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Патент USA US2131865

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Patented Oct. 4, 1938
2,131,865
UNITED STATES PATENT OFFICE‘
‘
PROCESS OF
C’YANI ‘DYE
Walter Zch, Dessau in Anhalt, Germany,
or to'Agfa Ansco Corporation,
N. Y., a corporation of New York
‘
assign
Binghamton,
N0 Drawing. Application ‘May 28, 1934, Serial
No. 728,043. In Germany June 3, 1933
6 Claims. (01. 260-240)
My present invention relates-to dyes of the
polymethine series.
,
that nevertheless the formation of intermediate
One of its objects is to provide a process of
producing dyes from the polymethine series. An
‘5 other object are the dyes of, the polymethine
series which have proved to be valuable sensitiz
ers. Further objects will be seen from the de
tailed speci?cation following hereafter.
The symmetrical pentamethinecyanines have
10 already been proposed as sensitizers for the range
of wave lengths between 650% and 1000”.
vAccording to'this invention I have found, that
the unsymmetrical pentamethinecyanines are well
suited for sensitizing a silver halide emulsion for
15 this range of, wave lengths. The progress in
volved by the new sensitizers resides not only in
‘the fact that an extraordinary great number of
suitable dyes is now available, but also in the
fact, that by suitably combining different quater
product occurs are the amines.
In case of using
pyridine or condensing agents of similar action
which simultaneously are used as solvents, there
may be used an excess for obvious reasons. It is
advisable to use an amount of the propene com
'
pound substantially exceeding the quantity equiv
alent ‘to that of the base; preferably there is used
a more than 10 per cent excess in order to avoid
as far as possible the undesired formation of 10
symmetrical dye.
'
If as heterocyclic base there is used, for ex
ample, benzthiazole, the reaction of the 2-methyl
benzthiazole alkyl iodide with oz-IlhBIlYlEtll'lidO-y
phenylimidopropene hydrochloride in the pres 15
ence of piperidine to form a tetramethine dye
probably proceeds according to the following
schemez‘
‘
nary ammonium salts of heterocyclic nitrogenous
bases containing a methyl group capable of re
action nearly. any desired maximum of ‘sensitiza
tion may be obtained in the infra-red portion of
the spectrum. Thus it is possible to adjust the
20
25 sensitivity of the emulsion according to require
ment.
,
'
For the preparation of the unsymmetrical
pentamethinecyanines there is ?rst made‘ an in
termediate product by condensing in the presence
30 of an alkaline condensing agent equivalent por
tions of a quaternary ammonium salt of a hetero
cyclic base containing a methyl group capable of
> reaction and of a propene, compound of the gen?
eral formula:
,
35
30
For the production of the pentamethinecya
nine dye, the tetramethine dye formed as inter
mediate product is caused to react in the presence
of an alkaline condensing agent with a quaternary
ammonium salt of another heterocyclic base con
taining a reactive methyl group. The reaction ‘
probably proceeds according to the following _
where R1 stands for alkyl or hydrogen, R2 for
40 aryl and X for an acid radical.
-
As alkaline condensing agent I have found suit
scheme:
s
40
able, for instance, primary, secondary and ter
tiary amines, such as methylamine, diethylamine,
trimethylamine, triethylamine, piperidine, pyri
45 dine, or sodium ethylate, or ethanolamines. The
amount of condensing agent used is preferably a
quantity ‘at most equivalent to that of the base
which ‘is used, because an increasing amount ,of
condensing agent promotes the formation of sym
metrical dye from which the intermediate prod
uct must be separated, usually by physical means
(crystallization, decocting). The most‘ suitable
amount to be used of each condensing agent can
easily be determined by experiment. Condensing
55 ' agents which may casually be applied
in excess so '
For the condensation with the propene com
pound and with the tetramethine dye there are
suitable all ‘het'erocyclic bases which contain a
reactive‘methyl group, for example, mono-.- and
poly-nuclear Z-methylthiazoles, 2-methyl-selen
2,131,865
2
pentamethenyl chain. _ If Y is CH=CH, Z is
azoles, and 2- or 4-methyl-quinolines. As alka
line condensing agents there may be mentioned,
sulfur,
R1—-C—
for example, pyridine, piperidine, ethanolamine,
alkyl-amines and sodium ethylate.
By use of suitable of heterocyclic bases, there‘
are obtained in accordance with the invention
is phenylene, R3 and R4 are hydrogen, there re
sults a dye in which a quinoline nucleus is linked
together with a thiazole nucleus by a penta
pentamethinecyanine dyes of the general formula:
‘ methenyl chain and is called a quinoline-thiazole
pentamethinecyanine. The quinoline nucleus
10
maybe linked in 2 or 4 position. The benzene
rings ‘or polynuclear rings fused on the hetero
_ cyclic rings ‘containing a nitrogen atom may be
R6
X
7
a
.
' substituted for instance by alkyl, alkoxy, aryl,
R6
In this formula
15
halogen, substituted or unsubstituted amino
The radicals R5 and R6 linked to the
nitrogen atoms of the heterocyclic rings linked
> groups.
together by the pentamethenyl chain represent
20
nsubstituted or substituted phenylene, naph
thylene or other polynuclear arylenegroups;
suitable substituents are alkyl, aryl, alkoxy,
25
carbethoxy, thioalkyl, seleno-alkyl, substituted
and unsubstituted amino-groups.
.
A necessary condition is that either Y and Z or
R1, R.2 and R3, R4 shall differ from one another.
R5
and R6=alkyl,
'30
X=an inorganic or organic acid radical, for
example Cl, Br, I, C104, CH3--CsH4-—SO3,
CH3——SO4, C2H5——SO4.
35
>
_
The quinoline nucleuswhich results in case of
Y being --CH=CH- may be linked to the poly
methenyl chain in 2 or 4 position. Individual
hydrogen atoms of the pentamethine chain can
be replaced by alkyl groups, for example by
methyl or ethyl.
,
In the general formula Y and Z may represent
40
sulfur, selenium or the vinyl group CH==CI-I.v In
the case of dyes in which, for instance, a thiazole
nucleus and a selenazolev nucleus arellinked to
45
gether by a pentamethenyl chain R1, R2, R3 and
R4 may represent hydrogen, or they may repre
sent alkyluor aryl or carbethoxy.
m~o~
-
It
orene or acetnaphthene.
1i
Ri—'C-—
" -
-
——C-—Ra
containing 1 milligram of [3-ethyl-5-methoxy
5
0
tion.
.
Example 1.-—2 grams of 2-methylbenzthiazole
ethiodide, 2 grams of a-phenylamido-v-phen OX 5
ylimidopropene hydrochloride (prepared accord
ing to Claisen, Berichte der deutschen ohemischen
Gesellschaft, vol. 36, page 3667) and 10 cc. of
alcohol are heated to boiling,,0.5 cc. of piperidine
H and
Rz-“C-
a bath in which the dye is dissolved. Such a
treatment may be as follows: The photographic
material to be sensitized is bathed in a solution
The following examples illustrate the inven
In the case of Y being
'
by bathing the finished photographic material in
1000 cc. of an aqueous solution of methanol of 50
per cent strength for about 5 minutes. The ma
terial is then dried, whereupon it is ready for use.
——-C~R4
sulfur, Z being selenium,
parative experiments. The dyes may be added
to the emulsion in form of solutions. Suitable
solvents are the alcohols, for instance, methyl 35
or ethyl alcohol which may be used anhydrous
or diluted with water. The dyes are applied to
the emulsion during any stage of its production,
however, they are preferably added to the fin
ished emulsion before casting.
40
The dyes maylikewise be added to the emulsion
line-(2)lrpentamethinecyanine iodide in 500 to
may represent phenylene, or naphthylene or a
polynuclear arylene group, for instance, the cor
responding radical of anthracene, chrysene, ?u
55
amount will in each case be found by a few com
benzselenazole-(Z) '] - [3-ethyl-6-methyl - quino
—o—m
Rz-G-
50
-
alkyl. X represents an anion, for instance those 20
disclosed above.
The dyes are obtainable according to the de
sired solubility in form of the bromide, iodide,
perchlorate etc. and are used in a quantity such
as is usual for the known sensitizing dyes. This
quantity may amount to about 0.5 to 2 milli
grams per 1 kg. of emulsion ready for being cast
which contains about 9 per cent of gelatin, 4.5
per cent of silver halide and the rest water.
However, I do not wish to limit my invention to
the quantities just indicated, the most suitable
are added and the whole is boiled for about a fur
60
ther half hour. On cooling, there separates the
-—C-—R4
being phenylene, the dye is a benzthiazole-benz
tetramethine dye (intermediate product) of the
following probable constitution:
selenazole-pentamethinecyanine. If Y is seleni
um, Z is sulfur,
65
.
R1-'C-—
is phenylene, and R3 and R4 are hydrogen the
dye is a benzselenazole-thiazole—pentamethine
70 cyanine. This not only illustrates the dyes which The dye is recrystallized from alcohol.
are contemplated by the invention but also the ‘
In alcoholic solution, the dye has an absorption
nomenclature. In the case of Y being CHZCH,
maximum
at 515/.t/L.
Z being sulfur and R1, R2, R3, R4 being hydrogen,
1 gram of the intermediate product so obtained,
there result dyes in which a pyridine nucleus is 1 gram of 2:5 :5—trimethylbenzselenazole ethiodide
75 linkedtogether with a thiazole nucleus by a‘
65
2,131,865
and 5 cc. of alcohol are heatedmto boiling and
3
reaction mass the'intermediate dye of the prob
there is then added gradually about 1 cc. of di
able constitution:
ethylamine, boiling being continued until the
.
reaction mixture has become deep blue. On cool
ing, IS-ethyhbenzthiazole- (2) l-[3-ethyl-5.6-di
methyl - benzselenazo'le- (2)] - pentamethinecya~
nine iodide of the probable formula:
I
' The alcoholic'solution of the dye has an ab
sorption maximum at 540M,“
separates in the form of coarse green crystals.
The alcoholic solution of the dye has an absorp
tion maximum at a wave length ofabout 670W.
25
10 cc. of hot alcohol and the solution is heated
'
to boiling, whilst 0.5 cc. diethylamine is gradu
ally added, until the reaction mixture becomes 20
deep blue. By the addition of about 5 cc. of a
solution of sodium perchlorate of 10 per cent
oxy-benzthiazole ethiodide and 2 grams of O6"
strength,
phenylamido-'y-phenylimido-propene hydrochlo
(2)] - [3-ethylbenzthiazole-(2)l -'pentamethine -
ride are dissolved in 10 cc. of boiling alcohol, then
0.5 cc. of triethanolamine is added and the whole
is maintained boiling for about 30 minutes. From
is
1 gram of'the dye obtained and 0.6 gram of
Z-methylbenzthiazole ethiodide are‘ dissolved in
‘ Incorporated in a silver bromide emulsion con
600W to 800% with a maximum of about 715ml.
Example 2.-—2 grams of 2~methyl-5:6-dimeth
s
in the form of blackish-brown crystals.
rzHs
20 taining about 4 per cent of silver iodide the dye
imparts to it a range of sensitivity from about
g
[3-ethyl-{naphto-2’.1’:4.5-thiazole}
cyanine perchlorate of the probable formula:
25
the deep red solution, the intermediate dye of the
30
probable formula
-
30
1130 O—
35
is precipitated. The dye crystallizes from alco-1 35
precipitates in the form of blue-red crystals.
From alcohol the dye crystallizes as a red-brown
crystalline powder. Its alcoholic solution has an
hol as a blue-black crystalline powder.
The alcoholic solution of_ the dye has an ab
sorption maximum at a wave length of about
680/LIL.
'
.
'
Incorporated in a silver bromide emulsion con
40
inde?nite absorption maximum at about 525,114].
taining about 4 per cent of silver iodide the dye
The intermediate product has a medium sensi
imparts to it a range of sensitivity from about
tization intensity. Its maximum of sensitization
45 is 560/.L/L and its range of sensitization is about
510 to 600W.
~»
1 gram of the intermediate product thus ob
tained and 2 grams of 2:4-dimethylthiazole ethio
‘700% to 800% with a maximum of about 713ml.
Example 4.—For the production of [3-ethyl
benzselenazole-(2)l - [3-ethyl-4-methylthiazole -
(2)]pentamethinecyanine iodideof the follow
ing formula:
45
dide are heated in 10 cc. of alcohol to boiling for
50 about 10 minutes with‘ the addition of 1 cc. of
diethylamine. On cooling there separates from
50
the deep blue reaction liquid [3-ethyl-5.6-dimeth
oxy-benzthiazole-(2)l - [3-ethyl-4-methyl-thia
zole- (2) l-pentamethinecyanine methylthio-pen
55 tacarbocyanine, iodide of the probable formula
a mixture of 2 grams of Z-methylbenzselenazole
ethiodide and 2 grams of a-phenylamido-v-phem 55
yl-imidopropene hydrochloride‘is ?rst heated for
half an hour in 10 cc. of alcohol with the addi
tion of 1.5 cc. of triethanolamine. On cooling
the intermediate product of the probable for— 60
60
mula:
65
. The alcoholic solution of the dye has an ab
sorption maximum at a Wave length of'about
665,LL,u..
.
'
-
'
——Se
'
.65
Incorporated in a silver bromide emulsion con
taining about 2 per cent of silver iodide the dye
imparts to it a range of sensitivity from about
GOO/14L to 800%“ with a maximum of about 705m».
Example 3.--A mixture of 2 grams of 2-methyl
[naphto-2'.1’ :4.5-thiazole] ethiodide and 2 grams
of u-phenylamido-'y-phenylimidopropene hydro
chloride in 10 cc. of alcohol is heated to boiling
for about 1/2 hour with 0.5 cc. of diethylamine.
75 On cooling, there, separates from the red-violet
\
02115 I
H
separates from_ the violet-red reaction liquid in
the form of dark green crystalline tablets. The 70
alcoholic solution of the product has an inde?nite
absorption maximum at about 525”. The prod
uct is a sensitizer for orange.
Incoporated in a silver bromide emulsion con
taining about 2 per cent of silver ‘iodide the dye 75
2,131,865
4
imparts to it a range of sensitivity from about
510% to 590% with a maximum at about 535W.
1 gram of the intermediate product and 2
grams of 2:4-dimethylthiazo-le ethiodide are dis
solved in 10 cc. of alcohol and the solution is
heated to boiling Whilst about 3 cc. of an alco
holic solution of sodium ethylate (containing 3
per cent of sodium) are ‘gradually added, until
the mass becomes blue. The unsymmetrical pen
1 gram of this intermediate product and 1
gram of 2-methylbenzthiazole ethiodide are heat
ed in 5 cc. of alcohol together with about 0.5
cc. of diethylamine until the reaction mass be
comes dark green. On cooling the [l-methyl
quinoline—(4)] - [3-ethyl-benzthiazole-(2) l-pen
5
tamethinecyanine iodide separates. The dye has
probably the formula:
10
tamethinecyanine which is precipitated on cool
10
ing crystallizes from alcohol as a blue-black
crystalline-powder.
The alcoholic solution of the dye has an ab
sorption maximum at a wave length of about
CzHb
15
660,114‘.
Incorporated in a silver bromide emulsion con
taining about 2 per cent of silver iodide the dye
imparts to it a range of sensitivity from about
570[L}L to 780% with a maximum at about 680%.
Example 5.--The intermediate product of the
probable formula:
It crystallizes from alcohol in bronze colored
deformed crystals.
Incorporated in a silver bromide emulsion con
taining about 2 per cent of silver iodide the dye 20
imparts to it arange of sensitivity from about
600 to 850W with a maximum at about ‘775%.
Emample 7.-—2 grams of para-toluquinaldine
ethiodide and 2 grams of a-phenylamido-y-phen
ylimidopropene hydrochloride in 10 cc. of alcohol 25
/
11
CzHs I
is obtained by using in Example 4 the 5-meth
30
oxy-2-methyl-benzselenazole ethiodide instead of
2-methyl-benzselenazole ethiodide. It crystal
are heated for about 3 hours at 100° C. while
adding 0.5 cc. of triethanolamine. The reaction
product which separates after cooling is recrys
tallized from alcohol. The intermediate product
30
of the probable formula:
lizes from alcohol in the form of a dark brown
crystalline powder the alcoholic solution of which
has an absorption maximum at 540%.
1 gram of the intermediate product so obtained
is heated together with 0.6 gram of paratoluquin
aldine ethiodide in 10 cc.' of alcohol after the
addition of 0.4 cc. of triethanolamine until the
reaction mixture becomes dark green. [3-ethyl
5 - methoxy-benzselenazole - (2)] - [ l- ethyl - 6 -
40
methyl-quinoline- (2) l-pentamethinecyanine io
dide which separates on cooling and has prob
ably the formula:
45
1130-’
\
—CH=OH——CH=CH—N-—C H
\/\N/
/ \
‘
H
35
o 6
is thus obtained in form of red-brown crystal
40
line little rods.
An alcoholic solution of the product has an
inde?nite absorption maximum at about 535lL/L.
1 gram of the intermediate product is heated
in 10 cc. of alcohol with 0.8 gram of 2-methyl
benzthiazole ethiodide with addition of about 0.5 45
cc. of diethylamine drop by drop, until the reac
tion mixture becomes blue-green. [1-ethyl-6
methyl-quinoline - (2) l - [3 - ethyl-benzthiazole -
(2)1-pentamethinecyanine iodide which sepa
crystallizes from alcohol in small copper-colored
50
deformed tablets.
rates on cooling and has probably the formula:
The alcoholic solution of the dye has an ab
sorption maximum at a wave length of about
690W"
60
grams of u-phenylamido-v-phenylimidopropene
hydrochloride, 10 cc. of alcohol and 0.5 cc. of tri
-ethanolamine are heated to boiling for about 1
hour. On cooling, there separates from the red
violet solution the intermediate product of the
.65
55
_
Incorporated in a silver bromide emulsion con
taining about 2 per cent of silver iodide the dye
imparts to it a range of sensitivity from about
GlO/LIL to 810/141. with a maximum at‘ about 730/.L/L.
Example 6.—2 grams of lepidine methiodide, 2
probable formula:
CgHs
crystallizes from alcohol in brown-green de
formed crystals.
60
The alcoholic solution of the dye has an ab
sorption maximum at about 665W.
Incorporated in a silver bromide emulsion con
taining about 2 per cent of silver iodide the dye
imparts to it a range of sensitivity from about 65
600W. to 800p.” with a maximum at about 705%.
Example 8.—2 grams of Z-methylbenzthiazole
ethiodide and 2 grams of a-phenylamido-y-phen
.C)
C
02115 I
ylimido-p-methylpropene hydrochloride (obtain
able analogously to a-phenylamido-'y-phenylimi
E
This product is a dye which crystallizes from
alcohol in brown-black crystalline fragments. Its
alcoholic solution has an absorption maximum
at about 580mm
dopropene hydrochloride from the correspond
ingly substituted propargyl aldehyde-acetal) are
dissolved in 10 cc. of alcohol, and, after the addi
tion of 0.4 cc. of piperidine, the solution is heat
ed to boiling for about half an hour. On cooling
70
2,131,865
there separates the intermediate product of the.
probable formula:
.
-
.
mixture the intermediate product of‘the prob
able formula:
C2€[B\I
‘
cal benzthiazole-‘pentamethinecyanine. By re
crystallization from alcohol, thereis' obtained a
red-brown, crystalline powder, whose ” alcoholic
solution has an absorption maximum‘ at about
513/m.
'
.
‘i
For forming the [3-ethyl-benzthiazole-(2)1-‘
[3-ethyl-{naphto -.-‘2’.l’:4.5 - thiazole} .-'(2‘)‘]'-'y
able formula:
.
1
l
'
1
is precipitated by the addition of about 10 cc. of
a solution of potassium iodide of 5 per cent 10
strength. The dye crystallizes from alcohol in
small red-violet rods. Its alcoholic solution has
an inde?nite absorption maximum at 530%.
1 gram of the intermediate product and 1 gram
of
2—methyl-5:6 - ethylenedioxy — benzselenazole 15
ethiodide are heated together. in 5 cc. of alcohol,
with the addition of, about 1 ccuof diethylamine,
Inethyl-pentamethinecyahine iodide, of the prob
20
'
.
10 together with a small quantityjof the symmetri
15
.
until the reaction mixture assumes a permanent
.
green color. ‘Crystals of the [3-ethyl-benzselen
azole- (2) ]- [3-ethyl-5.6-ethylenedioxy-benzselen— ' 20
azole- (2) l-t-methylepentamethinecyanine iodide
which is formed and has probably the formula:
25
25
01115
.301 1 gram of the intermediate product prepared as
above
described
and - 1
gram
of
are deposited on the walls of the vessel. 'From 30
2~methyl
[naphto-2'.1’:4.5-thiazole]-ethiodide- are heat
alcohol, the dye crystallizes in green rhomboids.
ed at 130° C. in 10 cc, of pyridine for about half
an hour until the reaction mixture becomes deep
sorption maximum at about ‘685ml.
‘.1 blue.
On cooling .‘the‘ unsymmetrical penta
methinecyanine separates in theform of green
crystals. It crystallizes from alcohol inthe form
ofgreen
rhomboids.
.
l
‘
'
r
The alcoholic solution. of the dye has’an ab-'
sorption maximum at about 665%.
40
. The alcoholic solution of the dye has an ab
Incorporated in a silver bromide emulsion con
‘
taining about 4 per cent of silver iodide the dye 35
imparts to it a range of sensitivity from about
580% to 830% with a maximum at about 715W.
Example 11.~—For preparing the dye [3-ethyl
6-ethoxy - benzthiazole - (2) ]-[3 - ethyl-{anthra
Incorporated in a silver. bromide emulsion‘ con-2 ceno? L 2’.1':4.5 - thiazole}- (2) l -pentamethinecy - 40
taining about 4 per cent of silver iodide the dye anine iodide corresponding with the formula:
imparts to it va range ‘of ‘sensitivity ‘from about
590W to 800a,“ with a maximum at about 710%.
Example 9.-For preparing _[3~ethyl-benzthi
45
azole-(2)]-[1 -methyl - quinoline -_(4) ]-5-methyl—
pentamethinecyanine iodide of L the probable
formula
45
’
50'
Edam/7L8
50
55.
1 gram of the intermediate product described in
Example 8 and 1 gram of lepidine methiodide
are heated in 10 cc. of alcohol with the addition
of about 1 cc. of diethylamine, until the reaction
6.0 >mixture assumes a permanent green color. The
unsymmetrical 'pentamethinecyanine which sep
arates on cooling is ?ltered by suction, washed
with acetone and recrystallized from alcohol,
whereby it is obtained in the form of a black
65 ‘brown crystalline powder.
Incorporated in a sliver bromide emulsion con—
- taining about 2 per cent of silver iodide the dye
imparts to it a range of sensitivity from about
70
600,141. to 850%, with a. ‘maximum at about 770%.
Example 10.—-2, grams of 2-methylbenzselen
azole ethiodide, 2 grams of a-phenylamido-y
‘ phenylimido-[i-methylpropenei hydrochloride, 10
cc. of alcohol and 0.5 cc; of diethylamine are
heated in 10 cc._ of alcohol to boiling for about
‘ 7.5.
halt an hour. i From the bluish-red reaction
4 grams of Z-methyl-G-ethoxybenzthiazole ethi
odide and 4 grams of u-phenylamido-ymhenyl 55
imidopropene hydrochloride are heated in alcohol
until dissolution occurs. Then there is added
1 cc, of piperidine while boiling the mixture and
boiling is continued for about 1 hour. After cool 60
ing the dye separates in form of bluish red
crystals.
7
The tetramethine dye is condensed with 2
methyl- [anthraceno-2'.1' :4.5-thiazole] ethiodide
in its alcoholic solution While boiling and in the
presence of diethyl amine to the unsymmetrical 65
pentamethinecyanine.
‘
The alcoholic solution of the dye has an absorp
tion maximum at a Wave length of about 6.95pm.
Incorporated in a silver bromide emulsion con
taining about 4 per cent of silver iodide the dye
impartsto it a range of sensitivity from about
650W to 790p,“ with a maximum at about 740%.
Example 12.—'I'he dye [3-‘ethyl-5-diethylami
no-benzthiazole- (2) ]- [3-ethyl-{naphto-2'.1' :4.5~
70
2,181,865
6.
thiazole}- (2) l-pentamethinecyanine perchlorate ‘
corresponding with the formula:
'
in' form' of red crystals.
In order to complete
the precipitation of the intermediate product
there are added 5 cc. of a 10 per cent solution
of potassium iodide. After ?ltering and washing
with alcohol of 50 per cent strength the com
pound is recrystallized from alcohol.
The alcoholic solution of the intermediate prod
uct has an absorption maximum at a wave length
of about 540,114‘.
The intermediate product thus obtained and
0.8 gram of 2-methyl-4-phenylthiazole ethiodide
10
may be prepared by boiling 4 grams of 2-methyl-
5-diethyl-aminobenzthiazole ethiodide with 3.5
15 grams
of a-phenyl - amido- v -phenylimidopro
pene hydrochloride in 20 cc. of alcohol and adding
1.6 grams of triethanolamine. The bluish red
mixture is cooled and mixed with 10 cc. of a 10
per cent solution of sodium perchlorate, where
20 by the tetramethine dye corresponding probably
with the formula:
are dissolved in 10 cc. of hot alcohol. The mix
ture is boiled while adding slowly 1 to 2 cc. of di
ethylamine until the mixture assumes a deep
green color. After cooling the dye separates in 16
form of green crystals.
The alcoholic solution of the dye has an ab
sorption maximum at about 665/14L.
Incorporated in a silver bromide emulsion con
taining about 2 per cent of silver iodide the dye 20
imparts to it a range of sensitivity from about
570,114L to ‘790W with a maximum at about 700ml.
Example 14.—For preparation of the dye [3
ethyl-5.6-diethoxy - benzthiazole-(2)l - [3-ethyl
4-methyl - thiazole — (2) l - pentamethinecyanine
25
25
iodide corresponding with the formula:
C2115
C104’
is precipitated in form of crystals. From alco
hol the dye crystallizes in form of red-brown
30
30
crystals.
The alcoholic solution of the compound has an
absorption maximum at a wave length of about
(35115 I
CQHIS
540,1L/L.
2 grams of 2-methyl-5.6-diethoxybenzthiazo1e 35
ethiodide together with 2 grams of a-phenyl
[naphto-2'.1’:4.5-thiazole diethylsulfate in 5 cc.
amido-'y-phenylimidopropene hydrochloride are
of alcohol and there are slowly added about 0.3 cc.
of diethylamine, whereby the mixture assumes a
blue-violet color. On the addition of a few cc. of
a 10 per cent solution of sodium perchlorate the
By adding about 20 cc. of a 5 per cent solution of
1 gram of the intermediate product thus ob
35 tained is boiled with 0.6 gram of 2-methyl
dye is precipitated.
The dye crystallizes from
alcohol in form of brown-red small leaves.
The alcoholic solution of the dye has an ab
45
dissolved while warming, in 10 cc. of alcohol and
then boiled for 2 hours with 1 cc. of an alcoholic
solution of trimethylamine of 50 per cent strength. 40
potassium iodide, the intermediate product cor
responding probably with the formula:
sorption maximum at about ‘705141..
45
Incorporated in a silver bromide emulsion con
taining about 4 per cent of silver iodide the dye
imparts to it a range of sensitivity from about
650/.L/L to 810,141. with a maximum at about
50
750ml.
E
C2115
I
,
50
}
Example 13.—The dye [3-ethyl-5-methoxy
benzselenazole — (2) ]- [3~ethyl-‘l-phenyl-thiazole
(2)l-pentamethinecyanine iodide corresponding
with the formula:
55
is separated from the dark-red reaction liquid as
a dark-red tough oil which may be recrystallized
from alcohol after washing with water in the
‘form of bluish red lea?ets.
The alcoholic solution of the compound has an
absorption maximum at a wave length of about
535%.
l
60
65
C 2115
I
C 2115
may be obtained by boiling 2 grams of 2-methyl
5-methoxy-benzselenazole ethiodide and 2 grams
for 10 minutes in a steam bath.
of wphenylamido-'y-phenylimidopropene hydro
ture changes into a bluish-violet.
chloride in 10 cc. of pyridine for about 3 minutes.
the precipitate is ?ltered off, washed with acetone
and recrystallized from alcohol in the form of
green felted needles.
The alcoholic solution of the dye has an ab
sorption maximum at about 675%.
From the reaction mixture which assumes a deep '
red color there is precipitated the intermediate
product corresponding probably with the formula
70
1 gram of the intermediate product thus ob
tained is boiled with 1 gram of 2.4-dimethyl
thiazole ethiodide in 10 cc. of alcohol, and, after 60
the addition of about 2 cc. of diethylamine, heated
While the un
symmetric dye separates the color of the mix
After cooling,
Incorporated in a silver bromide emulsion con
70
taining about 2 per cent of silver iodide the dye
imparts to it a range of sensitivity from about
GOO/LIL to 800% with a maximum at about 7 101m.
Example 15.——In order to obtain [3~ethyl~5
75
methoxy - benzselenazole — (2)1 — [1.6 - dimethyl
75
v
7,
. 2,131,865
quinolinelfll) lépentamethinecyanine ‘iodide _cor—'
taine'd; probably corresponding’with the formula: '
responding with the formula: ‘V
CH3 “
‘ J,/\'
\l\{
.
‘ >—oH='oH--oH=oH—N-o,m
|'~c
I
.
.
H
‘
.
'
and 0.7 gram of 2.4-dimethylthiazole inetliiodidel
are heated to boiling in 10 cc. of alcohol, while
addingabout 1 cc. of diethylamine, until. the
mixture‘assumes a violet-‘blue’ color. The dye 10
stuif which separates on cooling is sucked on‘? and
Washed with acetone, If ntil the acetone runs out
10
1 gram of the tetramethine dyestuff obtained ac
cording to Example 13 and corresponding with
the formula:
.
7
in a pure blue coloration.
15
j _
f I.
,The dyestu? crystallizes from alcohol in the
form‘ of copper brown crystals.
‘ gl5
5
Incorporated in a silver bromide emulsion con
otés \I
20
taining about 2% of silver iodide the dye im‘é
H
parts to it a range of sensitivity from about 650/141.“
to ‘830% with a maximum at about 790,1.p..
Example 18.-—In order to prepare‘ [l-ethyl
is dissolved, while warming, togetherwith 1 gram
of'4.6-dimethylquinoline methiodide in 10 cc. of
alcohol and the mixture is maintained boiling for
5 minutes after adding about 1 cc. of diethylamine.
25 On cooling, the ‘dyestuif separates from the
20
quinoline- (2) ]- [3.4-dimethyl-5-carbethoxy-thia
zole- (2)] - pentamethinecyanine
sponding with the formula:
iodide
V
corre
brownish green reaction liquid and crystallizes
25
from‘alcohol in the form of brownish black rods.
Incorporated in a silver bromide emulsion con- ‘
.
Example 16.—[3~ethyl-6-’ethoxy-benzthiazole
(2) ] -[3-ethyl-3'emethyl-{naphto-‘1H2’ 24.5 - thia
zole}-(2) l-pentamethinecyanine iodide
35
sponding with the formula:
corre
'
'
CHa
_.
__
_
_
_l2
-/ \
30 imparts to it a range of sensitivity ‘from about
650,£L,£L to 880% with a maximum at about 770/.L1L.
2
ozHs
c
l
I
'
'
CH3
‘,1
a mixture of 3 grams of quinaldine ethiodide and ‘
3 grams of a-phenylamido-'y-phenylimidopropenel‘
hydrochloride is heated to weakly boiling for a "
short period in 10 cc. of pyridine. By adding
10 cc. of a 10 per cent solution of potassium iodide,
the intermediate product is precipitated from the 35
deep red solution in the form of ‘red ?occules.
The tetramethine dyestuif having probably the
formula:
40
40-CH
“8 ‘\llIfOH-OH oH__oH on?gr/
taining about 4 per cent of silver iodide the dye
'
.
40
‘is obtained according to Example 11 by condens
ing the intermediate dyestu? with 2.6-dimethyl-'
4.5-benzobenzthiazole ethiodide. The dyestuff
crystallizes from alcohol in the form of dark green
lea?ets.
50
The alcoholic solution of the dye has an ab
sorption maximum at about 685/LM.
Incorporated in a silver bromide emulsion con
taining about 2 per cent of silver iodide the dye
imparts to it a range of sensitivity from about
55
640% to 770p.” with a maximum at about 730%.
' Ezmmple 17.—-In order to obtain ll-methyl
quinoline- (4)] - [3.4 - dimethyl - thiazole - (2) ]
pentamethinecyanine iodide having the formula:
60
‘
‘
Qz?s \I
c
>
‘
H
.
‘
'
.
crystallizes from alcohol in the form of violet red
rods.-
"
‘v
1
~
g
l
. ;1_gram of the intermediate product and. 1 gram’
of 2.4-dimethyl~5-carboethoxythiazole methiodide
are boiled, in 10 cc. of alcohol, carefully mixed 50
with about 1 cc. of diethylamine and kept boiling
untilthe coloration changes to violet-blue. After
cooling, the dyestuff separated, is sucked off,.
washed with ‘acetone and recrystallized from
alcohol.
-
‘
I ‘The alcoholic solution of the dye has an
sorption maximum at about 685,!L/L'. .
.
55
tab
Incorporated in a silver bromide emulsion con
taining about 2% of silver iodide the dye im
parts to it a range of sensitivity from about 570/144 60
to 82011.,“ with a. maximum ‘at about 730,LL,IL.
Example 19._In order to prepare [3-ethyl-6
ethoXy-benzthiazole-'(2)] - [3-ethyl—{-t'etrahydro
I
OH:
65
. 2 grams of lepidine methiodide and 2 grams of
a-phenyl-‘amidoMpphenylimidopropene hydro
naphto - 2'1’ :45 - thiazole}-(2) l-pentamethine
cyanine iodide corresponding with the formula: , ‘
chloride are dissolved in 10 cc. of‘ alcohol and
boiled for 2 hours after adding 1 cc. of diethyl-.
amine. ;‘After cooling, the intermediate product
crystallizes from alcohol.
The alcoholic solution of the dye has an ab
scorption maximum at a wave length of about
580mb;
75
'
I
.
.
.
65
CHz A
H2O
OH,
CH;
(U
.
‘0.7 gram of the tetramethine dyestu? thus ob
15.
2,131,865
1' g'ram'of l-ethyl-6-ethoxybenzthiazole tetra
methinephenylamido iodide (intermediate prod
uct) obtained according to Example 11 and 1
gram
tion'of triethanolamine. ' On ‘cooling; the tetra
methine dye probably’ corresponding with the
formula:
of 2 - methyltetrahydro - p3 - naphthiazole
ethiodide are heated to boiling for 5 minutes in
10 cc. of alcohol While adding about 1 cc. of di
ethylamine. On cooling, the dye separates from
the deep blue reaction liquid and forms light green
crystals.
7
‘
.
10
.
' It is puri?ed by recrystallization from alcohol.
1 (Y
The alcoholic solution of the dye has an ab
sorption maximum at about 670%.
,
Incorporated in a silver bromide emulsion con
taining about 4% of silver iodide the dye im
5 parts to it a range of sensitivity from about 610%
to 78011-11. with a maximum at about ‘710w.
. Example 20.-—For the preparation of [3-ethyl
separates in the form of red violet crystals.
The alcoholic solution of the dye has an ab
sorption maximum at a wave length’of about
538lL/L.
5'-ethoxy — benzselenazole - (2)] — [3.4 - dimethyl
thiazole-(2) l-pentamethinecyanine iodide corre
20. sponding with the formula:
For the condensation of [l-ethyl-quinoline
(2) l-[3-ethy1-6-acetylamino-benzthiazole-(2) l -
pentamethinecyanine iodide 1.2 grams of the
above intermediate product and 1 gram of 2
methyl-6~acetylaminobehzthiazole diethyl sul
fate are boiled with about 1 cc. of an alcoholic
solution of triethanolamine until the dyestu?
crystallizes out.
The alcoholic solution of the dye has an ab
sorption maximum at about 695/L1L.
25
2 grams of 2-methyl-5-ethoxybenzselenazole_
ethiodide and 2 grams of a—phenylamido-'y—
phenylimidopropene hydrochloride are slowly
30. boiled for about 3 minutes in 10 cc. of pyridine.
On cooling, the intermediate product probably
having the formula:
Example .22.—In order to obtain [3->ethyl-5.6
dimethyl-benzthiazole- (2) l- [3-methyl-4-phenyl
thiazole - (2)1-5 - methyl - pentamethinecyanine
iodide having the formula:
'
-——Se
35
mclo,
'
CH=CH—CH=CH-—N—-Cel15
\N/
i
\
‘
40
Incorporated in a silver bromide emulsion con
taining about 4 per cent of silver iodide the dye
imparts to it a range of sensitivity from about
610 to 800% with a maximum at about 730%.
C2115
H
I
separates. In order to complete the separation,
5 cc. of a 10 per cent solution of potassium iodide
are added, the precipitate is ?ltered off, washed
2 grams of 2.5.G-trimethylbenzthiaZole ethic 40
dide and 2 grams of u-phenylamido-v-phenyli
mido-p-methylpropene hydrochloride are heated
with water and recrystallized from alcohol.
to boiling after dissolution in 10 cc. of hot alco
hol with 0.5 cc. of an alcoholic solution of tri
The alcoholic solution of the dye has an ab
sorption maximum at a wave length of about
ethanolamine. After cooling the intermediate,
dyestu? probably having the formula:
45
5351L/L.
1 gram ofthe intermediate product thus ob
tained and 1 gram of 2.4-dimethylthiazole meth
HaC-—
/ \
C2115
The dyestuff crystallizes from alcohol in the
form of ?ne green felted crystals.
The alcoholic solution of the dye has an ab
sorption maximum at- about 655;.Lll.
Incorporated in a silver bromide emulsion con
taining about 2% of silver iodide the dye imparts
to it a range of sensitivity from about 550W. to
7901141. with a maximum at about 690%.
Example 21.-—In order to prepare [l-ethyl
quinoline - (2) l-[3-ethyl — 6-acetylamino - benz
thiazole-(2)l~pentamethinecyanine iodide cor
responding With the formula:
65
OH:
50
iodide are boiled in 5 cc. of alcohol, while adding
about 2 cc. of an alcoholic solution of triethyl-'
amine of 50 per cent strength.
H
I
separates as a brown-violet crystalline mass. The
precipitate is ?ltered o?, washed with cold al
cohol and recrystallized from alcohol for the pur
pose of puri?cation.
55
'
LThe alcoholic solution of the dye has an ab
sorption maximum at a Wave length of about
53mm.
‘f
In order to prepare the unsymmetrical dye,
0.8 gram of the intermediate product thus ob
tained and 1 gram of 2-methyl-4-phenylthiazole
methiodide are boiled for 10 minutes, while add
ing about 2 cc. of an alcoholic solution of di
65
ethylamine. The resulting dyestu? separates in
greenish crystals already during heating.
The alcoholic solution of the dye has an ab
sorption maximum at about 665ml.
C2115
C 2115
a mixture of 3 grams of quinoldine ethiodide and
3 grams of a-phenylamide-»y-phenylimidopropene
hydrochloride are'dissolved in 10 cc. of hot al
cohol and heated for about 3 hours to 100° C.
after the addition of 1 cc. of ‘an alcoholic solu
'Incoroporated in a silver bromide emulsion con
taining about 2 per cent oi silver iodide the dye
imparts to it a' range of sensitivity from about
590/L/L to 7501/41. ‘with a maximum at about 695111;.
Example 23.—In order to prepare [3-ethyl-_5.6
dimethyl- benzthiazole- (2) l - [l - ethyl-G-methyl
70
" 9
quinoline- (2) ] -. S-methyi “- ‘pentametlunecyanine
‘1
lgraniwiof2J4-'-dimethyl-5¥oarbethoxythiazole
perchlorate correspondingjwithl the’ formula: 0
. ethiodide‘ ‘ "and I 1 I gram’; ‘of. ‘
e-phenylamido~6.7
benzobenzthiazotetramethine Rehiodide as ob»
tained‘according to Example 3‘: a‘re‘heated in
15cc. of alcohol: while adding about‘ 37cc. of ‘an
alcoholic solution of trimethylamine of 50 per
cent “strength until the dyestuff separates in the
form
-1 ‘gram ofp-tomqui ' Maine 'ethiodide?ahdil" gram
of bronzeacrystals.
I
‘
v
t
‘
'
<1The:lalcoholieifsolution' of“ the dye has an ab
of _ e-‘ph'e'nylamidb#516immethymenztmb-tgmethc , sorptidn tin'axilmumrat?about 675m“.
at
I
16
_y‘yltetraniethin‘e1 ethiodide as obtained" according ' iiiIncorporated" ihiar silver bromide emulsion con
to Example 2,2. are mixedewith'about? cc. of an
alcoholic‘ solution‘ Of ' diethylalnine‘i‘ While boiling
taiiiing aboutnz per-‘.centtof': silver iodide the‘dye
imparts"
w it a range‘v of ‘sensitivity from v‘about
15 m 15 cc. ‘of aleohol'and-"kept benin' ‘untlli-thé' seen-to 'l??mi'with' ‘ahm'aximum at ‘about 730%.
green coloration? remains.’ T’By‘addin'e 15‘ era: of -->;Ea:ample‘-.265;‘-In order to‘ obtain [3-ethy1-5-:
10 ’ per‘ cent} solution or "sodium perchlorate; ‘the ethoxy-benzselenazole- (2) 1-‘ [3,-ethy1-5-chloro-6
unsymmetrical {pen methi-ne'cyariine' Pisfprecipié
20
methylbenzthiazole - (2),] - pentamethinecyanine
tated‘in blue floccules‘:v - »‘ Ablufsh black‘ ory‘s'talline
powder crystallizesfrom al'éolioli" 1*”
'
5'»
' *1
The alcoholic solution of the; dye‘hasan‘a'bl
sorption
WIncorporate‘d
maximllmiat
in ya; silver-bromide‘
1about{670;i;z."i‘reunion’
' (3on4
ta'ining aboutlill per cent ofsilv‘er iodide ‘the dye
25
imparts town arangeofvsensititity from?about
cootttolsooml with aym'aximum‘at about 720W;
‘ 5 * ethoxyibe'nzselenazolei (zilltiafA-methyl L‘thiY
iodide ‘as’‘ebl'ai'nedv ac 'ording to Example. 20 and 25
corresponding-‘with the‘formula’:
ethiod'ideware boiledilinll'o 00,01" alcohol, then
az‘ole-‘_(2)'l+6;methyl-pentamethinecyanine5iodide
30
1":':gran1 . of" p‘Z65dimethyl-5;pchlorobenzthiazole
'
mixed ‘witli' 2.5 do.’ 'of'a’sjolutio’n of sodium ethyl
ate containing 3 per cent of sodium and heated
36
until the resulting dye separates from the brown
ish green reaction liquid. 'I‘he'dye crystallizes
in the ,form ‘ of ‘blackish-green 1 tablets from
alcoholi'
2 gram = [f Y '52emethyl-liiethokybenzselenoaiole
ethiodide‘ and 2 ‘grams
'
‘
‘
‘1
‘
The alcoholic solution of the dye has an ab
sorptionvmaximum at about 675%.
35
V
wlncorporated in‘ a silver“ bromide emulsion containing about 4 per cent of silver iodide the dye
imparts to“ it‘ a‘; range ‘ of ‘sensitivity from about‘
610m’. to;780;mewith‘la‘gmaximum‘at about 720%.
Example 27.—In order to prepare [3-ethyl-6
meth‘yLr-I benzthiazole~ (‘2).‘1 ~£3- ethyl - {acenaph
~the‘noe5f A’; 4.5;; thia‘zol‘e} -.‘( 2):] épen‘tamethinecya
nine'iodide corresponding with ltheformula: I
_>r:
.
.1
'
about;
V 101cc: ‘of'
G2€I5\I
"a “10f” per " ‘cent *soluti‘on bf
,. t l pm
-
tassium-i *i'odid‘e? are Tladde‘ ; Pto' 1‘ the red‘ reaction
liquid, then tne'mixtureisnuered and; the résiei
the
due washedll-with water;- "Gre'yi‘sh' redléa?ets
crystallize from‘ alcohol}; ‘
‘l 1
The ‘ ‘alcoholic solution‘ “ oflth-el dye 'has'Yan' "ab’f'l
'sorpti‘on “maximum'jl-at a-waveqengui ‘
“event
' so
2aerating-i6rK2ImegmI-ptbmunmime ethiodide
and v2‘ igrarn‘s‘ "of‘ulphenylalmido~7-phenylimido
propene‘hydrochloride are dissolved in about 1O
“ 1 gram ‘ or‘ this ‘tetrame'thine- aye‘ana 1 > ‘gram 7 cc; bf ‘hdt'a‘looholiand'heated to'boiling for about t
55
2 hours after adding 0.6 gram ofipiperidine. The
of 2.4-dimethylthi‘a2ole“inethiodideiarei-boiléd in intermediateproduct ‘which separates on cool
10"ccfiof‘alcohbL'lwhile‘ adding 1151202100. 50f di
ethylamine,‘ until Ia; ‘deep ' blue-Ivioletl'coloration ing and probably corresponds with the formula:
occurs. ‘ Thei‘dyes'tuff‘ Fcrystallizesi ‘from alcohol‘
60
in the form‘ of:'a‘bluish"black='orystalline powder.
:Ea'ample 25.—-In order‘ vto prepare'
[3-ethyl-*
{naphto - 22124.5 - thiazole}-'(2) ]-[3-‘-‘ ethyl - 4 :'
65: methyl - 5 - carbethoxyl- thiaz‘ol‘e- (2) ] -pentameth
inecyanine iodide‘ having" theforrnula:
>
isiecrystallized’flrom alcohol in ‘order to free
65
it‘ from‘ symmetrical pentamethinecyanine formed
simultaneously.
‘
_‘~
_
‘ o
-
yelalcoholic‘ solution of‘ the‘dyestuff has an
absorption maximum at 'a wave length of about
515m‘:
\
‘
=
l
>
'
l.
l
c
_
In order to produce [3-ethyl-6-methyl-benz
thiazole-(2) l-3-ethyl - {acenaphtheno - 5'.4’ :45
75
I
02115
thiazole}-(2)]-lpentamethinecyanine iodide, 0.5
gram of the tetramethine dyestu? and 0.5 gram
75
2,131,865
10
lines, and wmethylquinolines in the presence of
an alkaline condensing agent.
2. The process of producing an unsymmetrical
methinecyanine which comprises reacting on the
quaternary ammonium salt of a nitrogeneous
heterocyclic base selected from the group consist
of 2-methylacenaphthenethiazole ethiodide are
boiled in 10 cc. of alcohol together with 10.5 cc.
of piperidine.
The unsymmetrical dyestu?
which separates out in the form of green crystals
crystallizes from alcohol in the form of hair
?ne green needles.
_
.'
ing of a-methylthiazoles, a-methylselenazoles, oz
The alcoholic solution of the dye has an ab
imparts ‘to it a range of sensitivity from about
methylquinolines, and 'y-methylquinolines with an
amount. of an u-phenylamido-'y-phenylimidopro
pene hydrohalide substantially surpassing the 10
quantity equivalent ‘to that of the base in the
600ml to 790% with amaximum at about 715”.
Example 28.-'-For the preparation of. [Ev-ethyl-v
to that ofvthe base, and condensing the resulting
sorption maximum at about 675(1-[LL
'
Incorporated in a'silver bromidefemulsion con
10 taining about 4 per ‘cent of silver iodide the dye
presence of an amountof alkaline condensing
agent not greater than the quantity equivalent
5.?-dimethyl-benzthiazole- (2) l- [3-ethyl-5-chlo '
intermediate‘ product with another quaternary
ro-benzselenazole- (2) l-pentamethinecyanine io
15
dide corresponding with the formula:
‘l
a2
20
Nf
from the group consisting of a-methylthiazoles,
a-methylselenazoles, a-methylquinolines, and 7
\‘
o11=on-o121:011-011-2 a
-\N
\I
CgHs
.
4
methylquinolines in-the presence of an alkaline
65
condensing agent.
01
0211:
ethiodide and 5 grams of a-phenylamido-q-phen
ing with 1 cc. ofv piperidine for about '2 hours
in 20 cc. of alcohol; The int'ermediate‘product
methylquinolines, and 'y-methylquinolines with an
amount of an a-phenylamidowephenylimidopro
pene hydrohalide substantially surpassing the
which separates on cooling-and probably has the
quantity equivalent to that of the base in the
25 ylimidopropene hydrochloride are‘ heated to boil
formula:
20
3. The process of producing an unsymmetrical
methincyanine which comprises reacting on the
quaternary ammonium salt of a nitrogenous
heterocyclic base selected from the group consist
ing of a-methylthiazoles, a-methylselenazoles, a
a mixture of 4 grams of 5.6-trimethylbenzthiazole
30
15
ammonium salt of a nitrogenous base selected
presence of an amount of an amine not greater
’
than the quantity equivalent to that of the base,
and. condensing the resulting intermediate prod
uct“ with another quaternary ammonium salt of
1130'-
a nitrogenous base selected from the group con
‘ LCH=OH——CH=CH-N—O¢Hi"
N/
can
l
I
-
.
_
sisting of a-methylthiazoles, a-methylselenazoles,
.
.
‘
.
is recrystallized from alcohol and forms 'carmine
red
little
rods.
-
'
.
'
‘
.The alcoholic solution of‘the dye has .an- ab
40 sorption ;maximum at a .wave length of-about
525mb.
'
"
"
~
'.
'
"
vvIn order to obtain -1.1'-diethyl;5.6-dimethylbenzthio - 6’- chlorobenzselenopentacarbo‘cyanine
iodide 1 gram of the tetramethine dye’ and ‘1
45 gram of 2-methyl-5-chlorobenzselenoazole are
heated to boiling for about 10 minutes in 15 cc.
of pyridine. On adding 15 cc. of a 5 per cent
50
4. The process of producing [3-ethyl-benz
selenazole- (2) ]- [3-ethy1-4-methyl-thiazole- (2) l
pentamethinecyanine iodide, which comprises re (0
actingon Z-methyl-gbenzselenazole ethiodide with
a-phenylamido-'y-phenylimidopropene hydrochlo
ride in the presence of an amount/of triethanol
amine not greater than the quantity equivalent to
that of said heterocyclic base, and condensing 45
the resulting intermediate product with 2.4-di
methylthiazole ethiodide in the presence of sodi
solution of potassium iodide the .dyestuff sepa
rates. From alcohol the dyestuff crystallizes in
um ethylate.
the form of ?ne green needles.
thinecyanine iodide, which comprises reacting on
'
V _
The alcoholic solution of the dye has an ab
sorptionmaximum at about 665”.
'
: Incorporated in a silver bromideemulsion; con:
taining about 4 per cent of ‘silver iodide the dye
sensitivity from about‘
55 imparts to it .a range of
GOO/LIL to 770% with a maximum at about ‘705w.
What I claim is:
l. The process of producing an unsymmetrical
methinecyanine which comprises reacting’ on the
60 quaternary ammonium salt of a nitrogenous
heterocyclic base selected from the group consist
ing of a-methylthiazoles, wmethylselenazoles,
oc-II'lCthYlClllll’lOllXlGS and v-methylquinolines with
an u-phenylamido-'y-phenylimidopropene hydro
in the presence of an amount of alkaline
65 halide
condensing agent not greaterthan therquantityl
equivalent to that of the base, and condensing the
resulting intermediate product with-another qua
70
a-methylquinolines and 'y-methylquinolines in the
presence of an amine.v
ternary ammonium salt of .aynitrogenous base
selected from the group consisting of q-methyl
thiazoles, a-methylselenazoles, oc-IIIEthYlQlliIlO
.
..-5. Theprocess of producing [1-methyl-quino~
line- (4) l- [3 - ethyl ~benzthiazole- (2) l - pentame
60
lepidine methiodide with a-phenylamido-v-phen
ylimidopropene hydrochloride in the presence of
an amount of triethanolamine not greater than
the quantity equivalent to that of said hetero 55
cyclic base, and condensing the resulting inter
mediate product with Z-methylbenzthiazole ethi
odide in the presence of diethylamine.
. 6. The process of producing [3-ethyl-5.6-di
methylbenzthiazole- (2) l - [I-ethyI-G-methylquin
oline - (2) l - 6 - methylpentamethinecyanine
60
per
chlorate, which comprises reacting on 2.5.6-tri
methylbenzthiazole ethiodide with a—phenylami
no-q-phenylimido '- ,3 - methylpropene
hydrochlo
ride in the presence of an amount of triethanol
65
amine not’ greater than the quantity equivalent
to that of said heterocyclic base, and condens
ing the resulting intermediate product with p
toluquinaldine ethiodide in the presence of di
ethylamine.
70
WALTER ZEH.
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