JPH01242558A - Novel 4,6-diiodo-1,3-benzenediamine, its amine derivative and production thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to 4,6-diami2-1.3, which is a monomer of polybenzobisoxazole (hereinafter abbreviated as PBO).
- Intermediates useful in the synthesis of benzenediol dihydrochloride and methods for their production.

[Conventional technology]

Threads and membranes made from liquid crystal dope, which is a polyphosphoric acid solution of PBO, are polymers with high strength and high elastic modulus, as well as excellent heat resistance and chemical resistance, and are extremely useful in industry. Highly useful.

(Special Publication No. 61-501452).

The general structural formula of PBO is shown below.

PBO On the other hand, 4,6-diamitu-1,3-benzenediol dihydrochloride (hereinafter abbreviated as DAOH) and terephthalic acid are used as monomers for synthesizing PBO. Conventionally, D^OH' has been obtained, for example, by the following reaction process. (Ber, Dtsch, Chem,
Ges,.

16, 552 (1883), ) [Problems to be Solved by the Invention] However, in the conventional technology, when resorcinol is nitrated, a trinitro compound is produced, but this can be produced by rapidly heating or applying a strong impact. It has strong explosive properties. The dinitro monomer also had explosive properties and was not desirable for monomer production. In addition, the nitration efficiency was also poor at 30%.

An object of the present invention is to provide a novel compound useful as an intermediate raw material for the above-mentioned monomer DAOH, and a method for producing the same.

[Means for solving problems]

In order to achieve the above object, the novel compound of the present invention comprises 4.
It is 6-sido-1,3-benzenediamine (hereinafter abbreviated as DIBA) and its derivatives, and is as shown in the following formula.

However, in the formula, R is -I+, -COCH3(a)4,
6-Sifudo-1,3-benzenediamine (DIBA)
can be obtained by the following method.

(a) The method for producing DIBA is characterized by reacting 1,3-benzenediamine and iodine in a solution state.

Preferably, a neutral salt is added to a solution of 1,3-benzenediamine and iodine which has been substituted with an inert gas, and the reaction is carried out at 0 to 80°C under an inert gas atmosphere.

More preferably, DIBA can be synthesized in high yield in a short time by performing the above reaction at 10 to 20"C. The inorganic neutral salt used in the present invention includes hydrogen carbonate, carbonate, phosphate, etc. However, more preferred are their sodium salts and potassium salts, such as sodium hydrogen carbonate, sodium carbonate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium carbonate, potassium hydrogen carbonate, potassium phosphate, and phosphoric acid. These are potassium hydrogen and potassium dihydrogen phosphate.These inorganic neutral salts accelerate the reaction by consuming iodine anions, which are byproducts produced in the iodination reaction process, as neutral salts.

Since the DIBA obtained above is easily denatured when left at room temperature, it is stored at 25° C. or lower under an inert gas atmosphere or vacuum.

Furthermore, in order to obtain DIBA more efficiently, it is also possible to use, for example, the electrolytic oxidation method of iodine described in JP-A No. 62-63527.

(1) Since the obtained 4,6-cyfudo-1,3-benzenediamine (DIBA) is easily modified by heat or oxygen in the air, it can be stabilized as an amine derivative. Amine derivatives can be obtained by reacting DIBA with acetic anhydride or acetyl chloride.

Amine derivatives are usually obtained by the methods shown below.

The present invention is characterized by obtaining a diacetylated product of DIBA, which is a new substance, by acetylating the product after the iodination reaction. That is, according to the findings of the present inventors, in the method of obtaining the amine derivative of DIBA by first obtaining the amine derivative of 1,3-diaminobenzene as a starting material and then reacting this derivative with iodine, the iodine The conversion reaction rate is very poor. Therefore, by introducing DIBA obtained after the iodination reaction into an amine derivative, the amine derivative of DIBA can be obtained very efficiently. Moreover, the obtained amine derivative can be recrystallized by a known method.

DIBA-Ac is hydrolyzed, the amino group is deacetylated, and then converted into a hydrochloride to obtain DAQH, which is a monomer of PBO, as shown below.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples. In addition, 4,6-diamitu-1,3-benzenediamine (DIBA) obtained in Example 1 and 4, obtained in Example 2,
The identification results of the diacetylated product of 6-diami2-1,3-benzenediamine (DIBA-Ac) will be shown later.

Example 1 1.3-diaminobenzene 1.0814g (0,01
A 100 mff1 aqueous solution in which 5.0760 g (0.02 mole) of iodine and 7 g of potassium iodide were dissolved in a 100-aqueous solution containing 2 g of sodium bicarbonate and 2 g of sodium bicarbonate was added under stirring in a nitrogen gas stream. The mixture was added dropwise at 20°C over 2 hours. Note that water purged with nitrogen gas was used for the reaction. After that, stirring was continued for another 2 hours, and after the reaction was completed, the reaction product was filtered, and 0.1N sodium thiosulfate aqueous solution 100%
ml to obtain 2.8 g of a brown dry product (containing 80% of the theoretical amount of DIBA). The obtained compound was confirmed to be DIBA. The identification method and its results are shown below after Example 2 together with the identification results of DIBA.Ac.

Example 2 3.6 g of DIBA obtained by the method of Example 1, 5.0 g of acetic anhydride, and 5.0 g of sodium acetate were dissolved in 100-methanol, and after stirring at 50 ° C. for 6 hours under a nitrogen gas atmosphere, It was dried under reduced pressure at 60°C to obtain a dry crude product.

The dried crude product was dissolved in 350 ml of methanol at 60°C, and undissolved matter was filtered and removed. The filtrate was cooled to 10°C, and the crystals were filtered and washed with methanol to give 3.2 g of a gray-brown dry product (DIBA-Ac: 99% of theory).
I got it. The obtained compound was confirmed to be a DIBA compound. The identification method and its results are shown below together with the identification results of old BA.

Table 1 shows the elemental analysis of the novel substance DIBA of the present invention and DIBA-vesicle, and Table 2 shows the molecular weight (mass spectrum).

Table 1 Table 2 Infrared absorption spectra by the KBr method are shown in Figure 1 for DIBA and Figure 2 for DIBA.Ac.

Liquid chromatograph (Toyo Soda HLC), detector UV
(254 nm), column TSKgel, ODS, 80
TM,? Eluent: methanol/water = 7/3. flow 10
．． 5m1m1n, -' When separated at room temperature, DIBA has a detection peak at 9.3 minutes and DrBA-Ac has a detection peak at 5.3 minutes.

The C"-NMR spectrum of DIBA-Ac at 90 MHz in dimethyl sulfoxide (DMSO) is shown in FIG. 3, and the H'-NMR spectrum is shown in FIG.

The C''-NMR spectrum of DrBA-Ac shows the following absorptions, and each absorption is assigned to carbon in the structural formula shown below.

(f) δ+=24.9ppm (a) δ=9
3.6ppm (e)δ=125.3
pp custom (d) δ=140.2 ppm
(c) δ-146,4ppm
(f) δ-rich 168.4 ppm (
b) Furthermore, the H''-NMR spectrum of DIBA.Ac shows the following absorptions, and each absorption is attributed to hydrogen in the structural formula shown below.

+1 1+δ=2
．． 05 ppm (a) δ-7,4
5ppm (c)δ=8.20ppm
(d) δ=9.35 ppm
(b) The absorption seen at 40.8 ppm in FIG. 3 is from the solvent DMSO. Similarly, the absorption seen at 2.5 ppm in Figure 4 is also due to DMS.
It is from O.

Thermal analysis of DIBA-Ac under nitrogen flow (TG,
DTA) is shown in FIG. DIBA-Ac is 265
Shows weight loss due to decomposition at around ℃. Note that the weight loss at 100°C is from water.

〔Effect of the invention〕

In the present invention, a new compound DIBA (!: DIBA
-Ac and a new method for producing them. Moreover, these are useful as intermediate raw materials for Natsuma-DAO-H for synthesizing PBO.

[Brief explanation of the drawing]

FIG. 1 is an infrared absorption spectrum of DIBA. Figure 2 shows the infrared absorption spectrum of old BA/AC. Figure 3 is the C"-NMR spectrum of DIBA-Ac. Figure 4 is the H'-NMR spectrum of DIBA-Ac. Figure 5 is the thermal analysis results of DIBA-AcO. Patent applicant: Asahi Kasei Corporation Co., Ltd. Figure 4 11) prnl Figure 5 TEMP C (Heating 1 Procedural Amendment (Voluntary) December 2, 1985 Director General of the Patent Office Yoshi 1) Moon Yi 1, Indication of Case Patent Application No. 65887 of 1988 2. Title of the invention New 4.6-syodo1.3-benzenediamine and its amine derivatives and their manufacturing method 3. Person making the amendment Relationship to the case: Patent applicant 1-2 Dojimahama, Kita-ku, Osaka-shi, Osaka Prefecture Number 6 (003)
Asahi Kasei Kogyo Co., Ltd. 4, Subject of amendment 5, Contents of amendment (1) Specification, page 4, 8th line from the bottom, ``atmosphere'' is corrected to ``under atmosphere.'' (2) Same, page 6 (first line) and page 7 (first line) (
3) Same, page 6, line 13 from the bottom, “Diacetylated product” is corrected as “Diacetylated product (DI BA-AC) J. (4), same, page 7 (line 15 from the bottom and line 13 from the bottom) )
"Correct 4,6-diamino J to "4,6-siodo." (5) Same, 12th line from the bottom of page 7, “After the results of the draw” was changed to “
The identification results are shown in Table 1, Table 2, and Figures 1 to 5.''

Claims (2)

[Claims] (1) 4,6-diiodo-1,3-benzenediamine and its derivatives of the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ However, in the formula, R_1 is -H, -COCH_3 (2) A solution of 1,3-benzenediamine and iodine or
Method for producing 4,6-diiodo-1,3-benzenediamine, characterized by reacting it with an iodine solution (3) 4,6-diiodo-1,3-benzenediamine obtained in claim (2) and acetic anhydride or acetyl chloride.