SULFONE COMPOUNDS AND PHOTOGRAPHIC PRODUCTS AND PROCESSES

COMPOSES AU SULFONE, ET PRODUITS ET PROCEDES PHOTOGRAPHIQUES CONNEXES

English Abstract

ABSTRACT OF THE DISCLOSURE
There are disclosed novel sulfone compounds which
are represented by the formula
<IMG>
wherein X represents the nonmetallic atoms necessary to
form a nucleus which completes a 5- or 6-membered hetaroc?lic
moiety including substituted rings and fused rings and R is
alkyl, preferably having from 1 to 6 carbon atoms, aryl such
as phenyl or substituted aryl. The compounds are useful in
photographic applications and provide controlled release of
a photographically useful material during processing of
photographic elements with an aqueous alkaline processing
composition. In particularly preferred embodiments the
sulfone compounds are utilized in diffusion transfer
photographic products and processes.

Claims

C267
1. A compound represented by the formula
<IMG>
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
<IMG>
5. A compound as definred in Claim 4 which is
represented by the formula
<IMG>
6. A compound as defined in Claim 4 which is
represented by the formula
<IMG>
-40-

7. A compound as defined in Claim 4 which is
represented by the formula
<IMG>
8. A compound as defined in Claim 4 which is
represented by the formula
<IMG>
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
<IMG>
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;

<IMG>
<IMG> and <IMG> 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; <IMG> or -SO2-NH2.
13. A compound as defined in Claim 10 which is
represented by the formula
<IMG>
wherein R1 is -OH, <IMG> 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
<IMG>
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.
-42-

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
<IMG>
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
<IMG>
27. A photographic element as defined in claim 22
wherein said compound is represented by the formula
-43-

<IMG>
28. A photographic element as defined in claim 22
wherein said compound is represented by the formula
<IMG>
29. A photographic element as defined in Claim 22
wherein said compound is represented by the formula
<IMG>
30. A photographic element as defined in Claim 16
wherein said compound is represented by the formula
<IMG>
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.
-44-

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;
<IMG> ; and <IMG> 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
<IMG>
wherein R1 is -OH, <IMG> 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
-45-

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
<IMG>
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
<IMG>
41. The product as defined in Claim 40 wherein said
compound is represented by the formula
-46-

<IMG>
42. The product as defined in Claim 40 wherein
said compound is represented by the formula
<IMG>
43. The product as defined in Claim 40 wherein
said compound is represented by the formula
<IMG>
44. The product as defined in Claim 40 wherein
said compound is represented by the formula
<IMG>
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-

47. The product as defined in Claim 36 wherein said
compound is represented by the formula
<IMG>
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; <IMG> ; and <IMG>, 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; <IMG> or -SO2-NH2.
50. The product as defined in Claim 47 wherein said
compound is represented by the formula
<IMG>
-48-

wherein R1 is -OH, <IMG> 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
<IMG>
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
-49-

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
<IMG>
60. The process as defined in Claim 59 wherein
said compound is represented by the formula
<IMG>
61. The process as defined in Claim 59 wherein
said compound is represented by the formula
<IMG>
-50-

62. The process as defined in Claim 53 wherein said
compound is represented by the formula
<IMG>
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;
<IMG> ; and <IMG> , 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, <IMG> or -SO2NH2.
65. The process as defined in Claim 62 wherein
said compound is represented by the formula
<IMG>
wherein R1 is -OH , <IMG> or SO2NH2.
-51-

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.
-52-

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
1H
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
X 11
`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
-- 6 --

'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 =
CH3

7~
N--N
~ )1 S ~CH2~ 2 - S2 - C~I3 (VII)
N
S2NH2
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.
--10

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
-12-

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
-14-

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
-15-

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
-17-

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
--19--

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.
-20-

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-
-22-

8~
CH
HC~ NH ~ O~S
CH2
, ~ 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
CH2
~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
-23-

~17'7~
~H
H2)
--(C~2!3 ~50
(CH2)3
0
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
-24-

'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 ;
-25-

(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
~/ .
-26-

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.
-27-

'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.
-28-

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
--29--

~ 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

7 7
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 ~
-32-

~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 "
33-

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
35C
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
34-

~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
36-

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.
-37-

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
-38-

~l7~3~
which are wi thin the spirit of the invention and the scope oi~
the appended claims.
. 39