JPS63239257A - Production of diaminobenzanilide derivative - Google Patents

Abstract

PURPOSE:To produce a diaminobenzanilide derivative having alkoxy group at a specific site, by producing a dinitrobenzanilide derivative from a 4- nitroaniline derivative and a nitrobenzoic acid halide derivative and reducing the obtained derivative. CONSTITUTION:The objective compound of formula VIII can be produced by reacting a 4-nitroaniline derivative of formula I with a 4-nitrobenzoic acid halide derivative of formula II (R1-R4 are H, alkyl, alkoxy or halogen; at least one of them is alkoxy; X is halogen), reducing the resultant dinitrobenzanilide of formula III to diaminobenzanilide derivative of formula IV, reacting the obtained derivative with especially a compound of formula V (R5 is alkyl) and a compound of formula VI and reducing the obtained compound of formula VII. A compound containing alkoxy group introduced at a specific site of diaminobenzanilide is useful as a production raw material for resin material having low thermal expansion coefficient.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing diaminobenzanilide derivatives useful as raw materials for producing polyimides, polyamideimides, dyes, and the like.

[Prior Art] Diaminobenzanilide or its derivatives are known as synthetic intermediates for dyes, for example (Japanese Patent Laid-Open No. 48-62.
Publication No. 828). This compound is also known to be used as a raw material for producing aromatic polyimide, aromatic polyamideimide, etc. (U.S. Pat. No. 3,179,635
No. Specification).

However, when diaminobenzanilide is used as a raw material for producing these resins, problems such as increased water absorption and poor solder resistance occur.

However, through research by the present inventors, it has been found that this problem can be solved by introducing an alkoxy group into a specific position of this diaminobenzanilide.

[Problems to be Solved by the Invention] An object of the present invention is to provide a novel method for producing diaminobenzanilide derivatives that are particularly useful as raw materials for producing low thermal expansion resin materials.

[Means for solving the problems] That is, the present invention provides 4-
A nitroaniline derivative and 4 represented by the following general formula (2)
-Nitrobenzoic acid halide derivative (general formula (1)
and (2) in which R1 to R4 represent hydrogen, a lower alkyl group, a lower alkoxy group, or a halogen, at least one of which is an alkoxy group, and X represents a halogen) to form the following general formula ( 3) (However, in the formula, R1 to R4 are the above general formulas (1) and (2)
The dinitrobenzanilide derivative represented by the general formula (3) is then reduced to produce a dinitrobenzanilide derivative represented by the following general formula (wherein R1 to R4 are the same as those described above). General formulas (1) and (2)
This is a method for producing a diaminobenzanilide derivative, which produces a diaminobenzanilide derivative represented by

In the present invention, hydrogen, a lower alkyl group, a lower alkoxy group, or a halogen can be selected as R1 to R4. The term "lower" in lower alkyl and lower alkoxy groups refers to those having less than 10 carbon atoms, and when the number is 10 or more, it is difficult to reduce the thermal expansion of the resin obtained by using the compound of the present invention.

In general, in the present invention, at least one of these R1 to R4 needs to be an alkoxy group. Without this alkoxy group, the water absorption resistance and mechanical properties of the polyimide or polyamideimide resin obtained using the compound of the present invention will be poor, which is not preferable.

As for the nitrobenzoic acid halide derivative used as a raw material for synthesizing the diaminobenzanilide derivative, any halogen can be selected, but nitrobenzoic acid chloride derivatives are preferred because of their low cost.

In the synthesis reaction for synthesizing the dinitrobenzanilide derivative, which is the raw material for producing the compound of the present invention, from the nitroaniline derivative and the nitrobenzoic acid halide derivative, the yield will decrease if active hydrogen and water are present in the reaction system. Since this is not preferred, it is desirable to use a solvent or mixed solvent that does not have active hydrogen. Here, active hydrogen is 10H, -3H
, -NHl-COOHl-303H, etc., and is highly reactive hydrogen that can react with acid halides.

In addition, in order to remove the hydrogen halide generated in the reaction system from the system, it is preferable to carry out the reaction under reduced pressure or in the presence or dropwise addition of a basic compound such as a tertiary amine. To avoid this, it is desirable to carry out the reaction under cooling.

Any known method can be applied to the reaction of reducing the nitro group of the dinitrobenzanilide derivative as the second reaction. For example, pt, Ra-Ni.

A method of reducing with hydrogen gas using a catalyst such as Pd-C,
LiA group. Examples include a method of reduction using a metal catalyst such as re, Zn, etc., and a method of reduction in a proton solvent.

General methods such as recrystallization and distillation can be applied to separate and purify the obtained product. Recrystallization is more preferable for applications requiring high purity of 95% or more, for example, for use as a resin raw material.

[Example] An embodiment of the present invention will be described below.

2, l with reflux condenser and stirrer! 2-methoxy-4-nitroaniline in a reactor of 102. l (0゜611
mol) and 700 d of pyridine were charged and dissolved by stirring under a nitrogen atmosphere. The reaction system was cooled to 5°C with ice water, and 113.4 g (0°611 mol) of 4-nitrobenzoic acid chloride was gradually added under a nitrogen atmosphere.
After the exotherm ended, the reaction system was stirred at room temperature for 2 hours.

The reaction mixture was poured into water, the precipitated yellow powder was separated by filtration, and 1
．． After washing with Il water 4 times, drying under reduced pressure at 90°C, the crude 2
゛-Methoxy4,4°-dinitrobenzanilide 18
4.1 g was obtained.

The obtained crude 2°-methoxy 4,4°-dinitrobenzanilide, 10 g of Pd-C (manufactured by JGC Chemical ■: Palladium Carbon Pd 5%) and dimethylacetohydrogen ([)M to C>1000rn1 were placed in a reactor of 21. When hydrogen gas was bubbled through a ball filter at a rate of 1 ρ/min while stirring at 70°C, absorption of hydrogen gas was confirmed.

After reacting for about 10 hours and no longer absorbing hydrogen gas,
After cooling, Pd-C was separated by filtration, 1500 mg of water was added to the obtained 0HAc solution, heated to 80°C, left to cool, and precipitated pale brown crystals were filtered off. The obtained crystals were dried under reduced pressure at 90°C to obtain 134.57 pure 2°-methoxy-4,4°-diaminobenzanilide (yield: 85°6%) with a melting point of 155-157°C.

Example 2 A 500 d reactor was used and 2-methoxy-4-
25.4 g (0,151 mol) of nitroaniline and 200 d of pyridine were charged, and 28.0 g (0,151 mol) of 3-nitrobenzoic acid chloride was prepared in the same manner as in Example 1.
were reacted to obtain 47.2 g of crude 2'-methoxy-3,4'-dinitrobenzanilide.

The obtained crude 2°-methoxy 3,4°-dinitrobenzanilide, 5 g of Ra-Ni and diethylene glycol dimethyl ether (diglyme >230 d) were charged into a 1.l! autoclave, and the temperature was raised to 80° C. with stirring. When the pressure was increased to 30 atmospheres using hydrogen gas, absorption of hydrogen gas was confirmed.

After reacting for about 4 hours and absorbing no hydrogen gas, it was cooled and Ra-Ni was separated by filtration. 400 mff of water was added to the resulting diglyme solution, heated to 80°C, left to cool, and precipitated. The pale brown crystals were filtered off. The obtained crystals were dried under reduced pressure at 70°C to obtain 32.7 g (yield: 84.2%) of pure 2°-methoxy-3,4°-diaminobenzanilide with a melting point of 88 to 90°C.

The elemental analysis value of this product is the theoretical value as follows: C: 65.35%: @: 5.87%
: N: 16.34χ Actual value: C: 65.38
%: H: 5.85%: N: IB, 36%, and as a result of "'C-N)fR analysis, the following absorption 16
5.4pl)m, 152.7ppm, 148.
8p1)m, 147.2E)l)Ill.

135.8ppm, 128.9pl)m, 125.
61)pm, 116.6pl)m.

115.8ppm, 114.3ppm, 112.8
ppm, 105.2 ppm.

97.7 pl) m, 55.3 ppm were confirmed, and as a result of '+1-NHR analysis, the following absorptions were 8.80 ppm (IH), 7.30 ppm (1 old,
6.96-7.21 pl) m (3H).

6.71ppm (IH), 6.30ppm (ltl
), 6.15 ppm (IH).

5.251X)m(2H), 5.03pl)m(2
H), 3.72 ppm (3N) was confirmed, and it was confirmed that it was the target product. Further, as a result of infrared absorption spectrum analysis, absorption of an amide bond was observed at 1,628 cm-1.

Example 3 2-methoxy-5-nitroaniline 25.49 (0°151 mol) and 3-nitrobenzoic acid chloride 28.
0 g (0,151 mol) and reacted in the same manner as in Example 2 above to obtain 28.0 g of pale brown crystals of 2'-methoxy-3,5'-diaminobenzaniline (yield 72.1%).
> obtained.

The melting point of this product is 61.0 to 69.0°C, and its elemental analysis values are theoretical values as follows: C: 65.35%: H: 5.87%;
N: 1B, 34% Actual value: C: 65.20%
: H: 5.95% S N: 16.37%, and as a result of "'C-NHR analysis, the following absorption 165
．． 2f) Dm, 149.01) pIn, 142
．． 4ppm, 141.5ppm.

135.8ppm, 129.21)pm, 127.
7ppm, 117. OpI)m.

114.2pm, 112.5ppm, 109
．． 7ppm, 108.8ppm.

56.5ppHl was confirmed, and furthermore, 'H-NHR car N8 fruit, the following absorption 8.80ppm (IH), 7.38ppm (IN)
, 7.15 ppm (II).

7.09ppm (ltl), 7.01ppm (18
), 6.65-6.88 ppm (2H).

6.331)I)m(1)1), 5.3Apl)m
(2+1), 4.721)l)m(2N).

3.73 ppm (3 tl) was confirmed, confirming that it was the target product. Further, as a result of infrared absorption spectrum analysis, absorption of an amide bond was observed at 1,657 cm-1.

Example 4 25.4 g of 2-methoxy-5-nitroaniline (0°1
51 mol) and 4-nitrobenzoic acid O-ride 28.0
g (0,151 mol) and reacted in the same manner as in Example 2 above to obtain 31.5 g of light brown crystals of 2°-methoxy-4,5′-diaminobenzaniline (yield 81.1%).
I got it.

The melting point of this product ranges from 145.8 to 146.3°C, and its elemental analysis values are theoretical as follows: C: 65.35%: H: 5.87%:
N: 16.34% Actual value: C: 65.40%
; To1: 5.86%: N: 16.30%, and as a result of "'C-NHR analysis, the following absorption 16
4.3ppm, 152. lppm, 142.3DI
) m, 141. Apl) m.

128.81)pm, 128.1pl)m, 121
．． Opl)m, 112. apl) m.

112.3pIII, 109. lppm, 108
．． apl)m, 56.41)I)m was confirmed, and further, as a result of 1H-NHR analysis, the following absorption 8.65ppm (1 old, 7.631)l)Ill(
211), 7.3 sppm (1) 1>.

6.75pDIII (1N), 6.600pm (2
11), 6.301)l)m(IH).

5.75ppm (2tl), 4.67ppm (2t
( ), 3.73 ppm (3t-t) was confirmed, and it was confirmed that it was the target product. Further, as a result of infrared absorption spectrum analysis, absorption of an amide bond was observed at 1,655 cm-'.

Example 5 In the same manner as in Example 2, 25.59 (0.14 mol) of 2-ethoxy-4-nitroaniline and 26.0 g (0.14 mol) of 4-nitrobenzoic acid chloride were used.
-Ethoxy-4,4°-diaminobenzanilide was synthesized to obtain 28.9 g of pale brown crystals (yield 76.0%).

The melting point of this product is 138-140'C, and the elemental analysis value is the theoretical value: Q: 68.40%:)-1:6.32%
: N: 15.49% Actual value: C: 66.33
%; l-1: 6.35%: N: 15.54%.

In addition, as a result of 'tl-N)fR analysis, a, 27ppm (IN), 8.01ppm (ltl
), 7.63 ppm (2 tl).

6.67ppm (2tl), 6.24t)I)m(
2N), 5.08ppm (2N).

4.37ppm (2N), 4.00ppm (2N)
, 1.39 ppm (3N) was confirmed, confirming that it was the desired product. Further, as a result of infrared absorption spectrum analysis, absorption of an amide bond was confirmed at 1,640 cm''.

Application Example 2°-Methoxy-4,4°-diaminobenzanilide 0.0. 075 mol and D) lAc17
After stirring, 0.075 mol of pyromellitic anhydride was gradually added and reacted while cooling to below 10°C. After reacting for about 20 minutes, 0.025 mol of diaminodiphenyl ether, 0.025 mol of benzophenone tetracarboxylic anhydride, and 50 m (l) of DHAc were added and stirred for an additional 2 hours to obtain an attractive resin solution.

The obtained resin solution was fixed on a Pyrex glass plate, and a film with a thickness of about 2
It was coated with an applicator to a thickness of 5 μm, heated sequentially at 100°C, 130°C, and 160°C in a strong draft oven, and then raised to 330°C over 15 minutes to perform an imidization reaction. .

This copper-clad product is almost flat, and the temperature of the resin is 100-240℃.
The coefficient of linear expansion was extremely small at 8 x 10'(K-'). Further, the bending resistance (8STHD 217B-63T) of this resin was 20,000 times or more, indicating high flexibility. Furthermore, the water absorption rate after 24 hours of dispersion was 2.8%, which was much improved compared to conventional polyamideimide.

[Effects of the Invention] The compounds of the present invention are useful as synthetic intermediates used for various purposes, and are particularly useful as raw materials for low thermal expansion resin materials.

Claims (2)

[Claims] (1) 4-nitroaniline derivative represented by the following general formula (1) and 4-nitrobenzoic acid halide derivative represented by the following general formula (2) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (1) ▲ There are mathematical formulas, chemical formulas, tables, etc.▼(2) (However, in general formulas (1) and (2), R_1 to R_4 represent hydrogen, lower alkyl group, lower alkoxy group, or halogen, and at least one of these represents is an alkoxy group, and X represents a halogen) to react with the following general formula (3
) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(3) (However, in the formula, R_1 to R_4 are the general formulas (1) and (
A dinitrobenzanilide derivative represented by formula (2) is produced, and then this dinitrobenzanilide derivative represented by general formula (3) is reduced to obtain the following general formula ▲ mathematical formula, chemical formula, table, etc. Yes▼ (However, R_1 to R_4 in the formula are the above general formulas (1) and (
A method for producing a diaminobenzanilide derivative, which comprises producing a diaminobenzanilide derivative represented by (same as in case 2). (2) 2-alkoxy-4 represented by the following structural formula (4)
- Nitroaniline and 4-nitrobenzoic acid halide represented by the following general formula (5) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (4) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (5) (However, general (In formulas (4) and (5), R_5 is an alkyl group and X represents a halogen) to form the following structural formula (6) 2'-alkoxy-4,4'-dinitrobenzanilide represented by the formula (R_5 is the same as in general formula (4)) is produced, and then this 2'-methoxy-4
, 4'-dinitrobenzanilide is reduced to produce 2-alkoxy represented by the following structural formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, R_5 in the formula is the same as in the case of general formula (4)) A method for producing a diaminobenzanilide derivative according to claim 1, wherein -4,4'-diaminobenzanilide is produced.