JPS62169754A - Novel benzanilide compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R1-R4 are amino, methoxy, methyl, ethyl, propyl, sulfoxyl, carboxyl, isocyanato, methoxy or OH). EXAMPLE:3,3',5,5'-Tetranitrobenzanilide. USE:A material for semipermeable composite membrane. It has an active layer having high crosslinking density and has excellent durability, heat-resistance and pressure-resistance. An excellent performance can be attained by forming a reverse osmosis membrane with an acid chloride. PREPARATION:The compound of formula I can be produced by reacting dinitroaniline of formula II with dinitrobenzoyl chloride of formula III in anhydrous tetrahydrofuran, dissolving the resultant compound of formula IV in dioxane, adding a Pt/C catalyst to the solution and reacting the components under hydrogen pressure.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention can desalinate and desalinate components of liquid mixtures, especially seawater and can water, and can also desalinate components of liquid mixtures, particularly seawater and can water, and can also A novel material useful as a material for semipermeable composite membranes that can selectively remove or recover pollutants or effective substances contained in sewage, which is the cause of pollution, and ultimately contribute to the closure of wastewater. Relating to benzanilide compounds.

[Prior art] Conventionally, materials for semipermeable membranes used industrially include:
Cellulose acetate (e.g., U.S. Pat. No. 3.133.13)
2 and 3,133,137), aromatic polyamides, polyamide hydrazides (U.S. Pat.
, 567.632), aromatic diamines (JP-A-55-147106), ethylenediamine, piperidine (e.g., JP-A-59-179103, JP-A-59-179188), polyamine ethers (
Japanese Unexamined Patent Publication No. 58-24304) and the like are disclosed.

[Problems to be solved by the invention] Various compounds having reactive amino groups have been studied, but the composite films formed have problems in terms of durability, heat resistance, and pressure resistance. there were. Therefore, in order to obtain a composite membrane having an active layer with a high crosslinking density, there has been a strong desire for the emergence of an aromatic amino compound having a reactive amino group of 3 or more functionalities.

The present invention provides an aromatic amino compound having a specific trifunctional or higher functional reactive amino group, which is useful for obtaining a composite membrane having an active layer with high crosslink density.

[Means for solving problems] In order to achieve the above object, the present invention consists of the following configuration.

"A benzanilide compound represented by the general formula below.

(In the formula, R1, R2, R3, R4 represent an amino group or a methoxy group.) Among R1, R2, R3, and R4 in the benzanilide compound represented by the general formula (A) of the present invention, the amino group can take any number, but is preferably 3 to 4, and particularly preferably 4 from the viewpoint of crosslink density. Substituents other than amine groups include methyl, ethyl, propyl,
Examples include sulfoxyl, carboxyl, isocyanate, methoxy, and hydroxyl groups, but from the viewpoint of hydrophilicity, sulfoxyl, carboxyl, methoxy, and hydroxyl groups are preferable, and from the viewpoint of gold releasability, methoxy group is more preferable. . The position of the substituent can be chosen from any position, but considering reactivity, 3.3', 5.5'
-, 2°, 3,4°, 5-12°, and 3,5.5- are preferred.

The compound of formula (A>) of the present invention is produced, for example, according to the following production method.

First step: In anhydrous tetrahydrofuran, dinitroaniline and dinitropencil chloride are reacted to form the formula (B).
Manufacture the compound.

The second step is to dissolve the compound of formula (B) in dioxane,
Adding a platinum/carbon catalyst and performing hydrogen pressure non-reaction, the formula (A
＞ is produced.

Example 1 ■ 3.3-. Synthesis of 5.5''-tetranitrobenzanilide 3.5-dinitroaniline 2.46C1 was dissolved in dehydrated tetrahydrofuran, and triethylamine 1.76C was dissolved therein.
Added CI. Keep the inside of the reaction vessel in a nitrogen atmosphere, 3.5
A solution of 3.40 g of -dinitrobenzoyl chloride in dehydrated tetrahydrofuran was added dropwise, and after stirring at room temperature for 4 hours, the mixture was further heated under reflux for 4 hours. After separating the precipitate from P, the mother liquor of tetrahydrofuran was distilled off under reduced pressure, methanol was added, and the precipitated powder was dried after separating from P to obtain 3.5IQ of white powder.

■ Analysis results (infrared absorption > 3290.3080, 1660°16
22.1540, 1340rm-1 nuclear magnetism 11j6
(CDCf13.TMS): δ11.85 (S, IH
), 9.55-7.24 (m, 6H) 00m ■ Synthesis of 3.3",5.5'-tetraaminobenzanilide In a pressurized container, 3.3-.5.5'-tetranitro Benzanilide 50.00g, platinum/carbon (5%>5.OO
g and dioxane 500m and hydrogen pressure 4-2ki/
cnf, reacted at 80'C for 3 hours. After cooling, the catalyst was separated and dioxane was distilled off under reduced pressure to obtain a yellow 1/2 powder.
I got g.

■ Analysis results (infrared absorption> 3420.1660.1640~15
90, 1540 cm' (Fig. 1) Nuclear magnetic resonance (DMS)
O-δ6. TMS): δ9゜2'5 (S, 1H),
6.25-5.58 (m, 6H>, 4.80 (
S, 8H>ppm ■ Application example: A composite membrane obtained by applying an aqueous solution of 3.3',5.5-1-tetraaminobenzanilide on a polysulfone support and crosslinking this with a trimesic acid chloride solution. , the salt concentration is 1500 pl) m.

When reverse osmosis performance was evaluated at an evaluation pressure of 15 kg/cot, the salt rejection rate was 98.0%, and the amount of fresh water produced was 0°29.
A performance of m'/m2·day was obtained.

Example 2 (1) Synthesis of 2'',3.4-.5-tetranitrobenzanilide 18.05q of 2,4-dinitroaniline, 12.97G of triethylamine, and 750d of benzene were added and stirred under a nitrogen atmosphere. , 25.0 OCI of 3°5-dinitrobenzoyl chloride was added, and the mixture was then heated under reflux for 6 hours.The reaction solution was filtered hot, and when the mother liquor was cooled, crystals were precipitated, so they were separated.

■ Analysis results (infrared absorption) 3100, 1677.1540-15
10, 1355-1340ctn-' nuclear magnetic resonance (DM
SO-δ6. MS): δ11゜90 (S, 1H),
9.15-7.95 (m, 6+-+ > ppm ■ Synthesis of 2-.3,4-.5-tetra-aminobenzanilide 2" 3.4-.5-tetranitrobenzanilide in a pressurized vessel 3.00 (), 0.18 g of platinum/carbon (5%), and 85 m of dioxane!!, and hydrogen pressure was 3 to 1 kg.
/cut, and the reaction was carried out at 80'C for 10 hours. After cooling, the catalyst was separated and dioxane was distilled off under reduced pressure.
A brown powder was obtained.

■ Analysis results (infrared absorption > 3400.3330, 3210°16
60.1620, 1594.1520c! 'Nuclear magnetic resonance (DMSO-δ6.TMS): δ8°96 (S, 1H
), 6.77-5.82 (m, 6H), 4.83 (
S, 2H>, 4.68 (S, 1)-1>, 4.49
(S, IH) ppm■ Application example A composite membrane obtained by applying an aqueous solution of 2', 3.4', 5-tetraaminobenzanilide to a polysulfone support and crosslinking this with a trimesic acid chloride solution. , salt concentration 1500 pI) m.

When reverse osmosis performance was evaluated at an evaluation pressure of 15 kg/cffl, the salt rejection rate was 93.0% and the amount of water produced was 0°1.
A performance of 8 m'/m2・day was obtained.

Example 3 ■ Synthesis of 2-methoxy-3,5,5-trinitrobenzanilide 16.820 2-amino-4-nitroanisole was dissolved in dehydrated tetrahydrofuran, then 12.14 CI of triethylamine was added, and the mixture was heated under a nitrogen atmosphere. I kept it. Cool the reaction vessel and add 25.0 g of 3.5-dinitrobenzoyl chloride.
00 was added little by little.

After heating under reflux for 1 hour at room temperature and then for 6 hours, the mixture was allowed to cool and the precipitate was separated to obtain white powder 25.7(1).

■ Analysis results Nuclear magnetic resonance (DMSO-δ6.TMS): δ10°65
(S, 1H), 9.13-7.32 (m, 6H>,
4.01 (S, 3H>I)pm 2-methoxy-3
, 5,5-monotriaminobenzanilide In a pressurized vessel, dioxane 300d, 2-methoxy 3.5,5-trinitrobenzanilide 20.
0CI and platinum/carbon (5%>1.0cx) were added, and the hydrogen pressure was kept at 4-2 kg/c/, the temperature was maintained at 80°C, and the reaction was carried out for 2 hours. After cooling, the catalyst was separated, and the dioxane was removed. Distillation under reduced pressure and further drying under reduced pressure yielded a yellow powder 11.7
C] was obtained.

■ Analysis results Nuclear magnetic resonance (DMSO-δ6.TMS): δ10°42
(S, 'IH), 7.49-5.97 (m, 6H)
, 4.91 (3,6H>, 3.78 (3,3H)
I) l) m ■ Application example 2-methoxy-3°5.5” on a polysulfone support
- A composite membrane obtained by applying a triaminobenzanilide aqueous solution and crosslinking it with a trimesic acid chloride solution was prepared at a salt concentration of 150 oppm and an evaluation pressure of 15 kc.
When reverse osmosis performance was evaluated in J/cIIV, the salt rejection rate was 90.0%.

Water generation amount 0.05m! /m2・day.

[Effects of the Invention] The present invention was able to provide a novel aromatic amino compound having a trifunctional or higher functional reactive amino group, which is useful for obtaining a composite membrane having an active layer with a high crosslink density.

In particular, when the novel benzanilide compound of the present invention was made into a reverse osmosis membrane using acid chloride, it could be made to have excellent performance.

[Brief explanation of drawings]

FIG. 1 shows an infrared absorption spectrum of the novel benzanilide compound of the present invention obtained in Example 1 of the present invention.

Claims (4)

[Claims] (1) A benzanilide compound represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1, R_2, R_3, R_4 are amino group, methoxy group, methyl group, ethyl group, propyl group, sulfoxyl group, carboxyl group, isocyanate group, methoxy group) , represents one or more groups selected from hydroxyl groups.) (2) R_1, R_2, R_3, R_4 are amino groups,
The benzanilide compound according to claim (1), characterized in that the benzanilide compound represents one or more groups selected from methoxy groups and methoxy groups. (3) The benzanilide compound according to claim (1), wherein R_1, R_2, R_3, and R_4 are amino groups and have three or more groups. (4) The positions of the substituents of R_1, R_2, R_3, and R_4 are 3,3',5,5'-, 2',3,4',5-,2
',3,5,5'- benzanilide compound according to claim (1).