JPS5842178B2 - Method for producing 1-naphthol derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is an alternative method for producing acylated 1-naphthol derivatives with carboxyl-containing groups useful as intermediates for dyes and organic pigments.

The typical method for synthesizing the 1-naphthol derivative acylated with a group containing a carboxyl group is as follows:
There is a method using the Friedel-Crach reaction or a similar reaction.

In addition to aluminum chloride or aluminum bromide as catalysts, ferric chloride, boron trifluoride, or zinc chloride are also used as reagents for similar reactions, and the knowledge of reactions using these catalysts is detailed in the literature. Are known.

However, in the acylation by Friedel-Crach type reaction, when the 4-position of the ■-naphthol compound is unsubstituted, the acylation reaction occurs preferentially at the 4-position.

In this case, even if the ratio of isomer production does not matter, the product is obtained as a mixture of 2- to 4-substituted compounds, so it is necessary to separate the isomers from the mixed product to obtain the desired product.

On the other hand, reaction examples using orthoboric acid (H2SO4) as a condensing agent are also known in the literature.

For example, Chr, Deichler, Ch, Weiz
Mann et al. (Ber, 36°547-560 (1903
)) is 50 g of phthalic anhydride and 50 g of 1-naphthol and 200 g of boric acid! It is reported that 2-(2'carboxybenzoyl)-1-naphthol was obtained together with naphthofluorane by melting and heating it in J.

From this, it is known that boric acid also functions as an effective condensing agent in this type of condensation reaction.

However, the disadvantages of performing a melt reaction at high temperatures using a large amount of boric acid are that if a certain amount of water is released, it will solidify and become impossible to stir, resulting in equipment damage. This results in a glassy, strong crystalline solid that requires unreasonable effort to crush or elute.

The present invention was discovered to solve these problems of the conventional method, and the method of the present invention uses boric anhydride and a high boiling point organic solvent to produce a solid-liquid. In addition, when boric acid or a mixture of boric acid and boric anhydride is used, the moisture generated during the reaction is successively expelled from the thread through azeotropy with an organic solvent, allowing the initial intended reaction to proceed with smooth stirring throughout. can be completed.

That is, the present invention provides a compound represented by the general formula (II) (wherein R represents a hydrogen atom, a halogen atom, a hydroxyl group, or a lower alkoxy group, and is substituted at a position other than the 2- and 3-positions of the naphthalene nucleus). 1-Naphthol compound and general formula (1) (wherein A is a nitro group, a halogen atom, a hydroxyl group, a carboxyl group or an ester residue thereof, or a benzene nucleus or a naphthalene nucleus, which may be substituted with a lower alkoxy group, - CH2-CH
A dicarboxylic acid anhydride represented by 2CH2-CH2-CH2-CH2 -CH=CH- or -CHCH- is reacted with boric acid at a boiling point of 110°C or higher in the presence of boric anhydride and/or boric acid. in an organic solvent with no properties, 110-22
React at a temperature of 0 ° C. while removing water in the reaction system from the reaction system, more specifically (1) in the presence of boric anhydride,
The reaction is carried out by heating in an organic solvent having a boiling point of 110° C. or higher and having no reactivity with boric acid, or (2) in the presence of boric acid or a mixture of boric acid and boric anhydride, with a boiling point of 110° C. or higher. A general formula characterized in that the reaction is carried out by heating in an organic solvent that does not have reactivity with boric acid and can be azeotropically distilled with water, and the water produced is removed from the reaction system together with the solvent. (I) A method for producing a 1-naphthol derivative represented by the formula (wherein R and A have the same meanings as in general formulas (n) and (1)).

The 1-naphthol compound used in the present invention is a compound represented by the above general formula (II).

Examples of such 1-naphthol compounds include:
■-Naphthol, 4-chloro-1-naphthol, 5-chloro-1-naphthol, 6-chloro-1-naphthol,
4-bromo-1-naphthol, 5-bromo-1-naphthol, 6-bromo-1-naphthol, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 4-bromo-1-naphthol,
Examples include methoxy-1-naphthol and 5-methoxy-1-naphthol.

Further, the dicarboxylic acid anhydride used in the method of the present invention is a compound represented by the above general formula (III).

For example, phthalic anhydride, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, 3-chlorophthalic anhydride, 4-chlorophthalic anhydride, 3,6-dichlorophthalic anhydride, 3-hydroxyphthalic anhydride 4-hydroxyphthalic anhydride, 3-methoxyphthalic anhydride,
3,4,5゜6-Tetrachlorophthalic anhydride, 3-bromphthalic anhydride, 4-bromphthalic anhydride, maleic anhydride, succinic anhydride, hexahydrophthalic anhydride, naphthalene-2, 3-dicarboxylic anhydride, naphthalene-1,2-dicarboxylic anhydride, 5-bromonaphthalene-2,3-dicarboxylic anhydride, 5,8-dibromnaphthalene-2°3-dicarboxylic anhydride, tri- Examples include mellitic anhydride and trimellitic anhydride monoethyl ether.

In the method of the present invention, the ratio of the dicarboxylic acid anhydride of general formula (1) to the naphthol compound of general formula (II) ranges from 1 molar ratio to 10 molar ratio, preferably from 1 molar ratio to 3 molar ratio. range.

In the method of the present invention, the above-mentioned 1-naphthol compound and dicarboxylic acid anhydride are mixed in boric anhydride and/or boric acid in a specific organic solvent at a temperature of 110 to 220°C to remove water in the reaction system. React while removing.

That is, in more detail, a 1-naphthol compound and a dicarboxylic acid anhydride are subjected to a heating reaction in the presence of boric anhydride (1) in an organic solvent having a boiling point of 110° C. or higher and having no reactivity with boric acid; or (2) the boiling point is 110
In the presence of boric acid or a mixture of boric acid and boric anhydride in an organic solvent that is reactive with boric acid and capable of azeotroping with water at temperatures above The 1-naphthol derivative represented by the general formula (I) can be obtained by heating the mixture while distilling it out of the reaction system by azeotropy to preferentially acylate the 2-position of the -naphthol compound.

The organic solvent used in the method of the present invention, i.e., has a boiling point of 110
Examples of organic solvents that have no reactivity with boric acid at temperatures above 110°C, and organic solvents that have a boiling point of 110°C or above, have no reactivity with boric acid, and are capable of azeotroping with water include hydrocarbons or A halogenated hydrocarbon solvent can be used.

Namely, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, amylbenzene, cymene, tetralin, decalin, tetrachloroethylene,
Any one selected from the group consisting of tetrabromoethylene, trichloropropane, chlorobenzene, dichlorobenzene, trichlorobenzene, chlorotoluene, and bromobenzene.

The amount of these organic solvents to be used is preferably 1 part by volume or more, based on 1 part by weight of the raw material 1-naphthol compound, assuming a specific gravity of 1.0, preferably 3 parts by volume.
It is preferable to use the ratio appropriately in a range of 10 parts by volume depending on the solubility of the solute.

In addition, the usage ratio of boric anhydride (in the case of using boric acid, it is converted to boric anhydride) is 0 to the 1-naphthol compound of the raw material.
．． The molar ratio is 5 or more, and preferably, the molar ratio is from 0.4 to 2.0 molar relative to the raw material dicarboxylic anhydride.

The reaction temperature ranges from 110°C to 220°C.

It is preferable to carry out the reaction while removing the water produced in the condensation reaction from the system using an azeotropic phenomenon. Particularly when the reaction is carried out in the presence of boric acid or a mixture of boric acid and boric anhydride, water is removed from the system. By carrying out the reaction while removing from the system using an azeotropic phenomenon, the formation of a solid solution can be avoided and the desired reaction can be completed with smooth stirring from beginning to end.

Hereinafter, the present invention will be explained by examples.

In the text, parts refer to parts by weight.

Example 1 1-naphthol 1009 (0,69 mol) boric anhydride I
on and phthalic anhydride 300. ! i' (2.03 mol) is placed in 500 Tnl of O-dichlorobenzene and heated in an oil bath.

Moisture begins to distill from the time the internal temperature reaches 187°C.
The contents are dissolved in O-dichlorobenzene.

After the temperature reaches 190°C, an orange precipitate gradually forms, but the mixture is kept at 190°C while stirring for about 5 hours.

During this time, the water distilled out is distilled out of the reactor.

After the reaction is complete, O-dichlorobenzene is recovered by steam distillation.

The residue was stirred with a total volume of 3,000 ml of hot water and then filtered while hot. The resulting filtrate was thoroughly washed with hot water to remove water-soluble impurities, and the insoluble matter was further stirred with a caustic soda aqueous solution to remove the insoluble matter. 2-(2'carboxybenzoyl)-1
- pale yellow crystals of naphthol (mpl 86-7°C) 1
38 g (yield based on naphthol; 72%) was obtained.

Example 2 Phthalic anhydride 30. ! 7 (0,203 mol), IO g of 4chloro-1-naphthol (0,056 mol) and 10 g of boric anhydride in 50 TLl of O-dichlorobenzene.
The reaction and treatment were carried out in the same manner as in Example 1 to obtain pale yellow crystals (mp 211°C) of 2(2'-carboxybenzoyl)-4-chloro-1=naphthol.

Example 3 3456-tetrachlorophthalic anhydride 30!9 (0,105 mol), ■-naphthol 10.9
(0,069 mol), 5 g of boric anhydride in tetralymph O
After heating and condensing in mJ at 200°C for 3 hours, the treatment according to Example 1 yielded 2-(2'-carboxy-3/, 4/, 5/, 6/-tetrachlorobenzoyl)- Yellow crystals of 1-naphthol (m92
12°C).

Examples 4 to 8 3,6-dichlorophthalic anhydride instead of 3,4,5,6-tetrachlorophthalic anhydride in Example 3,
The following procedure was carried out in the same manner except that 3-methoxyphthalic anhydride, 3-nitrophthalic anhydride, trimellitic anhydride or 4-hydroxyphthalic anhydride was used to obtain the 1-naphthol derivatives shown in the following table.

Example 9 20 g of naphthalene-2,3-dicarboxylic anhydride (0,
101 mol), 15 g (0.104 mol) of 1-naphthol, and 1 (l) of boric anhydride were heated and reacted in 100 TIL of 1.2.4-trichlorobenzene at 200°C for 3 hours, and post-treated according to Example 1. and 2-(3'-carboxy-
Pale yellow crystals of 2'-naphthoyl)-1-naphthol (m
p256-7°C (decomposition)).

Example 10 1.5-dihydroxynaphthalene 20 g (0,125 mol), phthalic anhydride 20. ! 9 (0,135 mol) in 1001 rL of xylene with 10 g of boric anhydride,
After heating under reflux for 10 hours, treatment was carried out according to Example 1 to give pale yellow crystals of 2-(2'-carboxybenzoyl)-5-hydroxy-1-naphthol (mp 221°C).
get.

Example 11 5-methoxy-1-naphthol was used instead of 1,5-dihydroxynaphthalene in Example 10, and the reaction and treatment were carried out in the same manner as in Example 10, except that 2-(2'
-carboxybenzoyl)-5-methoxy-1-naphthol (mp 210-212°C) was obtained.

Example 12 After reacting 10 g (0,102 mol) of maleic anhydride, 1 M (0,069 mol) of 1-naphthol, and io, y of boric anhydride in 50 ml of monochlorobenzene under reflux for 10 hours,
Work up as in Example 1 to obtain 2-(3'-carboxypropenoyl)-1-naphthol (mp 173°C).

Example 13 Hexahydrophthalic anhydride was used instead of maleic anhydride in Example 12, and the reaction and treatment were otherwise carried out in the same manner as in Example 12 to produce 2-(2'-hydroxyhexahydrobenzoyl). -1-naphthol (mp 194~
196°C).

Example 14 ■-Naphthol 10 (1, 50 g of boric acid and 300 g of phthalic anhydride are heated together with 500 ml of O-dichlorobenzene in an oil bath.

Water is generated actively, and when the water generation stops, the contents become a homogeneous solution.

Even if the reaction continues at this stage, the quality and yield of the target product will be poor.

Here, 3 (l) of boric anhydride is added and the reaction is carried out for 3 hours while the solvent is refluxed.

After cooling, the contents were treated in the same manner as in Example 1 to obtain 2-(2'-
(carboxybenzoyl)-1-naphthol is obtained.

If 50 g or more of boric acid is initially used in this reaction, a glassy solid mass will precipitate, making stirring difficult.

Also, instead of adding boric anhydride in the latter stage, 50% boric acid!
! The reaction can also be carried out by adding a small amount of the compound over several hours to avoid precipitation of glass bodies.

The reaction proceeds in the presence of boric anhydride produced by dehydration.

Example 15 1-naphthol 100g, boric acid 50g, phthalic anhydride 300g. ! 9 was heated in an oil bath with 500 ml of O-dichlorobenzene.

Water was actively generated, and by the time the water generation stopped, the contents became a homogeneous solution.

Next, boric acid 5 (L9) was added little by little over several hours so as not to precipitate a glass body, and the mixture was stirred and at the same time the produced water was distilled off.

The content is a liquid containing a suspension as in Example 1, which is treated in the same manner as in Example 1 to produce pale yellow crystals of 2-(2'-carboxybenzoyl)-1-naphthol with a yield of about 70%. I got it.

Claims (1)

[Scope of Claims] 1 Represented by the general formula (n) (wherein R represents a hydrogen atom, a halogen atom, a hydroxyl group, or a lower alkoxy group, and is substituted at a position other than the 2- and 3-positions of the naphthalene nucleus) 1-naphthol compound and general formula (1) (wherein A is a benzene nucleus, a naphthalene nucleus, which may be substituted with a nitro group, a halogen atom, a hydroxyl group, a carboxyl group or an ester residue thereof, or a lower alkoxy group, -CH2-CH
2CH2-CH2-CH2-CH2 -CH=CH- or -CHCH-) in the presence of boric anhydride and/or boric acid, toluene, xylene,
Ethylbenzene, diethylbenzene, isopropylbenzene, amylbenzene, cymene, tetralin, decalin, tetrachlorethylene, tetrabromoethylene, trichloropropane, chlorobenzene, dichlorobenzene,
The reaction is carried out in any one organic solvent selected from the group consisting of trichlorobenzene, chlorotoluene, and bromobenzene at a temperature of 110 to 220°C while removing water in the reaction system from the reaction system. The general formula (I
) (wherein R and A have the same meanings as in general formulas (II) and (1)).