JP2983515B2 - Method for producing bisbenzotriazolylphenol compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to the Ru <br/> relates to a manufacturing how the polycondensation reactive bis-benzotriazolyl phenol compound.

[0002]

2. Description of the Related Art 2-Hydroxyphenylbenzotriazole compounds are known as so-called ultraviolet absorbers which are useful for protecting plastics from being damaged by ultraviolet rays.
However, most of conventionally known ultraviolet absorbers are low molecular compounds, and thus have many problems.

For example, the above-mentioned benzotriazole-based UV absorber has a low vapor pressure due to its low molecular weight, and evaporates when it is blended with a resin for molding to contaminate the working environment or stain the mold. Problems are known to occur.
Further, ultraviolet absorbers such as the above-mentioned benzotriazole-based ultraviolet absorbers are additive types, and are used by simply mixing them with the base resin. In addition, there is a possibility that the product cannot be provided with an ultraviolet absorbing effect (light stability) for a long period of time due to, for example, outflow due to rain or water containing a detergent in a use environment.

[0004] In recent years, even in applications having a large specific surface area such as coatings and fibers, and in use forms such as molding and coating at high temperatures, high-molecular-weight ultraviolet absorbing materials which are less likely to bleed out or evaporate from the surface of the resin molded product. Agents have been developed as high performance weathering agents. The polymer type ultraviolet absorber is obtained by polymerizing a low molecular weight compound having an ultraviolet absorbing property, has a very low vapor pressure, and is less likely to evaporate even during a molding process requiring a high temperature.

JP-A-38-25036 and JP-A-6-25036
JP-A-5-51181 and JP-A-61-112062 disclose an addition-polymerized benzotriazole-based compound and a polymer ultraviolet absorber produced from this compound. Also, JP-A-2-188581 and JP-A-3
-200788, JP-A-3-39326,
JP-A-9-316060 discloses a condensation-polymerized benzotriazole-based compound.

[0006] These publications disclose reactive benzotriazole compounds having a polymerized side chain (reactive ultraviolet absorber).
And the usefulness of the polymeric ultraviolet absorber which can be derived therefrom. That is, such a polymer ultraviolet absorber has excellent ultraviolet absorbing ability, and furthermore, since the unit for absorbing ultraviolet light is chemically bonded to the polymer, the polymer ultraviolet absorber has a high absorption capacity. It can provide the resin with long-term weather resistance without causing transpiration or bleed-out.

[0007]

However, reactive UV absorbers, which are monomers of these high molecular UV absorbers, are themselves reactive (high in reactivity) and therefore have difficulty in synthesis. And has been. For example, JP-A-9-31
No. 6060 discloses a polycondensation reaction type bisbenzotriazolylphenol compound, that is, 2,2′-methylenebis [6- (2H-benzotriazol-2-yl)-.
The 4- (hydroxyalkyl) phenol compound uses 2-hydroxy-5-hydroxyalkylphenyl-2H-benzotriazoles as a synthetic intermediate, converts this compound into a Mannich base, and then performs a coupling reaction. It is manufactured by performing.

[0008] However, the above 2-hydroxy-5-
Since the hydroxyalkylphenyl-2H-benzotriazole compound has a hydroxyalkyl group having a higher reactivity than the phenolic hydroxyl group in the molecule, it is used for preparing the Mannich base and for preparing 2,2′-methylenebis [6- ( 2H-benzotriazol-2-yl) -4- (hydroxyalkyl) phenols cause many side reactions in any of the production steps in conducting the coupling reaction, so that the target compound is synthesized in good yield. Was sometimes difficult.

In addition, the above 2,2'-methylenebis [6
-(2H-benzotriazol-2-yl) -4- (hydroxyalkyl) phenols, 2-hydroxy-5-hydroxyalkylphenyl which is a synthetic intermediate thereof
2H-benzotriazoles and by-products produced by side reactions all have similar chemical properties, and it is difficult to separate and purify the desired product.

[0010] Therefore, when purifying the above-mentioned target substance, it is necessary to use a conventional method such as activated carbon treatment and recrystallization a plurality of times, which not only lowers the yield but also greatly increases the production cost in industrialization. There was a problem. The present invention provides a method for easily and efficiently synthesizing the 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (hydroxyalkyl) phenol compound (2), and a method for synthesizing the same. An object of the present invention is to provide a synthetic intermediate useful for a production method.

[0011]

SUMMARY OF THE INVENTION In view of the above-mentioned problems in the prior art, the present inventors have proposed 2,2'-methylenebis [6-
As a result of intensive studies to develop a method for efficiently and easily synthesizing the (2H-benzotriazol-2-yl) -4- (hydroxyalkyl) phenol compound (2), the following general formula (1) was obtained. The novel methylene bisphenol compound described in the literature not described is an important synthetic intermediate for efficiently and conveniently synthesizing the compound (2), and the methylene bisphenol compound (1)
The present inventors have found that the compound (2) can be simply and efficiently synthesized without generating a by-product when is used as a synthesis intermediate, and have completed the present invention.

General formula (1):

[0013]

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[0014] [wherein A is wherein the alkylene group of carbon number 1 to 6, group: -C (CH3) 2 - or a group: -C (C2
H5) (CH3) - . R ¹ and R ² are
The same or different is a hydroxyl group or a linear or branched hydroxyalkyl group having 1 to 12 carbon atoms. ]
That is, the bisbenzotriazolylphenol compound (2) of the present invention:

[0015]

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[0016] [In the formulas, A is an alkylene group of carbon number 1 to 6, group: -C (CH3) 2 - or a group: -C (C2
H5) (CH3) - . R ¹ and R ² are
The same or different is a hydroxyl group or a linear or branched hydroxyalkyl group having 1 to 12 carbon atoms. R
³ and R ⁴ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. The manufacturing method of
General formula (1):

[0017]

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[0018] [In the formulas, A is an alkylene group of carbon number 1 to 6, group: -C (CH3) 2 - or a group: -C (C2
H5) (CH3) - . R ¹ and R ² are
The same or different is a hydroxyl group or a linear or branched hydroxyalkyl group having 1 to 12 carbon atoms. ]
Wherein the methylene bisphenol compound represented by the formula (1) is used as a synthetic intermediate.

The methylene bisphenol compound represented by the above general formula (1) is most useful, for example, for easily and efficiently synthesizing a bisbenzotriazolylphenol compound (2) which is a polycondensation reaction type ultraviolet absorber. A synthetic intermediate. Such a methylene bisphenol compound of the present invention
When the above bisbenzotriazolyl phenol compound (2) is produced by using (1), JP-A-9-316060
Patent No. 5,049,098, such as the Mannich base compound of benzotriazole used in the production method disclosed in the publication, without any influence of a highly reactive hydroxyalkyl group having in the molecule, the functional group selectively phenolic hydroxyl group Since the reaction proceeds at the ortho position, only the target product, bisbenzotriazolylphenol compound (2), can be produced in high yield.

Further, the obtained bisbenzotriazolylphenol compound (2) has high purity with no by-products and low coloring degree, so that the purification step can be omitted in some cases. It can be manufactured at extremely low cost industrially.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below.
Each group represented by the above general formula (1) will be specifically described as follows. Examples of the alkylene group having 1 to 6 carbon atoms include methylene, ethylene, trimethylene, 2-methyltrimethylene, 2,2-dimethyltrimethylene,
-Alkylene groups such as methyltrimethylene, methylmethylene, ethylmethylene, tetramethylene, pentamethylene, hexamethylene and the like.

Examples of the linear or branched hydroxyalkyl group having 1 to 12 carbon atoms include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 2,3-dihydroxypropyl, 4-hydroxybutyl and , 1-dimethyl-2-hydroxyethyl, 5,
5,4-trihydroxypentyl, 5-hydroxypentyl, 6-hydroxyhexyl, 1-hydroxyisopropyl, 2-methyl-3-hydroxypropyl, 7-hydroxyheptyl, 8-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxy Examples thereof include a linear or branched alkyl group having 1 to 3 carbon atoms and having 1 to 3 hydroxyl groups such as decyl, 11-hydroxyundecyl and 12-hydroxydodecyl.

Further, each group represented by the above general formula (2) will be specifically described as follows. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl,
Alkyl groups such as isopropyl, butyl, isobutyl, t-butyl and the like can be mentioned. Examples of the alkoxy group having 1 to 4 carbon atoms include alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, and t-butoxy.

Examples of the halogen atom include a chlorine atom,
Examples thereof include a bromine atom, a fluorine atom, and an iodine atom.
Examples of the aryl group include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group and a naphthyl group which may have a halogen atom or the like on a phenyl ring.

The methylene bisphenol compound of the present invention
Specific examples of the compound (1) are shown below. 2,2′-methylenebis (1,4-dihydroxybenzene), 3,3 ′
-Methylenebis (4-hydroxybenzyl alcohol), 3,3'-methylenebis (4-hydroxyphenethyl alcohol), 2,2'-methylenebis [4- (3
-Hydroxypropyl) phenol], 2,2'-methylenebis [4- (2-hydroxypropyl) phenol], 2,2'-methylenebis [4- (4-hydroxybutyl) phenol), 2,2'-methylenebis [ 4-
(3-hydroxybutyl) phenol), 2,2′-methylenebis [4- (2-hydroxybutyl) phenol), 2,2′-methylenebis [4- (5-hydroxyamyl) phenol), 2,2′- Methylene bis [4-
(4-hydroxyamyl) phenol), 2,2′-methylenebis [4- (6-hydroxyhexyl) phenol), 2,2′-methylenebis [4- (7-hydroxyheptyl) phenol), 2,2′- Methylene bis [4
-(8-hydroxyoctyl) phenol), 2,2 '
-Methylenebis [4- (10-hydroxydecyl) phenol), 2,2'-methylenebis [4- (12-hydroxydodecyl) phenol).

The methylenebisphenol compound of the present invention represented by the above general formula (1) can be easily produced by various known methods. One preferred example is, for example, the following general formula (5):

[0027]

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[Wherein, R ¹ is a hydroxyl group or a group having 1 to 1 carbon atoms.
2 represents a linear or branched hydroxyalkyl group. Is aminomethylated by a Mannich reaction, and then, under basic conditions, another molecule of the hydroxyphenol (5 ′)

[0029]

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Wherein R ² is a hydroxyl group or a group having 1 to 1 carbon atoms.
2 represents a linear or branched hydroxyalkyl group. Or by reacting the above two molecules of hydroxyphenols (5) and (5 ′) with a predetermined aldehyde or ketone in an appropriate solvent in the presence of an acid catalyst. Thus, the desired methylenebisphenol compound represented by the general formula (1) can be produced.

Next, the manufacturing method of the present invention will be described. Using the methylene bisphenol compound represented by the general formula (1) as a synthetic intermediate, a compound represented by the general formula (2) according to a known method, for example, the production disclosed in Japanese Patent Publication No. 53733/1994.
2,2′- which is a polycondensation reaction type ultraviolet absorber represented by
Methylenebis [6- (2H-benzotriazole-2-
Yl) -4- (hydroxyalkyl) phenols can be produced.

Specifically, an o-nitroaniline derivative is reacted with sodium nitrite according to a conventional method, and is prepared by the following general formula (3):

[0033]

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[In the formula, R ³ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, an alkoxy group having 1 to 4 carbon atoms or a halogen atom. And a diazonium salt represented by the general formula (3 ′):

[0035]

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[In the formula, R ⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, an alkoxy group having 1 to 4 carbon atoms or a halogen atom. Azo coupling reaction of the diazonium salt represented by the formula (1) with the above methylenebisphenol compound (1) in a suitable solvent to give a general formula (4):

[0037]

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[0038] [wherein A is an alkylene group ,, group having a carbon number of 1~6: -C (CH3) 2 - or a group: -C (C
2H5) (CH3) - . R ¹ and R
² is the same or different and has a hydroxyl group or 1 to 12 carbon atoms
Is a straight-chain or branched-chain hydroxyalkyl group. R ³ and R ⁴ are the same or different and each represent a hydrogen atom,
C1-C4 alkyl group, aryl group, C1-C4
Represents an alkoxy group or a halogen atom. And then subjecting the bisazobenzene compound (4) to a reduction reaction under basic conditions to obtain a bisbenzotriazolyl phenol represented by the general formula (2). Compounds can be prepared.

The above methylene bisphenol compound
The azo coupling reaction between (1) and diazonium salts (3) and (3 ′) is preferably performed under basic conditions. In that case, as the base used, for example, lithium hydroxide,
Examples include lithium carbonate, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, potassium carbonate, potassium hydrogen carbonate, magnesium hydroxide, calcium hydroxide, calcium carbonate and the like. The amount of the compound used is 0.1% based on the methylenebisphenol compound (1).
The molar amount is 1 to 10 times, preferably 1 to 5 times.

Any solvent can be used as long as it does not affect the reaction. Examples of the solvent include ethers such as diethyl ether, dibutyl ether, tetrahydrofuran and dioxane; halogenated hydrocarbons such as methylene chloride and chloroform; Examples include aromatic hydrocarbons such as benzene and toluene, and mixed solvents thereof.

The azo coupling reaction is usually carried out at -20
About 50 ° C., preferably 0-20 ° C.
It ends in about 24 hours. Examples of the reduction method include a catalytic reduction method and a method using a reducing agent such as lithium aluminum hydride, sodium borohydride, lithium borohydride, diborane, and Raney nickel. The reduction of the bisazobenzene compound (4) is preferably performed under basic conditions. Examples of the base to be used include those described above.

The amount of the reducing agent used is 0.5 to 10 equivalents, preferably 2 to 5 equivalents, based on the bisazobenzene compound (4). The reduction reaction is usually performed at 10 to 150 ° C.
Degree, preferably at 40-120 ° C, 0.5-2
It takes about 4 hours. Next, a hydroxyphenol represented by the general formula (5) or (5 ′) is reacted with an aldehyde or a ketone in an appropriate solvent in the presence of an acid catalyst to obtain a desired methylenebisphenol compound.
The reaction for obtaining (1) will be described below.

The above methylene bisphenol compound (1)
Can be produced by reacting 4-hydroxyphenols (5) or (5 ′) with 1.0 to 3.0 equivalents of aldehydes or ketones in a suitable solvent in the presence of an acid catalyst for 1 to 50 hours. . In addition, the reaction can be carried out without a solvent or using a liquid acid catalyst such as sulfuric acid or an organic acid of hydrochloric acid as a solvent depending on the purpose.

The aldehydes used herein are not particularly limited, and conventionally known aldehydes can be widely used.
Specifically, formaldehyde and its aqueous solution, acetaldehyde, lower aliphatic aldehydes such as propionaldehyde, linear oligomers such as paraformaldehyde, trioxane, cyclic oligomers such as tetraoxymethylene, and in some cases, such as dimethyl acetal Aldehyde derivatives are preferably used.

The ketones are not particularly limited.
Conventionally known ones can be widely used. Specifically, acetone, 2-butanone, 2-pentanone, 3-pentanone,
Further, in some cases, a derivative of a ketone such as dimethyl ketal is preferably used. The acid catalyst is not particularly limited as long as it is a strong acid, and conventionally known ones can be widely used. Specifically, inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid; phosphotungstic acid, phosphomolybdic acid, phosphomolybdungstic acid, phosphomolybdovanadic acid, heteropolyacids such as silicotungstic acid and silicomolybdic acid; Ion exchange resins, organic acids such as oxalic acid, and solid acids such as aluminosilicate. These can be used alone or in combination of two or more depending on the purpose.

The amount of the catalyst to be used is not particularly limited and is selected in a wide range, but is usually 0.01 to 10% based on the methylene bisphenol compound represented by the general formula (1).
500% by weight is preferred. As the solvent, any solvent can be used as long as it does not affect the reaction.For example, organic acids such as formic acid, acetic acid, and propionic acid, ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, and ethylene glycol dimethyl ether can be used. And nitriles such as acetonitrile, and aliphatic hydrocarbons such as petroleum ether, hexane and heptane. These can be used alone or in combination of two or more depending on the purpose.

The amount of the solvent used is not particularly limited, and is selected from a wide range according to the ease of stirring, the reaction temperature, and the solubility in the substrate.
10 to 50 with respect to the methylene bisphenol represented by
0% by weight is preferred. The reaction temperature is -20C to 200C,
Preferably, it is appropriately selected in the range of 0 ° C. to 150 ° C. according to the type of the solvent or the substrate.

The methylene bisphenol compound represented by the general formula (1) thus obtained can be directly used for the production of a bisbenzotriazolyl phenol compound represented by the general formula (2). It is more preferable to purify using general-purpose means such as crystals. The methylene bisphenol compound (1) obtained by the above method can be easily and highly purely converted into a bisbenzotriazole phenol represented by the general formula (2), which is a polycondensation reaction type ultraviolet absorber, by a conventionally known method. Is done.

The bisbenzotriazolylphenol compound represented by the general formula (2) obtained by the above method has such a high purity that a decolorization step and a purification step which are usually required in the production step are not required. The crystals obtained by concentrating most of the reaction solution are simply washed with water and dried, or extracted with an inert solvent such as dioxane and then recrystallized and dried to obtain a simple isolation method. Can be.

[0050]

The present invention will be described below with reference to examples and production examples. Example 1 13.8 g of 4- (2-hydroxyethyl) phenol
(100 mmol) was dissolved in 20 ml of sulfuric acid, and 0.75 g (50 mmol) of paraformaldehyde was added thereto, followed by stirring at room temperature for 12 hours. The reaction mixture is then added to water 200
After stirring for 1 hour, the precipitated crystals were separated by filtration, and the obtained filtrate was washed with water and dried under reduced pressure for 24 hours to obtain 3,3′-methylenebis ( 10.1 g of 4-hydroxyphenethyl alcohol) was obtained as white crystals (yield: 71.4%).

¹ H-NMR (CDCl ₃ ): δ (pp
m) = 2.92 (t, 4H, CH ₂ ), 3.92 (t,
4H, CH ₂ O), 4.28 (s, 2H, CH ₂ ),
6.64 (d, 2H, Ar-H), 6.97 (d, 2
H, Ar-H), 7.10 (s, 2H, Ar-H), 1
2.22 (s, 2H, Ar-OH). Example 2 Instead of 4- (2-hydroxyethyl) phenol, 4
-(3-Hydroxypropyl) phenol 15.2 g
(100 mmol), and the reaction was carried out in the same manner as in Example 1 to obtain 2,2′-
11.5 g of methylenebis [4- (3-hydroxypropyl) phenol] was obtained as colorless crystals (yield 7).
4.0%).

¹ H-NMR (CDCl ₃ ): δ (pp
m) = 1.87 (q, 4H, Ar-CH2), 2.65
_{(T, 4H, CH 2)} , 3.70 (t, 4H, CH
₂ O), 4.28 (s, 2H, CH2), 6.64
(D, 2H, Ar-H), 6.97 (d, 2H, Ar-
H), 7.09 (s, 2H, Ar-H), 12.22.
(S, 2H, Ar-OH). Reference Example 1 10.5 g (75 mmol) of o-nitroaniline was added to 42 ml of concentrated hydrochloric acid, stirred at 70 ° C. for about 30 minutes, and then cooled to 0 ° C. using an ice bath. Then, 5.4 g (75 mmol) of sodium nitrite was previously added to water 2
An aqueous solution prepared by dissolving in 8 ml was added dropwise in about 1 hour. During the dropwise addition, the temperature of the mixture was kept at 5 ° C. or lower. The mixture was further stirred at 5 ° C. or lower for 1 hour to prepare a diazonium salt of o-nitroaniline. Reference Example 2 In place of 10.5 g (75 mmol) of o-nitroaniline, 13.1 g (75%) of 4-chloro-2-nitroaniline was used.
The reaction was carried out in the same manner as in Reference Example 1 except that (mmol) was used to prepare a diazonium salt of 4-chloro-2-nitroaniline. Reference Production Example 1 2,2′-methylenebis [4- (2
-Hydroxyethyl) phenol] 10.1 g (35.
1 mmol) and 30 g (0.36 mmol) of sodium carbonate were dissolved in 150 ml of isopropanol, and the mixture was heated to about 5 ° C. or lower while maintaining the hydrochloric acid solution of the diazonium salt of o-nitroaniline prepared in Reference Example 1 at about 5 ° C. or lower. 1
It was dropped over time.

After the dropwise addition, the mixture was stirred at room temperature for 12 hours, and the precipitated crystals were separated by filtration and dried under reduced pressure to give methylene bis 2,2'-
Methylenebis {4- (2-hydroxyethyl) -6
19.2 g of [(2-nitrophenyl) azo] phenol} was obtained as red crystals (yield 94%). Reference Production Example 2 The procedure of Reference Production Example 1 was repeated, except that the hydrochloric acid solution of the diazonium salt of 4-chloro-2-nitroaniline prepared in Reference Example 2 was used instead of the hydrochloric acid solution of the diazonium salt of o-nitroaniline. To obtain 21.2 g of methylenebis 2,2'-methylenebis {4- (2-hydroxyethyl) -6-[(4-chloro-2-nitrophenyl) azo] phenol} as red crystals. (Yield 92%). Reference Production Example 3 2,2′-methylenebis [4- (2-hydroxyethyl) phenol] was replaced with 10.1 g (35.1 mmol) of 2,2′-methylenebis [4] synthesized in Example 2.
-(3-hydroxypropyl) phenol] in 11.5
Reference Production Example 1 except that g (36.4 mmol) was used.
Methylenebis 2,2
2'-methylenebis {4- (3-hydroxypropyl)
20.6 g of -6-[(2-nitrophenyl) azo] phenol} was obtained as red crystals (yield 95%). Production Example 1 Crude 2,2'-methylenebis @ 4 synthesized in Reference Production Example 1
-(2-hydroxyethyl) -6-[(2-nitrophenyl) azo] phenol ア ゾ 10.5 g (18 mmol)
Was dissolved in 36 ml of a 2N aqueous solution of sodium hydroxide, and then 18 ml of a previously prepared 25% aqueous solution of sodium hydroxide and 10.8 g of zinc powder (16%).
6 mmol) were added simultaneously over about 3 hours.

Next, the temperature of the reaction mixture was raised to 70 ° C.
After stirring for about 2 hours, the reaction mixture was cooled to room temperature, and the inorganic substances were separated by filtration. The mother liquor obtained here was acidified using concentrated hydrochloric acid. The yellow crystals precipitated at this time are separated by filtration and then recrystallized in dioxane to give 2,2′-.
Methylenebis [6- (2H-benzotriazole-2-
Il) -4- (2-hydroxyethyl) phenol] as white crystals (yield 84%, purity 9).
8.9%).

¹ H-NMR (CDCl ₃ ): δ = 2.8
_{9 (t, 4H, CH 2} ), 3.89 (t, 4H, CH 2
OH), 4.28 (s, 2H , CH 2), 7.26
(S, 2H, Ar-H), 7.47 (dd, 4H, Ar
-H), 7.92 (dd, 4H, Ar-H), 8.18
(S, 2H, Ar-H), 11.59 (s, 2H, Ar
-OH) Production Example 2 Crude 2,2'-methylenebis @ 4 synthesized in Reference Production Example 1
-(2-hydroxyethyl) -6-[(2-nitrophenyl) azo] phenol ア ゾ 10.5 g (18 mmol)
Instead of the crude methylene bis 2, synthesized in Reference Production Example 2,
2'-methylenebis {4- (2-hydroxyethyl)-
6-[(4-Chloro-2-nitrophenyl) azo] phenol} The reaction was carried out in the same manner as in Production Example 1 except for using 11.8 g (18 mmol) of 2, to give 2,2.
9.7 g of 2'-methylenebis [6- (5-chloro-2H-benzotriazol-2-yl) -4- (2-hydroxyethyl) phenol] was obtained as pale yellow crystals (yield 90.0%). , Purity 99.0%).

¹ H-NMR (CDCl ₃ ): δ (pp
m) = 2.89 (t, 4H , CH 2), 3.89 (t,
4H, CH ₂ OH), 4.28 (s, 2H, CH ₂ ),
7.26 (s, 2H, Ar-H), 7.37 (d, 2
H, Ar-H), 7.82 (d, 2H, Ar-H),
7.84 (s, 2H, Ar-H), 8.18 (s, 2
H, Ar-H), 11.59 (s, 2H, Ar-O
H). Production Example 3 Crude 2,2'-methylenebis @ 4 synthesized in Reference Production Example 1
-(2-hydroxyethyl) -6-[(2-nitrophenyl) azo] phenol ア ゾ 10.5 g (18 mmol)
Was replaced with crude methylenebismethylenebis2,2′-methylenebis {4- (3-hydroxypropyl) -6-[(2-nitrophenyl) azo] phenol} 11.1 g (18 The reaction was carried out in the same manner as in Production Example 1 except that
8.9 g of 2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (3-hydroxypropyl) phenol] was obtained as white crystals (yield: 89.
2%, purity 99.0%).

[0057]¹H-NMR (CDCl_Three): Δ (pp
m) = 1.89 (q, 2H, Ar-CH _Two−), 2.8
2 (t, 4H, CH_Two), 3.81 (t, 4H, CH_Two
OH), 4.28 (s, 2H, CH_Two), 7.26
(S, 2H, Ar-H), 7.47 (dd, 4H, Ar
-H), 7.92 (dd, 4H, Ar-H), 8.18
(S, 2H, Ar-H), 11.59 (s, 2H, Ar
-OH).

[0058]

When the bisphenol compound (1) of the present invention is used as a synthetic intermediate, a bisbenzotriazolylphenol compound (excellent in ultraviolet absorption) capable of imparting long-term weather resistance to a resin or the like ( Polycondensation ultraviolet absorber) can be provided very easily and in good yield.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-8-245463 (JP, A) JP-A-52-85128 (JP, A) JP-B-6-53733 (JP, B2) International publication 97/12882 (WO, A1) WO 97/35847 (WO, A1) Chemical Abstracts; vol. 68 (No. 16) (1968. 4.15) p6718 Abstract No. 69421j (58) Fields investigated (Int. Cl. ⁶ , DB name) C07D 249/20 C07C 39/15-39/16 CAPLUS (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] [Claim 1] General formula (1): [In the formula, A is an alkylene group of carbon number 1 to 6, group: -C
(CH3) 2- or a group: -C (C2H5)
(CH3) - . R ¹ and R ² are the same or different and each represents a hydroxyl group or a linear or branched hydroxyalkyl group having 1 to 12 carbon atoms. Wherein the methylene bisphenol compound represented by the general formula (2) is used as a synthetic intermediate. [In the formula, A is an alkylene group of carbon number 1 to 6, group: -C
(CH3) 2- or a group: -C (C2H5)
(CH3) - . R ¹ and R ² are the same or different and each represents a hydroxyl group or a linear or branched hydroxyalkyl group having 1 to 12 carbon atoms. R ³ and R
⁴ is the same or different and represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, an alkoxy group having 1 to 4 carbon atoms or a halogen atom. ] The manufacturing method of the bisbenzotriazolylphenol compound represented by these. 2. The methylene bisphenol compound (1)
And the general formula (3): [In the formula, R ³ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. And a diazonium salt of an o-nitroaniline derivative represented by the general formula (3 ′): [In the formula, R ⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. Azo-coupling with a diazonium salt of an o-nitroaniline derivative represented by the general formula (4): [In the formula, A is an alkylene group of carbon number 1 to 6, group: -C
(CH3) 2- or a group: -C (C2H5)
(CH3) - . R ¹ and R ² are the same or different and each represents a hydroxyl group or a linear or branched hydroxyalkyl group having 1 to 12 carbon atoms. R ³ and R
⁴ is the same or different and represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, an alkoxy group having 1 to 4 carbon atoms or a halogen atom. And a bisazobenzene compound represented by the formula (4):
The method for producing a bisbenzotriazolyl phenol compound according to claim 1, which is performed by reducing