close

Вход

Забыли?

вход по аккаунту

?

Патент USA US2107379

код для вставки
2,107,379
Patented Feb. 8, 1938
UNITED STATES PATENT OFFICE
2,107,379
MANUFACTURE OF CARBOCYANINE DYES v
Robert Koslowsky, Dessau-Ziebigk in Anhalt,
Germany, assignor to Agfa Ansco Corporation,
Binghamton, N. Y., a corporation of New York
No Drawing. Application January 14, 1933, Se
rial No.v 651,811., In Germany January 18,
1932
26 Claims.
My present invention relates to the manufac
ture of carbocyanine dyes.
(Cl'. 260-44)
In the above formulae Y may represent sulfur,
selenium, oxygen or the group
One of its objects is a process of manufacturing ~
symmetrical and unsymmetrical carbocyanine
C
5 dyes substituted at the central carbon atom of the
trimethenyl chain which are suitable for sensitiz
ing a silver halide emulsion. Another object is
the unsymmetrical dyes. Further objects will be
seen from the detailed speci?cation following
10 hereafter. Reference is made to the accompany
ing drawing which instances the spectral region
to 'which'a silver-halide gelatin emulsion sensi
tized by. my new dyes is sensitive and the spectro
gram of an unsensitized emulsion.
,
I have found that symmetrical and unsym
metrical dyestu?s of the polymethine" series
which are substituted at the central carbon atom
of the polymethine chain can be obtained by con
densing the salt of a quaternary ammonium base
containing in a-position a methyl group capable
of reaction and corresponding with the general
formula
'
/
R1
wherein R1 and R2 represent an alkyl group, for
instance, methyl or ethyl groups or aryl radicals,
for instance, phenyl and R1 and R: can be the 10
same group or different groups.
1' can be alkyl,
for instance, methyl or ethyl. R-may represent
vinylene, phenylene, naphthylene, or the radical
of a polynuclear ring system, for instance, the
radical of anthracene, phenanthrene, ?uorene, di-V 15
phenylene oxide, etc. X .may be halide, per
chlorate,
alkylsulfate, para-toluenesulionate,
nitrate or any other suitable anion.
Ra stands
for alkyl, for instance, methyl, ethyl, propyl,
butyl, amyl, isoamyl etc. or for an aryl radical, 20
for instance, phenyl or for a substituted aryl rad
ical, for instance, substituted by an alkyl group
or an alkoxyl group.
R4 stands for alkyl, for
instance, methyl, ethyl, propyl,‘ butyl, amyl, iso
amyl, etc. R5 stands for phenyl or a substituted
product of phenyl, for instance phenyl substi
25
tuted by a methyl group or a nitrogen group.
Symmetrical dyes may be produced by con
densing 1 molecular proportion of a quaternary
, ammonium salt and about 1/g—11/g molecular pro
portions of thioimide in presence of a basic con
30
densing agent, for instance, pyridine. The prin
R=vinylene, phenylene, nap'hthylene, etc,
X=Cl, Br, I, SO4CH3, C104 or another acid radical
capable of precipitating the dye with an
' alkyl ester of an arylated thiomide corre
sponding with the general formula
SR4
R3—C
40 (2)
' Rsw=alkyl or aryl
R4=alkyl
45
'
-
Rq=phenyl or substituted phenyl.
cipal advantage of the manufacture of the sym
metrical dyestuffs according to the present proc
ess lies in the replacement of the expensive ortho 35
esters hitherto used by the cheaper thioimides.
The unsymmetrical dyes substituted at the cen
tral carbon atom of the polymethine chain may
be produced by condensing 1 molecular propor
tion of quaternary ammonium salt with about 40
11/2 molecular proportions of thioimide. The con
densation is conducted in the presence of an acid
condensing agent, for instance, acetic anhydride,
propionic anhydride, or glacial acetic acid, the
first named being preferred. The condensation
.2
2,107,379
may however also be conducted by heating the
quaternary ammonium salt with the thioimide
without any addition. The method ?rst described,
i. e. the condensation in the presence of an acid
condensing agent is preferred for the production
of dyes substituted at the central carbon atom
of the polymethine chain by a methyl group,
whereas the condensation by simply heating the
components without any addition is preferred for
10 those substituted at the ‘central carbon atom by
an ethyl group.
This condensation yields an
intermediate product which is then condensed in
the presence of a basic agent, for instance, pyri
. dine, with a quaternary ammonium salt different
from that used for the production of the inter
mediate product. The reaction for obtaining the
intermediate product by condensation in the pres—
ence ,of an acid agent is illustrated by the follow
ing equation in this case, in general Formula (1)
20 Y is S, R is phenylene, r is methyl and X is iodine,
and in the general Formula (2) R: is CH3, R4 is
‘02115 and R5 is CoHsZ
It is obvious that by condensing the interme
diate product with the same quaternary am
monium salt as used for the production of the
intermediate product a symmetrical dye will be
obtained. The symmetrical dyes can therefore
be obtained according to a singleystage process
or by a two stage process.
‘
The dyes obtainable according to this inven
tion, the symmetrical dyes as well as the unsym
metrical dyes are powerful sensitizers for photo
graphic silver halide emulsions.
10
'
The unsymmetrical dyes substituted at the.
central carbon atom of the polymethine chain
which, up to date, could not be produced corre
spond with the following general formula:
(3)
N/
\N/
is.
.I»
20
In this formula Y and Y’ stand for the same
25
25
30
From the intermediate productv a dye may ‘be
obtained, for instance, by condensation with ben
zoselenazole ethiodide according to the following
equation:
radicals as indicated for Y in general Formula
(1), R and R’ stand for the same radicals as in
dicated for R in Formula (1), r and r’ stand for
the same radical as indicated for r in Formula
35
40
45
When making the intermediate product by simply
heating the components without any addition, the
reaction probably takes the following course; in
this case R3 is C2H5I
/
50
(1), X stands for the same radicals as indicated
in Formula (1) and R3 stands for the same radi
cals as indicated for Rs in Formula (2).
The unsymmetrical character of the dyes may
55
60
The formation of the dye from this interme
diate product probably'proceeds as follows:
c H,
have the following causes. Two di?erent bases
may be linked to the ends of the polymethine
chain, for instance, a benzthiazole nucleus to the
one end and a benzselenazole nucleus to the other
70
end. Furthermore the nuclei linked to both‘ ends
of the polymethine chain may be substituted by
diiTerent radicals, or they may contain the same
radical in different positions or they may con
70
pyridine)
"15
'i
r
2,107,879
tain different radicals in different positions. This
is illustrated by thev following formulae:
3
en Chemischen Gesellschaft, vol. 21, page 2627)
.into the thioacet-compound by means of phos~
phoruspentasul?de. By oxidation with potas
sium ferricyanide in alkaline solution the sub
’ stituted benzthiazoles are obtained.
For the production of 2-methylbenzthiazoles
substituted _in the benzene nucleus which do not
appear to have been described as yet, the zinc
salt of a correspondingly substituted ortho-amino
10
seleno-phenol of the formula
15
Y
“”
20
.
v
Y
Iii‘ EL
N/
-—V
R=alkyl, alkoxy, substituted amino groups, hal
i
usv
ogen is boiled with acetic anhydride, or a disub
N
‘
stituted ortho-diamino-diphenyl-diselenideof the
formula
Se
S e\
R—~ -
.
.25
The unsymmetrical character of the dyes may
be due to other variations in the substituents,
for instance, to a di?erence in the radicals r and‘
r". The benzene nucleus may be substituted by
30 other nuclei as seen from the‘ description of
Formulae (1) and (3). The substituents V and
W stand for any suitable radical, for instance,
an alkyl group, for instance, methyl or ethyl,
or an alkoxyl group, such as a methoxy group
or an ethoxy group, or halide, or an amino group,
or a substituted amino group, for instance, a di
alkylamino group, or an acyl amino group.
The nomenclature employed in the description
is familiar to the chemist skilled in the art and
40 is believed to have the advantage of clearness.
In the case of the dyes numbering is commenced
from the nitrogen atom of the 5 ring and in the
case of the basesv numbering is commenced from
y of the 5 ring.
45
10
' The dyes are obtainable according to the de
sired solubility in form of the bromide, iodide,
20
- —R
\/\Nm mN/V
is boiled with acetic acid with addition of ‘zinc 25
dust.
-
'
So, for instance, for producing the 5-ethoxy-2
methylabenzselenazole, the 1-amino-2-nitro-4
ethoxybenzene is converted according to the
method of Bauer (Berichte der Deutschen Chem
ischen Gesellschaft, vol. 46, 1913, pages 92-97).
into 4.4’-diethoxy-2.2'-diaminoao-rtho-diphenyl
diselenide .by way of the intermediate product
2 - nitro-4-ethoxy-pheny'l-seleno-cyanide.
diselenide is boiled with zinc dust whereby the 35
5-ethoxy-2-methyl-benzselenazole is formed.
I
In a completely analogous manner other benz
selenazoles substituted in'the benzene nucleus
may be obtained.
~
>
The production of the 4-, 5-, or 7-amino sub
stituted Z-methyl-benzthiazoles serving as a
starting material for preparing the dyes is as
follows:
.
The preparation of 2-methyl-6-amino-benz
thiazole corresponding to the formula
perchlorate etc. and are used in a quantity as
usual for the known sensitizing dyes. This quan
tity amounts to about 5 to 30 milligrams for the
50 unsymmetrical carbocyanines substituted at the
central carbon atom of the trimethine chain by
the methyl group and for the unsymmetrical
carbocyanines substituted at the central carbon
atom by the ethyl group to about 10 to 40 milli
55 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, the rest being water.
However, I do not wish to limit my invention to
the quantities just indicated as, the most suitable
60 amount will in' each case be found by a few
comparative experiments. The dyes may be in
corporated in the emulsion during its produc
tion or after it has been applied to a support.
The dyes are suited for sensitizing an emulsion
made according to the boiling process as well
as for sensitizing an emulsion made according
to the ammonia process.
The preparation of the bases serving as a
starting material is analogous to known methods.
70 In the production of substituted benzthiazoles
one starts from the correspondingly substituted
amino-benzenes, which are made by means of
acetic anhydride- into their acetyl compound.
' This latter is converted, according to the method
75 ‘of Jacobson and Siillwald (Berichte der Deutsch
is described in U. S. Patent 1,758,385, and refer
ence is made thereto.
_
The base 2-methyl-5-amino-benzthiazole cor
responding to the formula
is obtained by reducing the corresponding nitro (H)
compound 'whose method of preparation is known .
(cf. Friese, Ann. 454, page 177), for instance,
with iron and acetic acid. The amino compound
is easily soluble in alcohol, glacial acetic acid
and benzene. It can be easily recrystallized from .
water or benzene and forms colorless crystals
which melt at about 103° C.
The base 2.6-dimethyl-5-amino-benzthiazole
corresponding to the formula
V
can be obtained in two ways.
2,107,379
4
lows: 2-amino-4-acetylamino-toluol correspond
ing to U. ‘5. Patent 1,243,710 the corresponding
o-amino-mercaptane corresponding to the for
ing to the formula
mula
According to the first way one proceeds as fol
on,
on:
N H:
H
\
N
/
SH
HsC-OC
is obtained.
10
\
.
By heating this compound with
acetic anhydride it is transformed into 2.4-di
methyl-6-acety1-amino-benzthiazole which crys
00cm
is first rhodanated with NH4 SCN and Br in its
methylalcoholic solution in the manner described
in U. S. Patent 1,787,315 and then with an aque
ous ammoniacal solution. The formed product,
probably the 2.5-diamino-?-methyl-benzthiazole
corresponding to the formula
tallizes from its aqueous solution in the form of
colorless crystals melting at about 177° C. By
saponi?cation with hydrochloric acid results the
2.4-dimethyl-?-amino-benzthiazole ' which forms
colorless crystals melting at about 118° C.
The base 2.4.6¢trimethyl-7-amino-benzthiazole
corresponding to the formula
\\
obtained from its aqueous solution in form ‘of
colorless crystals which melt at about 200° C. is
split up by heating the same with an aqueous
solution of caustic potassium of about 50_per cent
strength in the manner described in U. S. Patent -
20
I—C H:
25
.
.
is“ obtainable as follows. Amino-acetylamino
xylidin corresponding to the formula
30
‘em
~
CH:
-
N
30 1,788,297 in a compound corresponding to the
formula
_
NH]
'
The zinc mercaptide of this compound is trans
formed into the 2.6-dimethyl-5-acetylaminobenz
thiazole with a melting point of about 178° C.
is rhodanated according to U. S. Patent‘ 1,787,315 40
whereby
2 - amino-4.6-dimethyl-7-acetylamino
benzthiazole corresponding to the formula
corresponding to the above formula by heating .
the aforesaid mercaptide with acetic anhydride. ‘
H
N
According to the second-way 3-chloro-4-acetyl
amino-?-nitro-toluene having a melting point
of 143° C. is transformed into 2.6-dimethyl-5
'\ coon;
‘
PEG is
nitro-benzthiazole forming compact, colorless
crystals when crystallized from alcohol, which
The base 2.4-dimethyl-6—amino-benzthiazole
,
Sl
;|—Nliz
v
2.6-dimethyl-5-amino-benzthiazole when reduced‘
vcorresponding to the formula
7
‘
melt at about 106° C. This compound yields the
with iron and acetic acid, forming colorless crys
tals which melt at about 143° C. The thiazole
can be easily acetylated.
/
50
cm
and melting at about 285° 'C. is obtained: By
boiling this compound with a strong aqueous
solution of caustic alkali according‘ to U. S. Pat
ent 1,788,297 it is split up to the corresponding
o-amino-mercaptane, which may be separated,
from the reaction mixture in form of the zinc
mercaptide. By heating with acetic anhydride
the 2.4.6-trimethyl-7-acetylarnino-benzthiazole is
(H)
I is obtained as
‘on,
follows. Acetyl-toluylene~diaminc
corresponding to the formula
in“
obtainable. After recrystallization from its al 60
coholic solution this compound forms colorless
crystals melting at about 208° C. By saponi?ca
tion with hydrochloric acid the 2.4.6-trimethyl
7-amino-bénzthiazole is obtainable in form. of
colorless crystals melting at about 128° C.
azole corresponding to the formula
H30
‘
I
' \N_ 6 7
mc-oo/
is by means of SzClz transformed into the thiaz
thionium compound in the manner described in
U. S. Patent 1,637,023. When treating this com
pound with a solution of caustic alkali accord
'
The base 2-methyl-6-dimethylamino-benzthi—
H3O
I5
4
1244,":
has already been described; cf. vBernthsen, Ann.
251, page 29.
>
~
75
5
2,107,879 I
The base 2-methyl-?-diethyl-amino-benzthia
zole corresponding to the formula
v
>
.
(Cnmm?s
3 240B;
is obtainable analogously to the above described
10
may be produced by converting 2-amino-‘7-meth
oxy-naphthylamine
preparation of the dimethyl ‘compound.
The
chloride forming colorless crystals is easily solul
ble in water and decomposes when heated to a
temperature of about 160° C. under strong evolu
tion of gas. If the base is not free from the
15 chloride by means of an aqueous solution of
caustic alkali it separates in form of fa yellow
with acetic anhydiqide into its acetyl compound.
‘This latter is converted, according to the meth
l0
od of ‘Jacobson and Siillwald (Berichte der
deutschen chemischen Gesellschaft. vol. 21,‘ page
2627), into the thiaceto-compound by means
of phosphorus-pentasulphide. By oxidation with 16
potassium ferricyanide in alkaline solution the
2-methyl-8-methoxy-?-naphthothiazole is ob
oil which solidi?es upon cooling.
'
tained.
The base 2-methyl-5-dimethylamino-benzthi-_ The following
azole corresponding to the formula
tion:
examples illustrate the inven
'
Example 1.—A mixture of 10 grams of 2-meth
ylbenzthiazole ethiodide '7 grams of ethylisothio
acetanilide and 25 cc. of acetic anhydride are
boiled for about 4 hours under re?ux. After
20
7
,12 i
. cooling and the addition of much ether a thickly
25
is obtainable as follows. p-bromo-dimethylani
line is nitrated in a mixture of concentrated
nitric and sulfuric acid. The formed p-bromo
nitro-dimethylaniline"(orange crystals) is con
verted into p.p'-tetramethyl-diamino-o.o’-dini_
liquid brown mass separates. ‘The ether is de
canted and the mass is again washed twice with
ether by decantation. ‘The residue» is dissolved
in about 12 cc. of alcoholaat a temperature of
about 50 to 60° G. After cooling an intermedi-v 30
trodiphenyl-disul?de (red crystals when crystal- _ ate product corresponding probably i with the
lized from chlorobenzene) by heating it with the
calculated quantity of NazSz. ‘From this com
pound results p-dimethylamino-o-amino-thio
phenol by reduction with sodium sulfide in an
aqueous alkaline suspension.
The latter ‘com
pound is transformed into 2-methyl-5-dimethyl
amino-benzthiazole by a treatment with, acetic
anhydride. The chloride forms colorless crystals
which are insoluble in ether, but easily'soluble
in
water.
_
~
.
y
-
The base 2.4-dimethyl-S-phenyIamino-benz
thiazole corresponding to the formula
45
\
S
r
5
2
4
Il‘iIfCH:
separates in form of crystals.
Crystallization
40
may be hastened by rubbing the wall of the
vessel with a glass rod and. the addition of ether
may increase the yield.
3 grams of said intermediate product, 3 grams
of 2-methylbenzthiazole ethiodide. 15 cc. of
pyridine and 2 cc. of piperidine are mixed and
boiled for about 2 hours under re?ux. The dye
1.1’ - diethyl -mesoemethyl-benzthiocarbocyanine
iodide corresponding probably with’, the formula 50
is obtainable by heating'-2-amino-3-methyl-5-'
phenylamino-thiophenol-zinc (cf. ‘U. S. Patent
1,588,384) with acetic anhydride. After crystal
s‘
j
lization of the compound from benzene it forms
55 colorlesscrystals which melt at about 138° C.
and are easily soluble in benzene, alcohol and
2_
02H:
glacial acetic acid.
/
\
I
s
H
__
CH3 H
__
'
3' '
55
2'
l
’
ciHl
Other bases than those mentioned above may
60 be produced in an analogous manner.
,
Naphthothiazoles substituted in a naphthalene
nucleus may be produced in a manner analogous
to the following description:
2-methyl-8-methoxy-naphtho-thiazoiev corre
65 sponding to the formula
OCH:
is precipitated on addition of a solution of potas
60
sium iodide; it is recrystallized from alcohol.
The alcoholic solution of the dye has an ab
sorption maximum at a wave length of about
550F4L.
,
Incorporated in a gelatino-silver-bromide 65
emulsion containing about 4 per cent of silver
iodide the dye impartsvto it a range of sensi
tivity from about 490mm to about 680% with a
maximum at about 590”.
Example 2.—3 grams of the intermediate prod 70
uct as described in Example 1, 4 grams of 2
'methyl-él. -benzobenzthiazole dimethylsulfate, 12
cc. of pyrggne are boiled for 1 to 2 hours under
75
re?ux. ‘IQ-‘1e dye l-ethyl-1'-methyl-6'.'7'-benzo 75
6
2,107,379
mesomethyl-benzthiocarbocyanine iodide corre
sponding probably with the following formula:
s
5
II
(Inn II
3'
5
2__ ___._ _2' ,
CgHl
ylisothioacetanilide and 15 cc. of acetic acid an
' hydride are boiled for 5 hours. On allowing the
4/ .
5-
a
Example 5.—-A mixture of 10 grams of 2—
methylbenzselenazole-ethiodide, '7‘ grams of eth
reaction mass to stand forv several hours the in
n’
termediate product corresponding probably with
the formula:
I
10
10
is precipitated on addition of ‘a solution of potas
sium iodide. By fractional crystallization from
alcohol the unsymmetrical carbocyanine can be
separated from the by-products formed.‘
15
The alcoholic solution of the dye has an ab
sorption maximum at a wave length of about
565141‘.
Incorporated in a gelatino-silver-bromide
emulsion containing about 4 per cent of silver
20 iodide the dye imparts to it a range of sensi
tivity from about 495ml. to about 690/144. with a
maximum at about 610”.
Example 3.-—A mixture of 2 grams of the inter
mediate product described in Example 1, 3 grams
/
CzHs
I
precipitates in a crystalline form. The precipi
tation may be hastened by the addition of ether.
A mixture of 3,2 grams of this intermediate
product, 3 grams of 2-methylbenzselenazole
ethiodide, 15 cc. of pyridine and 2 cc. of piperidine
is boiled for about 3 hours. There results the dye
1.1 '-diethyl-mes.omethyl - benzselenocarbocyanine
iodide corresponding probably with the formula
25 of» 5 - diethylamino-2-methylbenzthiazole-ethio~
dide and 10 cc. of pyridine is heated until boil
ing and, on addition of 2 cc. of piperidine boiled
for 21/2 hours. The dye 1.1'-diethyl-6’-diethyl
30
amino-mesomethyl-benzthiocarbocyanine iodide
corresponding probably with the formula
s
a
2
H
|_
cm H
— 4',
a’
5
Q.”
6.!
555ml.
7/ _N(C2Ii5)Z
35
0,41,\i
The alcoholic solution of the dye has an ab
sorption maximum at a wave length of about
Incorporated
(Inn,
in
a
gelatino-silver-bromide
emulsion containing about 4 per cent of silver
is precipitated by addition of a solution of po-‘ iodide the dye imparts to it'a range of sensitivity
tassium iodide. By a fractional crystallization from about. 500% to about 675” with a maxi
from alcohol the unsymmetrical carbocyanine mum at about 605/L/L.
40
Example 6.—-A mixture of 3,2 grams of the in 40
may be separated from the by-products formed.
termediate product described in Example 5, 6
The alcoholic solution of the dye has an ab
sorption maximum at a wave length of about grams of Z-methyl-5-diethylaminobenzthiazole
ethiodide, 25 cc. of pyridine, and 2 cc. of piperidine
58514;‘.
Incorporated in a gelatino-silver-bromide are boiled for 11/2 to 2 hours. From the reaction
45
emulsion containing about 4 per cent of silver mixture the unsymmetrical dye 1.1'-'diethyl-6’
iodide‘ the dye imparts to it a range of sensitivity diethylaminomesomethyl - benzseleno - benzthio
carbocyanine iodide corresponding probably with
from about 500/14!- to about 725ml with a maxi
the formula
mum at about 620/411 which is very ?at.
Example
4.—-3
grams
of
the
intermediate
prod
50
uct described in Example 1, 4 grams of 2~methyl~
50
6.7-benzobenzthiazole-diethylsulfate, 17 cc. of
pyridine are caused to interact as described in
Example 2.
55
The dye 1.1'-diethyl-4'.5’-benzo
mesomethylbenzthiocarbocyanine corresponding
probably with the formula
is precipitated from the reaction mixture on ad
dition of a solution of potassium iodide and freed
from by-products by fractional crystallization. ’
00'
The alcoholic solution of the dye has an ab C.)
sorption maximum at a wave length of about
585,u,u..
65
]N
I
01m
_
v
is isolated by a fractional crystallization from
alcohol.
The alcoholic solution of the dye has an ab
sorption maximum at a wave length of about
70
565,4‘.
Incorporated
,
in
a
.
‘
mum at about 620m; which is very ?at.
<
Example '7.--A mixture of 2 grams of the in7 I
termediate product described in Example 5, 3
grams
of
2 - methyl - 4.5-benzobenzthiazole-di
gelatino-silver-bromide
methylsulfate, 20 cc. of pyridine and 2.5 cc. of
' emulsion containing about 4 per cent of silver
piperidine are boiled for 11/2 to 2 hours. The
further treatment is the same as in Example 5.
iodide the dye imparts to it a range of sensitivity
from about 50014‘ to about 670” with a. maxi
75
’
Incorporated in a gelatino-silver-bromide
emulsion containing about 4 per cent of silver
iodide the dye imparts to it a range of sensitivity
from about 500/L/L to about 715w with a maxi
mum at about 59514,“.
-
'
There is obtained the dye 1.-ethyl-1'-methyl
6’.7' - benzo-mesomethyl-benzselenobenzthiocar
75
7
2510712379‘
bocyanine iodide corresponding probably with.
theiformula
ture a few cc. of a 10 per cent aqueous solution
of potassium iodide and. a, small amount of
water. After cooling the dye 1.1'-diethyl-6'
methoxy - mesoethyl-benzthiobenzselenocarbocy
anine iodide separates in form of crystals. The
dye may also be precipitated by the addition oi’ a
large quantity of water. In this case it may sep
CI
arate in form of an oil which, however, will solid
10
The alcoholic solution of the dye has an ab
sorption maximum at a wave length of about
570141..
Incorporated
in
a
iiy after prolonged standing. The dye which is
washed with ether and recrystallized from alcohol
corresponds probably'with the formula
gelatino-silver-bromide
emulsion containing about 4 per cent of silver
iodide the dye imparts to it a range of sensi
tivity from about 500m’. to about 695IL/J- with a
maximum at about 610”.
Example 8.-—10 grams of 5-methoxy-2-methyl
benzselenazole-ethiodide, '7 cc. of ethylisothio
propionanilide and '7 cc. of pyridine are heated
. for 11/2 to 2 hours in an oil bath having a tem
perature of about 130° C. while stirring fre
quently.
'
The reaction mixture is then cooled to about
50° C. and there are added 10 cc. of methanol and
11 cc. of a 10 per cent aqueous solution of sodium
perchlorate. After cooling the dye 1.1'-diethyl
6.6’ - dimethoxy - mesoethyl - benzselenocarbocy
30
ll)
anine perchlorate precipitates. and is separated
by ?ltration washed with a large amount of ether
and recrystallized from alcohol. The dye is ob
tained inform of green, or frequently copper
colorecl crystals.
"
_
35
The alcoholic solution of the .dye has an absorp
tion maximum at a wave length of about 58°[L/L.
Incorporated in a gelatino-silver-bromide
emulsion containing about 4 per cent of silver
iodide the dye imparts to it a range of sensitivity
in from about 500W. to about 710/141. with a maximum
at about 670/14!"
02115 I
(‘3211s
The alcoholic solution of the dye has a. large
absorption maximum at a wave length of about
565 to 57°].LIL.
Incorporated in a gelatino-silver-bromide
emulsion containing about 4 per cent of silver
iodide the dye imparts to it a range of sensitivity
from about 500ml to about 705;“; with a maxi
mum at about 650%.
Example 1_0.—By operating in the manner de
scribed in Example (9b) and starting from a
mixture of 5 grams of the intermediate product 30
described in Example (9a), 5 grams of 2-methyi
4.5-benzobenzthiazole dimethyl-sulfate and 20 cc.
of pyridine there is produced the dye l-ethyl-1'—
methyl-6'37’ - benzomesoethyl - benzthiocarbocy
anine iodide corresponding with the formula ,
40
‘
The dye corresponds probably with the follow
ing formula:
5 4 —Se
‘
mco-6
se-— 4'5,
at Ill $211.51]!0:311‘?
3'
2
7,6’ 00H,
The alcoholic solution of the dye has an absorp
tion maximum at a wave length of about 570m‘.
Incorporated
in
a
gelatino-silver-bromide
emulsioncontaining about 4 per cent of silver
iodide the dye imparts to it a range of sensitivity _
The same dye is obtainable by substituting in the
foregoing example ethylisothiopropion-nitran
ilide (I) or ethylisothiopropiontoluide (II) for
ethylisothiopropionanilide.
from about 500ml to about 695,141. with a maxi
mum at about 630;!4L which is very flat.
ExampleJL-By operating as described in Ex
‘ ample (912)‘, but using 5 grams of the interme
diate product described in, Example (9a), 5
grams of 2-methylbenzthiazole ethiodide and 20
cc. of pyridine, there is obtained the- dye 1.1’
diethylmesoethyl-benzthiocarbocyanine
Example 9.(a).-—10 grams of 2-methylbenz
60 thiazole-ethiodide and 9 cc. of ethylisothiopro
iodide
corresponding probably with the formula
60
pionanilide are heated for 4 hours to 165° C. to
170° C. while repeatedly stirring.
After cooling the solidi?ed melt is dissolved in
15 cc. of warm alcohol and the cooled solution is
mixed with ether. After a short time the dye
stu?-intermediate separates, is filtered; washed
with ether and recrystallized from alcohol. The
puri?ed product melts at 185° C. to 186° C.
Example 9(b).—5 grams of said intermediate
product, 5 grams of 2-methyl-5-mjethoxybenz
selenazole ethiodide and 20 cc. of pyridine are
heated for about 1% hours on an oil bath having
a temperature of 140° C., so that about half of
the employed pyridine quantity evaporates.
Hereafter there are added to the reaction mix
I
C3115
The alcoholic‘ solution of the dye has an- ab
sorption maximum at a wave length of about
5551141..
Example 12.-By operating in the manner de
scribed in Example (9b) and starting from 4
grams of the intermediate product described in
Example (9a), 4.5 grams of 2—methyl-6.'l-benzo
benzthiazole diethylsulfate and 25 cc. of pyridine
70
8
2,107,379
there is obtained the dye 1.1’-diethyl-4'.5’-benzo
mesoethyl~benzthiocarbocyanine iodide
sponding probably with the formula
corre
‘
l]
Incorporated in a gelatino-silver-bromide
emulsion containing about 4 per cent of silver
iodide the dye imparts to it a range of sensitivity
. from about 505” to about 700ml. with a maximum
at about 655/141.
Example 15.-—When working according to the
preceding example and starting from 5 grams of
the intermediate product described in this ex
ample, 5 grams of 2-methyl-4.5-benzobenz
thiazole dimethylsulfate and 20 cc. of pyridine
there is obtained the dye 1-ethyl-1'-methyl
6’.7' - benzomesoethyl - benzselenobenzthiocarbo
The alcoholic solution of the dye has an ab
sorption maximum at a wave length of about
570/141.
cyanine perchlorate corresponding probably with
the formula
\
Incorporated
in
a
gelatino-silver-bromide
emulsion containing about 4 per cent of silver
iodide the dye imparts to it a range of sensi
tivity from about 500W. to about 680” with a
maximum at about 6201!,“ which is very ?at.
_
'
Example 13.—-By operating in the manner de
scribed in Example (9b) but starting from 5
grams of the intermediate product described in
- Example (9a), 5 grams of 2-methylbenzselenazole
"' ethiodide and ‘20 cc. of pyridine there is ob
tained the dye 1.l’-diethyl-mesoethyl-benzthio
benzselenocarbocyanine iodide‘ corresponding
probably with the formula
C2115 H
The alcoholic solution of the dye has an ab
sorption maximum at wave length of about
575’lL/L.
Incorporated in a gelatino-silver-bromide
emulsion containing about 4 per cent ‘of silver
iodide the dye imparts to it a range of sensitivity
from about 500,114]. to about 725,“,11. with a maxi
'
Se
3'
mum at about 650ml.
/ \
02115
I.
C2115
The alcoholic solution of the dye has an ab
sorption maximum at a Wave length of about
555% to about 560,!LfL.
'
Incorporated in a gelatino-silver-bromide
emulsion containing about 4 per cent of silver
iodide the dye imparts to it a range of sensi
tivity from about 500% to about 685% with a
maximum at about 630W.
Example 14(a).—-10 grams of 2-methylbenz
_,-) selenazole ethiodide and 9 cc. of ethylisothio
"
'
Ewample 16(a).-—10 grams of 2-methylbenz
I
propionanilide are heated to about 165 to 170° C.
thiazole methiodicle and 9 cc. of ethylisothiopro
pionanilide are heated for about 11/; hours to 165
to 170° C. After cooling the solidi?ed melt is
dissolved in about 15 cc. of alcohol, and the
intermediate product is precipitated with ether.
Example 16(b).—-2 grams of the intermediate
product, 2 grams of 2-methyl-6.7-benzobenz
thiazole diethylsulfate are worked up according
to Example (917). There is obtained the dye
l-methyl-1’-ethyl-4’.5’-benzo - meso-ethyl-benz
thiocarbocyanine iodide corresponding probably .
with the formula
for about 1% hours while repeatedly stirring.
There is'produced a homogeneous melt of dark
color which is dissolved in 15 cc. of alcohol.
5., This solution is mixed with about 20 cc. of ether
‘ while stirring. The intermediate product which
crystallizes is filtered and recrystallized from
alcohol.
.
Example 14(>b).—5 grams of this intermediate
55 product, 5 grams of Z-methyl-5-methoxy<benz
' selenazole ethiodide and 20 cc. of pyridine are
heated for about 11/2 hours on an oil bath having
a temperature of 140° C., so that about half of
the employed pyridine evaporates. Hereafter a
0;) 10 per cent aqueous solution of sodium per
chlorate and much water are added to the reac
tion mass.‘ The dye 1.1’-diethyl-6'-methoxy
mesoethyl-benzselenocarbocyanine
perchlorate
corresponding probably with the formula
(35
I
The alcoholic solution of the dye has an ab
sorption maximum_at a wave length of about
565”.
~
'
Incorporated in a gelatino-silver-bromide 60
emulsion containing about 4 per cent of silver
iodide the dye imparts to it a range of sensitivity
from about 510% to about 690,114]. with a maxi
mum at about 650/L/L.
Example 17.—-20 grams of 2-methyl-5-me
thoxybenzselenazole ethiodide, 14 cc. of ethyliso
thiobutyranilide and 14 cc. of pyridine are heated .
for about 11/2 hours on an oil bath having a tem
perature of about 140° C., so that half of the
7.‘;
separates.
The further working up is made as
described in Example (14b).
.
The alcoholic solution of the dye has a large
absorption maximum at a wave length of about
"-5 570 to 575ml.
employed-pyridine is evaporated.
Hereafter 10
cc. of methanol, 25cc. of a 10 per cent aqueous
solution of sodium perchlorate and much water
are added to the mixture. The raw dye 1.1’
diethyl-6.6'-dimethoxy - mesopropyl -benzselen0
75
9
2, 107,879
'carbocyanine perchlorate corresponding probably
with the formula
'
.
mum at about 63514,‘. The emulsion has a dis
tinct absorption gap in the green region 01' the
spectrum;
\
*
'
'
My‘invention is not limited to the ioregoin
examples nor ‘to the speci?c details given there
in. Numerous other,embodiments are possible
and I contemplate as included within my inven
tiomall such modifications and equivalents as
separates in form of an oil which by cooling in within the ‘scope of the appended claims. So,
10 ice congeals to a semi-solid mass. The residue for instance, other vnuclei which may be substi— 10
which remains after decanting the supernatant tuted or unsubstituted than those shown in the
_mixture of water and pyridine is dissolved in ‘' examples may be fused on the heterocyclic rings
about 30 to 40 cc. of warm alcohol. From this linked to ‘both ends of the polymethine chain.
solution the dye separates on cooling in form The substituents of the nuclei may be linked to
15
of green crystals.
7
The alcoholic solution of the dye has an ab
sorption maximum at a wave length of about
585m‘.
Incorporated
'
in
a
-
gelatino-silver-bromide
20 emulsion containing about 4 per cent of silver‘
iodide the dye imparts to it a range of sensi
any position and the nuclei may contain one or 15
more substituents. Other quaternary ammonium
salts containing in a-position to the nitrogen
atom a methyl group capable of reaction than
those covered by general Formula (1) likewise
may be suitable as a starting material.
20
The formula: or the dyes as given herein
tivity from about 500M‘ to about ‘705/141. with a represent the molecular structure of my new
maximum at about 665/L/L.
dyes so far as known. If, however, in future it
Example 18.--When starting from 5 grams of should become evident that the formulae do not
25 the intermediate product described in Example exactly correspond with the dyes this fact will 25
(9a), 5 grams of 2-methylbenzoxazole ethiodide’ ,not affect my invention, since the dyes will be
and 20 cc. of pyridine, and'working according easily identi?ed by the method of producing the
same which has been fully described in the ex
to Example (9b) there is obtained the dye 1.1’
diethyl-meso-ethyl-benzthiobenzoxocarbocyanine
30 iodide corresponding with the formula
amples.
'
What I claim is:
30
1. The process which comprises acting while
heating upon a quaternary ammonium salt cor
responding with the formula
35
35
CH1
The alcoholic solution of the dye /has an ab
sorption maximum at a wave length of about
40
525W.
Incorporated in a gelatino-silver-b'romide
emulsion containing about 4 percent of silver
iodide the dye imparts to it a range of sensitivity
from about 500% to about 625a,“ with a maxi
mum at about 560/141,.
45
1
Example 19.--10 grams of 2-methyl-5-me
thoxybenzselenazole ethiodide are heated with
7 cc. of ethylisothio-p-methoxybenzanilide cor
wherein Y is a member of the group consisting of 40
S, Se, 0,
R is a member of the group consisting of
phenylene and naphthylene,
r=alkyl,
a:=an‘ acid radical,
45
with a thioimide corresponding with the formula
-
SR4
'
responding probably with the formula
BCrHI
50
mcomm-c
.
NCtHs
and 8 cc. of pyridine for about 2 hours to 130° C.
55
The dye 1.1’-diethyl-6.6’-methoxy-mesomethoxy
phenyl-benzseleno-carbocyanine iodide is pre
cipitated from the reaction mixture by addition
of a few cc. of a 10 per cent aqueous solution of
potassium iodide and water.
The raw product
wherein R3 is a member of the group consisting 50
of alkyl radicals and monocyclic aryl
radicals
R4=a1ky1
R5=a phenyl.
-
2'. The process which comprises acting while
55
heating upon a quaternary ammonum salt corre
responding with the formula
‘
60 obtained is recrystallized from alcohol. The dye
corresponds probably with the formula
OH:
CgHg-OCHI
wherein Y is a member of the group consisting of 65
65
s! Se, 0,
‘ an.
The dye has a principal absorption maximum
at a wave length of about GOOIL/L and a less de?
nite maximiun at a wave length of about 560”.
Incorporated in a gelatino-silver-bromide
emulsion containing about 4 per cent of silver
iodide the dye imparts to it a sensitivity to waves
from about 525/l-[L to about 'il5lnrwlth a maxi-
.
l
R is a member of the group consisting of
phenylene and naphthylene,
r=alkyl,
X=an acid radical,
with a thioimide corresponding with the formula
SR4
75
2,107,379
10
wherein R: is a member of the group consisting
with a thioimide corresponding with the formula
of alkyl radicals and monocyclic aryl
radicals
=alkyl,
‘
.
SR4
Ill-C
~
Rs=a phenyl,
-
in the presence of an acid condensing agent.
3. The process which comprises‘ acting upon a
quaternary ammonium salt corresponding with
\
NR3
wherein 'R': is a member of the group consisting
of alkyl radicals and monocyclic aryl
the formula
radicals
‘
R4=alkyl,
10
Rs=a phenyl,
3\N/
lion.
I
lligoheating the two compounds to about 165 to
° C.
'
6. The process which comprises acting while 15
15
wherein Y is a member of the group consisting of
\‘
8, Se, 0,
heating upon a quaternary ammonium salt cor
responding with the formula
R. is a member of the group consisting of
phenylene and naphthylene,
20
1'=s1ky1.
20
»
a:=an acid radical,
with a thioimide corresponding with the formula
>Rr-C\
25
\Nm
'7
,
' of S, Se, 0,
wherein R: is a member 01’ the group consisting
of alkyl radicals and monocyclic arylv
radicals
so
R is a member of the group consisting
of phenylene and naphthylene,
r=alkyl,
'
R4=alkyl,
‘
Rs=a phenyl,
30
_
:r=an acid radical,
,
with‘ a thioimide corresponding with the formula
‘
by‘ heating the two compounds.
.
l
4. The process which comprises acting while
heating upon a quaternary ammonium salt cor
35
25
wherein Y_ is a member of the group consisting
‘as
responding with the formula
wherein R3 is a member of the group consisting
' " of allwl radicals and monocyclic aryl 40
40
I’
radicals,
I
wherein Y is a member of the group consisting of
s! &I o’
R is a member of the group consisting of
45
phenylene and naphthylene,
r=alky1,
'
~
vR4=alkyl,
- R5=a phenyl,
in the presence of a basic condensing agent.
'7. The process which comprises acting while
heating upon a quaternary ammonium salt cor
responding with the formula
=an acid radical,
with a thioimide corresponding with the formula
Y
8 R4
50
“(2011,
R:—C\\NRs
/ \I
wherein Ra is a member of the group consisting
of alkyl radicals and monocyclic aryl
radicals
‘‘
‘
wherein Y is a member of the group consisting
-
R.4=alkyl.
_ of S, Se, 0,
'
of phenylene and naphthylene,
' in the presence of acetic anhydride.
69
>
R is a member of the group consisting‘
Rs=a, phenyl,
5. The process which comprises acting upon a
quaternary ammonium salt corresponding with
the formula
‘
60
/r=alkyl,
x=an acid radical,
with a thioimide corresponding with the formula
65
NRI
wherein Y is a member of the group consisting of
8, Se, 0,
I
,
Risa member of the group consisting of
pheny‘lene and naphthylene,
r=alkyl,
75
z=an acid radical,
wherein R3 is a member of the group consisting 70
of alkyl radicals and monocyclic aryl
radicals,
R4=alkyl,
R5=a phenyl,
in the presence of pyridine.
‘
11
9,107,879
8. The process which comprises acting while
heating upon a quaternary ammonium salt cor
responding with the formula
11. The‘ process which comprises acting upon
a quaternary ammonium salt corresponding with
the formula
/Y
‘R\N/
LOH:i
/ \
10 wherein Y is a member of the group consisting
of S, Se, 0,
_
S, Se, 0,
R is
R is a member of the group consisting
r=alkyl,
r=alkyl, I
.
:r='an acid radical,
with a thioimide corresponding with the formula
‘
x=an acid radical,
with a thioimide corresponding with the formula
SR;
SR4
Fri-:0
20
I
HsCz-C
\
NR5
NR5
wherein R3 is a member of the group consisting
of alkyl radicals and monocyclic aryl
radicals,
R4=alkyl,
25
member of the group consisting
of phenylene and naphthylene,
of phenylene and naphthylene,
15
10
wherein Y is a member of the group consisting of
wherein R4=alkyl, _
Rs=a phenyl,
‘
by heating the two components to about 165 to
170° C.
25
.
12. The process which comprises acting while
R5=a phenyl,
in the presence of a mixture of pyridine and
heating upon a quaternary ammonium salt cor
piperidine.
responding with the formula
9. The process which comprises acting while
heating upon a quaternary ammonium salt cor
30
responding with the formula
1\/Y>011.
35
N
30
wherein Y is a member of the group consisting
35
.
of S, Se, 0,
~
R is a member of the group consisting
wherein Y is a member of the group consisting ,
of S, Se, 0,
R is a member of the group consisting
40
of phenylene and naphthylene,
r=alkyl,
of phenylene and naphthylene,
r=a1kyl,
.
_
with a thioimide corresponding with the formula
>
SR4
:c=an acid radical,
with a thioimide corresponding with the formula
H3CO-CsH4—-C
45
NR5
SR4
45
wherein R4=alkyl,
R5=a phenyl,
HaC——-C\\NR5
in the presence of pyridine.
13. The process which comprises acting while
wherein R4=alkyl,
R5=a phenyl,
50
40
:c=an acid radical,
e
in the presence of an acid condensing agent.
heating upon a quaternary ammonium salt cor
50
responding with the formula
10. The process which comprises acting while
heating upon a quaternary‘ ammonium salt cor
responding with the formula
f
2
wherein Y is a member of the group consisting
of S, Se, 0,
60
R is a member of the group consisting
wherein Y is a member of the group consisting
of S, Se, 0,
w
R is a member of the group consisting
of phenylene and naphthylene,
65
r=alkyl§
60
of phenylene and naphthylene,
-r=alkyl,
'
:c=an acid radical,
_
_
_
with a thioimide corresponding with the formula
SR4
:r=an acid radical,
with a thioimide corresponding with the formula
R:—-C\
7
NR;
wherein R3 is a member of the group consisting 70
of alkyl radicals and monocyclic aryl
radicals
' wherein R4=alkyl,
R5=a phenyl,
75 in the presence of acetic anhydride.
.
R4=alkyl,
R5=a phenyl,
-
in the presence of an acid condensing agent and 75
12
2,101,370
,
condensing the resulting product in the presence
of a basic condensing agent with a quaternary
ammonium salt corresponding with the formula
uct formed of the 2-methylbenzthiazole ethiodide
and'the ethylisothioacetanillde, and condensing
said intermediate product with 2-methyl-4.5-ben
zobenzthiazole dimethylsulfate in the presence oi.’
Dyrldlne-
’
1'1. The process which comprises heating a
quaternary ammonium salt of a heterocyclic base"
containing in its molecule a nucleus selected from
.the group consisting of. the thiazole nucleus the
wherein Y’ is a member ofv the group consisting selenazole nucleus and the oxazole nucleus hav
ing a methyl group capable of reaction in a-DO 10
of 8, Se, 0,
,
'
R’ is a member of the group consisting sition to the nitrogen atom, with the alkyl ester
. ' of vinylene, phenylene Bi'ld naphthyl- , .of a thloimidic acid substituted by a monocyclic
aryl radicle.
'
ene,
15
18. An unsymmetrical carbocyanine salt having
r'=alhl,
a:'=an acid radical,
7 a heterocyclic group and a heterocyclic group in 15
_
and in which Y’, R’ and 1" may be the same or
salt form, selected from the group consisting of
diiferent radicals as Y, R and r.
benzothiazoles,v naphthothiazoles, benzoselena
‘
14. The process which comprises acting upon soles, naphthoselenazoles, benzoxazoles and
a quaternary ammonium salt corresponding with I naphthoxazoles linked in a-posltion to the nitro 20
the formula
'
gen atom each to one end of a trimethenyl chain
whichcarries a substituent at the'central carbon
atom selected from the class consisting of alkyl
and monocyclic aryl radicles, the‘ sum of the
atoms of the one heterocyclic group being diifer
,ent from that of ‘the other while disregarding
the salt forming anion.
wherein Y is a member vof the group consisting of
of S, ~Se, O,
30'
Y
,
'
R is a member of the group consisting of
phenylene and naphthylene,
_
35
z'=an acid radical,
'
a
an.
' Its-O:
.
ving a heterocyclic group and a heterocyclic group
in salt form, selected from the group consisting
of benzothiazoles, naphthothiazoles, benzoselen 30
azoles, naphthoselenazoles, benzoxazoles and
naphthoxazoles linked in a-position to the nitro
.
with a thioimide corresponding .with the formula
'
_
19. An unsymmetrical carbocyanine salt hav
gen atom each to one end of a trimethenyl chain '
which carries an alkyl group at the central car
bon atom, the two heterocyclic'groups being dif
ferent in structure while disregarding the salt
forming anion.
\
‘
\NR.
wherein R: is a member of the group consisting
_ 20. An unsymmetrical carbocyanine salt having
a heterocyclic group and a heterocyclic group in
of alkyl' radicals and monocywclic aryl
salt form, selected from the group consisting of 40
radicals
benzothiazoles, naphthothiazoles, benzoselena—
'
Rl=81k¥1
\
Rs=a phenyl,
zoles,
‘
naphthoselenazoles,
benzoxazoles
and
naphthoxazoles linked in a-DOSltlOli to the nitro
.
45 by heating the two compounds and condensing
the resulting product in the presence of a basic
condensing agent with a quaternary ammonium
_. salt corresponding with the formula
50
gen atomeach to one end of a tri-methenyl chain
which carries a methyl group at the central car 45
bon atom, the two heterocyclic groups being dif
ferent in structure while vdisregarding the salt
forming anion.
21; An unsymmetrical carbocyanine salt having ‘
a heterocyclic group and a heterocyclic group 50
in salt form, selected from“the group consisting _ I
of benzothiazoles, naphthothiazoles, benzoselen
azoles, naphthoselenazoles, benzoxazoles and
55
wherein Y' is a member of the group consisting
of 8, Se, 0,
_
‘
.
-
“R’=vinylene, phenylene and naphthyl
,
e119.
_
naphthoxazoles linked in a-DOSltlOIl to the nitro
ferent in structure while disregarding the salt
f'=?lb1,
z’=an acid radical,
forming anion.
4
and in which Y’, R’ and 1" may be the same or
din'erent radicals as Y, R and r.
_
v
22. 'I‘rimethinecyanine dyes having the gen
eral formula
15. The process which-comprises heating _2
65 methylbenzthiaaole ethiodide' and ethylisothio
propionanilide to about 165 to 170° C., separat
ing from the reaction mixture the intermediate
product formed from said compounds, and con-‘
densing said
710
intermediate . product
_
_
16. The process which comprises boiling a mix
16.
‘
.
Y
n _
.
z
Y’
H J: H
/
c= —c
alky( \mt
with 2
methyl-li-methoxybenzselenazole ethiodide in the
presence of pyridine.
55
gen atom- each to one end of a tri-methenyl chain
which carries an ethyl group at the central car
bon atom, the two heterocyclic groups being .dif- .
‘
n’
N
alk'yl
group
wherein
Y and Y' are selected from the class consisting of
8, Se and 0,
ture of 2-methylbenzthiasole ethiodide, ethylisc
thioacetanilide and acetic anhydrlde, separating 'R' and R’ are selected from the group consisting
from the reaction mixture the intermediate prod
of phenylene, naphthylene, alkyl phenylene,
65
2,107,379
alkoxy phenylene, amino phenylene and alkyl
amino phenylenei
F
Y being di?erent from Y’ when .R is the same
as R’ and‘
\
5 R being different from B.’ when Y is the same as
Y’;
and
-
'
'
Z being selected from the class consisting of alkyl
and mon'ocyclic aryl radicles.
23. The process which comprises heating 2
1° methylbenzthiazole ethiodide and ethylisothio
propionanilide to about 165 to 170° 0., separat
13
ing from the reaction mixture the intermediate
product formed from said compounds and con
densing said intermediate product with 2-methy1
benzoxazole ethiodide in the presence of pyridine.
24. The dye 1.1'-diethyl-6'.7'-benzobenzthio
mesomethyl-carbocyanine iodide.
25. The dye 1.1"-diethy1-6'-methoxy-benzthio
benzselenomesoethyl-carbocyanine iodide.
26. The dye 1.1'-diethy1-mesoethyl-benzthio
benzoxo-carbocyanine iodide.
.
'
ROBERT KOSLOWSKY.
Документ
Категория
Без категории
Просмотров
0
Размер файла
1 355 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа