JPS5855144B2 - 3-acylamino-5-pyrazolone fluoride - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved method for producing 3-acylamino-5-pyrazolones, particularly for producing 3-acylamino-5-pyrazolones having a substituent containing a sulfo group at the 1-position. It is something.

3-amylamino-5-pyrazolones having a sulfo group can be used as magenta color formers (couplers) for silver halide color photographic materials, and as sensitizing dyes (e.g. methine dyes) for silver halide photographic materials. It is an extremely important compound as an intermediate for dyes (for example, filter dyes).

The amino group at the 31st position of 3-amino-5-pyrazolones having a sulfo group at the 1st position has low activity.

For the acylation reaction of this amino group, there is a method of acylating with an organic acid . known (US Pat. No. 1,007,847).

However, due to the low solubility of the reactants used in this method,
It is a heterogeneous reaction, and it is difficult to remove the L. Lewis acid from the product after the reaction.

(Even after repeated purification, Lewis acid remains.)

In addition, in the isolation or purification process of the product, it is handled in the form of a salt with an alkali metal salt or an alkaline earth metal, and the process is complicated.

Compounds having a sulfo group are usually isolated from reaction mixtures or treated in the form of salts with alkali metals or alkaline earth metals at °C during the purification process.

Alkali metal or alkaline earth metal salts have extremely high solubility in water, but on the contrary, their solubility in organic solvents is significantly reduced.

Therefore, it is advantageous for reactions in aqueous systems, but disadvantageous for reactions in organic solvents.

Organic chemical reactions are more often carried out in organic solvent systems than in water systems, and organic solvent systems are also more advantageous for operations such as isolation and purification of reaction products.

Organic compounds having sulfo groups become soluble in certain organic solvents if they are in the form of free acids or salts with ammonia or organic bases rather than salts of alkali metals or alkaline earth metals; It becomes possible to perform various organic chemical reactions.

There are various organic compounds with sulfo groups that are used in photographic materials, but in their production, the raw organic compounds with sulfo groups are used in the form of free acids or salts of organic bases. It is desirable that there be.

Therefore, an object of the present invention is to provide a novel manufacturing method that can obtain 3-acylamino-5-pyrasolones having a sulfo group with high quality and high yield.

Another object of the present invention is to provide a new method for the preparation of 3-acylamino-5=pyrazolones having a sulfo group obtained with salts of organic bases.

The object of the present invention was achieved by the following manufacturing method.

That is, the present invention relates to the noacylation reaction of 3-amino-5-pyrazolones having a sulfo group represented by the general formula (n) with an organic acid represented by the general formula (III) and the general formula (
This is a method for producing 3-acylamino-5-pyrazolones having a sulfo group represented by general formula (I) by carrying out the process in a mixed system of a sulfonyl halide represented by IV) and an organic base.

In the formula, R1 is an aliphatic group, R2 is an aliphatic group or an aryl group, and Q has at least one sulfo group.
X represents an aliphatic group, an aralkyl group, or an aryl group, and each represents a halogen atom.

The general formula (I), (II), (III), (IV),
Preferably, R1 is an alkyl group having 1 to 5 carbon atoms (for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, etc.), and R2 is an alkyl group having 1 to 5 carbon atoms (for example, methyl , ethyl, n-propyl, n-butyl, etc.), substituted alkyl groups having 1 to 3 carbon atoms (e.g., trichloromethyl, trifluoromethyl, chloroethyl, etc. having -.logen as a substituent), phenyl group or substituted phenyl group (for example, an alkyl group or a halogen atom as a substituent, such as 4-methyl-phenyl, 2-chlorophenyl, etc.), and Q is an alkyl group having 1 to 5 carbon atoms substituted with at least one sulfo group (for example, 2- sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, etc.),
Number of carbon atoms (alkyl residue) having a sulfo group and a substituent other than a sulfo group (e.g., halogen, alkoxy, etc.)
2 to 5 substituted alkyl groups (e.g. 2-sulfo-2-methyl-ethyl, 3-sulfo-3-methyl-propyl, 4
-sulfo-2-methoxybutyl, 1-sulfo-2chloropropyl, etc.), aralkyl groups substituted with at least one sulfo group (e.g. 3-sulfobenzyl, 3-sulfophenethyl, etc.); or an aryl group substituted with a sulfoalkyl group having 1 to 3 carbon atoms (e.g., 4-sulfophenyl, 3-sulfophenyl, 3-sulfomethyl-phenyl, 2,5 disulfophenyl, 2,4-disulfophenyl, 3・5-
disulfophenyl 2-chloro-4-sulfophenyl,
4-phenoxy-3-sulfophenyl, 2-methyl-
5-sulfophenyl, 2,5-dichloro-4-sulfophenyl, 4,8-disulfonaphthyl-(2), 6,8-
disulfonaphthyl-(2), etc.), and X represents a fluorine, chlorine, or bromine atom, respectively.

As described in detail above, it is particularly advantageous for the sulfo group to be in the form of a free acid or a salt of ammonia or the above-mentioned organic base for the synthetic reaction.

Among these, the free acid form or the salt form of an organic base is preferred.

Moreover, the 3-3-
Acylamino-5-pyrazolones (those in which the sulfo group is in the form of a free acid or a salt of ammonia or an organic base) have the sulfo group converted to the form of an alkali metal or alkaline earth metal salt, if necessary. can do.

For example, a potassium salt can be precipitated and isolated by adding a methanol solution of potassium acetate or potassium hydroxide to a pyrazolone solution.

However, it is extremely difficult to convert and isolate the sulfo group from a solution of an alkali metal or alkaline earth metal salt of pyrazolone into the free acid form or amine salt form.

In the present invention, the organic base is preferably a tertiary aliphatic or aromatic amine, such as trimethylamine, triethylamine, n-)liprobylamine, pyridine,
Preferred are N-N-dimethylaniline, N-N-diethylaniline, and the like.

One of the important features of the present invention is that the acylation reaction of 3-amino-5-pyrazolones having a sulfo group represented by the general formula (n) is carried out using an organic acid represented by the general formula (m), (
As shown in IV), the reaction is carried out in a mixed system with a rhodanated sulfonyl compound and an organic base.

In the present application, "reacting in a mixed system of an organic acid, a sulfonyl halide, and an organic base" means that in a mixture of an organic acid, a sulfonyl halide, and an organic base, the
~Amino-5-pyrazolones complete the acylation reaction to form the product, 3-acylamino- with a sulfo group.
This means producing 5-pyrazolones, and the order of addition of the pyrazolone reactant, organic acid, sulfonyl halide, and organic base does not matter.

The second feature is that when the organic acid and organic base coexist,
The pyrazolone reactant is soluble in the system, and the mixed acid anhydride formed from the organic acid and the sulfonyl halide can very effectively contribute to the acylation reaction.

The amount of the organic base used is 0.5 to 0.5 to 3-amino-5-pyrazolones having a sulfo group used in the present invention.
The amount of the organic acid used is 1 to 20 times the volume of the pyrazolones, and the sulfonyl rhodanide is used in a molar ratio of 1 to the pyrazolones.
．． A rough guideline can be 0 to 0.5 times.

Preferably, the amount of the organic base used is 2 to 5 times the volume of the pyrazolones, and the amount of the organic acid used is 2 to 5 times the volume of the pyrazolones.
At ~5 times the amount, the alihalogenated sulfonyl compounds have a molar ratio of 1
．． It is 0 to 1.5 times.

In the present invention, the reaction temperature is from room temperature to about 130°C, and the preferred reaction temperature is 40°C.
~90°C.

The reaction time is determined by the above-mentioned reaction temperature.
It takes about 1 hour to 3 days.

There are various ways to tell when the reaction is complete, but for example, take = part of the reaction solution and pass it through a thin layer chromatograph.
You can tell them apart by observing their spectra.

Compared to the conventional method of acylating using an organic acid halide, a Lewis acid (e.g., aluminum chloride), and a solvent such as ethylene dichloride or nitrobenzene, the production method of the present invention does not contain impurities (e.g., Lewis acid) in the acylated product. It is superior in that it does not require the use of solvents that cause pollution such as ethylene dichloride and nitrobenzene, and the reaction process is simple. .

As mentioned above, the 5-pyrazolones produced according to the present invention can be used as intermediates for azo dyes, sensitizing dyes and photographic dyes.

These dyes and pigments obtained using this intermediate have excellent mordant properties and decolorizing properties, and are therefore very useful.

Azo dyes are used, for example, as dyes for textiles and knitted fabrics, and for photographic materials, such as filters.

It can be used for dyes such as silver dye bleaching method and diffusion transfer method.For example, "Color Index"
Index Third Edition (Th1rd E
d,), Volium (vol,) 4, The Society Off Dyers End Chikara Lists (The
5ociety□f 1) yers and Co
1ourists), pages (P) 4124-413
It can be manufactured according to the method described in 3.

In addition, sensitizing dyes (for example, methine dyes) are used, for example, in U.S. Pat.
It can be manufactured according to the method described in No. 187 and the like.

Further, photographic dyes (for example, filter dyes) can be produced according to the methods described in, for example, British Patent No. 506385, US Patent No. 2274782, Japanese Patent Publication No. 39-22069, and Japanese Patent Application No. 141519-1982 can.

Examples of filter dyes include oxonol dyes,
Examples include hemioxonol dyes, merocyapine dyes, and azo dyes.

Representative examples of the compound represented by general formula (I) are listed below.

Specific examples of the organic acid represented by the general formula (III) include acetic acid, propionic acid, and butyric acid.

Specific examples of the sulfonyl halides represented by the general formula (■) include methanesulfonyl chloride, trifluoromethanesulfonyl chloride, and p-toluenesulfonyl chloride.

Example 1 3-acetamido-1-(4'-sulfophenyl)-5
-Synthesis of pyrazolone-triethylamine salt 3-amino-
1-(4'-sulfophenyl)-5-pyrazolone triethylamine salt7. If (0.02 mol), glacial acetic acid 20r
Suspend 10 ml of fL11 triethylamine and add 2.3 f? of methanesulfonyl chloride. (0.02 mol) was added and stirred while heating on a steam bath.

After becoming a homogeneous solution, crystals began to precipitate in 1 hour.

The mixture was further heated and stirred for 3 hours. After cooling with ice water, the crystals were collected.

Recrystallization from methanol gave 5.0 g of prism crystals with a melting point of 269-271°C.

Analysis value; C151, 83%; N16.93%; N, 13
．． 64% (calculated value as C18H26N405S-N20; C
, 51,91; H, 6,78; N, 13.45) Example 2 3-acetamido-1-(3,5-disulfofenyl/L
/ ) -5-Hirazolone C41): Synthesis of r-f-ruamine salt 3-amino-1-(3,5-disulfophenyl)5-pyrazolone ditriethylamine salt 10.4tiI (0,0
2 mol), glacial acetic acid 20rnl! , triethylamine 10
Suspend m1 and add trifluoromethanesulfonyl chloride3.
6? (0.02 mol) was added, and the mixture was heated and stirred on a steam bath.

After becoming a homogeneous solution, crystals were precipitated in 1 hour.

The mixture was further heated and stirred for 3 hours. After cooling with ice water, the crystals were separated.

Recrystallization from methanol yielded 8.31 prismatic crystals with a melting point of 275-278°C.

Analysis value; C135, 72%; H, 5, 23%; N, 15
．． 95% (calculated value C as C13H22N508S2, 35
, 46%; H, 504%; N1 15.89%) Example 3 3-propioamide-1-(4'-sulfophenyl)-
Synthesis of 5-pyrazolone-triethylamine salt 3-amino-1-(4'-sulfophenyl)-5-pyranolone-triethylamine salt7. Of (0.02 mol), propionic acid 30ml 11 triethylamine 15m
1 was suspended, p-4 luenesulfonyl chloride 3.89
(0.02 mol) was added, and the mixture was heated and stirred on a steam bath.

A homogeneous solution was obtained, and the mixture was heated and stirred for 6 hours.

The reaction mixture was concentrated under reduced pressure and then cooled with ice water to precipitate crystals.

Recrystallization from methanol gave 55 g of prismatic crystals with a melting point of 249-250°C.

Analysis value; C15398%; N16.90%; N, 13.
46% (calculated value as C19N28 N405 S; C15
3,76%; N16.64%; N113.19%) Example 4 Synthesis of 3-acetamido-1-(γ-sulfopropyl)5-pyrazolone-triethylamine salt 3~Amino-1-
(γ-sulfopropyl)-5 pyrazolone 6.41 (0,
02 mol), 20 liters of glacial acetic acid, 10+n of triethylamine
/! was suspended, and methanesulfonyl chloride 2.39 (0
, 02 mol) and heated and stirred on a steam bath.

A homogeneous solution was obtained, and the mixture was heated and stirred for 4 hours.

The reaction mixture was concentrated under reduced pressure and then cooled with ice water to precipitate crystals.

Recrystallization from methanol gave prismatic crystals 5,11 with a melting point of 243-246°C.

Analysis value; C146.08%: H17.82%: N, 15
．． 12% (calculated value as C14H28N405S C,46,1
5%; H, 7,74%; N, 15.36%) Example 5 3-propioamide-1-(γ-sulfopropyl)-5
-Synthesis of pyrazolone-triethylamine salt 64 g (0.02 mol) of 3-amino-1-(r-sulfopropyl)-5-pyrazolone, 20 ml of glacial acetic acid. Suspend 10ml of triethylamine and 3.8ml of p-toluenesulfonyl chloride. (0.02 mol) was added thereto, and the mixture was heated and stirred on a steam bath.

After the solution became homogeneous, it was further heated and stirred for 6 hours.

The reaction mixture was concentrated with reduced volume and then cooled with ice water.
Crystals precipitated.

Recrystallization from methanol gave 4.71 prismatic crystals with a melting point of 235-238°C.

Analysis value: C147, 34%; H, 8,03%; N, 14
．． 54% ((, + 5 Calculated value as H2ON4058 C, 4
7,58%; H, 7,98%: N, 14.79%) Example 6 3-acetylamide-1-(4'-sulfobenzyl)-
Synthesis of 5-pyrazolone-triethylamine salt 7.2 f (0.02 mol) of 3-amino-1-(4'-sulfobenzyl)-5-pyrazolone, 20 m7 of glacial acetic acid! ,
10 ml of triethylamine was suspended, 2.3 P (0.02 mol) of methanesulfonyl chloride was added thereto, and the mixture was heated and stirred on a steam bath.

The solution became homogeneous, and crystals were precipitated in 1 hour.

The mixture was further heated and stirred for 3 hours. After cooling with ice water, one collection of crystals was collected.

Recrystallization from methanol gave 4.91 prismatic crystals with a melting point of 247-251'C.

Analytical values: C, 5359%; H, 6,91%.

N, 13.50% (calculated value as C19H28N405S C153,7
6%; H16, 64%; N, 13.19%)

Claims (1)

[Scope of Claims] 1. The acylation reaction of 3-amino-5-pyrazolones having a sulfo group represented by the general formula (II) is carried out using the general formula (III).
) A fatty acid represented by the general formula (TV)...3 having a sulfo group represented by the general formula ('') characterized by being carried out in a mixed system of a rokenized sulfonyl compound and an organic base
-Production method of acylamino-5-pyrazolones. In the formula, R1 is an aliphatic group, R2 is an aliphatic group or an aromatic group, Q is an aliphatic group, an aralkyl group, or an aromatic group having at least one sulfo group, and X is an aliphatic group.・Represents each rogen atom.