JPH1135548A - Production of arylsulfonylureid compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound useful as a developer for thermosensitive recording agents in a high yield and in a high purity in simple operations by reacting an arylsulfonamide compound with an aromatic isocyanate compound in specific conditions. SOLUTION: This method for producing an arylsulfonylureid compound of formula III [Ar<1> is an aromatic residue; Ar<2> is a di or tri-valent aromatic residue; (n) is 2, 3], such as 4,4'-bis[N' -(p-toluenesulfonyl) ureido] diphenylmethane, comprises reacting an arylsuolfonamide compound alkali metal of formula I (B is an alkali metal) (e.g. p-toluenesulfonamide sodium salt) with an aromatic isocyanate compound of formula III (e.g. diphenylmethane -4,4' -diisocyanate) in one or more kinds of solvents, such as acetonitrile containing 1-10 wt.%, at 10-50 deg.C and subsequently removing the alkali metal from the obtained product.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an organic compound having two or three specific arylsulfonyluureido groups. More particularly, the present invention relates to a method for producing an arylsulfonylureide compound used as a color developer of a heat-sensitive recording material having excellent oil resistance and plasticizer resistance of a color image.

[0002]

2. Description of the Related Art Thermosensitive recording materials have the advantage that the recording apparatus is inexpensive and easy to maintain, but also has the disadvantage that the color image undergoes fading over time because the color reaction is reversible. ing. This fading phenomenon is accelerated by light exposure or contact with a plasticizer, oil, or the like, and the color image may disappear completely.

The method of producing an arylsulfonylureide compound as a color developer which is effective in improving the discoloration problem, particularly oil resistance and plasticizer resistance, is disclosed in JP-A-5-148220 and JP-A-5-301455. JP-A-6-239
No. 030.

[0004] In Japanese Patent Application Laid-Open No. Hei 5-148220, on the upper right column to the lower left column on page 3, the following (1) or (2) is described as a process for producing 4,4'-bis (p-toluenesulfonylaminocarbonylamino) diphenylmethane. Routes are disclosed. (1) Synthesis from 2 mol of p-toluenesulfonyl isocyanate and 1 mol of 4,4'-diaminodiphenylmethane (2) 2 mol of p-toluenesulfonamide and 4,4 '
-Synthesis from 1 mol of diphenylmethane diisocyanate

As the reaction solvents (1) and (2), the same publication discloses non-aromatic solvents, particularly aliphatic halides, aliphatic nitriles, aliphatic esters, aliphatic ethers and fatty acids. It is stated that group ketones are preferred.

However, in the above method (1), p-toluenesulfonyl isocyanate used as a reaction raw material is difficult to obtain in large quantities and is expensive, so that it is generally not suitable as a raw material on an industrial scale. is there.

On the other hand, in the method (2), the raw materials used are easily available, but the progress of the reaction is very slow.

JP-A-5-301455 discloses that an arylsulfonyl carbamate is reacted with a polyvalent amino compound, and immediately before the end of the reaction, the arylsulfonyl isocyanate is added to the reaction system to react with the unreacted amino compound. A method for producing a compound having an arylsulfonylaminocarbonylamino group is disclosed. In this method, there is a problem in availability of the arylsulfonyl carbamate, and it is difficult to determine the amount of the arylsulfonyl isocyanate added immediately before the completion of the reaction. That is, if the added amount of arylsulfonyl isocyanate is small, the yield will be low, and if it is large, insolubles will be generated and purification will be difficult. Further, arylsulfonyl isocyanate is disadvantageous in terms of cost because it is expensive.

JP-A-6-239030 discloses that an aqueous solution of an alkali metal salt of an arylsulfonamide is prepared by dissolving an arylsulfonamide in an aqueous solution of an alkali metal salt. Two or more arylsulfonyl (thio) ureido groups, which are dissolved in an organic solvent having a water solubility of 50% by weight or more and a mixture of the two solutions is reacted in a homogeneous mixed solvent composed of the organic solvent and water. A method for producing an organic compound having the formula:

However, in this method, it is difficult to produce a high-quality arylsulfonyl (thio) ureido compound in high yield. The reason is that an aqueous solution of an alkali metal salt of an arylsulfonamide is used in the reaction, and the reaction solvent during the reaction contains a relatively large amount of water.
This is probably because a large amount of by-products derived from the decomposition of the aromatic polyiso (thio) cyanate by water are generated.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing an arylsulfonylureide compound by a simple operation in a high yield and a high purity.

[0012]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, completed the present invention.

That is, the present invention provides a compound represented by the general formula (1):

Embedded image (In the formula (1), Ar ¹ represents an aromatic residue, Ar ² represents a divalent or trivalent aromatic residue, and n represents 2 or 3. However, when Ar ² is divalent, n represents And n is 3 when Ar ² is trivalent
It is. In the production of the arylsulfonylureido compound represented by the formula (2),

[0014]

Embedded image (In the formula (2), Ar ¹ has the same meaning as Ar ¹ in the formula (1), and B represents an alkali metal.) An alkali metal salt of an arylsulfonamide compound represented by the general formula (3)

[0015]

Embedded image (In the formula (3), Ar ² and n represent A in the formula (1).
Synonymous with r ² and n. ) Is at least one selected from acetonitrile, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, tetrahydrofuran, ethyl acetate and butyl acetate, and water is 1 to 10
The present invention relates to a method for producing an alkali metal salt of an arylsulfonyl ureide compound, which is reacted in a solvent containing 1% by weight of the obtained arylsulfonylureide compound while maintaining the suspension state throughout the reaction step, and removing the alkali metal in the same solvent.

[0016]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the production method of the present invention will be specifically described.

Ar ¹ in the general formulas (1) and (2)
As the aromatic residue represented by, a benzene-based aromatic residue which may have a substituent can be preferably used. As the residue, a phenyl group and a naphthyl group are particularly preferable.
As the substituent, for example, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, or the like is preferable. Particularly preferred examples of Ar ¹ include a phenyl group, a tolyl group, a chlorophenyl group, and a 2,4-xylyl group.

Specific examples of the arylsulfonamide as a raw material of the alkali metal salt of the arylsulfonamide represented by the general formula (2) include benzenesulfonamide, toluenesulfonamide, chlorobenzenesulfonamide, bromobenzenesulfonamide, Methoxybenzenesulfonamide, ethoxybenzenesulfonamide, ethylbenzenesulfonamide, xylenesulfonamide, diethylbenzenesulfonamide, trimethylbenzenesulfonamide, ethoxytoluenesulfonamide, methoxytoluenesulfonamide, chlorotoluenesulfonamide, chloromethoxybenzenesulfonamide, chloroethoxy Benzenesulfonamide, naphthalenesulfonamide, methylnaphthalenesulfonamide,
Examples thereof include dimethylnaphthalenesulfonamide, methoxynaphthalenesulfonamide, and chloronaphthalenesulfonamide.

The alkali metal represented by B in the general formula (2) includes lithium, sodium, potassium and the like, and sodium and potassium are preferred.

Ar ² in the general formulas (1) and (3)
Examples of the divalent or trivalent aromatic residue represented by (A) include those having a benzene and naphthalene skeleton,
(B) having a biphenyl skeleton, (C) having a diphenylmethane and diphenylethane skeleton, (D)
Those having a phenylenedibenzyl skeleton, (E) having a triphenylmethane skeleton, (F) having a triphenylamine skeleton, (G) having a diphenylketone skeleton, (H) having a diphenylsulfone skeleton, (I) having a diphenyl ether skeleton,
(J) having a diphenyl sulfide skeleton, (K)
Examples thereof include those having a triphenylphosphoric acid skeleton, and for example, those shown below can be used.

[0021]

Embedded image

[0022]

Embedded image

Among the above aromatic groups, (A)
Those having a benzene or naphthalene skeleton and those having a (C) diphenylmethane or diphenylethane skeleton are preferred.

Particularly preferred specific examples of Ar ² include:
1,2-phenylene group, 1,4-phenylene group, 2,4
A -tolylene group, a 2,6-tolylene group, a 1,4-naphthylene group, a 1,5-naphthylene group, a 1,8-naphthylene group,
Examples thereof include a 2,6-naphthylene group, a methylenebis (1,4-phenylene) group, and a 2,2-propylenebis (1,4-phenylene) group.

Specific examples of the aromatic isocyanate compound represented by the general formula (3) include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate,
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,5-tolylene diisocyanate, 3,5-tolylene diisocyanate, 1,3-dimethylbenzene-2,4-diisocyanate , 1,3-dimethylbenzene-4,6-diisocyanate, 1,4-
Dimethylbenzene-2,5-diisocyanate, ethylbenzene-2,4-diisocyanate, naphthalene-
1,4-diisocyanate, naphthalene-1,5-diisocyanate, naphthalene-2,6-diisocyanate, naphthalene-2,7-diisocyanate, biphenyl-2,4′-diisocyanate, biphenyl −4
4'-diisocyanate,

3,3'-dimethylbiphenyl-4,4 '
Diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 2-nitrobiphenyl-4,4'-diisocyanate, diphenylmethane-
4,4'-diisocyanate, 2,2'-dimethyldiphenylmethane-4,4'-diisocyanate, diphenyldimethylmethane-4,4'-diisocyanate, 2,
5,2 ′, 5′-tetramethyldiphenylmethane-4,
4'-diisocyanate, 3,3'-dimethoxydiphenylmethane-4,4'-diisocyanate, 4,4'-
Dimethoxydiphenylmethane-3,3'-diisocyanate, 4,4'-diethoxydiphenylmethane-3,
3'-diisocyanate, 2,2'-dimethyl-5,
5'-dimethoxydiphenylmethane-4,4'-diisocyanate, 3,3'-dichlorodiphenylmethane-
4,4′-diisocyanate, 1,2-diphenylethane-p, p′-diisocyanate, 1,2-diphenylethane-o, p-diisocyanate,

Benzophenone-3,3'-diisocyanate, α, β-diphenylethane-2,4-diisocyanate, toluene-2,4,6-triisocyanate,
1,3,5-trimethylbenzene-2,4,6-triisocyanate, naphthalene-1,3,7-triisocyanate, biphenyl-2,4,4′-triisocyanate, diphenylmethane-2,4 4′-triisocyanate, 3-methyldiphenylmethane-4,6,4′-triisocyanate, p-phenylenedibenzyl-4,
4'-diisocyanate, triphenylmethane-4,
4 ', 4 "-triisocyanate, triphenylamine-4,4', 4" -triisocyanate, 3,6-dimethoxytriphenylamine-4,4 ', 4 "-triisocyanate, tris-4 , 4 ', 4 "-isocyanatophenylphosphate and the like.

Specific examples of the arylsulfonylureido compound represented by the general formula (1) produced by the present invention include 1,3-bis [N '-(p-toluenesulfonyl)
Ureido] benzene, 1,4-bis [N '-(p-toluenesulfonyl) ureido] benzene, 2,4-bis [N'-(p-toluenesulfonyl) ureido] toluene, 2,6-bis [N ' -(P-toluenesulfonyl)
Ureido] toluene, 2,4-bis [N ′-(o-toluenesulfonyl) ureido] toluene, 2,4-bis [N ′-(o-chlorobenzene) ureido] toluene,
2,4-bis [N '-(naphthalene-1-sulfonyl)
Ureido] toluene, 2,4-bis [N '-(benzenesulfonyl) ureido] toluene, 2,5-bis [N'
-(P-toluenesulfonyl) ureido] toluene,
3,5-bis [N '-(p-toluenesulfonyl) ureido] toluene, 1,3-dimethyl-2,4-bis [N'-(p-toluenesulfonyl) ureido] benzene, 1,3-dimethyl- 4,6-bis [N ′-(o-toluenesulfonyl) ureido] benzene, 1,3-dimethyl-2,5-bis [N ′-(p-toluenesulfonyl) ureido] benzene,

2,4-bis [N '-(p-toluenesulfonyl) ureido] ethylbenzene, 4,4'-bis [N'-(p-toluenesulfonyl) ureido] diphenylmethane, 4,4'-bis [N '-(O-Toluenesulfonyl) ureido] diphenylmethane, 4,4'-bis [N'-(p-methoxybenzenesulfonyl) ureido] diphenylmethane, 4,4'-bis [N '-(p-
Chlorobenzenesulfonyl) ureido] diphenylmethane, 4,4'-bis [N '-(p-ethylbenzenesulfonyl) ureido] diphenylmethane, 4,4'-bis [N'-(p-benzenesulfonyl) ureido] diphenylmethane, 4,4 '-Bis [N'-(naphthalene-2
-Sulfonyl) ureido] diphenylmethane, 2,2 ′
-Dimethyl-4,4'-bis [N '-(p-toluenesulfonyl) ureido] diphenylmethane, 2,5
2 ', 5'-tetramethyl-4,4'-bis [N'-
(P-toluenesulfonyl) ureido] diphenylmethane, 3,3′-dimethoxy-4,4′-bis [N′-
(P-toluenesulfonyl) ureido] diphenylmethane,

4,4'-Dimethoxy-3,3'-bis [N '-(p-toluenesulfonyl) ureido] diphenylmethane, 2,2'-dimethyl-5,5'-dimethoxy-4,4'-bis [N '-(o-toluenesulfonyl) ureido] diphenylmethane, 4,4'-bis [N'-(2 ", 4" -dimethylbenzenesulfonyl)
Ureido] diphenylmethane, 4,4'-bis [N'-
(2 ", 4", 6 "-trimethylbenzenesulfonyl)
Ureido] diphenylmethane, 4,4'-bis [N'-
(2 "-ethoxy-4" -methylbenzenesulfonyl)
Ureido] diphenylmethane, 4,4'-bis [N'-
(2 "-methoxy-4" -methylbenzenesulfonyl)
Ureido] diphenylmethane, 4,4'-bis [N'-
(2 "-chloro-4" -methylbenzenesulfonyl) ureido] diphenylmethane, 4,4'-bis [N'-
(2 "-chloro-4" -methoxybenzenesulfonyl)
Ureido] diphenylmethane, 4,4'-bis [N'-
(2 "-chloro-4" -ethoxybenzenesulfonyl)
Ureido] diphenylmethane, 4,4'-bis [N'-
(Naphthalene-2 ″ -sulfonyl) ureido] diphenylmethane, 4,4′-bis [N ′-(naphthalene-1 ″)
-Sulfonyl) ureido] diphenylmethane,

4,4'-bis [N '-(4 "-methylnaphthalene-2" -sulfonyl) ureido] diphenylmethane, 4,4'-bis [N'-(4 "-methoxynaphthalene-2" -sulfonyl) ) Ureido] diphenylmethane, 2,4-bis [N ′-(p-toluenesulfonyl)
Ureido] -α, β-diphenylethane, 3,3′-bis [N ′-(p-toluenesulfonyl) ureido] benzophenone, 2,2′-bis [4 ′, 4 ″-{N′-
(P-toluenesulfonyl) ureido] phenyl] propane, 2,2′-bis {3,3′-dichloro-4 ′,
4 "-[N '-(p-toluenesulfonyl) ureido]
Phenyl dipropane, 1,4-bis [N '-(p-toluenesulfonyl) ureido] naphthalene, 1,5-bis [N'-(o-toluenesulfonyl) ureido] naphthalene, 2,6-bis [N ' -(O-toluenesulfonyl) ureido] naphthalene, 2,7-bis [N '-(o
-Methoxytoluenesulfonyl) ureido] naphthalene, 2,4'-bis [N '-(o-toluenesulfonyl) ureido] diphenyl, 4,4'-bis [N'-
(O-bromobenzenesulfonyl) ureido] diphenyl, 3,3′-dimethyl-4,4′-bis [N ′-(p
-Toluenesulfonyl) ureido] diphenyl,

3,3'-dimethoxy-4,4'-bis [N '-(p-toluenesulfonyl) ureido] diphenyl, 2,4,6-tris [N'-(p-toluenesulfonyl) ureido] toluene 2,4,6-tris [N '-(o-toluenesulfonyl) ureido] benzene, 1,3,7-tris [N'-(benzenesulfonyl) ureido] naphthalene, 2,4,4'-tris [ N ′-(p-toluenesulfonyl) ureido] diphenylmethane, 4,4 ′, 4 ″ -tris [N ′-(p-toluenesulfonyl) ureido] triphenylmethane,
4,4 ', 4 "-tris [N'-(p-toluenesulfonyl) ureido] triphenylamine, 3,6-dimethoxy-4,4 ', 4" -tris [N'-(p-toluenesulfonyl) Ureido] triphenylamine, 4,
4 ', 4 "-tris [N'-(p-toluenesulfonyl) ureido] triphosphate and the like.

In the production method of the present invention, an alkali metal salt of an arylsulfonamide compound of the above general formula (2) which is not in an aqueous solution state and an aromatic isocyanate compound of the above general formula (3) are mixed with acetonitrile, Reaction in a solvent containing at least one selected from acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, tetrahydrofuran, ethyl acetate and butyl acetate, and containing 1 to 10% by weight of water (hereinafter referred to as the aqueous solvent). The reaction is carried out while maintaining the suspension throughout the process to produce an alkali metal salt of an arylsulfonylureido compound represented by the following formula (1 ′).

[0034]

Embedded image (In the formula, Ar ¹ , Ar ² , and n have the same meanings as those in the general formula (1).)

The arylsulfonylureide compound can be obtained in high purity and high yield by removing the alkali metal from the alkali metal salt of the arylsulfonylureide compound formed above using a mineral acid as an inorganic salt.

The molar ratio of the alkali metal salt of the arylsulfonamide compound of the general formula (2) to the aromatic isocyanate compound of the general formula (3) is such that when n = 2 in the general formula (3), (2): General formula (3) = 1.8: 1
To 2.4: 1, more preferably 2: 1 to 2.2: 1. Further, when n = 3, it is preferable that general formula (2): general formula (3) = 2.7: 1 to 3.6: 1, and 3: 1 to 3: 1.
3.3: 1 is more preferred.

The amount of the water-containing solvent used is 1 to 20 times, more preferably 3 to 10 times the weight of the alkali metal salt of the arylsulfonamide compound of the general formula (2). If the amount used is less than 1 weight, stirring is difficult,
If the weight is more than 20 times the weight, the suspension may not be maintained and may be in a dissolved state.

In the method of the present invention, an aromatic isocyanate compound of the general formula (3) is added to an alkali metal salt of an arylsulfonamide compound of the general formula (2) suspended in the present water-containing solvent. It is more preferable because the amount of by-products is small.

In the production method of the present invention, the dispersion medium of the alkali metal salt of the arylsulfonamide compound of the general formula (2) is a reaction solvent which is a specific organic solvent such as acetonitrile having a low water content. The solubility of the alkali metal salt of the arylsulfonamide compound of the formula (2) is low, and the suspension can be maintained throughout the reaction process.

The method of adding the aromatic isocyanate compound of the general formula (3) to a suspension of the alkali metal salt of the arylsulfonamide compound of the general formula (2) and the aqueous solvent is as follows.
Powder or liquid may be added little by little, or may be added as a solution dissolved in a solvent.

When added in the form of a solution, a solvent similar to the present water-containing solvent but containing substantially no water, that is, acetonitrile, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, tetrahydrofuran, ethyl acetate and butyl acetate is used. It is desirable to add a solution obtained by dissolving the aromatic isocyanate compound of the general formula (3) in at least one selected solvent and containing substantially no water.

In the present invention, the term “suspended state” refers to a heterogeneous state in which at least a part of the reaction raw material or product is not completely dissolved from the beginning of the reaction to the end of the reaction, and preferably the reaction raw material or the product is Is dispersed without dissolving in a solvent. In the case of a uniform state, the amount of by-products tends to increase.

In the present invention, the alkali metal salt of the arylsulfonamide compound of the general formula (2) is not used as an aqueous solution, and the amount of water in the water-containing solvent is small. And does not form a uniform state.

When the aromatic isocyanate compound of the general formula (3) is added to the suspension of the alkali metal salt of the arylsulfonamide compound of the general formula (2), the temperature of the reaction solution is as follows:
Depending on the reactivity of the aromatic isocyanate compound,
The temperature is preferably from 0 to 70C, more preferably from 10 to 50C.

The addition time of the aromatic isocyanate compound of the formula (3) to the suspension of the alkali metal salt of the arylsulfonamide compound of the formula (2) is from 30 minutes to 20 minutes.
Time is preferred, and 1 hour to 8 hours is more preferred.

The reaction time is preferably 30 minutes to 2 hours, and the reaction temperature at this time is preferably the same as the temperature of the reaction solution at the time of addition. The reaction is completed within 2 hours after the addition, but if the temperature of the reaction solution is kept at 30 ° C. or lower, there is no particular adverse effect even if stirring is continued for 2 hours or more.

In the present invention, the water content of the present water-containing solvent is 1
10 to 10% by weight, more preferably 1 to 5% by weight. When the water content of the present water-containing solvent is lower than 1% by weight, the reaction between the compound of the general formula (2) and the compound of the general formula (3) becomes slow or hardly proceeds.

When the water content of the present water-containing solvent is higher than 10% by weight, the aromatic isocyanate of the general formula (3) is liable to be hydrolyzed, and a compound such as a compound in which aromatic isocyanates are urea-bonded. A large amount of by-products are generated, and the purity of the target arylsulfonyluride compound is reduced.

The aromatic isocyanate compound of the general formula (3) is added to the suspension of the alkali metal salt of the arylsulfonamide compound of the general formula (2) in the present aqueous solvent, although the aromatic isocyanate compound of the same type as the present aqueous solvent is substantially used. When a solution dissolved in a solvent containing no water is added to the suspension, the water content of the suspension decreases with the addition of the solution.
It is preferably 0% or less and 1% or more after completion of the addition.

The alkali metal salt of an arylsulfonamide of the general formula (2) is, for example, a compound of the general formula (2 ′)

Embedded image (Wherein, Ar ¹ is represented by the general formula (1) have the same meanings as Ar ¹ in.) Arylsulfonamide compound dispersed in toluene, to which an alkaline aqueous solution of the aryl sulfonamide compounds with an equimolar amount added, The reaction can be carried out by azeotropic dehydration with toluene by heating to obtain a suspension in toluene. By removing toluene by filtration or distillation, an alkali metal salt of arylsulfonamide containing no water can be easily obtained.

As the alkali metal, lithium, sodium, potassium, etc., as the alkali metal hydride, lithium hydride, sodium hydride, potassium hydride, etc., and as the alkali hydroxide, lithium hydroxide,
Sodium hydroxide, potassium hydroxide and the like,
Particularly, sodium hydroxide and potassium hydroxide can be preferably used.

The alkali metal salt of the arylsulfonyl ureide compound of the general formula (1 ') is preferably reacted with an acid to remove the alkali metal, whereby an arylsulfonyl ureide compound can be obtained.

As the acid, mineral acids such as hydrochloric acid, sulfuric acid and nitric acid are preferable.

The acid to be added may be a dilute acid or a concentrated acid.
Is preferably added until the pH is in the range of 5 to 7, and more preferably until the pH is in the range of 6 to 7.

As the solvent used in the step of desorbing the alkali metal, the present water-containing solvent can be used as it is, or another solvent, for example, an ether solvent such as diethyl ether or diisopropyl ether can be used. In addition, the present hydrated solvent or ether solvent is
It can be used by mixing with water of up to 5 times the weight.

The arylsulfonyl ureido compound of the general formula (1) obtained by elimination of an alkali metal can be obtained in high purity by removing simultaneously formed inorganic salts by washing with water and drying.

In the present invention, a step of reacting an alkali metal salt of an arylsulfonamide compound of the general formula (2) with an aromatic isocyanate compound of the general formula (3); Through the step of desorbing the alkali metal from the metal salt, the reaction can be carried out using the same kind of solvent and with good volumetric efficiency, so that the operation is easy and the production cost is advantageous.

[0058]

The present invention will be described more specifically with reference to the following examples.

Example 1 19.3 g of sodium salt of p-toluenesulfonamide was dispersed in 61.4 g of acetonitrile containing 4.7% by weight of water, and diphenylmethane-4,4'-diisocyanate was added to the dispersion. Nart 12.5
g in 30 g of acetonitrile was added to 23-27.
It was added dropwise at 4 ° C. for 4 hours. The water content of the reaction solvent at the end of the dropwise addition was 3.17% by weight. After dropping,
The mixture was stirred at the same temperature for 1 hour. The reaction mixture was cooled to 15 ° C and 5.0 g of 98% sulfuric acid was added dropwise at 15-20 ° C over 10 minutes. After stirring at the same temperature for 2 hours, the precipitate was separated by filtration and 5
Washed four times with 0 ml of water. After drying, 26.3 white powder
g (yield 90%) was obtained.

According to NMR, elemental analysis and infrared absorption spectrum, this was the target 4,4′-bis [N ′-(p-
Toluenesulfonyl) ureido] diphenylmethane was identified. The purity by high performance liquid chromatography was 98.1%.

(Examples 2 to 6) Instead of the sodium salt of p-toluenesulfonamide in Example 1, an alkali metal salt of an arylsulfonamide compound shown in Table 1 was used, and 3.17% by weight of water was used as a reaction solvent. Using the same operation and analysis method as in Example 1 except that the reaction solvent shown in Table 1 was used instead of acetonitrile, an arylsulfonylureide compound was obtained and confirmed to be the target compound. Table 1 shows the results.

(Examples 7 to 9) Instead of 3.17% by weight aqueous acetonitrile, which is the reaction solvent in Example 1, 3.17% by weight aqueous terahydrofuran (Example 7), 3.17% by weight aqueous Ethyl acetate (Example 8),
Even if 3.17% by weight of water-containing butyl acetate (Example 9) is used, the target product can be produced in the same manner.

Comparative Examples 1 and 2 Instead of the sodium salt of p-toluenesulfonamide in Example 1, an alkali metal salt of an arylsulfonamide compound shown in Table 1 was used, and 3.17% by weight of water was used as a reaction solvent. Using the same operation and analysis method as in Example 1 except that the reaction solvent shown in Table 1 was used instead of acetonitrile, an arylsulfonylureide compound was obtained and confirmed to be the target compound. Table 1 shows the results.

In the case of Comparative Example 1, the reaction almost stopped proceeding from about 2 hours after the dropping of the acetonitrile solution of diphenylmethane-4,4'-diisocyanate, and the operation was stopped.

Comparative Example 3 40 g of water and 4.8 g of caustic soda were added to 17.1 g of p-toluenesulfonamide and dissolved by stirring. 50 ml of acetone was added to this solution for dilution, and 12.5 g of diphenylmethane-4,4′-diisocyanate dissolved in 150 ml of acetone was added.
Dropped in time. After the dropping, the raw material mixture in a uniform state was gently refluxed for 2 hours. After distilling off acetone, 15
0 g of water was added and insolubles were removed by filtration. 5 filtrates
% Hydrochloric acid was added to adjust the pH to 2. The precipitate is collected by filtration and dried,
14.0 g (yield 48%) of a pale yellow powder was obtained.

The melting point was 120-130 ° C. The purity by high performance liquid chromatography was 70.6%.

[0067]

[Table 1]

[0068]

According to the method of the present invention, an arylsulfonylureide compound can be obtained in a high yield and a high purity by a simple operation.

Continued on the front page (72) Inventor Toshihiko Kawabata 1-43, Yugecho Minami, Yao-shi, Osaka Yamamoto Kasei Co., Ltd.

Claims (3)

[Claims] 1. A compound of the general formula (1) (In the formula (1), Ar ¹ represents an aromatic residue, Ar ² represents a divalent or trivalent aromatic residue, and n represents 2 or 3. However, when Ar ² is divalent, n represents And n is 3 when Ar ² is trivalent
It is. In the production of the arylsulfonylureido compound represented by the general formula (2), (In the formula (2), Ar ¹ has the same meaning as Ar ¹ in the formula (1), and B represents an alkali metal.) An alkali metal salt of an arylsulfonamide compound represented by the general formula (3) Embedded image (In the formula (3), Ar ² and n represent A in the formula (1).
Synonymous with r ² and n. ) Is at least one selected from acetonitrile, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, tetrahydrofuran, ethyl acetate and butyl acetate, and water is 1 to 10
Wherein the reaction is carried out while maintaining a suspension state in a solvent containing by weight in a reaction step, and an alkali metal is eliminated from the obtained alkali metal salt of an arylsulfonylureido compound, characterized by the general formula (1) A method for producing an arylsulfonyluureide compound. 2. The method according to claim 1, wherein the reaction is carried out in a solvent containing 1 to 5% by weight of water. 3. Ar ¹ in the general formulas (1), (2) and (3) has, as a substituent, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a halogen atom. A phenyl group or a naphthyl group;
r ² is a 1,2-phenylene group, a 1,4-phenylene group,
2,4-tolylene group, 2,6-tolylene group, 1,4-naphthylene group, 1,5-naphthylene group, 1,8-naphthylene group, 2,6-naphthylene group, methylenebis (1,4-
Phenylene) group or 2,2-propylenebis (1,4
The method according to claim 1, wherein the compound is a (phenylene) group, B is sodium or potassium, and n is 2. 4.