JP2003267938A - Method for producing aminonaphthoquinones - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing aminonaphthoquinones. <P>SOLUTION: This method for producing the aminonaphthoquinones comprises reacting a naphthoquinone compound expressed by general formula (I) (lines 2-2' and 3-4 are each a double bond and lines 2-3 and 4-4' are each a single bond, when X<SB>a</SB>is O and Y<SB>a</SB>is H; lines 2-2' and 3-4 are each a single bond and lines 2-3 and 4-4' are each a double bond, when X<SB>a</SB>is H and Y<SB>a</SB>is O; and R<SB>1</SB>is a halogen, a hydrocarbon residue or the like) with a hydroxylamine salt expressed by formula (II): (NH<SB>2</SB>OH)<SB>m</SB>.H<SB>n</SB>A (H<SB>n</SB>A is a mineral acid; and m is 1-3) in the presence of a metal hydroxide to form the aminonaphthoquinone expressed by formula (III) (lines 2-2' and 3-4 are each a double bond and lines 2-3 and 4-4' are each a single bond, when X<SB>b</SB>is O and Y<SB>b</SB>is amino; and lines 2-2' and 3-4 are each a single bond and lines 2-3 and 4-4' are each a double bond, when X<SB>b</SB>is amino and Y<SB>b</SB>is O). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing aminonaphthoquinones.

[0002]

BACKGROUND OF THE INVENTION Aminonaphthoquinones are useful as raw materials or intermediates for fungicides, pharmaceuticals and agricultural chemicals, or as an intermediate for couplers such as photographic films. As a production method thereof, there is known a method of aminating naphthoquinones with O-alkylhydroxylamine hydrochlorides such as O-benzylhydroxylamine hydrochloride, hydroxylamine hydrochloride, O-methylhydroxylamine hydrochloride and triethylamine. (Synthesis, 917 (199
Four)). However, in such a conventional manufacturing method, triethylamine is used as a base, but there is a concern that triethylamine, which is an organic amine compound, may be mixed in the product. In addition, in these reactions, a general formula (I
V) [In the formula, Xa and Ya are different from each other and are oxygen atom or NO.
Representing H group or hydrogen atom, the double line of dotted line and solid line is
Represents a single or double bond. Xa is an oxygen atom or N
When Ya is a hydrogen atom in the OH group, 2-2 ′ and 3
Between -4 represents a double bond, and between 2-3 and 4-4 'represents a single bond. When Xa is a hydrogen atom and Ya is an oxygen atom or a NOH group, 2-2 ′ and 3-4 represent a single bond, and 2-3 and 4-4 ′ represent a double bond. R ₁ represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a lower alkoxy group, an aryl group, an aryloxy group, an aralkyl group or a hydroxyl group. ] There was a problem such as formation of naphthoquinone oximes.

[0003]

Therefore, as a result of intensive investigations by the present inventors to develop a method capable of producing aminonaphthoquinones with higher selectivity and high yield, a method for producing aminonaphthoquinones from naphthoquinones In the case of using a metal hydroxide as a base in the above, a large amount of naphthoquinone oxime which is a reaction by-product is produced in O-alkylhydroxylamine salts, whereas hydroxylamine salts, which are relatively inexpensive, are highly selective and yield high. The inventors have found that aminonaphthoquinones are produced and have reached the present invention.

[0004]

That is, the present invention provides a compound represented by the general formula (I) [In the formula, Xa and Ya are different from each other and represent an oxygen atom or a hydrogen atom, and a double line of a dotted line and a solid line represents a single or double bond. When Xa is an oxygen atom and Ya is a hydrogen atom, a double bond is present between 2-2 ′ and 3-4.
And between 4 and 4'represents a single bond. Xa is a hydrogen atom and Y
When a is an oxygen atom, between 2-2 ′ and 3-4,
It represents a single bond and represents a double bond between 2-3 and 4-4 '. R ₁ represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a lower alkoxy group, an aryl group, an aryloxy group, an aralkyl group or a hydroxyl group. ] And naphthoquinones represented by the general formula (II) [In the formula, m represents an integer of 1 to 3, and HnA represents a mineral acid. ] It reacts with the hydroxylamine salt shown by these in the presence of metal hydroxide, General formula (III) characterized by the above-mentioned. [In the formula, Xb and Yb are different from each other and represent an oxygen atom or an amino group, and a double line of a dotted line and a solid line represents a single or double bond. When Xb is an oxygen atom and Yb is an amino group, 2-2 ′ and 3-4 represent a double bond and 2-3
And between 4 and 4'represents a single bond. Xb is an amino group and Y
When b is an oxygen atom, between 2-2 'and 3-4,
It represents a single bond and represents a double bond between 2-3 and 4-4 '. R ₁ has the same meaning as described above. ] The manufacturing method of aminonaphthoquinone shown by these is provided.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the naphthoquinones represented by the general formula (I), examples of the halogen atom in R ¹ include fluorine, chlorine, bromine and iodine atoms.
Examples of the aliphatic hydrocarbon group of 10 include a methyl group,
Examples of the linear or branched saturated or unsaturated aliphatic hydrocarbon group such as ethyl group, propyl group, t-butyl group, allyl group and vinyl group, and lower alkoxy group include methoxy, ethoxy and t-butoxy groups. A linear or branched lower alkoxy group, an aryl group such as a phenyl group or a 3-methylphenyl group, and an aryloxy group such as a phenoxy group or a 3-methylphenoxy group or an aralkyl group. Examples thereof include a benzyl group.

Examples of such naphthoquinones (I) include 1,4-naphthoquinone, 5-chloro-1,4-naphthoquinone, 6-chloro-1,4-naphthoquinone, 5-bromo-1,4-naphthoquinone, 6 -Bromo-1,4-naphthoquinone, 5-methyl-1,4-naphthoquinone, 6-
Ethyl-1,4-naphthoquinone, 5-methoxy-1,4
-Naphthoquinone, 6-t-butoxy-1,4-naphthoquinone, 6-hydroxy-1,4-naphthoquinone, 6-phenyl-1,4-naphthoquinone, 5-benzyl-1,4
-Naphthoquinone, 1,2-naphthoquinone, 5-chloro-
1,2-naphthoquinone, 6-chloro-1,2-naphthoquinone, 5-bromo-1,2-naphthoquinone, 6-bromo-1,2-naphthoquinone, 5-methyl-1,2-naphthoquinone, 6-ethyl- 1,2-naphthoquinone, 5-methoxy-1,2-naphthoquinone, 6-t-butoxy-1,
2-naphthoquinone, 6-hydroxy-1,2-naphthoquinone, 6-phenyl-1,2-naphthoquinone, 5-benzyl-1,2-naphthoquinone and the like can be mentioned.

Mineral acids represented by HnA in hydroxylamine salts (II) include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid. Examples thereof include hydroxylamine hydrochloride,
Examples thereof include hydroxylamine sulfate, hydroxylamine nitrate, hydroxylamine phosphate and the like. Hydroxylamine hydrochloride and hydroxylamine sulfate are preferably used. When the amount of m is 1, the amount of the hydroxylamine salt (II) is usually 0.8 mol times, preferably 1 mol times or more, and usually 10 mol times or less, preferably 10 mol times, relative to the naphthoquinone (I). Is 5 mol times or less, and when m is 2, naphthoquinones (I)
In contrast, the amount is usually 0.4 mol times, preferably 0.5 mol times or more, usually 5 mol times or less, preferably 2.5 mol times or less, and when m is 3, naphthoquinones (I )
On the other hand, it is usually 0.27 mol times or more, preferably 0.33 mol times or more, and usually 3.33 mol times or less, preferably 1.67 mol times or less.

Examples of metal hydroxides include alkali metal hydroxides and alkaline earth metal hydroxides. Specific examples of metal hydroxides include, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, and hydroxide. Cesium, calcium hydroxide, barium hydroxide and the like can be mentioned, with preference given to sodium hydroxide and potassium hydroxide. The amount of such metal hydroxides used is usually 0.8 equivalents, preferably 1 equivalent or more, and usually 10 equivalents or less, preferably 5 equivalents or less with respect to the naphthoquinones (I).

The reaction of such naphthoquinones (I), hydroxylamine salts and metal hydroxides is usually carried out in a solvent. Examples of the solvent include alcohol solvents such as methanol, ethanol, isopropanol and t-butanol, aprotic solvents such as N, N-dimethylformamide and dimethylsulfoxide, diethyl ether, diisopropyl ether, diethylene glycol dimethyl ether and 1,4-dioxane. , An ether solvent such as tetrahydrofuran, a halogen solvent such as dichloromethane, dichloroethane, chlorobenzene and dichlorobenzene, an aromatic hydrocarbon such as benzene, toluene and xylene, and an aliphatic hydrocarbon such as hexane and heptane. These organic solvents are used alone or in combination of two or more, and the amount thereof is usually 1 times by weight or more and 200 times that of the naphthoquinones (I).
The weight is not more than twice, preferably not less than 2 times and not more than 100 times. Among these solvents, alcohol solvents are desirable.

To react with naphthoquinones (I), hydroxylamine salts and metal hydroxides, the hydroxylamine salts and metal hydroxides are mixed in a solvent under an inert gas atmosphere such as nitrogen gas, and then, Add naphthoquinones. Naphthoquinone may be added as it is, or may be dissolved in a solvent and added dropwise. At this time, all of the naphthoquinones (I) and the metal hydrides may be dissolved in the organic solvent, or some of them may be present as a solid in the organic solvent without being dissolved. The reaction temperature is usually −40 ° C. or higher, preferably 0 ° C. or higher, usually 120 ° C. or lower, and when the boiling point of the organic solvent is lower than 120 ° C., it is the boiling point or lower. The reaction time is usually 0.
It is 1 hour or more and 72 hours or less, preferably about 0.5 hour or more and 24 hours or less.

Thus, the naphthoquinones (I) react with hydroxylamine salts to produce the desired aminonaphthoquinones (III).
In order to take out I), for example, when crystals are precipitated, they are crystallized as they are, and aminonaphthoquinones (III) are obtained.
The aminonaphthoquinones (III) may be taken out as crystals by mixing the reaction mixture with a poor solvent such as water to precipitate the aminonaphthoquinones (III). To mix the reaction mixture with the poor solvent, the poor solvent may be added to the reaction mixture, or the reaction mixture may be added to the poor solvent. The crystals can be easily taken out by a method such as filtration. Further, the solvent was distilled off from the reaction mixture, and then the aminonaphthoquinones (I
II) may be solvent extracted. After extraction, the solvent is distilled off to obtain crystals of aminonaphthoquinone (III). Aminonaphthoquinones taken out (II
I) may be purified by a method such as chromatography or recrystallization.

[0012]

According to the production method of the present invention, aminonaphthoquinones (III) can be produced in good yield.

[0013]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 Hydroxyamine hydrochloride 278.0 mg under nitrogen atmosphere
(4 mmol) and 16 ml of ethanol were mixed and cooled to 0 ° C. Next, 224.4 mg of potassium hydroxide (4
mmol) was added and the mixture was stirred at the same temperature for 15 minutes. 314.1 mg (2 mm of 1,4-naphthoquinone was added to the reaction mixture.
ol) in ethanol (3 ml) was added dropwise at the same temperature over 15 minutes, the temperature was raised to 25 ° C., and the reaction mixture after stirring was analyzed by gas chromatography and gas chromatography gravimetric analysis, and aminonaphthoquinones (I
II) and the by-product naphthoquinone oxime (I
The yield of V) was calculated and the results are shown in Table 1.

Comparative Example 1 The reaction was carried out in accordance with Example 1 except that O-methylhydroxylamine hydrochloride was used instead of hydroxylamine hydrochloride. The reaction mixture after stirring was analyzed by gas chromatography and gas chromatography gravimetric analysis to calculate the yields of aminonaphthoquinones (III) and by-product naphthoquinone oxime (IV), and the results are shown in Table 1. .

[Table 1]

Continued front page    F-term (reference) 4H006 AA02 AC52 BA02 BA03 BA04                       BA06 BA29 BE90 BJ50 BR80                       BU46                 4H039 CA71 CD10

Claims (3)

[Claims] 1. A general formula (I) [In the formula, Xa and Ya are different from each other and represent an oxygen atom or a hydrogen atom, and a double line of a dotted line and a solid line represents a single or double bond. When Xa is an oxygen atom and Ya is a hydrogen atom, a double bond is present between 2-2 ′ and 3-4.
And between 4 and 4'represents a single bond. Xa is a hydrogen atom and Y
When a is an oxygen atom, between 2-2 ′ and 3-4,
It represents a single bond and represents a double bond between 2-3 and 4-4 '. R ₁ represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a lower alkoxy group, an aryl group, an aryloxy group, an aralkyl group or a hydroxyl group. ] And naphthoquinones represented by the general formula (II) [In the formula, m represents an integer of 1 to 3, and HnA represents a mineral acid. ] It reacts with the hydroxylamine salt shown by these in the presence of metal hydroxide, General formula (III) characterized by the above-mentioned. [In the formula, Xb and Yb are different from each other and represent an oxygen atom or an amino group, and a double line of a dotted line and a solid line represents a single or double bond. When Xb is an oxygen atom and Yb is an amino group, 2-2 ′ and 3-4 represent a double bond and 2-3
And between 4 and 4'represents a single bond. Xb is an amino group and Y
When b is an oxygen atom, between 2-2 'and 3-4,
It represents a single bond and represents a double bond between 2-3 and 4-4 '. R ₁ has the same meaning as described above. ] The manufacturing method of aminonaphthoquinone shown by these. 2. The method according to claim 1, wherein the hydroxylamine salt is hydroxylamine hydrochloride or hydroxylamine sulfate. 3. The metal hydroxide is lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide or barium hydroxide.
The manufacturing method described in.