JPH05170754A - Production of monoglycidyloxy compound - Google Patents

Abstract

PURPOSE:To obtain the subject compound useful as an image preservation stabilizer, etc., for heat-sensitive recording charts in high yield by reacting a specific aromatic hydroxy compound with a specified epihalohydrin in the presence of a tertiary amine, etc. CONSTITUTION:An aromatic hydroxy compound expressed by formula I [R<1> is lower alkyl, lower alkenyl, (substituted)benzyl, etc.; R<2> and R<3> are lower alkyl, lower alkoxy or lower alkenyl ; A is C(CH3)2, CO, SO2 or S; (m) and (n) are 0-4] is made to react with an epihalohydrin expressed by formula II (R<4> is H or lower alkyl; X is halogen) in the presence of one or more of quaternary ammonium salts, tertiary amines, phosphonium salts and sulfonium salts which are catalysts to produce a 2-propanol compound expressed by formula III, which is then allowed to react in the presence of a dehydrohalogenating agent to provide the objective compound expressed by formula IV.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a monoglycidyloxy compound useful as an image storage stabilizer for heat-sensitive recording paper.

[0002]

2. Description of the Related Art Generally, a compound having a glycidyloxy group has a plurality of glycidyloxy groups and is mainly used as a raw material for an epoxy resin. And many manufacturing methods of them are proposed. For example, Japanese Patent Laid-Open No. 61-178974 discloses a method for reacting a polyhydric alcohol, in which boron trifluoride ethyl ether is preferable as a catalyst, with epihalohydrin, wherein an acrylamide group and a hydroxyl group using a quaternary ammonium salt are used as a catalyst. A production method of reacting an aromatic ring binuclear compound having one or more with epihalohydrin is disclosed in Japanese Patent Publication No. 2-51550. On the other hand, the monoglycidyloxy compound produced by the method of the present invention is a novel compound used as an image storage stabilizer for preventing the colored image on the thermosensitive recording paper from being erased by the packaging resin.

[0003]

This is a method for producing a monoglycidyloxy compound represented by the general formula (I) in good yield.

[0004]

The present invention has the general formula (II)
And an aromatic hydroxy compound represented by the general formula (III)
To produce a 2-propanol compound represented by the general formula (IV) by reacting with epihalohydrin represented by the formula (1) in the presence of one or more of a quaternary ammonium salt, a tertiary amine, a phosphonium salt and a sulfonium salt which are catalysts. And then reacting in the presence of a dehydrohalogenating agent, a method for producing a monoglycidyloxy compound represented by the general formula (I). (In the above general formula, R ¹ represents a lower alkyl group, a lower alkenyl group and an optionally substituted benzyl group, a phenethyl group and a naphthylmethyl group, and R ² and R ³ represent a lower alkyl group, a lower alkyl group and a lower alkyl group. An alkoxy group and a lower alkenyl group, R ⁴ represents a hydrogen atom and a lower alkyl group, X represents a halogen atom, and A represents —C (CH ₃ ).
₂ -, - CO -, - indicating and -S- - SO _2. m and n represent an integer of 0 or 4 or less. ) In the substituents in the general formula of the present invention, a lower alkyl group is a side chain such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, an amyl group and an isoamyl group. A lower alkenyl group is a vinyl group, a 2-propenyl group, a 1-propenyl group, a 1-butenyl group, a 2-butenyl group. , A 3-butenyl group, an isobutenyl group, and the like, which means an alkenyl group having 2 to 5 carbon atoms which may have a side chain, and a lower alkoxy group is a methoxy group, an ethoxy group, a propoxy group, iso 1 to 5 carbon atoms which may have a side chain such as propoxy group, butoxy group, isobutoxy group, tert-butoxy group, amyloxy and isoamyloxy group.
Means an alkoxy group. The substituents of the benzyl group, the phenethyl group and the naphthylmethyl group which may have a substituent mean the lower alkyl group, the lower alkoxy group and the halogen atom which are synonymous with the above. The naphthylmethyl group includes α-naphthylmethyl group and β-naphthylmethyl group.

Next, as epihalohydrin represented by the general formula (III), epichlorohydrin, epibromohydrin, epiiodidohydrin, 2-methylepichlorohydrin, 2-ethylepichlorohydrin, 2 -Propyl epichlorohydrin, 2-methyl epibromohydrin, 2-ethyl epibromohydrin, 2-propyl epibromohydrin, 2-methyl epiiodidohydrin,
Typical examples include 2-ethylepiiodidohydrin and 2-propylepiiodidohydrin.

Typical examples of the quaternary ammonium salt, tertiary amine, phosphonium salt and sulfonium salt which are catalysts include the following. Examples of the quaternary ammonium salt include ammonium chloride, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide,
Tetraethylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrahexylammonium iodide, benzyltriethylammonium chloride, trioctylmethylammonium chloride, benzyltributylammonium chloride, diethanolmethyldecane ammonium bromide, di Examples include methanol methyldecane ammonium bromide.
Examples of the tertiary amine include 4-dimethylaminopyridine, triethylamine, triethanolamine, pyridine, picolines and the like. Examples of the phosphonium salt and sulfonium salt include tetrabutylphosphonium bromide and trimethylsulfonium iodide.

In the production method of the present invention, an aromatic hydroxy compound represented by the general formula (II) is subjected to an addition reaction with an epihalohydrin represented by the general formula (III) in the presence of a catalyst to obtain the compound represented by the general formula (IV). It consists of two reactions in which the 2-propanol compound represented is prepared and then epoxy-cyclized with a dehydrohalogenating agent to prepare the monoglycidyloxy compound represented by the general formula (I). These reactions will be described in detail.

The first reaction also has a catalytic effect for promoting the dehydrohalogenation reaction of the 2-propanol compound of the general formula (IV) produced by the catalyst used, and a part of the 2-propanol compound is The target compound is a monoglycidyloxy compound of the general formula (I). This characteristic is considered preferable, but industrially, the released hydrogen halide is added to epihalohydrin to open the epoxy ring and consumes expensive epihalohydrin, which is rather a drawback. The inventors have found that a hydrogen halide-epihalohydrin adduct having an epoxy ring opened can be converted to the original epihalohydrin by dehydrohalogenation when heated to a boiling temperature under normal pressure. Incidentally, the liberated hydrogen halide undergoes a reaction opposite to the above characteristic and is added to the monoglycidyloxy compound to form the 2-propanol compound. The present invention has completed a method for producing epihalohydrin that does not participate in the reaction with a high recovery rate even if a large amount of expensive epihalohydrin is used. That is, in the first reaction, 1 part by weight of an aromatic hydroxy compound is dissolved or dispersed in 4 parts by weight or more, preferably 6 to 8 parts by weight of epihalohydrin, a catalyst is added, and a reaction temperature of 70
It is a method of reacting at ˜130 ° C. for 2 to 24 hours, and after completion of the reaction, excess epihalohydrin is recovered under normal pressure and completed. In this case, the proportion of the catalyst used is 10 to 0.01 parts by weight per 100 parts by weight of the aromatic hydroxy compound,
It is preferably 5.0 to 0.05 parts by weight. This reaction is
For example, toluene, xylene, cumene, chlorobenzene,
It can also be carried out in an inert organic solvent such as dichlorobenzene. However, it is not a preferable method because the reaction rate decreases in an organic solvent and the recovery of epihalohydrin becomes difficult.

In the second reaction, after the epihalohydrin is recovered, it is heated and dissolved / dispersed in an inert organic solvent such as toluene, xylene, cumene, chlorobenzene or dichlorobenzene to obtain a solid dehydrohalogenating agent or an aqueous solution thereof. In addition, heating is performed to completely epoxidize the 2-propanol compound to produce a monoglycidyl compound. As the dehydrohalogenating agent used here, for example, alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like are preferable, and the amount thereof is 1.0 part by weight of the aromatic hydroxy compound. On the other hand, 1.0 to 1.3 parts by weight is preferable. The monoglycidyl compound represented by the general formula (I) thus produced was highly pure white crystals, and they were effective as an image storage stabilizer for heat-sensitive recording materials.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. Example 1 34 g (0.1 mol) of 4-hydroxy-4′-benzyloxydiphenyl sulfone in 300 ml Kolben, 2-
Methyl epichlorohydrin 85.3 g (0.8 mol) and tetrabutylammonium bromide 1.0 g (0.
003 mol) was added, and the mixture was reacted by heating and stirring at a reaction temperature of 85 to 90 ° C. for 6 hours. After completion of the reaction, excess 2-methylepichlorohydrin used as a solvent was recovered under normal pressure. The recovery rate was 95% of the amount not involved in the reaction. Next, 200 ml of toluene was added to the product and the product was heated and dissolved. 22 g of a 20% aqueous sodium hydroxide solution was added, and the mixture was heated under reflux for 1 hour. The toluene layer was washed with water, concentrated, cooled, filtered and dried to give white crystals of 4- (2-methylglycidyl) oxy-4′-benzyloxydiphenylsulfone, melting point 160-162 ° C., 38.2 g. 4-
The yield from hydroxy-4′-benzyloxydiphenyl sulfone was 93%. Example 2 In place of the tetrabutylammonium bromide of Example 1, 0.13 g (0.09 mol) of triethanolamine was used, and the reaction was carried out at 100 ° C. at a reaction temperature of 100 ° C. (2-methylglycidyl) oxy-
White crystals of 4'-benzyloxydiphenyl sulfone,
37.8 g of melting point 160-162 degreeC was obtained. The yield in this case was 92%. Example 3 Instead of the tetrabutylammonium bromide of Example 1, benzyltriethylammonium chloride 0.7
g (0.003 mol) was used and reacted in the same manner as in Example 1 to give 4- (2-methylglycidyl) oxy-4 ′.
-White crystals of benzyloxydiphenyl sulfone, melting point 160-162 [deg.] C, 38.1 g were obtained. The yield in this case was 93%. Example 4 In the same manner as in Example 1, 29.3 g (0.1 mol) of 4-hydroxy-4′-isopropoxydiphenyl sulfone was used.
And epichlorohydrin 55.0 g (0.6 mol) are used, and catalyst trimethylsulfonium iodide 1.0 g
Reacting in the presence of (0.0049 mol), white crystals of 4-glycidyloxy-4′-isopropoxydiphenyl sulfone, melting point 132.8-133.9 ° C., 32.3.
g was obtained. The yield in this case was 93%.

Example 5 Various compounds replacing 4-hydroxy-4'-benzyloxydiphenyl sulfone of Example 1 and 2-methylepichlorohydrin were prepared according to Example 1. The compound and melting point are shown below. The yield of these is 90
Was ~ 95%. 4- (2-Methylglycidyl) oxy-4 ′-(2-chlorobenzyl) oxydiphenylsulfone Melting point 139-145 ° C. 4- (2-Methylglycidyl) oxy-4 ′-(4-chlorobenzyl) oxydiphenylsulfone Melting point 164-166 ° C. 4- (2-Methylglycidyl) oxy-4 ′-(4-methylbenzyl) oxydiphenylsulfone Melting point 143-145 ° C. Example 6 4-hydroxy-4′-benzyloxydiphenylsulfone of Example 1 Various alternative compounds and epichlorohydrin were prepared according to Example 1. The compound and melting point are shown below. The yield of these was 90 to 95%. 4-glycidyloxy-4 '-(4-chlorobenzyl) oxydiphenylsulfone, melting point 140-141 ° C 4-glycidyloxy-4'-(4-methylbenzyl) oxydiphenylsulfone, melting point 126-127 ° C 4-glycidyloxy -4'-allyloxydiphenyl sulfone Melting point 164-165 ° C 4-Glycidyloxy-4 '-(α-naphthylmethyl) oxydiphenylsulfone Melting point 193-194 ° C Comparative Example 1 The tetrabutylammonium bromide of Example 1 is not used. Then, the reaction is performed in the same manner as in Example 1 below, and 4-
White crystals of (2-methylglycidyl) oxy-4′-benzyloxydiphenyl sulfone, melting point 159-162.
C., 19.0 g was obtained. The yield in this case was 46%, and the yield was significantly reduced by the method using no catalyst.

[0012]

INDUSTRIAL APPLICABILITY When a monoglycidyloxy compound represented by the general formula (I) which is an image stabilizer for heat-sensitive recording paper is produced, a quaternary ammonium salt, a tertiary amine, a phosphonium salt or a sulfonium salt is used as a catalyst. By reacting using one or more, a high yield of 90 to 95% from the aromatic hydroxy compound could be obtained. Even if expensive epihalohydrin is used as a solvent, it is an economically excellent production method which can be obtained with a high recovery rate.

Claims (2)

[Claims] 1. A quaternary ammonium salt which is a catalyst of an aromatic hydroxy compound represented by the general formula (II) and an epihalohydrin represented by the general formula (III), a tertiary amine,
A general formula (I) in which a 2-propanol compound represented by the general formula (IV) is produced by reacting in the presence of at least one of a phosphonium salt and a sulfonium salt, and then reacted in the presence of a dehydrohalogenating agent. The manufacturing method of the monoglycidyl oxy compound represented by. (In the above general formula, R ¹ represents a lower alkyl group, a lower alkenyl group and an optionally substituted benzyl group, a phenethyl group and a naphthylmethyl group, and R ² and R ³ represent a lower alkyl group, a lower alkyl group and a lower alkyl group. An alkoxy group and a lower alkenyl group, R ⁴ represents a hydrogen atom and a lower alkyl group, X represents a halogen atom, and A represents —C (CH ₃ ).
₂ -, - CO -, - indicating and -S- - SO _2. m and n represent an integer of 0 or 4 or less. ) 2. A method for producing a monoglycidyloxy compound represented by the general formula (I) according to claim 1, wherein A is —SO ₂ — in the general formula.