JP2001294569A - Para-phenylenediamine derivative salt and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a p-phenylenediamine derivative salt that has high solubility and can inhibit a photography treatment solution from creeping up and a method for producing the same in high yield. SOLUTION: This invention provides solid N-Ethyl-N-[2-(methane-sulfonamide) ethyl]-3-methyl-4-amino]-ethylaniline p-toluenesulfonate salt of >=95% purity and methds for producing the same by (1) converting N-ethyl- N-[2-(methanesulfonamide)ethyl]-3-methyl-4-aminoaniline sulfate to its free form with a base followed by reaction the free product with p-toluensulfonic acid, or by (2) reducing N- 2-[ethyl-(3-methyl-4-nitrosophenyl)aminol]ethyl}methane- sulfonamide followed by reaction of the resultant free amine product with p- toluenesulfonic acid, or by (3) reducing n- 2-[ethyl-(3-methyl-4-nitrosophenyl) amino]-methansulfonamide in the presence of p-toluenesulfonic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a salt of a p-phenylenediamine derivative which is particularly useful in the field of photography (particularly for a developing solution) and a method for producing the same.

[0002]

2. Description of the Related Art Heretofore, as a salt of N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline, Chemical Abstracts Service
Component Registry Number (CAS) 79832-45-4
(Benzene-1,2,4,5-tetracarboxylate),
79067-38-2 (dodecyl sulfonate), 78802-96-7 (tetra (chlorophenyl) boron salt), 78802-95-6 (tetraphenylboron salt), 74292-69-6 (sulfate), 71633 -
52-8 (monomethyl ester phosphate), 65501-85-1 (sulfate), 62947-37-9 (4-ethylbenzenesulfonate), 59777-99-0 (phosphate), 59777-98-9 ( Phosphate),
56773-57-0 (hydrochloride), 56046-61-8 (phosphate), 27789-
88-4 (sulfate), 25646-71-3 (sulfate), 24567-76-8
(Sulfate), 20191-53-1 (sulfate), 7207-43-4 (sulfate), 92-09-1 (no counter anion), 150627-19
-3 (sulfate), 171899-36-8 (no counter anion), 120018-37-3 (sulfate), 117186-47-7 (hydrochloride), 103551-72-0 (di (n-butyl phosphate) ) Ester salt), 102091-34-9 (sulfuric acid, phosphate), 93552-42-2 (PF ₆
Salt), 82151-60-8 (monocyclohexyl sulfate salt), 82139-11-5 (acetic acid-2-sulfosulfanylmethyl-phenyl ester), 82138-86-1 (hexadecanoyl-methyl-sulfamate) , 82138-84-9 (1,
1,3,3-tetramethyl-butylsulfamic acid),
82098-49-5 (hydrochloride), 81608-76-6 (sulfate), 81349-
10-2 (mono [2-tert-butyl-4- (1,1-dimethylpropyl) -phenyl] -sulfate sulfate), 80527-5
8-8 (3-phenyl-propinoic acid hydroxyamide salt), 80234-85-1 (4-methylbenzenesulfinic acid salt), 80280-03-1 (pentachlorophenol salt), 80527-57-7 ( N-hydroxy-4-methylbenzenesulfonamide salt), 79871-68-4 (didodecyl phosphate salt), 79850-88-7 (bis (3-chloro-phenyl) phosphate salt) have been isolated. And p-toluenesulfonate is not isolated as a solid.

In JP-A-49-088829, 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline and its sulfate have been synthesized, but p-toluenesulfone has been synthesized. The acid salt has not been synthesized or isolated. As a general description, only p-toluenesulfonic acid is described as one of the acids that may be salt-formed. Also, unlike the case of the present invention, the raw material (precursor)
3-Methyl-4-nitro-N-ethyl-N- (β-methanesulfonamidoethyl) aniline is used. The reaction via this nitro form has problems that the conditions are severe and that there are many by-products. JP-A-62-23416
No. 1 discloses p-toluenesulfonic acid (compound I-32) as one of the sulfonic acids that are preferably used in combination with a developing agent.
Are listed. Therefore, in the developer, 4-amino-3-
Methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline and p-toluenesulfonate coexist. However, since the developer is usually alkaline, 4-amino-3-methyl-N-ethyl-N-
(Β-methanesulfonamidoethyl) aniline is not protonated (development activity is reduced if it is protonated), and it is generally considered that these two compounds do not form a salt. Rather, it is considered that a strongly acidic compound such as p-toluenesulfonic acid forms a salt with potassium or sodium when alkaline. Further, there is no description that the p-toluenesulfonate of 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline was isolated as a solid state, and much less about the production methods thereof. There is no description.

JP-A-3-240055 describes that the developing agent is a salt of p-toluenesulfonic acid, but the compounds mentioned as developing agents are completely different in structure from the compound of the present invention. . JP-A-5-134376 discloses 4-amino-3-methyl-N as compound [X-1].
Describes a compound (salt) of -ethyl-N- (β-methanesulfonamidoethyl) aniline with hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid or p-toluenesulfonic acid, but describes a solid salt isolated and purified. There is no. In the examples, only sulfates are used, and there is no example of p-toluenesulfonate. In addition, the document only describes that sulfate is added in a molar unit, and it cannot be determined from this alone whether or not it is a solid. Further, no reference literature is cited as to the method for synthesizing and isolating the salt, and there is no description that seems to have actually performed the isolation. JP-A-5-289274 discloses that
As the compound I-4 represented by the general formula [I], 4-amino-
2- (p-toluenesulfonic acid) of 3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline
Salts are described. However, there is no description about a high-purity solid salt that has been isolated and purified, and the text does not describe a method for synthesizing or isolating the salt, and does not even mention any references. Further, in the examples, the compound I-4 was not used, and there is no description that seems to be actually isolated. JP-A-6-202290 discloses a compound represented by the general formula [II]
Is described as 2- (p-toluenesulfonic acid) salt of 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline. However, there is no description that it is a high-purity solid salt that has been isolated and purified.
No isolation methods are described, nor are any references cited. There is no description that seems to have actually been isolated. The solid salt of the p-phenylenediamine derivative obtained in such a conventional production method contains, as impurities, unreacted components of starting materials, reaction intermediates, decomposition products of products, and the like. For this reason, when this was used as a photographic developing agent, it was not satisfactory because it adversely affected photographic processing and photographic properties, which required precision.

JP-A-7-261352 describes a salt of a developing agent and p-toluenesulfonic acid, but the type of the developing agent is completely different from that of the present invention. That is, 4-amino-3-methyl-N-ethyl-N-
The p-toluenesulfonate of (β-methanesulfonamidoethyl) aniline is not described. JP-A-7-3
No. 11453 describes a developer in which a developing agent and a sulfonic acid are used in combination. However, the skeleton of the developing agent mentioned in the specific example was not a paraphenylenediamine skeleton but only an aniline skeleton. JP-A-8-25480
No. 3 includes 4-amino-3-methyl-N-ethyl-N-
There is a description that (β-methanesulfonamidoethyl) aniline may be used in combination with p-toluenesulfonic acid in a developing solution, but these salts are not actually isolated and used. Has been added. Therefore, a state in which both compounds coexist is created in the developer, but since the developer is alkaline, 4-amino-3-methyl-N-ethyl-N- (β- Methanesulfonamidoethyl) aniline is not protonated and is hardly said to form a counter salt.

4-amino-3-methyl-N-ethyl-N
Among the salts of-(β-methanesulfonamidoethyl) aniline, sulfate is the most frequently used, and is used as a developing agent for color photography. The photographic light-sensitive material is subjected to processing such as color development, bleaching, fixing, washing with water and drying after exposure, but N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-amino. The aniline sulfate is added to the color developing bath. Recently, there has been a strong demand for speeding up processing, and development for that purpose has been promoted. However, since the sulfate of N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline is not so high in solubility, it can be rapidly prepared by increasing the concentration in the processing solution. Conversion was limited. In addition, the developer has a phenomenon that the solution creeps up, and when developing a photograph, the solution is transferred to the adjacent tank tank, or dried on the device in the middle, causing a streak on the photograph There was a point. Therefore, there has been a demand for a developing agent having a higher solubility and a smaller rise. At the same time, a method for producing the same has been required.

[0007]

SUMMARY OF THE INVENTION Accordingly, it is a first object of the present invention to provide a high-purity N-ethyl-N- [2- (methanesulfonamide) which has high solubility and prevents creeping after photographic processing. [Ethyl] -3-methyl-4-aminoaniline. The second object is to provide N-ethyl-N- [2- (methanesulfonamido) ethyl] -3 having high solubility and low creep.
An object of the present invention is to provide a method for producing p-toluenesulfonic acid salt of -methyl-4-aminoaniline in high yield.

[0008]

The present inventors have conducted intensive studies to solve the above-mentioned problems and found that N-ethyl-N
Adding a solid isolate of [-(2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline p-toluenesulfonate to the developer, (substantially the processing solution removes sulfate ions; (Not included), it has been found that the solubility can be drastically increased, and the crawling of the processing solution can be significantly improved. That is, the above objects have been achieved by the present invention (1) to (6). (1) A derivative of N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline sulfate with a base is reacted with p-toluenesulfonic acid. A method for producing p-toluenesulfonic acid salt of ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline. (2) N- {2- [ethyl- (3-methyl-4-nitrosophenyl) amino] ethyl} methanesulfonamide is reduced, and then p-toluenesulfonic acid is reacted, N-ethyl-N- [ 2- (methanesulfonamide)
A method for producing p-toluenesulfonic acid salt of [ethyl] -3-methyl-4-aminoaniline. (3) N- {2- [ethyl- (3-methyl-4-nitrosophenyl) amino] in the presence of p-toluenesulfonic acid
N-ethyl-N- [2- (methanesulfonamido) ethyl]-for reducing ethyl @ methanesulfonamide
A method for producing p-toluenesulfonic acid salt of 3-methyl-4-aminoaniline. (4) N-ethyl- having a purity of 95% or more and being solid
P-Toluenesulfonic acid salt of N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline. (5) p- of N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline obtained by any of the methods described in (1) to (3).
Toluene sulfonate. (6) The photographic developing agent described in (4) or (5) above.
P-Toluenesulfonate of N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline.

[0009]

Next, the p-phenylenediamine derivative salt of the present invention will be described in detail. P- of the present invention
In a phenylenediamine derivative salt, N-ethyl-N-
The preferred ratio of [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline to p-toluenesulfonic acid is N-ethyl-N- [2- (methanesulfonamido) ethyl] in molar ratio. -3-methyl-4-aminoaniline: p-toluenesulfonic acid = 1: 1 to 4, more preferably 1: 1.5 to 3, and most preferably 1: 1.8 to 2.2. (Even if the ratio is 1: 2, it is unavoidable that the ratio slightly fluctuates in production. Therefore, the ratio is set to 1.8 to 2.2 in consideration of including about 10% of an error. N-ethyl-N- [2
-(Methanesulfonamido) ethyl] -3-methyl-4
-The term "aminoaniline 2 (p-toluenesulfonic acid) salt" means that the ratio of p-toluenesulfonic acid is about 10%. This salt is isolated as a solid, and may be in any form of powder, granule, or solid (solidified). This solid may also contain water of crystallization. However, the amount of the water of crystallization is between 0 and 10 molecules per N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline molecule, preferably 0 molecule. The number of molecules is from three to more, and more preferably zero. In addition, the purity is essential to be 95% or more (referred to as mass%; the same applies hereinafter), more preferably 98% or more and the content of sulfate ions is less than 2%, more preferably 99% or more. The content of sulfate ions is less than 1%.

The following describes the p-type of N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline isolated as a solid having a purity of 95% or more.
Preferred examples of the toluenesulfonic acid salt are shown below. The following are shown in the order of preference. 1) N-ethyl-N- [2- (methanesulfonamide)
Ethyl] -3-methyl-4-aminoaniline: p-toluenesulfonic acid salt = 1: 1 to 4 2) N-ethyl-N- [2- (methanesulfonamide)
Ethyl] -3-methyl-4-aminoaniline: p-toluenesulfonate = 1: 1.5-3 3) N-ethyl-N- [2- (methanesulfonamide)
Ethyl] -3-methyl-4-aminoaniline: p-toluenesulfonate = 1: 1.8 to 2.2 4) N-ethyl-N- [2- (methanesulfonamide)
Ethyl] -3-methyl-4-aminoaniline: p-toluenesulfonic acid salt = 1: 1.8-2.2 and water of crystallization is 0
5) N-ethyl-N- [2- (methanesulfonamide)
Ethyl] -3-methyl-4-aminoaniline: p-toluenesulfonic acid salt = 1: 1.8 to 2.2 and 0 water of crystallization 6) N-ethyl-N- [2- (methanesulfone Amide)
[Ethyl] -3-methyl-4-aminoaniline: p-toluenesulfonic acid salt = 1: 1.8-2.2, 0 water of crystallization and powder

Next, the method for producing the p-phenylenediamine derivative salt of the present invention will be described in detail. N of the present invention
The p-toluenesulfonic acid salt of -ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline is a precursor of N-ethyl-N- [2-
(Methanesulfonamido) ethyl] -3-methyl-4-
By mixing aminoaniline and p-toluenesulfonic acid in a solution, and concentrating and adding a poor solvent, the compound can be isolated in high yield and high purity. Raw material N-ethyl-N-
[2- (Methanesulfonamido) ethyl] -3-methyl-4-aminoaniline is based on N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline sulfate. May be used, or a compound having no counter salt may be synthesized and used from the beginning.
Preferably, N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline sulfate is freed with a base. More preferably
N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline 3/2 sulfate 1
It is a hydrate free from base. Examples of the base that can be used for the freeing include hydroxides of alkali metals (eg, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide) and hydroxides of alkaline earth metals (eg, calcium hydroxide) , Barium hydroxide), alkali metal salts (eg, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, disodium hydrogenphosphate, tripotassium phosphate, dipotassium hydrogenphosphate, sodium pyrophosphate) , Sodium borate, sodium aluminate, sodium silicate), tertiary amines (eg, trimethylamine, triethylamine, tripropylamine, tributylamine, diisopropylethylamine), pyridines (eg, pyridine, 4-picoline, 2,6-lutidine) ), Hydroxylation Quaternary ammonium compounds (tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, cetyltrimethylammonium hydroxide, cetylpyridinium hydroxide), metal alkoxides ( For example, sodium methoxide, sodium ethoxide, potassium ethoxide, potassium t-butoxide) and the like can be mentioned. These bases may be used alone or in any ratio. The base used in these is preferably an alkali metal hydroxide, an alkali metal salt, or a metal alkoxide, and more preferably an alkali metal salt.

As the solvent that can be used for the freeing, any solvent may be used as long as it does not participate in the reaction. For example, water, alcohols (eg, methanol, ethanol, 2-propanol, n-butanol), ketones (eg, Acetone, methyl ethyl ketone), esters (eg, methyl acetate, ethyl acetate, butyl acetate), aliphatic hydrocarbons (eg, n-pentane, n-hexane, cyclohexane), and aromatic hydrocarbons (eg, benzene,
Examples thereof include toluene, xylene), ethers (eg, diethyl ether, tetrahydrofuran, dioxane), acetonitrile, dimethylformamide, dimethylacetamide and the like. Water, preferably as a solvent,
Methanol, ethanol, isopropyl alcohol, acetonitrile, acetone, methyl ethyl ketone, ethyl acetate, toluene, more preferably water, methanol, isopropyl alcohol, acetone, ethyl acetate,
Toluene, more preferably water, ethyl acetate and toluene. Further, it is preferable to use two or more solvents at the same time as compared to a single solvent.
A mixed solvent system is preferred. Preferred combinations include water-ethyl acetate, water-toluene, water-methanol,
Water-isopropyl alcohol, water-acetone and water-acetonitrile, more preferably water-ethyl acetate and water-toluene. Further, in the case of freeing with two or more solvent systems containing water, it is preferable to remove the aqueous layer and use only the organic layer for the next reaction. When the solvent is freed with a single solvent, it is preferable to separate the precipitated salt by filtration or wash the salt with water and use it in the next reaction.

The precursor N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline of the p-phenylenediamine derivative salt of the present invention is prepared by a conventionally known synthesis method. Can be synthesized. For example, by reacting ethyl-m-tolyl-amine with N- (2-chloroethyl) methanesulfonamide, N- [2-
(Ethyl-m-tolylamino) ethyl] methanesulfonamide (intermediate A) is synthesized (Reaction 1). Next, a nitroso group was introduced into intermediate A with sodium azide, and N- {2-
[Ethyl- (3-methyl-4-nitrosophenyl) amino] ethyl} methanesulfonamide (Intermediate B) is synthesized (Reaction 2). This intermediate B is reduced with hydrogen gas in the presence of a catalyst to obtain N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline (intermediate C) (reaction 3). .

In the reaction 1, a base may be used, for example, an alkali metal hydroxide (eg, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide),
Alkaline earth metal hydroxides (eg, calcium hydroxide, barium hydroxide), alkali metal salts (eg, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, trisodium phosphate, disodium hydrogen phosphate, phosphorus Tripotassium acid, dipotassium hydrogen phosphate, sodium pyrophosphate, sodium borate, sodium aluminate, sodium silicate), tertiary amines (eg, trimethylamine, triethylamine, tripropylamine, tributylamine, diisopropylethylamine), pyridines (Eg pyridine, 4-picoline,
2,6-lutidine), quaternary ammonium hydroxide compounds (tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide,
Tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, cetyltrimethylammonium hydroxide, cetylpyridinium hydroxide), metal alkoxides (eg, sodium methoxide, sodium ethoxide, potassium ethoxide, potassium t-butoxide) and the like. . These bases may be used alone or in any ratio. Preferably, the base used is
Alkali metal hydroxides, alkali metal salts and metal alkoxides, more preferably alkali metal salts. However, this reaction proceeds without using a base,
Rather, there is an advantage that by-products are small. Therefore, preferably, no base is used in reaction 1. In the reaction 2, it is necessary to carry out the reaction in an acid, and hydrochloric acid is preferable as the acid. In addition, before the acidification and the reaction, the alkali is once made alkaline and the raw material is completely dissolved, and then the acid is made acidic, so that the reaction proceeds more smoothly. Reaction 3
May be reacted as it is without adding acid or base,
To minimize by-products it is preferred to have an acid such as sulfuric acid. Among the acids, it is more preferable to coexist p-toluenesulfonic acid used in the production method of the present invention.

Further, in mixing N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline and P-toluenesulfonic acid, contact with oxygen is minimized. It is preferable to flow nitrogen gas, argon gas or helium gas. It is more preferable to flow nitrogen gas. Also, it is preferable to mix in a container that can block light. N-ethyl-N- [2- (methanesulfonamido) ethyl]-
When 3-methyl-4-aminoaniline and P-toluenesulfonic acid are mixed, the initial temperature is preferably from 0 to 70 ° C, more preferably from 5 to 50 ° C, and most preferably from 10 to 40 ° C.

The solvent used for mixing may be any solvent as long as it does not participate in the reaction. For example, water, alcohols (eg, methanol, ethanol, 2-propanol, n-butanol), ketones (eg, acetone, methyl ethyl ketone), esters (Eg, methyl acetate, ethyl acetate, butyl acetate), aliphatic hydrocarbons (eg, n-pentane,
Examples thereof include n-hexane, cyclohexane), aromatic hydrocarbons (eg, benzene, toluene, xylene), ethers (eg, diethyl ether, tetrahydrofuran, dioxane), acetonitrile, dimethylformamide, dimethylacetamide, and the like. Preferably, the solvent is water, methanol, ethanol, isopropyl alcohol, acetonitrile, acetone, methyl ethyl ketone, ethyl acetate, toluene, more preferably water, methanol, isopropyl alcohol, acetone, ethyl acetate, toluene, further preferably water , Ethyl acetate and toluene. It is more preferable to use two or more solvents at the same time than to use them alone, and it is particularly preferable to use a mixed solvent of water and an organic solvent. Preferred combinations include water-ethyl acetate, water-toluene,
Water-methanol, water-isopropyl alcohol, water-acetone, water-acetonitrile, and more preferably water-methanol and water-isopropyl alcohol.

For concentration after mixing, concentration under reduced pressure by heating is preferable to concentration by heating alone. Crystallization can be performed by adding a seed crystal, but it is preferable to add a poor solvent to improve the yield. Any organic solvent may be used as the poor solvent, but ethyl acetate and toluene are particularly preferred. The crystallization temperature is preferably from 0 to 50 ° C, more preferably from 0 to 30 ° C. A mixture of N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline and p-toluenesulfonic acid is obtained by mixing N-ethyl-
After the salt of N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline is made free, it may be carried out without isolation. It is preferable to mix with p-toluenesulfonic acid without isolation rather than isolation. The amount of p-toluenesulfonic acid added during mixing depends on the ratio of the salt to be isolated, but may be N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline. It is 1 to 4 moles, more preferably 1.5 to 3 moles, and most preferably 1.8 to 1 mole per 1.
2.2 times mol. The concentration of p-toluenesulfonic acid is preferably 0.01 mol / L to 5 mol / L, more preferably 0.1 to 2 m / L.
ol / L, more preferably 0.2 to 1 mol / L.
L. It is preferable that p-toluenesulfonic acid is added in a state of being dissolved in a solvent in advance. As the solvent that can be used at that time, those listed as solvents that can be used for mixing can be applied. Preferred are water and alcohols, and more preferred are alcohols.

Alternatively, N- {2- [ethyl- (3-methyl-4-nitrosophenyl) amino] ethyl} methanesulfonamide is reduced in the presence of p-toluenesulfonic acid to give N-ethyl-N- [2- (Methanesulfonamido) ethyl] -3-methyl-4-aminoaniline p-toluenesulfonate can be produced and isolated in high yield. In addition, when a photographic processing solution is used, the rise of the solution is greatly improved, and there is no problem in other photographic properties. The amount of p-toluenesulfonic acid required for reducing N- {2- [ethyl- (3-methyl-4-nitrosophenyl) amino] ethyl} methanesulfonamide is N- {2- [ethyl- (3-Methyl-4-nitrosophenyl) amino] ethyl @ methanesulfonamide 1 to 1 to 4 moles, more preferably 1.5 moles.
The molar ratio is 1.8 to 2.2 times, most preferably 1.8 to 2.2 times.

As the reducing agent, all reducing agents generally known as nitroso group reducing agents can be used. Preferably, reduction with hydrogen gas using a catalyst,
Reduction using ammonium chloride and iron, and more preferably reduction using hydrogen gas using a catalyst. The catalyst used in the case of reduction with hydrogen gas is a noble metal catalyst, preferably Pd / C or the like. As the solvent, for example, those mentioned as solvents that may be used at the time of mixing can be applied. In the case of the reduction using ammonium chloride and iron, as the solvent, for example, those mentioned as solvents that may be used during mixing can be applied. Preferred are alcohols and / or water, more preferred is isopropyl alcohol and / or water, and particularly preferred is a mixed system of isopropyl alcohol and water. Isolation was performed using N-ethyl-N- [2- (methanesulfonamide)
Ethyl] -3-methyl-4-aminoaniline and p-toluenesulfonic acid can be mixed in the same manner as when a salt is synthesized.

[0020]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 Synthesis of 2 (p-toluenesulfonic acid) salt of N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline N-ethyl-N- [ 2- (methanesulfonamido) ethyl] -3-methyl-4-amino-aniline 3 / 2H ₂ SO ₄
-10 g (0.027 mol) of monohydrate and 100 ml of ethyl acetate were put into a 300 ml three-necked eggplant-shaped flask, and the mixture was stirred well while flowing nitrogen. 100 ml of water and 8.6 g (0.081 mol) of sodium carbonate were added little by little while paying attention to foaming. After further stirring for about 5 minutes, the entire reaction solution was transferred to a separating funnel and shaken well.
After standing, the aqueous layer was separated and discarded, and the organic layer was transferred to a 200 ml beaker. On the other hand, 10.27 g (0.054 mol) of p-toluenesulfonic acid monohydrate was added to 50 m of methanol.
and added little by little to the organic layer transferred to a beaker. After concentration under reduced pressure, seed crystals are added, and the mixture is stirred while being cooled to 20 ° C. or lower, whereby N-ethyl-N- [2- (methanesulfonamido) ethyl] -3 having a purity of 99% or more is obtained.
16.1 g (yield 96.8%) of 2- (p-toluenesulfonic acid) salt of -methyl-4-aminoaniline was obtained.

Example 2 Synthesis of 1- (p-toluenesulfonic acid) salt of N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline N-ethyl-N- [ 2- (methanesulfonamido) ethyl] -3-methyl-4-amino-aniline 3 / 2H ₂ SO ₄
-10 g (0.027 mol) of monohydrate and 100 ml of ethyl acetate were put into a 300 ml three-necked eggplant-shaped flask, and the mixture was stirred well while flowing nitrogen. 100 ml of water and 8.6 g (0.081 mol) of sodium carbonate were added little by little while paying attention to foaming. After further stirring for about 5 minutes, the entire reaction solution was transferred to a separating funnel and shaken well.
After standing, the aqueous layer was separated and discarded, and the organic layer was transferred to a 200 ml beaker. On the other hand, 5.14 g (0.027 mol) of p-toluenesulfonic acid monohydrate was added to 25 ml of methanol.
And added little by little to the organic layer transferred to the beaker. After removing the organic solvent almost completely by vacuum concentration,
A seed crystal was added and crystallized by standing overnight in a refrigerator. N-ethyl-N- [2- (methanesulfonamido) ethyl] having a purity of 99% or more was handled while handling with a small amount of ethyl acetate. 10.8 g (yield 90.2%) of 1- (p-toluenesulfonic acid) salt of -3-methyl-4-aminoaniline was obtained.

Example 3 Synthesis of 3 (p-toluenesulfonic acid) salt of N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline N-ethyl-N- [ 2- (methanesulfonamido) ethyl] -3-methyl-4-amino-aniline 3 / 2H ₂ SO ₄
-10 g (0.027 mol) of monohydrate and 100 ml of ethyl acetate were put into a 300 ml three-necked eggplant-shaped flask, and the mixture was stirred well while flowing nitrogen. 100 ml of water and 8.6 g (0.081 mol) of sodium carbonate were added little by little while paying attention to foaming. After further stirring for about 5 minutes, the entire reaction solution was transferred to a separating funnel and shaken well.
After standing, the aqueous layer was separated and discarded, and the organic layer was transferred to a 200 ml beaker. On the other hand, 15.40 g (0.081 mol) of p-toluenesulfonic acid monohydrate was added to 75 m of methanol.
and added little by little to the organic layer transferred to a beaker. After concentration under reduced pressure, seed crystals were added, and the mixture was stirred while being cooled to 10 ° C. or lower, whereby N-ethyl-N- [2- (methanesulfonamido) ethyl] -3 having a purity of 99% or more was obtained.
20.2 g (yield 95.1%) of 3 (p-toluenesulfonic acid) salt of -methyl-4-aminoaniline could be obtained.

Example 4 N-Ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline by reduction
Synthesis of (p-toluenesulfonic acid) salt N- {2- [ethyl- (3-methyl-4-nitrosophenyl) amino] ethyl} methanesulfonamide 10 g
(0.035 mol) and 13.3 g (0.070 mol) of p-toluenesulfonic acid monohydrate in toluene: water =
It was dissolved in 100 ml of a 1: 1 mixed solvent and placed in an autoclave. 0.5 g of 10% Pd / C catalyst was added, the pressure of hydrogen gas was adjusted to 20 kg / cm ² , and the reaction was performed at an internal temperature of 50 to 60 ° C. for 3 hours. After confirming that a predetermined amount of hydrogen gas had been consumed, the reaction solution was filtered through celite to remove the catalyst. After concentrating under reduced pressure, water and toluene were distilled off, and a small amount of ethyl acetate and seed crystals were added to a syrupy place, followed by slow stirring at room temperature. The precipitated crystals were collected by filtration, washed with ethyl acetate and air-dried. 19.2 g of 2 (p-toluenesulfonic acid) salt of N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline having a purity of 98% (87.5% yield) ).

Example 5 Reduction of N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline by reduction
Synthesis of (p-toluenesulfonic acid) salt 2 N- {2- [ethyl- (3-methyl-4-nitrosophenyl) amino] ethyl} methanesulfonamide 10 g
(0.035 mol), 13.3 g (0.070 mol) of p-toluenesulfonic acid monohydrate in methanol 10
It was dissolved in 0 ml and placed in an autoclave. 1.5 g of Raney nickel was added, and the pressure of hydrogen gas was increased to 10 kg / cm.
² , and reacted at room temperature for 4 hours. After confirming that a predetermined amount of hydrogen gas had been consumed, the reaction solution was filtered through celite to remove the catalyst. After concentrating under reduced pressure, methanol was distilled off, and a small amount of ethyl acetate and seed crystals were added to a candy-like portion, followed by slow stirring at room temperature. The precipitated crystals were collected by filtration, washed with ethyl acetate and air-dried. N-ethyl-N- [2-
(Methanesulfonamido) ethyl] -3-methyl-4-
2 (p-toluenesulfonic acid) salt of aminoaniline
9.0 g (85.3% yield) could be obtained.

Example 6 Reduction of N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline by reduction
Synthesis of (p-toluenesulfonic acid) salt 3 N- {2- [ethyl- (3-methyl-4-nitrosophenyl) amino] ethyl} methanesulfonamide 10 g
(0.035 mol) was dissolved in 100 ml of methanol and placed in an autoclave. Raney nickel 1.5
g, and the pressure of hydrogen gas was adjusted to 10 kg / cm ² , and the mixture was reacted at room temperature for 4 hours. After confirming that a predetermined amount of hydrogen gas had been consumed, the reaction solution was filtered through celite to remove the catalyst.
13.3 g of p-toluenesulfonic acid monohydrate (0.0
(70 mol) was dissolved in 20 ml of water and added to the filtrate. After salt formation with heating, the mixture was concentrated under reduced pressure to remove water and methanol, and isopropyl alcohol and seed crystals were added to a syrupy mixture, followed by slow stirring at room temperature. The precipitated crystals were collected by filtration, washed with isopropyl alcohol, and air-dried. 18.3 g of 2 (p-toluenesulfonic acid) salt of N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline having a purity of 97% (82.2% yield) ).

Example 7 Reduction of N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline by reduction of p
Synthesis of Toluenesulfonate N- {2- [ethyl- (3-methyl-4-nitrosophenyl) amino] ethyl} methanesulfonamide 10 g
(0.035 mol), 5.6 g of ammonium chloride
(0.11 mol) in isopropyl alcohol: water =
The mixture was dissolved in 200 ml of a 9: 1 mixed solvent, and heated and stirred at 80 ° C. 2 g of iron powder was added little by little while paying careful attention not to cause bumping. After heating under reflux for 2 hours, the mixture was cooled and filtered through celite. 6.7 g (0.035 mol) of p-toluenesulfonic acid monohydrate was dissolved in 20 ml of water and added to the filtrate. After stirring well, isopropyl alcohol and water were distilled off under reduced pressure, 50 ml of isopropyl alcohol and seed crystals were added, and the mixture was slowly stirred at room temperature. The precipitated crystals were collected by filtration and recrystallized from isopropyl alcohol. 12.0 g of p-toluenesulfonic acid salt of N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline having a purity of 99%.
(76.7% yield).

Example 8 Evaluation of Photographic Properties and Evaluation of Liquid Crawling A multilayer color photographic paper (sample 001) described in Example 4 of JP-A-5-303186 and the following processing solutions were prepared. [Color developer] Tank solution Replenisher Cation exchange water 800.0ml 800.0ml Compound M 0.1g 0.1g

[0029]

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Triisopropanolamine 15.0 g 15.0 g Potassium hydroxide 3.0 g 3.0 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.5 g 0.5 g Potassium chloride 14.5 g-potassium bromide 0.04 g-optical brightener (compound N) 2.5 g 3.0 g

[0031]

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Sodium sulfite 0.1 g 0.1 g disodium-N, N-bis (sulfonatoethyl) hydroxylamine 8.5 g 11.0 g N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4 -Salts of aminoaniline listed in Table 1 0.011 mol 0.026 mol Potassium carbonate 26.3 g 26.3 g Water is added 1000.0 ml 1000.0 ml pH (adjusted at 25 ° C / KOH or sulfuric acid) 10.15 11.15

[Bleach-fixing solution] Water 700.0 ml 700.0 ml ammonium thiosulfate (750 g / liter) 100.0 ml 250.0 ml ammonium sulfite 35.0 g 88.0 g p-aminobenzenesulfinic acid 5.0 g 12.5 g imidazole 8.0 g 20.0 g ethylenediaminetetraacetic acid 32.1 g 81.8g Ferric nitrate-9 hydrate 40.4g 101g Add water 1000.0ml 1000.0ml pH (at 25 ° C / nitric acid or aqueous ammonia) 7.0 6.8

[Rinse] (1) to (4) Common chlorinated sodium isocyanurate 0.02 g 0.02 g Deionized water (conductivity 5 μS / cm or less) 1000.0 ml 1000.0 ml pH 6.5 6.5

[Processing process ( _PBlix )] [Process] [Temperature] [Time] [Replenishment amount ^* ] [Tank volume] Color development 39 ° C 45 seconds 70 ml 20 liter Bleaching and fixing 35 ° C 45 seconds 60 ml ^{* *} 20 l rinse 35 ° C. 20 seconds - 10 l rinse 35 ° C. 20 seconds - 10 l rinse 35 ° C. 20 seconds 360 ml 10 l drying 80 ° C. 60 seconds (* photosensitive material 1 m ² per replenishment amount) (to rinse → 3 and a tank countercurrent system) (in addition to ** the 60 ml, poured the photosensitive material 1 m ² per 120ml from rinse)

After exposing the sample 001 to wedges, the sample was processed according to the above-described processing steps. After processing, the maximum density (Dma) of the red filter light density (cyan dye density) of each sample
x) was measured in reflection density. Next, continuous processing was performed until the replenishment amount was twice the replenishment amount of the color developing tank, and the degree of liquid crawling in the developing bath of the processor was confirmed.

[0037]

[Table 1]

As shown in Table 1, the p-phenylenediamine derivative salt of the present invention could be used as a developing agent as well as sulfate, and the Dmax concentration was rather high. In addition, the derivative salt of the present invention (runs 5 to 7) was at a level at which there was no problem in terms of creeping up of the solution. In the case of run 4 as well, there was no problem in terms of Dmax and creeping of the solution, but free N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline was It has poor stability against oxidation and cannot be used as a commercial product. From the above, the p-phenylenediamine derivative salt of the present invention was found to be excellent.

[0039]

The p-phenylenediamine derivative salt of the present invention is suitable for photographic use, and is particularly excellent in that rapid processing with a high-concentration processing solution can be realized as a developing agent, and at the same time, crawling can be prevented. . Further, among the production methods of the present invention, the method of claim 2 or 3 is excellent in that the derivative salt can be produced with high yield and high purity without using sulfate ions.

Claims (5)

[Claims] 1. A method in which a sulfate of N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline is derivatized with a base, followed by reaction with p-toluenesulfonic acid. A method for producing p-toluenesulfonic acid salt of N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline. 2. N- {2- [ethyl- (3-methyl-4)
N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-amino, which is treated with p-toluenesulfonic acid after reduction treatment of -nitrosophenyl) amino] ethyl @ methanesulfonamide Aniline p
-A process for the production of the toluenesulfonate. 3. The method of claim 1, wherein N-
{2- [Ethyl- (3-methyl-4-nitrosophenyl) amino] ethyl} methanesulfonamide is reduced to give N-ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4. -P- of aminoaniline
A method for producing a toluenesulfonic acid salt. 4. A solid N having a purity of 95% or more and being solid
-Ethyl-N- [2- (methanesulfonamido) ethyl] -3-methyl-4-aminoaniline p-toluenesulfonate. 5. The N- according to claim 4, which is a photographic developing agent.
Ethyl-N- [2- (methanesulfonamido) ethyl]
P-Toluenesulfonic acid salt of -3-methyl-4-aminoaniline.