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Патент USA US2126852

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Patented Aug. 16, 1938
2,126,852.
UNITED STATES PATENT oFFicg
2,126,852
CARBOCYANINE DYEST'UFFS AND A PROC
ESS 0F PREPARING THEM
Paul Wol?’ and Adolf Sieglitz, Frankfort-on~tlie
Main, Germany, assignors to Agfa Ansco Cor
poration, Binghamton, N._Y., a corporation of
New York
No Drawing. Application May 10, 1934., Serial
No. 725,010. In Germany May 16, 1933
'7 Claims.
The present invention relates to carbocyanine
dyestuffs and to a process of preparing them.
Hitherto carbocyanine dyestuiis have been pre
pared by linking together heterocyclic nitrogen
compounds containing reactive methyl groups or
methylene groups, in the form of their quaternary
salts by means of agents such as formaldehyde,
ortho-formic acid esters, sodium formate or the
like.
Now, we have found that valuable dyestuffs of
the carbocyanine series are obtainable by con
densing in the presence or absence of a condensing
(Cl.
260-44) .
‘
stirred for 2 hours, then diluted with 150 parts of
ortho-dichlorobenzene and cooled to +5° C.; at
this temperature, 170 parts of 1.3.3-trimethyl-2
methylene indoline are gradually added;_ after
about 15 hours the batch is freed from dichloro
benzene, methylaniline and any unchanged 1.3.3
trimethy1-2-methylene indoline which might be
present by alkaline steam-distillation and the
non-volatile residue is dried and then recrystal
lized fromligroin. The 1.3.3-trirnethylindoline-2 10
methylene-w-aldehyde of the following constitu
tiOIlI
agent such as, for instance, phosphorus oxychlo
CH3
I CH3
ride or piperidine, and advantageously in a sol
15 vent, such as, for instance, pyridine, nitroben
J=OH—-O//°
zene or acetic anhydride, an indoline compound
which contains a reactive methylene group in
alpha-position to the nitrogen and in which one
hydrogen atom of this methylene group is re
placed by the aldehyde group with the same or
N
\
l
15
H
C H3
another heterocyclic nitrogen compound, in the
form of its quaternary salt, containing in alpha
crystallizes in the form of coarse large crystals,
melting at 118° C. The yield amounts to about 20
75% of the theoretical.
or gamma-position to the nitrogen a reactive
methyl group. As aldehydes there may be men
ene-indoline, 1-ethyl-3.3-dimethyl-2-methylene
25 tioned, for instance, those of the following for
mula:
if’
C
30
P‘
\N/
l
(.II—CH—C%
By using, instead of 1,3.3-trimethyl-2-methy1
indoline or 1.3.3~triethyl-Z-methylene-indoline or
1-methy1-3.3-diethyl-2-methylene-indoline there
Instead of phosphorus Ioxychloride, thionyl
o
chloride or sulfurylchloride may be used with a
like result.
160 grams of phosphorus oxychloride are run 30
H
X
wherein X means methyl or ethyl, the two Y’S
mean two methyl or two ethyl groups and 21
35
means hydrogen, methyl, ethyl, methoxy, ethoxy,
amino, dimethylamino, diethylamino, or phenyl.
These aldehydes may be prepared as described
in the application of Paul Wol?, one of the present
40 applicants, Serial No. 725,009, ?led May 10, 1934,
as follows:
1.3.3-trimethyl-2-methylene-indoline is treated
into 140 grams of methylformylaniline in the
course of 1/2 hour at ordinary temperature, While
stirring. Stirring is continued for 3 hours, the
mixture is diluted with 300 grams of chloroben
ze'ne and cooled to +5° C. Thereupon, 200 35
grams of 1.3.3-trimethyl-2-methy1ene-5-methox
yindoline are gradually added thereto and the
product is worked up as described in Example 1.
In this manner 1.3.3-trimethyl-5-methoxyindo
line-Z-methyIene-w-aIdehyde of the following 40
constitution
with formylmethylaniline in the presence of
phosphorus oxychloride or thionylchloride or
45 sulfuryl chloride by causing the components to
CHa
I OH:
CHaO—
45
react either alone or in, an indi?erent solvent.
In this manner there is obtained, for instance,
1.3.3-trimethyl-indoline-2-methylene-w-aldehyde.
The process may be applied generally to indole
compounds containing methylene groups which
are capable of reaction.
For example, 155 parts of phosphorus oxychlo
ride are run into 135 parts of methylformylaniline
in the course of lé hour at ordinary temperature,
The mixture is subsequently
55 while stirring.
25
are obtained aldehydes of similar properties.
l
CH:
H
‘
is obtained in a yield of about ‘70% of the theo
retical. It melts at 105° C.
Similar aldehydes may be obtained by starting
50
from indoles which contain, instead of the
methoxy group, other substituents, such as, for
instance, an ethoxy or an alkyl or aryl group.
Said aldehydes may be prepared by the process 55
2
2,126,852
described in U. S. Patent No. 1,807,693 in the name
of Kalischer et al. Said aldehydes and their
preparation are not to be claimed in this appli
cation.
'
As heterocyclic nitrogen compounds in the form
of their quaternary salts there may be used, for
instance, those of the following formula:
m
p_
/
p_.
\N/
/ C-CH:
10
of 13.3-trimethyl-2-methylene-indoline with so
dium formiate in the presence of acetic anhy
dride.
By using an aldehyde in which the methyl
groups are replaced by ethyl groups or which is
substituted in the benzene nucleus by a substit
uent as, for instance, a nitro, amino, alkyl or
O-alkyl group, dyestuffs of similar properties are
obtained.
(2) 20 parts of 1.3.3-trimethylindoline-2-meth
ylenew-aldehyde and 20 parts of 1.3.3-trimethyl
5-methoxy-2-methylene-indoline are dissolved in
X halogen
wherein X means methyl or ethyl, 112 means one
of the bivalent values =C(methyl)z, -—O—-,
—S-—, —Se— and —CI-I=CH— and p means
hydrogen, methyl, ethyl, methoxy, ethoxy, amino,
dimethylamino or diethylamino.
These compounds may also be used as starting
materials if they are not present in the form of
their quaternary salts. but of the methylene bases.
In this case there must be used, as described in
Example 1, a condensing agent which yields
hydrohalic acid. There is intermediarily formed
100 parts of benzene and condensed, as described
in Example 1, with addition of 6 parts of phos 15
phorus oxychloride. There is obtained a water
soluble basic dyestuff which has a somewhat bluer
tint than rhodamine and by far surpasses it as
regards clearness of shade and fastness to light.
(3) By condensing 23 parts of 1.3.3-trimethyl 20
5emethQXyeiIld0line-2-methy1ene—w-aldehyde and
20 parts of l.3.3-trimethy1-5-methoxy-2-methyl
one-indoline as described in Example 1, there is
obtained a ‘water-soluble basic violet dyestu?
thequaternary salt of the heterocyclic nitrogen
which has'good fastness properties and by far 25
compound.
surpasses the hithereto known basic violet dye
stuifs as regards clearness of shade.
(4) 30.5 parts of 2-methyl-benzthiazol-iodine
The process of the present invention offers the
great advantage over the methods hitherto known
for the preparation of carbocyanine dyestuffsthat
30 it allows of obtaining in a simple manner the
preparation of symmetrical as well as of unsym
metrical dyestuffs of the carbocyanine series.
According to the new process dyestuffs of, for
1:: LI
identical with the dyestuif obtainable by reaction
instance, the following general formula are
obtained:
ethylate and 20.1 parts of 1.3.3-trimethylindoline
2-rnethylene—w.-aldehyde are dissolved in 500 30
parts of anhydrous pyridine and boiled under
re?ux for 11/2 hours whereby the formation of
the dyestuff' is ?nished, The pyridine, is expelled
and the dyestuff is recrystallized from alcohol.
It dyes wool vand tanned cotton bluish-red tints.
By replacing 2emethylbenzthiazol-iodine-ethylate
by other halogen alkylates of Z-methylbenzthiazol
similar dyestuffs are obtained.
(5) 23.1parts of 5-methoxy-1.3.3-trimethyl-2
methylene-indoline-w-aldehyde and 38.2 parts of .
40
5-meth0xy-2-methyl-benzselenazol-iodine -ethyl
wherein X meansmethyl or ethyl, the two Y’s
mean two methyl groups or two ethyl groups,
ate (selenium; position numbered one) are boiled
inpyridine as described in Example 4. There is
obtained a- dyestu? which dyes wool and tanned
m means one of the bivalent values =C(methyl) 2,
cotton violet tints.
--O-—, —S—, —-Se-— and -CH==.CH-—, the com
pounds being substituted in at least one of the
(6) 33.3 parts of 2.5.G-trimethylbenzthiazol
iodine-ethylate are condensed with 22.9 parts of
45
positions a by methyl. ethyl. methoxy. ethoxy,
1.3.3.5 .6 - pentamethyl - indoline - 2 - methylene - w -
amino, dimethylamino, diethylamino or phenyl.
The carbccyanine dyestuffs obtainable accord
ing to the present process are, for instance, suit
able tor sensitizing photographic silver halide
emulsions: they may be used with special ad
vantage for sensitizing ammonia emulsions.
aldehyde as described in Example 4. There is
obtained a dyestuff which dyes wool and tanned 50
cotton violet-red tints.
The following examples serve to illustrate the
invention but they are notintended to limit it
otherwise proceeding as indicated in that ex
theretd'the parts being by weight:
(7) By using in Example _6 instead of 2.5.6-tri
methylbenzthiazol-iodine-ethylate 31.7 parts of
21516 - trimethylbenzoxazol - iodine — ethylate
and
:11 Cl
ample, a dyestu?" is obtained which corresponds
to the following formula:
(1) 17.3 parts of 1;3.3-trimethyl-2-methylene—
indoline and 20.1 parts of 1.3.3-trimethylindoline
60 2-methylene-wraldehyde
are dissolved in 100
parts of benzene and 6 parts of phosphorus oxy
chloride are added drop by drop. Thereupon,
the Whole is boiled until the formation of the dye
stu? is ?nished. The benzene is expelled. The
dyestuff which has the following constitution:
CH3 CH3
_t/
CH3
CH3
\t
N%CIE—CH=CH—CH=(|I\N
(‘3H\3-c1
OH:
is dissolved'in water and may be salted out in
the form of cristals having a metallic luster. It
75 dyes tanned cotton bright bluish-red tints and is
60
It dyesv wool and tanned cotton yellowish red
tints.
(8) By using 36.5 parts of 2—methyl-5.6-.di
methoxybenzthiazol-iodineeethylate instead of 2
methylbenzthiazol-iodine~ethylate, mentioned in
Example '4, and otherwise proceeding as described 70
in Example 4, a dyestuff is obtained which dyes
wool and tanned cotton violet-red tints.
(9) By using instead of 2-methylbenzthiazol
iodine-ethylate, mentioned in Example 4, 34.7
parts‘ of ‘ 6-dimethyl-amino-2~methylbenzthiazol 76
P’
2,126,852
iodine-ethylate (sulfur position numbered one)
and otherwise proceeding as described in Ex
ample 4, a dyestuif is obtained which dyes wool
and tanned cotton currant tints.
(10) By using 35.5 parts of 4.5-benzo-2-methyl
benzthiazol-iodine-ethylate instead of 2-methyl
benzthiazol-iodine-ethylate, mentioned in Exam
ple 4, and otherwise proceeding as described in
Example 4, a dyestu? is obtained which dyes wool
10 and tanned cotton violet-red tints.
(11) 29.9 parts of quinaldine-iodine-ethylate
and 20.1 parts of 1.3.3-trimethyl-2-methylene
indoline-w-aldehyde are boiled for 9 hours under
re?ux in 500 parts of anhydrous pyridine. After
removal of the pyridine, a dyestuff is obtained
3
pentamethylindolin - 2 - methylen-w-aldehyde
in
'
anhydrous pyridine.
2. The process which comprises boiling under
re?ux for about 11/2 hours a solution of 2-meth
ylbenzox'a'zol-bromo-methylate
and 5-phenyl
31
1.3.3-trimethyl-2-methylenindolin-w-aldehyde.
3. The process which comprises boiling under
re?ux for about 11/2 hours a solution of G-meth
oxy-2-methyl - benzoxazol - iodine ethylate
and
1.3.3.5-tetra-methyl - 2 - methylenindolin-w-alde
10
hyde.
4. The process which comprises condensing an
aldehyde compound of the general formula:
which, when recrystallized from alcohol, dyes
wool violet tints. By using instead of quinaldine
iodine-ethylate other quaternary salts of quinal
dine or quaternary salts of quinaldine derivatives
which contain in the benzene nucleus of the quin
aldine substituents such as methyl, methoxyl,
ethoxyl, dimethylamino or diethylamino groups,
similar dyestu?s are obtained.
30
wherein X means a substituent of the group
consisting of methyl and ethyl, the two Y’s
(12) By using instead of the quinaldine-iodine
ethylate mentioned in Example 11 the equal
weights of lepidine-iodine-ethylate and proceed
mean identical alkyl radicals of the group con—
ing as indicated in Example 11, a dyestu? is ob
tained which dyes wool and tanned cotton clear
dimethylamino, diethylamino and phenyl
light-blue tints.
By using instead of lepidine-iodine-ethylate
sisting of methyl and ethyl and p1 and p2 rep
resent members of the group consisting of hy- =
drogen, methyl, ethyl, methoxy, ethoxy, amino,
with a compound of the general formula:
P:
other quaternary salts of lepidine or such deriv
30
/m
atives of lepidine as are substituted in the ben
zene nucleus by methyl, methoxyl, ethoxyl, dial
P4
kylamino or other groups, similar blue dyestuffs
L’) Li are obtained.
(13) 27.’? parts of 5-phenyl-1.3.3-trimethyl-2
methylene-indoline-w-a1dehyde and 22.8 parts of
2 - methylbenzoxazol - bromine - methylate
are
boiled in pyridine as indicated in Example 4.
40 There is obtained a dyestu? which dyes wool and
tanned cotton red tints and which has the fol
lowing constitution:
CH3
/C—C Ha _
N/
l\
X halogen
wherein X means a substituent of the group
consisting of methyl and ethyl, m means a
member of the group of bivalent values con- ~
sisting of =C(methyl)2, —O—, —S—, —Se—
and -CH=CH and p3 and p4 represent mem
bers of the group consisting of hydrogen,
methyl, ethyl, methoxy, ethoxy, amino, dimeth
ylamino, diethylamino and phenyl.
CH3
5. The process which comprises boiling in
presence of a solvent an aldehyde compound of
45
the general formula:
(14) 21.5 parts of 1.3.3.5-tetramethyl-2-meth
ylenindoline-w-aldehyde and 31.9 parts of 6
methoxy-Z-methylbenzoxazol-iodine-ethylate are
condensed in pyridine as indicated in Example
There is obtained a dyestu? which dyes wool
4.
and tanned cotton red tints and which has the
following constitution:
OCH:
wherein X means a substituent of the group
consisting of methyl and ethyl, the two Y’s 55
mean identical alkyl radicals of the group con
CH3
—-0
60
50
CH3
\C/
(‘J—oH=cH—oH=|o
N/
\N
C2/H5 \J
(‘7H3
—CH3
sisting of methyl and ethyl and p1 and p2
represent members of the group consisting of
hydrogen, methyl, ethyl, methoxy, ethoxy,
amino,
phenyl
dimethylamino,
diethylamino
and
with a compound of the general formula:
By using instead of the indoline—2-methylene-w
aldehydes mentioned in the foregoing examples
aldehydes from more highly alkylated indolines,
for instance, the ethyl derivatives, or from such
indolines as contain in the benzene nucleus fur
ther substituents, for instance, the N02, Nil-I2, an
alkyl or O-alkyl group or as contain a naphtha
lene nucleus, similar dyestuffs are obtained.
We claim:
1. The process which comprises boiling under
re?ux for about 11/2 hours a solution of 2.5.6-tri
75 methylbenzoxazol-iodine-ethylate and 1.3.3.5.6
wherein X means a substituent of the group
consisting of methyl and ethyl, m means a
member of the group of bivalent values con
sisting of =C(methyl)2, —O—, —S—, —Se—
and —CH=CH—- and p3 and 104 represent
members of the group consisting of hydrogen
)
60
4-
2,126,862
I methyl,‘ ethyl,‘ methoxy, ethoiimniamino, ‘ di
methylamino, diethylamino and-phenyl.
6. The process" which comprises; condensing an
7. The process which comprises boiling in pres
ence of a solvent an aldehyde compound of the
general formula:
aldehyde compound ofvthe generarformula:
,
.7
opl
.
p
10
‘sf/Y
——-c|;
’
g
p
I '~/o
'. .
consisting of methyl and ethyl, the two Y’s
sisting of methyl and ethyl and p1 and p2
represent members of the group consisting of
hydrogen, methyl, ethyl, methoxy, ethoxy,
amino, dimethylamino, diethylamino and
sisting of methyl and ethyl and p1 and :22
represent members of the group consisting of
hydrogen, methyl, ethyl, methoxy, ethoxy,
amino, dimethylamino, diethylamino and
phenyl
with a compound of the general formula:
Pa
Pa
/O\ C-CH:
P4
N/
I\
hydrogen, methyl, ethyl, methoxy, ethoxy,
phenyl.
l\
wherein X means ‘a substituent of the group
consisting of methyl and ethyl and 233 and 174
represent members of the group consisting of
dimethylamino.
l
X halogen
X halogen
amino,
20
/O
C—C Ha
wherein X means a. substituent of the group
30
mean identical alkyl radicals of they group con
phenyl
with a compound of the general formula:
25
10
consisting of methyl and ethyl, the two Y’s
mean identical alkyl radicals, of the group con
Pr-
Cl
x
wherein X means a substituent of the group
wherein X means a substituent of the group
20
O
\1]‘/J>=CH—C<H
\H
I
X
15
——0
/
.
c"=olH—o/
N
v
a
diethylamino
and
consisting of methyl and ethyl and, p3 and 2M
represent members of the group consisting of
hydrogen, methyl, ethyl, methoxy, ethoxy,
amino, dimethylamino, diethylamino and
phenyl.
PAUL WOLFF.
ADOLF SIEGLITZ.
25
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