JPH0368530A - Method for recovering phenol or thiophenol derivative - Google Patents

Abstract

PURPOSE:To simply, inexpensively and efficiently obtain p-phenoxyphenol, etc., useful as an intermediate for insecticide by reacting 2-(4-phenoxyphenoxy)-1- propanol, etc., with a base and then neutralizing the reaction product. CONSTITUTION:1 pts.wt. of one or more kind of compounds expressed by formu la I (R1 and R2 are H, halogen, alkyl, alkoxy, haloalkyl, etc.; R3 is halogen or CH3; R4 and R5 are H, halogen or CH3; Y is O or S; Z is O, S or methylene; m is 0-4; n is 0-2) is reacted with 0.5-10 pts.wt. base (e.g. NaOH) at -10-300 deg.C for 30 min to 100hr and the reaction product is extracted with an organic sol vent in order to remove impurities and then neutralized with hydrochloric acid, etc., to provide the compound expressed by formula II. A phase-transfer catalyst of 18-crown-6, etc., can be also used as a reaction assistant in an amount of 0.00001-1 pts.wt. based on 1 pts.wt. raw material.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for recovering phenol or thiophenol derivatives useful as intermediates for insecticides.

<Prior art and problems to be solved by the invention> In US Pat. No. 4,751.225, it is known that, for example, a compound represented by the following general formula (I) can be used as an active ingredient of an insecticide. ing.

[In the formula, R1 and R2 are the same or different, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or a haloalkyl group having 1 to 4 carbon atoms. ~4 haloalkoxyl group. R8 represents a halogen atom or a methyl group, and R4 and R6 are the same or different and represent a hydrogen atom, a halogen atom or a methyl group. Y represents an oxygen atom or a sulfur atom, and Z represents an oxygen atom, a sulfur atom or a methylene group. m represents an integer of 0 to 4, and n represents an integer of 0 to 2. ] For example, among the compounds represented by the general formula (I), a typical example is pyrifenoxyphene represented by the formula (E').

Now, the intermediate of the birifenoxifene, the formula (II
) 1-(4-phenoxyphenoxy)-2-propanol can be obtained by reacting 4-phenoxyphenol and propylene oxide in the presence of a base. During this reaction, the above-mentioned 2-propanol (n
2-(4-phenoxyphenoxy)-1-propanol, which is an isomer of formula (III), is also produced to some extent.

Therefore, for example, 2-propanol (II) and 1-propanol (III) are crystallized from a mixture of 2-propanol (II) and 1-propanol (III).
- Crystallization fil (2-
If expensive 4-phenoxyphenol, which is a common raw material, can be recovered from a mixture of propanol (It) and 1-propanol (ffl), the method would be extremely useful industrially.

Means for Solving the Problems> In view of this situation, the inventors of the present invention have made various studies and found that n in general formula (IV) has the same meaning as above. ] By reacting one or more alcohol derivatives represented by with a base and then neutralizing with an acid, the general formula (V) [wherein R1, R2, R8, Y, Z and m are the same as above] express meaning. ] It was discovered that the phenol or thiophenol derivative represented by these can be efficiently recovered, leading to the present invention.

Although a solvent is not necessarily required for the reaction of converting the alcohol derivative represented by the general formula (IV) into the phenol or thiophenol derivative represented by the general formula (■)', if a solvent is used, Examples of solvents include alcohols such as methanol, ethanol, isopropanol, butanol, cyclohexanol, ethylene glycol, polyethylene glycol, and glycerin; aromatic hydrocarbons such as benzene and toluene-chlorobenzene;
Ethers such as ether tetrahydrofuran and dioxane, aliphatic hydrocarbons such as pentane, hexane, heptane, and cyclohexane, halogenated hydrocarbons such as dichloromethane, dichloroethane, and chloroform, acetone,
Ketones such as methyl isobutyl ketone% N+N-dimethylformamide, amides such as N,N-dimethylacetamide, sulfoxides such as dimethyl sulfoxide and sulfolane, nitriles such as acetonitrile and benzonitrile, pyridines such as pyridine and picoline, Water or mixtures thereof can be used.

Examples of bases include hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide; carbonates such as sodium carbonate and potassium carbonate; bicarbonates such as sodium hydrogen carbonate; side, metal alkoxides such as sodium methoxide, metal hydrides such as sodium hydride and potassium hydride, aliphatic amines such as triethylamine, aromatic amines such as aniline, and pyridines such as pyridine and picoline. , ammonium hydroxides such as tetrabutylammonium hydroxide, or mixtures thereof. In addition, the amount of base used in the reaction is determined by the general formula (I
The amount is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 1 part by weight of the compound represented by V) or a mixture thereof. The reaction temperature range is -3°C to 500°C
1, preferably from -10°C to 30°C, and the reaction time ranges from 5 minutes to 200 hours, preferably from 80 minutes to 100 hours.

In addition, as reaction aids, ammonium salts such as tetrabutylammonium promide trimethylbenzyl ammonium chloride, ethers such as 18-crown-6, phase transfer of tris(8,6-dioxohbutyl)amine (TDA-1), etc. o, oooot to 1 part by weight of the compound represented by the formula (IV) or a mixture thereof;
~1 part by weight can also be used.

For example, the reaction solution after the completion of the reaction is directly extracted with an organic solvent to remove impurities, then neutralized with hydrochloric acid, etc., and then subjected to conventional post-treatments such as organic solvent extraction and concentration or filtration and drying, and if necessary. By purification by operations such as , recrystallization, etc., the desired phenol or thiophenol derivative represented by the general formula (■) can be obtained.

<Example> Next, the present invention will be explained in detail with reference to production examples, but the present invention is not limited only to these production examples.

Production Example 1 15 parts of a mixture of 2-(4-phenoxyphenoxy)-1-propanol and 1-(4-phenoxyphenoxy)-2-propanol was added to 80 parts of ethylene glycol under a nitrogen stream.
Dissolved in f.

this#! Add 14.74 fl of sodium hydroxide to liquid i (
0.87 mol) and stirred the reaction mixture.
The reaction was carried out at 0°C for 2 hours and 30 minutes. The reaction mixture was then poured into 200 g of ice water and extracted twice with 100 g of toluene. Combine the toluene layers and add 10% sodium hydroxide solution H.
, 100- for eight times.

All the aqueous layers were combined, neutralized with 8696HC/, extracted twice with 100 gt of toluene, and the organic layers were combined and dried over anhydrous magnesium sulfate. 10.1 f of crude p-phenoxyphenol was then concentrated under reduced pressure.
I got l.

Production Example 2 A mixture 301 of 2-(4-phenoxyphenoxy)-1-propanol and 1-(4-phenoxyphenoxy)-2-propanol was mixed with polyethylene glycol under a nitrogen stream.
It was dissolved in 60020g. Add 8 parts of potassium hydroxide to this solution.
4.49 (0.68 mol) was added to make the reaction mixture membrane 150
The mixture was heated to °C and aged under stirring for 2 hours and 80 minutes. The reaction mixture was then poured into 200ml of ice water and extracted twice with 100ml of toluene. The toluene layers were combined and extracted eight times with 10% aqueous sodium hydroxide @ water layer 00-. Combine all the water layers,
Neutralized with 36% 11C1. Toluene 1 from this aqueous solution
The organic layers were combined and dried over anhydrous magnesium sulfate. Next, concentrate under reduced pressure!
:blip-phenoxyphenol 19.0f obtained 1=
.

<Effects of the Invention> The present recovery method is efficient, simple, and inexpensive, and is effective as a method for recovering phenol or thiophenol derivatives that are useful as intermediates for insecticides and the like.

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R_1 and R_2 are the same or different, hydrogen atom, halogen atom, alkyl group having 1 to 4 carbon atoms, 4 alkoxyl group, a C1-C4 haloalkyl group, or a C1-C4 haloalkoxyl group. R_3 represents a halogen atom or a methyl group, and R_3 represents a halogen atom or a methyl group;
_4 and R_5 are the same or different and represent a hydrogen atom, a halogen atom or a methyl group. Y represents an oxygen atom or a sulfur atom, and Z represents an oxygen atom, a sulfur atom or a methylene group. m represents an integer from 0 to 4, n is 0
Represents an integer between ~2. ] General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1, R_2, R_3, Y, Z and m have the same meanings as above. ] A method for recovering phenol or thiophenol derivatives.