JPH08208628A - Benzotriazole and production thereof - Google Patents

Abstract

PURPOSE: To provide a new benzotriazole compound which is useful as an ultraviolet absorber for preventing a variety of resins, synthetic rubbers and latices from being deteriorated by ultraviolet rays. CONSTITUTION: This compound is represented by formula I (R<1> is H, a halogen, a 1-12C alkyl, an alkoxy; R<2> , R<4> are each H, a 1-10C alkyl, aryl, aralkyl, alkoxy, phenoxy; R<3> is a 1-12C alkyl, aryl, aralkyl, aloxy, phenoxy), typically 2-(2'- hydroxy-3'-hydroxymethyl-5'-methylphenyl)benzotriazole. The compound of formula I is obtained by coupling reaction of a phenol of formula II with a diazonium sal of an amine of formula III, followed by reduction of the product. This compound can be readily produced and has excellent ultraviolet-absorbing action. Further, when this compound bears an alcoholic functional group, other compounds can have ultraviolet ray-absorbing ability by reacting with this triazole.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel benzotriazole compound useful as an ultraviolet absorber for preventing deterioration of various resins, synthetic rubber, latex and the like due to ultraviolet rays in industry, and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Conventionally, 2- (2-hydroxyphenyl)
It is well known that benzotriazoles have an excellent action of preventing deterioration of various resins by ultraviolet rays. For example, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) benzotriazole, 2- (2-hydroxy-5-t-octylphenyl) Benzotriazole,
2- (2-Hydroxy-3-t-butyl-5-methylphenyl) benzotriazole and the like are commercially available.

However, when the processing conditions have been varied with the widespread use of various resins, and particularly high fastness is required even in high temperature processing, these known benzotriazoles have a molecular weight higher than that of polymer materials. Since it has a relatively low molecular weight and is easily volatilized, the amount thereof is easily reduced, and the volatile benzotriazole adheres to equipment such as a molding machine or deteriorates the surrounding environment. Further, these known benzotriazoles have only phenolic OH as a functional group, and depending on the use, the number of hydrocarbons in the side chain of the benzene ring to which OH is bonded is changed to change the melting point or polymer. There are many points to be improved, such as only changing the compatibility with materials and the like, and limiting the range of synthesis from the industrially usable phenol.

In order to improve such a defect, a functional group is introduced into a phenol in advance.
For -188581, -COOH is used, and (b) Japanese Patent Publication No. 41-1.
At 687, there is CH ₂ CH ₂ COOR. In addition, after the synthesis of triazole, (c) in JP-B-47-560, an amino group is introduced and methacrylic acid is added to polymerize, or (d) JP-A-61-118373 and JP-A-61-118374.
Then, make methylene bis form with formaldehyde,
(e) Japanese Patent Publication No. 56-5279 describes a tetrahydroanhydrocap
An N-methylol derivative of acid imide is added to increase the molecular weight. Further, (f) benzotriazol is also found in the structures of the photographic chemicals of JP-A-61-53253 and the dye of JP-A-3-241069.
Le improves the light resistance of photographic drugs and dyes.

[0005]

[Problems to be Solved by the Invention]
The known benzotriazoles (a) to (f) have an economical problem because the manufacturing process is complicated and expensive.

An object of the present invention is that it can be produced by a simple process and has an ultraviolet absorbing property, and it itself serves as an ultraviolet absorber and, by having a functional group, reacts with the functional group to easily absorb the ultraviolet ray. It is an object of the present invention to provide a novel benzotriazole compound capable of providing a function and a method for producing the same.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have noticed that UV absorbers are used in a wide range of industries including synthetic resins and synthetic rubbers, as well as paints, dyes, cosmetics, and in some cases pharmaceuticals and agrochemicals. , 2- (2-hydroxyphenyl) benzotriazoles have been earnestly studied, and as a result, they have industrially easy production, excellent ultraviolet absorption ability, and
The present invention has led to the finding of an intermediate having a high reactivity, which has an alcoholic functional group and can easily react with other chemicals to have an ultraviolet absorbing ability.

That is, according to the present invention,
Having ₂ OH 2- (2- hydroxy-3-hydroxymethyl) benzotriazole - with finding Le, which is reacted with other chemicals as intermediate by novel benzotriazole - providing and existing UV Le ultraviolet absorber It is intended to provide a novel method for producing an absorbent.

The present invention has the general formula (1)

[0010]

[Chemical 10]

(Wherein R ¹ is a hydrogen atom, a halogen atom,
R represents a C _{1 to} C ₁₂ alkyl group or alkoxy group, and R
² and R ⁴ represent a hydrogen atom, a C ₁ -C ₁₀ alkyl group, an aryl group, an aralkyl group, an alkoxy group or a phenoxy group, and R ³ represents a C ₁ -C ₁₂ alkyl group, an aryl group, an aralkyl group, an alkoxy group. Represents a group or a phenoxy group. ) Is a benzotriazole compound represented by.

Examples of the halogen atom represented by the general formula R ¹ include a chlorine atom and a bromine atom, and a chlorine atom is preferable from the viewpoint of industrial utilization. Examples of the alkyl group, aryl group and aralkyl group of R ¹ , R ² , R ³ and R ⁴ include methyl, ethyl, propyl, isopropyl and n-
Butyl, sec-butyl, t-butyl, amyl, sec
-Amyl, t-amyl, octyl, t-octyl, 2-
Examples include ethylhexyl, dodecyl, phenyl, cumyl and the like. As the alkoxy group, methoxy, ethoxy, propoxy, isopropoxy, butoxy, tertiary butoxy,
Examples include octoxy and phenoxy.

It has been conventionally known that a phenol compound having a nuclear methylol group represented by the following general formula reacts with a diazonium salt to cause demethylol to undergo coupling. (J.Am.Chem.Soc., 73,5475 (1951) .ibid., 7
7,3384, (1955))

[0014]

[Chemical 11] (In the formula, R is a hydrogen atom, a methyl group, a formyl group)

Further, 2,6-dihydroxymethyl-p-
It is known that cresol reacts as in the following formula to produce a compound in which one hydroxymethyl group remains.
(J. Am. Chem. Soc., 33, 5475 (1951)).

[0016]

[Chemical 12]

However, 2- (2-hydroxy-3-hydroxymethyl) benzotriazole having a methylol group represented by the general formula (1) is not known.

The present inventors have found that the compound of the general formula (1) can be obtained in a high yield as a result of a reaction using a nitroazo compound of the following general formula (8) as a raw material by a conventional method.

[0019]

[Chemical 13]

(Wherein R ¹ is a hydrogen atom, a halogen atom,
R represents a C _{1 to} C ₁₂ alkyl group or alkoxy group, and R
² and R ⁴ represent a hydrogen atom, a C ₁ -C ₁₀ alkyl group, an aryl group, an aralkyl group, an alkoxy group or a phenoxy group, and R ³ represents a C ₁ -C ₁₂ alkyl group, an aryl group, an aralkyl group, an alkoxy group. Represents a group or a phenoxy group. )

That is, --CH ₂ OH of the nitroazo compound represented by the general formula (8) does not show any expected instability and is stable even after taking out after coupling, and then by a known reduction treatment. Found that the benzotriazole compound (1) can be synthesized in a stable and high yield,
The present invention has been achieved.

The compound of the general formula (1) of the present invention can be synthesized by the method shown below. As an intermediate of the compound of the general formula (1) of the present invention, the compound of the general formula (4) is added to formaldehyde in an alkaline medium to synthesize the compound of the general formula (5).

[0023]

Embedded image (In the formula, R ² and R ⁴ represent a hydrogen atom, a C ₁ -C ₁₀ alkyl group, an aryl group, an aralkyl group, an alkoxy group or a phenoxy group, and R ³ represents a C ₁ -C ₁₂ alkyl group,
An aryl group, an aralkyl group, an alkoxy group or a phenoxy group is shown. )

On the other hand, the general formula (6)

[0025]

[Chemical 15]

(In the formula, R ¹ is a hydrogen atom, a halogen atom,
An alkyl or alkoxy group C ₁ -C _12. )

The compound represented by the formula (1) is converted into an o-nitrodiazonium salt by a conventional method, and this is subjected to a diazo coupling reaction with the compound represented by the general formula (5) to obtain an azo compound represented by the general formula (8). The azo compound represented by the general formula (8) is reduced with zinc powder under alkaline conditions or reduced with hydrazine, formalin or the like to give the N-oxide represented by the general formula (9), and By reducing with zinc dust in the presence of sulfuric acid or the like, the desired benzotriazole of the present invention having a methylol group represented by the general formula (1) can be obtained.

[0028]

Embedded image

(In the formula, R ¹ is a hydrogen atom, a halogen atom,
R represents a C _{1 to} C ₁₂ alkyl group or alkoxy group, and R
² and R ⁴ represent a hydrogen atom, a C ₁ -C ₁₀ alkyl group, an aryl group, an aralkyl group, an alkoxy group or a phenoxy group, and R ³ represents a C ₁ -C ₁₂ alkyl group, an aryl group, an aralkyl group, an alkoxy group. Represents a group or a phenoxy group. )

In the present invention, the 2,6-dimethylol compound represented by the general formula (5) is not taken out of the system after the reaction between phenol and formaldehyde, and is allowed to undergo a coupling reaction with the next diazo solution as it is. May be. Further, as the formaldehyde, formalin aqueous solution or paraformaldehyde may be used. Regarding the reduction, there is no problem even if the reduction is performed by an alcohol other than the above, hydrogen gas, carbon monoxide or the like. Further, the obtained compound represented by the general formula (1) is reacted with other chemicals to give a compound according to claim 2, 3, 4,
General formulas (2), (3), (4), and (7) shown in FIG.
In the synthesis of the compound represented by, the compound represented by the general formula (1) may be reacted by an operation such as extraction without taking it out of the system.

General formula (2)

[0032]

[Chemical 17]

(In the formula, R ¹ is a hydrogen atom, a halogen atom,
R represents a C _{1 to} C ₁₂ alkyl group or alkoxy group, and R
² and R ⁴ represent a hydrogen atom, a C ₁ -C ₁₀ alkyl group, an aryl group, an aralkyl group, an alkoxy group or a phenoxy group, and R ³ represents a C ₁ -C ₁₂ alkyl group, an aryl group, an aralkyl group, an alkoxy group. Represents a group or a phenoxy group. )

The compound represented by the formula (1) can be obtained by dissolving the compound of the general formula (1) in a solvent such as methyl ethyl ketone or methyl isobutyl ketone, and then refluxing and dehydrating it under an acidic catalyst such as methanesulfonic acid. it can.

General formula (3)

[0036]

Embedded image

(In the formula, R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above, and R ⁵ represents a C _{6 to} C ₂₀ aryl group.)

The compound represented by the formula (1) is prepared by dissolving the compound of the general formula (1) in a solvent such as benzene, toluene, xylene,
It can be obtained by reflux dehydration in the presence of an acidic catalyst such as methanesulfonic acid.

General formula (4)

[0040]

[Chemical 19]

(In the formula, R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above, R ⁶ represents a C _{1 to} C ₂₀ alkyl group, an aryl group or an aralkyl group, and n is 1 to 4). Indicates the integer of.)

The compound represented by the formula (1) is prepared by dissolving the compound of the general formula (1) and an acid in a suitable solvent, and then, if necessary, adding an acid catalyst such as sulfuric acid or methanesulfonic acid at room temperature to reflux temperature. , And can be obtained by treating by a conventional method.
Examples of the acid include acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, benzoic acid, salicylic acid, 3,5-di-t-
Butyl-4-hydroxybenzoic acid, monobasic acid such as thioglycolic acid, oxalic acid, malonic acid, succinic acid, maleic acid, adipic acid, sebacic acid, phthalic acid, 3,3′-thiodipropionic acid, Examples thereof include dibasic acids such as 3,3′-dithiodipropionic acid, and polybasic acids such as pyromellitic acid and butanetetracarboxylic acid. Further, in the case of acid anhydrides such as succinic anhydride, maleic anhydride, and phthalic anhydride, an ester having —COOH remaining on one side can be obtained. Acid chloride may be used instead of acid.

Further, the urethane compound can be obtained by dissolving the compound represented by the general formula (1) and the isocyanate in a suitable solvent and then treating them by a conventional method. Suitable isocyanates include phenyl isocyanate, toluene diisocyanate, methylene bis (4-phenyl isocyanate) and the like.

Conventional general formula (7)

[0045]

Embedded image

(In the formula, R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above.)

The methylene bis compound represented by the formula (1) is a method in which the benzotriazole represented by the general formula (10) is previously synthesized and reacted with formaldehyde.

[0048]

[Chemical 21]

For example, (a) benzotriazole of the general formula (10) is dimerized with formaldehyde in a strong acid.
(b) JP-A-61-115073, JP-A-61-11833
73 and JP-A-61-118374, benzotriazole is reacted with amines and formaldehydes in a solvent to give a Mannich compound represented by the general formula (11), and the Mannich compound is reacted with the general formula (10). Alternatively, the Mannich compound of the general formula (11) is dimerized. (c) Japanese Patent Application Laid-Open No. 4-290877 is also characterized in that a solvent is not used in the Mannich compound routed method.

However, in the method (a), the substituent at the 4-position is eliminated due to severe reaction conditions in a strong acid, and the desired methylene bis compound cannot be obtained in a high yield due to a side reaction. Although the methods (b) and (c) can be obtained in a relatively high yield, amines having a strong odor such as dimethylamine, diethylamine, and dibutylamine for producing Mannich compounds are used. In order to obtain the above, it is necessary to recover and recycle these amines at a high temperature under reduced pressure equipment. In addition, the method (c) is characterized in that it can be produced in one pot without using a solvent, but it is not necessarily industrially easy because it requires a vacuum and pressure resistant reactor. .

As a result of various studies on the reaction of the compound represented by the general formula (1), the present inventors have found a novel method for producing a methylenebis compound. That is, it was found that the methylenebis compound represented by the general formula (7) can be easily obtained only by dissolving the compound represented by the general formula (1) in a solvent, followed by heating and refluxing under an acid catalyst. It has come. In this case, solvents such as toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, sulfuric acid, methanesulfonic acid,
By changing the kind of the acid such as p-toluenesulfonic acid, an ether body represented by the general formula (2) and a compound represented by the general formula (3) are by-produced, but they are separated by crystallization or the like. It is possible.

A stable composition can be prepared by adding the compounds represented by the general formulas (1) to (4) of the present invention as an ultraviolet absorber to synthetic resins and synthetic rubbers. Polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polymethylmethacrylate, polyacrylonitrile, polyester, polyamide, polyurethane, unsaturated polyester, polycarbonate, alkyd resin, epoxy resin, urea resin, melanin resin, It can be used for synthetic resin such as phenol resin, SBR, NBR and synthetic rubber. When the compounds represented by the general formulas (1) to (4) of the present invention are used as an ultraviolet absorber, they can be used alone or in combination of two or more. Of course, it can be used in combination with a conventionally known ultraviolet absorber, antioxidant, light stabilizer and the like.

Examples of UV absorbers that can be used in combination include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy-.
4-octoxybenzophenone, 2-hydroxy-4-
Benzophenone-based UV absorbers such as dodecyloxybenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-
t-butylphenyl) benzotriazole, 2- (2-
Hydroxy-5-t-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-). Amylphenyl)) benzotriazol 2- (2-hydroxy-3,5-di-t-butylphenyl) -5-chlorobenzotriazol, 2- (2
-Hydroxy-3-t-butyl-5-methylphenyl)
Benzotriazol such as 5-chlorobenzotriazol
And a salicylate-based ultraviolet absorber such as phenyl salicylate and 4-t-butylphenyl salicylate.

Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol and stearyl-
β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and other monophenol antioxidants,
2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-
Ethyl-6-t-butylphenol)), 4,4'-thiobis- (3-methyl-6-t-butylphenol),
4,4'-butylidene-bis- (3-methyl-6-t-
Butylphenol), 3,9-bis- [1,1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5
-Methylphenyl) propionyloxy} ethyl]-
Bisphenol type antioxidants such as 2,4,8,10-tetraoxaspiro [5,5] undecane, tetrakis-
[Methylene-3- (3 ', 5'-di-t-butyl-4'
-Hydroxyphenyl) propionate] methane, bis- [3,3'-bis- [3,3'-bis- (4'-hydroxy-3-t-butylphenyl) butyric acid] glycol ester, 1 , 3,5-Tris (3 ',
5'-di-t-butyl-4'-hydroxybenzyl)-
Polymeric phenolic antioxidants such as s-triazine-2,4,6- (1H, 3H, 5H) trione, dilaurylthiodipropionate, dimyristylthiodipropionate, penta Examples thereof include sulfur antioxidants such as erythritol-tetrakis- (3-laurylthiopropionate).

Examples of the light stabilizer include bis- (2,
2,6,6-Tetramethylpiperazyl) sebacate, 4
-Benzoyloxy-2,2,6,6-tetramethylpiperidine, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine heavy compound, poly [{6- (1,1,3,3
-Tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2
2,6,6-Tetramethyl-4-piperidyl)) imino}]-8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,3,8-triazaspiro [4.
5] -Undecane-2,4-dione and the like hindered amines.

Other stabilizers include, for example, [2,
2-Thio-bis- (4-t-octylphenolate)]
Examples thereof include nickel compounds such as -n-butylamine-nickel (II) and [2,2-thio-bis- (4-t-octylphenolato)]-2-ethylhexylamine-nickel (II).

When the compound of the present invention is used as an ultraviolet absorber, it can be used in combination with, for example, a plasticizer, an emulsifying agent, a lubricant, a pigment, a fluorescent whitening agent, a flame retardant, an antistatic agent and the like.

[0058]

The compounds represented by the general formulas (1) to (4) of the present invention are novel compounds and can be used as an ultraviolet absorber for various synthetic resins, rubbers, latexes, paints and the like. In this case, 0.001 to 15% by weight, preferably 0.05 to 15% by weight, of the resin or the like is preferably added. Further, since it has an alcoholic functional group, the same reaction as a normal alcohol reaction is possible,
For example, as represented by the general formula (4), a carboxylic acid,
It is also possible to increase the molecular weight by a reaction such as esterification with sulfonic acid or a chloride thereof, and by reacting with a compound having a double bond such as (meth) acrylic acid. It is also possible to synthesize benzotriazole having a polymerizable ultraviolet absorbing ability. Furthermore, it is also possible to synthesize a dye, a photographic chemical or the like having an ultraviolet absorbing ability by reacting a dye or a photographic chemical with the compound of the present invention. As mentioned above,
The compound of the present invention acts not only as an ultraviolet absorber by itself, but also as an intermediate, the reaction further facilitates the synthesis of a compound having an ultraviolet absorbing ability.

[0059]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these.

(Example 1) 36 g of o-nitroaniline,
To a suspension of 62.5% sulfuric acid (40 ml) and water (220 ml), a solution of 19 g of sodium sulfite and 40 ml of water was added dropwise at a temperature of 0 to 5 ° C over 1 hour, and a yellow diazo solution was obtained by stirring for 1 hour. can get. Sulfamic acid is then added to quench excess nitrous acid. On the other hand, 2,6-di-hydroxymethyl-p-cresol 45 obtained by the method of Ber.40,2532 (1907).
g, 400 ml of water, 39 ml of 48% caustic soda were cooled to 10 ° C. or lower, and the diazo solution obtained above was added dropwise to the mixture under stirring for 1 hour, and the mixture was further stirred for 1 hour. The mixture was hydrated, filtered, washed with water, and dried to give 69.6 g of a 96% pure azo compound (yield: 8
9.2%). 69.6 g of the azo compound, 27 of water
0 ml, toluene 150 ml, 48% caustic soda 17 m
After adding 0.5 g of hydroquinone to the mixture of 1
Then, 9 ml of 80% hydrazine solution is added dropwise, and the mixture is further stirred for 2 hours. After liquid separation, the toluene layer was neutralized, cooled, filtered, washed with water and dried to obtain 57.8 g of N-oxide (yield 91.6% from the azo compound). A suspension of 57.8 g of this N-oxide, 750 ml of water, 420 ml of toluene, and 32.8 g of zinc dust was heated to 70 to 75 ° C., and 62.5% sulfuric acid 98 m was added.
1 is added dropwise over 2 hours, and stirring is continued for another 2 hours. Then, the toluene layer is separated by liquid separation, and after washing with water, the toluene is recovered and the desired pale yellow 2- (2'-hydroxy-
51.2 g of 3'-hydroxymethyl-5'-methylphenyl) benzotriazole (yield 94.
2%) was obtained. Characteristics Melting point: 168.0-169.1 ℃, UV absorption: λ (Max) 341 nm ε = 15900

Example 2 12.7 g of the benzotriazole obtained in Example 1 was added to 300 ml of methyl ethyl ketone.
, Methanesulfonic acid (1 g) is added, and the mixture is refluxed for 24 hours for dehydration. The reaction solution was poured into 1000 ml of water, and the precipitated crystals were separated by filtration and washed with isopropyl alcohol (hereinafter, IPA).
Abbreviated. ) And then dried to give 8.3 g of 3,3'-bis (2H-benzotriazol-2yl) -2,2'-.
Dihydroxy-5,5'-dimethylbenzyl ether was obtained. The melting point was 231 to 232 ° C, and it was confirmed from the elemental analysis and the NMR measurement that the compound had the following structure.

[0062]

[Chemical formula 22]

Example 3 12.7 g of bezotriazole obtained in Example 1 was dissolved in 300 ml of toluene, 0.5 g of methanesulfonic acid was added, and the mixture was refluxed and dehydrated for 24 hours. Then, the reaction solution is washed with 100 ml of warm water three times, and then toluene is distilled off under reduced pressure. The remaining crystals were recrystallized with isopropyl alcohol water to obtain 9.2 g of white crystals. The melting point was 144 to 146 ° C., and it was confirmed from the elemental analysis and NMR measurement that the compound had the following structure.

[0064]

[Chemical formula 23]

Example 4 12.7 g of the benzotriazole obtained in Example 1 was added to methyl isobutyl ketone (MI).
BK) dissolved in 300 ml, methanesulfonic acid 0.5 g
Add and dehydrate under reflux for 24 hours. Then, the reaction solution is water 1
After washing with 00 ml, 150 ml of MIBK is collected under reduced pressure and cooled. The precipitated crystals were filtered off, washed with IPA and dried to give 4.3 g of 3,3′-bis (2H-benzotriazol-2-yl) -2,2′-dihydroxy-5,5′-dimethyl. Benzyl ether was obtained. Melting point
The temperature was 230.5 to 232 ° C. The solvent was distilled off from the filtrate under reduced pressure, and the residue was recrystallized with toluene to obtain 4.6 g of pale yellowish white crystals having a purity of 97.2%. This crystal is recrystallized again from toluene to have a purity of 99.8% and a melting point of 283 to 284 ° C.
Got one. From the melting point, elemental analysis and NMR measurement, it was a methylenebis compound having the following structure.

[0066]

[Chemical formula 24]

(Example 5) 2,6-di-hydroxymethyl-4-t-butylphenol was prepared according to J. Prakt. Chem., 153, 32.
It was synthesized by the method of 7 (1939). 2,6-di-of Example 1
2,6-instead of hydroxymethyl-P-cresol
Di-hydroxymethyl-4-t-butylphenol 57
Example 1 was repeated except that g was used. As a result, 81.3 g of an azo compound having a purity of 90.1% (yield 85.3) was obtained.
%) And 60.9 g of N-oxide (yield 87.4%). The target amount of 2- (2'-hydroxy-3'-hydroxymethyl-5'-t-butylphenyl) benzotriazole was 53.0 g (yield 91.8%). Characteristics Melting point: 162.8 to 164.0 ℃ UV absorption: λ (max) 340nm ε = 16400

300 ml of 14.9 g of this triazole was added.
Dissolved in water, heated to 55 ° C., and then charged with phenyl isocyanate 6
g and 0.2 g of pyridine are added and reacted for 24 hours.
After the reaction, the toluene layer was washed 4 times with 200 ml of warm water,
Toluene is distilled off under reduced pressure, then dissolved in 150 ml of IPA and cooled to 10 ° C. for crystallization. The precipitated crystals were separated by filtration, washed with IPA and dried to obtain 14.4 g of the following compound as white crystals. Melting point: 147.0-147.8 ° C

[0069]

[Chemical 25]

Example 6 Instead of 2,6-di-hydroxymethyl-P-cresol in Example 1, 2,6-di-
The same procedure as in Example 1 was carried out except that 57 g of hydroxymethyl-4-t-butylphenol was replaced with 45 g of 4-chloro-2-nitroaniline in place of o-nitroaniline, and as a result, 87.1 g (purity: 93 .7%,
Yield 86.1%), 67.0 g of N-oxide (yield 8
5.8%) was obtained. The desired 2- (2-hydroxy-
3'-hydroxymethyl-5'-t-butylphenyl)
56.8 g of -5-chlorobenzotriazole (yield 8
8.9%). Characteristics Melting point: 134.2-135.2 ° C, UV absorption: λ (max) 347 nm ε = 18100

33.2 g of this triazole was added to acetone 1
After dissolving in 000 ml and adding 15.2 g of triethylamine, 12.5 g of methacrylic acid chloride is added dropwise at room temperature over 1 hour. After dropping, stir for 24 hours, 30%
Neutralize with hydrochloric acid. After filtering off the precipitated triethylamine hydrochloride, acetone was distilled off under reduced pressure to obtain 300 ml of IPA.
To crystallize. The crystals obtained were washed with IPA and dried to give 25.7 g of white crystals, melting point 135.5-13
It was 7.5 ° C. It was the following compound by elemental analysis and NMR measurement.

[0072]

[Chemical formula 26]

Example 7 4-Methoxyphenol 35
g, 48% caustic soda 39 ml, water 400 ml, 35%
A solution of 55 g of formalin water was heated to 50 ° C., the reaction was continued for 2 hours, then cooled to 5 to 10 ° C., coupled in the same manner as in Example 1, and further reduced to give 6 by an azo compound.
6.3 g (purity 90.8%, yield 76.2%) and 50.4 g (yield 88.3%) of N-oxide were obtained. The desired 2- (2'-hydroxy-3'-hydroxymethyl-
5'-methoxyphenyl) benzotriazole is 41.
It was 6 g (yield 87.5%). Characteristics Melting point: 123-124 ° C UV absorption: λ (max) 301 nm ε = 16700 357 nm ε = 14400

10 g of this triazole and 11.8 g of β-mercaptopropionic acid were dissolved in 150 ml of toluene, 0.5 g of 62.5% sulfuric acid was added, and the mixture was refluxed and dehydrated for 4 hours. When the reaction is over, the reaction mixture is cooled and the precipitated crystals are separated by filtration.
Then, it is recrystallized with toluene and has a melting point of 167.5-168.
8.6 g of crystals at 5 ° C. were obtained. It was the following compound from elemental analysis and NMR measurement.

[0075]

[Chemical 27]

Example 8 65 g of o-nitroaniline,
In a suspension of 75 ml of 62.5% sulfuric acid and 400 ml of water, 0
Dissolve 33 g of sodium nitrite in 65 ml of water at -5 ° C to prepare 1
A yellow diazo solution is obtained by adding dropwise over a period of time and further stirring for 1 hour, and excess nitrous acid is extinguished with sulfamic acid. On the other hand, 61 g of 3,4-dimethylphenol was dissolved in 128 g of 35% formalin water, 50 g of triethylamine and 9 g of a surfactant (trade name Lipal SK-860) were added to give 50 g.
After reaction for 5 hours at ℃, after the reaction is completed, 2000 ml of water, 4
Add 83 ml of 8% caustic soda and cool to 0-5 ° C.
The diazo solution obtained above was added dropwise to this over 2 hours,
The mixture is stirred at the same temperature for 3 hours, neutralized with sulfuric acid, filtered, and washed with water to obtain an azo compound. This azo compound was added to 600 ml of water, 80 ml of toluene, 25 ml of 48% caustic soda and 0.5 g of hydroquinone, and then 8
17 ml of 80% hydrazine solution was added dropwise at 0 ° C, and further 2
Stir for hours. After separation, the toluene layer is neutralized, cooled, filtered, washed with water and dried to give 121.9 g (o-
Yield 90.8% from nitroaniline) was obtained. This N
-To a suspension obtained by adding 600 ml of water, 600 ml of toluene, and 40 g of zinc dust to the oxide, raise the temperature to 70 to 75 ° C,
60 ml of 62.5% sulfuric acid was added dropwise over 4 hours, and further 2
Continue stirring for hours. The toluene layer was separated by liquid separation, washed with water, and the toluene was recovered to obtain the desired pale yellow 2- (2'-hydroxy-3'-hydroxymethyl-4 ', 5'-dimethylphenyl) benzotriazole 91.6 g. (Yield from o-nitroaniline 72.3%) was obtained. This was recrystallized from toluene to obtain 83.7 g of pale yellowish white crystals, and the melting point was 186 to 187 ° C. To 10 g of this triazole, 39 g of 3,3'-dithiodipropionic acid,
Toluene (300 ml) and 62.5% sulfuric acid (1 g) were added and the mixture was refluxed and dehydrated for 6 hours. After completion of the reaction, the toluene layer was washed with warm water and 3% ammonia water, and the toluene was distilled off under reduced pressure.
Crystallization with PA gave pale yellowish white crystals with a melting point of 149 to 152 ° C in a yield of 82%. The following compounds were confirmed by elemental analysis and NMR.

[0077]

[Chemical 28]

The compounds obtained by reacting the compound represented by the general formula (1) by a known method are shown in Table 1 below.

[0079]

[Table 1]

[0080]

As described above, the present invention has the following general formulas (1) to
Since it is a novel benzotriazole compound represented by (4), it is easy to manufacture industrially, has excellent ultraviolet absorption ability, and has an alcoholic functional group, so other chemicals It is a highly reactive substance that can easily be made to have an ultraviolet absorbing ability by reacting with. Therefore, the manufacturing process is simple and the economy is good, and it is useful as an ultraviolet absorber for preventing deterioration of various resins, synthetic rubber, latex, paints, dyes, cosmetics, pharmaceuticals and agricultural chemicals due to ultraviolet rays. .

Claims (7)

[Claims] 1. A compound represented by the general formula (1): (In the formula, R ¹ represents a hydrogen atom, a halogen atom, a C ₁ -C ₁₂ alkyl group or an alkoxy group, and R ² and R ⁴ represent a hydrogen atom, a C ₁ -C ₁₀ alkyl group, an aryl group, an aralkyl group. , An alkoxy group or a phenoxy group, R
³ represents a C _{1 to} C ₁₂ alkyl group, aryl group, aralkyl group, alkoxy group or phenoxy group. ) The benzotriazole compound represented by this. 2. A compound of the general formula (2) (In the formula, R ¹ represents a hydrogen atom, a halogen atom, a C ₁ -C ₁₂ alkyl group or an alkoxy group, and R ² and R ⁴ represent a hydrogen atom, a C ₁ -C ₁₀ alkyl group, an aryl group, an aralkyl group. , An alkoxy group or a phenoxy group, R
³ represents a C _{1 to} C ₁₂ alkyl group, aryl group, aralkyl group, alkoxy group or phenoxy group. ) The benzotriazole compound represented by this. 3. A compound represented by the general formula (3): (In the formula, R ¹ represents a hydrogen atom, a halogen atom, a C ₁ -C ₁₂ alkyl group or an alkoxy group, and R ² and R ⁴ represent a hydrogen atom, a C ₁ -C ₁₀ alkyl group, an aryl group, an aralkyl group. , An alkoxy group or a phenoxy group, R
³ represents a C ₁ -C ₁₂ alkyl group, an aryl group, an aralkyl group, an alkoxy group or a phenoxy group, and R ⁵ represents C
An aryl group having ₆ -C _20. ) The benzotriazole compound represented by these. 4. A compound represented by the general formula (4): (In the formula, R ¹ represents a hydrogen atom, a halogen atom, a C ₁ -C ₁₂ alkyl group or an alkoxy group, and R ² and R ⁴ represent a hydrogen atom, a C ₁ -C ₁₀ alkyl group, an aryl group, an aralkyl group. , An alkoxy group or a phenoxy group, R ³
Represents a C ₁ -C ₁₂ alkyl group, aryl group, aralkyl group, alkoxy group or phenoxy group, and R ⁶ represents C
_{1 to} C ₂₀ alkyl group, aryl group or aralkyl group is shown, and n is an integer of 1 to 4. ) The benzotriazole compound represented by these. 5. An ultraviolet absorber containing the benzotriazole compound according to claim 1, 2, 3 or 4 as an active ingredient. 6. A compound represented by the general formula (5): (In the formula, R ² and R ⁴ represent a hydrogen atom, a C ₁ -C ₁₀ alkyl group, an aryl group, an aralkyl group, an alkoxy group or a phenoxy group, and R ³ represents a C ₁ -C ₁₂ alkyl group,
An aryl group, an aralkyl group, an alkoxy group or a phenoxy group is shown. ) Is represented by the general formula (6): (In the formula, R ¹ represents a hydrogen atom, a halogen atom, a C _{1 to} C ₁₂ alkyl group or an alkoxy group.) Coupling with a diazonium salt of an amine represented by the general formula (1 ) [Chemical 7] (In the formula, R ¹ represents a hydrogen atom, a halogen atom, a C ₁ -C ₁₂ alkyl group or an alkoxy group, and R ² and R ⁴ represent a hydrogen atom, a C ₁ -C ₁₀ alkyl group, an aryl group, an aralkyl group. , An alkoxy group or a phenoxy group, R
³ represents a C _{1 to} C ₁₂ alkyl group, aryl group, aralkyl group, alkoxy group or phenoxy group. ) A benzotriazole represented by the formula (4) is produced. 7. A compound represented by the general formula (1): (In the formula, R ¹ represents a hydrogen atom, a halogen atom, a C ₁ -C ₁₂ alkyl group or an alkoxy group, and R ² and R ⁴ represent a hydrogen atom, a C ₁ -C ₁₀ alkyl group, an aryl group, an aralkyl group. , An alkoxy group or a phenoxy group, R
³ represents a C _{1 to} C ₁₂ alkyl group, aryl group, aralkyl group, alkoxy group or phenoxy group. ) The benzotriazole compound represented by the formula (7) is heated under an acidic catalyst to give a compound represented by the general formula (7): (In the formula, R ¹ represents a hydrogen atom, a halogen atom, a C ₁ -C ₁₂ alkyl group or an alkoxy group, and R ² and R ⁴ represent a hydrogen atom, a C ₁ -C ₁₀ alkyl group, an aryl group, an aralkyl group. , An alkoxy group or a phenoxy group, R
³ represents a C _{1 to} C ₁₂ alkyl group, aryl group, aralkyl group, alkoxy group or phenoxy group. ) A benzotriazole represented by the formula (4) is produced.