JPH06340608A - Production of naphihalenediurethane compound and naphthalenediamine compound - Google Patents

Abstract

PURPOSE:To produce the subject compound under mild conditions in a few process number by subjecting a naphthalene dicarboxylic acid compound to a new Crutius reaction with an azide compound and an alcohol in a heterogeneous system. CONSTITUTION:A naphthalenedicarboxylic acid compound of formula I is made to react with an azide compound of formula II (R<1> is alkyl or aryl) and an alcohol of formula III (R<2> is alkyl or aryl), as necessary, in a solvent in the presence of a base to provide the objective naphthalene diurethane compound of the formula IV (R<3> and R<4> are alkyl, aryl). Then, the naphthalene-diurethane compound of formula IV is subjected to deprotection reaction of urethane type protecting group to provide the objective naphthalene diamine of formula V. By using this method, a condensed ring amino compound useful for dyes, functional resins, etc., can be synthesized under mild conditions.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a naphthalenediamine compound and a method for producing a naphthalenediurethane compound which is an intermediate for obtaining the same.

[0002]

2. Description of the Related Art Conventionally, a method by reduction of a nitro compound has been carried out as a method for synthesizing an aromatic or condensed ring amine.
In the condensed ring, there is a substitution position where introduction of a nitro group becomes extremely difficult when trying to obtain a corresponding nitro compound in order to obtain a compound having a plurality of amino groups. Therefore, there are condensed ring diamines that are difficult to reduce by the nitro group, and for example, amine synthesis is carried out by converting a functional group of a carboxyl group into an amino group.

As a method of synthesizing an amine from a carboxylic acid by converting a functional group, the Hoffman reaction (18
81), Curtius reaction (1890), and Schmidt reaction (1923). In the method utilizing the Hoffmann reaction, an acid amide is synthesized from a carboxylic acid, 1 mol of bromine is allowed to act on the acid amide, and an excess sodium hydroxide is heated to obtain an amine. The method of utilizing the Curtius reaction is to convert carboxylic acid into acid chloride, react with sodium azide to form acid azide, and then heat in alcohol to synthesize urethane through isocyanate and then hydrolyze this. Obtain the amine. In the Schmidt reaction, carboxylic acid is reacted with sulfuric acid and hydrazoic acid in benzene to obtain an amine.

Salting is a reaction of an aliphatic carboxylic acid compound represented by the general formula (VI) with an azide compound represented by the general formula (II) and an alcohol represented by the general formula (III) in the presence of a base. It has been reported that a urethane compound is obtained by the reaction, and that the amine is obtained in a homogeneous system by hydrolyzing the compound [Takayuki Shioiri, Shunichi Yamada, Journal of Organic Chemistry, Vol. 31, No. 8, 666-]. 674 (1973)
Year)〕.

[0005]

The method utilizing the Hoffman reaction, the Curtius reaction, the Schmidt reaction, etc. has a drawback that it requires severe reaction conditions or multistep reactions, resulting in poor practicality. The present invention provides a method for producing a naphthalenediamine compound which can be performed under mild conditions by applying the new Curtius reaction in a heterogeneous system and has a small number of reaction steps.

[0006]

The naphthalenediamine compound obtained by the production method of the present invention has the general formula (V)

[Chemical 6] It is represented by.

The compounds represented by the general formula (V) include 1,2-naphthalenediamine, 1,3-naphthalenediamine, 1,4-naphthalenediamine, 1,5-naphthalenediamine, 1,6-naphthalenediamine, 1,7-naphthalenediamine, 1,8-naphthalenediamine, 2,
Examples include 3-naphthalenediamine, 2,5-naphthalenediamine, 2,6-naphthalenediamine, and 2,7-naphthalenediamine.

The naphthalenediamine compound represented by the general formula (V) can be produced by subjecting the naphthalenediurethane compound represented by the general formula (IV) to a deprotection reaction of a urethane type protecting group. . Here, the urethane type protecting group is specifically -CO in the general formula (IV).
It means OR ³ and —COOR ⁴ .

The above deprotection reaction can be carried out, for example, by the following method. In a liquid obtained by dissolving or dispersing the naphthalene diurethane compound in an organic solvent such as ethyl acetate, dimethylformamide, dimethylacetamide, benzene, xylene, acetone, or tetrahydrofuran in the presence of palladium carbon or the like, hydrogen gas is added at 0 to 100 ° C. (especially Method of passing hydrogen gas (preferably around room temperature) (time for passing hydrogen gas may be appropriately determined, but 1 to 10 hours is usually sufficient), and the naphthalene diurethane compound is dissolved or dispersed in an organic solvent as described above. , HF, HBr, HC
1, a method in which a hydrogen acid such as H ₂ SO ₄ is added and reacted (hydrogen acid is preferably reacted in an amount equivalent to or more than the naphthalene diurethane compound, and when HF is used, it is lower than room temperature, particularly 0 ° C.). The reaction is preferably carried out below, and with other hydrogen acids, it is preferable to carry out the reaction at 0 to 100 ° C., particularly near room temperature, and the reaction time is appropriately determined,
Usually, when HF is used, 0.1 to 1 hour is necessary, and when other hydrogen acid is used, 1 to 10 hours is sufficient), the naphthalene diurethane compound is sodium hydrogen carbonate,
Method of reacting in the presence of a basic compound such as potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide and water (water is preferably used in an equivalent amount or more with respect to the naphthalene diurethane compound, and the reaction is carried out in the above-mentioned organic Other than the solvent, water, methanol, ethanol, cresol or the like may be used as a solvent). The naphthalenediamine compound represented by the general formula (V) thus obtained can be purified by recrystallization from alcohol or the like.

The naphthalene diurethane compound represented by the general formula (IV) is represented by the general formula (I)

[Chemical 7] A naphthalenedicarboxylic acid compound represented by

[0011]

[Chemical 8] (However, in the formula, R ¹ represents an alkyl group which may have a substituent or an aryl group which may have a substituent), in a solvent or without a solvent, with a base. It can be produced by reacting in the presence of.

The naphthalenedicarboxylic acid represented by the general formula (I) is α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, 1,4-naphthalenedicarboxylic acid,
2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid-2 potassium salt, 1-naphthol-2-carboxylic acid, 2-naphthol-3-carboxylic acid, 2-naphthol- 6-carboxylic acid and the like.

As the compound represented by the general formula (II),
There are diphenylphosphoryl azide, diethylphosphoryl azide, di-p-nitrophenylphosphoryl azide, dimorpholylphosphoryl azide and the like.

Examples of the alcohol represented by the general formula (III) include methanol, ethanol, propanol, i-propanol, butanol, pentanol, hexanol, heptanol, octanol, phenol and benzyl alcohol.

For the synthetic reaction for obtaining the naphthalene diurethane compound represented by the general formula (IV), Takayuki Shioiri, Shunichi Yamada,
The new Curtius reaction, as shown in Journal of Organic Synthetic Chemistry, Vol. 31, No. 8, pp. 666-674 (1973), can be applied. That is, by reacting the dicarboxylic acid compound represented by the general formula (I) with the azide compound represented by the general formula (II) and the alcohol represented by the general formula (III) in the presence of a base, A naphthalenediurethane compound can be obtained. As the base, it is preferable to use a tertiary amine such as trimethylamine, triethylamine or pyridine. The above reaction is
It is carried out in an organic solvent or using an alcohol represented by the general formula (III) also as a solvent. As the organic solvent, it is preferable to use benzene, toluene, tetrahydrofuran, dioxane, diethyl ether or the like.
These solvents may be used as a mixture of two or more if they are compatible with each other.

In the above reaction, the dicarboxylic acid compound represented by the general formula (I) and the azide compound represented by the general formula (II) react in the middle so that the carboxylic acid azide and the carboxylic acid azide undergo thermal transfer. Although an isocyanate compound is formed by the reaction, these intermediates can be isolated once or with no isolation. The conditions of the above reaction vary depending on the reagents used and are not particularly limited, but the following conditions are preferable.

First, the dicarboxylic acid compound represented by the general formula (I), the azide compound represented by the general formula (II), the tertiary amine and the alcohol represented by the general formula (III) are mixed at once. When the reaction is carried out to apparently obtain the desired naphthalene diurethane compound in one step, the reaction temperature is −80.
To 250 ° C. is preferable, and room temperature to 150 ° C. is particularly preferable. The azide compound, the tertiary amine, and the alcohol are each 0.5 to 5.0 molar equivalents, 0.5 to 3.0 molar equivalents, and 0.5 molar equivalents to the naphthalene dicarboxylic acid compound. It is preferably used in excess.

Secondly, when the carboxylic acid azide is once isolated, first, the naphthalene dicarboxylic acid compound is reacted with the azide compound in the presence of the tertiary amine to isolate the resulting carboxylic acid azide. . At this time,
The reaction temperature is preferably −80 to 100 ° C., and the azide compound and the tertiary amine are preferably used at 0.5 to 5.0 molar equivalents and 0.5 to 3.0 molar equivalents with respect to the carboxylic acid compound, respectively. . Then, the isolated carboxylic acid azide can be reacted in 0.5 mol equivalent to a large excess of alcohol relative thereto to obtain the desired naphthalene diurethane compound. The reaction temperature at this time is -8
0-100 degreeC is preferable.

Thirdly, when the isocyanate compound is once isolated, first, the dicarboxylic acid compound and the general formula (II)
The azide compound represented by is reacted in the presence of a tertiary amine, and the resulting isocyanate is isolated. At this time, the azide compound of 0.5 to the dicarboxylic acid compound
It is preferable to use 5.0 molar equivalents and the above tertiary amine 0.5 to 3.0 molar equivalents, and the reaction temperature is -80 to 250 ° C.
Is preferred. Then, the obtained isocyanate is reacted in an alcohol in an amount of 0.5 molar equivalent to a large excess thereof, whereby a naphthalene diurethane compound can be obtained. At this time, the reaction temperature is −80 to 250 ° C.
Is preferred.

The above-mentioned first to third methods are appropriately selected in consideration of yield and the like. The naphthalenedicarboxylic acid compound thus obtained is methanol, ethanol, n
-Can be purified by recrystallization from propanol, isopropanol, hexane and the like.

[0021]

【Example】

Example 1 (Synthesis of 2,6-bis (N- (t-butyloxycarbonyl) amino) naphthalene) 2,6-naphthalenedicarboxylic acid 8.65 g (40 mm)
ol), 26.4 g of diphenylphosphoryl azide (96
mmol), 9.71 g of triethylamine (96 mmo
l), in 20 ml of t-butanol at reflux temperature.
Reacted for hours. After completion of the reaction, the reaction solution was allowed to reach room temperature and the unreacted material was filtered off. The t-butanol of the filtrate was distilled off, 300 ml of benzene was added thereto, and the insoluble portion was filtered off. This insoluble part is dried to obtain the desired product, 2,6
-Bis (N- (t-butyloxycarbonyl) amino)
6.48 g (yield 45%) of naphthalene was obtained.

Example 2 (Synthesis of 2,6-naphthalenediamine) 6.00 g (2,6-bis (N- (t-butyloxycarbonyl) amino) naphthalene obtained in Example 1
6.8 mmol) was dispersed in 360 ml of a 12N hydrochloric acid / ethyl acetate 1/3 mixture solution. After reacting for 4 hours at room temperature, the precipitate was filtered off. Dissolve the whole precipitate in 200 ml of water,
A white precipitate formed when 150 ml of an aqueous aOH solution was added. The precipitate was filtered off, washed with water and dried to obtain the desired product, 2,6-naphthalenediamine (2.63 g, yield 99%).
Got

(Identification of Compounds) The compounds obtained in Examples 1 and 2 were identified by 1 H-NMR and IR measurements. (1) 1H-NMR spectrum (solvent weight DMSO, DMSO standard) of the compound obtained in Example 1 (FIG. 1) 9.46 ppm (2H, NH, s), 7.98 ppm
(2H, aromatic ring, s) 7.66ppm (2H, aromatic ring, t), 7.40ppm
(2H, aromatic ring, t) 1.49ppm (18H, t-Butyl, s) [() indicates the integrated intensity ratio of hydrogen, the base group for absorption, and the type of peak, where s is a singlet , T indicates a triplet. (2) IR absorption spectrum of the compound obtained in Example 1 (FIG. 2) 3368 cm −1 (NH, urethane), 1700 cm −1
(C = O, urethane) 1540 cm-1 (NH, urethane) (3) 1H-NMR spectrum (solvent weight DMSO, DMSO standard) of the compound obtained in Example 2 (Fig. 3) 4.82 ppm (4H, NH ₂ , s), 7.23 ppm
(2H, aromatic ring, d) 6.78ppm (2H, aromatic ring, d), 6.68ppm
(2H, aromatic ring, d) [() indicates the integrated intensity ratio of hydrogen, the group that is the basis of absorption, and the type of peak, s is a singlet, and t is a triplet. (4) IR absorption spectrum of the compound obtained in Example 2 (FIG. 4) 1628 cm ⁻¹ (NH, amine), 1276 cm ⁻¹ (N
H, amine) 1540 cm ^-1 (NH, urethane) From the above results, formation of the target substance was confirmed.

[0024]

EFFECTS OF THE INVENTION The condensed ring amino compounds useful for dyes, functional resins and the like can be synthesized under mild conditions by the methods of claims 1 and 2.

[Brief description of drawings]

1 is the 2,6-bis (N- (t-
1 is a 1H nuclear magnetic resonance spectrum of butyloxycarbonyl) amino) naphthalene.

FIG. 2 is an infrared absorption spectrum of 2,6-bis (N- (t-butyloxycarbonyl) amino) naphthalene.

FIG. 3 is a ¹ H nuclear magnetic resonance spectrum of 2,6-naphthalenediamine obtained in Example 2.

FIG. 4 is an infrared absorption spectrum of 2,6-naphthalenediamine.

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Claims (2)

[Claims] 1. A general formula (I) of Chemical Formula 1 A naphthalenedicarboxylic acid compound represented by the following formula and a general formula (II) of the following formula: (R1 represents a lower alkyl group or an aryl group.) And a general formula (III) of Formula 3 ## STR3 ## R ² OH (III) (R ² has a substituent Represents an optionally substituted alkyl group or an aryl group which may have a substituent) in a solvent or without a solvent in the presence of a base,
A general formula (IV) of the chemical formula 4 characterized by reacting (R ³ and R ⁴ represent an alkyl group which may have a substituent or an aryl group which may have a substituent). 2. A naphthalene diurethane compound represented by the general formula (IV) according to claim 1 is subjected to a deprotection reaction of a urethane-type protecting group, and the general formula (V) of the chemical formula 5 A method for producing a naphthalenediamine compound, which comprises producing a compound represented by: