Title: Silver halide color photosensitive material
Abstract: A silver halide color photosensitive material comprises at least one layer on a support. At least one of the layers contains a coupler represented by general formula (I): ##STR1##wherein X represents H or split-off group; R.sup.1 and R.sup.2 independently represents an electron withdrawing group whose Hammett .sigma.p value is 0.20 or greater, provided that the sum of R.sup.1 and R.sup.2 .sigma.p values is 0.65 or greater; R.sup.3 represents a group selected from alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl and heterocyclic, each of which may have a substituent; R.sup.4 represents H, or a group selected from alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, acyl, alkoxycarbonyl, aryloxycarbonyl and carbamoyl, each of which may have a substituent, provided that R.sup.3 and R.sup.4 may be bonded to form a ring; R.sup.11, R.sup.12 and R.sup.13 independently represent an alkyl group having 1-30 carbon atoms; R represents a substituent; and n represents an integer of 0-3.
Patent Number: 6,858,380 Issued on 02/22/2005 to Kato, et al.
| Inventors:
|
Kato; Yasuhiro (Minami-Ashigara, JP);
Mikoshiba; Hisashi (Minami-Ashigara, JP);
Matsuda; Naoto (Minami-Ashigara, JP)
|
| Assignee:
|
Fuji Photo Film Co., Ltd. (Kanagawa, JP)
|
| Appl. No.:
|
352035 |
| Filed:
|
January 28, 2003 |
Foreign Application Priority Data
| Jan 30, 2002[JP] | 2002-022349 |
| Current U.S. Class: |
430/558; 430/384; 430/385; 430/543 |
| Intern'l Class: |
G03C 001//08; G03C 007//26; G03C 007//32 |
| Field of Search: |
430/558,543,384,385
|
References Cited [Referenced By]
U.S. Patent Documents
| 6159671 | Dec., 2000 | Matsuda | 430/558.
|
| 6322959 | Nov., 2001 | Matsuda | 430/558.
|
| 6399291 | Jun., 2002 | Tateishi et al.
| |
| 6541192 | Apr., 2003 | Kato et al. | 430/558.
|
| 2002/0115029 | Aug., 2002 | Kato et al.
| |
| Foreign Patent Documents |
| 2002-162715 | Jun., 2002 | JP.
| |
Primary Examiner: Letscher; Geraldine
Attorney, Agent or Firm: Sughrue Mion, PLLC
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is based upon and claims the benefit of priority from the
prior Japanese Patent Application No. 2002-22349, filed Jan. 30, 2002, the
entire contents of which are incorporated herein by reference.
Claims
What is claimed is:
1. A silver halide color photosensitive material comprising at least one
layer on a support, wherein at least one of the layers contains a compound
represented by the following general formula (I):
##STR22##
wherein X represents a hydrogen atom or a split-off group; each of R.sup.1
and R.sup.2 represents an electron withdrawing group whose Hammett
substituent constant .sigma.p value is 0.20 or greater, provided that the
sum of R.sup.1 and R.sup.2 .sigma.p values is 0.65 or greater; R.sup.3
represents a substituted or unsubstituted alkyl group, substituted or
unsubstituted alkenyl group, substituted or unsubstituted alkynyl group,
substituted or unsubstituted cycloalkyl group, substituted or
unsubstituted cycloalkenyl group, substituted or unsubstituted aryl group,
or substituted or unsubstituted heterocyclic group; R.sup.4 represents a
hydrogen atom, a substituted or unsubstituted alkyl group, substituted or
unsubstituted alkenyl group, substituted or unsubstituted alkynyl group,
substituted or unsubstituted cycloalkyl group, substituted or
unsubstituted cycloalkenyl group, substituted or unsubstituted aryl group,
substituted or unsubstituted acyl group, substituted or unsubstituted
alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group,
or substituted or unsubstituted carbamoyl group, provided that R.sup.3 and
R.sup.4 may be bonded with each other to thereby form a ring; each of
R.sup.11, R.sup.12 and R.sup.13 independently represents a linear,
branched or cyclic alkyl group having 1 to 30 carbon atoms; R represents a
substituent; and n represents an integer of 0 to 3.
2. A method of forming an image by using the silver halide color
photosensitive material according to claim 1.
3. The silver halide color photosensitive material according to claim 1,
wherein the silver halide color photosensitive material is a reversal
photosensitive material.
4. A method of reducing a magenta stain of a silver halide color
photosensitive material by using the silver halide color photosensitive
material according to claim 1.
5. A silver halide color photosensitive material comprising at least one
layer on a support, wherein at least one of the layers contains a compound
represented by the following general formula (I):
##STR23##
wherein X represents a hydrogen atom, halogen atom, alkoxy group having 1
to 32 carbon atoms, aryloxy group having 6 to 32 carbon atoms, alkylthio
group having 1 to 32 carbon atoms, arylthio group having 6 to 32 carbon
atoms, heterocyclic thio group having 2 to 32 carbon atoms,
alkoxycarbonyloxy group having 2 to 32 carbon atoms, aryloxycarbonyloxy
group having 7 to 32 carbon atoms, carbamoyloxy group having 1 to 32
carbon atoms, heterocyclic carbonyloxy group having 3 to 32 carbon atoms,
or 5 or 6-membered nitrogen-containing heterocyclic group having 2 to 32
carbon atoms, the heterocyclic group bonding to the coupling active site
with its nitrogen atom; R.sup.1 represents a cyano group; R.sup.2
represents an alkoxycarbonyl group; R.sup.3 represents a substituted or
unsubstituted alkyl group, substituted or unsubstituted alkenyl group,
substituted or unsubstituted alkynyl group, substituted or unsubstituted
cycloalkyl group, substituted or unsubstituted cycloalkenyl group,
substituted or unsubstituted aryl group, or substituted or unsubstituted
heterocyclic group; R.sup.4 represents a hydrogen atom, substituted or
unsubstituted alkyl group, substituted or unsubstituted alkenyl group,
substituted or unsubstituted alkynyl group, substituted or unsubstituted
cycloalkyl group, substituted or unsubstituted cycloalkenyl group,
substituted or unsubstituted aryl group, substituted or unsubstituted acyl
group, substituted or unsubstituted alkoxycarbonyl group, substituted or
unsubstituted aryloxycarbonyl group, or substituted or unsubstituted
carbamoyl group, provided that R.sup.3 and R.sup.4 may be bonded with each
other to thereby form a ring; each of R.sup.11, R.sup.12 and R.sup.13
independently represents a linear, branched or cyclic alkyl group having 1
to 30 carbon atoms; R represents a substituent; and n represents an
integer of 0 to 3.
6. A method of forming an image by using the silver halide color
photosensitive material according to claim 5.
7. The silver halide color photosensitive material according to claim 5,
wherein the silver halide color photosensitive material is a reversal
photosensitive material.
8. A method of reducing a magenta stain of a silver halide color
photosensitive material by using the silver halide color photosensitive
material according to claim 5.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a pyrrolotriazole compound having a
specific structure, and relates to a silver halide color photosensitive
material having its color reproduction and color image durability
enhanced, having its staining in various forms inhibited and having its
processing stability enhanced by the use of a cyan coupler of the
pyrrolotriazole compound.
2. Description of the Related Art
With respect to silver halide color photosensitive materials, it is well
known that an oxidized aromatic primary amine color developing agent,
which uses exposed silver halides as an oxidizer, reacts with a coupler to
thereby produce dyes of indophenol, indoaniline, indamine, azomethine,
phenoxazine, phenazine, etc. leading to image formation. In this system of
photography, use is made of the subtractive color process, and color
images are formed by yellow, magenta and cyan dyes.
In the formation of cyan dye images among these, a phenol-type or
naphthol-type coupler is commonly employed. However, the dyes formed from
these couplers exhibit undesirable absorption in the yellow to magenta
region, thereby posing a problem of deterioration of color reproduction.
Therefore, it is demanded to resolve this problem.
Especially in recent years, demands on the system in which image
information is digitized and subjected to image processing, and thereafter
the image information is exposed to a silver halide color photosensitive
material, known as the digital photography, are increasing. Particularly
in this system, there is a strong demand for a silver halide color
photosensitive material of large color reproduction range wherein formed
dyes do not exhibit the above undesirable absorption.
On the other hand, high saturation and large color reproduction range are
demanded on reversal films. Since the method of emphasizing an interlayer
effect has a drawback of, for example, deterioration in processing
dependence, it is demanded to realize the high saturation and large color
reproduction range by the use of a coupler of excellent hue.
As means for solving this problem, there have been proposed heterocyclic
compounds as described in, for example, U.S. Pat. Nos. 4,728,598 and
4,873,183 and EP 0249453A2. However, the couplers described therein have
fatal drawbacks such as low coupling activity and poor dye durability.
As a coupler which overcomes these problems, there have been proposed
pyrrolotriazole couplers as described in U.S. Pat. No. 5,256,526 and EP
0545300. It has been revealed that these couplers, although being
excellent in hue and coupling activity, need further improvement because
color photosensitive materials wherein these couplers are employed are not
satisfactory in color image durability. Further, the pyrrolotriazole
couplers pose such a problem that at bleach-fix processing, the color
formation efficiency is lowered by conversion of dyes to leuco compounds
(discoloring of some dyes by reduction), the problem known as the blix
color fading. Still further, the couplers pose a problem of cyan staining
in various forms. Still further, the conventional pyrrolotriazole cyan
couplers have a drawback in that when processed with the use of formalin,
the photosensitive material containing the couplers suffer magenta
staining upon aging.
Moreover, shortening of processing steps and reduction of replenishment
rate are demanded on the color reversal films. The inventors have
conducted investigations, and as a result it has been found that there is
such a problem that the maximum density drop of cyan is inevitably
increased when reduction of replenishment rate has been carried out for
not only the color developer but also the reversal bath. Furthermore, this
problem is often aggravated in the use of hitherto proposed
pyrrolotriazole couplers as compared with the use of conventional
phenol-type cyan couplers. Solving this matter is strongly demanded.
BRIEF SUMMARY OF THE INVENTION
Therefore, it is an object of the present invention to provide a novel
pyrrolotriazole compound of specific structure which is useful as a
coupler of silver halide color photosensitive material and which can be a
useful intermediate of chemical, medicinal and agricultural-chemical
organic compounds (1). It is another object of the present invention to
provide a silver halide color photosensitive material which by virtue of
the use of the pyrrolotriazole cyan coupler, is excellent in color
reproduction and color image durability (2), and which further realizes
reduction of cyan stain resulting from reaction with any remaining color
developing agents, reduction of blix fading, extreme reduction of magenta
stain and enhancement of processing stability (3).
The inventors have conducted extensive studies on the 2-position
substituent and split-off groups with respect to pyrrolotriazole-type
couplers of excellent hue. As a result, it has been found that the above
objects can be attained by a coupler of unknown really novel structure
represented by the following general formula. That is, the above objects
have been attained by the following means.
(1) A silver halide color photosensitive material comprising at least one
layer on a support, wherein at least one of the layers contains a coupler
represented by the following general formula (I):
##STR2##
In the general formula (I), X represents a hydrogen atom or a split-off
group; each of R.sup.1 and R.sup.2 represents an electron withdrawing
group whose Hammett substituent constant .sigma.p value is 0.20 or
greater, provided that the sum of R.sup.1 and R.sup.2 .sigma.p values is
0.65 or greater; R.sup.3 represents a substituted or unsubstituted alkyl
group, substituted or unsubstituted alkenyl group, substituted or
unsubstituted alkynyl group, substituted or unsubstituted cycloalkyl
group, substituted or unsubstituted cycloalkenyl group, substituted or
unsubstituted aryl group, or substituted or unsubstituted heterocyclic
group; R.sup.4 represents a hydrogen atom, a substituted or unsubstituted
alkyl group, substituted or unsubstituted alkenyl group, substituted or
unsubstituted alkynyl group, substituted or unsubstituted cycloalkyl
group, substituted or unsubstituted cycloalkenyl group, substituted or
unsubstituted aryl group, substituted or unsubstituted acyl group,
substituted or unsubstituted alkoxycarbonyl group, substituted or
unsubstituted aryloxycarbonyl group, or substituted or unsubstituted
carbamoyl group, provided that R.sup.3 and R.sup.4 may be bonded with each
other to thereby form a ring; each of R.sup.11, R.sup.12 and R.sup.13
independently represents a linear, branched or cyclic alkyl group having 1
to 30 carbon atoms; R represents a substituent; and n represents an
integer of 0 to 3.
Additional objects and advantages of the invention will be set forth in the
description which follows, and in part will be obvious from the
description, or may be learned by practice of the invention. The objects
and advantages of the invention may be realized and obtained by means of
the instrumentalities and combinations particularly pointed out
hereinafter.
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below. First, the
expression "Hammett substituent constant .sigma.p value" used herein will
be briefly described. Hammett's rule is a rule of thumb advocated by L. P.
Hammett in 1935 for quantitatively considering the effect of substituents
on the reaction or equilibrium of benzene derivatives, and the
appropriateness thereof is now widely recognized. The substituent constant
determined in the Hammett's rule involves .sigma.p value and .sigma.m
value. These values can be found in a multiplicity of general
publications, and are detailed in, for example, "Lange's Handbook of
Chemistry" 12th edition by J. A. Dean, 1979 (Mc Graw-Hill) and "Kagaku no
Ryoiki" special issue, no. 122, p.p. 96 to 103, 1979 (Nankodo). Although
in the present invention, substituents are defined by the Hammett
substituent constant .sigma.p or described thereby, this should not be
construed as limitation to only substituents whose values are known by
literature and can be found in the above publications, and should
naturally be construed as including substituents whose values, even if
unknown by literature, would be included in stated ranges when measured
according to the Hammett's rule. Further, although the compounds
represented by the general formula (I) of the present invention are not
benzene derivatives, the .sigma.p value is used, irrespective of the
position of substitution, as a scale for evaluating the electronic effect
of substituents thereof.
In the present invention, the .sigma.p value will be used in the above
meaning below. The terminology "lipophilicity" used in the present
invention refers to a solubility in water at room temperature being 10% or
less.
Herein, the heterocycle refers to a ring having a heteroatom therein. The
heterocycles include those having aromaticity, and may be condensed with
benzene rings, other heterocycles, etc. Further, the heterocycles may have
substituents. As the heteroatom, there can be mentioned N, S, O or P.
Herein, the substituents and substituents which may be had by the alkyl
group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group,
aryl group and heterocycle are not limited as long as they are capable of
substituting unless otherwise specified. For example, the substituents can
be any of an alkyl group, alkenyl group, alkynyl group, cycloalkyl group,
cycloalkenyl group, aryl group, heterocyclic group, acyl group, acyloxy
group, acylamino group, alkoxy group, aryloxy group, heterocyclic oxy
group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic
oxycarbonyl group, alkylcarbamoyl group, arylcarbamoyl group,
alkylsulfonyl group, arylsulfonyl group, alkylsulfamoyl group,
arylsulfamoyl group, alkylsulfonamido group, arylsulfonamido group,
alkylamino group, arylamino group, alkylsulfinyl group, arylsulfinyl
group, alkylthio group, arylthio group, mercapto group, hydroxyl group,
cyano group, nitro group, hydroxylamino group, halogen atom and the like.
The cyan couplers represented by the general formula (I) of the present
invention will be described in detail below.
In the general formula (I), X represents a hydrogen atom or a split-off
group (namely, a group which can be split off at a coupling reaction with
an oxidized color developing agent). The split-off groups represented by X
preferably include a halogen atom (a fluorine atom, chlorine atom, bromine
atom or iodine atom), alkoxy group having 1 to 32 carbon atoms, aryloxy
group having 6 to 32 carbon atoms, alkylthio group having 1 to 32 carbon
atoms, arylthio group having 6 to 32 carbon atoms, heterocyclic thio group
having 2 to 32 carbon atoms, alkoxycarbonyloxy group having 2 to 32 carbon
atoms, aryloxycarbonyloxy group having 7 to 32 carbon atoms, carbamoyloxy
group having 1 to 32 carbon atoms, heterocyclic carbonyloxy group having 3
to 32 carbon atoms, 5 or 6-membered nitrogen-containing heterocyclic group
having 2 to 32 carbon atoms, the heterocyclic group bonding to the
coupling active site with its nitrogen atom, and the like.
The substituent X is preferably a hydrogen atom, halogen atom, arylthio
group, carbamoyloxy group or heterocyclic carbonyloxy group. The
substituent X is more preferably a hydrogen atom or heterocyclic
carbonyloxy group, and most preferably a hydrogen atom.
With respect to the cyan couplers of the present invention, the color
formation as cyan images is realized by such a limitation that R.sup.1 and
R.sup.2 both represent electron withdrawing groups of 0.20 or greater
.sigma.p value, the sum of R.sup.1 and R.sup.2 .GAMMA.p values being 0.65
or greater. The sum of R.sup.1 and R.sup.2 .sigma.p values is preferably
0.70 or greater, and the upper limit thereof is about 2.0.
Each of R.sup.1 and R.sup.2 represents an electron withdrawing group of
0.20 or greater Hammett substituent constant .sigma.p value, preferably an
electron withdrawing group of 0.30 or greater Hammett substituent constant
.sigma.p value. The upper limit of the Hammett substituent constant
.sigma.p value is 1.0 or less.
As examples of R.sup.1 and R.sup.2 groups which are electron withdrawing
groups of 0.20 or greater .sigma.p value, there can be mentioned an acyl
group, acyloxy group, carbamoyl group, alkoxycarbonyl group,
aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group,
diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group,
arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy
group, acylthio group, sulfamoyl group, thiocyanato group, thiocarbonyl
group, halogenated alkyl group, halogenated alkoxy group, halogenated
aryloxy group, halogenated alkylamino group, halogenated alkylthio group,
aryl group substituted with another electron withdrawing group of 0.20 or
greater .sigma.p value, heterocyclic group, halogen atom, azo group and
selenocyanato group.
The groups capable of further having a substituent among the R.sup.1 and
R.sup.2 groups may further have the following substituents. These
substituents can be, for example, a halogen atom, alkyl group, alkenyl
group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group,
heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl
group, sulfo group, amino group, alkoxy group, aryloxy group, acylamino
group, alkylamino group, anilino group, ureido group, sulfamoylamino
group, alkylthio group, arylthio group, alkoxycarbonylamino group,
sulfonamido group, carbamoyl group, sulfamoyl group, sulfonyl group,
alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group,
carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imido
group, heterocyclic thio group, sulfinyl group, phosphonyl group,
aryloxycarbonyl group, acyl group and the like.
More specifically, the substituents of the R.sup.1 and R.sup.2 groups can
be, for example, a halogen atom (e.g., a chlorine atom or bromine atom);
alkyl group, alkenyl group, alkynyl group, cycloalkyl group and
cycloalkenyl group (e.g., a linear or branched alkyl group having 1 to 32
carbon atoms, aralkyl group having 7 to 38 carbon atoms, linear or
branched alkenyl group having 2 to 32 carbon atoms, linear or branched
alkynyl group having 2 to 32 carbon atoms, linear or branched cycloalkyl
group having 3 to 32 carbon atoms and linear or branched cycloalkenyl
group having 3 to 32 carbon atoms, such as methyl, ethyl, propyl,
isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl,
3-(3-pentadecylphenoxy)propyl,
3-{4-{2-[4-(4-hydroxyphenylsulfonyl)phenoxy]dodecanamido}phenyl}propy
1,2-ethoxytridecyl, trifluoromethyl, cyclopentyl,
3-(2,4-di-t-amylphenoxy)propyl, vinyl, 1-propenyl and 2-pentenyl); aryl
group (e.g., phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl or
4-tetradecanamidophenyl); heterocyclic group (e.g., imidazolyl, pyrazolyl,
triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl or 2-benzothiazolyl); cyano
group, hydroxyl group, nitro group, carboxyl group, sulfo group and amino
group; alkoxy group (e.g., methoxy, ethoxy, 2 methoxyethoxy,
2-dodecylethoxy or 2-methanesulfonylethoxy); an aryloxy group (e.g.,
phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy,
3-t-butyloxycarbamoylphenoxy or 3-methoxycarbamoylphenoxy); acylamino
group (e.g., acetamido, benzamido, tetradecanamido,
2-(2,4-di-t-amylphenoxy)butanamido,
4-(3-t-butyl-4-hydroxyphenoxy)butanamido or
2-{4-(4-hydroxyphenylsulfonyl)phenoxy}decanamido); alkylamino group (e.g.,
methylamino, butylamino, dodecylamino, diethylamino or methylbutylamino);
anilino group (e.g., phenylamino, 2-chloroanilino,
2-chloro-5-tetradecanaminoanilino, 2-chloro-5-dodecyloxycarbonylanilino,
N-acetylanilino or
2-chloro-5-{2-(3-t-butyl-4-hydroxyphenoxy)dodecanamido}anilino); ureido
group (e.g., phenylureido, methylureido or N,N-dibutylureido);
sulfamoylamino group (e.g., N,N-dipropylsulfamoylamino or
N-methyl-N-decylsulfamoylamino); alkylthio group (e.g., methylthio,
octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio or
3-(4-t-butylphenoxy)propylthio); arylthio group (e.g., phenylthio,
2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio
or 4-tetradecanamidophenylthio); alkoxycarbonylamino group (e.g.,
methoxycarbonylamino or tetradecyloxycarbonylamino); sulfonamido group
(e.g., methanesulfonamido, hexadecanesulfonamido, benzenesulfonamido,
p-toluenesulfonamido, octadecanesulfonamido or
2-methoxy-5-t-butylbenzenesulfonamido); carbamoyl group (e.g.,
N-ethylcarbamoyl, N,N-dibutylcarbamoyl, N-(2-dodecyloxyethyl)carbamoyl,
N-methyl-N-dodecylcarbamoyl or
N-{3-(2,4-di-t-amylphenoxy)propyl}carbamoyl); sulfamoyl group (e.g.,
N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-(2-dodecyloxyethyl)sulfamoyl,
N-ethyl-N-dodecylsulfamoyl or N,N-diethylsulfamoyl); sulfonyl group (e.g.,
methanesulfonyl, octanesulfonyl, benzenesulfonyl or toluenesulfonyl);
alkoxycarbonyl group (e.g., methoxycarbonyl, butyloxycarbonyl,
dodecyloxycarbonyl or octadecyloxycarbonyl); heterocyclic oxy group (e.g.,
1-phenyltetrazol-5-oxy or 2-tetrahydropyranyloxy); azo group (e.g.,
phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo or
2-hydroxy-4-propanoylphenylazo); acyloxy group (e.g., acetoxy);
carbamoyloxy group (e.g., N-methylcarbamoyloxy or N-phenylcarbamoyloxy);
silyloxy group (e.g., trimethylsilyloxy or dibutylmethylsilyloxy);
aryloxycarbonylamino group (e.g., phenoxycarbonylamino); imido group
(e.g., N-succinimido, N-phthalimido or 3-octadecenylsuccinimido);
heterocyclic thio group (e.g., 2-benzothiazolylthio or
2,4-diphenoxy-1,3,5-triazole-6-thio or 2-pyridylthio); sulfinyl group
(e.g., dodecanesulfinyl, 3-pentadecylphenylsulfinyl or
3-phenoxypropylsulfinyl); phosphonyl group (e.g., phenoxyphosphonyl,
octyloxyphosphonyl or phenylphosphonyl); aryloxycarbonyl group (e.g.,
phenoxycarbonyl); acyl group (e.g., acetyl, 3-phenylpropanoyl, benzoyl or
4-dodecyloxybenzoyl); and the like.
The alkyl of a group having alkyl moiety represented by R.sup.1 or R.sup.2
means a linear or branched alkyl or cycloalkyl. The substituted alkyl
groups comprehend an aralkyl, an alkenyl, an alkynyl and a cycloalkenyl.
Accordingly, the alkoxycarbonyl groups comprehend linear or branched
alkoxycarbonyl, aralkyloxycarbonyl, alkenyloxycarbonyl,
alkynyloxycarbonyl, cycloalkoxycarbonyl and cycloalkenoxycarbonyl groups.
R.sup.1 and R.sup.2 will be described in greater detail below. As the
electron withdrawing group of 0.20 or greater .sigma.p value, there can be
mentioned an acyl group (e.g., acetyl, 3-phenylpropanoyl, benzoyl or
4-dodecyloxybenzoyl); acyloxy group (e.g., acetoxy); carbamoyl group
(e.g., carbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl,
N,N-dibutylcarbamoyl, N-(2-dodecyloxyethyl)carbamoyl,
N-(4-n-pentadecanamido)phenylcarbamoyl, N-methyl-N-dodecylcarbamoyl or
N-{3-(2,4-di-t-amylphenoxy)propyl}carbamoyl); alkoxycarbonyl group (e.g.,
methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl,
tert-butyloxycarbonyl, isobutyloxycarbonyl, butyloxycarbonyl,
dodecyloxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl or
cyclohexenoxycarbonyl); aryloxycarbonyl group (e.g., phenoxycarbonyl);
cyano group; nitro group; dialkylphosphono group (e.g.,
dimethylphosphono); diarylphosphono group (e.g., diphenylphosphono);
diarylphosphinyl group (e.g., diphenylphosphinyl); alkylsulfinyl group
(e.g., 3-phenoxypropylsulfinyl); arylsulfinyl group (e.g.,
3-pentadecylphenylsulfinyl); alkylsulfonyl group (e.g., methanesulfonyl or
octanesulfonyl); arylsulfonyl group (e.g., benzenesulfonyl or
toluenesulfonyl); sulfonyloxy group (e.g., methanesulfonyloxy or
toluenesulfonyloxy); acylthio group (e.g., acetylthio or benzoylthio);
sulfamoyl group (e.g., N-ethylsulfamoyl, N,N-dipropylsulfamoyl,
N-(2-dodecyloxyethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl or
N,N-diethylsulfamoyl); thiocyanato group; thiocarbonyl group (e.g.,
methylthiocarbonyl or phenylthiocarbonyl); halogenated alkyl group (e.g.,
trifluoromethane or heptafluoropropane); halogenated alkoxy group (e.g.,
trifluoromethyloxy); halogenated aryloxy group (e.g.,
pentafluorophenyloxy); halogenated alkylamino group (e.g.,
N,N-di(trifluoromethyl)amino); halogenated alkylthio group (e.g.,
difluoromethylthio or 1,1,2,2-tetrafluoroethylthio); aryl group
substituted with another electron withdrawing group of 0.20 or greater
.sigma.p value (e.g., 2,4-dinitrophenyl, 2,4,6-trichlorophenyl or
pentachlorophenyl); heterocyclic group (e.g., 2-benzoxazolyl,
2-benzothiazolyl, 1-phenyl-2-benzimidazolyl, 5-chloro-1-tetrazolyl or
1-pyrrolyl); halogen atom (e.g., chlorine atom or bromine atom); azo group
(e.g., phenylazo); or selenocyanato group.
The groups capable of further having a substituent among these substituents
may further have the above substituents.
As preferred examples of R.sup.1 and R.sup.2 groups, there can be mentioned
an acyl group having 2 to 32 carbon atoms, acyloxy group having 2 to 32
carbon atoms, carbamoyl group having 1 to 32 carbon atoms, alkoxycarbonyl
group having 2 to 32 carbon atoms, aryloxycarbonyl group having 7 to 32
carbon atoms, cyano group, a nitro group, alkylsulfinyl group having 1 to
32 carbon atoms, arylsulfinyl group having 6 to 32 carbon atoms,
alkylsulfonyl group having 1 to 32 carbon atoms, arylsulfonyl group having
6 to 32 carbon atoms, sulfamoyl group having 0 to 32 carbon atoms,
halogenated alkyl group having 1 to 32 carbon atoms, halogenated alkoxy
group having 1 to 32 carbon atoms, halogenated alkylthio group having 1 to
32 carbon atoms, halogenated aryloxy group having 7 to 32 carbon atoms,
aryl group having 7 to 32 carbon atoms substituted with two or more other
electron withdrawing groups of 0.20 or greater .sigma.p value, and 5 to
8-membered heterocyclic group having 1 to 36 carbon atoms wherein a
nitrogen atom, oxygen atom or sulfur atom is contained.
As more preferred examples of R.sup.1 and R.sup.2 groups, there can be
mentioned an alkoxycarbonyl group having 2 to 32 carbon atoms, nitro
group, cyano group, arylsulfonyl group having 6 to 32 carbon atoms,
carbamoyl group having 1 to 32 carbon atoms and halogenated alkyl group
having 1 to 32 carbon atoms. R.sup.1 most preferably represents a cyano
group. R.sup.2 especially preferably represents an alkoxycarbonyl group
having 2 to 32 carbon atoms, and most preferably represents a branched
alkoxycarbonyl group having 4 to 32 carbon atoms (in particular,
cycloalkoxycarbonyl group).
In the general formula (I), R.sup.3 represents a substituted or
unsubstituted alkyl group, substituted or unsubstituted alkenyl group,
substituted or unsubstituted alkynyl group, substituted or unsubstituted
cycloalkyl group, substituted or unsubstituted cycloalkenyl group,
substituted or unsubstituted aryl group, or substituted or unsubstituted
heterocyclic group.
More specifically, the alkyl, alkenyl, alkynyl, cycloalkyl and cycloalkenyl
groups represented by R.sup.3 can be a linear or branched alkyl group
having 1 to 32 carbon atoms, aralkyl group having 7 to 32 carbon atoms,
alkenyl group having 2 to 32 carbon atoms, alkynyl group having 2 to 32
carbon atoms, cycloalkyl group having 3 to 32 carbon atoms and
cycloalkenyl group having 3 to 32 carbon atoms. Still more specifically,
they can be, for example, methyl, ethyl, propyl, isopropyl, t-butyl,
tridecyl, 2-methanesulfonylethyl, 3-(3-pentadecylphenoxy)propyl,
3-{4-{2-[4-(4-hydroxyphenylsulfonyl)phenoxy]dodecanamido}phenyl}propy 1,
2-ethoxytridecyl, trifluoromethyl, cyclopentyl,
3-(2,4-di-t-amylphenoxy)propyl, vinyl, 1-propenyl and 2-pentenyl. With
respect to the aryl group, one having 6 to 36 carbon atoms is preferred,
and monocyclic one is more preferred. The aryl group can be, for example,
phenyl, 4-t-butylphenyl, 2-methylphenyl, 2,4,6-trimethylphenyl,
2-methoxyphenyl, 4-methoxyphenyl, 2,6-dichlorophenyl, 2-chlorophenyl,
2,4-dichlorophenyl or the like. With respect to the heterocyclic group, a
5 to 8-membered heterocycle having 1 to 36 carbon atoms wherein a nitrogen
atom, oxygen atom or sulfur atom is contained is preferred. A 5 or
6-membered heterocycle bonding to --NR.sup.4 of the general formula (I)
through the nitrogen atom contained in the heterocycle is more preferred.
Such a heterocycle may form a condensed ring in cooperation with a benzene
ring or another heterocycle. The heterocyclic group can be, for example,
any of imidazolyl, pyrazolyl, triazolyl, piperidino, pyrrolidyl, pyrrolyl,
morpholino, pyrazolidyl, thiazolidyl and the like, among which pyrrolidyl
is preferred.
The groups capable of further having a substituent among these substituents
may further have the substituents set forth above as examples with respect
to R.sup.1 and R.sup.2.
Preferably, R.sup.3 represents a substituted or unsubstituted alkyl group,
substituted or unsubstituted alkenyl group, substituted or unsubstituted
alkynyl group, substituted or unsubstituted cycloalkyl group, or
substituted or unsubstituted cycloalkenyl group.
R.sup.4 represents a hydrogen atom, substituted or unsubstituted alkyl
group, substituted or unsubstituted alkenyl group, substituted or
unsubstituted alkynyl group, substituted or unsubstituted cycloalkyl
group, substituted or unsubstituted cycloalkenyl group, substituted or
unsubstituted aryl group, substituted or unsubstituted acyl group,
substituted or unsubstituted alkoxycarbonyl group, substituted or
unsubstituted aryloxycarbonyl group, substituted or unsubstituted
carbamoyl group or the like.
More specifically, R.sup.4 can be a hydrogen atom, and the alkyl, alkenyl,
alkynyl, cycloalkyl and cycloalkenyl groups represented by R.sup.4 can be
a linear or branched alkyl group having 1 to 32 carbon atoms, aralkyl
group having 7 to 32 carbon atoms, alkenyl group having 2 to 32 carbon
atoms, alkynyl group having 2 to 32 carbon atoms, cycloalkyl group having
3 to 32 carbon atoms and cycloalkenyl group having 3 to 32 carbon atoms.
Still more specifically, they can be, for example, methyl, ethyl, propyl,
isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl,
3-(3-pentadecylphenoxy)propyl,
3-{4-{2-[4-(4-hydroxyphenylsulfonyl)phenoxy]dodecanamid o}phenyl}propyl,
2-ethoxytridecyl, trifluoromethyl, cyclopentyl,
3-(2,4-di-t-amylphenoxy)propyl, vinyl group, 1-propenyl group and
2-pentenyl group. With respect to the aryl group, one having 6 to 36
carbon atoms is preferred, and monocyclic one is more preferred. The aryl
group can be, for example, phenyl, 4-t-butylphenyl, 2-methylphenyl,
2,4,6-trimethylphenyl, 2-methoxyphenyl, 4-methoxyphenyl,
2,6-dichlorophenyl, 2-chlorophenyl, 2,4-dichlorophenyl or the like. The
acyl group is preferably one having 2 to 32 carbon atoms, and can be, for
example, acetyl, pivaloyl, octanoyl or benzoyl. Examples of the
alkoxycarbonyl, aryloxycarbonyl and carbamoyl groups can be, for example,
those described above with respect to groups employed for substitution of
R.sup.1 and R.sup.2.
The groups capable of further having a substituent among these substituents
may further have the substituents set forth above as examples with respect
to groups employed for substitution of R.sup.1 and R.sup.2.
Preferably, R.sup.4 represents a substituted or unsubstituted alkyl group,
substituted or unsubstituted alkenyl group, substituted or unsubstituted
alkynyl group, substituted or unsubstituted cycloalkyl group, substituted
or unsubstituted cycloalkenyl group, or substituted or unsubstituted aryl
group.
R.sup.3 and R.sup.4 may be bonded with each other to thereby form a 5 or
6-membered heterocycle bonding to the benzene ring of the general formula
(I) trough the nitrogen atom of the general formula (I). This heterocyclic
group can be, for example, any of imidazolyl, pyrazolyl, triazolyl,
piperidyl, piperidino, pyrrolidinyl, pyrrolyl, morpholyl, morpholino,
pyrazolidinyl, thiazolidinyl, pyrazolinyl, piperadinyl and the like. These
heterocycles may form a condensed ring in cooperation with a benzene ring
or another heterocycle.
With respect to R.sup.3 and R.sup.4, those which form a ring structure are
preferred to those which do not form any ring structure. In particular,
groups which form a 6-membered heterocycle bonding to the nitrogen atom
are preferred, and those which form morpholino, piperadinyl substituted
with an acyl group, piperidino or piperidino substituted with a carboxyl
group are more preferred.
In the general formula (I), each of R.sup.11 and R.sup.12 represents a
linear, branched or cyclic alkyl group having 1 to 30 carbon atoms. In
particular, an unsubstituted alkyl group is preferred.
As examples of the substituents represented by R.sup.11 and R.sup.12 in the
general formula (I), there can be mentioned methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, n-hexyl,
cyclohexyl, n-heptyl, n-octyl, t-octyl, n-nonyl, n-decyl, undecyl, dodecyl
and the like.
Preferably, each of R.sup.11 and R.sup.12 represents methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl,
n-hexyl or cyclohexyl.
More preferably, each of R.sup.11 and R.sup.12 represents methyl, ethyl,
n-propyl, isopropyl or n-butyl group. Most preferably, each of R.sup.11
and R.sup.12 represents n-propyl.
In the general formula (I), R.sup.13 represents a linear, branched or
cyclic alkyl group having 1 to 30 carbon atoms.
As examples of the alkyl group represented by R.sup.13 in the general
formula (I), there can be mentioned methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, n-hexyl, cyclohexyl,
n-heptyl, n-octyl, t-octyl, n-nonyl, n-decyl, undecyl, dodecyl and the
like. Of these, tertiary alkyl groups are preferred, which are, for
example, t-butyl and t-octyl. A t-octyl group is most preferred.
With respect to the substitution positions of substituents --OR.sup.11,
--OR.sup.12 and --R.sup.13 in the general formula (I), it is preferred
that --OR.sup.11, --OR.sup.12 and --R.sup.13 be located at 2-position,
5-position and 4-position to the group NHSO.sub.2 --, respectively, or
that --OR.sup.11, --OR.sup.12 and --R.sup.13 be located at 2-position,
3-position and 5-position to the group NHSO.sub.2 --, respectively.
In the general formula (I), R represents a substituent, and n is an integer
of 0 to 3.
As examples of substituents represented by R in the general formula (I),
there can be mentioned those set forth above with respect to R.sup.1.
An alkyl group and alkoxy group can be mentioned as preferred examples of
substituents represented by R in the general formula (I).
In the general formula (I), n is most preferably 0.
For constituting the cyan coupler represented by the general formula (I) of
the present invention, it is preferred to employ such a combination that X
represents a hydrogen atom, halogen atom, arylthio group, carbamoyloxy
group or heterocyclic carbonyloxy group; each of R.sup.1 and R.sup.2
independently represents a group selected from among a cyano group,
alkoxycarbonyl group, nitro group, arylsulfonyl group, carbamoyl group and
halogenated alkyl group; R.sup.3 and R.sup.4 are those which form a ring
structure; each of R.sup.11 and R.sup.12 represents an alkyl group having
6 or less carbon atoms; R.sup.13 represents a t-butyl group or t-octyl
group; and n is 0.
For constituting the cyan coupler represented by the general formula (I),
it is more preferred to employ such a combination that X represents a
hydrogen atom, halogen atom or heterocyclic carbonyloxy group; R.sup.1
represents a cyano group; R.sup.2 represents a branched alkoxycarbonyl
group; R.sup.3 and R.sup.4 are those which form a 6-membered ring
structure; each of R.sup.11 and R.sup.12 represents an alkyl group having
2 to 4 carbon atoms; R.sup.13 represents a t-butyl group or t-octyl group;
and n is 0.
For constituting the cyan coupler represented by the general formula (I),
it is most preferred to employ such a combination that X represents a
hydrogen atom; R.sup.1 represents a cyano group; R.sup.2 represents a
branched alkoxycarbonyl group; R.sup.3 and R.sup.4 are those which form a
6-membered ring structure; each of R.sup.11 and R.sup.12 represents an
n-propyl group; R.sup.13 represents a t-octyl group; and n is 0.
For causing the cyan coupler of the present invention to be contained in a
silver halide photosensitive material, preferably a red-sensitive silver
halide emulsion layer, it is preferred that the cyan coupler be a
so-called incorporated coupler. For this purpose, it is preferred that the
total number of the carbon atoms of R.sup.11 to R.sup.13 be 10 or more.
With respect to the cyan couplers and pyrrolotriazole compounds defined in
the present invention, specific examples will be shown below, which
however in no way limit the scope thereof.
##STR3##
##STR4##
##STR5##
##STR6##
##STR7##
##STR8##
The compounds of the general formula (I) can be synthesized by the below
illustrated processes.
Specific synthetic examples for obtaining pyrrolotriazole compounds
according to the present invention will be described below.
Synthetic Example 1 (Synthesis of Exemplified Compound 1)
Exemplified compound (1) was synthesized in accordance with the following
synthetic route:
##STR9##
##STR10##
##STR11##
Synthesis of Compound (A):
At 10.degree. C. or below, 76.3 mL (1.05 mol) of thionyl chloride was
dropped into a solution obtained by dissolving 202 g (1 mol) of
4-chloro-3-nitrobenzoic acid in 500 milliliters (hereinafter also referred
to as "mL") of toluene and 1 mL of N,N-dimethylformamide. The resultant
reaction mixture was heated and agitated at reflux temperature for 90 min
(the reaction mixture changed from a suspension to a homogeneous liquid).
Subsequently, the toluene was distilled off in vacuum. Thus, 220 g of waxy
solid (A) was obtained.
Synthesis of Compound (B):
A solution obtained by dissolving 220 g (1 mol) of compound (A) in 300 mL
of acetonitrile was slowly dropped into a solution obtained by dissolving
136.2 g (2 mol) of imidazole in 3000 mL of acetonitrile at 5.degree. C. or
below. Subsequently, 150 g (3 mol) of hydrazine monohydrate was dropped
into the mixture at 13.degree. C. or below. The resultant reaction mixture
was agitated at 15.degree. C. for 90 min, and the thus obtained
precipitate was harvested by filtration and satisfactorily washed with
water. The thus obtained crystal was dried at 5.degree. C. overnight,
thereby obtaining 166 g (yield 77%) of compound (B) (melting point:
170-172.degree. C., dec.).
Synthesis of Compound (C):
104.6 mL (0.75 mol) of triethylamine was slowly dropped into a solution
obtained by dissolving 146.7 g (0.75 mol) of compound (.alpha.-HCl salt)
in 500 mL of ethyl acetate at room temperature under agitation, and
agitated at room temperature for 30 min. 500 mL of water was added to the
mixture, and subjected to liquid separating extraction. An organic layer
was separated and washed with a saline solution. The organic layer was
dried over magnesium sulfate, and the ethyl acetate was distilled off in
vacuum. Thus, 119 g of oily substance (.alpha.) was obtained. The obtained
119 g of oily substance (.alpha.) was poured into a solution obtained by
dissolving 161.7 g (0.75 mol) of compound (B) in 1000 mL of toluene at
room temperature under agitation. Subsequently, the reaction mixture was
heated, and formed ethanol was distilled off while maintaining the
internal temperature thereof at 80.degree. C. Further, the internal
temperature was raised to 110.degree. C., distilling off formed water over
a period of 3 hr. Thereafter, 500 mL of toluene was distilled off in
vacuum, and the internal temperature was lowered to 70-75.degree. C. 500
mL of acetonitrile was slowly poured into the mixture, agitated under
reflux for 1 hr, and very slowly cooled until the internal temperature
reached room temperature. The mixture was further agitated for 30 min
while cooling with water. Separated crystal was harvested by filtration,
washed with cold acetonitrile, and dried at 40.degree. C. overnight. Thus,
163 g (yield 70%) of compound (C) (melting point: 152-153.degree. C.) was
obtained.
Synthesis of Compound (D):
100 g (2.5 mol) of granular sodium hydroxide was slowly divided and added
to a solution obtained by dissolving 155.4 g (0.5 mol) of compound (C) in
1600 mL of methanol under agitation while maintaining the temperature
thereof at 10.degree. C. or below by cooling with ice. The resultant
reaction mixture was heated to 40.degree. C., and agitated at 40.degree.
C. for 90 min. Thereafter, the reaction mixture was cooled to an internal
temperature of 30.degree. C., and slowly poured into a solution consisting
of 430 mL of hydrochloric acid, 2000 mL of water and 1 kg of crushed ice
to thereby effect acid precipitation. Further, the mixture was agitated at
10.degree. C. for 90 min. Crystal was harvested by filtration, washed with
water, washed with cold acetonitrile, and dried at 40.degree. C.
overnight. Thus, 140 g (yield 99%) of compound (D) (melting point:
133-152.degree. C.) was obtained.
Synthesis of Compound (E):
48.1 g (0.49 mol) of potassium acetate was divided and added to a solution
obtained by dissolving 111 g (0.49 mol) of
2,6-di-t-butyl-4-methylcyclohexanol and 138.5 g (0.49 mol) of compound (D)
in 1500 mL of ethyl acetate at room temperature under agitation. The thus
obtained reaction mixture was cooled to 10.degree. C. or below, and 236 mL
(2.5 mol) of acetic anhydride was slowly dropped thereinto while
maintaining the internal temperature thereof at 15.degree. C. or below.
Subsequently, the reaction mixture was agitated at 40 to 45.degree. C. for
90 min, and the internal temperature thereof was lowered to 5.degree. C.
The thus separated crystal was harvested by filtration, satisfactorily
washed with water so as to remove any inorganic matter, and finally washed
by sprinkling cold acetonitrile. The obtained crystal was dried at
50.degree. C. overnight. Thus, 206.4 g (yield 79%) of compound (E)
(melting point: 178-179.degree. C.) was obtained.
Synthesis of Compound (F):
39.2 mL of concentrated hydrochloric acid was slowly dropped into a
solution obtained by dissolving 203 g (0.38 mol) of compound (E) in 600 mL
of acetonitrile at room temperature. The thus obtained reaction mixture
was heated and agitated under reflux for 2 hr. Thereafter, the internal
temperature thereof was lowered to 40.degree. C., and 600 mL of water was
dropped into the mixture and agitated at room temperature for 1 hr.
Separated crystal was harvested by filtration, washed with water, and
dried at 50.degree. C. overnight. Thus, 185.1 g (yield 99.2%) of compound
(F) (melting point: 191-195.degree. C.) was obtained.
Synthesis of Compound (G):
108.7 g (0.38 mol) of 1,3-dibromo-5,5-dimethylhydantoin was added to a
solution obtained by dissolving 181.7 g (0.37 mol) of compound (F) in 700
mL of acetonitrile at room temperature. Subsequently, 0.44 g of
methanesulfonic acid was dropped thereinto, and the reaction mixture was
heated and agitated under reflux for 90 min. The internal temperature
thereof was lowered to 30.degree. C., and 370 mL of N,N-dimethylformamide
was poured into the mixture. Further, while cooling with water, a solution
obtained by dissolving 45.7 g (0.82 mol) of potassium hydroxide in 150 mL
of water was dropped into the mixture at 20 to 25.degree. C. The resultant
reaction mixture was agitated at 60.degree. C. for 90 min and cooled to
room temperature. 1000 mL of ethyl acetate and 1000 mL of water were added
to the mixture to thereby effect extraction. The thus obtained ethyl
acetate layer was washed with water and a saline solution, and dried over
magnesium sulfate. The solvent was distilled off in vacuum, and
recrystallization from acetonitrile was performed. Thus, 178.3 g (yield
95.4%) of compound (G) (melting point: 195-197.degree. C.) was obtained.
Synthesis of Compound (H):
186 g (3.5 mol) of acrylonitrile was poured into a solution obtained by
dissolving 176.8 g (0.35 mol) of compound (G) in 370 mL of
N,N-dimethylformamide at room temperature. Further, 63.9 g (0.42 mol) of
DBU (1,8-diazabicyclo[5.4.0]-7-undecene) was poured thereinto, and the
reaction mixture was agitated at 80.degree. C. for 4 hr. The resultant
reaction mixture was cooled to room temperature, and 500 mL of
acetonitrile was poured thereinto. Further, 72.3 mL of concentrated
hydrochloric acid and 1500 mL of water were slowly dropped into the
mixture at room temperature. The reaction mixture was agitated at room
temperature for 1 hr, and separated crystal was harvested by filtration
and washed with water. Crude crystal was subjected to recrystallization
from acetonitrile. Thus, 133.3 g (yield 70.5%) of compound (H) (melting
point: 265.degree. C., dec.) was obtained.
Synthesis of Compound (J):
A solution obtained by dissolving 77.1 mL (0.5 mol) of ethyl nipecotate and
6.9 g (0.05 mol) of potassium carbonate in 65 mL of N,N-dimethylacetamide
was heated under agitation until the internal temperature thereof reached
80.degree. C. A solution obtained by dissolving 27 g of compound (H) in 35
mL of N,N-dimethylacetamide was dropped thereinto, and continued the
agitation at 85.degree. C. for 2 hr. The thus obtained reaction mixture
was cooled to room temperature, and 150 mL of ethyl acetate and 500 mL of
water were added to the mixture to thereby effect extraction. The thus
obtained ethyl acetate layer was washed with water and a saline solution,
and dried over magnesium sulfate. The solvent was distilled off in vacuum,
and recrystallization from acetonitrile was performed. Thus, 25.5 g (yield
77%) of compound (J) (melting point: 178-180.degree. C.) was obtained.
Synthesis of Compound (L):
While nitrogen bubbling, 2,5-di-t-octylhydroquinone (2 kg), propyl tosylate
(4.23 kg) and N,N-diethylhydroxylamine (159.4 g) were added to ethanol (6
L). The external temperature was set for 20.degree. C., and when the
internal temperature reached 20.degree. C., an aqueous solution of KOH
(obtained by dissolving 1.58 kg of KOH in 1.6 liters (hereinafter also
referred to as "L") of water) was dropped thereinto while maintaining
40.degree. C. or below. After the completion of dropping, the mixture was
agitated at room temperature for 2 hr, and the completion of reaction was
ascertained. Water (8 L) was added thereto, and crystal was harvested by
filtration. Thus, 2.41 kg of crude crystal of
1,4-dipropoxy-2,5-di-t-octylhydroquinone was obtained. This crude crystal
was purified (yield 79.1%) by dispersing the same in acetonitrile (6 L),
agitating the dispersion at room temperature for 30 min, cooling the same
with ice, agitating the dispersion for more 30 min and effecting
filtration thereof. 1.98 kg of thus obtained crystal was dispersed in
methylene chloride (5.94 L), and chlorosulfonic acid (630 mL) was dropped
into the dispersion at an internal temperature of 11.degree. C. After the
completion of dropping, the external temperature was raised to room
temperature, and the mixture was agitated for 30 min. After the
elimination of raw materials was ascertained, the mixture was again
cooled, and N,N-dimethylacetamide (1.98 L) was dropped thereinto at an
internal temperature of 12.degree. C. After the completion of dropping, at
an internal temperature of 13.degree. C., phosphorus oxychloride (0.88 L)
was dropped thereinto. After the completion of dropping, the external
temperature was raised to room temperature. The mixture was agitated at
room temperature for 30 min, and hexane (9.9 L) was added. Lower layer was
removed by liquid separating operation. The hexane layer was washed with a
5% aqueous sodium bicarbonate solution (15 L) and a 5% aqueous
hydrochloric acid solution (7.4 L). The external temperature was raised to
60.degree. C., and the solvent, methylene chloride, was distilled off at
atmospheric pressure. Acetonitrile (9.9 L) and water (2.48 L) were added
to the residue to thereby produce three layers. Lower two layers of the
produced three layers were removed by liquid separating operation. Once
more, acetonitrile (9.9 L) and water (2.48 L) were added thereto to
thereby produce three layers. Lower two layers of the produced three
layers were removed by liquid separating operation. The thus obtained
organic layer was completely concentrated by means of an evaporator. As a
result, oily compound (L) (1.55 kg, 80.9%) was obtained.
Synthesis of Compound (K):
20 g of reduced iron was divided and added to a solution consisting of 2 g
of ammonium chloride, 40 mL of water and 200 mL of isopropyl alcohol at
room temperature under agitation. Subsequently, the resultant reaction
mixture was heated to reflux, and 20 g of compound (J) was slowly divided
and added thereto. The mixture was agitated under reflux for 30 min. The
thus obtained reaction mixture was subjected to hot Celite filtration, and
100 mL of ethyl acetate and 500 mL of water were added to the filtrate to
thereby effect extraction. The ethyl acetate layer was washed with water
and a saline solution, and dried over magnesium sulfate. The solvent was
distilled off in vacuum, and recrystallization from acetonitrile was
performed. Thus, 17.7 g of intermediate (--NH.sub.2 derivative) was
obtained. Subsequently, 6.5 g (10.32 mmol) of obtained intermediate was
divided and added to a solution obtained by dissolving 5.02 g (12.39 mmol)
of 2,5-dipropoxy-4-t-octylbenzenesulfonyl chloride (L) in 80 mL of
acetonitrile at 50.degree. C. Further, 2 mL of pyridine was dropped
thereinto, and agitated under reflux for 1 hr. The reaction mixture was
cooled to room temperature, and 150 mL of ethyl acetate and 500 mL of
water were added thereto to thereby effect extraction. The ethyl acetate
layer was washed with water and a saline solution, and concentrated.
Methanol was added to the concentrate, thereby obtaining 8.66 g (yield
89%) of crystal of compound (K) (decomposed at 270.degree. C.)).
(Synthesis of Compound Example 1)
7 mL of methanol, 1.6 mL of water and 0.7 g of potassium hydroxide were
added to 1.90 g of compound (K), and agitated for 2 hr while heating at
70.degree. C. After the completion of reaction, the methanol was distilled
off in vacuum, and ethyl acetate and water were added to the residue to
thereby effect extraction. The thus obtained ethyl acetate layer was
washed with water and a 5% aqueous hydrochloric acid solution, and dried
over magnesium sulfate. The solvent was distilled off in vacuum, and
recrystallization from ethyl acetate/acetonitrile was performed. Thus,
1.59 g (yield 86%) of crystal of compound example (1) was obtained.
The structure of exemplified compound (1) was identified by .sup.1 H-NMR.
.sup.1 H-NMR (in DCDl.sub.3) of exemplified compound (1): 12.65(s,1H),
12.0-11.3(bt,1H), 8.17(s,1H), 7.96(s,1H), 7.90(d,1H), 7.45(s,1H),
7.40(s,1H), 7.26(s,1H), 7.22(d,1H), 6.86(s,1H), 5.99(s,1H),
4.01-3.95(m,4H), 3.3-3.0(m,3H), 3.0-2.8(m,1H), 2.60-2.35(m,2H),
2.00-1.5(m,14H), 1.4-1.2(m,8H), 1.2-1.0(m,9H), 0.92(s,9H), 0.90(s,9H),
0.44(s,9H)
Synthetic Example 2 (Synthesis of Exemplified Compound 2)
Exemplified compound 2 was synthesized in the same manner as in Synthetic
Example 1 except that 2,5-diethoxy-4-t-octylbenzenesulfonyl chloride was
used in place of 2,5-dipropoxy-4-t-octylbenzenesulfonyl chloride.
Other exemplified compound can also be synthesized in substantially the
same manner as in Synthetic Example 1.
The suitable coating amount of cyan coupler according to the present
invention is in the range of 0.01 to 2 g/m.sup.2, preferably 0.05 to 1.0
g/m.sup.2.
The silver halide color photosensitive material of the present invention is
only required to have at least one light-sensitive layer on a support.
Typical example thereof is a silver halide photosensitive material having
at least one light-sensitive unit layer comprising a plural of silver
halide emulsion layers each having the substantially the same color
sensitivity but different in speed. The light-sensitive unit layer is a
unit layer having color sensitivity to any one of blue light, green light
and red light. In a multi-layered silver halide color photosensitive
material, the arrangement of the unit layer is generally, in the order,
from a support, of a red-sensitive layer, green-sensitive layer and
blue-sensitive layer. However, the arrangement order may be reversed
depending on the purpose of the photographic material. And such an
arrangement order that a light-sensitive layer having a different color
sensitivity is sandwiched between layers having the same color
sensitivity, may be acceptable. A non lightsensitive layer can be formed
between the silver halide lightsensitive layers and as the uppermost layer
and the lowermost layer. These intermediate layers may contain, e.g.,
couplers to be described later, DIR compounds and color-mixing inhibitors.
As for a plurality of silver halide emulsion layers constituting
respective unit lightsensitive layer, a two-layered structure of high- and
low-speed emulsion layers can be preferably used in this order so as to
the speed becomes lower toward the support as described in DE (German
Patent) 1,121,470 or GB 923,045, the entire contents of which are
incorporated herein by reference. Also, as described in JP-A's-57-112751,
62-200350, 62-206541 and 62-206543, the entire contents of which are
incorporated herein by reference, layers can be arranged such that a
low-speed emulsion layer is formed farther from a support and a high-speed
layer is formed closer to the support.
More specifically, layers can be arranged from the farthest side from a
support in the order of low-speed blue-sensitive layer (BL)/high-speed
blue-sensitive layer (BH)/high-speed green-sensitive layer (GH)/low-speed
green-sensitive layer (GL)/high-speed red-sensitive layer (RH)/low-speed
red-sensitive layer (RL), the order of BH/BL/GL/GH/RH/RL or the order of
BH/BL/GH/GL/RL/RH.
In addition, as described in Jpn. Pat. Appln. KOKOKU Publication No.
(hereinafter referred to as JP-B-) 55-34932, the entire contents of which
are incorporated herein by reference, layers can be arranged from the
farthest side from a support in the order of blue-sensitive
layer/GH/RH/GL/RL. Furthermore, as described in JP-A's-56-25738 and
62-63936, the entire contents of which are incorporated herein by
reference, layers can be arranged from the farthest side from a support in
the order of blue-sensitive layer/GL/RL/GH/RH.
As described in JP-B-49-15495, the entire contents of which are
incorporated herein by reference, three layers can be arranged such that a
silver halide emulsion layer having the highest sensitivity is arranged as
an upper layer, a silver halide emulsion layer having sensitivity lower
than that of the upper layer is arranged as an interlayer, and a silver
halide emulsion layer having sensitivity lower than t
