JP3534811B2 - Method for producing phenethyl alcohol derivative (3) - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a phenethyl alcohol derivative for improving the storage stability of a color image in a thermosensitive recording material. Conventionally, when a compound having an ether bond is produced by reacting a phenol (alcohol) with a compound having an epoxy group, a tertiary amine, a quaternary ammonium salt or the like is used as a catalyst. In general, a method of performing an addition reaction in an organic solvent or the like is known. However, it is known that there are α-cleavage and β-cleavage in the direction of cleavage of the epoxy ring (Makromol. Chem., 183.
587 (1982)), making it difficult to obtain only one target product in high yield. [0003] Further, to a compound having two or more phenolic hydroxyl groups, such as a dihydroxydiphenylsulfone compound, a reaction of selectively adding a compound having an epoxy group to only one of the hydroxyl groups without using a protecting group is performed. It was very difficult to tighten. Further, it is known that a compound having an epoxy group is generally unstable in the presence of an acidic or alkaline compound and is liable to form a polymer. The addition reaction was not easy. SUMMARY OF THE INVENTION The present invention provides a reaction between a styrene oxide compound and a dihydroxydiphenylsulfone compound, wherein one of the hydroxyl groups and the epoxy group reacts selectively, and an α-cleaved ether bond is formed. The present invention proposes a production method for selectively obtaining a compound having the same. [0006] The present invention relates to a method for converting a styrene oxide compound and a dihydroxydiphenylsulfone compound represented by the general formula (II) into an alkali metal or alkaline earth metal halide. The following is a method for producing a phenethyl alcohol derivative represented by the general formula (I), wherein the reaction is carried out in a two-layer solvent of water-organic solvent. Formula (I) Formula (II) (Wherein, R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkenyl group, R ⁴ represents a hydrogen atom, a lower alkyl group or a phenyl group, n, m And p each represent an integer of 1 to 4.) The production method of the present invention will be described in detail below. In the production method of the present invention, the mixing ratio of water to the water-insoluble organic solvent is 0.1 to 1 with respect to 1 volume of water.
0 volume, preferably approximately the same volume. In such a two-layer system, a halide of an alkali metal or an alkaline earth metal and a 4,4′-dihydroxydiphenyl sulfone compound represented by the general formula (III) are contained. In addition, a styrene oxide compound is further added and reacted for several hours to several tens of hours. In the production method of the present invention, the reaction temperature is 5
The temperature is preferably from 0 to 90 ° C, more preferably from 80 to 90 ° C. If the temperature is lower than 50 ° C., the yield decreases, and if the temperature is higher than 90 ° C., the yield tends to decrease due to the decrease in selectivity, and the production of di-substituted products tends to increase. In the present invention, the amount of each used per mole of the diphenyl sulfone compound is 0.5 to 2 in the case of a halide of an alkali metal or an alkaline earth metal.
Mol, preferably 0.8 to 1.2 mol, and in the case of a styrene oxide compound, 0.2 to 1 mol, preferably 0.4 to 0.5 mol. The general formula (II) used in the present invention
As dihydrocyphenylsulfone represented by 4,
4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3'-dichlorodiphenylsulfone,
4,4′-dihydroxy-3,3′-dibromodiphenylsulfone, 4,4′-dihydroxy-3,3 ′, 5,
5'-tetrachlorodiphenylsulfone, 4,4'-dihydroxy-3,3 ', 5,5'-tetrabromodiphenylsulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone, 4,4' -Dihydroxy-
3,3 ′, 5,5′-tetramethyldiphenylsulfone, 4,4′-dihydroxy-3,3′-diallyldiphenylsulfone, 4,4′-dihydroxy-3,3 ′,
5,5′-tetraallyldiphenyl sulfone, 4,4 ′
-Dihydroxy-3,3'-dichloro-5,5'-dimethyldiphenylsulfone, 4,4'-dihydroxy-
3,3′-dibromo-5,5′-dimethyldiphenylsulfone, 4,4′-dihydroxy-3,3′-dimethyl-5,5′-diallyldiphenylsulfone and the like are exemplified. The styrene oxide compounds used in the present invention include styrene, α-methylstyrene, α
-Phenylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2-methylstyrene,
3-methylstyrene, 4-methylstyrene, 2-bromostyrene, 3-bromostyrene, 4-bromostyrene,
α-methyl-2-chlorostyrene, α-methyl-2-chlorostyrene, α-methyl-3-chlorostyrene, α-
Methyl-4-chlorostyrene, α-phenyl-2-chlorostyrene, α-phenyl-3-chlorostyrene, α-
Examples thereof include phenyl-4-chlorostyrene, α-methyl-2-methylstyrene, α-methyl-3-methylstyrene, and α-methyl-4-methylstyrene. In the present invention, examples of the water-insoluble organic solvent used include aromatic organic solvents such as benzene, toluene, chlorobenzene and dichlorobenzene, and methyl isobutyl ketone, diethyl ketone and ethyl butyl ketone. Examples thereof include ketone organic solvents, ester organic solvents such as ethyl acetate, and aliphatic halogenated solvents such as chloroform and carbon tetrachloride. The halides of alkali metals or alkaline earth metals used in the present invention include, for example, sodium chloride, potassium chloride, calcium chloride,
Examples include magnesium chloride, barium chloride, sodium bromide, potassium bromide, magnesium bromide, sodium iodide, potassium iodide, magnesium iodide and the like. In the production method of the present invention, various treatment methods after completion of the reaction are possible. For example, an acidic compound such as sulfuric acid is added to the reaction solution to adjust the pH to slightly alkaline, and the aqueous layer is separated. Thereafter, there is a method in which a target compound is obtained by adding a hot alkaline substance aqueous solution to the organic solvent layer, extracting the target compound into the aqueous layer, and cooling or acidifying to precipitate crystals. According to the production method of the present invention, α
The cleaved target compound is obtained. If necessary, the reaction product can be obtained by using an organic solvent such as acetates and dialkyl ketones or an aqueous solution of a heated alkaline compound. it can. The present invention will be described below in more detail with reference to Reference Examples and Examples. (Example 1) 50 ml of water, 8.3 g (0.05 mol) of potassium iodide, 25 g (0.1 mol) of 4,4'-dihydrosidiphenyl sulfone (hereinafter abbreviated as "BPS") in a 300 ml four-diameter flask ) And 30 ml of methyl isobutyl ketone (hereinafter abbreviated as “MIBK”). Next, 6 g (0.05 mol) of styrene oxide was added, and the mixture was reacted at 85 to 90 ° C. for 5 hours. After the completion of the reaction, the aqueous layer was made acidic by adding dilute sulfuric acid, and separated. When the organic solvent layer was analyzed by high performance liquid chromatography, the target substance, 4- (4- (2-hydroxy-1-phenylethyloxy) phenylsulfonyl) phenol, was 8.3 g.
The selectivity of the target product was 86%, and the yield from styrene oxide was 45%. (Example 2) In the same manner as in Example 1, water 5
0 ml, 2.9 g (0.05 mol) of sodium chloride, B
Using 25 g (0.1 mol) of PS, 50 ml of MIBK, and 6 g (0.05 mol) of styrene oxide, 85
The reaction was performed at ９０90 ° C. for 5 hours. After the same treatment as described below, the organic solvent layer was analyzed by high performance liquid chromatography, and the result was 4- (4- (2-hydroxy-1-phenylethyloxy) phenylsulfonyl), which was the target substance.
Contains 4.0 g of phenol and has a selectivity of 7 for the target product.
8%, and the yield from styrene oxide was 22%. Example 3 In the same manner as in Example 1, water 5
0 ml, potassium bromide 6.0 g (0.05 mol), BP
S25 g (0.1 mol), MIBK 50 ml, and styrene oxide 6 g (0.05 mol)
The reaction was performed at 90 ° C. for 5 hours. After the same treatment as described below, the organic solvent layer was analyzed by high performance liquid chromatography, and the result was 4- (4- (2-hydroxy-1-phenylethyloxy) phenylsulfonyl), which was the target substance.
It contains 4.4 g of phenol and has a selectivity of 7 for the target product.
The yield based on 9% and styrene oxide was 24%. Comparative Example In the same manner as in Example 1, water 50
ml, BPS 25g (0.1 mol), MIBK50m
1 and 6 g (0.05 mol) of styrene oxide were reacted at 85 to 90 ° C. for 5 hours. After the same treatment was performed, the organic solvent layer was analyzed by high performance liquid chromatography, and the result was 4- (4- (2-
The yield of hydroxy-1-phenylethyloxy) phenylsulfonyl) phenol from styrene oxide was 4%, and the conversion was very low. According to the present invention, when a dihydroxydiphenylsulfone compound is directly reacted with a styrene oxide compound, an extremely large number of by-products are produced depending on the disubstituted product, the polymer and the direction of cleavage of the epoxy group. However, according to the production method of the present invention, one hydroxyl group and a halogen group react with each other, and a phenethyl alcohol derivative having an α-cleaved ether bond can be easily obtained with a high yield.

Continuation of the front page (56) References JP-A-5-246924 (JP, A) JP-A-6-166649 (JP, A) JP-A-6-166648 (JP, A) International Publication No. 94/07832 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 315/04 C07C 317/22 C07C 41/03 C07C 43/23 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (1)

(57) [Claim 1] A styrene oxide compound and a compound represented by the general formula (I)
Reacting the dihydroxydiphenylsulfone compound represented by I) in a water / organic solvent two-layer system solvent in the presence of an alkali metal or alkaline earth metal halide; A method for producing the represented phenethyl alcohol derivative. Formula (I) Formula (II) (Wherein, R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkenyl group, R ⁴ represents a hydrogen atom, a lower alkyl group or a phenyl group, n, m And p each represent an integer of 1 to 4.)