JPH08310999A - Production of 4-halo-1-naphthol compound - Google Patents

Abstract

PURPOSE: To easily obtain at a low cost in high purity and yield the subject compound useful as e.g. a naphthol coupler to be used for silver halide color photograph photosensitive materials, by using a specific hydantoin. CONSTITUTION: This compound of formula I (R<1> is an alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylsulfonyl or arylsulfonyl; R<2> is an alkylamino, arylamino, aryloxy or hydroxyl; (n) is 0 or 1; X<1> is a halogen) is obtained by halogenating a compound of formula II with a 1,3- dihalo-5,5-dimethylhydantoin (e.g. 1,3-dichloro-5,5-dimethylhydantoin) in an organic solvent other than a halogen-based one (e.g. toluene, ethyl acetate) at e.g. 15-30 deg.C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel method for producing a 1-naphthol cyan coupler used in a silver halide color photographic light-sensitive material and a synthetic intermediate thereof.

[0002]

2. Description of the Related Art Phenols and naphthols are mainly used as cyan couplers used in color photographic light-sensitive materials. From the viewpoint of silver saving, a halogen atom or an alkoxy group is used during a coupling reaction with an oxidized product of a developing agent. So-called 2-equivalent couplers are widely used in which an aryloxy group, an alkylthio group, a 5-membered heterocyclic group and the like are released.

Especially for color negative films, naphthols, which have a high coupling rate with the oxidized product of the developing agent, are often used. The 2-equivalent naphthol coupler can be synthesized by various synthetic methods. As shown in the following scheme, the 4-halo-1-naphthol compound is a coupler itself and a coupler which leaves an alkoxy group or the like. It occupies an important position as a synthetic intermediate (see JP-A-62-123158).

[0004]

Embedded image

(R ¹ : alkylcarbonyl group, arylcarbonyl group, etc., R ² : alkylamino group, arylamino group, etc., R ³ : alkyl group, n: 0 or 1, X
¹ : Halogen atom) As a synthetic method thereof, conventionally, when X ¹ is a chlorine atom, chlorine or sulfuryl chloride is used as a halogenating agent.
^{When 1} is a bromine atom, bromine is often used.

However, when these halogenating agents are used, the reactivity of the halogenating agents is so high that they are partially dihalogenated, which may result in the formation of colored components such as naphthoquinone. Further, since hydrogen halide is generated, the decomposition thereof may occur when the acid has a weak substituent.
Furthermore, halogen-based solvents such as methylene chloride, which are associated with environmental problems, are often used because they are inert to these halogenating agents.

[0007] As described above, the use of a conventionally known halogenating agent causes a side reaction, which lowers the purity of the target product, and therefore is desired to be improved. Further, recently, environmentally friendly technical development has been strongly called for, and it is desired to limit the use of halogen-based solvents as much as possible.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems based on the above-mentioned demand, and to provide a naphthol coupler used in a silver halide color photographic light-sensitive material and a naphthol coupler thereof. It is an object of the present invention to provide a method for producing a synthetic intermediate conveniently, at low cost, in high purity and in good yield.

[0009]

The objects of the present invention have been achieved by the following method. That is, the present invention uses (1) 1,3-dihalo-5,5-dimethylhydantoin represented by the following general formula (II): 4-halo-1
-A method for producing a naphthol compound,

[0010]

[Chemical 4]

(Wherein R ¹ represents an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group or an arylsulfonyl group, and R ² represents an alkylamino group, an arylamino group or an aryloxy group. Represents a group or a hydroxy group, n represents 0 or 1, and X ¹ represents a halogen atom.) (2) 1,3-containing a compound represented by the following general formula (I)
Halogenated with dihalo-5,5-dimethylhydantoin to give 4-halo-1 represented by the general formula (II).
A naphthol compound, the production method according to item (1),

[0012]

Embedded image

(Wherein R ¹ represents an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group or an arylsulfonyl group, and R ² represents an alkylamino group, an arylamino group or an aryloxy group. Represents a group or a hydroxy group, n represents 0 or 1, and (3) 1,3-dihalo-5,5-dimethylhydantoin is 1,3-dichloro-5,5-dimethylhydantoin or 1,3- Dibromo-5,5-dimethylhydantoin (1) or (2), wherein the production method is (4) an organic solvent other than a halogen-based solvent is used (1), ( (2) or the production method described in (3), (5) using toluene or ethyl acetate as a solvent ( 1), (2) or (3) the production method according to the above item, and (6) 1,3-dihalo-5,5-dimethylhydantoin is 1,3-dichloro-5,5-dimethylhydantoin The manufacturing method according to (1), (2), (4) or (5) is provided.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION First, the compound will be described in detail. In the definitions of the general formulas (I) to (II) in the present specification, alkyl and aryl in each group are meant to include both substituted and unsubstituted unless otherwise specified.

R ¹ is preferably a substituted or unsubstituted alkylcarbonyl group having 2 to 18 carbon atoms (eg, acetyl,
Trifluoroacetyl), preferably a substituted or unsubstituted arylcarbonyl group having 7 to 18 carbon atoms (for example, benzoyl, pentafluorobenzoyl, p-nitrobenzoyl), preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 18 carbon atoms. A group (for example, methoxycarbonyl, i-butoxycarbonyl, 2-ethylhexyloxycarbonyl), preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 18 carbon atoms (for example, phenoxycarbonyl, naphthoxycarbonyl), preferably 1 carbon atom ~ 18 substituted or unsubstituted alkylsulfonyl group (for example, methanesulfonyl, butanesulfonyl),
Or preferably a substituted or unsubstituted arylsulfonyl group having 6 to 18 carbon atoms (for example, benzenesulfonyl, p
-Toluenesulfonyl). R ¹ more preferably represents an alkoxycarbonyl group having 2 to 18 carbon atoms,
Particularly preferably, it represents an i-butoxycarbonyl group. R
² is preferably a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms (eg, propylamino, butylamino), preferably a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms (eg, anilino, naphthylamino) , Preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms (eg, phenoxy, p-nitrophenoxy) or a hydroxy group.

The substituent may be any known substituent for a photographic cyan coupler, and is preferably a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms (eg methoxy, dodecoxy, octadecoxy). Is a substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms (for example, phenoxy, 2,4-di-tert-
Amylphenoxy), preferably a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms (eg, methyl, ethyl, propyl, octyl), preferably a substituted or unsubstituted aryl group having 6 to 26 carbon atoms (eg, phenyl, naphthyl). ), A halogen atom (for example, a fluorine atom, a chlorine atom),
Cyano group, nitro group, preferably substituted or unsubstituted alkylsulfonyl group having 1 to 18 carbon atoms (for example, methanesulfonyl, butanesulfonyl, hexadecanesulfonyl), preferably substituted or unsubstituted alkoxycarbonyl group having 2 to 18 carbon atoms (Eg methoxycarbonyl,
Ethoxycarbonyl) and the like.

R ² is preferably unsubstituted C 1-18
Of 1 to 4 carbon atoms, an alkylamino group of 1 to 18 carbon atoms or an aryloxy group of 6 to 18 carbon atoms, preferably an alkoxy group of 1 to 18 carbon atoms. And an anilino group, a phenoxy group or a hydroxy group, particularly preferably an unsubstituted alkylamino group having 1 to 18 carbon atoms, 3-dodecoxypropyl group, 3- (2,4-di-tert-amylphenoxy). It represents a propylamino group, a 4- (2,4-di-tert-amylphenoxy) butylamino group, a phenoxy group or a hydroxy group. n is 0 or 1
Represents X ¹ represents a halogen atom, preferably a chlorine atom or a bromine atom. X ¹ is 1,3-dihalo-5,5
-Corresponding to a halogen atom possessed by dimethylhydantoin. R ¹ represents an alkoxycarbonyl group having 2 to 18 carbon atoms (n = 1), and R ² has 1 to 1 carbon atoms
A combination in which an alkoxy group having 8 or an arylamino group having 6 to 18 carbon atoms is substituted with an alkylamino group having 1 to 4 carbon atoms and X ¹ is a chlorine atom or a bromine atom is particularly preferable. The compounds represented by formula (I) are disclosed in JP-A-62-123158, JP-B-45-6993,
No. 50-14523, Japanese Examined Patent Publication No. 5-21223, etc., and the production thereof can be easily carried out by the method described therein.

Next, the manufacturing method will be described in detail. The 1,3-dihalo-5,5-dimethylhydantoin used as the halogenating agent in the present invention can be easily obtained by halogenating 5,5-dimethylhydantoin under alkaline conditions, and NBS (N- It is a compound that can be obtained at a lower cost than bromosuccinimide). More specifically, 1,3-dichloro-5,5-dimethylhydantoin, 1-bromo-3-chloro-5,5-
Dimethylhydantoin, 3-bromo-1-chloro-5,
5-dimethylhydantoin, 1,3-dibromo-5,5
-Dimethylhydantoin is preferably used. 1,3
-Dichloro-5,5-dimethylhydantoin, 1,3-
Dibromo-5,5-dimethylhydantoin is particularly preferably used. Two halogen atoms in these 1,3-dihalo-5,5-dimethylhydantoins can be effectively used for halogenation, and 1 mol of the 4-halo-1-naphthol compound represented by the general formula (II) is used. Often, use of about 0.5 moles is sufficient to obtain Preferably 0.4 to 1.2 mol, particularly preferably 0.45 to
0.6 mol is used. Chem. Products
and Chemical News, 23 , 299.
(1960) discloses bromination of phenol using 1,3-dibromo-5,5-dimethylhydantoin, but the reaction is carried out in a halogenated hydrocarbon solvent or water, and other than halogenated solvents. No mention is made of carrying out the reaction in a solvent. As the reaction solvent, ester solvents such as methyl acetate and ethyl acetate, halogen solvents such as methylene chloride and dichloroethane, aromatic hydrocarbon solvents such as benzene and toluene,
Amide solvents such as N, N-dimethylacetamide and DMI (1,3-dimethyl-2-imidazolidone), ketone solvents such as acetone and methyl ethyl ketone, and acetonitrile are used. The above organic solvents other than the halogen-based solvent are preferably used. Particularly preferably toluene or ethyl acetate is used as solvent. In addition,
As the reaction solvent, this reaction may be carried out as it is in the solvent used for producing the compound represented by the general formula (I), but it is preferable to carry out the reaction after taking out the compound of the general formula (I). Better to do. The reaction temperature is preferably −
The temperature is 80 to 100 ° C, more preferably 0 to 80 ° C, particularly preferably 10 to 40 ° C, and most preferably 15 to 30 ° C.

Specific examples of the compound represented by the general formula (II) are shown below, but the invention is not limited thereto.

[0020]

[Table 1]

[0021]

[Table 2]

[0022]

[Table 3]

[0023]

[Table 4]

[0024]

[Table 5]

[0025]

[Table 6]

[0026]

[Table 7]

[0027]

[Table 8]

[0028]

[Table 9]

[0029]

EXAMPLES The production method of the present invention will be described below in more detail with reference to Examples, but the present invention is not limited thereto. Example 1 (Synthesis of (II) -19) 2 synthesized by the method described in JP-A-62-123158
-(3-Dodecoxypropylcarbamoyl) -5-isobutoxycarbonylamino-1-naphthol 5.28 g
(0.01 mol) is dissolved in 30 ml of methylene chloride,
1,3-Dichloro-5,5-dimethylhydantoin 1.
00 g (0.005 mol) was added, and the mixture was stirred at room temperature for 3 nights. Wash with 5% aqueous sodium hydroxide, then water,
After distilling off the solvent, crystallization was performed using acetonitrile to obtain (II) -19 (5.24 g, yield 93%). Melting point 71-73 ° C

Example 2 (Synthesis of (II) -19) 1,3-Dichloro-5,5-dimethylhydantoin 2.
Under the same conditions as in Example 1, except that 00 g (0.01 mol) was used, the mixture was stirred at room temperature for 2 hours. The same post-treatment and purification as in Example 1 were carried out to obtain 5.40 g of (II) -19 in a yield of 96%.

Example 3 (Synthesis of (II) -19) The mixture was stirred at room temperature for 2 hours under the same conditions as in Example 2 except that the same amount of acetone was used as the solvent instead of methylene chloride. Ethyl acetate (50 ml) was added, the mixture was washed with 5% aqueous sodium hydroxide solution and then with water, and the solvent was distilled off. Then, crystallization was carried out using acetonitrile, and (II) -19 was added to 5.1.
7 g, yield 92% were obtained.

Example 4 (Synthesis of (II) -19) Reaction, post-treatment and purification were carried out under the same conditions as in Example 3 except that the same amount of N, N-dimethylacetamide was used as a solvent. II) -19 was obtained at 5.28 g in a yield of 94%.

Example 5 (Synthesis of (II) -20) Except that equimolar 1,3-dibromo-5,5-dimethylhydantoin was used instead of 1,3-dichloro-5,5-dimethylhydantoin. Reaction, post-treatment, and purification were carried out under the same conditions as in Example 1 to obtain 5.38 g of (II) -20.
The yield was 88%. Melting point 87-89 ° C

Example 6 The melting points of typical examples of the compound represented by the general formula (II) of the present invention obtained under the same conditions are shown below. (II) -21 120-122 ° C (II) -49 105-106.5 ° C (II) -57 129-131 ° C

The 4-halo-1-naphthol compound represented by the general formula (II) obtained by the production method of the present invention can be prepared by the method described in JP-A-62-123158 mentioned above. The halogen atom at the position can be a leaving group such as an alkoxy group. An example is shown below.

Example 7 (Synthesis of 2-hydroxyethoxy releasing naphthol cyan coupler using (II) -20) 3.46 g (0.025 mol) of potassium carbonate was added to 50 ml of ethylene glycol under a nitrogen atmosphere, and the mixture was steamed. Heat to a uniform solution. Then, under cooling with water, 0.10 g (0.001 mol) of cuprous chloride was added and stirred for 10 minutes. After that, 6.10 g (0.0) of (II) -20
1 mol), 50 ml of pyridine was further added, and the mixture was stirred at room temperature for 3 hours. 150 ml of ethyl acetate in the reaction solution,
150 ml of water was added and the aqueous layer was carefully acidified with hydrochloric acid. After extraction and liquid separation, the organic layer was washed twice with water, dried with sodium sulfate, the solvent was distilled off, and then crystallization was performed with a mixed solvent of n-hexane and ethyl acetate. The precipitated crystals are filtered,
(3-dodecyloxypropylcarbamoyl) -4-
4.89 g of (2-hydroxyethoxy) -5-iso-butoxycarbonylamino-1-naphthol, yield 8
Obtained at 3%. Melting point 121-123 ° C

Example 8 (Synthesis of (II) -19) The procedure of Example 3 was repeated, except that the same amount of toluene was used as the solvent instead of methylene chloride, and the mixture was stirred at room temperature for 5 hours. After the reaction, the same post-treatment and purification as in Example 3 were carried out to obtain (II) -19 (5.34 g, yield 95%).

Example 9 (Synthesis of (II) -19) The reaction, post-treatment and purification were carried out in exactly the same manner as in Example 3 except that the same amount of ethyl acetate was used as the solvent instead of methylene chloride. , (II) -19 5.45 g, yield 9
Obtained at 7%.

Example 10 (Synthesis of (II) -20) Reaction, post-treatment and purification were carried out in exactly the same manner as in Example 5 except that the same amount of acetone was used as the solvent instead of methylene chloride. , (II) -20, 5.62 g, yield 9
Obtained at 2%.

Example 11 (Synthesis of (II) -20) Reaction, post-treatment and purification were carried out in exactly the same manner as in Example 5 except that the same amount of toluene was used as the solvent instead of methylene chloride. , (II) -20 5.80 g, yield 9
Obtained at 5%.

Example 12 (Synthesis of (II) -20) Reaction, post-treatment and purification were carried out in exactly the same manner as in Example 5 except that the same amount of ethyl acetate was used as the solvent instead of methylene chloride. , (II) -20, 5.74 g, yield 94
%.

Example 13 (Synthesis of (II) -18) 2 synthesized by the method described in JP-A-62-123158.
-Butylcarbamoyl-5-isobutoxycarbonylamino-1-naphthol 3.58 g (0.01 mol) was dissolved in 30 ml of toluene, and 1,3-dibromo-5,5-
After adding 1.43 g (0.005 mol) of dimethylhydantoin and stirring at an internal temperature of 60 ° C. for 5 hours and returning to room temperature, the same post-treatment as in Example 1 was carried out, and (II) -18 was added to 4. Obtained in 15 g, yield 95%.

[0043]

According to the present invention, the cyan coupler of silver halide color photographic light-sensitive material and its synthetic intermediate can be simply and efficiently synthesized.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C07C 311/21 7419-4H C07C 311/21 G03C 7/34 G03C 7/34

Claims (6)

[Claims] 1. A compound represented by the following general formula (II) using 1,3-dihalo-5,5-dimethylhydantoin.
A method for producing a halo-1-naphthol compound. Embedded image (In the formula, R ¹ represents an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group or an arylsulfonyl group, and R ² represents an alkylamino group, an arylamino group, an aryloxy group or a hydroxy group. Represents a group, n represents 0 or 1, and X ¹ represents a halogen atom.) 2. A compound represented by the following general formula (I) is halogenated with 1,3-dihalo-5,5-dimethylhydantoin to give a compound represented by the above general formula (II):
The method according to claim 1, which is a halo-1-naphthol compound. Embedded image (In the formula, R ¹ represents an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group or an arylsulfonyl group, and R ² represents an alkylamino group, an arylamino group, an aryloxy group or a hydroxy group. Represents a group, and n represents 0 or 1.) 3. The 1,3-dihalo-5,5-dimethylhydantoin is 1,3-dichloro-5,5-dimethylhydantoin or 1,3-dibromo-5,5-dimethylhydantoin. The manufacturing method according to claim 1. 4. The method according to claim 1, 2 or 3, wherein an organic solvent other than the halogen-based solvent is used. 5. The method according to claim 1, 2 or 3, wherein toluene or ethyl acetate is used as a solvent. 6. The 1,3-dihalo-5,5-dimethylhydantoin is 1,3-dichloro-5,5-dimethylhydantoin, wherein the 1,3-dihalo-5,5-dimethylhydantoin is 1,3-dihalo-5,5-dimethylhydantoin.
The manufacturing method described.