JPS60186567A - Pyrazolo(1,5-b)(1,2,4)triazole dye - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I [R1 and R2 are H, or substituent group; R11 and R12 are H, or (substituted) alkyl; R12 is H, halogen, or (substituted)alkyl; n is 1 or 2]. EXAMPLE:A compound shown by the formula II. USE:Magenta dye for forming color image, a magenta filter for photography, or a magenta filter for solid camera tube. Also usable as a blue or a red filters by blending the titled dye with cyan dye and yellow dye. PREPARATION:An intermediate (preferably compound shown by the formula IV, etc.) shown by the formula III (X is H, or group to be released in coloring process) is oxidized and coupled with an aromatic primary amine (e.g., 4-amino-N- ethylaniline, etc.) shown by the formula V.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to novel 1H-pyrazolo[1,5-b)(1,2
, 4] relates to dyes produced from triazole derivatives.

(Background of the Invention) 1H-pyrazolo[1,3-b)(1,2.4) triazole visiting conductor is a novel heterocyclic compound, and exhibits twisted characteristics as a magenta coupler in color photography.
It is disclosed in Japanese Patent Application No. 8-45512 filed by the present inventors. As a result of extensive research, the present inventors have discovered that a bright magenta dye with less yellow sub-absorbing components can be obtained from this derivative, and has accomplished the present invention.

(Mechanism of the Invention) That is, the dye of the present invention has the following general formula (1) (wherein R
1 and R2 represent a hydrogen atom or a substituent, R11 and R12 represent a hydrogen atom, an alkyl group, or a substituted alkyl group, and these may be the same or different. R13 represents a hydrogen atom, a halogen atom, an alkyl group, or a substituted alkyl group. n is the number of substituents R13, and represents 1 or 2. ) represented by biranoro [/, tar b] (1
, 2.4] triazole yarn azomethine dye.

The 1H-pyrazolo(1,5-b)(1,2,4) triazole derivative useful as the U-isomer during the production of the dye represented by the general formula (1) above is represented by the following general formula [11]. or/and is represented by the general formula [11]: (
It is a polymer containing repeating units induced by an ethylene-like monomer having 15 minutes in the side chain.

(In the formula, R1 and R2 represent a hydrogen atom or a substituent, and X represents a hydrogen atom or a group that leaves ~1 in the coloring process.) Specifically, R1 and R2 represent a hydrogen atom or a group conventionally used as a color coupler. Examples include halogen atoms, alkyl groups, aryl groups, heterocyclic groups, cyano groups, alkoxy groups, aryloxy groups, acylamino groups, anilino groups, ureido groups, sulfamoylamino groups, and alkylthio groups. group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclicoxy group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group , represents a heterothio, sulfinyl group, phosphonyl group, aryloxycarbonyl group, or acyl group;
Alternatively, R1 represents a group that is bonded to the carbon at the coupling position via a sulfur atom and is decoupled by coupling;
R2 or Represents an attached or connecting group, and connects the general formula [
The moiety represented by [2] is bonded to ethylenic unsaturation.

More specifically, R1 and R2 are each a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), an alkyl group (
Straight chain or branched alkyl groups, aralkyl groups, alkenyl groups, alynyl groups, cycloalkyl groups having 1 to 32 carbon atoms,
A cycloalkenyl group, which may be substituted with an oxygen atom, a nitrogen atom, a sulfur atom, a substituent linked with a carbonyl group, a hydroxy group, an amino thread, a nitro group, a carboxy group, a cyano group, or a halogen atom. ,for example,
Methyl group, propyl group, t-butyl group, trinormeromethyl group, tritenyl 1,2-methanesulfonylethyl group, 3-(3-pentadecylphenoxy)propyl group,
3-(4-(2-[4-(4-hydroxyenylsulfonyl)phenoxy]dodecanamido)phenyl)propyl group 1.2-ethoxytridecyl group, trinorolomenalur, cyclo is butyl group% 3- (2, Hiroji-t
-amylphenoquine)propyl M, etc.), aryl group (
For example, phenyl group, 4-t-butylphenyl group, 2,
4-di-t-amylphenyl group, Hiro-detradecanamidophenyl group, etc.), heterobases (e.g., 2-furyl group, nochenyl group, -1-pyrimidinyl group, λ-benzothiazolyl group, etc.), cyano group , alkoxy groups (e.g. methoxy group, ethoxy group).

7 2-methoxyethoxy groups, 2-doacyl ethoxy groups, 2
- methanesulfonyl ethoxy group, etc.), aryloxy group (e.g., phenoxy group, 2-methylnoenoxy group, Hirotithylphenoxy group, etc.)% acylamino group (e.g., acetamide group, benzamide group, tetradecaneamide group) , α-(,2゜Hiro-di-t-amylphenoxy)butyramide group, r-(J-t-butyl-Hiro-hydroxyphenoxy)butyramide group, α-(F-(Hiro-hydroxyphenylsulfonyl)phenoxy) decanamide group, decanamide group, -anilino group (e.g. phenylamino group, no-chloroanilino group, J-chloro-tertetradecanamideanilino group, -chloroS-dobnoloxycarbonylanilino group, 1N- acenalanilino group, !-chloro5-(α-(3-t-funaluhiro-
Hydroxynoenoxy)dodecaneamide)anilino group%
etc.), ureido group (ipQ, noenyl ureido group,
methylunoid group, "N.

1N dibutyl ureido group, %), sulfamoyl γ amino and (1 R 1, to, N-dipropylsulnoamoylamino g % hemeterupedecylsulf γ 7yl
Minohana, etc.), alkylthioyl (e.g. V, butylthio, octylthio, tetrazolthio; A-J, g,!
-Noenoxyetherteol, 3-phenoxyprobylthio group, 3-(tA-t-bunalnoenoquino)propylthio group, W), arylthio thread (e.g. L, phenylthio, 2-butoxy-1-1-octyl) phenylthio group,
3-pentadecylphenylthio$, 2-carboxyphenylthio group, V-detradecanamidophenylthio group.

etc.), alkoxycarbonylamino groups (methoxycarbonylamino groups, tetraketyloxycarbonylamino groups, etc.), sulfonamide groups (e.g.
Methanesulfonamide, hexane fucansulfonamide °-1, and benzenesulfonamide N.

p-toluenesulfonamide group, octadecanesulfonamide group:, λ-methyloxy-1-1-butylbenzenesulfonamide Jj;, carlevamoyl group (for example, N-ethercarbamoyl group, N.

N-dibutylcarbamoyl group % N-(2-dodecyloxyethyl)carbamoyl J, t, N-methyl-N-dodecylcarbamoyl, IN -(3-(2').

V-di-tert-amylphenoxy)propyl)carbamoyl group, etc.), sulfa-7yl culture (j+Il,
N-ethylsulfamoyl group, N, N-c! Lopylsulfamoyl group, N-(,2-dodecyloxyether)
sulfamoyl group, H-ethyl-IN-dodecylsulfamoyl group, N,N-diethylsulfamoyl group', etc.), sulfonyl-$ (eg.

Methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl JL'J), alkoxycarbonyl! l: (e.g. methor-dicarbonyl group, bunaloxocarbonyl thread, dodecylcar+1
% heterocyclic oxy group (e.g., V, /-phenyltetrazole-j-
oxy group % nautitrahydropinyloxy group 1 etc.),
Acyloxy (e.g., acetoxy group, etc.) Carbamoyloxy group (e.g., acetylaminooxyno-, benzylaminooxy group, etc.) Silyloxy group (*Il
! Eha, trimethylsilyloxy group, dibutylmethylsilyloxy group.

Bp) Aryloxycarbonylamino (e.g., r, noenocarponylamino group, etc.), imide group (4pQeV, N-succinimide group%IN-phthalimide group, 3-octadecenylsulcinimide) basis,
etc.) Hetero 1-button thiono-' (Iyile is 1,2-benzthyanylthio group, λ, Goosey phenoxy/, 3゜5-triazole-6-thio group, λ-pyridylthio group, etc.) Sulfinyl group ( 91!μ, dodecanesulfinyl group, 3-pentadecylphenylsulfinyl group, 3-cyanoxyprobylthio group, etc.) phosphonyl group (6; 14, for example, phenoxyphosphonyl group, octyloxyphosphonyl group, phenylphosphonyl group , etc.) Aryl ratio carbonyl group (i+lle is phenoxycarbonyl g, etc.) Acyl ratio (e.g., acetyl group, 3
- represents a phenylpropanoyl group, benzoyl group, μm dodecyloxybenzoyl group, and X is a hydrogen atom,
A halogen atom (for example, a chlorine atom, a certain atomic atom, an iodine atom, etc.), a carboxy group, a group connected through an oxygen atom (for example, an acetoxy group, a propanoyloxy group,
Benzoyloxy, λ, Hironchlorobenzoyloxy, ethoxyoxaloyloxy, bilbinyloxy, cinnamoyloxy, phenoxy, Hiro-cyanophenokidyl, etc., Hiro-methanesulfonamidophenokidino, Hiro -Methanesulfonylphenoxy group, α-naphthoxy group, 3-tadecylphenoquine, benzyloxycarbonyloxy group, ethoxy group, -monocyanoethquine group, benzyl bud-? % λ-phenethyloxy M, -z-: phenoxyethoxy group, 5-phenyltetrazolyloxy, λ-benzothiazolyloxy,
etc.), a group linked by an yatom (for example, a pencenesulfonamide group, an IN-ethyltoluenesulfo/amide group).

Bezotafluoroptan γmide, λ, 3. ≠＋ ' 1
Name - is N, N, N-
Diethylsurun amoylamino group% l-biphosphorus group, j,j-dimethyl-,2,g-dioxo-3-oxazinonyl group, /-benzyl-ethoxy-3-hytantoynyl group 1.2 tl-/.

/-dioxy-3(211)-oxo-/, 2-benzisothiazolyl group 1.2-oxo/2.2-dipidoro-l-vininylka 1-, imidazolyl;, bifuzolyl group, 3.5-diethyl- 7,2, Hiro-Triazole-
/-yl, 5-yo/ko&'j: j-promobenzotriazol-7-yl, j-methyl-/.

Co, j, 4l--l・'J 7zo-ru/-yl, pensimidazolyl group, Hiro-methothenthodiphenylazo group, ≠
- bivalor 1-ruaminophenyl azo group, no-hydroxy-ψ-propanoylphenylazo group, etc.), groups linked by a sulfur atom (e.g., phenylname group 1,2-calphokydiphenylthio group, λ-methoxy 5-t -octylphenylthio group, V-notanesulfonylphenylthio group, ψ-octanesulfonamidophenylthio group, benzylthio group 1.2-cyanoethylthio group, l-ethoxycarbonyltridecylthio group, j-phenyl=2,3 .I
A.

j-tetrazolylthio group, -penzoteazolyl, thiocyano group, N-diethylthiocarbonylthio group,
Dodecyloxythioluponyltheo group, etc., groups linked by carbon atoms (e.g., triphenylmethyl group, hydroxymethyl group, %N-7-polinomethyl group, atom, alkyl group, aryl group, heterocyclic group, R
1, R2 has the same meaning as already defined, etc.).

To describe in more detail the divalent group in which R1, R2, or
Ethylene group %/, 10-decylene group, -CH2CH2-
O-CH2CH2-, etc.), a substituted or unsubstituted phenylene group (e.g., 1,4-phenylene group, 1,3-phenylene group).

-NHCO-R3-CONH- group (R3 represents a substituted or unsubstituted alkylene group or phenylene group, e.g. -NCOCH2CH2CONH-, (R3 represents a substituted or unsubstituted alkylene group, e.g. -S-CH
2CH2-S- represents the above-mentioned leaving group bonded with the above-mentioned divalent linking group.

The divalent linking group represented by either R1 or R2 when contained in the ethylene-like monomer in the general formula (11) is an alkylene group (substituted or unsubstituted alkylene group). A group, for example, methylene group, ethylene group, 1,10-decylene group, -CH2CH2OCH2CH
2-, etc.), phenylene groups (substituted or unsubstituted phenyl groups, such as 1,4-phenylene groups, 1,3-phenylene groups, -CONH-, -O-, -0CO-), and aralkylene groups (such as , , etc.).

Preferred linking groups include the following.

-INIIC(J-, -Cfl 2 C1i 2, -C
112U112NllCU-1-C11°Cll2-(
J-c-1-CuN11-t, :+12CI-12N
HcU-.

-Cj12Ci12 (J-C1-12c112-INl
-ICU-, and the ethylenically unsaturated group part has the general formula (■
) may have a substituent in addition to the moiety represented by .) Preferred substituents are a hydrogen atom, a chlorine atom, or a group having 1 to 1 carbon atoms.
Contains four lower alkyl groups (eg, methyl, ethyl).

(2) The polymer containing a repeating base derived from the monomer represented by the general formula (1) may be copolymerized with at least one ethylene-like ML polymer that can be copolymerized with the monomer.

Specific examples of copolymerizable ethylene monomers include methyl acrylate, ether acrylate, butyl acrylate,
bunal methacrylate and 2-ethylhexyl acrylate.

Pyrazolo of the present invention (/, ff-b) (/, 2. Hiroshi J.
A preferred production intermediate for producing triazole dyes is represented by the first-order general formula CIIA).

(In the formula, R13 and R2a represent a group selected from a hydrogen atom, an alkyl group, and a phenyl group, and these groups may be the same or different from each other, and these groups may have a substituent. , X represents a hydrogen atom, a halogen atom, a substituted amino group, or another coupling-off group listed in general formula (11).) In the compound of the present invention, R1a, R2
The alkyl group of a is a lower alkyl group such as methyl, ethyl, propyl, butyl group to a straight alkyl group having up to 2 carbon atoms, such as pentyl group, hexyl group, heptyl group, octyl group, decyl group, It means an undecyl group, a tridecyl group, an octadecyl group, etc., and may be a straight chain or a branched chain.

Further, the halogen atom of X means chlorine, bromine, iodine, etc., and the acyl group means an acyl group derived from an aliphatic or aromatic carboxylic acid. Further, as the (1) essential amino group of X, two substituents may form a ring structure containing the nitrogen atom of the amino group.

Next, typical examples of the pyrazolo[1,5-b](1,2,4) triazole derivative represented by the general formula (■A) which is an intermediate for producing the dye of the present invention are illustrated.

The dye production intermediate represented by the general formula (■A) can be synthesized by many methods. I have given three examples of typical reaction processes. Reaction step (1) starts from oxydiazole (■) and protects 1, 2, and 4-positions.
4-Triazole (■) is aminated to form (V), and then (V) and an acid anhydride are cyclized and condensed under basic conditions. Reaction, step (2) is 5-aminopyrazole (■
) and an orthoester, the imidoester (X) of the pyrazole is reacted with hydroxylamine to produce amidomequim (xI), which is further dehydrated to obtain the desired hetero-ester. In the reaction step (3), as in the previous step, starting from 5-aminopyrazole, the intermediate (■■) is prepared, and this is oxidized to give ■-virazolo (1,5-b) (1,2 , 4] for producing triazoles. 9 A more detailed explanation of the method is given in Japanese Patent Application No. 5
No. 8-23434 and the Fujifilm patent application filed on February 16, 1980 (agent: Toshizo Iida).

Reaction step (1) Reaction step (2) Reaction step (3) The dye represented by the general formula (1) of the present invention is represented by the general formula (■)
It is obtained by oxidative coupling of the intermediate represented by the following formula (■■) and an aromatic amine represented by the following general formula (■■).

(In the formula, R11 and R12 represent a hydrogen atom or an alkyl group that may have a substituent, and these may be the same or different from each other. R13 is a hydrogen atom, a halogen atom, or a substituted alkyl group. represents a good alkyl group. n is R1
The number of substitutions of 3 indicates 1 or 2, and when it is 2, R1
3 may be the same or different. ) When the amine represented by (■■) is used as a salt with a mineral acid or an organic acid, air oxidation can be easily prevented and the dissolution rate can be improved.

R11 and R12 in the general formula (■■) are preferably hydrogen atoms, aru? represents a substituted alkyl group such as a hydroxyalkyl group, an alkoxyalkyl group, an alkoxyalkoxyalkyl group or an alkylsulfonamidoalkyl group.

Examples of the alkyl group, alkoxy group and substituted alkyl group and alkyl of the alkoxy group related to the salaniphenylenediamine derivative (■■) are t, methyl, ether, n7 proyl, '1so-10 pyl, n-butyl, 1
Charcoal such as so-butyl, 5ec-butyl, t-butyl etc.
Lower alkyl groups with numbers from l to hiro, and n-amyl, d
l-2-methyl-1-butyl, iso-amyl, sec
-amyl, t-amyl, n-hexyl, methylamyl.

noretherbutel, n-hemethyl, 2-hemethyl, 3-
Any higher alkyl group having 5 to 18 carbon atoms such as heptyl, n-octyl, 2-octel, no-ethylhexyl, n-dodecyl, n-octadecyl, and cyclohexyl may be used, and straight-chain, branched, and cyclic Includes: Examples of halogens include chlorine, odor, and iodine. ``The primary amine (Xllll) used to synthesize the dyes of the present invention is preferably ortho or para, more preferably para-enylene diamine;
Specific examples include: 1Jx) V--Amino-1N-ethelaniline 1)z)
41-amino-1~, rN-diethylaniline υ3)
ψ-γ minnow 3-methy/l/-IN, those having an N-alkyl group such as N-diethylaniline, 1) 4)≠-amino-N-ethyl-N-(β-hydroxyethyl)aniline υ5) ψ- Amino-3-menal-1N=ethyl-14=
(β-hydroxyethylaniline) and other IN-hydroxyalkyl groups /l-1,
1)6) Hiro-amino-3-methyl-19-ether-(7
fumethoxyedel) aniline 1J7) ≠ -amino-3-methyl diN-ether-N-methoxybunalaniline L) 8) Hiro-γ minnow 3-methyl-be ether N-(
β-ethoxyethyl)aniline 1J9) <z-amino-3-propyl-he-ethyl N
-(β-methoxyether)aniline υ10)ψ-7mi/-J-1'lopyl-1\-j-thyl-N-(β-methoxyether)aniline L)11)≠-amino-3-methoxyN- Ether-he-(β-methoxy ether)aniline D12) 41-7mi/-j-metherheether~
- Those containing N-alkoxyalkyl groups such as <79-butyethyl]aniline, D13
) Hiro-amino-3-methyl-IN-enal-1'1l-
(β-(β-methoxy7ethoxy)ethyl)aniline 1J14) to Hiro-amino-3-butyl-heether (
β-(β-ethoxyethoxy)ethyl)aniline L) 15) Hiro-amino-3-metaluhenaru N-
(β-<p'--i toxyethoxy/)ethylnoaniline 1J16) ψ-amino-3-metherhemethyl-N-
(β-(I-ethoxyethquin)ethyl)aniline 1JJ7)11. -No'minor N-ether-to-(β-
(β-methoxyethoxy)ethyl)aniline IJ1B)
≠-Amino-N-ethyl-1i-(β-(β-ethoxyl-ethyl)ethel)

D19) Ll, -amino-he-upper chiluhe-(β-methylsulponamidoethyl)aniline IJ20) tl, -nomino-3-menal-1\-ethyl-N-(β-methylsulponamidoethyl)aniline D21)<t-amino-3-chloro-N-ethyl-N(
β-methylsulfonamidoethyl) aniline j, h°2) 4t-amino-~-ethyl-(β-methylsulfonamidoethyl)-3,5-xylyzinya IN-alkylsulfonamidoalkyl 1sui) etc. Deru2ru. Examples of these salts are:

Mineral acid salts of the above-mentioned noenylenediamine derivatives, such as hydrochloride,
Inorganic acid salts such as hydrobromide, hydrogen iodide, hydrohalogenates, eroding salts, phosphates, carbonates, or formates, butyrates, propionic acids, etc. Aliphatic carboxylic acids, benzoates, aromatic carboxylic acids such as naphthalene-α-carboxylate, naphthalene-β-carboxylate, aliphatic sulfonates such as methanesulfonate, naphthalene-α-sulfone They are organic acid salts such as naphthalene-β-sulfonate, p-toluenesulfonate, etc., and it is difficult to select them appropriately depending on the manufacturing requirements of the dye. When used as a medicine, it is preferable to use one that does not adversely affect photographic properties. For this purpose, mineral acid salts such as sulfates or aromatic sulfone opening groups such as p-toluenesulfonic acid are usually used.

As the phenylene diamines used in the present invention, the compounds of the above specific examples 3), 5), 6) and 19) are particularly preferred in that they provide magenta dyes with particularly good hue. Additionally, substituents at the 3-position are useful for adjusting the coupling rate; electron-withdrawing groups such as chlorine atoms improve the coupling rate, and electron-donating substituents such as the methyl group increase the coupling rate. It has a slowing effect.

As a preferable dye production intermediate in the present invention, the general formula (
■Use a compound corresponding to A) and combine it with the general formula (■■
) with the corresponding phenylene diamine, the dye of the following general formula [IA] is obtained.

(In the formula, R1 and R2 represent a group selected from a hydrogen atom, an alkyl group, and a phenyl group, and these groups may be the same or different from each other, and these groups may have a substituent. R11 and R12 represent a hydrogen atom or an alkyl group that may have a substituent, and these may be the same or different. R13 is a hydrogen atom, a halogen atom, or an alkyl group that may be substituted. (r is the number of the substituent R13, and represents 1 or 2.) Exemplary compounds of the general formula (1A) are azomethine dyes represented by the general formula (1).

A coupler represented by the general formula (■), which is a dye intermediate,
It can be synthesized in the coexistence of phenylene cyanide represented by the general formula (■■) and an oxidizing agent. This coupling reaction is T
．． H. James “The Theory of th”
e Photographic Process” (4th
(Ed.) (Macmillan, 1977), No. 72
As shown in Figure 1, a leuco nest dye is formed by the nuclear attack of the coupler anion on the quinone diimine formed by oxidation of phenylenecyamine, and then becomes an azomethine dye. Reactions 1 and 6 are preferably carried out under stable conditions, and the reaction medium may be an organic medium, an aqueous organic solvent or an aqueous solution. When reacting in a basic aqueous solution, the coupler may be an oil-in-water dispersion, and the dispersion may be present in a hydrophilic colloid medium such as gela nano.

Any oxidizing agent, organic or inorganic, can be used as long as it has the potential to oxidize phenylenediamine, and even if it is commonly understood that this oxidizing agent is dispersed in the reaction medium, Good too. When the coupling elbow is not attached to the 7-position of the coupler, phenylenecyamine of the general formula (■■) is added in an amount of 0.1 to 10 mol, preferably 0.1 to 10 mol, preferably 0.1 to 10 mol, of the general formula (■■) per 1 mol of the coupler of the general formula (11). The amount of oxidizing agent is at least 4 equivalents, preferably 4.4 equivalents.
~20 equivalents are used. When the coupler has a coupling-off group at the 7-position, the dye of general formula (■) is synthesized in the same manner as above, except that at least 2 equivalents, preferably 2.2 to 10 equivalents, of the oxidizing agent are used. can. When coupling the aqueous medium, pi is preferably 8 or more, preferably between 10 and 12. As an oxidizing agent, silver halide,
Hydrogen peroxide, manganese dioxide, potassium persulfate, oxygen,
Other Fieser, Organic R by Fieser
Compounds described in agents can be used.

The magenta color score of the present invention can be formed into an image according to the method of silver halide color photography as described in Japanese Patent Application No. 58-45512.

In order to improve the stability of the dye of the present invention against light or heat, known stabilizers can be used in combination. To achieve this purpose, U.S. Patent No. 3.935,016 and U.S. Pat.
, 982, 944, U.S. Pat. No. 4,254,216, JP-A-55-21,
Hydroquinone diether derivatives described in JP-A No. 004, phenol derivatives described in JP-A-54-145, 520, U.S. Pat.
Spiroindane derivatives and methylenedioxybenzene derivatives described in US Pat. No. 62,888, U.S. Pat. No. 3,76
4, No. 337, No. 3, 432.300, No. 3, 574
, No. 627, No. 3, 573, 050, JP-A No. 1983-1
No. 52,225, No. 53-20, No. 327, No. 53-1
Chroman derivatives, spirochroman derivatives, coumaran derivatives, etc. described in No. 7,729, JP-A-55-63
Hydroquinone monoether derivatives and para-aminophenol derivatives described in British Patent Publication No. 1,347,556, British Patent Publication No. 2.066,975, and Japanese Patent Publication No. 12,337/1983, British Patent Publication No. 48-31, 625 ,
Examples include bisphenol derivatives described in US Pat. No. 3,700,455.

In order to improve the stability against heat or heat,
The combined use of metal complexes is also effective. Such metal complexes are disclosed in U.S. Pat.
It's listed in issue 78.

Representative examples of compounds are shown below.

Pyrazolo (1, 5-b) (1, 2, 4) in the present invention
In the triazole skeleton, the nitrogen atom at the bridge position and 1
The lone pair of electrons on the λ nitrogen atoms of the −-position nitrogen atom and the three nitrogen bonds on the condensed ring together have an isoelectronic electronic structure with the naphthalene skeleton. Therefore, in a broad sense, dyes represented by the following general formulas (A) and (B) can be formed. In the formula, Q and Q' each represent an atomic group necessary to complete the coloring system. The compound represented by the general formula (1) has almost no absorption in the visible region.

However, when the group is -N=N- (aryl group) or esterified carboxyl group, it corresponds to general formula (A) and becomes a yellow dye. For example, dyes other than azomethine dyes represented by the general formula (B) and derived from the N' formula ([1) include methine dyes, cyanine dye salts used as photographic sensitizing dyes, Includes dyes such as cyanine dye bases and merocyanine.

That is, dyes represented by general formulas (■■) to (■■) are included.

(In the formula, 1 no J, J-h 2 , , L-3...1
ノ11 is Metin 7.1・Father ko, 1,! (,〈Menan 7 Clothed in Tang, It23 ke, υW[H Hou Young I+
', □1゛Asa)1. This alkyl group can also be converted to Naomata-cho.1. Niphenyl7. jj and 1.
L24 antihi 1 and 25 are water atoms, rrugilji δ:,
γ-aryl group, di, same or different, shi, yo7
(/-) or more σ)1α conversion may also be present. IL
'1, i'+' Yohi 1 mo 2 is 1jiJ Jinki-lC R1, H+2 of formula (11) and k)! 7, preferably +jIJ, self-; dazzling style (11 eight, 7'l';
d 7'L lCI et al. 1a Friend 1 is also synonymous with 2a. ulJ For example, the 1 defined by the -dispersion formula (X1ll > is also the same as 13C3-(, C), and r is the same as the 1 punched in the -dispersion formula.

ZliJ ri negative or A negative connotation-I-4 original momme: 4 J
J: It is necessary to make ・ into shape; ARM is necessary;! Nai QM atom 4'f"t ,, 4; wa L, Z 2 (j', 3L
4. ;/:c Ishi Otsu;-L's (';'t, I) knee \ te [] ketomethylene crosspiece form h −
<Iby 297. C+):' i, r21"m J3
A child: represents p, I, fl.

1) , 13・Yohiq +j2-''''゛ノ' also shows a positive pull, 111 is / C' as Ding! Noi-J'>-S sword S Zoroi 4 no, Shi-ha-11 songs with negative ions I9
, Yl, represents an alkyl group, and S
(↓71 is selected so that the charge of the molecule of λri, general 'A, and (Xν11) is 11). The reeding device 8 is a cyanine dye (Itv: Heterogeneous dye used, J91 is indononine, benzothiaso/l, hexoxysol, benzoselenazole, benzoselenazole, quinoline. , Inyanoline etc. ``Table 12 of the atomic groups that are indispensable in rough seas.

The substituent Z2 is conventionally used in merocyanine.
With heterologous ketomethylene cedar, such as hydantoin, thiohydantoin, rotanine, Barbir R4,
Theopalhisor city! -thiazolidine-ψ-on, Koname, 2,! ,-Oh? Length Dashirijin Dione 2
〜Represents the base material necessary for converting imidacillin-one, nopyrazoline-teron or indacion.

In the present invention, compounds represented by general formulas (XIV) to (Xi, 4if) with ≧1 are not used as photographic sensitized images.
Shi, Part 4. L body (effect of the invention) -・The present invention σ which is expressed by the false formula (1)) Dye (well, color ++!j I is used as a magenta dye for A1. f7υ copy"\ magenta filter j:i'
L< can also be used as a magenta filter for 1.5J todotsuj''o1 elephant/IR. When combined with zoinsuchier or yellow nest with dou, it can also be used as 11' or red filter. can.

The dyestuff of the present invention has good properties, has a bright color, and has good fastness to heat.1. It is magenta tartar. Compared to the conventional j-pyrazolone system, there is no sub-absorption near ζj,
The tail of the long wavelength 1 is 7-). The dye of the present invention is a dye with far more light fastness than macenta east 7- + tobisaka obtained from oviparous cabrani. Become.

The coupler Δ of the present invention and the following chemical formula 8:
The comparative couplers to be prepared, / and /m mol, respectively, were added to 10 m0 of ethanol (/, in which the color developing main ethyl-1'
J-(,2-methanesulfuramidefur)aminomethylaniline (1) J9) / sulfuric acid j beans /, 311] mol yyH, mixed with anhydrous charcoal 1 mol. Y to moles, 5'
Add the precipitated water Yd solution to the water of nIp and let it cool at room temperature.
I stirred it. Because of this mixture, >(, li (L'il
Since the water bath containing 10 InQ contained 11 moles of Caliuno-0≠I, it was reduced to 11)5.

After stirring well for 7 hours at room temperature, add somp's Takumi 1-tabi ethyl and 30 cups of water to extract the mixture. n,
F the acid enal layer! L! 1) After thoroughly washing with J-basin water, the solvent was removed, and the remaining lrF was separated by Nori gel column chromatography. 761411i? F5- and ether were used.

The coupler of the present invention (1) has a magenta color that can be obtained
/'s NM concentration is % sword chloroform (C1) α
Among the three, they are as follows.

/ , -Hiro (3H% t, J- = 7.z), z, g5-
■１轡－■￥輌－－ゆう－－■■■――■－－－□,.

(3ii, s)2. t, z (Otsu 11.S) j, 9
f (3HlS), i, 2 (7-~j, 71r (7fl
)4+,,4g(/H,br t%'J=7)A,t
O~A, f(7(,2,il-1), a'('(/
H1d1 J = ri, θ) Shown by under 1 ≠ one methi/L7-JII
The absorption of : satisfies the following structural formula 13. What is the melting point of this dye? Hirohiro~2ψ5°.

〜〜〜 The mark indicates a methyl group indicating a chemical reaction in proton N1\11mo. From the coupler of the present invention, A (t dye &'j 2, comparative coupler A7 Saha ra-shaped kite, J dye and λI?) a and X are the same, and the sub-absorption in the vicinity of 00 to 30 nm is The hem on the wavelength side is sharply cut, and the color is '14. jj4
It is useful for reproducers when used in optical materials.

Patent Applicant: Yashi Photo Film Co., Ltd. Procedural Amendment Written in May 1982, 2-[1! 1', '+, Chief Minister Hsu's Palace 1, Incident Display Showa! Patent Application No. 'I/73g No. 2
, Name of invention Villazo O [/,! r-b)[/,,2.
K) Triazole dye 3, relationship with the case of person making corrections Patent application masterpiece Location: Minamiashigara City, Kanagawa Prefecture? i & 210 address name (
520) m: IrM Film Co., Ltd. 4, subject to correction
Specification 5. We will submit the details of the amendment 1 ((, #1 (no changes to the content)).

Claims (1)

[Claims] General formula (wherein R1 and R2 represent a hydrogen atom or a substituent,
R11 and R12 represent a hydrogen atom, an alkyl moiety, or a substituted alkyl group, and these may be the same or different. R13 represents a hydrogen atom, a halogen atom, an alkyl group, or a substituted alkyl group. pyrazolo[1, n is the number of substituents R13 and represents 1 or 2]
5-b) (1, 2, 4) triazole yarn dye.