JPH0812655A - Substituted acetyl compound - Google Patents

Abstract

PURPOSE:To obtain a new compound useful as a synthetic intermediate for yellow couplers used as a recording material and as a synthetic intermediate for medicines. CONSTITUTION:This substituted acetyl compound is expressed by the formula R<1>-COCH2R<2> [R<1> is tert-butyl or phenyl having a 1-18C alkoxy at the p-position; R<2> is formula I or II (R<3> is a 1-18C alkoxy or anilino; R<4> and R<5> are each a 1-18C alkyl)]. The compound is obtained by reacting an alpha-haloacetyl compound of the formula, R<1>COCH2X (X is a halogen) with a heterocyclic ring containing nitrogen in the presence of a base (e.g. triethylamine) in a solvent (e.g. acetonitrile) at 0-140 deg.C for 0.5-10hr. A yellow coupler derived from the acetyl compound is useful as the yellow coupler for a silver halide color photographic material, especially color photographic paper and readily prepared in a short step.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel substituted acetyl compound used as a synthetic intermediate in the production of yellow couplers used in recording materials such as silver halide color photographic light-sensitive materials and the production of pharmaceutical intermediates. .

[0002]

2. Description of the Related Art Many 2-equivalent couplers having a substituted imidazolyl group at the coupling position are known as yellow couplers used in color photographic light-sensitive materials. (U.S. Pat. No. 4,046,575; U.S. Pat. No. 4,049,
458; U.S. Pat. No. 4,133,958; U.S. Pat. No. 4,032,347). As a synthesis method thereof, Scheme 1 is known as shown below. That is, it is general that β-ketoester compound 1 is used as a key intermediate, β-ketoanilide compound 2 is obtained by reaction with an aniline compound, and then halogenation (obtaining 3 ) and substitution reaction (obtaining 4 ) are performed. .

[0003]

[Chemical 4]

However, from the β-ketoester compound, β-
High temperature is required in the step of converting into a ketoanilide compound, partial reductive dehalogenation occurs in the step of introducing a leaving group, it is necessary to use the leaving group in excess.
Although attempts have been made to improve this method (see US Pat. No. 4,230,851), a satisfactory method has not yet been developed.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to overcome the conventional problems associated with the synthesis of yellow couplers and to usefully synthesize yellow couplers used in silver halide color photographic light-sensitive materials. It is to provide a novel synthetic intermediate.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to overcome the problems in the production of conventional yellow couplers, and as a result, (1) general formula (I)

[0007]

Embedded image

(Wherein R ¹ represents a tert-butyl group or a phenyl group having an alkoxy group having 1 to 18 carbon atoms in the para position, and R ² represents a group represented by the general formula (II) or the general formula (III) ) Represents a group represented by.)

[0009]

[Chemical 6]

[0010]

[Chemical 7]

The substituted acetyl compound represented by the formula (R ³ represents an alkoxy group having 1 to 18 carbon atoms or an anilino group, and R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 18 carbon atoms). It was found that it was suitable as a synthetic intermediate of a yellow coupler. The substituted acetyl compound of the present invention is preferably (2) the general formula (I).
In, represented by the general formula (II) 1-imidazolyl group has a second place -COR ³ group, wherein R ³ is an anilino group (1) substituted acetyl compound as claimed in claim, and ( 3) In the general formula (I), the general formula (II)
In represented by 1-imidazolyl group has a -COR ³ group in the 4-position or 5-position, R ³ is a substituted acetyl compound of an alkoxy group having 1 to 18 carbon atoms (1) above, wherein.

The compound of the present invention will be described in detail below. R ¹ is a tert-butyl group or an alkoxy group having 1 to 18 carbon atoms in the para position (eg, methoxy, ethoxy,
It represents a phenyl group having hexadecyloxy and octadecyloxy). R ¹ is more preferably tert-
It represents a butyl group, a p-methoxyphenyl group, a p-hexadecyloxyphenyl group, and a p-octadecyloxyphenyl group. R ¹ is particularly preferably a tert-butyl group,
Represents a p-hexadecyloxyphenyl group. R ³ represents an alkoxy group having 1 to 18 carbon atoms, preferably 1 to 6 carbon atoms (eg, methoxy, hexyloxy, hexadecyloxy) or an anilino group. When R ³ represents an alkoxy group, the substitution position of the —COR ³ group is 4 in the imidazole ring.
It is more preferable that the position is 5 or 5. At this time, R ¹
Is particularly preferably a tert-butyl group. R ³
Is an anilino group, it is more preferable that the substitution position of the —COR ³ group is the 2-position of the imidazole ring. R
⁴ and R ^{5 each} represent an alkyl group having 1 to 18 carbon atoms (eg, methyl, ethyl, propyl, butyl, octadecyl). R ⁴ and R ⁵ are preferably lower alkyl groups, particularly preferably methyl groups. Particularly preferable combinations of substituents in the compound of the present invention are shown below. (1) R ¹ represents a tert-butyl group or a phenyl group having an alkoxy group having 1 to 18 carbon atoms in the para position,
R ² represents a 1-imidazolyl group having a —COR ³ group at the 2-position, and R ³ represents an anilino group. (2) R ¹ represents a phenyl group having an alkoxy group having 1 to 18 carbon atoms in the para position, R ² represents the general formula (III), and R ⁴ and R ⁵ each represent a lower alkyl group. (3) In (2), R ⁴ and R ⁵ represent a methyl group. (4) R ¹ represents a tert-butyl group or a phenyl group having an alkoxy group having 1 to 18 carbon atoms in the para position,
R ² represents the general formula (II), —COR ³ represents the 4-position or 5-position of the imidazole ring, and R ³ represents an alkoxy group having 1 to 18 carbon atoms. (5) In the above (4), R ¹ represents a tert-butyl group.

Next, a method for producing the compound of the present invention will be described. As shown below, the compound of the present invention can be obtained in good yield by reacting an α-haloacetyl compound with a nitrogen-containing heterocycle under basic conditions. The reaction molar ratio of the α-haloacetyl compound and the nitrogen-containing heterocycle is usually 1: 5 to 5: 1, preferably 1: 2 to 2: 1.

[0014]

Embedded image

As the base used in the reaction, inorganic bases such as sodium hydride, potassium tert-butoxide, sodium carbonate, potassium carbonate, sodium methoxide, sodium ethoxide, sodium hydroxide and potassium hydroxide, 1,8- Diazabicyclo [5.4.0]-
Organic bases such as 7-undecene (DBU), 1,5-diazabicyclo [4.3.0] -5-nonene (DBN) N, N-diisopropylethylamine and triethylamine can be given. The amount of the base used is not particularly limited, but is usually 0.5 to 2 equivalents, preferably 0.8 to 1.2 equivalents, relative to the nitrogen-containing heterocycle. As the reaction solvent, ether, tetrahydrofuran (THF), dioxane acetonitrile, N, N-dimethylformamide (DMF),
N, N-dimethylacetamide (DMAc), 1,3-
Dimethyl-2-imidazolidone (DMI), 1-methyl-2-pyrrolidone (NMP) and the like are used. The reaction temperature is 0 ° C to 140 ° C, preferably 10 to 100 ° C. The reaction time is not limited, but usually 0.5 to 10 hours,
It is preferably 1 to 5 hours.

The compounds of the present invention are useful as synthetic intermediates for photographic yellow couplers as shown below.

[0017]

[Chemical 9]

The compound of the present invention contains 0.5 mol to 2 mol of 1 mol thereof.
By reacting with an isocyanate compound or a phenylurethane compound, which is a precursor thereof, in a molar amount, preferably 0.8 to 1.2 mol, in the presence of a base, a yellow coupler can be obtained in good yield. The isocyanate compound can be easily synthesized from the corresponding aniline derivative and phosgene. The phenylurethane compound can be easily synthesized from the corresponding aniline derivative and phenyl chlorocarbonate. Examples of the base used include LDA (lithium diisopropylamide) sodium hydride, potassium tert-butoxide, sodium methoxide and the like.

The amount of base used is based on the compound of the present invention.
0.9 to 5 mol, preferably 1 to 3 mol is used. A method for synthesizing a β-ketoanilide compound from an acetyl compound and an isocyanate compound is known, and the following ones are known as typical ones.

[0020]

[Chemical 10]

Specific examples of the compound of the present invention are shown below.
The compounds of the present invention are not limited to these.

[0022]

[Table 1]

[0023]

[Table 2]

[0024]

[Table 3]

[0025]

[Table 4]

[0026]

[Table 5]

[0027]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto.

Example 1. Synthesis of (9) First, 2-phenylcarbamoylimidazole was synthesized by the method described in the literature (J. Org. Chew., 4
2 , 3925 (1977)). That is, 13.6 g (0.2 mol) of imidazole 2 and phenyl isocyanate 2
To 3.8 g (0.2 mol), 50 m of o-nitrotoluene
1 was added, and the mixture was heated with stirring at an oil bath temperature of 230 ° C. for 1.5 hours. The mixture was returned to room temperature, 200 ml of carbon tetrachloride was added, and the precipitated crystals were filtered to obtain 26.0 g of 2-phenylcarbamoylimidazole as crude crystals. By dispersing in 100 ml of acetonitrile and filtering, 18.5 g of a purified product of 2-phenylimidazole was obtained. Yield 50
%. Then, 3.74 g of 2-phenylcarbamoyl
(0.02 mol), 700 pinacolone 3.0 g (0.0
(22 mol) was dispersed in 50 ml of acetonitrile, 3.1 ml of triethylamine was added, and the mixture was heated under reflux for 15 hours. The mixture was returned to room temperature, ethyl acetate water was added, the layers were separated, washed with water, and the solvent was evaporated. Add 20 ml of acetonitrile,
The mixture was heated under reflux for 20 minutes, returned to room temperature, and the precipitated crystals (recovered 2-phenylcarbamoylimidazole) were filtered (1.0 g), the filtrate was concentrated, and purified by silica gel column chromatography (n-hexane / ethyl acetate =
After 2/1), crystallization was performed from n-hexane to obtain 3.2 g of compound (9). Yield 56%. Melting point 141-143 ° C ¹ H-NMR (300 MHz: COCl ₃ ) δppm 1.31 (s, 9H) 5.59 (s, 2H) 6.95 (s, 1H) 7.12 (m, 2H) 7. 32 (m, 2H) 7.60 (d, 2H, J = 8.0Hz) 9.23 (bs, 1H)

Example 2. Synthesis of (12) Example 1. (12) was synthesized by a method similar to. Melting point 178-180 ° C. ¹ H-NMR (200 MHz: COCl ₃ ) δppm 3.89 (s, 3H) 6.02 (s, 2H) 6.98 (d, 2H, J = 8.7 Hz) 7.05- 7.4 (m, 5H) 7.60 (d, 2H, J = 8.0Hz) 8.02 (d, 2H, J = 8.7Hz) 9.28 (bs, 1H)

Example 3. Synthesis of (15) Example 1. (15) was synthesized by a method similar to. Melting point 120-123 ° C. ¹ H-NMR (200 MHz: COCl ₃ ) δppm 0.89 (t, 3H, J = 6.3 Hz) 1.27 (m, 26H) 1.82 (m, 2H) 4.05 ( t, 2H, J = 6.3Hz) 6.03 (s, 2H) 6.97 (d, 2H, J = 10.0Hz) 7.1-7.4 (m, 5H) 7.59 (d, 2H, J = 8.0 Hz) 8.00 (d, 2H, J = 10.0 Hz) 9.30 (bs, 1H)

Example 4. Synthesis of (22) 2.29 g (0.01 p-methoxyphenacyl bromide)
Mol) and 1.80 g (0.01 mol) of theophylline are dispersed in 30 ml of acetonitrile, and triethylamine 1.
6 ml was added, and the mixture was stirred at room temperature for 20 hours. 50m water
l was added, and the precipitated crystals were filtered to obtain 2.8 g of (22) as colorless crystals. Yield 85%. Melting point 201-203 ° C. ¹ H-NMR (200 MHz: COCl ₃ ) δppm 3.37 (s, 3H) 3.64 (s, 3H) 3.93 (s, 3H) 5.79 (s, 2H) 7. 00 (d, 2H, J = 9.0 Hz) 7.66 (s, 1H) 8.01 (d, 2H, J = 9.0 Hz)

Example 5. Synthesis of (24) 27.2 g (0.2 mol) of p-hydroxyacetophenone and 61.0 g (0.2 mol) of hexadecyl bromide.
Was dissolved in 300 ml of N, N-dimethylformamide,
To this was added 27.8 g (0.2 mol) of potassium carbonate,
The mixture was stirred at an inner temperature of 80 to 90 ° C for 4 hours. Return to room temperature,
500 ml of water was added, and the precipitated crystals were filtered to obtain 70.0 g of p-hexadecyloxyacetophenone. Yield 9
7%. 27.5 g (0.11 mol) of copper (II) bromide was dispersed in 125 ml of ethyl acetate, and p-hexadecyloxyacetophenone 1 obtained above was heated to reflux.
A solution prepared by dissolving 8.0 g (0.05 mol) in 60 ml of chloroform was added dropwise over 30 minutes. 2 more after dropping
The mixture was heated under reflux for a period of time, returned to room temperature, the precipitated crystals of copper (I) bromide were filtered, ethyl acetate was added to the filtrate, and the mixture was washed twice with water. It was dried with magnesium sulfate, the solvent was distilled off, and crystallization was performed with methanol to obtain 20.0 g of p-hexadecyloxyacetophenone. Then, 4.39 g of p-hexadecyloxyacetophenone (0.01
1.80 g (0.01 mol) of theophylline was added to 30 mol, and triethylamine 1.
6 ml was added, and the mixture was stirred at room temperature for 20 hours. Add water,
The precipitated crystals are filtered to obtain 4.24 g of compound (24).
Obtained. 79% yield. Melting point 109-112 ° C. ¹ H-NMR (200 MHz: COCl ₃ ) δppm 0.88 (t, 3H, J = 6.7 Hz) 1.28 (m, 26H) 1.80 (m, 2H) 3.35 ( s, 3H) 3.63 (s, 3H) 4.04 (t, 2H, J = 6.7Hz) 5.75 (s, 2H) 6.96 (d, 2H, J = 9.3Hz) 7. 65 (s, 1H) 7.98 (d, 2H, J = 9.3 Hz)

Example 6. Synthesis of (28) or (29) First, according to the method in the literature (Synthesis, 1975 , 162), 4-
Methoxycarbonylimidazole was synthesized. Then
4-methoxycarbonylimidazole 1.10 g (8.
7 mmol), 1.20 g of α-chloropinacolone (8.
7 mmol) N, N-dimethylformamide 30 ml
Was dissolved in water, 1.32 g (9.5 mmol) of potassium carbonate was added thereto, and the mixture was stirred at room temperature for 20 hours under a nitrogen atmosphere. 50 ml of ethyl acetate and 100 ml of water were added, liquid separation was carried out, washing with water was carried out twice, and the solvent was distilled off. To the obtained oily substance, 30 ml of n-hexane and 15 ml of ethyl acetate were added, and the precipitated crystals were filtered to obtain the desired (28) or (29) as a single substance. Melting point 153-155 ° C. ¹ H-NMR (300 MHz: CDCl ₃ ) δppm 1.26 (s, 9H), 3.89 (s, 3)
H), 4.96 (s, 2H), 7.45 (s, 1H),
7.53 (s, 1H) Next, typical examples of the yellow coupler synthesized from the compound of the present invention will be shown.

[0034]

[Table 6]

[0035]

[Table 7]

The melting points of typical yellow couplers are shown below. (Y-3) 116-118 [deg.] C. (Y-4) 83-86 [deg.] C. (Y-5) 109-111 [deg.] C. As described above, the compound of the present invention is a useful synthetic intermediate of an imidazole-elimination type 2 equivalent yellow coupler. It is the body. Reference example. Synthesis of yellow coupler (Y-5) using compound (24) of the present invention 15.3 g (0.1 mol) of 2,5-dimethoxyaniline
Was dispersed in 100 ml of acetonitrile, and 13.4 ml of phenyl chlorocarbonate was added dropwise over 10 minutes under ice cooling. Three
After stirring for 0 minutes, 8.3 ml of viridine was added dropwise over 10 minutes. React for an additional 1 hour, add ethyl acetate and water,
Liquid separation and washing were performed, and the solvent was distilled off. Methylene chloride 200
ml, 50 g of silica gel were added and stirred, and the coloring component was adsorbed on silica gel, eluted with methylene chloride, concentrated, and then crystallized with n-hexane to give N- (2,5-dimethoxyphenyl) phenoxycarboxylic acid. Amide 24.3
g was obtained. Yield 89%, melting point 92-94 ° C. Then 0.26 g (6.6 mmol) of sodium hydride (60%)
Was dispersed in 20 ml of N, N-dimethylformamide, and under a nitrogen atmosphere, 1.62 g (3 mmol) of the compound (24) of the present invention and N- (2,5-dimethoxyphenyl) phenoxycarbonamide (0.1) synthesized above were synthesized. 82 g was added, and the mixture was stirred at room temperature for 3 hours. Water and ethyl acetate were added, liquid separation,
After washing with water, the solvent was distilled off and silica gel column chromatography (n-hexane / ethyl acetate = 1/1 to 1/2).
And then crystallized with n-hexane,
1.20 g of a yellow coupler (Y-5) was obtained. Yield 5
6%. Melting point 109-111 ° C. ¹ H-NMR (200 MHz: COCl ₃ ) δppm 0.88 (t, 3H, J = 6.3 Hz) 1.28 (m, 26H) 1.82 (m, 2H) 3.46 ( s, 3H) 3.63 (s, 3H) 3.70 (s, 3H) 3.72 (s, 3H) 4.04 (t, 2H, J = 6.3Hz) 6.57 (dd, 1H, J = 8.0, 3.3 Hz) 6.75 (d, 1H, J = 8.0 Hz) 7.02 (d, 2H, J = 8.7 Hz) 7.77 (s, 1H) 7.90 ( d, 1H, J = 3.3Hz) 8.12 (d, 2H, J = 8.7Hz) 8.40 (s, 1H) 8.60 (s, 1H)

The acetyl compound of the present invention is a starting material R ²
-H is inexpensive and easily available, and thus a 2-equivalent yellow coupler can be provided at low cost. Further, (Y-5), which is a typical example of a yellow coupler derived from the acetyl compound of the present invention, is known to be a highly active 2-equivalent yellow coupler (US Pat. No. 4,032,347).
No.) It is particularly useful as a yellow coupler for a color photographic light-sensitive material, particularly a color photographic paper, because it can reduce the amount of silver halide used, and is particularly useful for cost reduction.

[0038]

The compound of the present invention is used as a synthetic intermediate capable of synthesizing a yellow coupler by a simple method. According to the compound of the present invention, the yellow coupler can be easily produced on an industrial scale in a short process.

Claims (3)

[Claims] 1. A compound of the general formula (I) (In the formula, R ¹ is a tert-butyl group, or 1 to 1 carbon atoms.
18 represents a phenyl group having an 18 alkoxy group in the para position, and R ² represents a group represented by the general formula (II) or a general formula (I
It represents a group represented by II). ) A substituted acetyl compound represented by: Embedded image Embedded image (R ³ represents an alkoxy group having 1 to 18 carbon atoms or an anilino group, and R ⁴ and R ⁵ each independently have 1 carbon atom.
Represents an alkyl group of -18. ) 2. The substituted acetyl group according to claim 1, wherein in the general formula (I), the 1-imidazolyl group represented by the general formula (II) has a —COR ³ group at the 2-position and R ³ is an anilino group. Compound. 3. In the general formula (I), the 1-imidazolyl group represented by the general formula (II) has a —COR ³ group at the 4-position or the 5-position, and R ³ is an alkoxy group having 1 to 18 carbon atoms. The substituted acetyl compound according to claim 1, which is