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Патент USA US3090792

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United States Patent 0 l ice
3,090,782
Patented May 21, 1963
2
1
Q are the supplementary members of a heterocyclic
ring system selected from the group consisting of indoline
3,090,782
PROCESS FOR THE PRODUCTION OF
CYANINE DYESTUFFS
Max Coenen, Gruiten, Rhineland, Oskar Weissel, Krefeld
Urdingen, and Walter Wonder, Leverkusen, Germany,
assignors to Farbcnfabriiren Bayer Aktiengesellschaft,
Leverkusen, Germany, a corporation of Germany
No Drawing. Filed Mar. 4, 1959, Ser. No. 797,057
Claims priority, application Germany Mar. 6, 1958
7 Claims. (Cl. Mil-240.6)
The present invention is concerned with new cyanine
and benzothiazole ring systems,
R3 is a saturated alkyl radical with up to 18 carbon
atoms,
R, is an auxochrome group,
R5 is a saturated alkyl radical with up to 4 carbon
atoms, or a phenyl group,
R6 is a hydrogen atom or a saturated alkyl radical with
10 up to 4 carbon atoms, and n is zero or the integer l, in
the presence of an acidic condensing agent.
More particularly, in Formula I the group
dyestu?s and with a process for the production thereof.
It is known to produce cyanine dyestuffs having a
cyano radical (—CEN) in the alpha position on the
I’A\\
methine chain by reacting quaternary cyclic ammonium 15
salts, which contain in the reactive position a thio-ether,
-1~i
b:
may be, for instance,
a seleno-ether or a substituted or unsubstituted amino
group, in the presence of condensing agents which are
usually basic, with either N-substituted heterocyclic cya
nomethylene compounds or their salts or reacting them 20
with unsubstituted cyanomethylene heretrocyclic com
pounds and quaternizing the thus formed cyanine bases.
We have now found that cyanine dyestuffs, the methine
wherein E1, E2, E3, and E4 may be, for instance,
(methylidyne) chain of which is substituted by at least
one cyano group, can be produced in a technically simple 25
manner and usually with excellent yields by reacting an
aldehyde of the general formula:
(I)
,a
Rl-N—b (=o-cH),,.=e-oH0
2
—N (caHs) (C2H4CN), -N(C4Ha) lca?scl)
—NHCOCH3, --NHCOC2H5
CN
—NHCOC8H5(phenylcarbonylamino)
wherein A are supplementary members of an indolenine
—NHSO2C6H5(phenylsulfonamido), —COOH, —CN
ring system,
R, is a saturated alkyl radical with up to 18 carbon
atoms,
35
R; is a substituent selected from the group consisting of
(a) hydrogen, cyano, a lower alkoxycarbonyl radical
(R—O~—OC--), the alkoxy radical of which contains not
—CONHC6H5(phenylaminocarbonyl) , —SO2NHC2H5
more than 4 carbon atoms, or a carbamoyl (NH;CO—-) 40
Or an alkylcarhamoyl or arylcarbamoyl (R—-NH—-CO—)
radical, or (b) a lower alkanoyl (R—CO--) radical hav~
ing not more than 4 carbon atoms, or a benzoyl radical,
and m is zero or the integer l,
with a compound of the general formula:
(II)
--COOCH3, —COOC3H5, —COOCgHq, —COOC,H9
—-COOC5H5(phen0xycarbonyl), —CONHCHa
—C0NHC2H5, —CONHC3H7, ~CONHC4H9
N02; G1 and 6; may be, for instance, —CH3, —CgHs,
—C3l-l7, —C4H9, —C8H5(phenyl); the group
,A,‘
further may be, for instance,
45
T-X
wherein X is a radical selected from the group consisting
of (a) a radical of the general formula:
50
wherein G1 and G2 have the same signi?cance as above.
In Formula II the group
(b) a radical of the general formula:
__D._R4
(c) a radical of the general formula:
"""" "B ___‘“~
55
—OH=O'E;OH:CH);:N—R:
may be, for instance,
l
R:
60
(d) a radical of the general formula:
,Q\
—O=O—-—N—~R3
65
wherein B are the supplementary members of a 5 or 6
atom heterocyclic ring system,
D is a phenylene radical,
Z are the supplementary members of an indole ring 70
system,
M has the same signi?cance as R2,
3,090,782
4
R1 in Formula I, and R3, L and T in Formula II may
be, for instance, —-CH3, -C2H5, —-C3H7, ——C4H9,
—-C5Hn, and so on to C18H31.
R2 in Formula I may be, besides the signi?cance al
ready speci?ed hereinbefore, for instance, -COOCH3i
-—COOC2H5, -COOC3H7, —COOC4HB, —CONHz,
—CONHCH3, —-CON(CH3)2, —-CONHC2H5,
—CON(C2H5)2, --CONHC6H5 (phenylaminoearbonyl),
10
15
-—COCH3, —-COC2H5, -—COC4H9.
R4 in Formula II may be, for instance, ——OCH3,
-—N(C4H9) (C2H4Cl), —N(CH3) (C6H5) (methylphen
ylamino), -—N(C2H5) (C6H5) (ethylphenylamino)
-—N(CH3) (C6H4OCH3)
(methylmethoxyphenylamino) .
R5 and R6 in Formula 11 may be, besides the signi?
20
cance given above, for instance, —~CH3, —-C2H5, ——C3H7,
and C4119.
Suitable aldehydes of the mentioned type are, for ex
ample,
1,3 ,3-trimethyl-Z-cyanomethylene-inodoline-w-aldehyde,
25
1, 3, 3 -trimethyl-5-chloro-Z-cyanomethylene
indoline-w-aldehyde,
1,3,3 -trimethyl-5-methyl-2-cyanomethylene-indoline
w-aldehyde,
1,3 ,3 -trimethyl-5-ethoxy-Z-cyanomethylene
indoline-w-aldehyde,
1,3,3 -trimethyl-5<phenyl-2-cyanomethylene-indoline
(ii-aldehyde,
1,3 ,3-trimethyl-S-carbornethoXy-2-cyan0rnethy1ene
indoline-w-aldehyde,
35
1,3-dimethyl-3-ethyl-2-cyanomethylene-indoline-w
aldehyde,
1-ethyl~3,3-dimethyl-5-methoxy-2-cyanomethylene
indoline-w-aldehyde,
40
1-octadecyl-3 ,3 -dimethyl-Z-cyanOmethyIene-indoline
w-aldehyde,
1,3,3 -trimethyl-S-dimethylamino-Z-cyanomethylene
indoline-w-aldehyde,
1,3, 3-trimethyl-5,7-dimethoxy-2-cyanomethylene
indoline-w-aldehyde,
1, 3 ,3 ,5 ,6-pentamethyl-2-cyanomethylene-indoline
w-aldehyde,
1,3 ,3 -trimethyl-4-methoxy‘7-methyLZ-cyanomethylene
indoline~w-aldehyde,
1,3 ,3 -trimethyl-6,7-benzo-2-cyanome thylene-indoline
aldehyde,
1,3 ,3-trimethyl-2 (m,'y-dicyanopropenylidene ) -
indoline-w-alclehyde and
1, 3 ,3-trimethy1-2d( 'y-cyanopropenylidene ) indoline-w
aldehyde.
Such aldehydes are obtainable, for example, by the
action of N-methyl formanilide in the presence of phos
phorus oxychloride on the corresponding cyanomethyl
ene indoline derivatives, for examples, by the process de
60
70
scribed in US. patent application Serial No. 737,474,
?led May 26, 1958, now US. Patent No. 2,957,005.
Suitable methylene bases of the hereinbefore speci?ed
type are, for example,
1,3,3-trimethyl-2-methylene-ind0line,
1,3,3-trirnethyl-S-chloro-2-methylene-indoline,
1,3,3-trimethyl-5-methyl-2-methylene-indo1ine,
1,3,3-trimethyl-5-ethoxy-2-methylene~indoline,
1,3,3-trimethyl-5-phenyl-2-methylene-indoline,
1,3,3-trimetl1yl-5 -carb0rnethoXy~2-rnethylene-indoline,
1,3-dimethyl-3 -ethyl-2-methylene-indoline,
1 ethyl-3,3-dimethyl-S-methoxy-Z-methylene-indoline,
1 octadecyl-3,3-dimethyl-2-methylene-indoline,
1,3,3 -trimethyl-5 -dimethylamino-2-methylene-indoline,
1,3 ,3-trirnethyl-5,7-dimethoxy-2-methylene—indoline,
1,3,3,5,?-pentamethyl-Z-methylene-indoline,
3,090,782
1 ,3,3-trimethyl-4-methoxy-7-methyl-2-methylene
indoline,
A special class of new dyestuffs of the kind mentioned
above corresponds to the following formula:
l,3,3-trimethyl-6,7-benzo-2-methylene-indoline,
l ,3,3 -trimethy‘l-Z-cyanomethylene-indoline,
1,3,3-trimethyl-5-chloro-Z-cyanomethylene-indoline,
1,3,3-trimethyl-5-rnethyl-2-cya.nomethylene-indoline,
1,3,3-trimethyl-5 -ethoxy-2-cyanomethylene-indoline,
N
wherein A, M, Q, R1, R3 and Y- have the signi?cance as
1 ,3, 3 ~trimethyl-5 -phenyl-2-cyanomethylene-indoline,
described above.
1 , 3 , 3 -trimethyl-5 -carbometh oxy-2-cyanomethylene
Speci?c preferred examples of compounds conform
indoline,
l,3-dimethyl-3-ethyl-2-cyanomethylene-indoline,
1-ethyl-3,3-dimethyl-S-methoxy-Z-cyanomethylene
ing to this formula, whose preparations and uses are de
scribed respectively in Examples 17, 16, 11, 10, and 19,
are the following:
indoline,
l-octadecyl-3,3-dimethyl-2-cyanomethylene-indoline,
l,3,3-trimethyl-5-dimethylamino-Z-cyanomethylene
indoline,
l,3,3~trimethyl-5,7-dimethoxy-2-cyan0methylene
indoline,
1,3,3,5,6-pentamethyl-Z-cyanomethylene-indoline,
1,3,3-trimethyl-4-methoxy-7-methyl-2-cyanomethyl
ene-indoline, and 1,3,3-trimethyl-6,7-benzo-2-cyano
l
M
CH;
C H;
C Ha
C H;
+
15
Cl
611,
20
methylene-indoline.
CH:
CH;
bluish
red
hm
CH:
CH;
+
Suitable reactive indoles are, for example, l-methyl-Z
phenyl-indole and Z-methyl-indole. As examples of suit
able quaternary cyclic ammonium salts there may be
mentioned 2,3-dimethyl-benzthiazolinium salts.
The mentioned cyanomethylene bases can be obtained,
for example, by the action of cyanogen halides on the
corresponding methylene indoline derivatives, for exam
ple, by the process described in US. patent application 30
Serial No. 735,992, ?led May 19, 1958, now US. Patent
No. 2,993,907.
As acidic condensing agents there are advantageously
used inorganic acid chlorides, such as phosphorus oxy
chloride or thionyl chloride.
Further suitable acidic con
densing agents are organic acid chlorides and anhydrides,
such as acetyl chloride and acetic anhydride, as well as
concentrated mineral acids, such as sulphuric acid and
phosphoric acid.
In some cases it is recommended to use 40
glacial acetic acid-triethylamine as the condensing agent.
Suitable solvents are, for example, aromatic; aliphatic
and cycloaliphatic hydrocarbons, such as benzene, ligroin
and cyclohexane, aliphatic, araliphatic and aromatic
ethers, chlorinated aliphatic and aromatic hydrocarbons,
such as chloroform and chlorobenzene, aliphatic ketones,
such as acetone, as well as low molecular weight fatty
acids, such as acetic acid.
The reaction usually proceeds even at room tempera
ture.
In other cases it can be advantageous to increase
the temperature somewhat to, for example, 40-100” C.
A smooth reaction of this type of the aldehydes to be
used according to the invention of the Formula I with
compounds of the Formula II was not to be foreseen
since it was to be expected that the reactivity of the
aldehyde group would be strongly in?uenced by the 55
cyano group present on the same carbon atom in the
same manner as the methylene hydrogen in the cyano
methylene-indolines obtainable by the process according
to US. Patent Application Serial. No. 735,992, methyl
ene hydrogen of which is frequently inert in the case of 60
many reactions due to the cyano 0 group present so that,
for example, alkylations or acylations were not success
The dyestuffs obtainable according to the invention are
ful.
in the same way as the already known cyanine dyestulfs,
According to the invention new dyestuffs of the general
65 valuable sensitizers for photographic silver halide emul‘
formula may be obtained.
sions. Furthermore they are suitable for dyeing and
printing materials such as ?bres, threads, strips and
woven materials, made from polyacrylonitrile, acryloni
1
ON
' trile-containing mixed polymers or acetate rayon.
The dyeings and printings obtained with the dyestuffs
wherein A, X, R1, R2 and m have the same signi?cance 70 according to the invention on these materials are char
as mentioned above and Y‘ is an anion, for instance,
Cl’, Br’, 1', 80,", N03’, H2PO4', HPO4", C104’,
CHaCOO’, C2H5COO', CCl3C0O', C6H5SO3',
acterized by very good fastness and especially by excel
lent stability to light and are clearly superior, in this re
spect, to the already known dyestuffs of the Astraphloxine
75 type that are devoid of cyano radicals.
3,090,782
8
7
Example 3
Production of 2-(1,3,3-trimethy1-5-methoxy-indole)-2'
It is known that the cyano group attached to the methine
chain is saponi?ed very quickly and completely by heat
ing in an aqueous acid medium. Since the free carboxylic
(1',3 ’,3'-trimethyl-5’-methoxy-indole) -a-cyano-trimethine
acids which result are immediately decarboxylated under
cyanine chloride.
the reaction conditions, compounds devoid of cyano radi
cals can be very easily produced in this manner.
Not only the rapid ability to hydrolyze of the cyano
group but also the instability to light that is to be expected
with the sensitizing effect appeared to exclude the use of
these dyestuffs for the dyeing of textiles, for instance.
It was, therefore, surprising, that the dyestu?s accord
ing to the invention, containing cyano groups, are suitable
for printing and dyeing material such as those speci?ed
12.8 grams 1,3,3-trimethyl-5-methoxy-2-cyanomethy1ene
above.
indoline-w-aldehyde, 10.2 grams 1,3,3-trimethyl-5-meth
The dye baths and printing pastes can contain the usual 15 oxy-2-methylene-indoline and 7.5 grams phosphorus oxy
additives, including levelling agents, such as substituted
chloride are reacted in the presence of 20 milliliters chloro
polyglycol ethers, condensation products of aromatic
form in the same manner as in Example 2.
Greenish
sulpho acids or condensation products of ‘high molecular
shining crystals are obtained. Yield: 19.2 grams, color of
weight aliphatic amines with ethylene oxide, or dispersion
solution in water: bluish-red.
agents, such as fatty alcohol sulphonates, condensation 20
Example 4
products of high molecular weight alcohols and ethyl
ene oxide or cellulose sulphite waste liquor products.
Production of 2-(1,3,3-trimethyl-5-chloro-indole)-2’-(1',
One can dye and print with these dyestuffs by the usual
3',3’-trimethyl - 5' - chloro - indole)-a-cyano-trimethine
methods, for example, by boiling the materials to be dyed
cyanine chloride.
in aqueous dye baths, optionally with the addition of 25
acids, or by treating the materials with printing pastes
containing the dyestuffs, and subsequently steam treating.
The following examples are given for the purpose of
illustrating the invention:
30
Example 1
Production of 2-(1,3,3,S-tetramethyl-indole)-2'-(1’,3',
3',S'-tetramethyl-indole)~a-cyano-trimethinecyanine chlo
ride.
CH3
CH5
CH3
CH3
1’
Cl
(EH!
CH5
red
13.0 grams 1,3,3-trimethyl-5-chloro-2~cyanomethylene-in
doline-w-aldehyde, 10.4 grams 1,3,3-trimethyl-5echloro-2
35 methylene-indoline, 7.6 grams phosphorus oxychloride
and 40 milliliters chloroform are heated together under
re?ux for 30 minutes. The reaction mixture is evaporated
to dryness. The so-obtained crude dyestuff is boiled with
50 milliliters water, ?ltered and washed with water. A
40 brown powder is obtained. Yield: 25.7 grams, color of
solution in water: scarlet-red.
A mixture of 120 grams 1,3 ,3,S-tetramethyl-Z-cyanometh
Example 5
ylene-indoline-w-aldehyde, 93.5 grams 1,3,3,5-tetrameth
Production of 2-(1,3,3 - trimethyl-S-carbomethoxy-in
yl-2~methylene-indoline and 200 milliliters chloroform are
dole)-Z'-(1',3',3'-trimethyl - indole)-ot-cyano - trimethine
heated to boiling and 75 grams phosphorus oxychloride
cyanine chloride.
added dropwise in the course of 25 minutes. The reac
tion ‘mixture is subsequently heated under re?ux for a
Example 2
Production of 2-(1.3,3-trimethyl-5-methoxy-indole)-2'
CH:
CH;
further 15 minutes, evaporated to dryness and the residual
crude dyestutf recrystallized from water. Metallic shining 50
crystals are obtained. Yield: 181 grams, color of solu
tion in water: scarlet red.
55
\
omooo
l/
CH:
OH!
+
o
\
01
bluish
red
(1',3',3’-trimethyl-indole)-a-cyano - trimethine - cyanine
17.1 grams of dyestuft are obtained when 13.1 grams 1,3,3
chloride.
trimethyl-5-carbomethoxy-Z-cyanomethylene - indolinc-w
/
on,
aldehyde ‘and 8.7 grams 1,3,3-trimethyl~2-methylene-in
on,
doline were reacted and recovered in the same manner as
\
60 described in Example 2.
A ?ne crystalline powder is ob
tained. Color in methanol: bluish-red.
Example 6
Production of 2-(1,3,3-trimethyl-5,7-dimethoxy-indole)
bluish-red
65
A mixture of 12.8 grams 1,3,3-trimethyl-5-methoxy-2
2’-(1’,3',3'-trimethyl - 5' - chloro - indole)-a-cyano-tri
methine-cyanine chloride.
cyanomethylene-indoline~w-aldehyde, 8.7 grams 1,3,3-tri
methyl-2-methylene-indoline and 20 milliliters chloroform
is mixed in the course of 2 minutes with 7.5 grams phos
phorus oxychloride. The ‘mixture automatically warms 70
up to boiling point. It is boiled under re?ux for an addi
tional period of 5 minutes, then evaporated to dryness and
the residual crude idyestul’f recrystallized from water.
Crystals having a metallic sheen are obtained. Yield:
75 By the reaction of 6.8 grams 1,3,3-trimethyl-5,7-dimeth
22.0 grams, color of solution in water: bluish-red.
8,090,782
V
grams of dyestulf. This is a brown powder.
methanol: bluish-red.
zene is mixed with 6.0 grams thionyl chloride and heated
under re?ux for 10 minutes. After cooling the dyestutf
formed is ?ltered off with suction and washed with ben
zene. The dyestuff is in the form of red-brown crystals.
Yield: 21.0 grams, color of the solution in water: red
Color in
Example 7
Production of 2-(1,3,3,5,6-pentamethyl-indolc)-2’-(1‘,3’,
orange.
3'-trimethyl-S’ecarbomethoxy - indole)-a-cyanotrimethine
cyanine chloride.
on,
on,
on.
\0/
CH
+
/
/ ‘EN
’
Example 11
Production of 2-(l,3,3-trimethyl-S-methoxy-indole)-2'
( 1', 3’,3 ',5 ’-tetramethy1-indole ) ~a-7-dicyano-trimethine-cy
anine chloride.
o o 0 CH;
O=O—OH=0H-C
on
10
\O
\
-
on,
10
ene-indoline-w-aldehyde and 11.6 grams l,3,3-trimethyl-5—
chloro-2-cyanomethylene-indoline in 100 milliliters ben
oxy-2ecyanornethylene-indoline-w-aldehyde and 5.2 grams
1,3,3-trimethyl-2-methylene-indoline in accordance with
the method described in Example 2 there is obtained 8.6
-
CH3
Cl
\\
N
N
bluish
d5.
$11,
red
CH3
\
*
CHaO
By the reaction of 6.6 grams l,3,3,5,6—pentamethyl-2
l
bluish
cyanometihylene-w-aldehyde and 5.7 grams 1,3,3-trimethyl
CH;
CH:
red
5-carbomethoxy-2-tnethylene~indoline in accordance with 20
12.8 grams 1,3,3-trimethyl-S-methoxy-Z-cyanomethylene
the method described in Example 2, 7.8 grams of dyestu?
indoline-w-aldehyde, 10.6 grams 1,3,3,5-tetramethyl-2-cy
are obtained. This is a ?ne crystalline powder. Color in
ianomethylene-indoline and 6.0 grams thionyl chloride are
methanol: bluish-red.
reacted in the presence of 100 milliliters benzene in the
Example 8
manner described in Example 5. The dyestutf is obtained
Production of 2~(1-ethyl-3,3-dimethyl-5-methoxy-in
in the form of dark red crystals. Yield: 24.3 grams, color
of solution in water: bluish-red.
dole)'2’-(l’~ethyl-3',3'-dimethyl - 5' - methoxy-indole)-a
cyano-trirnethineeyanine chloride.
30
Example 12
Production of 2-(1,3,3-trimethyl-indole)-2'-(l',3’,3’-tri
methyl-indole ) -aq-dicyano-pentamethine-cyanine perchlo
rate.
By the reaction of 6.8 grams l-ethyl~3,3-dimethyl-S-meth
oxy-Z-cyanomethylene-indoline-w-aldehyde with 5.5 grams
l-cthyl-3,3-dimethyl - 5 - rnethoxy-Z-rnethylene-indoline
according to the method described in Example 2, 9.5
40
2.3 grams 1,3,3-trimethyl-2-(uq-dicyano-propenylidene)~
indoline-w-aldehyde, 1.5 grams 1,3,3-trirnethyl-2-methyl
ene-indoline, 1.3 grams phosphorus oxychloride and 35
grams of dyestuff are obtained. This is in the form of
metallic shining crystals. Color in methanol: bluish-red.
Example 9
Production of 2-(1 ,3,3-trimethyl-5-phenyl~indole)-2'-( l ’,
milliliters chloroform are heated together under re?ux for
two hours. The reaction mixture is then evaporated to
dryness. The residue is taken up in 150 milliliters meth
anol, ?ltered and mixed with 10 milliliters 10 percent am
3’, '~tritnethyl - 5' - methoxy-indole)-a-cyano-trimethine
cyanine chloride.
CH3
\ /
CH1
CH1
CH3
N
éHl
2111:
bluish
red
By the reaction of 7.6 grams 1,3,3-trimethyl-5-phenyl-2
cyano-methylene-indolinew-aldehyde with 5.1 grams 1,3,3
monium perchlorate. The dyestutf perchlorate precipi
trimethyl-S-methoxy-Z-methylene - indollne according to
with isopropanol.
methanol: violet.
tates out as a blue powder.
the method described in Example 2, 9.7 grams of dyestuff
are obtained. This is a brown crystalline powder. Color 60
in methanol: bluish-red.
(3'-methyl~benzthiazole)-a-cyano - trimethine - cyanine
methylsulphate.
3’,3'-trimethyl~indole)-a-'y-dicyano - trimethine - cyanine 65
chloride.
OH;
0
Example 13
Production of 2-(1,3,B-trimethyl-S-methoxy-indole)-2'
Example 10
Production of 2-( l,3,3~trimethyl-5-chloro-indole)-2'-(1',
CH;
7
It is separated olf and washed
Yield: 2.0 grams, color of solution in
OH:
CH:
OH:
\
1‘
0
C1
70
N/ t... a... \N/
(‘1H5
|
CH3
red-orange
A mixture of 2.6 grams 1,3,3-trimethyl-S-methoxy-Z-cy
nno-methylene-indolmew-aldehyde, 2.8 grams 2,3-dimeth
A solution of 11.3 grams 1,3,3-trimethyl-2-cyanomethyl 75 yl-benzthiazolium-mcthyl-sulphate, 1.0 gram triethylamine
3,090,782
12
11
time, the dyestu? precipitates. The mixture is diluted with
100 milliliters benzene, the precipitate is separated and
and 20 milliliters glacial acetic acid is heated under re?ux
for 15 minutes. The reaction mixture is then diluted with
50 milliliters hot water. After cooling, the dyestuff,
which is obtained in the form of metallic shining crystals,
is separated o?'. Yield: 4.1 grams, color of solution in
methanol: bluish-red.
Washed with benzene. One obtains a light orange pow
der. Yield: 24.3 grams, color of solution in water is
scarlet red.
Example 17
Example 14
Production of 2—(1,3,3-trimethyl-indole)-3'-(1’,-methyl
2'-phenyl-indole)-a—cyano-dimethine-cyanine perchlorate.
Production of 2-(1,3,3-trimethyl - 5 - methoxy-indole)
2’-( l’,3’,3'-tnimethyl - 5'-methoxy-indole) - a?-dicyano
10
trimethine-cyanine-chloride.
A mixture of 12.8 grams 1,3,3-trimethyl-5-methoxy
20
Z-cYanomethyIene-indoline-w-aldehyde, 11.4 grams 1,3,3
trimethyl-S - methoxy~2 - cyanomethylene-indoline, 7.7
orange-red
grams phosphorus oxychloride and 20 milliliters chloro
A solution of 10.0 grams l,3,3-trimethyl-2-cyanomethyl
form are refluxed for 10 minutes. Then the chloroform
ene-indoline-w-aldehyde, 8.3 grams l-methyl-Z-phenyl-in
dole and 4 milliliters phosphorus oxychloride in 40 milli
and the unreacted phosphorus oxychloride are distilled
oil, ?rst under atmospheric pressure and ?nally under
liters chloroform is heated under re?ux for 60 minutes.
reduced pressure. The remaining raw dyestuff is re
The reaction mixture is then evaporated to dryness. The
crystallized in 800 milliliters water. On obtains a brown
residual crude dyestu?' is dissolved in 500 milliliters meth
powder. Yield: 16.0 grams, solution color in water:
anol and precipitated out as the perchlorate with 70 milli
bluish red.
liters 10 percent ammonium prechlorate solution. The
Example 18
dyestutf perchlorate is separated oil and washed with a 30
little methanol. The dyestulf is a red-brown powder.
Production of 2-(1,3,3,5-tetramethyl-indole)-2'-(l',3’,
Yield: 17.0 grams, color of solution in methanol: orange
3',5'-tetramethyl-indole) - aq-dicyano - trimethine-cy
red.
anine-chloride.
1,. t
Example 15
Production of 2-(l,3,3-trimethyl-indole)-3'-(2'-methyl
indole)-wcyano-dimethine-cyanine chloride.
40
scarlet
red
12.0 grams
l,3,3,5-tetramethyl-2 - cyanornethylene-in
doline-w-aldehyde, 10.6 grams 1,3,3,5-tetramethyl-2-cy
ano-methylene-indoline and 7.7 grams phosphorus oxy
6.4 grams phosphorus oxychloride is added dropwise in
chloride are reacted according to Example 17. The raw
the course of 5 minutes to a solution of 9.5 grams 1,3,3
dyestu? is recrystallized in 350 milliliters water.
trimethyl-Z-cyanomethylene-indoline-w~aldehyde and 5.5
obtains a red powder. Yield: 13.6 grams, solution color
in Water is scarlet red.
grams a-methyl-indole in 50 milliliters chloroform.
The
reaction mixture is then heated under re?ux for an addi
The following examples demonstrate the dyeing process
tional period of 5 minutes and subsequently evaporated
to dryness.
with some new dyestuffs.
The residue is preferably heated up with a
Example 19
1 part by weight of the dyestuff of the formula:
little water. After cooling, the undissolved dyestuff is
separated off. It is in the form of ‘a brown powder.
Yield: 13.1 grams, color of solution in methanol: orange
red.
0E.
Example 16
CH3‘)
Production of 2-(1,3,3,5 - tetramethyl-indole)-2-(1',
3',3',-trimethyl-5-chloroindole)-|x,'y - dicyano-trimethine
cyanine-chloride.
CH3
CH8
One
60
on,
/c\
OH:
\0/
\ N/ G=C—CH=(|3—O/
0N CN \N
([JH I
+
\
OH.
é H1
+
1
I ol
bluish
red
is dissolved in 300 parts by weight of water. 3 parts by
weight 30% acetic acid and one part by weight sodium
acetate are added to the solution.
100 parts by weight
of a woven textile made from polyacrylonitrile or an
acrylonitrile-containing mixed polymer are immersed in
this dye solution at about 50° C., the temperature in
12.0 grams 1,3,3,5-tetramethyl—Z-cyanomethylene- in 70 creased in the course of 20 to 30 minutes to boiling point
and dyeing carried out at the boiling temperature for
doline-w-aldehyde and 11.6 grams 1,3,3-trimethyl-5- chlo
ro-2-cyanomethylene-indoline are dissolved in 50 milli
liters hot benzene, and after cooling the solution 6.0
grams thionylchloride are added.
The mixture auto
matically warms up to the boiling point.
one to one and half hours. After washing and drying,
a strong bluish-red dyed material is obtained, which
possess excellent fastness and an exceptionally good sta
After a short 75 bility to light.
8,090,782
14
13
Example 20
1 part by weight of the dyestuff having the formula
whose preparation is described in Example 17 herein
and
(b) a 1,3,3-trialkyl-Z-cyanomethyleneindoline of
the formula
before:
Gi
CH;
CH:
CH:
\ /
CH:
G5
*
/ a
10
l.
bluish
red
in which formulae
is dissolved in 3000 parts by weight of water and used
in the manner described in Example 19 hereinbefore for 15
dyeing 100 parts by weight of polyacrylonitrlle thread,
R1 and R5 are each an alkyl radical having up to 18
if desired with the addition of a levelling and/or disper
sion agent. A material is obtained which is dyed with a
G1 and G, are each a radical of the group consisting
carbon atoms,
of alkyl and phenyl, and
clear bluish red and possesses very good fastness and an
especially good light stability.
20
Example 21
1 part by weight of the dyestuff having the formula
E3 is a radical of the group consisting of hydrogen,
lower alkyl, lower alkoxy, and halogen.
3. A cyanine dyestuff of the formula
whose preparation is described in Example 18 herein
25
30
4. A cyanine dyestuff of the formula
is dissolved in 3000 parts by weight of water. 100 parts 35
by weight of material made from polyacrylonitrile or a
mixed polymer containing acrylonitrile are placed on this
dye solution at about 50° C., the temperature is increased
within a period of 20 to 30 minutes ‘to boiling point and
maintained at this temperature for l to 1% hours. After 40
washing and drying, a material is obtained dyed with a
very clear scarlet shade which possesses very good fast
ness and an excellent stability to light.
We claim:
1. A cyanine dyestu? of the formula
45
G:
G:
G1
G:
011,
\ /
CH;
CH3
CH:
5. A cyanine dyestutf of the formula
CH;
CH;
CH]
t
6. A cyanine dyestuff of the formula
in which
55
R1, R3, 6;, and G2 are each lower alkyl,
E3 is a radical of the group consisting of hydrogen, lower
OHl
011g
0 HI
alkyl, lower alkoxy, and halogen, and
Y" is an anion.
2. A process for the production of a cyanine dyestuff
which comprises mixing in an inert solvent in the pres
60
ence of an ‘acidic condensing agent at a temperature be
tween room temperature and about 100° C., approximate
ly equimolecular amounts of
65
(a) a cyanomethyleneindoline carboxaldehyde of
the formula
1
70
75
7. A cyanine dyestu? of the formula
OH:
[CHO
/
OH:
Cg: / CHI
O
/
N
$11;
a
an \
(SH;
(References on following page)
3,090,782
15
16
References Cited in the ?le of this patent
FOREIGN PATENTS
UNITED STATES PATENTS
2,158,287
Konig _______________ __ May 16, 1939
2,165,337
Brooker ______________ __ July 11, 1939
2,345,094
BI'OOk?I' et a1 _________ .... Mar. 28, 1944
2 ’ 542401
’
Doyle etal ____________ __ Feb. 20 ’ 1951
2’848’296
‘Heller """"""""" "' Aug‘ 19’ 1958
620,802
Great Britain _________ __ Mar. 30, 1949
éusma —————————————— -— Df-l 1;’ £1‘;
5
2,893,816
Tsang _________________ .._ July 7, 1959
2,918,369
2,953,561
Dorrenbos ____________ __ Dec. 22, 19159 10
Dorrenbos ___________ __ Sept. 20, 1960
1
"many -------------- --
“ Y
1
OTHER REFERENCES
.
. Dyes, vol.
Venkatararnan: The Chem1stry
of Synthetic
II, page 1175, Academic Press Inc., N.Y., 1952.
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