarbons such as hexane and heptane; aromatic compounds such as benzene and toluene; These include protic polar solvents, which can be used singly or in combination of two or more. Preferred are acetate esters.

Hydrogen pressure is normal pressure to 150 kg/'cr! G, reaction temperature = 20°C to 100°C, preferably 10
℃ to 60℃.

The catalytic reduction catalyst is 0.00001 part to 0.5 parts, preferably n, 001 parts, per part of 2-(3-halogeno-4-alkoxyphenyl)-2-methylpropyl chloride.
~0.2 parts, if a base is required, 0.5 parts to 10 parts, preferably 1.0 to 2.0 parts of base, and if a solvent is required (1.1 to 30 parts, preferably J, , 10 parts of solvent are used. If the amount used is large, productivity will decrease.

A general embodiment of the manufacturing method of the present invention is as follows.

2-(3-halogeno-4-alkoxyphenyl)-2-
Methylpropyl chloride, a catalytic reduction catalyst, and if necessary, a base and a solvent are charged into a reactor, hydrogen is brought to a predetermined pressure of normal pressure to 150 kglcrlG, heated or cooled to a predetermined temperature, and then heated or cooled to a predetermined temperature. Stir the time. After the reaction is completed, the reaction mixture is filtered, and the solvent in the organic layer is distilled off. It can be used for the next reaction as it is, but if necessary, it can be purified by distillation, column chromatography, etc.

Example 1 2-(3-chloro-4-ethoxyphenyl)-2-methylpropyl chloride5. (10g5%Pd-C(50
% water content) ('1.4q, sodium acetate (anhydrous) 1.
Charge 25q of 65'7 ethyl acetate into a 200-autoclave, replace the inside of the autoclave with nitrogen and then with hydrogen, pressurize with hydrogen to 25kg/clG, and stir while stirring.
Heat to 0°C. Thereafter, the mixture was stirred at the same temperature for 4 hours.

After the reaction was completed, the reaction mixture was filtered and the residue was washed with ethyl acetate. The solvent was distilled off from the filtrate and washing liquid to obtain crude 2-
4.6'l of (4-ethoxyphenyl)-2-methylpropyl chloride was obtained. The obtained product was analyzed by gas chromatography and the results were 2-(4-ethoxyphenyl)-2-
It contained 81.9% methylpropyl chloride.

Yield 91.1% Example 2 2-(3-I'rollo-4-ethoxyphenyl)-2-methyl-propyl chloride5. nOq, 5% Pd-C (5
0% quartz) 0.5+7, sodium hydroxide 0°81
, 11-butyl acetate 259 to 200 wI7! The autoclave is charged, and the interior of the autoclave is purged with nitrogen and then with hydrogen, pressurized with hydrogen to 25 kg/cri G, and heated to 60°C while stirring. Thereafter, the mixture was stirred at the same temperature for 4 hours. After the reaction was completed, the reaction mixture was filtered, and the filter residue was washed with benzene. One part of the solution was distilled off from the filtrate and washing liquid to obtain 4.82q of crude 2-(4-ethoxyphenyl)-2-methylpropyl chloride. Analysis of the obtained product by gas chromatography revealed that it contained 65.1% of 2-(4-ethoxyphenyl)-2-methylpropyl chloride. Yield 74.4% Example 3 2-(3-chloro-4-ethoxyphenyl)-2-methylpropyl chloride 7.5]7.5% Pd-C (50%
quartz) 0.75, sodium hydroxide 1.28,
30 liters of N,N-dimethylimidazolidinone are placed in a 200d autoclave, the interior of the autoclave is purged with nitrogen and then with hydrogen, pressurized with hydrogen to 25/9/εrJG, and heated to 60° C. with stirring. Thereafter, the mixture was stirred at the same temperature for 8 hours. After the reaction is complete, add approximately 150 ml to the reaction mixture.
of water was added and extracted with benzene.

After washing the benzene layer with water and drying it, the solvent was distilled off to obtain crude 2-
4.93 g of (4-ethoxyphenyl)-2-methylpropyl chloride was obtained. As a result of analyzing the obtained product by gas chromatography, 2-(4-ethoxyphenyl)-
It contained 66.5% 2-methylpropyl chloride. Yield 76.2% Example 4 2-(3-chloro-4-methoxyphenyl)-2 as raw material
- The same procedure as in Example 1 was carried out except that 4.71!12 of methylpropyl chloride was used.

As a result, 4.48 g of crude 2-(4-methoxyphenyl)-2-methylpropyl chloride was obtained. Analysis of the obtained material by gas chromatography revealed that 2-(4-methoxyphenyl)-2-methylpropyl chloride was 80.2
% was included.

Yield 9, 4% Patent Applicant Mitsui Toatsu Chemical Co., Ltd. Procedures Amendment Written December 27, 1980 Manabu Shiga, Commissioner of the Patent Office 1, Indication of Case Patent Application No. 5525, 1982 2, Invention Name 2 - Process for producing (4-alkoxyphenyl)-2-methylpropyl chloride 3 Relationship with the case of the person making the amendment Patent applicant address Chiyoda-ku, Tokyo - 2-5-4 Mazai-chome; Date of amendment order Vol. 5, “Detailed Description of the Invention” of the specification to be amended, Part 4, Contents of amendment (1) Specification, page 3, line 13 (line 6 from the bottom) “
It is a new insecticide. 3-7 Enoki °° is corrected to ``3-7 Enoki, a new insecticide''.

(2) Specification, page 3, line $17 (second line from the bottom) “
Correct the expression 2-(4-alkoxy), which is an isomer, to 2-(4-alkoxy).

(3) Specification, page 8, line 14 (fourth line from the bottom)
The phrase "-2-methyl-propyl" is corrected to "-2-methylpropyl."

(4) Akira, l+lII Homare, page 8, line 16 (second line from the bottom), "-2-methylpropyl" is corrected to "-2-methylpropyl J.

(5) In the specification, page 9, line 1, "°-2-methyl-propyl" is corrected to "-2-methylpropyl."

(6) Specification, page 11, line 13: ``0.00001''
Part to 0.5 part, corrected to ``IO, 00001 part to 0.5 part (metal equivalent)''.

(7) Ming #l Cao, page 11, line 14 “0.001~
Correct it to 0.2 parts.ro,oooi~0.2 parts.

(8) Specification, page 11, line 14 to line 17 “’
If a base is required, it is 0.5 parts to 10 parts, preferably 1.
0 to 2.0 parts of base, or 0.1 to 3 parts if a solvent is required.
0 parts of solvent are used, preferably 1.0 to 10 parts. If the amount used is large, productivity will decrease. 'If a solvent is required, it should be 0.1 to 30, preferably 1.
0 to 10 parts of solvent are used. If the amount used is large, productivity will decrease. If a base is required, 0.5 to 10 equivalents, preferably 1.0 to 2.0 equivalents of base per equivalent of 2-(3-halogen-4-alkoxyphenyl)-2-methylpropyl chloride. use. ” he corrected.

(9) Specification, page 12, line 7: "Solvent for organic layer"
Correct the phrase “solvent.”

(10) Specification, page 12, line 12 K”5.00f5
%Pd-C". Correct to 5.0 (Jf, 5% pd-Cl.

(11) In the specification, page 12, line 19, the phrase ``residue after removal'' is amended to read ``after removal, remainder after filtration''.

Claims (2)

[Claims] (1) General formula (i) (In formula (1), 1t represents a lower alkyl group, and X represents a chlorine atom-bromine atom) 2-(3-haO)y'/-4- The general formula (■
); A method for producing 2-(4-alkoxyphenyl)-2-methylpropyl chloride represented by (Formula Ql), in which R represents the above meaning. (2) In general formula (I), () is a methyl group or an ethyl group, the manufacturing method described in item 1 of the patent scope.