Hydroxyquinoline cyan couplers and their process of production

8-hydroxyquinoline and 5-hydroxyquinoline compounds of the following formulae: ##STR1## , wherein: R.sub.1 is a substituted or unsubstituted alkyl group with 8 to 30 carbon atoms; PA1 R.sub.2 is hydrogen or another substituent; PA1 X is a group capable of being released by a coupling reaction with an oxidized aromatic primary amine developing agent; and PA1 Z is a nonnucleophilic substituent or a group not capable of being eliminated during or following a coupling reaction with an oxidized color developer have been found to be useful in photographic materials as cyan dye-forming couplers. A process in which a substituted aminophenol salt reacts with two molar equivalents of an enolizable aldehyde containing at least two a-substituted hydrogen atoms is used to make these couplers and other hydroxyquinoline compounds.

FIELD OF THE INVENTION 
The present invention relates to photographic materials containing 
8-hydroxyquinoline and 5-hydroxyquinoline cyan dye-forming couplers and a 
process of making these couplers. 
BACKGROUND OF THE INVENTION 
A dye imaging in a silver halide-containing photographic material is formed 
by reacting an exposed silver halide with a color developer, generally a 
p-phenylenediamine compound. An oxidized form of the developer is produced 
which then reacts with a compound called a coupler to yield a dye. Full 
color reproduction of an image is generally achieved through a subtractive 
color process, in which the primary colors red, green and blue are 
reproduced by forming dyes of their complementary colors--i.e. cyan, 
magenta, and yellow, respectively. The subtractive color process is 
described in T. H. James, ed., The Theory of the Photographic Process, 
Fourth Edition, Macmillan, New York, 1977, pp. 336 ff. 
For the formation of cyan dye images, the most commonly used couplers are 
variously substituted phenols and naphthols. A substituent of the coupler, 
called a coupling off group, is located at the position of reaction 
between the oxidized developer and the phenol or naphthol and is 
eliminated in the process of dye formation. In most color photographic 
materials, the coupler is incorporated in a layer containing silver halide 
and is immobilized in that layer by a high molecular weight ballast 
substituent on the coupler. Cyan couplers are discussed in The Theory of 
the Photographic Process, pp. 358 ff. 
Various hydroxyquinoline compounds have been described as couplers in color 
photographic materials. U.S. Pat. Nos. 2,449,966, 2,455,169, and 2,584,349 
disclose 8-hydroxyquinolines with arylazo coupling off groups, which can 
be used as masking couplers for color correction. U.S. Pat. No. 2,524,725 
and 2,524,741 relate to 8-hydroxyquinoline couplers that react with 
o-phenylenediamine developers to form intermediate compounds that can be 
cyclized to form magenta-colored phenazonium dyes. The couplers disclosed 
in U.S. Pat. No. 2,886,436 are derivatives of 6-amino-8-hydroxyquinoline 
that undergo cyclization after reaction with oxidized p-phenylenediamine 
developer to product magenta-colored azine dyes. 
U.S. Pat. No. 4,296,199 and 4,296,200 disclose a larger number of different 
types of cyan couplers with thiosubstituted alkoxy coupling off groups. 
Included amongst these compounds are hydroxyquinoline cyan couplers, but 
no specific structures are mentioned. 
U.S. Pat. No. 4,770,988 discloses a broad class of cyan couplers used in 
combination with phenol cyan couplers, while U.S. Pat. No. 4,898,812 
relates to the use of a cyan coupler in combination with a development 
accelerator contained in the same layer. Both U.S. Pat. Nos. 4,770,988 and 
4,898,812 disclose one specific 8-hydroxyquinoline, containing a high 
molecular weight substituted benzamido group in the 7-position and a 
chloro coupling off group in the 5-position. There is no indication that 
this compound can be substituted at the 1 or 2 positions with alkyl 
ballast groups. 
One of the most general synthesis of quinoline compounds is the Doebner-von 
Miller reaction, in which an aromatic amine is condensed with an 
.alpha.,.beta.-unsaturated carbonyl compound at high temperature in the 
presence of a strong acid (G. Jones, ed. "Quinolines," Part I, in A. 
Weissberger and E. C. Taylor, eds., The Chemistry of Heterocyclic 
Compounds, vol. 32, John Wiley & Sons, New York 1977, p. 100) as shown in 
the following formula: 
##STR2## 
When R.sub.1 is --OH, the product is a hydroxyquinoline. Because of the 
drastic reaction conditions utilized in this process, the yield of desired 
product is low, and its separation from a mixture of tarry by-products is 
difficult. Many attempts have been made to improve the yield of quinoline 
compounds from this synthesis. For example, R. Manske et al., Can. J. Res. 
27, 1949, p. 359 discloses a Skraup variation of the Doebner-von Miller 
reaction where a mixture of aminophenols, corresponding nitro compounds, 
and excess glycerol in concentrated sulfuric acid react and achieve good 
yields of hydroxyquinoline compounds as follows: 
##STR3## 
wherein R is H or Cl Isolation and purification of the products of this 
reaction, were still tedious, and the use of glycerol precluded 
introduction of substituents into the heterocyclic nucleus. 
Another approach to improving the synthesis of hydroxyquinoline utilized 
derivatives of the starting .alpha.,.beta.-unsaturated carbonyl compounds. 
For example, in Y. Oi, E. Omori, Jap. Pat. 70 16948, C.A. 73, 98820 
(1970), 2-aminophenols were condensed with the diacetyl derivative of 
acrolein to yield 8-hydroxyquinolines as follows: 
##STR4## 
Similarly, in H. J. Teuber, S. Benz, Chem. Ber. 100, 2918 (1967), 
3-aminophenols reacted with 3-ethoxyacrolein diethyl acetal to give 
5-hydroxyquinoline compounds as follows: 
##STR5## 
However, as with the previous procedures, these latter two reactions did 
not allow for the presence of substituents in the heterocyclic ring. 
The Doebner-von Miller synthesis and its variants are thus limited to the 
production of simple quinolines of low molecular weight. Further, the 
difficulty of preparing complex .alpha.,.beta.-unsaturated carbonyl 
compounds restricts the introduction of substituents into the heterocyclic 
nucleus. Finally, the drastic reaction conditions, i.e. strong acid and 
high temperatures, generally result in low yields of the desired products 
and difficult isolation of them from a myriad by-products. A need thus 
exists for a simple synthetic method, carried out under mild conditions, 
to produce hydroxyquinoline compounds and, particularly, the 
8-hydroxyquinoline and 5-hydroxyquinoline cyan couplers of the present 
invention. 
BRIEF SUMMARY OF THE INVENTION 
The present invention relates to 8- and 5-hydroxyquinoline cyan dye-forming 
couplers of the formulae shown below and their uses in color photographic 
materials: 
##STR6## 
, wherein R.sub.1 is a substituted or unsubstituted alkyl group with 8 to 
30 carbon atoms; 
R.sub.2 is hydrogen or another substituent; 
X is a coupling off group that is released in a coupling reaction with an 
oxidized aromatic primary amine color developer; and 
Z is a non-nucleophilic substituent or group not capable of being 
eliminated during or following a coupling reaction with an oxidized color 
developer. 
This invention further relates to a process of preparing hydroxyquinoline 
compounds, including the 8-and 5-hydroxyquinoline cyan couplers of the 
present invention by reacting substituted aminophenol salt with two molar 
equivalents of an enolizable aldehyde containing at least one 
.alpha.-substituted hydrogen atoms as follows: 
##STR7## 
, wherein R.sub.1 is a substituted or unsubstituted alkyl group with one 
to 30 carbon atoms; 
R.sub.2 and R.sub.3 is hydrogen or other substituents; and 
HY is a strong organic or inorganic acid 
This process is carried out under very mold reaction conditions, at room 
temperature or below, and in the presence of a solvent, such as methanol 
or ethanol. The desired hydroxyquinoline compounds generally separate 
either as salts or as free bases from the reaction mixture and are readily 
isolated in good yields. An added advantage of this technique is the 
ability to substitute ballast groups of variable size at the 1 and 2 
positions of the hydroxyquinoline compounds. Thus, the process of the 
present invention is much more convenient and versatile than previously 
known methods of synthesizing hydroxyquinolines and can be used to prepare 
not only the 8hydroxyquinoline and 5-hydroxyquinoline cyan couplers of the 
present invention but also other 6- and 7-hydroxysubstituted quinoline 
compounds. 
DETAILED DESCRIPTION OF THE INVENTION 
The present invention relates to 8-hydroxyquinoline and 5-hydroxyquinoline 
cyan couplers of the following structures: 
##STR8## 
wherein R.sub.1 is a substituted or unsubstituted alkyl group with 8 to 30 
carbon atoms; 
R.sub.2 is hydrogen or another substituent; 
X is a coupling off group that is released in a coupling reaction with an 
oxidized aromatic primary amine color developer, preferably a 
p-phenylenediamine; and 
Z is a non-nucleophilic substituent not capable of being eliminated during 
or following a coupling reaction with an oxidized color developer. 
The R.sub.2 substituents can be, in addition to hydrogen, a halogen, 
--OR.sub.3, cyano, --NHCOR.sub.3, --NHSO.sub.2 R.sub.3, CONHR.sub.3, and 
--NHCONHR.sub.3, where R.sub.3 is an unsubstituted or further substituted 
alkyl group or an unsubstituted or substituted aryl group. The Z 
substituent can be, in addition to hydrogen, --OR.sub.3, cyano, 
--NHCOR.sub.3, CONHR.sub.3, and --NHCONHR.sub.3, where R.sub.3 is a 
substituted or unsubstituted alkyl group or a substituted or unsubstituted 
aryl group. The coupling off group X can be halogen, alkoxy, aryloxy, 
arylthio, acyloxy, thiocyano, sulfonamido, and sulfonyloxy, among others, 
as described in The Theory of the Photographic Process, pp. 360 ff, and in 
U.S. Pat. Nos. 3,476,563; 3,311,476; 3,214,437; 3,737,316; 4,046,573; 
3,749,735; 4,296,199; and 4,296,200. 
Examples of suitable couplers, in accordance with the present invention, 
include the following: 
##STR9## 
In most modern color photographic materials, the coupler compound is 
incorporated in a layer of the photographic material during manufacture 
and is rendered immobile in the layer as a result of the bulk provided by 
one or more ballast groups. As to the present invention, such ballast is 
furnished by the R.sub.1 groups at the 1 and 2 positions. Incorporation 
of the coupler in the layer is accomplished by dispersing it in a high 
boiling organic solvent. Use of low boiling auxiliary solvents such as 
ethyl acetate has become common practice. 
The hydroxyquinoline cyan couplers of this invention can be incorporated in 
silver halide emulsions, and the emulsions can be coated on a support to 
form a photographic element by techniques well known in the art. U.S. Pat. 
No. 2,949,360 provides details regarding the use of ethyl acetate as an 
auxiliary solvent for dispersing the coupler. Alternatively, the coupler 
can be incorporated in photographic elements adjacent the silver halide 
emulsion where, during development, the coupler will be in reactive 
association with development products such as oxidized color developing 
agent. The coupler can be associated with an image modifying coupler, as 
described in U.S. Pat. No. 5,021,555 to Szajewski and Taber. 
The photographic elements can be either single color or multicolor 
elements. In a multicolor element, the cyan dye-forming coupler is usually 
associated with a red-sensitive emulsion, although it could be associated 
with an unsensitized emulsion or an emulsion sensitized to a different 
region of the spectrum. Multicolor elements contain dye image-forming 
units sensitive to each of the three primary regions of the spectrum. Each 
unit can be comprised of a single emulsion layer or of multiple emulsion 
layers sensitive to a given region of the spectrum. The layers of the 
element, including the layers of the image-forming units, can be arranged 
in various orders as known in the art. 
A typical multicolor photographic element comprises a support bearing a 
cyan dye image-forming unit comprising at least one red-sensitive silver 
halide emulsion layer having associated therewith at least one cyan 
dye-forming coupler, a magenta image forming unit comprising at least one 
green-sensitive silver halide emulsion layer having associated therewith 
at least one magenta dye-forming coupler, and a yellow dye image-forming 
unit comprising at least one blue-sensitive silver halide emulsion layer 
having associated therewith at least one yellow dye-forming coupler. Such 
an element, in accordance with the present invention, contains a 
hydroxyquinoline cyan coupler of the present invention. The element can 
contain additional layers, such as filter layers, interlayers, overcoat 
layers, subbing layers, and the like. 
In the following discussion of suitable materials for use in the elements 
of this invention, reference will be made to Research Disclosure, December 
1989, Item 308119, published by Kenneth Mason Publications, Ltd., The Old 
Harbourmaster's, 8 North Street, Emsworth, Hampshire P010 7DD, ENGLAND. 
This publication, hereby incorporated by reference, will be identified 
hereafter by the term "Research Disclosure." 
The silver halide emulsions employed in the elements of this invention can 
be comprised of silver bromide, silver chloride, silver iodide, silver 
chlorobromide, silver chloroiodide, silver bromoiodide, silver 
chlorobromoiodide or mixtures thereof. The emulsions can include silver 
halide grains of any conventional shape or size. Specifically, the 
emulsions can include coarse, medium, or fine silver halide grains. High 
aspect ratio tabular grain emulsions are specifically contemplated, such 
as those disclosed in U.S. Pat. Nos. 4,434,226; 4,414,310; 4,399,215; 
4,433,048; 4,386,156; 4,504,570; 4,400,463; 4,414,306; 4,435,501; 
4,643,966; 4,672,027; and 4,693,964. Also specifically contemplated are 
those silver bromoiodide grains with a higher molar proportion of iodide 
in the core of the grain than in the periphery of the grain, such as those 
described in GB 1,027,146; JA 54/48,521; EP 264,954; and U.S. Pat. Nos. 
4,379,837; 4,444,877; 4,665,012; 4,686,178; 4,565,778; 4,728,602; 
4,668,614; and 4,636,461. The silver halide emulsions can be either 
monodisperse or polydisperse as precipitated. The grain size distribution 
of the emulsions can be controlled by silver halide grain separation 
techniques or by blending silver halide emulsions of differing grain 
sizes. 
Sensitizing compounds, such as compounds of copper, thallium, lead, 
bismuth, cadmium, and Group VIII noble metals, can be present during 
precipitation of the silver halide emulsion. 
The emulsions can be surface-sensitive emulsions, i.e., emulsions that form 
latent images primarily on the surfaces of the silver halide grains, or 
internal latent image-forming emulsions, i.e., emulsions that form latent 
images predominantly in the interior of the silver halide grains. The 
emulsions can be negative-working emulsions, such as surface-sensitive 
emulsions or unfogged internal latent image-forming emulsions, or 
direct-positive emulsions of the unfogged, internal latent image-forming 
type, which are positive-working when development is conducted with 
uniform light exposure or in the presence of a nucleating agent. 
The silver halide emulsions can be surface sensitized. Noble metal (e.g., 
gold), middle chalcogen (e.g., sulfur, selenium, or tellurium), and 
reduction sensitizers, employed individually or in combination, are 
specifically contemplated. Typical chemical sensitizers are listed in pi 
Research Disclosure, cited above, Section III. 
The silver halide emulsions can be spectrally sensitized with dyes from a 
variety of classes, including the polymethine dye class, which includes 
the cyanines, merocyanines, complex cyanines and merocyanines (i.e., tri-, 
tetra-, and poly-nuclear cyanines and merocyanines), oxonols, hemioxonols, 
styryls, merostyryls, and streptocyanines. Illustrative spectral 
sensitizing dyes are disclosed in Research Disclosure, cited above, 
Section IV. 
Suitable vehicles for the emulsion layers and other layers of elements of 
the invention are described in Research Disclosure, Section IX and the 
publications cited therein. 
In addition to the cyan couplers described herein the elements of this 
invention can include additional cyan couplers as described in Research 
Disclosure, Section VII, paragraphs D, E, F and G and the publications 
cited therein. These additional couplers can be incorporated as described 
in Research Disclosure, Section VII, paragraph C and the publications 
cited therein. 
The photographic elements of this invention can contain brighteners 
(Research Disclosure Section V), antifoggants and stabilizers (Research 
Disclosure Section VI), antistain agents and image dye stabilizers 
(Research Disclosure Section VII, paragraphs I and J), light absorbing and 
scattering materials (Research Disclosure Section VIII), hardeners 
(Research Disclosure Section X), coating aids (Research Disclosure Section 
XI), plasticizers and lubricants (Research Disclosure Section XII), 
antistatic agents (Research Disclosure Section XIII), matting agents 
(Research Disclosure Section XVI), and development modifiers (Research 
Disclosure Section XXI). 
The photographic elements can be coated on a variety of supports as 
described in Research Disclosure Section XVII and the references described 
therein. 
Photographic elements can be exposed to actinic radiation, typically in the 
visible region of the spectrum, to form a latent image as described in 
Research Disclosure Section XVIII and then processed to form a visible dye 
image as described in Research Disclosure Section XIX. Processing to form 
a visible dye image includes the step of contacting the element with a 
color developing agent to reduce developable silver halide and oxidize the 
color developing agent. Oxidized color developing agent in turn reacts 
with the coupler to yield a dye. 
Preferred color developing agents are p-phenylenediamines. Especially 
preferred are 4-amino-3-methyl-N,N-diethylaniline hydrochloride, 
4-amino-3-methyl-N-ethyl-N--(methanesulfonamido)-ethylaniline sulfate 
hydrate, 4-amino-3-methyl-N-ethyl-N--hydroxyethylaniline sulfate, 
4-amino-3--(methanesulfonamido)ethyl-N,N-diethylaniline hydrochloride and 
4-amino-N-ethyl-N-2-methoxy-ethyl)-m-toluidine di-p-toluenesulfonic acid. 
With negative working halides this processing step leads to a negative 
image. To obtain a positive (or reversal) image, this step can be preceded 
by development with a non-chromogenic developing agent to develop exposed 
silver halide, but not form dye, and the uniform fogging of the element to 
render unexposed silver halide developable. Alternatively, a direct 
positive emulsion can be employed to obtain a positive image. 
Development is followed by the conventional steps of bleaching, fixing, or 
bleach-fixing, to remove silver and silver halide, washing and drying. 
The 8- and 5hydroxyquinoline cyan couplers and other 6- and 
7-hydroxyquinoline compounds are prepared by the reaction of a substituted 
aminophenol salt with two molar equivalents of an enolizable aldehyde 
containing at least one .alpha.-substituted hydrogen atoms as follows: 
##STR10## 
, wherein R.sub.1 is a substituted or unsubstituted alkyl group with one 
to 30 carbon atoms; 
R.sub.2 and R.sub.3 is hydrogen or other substituents; and 
HY is a strong organic or inorganic acid 
The aldehyde is enolizable to the following structure: 
##STR11## 
The process of the present invention is carried out under very mild 
reaction conditions, at temperatures from about 15.degree. C. to about 
30.degree. C., preferably 23.degree. C., and in the presence of a solvent, 
such as methanol or ethanol. The desired hydroxyquinoline compounds 
generally separate either as salts or as free bases from the reaction 
mixture and are readily isolated in good yields. 
In this process, any aminophenol having an unsubstituted position ortho to 
the amino group can be used. Examples of useful aminophenols are 
2-hydroxyquinoline; 2-hydroxy-5-chloroaniline; 
2-hydroxy-3,5dichloroaniline; 2-hydroxy-3,5-dichloro-4-ethylaniline; 
2-hydroxy-4alkylamido-5-chloroaniline, where the alkyl group is 
substituted or unsubstituted; 2-hydroxy-4-arylamido-5-aryloxyaniline, 
where the aryl groups are phenyl or substituted phenyl; 
2-hydroxy-3-carbamyl-aniline, where the carbamyl group is substituted or 
unsubstituted; 2-hydroxy-3-ureido-5-fluoroaniline, where the ureido group 
is substituted or unsubstituted; 3-hydroxy-6-chloroaniline; 
3-hydroxy-4-arylamidoaniline; where the aryl group is phenyl or 
substituted phenyl; 3-hydroxy-4-arylamido-6-chloroaniline, where the aryl 
group is phenyl or substituted phenyl; 
3-hydroxy-4-alkylamido-6-aryloxyaniline, where the alkyl group is 
substituted or unsubstituted and the aryl group is phenyl or substituted 
phenyl; 4-hydroxy-3,5-dichloroaniline; 4-hydroxy-2-methylaniline; and 
4-hydroxy-3-cyanoaniline. These aminophenols are typically used in the 
process of the present invention as their salts, formed with strong acids, 
organic or inorganic, such as hydrochloric, sulfuric, and 
p-toluenesulfonic acids. 
The process of the present invention can utilize any alkyl or substituted 
alkyl aldehyde containing at least one .alpha.-substituted hydrogen atoms. 
The aldehyde can contain from 2 to about 30 carbon atoms. Particularly 
useful aldehydes for the process of the invention are acetaldehyde, 
propionaldehyde, t-butylacetaldehyde, phenylacetaldehyde, octylaldehyde, 
decylaldehyde, dodecylaldehyde, and octadecylaldehyde. 
The process of the invention is carried out in a solvent, preferably a 
polar one in which the salt of the aminophenol is soluble. Examples of 
useful solvents are methanol, ethanol, ethylene glycol, acetonitrile, 
acetic acid, dimethylformamide, and mixtures thereof. Once the reaction is 
complete, the hydroxyquinoline product can be recovered from the liquid as 
a solid precipitate. 
The process of the present invention is advantageous because it is carried 
out at low temperatures without oxidants or large amounts of strong acids. 
Further, it can be used to incorporate ballast of any selected size at the 
1 and 2 positions of the hydroxyquinoline. Such versatility is 
advantageous, because it eliminates additional synthetic steps in the 
attachment of ballast groups to the coupler compound. 
Aside from the compounds previously identified as Structures 1-9, the 
process of the present invention can be utilized to produce compounds of 
the following formulae: 
##STR12##

EXAMPLES 
The following examples further illustrate the invention: 
EXAMPLE 1 
Preparation of 2-undecyl-3-decyl-5,7-dichloro-8-hydroxyquinoline (Structure 
2) 
To a stirred suspension of 21.5 g (0.10 mole) of 2-amino-4,6-dichlorophenol 
hydrochloride in 250 ml of ethanol was added 36.9 g (0.20 mole) of dodecyl 
aldehyde. The resulting mixture was stirred at room temperature for 2 
hours, during which time all the solid dissolved. The mixture was filtered 
and refrigerated overnight. The white solid that crystallized from 
solution was collected and dried to give 31 g (61%) of product, m.p. 
46.degree.-47.degree. C. The H.sup.1 NMR spectrum of the product was 
consistent with the expected structure. Analysis: Calculated for C.sub.3 
0H.sub.47 C.sub.12 NO: C, 70.85; H, 9.31; Cl, 13.94; N, 2.75. Found: C, 
70.77; H, 9.15; Cl, 14.03; N, 2.68. 
EXAMPLE 2 
Preparation of 2-undecyl-3-decyl-5,7-dichloro-6-methyl-8-hydroxyquinoline 
(Structure 1) 
The procedure of Example 1 was repeated except that the starting 
aminophenol salt was 2-amino-4,6-dichloro-5-methylphenol hydrochloride. A 
65% yield of white crystalline needles, m.p. 54.5.degree.-56.degree. C., 
was obtained. The H.sup.1 NMR spectrum of the product was consistent with 
the expected structure. Analysis: Calculated for C.sub.31 H.sub.49 
C.sub.12 NO: C, 71.28; H, 9.38; Cl, 13.59; N, 2.68. Found: C, 70.85; H, 
9.21; Cl, 14.01; N, 2.61. 
EXAMPLE 3 
Preparation of 2,6-dimethyl-5,7-dichloro-8-hydroxyquinoline (Structure 10) 
The procedure of Example 1 was repeated except that the starting 
aminophenol salt was 2-amino-4,6-dichloro-5-methylphenol hydrochloride and 
the starting aldehyde was acetaldehyde. The light brown crystalline 
product, m.p. 234.degree.-236.degree. C., that separated was the 
hydrochloride salt of the desired hydroxyquinoline compound; the yield was 
57%. The free hydroxyquinoline, which was obtained by treating a methanol 
solution of the salt with an aqueous solution of sodium bicarbonate, was 
recrystallized from ethanol to give brown needles, m.p. 
118.degree.-119.degree. C. Analysis: Calculated for C.sub.11 H.sub.9 
C.sub.12 NO: C, 54.57; H, 3.75; Cl, 29.29; N, 5.79. Found: C, 54.49; H, 
3.74; Cl, 29.10; N, 5.79. 
EXAMPLE 4 
Preparation of 2-methyl-6-benzamido-8-chloro-5-hydroxyquinoline (Structure 
12) 
To a solution of 43.3 g (0.10 mole) of 3-amino-4-chloro-6-benzamidophenol 
p-toluenesulfonic acid salt in 500 ml of ethanol was slowly added, with 
stirring, 17.6 g (0.40 mole) of acetaldehyde. The mixture was stirred at 
room temperature for 8 hours; the yellow solid that precipitated during 
this time was collected by filtration, washed with ethanol, and dried. The 
yield of product, which was the p-toluenesulfonic acid salt of the desired 
hydroxyquinoline compound, was 21 g (67%); its m.p. was 
184.degree.-185.degree. (dec.). The free hydroxyquinoline, which was 
obtained by treating a methanol solution of the salt with an aqueous 
solution of sodium bicarbonate, was recrystallized from ethanol to give 
white needles, m.p. 189.degree.-191.degree. C. Analysis: Calculated for 
C.sub.17 H.sub.13 ClN.sub.2 O.sub.2 : C, 65.4; H, 4.2; Cl, 11.3; N, 9.0. 
Found: C, 65.5; H, 4.5; Cl, 10.9; N, 8.9. 
EXAMPLE 5 
Preparation of 2-undecyl-3 -decyl-5-chloro-7-acetamido-8-hydroxyquinoline 
(Structure 6) 
A solution of 11.5 g (0.050 mole) of 2-nitro-4-chloro-6-acetamidophenol in 
150 ml of ethanol containing a small amount of 10% Pd-charcoal catalyst 
was reduced under hydrogen at 40 psi. After reduction was complete, the 
catalyst was removed by filtration. To the filtration was added, with 
stirring, 4.4 ml (0.05 mole) of concentrated hydrochloric acid, followed 
by 18.4 g (0.10 mole) of dodecyl aldehyde. The mixture was stirred at room 
temperature for 3 hours, then poured into water. The brown-colored gum 
that precipitated was dissolved in dichloromethane and chromotographed on 
a silica gel column. The fractions containing the product were combined, 
and the solvent was removed to give 12 g (45%) of a white solid, m.p. 
120.degree.-121.degree. C. The H.sup.1 NMR spectrum of this solid was 
consistent with the expected structure. Analysis: Calculated for C.sub.32 
H.sub.51 ClN.sub.2 O.sub.2 : C, 72.35; H, 9.68; Cl, 6.67; N, 5.27. Found: 
C, 72.25; H, 9.50; Cl, 6.65; N, 5.21. 
EXAMPLE 6 
Preparation of 2-undecyl-3-decyl-5-chloro-7-benzamido-8-hydroxyquinoline 
(Structure 4) 
The procedure of Example 5 was repeated except tat the starting nitro 
compound in the reduction step was 2-nitro-4-chloro-6-benzamidophenol. The 
crude product obtained by pouring the reaction mixture into water was 
purified by chromatography on a silica gel column to give 52% of a white 
amorphous solid. The H.sup.1 NMR spectrum of this solid was consistent 
with the expected structure. Analysis: Calculated for C.sub.37 H.sub.53 
ClN.sub.2 O.sub.2 : C, 74.91; H, 9.0; N, 4.72. Found: C, 75.01; H, 8.61; 
N, 4.30. 
EXAMPLE 7 
Preparation of 
2-propyl-3-ethyl-6-(3-hexadecanesulfonamidobenzamido)-8-chloro-5-hydroxyqu 
inoline (Structure 14) 
The reaction of 3-amino-4-chloro-6-(3-hexadecanesulfonamidobenzamido)phenol 
and propionaldehyde was carried out as in Example 1 except that the 
reaction mixture was poured into water. The gum that precipitated was 
purified by chromatography on a silica gel column. The yield of product 
was 40%. The H.sup.1 NMR of this product was consistent with the expected 
structure. Analysis: Calculated for C.sub.37 H.sub.54 ClN.sub.3 O.sub.4 S: 
C, 66.14; H, 8.11; N, 6.26. Found: C, 66.37; H, 8.22; N, 6.61. 
PHOTOGRAPHIC EXAMPLES 
Dispersions of the couplers of the present invention were prepared in the 
following manner: In one vessel, the coupler, dibutyl phthalate, and ethyl 
acetate were combined and warmed to form a solution. In a second vessel, 
17.6 g of 12.5% gelatin, 2.22 g of Alkanol XC.RTM. (E.I. DuPont de Nemours 
Co., Wilmington, Del.), and water were combined and warmed to about 
40.degree. C. The two mixtures were combined and passed three times 
through a colloid mill. The ethyl acetate was removed by evaporation and 
water was added to restore the mixture to the weight before evaporation. 
EXAMPLE 8 
Photographic Dispersion of 
2-undecyl-3-decyl-5,7-dichloro-6-methyl-8-hydroxyquinoline (Structure 1) 
A dispersion was prepared by the procedure described above from 1.24 g of 
the 2-undecyl-3-decyl-5,7-dichloro-6-methyl-8-hydroxyquinoline of Example 
2, 1.24 g of dibutyl phthalate, 3.72 g of ethyl acetate, and 10.82 g of 
water. 
EXAMPLE 9 
Photographic Dispersion of 
2-undecyl-3-decyl-5,7-dichloro-8-hydroxyquinoline (Structure 2) 
A dispersion was prepared by the procedure described above from 1.20 g of 
2-undecyl-3-decyl-5,7-dichloro-8-hydroxyquinoline of Example 1, 1.20 g of 
dibutyl phthalate, 3.61 g of ethyl acetate, and 11.00 g of water. 
EXAMPLE 10 
Photographic Dispersion of 
2-undecyl-3-decyl-5-chloro-6-benzamido-8-hydroxyquinoline (Structure 4) 
A dispersion was prepared by the procedure described above from 1.41 g of 
2-undecyl-3-decyl-5-chloro-6-benzamido-8-hydroxyquinoline of Example 6, 
1.41 g of dibutyl phthalate, 4.22 g of ethyl acetate, and 10.00 g of 
water. 
EXAMPLE 11 
Photographic Dispersion of 
2-propyl-3-ethyl-6-(3-hexadecanesulfonamidobenzamido)-8-chloro-5-hydroxyqu 
inoline (Structure 8) 
A dispersion was prepared by the procedure described above from 1.59 g of 
2-propyl-3-ethyl-6-(3-hexadecanesulfonamidobenzamido)-8-chloro-5-hydroxyqu 
inoline of Example 7, 1.59 g of dibutyl phthalate, 4.77 g of ethyl acetate, 
and 9.07 g of water. 
EXAMPLE 12 
Evaluation of Elements Containing Photographic Dispersions 
Photographic elements containing dispersions of couplers of the present 
invention were prepared by coating the following layers in the order 
listed on a resin-coated paper support. All quantities are in grams per 
square meter except as noted. 
______________________________________ 
1st Layer 
Gelatin 3.23 
2nd Layer 
Gelatin 1.61 
Coupler Dispersion 4.3 .times. 10.sup.-7 mole 
coupler/m.sup.2 
Green-sensitized AgCl emulsion 
0.17 mg Ag/m.sup.2 
3rd Layer 
Gelatin 1.33 
2-(2H-benzotriazol-2-yl)- 
0.73 
4,6-bis-(1,1-dimethylpropyl)phenol 
Tinuvin 326 (Ciba-Geigy Corp.) 
0.13 
4th Layer 
Gelatin 1.40 
Bis(vinylsulfonylmethyl)ether 
0.14 
______________________________________ 
The photographic elements were given stepwise exposures to green light and 
processed as follows at 35.degree. C. 
______________________________________ 
Developer 45 seconds 
Bleach-Fix 45 seconds 
Wash (running water) 
1 minute, 30 seconds 
______________________________________ 
The developer and bleach-fix were of the following compositions: 
______________________________________ 
Developer 
Water 700.00 mL 
Triethanolamine 12.4l g 
Blankophor REU (Mobay Chemical Corp., 
2.30 g 
Pittsburgh, Pa.) 
Lithium polystyrene sulfonate 
0.30 g 
N,N-Diethylhydroxylamine (85% soln.) 
5.40 g 
Lithium sulfate 2.70 g 
N-(2-[(4-amino-3-methylphenyl) 
5.00 g 
ethylamino]ethyl)-methanesulfonamide, 
sesquisulfate 
1-Hydroxyethyl-1,1-diphosphonic acid 
0.81 g 
(60% soln.) 
Potassium carbonate, anhydrous 
21.16 g 
Potassium chloride 1.60 g 
Potassium bromide 7.00 mg 
Water to make 1.00 L 
pH @ 26.7.degree. C. adjusted to 10.04 0.05 
Bleach-Fix 
Water 700.00 mL 
Solution of ammonium thiosulfate (56.4%) 
127.40 g 
+ Ammonium sulfite (4%) 
Sodium metabisulfite 10.00 g 
Acetic acid (glacial) 10.20 g 
Solution of ammonium ferric 
110.40 g 
ethylenediaminetetraacetate (44%) + 
ethylenediaminetetraacetic acid (3.5%) 
Water to make 1.00 L 
pH @ 26.7.degree. C. adjusted to 6.7 
______________________________________ 
Cyan dyes were formed upon processing. The maximum and minimum densities 
(D-max and D-min) to green light (Status A) and the wavelength of peak 
absorption at a density of 1.0 for each coupler are set forth in Table 1. 
TABLE 1 
__________________________________________________________________________ 
Absorption 
Coupler Example 
D-max 
D-min 
maximum (nm) 
__________________________________________________________________________ 
2-undecyl-3-decyl-5,7-dichloro- 
8 1.45 
0.075 
644 
6-methyl-8-hydroxyquinoline 
2-undecyl-3-decyl-5,7-dichloro- 
9 2.42 
0.077 
644 
8-hydroxyquinoline 
2-undecyl-3-decyl-5-chloro- 
10 2.24 
0.089 
671 
6-benzamido-8-hydroxyquinoline 
2-propyl-3-ethyl-6-(3-hexadecane- 
11 2.10 
0.080 
618 
sulfonamidobenzamido)-8-chloro- 
5-hydroxyquinoline 
__________________________________________________________________________ 
Although the invention has been described in detail for the purpose of 
illustration, it should be understood that such detail is solely for that 
purpose, and variations can be made therein by these skilled in the art 
without departing from the spirit and scope of the invention which is 
defined by the following claims.