Photographic products and processes employing novel nondiffusible heterocyclyazonaphthol dye-releasing compounds

Photographic elements, diffusion transfer assemblages and processes are described which employ a novel nondiffusible compound having a releasable 2-(2-heterocyclylazo)-1-naphthol dye moiety which contains a nitrogen atom adjacent to the point of attachment to the azo linkage. The compound contains a ballasted carrier moiety which is capable of releasing the diffusible azo dye under alkaline conditions. The dye is transferred imagewise to an image-receiving layer where it is contacted with metal ions to form a metal-complexed azo dye transfer image of excellent stability.

This invention relates to photography and more particularly to color 
diffusion transfer photography employing certain nondiffusible azo 
dye-releasing compounds which, as a function of development of a silver 
halide emulsion layer, release a diffusible, metallizable 
2-(2-heterocyclylazo)-1-naphthol dye which contains a nitrogen atom 
adjacent to the point of attachment to the azo linkage. Highly stable 
metal complexes of this dye are formed in an image-receiving layer. 
Azo dye developers containing metallizable groups are disclosed in U.S. 
Pat. Nos. 3,081,167; 3,196,014; 3,299,041; 3,453,107; 3,563,739; 3,544,545 
and 3,551,406. Since it is a reactive species, however, the developer 
moiety of such dye developers is capable of developing any exposed silver 
halide emulsion layer with which it comes into contact, rather than just 
developing the adjacent silver halide emulsion with which it is 
associated. Unwanted wrong-layer development, therefore, can occur in dye 
developer systems which results in undesirable interimage effects. 
Accordingly, it is desirable to provide an improved transfer system in 
which the dye is not attached to a "reactive" moiety, such as a developer 
moiety, so that such dye can diffuse throughout the photographic film unit 
without becoming immobilized in undesired areas. 
In U.S. Pat. 4,076,529, issued Feb. 28, 1978, nondiffusible dye-releasing 
compounds are disclosed. Among the various dye moieties disclosed which 
can be released are "metal complexed dyes". No specific structures are 
shown, however. 
Anderson and Nickless, Analyst 93, 13 and 20 (1968) describe pyridylazo and 
pyrimidylazonaphthol dyes as colorimetric indicators for the analytical 
determination of metal ions such as copper. The compounds employed in the 
instant invention nor their use in photographic products are not shown, 
however. 
In U.S. Pat. Nos. 3,931,144; 3,932,380; 3,942,987; 3,954,476; 4,001,209; 
4,013,633 and 4,013,635, various non-diffusible azo dye-releasing 
compounds are disclosed. The released dyes, however, are not disclosed as 
being metallized or metallizable. 
The April 1977 edition of Research Disclosure, pages 32 through 39, 
discloses various nondiffusible dye-releasing compounds and various 
metallized azo dye fragments. Such premetallized dyes are large molecules 
which diffuse more slowly than unmetallized dyes, resulting in long access 
times for image formation. In any event, however, the specific compounds 
employed in the instant invention are not disclosed. 
U.S. Pat. Nos. 3,086,005; 3,492,287 and 3,985,499 disclose various azo 
dyes, U.S. Pat. Nos. 2,348,417; 2,495,244; and 2,830,042 and French Patent 
Nos. 1,124,882 and 1,200,358 disclose various dyes from azopyridines, 
while U.S. Pat. Nos. 2,868,775; 2,938,895; 3,097,196; 3,691,161; and 
3,875,139; British Patent No. 899,758; and an article entitled "The 
Irgalan Dyes--Neutral-Dyeing Metal-Complex Dyes" by Guido Schetty, J. Soc. 
Dyers and Colourists, Volume 71, 1955, pages 705 through 724, disclose 
various metal complexed dyes. Again, however, neither the specific 
compounds employed in the instant invention nor the results obtained 
therewith are disclosed. 
In U.S. Pat. No. 4,142,891 of Baigrie et al, issued Mar. 6, 1979, there is 
a generic description of metallizable compounds which include those of the 
instant invention. The compounds of the instant invention are not 
specifically taught by Baigrie et al, however, and the results obtained 
with the instant invention are unexpectedly superior, as described below. 
It would be desirable to provide improved dye-releasing compounds 
containing chelating dye moieties, so that the dye which is released 
imagewise during processing can diffuse to an image-receiving layer 
containing metal ions to form a metal-complexed, dye transfer image having 
better hues, rapid diffusion rates and shorter access times than those of 
the prior art, as well as good stability to heat, light and chemical 
reagents. The dyes of the present invention, when chelated by metal ions 
such as nickel (II) ions, have a good magenta or cyan hue with minimal 
unwanted absorption. They have superior stability to fading by light in a 
variety of environments. The absorption of the non-diffusible compounds of 
the present invention in a photographic element before processing is, to a 
large extent, shifted out of the desired region of the spectrum, 
particularly at low pHs. When the released dye is metallized in a 
receiving element, however, a magenta or cyan dye with excellent hue for 
use in color photography is produced. 
A photographic element in accordance with the invention comprises a support 
having thereon at least one photosensitive silver halide emulsion layer 
having associated therewith a nondiffusible compound having at least one 
releasable 2-(2-heterocyclylazo)-1-naphthol dye moiety, said compound 
containing a ballasted carrier moiety which is capable of releasing said 
diffusible azo dye under alkaline conditions, such as, for example, as a 
function (either direct or inverse) of development of the silver halide 
emulsion layer, the heterocyclyl moiety containing a nitrogen atom 
adjacent to the point of attachment to the azo linkage. 
Good dyes may be obtained in a preferred embodiment of the invention when 
the 2-(2-heterocyclylazo)-1-naphthol dye-releasing compound is represented 
by the formula: 
##STR1## 
wherein: 
G is a hydroxy group or a salt thereof (e.g., a sodium salt, a 
tetramethylammonium salt, etc,) or a hydrolyzable precursor thereof (e.g., 
an acyloxy group having the formula --OCOR.sup.1, --OCOOR.sup.1, or 
--OCON(R.sup.1).sub.2, wherein each R.sup.1 is an alkyl group having 1 to 
about 8 carbon atoms, such as methyl, ethyl, isopropyl, butyl and the 
like, or an aryl group having 6 to about 12 carbon atoms, such as phenyl, 
etc.;) or a group which together with 
##STR2## 
is CAR which is bonded to the naphthalene group through the oxygen of the 
##STR3## 
(the oxygen being bonded directly to the naphthalene ring); 
Z represents the atoms necessary to complete a heterocyclic ring; 
CAR represents said ballasted carrier moiety; and 
t is a positive integer of 1 to 2. 
Z in the above formula, together with the nitrogen atom to which it is 
attached, can represent a wide variety of heterocyclic rings, such as 
pyridine, pyrimidine, quinoline, isoquinoline, pyrazine, pyridazine, 
thiazole, thiadiazole, triazole, benzothiazole, acinaphthothiazole, etc. 
In general, Z and the nitrogen atom to which it is attached are an 
aromatic or non-aromatic, 5- or 6-membered heterocyclic 
nitrogen-containing ring. In a preferred embodiment, the ring is aromatic. 
In another preferred embodiment, the ring contains six members. This ring 
may also have other rings fused thereon. 
In still another preferred embodiment of the invention, t is 1, G is OH and 
Z represents the atoms necessary to complete a pyridine or pyrimidine 
ring. 
Other substituents may also be present in either of the two ring systems in 
the formula above, such as alkyl of 1 to 6 carbon atoms, alkoxy, halogens, 
solubilizing groups such as sulfonamido, sulfamoyl, carbamoyl, 
alkoxycarbonyl, carboxy, sulfo, hydrolyzable precursors thereof, etc. The 
heterocyclic ring may not be substituted with a nitro group, however. 
In another preferred embodiment of the invention, CAR may have attached 
thereto two azo dye moieties as shown by the formula above, in which case 
two dye moieties will be released from one CAR moiety. 
When hydrolyzable precursors of the dye moiety of the above compounds are 
employed, the absorption spectrum of the azo dye is shifted to shorter 
wavelengths. "Shifted dyes" of this type absorb light outside the range to 
which the associated silver halide layer is sensitive. In some cases, the 
absorption spectrum of the unmetallized azo dye ligand is substantially 
shifted to shorter wavelengths at neutral pH (e.g., 5 to 8). 
There is great latitude in selecting a CAR moiety which is attached to the 
2-(2-heterocyclylazo)-1-naphthol dye-releasing compounds described above. 
Depending upon the nature of the ballasted carrier selected, various 
groups may be needed to attach or link the carrier moiety to the dye. Such 
linking groups are considered to be a part of the CAR moiety in the above 
definition. It should also be noted that when the dye moiety is released 
from the compound, cleavage may take place in such a position that part or 
all of a linking group if one is present, and even part of the ballasted 
moiety may be transferred to the image-receiving layer along with the dye 
moiety. In any event, the dye nucleus as shown above can be thought of as 
the "minimum" which is transferred. 
CAR moieties useful in the invention are described in U.S. Pat. Nos. 
3,227,550; 3,628,952; 3,227,552; and 3,844,785 (dye released by 
chromogenic coupling); U.S. Pat. Nos. 3,443,939 and 3,443,940 (dye 
released by intramolecular ring closure); U.S. Pat. Nos. 3,698,897 and 
3,725,062 (dye released from hydroquinone derivatives); U.S. Pat. No. 
3,728,113 (dye released from a hydroquinonylmethyl quaternary salt); U.S. 
Pat. Nos. 3,719,489 and 3,443,941 (silver ion induced dye release); and 
U.S. Pat. Nos. 3,245,789 and 3,980,497; Canadian Patent No. 602,607; 
British Patent No. 1,464,104; Research Disclosure 14447, April 1976; and 
U.S. Pat. No. 4,139,379, issued Feb. 13, 1979 of Chasman et al (dye 
released by miscellaneous mechanisms), the disclosures of which are hereby 
incorporated by reference. 
In a further preferred embodiment of the invention, the ballasted carrier 
moiety or CAR as described above may be represented by the following 
formula: 
EQU (Ballast-Carrier-Link) - 
wherein: 
(a) Ballast is an organic ballasting radical of such molecular size and 
configuration as to render the compound nondiffusible in a photographic 
element during development in an alkaline processing composition; 
(b) Carrier is an oxidizable acyclic, carbocyclic or heterocyclic moiety 
(see "The Theory of the Photographic Process", by C. E. K. Mees and T. H. 
James, Third Edition, 1966, pages 282 to 283), e.g., moieties containing 
atoms according to the following configuration: 
EQU a (--C.dbd.C).sub.b -- 
wherein: 
b is a positive integer of 1 to 2; and 
a represents the radicals OH, SH, NH-, or hydrolyzable precursors thereof; 
and 
(c) Link represents a group which upon oxidation of said Carrier moiety is 
capable of being hydrolytically cleaved to release the diffusible azo dye. 
For example, Link may be the following groups: 
##STR4## 
wherein * represents the position of attachment to Carrier. 
The Ballast group in the above formula is not critical as long as it 
confers nondiffusibility to the compound. Typical Ballast groups include 
long-chain alkyl radicals linked directly or indirectly to the compound as 
well as aromatic radicals of the benzene and naphthalene series indirectly 
attached or fused directly to the ring, etc. Useful Ballast groups 
generally have at least 8 carbon atoms such as substituted or 
unsubstituted alkyl groups of 8 to 22 carbon atoms, a carbamoyl radical 
having 8 to 30 carbon atoms such as --CONH(CH.sub.2).sub.4 --O--C.sub.6 
H.sub.3 (C.sub.5 H.sub.11).sub.2, --CON(C.sub.12 H.sub.25).sub.2, etc, a 
keto radical having 8 to 30 carbon atoms such as --CO--C.sub.17 H.sub.35, 
--CO--C.sub.6 H.sub.4 (t--C.sub.12 H.sub.25), etc. 
For specific examples of Ballast-Carrier-Link moieties useful as the CAR 
moiety in this invention, reference is made to the November 1976 edition 
of Research Disclosure, pages 68 through 74, and the April 1977 edition of 
Research Disclosure, pages 32 through 39, the disclosures of which are 
hereby incorported by reference. 
In a highly preferred embodiment of the invention, the ballasted carrier 
moiety or CAR in the above formulas is a group having the formula: 
##STR5## 
wherein: 
(a) Ballast is an organic ballasting radical of such molecular size and 
configuration (e.g., simple organic groups or polymeric groups) as to 
render the compound non-diffusible in a photographic element during 
development in an alkaline processing composition; 
(b) D is OR.sup.2 or NHR.sup.3 wherein R.sup.2 is hydrogen or a 
hydrolyzable moiety and R.sup.3 is hydrogen or a substituted or 
unsubstituted alkyl group of 1 to 22 carbon atoms such as methyl, ethyl, 
hydroxyethyl, propyl, butyl, secondary butyl, tert-butyl, cyclopropyl, 
4-chlorobutyl, cyclobutyl, 4-nitroamyl, hexyl, cyclohexyl, octyl, decyl, 
octadecyl, dodecyl, benzyl, phenethyl, etc. (when R.sup.3 is an alkyl 
group of greater than 8 carbon atoms, it can serve as a partial or sole 
Ballast); 
(c) Y represents the atoms necessary to complete a benzene nucleus, a 
naphthalene nucleus, or a 5 to 7 membered heterocyclic ring such as 
pyrazolone, pyrimidine, etc; 
(d) j is a positive integer of 1 to 2 and is 2 when D is OR.sup.2 or when 
R.sup.3 is hydrogen or an alkyl group of less than 8 carbon atoms; and 
(e) L is a linking group which is [X-(NR.sup.4 -J).sub.q ].sub.m - or 
X-J-NR.sup.4 - wherein: 
(i) X represents a bivalent linking group of the formula -R.sup.5 -L'.sub.n 
-R.sup.5.sub.p - where each R.sup.5 can be the same or different and each 
represents an alkylene radical having 1 to about 8 carbon atoms, such as 
methylene, hexylene and the like; a phenylene radical; or a substituted 
phenylene radical having 6 to about 9 carbon atoms, such as methoxy 
phenylene; 
(ii) L' represents a bivalent radical selected from oxy, imino, carbonyl, 
carboxamido, carbamoyl, sulfonamido, ureylene, sulfamoyl, sulfinyl or 
sulfonyl; 
(iii) n is an integer of 0 or 1; 
(iv) p is 1 when n equals 1 and p is 1 or 0 when n equals 0, provided that 
when p is 1 the carbon content of the sum of both R.sup.5 radicals does 
not exceed 14 carbon atoms; 
(v) R.sup.4 represents a hydrogen atom, or an alkyl radical having 1 to 
about 6 carbon atoms; 
(vi) J represents a bivalent radical selected from sulfonyl or carbonyl; 
(vii) q repreents an integer of 0 or 1; and 
(viii) m represents an integer of 0, 1 or 2. 
Especially good results are obtained in the above formula when D is OH, j 
is 2, and Y is a naphthalene nucleus. 
Examples of the CAR moiety in this highly preferred embodiment are 
disclosed in U.S. Pat. No. 4,076,529; U.S. Pat. No. 3,928,312; French 
Patent No. 2,284,140; and German Patent Nos. 2,406,664; 2,613,005; and 
2,505,248, the disclosures of which are hereby incorporated by reference, 
and include the following: 
##STR6## 
In another highly preferred embodiment of the invention, the ballasted 
carrier moiety or CAR in the above formulas is such that the diffusible 
azo dye is released as an inverse function of development of the silver 
halide emulsion layer under alkaline conditions. This is ordinarily 
referred to as positive-working dye-release chemistry. In one of these 
embodiments, the ballasted carrier moiety or CAR in the above formulas may 
be a group having the formula: 
##STR7## 
wherein: 
Ballast is an organic ballasting radical of such molecular size and 
configuration as to render the compound nondiffusible in a photographic 
element during development in an alkaline processing composition; 
W.sup.2 represents at least the atoms necessary to complete a benzene 
nucleus (including various substituents thereon); and 
R.sup.7 is an alkyl (including substituted alkyl) radical having 1 to about 
4 carbon atoms. 
Examples of the CAR moiety in this formula I include the following: 
##STR8## 
In a second embodiment of positive-working dye-release chemistry as 
referred to above, the ballasted carrier moiety or CAR in the above 
formulas may be a group having the formula: 
##STR9## 
wherein: 
Ballast is an organic ballasting radical of such molecular size and 
configuration as to render the compound nondiffusible in a photographic 
element during development in an alkaline processing composition; 
W.sup.1 represents at least the atoms necessary to complete a quinone 
nucleus (including various substituents thereon); 
r is a positive integer of 1 or 2; 
R.sup.6 is an alkyl (including substituted alkyl) radical having 1 to about 
40 carbon atoms or an aryl (including substituted aryl) radical having 6 
to about 40 carbon atoms; and 
k is a positive integer of 1 to 2 and is 2 when R.sup.6 is a radical of 
less than 8 carbon atoms. 
Examples of the CAR moiety in this formula II include the following: 
##STR10## 
In using the compounds in formulas I and II above, they are employed in a 
photographic element similar to the other nondiffusible dye-releasers 
described previously. Upon reduction of the compound as a function of 
silver halide development under alkaline conditions, the metallizable azo 
dye is released. In this embodiment, conventional negative-working silver 
halide emulsions, as well as direct-positive emulsions, can be employed. 
For further details concerning these particular CAR moieties, including 
synthesis detals, reference is made to U.S. Pat. No. 4,139,379 of Chasman 
et al, issued Feb. 13, 1979, the disclosure of which is hereby 
incorporated by reference. 
In a third embodiment of positive-working dye-release chemistry as referred 
to above, the ballasted carrier moiety or CAR in the above formulas may be 
a group having the formula: 
##STR11## 
wherein: 
Ballast, W.sup.2 and R.sup.7 are as defined for formula I above. 
Examples of the CAR moiety in this formula III include the following: 
##STR12## 
For further details concerning this particular CAR moiety, including 
synthesis details, reference is made to commonly assigned copending U.S. 
application Ser. No. 534,966 of Hinshaw et al, filed Dec. 20, 1974, the 
disclosure of which is hereby incorporated by reference. 
In a fourth embodiment of positive-working dye-release chemistry as 
referred to above, the ballasted carrier moiety or CAR in the above 
formulas may be a group having the formula: 
##STR13## 
wherein: 
Ballast, r, R.sup.6 and k are as defined for formula II above; 
W.sup.2 is as defined for formula I above; and 
K is OH or a hydrolyzable precursor thereof. 
Examples of the CAR moiety in this formula IV include the following: 
##STR14## 
For further details concerning this particular CAR moiety, including 
synthesis details, reference is made to U.S. Pat. No. 3,980,479 of Fields 
et al, issued Sept. 14, 1976, the disclosure of which is hereby 
incorporated by reference. 
A bivalent linking group, e.g., L or X as defined above, may be used, if 
desired, to link the CAR moiety described in formulas I through IV above 
to the dye moiety previously described. 
Representative compounds included within the scope of the invention include 
the following: 
##STR15## 
A process for producing a photographic transfer image in color according to 
the invention comprises: 
(a) treating an imagewise-exposed photographic element as described above 
with an alkaline processing composition in the presence of a silver halide 
developing agent to effect development of each of the exposed silver 
halide emulsion layers, 
(b) the dye-releasing compound then releasing the diffusible azo dye as 
described above imagewise as a function of the development of each of the 
silver halide emulsion layers, 
(c) at least a portion of the imagewise distribution of the azo dye 
diffusing to a dye image-receiving layer; and 
(d) contacting the imagewise distribution of azo dye with metal ions, 
thereby forming a metal-complexed azo dye transfer image. 
In another preferred embodiment of the invention, a process for producing a 
photographic transfer image in color according to the invention comprises: 
(a) treating an imagewise-exposed photographic element as described above 
wherein CAR in the compound has the formula: 
##STR16## 
D, Y, L and j being defined as above, with an alkaline processing 
composition in the presence of a silver halide developing agent to effect 
development of each of the exposed silver halide emulsion layers, thereby 
oxidizing the developing agent; 
(b) the oxidized developing agent thereby cross-oxidizing the dye-releasing 
compound; 
(c) the cross-oxidized dye-releasing compound then cleaving as a result of 
alkaline hydrolysis to release the diffusible azo dye imagewise as a 
function of the imagewise exposure of each of the silver halide emulsion 
layers; 
(d) at least a portion of the imagewise distribution of the azo dye 
diffusing to a dye image-receiving layer; and 
(e) contacting the imagewise distribution of azo dye with metal ions, 
thereby forming a metal-complexed azo dye transfer image. 
The tridentate azo dye ligand which is released from the dye-releasing 
compounds in accordance with the present invention will form a 
coordination complex in the image-receiving layer with polyvalent metal 
ions. The metal ions can be present in the image-receiving layer itself or 
in a layer adjacent thereto or the image-receiving layer can be contacted 
with metal ions in a bath after diffusion of the dye has taken place. 
Metal ions most useful in the invention are those which are essentially 
colorless when incorporated into the image-receiving element, are inert 
with respect to the silver halide layers, react readily with the released 
dye to form a complex of the desired hue, are tightly coordinated to the 
dye in the complex, have a stable oxidation state, and form a dye complex 
which is stable to heat, light and chemical reagents. In general, good 
results are obtained with polyvalent metal ions such as copper (II), zinc 
(II), nickel (II), platinum (II), palladium (II) and cobalt (II) ions. 
For example, it is believed that the coordination complex which is formed 
from the tridentate azo dye ligand according to the invention in one of 
the preferred embodiments thereof has the following structure: 
##STR17## 
where Z is as defined previously, Me is metal and Lig is one or more 
ligand groups depending upon the coordination number of the metal ion, 
such as H.sub.2 O, Cl, pyridine, etc. 
Thus, in accordance with another embodiment of the invention, a 
photographic element is provided which comprises a support having thereon 
a coordination complex of a polyvalent metal ion and a compound having the 
formula: 
##STR18## 
wherein Z is as described above. The element usually contains a 
photographic mordant or image-receiving layer to bind the dye or 
coordination complex thereto. The structures shown above may also, of 
course, be substituted in the same manner as described above for the 
starting compounds from which they are released, e.g., the heterocyclic 
ring Z may be substituted in the 3-position with a methyl group, etc. 
It will be appreciated that, after processing the photographic element 
described above, there remains in it after transfer has taken place an 
imagewise distribution of azo dye in addition to developed silver. A color 
image comprising residual nondiffusible compound may be obtained in this 
element if the residual silver and silver halide are removed by any 
conventional manner well known to those skilled in the photograhic art, 
such as a bleach bath followed by a fix bath, a bleach-fix bath, etc. Such 
a retained dye image should normally be treated with metal ions to 
metallize the dyes to increase their light fastness and shift their 
spectral absorption to the intended region. The imagewise distribution of 
azo dye may also diffuse out of the element into these baths, if desired, 
rather than to an image-receiving element. If a negative-working silver 
halide emulsion is employed in certain preferred photosensitive elements, 
described above, then a positive color image, such as a reflection print, 
a color transparency or motion picture film, may be produced in this 
manner. If a direct-positive silver halide emulsion is employed in such 
photosensitive elements, then a negative color image may be produced. 
The photographic element in the above-described process can be treated with 
an alkaline processing composition to effect or initiate development in 
any manner. A preferred method for applying processing composition is by 
use of a rupturable container or pod which contains the composition. In 
general, the processing composition employed in this invention contains 
the developing agent for development, although the composition could also 
just be an alkaline solution where the developer is incorporated in the 
photographic element, image-receiving element or process sheet, in which 
case the alkaline solution serves to activate the incorporated developer. 
A photographic film unit which can be processed in accordance with this 
invention is adapted to be processed by passing the unit between a pair of 
juxtaposed pressure-applying members, such as would be found in a camera 
designed for in-camera processing, and comprises: 
(1) a photographic element as described above; 
(2) a dye image-receiving layer; and 
(3) means for discharging an alkaline processing composition within the 
film unit, such as a rupturable container which is adapted to be 
positioned during processing of the film unit so that a compressive force 
applied to the container by the pressure-applying members will effect a 
discharge of the container's contents within the film unit; the film unit 
containing a silver halide developing agent. 
In the embodiment described above, the dye image-receiving layer may itself 
contain metal ions or the metal ions may be present in an adjacent layer, 
so that the tridentate azo dye ligand which is released will form a 
coordination complex therewith. The dye thus becomes immobilized in the 
dye image-receiving layer and metallized at the same time. Alternatively, 
the dye image in the dye image-receiving layer may be treated with a 
solution containing metal ions to effect metallization. The formation of 
the coordination complex shifts the absorption of the dye to the desired 
hue, usually to longer wavelengths, which have a different absorption than 
that of the initial dye-releasing compound. If this shift is large enough, 
then the dye-releasing compound may be incorporated in a silver halide 
emulsion layer without adversely affecting its sensitivity. 
The dye image-receiving layer in the above-described film unit can be 
located on a separate support adapted to be superposed on the photographic 
element after exposure thereof. Such image-receiving elements are 
generally disclosed, for example, in U.S. Pat. No. 3,362,819. When the 
means for discharging the processing composition is a rupturable 
container, it is usually positioned in relation to the photographic 
element and the image-receiving element so that a compressive force 
applied to the container by pressure-applying members, such as would be 
found in a typical camera used for in-camera processing, will effect a 
discharge of the container's contents between the image-receiving element 
and the outermost layer of the photographic element. After processing, the 
dye image-receiving element is separated from the photograhic element. 
The dye image-receiving layer in the above-described film unit can also be 
located integral with the photographic element between the support and the 
lowermost photosensitive silver halide emulsion layer. One useful format 
for integral receiver-negative photographic elements is disclosed in 
Belgian Pat. No. 757,960. In such an embodiment, the support for the 
photographic element is transparent and is coated with an image-receiving 
layer, a substantially opaque light-reflective layer, e.g., TiO.sub.2, and 
then the photosensitive layer or layers described above. After exposure of 
the photographic element, a rupturable container containing an alkaline 
processing composition and an opaque process sheet are brought into 
superposed position. Pressure-applying members in the camera rupture the 
container and spread processing composition over the photographic element 
as the film unit is withdrawn from the camera. The processing composition 
develops each exposed silver halide emulsion layer and dye images are 
formed as a function of development which diffuse to the image-receiving 
layer to provide a positive, right-reading image which is viewed through 
the transparent support on the opaque reflecting layer background. For 
other details concerning the format of this particular integral film unit, 
reference is made to the above-mentioned Belgian Pat. No. 757,960. 
Another format for integral negative-receiver photographic elements in 
which the present invention can be employed is disclosed in Belgian Pat. 
No. 757,959. In this embodiment, the support for the photographic element 
is transparent and is coated with the image-receiving layer, a 
substantially opaque, light-reflective layer and the photosensitive layer 
or layers described above. A rupturable container containing an alkaline 
processing composition and an opacifier is positioned adjacent the top 
layer and a transparent top sheet which has thereon a neutralizing layer 
and a timing layer. The film unit is placed in a camera, exposed through 
the transparent top sheet and then passed through a pair of 
pressure-applying members in the camera as it is being removed therefrom. 
The pressure-applying members rupture the container and spread processing 
composition and opacifier over the negative portion of the film unit to 
render it light-insensitive. The processing composition develops each 
silver halide layer and dye images are formed as a result of development 
which diffuse to the image-receiving layer to provide a positive, 
right-reading image which is viewed through the transparent support on the 
opaque reflecting layer background. For further details concerning the 
format of this particular integral film unit, reference is made to the 
above-mentioned Belgian Pat. No. 757,959. 
Still other useful integral formats in which this invention can be employed 
are described in U.S. Pat. Nos. 3,415,644; 3,415,645; 3,415,646; 
3,647,437; and 3,635,707. In most of these formats, a photosensitive 
silver halide emulsion is coated on an opaque support and a dye 
image-receiving layer is located on a separate transparent support 
superposed over the layer outermost from the opaque support. In addition, 
this transparent support also preferably contains a neutralizing layer and 
a timing layer underneath the dye image-receiving layer. 
Another embodiment of the invention uses the image-reversing technique 
disclosed in British Pat. No. 904,364, page 19, lines 1 through 41. In 
this process, the dye-releasing compounds are used in combination with 
physical development nuclei in a nuclei layer contiguous to the 
photosensitive silver halide negative emulsion layer. The film unit 
contains a silver halide solvent, preferably in a rupturable container 
with the alkaline processing composition. 
The film unit or assembly used in the present invention may be used to 
produce positive images in single- or multicolors. In a three-color 
system, each silver halide emulsion layer of the film assembly will have 
associated therewith a dye-releasing compound which releases a dye 
possessing a predominant spectral absorption within the region of the 
visible spectrum to which said silver halide emulsion is sensitive 
(initially or after forming the coordination complex), i.e., the 
blue-sensitive silver halide emulsion layer will have a yellow or 
yellow-forming dye-releaser associated therewith, the green-sensitive 
silver halide emulsion layer will have a magenta or magenta-forming 
dye-releaser associated therewith, and the red-sensitive silver halide 
emulsion layer will have a cyan or cyan-forming dye-releaser associated 
therewith, at least one of the dye-releasers being a compound in 
accordance with the present invention. The dye-releaser associated with 
each silver halide emulsion layer may be contained either in the silver 
halide emulsion layer itself or in a layer contiguous to the silver halide 
emulsion layer. 
The concentration of the dye-releasing compounds that are employed in the 
present invention may be varied over a wide range, depending upon the 
particular compound employed and the results which are desired. For 
example, the dye-releasers of the present invention may be coated in 
layers by using coating solutions containing between about 0.5 and about 8 
percent by weight of the dye-releaser distributed in a hydrophilic 
film-forming natural material or synthetic polymer, such as gelatin, 
polyvinyl alcohol, etc, which is adapted to be permeated by aqueous 
alkaline processing composition. 
Depending upon which CAR is used in the present invention, a variety of 
silver halide developing agents can be employed. In certain embodiments of 
the invention, any silver halide developing agent can be employed as long 
as it cross-oxidizes with the dye-releasers described herein. The 
developer may be employed in the photosensitive element to be activated by 
the alkaline processing composition. Specific examples of developers which 
can be employed in this invention include: 
N-methylaminophenol 
Phenidone (1-phenyl-3-pyrazolidone) 
Dimezone (1-phenyl-4,4-dimethyl-3-pyrazolidone) 
aminophenols 
1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 
N,N-diethyl-p-phenylenediamine 
N,N,N',N'-tetramethyl-p-phenylenediamine 
3-methyl-N,N-diethyl-p-phenylenediamine 
3-methoxy-N-ethyl-N-ethoxy-p-phenylenediamine, etc. 
The non-chromogenic developers in this list are preferred, however, since 
they avoid any propensity of staining the dye image-receiving layer. 
In a preferred embodiment of the invention, the silver halide developer 
employed in the process becomes oxidized upon development and reduces 
silver halide to silver metal. The oxidized developer then cross-oxidizes 
the dye-releasing compound. The product of cross-oxidation then undergoes 
alkaline hydrolysis, thus releasing an image-wise distribution of 
diffusible azo dye which then diffuses to the receiving layer to provide 
the dye image. The diffusible moiety is transferable in alkaline 
processing composition either by virtue of its self-diffusivity or by its 
having attached to it one or more solubilizing groups, for example, a 
carboxy, sulpho, sulphonamido, hydroxy or morpholino group. 
In using the dye-releasing compounds according to the invention which 
produce diffusible dye images as a function of development, either 
conventional negative-working or direct-positive silver halide emulsions 
may be employed. If the silver halide emulsion employed is a 
direct-positive silver halide emulsion, such as an internal-image emulsion 
designed for use in the internal image reversal process or a fogged, 
direct-positive emulsion such as a solarizing emulsion, which is 
developable in unexposed areas, a positive image can be obtained in 
certain embodiments on the dye image-receiving layer. After exposure of 
the film unit, the alkaline processing composition permeates the various 
layers to initiate development of the exposed photosensitive silver halide 
emulsion layers. The developing agent present in the film unit develops 
each of the silver halide emulsion layers in the unexposed areas (since 
the silver halide emulsions are direct-positive ones), thus causing the 
developing agent to become oxidized imagewise corresponding to the 
unexposed areas of the direct-positive silver halide emulsion layers. The 
oxidized developing agent then cross-oxidizes the dye-releasing compounds 
and the oxidized form of the compounds then undergoes a base-catalyzed 
reaction to release the dyes imagewise as a function of the imagewise 
exposure of each of the silver halide emulsion layers. At least a portion 
of the imagewise distributions of diffusible dyes diffuse to the 
image-receiving layer to form a positive image of the original subject. 
After being contacted by the alkaline processing composition, a 
pH-lowering layer in the film unit or image-receiving unit lowers the pH 
of the film unit or image receiver to stabilize the image. 
Internal-image silver halide emulsions useful in this invention are 
described more fully in the November 1976 edition of Research Disclosure, 
pages 76 through 79, the disclosure of which is hereby incorporated by 
reference. 
The various silver halide emulsion layers of a color film assembly employed 
in this invention can be disposed in the usual order, i.e., the 
blue-sensitive silver halide emulsion layer first with respect to the 
exposure side, followed by the green-sensitive and red-sensitive silver 
halide emulsion layers. If desired, a yellow dye layer or a yellow 
colloidal silver layer can be present between the blue-sensitive and 
green-sensitive silver halide emulsion layers for absorbing or filtering 
blue radiation that may be transmitted through the blue-sensitive layer. 
If desired, the selectively sensitized silver halide emulsion layers can 
be disposed in a different order, e.g., the blue-sensitive layer first 
with respect to the exposure side, followed by the red-sensitive and 
green-sensitive layers. 
The rupturable container employed in certain embodiments of this invention 
can be of the type disclosed in U.S. Pat. Nos. 2,543,181; 2,643,886; 
2,653,732; 2,723,051; 3,056,492; 3,056,491 and 3,152,515. In general, such 
containers comprise a rectangular sheet of fluid- and air-impervious 
material folded longitudinally upon itself to form two walls which are 
sealed to one another along their longitudinal and end margins to form a 
cavity in which processing solution is contained. 
Generally speaking, except where noted otherwise, the silver halide 
emulsion layers employed in the invention comprise photosensitive silver 
halide dispersed in gelatin and are about 0.6 to 6 microns in thickness; 
the dye-releasers are dispersed in an aqueous alkaline solution-permeable 
polymeric binder, such as gelatin, as a separate layer about 0.2 to 7 
microns in thickness; and the alkaline solution-permeable polymeric 
interlayers, e.g., gelatin, are about 0.2 to 5 microns in thickness. Of 
course, these thicknesses are approximate only and can be modified 
according to the product desired. 
Scavengers for oxidized developing agent can be employed in various 
interlayers of the photographic elements of the invention. Suitable 
materials are disclosed on page 83 of the November 1976 edition of 
Research Disclosure, the disclosure of which is hereby incorporated by 
reference. 
Any material can be employed as the image-receiving layer in this invention 
as long as the desired function of mordanting or otherwise fixing the dye 
images is obtained. The particular material chosen will, of course, depend 
upon the dye to be mordanted. Suitable materials are disclosed on pages 80 
through 82 of the November 1976 edition of Research Disclosure, the 
disclosure of which is hereby incorporated by reference. 
Use of a pH-lowering material in the film units employed in this invention 
will usually increase the stability of the transferred image. Generally, 
the pH-lowering material will effect a reduction in the pH of the image 
layer from about 13 or 14 to at least 11 and preferably 5 to 8 within a 
short time after imbibition. Suitable materials and their functioning are 
disclosed on pages 22 and 23 of the July 1974 edition of Research 
Disclosure and pages 35 through 37 of the July 1975 edition of Research 
Disclosure, the disclosures of which are hereby incorporated by reference. 
A timing or inert spacer layer can be employed in the practice of this 
invention over the pH-lowering layer which "times" or controls the pH 
reduction as a function of the rate at which alkali diffuses through the 
inert spacer layer. Examples of such timing layers and their functioning 
are disclosed in the Research Disclosure articles mentioned in the 
paragraph above concerning pH-lowering layers. 
The alkaline processing composition employed in this invention is the 
conventional aqueous solution of an alkaline material, e.g., alkali metal 
hydroxides or carbonates such as sodium hydroxide, sodium carbonate or an 
amine such as diethylamine, preferably possessing a pH in excess of 11, 
and preferably containing a developing agent as described previously. 
Suitable materials and addenda frequently added to such compositions are 
disclosed on pages 79 and 80 of the November 1976 edition of Research 
Disclosure, the disclosure of which is hereby incorporated by reference. 
While the alkaline processing composition used in this invention can be 
employed in a rupturable container, as described previously, to 
conveniently facilitate the introduction of processing composition into 
the film unit, other methods of inserting processing composition into the 
film unit could also be employed, e.g., interjecting processing solution 
with communicating members similar to hypodermic syringes which are 
attached either to a camera or camera cartridge. The processing 
composition may also be applied by means of a swab or by dipping in a 
bath, if so desired. 
The alkaline solution-permeable, substantially opaque, light-reflective 
layer employed in certain embodiments of photographic film units used in 
this invention are described more fully in the November 1976 edition of 
Research Disclosure, page 82, the disclosure of which is hereby 
incorporated by reference. 
The supports for the photographic elements used in this invention can be 
any material as long as it does not deleteriously affect the photographic 
properties of the film unit and is dimensionally stable. Typical flexible 
sheet materials are described on page 85 of the November 1976 edition of 
Research Disclosure, the disclosure of which is hereby incorporated by 
reference. 
While the invention has been described with reference to layers of silver 
halide emulsions and dye image-providing materials, dotwise coating, such 
as would be obtained using a gravure printing technique, could also be 
employed. In this technique, small dots of blue-, green- and red-sensitive 
emulsions have associated therewith, respectively, dots of yellow, magenta 
and cyan color-providing substances. After development, the transferred 
dyes would tend to fuse together into a continuous tone. 
The silver halide emulsions useful in this invention, both negative-working 
and direct-positive ones, are well known to those skilled in the art and 
are described in Product Licensing Index, Volume 92, December 1971, 
publication 9232, page 107, paragraph I, "Emulsion types"; they may be 
chemically and spectrally sensitized as described on page 107, paragraph 
III, "Chemical sensitization", and pages 108 and 109, paragraph XV, 
"Spectral sensitization", of the above article; they can be protected 
against the production of fog and can be stabilized against loss of 
sensitivity during keeping by employing the materials described on page 
107, paragraph V, "Antifoggants and stabilizers", of the above article; 
they can contain development modifiers, hardeners, and coating aids as 
described on pages 107 and 108, paragraph IV, "Development modifiers"; 
paragraph VII, "Hardeners"; and paragraph XII, "Coating aids", of the 
above article; they and other layers in the photographic elements used in 
this invention can contain plasticizers, vehicles and filter dyes 
described on page 108, paragraph XI, "Plasticizers and lubricants", and 
paragraph VIII, "Vehicles", and page 109, paragraph XVI, "Absorbing and 
filter dyes", of the above article; they and other layers in the 
photographic elements used in this invention may contain addenda which are 
incorporated by using the procedures described on page 109, paragraph 
XVII, "Methods of addition", of the above article; and they can be coated 
by using the various techniques described on page 109, paragraph XVIII, 
"Coating procedures", of the above article, the disclosures of which are 
hereby incorporated by reference. 
The term "nondiffusing" used herein has the meaning commonly applied to the 
term in photography and denotes materials that for all practical purposes 
do not migrate or wander through organic colloid layers, such as gelatin, 
in the photographic elements of the invention in an alkaline medium, and 
preferably when processed in a medium having a pH of 11 or greater. The 
same meaning is to be attached to the term "immobile". The term 
"diffusible" as applied to the materials of this invention has the 
converse meaning and denotes materials having the property of diffusing 
effectively through the colloid layers of the photographic elements in an 
alkaline medium in the presence of "nondiffusing" materials. "Mobile" has 
the same meaning. 
The term "associated therewith" as used herein is intended to mean that the 
materials can be in either the same or different layers so long as the 
materials are accessible to one another. 
The compounds of the present invention can generally be synthesized by one 
of the following methods (reference to pyridine also applies to 
pyrimidine): 
(1) Reaction of a 2-hydrazinopyridine (or analogous heterocycle) with 
1,2-naphthoquinone, and 
(2) Reaction of a 1-naphthol with an alkali metal 2-pyridinediazoate 
generated by the reaction of 2-aminopyridine and an alkyl nitrite in the 
presence of a strong base such as an alkali metal alkoxide.

EXAMPLE 1--Preparation of Compound 1 
4-Amino-N-[4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-2-naphthamide (see 
U.S. Pat. No. 4,013,635, column 24) (70 g) was dissolved in dry methylene 
chloride (1.5 l) and 4-benzoyloxy-3-(2-pyridylazo)-1-naphthalenesulfonyl 
chloride (50 g) was added with stirring. An atmosphere of nitrogen was 
maintained throughout the reaction. Pyridine (12 g) was added to the 
reaction mixture and the reaction allowed to proceed overnight. 
The solvent was removed and methanol added to the residue to enable it to 
be transferred for hydrolysis. In the meantime, a stream of nitrogen was 
passed through a 5 percent potassium hydroxide solution (750 ml) 
maintained at 60.degree. C. on the steam bath. The methanol slurry was 
added to the basic solution and the hydrolysis carried out for 20 minutes. 
At the end of this time, the flask was cooled and the mixture acidified 
with hydrochloric acid. The product was filtered off and dried in the 
vacuum oven. After two recrystallizations from ethyl acetate, the yield 
was 65 g (56 percent), m.p. 195.degree. to 196.degree. C. 
.epsilon.=1.8.times.10.sup.4 in ethanol. 
Intermediates: 
4-Benzoyloxy-3-(2-pyridylazo)-1-naphthalenesulfonyl chloride. 
4-Benzoyloxy-3-(2-pyridylazo)-1-naphthalenesulfonic acid (70 g) was added 
to thionyl chloride (300 ml). Dimethylformamide (30 ml) was added in 
portions while the reaction mixture was being stirred. After 1 hour the 
starting material was all in solution. The reaction mixture was poured 
into a large quantity of ice after a further 4 hours' stirring. The 
product was filtered off and dissolved in chloroform. The chloroform layer 
was shaken with water to destroy any remaining thionyl chloride and dried 
over magnesium sulfate. 
Evaporation of the chloroform solution to one-quarter volume followed by 
cooling precipitated the sulfonyl chloride 40 g. Further concentration 
yielded another 15 g. Total yield 55 g, m.p. 200.degree. to 201.degree. C. 
4-Benzoyloxy-3-(2-pyridylazo)-1-naphthalenesulfonic acid. 
4-Hydroxy-3-(2-pyridylazo)-1-naphthalenesulfonic acid (110 g) was added to 
pyridine (350 ml) followed by benzoyl chloride (250 ml). Triethylamine 
(100 ml) was added slowly and the reaction mixture got warm. After 1 hour 
the mixture was diluted with five times its volume of acetone and 
filtered. The product was washed with acetone and allowed to suck dry. It 
was dissolved in water (minimum volume) and neutralized with hydrochloric 
acid. After filtration, the product was washed with acetone and ether. 
Yield 120 g (83 percent). 
4-Hydroxy-3-(2-pyridylazo)-1-naphthalenesulfonic acid. 
1,2-Naphthoquinone-4-sulfonic acid sodium salt (26 g) was dissolved in a 
mixture of water (500 ml) and concentrated hydrochloric acid (250 ml). To 
this solution was added 2-pyridylhydrazine (11 g) in water (100 ml). The 
reaction mixture became warm and the product started to precipitate. After 
30 minutes of cooling, the product was filtered off and washed with a 
small volume of water, acetone and ether. Yield 32 g (96 percent). 
Example 2--Preparation of Compound 7 
2,5-Bis[N-(3-aminophenoxycarbonyl)-N-methylaminomethyl]-3-hexadecyl-6-propy 
lbenzoquinone (5.8 g, 8 mmol) was dissolved in 50 ml dry pyridine and 
treated with 3.5 g of 4-benzoyloxy-3-(2-pyridylazo)-1-naphthalenesulfonyl 
chloride (Example 1) in small portions. After the mixture was allowed to 
react for 1.5 hours, the solution was poured on ice and acidified with 
hydrochloric acid. The crude precipitate was slurried with 100 ml ethanol 
and 10 ml ammonia to remove the benzoyl group, acidified with aqueous 
hydrochloric acid, the solvent evaporated, the precipitate washed with 
aqueous acid and filtered off. It was purified by chromatography on a 
silica column and eluted with 2 percent ethanol in dichloromethane. 2.4 g 
of product was obtained having a visible spectrum .lambda..sub.max 480 nm, 
.epsilon.=3.6.times.10.sup.4. 
Intermediates: 
A. Preparation of 
2,5-bis[N-(3-aminophenoxycarbonyl)-N-methylaminomethyl]-3-n-hexadecyl-6-n- 
propylquinone, I. 
##STR19## 
Compound II was oxidized by suspending 72 g in 1440 ml of methylene 
chloride and adding 180 g of PbO.sub.2. The quinone dissolves as oxidation 
proceeds. After 1 hour, the solution is filtered, the solids washed with 
methylene chloride and the filtrates and washings concentrated to produce 
a yellow solid melting at 107.degree. to 108.5.degree. C. 
B. Preparation of 
2,5-bis[N-(3-aminophenoxycarbonyl)-N-methylaminomethyl]-3-n-hexadecyl-6-n- 
propylhydroquinone, II. 
##STR20## 
A sample of 111 g of Compound III in about 1500 ml of tetrahydrofuran was 
hydrogenated in the presence of 12 g of 10 percent platinum on carbon 
catalyst. Uptake of hydrogen was rapid and reaction was complete in about 
1 hour. The mixture was filtered, the filtrate concentrated, and the 
residue slurried with acetonitrile. The colorless solid was collected, 
washed with acetonitrile, and air dried. The product melted at 190.degree. 
to 192.5.degree. C. 
C. Preparation of 
3-n-hexadecyl-2,5-bis[N-methyl-N-(3-nitrophenoxycarbonyl)aminomethyl]-6-n- 
propylhydroquinone, III. 
##STR21## 
A suspension of 1 mole of Compound IV in about 7900 ml of methylene 
chloride was treated with 4 moles of N,N-diisopropyl-N-ethylamine, then 
slowly with 2 moles of a methylene chloride solution of m-nitrophenyl 
chloroformate. After stirring for 30 minutes, the solution was washed with 
a mixture of ice/2 N hydrochloric acid solution, then with water. The 
washed methylene chloride solution was dried over sodium sulfate and the 
solvent was removed by evaporation. Although the crude oil obtained is 
used in the next step, a sample was crystallized to produce a colorless 
solid melting at 89.degree. to 95.degree. C. 
D. Preparation of 
3-hexadecyl-2,5-bis(methylaminomethyl)-6-n-propylhydroquinone 
hydrochloride, IV. 
##STR22## 
The bisoxazine, Compound VII (246 g, 0.505 mole), is refluxed for 48 hours 
in 2500 ml of methanol and 500 ml of concentrated hydrochloric acid. 
The solution is evaporated to a solid using reduced pressure, and the light 
beige material is triturated with hexane and recrystallized from 
isopropanol. 
The combined first and second crops yielded 149 g (55 percent). 
E. Preparation of 
5-hexadecyl-2,3,4,7,8,9-hexahydro-3,8-dimethyl-10-propylbenzo[1,2-e:4,5-e' 
]bis[1,3]oxazine, VII. 
##STR23## 
3-Hexadecyl-6-propylhydroquinone (226 g, 0.6 mole) and 250 g (1.236 moles) 
of N,N-(diisobutoxymethyl)methylamine are dissolved in 1500 ml of xylene 
and refluxed under nitrogen for 24 hours. 
The xylene is concentrated off using reduced pressure and the light amber 
oil is poured into a beaker and allowed to solidify. The solid is broken 
up and washed with a small amount of cold hexane. 
There is obtained 246 g of product (84 percent) which appears as one major 
spot on thin layer chromatography. 
Example 3--Preparation of Compound 11 
4-Hydroxy-3-(4-hydroxy-6-methyl-2-pyrimidylazo)-1-naphthalenesulfonic acid 
(2.8 g, 8 mmol) was dissolved in 25 ml of pyridine with the aid of 2.5 ml 
triethylamine. To this solution was added the difunctional acid chloride, 
Compound VIII (2.4 g, 4 mmol); and the mixture was allowed to react for 3 
hours. The product was precipitated with 2 l of ethyl ether. The viscous 
precipitate was dissolved in methanol and the solution evaporated to 
dryness, leaving 4.3 g of solid. That the attachment of the carrier to the 
dye took place at the oxygen atom on the pyrimidine ring was demonstrated 
by the formation of a nickel complex with NiCl.sub.2. Visible spectrum 
(ethanol) .lambda..sub.max 470 nm, .epsilon.=2.4.times.10.sup.4. 
Intermediates: 
F. Preparation of 
3-hexadecyl-2,5-bis(N-methylchloroformamidomethyl)-6-propylbenzoquinone, 
VIII. 
##STR24## 
149 g of Compound IV from Example 2 are dissolved in 150 ml of 
tetrahydrofuran and 20 ml of water, and stirred vigorously with 12.4 g of 
PbO.sub.2 at room temperature until presence of hydroquinone is no longer 
detectable by thin layer chromatography (AgNO.sub.3 /NH.sub.3 test). The 
mixture is filtered through a medium frit glass funnel to remove PbO.sub.2 
and PbO, and the THF solution is stirred into a mixture of 200 ml of 
methylene chloride, 50 ml of water and 6 g of sodium carbonate to produce 
the free base. The methylene chloride phase is separated, dried over 
sodium sulfate, treated with 7 ml of triethylamine and added to an 
ice-cold solution of phosgene in 60 ml of benzene and 50 ml of 
tetrahydrofuran. The mixture is allowed to come to room temperature (about 
1 hour), then is stirred vigorously while adding 100 g of Woelm dry column 
grade silicon dioxide to adsorb the amine hydrochlorides. The SiO.sub.2 is 
removed by filtration, and solvents removed by evaporation. The product, 
11.7 g of an oil which crystallizes on standing is recrystallized with 
about 4 to 6 parts hexane to produce an off-white solid. 
Example 4--Photographic Test - Compound 1 
A single-color integral-imaging receiver element was prepared by coating 
successively on a polyester film support (1) a metallizing layer 
comprising gelatin (1.08 g/m.sup.2) and nickel sulfate hexahydrate (0.58 
g/m.sup.2), (2) a receiving layer comprising a mixture of gelatin and 
poly(4-vinylpyridine), (each at 2.15 g/m.sup.2), (3) a reflecting layer 
comprising titanium dioxide and gelatin in a 6.25/1 ratio, (4) an opaque 
layer of carbon dispersed in gelatin, (5) a layer comprising gelatin and a 
dispersion of Compound 1 (0.84 g/m.sup.2), (6) a layer of a 
green-sensitized internal image emulsion as described in Evans, U.S. Pat. 
No. 3,761,276 (2.69 g/m.sup.2 Ag, 2.69 g/m.sup.2 gelatin), with fogging 
agents NA-16 and H-25 of Leone et al, U.S. Pat. No. 4,030,925, issued June 
21, 1977, and 5-octadecylhydraquinone-2-sulfonic acid (16 g/mole Ag), (7) 
a layer of didodecylhydroquinone (1.29 g/m.sup.2) dispersed in gelatin 
(1.61 g/m.sup.2), and (8) a gelatin overcoat layer. In a comparative 
coating in which no metal ion is used to chelate the dye, the entire layer 
1 was omitted. Layers 1 and 2 above form no part of the invention, as they 
are the subject of an invention by our coworkers Brust, Hamilton and 
Wilkes. 
This integral element was exposed to a multicolor test object, then 
processed by spreading between it and a processing cover sheet, as 
described in U.S. Pat. No. 4,061,496 of Hannie et al, issued Dec. 6, 1977, 
at 22.degree. C., a viscous processing composition, as described in said 
U.S. Pat. No. 4,061,496, by passing the transfer "sandwich" between a pair 
of juxtaposed rollers so that the liquid layer was about 75 .mu.m. The dye 
reflection density in the unexposed areas (i.e., D.sub.max areas) was 
measured at selected intervals up to 24 hours with a recording 
spectrophotometer. The density at .lambda..sub.max after 4 minutes was 
determined from these plots. From the spectrophotometric curves, the final 
D.sub.max, the .lambda..sub.max (i.e., wavelength at D.sub.max) and "half 
band width" (1/2 BW) were determined and recorded in Table I. The "half 
band width" is the wavelength range at half the D.sub.max, a measure of 
purity of hue: The narrower the 1/2 BW, the purer the hue. The light 
stability was determined by exposing part of the strip to a high intensity 
daylight (5000 footcandles) light source for two days. Values are given 
for the original density D.sub.o, the final faded density D.sub.F, and the 
density loss .DELTA.D. 
TABLE I 
______________________________________ 
Hue 
.lambda..sub.max 
1/2 BW Light Stability 
Metallization 
(nm) (nm) D.sub.o 
D.sub.F 
.DELTA.D 
______________________________________ 
Ni.sup.++ 535,575 115 1.00 1.00 0 
None (H) 505 150 0.78 0.55 -0.23 
______________________________________ 
Example 5--Photographic Test - Compound 7 
A single-color photosensitive element was prepared by coating on a subbed 
polyester film support (g/m.sup.2 in parentheses unless otherwise 
specified) (1) a green-sensitive 0.8 .mu.m monodispersed silver bromide 
gelatin emulsion (1.1 Ag, 3.2 gelatin) and a dispersion of a mixture of 
(a) Compound 7 (0.51) and (b) a ballasted reducing agent precursor 
4-(2-acetoxy-2-pivaloylacetamido-N-[4-(2,4-di-t-pentylphenoxy)-butyl-]-1-h 
ydroxy-2-naphthamide (1.02) dissolved in diethyllauramide (1.53), and (2) 
an overcoat layer of gelatin (0.55). This element was exposed through a 
graduated density step tablet to a light source. It was then processed by 
spreading between it and an image receiving element at 22.degree. C. a 
viscous developing composition by passing the transfer "sandwich" between 
a pair of juxtaposed rollers so that the liquid layer was 75 .mu.m. The 
receiving element comprised a polyester film support having thereon (1) a 
metallizing layer comprising gelatin (1.08) and nickel sulfate hexahydrate 
(0.58), and (2) a receiving layer comprising a mixture of gelatin (2.15) 
and poly(4-vinylpyridine) (2.15). The viscous composition contained (per 
liter of water) 51 g potassium hydroxide, 3 g 
4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone, 20 g potassium 
bromide, 1.0 g 5-methylbenzotriazole, and 30 g carboxymethylcellulose. 
After 5 minutes, the elements were peeled apart and the receiving element 
washed in water and dried. A transmission spectrum was obtained and 
normalized to a density of 1.0; .lambda..sub.max was 543, 570 nm. 
Example 6--Spectral Data on Dyes 
Table II shows the hue, diffusion, and light stability data for dyes which 
have not been linked to dye-releasing carriers but which have the 
structural characteristics of the invention. 
Dye 26 was dissolved at a concentration of 5.times.10.sup.-3 molar in 0.5 M 
sodium hydroxide solution containing hydroxyethylcellulose (Natrosol 250H, 
30 g/l) as a thickener. It was spread in a thin layer between a cover 
sheet of polyester film support and a receiving element which consists of 
a polyester film support and a layer containing a mordant mixture of 
gelatin (2.2 g/m.sup.2) and a latex, 
poly(styrene-co-N-benzyl-N,N-dimethyl-N-vinylbenzylammonium 
sulfate-co-divinylbenzene) (2.2 g/m.sup.2) and containing 
bis(acetylacetonato)nickel (II) (0.65 g/m.sup.2). The thickness of the dye 
layer is selected to give an optical density on the receiving element, 
generally around 1.5. When the dye is adsorbed to the mordant, the sheets 
are peeled apart, and the dyed sheet is washed and dried. 
Hue: The wavelength at the maximum density (.lambda..sub.max) of the 
spectrophotometric curves is recorded in the Table along with the "half 
band width" (1/2 BW). 
Light Stability: The above dye-receiving elements were subjected to 5 days 
of a high-intensity daylight (5000 footcandles) fading test. The loss in 
density (.DELTA.D) was monitored spectrophotometrically. 
Dyes 27, 28 and 29 were dissolved in viscous alkaline solutions as above. 
Each solution was imbibed into an image-receiving element which comprised 
three layers coated on a transparent polyester film support: (1) a mordant 
layer, a mixture of gelatin, and the polymeric latex as above, (2) a 
reflecting layer of titanium dioxide (21.5 g/m.sup.2) and gelatin (3.2 
g/m.sup.2), and (3) an opaque layer of carbon (2.7 g/m.sup.2) and gelatin 
(1.7 g/m.sup.2). This receiving element was laminated to a processing 
cover sheet and a viscous processing composition both as described in U.S. 
Pat. No. 4,061,496 referred to above. The hue and light stability data 
were obtained from spectrophotometric curves obtained by reading the 
optical density by reflection through the transparent support. The "half 
band width" is generally greater by reflection than by transmission. 
Dyes 30 and 31 were dissolved in 1 N potassium hydroxide. A strip of 
polyester film support, containing a mordant layer of gelatin and 
polymeric latex as above, was soaked in the alkaline solution until the 
dye was adsorbed to a density of 1.0 or greater and washed with water. It 
was then soaked in a solution of nickel (II) acetate, rinsed, soaked in an 
aqueous buffer solution at pH 4, washed with water and dried. The 
spectrophotometry was by transmission through the transparent film strip. 
TABLE II 
__________________________________________________________________________ 
DYE UNLINKED TO CARRIER 
##STR25## 
Hue Chelating 
Light 
Dye .lambda..sub.max 
1/2 BW 
Metal ion, 
Stability 
Number 
Y.sup.1 
Y.sup.11 
R.sup.8 
R.sup.9 
(nm) 
(nm) 
Me.sup.++ 
Days 
D.sub.o 
.DELTA.D 
__________________________________________________________________________ 
26 4-SO.sub.2 NH.sub.2 
CH H H 539,573 
113 Ni 5 1.40 
-.07 
27 4-SO.sub.3 H 
N H H 548,587 
120 Ni 2 2.09 
-.04 
28 H N OH CH.sub.3 
551 122 Ni 2 1.05 
-.08 
29 4-SO.sub.3 H 
N OH CH.sub.3 
543 
119 Ni 2 1.53 
-.09 
30 4-SO.sub.2 NH.sub.2 
N H H 545,580 
100 Ni -- -- -- 
31 4-SO.sub.2 NH.sub.2 
CH H CH.sub.3 
535,574 
106 Ni -- -- -- 
__________________________________________________________________________ 
Example 7--Preparation of Dye 32 
##STR26## 
4-(1-Carboxyethoxy)-1,2-naphthoquinone (0.26 g, 1.06.times.10.sup.-3 mole) 
and 2-hydrazino-5-sulfamoylpyridine (0.2 g, 1.06.times.10.sup.-3 mole) 
were added to acetic acid (5 ml), along with 2 to 3 drops of concentrated 
hydrochloric acid. After stirring for 3 hours, at room temperature, the 
mixture was filtered to remove traces of solid. The filtrate was poured 
into distilled water (30 ml) and filtered again. The precipitate was 
washed with water and air dried; yield 0.26 g (59 percent). 
Intermediates: 
##STR27## 
5-Amino-2-chloropyridine (10.0 g, 0.078 mole) was added to concentrated 
hydrochloric acid (160 ml), and the solution was cooled to -8.degree. C. 
(CH.sub.3 OH/ice bath). A solution of sodium nitrite (5.37 g, 0.078 mole) 
in water (20 ml) was added below the solution surface at a rate to 
maintain the temperature below -5.degree. C. 
Cupric chloride dihydrate (4.4 g) was added to acetic acid (160 ml) 
saturated with sulfur dioxide at 3.degree. C. 
The diazonium salt solution described above was added to the SO.sub.2 
mixture. After stirring for 15 minutes at 0.degree. C. and 30 minutes at 
room temperature, the reaction mixture was poured into ice/water (500 ml). 
The precipitate was collected by filtration and dried in vacuo at room 
temperature over calcium sulfate. The purple solid (8.8 g) was dissolved 
in tetrahydrofuran (200 ml), slurried with carbon and filtered. The 
filtrate was concentrated to an oil which crystallized to a white solid; 
yield 8.12 g (49 percent), m.p. 46.degree. to 48.degree. C. 
##STR28## 
2-Chloro-5-chlorosulfonylpyridine (2.84 g, 0.0134 mole) was added to 
concentrated ammonium hydroxide (50 ml) and the mixture was boiled. After 
adding more concentrated ammonium hydroxide (50 ml), and extending boiling 
until the reaction volume was approximately 50 ml, the reaction mixture 
was cooled in an ice bath to cause precipitation of the product. The solid 
was collected by filtration, washed with water and air dried; yield, 2.17 
g (84 percent), m.p. 153.degree. to 155.degree. C. A melting point of 
155.degree. to 156.degree. C. was observed after recrystallization from 
water. 
##STR29## 
2-Chloro-5-sulfamoylpyridine (1.0 g, 0.005 mole) was added to methanol (20 
ml) and the reaction mixture was cooled to 5.degree. C. before adding 
hydrazine hydrate (0.50 ml, 0.52 g, 0.01 mole). After stirring for 10 
minutes at 5.degree. C., the mixture was refluxed for 45 minutes. 
Additional hydrazine hydrate (1.0 ml) was added and the mixture was 
refluxed for approximately 12 hours. The reaction mixture was concentrated 
in vacuo to an oil which was slurried with 40 ml of boiling ethanol. The 
ethanol layer was collected by decantation and cooled in an ice bath to 
produce a white solid which was collected by filtration and air dried; 
yield, 0.69 g (73 percent). 
##STR30## 
To a solution of 38.0 g potassium dihydrogen phosphate in 7.5 liters of 
distilled water (pH 4.0) was added 89.4 g (0.33 mole) of potassium 
nitrosodisulfonate (Fremy's reagent). To this solution was added 
immediately a solution of 34.8 g (0.15 mole) of 
2-(4-hydroxy-1-naphthoxy)propionic acid in 125 ml ethanol. The mixture was 
stirred for 2.5 hours under nitrogen at room temperature. The yellow-brown 
solid was collected, washed with a little water and dried (under 
nitrogen). The yield was 30.0 g (81 percent). The crude product melted at 
182.degree. to 184.degree. C. 
Example 8--Photographic Test--Dye 32 
A receiving element was prepared by coating on a poly(ethylene 
terephthalate) film support (1) a metallizing layer comprising gelatin 
(1.08 g/m.sup.2) and nickel sulfate hexahydrate (0.58 g/m.sup.2), and (2) 
a receiving layer comprising a mixture of gelatin and 
poly(4-vinylpyridine) (each at 2.15 g/m.sup.2). 
The receiving element was immersed in an alkaline solution of dye 32. The 
receiver was removed from the dye solution, washed in distilled water, 
placed in a pH 6.5 buffer solution and dried. A transmission spectra was 
obtained and normalized to a density of 1.0. The .lambda..sub.max was 637 
nm, and the half band width (1/2 BW) was 130 nm. 
Example 9--Preparation of Dye 33 
##STR31## 
4-(1-Carboxyethoxy)-1,2-naphthoquinone (0.22 g, 9.times.10.sup.-4) and 
2-hydrazino-3-methoxy-5-sulfamoylpyridine (0.2 g, 9.times.10.sup.-4 mole) 
were added to acetic acid (15 ml), along with 2 to 3 drops of concentrated 
hydrochloric acid. After stirring overnight, the resulting precipitate was 
collected by filtration, air dried, slurried twice with boiling acetic 
acid (5 ml) and isolated again by filtration; yield, 80 mg (20 percent). 
Intermediates: 
4-(1-Carboxyethoxy)-1,2-Naphthoquinone 
See Example 7 above. 
##STR32## 
Sodium hydroxide (8.6 g, 0.215 mole) and 2,3-dihydroxypyridine (22.0 g, 
0.20 mole) were added to distilled water (75 ml). After cooling to 
5.degree. C., dimethylsulfate (25.0 g, 0.21 mole) was added dropwise; the 
reaction mixture was stirred for 20 hours while slowly warming to room 
temperature. The water was removed in vacuo (approximately 65.degree. C.) 
to obtain a syrup which was dissolved in concentrated sulfuric acid (50 to 
60 ml) at 5.degree. C. A cold mixture of concentrated nitric acid (20 ml) 
in concentrated sulfuric acid (20 ml) was added at a rate to maintain the 
reaction mixture between 10.degree. to 15.degree. C. After the addition 
was complete, the mixture was stirred for 30 minutes at 5.degree. C. and 
then poured onto ice (approximately 400 ml). The resulting red precipitate 
was collected by filtration and recrystallized from water; yield, 5.8 g 
(17 percent). 
##STR33## 
3-Methoxy-5-nitro-2-pyridone (5.7 g. 0.034 mole) was added to a combination 
of phosphorus pentachloride (5.0 g) and phosphorus oxychloride (40 ml); 
the reaction mixture was refluxed for 2.5 hours, cooled, poured over 
ice/water (300 ml) and stirred for 30 minutes. The resulting solid was 
collected by filtration, washed with water and air dried; yield, 1.72 g 
(27 percent), m.p. 40.degree. to 41.degree. C. 
##STR34## 
2-Chloro-3-methoxy-5-nitropyridine (1.5 g, 0.008 mole) was added to 
concentrated hydrochloric acid (15 ml) at 5.degree. C. followed by 
stannous chloride (5.0 g). The reaction mixture was stirred for 10 minutes 
at 5.degree. C., heated for 30 minutes on a steam bath, cooled, 
neutralized with aqueous sodium hydroxide (20 percent by weight) and 
extracted with 1,1,1-trichloroethane. The trichloroethane extract was 
dried over MgSO.sub.4 and evaporated in vacuo to yield a white solid; 
yield, 1.02 g (91 percent), m.p. 93.degree. to 94.degree. C. 
##STR35## 
5-Amino-2-chloro-3-methoxypyridine (0.75 g, 4.7.times.10.sup.-3 mole) was 
added to concentrated hydrochloric acid (20 ml) at -8.degree. C. followed 
by slow addition of sodium nitrite (0.33 g) in water (5 ml) below the 
surface of the reaction mixture. 
Cupric chloride dihydrate (0.3 g) was added to acetic acid (20 ml) 
saturated with sulfur dioxide at 5.degree. C., followed by rapid addition 
of the above-described diazonium solution. The reaction mixture was 
stirred in an ice bath for 10 minutes, then at room temperature for 30 
minutes and poured over ice/H.sub.2 O (approximately 200 ml) which caused 
the formation of an oil. The oil was extracted with ethyl acetate. The 
extract was dried over MgSO.sub.4 and evaporated in vacuo to yield an oil 
which was used directly for the next intermediate. 
##STR36## 
The above-described oil was added to concentrated ammonium hydroxide (10 
ml). After heating the mixture to the boiling point, an additional 10 ml 
of concentrated ammonium hydroxide was added. The reaction mixture was 
concentrated to approximately 10 ml by boiling and cooled in an ice bath. 
The resulting precipitate was collected by filtration, washed with 
distilled water and air dried; yield, 0.45 g (43 percent), m.p. 
156.degree. to 158.degree. C. 
##STR37## 
2-Chloro-3-methoxy-5-sulfamoylpyridine (0.3 g, 1.35.times.10.sup.-3 mole) 
and hydrazine hydrate (0.53 g, approximately 0.01 mole) were added to 
methanol (20 ml). After refluxing overnight, the reaction mixture was 
stripped of methanol in vacuo to yield an oil which was cooled in an ice 
bath and triturated with water (5 ml). The precipitate was collected by 
filtration and air dried; yield, 0.22 g (75 percent). 
Example 10--Photographic Test--Dye 33 
Dye 33 was mordanted and metallized as described in Example 8. Samples of 
the receiving element were buffered at pH 4.65 and 7.0 and subjected to a 
high-intensity daylight (5000 foot-candles) fading test. The percent dye 
density, measured spectrophotometrically, remaining after 2 days was 94 
percent and after 10 days was 90 percent. A transmission spectrum was 
obtained and normalized to a density of 1.0. The .lambda..sub.max was 661 
nm. 
Example 11--Preparation of Compound 16 
Dye 33 (2.08 g, 2.6.times.10.sup.-3 mole), prepared as described in Example 
9, N-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline (3.25 g, 0.013 mole) and 
2,5-Bis{[N-(3-aminophenoxycarbonyl)-N-methylamino]methyl}-3,6-didodecylben 
zoquinone (2.08 g, 2.6.times.10.sup.-3 mole) were added to 
dimethylformamide (50 ml, stored over molecular sieves) under nitrogen 
gas. After stirring for 90 minutes under nitrogen at room temperature and 
heating for 15 minutes on a steam bath, the reaction mixture was cooled 
and poured into dilute hydrochloric acid (800 ml). The precipitate was 
collected by filtration, slurried with water (200 ml), filtered and air 
dried; yield, 4.28 g (99 percent crude). The crude product was purified by 
column chromatography on silica gel, eluted with acetic acid (2 
percent)/dichloromethane, followed by 2 percent acetic acid/20 percent 
ethyl acetate in dichloromethane. 
Example 12--Preparation of Dye 34 
##STR38## 
A mixture of 2-hydrazino-3-methoxy-5-sulfamoylpyridine (0.25 g, 
1.15.times.10.sup.-3 mole) prepared as described in Example 9, 
4-isoproxy-1,2-naphthoquinone (0.26 g, 1.2.times.10.sup.-3 mole) and 
acetic acid (10 ml) was stirred for 1 hour, filtered, washed with acetic 
acid and water, and air dried; yield, 0.36 g. The crude product was 
extracted with ethanol; the extract upon chilling yielded a solid; yield, 
0.19 g (40 percent), m.p. 289.degree. C. 
Example 13--Photographic Test--Dye 34 
Dye 34 was tested for light stability in the same manner as described in 
Example 10. The results were as follows: 
______________________________________ 
pH 2 Days 10 Days 
______________________________________ 
4.65 97 percent 92 percent 
7.0 98 percent 95 percent 
______________________________________ 
A transmission spectrum was obtained and normalized to a density of 1.0. 
The .lambda..sub.max was 650 nm. 
Example 13--Preparation of Compound 17 
A mixture of 4-(1-carboxyethoxy)-1,2-naphthoquinone (0.11 g, 
4.9.times.10.sup.-4 mole), 
4-(2-hydrazino-3-methoxy-5-pyridylsulfonamido)-N,N-dioctadecyl-1-hydroxy-2 
-naphthamide (0.80 g, 8.76.times.10.sup.-4 mole) and acetic acid (10 ml) 
was stirred for 18 hours, filtered, washed with acetic acid, water and air 
dried; yield, 0.30 g. A portion of the crude product (0.25 g) was stirred 
in dichloromethane and collected again by filtration; yield, 0.15 g (31 
percent), m.p. 145.degree. C. 
Intermediates: 
4-(1-Carboxyethoxy)-1,2-naphthoquinone 
See Example 7 above. 
##STR39## 
A mixture of 2-chloro-5-chlorosulfonyl-3-methoxypyridine (0.65 g, 
2.68.times.10.sup.-3 mole) (see Example 9), 
4-amino-N,N-dioctadecyl-1-hydroxy-2-naphthamide (1.40 g, 
1.98.times.10.sup.-3 mole) and pyridine (0.20 g, 2.5.times.10.sup.-3 mole) 
was stirred overnight at room temperature. Additional pyridine (7 drops) 
was employed after the first 21/2 hours of stirring. The reaction mixture 
was concentrated in vacuo and diluted with water to precipitate an oil 
which changed to a waxy solid upon trituration with water. The waxy solid 
was dissolved in toluene and purified by column chromatography on silica 
gel using toluene. The toluene fraction was concentrated to a solid which 
was recrystallized from ethanol; yield, 0.40 g (22 percent), m.p. 
85.degree. to 87.degree. C. 
##STR40## 
A mixture of 
4-(2-chloro-3-methoxy-5-pyridylsulfonamido)-N,N-dioctadecyl-1-hydroxy-2-na 
phthamide (0.80 g, 8.76.times.10.sup.-4 mole), hydrazine hydrate (95 
percent, 0.1 g, 3.times.10.sup.-4 mole) and methanol (25 ml) was heated 
for 17 hours on a steam bath. The reaction mixture was filtered hot to 
yield 0.62 g precipitate which was dissolved in toluene and 
chromatographed on silica gel. Toluene removed the impurities and the 
product was obtained with toluene/dichloromethane (1:1) and then pure 
dichloromethane. These fractions were concentrated to an oil which was 
dissolved in ethanol and cooled to yield a solid; yield, 0.38 g (48 
percent), m.p. 99.degree. to 101.degree. C. 
Example 14--Preparation of Compound 18 
A mixture of 4-isoproxy-1,2-naphthoquinone (0.60 g, 2.8.times.10.sup.-3 
mole), 
4-(2-hydrazino-3-methoxy-5-pyridylsulfonamido)-N,N-dioctadecyl-1-hydroxy-2 
-naphthamide (Example 13, 2.0 g, 2.2.times.10.sup.-3) and acetic acid (53 
ml) was stirred for 15.5 hours at room temperature. A solid was filtered 
off, washed with water and air dried. The solid was recrystallized with 
difficulty from ligroin; yield, 0.50 g (21 percent), m.p. 108.degree. to 
110.degree. C. 
Example 15 
Tables III through VII show absorption maxima for dyes which have not been 
linked to dye-releasing carriers, but which have the structural 
characteristics of the invention. The dyes in Tables III and VII were 
mordanted and metallized as in Example 8. The dyes in Tables IV, V and VI 
were dissolved in a 1:1 dioxane/water solution containing nickel ions. The 
following absorption maxima of the dyes in solution were obtained: 
TABLE III 
__________________________________________________________________________ 
##STR41## 
Dye .lambda..sub.max 
Number 
R.sup.10 R.sup.11 
R.sup.12 R.sup.13 
R.sup.14 
(nm) 
__________________________________________________________________________ 
35 
##STR42## H H H H 610* 
36 
##STR43## H SO.sub.2 NH.sub.2 
H CH.sub.3 
645 
37 
##STR44## H CONH.sub.2 H H 634 
38 
##STR45## H CN H H 641 
39 
##STR46## H SO.sub.2 NHCH.sub.3 
H OCH.sub.3 
660 
40 
##STR47## H SO.sub.2 NHC(CH.sub.3).sub.3 
H OCH.sub.3 
661 
41 
##STR48## H SO.sub.2 NH.sub.2 
H OCH.sub.3 
650 
42 
##STR49## H SO.sub.2 NH.sub.2 
H OCH.sub.3 
651 
43 
##STR50## H 
##STR51## H OCH.sub.3 
664 
44 CH.sub.3 H 
##STR52## H OCH.sub.3 
655 
45 CH(CH.sub.3).sub.2 
H 
##STR53## H OCH.sub.3 
665 
46 
##STR54## H 
##STR55## H OCH.sub.3 
-- 
47 CH(CH.sub.3).sub.2 
H 
##STR56## H OCH.sub.3 
652* 
48 
##STR57## H 
##STR58## H OCH.sub.3 
645* 
49 
##STR59## H H H SO.sub.2 NH.sub.2 
625 
50 
##STR60## H NHSO.sub.2 CH.sub.3 
H H 625* 
51 
##STR61## H SO.sub.2 NH.sub.2 
H Cl 641 
52 
##STR62## H NH.sub.2 H H 630* 
53 
##STR63## H H H OCH.sub.3 
632* 
54 
##STR64## H SO.sub.2 NH.sub.2 
H SO.sub.2 NH.sub.2 
626 
55 CH(CH.sub.3).sub.2 
Cl H CO.sub.2 H 
H 626* 
56 CH(CH.sub.3).sub.2 
Cl H CONH.sub.2 
H 637* 
57 CH(CH.sub.3).sub.2 
H H CO.sub.2 H 
H -- 
58 CH(CH.sub.3).sub.2 
H H CONH.sub.2 
H 625* 
59 
##STR65## H SO.sub.2 CH.sub.3 
H H 634 
60 
##STR66## H CN H Cl 644 
61 
##STR67## H CO.sub.2 H H Cl 639 
__________________________________________________________________________ 
*.lambda..sub.max (1:1 Dioxane/H.sub.2 O + Ni.sup.++) 
TABLE IV 
______________________________________ 
##STR68## 
Dye .lambda..sub.max 
Number R.sup.15 R.sup.16 
R.sup.17 
R.sup.18 
(nm) 
______________________________________ 
62 
##STR69## H H H 590 
63 
##STR70## H H OCH.sub.3 
617 
64 
##STR71## H Cl H 585 
______________________________________ 
TABLE V 
______________________________________ 
##STR72## 
Dye .lambda..sub.max 
Number R.sup.19 R.sup.20 
R.sup.21 
R.sup.22 
(nm) 
______________________________________ 
65 
##STR73## H H H 626 
66 
##STR74## H H Cl 628 
67 
##STR75## H H OCH.sub.3 
646 
______________________________________ 
TABLE VI 
__________________________________________________________________________ 
##STR76## 
Dye .lambda..sub.max 
Number 
R.sup.23 
R.sup.24 
R.sup.25 (nm) 
__________________________________________________________________________ 
68 
##STR77## 
H 
##STR78## 640 
69 CH.sub.3 
H 
##STR79## 581/615 
70 CH.sub.3 
H 
##STR80## 560 
71 CH.sub.3 
H 
##STR81## 611 
72 CH.sub.3 
H 
##STR82## -- 
73 CH.sub.3 
H 
##STR83## -- 
74 CH.sub.3 
H 
##STR84## -- 
75 H 8-NHSO.sub.2 CH.sub.3 
##STR85## 665 
76 CH.sub.3 
H 
##STR86## 635 
77 CH.sub.3 
H 
##STR87## 630 
78 CH.sub.3 
H 
##STR88## 590/620 
79 CH.sub.3 
H 
##STR89## 633 
80 
##STR90## 
H 
##STR91## 648 
81 CH.sub.3 
H 
##STR92## -- 
82 
##STR93## 
H 
##STR94## -- 
__________________________________________________________________________ 
TABLE VII 
__________________________________________________________________________ 
##STR95## 
Dye .sup..lambda. max 
Number 
R.sup.26 
R.sup.27 R.sup.28 R.sup.29 
(nm) 
__________________________________________________________________________ 
83 H 
##STR96## H H 598* 
84 H 
##STR97## NHSO.sub.2 CH.sub.3 
H 612* 
85 H 8-NHSO.sub.2 CH.sub.3 
NHSO.sub.2 CH.sub.3 
H 608* 
86 OCH.sub.3 
##STR98## SO.sub.2 NH.sub.2 
H 654 
87 H 8-NHSO.sub.2 CH.sub.3 
##STR99## OCH.sub.3 
649 
88 H 8-NHSO.sub.2 CH.sub.3 
SO.sub.2 NH.sub.2 
OCH.sub.3 
648 
89 OCH.sub.3 
8-NHSO.sub.2 CH.sub.3 
SO.sub.2 NH.sub.2 
OCH.sub.3 
674 
90 H 8-NHSO.sub.2 CH.sub.3 
SO.sub.2 NH.sub.2 
OCH.sub.3 
650 
6-SO.sub.2 NH.sub.2 
91 H 8-NHSO.sub.2 CH.sub.3 
##STR100## OCH.sub.3 
651 
6SO.sub.2 NH.sub.2 
92 OCH.sub.3 
8-NHSO.sub.2 CH.sub.3 
##STR101## OCH.sub.3 
676 
93 H 8-NHSO.sub.2 CH.sub.3 
SO.sub.2 NH.sub.2 
H 623 
6-SO.sub.2 NH.sub.2 
94 H 6-SO.sub.2 NH.sub. 2 
SO.sub.2 NH.sub.2 
OCH.sub.3 
639 
95 H 7-OCH.sub.3 SO.sub.2 NH.sub.2 
OCH.sub.3 
648 
96 OCH.sub.3 
6-SO.sub.2 NH.sub.2 
SO.sub.2 NH.sub.2 
OCH.sub.3 
669 
97 OCH.sub.3 
8-NHSO.sub.2 CH.sub.3 
SO.sub.2 NH.sub.2 
OCH.sub.3 
676 
6-SO.sub.2 NH.sub.2 
98 OCH.sub.3 
8-NHSO.sub.2 CH.sub.3 
SO.sub.2 NH.sub.2 
Cl 668 
6-SO.sub.2 NH.sub.2 
99 OCH.sub.3 
8-NHSO.sub.2 CH.sub.3 
##STR102## OCH.sub.3 
683 
6-SO.sub.2 NH.sub.2 
100 OCH.sub. 3 
8-NHSO.sub.2 CH.sub.3 
##STR103## OCH.sub.3 
667* 
101 H 6-SO.sub.2 NH.sub.2 
##STR104## OCH.sub.3 
670 
__________________________________________________________________________ 
*.lambda..sub.max (3:1 Dioxane/H.sub.2 O + Ni.sup.++) 
The invention has been described in detail with particular reference to 
preferred embodiments thereof, but it will be appreciated that variations 
and modifications can be effected within the spirit and scope of the 
invention.