JPH0452452B2 - - Google Patents

Description

[Detailed description of the invention] The present invention is useful for image formation such as silver halide photographic materials.
useful in materials and image forming processes,
chromogenic p-sulfonamide diphenylamine,
and regarding the corresponding sulfonimide dyes. Photographic materials for forming silver and dye images are publicly available.
It is knowledge. Dye painting in such known materials
When forming an image, the coupling reaction
It is common to do this. That is, the cup
Development of photographic silver halide according to the ring reaction
oxidize the developer by and then obtain
Cuts off oxidized developer (oxidized form of developer)
react with a coloring agent to form a dye image. this
The method is, for example,Research Disclosure, 1978
December, Item No. 17643, Publisher: Industrial
Opportunities Limited, Homewell, Havant,
Listed in Hampshire, United Kingdom
There is. Image is formed by oxidation of leuco dye
The method is described, for example, in U.S. Pat. No. 3,938,995.
has been done. Currently improves dye images, especially silver images
We present an alternative means for forming dye images that can
It is hoped that this will be provided. According to the invention, diphenylamine, phenyl
selected from the group consisting of naphthylamine or its acid salts;
Discovered color-forming dye precursor compounds
The first benzene contained in the color-forming compound is
Zene ring connects to second benzene ring or
is bonded to the naphthalene nucleus, in which case, (a) The first benzene ring has an electron donating group on its member.
It has it in the ter position or the para position, (b) The second benzene ring or naphthalene nucleus is
It has a sulfonamide group at its para-position, (c) the compound is present in each of its ortho-positions;
does not have a sulfonamide group, and (d) In the oxidized state, the sulfonimide color
It is possible to form elements, In addition, all the ring positions mentioned above are related to the −NH− group.
Such chromogenic dye precursors, which are in the position of
A sacer compound is provided. This color-forming compound is a preferred embodiment of the present invention.
According to the following equation, or its
It is an acidic salt. In the above formula, R is located at the meta or para position,
and [Formula] has 1 to 20 carbon atoms Alkoxy groups, such as methoxy groups, ethoxy groups,
hexyloxy group and octadecyloxy group,
Aryloxy groups with 620 carbon atoms, e.g.
For example, phenoxy group, 2,4-di-t-amylphene
Noxy group, 3,4,5-trimethylphenoxy group
and halophenoxy group, hydrazino group, sulfone
Amide group, ureido group, e.g. N-octylure
ide groups, and carboxamide groups, e.g.
toamide group, propionamide group and N-methyl
an electron donor selected from the group consisting of acetamide groups;
represents a substituent, R¹is located at the ortho or meta position.
and hydrogen, atom having 1 to 20 carbon atoms.
alkyl groups, such as methyl, ethyl, propyl
group, benzyl group, decyl group and eicosyl group, carbon
ruboxamide group, sulfonamide group, carbamo group
yl group, alkoxy having 1 to 3 carbon atoms
groups such as methoxy, ethoxy and propoxy groups
cy group, alkylsulfur having 1 to 5 carbon atoms
Honyl group, e.g. methylsulfonyl group, pentyl group
Sulfonyl group, ethylsulfonyl group and propyl group
Sulfonyl group, ants having 6 to 12 carbon atoms
lsulfonyl group, e.g. phenylsulfonyl group
and methylphenylsulfonyl group, chlorine, bromine,
represents iodine or fluorine, and R¹is sulhona
When representing a mido group, it is located at the meta-position, R²is located at the ortho or meta position.
and hydrogen, atom having 1 to 3 carbon atoms.
alkyl groups, such as methyl, ethyl and propylene
carbamoyl group, having 1 to 3 carbon atoms
alkoxy groups such as methoxy, ethoxy
and propoxy groups, having 1 to 5 carbon atoms
an alkylsulfonyl group, such as methylsulfonyl
group, ethylsulfonyl group and pentylsulfonyl group
arylsulfur having 6 to 12 carbon atoms
Honyl groups, such as phenylsulfonyl groups and methyl
Ruphenylsulfonyl group, chlorine, bromine, iodine or
represents fluorine, R³is hydrogen, carbon atoms having 1 to 3 carbon atoms;
1 to 20 carbon atoms, including lyhaloalkyl groups
an alkyl group having, for example, tribromomethyl
group, 2,2,2-tribromoethyl group, 2,2,
2-trichloroethyl group and 3,3,3-trib
lomopropyl group, atom having 1 to 20 carbon atoms
alkoxy groups, such as methoxy groups, ethoxy groups,
xyloxy group and octadecyloxy group, 1-
alkoxycarbonyl with 20 carbon atoms
groups, such as methoxycarbonyl groups, ethoxycarbonyl groups,
Bonyl group, propyloxycarbonyl group and stereo
Allyloxycarbonyl group, carboxy group, carboxyl group,
Boxamide groups, e.g. acetamido groups, N-methane
tylacetamide group and propionamide group, salt
element, bromine, iodine, fluorine, carbamoyl group, sulfo
acid group, sulfamoyl group, 1 to 5 carbon atoms
an alkylsulfonyl group, such as methylsulfonyl
Sulfonyl group, ethylsulfonyl group and propyl group
sulfonyl group, aryl having 6 to 20 carbon atoms
sulfonyl groups, such as phenylsulfonyl groups and
and methylphenylsulfonyl group, ureido group or
Carbocyclic groups having 6 to 12 carbon atoms, e.g.
Cyclopentyl group, cyclohexyl group, alkyl group
-represents a substituted cyclohexyl group and phenyl group
death, R^Fouris hydrogen, hydrogen having 1 to 3 carbon atoms
1 to 20 carbon atoms, including lyhaloalkyl groups
an alkyl group having, for example, tribromomethyl
group, 2,2,2-tribromoethyl group, 2,2,
2-trichloroethyl group and 3,3,3-trib
lomopropyl group, atom having 1 to 20 carbon atoms
alkoxy groups, such as methoxy groups, propoxy groups,
Hexyl group and octadecyloxy group, 1 to 20
an alkoxycarbonyl group having carbon atoms, e.g.
For example, methoxycarbonyl group, ethoxycarbonyl group
group, butoxycarbonyl group and stearyloxy
Carbonyl group, carboxy group, carboxamide
groups, such as acetamido groups, N-methylaceto
Mido and propionamide groups, chlorine, bromine, iodine
element, fluorine, carbamoyl group, sulfonic acid group, sulfur
fumoyl group, an alkyl group having 1 to 5 carbon atoms
Kylsulfonyl groups, such as methylsulfonyl groups,
ethylsulfonyl group and propylsulfonyl group,
Arylsulfonyl having 6 to 20 carbon atoms
groups, such as phenylsulfonyl groups and methylphenylsulfonyl groups,
Nylsulfonyl group, ureido group, e.g. N-oc
thylureido group, or having 6 to 12 carbon atoms
carbocyclic groups such as phenyl, cyclohexy
group, alkyl-substituted cyclohexyl group (e.g.
dimethylcyclohexyl group) or condensation on benzene.
represents a union, R^Fiveis alkyl having 1 to 20 carbon atoms
groups, such as methyl, ethyl, propyl,
Syl group, dodecyl group, eicosyl group and benzyl group
or aryl having 6 to 20 carbon atoms,
For example, phenyl group, halophenyl group, tolyl group,
Naphthyl group, 2,4,6-triisopropylphene
Nyl group, 2,6-diisopropylphenyl group and
represents a 2,4,6-trimethylphenyl group, R⁶is hydrogen, atom having 1 to 20 carbon atoms
alkyl groups, such as methyl, ethyl, propyl
group, decyl group and dodecyl group, [Formula] or 6- Aryl groups with 20 carbon atoms, e.g.
Nyl group, naphthyl group, halophenyl group, 2,4,
6-trimethylphenyl group, 2,6-diisopropro
May represent pylphenyl and tolyl groups
is R⁷With, for example, pyridino group, morpholin group, etc.
5- or 6-membered complexes such as
necessary to complete a heterocyclic group containing a heterocyclic group.
represents multiple atoms, R⁷has hydrogen or 1 to 20 carbon atoms
Represents an alkyl group or R⁶With,
5- or 6-membered heterocyclic groups, e.g. 1-pyrazo
Multiple atoms needed to complete lu-5-one
represents, and R⁸is alkyl having 1 to 20 carbon atoms
groups, such as methyl, ethyl, benzyl,
represents a ctyl group, a decyl group and an eicosyl group,
At that time, the above-mentioned alkyl group, alkoxy group,
All lyl and aryloxy groups are optional.
may be replaced with . p-sulfonamido diphenyla according to the invention
From min, their corresponding sulfonimide colors
element, especially the sulfonimide color represented by the formula
can form elements. In the above formula, R, R¹,R²,R³,R^Fourand R^Five
are respectively the same as defined above. p-sulfonamide diphenylamine, and
The corresponding sulfonimide dyes were mentioned at the beginning.
images such as silver halide photographic materials
Useful in forming materials. For example, the present invention
Using p-sulfonamide diphenylamine as an example,
When taken, the corresponding components in silver halide photographic materials
their conversion to form sulfonimide dyes.
Compounds are useful. Sulfonimides according to the invention
The dye is developed using a sulfonamide using a cross-oxidation developer.
By cross-oxidation of dodiphenylamine, the photo
Generally, it is formed in a material. child
The sulfonimide dye formed as
Useful as an image dye. This dye further
Also for improving silver images in photographic materials.
Also useful. p-sulfonamido diphenyla according to the invention
Min, and the corresponding sulfonimide dyes are
In addition, printing out in imaging materials and printing plates
As a compound, carbonless paper and thermal paste
Image former (image form) in printing paper for printer
photographic materials and processes), and as photographic materials and processes.
It is also useful in other applications. Book
Other compounds in which the compounds of the invention may be useful
Materials include fabrics and fibers as well as redox indicators.
It includes. As shown above, "alkyl group", "aryl group"
"group", "alkoxy group" and "aryloxy group"
terms, respectively, represent unsubstituted and substituted groups.
It includes both groups. These groups are easily
As understood, the sulfonamide according to the invention
Dodiphenylamine or corresponding sulfonimide
Use a base that does not have a negative effect on the dye.
has been replaced. suitable substituted alkyl
Examples of groups are trihaloalkyl groups, and e.g.
CH₃S.O.₂NHCH₂CH₂sulfonamides such as -
groups, carboxamide groups, such as methoxy groups or
Alkoxy group such as ethoxy group, carboxyl group
a group (-COOH), such as a phenyl group or a tolyl group
has an aryl group such as, and a carbonyl group
It includes an alkyl group. appropriate replacement
Examples of aryl groups are, for example, methoxy or ethoxy groups.
Alkoxy groups such as cy groups, carboxy groups, e.g.
Methyl group, ethyl group, propyl group and butyl group
with an alkyl group such as, and a hydroxy group
contains a phenyl group. Especially useful
The substituted aryl group is an alkyl-substituted aryl group.
groups, such as tolyl, 2,4,6-triisopropro
Pylphenyl group and t-butylphenyl group
Ru. A useful class of chromogenic p-sulfonamides
An example of diphenylamine is expressed by the following formula:
I can do it. In the above formula, R⁹is alkyl having 1 to 20 carbon atoms
groups, such as methyl, ethyl, propyl,
represents a syl group and an eicosyl group, R^Tenrepresents hydrogen or 1 to 20 carbons
Alkyl groups with elementary atoms, such as methyl groups,
Tyl group, propyl group, decyl group and eicosyl group
represents, and R″ is an alkali with 7 to 20 carbon atoms
group, such as methyl phenyl group, butyl phenyl group,
group and 2,4,6-triisopropylphenyl
represents a group. For example, in imaging materials and processes.
Especially useful p-sulfonamide diphenylamine
and the corresponding sulfonimide dyes, e.g.
having a stabilizing group represented by R″
It's something like this. The term “stabilizing group” refers to
When used herein, the sulfonate
When used as a substituent on midodiphenylamine
sulfonamide diphenylamine and the corresponding
Enhanced stability against sulfonimide dyes
It means a group that can give especially useful
The stabilizing group is 2,4,6 represented by the following formula.
-triisopropylphenyl group. In the present specification, this group is represented by the following formula:
Sometimes. 2,4,6-triisopropylphenyl group is particularly
Although it is a useful stabilizing group for
Stabilizing groups are also useful. Chromogenic p-sulfonamide containing stabilizing group
An example of diphenylamine is represented by the above formula ().
Sorry, and R in the formula^Fiveis 2,4,6-trii
It is like a sopropylphenyl group.
Examples of useful corresponding sulfonimide dyes are listed above.
It is expressed by the formula (), and R in the formula^Fiveis 2,
4,6-triisopropylphenyl group
It is something. Color-forming p-sues according to the invention containing stabilizing groups
sulfonamide diphenylamine dye precursor
A few examples in particular are as follows. 4-dihexylamino-4'-(2,4,6-t
lyisopropylbenzenesulfonamide) diphene
Nylamine: 4-n-hexyloxy-3'-methyl-4'-
(2,4,6-triisopropylbenzene sulfonate)
(amide) diphenylamine: 4-N,N-diethylamino-4'-(2,4,
6-triisopropylbenzenesulfonamide)
Diphenylamine: 4-N,N-dimethylamino-2-phenyls
sulfonyl-4'-(2,4,6-triisopropyl
Benzenesulfonamide) diphenylamine: Useful chromogenic p-sulfonamide diphenyl
Another class of min is shown in the following equation.
carboxamide-substituted
Chromogenic p-sulfonamide diphenylamine
It is Russ. In the above formula, R¹²is located at the meta or para position.
and [Formula] 1 to 20 carbon atoms an alkoxy group, such as a methoxy group, an ethoxy group,
cy group, hexyloxy group and dodecyloxy group,
aryloxy group having 6 to 12 carbon atoms,
For example, phenoxy groups and alkyl-substituted phenoxy groups
cy group, carboxamide group, e.g. acetamide
group and N-methylacetamide group, and urei
from the group consisting of do groups, such as octylureido groups
represents a selected electron-donating substituent, R¹³is located at the ortho or meta position.
and hydrogen, atom having 1 to 3 carbon atoms.
alkyl groups, such as methyl, ethyl and propylene
carbamoyl group, having 1 to 3 carbon atoms
alkoxy groups such as methoxy, ethoxy
and propoxy groups, having 1 to 5 carbon atoms
an alkylsulfonyl group, such as methylsulfonyl
group, ethylsulfonyl group and pentylsulfonyl group
arylsulfur having 6 to 12 carbon atoms
Honyl groups, such as phenylsulfonyl groups and methyl
Ruphenylsulfonyl group, chlorine, bromine, iodine, fluorine
base or sulfonamide group (located in meta-position)
represents, R¹⁴is hydrogen, atom having 1 to 3 carbon atoms
alkyl groups, such as methyl, ethyl and propylene
carbamoyl group, having 1 to 3 carbon atoms
alkoxy groups such as methoxy, ethoxy
and propoxy groups, having 1 to 3 carbon atoms
an alkylsulfonyl group, such as methylsulfonyl
group, ethylsulfonyl group and propylsulfonyl group
arylsulfur having 6 to 12 carbon atoms
Honyl groups, such as phenylsulfonyl groups and tri-
Represents sulfonyl group, chlorine, bromine, iodine or fluorine
eagle, I, R¹⁵represents hydrogen or carboxyl
Mido group, e.g. acetamido group, propionamide group
represents a do group, a pivalamide group and a ureido group, R¹⁶represents hydrogen or carboxyl
Mido group, e.g. acetamido group, propionamide group
represents a do group, a butylamide group and a pivalamide group.
death, R¹⁷is alkyl having 1 to 20 carbon atoms
groups, such as methyl, ethyl, propyl,
Represents a syl group or an eicosyl group, or 6-
Aryl groups with 20 carbon atoms, e.g.
Nyl group, naphthyl group, tolyl group and 2,4,6-
represents a triisopropylphenyl group, R¹⁸is hydrogen, atom having 1 to 20 carbon atoms
alkyl groups, such as methyl, ethyl, propyl
group, decyl group and eicosyl group, or 6 to 12
Aryl groups with carbon atoms, e.g. phenyl groups
and represents a tolyl group, and R¹⁹represents hydrogen or 1 to 20 carbons
Alkyl groups with elementary atoms, such as methyl groups,
Tyl group, propyl group, decyl group and eicosyl group
represents. Here, the above R¹⁶is a carboxamide
When representing a group, R¹⁵represents carboxamide group
However, the above-mentioned alkyl groups, aryl groups,
Koxy and aryloxy groups are all optional.
may be replaced with . The preferred sulfonamide group used here is
It can be expressed by the following equation. −NHSO₂R²⁰ In the above formula, R²⁰is the diphenylene according to the present invention.
Adverse effect on amine compounds or imide dyes
Represents a substituent that does not have any negative effect. R²⁰
is, for example, an alkyl group having 1 to 20 carbon atoms.
group, such as methyl group, ethyl group, propyl group,
Butyl group, decyl group and eicosyl group, or 6-
Aryl groups with 20 carbon atoms, e.g.
Nyl group, tolyl group and 2,4,6-triisopropropyl group
Represents a pylphenyl group. Examples of such groups are
2,4,6-triisopropylphenyl sulfone
Amide group, methylsulfonamide group and tolylus
Contains a sulfonamide group. Particularly useful carboxamide-substituted compounds
Indicates chromatic p-sulfonamide diphenylamine
It can be expressed as the following equation. In the above formula, R^{twenty one}is an alkoxy group having 1 to 20 carbon atoms
Represents a group or [formula], R^{twenty two}represents hydrogen or [formula], R^{twenty three}is alkyl having 1 to 20 carbon atoms
groups, such as methyl, ethyl, propyl, butyl
Tyl group, decyl group, dodecyl group and eicosyl group
groups, aryl groups having 6 to 12 carbon atoms, e.g.
For example, phenyl group and 2,4-diisopropylphene
Nyl group, alkoxy having 1 to 4 carbon atoms
groups such as methoxy, ethoxy and butoxy
radical, aryloxy having 6 to 12 carbon atoms
groups, such as phenoxy groups and 3,4,5-trimethane groups.
Tylphenoxy group, or -NHR²⁷represents, R^{twenty four}has hydrogen or 1 to 20 carbon atoms
Alkyl groups, such as methyl, ethyl, propylene
represents a ru group, a decyl group and an eicosyl group, R^{twenty five}has hydrogen or 1 to 20 carbon atoms
Alkyl groups, such as methyl, ethyl, propylene
group, butyl group, decyl group and eicosyl group, or
is an aryl group having 6 to 12 carbon atoms, e.g.
phenyl group and 2,4-diisopropylphenyl group
represents a group, R²⁶is alkyl having 1 to 20 carbon atoms
groups, such as methyl, ethyl, propyl,
Syl and eicosyl groups, 5 to 20 carbon atoms
cycloalkyl groups, such as cyclopentyl
groups, cyclohexyl groups and substituted cyclohexyl groups
Syl group, aryl with 6 to 12 carbon atoms
groups, such as phenyl and tolyl groups, 1 to 4
Alkoxy groups with carbon atoms, e.g. methoxy
groups, ethoxy and butoxy groups, 6 to 12 carbons
Aryloxy groups with atoms, e.g.
cy group and 3,4,5-trimethylphenoxy group,
or −NHR²⁸represents, and R²⁷and R²⁸are 1 to 20 carbon sources, respectively.
Alkyl groups with children, such as methyl, ethyl
group, propyl group, butyl group, decyl group and eico
Syl group, aryl with 6 to 12 carbon atoms
groups, such as phenyl and tolyl groups, 1 to 4
Alkoxy groups with carbon atoms, e.g. methoxy
groups, ethoxy and butoxy groups, or 6 to 12
Aryloxy groups with carbon atoms, e.g.
noxy group and 2,4,5-trimethylphenoxy
represents a group. Here, the above-mentioned alkyl group, ali
ol group, alkoxy group and aryloxy group,
All have been arbitrarily substituted. Another useful carboxamide-substituted color
An example of p-sulfonamide diphenylamine is shown below.
Then, the result is as follows. 4-[N-ethyl-N-(β-methanesulfona
(midoethyl)amino]-2-methyl-2',5'-di
Pivalamide-4'-(2,4,6-triisopropropylene)
pyrubenzenesulfonamide) diphenylamide
hmm: 4-n-hexyloxy-2',5'-dipivalua
Mido-4'-(2,4,6-triisopropylben
Zensulfonamide) diphenylamine: carboxamide group and at least two sulfonamides
Other color-forming p-sulfona containing a do group
The midodiphenylamine compound is shown by the following formula:
can be expressed as In the above formula, R²⁹is alkyl having 1 to 20 carbon atoms
groups, such as methyl, ethyl, propyl,
Syl and eicosyl groups, 1 to 20 carbon atoms
an alkoxy group, such as a methoxy group, an ethoxy group,
cy group, hexyloxy group and dodecyloxy group,
or represents [formula], R³⁰is alkyl having 1 to 20 carbon atoms
groups, such as methyl, ethyl, propyl, but
thyl group, decyl group and eicosyl group, or 6 to 12
an aryl group having 4 carbon atoms, e.g.
represents a ru group and a 2,4-dimethylphenyl group, R³¹represents hydrogen or [formula], R³²has hydrogen or 1 to 20 carbon atoms
Alkyl groups, such as methyl, ethyl, propylene
represents a ru group, a decyl group and an eicosyl group, R³³is hydrogen, atom having 1 to 20 carbon atoms
methyl, e.g. methyl, ethyl, propyl
group, decyl group and eicosyl group, or 6 to 12
Aryl groups with carbon atoms, e.g. phenyl groups
and 2,4-dimethylphenyl group, R³⁵is alkyl having 1 to 20 carbon atoms
groups, such as methyl, ethyl, propyl,
Syl and eicosyl groups, 6 to 12 carbon atoms
aryl groups, such as phenyl groups and 2,4
-dimethylphenyl group, having 1 to 4 carbon atoms
alkoxy groups such as methoxy, ethoxy
and butoxy groups, or have 6 to 12 carbon atoms.
aryloxy groups, such as phenyl groups and
represents a 3,4,5-trimethylphenoxy group,
and R³⁶is alkyl having 1 to 12 carbon atoms
groups such as methyl, ethyl, propyl and
Represents a dodecyl group. Here, the alkyl mentioned above
groups, aryl groups, alkoxy groups and arylox
All si groups are optionally substituted. This way
una, carboxamide group and at least two sulfones
Color-forming p-sulfonamide containing an amide group
Some examples of diphenylamines are:
It is. 3-Methanesulfonamido-4-methyl-2'-
Palmitamide-4'-(2,4,6-triisopropylene)
ropylbenzenesulfonamide) diphenylamide
hmm: 3-methanesulfonamide-4-methoxy-
2'-pivalamide-4'-(2,4,6-triiso
Propylbenzenesulfonamide) Diphenyla
Min: Chromogenic p-sulfonamide diphene according to the present invention
When preparing nylamine, there are four methods described below.
Do it by at least one method of law.
cormorant: 1 The first method may be phenylenediamine.
is an ether-substituted aniline substituted with a halonitrobene.
and then reduce the nitro group.
and subsequent sulfonylation of the amine.
It is based on that. To explain this, the following
It becomes a composite expression like . X in the formula is, for example, bromine, chlorine or fluorine.
represents a halogen, and R and R^Fiveteeth,
Each is the same as the definition above. DMF is
In this case, we mean dimethylformamide.
Ru. DMSO is in this case dimethyl sulfo
It means Sid. In this case, Pd-C is
Parameters suitable for catalyzing hydrogen reduction of nitro groups
Denotes a dium-charcoal catalyst. 2 The second method is to convert the halonitroaniline into a chloride solution.
condensation with sulfonyl, which is subsequently combined with phenylated
condensed with diamine or aniline, and
, then reduce the nitro group, and subsequently
to acylate the amine and form a carboxamide.
Obtaining converted sulfonamide diphenylamine
It is made up of In this method, halo nitro
Sulfonamidobenzene (phenylenediamine)
or directly condensed with aniline)
So the sulfonylation step can be avoided.
Ru. To explain this second method, the following
It becomes a composite formula. In the above formula, X, R, R^Fiveand R^{twenty three}That's it
The definitions are the same as above. 3 The third method is to convert the substituted aniline into a sulfonyl chloride.
followed by ferricyanide and
phenylenediamine and acid in the presence of base and base.
to obtain the dye, and then this color
It originates from reducing the element to a leuco state.
There is. Carboxa prior to oxidation coupling
Introducing an amide group. Explaining this third method
Then, we get the following composition formula. In the above formula, R, R^Fiveand R^{twenty three}are each
Same as above definition. 4 The fourth method involves direct nucleophilic condensation of the preparation.
For those where the reaction is insufficient
It consists of the Smiles dislocation method.
This Smiles rearrangement can be carried out using weakly basic aniline or
is an aniline with steric hindrance at the ortho position (direct
1-halo-4-nito by direct nucleophilic condensation reaction
Sufficient condensation even when condensing with lobenzene
can be applied to child
To explain the method, we get the following composition formula. In the above formula, R and R^Fiveare respectively before
Same as above definition. Preferably prepared by the fourth method above
Examples of the compounds are as follows. 4-N,N-dimethyl-2-phenylsulfony
-4'-(2,4,6-triisopropylbenze
sulfonamide) diphenylamine: 4-(N,N-diethylamino)-2-methyl-
3'-Methyl-4'-(2,4,6-triisopropyl
Rubenzenesulfonamide) diphenylamine: In methods 1, 2, 3 and 4 above, it
Optimal reaction conditions and reactants when carrying out the method of et al.
For example, the concentration of
Honamide diphenylamine, and certain reactions
It will depend on factors such as the body. Chromogenic sulfonamide diphenylamine,
and their corresponding sulfonimide dyes.
Therefore, those compounds shown here are in non-salt form.
ing. Chromogenic sulfonamide diphenyl amide
and their corresponding dyes are described herein.
, including both salt and non-salt forms.
There is. The described p-sulfonamide diphenyl
An example of a suitable salt of amine is p-toluenesulfonic acid.
salt, 1,5-naphthalenedisulfonate, and
Includes benzene sulfonate. p-sulfonamide diphenylamine as a photographic material
When used in materials, it can be used over a wide concentration range.
They are useful. Optimal concentration of p-sulfona
Choosing midodiphenylamine is an example of
For example, the desired image, specific photographic material, processing step, etc.
and conditions, other components in the photographic material, and special
p-sulfonamide diphenylamine
It will depend on the factors. p-sulfone
Useful concentrations of amidodiphenylamine are photographic materials
per mole of silver halide contained in the material.
At concentrations containing amines ranging from 0.08 to 0.6 molar
be. Particularly useful concentrations are those contained in the photographic materials described.
p as described above for 1 mole of silver halide
- 0.1 to 0.2 moles of sulfonamide diphenylamine
The concentration is within the range of silver halide copy
In the true element, p-sulfonamide diphenyl
Useful concentrations of amines are 0.5 to 22 mg (1 dm of support²Current
), preferably 5 to 11 mg (support 1 dm²hit)
be. Chromogenic p-sulfonamide diphenylamine?
The hues of the pigments formed from these materials are diverse;
These dyes, for example, have specific groups or treatments on the color former.
conditions, and p-sulfonamide diphenyl
Other ingredients in photographic materials containing min, e.g.
Varies depending on factors such as dispersion solvent,
do. p-sulfonamide diphenylamine is
It is usually added to the photographic material before it is subjected to processing.
colorless or very lightly colored
It's nothing more than that. Suitable p-sulfonamide diphenyl
Some of the color formers are used in photographic materials.
It has a pale yellow color. Such a light color
This can be considered to be within the permissible range. In some cases, p-sulfonamide diphenyl
Amines are radioactive rays in a specific region of the electromagnetic spectrum.
In other words, the properties described above and the places formed after processing
to ensure that it does not have a negative effect on the desired image.
absorbs radiation in specific areas such as The present invention further provides a support and a
The following are reactively combined in a binder:
Substance of: (a) photosensitive silver halide, and (b) a chromogenic dye precursor compound according to the invention; Provides a photographic element comprising: The term “reactively combined” means that
When used herein, photosensitive halogen
p-sulfonamide diphenylar described as silver chloride
Min color forming agent is in one positional relationship with each other, i.e.
The desired dye image and
The desired silver image can be formed after processing.
This means that they are in a position that allows them to Chromogenic p-sulfonamide diphene according to the present invention
Nylamine is essentially a photographic silver halide.
It is particularly useful in photographic materials containing light-sensitive components.
be. Many photographic silver halides are present in photographic materials.
It is useful. Examples of useful photographic silver halides are:
Silver chloride, silver bromide, silver bromoiodide, silver chlorobromoiodide, silver iodide
or a mixture thereof. Photographic silver halide is
Usually, an emulsion (photographic silver halide) is added to the photographic material.
present in the form of (dispersed in a binder)
There is. Furthermore, photographic silver halide is produced from fine grains.
Present in a particle size range up to coarse particles. photo halo
When preparing compositions containing silver germide, e.g.
BaResearch Disclosure, December 1978, Item No.
Publicly available in the field of photography as listed in 17643
You can do this using any known method.
Wear. Chemically sensitizing photographic silver halide compositions
It is common to For example, when spectrally sensitizing silver halide,
I quoted earlierResearch Disclosure, 1978
December, spectral sensitizing dyes as described in Item No. 17643
You can do that using . spectral sensitization
Pigments can be from different classes, e.g.
Anine, merocyanine, cyanine and merocyanine
complexes (trinuclear, tetranuclear and polynuclear cyanine and metal complexes)
Polymethine dyes containing
Rabi oxonol, hemioxonol, stylized
Contains merostyryl, merostyril and streptocyanin
are doing. Some combinations of spectral sensitizing dyes are available.
It is for use. Chromogenic p-sulfonamide diphenylamine
When used in photographic elements, as desired after processing
at any suitable location that produces a pigment
These amines are useful. p-sulfonamide
Dodiphenylamine was added to photosensitive silver halide.
Together, the desired dye image and the desired silver painting
The image should be placed in such a position that it will form after processing.
be. p-sulfonamide diphenylamine,
Improved performance with dyes in relation to photographic silver halide
Form a stamped silver image after appropriate processing
It is preferable to place it in such a position. depending on the case
adjacent to the light-sensitive silver halide-containing layer of the photographic element.
A layer containing sulfonamide diphenylamine
part can exist. p-sulfonamido diphenyla according to the invention
When amine is reacted with a suitable oxidizing agent, sulfonimine is formed.
A pigment is produced. A suitable oxidizing agent is Felicia
potassium dichromate, potassium dichromate, permanganese
Potassium acid, organic peroxide, inorganic peroxide,
silver halide developer in oxidized form, e.g.
3-pyrazolidone developer in the form of
There is. p-sulfonamide diphenylamine acid
oxidation is to implement it in silver halide photographic materials.
It is preferable to apply However, p-sulfonate
The oxidation of amide diphenylamine in a different environment
For example, in clinical chemistry analyzes where suitable oxidizing agents are present.
Image forming materials in graphic arts
carried out on paper and non-carbon copy paper.
It is also appropriate to Chromogenic p-sulfonamide diphenylamine
For developing images in photographic materials containing
Therefore, many developers are useful. any halogen
A silver oxide developing composition, the composition of which is a sulfonamide
A compound that cross-oxidizes with diphenylamine.
It is useful as long as it contains a loss oxidized developer.
be. Such a silver halide developer (here
(referred to as cross-oxidation developer) is used after exposure during development.
Because it reduces silver halide to silver metal, it does not oxidize.
The state changes to a state of This oxidized
The developer chromatizes the sulfonamide diphenylamine.
oxidizes. Using cross oxidation developer (COD)
sulfonamide diphenylamine in photographic materials.
It becomes possible to achieve a standardized state, and at that time,
Sulfonamido diphenylamine itself is a silver
There is no need to develop it. Cross oxidation developer is an electronic
Transfer agents, i.e., developing silver halides and sulfones
transfer electrons between amidodiphenylamine and
It is considered to be an electron transfer agent. Requirements for cross-oxidized developers are generally
To: (a) No halogenation after exposure under the conditions of use.
have sufficient electrochemical potential to develop
and, (b) When in the oxidized state, the sulfonamide di
Electrochemical electricity that oxidizes phenylamine
must have a rank, and (c) When in the oxidized state, sulfonamide di
Although it undergoes a redox reaction with phenylamine
Other chemical reactions over a sufficient length of time
be stable against decomposition by It is. If any of these requirements (a), (b) or (c)
If any one of the above is not satisfied, the current
The developer cannot be called a cross-oxidation developer. Certain developers may cause cross-oxidation as described above.
Whether the developer meets the requirements depends on which
Is development carried out under such conditions?
That is, it depends on the development conditions.
Other components in the developing composition, PH of the developing composition
value, the temperature of the development process and the length of the development time.
Are all cross-oxidation developer requirements met?
It affects whether or not. Under development conditions
Which cross-oxidation developer can meet the requirements?
Other developers are also useful. As a cross oxidation developer
Examples of useful and preferred developers include:
1-phenyl-3-pyrazolidone, 1-phenyl
-4,4-dimethyl-3-pyrazolidone, and
4-hydroxymethyl-4-methyl-1-phenylene
3-pyrazolidone. like this
cross-oxidized developers are described, for example, in U.S. Pat.
Described in No. 3938995. If necessary,
Combinations of developers such as
be. Non-cross oxidation developer and cross oxidation developer
a combination of smaller proportions, generally 10
% by weight, as long as non-cross-oxidized developer is present.
It is useful in Non-cross oxidation developer and
For example, a combination with a loss oxidation developer
For example, 4-hydroxymethyl-4-methyl-1-phenyl
enyl-3-pyrazolidone and a small amount of at least one
Non-cross oxidation developers, such as ascorbic acid,
Including combinations with hydroquinone or pyrimidine
Contains. Optimal silver halide developer or development
Selection of combinations of agents can be made as desired, e.g.
Factors such as those mentioned above, including images that
Depends on specific photosensitive silver halide, processing conditions, etc.
There will be. Silver halide developer, silver halide developer set
mixture or its precursor mixed into photographic materials
It is useful to do so. However, generally
In this method, the developer is included in the processing solution, and the
The photographic materials described are processed to produce the desired dye image and
It is most useful to form a silver image. The combined image of the silver image and the dye image is added to the photographic material.
You can get it. The tone of this combined image is, for example,
Silver morphology of developed silver images, covering power of silver materials
ring power), specific pigments or pigments formed
combination, specific developer, processing conditions, etc.
It changes in various ways depending on factors such as
There will be. According to the present invention, a brown silver image is formed.
for photographic materials formed from the color formers mentioned.
Dyes are particularly useful. Because this dye
This is because the hue of is complementary to the silver image. Photographic materials contain various binders;
These binders may be used alone or in combination.
The binders described herein are naturally occurring substances, e.g.
proteins, such as gelatin, gelatin derivatives,
Cellulose derivatives, polysaccharides such as dextra
rubber, arabic gum, etc., and synthetic polymer materials,
water-soluble, such as poly(vinylpyrrolidone)
Polyvinyl compounds and acrylamide polymers
It includes both. The photographic elements described here are designed to achieve the desired properties.
Therefore, an overcoat layer and (or
) contains an interlayer and/or a subbing layer. O
- Barcoat layer, for example, abrasion resistant or on the element
It works to increase resistance to other stain formation.
have. Overcoat layer, intermediate layer or undercoat
layer may be included alone, otherwise the
including in combination with a vehicle or binder
Good too. A particularly useful binder is gelatin. Photographic elements are comprised of a variety of supports. useful
The support has structural preferences due to processing conditions.
It is resistant to unforeseen changes and
Negative impact on the desired centometric properties of the material
It is such that it has no effect on common support
is cellulose ester, poly(vinyl aceter)
), poly(ethylene terephthalate) and poly(ethylene terephthalate)
Carbonate film and related films
and resinous materials. glass, paper, gold
Supports such as genus, etc. are also useful. one
Generally, flexible supports are the most useful.
Ru. Chromogenic p-sulfonamide diphenylamine
When preparing a composition containing
Dispersing solvents, also called solvents, are used to prepare coating compositions.
Useful for manufacturing. Sulfonamide diphenyl amide
in the field of photographic technology to assist in the dispersion of
Any suitable coupler solvent known in the art is useful.
Ru. Examples of useful coupler solvents include N-n-butyl
Ruacetanilide, diethyl lauramide, di-
n-butyl phthalate, and 2,4-di-tert.
- Contains amylphenol. In addition,
sulfonamide diphenylamine in latex.
may be added or otherwise undissolved if desired.
Agent dispersions may also be prepared. In addition, it is known for its usefulness in the field of photographic technology.
Other additives that are also present in photographic materials are
Useful. These additives, for example, whitening
agents, antifoggants, stabilizers, light absorbing and scattering substances
quality, hardener, coating aid, plasticizer, lubricant, antistatic agent
substances, and matting agents. these
Additives are alsoResearch Disclosure, 1978
Also listed in December, Item No. 17643. Chromogenic p-sulfonamide diphenylamine
The photographic material containing the photographic material is placed on a suitable support using photographic techniques.
be useful for coating photographic layers in the field of
It is applied by a known method. hands like this
Methods include, for example, dipping or dip coating methods, roller
-Coating method, reverse roll coating method, air knife
Application method, doctor blade application method, spray application
method, extrusion coating method, bead coating method, stretching
-Includes flow coating method and curtain coating method
ing. Using photographic elements with various forms of energy
image exposure. This form of energy is
In contrast, photosensitive silver halide has a sensitivity to
purple on the electromagnetic spectrum.
external, visible and infrared regions as well as electron beam, base
rays, gamma rays, X-rays, alpha particles, neutrons
radiation, and other forms of radiation, e.g.
Incoherent (phase
form or coherence of
(the phase is aligned)
Contains particle wave-like radiation energy. dew
The light depends on the spectral sensitization of photosensitive silver halide
Monochromatic, orthochromatic or bread
It is chromatic. Image exposure is a developable latent image
for sufficient time to form in the photographic element.
It is common to do this for strength and strength. The photographic element described above, if the photographic element contains a silver image.
Forms a positive dye image regardless of whether it is
method or method of forming a negative dye image.
It can be processed at either location. As stated
photosensitive silver halide contained in photographic elements.
Exposure is followed by processing, silver halide and aqueous
containing an alkaline medium in the medium or as an element.
reactively combined in the presence of a developer
A visible image is formed by It is rare to obtain an inverted dye image in a photographic element.
included in the exposed element, if desired.
Non-cross oxidation development of the latent image as the first development step
The method of developing with a composition is the most useful.
During this process, the silver halide after exposure is
reduced by the oxidized developer composition, thus reducing the elemental
Changes to silver. This non-cross oxidation developing composition
oxidizes sulfonamide diphenylamine.
cannot be oxidized to convert it to the corresponding dye.
stomach. Non-cross oxidation developing composition useful in the above process
Generally, alkaline materials with non-cross-oxidized developers
It is a potassium solution. Non-cross oxidation developer photo
well known in the field of technology and
Reducing silver halide to silver after light
, oxidizes p-sulfonamide diphenylamine.
Many of them do not change to the corresponding dye.
contains a silver halide developer. In the second step, i.e. the inverted dye image
In the second step of the method for forming
exposing true elements to light or the field of photographic technology
By using a fog-forming composition known in
Fog-shaped by twisting and chemically fogging
achieve success. This fog formation is caused by chromogenic p-staining.
Negative effect on sulfonamide diphenylamine
It will not cause any adverse effects. Following the fogging process described above, a second halo
Carry out a silver germide development step. This is a cross acid
This is carried out by using a chemical development composition. color
It is in this step that a raw image is formed. This work
In such cases, any silver halide developing composition is useful.
It is. However, if the composition is p-sulfonamide
Cross-oxidize the diphenylamine to make it the desired
This is limited to cases where the dye is changed to a dye that This kind of ha
Silver halide developing compositions are cross-oxidized silver halide
Contains developer. This cross oxidation developer is
Silver halide during development, after exposure or after fogging
is reduced to silver metal, leaving it in an oxidized state.
Ru. This oxidized developer is then converted into p-sulfonate.
cross-oxidizes amide diphenylamine and
contains an amount of dye that is inversely proportional to the exposure of the photographic element.
A desired pigment having the following properties is produced. In other words, anti
A positive dye image, also called a transferred dye image, is produced.
Ru. Any unwanted silver image will be removed during the bleaching process and subsequent
Bleach-fixing by or combined with a fixing step
It can be removed by a process. One of the methods using the color-forming compound according to the present invention
For example, positive-working dyes in photographic elements after image exposure.
Examples include image forming methods. used here
The photographic element used consists of a support and a
It is a combination of reactive and reactive elements.
Substances in gelatin binder such as: (a) a photosensitive gelatin-silver halide emulsion, and (b) essentially 4-dihexylamino-4'-(2,
4,6-triisopropylbensulfonamide
d) Sulfonamide consisting of diphenylamine
Diphenylamine color former, Contains. This method is based on (A) cross-oxidized halogen
Alkaline photographic development in the absence of silver-genide developer
Developing the photographic element in a developing solution and then (B)
uniformly expose the element to a flash exposure and then
Subsequently, (C)4-methyl-4-hydroxymethyl-
Alkaline aqueous solution of 1-phenyl-3-pyrazolidone
Photographs are taken in an alkaline cross-oxidation developer consisting of a liquid
developing the element and (D) silver halide photographic element.
Bleach and fix in a bleach/fix solution to create a positive dye image
from having an image formed in the photographic element.
It's on. Here, after step (A) and before step (B),
The photographic element is prepared by using the development stop bath described above.
It is particularly useful to process. Photographic elements according to the invention, direct positive photography
It is a positive dye image containing silver halide
and useful in forming positive-working silver images.
A support and an anti-reflection material formed above the support.
The following binders are combined in a suitable manner.
Substance inside: (a) direct positive photographic silver halide, and (b) Chromogenic p-sulfonamide diphenylamine
dye precursor, In a photographic element after image exposure comprising a positive
1 for forming a type dye image and a positive type silver image
The method is as follows: (A) The photographic element is exposed to an alkaline cross-oxidized photographic material.
Developed in a true silver halide developing composition and then
(B) Fixing the resulting photographic element to a positive dye image
and a positive silver image.
Ru. Useful direct positive silver halides include, for example:
Research Disclosure, December 1978, Item No.
17643, pages 22-31. photo elements
Fixing may be accomplished using, for example, a sodium thiosulfate fixing composition.
Fixing compositions known in the photographic field such as
It can be achieved by using
Ru. Chromogenic p-sulfonamide diphene according to the present invention
One of the advantages of nilamine is the enhancement of dye images.
It has a certain stability. That is, the treatment according to the present invention
In the case of sulfonimide dyes formed after processing,
Desired conditions for post-processing conditions and visible light exposure
It has the advantage of having stability. Main departure
p-sulfonamide diphenylamine according to
Desirability regarding dye images formed from colorants
One simple test is performed to establish the level of stability.
Useful. Such tests are in the field of photographic technology.
This is a test that is publicly known in Japan.
True element average temperature 21℃ and relative humidity (RH) 45%
Exposure to simulated average North American skylight (SANS) at
(continuous exposure of 5400 lux). this
When the test compared the stability of the test dye with the control,
What is the level of stability of the dye?
You can ask for it. In one aspect of the invention, the photographic material described above is
Contains silver halide developer. silver halide
If an image agent is present in the above photographic material, the photographic material
After image exposure of the true material, the material is treated with an alkaline activator solution.
solution (this is used for the development of silver halide after exposure and
It has the function of enabling the formation of the desired pigment.
developed image by contacting with
can be formed. As mentioned above containing adulterated silver halide
When performing image development on photographic elements,
Many alkaline activators are useful. Above photo required
When developing an image in the original state, the photographic technology
common in the field, e.g. in stabilization treatments.
All alkaline activators used in
It is. An example of a useful alkaline activator is sodium hydroxide.
Thorium, potassium hydroxide, trisodium phosphate
12H₂O (PH=12), sodium metaborate (PH=
12), disodium phosphate, and monosodium phosphate
It encompasses the The most suitable alkaline activator is e.g.
For example, the desired image, specific developer, processing conditions, etc.
Depends on various factors such as
will. A particularly useful alkali activator is phosphoric acid.
Consists of trisodium (PH=12). Alkaline activators are useful over a wide concentration range.
be. Indicating the useful concentration of alkaline activator,
This is the activator solution 1 (with a pH value in the range of 11-12).
) ranges from 10 to 50 g. The optimal concentration of alkaline activator is
agent, desired image, processing conditions, and specific photosensitive materials.
Depends on factors like silver chloride, etc.
There will be. The photographic material according to the invention is made by exposing and processing it
has a sulfonimide dye image after being subjected to
or, in some cases, sulfonimide color.
It has a plain image and a silver image. sulfonimide
A dye image is essentially a color image represented by the following equation:
It is made of sulfonimide dye. In the above formula, R, R¹,R²,R³,R^Fourand R^Fiveteeth
Each is the same as the definition above. Preferably,
R contained in this dye^Fiveis a stabilizing group, e.g. 2,
It is a 4,6-triisopropylphenyl group. In the photographic material after exposure and processing according to the invention
Here are some examples of useful sulfonimide dyes:
And as follows. N-(4-dihexylaminophenyl)-N'-
(2,4,6-triisopropylbenzene sulfonate)
nyl)-p-benzoquinone diimine: N-(4-hexyloxyphenyl)-N'-
(2,4,6-triisopropylbenzene sulfonate)
nyl)-3-methyl-p-benzoquinonediimide
hmm: N-(dihexylaminophenyl)-N'-(2,
4,6-triisopropylbenzenesulfonyl)
-3-methyl-p-benzoquinone diimine: N-(4-dihexylaminophenyl)-N'-
(2,4,6-triisopropylbenzene sulfonate)
nyl)-2-methylsulfonyl-p-benzoquino
Njiimin: N-(4-dihexylaminophenyl)-N'-
(2,4,6-triisopropylbenzene sulfonate)
nyl)-2-pivalamide-p-benzoquinone di
Imin: N-(4-hexyloxyphenyl)-N'-
(2,4,6-triisopropylbenzene sulfonate)
nyl)-p-benzoquinone diimine: N-[4-N-ethyl-N-(β-methanesulfonate)
(amidoethyl)amino]-N'-(2,4,6-
triisopropylbenzenesulfonyl)-2,5
-Dipivalamide-p-benzoquinone diimine: N-(4-n-hexyloxyphenyl)-
N'-(2,4,6-triisopropylbenzene
sulfonyl)-2,5-dipivalamido-p-ben
Zoquinone diimine: N-(4-methyl-3-methanesulfonamide
phenyl)-N'-(2,4,6-triisopropylene
(rubenzenesulfonyl)-2-palmitamide-
p-benzoquinone diimine: N-(4-methoxy-3-methanesulfonamide
dophenyl)-N'-(2,4,6-triisopropro
Pyrbenzenesulfonyl)-2-pivalamide-
p-benzenequinone diimine: Next, the invention will be explained in more detail by means of the following examples.
explain. Example 1: 4-dihexylamino-4'-benzenesulfone
Preparation of amidodiphenylamine in dimethylformamide (DMF) (150ml)
N,N-dihexyl-p-phenylenediamine-
Di-p-toluenesulfonate (30.8g, 0.05mol)
Samples of (1) were stirred under a nitrogen atmosphere. Heavy coal
Sodium chloride (16.8g) and p-fluoronitro
Benzene (7.05 g, 0.05 mol) was added sequentially to the mixture.
added. This mixture was stirred at 90-100 °C overnight.
After that, the reaction mixture was poured into ice water and acetic acid was added.
Extracted with ethyl. Wash the extract with water and dry
and the solvent was removed. Woelm liquid residue
Chromatography (elution) from silica gel manufactured by
(using benzene as an agent), 4-dihe
Xylamino-4'-nitrodiphenylamine is red
Obtained as a colored oil (12.4g). This intermediate
was characterized by NMR (nuclear magnetic resonance). This nitro intermediate is prepared as described in the example below.
to the corresponding amine and the crude benzene
sulfonamide diphenylamine (17g, dark gray)
(colored oil). This crude material is used as an eluent.
using the Woelm series using chloroform.
By chromatography from Kagel
Purified. Mix the liquid residue with methanol and hexane.
When recrystallized from the compound, it had a melting point of 108-112℃.
4-dihexylamino-4'-benzenesulfate with
Yellow-brown leaves consisting of honamide diphenylamine
A solid crystal (4.7 g) was obtained. with the desired product
This was confirmed by conventional analytical methods. Example 2: 4-diethylamino-4'-benzenesulfona
Preparation of midodiphenylamine N,N-diethyl-p-phenylenediamine
(16.4 g, 0.10 mol) and p-fluoronitrobe
(14.1 g, 0.10 mol) was dissolved in 200 ml of DMF.
The resulting solution was heated at a temperature of 85 to 90°C under a nitrogen atmosphere.
and sodium bicarbonate (16.8 g, 0.20 mol).
was also stirred overnight. Pour the reaction mixture into ice water.
and extracted with ethyl acetate. evaporate the solvent
4-diethylamino-4'-nitro
Diphenylamine was obtained. This product was recrystallized from methanol.
6.2 g of red-purple foliate crystals (melting point 139-141°C)
was gotten. This product was analyzed using conventional analytical methods.
Established. The above nitro in tetrahydrofuran (100ml)
intermediate (5.7g) at 275 kilopascals (kPa)
over palladium-charcoal catalyst (1.2 g) in a Parr apparatus.
Hydrogenated with Using benzenesulfonyl chloride
the corresponding amine by its benzene
Converted to sulfonimidodiphenylamine.
When recrystallized from methanol, the temperature was 145-146℃.
A gray solid (3.58 g) with melting point was obtained. child
of compounds by NMR and other commonly used analytical methods.
The characteristics were determined. Example 3: 4-Methoxy-4'-benzenesulfonamidodi
Preparation of phenylamine p-anisidine (49.2 g, 0.4 mol) and p-
Fluoronitrobenzene (28.2g, 0.2mol)
Steam the solution obtained by dissolving it in dimethyl sulfoxide.
Stirred on bath for 24 hours. red reaction mixture
The material was poured into water (500ml) and ethyl acetate
Extracted with. Wash the extract with water and then
Dry over anhydrous magnesium sulfate. Rig the residue
Slurry it in the loin, then strain it.
A brick red solid was obtained. This solid
Dissolve in ethyl acetate, warm with charcoal, and
The solution was then passed through the solution. evaporated liquid
and the residue was recrystallized from ethyl acetate.
4-methoxy- with a melting point of 149-151°C
4'-Nitrodiphenylamine (28g) bright orange
Obtained in the form of colored needles. This intermediate is commonly used
Identification was made by chemical analysis. The above nitro compound intermediate (24.4 g, 0.1 mole)
solution obtained by dissolving 250ml of ethyl acetate
on 5% palladium-charcoal catalyst (1.5 g)
The corresponding amino acid was obtained by hydrogenation at 415 pKa.
It was converted into After evaporation, remove the solvent under vacuum.
and the bright purple solid in pyridine (150ml)
dissolved in. This is benzenesulfonyl chloride
(17.7 g, 0.1 mol) at 25°C under nitrogen atmosphere.
Allow the reaction to occur by stirring for a period of time.
Ta. After dilution with water (500 ml), the organic phase was washed with water and
Then remove the solvent and place on magnesium sulfate
Dry. The resulting red oil was dissolved in chloroform.
Dissolve and add 75 g of overcomposition (Florisil)
I went through it. Chloroform-rig the excess residue.
After recrystallizing from the loin three times,
A white powder (12 g) with a melting point of 133-135 °C was obtained.
It was done. This desired product is then subjected to routine chemical analysis.
Identified by method. Example 4: 4-dihexylamino-4'-(2,4,6-t
lyisopropylbenzenesulfonamide) diphene
Preparation of nylamine 4-dihexylamino-4'-nitrodiphenyl
A sample of amine (prepared as in Example 1 above)
sample (5.24 g, 0.013 mol) in a Parr apparatus.
(275 kPa) on palladium-charcoal catalyst (1.2
g) anhydrous tetrahydrofuran (100 ml) containing
It was reduced with hydrogen inside. Remove the solvent from the liquid under vacuum.
The resulting 4′-amino derivative was dissolved in anhydrous pyridine.
(25 ml) and at 5°C.
Lysopropylbenzenesulfonyl chloride
(4.5 g, 0.015 mol). 3 o'clock at 25℃
After stirring for a while, the reaction mixture was
(200 ml) and ice water. organic phase
Wash 5 times with water, dry, concentrate to about 50ml, and
Chromatographed on Woelm silica gel.
I got paid. Remove solvent from chloroform eluent
and recrystallize the liquid residue from methanol.
Ta. Crystalline product in methanol/water composition
(10:1 parts by volume), dried, and
Characterized by NMR and elemental analysis. desired and
The product (4.85g) has a melting point of 127-129℃
was. Example 5: 4-diethylamino-4'-(2,4,6-tri
isopropylbenzenesulfonamide) dipheni
Preparation of rumamine N,N-diethyl-p-phenylenediamine
(16.4 g, 0.01 mol) and p-fluoronitrobe
(14.1g, 0.10mol) in 200ml dimethyl
The solution obtained by dissolving in formamide was diluted with sodium bicarbonate.
(16.8 g, 0.20 mol) under nitrogen atmosphere.
Stir overnight at 85-90°C. This reaction mixture
Poured into ice water and extracted with ethyl acetate.
When the solvent was evaporated, 4-diethylamino-
4'-nitrodiphenylamine was obtained. this life
When the product was recrystallized from methanol, 139~
Red-purple foliate crystals (6.2g) with a melting point of 141℃
Obtained. This desired product was also analyzed by elemental analysis.
It was identified by A sample of the above intermediate product was reduced to 0.015
mole of 4-diethylamino-4'-aminodipheni
amine, and then the amine was dissolved under a nitrogen atmosphere.
dissolved in anhydrous pyridine (25 ml) at 5°C, and
2,4,6-triisopropylbenzenesulfony
chloride (4.52 g, 0.015 mol).
Corresponding triisopropylbenzenesulfonamide
A chromatograph made from silica gel manufactured by Woelm
roughy (using chloroform as eluent)
More refined. Reconsolidate the product from aqueous methanol
crystallized. Grayish tan solid (2.9g, molten)
152-154°C) was obtained. This desired generation
The substance was also identified by elemental analysis. Example 6: 4-hexyloxy-3'-methyl-4'-(2,
4,6-triisopropylbenzenesulfonamide
D) Preparation of diphenylamine p-hexyloxyaniline (15 g, 0.08 mole
) and 5-fluoro-2-nitrotoluene
(6.4g, 0.04mol) in dimethyl sulfoxide
(150ml) and heat the resulting solution at 90℃ overnight.
did. The reaction mixture was poured into ice water and diluted with
Extracted with chill ether. Dissolved from dried extract
Remove the agent and add a mixture of benzene and hexane.
using the compound (1:1 parts by volume) as eluent.
Chromagraph the liquid residue on Woelm silica gel.
Tographed. Then retained in the column
The fractions were eluted with ethyl acetate and again
When chromatographed, 2.75g (melting point 74)
4-hexyloxy-3'-methyl-
4'-nitrodiphenylamine was obtained. This a
was characterized by its NMR spectrum.
Ta. This is reduced to the corresponding 4′-amino derivative.
2, 4, 6-
Converted to triisopropylbenzenesulfonamide
did. Then, the obtained sulfonamide was
When recrystallized from lopanol-acetone,
Tan solid (3.1 g) with a melting point of 151-152 °C
was gotten. This desired product was obtained by NMR.
The characteristics were determined. This product was also analyzed by elemental analysis.
I identified it. Example 7: 4-dihexylamino-2'-[delta-2,4
-di-tert.-amylphenoxy)butylsulfur
moyl]-4′-benzenesulfonamide diphenylene
Preparation of rumamine 2,4-di-tert.-amylphenoxybutyla
Min (3.05 g, 0.01 mol) was dissolved in anhydrous dioxane (25
ml) and the resulting solution was dissolved in 2-chloro-5-nito
Lobenzenesulfonyl chloride in anhydrous dioxane
solution and the resulting mixture at 100 °C.
Stirred for 3 hours. Add this stirred mixture to water.
(200ml) and stirred for 1 hour.
The pale yellow solid was then recrystallized from methanol.
Ta. The obtained nitro intermediate (2.6 g) is 154-156
It had a melting point of °C. This desired intermediate
Identified by elemental analysis. This intermediate can be converted to N,N-dihexyl as described above.
Le-p-phenylenediamine p-toluenesulfo
condensed with nate and chromatographically
The products were characterized by elemental analysis. The product is
It was an orange oil (2.45g). reduce the above product to the corresponding amine, and
Next, the benzene sulfonate is added as described above.
Converted to Mido. This product is an amber glass
(1.4g), which crystallizes when left standing.
It became. This desired product is subjected to elemental analysis.
Identified it. Example 8: 4-[N-ethyl-N-(β-methanesulfona
midoethyl)amino]-2-methyl-2'-octa
Amido-4'-(2,4,6-triisopropyl
Preparation of benzenesulfonamide) diphenylamine
made Preparation of the desired intermediate is carried out as follows.
did. 4-fluoro-3-nitroaniline (15.6g,
0.1 mol) in pyridine (400 ml).
The solution was stirred at room temperature and the 2,4,6-triiso
Propylbenzenesulfonyl chloride (30.2g,
0.1 mol) was added in bulk. Tighten the resulting solution.
Close the stopper and leave it at room temperature (about 20℃) overnight (about 18℃).
time) and stirred. Then, the reaction mixture was poured into ice and hydrochloric acid.
(aqueous) (500 g of ice and 500 g of aqueous concentrated hydrochloric acid)
ml). Filter the separated oily solid.
I twisted it and removed it. Repeat from methanol and water
When recrystallized, it had a melting point of 151-152℃.
30.2 g of bright golden crystals were obtained. this place
Identify the desired intermediate product by elemental analysis.
Ta. Next, the following reaction was carried out. This reaction was carried out as follows. 42.2 g (0.1 mol) of 2-fluoro-5-(2,
4,6-triisopropylbenzenesulfonamide
d) 275 ml of 1-picoline containing nitrobenzene
, 40.6 g (0.15 mol) of 4-amino-3-methylene
-N-ethyl-N-(β-methanesulfonamide)
doethyl) aniline (in free base form)
Then, the mixture was stirred at reflux for 3 days under nitrogen.
The reaction solution was cooled to room temperature and mixed with ice water.
mixture (1.5). Add this mixture to the red
Allow to stand until brown oil separates. oil layer
It was decanted from the solid material. CH oily substance₂
Cl₂(approximately 400 ml). Then this chloride
Add 5% hydrochloric acid to the tyrene solution while stirring vigorously.
(50ml concentrated HCl plus 380.5ml water) 4 times (500ml
ml), then 5% NaHCO₃(4 times, 500ml)
and finally with 500ml of water (4 times).
Purified. Methylene chloride layer using sodium sulfate
dried and then with overcomposition (Florisil)
Vortex mixed to remove purple residue. evaporate the solvent
A red oily substance was obtained. this oil
The mixture was added to approximately 150 ml of boiling methanol. profit
Cool the methanol solution to room temperature overnight.
Rejected. Yellow-orange crystals with a melting point of 164-166 °C
Product (42.8g) was formed. silica gel glass
Perform thin layer chromatography on top and vinegar
When recrystallized from ethyl acid, the desired
A pure product (identified by elemental analysis) is obtained.
Ta. Next, the following reaction was carried out. 6.7 contained in about 75 ml of tetrahydrofuran
g (0.01 mol) of nitro compound with 10% palladium
Reduced on charcoal. This reduction takes place in a hydrogen atmosphere.
at 275kPa until hydrogen consumption ends.
(within approximately 2.5 hours). Purify the reaction mixture with nitrogen.
Gas seal and remove from Parr apparatus
Ta. At this point, do not attempt to remove the catalyst.
Ta. Calcium hydroxide as an HCl scavenger
(0.41 g, 0.055 mol) in bulk into the reaction mixture.
Added. Then octanoyl chloride (1.8
g, 0.01 mol) was added in bulk to the reaction mixture.
The resulting reaction mixture was tightly stoppered and allowed to cool to room temperature.
The mixture was stirred for 3 hours. Pyrogenicity was not observed.
Nakatsuta. Catalyst and calcium salts are removed by filtration.
I left. When the solvent was evaporated, a brown oil appeared.
was generated. Add this oil to boiling ether
Ta. The oil dissolves and a precipitate begins to form.
Ta. When I went through the trouble, I found a strong octanoylc.
A colorless solid with a loride odor was obtained. this solid
was resuspended in boiling ether (100 ml) and then
and dried under vacuum at room temperature. 98～
A very pale yellowish solid with a melting point of 100°C.
A total weight of 6.0 g was obtained. silica gel on glass
When we performed thin layer chromatography, we found that
Various solvents (ethyl acetate, methylene chloride, acetic acid
One component with acetonitrile) was recognized.
It was done. This compound was further analyzed by infrared analysis, NMR,
Characterized by mass spectrometry and elemental analysis. water
Oxidation with potassium ferricyanide
A green pigment was produced. Example 9: 4-hexyloxy-2'-pivalamide-4'-
(2,4,6-triisopropylbenzene sulfonate)
Preparation of diphenylamine 4-fluoro-3-nitroaniline and 2,
4,6-triisopropylbenzenesulfonyl
The same as in Example 8 above as the reaction product of loride.
42.2g (0.10mol) of fluoronitro compound
21.2g of the substance contained in 100ml of picoline
(0.11 mol) of p-hexyloxyaniline and
Stir at reflux overnight (approximately 24 h) under nitrogen.
Ta. This reaction is explained as follows. The reaction mixture was then poured into a mixture of ice and water (approximately
1.5) Pour on top. Although the oily substance separated
It also did not crystallize. Decant the water,
The oil was then added to methylene chloride (150ml).
Ta. Wash the methylene chloride solution thoroughly with water and remove the sulfuric acid solution.
Dry with thorium and leave a reddish-brown oil.
It was evaporated until it became solid. Boiling this oil
Added to 95% ethanol. Red crystalline after cooling
A solid separated. Apply a thin layer of silica gel on glass.
Perform romatography and then ethyl acetate.
Purification is carried out with luligroin (1:4 parts by volume).
However, only a small amount of impurity was observed. A second recrystallization was performed from 95% ethanol.
However, a red crystalline solid with a strong picoline odor.
was gotten. This solid was mixed with (a) 95% methanol and 5
% ethanol and (b) water mixture (1:1 parts by volume)
Stir in 250 ml for 30 minutes, then strain,
And air dried. Desired to have a melting point of 147-148℃
of product (49.5 g) was obtained. This desired generation
The substance was also identified by elemental analysis. Next, the following reaction was carried out. 15.0g (0.025mol) of nitro compound at room temperature
Dissolved in 100ml of tetrahydrofuran, and
of charcoal with 10% palladium on a Parr style sheaker
It was reduced to the bottom with a hydrogen pressure of 275kPa. This reduction is
The test was carried out until the consumption of the raw material was completed (about 2 hours). first
The orange solution turned colorless at this point. Previous
For preparation, by filtration under nitrogen.
The catalyst was removed. If you do this, the result will be
A slight discoloration occurred (because the amine has a tendency to oxidize).
(This is because there is). For this purpose, calcium hydroxide
(1.11 g, 0.015 mol) directly into the reflux mixture.
and then pivaloyl chloride (3.63
g, 0.03 mol) of mass was added. to this mixture
Cap tightly and stir for 1 hour.
Ta. Ethyl acetate:ligroin (1:4 parts by volume)
Thin layer chromatography on silica gel/glass using
When I performed the feed, there was no unreacted amine.
(both amine and product)
is oxidized by aqueous potassium helisinate, and
It turned into a red pigment). Then this mixture
Calcium chloride and catalyst were removed.
Removal of the solvent under reduced pressure revealed a bright rose-colored oil.
A similar substance was obtained. Heat 100ml of this oil.
Added during in-line. After cooling, a little crystal will form
However, most of the product was boiled. centre
Place the flask on a vacuum evaporator and evaporate the solvent.
I let it happen. After removing just a few millimeters of solvent
The product solidified. Passing through the red mother liquor
Then remove the colorless solid and
Washed with a large amount of ligroin. Melting point of 122-124℃
15.0 g of a colorless, air-dried solid was obtained. this place
The desired product was identified by elemental analysis. Example 10: 4-diethylamino-2-methyl-2'-methoxy
C-5'-pivalamide-4'-(2,4,6-tri
isopropylbenzenesulfonamide) dipheni
Preparation of rumamine The following reaction was carried out. 13.3 g (0.05
mole) of the nitro compound at 10% concentration at room temperature (approximately 20°C).
Reduction was carried out on radium-backed charcoal at a hydrogen pressure of 275 kPa.
This reduction is continued until the hydrogen is consumed (1.5 hours).
carried out. The catalyst is removed by filtration and the solvent
was removed by evaporation. A colorless crystalline solid is obtained.
It was. This solid is the desired amine and
was used directly for that purpose. This colorless solid
Dissolve in 250ml pyridine and the resulting solution
was cooled in an ice bath. Then triisopropyl
Benzenesulfonyl chloride (15.1g, 0.05mol)
When I added it in several parts, it turned out bright.
A yellow solution was obtained. Warm this solution to room temperature.
and stirred overnight (approximately 18 hours). This mixture
The mixture was mixed with ice (400 g) and concentrated hydrogen chloride (300 ml).
When poured into a mixture, a colorless solid was formed.
Ta. and recrystallized from acetonitrile.
However, a colorless crystal with a melting point of 177-178℃
18.6 g of solid was formed. This desired intermediate
was identified by elemental analysis. Next, the following reaction was carried out. In addition, in the formula, the group [formula] is [Formula]. The following solution was prepared. Solution A: 10.0 g (0.02
molar) starting intermediate. Solution B: 4.2 g (0.02 mol) of N,N-di in 60 ml of water
Ethyl-3-methyl-p-phenylenediamine
Hydrochloride. Solution C: 26.3 g (0.08 mol) of Felicia in 125 ml of water
Potassium anhydride. Solution D: 11.0 g (0.08 mol) of potassium carbonate in 25 ml of water
Mu. Add solution A and then solution B to solution D.
However, no color change occurred. Next, the first
Solution C was added dropwise to the mixture over a period of 15 minutes.
A green pigment was produced. After the addition is complete, the mixture is
Stir for an hour and then dilute to 1 with water.
I interpreted it. Extract the dye into methylene chloride and rinse with water.
Wash thoroughly, dry with sodium sulfate, and
and evaporated under reduced pressure. Crude green pigment is viscous
Obtained as an oil (approximately 15 g). This crude pigment
was dissolved in tetrahydrofuran and 10% para
Reduced on charcoal with hydrogen under hydrogen pressure of 275 kPa at room temperature.
Ta. This reduction is continued until the hydrogen is consumed (30 minutes).
(during) was carried out. Magenta-brown solution upon filtration
was gotten. Evaporate the solvent and methylene chloride
(approximately 300ml). This magenta brown
Add Florisil (10g) to the color solution
The mixture was made into a slurry and filtered. pale green
A solution was obtained. When the solvent was evaporated, the crude
A pale green solid was obtained. methanol - from water
Removes any traces of pigment that are recrystallized but still exist.
I couldn't get it out. Then this sample
from ether-hexane until constant melting point
It was recrystallized until it was obtained. desired product
The melting point was 201-202°C. This desired raw material
The components were identified by elemental analysis. Example 11: 4-[N-ethyl-N-(β-methanesulfona
(midoethyl)amino]-2-methyl-2',5'-di
Pivalamide-4'-(2,4,6-triisopropropylene)
pyrubenzenesulfonamide) diphenylamine
preparation of The following reaction was carried out. 15.3 g (0.1 mole) of 4-nitro-o-phenylene
Dissolve the diamine in 200ml of pyridine and
The resulting solution was cooled in an ice bath. 1 hour later
31.2 g (0.1 mol) of 2,4,6-triisopro
100ml of pyrubenzenesulfonyl chloride
The solution obtained by dissolving in lahydrofuran is used as an amine solution.
added to. Stir the resulting mixture overnight at room temperature.
and then ice (400g) plus 300ml glacial acetic acid
Added on top. The oil will separate and leave to stand.
It solidified. The crude solids were removed by filtration and
and recrystallized twice from methanol-water.
Ta. Yellow crystalline solid with a melting point of 187-191℃
(27.6g) was obtained. Thin layer chromatography on silica gel
Matography (hexane: ethyl acetate; volume ratio
3:2), the main component and subordinate component were
It is found that the mixture is represented by the above structural formula.
Ta. Identification of this desired intermediate by elemental analysis
did. Next, the following reaction was carried out. 21.0 g (0.05 mol) of crude amine was added to 250 ml of tea.
Dissolved in trahydrofuran and 6.6 g (0.05
mol) acid scavenger, N,N-dimethyla
Nirin was added in chunks. Add 6.6g to this solution.
(0.05 mol) of pivaloyl chloride 15 drops each
Added over a period of minutes. Overnight at room temperature (approx. 20℃)
After stirring for a while, a thin layer of crack indicates an incomplete reaction.
Confirmed by romatography. Therefore,
Add 5 mmol of acid chloride and a base,
The mixture was stirred again overnight. this mixture
diluted with methanol (100ml) and then 1
quenched in water. Oil separates and solidifies
did. The obtained solid was recrystallized from methanol-water.
As a result, 24.6 g of
A solid was obtained. This substance contains small amounts (less than 2%).
The following isomeric compounds of (lower) were included. The desired product was identified by elemental analysis. Next, the following reaction was carried out. 10.1g (0.02mol) of nitro compound in 125ml
in tetrahydrofuran until hydrogen consumption is complete.
(1.5 hours) with 10% palladium at 275 kPa hydrogen pressure.
Reduced on charcoal at room temperature. Remove the catalyst by filtration.
I left. 2.5g (0.021mol) acid scavenger
-, N,N-dimethylaniline, added in chunks
and then 2.5 g (0.021 mol) pivaloyl
Chloride was added in bulk. Stopper the mixture and set aside.
and stirred overnight at room temperature. Then evaporate the solvent
When the mixture was allowed to dry, an amber oil was obtained. child
The oil was crystallized from ethanol-water.
10.2 g of a colorless solid with a melting point of 196°C was obtained.
It was done. This desired intermediate was determined by elemental analysis.
Identified. The structure of this intermediate can be converted to the same compound as shown below.
Confirmed by preparing by another synthetic method.
did. 10.5g (0.02mol) of Kuplar (A) and 5.4g
(0.02 mol) of reducing agent (B) in 200 ml of tetrahydrofuran
Dissolved in orchid. Add potassium carbonate while stirring quickly.
Aqueous solution of um (11.0 g, 0.08 mol in 50 ml water)
is added to the tetrahydrofuran solution of (A) and (B) above.
did. Finally, potassium ferricyanide aqueous solution
(26.3g, 0.08mol in 150ml water) drop by drop
was added to the above solution. green color while making the addition.
pigment began to form. Following the addition, the reaction
The mixture was stirred for 45 minutes and then 1
quenched in water. Extract the dye into methylene chloride.
Remove, wash thoroughly with water, and remove sodium sulfate.
It was dried using Next, evaporation was performed.
A green oil was obtained. This oily substance
Ethyl acetate using Woelm silica gel
Chromatograph using hexane (8:2 parts by volume) as eluent.
When I fed it, 12.0g of green pigment turned out to be green.
Obtained as a solid (maximum absorption in butyl acetate)
Acquisition: 672nm). This glassy substance is further refined.
I used it directly. The following reaction was carried out. The glassy substance obtained as above is converted into tetrahydride.
Wood dissolved in Lofuran and with 10% palladium
on the charcoal until the hydrogen is consumed (about 5 minutes).
Reduction was carried out at room temperature (approximately 20°C) and hydrogen pressure of 275 kPa.
The catalyst was removed by filtration and the solvent was evaporated under reduced pressure.
When released, a bright blue oil was obtained.
Ta. This oil was mixed with ether-hexane (2.5:1
When recrystallized from 166-168℃ (by volume),
8 g of colorless solid with spots were obtained. this desire
The product was identified by elemental analysis. Example 12: 3-Methanesulfonamide-2'-octanamide
Do-4'-(2,4,6-triisopropylbenze
Preparation of (sulfonamide) diphenylamine The following reactions were carried out. Meta-methane sulfone in 25 ml alpha-picoline
Amidoaniline (1.86 g, 0.01 mol) and 2-ph
fluoro-5-(2,4,6-triisopropylbene)
(benzenesulfonamide) nitrobenzene (4.29
g, 0.01 mol) was refluxed for 29 hours.
did. Mix this mixture with 100g of ice and 100ml of 1N salt.
into the acid mixture and the separated oil
Extracted with 100ml of ethyl acetate. Mix this oil with water.
and dried with anhydrous sodium sulfate,
Then the solvent was removed. The resulting oil was eluted
manufactured by Woelm using methylene chloride as the agent.
Chromatography was performed on silica gel. Kara
1:1 part by volume of methylene chloride
Elute with ethyl acetate, remove solvent and
3-methanesulfonamide-2'-nitro-4'-
(2,4,6-triisopropylbenzene sulfonate)
It was characterized as diphenylamine.
This compound was identified by NMR. 2.9g oily
Pour the product into 150 ml of 1:1 methanol-tetrahydride.
Dissolved in Lofuran and using a Parr apparatus
and reduced with hydrogen over a palladium-charcoal catalyst.
After removing the catalyst and solvent, the solid product is
3-Methanesulfonamide-2'-a by NMR
Mino-4'-(2,4,6-triisopropylben
Specially used as diphenylamine (zensulfonamide)
Signed. Then 1.5 g (0.003 mol) of this
Dissolve the compound in 20 ml of anhydrous pyridine and add 20 ml
6.5 g of octano in anhydrous tetrahydrofuran
It was reacted with yl chloride at 5°C. 18 hours at 25℃
After that, the reaction mixture was placed in ice and 20ml of concentrated hydrochloric acid.
and the separated oil with methylene chloride.
Extracted. Add this extract to 10% sodium bicarbonate in water.
and the solvent was removed. obtained
Purification of oil by pressurized liquid chromatography
As a result, 1.3 g of glassy material was obtained. child
When the substance was recrystallized from ether-hexane,
A white foliate crystal was obtained. This desired raw material
The product was characterized by NMR. Also, 146~
It had a melting point of 148°C. A sample of this compound
Ferric acid in butyl acetate in PH=10 buffer.
Maximum absorption when oxidized with potassium anhydride
A yellow dye with a wavelength of 429 nm was obtained. Example 13: N-benzenesulfenyl-N'-(4-diethyl
aminophenyl)-p-benzoquinone diimine
Preparation of Anne dye 4-diethylamino-4'-(phenylsulfone
Amido) diphenylamine (2g, 0.005mol)
Dissolve the resulting solution in 50 ml of ethyl acetate.
With potassium carbonate (2.76g, 0.02mol) in water
The mixture was stirred for 50 minutes. Then, Felici
Potassium anide (3.29g, 0.01mol) in 30ml water
Add the solution obtained by dissolving it drop by drop under a nitrogen atmosphere.
and continued stirring for up to 15 minutes. organic phase
Separate (cyan hue), wash with water and anhydrous sulfur
dry over sodium chloride and then evaporate to dryness.
Ta. The resulting crude dye residue was treated with hot acetonitrile.
When recrystallized from rill, a black amorphous solid was obtained.
(1.65 g) was deposited. This solid is dimethyl fluoride.
Especially for mixtures of lumamide and tetrahydrofuran.
It is soluble in water and loses its cyan hue.
Ta. Spectroscopic analysis and thin layer chromatography analysis
, a non-negligible amount of color-forming pigment is mixed in amorphous form.
It turns out that it exists in things. elemental analysis
As a result, the following structural formula was found. Subsequently, alkaline (1N potassium hydroxide)
An amorphous mixture of K in ethyl acetate₃Fe(CN)₆in
When processed, a soluble cyan dye was obtained.
Ta. This regenerated cyan dye was subjected to thin layer chromatography.
When analyzed by
It turned out that it would. p-sulfonamide diphenylene as starting material
A monolayer of Ruamine using potassium ferricyanide
When oxidized in an aqueous alkaline environment, the following results were obtained.
Una desulfonated aminoindoanine dye was obtained.
Ta. Example 14: Use in silver halide photographic materials Chromogenic compound synthesized by the method described in Example 5 above
The compound was incorporated into a silver halide photographic material. Halogen consisting of a color-forming compound dispersed in a solvent
preparing a coating composition containing a silver photographic emulsion;
and poly(ethylene terephthalate) with primer.
g) It was coated on a film support. Photo obtained
The silver coverage of the element is 11.2mg/dm²It was hot. This coating
The membrane contains silver bromide in a gelatin emulsion and also contains silver bromide in a gelatin emulsion.
N-n-butylacetanilide 9.7 mg/d
m² 4.9mg/dm of chromogenic compound dissolved in²minutes
Contains a dispersion. A sample of the photographic element was measured with a commercially available sensitivity meter at 1.0 neutral.
10 through density filter^-FourImage dew for seconds
It shone. This exposure creates a developable latent image in the photograph.
formed into elements. Perform the process as follows:
Ivy. Developed for 60 seconds in the following developer: Sodium hexametaphosphate and tripolyphosphate
Salt 2.0g N-methyl-p-aminophenolsulfe
(developer) 6.0g Anhydrous sodium sulfite 50.0g Anhydrous sodium carbonate 30.0g Hydroquinone (developer) 6.0g Potassium bromide 2.0g Sodium thiocyanate 1.3g Sodium hydroxide 2.0g Potassium iodide (0.1% aqueous solution) 6.0ml Add water to total volume 1 (PH=10.1-10.3) After development, wash the element in water for 60 seconds
and then re-exposed using a flash exposure.
Ta. Then a developer that buffers this element to PH=12
solution (1 g/4-methyl-4-hydroxymethane)
Chill-1-phenyl-3-pyrazolidone, 1g/
of potassium bromide and 10ml of benzyl alcohol
The sample was immersed for 30 seconds in the solution (containing water) for 30 seconds. Next
and wash the resulting element in water for 60 seconds.
and then 60 seconds in the bleach-fix composition described below.
Rinse in between. N.H._FourFeEDTA 40g EDTA acid 4g Potassium iodide 1g 20% ammonia solution 10ml Crystalline ammonium thiosulfate 100g Anhydrous sodium sulfite 2g Ammonium thiocyanate 50ml (20% solution) Add water to total 1000ml (PH=6.2-6.5) After rinsing, wash the element with water and indoors
Air dried. In this way, the maximum image of just the dye
Image density 1.41 and minimum density 0.17 (at 680nm)
An inverted cyan dye image was obtained. Example 15: Color-forming compounds in print-out imaging materials
use The chromogenic compound described in Example 8 above is used in an imaging element.
A negative dye image was obtained using . This image formation
In the case of materials, the composition is as follows:
Supported by poly(ethylene terephthalate) film
It was applied on the body. Chromogenic compound described in Example 8 above 4.2mg/dm² Lofin dimer represented by the following formula
10.8mg/dm² (= phenyl group) Poly(methyl methacrylate) (binder)
32.4mg/dm² Elvacite2010: This is an American DuPont company (E.I.
du Pont de Nemours and Company) trademark
and available from there. After drying the obtained element, it is
Printing plate production equipment (Nu-Arc Company, Inc., USA)
More commercially available NuArc plate manufacturers)
imagewise exposed to high-intensity light. This high-intensity exposure
The maximum image density when reading with red light is 0.51.
A visible image with a minimum density of 0.06 is obtained.
Ta. Example 16: 4-(N,N-dimethylamino)-2-phenyl
Sulfonyl-4'-(2,4,6-triisopropylene)
Rubenzenesulfonamide) diphenylamine
preparation p-Nitrophenoxyacetic acid (10g, 0.05mol)
was dissolved in an excess amount of thionyl chloride (approximately 50 ml) and
To this add a few drops of dimethylformamide to obtain
The solution was refluxed for 2 hours. salt under reduced pressure
The thionyl chloride was removed and the residue was washed twice with hexane.
It was then treated and then evaporated. Te solid
Dissolved in trihydrofuran and then tetrahydrofuran
4-dimethylamino-2-phenylene in dorofuran
Rusulfonylaniline (13.8g, 0.05mol) and
N,N-diisopropylethylamine (7.0g,
0.055 mol) dropwise. After stirring at room temperature for 18 h, the reaction mixture
The salt was removed by filtration. Solidification due to evaporation of liquid
I got a body. Cool this solid from the flask with meth
Rinse with nol, strain, dry, and 222~
4-dimethylamino-2- with a melting point of 225°C
Phenylsulfonyl-α-(4-nitrophenoxy)
c) Characterized as acetanilide (19.4g)
Ta. This product was also identified by NMR. Up
The above substance (4.6 g, 0.01 mol) was dissolved in 2-methoxyethane.
Nol (70ml), ethanol (90ml) and hydroxide
Solution obtained by dissolving in sodium (10ml, 2.5N)
was refluxed for 1.5 hours, acidified with acetic acid,
Then it was cooled. The collected liquid (2.8g) was CH₃CN
When recrystallized from
4-dimethylamino-4'-nitro-2-phenylene
Obtained rusulfonyldiphenylamine (2.3g)
It was. This product was further identified by NMR.
did. The obtained substance (2.1 g, 0.0053 mol) was
Hydrogenation was carried out over charcoal at a hydrogen pressure of 275 kPa. water
Hydrogenation was carried out until the hydrogen was consumed (3 hours)
did. The desired amine is produced by this hydrogenation.
did. Pass through a supercomposition (Celite).
After removing the catalyst by washing sodium sulfate
Dry the liquid by using
4,6-triisopropylbenzenesulfonyl
loride (1.6 g, 0.053 mol) and N,N-diiso
Propylethylamine (0.7g, 0.0053mol)
Added. Place the solution under nitrogen atmosphere for 18 hours.
Reflux, cool, strain to remove salts, and
and evaporated. CH the residue₃Recrystallized from CN.
This desired product has a melting point of 221-225°C
This product was further analyzed by NMR.
Identified. This product was also identified by elemental analysis.
did. Example 17: 4-(N,N-diethylamino)-2-methyl-
3'-Methyl-4'-(2,4,6-triisosul
Preparation of honamido) diphenylamine To prepare the desired intermediate, the following
Synthesis was carried out. 15.3 g of 3-methyl-4-nitrophenol and
Dissolve 13 g of ethyl chloroacetate in acetone,
and over 2 days on 16g of potassium carbonate.
It refluxed. Strain the solution, pour the liquid into water,
Then, it was extracted with ethyl acetate. ethyl acetate extract
was evaporated to obtain an oil, and this oil was added to 300 ml of
Dissolved in ethanol. To this, 10 in 50ml of water
g of potassium hydroxide was added. Steam bath the mixture
Heat for 2 hours on top, and remove most of the ethanol.
evaporate, acidify with hydrochloric acid, dilute with water and filter
and the solid was dried. solid to acetonitrile
When recrystallized from the glass, 8.5 g of the desired raw material
A product was obtained. Next, the following reaction was carried out. 8.4 g (0.04 mol) of (3-methyl-4-nito
(lophenoxy) acetic acid with 3 drops of dimethylformamide
dissolved in approximately 35 ml of thionyl chloride containing
Heated for 2 hours. Evaporate excess thionyl chloride
The residue was dissolved in methylene dichloride and diluted twice.
evaporated over a period of time. The residue was then dissolved in glacial acetic acid.
Dissolve and dissolve 8.6 g of N,N-diethyl in acetic acid.
-3-methyl-p-phenylenediamine hydrochloride
added to. Add 8.0g of sodium acetate,
The solution was then warmed up. After stirring for 2 hours, the solution
The liquid was poured into water. Take the precipitated solid and
and dried. Reconstituted twice from methanol.
When crystallized, the desired product has a melting point of 141-142°C.
A compound was obtained. This compound to NMR
Identified it more. Obtained from carbon-hydrogen-nitrogen analysis.
The compound obtained is recognized to be the desired product.
Ta. Next, the following reaction was carried out. 7g of compound (A) was added to 140ml of 2-methoxyethano
solution obtained by dissolving in ethanol and 140 ml of ethanol
Dissolve 2g of sodium hydroxide in 20ml of water.
The resulting solution was added. The combined solution was then heated for 2 hours.
Reflux for a period of time, cool and acidify with acetic acid.
It became. Remove most of the ethanol and leave the rest
was poured into the water. In this way, a solid is formed.
then take this solid and dry it
did. When recrystallized from acetonitrile,
The desired compound with a melting point of 132-133°C is obtained.
It was done. Next, the following reaction was carried out. 1.8g (0.006mol) of compound (B) in 100ml of tet
Dissolved in lahydrofuran and palladium-wood
It was reduced with hydrogen over a charcoal catalyst at a hydrogen pressure of 275 kPa. touch
Separate the medium and dry the liquid over sodium sulfate.
It was dry. Add 1.74g (0.13mol) of sulfonate to this solution.
Nyl chloride and N,N-diisopropylethyl
Amines (often called Hu¨nig bases)
Added. This solution was refluxed overnight under nitrogen.
Heated. After evaporating the tetrahydrofuran,
Dissolve the dark blue residue in ethyl acetate and wash with water.
, dried, and concentrated. Then salt the residue
Dissolved in methylene chloride and added silica from Woelm.
Chromatography on Kagel to remove impurities
removed. Separate the main component fractions
and concentrated. Tetrahydrofuran again
and hydrogen pressure over the palladium-charcoal catalyst.
Hydrogen reduction was performed at 275 kPa. Pass the catalyst
and concentrated the liquid to give a yellow oil.
Ta. This oil was dissolved in hot hexane. blend
Upon cooling, a white solid was formed. this
The desired product is a white solid with a melting point of 152-154 °C
It was hot with stuff. This product was analyzed by NMR and further
Identified by elemental analysis. The compounds described in Examples 18 to 179 below were added to Example 1.
~Prepared according to the same procedure as described in Example 17
Ta. Example 18: 4-morpholino-4'-(2,4,6-triiso
Propylbenzenesulfonamide) Diphenyla
Min (melting point 203-205℃) Example 19: 4-(N,N-dimethylamino)-4'-(2,4,
6-triisopropylbenzenesulfonamide)
Diphenylamine (melting point 166-168℃) Example 20: 4-N,N-dihexylamino)-2'-chloro
-4'-(2,4,6-triisopropylbenzene
sulfonamide) diphenylamine Example 21: 4-(N,N-dihexylamino)-2'-[δ-
(2,4-di-t-amylphenoxy)butylka
Rubamoyl]-4'-(2,4,6-triisopropylene
rubenzenesulfonamide) diphenylamine
(Melting point 151-152℃) Example 22: 4-(N,N-didodecylamino)-3'-methyl
-4'-(2,4,6-triisopropylbenzene
sulfonamide) diphenylamine, p-toluene
sulfonate (melting point 172-174℃) Example 23: 4-[N-ethyl-N-(octanoylmethyl)
Amino]-3'-methyl-4'-(2,4,6-triyl
Sopropylbenzenesulfonamide) diphenyl
Amine (melting point 86-88℃) Example 24: 4-(N,N-didodecylamino)-2'-[δ-
(2,4-di-t-amylphenoxy)butyls
[rufuamoyl]-4'-(2,4,6-triisopropropylene)
pyrubenzenesulfonamide) diphenylamide
p-toluenesulfonate (melting point 154-155
℃) Example 25: 4-methoxy-2-methyl-2'-(4-decyl)
Benzamide-4'-(2,4,6-triisopropropylene)
pyrubenzenesulfonamide) diphenylamine Example 26: 4-(N,N-dihexylamino)2-phenylene
rusulfonyl-4'-(2,4,6-triisopropropylene)
pyrubenzenesulfonamide) diphenylamine
(Melting point 144℃) Example 27: 4-(N,N-diethylamino)-2-methyl-
4'-(2,4,6-triisopropylbenzene
sulfonamide) diphenylamine (melting point 158-159
℃) Example 28: 4-(N,N-diethylamino)-2,3'-dime
Chyl-4'-(2,4,6-triisopropylben
Zensulfonamide) diphenylamine (melting point
152-154℃) Example 29: 4-[N-ethyl-N-(β-methoxyethyl)
Amino]-2-methyl-2'-[(4-morpholino)
sulfamoyl]-4-(2,4,6-triisopropylene)
ropylbenzenesulfonamide) diphenylamide
(melting point 168-169℃) Example 30: 4-(N,N-dimethylamino)-2-methyl-
5-methoxy-4'-(2,4,6-triisopropropylene)
pyrubenzenesulfonamide) diphenylamine Example 31: 4-(N,N-dimethylamino)-2-methyl-
5-Methoxy-2'-octanamide-4'-(2,
4,6-triisopropylbenzenesulfonamide
D) Diphenylamine (melting point 190-194℃) Example 32: 4-[N-ethyl-N-(β-methanesulfona
midoethyl)amino]-2-methyl-2'-pival
Amido-4'-(2,4,6-triisopropylbene)
(benzenesulfonamide) diphenylamine (melting point
143-145℃) Example 33: 4-hexyloxy-2'-(4-methoxyphenate)
noxy)formamide-4'-(2,4,6-tri
isopropylbenzenesulfonamide) dipheni
Ruamine Example 34: 4-(N,N-dihexylamino)-3'-pival
Amido-4'-(2,4,6-triisopropylbene)
(benzenesulfonamide) diphenylamine (melting point
146-148℃) Example 35: 4-[N-ethyl-N-(β-methoxyethyl)
Amino]-2-methyl-2'-octanamide-
4'-(2,4,6-triisopropylbenzene
sulfonamide) diphenylamine (melting point 137-138
℃) Example 36: 4-[N-ethyl-N-(β-methanesulfona
(midoethyl)amino]-2-methyl-2',5'-di
Pivalamide-4'-(2,4,6-triisopropropylene)
pyrubenzenesulfonamide) diphenylamine Example 37: 4-Piperidino-2'-methoxy-5'-pivalua
Mido-4'-(2,4,6-triisopropylben
Zensulfonamide) diphenylamine (melting point
209~210℃) Example 38: 4-hexyloxy-2'-acetamido-4'-
(2,4,6-triisopropylbenzene sulfonate)
(amide) diphenylamine Example 39: 4-[N-ethyl-N-(β-methanesulfona
(midoethyl)amino]-2-methyl-2',5'-di
Dodecyloxy-4-(2,4,6-triisopropylene)
ropylbenzenesulfonamide) diphenylamide
(melting point 75-78℃) Example 40: 4-(N,N-diethylamino)-2-methyl-
2'-Methoxy-5'-[α-(2,4-di-t-amino)
ruphenoxy)hexanamide]-4'-(2,4,
6-triisopropylbenzenesulfonamide)
Diphenylamine (melting point 107-110℃) Example 41: 4-[N-ethyl-N-(β-methanesulfona
(midoethyl)amino]-2-methyl-2',5'-di
Pivalamide-4'-(methanesulfonamide) di
phenylamine Example 42: 4-[N-ethyl-N-(β-methanesulfona
(midoethyl)amino]-2-methyl-2',5'-di
Pivalamide-4'-benzenesulfonamide dif
enylamine Example 43: 4-[N-ethyl-N-(β-methanesulfona
(midoethyl)amino]-2-methyl-2',5'-di
Pivalamide-4'-(2,4,6-trimethylbase)
(benzenesulfonamide) diphenylamine Example 44: 4-phenoxy-3'-methyl-4'-(2,4,
6-triisopropylbenzenesulfonamide)
Diphenylamine (melting point 140-142℃) Example 45: 4-(2,6-dimethylphenoxy)-3'-methy
-4'-(2,4,6-triisopropylbenze
sulfonamide) diphenylamine (melting point 210
℃) Example 46: 4-(2,6-diisopropylphenoxy)-
3'-Methyl-4'-(2,4,6-triisopropyl
rubenzenesulfonamide) diphenylamine
(Melting point 124-126℃) Example 47: 4-[2,6-di(1-methylpropyl)phene
[Noxy]-3'-methyl-4'-(2,4,6-triyl
Sopropylbenzenesulfonamide) diphenyl
Amine (melting point 163-164℃) Example 48: 2,4-dimethoxy-2'-[δ-(2,4-di-
t-amylphenoxy)butylsulfamoyl]
-4'-(2,4,6-triisopropylbenzene
sulfonamide) diphenylamine (melting point 139~
140℃) Example 49: 4-hexyloxy-2'-[δ-(2,4-di-
t-amylphenoxy)butylcarbamoyl]-
4'-(2,4,6-triisopropylbenzene
sulfonamide) diphenylamine Example 50: 4-hexyloxy-2'-methylsulfonyl-
4'-(2,4,6-triisopropylbenzene
sulfonamide) diphenylamine (melting point 136-138
℃) Example 51: 4-hexyloxy-2'-carboxy-4'-
(2,4,6-triisopropylbenzene sulfonate)
Diphenylamine (melting point 179-181℃) Example 52: 4-hexyloxy-3'-ethoxycarbonyl
-4'-(2,4,6-triisopropylbenzene
sulfonamide) diphenylamine Example 53: 4-hexyloxy-2'-(2-methyl)buta
Amido-4'-(2,4,6-triisopropyl
benzenesulfonamide) diphenylamine Example 54: 4-hexyloxy-3'-pivalamide-4'-
(2,4,6-triisopropylbenzene sulfonate)
Diphenylamine (melting point 120-122℃) Example 55: 4-octyloxy-2'-pivalamide-4'-
(2,4,6-triisopropylbenzene sulfonate)
Diphenylamine (melting point 95-100℃) Example 56: 4-Methoxy-2-methyl-2'-pivalamide
-4'-(2,4,6-triisopropylbenzene
sulfonamide) diphenylamine Example 57: 4-Methoxy-2-methyl-2'-octanami
Do-4'-(2,4,6-triisopropylbenze
sulfonamide) diphenylamine (melting point 146
~148℃) Example 58: 4-methoxy-2-methyl-2'-n-hexyl
Ureido-4'-(2,4,6-triisopropyl
benzenesulfonamide) diphenylamine
point 124-126℃) Example 59: 4-hexyloxy-2'-[α-(2,4-di-
t-Amylphenoxy)hexanamide]-4'-
(2,4,6-triisopropylbenzene sulfonate)
(amide) diphenylamine Example 60: 4-hexyloxy-2'-(N-methyl)acetate
toamide-4'-(2,4,6-triisopropyl
benzenesulfonamide) diphenylamine
point 67~75℃) Example 61: 4-hexyloxy-3-methoxy-4'-(2,
4,6-triisopropylbenzenesulfonamide
D) Diphenylamine (melting point 142-143℃) Example 62: 4-hexyloxy-3'-methylsulfonyl-
4'-(2,4,6-triisopropylbenzene
sulfonamide) diphenylamine (melting point 118℃) Example 63: 4-hexyloxy-3-methyl-4'-(4-
hydroxyphenyl) sulfonamide diphenyl
amine Example 64: 3-(4-dodecyloxyphenyl)sulfone
Amido-4'-(2,4,6-triisopropylbene)
(benzenesulfonamide) diphenylamine (melting point
154-155℃) Example 65: 3-(2,4-di-t-amylphenoxy)a
Cetamide-4'-(2,4,6-triisopropylene)
rubenzenesulfonamide) diphenylamine
(Melting point 153-154℃) Example 66: 4-(2,4-di-t-amylphenoxy)a
Cetamide-4'-(2,4,6-triisopropylene)
rubenzenesulfonamide) diphenylamine
(Melting point 182-183℃) Example 67: 4-n-octylureido-4'-(2,4,6
-triisopropylbenzenesulfonamide) di
Phenylamine (melting point 200-203℃) Example 68: 4,4'-bis(2,4,6-triisopropyl
benzenesulfonamide) diphenylamine
point 211-212℃) Example 69: 4-hexyloxy-2'-(2-ethyl)buta
Amido-4'-(2,4,6-triisopropyl
benzenesulfonamide) diphenylamine Example 70: 4-hexyloxy-2'-octanamide-
4'-(2,4,6-triisopropylbenzene
sulfonamide) diphenylamine Example 71: 4-(N,N-diethylamino)-4'-(4-n
-dodecyloxybenzenesulfonamide) diphenyl
Enylamine (melting point 171-172℃) Example 72: 4-(N,N-diethylamino)-4'-methane
sulfonamide diphenylamine (melting point 106-108
℃) Example 73: 4-hexyloxy-2'-(2-ethyl)hex
Sanamide-4'-(2,4,6-triisopropylene)
rubenzenesulfonamide) diphenylamine Example 74: 4-(N,N-dihexylamino)-4'-(2,
4,6-trimethylbenzenesulfonamide) di
Phenylamine, p-toluenesulfonate (fused)
point 123~124℃) Example 75: 4-hexyloxy-2'-cyclohexanecal
Boxamide-4'-(2,4,6-triisopropropylene)
pyrubenzenesulfonamide) diphenylamine Example 76: 4-(N,N-dihexylamino)-3'-methyl
-4'-benzenesulfonamide diphenylamine
(Melting point 76-78℃) Example 77: 4-(N,N-dihexylamino)-3'-methyl
-4'-(2,4,6-triisopropylbenzene
sulfonamide) diphenylamine (melting point 81-82
℃) Example 78: 4-(N,N-dihexylamino-2'-methyl
Sulfonyl-4'-benzenesulfonamide diphene
Nylamine (melting point 141℃) Example 79: 4-(N,N-dihexylamino)-2'-methyl
Sulfonyl-4'-(2,4,6-triisopropylene)
rubenzenesulfonamide) diphenylamine
(Melting point 115-116℃) Example 80: 4-(N,N-dihexylamino)-2'-(N,
N-diethylsulfamoyl)-4'-benzene
sulfonamide diphenylamine Example 81: 4-(N,N-dihexylamino)-3'-trif
fluoromethyl-4'-benzenesulfonamide diphenyl
enylamine, p-toluenesulfonate (melting point
164-165℃) Example 82: 4-(N,N-dihexylamino)-2'-trif
fluoromethyl-4'-benzenesulfonamide diphenyl
enylamine, p-toluenesulfonate (melting point
165-166℃) Example 83: 4-hexyloxy-2'-hexadecaneamide
-4'-(2,4,6-triisopropylbenzene
sulfonamide) diphenylamine Example 84: 4-hexyloxy-2'-benzamide-4'-
(2,4,6-triisopropylbenzene sulfonate)
(amide) diphenylamine Example 85: 4-hexyloxy-4'-benzenesulfona
Midodiphenylamine (melting point 119-120℃) Example 86: 4-hexyloxy-4'-(2,4,6-tri
isopropylbenzenesulfonamide) dipheni
Ruamine (melting point 127℃) Example 87: 4-Hexyloxy-3'-methyl-4'-benze
sulfonamide diphenylamine (melting point 129~
131℃) Example 88: 4-hexyloxy-2'-(4-n-pentyl)
Benzamide-4'-(2,4,6-triisopropropylene)
pyrubenzenesulfonamide) diphenylamine Example 89: 4,4'-di(p-toluenesulfonamide)di
phenylamine Example 90: 4-[N-ethyl-N-(β-methanesulfona
midoethyl)amino]-2-methyl-2'-octa
4′-benzenesulfonamide diphenylene
Ruamine Example 91: 4-[N-ethyl-N-(β-methanesulfona
midoethyl)amino]-2-methyl-3'-pival
Amido-4'-(2,4,6-triisopropylbene)
(benzenesulfonamide) diphenylamine Example 92: 4-{N-ethyl-N-[β-methylmethanesulfate
Honamido)ethyl]amino}-2-methyl-
2'-octanamide-4'-(2,4,6-triyl
Sopropylbenzenesulfonamide) diphenyl
amine Example 93: 4-[N-ethyl-N-(β-methanesulfona
midoethyl)amino]-2-methyl-2'-(3-o)
cutylsulfamoyl)benzamide-4'-(2,
4,6-triisopropylbenzenesulfonamide
D) Diphenylamine (melting point 73-80℃) Example 94: 4-(N,N-dimethylamino)-3-methoxy
-2-methyl-2'-methanesulfonyl-4'-(2,
4,6-triisopropylbenzenesulfonamide
D) Diphenylamine (melting point 110-113℃) Example 95: 4-(N,N-diethylamino)-2-methyl-
4′-Benzenesulfonamide naphthylphenyla
Min (melting point 213-216℃) Example 96: 4-(N,N-diethylamino)-2-methyl-
2'-[α-(2,4-di-t-amylphenoxy)
hexaneamide]-4'-benzenesulfonamide
Naphthyl phenylamine (melting point 148-152℃) Example 97: 4-[N-ethyl-N-(β-methanesulfona
(midoethyl)amino]-2-methyl-4'-benze
sulfonamide naphthylphenylamine (melting point
156-158℃) Example 98: 4-[N-ethyl-N-(β-methanesulfona
midoethyl)amino]-2-methyl-4'-(4-do)
Decyloxy)benzenesulfonamide naphthyl
Phenylamine (melting point 113-115℃) Example 99: 4-[N-ethyl-N-(β-methanesulfona
(midoethyl)amino]-2-methyl-2'-decane
Amido-4-benzenesulfonamide naphthylph
enylamine Example 100: 4-[N-methyl-n-acetamido]amino
-2'-octanamide-4'-(2,4,6-tri
isopropylbenzenesulfonamide) dipheni
Ruamine Example 101 4-n-ocluureido-2'-octanamide
-4'-(2,4,6-triisopropylbenzene
sulfonamide) diphenylamine (melting point 114~
115℃) Example 102: 1,4-bis{N-[4,4′-bis(2,4,
6-triisopropylbenzenesulfonamide)
-2,2'-bisoctanamide]} phenyl
Enylene diamine (melting point 185-186℃) Example 103: 4-Methoxy-2-methyl-2'-hexadecane
Amido-4'-(2,4,6-triisopropylbene)
(benzenesulfonamide) diphenylamine Example 104: 4-Methoxy-2-methyl-2'-[(3-aceto
xy)propionamide]-4'-(2,4,6-t
lyisopropylbenzenesulfonamide) diphene
Nylamine (melting point 150-151℃) Example 105: 4-Methoxy-2-methyl-2'-[(3-carbo
xy)propionamide]-4'-(2,4,6-t
lyisopropylbenzenesulfonamide) diphene
Nylamine (melting point 174℃) Example 106: 4-hexyloxy-2'-(4-n-decyl)
Benzamide-4'-(2,4,6-triisopropropylene)
pyrubenzenesulfonamide) diphenylamine Example 107: 2,4-dimethoxy-3'-methyl-4'-(2,
4,6-triisopropylbenzenesulfonamide
D) Diphenylamine (melting point 154-155℃) Example 108: 2,4-dimethoxy-2'-octanamide-
4'-(2,4,6-triisopropylbenzene
sulfonamide) diphenylamine (melting point 133-135
℃) Example 109: 4-Methoxy-3-methanesulfonamide-
2'-octanamide-4'-(2,4,6-triyl
Sopropylbenzenesulfonamide) diphenyl
amine Example 110: 4-Methoxy-3-(N-methyl)methanesul
Honamide-2'-octanamide-4'-(2,4,
6-triisopropylbenzenesulfonamide)
diphenylamine Example 111: 4-Methoxy-3-methanesulfonamide-
2'-pivalamide-4'-(2,4,6-triiso
Propylbenzenesulfonamide) Diphenyla
Min (melting point 165-167℃) Example 112: 3,4,5-trimethoxy-2'-hexadecane
Amido-4'-(2,4,6-triisopropylbene)
(benzenesulfonamide) diphenylamine (melting point
110-112℃) Example 113: 4-Methoxy-3,5-dibromo-2',5'-di
Pivalamide-4'-(2,4,6-triisopropropylene)
pyrubenzenesulfonamide) diphenylamine
(Melting point 186-187℃) Example 114: 4-Methoxy-3-bromo-2',5'-dipival
Amido-4'-(2,4,6-triisopropylbene)
(benzenesulfonamide) diphenylamine (melting point
214-215℃) Example 115: 4-Methoxy-2',5'-dipivalamide-4'-
(2,4,6-triisopropylbenzene sulfonate)
Diphenylamine (melting point 201-202℃) Example 116: 4-Methoxy-3,5-dichloro-2',5'-di
Pivalamide-4-(2,4,6-triisopropropylene)
pyrubenzenesulfonamide) diphenylamine
(Melting point 186-187℃) Example 117: 4-ethylcarbonylmethyleneoxy-2'-o
Cutanamide-4'-(2,4,6-triisopropropylene)
pyrubenzenesulfonamide) diphenylamine
(Melting point 126-127℃) Example 118: 4-Carboxymethyleneoxy-2'-octane
Amido-4'-(2,4,6-triisopropylbene)
(benzenesulfonamide) diphenylamine (melting point
108~110℃) Example 119: 4-[N-β-(4-methoxybenzoyl)hydro
Radino]-2-octanamide-4'-(2,4,6
-triisopropylbenzenesulfonamide) di
Phenylamine (melting point 166-168℃) Example 120: 4-hexyloxy-2',5'-dipivalamide
-4'-(2,4,6-triisopropylbenzene
sulfonamide) diphenylamine Example 121: 4-hexyloxy-3'-pipalamide-4'-
(2,4,6-triisopropylbenzene sulfonate)
Diphenylamine (melting point 120-122℃) Example 122: 4-hexyloxy-2'-[α-(2,4-di-
t-Amylphenoxy)hexanamide]-4'-
(2,4,6-triisopropylbenzene sulfonate)
(amide) diphenylamine Example 123: 4-hexyloxy-2'-[α-(3-t-butyl
(4-acetoxyphenyl)tetradecanami
]-4'-(2,4,6-triisopropylbenze
sulfonamide) diphenylamine Example 124: 4-hexyloxy-2'-[α-(3-t-butyl
-4-hydroxyphenyl)tetradecanami
]-4'-(2,4,6-triisopropylbenze
sulfonamide) diphenylamine Example 125: 4-hexyloxy-2'-(3-octylsul
fuamoyl)benzamide-4'-(2,4,6-
Triisopropylbenzenesulfonamide) Diph
Enylamine (melting point 65-75℃) Example 126: 4-hexyloxy-2'-[3-(N-methyl)
Octylsulfamoyl]benzamide-4′-
(2,4,6-triisopropylbenzene sulfonate)
(amide) diphenylamine Example 127: 4-hexyloxy-2'-(3-ethoxyl
Bonylmethylenesulfamoyl)benzamide
4'-(2,4,6-triisopropylbenzene
sulfonamide) diphenylamine (melting point 90-93
℃) Example 128: 4-hexyloxy-2'-methyl-6'-octa
Amido-4'-(2,4,6-triisopropyl
benzenesulfonamide) diphenylamine
point approx. 45℃) Example 129: 3,5-bis{N-[2-(N-hexoxylph)
enyl)amino-5-(2,4,6-triisopropylene)
(ropylbenzenesulfonamide) phenylcal
bamoyl}isoamylphenoxybenzene (melting point
82-87℃) Example 130: 4-hexyloxy-3'-chloro-4'-(2,
4,6-triisopropylbenzenesulfonamide
D) Diphenylamine (melting point 143-144℃) Example 131: 4-hexyloxy-4'-(2,4,6-tri
isopropylbenzenesulfonamide) naphthyl
Phenylamine (melting point 161-162℃) Example 132: 4-hexyloxy-4'-(4-dodecyloxy
Cybenzenesulfonamide) Naphthylphenyla
Min (melting point 101-102℃) Example 133: 4-Hexyloxy-2'-octanamide-
4′-Benzenesulfonamide naphthylphenyla
Min (melting point 142-144℃) Example 134: 4-Hexyloxy-3'-methyl-5'-phenylated
rusulfonyl-4'-(2,4,6-triisopropropylene)
pyrubenzenesulfonamide) diphenylamine
(Melting point 167-168℃) Example 135: 4-Hexyloxy-2',3'-dimethanesulfo
Nyl-4'-(2,4,6-triisopropylben
Zensulfonamide) diphenylamine (melting point
152-153℃) Example 136: 4-hexyloxy-2'-(4-methoxy)base
nzamide-4'-(2,4,6-triisopropylene)
rubenzenesulfonamide) diphenylamine Example 137: 3-(N-methyl)methanesulfonamide-
2'-octanamide-4'-(2,4,6-triyl
Sopropylbenzenesulfonamide) diphenyl
amine Example 138: 3-(N-methyl)methanesulfonamide-
2'-hexadecanamide-4'-(2,4,6-t
lyisopropylbenzenesulfonamide) diphene
Nylamine (melting point 110-118℃) Example 139: 3-methanesulfonamido-4-methyl-2'-
Hexadecaneamide-4'-(2,4,6-triyl)
Sopropylbenzenesulfonamide) diphenyl
Amine (melting point 63-67℃) Example 140: 2,4-dimethyl-5-methanesulfonamide
-2'-hexadecanamide-4'-(2,4,6-
Triisopropylbenzenesulfonamide) Diph
Enylamine (melting point 63-68℃) Example 141: 2-Methoxy-5-methanesulfonamide-
2'-octanamide-4'-(2,4,6-triyl
Sopropylbenzenesulfonamide) diphenyl
amine Example 142: 3-methanesulfonamide-2',5'-dipival
Amido-4'-(2,4,6-triisopropylbene)
(benzenesulfonamide) diphenylamine Example 143: 3-acetamido-2'-octanamide-4'-
(2,4,6-triisopropylbenzene sulfonate)
Diphenylamine (melting point 75-83℃) Example 144: 4-[N-ethyl-N-(β-methanesulfona
midoethyl)amino]-2-methyl-4'-(2,
4,6-triisopropylbenzenesulfonamide
D) Diphenylamine Example 145: 4-hexyloxy-2'-(4-chloro)ben
Zuamide-4'-(2,4,6-triisopropyl
benzenesulfonamide) diphenylamine Example 146: 4-hexyloxy-2'-(4-cyano)ben
Zuamide-4'-(2,4,6-triisopropyl
benzenesulfonamide) diphenylamine Example 147: 4-hexyloxy-2'-(nt-butyl)
Ureido-4'-(2,4,6-triisopropyl
benzenesulfonamide) diphenylamine Example 148: 4-hexyloxy-2'-(n-octyl)
Reid-4'-(2,4,6-triisopropylbenzene)
(benzenesulfonamide) diphenylamine Example 149: 4-hexyloxy-2'-(n-octadecyl)
Ureido-4'-(2,4,6-triisopropyl
benzenesulfonamide) diphenylamine Example 150: 4-hexyloxy-2'-cyclohexylure
Ido-4'-(2,4,6-triisopropylben
Zensulfonamide) diphenylamine Example 151: 4-hexyloxy-2'-phenylureido-
4'-(2,4,6-triisopropylbenzene
sulfonamide) diphenylamine Example 152 4-hexyloxy-2'-(4-methylphenylene)
) ureido-4'-(2,4,6-triisopropropylene)
pyrubenzenesulfonamide) diphenylamine Example 153 4-hexyloxy-2'-(4-methoxyphenate)
ureido-4'-(2,4,6-triisopropylene)
ropylbenzenesulfonamide) diphenylamide
hmm Example 154: 4-hexyloxy-2'-(4-chlorophenylene)
) ureido-4'-(2,4,6-triisopropropylene)
pyrubenzenesulfonamide) diphenylamine Example 155: 4-hexyloxy-2'-(4-cyanopheni
) ureido-4'-(2,4,6-triisopropropylene)
pyrubenzenesulfonamide) diphenylamine Example 156: 4-hexyloxy-2'-butoxyformamide
Do-4'-(2,4,6-triisopropylbenze
sulfonamide) diphenylamine Example 157: 4-hexyloxy-2'-octyloxyform
Muamide-4'-(2,4,6-triisopropyl
benzenesulfonamide) diphenylamine Example 158: 4-hexyloxy-2'-phenoxyformua
Mido-4'-(2,4,6-triisopropylben
Zensulfonamide) diphenylamine Example 159: Inversion processing to form a positive dye image Represented by the following formula prepared in Example 5 above:
Chromogenic sulfonamide diphenylamine pigment
Recasa, i.e. 4-diethylamino-4'-
(2,4,6-triisopropylbenzene sulfonate)
(amide) diphenylamine: (Compound 1e) obtained by dispersing in N-n-butylacetanilide
A gelatin-silver bromide photographic emulsion containing a dispersion of
Prepared. This emulsion was deposited on a film support with silver
(Ag⁺) Coverage amount 104mg/ft²(11.2mg/dm²),
and compound 1e45mg/ft²and N-n-butyla
Cetanilide 90mg/ft²(4.9 and 9.7, respectively)
mg/dm²(corresponding to). the obtained film
sample with a 1.0 neutral concentration film using a commercially available sensitivity meter.
10 through the tar^-FourImage exposed for 2 seconds
A developable latent image was formed on the film. exposure
The subsequent processing of the film was carried out as follows. 1 Develop for 60 seconds in the following developer (a) Sodium hexametaphosphate 2.0g (b) N-methyl-p-aminophenolsulf
Eight 6.0g (c) Sodium sulfite (anhydrous) 50.0g (d) Sodium carbonate (anhydrous) 30.0g (e) Hydroquinone 6.0g (f) Potassium bromide 2.0g (g) Sodium thiocyanate 1.3g (h) Sodium hydroxide 2.0g (i) Potassium iodide (0.1% solution) 6.0ml (j) Add water to total volume 1 (PH10.1-10.3) 2 Washing in water for 60 seconds 3 Re-exposure with uniform flash exposure 4 Development buffered to PH=12 containing the following ingredients:
30 seconds development in liquid (a) 4-hydroxymethyl-4-methyl-1-
Phenyl-3-pyrazolidone (cross-oxidized
Image agent) 1g/ (b) Potassium bromide 1g/ (c) Benzyl alcohol 10ml/ (d) Add water and total amount 1 5 Wash in water for 60 seconds 6 The following bleaching and fixing compositions (Compositions B-F)
Rinse for 60 seconds in (a) (NaFe or NH_FourFe) Ethylenediamine 4
Acetic acid 40.0g (b) Ethylenediaminetetraacetic acid (EDTA) 4.0g (c) Potassium bromide 1g (d) Ammonia (20% aqueous solution) 10ml (e) Ammonium thiosulfate, crystal liquid 100g (f) Sodium sulfite, anhydrous 2g (g) Sodium or ammonium thiocyanate
(20% aqueous solution) 50ml (h) Add water to total volume 1 (PH6.2-6.5) 7. Wash in water for 120 seconds 8 Air dry indoors at 22℃ Dye-only image, i.e. cyan positive image
was obtained with this photographic film. This dye image
has a maximum density of 1.41 and a minimum density of 0.17.
Was. The absorption maximum of this dye image is 680nm
It was at that time. Examples 160 to 169: Again, a dye image was created according to the method described in Example 1 above.
was prepared. However, in the case of this example, as described in Example 1 above
A chromogenic sulfonamide diphenylamine pigment
Use that from the table below instead of Recasa
did. The absorption of the dye obtained is listed in the table below.
That's right. These values can be converted to
I got it accordingly. Certain chromogenic sulfonamide diphenylamines
Dye precursor sample (3-18 mg, solution of light
(based on the expected value of 1.0 for the academic concentration)
Butyl acetate (50ml) or for dye precursor
Dissolved in similar solvent. Add this solution to phosphoric acid with pH=12.
Excess K in salt buffer₃Fe(CN)₆solution and baldness
Mix well. The organic phase was washed three times with water and
It was then diluted to 100 ml for spectrophotometric analysis.
This method uses chromogenic sulfonamide diphenyls before sorting.
useful for acylamine dye precursors.
Ru. Because the resulting hue, λ_nax(Maximum absorption
wavelength) and molar absorption value (ε) in the photographic element.
Because it is comparable to the properties of the image dye formed
It is. Chromogenic sulfonamide diphenylamine
If a dye precursor is proposed, then
K₃Fe(CN)₆suitable dye in the process of reaction with
If the dye precursor is not produced, then the dye precursor
To form image dyes in photographic elements
I can't say it's useful at all. 【table】 【table】 【table】 Examples 170 to 179: Contains sulfonamide diphenylamine dye
Establishment of elements that It was prepared as described in Example 1 above.
photographic silver halide and the compounds listed in the table below.
Chromatic sulfonamide diphenylamine dye preca
The film strip () containing the
It was processed as follows. 1.30 in a fixer solution (fixer composition A) as follows:
Fixation in seconds (a) Sodium thiosulfate (crystalline) 160.0g (Otherwise, thiosulfate Monium 120g) (b) Potassium metabisulfite 20.0g (c) Add water and total amount 1 2 Thorough cleaning in water for 120 seconds 3. Dip the film into the following composition.
Chromogenic sulfonamide diphenyl amide
Oxidation of dye precursor (a)K₃Fe(CN)₆(1 in benzyl alcohol
Weight%) 20.0g (b) Add water to total volume 1 (buffered to PH = 12) 4. Wash in water for 120 seconds. Color-forming sulfonamide diphenyl same as above
A second set of comparisons containing amine dye precursors
film strip () to the film strip
Processed using the same technique as applied to tup().
Ta. However, in this example, after step 4, the film
Trip in Fixing Composition A for an additional 30 seconds.
and then recolonized in water for 120 seconds.
I washed it. Dye density loss (%) due to fixation is as follows:
I calculated it. Density loss due to fixing (%) = D〓−D〓/D〓×100 Here, D〓 and D〓 are respectively
It is the density for trip and complementary color light.
Ta. 【table】 【table】 The table above shows 4'-triisopropylbenzene
Sulfonamide cyanogen dye forming substances 1a and 1b
In some cases, only 6-9% concentration loss occurs.
However, it is homologous to these and stabilizes (balance).
40-100% for those that have not been
It indicates that a loss has been experienced. combination
Losses for objects 1e and 1f respectively (16% vs. 96
%), both ortho-
4′-ballast with isopropyl group in position
It turns out that the group is important. Stability of compound 1d
is excellent (4% loss), but this
The large substituent at the 2′-ring position is
It has been demonstrated that
ing. In addition, magenta dye precursor 1h and
and the respective density losses for dye precursor 2f.
(0% vs. 33%), triisopropyl
Benzene sulfonamide ballast group at 4′-position
I understand the importance of introducing it. Examples 180 to 197: Processing photo elements A Prepared as described in Example 1 above.
Photographic silver halide and Table A below.
Chromogenic sulfonamide diphenylamine described
Film strips containing dye precursors
Chemically treat the sample at 22.2°C according to the following procedure:
I understood. (1) Fixing for 30 seconds in fixing composition A (2) Rinse with water for 60 seconds (3) 10g/K₃Fe(CN)₆,10ml/ben
Dyl alcohol, 1g/KBr and total amount
pH containing water necessary to make 1 =
12.0 Na₃P.O._Four30 seconds in buffer (4) Washing in water for 5 minutes (5) Kodak Photo
Flo, Trademark) for 10 seconds, then with distilled water.
120 second wash Then, apply the treated strip to your aperture.
the emulsion side toward the light source.
SANS test at 21℃ and 45%RH (relative humidity)
(see below). For exposure, 5400lux
radiation for 1 day, 3 days, and 7 days.
I used it. Following these days fading (%)
I calculated it like this. Fading (%) = D initial stage - Dn days later / D initial stage x 100 Here, D is the response to complementary color light after n days have passed.
It shows the concentration. used here
The term “SANS” refers to Simulated Average
Northern American Skylight (simulated average North American skylight)
It is an abbreviation of ``Tenku Hikari''. B Prepared as described in Example 1 above.
Photographic silver halide and table B below.
Chromogenic sulfonamide diphenylamine described
Film strips containing dye precursors
Photoprocess the sample at 22.2°C according to the following steps:
Ta. (1) Forming a developable latent image through imagewise exposure (2) Activate for 30 seconds in the following developer solution.
Sexualization: 1 g of 4-hydroxymethyl-4-methyl-1
-phenyl-3-pyrazolidone, 10 ml benzyl
Alcohol, 1g KBr and total amount to 1
Na with pH=12 containing the water necessary for₃P.O._Fourbuffer solution (3) Washing in water for 2 minutes (4) Fixing for 30 seconds in fixing composition A (5) Washing in water for 2 minutes (6) Air dry indoors Mount the dried strip as described above.
and exposed to SANS light. 【table】 【table】 【table】 【table】 【table】 SANS fading results (chemically oxidized without development)
coating film) as summarized in Table A above.
However, triisopropylbenzene sulfonate
These results demonstrate the benefits of the midoballast group.
There is. Each 7 day dye for dye 1a
The loss is about 23%, and in contrast,
For non-stabilized dyes it is almost complete fading
(83-100%). Similarly, for dye 1b
The 7-day loss was 9%, compared to
For the standardized cyan dye 1j it is 59% and
Ta. In addition, the destruction of the dye in Example 20 was 100%.
In contrast, the loss for compound 1e was 19% and
Ta. Stabilized magenta pigment forming substance 1h is 7
while showing 4.5% fading in SANS for days
The non-stabilizing compound described in Example 22 caused 58% dye regression.
Indicated. Density values of images formed for the listed dyes
(See Table B)
(I want to be). 【table】 Examples 198 to 201: Chromogenic p-stains as listed in Table A below.
sulfonamide diphenylamine dye precursor
The dispersion was mixed with 1 part dye precursor and 2 parts acetic acid.
chill and 2 parts of N-n-butylacetanilide
Prepared by dissolving in (Kuplar solvent)
did. This organic mixture is combined with an aqueous gelatin solution,
It was then passed through a colloid mill five times. the resulting mixture
The substance is combined with a gelatin-silver halide photographic emulsion, and the
Silver 11.7mg/dm²Transparent poly(ethylene) with a ratio of
(terephthalate) coated onto a film support.
Ta. The resulting photographic element was measured at 1.0 neutral using a commercially available sensitivity meter.
After image exposure through a density filter, it was developed.
A possible latent image was formed in the element. After exposure the photographic element has the following components: 4-methyl-4-hydroxymethyl -1-phenyl-3-pyrazolidone (Cross oxidation developer) 1g Na₃P.O._Four・12H₂O 47.52g KBr 1g Add water and total amount 1 for 30 seconds at 22°C in a developer composition comprising
I took care of it. Next, 5-(2-hydride represented by the following formula)
(loxyethyl)tetrahydro-S-triazine-
2(1H)-thione: Fix the photographic element for 2 minutes in an aqueous solution of
Ta. The photographic element is then washed in water for 5 minutes.
Purified. The following Table A lists the chromogenic sulfonamides.
Dodiphenylamine dye precursor and processing
Describe the absorption maximum of the corresponding dye formed later.
Ru. 【table】 【table】 Benzene sulfonamide
phenylamine
201 43a 4-methyl-4'-p-tolyl
Sulfonamide diphenyl
amine
Example 202: Use in direct positive silver halide photographic materials The following composition is poly(ethylene terephthalate)
g) Photocoating by coating on a film support.
True elements were prepared. Gelatin-silver chloroiodide emulsion (0.4 mol%, 0.24 micron cubic particles, surface fog, chemically sensitized, internally doped) (as Ag°) 9.7mg/dm² Gelatin [bis(vinylsulfonylmethyl)] Duralized using ether] 43.2mg/dm² Chromogenic dye precursor (di-n-butyl (dispersed in phthalate) 5-4mg/dm² Bis(vinylsulfonylmethylene) is added to the resulting emulsion layer.
10.8mg/dm hardened with ether²gelatin
overcoated the skin. obtained in this way
Imagewise exposure of a photographic element according to the invention is carried out using a commercially available sensitometer.
As a result, the developable image was formed in the emulsion layer.
accomplished. The photographic element after exposure is then
It was processed as follows. (1) Activation for 30 seconds in the following composition Phosphate buffer (PH=12) 4-hydroxymethyl-4-methyl -1-phenyl-3-pyrazolidone
1g/ Benzyl alcohol (1% by volume) (2) Washing in water for 60 seconds (3) Fixing for 30 seconds in fixing composition (PH=10) (4) Washing in water for 120 seconds In this way, the dye image and silver image are combined in the emulsion layer.
was formed in Dry the treated elements in the air.
Dry. Red filter the density of the obtained image
When I read it through, D_nax=1.57 and D_nio=
It was 0.41. A reversed image was formed. Fixing the second sample of the photographic element after image exposure
and oxidized using potassium ferricyanide.
As a result, a maximum concentration of 1.40 was obtained. Example 203: Typical developer A The photographic composition below was mixed with poly(ethylene terephthalate).
rate) coated on a film support. AgBr (octahedral particles) 9.4mg/dm² Gelatin (binder) 43.2mg/dm² Bis(vinylsulfonylmethyl)ether (hard)
Film agent 0.4mg/dm² Di-n-butyl phthalate (Kuplar solvent)
5.4mg/dm² Chromogenic p-sulfonamide diphenylene
5.4mg/dm² Luamine dye precursor: (Compound 203A) (cyan) Potassium nitrate 0.6mg/dm² Next, bis(vinyl sulfonate) is added to the resulting emulsion layer.
Nylmethyl)ether (0.108mg/dm²) at dura mater
gelatin (10.8mg/dm²) overcode
I did it. The resulting photographic element is measured using a commercially available sensitivity meter.
image exposed through a step tablet.
, a developable latent image is formed in the emulsion layer.
Ta. While stirring the treatment solution, treat it at 22℃ as follows.
carried out the process. (a) Developed for 30 seconds in the following developer solution: N.A.₃P.O._Four・12H₂O 47.5g Na₂S.O.₃ 5.0g N,N-diethylhydroxyl 1.0ml Amine (H₂85% in O) 4,4-dimethyl-
1-phenyl-3-pyrazolidone 5mM KBr 1.0g Add water to total volume 1 (PH=12.0) (b) Rinse in water for 60 seconds. (c) Set for 30 seconds in the following composition: Na₂S₂O₃・5H₂O 248g Na₂C.O.₃・H₂O 30.0g NaHCO₃ 5.0g Add water to total volume 1 (PH=10.0) (d) Washing in water for 5 minutes. (e) Air drying A cyan image was formed. The above procedure was repeated. However, here, the above
In place of compound 203A, a chromogenic sulfonate such as the following formula can be used.
Uses amide diphenylamine dye precursor
did. (Compound 203B) (Magenta) This compound 203B was added at 9.6mg/dm²cutlet puller
Together with solvent, 9.6mg/dm²The emulsion layer was coated with Images formed using compound 203B are
1.25 maximum for green light when measuring the concentration of
density, and at the 11th step of the image 0.41
Each had its own concentration. Using compound 203A
The image formed using 1.12 for red light
maximum density, and at the 11th step of the image
Each had a concentration of 0.80. B The procedure of A above was repeated. However, in this place
4,4-dimethyl-1-phenyl-3-p
N-(p-hydroxyphene) instead of lazolidone
pyrrolidine was used. Compound 203B
The image formed using a maximum density of 1.41,
It had an 11th step concentration of 0.43. Compound
Images formed using 203A have a maximum of 1.56
concentration, and has an 11th step concentration of 0.59
Ta. C The procedure of A above was repeated. However, in this place
4,4-dimethyl-1-phenyl-3-p
p-N,N-dimethyl-p instead of lazolidone
-Aminophenol was used. Compound 203B
Images formed using a maximum density of 0.80,
and had an 11th step concentration of 0.21. combination
The image formed using object 203A has a maximum of 1.42
Has a large concentration, and an 11th step concentration of 0.28
Ta. D The procedure of A above was repeated. However, in this place
4,4-dimethyl-1-phenyl-3-p
N,N,N',N'-tetone instead of lazolidone
lamethyl-p-phenylenediamine dihydroc
I used Lorido. Formed using compound 203B
The resulting image has a maximum density of 1.30, and a maximum density of 0.38.
It had an 11th step concentration. Using compound 203A
The image formed with a maximum density of 1.34 and
It had an 11th step concentration of 0.72. E The procedure of A above was repeated. However, in this place
4,4-dimethyl-1-phenyl-3-p
6-amino-1-hydroxy instead of lazolidone
ethyl-2,2,4-trimethyltetrahy
Droquinoline dihydrochloride was used. transformation
The image formed using compound 203B is 1.23
maximum concentration, and has an 11th step concentration of 0.22
there was. The image formed using compound 203A is
maximum concentration of 1.32, and 11th step concentration of 0.40
had. In examples 203A, B, C, D and E above.
Regarding the images formed, their respective maximum
The large concentration value has a neutral metallic silver concentration of approximately 0.40.
Ta. Example 204: mixture of dye precursors 4-dihexylamino-4'-(2,4,6-t
lyisopropylbenzenesulfonamide) diphene
Nylamine (see dye 1a in Example 1 above)
A dispersion of this first chromogenic dye precursor
3.0g to 8.0g N-n-butylacetanilide
Prepared by dissolving. Obtained dispersion
was designated as dispersion liquid 204A. 4-hexyloxy-
3'-Methyl-4'-(2,4,6-triisopropyl
rubenzenesulfonamide) diphenylamine
(see dye 1h in Example 159 above)
8.0 g of this second chromogenic dye precursor
g of N-n-butylacetanilide and 8.0 g of
Prepared by dissolving in ethyl acetate. profit
The resulting dispersion was designated as dispersion 204B. The first photographic silver bromide composition described below was
(terephthalate) coated onto a film support.
Ta. Red sensitized gelatin - silver bromide photography Emulsion 9.7mg/dm² Dispersion liquid 204A: 4-dihexylamino-4'-(2,4,6-t
diisopropylbenzenesulfonamide)
Enylamine (dye precursor) 4.1mg/dm² N-n-butylacetanilide 10.8mg/dm² Gelatin (binder) 43.2mg/dm² Bis(vinylsulfonylmethyl)ether (hard)
Film agent) 0.4mg/dm² Apply the following intermediate layer above the first layer obtained.
Ta. 2,5-di-s-dodecyl-1,4-dihydro
Xybenzene 12.9mg/dm² Gelatin (binder) 16.8mg/dm² Bis(vinylsulfonylmethyl)ether (hard)
Film agent) 0.17mg/dm² Then, above the obtained intermediate layer, the following second layer is applied.
A photographic silver bromide composition was applied. Green sensitized gelatin - silver bromide Photographic emulsion 9.7mg/dm² Dispersion liquid 204B: 4-hexyloxy-3'-methyl-4'-(2,
4,6-triisopropylbenzenesulfona
(mid) diphenylamine (dye precursor)
5.4mg/dm² N-n-butylacetanilide 10.8mg/dm² Gelatin (binder) 43.2mg/dm² Bis(vinylsulfonylmethyl)ether
0.4mg/dm² The obtained photographic element was designated as element 204. 2,
5-di-s-dodecyl-1,4-dihydroxybe
Another copy identical to the above except that the
True elements were prepared. Add this photo element to element 204
And so. Each of these photographic elements can be
After image exposure using a rust spectrograph, the development
A possible latent image was formed on the element. Then,
Treat these elements at 22°C as follows:
Ta. (1) Activation for 30 seconds in the following composition Na₃P.O._Four(PH=12) (buffer) 4-hydroxymethane
Tyl-4-methyl-1-phenyl-3-pyrazo
Lydon 1g Benzyl alcohol 10ml KBr 1g Add water and total amount 1 (2) Washing in water for 2 minutes (3) Fixing for 30 seconds in the following fixing composition Sodium thiosulfate (otherwise, sodium thiosulfate
Ammonium 120.0g) 160.0g Potassium metabisulfite 20.0g Add water to total volume 1 (PH=4.7) (4) Washing in water for 2 minutes (5) Air drying From these photographic elements, developed silver,
A dye image was formed. For each element
The image formed by white light, red light, and green light
According to the reading, the maximum transmission is as follows.
and minimum dye density (negative) were observed. element 204 D _nax D _nio White light 1.47 0.23 Red light 1.66 0.39 Green light 0.31 0.09 element 204 D _nax D _nio White light 1.47 0.10 Red light 1.62 0.17 Green light 0.74 0.09 The above data includes photo elements 204 and 204.
Silver with an overall enhanced blue pigment when used
This proves that images can be obtained. When comparing the maximum density values for green light,
It can be seen that color contamination has occurred in element 204.
Note that this contamination is due to the oxidized form of 3-pyrazoli
This is caused by the developer floating between the layers of the element.
This is what happened. Element 204 is a pure color component
Release was observed and oxidized 3-pyrazolidone development
There is no evidence that the agent floated through the interlayer.
Ta. Example 205: Comparison of stability in photographic materials Color-forming sulfonamide diphenyls such as:
Dye precursors and their corresponding sulfonimines
dye (in the silver halide photographic material according to the invention)
A comparison was made regarding the stability of 205A4-hexyloxy-4'-(2,4,6-t
Lyisopropylbenzenesulfonamide
D) Diphenylamine 205B4-n-hexyloxy-2'-pivalami
Do-4'-(2,4,6-triisopropropylene)
pyrubenzenesulfonamide) diphene
nilamine 205C4-hexyloxy-3'-pivalamide-
4'-(2,4,6-triisopropyl
benzenesulfonamide) diphenyl
amine 205D2′,5′-dipivalamide-4-n-hexyl
Oxy-4'-(2,4,6-triiso
propylbenzenesulfonamide) di
phenylamine Halo each one of these dye precursors
Contaminated with silver genide photographic elements. The photo used here
The true element is primed poly(ethylene terephthalate)
rate) film support and provided above it.
Ta, (1) Silver bromide (particle size 0.8 microns, octahedral particles, sulfur
chemically sensitized with yellow and gold sensitizers) (9.7mg/
dm²), and (2) Bis(vinylsulfonyl methyl ether)
(1% by weight) gelatin (43.2mg/
dm²) (binder), It consisted of a layer containing Chromogenic p-sulfonamide diphenylamine color
3.8 to 16.2 mg/dm of elementary precursor in the above layer²in
It was dispersed in a solvent (1:1 to 1:2 parts by weight). photo
Uniformly expose each true element using a commercially available sensitivity meter.
However, if a developable image is formed in the element,
It was. Each photographic element was then exposed to the following conditions at 22°C:
I processed it like this. (a) Activation for 30 seconds in the following composition: 4-Methyl-4-hydroxymethyl-1-phenylene
Ru-3-pyrazolidone 1g Potassium bromide 1g Benzyl alcohol 10ml Na₃P.O._Four・12H₂O 47.5g Add water and total amount 1 (Adjust PH to 12.0) (b) Washing in water for 30 seconds (c) Fixing for 30 seconds in the following composition: Na₂S₂O₃・5H₂O 248g Na₂C.O.₃・H₂O 30.0g NaHCO₃ 5.0g Add water to total volume 1 (PH=10.0) (d) Washing in water for 2 minutes. A dye image and a silver image are formed on each of the photographic elements.
accomplished. These developed images have the following maximum
and the lowest concentration value. pigment Precasa D_nax (maximum absorption (measured in wavelength)D _nio (Determined from unexposed photographic element by dye λ _nax ) 205 1.03 0.08 205B 0.72 0.08 205C 1.49 0.07 205D 1.71 0.08 Each of the processed photographic elements was exposed to light in the SANS test. After 7 days, the fading (%) of the dye image was observed. The following results were obtained. Dye Precursor Fading (%) 205A 13.3 205B 5.6 205C 26.2 205D 0 This indicates the degree of stability to light afforded by the dye image according to the invention. A separate sample of each photographic element after processing was subjected to a "wet oven test." That is,
The photographic element was placed in an oven and maintained at 60°C and 70% RH. The fading (%) of the dye image was observed for 7 days. The following results were observed. Dye Precursor Fading (%) 205A 100.0 205B 6.3 205C 100.0 205D +1.9 (Dye image of 205D has increased density) This is because the sulfonimide dye image formed from dye precursors 205B and 205D is formed from compounds 205A and 205C. This shows that the dyes are more stable than the sulfonimide dyes used. It has been found that the following dye precursors also form the corresponding sulfonimide dyes according to the present invention. Example 206: Prepare a photographic silver halide composition as follows,
It was then coated onto a poly(ethylene terephthalate) film support. Gelatin-silver bromide photographic emulsion 9.7mg/dm ² (grain size 0.8 microns, octahedral grains, chemically sensitized with sulfur and gold) Gelatin 43.2mg/dm ^2bis (vinylsulfonylmethyl)ether (hardener) 0.43 mg/dm ² N-n-butylacetanilide 6.5 mg/dm ² (Kupler solvent) 3-methanesulfonamide-2'-octaamide-4'-(2,4,6-triisopropylbenzenesulfonamide) diphenylamine
6.5 mg/dm ² (dye precursor) The resulting photographic element was imagewise exposed in a commercially available sensitometer through a step tablet and a neutral density filter to form a developable latent image in the silver bromide photographic layer. This exposed element is then 22
℃ as follows. (1) Activated 4-hydroxymethyl-4-methyl-1-phenyl-3- for 30 seconds in the following composition:
Pyrazolidone 1g Benzyl alcohol 10ml PH=12, Na ₃ PO ₄ Add buffer water to make total volume 1 (2) Fix in the following fixing composition until it becomes clear NaHCO ₃ 0.5g Na ₂ CO ₃ 40g Na ₂ S ₂ O ₃ Add 100g water to total amount 1 In this way, develop a silver image with a maximum density of 0.92,
A dye image was then formed. Absorption maximum (λ _nax )
was 435nm. The above procedure was repeated. However, this time, instead of fixing the developed photographic element in the described fixing composition, the photographic element was bleached.
processed in a fixing composition. In this way the silver image was removed. The maximum density of the obtained dye image is 0.3
(435nm). Examples 207-224: The chromogenic p-sulfonamide diphenylamine dye precursors described below also provided corresponding sulfonimide dyes similar to the dye images formed in Example 206 above. In each case,
The dye precursor was prepared as a dispersion in N-n-butylacetanilide (1:1 to 1:2 weight ratio) and 3.8 to 16.2 mg/silver at a concentration sufficient to obtain a dye and silver image density of about 2.0. Coated in a dm ² silver halide photographic layer. Developing process 26-27
The process was carried out in an aqueous processing solution (buffered to PH=12.2) containing 1 g/l of 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone (cross-oxidized developer) at <RTIgt;C. The absorption maximum wavelengths of each of the corresponding sulfonimide dyes formed are listed below for each of the dye precursors. Many of the ionizable 3-methanesulfonamide-substituted dye precursors exhibited improved reactivity compared to the corresponding 4-methoxy compounds. Example 207: 3-methanesulfonamide-4-methoxy-
2'-octanamide-4'-(2,4,6-triisopropylbenzenesulfonamide) diphenylamine (475nm) Example 208: 3-(N-methyl)methanesulfonamide-4
-methoxy-2'-octanamide-4'-(2,4,
6-triisopropylbenzenesulfonamide)
Diphenylamine (472nm) Example 209: 3-methanesulfonamide-4-methoxy-
2'-Pivalamide-4'-(2,4,6-triisopropylbenzenesulfonamide) diphenylamine (478nm) Example 210: 3-Methanesulfonamide-2'-octanamide-4'-(2,4,6- Triisopropylbenzenesulfonamide) diphenylamine (429nm) Example 211: 3-(N-Methyl)methanesulfonamide-
2'-octanamide-4'-(2,4,6-triisopropylbenzenesulfonamide) diphenylamine (430nm) Example 212: 3-methanesulfonamide-2'-palmitamide-4'-(2,4,6- Triisopropylbenzenesulfonamido) diphenylamine (429nm) Example 213: 3-methanesulfonamido-4-methyl-2'-
Palmitamide-4'-(2,4,6-triisopropylbenzenesulfonamide) diphenylamine (438nm) Example 214: 3-methanesulfonamide-4,6-dimethyl-2'-palmitamide-4'-(2,4, 6-Triisopropylbenzenesulfonamide) diphenylamine (433nm) Example 215: 3-Methanesulfonamide-6-methoxy-
2'-octanamide-4'-(2,4,6-triisopropylbenzenesulfonamide) diphenylamine (419nm) Example 216: 3-acetamido-2'-octanamide-4'-
(2,4,6-triisopropylbenzenesulfonamide) diphenylamine (429nm) Example 217: 4-[N-(β-methylsulfonamido)ethyl-N-ethyl]-amino-2-methyl-2'-octanamide -4'-(2,4,6-triisopropylbenzenesulfonamido)diphenylamine (641nm) Example 218: 4-[N-(β-N-methylmethanesulfonamido)ethyl-N-ethyl]amino-2-methyl −
2'-Octaneamide-4'-(2,4,6-triisopropylbenzenesulfonamide) diphenylamine (642nm) Example 219: 3-(4-dodecyloxybenzene)sulfonamide-4'-(2,4,6 -triisopropylbenzenesulfonamido) diphenylamine (484 nm) Example 220: 3-(2,4-di-t-amylphenoxy)acetamido-4'-(2,4,6-triisopropylbenzenesulfonamido) diphenylamine (479 nm) Example 221: 4-methoxy-2-methyl-2'-octanamide-4'-(2,4,6-triisopropylbenzenesulfonamide) diphenylamine (515nm) Example 222: 4-hexyloxy-2'-[α- Dodecyl-α
-(3-t-butyl-4-acetoxyphenoxy)
Example 223: 4-hexyloxy-2'-[α-dodecyl-α
-(3-t-butyl-4-hydroxyphenoxy)
Acetamide]-4'-(2,4,6-triisopropylbenzenesulfonamide)diphenylamine (504nm) Example 224: 2,4-dimethoxy-2'-octanamide-
4'-(2,4,6-triisopropylbenzenesulfonamide) diphenylamine (533nm)

Claims (1)

[Scope of Claims] 1. A color-forming dye precursor compound selected from the group consisting of diphenylamino, phenylnaphthylamine, or acid salts thereof, wherein the first benzene ring contained in the color-forming compound has an -NH- group. (a) said first benzene ring has an electron-donating group in its meta- or para-position, and (b) said second benzene ring or naphthalene nucleus has a sulfonamide group in its para-position; (c) said compound has no sulfonamide group in each of its ortho-positions; and (d) ) A chromogenic dye precursor compound capable of forming a sulfonimide dye in the oxidized state, and all of the ring positions described above are relative to the -NH- group.