Note: Descriptions are shown in the official language in which they were submitted.
~(~5~
POSITIYE-~ORKI~G I~MOBILE P~IOTOGRA~HIC COMP~UN~S
~ND PHOTOGRAPHIC ELE~IE~TS CONl`AI~ING SAME
This invention relates ~o r.ew compour.ds, photograp~ic
elements and processes for for~.ing image records in pnoto-
graphic elements. In one aspect, this invention relates to
image dye-providing materials which are immobile or ballast-
ed compounds as incorporated into photographic elements. In
another aspect, this invention relates to dye image-provid- -
ing materials which can be used in image transfer film units.
It is known in the art to use image dye-providing
materials in photographic elements such as image transfer film
units. Image dye-providing materials which are initially
mobile in the film units have been employed, for example,
such as the mobile couplers and developers disclos~d in U.S.
Patent 2,698,244 where a dye is synthetized in the receiver
layer. Preformed mobile dyes which Teact with mobile oxidiz-
ed color developers are disclosed in U.S. Patent 2,774,668.
i Further disclosures of the use of mobile preformed dyes are
found in U.S. Patent 2,983,606. However, the initially
mobile dye image-providing materials have certain disad~-antages
in photographic elements: They can diffuse prematurely to
adjacent layers thereby affecting interimage color reproduc-
tion and they can remain reactive when diffusing through
adjacent layers after development thereby causing drop-off
in color scales.
Image dye-providing materials which are initially
immobile in a photographic element or are ballasted overcome
several of the problems with initially mobile compounds. The
dyes could be temporarily baliasted by a heavy counter ion such
as a barium salt as disclosed in U.S. Patent 2,756,142. The
dyes can contain a removable ballast group as described ir.
Canadian Patent 602,607 and U.~. Patents 3~227J~5~ ana 3,62~,~52.
Compounds which undergo intramolecular ring closure upon o~ida-
105;~10
tion to split off a dye are disclosed in U.~. ~atents 3,443,~9,3,443,5~40 and 3,~43,941. Improved initially immobile compounds
which ~Indergo a redox reaction followed by alkali cleavage to
split off a dye or dye precursor moiety are disclosed in Belgian
Patent 788,268. However, these image dye-providing materials
are generally limited in application because the dye is releas-
ed in the areas where oxidation takes place. Thus direct- .
positive silver halide emulsions or some other reversing mech-
anism, such as use of development nuclei in layers adjacent
the recording layer, are used if a positive transfer image is
desired.
It would be desirable to provide an image dye-providing
material which is lnitially immobile or ballasted in a photo-
graphic element to prevent premature movement, and have this
material function to provide a positive transfer image with
a simple negative silver halide emulsion. Moreover, it would
be desirable to provide an image dye-providing material where-
in the diffusing material is relatively inert to further reaction
in the photographic element after it is released from the parent
compound.
We have now discovered a class of compounds which can be
used in photographic elements and in processes for producing
image records which overcome many inherent limitations of the
systems known in the art. These compounds are immobile or
ballasted compou~ds which can undergo a reaction such as a
nucleophilic displacement reaction in their reduced form to
release a mobile and diffusible photographically useful moiety.
The compounds can be oxidized, such as by a redox reaction in a
photographic element, to lower substantially the rate of release
of the photographically useful moiety. Thus, the compounds can
be used to provide a positive transfer image from negative sil-
ver halide emulsions. In one embodiment of this invention the
compound has a m.oiety which is released upon nucleophilic dis-
.
1~)5~S~O
placement to provide a mobile image-~ye or image-d~re precursor.
The photographic elements of this invention include a
support having thereon at least olle alkali-permeable layer
which layer colltains an immoDile compound having a photo-
graphically useful moiety such as an image-dye or image-dye
prècursor. ~he immobile compound is capabie or releasing
the photographically useful moiety under alkaline conditions
and is capable of reaction with an imagewise pattern of an
oxidized silver halide developing agent before su~stantial
release of said photographically useful moiety occurs, to low-
er substantially the rate of release of the photographically
useful moiety under alkaline conditions.
The compounds of this invention when used in photo-
graphic elements generally have a rate of release of the
photographically useful moiety which rate is slower than the
rate at which the compounds react with oxidized silver halide
developing agent, but faster than the rate of fog formation in
the unexposed areas of the photographic element. The rate of
fog formation can be controlled by using slowly developing
silver halide emulsions or the use of addenda which restrain
or suppress further development after the initial imagewise
development has occurred. Typical useful addenda to suppress
further development include antifoggants, development restrainers
and hydrolyzable precursors thereof.
In one embodiment, the compounds of this invention are
organic compounds which contain 1) an oxidizable nucleophilic
group and 2) an electrophilic group which is located between
a moiety which is photographically useful and another moiety
which functions as a ballast for the compound. When the
compounds are used in a photographic system, the nucleophilic
group functions by reacting at the electrophilic group, dis-
placing either the ballast moiety or the photographically use-
iOS~ ~0 _ 4 _
ful moiety from the compound. The photographically useful moietyupon release from the ballast moiety can thcn diffuse within the
immediate layer, to adjacent layers or to receiver elements where
it can carry out its ~unction in the system. ~owever, where the
nucleo~hilic group is oxidized, such as by redox reaction with
an oxidized silver haiide developer, the electrophilic group
remains substantially unaffected by the oxidized nucleophilic
group and the photographically useful moiety remains immobile and
nondiffusible in its initial location.
The compounds of this invention are especially useful in
photographic systems where the photographically useful moiety
is an image dye-providing material such as a dye or dye pre-
cursor. When the compounds are incorporated in a photographic
element in association with a silver halide emulsion, the com-
pounds function to provide a positive transfer of image dye-
providing material with a negative silver halide emulsion.
Since the compounds are ballasted or immobile as incorporated
in the photographic element, additional parameters of control
are provided with resultant improved image quality. In certain
preferre~ embodiments, a dye can be released which can diffuse
through adjacent layers with a minimum of interaction ~ith silver
halide or other compounds in the adjacent layers. S~ill another
advantage is attained in certain embodiments where a shifted
or preformed dye can be released from an immobile compound
associated with a negative silver halide emulsion to produce
an image record without the necessity of oxidation reactions
on the receiver sheet, such as is required with oxichromic
compounds, leuco compounds, and color couplers which generally
require oxidation reactions to provide the image dye.
In a preferred embodiment, this invention relates to
photographic elements which include a support having thereon
a red-sensitive silver halide emulsion having assoclated there-
with an int.zmolecular nucleophilic dicpl~cement compound hav-
ing a cyan image dye-providing moiety, a layer containing a
~?5~SlO - 5-
green-sensitive silver hali~e emulsioJl having associated there-
with an intramolecular nucleophilic displacement compound hav-
ing a ~.agenta image dye-providing moiety, and a layer con-
taining a blue-sensitive silver halide emulsion having asso-
ciatecl therewith an intramolecular nucleophilic displacement
compound having a yellow image dye-providing moiety.
In a specific embodiment in accordance with this inven-
tion, a photographic film unit is provided which is adapted
to be processed by passing the unit between a pair of juxta-
posed pressure-applying members, such as would be found in a
camera designed for in-camera processing. The unit comprises 1)
a photosensitive element which contains a silveT halide emulsion
having associated therewith an immobile intramolecular nucleo-
philic displacement compound having an image dye providing
moiety, 2) an image dye-receiving layer, 3) means for discharg-
ing an alkaline processing composition within the film unit
such as a rupturable container which is adapted to be position-
ed during processing of the film so that a compressive force
applied to the container by the pressure-applying members will
effect a discharge of the container's contents within the film,
and 4) a silver halide developing agent which is soluble in
alkaline processing composition located within said film unit.
; In still another embodiment, this invention relates to
a new process whereby an alkaline processing composition is
applied to an imagewise-exposed photographic element includ-
ing a support having thereon at least one layer containing a
photographic recording material, such as silver halide, and
at least one layer thereon containing a nondiffusible compound
having a photographically useful moiety. The compound being
capabl~ of releasing the photographically useful moiety under
alkaline conditions, and also being capable of reaction with
an oxidi~ed developing agent for said photographic recording
material, wherein the reaction product has a substantially
lQ5'~0
~ower rate of release of the photographically useful group.
The process also includes providing the developing agent ~or
the photographic recording material duri~lg application of the
alkali.ne processing composition under conditions to effect
ima~ewise release of the photographically useful moiety as
an inverse Iunction of development oi the photograp;lic recording
material, whereby an image record is obtained in the photographic
element.
ln a highly preferred embodiment, this invention relates
to a photographic transfer process of:
a) treating an exposed photographic eler,lent which
includes a support havi.ng thereon at least one
alkali-permeable layer which layer contains an
immobile compound having a photographically use-
ful moiety with an alkaline processing composi-
~ tion in the presence of a silver halide develop-
: ing agent to effect development of each of the
exposed silver halide emulsion layers, thereby
oxidizing the developing agent;
. b) cross-oxidizing the immobile compound by the
oxidized developing agent as a function of
development before substantial release of the
photographically useful moiety occurs whereby
the cross-oxidation substantially reduces the
rate of release of the photographically useful
.~ moiety.
c) maintaining the photographic element in an alkaline
medium for a time sufficient to release the photo-
graphically useful moiety from the immobile compound
which has not reacted with the developing agent; and
whereby at least a portion of the photographically
useful moiety provides a positive image record.
105;~ 0 ,7,
In this highly preferred embodiment, the photographically
usefull moiety is preferably an image dye or image-dye precursor.
The photograp}lic transfer process is preferably carried out in
an in1:egral negative-receiver image t.ansfer element ha~ing
the image-receivin~ layer and the photographic recording layers
coated on the same support. Preferably an opaque layer which
is reflective to light is located between the receiving layer
and the recording layers. The alkaline processing composi-
tion can be applied between the outer recording layers of the
photographic element and a cover sheet which can be transparent
and superposed before exposure.
Reversal images can be readily obtained with photo-
graphic elements of this invention, and especially those ele-
ments which contain a immobile compound which contains a hydro-
ly~able precursor or the nucleophilic group. The elements
can be first developed with a developing agent in an environment
having a pH below that necessary to hydrolyze the precursor for
the nucleophilic group; then the photographic element can be
fogged, light-flashed, and developed in a solution having a
pH suffiriently high to effect intramulecular nucleophilic
displacement of the immobile compounds.
Generally, the immobile compounds contain a nucleophilic
group a~d an electrophilic group so chosen that, when the
compound is incorporated into a photographic element, the rate
of oxidation of the nucleophilic group is substantially great-
er than the rate of intramolecular nucleophilic displacement
:
or cleavage at the electrophilic group. Since the rate of
oxidation is substantially greater than the rate of nucleo-
philic displacement, an imagewise pattern of the more mobile
group will be produced after displacement; i.e., where the
compound contai~s an image dye wh~ch is diffusible after
nucleophiliG displacement, an image record can be observed
in layers adjacent the layer of initial location of the com-
10526~0 _ ~~ound. Ceneral.y, tl~a~ will be ~t 'e~st 1~ ~nd pre~erablr
at least 100~ more of the nucl~ophilic displacement in the un-
oxidized areas than in the oxidized areas, and preferably there
is substantially no nucleophilic displacement in the areas of the
photographic element where all of the compound is oxidized.
~here dyes or dye precursors are released, generally at least
two times ~nd preferably at least five time~ more dye or dye
precursor is released in the unoxidized areas than in the OXi~lZ-
ed areas.
In ~ertain highly preferred embodiments, the compounds
of this invention contain a group which is a hydrolyzable pre-
cursor for the oxidizable nucleophilic group, for example,
a hydrolyzable precursor for a hydroxylamine group. In com-
pounds where the nucleophilic group is blocked, the possibility
of premature reactions' releasing the photographically useful
moiety is substantially eliminated. Moreover, by controliing
the development conditions, the availability of the nucleophilic
group for reaction and intramolecular nucleophilic displacement
can be delayed, if desired.
In certain preferred embodiments, the compounds of this
invention are defined as intramolecular nucleophilic displace-
ment compounds. The term "intramolecular nucleophilic dis-
placement" is understood to refer to a reaction in which a
nucleophilic center attached to a compound reacts at another
site on the compound, which is an electrophilic center, to
effect displacement of a moiety attached to the electrophilic
g~roup. Generally, the intramolecular nucleophilic displace-
ment compounds are those compounds which have the nucleophilic
group and the electrophilic group juxtaposed by the three-
dimensional configuration of the molecule to promote close
proximity of the groups where~y the reaction can take place.
~enerally, the respective electrophilic and nucleophilic groups
can be put on any compound where the groups are held in *he pos-
- lOS'~10 - 9
sible reactioll ~o~itlons, lnclu~in~ ~olymc3ic compounas, maoro-
cyclic compounds, polycyclic compounds, en7yme-like structures
and t~he li`~e.
~ lowever, the nucleophilic grou~)s and electrophilic groups
are preferably located on compounds wherein a cyclic organic
ring or a transient cyclic organic ring can be easily formed
by intramolecular reaction of the nucleophilic group at the
e~ectrophilic center. Cyclic groups can be generally formed
with 3-7 atoms thereon, and preferably in accordance with this
invention the nucleophilic group and the electrophilic group
are positioned on a compound where they can forma 3- or 5-
to 7-membered ring, and more preferably a 5- or 6-membered
ring (4-membered rings are generally known to be difficult to
form in organic reactions). Intramolecular nucleophilic dis-
placement occurs with the compounds of this invention when the
compound is in the reduced state and the rate of nucleophilic
displacement appears to be substantially reduced and prefer-
ably eliminated when the nucleophile is oxidized. The mech-
anism of the above compounds as described is belie~ed to be
different in kind from compounds known in the art which are
oxidized to provide an electrophilic center with subsequent intra-
molecular reaction followed by release of a dye.
Compounds which undergo intramolecular nucleophilic ~ -
displacement can generally be readily distinguished from com-
pounds which undergo intermolecular nucleophilic displacement
by observing the reaction characteristics of the respective
compounds. In one test, a mixture of compounds according to
this invention, which have been modified by blocking the nucleo-
philic groups on some and using a different, readily distinguish-
able release group on others, will undergo release of the photo-
graphically useful moiety much slower from the blocked compounds
than from the unblocked compounds, especially when carried out
in an aqueous alkaline medium, i.e., such as an alkali-permeable
hydrophilic colloid saturated with mildly alkaline solutions.
1(~5'~0
lhe conlpoun~s o~ this inve~ oll preiel~ably con~aln tne
nucleophilic groùps and the electrophilic groups connected
throu~h a ~inka~e which can be ac~clic, but is preferably a
cyclic group to provide more favorable juxtaposition of the
groups whereby intramolecular nucleophilic attack on the elec-
trophilic center is favored. In certain highly preferred
embodiments. the nucleophilic group and the electrophilic
group are both attached to the same aromatic ring structùre,
which includes fused rings wherein each group can be on a
different ring; preferably, both groups are attached to the
same aromatic ring.
In certain embodiments, the compounds of this inven-
tion contain from 1 to about 5 atoms and preferably 3 or 4
atoms between the nucleophilic center of the oxidizable
nucleophilic group and the atom which forms the electrophilic
center, whereby the nucleophilic center, taken together with
the center of the electrophilic group, is capable of forming a
ring or a transient ring having from 3 to 7 atoms therein and
preerably 5 or 6 atoms therein.
The new compounds of this invention have the following
structure:
;
Nu E-Q-X2
tR2)"1 1 tR3)n-1
\ l
R
. Xl
R is a acyclic, cyclic, or polycyclic organic group. R
preferably has from 5-7 members in the ring in which Nu and
E are attached, and is more preferably an aromatic ring includ-
ing fused rings or substituted aromatic rings. Prefera~ly
contains less than 50 atoms and more preferably less than 15
atoms. l~
~05'~6~0
R and R3 are bivalent org~nic groups containing from 1-3
atoms in the bivalent lin~age, such as alkylene, oxal~ylene, or
thialkylene ~roups. R3 contains a carbon atom covalently bond-
ed to E.
Nu is an oxidi.zable nucleophilic group or a precursor for
an oxidizable nucleophilic group inc,uding precursors such as
hydrolyzable cyclic groups formed together with substituents on ~-
Rl. Oxidizable nucleophilic groups include for example, a
hydrazine group:
(-N-N-R4),
H H
a hydroxyamino group: .
R5
. (-N-O~),
including a hydrolyzable precursor for a hydroxyamino group
such as:
R4
-C/ or (-N-O-R ), :~
O
: a hydroxy group (-~H) including precursors for a hydroxy group
such as ~-o-R6), a primary amino group t-NH2) including precur-
sors for a primary amino group, such as:
.i H
_N-R6
R6 can be a hydrolyzable group such as an acyl group compris-
ing from 2-10 carbon atoms. R4 is an alkyl group haYing from
1-10 carbon atoms including substituted alkyl groups, an aryl
group ha~ing from 6-20 carbon atoms including substituted aryl
groups or a group mentioned for R6. R5 can be a hydrogen atom
or any group useful for R4.
.'~ '
.
-11 -
1~5Z6~0 ` _ / ~
is an electrophilic group and is preferably a carbonyl gI`OUp
~-C-) or a sulfonyl group (-SO2-).
Q is a bivalent group providing a mono atom linkage be-
tween E and X2 wherein said mono atom îs a nonmetallic atom of
group V~ or VIA of the periodic table in its -2 or -3 valence
state, such as a nitrogen atom, a oxygen atom, a sulfur atom,
a seleniw~ m and the like. The mono aton-. provides the two
covalent bonds linking X2 to E, and when it is a trivalent
atom it can be monosubstituted with a hy~rogen atom, an alkyl
group containing from 1-10 carbon atoms, including substituted
carbon atoms and carbocyclic groups, or an aryl group contain-
ing from 6-~0 carbon atoms including substituted aryl groups.
One of Xl or Q-X2 is a ballasting group of sufficient
size to render the compound immobile in an alkali-permeable
layer of a photographic element, and one of Xl and Q-X2 is a
photographically useful moiety such as an image dye, an image-
dye precursor, an antifoggant moiety, a toner moiety, a fix-
ing agent, a development accelerator, a developing-agent moiety,
a hardener moiety, and the like, including the necessary linking
groups to attach the respective moiety to E or Rl. n and m
are positive integers of 1 or 2.
Rl, R2 and R3 are selected to provide substantial
proximity of Nu to E to permit intramolecular nucleophilic
cleavage of Q from E and are preferably selected to provide
1 or 3 to 5 atoms between the atom which is the nucleophilic
center of said nucleophilic group and the atom which is the
electrophilic center, whereby the compound is capable of form-
ing a 3- or 5- to 7-membered ring and most preferably a 5-
or 6-membered ring upon intramolecular nucleophilic displace-
ment ~f the group -Q-X2 from the electrophilic group.
In the above formula where Q-X2 is the photographi-
~ally useful moiety, a photographically active group can be
made available by Q upon cleavage of Q-X from the remainder
of the compound, i.e., such as where Q-X forms a mercapto-
- `~
105;~610
te!trazole and the like. However, where xl is the photograph-
ic:ally useful group, the group should be attached in a manner
so that it does not rely upon the cleavage to provide a
photogr~phically useful species.
The nature of the ballasting groups in the above com-
pounds is not critical as long as the portion of the compound
on the ballast side of E is primarily responsible for the
immobility. The other portion of the molecule on the re-
maining side of E generally contains sufficient solubilizing
10 groups to render it mobile and diffusible after cleavage.
Thus, Xl could be a hydrogen atom if R , R and R confer
sufficient insolubility to the compound to render it immobile.
However, when Xl or X2 serve as the ballast function, they
generally comprise long-chain alkyl radicals, as well as
lS aromatic radicals of the benzene and naphthalene series.
Typical, useful groups for the ballast fun~tion contain at
least 8 carbon atoms and preferably at least 14 carbon atoms.
The term "nucleophilic group" as used herein refers
to an atom or group of atoms which have an electron pair
; 20 capable of forming a covalent bond. Groups of this type are
sometimes ionizable groups which react as anionic groups.
The term "oxidizable nucleophilic group" refers to that nu-
cleophilic group which can be oxidized, thus causing a sub-
stantial reduction in the rate of intramolecular nucleophilic
displacement relative to the electrophilic group. Generally,
the groups are less nucleophilic in character upon oxidation
or have a structure which adversely affects the proximity of
the nucleophilic center w-th respect to the electrophilic
; center.
The nucleophilic group can contain only one nucleo~
- philic center such as the oxygen atom in an hydroxy group,
~ - 13 -
lOSZ610
or it can contain more than one nucleophilic center such
as in the case of an hydroxylamine group where either the
nitrogen atom or
- 13a -
~ )5'~61V
the oxygcll atom can be the nucleopl1ilic ccnter. I~lhere more than
one nucleo~hilic ceJIter is present in the nucl~ophilic group on
the intramolecular nucleophilic displaccmcnt cor.lpowlds of this
inven1;ion, the nucleophilic attack and displacement will gener-
ally occur through the center which is capable of forming the
most favored ring structure, i.e.; if the oxygen atom of the
hydroxylamine group would form a 7-membered ring and the nitro-
gen atom would form a 6-membered ring, the active nucleophilic
center would generally be the nitrogen atom.
The term "electrophilic group" refers to an atom or group
of atoms which are capable of accepting an electron pair to
form a covalent bond. Typical electrophilic groups are as
defined above for E. The term "electrophilic cleavage group"
is used herein to refer to a group ~-E-Q-) wherein E and Q
are as defined above.
Bi~alent groups are referred to in the above formula
definitions. It is understood that the linkage in said bivalent
groups refers to the shortest chain of atoms in the respective
groups between the covalent bonds shown in said formula.
; The term "nondiffusing" used herein has the meaning
commonly applied to the term in photography and denotes materi-
als which for all practical purposes do not migrate or wander
through organic colloid layers of photographic elements in an
alkaline medium. The same meaning is to be attached to the
term "immobile".
- The term "diffusible" as applied to the materials of this
invention has the converse meaning and denotes materials having
the property of diffusing effectively through the colloid layers
o~ the photographic elements in an alkaline medium in the presence
of "nondiffusing" materials. "Mobile" has the same meaning.
In one highly preferred embodiment, the immobile com-
pounds of this invention are 2,1-benzisoxazolones linked to a
photographically usoful moiety such as a dye or ~ye precursor.
-14-
. .......... .
~05~610
The dye can be connected to the ben~isoxa~olollc moi~ty through
an electrophilic clcavage group or it can be attachcd directly
to the benzisoxazolone moiety with the provision that a ballast
group is attached to thc benzisoxazolone moiet~ through an
electrophilic cleavage group. These compounds can be represent-
ed by thc fcrmula:
(R3)m l-E-Q-X2
X~ 2)n-1~N-R~
o=c o
wherein Xl, X2, E, Q, and R4 are as defined above. R2 and R3
are bivalent organic groups containing 1 or 2 atoms in the
bivalent linkage and n and m are ~. Q-X2 is preferably a dye
or dye precursor including the necessary linking groups to
attach the dye or dye precursor to Q or the benzene ring of
said formula. E is preferably a carbonyl group; and Q is a
bivalent group containing a nitrogen atom linking E to X2.
Typical immobile compounds of this invention are shown
below. The symbol ~ represents a phenyl group.
..
- CH3
CH3-N-CH2CH2N ~N=N~S02NH2
O-C CH3 ~2~I5
; ~18H37-M-C ~N,~o Compound I
CH3 O
. C~3
CH3~ CH2CH2NSC2~ N-N~OH
C18H37-N-C ~ ~ Cl
CH3 O
,- .
-15-
105~10
c, ~13
N-cH2c'l2c~l2'`l~Iso2 i~
O=C ÇH3 ~ 802CH3
- Co~ o~ld III OH
CH3 C~3 ~N=N~ OC0 0
,N-C~I2CH2-N--S2 C-N
O=C ~H3
~ N Conlpov.nd IV
CH3 r~ O
H37C~ `iCO~ C~
O
,
C, H3 ,C~3
N-CH2CH2-M-S02~j
O=C C,H3 ~
H37CIS-NCO~ C~ N NHS02C}-13
: . ¢~ ,, ._'
' ' ' ' ' . '
OC00
'~,H3 CH3 ¢~
N-CH2CH2-N-s02 ~SO2r~I N
H37C18i~C ~ ,C,' ornpo !~S02CH3
N02
~(~5;~610
The photogralhic processes usin~ thc immobile com-
pounds are generally carried out in an alkaline mèdinm where-
in the nucleophilic displacement can easily take place. In
certain embodiments, the processes are carried out in an
alkaline medium having a pH of above 12. At a hi~h p~l-, silver
halide development proceeds rapidly and dye mobility is generally
high. High-p~l conditions are especially prefer~ed for image-
transfer processes using the compounds of this invention. ~iore-
over', when the 2,1-benzisoxazolone compounds as described above
are used in photographic elements, they are generally contact-
ed with an alkaline solution at a pH sufficiently high to hydrolyze
the isoxazolone ring to form an hydroxylamino group. The compound
can then react with an oxidized silver halide developer to re-
duce the rate of release of the photographically useful group;
however, where the compound remains unoxidized, the photographi-
cally useful group is released.
The compounds of this invention can generally be prepared
by using conventional techniques used in organic chemistry
wi~h proper selection of the starting materials. The photo-
graphically useful group can be synthesized by methods known in
the art with the appropriate linkages and groups for reaction
with the remainder of the compound. The examples define a
typical preferred procedure where the acid chloride of a 2,1-
benzisoxazolin-3-one is reacted with,a dye with an amine group
thereon by a Schotten-Baumann reaction to produce compounds in
accordance with this invention.
In certain preferred e,mbodiments, the compounds of this
invention contain a moiety which is an image dye-providing
material. Preferably, the image dye-providin~ moiety is a pre-
formed dye or a shifted dye. Dye materials o~ this type are
well-known in the art and include dyes such as azo dyes, azo-
methine (imine) dyes, anthraquinone dyes, ali~arin dyes, mero-
cyanine dyes, quinoline dyes, cyanine dyes and th~ like. The
_ 1 7 _
105;~6~0 ~ /~
shift~d dyes inclu~e those compoull~s whcrein the li~ht ahsorp-
tion characteristics are shifted hypsocllromically or bathochro-
mically t~hen subjected to a different environment such as a
change in pll, reactioll with a material to form a complex, tauto-
merization, reactions to chan~e the p~a of the compound, and
removal of ~ ~roup such as a hydroly~able acyl group connect~d
to an atom of the chromophore as mentione~ in U.S. Patent
3,260,597.
The shifted dyes are highly preferred and especially
those containing a hydrolyzable group on an atom affecting
the chromophore resonance structure are highly preferred,
because the compounds can be incorporated directly in a silver
halide emulsion layer or even on the exposure side thereof with-
out su~stantial reduction in the recordi.ng light exposure.
After exposure, the dye can be shifted to the appropriate
color such as, for example, by hydrolytic removal of an acyl
group to provide the respective image dye.
Irl another e~lbodiment, the compounds of this invention
contain a moiety which is an image-dye precursor. The term
"image-dye precursor" is understood to refer to those compounds,
which u~dergo reactions encountered in a photographic imaging
system to produce an image dye, such as color couplers, or
oxichromic compounds.
When color couplers are present in the compounds of
this inventio~, the coupler can be released in areas where no
development occurs and can diffuse to an adjacent layer where
they can be reacted with an oxidized color developer such as
a primary aromatic amine to form the image dye. Generally,
~he color coupler and the color developer are so chosen that
the reaction product is immobile. Typical us~ful color
couplers include the pyrazolone couplers, pyrazolotriazole
couplers, open-chain ketomethylene couplers, and phenolic
couplers. Further reference to the descri~tion of appropriate
couplers is found in U.S. Patent 3,620,747.
10~ 610 ~ 1
The photograpilically useful moiety represented by Q-X2
or Xl in the above formula can be a silver halide development
innibitor including triazole~ and tetrazoles such as a 5-mer-
capto-1-phenyltetrazole, a 5-methylbenzotriazole, a 4,5-dichlo-
robenzotriazole and the like, and it can also be an antifoggant
including azaindenes such as a tetrazaindene and the like. The
compounds which contain releasable silver halide development
inhibitors or antifoggants can generally be used in the photo-
graphic elements in association with silver halide layers
wherein said compound can be incorporated in amounts such as 1
to 100 mg./ft.2 dissolved in a coupler solvent such as diethyl
lauramide. When these compounds are incorporated in photo-
graphic elements in association with negative silver halide
emulsions, a positive imagewise distribution of inhibitor or
antifoggant will be produced upon development. Thus, silver
development is inhibited or restrained in the low-exposure toe
as seen on the H and D curve, but not in the more fully exposed
shoulder as seen on the H and D curve. Development inhibition
of the unexposed areas is thereby achieved selectively. When
the silver halide emulsions also h~ve dye releasers in accor-
dance with this invention associated therewi~h, the overall
effect of the inhibitor or antifoggant is to release more dye in
the unexposed regions, improving maximum image dye density to
the image-receiving layer without increasing the amount of dye
released n the exposed regions.
The photographically useful moiety represented by Q-X2
or Xl can also be a silver halide development accelerator such
as a benzyl alcohol, a benzyl ~-picolinium bromide and the li~e,
a foggant including hydrazines and hydrazides such as an ace~yl-
phenylhydrazine and the like, or an auxiliary developer such as
a hydroquinone, a l-phenyl-3-pyrazolidone, an ascorbic acid and
the like. When these compounds are used in photographic ele-
k
~ -18a
~OSZ610
ments in association with silvel halide emulsions which also
have associated t~lerewith image dye-providing materials in
accordance with this invention, the released dye density of all
dyec; in the unexposed regions would be somewhat reduced by fog
development. If, however, one layer was unexposed while the
other t-:o ~,ere given an imagewise exposure, the amount of fog-
gant or development accelerator reaching the unexposed layer
from the other two layers would be less where those layers were
exposed. Hence, the Dmax of the unexposed layer would increase
as a function of exposure of the other two layers. This greatly
enhances the saturation of single colors in a photograph.
-18b-
i()5~610
The compounds of this invention oontaining oxichromic
moieties can also be advantageously used in a photographic
system since they are generally colorless materials due to the
the absence of an image-dye chromophore. Thus, they can also
be used directly in the photographic emulsion or on the ex-
posure side thereof without competitive absorption. Com-
pounds of this type are those compounds which undergo chromo-
genic oxidation to form the respective image dye. The oxi-
dation can be carried out by aerial oxidation, mncorporation
of oxidants into the photographic element or film unit, or
use of an oxidant during processing. Compounds of this type
have been referred to in the art as leuco compounds, i.e.,
compounds which have no color. Typical useful oxichromic
compounds include leuco indoanilines, leuco indophenols, leuco
anthraquinones and the like. In certain preferred embodiments
the compounds of this invention contain oxichromic moieti~s
as described in Belgian Patent 792,598.
The compounds described herein have particular appli-
cation in a diffusion transfer process where it is desired to
have a dye entity transferred to an adjacent layer or a re-
ceiving element. However, it has broad application to photo-
graphic processes in which it is desired to release an image-
wise distribution of a diffusible photographically useful
compound. Thus, the photographically useful group may also
be, for ex~mple, a silver complexing agent, a silver halide
solvent, a fixing agent, a toner, a hardener, an antifoggant,
a fogging agent, a coupler, a sensitizer, a desensitizer, a
developer or an oxidizing agent. In other words, Xl and Q-X2
in the above formula may represent any moiety which, in coml
bination with a hydrogen atom, forms a photographically useful
compound upon oleavage.
-- 19 --
~05;~6~0
The compow~ds of this invention are particularly
useful in photographic ~lements and in photographic processes
t:o provide an imagewise distribution o~ a photographically
useful compound. The photographic element can contain the
immobile compounds in association with any photographic
material which produces an oxidation product during develop-
ment which in turn can react with the nucleophilic group on
said compound. In certain preferred embodiments, where sil-
ver halide emulsions are used as the recording means, the
emulsion can be a negative, direct-positive or reversal
emulsion and the like which undergo development with a silver
halide developing agent to produce oxidized silver halide
developer. The oxidized silver halide developing agent can
react with the nucleophilic group to producè an addition pro-
duct and the like, but preferably the silver halide de~elop-
ing agent is so chosen that a simple redox reaction takes
place to reduce substantially the rate of release of the
photographically useful moiety.
Black-and-white or one-color systems can be made
which employ as few as one silver halide emulslon and com-
pounds according to this invention which comprise the required
image dye-providing moieties to provide the desired net color
effect. Preferably, the compounds of this invention are used
in three-color systems such as, for example, photographic
elements having a layer containing a red-sensitive silver
halideemulsion having associated therewith an intramolecular
nucleophilic displacement compound having a cyan image dye-
providing moiety, a layer containing a green-sensitive silver
halide emulsion having associated therewith an intramolecular
nucleophilic displacement compound which has a magenta image
dye-providing moiety, and a layer containing a blue-sensitive
- 20 -
-- lOS;~610
silver halide emulsion having associated therewith an intra-
molecular nucleophilic displacement compound which has a
yellow image dye-providing moiety.
The photographic element can be designed to provide
an image record in either the image dye-providing material re-
leased and made diffusible or in the immobile dye remaining
in the initial location attached to the oxidized compound and
associated with the respective photographic recording mater-
ial or, in certain instances, both image records can be used.
The residual nondiffusible dye can provide an image record
which will be present as a function of silver halide develop-
ment. The silver and silver halide remaining after develop-
ment can be removed, if desired, to provide better color pro-
perties in the~-record.
In certain preferred embodiments, the photographic
element is used in an image-transfer film unit where the dye
image-providing material upon release diffuses to an adjacent
image-receiving layer. The compounds of this invention can be
used in any image-transfer film unit where either initially
mobile comPounds are used, such as dye developmrs, or where
the initially immobile compounds are used, such as ballasted
redox releasing compounds. Typical useful image-trans~er
fi~m units are disclosed în U.S. Patents 2,543,181, 2,661,293,
2,774,668, 2,983,606, 3,227,550, 3,227,552, 3,309,B01,
3,415,644, 3,415,645, 3,415,6a6, and 3,635,707, Canadian Pa-~
tent 674,082, and Belgian Patents 757,959 and 757,960. How-
ever, the appropriate silver halide emulsions will have to be
used in each unlt since the present compounds yield a positive
image in di~fusible dye with a negative recording and develop-
ing emulsion.
- 21 -
`lOS;~610
In certain embodiments, the photo~raphic elements of
this invention are processed in the presence of a silver
halide developing agent which is preferably a silver halide
developing agent which as a redox potential whereby it will
cross-oxidize when oxidized with immobile compounds of this
invention. Typical useful silver halide developers include
hydroquinone campounds such as hydroquinone, 2,5-dichloro-
hydroquinone, and 2-chlorohydroquinone; aminophenol compounds
such as 4-aminophenol, N-methylaminophenol, 3-methyl-4-
aminophenol, and 3,5-dibromoaminophenol; catechol compounds
such as catechol, 4-cyclohexylcatechol, 3-methoxycatechol,
and 4-(N-octadecylamino)-catechol; phenylenediamine compounds
such as N, N-diethyl-~-phenylenediamine, 3-methyl-N,N-diethyl-
~-phenylene-diamine, and 3-methyoxy-N-ethyl-N-ethoxy-~-
phenylenediamine; 3-pyrazolidone compounds such as l-phenyl-
3-pyrazolidone, 1-pheyl-4,4-dimethyl-3-pyrazolidone, 4-hy~
droxymethyl-4-methyl-1-phenyl-3-pyrazolidone, 1-m-tolyl-3-
pyrazolidone, l-~-tolyl-3-pyrazolidone, 1-phenyl-4-methyl-3-
pyrazolidone, l-phenyl-5-methyl-3-pyrazolidone, 1-phen~1-4,4-
bis-(hydroxymethyl)-3-pyrazolidone, 1,4-dimethyl-3-pyrazoli-
done, 4-methyl-3-pyrazolidone, 4,4-dimethyl-3-pyrazolidone,
1-(3-chlorophenyl)-4-methyl-3-pyrazolidone, 1-(4-chloro~
phenyl)-4-methyl-3-pyrazolidone, 1-(3-chlorophenyl~-3-pyra-
zolidone, 1-(4-chlorophenyl)-3-pyrazolidone, 1-(4-tolyl-4-
methyl-3-pyrazolidone~, 1-(2-tolyl~-4-methyl-3-pyrazolidone,
1-(4-tolyl)-3-pyrazolidone, 1-(3-tolyl~-3-pyrazolidone, 1-
(3-tolyl~-4,4-dimethyl-3-pyrazolidone, 1-(2-trifluoroethyl~-
~ 4,4-dimethyl-3-pyrazolidone, and 5-methyl-3-pyrazolidone.
: A plurality of developing agents such as those dis-
closed in U.S. Patent 3,039,869 can also be employed. Such
- 22 -
1~5;~610 `
developing agents can be employed in the liquid processing
composition or may be contained, at least in part, in any
layer or layers of the photographic element or film unit
such as the silver halide emulsion layers, the dye image-
providing material layers, interl~yers, image-receiving ;~
layer, etc.
In highly preferred embodiments of this invention, the
photographic element or film unit contains a compound in addi-
tion to said immobile compounds, which is an antifoggant or ` `
development restrainer which substantially prevents any
further development of a silver halide emulsion after the
initial imagewise development has occurred. Generally, the
compound is one which will at least prevent fog buildup in
a silver halide layer during the time necessary to release a
substantial amount of the photographically useful group from
the unoxidiz~d compound. Typical useful develppment restrain-
er precursors which can be used to permit initial develop-
ment but restrain development thereafter are disclosed in
U.S. Patent 3,260,597. Conventional development restrainers
can also be used in the photographic elements or film units
wherein they are located in the processing composition, in
layers adjacent the silver halide emulsion layers, in the
receiving element, in a cover sheet/ etc., where contact with
the silver halide emulsion is delayed until after the initial
image-recording development has occurred.
In a photographic element according to the invention,
each silver halide emulsion layer containing a dye image-
~ providing material or having the dye image-prouiding material
; present in a contiguous layer may be separated f~om the other
silver halide emulsion layers in the negative portion of the
lOS~610
film unit by materials in addition ~ those described above,
including gelatin, calcium alginate, or any of those disclosed
in U.S. Patent 3,384,483, polymeric materials such as poly-
vinylamid~s as disclosed in U.S. Patent 3,421,892, or any
oi those disclosed in French Patent 2,028,236 or U.S. Patents
2r992,104, 3,043,692, 3,044,873, 3,061,428, 3,069,263,
3,069,264, 3,121,011 and 3,427,158.
Generally speaking, except where noted otherwise, the
silver halide emulsion layers in the invention comprise photo-
sensitive silver halide dispersed in gelatin and are abo~t 0.6
to 6 microns in thickness. The dye image-providing materials
are dispersed in an aqueous alkaline solution-permeable poly-
meric binder, such as gelatin, in the same layer as the silver
halide emulsion or as a separate layer about 1 to 7 microns
in thickne3s. The alkaline solution-permeable polymeric
interlayers, e.g., gelatin, are about 1 to 5 microns in
thickness. Of course, these thicknesses are approximate only
and can be modified according to the product desired. In
addition. to gelatin, other suitable hydrophilic materials
incl~de both naturally occurring substances such as proteins,
cellulose derivatives, polysaccharides such as dextran, and
gum arabic; and synthetic polymeric substances such as water-
soluble polyvinyl compounds like poly tvinylpyrrolidone)~ and
acrylamide polymers.
- 25 The photographic emulsion layers and ~ther layers of
a photogra~hic element employed in the practice of this
invention ca~ also contain, alone or in combination with
hydrophilic, water-permeable colloids, other synthetic poly-
meric compQunds such as dispersed vinyl compounds such as in
~0 latex form, and particularly those whihh increase the dimen-
- 24 -
105~6iO ` `
sional sta~ility of the photographic materials. Suitable
synthetic polymers include those described in U.S. ~atents
3,142,568, 3,193,386, 3,062,674, 3,220,844, 3,287,289 and
3,411,911. Particularly effective polymers are water-
insoluble polymers of alkyl acrylates and methacrylates,acrylic acid, sulfoalkyl acrylates or methacrylat~s, those
polymers which have cross-linking sites which facilitate
hardening or curing r and those polymers havl~g recurring
sulfobetaine units as described in Canadian Patent 774,054.
Any material can be employed as the image-receiving
layer in the film units of this invention as long as the
desired function of mordanting or otherwise fixing the dye
images will be obtained. The particular material chosen will,
or course, depend upon the dye image to be mordanted as meh-
tioned hereinbefore. ,
Use of a pH-lowering layer in the film units of the
invention will usually increase the stability of the trans-
ferred image. ~nerally,the p~-lowering layer will effect
a reduction in the pH of the image layer from about 13 or 14
to at least 11 and preferably 5-8 within a short time after
;nhibition. Far example, polymeric acids as disclosed in
U.S. Patents 3,362,819, 2,584,030, or 2,548,575, or Belgian
Patent 603,747 may be employed in the p~-lowering layer.
Such polymeric acids reduce the p~ of the film unit after
development to terminate development and substantially reduce
further dye transfer and thus stabilize the dye image. Suah
polymeric acids comprise polymers containing acid groups,
such as carboxylic acid and sulfonic acid groups, Which are
capable of forming salts with alkali metals, such as sodium
or potassium, or with organic bases, particularly quaternary
ammonium bases, such as tetramethyl ammonium hydroxide. The
- 25 -
lOSZ6~0 '~
polymers can also contain potentially acid-yielding groups
such as anhydrides or lactones or other groups which are
capable of reacting with bases to capture and retain them.
Generally, the most useful polymeric acids contain free
s carboxyl groups, being insaluble in water in the free acid
form and which form water-soluble sodium and/or potassium
salts. Examples of such polymeric acids in~lude dibasic
acid half-ester derivatives of cellulose, which derivatives
contain free carboxyl groups, e.g., cellulose acetate hydro-
gen phthalate, cellulose acetate hydrogen gluturate, cellu-
lose acetate hydrogen succinate, ethyl cellulose hydrogen
succinate, ethyl cellulose acetate hydrogen succinate,
cellulose acetate succinate hydrogen phthalate; ether and
- ester derivatives of cellulose modified with sulfoanhydrides,
e.g., with ortho-sulfobenzoic anhydride; polystyrene sulfonic
acid; carboxymethyl cellulose; polyvinyl hydrogen phthalate;
polyvinyl acetate hydrogen phthalate; polyacrylic acid,
acetals of polyvinyl alcoho~ with carboxy or sulfo-substi-
tuted aldehydes, e.g., o-, m- or p-benzaldehyde sulfonic
acid or carboxylic acid; partial esters of ethylene/maleic
anhydride copolymers; partial esters of methylvinyl ether/
maleic an~ydride copolymers; etc.~ In addition, solid mono-
meric acid materials could also be used such as palmitic
acid, oxalic acid, sebacic acid, hydrocinnamic acid, meta-
~5 nilic acid,- paratoluenesulfonic acid and benzenedisulfonic
acid. Other suitable materials are disclosed in U.S. Pa-
tents 3,422,075 and 2,635,048.
The pH-lowering layer is usually about ~.3 to about
1.5 mils in thickness and can be located in the receiver
portion of the film unit between the support and the image-
- 26 -
lOS'~610
receiving layer, on the cover sheet, or anywhere within the
film unit as long as the desired function is obtained.
An inert timing or spacer layer coated over the pH-
lowering layer may also be used to "time" or control the pH
reduction of the film unit as a function of the rate at
which the alkali diffuses through the inert spacer layer.
Timing layers can also be used effectively to isolate devel-
opment restrainers in a layer adjacent the image-receiving
layer wherein restrainers will be released after alkali
breakdown of the timing layer. Examples of such timing
layers include gelatin, polyvinyl alcohol or any of those
disclosed in U.S. Patent 3,455,686. The timmng layer is
also effective in evening out the various reacti~n rates ~èr
a wide range of temperatures, e.g., premature pH reduction
is prevented when i~ibition is effected at temperatures
above room temperature, for example, at 95 to 100F. The
; timing layer is usually about 0.1 to about 0.7 mil in thick-
ness. Especially good results are obtained when the timing
layer comprises a hydrolyzable polymer or a mixture of such
~ 20 polymers which are slowly hydrolyzed by the processing
i ' composition. Examples of su~h hydrolyzable polymers include
polyvinyl acetate, po~lyami~e~,~ cellulose esters, etc.
; The ~lkal ne processing composition employed in this
; invention can be conventional aqueous solutions of an alka-
line material, e.g., sodium hydroxide, sodium carbonate or
an amine such as diethylamine, preferably possess~ng~-a pH
in exc~ss of 12, and preferably contains a developing agent
as described previously. The solution also preferably
contains a viscosity-încreasing compound such as a high-mole-
cular-weight polymer, e.g., a water-soluble ether inert to
- 27 -
~ ^ -
1(~5'~6~0
alkaline solutions such as hydroxyethyl cellulose or alkali
metal salts of carboxymethyl cellulose such as sodium carboxy-
methyl cellulose. A concentration of viscosity-increasing
compound of about l to about 5% by weight of the processing
solution is preferred which will impart thereto a viscosity
of about lO0 cps. to about 200,000 cps.
The alkaline processing composition can also con-
tain a desensitizing agent such as methylene blue, nitro-
substituted heterocyclic compoun*s, 4,~'~bipyridinium salts,
etc., to insure that the photosensitive element is not fur-
ther exposed after it is removed from the camera for pro-
cessing.
While the alkaline processing composition can be
employed in a rupturable container, as described previously,
to facilitate conveniently the introduction of processing
composition into the film unit, other means of discharging
processing composition within the film unit could also be
employed. For example, processing solution can be interjected
by communicating members similar to hypodermic syringes
which are attached either to a camera or camera cartridge,
as described in U.S. Patent 3,352,674.
In certain embodiments of our invention, and espe-
cially with integral format film units, an opacifying agent
can be employed in the processing composition in our inven-
tion. Examples of opacifying agents include carbon b~ck,
- barium sulfate, zinc oxide, barium stearate, silver flake,
silicates, alumina, zirconium oxide, zirconium acetyl ace-
tate, sodium zirconium sulfate, ka~lin, mica, titanium di-
oxide, organic dyes such a9 the nigrosines, or mixtures there-
of ~n ~dely varyin~ a~ount~ de~pe~d~n~ upon t~e degree of
~ - 28 -
105;~0
opacity desired. In general, the concentration of opaci-
fying agent should be sufficient to prevent further expo-
sure of the film unit's silver halide emulsion or emulsions
by ambient actinic radiation through the layer of process-
ing composition, either by direct exposure through a supportor by light piping from the edge of the element. For example,
aarbon black or titanium dioxide will generally provide
sufficient opacity when they are present in the processing
solution in an amount of from about S to 40% by weight.
After the processing solution and opacifying agent have been
distributed into the film unit, processing may take place
out of the camera in the presence of actinic radiation in
' view of the fact that the silver halide emulsion or emulsions
, of the laminate are appropriately protected by incident ra~
diation, at one major surface by the opaque processing com-
position and at the remaining major surface by the alkaline
solution-permeable opaque layer. In certain embodiments,
ballasted indicator dyes or dye precursors can be incorpo~
r,a~d in a layer on the exposure side of the photosensitive
layers; the indicator dye is preferably transparent during
exposure and becomes opaque when contacted with the process-
ing composition. Opaque binding tapes can also be used to
prevent edge leakage of actinic radiation incident on the
silver halide emulsion.
- 28a-
105;~610
When titanium dioxide or other white pigments are
employed as the opacifying agent it may also be desirable
to employ in cooperative relationship therewith a pH-sensi-
tive opacifying dye such as a phthalein dye. Such dyes are
light-absorbing or colored at the pH at which image formation
is effected and colorless or not light-absorbing at a lower
pH. Other details concerning these opacifying dyes are
described in French Patent 2,026,927.
The alkaline solution-permeable, substantially
opaque, light-reflective layer in the integral negative re-
ceiver film units of our invention can generally comprise
any opacifier dispersed in a binder as long as it has the
desired properties. Particularly desirable are white light-
reflective layers since they would be esthetically pleasing
backgrounds on which to view a transferred dye image and
would also possess the optical properties desired for re-
flection of incident radiation. Suitable opacifying agents
include titanium dioxide, barium sulfate, zinc oxide, barium
stearate, silver flake, silicates, alumina, sirconium oxide,
zirconium acetyl acetate, sodium zirconium sulfate, kaolin,
mica, or mixtures thereof in widely varying amounts depend-
ing upon the degree of opacity desired. The opacifying
agents may ~e dispersed in any binder such as an alkal~ma~
solution-permeable polymeric matrix such as, for example,
gelatin, or polyvin~l alcohol. Brightening agents such as
the stibenes, coumarins, triazines and the oxaxoles can also
be added to the light~reflective layer, if desired. When it
is desired to increase the opacifying capacity of the light-
re~lective layer, dark-colored opacifying agents may be
added to it, e.g., carbon black, nigrosine dyes, etc. An-
other technique to increase the opacifying capacity of the
- 29 -
lOS~ O
light-reflective layer is to employ a separate opaque layer
underneath it comprising, e.g., carbon black, nigrosine dyes,
e1:c., dispersed in an alkaline solution-permeable polymeric
matrix such as, for example, gelatin, or polyvinyl alcohol.
Such an opaque layer would generally have a density of at
least 4 and preferably greater than 7 and would be substan-
tially opaque to actinic radiation. The opaque layer may
also be combined with a developer scaven~er layer if one is
present. The light-reflective and opaque layers are ganer~l~y
l to 6 mils in thickness, although they can be varied de-
pending upon the opacifying agent employed, the degree of
opacity desired, etc~
The supports of the film elements of this invention
can be any material as long as it does not deleteriously
affect the photographic properties of layers thereon and is
substantially dimen~ionally stable. Typical useful supports,
include cellulose nitrate film, cellulose acetate fi~m, poly-
(vinyl acetal) film, polystyrene film, poly(ethyleneterephtha~ -
latë3 film, polycarbonate film, poly-~-olefins such as poly-
ethylene and p~lypropylene film, and relatedr^films or resin-
ous materials, as well as glass. In those embodiments where
the support is transparent, it is usually about 2 to 6 mils
in thickness and may contain an ultraviolet absorber if
desired.
The support of the integral negative recèiver film
assemblies and the cover sheet used with these assemblies of
this invention can be any of the materials mentioned above
for the support. If desired, an ultraviolet-absorbing ma-
; terial can be employed in the support or cover sheet.
The photosensitive substances used in this invention
,
- 30 -
lOSf~610
are preferably silver halide compositions and can comprise
silver chloride, silver bromide, silver bromoiodide, silver
chlorobromoiodide and the like, or mixtures thereof. The
emulsions may be coarse- or fine-grain and can be prepared
b~ any of the well-known procedures, e.g., single-jet emul-
sions, double-jet emulsions, such as Lippmann emulsions,
ammoniacal emulsions, thiocyanate or thioether ripened emul-
sions such as those described in U.S. Patents 2,~22,264,
3,320,069, and 3,271,157. Surface-image emulsions can be
used or internal-image emulsions can be used such as those
described in U.S. Patents 2,592,250, 3,206,313, and 3,447,
927. The emulsions may be re~ular-grain emulsions such as
the type described in Klein and Moisar, J. Phot. Sci., vol.
12, No. 5, Sept.~Oct., 1964, pp. 242-251. If desired, mix-
tures of surface-and internal-image emulsions can be used
as described in Luckey et al, U.S. Patent 2,996,382.
Negative-type emulsions can be used or direct-posi-
tive emulsions can be used such as those described in U.S.
Patents 2,184,013, 2,541,472, 3,367,778, 3,501,307, 2,563,
785, 2,456,953, and 2,861,~85 and British Patent 723,019.
~n still another embodiment, the intramolecular
nucleophilic displacement compounds can be coated in a layer
in an alkali-permeable binder Dn a support to pro~ide what
is referred to as a receiver element. The receiver element
can be proeessed by positioning it in interfacial contact
with a photographic silver halide element in the presence of
an alkaline solution and a silver halide developer. In those
areas where oxidized developer diffuses to the receiver layer,
the nucleophilic displacement compound will be oxidized, and
i~ it contains a dye moiety it will provide a permanent image
31
~05;~610
dye record in the areas corresponding to silver halide
development. The remainder of the dye can be removed from
the element, for example, by washing, after intramolecular
nucleophilic displacement. With proper sélection of the
image dye-providing moieties, a black-and-white image can
be obtained. Also, if the nucleophilic compound contains
a tanning agent as the photographically useful moiety, it is
possible to obtain a tanned image record in areas where
silver halide development does not take place, i.e., a posi-
tive image record if a negative emulsion is used.
In this application, certain groups are identified
with reference to the periodic table. The reference table ~;
is located on pp. 400-1 of the Handbook of Chemistry and
Physics, 39th Ed., Chemical Rubber Publishing Co.
15, The photographic elements, as described above,
generally comprise at least one layer containing photographic
recording material, such as silver halide, having associated
therewith an immobile compound. The term "associated there~
with" is a term of art in the photographic industry and -
generally refers to said immobile compound in alkaline-perme-
able relationship with said photographic recording material.
The respective materials can be coated in the same layers or
separate layers, as long as they are effectively associated
and isolated to provide for the desired reactions before a
substantial amount of the intermediate reactant products
diffuse into adjacent photographic record~ng layers, etc.
The invention can be further illustrated by the
following examples.
,
- 32 -
105'~10
Example l-A: Preparation of 7-chloroformyl-1-methyl-2,1-
benz-isoxazolin-3-one-5-N-methyloctadecyl-
carboxamide
(lA)
O=CCl CH3
~ , 3
o
a) 2-nitrotrimesic aci~ (lB~
To a solution of 40.0 g. (1 mole) of sodium hydroxide
in 1000 ml. water are added 64 g. (0.33 mole) of a mixture of
nitro-3,5-dimethylbenzoic acids (Chem. Ber. 34, 27, i901).
The yellow solution is brought to boiling and 220 g. potassium
permanganate are added in portions as fast as the purple color
is discharged. After the permanganate addition, the reaction
is refluxed an additional 30 min.~ and then cooled to room
temperature. The manqanese dioxide precipitate is removed
by suction filtration through a celite pad. The deep green
filtrate is made acidic with concentrated hydrochloric acid
(200 ml). The aqueous solution is then continuously extracted
with ether over night. Evaporation of the dried ether ex-
tracts gives 30 g~. of pale yellow 2-nitrotrimesic acid,
M.P. 290C. dec.
b) 5,7-dicarboxy-2,1-benzisoxazolin-3-one ~lC)
A solution of 2.0 g. of lC in 5 ml. of 1:1 ethanol:
~ water, 2M in sulfuric acid, is electrolyzed at aontrolled
; potential (E 1/2 vs. SCE, -0.07 volt) using a mercury work-
25- ing electrode. After the electrolysis, the yellow solution
~- is concentrated under reduced pressure until most of the
ethanol has been removed. The precipitate which has formed
is collected and washed with cold water. The yield of lC is
1.0 g. The crude material which turns yellow on standing is
.~
- - 33 -
10526~0
used directly in the next step.
c) l-methyl-5,7-dicarboxy-2,1-benzisoxazolin-3-one (lD~'
Crude lC is dissolved in a slight excess of aqueous
sGdium carbonate solution and treated with a 10~ excess of
dimethylsulfate. The reaction is warmed on a steam bath
under nitrogen with swirling until the solution becomes homo-
geneous. The warm reaction mixture is immediately made
acidic with concentrated sulfuric acid and allowed to cool.
The precipitate which forms on cooling is collected, dried
and used directly in the next step. Mass spectrum, m/e 237
(m+).
d) 7-carboxy-1-methyl-2,1-benzisoxazolin-3-one-5-N= ~ ;
methyl-octadecylcarboxamide (lE)
The above product lD i8 slurried in an excess of ~;
neat thionyl chloride and boiled under reflux for 2 hrs.
During this time all thé solid goes into solution, giving a
clear yellow reaction ~ixture. The excess thionyl chloride
is removed under reduced pressure, leaving 5,7-bis~chloro-
formyl~ methyl-2,1-benzisoxazolin-3-one (lE) as a yellow
~' 20 oil which solidifie~.
The bis-acid chloride (lE) is immediately dissolved
in tetrahydrofuran and treated with 4 equivalents of N-
methyloctadecylamine dissolved in tetrahydrofuran. The
reaction is stirred under nitrogen at room temperature for
15 min. The precipitated N-methyloctadecylamine hydrochlor-
ide is removed by filtratLon and the tetrahydrofuran filtrate
is concentrated under reduced pressure, giving the bis-amide
l-methyl-2,1-benz}soxaz~lin-3-one-5,7-bis(N-methyloctadecyl-
carboxamide) (lF~ which is used directly.
` 30 A 10% solution of lF in warm ethanol is treated with
an equal volume of 20% aqueous potassium hydroxide solution
- 34 -
1052610
under a good nitrogen atmosphere. The yellow reaction
mixture is stirred under nitrogen for 15 min. and then made
acidic with concentrated hydrochloric ec~d. The white
precipitate is col~ected and washed well with water. The
white solid is treated with tetrahydroîuran and the insol-
u~le N-methyloctadecylamine hydrochloride is removed by
filtration. The tetrahydrofuran filtrate is dried over
an~ydrous calcium sulfate and concentrated under reduced
pressure. The solid residue is recrystallized from ethanol-
petroleum ether to give the acid-amide lG as a white solid,
M.P. 135-136C; mass spectrum, m/e 502 (m+).
e) 7-chloroformyl-1-methyl-2,1-benzisoxazolin-3-one-
5-N-methyloctadecylcarboxamide (lA)
A solution of acid-amide lG in excess neat thionyl
chloride is boiled under reflux for 2 hr. The excesssthionyl
is chloride is removed under reduced pressure, leaving the de-
sired acid chloride (lA) as a yellow solid.
Example l-B: Preparation of Compound I
Step ~: A solution of 1.72 g. (0.01 mole~ of ~-aminoben-
zenesulfonamide in 10 ml. of 3N aqueous HCl (0.03 mole) is
,
cooled in an ice bath. A precipitate forms. A solution of
0.7 g. (0.01 mole-+S of sodium nitrite in 5 ml of water pre- -
viously cooled in ice is then added slowly with stirring.
All of the precipitate dissolves to a very pale yellow solu-
tion. The mixture is allowed to stand in ice for about 10
min. Then a co~]ed solution of 1.92 g. (0.01 mole) of N-
ethyl-N-(2-methylaminoethyl)-_-toluidine in 1 ml. of acetic
- acid is added slowly with stirring. After the addition, the
dark red mixture is stirred in ice for sevexal minutes.
Excess sodium bicarbonate is then added slowly to the reaction
and the orange solid is collected and washed with water.
- 35 -
: ', ` . :
10526~0
The crude product is separated into fast-1~and slow-moving
fxactions by column chromatogrRphy, using silica gel. The
slow-moving fraction is collected and used in Step 2.
Step 2: The acid chloride compound of Example l-A
(0.78 g., 0.00149 mole) is dissolved in 75 ml. of tetra-
hydrofuran, and 0.55 g. (0.00149 mole) of the purified azo
dye of 9tep 1 and 0.38 g. (0.003 mole) of N,N-diisopropyl-
ethylamine is added. The mixture is stirred at room tempera-
ture for 3 hrs. At the end of this period, a clear orange
solution is obtained. The solution is concentrated to a
small volume. The concentrate is applied to a column of
silica gel and eluted with acetonitrile to yield 1.0 g. of
orange-colored Compound I.
Example 2: Preparation of Compound II
Step 1: Compound 2-A and N,N'-dimethylethylenediamine
are reacted in the same manner as described in Step 1,
Example 4.
Compound 2-A is as follows:
CH37O- ~ N=N ~ SO2Cl
.' O
St~p 2: To a slurry of 1.18 g. (0.00284 mole) of the
':
yellow dye HCl of Step 1 in 75 ml. of tetrahydrofuran is
added 0.588 g.~ (0.00568 mole) of anpydrous sodium carbonate
followed ~y about 5 ml. of water. The mixture is stirred
for a few minutes until all of the material has dissolved,
and 1.47 g. (0.00284 mole) of the acid chloride lA of Bxample
l-A in 50 ml. of tetrahydrofuraa are added dropwise. After
the addition, the reaction is stirred at room temperature
- 36 -
1052610
for 30 min. and then anhydrous hydrogen chloride is passed
in until the mixture becomes acidic. The solution is decanted
from some insoluble salts and concentrated on a rotary evap-
orator. The residue is dissolved in dichloromethane and
applied to a dry column o~ silica gel. Upon elution with
a 1:1 mixture of acetone and ethyl acetate, a yellow band
is collected and concentrated. The yield of Compound II is
1.5 g.
Example 3: Preparation of Compound III
Step 1: A solution of 9.64 g. (0.02 mole) of Compound
3-A in 75 ml. tetrahydxofuran is mixed with 5.04 g. (0.05
mole) of N,N-dimethyl-1,3-propanediamine and 7.74 g. (0.06
mole) of diisopropylaminoethylamine. A mild exotherm resùlts,
yielding magenta solution and a gummy precipitate. The mix-
ture is heated in an oil bath for 1 hr., cooled and filtered.
The re~idue is washed with tetrahydrofuran. The washings
and filtrate are combined and concentrated to a purple syrup.
Compound 3-A is as follows:
1l
~O-C--O--CH2 -CH3
NHS02CH3
~ ~LS02Cl
Compound 3A, 3-44-hydroxy-8-methylsulfonamidonaphthylazo)ben-
zenesulfonyl chloride, can be prepared in the following ---
manner. The product of the reaction of 5-amino-1-naphthol
and methanesulfonyl chloride is dissolved in alkali and pre-
cipitated with acid. The resulting 5-methylsulfonamido-1-
- 25 naphthol is coupled with diazotized metanilic acid. The pro-
duct of the coupling reac~ion is treated with ethyl chloro-
105~610
formate to block the free hydroxyl group and then it is
reacted with a mixture of thionyl chloride and dimethyl-
formamide to yield the desired Compound 3A.
6tep 2: The syrup from Step 1 is warmed gently at re- ~-
flux for 1 hr. with 15 g. of ethyl chloroformate and~l25.ml.
of tetrahydrofuran. Then 5.2 g. (0.04 mole) of N,N-diiso-
propylethylamine are added and the mixture is refluxed
gently for 1 additional hour. The reaction mixture is con-
centrated to a syrup and chromatographed on a silica gel
column, using acetone to elute front-running material which
- crystallizes.
Step 3: The product of Step 2 (1.50 g.) and 1.50 g. of
potassium hydroxide pellets are refluxed for 2 hrs. in a
mixture of 60 ml. methanol and 15 ml.n~ater. An additional
4.5 g. of potassium hydroxide are added and gentle refluxing
is continued for 2 hrs. At the end of this time the methanol
is distilled off, the residue i8 diluted to 100 ml. with
water, and an additional 4.0 g. potassium hydroxide are
added to make about a 10% solution. The mixture is heated
overnight on an oil bath at reflux. After cooling, the reac-
tion mixture is slowly acidified with concentrated HCl
followed by 5% HCl until the magenta solution turns orange,
. .
- giving a precipitate oflfine orange needles. After standing
:
for 30 min., the crystals age collected and dried, yielding
1.15 g. pf product.
- Step 4: To a slurry of 0.990 g. (0.00187 mole) of the
product of Step 3 in 50 ml. of tetrahydrofuran is added
0.396 g. (0.00324 mole) of anhydrous sodium carbon~te,
followed by about 2 ml. of water. ~hen all the material
has dissolved, a solution of 0.974 g. tO.00787 mole) of the
. , .
- 38 -
~05Z610
acid chloride lA of Example l-A in 35 ml. of tetrahydro-
furan is added dropwise. After stirring at room temperature
for about 30 min., the mixture is made acidic with anhydrous
hydrogen chloride. The solution is concentrated on a rotary
evaporator and the residue is dissolved in dichloromethane.
The solution is chromatographed on a column of silica gel.
The eluted product is Compound III.
- Example 4: Preparation of Compound IV
Step 1: To a stirred solution at room temperature of
39~0 g. (0.44 mole) of N,N'-dimethylethylenediamine and 5.68
g. (0.044 mole) of N,N-diisopropylethylamine in tetrahydro-
furan are added 17.8 g. (0.0417 mole) of Compound 4-A in por-
tions over a period of 5 min. After stirring for 30 min. at
room temperature, the mixture is filtered and the filtrate is
concentrated to a syrup. The syrup is triturated in three
250-ml. portions of a 5:1 mixture of ether and ligroine
(B.P. 35-55C.). The residual syrup is treated with 500 ml.
of a 2% aqueous HCl solution to yield a yellow crystalline
product which is cooled to 0C. with st~rring, filtered and
dried. The yield of product is 13.3 g.
Compound 4-A is:
Il
~CC6H5
'
~ IN
~ S02Cl
`:
'
- 39 -
., - ~, :
` ~05;~10
Ste~ 2: The product of Step 1 is reacted with the
acid chloride lA of Example l-A in the manner of Step 2 of
Example 2.
Step 3: To a solution of 1.0 g. (0.0012 mole) Qf the
product of Step 2 in 50 ml. acetone is added 0.5 g. pyridine
followed by 0.17 g. (0.0012 mole) of benzoyl chloride. The
mixture is stirred for 30 min. and concentrated under re-
duced pressure. The residue is dissolved in dichloromethane,
applied to a column of silica gel and eluted with a mixture
of 25:75 ethyl acetate and dichloromethane. The yield is
1.0 g. of Compound IV.
Example 5: Preparation of Compound V
Step 1: Compound 3-A is reacted with N,N'-dimethylethyl-
enediamine according to the procedure of Step 1 ~f Example 4.
Step 2: The product of Step 1 above is reacted with
the acid chloride product of Example 1-A in the manner of
Step 2 of Ex~ 2.
Step 3: To a solu~ion of 1.23 g. (0.00127 mole) of the
product of Step 2 is added 0.5 g. pyridine followed by 0.178
;; 20 g. (0.00127 mole) of benzoyl chloride. The mixture is stirred
for 30 min. and concentrated under reduced pressure. The
residue is dissolved in aichloromethane, applied to a column
of silica gel and eluted with a mixture of 25:75 ethyl acetate
and dichloromethane. The yield of Compound V is 0.92 g.
Example 6: Preparation of Compound VI
Step 1: Compound 6-A is r~acted with N,N'-dimethyl-
ethylenediamine as described in Step 1 of Example 4 followed
by Steps 2 and 3 of Example 4.
Compound 6-A is:
- 40 -
lOS~f~10
~H
~ `:
~ NHSO2 ~
02CH3 5(~2F ,-
N2
Compound 6-A, 3-[5-hydroxy-8-(2-methylsulfonyl-g-nitrophenyl-
azo)naphthylsulfamoyl]benzenesulfonyl fluouide, is prepared
by coupling diazotized 2-methylsulfonyl-4-nitroaniline with
5-(3-fluorosulfonylphenylsulfonamido)-1-naphthol, made by
reacting 5-amino-1-naphthol with 3-~hlorosulfonylbenzenesul-
fonyl fluoride.
Example 7:
A photographic element is prepared by coating on a
cellulose acetate film support a layer containing a gelatinous
negative silver halide (0.8 micron bromide) e~ulsion at 158
mg. silver/ft.2 a~d 183 mg. gelati~jft.2,1-phenyl-3-pyrazoli-
done at 15 mg./ft.2, Compound I at 50 mg./ft.2 dissolved in
I diethyl lauramide at 50 mg./ft.2.
The photographic element is exposed to a graduated-
d~nsity test object and processed at room temperature with an
a~ueous solution comprising 70 g./l. potassium hydroxide, 40
g./l. potassium bromide, 3~ g./l hydroxyethyl cellulose, and
; water to 1 liter, while in contact with a mordanted receiver.
Upon separation of the photographic negative element from
the mordanted receiver, a well-defined positive yellow dye
image is obtained in the receiver.
Example 8:
The procedure of Exam~le 7 i`s repeate~ exce~t 5Q mg.
- 41 -
105;~610
Compound II are used in preparing the photographic element
in place of Compound I. In addition, 7 mg./ft.2 of 5-(2-
cyanoethylthio)-l-phenyltetrazole dissolved in tricresyl
phosphate at 21 mg./ft.2 are incorporated into the emulsion
layer. A well-defined positive dye image is obtained in the
receiver sheet.
Example 9:
The procedure of Example 8 is repeated except
Compound II is replaced with 38 mg./ft.2 Compound III dis-
solved in 38 mg./ft.2 diethyl lauramide. Upon separation of
- the receiver sheet from the negative photographic element,
a well-defined magenta dye image is obtained in the receiver.
Example 10:
... .
A photographic element is prepared as follows:
~ 1~ transparent film support;
1 2) layer containing a red-sensitive negative silver
halide emulstion at 158 mg. silver/ft.2 (0.4 micron
AgBr), gelatin at 183 mg./ft.2, Compound III at 38
; mg./ft2, dissolved in diethyl lauramide at 38
mg./ft2, 1-phenyl-3-pyrazolidone at 15 mg./ft.2
and 5-(2-cyanoethylthio)-1-phenyltetrazole at 7 mg./
ft.2 dissolved in tricresyl phosphate at 21 mg./ft.2;
3~ layer containing gelatin at lS0 mg./ft.2, 2,5-di-
sec-dodecyl hydroquinone at 70 mg./ft.2 dissolved
in diethyl lauramide at 28 mg./ft.2 and a yellow
filter dye at 100 mg./ft.2;
4) layer containing a blue-sensitive negative silver
halide emulsion at 158 mg. Ag/ft.2 ~0,4 micron AgBr),
gelatin at 183 mg./ft.2, Compound II at 50 mg./ft.2
dissolved in diethyl lauramide at 50 mg./ft.2, 1-
phenyl-3-pyrazolidone at 15 mg./ft.2, and 5-(2-
- 42 -
~05;~6~0
cyanoethylthio)-l-phenyltetrazole at 7 mg./ft.2
diseolved in tricr~syl phosphate at 21 mg./ft.2;
5) layer containing gelatin at 82 mg./ft.2.
The negative photographic element is exposed to a
m~llticolor, graduated-density test object and processed as
described in Example 7. Upon separation of the negative
photographic element from the receiver sheet, well-defined
positive image records are obtained in the photographic
element exhibiting color separation.
Example 11:
:
A multicolor photographic element is prepared by
coating a photographic film support with the following layers
in ~rder from the support:
1) layer containing a red-sensitvve negative-silver
halide emulsion ~1.2 ~ average grainAgBr) at 150
mg. silver/ft.2, gelatin at 170 mg./ft.2, Compound
VI at 60 mg./ft.2 dissolved in diethyl lauramide at
30 mg./ft.2, 1-phenyl-3-pyrazolidone at 15 mg./ft.2,
and 5~(2-cyanoethylthio)-1-phenyltetrazole at 12 mg./
ft.2 dissolved in tricresyi phosphate at 36 mg./ft.2;
2) layer containing gelatin at 70 mg./ft.2 and 2,5-di-
sec-dodecyl hydroquinone at 70 mg./ft.2 diseolved
in diethyl lauramide at 23 mg./ft.2;
3) layer containmng a green-sensitive negative silver
halide emulsion (1.2 ~ average grain AgBr) at 150
; mg. siluer/ft.2, gelatin at 170 mg./ft.2, Compound
V at 45 mg./ft.2 dissolved in diethyl lauramide at
23 mg./ft.2~ 1-phenyl-3-pyrazolidone at 15 mg./ft.2,
and 5-C2-cyan~et~y~lthl'o~ en~ltetraz~le at 12 mg./
mg./ft.2 d~s~olved ~n t~cres~l phos~Rate at 36 mg./
i
- 43 ~
105z6~
ft.2;
4) layer containing gelatin at 70 mg./ft.2, 2,S-di-
seP-dodecyl hydroquinone at 70 mg./ft.2 dissolved
in diethyl lauramide at 23 mg./ft.2, and Carey Lea
S silver at 17 mg./ft.2;
5) layer containing a blue-sensitive negative silver
halide emulsioni~tl.2 ~ average grain AgBr) at 150
mg./ft2, gelatin at 170 mg./ft.2, Compound IV at 70
mg./ft2 dissolved in diethyl lauramide at 35 mg./
ft.2, 1-phenyl-3-pyrazolidone at 15 mg./ft.2, and
5-(2-cyanoethylthio)-1-phenyltetrazole at 12 mg./
ft.2 dissolved in tricr~syl phosphate at ~6 mg./
6) layer containing gelatin at 50 mg./ft.2.
The photographic element is exposed to a multicolor,
graduated-density test object and processed at room tempera-
ture with a viscous aqueous solution aomprising S0 g. potas-
sium hydroxide and 30 g. hydroxyethyl cellulose/l. of water,
while in contact wlth a mordanted receiver comprlsing a poly-
ethylene-coated paper support coated with a l~yer containing
copolylstyrene--N-benzyl-N,N-dimethyl-N-(3-maleimidopropyl)-
ammonium chloride] at 200 mg./ft.2 and gelttin at 200 mg./
ft.2 add overcoated with a layer containing S0 mg./ft.2
gel~t~n.
; 25 Upon separation of the photographic element from
the receiver, the receiver is washed, and a well-defined
multicolor reproduction of the test object is obtained.
Exampls 12
An integral color trans~er photographic element is
prepared by coatlng a tranaparent film support with the
~`
"
, ~. . .
,:
. ~
lOS'~
following layers in order from the support:
1) layer containing the mordant copoly[styrene--N-
benzyl-N,N-dimethyl-N-(3-maleimidopropyl)ammonium
chloride] at 200 mg./ft.2 and gelatin at 100 mg./
ft.2;
2) layer containing titanium dioxide at 2000 mg./ft.2
and gelatin at 200 mg./ft.2;
3) layer containing carbon at 250 mg./ft.2 and gelatin
at 156 mg./ft.2;
~0 4) layer containing a red-sensitive negative silver
halide emulsion (1.2 ~ average grain AgBr) at 150
mg. silver/ft.2, gelatin at 170 mg./ft.2, Compound
VI at 60 mg./ft.2 dissolved in diethyl lauramide at
30 mg./ft.2, 1-phenyl-3-pyrazolidone at 15 mg./ft.2, ~;
and 5-(2-cyanoethylthio~-1-phenyltetrazole at 12 mg./
ft.2 dissolved in tricresyl phosphate at 36 mg./ft.2;
5) layer containing gelatin at 70 mg./ft.2 and 2,5-di-
sec-dodecyl hydroquinone ah 70 mg./ft.2 dissolved
in diethyl lauramide at 23 mg./ft.2;
6) layer containing a green-sensitive negative silver
halide emulsion (1.2 ~ average grain AgBr) at 150
mg. silver/ft.2 gel~tin at 170 mg./ft.2, Compound
V at 45 mg./ft.2 dissolved in diethyl lauramide at
23 mg./ft.2, 1-phenyl-3-pyrazolidone at 15 mg./ft.2,
and 5-(2-cyanoethylth~o)-1-phenyltetrazole at 12 mg./
ft.2 dissolved ln tricresyl phosphate at 36 mg./ft.2;
7) layer containing gelatin at 70 mg./ft.2, 2,5-di-
sec-dodecyl hydroquinone at 70 mg./ft.2 dissolv~d
in diethyl lauramide at 23 mg./ft.2, and Carey Lea
silver at 17 mg./ft.2;
- 45 -
.:-
:- .
~05;~61(~ .
8) layer containln~ ~ blue-sensitive negative silver hal-
ide emulsion (1.2 ~u average grain AgBr) at 150
mg./ft.2, gelatin at 170 mg./ft.2, Compound IV at 70
mg./ft.~ dissolved in diethyl lauramide at 35 mg./ft.2,
l-phenyl-3-pyrazolidone at 15 mg./ft.2, and 5-(2-cyano-
ethylthio)-l-phenyltetrazole at 12 mg./ft.2 dissolved
in tricresyl phosphate at 36 mg./ft.2;
9) layer containing gelatin at 50 ~./ft.2
The photographic element is exposed to a multicolor,
graduated-density test object and processed at room temperature
by rupturing a pod containing a viscous solution comprising 100
g. potassium hydroxide and 30 g. hydroxyethy~ cellulose/l. of
water between the photographic element and an opaque cover
sheet.
A~ter a few minutes, a well-defined multicolor repro-
duction of the test object is viewed through the transparent
support of the photographic element.
Example 13:
The photographic elements can be processed to pro~ide
a good positive image in the exposed element by a reversal pro-
cess.
A photographic element is prepared by coating the lay-
; ers on the support as follows:
1) support;
2) layer containing 40 mg./ft.2 of Compound VII dissolved in 20
mg./ft.2 of diethyl lauramide, 10 g./ft.2 of 5-(2-cyanoethyl-
thio)-l-phenyltetrazole dissolved in 30 mg./ft.2 of tricresyl
phosphate, and gelatin at 125 mg./ft.2;
3) layer containing a negative silver bromoiodide emulsion coated
at 100 mg./ft.2 based on silver and gelatin at 100 mg./ft.2;
4) layer containing gelatin at 50 mg./ft.2.
Compound VII is as follows:
~.
_L~6_
105'~610
o}i `
",02CH3
H N-N~ N2
S02-NCH2CH2-N-C li3
C~13 C =o (~H3
H37C18-N~
A sample of the photographic element is exposed image-
wise to a step wedge and processed in Kodak ~ Developer DK-50 at
a pH of 9.0 for 15 min. at 20 C. The element is then washed
for 5 min., dried, and exposed to room light. The sample is
then brought into interfacial contact wlth an image-receiving
element containing a dye mordant with a viscous processing solu-
tion inserted between the photographic element and the image-
receivlng element. The viscous processing solution has the for-
mula: -
potassium hydroxide 60 g.
hydroxyethyl cellulose 30 g.
4-hydroxymethyl-4-methyl-1-phenyl-3- 3 g.
pyrazolidone
sodium thiosulfate 3 g.
potassium bromide 10 g.
water to 1 liter
After 10 min. the elements are separated. The receiver is
washed and dried to provide a good negative image. The photo-
~ .
sensitive element is washed, bleached, washed, fixed, washed and
dried. A good positive cyan dye image is obtained in this ele-
ment.
Example 14:
Intermediates can be prepared for use in Example l-B
by the following procedure:
~- '
~ .
`
105;~610
5,7-dicarboxy-2,1-benzisoxazolin-3-one
To a stirred solution of 12.8 g. of nitrotrimesic
ac:id (prepared by alkaline potassium permanganate cxidation
of nitromesitylene) in 200 ml. of water containing 30 g. of
S s~llfuric acid are added 6.5 g. of zinc dust in portions at
such a rate so as to maintain a temperature of about 25C.
After the addition, the mixture is stirred for an additional
1 hr. After this time, 200 ml. of ethyl acetate are added
and the m xture is rapidly stirred for 15 min. The reaction is
then filtered by suction through a pad of filter aid. The
organic layer is s~parated, dried and concentrated under re-
duced pressure, leaving 9.6 g. of crude product which is
used directly in the neXt step.
~ ~ \ CH30
HOOC ~ O ~ CH300C ~
5,7-dicarboxy-2,1-benzisoxazolin-3-one dimethyl ester
A slurry of 10.1 g. of 5,7-dicarboxy-2,1-benzisoxa-
zolin-3-one in 75 ml. of methanol containing dry hydrogen
chloride gas is boiled under reflux overnight. After this
time the reaction is cooled to room temperature and the solid
is collected and washed with a little methanol to give 9.8 g.
(86%) of 5,7-dicarboxy-2,1-benzisoxazolin-3-one dimethyl
ester, m.p. 166-167~ dec.
CH300C H CH300C~ R
CH300C ~ O ~ CH300C ~ O
., O
l-ethyl-5,7-dicarboxy-2,1-benzisoxazolin-3-one dimethyl ester
To a solution of 25.1 g. of 5,7-dicarboxy-2,1-
:`
- 48 -
105Z6~0
benzisoxazolin-3-one dimethyl ester in 250 ml. of dimethyl-
formamide are added 6.9 g. of an~ydrous potassium carbonate,
followed by 18 g. of diethyl sulfate. The mixture is stirred
and heated to about 100C. until the orange color fades ~
(about 30 min.). The cooled reaction mixture is poured into
1000 ml. of rapidly stirred aqueous sodium bicarbonate sol-
ution. The solid is collected and washed well with water
and dried. The crude product is recrystallized from 60:40
ethanol:water to give 20.7 g. (74%) of white crystals of 1-
ethyl-5,7-dicarboxy-2,1-benzisoxazolin-3-one dimethyl ester;
m.p. 83-84.
Similarly prepared using the appropriate dialkyl
sulfate are the following l-substituted 2,1-benzisoxazolin-
3-ones:
1-methyl-5,7-dicarboxy-2,1-benzisoxazolin-3-one
~imethyl ester; m.p. 151-152
l-isopropyl-5,7-dicarboxy-2,1-benzisoxaz~lin-3-
one dimethyl ester; m.p. 122-124
1-(2-fluoroethyl)-5,7-dicarboxy-2,1-benzisoxa-
zolin-3-one dimethyl ester
l-ethyl-5,7-dicarboxy-2,1-benzisoxazolin-3-one
, :
To a solution of 13.95 g. of 1-ethyl-5,7-dicarboxy-
2,1-benzisoxazolin-3-one dimethyl ester in 50 ml. of tetra-
hydrofuran are added 125 ml. of methanol. Nitrogen gas is
bubbled into the stirred solution for several minutes. A
solution of 6.0 g. of sodium hydroxide in 50 ml. of water is
~` i then added, and the solution is stirred at room temperature
with continued nitrogen bubbling for 15 min. The reaction
mixture is then made acidic with concentrated hydrochloric
acid, followed by the addition of 300 ml. of water. The mix-
ture is then extracted with ethyl ac~tate. The extracts are
washed with water and dried over anhydrous calcium sulfate
and filtered. The solvent is removed under reduced pressure,
- 49 -
: - . . .:
1()5'~610
leaving 11.6 g. (93%) of white 1-~thyl-5,7-dicarboxy-2,1-
benzisoxazolin-3-one; m.p. 320 dec.
_~7-bis(chloroform~l)-1-ethyl-2,1-benzisoxazolin-3-one
A slurry of 10.05 g. of 1-ethyl-5,7-dicarboxy-2,1-
benzisoxazolin-3-one in 75 ml. of thionyl chloride contain-
ing 5 drops of dimethylformamide is boiled under reflux for
30 min. The clear yellow solution is concentrated under
reduced pressure. The residue is treated with benzene and
again concentrated to dryness. The resulting yellow oil
is used directly in the next step.
7-carboxy-1-ethyl-2,1-benzisoxazolin-3-one-5-N-methylocta-
decylearboxamide
To a solution of the above bis-acid chloride in 200
ml. of tetrahydrofuran cooled in an ice bath is added drop-
wise a solution of 22.6 g. of N-methyloctadecylamine and 9
g. of triethylamine in 100 ml. of tetrahydrofuran. After
the addition, the reaction is made acidic with dry hydrogen
chloride gas. The precipitated amine hydrochlorides are re-
moved by filtration and the filtrate is concentrated under
reduced pressure to a solid which is used directly in the
next step.
A 10% solution of the above bis-amide in warm ethanol
is treated with an equal volume of aqueous sodium hydroxide
(3 equivalents) under a good nitrogen atmosphere. The reac-
tion mixture is stirred at room temperature under nitrogenfor 15 min. and then made acidic with hydrochloric acid. The
~ white precipitate is collected, washed well with water and
- dried. The dried product is then treated with tetrahydro-
furan and the insoluble N-methyloctadecylamine hydrochloride
is removed by filtrati~n. The tetrahydrofuran filtrate is
concentrated under reduced pre~sure. The res~due ~s recrys-
- ~Q -
~05A~6~0
tallized from ethanolpetroleum ether to give white 7-carboxy-
l-ethyl-2,1-benzisoxazolin-3-one-5-N-methyloctadecylcarbox-
amide; m.p. 73-75.
Using procedures similar to the above, the following
N-substituted 7-carboxy-2,1-benzisoxazolin-3-one-5-N-methyl-
octadecylcarboxamides are prepared:
7-carboxy-1-methyl-2,1-benzisoxazolin-3-one-5-N-
methyloctadecylcarboxamide
7-carboxy-1-isopropyl-2,1-benzisoxazolin-3-one-5-
N-methyloctadecylcarboxamide
7-carboxy-1-(2-fluoroethyl)-2,1-benzisoxazolin-3-
one-5-N-methyloctadecylcarboxamide
Each of the above acid amides are then reacted sepa-
rately by boiling in excess neat thionyl chloride aDntaining
a trace of diethyl formamide for 30 min. to 1 hr. The ex-
cess thionyl chloride is removed under redu~ed pressure,
leaving the desired acid chlorides as solids or oils which
are used directly to prepare compounds by the procedure of
Example l-B.
Example 15:
Another procedure for preparing compounds of this
inven~ion is as follows:
I. Preparation of 7-carboxy-1-methyl-5-octadecyloxy-2,1-
benxisoxazolin-3-one
A. Dimethylisophthalate
A slurry of 36 g. o~ 5-hydroxyisophthalic acid in
100 ml. of methanol containing dry hydrogen chloride gas is
boiled under reflux for 20 hr. After this time, the reaction
is cooled to room temperature. The solid cake which has
formed is broken up and the product is collected and washed
with a little cold methanol; m.p. 158-159.
B. Dimethyl-5-hydroxy-2-nitroisophthalate
' ,
- 51 -
.. . .
.
~OSZ6~0
To a suspension of 60 g. of dimethylisophthalate
in 600 ml. of methylene chloride are added 200 ml. of con-
centrated nitric acid, and the mixture is rapidly stirred
at room temperature for about 45 min. After this time,
300 ml. of ice water are added, followed by 700 ml. of ethyl
acetate. The organic layer is separated, washed with two
portions of saturated brine, and dried over anhydrous sodium
sulfate. The solvent is removed under reduced pressure,
leaving a sticky solid which is triturated with 100 ml. of
warm benzene. The insoluble material is ~ollected and
washed with benzene to give 19.5 g. (27%) of white to pale
yellow solid, m.p. 183-186.
C. Dimehhyl-2-nitro-5-octadecyloxyisophthalate
To a solution of 19.5 g. of dimethyl~5-hydroxy-2-
. 15 nitroisophthalate in 150 ml. of dry ethanol are added 8.8
g. of tetramethylguanidine, followed by 29.1 g. of octa-
decyliodide. The mixture is refluxed for 16 hr., cooled,
and poured into 700 ml. of water. The precipitate is col-
lected and washed well with water. The dried crude product
is triturated with methanol. The insoluble solid is col-
lected, giving 32.6 g. of product, m.p. 65-68, which is
used wit~out further purification.
D. 7-carboxy-5-octadecyloxy-2,1-benzisoxazolin-3-one
methyl ester
2~ To a solution of 20.4 g. of dimethyl-2-nitro-5-
octadecyloxyisophthalate in 100 ml. of methylene chloride
and 100 ml. of ether is added a solution of 8 g. of ammo~
nium chloride in 175 ml. of water. The mixture is rapidly
stirred and 16 g. of zinc dust are added all at once. The
reaction is stirred at room temperature for 16 hr. After
this time, the orange mixture is filtered by suction through
- 52 -
105Z6~0
a celite pad. To the orange filtrate are added 100 ml. of
dilute hydrochloric acid, and the mi~ture is shaken until
the orange color fades to yellow. The yellow organic layer
is separated, dried over anhydrous cal¢ium sulfate and fil-
S tered. The solvent is removed under reduced pressure. Theremaining residue is dissolved in 125 ml. of hot methanol.
The solution is cooled somewhat and 50 ml. of petroleum
ether are added. ,The ~oLution is al~wed t,o cool
slowly to -12C ,inlia freezer. The yellow~ solid
which has formed -is,collect~ed Land wa~hed w,,ith~ ol,~;
~e,thanpl.~ y!ield: 10,6, gi ,m.~p.~-,89~dec.
~ ~ j
. . .
E. 7-carboxy-1-methyl-5-octadecyloxy-2,1-benzisoxazo-
lin-3-one methyl ester
To a slurry of 1.85 g. of 7-carboxy-5-octadecyloxy-
2,1-benzisoxazolin-3-one methyl ester in 30 ml. of dimethyl-
formamide is added 0.28 g. of powdered an~ydrous potassium
carbonate. The deep red mixture is warmed to about 40C.,
whereupon all the material goes ihto solution. With stirring
and at a temperature of about 40C., 0.63 g. of dimethylsul-
fate is added dropwise. The red color is rapidly discharged.
The reaction is then cooled to room temperature and poured
into 200 ml. of rapidly stirred ice-cold 1% hydrochloric
acid. The precipitate is collected, washed well with water
and used directly in the next step.
. `
' F. 7-carboxy-1-methyl-5-octadecyloxy-2,1-benzisoxazo-
, ' lin-3-one
To a solution of the above crude 7-carboxy-1-methyl-
5-octadecyloxy-2,1-benzisoxazolin-3-one methyl ester in 10
ml. of tetrahydrofuran are added 25 ml. of ethanol. Nitrogen
is bubbled into the solution for about 15 min. With con-
- 53 -
;
105A~6~0
tinued nitrogen bubbling, a solution of 0.4 g. of sodium
hydroxide in 5 ml. of water is added. The mixture is rapid-
ly~ stirred under nitrogen at room temperature for 15 min.,
then carefully made acidic with dilute hydrochloric acid
anld poured knto 100 ml. of water. The solid is collected
and washed with water. The dried solid is recrystallized
from benzene, giving 0.5 g. of white to pale yellow solid
product; m.p. 137-139.
G. 7-chloroformyl-1-methyl-5-octadecyloxy-2,1-benzi-
soxazolin-3-one
A mixture of 461 mg. of 7-carboxy-1-methyl-5-octa-
decyloxy-2,1-benzisoxazolin-3-one and 25 ml. of thionyl
chloride containing 1 drop of dimethylformamide is boiled
under reflux for 15 min. The mixture is concentrated under
reduced pressure to give the acid chloride as a yellow solid
which is used directly.
II. Preparation of Compound VIII
H0
CH ~H
~ 52CH3 502 CII,C;~H
A solution of 7-chloroformyl-1-methyl-5-octadecyloxy-
2,1-benzisoxazolin-3-one (prepared from 461 mg. of the acid)
in 10 ml. of tetrahydrofuran is added dropwise to a stirred
mixture of 712 mg. of dye (prepared as in Example 6, Step 1)
:
- 54 -
105'~6~0 ~
and 250 mg. of triethylamine in 20 ml. of tetrahydrofuran.
A~Eter the addition, the reaction is made acidic with dry
hydrogen chloride gas and the precipitated amine hydrochlor-
ide is removed by filtration. The filtrate is concentrated
under reduced pressure and the residue is dissolved in 80:20
ethyl acetate:acetone and filtered through a short column
of silica gel. The deep cyan filtrate is concentrated to
dryness and the residue is d.i~ssolved in a small amount of
methylene chloride. Petroleum ether is slowly added to the
methylene chloride solution until no more solid forms. The
product is collected to give 615 mg. of green-blue solid
with a metallic luster.
Example 16:
Compounds in accordance with this invention which -
contain dye precursors such as color couplers or oxichromic
compounds can be prepared, such as by the following pro-
cedures:
A., Preparation of 2-(N-benzyloxycarbonyl-N-methylamino)-
ethane sulfonyl chloride
To a solution of 2.47 g. of a,65% aqueous solution
of N-methyltaurine sodium salt (0.01 mole) in 25 ml. of
water are added 1006 g. of anhydrous sodium carbonate. The
solution is rapidly stirred and 1.8 g. of benzyl chloroform-
ate are added. The mixture is stirred at room temperature
for 1 hr~, after which time the reaction is extracted once
', with ether to remove organic soluble material. The remaining
, aqueous solution is concentrated to dryness under reduced
, pressure. The dry white solid i5 suspended in 50 ml. of
; dimethylformamide, and with stirring 3 ml. of thionyl chlor-ide are added. The mixture is stirred at room temperature
for 30 min., then poured into crushed ice. The aqueous mix-
- 55 -
105'~6~0
ture is extracted with ether and the combined ether extracts
are back-extracted with two portions of water to remove di-
methylformamide. The dried ether extracts are concentrated
under reduced pressure to a nearly colorless oil which is
S directly pure by NMR and mass spectral analysis.
B. The sulfonyl chloride of part A is then raacted
with the following amino compound (the amino compound is
readily available from the corresponding nitro compound by
catalytic hydrogenation):
CH3 ~ ~
sulfonyl chloride of Part A
OH
~ N-IC ~ fH3
I_SO2(cH2)2-N
H C=O
OCH2
Compound l~B
C-l. If a releasable coupler is desired, Compound 16B
can be transformed by catalytic hydrogenolysis which removes
the benzyloxycarbonyl protecting group. This compound can
then be reacted with the acid chloride of Example l-A to pro-
vide the compound having a releasable color coupler thereon.
C-2. If an oxichromic moiety is desired on the com-
pound, then Compound 16B is reacted with oxidized 2,6-di-
chloro-~-amino~henol in an alkaline medium to provide the
azomethine dye. This compound containing the azomethine dye
can then be subjected to catalytic hydrogenation, reducing
- 56 -
lOSZ6~0
the dye forming an oxichromic moiety and also providing
concomitant hydrogenolysis of the benzyloxycarbonyl protect-
ing function.
This compound containing the oxichromic moiety can
then be reacted with the acid chloride of Example l-A to
provide a compound having a releasable oxichromic moiety
thereon.
The compounds of C-l or C-2 can be coated in a photo-
graphic element in association with a silver halide layer.
The compounds are generally coated at levels of about 50
to 150 mg./ft.2 dissolved in 50 to 150 mg./ft2 of a solvent
such as diethyl lauramide in a gelatin layer containing 50 ;~
to 200 mg./ft.2 Of silver halide. Exposure and processing
of the element as described in Example 12 gives a positive
image in the released coupler or oxichromic moiety and a
neg~tive image in the unre~eased coupler or oxichromic moiety.
Where the oxichromic moiety diffuses out of the photosensi-
tive layers, such as to a receiver layer, a dye image can
be observed upon exposure of the element to air wherein the
` 20 positive image appears in the receiver layer and a negative
; image appears in the silver halide layers. Where the coupler
diffuses out of the photosensitive layers, such as to an
image-receiving layer, the respective positive and negative
dye images can be obtained by treating the elements with
oxid~zed colour developer such as N-ethyl-N-hydroxyethyl-p-
phenylenediam~ne.
Exam~le 17.
In certain preferred embodiments, the benzisoxa-
æolone has a ~enzyl group substituted in the l-position and
can be made ~ the follo~ng procedure:
- 57 -
: :` . ` :
105;~61~
I. Preparation of 7-chloroformyl-1-benzyl-5-(N,N'-dihexyl-
acetamidoxy)-2,1-benzisoxazolin-3-one
A. tert-butyl-(3,5-dicarbomethpxy-4-nitrophenoxy)acetate
To a solution of 2.55 g. of dimethyl-5-hydroxy-2-
S nitroisophthalate (prepared as in Example 15, ~art B) in 25
mL. of acetone is added 0.69 g. of anhydrous potassium car-
bonate, followed by 1.95 g. of tert-butylbromoacetate. The
mixture is stirred and refluxed for 20 hr. After this time,
the cooled reaction mixture is poured with rapid stirring
into 200 ml. of ice-cold 1% hydrochloric acid. The solid
is collected and washed well with water. Yield 3.4 g.; m.p.
106-108.
B. (3,5-dicarbomethyoxy-4-nitrophenoxy)acetic acid
To a solution of 3.28 g. of tert-butyl-(3,5-dicar-
bometh~xy-4-nitrophenoxy)acetate in 20 ml. of benzene are
added 100 mg. of ~-toluenesulfonic acid monohydrate. The
solution is stirred and refluxed for 30 mins. After this
time, the reaction is cooled and the precipitate collected.
Yield 2.4 g.; m.p. 151-152.
C. (3,5-dicarbomethQx~-4-nitrophenoxy)acetyl chloride
A solution of (3,5-dicarbomethoxy-4-nitrophenoxy)
acetic acid in neat thionyl chloride containing a trace of
dimethylformamide is boiled under reflux for 30 min. The
excess thionyl chloride is removed under reduced pressure,
leaving the acid chloride as an oil which is used directly.
D. (3,5-dicarbomethoxy~4-nitrophenoxy)-N,N-dihexyl-
acetamide
A stirred solution of (3,5-dicarbomethoxy-4-nitro-
phenoxy)acetyl chloride in tetrahydrofuran, cooled in an
ice bath, is treat~d dropwise ~it~ ~ tetrahydrofuran solu-
tion containing 1 equivalent each of dihexylamine and tri-
- 58 -
i{~S'~610
ethylamine. After the addition, the precipitated amino
hydrochloride is removed by filtration and the tetrahydro-
furan filtrate is concentrated under reduced pressure to
an oil which is used directly in the next step.
E. (3,5-dicarboxy-4-nitrophenoxy)-N,N-dihexylacetamide
A solution of crude (3,5-dicarbomethoxy-4-nitro-
phenoxy)-N,N-dihexylacetamide in ethanol is treated with
aqueous sodium hydroxide (3 equivalents) at room temperature
for 15 min. After this time, the reaction was poured into
cold dilute hydrochloric acid. The diacid product which `~
precipitates is collected and washed well with water; m.p.
180-184.
F. [3,5-dicarbo(~-methoxy)benzyloxy-4-nitrophenoxy]-
N,N-dihexylacetamide
HO~ ~ ~OH ;~
C~H13
¦ O \C6H13
CB~O ~ CH2O-C ~ -OCH2 ~ OCH3
OCH2CN~ 6 13
O 6 13
To a solution of (3,5-dicarboxy-4-nitrophenoxy)-
N,N-dihexylacetamide in dimethylformamide containing two
equivalants of triethylamine are added two equivalents of
~-methoxybenzylchloride. The mixture is stirred and heated
to about 100C. for 1 hr. After this time, the reaction is
cooled to room temperature and poured into ice water. The
aqueous mixture is extracted with 2 portions of methylene
.
- 59 -
105'~6~0
chloride. The c~mbined extracts are back-extracted with
water to removedimethylformamide~ dried over anhydrous cal-
cium sulfate, filtered and concentrated under reduced pres-
sure. The remaining oil which was not induced to crystal-
lize is analyzed by MMR and used directly in the next step.
G. 7-carboxy-1-benzyl-S-(N,N'-dihexylacetamidoxy)-2,1-
benzisoxazolin-3-one)-~-methoxybenzyl ester
.
CH30~CH20~x~H2o
C=o il
I C~H13
C6H13
To a solution of 0.01 mole of [3,5-dicarbo-(~-meth-
oxy)benzyloxy-4-nitrophenoxy]-N,N-dihexylacetamide in 25 ml.
of methylene chloride and 25 ml. of ethyl ether is added a
solution of 2 g. of ammonium chloride in 40 ml. of water.
The mixture is rapidly stirred and 4 g. of zinc dust are
added all at once. The reaction is stirred at room temperature
for 3 hr., then filtered by suction through a celite pad. The
orange filtrate is shaken with dilute hydrochloric acid un-
til the initial orange color fades to y~llow. The organic
layer is separated and dried over anhydrous calcium sulfate.
The solvent is removed under reduced pressure, leaving an
oil which is used directly.
The above crude oil is dissolved in 40 ml. of dimeth-
ylformamide containing 2.1 g. of triethylamine. The deep
red solution is warmed with stirring to about 40C. and 1.5
g. of benzyl bromide are added dropwise. The red color is
rapidly discharged. The reaction mixture is cooled to room
- 60 -
lOS;~610
temperature and poured into 200 ml. Qf water. The aqueous
mixture is extracted with~methylene chloride. The combined,
dried extracts are concentrated under reduced pressure to an
oil. The oil is dissolved in methylene chloride and applied
to a column of silica gel. Elution with methylene chloride
and collection of the front-running, highly fluorescent com-
ponent gives 2.6 g. of the desired product as an oil which
will not crystallize.
H. 7-carboxy-1-benzyl-5-(N,N'-dihexylacetamidoxy)-2,1-
benzisoxazolin-3-one
A solution of 2.6 g. of 7-carboxy-1-benzyl-5-(N,N'-
dihexylacetamidoxy)-2,1-benzisoxazolin-3-one-~-methoxybenzyl
ester in 30 ml. of benzene containing 200 mg. of p-toluenesul-
: fonic acid monohydrate is refluxed for 48 hr. After this
time, the reaction is cooled to room temperature and the white
precipitate which forms is collected and washed w~th ben-
zene to give 500 mg. of product, m.p. 157-159.
I. 7-chloroformyl-1-benzyl-5-(N,N'-dihexylacetamidoxy)-
2,1-benzisoxazolin-3-one
A solution of 7-carboxy-1-benzyl-5-(N,N'-dihexylacet-
amidoxy)-2,1-benzisoxazolin-3-one in neat oxalyl chloride is
boiled for 15 min. The excess oxalyl chloride is removed
under reduced pressure to give the acid chloride as an oil
which is used directly.
II.
The acid chloride of part I-I. is then used in Example
l-B to prepare release compounds containing releasable dyes.
The benzisoxazole compounds containing the dyes can
be ~sed in photographic elements, which elements are exposed
and processed as described in Example 12 to provide image
records in the form of the re~ased dye.
,
- 61 -
~OS;~610
Although the invention has been described in consid-
erable detail with particular reference to certain preferred
embodiments thereof, variations and modifications can be
effected within the sp~Fit and ccope of the invention.
.
:.
:,
.~:
" ~
,
- 62 -
.,
.
