JPH0532591A - Production of metallic complex of o-hydroxynitroso aromatic compound - Google Patents

Abstract

PURPOSE:To readily obtain the subject compound, useful as a synthetic intermediate such as functional coloring matters, etc., and having various substituent groups at the p-position with respect to the nitroso group and the m-position with respect to the hydroxy group according to a specific method. CONSTITUTION:A metallic complex of an o-hydroxynitroso aromatic compound expressed by formula I [R<1> is hydroxy, amino, etc.; (n) is 0-3; the alpha-rind is 1-18C rind, provided that the absence of the alpha-ring is also included] is reacted with a compound expressed by the formula HX (X is amino, 1-20C alkylthione, etc.), preferably at 20-150 deg.C for 0.1-48hr to afford the objective compound expressed by formula II. In the reaction, a basic compound such as triethylamine is preferably made to coexist to smoothly advance the reaction. Thereby, e.g. copper (II) complex of 1-nitroso-2-naphthol is cited as the complex of the aforementioned compound expressed by formula I. For example, piperidine is cited as the compound expressed by formula HX.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a metal complex of an o-hydroxynitroso aromatic compound, which is useful as a synthetic intermediate for functional dyes and the like.

[0002]

2. Description of the Related Art As a method for producing a metal complex of an o-hydroxynitroso aromatic compound, a method of mixing an o-hydroxynitroso aromatic compound and a metal ion in a solution to form a complex is known. An example of this is
Nihon Kagaku Magazine Vol. 92 No. 1 (1971) 92-93
There is a description on the page.

Another method for producing a metal complex of an o-hydroxynitroso aromatic compound is a method of reacting a hydroxy aromatic compound with a nitrosating reagent in the presence of a metal ion. Such an example is described in J. Or
g. Chem. , 32 , 2516 (1967), Bu
ll. Chem. Soc. Jpn. , 43 , 139 (1
970), Bull. Chem. Soc. Jpn. ，
43 , 182 (1970), J. Am. Org. Che
m. , 12 , 1 (1947), J. Org. Che
m. , 12 , 7 (1947), J. Org. Che
m. , 12 , 20 (1947), PCT WO 88
/ 02371, USP 4,785,097 etc.

Another method for producing a metal complex of an o-hydroxynitroso aromatic compound is a method of reacting an unsubstituted aromatic compound with an oxidizing agent and a nitrosating reagent in the presence of a metal ion. An example of this is
J. Am. Chem. Soc. , 63 , 622 (194
1), Science, 92 , 336 (1940).

[0005]

However, in the conventional method, a substituent X (X is an amino group, a monosubstituted amino group having 1 to 20 carbon atoms, and a carbon number 2 at the para position of the nitroso group and the meta position of the hydroxy group is used. To 40 disubstituted amino groups, 1 to 1 carbon atoms
20 alkoxy group, C 7-15 aralkoxy group, C 6-14 aryloxy group, C 1-20
Of an alkylthio group, an aralkylthio group having 7 to 15 carbon atoms, and an arylthio group having 6 to 14 carbon atoms) is used to produce a metal complex of an o-hydroxynitroso aromatic compound. Was generally difficult.

In the above-described method of mixing an o-hydroxynitroso aromatic compound and a metal ion in a solution to form a complex, a compound having a substituent X at the para position of the nitroso group and the meta position of the hydroxy group is used. -It is necessary to use a hydroxynitroso aromatic compound as a raw material.
Hydroxynitroso aromatic compounds are difficult to synthesize and there are few types. Similarly, in the method of reacting a hydroxyaromatic compound with a nitrosating reagent in the presence of a metal ion, it is necessary to have a substituent X at an appropriate position of the starting hydroxyaromatic compound. Many group compounds are difficult to synthesize, and there are few kinds. Even when a suitable hydroxyaromatic compound is available, a rearrangement of the hydroxy group may occur, so that an o-hydroxynitrosoaromatic compound having a substituent X at the para position of the nitroso group and the meta position of the hydroxy group may be obtained. A metal complex is not always obtained. Further, in the method of reacting an unsubstituted aromatic compound with an oxidizing agent and a nitrosating reagent in the presence of a metal ion, an o-hydroxynitroso aromatic compound having a substituent X at the para position of the nitroso group and the meta position of the hydroxy group is used. No metal complex of a group compound can be formed.

The present invention is intended to solve the drawbacks of the prior art, and provides an o-hydroxynitroso aromatic compound having a wide variety of substituents X in the para position of the nitroso group and the meta position of the hydroxy group. It is an object to provide a method for easily producing a metal complex.

[0008]

In order to solve such a problem, the present invention has the following constitution.

"General formula (I)

[0010]

[Chemical 3]

A metal complex of an o-hydroxynitroso aromatic compound represented by the formula (II) characterized by reacting a compound represented by the formula HX.

[0012]

[Chemical 4]

A method for producing a metal complex of an o-hydroxynitroso aromatic compound represented by:

[In each formula, R ¹ is a hydroxy group, an amino group, a monosubstituted amino group having 1 to 20 carbon atoms, or 2 to 40 carbon atoms.
A disubstituted amino group, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, and an alkyl group having 1 to 20 carbon atoms. An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogeno group, a cyano group, a carboxylic acid group, a nitro group, 1 to 2 carbon atoms
Selected from an acyl group having 0 to 2 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a sulfonic acid group, an alkoxysulfonyl group having 1 to 20 carbon atoms, and a sulfamoyl group having 0 to 20 carbon atoms. Represents a substituent.

N represents an integer of 0 to 3.

X is an amino group, a monosubstituted amino group having 1 to 20 carbon atoms, a disubstituted amino group having 2 to 40 carbon atoms, and 1 to 1 carbon atoms.
20 alkoxy group, C 7-15 aralkoxy group, C 6-14 aryloxy group, C 1-20
Represents an alkylthio group, a aralkylthio group having 7 to 15 carbon atoms and an arylthio group having 6 to 14 carbon atoms.

The α ring represents a ring having 3 to 18 carbon atoms, but includes the case where there is no α ring. ] In general formula (I) and general formula (II) of the present invention,
The α ring represents a ring having 3 to 18 carbon atoms, provided that there is no α ring,

[0018]

[Chemical 5]

Specific examples of the ring represented by: naphthalene ring, phenanthrene ring, anthracene ring, naphthacene ring, acephenanthrylene ring, indene ring, fluorene ring, quinoline ring, quinoxaline ring, benzofuran ring, benzothiophene ring , Dibenzofuran ring, coumarin ring, chroman ring, carbazole ring, tetrahydronaphthalene ring, dihydroanthracene ring and the like, and α
The present invention also includes a case where there is no ring but only a benzene ring.
The α ring may be unsubstituted or may have a substituent. When the α ring has a substituent, the substituent is
The same as R ¹ can be mentioned.

R ¹ is a hydroxy group, an amino group, a monosubstituted amino group having 1 to 20 carbon atoms, a disubstituted amino group having 2 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a carbon number 7
To 15 aralkoxy groups, C6 to C14 aryloxy groups, C1 to C20 acyloxy groups, C1 to C2
0 alkyl group, C 2-20 alkenyl group, C 2-20 alkynyl group, C 7-15 aralkyl group, C 6-14 aryl group, halogeno group, cyano group, carboxylic acid group , Nitro group, acyl group having 1 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, carbamoyl group having 1 to 20 carbon atoms, sulfonic acid group, alkoxysulfonyl group having 1 to 20 carbon atoms and 0 to carbon atoms
It represents a substituent selected from 20 sulfamoyl groups. n
Represents an integer of 0 to 3. However, R ¹ does not exist in the para position of the nitroso group and the meta position of the hydroxy group.

The metal complex of the o-hydroxynitroso aromatic compound represented by the general formula (I) used in the present invention can be obtained by the method mentioned in the section of the prior art. The metals include copper, nickel, cobalt, iron,
Silver, chromium, mercury, gold, titanium, zirconium, lanthanum, cerium, palladium, manganese, cadmium, zinc, platinum, aluminum, lead, tin and the like are preferably used.

The metal complex of the o-hydroxynitroso aromatic compound represented by the general formula (I) may be isolated and then used, or may be produced by the method described in the section of the prior art without isolation. The material may be used as it is in situ.

The compound represented by the formula HX is ammonia,
Monosubstituted amine having 1 to 20 carbon atoms, disubstituted amine having 2 to 40 carbon atoms, alcohol having 1 to 20 carbon atoms, and 7 to 1 carbon atoms
5 hydroxy aralkyl compound, C 6-14 hydroxy aromatic compound, C 1-20 alkyl thiol, C 7-15 aralkyl thiol, C 6
~ 14 aryl aryl thiol, having 2 to 40 carbon atoms
The di-substituted amine also includes cyclic amines such as piperidine, pyrrolidine, morpholine and thiomorpholine.

When the metal complex of the o-hydroxynitroso aromatic compound represented by the general formula (I) is reacted with the compound represented by the formula HX, one or more other compounds may coexist. . Examples of other compounds include reaction solvents, basic compounds, impurities and the like.

As the reaction solvent of the present invention, various solvents can be used, or no solvent may be used. When the compound represented by the formula HX is a liquid, good results can be obtained in terms of yield etc. by reacting the compound represented by the formula HX with a solvent amount without using any other solvent. There are many.

In the reaction of the present invention, when the metal complex of the o-hydroxynitroso aromatic compound represented by the general formula (I) is reacted with the compound represented by the formula HX, a basic compound is allowed to coexist. The reaction proceeds smoothly. Examples of the basic compound include tertiary amines such as triethylamine and pyridine; metal alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butoxide; metal hydroxides such as sodium hydroxide and potassium hydroxide. it can.

The reaction time of the present invention is preferably 0.1 to 48 hours, more preferably 1 to 24 hours from the viewpoint of reaction yield and work efficiency. When the reaction time is shorter than 0.1 hours, the reaction does not proceed sufficiently, so that the reaction yield tends to be lowered, and when the reaction time is longer than 48 hours, working efficiency is lowered. Moreover, since the reaction time is too long, the reaction yield may decrease due to side reactions such as decomposition.

The reaction temperature of the present invention is 0 from the viewpoint of reaction yield.
-200 degreeC is preferable and 20-150 degreeC is more preferable. When the reaction temperature is lower than 0 ° C., the reaction does not proceed sufficiently, so that the reaction yield tends to decrease. Also, when the reaction temperature is higher than 200 ° C., side reactions such as decomposition may cause The reaction yield tends to decrease.

In the reaction of the present invention, the mixing molar ratio of each substance is such that the compound represented by the formula HX is 0 with respect to 1 mol of the metal complex of the o-hydroxynitroso aromatic compound represented by the general formula (I). 0.2 mol or more is preferable, and 1-100 mol is more preferable. In addition, in the reaction of the present invention, when a basic substance is allowed to coexist, the number of moles of the substance is represented by the general formula (I)
The amount is preferably 0.01 to 2 mol per 1 mol of the metal complex of the o-hydroxynitroso aromatic compound represented by. If it is out of this range, the yield may decrease.

The metal complex of the o-hydroxynitroso aromatic compound represented by the general formula (I) can be purified by recrystallization with various solvents, solvent extraction with various solvents, chromatography, activated carbon treatment. Etc. are preferably used.

The metal complex of the o-hydroxynitroso aromatic compound represented by the general formula (II) obtained by the production method of the present invention is prepared by removing the metal by a generally known suitable treatment, It can be converted to an o-hydroxynitroso aromatic compound represented by (II). One of such treatment methods is a method in which an acid such as hydrochloric acid or sulfuric acid is allowed to act on the metal complex of the o-hydroxynitroso aromatic compound represented by the general formula (II). More specifically, a method in which a metal complex of an o-hydroxynitroso aromatic compound represented by the general formula (II) is suspended in hydrochloric acid or sulfuric acid and then extracted with an organic solvent; A method of dissolving or suspending the indicated metal complex of an o-hydroxynitroso aromatic compound in an organic solvent immiscible with water, adding hydrochloric acid or sulfuric acid thereto, and then stirring or shaking the mixture to obtain an organic layer. And the like are preferred examples.

[0032]

EXAMPLES The present invention will now be described with reference to examples, but the present invention is not limited thereto.

Example 1 A copper (II) complex of 1-nitroso-2-naphthol was prepared by
Prepared according to the method described in Example 1 of USP 4,785,097. 20.4 g of the obtained copper (II) complex of 1-nitroso-2-naphthol was reacted in the presence of 5.4 g of sodium ethoxide in 400 ml of absolute ethanol at a reflux temperature for 3 hours.

After the reaction, ethanol was distilled off under reduced pressure,
The obtained solid was washed with water and ethanol, and further dried under reduced pressure to obtain a copper (II) complex of 4-ethoxy-1-nitroso-2-naphthol.

1.0 g of the obtained copper (II) complex of 4-ethoxy-1-nitroso-2-naphthol, 1-3,
1.0 g of 3-trimethyl-2-methylene-indoline
Was reacted in 20 ml of ethanol at a reflux temperature for 20 hours, and the following formula (III)

[0036]

[Chemical 6]

A compound of formula was produced. From this, it was confirmed that a copper (II) complex of 4-ethoxy-1-nitroso-2-naphthol was produced by the method of Example 1-.

Example 2 20.4 g of a copper (II) complex of 1-nitroso-2-naphthol prepared according to the method described in Example 1 of USP 4,785,097 and 10 g of piperidine were added to 40
The reaction was carried out in 0 ml of absolute ethanol at the reflux temperature for 3 hours.

After the reaction, ethanol was distilled off under reduced pressure,
The obtained solid was washed with water and ethanol, and further dried under reduced pressure to obtain a copper (II) complex of 1-nitroso-4-piperidino-2-naphthol.

1.0 g of the obtained copper (II) complex of 1-nitroso-4-piperidino-2-naphthol and 1-
3,3-trimethyl-2-methylene-indoline 1.0
g in 20 ml of ethanol at a reflux temperature for 20 hours, the following formula (IV)

[0041]

[Chemical 7]

A compound of formula was produced. From this, it was confirmed that a copper (II) complex of 1-nitroso-4-piperidino-2-naphthol was produced by the method of Example 2-.

[0043]

INDUSTRIAL APPLICABILITY According to the production method of the present invention, various substituents X (X is an amino group, a monosubstituted amino group having 1 to 20 carbon atoms, at the para position of the nitroso group and the meta position of the hydroxy group,
Disubstituted amino group having 2 to 40 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aralkoxy group having 7 to 15 carbon atoms, aryloxy group having 6 to 14 carbon atoms, alkylthio group having 1 to 20 carbon atoms, and 7 carbon atoms ~ 15 aralkylthio groups, 6 carbon atoms
A metal complex of an o-hydroxynitroso aromatic compound having a substituent selected from an arylthio group of -14) can be easily produced.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Reference number within the agency FI Technical indication C07C 309/47 9160-4H 309/76 9160-4H 311/39 7419-4H 319/14 323/38 7419-4H C07D 307/78 7729-4C 307/87 7729-4C 307/91 7729-4C 333/52 7729-4C 333/72 7729-4C C07F 1/08 Z 6742-4H // C07D 215/38 7019-4C

Claims (4)

[Claims] 1. A compound represented by the general formula (I): A metal complex of an o-hydroxynitroso aromatic compound represented by the formula (II) and a compound represented by the formula HX are reacted. A method for producing a metal complex of an o-hydroxynitroso aromatic compound represented by: [In each formula, R ¹ is a hydroxy group, an amino group, a monosubstituted amino group having 1 to 20 carbon atoms, or 2 to 4 carbon atoms.
A disubstituted amino group of 0, an alkoxy group having 1 to 20 carbon atoms,
Aralkoxy group having 7 to 15 carbon atoms, aryloxy group having 6 to 14 carbon atoms, acyloxy group having 1 to 20 carbon atoms, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, and 2 to 20 carbon atoms. Alkynyl group, aralkyl group having 7 to 15 carbon atoms, aryl group having 6 to 14 carbon atoms, halogeno group, cyano group, carboxylic acid group, nitro group, 1 to 2 carbon atoms
Selected from an acyl group having 0 to 2 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a sulfonic acid group, an alkoxysulfonyl group having 1 to 20 carbon atoms, and a sulfamoyl group having 0 to 20 carbon atoms. Represents a substituent. n represents an integer of 0 to 3. X is an amino group, a monosubstituted amino group having 1 to 20 carbon atoms, a disubstituted amino group having 2 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 7 to 7 carbon atoms.
15 aralkoxy group, C6-14 aryloxy group, C1-20 alkylthio group, C7-15
Represents a substituent selected from an aralkylthio group and an arylthio group having 6 to 14 carbon atoms. α ring has 3 to 18 carbon atoms
Represents the ring, but also includes the case where there is no α ring. ] 2. A metal complex of an o-hydroxynitroso aromatic compound represented by the general formula (I) according to claim 1,
A compound of formula HX at 0-200 ° C.
A method for producing a metal complex of an o-hydroxynitroso aromatic compound, which comprises reacting for 48 hours. 3. The method according to claim 1, wherein 0.2 mol or more of the compound represented by the formula HX is reacted with 1 mol of the metal complex of the o-hydroxynitroso aromatic compound represented by the general formula (I). A method for producing a metal complex of an o-hydroxynitroso aromatic compound, which is characterized. 4. The method according to claim 1, wherein a metal complex of an o-hydroxynitroso aromatic compound represented by the general formula (I), a compound represented by the formula HX and a basic compound are reacted. Process for producing metal complex of hydroxynitroso aromatic compound.