JPH0660143B2 - Novel diamine compound and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel diamine compound and a method for producing the same.

[Conventional technology]

BACKGROUND ART Conventionally, diamine compounds have been widely used as raw materials for heat-resistant polyimide resins, polyamide resins, polyamideimide resins, etc., as curing agents for epoxy resins, and as intermediates for dyes and the like.

[Problems to be solved by the invention]

However, aromatic diamines such as 4,4′-diaminodiphenyl ether and 4,4′-diaminodiphenylmethane, which are widely used at present, are obtained when polyimide resins, polyamide resins, polyamideimide resins, etc. are produced from them. The obtained resin has good heat resistance, but has problems in moldability and the like. Therefore, in order to balance these advantages and disadvantages, mixing of an epoxy resin with a polyimide resin, a polyamide resin, a polyamideimide resin, or the like is being studied, but the situation is still insufficient. The main obstacle is that the resulting resin becomes insoluble or difficult to dissolve in a solvent, and that the obtained resin and epoxy resin do not mix in a desired composition,
Therefore, the expected characteristics were not expressed.

[Problems to be solved]

An object of the present invention is to provide a diamine compound which can be uniformly mixed with an epoxy resin and is useful as a raw material for a polyimide resin, a polyamide resin, a polyamideimide resin, or the like.

[Means for solving problems]

The present invention has the general formula (In the formula, R is a group Or a C ₁ -C ₁₂ -alkylene group, R ¹ represents a hydrogen atom, a C ₁ -C ₆ lower alkyl group, a halogen atom, a nitrile group, a nitro group, a C ₁ -C ₆ alkoxy group or a hydroxyl group. ) Is a diamine compound.

Substituents on the compound of formula 1 Is the base Is. Each R ¹ may be the same or different.

Examples of the compound represented by the general formula (1) include the following compounds. N, N'-bis (2-aminophenyl) -5-hydroxyisophthalamide, N, N'-bis (3-aminophenyl) -5-hydroxyisophthalamide, N, N'-bis (4-aminophenyl) -5 Hydroxyisophthalamide, N, N'-bis (2-aminophenyl) -2-hydroxyterephthalamide, N, N'-
Bis (3-aminophenyl) -2-hydroxyterephthalamide, N, N'-bis (4-aminophenyl) -2-
Hydroxyterephthalamide, N, N'-bis (2-aminophenyl) -2-hydroxyphthalamide, N, N'-
Bis (3-aminophenyl) -2-hydroxyphthalamide, N, N'-bis (4-aminophenyl) -2-hydroxyphthalamide, N, N'-bis (2-aminophenyl) -3-hydroxyphthalamide, N , N'-bis (3
-Aminophenyl) -3-hydroxyphthalamide, N,
N'-bis (4-aminophenyl) -3-hydroxyphthalamide, N, N'-bis (4-amino-3,5-dimethylphenyl) -5-hydroxyisophthalamide, N, N '
-Bis (4-amino-3,5-dimethylphenyl) -2-
Hydroxyterephthalamide, N, N'-bis (4-amino-3,5-dimethylphenyl) -2-hydroxyphthalamide, N, N-bis (4-amino-3,5-dimethylphenyl) -3 -Hydroxyphthalamide, N, N'-bis (4
-Amino-n-butyl) -5-hydroxyisophthalamide, N, N'-bis (6-amino-n-hexyl) -5
-Hydroxyisophthalamide, N, N'-bis (4-amino-n-dodecyl) -5-hydroxyisophthalamide and the like.

The diamine compound of formula I is, for example, of the general formula It is obtained by reducing a dinitro compound represented by the formula (wherein R has the above meaning).

The compound of formula II may be, for example: In the general formula _{H 2 N-R-NO 2} (IV) a dicarboxylic acid or a derivative thereof represented (wherein R is as defined above) can be obtained by reacting a nitramine or a derivative thereof represented by.

Examples of the dicarboxylic acid of the formula III include 2-, 4- or 5-hydroxyisophthalic acid, 2-hydroxyterephthalic acid, 3- or 4-hydroxyphthalic acid and the like. Examples of the nitroamine of the formula IV include o-, m- or p-nitroaniline, 3,4-, 4,5- or 3,5-dimethyl-2-nitroaniline, 4,5- or 4,6-dimethyl. -3
-Nitroaniline, 3,5-dimethyl-4-nitroaniline, 4-nitro-n-butylamine, 6-nitro-n-
Hexylamine, 12-nitro-n-dodecylamine,
2,2-dimethyl-3-nitropropylamine and the like can be mentioned.

The reaction of dicarboxylic acid (III) and nitroamine (IV) is preferably carried out in a solvent in the presence of a condensing agent.

Examples of the solvent include toluene, benzene, chlorobenzene, dichlorobenzene, acetonitrile, pyridine, tetrahydrofuran, acetic anhydride, dichloromethane, hexane, cyclohexane, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methyl-2.
-Pyrrolidone, hexamethylphosphoric triamide, etc. are used. If necessary, inorganic salts such as lithium chloride and calcium chloride may be added to the reaction system in order to increase the solvation power of the protic solvent and suppress side reactions.

Examples of the condensing agent include triphenyl phosphite, diphenyl phosphite, tri-o-tolyl phosphite, and di-o-phosphite.
Trilyl, tri-m-tolyl phosphite, di-m-phosphite
Trilyl, tri-p-tolyl phosphite, di-p-phosphite
Trilyl, di-o-chlorophenyl phosphite, tri-p-chlorophenyl phosphite, di-p-chlorophenyl phosphite, dicyclohexylcarbodiimide, triphenyl phosphonate, diphenyl phosphonate and the like are used.

The reaction temperature is preferably in the range of 60 to 150 ° C. The reaction is usually completed within a few minutes to 24 hours. In some cases, excess nitroamine may be used, the reaction solution may be heated to a high temperature, or water produced may be removed to shift the equilibrium to the production system.

The produced dinitro compound can be isolated as a precipitate by pouring the reaction mixture into methanol, and after the isolation, appropriate washing, drying and the like can be performed.

The compound of the formula II also includes a reaction between an acid halide and an amine (eg, Journal of Organic Chemistry, Vol. 32, p. 3069 or less, 1967), a reaction between a carboxylic acid and an isocyanate (for example, Chemical Revise 57, 47.
Pp. 1957), reaction between ester and amine (Tetrahydrone Letters 1970, pp. 1791) and the like.

As the reduction method of the compound of formula II, a catalytic reduction method (catalytic hydrogenation method), an acidic reduction method, a basic reduction method and the like are used.

In the case of the catalytic hydrogenation method, the reaction is usually carried out in a solvent under a hydrogen atmosphere using a catalyst.

As the catalyst, a metal catalyst such as activated carbon with palladium, strontium carbonate with palladium, sodium borohydride with palladium, platinum (IV) oxide, Raney-Nickel, rhenium oxide or the like is used. The amount of the metal catalyst used is preferably 5 to 10% by weight of the above dinitro compound.

As the solvent, ethanol, methanol, acetic acid, dioxane, cyclohexane, water, tetrahydrofuran, ethyl acetate, dimethylformamide and the like can be used. Dimethylformamide is particularly preferable.

The reaction temperature is usually in the range of room temperature to reflux temperature, especially 25
-50 degreeC is preferable. The reaction is usually completed in 4 to 48 hours.

The resulting diamine compound of formula I can be obtained as a precipitate in aqueous solution and purified by recrystallization from methanol.

Example 1 (A) N, N'-bis (3-nitrophenyl) -5-hydroxyisophthalamide m-nitroaniline 27.6 g (200 mmol) and 5-
18.2 g (100 mmol) of hydroxyisophthalic acid was added to N
-Dissolved in 200 ml of methyl-2-pyrrolidone, 50 ml of pyridine and 62 g of triphenyl phosphite (20 g) were added to this solution.
0 mmol) and 10.6 g (250 mmol) of lithium chloride were sequentially added, and the mixture was stirred at 100 ° C. for 6 hours. After cooling down,
The reaction mixture was poured into 3000 ml of methanol and stirred at room temperature for 1 hour, and the precipitated solid was separated. The obtained solid was washed with hot methanol and then dried to obtain 33.7 g (yield 80%) of the title compound.

IR spectrum (cm ⁻¹ : KBr method) 3250, 1660, 1528, 1350 ¹ H-NMR spectrum (δ: DMSO-d ⁶ , TMS standard) 7.53 to 8.86 (11H, m) 10.90 (2H, s) (B) A suspension of 20 g (48 mmol) of the compound obtained from N, N'-bis (3-aminophenyl) -5-hydroxyisophthalamide (A), 2 g of activated carbon with palladium and 150 ml of dimethylformamide under a hydrogen atmosphere at 50 ° C. Heated at 12 hours. After removing the activated carbon with palladium, the solution was poured into 1000 ml of water. The precipitated solid was separated, dried, and extracted with Soxhlet using methanol. Methanol was removed from the extract under reduced pressure to obtain 15.4 g of the target compound (yield 88%).

IR spectrum (cm ⁻¹ : KBr method) 3203, 1660 ¹ H-NMR spectrum (δ: DMSO-d ⁶ , TMS standard) 3.40 (4H, bs) 6.13 to 7.93 (11H, m) 10.00 (2H, s) Example 2 (A) N, N'-bis (nitrophenyl) -5-hydroxyisophthalamide 27.6 g (200 mmol) p-nitroaniline and 5-
18.2 g (100 mmol) of hydroxyisophthalic acid was added to N
-Dissolved in 200 ml of methyl-2-pyrrolidone, 50 ml of pyridine and 62 g of triphenyl phosphite (20 g) were added to this solution.
0 mmol) and 10.6 g (250 mmol) of lithium chloride were sequentially added, and the mixture was stirred at 100 ° C. for 6 hours. Thereafter, the same treatment as in Example 1 (A) was carried out to obtain 35.2 g (yield: 83%) of the title compound.

IR spectrum (cm ⁻¹ : KBr method) 3255, 1652, 1524, 1346 ¹ H-NMR spectrum (δ: DMSO-d ⁶ , TMS standard) 7.42 to 8.91 (11H, m) 11.02 (2H, s) (B) A suspension of 20 g (48 mmol) of the compound obtained from N, N'-bis (4-aminophenyl) -5-hydroxyisophthalamide (A), 2 g of activated carbon with palladium and 150 ml of dimethylformamide under a hydrogen atmosphere at 50 ° C. Heated at 12 hours. Thereafter, the same treatment as in Example 1 (B) was conducted to give 15.0% of the target compound.
g (yield 85%) was obtained.

IR spectrum (cm ⁻¹ : KBr method) 3211, 1661 ¹ H-NMR spectrum (δ: DMSO-d ⁶ , TMS standard) 3.45 (4H, bs) 6.08 to 8.01 (11H, m) 10.05 (2H, s) Example 3 (A) N, N'-bis (6-nitro-n-hexyl) -5-hydroxyisophthalamide 29.2 g (200 mmol) 6-nitrohexylamine and 18.2 g (100 mmol) 5-hydroxyisophthalic acid Dissolve in 200 ml of N-methyl-2-pyrrolidone,
Add 50 ml of pyridine and 62 parts of triphenyl phosphite to this solution.
g (200 mmol) and 10.6 g (250 mmol) of lithium chloride were sequentially added, and the mixture was stirred at 100 ° C. for 6 hours. Thereafter, the same treatment as in Example 1 (A) was conducted to give 34.6 of the title compound.
g (yield 79%) was obtained.

IR spectrum (cm ⁻¹ : KBr method) 3240, 1645, 1526, 1341 ¹ H-NMR spectrum (δ: DMSO-d ⁶ , TMS standard) 1.52 (12H, s) 7.52 to 8.82 (11H, m) 10.98 (2H , S) (B) N, N'-bis (6-amino-n-hexyl) -5-hydroxyisophthalamide 21 g (48 mmol) of the compound obtained in (A), 2.1 g of activated carbon with palladium and 150 ml of dimethylformamide.
The suspension was heated under a hydrogen atmosphere at 50 ° C. for 12 hours.
Thereafter, the same treatment as in Example 1 (B) was conducted to give 14.9% of the target compound.
g (yield 82%) was obtained.

IR spectrum (cm ⁻¹ : KBr method) 3211, 1661 ¹ H-NMR spectrum (δ: DMSO-d ⁶ , TMS standard) 1.50 (12H, s) 2.71 (4H, bs) 6.51 to 7.88 (11H, m) 10.25 (2H, s)

Claims (2)

[Claims] 1. A general formula (In the formula, R is a group Or a C ₁ -C ₁₂ -alkylene group, R ¹ represents a hydrogen atom, a C ₁ -C ₆ lower alkyl group, a halogen atom, a nitrile group, a nitro group, a C ₁ -C ₆ alkoxy group or a hydroxyl group. ) The diamine compound represented by. 2. General formula (In the formula, R is a group Or a C ₁ -C ₁₂ -alkylene group, R ¹ represents a hydrogen atom, a C ₁ -C ₆ lower alkyl group, a halogen atom, a nitrile group, a nitro group, a C ₁ -C ₆ alkoxy group or a hydroxyl group. ) The dinitro compound represented by these is reduced, The manufacturing method of the diamine compound of Claim 1 characterized by the above-mentioned.