JPH08268978A - Production of n,n-di-substituted-p-phenylenediamine derivative - Google Patents

Abstract

PURPOSE: To obtain an N,N-di-substituted-p-phenylenediamine derivative of high quality and high purity in high yield by allowing an N,N-di-substituted- nitrosoaniline to react with hydrazine using inexpensive activated carbon and an iron compound as catalysts. CONSTITUTION: (A) An N,N-disubstituted-4-nitrosoaniline of formula I (R<1> is a 1-6C alkyl, -OH, a lower alkoxy, a 1-6C alkyl substituted with sulfo or alkylsulfonamide; R<3> is H, a 1-4C alkyl) us allowed to react with (B) hydrazine in water or a solvent such as an alcohol of 1-6 carbon atoms in the presence of (C) activated carbon and (D) an iron compound, preferably a compound of ferrous or ferric ion to give (E) an N,N-di-substituted-p-phenylenediamine or its acid adduct. The amount of the activated carbon is preferably 0.02-2.0 times the component (A), while the iron compound is 0.001-0.2 time the component (A).

Description

Detailed Description of the Invention

[0001]

The present invention relates to N, N-disubstituted-P-
The present invention relates to a method for producing a phenylenediamine derivative.

[0002]

The N, N-disubstituted-P-phenylenediamine derivative obtained by the present invention is an important compound as a color developing agent for color photography, and is widely used at present.

A method for producing N, N-disubstituted-P-phenylenediamine is described in, for example, J. A. C. S. 73 3100-3
125 (1951) and Japanese Patent Application Laid-Open No. 5-117207, a method of reducing N, N-disubstituted-4-nitrosoanilines with hydrogen using a catalyst is known. However, these methods require special reaction equipment due to the high pressure, and expensive catalysts must be used.

Further, Japanese Patent Application Laid-Open No. 50-129526 proposes a method of reducing N, N-disubstituted-4-nitrosoanilines with hydrazine without using a catalyst. However, in this method, the reaction is performed under violent conditions because there is no catalyst, so many undesirable by-products are produced, the yield is low, and its economic value is low. By the way, the purity of the reaction product obtained as a result (shown as Comparative Example 1) of the invention disclosed in JP-A-50-129526 was not satisfactory.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to catalyze common inexpensive materials without the need for special reactors that are pressure resistant and without the use of expensive catalysts such as precious metals. As a result, a method for producing an N, N-disubstituted-P-phenylenediamine derivative with high quality (high purity without recrystallization) and high yield is provided.

[0006]

The inventor of the present invention has reached the present invention as a result of intensive studies to solve the above-mentioned problems. That is, the present invention provides the formula (1)

Embedded image (In the formula, R ¹ represents an alkyl group having ¹ to 6 carbon atoms, R ² has an alkyl group having 1 to 6 carbon atoms or 1 to 6 carbon atoms, an OH group, An alkyl group substituted with a lower alkoxy group, a sulfo group or an alkylsulfonamido group, wherein R ³ is hydrogen or 1
A N, N-disubstituted-4-nitrosoaniline represented by an alkyl group having 4 to 4 carbon atoms) is reacted with hydrazine in the presence of activated carbon and an iron compound in water or a solvent to give a compound of the formula ( 2)

[Chemical 4] (In the formula, R ¹ represents an alkyl group having ¹ to 6 carbon atoms, R ² has an alkyl group having 1 to 6 carbon atoms or 1 to 6 carbon atoms, an OH group, An alkyl group substituted with a lower alkoxy group, a sulfo group or an alkylsulfonamido group, wherein R ³ is hydrogen or 1
To an alkyl group having 4 carbon atoms), N, N-disubstituted-P-phenylenediamines or acid addition salts thereof.

Examples of the compound of the formula (1) used in the present invention include N, N-dimethyl-4-nitrosoaniline, N, N-diethyl-4-nitrosoaniline, N-ethyl-N-hydroxyethyl- 4-nitrosoaniline,
N, N-diethyl-3-methyl-4-nitrosoaniline, N-ethyl-N-methanesulfonylaminoethyl-
3-methyl-4-nitrosoaniline, N-ethyl-N-
Methoxyethyl-3-methyl-4-nitrosoaniline and the like can be mentioned. Compounds of formula (1) are described, for example, in J. A.
C. S. It can also be obtained by the method described in 73 3100 to 3125 (1951).

The activated carbon used in the present invention is N,
The N-disubstituted-4-nitrosoanilines may be used in a large amount, preferably 0.01 to 2.0 times (weight ratio), more preferably 0.05 to 0.5 times. use.

The iron compound in the present invention may be an ionic iron compound of Fe ²⁺ , Fe ³⁺ which is usually obtained. Specific examples include ferrous chlorides such as ferrous chloride and ferrous bromide, ferric halides such as ferric chloride and ferric bromide, and ferrous sulfate. Inorganic acid salts such as ferric sulfates such as ferric sulfate and organic acid salts such as iron acetates and iron formates are used.

The iron compound is preferably 0.001 to 0.2 times the amount (weight ratio) of the N, N-disubstituted-4-nitrosoanilines, more preferably 0.005 to 0.05.
Use in double the amount.

The reaction is carried out in water and / or an organic solvent, preferably methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, butyl alcohols, pentyl alcohols, hexyl alcohols, methyl cellosolve and the like. Alcohols having 1 to 6 carbon atoms such as alkoxy alcohols are used.

As the hydrazine to be used, an aqueous hydrazine hydrate solution is usually used, but a hydrazine salt such as hydrazine hydrate, hydrazine or hydrazine sulfate may be used. The amount of hydrazine to be used may be a theoretical amount or a slight excess of the theoretical amount.

The reaction temperature is 0 to 100 ° C., preferably 3
It is 0 to 60 ° C. The reaction time is 10 minutes to 12 hours.

After completion of the reaction, activated carbon and iron compounds may be filtered, water and / or solvent may be distilled off, and free N, N-disubstituted-P-phenylenediamines may be taken out.
Alternatively, after filtering the activated carbon and the iron compound, acids such as hydrochloric acid or sulfuric acid may be added to the filtrate and taken out as an acid addition salt thereof.

[0015]

EXAMPLES The present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1 In a 300 ml four-necked flask, 100 ml of isopropyl alcohol, 5.0 g of activated carbon (containing 50% water), 0.5 g of ferrous chloride tetrahydrate and an aqueous solution of 80% hydrazine monohydrate 18 0.8 g was added, and N-ethyl-N-methanesulfonylaminoethyl-3-methyl- was added at 35 to 45 ° C.
4-nitrosoaniline [R ¹ : C ₂ H ₅ and R ^{2 in the} formula (1):
C ₂ H ₄ NHSO ₂ CH ₃ , R ³ : CH ₃ ] 71.3 g (HP
LC purity 98.5%) was added in 1 hour. 40-50
After stirring at ℃ for 2 hours, activated carbon and iron compounds were filtered, washed with 50 ml of isopropyl alcohol, and the filtrate was 70%.
Sulfuric acid 71.0 g was added dropwise, and the precipitated crystals were filtered and dried to give 4- (N-ethyl-N-methanesulfonylaminoethyl) -2-methyl-P-phenylenediamine sesquisulfate monohydrate 107.4 g. Got Yield 98
%. HPLC purity 99.8%.

Comparative Example 1 [Based on Example 4 of JP-A-50-129526] N-ethyl-N-methanesulfonylaminoethyl-3-
30 g of water was added to 23.0 g of methyl-4-nitrosoaniline, and 8.2 g of 80% hydrazine hydrate was added at 80 to 90 ° C.
Dropped over time. After reacting at the same temperature for 2 hours, the reaction product was analyzed by HPLC. HPLC purity 91.4%.

[0018] Example 2 N, N-diethyl-3-methyl-4-nitroso aniline ^{_{(R 1: C 2 H 5}} , R 2: C 2 H 5, R 3: CH 3) 48.0g
In the same manner as in Example 1 except that was used, 68.2 g of 4- (N, N-diethyl) -2-methyl-P-phenylenediamine sulfate was obtained. Yield 99%. HPLC purity 99.9%.

Example 3 In a 300 ml four-necked flask, 80 ml of ethanol,
20 ml of water, 10.0 g of activated carbon (containing 50% water), 0.8 g of ferric chloride hexahydrate and 18.8 g of 80% hydrazine monohydrate aqueous solution were added, and N-ethyl-at 35-45 ° C was added. N- hydroxyethyl-3-methyl-4-nitroso aniline ^{_{(R 1: C 2 H 5}} , R 2: C 2 H 4 OH, R 3: C
The H ₃₎ 52.0 g was added in 1 hour. After stirring at 40 to 50 ° C. for 2 hours, the mixture was filtered and concentrated to give 4 (N-ethyl-N-hydroxyethyl) -2-methyl-P-phenylenediamine 48.0 g. Yield 99%. HPLC purity 99.
9%.

Example 4 N-ethyl-N-methoxyethyl-3-methyl-4-nitrosoaniline (R ¹ : C ₂ H ₅ , R ² : C ₂ H ₄ OCH ₃ ,
R ³ : CH ₃ ) 4- (N-ethyl-N-methoxyethyl) -2-as in Example 3 except using 55.5 g.
52.0 g of methyl-P-phenylenediamine was obtained. Yield 100%. HPLC purity 99.9%.

[0021]

According to the present invention, a large amount of N, N-disubstituted-P-phenylenediamine derivative, which is required as a developing agent for color photography, can be obtained without using a special high-pressure reactor.
In addition, without using an expensive catalyst, even if recrystallization is not performed, extremely high purity (99% or more in all of the Examples) is obtained in high yield (98% or more in all Examples). Can be obtained at

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07C 217/08 7419-4H C07C 309/24 309/24 7419-4H 311/35 311/35 C07B 61 / 00 300 // C07B 61/00 300 B01J 23/74 301X

Claims (5)

[Claims] 1. Formula (1): (In the formula, R ¹ represents an alkyl group having ¹ to 6 carbon atoms, R ² has an alkyl group having 1 to 6 carbon atoms or 1 to 6 carbon atoms, an OH group, An alkyl group substituted with a lower alkoxy group, a sulfo group or an alkylsulfonamido group, wherein R ³ is hydrogen or 1
A N, N-disubstituted-4-nitrosoaniline represented by an alkyl group having 4 to 4 carbon atoms) is reacted with hydrazine in the presence of activated carbon and an iron compound in water or a solvent to give a compound of the formula ( 2) [Chemical 2] (In the formula, R ¹ represents an alkyl group having ¹ to 6 carbon atoms, R ² has an alkyl group having 1 to 6 carbon atoms or 1 to 6 carbon atoms, an OH group, An alkyl group substituted with a lower alkoxy group, a sulfo group or an alkylsulfonamido group, wherein R ³ is hydrogen or 1
Is an alkyl group having 4 to 4 carbon atoms), N, N-disubstituted-P-phenylenediamines or an acid addition salt thereof. 2. The amount of the activated carbon used is N, N-di-substituted-
The method for producing the N, N-disubstituted-P-phenylenediamines or acid addition salts thereof according to claim 1, which is 0.01 to 2.0 times the amount of 4-nitrosoanilines. 3. The N, N according to claim 1, wherein the iron compound is an ionic iron compound of Fe ²⁺ or Fe ^3+.
-A method for producing di-substituted-P-phenylenediamines or acid addition salts thereof. 4. The amount of the iron compound used is 0.001 to 0.2 with respect to N, N-disubstituted-4-nitrosoanilines.
The method for producing N, N-disubstituted-P-phenylenediamines or acid addition salts thereof according to claim 1, 2 or 3, which is a double amount. 5. The N, N-disubstituted-P-phenylenediamines or acid addition thereof according to claim 1, 2, 3 or 4, wherein the solvent used is an alcohol having 1 to 6 carbon atoms. Method for producing salt.