JPH0489869A - Beta,gamma-unsaturated nitrile azomethine coloring matter - Google Patents

Abstract

PURPOSE:To obtain a coloring matter having excellent spectral properties for forming an image and for a filer by forming a beta,gamma-unsaturated nitrile azomethine coloring matter shown by a specified structural formula. CONSTITUTION:A beta,gamma-unsaturated nitrile azomethine coloring matter shown by formula 1, wherein R<1>, R<2>, R<3>, and R<4> are each a hydrogen atom or a nonmetallic substituent; R<5> and R<6> are each a hydrogen atom, alkyl, aryl or a heterocyclic group; V is a nitrogen atom or a group of formula II; X, Y, and Z are each a nonmetallic substituent; at least one of Y and Z is an electron attracting substituent; X and Y and/or, Y and Z and/or, R<1> and R<2> and/or, R<2> and R<5> and/or, R<5> and R<6> and/or, R<3> and R<6> and/or, R<3> and R<4> may be combined together to form a cyclic structure; X, Y, Z, R<1>, R<2>, R<3>, R<4>, R<5>, and R<6> may further be substituted; formula III shows that Y and X may be cis or trans as to a double bond.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to dyes for image formation in color photography, color electrophotography, inkjet type, hard copy, thermal transfer type, printing, etc. The present invention relates to a β, γ-unsaturated nitrile azomethine dye useful as a filter dye for image pickup tubes and color liquid crystal televisions.

(Prior art) Azomethine dyes, especially azomethine dyes in which a p-dialkylaminophenyl group is bonded to the nitrogen atom of an imine, are active methylenes and phenols and N,N dialkyl-p-
It is formed by an oxidative coupling reaction with phenylene diamines, and has a color tone of yellow, red, magenta,
Since it has a wide variety of colors such as blue and cyan, it has been widely used as an image-forming dye in silver halide color photographic materials using a subtractive color method by color mixing of yellow, mazeil, and methine. Phenols, naphthols and 2
．． Blue or methine dyes are formed from 4-diphenylimidazoles, etc., and 5-pyrazolones, anruacetonitriles, IH-hirazolo (15-a) henguimidazoles, IH pyrazolo [5, I-c) -1 ，
2,4-1 Rhiazoro, IH-Hirazoro [2,3-b
)-12,4-triazoles and the like form magenta to blue dyes, and anruacetonitris, diacylmethanes, malondianilides and the like form yellow dyes. Regarding such dyes, Japanese Patent Application Laid-Open No. 1986-
No. 186567, No. 63-145281 and No. 63-
It is described in No. 113077, etc.

In recent years, new color image forming methods such as color electrophotography, inkjet, and thermal transfer methods have been proposed, and along with the development of electronic imaging, the use of solid-state image pickup tubes and filters for color LCD televisions has improved. As demand increased, azomethine dyes began to be applied and investigated not only for color photography but also for various systems and products.

(Problems to be Solved by the Present Invention) Among azomethine dyes, phenol-based indoaniline dyes and naphthol-based indoaniline dyes are known as cyan dyes. However, these dyes have the disadvantage that absorption is broad and sub-absorption exists in the yellow region.

Also, JP-A-63-113077, JP-A-111056
No. 5, JP-A No. 2-668, JP-A No. 2-53866, JP-A No. 2-53866, JP-A No. 2-53866, No. 2
No. 53865 discloses an imidazole azomethine dye as a cyan dye.

However, the above-mentioned dyes also have drawbacks in that absorption is not sufficient for color reproduction and synthesis is extremely difficult.

Further, pyrazoloazole azomethine dyes are disclosed as cyan dyes in Japanese Patent Application Laid-open Nos. 64-48862 and 64-48863.

However, these dyes had the drawback of being extremely difficult to synthesize.

Furthermore, among azomethine dyes, pyrazolone-based azomethine dyes are disclosed as magenta dyes in JP-A-63205288 and other publications. However, this dye had unnecessary sub-absorption in the yellow region.

Furthermore, virazolohenzimidazole-based azomethine dyes are disclosed in JP-A-1-176592 and the like. However, this dye had low fastness.

In addition, pyrazoloazole azomethine dyes are disclosed in JP-A No. 64-63194 and the like. However, this dye was difficult to synthesize and expensive.

As mentioned above, conventionally known azomethine dyes have various drawbacks, and it has been desired to develop a dye that is easy to synthesize, low in cost, and has excellent absorption.

(Objective of the present invention) An object of the present invention is to provide an azomethine dye having excellent spectral properties for use in image formation and filter use.

Another object of the present invention is to provide an azomethine dye that is easy to synthesize.

Another object of the present invention is to provide an azomethine dye with low cost.

Another object of the present invention is to provide an azomethine dye with high fastness.

(Means for Solving the Problems) The above objects of the present invention have been achieved by the following azomethine dye.

β-γ-unsaturated unsaturated nitrile azomethylene 7 b/ゝR5 represented by the following general formula (+) In the formula, R', R'', R' and R4 represent a hydrogen atom or a nonmetallic substituent. represent.

R5 and Rh represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

■ represents a nitrogen atom or ~, 2.

X, Y, and Z represent nonmetallic substituents.

At least one of Y and Z represents an electron-withdrawing substituent.

X and Y and/or Y and Z and/or R and R2 and/or R2 and R5 and/or R5 and R6 and/or R3 and R6 and/or R3 and R4 are bonded to each other. It may form a ring structure.

represents a group, n represents an integer of O to 2, Q represents X, Y
, Z, R', R2, R', R', R5
R6 may be further substituted.

This notation indicates that it can be either cis or trans. ) Among the dyes represented by the general formula (1), the following general formula (I
Dyes represented by t) or (Ill) are preferred.

R6-"\R5 In the formula, S, T and U are each a nitrogen atom, a methine group, or a methine group having an electron-withdrawing group, and at least one of them is a methine group having an electron-withdrawing group. 5 Together with the residue, it represents a group of nonmetallic atoms necessary to form an aromatic ring or an aromatic carbon ring.

RI XRZ , R3 and R4 represent a hydrogen atom or a nonmetallic substituent.

R5 and R6 are hydrogen atoms, alkyl groups, aryl groups,
Represents a heterocyclic group.

R1 and R2 and/or Rt and R5 and/or R5
and R6 and/or R3 and R6 and/or R3 and R4
may be bonded to each other to form a ring structure.

X, Y, Z, R', R2, R', R', R5R6
may be further substituted.

In the formula, at least one of R7 and RI represents an electron-withdrawing substituent, and the other represents a substituent.

R', R'', R' and R4 represent a hydrogen atom or a nonmetallic substituent.

R5 and R6 are hydrogen atoms, alkyl groups, aryl groups,
Represents a heterocyclic group.

R' and R1 and/or R2 and R5 and/or R
5 and R6 and/or R4 and R6 and/or R3 and R' may be bonded to each other to form a ring structure.

X, Y, Z, R', R2, R', R', R'R6
may be further substituted.

General formula (1) will be described in detail below.

R', R2, R3 and R4 represent a hydrogen atom or a non-metallic atomic group, among which hydrogen atom, alkyl group, alkokene group, aryloxo group, halogen atom, acylamino group, alkokinocarbonyl group, methine group, alkoxoluponylamino group, aryoloxycarbonylamino group, aminocarbonylamino group, sulfonylamino group, carbamoyl group, sulfamoyl group, aryol group, alkylthio group, aryolthio group, sulfonyl group,
Acyl groups and amino groups are preferred.

Specific examples thereof include hydrogen atoms, alkyl groups (including those with substituents, having 1 to 2 carbon atoms), such as methyl, ethyl,
isopropyl, butyl, methoxyethyl, cyclohexynol, phenethyl), alkoxy groups (including those with substituents, carbon number 1-12, e.g. methquine, ethquine,
isopropoxy, methoxyethoxy), aryloxy groups (including those with substituents, having 6 to 12 carbon atoms, such as phenoxy, p-methoxyethoxynoquine, p-lylolophenoquine, p-methylphenoquine), halogen atoms (e.g. ), element, chlorine, bromine), acylamino group [1 carbon number
~10 alkylcarbonylamino groups (including those with substituents; for example, formylamino, acetylamino,
propionylamino, isobutylamino, hexahydrohensylamino, pivaloylamino, trifluoroacetylamino, heptafluorobutyrylamino, chloropropionylamino, cyanoacetylamino, phenoxyacetylamino), vinylcarbonylamino group having 3 to 10 carbon atoms (substituted (e.g., acryloylamino, methacryloylamino, crotonoylamino), arylcarbonylamino groups having 7 to 15 carbon atoms (including those having a W substituent; e.g., benzoylamino, p-tolylamino, penta-tolylamino, Fluoropenduylamino, 0-fluorohensylamino, m-methquinhendylamino, p-trifluoromethylhendylamino, 24-dichlorohendylamino, p-methoxoluponylbenzuylamino, 1 -naphthoylamino), hetyrylcarbonylamino groups having 5 to 13 carbon atoms (including those with substituents; for example, picolinoylamino,
nicotinoylamino, pyrrole-2-carbonylamino, thiophene-2-carbonylamino, furoylamino, piperidine-4-carbonylamino)], niano group,
Alcoquinocarbonyl group (including those with substituents).

carbon number 2~]0, e.g. methquinocarbonyl, ethquinocarbonyl), alkoxycarbonylamino group device 11
! ! Including those with groups. 2 to 10 carbon atoms, such as methanesulfonylamino, ethoxycarbonylamino, isopropoxycarbonylamino, methoxycarbonylamino, N-methylmethoxycarbonylamino,
t-butoxycarbonylamino, hekynoquinoluponylamino), ri-luoquinoluponylamino group (including those with substituents, carbon number 7 to 15, e.g. phenylsulfonylamine, ortho-chlorophenoquinocarbonylamino), aminocarbonylamino groups (including those with substituents; 1 to 10 carbon atoms, e.g. methylaminocarbonylamino, dimethylaminocarbonylamino, butylaminocarbonylamino), sulfonylamino groups (1 to 10 carbon atoms, methanesulfonylamino, ethanesulfonylamino) , N-methylmethanesulfonylamino, phenylsulfonylamine), carbamoyl group [alkylcarbamoyl group having 1 to 12 carbon atoms (including those having substituents).

For example, methylcarbamoyl, dimethylcarbamoyl, butylcarbamoyl, isopropylcarbamoyl, t-butylcarbamoyl, nclopentylcarbamoyl, cyclohexylcarbamoyl, allylcarbamoyl, methoxyethylcarbamoyl, chloroethylcarbamoyl, cyanethylcarbamoyl, ethylcyanethylcarbamoyl, hensylcarbamoyl, ethoxycarbonylmethylcarbamoyl, furfurylcarbamoyl, tetrahydrofurfurylcarbamoyl, phenoxymethylcarbamoyl), carbon number 7-15 -rucarhamoyl group (including those with substituents, e.g. phenylcarbamoyl, p-)ruylcarhamoyl , m-methoxyphenylcarbamoyl, 45-dichlorophenylcarbamoyl, p
= noanophenylcarbamoyl, p-acetylaminophenylcarbamoyl, p-methoquinocarbonylphenylcarbamoyl, m-)lifluoromethylphenylcarbamoyl, 0-fluorophenylcarbamoyl, 1-naphthylcarbamoyl), having 4 to 12 carbon atoms Hetyrylcarbamoyl group (including those with substituents; for example, 2-pyridylcarbamoyl, 3-pyridylcarbamoyl, 4-pyridylcarbamoyl
Pyridylcarbamoyl, 2-thiaprylcarhamoyl,
2-henzimidazolyl-ruhamoyl, 2-henzimidazolyl-ruhamoyl, 2-(4-methyl)pyridylcarbamoyl, 2-(5-methyl)1,34-thiacyaprilcarbamoyl)], sulfamoyl group (carbon 0-12,
For example, methylsulfamoyl, dimethylsulfamoyl, butylsulfamoyl, phenylsulfamoyl),
Arylthio groups (including those with substituents; e.g., phenyl, p-tolyl, p-methoxyphenyl, p-chlorophenyl), alkylthio groups (including those with substituents, e.g., methylthio, butylthio), arylthio Groups (including those with substituents; for example, phenylthio,
p-)lylthio), sulfonyl groups (e.g. methanesulfonyl, butanesulfonyl, phenylsulfonyl), acyl groups (e.g. acetyl, butyroyl), and amino groups (e.g. methylamino, dimethylamino, anilino). .

Preferred among R2, R3 and R4 is a hydrogen atom.

More preferred among R1 are electron donating groups and hydrogen bonding groups. For example, an alkyl group (1 to 14 carbon atoms, e.g. methyl, ethyl, isopropyl, methquinethyl, pmethquinphenoxmethyl)
, Alcoquino group (1 to 14 carbon atoms, e.g. methoxy, ethoxy, isopropoquine), Anruamino group (2 carbon atoms)
-14°For example, acetylamino group, pivaloylamino group), alkoxycarbonylamino group (carbon number 2-14.
For example, metquincarbonylamino, ethoxycarbonylamino, isopropoxycarbonylamino, aminocarbonylamino group (2 to 14 carbon atoms, methylaminocarbonylamino, ethylaminocarbonylamino, dimethylaminocarbonyl 7-mino), sulfonylamino group (carbon Numbers 1 to 14, methanesulfonylamino, p-
t-luenesulfonylamino)).

Among these, an anruamino group, an alkoxyamino group, and an aminocarbonylamino group are most preferred.

R5 and R6 are hydrogen atoms, alkyl groups (including those with substituents) having 1 to 12 carbon atoms, such as methyl, ethyl,
Isopropyl, butyl, cyclopentyl, cyclohexyl, 2-methoxyethyl, 2-chloroethyl, 2-hydroquinethyl, 2-noanoethyl, noatumethyl, 2-methylsulfupmoylethyl, 2-methylsulfonylaminoethyl, 2-methoxycarbonylethyl, 2-acetoxyethyl, methoxycarbonylmethyl, hensyl, allyl) or aryl groups (including those with substituents).

6-12 carbon atoms, e.g. phenyl, p-)lyl, m-chlorophenyl) or heterocyclic groups (including those with substituents; 4-1 carbon atoms) Among R4 and R2, preferred are 1-6 carbon atoms. is an alkyl group.

Preferred examples include a ring which may be formed by combining R4 and R3, and a ring which may be formed by combining R3 and R4 or R1 and R1.

In general formula (1), X is a hydrogen atom, a halogen atom,
Preferably an aliphatic group having 1 to 36 carbon atoms, preferably an aromatic group having 6 to 36 carbon atoms (e.g. phenyl, naphthyl),
Heterocyclic groups (e.g. 3-pyridyl, 2-furyl), alkoxy groups (e.g. methoxy, 2-methoxyethoxy), aryloxy groups (e.g. 2,4-di-tert-amylphenoxy, 2-chlorophenoxy, 4-cyano phenoxy), alkenyloxy groups (e.g. 2-propenyloxy), acyl groups (e.g. acetyl, benzoyl),
Ester groups (e.g. butoxycarbonyl, phenoxycarbonyl, acetoxy, hendiyloxy, butoxysulfonyl, toluenesulfonyloquine), amide groups (e.g. acetylamino, ethylcarbamoyl, dimethylcarbamoyl, methanesulfonamide, butylsulfamoyl), sulfamide groups (e.g. dipropylsulfamoylamino), imide groups (e.g. sacnonimide, hydantoynyl), ureido groups (e.g. phenylureido,
dimethylureido), aliphatic or aromatic sulfonyl groups (e.g. methanesulfonyl, phenylsulfonyl),
It represents an aliphatic or aromatic thio group (eg, ethylthio, phenylthio), cyano group, carboxy group, nitro group, sulfo group, etc.

In the present specification, the term "aliphatic group" refers to a linear, branched or cyclic aliphatic hydrocarbon, such as alkyl, alkenyl,
It is meant to include saturated and unsaturated groups such as alkynyl groups. Representative examples include methyl group, ethyl group,
Butyl group, dodecyl group, octadecyl group, alkynyl group, 1so-propyl group, tert-butyl group, tert
-octyl group, tert dodecyl group, cyclohexyl group, cyclopentyl group, allyl group, vinyl group, 2-hexadecenyl group, propargyl group, etc.

In general formula (1), when ■ represents -C=, at least one of Y and Z represents an electron-withdrawing substituent, and preferably the value of Hammett's substituent constant σ2 is 0.
Represents 10 or more substituents, more preferably 0.35
It represents the above substituents, and more preferably represents a substituent with a value of σ2 of 0.60 or more. This σ2 value is preferably 2 or less. The value of Hammett's substituent constant σ2 here is based on the report by Hansch+ C, Leo et al. (for example, J. Med.

Chelm, ±J1.1207 (1973); 1b
id, 20304 (1977)) is preferably used.

As substituents or atoms with a value of σ2 of 0.10 or more,
Chlorine atom, bromine atom, iodine atom, substituted alkyl group (e.g. trichloromethyl, trifluoromethyl, chloromethyl, trifluoromethylthiomethyl, trifluoromethanesulfonylmethyl, perfluorobutyl), nitrile group, acyl group (e.g. formyl, acetyl, carboxyl group, substituted or unsubstituted carbamoyl group (e.g. carbamoyl, methylcarbamoyl), alkoxycarbonyl (e.g. methoxycarbonyl, ethoxycarbonyl, diphenylmethylcarbonyl), substituted aromatic group (e.g. pentachlorophenyl, pentafluorophenyl), Complex m residues (e.g. 2-hendioxazolyl, 2-benzthiazolyl, 1-phenyl-2-benzimidazolyl, 1-tetrazolyl), nitro groups, azo groups (
phenylazo), substituted amino groups (e.g. ditrifluoromethylamino), substituted alkoxy groups (e.g. trifluoromethoxy), alkylsulfonyloxy groups (e.g. methanesulfonyloxy), acyloxy groups (e.g. acetyloxy, benzoyloxy), arylsulfonyloxy groups (e.g. benzenesulfonyloxy), phosphoryl groups (e.g. dimethoxyphosphonyl, diphenylphosphonyl), sulfamoyl groups, sulfonyl groups (e.g. trifluoromethanesulfonyl, methanesulfonyl,
Hensensulfonyl), etc.

Substituents with a value of σ of 0.35 or more include substituted alkyl groups (e.g. trifluoromethyl, perfluorobutyl)
, nitrile groups, acyl groups (e.g. acetyl, hendiyl, formyl), carboxyl groups, carbamoyl groups (e.g. carbamoyl, methylcarbamoyl), alkoxycarbonyl groups (e.g. methquinocarbonyl, ethquinocarbonyl, diphenylmethylcarbonyl), substituted aromatics. groups (e.g. pentafluorophenyl), heterocyclic residues (e.g. 1-tetrazolyl), nitro groups, ab groups (e.g. phenylazo), substituted amino groups (e.g. ditrifluoromethylamino), substituted alkoke groups (e.g. trifluoromethoquine), Examples include alkylsulfonyloxy groups (eg, methanesulfonyloxy), phosphoryl groups (eg, dimethoxyphosphonyl, diphenylphosphoryl), sulfamoyl groups, sulfonyl groups (eg, trifluoromethanesulfonyl, methanesulfonyl, hensensulfonyl), and the like.

Examples of the substituent having a value of σ9 of 0.60 or more include a nitrile group, a nitro group, a sulfonyl group (eg, trifluoromethanesulfonyl, difluoromethanesulfonyl, methanesulfonyl, hensensulfonyl), and the like.

When Y or 2 is not an electron-withdrawing group, examples of the WA group include aliphatic groups (e.g. methyl, ethyl or octyl), alkoxy groups (e.g. methoxy, nidoquino, 1
'decyloquino), or amide groups (e.g. acetamide, piharylamide, or octanamide), aromatic groups (e.g. phenyl, 4-alcoquinphenyl), heterocyclic groups (e.g. 2-furyl, 2-thienyl, 2-thiazolyl) represents.

Next, general formula (II) will be explained.

In the -m formula (It), those represented by R1, R2, R3 and R4 have the same meanings as those represented by RR2, R3 and R4 in the -m formula (1). Specific examples and preferred examples thereof include those described in formula (1).

-m In formula (Il), S, T and U are each a nitrogen atom, a methine group, or a methine group having an electron-withdrawing group, at least one of which represents a methine group having an electron-withdrawing group, and S When represents a methine group as described above, it represents -0-, when T represents a methine group as described above, it represents C=, and when U represents a methine group as described above, it represents -C=. When S and T each represent a methine group as described above, R9 and Rlo may be the same or different, and may be bonded to each other to form a ring. Similarly, when T and U each represent a methine group as described above, RIO and R1+ may be the same or different, and may be bonded to each other to form a ring.

In that case, it is preferably a fused ring, such as a Hensen fused ring or a pyridine fused ring.

Examples of the substituents Rq, R1fi and RI' include the substituents listed for X above. Substituent R9, R'
At least one of ° and Rl + 42 is an electron-withdrawing group, preferably a substituent having a Hammett's substituent constant σ2 of 0.10 or more, more preferably 0.35 or more. represents a substituent, and more preferably represents a substituent having a value of σ2 of 0.60 or more. Examples of the substituent include the substituents listed for Y or Z above.

-m In formula (II), Q represents an atom or atomic group necessary to form an aromatic heterocycle or an aromatic carbocycle together with the carbon atom or nitrogen atom to which it is bonded.

In particular, when n is 1, the divalent group forming the ring represents a divalent amino group, ether bond, thioether bond, alkenylene group, imino group, carbonyl group, etc., and these have a substituent. You can leave it there. Examples of the substituent here include the substituents listed for R1 above.

Particularly preferably, Q is a 1,000-onythyl bond or an imino group.

Specific examples of the heterocycle formed by Q include the following, but the present invention is not limited thereto.

R+2 RIZI" R1 (1 RI2 R+2 R1゜R", \/R ん/ 11 ゝ7.l, っbe lI R12, 7 p+2 h 2・ノ<7., R" N Ii' i ')' p+2 Furthermore, the following ring condensed to the above heterocycle may be used.

I2 R12R Here, R12 represents the same thing as R9, R101R1+.

Next, general formula (III) will be explained.

In general formula (III), R1, R2, R:l and R
4 is RR2, R3 in the general formula
and R4 have the same meaning.

Specific examples and preferred examples thereof include those mentioned in 2 (+).

In general formula (III), at least one of R7 and R8 represents an electron-withdrawing substituent, preferably represents a substituent with a value of Hammett's substituent constant σ2 of 010 or more, more preferably a value of σ2 of It represents a substituent with a value of 0.35 or more, more preferably a substituent with a value of σ2 of 0.60 or more. Examples of substituents include the substituents listed for Y or Z above.

When R7 or R8 represents a substituent, for example, preferably an aliphatic group having 1 to 36 carbon atoms (such as methyl, propyl, t-butyl, tridecyl, 3(2,4,-di-t-
amylphenoquine) propyl, 2-dodecyl oquinoethyl, 3-phenoquinopropyl, noclopentyl, hensyl, allyl, propargyl), preferably 6 to 3 carbon atoms
6 aromatic groups (eg, phenyl, naphthyl), heterocyclic groups (eg, 2-furyl, 2-thienyl, 2-pyrimidyl, 2-thiazolyl), and the like.

The dye of the present invention may have an atomic group within the dye molecule that has the effect of suppressing dark color. This is particularly preferred when high image fastness is required.

The atomic group that has the effect of suppressing fading is the dye formula (1)
R,, R2, R3, R4, Rs, Ra, x, y, z
It may be bonded to any part of the throat.

As an atomic group having the effect of suppressing gray color, Japanese Patent Application Hei 1-
All those described in No. 27078 can be used.

Specific examples of atomic groups having the effect of suppressing fading will be given, but the present invention is not limited thereto.

CH3 CR3 Hz CH3 0\ 0 \ O\ H 0″″ 0' 0' C.L. CHs OCH.

CH2) 1゜ OCH.

O\ OCH.

0 \ 0 \ CH3 〇- 0'θ' The azomethine dye of the present invention is magenta, flunoan,
Although it is possible to give various tones such as violet, the dye represented by formula (II) generally has a magenta tone, and the dye represented by formula (III) generally has a blue or cyan tone. be.

Specific compound examples of the dye of the present invention are shown below, but the present invention is not limited thereto.

N HsCz/ゝC2H5 H6C2'ゝCzHs H7C3′ゝCJ.

HsCz”’ゝCJs N ／　＼ HsCz　　　CzHs C1l.

N ／　＼ l　s　Cz　　　Cz　Hs HsCz′ゝC,H5 H3O2″C2H5 ／　＼ HsCz CzHs H5C2'XC2H4-N SO□CH.

N H, C2C2H4N5O□CH4 HsCz′XCzl’1JSO□CH.

/ \ H, C Go C3H? / \ HyC+ C0IL HsCz CtH4NSOtCHzHsCz
CJJSO□CH.

C C.B.

/ \ 1 (+tCs C@H+t N / \ HsCz CJs / \ )1. C,CoHs The dye of the present invention is synthesized by oxidative coupling of a coupler compound (A) and a color developing agent (B).

Ht R6'ゝR5 (A) (B) Formula (A)
In the formula, L represents a hydrogen atom or a group that leaves during the oxidative camping reaction.

Alternatively, the dye used in the present invention may be a coupler compound (
A) and the nitrolytic compound (C) are synthesized by dehydration condensation.

However, in this case, the atom in the coupler compound is a hydrogen atom.

N.

4a 4゜1〆 Coco R6'XR5 / \ HsCt Czl (s / \ HsCz Cz) Is Step 1 Add compound a to 40 g of sodium hydride (60%) and 18 ONl of tetrahydrofuran while stirring at room temperature.
A solution of 51.5 g and 41 g of acetonitrile dissolved in 30% of tetrahydrofuran was added dropwise. After stirring at 30°C for 10 hours, the mixture was reacted at 50°C for 6 hours. After cooling, water 5
The reaction solution was poured into 001d and extracted with ethyl acetate. After drying over magnesium sulfate, the solvent was distilled off under reduced pressure. The crude product was recrystallized using ethyl acetate and n-hexane to obtain 17.5 g of compound S. (Yield 24.3%).

Step 2.4 g of dual compound b, 1.2 g of malonitrile, and 10 g of ethanol were refluxed for 3 hours, and then the reaction solution was poured into ice water.

Thereafter, concentrated hydrochloric acid was added to bring the pH of the solution to 1, and a brownish oily substance was separated. When the stirring was continued, the oil crystallized, so it was filtered. The crystals were washed with water and dried to obtain 5 g of Compound C2. (Yield 77.5%
).

, Step 2 - 6.2 g of acetic anhydride was added dropwise to 200 g of tanol being stirred at an internal temperature of 20°C. After stirring for 10 minutes, crystals were precipitated and were collected by filtration. The crystals were washed with ethanol and dried to obtain 12.0 g of Compound-1. (Yield 75.3% mp 170-171°C).

λ ax (in ethyl acetate) 610n ε: 5.
20X10'1-mol-', in ethyl acetate Compound c4. og, compound e5.9g, ethanol 10
While stirring 0- at room temperature, add acid anhydride f110.
Added cc. After reacting at room temperature for 1 hour, saturated brine and ethyl acetate were added to perform extraction.

The organic layer was washed twice with water, dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure.

The crude product was purified using silica gel column chromatography to obtain 5.0 g (yield 52%) of Compound 3.

λ■ax (Ethyl acetate: 587n) (Synthesis Example-3) Synthesis of Compound 5 It was easy to synthesize.

Anhydrous M1.Og was added to the tanol 2 (ld) being stirred at room temperature. After stirring at room temperature for 2 hours, saturated brine and ethyl acetate were added for extraction.

After washing the organic layer twice with water, it was dried using magfusium sulfate, filtered, and the solvent was distilled off under reduced pressure.

The crude product was purified using silica gel column chromatography to obtain 2.0 g (yield 52%) of Compound 5.

λ1Iax (in ethyl acetate) 595r+++ (Synthesis Example-4) Synthesis of Compound 11 Compound g Compound g could be easily synthesized according to Synthesis Example 1.

Compound g4. og, compound 22.5g, ethanol 10
Reaction and purification were performed using 1.2 g of 0-2 acetic anhydride in the same manner as in Synthesis Example 2. 4.2g of Compound 11 was obtained. (
yield 66%).

λMax (in ethyl acetate): 596nII/ / \'5' //\ / / / / / / / / / / The compound used for the synthesis of compound 14 can be easily synthesized according to Synthesis Example] Ta.

Reaction and purification were carried out in the same manner as in Synthesis Example 2 using 1.0 g of Tanol 20-1 and acetic acid.

2.4 g of Compound 14 was obtained. (Yield 61%).

λmax (in ethyl acetate): 590 nm (synthesis example-
6) Synthesis of Compound 18 Satoru S (compound used in the synthesis of Compound 18) could be easily synthesized according to Synthesis Example 1.

Reaction and purification were performed in the same manner as in Synthesis Example 2 using 40w11 tanol and 1.0 g of acetic anhydride. As a result, 1.8 g of Compound 1 λax 8 was obtained.

(Yield: 43%) (in ethyl acetate): 92 nm / / / / / / Step-1 Tanol 20- was refluxed for 1 hour. After that, add 20 -
In addition, 5 ml of ammonia water was added.

An oily substance began to precipitate from the reaction solution, but as it continued to be stirred, it crystallized, so it was passed through a furnace.

After washing the crude crystals with water, recrystallization was performed using isopropanol-water to obtain 1.2 g of Compound 1.

(Yield 60%).

Step-2 Reaction and purification were performed in the same manner as in Synthesis Example 2 from 1.0 g of Tanol 20-1 acetic anhydride. As a result, compound 34
1.2g of was obtained. (Yield 51%).

Novaax (in ethyl acetate): 515ni
After reacting with 2Y-30(ld) at 50°C for 6 hours, water and ethyl acetate were added to perform extraction. The organic layer was washed twice with water,
After drying with magnesium sulfate and filtration, the solvent was distilled off under reduced pressure, and the crude product 6 was purified using silica gel column chromatography to obtain Compound 0. (7.3 g, yield 20%).

Reaction and purification were performed in the same manner as in Synthesis Example 2 from 1.0 g of Tanol 40-1 acetic anhydride.

As a result, 2.1 g of Compound 35 was obtained. (yield 59%)
.

λwax (in ethyl acetate): 505nm

[Brief explanation of drawings]

Figures 1, 2, 3, and 4 are for compounds 1.9 and 4, respectively.
44.45 is a graph showing an absorption spectrum. Patent applicant: FUJI PHOTO PHOTO A Co., Ltd. Procedural Amendment 1991 y, 24th, 2011 "Explanation" column and drawings

Claims (3)

[Claims] (1) A β-γ-unsaturated nitrile azomethine dye represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) In the formula, R^1, R^2, R^3 and R^4 represent a hydrogen atom or a nonmetallic substituent. R^5 and R^6 are hydrogen atoms, alkyl groups, aryl groups,
Represents a heterocyclic group. V represents a nitrogen atom or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. X, Y, and Z represent nonmetallic substituents. At least one of Y and Z represents an electron-withdrawing substituent. X and Y and/or Y and Z and/or R^1 and R
^2 and/or R^2 and R^5 and/or R^
5 and R^6 and/or R^3 and R^6 and/or R^3 and R^4 may be bonded to each other to form a ring structure. X, Y, Z, R^1, R^2, R^3, R^4, R^5
, R^6 may be further substituted. (In the formula, ▲ includes mathematical formulas, chemical formulas, tables, etc.) is a notation that indicates that Y and X can be either cis or trans with respect to the double bond.) (2) The dye represented by the general formula (I) is the following general formula (
Claim (II)
The dye described in 1). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) In the formula, S, T and U are each a nitrogen atom, a methine group, or a methine group having an electron-withdrawing group, at least one of which is an electron-withdrawing group. represents a methine group having a group, n is 0
Represents an integer from ~2, and Q represents a ▲numerical formula, chemical formula, table, etc.▼ together with a residue, a group of nonmetallic atoms necessary to form an aromatic heterocycle or an aromatic carbocycle. R^1, R^2, R^3 and R^4 represent a hydrogen atom or a nonmetallic substituent. R^5 and R^6 represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R^1 and R^2 and/or R^2 and R^3 and/or R^5 and R^6 and/or R^3 and R^6 and/or R^3 and R^4 are combined with each other may form a ring structure. X, Y, Z, R^1, R^2, R^3, R^4, R^5
, R^6 may be further substituted. (3) The dye represented by the general formula (I) has the following general formula (
The dye according to claim (1), which is represented by III). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) In the formula, at least one of R^7 and R^8 represents an electron-withdrawing substituent, and the other represents a substituent. R^1, R^2, R^3 and R^4 represent a hydrogen atom or a nonmetallic substituent. R^5 and R^6 represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R^1 and R^2 and/or R^2 and R^5 and/or R^5 and R^6 and/or R^3 and R^6 and/or R^3 and R^4 are mutually They may be combined to form a ring structure. X, Y, Z, R^1, R^2, R^3, R^4, R^5
, R^6 may be further substituted.