JPH02237968A - New diamine compound and production thereof - Google Patents

Abstract

NEW MATERIAL:The diamine compound of formula I [R is group of formula II (R1 is H, lower alkyl, halogen, nitrile, nitro, alkoxy or OH) or (substituted) 1-22C alkylene]. EXAMPLE:N,N'-bis(3-aminophenyl)-5-hydroxyisophthalamide)-5-hydroxy- isophthalamide. USE:Useful as a raw material for polyimide resin, polyamide resin, polyamide imide resin, etc., homogeneously miscible with epoxy resin. PREPARATION:The compound of formula I can be produced by producing a dinitro compound of formula V e.g. by the condensation reaction of a dicarboxylic acid of formula III or its derivative with a nitrosamine of formula IV or its derivative in a solvent in the presence of a condensation agent and reacting the obtained compound of formula V in a solvent (e.g. dimethylformamide) in the presence of a hydrogenation catalyst (e.g. Pd/C) in H2 atmosphere at room temperature-refluxing temperature for 4-48 hr to effect the catalytic hydrogenation reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel diamine compound and a method for producing the same.

[Conventional technology]

Conventionally, diamine compounds have been widely used as raw materials for polyimide resins, polyamide resins, polyamideimide resins, etc. for the purpose of heat resistance, as curing agents for epoxy resins, and further as intermediates for dyes and the like.

[Problem that the invention seeks to solve]

However, aromatic diamines such as 4,4'-diaminodiphenyl ether and 4,4'-diaminodiphenylmethane, which are currently widely used, are difficult to obtain when polyimide resins, polyamide resins, polyamideimide resins, etc. are produced from them. Although the resin has good heat resistance, it has problems in moldability and the like.

Therefore, in order to balance these advantages and disadvantages, mixing of epoxy resin with polyimide resin, polyamide resin, polyamideimide resin, etc. has been studied, but the situation is still insufficient.

The main obstacles were that the obtained resin was insoluble or difficult to dissolve in the solvent, and that the obtained resin and epoxy resin were not mixed in the desired composition, so that the expected properties were not expressed.

[Problems to be solved]

The purpose of the present invention is to provide a homogeneous mixture with epoxy resin.

[Means for solving problems]

The present invention is based on the general formula 1 {I1 CI=CI! - represents an alkyl group, R1 is a hydrogen atom,
(meaning a lower alkyl group, halogen atom, nitrile group, nitro group, alkoxy group or hydroxyl group) R1 may be the same or different.

Examples of compounds represented by the general formula (R) include the following compounds: N,N'-bis(2-aminophenyl)-5-hydroxyisophthalamide,
Bis(3-aminophenyl)-5-hydroxyisophthalamide, N,N-bis(4-aminophenyl)-5
-Hydroxyisophthalamide, N, '-bis(2-amino7-functional)-2-hydroxyterephthalamide, N
, "-bis(3-aminophenyl)-2-hydroxyterephthalamide, N,N'-bis(4-aminophenyl)-2-hydroxyterephthalamide, N,". -bis(2-amino7enyl)-2-hydroxyphthalamide, N,N'-bis(3-aminophenyl)-2-hydroxyphthalamide, N,'-bis(4-aminophenyl)-2-hydroxyphthalamide , N, Corbis (2
-aminophenyl)-6-hydroxyphthalamide, N
．． N'-bis(3-aminophenyl)-6-hydroxyphthalamide, N,'-bis(4-aminophenyl)-
3-hydroxyphthalamide, N. N'-pis(4-amino-3,5-dimethylphenyl)-5-hydroxyin 7talamide, N,d-bis(4-amino-3,5-
dimethylphenyl)-2-hydroxyterephthalamide, N. I-bis(4-amino-3,5-dimethylphenyl)-2-hydroxyphthalamide, N,N-his(
4 7 mi/ 5t5 y methyl 7 enyl)-3
-Hydroxyphthalamide, N. "-bis(4-amino-n-butyl)-5-hydroxyisophthalamide, N
, N'-bis(4-amino-n-hexyl)-5-hydroxyisophthalamide, N,N'-bis(4-amino-n-dodecyl)-5-hydroxyisophthalamide, and the like.

Diamine compounds of formula I can be obtained, for example, by reducing dinitro compounds of the general formula 0H, in which R has the meaning given above.

The compound of formula (1) can be obtained by, for example, reacting a dicarboxylic acid represented by the following formula OH or a derivative thereof with a ditroamine represented by the general formula HzN-R NO2 (N)) (wherein R has the above meaning) or a derivative thereof. It can be obtained by

As the dicarboxylic acid of formula (2), for example, 2-4- or 5-
Examples include hydroxyisophthalic acid, 2-hydroxytere7thalic acid, 3- or 4-hydroxyphthalic acid.

Nitroamines of formula (1) include, for example, o-m- or p-
Nitroaniline, 5.4-4.5- or 3,5-
Dimethyl-2-nitroanili/, 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-nitroglobilamine, and the like.

The reaction between dicarboxylic acid (I[D) and nitramine (conversion) is
It is preferable to carry out the reaction 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, dimethylsulfoxide, N-methyl-2
-Virrolidone, hexamethylphosphoric triamide, etc. are used. If necessary, inorganic salts such as lithium chloride and calcium chloride can be added to the reaction system in order to increase the solvation power of the protic solvent and to suppress side reactions.

Examples of the condensing agent include triphenyl phosphite, diphenyl phosphite, and tri-phosphite. LiA/, di-0-tolyl phosphite, tri-m-monotolyl phosphite, di-m-}lyl phosphite, tri-p-tolyl phosphite, di-p-1lyl phosphite, phosphorous di-o-chlorophenyl acid, tri-p-chlorophenyl phosphite, di-p phosphite
-chlorotetraphenyl, dicyclohexylcarbodiimide,
Tri7enyl phosphate, cyphenyl phosphonate, etc. are used.

The reaction temperature is preferably in the range of 60 to 150°C. The reaction usually completes in a few minutes to 24 hours.

In some cases, reaction conditions may be used that shift the equilibrium toward the production system by using an excess of nitroamine, heating the reaction solution to a high temperature, or removing the water produced.

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

The compound of formula (III) can also be used in the reaction of an acid halide with an amine (e.g., Journal of Organic Chemistry, Vol. 32, pp. 3069 et seq., 1967), or the reaction of a carboxylic acid with incyanate (e.g., Chemical Reviews, Vol. 57, p. 47). pp. et seq., 1957), Reaction of Esters with Amines (Tetrahydrone Letters 1970, 17)
, p. 91 et seq.).

As a method for reducing the compound of formula ', a catalytic reduction method (catalytic hydrogenation method), an acidic reduction method, a basic reduction method, etc. are used.

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

As the catalyst, metal catalysts such as activated carbon with palladium, strontium carbonate with palladium, sodium borohydride with palladium, platinum oxide, Raney nickel, and rhenium oxide are used.

The amount of metal catalyst used is 5% of the dinitro compound described above.
~10% by weight is preferred.

As the solvent, ethanol, methanol, acetic acid, dioxane, cyclohexane, water, tetrahydrofuran, ethyl acetate, dimethylformamide, etc. are used. Particularly preferred is dimethylformamide.

The reaction temperature is usually in the range of room temperature to reflux temperature, especially 25
~50°C is preferred. The reaction is usually completed in 4 to 48 hours.

The generated diamine compound of formula (1) can be obtained as a precipitate in an aqueous solution, and can be purified by recrystallization from methanol.

Example 1 N,N'-bis(3-nitrophenyl)-5-hydroxyisophthalamide m-nitroaniline 2 7. 6. ! i' (2
00 mmol) and 5-hydroxyisophthalic acid 18
．． 11 (100 mmol) was dissolved in 200 ml of N-methyl-2-pyrrolidone, and pyridine 5Q was added to this solution.
ml, 62 g (200 mmol) of triphenyl phosphite, and 10.6 g (250 mmol) of lithium chloride were added in sequence, and the mixture was stirred at 100° C. for 6 hours. After cooling, the reaction mixture was poured into 3000 ml of methanol, stirred at room temperature for 1 hour, and the precipitated solids were separated. The obtained solid was washed with hot methanol, dried, and the title compound was dissolved in 3
3.7 g (yield: 80%) was obtained.

Elemental analysis value (C,.H,,N,) C HN Calculated value ■ 56.88 3.34 13.27 Actual value (f) 56.79 &51 13.29 Engineering R spectrum (crn-1: KBr method) 3250, 1
660, 1528, 1350'H-NMR spectrum (
δ: DMSO-d', TMS standard) 7.5 5~
8.8 6 (1 1 H, m) 10.90 (2
H,s) (B) 20 g (48 mmol) of the compound obtained from N,N'-bis(3-aminophenyl)-5-hydroxyisophthalamide (A), 2 g of palladium-attached activated carbon, and 15 dimethylformamide.
0 ml of the suspension was heated at 50° C. for 12 hours under hydrogen atmosphere. After applying palladium-coated activated carbon to each house, add F solution to 100% water.
Injected into 0rlLl. The precipitated solids were separated from each other, dried, and extracted using a Soxhlet machine using methanol. Methanol was removed from the extract under reduced pressure to obtain the target compound 15.
4.9 (yield 88%) was obtained.

Elemental analysis value (020H18N4) C HN Calculated value ■ 66.29 5.01 15.7!6 Actual value (f) 66.40 4.99 15.50 engineering R sect/l/ (cm-1: KBr method) 52
05,f660'H NMR spectrum (δ: DMSO-d',
'rMs standard) 3.40 (4H, bs) 6.1 5~7.95 (11 H1 m) 10.0
0 (2H,s) Example 2 (A)N. N'-bis(nitrophenyl)-5-hydroxyin 7-talamide p-nitroaniline 2 7. 6 F (2 0 0
mmol) and 5-hydroxyinphthalic acid 1 8.
2 g (100 mmol) was dissolved in 200 ml of N-methyl-2-pyrrolidone, and pyridine 5Q was added to this solution.
ml, tri7enyl phosphite 6211 (200 mmol) and lithium chloride 10.6.9 (250 mmol)
were added one after another, 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 the title compound at 35, 2. F
(yield 83%).

Elemental analysis value (C2.HI4N4) C H N calculation value (F)
56.88 5.54 13.27 Actual value■
57.01 3.39 14.03IR spectrum ((Ml-”r KBr method) 3255, 16
52, 1524, 1646'H-NMR spectrum (
δ: DMSO-d', TMS standard) 7.42~8
．． 91 (11H, m) 11.02 (2H, S) (B) 20 g (48 mmol) of the compound obtained with N,N'-bis(4-aminophenyl)-5-hydroxyisophthalamide (A) ), a suspension of 2 g of palladium-coated activated carbon and 150 rttl of dimethylborumamide was heated at 50°C under a hydrogen atmosphere.
Heated for 2 hours. Thereafter, the same treatment as in Example 1(B) was carried out to obtain the desired compound. 0. 9 (yield 85%)
Obtained.

Elemental analysis value (ct.Hl8N4) C H N Calculated value (F) 66.29 5. CN15.
46 actual measurement value (埒 66.22 5.05 j5
．． 4jIR Spect/I/ (c1r!-1: K
Br method) 3211, 1661 1H-NMR spectrum (δ: DMSO-d', TM
S standard) & 45 (4H, bs) 6.013~8.0 1 (1 1 HSm) 10
．． 05 (2HS S) Example 3 (A)N. u-bis(6-nitro-n-hexyl)-5
-Hydroxyisophthalamide 6-nitrohexylamine 2 9. 2 1 ( 2
0 a mmol) and 5-hydroxyisophthalic acid 18
．． 2 g (100 mmol) was dissolved in 200 ml of N-methyl-2-pyrrolidone, and in this solution was added pyridine 5QmJ,
Triphenyl phosphite 62g (200 mmol), lithium chloride 10.6,! 9 (250 mmol) were added one after another, and the mixture was stirred at 100°C for 6 hours. Thereafter, the treatment was carried out in the same manner as in Example 1(A) to obtain the title compound. 69 (yield 79%) was obtained.

Elemental analysis value (C!OH30N4) C H N calculated value%)
54.79 6.90 12.78 Actual value (
f) 56.01 6.95 12.76IR
Spectrum (cm-': KBr method) 3240, 1
645, 1526, 1641IH-Shoden spectrum (δ
: DMso-a6,'rMS standard) 1.52 (12H
, s) 7.52-8.82 (1 1H, m) 10.98 (2H, s) (B) N,N'-bis(6-amino-n-hexyl)-
21 g of the compound obtained with 5-hydroxyisophthalamide (A) (48 mi IJ
mole), activated carbon with palladium2. 1. ! A suspension of i+ and 150 m/dimethylformamide was heated at 50° C. for 12 hours under a hydrogen atmosphere. Thereafter, the same treatment as in Example 1(B) was carried out to obtain 14.9 g of the target compound (yield 82%).
Obtained.

Elemental analysis value (020H34N4) C H N Calculated value ■ 66.46 9.05 14.80
Actual value (F) 65.57 9.04 14.
74IR spectrum (an-': KBr method) 32
11, 1661′ H-NMR spectrum (δ: DMso-aa
, TMS standard) 1.50 (12H, s) 2.71 (4H, l) S) 6.51 to 7.88 (1 1H, m) 10.25 (2HS S) Applicant Tomogawa Paper Co., Ltd. Representative Patent Attorney Junichi Takahashi Procedural Amendment (voluntary) February 16, 1990 Commissioner of the Japan Patent Office Fumi Takeshi Yoshida 1. Incident display patent application No. 1-56192 2. Title of the invention: Novel diamine compound and method for producing the same 3. Relationship with the case of the person making the amendment Patent applicant address name Tomoekawa Paper Manufacturing Co., Ltd. 4. Agent address: 1-16-9 Toranomon, Minato-ku, Tokyo 5. Written date correction of amendment order (Japanese Patent Application No. 1-56-92) The following corrections are made in the specification.

1. The full text of the claims on pages 1 and 2 is revised as shown in the attached sheet.

2. "Alkyl group" on page 4, line 3 has been changed to "alkylene group."

3. Change "4-amino" to "6-amino" on page 6, line 4.

“Claim 1. General formula 0H 2. A diamine compound represented by a C1-C12-alkylene group, and R1 means a hydrogen atom, a lower alkyl group, a halogen atom, a nitrile group, a nitro group, a T-alkoxy group, or a hydroxyl group.

The general formula 0H represents a C + -C I 2-alkylene group, and R1
is a hydrogen atom, a lower alkyl group, a halogen atom, 2} I
"A method for producing a diamine compound according to claim 1, which is characterized by reducing a diamine compound represented by a diamine compound (representing a diamine group, a ditro group, an alkoxy group, or a hydroxyl group)" Patent Applicant Stock Company Tomoekawa Paper Mill

Claims (1)

[Claims] 1. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R is a group ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or optionally substituted C_1 to C_1_2- A diamine compound represented by an alkyl group, and R^1 means a hydrogen atom, a lower alkyl group, a halogen atom, a nitrile group, a nitro group, an alkoxy group, or a hydroxyl group. 2. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R is a group ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or an optionally substituted C_1-C_1_2-alkyl group, R ^1 means a hydrogen atom, a lower alkyl group, a halogen atom, a nitrile group, a nitro group, an alkoxy group, or a hydroxyl group. manufacturing method.