JPS61293952A - Hydroxybenzoate and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [R is alky, alkoxy or halogen; Rs may be the same or different substituent groups when >=2 R groups are present (n is >=2 and/or qis >=2); m and p are integers 1-5; n and q are 0 or integers 1-4; m+n is <=5 and p+q is <=5]. EXAMPLE:3-Hydroxyphenyl-2,4-dihydroxybenzoate. USE:An ultraviolet light absorber, raw material for hydroxybenzophenone which is an electronic material, light stabilizer for plastics and fibers, sunscreen agent, component stabilizer for dyestuff or perfume, etc. PREPARATION:A hydroxybenzene expressed by formula II (i is an integer 1-5; j is 0 or an integer 1-4; i+j is <=5) is reacted with phosgene in a solvent, e.g. nitrobenzene, at 50-150 deg.C to afford the aimed compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel hydroxybenzoate and a method for producing the same. The hydroxybenzoate of the present invention can be used as an ultraviolet absorber, as a light stabilizer for plastics and textiles, as a sun protection agent in the cosmetics field, as a component stabilizer for pigments, fragrances, etc., or as a raw material for hydroxybenzophenone used in electronic materials. It is used.

[Prior art]

Although the new hydroxybenzoate is used as a raw material for hydroxybenzophenone, conventional methods for producing 2゜2', 4,4'-tetrahydroxybenzophenone, which is typical among hydroxybenzophenones, include, for example, U.S. Patent No. 2,854, No. 485, No. 2.921
, 962, a method of reacting ρ-resorcinic acid and resorcin in the presence of zinc chloride and phosphoric acid and phosphorus oxychloride or phosphorus trichloride;
, 694, 729, a method is known in which resorcinol dimethyl ether and phosgene are reacted in the presence of aluminum chloride using a chlorinated hydrocarbon as a solvent.

[Problem that the invention seeks to solve]

However, these conventional methods have low yields and are colored, making it difficult to obtain highly pure 2.2', 4,4'-tetrahydroxybenzophenone.

[Means for solving problems]

The present invention provides hydroxybenzoate useful as a raw material for hydroxybenzophenone used in ultraviolet absorbers or electronic materials, and a method for producing the hydroxybenzoate in high yield.

As described below, hydroxybenzophenone can be obtained from hydroxybenzoate in high yield and with little coloration.

Specifically, the present invention general formula Hydroxybenzoate represented by

This is a method for producing hydroxybenzoate represented by the general formula, by reacting one or more hydroxybenzenes represented by the general formula with phosgene.

Droxybenzene used in the present invention is a compound represented by: R is a methyl group, an ethyl group, a propyl group,
Examples include alkyl groups having 1 to 12 carbon atoms such as butyl group and octyl group, and alkyl groups having 1 to 12 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group, and octoxy group. In addition, when j represents an integer of 2 or more, R
may be substituents of the same or different classes. Examples of the compound represented by the above general formula include catechol, resorcinol, hydroquinone, 1,2.8-)lyhydroxybenzene, resorcinol-
Monomethyl ether, resorcinol monooctyl ether, 8,5-dihydroxytoluene and the like can be mentioned.

These hydroxybenzenes are selected depending on the desired hydroxybenzoate and the type of hydroxybenzophenone derived therefrom.

For example, in the case of 3-hydroxyphenyl-2,4-dihydroxybenzoate, resorcinol is used.

Another reactant used in carrying out the process of the invention is phosgene. Both hydroxybenzene and phosgene can be purified to a high degree of purity, or they can be used as they are industrially produced. The method of the present invention can also be used without a catalyst.
It can also be carried out using zirconium halide as a catalyst. Preferably, the zirconium halide is a chloride, the Ffl is a bromide, or a mixture thereof.

Hydroxybenzene and phosgene are generally reacted in the presence of a solvent. That is, in the case of no catalyst, hydroxybenzene is dissolved or suspended in a solvent, or when zirconium halide is used as a catalyst,
Generally, a method is employed in which hydroxybenzene and zirconium halide are dissolved or suspended in a solvent and phosgene is blown thereinto to cause a reaction. As solvents, carbon disulfide, nitrobenzene, halogenated hydrocarbons such as l.

2-dichloroethane, chlorobenzene, bromobenzene, 0-dichlorobenzene, m-dichlorobenzene, etc. can be used.

When carrying out the reaction without a catalyst, the amounts of hydroxybenzene, solvent, and phosgene used are generally 8 to 40% by weight relative to the solvent, and the amount of phosgene used is the theoretical amount relative to hydroxybenzene. The amount used is about 0.5 to 8 times the mole, preferably about 1 to 4 times the mole. The reaction temperature is generally carried out at about 5.alpha.6 to 150.degree. C., preferably about 70.degree. to 130.degree. When the concentration of hydroxybenzene in the solvent exceeds about 40 M%, the proportion of by-products produced increases, while when the concentration decreases, productivity deteriorates. Further, even if a large amount of phosgene is used, a commensurate effect cannot be obtained, so it is generally used in about 0.5 to 8 times the molar amount, preferably about 1 to 4 times the molar amount. Regarding the reaction temperature, if the temperature is above a suitable temperature range, the amount of by-products will increase significantly, while if it is below a suitable temperature range, it will take a long time to complete the reaction.

When using zirconium halide as a catalyst, the amounts of hydroxybenzene, solvent, and phosgene to be used may be the same as in the case of no catalyst, and the amount of zirconium halide used as a catalyst is about 0.0% per mole of hydroxybenzene. The reaction temperature is generally about 0 to 90°C, preferably about 20 to 50°C. If the amount of zirconium halide used is approximately twice the mole or more, or if the temperature exceeds a suitable temperature range, the by-products will increase significantly and the proportion of hydroxybenzoate produced will decrease; If it is less than about 0.1 mole, or if the temperature is below the preferred range, it will take a long time to complete the reaction.

The time for blowing phosgene may be within a range that does not cause abnormal heat generation due to the blowing.

It is effective to provide an aging time of about 1 to 20 hours to complete the reaction after the introduction of phosgene. Regarding the difference between carrying out the reaction without a catalyst and carrying out the reaction in the presence of zirconium halide as a catalyst, when carrying out the reaction without a catalyst, the reaction must be carried out at a slightly higher temperature. However, it can be produced with a high yield of 70% or 80% or more and with good selectivity. When the reaction is carried out in the presence of zirconium halide as a reaction medium, in addition to the advantage that it can generally be carried out at a lower temperature, the zirconium halide itself is active in the Fries rearrangement of hydroxybenzoate, making it possible to produce hydroxybenzophenone. In this case, it has the advantage that the hydroxybenzoate can be easily converted to hydroxybenzophenone without isolating it by making slight changes in the reaction temperature, zirconium halide, etc. and reaction conditions.

The hydroxybenzoate produced by Tomoo can be isolated by washing the reaction product with water to remove unreacted hydroxybenzene, then evaporating and recovering the solvent, and performing concentration crystallization. Although a less colored hydroxybenzoate can be obtained by concentration crystallization, it is also possible to carry out further purification such as recrystallization, if desired.

Hydroxybenzoates obtained in this way include 3-hydroxyphenyl-2,4-dihydroxybenzoate, 2-hydroxyphenyl-8,4-dihydroxybenzoate, 4-hydroxyphenyl-2, depending on the hydroxybenzene used in the reaction. ,5-dihydroxybenzoate 2-hydroxyphenyl-2,4-dihydroxybenzoate 3-hydroxyphenyl-3,4-dihydroxybenzoate 4-hydroxyphenyl-2,4-dihydroxybenzoate 3-hydroxyphenyl-2,5-dihydroxybenzoate 2 -Hydroxyphenyl-2,5-dihydroxybenzoate 4-Hydroxyphenyl-8,4-dihydroxybenzoate 2.8-Dihydroxyphenyl-2,8,4-trihydroxybenzoate (3-hydroxy-5-methyl)phenyl-(2 ,4-
dihydroxy-6-methyl)benzoate 3-methoxyphenyl-(2-hydroxy-4-methoxy-)benzony 1 and the like.

[Effect of cleaning]

By the method of the present invention detailed above, a novel hydroxybenzoate used as a raw material for polyhydroxybenzophenone useful in ultraviolet absorbers and the like can be produced in high yield, and its industrial value is great.

〔Example〕

The method for producing hydroxybenzoate and various physical properties are shown below in Examples.

Example 1 (Reaction without catalyst) 1 kg of nitrobenzene and 110 y of resorcinol were charged into a 21 t four-bottle flask, and the temperature of the flask was raised to 100'C in a tank replaced with N2, and phosgene was
9 f. was blown under stirring for 10 hours.

As the phosgene was blown into the reactor, the color of the reaction solution changed from light brown to blackish brown, and it was observed that HCl gas was generated during the phosgene blowing. The reaction solution was once cooled to room temperature, washed three times with 500 y of cold water, and then the organic layer was subjected to shrinkage and crystallization on cooling to precipitate a white product. The white product was then filtered, washed with water, and dried under reduced pressure.
A colored powder was obtained. Yield: 89.5 g (equivalent to hydroxybenzoate purity 99.0%, yield 72.0%).

The crude hydroxybenzoate thus obtained was developed using a high-performance liquid chromatogram using water-methanol as an eluent, and 8-hydroxyphenyl and 2,4-dihydroxybenzoate were fractionated.

The optical properties, mass spectrometry, elemental analysis, and melting point of 3-hydroxyphenyl-2,4-dihydroxybenzoate were measured.

・Infrared absorption (see Figure 1) 8400cI&' 0-H extension IQ 1660z
C=C stretching vibration/mass spectrometry: 4 m, /e:st* 110.187.246 (parent peak) 0 elemental analysis: C (%) H (%) experimental value
63,58 8.95 Theoretical value 63.42 4.09 0 Melting point 169.5°C.

Example 2c Reaction in the presence of zirconium halide) 1
．． 1 kq of 2-dichlorothane, 110 g of lursorcin, and 2117 g of silconium chloride A 85 f'e were charged into a four-bottle flask, and the inside of the flask was replaced with N2 gas, and then the temperature was raised to 85°C. Next, phosgene was bubbled in at 150F for 7 hours with stirring while maintaining the temperature at 85C, followed by aging for 4 hours. After the completion of aging, the reaction product was cooled and analyzed by high performance liquid chromatography, and the yield of 8-hydroxyphenyl-2,4-dihydroxybenzoate was 65%.
%, and the conversion rate of resorcinol was 82%.

At this time, 7% of 2.2', 4,4'-tetrahydroxybenzophenone was produced.

Reference Example 1 Hydroxybenzoate 24.6f obtained in Example 1
1 nitrobenzene a o o y, zirconium chloride 1
2. Fill three 500 cc flasks with N2
After the fa exchange, the temperature was raised to 70°C, heat treated at 70°C for 4 hours, and then aged for 4 hours. After cooling, the reaction solution was analyzed by high-performance liquid chromatography, and it was found that 99% of the hydroxybenzoate was converted, and 2.2', 4.4'-tetrahydroxybenzophenone was produced in a 94% yield (based on hydroxybenzoate). I found out that it is.

Reference Example 2 Nitrobenzene t# and 110 g of resorcin were charged into a 211 four-bottle flask, and after replacing the inside of the flask with N2, 1
The temperature was raised to 00°C, and phytosgene was blown in at 99°F for 10 hours with stirring. As phosgene was blown in, the color of the reaction solution changed from light brown to blackish brown.
Generation of Cl gas was observed. After cooling the reaction solution to room temperature, the reaction solution was analyzed using high-performance liquid chromatography, and it was found that hydroxybenzoate was produced at a yield of 80% based on resorcinol.)Next, zirconium chloride j16 was added to the reaction solution. .5. After the temperature was raised to 70°, heat treatment was performed at 70°C for 2 hours. After the heat treatment, the reaction product was cooled with water, 7001 drops of water was added, and after leaving it for 1 hour with stirring, the reaction product was filtered, washed with water, and
Got a wet cake. The wet cake was dissolved in 2 parts of hot water, cooled and crystallized, and dried to obtain the desired 2°2
', 4.4'-tetrahydroxybenzophenone 9
0. (1' was obtained (yield 76% m, p.

(196-199℃) At this time, the conversion rate of resorcin was 89%.
The amount of unconverted hydroxybenzoate was 8% (based on resorcinol).

[Brief explanation of drawings]

The first figure shows an infrared absorption spectrum of 3-hydroxyphenyl-2,4-dihydroxybenzoate produced by the method of Example 1.

Claims (1)

[Claims] 1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [R represents an alkyl group, an alkoxy group, or a halogen atom, and when R is 2 or more (n≧2 and/or q≧2) may be the same substituent or different substituents. m and p are 1
an integer of ~5, n and q are 0 or integers of 1 to 4, m
+n≦5 and p+q≦5. ]Hydroxybenzoate. 2) The hydroxybenzoate according to claim 1, which is 3-hydroxyphenyl-2,4-dihydroxybenzoate represented by the formula ▲ (numerical formula, chemical formula, table, etc.). 3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. Also good. i is an integer of 1 to 5, j is 0 or an integer of 1 to 4, and i+j≦5. ] By reacting one or more hydroxybenzenes represented by phosgene with phosgene, the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [R represents an alkyl group, an alkoxy group, a halogen atom, In the case of 2 or more (n≧2 and/or q≧2), the substituents may be the same or different. m and p are integers of 1 to 5, n and q are integers of 0 or 1 to 4,
m+n≦5 and p+q≦5. ] A method for producing hydroxybenzoate. 4) The manufacturing method according to claim 3, wherein the hydroxybenzene is resorcinol and the hydroxybenzoate is 8-hydroxyphenyl-2,4-dihydroxybenzoate.