JPH04356042A - Photographic sensitive material containing naphthol-based coupler that can be washed away - Google Patents

Abstract

PURPOSE: To obtain a novel photographic naphthol type coupler capable of forming a dye by oxidation coupling. CONSTITUTION: A photographic naphthol type coupler having -CONH2 at the 2-position and a ballasted group releasable by coupling at the 4-position but not having a ballast group is incorporated into a photographic material. A dye formed by oxidation coupling can easily be washed off the photographic material during processing. Such a naphthol type coupler is useful for a photographic silver halide material and in photographic processing.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a novel photographic naphthol coupler which is capable of forming a dye by oxidative coupling and which, upon processing, can be washed out of a photographic light-sensitive material containing the coupler. This invention relates to silver halide compositions.

0002

BACKGROUND OF THE INVENTION Various couplers are known in photographic materials and photographic processing. Photographic couplers include naphthol couplers, which typically produce cyan dyes in photographic materials and photographic processing by oxidative coupling. These naphthol couplers generally produce cyan dyes by oxidative coupling with color developing agents. It is known that such naphthol couplers can form dyes by oxidative coupling and can be washed out of photographic materials by processing. These naphthol couplers are described, for example, in US Pat. No. 4,482,629.

Dye-forming naphthol couplers that can be washed out of photographic materials by photographic processing are
The group at the 2-position of the naphthol coupler contains a substituted water-soluble group, such as a carboxyl group or a sulfonic acid group.

0004

SUMMARY OF THE INVENTION It is an object of the present invention to provide a system which is less expensive to manufacture than the naphthol-based couplers described and which allows the use of lower concentrations of couplers in photographic elements without significant changes in the resulting image. It has been desired to provide naphthol couplers that provide useful dyes that can be washed out of photographic materials with additional benefits.

It is also an object of the present invention to provide such naphtholic couplers which contain a coupling-off group which enables a desired acutance and desired interlayer effect in color photographic silver halide and which enables low density processing of the coupler. has also been desired.

[0006]

[Means for solving the problems] The present invention solves the above problems,
A fixed naphthol coupler capable of producing a dye by oxidative coupling that can be washed out of a photographic silver halide composition by photographic processing, wherein -CON is present in the second position.
The solution is to provide a photographic silver halide composition containing a fixed naphthol coupler comprising an H2 group and a ballast group-free naphthol coupler moiety with a ballasted coupling-off group in the 4-position. The ballasted coupling-off group preferably comprises a releasable photographically useful group (PUG).

The above fixed naphthol coupler is generally represented by the following formula.

[Image Omitted] In the above formula, Z is a ballasted coupling-off group, and R1
are ballast-free substituents that do not adversely affect the intended properties of the coupler and dye, and z is 0.
, 1, 2 or 3. R1 does not contain ballast groups since such groups would adversely affect the washout properties of dyes produced from naphthol couplers.

The present invention will be explained in detail below. The ballasted coupling-off group (Z) allows the naphthol coupler to become fixed in the photographic element containing the intended photographic silver halide composition prior to exposure and processing. Upon exposure and processing of the intended composition, the naphthol coupler reacts with the oxidized color developing agent to form a dye that is washed out of the composition during processing. Coupling-off groups are also released during processing. The coupling-off group portion containing the ballast group remains where it was applied. Preferably, the coupling-off group is a releasable photographically useful group (PUG) released by the photographic element.
Contains. The PUG may remain immobilized at the location where it is applied, or it may be mobile to the extent that it can be moved to a location where it can perform its intended function after release.

The preferred naphthol couplers disclosed include a coupling-off group of the formula: -(LINK)n -(TIME)m -PUG where TIME is a releasable timing group that can be released from the LINK moiety during photographic processing, and LINK is released from the naphthol coupler moiety upon oxidative coupling of the naphthol coupler. n and m are independently 0, 1 or 2, PUG is a releasable photographically useful group, preferably a releasable development inhibiting group, and At least one of n and m is 1 or 2.

An imaging process having the described advantages comprises the steps of developing the exposed photographic element with a color developing agent in the presence of the naphthol coupler described and washing away the dye formed from the naphthol coupler.

All naphthols which can contain a -CONH2 group in the 2-position and a ballasted coupling-off group in the 4-position and which can be washed out of the composition by oxidative coupling of the coupler, especially dyes, coupler moieties are useful. It will depend on the particular developing agent and the particular processing mode, and it will be appreciated that the reaction product of the coupler moiety and the oxidized developing agent may be color-forming or colorless. Specific useful naphthol coupler moieties can be unsubstituted except for the necessary substituents at the 2- and 4-positions as described. Optionally, in addition to substituents at the 2- and 4-positions, the naphthol coupler moiety may contain other substituents that do not adversely affect the intended properties of the element or coupler. Such substituents include 5-NHSO2CH3, 5-NHCOCH3 or 6-NHSO2CH3. Useful naphthol coupler moieties include, for example, the following patents in which the group described at the 2-position is substituted with -CONH2, U.S. Pat.
No. 01, No. 2,474,293, No. 3,227,
No. 554, No. 4,482,629 and No. 4,8
No. 57,447, in particular those with ballasted coupling-off groups.

Any of the ballasting group-containing coupling-off groups known in the photographic art can be utilized at the 4-position of the naphthol coupler moiety. Specific examples of useful coupling-off groups include, for example, U.S. Pat.
No. 1,701. Preferred coupling-off groups include those capable of releasing the PUG by photographic processing, particularly those having a releasable timing group between the bond to the coupling position of the coupler and the releasable PUG. Preferred timing groups include, for example, U.S. Pat. Nos. 4,861,701 and 4,248,9.
No. 62, No. 4,409,323, No. 4,482,
No. 629 and No. 4,857,447.

A preferred naphthol coupler is represented by the following formula.

[Formula 2] In the above formula, X is 5 such as an aryl group or a heterocyclic group.
-, represents an atom that completes a 6- or 7-membered ring, and R1
is a substituent that does not contain a ballast group, and z is 0, 1,
2 or 3, BALL is a ballast group known in the photographic art, T2 is a release timing group,
R2 and R3 are independently hydrogen, unsubstituted or substituted alkyl or aryl, for example from 1 to 40 carbon atoms.
alkyl or aryl of 6 to 40 carbon atoms (e.g. phenyl or naphthyl group), and q
is 0, 1 or 2. For example, T2 is described in U.S. Pat. No. 4,248,962 and U.S. Pat.
is a releasable group of PUG by intramolecular nucleophilic substitution as described in No.

In the case of couplers that release PUG through a timing group, reaction of the coupler with oxidized color developing agent cleaves the bond between the coupler and the coupling-off group. The PUG and the remaining portion of the coupling-off group are then cleaved. Preferably, cleavage of the bond between PUG and the remaining portion of the coupling-off group is not accompanied by reaction of the oxidized color developing agent. Cleavage of the bond between PUG and the remainder of the coupling-off group may involve any reaction known in the photographic art for cleavage of such groups, such as an intramolecular nucleophilic substitution reaction or other removal reaction. can.

Any ballast group known in the photographic art can be utilized on the coupling-off group. A ballast group (BALL) herein is defined as having a size and shape that imparts sufficient bulk to the coupler molecule to render the coupler substantially non-diffusive from the coated layers of the photographic element prior to exposure and processing. means an organic group. Representative ballast groups include, for example, substituted or unsubstituted alkyl or aryl groups of 8 to 40 carbon atoms. Other useful ballast groups include sulfonamide groups, carbonamide groups, carbamoyl groups, sulfamoyl groups, ester groups, sulfone groups, ether groups, thioether groups, and amino groups of 8 to 40 carbon atoms.

Representative timing groups T2 are disclosed in US Pat. No. 4,861,701, US Pat. No. 4,857,440, US Pat.
It is a group capable of releasing PUG via an intramolecular nucleophilic substitution reaction as described in No. 2. Specific timing bases T2 include the following.

embedded image and other specifically described groups as described in US Pat. No. 4,857,447.

R4, R5, R6, R6a in the above structural formula
, R7, R8, R9, R10, R11, R12,
R13, R14, R15, R16, R17,
R18, R19, R20, R21, R22,
R23 and R24 are independently hydrogen or a substituent that does not adversely affect the intended properties of the naphthol coupler or dye produced, such as unsubstituted or substituted alkyl (e.g., methyl, ethyl, propyl, n-butyl,
t-butyl and eicosyl), or unsubstituted or substituted aryl (eg, phenyl or substituted phenyl), and PUG is a releasable, photographically useful group. At least one of the above groups on the coupling-off group is
It is a ballast group.

As used herein, the term "naphthol coupler" refers to a complete compound containing a coupler moiety and a coupling-off group. As used herein, the term "naphthol coupler moiety" refers to a coupler moiety other than a coupling-off group.

PUG can be any group commonly available in imagewise photographic elements. The PUG may be a photographic reagent or photographic element. Photographic reagents herein include moieties that are released by further reaction with components in the photographic element, such as development inhibitors, development accelerators, bleach inhibitors, bleach accelerators, couplers [e.g., competitive couplers,
Dye-forming couplers or development inhibitor-releasing couplers (D
IR coupler)], dye precursor, dye, developing agent (e.g.
competitive developing agents, dye-forming developing agents or silver halide developing agents), silver complexing agents, fixing agents, image toners, stabilizers,
Hardeners, tanning agents, fogging agents, UV absorbers, antifoggants, nucleating agents, chemical or spectral sensitizers or desensitizers may be mentioned.

PUG may be present as a preformed species in the coupling-off group, or it may be present in a protected state or as a precursor. For example, P.U.
G may be present at the point of attachment to the carbonyl group bonded to PUG in a preformed development inhibitor or coupling-off group, thereby protecting the development inhibiting function. Other examples include preformed dyes, dyes protected to shift their absorption, and leuco dyes.

Preferred naphtholic couplers as described have a negative divalent or trivalent valence attached to the naphtholic coupler moiety and the carbonyl group of the coupling-off group, and are heterovalent couplers derived from groups VIb or Vb of the periodic table. A photographic coupler containing PUG containing atoms.

Any couplers known to be useful in the photographic art can be used with the naphthol couplers described and in a variety of conventionally known configurations in photographic elements. The following is a list of patents and publications describing representative couplers that can be used in combination with the naphthol couplers described.

I. Couplers A. Couplers that form cyan dyes by reaction with oxidized color developing agents are described in U.S. Pat.
No. 162, No. 2,895,826, No. 3,002
, No. 836, No. 3,034,892, No. 2,47
No. 4,293, No. 2,423,730, No. 2,3
No. 67,531, No. 3,041,236, No. 4,3
No. 33,999 and “Farbkuppler-e
ine Literaterueversicht,”
[Published by Agfa Mitteilungen, Ba
nd III, pages 156-175 (1961)
] are described in representative patent specifications and publications such as . Preferably, such couplers are phenols and naphthols that produce cyan dyes upon reaction with oxidized color developing agents.

B. Couplers that produce magenta dyes by reaction with oxidized color developing agents are described in U.S. Pat.
No. 2,343,703, No. 2,311,082, No. 3,152,896, No. 3,519,429
No. 3,062,653, No. 2,908,57
No. 3 and “Farbkuppler-eine L
Iteraturuebersicht,” [Agfa
Published by Mitteilungen, Band II
I, pp. 126-156 (1961)]. Preferably, such couplers are pyrazolones and pyrazolotriazoles that produce magenta dyes upon reaction with oxidized color developing agents.

C. Couplers that produce yellow dyes upon reaction with oxidized color developing agents are described in U.S. Pat.
3,265,506, 2,298,443, 3,048,194, 3,447,928
issue and “Farbkuppler-eine Lit”
eraturuebersicht,” [Agfa M
Published by Band III,
112-126 (1961)] in representative patent specifications and publications. Preferably, such couplers are acylacetamides, such as benzoylacetanilides and pivaloylacetanilides, which produce yellow dyes upon reaction with oxidized color developing agent.

D. Couplers that produce colorless products upon reaction with oxidized color developing agents are described in British Patent No. 861,138 and U.S. Patent No. 3,632,345.
No. 3,928,041, No. 3,958,993
No. 3,961,959. Preferably, such couplers are cyclic carbonyl-containing compounds that produce colorless products upon reaction with oxidized color developing agents.

Any releasable P known in the photographic art
UG is also useful as a coupling-off group as described. Specific examples of useful PUGs include the following. PUGs

A. P which produces a development inhibitor upon release
UGs are U.S. Patent No. 3,227,554, 3,
No. 384,657, No. 3,615,506, No. 3
, No. 617,291, No. 3,733,201, No. 3,733,201, No.
No. 4,861,701 and British Patent No. 1,450,
It is described in the specifications of representative patents such as No. 479. Preferably, the development inhibitor is iodine and mercaptotetrazoles, selnotetrazoles, mercaptobenzothiazoles, selenobenzothiazoles, mercaptobenzoxazonals, selenobenzoxazoles, mercaptobenzimidazoles, selenobenzimidazoles, oxa Heterocyclic compounds such as diazoles, benzotriazoles and benzodiazoles. Preferred development inhibitor moieties include those represented by the following formula.

[0029]

[C4]

In the above formula, R29 is unsubstituted or substituted alkyl, such as butyl, 1-ethylpentyl and 2-ethoxyethyl, or alkylthio, such as butylthio and octylthio, and R25 and R26 are independently hydrogen, a carbon atom, 1 to 8 alkyl, such as methyl, ethyl or butyl, phenyl or substituted phenyl, and R27 and R28 are independently hydrogen or one or more halogens such as chloro, fluoro or bromo, 1 carbon atom ~4 alkyl, carboxyl, ester such as -COOCH3, or -N
HCOOCH3, -SO2OCH3, -OCH2
CH2SO2CH3, -OCOOCH2CH3,
-NHCOCOOCH3 or one or more groups such as a nitro group.

B. PUGs that are dyes or produce dyes by release include suitable dyes as well as azo dyes, azomethine dyes, azopyrazolone dyes, indoaniline dyes, indophenol dyes, anthraquinone dyes, triarylmethane dyes, alizarin dyes, nitro dyes. , dye precursors including quinoline dyes, indigoid dyes and phthalocyanine dyes, or leuco dyes, tetrazolium salts or shifted
It is a precursor of pigments such as pigments. These dyes can be metal complexes or metal complex-forming. A representative patent describing such pigments is U.S. Patent No.
No. 3,880,658, No. 3,931,144, No. 3,932,380, No. 3,932,381 and No. 3,942,987. Preferred dyes and dye precursors are azo dyes, azomethine dyes and indoaniline dyes and dye precursors thereof. Structural formulas of some preferred dyes and dye precursors include the following.

[0032]

[C5]

[C6]

C. Couplers PUGs The released couplers can be non-diffusive chromogenic couplers or non-chromogenic couplers or diffusible competitive couplers. Representative patents and publications describing competitive couplers include W. Pueschel's "On the
Chemistry of White Couple
rs,” (Agfa-Gevaert AG, Mi
tteilungen and Forschungs-L
aboratorium der Agfa-Gevae
rt AG, Springer Verlag,
1954, pp. 352-367), U.S. Patent No. 2,998,314, U.S. Patent No. 2,808,329,
No. 2,689,793, No. 2,742,832, West German Patent No. 1,168,769, and British Patent No. 907,274. Structural formulas of preferred competitive couplers include the following.

[0034]

embedded image In the above formula, R32 is hydrogen or alkylcarbonyl such as acetyl, and R33 and R34 are independently hydrogen or soluble groups such as sulfo, aminosulfonyl and carboxy.

[0035]

embedded image In the above formula, R35 is the same group as R34 above, and R36 is hydrogen, aryloxy, arylthio or a development inhibitor such as mercaptotetrazole, such as phenylmercaptotetrazole or ethylmercaptotetrazole.

D. PUGs that generate developing agents The released developing agent can be a color developing agent, a black and white developing agent, or a cross-oxidizing developing agent. These include aminophenols, phenylenediamines, hydroquinones and pyrazolidones. Representative patents include U.S. Patent Nos. 2,193,015 and 2,108,243.
No. 2,592,364, No. 3,656,95
No. 0, No. 3,658,525, No. 2,751,2
No. 97, No. 2,289,367, No. 2,772,
No. 282, No. 2,743,279, No. 2,753
, No. 256 and No. 2,304,953.

[0037] Preferred structural formulas of developing agents include the following.

embedded image In the above formula, R37 is hydrogen or alkyl of 1 to 4 carbon atoms, and R38 is hydrogen or one or more halogens such as chloro or bromo, or such as a methyl, ethyl or butyl group. Alkyl having 1 to 4 carbon atoms.

[0038]

[Chemical formula 10] In the above formula, R38 has the same definition as above.

[0039]

[Chemical formula 11]

In each of the above formulas, R39 is hydrogen or alkyl having 1 to 4 carbon atoms, and R40, R41, R
42, R43 and R44 are independently alkyl of 1 to 4 carbon atoms such as methyl or ethyl, 1 carbon atom such as hydroxymethyl or hydroxyethyl;
~4 hydroxyalkyl or sulfoalkyl of 1 to 4 carbon atoms.

E. Representative patents for PUGs, which are bleach inhibitors, are U.S. Patent Nos. 3,705,801 and 3,7.
No. 15,208 and West German Patent Publication No. 2,405
, No. 279. Preferred structural formulas of bleaching inhibitors include the following.

[0042]

embedded image In each of the above formulas, R45 is an alkyl group having 6 to 20 carbon atoms.

[0043]F. PUGs are bleaching accelerators

[Chemical formula 13]

In each of the above formulas, R46 is hydrogen, an optionally unsubstituted or substituted alkyl having 1 to 6 carbon atoms such as ethyl and butyl, alkoxy such as ethoxy and butoxy, or alkoxy such as ethylthio and butylthio. alkylthio, R47 is hydrogen, alkyl or aryl such as phenyl, R48 and R49 are independently alkyl such as alkyl of 1 to 6 carbon atoms, such as ethyl and butyl, and z is 1
~6.

Image dye-forming couplers can be incorporated into the photographic element and/or the photographic processing solution, such as a developer solution, so that upon development of the exposed photographic element they combine with the oxidized developing agent and become reactive. It can become. Coupler compounds incorporated into photographic processing solutions must be of such molecular size and arrangement that they can be diffused through the photographic layers by the processing solution. As a general rule, when incorporated into photographic elements, coupler compounds must be non-diffusive, i.e. they
The molecular size and arrangement must be such that they do not significantly diffuse or leak out of the layer to which they are applied.

Photographic elements such as those described can be processed by conventional methods in which color couplers and color developing agents are incorporated separately into a processing solution or composition or element. Photographic elements into which the compounds of this invention are incorporated can be simple elements consisting of a support and a single silver halide emulsion layer, or they can be multilayer, multicolor elements. The compounds of the invention include at least one
one silver halide emulsion layer and/or at least one other layer, such as an adjacent layer, where they combine with the oxidized color developing agent developed silver halide in the emulsion layer. will become reactive. The silver halide emulsion layer may contain or be combined with other photographic coupler compounds such as dye-forming couplers, color masking couplers and/or competitive couplers. These other photographic couplers can produce dyes of the same or different color and hue as the photographic couplers of this invention. Additionally, the silver halide emulsion layer and other layers of photographic elements can contain additives normally included in such layers.

A typical multilayer, multicolor photographic element comprises supports and red-sensitive silver halide emulsion units in combination with a cyan dye image-bearing material, carried thereon, and a magenta dye image-bearing material in combination with a support. It may contain at least one green-sensitive silver halide emulsion unit and a blue-sensitive silver halide emulsion unit in combination with a yellow dye image-providing material, a silver halide emulsion unit in combination with a photographic coupler of the present invention. Each silver halide emulsion unit is 1
It can be composed of more than one layer and various types of units, and these layers can be arranged in separate positions in relation to each other.

These couplers can be incorporated into or combined with one or more layers or units of the photographic element. For example, a layer or unit affected by a PUG is
Control can be achieved by incorporating acquisition layers at appropriate locations on the element that can limit the effects of G. At least one layer of the photographic element can be, for example, a mordant layer or a barrier layer.

The light-sensitive silver halide emulsion may contain coarse silver halide crystals, regular silver halide crystals or fine silver halide crystals or mixtures thereof, and may contain silver chloride, silver bromide, bromo-iodide. It may comprise silver halides such as silver chloride, silver chlorobromide, silver chloroiodide, silver chlorobromoiodide and mixtures thereof. These emulsions are
It can be a negative working emulsion or a direct positive emulsion. They can form latent images primarily on the surface of or within the silver halide grains. They can be chemically and spectrally sensitized. Generally the emulsion can be a gelatin emulsion, although other hydrophilic colloids can also be used. Research Disclosure
, January 1983, Item No. Tabular grain photosensitive silver halides such as those described in No. 22534 and U.S. Pat. No. 4,434,226 are particularly useful.

Preferably, the coupling-off group comprises a releasable PUG. Couplers can be incorporated for different purposes and in different locations depending on the nature of the particular PUG. In the following description of materials suitable for use in the emulsions and elements of this invention, Research Disclo
sure, December 1978, Item 17643,
(Industrial Opportunity
s Ltd. , published by Homewell Havant
, Hampshire, P09 1EF, U. K
．． ) will be quoted. This publication is hereafter referred to as “Res.
``each disclosure''.

[0051] These photographic elements are
It can be coated on a variety of supports, such as those described in Disclosure, Section XVII and the references cited therein. Photographic elements are exposed to actinic radiation, typically in the visible region of the spectrum, to produce ResearchDi.
sclosure, a latent image can be formed as described in Section XVIII, and then processed to create a Rese
A visible dye image can be formed as described in Arch Disclosure, Section XIX. Processing to form a visible dye image consists of contacting the element with a color developing agent to reduce the developable silver halide and oxidize the color developing agent. The oxidized color developing agent in turn reacts with the coupler to provide a dye.

Preferred color developing agents that can be used in the present invention are p-phenylenediamines. Preferred specific examples include 4-amino-N,N-diethylaniline hydrochloride, 4-amino-3-methyl-N,N-diethylaniline hydrochloride, and 4-amino-3-methyl-N-ethyl- N-β-(methanesulfonamide)ethylaniline sulfate hydrate, 4-amino-3-methyl-N-ethyl-N
-β-hydroxyethylalinine sulfate, 4-amino-
3-β-(methanesulfonamide)-ethyl-N,N-diethylaniline hydrochloride, and 4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine di-
Examples include p-toluenesulfonic acid.

The use of negative-working silver halide in the above processing steps provides a negative image. To obtain a positive (or reversal) image, the exposed silver halide can be developed by processing this step with a developer containing a non-chromogenic developing agent, but without producing dye, and then The element is uniformly fogged to allow the unexposed silver halide to be developed. Also, a positive image can be obtained using a direct positive emulsion. After development, conventional bleaching, fixing or bleach-fixing steps are performed to remove silver and silver halide, followed by washing and drying steps.

Naphthol couplers such as those described can be prepared by reactions and methods known in the organic compound synthesis art. Similar reactions and methods include
It is described in US Pat. No. 4,482,629. Typically, naphthol couplers are manufactured by the following method.

[0055]

[Chemical formula 14]

[Chemical formula 15]

[Chemical formula 16]

Synthesis Example A Compound (A2) Phenyl-1,4-dihydroxy-2-naphthoate (100 mL) was added to deoxygenated tetrahydrofuran (500 mL).
0 g, 356.78 mmol) and then added deoxygenated methanol (500 mL). Ammonium acetate (
50.0 g, 648.63 mmol) was added followed by concentrated ammonium hydroxide (1.0 L). The reaction mixture was stirred for 3 hours and then added to ice-cold 2N HCl (4.0L
), and then concentrated hydrochloric acid was added until the pH reached 1. The obtained product, compound (A2), was collected by filtration, thoroughly washed with water, and then air-dried. The crude product was washed with dichloromethane and then air dried. Yield 62.0g (
72%).

Compound (A3) Compound (A2) (50 mL) was added to dry pyridine (150 mL).
．． (0 g, 0.246 mol) was dissolved and acetonitrile (75 mL) was added. Stir this solution and -5 to
Cooled to 0°C. Next, ethyl chloroformate (50 mL, 0.5
23 mol) was added dropwise. After addition, remove the cooling bath and
The temperature was returned to room temperature. Next, the reaction mixture was gradually heated until it boiled and the solvent was distilled off. This operation was continued until the temperature rose to approximately 120° C. and 150 mL of solvent was collected. Heating under reflux was continued for an additional hour. The reaction mixture was then cooled to about 50 °C and 2N
Poured into HCl (3.0 L). The suspension was then stirred for about 15 minutes, filtered, and the residue was washed thoroughly with water, then with acetonitrile and finally with ether. This product was pure enough to be used in the next step. Yield: 43.5g (77%).

Compound (A4) Compound (A3) (23.0 g, 100.35 mmol) was dissolved in deoxygenated dimethyl sulfoxide (250 mL), and then deoxygenated water (25 mL) was added. To this solution was added 85% potassium hydroxide (9.9 g, 150.53 mmol) while stirring at room temperature under a nitrogen atmosphere and stirring was continued until dissolved for about 15 minutes. 4-chloro-3-nitrobenzaldehyde (18.62 mmol) was then added in one portion and the resulting solution was stirred for 1 hour at 60°C. The reaction mixture was then added to ice-cold 2N HCl (2.0 L) and collected by filtration. The product, compound (A4), was washed with water, slurried wet in methanol, filtered, and then washed with ether. This product was pure enough to be used in the next step. Yield 28.0g (
74%).

Compound (A5) Powdered compound (A4) (28.0g, 74.01
mmol) was suspended in tetrahydrofuran (150 mL) and methanol (100 mL). Add water, then add sodium borohydride (2.8 g,
74.01 mmol) was added. Additional tetrahydrofuran (50 mL) was added to aid stirring. A complete solution was obtained at the end of the sodium borohydride addition. The reaction was continued for an additional 15 min, then cooled with ice-cold 2N HC.
1 (2.0 L) and the product was collected by filtration. The product compound (A5) was washed with methanol, suspended in ethanol while still wet with the solvent, and heated to reflux. The solution was cooled, filtered, then washed with methanol and ethanol, and finally air dried. A secondary product was obtained by concentrating the mother liquor. Total yield 19.5g (67%
).

Compound (A6) Compound (A5) (1
9.0 g, 50 mmol) were suspended. Methanol (50 mL) was added to this mixture and then 80°C for 1 hour.
heated with. The resulting dark yellow-brown solution was cooled and kept on ice for 2
Poured into N HCl (2.0 L). The yellow product was collected by filtration, washed with water and air dried. Yield 17.7g (
100%).

Compound (A7) Compound (A6) was dissolved in tetrahydrofuran (80 mL), and then methanol (300 mL) was added. Raney-Nickel, which had been washed several times with water, and methanol were added and the solution was hydrogenated for 2 hours at 55 psi, after which the hydrogenation was stopped. After filtering off the crystals, they were washed with methanol,
The filtrate was concentrated under reduced pressure to obtain a product, compound (A7). This product was deemed sufficiently pure to be used in the next step. Yield 100%.

Compound (A8) Compound (A7) (50 mL) was added to dry pyridine (150 mL).
．． Hexadecylsulfonyl chloride (16.2 g, 50.0 mmol) was added. The solution was stirred for 30 minutes at room temperature under nitrogen atmosphere. The pyridine was concentrated under reduced pressure and the residue was dissolved in ethyl acetate. The ethyl acetate solution was then washed with 2N HCl (3x), dried (MgSO4), filtered, and concentrated. The solvent was removed under reduced pressure and the residual oil was crystallized from acetonitrile. After filtration, the product compound (A8) was washed with acetonitrile and then dried to give a concentration of 16.3
g [yield 53% based on compound (A5)] was obtained.

Compound (A9) Compound (A8) in tetrahydrofuran (150 mL)
(16.3 g, 26.6 mmol) was added to pyridine (3.2 mL, 39.90 mmol) followed by chloroacetic anhydride (6.82 g, 39.89 mmol) in tetrahydrofuran (30 mL).
was added at a moderate rate. After stirring for 30 minutes at room temperature, the solvent was distilled off under reduced pressure and the residue was dissolved in ethyl acetate. The ethyl acetate solution was then washed with 2N HCl (2x), dried (MgSO4) and concentrated under reduced pressure. The residue was crystallized from acetonitrile to obtain compound (A9).
12.2g (66%) was obtained.

Compound (A10) Compound (A9) was added to dimethylformamide (150 mL).
) (12.2 g, 17.7 mmol) and potassium iodide (4.4 g, 25.55 mmol) and aniline (8.2 mL, 88.5 mmol)
was added and the reaction mixture was heated to 60° C. for 1.5 hours. The reaction mixture was poured into 2N HCl and extracted with ethyl acetate (twice). Combine the ethyl acetate extracts and add 2N HC
Washed with 1 ml (3x), dried (MgSO4), filtered and concentrated. This residue was used directly in the next reaction and could be crystallized from acetonitrile. The yield was almost 100%.

Compound (A11) Compound (A10) was added to tetrahydrofuran (800 mL).
) (83.0 g, 111.26 mmol) was dissolved and the solution was stirred at room temperature. N,N-4-diethylaniline (17.7 mL, 111.26 mmol)
was added followed by 12% phosgene in toluene (275 mL
, 333.78 mmol) solution was added. The reaction mixture was stirred for 15 minutes at room temperature, concentrated under reduced pressure, and the residue was used directly in the next step. product, compound (A
The yield of 11) was almost 100%.

Compound (A12) The above compound (A11) was added to dry pyridine (800 mL).
PMT (19.83g,
111.26 mmol) was added. This mixture was stirred for 1 hour at room temperature. Then it was concentrated under reduced pressure and the residue was dissolved in ethyl acetate. This ethyl acetate layer was dissolved in 2N HC
Washed (3 times) with 2.1 g of 2.1 g of 2.1 g of 2.1 g of 2.1 g of chloride, dried (MgSO4), filtered, and concentrated to an oil. This oil was dissolved in ethyl acetate/dichloromethane/heptane/acetonitrile (
20/20/56/4) and subjected to flash chromatography using the same solvent system as eluent to elute impurities from the column, then changing the composition ratio of the solvent system (27/50/20/4). ) and the product, compound (A1
2) was eluted. The product could be recrystallized from acetonitrile. Yield: 61.0g (58%). Elemental analysis As C50H59N7O8S2: Calculated values: %C=63.20, %H=6.26, %N=1
0.32, %S=6.75 Experimental value: %C=63.14, %H=6.29, %
N=10.23, %S=6.62

Compound (A13) Compound (A8) (4.0
g, 6.53 mmol) was suspended in ether (20
mL) in phosphorus tribromide (0.68 mL,
7.18 mmol) was added dropwise over 15 minutes. After addition, dilute the reaction solution with ether and dilute the ether solution with 2N
Washed with HCl (once), dried (MgSO4),
The mixture was filtered and then concentrated to obtain compound (A13). The yield was 100%.

Compound (A14) Compound (A13) in dimethylformamide (40 mL)
(6.53 mmol) was dissolved, and PMT (1.
51 g, 7.54 mmol) was added and the resulting solution was stirred for 1 hour at room temperature. The reaction mixture was poured into 2N HCl and extracted with ethyl acetate (twice) to obtain compound (A1
4) was isolated. Next, combine the ethyl acetate extracts and add 2N
Washed with HCl (3x), dried (MgSO4), filtered and concentrated. The residue was dissolved in a mixture of ethyl acetate/heptane/dichloromethane (15/30/5) and subjected to flash chromatography using the same solvent mixture as eluent. The first major absorption band was collected to obtain the product. Yield: 4.0g (79%). Elemental analysis As C41H52N6O5S2: Calculated values: %C=63.70, %H=6.78, %N=1
0.87, %S=8.30 Experimental value: %C=63.40, %H=6.80, %
N=10.76, %S=8.14

[0069]

[Chemical formula 17]

[Chemical formula 18]

Synthesis Example B: Compound (B16) Compound (A3) (3.4 g, 14.83 mmol) was dissolved in deoxygenated dimethyl sulfoxide (100 mL) and stirred at room temperature under nitrogen atmosphere. 85 to this solution
% potassium hydroxide (1.71 g, 25.95 mmol) followed by deoxygenated water (10 mL). The reaction mixture was stirred for 15 minutes at room temperature and then benzophenone (B15) (7.0 g, 14.83 mmol) was added in one portion as a solid. The dark colored solution was then heated to 60°C and stirring continued for 2.5 hours. The hot solution at 60° C. was poured into ice-cold 2N HCl (600 mL). After filtering the yellow product and washing with water and then methanol,
Dry. Yield of compound (B16): 8.8g (89%
).

Compound (B17) Compound (B16) (
8.8 g, 13.24 mmol) was dissolved therein, and methanol (20 mL) and water (20 mL) were added thereto. Sodium borohydride (0
．． 5 g, 13.24 mmol) was added. At the end of the addition, the dissolved solution was stirred for an additional 15 minutes. next,
Pour the reaction solution into ice-cold 2N HCl (600 ml),
The product compound (B17) was collected by filtration, washed with water and then with methanol, and then air-dried. Yield 7.9g (89%
).

Compound (B18) Compound (B17) (10.0 g, 1
5.0 mmol) was suspended in 85% potassium hydroxide.
(7.90 g, 120.0 mmol) and methanol (20 mL) were added together. Stir this mixture for 1 hour 8
Stirred at 0° C., cooled, then poured into ice-cold 2N HCl and the mixture was extracted with ethyl acetate (twice). The combined ethyl acetate extracts were then dried (MgSO4) and
Filter and then concentrate. The residual compound was used directly in the next reaction step. Yield (100%).

Compound (B19) Compound (B18) (15 mmol) was dissolved in ether (70 mL), and phosphorus tribromide (1.6 mL, 16.5 mmol) was dissolved in ether (15 mL).
It was added dropwise over 5 minutes. At the end of the dropwise addition, the reaction solution was further stirred at room temperature for 15 minutes. The solution was then diluted with ether, washed with 2N HCl (3 times) and dried (Mg
SO4), filtered and concentrated under reduced pressure. The compound (B19) thus obtained was of sufficient purity to be used in the next step. Yield 100%.

Compound (B20) Compound (B19) in dimethylformamide (50 mL)
was dissolved and treated with sodium PMT (3.55 g, 17.73 mmol) with stirring for 1 hour at room temperature. Then, the reaction solution was diluted with ethyl acetate and diluted with 2N H
Washed with Cl (4 times). Next, the organic layer was dried (Mg
SO4), filtered and concentrated under reduced pressure. The oil was dissolved in 25% ethyl acetate in heptane and subjected to flash chromatography eluting with the same solvent mixture. The first major absorption band is collected to form the product compound (B2
0) was obtained. Yield: 5.0 g [42% from compound (B17)]. Elemental analysis C46H52N6O5S: Calculated value: %
C=68.98, %H=6.54, %N=10.
49, %S=4.00 Experimental value: %C=69.07, %H=6.44, %
N=10.31, %S=4.12

Examples of couplers that can be produced by these synthesis methods include the following.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

[0076]

EXAMPLES The present invention will be explained in more detail with the following examples. Examples 1-3 Photographic elements were prepared by coating the following layers on a cellulose ester film support (the amounts of each component were m
(expressed in g/m2). Emulsion layer 1: gelatin-2420; red-sensitive silver bromoiodide (A
g)-1615; yellow image coupler dispersed in dibutyl phthalate (image-receiving layer) Intermediate layer: gelatin-860; didodecylhydroquinone-113 Emulsion layer 2: gelatin-2690; green-sensitive silver bromoiodide (A
g as) -1615; magenta image coupler dispersed in tritolyl phosphate; DIR compounds of Table A were dispersed in N,N-diethyl-dodecanamide, and after exposure to graded green light and processing, the original Applied at a level sufficient to provide 0.5 (half) of the contrast (Kouser layer) Protective Overcoat: Gelatin-5380; bisvinylsulfonyl methyl ether with 2% total gelatin.

The structure of the image couplers is as follows.

[Chemical formula 19]

[0078] Strips of each element were placed on graduated density step tablets.
Tablet) or exposed to green light via a 35% modulated fringe chart to measure sharpness, then developed for 3.25 minutes at 38°C in the following color developer, stopped, washed, bleached, Fixed, washed and then dried.

Color developer: distilled water

800mL Sodium pyrosulfite
2.78g
Sodium sulfite/anhydrous
0.3
8g CD-4*

4.52g Potassium carbonate, anhydrous
34.3g
potassium bicarbonate

2.32g sodium bromide

1.31g potassium iodide
1.20
mg hydroxylamine sulfate (HAS)

2.41g Thiethylenetriaminepentaacetic acid pentasodium salt (40% solution) 8.43g Adjust to 1 liter with distilled water Adjust to pH 10.0 * CD-4 is 4-amino-3-methyl-N-ethyl-N -β-hydroxyethylaniline sulfate.

Processed images were read with green light to determine contrast and AMT acutance. AMT acutance vs. each development inhibitor release (DIR) From the logarithm of the contrast for variations in compound application level,
Acutance was determined at a contrast of 0.5 compared to its original contrast without the presence of the DIR compound. The acutance of the logarithmic DIR coupler was subtracted from each AMT value to yield a relative sharpness value, which is shown in Table A as the difference in AMT. AMT is calculated using the following formula, "Theory", which indicates the cascade area under the system modulation curve.
of the Photographic Process
ss,” 4th edition, 1977 (edited by T.H. James)
Equation (21.104) on page 629 of AMT=
100+66Log [Cascade area/2.6696
M] where the magnification factor M is 3.8 for the 35 mm system AMT.

The use of CMT acutance is based on R. G
．． Gendron's "An Improved Ob"
jective Method of Rating
Picture Sharpness: CMT acu
tance”, Journal of SMPTE
, Vol. 82, pp. 1009-1012, (1
973). AMT is a further modification of CMT useful for evaluation systems that require observation of positive prints made from negatives.

[0082]

[Table 10]

TABLE 11 Relative to the control couplers, the couplers of Examples 1-3 provide improved acutance and interlayer effect.

Example 4 A photographic film was prepared, exposed and processed in the same manner as the films of Examples 1-3. The processed images were read with green light to determine the contrast. From the logarithmic plot of the contrast corresponding to the coating level of each DIR coupler, DI
Reactivity was determined as the amount of DIR coupler (in micromoles) per square meter to reduce the contrast (gamma) by half (0.5) compared to its original contrast in the absence of R coupler. The lower amount of DIR coupler required means that the DIR coupler is more reactive. Coupler 3 is the same as described in Example 3. The results are shown in Table B.

[0084]

[Table 12]

[Table 13]

[0085]

Effects of the Invention Photographic silver halide compositions as described containing fixed naphthol couplers are also inexpensive to produce and have the desired acutance and interlayer properties in color photographic silver halide materials. The present invention provides a material that allows the effect and allows processing at low concentrations of couplers.

Claims (1)

[Claims] 1. A fixed naphtholic coupler capable of producing by oxidative coupling a dye that can be washed out of a photographic silver halide composition by photographic processing, with a -CONH2 group in the 2-position and a ballasted uncoupling in the 4-position. 1. A photographic silver halide composition containing a fixed naphthol coupler comprising a naphthol coupler moiety having a ballast group and no ballast group.