JPS58144366A - Preparation of 3,3'-diaminodiphenylsulfone - Google Patents

Abstract

PURPOSE:To prepare the titled compound useful as a raw material of heat- resistant polyamide or polyimide resin, etc., economically, in high purity and yield, by reacting a diphenylsulfone compound in the presence of a reduction catalyst and a dehydrohalogenation agent. CONSTITUTION:The diphenylsulfone compound of formula (X and Y are same or different halogen) is dissolved or dispersed in a solvent such as methanol, dioxane, benzene, etc., and a reduction catalyst such as palladium, nickel, platinum, rhodium, copper, etc. is added thereto. Hydrogen is introduced into the system under stirring at 20-200 deg.C, preferably 20-100 deg.C to reduce the nitro group, and then a dehydro-halogenation agent (e.g. potassium carbonate, sodium hydroxide, ammonia, etc.) is added to the reaction mixture to effect the dehydrohalogenation and obtain the objective material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention comprises 5. The present invention relates to a novel method for producing '5'-diaminodiphenylsulfone. More specifically, the general formula (1
) A diphenylsulfone compound represented by the formula % (in the formula, X and Y represent the same or different halogen atoms) is catalytically reduced and dehalogenated in the presence of a reduction catalyst and a dehydrohalogenation agent. The present invention relates to a method for producing 3,3'-diaminodiphenylsulfone.

3.3'-Diaminodiphenylsulfone is useful as a heat-resistant polymer monomer, a pharmaceutical, a dye intermediate, etc., and is an important substance that is particularly a raw material for heat-resistant polyamides and polyimide resins.

3.3'-diaminodiphenylsulfone has conventionally been used in 6.
A method for producing 5'-dinitrodiphenyl sulfone by reducing it is known (N, P, □Jk, tt et al.

$, maA-LrIneiOmuhe, 4j(1) 1
55 (1976), Wang 61 et al., JP-A-56-2515
No. 0, N, R, A, yin α■a et al.

5yrJ, MuaLi Qtnrru, nLGaiLyn
i, 640 (1981), KtsLal, ek et al., 0. )4cJ, 15B, 469: OmA4-6
Mu,, L416955K (1976)).

In this method, the raw material 6,3'-dinitrodiphenylsulfone is produced by nitration of diphenylsulfone (0,A, Ba4JJ-z4).
et al., J.

Q4. y, QJm, 4 262 (1959), J.L.
αaazLz, Bz direction.

Sac, QlL edition, 551456-50 (19
24): OJ-cm.

hlrA14.1-9980) or a method of producing diphenyl sulfide by oxidizing and simultaneously nitrating it with fuming nitric acid [BcLfd6(j, ec, ca et al., c) a
,＞) OJ Isa, ImuJ.

76 113 19 (1946); 0J-aya, AA
afv, 407155 (1946)).

Furthermore, a method in which benzene is isolated as a by-product when nitrated in the presence of sulfuric anhydride [W.

Alama et al. B;, J., WtliAenr.
tz,) Jαd-T4(,J,, 1 3
57-66 (1964); Mu...73
349629 (1970)), and furthermore, there is a method [NQ
2W+:, nt+1+, -ra, Ta, KlvLn,
KL TcALpw1. , i 7 f3-9 (i 9
69); Higai, AAAM,, υ54962yt(
1970)] is known.

However, in the method of producing 3,6'-dinitro diphenyl sulfone from diphenyl sulfide into a diphenyl sulfone compound, the reaction product obtained by nitration is a mixture containing isomers, etc. In order to isolate the sulfone, a large amount of solvent must be used and recrystallization purification must be repeated repeatedly.

For this reason, the yield is drastically reduced, and there are also drawbacks such as the need for complicated steps such as recovery of the solvent used in purification, treatment of the residue, and treatment of the large amount of waste acid used in nitration. be.

On the other hand, by nitration of benzene and sulfonation of nitrobenzene in anhydrous sulfuric acid, 3'
- When dinitrodiphenyl sulfone is obtained, the yield is low and it is not manufactured for its own purpose, so there are supply problems, and furthermore, it is difficult to secure the necessary amount to meet increasing demand. There is.

The present inventors have made extensive studies on a method for producing 5,3'-diaminodiphenylsulfone that does not have the above drawbacks.

As a result, 3,6'-dinitro-4,4'-dihalogenodiphenylsulfone, which can be easily produced by nitration of 4,4'-dihalogenodiphenylsulfone, was used as a raw material for reduction catalyst and denomination/amination. It was discovered that 6,6'-diaminodiphenylsulfone could be produced in high yield by catalytic reduction and de-amination in the presence of a hydrogen agent, and the method of the present invention was completed.

That is, a diphenyl sulfone compound represented by the general formula (1) (in which X and Y are the same or different, representing an amine atom) is prepared in the presence of a reduction catalyst and a deno-hydrogenation agent, catalytic reduction,
This is a method for producing 6,5'-diaminodiphenylsulfone by removing/'%Rogge/conversion.

B,6'-dinitro used in the method of the invention 4.47
It is known that -cyhalogenodiphenylsulfo/ can be produced in high yield by nitrating 4,4'-dino-10chenodiphenylsulfone by selectively introducing a nitro group into the 3-16'-position.

Example: When 4,4'-dichlorodiphenylsulfone is nitrated with a mixed acid, 3,6'-dinitro-4,4'
-Dichlorodiphenyl sulfone is obtained with a yield of 90-97% [Takeya et al., JP-A-52-14744, W.
F, Ha4. t, et al, J, O+g, 0Lerr
L., 4735B (1962)).

On the other hand, the reduction reaction of 5,3'-dinitro 4,4'-dino logenodiphenyl sulfone is known; All original products are 3,6'-diamino-4,4'-di/%
Lochenosyphenyl sulfone [Bd-chile, Zl.

P Lulu Co., KJL, (L 侃罽トd) 45 2704-
10 (1972); (jmu, AAam, 78
83962z (1973), ~V,F.

Haa, et al., J, 04. g, 0LarL,,
27 33B (1962)).

However, the production of 6,5'-diaminodiphenylsulfone from 6,3'-dinitro-4,4'-dihalogenodiphenylsulfone and the production of 6,6'-dinitro-4,
, 4'-dihalogenodiphenylsulfone, there is no known method for reducing nitro groups to amino groups and dehalogenating them.
, 3'-diaminodiphenylsulfone can be produced industrially.

The raw material used in the method of the present invention is 6,3'-dinitro-4,4'-dihalogenodiphenylsulfone represented by the general formula (1), in which X,
The halogen atom represented by Y may be chlorine, fluorine, iodine, or bromine.

For example, 3'-dinitro-4,4'-dichlorodiphenylsulfone, ro, 3'-dinitro-4,4'-cyclomodiphenylsulfone, ro, 6'-dinitro-4,4
'-Cyfluorodiphenylsulfone, 3,3'-dinitro-4,4'-short diphenylsulfone, 3,3'
-dinitro-4-chloro-4'-bromodiphenylsulfone, 6,3'-dinitro-4-chloro-4'-iododiphenylsulfone, and the like. Among these, those in which the halogen is a chlorine atom are industrially advantageously used.

The reduction catalyst used in Akira Kio's method includes metal catalysts commonly used in catalytic reduction, such as nickel,
Palladium, platinum, rhodium, ruthenium, cobalt,
Copper etc. can be used.

Industrially it is preferred to use palladium catalysts. Although these catalysts can be used in the metal state, they are usually used by being attached to the surface of a carrier such as carbon, barium sulfate, silica gel, or alumina, and nickel, cobalt, copper, etc. are used as Raney catalysts. used. The amount of catalyst used is 3,6'-dinitro-4,4'- of the raw material.
0 as a metal for dihalogenodiphenylsulfone
The amount ranges from 0.01 to 10% by weight, and usually from 2 to 8% by weight when used as a metal, and from 0.1 to 5% by weight when attached to a carrier.

Dehydrohalogenation agents used in the process of the invention include alkali metal or alkaline earth metal oxides, hydroxides, carbonates, bicarbonate salts, or ammonia or common organic amines. .

For example, calcium carbonate, sodium hydroxide 1.1 culture magnesium, ammonium bicarbonate, calcium oxide, lithium hydroxide, barium hydroxide, potassium carbonate, potassium hydroxide, ammonia, triethylamine, tri-n-butylamine, triethanolamine, pyridine. and N
-Methylmorpholine and the like. Two or more of these dehydrohalogenating agents may be mixed if necessary. The amount of the dehydrohalogenating agent used is usually 0.5 to 5 times the mole, preferably 2 to 3 times the mole of the raw material 3,6'-dinitro-4,4'-dihalogenodiphenylsulfone. .

The method of the invention typically uses a reaction solvent.

The reaction solvent is not limited as long as it is inert to the reaction (e.g., alcohols such as methanol, ethanol, inglobil alcohol, ethylene glycol, fluoropylene gelyl, etc.). Glycols, ethers, dioxane, tetrahydrofuran, methyl alcohols such as methyl selon, aliphatic hydrocarbons such as hexane, cyclohexane, aromatic primary hydrocarbons such as benzene, toluene, xylene, vinegar, ethyl acetate, etc. , esters such as butyl acetate, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1.1.2-trichloroethane, tetrachloroethane, and N,N-dimethylformamide, dimethylsulfoxide, etc. If the reaction is slow when using a reaction solvent that is immiscible with water, you can add a commonly used phase transfer catalyst such as a quaternary ammonium salt or a quaternary phosphonium salt. It can be sped up.

The amount of solvent used is 3,3'-dinitro-4,4' of the raw material.
- Cyhalogenodiphenyl sulfonna An amount sufficient to suspend or completely dissolve is sufficient and there is no particular limitation, but usually 0.5 to 10 times the weight of the raw material is sufficient.

The reaction temperature is not particularly limited. Generally 20-200
The temperature range is preferably from 20 to 100°C (°C).

Moreover, the reaction pressure is usually 5Qkq/c=4-.

That's about it.

As a general embodiment of the method of the present invention,
A reduction catalyst was added to dinitro-4,4'-dihalogenodiphenylsulfone dissolved or suspended in a solvent, and then hydrogen was introduced at a predetermined temperature under stirring to reduce the nitro group. Either add a post-dehydrohalogenation agent and continue the dehalogenation reaction, or add the dehydrohalogenation agent at the time of addition of the reduction catalyst, and then introduce hydrogen at a predetermined temperature under stirring to reduce the nitro group. Examples include a method in which denomination and amination reactions are performed simultaneously.

In either case, the reaction proceeds smoothly, and the target substance is filtered and filtered.
- Diaminodiphenylsulfone can be produced.

However, the raw material 6,6'-dinitro-4,4
Since the 10-gen atom at the 4-position of '-dihalogenodiphenylsulfone has nucleophilicity, it may cause a side reaction with the dehydrohalogenation agent depending on the conditions, reducing the yield of the target product. Therefore, method (2) is preferable.

The progress of the reaction can be followed by the absorption of a large amount of hydrogen or by thin layer chromatography.

After removing the catalyst and inorganic salts from the reaction solution obtained by the above method by hot extraction or extraction, it is concentrated if necessary to precipitate 6'-diaminodiphenylsulfone as crystals. Alternatively, 3,6'-diaminodiphenylsulfone can be isolated as a hydrochloride by blowing hydrogen chloride gas into the reaction solution from which the catalyst and inorganic salts have been removed.

The method of the present invention enables the production of 6,3'-diaminodiphenylsulfone in high yield and at low cost, without the problems of environmental pollution caused by wastes associated with conventional methods, and in addition, the purity of the isolated product is high. It is suitable as an industrial production method because it has a high yield and does not require complicated purification steps.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 In a closed glass container equipped with a thermometer and a stirrer, 3! l
'l Zietlow 4,4'-dichlorodiphenylsulfone 115,9 (0,3 mol), 5% palladium/activated carbon
Catalyst (Japan Engelhard) 8.5. ! / and 500 ml of dioxane were charged, and hydrogen was introduced while stirring at a temperature of 70 to 80°C.
1 (1.79 mol) of hydrogen was absorbed. Next, 80 g (0.6 mol) of 60% sodium hydroxide aqueous solution was added, and hydrogen was continuously introduced while stirring at a temperature of 70 to 80°C. 14.56 (0,/) 5 mol) was absorbed in 5 hours. did.

At the same temperature, the reaction solution was filtered to remove the catalyst, and when allowed to cool, 6,6'-diaminodiphenylsulfone was precipitated as pale brown crystals. The crystals were separated, washed with 30ml of a 50% dioxane aqueous solution, and then dried.

Yield 66I (Yield 89I) Melting point 170-172°C Recrystallized from ethanol? A pure product of ff1e prism crystal was obtained. Melting point 1725-1700 Elemental analysis CHN S YujuF! -1st shift (9g15B, 0 4.9
1 131 2.9 E11 constant value (eE) 5B, 3 4
,8 11,3 12.5 Examples 2 to 9 Type of raw material 3,3'-dinitro-4,4'-dihalogenodiphenylsulfone, type and amount of catalyst used, type and amount of solvent used, dehalogenation The reaction was carried out in the same manner as in Example 1, except that the hydrogenating agent A4;:Ii, the amount used, the reaction temperature and the pressure were changed as shown in Table 1 to obtain the desired product.

The results are shown in Table-1.

Example 10 In a glass sealed container equipped with a thermometer and a stirrer,
5 s g (o, i mol) of -4,4'-dichlorodiphenylsulfone, 1 g of haladium black catalyst and 200 ml of benzene were charged at a temperature of 6
When hydrogen was introduced with stirring at 5-70°C, 131 (0.58 mol) of hydrogen was absorbed in about 9 hours.

Next, 60% sodium hydroxide aqueous solution 140103 mol)
and 2 g of trioctylmethylammonium chloride 90% water-soluble (Tokyo Kasei Reagent) were added, and hydrogen was subsequently introduced at a temperature of 65 to 70°C with stirring, resulting in 54 (0.22 mol) hydrogen absorbed. The reaction solution was filtered for t'J at the same temperature to remove the catalyst, etc., and then P
M was separated to obtain an organic layer. After the organic layer was dehydrated with magnesium sulfate, dry hydrogen chloride gas was blown into the mixture until it was saturated, and a white precipitate was deposited. The precipitate was separated and washed with 30 Tnl of benzene to obtain 6'-diaminodiphenylsulfo/hydrochloride. Yield 25.5.9 (yield 80
) Recrystallized from 10% hydrated isopropanol to obtain pure white needle crystals. Melting point 262-264°00 Elemental analysis OII N S C4 Calculated value (Archive 44.8 4.4 B, 7 10
,0 22.1 measured value (91; l 44.9 4
．． 6 8,7 10.1 22.2 real, sideways 11 3.3'-dinitro-<, 4'-dichlorodiphenylsulfone 38 g (0.1 mol), magnesium rl chloride 6 g (0.15 mol), 2 g of the 5th stage palladium/alumina catalyst and saaml of 1,2-dichloroethane are charged into an autoclave. Hydrogen was introduced with stirring at a temperature of 50 to 65° C. for 10 hours while the pressure was constantly maintained at 10 k'j/C1-G. After the reaction was completed, the reaction mixture was heated to 70°C and heated for 1 time to remove the catalyst and the like. By leaving it to cool 3
, 3'-diaminodiphenylsulfone was precipitated as light brown crystals. Separate 1 crystal, 10 12-dichloroethane
After washing with mg, it was dried.

Yield 16g (yield 64.5chi) Melting point 171-172°C Patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1) Catalytic reduction of a diphenylsulfone compound represented by general formula (1) (in the formula, x and y represent the same or different halogen atoms) in the presence of a reduction catalyst and a dehydrohalogenation agent. A method for producing 6,3'-diaminodiphenylsulfone, which comprises dehalogenation.