JP2003081921A - Method for producing 1,5-diaminonaphthalene - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce wastes in producing a 1,5-diaminonaphthalene from an ortho-alkylnitrobenzene and a vinyl compound as raw materials. SOLUTION: In this method for producing the 1,5-diaminonaphthalene through a 4-(2-nitrobenzene)propane and a 5-nitro-1-tetralone an acid obtained in another process is used for the neutralization treatment of a base used for the reaction. Thereby, wastes in producing the 1,5-diaminonaphthalene compound can be reduced.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing 1,5-diaminonaphthalene compounds. The 1,5-diaminonaphthalene obtained by the method of the present invention is useful as a compound as a raw material for various synthetic resins. 1,5-Diaminonaphthalene is used as a polyurethane resin raw material by reacting it with phosgene or the like to convert it to diisocyanate, or as a polyamide resin by reacting it with a dicarboxylic acid derivative or the like.

[0002]

2. Description of the Related Art Conventionally, 1,5-diaminonaphthalene has been produced by nitrating naphthalene to give dinitronaphthalene, and then reducing the nitro group to an amino group.

However, in the dinitration reaction of naphthalene, a large amount of 1,8-dinitro compound is produced in addition to the desired 1,5-dinitro compound. For example, in Japanese Patent Laid-Open No. 51-070757, 1-
Nitronaphthalene is nitrated in a chlorine-containing organic solvent, but the yield of 1,5-dinitro compound is 30%, whereas
-The yield of dinitro compound is 65%, and more than twice as much 1,8-dinitro compound is produced as 1,5-dinitro compound. The 1,8-dinitro compound is a compound that is used as a raw material for dyes and the like, but when the demand for the 1,8-compound is low, the production amount of the 1,5-compound is also linked, so the required amount It becomes difficult to produce 1,5-diaminonaphthalene.

Under these circumstances, an attempt has been made to increase the amount of 1,5-form produced in the dinitration reaction of naphthalene. For example, in WO9912887, 1-nitronaphthalene is nitrated with nitric acid using Nafion, and the yield of 1,5-dinitro compound is 34.1.
%, The yield of 1,8-dinitro compound was 38.0%, and we succeeded in increasing the ratio of 1,5-dinitro compound. Absent.

As described above, according to the currently adopted production route, a large amount of 1,8-dinitro compound is produced in addition to 1,5-dinitronaphthalene, and therefore, a selective method for producing 1,5-diaminonaphthalene. Was desired.

In addition to the dinitration / nitro group reduction method of naphthalene, a method of aminating 1,5-dihydroxynaphthalene as a raw material (US5113025, JP-B-59-29061), 5-halogeno-1-aminonaphthalene and 1, Method for aminating 5-dihalogenonaphthalene (JP-A-7-278066, US3787496), 1,5
-A method for aminating sodium naphthalenedisulfonate (Journal of the Chemical Society of Japan 522 (1974)) and the like have been proposed. However, when attempting to produce 1,5-dihydroxynaphthalene by the cumene method, 1,5-diisopropylnaphthalene, which is the starting material, tends to transfer an isopropyl group to the β-position due to its steric hindrance, resulting in a dinitration / nitro group reduction method. Similarly, it is hard to say that it is a selective method. Halogenation and sulfonation of naphthalene are also methods lacking in selectivity. On the other hand, the present inventors have found a method for selectively producing 1,5-diaminonaphthalene by using an orthoalkylnitrobenzene compound and a vinyl compound as starting materials and passing through 5-nitro-1-tetralones. (Japanese Patent Application 2001-136962, Japanese Patent Application 2001-161619, Japanese Patent Application 2001-2711763).

[0007]

The above-mentioned orthoalkylnitrobenzene compound and vinyl compound are used as starting materials and 5-
In the method for producing 1,5-diaminonaphthalene via nitro-1-tetralone, when a 4- (2-nitrobenzene) propane compound is obtained by reacting an orthoalkylnitrobenzene compound with a vinyl compound, the reaction Can be obtained with
4- (2-nitrobenzene) propane compound requires 1 equivalent or more of base, and 4- (2-nitrobenzene) propane
In the cyclization reaction step for converting propane compounds to 5-nitro-1-tetralones, a large excess of super-strong acid is used, part of which is decomposed by water generated in the cyclization reaction, and acid such as sulfuric acid is added as a by-product. To live.

Therefore, in view of economic efficiency and environmental problems associated with wastewater treatment, there is a strong demand for efficient treatment of a large amount of base or superacid. The problem to be solved by the present invention is a method for producing 1,5-diaminonaphthalene compounds using the orthoalkylnitrobenzene compound and a vinyl compound as starting materials, in which the base or superacid used in each step is effectively used, which is economical. An object of the present invention is to provide a method for producing 1,5-diaminonaphthalene, which has excellent properties and has a low environmental load.

[0009]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors separate or recover / reuse the base used in each step, a super strong acid, or the acid produced by the reaction. Thus, a method for efficiently producing 1,5-diaminonaphthalene compounds was found, and the present invention was completed.

That is, the present invention provides [1] general formula (1):

[0011]

[Chemical 6]

(In the general formula (1), R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom or a carbon number of 1 to 4).
Represents an alkyl group, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a halogen atom. And an orthoalkylnitrobenzene compound represented by the general formula (2):

[0013]

[Chemical 7]

(In the general formula (2), R ⁵ and R ⁶ are the same or different and each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and R ⁵ and R ⁶ are cis or A vinyl compound represented by the formula (3): in the position of trans, and X represents an electron-withdrawing group.

[0015]

[Chemical 8]

(In the general formula (3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ and X represent the groups defined by the general formula (1) and the general formula (2). And a step (I) for obtaining a 4- (2-nitrobenzene) propane compound represented by the formula (4)
A cyclization reaction of a (2-nitrobenzene) propane compound in the presence of a superacid is carried out by the general formula (4):

[0017]

[Chemical 9]

(In the general formula (4), R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ represents a group defined by the general formula (1) and the general formula (2). ) In the step (II) of converting to 5-nitro-1-tetralones, and the 5-nitro-1-tetralones represented by the general formula (4) in the general formula (5):

[0019]

[Chemical 10]

(In the general formula (5), R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ represents a group defined by the general formula (1) and the general formula (2). In the process for producing 1,5-diaminonaphthalene, which comprises the step (III) of converting to 1,5-diaminonaphthalene, the super strong acid used in the step (II) is recovered by distillation after the cyclization reaction. And reusing in the reaction, the method for producing 1,5-diaminonaphthalene represented by the general formula (5), [2] part of the super strong acid used in the step (II) is a ring. The method according to [1], wherein the acid generated by decomposition during the chemical reaction is used for the neutralization treatment of the base used in the step (I).
[3] In the general formula (2) and the general formula (3), X is a nitrile group, a carboxyl group or a group represented by CO ₂ R ⁷ , and the method according to [1] or [2]. (Here, R ⁷ represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a benzyl group).

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION R ¹ , R ² , R ³ , R of the orthoalkylnitrobenzene compound represented by the general formula (1) and the vinyl compound represented by the general formula (2) used in the present invention.
⁴ are the same or different, each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a halogen atom, and R ⁵ and R ⁶ are the same or different. , A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have 1 carbon atom
The alkyl groups of 4 to 4 are methyl group, ethyl group, n-
Examples thereof include propyl group, isopropyl group, n-butyl group, i-butyl group, and t-butyl group. R ¹ , R ² , R
Examples of the aromatic hydrocarbon group of ³ and R ⁴ include a phenyl group, a tolyl group and a xylyl group.

Examples of the halogen atom of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. X is a nitrile group,
A carboxyl group and a group represented by CO ₂ R ⁷ , wherein R ⁷ represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a benzyl group.

Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group and n-
A hexyl group and the like can be mentioned. Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a xylyl group and the like.

Examples of the orthoalkylnitrobenzene compound represented by the general formula (1) used in the present invention include 2-nitrotoluene, 2,4-dimethylnitrobenzene and 2,5
-Dimethylnitrobenzene, 2,6-dimethylnitrobenzene, 2-methyl-4-ethylnitrobenzene, 2-methyl-4
-Isopropylnitrobenzene, 2-methyl-5-t-butylnitrobenzene, 2-methyl-4-chloronitrobenzene, 2-methyl-4-fluoronitrobenzene and the like. 2-
Nitrotoluene is particularly preferred because it provides useful 4- (2-nitrobenzene) propane compounds.

Examples of the vinyl compound represented by the general formula (2) include acrylonitrile, methacrylonitrile, crotononitrile, 2-chloroacrylonitrile,
3-chloroacrylonitrile, 3-ethylacrylonitrile, 3-chloromethacrylonitrile, acrylic acid, methacrylic acid, crotonic acid, 2-chloroacrylic acid, 3-chloroacrylic acid, acrylic acid methyl ester, methacrylic acid methyl ester, crotonic acid Methyl ester, 2-chloroacrylic acid methyl ester, 3-chloroacrylic acid methyl ester, 3-ethylacrylic acid methyl ester, 3
-Chloromethacrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid-i-propyl ester, methacrylic acid ethyl ester, methacrylic acid-t-butyl ester, crotonic acid-i-propyl ester and the like. Acrylonitrile, acrylic acid methyl ester and acrylic acid ethyl ester are particularly preferred because they provide useful 4- (2-nitrobenzene) propane compounds.

(Step (I): Michael Type Addition Reaction) The Michael type addition reaction of the compounds represented by the general formulas (1) and (2) of the present invention is carried out using a strong base. Strong bases include NaOH, KOH, LiOH, Na ₂ CO ₃ , K ₂ CO ₃ , CH ₃ O
Na, t-BuOK, NaH, C 6 H 5 ONa, (CH 3) 4 N + OH -, Bu 4 N + OH over,
Solid bases such as DBU and basic ion exchange resins are used, and particularly preferred bases are NaOH and KOH.
These bases may be used together with a solvent that dissolves at least a part of the base, and / or a catalyst that dissolves the base.

As a solvent for at least partially dissolving the base used, 1,3-dimethyl-2-imidazolidinone, formamide, N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N- Lower alcohols such as dimethylacetamide, hexamethylphosphoramide, dimethyl sulfoxide, sulfolane, pyridine, morpholine, tetrahydrofuran, 1,4-dioxane, acetonitrile, propionitrile, methanol, ethanol and isopropanol are used. These solvents may be mixed with water or a mixture of several kinds of solvents in order to increase the solubility of the base.

When using a catalyst that dissolves a base, any solvent can be used as long as it is a solvent inert to the reaction. 1,3-dimethyl-as a preferred solvent
An example is a mixture of 2-imidazolidinone and water.

As a catalyst for dissolving the base, a phase transfer catalyst is exemplified. Examples of the phase transfer catalyst include cetyl trimethyl ammonium bromide, tetrabutyl ammonium chloride, tetrabutyl ammonium hydroxide and the like.

The molar ratio of the raw materials used is, in the synthesis of the nitrobenzene nitrile compound, base / orthoalkyl nitrobenzene compound / acrylonitrile compound = 0.01-
1.0 / 1 / 0.1-5, and in the synthesis of a nitrobenzenecarboxylic acid ester compound and / or a nitrobenzenecarboxylic acid compound, base / orthoalkylnitrobenzene compound / acrylic acid ester compound or acrylic acid compound = 0.01 to 1.0 / 1 / 0.1-10 is preferable. The amount of the solvent used is 0.1 to 20 times the mass of the orthoalkylnitrobenzene compound, preferably 0.1.
It is 5 to 20 times by mass, and the catalyst amount for dissolving the base is 0.1 to 1 with respect to the orthoalkylnitrobenzene compound.
0 mol% may be used.

The reaction temperature will differ depending on the base and solvent used, but it is necessary to carry out the reaction at a temperature below the temperature at which the orthoalkylnitrobenzene compound decomposes, preferably below 150 ° C. The reaction time is usually in the range of 1 minute to 6 hours.

The reaction pressure may be normal pressure, increased pressure, or reduced pressure as long as the raw material and the solvent are not removed to the outside of the system, but it can be usually performed under normal pressure. The reaction is preferably carried out in the absence of oxygen.

When an acrylic ester is used as a raw material and water is mixed in the solvent, the product contains a nitrobenzenecarboxylic acid compound.

The reaction can be carried out batchwise or continuously. The reaction mixture obtained by the reaction is poured into ice water to stop the reaction, neutralized with an acid until the pH becomes 6 to 7, and oil-water separation is carried out with an organic solvent, and then the organic solvent is removed to obtain the objective. A viscous liquid containing a 4- (2-nitrobenzene) propane compound is obtained.

The extraction solvent used here is isopropyl ether, ethyl acetate, butyl acetate, carbon disulfide,
Examples include carbon tetrachloride, hexane, cyclohexane, petroleum ether, toluene, xylene, chloroform, dichloromethane, 1,2-dichloroethane, trichloroethylene, 1,2-dichlorobenzene, chlorobenzene, benzonitrile, nitromethane, nitrobenzene, anisole and diethylene glycol dimethyl ether. Other than the above compounds, the compound of interest can be dissolved, separated from water, stable under oil-water separation conditions, and having physical properties such as boiling points within the preferred ranges.

By subjecting the obtained viscous liquid to column chromatography or vacuum distillation, a highly pure nitrobenzenenitrile compound, nitrobenzenecarboxylic acid compound or nitrobenzenecarboxylic acid ester compound can be obtained. When the nitrobenzene carboxylic acid compound and the nitrobenzene carboxylic acid ester compound are a mixture, they may be separately collected by column chromatography or distillation, or the mixture of both may be esterified or hydrolyzed to form a carboxylic acid into an ester, and The ester may be converted into a carboxylic acid and recovered.

These compounds are recovered by recrystallization or column chromatography when the melting point is high or the crystallinity is good, and by vacuum distillation or column chromatography when the melting point is low or the crystallinity is poor and the thermal stability is good. , Can be purified.

Examples of the 4- (2-nitrobenzene) propane compound represented by the general formula (3) obtained by the reaction of the general formulas (1) and (2) include 4- (2-nitrobenzene) butanonitrile, 4 -(2-nitrobenzene) -2-methylbutanonitrile, 4- (2-nitrobenzene) -3-methylbutanonitrile, 4- (2-nitrobenzene) -3-ethylbutanonitrile, 4- (2-nitrobenzene ) -3-Chlorobutanonitrile, 4- (2-nitro-3-isopropylbenzene) butanonitrile, 4- (2-nitro-3-butylbenzene) butanonitrile, 4- (2-nitro-4-t-butylbenzene) ) Butanonitrile, 4- (2-nitro-5-methylbenzene) butanonitrile,
4- (2-nitro-3-methylbenzene) -2-methylbutanonitrile, 4- (2-nitro-5-isopropylbenzene) butanonitrile, 4- (2-nitro-5-chlorobenzene) butanonitrile,

4- (2-nitrobenzene) butyric acid, 4- (2-nitrobenzene) -2-methylbutyric acid, 4- (2-nitrobenzene) -3-methylbutyric acid, 4- (2-nitrobenzene) -3-ethylbutyric acid , 4- (2-
Nitro-5-isopropylbenzene) butyric acid, 4- (2-nitro-5
-Chlorobenzene) butyric acid, 4- (2-nitrobenzene) -3-chlorobutyric acid, 4- (2-nitro-3-isopropylbenzene) butyric acid,
4- (2-nitro-3-butylbenzene) butyric acid, 4- (2-nitro-4-
t-butylbenzene) butyric acid, 4- (2-nitro-5-methylbenzene) butyric acid, 4- (2-nitro-3-methylbenzene) -2-methylbutyric acid, 4- (2-nitrobenzene) butyric acid methyl ester, 4- (2-
Nitrobenzene) -2-methylbutyric acid methyl ester, 4- (2-
Nitrobenzene) -3-methylbutyric acid methyl ester, 4- (2-
Nitrobenzene) -3-ethylbutyric acid methyl ester, 4- (2-
Nitrobenzene) -3-chlorobutyric acid methyl ester, 4- (2-
Nitro-3-isopropylbenzene) butyric acid methyl ester, 4- (2-nitro-3-butylbenzene) butyric acid methyl ester, 4- (2-nitro-4-t-butylbenzene) butyric acid methyl ester, 4- (2- (Nitro-5-methylbenzene) butyric acid methyl ester, 4- (2-nitro-3-methylbenzene) -2-methylbutyric acid methyl ester, 4- (2-nitro-5-isopropylbenzene)
Butyric acid methyl ester, 4- (2-nitro-5-chlorobenzene)
Butyric acid methyl ester,

4- (2-nitrobenzene) butyric acid ethyl ester, 4- (2-nitrobenzene) -2-methylbutyric acid ethyl ester, 4- (2-nitrobenzene) -3-methylbutyric acid ethyl ester, 4- (2-nitrobenzene ) -3-Ethylbutyric acid ethyl ester, 4- (2-nitrobenzene) -3-chlorobutyric acid ethyl ester, 4- (2-nitrobenzene) butyric acid ethyl ester, 4- (2-
Nitro-3-isopropylbenzene) butyric acid ethyl ester, 4- (2-nitro-3-butylbenzene) butyric acid ethyl ester, 4- (2-nitro-4-t-butylbenzene) butyric acid ethyl ester, 4- (2- (Nitro-5-methylbenzene) butyric acid ethyl ester, 4- (2-nitro-3-methylbenzene) -2-methylbutyric acid ethyl ester, 4- (2-nitro-5-isopropylbenzene)
Butyric acid ethyl ester, 4- (2-nitro-5-chlorobenzene)
Examples include butyric acid ethyl ester, 4- (2-nitrobenzene) butyric acid cyclohexyl ester, 4- (2-nitrobenzene) butyric acid phenyl ester, and 4- (2-nitrobenzene) butyric acid benzyl ester. In particular, 4- (2-nitrobenzene) butanonitrile, 4- (2-nitrobenzene) butyric acid and 4- (2-nitrobenzene) butyric acid methyl ester and 4- (2-nitrobenzene) butyric acid ethyl ester are the most versatile 5-nitro-1. -It is preferable because it can be easily converted into tetralone.

(Step (II): Cyclization Reaction) General Formula (3)
Of a 4- (2-nitrobenzene) propane compound represented by
In the cyclization reaction to the 5-nitro-1-tetralone compound represented by the general formula (4), a super strong acid having an acidity function (Ho) of -14 or less is used. As the super strong acid, a liquid super strong acid such as FSO ₃ H or ClSO ₃ H is preferable, and a small amount of SO ₃ or Sb is added to FSO ₃ H or ClSO ₃ H.
Lewis acids F ₅ such as a super strong acid may be used with the addition. Moreover, solid superacids such as sulfated zirconia or sulfated tin oxide are also exemplified. The amount of the super strong acid used is 1 equivalent or more with respect to the substrate represented by the general formula (3). The cyclization reaction may be carried out in a super strong acid, or a solvent inert to the super strong acid may be used.

The reaction temperature is 20 ° C to 200 ° C, preferably 50 to 150 ° C. The reaction time is 5 minutes to 3 hours, preferably 20 minutes to 1.5 hours. The reaction can be carried out under normal pressure, under pressure, or under reduced pressure if the reaction temperature can be maintained. The reaction may be carried out batchwise or continuously.

After the acid was recovered from the reaction mixture obtained by the reaction by distillation, water was added, oil-water separation was carried out with an organic solvent, the organic layer was washed with water, and the organic solvent was removed. -1-Tetralone compound is obtained. The acid recovered by distillation can be repeatedly used in the cyclization reaction.

Further, the acid consumed in the cyclization reaction is decomposed into water and methanol produced together with tetralone to become HF and sulfuric acid. The sulfuric acid thus produced is the base used in the production of the 4- (2-nitrobenzene) propane compound represented by the general formula (3) obtained by the reaction between the general formulas (1) and (2). Is preferably used for the neutralization treatment.

The organic solvent used here is isopropyl ether, ethyl acetate, butyl acetate, carbon disulfide, carbon tetrachloride, hexane, cyclohexane, petroleum ether, toluene, xylene, chloroform, dichloromethane, 1,2-.
Examples thereof include dichloroethane, trichloroethylene, o-dichlorobenzene, chlorobenzene, benzonitrile, nitromethane, nitrobenzene, anisole and diethylene glycol dimethyl ether, with isopropyl ether, ethyl acetate and butyl acetate being particularly preferred. Other than the above compounds, the compound of interest can be dissolved, separated from water, stable under oil-water separation conditions, and having physical properties such as boiling points within the preferred ranges.

The crude 5-nitro-1-tetralone compound can be purified by recrystallization when its melting point is high or its crystallinity is good, and by distillation when its melting point is low or its crystallinity is poor.

Examples of the 5-nitro-1-tetralone compound represented by the general formula (4) include 5-nitro-1-tetralone, 5
-Nitro-2-methyl-1-tetralone, 5-nitro-3-methyl-1
-Tetralone, 5-nitro-3-ethyl-1-tetralone, 5-nitro-3-chloro-1-tetralone, 5-nitro-4-n-propyl-
1-tetralone, 5-nitro-6-isopropyl-1-tetralone, 5-nitro-6-n-butyl-1-tetralone, 5-nitro-7-t
-Butyl-1-tetralone, 5-nitro-8-methyl-1-tetralone, 5-nitro-8-chloro-1-tetralone, 5-nitro-2,6-
Examples include dimethyl-1-tetralone, 5-nitro-4,8-dimethyl-1-tetralone, 5-nitro-8-isopropyl-1-tetralone and the like. Particularly, 5-nitro-1-tetralone is preferable because it can be converted to 1,5-diaminonaphthalene.

(Step (III): Conversion Reaction to 1,5-Diaminonaphthalene) 5-nitro-1 represented by the general formula (4)
-The tetralone compound is then subjected to 1) oximation reaction,
A production route by either the subsequent conversion reaction to 5-nitro-1-aminonaphthalene and the reduction reaction of the nitro group, 2) imination reaction and the subsequent aromatization / reduction reaction of the nitro group. , Is converted to the desired product, 1,5-diaminonaphthalene.

The oximation reaction of 5-nitro-1-tetralone can be carried out by a usual oximation reaction. Hydroxylamine or a salt of hydroxylamine can be used as the oxime-forming agent. Examples of the hydroxylamine salt include hydroxylamine hydrochloride and hydroxylamine sulfate. Hydroxylamine may be obtained by neutralizing these salts with a basic compound or by reacting ammonia with a peroxide such as hydrogen peroxide. Further, hydroxylamine may be isolated by distillation or the like, or may be extracted and used,
You can use it as it is. As the reaction solvent for oximation, any solvent can be used as long as it is an inert solvent for the reaction. Examples thereof include alcohol solvents and alcohol solvents containing acidic compounds such as acetic acid.

The reaction temperature may be in the range of 50 ° C. to the temperature at which hydroxylamine or its salt decomposes. The pressure may be atmospheric pressure, but it may be increased or decreased as long as the reaction temperature can be maintained. The reaction time is
1 minute or more. The product may be isolated by distillation, recrystallization, reprecipitation, column chromatogram, etc.,
A part of the reaction solvent may be distilled off, or if the reaction solvent is inert in the next step, it may not be concentrated and isolated as it is.

In the conversion of the oxime form into 5-nitro-1-aminonaphthalene, a reagent capable of cleaving the N--O bond of the oxime group by a dehydration type reaction can be used. For example, the desired 5-nitro-1-aminonaphthalene can be obtained as a hydrochloride by heating the oxime compound in an acetic acid solvent in the presence of hydrochloric acid. The reaction temperature and reaction time vary depending on the reaction agent used, but as described above, it is sufficient that the N-O bond of the oxime group can be cleaved by a dehydration reaction. In order to facilitate elimination of the OH group, OH of the oxime group may be converted into OCOCH ₃ group with acetic anhydride or the like.
The reaction pressure may be normal pressure or increased pressure. When the dehydrating agent is a gaseous substance, it can be circulated at normal pressure, but pressurization is more advantageous.

Subsequent to the oximation, conversion to 5-nitro-1-aminonaphthalene is carried out, but this reaction may be carried out in one step.

For the reduction of the nitro group to the amino group, the method of converting nitrobenzenes to anilines can be used as it is, but the method of reducing with hydrogen using a hydrogenation catalyst is the most economical method. Is. As a hydrogenation catalyst,
Raney metal such as Raney Ni, Raney Co or Pd / C,
A white metal catalyst such as Pt / alumina can be used. The reaction may be carried out in either the gas phase or the liquid phase.
As the solvent used in the liquid phase reaction, any solvent can be used as long as it is inert to the reaction. Solvents such as alcohols and amides can be mentioned as preferable solvents. The reaction temperature is in the range of normal temperature to 150 ° C, preferably 50 to 100 ° C. The reaction pressure may be atmospheric pressure or higher.

Further, oximation, aminonaphthalene,
All the reactions of reducing the nitro group may be carried out batchwise or continuously.

On the other hand, it is also possible to convert 5-nitro-1-tetralone into 1,5-diaminonaphthalene by a method of passing through an imine without passing through an oxime.

The imination of 5-nitro-1-tetralone can be carried out by reacting with excess ammonia and / or a salt compound of ammonia. At this time, a dehydrating agent may be added. The reaction can be carried out either under normal pressure or under pressure, but when ammonia is used, the reaction is preferably carried out under pressure.

The aromatization of the tetralin ring and the reduction of the nitro group, which are carried out after the imination, are carried out by hydrogenation catalysts such as Raney Ni,
A Raney metal such as Raney Co or a white metal catalyst such as Pd / C or Pt / alumina can be used to proceed with hydrogen transfer. Further, hydrogen can be coexistent with hydrogen to reduce a part of the remaining nitro group or nitroso group. Aromatization of the tetralin ring and reduction of the nitro group may be performed in one step. That is, the imine compound can be converted into 1,5-diaminonaphthalene compounds by using a hydrogenation catalyst in the presence of hydrogen.

It is also possible to convert 5-nitro-1-tetralones to 1,5-diaminonaphthalene using a hydrogenation catalyst in the presence of hydrogen in the presence of ammonia and / or a salt compound of ammonia. I can.

All of these imination, aromatization, and nitro group reduction reactions may be carried out in either a gas phase or a liquid phase, or may be carried out batchwise, so that the reactions are carried out continuously. You can go.

The 1,5-diaminonaphthalene compound which is a product of the present invention means a compound represented by the general formula (5). Here, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are represented by the general formula (1)
And as defined in the general formula (2).

Examples of 1,5-diaminonaphthalene used in the present invention include 1,5-diaminonaphthalene and 2-methyl-1,5.
-Diaminonaphthalene, 3-methyl-1,5-diaminonaphthalene, 3-ethyl-1,5-diaminonaphthalene, 3-chloro-1,5-
Diaminonaphthalene, 4-n-propyl-1,5-diaminonaphthalene, 6-isopropyl-1,5-diaminonaphthalene, 6-n
-Butyl-1,5-diaminonaphthalene, 7-t-butyl-1,5-diaminonaphthalene, 8-methyl-1,5-diaminonaphthalene, 6-chloro-1,5-diaminonaphthalene, 2,6-dimethyl -
Examples include 1,5-diaminonaphthalene and 4,8-dimethyl-1,5-diaminonaphthalene.

[0063]

The present invention will be further described below with reference to specific examples, but the present invention is not limited thereto.

(Example 1) Synthesis of 4- (2-nitrobenzene) propane compound A four-necked flask having an internal volume of 2 L equipped with a condenser, a thermometer, a dropping funnel, and a stirrer was set in an ice water bath, and 96 % NaO
50 g (1.2 mol) of H and 64 g of water are added and dissolved. to this
Add 1.2 L of 1,3-dimethyl-2-imidazolidinone (hereinafter abbreviated as DMI) and stir. To this, 164.6 g (1.2 mol) of 2-nitrotoluene is dissolved in 360 ml of DMI and added dropwise from the dropping funnel over about 1 hour. Then, 106.5 g (1.2 mol) of acrylic acid methyl ester was DM
It is dissolved in 360 ml of I and added dropwise from the dropping funnel over about 3 hours. During this period, the reaction temperature is maintained at 0 to 4 ° C. The reaction solution is poured into about 5 L of ice water, and the sulfuric acid, which is a decomposition product of the super strong acid used in the reaction of the next step described in Example 2, is effectively utilized as follows for neutralizing the base. That is, 4-
FSO ₃ H used in the cyclization reaction of (2-nitrobenzene) propane compound was distilled and recovered after the reaction was completed, and the pH was adjusted by the remaining sulfuric acid.
Neutralize until 5-7. Next, ethyl acetate 300
After extracting with ml and dehydrating with Na ₂ SO ₄ , it was dried under reduced pressure (4 × 10
^-4 MPa) to give 160.6 g of a yellow viscous liquid. The purity as 4- (2-nitrobenzene) butyric acid methyl ester was 99%, and the yield based on acrylic acid methyl ester was 60%.

Next, 4- (2-nitrobenzene) butyric acid can be obtained by treating the above-mentioned methyl ester compound as follows. That is, 55 g (0.247 mol) of 4- (2-nitrobenzene) butyric acid methyl ester was dissolved in 200 ml of acetic acid, 44 g (2.47 mol) of water and 5 g of 3N HCl aqueous solution were added, and hydrolysis reaction was carried out for 5 hours under reflux. It was After acetic acid and water were distilled off from the reaction mixture, it was dissolved in 300 ml of ethyl acetate and washed 3 times with water. After dehydration with Na ₂ SO ₄ , a part of ethyl acetate was distilled off and upon cooling, pale yellow crystals were precipitated. After filtration and drying, 45 g of pale yellow crystals were obtained. 4-
The purity as (2-nitrobenzene) butyric acid was 99.5%, and the yield based on the ester was 87%.

(Example 2) Internal volume 3 equipped with a cooler, a thermometer, a dropping funnel, and a magnetic stirrer tip
Charge 75 g of FSO ₃ H into a 00 ml _three- necked flask, and
From a dropping funnel while stirring in an oil bath heated to 00 ° C
10.45 g of 4- (2-nitrobenzene) butyric acid was added dropwise over 60 minutes to carry out a cyclization reaction to produce 5-nitro-1-tetralone.

After completion of the reaction, a small distillation column was attached to the flask and distilled under reduced pressure at (0.027 MPa) to recover 65 g of FSO ₃ H. Even when the recovered FSO ₃ H was repeatedly used in the cyclization reaction, the activity of the cyclization reaction did not decrease. A mixture containing 5-nitro-1-tetralone and sulfuric acid generated by decomposition of a part of the super strong acid was poured into 500 ml of ice water and extracted twice with 150 ml of butyl acetate. The extract was washed 3 times with 100 ml of water, dehydrated with sodium sulfate, and then butyl acetate was distilled off to obtain 9.0 g of crystals containing brownish 5-nitro-1-tetralone. As a result of taking a part of the crystal and quantifying it by GC, the conversion rate of 4- (2-nitrobenzene) butyric acid was 100%, and the target 5-nitro-1-tetralone was obtained at a yield of 68%. , Isomers with different carbonyl group substitution positions were not detected.

The aqueous solution containing sulfuric acid obtained by separating the reaction mixture from oily water with butyl acetate can be effectively used for the neutralization of the aqueous solution containing the base used in Example 1.

[0069]

INDUSTRIAL APPLICABILITY In the step of producing a corresponding 1,5 diaminonaphthalene compound from an orthoalkylnitrobenzene compound and a vinyl compound as raw materials via a 5-nitro-1-tetralone compound, a first Michael addition reaction step The by-product of the reaction can be effectively utilized by carrying out the neutralization treatment of the base used in the above step with the sulfuric acid which is a decomposition product of the super strong acid used in the second stage cyclization reaction.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4H006 AA02 AC21 AC28 AC52 AD11                       BA10 BA11 BA13 BA36 BA37                       BA66 BA67 BA68 BA83 BA85                       BD40 BD70 BE20                 4H039 CA40 CH20

Claims (3)

[Claims] [Claim 1] General formula (1): (In the general formula (1), R ¹ , R ² , R ³ and R ⁴ are the same or different and each is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms. Or a halogen atom), and an orthoalkylnitrobenzene compound represented by the general formula (2): (In the general formula (2), R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and R ⁵ and R ⁶ are at the cis or trans position. In which X represents an electron-withdrawing group) is reacted in the presence of a base to give a compound of the general formula (3): (In the general formula (3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and X represent the groups defined in the general formula (1) and the general formula (2)). A step (I) of obtaining a 4- (2-nitrobenzene) propane compound and a cyclization reaction of the 4- (2-nitrobenzene) propane compound represented by the general formula (3) in the presence of superacids are carried out. 4): [Chemical 4] (In the general formula (4), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent the groups defined in the general formula (1) and the general formula (2)). -Conversion to nitro-1-tetralones (I
I) and 5-nitro-1-tetralones represented by the general formula (4) are represented by the general formula (5): (In the general formula (5), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ represent the groups defined in the general formula (1) and the general formula (2)) 1. Step of converting to 5,5-diaminonaphthalene (II
In the process for producing 1,5-diaminonaphthalene consisting of I), the super strong acid used in the step (II) is distilled and recovered after the cyclization reaction and reused in the reaction. The manufacturing method of 1,5- diamino naphthalene shown by these. 2. The acid generated by decomposing a part of the super strong acids used in the step (II) during the cyclization reaction is used for the neutralization treatment of the base used in the step (I). The method according to claim 1, wherein: 3. In the general formula (2) and the general formula (3), X is a nitrile group, a carboxyl group, or a group represented by CO ₂ R ^7; (Wherein R ⁷ represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a benzyl group).