JPH05246924A - Production of 2-propanol compound - Google Patents

Abstract

PURPOSE:To obtain the subject compound in good yield by reacting an aromatic dihydroxy compound with a glycidyl ether compound in a polar organic solvent using either one of a quaternary salt, tert. amine, a phosphonium salt and a sulfonium salt as a catalyst. CONSTITUTION:An aromatic dihydoxy compound of formula II is reacted with a glycidyl ether compound of formula III [R<1> to R<3> are halogen, alkyl, etc.; R<4> is H or alkyl; X is C(CH3)2, CO, SO2, etc.; (m), (n) and (p) are 0-4] to provide a new 2-propanol compound of formula I [e.g. 1-phenoxy-3-[4-(4- hydroxyphenylsulfonyl)-phenoxy]-2-propanol]. The reaction is carried out using one or more kinds of a quaternary ammonium salt, a tertiary amine, a phosphonium salt and a sulfonium salt (e.g. triethanolamine) as a catalyst in a polar organic solvent (e.g. methylisobutyl ketone). According to this method, the compound of formula I is obtained by subjecting the compound of formula III to additional reaction with only either one hydroxy group of a compound of formula II without using a specific protecting group, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a 2-propanol compound useful as an image storage stabilizer for heat-sensitive recording paper.

[0002]

2. Description of the Related Art Generally, the reaction between an epoxy compound and a phenolic compound is aimed at the synthesis of a polymer resin such as an epoxy resin or a polyether resin. For example, a method of reacting epichlorohydrin and two molecules of phenols in water or a suitable solvent in the presence of a basic catalyst to synthesize a glycerol α, α′-diaryl ether compound is O, Stephenson JCS, .1954, 1571. US Pat. No. 2,359,622 discloses a method of reacting an alkali metal salt of a diphenol compound represented by the general formula (II) with an olefin halohydrin to add an olefin halohydrin to both phenolic hydroxyl groups. No. However, as described above, although there are many reports of synthesis aimed at polymer resins, there is no example of addition reaction of an epoxy compound to only one hydroxyl group of a diphenol compound as in the present invention. On the other hand, the 2-propanol 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 thermal recording paper from being erased by the packaging resin.

[0003]

The glycidyl compound is added to only one hydroxy group of the aromatic dihydroxy compound without using a special protecting group or the like, and is represented by the general formula (I) containing few impurities. This is a method for producing a 2-propanol compound in good yield.

[0004]

The present invention has the general formula (II)
And an aromatic dihydroxy compound represented by the general formula (II
A glycidyl ether compound represented by I) and a catalyst of 4
A method for producing a 2-propanol compound represented by the general formula (I), which comprises reacting in a polar organic solvent in the presence of at least one of a secondary ammonium salt, a tertiary amine, a phosphonium salt and a sulfonium salt. (In the above general formula, R ¹ , R ² and R ³ represent a halogen atom, a lower alkyl group, a lower alkoxy group and a lower alkenyl group, R ⁴ represents a hydrogen atom and a lower alkyl group, and X represents —C ( _{CH 3) 2 -, - CO} -, - SO 2
-And-S- are shown, ring A is a benzene ring or a naphthalene ring, and m, n, and p are 0 or an integer of 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. Means an alkyl group having 1 to 5 carbon atoms which may have, a lower alkoxy group is a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tert-butoxy group. 1 to 5 carbon atoms which may have a side chain such as a group, amyloxy and isoamyloxy group
The lower alkenyl group means a vinyl group, 1-propenyl group, 2-propenyl group,
2 carbon atoms which may have a side chain such as 1-butenyl group, 2-butenyl group, 3-butenyl group and isobutenyl group
~ 5 alkenyl groups are meant.

As the aromatic dihydroxy compound represented by the general formula (II), 4,4'-dihydroxydiphenylsulfone and its derivative, 2,2'-bis (4-hydroxyphenyl) propane and its derivative, di ( 4-hydroxyphenyl) ketone and its derivatives, 4,4'-
Examples thereof include dihydroxydiphenyl thioether and derivatives thereof, and each derivative has the above substituents in any combination. Specifically, 4,4'-dihydroxydiphenyl sulfone, 3,3'-diallyl-4,4'-
Dihydroxydiphenyl sulfone, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfone, 2,
Typical examples include 2'-bis (4-hydroxyphenyl) propane, di (4-hydroxyphenyl) ketone, di (4-hydroxyphenyl) thioether and the like.

Next, as the glycidyl ether compound represented by the general formula (III), a lower alkylphenyl group such as phenyl group and tolyl group, a halogenated phenyl group such as chlorophenyl group, an alkoxyphenyl group such as methoxyphenyl group, Examples thereof include a glycidyl ether compound having an alkenylphenyl group such as an allylphenyl group as a substituent and a 2-alkyl-substituted glycidyl ether compound. Specifically, o-tolyl glycidyl ether, m-tolyl glycidyl ether, p-tolyl glycidyl ether, p-chlorophenyl glycidyl ether, m-chlorophenyl glycidyl ether, 2,4-dimethylphenyl glycidyl ether, 3,5-dimethylphenyl glycidyl Ether, p-ethylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, p-phenylphenyl glycidyl ether, p-methoxyphenyl glycidyl ether, 2,4,6-trimethylphenyl glycidyl ether, β-naphthyl glycidyl ether, phenyl -2-methyl glycidyl ether, p-chlorophenyl-2-methyl glycidyl ether, 3,5-dimethylphenyl-2-methyl glycidyl ether, p-ethyl Phenyl-2-methylglycidyl ether, p-tert-butylphenyl-2-methylglycidyl ether, p-phenylphenyl-2-methylglycidyl ether, 2,4,6-trimethylphenyl-2-methylglycidyl ether, β-naphthyl −
2-Methyl glycidyl ether etc. are mentioned as a typical thing.

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 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, diethanolmethyldecaneammonium bromide, dimethanolmethyldecaneammonium bromide and the like can be mentioned. As a tertiary amine,
Examples thereof include 4-dimethylaminopyridine, triethylamine, triethanolamine, pyridine, 1,8-diazabicycloundecene, 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, only one hydroxy group of the aromatic dihydroxy compound represented by the general formula (II) is used in the general formula (III) without using a special protecting group or the like.
Is a method for selectively producing a 2-propanol compound represented by the general formula (I) by addition-reacting a glycidyl ether compound represented by. That is, the general formula (I
An aromatic dihydroxy compound represented by I), a catalyst, and a polar organic solvent are added, and the mixture is heated and dissolved or dispersed. Then, the reaction temperature is 100 to 150 ° C, preferably 110 to 130 ° C.
Then, the glycidyl ether compound represented by the general formula (III) is added and reacted for 3 to 12 hours to produce a 2-propanol compound of the general formula (I). At this time, when the reaction temperature is high, the production of by-products such as polymerization is increased, and when the reaction temperature is low, the reaction progresses slowly.
The reaction temperature is preferably a method in which the polar organic solvent used is refluxed from the viewpoint of industrial operability. After completion of the reaction, the polar organic solvent layer may be subjected to post-treatment such as concentration to obtain a crude product of the target compound, which may be purified by recrystallization with an appropriate polar organic solvent or non-polar organic solvent. At that time, an alkaline aqueous solution is added to the reaction solution to make it alkaline, preferably pH 10 or less, to recover an excess of the aromatic dihydroxy compound, or to make it strong alkaline, and the target compound is extracted into an aqueous layer to obtain a by-product. It can also be purified by leaving it in the polar organic solvent for separation, then neutralizing the aqueous layer and extracting the target compound into an appropriate polar organic solvent or a nonpolar organic solvent, in any combination. In the reaction, the amount of the aromatic dihydroxy compound of the general formula (II) used is 1.0 to 3 mol, preferably 1.2 to 1.8 mol, per 1 mol of the glycidyl ether compound of the general formula (III). The ratio of the catalyst used is 0.01 mol or more per 1 mol of the glycidyl ether compound, and the catalyst may be used instead of the solvent in some cases.

In this reaction, a polar organic solvent is used, but this increases the solubility of the aromatic dihydroxy compound of the general formula (II) in the reaction system, and the polar organic solvent with the glycidyl ether compound of the general formula (III) is used. Improves reactivity and increases the general formula (I)
To increase the selectivity to the 2-propanol compound. That is, the polar organic solvent of the present invention is inert to the reaction system, has a boiling point of 100 ° C. or higher, and is represented by at least the aromatic dihydroxy compound represented by the general formula (II) and the general formula (I). -A polar organic solvent that dissolves the propanol compound is preferred. Examples of such an organic solvent include solvents such as methyl isobutyl ketone, dimethyl sulfoxide, dimethylformamide, butanol and hexanol. The 2-propanol 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 2 l Kolben with 500 ml of methyl isobutyl ketone, 4,
187.5 g of 4'-dihydroxydiphenyl sulfone
(0.75 mol), triethanolamine 7.5 g
(0.05 mol) was added and the mixture was heated and dissolved. Then add 75 g (0.5 mol) of phenyl glycidyl ether and add 4
The mixture was heated to reflux for reaction. After the reaction is completed, 4% in the reaction solution
Aqueous sodium hydroxide solution was added to adjust the pH of the aqueous layer to 9.8 for washing. When the aqueous layer separated and separated was acidified with hydrochloric acid, 57 g of 4,4′-dihydroxydiphenyl sulfone as a raw material could be recovered. Furthermore, the washed water layer is p
An 8% aqueous sodium hydroxide solution was added until H12 or more, the target compound was transferred to the aqueous layer, and the aqueous layer was separated. The aqueous layer was acidified with hydrochloric acid to obtain a free crude oily target compound. The crude product was recrystallized from ethyl acetate to obtain white crystals of the target compound, 1-phenoxy-3- (4- (4-hydroxyphenylsulfonyl) phenoxy) -2-propanol, melting point 140-142 ° C, 152 g. .. The yield from phenylglycidyl ether is 76.
%Met. Example 2 In 200 ml Kolben, 12.5 g (0.058 mol) of 4,4'-dihydroxybenzophenone, 40 ml of methyl isobutyl ketone, 0.5 g of triethanolamine.
(0.003 mol) was added and the mixture was heated and dissolved. Then, 7 g (0.047 mol) of phenylglycidyl ether was added, and the same treatment as in Example 1 was performed to obtain the target compound, 1-
Phenoxy-3- (4- (4-hydroxybenzoyl)
Phenoxy) -2-propanol white crystals, melting point 10
Obtained was 12.2 g at 8 to 109 ° C. The yield from phenylglycidyl ether was 72%.

Comparative Example 1 Reaction was carried out for 8 hours in the same manner as in Example 1 except that triethanolamine was not used. After completion of the reaction, 4% aqueous sodium hydroxide solution was added to the reaction solution to adjust the pH of the aqueous layer to 9.8, and the aqueous layer was separated. When the aqueous layer was acidified with hydrochloric acid, most of the raw material 4,4′-dihydroxydiphenyl sulfone was recovered. Comparative Example 2 The reaction was performed in the same manner as in Example 1 except that xylene was used instead of the methyl isobutyketone of Example 1 in the scale of 0.1 times that in Example 1. The same treatment was performed to obtain 1-phenoxy-3- (4- (4-hydroxyphenylsulfonyl) phenoxy) -2-propanol as white crystals, melting point 139 to 141 ° C, and 7.2 g. The yield from phenylglycidyl ether was 36%. In addition, pH 1
From the xylene residual liquid layer after separating the aqueous layer after making 2 or more,
By-product bis [4], in which two molecules of phenylglycidyl ether are bonded to 4,4'-dihydroxydiphenyl sulfone
8.1 g of-(3-phenoxy-2-hydroxypropoxy) phenyl] sulfone was obtained, and it was revealed that a large amount of by-products were formed when a nonpolar solvent was used.

[0012]

INDUSTRIAL APPLICABILITY In the present invention, the glycidyl ether compound can be added to only one of the hydroxy groups in a high yield without introducing a special protecting group into the aromatic dihydroxy compound, and the obtained 2 The propanol compound has a high purity and can be used as an image stabilizer for heat-sensitive recording paper without stains on the background.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical indication C07C 45/64 49/84 G 6917-4H 315/04 317/22 7419-4H 319/20 323/20 7419- 4H

Claims (2)

[Claims] 1. An aromatic dihydroxy compound represented by the general formula (II) and a glycidyl ether compound represented by the general formula (III) among quaternary ammonium salts, tertiary amines, phosphonium salts and sulfonium salts. A method for producing a 2-propanol compound represented by the general formula (I), which comprises reacting in a polar organic solvent in the presence of one or more kinds. (In the above general formula, R ¹ , R ² and R ³ represent a halogen atom, a lower alkyl group, a lower alkoxy group and a lower alkenyl group, R ⁴ represents a hydrogen atom and a lower alkyl group, and X represents —C ( _{CH 3) 2 -, - CO} -, - SO 2
-And-S- are shown, ring A shows a benzene ring or a naphthalene ring, and m, n, and p show an integer of 0 or 4 or less. ) 2. The method for producing a 2-propanol compound represented by the general formula (I) according to claim 1, wherein X is —SO ₂ — or —CO— in the general formula.