Dye-forming coupler, silver halide photographic light-sensitive material, and method for producing an azomethine dye Number:6,803,181 from the United States Patent and Trademark Office (PTO) owispatent A dye-forming coupler of the formula (I). A silver halide photographic light-sensitive material that contains at least one dye-forming coupler of the formula (I). A method for producing an azomethine dye, which method comprises using a compound of the formula (I): ##STR1##wherein E is an aryl, heterocyclic, or --C(.dbd.O)W group, in which W is a nitrogen-containing heterocyclic group, Z is an aryl or heterocyclic group, and X and Y each independently are .dbd.O, .dbd.S or .dbd.N--R, in which R is a substituent, with the proviso that when E is an aryl or heterocyclic group, X and Y each are .dbd.O, and that when E is a --C(.dbd.O)W group, Z is a substituted aryl group.<H photographic, azomethine, Dye, forming, cou, 6803181.html, Patent, pto, 6803181

Title: Dye-forming coupler, silver halide photographic light-sensitive material, and method for producing an azomethine dye

Abstract: A dye-forming coupler of the formula (I). A silver halide photographic light-sensitive material that contains at least one dye-forming coupler of the formula (I). A method for producing an azomethine dye, which method comprises using a compound of the formula (I): ##STR1##wherein E is an aryl, heterocyclic, or --C(.dbd.O)W group, in which W is a nitrogen-containing heterocyclic group, Z is an aryl or heterocyclic group, and X and Y each independently are .dbd.O, .dbd.S or .dbd.N--R, in which R is a substituent, with the proviso that when E is an aryl or heterocyclic group, X and Y each are .dbd.O, and that when E is a --C(.dbd.O)W group, Z is a substituted aryl group.

Patent Number: 6,803,181 Issued on 10/12/2004 to Uehira, et al.

Inventors: Uehira; Shigeki (Minami-ashigara, JP); Ogasawara; Jun (Minami-ashigara, JP); Takeuchi; Kiyoshi (Minami-ashigara, JP); Shimada; Yasuhiro (Minami-ashigara, JP); Deguchi; Yasuaki (Minami-ashigara, JP)
Assignee: Fuji Photo Film Co., Ltd. (Kanagawa-Ken, JP)

Appl. No.: 10/270,055

Filed: October 15, 2002

Foreign Application Priority Data


Sep 27, 2000 [JP]			2000-294964
Sep 28, 2000 [JP]			2000-297609
Mar 30, 2001 [JP]			2000-101418

Current U.S. Class: 430/558 ; 430/503; 430/543

Current International Class: G03C 7/38 (20060101)

Field of Search: 430/558,543,502,503

References Cited [Referenced By]

U.S. Patent Documents


3201410	August 1965	Morel et al.
3759938	September 1973	Giraudon
3806597	April 1974	Giraudon
4977270	December 1990	Wee

Foreign Patent Documents


2135736	Jan., 1972	DE
52-148070	Dec., 1977	JP

Other References

Research Disclosure Item 9939 (1972) pp. 74-76. .
STN International R CAPLUS Database, RN 10319-47-8; J. Org. Chem, (1967), 32(2), 383-8. .
Abstract, JP 53/075930A, Jul. 5, 1978 (XP002189696). .
Abstract, JP 56/1500070A, Nov. 20, 1981 (XP002189697). .
XP002189695 (Beilstein Registry No. 5975454, CAS Registry No. 83490-80-6)..

Primary Examiner: Letscher; Geraldine
Attorney, Agent or Firm: Sughrue Mion, PLLC

Parent Case Text

This is a continuation of application Ser. No. 09/962,335 filed Sep. 26, 2001, now abandoned the disclosure of which is incorporated herein by reference.

Claims

What we claim is:

1. A silver halide photographic light-sensitive material, containing at least one dye-forming coupler represented by the following formula (I): ##STR118## wherein E represents an aryl group or heterocyclic group, or a --C(.dbd.O)W group, in which W represents a nitrogen-containing heterocyclic group, Z represents an aryl group or a heterocyclic group, and X and Y each independently represent .dbd.O, .dbd.S, or .dbd.N--R, in which R represents a substituent, with the proviso that when E represents an aryl group or a heterocyclic group, X and Y each represent .dbd.O, and that when E represents a --C(.dbd.O)W group, Z represents a substituted aryl group.

2. The silver halide photographic light-sensitive material as claimed in claim 1, wherein the dye-forming coupler represented by formula (I) is represented by the following formula (IA): ##STR119## wherein, in formula (IA), E.sub.A and Z.sub.A each independently represent an aryl group or a heterocyclic group.

3. The silver halide photographic light-sensitive material as claimed in claim 2, wherein, in the dye-forming coupler represented by formula (IA), E.sub.A is an aryl or heterocyclic group, having a substituent on at least one position adjacent to the carbon atom bonded to the oxazolidinedione ring.

4. The silver halide photographic light-sensitive material as claimed in claim 2, wherein, in the dye-forming coupler represented by formula (IA), E.sub.A is an aryl or heterocyclic group, having substituents on both of positions adjacent to the carbon atom bonded to the oxazolidinedione ring.

5. The silver halide photographic light-sensitive material as claimed in claim 2, wherein, in the dye-forming coupler represented by formula (IA), E.sub.A is a heterocyclic group.

6. The silver halide photographic light-sensitive material as claimed in claim 5, wherein the dye-forming coupler represented by formula (IA) is represented by the following formula (II): ##STR120## wherein, in formula (II), Z.sub.A represents an aryl group or a heterocyclic group, Q represents a group of atoms composed of carbon atoms and/or hetero atoms necessary to form, together with the N--C.dbd.N, a 5-, 6- or 7-membered ring, and R.sub.1 represents a substituent.

7. The silver halide photographic light-sensitive material as claimed in claim 6, wherein, in the dye-forming coupler represented by formula (II), Q is represented by the following formula (III): ##STR121## wherein, in formula (III), L.sub.Q represents a carbonyl or sulfonyl group, and R.sub.2 and R.sub.3, which are the same or different, each represent a hydrogen atom or a substituent, or R.sub.2 and R.sub.3 may bond together to form a ring.

8. The silver halide photographic light-sensitive material as claimed in claim 7, wherein when Q in the dye-forming coupler represented by formula (II) is represented by the formula (III), said L.sub.Q is a carbonyl group.

9. The silver halide photographic light-sensitive material as claimed in claim 2, wherein, in the dye-forming coupler represented by formula (IA), Z.sub.A is a heterocyclic group.

10. The silver halide photographic light-sensitive material as claimed in claim 2, wherein, in the dye-forming coupler represented by formula (IA), Z.sub.A is an aryl group having a substituent on an ortho position thereof.

11. The silver halide photographic light-sensitive material as claimed in claim 2, wherein the dye-forming coupler represented by formula (IA) is represented by the following formula (IV): ##STR122## wherein, in formula (IV), E.sub.A represents an aryl group or a heterocyclic group; R.sub.4 represents a halogen atom, an alkoxy group, or an aryloxy group; R.sub.5 represents a substituent; and n is an integer of 0, or 1 to 4; when n is an integer of 2 to 4, R.sub.5 's each are the same or different; or the groups adjacent to each other among R.sub.4 and R.sub.5 ('s) may bond together to form a ring.

12. The silver halide photographic light-sensitive material as claimed in claim 2, wherein the dye-forming coupler represented by formula (IA) is represented by the following formula (V): ##STR123## wherein, in formula (V), Q is a group represented by the following formula (III), R.sub.1 represents a substituent, R.sub.4 represents a halogen atom, an alkoxy group, or an aryloxy group, R.sub.5 represents a substituent, n is an integer of 0 or 1 to 4; when n is an integer of 2 to 4, R.sub.5 's each may be the same or different, or the groups adjacent to each other among R.sub.4 and R.sub.5 ('s) may bond together to form a ring: ##STR124## wherein, in formula (III), L.sub.Q represents a carbonyl or sulfonyl group, R.sub.2 and R.sub.3, which are the same or different, each represent a hydrogen atom or a substituent, or R.sub.2 and R.sub.3 may bond together to form a ring.

13. The silver halide color photographic light-sensitive material as claimed in claim 1, wherein the dye-forming coupler represented by formula (I) is represented by the following formula (IB): ##STR125## wherein, in formula (IB), W represents a nitrogen-containing heterocyclic group, Z.sub.B represents a substituted aryl group, and X and Y each independently represent .dbd.O, .dbd.S, or .dbd.N--R, in which R represents a substituent.

14. The silver halide color photographic light-sensitive material as claimed in claim 13, wherein, in the formula (IB), Z.sub.B is a phenyl group substituted by a halogen atom or an alkoxy group on the 2-position thereof, and having a substituent on the 5-position thereof.

15. The silver halide color photographic light-sensitive material as claimed in claim 13, wherein, in the formula (IB), Z.sub.B is a phenyl group substituted by a halogen atom or an alkoxy group on the 2-position thereof, and having a substituent on the 5-position thereof; and X and Y each represent .dbd.O.

Description

FIELD OF THE INVENTION

The present invention relates to a novel dye-forming coupler to form an azomethine dye, upon a coupling-reaction with an oxidized product of a developing agent, and to a silver halide photographic light-sensitive material containing said coupler. The present invention also relates to a method for producing an azomethine dye by using the above-mentioned reaction.

BACKGROUND OF THE INVENTION

In a silver halide photographic light-sensitive material (which may be referred to simply as a "light-sensitive material" hereinafter) using subtractive color processes, a color image can be formed from dyes having three primary colors, i.e. yellow, magenta, and cyan. In color photography using a current p-phenylenediamine-series color-developing agent, a .beta.-acylacetanilide-series compound is used as a yellow coupler. However, the hue of the yellow dye obtained from this coupler is reddish, and it is difficult to obtain a hue of yellow having high purity. This dye has a small molecular extinction coefficient. Thus, in order to obtain a desired developed color density, a large amount of the coupler or silver halide is required. Therefore, the film thickness of the light-sensitive material becomes large, so that the sharpness of a resultant color image may drop. Such problems are caused. Furthermore, the above-mentioned dye is easily decomposed under high temperature and high humidity conditions, and the image storability thereof after development processing is insufficient. Thus improvement in this point is desired.

In order to solve these problems, the acyl group or the anilido group has been improved. Recently, the following have been proposed as improved couplers of conventional acylacetanilide: for example, 1-alkylcyclopropanecarbonylacetanilide-series compounds as described in JP-A-4-218,042 ("JP-A" means unexamined published Japanese patent application); cyclic malonediamide-type couplers as described in JP-A-5-11416; pyrrole-2 or 3-yl- or indole-2 or 3-yl-carbonylacetanilide-series couplers, as described, for example, in EP-953870A1, EP-953871A1, EP-953872A1, EP-953873A1, EP-953874A1 and EP-953875A1. Dyes formed from these couplers have improved hue and an improved molecular extinction coefficient, compared with conventional dyes. However, their image storability is still insufficient. Moreover, the synthesis routes of the couplers are long, since their structures have been made complicated. Thus, costs of the couplers are high. For these reasons, the couplers are not practical.

Research Disclosure Item 9939 (page 74, 1972) and JP-A-52-148070 describe couplers having a 2,4-oxazolidinedione structure. However, these couplers are unsatisfactory to solve the problems of the conventional couplers in both hue and a molecular extinction coefficient of the resultant dye.

SUMMARY OF THE INVENTION

The present invention is a dye-forming coupler represented by the following formula (I): ##STR2##

wherein E represents an aryl group or heterocyclic group, or a --C(.dbd.O)W group, in which W represents a nitrogen-containing heterocyclic group, Z represents an aryl group or a heterocyclic group, and X and Y each independently represent .dbd.O, .dbd.S, or .dbd.N--R, in which R represents a substituent, with the proviso that when E represents an aryl group or a heterocyclic group, X and Y each represent .dbd.O, and that when E represents a --C(.dbd.O)W group, Z represents a substituted aryl group.

Further, the present invention is a silver halide photographic light-sensitive material, which contains at least one dye-forming coupler represented by the above formula (I).

Still further, the present invention is a method for producing an azomethine dye, which method comprises using a compound represented by the following formula (IA): ##STR3##

wherein E.sub.A and Z.sub.A each independently represent an aryl group or a heterocyclic group.

Other and further features and advantages of the invention will appear more fully from the following description.

DETAILED DESCRIPTION OF THE INVENTION

According to the present invention, there are provided the following means:

(1) A dye-forming coupler represented by the following formula (I): ##STR4##

wherein E represents an aryl group or heterocyclic group, or a --C(.dbd.O)W group, in which W represents a nitrogen-containing heterocyclic group, and Z represent an aryl group or a heterocyclic group, and X and Y each independently represent .dbd.O, .dbd.S, or .dbd.N--R, in which R represents a substituent, with the proviso that when E represents an aryl group or a heterocyclic group, X and Y each represent .dbd.O, and that when E represents a --C(.dbd.O)W groyup, Z represents a substituted aryl group.

(2) The dye-forming coupler according to the above item (1), wherein the dye-forming coupler represented by formula (I) is represented by the following formula (IA): ##STR5##

wherein, in formula (IA), E.sub.A and Z.sub.A each independently represent an aryl group or a heterocyclic group.

(3) The dye-forming coupler according to the above item (1), wherein the dye-forming coupler represented by formula (I) is represented by the following formula (IB): ##STR6##

wherein, in formula (IB), W represents a nitrogen-containing heterocyclic group, Z.sub.B represents a substituted aryl group, and X and Y each independently represent .dbd.O, .dbd.S, or .dbd.N--R, in which R represents a substituent.

(4) A silver halide photographic light-sensitive material, containing at least one dye-forming coupler represented by the following formula (I): ##STR7##

wherein E represents an aryl group or heterocyclic group, or a --C(.dbd.O)W group, in which W represents a nitrogen-containing heterocyclic group, Z represents an aryl group or a heterocyclic group, and X and Y each independently represent .dbd.O, .dbd.S, or .dbd.N--R, in which R represents a substituent, with the proviso that when E represents an aryl group or a heterocyclic group, X and Y each represent .dbd.O, and that when E represents a --C(.dbd.O)W group, Z represents a substituted aryl group.

(5) The silver halide photographic light-sensitive material according to the above item (4), wherein the dye-forming coupler represented by formula (I) is represented by the following formula (IA): ##STR8##

wherein, in formula (IA), E.sub.A and Z.sub.A each independently represent an aryl group or a heterocyclic group.

(6) The silver halide photographic light-sensitive material according to the above item (5), wherein, in the dye-forming coupler represented by formula (IA), E.sub.A is an aryl or heterocyclic group, having a substituent on at least one position adjacent to the carbon atom bonded to the oxazolidinedione ring.

(7) The silver halide photographic light-sensitive material according to the above item (5), wherein, in the dye-forming coupler represented by formula (IA), E.sub.A is an aryl or heterocyclic group, having substituents on both of positions adjacent to the carbon atom bonded to the oxazolidinedione ring.

(8) The silver halide photographic light-sensitive material according to any one of the above items (5) to (7), wherein, in the dye-forming coupler represented by formula (IA), E.sub.A is a heterocyclic group.

(9) The silver halide photographic light-sensitive material according to the above item (8), wherein the dye-forming coupler represented by formula (IA) is represented by the following formula (II): ##STR9##

wherein, in formula (II), Z.sub.A represents an aryl group or a heterocyclic group, Q represents a group of atoms composed of carbon atoms and/or hetero atoms necessary to form, together with the N--C.dbd.N, a 5-, 6- or 7-membered ring, and R.sub.1 represents a substituent.

(10) The silver halide photographic light-sensitive material according to the above item (9), wherein, in the dye-forming coupler represented by formula (II), Q is represented by the following formula (III): ##STR10##

wherein, in formula (III), L.sub.Q represents a carbonyl or sulfonyl group, and R.sub.2 and R.sub.3, which are the same or different from, each represent a hydrogen atom or a substituent, or R.sub.2 and R.sub.3 may bond together to form a ring.

(11) The silver halide photographic light-sensitive material according to the above item (10), wherein when Q in the dye-forming coupler represented by formula (II) is represented by the formula (III), said L.sub.Q is a carbonyl group.

(12) The silver halide photographic light-sensitive material according to any one of the above items (5) to (11), wherein, in the dye-forming coupler represented by formula (IA), Z.sub.A is a heterocyclic group.

(13) The silver halide photographic light-sensitive material according to any one of the above items (5) to (11), wherein, in the dye-forming coupler represented by formula (IA), Z.sub.A is an aryl group having a substituent on an ortho position thereof.

(14) The silver halide photographic light-sensitive material according to the above item (5), wherein the dye-forming coupler represented by formula (IA) is represented by the following formula (IV): ##STR11##

wherein, in formula (IV), E.sub.A represents an aryl group or a heterocyclic group; R.sub.4 represents a halogen atom, an alkoxy group, or an aryloxy group; R.sub.5 represents a substituent; and n is an integer of 0, or 1 to 4; when n is an integer of 2 to 4, R.sub.5 's each are the same or different; or the groups adjacent to each other, among R.sub.4 and R.sub.5 ('s), may bond together to form a ring.

(15) The silver halide color photographic light-sensitive material according to the above item (4), wherein the dye-forming coupler represented by formula (I) is represented by the following formula (IB): ##STR12##

wherein, in formula (IB), W represents a nitrogen-containing heterocyclic group, Z.sub.B represents a substituted aryl group, and X and Y each independently represent .dbd.O, .dbd.S, or .dbd.N--R, in which R represents a substituent.

(16) A method for producing an azomethine dye, comprising using a compound represented by the following formula (I): ##STR13##

wherein E represents an aryl group or heterocyclic group, or a --C(.dbd.O)W group, in which W represents a nitrogen-containing heterocyclic group, Z represents an aryl group or a heterocyclic group, and X and Y each independently represent .dbd.O, .dbd.S, or .dbd.N--R, in which R represents a substituent, with the proviso that when E represents an aryl group or a heterocyclic group, X and Y each represent .dbd.O, and that when E represents a --C(.dbd.O)W group, Z represents a substituted aryl group.

(17) The method according to the above item (16), wherein the compound represented by formula (I) is represented by the following formula (IA): ##STR14##

wherein, in formula (IA), E.sub.A and Z.sub.A each independently represent an aryl group or a heterocyclic group.

(18) The method according to the above item (17), wherein a p-phenylenediamine compound is used together with the compound represented by formula (IA).

(Herein, the dye-forming coupler represented by formula (IA) (e.g. those described in the above item (2)), and the light-sensitive material (e.g. those described in the above items (5) to (14)) and the method for producing an azomethine dye (e.g. those described in the above items (17) and (18)), each of which utilizes said compound of the formula (IA) are collectively referred to as a first embodiment of the present invention.)

(Herein, the dye-forming coupler represented by formula (IB) (e.g. those described in the above item (3)), and the light-sensitive material (e.g. those described in the above item (15) and the method for producing an azomethine dye, each of which utilizes said compound of the formula (IB) are collectively referred to as a second embodiment of the present invention.)

Herein, the present invention means to include both the first embodiment and the second embodiment, unless otherwise specified.

Hereinafter, the present invention will be described in detail.

(Dye-forming Coupler)

The dye-forming coupler of the present invention will be explained below, referring to the formulae (IA) and (IB), and these explanations, as they are, can also be applied to the formula (I) that includes said formulae (IA) and (IB).

The compound that may also be referred to as the dye-forming coupler, herein, represented by formula (IA), which is the first embodiment of the compound represented by formula (I) of the present invention, will be described in more detail. ##STR15##

wherein E.sub.A and Z.sub.A each independently represent an aryl or heterocyclic group.

The aryl group represented by E.sub.A or Z.sub.A is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. Examples thereof include phenyl, p-tolyl, naphthyl, m-chlorophenyl, and o-hexadecanoylaminophenyl. The heterocyclic group represented by E.sub.A or Z.sub.A is preferably a monovalent group in which one hydrogen atom is removed from a 5- or 6-membered, substituted or unsubstituted, and aromatic or non-aromatic heterocyclic compound; and it is more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. Examples thereof include 2-furyl, 2-thienyl, 2-pyrimidinyl, and 2-benzothiazolyl.

Examples of the substituent in the substituted aryl or substituted heterocyclic group (that is, the substituent which the aryl or heterocyclic group may have) include halogen atoms, alkyl (including cycloalkyl and bicycloalkyl), alkenyl (including cycloalkenyl and bicycloalkenyl), alkynyl, aryl, heterocyclic, cyano, hydroxyl, nitro, carboxyl, alkoxy, aryloxy, silyloxy, heterocyclic oxy, acyloxy, carbamoyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, amino (including alkylamino and anilino), acylamino, aminocarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfamoylamino, alkyl- and aryl-sulfonylamino, mercapto, alkylthio, arylthio, heterocyclic thio, sulfamoyl, sulfo, alkyl- and aryl-sulfinyl, alkyl- and aryl-sulfonyl, acyl, aryloxycarbonyl, alkoxycarbonyl, carbamoyl, aryl azo and heterocyclic azo, imido, phosphio, phosphinyl, phosphinyloxy, phosphinylamino, and silyl groups.

When the aryl or heterocyclic group is substituted with plural substituents, these substituents may be the same or different, or the substituents adjacent to each other may be bonded to each other to form a ring, preferably a 5- or 6-membered, saturated or unsaturated ring.

The above-mentioned substituent may be substituted with a substituent. Examples of this substituent are the same as described as the examples of the above-mentioned substituent.

The following will describe the substituent that the aryl or heterocyclic group represented by E.sub.A or Z.sub.A may have more specifically.

Examples of the substituent include the followings: halogen atoms (for example, chlorine, bromine and iodine atoms); alkyl groups (straight-chain or branched, substituted or unsubstituted alkyl groups, preferably alkyl groups having 1 to 30 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, and 2-ethylhexyl); cycloalkyl groups (preferably, substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, for example, cyclohexyl, cyclopentyl, and 4-n-dodecylcyclohexyl; and including polycycloalkyl groups, for example, groups having a polycyclic structure, such as bicycloalkyl groups (preferably, substituted or unsubstituted bicycloalkyl groups having 5 to 30 carbon atoms, for example, bicyclo[1,2,2]heptane-2-yl and bicyclo[2,2,2]octane-3-yl), and tricycloalkyl groups. A monocyclic cycloalkyl and bicycloalkyl groups are preferred, and a monocyclic cycloalkyl group is particularly preferred.); alkenyl groups (straight-chain or branched, substituted or unsubstituted alkenyl groups, preferably alkenyl groups having 2 to 30 carbon atoms, for example, vinyl, allyl, prenyl, geranyl and oleyl); cycloalkenyl groups (preferably, substituted or unsubstituted cycloalkenyl groups having 3 to 30 carbon atoms, for example, 2-cyclopentene-1-yl and 2-cyclohexene-1-yl; further including polycycloalkenyl groups, for example, bicycloalkenyl groups (preferably, substituted or unsubstituted bicyloalkenyl groups having 5 to 30 carbon atoms, for example, bicyclo[2,2,1]hept-2-ene-1-yl and bicyclo[2,2,2]oct-2-ene-4-yl), and tricycloalkenyl groups. A monocyclic cycloalkenyl group is particularly preferred.); alkynyl groups (preferably, substituted or unsubstituted alkynyl groups having 2 to 30 carbon atoms, for example, ethynyl, propalgyl, and trimethylsilylethynyl); aryl groups (preferably, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, for example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl); heterocyclic groups (preferably, 5- or 6-membered, substituted or unsubstituted, and aromatic or non-aromatic heterocyclic groups, more preferably heterocyclic groups that have at least one hetero atom of nitrogen, oxygen or sulfur atoms and whose ring(s) is/are composed of atoms selected from carbon, nitrogen and sulfur atoms, and still more preferably 5- or 6-membered aromatic heterocyclic groups having 3 to 30 carbon atoms, for example, 2-furyl, 2-thienyl, 2-pyrrimidynyl, 2-benzothiazolyl); cyano group; hydroxyl group; nitro group; carboxyl group; alkoxy groups (preferably, substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms, for example, methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, and 2-methoxyethoxy); aryloxy groups (preferably, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy); silyloxy groups (preferably, silyloxy groups having 3 to 20 carbon atoms, for example, trimethylsilyloxy, and t-butyldimethylsilyloxy), heterocyclic oxy groups (preferably, substituted or unsubstituted heterocyclic oxy groups having 2 to 30 carbon atoms, the heterocyclic moiety thereof being preferably the heterocyclic moiety described about the above-mentioned heterocyclic group, for example, 1-phenyltetrazole-5-oxy, and 2-tetrahydropyrranyloxy); acyloxy groups (preferably, formyloxy, substituted or unsubstituted alkylcarbonyloxy groups having 2 to 30 carbon atoms, and substituted or unsubstituted arylcarbonyloxy groups having 6 to 30 carbon atoms, for example, formyloxy, acetyloxy, pyvaloyloxy, stearoyloxy, benzoyloxy, and p-methoxyphenylcarbonyloxy); carbamoyloxy groups (preferably, substituted or unsubstituted carbamoyloxy groups having 1 to 30 carbon atoms, for example, N,N-dimethylcarbamoyloxy, N,N-diethylcarbamoyloxy, morpholinocarbonyloxy, N,N-di-n-octylaminocarbonyloxy, and N-n-octylcarbamoyloxy); alkoxycarbonyloxy groups (preferably, substituted or unsubstituted alkoxycarbonyloxy groups having 2 to 30 carbon atoms, for example, methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, and n-octylcarbonyloxy); aryloxycarbonyloxy groups (preferably, substituted or unsubstituted aryloxycarbonyloxy groups having 7 to 30 carbon atoms, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, and p-n-hexadecyloxyphenoxycarbonyloxy); amino groups (preferably, amino group, substituted or unsubstituted alkylamino groups having 1 to 30 carbon atoms, substituted or unsubstituted arylamino groups having 6 to 30 carbon atoms, and heterocyclic amino groups having 0 to 30 carbon atoms, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-1,3,5-triazine-2-ylamino); acylamino groups (preferably, formylamino group, substituted or unsubstituted alkylcarbonylamino groups having 1 to 30 carbon atoms, and substituted or unsubstituted arylcarbonylamino groups having 6 to 30 carbon atoms, for example, formylamino, acetylamino, pyvaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino); aminocarbonylamino groups (preferably, substituted or unsubstituted aminocarbonylamino groups having 1 to 30 carbon atoms, for example, carbamoylamino, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, and morpholinocarbonylamino), alkoxycarbonylamino groups (preferably, substituted or unsubstituted alkoxycarbonylamino groups having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, and N-methyl-methoxycarbonylamino); aryloxycarbonylamino groups (preferably, substituted or unsubstituted aryloxycarbonylamino groups having 7 to 30 carbon atoms, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, and m-n-octyloxyphenoxycarbonylamino); sulfamoylamino groups (preferably, substituted or unsubstituted sulfamoylamino groups having 0 to 30 carbon atoms, for example, sulfamoylamino, N,N-dimethylaminosulfonylamino, and N-n-octylaminosulfonylamino); alkyl- and aryl-sulfonylamino groups (preferably, substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms, and substituted or unsubstituted arylsulfonylamino groups having 6 to 30 carbon atoms, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, and p-methylphenylsulfonylamino); mercapto group; alkylthio groups (preferably, substituted or unsubstituted alkylthio groups having 1 to 30 carbon atoms, for example, methylthio, ethylthio, and n-hexadecylthio); arylthio groups (preferably, substituted or unsubstituted arylthio groups having 6 to 30 carbon atoms, for example, phenylthio, p-chlorophenylthio, and m-methoxyphenylthio); heterocyclic thio groups (preferably, substituted or unsubstituted heterocyclic thio groups having 2 to 30 carbon atoms, the heterocyclic moiety thereof being preferably the heterocyclic moiety described about the above-mentioned heterocyclic group, for example, 2-benzothiazolylthio, and 1-phenyltetrazole-5-ylthio); sulfamoyl groups (preferably, substituted or unsubstituted sulfamoyl groups having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N-(3-dodecyloxypropyl)sulfamoyl, N,N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N-(N'-phenylcarbamoyl)sulfamoyl); sulfo group; alkyl- and aryl-sulfinyl groups (preferably, substituted or unsubstituted alkylsulfinyl groups having 1 to 30 carbon atoms, and substituted or unsubstituted arylsulfinyl groups having 6 to 30 carbon atoms, for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, and p-methylphenylsulfinyl); alkyl- and aryl-sulfonyl groups (preferably, substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, and substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms, for example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl); acyl groups (preferably, formyl group, substituted or unsubstituted alkylcarbonyl groups having 2 to 30 carbon atoms, and substituted or unsubstituted arylcarbonyl groups having 7 to 30 carbon atoms, for example, acetyl, pyvaloyl, 2-chloroacetyl, stearoyl, benzoyl, and p-n-octyloxyphenylcarbonyl); aryloxycarbonyl groups (preferably, substituted or unsubstituted aryloxycarbonyl groups having 7 to 30 carbon atoms, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, and p-t-butylphenoxycarbonyl); alkoxycarbonyl groups (preferably, substituted or unsubstituted alkoxycarbonyl groups having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, and n-octadecyloxycarbonyl); carbamoyl groups (preferably, substituted or unsubstituted carbamoyl groups having 1 to 30 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N,N-dimethylcarbamoyl, N,N-di-n-octylcarbamoyl, and N-(methylsulfonyl)carbamoyl); aryl azo and heterocyclic azo groups (preferably, substituted or unsubstituted aryl azo groups having 6 to 30 carbon atoms, and substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms (the heterocyclic moiety thereof being preferably the heterocyclic moiety described about the above-mentioned heterocyclic group), for example, phenyl azo, p-chlorophenyl azo, 5-ethylthio-1,3,4-thiadiazole-2-ylazo); imido groups (preferably, substituted or unsubstituted imido groups having 2 to 30 carbon atoms, for example, N-succinimido and N-phthalimido); phosphino groups (preferably, substituted or unsubstituted phosphino groups having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino, and methylphenoxyphosphino); phosphinyl groups (preferably, substituted or unsubstituted phosphinyl groups having 2 to 30 carbon atoms, for example, phosphinyl, dioctyloxyphosphinyl, and diethoxyphosphinyl); phosphinyloxy groups (preferably, substituted or unsubstituted phosphinyloxy groups having 2 to 30 carbon atoms, for example, diphenoxyphosphinyloxy, and dioctyloxyphosphinyloxy); phoshinylamino groups (preferably, substituted or unsubstituted phoshinylamino groups having 2 to 30 carbon atoms, for example, dimethoxyphoshinylamino, and dimethylaminophoshinylamino); and silyl groups (preferably, substituted or unsubstituted silyl groups having 3 to 30 carbon atoms, for example, trimethylsilyl, t-butyldimethylsilyl, and phenyldimethylsilyl).

About a group having a hydrogen atom, among the above-mentioned functional groups, it is allowable to remove the hydrogen atom and further substitute the group with another group (substituent) as described above. Examples of such a functional group include alkylcarbonylaminosulfonyl groups, arylcarbonylaminosulfonyl groups, alkylsulfonylaminocarbonyl groups, and arylsulfonylaminocarbonyl groups. More specific examples thereof include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl.

The substituents adjacent to each other may be bonded to each other to form a ring, preferably a 5- or 6-membered, saturated or unsaturated ring. The ring may be alicyclic, aromatic or heterocyclic. Examples thereof include benzene, furan, thiophene, cyclopentane, and cyclohexane rings.

The ring formed by binding each one of the substituents singly or a plurality of the substituents each other may be further substituted with a substituent, examples of which are groups given as examples of the substituent that the aryl or heterocyclic group represented by E.sub.A or Z.sub.A may have.

The total number of the carbon atoms in the substituent which the aryl or heterocyclic group represented by E.sub.A or Z.sub.A may have is preferably from 2 to 50, more preferably from 8 to 45, and still more preferably from 15 or 40.

The number of the carbon atoms of one or more substituents, among the substituents which E.sub.A or Z.sub.A may have, is preferably from 1 to 30, more preferably from 6 to 30, still more preferably from 8 to 30, and most preferably from 10 to 25.

Among the above-mentioned substituents, preferred are halogen atoms, and alkyl, alkenyl, aryl, heterocyclic, alkoxy, aryloxy, alkylthio, arylthio, cyano, acylamino, alkoxycarbonyl, carbamoyl, sulfamoyl, alkylamino and arylamino groups.

In the case that E.sub.A is an aryl group, E.sub.A preferably has an electron withdrawing substituent whose Hammett's substituent constant (.sigma..sub.p) is more than 0, and more preferably has an electron withdrawing substituent whose .sigma..sub.p is from 0 to 1.5.

Hammett's substituent constants .sigma..sub.p and .sigma..sub.m are explained in detail, for example, in the following literatures: "Hammett Rule -Structure and Reactivity-", written by Naoki Inamoto (published by Maruzen), "New Experimental Chemical Course 14, Synthesis and Reaction V of Organic Compounds", p. 2605, edited by the Chemical Society of Japan (published by Maruzen), "Explanation on Theoretical organic Chemistry", p. 217, written by Tadao Nakaya (published by Tokyo Kagaku Dojin), and "Chemical Review", Vol. 91, pp. 165-195 (1991).

E.sub.A is preferably an aryl or heterocyclic group having a substituent (preferably, any one of the above-mentioned preferred substitutes, more preferably halogen atoms, alkyl, aryl, heterocyclic and alkoxy groups, and particularly preferably halogen atoms, and alkyl and alkoxy groups) on at least one position adjacent to the carbon atom bonded to the oxazolidinedione ring. E.sub.A is more preferably an aryl or heterocyclic group having substituents (preferably, the above-mentioned preferred substitutes, more preferably a halogen atom, or an alkyl, aryl, heterocyclic or alkoxy group, and particularly preferably a halogen atom, or an alkyl or alkoxy group) at both positions adjacent to the carbon atom bonded to the oxazolidinedione ring. E.sub.A is particular preferably a heterocyclic group that may have the substituent(s) as above.

When E.sub.A is a heterocyclic group, compounds represented by the following formula (II) are preferred. ##STR16##

In the formula (II), Z.sub.A represents an aryl or heterocyclic ring, Q represents a group of atoms selected from carbon atoms and/or hetero atoms necessary to form, together with the N--C.dbd.N, a 5-, 6- or 7-membered ring; and R.sub.1 represents a substituent. Examples of the substituent include the same as described as the examples of the substituent which E.sub.A or Z.sub.A may have.

When E.sub.A is a heterocyclic group, compounds in which Q is represented by the following formula (III) are more preferred. ##STR17##

In the formula (III), L.sub.Q represents a carbonyl or sulfonyl group; R.sub.2 and R.sub.3, which may be the same or different, each represent a hydrogen atom or a substituent, or R.sub.2 and R.sub.3 may be bonded to each other to form a ring. Examples of the substituent include the same as described as the examples of the substituent which E.sub.A or Z.sub.A may have.

When E.sub.A is a heterocyclic group, L.sub.Q is most preferably a carbonyl group.

It is preferred that Z.sub.A is an aryl or heterocyclic group and said group has an electron withdrawing substituent whose Hammett's substituent constant (.sigma..sub.p) value is more than 0. It is more preferred that said group has an electron withdrawing substituent whose .sigma..sub.p is from 0 to 1.5.

The sum total of the .sigma..sub.p values of the substituents which an aryl or heterocyclic group represented by Z.sub.A has is preferably 0 or more, more preferably 0.40 or more, still more preferably 0.60 or more, and most preferably 0.80 or more. The sum total of the .sigma..sub.p values is preferably 3.90 or less.

Z.sub.A is preferably a heterocyclic group or an aryl group that has at its ortho position a substituent (preferably, the above-mentioned preferred substituent, particularly preferably a halogen atom, an alkoxy or aryloxy group).

Among the compounds represented by formula (IA), compounds represented by the following formula (IV) are more preferred. ##STR18##

In the formula (IV), E.sub.A is an aryl or heterocyclic group; R.sub.4 represents a halogen atom, an alkoxy group, or an aryloxy group; R.sub.5 represents a substituent; n is an integer of 0, or 1 to 4; when n is an integer of 2 to 4, R.sub.5 's may be the same or different; or the groups adjacent to each other, among R.sub.4 and R.sub.5 ('s), may be bonded to each other to form a ring.

E.sub.A has the same meaning as in the formula (IA), and the preferred scope thereof is also the same as about the formula (IA).

The halogen atom, the alkoxy group, and the aryloxy group, each of which is represented by R.sub.4, have the same meanings as the halogen atom, the alkoxy group, and the aryloxy group, which are described as the substituent that the aryl group represented by Z.sub.A in the formula (IA) may have. The preferred scope thereof is also the same as about them. Examples of R.sub.5 are the same as described as the examples of the substituent that the aryl group represented by Z.sub.A in the formula (IA) may have. The preferred scope thereof is also the same as about the substituent.

Preferred specific examples of the couplers represented by formula (IA) in the present invention are shown below. The present invention is not limited to these compounds. Tautomers wherein the hydrogen atom in the oxazolidinedione ring is transferred onto the carbonyl group or E.sub.A are also included in the present invention. ##STR19## ##STR20## ##STR21## ##STR22## ##STR23## ##STR24## ##STR25## ##STR26## ##STR27## ##STR28## ##STR29## ##STR30## ##STR31## ##STR32## ##STR33##

When any one of the exemplified compounds (which may also be referred to as dye-forming couplers) shown above is referred to in the following description, a number X put in parentheses, that is, (X) attached to the exemplified compound is used to express the compound as "the coupler (X)".

The following will describe specific synthetic examples of the compounds represented by formula (IA).

Synthetic Example 1

Synthesis of the Coupler (48)

The coupler (48) was synthesized according to the following route: ##STR34##

To 50 ml of a solution of 0.73 g of zinc iodide and 11.9 g of 2,6-dichlorobenzaldehyde in acetonitrile, was dropwise added 7.4 g of trimethylsilylcyanide at 0.degree. C. under the atmosphere of nitrogen. The temperature of the resultant system was returned to room temperature and the solution was stirred for 2 hours. Thereafter, the solution was poured into ice water, and ethyl acetate was added thereto, to perform extraction. The organic phase was washed with saturated brine. The organic phase was dried over anhydrous magnesium sulfate and then the solvent was distilled off under reduced pressure, to give a compound (A-1) as a liquid. Thereto was added 10 ml of water, and then 150 ml of 35% aqueous hydrochloric acid was added thereto. The resultant solution was stirred for 2 hours while refluxed under heating. The temperature of the system was lowered to 0.degree. C., and then the solution was made to weak alkalinity with 2% aqueous potassium hydroxide solution. Ethyl acetate was added to the resultant solution, to separate the solution into two liquid phases. The aqueous phase was made to weak acidic with 1N aqueous hydrochloric acid. This aqueous phase was extracted with ethyl acetate and the organic phase was dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure, to give 12.4 g of a compound (A-2).

Into 70 ml of methyl alcohol was dissolved 10 g of the compound (A-2), and then 4 or 5 drops of concentrated sulfuric acid were added thereto. This solution was stirred for 2 hours while refluxed under heating. The solution was cooled, and then 10% aqueous potassium carbonate solution and ethyl acetate were added thereto, to perform extraction. The organic phase was washed with saturated brine. The organic phase was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure, to give 9.1 g of a compound (A-3).

A 80 ml solution of 9 g of the compound (A-3), 7.2 g of 2,5-dichlorophenylisocyanate, and 3.9 g of triethylamine in N,N-diemethylacetoamide was heated to 110.degree. C. and stirred for 3 hours. The system was cooled and then water and ethyl acetate were added thereto, to perform extraction. The organic phase was washed with saturated brine. The organic phase was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The resultant residue was subjected to crystallization from a mixed solvent of ethyl acetate and hexane, to give 8.2 g of the coupler (48).

Synthetic Example 2

Synthesis of the Coupler (11)

The coupler (11) was synthesized according to the following route: ##STR35##

To 50 ml of a solution of 0.96 g of zinc iodide and 15.1 g of 2-nitrobenzaldehyde in acetonitrile, was dropwise added 10.9 g of trimethylsilylcyanide at 0.degree. C. under the atmosphere of nitrogen. The temperature of the system was returned to room temperature and the resultant solution was stirred for 2 hours. Thereafter, the solution was poured into ice water, and ethyl acetate was added thereto, to perform extraction. The organic phase was washed with saturated brine. The organic phase was dried over anhydrous magnesium sulfate and then the solvent was distilled off under reduced pressure, to give a compound (B-1) as a liquid. Thereto was added 10 ml of water, and then 200 ml of 35% aqueous hydrochloric acid was added thereto. The solution was stirred for 5 hours while refluxed under heating. The temperature of the system was lowered to 0.degree. C., and then the solution was made to weak alkalinity with 2% aqueous potassium hydroxide solution. Ethyl acetate was added to the solution, to separate the solution into two liquid phases. The aqueous phase was made to weak acidic with 1N aqueous hydrochloric acid. This aqueous phase was extracted with ethyl acetate and the resultant organic phase was dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure, to give 8.4 g of a compound (B-2).

Into 50 ml of methyl alcohol was dissolved 7.5 g of the resultant compound (B-2), and then 4 or 5 drops of concentrated sulfuric acid were added thereto. This solution was stirred for 1.5 hour while refluxed under heating. The solution was cooled, and then 10% aqueous potassium carbonate solution and ethyl acetate were added thereto, to perform extraction. The organic phase was washed with saturated brine. The organic phase was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure, to give 8 g of a compound (B-3).

A 50 ml solution of 8 g of the compound (B-3), 4.8 g of phenylisocyanate, and 3.9 g of triethylamine in N,N-dimethylacetoamide was heated to 110.degree. C. and stirred for 4 hours. The temperature of the system was lowered and then water and ethyl acetate were added thereto, to perform extraction. The organic phase was washed with saturated brine. The organic phase was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The resultant residue was subjected to crystallization from a mixed solvent of ethyl acetate and hexane, to give 5.1 g of the coupler (11).

Synthetic Example 3

Synthesis of the Coupler (10)

The coupler (10) was synthesized according to the following route: ##STR36##

The following were mixed: 74.1 g of mesithylene, 11.4 g of .beta.-cyclodextrin, 5.7 g of benzyltriethylammonium chloride, and 100 g of chloroform. The resultant mixture was stirred at 50.degree. C. for 20 minutes. Thereto were dropwise added a solution of 100 g of sodium hydroxide in 100 ml of water, at an internal temperature of 50 to 60.degree. C., under cooling with water, over 30 minutes. The resultant solution was stirred at 50.degree. C. for 4 hours, and it was then refluxed under heating for 5 hours. Ethyl acetate and water were added thereto, to separate the solution into two liquid phases. The aqueous phase was made to acidity with aqueous hydrochloric acid. This aqueous phase was extracted with ethyl acetate and the resultant organic, phase was dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure and the resultant residue was subjected to crystallization from a mixed solvent of ethyl acetate and hexane, to give 36.2 g of a compound (C-1).

Then, 15.5 g of the compound (C-1) and 1.5 ml of concentrated sulfuric acid were dissolved into 150 ml of methanol, and then the resultant solution was refluxed under heating for 6 hours. Ethyl acetate and water were added thereto, to perform extraction, and then the organic phase was washed with aqueous sodium bicarbonate and saturated brine. The resultant solution was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was then subjected to crystallization from a mixed solvent of ethyl acetate and hexane, to give 14.6 g of a compound (C-2).

Into 230 ml of tetrahydrofuran (THF) was dissolved 5.4 g of triphosgene. Under cooling with water, 10.7 g of 2,5-dichloro-4-dioctylsulfamoylaniline was added thereto. The resultant solution was stirred at 10 to 12.degree. C. for 1 hour. To this solution were dropwise added a mixed solution of 12.9 ml of triethylamine and 150 ml of THF under cooling with ice over 25 minutes. The resultant solution was stirred under cooling with ice for 15 minutes. Thereafter, 8.4 g of the compound (C-2) was added thereto under cooling with ice. Furthermore, a mixed solution of 6.5 ml of triethylamine and 30 ml of THF was dropwise added thereto over 5 minutes. The resultant solution was stirred at room temperature for 1 hour. Ethyl acetate and water were added thereto, to perform extraction, and then the organic phase was washed with aqueous dilute hydrochloric acid and saturated brine. The resultant solution was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was then subjected to crystallization from a mixed solvent of ethyl acetate and hexane, to give 14.4 g of a compound (C-3).

Into 250 ml of 1,3-dimethyl-2-imidazolidinone was dissolved 12.6 g of the compound (C-3). Thereto was added 4.6 ml of diisopropylethylamine. The solution was stirred at 120.degree. C. for 3.5 hours. Ethyl acetate and water were added thereto, to perform extraction, and then the organic phase was washed with aqueous dilute hydrochloric acid and saturated brine. The solution was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified with column chromatography. The resultant crude product was then subjected to crystallization from a mixed solvent of ethyl acetate and hexane, to give 3.4 g of the coupler (10).

Synthetic Example 4

Synthesis of the Coupler (16)

The coupler (16) was synthesized according to the following route: ##STR37##

To 10 ml of concentrated sulfuric acid was dropwise added 10 ml of concentrated nitric acid (specific gravity: 1.38) under cooling with ice, and then the resultant mixture of acids was stirred for 10 minutes. To this solution, was dropwise added a solution of 1.1 g of the coupler (10) dissolved in 5 ml of methylene chloride, over 5 minutes, under cooling with ice. Thereafter, the resultant solution was stirred at room temperature for 1 hour. The reaction mixture was poured into ice water, and the solution was extracted with ethyl acetate. The organic phase was washed with aqueous sodium bicarbonate and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was then distilled off under reduced pressure. The residue was purified by column chromatography and was then subjected to crystallization from a mixed solvent of ethyl acetate and hexane, to give 0.7 g of the coupler (16).

Synthetic Example 5

Synthesis of the Coupler (53)

The coupler (53) was synthesized according to the following route: ##STR38##

To 1 liter of a solution of 163 g of isatoic anhydride in acetonitrile, was dropwise added 232.5 g of a 40% aqueous solution of methylamine. The resultant solution was stirred at room temperature for 1 hour. Ethyl acetate and water were added thereto, to separate the solution into two liquid phases. The organic phase was dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure and the residue was subjected to crystallization from a mixed solvent of ethyl acetate and hexane, to give 102.3 g of a compound (D-1).

102.3 g of the compound (D-1) and 1 liter of a solution of 333 g of hydrochloride of iminoether in ethyl alcohol were stirred for 1 hour while refluxed under heating. After the solution was cooled, water was poured into the solution, to precipitate 160 g of crystal of a compound (D-2).

To a 1 liter solution of 73.8 g of the compound (D-2) in methylene chloride was dropwise added a 200 ml solution of 47.9 g of bromine in methylene chloride under cooling with ice. The solution was stirred at room temperature for 10 minutes, and then water was added thereto, to separate the solution into two liquid phases. The organic phase was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. Thereto was added 500 ml of N,N-dimethylacetoamide. The resultant solution was dropwise added a 1 liter solution of 88.3 g of potassium acetate in N,N-dimethylacetoamide. The solution was stirred at room temperature over night. Ethyl acetate and water were added thereto, to separate the solution into two liquid phases. The organic phase was dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure. Thereto were added 800 ml of ethyl alcohol and 82.9 g of potassium carbonate. The resultant solution was stirred at room temperature for 3 hours. Ethyl acetate and water were added thereto, to separate the solution into two liquid phases. The separated aqueous phase was extracted with ethyl acetate, and the resultant organic phase was dried over anhydrous magnesium sulfate. The dried organic phase was purified by column chromatography, and the resultant crude product was subjected to crystallization from a mixed solvent of ethyl acetate and hexane, to give 57 g of a compound (D-3).

Into 500 ml of THF was dissolved 13.1 g of triphosgene. Under cooling with water, 40 g of 2-alkoxymethyl-5-tetradecanolcarbonylaniline was added thereto. The resultant solution was stirred at 10 to 12.degree. C. for 1 hour. To this solution was dropwise added a mixed solution of 30.7 ml of triethylamine and 200 ml of THF over 30 minutes under cooling with ice. The resultant solution was stirred for 1 hour under cooling with ice. Thereafter, the temperature of the system was returned to room temperature. The solution was further stirred for 1 hour, and then 26.2 g of the compound (D-3) was added thereto under cooling with ice. To this solution was dropwise added a mixed solution of 30.7 ml of triethylamine and 50 ml of THF over 5 minutes. The solution was stirred at room temperature for 1 hour. Ethyl acetate and water were added thereto, to perform extraction, and then the organic phase was washed with aqueous dilute hydrochloric acid and saturated brine. The resultant solution was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was then subjected to crystallization from a mixed solvent of ethyl acetate and hexane, to give 52.8 g of a compound (D-4).

Into 200 ml of 1,3-dimethyl-2-imidazolidinone was dissolved 22.8 g of the compound (D-4). Thereto was added 6.7 ml of diisopropylethylamine. The resultant solution was stirred at 150.degree. C. for 10 minutes. Ethyl acetate and water were added thereto, to perform extraction, and then the organic phase was washed with aqueous dilute hydrochloric acid and saturated brine. The solution was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography. The resultant crude product was then subjected to crystallization from a solvent, acetonitrile, to give 12 g of the coupler (53).

Synthetic Example 6

Synthesis of the Coupler (50)

The coupler (50) was synthesized according to the following route: ##STR39##

To a 200 ml solution of 48.9 g of isatoic anhydride in acetonitrile was dropwise added 32.2 g of benzylamine. The resultant solution was stirred. The temperature of the system was raised to 60.degree. C., and the resultant solution was further stirred for 10 minutes. Ethyl acetate and water were added thereto, to separate the solution into two liquid phases. The organic phase was dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure, and the residue was subjected to crystallization from a mixed solvent of ether and hexane, to give 54.6 g of a compound (E-1).

24.9 g of the compound (E-1), 21.6 g of hydrochloride of iminoether, and a 200 ml solution of 10.5 g of p-toluenesulfonic acid monohydrate in ethyl alcohol were stirred for 3 hours while refluxed under heating. After the solution was cooled, 21.6 g of hydrochloride of iminoether was added thereto. The solution was further stirred for 1 hour while refluxed under heating. Ethyl acetate and water were added thereto, to separate the solution into two liquid phases. The organic phase was dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure, and then the residue was subjected to crystallization from a mixed solvent of ether and hexane, to give 33.6 g of a compound (E-2).

To a 300 ml solution of 32.2 g of the compound (E-2) in methylene chloride was dropwise added a 25 ml solution of 15.8 g of bromine in methylene chloride under cooling with ice. The solution was stirred at room temperature for 10 minutes, and then water was added thereto, to separate the solution into two liquid phases. The organic phase was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. Thereto was added 80 ml of N,N-dimethylacetoamide. The resultant solution was dropwise added to a 300-ml solution of 29.4 g of potassium acetate in N,N-dimethylacetoamide. The solution was stirred at room temperature over night. Ethyl acetate and water were added thereto, to separate the solution into two liquid phases. The organic phase was dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure. Thereto were added 400 ml of ethyl alcohol and 24.4 g of potassium carbonate. The solution was stirred at room temperature for 3 hours. Ethyl acetate and water were added thereto, to separate the solution into two liquid phases. The aqueous phase was extracted with ethyl acetate, and the resultant organic phase was dried over anhydrous magnesium sulfate. The dried organic phase was subjected to crystallization from a mixed solvent of ethyl acetate and hexane, to give 24 g of a compound (E-3).

Into 100 ml of THF was dissolved 2.6 g of triphosgene. Under cooling with water, 8.0 g of 2-alkoxymethyl-5-tetradecanolcarbonylaniline was added thereto. The solution was stirred at 10 to 12.degree. C. for 1 hour. To this solution was dropwise added a mixed solution of 6.1 ml of triethylamine and 50 ml of THF over 10 minutes under cooling with ice. The solution was stirred for 1 hour under cooling with ice. The temperature of the solution was returned to room temperature and further stirred for 1 hour. Thereafter, 6.7 g of the compound (E-3) was added thereto under cooling with ice. Furthermore, a mixed solution of 6.1 ml of triethylamine and 12 ml of THF was dropwise added thereto. The solution was stirred at room temperature for 2 hours. Thereafter, ethyl acetate and water were added thereto, to perform extraction, and then the organic phase was washed with aqueous dilute hydrochloric acid and saturated brine. The resultant solution was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography. The resultant crude product was then subjected to crystallization from a mixed solvent of ethyl acetate and hexane, to give 13.1 g of a compound (E-4).

Into 130 ml of 1,3-dimethyl-2-imidazolidinone was dissolved 13.1 g of the compound (E-4). Thereto was added 3.7 ml of diisopropylethylamine. The resultant solution was stirred at 150.degree. C. for 30 minutes. Ethyl acetate and water were added thereto, to perform extraction, and then the organic phase was washed with aqueous dilute hydrochloric acid and saturated brine. The resultant solution was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography. The resultant crude product was then subjected to crystallization from a solvent, acetonitrile, to give 5.5 g of the coupler (50).

Synthetic Example 7

Synthesis of the Coupler (51)

The coupler (51) was synthesized according to the following route: ##STR40##

To a 200 ml solution of 34.3 g of isatoic anh