JPH04173772A - Production of phenoxyacetamides - Google Patents

Abstract

PURPOSE:To obtain the subject high-purity compounds useful as an additive for a recording material such as a heat sensitive paper in a high yield using simple operations by reacting a phenol with a halogenacetic acid ester, etc., in the presence of a base and subsequently reacting the resultant reaction product with an amine. CONSTITUTION:A compound of formula 1 (R<1> and R<2> are H, halogen, alkyl or alkoxy; X is O or S) is made to react with a compound of formula 2 (R<3> is H or alkyl; R<4> is alkyl; Y is halogen) in the presence of a base (preferably potassium carbonate), preferably in a polar solvent at 0-130 deg.C, especially 60-120 deg.C, thus obtaining the objective phenoxyacetic acid ester of formula 3. The resultant compound of formula 3 is then allowed to react with a compound of formula 4 (R<5> and R<6> are H or alkyl) at 0-130 deg.C, especially 10-120 deg.C to obtain the objective compound of formula 5. After completion of the reaction, the objective high-purity compound can be obtained without recrystallization only by simple operations, i.e., only by adding water and cooling.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing phenoxyacetic acid amide, and more particularly to a method for producing phenoxyacetic acid amide useful as an additive for recording materials such as thermal paper.

(Prior Art) In recent years, research has been actively conducted on diazo color-forming heat-sensitive recording materials as heat-sensitive recording materials with high image reliability. As disclosed in JP-A No. 62-132675, etc., the present inventors have discovered that a core material contains at least one component involved in a color reaction, and a wall is formed around this core material by polymerization. It has been found that an excellent heat-sensitive recording material can be obtained by the method of microencapsulation. Furthermore, the present inventors have found that the recording material has excellent thermal responsiveness by adding phenoxyacetic acid amides to the recording layer, and a patent application is pending. As a method for producing phenoxyacetic acid amides used here, a reaction between a phenol and a halogenoacetic acid amide is generally considered from the viewpoint of the number of steps.

However, this method does not give a sufficient yield;
In addition, there were problems with the reaction operability associated with temperature control, the use of inert gas to prevent coloration, purification by recrystallization, etc., and the treatment of waste water of the reaction solution containing halogenoacetic acid amide, etc., and improvements were desired.

(Objective of the Invention) An object of the present invention is to provide a manufacturing method for easily obtaining high-purity phenoxyacetic acid amides with good yield and operability.

(Means for Solving the Problems) The object of the present invention is to react phenols and halogenoacetic esters in the presence of a base to form phenoxyacetic esters, and then react them with amines, as shown below. The problem was solved by developing a manufacturing method to obtain phenoxyacetic acid amides.

[First step]

(1) (2)
+31C9J two steps] In the above formula, R' and R' each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, X represents an oxygen atom or a sulfur atom, and R' represents a hydrogen atom or an alkyl group. R' represents an alkyl group, Y represents a halogen atom, R' and R' each independently represent a hydrogen atom, and s< represents an alkyl group.

Specific examples of the compound of formula (1) include the following.

Specific examples of the compound of formula (2) include the following.

BrCH, CO0Et, CICH, COOMe,
BrCH,COOMaBraHCOOEt,
Specific examples of the compound of the CICHCOOMe formula (4) include the following.

NH,, MeNH7, EfNH,, PrNl-12 In the method of the present invention, the reaction can be carried out under mild conditions and with simple operations, and by selecting the molar equivalent ratio of the base, reaction solvent, and raw materials used. , it is possible to obtain the target product with high purity in good yield.

In the first step, it is preferable to use a polar solvent as the solvent, such as sulfolane, dimethylformamide,
Dimethylacetamide, N-methyl biOlidone, etc. are mentioned. Bases include sodium carbonate, potassium carbonate,
Examples include sodium hydroxide, potassium hydroxide, etc., and potassium carbonate is preferable in consideration of ester resistance to hydrolysis, reactivity, etc. In the second step, a polar solvent such as water or alcohol is used as the solvent.

The molar ratio of phenols and halogenoacetic esters in the first step is preferably in the range of 1:0.6 to i:i,8, particularly preferably 1:0.8 to 1:1.4.

The molar ratio of phenols to base is 1:0.8 to 1:3.
O is preferably in the range of 1:0.8 to 1:2.
, 6 are preferred. Reaction temperature is preferably 0 to 130°C
However, 60 to 120@C is particularly preferred. The reaction time is about 0.5 to 6 hours. The molar ratio of esters and amines in the second step is preferably in the range of 1:0.9 to 1:6, particularly preferably 1:1 to 1:4. The reaction temperature is preferably 0 to 130@C, particularly preferably 10 to 120@C.

The reaction time is about 0.5 to 5 hours.

According to this method, after the reaction in the second step, an extremely pure target product can be obtained in high yield without recrystallization by a simple operation of adding water and cooling.

(Example) Examples are shown below, but the present invention is not limited thereto.

Example 1 27.69 4-ethoxyphenol and 26.09 methyl α-chloroacetate were added to 90 cc of dimethylformamide, and 349 cc of anhydrous potassium carbonate was added and the mixture was heated at 906C for 3
Stir for hours. To this reaction solution, 200 cc of water and 2 cc of toluene.
After extracting the organic layer by adding 00 cc of the organic layer, the organic layer was washed with water, the solvent was distilled off, and the residue was distilled to obtain 39.59 ml of methyl α-(4-ethoxyphenoxy)acetate. bp 137-139”C
/3□□H1 Next, 600C of methanol was added to this compound 39,5 (), and 40cc of 27% ammonia water was added to 40
The mixture was added dropwise at 40°C or below, and further stirred at 40°C for 2 hours.

Next, 40 cc of water and 21 cc of acetic acid were added to neutralize the reaction solution, and the mixture was stirred for 1 hour at 5 IC or less. The precipitated crystals were filtered, washed with water, and dried to obtain the desired α-(
4-Ethoxyphenoxy)acetic acid amide 339 was obtained. m
p 138-139' Yield from C4-nitoxyphenol is 85%, purity by HLC is 99.8%
That was it.

Examples 2 to 4 The following compounds were obtained in the same manner as in Example 1, except that various phenols and amines were used in place of 4-ethoxyphenol and aqueous ammonia in Example 1.

α-(3-methylphenoxy)acetic acid amide mp 119
~120''C yield 88% α-(2-fluorophenoxy)acetic acid amide mp 12El-129@C yield 8
2% α-(4-methylphenylthio)acetic acid amide mp
118-119 @ C Yield 85% Comparative Example 27.69 of 4-ethoxyphenol and 34.09 of α-riO-roacetic acid amide were added to 90 cc of dimethylformamide, and further 349 cc of anhydrous potassium carbonate was added and the mixture was heated at 90°C for 3
Stir for hours. By adding 200 cc of water to this reaction solution and filtering the precipitated crystals, washing with water and drying, α-(
4-ethoxyphenoxy)acetic acid amide 279 was obtained. m
p 137-139°C Since solvent odor and coloration were observed in the above compound, it was recrystallized with 80 cc of methanol to obtain purified product 249. +np 13El~139 @C4-
The yield from ditoxyphenol was 62%, HLC
The purity was 99.5%.

(Effect of the invention) According to the manufacturing method of the present invention, although the number of steps is two,
The reaction can be carried out under mild conditions with simple operations, and the target product of high purity can be obtained in good yield.

Claims (1)

[Claims] 1. A method for producing phenoxyacetic acid amides, which comprises reacting phenols and halogenoacetic esters in the presence of a base to produce phenoxyacetic esters, and then reacting them with amines.