JPH0429953A - Production of halogen-substituted phenyl benzyl ethers - Google Patents

Abstract

PURPOSE:To obtain the title compound at a relatively low temperature in a short time by one process and in high yield, by reacting a phenol with a benzyl halide as raw materials in the presence of an alkali metal compound and a phase transfer catalyst in a solvent under normal pressure. CONSTITUTION:A phenol or a halogen-substituted phenol shown by formula I [(m) is 0 or integer; X is halogen; Y is R (R is H or alkyl), COOR or OR] is made to react with a benzyl halide or a halogen-substituted benzyl halide shown by formula II ((n) is (m)) in the presence of an alkali metal compound such as KOH and a phase transfer catalyst such as quaternary ammonium salt, e.g. benzyltrimethylammonium chloride, in a solvent such as dioxane under normal pressure at 70 deg.C for 4 hours to give the objective compound shown by formula III (when (m) is 0, (n) is integer, and when (n) is 0, (m) is integer) having antimicrobial and deodorant effects with extremely little danger, industrially and advantageously in high yield.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a method for producing halogen-substituted phenylbenzyl ethers useful as "antibacterial and deodorant processing agents".

[Conventional technology]

In recent years, antibacterial and deodorizing treatments have been applied to base materials such as fibers to prevent bad odors, discoloration, and embrittlement of fibers caused by the growth of bacteria and mold, and to prevent pathogens on human skin and other areas. It's coming. Halogen-substituted phenylbenzyl ethers are used in a wide range of fields, including antibacterial and deodorizing treatments, sterilizing and insect repellent agents such as agricultural chemicals, and disinfectants mixed into soaps and cosmetics. Conventionally, phenylbenzyl ethers have been produced by a method in which phenol and benzyl chloride are reacted by boiling them using a sodium methylate or ethylate solution (CLAIS
EN, A, 442.237, VAN ALPHE
N, R, 46°804), a method of synthesis by boiling phenol and benzyl chloride in a dilute aqueous sodium solution (SHORT, 5TEWART,
Soc, 1929.554), method of synthesis using potassium carbonate in acetone (POWELL, ADAM
S, Am, Soc, 42.656), excess phenol and penzole sulfonic acid benzyl ether
Synthesis method by heating at 0°C (FOLDl,
B, 61.1613), a method of synthesis by boiling 2-chlorophenol and dimethylphenylbenzylammonium chloride in a dilute aqueous sodium solution (BAW, J, Indian chem,
Soc, 3.104; C, 1926II, 164
3) etc.

[Problem to be solved by the invention]

However, the conventional method described above has a problem in that it is highly dangerous because the reaction must be carried out at a high temperature. Furthermore, the method of using sodium methylate or sodium ethylate as a base has the problem that sodium methylate or sodium ethylate is extremely hygroscopic and is therefore not suitable for industrial use. Moreover, the yield of the product was also very poor. In view of the above circumstances, an object of the present invention is to provide a novel method for producing halogen-substituted phenylbenzyl ethers that solves the above problems.

[Means to solve the problem]

In order to achieve such an object, the present invention has the following general formula: X halogen, Y=
-R, -COOR, -0R (where R=H or an alkyl group)] In order to obtain the halogen-substituted phenylbenzyl ethers represented by the general formula, [in formula (A), m=
o or integer, X-halogen, Y=-R, -COOR,
-0R (where R=H or an alkyl group)] or halogen-substituted phenols, and the general formula, h [in formula (B), n=o or an integer, X-halogen] The gist is a method for producing halogen-substituted phenylbenzyl ethers, which is characterized by reacting a halogenated benzyl compound or a halogen-substituted halogenated benzyl compound with an alkali metal compound in the presence of a phase transfer catalyst in a solvent at normal pressure. . Moreover, it is preferable to use a quaternary ammonium salt as the phase transfer catalyst.

[For production]

When a phase transfer catalyst (Q+X-) is introduced into the reaction system, the reaction rate increases, and
In the process, the desired general formula is produced in good yield through the reaction mechanisms shown in the following ■ to ■.
- integer, when n=0, m=integer), X=halogen, Y-
=R, -COOR, -0R (however, R=H or an alkyl group)] Halogen-substituted phenyl group

【Example】

The present invention will be described in detail below with reference to examples thereof. The phenols or halogen-substituted phenols represented by the general formula (A) include phenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, 2,3-dichlorophenol, ．． 4. Examples include 6-trichlorophenol, 3-methyl-4-chlorophenol, methyl paraoxybenzoate, ethyl paraoxybenzoate, butyl paraoxybenzoate, methyl salicylate, and 2-methoxyphenol. Examples of the halogenated benzyls or halogen-substituted halogenated benzyls represented by the general formula (B) include benzyl chloride, benzyl bromide, benzyl iodide, 2-chlorobenzyl chloride, 3-chlorobenzyl chloride, 4-
Chlorobenzyl chloride, 2,4-dichlorobenzyl chloride, 2゜3-dichlorobenzyl chloride, 3,4-
Examples include dichlorobenzyl chloride and 2,4,6-dolichlorobenzyl chloride. Examples of the alkali metal compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and the like. Examples of the phase transfer catalyst include quaternary ammonium salts, phosphonium salts, sulfonium salts, etc. Among them, quaternary ammonium salts are particularly preferred from both a cost and an industrial standpoint. Examples of quaternary ammonium salts include benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltributylammonium chloride,
Benzyltrimethylammonium bromide, benzyltriethylammonium bromide, penzyltrimethylammonium fluoride, tetramethylammonium chloride, tetramethylammonium bromide, trioctylmethylammonium chloride, trioctylpropylammonium chloride, tetraphenylammonium bromide, tetrabutyl Examples include ammonium bromide and hexadecyltriethylammonium bromide. (Example 1) 4-chlorophenol 15.43 g (0.12 mol),
2.4-dichlorobenzyl chloride 19.55g (0,
1 mol), benzyltrimethylammonium chloride 1
．． 855 g (0.01 mol) and 20 g of potassium hydroxide were placed in 100-dioxane as a solvent and stirred at 70° C. for 4 hours. After 4 hours of stirring, 100% reaction had progressed. After that, by thoroughly washing with water and drying, 4chlorophenyl-[2-,4-dichlorobenzyl coether 28
．． 7 g was obtained. The yield was 100%. This 4-chlorophenyl-[2-,4-dichlorobenzyl coether was recrystallized from ethanol to obtain colorless needle-like crystals. The melting point of this needle-shaped crystal was 71-73°C. (Example 2) 2,4-dichlorophenyl-
[2-,4-dichloropenzyl coether 32.2
I got g. The yield was 100%. This 2,4-dichlorophenyl-[2-,4-dichloropenzyl coether was recrystallized from ethanol to obtain colorless needle crystals. The melting point of this needle-like crystal is 104-106℃
Met. (Example 3) 4-Chloro-3-methyl 60.3 g of phenyl-[2-,4-dichlorobenzyl 1 ether were obtained. The yield was 100%. This 4-chloro-3-methylphenyl-[2-. 4-Dichloropenzylcoether was recrystallized from ethanol to obtain colorless needle-like crystals. The melting point of this needle crystal is 68
The temperature was ~70°C. In addition, the CH ratio was theoretically (calculated) C: 62.94%, H: 4.53%, whereas the measured values were C: 63.11%, H: 4.66%. . (Example 4) 24-C')lorophenyl- [4--Chlorobenzyl coether28.
7 g was obtained. The yield was 100%. This 2,4-dichlorophenyl-[2'-chlorobenzyl coether was recrystallized from ethanol to obtain colorless needle crystals. The melting point of the needle-like crystals was 66-68°C. (Example 5) 2゜4-dichlorophenyl-[ 2'-chlorobenzyl coether 28.7
I got g. The yield was 100%. This 2. 4-Dichlorophenyl-[2-chlorobenzyl coether was recrystallized from ethanol to obtain colorless needle-like crystals. The melting point of this needle-shaped crystal was 64-65°C. (Example 6) 4-Carboxymethyl-[
2', 4-dichloropenzyl coether 31.1
I got g. The yield was 100%. This 4-carboxymethyl-[2-,4-dichloropenzyl coether was recrystallized from ethanol to obtain colorless needle crystals. The melting point of this needle-shaped crystal was 147-148°C. In addition, the theoretical value (calculated value) of the CH ratio is C:
57.90%, H: 3.89%, the measured value is C
: 57.79%, H: 3.95%. (Example 7) 4-Carboxyethylphenyl-[2', 4--Dichloropenzylcoether 3
1.1 g was obtained. The yield was 100%. This 4-carboxyethylphenyl-[2',4-dichloropenzyl coether was recrystallized from ethanol to obtain colorless needle crystals. The melting point of this needle crystal is 101~1
The temperature was 0.2°C. Furthermore, the CH ratio was theoretically (calculated) C: 59.10%, H: 4.34%, whereas the measured values were C: 59.17%, H: 4.21%. . (Example 8) 2-Methoxyphenyl-[2-,4
28.3 g of '-dichloropenzylcoether was obtained. The yield was 100%. This 2-methoxyphenyl-[2-,4''-dichloropenzyl coether was recrystallized with ethanol to obtain colorless needle crystals. The melting point of the needle crystals was 95 to 96°C. The theoretical value (calculated value) of the CH ratio is C:56
．． 21%, H: 4.04%, the measured value is C.5
6.15%, H: 4.08%. (Example 9) 110 g (1,0 mol) of catechol, 2. ．． 19.55 g (0.1 mol) of 4-dichlorobenzyl chloride, 12 g (0.3 mol) of sodium hydroxide, 3.71 g (0.02 mol) of benzyltrimethylammolium chloride
was added to 250 ml of dioxane and stirred at 70'C for 4 hours. As a result of this stirring, the reaction proceeded to 100%, and 23.5 g of 2-hydroxyphenyl-[2-,4-dichlorobenzyl coether was produced (yield: 87%; the remaining 13% was catechol benzyl ether as a by-product). obtained). As a post-treatment, a large amount of water was added to this, acidified with dilute sulfuric acid, extracted with benzene, further washed with water, and then dehydrated with anhydrous magnesium sulfate and concentrated. After dissolving this concentrate in cold ethanol (by-product acids are difficult to dissolve in ethanol), the solution is filtered, and the filtrate is concentrated again, recrystallized using a solvent such as hexane, and dried. pure 2-hydroxyphenyl-[2-,
Colorless needle-like crystals of 4-dichlorobenzyl coether were obtained. The melting point of this needle-shaped crystal was 68-70°C. Also,
The theoretical value (calculated value) of the CH ratio is C: 58.02%,
H: 3.75%, while the measured value is C: 58.21%
, H: 3.87%. (Example 10) 4-bromophenyl-[4 --29.7 g of bromobenzyl coether was obtained. The yield was 100%. This 4-bromophenyl-[4'-bromobenzyl coether was recrystallized from ethanol to obtain colorless needle-like crystals. The melting point of this needle-like crystal was 92-94°C. (Example 11) 30.22 g (0.12 mol) of 2,4-dibromophenol was used instead of 4-chlorophenol, and 24.98 g of 3-bromobenzyl bromide was used instead of 2°4-dichlorobenzyl chloride. 42.0 g of 2,4-dibromophenyl-[3'-bromobenzyl coether was obtained in the same manner as in Example 1, except that 2,4-dibromophenyl-[3'-bromobenzyl coether was used. The yield was 100%. This 2,4-dibromophenyl-[3'-bromobenzyl coether was recrystallized from ethanol to obtain colorless needle crystals. The melting point of this needle-like crystal was 49-51°C. Using each product constructed in the above examples, 1% o
Processed to adhere to wl, 5 tapylococcu
When the antibacterial and deodorizing effects were measured using S. aureus IFO12732 (Staphylococcus aureus) (measured by shake flask method and bacterial counting method), each product showed sufficient antibacterial and deodorizing effects.

【Effect of the invention】

Since the method for producing halogen-substituted phenylbenzyl ethers according to the present invention is configured as described above,
Since the reaction can be completed in a short time under normal pressure and at a relatively low temperature, there is very little danger, and a product with excellent antibacterial and deodorizing effects can be obtained in high yield. Moreover, since the reaction is completed in step (1), it is also industrially useful. Patent applicant: Waka Prefecture, Miki Riken Kogyo Co., Ltd. Agent: Patent attorney Masaru Sugimoto Tokudo Patent attorney: Sugimoto
Iwao

Claims (2)

[Claims] (1) General formulas, ▲ Numerical formulas, chemical formulas, tables, etc. =Halogen, Y
To obtain halogen-substituted phenylbenzyl ethers represented by =-R, -COOR, -OR (where R=H or an alkyl group), there are general formulas, ▲mathematical formulas, chemical formulas, tables, etc.▼...( A) [In formula (A), m = 0 or an integer, X = halogen, Y =
There are phenols or halogen-substituted phenols represented by -R, -COOR, -OR (where R=H or an alkyl group), general formulas, ▲mathematical formulas, chemical formulas, tables, etc.▼...(B ) [In the formula (B), n = 0 or an integer, A method for producing halogen-substituted phenylbenzyl ethers, which comprises reacting them. (2) The method for producing halogen-substituted phenylbenzyl ethers according to claim 1, wherein the phase transfer catalyst is a quaternary ammonium salt.