JP2000264872A - Synthesis of aminobenzenesulfonic acid derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To simply synthesize an aminobenzenesulfonic acid derivative in high yield that is useful as a synthetic intermediate for dyes, medicines, agrochemicals, an organic synthetic intermediate and a synthetic intermediate for an image-forming compound by allowing a specific aniline derivative to react with sulfamic acid. SOLUTION: An aniline derivative of formula I or II (R1 and R2 are each H, an alkyl; R11 to R13, R21 to R23 are each H, a substituent) is allowed to react with sulfamic acid, preferably in an amount of 1-2 moles per mole of the aniline in the absence or presence of solvent under stirring with heat to prepare the objective compounds of formula III or IV (X is an electron attracting group; M is H, a monovalent or divalent metal atom, a quaternary ammonium salt) corresponding to formula I or II. In a preferred embodiment, sulfolane, alcohol or the like is used as a reaction solvent, while the reaction temperature is 80-170 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for synthesizing an aminobenzenesulfonic acid derivative having an electron-withdrawing group using sulfamic acid. The aminobenzenesulfonic acid derivative having an electron-withdrawing group obtained by the present invention is important as a raw material for dyes, pharmaceuticals, agricultural chemicals, organic synthesis intermediates, and the like. Particularly, it is useful as an intermediate for synthesizing an image forming compound used in a color photographic light-sensitive material by a diffusion transfer method. Further, it is also useful as a starting material of 3-amino-2,1-benzoisothiazole-5-sulfonic acid used as a synthetic intermediate of an image forming compound.

[0002]

2. Description of the Related Art However, at present, an effective method for synthesizing a derivative of aminobenzenesulfonic acid having an electron-withdrawing group has not been known so far. For example, Japanese Unexamined Patent Publication (Kokai) No. 2-193959 describes a part of a derivative of aminobenzenesulfonic acid having an electron-withdrawing group, but does not describe a method for synthesizing these compounds at all. Under the circumstances described above, there has been a demand for a synthesis method capable of easily obtaining a sulfonic acid derivative of aniline having an electron-withdrawing group at the ortho or para position in a high yield.

[0003]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a method for synthesizing a desired derivative of aminobenzenesulfonic acid having an electron-withdrawing group in a high yield and simply.

[0004]

Means for Solving the Problems The present inventors have made intensive studies and as a result have achieved the above object. That is, the aniline derivative represented by the following general formula (1) or (2) is reacted with sulfamic acid, and the aminobenzene of the general formula (3) or (4) corresponding to the general formula (1) or (2) is reacted. A synthesis method characterized by synthesizing a sulfonic acid derivative.

[0005]

Embedded image

In the formula, R ₁ and R ₂ represent a hydrogen atom or an alkyl group, and R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ each represent a hydrogen atom or a substituent. X represents an electron-withdrawing group. M represents a hydrogen atom, a monovalent or divalent metal atom and a quaternary ammonium salt.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the general formulas (1) to (4), R ₁ or R
₂ represents a hydrogen atom or an alkyl group, wherein the alkyl group is a straight or branched chain having 1 to 12 carbon atoms, or R ₁ and R
₂ may form a ring, and these may have a substituent or may be unsubstituted. Examples of the alkyl group represented by R ₁ or R ₂ include a methyl group, an ethyl group, an isopropyl group, a t-butyl group, and a 1-octyl group. Of these, it is preferred that R ₁ and R _{2 in} the combination of R ₁ and R ₂ are both hydrogen atoms.

R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ , and R
₂₃ may be the same or different and each represents a hydrogen atom or a substituent.

As a substituent, a halogen atom (for example,
A fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group (preferably a linear or branched alkyl group having 1 to 40 carbon atoms, for example, a methyl group, an ethyl group, a propyl group,
An isopropyl group, a butyl group, a t-butyl group, a 1-octyl group, a tridecyl group, etc., a cycloalkyl group (preferably a cycloalkyl group having 3 to 40 carbon atoms, for example, a cyclopropyl group, 1-ethylcyclopropyl Group,
A cyclopentyl group, a cyclohexyl group, a 1-norbornyl group, a 1-adamantyl group, etc., an alkenyl group (preferably an alkenyl group having 2 to 40 carbon atoms, for example, a vinyl group, an allyl group, a 3-buten-1-yl group, etc. ), An aryl group (preferably an aryl group having 6 to 32 carbon atoms, such as a phenyl group, a 1-naphthyl group, and a 2-naphthyl group);

A heterocyclic group (preferably having 5 to 32 carbon atoms);
~ 8-membered heterocyclic group, for example, 2-thienyl group, 4-
Pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-
Pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-2-yl group, etc., cyano group, silyl group (preferably having 8 carbon atoms)
To 40 silyl groups, for example, a trimethylsilyl group, a triethylsilyl group, a tributylsilyl group, a t-butyldimethylsilyl group, a t-hexyldimethylsilyl group, etc., a carboxyl group, a nitro group, an alkoxy group (preferably having 1 to 40 alkoxy groups, for example, methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy, etc., cycloalkyloxy (preferably carbon A cycloalkyloxy group having 3 to 8 atoms, such as a cyclopentyloxy group and a cyclohexyloxy group, and an aryloxy group (preferably having 6 to 40 carbon atoms).
Aryloxy group, for example, phenoxy group, 2
-Naphthoxy group),

A heterocyclic oxy group (preferably having 1 to 4 carbon atoms)
0, for example, a 1-phenyltetrazole-5-oxy group, a 2-tetrahydropyranyloxy group, a 2-furyloxy group, etc., a silyloxy group (preferably a silyloxy group having 1 to 40 carbon atoms) And
For example, a trimethylsilyloxy group, a t-butyldimethylsilyloxy group, a diphenylmethylsilyloxy group, etc., an acyloxy group (preferably an acyloxy group having 2 to 40 carbon atoms, for example, an acetoxy group, a pivaloyloxy group, a benzoyloxy group, A dodecanoyloxy group or the like), an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 40 carbon atoms, such as an ethoxycarbonyloxy group or a t-butoxycarbonyloxy group), a cycloalkyloxycarbonyloxy group ( It is preferably a cycloalkyloxycarbonyloxy group having 4 to 40 carbon atoms, for example, a cyclohexyloxycarbonyloxy group or the like, an aryloxycarbonyloxy group (preferably having 7 to 4 carbon atoms).
A carbamoyloxy group (preferably a carbamoyloxy group having 1 to 40 carbon atoms, for example, an N, N-dimethylcarbamoyloxy group, an N- Butylcarbamoyloxy group),

A sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 40 carbon atoms;
N, N-diethylsulfamoyloxy group, N-propylsulfamoyloxy group, etc., alkanesulfonyloxy group (preferably alkanesulfonyloxy group having 1 to 40 carbon atoms, for example, methanesulfonyloxy group, hexadecane An arenesulfonyloxy group (preferably an arenesulfonyloxy group having 6 to 40 carbon atoms, such as a benzenesulfonyloxy group), and an acyl group (preferably having 1 carbon atom).
To 40 acyl groups, for example, formyl group, acetyl group, pivaloyl group, benzoyl group, tetradecanoyl group, etc., alkoxycarbonyl group (preferably alkoxycarbonyl group having 2 to 40 carbon atoms, for example, methoxy group) A carbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group and the like, a cycloalkyloxycarbonyl group (preferably a cycloalkyloxycarbonyl group having 4 to 40 carbon atoms, for example, a cyclohexyloxycarbonyl group and the like), an aryloxycarbonyl group ( Preferably an aryloxycarbonyl group having 7 to 40 carbon atoms, such as a phenoxycarbonyl group),

A carbamoyl group (preferably having 1 to 4 carbon atoms)
A carbamoyl group, for example, a carbamoyl group,
N, N-dibutylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N-propylcarbamoyl group, etc., azo group (preferably an azo group having 1 to 40 carbon atoms, such as phenylazo group), alkylthio Group (preferably an alkylthio group having 1 to 40 carbon atoms,
For example, an ethylthio group, an octylthio group and the like, a cycloalkylthio group (preferably a cycloalkylthio group having 3 to 40 carbon atoms, such as a cyclohexylthio group), and an arylthio group (preferably an arylthio group having 6 to 40 carbon atoms) Yes, for example, a phenylthio group),
A heterocyclic thio group (preferably a heterocyclic thio group having 1 to 40 carbon atoms, for example, a 2-benzothiazolylthio group,
Pyridylthio group, 1-phenyltetrazolylthio group, etc.), alkylsulfinyl group (preferably having 1 to carbon atoms)
40 alkylsulfinyl groups, such as a dodecanesulfinyl group),

An arenesulfinyl group (preferably an arenesulfinyl group having 6 to 40 carbon atoms;
A benzenesulfinyl group, an alkanesulfonyl group (preferably an alkanesulfonyl group having 1 to 40 carbon atoms, such as a methanesulfonyl group and an octanesulfonyl group), an arenesulfonyl group (preferably, an arenesulfonyl group having 6 to 40 carbon atoms) A benzenesulfonyl group, a 1-naphthalenesulfonyl group and the like, an alkoxysulfonyl group (preferably having 1 to 1 carbon atoms).
For example, a methoxysulfonyl group, an ethoxysulfonyl group, etc.), a cycloalkyloxysulfonyl group (preferably having 3 to 4 carbon atoms).
0, such as a cyclopropyloxysulfonyl group, an aryloxysulfonyl group (preferably an aryloxysulfonyl group having 6 to 40 carbon atoms, such as a phenoxysulfonyl group and a p-methylphenoxy group. A sulfamoyl group), a sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, for example, a sulfamoyl group,
N, N-dipropylsulfamoyl group, N-ethyl-N
-Dodecylsulfamoyl group), a sulfo group, and a phosphonyl group (preferably a phosphonyl group having 1 to 40 carbon atoms, such as a phenoxyphosphonyl group, an octyloxyphosphonyl group, and a phenylphosphonyl group). .

Among these, a hydrogen atom, a halogen atom,
Alkyl, aryl, and alkoxy groups are preferred, and most preferred is when all of R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ , and R ₂₃ are hydrogen.

In the general formulas (1) to (4), X represents an electron-withdrawing group, and examples of the electron-withdrawing group include sulfo, nitro, cyano, fluoroalkyl, alkylsulfonyl, and arylsulfonyl groups. Represent. The alkylsulfonyl group may have a substituent and may have 12 carbon atoms.
Hereinafter, an alkylsulfonyl group having preferably 6 or less carbon atoms, such as a methanesulfonyl group and a butanesulfonyl group. The arylsulfonyl group may be substituted and may be an arylsulfonyl group having 12 or less carbon atoms, preferably 8 or less carbon atoms, such as a benzenesulfonyl group. Examples of the fluoroalkyl group include a trifluoromethyl group and a heptafluoropropyl group. As the electron-withdrawing group represented by X, a cyano group and a methanesulfonyl group are particularly preferable.

In the general formulas (3) and (4), M represents a hydrogen atom, a monovalent or divalent metal atom and an ammonium salt. Examples of the monovalent or divalent metal atom include a sodium atom, a potassium atom, a calcium atom, a barium atom and the like. Examples of the quaternary ammonium salt include triethylammonium and tetrabutylammonium. Preferred M includes a hydrogen atom, a sodium atom and a potassium atom.

Next, a method for synthesizing the aminobenzenesulfonic acid derivative of the general formula (3) or (4) from the aniline derivative of the general formula (1) or (2) will be described.
By heating the aniline derivative of the general formula (1) or (2) and sulfamic acid without stirring or in the presence of a suitable solvent while stirring, an aminobenzenesulfonic acid derivative of the general formula (3) or (4) is obtained. I can do it. Sulfamic acid is added in a molar ratio to the aniline derivative, preferably 0.8 to 5 times, more preferably 1 to 2 times. Examples of the reaction solvent that can be used include alcohols, acetonitrile, toluene, chlorobenzene, nitrobenzene, dimethylacetamide, dimethylsulfoxide, sulfolane, N-methylpyrrolidone, and the like. Preferred examples of the reaction solvent include sulfolane. Reaction temperature is from room temperature to 200
° C, preferably 80 to 170 ° C.

Tables 1 and 2 show specific examples of the aminobenzenesulfonic acid derivative of the general formula (3) or (4) obtained by the present invention. However, the present invention is not limited by these.

[0020]

[Table 1]

[0021]

[Table 2]

[0022]

EXAMPLES Specific examples of the synthesis of the present invention are shown below, but the present invention is not limited by these examples. Example 1 Synthesis of compound 7 1.2 liters of sulfolane and 2-aminobenzonitrile 8
80 g is charged into a three-necked flask and heated with stirring. While maintaining the internal temperature at 130 to 140 ° C, sulfamic acid 86
8 g are added in portions in about 1 hour (four times), and a post-reaction (meaning that the reaction is continued while stirring while maintaining the above temperature) is performed for 2 hours. Cool the internal temperature to 90 ° C or less, and add water 900
To the mixture, 900 ml of concentrated hydrochloric acid was added at 30 ° C. or lower, and the precipitated crystals were collected by filtration, washed with 1.2 liters of 4N hydrochloric acid and 1 liter of methanol, and washed at 40 ° C. overnight. Blow dry. 1100 g of compound 7 was obtained. Yield 7
4% Melting point 300 ° C. or higher ¹ HNMR (DMSO d6) TMS standard σ = 7.5
(1H, s), σ = 6.7 (3H, broad), σ =
6.75 (1H, d) Elemental analysis; (actual) C42.13 H3.30 N13.98 (calculated) C42.42 H3.05 N14.13

Example 2 Synthesis of Compound 2 150 ml of sulfolane and 153 g of 4-chloro-2-methanesulfonylaniline were charged into a three-necked flask and heated with stirring. While maintaining the internal temperature at 140 to 150 ° C., 87 g of sulfamic acid was added in portions over about 1 hour (4
Times) and post-reaction is carried out for 3 hours. Cool the internal temperature to 90 ° C or less,
120 ml of water and 150 ml of ethyl acetate were added, and 30
At 90 ° C or lower, 90 ml of concentrated hydrochloric acid was added, and the precipitated crystals were collected by filtration.
The mixture was washed with 150 ml of hydrochloric acid and 100 ml of methanol, and dried by blowing at 40 ° C. overnight. 170 g of compound 2 was obtained. Yield: 80% Melting point: 300 ° C. or higher Elemental analysis value: (actual value) C29.16 H2.80 N4.71 (calculated value) C29.42 H2.82 N4.90

Example 3 Synthesis of compound 24 1.2 liters of sulfolane and 4-aminobenzonitrile 8
80 g is charged into a three-necked flask and heated with stirring. While maintaining the internal temperature at 130 to 140 ° C, sulfamic acid 86
8 g are added in portions in about 1 hour (four times) and the post-reaction is carried out for 2 hours. The internal temperature was cooled to 90 ° C. or lower, 900 ml of water and 1.2 liter of ethyl acetate were added, and 900 ml of concentrated hydrochloric acid was added thereto at 30 ° C. or lower. The precipitated crystals were collected by filtration, and 1.2 liter of 4N hydrochloric acid and 1 liter of methanol were added. And washed with air at 40 ° C. overnight. 1000 g of compound 7 was obtained. Yield: 67% Melting point: 300 ° C. or higher Elemental analysis value: (actual value) C42.30 H3.00 N13.99 (calculated value) C42.42 H3.05 N14.13

[0025]

According to the present invention, a derivative of aminobenzenesulfonic acid having an electron-withdrawing group can be obtained simply and in high yield.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 317/36 C07C 317/36 (72) Inventor Takayoshi Kamio 210 Nakanuma, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo Film Co., Ltd. F term (reference) 4H006 AA02 AC61 TA02 TB02 TB04 TB13 TC35

Claims (1)

[Claims] An aniline derivative represented by the following general formula (1) or (2) is reacted with sulfamic acid to obtain a compound represented by the general formula (3) or (4) corresponding to the general formula (1) or (2): A method for synthesizing an aminobenzenesulfonic acid derivative of Embedded image In the formula, R ₁ and R ₂ represent a hydrogen atom or an alkyl group, and R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ , and R ₂₃ each represent a hydrogen atom or a substituent. X represents an electron-withdrawing group. M represents a hydrogen atom, a monovalent or divalent metal atom and a quaternary ammonium salt.