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Патент USA US2411951

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2,411,951
Patented e... a, 1946
STATES PATENT OFFICE .
2,411,951
-
4, '-BIS (PYRAZOLONE) coUrLEas ron COLOR rno'roenarnr ~
Abraham Bav'iey, Binghamton, N. Y.,- assignor to
General Aniline & Film Corporation, New York,
N. _Y~., a corporation of Delaware
No Drawing. Application September as, 1944,
Serial No. 556,273
12 Claims. (0!. 95-6)
A still further object is to provide ?nished pho
This invention relates to the production of col
tographs which contain stable dye images. ,
ored photographic .imagesiby color development,
The above and other objects are accomplished
according to the present invention by the use of
substituted and unsubstituted bis-pyrazolones oi
and more particularly ‘to substituted and unsub
stituted .‘bis-pyrazolohes ‘as new color forming’
coupler compounds’therefor.
'
the general formula:
The, formation of colored photographic images
by coupling the development product of an arc
matic amino developingagent with color form
ing or coupling compounds is well known, and is
generallyreferredtoascolor forming development.
10
In these vmethods the subtractive process of color
formation, ordinarily used and the image dyes
,
are intended to boot the complementary primary
colors, cyan .or blue-green, magenta and yellow.
it
wherein R represents hydrogen, or an alkyl group
' The couplers, which produce magenta dyes are 15 e.‘ g., methyl, ethyl, propyl, 'butyl, octyl, decyl,
ordinarily pyrazolones J or cyano 'acetyl com , ' heptadecyl, octadecyl, stearyl, or any other alkyl
pounds. iThe dyes produced by-coupling are azo
radical containing up to 24' carbon. atoms, car
_ methines, indamines'or indophenols, depending
balkoxy alkyl, e, g., acetic ethyl ester and the like,
upon the composition of the coupler and of the
' developer.
The couple? or color former-may be
present in the emulsion or in the developing so
alkylcarboxy, e. g., carbomethoxy, carbethoxy,
2? carbopropoxy; etc., aryl', e. g., phenyl, naphthyl,
anthranyl, diphenyl, etc., or aralkyl, e. g., benzyl,
lution which during .the development process‘ '
methyl bénzyL-ethyl benzyl and the like, alkyl-
couples with 'the oxidation product of the arc
amino, e. g., amylamino and the like, arylamino,
e. g., anilino,‘ anisylamino and the like, acetaryl
the emulsion. ~ The developed emulsion may then 25 amido, e. g.,‘ acetanilido, acetanisido, acetdimeth
be bleached for removal of the silver image leav
ylanilido, acetnap'hthylamido, etc., sulfamylphen
ing the color image in the emulsion.
ylamino and the like, R1 represents either hydro
I have discovered that-substituted and unsub
gen, alkyl, aryl, or aralkyl of the same value as’ R,
matic aminov'developer to form a dye image in
stituted bis-pyra'zolon‘es are especially valuable
color formers which couple with the. oxidation
product of an aromatic primary amino developer
toform amagenta'dye imagein the emulsion. The
' or a heterocyclic nucleus, e. g., thiazolyl, benzo
30 'thiazolyl, quinolyl, pyridyl, naphthiazolyl and the
like. Said alkyl, aryl, aralkvl, radicals given as
values for R and R1 may be substituted by a halo
gen such as chlorine, bromine or iodine, acetamido‘
' substituted and unsubstituted ibis-pyrazolones are
permeable to blue rays and showv a high trans
‘group, imino group, nitro group, alkoxype. g.,
parency, with the result that a satisfactory color
methoxy, ethoxy, propoxy, butoxy, etc., amino
for subtractive color‘ processes is-obtained upon
‘
group, e. g., primary amino, secondary amino
coupler development.
such as methyl amino, phenyl amino-and the like,
It is an object of the presentinvention to pro
or a tertiary amino such as dimethyl amino, di
' vide anew class of color formers forproducing
phenyl amino etc., sulioamino, or vsolubilizing
magenta dye images by color forming develop 40 groups such as sulfonio or carboxylic acid groups.
ment.
.
‘
1.
3
Y
-
'
Compounds representingv thlsgeneral classi?
-
A further object is to provide photographic de
veloper solutions and emulsions which‘ contain a '
new class of color formers-tor producing'magenta
dye images in situ with photographic images.‘
- cation are as follows:
45
4,4"-bis(1-phenyl-3-methyl-5-pyra2olone) _.
4,4'-bis (lep-nitrophenyl-3hmethylb?-pyrazolone)
2,411,951
4
4,4’-bis(1-a—naphthyl-3-methyl-5-pyrazolone)
4,4'- bis(l - phenyl - 3 - (undecyl - 3’-carbox ~
ylic acid) -5-pyrazolone)
In general, the coupling compounds of the
present invention which do not contain solubiliz
4,4'-bis(1 - p - bromophenyl - 3 - methyl - 5 pyrazolone)
-
4,4'-bis-5-pyrazolone (unsubstituted)
4,4’-bis(3-phenyl-5-pyrazolone)
I
ing groups, are water insoluble. Their solubility
4,4'-bis(1-pheny1-3-acetic ethyl ester-5-pyraz
in water, however, is accomplished by the intro
olone)
4,4'-bis(1-phenyl-3-acetanilido-5-pyrazolone)
4,4'- bis(1 - phenyl - 3 - p - chlor - acetanilido -
5-pyrazolone)
‘4,4'- bis(1 - phenyl - 3.- acet - m - naphthyl amido-5-pyrazolone)
,
4,4’-bis(1-?-naphthy1-3-acetic ethyl ester-5-py
razolone)
'
4,4’- bis(1 - B - naphthyl - 3-- acet — o - anisido . 5-pyrazolone)
duction of suitable solubilizing groups, e. g., sul
fonic or carboxylic acid groups into the groups
represented
by R in the above general formula.
10 The condensation
reaction is carried out by re
?uxing a substituted or unsubstituted pyrazolone
in the presence of phenyl hydrazine according to
the methods known in the art.
The substituted pyrazolones are prepared ac
15
cording to the methods described in U. S. Patents
2,200,306; 2,265,221; 2,334,495; 2,343,703; and
4,4'- bis(1 - phenyl - 3 - acet - a - naphthyl amido-S-pyrazolone)
~
U. S. Patent Re. 22,329. These substituted pyraz- ‘
clones are characterized by having an active
methylene group in the 4 position and have the
4,4’- bis(l - p - tolyl - 3 - (acct - 2',4'- dimethyl _
anilido) ~5-pyrazo1one)
20 general formula
4,4’-bis(3-anilino-5-pyrazolone)
4,4'-bis(1-acetyl-3-anilino-5-pyrazolone)
“'
R--C———CH:
4,4’ -bis ( 3-a-naphthylamino-5-pyrazolone)
4,4'-bis(3-o-bromanilino-?-pyrazolone)
4,4’ -bis (3-n-amylamino-S-pyrazolone)
25
4,4'-bis(1-benzoyl-3-anilino-5-pyrazolone)
4.4'-bis(1-phenyl-3-anilino-5~pyrazolone)
l3 ‘i
2
5 o
\t/
I
.
R1
4,4'- bis(1 _ phenyl - 3 - p ,- anisyl - amino - 5 -
pyrazolone)
4,4'- bis(1 - phenyl - 3 - p - suliamyiphenyl -
amino-5-pyrazolone)
4,4'~ bis(1 - phenyl - 3 - p - (p — tert. amyl -
phenoxy) -phenylamino-5-pyrazolone)
4,4'- bis(1 ~ (3 - carboxyphenyl) - 3 - heptadecyl -
S-pyrazolone)
4,4’- bis(1 - (phenyl - 4'-sulfonic acid) - 3 - hep -
tadecyl-5-pyrazolone)
4,4'- bis(1 - (phenyl - 3'-sulfonic acid) - 3 - hep tadecyl-S-pyrazolone)
.
'
4,4’- ‘bis(1 - (phenyl - 3'- carboxylic acid) - 3 -
undecyl-E-pyrazolone)
4,4’-bis(1-ethane sulfonic acid-B-p-nitrophenyl
5-pyrazolone) .
razolone)
4,4'-bis(1—ethane sulfonic acid-3-heptadecyl-5~
pyrazolone)
4,4’- bis(1 - (phenyl - 4'-ethoxy) - 3 - methyl v
4,4'- bis(1 - (phenyl - 4'-nitro) - 3 - methyl - 5 —
pyrazolone)
_
.
yl-S-pyrazolone)
4.4'- bis(1 - (phenyl - 4'- sulfo) - 3 - methyl - 5 -
pyrazolone)
4,4'- bis(1 - (2'- benzothiazolyl) - 3 - anilino -
5-pyrazo1one)
4,4'- bis(1 - (a - quinolyl) - 3 - anilino - 5 - py -
they may contain other substituent groups as
well as those included in the above general
formula.
During the experimentation with and the prac
40 ticing of this invention, I have discovered that
the nature of R and R1 substituents in the above
general formula is immaterial since any substi
dense in the presence of phenyl hydrazine to give
the corresponding bisymmetrical product, and
such product will function as a color former.
The color formers may be added to the devel
oper, providing they are not fast to di?usion in
50 gelatin, or to the silver-halide emulsion in the
solvent, such as, l-N-alcoholic sodium or potassi
um hydroxide, acetone, ethyl alcohol, isopropyl
alcohol, etc. Dispersing agents such as isopropyl
naphthalene sulfonic acid or any of the dispers
ing agents disclosed in U. S. 2,186,717 may be used
in preparing the suspension of the water insoluble
color formers for incorporation into developers or
silver-halide emulsions. Instead of gelatin, the
'
4,4'- bis(1 - (a - pyridyl) - 3 - anilino - 5 - py razolone)
35 ents are exemplary only, it being understood that
form of a solution or a suspension in a suitable
4,4’-bis(1 - (or - naphthyl - 4’ - sulfo) - 3 - meth
razolone)
shown.
The examples of the substituted pyrazolones
disclosed herein and in the above mentioned pat
tuted or unsubstituted pyrazolone, having an ac
tive methylene group at the 4 position, will con
4,4'-bis(1-ethane sulfonic acid-3-methyl-5-py
?-pyrazolone)
wherein R and R1 have the same values as above.
30 The commonly accepted nomenclature is used
and the positions from 1 to 5 are numbered as
loidal materials such as, organic esters of cellu
'
4,4'-bis(3-methyl-5-pyrazolone)
4,4'-bis(1-phenyl-3-phenyl-5-pyrazolone)
lose, super-polyamides, polyesters or synthetic
4,4'-bis(1-p-tolyl-3-methyl-5-pyrazolone)
4,4'- bis<1 - (2'-methylphenyl - 5'-sulfonic acid) -
3-heptadecyl-5-pyrazolone)
4,4'-bis (1- (2'-methoxyphenyl-5'-sulfonic acid) -
3- ( 3' -stearylaminophenyl) e5-pyrazolone)
4,4'-bis(1-(2'-phenoxyphenyl-3'-sulfonic
sodium-3-heptadecyl-5-pyrazolone)
60 color formers may be incorporated in other col
acid)
4,4'- bis(1 - (3 - carboxyphenyl) - 3 - hepta decyl-5-pyrazolone)
.
4,4'- bis(1 - phenyl - 3 - (heptadecyl - 4’-su1ionic
acid)-5-pyrazolone) and
'
resins. The emulsion may be carried by a trans
parent medium such as cellulose esters, super
65 polyamides, synthetic resins or a non-transparent
re?ecting medium such as paper or an opaque
cellulose ester. The emulsion may be coated as
a single layer on the support. or superposed layers
containing the couplers may be coated on‘one or
both sides of the support. The superposed layers
may be differentially sensitized for the formation
of a color image in the well known manner.
When incorporating the color formers into
photographic silver-halide emulsions. it is essen
75 tial that the substituents ofR in the above :en- 7
2,411,951
Many speci?c objects, featuresand advantages
eral formula be such that they will prevent the
of my invention will become apparent to those
skilled-in the art from the speci?c examples ap
pearing below. The following examples are not
color formers from migrating from one layer to
another, otherwise color distortion will result
upon color-forming development. Several meth
ods have been proposed to prevent migration of
to be considered as limiting my invention but are
merely illustrative of methods of carrying it out.
color formers from silver-halide emulsion layers
by rendering such color formers “fast to diffusion
in gelatin.” This result may be accomplished in
several ways, as for example, by substituting the
1 and/ or 3 position of the pyrazolone nucleus with 10
suitable groups which impart substantive charac
teristics to the color formers which combine per
manently with the gelatin and other colloidal ma
terials of the silver-halide emulsion, or by en-.
larging the substituent group of the color former 15
with a long chain alkyl radical’ so that the color
former is incapable of diffusing from the gelatin
or other colloidal materials. Examples of such
methods which render color formers fast to dif
fusion‘ by imparting substantive’ characteristcs, 20
thereto are disclosed in U. S. 2,179,228. Exam
This compound was prepared according to‘ the
ples of color formers which are rendered fast to
Y method given in Ann., 238, "167 and Ben, 17, 2044,
diffusion by enlarging the substituent groups (R
and/or R1) are disclosed in U. S. Patents 2,175,
512; 2,179,238-9; 2,179,234; 2,178,612; 2,179,344 ;‘
2,179,244;v 2,186,719; 2,186,851-2; 2,186,732-3-4;
2,186,849; 2,186,045; 2,200,306; 2,280,722; ‘2,292,
25
575; 2,303,928 and 2,307,399. By reference to the
latter patents, it will be noted that the color
'by re?uxing 5 grams of l-phenyl'e3-methyl-5
pyrazolone with 15 cc. of phenyl hydrazine for 1
hour. The reaction mixture was allowed'to cool
and the precipitated product was then ?ltered
and recrystallized from ethyl‘ alcohol. _
1 gram of the above productwas dissolvedin
forn'i’érs'are modi?ed "by theinclusion of radicals 30 Y 20 cc. of ethyl alcohol. 2 ccQof the solution were
then added to the developing-solution and used
of resins, polypetides, hydrogenated ring systems,
for the development of anexposed silver-halide
carbohydrates, long alkyl chains, and by having
emulsion. A‘ magenta image‘was obtained to
the substituent radical recur a number of times
in the ?nal molecule. It is to be understood that
gether with the silver image. '
the substituent groups of the color formers of ‘the
present invention in addition to those previously
I
__
'
mentioned, include substantive groups or molecu
lar enlarging groups for the purpose of render
ing the bls-pyrazolones fast to. diiiusion.
-
Example II-jiv '
v
4,4'-bls(3-methyl45-pyraaolone)
I
As examples of suitable aromatic primary ami
no developing agents whichjvmay be employed
with the color coupling compounds of the present‘
invention, there may be mentioned p-phenylene,
diamine, mono ethyl-p-phenylene diamine, die
ethyl-o-phenylene diamine, 4,4’-diamino-diphe
nylamine, .p-amino dialkyl anilines, e. g., p-ami
no dimethyl aniline and p-amino-diethyl aniline.
These developing agents are preferably used in ,
the form of their salts such as the hydrochloride,
This compound was prepared according to the
method of Max Edam, Dissertation Jena, 1893,
pages 16 and 29, by re?uxing -5v grams of 3
methyl-5-pyrazolone with‘ 20 cc. of phenyl hydra
since they are more soluble and stable than the 50 zine for 1 hour.
free base. They are characterized" by the pres
ence of a free or primary amino group in the phe
nyl nucleus which enables the oxidation product
of the developer to couple with the ‘color former
to‘ form a dye image in the emulsion adjacent to
the individual particles of the silver image.v The
silver image may be removed by bleaching in the
well known manner to leave the color image in
the emulsion.
'
'
r
v
A suitable developing solution is prepared as
follows:
-
The reaction mixture was al
lowed to cool and the- precipitated product'was
then ?ltered and recrystallized ‘from ethyl alco
hol.
~
.
T
.
-
1 gram of the above product was dissolved in 20
cc. of ethyl alcohol. _2 cc. of the solution were
then added to the developing‘ solution and used
for the development or anv exposed silver-halide
emulsion. A magenta image was obtained to
gether with the silver image. ,
'
.
Example In
4,4'~bis ( 1-phenyl-3-pl1enyl-5-pyrazolone)
<
"p-Amino-diethylaniline' I-ICl ____ __'_grams__. 2.0
Sodium carbonate (anhydrous) ____ __do___ 50.0 65
Sodium sul?te (anhydrous) ________ ....do___ 2.0
Potassium bromide
»
'
do
0.2
Water to make___,_ ___________ __'.’__._'_liter__
1
The exposed silver-halide emulsions‘ are de 70
veloped in the above solution in thevusual man
ner. A solution or suspension of the ‘color former
is only added .to the developing solution where
' thecolor .former is not
halide emulsion.
present in the silver
' -
'
~
This compound was prepared according to the
2,411,951
.
7
directions given in Ber. 20, p. 2548, by re?uxing 5
grams of i-phenyl-3-phenyl-5-pyrazolone with
20 cc. of phenyl hydrazine for 1 hour. The reac
tion mixture was allowed to cool and the precipi
tated product was then filtered and recrystallized
from ethyl alcohol.
1 gram or the above product was dissolved in
20 cc. of ethyl alcohol. 2 cc. of the solution were
then added to the developing solution and used
for the development of an exposed silver-halide 10
emulsion. A magenta image was obtained to
gether with the silver image.
Example IV
4,4'-bis (1-p-toiyl-3Fmethyl-?-pyrazolone)
16
H
‘ (pheny1-4'-nltro) -3-methy1-5-pyrazolone with 20
t
cc. of phenyl hydrazine for 2 hours. The reac
tion mixture was allowed to cool and the precipi
1110-01- — —-—C—CHa
it
to o
\/
it
\NK
:1 : ;H:
20 tated product was then ?ltered and recrystallized
from ethyl alcohol.
1' gram or the above product was dissolved
in 20 cc. of ethyl alcohol. 2 cc. of the solution
were then added to the developing solution and
25 used for the development or an' exposed silver
halide emulsion. A magenta image was obtained
together with the silver image.
This compound was prepared according to the 30
method of C. T. Sprague, Dissertation Gottinger,
1890, page 46 (can also be prepared according to
the method of W. Hippmeir, Diss., ‘Jena, 1894, s.
17), by re?uxing 5 grams of 1-p-tolyl-3-methyl
S-pyrazolone with 15 cc. of phenyl hydrazine for 35
2 hours.
This compound was prepared according to the‘
method of Example 5 by re?uxing 5 grams of 1
Example VII
4,4'-bie (1- (a-naphthyl-4'-snlto) -3-metl1y1-5-'pyrazolone)
E
H
v
nic-c--.d--<li-_-o-cm
The reaction mixture was allowed to
cool and the precipitated product wascthen ?l
tered and recrystallized from ethyl alcohol.
1 gram of the above product was dissolved in
20 cc. of ethyl alcohol. 2 cc. of the solution were 40
then added to the developing :solution and used
for the development of an exposed silver-halide
emulsion. A magenta image was obtained to
80:11
SOIH
This compound was prepared according to the
method of M. Mueller, Dissertation Jena, 1892,
page 22, by re?uxing 5 grams or 1-(a-naphthyl
4'-sulfo)-3-methyl-5-pyrazolone with 15 cc. of
phenyl hydrazine for 2 hours. The reaction mix
gether with the silver image.
Example V
4,4’-bis (1- (pb enyl-4'-ethoxy) -3-methyl-5-pyrazolone)
ture was allowed to cool and the precipitated
50 product was then ?ltered and recrystallized from
ethyl alcohol.
1.8 grams of the above color former were dis
solved in 2.0 cc. of l-N-alcoholic KOH and added
with thorough mixing to 100 cc. of a gelatin sil
ver bromide-iodide emulsion. After coating the
emulsion containing the color former onto a suit
able support and drying, the ?lm was exposed
and developed to yield a magenta image together '
with the, silver image.60
This compound was prepared according to the
method of J. Grenzfelder, Dissertation Jena, 1894,
page 17, by re?uxing 5 grams of 1-(phenyl-4'
ethoxy) -3-methyl-5-pyrazolone with 20 cc. of 65
phenyl hydrazine for 2 hours. The reaction
Example VIII
7
’
4,4'-bis (1-(pl1enyl-4'-sulto) -3-methy1-5-pyrazolone)
‘
H
HaC--C——-('J—-—é§-—C—CH:
I
0 O
l
mixture was allowed to cool and the precipitated
product was then ?ltered and recrystallized from
ethyl alcohol.
1 gram or the above product was dissolved in 70
20 cc. of ethyl alcohol. 2 cc. of the solution were
then added to the developing solution and used
for the development of an exposed silver-halide
emulsion. A magenta image was obtained to
gether with the silver image.
745 . This compound was prepared according to the
2,411,951
a
.
I
‘
9
7
method of Example 7‘ by re?uxing 5 grams of i
-
the product of Example 9 with sulfuric acid con
taining 30% S0: with cooling.
After recrystallization from water, 1.8 grams
of the resulting product were dissolved in 2.0 cc.
(phenyl-4'-sulfo) -3-methyl-5-pyrazolone with 15
cc. of phenyl hydrazine for 2 hours. ‘The reac
tion mixture was allowed to cool and the precipi
tated product was then ?ltered and recrystallized
from ethyl alcohol.
10
This compound was obtained by sulionating
of water and the solution added to 100 cc. of a
‘
gelatin silver bromide-iodide emulsion. The
1.8 grams of the above color former were dis
emulsion was coated onto a cellulose acetate
solved in 2.0 cc. or l-N-alcoholic KOH and added
base and after drying, the ?lm was exposed and
with thorough mixing to 100 cc. of a gelatin silver
bromide-iodide emulsion. After coating the emul 10 developed. A dye image of excellent magenta.
color was formed in the emulsion.
sion containing the color former onto a suitable
support and drying. the mm was exposed and de
veloped to yield a magenta image together with
the silver image.
Example XI
4,4'-bie(l-phenyl-5-pyrazolone3-acetic ethyl ester)
15
Example IX
4,4'-bil(I-pheuylf3-heptadecyl-?-pyrazolone)
~ \
It
tool
ii
20
25
Five grams of 1-phenyl-5-pyrazolone-3-acetic
' ethyl ester,.;prepa,r.ed_according. to Example I of
This compound was prepared’by re?uxing 5v 30 U. S. Patent 2,334,495, were re?uxed with 20 cc.
grams
of
of phenyl hydrazine for 2 hours. The reaction
mixture was allowed to cool and the precipitated
product was then ?ltered and recrystallized from
1-phenyl-3-heptadecyl-5-pyrazolone
with 20 cc. of phenyl hydrazine for 2 hours. The
reaction mixture was allowed to‘cool and the pre
cipitated product was then ?ltered and recrys
tallized from ethyl alcohol.
_
'
1.8 grams of the resulting product were dis
solved in 2 cc.'of water and‘ the solution added to
100 cc. of a gelatin silver bromide-iodide emul
ethyl alcohol.
35
'
1.8 grams of the above color. ‘former were dis
solved in 2.0 cc. of l-N-alcoholic KOH and added
with thorough mixing to 100 cc. of a gelatin
silver bromide-iodide emulsion. 'After coating
the emulsion containing the color former onto a
sion. The emulsion was coated onto a cellulose
acetate base and after drying,‘ the ?lm was ex 40 suitable support and drying, the ?lm was ex- .
posed and‘developed. A dye image of excellent
magenta color was formed in the emulsion.
posed and developed to yield a magenta imag
together with the silver image.
.
Example XII
4,4'-bis(l-B-naphthyl-Spmhloracetanilido-iiepyrazolone)
Five grams of 1-p-naphthyl-3-p-chloroacetan- '
ilido~5§pyrazolone, prepared according to Ex
ample 8 of U. S. Patent 2,334,495, were re?uxed
, with 20 cc. of phenyl hydrazine for 2 ‘hours. The
reaction mixture was allowed to cool and the pre
cipitated product was then ?ltered and recrystal
lized from ethyl alcohol,
'
1.8 grams of the resulting product were dis
70 solved in 2 cc. of water and the solution added
to'100 cc. of a gelatin silver bromide-iodide emul
sion. The emulsion was coated onto a cellulose
acetate base and after drying, the film was ex
posed and developed. A dye image of excellent
75, magenta color was formed in the emulsion.
2,411,951
11
12
‘
Eaample XIII
4,4'-bi|(l-phenyi-S-acot-c-naphthylamido-B-pynrolm)
it
$006
ii
55
Five grams of 1-phenyl-3-aoet-¢-naphthyla
emulsion containing the color former onto a suit
able support and drying, the illm was exposed and
,mido-5-pyrazolone prepared according to Exam
ple 6 of U. 8. Patent 2,334,495, were re?uxed with
developed to yield a magenta image together with
20 cc; of phenyl hydrazine for 2 hours. The re 20 the silver image.
I
action mixture was allowed to cool and the pre
Example
XVI
cipitated product was then ?ltered and recrys
4,4'-bis (1- (S-carboxyphenyl) -3-heptadecyl-5-pyrazolone)
tallized from ethvl alcohol.
1.8 grams of the resulting product were dis
solved in 2 cc. of water and the solution added to 25.
100 cc. of a gelatin silver bromide-iodide emul
sion. The emulsion was coated onto a cellulose
acetate base and after drying, the ?lm was ex
n
-
HuC|r~C-—to
H
.
’
$—‘C—C|1Hu '
0t
\
posed and developed. A dye image of excellent
magenta color was formed in the emulsion.
Example‘ XIV
00011
4,4'-bia (3-anlllno-5-pyrazolone)
@e-g-ijqmQ
35
00011
Five grams of 1-(3-carboxyphenyl) -3-hepta
decyi-?-pyrazolone prepared according to Ex
ample I of U. S. Patent 2,200,306 were re?uxed
with 20 cc. of phenyl hydrazine for 2 hours. The
reaction‘ mixture was allowed to cool and the
precipitated
product was' then ?ltered and re
Five grams or 3-anilino-5-pyrazolone prepared 40
crystallized
trom
ethyl alcohol.
according to the directions given in U. S. Patent
1.8 grams or the above color former were dis
Re. 22,329, were re?uxed with 15 cc. of phenyl
solved in 2.0 cc. of l-N-alcoholic KOH and’ added
hydrazine for 1 hour. The reaction mixture was’
with thorough mixing to 100 cc. of a gelatin silver
allowed to cool and the precipitated product was
bromide-iodide emulsion. After coating the
then ?ltered and recrystallized from ethyl al
- emulsion containing the color former onto a suit
cohol.
able support and drying. the ?lm was exposed and
1.8 grams of the resulting product were dis
developed to yield a magneta image together with
solved in 2 cc. of water and the solution added to‘
the silver image.
\r
r
100 cc. of a gelatin silver bromide-iodide emul
sion. The emulsion was coated onto a cellulose
acetate base and after drying, the ?lm was ex
Example XVII
4,4'-bls (1- (a-quinolyl) -3-aniliho-5~pyrazolone)
posed and developed. A dye image of excellent
- magenta color was formed inkthe emulsion.
Example XV
4,4'-bis(1-phenyl-3~p-anisyl-amino-?-pyrazolone)
H
H
60
Five grams of 1-(a-quinolyl)-3-anilino-5-py
razolone) prepared in the usual manner were re
Five grams. of 1-phenyl-3-p-anisyl-amino-5
pyrazolone prepared according to the directions
given in U. S. Patent 2,343,703, were re?uxed with
20 cc. of phenyl hydrazine for 2 hours. The re
action mixture was allowed to cool and the pre—
cipitated product was then ?ltered and recrystal
lized from ethyl alcohol.
1.8 grams of the above color former were dis
solved in 2.0 cc. of l-N-alcoholic KOH and added
?uxed with 720 cc. of phenyl hydrazine for 2 hours.
The reaction mixture was allowed to cool and the
precipitated product was then ?ltered and re
crystallized i'rom ethyl alcohol.
1.8 grams of the above color former were dis
solved in 2.0 cc. of 1-N-alcoholic KOH and added
with thorough mixing to 100 cc. of a gelatin silver
bromide-iodide emulsion. After coating the
emulsion containing the color former onto a suit
able support and drying, the ?lm was exposed and
with thorough mixing to 100 cc. of a gelatin silver
developed to yield a magnets. image together with
bromide-iodide emulsion. . After coating the 75 the silver image. 7
i
2,411,951
13
~
'
H
14'
emulsion layer which comprises exposing the lay
Example XVIII
4,¢i'-bia(1-ethane sulfonic acid-3-methyl-5-pyrazclone)
er and developing it with an aromatic primary
amino developing agent in the presence of a
H
coupler compound having the general formula:
5
\N/
HOiSHgCHhé
éHlCHISOaH
Five grams of l-ethane sulfonic acid-3-methyl
10
o-pyrazolone prepared according to. Example 2
of U. S. Patent 2,265,221 were re?uxed with 20 cc.
B1
in which R is selected from the class consisting
of hydrogen, alkyl, aryl arylamino, acetarylamido,
and aralkyl groups, and R1 is selected from the‘
of phenyl hydrazine for 2 hours. The reaction
mixture wasallowed to cool and the precipitated 5 class consisting of hydrogen, aliayl, aryl, aralkyl
product was then filtered and recrystallized from
ethyl alcohol.
.
1.8 grams of the above color former were dis
solved in 2.0 cc. of l-N-alcoholic KOH and added
with thorough mixing to 100 cc. of a gelatin silver
and heterocyclic groups.
-
6. The method of producing a magenta color
photographic image in gelatino silver-halide
emulsion layer which comprises exposing the layer _ '
and developing it with an aromatic primary
After coating the 2 or amino developing agent containing 4,4'-biS(1-(u
bromide-iodide emulsion.
emulsion containing the color former onto a suit-‘
‘ able support and drying, the ?lm was exposed and
developed to yield a magenta image together with
naphthyl-4'-sulf 0) -3 -methyl-5-pyrazolone) .
7. The'method of producing a magenta color
photographic image in gelatino silver-halide
the silver image.
'
While I‘ have disclosed the preferred embodi Gil emulsion ‘layer which comprises, exposing the
layer and developing it with an aromatic primary
ments of my invention and the preferred modes
amino developing agent containing 4,4'-bis(1
of carrying the same into effect, it will be readily
apparent to those skilled in the art that many
variations may be made therein without depart
(phenyl-4'-sulfo) -3-methyl-5-pyrazolone) .
8. The method of producing a magenta color
Accordingly. the 30 photographic image in a gelatino silver-halide
emulsion layer which comprises exposing the layer
scope of my invention is to be limited solely by
and developing it with an aromatic primary ami
the following claims.
- ‘
no developing agent containing 4,4'-bis(1-phen
a I claim:
7
yl-3-heptadecyl-5-pyrazolone) .
1. A color forming photographic developer com
prising an aromatic primary amino developing 3 Ol 9. A photographic silver-halide emulsion con
- taining a coupler compound having the general
agent and a coupler compound having the gen
ing from the spirit thereof.
eral formula:
1
'
formula:
>
"
TLlj__o-n
\N/
it
i.
is
i.
in whichR is selected from the class consisting 45 ‘in which R is selected from the class consisting
of hydrogen. alkyl, aryl arylamino, ‘acetarylamie
of hydrogen, alkyl, aryl, arylamino, acet'aryl
amido, and aralkyl groups, and R1 is selected from
the class consisting of hydrogen, alkyl, aryl,
aralkyl and heterocyclic groups.
-
' 2. A color forming photographic developer 50
comprising an aromatic primary amino develop
in: agent and 4,4'-bis(1-(¢-naphthy1-4'-sulfo)
3-methyl-5-pyrazolone) .
_
. 8. A color forming photographic . developer
comprising an aromatic primary amino develop 55
in: agent and 4,4'-bis(1-phenyl-4'-sulfo).-8
methyl-B-pyrazclone).
'
.
4. A color forming photographic deyeloper
comprising an aromatic primary amino develop
do, and aralkyl groups. and R1 is selected from
the class consisting of hydrogen. alkyl, aryl,
aralkyl and heterocyclic groups.
10. A photographic silver-halide emulsion for ‘
forming color images comprising a colloidal car- I
rier containing a sensitive silver-halide and 4,4’
bisue (a-naphthyl-4'- sulfo) -3~methyl-5-pyrazo
lone).
.
11. A photographic silver-halide emulsion for
forming color images comprising a colloidal car
rier containing a sensitive silver-halide and 4,4’
. bis(1-(phenyl-4'-suli'o) -3'-methyl-5-.pyrazolone) .
12. A photographic silver-halide emulsion for
in: agent and 4,4'-bis(1-phenyi-3-heptadecyl-5 00 forming'color images comprising a colloidal car
pyrazolcne).
'
,
5. The method of producing a magenta color
photographic image in a gelatinc silver-halide
rier containing a sensitive silver-halide and 4,4’
bis(1-phenyl-8-heptadeoyl-5-pyrazolone) .
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