JPH0474148A - Production of 2-aryloxy-1-substituted alkane - Google Patents

Abstract

PURPOSE:To readily obtain the subject compound in high yield at a low cost by reacting a 2-bromo-1-chloroalkane with the first phenolic derivative under alkaline conditions and then the second phenolic or a carboxylic acid derivative therewith. CONSTITUTION:A 2-bromo-1-chloroalkane, preferably 2-bromo-1-chloropropane is reacted with the first phenolic derivative under alkaline conditions to selectively provide a 2-phenoxy-1-chloroalkane, which is then reacted with the second phenolic or a carboxylic acid derivative to afford the subject compound useful as a heat fusible substance for recording materials in excellent yield with advantages such as the first and second aforementioned compounds can be optionally selected by easy handling with hardly any coloring of the product. Furthermore, the reaction temperature is preferably 20-170 deg.C, especially 40-90 deg.C in the first-stage reaction and 60-150 deg.C in the second-stage reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to a process for producing 2-aryloxy-1-substituted alkanes useful as thermofusible materials for recording materials.

(Prior Art) As a conventional method for producing 2-aryloxy-1-substituted alkanes, 1) a phenol derivative is reacted with fullylene oxide or alkylene carbonate to form a corresponding aryloxydiakanol, and then this alcohol derivative is reacted with an active halogen. derivatives or active ester derivatives.

2) a method of reacting the first phenol with a dihalide or diactive ester of an alkylene diol, and further reacting the first phenol with a second phenol derivative or a carboxylic acid derivative; 3) A method is known in which a corresponding haloalcohol and a first phenol derivative are reacted under alkaline conditions, transformed into an active halogen derivative or an active ester derivative, and then further reacted with a second phenol derivative or carboxylic acid derivative. However, in these methods,
There were problems with low yield, handling, cost, and safety.

(Object of the Invention) An object of the present invention is to provide a method for producing 2-aryloxy-1-substituted alkanes with high yield, easy purification, and low cost.

(Structure of the Invention) The object of the present invention is to react a first phenol derivative with 2-bromo-1-chloroalkane under alkaline conditions, and then react with a second phenol derivative or a carboxylic acid derivative. 2-aryloxy-1-
This was achieved by developing a method for producing substituted alkanes.

The 2-bromo-1-chloroalkane according to the present invention is
-Bromo-1-chloropropane, 2-bromo-1-chlorobutane, 2-bromo-1-chlorohexane, 2-bromo-1-chlorobutane.

etc., but 2-bromo-1-chloropropane is preferred.

The phenol derivative according to the present invention is represented by the following general formula.

ArOH (1) In the above formula, Ar represents a phenyl group or a naphthyl group which may have a substituent.

Examples of substituents for Ar include alkyl groups, alkoxy groups,
Examples include a halogen atom, a nitro group, a cyano group, an acyl group, a phenyl group, etc., and particularly preferred are an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a chlorine atom.

Specific examples include phenol, p, m, or 0-cresol, p, m, or 0-ethylphenol, plm
or 0-propylphenol.

p, m, or 0-methoxyphenol, plm.

or 0-ethoxyphenol + pl m, or 〇-
Chlorophenol, α-naphthol, β-naphthol,
Examples include nitrophenol, cyanophenol, acetylphenol, phenylphenol and the like. Preferred examples of the phenol derivatives reacted in the first step include phenol, p-cresol, p-ethylphenol, p-
-methoxyphenol, p-ethoxyphenol, p-
Examples include chlorophenol, p-phenylphenol, and β-naphthol. A preferred example of the phenol derivative reacted in the second step is phenol.

Examples include p-cresol, p-ethylphenol, p-methoxyphenol, p-ethoxyphenol, p-chlorophenol, and β-naphthol.

The carboxylic acid derivative according to the present invention has the following general formula (11)
Say what is expressed by.

RCOOH(I+> In the above formula, R represents a phenyl group, a naphthyl group, which may have a substituent, or an alkyl group, which may have a substituent.

Examples of substituents for the phenyl group or naphthyl group represented by R include an alkyl group, an alkoxy group, a halogen atom, a nitro group, a cyano group, an acyl group, and a phenyl group. Examples of substituents for the alkyl group represented by R are:
Examples include phenyl group, phenoxy group, and halogen atom.

Specific examples include benzoic acid, anisic acid, toluic acid, chlorobenzoic acid, phenylacetic acid, phenoxyacetic acid, and the like.

The reaction temperature when carrying out the production method of the present invention is 20 to 17
0°C is preferable, especially 40-90° for the first stage reaction.
It is preferable to carry out the second stage reaction at 60 to 15
0°C is preferable; if the temperature is 1700°C or higher, side reactions tend to occur and it is difficult to obtain a highly pure product.

When carrying out the production method of the present invention, it can be carried out in water, a mixture of water and an organic solvent, or an organic solvent, but it is preferably carried out in a mixture of water and an organic solvent or an organic solvent. In the first-stage reaction and the second-stage reaction, the solvent used may be changed.1 Examples of organic solvents used when carrying out the production method of the present invention include alcohols and ketones.

Polar solvents such as esters, nitriles, amides, sulfones,
Examples include halogenated hydrocarbons and aromatic hydrocarbons.

Specifically, methanol, ethanol, propatool,
Examples include acetone, methyl ethyl ketone, acetonitrile, dimethylformamide, dimethylacetamide, sulfolane, and toluene.

The base used in carrying out the production method of the present invention is preferably a sodium compound or a potassium compound.

Specific examples of bases include caustic soda and caustic potash.

Examples include soda carbonate, potassium carbonate, and sodium methylate. Among these, caustic soda and caustic potash are particularly preferred.

The amount of base used is 1 per mole of phenol derivative.
-3 mol is preferable, and 1-2 mol is especially preferable.

When implementing the production method of the present invention, it is preferable that the solid content concentration at the time of charging is 50% or less from the viewpoint of undoing.

The reaction can also be carried out under an inert gas atmosphere.

This is preferable from the viewpoint of preventing coloring of the product.

When carrying out the production method of the present invention, a phase transfer catalyst may be used in combination.

Quaternary ammonium salt, polyalkylene glycol.

Examples include crown ether, among which,
A quaternary ammonium salt represented by the following general formula (11) is preferred.

R1-N-R,X [11] In the above formula R, ~
R4 is an alkyl group or an aryl group, and X is a residue of an inorganic or organic acid, such as CBr, l, OSO, R, (R is ○
H, aryl group.

represents ONR, R, R3R, and represents an acid group.

Specific examples of quaternary ammonium salts include tetramethylammonium bromide, tetraethylammonium bromide,
Tetra-n-butylammonium bromide, Tetra-n bromide
-Octylammonium tetra-n-butylammonium chloride, tetraethylammonium chloride, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylbenzylammonium chloride.

trioctylbenzylammonium bromide, tributylbenzylammonium chloride, tributylbenzylammonium bromide, N-laurylpyridinium chloride, tetraethylammonium hydroxide, triethylbenzylammonium hydroxide, trimethylphenylammonium bromide, tetra-n-butylammonium hydrogen sulfate , N-pendylpicolium chloride, tetraethylammonium iodide, tetra-n-butylammonium iodide, N-lauryl-4-picolinium chloride, and the like.

The amount of the quaternary ammonium salt to be used is preferably 0.01 to 3 mol, particularly preferably 0.1 to 1 mol, per 1 mol of 2-bromo-1 chloroaldine.

2- in the first stage reaction of the production method according to the present invention
The amount of bromo-1-chloroalkane and first phenol derivative to be used is preferably 0.8 to 1.2 mol of the first phenol derivative per 1 mol of 2-bromo-1-chloroalkane, particularly 0° The reaction product of the first stage, which is preferably 9 to 1.1 mol, may be used as it is in the second stage reaction, or may be taken out and purified etc. in the second stage reaction. The amount of 2-phenoxy-1-chloroalkane and the second phenol derivative or carboxylic acid derivative used is 0% of the phenol derivative or carboxylic acid derivative per mol of 2-phenoxy-1-chloroalkane.
．． It is preferably 8 to 2.0 mol, particularly 0.9 to 1.5 mol.

In the production method according to the present invention, since the bromine atom selectively reacts with the phenol derivative in the first step, by-products are small. There are 8 things to choose from. In addition, it has many advantages such as a very good yield, little coloring of the product, and easy handling.

(Example of the invention) The present invention will be specifically explained below with reference to Examples.

The invention is not limited to the examples.

Example 1 Synthesis of l-p-methoxyphenoxy-2-phenoxypropane In a three-necked flask equipped with a stirrer, 2-bromo-1
-1.0 mol of chloropropane, 1 mol of sodium phenolate
．． Weigh out 0 mol and 100 m of methanol. 100 ml of dimethylacetamide and 1 ml of p-methoxyphenol were added to the two reaction mixtures, which were reacted for 3 hours at 60°C with stirring.
．． 1 mole.

Add 1.3 mol of caustic soda, heat to 100°C, and continue the reaction for 3 hours while distilling methanol. 1. Pour the reaction mixture into water, collect the precipitated crystals by filtration, and recrystallize from methanol. Obtained the object. Yield 83%, melting point 87
°C Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except that 2-bromo-1-chloropropane was replaced with 1,2-dibromopropane.The reaction mixture was poured into water, but crystals did not precipitate. As a result of analyzing the 0 reaction product that was not present, the 9 reaction product was 1.2-
It was a mixture of diphenoxypropane, 2-phenoxy-+-p-methoxyphenoxypropane, 1-phenoxy-2-p-methoxyphenoxypropane, and 1,2-bis-p-methoxyphenoxypropane.

Example-2 Synthesis of 1-p-methoxyphenoxy-2-phenoxypropane In a three-neck flask equipped with a stirrer, 2-bromo-1
-1.0 mol of chloropropane, 1 mol of radium phenolate
．． Weigh out 0 mol and 100 m of methanol. 50% water was added to the reaction mixture, which was reacted for 3 hours at 60°C with stirring.
m1. 100 ml of toluene and 1.1 mol of p-methoxyphenol.

Added 1.3 mol of caustic soda and 0.3 mol of tetra-n-butylammonium bromide, heated to 100°C, and continued reaction for 4 hours. Water was added to the reaction mixture, and the toluene layer was separated and washed with water. I did it twice. Toluene is distilled off under reduced pressure,
Recrystallization was performed by adding methanol to obtain the desired product. Yield 7
7%, melting point 87C Examples 3 to 8 The phenol derivatives shown in the table below were reacted in the same manner as in Example 1.

(naphthyl)oxypropane (melting point 989C).

(Example-8) 1-p-medylphenoxy 2-(2-
naphthyl)oxypropane (melting point 976C)

Claims (1)

[Claims] 2-aryloxy-1-substituted alkane, which is characterized in that a first phenol derivative is reacted with 2-bromo-1-chloroalkane under alkaline conditions, and then a second phenol derivative or a carboxylic acid derivative is reacted with the 2-bromo-1-chloroalkane. Production method