close

Вход

Забыли?

вход по аккаунту

?

Патент USA US2411527

код для вставки
Patented Nov. 26,
2,411,523
I
s PATENT OFFICE
Y.‘
,_
'
.
2,411,521
,
n-rnosrna'roaarnmvnnmmns
‘ . 'JosephB. Dickey and James G. McNally, Roch-.
ester, N. Y., minors to Eastman Kodak Company, Rochester, N.~ Y, a corporation of New
g
I
Q‘
_
'3
v
_
‘
1 ‘
Jersey
“
No
Drawing. Application March 4, 1943,
Serial No. 478,002
-
'9 Claims. (01. 260-461)
This invention relates to aryl amino compounds
as
- and to a process for the preparation thereof,
well as to photographic developing agents com
prising such aryl amino compounds. This appli
cation is a. continuation-in-part of our copend
ing application, Serial No. 301,467, filed October
26, 1939.
g
It is known that 0- and
p-phenylenediamines
Of this group of lower molecular weight com
pounds, the p-phenylene compounds in which R’
represents an aliphatic group, e. 3., methyl, ethyl
or p-hydroxyethyl are especially useful as photo
graphic developers in color photography.v
Our new compounds can be prepared by re
ducing the appropriate nitro compounds, 1. e. ni
tro compounds of the following general formulas:
and some of their N-substituted derivatives act
10
as photographic developers.
phenylenediamine is used as a photographic de
veloping agent in color photography.
We have now found new phosphato ‘and phos
phito derivatives of o- and p-arylenediamin ,and
have further found that these derivatives are 15
.e?lcacious photographic developers.
.
_
It is, accordingly, an object of our invention to
provide new arylenediamine. .derivatives and a
III
process for the preparation thereof. A further 20
object is to provide new photographic developing
whereinD, R, R’, R", R'" and X have the values
' agents comprising these new derivatives. Other
given above. Such nitro compounds are prepared
objects will appear hereinafter.
by condensing nitro-N-hydroxyalkylarylamines
derivatives
can
be
Our new arylenediamine
with phosphorous chlorides, in accordance with
represented _by the following general formulas:
25v the following chemical equations:
BI"
wherein D represents an o- and p-arylene group, Q
e. g. an o- and p-phenylene group, R represents
an alkylene group of two or more carbon atoms,
e.‘ g, ethylene, propylene, etc., R’ represents hy-.
drogen or an alcohol radical, e. g., methyl, ethyl,
cyclohexyl, benzyl p-hydroxyethyl, etc., R" and
I
R',"
each represents hydrogen, a hydroxyl group.
an alkoxyl group, an alkylthio group or an amino - 45 In these equations D, R, R’, R", R?" and X have
group, and X represents oxygen or sulfur.
the values given above.
The . compounds of lower molecular weightv are
:As acid-binding‘ agents 'in the above processes,’
photographic
developers,
e.
g'.,
the'most e?icacio'us
tertiary amines, e. g., pyridine, vl‘I-methylpiperi-’
those in which D’r’epr'esents an 0-‘ or p-phenylene ' dine and dimethylaniline, are advantageously em
group,‘ in 'wh'ch It represents ethylene, in which ,50 ployed. The‘ condensation of the nitro-N-hy
v‘methyl, ‘ethyl or ?-hy
R’ represents, hydrogen,
droxyallryl arylam'ines with thephosphorous chlo
droxyethyl and in which 37 and Rf" each 'repre- '
, is advantageously effected at about, 0°, C.
‘sent; a‘ hydroiiyl" group, a methoxyl' or ethoxyl ‘rides
Nitro-N-hyciroxyalkylarylamines can be prepared
ethylthio‘ group or an
by condensing nitrocliloroarylhydrocarbons (er a.
' amino‘gr'oup. Thep-iphenylene compounds are
v-nitrwhlombeezene iwmttechlorobenme. and
.55
‘ ~gen‘'erally‘siiiierior to the :0 inhenvlene eommunds
2,411,027
4-nitro-1-chloronaphthalene) with hydroxyalkyl
maintained at that temperature for one hour.
amines, in accordance with the process described
The mixture was then treated with an aqueous
by Kremér-J. Am. Chem. Soc. 61, 1321 (1939). A
number of the phosphorous chlorides employed in
solution of 0.15 gram-mole of sodium bicarbonate
at 0° for several hours. The water and pyridine
our invention are well known substances. Dialkyl 5. were then removed from the mixture under re
esters of the monochloride of phosphoric acid can
duced pressure and the resulting yellow crystal
be prepared as described by Wichelhaus-Ann.
line
compound was washed with water and dried.
(suppl.) 6, 264 (1868) . Dialkyl esters of the
The yield was nearly quantitative. This yellow.
monochloride of dithiophosphoric acid can be
similarly prepared employing mercaptans instead 10 -
oi’ alcohols.
crystalline compound, viz. N-cyclohexyl-N-(?-di
methylphosphatoethyl)-p-nitroaniline, was dis
solved in 200 cc. of methanol. 2 g. of Raney'
nickel catalyst were mixed with the solution. The
The nitro compounds can be reduced in any ad
vantageous manner. We have found that the re
resulting mixture was subjected to hydrogena
ductions are most advantageously accomplished
tion
at 50° C. under a hydrogen pressure?oi 1500
by hydrogenating the nitro compounds in the 15 pounds.
Reduction’ was complete in about 30
presence of Raney nickel.
minutes. When cool, the reduction mixture was
Alternatively ‘our new phenylenediamine de
?ltered to remove the nickel, and any desired salt
rivatives can be prepared as illustrated in the
is prepared in the usual manner, viz. by treating
following speci?c example:
the ?ltered reduction mixture with a molecularly
/C!H!
N
\
_
20 equivalent amount of an acid, e. g. 10 percent sul-.
(Ii/o on.
crn-cm-on
+ Cl-P
\
furic acid, and concentrating (in vacuo) and
chilling until the salt separates out. The free
base is not stable in air.
pyridine
__.
OCH;
CH:
.
(l)
02H;
25
I‘<cnr-cul-o-r(Ii/OCH:+ H0]
_
H0
\
I
can
N=N-Cl +
1
N<
'
H‘
c111
‘ HzNON/
\
_
fll/o CH;
CHz-OHrO-P\
-_o
OCH:
02H:
N=NQN< ‘
cm
.
?ll/OCH;
CHrCHl-0-P\
N=N
N<
H‘
22.4 g. (0.1 mole) of p-nitro-N-ethyl-N-(w-hy
droxypropyl) -aniline were dissolved in 500 cc. of
35 dry pyridine. The mixture was cooled to 0° C.
To the cooled mixture was added 28.4 g. (0.15
mole) of the dimethyl ester of the monochloride
of dithio phosphoric acid having the formula:
+ H0]
OCH:
can .
I
0 SCH-z
4o
(Ii/0cm ’ .
cm-cm-o-rk
‘
'
/C
NH: + BIN
'
l
>
the resulting product, viz. N-ethyI-N-(y-dL
methyldithiophosphatopropyl) - p - phenylenedi
I
N\
H,
our
SCH:
The mixture was worked up as in Example 1 and
+ 2H‘ -_.
OCH:
(a)
0|| /son.
so
(2)
> 1
phatopropyl) -p-phenylenediami7ze
.
OCH:
'
Example 2.—-N-ethyl-N- ('y-dimethyldithiophos
amine, was then reduced as in Example 1, and
isolated as the sulfate.
(“l/00H;
cnl-cnl-o-
\
-
Example 3.,—N- (?-phosphatoethyl) -p-phenyl
enediamine
Similarly our other phenylenediamine derivatives
can be prepared.
-
The following examples will serve to illustrate
further the manner of obtaining our new com
pounds. These examples are not intended to 55
OH
18.2 g. (0.1 mole) of N-(p-hydroxyethyl) -o
nitroaniline were dissolved in 250 cc. of pyridine.
The mixture was cooled to 0° C. To the cooled
mixture were added 18.2 g. (0.12 mole) of phos
limit our invention. _
Example 1.—N-cyclohe:ryl-N-(p-dimethylphos
phatoethyl) -p-phenylenediamine
60 phorous oxytrichloride, dropwise with stirring,
26.4 g. (0.1 mole) of D-nitro-N-(p-hydroxy- }
ethyl) -N-cyclohex_ylaniline were dissolved in 500
over a period of one hour. The reaction mixture
was stirred for four hours and warmed to 50°
to 60° C. over a period of two hours and main
tained at that temperature for one hour. The
mixture was then treated with an aqueous solu
tion of 0.36 gram-mole of sodium bicarbonate at
0° C. for several hours. The water and pyridine
were then removed from the mixture under‘ re
cc. of dry pyridine. The mixture was cooled to
0° C. To the cooled mixture were added 21.6 B. 70 duced pressure and the resulting yellow crystal
line compound was washed and dried. ‘ This yel
(0.15 mole) of the dimethylester of the mono
chloride of phosphoric acid, dropwise with stir
ring, over a period of one hour.
The reaction
mixturewasstirredforfourhoursandwarmed
to50°to60°C.overaDeriod01twoh9\lr§8-lld 75
low crystalline compound, viz. N-(pephosphato
ethyl) —o-nitroeniline, was dissolved in methanol
and reduced as in Example 1. The resulting
phenylenediamine deriva?ve is unstable in air,
but white in color when air is excluded.
was
mile L-I-etML-zl-(pa
'
warmed
toiO'toU'Qoveraperlodof 710F318 hour.
‘maintained at ?ilt.
'?iemixturewasthmtreatedwlth-anoqmus
.- ..
“lull-14mm
solution or 0.45 gram-mole or sodium bicarbonate‘
I
Bi"
' H\
?lm
»
at 0' C. for several hours.‘ The water and pyri
0' am
dinewerethenremovediromthemixtureunder
reducedpressureandtheremltincyellowcrystcl
crn-cnr-o-r
.
-
\
line compound was washed and dried. This yel
NH:
as g. (0.1 mole) o? N-etbyl-N-(B-hydmxy
ethyll-i-amino-d-nitronaphthalene were dis
soiveddnmccoidrypyrldine. Themixturewas
cooléitoO' C. Tothecooledmixhirewere
lpw crystalline compound. viz. N-eth'yl-N-(p
phosphitoethyl) -'p-nitroani]ine wasreduced as in
Example 1 to give the phenylenediamine deriva
tive.
'-
‘
_ Our new phenylenediamine derivatives can be
_ added 11.1 g. (0.15 mole) of chlorophosphoryl
used
to form photographic images by develop’
15
diamide (prepared as described in Ann. 326, 236,
ment oi exposed silver halide contained in the
stirring,
over
a
period
of
. 19oz), dropwlse with
usual gelatinv carrier or in carriers, such as col
one hour. The reaction mixture was stirred for
_
lodion, cellulose esters or -resins.\_ Those of our
four hours and warmed to 50° to 00° C. over a
new phenylenediamine derivativeswhich are es
period of two hours and maintained at that tem
perature for one hour. The mixture was then
treated with an aqueous solution of $.15 gram
mole of sodium bicarbonate ‘at 0° C. for several
‘hours. The water‘and pyridine were then re
moved from the mixture. under reduced pressure
peciallv adapted to use in color photography (see
-above) can be used to develop visible images
from latent images in'silverhalide emulsions or '
to develop silver images from silver halide images
which are obtained by a so-called reversal proc
ess or by rehalogenizing a visible silver image.
and the resulting yellow crystalline compoimd
was washed and dried. This yellow crystalline
when employed in connection with color photog-'
raphy, the phenylenediamine derivatives act as
developers in the presence of couplers and the
ethyl) -1,4-naphthaiene was dissolved in meth
oxidation
products of the phenylenediamine de
anol and reduced as in Example 1 to give the
30 rivatives, arising from the developing action.
naphthylenediamine derivative.
couple with the couplers or color-formers to give
Example 5.—lV-ethyl - N -(p-dimetnylpnosphato
colored bodies or dyes. When used for the for
ethyl) -1,4-diamino-Z-methylbenzene
mation of colored photographic images, the
compound, viz. N-ethyl-(N-p-diamidophosphato
,
phenylenediamine derivatives can be used in con
.
35 junction with any well known coupler compounds.
such as those described in Fischer U. S. Patent
1,102,028, dated June 30, 1914; Mannes and
CH;
Godowsky U. S. Patent 2,108,602, dated February
15, 1938; Mannes, Godowsky and Peterson U. S.
.
7
~-
__
00H:
'21:; g. (0.1 mole) of N-ethyl-N-(p-dimethyl
phosphatoethyl) -m-toluidine (prepared from N
ethyl-N-(p-hydroxyethyl) -m-toluidine and the
dimethyl ester of the monochloride of phosphoric
acid according to the process described in Ex
ample 1) were dissolved in 200 cc. of cold acetic
acid. To the cold solution were added 0.1 gram
40
Patent 2,115,934, dated April 26, 1938; and
Mannes, Godowsky and Peterson U. S. Patent
2,126,337, dated August 9, 1938.
All the phenylenediamine derivatives described
herein can be used for the purpose of produc
; 'ing black-and-white images from exposed pho
tographic silver halide emulsions.
mole of o-chlorobenzene diazonium chloride.
The coupling was completed by the addition of
Developing solutions comprising our new
phenylenediamine
derivatives can be made up in
sodium bicarbonate. The azo compound was pre
the usual manner, using sodium sul?te and so
cipitated from thereaction mixture by the addi
carbonate.
tion, or water. The precipitated azo compound 50 dium
The term “alcohol radical,” in accordance with ‘
was ?ltered of! and washed free from acid. The
customary usage, is intended to mean an orazo compound was dissolved in methanol and
hydrogenated in the presence of Raney nickel. I ganic radical, which corresponds to an alcohol
and is derived therefrom by dropping the hy
The resulting reduction mixture was ?ltered to
' droxyl group, e. g., n-propyl is derived from
remove the nickel. The methanol was removed
n-propyl alcohol by dropping the OH group.‘
by distillation under reduced pressure and the
benzyl is derived from benzyl alcohol by drop
distilled
to
remove
o-chloro-.
residuevwas steam
ping the OH group, and tertiary butyl is derived
aniline. The residue was treated with sulfuric
by dropping the OH. group from tertiary butyl al
acid to convert the phenylenediamine derivative
to zlele sulfate which was then recrystallized from
wa
r.
-
Example 6 .—N-eth1ll - N -(p- phosphitoethyl) -p
I
60
who].
We‘ claim:
1. A compound’ characterized by the following _
general formula:
phenylenediamine
HzN-D-N
OH
'
/B'
.
"
a-o-P-
"
RI!
wherein D represents a member selected from the
22.1 g. (0.1 mole) of N-ethyl-N-(p-hydroxy 70 group consisting of o-arylene and p-arylene
groups, It represents an alkylene group having
.ethyl) -p-nitroaniline were dissolved in 500 cc. oi
at least- two carbon atoms, R’ represent a mem
dry pyridine. The mixture was cooled to 0° C.
ber selected from the group consisting of hydro
To the cooled mixture were added 20.6 g. (0.15
gen‘ and alcohol radicals, R" represents a, mem
trichloride,
dropwise
with
mole) of phosphorous
ber selected from the group consisting‘oi hydro?l
The
reaction
stirring, over a period of one hour.
8,411,587
1
e
I
e
_
o
>
8.
.
ilolthe'fmmgm.
mimsmmsamxtsvmmmea-
nmh:
ed?mthemms?m?fomenmdmm.
2- A mpound of the following M 1201l
‘wherein R rem“ an While 811ml! having
kyl??o mp: Ind amino,
at least two carbon atoms, R’ represents a mem-
' s- A '
of the foam”! mm'mh:
ber selected farm the group'consisting of hydro-l
I'm
gen and alcohol radicals, R" mpresents a mm- 15
NH
N
but selected from the group ‘consisting of hy' ‘ ,
m
f
-
-
B
25
I
V
98. A mom
wherein R represents an alky'lene gmcmp having at
mm“:
least two carbon atoms, R’ represents a member
7 '
selected
imm the group
consisting of hydrogen
and aliphatic
R” represents a member
,
‘(whom-0d’
_
on
_
_
m
_
[3w
N/
/
n’
‘
‘
wherein R’ W
n o
is an :a‘h1 gm
35
of :a. hydroxyl email, may!
I
'81- ’
:
‘
I
wherein R’ represents an alkyd group and R”
-
e
,
Sistine of hy?mxyl groups, ralkoxyl groups, alv_
, Elm .
4»
remesents a member selected from the group rcon-
.
vand R"
kylthio
and amino groups.
9. A compound of the following I
\onrom-mil-n"
kylth'o groups and amino emu
ill
'EHPWM%_R"
nmepzresentsamem‘bersebcbedfmmihegmupcm
0
.
:Ior
’
_
L A mmpmmd ‘0f the f0Euwmg general in!"
131m:
,
of ‘the f
HRFQN/
\
lthio groups and
mm“ EFWPS-
formula:
‘
‘selected from the group consisting ‘of 'hydroxyl M
1 groups,
I
H
’
H
'
that’!
mm‘
.
'
B—-'O—ZP—R"
cm
‘I
' onr“
7. A oompmmd of the 1
R’NOIK
_ ‘I
'
,
3. A compound of the following general Ior_
0 mm,
\m!
droxyl gmups, alkoxyl groups, alkylthio groups
and amino groups.
‘
mula:
7
"
‘
(
L
‘
$15,
\ v
‘SCH’
JOSEPH B. DIQKEY.
45
JAMES G. MEHMILYQ
Документ
Категория
Без категории
Просмотров
0
Размер файла
457 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа