JPH02295975A - Production of 3-n-monosubstituted amino-4-substituted-5-pyrazolenes - Google Patents

Abstract

PURPOSE:To obtain 3-N-monosubstituted amino-4-substituted-5-pyrazolones having a substituent group bound to the 4-position through N or S atom in high yield in one stage by using a 5-pyrazolone having bromine atom at the 4-position as a starting compound. CONSTITUTION:3-N-Substituted amino-4-bromo-5-pyrazolones expressed by formula I [R1 is aliphatic hydrocarbon, aryl or heterocyclic ring; R2 is alkyl, aryl or heterocyclic ring; R3 is H or COR3' (R3' is alkyl, aryl, alkoxy or aryloxy)] are reacted with a compound expressed by formula II (W is 5- to 6-membered heterocyclic ring containing >=2N atoms, alkylthio or arylthio) in the presence of a base to afford 3-N-monosubstituted amino-4-substituted-5-pyrazolones, expressed by formula III and having a substituent group bound to the 4-position through N or S atom without protecting the 3-position with an acyl group. The resultant compounds are useful as a magenta coupler or an intermediate for dyes, medicines, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an improved method for producing 3-N-monosubstituted amino-4-substituted-5-pyrazolones. For more information,
The present invention relates to a method for producing the above-mentioned pyrazolones having a substituent bonded to the 4-position through an N or S atom.

(Prior Art) 5-pyrazolones are important compounds as magenta couplers in the field of silver halide photography, and are also important as synthetic intermediates for many dyes and medicines.

In the photographic field, oxidative coupling with a phenylenediamine-based developing agent, etc. is performed using a color development method.
5-pyrazolones are frequently used as magenta couplers, which are the corresponding azomethine dyes.

A coupler having a so-called leaving group at the 4-position of the 5-pyrazolone coupler is widely used as a 2-equivalent magenta coupler. Also, a coupler in which this leaving group is a development inhibitor is well known as a so-called DIR coupler, and is disclosed in a US patent. Box 3.227.554, Box 4.477.56
It is stated in No. 3, etc.

Couplers in which the 3-position of 5-pyrazolone is substituted with alkylamino, arylamino, or heterocyclic-substituted amino are important photographic materials because the derived azomethine dyes have excellent color fastness and color development. Methods for synthesizing 2-equivalent 3-N-monosubstituted amino-5-pyrazolones are described in Nobuo Furudate et al., JP-A-52-93768 and JP-A-53-63377, and Kotabe Nakamura et al., JP-A-61-19633. It is disclosed in the publication number etc. Generally, in order to introduce a leaving group bonded with S or N to the 4-position of 5-pyrazolone, a synthetic method using a chloro-substituted product at the 4-position as an intermediate is specifically exemplified. This intermediate 3-N-monosubstituted amino-
In the synthesis of 4-chloro-5-pyrazolones, 4
, 4-dichlor as a by-product, it is common to protect the secondary amino group at the 3-position with an acyl group before chlorination, as shown in the following formula.

C0CH.

Here, when WH is a nitrogen-containing heterocycle, the 4-
Although the introduction of the compound proceeds at a relatively high yield, it is desirable to proceed at an even higher yield. Particularly when WH is an arylthiol or an alkylthiol, the reaction yield is extremely low.

In addition, R1 and Rt in the above formula have the same meanings as described below.

(Problems to be Solved by the Invention) The object of the present invention is to provide a method for synthesizing 3-N-mono-substituted amino-4-substituted-5-pyrazolones that can introduce a cyclic nitrogen-containing heterocycle into a leaving group in an extremely high yield. Our goal is to provide the following.

A second object of the present invention is to provide a method for synthesizing the above-mentioned 5-pyrazolones, which can introduce an arylthio group or an alkylthio group as a leaving group in good yield.

(Means for Solving the Problems) The above aspects of the present invention have been achieved by the following manufacturing method. That is, the present invention relates to 3-N-substituted amino-4-bromo-5-pyrazolones represented by formula (1) and formula (If).
This is a method for producing a compound represented by the formula (■), which is characterized by reacting the compound represented by the formula (■) with the compound represented by the formula (■) in the presence of a base.

R.

-H (II) R represents an aryl group, an aliphatic hydrocarbon group, or a heterocycle.

Ro represents an alkyl group, an aryl group, or a heterocyclic group, R1 represents a hydrogen atom or -COR+'(R3' represents an alkyl group, an aryl group, an alkoxy group, or an aryloxy group), and W represents a nitrogen atom, A 5- or 6-membered heterocyclic group, an alkylthio group, or an arylthio group containing three or more members.

The present invention will be explained in detail below.

In the above general formula, R represents an aliphatic hydrocarbon group having 1 to 35 carbon atoms (i.e., a linear or branched alkyl group, an alkenyl group, an alkynyl group, and a cycloalkenyl group), an aryl group, or a heterocyclic group. , these groups may have one or more substituents.

R3 represents an alkyl group, an aryl group, or a heterocyclic group having 1 to 35 carbon atoms.

R1 represents a hydrogen atom or -COR,'(R,' represents an alkyl group, an aryl group, an alkoxy group, or an aryloxy group), and a hydrogen atom is particularly preferred.

W is a 5- or 6-membered heterocyclic group containing two or more nitrogen atoms,
Represents an alkylthio group or an arylthio group.

That is, W-H(n) is a compound represented by the following formula (TV) or (V).

11.・Q・.

N N-H(rv) Here, Q represents a group of nonmetallic atoms necessary to form a 5- or 6-membered heterocycle containing two or more nitrogen atoms.

R, SH(v) Here, R4 is an alkyl group or an aryl group.

Hereinafter, the six groups of the above general formula will be explained in more detail.

In the above general formula, R1 represents any one of the following (a) to (c), preferably (b).

(a) Straight or branched alkyl groups having 1 to 35 carbon atoms, preferably 1 to 22 carbon atoms (e.g. methyl, isopropyl, tert-butyl, hexyl, dodecyl), alkenyl groups (e.g. allyl), cyclic alkyl groups ( (e.g. cyclopentyl, cyclohexyl, norbornyl), aralquit groups (e.g. benzyl, β-phenylethyl),
and cyclic alkenyl groups (e.g. cyclopentenyl, cyclohexenyl).

(These groups include halogen atoms, nitro, cyanoaryl, alkoxy, aryloxy, carboxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, sulfo, acyloxy, sulfamoyl, carbamoyl, acylamino, diacylamino, ureido, thioureido, Urethane, thiourethane, sulfonamide, heterocycle, arylsulfonyloxy, alkylsulfonyloxy, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylsulfinyl, arylsulfinyl, alkylamino, dialkylamino, anilino, N-arylanilino, N (Optionally substituted with a substituent selected from -alkylanilino, N-acylanilino, hydroxy and mercapto groups) (b) Aryl group (e.g. phenyl, α- or β-
naphthyl) and aryl groups with one or more substituents (
Examples of this substituent include alkyl, alkenyl, cyclic alkyl, aralkyl, cyclic alkenyl, halogen atom, nitro, cyano, aryl, alkoxy, aryloxy,
Carboxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl,
Sulfo, acyloxy, sulfamoyl, carbamoyl, acylamino, diacylamino, ureido, thioureido, urethane, thiourethane, sulfonamide, heterocycle, arylsulfonyloxy, alkylsulfonyloxy, arylsulfonyl, alkylsulfonyl, arylthi, alkylthio, alkylsulfinyl, (selected from arylsulfinyl, alkylamino, dialkylamino, anilino, N-alkylanilino, N-arylanilino, N-acylanilino, hydroxy, and mercapto groups).

(c) Heterocyclic group (for example, a 5- or 6-membered heterocyclic ring containing a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom,
Fused-ring heterocyclic groups, such as pyridyl, quinolyl, furyl, benzothiazolyl, oxasilyl, imidazolyl, and naphthoxacylyl) and heterocyclic groups substituted with the substituents listed above for aryl groups.

In the above general formula, R2 is a hydrogen atom, an aryl group (e.g. evaphenyl, alkylphenyl, 2-chloro-5-nitrophenyl, 2-methoxyphenyl, 2chloro-5-tetradecyloxycarbonylaminophenyl, 2-chloro-5
-sulfamoylphenyl, 2-chloro-5-carbamoylphenyl, 2-chloro-5-tetradecanamidophenyl), alkyl groups (e.g., n-butyl, L-butyl, n-octadecyl, n-tetradecyl, benzyl,
cycloalkyl) or heterocyclic groups (e.g. 2-pyridyl,
4-nitro-2-pyridyl, 4-tetradecanamide-
6-pyrimidyl, 1-N dodecyl-5-tetrazolyl)
represents.

In It, W is a 5- or 6-membered heterocyclic group containing two or more N atoms (e.g. pyrazolyl, benzotriazolyl, 5-methoxybenzotriazolyl, 5-carboxybenzotriazolyl). zolyl, 5-phenoxycarbonylbenzotriazolyl), alkylthio groups (e.g. n-butylthio, L-butylthio, n-hexylthio, n-octylthio, n-decylthio, n-dodecylthio) or arylthio groups (benzenethio, 4- t-butylbenzenethio, 20-butoxy-4-t-octylbenzenethio, 2-dodecyloxy-4-methylbenzenethio).

In the above general formula, R and l of 1 COR,' represented by R1 are straight-chain or branched-chain alkyl groups having 1 to 10 carbon atoms (
aryl groups (e.g. phenyl, naphthyl, 4-chlorophenyl, 2,4-6-dolychlorophenyl), alkoxy groups (e.g. methoxy, ethoxy, isopropoxy, hensyloxy) or aryloxy groups (e.g. methyl, isopropyl, ethyl, hexyl), phenyloxy, 2
゜4-chlorophenyloxy, naphthyloxy, 4-nitrophenyloxy).

Details of each step of the present invention are shown below.

3-N-1f-substituted-anilino-5-pyrazolones are already known in JP-A-50-71333, etc., but in the present invention, when R1 is -COR,', the IN used
-Substituted anilino 5-pyrazolones are used as a protecting group and are subsequently removed by a suitable step, such as hydrolysis.

Preferred combinations of substituents when the 5-pyrazolones of the present invention are used as couplers are as follows: 2.4.6-dolichlorophenyl, 2,5 dichlorophenyl, or 2-chloro-4,6-dimethylphenyl; R2 is 2-chloro-5-tetradecanamide anilino R3 is hydrogen atom W is pyrazolyl, 5-phenoxycarbonylbenzotriazolyl, n-dodecylthio, or 2-n-butoxy-4-
t-octylbenzenethio.

The bases used in the production method of the present invention include potassium carbonate, calcium carbonate, sodium carbonate, potassium hydroxide,
These include sodium hydroxide, calcium hydroxide, triethylamine, and sodium methylate.

The manufacturing conditions of the present invention will be explained in detail.

The compound of formula (I[l) can be obtained by the following method.

When formula (n) is a heterocycle, add 1 to 5 equivalents of the compound of formula (n) to the compound of formula (I), add 1 to 5 equivalents of a base, and heat at 50 to 120°C.
Preferably, the reaction can be carried out in the temperature range of formula (II
) and the base are used in equivalent amounts, and the base used is potassium carbonate, sodium carbonate, or calcium carbonate.

When II (II) is a mercaptan, add 1 to 3 equivalents of formula (If) to formula (1), add 1 to 3 equivalents of a base, and react in a temperature range of 20 to 100'C. I can do it. Preferably, the compound of formula (1) is
It is important to use an equivalent amount of the compound () as the base, and to use a methanol solution of potassium hydroxide or sodium hydroxide, a methanol solution containing sodium methylate, or an ethanol solution containing sodium ethylate as the base.

Reaction solvents include halogenated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (ethyl ether, dioxane, tetrahydrofuran, etc.), aprotic polar solvents (dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone), Alcohols (ethanol, methanol, etc.), aromatic hydrocarbons (benzene, toluene, etc.), acetonitrile, etc. can be used.

When using a carbonate as a base, it is preferable to use an aprotic polar solvent such as N-methylpyrrolidone which has excellent solubility of the carbonate.

The reaction is completed after about 1 to 24 hours.

After the reaction is completed, it is extracted with a solvent with high extraction ability such as ethyl acetate or chloroform, and washed with alkaline water to remove excess formula (I).
The compound represented by formula (III) can be obtained by removing the compound I) and the reaction solvent by washing with water, then removing the extraction solvent, and performing crystallization.

Next, examples of 5-pyrazolones that can be produced according to the present invention will be shown.

death! l01 11° death! 12° 16° Shit Hs 1B.

23°20°21°24°Example 1 Synthesis examples of exemplary couplers (1), (2) and (3) are shown below.

Step 1; 1-(2,4,6-dolichlorophenyl)-3
Synthesis of -N-i-butoxycarbonyl-(2-chloro-5-tetradecanamido)anilino-5-oxo-2-biraprine: ShiL 1-(2,4,6-1lichlorophenyl)-3(2-chloro -5-tetradecanamido)anilino-5-oxo-2-pyrazoline 122. 8 g (02 mol) was dissolved in 300 mff1 of toluene and heated to reflux at 140°C on an oil bath. Add to this 81% isobutyl chloroformate. 9g
(0.6 mol) was added dropwise over 40 minutes. After further reaction under heating and reflux for 4 hours, toluene was removed under reduced pressure,
250 mjl of acetrinyl for the residual fragrance oil! White crystals with a melting point of 124-126°C were obtained in a yield of 85%.

Step If: 1-(2,4,6-dolichlorophenyl)-
3-N-i-butoxycarbonyl-(2-chloro-5-
Synthesis of (tetradecanamido)anilino-4-bromo-5-oxo-2-biraprine: 107.1 g (0.15 mol) of the compound obtained in the above step -① was added to 500 m! ! was dissolved in methylene chloride, and 24 g (0.15 mol) of bromine was added dropwise over 30 minutes while cooling with water, and stirring was continued for 30 minutes after the dropwise addition.

After the reaction was completed, water was added and the methylene chloride layer was thoroughly washed with water.

After about 300 ml of methylene chloride was distilled off at normal pressure, 600 ml of acetonitrile was added and crystallized to give a melting point of 173.
White crystals at ~175°C were obtained in a yield of 96°3%.

Step m: Synthesis of 1-(2,4,6-1-lichlorophenyl)-3-(2-chloro-5-tetradecanamido)anilino-4-bromo-5-oxo-2-virapurine: Shi! Compound 23 obtained in step ① above. 7g (0°03
60 ml of methanol was added to the mixture (mol), and then a solution of 15.4 g (0.27 mol) of potassium hydroxide dissolved in 60 m 2 of water was added, and the mixture was heated and reacted at 60°C for 1 hour.

Next, add 500 mjl of the reaction solution! The precipitated solid was collected by filtration and washed with water to yield 21 g of white crystals (Wet).
Obtained.

Melting point, 73°C (decomposed). Since this white crystal was unstable, it was used in the next step without drying.

coupler 1 person 1, 2. 3-benzotriazole 14.23g (0
, 12 mol), N-methylpyrrolidone 120°6mff
1. Prepare 8.51 g (0.06 mol) of potassium carbonate, heat and stir on an oil bath at 90 to 100'C for 1 hour, and then proceed to step ①.
21 g of the compound obtained above was added, and the mixture was heated and stirred for 2.5 hours. After cooling, 200 ml of ethyl acetate was added to the reaction solution to dilute it, and then 120 ml of an aqueous solution containing 6.4 g of potassium carbonate was added.
The ethyl acetate layer was washed three times with No. 1 to remove excess benzotriazole.

Next, 5 ml of hydrochloric acid and 100 mff1 of water are added to wash the ethyl acetate layer, and crystals are precipitated. The precipitated crystals were collected by filtration, and acetonitrile/ethyl acetate = 50mf (1/1)
The light brown coupler (1) after washing with melting point 121-128
Obtained in 50% yield at °C (decomposition).

Kaboo 2 A hexyl mercaptan 1.18 g (0.0 fmol),
28% sodium methylate methanol solution 1.93g
(0.01 mol) 1, N-methylpyrrolidone 10. m
Prepare 4 and heat to 60°C.

Next, compound 7 obtained in step (1). After adding 9 g (0.01 mol) and stirring at 60°C for 2 hours, ethyl acetate loOmj! , 100 mf of water, and 5 ml of hydrochloric acid were added to perform extraction, washing with water, and liquid separation. Furthermore, the ethyl acetate layer was washed twice with water, and the ethyl acetate was distilled off under reduced pressure.
The precipitated white crystals were collected by filtration to obtain coupler (2) (melting point, 104-110°C) in a yield of 74.5%.

Kapoo 3 people p-tert-butylbenzenethiol 3.33g (0
, 02 mol), 28% sodium methylate methanol solution 3.87 g (0.02 mol), N-methylpyrrolidone 10. Pour ml and heat to 60°C. Next process ■
Add 7.9 g (0.01 mol) of the compound obtained in
After heating and stirring at 60°C for 4 hours, add 100mj of ethyl acetate.
2. Add 100 mff of water and 5 mf of hydrochloric acid, extract.
Washed with water and separated.

Furthermore, the ethyl acetate layer was washed twice with water, and the ethyl acetate was distilled off under reduced pressure. Ethyl acetate/acetonitrile = 20mf/20ml was added to the residual oily substance, and the precipitated white crystals were collected by filtration, with a yield of 83.4%. Coupler (3) (melting point, 125.O
~127.0°C) was obtained.

Comparative experimental data (reaction example using 4-chloro form instead of 4-pro form obtained in step ①) Coupler 2 1.18 g (0.01 mol) of hexyl mercaptan, 2
8% sodium methylate methanol solution 1.93g
(0.01 mol) and N-methylpyrrolidone 60
Heat to °C. Next, 6.49 g (0.01 mol) of 1-(2°4.6-)lichlorophenyl)-3-(2-chloro-5-tetradecanamido)anilino-4-chloro-5-oxo-2-pyrazoline was added and a heating reaction was carried out at 60°C. However, even after 10 hours of heating, 80% of the raw material chloride remained in the reaction solution, and only 10% of coupler 2 was formed, and even after post-treatment, coupler (2) remained crystallized. could not be obtained as such.

〔Effect of the invention〕

According to the present invention, a 3N-monosubstituted amino-4-substituted-5-pyrazolone coupler is converted into a pyrazolone-
It can be obtained in extremely high yield without protecting the 3-position with an acyl group.

Claims (2)

[Claims] (1) 3-N-substituted amino-4- represented by formula (I)
Formula (I), which is characterized by reacting bromo-5-pyrazolones with a compound represented by formula (II) in the presence of a base.
II) A method for producing the compound shown in II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) W-H(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) Here, R_1 represents an aliphatic hydrocarbon group, an aryl group, or a heterocyclic group. where R_3 represents an alkyl group, aryl group or heterocyclic group, R_3 is a hydrogen atom or -COR_3
'(R_3' represents an alkyl group, aryl group, alkoxy group, or aryloxy group), W represents a 5- or 6-membered heterocyclic group containing two or more nitrogen atoms, an alkylthio group, or an arylthio group. . (2) R_3 is a hydrogen atom, W-H(II) is the formula (I
V) or formula (V), ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (Q is a compound necessary to form a 5- or 6-membered heterocycle containing two or more nitrogen atoms. R_4SH (V) R_4 represents an alkyl group or an aryl group) and the base (III) is an alkali hydroxide, an alkali metal carbonate, a trialkylamine or an alkali metal alcoholade ( The manufacturing method described in 1).