CA1177082A - Sulfone compounds and photographic products and processes - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

There are disclosed novel sulfone compounds which are represented by the formula

Description

BACKGR0UND O~ T~IE INWENTION
This application relakes generally to novel compounds and, more particularly, to compounds which are us~eful in photographic applications.
It is known in the art to utllize development restrainers and development restrainer precursors in photographic applications. Of course, in photographic applications it is necessary that the desired development take place before the development restrainers or development restrainer precursors function to substantially prevent any additional development from taking place. The blocked development restrainers are designed to provide a 10 timed release of the development restrainer during the development process.
Such blocked development restrainers are disclosed, for example, in U.S. Patents3,260,597 and 3,265,498 which disclose hydrolyzable blocked restrainers; U.S.
Patent 3,698,898 ~lich discloses ~he use of quinone- or naphthoquinone-methi~e precursors which release a photographic reagent such as l-phenyl-5-mercaptotetrazole in the presence of alkali; U.S. Patent 4,009,02~ which discloses a class of cyanoethyl-containing blocked development restrainers; and German Offenlegungsschrift 2,427,813 which discloses various blocked developmentrestrainers.
The present application relates to novel sulfone compounds which are useful in photographic applications as well as photographic products and processes which utilize these compounds.
SUMMARY OF THE INVENTION
This invention seeks to provide novel sulfone compounds, which are useful in photographic applications.
In another aspect this invention seeks to provide sulfone compounds which are useful in photographic applications as blocked development restrainers.

~' .~; ~ 1 - .

~ ~t~ ~3 ~ ~
In a further aspeck this invention seeks to provid~ sulfone compounds which allow controlled release o~ a photographically useful material during processing of a photographic element In still another aspect this invention seeks to provide photographic products and processes utilizing such sulfone compounds.
BRIEF SUMMARY OF THE INVENTION
Thus in accordance with a first aspect of the invention are provided compounds which are represented by the formula N - C - S - (CH2)2 ~ S2 ~ R

FORMULA A
wherein X represents the nonmetallic atoms necessary to form a nucleus which completes a 5- or 6-membered heterocyclic moiety including substituted rings and fused rings and R is alkyl, preferably having from 1 to 6 carbon atoms, aryl such as phenyl or napthyl, or substituted aryl. The aryl moiety may be substituted, preferably in the para position, with substituents such as, for example, alkyl, halogen, electron donating groups such as alkoxy or dialkyl-amino and electron withdrawing groups such as acetyl and nitro.
In a second aspect this inven~ion provides a photographic element comprising a support and at least one layer thereon containing a silver halide emulsion having associated therewith a compound represented by the formula , X ~
N _ C - S - (CH2)2 - S02 - R

wherein X represents the nonmetallic atoms necessary to form a nucleus which completes a 5- or 6-membered heterocyclic moiety and R is alkyl, aryl or subs*ituted aryl.

. ~ ~
~ ~ ~ - 2 _ In a third aspect this invention provides a photographic product for use in forming a multicolor diffusion trans:Eer image comprising a photo-sensitive element comprising a support carrying a blue-sensitive silver halide emulsion having a yellow dye developer associated therewith, a green-sensitive silver halide emulsion having a magenta dye developer associated therewith and a red- sensitive silver halide emulsion having a cyan dye developer associated therewith, a second sheet-like element positioned in superposed or superposable relationship with said photosensitive element, an image-receiving layer posi-tioned in one of said elements~ a rupturable container releasably holding an 10. aqueous alkaline processing composition adapted, when distributed between a pair of predetermined layers carried by said photosensitive element and said second element, to develop said silver halide emulsions and provide a multi-color diffusion transfer image on said image receiving layer, at least one of said photosensitive and second elements including a compound represented by the formula .~X~
N _ C - S - ~CH2~2 - S02 - R

wherein X represents the nonmetallic atoms necessary to form a nucleus which completes a 5- or 6-membered heterocyclic moiety a~d R is alkyl, aryl or substituted aryl, In a fourth aspect this invention provides a diffusion trans:Eer photographic process comprising exposing a film unit comprising a photo-sensitive element and a second element, said photosensitive element comprising a support carrying at least one silver halide emulsion having image dye-providing material a.ssociated therewith~ applying an aqueous alkaline processing composition to sai.d exposed photosensi~ive element to effect development and to form an imagewise distribution of image dye-providing material as a function of development and transferring at least a portion of said imagewise _ 2a -distribution of image dye-providing material to an image receiving layer in superposed or superpossable relationship therewith to thereby provide a diffusion transfer image, at least one of said photosensitive and second ele-ments including a compound represented by the formula ,- X ~
N - - - C-S-~CH2)2-S02-R

wherein X represents the nonmetallic atoms necessary to form a nucleus which completes a 5- or G-membered heterocyclic moiety and R is alkyl, aryl or substituted aryl, The sulfone compounds of the invention are generally azoles which cleave in alkaline compositions to provide mercaptoazoles which are diffusible in aqueous alkaline photographic processing compositions. The preferred heterocyclic rings within the formula include groups where the heterocyclic atoms, - 2b -7~
i.e., atoms other than carbon, are members o~ a sinyle heter~-cyclic ring rather than used or condensed heterocyclic rings wherein the hetexocyclic atoms are members of more than one heterocyclic ring. The compounds include monoazoles such as benzoxazoles, benzothiazoles, etc.; imidazoles; triazoles such as 1,2,4-triazoles/ benzotriazoles, etc.; tetrazoles and pyri-midines. The most preferred heterocyclic rings are tetrazoles and a particularly preferred heterocyclic ring is a phenyl substituted tetrazole. Where ths heterocyclic moiety is substi-tuted the substituent~s) may be attached to either a nitrogen atom or a carbon atom o~ the azole moiety.
The sulfone moiety of the compounds provides a timed release of a photographically useful material in the alkaline environment typically encountered in the processing of photographic elements and particularly where the alkaline medium has a pH in the range of from about 12 to about 14.
The ra~e of release is dependent upon the hydroxyl ion concentration and therefore the rate of release incxeases as the pH increases. Upon cleavage of the molecule the heterocyclic ring taken together with the sulfur atom provides a photographically use~ul material. The cleavage reaction occurs according to the following sequence:

~X~ ~X~
C-S~ (CH2) 2S2R ~ N CH2 CH SO2R
CH2--CH~SO2R OH ~ CH2~CH-SO2-R

The rate of release of the substituted phenylmercapto-azole moiety is also temperature dependent, that is, more is released as the temperature at which processing of the film unit is effected rises. Thus, more o~ the mercaptoazole '7(~

moiety is made available at elevated temperatures, i.e.l above room temperature, where more is typically desired, less is released at r~om temperature and even less below room temperature where lesser amounts are needed. Thus, these blocked compounds which are utilized according to the invention provide more uniform sensitometry for the film units of the invention over a wide temperature range of processing. In other words, the sensitometry of the film units which include such blocked compounds according to the invention is less temperature d~pendent than would otherwise be the case.
In one preferred embodiment such as, for example, where the azole moiety is a phenyl substituted tetrazole, the compounds of the invention are useful in photographic applications as blocked development restrainers. When incorporated into a photographic element these compounds permit initial development to occur during processing of the element with an aqueous alkaline processing composition and then undergo cleavage to substantially restrain further development. Upon cleavage o~ the molecule th~ hetcrocyclic ring taken together with the sulfur atom provides a silver halide development restrainer. As mentioned above, the sul~one moiety provides timed release of the development restrainer moiety in the alkaline environment encountered during photographic processing~ When the azole moiety is substituted with a phenyl xing the latter may be attached to a nitrogen atom or a carbon atom.
A preferred group of compounds according to the invention are those which are useful in diffusion transfer photographic applications and which are represented by the formula -~ ~ x-- ~
N ¦-. C~S-~C~2)2-SO2-R

Rl FORMULA B

wherein Rl is either a group which has a pKa of from about 7 to about 14, preferably at least about 8.5 or higher, which is ionizable to an anion and wherein the silver salt of the mercaptan resulting from cleavage of the -CH2-CH2-SO2-R
group is rendered more soluble in the pH range within which Rl is ioni~ed to an anion than it is below that pH ranye, or a precursor of such a group. Typical ~uitable substituents O O
which are useful as Rl include: -OH; -e-CH3; ~O-C-CH3; -SO~NH2;

-SO2NHCH3; -SO2NHC8H17; NHSO2C 3; 2 ~ CH3, and N-OH
-~-Z where Z is alkyl having from 1 to 10 carbon atoms, aralkyl such as benzyl or phenethyl, phenyl or substituted phenyl. Up4n cleavage o~ the molecule as described above there is provided a photographically u~eful material which provides desirable results such as will be described in detail below herein.
As stated above, Rl may also be a precursor of a substituent which has the requisite properties and the desired substituent may be formed in situ. For example, it is possible to incorpor~te in the film unit as a precursor a compound within Formula B which has a hydrolyzable ester group on the phenyl ring and generate the desired hydroxy ~L7~

group in situ during photographic processing. It should be noted here that the acetyl group which can be substitu~ed on the phenyl ring does not ionize to any appreciable extent to form an anion in an aqueous alkaline processing cornposition. However, the presence in a film unit of a compound within Formula B having an acetyl group substituted on the phenyl ring can provide advantageous results. It would appear that the compound under-goes a change in aqueous alkaline processing composition and that the acetyl substituent is a precursor of a group which has the requisite properties described above which provide the desired results.
A diffusion transfer photographic system wherein development of an exposed photosensitive element with an aqueous alkaline processing composition is effected in the presence of a compound represented by the formula ,-N

`1~ c - s - Y
~ .

Rl where Y is H, an alkali metal or a group which is cleavable in Q
photographic aqueous alkaline processing composition is disclosed and claimed in copending Canadian patent application of Avinash C. Mehta, George H. Nawn and Lloyd D. Taylor, No. 393,496; see also United States patent 4~390,613.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Preferred compounds according to the invention are represented by the formulas '7~

N--N
s ~CH2~ 2 - S2 3 (I) N

~3 N --N
N ~1 - S- (CII2) 2 - S~)2 ~) (II) N

0 \o)L 5 (C~{2) 2 - 502 ~ (III) N--N
oJL S- ~C112) 2 ~ 52 C113 ~IV) I --N

N~ ~ - S- (CH2) 2 - SO, - CH3 (V) ~1 , OH
N--N
)I s (CH2) 2 - S2 ~- C~I3 (VI) C =

7~

N--N
~ )1 S ~CH2~ 2 - S2 - C~I3 (VII) N

N--N
J ~ CH2 ) 2 ~- SO~-- C H ( VI I I ) N
OH

~C~2) 2 S2~ (IX) );~ N

~ N~

S (c~i~) 2 - so2-cH3(X) J~N
~S~ ' '7~2 The sulfone compounds of the lnvention typically exhibit very good release kinetics in solution. The tl/2 times 7 in solution, i.e., the time required for one-half of the molecules to undergo cleavage and release the mercapto-heterocyclic azole moiety, for some of the compounds illustrated above are shown in Table l. These data were obtained using l x 10-4 molar concentrations in 30% acetonitrile/0.25 N aqueous KOH solution at a temperature of 22 i 0.1C.
TABLE I
~OMPOUND tl/2(sec) I 0.94 II 0.165 III 0.274 IV 1.02 The compounds of the invention may be prepared by reactions which are known to those skilled in the art. For example, the compounds within Formula A may be formed by reaction of the appropriate heterocyclic thiol with the appropriate vinyl sulfone derivative, usually in the presence of a suitable basic catalyst. Compounds within Formula ~ may be prepared by first preparing the appropriate substituted heterocyclic thiol and reacting it with the appropriate vinyl sulfone compound.
The sulfone compounds may be present in the photo-graphic elements of the invention in any appropriate location and in any amount which is required to accomplish their intended purpose. The amount necessary in any particular 7~

instance is dependent upon a number of ~actors such as, ~or example, the compound utilized, the type of photographic element, the location o~ the compound in the photographic element and the result desired. Routine scoping tests may be used to ascertain the concentration appropriate for any given photographic element. In a preferred embodiment of the invention, the sulfone compounds are incorporated in diffusion transfer photographic film units as will be discussed in more detail below herein. In such film units the compounds may be incorporated in either the photosensitive element or the image-receiving element.
The novel sulfone compounds of the invention may be utilized in any photographic system wherein the presence of a development restrainer is desired during processing.
The compounds can be utilized in various layers of a multilayer photographic system to ensure ~he desired distribution of the development restrainer during processing As disclosed previously, the compounds which are within Formula B are particularly use~ul in dif~usion transfer photographic system~. Ge~erally such compounds can provide desirable results when the dif~usion transfer photographic processing is carried out at room temperature and particularly where the processing is carried out at elevated temperature, e.g., about 95F. These desirable results include a speed increase for one or more of the silver halide emulsions in a multicolor diffusion transfer process and, a the same time, an increase in the DmaX of one or more of the individual colors due to control o~ fo~ development. As pointed out above, these blocked compounds provide more uniform sensitometry ov~r a wide temperature xange o~ processing.

J ~'7'7~

The advantageous results obtained ~hrough the use o~
the substituted mercaptoaæole compounds according to the invention are not completely understood. However, to further aid those skilled in the art to understand and practice the invention, S the proposed theoretical mechanism by which the advantageous results axe thought to be effected will be discussed here. It should be understood, however, that the diffusion transfer pho~ographic system has been proved to be operative and highly effective through extensive experimentation and the proposed theoretical mechanism is not to be construed as being limiting of the invention.

Y

-lOA-It is theorized that such results are obtainable because the compounds which are released as a result of the cleavage of the sulfone moiety dwring processing perform different functions at different stages of the developmenk process, that is, as weak silver solvents and promoter~ of development at one stage of the development process and as development restrainers, or inhibitors, at another stage of the process, and that the dual functions of these compounds within the diffusion transfer photographic system are pH
dependent.
It is well known that in the diffusion transfer development process the pH of any particular location within the film unit varies with time. Typically, the processing composition employed in the process has a very high pH, e.g., from about 13-14 and during the development process each layer of the multilayer film unit goes through a broad pH
range which includes very high pH levels and relatively low pH levels. When the pM is substanl-ially equal to or abovo the pKa of the substituent Rl on the phenyl ring, the dianion is formed, for example, N - N
Il N ~ S~

and acts as a weak silver solvent to form relatively soluble silver salts, thus promoting development. When ~he pH falls below the pKa of the substituent Rl, the monoanion is formed, for example, ~7~7~2 N - N
11 ILS~
~ ,~
N
~., Rl and the silver salt of the monoanion o~ the compound is very low in solubility resulting in a developm~nt restrainer action.
In view of the foregoing, it will be understood that when it is desired to utilize both ~unctions, development of the exposed photosensitive element in the presence of the compounds o~ Formula B is carried out with a procassing composition having a pH substantially equal to or abo~e the pKa of the particular substituent, at least for some period of time, when the processing composition comes into contact with the compound so as to enable the sulfone moiety to cleave and the substituent (Rl) to ionize to ~orm the dianionO
In addition, at some polnt during the development process, the pH of the envi~onment where the compo~nd i5 located will go below the pKa of the substituent so as to enable the monoanion to be formed agaln. Of course, if it is desired to utiliæe only the development restrainer effect a processing composition having a pH lower th~n the pKa of the substituent could be used.
The sulfone compounds of the invention may be used in conjunction with any photographic emulsion. It is preferred to use these compounds in a diffusion transfer photographic system, particularly one which includes a negative working silver halide emulsion, i.e., one which 7'~ 2 develops in the areas of expos~re. Fur~her these compounds may be used in association with any image dye-providiny materials. In a particularly preferred embodiment the diffusion transfer photographic film elements of the invention include one or more image dye-providing materials which may be initially diffusible or nondiffusible. In diffusion trans~er photographic systems the image dye-providing materials which can be utiliæed generally may be characterized as either ~1) initially soluble or diffusible in the processing composition but which are selectively rendexed nondiffusible imagewise as a function of development; or

(2) initially insoluble or nondiffusible in the processing composition but which selectively provide a di~fusible product imagewise as a function of development. The image dye-providing materials may be complete dyes or dye intermediates, e.g., color couplers. The requisite differential in mobility or solubility may be obtained, for example, by a chemical reaction such as a redox reaction, a coupling reaction or a cleavage reaction. In a particularly preferred embodiment of the invention the imag~ dye-provid.ing materials are dye developers which are initially diffusible materials. The dye developers contain, in the same molecule, both the chromophoric system Qf a dye and a silver halide developing function as is described in U. S. Patent 2,983,606.
Other image dye-providing materials which may be used include, for example, initially diffusihle coupling dyes such as are use~ul in the diffusion transfer process described in U. S.
Patent 3,087,817 which are rendered nondiffusible by coupling with the oxidation product of a color developer; initially nondiffusible dyes which release a diffusible dye following -7~

oxidation, sometimes referred to as "redox dye releaser" dyes, described in U. S. Patents 3,725,062 and 4,076,529; initially nondiffusible image dye-providing materials which release a diffusible dye following oxidation and intramolecular ring closure as are described in UO S. Patent 3,433,939 or those which undergo silver assisted cleavage to release a diffusible dye in accordance with the disclosure of U. S. Patent 3,719,489;
and i~itially nondi~fusible image dye-providing materials which release a diffusible dye following coupling with an oxidized color developer as described in U. S. Patent 3,227,550.
The effect obtained upon any individual image dye-providing material will be dependent, at least in part, upon the distance between the sulfone compound and the image dye-providing material in the film unit.
The sulfone compounds may be incorporated into the photographic elements by any suitable technique. The compounds can be incorporated in the photographic element typically by being coated ~rom a water or oil dispersion and the layer~s) in which they reside typically include a binder material such as gelatin or the like~
~n a pre~erred embodiment of the invention, the sulfone compounds are utilized in diffusion transfer photo-graphic film units in conjuction with initially diffusible dye developers as the image dye-providing materials. As des-cribed in U.S. Patent 2,983,606 a photosensitive element containing a dye developer and a silver halide emulsion is photoexposed and a processing composition applied thereto, for example, by immersion~ coating, spraying, flowing, etc., in the dark. The exposed photosensitive element is super-posed prior to, during, or after the processing composition is applied, on a sheet-like support element which may be utilized as an image-receiving element~ In a pr~ferred embodiment, the processing composition is applied -to the exposed photosensitive element in a substantially uniform layer as the photosensitive element is brought into swper-posed relationship with the image-receiving layer. The processing composition, positioned intermediate the photo sensitiva element and the image-rece~ving layer, permeates the emulsion to initiate development of the latent image contained therein. The dye developer is immobilized or precipitated in exposed areas as a consequence of the development of the latent image. This immobilization is apparently, at least in part, due to a change in the solu-bility characteristics of the dye developer upon oxidation and especially as regards its solubility in alkaline solutions.
It may also be due in part to a tanning effect on the emulsion lS by oxidized developing agent, and in part to a localized exhaustion of alkali as a result of development. In unexposed and partially exposed areas of the emulsion, the dye developer is unreacted and diffu~ible and thus provides an imagewise distribution of unoxidized dye developer, diffusible in the processing composition, as a ~unction of the point-to-point degree of exposure of the silver halide emulsion. At least part o~ ~his imagewise distribution o~ unoxidized dye developer is transferred, by imbibition, to a superposed image-receiving layer or element, said transfer substantially excluding oxi-dized dye developer. The image-receiving layer receives a depthwise diffusion, from the developed emulsion, of unoxidized dye developer without appreciably disturbing the imagewise distribution thereof to provide a reversed or positive color ima~e of the developed image. Th image-receiving element may contain agents adapted to mordant or otherwise fix the difused, unoxidized dye developer. In a preferred embodiment of said U.S. Patent No. 2,983,606 and in certain commercial applications thereof, the desired positive image is revealed by separating the image-receiving layer from the photosensitive element at the end of a suitable imbibition period. Alternatively, as also disclosed in said U.S. Patent No. 2,983,606, the image-receiving layer need not be separated from its superposed contact with the photosensi-tive element, subsequent to transfer image formation, if the support for the image-receiving layer, as well as any other layers intermediate said support and image-receiving layer, is transparent and a processing composition containing a substance, e.g., a white pigment, effective to mask the developed silver halide emulsion or emulsions is applied between the image-receiving layer and said silver halide emulsion ox emulsions. .
Dye developers, as noted in said U.S. Patent No.
2,983,606, are compounds which contain, in the same molecule, both the chromophoric system of a dye and also a silver halide developing function. By "a silver halide developing function"
is meant a grouping adapted to develop exposed silver halide~
A pre~erred silver halide development function is a hydro-quinonyl group. In general, the development ~unction includes a benzonoid developing function, that isl an aromatic developing group which forms quinonoid or quinone substances when oxidized Multicolor images may be obtained using dye developers in diffusion transfer processes by several techniques. One such technique contemplates obtaining multicolor transfer images utilizing dye developers by employment of an integral multilayer photosensitive element, such as is disclossd in the aforementioned U.S. Patent No. 2,983,606 and in U.S. Patent No.

3,345,163, wherein at least two selectively sensiti2ed photo-sensitive strata, superposed on a single support, are processed, ~:1'7'~3~

simultaneously and without separation, with a sinyle common image-recei.ving layer. A suitable arrangement o~ this type omprises a support carrying a red-sensitive silver halide emulsion stratum, a green-sensitive silver halide emulsion stratum and a blue-sensitive silver halide emulsion stratum, said emulsions having associated therewith, respectively, for example, a cyan dye developer, a magenta dye developer and a yellow dye developer. The dye developer may be utilized in the silver halide emulsion stratum, ~or example in the form of particles, or it may be disposed in a stratum behind the appropriate silver halide emulsion strata. Each set of silver halide emulsion and associated dye developer strata may be separated from other sets by suitable interlayers, for example, by a layer or strat~m of gelatin or polyvinyl alcohol.
In certain instances, it may be desira~le to incorporate a yellow filter in front of the green-sensitive emulsion and such yellow filter may be incorporated in an interlayer.
However, where desirable, a yellow dye developer o~ the appro-priate spectral characteristics and present in a state capable of functioning as a yellow filter may be so employed and a separate yellow filter omitted.
Particularly useful products for obtaining multi-color dye developer images are disclosed in U.S~ Patent No.
3,415,644. This patent discloses photographic products wherein a photosensitive elament and an image-receiving element are maintained in fixed relationship prior to exposure, and this relationship is maintained as a laminate after processing and image formation. In these products, the final image is viewed through a transparent (support) element against a light-reflecting, i.e., white background. Photoexposure is made through said transparent element and application of the processing composition provides a layer of light-reflecting material to pxovide a whi~e background. The light-xeflecting material ~referred to in said patent as an "opacifying agent") is preferably titanium dioxide, ar.d it also performs an S opacifying function, i.e., it is effective to mask the developed s.ilver halide emulsions so that the transfer image may be viewed without interference therefrom, and it also acts to protect the photoexposed silver halide emulsions from post-exposure fogging by light passing through said transparent layer if the photoexposed film unit is removed from the camera before image-formation is completed.
U.S. Patent No. 3,647,437 is concerned with improve-ments in products and processes disclosed in said U.S. Patent No. 3,415,644, and discloses the provision of light-absorbing materials to permit such processes to be performed, outside of the camera in which photoexposure is effected, under much more intense ambient light conditions. A light-absorbing material or reagent, preferably a pH-sensitive phthalein dye, is pro-vided so positioned and/or constituted as not to interfcre ~ with phokoexposure but so positioned between the photoexposed silver halide emulsions and the transparent support during processing after photoexposure as to absorb light which other-wise might fog the photoexposed emulsions. Furthermore, the light-absorbing material is so positioned and/or constituted after processing as not to interere with viewing the desired image shortly after said image has been formed. In the pre-ferred embodiments, the light-absorbing material, also sometimes reEerred to as an optical filter ay~nt, is initially contained in the processing composition together with a light-reflecting material, e.g., titanium dioxide. The concentration of the light absorbing dye is selected to provide the light '7~

transmission opacity required to per~orm ~he particular process under the selezted light conditions.
In a particularly useful embodiment, the light-absorbing dye is highly colored at the pH of the procsssing composition, e.g., 13-14, but is substantially non-a~sorbing of visible liyht ~t a lower pH, e.g., less than 10-12. This pH reduction may be effected by an acid-reacting reagent appropriately positioned in the film unit, e.g., in a layer between the transparent support and the image-receiving layer.
The dye developers are pr~ferably salected for their ability to provide colors that are useful in carrying out subtractive color photography, that is, the previously mentioned cyan, magenta and yellow. The dye devslopers employed may be incorporated in the respective silver halide emulsion or, in the preferred embodiment, in a separate layer behind the respective silver halide emulsion, and such a layer of dye developer may be applied by use o~ a coating solution containing the respective dye developer distributed, in a con¢entration calculated to give the desired coveraye of dye developer per unit area, in a film-~orming nakuxal, or syn thetic, polymer, ~or example, yelatin, polyvinyl alcohol, and the like, adapted to be permeated by the processing composition~
Other diffusion transfer products and processes in which the dye developers of the present invention may be utilized are described in U.S. Patents 3,573,043 and 3,594,1~50 For convenience, the entire disclosure of each of the six patents referred to immediately above is hereby incorporated by reference herein.
A particularly useful film unit according to the invention i5 one wherein the photosensitive element includes LD~

a light-refl~cting layer between the silver haiide la~er and the image dye-providing material layer (as described in Canadian Patent 668,592), the substrate of the photosensitive element carries the polymeric acid neutralizing layer which in turn carries the timing layer (as described in U.S. Patent 3,573,043) and the processing composition includes an oximated polydiacetone acrylamide thickening agent (as described in U.S. Patent 4,202,694).
In a preferred diffusion transfer film unit according to the invention a development restrainer precursor of the invention is incorporated in the photosensitive element in a layer between the support of the element and the silver halide emulsion closest to that support. This structure combines a delay in the cleavage of the material with a delay in the diffusion of the released development restrainer through the film unit.
In another preferred multicolor diffusion transfer film unit accordiny to the invention a development restrainer precursor of the invention is incorporaked in the magent~
dye developer layer and in a top coat gelatin layer of the photosensitive element and the film unit is processed with a processing composition which includes 4-hydroxy phenlymercaptotetrazole. Excellent photographic results have bee~ obtained utilizing compound I in a film unit of this type and processing over a wide temperature range, i.e. 13~C, 24C
and 35C.
The invention will now be described ~urther in detail with re.spect to specific preferred embodiments by way of examples, it ~eing understood that these are illustrative on~y and the invention is not intended to be limited to the materials, 3a conditions process parameters, etc. which are recited therein.
All parts and percentages are by weight unless otherwise indicated.

r~

EXAMPLE :[
PREPARATION O~ ~OMPOUND I
Phenylmercaptotetrazole (30 g, 0.168m) was stirred under dry nitrogen with 210 ml of dry methanol and to the mixture there was added methyl vinyl sulfone (17.8 g, 0.168 m) followed by 5 ml of Triton B~ (a 40% solution of benzyl-trimethylammonium hydroxide in methanol available from Eastman Organic Chemicals). The mixture was refluxed for 25 hours and allowed to cool and stand at room temperature for 2 hours. The crystalline solid which formed was filtered off and the filter calce washed clean with cold methanol.
The material was allowed to air dry and was recrystallized from 150 ml of methyl cellosolve to give the desired product as white plates. The product was collected by filtration, washed with cold methanol and dried to constant weight to give 20.7 g (44% yield) of compound I, m.p. 14ll-11~6C
N4O2S2CloH12 requires 42.2Ll% C, 4.25% H, 19.70% N and 22.55% S. Elemental analysis found 1l2.26% C, 4.32% H, 19.63% M
and 22.45% S.
The structure of the desired product was confirmed by NMR and IR spectra.
EXAMPLE II
The sodium salt Or l-phenyl-lH-tetrazole~5-thio (69 g, 0.344m) was stirred under dry nitrogen with chloroethyl phenyl sulfone (72 g~ 0.344 m) in 475 ml of dry methanol. The mixture was refluxed for 24 hours, cooled and the precipitated sodium chloride removed by filtration. The filtrate was evaporated off and the residual gum stirred with ether until the product crystallized. The yellow solvent was decanted and the process repeated several times until the ether was colorless.
~Trade Mark - 21 -7t~

The crystalline material was dissolved in acetone, precipitated into water, collected by filtration and air dried. The crystalline material was then recrystallized from 1 liter of dry metha~ol and filtered at the boiling pointO Upon cooling heavy white needles were deposited~ Irhe needles were collected by filtration, washed with cold methanol and dried to constant weight to give 63.5 g ~53~ yield) of compound II, m.p. 104-5C.
N4O2S2C15H14 required 52.01% C, 4.07~ ~I, 16.17% N
and 18.51~ S. Elemental analysis found 51.99~ C, 4.17% H, 16.05% N and 18.54% S.
The structure of the desixed product was confirmed by NMR and IR spectra.
ExaMPLE III
As a control a film unit (A) was prepared as follows:
The negative element of the film unit comprised an opaque subcoated polyethylene terephthalate film base on which the following layers were coated in succession:
(1) a layer of sodium cellulose sulfate coated at a coverage of about 21 mgs/m2;
(2) a cyan dye developer layer comprising about 635 mgs/m of cyan dye develop r represented by the fo~m~l-8~

CH
HC~ NH ~ O~S

, ~ N=C C--N
f~ ~OH ~ H3 HO~ ~ S02~N~I--CH
~ \ / ~,/~, C~'2 l N - Cu -N
CIH3 ~ ~ C ~ C ~ HO
HC -N~ - O2S ¦ N I Cd 52 - NH - fH

~0~1 H ~
about 429 mgs./m.2 of gelatin, about 238 mgs./m.2 of dodecylaminopurine and about 128 mgs./m.2 of 4~ methyl phenyl hydroquinonei (3) a red-sensitive gelatino silver iodobromide tl.8 microns) emulsion layer coat~d at a coverage o~ about 1500 mgs/m2 of silver and ahout 900 mgs/m2 of gelatin;
(4~ an interlayer comprising about 2000 mgs/m2 of a 60-30-4~6 tetrapolymer of butylacrylat~, diacatone acryl-amide/ styrene and methacrylic acid and about 15 mgs~m2 of polyacrylamide;
~5~ a magenta dye developer layer comprising about 646 mgs/m2 of a magenta dye developer represented by the formula ~17'7~

~H
H2) --(C~2!3 ~50 (CH2)3 about 323 mgs~m2 of gelatin and about 150 mgs/m2 of dodecylaminopuri~e;
(6) a green-sen~itive silver iodobromide (1.11 microns) emulsion layer coated at a coverage of about 700 mgs/m of silver and about 308 mgs/m of gelatin;
(7) a green-se~sitive silver iodobromide (l. 8 micronsJ
emulsion layer coated at a coverage of about 600 mg~./m2 of silver and about 288 mgs./m~2 of gelatin;
(8) an interlayer comprising about 1200 mgs./m2 of a 60-30-4-6 tetrapolymer of butylacrylate, diacetone acryl-amide, styrene and methacrylic acid and about 15 m~s./m.2 of polyacxylamide;
(9) a spacer layer comprising about 207 mgs./m~2 of 2-phenylbenzimidazole and about 150 mgs./m.2 of gelatin;
(lO~ a yellow dye developer layer comprising about 820 mgs./m. of a yellow dye developer represented by the formula '7~

.OC3~17 NO2 C3~70~ ~11c~

~ Cr ~ ~l2 0/ \o 01~

C~C1l2~3 OH
and about 328 mg~/m of gelatin;
(11) a blue-sensitive silvex iodo~romide layer coated at a coverage of about 960 mgs/m2 of silveri about 615 mgs/m2 of gelatin; and about 306 mgs/m2 of 4'-methyl phenyl hydroquinone; and (12) an overcoat layer made up of about 484 mgs/m2 of gelatin.
The image-receiving element comprised a transparent subcoated polyethylene terephthalate film base on which the following layers were coated in succession:
(1) as a polymeric acid layer approximately 9 parts of a 1/2 butyl ester of polyethylene/maleic anhydride copolymer and 1 part of polyvinyl butyral coated at a coverage of about 2450 mgs/ft2 (26,372 mgs/m2);
(2) a timing layer coated at a coverage of about 800 mgs/ft2 (8611 mgs/m2) of a graft copolymer comprised of diacetone acrylamide (DAA), acrylamide (AA), betacyanoethy-acrylate (BCEA) and acrylamidopropane~ulfonic acid (APSA) grafted onto polyvinylalcohol (PVA) at a ratio DAA/AA/BCEA/APSA/PVA o-f 2.1/0.34/0.19/0.01/1 ;

(3) a polymeric image receiviny layer coated at a coverage of about 10 mgs/Et2 (108 mgs/m ) o~ 1,4-hutanediol diglycidyl ether and about 300 mgs/~t~ t3229 mys/m2) of:
(a) 3 parts of a mixture of 2 parts polyvinyl alcohol and l part poly-4-vinylpyridine and (b) l part of a gra~t copolymer comprised of 4-vinylpyridine (4VP) and vinyl benzyl trimethyl ammollium chloride (TMQ) grafted OlltO llydroxye~hyl cellulose (HEC) at a ratio HEC/4VP/TMQ of 2.2/2.2/1 ; and

(4) a topcoat layer of polyvinyl alcohol coated at a coverage of about 40 mgs/~t2 (430 mgs/m2).
The film unit was processed with a processing composition made up as follows:
Water 1642 ml TiO2 1520.0 grams Oximated polydiacetone acrylamide 32.0 Potassium hydroxide ~45% solution~ 451.4 Benzotriazole 22.0 4-aminopyrazolo-(3,4-d)pyrimidine 10.0 6-methyl uracil 12.0 N-hydroxyethyl-N,N',N'-tris-carboxymethyl ethylene diamine 30.0 Polyethylene glycol (M.W. 4000) 18.0 Bis(2-aminoethyl)sulfide 0.8 Colloidal silica (30~ solids) 37.0 N-phenethyl-~-picolinium bromide (50% solids) 102.0 50;~-C16~33 .0 U

1~ 11 ~/ .

7~7~

0~1 01 C18~37 ~ ~
\ / 62.3 IJ

The film unit was exposed (1/2 meter-candle-second) on a sensitometer to a test exposure scale, or step wedge, with white light and then processed at room temperature (24C) by passing it through a pair of rollers set at a gap spacing of about 0.0030 inch. The ~ilm unit was kept intact and viewed through the base of the image-receiving element.
An identical ~ilm unit was processed in the same manner at 34C. The neutral density columns of the images were read on a densitometer to obtain the DmaX and Dmin values ~or red, green and blue, respectively. In addition, the speed of the red, green and blue curves, respectively, (defined as the negative log o~ the relative exposure required to give red, green and blue absorption in the neutral column a reflection density of 0.75~ was measured.
The values obtained are shown in Table II~
EXAMPLE IV
... . _ The experiment described in Example III was repeated with the exception that in the film unit used (Film Unit B~, the negative element did not include any dodecylaminopurine (an antifoggant) in the cyan and magen~a dye developer layers.
The reflection densities and relative speeds of the neutral areas of the images are listed in Table II.

'7~

It is seen that the removal of the dodecylamino-purine from the cyan and magenta dve develsper layers of the negative eleme~t resulted in the red, green and blue DmaX
being significantly lower at 35C and slightly lower at room temperature.
EXAMPLE V
The experiment described in Example I was repeated with Film Units C-H. These film units did not include any dod~cylaminopurine in the cyan and magenta dye developer layers and in layer (1~ oE the negative, the sodium cellulose sulate was replaced by a layer comprising a development restrainer precursor of the invention dispersed in about 33 mgs/m of inert bone gelatin as follows:
FILM UNIT COMPOUND AMOUNT (MGS/M2) C I 20.5 D I 61.5 E II 25.0 F II 74.9 G III 25.0 H III 74.9 The layer containing the blscked development restrainer was coated in the form of a solid dispersion in water including the gelatin and minor amounts of a dispersing agent and a thickener.
~5 The re~lection densities and relative speeds of -the neutral areas of the images are listed iIl Table II.

7~

u~ r ~ L~ r o ~1 ~1 ~1 ~1 _I ~ ~ ~1 O ~ ~1 0 r~l O ~ ~J
a~ ....... ~q ....... .
~ ~~:J ~~ ~ ~ ~ ~ ~ ~ ~Y N ~ ~
a) ~
alI~ O ocn ~ ,~ r a) ,, ~ ~ r.) ~ ,1 ,J 1~
~O ~1 ~10 0 ~ ~ ~ ~ O ~ ~1 ~ ~ ~1 ~ ~1 U~ ~ ~ . " . . . . . Q ~.7 . . .
~ ~ ~ ~ ~ ~ ~ ~ u~ r ~i .
cr ~ ~ ~ 1-- u~ ~ ~1 ~ ,1 ~ o oo ~ ~r 1`
O ~ ~~1 0 0 ~ O ~ ~1~ ~ ~ ~1 0 ~ ~1 . . .. . . . . ~; P:; ~ .
~I t~`1 ~ N ~ ~ ~~ ~I N

~J ~ ~ ~ N
m . ~ ..... m .......
. o o o o O o o o o o o O o o o o ._-H ~J ~ ~ N ~ I ~ ~ t~
~ ~ t~
I O O O O O O O O a% O t, O O O O O O
~ ~ ~ ,~ ~ ~ ~ ~ ~ ,1 a~ o o o o E-l ~ ~ ~ ~J ~ ~ N VI ~J ~1 ~ ~ J N
~; . . . . . . ~ . P~ ~ . .
O O O O O O O O O O O O O O O O
t.) C~) ~ ~1 a~ ~1 ~1 ~1 ~ o ~1 ~ ~J r~ o ~1 o~ o m ..... , ~ ~ m ~ .... ~ .

~`J~1 ~ Hl~ O~ ~ r-l N U) U') I~ 111 O r~l X ¦ W ~ ~)~ ~~I N X ¦ ~ ~ 1~ O ~1 0 r-l O O
I ~~ C ~ I N ~i ~

O ~ ~ ~ ~1 ~1 ~1 ~ O O O ~1 0 0 ~ ~ . p~

E~
~I H
H Z
m o ~ m ~ m ~ w ~ 7~ ~ ~

It can be s~en tha~ in comparison to Film Unit B, which did not include any anti~oggant, the sulfone compounds of the invention served to incrsase the red, green and blue DmaX significantly at 35C and slightly at room temperature.
It is also apparent that there is no or only a minimal lo~s in the relative red, blue and green speeds due to the presence of the sulfone compounds. These data illustrate the contxolled release propexties of the compounds.
EXAMPLE_VI
A catalyst was prepared by stirring a mixture o~
Celite ~ (10 g.) (diatomaceous earth available from Johns Manville) and potassium fluoride dihydrate (15 g.) in 250 ml.
of distilled water for 30 minutes. The water was removed and the solids dried overnight at room ~emperature under high vacuum. The catalyst was further dried in a vacuum oven at 58-60C for about two days.
To a stirred solution of 1-(4-hydroxyphenyl)-5-mercaptotetrazole (5 g.) in dry tetrahydro~uran (50 ml.) at room temperature under nitrogen there were added methylvinylw sulfone (2.8 g.) and the potassium/Celite catalyst (1~
The reaction mixture was stirred slowly for 24 hours. The precipitate which formed was removed by filtration and the solvent was removed from the filtrate leaving behind a clear yellow-brown oil. Th~ oil was dried under vacuum to give a tacky gum-like material. Recrystalli2ation from meth~nol followed by drying to constant weiyht under vacuum gave a white solid, compound V, m.p. 139-141C.
The NMR spectrum of the material was consistent with compound V. 13CNMR (dmso~d6): ~159.28, 153.6~, 126.28, 124.05, 116.23, 53.01, 40.59, 25.29 ppm.

~30 E~MPLE VII
As a control a film unit was prepared as ~ollows:
the negative element comprised an opaque subcoated polye~hylene terephthalate film base on which the following layers were coated in succession:
1. as a polymeric acid layer approximately 9 parts of a 1/2 butyl ester of polyethylene/maleic anhydride copolymer and 1 part of polyvinyl butyral coated at a coverage of about 26,460 mgs./m.2;
2. a timing layer comprising about 97~ of a 60-29-6-4-0.4 pentapolymer of butylacrylate, diacetone acrylamide, methacrylic acid, styrene and acrylic acid and about 3% poly-vinlyalcohol coated at a coverage of about 3000 mgs./m.2;
3. a cyan dye developer layer comprising about 511 mgs.jm.2 of the cyan dye developer described in Example III, about 70 mgs.~m. of 4'methyl phenyl hydroquinone and about 317 mgs./m.2 of gelatin;
4. a red-sensitive silver iodobromide emulsion layer comprising about 1378 mgs./m.2 O~ silver and about 827 mgs./m.2 of gelatin;

5. an interlayer comprising about 2090 mgs./m.2 of the pentapolymer des~ribed in layer 2, about 110 mgs./m.2 o~
polyacrylamide and about ~4 mgs./m.2 of succinaldehyde;

6. a magenta dye developer layer oomprising about 460 mgs./m. of the magenta dye developer described in Example III and about 210 mgs./m.2 of gelatin;

7. a green~sensiti~e silver iodobromide emulsion layer compr sing about 723 mgs./m.2 O~ silver and about 318 mgs./m. of gelatini -~ ~ 7)7~8~

8. an interlayer comprising ~bout 1881 mgs7/m.2 of the pentapolymer described in layer 2 and about 99 mgs./m.2 of polyacrylamide;

9. a yellow dye developer layer comprising about ~89 mgs./m.2 of the yellow dye develoepr describ~d in Example III and about 265 mgs./m.2 of gelatin;

10. a blue~sensitive silver iodobromide emulsion layer comprising about 764 mgsO/m.2 of silver, about 499 mgs./m.2 of gelatin and about 265 mgs./m.2 of 4'-mekhyl phenyl hydroquinone; and

11. a topcoat layer of 400 mgs./m.2 of gelatin.
The image-receiving element comprised a transparent subcoated polyethylene terephthalate film b~se upon which there was coated an image receiving layer coated at a coverage of about 300 mgs./~t.2 (3229 mgs./m.2) of: (a) 3 parts of a mixture of 2 parts polyvinyl alcohol and 1 part poly 4-vinylpryidene and (b) 1 part of a graft copolymer comprised f 4-vinylpr~idene (4VP) and vinyl benzyl trimethyl ammonium chloride tTMQ) grafted onto hydroxyethyl cellulose (HEC) at a ratio HEC/4VP/TMQ of 2.2/2.2/1; and about 5 mgs./ft (53.8 mgs./m. ) of 1,4-butar.ediol diglycidyl ether.
The film unit was process with a processing composition made up as E ~

~7'~

Water 1632 ml TiO2 2312.0 grams Oximated polydiacetone a~rylam~de 32.0 Potassium hydroxide (45% solution) 468.0 "
Benzotriazole 22.0 "
4-aminopyrazole~(3,4-d)pyrimidine 10.0 6-methyl uracil 12.0 "
N-hydroxyethyl-N,N',N'-triscarboxymethyl ethylene diamine 30.0 "
Polyethylene glycol (M.W. 4000) 18~0 "
Bis(2Qaminoethyl)sulfide 0.8 Colloidal silica (30% solids) 37.0 "
N-phenethyl-a-picolinium bromide (50% solids) 102.0 "
Allopurinol 3-3 2-methyl imidazole 23.8 "
6-methyl-5-bromo azabenzimidazole 4.8 "
~-SO2-~16~33 ~ 1'1.0"

~ 0~
~00~ }lOC~
C lf~H370 6~.3 "

The negative element was exposed ~2 me~er-candle-seconds) on a sensitometer to a test exposure scal~ with white light, and then brought together with the image receiving element and process~d at room temperature (24C) by passing the film unit through a pair of rollers set at a gap spacing of about 0.0026 inch. ~he film unit was kept intact and viewed through the base of the image receiving element.
An identical ~ilm unit was processed in the same manner a~ 35C. The neu~ral density columns o~ the images were read on a densitomater to obtain the Dmax and Dmin values ~or red, green and blue, respectively. The values obtained are shown in Table III.
Two film units according to the invention were pre-pared. These were identical to the control with the exception that in one (Film Unit VII A) the negative also included a top coat layer comprising about 20 mg./ft~ (215 mgs./mO2) o~
compound V and about 20 mg./ft.2 of gelatin and in the other ~Film Unit VII B) the negativ~ includcd a top coat laycr com-prising about 20 mgs./ft.2 of compound VII and about 20 mgs./ft.2 of gelatin. The ~ilm units were processed as described above at 25C and at 35C. The results obtained are shown in Table III.
TABLE III
. _ 2~C
EILM Dmax Dmin UNIT R G B R G B
Control1.81 1.601.31 0.15 0.16 0.24 VIIA 1.60 1.481.40 0.18 0.17 0.24 VIIB 1.33 1.431.41 0.15 0.16 0.23 Dmax Dmin R G B R G B
Control1.43 1.200~95 0.16 0.17 0.25 VIIA 1.32 1.231.12 0.16 0.17 0.24 VIIB 1.07 1.131.11 0.16 0.17 0.25 ~L~'7~7~

It can be seen that in compari~on to the Control, Film Units VIIA and VIIB exhibited a small increas~ in the blue Dmax at room temperature and a larger incr~ase in the blue Dmax at 35~C.
- EXAMPLE VIII
PREPARATION OF COMPOUND VII
_ . .
To a suspension of 4-sulfonamido phenylmercaptotetrazole (2.166g, 8.43mmol) in methanol (10 ml) there were added, under nitrogen, 78~ methyl vinyl sulfone (1.44g, 8.42 mmol) and 0.25 ml of 40% benzyl trimethyl ammonium hydroxide in methano,l and the reaction mixture refluxed for twenty-four hours. The cooled reaction mixture was filtered to collect the white crystals which had formed. Thin layer chromatography showed that some starting materials were present. The desired product, compound VII, was separated by column chromatography follow~d by removal of the solvent, crystallization on standing and drying. The structure of thP product was confirmed by UV
and 13C NMR spectra.
EXAMPLE IX
PREPARATION OF COMPOUND IX
. . . _ . _ _ . . .
A mixture o~ 28 g. ~0.17 m.) of 2-hydr~zinobenza-thiazole and 23 g. (0.17 m.) of phenylisothiocyanate in 125 g.
of 1,2,4-txichlorobenzene was stirred under dxy nitrogen for 3-1/2 hours at reflux. The resulting yellow solution was allowed to cool and stand overnight. A cry3talline material precipitated out. The contents of the reaction vessel were stirred well, diluted with 100 ml. of dry benzene and the crystalline solid collected by filtration, washed with dry methanol, dried in air and then vacuum dried over potassium hydroxide to give 32 g. (91.5% yield) of a white crystalline solid ~35 Sl~

J~N
~N >~
S

m.p. 240-241C.
A mixture of 20.7 g. of the previous product and 5.6 g. of potassium hydroxide in 400 ml. of dry methanol was S stirred under dry nitrogen. The crystalline solid dissolved gradually and a fine white solid was suspended in the solvent.
The reaction mlxture was r~fluxed for 1 hour, cooled, 12.5 g.
of bromoethanol added and the mixture stirxed at reflux for 8 houxs. The reaction mixture was allowed to cool and stirred overnight. The resulting precipitate was collected by filtra-tion, washed well with water and dried under vacuum to give 28.4 g. of product, m.p. 159-161C.
The solid was recrystallized from 500 ml. of methyl cellosolve (peroxide free), filtered at the boiliny point through diatomaceous earth, and the Eiltrate cooled. The resulting crystals were collected and dried ko give 12 y. of S-(C~ OH

~S>~

m~p. 163-164C.
The filtrate was concentrated to about 2/3 of its volume, chilled ~nd allowed to stand overnight. The resulting crystals were collected and dried to give 3 g. of the product, m.p. 163-164C.
A mixture o 30 g. of the alcohol and 34.5 g. of triphenylphosphine in 1 liter o~ dry dimethylformamide was stirred under nitrogen at room temperature and to it there was added bromine (about 7 ml.) dropwise, while keeping the temperature under 40C, until the bromine orange color persisted. The mixture was stirred overnight. The reaction mixture was stirred into 4 volumes of an ice water mixture.
The resulting white crystalline solid was collected by filtration, washed with water and air-dried. The solid was then dissolved in 500 ml. of warm methyl cellosolve and the solution stirred into 1 liter of methanol. The needle-like solid which precipi~a~ed out was collected, washed with cold methanol and dried under vacuum to give 16 g. of S-~CH~)2 Br N

~s>~N

m~p. 120~121C.
A mixture of 3.1 g. of the pre~ious produçt and 2 g.
of benzenesulfinic acid sodium salt in 25 ml. of dry dimethyl~
sulvoxide was stirred in an oil bath at 75C for 3 hours.
Thin layer chromatography of the reaction mixture showed the absence of the starting bromine compo~md. The reaction mixture was cooled and stirred into 4 volumss of cold water.
The resulting white crystalline solid was collected by filtration, washed with methanol and dried over potassium hydroxida to give an off-white solid. The solid was recrystal-lized from 75 ml. of methyl cellosolve ~peroxide free) and filtered at the boiling point to give 2 g. of needle~like material, m.p. 155-157C. The product was recrystallized once from methyl cellosolve and once from n-butanol to give 1.3 g. of compound C, m.p. 161-162C.

1~7'7~

C~6H13N3O2S3 requir~s 51,18~ C; 3.49~ Hi ll.lg% N
and 25.62% S, Elemental analysis o~ the product ~ound 51.26%C;
3.55% H; 11.18% N and 25.76% S.
EXAMPLE X
PREP~RATION ~F COMPOUND X
A mixture of 5.5 g. of 2)2 N

~ >~N
and 2.1 g. of methansulfinic acid sodium salt in 50 ml. of dry dimethylsulfoxide was stirred at a temperature of 75-77C
under dry nitrogen for 3 hours. Thin layer chromatography of the reaction mixture showed no presenc~ of the starting bromine material. The cooled reaction mixture was poured into 150 ml.
of cold water and after a few minutes a white solid precipi-tated out. The solid was collected by filtration, washed with water, air-dried and recrystallized from 85 ml. of methyl cellosolve. The solution was filtered at the boiling point.
The needle like material which ~ormed in the ~iltrate was collected by filtration, washed wi.th dry methanol and vacuum dried over phcsphorous pentoxide to give 3.5 g. of compound D, m.p. 194-195C. The structure of the compound was confirmed by IR spectrum.
CllHllN3O2S3 requires 42.16% C; 3.54~ H; 13.41% N
and 30.69% S. Elemental a~alysis o the product found 42.37% C;
3.63% H; 13.30~ N and 30.35% S.
Although ~he invention has been described with respec-~ ~o speci~ic preferred embodiments it is not intended to be limi~ed thereto but rather those skillsd in the art will recognize that variations and modifications may be made therein ~l7~3~

which are wi thin the spirit of the invention and the scope oi~
the appended claims.

. 39

Claims (67)

1. A compound represented by the formula wherein X represents the nonmetallic atoms necessary to form a nucleus which completes a 5- or 6-membered heterocyclic moiety and R is alkyl, aryl or substituted aryl.

2. A compound as defined in Claim 1 wherein R is alkyl having from 1 to 6 carbon atoms.

3. A compound as defined in Claim 1 wherein R
is phenyl.

4. A compound as defined in Claim 1 which is represented by the formula

5. A compound as definred in Claim 4 which is represented by the formula

6. A compound as defined in Claim 4 which is represented by the formula

7. A compound as defined in Claim 4 which is represented by the formula

8. A compound as defined in Claim 4 which is represented by the formula

9. A compound as defined in Claim 4 wherein X
represents the nonmetallic atoms which complete a tetrazole ring.

10. A compound as defined in Claim 1 which is represented by the formula wherein R1 is either a group which has a pKa of from about 7 to about 14 which is ionizable to an anion and wherein the silver salt of the mercaptan resulting from cleavage of the -(CH2)2-SO2-R group is rendered more soluble in the pH range within which R1 is ioniæed to an anion than it is below that pH range, or a precursor thereof.

11. A compound as defined in Claim 10 wherein R1 is selected from the group consisting of -OH;

-?CH3; -O?-CH3; -SO2NH2; -SO2NHCH3; -SO2NHC8H17; -NHSO2CH3;

and wherein Z is alkyl having from 1 to 10 carbon atoms, aralkyl, phenyl or substuted phenyl.

12. A compound as defined in Claim 10 wherein R1 is -OH; or -SO2-NH2.

13. A compound as defined in Claim 10 which is represented by the formula wherein R1 is -OH, or -SO2 - NH2.

14. A compound as defined in Claim 13 wherein R
is alkyl having from 1 to 6 carbon atoms.

15. A compound as defined in Claim 13 wherein R is phenyl.

16. A photographic element comprising a support and at least one layer thereon containing a silver halide emulsion having associated therewith a compound represented by the formula wherein X represents the nonmetallic atoms necessary to form a nucleus which completes a 5- or 6-membered heterocyclic moiety and R is alkyl, aryl or substituted aryl.

17. A photographic element as defined in Claim 16 wherein R is alkyl having from 1 to 6 carbon atoms.

18. A photographic element as defined in Claim 16 wherein R is phenyl.

19. A photographic element as defined in claim 16 wherein said compound is located in a layer between said support and the silver halide emulsion closest to said support.

20. A photographic element as defined in Claim 16 wherein said layer containing said silver halide emulsion has associated therewith an image dye-providing material.

21. A photographic element as defined in Claim 20 wherein said image dye-providing material is a dye developer.

22. A photographic element as defined in Claim 16 wherein said compound is represented by the formula

23. A photographic element as defined in Claim 22 wherein R is alkyl having from 1 to 6 carbon atoms.

24. A photographic element as defined in Claim 22 wherein R is phenyl.

25. A photographic element as defined in Claim 22 wherein X represents the nonmetallic atoms which complete a tetrazole ring.

26. A photographic element as defined in Claim 22 wherein said compound is represented by the formula

27. A photographic element as defined in claim 22 wherein said compound is represented by the formula

28. A photographic element as defined in claim 22 wherein said compound is represented by the formula

29. A photographic element as defined in Claim 22 wherein said compound is represented by the formula

30. A photographic element as defined in Claim 16 wherein said compound is represented by the formula wherein R1 is either a group which has a pKa of from about 7 to about 14 which is ionizable to an anion and wherein the silver salt of the mercaptan resulting from cleavage of the -(CH2)2-SO2-R
group is rendered more soluble in the pH range within which R1 is ionized to an anion than it is below that pH range, or a precursor thereof.

31. A photographic element as defined in Claim 30 wherein R1 is selected from the group consisting of -OH;

-O?-CH3; -?-CH3; -SO2NH2; -SO2NHCH3; -SO2NH C8H17; -NH SO2 CH3;

; and wherein Z is alkyl having from 1 to 10 carbon atoms, aralkyl, phenyl or substituted phenyl.

32. A photographic element as defined in Claim 30 wherein R1 is -OH; -C-CH3 or -SO2NH2.

33. A photographic element as defined in Claim 30 wherein said compound is represented by the formula wherein R1 is -OH, or -SO2NH2.

34. A photographic element as defined in Claim 33 wherein R is alkyl having from 1 to 6 carbon atoms.

35. A photographic element as defined in Claim 33 wherein R is phenyl.

36. A photographic product for use in forming a multicolor diffusion transfer image comprising a photosensitive element comprising a support carrying a blue-sensitive silver halide emulsion having a yellow dye developer associated therewith, a green-sensitive silvex halide emulsion having a magenta dye developer associated therewith and a red-sensitive silver halide emulsion having a cyan dye developer associated therewith, a second sheet-like element positioned in superposed or superposable relationship with said photosensitive element, an image-receiving layer positioned in one of said elements, a rupturable container releasably holding an aqueous alkaline processing composition adapted, when distributed between a pair of predetermined layers carried by said photosensitive element and said second element, to develop said silver halide emulsions and provide a multicolor diffusion transfer image on said image receiving layer, at least one of said photosensitive and second elements including a compound represented by the formula wherein X represents the nonmetallic atoms necessary to form a nucleus which completes a 5- or 6-membered heterocyclic moiety and R is alkyl, aryl or substituted aryl.

37. The product as defined in Claim 36 wherein X
represents the nonmetallic atoms which form a tetrazole ring.

38. The product as defined in Claim 36 wherein R
is alkyl having from 1 to 6 carbon atoms.

39. The product as defined in Claim 36 wherein R
is phenyl.

40. The product as defined in Claim 36 wherein said compound is represented by the formula

41. The product as defined in Claim 40 wherein said compound is represented by the formula

42. The product as defined in Claim 40 wherein said compound is represented by the formula

43. The product as defined in Claim 40 wherein said compound is represented by the formula

44. The product as defined in Claim 40 wherein said compound is represented by the formula

45. The product as defined in Claim 36 wherein said second element includes said image receiving layer carried by a transparent support and said processing composition includes titanium dioxide.

46. The product as defined in Claim 45 wherein said compound is located in said photosensitive element in a layer between said support and the silver halide emulsion closest to said support.

47. The product as defined in Claim 36 wherein said compound is represented by the formula where R1 is either a group which has a pKa of from about 7 to about 14 which is ionizable to an anion and wherein the silver salt of the mercaptan resulting from cleavage of the -(CH2)2-SO2-R group is rendered more soluble in the pH range within which R1 is ionized to an anion than it is below that pH range or a precursor thereof.

48. The product as defined in Claim 47 wherein R1 is selected from the group consisting of -OH;

-?-CH3; -O-?CH3; -SO2NH2; -SO2NHCH3: -SO2NHC8H17;

-NHSO2CH3; ; and , wherein Z is alkyl having from 1 to 10 carbon atoms, aralkyl, phenyl or substituted phenyl.

49. The product as defined in Claim 47 wherein R1 is -OH; or -SO2-NH2.

50. The product as defined in Claim 47 wherein said compound is represented by the formula wherein R1 is -OH, or -SO2NH2.

51. The product as defined in Claim 50 wherein R is alkyl having from 1 to 6 carbon atoms.

52. The product as defined in Claim 50 wherein R
is phenyl.

53. A diffusion transfer photoyraphic process comprising exposing a film unit comprising a photosensitive element and a second element, said photosensitive element comprising a support carrying at least one silver halide emulsion having image dye-providing material associated therewith, applying an aqueous alkaline processing composition to said exposed photosensitive element to effect development and to form an imagewise distribution o image dye-providing material as a function of development and transferring at least a portion of said imagewise distribution of image dye-providing material to an image receiving layer in superposed or superposable relationship therewith to thereby provide a diffusion transfer image, at least one of said photosensitive and second elements including a compound represented by the formula wherein X represents the nonmetallic atoms necessary to form a nucleus which completes a 5- or 6-membered heterocyclic moiety and R is alkyl, aryl or substituted aryl.

54. The process as defined in Claim 53 wherein the photosensitive element comprises a support carrying a blue-sensitive silver halide emulsion layer having a yellow image dye-providing material associated therewith, a green-sensitive silver halide emulsion layer having a magenta image dye-providing material associated therewith and a red-sensitive silver halide emulsion layer having a cyan image dye-providing material associated therewith.

55. The process as defined in Claim 54 wherein said image dye-providing materials are dye developers and said emulsions are negative working emulsions.

56. The process as defined in Claim 55 wherein R
is alkyl having from 1 to 6 carbon atoms.

57. The process as defined in Claim 55 wherein R
is phenyl.

58. The process as defined in Claim 53 wherein X
represents the nonmetallic atoms which complete a tetrazole ring.

59. The process as defined in Claim 53 wherein said compound is represented by the formula

60. The process as defined in Claim 59 wherein said compound is represented by the formula

61. The process as defined in Claim 59 wherein said compound is represented by the formula

62. The process as defined in Claim 53 wherein said compound is represented by the formula wherein R1 is either a group which has a pKa of from about 7 to about 14 which is ionizable to an anion and wherein the silver salt of the mercaptan resulting from cleavage of the -(CH2)2-SO2-R group is rendered more soluble in the pH range within which R1 is ionized to an anion than it is below that pH range, or a precursor thereof.

63. The process as defined in Claim 62 wherein R1 is selected from the group consisting of -OH;

-?-CH3; -O-?-CH3; -SONH2; -SO2NHCH3; -SO2NHC8H17; -NHSO2CH3;

; and , wherein Z is alkyl having from 1 to 10 carbon atoms, aralkyl, phenyl or substituted phenyl.

64. The process as defined in Claim 62 wherein R1 is -OH, or -SO2NH2.

65. The process as defined in Claim 62 wherein said compound is represented by the formula wherein R1 is -OH , or SO2NH2.

66. The process as defined in Claim 65 wherein R is alkyl having from 1 to 6 carbon atoms.

67. The process as defined in Claim 65 wherein R
is phenyl.