JPH02270848A - Novel diamine compound and production thereof - Google Patents

Abstract

NEW MATERIAL:A diamine compound of formula I (Z is direct bond, O, S, CO, CH2, SO or SO2; R<1> and R<2> are H, lower alkyl, halogen, nitrile, alkoxy or OH). EXAMPLE:N,N'-Bis[4-(4-aminophenoxy)phenyl]-4 or 5-hydroxyisophthalamide. USE:A monomer for synthesizing polymers such as polyimide resins, polyamide resins or polyamideimide resins. PREPARATION:A dinitro compound of formula II is reduced to prepare the diamine compound of formula I. The dinitro compound of formula II is prepared by reacting a nitroamine compound of formula III with a dicarboxylic acid or a derivative thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel diamine compound, particularly a diamine compound useful as a monomer for polymer synthesis, 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 compounds, and 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 used to produce polyimide resins, polyamide resins, polyamideimide resins, etc.
The resulting resin has good heat resistance, but has problems in moldability and the like.

Therefore, in order to balance these advantages and disadvantages, composites of epoxy resins and polyimide resins, polyamide resins, polyamideimide resins, etc. are being considered, but the situation is still insufficient.

The main obstacles were that the resulting resin was insoluble or difficult to dissolve in the solvent, and that the desired properties were not achieved because the resulting resin and epoxy resin were not uniformly mixed in the desired composition.

An object of the present invention is to provide a diamine compound that has active sites for epoxy compounds and is useful as a raw material for polyimide resins, polyamide resins, polyamide-imide resins, etc. that can be composited with epoxy resins.

[Means to solve the problem]

The present invention is based on the general formula (where Z is a direct bond, an oxygen atom, a sulfur atom, a group \C=O
1-CH2-1-8〇- or -502-1R1 and/R2 are a diamine compound represented by a hydrogen atom, a lower alkyl group, a rogen atom, a nitrile group, an alkokene group, or a hydroxyl group.

Individual R1 and R2 may be the same or different.
.

Examples of the compound represented by formula (1) include the following compounds. N, Sobis[4-(4-aminophenoxy)phenyl]-4- or 5-hydroxyinphthalamide, N, N'-bis(4-(4-7minophenylsulfinyl)phenyl)-4= or 5-hydroxyinphthalamide, NIN'-bis(: 4-, (4-aminophenylsulfenyl)phenyl)-4- or 5-hydroxyinphthalamide, N,N'-bis[4-( 4-7
/phenylsulfonyl)phenyl]-4- or 5-hydroxyinphthalamide, N, Sobis[4-(4-
aminophenyl)phenyl]-4- or 5-hydroxyinphthalamide, N,N'-bis[4-(4-aminobenzoyl)phenyl]-4- or 5-hydroxyinphthalamide, N,N'-bis (4-(4-aminobenzyl)phenyl)-4- or 5-hydroxyinphthalamide, N,N'-bis[j-(3-aminoenoxy)phenyl-5-hydroxyinphthalamide,
N, I-bis(3-(3-aminophenylsulfinyl)phenyl)-5-hydroxyisophthalamide, N
, N'-bis[6-(3-7minophenylsulfenyl)phenyl-5-hydroxyisophthalamide, Nl
Ge-bis(3-(3-aminophenylsulfonyl)phenylcou-5-hydroxyinphthalamide, N,N'-
Bis(3-(3-aminophenyl)phenyl-5-hydroxyisophthalamide, N, Corbis(3-(3-
Aminobenzoyl)phenyl 5-hydroxyinphthalamide, N, Sobis(:3-(3-aminobenzoyl)phenyl 5-hydroxyinphthalamide, N
.

"-BisC4-(4-aminophenoxy)phenylcou-2-hydroxyterephthalamide, N.

N'-bis(4-(4-aminephenylsulfinyl)
Phenylcou 2-hydroxyterephthalamide, N, N
f-bis(:4-(4-ami/phenylsulfenyl)
phenyl)-2-hydroxyterephthalamide, N, Sobis[4-(4-aminophenylsulfonyl)phenyl-2-hydroxyterephthalamide, N, N'-
Bis[4-(4-aminophenyl)phenyl-2-hydroxyterephthalamide, N, Sobis[4-(4-
aminobenzoyl)phenyl-2-hydroxyterephthalamide, N, Sobis[4-(4-aminobenzyl)phenyl]-2-hydroxyterephthalamide, and the like.

The diamine compound of formula (1) is obtained by reacting a nitramine compound represented by the general formula (the symbols in the formula have the above meanings) with a dicarboxylic acid or a derivative thereof. It can be produced by reducing a dinitro compound represented by (having a meaning).

The compound of formula (2) in which the group Z is an oxygen atom or a sulfur atom can be prepared by the method of Williamson (for example, Journal of the American Chemical Society Vol. 61, 276).
4 et seq., 1939).

A compound of formula (2) in which the group Z is -5o- or -5O2- can be obtained by oxidizing a compound of formula (2) in which 2 is a sulfur atom. Examples of oxidizing agents include hydrogen peroxide,
Sodium periodate etc. are used. The compound of formula (2) in which Z is -SO- can be obtained by oxidation at low temperature using, for example, hydrogen peroxide. A compound in which Z is -802- can be obtained by oxidation at high temperature.

Formula (2
) can be prepared by the method of Friedel-Krauch [e.g.
(1184)].

A compound of formula (2) in which group 2 is an oxygen atom can be obtained, for example, by reacting an aminephenol derivative with a halogenated nitrobenzene derivative.

Examples of aminephenol derivatives include 0-1m- or p-aminophenol, 2-13- or 5-methyl-4
-aminephenol, 4-methyl-3-aminephenol, 3,5- or 2,6-dimethyl-4-aminoneenol, 3- or 5-n-butyl-4-aminephenol and derivatives thereof.

Examples of halogenated nitrobenzene derivatives include ha, o-
, m- or Hp-chloronitrobenzene, 2- or 3-methyl-4-chloronitrobenzene, 6-14-15- or 6-methyl-2-chloronitrobenzene, 2.6-
or 3,5-dimethyl-4-chloronitrobenzene, 2
-G' again! , 3-n-butyl-4-chloronitrobenzene and hiso derivatives.

The reaction between an amine phenol derivative and a halogenated dibenzene derivative is usually performed using a base such as sodium hydroxide, potassium hydroxide, sodium amide, potassium carbonate, sodium carbonate, triethylamine, barium oxide, silver oxide, or sodium hydride. Preferably, the reaction is carried out in the presence of a solvent. Alternatively, the amine phenol derivative may be used as phenoxyto, and this may be reacted with a halogenated nitrobenzene derivative in a solvent.

As the solvent, toluene, benzene, tetrahydrofuran, acetone, ether, water, methanol, ethanol, butanol, dimethylformamide, dimethylacetamide, dimethylsulfoxide, etc. are used.

The reaction temperature may be generally in the range of room temperature to reflux temperature, and is particularly preferably in the range of 80 to 160°C.

The reaction usually completes in a few minutes to 24 hours.

The generated nitramine compound is obtained by concentrating the reaction mixture.
It can be isolated as a precipitate by pouring it into water, and after isolation, it can be washed, dried, etc.

A dinitro compound (3) is obtained by reacting the nitramine compound (2) with a dicarboxylic acid or a derivative thereof.

Examples of dicarboxylic acids or derivatives thereof include aromatic dicarboxylic acids represented by the following formulas, such as 2-hydroxyinphthalic acid, 4-hydroxyinphthalic acid, 5-hydroxyinphthalic acid, 2-hydroxy/terentalic acid, and 3-hydroxyinphthalic acid. Examples include phthalic acid, 4-hydroxyphthalic acid, and derivatives thereof such as acid halides and esters.

The reaction between a dicarboxylic acid and a nitroamine is usually carried out in a solvent in the presence of a condensing agent.

・Solvent Toshiteha, toluene, benzene, chlorobenzene, dichlorobenzene, acetonitrile, pyridine, tetrahydrofuran, acetic anhydride, dichloromethane, hexane, cyclohexane, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methyl-2-
Pyrrolidone, hexamethyl phosphate triamide, etc. are used (・
It will be done.

If necessary, lithium chloride, to increase the solvation power of the protic solvent and to suppress side reactions.
Inorganic salts such as calcium chloride can also be added to the reaction system.

As a condensing agent, triphenyl phosphite, diphenyl phosphite, tri-tolyl phosphite, di-o-phosphite
Tolyl, phosphite tri-m-tolyl, phosphite di-m-
Tolyl, phosphite tri-p-tolyl, phosphite p-
Tolyl, di-0-chlorophenyl phosphite, tri-p-chlorophenyl phosphite, di-p-chlorophenyl phosphite, dicyclohexylcarbodiimide, triphenyl phosphate, diphenyl phosphonate, etc. are used.

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

In some cases, reaction conditions may be used that shift the equilibrium of the production system by using an excess of nitroamine, heating the reaction solution to high temperatures, or removing the water produced. 3) can be isolated as a precipitate by pouring the reaction mixture into methanol, and after isolation, washing, drying, etc. can be performed.

2) A catalytic reduction method (catalytic hydrogenation method), an acidic reduction method, a basic reduction method, etc. are used to reduce the o compound (6).

Reduction by catalytic hydrogenation is carried out in a solvent in the presence of a catalyst under a hydrogen atmosphere.

As a catalyst, a metal catalyst such as palladium on activated carbon, strontium carbonate with siladium, palladium on borohydride, platinum (IV) oxide, Raney nickel, rhenium oxide, etc. is used4).

The amount of the metal catalyst used is preferably 5 to 10% by weight of the dinitro compound.

As the solvent, ethanol, methanol-712, acetic acid, dioxane, cyclo'\yazan, water, futrahydrofuran, ethyl acetate, dimethylformamide, etc. are used. Particularly preferred is dimethylformamide.

The reaction temperature may be generally in the range of room temperature to reflux temperature, and is particularly preferably 25 to 50°C.

The reaction is usually completed in 4 to 48 hours.

The produced cyanide can be obtained as a precipitate in an aqueous solution, and can be purified by recrystallization using methanol.

The diamine compound of the present invention is particularly useful as a monomer for polymeric materials that require active sites for EBOKI 7 compounds and the like.

Example 1 (A) Sodium p-aminophenoxide 42°7,! 7 (326 mmol) tr,+-chloronitrobeni/zeni2. a, y (s1 mmol) of water 2
00 ml aqueous solution was refluxed for 8 hours. p by steam distillation
After removing -chloronitrobenzene, the precipitated solid was separated and recrystallized using methanol to obtain 14.5 g of 4-nitro-41-aminodiphenyl ether (yield: 7H%).

Elemental analysis value: C1□I-('1oN2 as CHN Calculated value (Approx. 62.61 4.38 12.17 Actual value (Approx. 62.59 4.41 12.121 R spectrum (cm': KBr method) 1524.1348 'H-NMR spectrum (δ:D) proverb 5o-d' T
MS standard) 3.50 (2H, s) 6.5: 2-8.26 (8H, m) (B) 4-
Nitro 47-aminodiphenyl ether 46&(2o
o mmol) and 18.2 g of 5-hydroxyisophthalic acid.
(100 mmol) of N-methyl-2-pyrrolidone 20
Dissolved in 0 ml, 5 Q ml of pyridine, 62 g (200 mmol) of triphenyl phosphite, 10.6 ml of lithium chloride.
g (250 mmol) were added sequentially to 1o o'c.
The mixture was stirred for 6 hours. After cooling, the reaction mixture was poured with 3000ml of water.
The mixture was poured into a flask and stirred at room temperature for 1 hour, and the precipitated solid was filtered out. The obtained solid was washed with hot methanol and then dried, and N,Corbis[4-(4-nitronenoxy)phenyl)-5-hydroxyisophthalamide was added to the
1.6 g (yield: 85%) was obtained.

Elemental analysis value: C3□H2□N, CHN Calculated value (%) 63.37 3.56 9.24 Actual value (%i 63.31 3.48 9.53 ■R sect/l/ (cm-' : KBr method) 6255.1
667.1520.1348'H-NMR spectrum (
δ: DMSO-d' TMS standard) 6.46-8.8
1 (19H, m) 11.10 (2H, 5) (c) N, Cibis[4-(4-nitrophenoxy)phenylcou 5-hydroxyinphthalamide 29g
(48 mmol), a suspension of 2 g of palladium-attached activated carbon and 150 ml of dimethylformamide was heated at 50 mL under a hydrogen atmosphere.
Heated at ℃ for 12 hours.

After separating the palladium-attached activated carbon from F, the p solution was poured into 1000 ml of water. The precipitated solids were separated, dried, and then subjected to Soxhlet extraction using methanol. Methanol was removed from the extract under reduced pressure, and N, '-bis[4-(
1 y, 8 g (yield: 68%) of 4-amitunoenoxy) phenylcy 5-hydroxyinfuclamide was obtained.

Elemental analysis value: CHN calculated value as C82H2, N4 ((4) 70.32 7.79 10.25 Actual value (餉) 70.25 7.71 10.191B spectrum (cm-': KBr method) 6213.1659' H-NMR spectrum (δ: DMSO+16TMS
Standard) 3.46 (4H, s) 6.41~8.33 (19H, m) 9.98 (2H
,s) Example 2 (A) Sodium p-aminothiophenoquine 4
8,! A solution of i' (326 mmol) and 12.8 g (8j mmol) of p-chloronitrobenzene in 200 = 16-ml water was refluxed for 8 hours. After removing p-chloronitrobenzene by steam distillation, the precipitated solid was separated and recrystallized using methanol.
16g of amino phenyl sulfide (yield: 80%)
Obtained.

Elemental analysis value CHN calculated value as Cl28ION2 ((6) 58,52 4.09 11.38 Actual value -58,603,9911,3411R spectrum (tyn-': KBr method) 1550.1638 'H-N)AR Spectrum (δ: DMSO-d6TM
S standard) 4.83 (2H,S) 6.55-8.00 (8H,m) (B) 45.2 g (200 mmol) of 4-nitro-4'-7 minodiphenyl sulfide and 5 -Hydroxyinphthalic acid 18.2. ! 9 (10 mmol) is N
- 200 ml of methyl-2-pyrrolidone, 50 ml of pyridine. 62 g (20 mmol) of triphenite/acid and 10.6 mmol (25 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 6,000 ml of water and stirred at room temperature for 1 hour, and the precipitated solids were separated. The obtained solid was washed with hot methanol and then dried to give 51 g of N,N'-bis[4-(4-nitrophenylsulfenyl)phenyl-5-hydroxyinphthalamide (yield;
80%).

Elemental analysis value: CHN calculated value (as C32H22N4) 60.18 3.47 8.77 Actual value (
%J 60.22 3.39 8.82 ■R square (cm-': KBr method) 3260.1661.1
520.1333'H-NMR spectrum (δ: DM
SO-d6TMS standard) 6.913-8.22 (19
H,m)10.92(2H,5) (C) N,N'-bis(:4-(4-nitrophenylsulfenyl)phenyl)-5-hydroxyinphthalic acid f゛30.6! ! A suspension of (4s mmol), 2g of palladium-attached activated carbon, and 15Qml of dimethylformamide was heated at 50°C for 12 hours under a hydrogen atmosphere. After separating the palladium-coated activated carbon, pour the F solution into 1000 m/! of water! I poured it inside. The precipitated solids were separated from each other, dried, and then extracted using methanol. Methanol was removed from the extract under reduced pressure, and N, Sobis[4-(4
-aminophenylsulfenyl) phenyl-5-hydroxyinphthalamide (16.7 g (yield: 60%)
Obtained.

Actual value (%) 66.37 4.45 9.74IR
Spectrum (cm −': KBr method) 3241.1
659'H-NMR spectrum (δ: DMSO-d'TM
S standard) 4.69 (4H, bs) 6.88~8.25 (19H, m) 10.01 (
2H,s) Example 6 (~ 4-nitro-47-aminodiphenyl sulfide 24.6!9 (100 mmol) obtained in Example 2 and 17 g (155 mmol) of 31% hydrogen peroxide solution A mixed solution of 50 ml of acetone was left at room temperature for 60 hours. After removing the acetone under reduced pressure, the precipitated solids were separated from each other.
The obtained solid was washed with hot water, dried, and
-nitro-47-aminodiphenylsulfoxide 16
g (yield: 61%) was obtained.

Elemental analysis value: CHN as Cl2H1oN2 Calculated value (%) 54.59 3.84 10.68 Actual value (%) 54.50 3.99 10.69■R
Schect # (cm-': KBr method)・1559.
1625'H-NMR spectrum (δ: DMSO-d'TM
S standard) 4.92 (2H, S) 6.85-8.42 (8H, m) (B) 52.5 g (200 mmol) of 4-nitro-4'-aminodiphenylsulfoxide and 5-hydroxyinphthalic acid 18.2 g (100 mmol) of N-methyl-2-pyrrolidone at 200 mA! Dissolved in pyridine 5
3 ml of triphenyl phosphite, 619 (200 mmol) of triphenyl phosphite, and 10.6 g (25 mmol) of lithium chloride were successively added thereto, and the mixture was stirred at 100° C. for 6 hours. After cooling, the reaction mixture was poured into 6000 ml of water and stirred at room temperature for 1 hour, and the precipitated isomorphic product was collected from house to house. The obtained solid was washed with hot methanol, dried, and N,N'-
53 g (yield: 79%) of bis[4-(4-nitrophenylsulfinyl)phenyl]-5-hydroxyisophthalamide was obtained.

Elemental analysis value: C32) (2°N, CHN calculated value 6%) 57.31 3.31 8.35 Actual value e%) 57.37 3.39 8.41 ■R sect/l/ (cm- ': KBr method) 3256.1
639.1528.1337'H-NMFI spectrum (δ: DMSO-d6TMS standard) 6.95-8.3
3 (19H,s)11,o2(2HSs) (C) N,N'-bis[4-(4-nitrophenylsulfinyl)phenylcou 5-hydroxyisophthalamide 32.2.9 (48 mmol), A suspension of 2.1 g of palladium-attached activated carbon and 150 ml of dimethylformamide was heated at 50° C. for 12 hours in a hydrogen atmosphere. Palladium-coated activated carbon was placed on the p-side edge, and the furnace liquid was poured into 10,100 O water. The precipitated solids were separated, dried, and then subjected to Soxhlet extraction using methanol. Methanol was removed from the extract under reduced pressure to obtain 17 g (yield: 58%) of N, Sobis(4-(4-aminophenylsulfinyl)phenyl-5-hydroxyisophthalamide).

Elemental analysis value '032H2604 CHN Calculated value (%J 62.94 4,29 9.17 Actual value J 66.11 4.34 9.09 IR spectrum (cm -': KBr method) 6230.1658 'H-NMR Spectrum (δ: DMSO-d6TMS
Standard) 4.88 (4H, s) 6.90-8.20 (19H, m) 10.11 (
2H,s) Example 4 (A) 24.6 g (100 mmol) of 4-nitro-4'-aminodiphenyl sulfide obtained in Example 2
was dissolved in 200ml of glacial acetic acid, and 25ml of 61% hydrogen peroxide solution was added.
0 m, l was added and heated under reflux for 1 hour.

After cooling, excess ice was added. Separate the precipitated solids from house to house,
The obtained solid was washed with hot water, dried, and
-nitro-4'-aminodiphenylsulfone 23.7
9 (yield: 85%) was obtained.

Elemental analysis value: CHN as C1□H, oN2 Calculated value (a) 51.79 3.62 10.07
Actual value ((6) 51.81 3.67 10.0
0IR spectrum (cm-': KBr method) 1549.
1320'H-NMR spectrum (δ: DMSO-d' TMS
Standard) 4.78 (2HSS) 6.95-8.52 (8H, m) (Bl, 55.7 g (200 mmol) of a-nitro-4'-aminodiphenylsulfone and 18.2 g of 5-hydroxyisophthalic acid .9 (100 mmol) -')
I: 1-N-methyl-2-pyrrolidone dissolved in 200 rnl,
Pyridine 5Qmf triphenyl phosphite 62.9 (20
0 mmol) and 6 g (250 mmol) of lithium chloride were sequentially added thereto, and the mixture was stirred at 100°C for 6 hours. After cooling,
The reaction mixture was poured into 3000 ml of water and stirred at room temperature for 1 hour, and the precipitated solids were collected from house to house. The obtained solid was washed with hot methanol and then dried to give N,t-bis[4-(4-nitrophenylsulfonyl)phenyl]
61°8.9 (yield: 88%) of -5-hydroxyinphthalamide was obtained.

Elemental analysis value: CHN calculated value as C32H2□04 (to) 54.7o 3.16 7.97
Actual value) 54.73 3.20 7.86IR
Spectrum (Crn”: KBr method) 3231.1656
．． 1534.1367'H-NMR spectrum (δ:
DMSO-d' TMS Standard) 7.2 (1-8, 39 (
19H,m) 11.10 (2H,s) =26- (C)NI mamas[4-(4-nitrophenylsulfonyl)phenylcy5-hydroxyisophthalamide 3
3.7 g (48 mmol), activated carbon with palladium 2.1
A suspension of 150 ml of dimethylformamide was heated at 50°C for 12 hours under a hydrogen atmosphere. After the palladium-coated activated carbon was separated from the furnace, the F solution was poured into 10,100 O of water. The precipitated solids were separated, dried, and then subjected to Soxhlet extraction using methanol. Methanol was removed from the extract under reduced pressure to obtain 2o& (yield: 65%) of N,U-bis[4-(4-aminophenylsulfonyl)phenyl)-5-hydroquinoinphthalamide.

Elemental analysis value: CHN calculated value as C3□H2604 (Reduced value) 59.80 7.08 8.72 Actual value ((6) 59,81 7,10 8.73
IR spectrum (tyF': KBr method) 3229.
1660'HNMT' (spectrum (δ: DMSO-d,'
TMS standard) 4.69 (4H1S) 722-8.45 (19H, m) 10.05 (2H, S) Example 5 (Al Sodium 5-amino-2-methylphenoxate 40.1.9 (326 mmol) ) and 12.8 g (81 mmol) of p-chloronitrobenzene in 200 g of water
ml aqueous solution was refluxed for 8 hours. p by steam distillation
- After removing the chloronitrobenzene, the precipitated solid was taken from house to house, recrystallized using methanol, and 4-nitro-
6'-amino-6'-methyldiphenyl ether to 16
．． El (yield: 70%) was obtained.

Elemental analysis value CHN calculated value as 13HI2N2 (Zeng 63.93 4.95 11.47 actual value) 62.69 4.43 12.011R spectrum (cm-': KBr method) 1567.1344'H-NMR spectrum (δ: DMSO-d6TMS
Standard) 2.22 (3H, s) 3.53 (2H, s) 6.49'-8,21 (7H, m) (B) 49 g of 4-nitro-3'-amino-6'-methyldiphenyl ether ( 200 mmol) and 18.2 g (10 mmol) of 5-hydroxyisophthalic acid were dissolved in 200 ml of N-methyl-2-pyrrolidone,
0ml, triphenyl phosphite 629 (200,?
1.1 mol) and 10.6 g (250 mmol) of lithium chloride were added one after another, and the mixture was stirred at 100°C for 6 hours. After cooling, the reaction mixture was poured into 3000 ml of water, stirred at room temperature for 1 hour, and the precipitated solid was filtered out. The obtained solid was washed with hot methanol and then dried to give 515 g of N,N'-bis(3-(4-nitrophenoxy)-4-methylphenyl-5-hydroxyisophthalamide) (yield: 89 %)Obtained.

Elemental analysis value: CHN as C32H2, N4 Calculated value (%) 66.434.35 9.68 Actual value (%
) 66.31 4.55 9.391R spectrum (tyn-': KBr method) 3248.1658.1
526.1340'H-NMR spectrum (δ: DM
SO-d' TMS standard) 2.31 (6H, S) 6.51~8.78 (+7H, m) 11.00 (
2H,5) (cj N,N'-bis[:3-(4-nitrophenoxy)-4-methylphenylcy) Suspension of 28 g (48 mmol) of 5-hydroxyisophthalamide, 2 g of palladium-coated activated carbon, and 150 ml of dimethylformamide The liquid was heated at 50°C for 12 hours in a hydrogen atmosphere. After the palladium-coated activated carbon was poured into each house, the F solution was injected into 1000 m/! of water. The precipitated solid was separated, and after drying, methanol was added (
- Soxhlet extraction was performed. Methanol was removed from the extract under reduced pressure to obtain 17.4 g of N,N'-bis[6-(4-aminophenoxy)-4-methylphenyl]-5-hydroxyisophthalamide (yield: 70%). Obtained.

Elemental analysis value: C32HsoN< as HN Calculated value (HN) 74.11 5.83 10.80 Actual value (/,) 74.31 5.69 10.68 IR spectrum (tvr': KBr method) 3225.164
9'HNMPf spectrum (δ: DMSO-d'T
MS standard) 2.25 (6 +, S) 3.48 (4) (, S) 6.55-8.01 (17 H, m) 10.03 (2 H, S) Example 6 (A) Sodium A solution of 40 g (326 mmol) of p-aminophenoxyto and 17.59 (81 mmol) of 2-chloro-4-nitrotoluene in 200 ml of water was refluxed for 8 hours. After removing p-chloronitrobenzene by steam distillation, the precipitated solid was separated and recrystallized using methanol.
13.6g of aminodiphenyl ether (yield: 69%)
)Obtained.

H NMR spectrum (δ: DMSO-d' TMS
Standard) 2.23 (3H, s) 3.45 (2H, s) 6.39'~8.36 (7H, m) (B) 6-nitro-6-methyl-4'-aminodiphenyl ether 49
g (200 mmol) of 5-hydroxyisophthalic acid 18.2.9 (100 mmol) of N-methyl-2-
Dissolved in 200 ml of pyrrolidone, sequentially added 5 Q ml of pyridine, 62.9 (20 mmol) of triphenyl phosphite, and 10.6.9 (250 mmol) of lithium chloride.
The mixture was stirred at 100°C for 6 hours. After cooling, the reaction mixture was poured into 3000 ml of water and stirred at room temperature for 1 hour, and the precipitated solids were separated. The obtained solid was washed with hot methanol and then dried to obtain N, Gobis [4-(3
-nitro-6-methylphenoxy)phenyl]-5-hydroxyisophthalamide 49.29 (yield; 85
%)Obtained.

Elemental analysis value: C, 2H, N, CHN calculated value (candle 66.43 4.35 9.68 actual value (
Shocking 66.51 4,25 9.56IR spectrum/l
/ (Cm-1: KBr method) 3240.1646.1
521.1348'H'-NMR spectrum (δ:DM
SOd' TMS standard) 2.35 (6H, s) 6.48~8.68 (17H, m) 10.88 (2
H,5) (C)N,R-bisC4-(3-nitro-6-
A suspension of 28 g (48 mmol) of methylphenoxy)phenyl)-5-hydroxyisophthalamide, 2 g of palladium-coated activated carbon, and 15 (3 mL) of dimethylformamide was heated at 50°C for 12 hours in a hydrogen atmosphere.The palladium-coated activated carbon was separated in a furnace. After that, the furnace liquid was poured into 1000 ml of water.The precipitated solids were separated, dried, and subjected to Soxhlet extraction using methanol.Methanol was removed from the extract under reduced pressure, [4-(6-〇l
- monoamino-6-methylphenoxy)phenyl]=5-hydroxyinphthalamide at 16.2.9 (yield; 65
%)Obtained.

Elemental analysis value: CHN calculated value as C32H3ON4 (% + 74.11 5.83 10.80 Actual value (throat 73.88 6.01 10.611R spectrum (cm-': KBr method) 3235.1648'H-NMFt Spectrum (δ: DMSO-d'T
MS standard) 2.30 (6H, s) 3.45 (4H, s) 6.48-8.25 (17H, m) 9.89 (2H
,s) Example 7 (A) 40.19 (326 mmol) of sthorium 5-amino-2-methylphenoxide and 2-chloro-
A solution of 17.5 g (8 j mmol) of 4-nitrotoluene in 200 ml of water was refluxed for 8 hours.

After removing p-chloronitrobenzene by steam distillation,
The precipitated solid was separated in a furnace and recrystallized using methanol to give 3-nitro-6-methyl-3'-amino-6-methyldiphenyl ether (15, 2,!). i'(yield; 7
3%) obtained.

Elemental analysis value CHN Calculated value as +4H14N2 (%) 64.92 5.29 11.02 XR spectrum (crF': KBr method) 1540.1643 'H-NMR spectrum (δ: DMSO-d'TM
S standard) 2.15 (3H, s) 2.28 (3H, s) 3.49 (2H, S) 6.25-8.01 (6H, m) (B) 3-nitro-6-methyl- 51.6 g (200 mmol) of 3'-amino-6-methyldiphenyl ether and 18.2.9 g (100 mmol) of 5-hydroxyisophthalic acid.
mmol) in 200ml of N-methyl-2-pyrrolidone, 5Qml of pyridine, and 62ml of triphenyl phosphite.
! ;I (2oo mmol), lithium chloride 10-6.9
(2so mmol) were added one after another and stirred at 100°C for 6 hours. After cooling, the reaction mixture was poured into 3000 m/+ of water, stirred at room temperature for 1 hour, and the precipitated solids were collected from house to house.

The obtained solid was washed with hot methanol and then dried to give 491 g of N,R-bis[:3-(3-nitro-6-methylphenoxy)-6-methylphenyl-5-hydroxyisophthalamide. (Yield: 82%).

Elemental analysis value: CKN calculated value as C34H3oN4 (4 67.32 4.98 9.24 actual measured value f
f,,) 67.18 5.06 9.32IR spectrum (cm-': KBr method) 3245.1651
．． 1560.1342'HNMR spectrum (δ: D
MSO-d' TMS standard) 2.24 (6H, s) 2.36 (6H1S) 6, 39-8.55 (j5 H, m) 11.10 (
2H,5) (c) N,R-bis[3-(3-nitro-6-methylphenoxy)-6-methylphenyl-5-hydroxyisophthalamide29. ! 7 (48 mmol), 2 g of palladium-coated activated carbon, and 150 ml of dimethylformamide
The suspension was heated at 50° C. for 12 hours under a hydrogen atmosphere.

After the palladium-coated activated carbon was separated from the furnace, the F solution was poured into 10,100 O of water. The precipitated solids were separated, dried, and then subjected to Soxhlet extraction using methanol. Methanol was removed from the extract under reduced pressure, and N,I-bis[6-(6
17.8 g of -amino-6-methylphenoxy)-6-methylphenyl-5-hydroxyinphthalamide
(yield: 68%).

Elemental analysis value: C34H34N, CHN Calculated value (%) 74.70 6.2710.25 Actual value (Zeng 74.65 6.21 10.53 IR spectrum # (tyrr': KBr method) 3226.164
6'H-NMR spectrum (δ: DMSO-d'TM
S standard) 2.24 (6H, s) 2.33 (6H, S) 3.55 (4HS s) 6.51-8.40 (15HS m) 10.00 (
2H, s) Applicant: Tomoekawa Paper Mills Co., Ltd. Representative, Patent Attorney Atsushi Takahashi - Procedural amendment written voluntarily) July 9, 1990

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, Z is a direct bond, an oxygen atom, a sulfur atom, a group ▲ Numerical formula,
There are chemical formulas, tables, etc. ▼, -CH_2-, -SO- or -SO_2-, R^1 and R^2 represent a hydrogen atom, a lower alkyl group, a halogen atom, a nitrile group, an alkoxy group, or a hydroxyl group) diamine compound. 2. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Z is a direct bond, oxygen atom, sulfur atom, group ▲ Mathematical formula,
There are chemical formulas, tables, etc. ▼, -CH_2-, -SO- or -SO_2-, R^1 and R^2 represent a hydrogen atom, a lower alkyl group, a halogen atom, a nitrile group, an alkoxy group, or a hydroxyl group) The method for producing a diamine compound according to claim 1, characterized in that the dinitro compound is reduced.