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Патент USA US2112140

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2,112,140
‘ Patented Mar. 22, 1938 ‘
UNITED STATES
PATENT OFFICE
2,112,140
'
PROCESS ron PREPARING CARBOCYANINE
1),YES
Leslie G. srBrookcr and Frank L. White, Roches
ter, N. Y., assignors, by memo assignments, to
Eastman Kodak‘ Company, Jersey City, N. J.,
a corporation of New Jersey
No Drawing. Application July 10, 1935,
Serial No. 30,736
24 (llalms. \ (Cl. 260-44)
This invention relates to carbocyanine dyes and reaction wherein the ketone, l-acetyl-methylene
more particularly to symmetrical and unsym
z-ethylbenzothiazoline, is condensed with the
metrical carbocyanine dyes, containing a sub
ethiodide of l-methylbenzothiazole, in the pres
ence of acetic anhydride:
stituent on the central carbon atom of the tri
.5
methenyl chain.
1
'
We have found the heretofore proposed meth
ods of preparing unsymmetrical carbocyanine
dyes, containing a substituent on the central car
bon atom of the trimethenyl chain, to be gener
ally unsatisfactory. In fact, most of such un
10
symmetrical carbocyanine dyes cannot "be pre
pared by the heretofore proposed methods. Now,
we have found that these unsymmetrical carbo
cyanine dyes can be prepared by condensing
1
cyclammonium quaternary salts containing a re
active methyl group with ketones of the follow
ing structure:
15
In a similar manner, quaternary salts of 1
methylbenzoxazole,' l-methylbenzoselenazole or
2~methyl-p-naphthothiazole‘or the like can be
condensed with the same ketone or related 20
20
t
wherein A represents a phenylene group, such as
the phenylene group, the methylphenylene group
25 or the chlorophenylene group, or a naphthylene
group, Y represents sulfur or selenium, R repre
sents an alkyl group and R’ represents an alkyl,
an aralkyl or an aryl group. Such ketones are
The condensations can be effected in the
absence of water-binding agents by heating, but
containing a substituent on the central carbon
cated in the appended claims.
EXAMPLE 1.—2,2'-Diethyl-8-methyl-3,4-benzothi
1
The object, therefore, of our invention is to
provide unsymmetrical carbocyanine dyes, con
of the trimethenyl chain. A further object is to
provide a process for the ‘preparation of sym
40 metrical and unsymmetrical carbocyanine dyes
containing a substituent on the central carbon
atom of the trimethenyl chain.. Other more spe
ci?c objects will become apparent upon a com:
plete perusal of these speci?cations.
In general, our process of preparing these car
bocyanine dyes comprises condensing a ketone of
the hereinabove described structure with
a
cyclammonium salt, containing a reactive methyl
group, in the presence of a water-binding agent.
50
dride.
atom of the trimethenyl chain.
taining a substituent on the central carbon atom
45
temperatures, in the presence of acetic anhy
method of producing symmetrical carbocyanines
Serial No. 29,916 filed July 5, 1935. We have
further found our new process to be a satisfactory
35
sations are usually accelerated by heating, al
though they do take ‘place slowly at ordinary 25
the results are generally not satisfactory.
The following examples serve to illustrate our
invention, but it is to be understood that our
invention is not limited thereby except as indi
fully described in our ‘co-pending application
30
ketones to yield symmetrical or unsymmetrical
dyes. Other quaternary salts, such as the alkyl
p-toluenesulfonates, can be used. The conden
The process can be illustrated by the following
acarbocyanine iodide
'
35
0.73 g. (1 mol.) of l-acetylmethylene-2-ethyl
benzothiazoline, 1.33 g‘. (1 mol.) of 2-methyl-p
naphthathiazole etho-p-toluenesulfonate werere
?uxed for ?fteen minutes in 10 cc. of acetic anhy 40
dride. The reaction mixture was cooled and the
dye precipitated with ether. The residue was dis
solved in methyl alcohol and the dye precipitated
as the iodide with potassium iodide. The dye was
then washed with water followed by acetone. 45
Recrystallization was effected from methyl al
cohol (260 cc. per gram of dye). The dye was
obtained as reddish coppery crystals which gave
a purplish solution in methyl alcohol.‘v The dye
sensitized a photographic silver bromide emul 50
2
2,112,140
sion to 680 millimicrons with maximum sensitiv
ity at 550 millimicrons and 615 millimicrons.
EXAMPLE 2.-2,2'~Diethyl-8-methyl-3A-benzo
ExAMPLE 7.—2’-AZlyl-8-ethyl-2-methyl-3,4 benze
thiacarbocyanine iodide
thiacarbocyanine iodide
ene-benzothiazoline and 3.85 g. (1 mol.) of 2-
2.45 g. (1 mol.) of 2-allyl-1-propionylmethyl
methyl-p-naphthothiazole metho-p-toluenesul
0.67 g. (1 mol.) of 2-acetylmethylene-l-ethyl
?-naphthathiazoline and 0.87 g. (1 mol.) of 1
methylbenzothiazole
fonate were re?uxed for ?fteen minutes with 15
cc. of acetic anhydride. The crude product was
etho - p - toluenesulfonate
isolated as in Example 1. Following recrystal
lization from methyl alcohol, the dye was ob~
were re?uxed for ?fteen minutes in 15 cc. of
10 acetic anhydride. The dye was isolated as in
tained as minute green crystals.
Example 1, and, of course, had the same proper
ties as the dye of Example 1.
~
EXAMPLE 3.—2'-Ethyl-2,8-dimethyl-3,4 benzox
EXAMPLE 8.--2,8-Diethyl-2'-n-proplyselenathia
athiacarbocyanine iodide
15
carb'icyanine iodide
2.2 g. (1 mol.) of 1-acetylmethylene-Z-ethyl
benzothiazoline. 3.6 g. (1 mol.) of Z-methyl-?
solved in methyl alcohol and the dye precipitated
as the iodide with potassium iodide. The crude
dye was washed with water and ?nally with
25 acetone. Recrystallization was effected from
methyl alcohol, the dye being obtained as minute
purplish crystals which gave a pink solution in
methyl alcohol. The dye sensitized a gelatine
propylbenzothiazoline and 3.52 g. (1 mol.) of l
methylbenzoselenazole ethiodide were re?uxed in
15 cc. of acetic anhydride 1'0r ?fteen minutes.
The crude product was isolated as in Example 6. 20
Following recrystallization from methyl alcohol,
the dye was obtained as dark blue crystals. Sen
sitized a gelatino-silver-bromide emulsion to 6'70
millimicrons, with maximum sensitivity at 615 25
and 485.
EXAMPLE 9.-—4’-C'hlor0-2,2’,8-triethyZ-3,4-benzo
thiacarbocyanine iodide
0.89 g. (1 mol.) oi.’ 4-chloro-2-ethyl-I-propionyl
methylene-benzothiazoline and 1.33 g. (1 mol.) 30
silver-bromide emulsion to 630 millimicrons with
30 maximum sensitivity at 555 millimicrons.
EXAMPLE 4.-—4-ChZoro-2,8-diethyl-2’-methylthia
of 2-rnethyl-,6-naphthothiazole etho-p-toluene
carbocyam'ne iodide
sulfonate were re?uxed in 10 cc. of acetic an
0.73 g.
(1 mol.)
hydride for ?fteen minutes. The crude product
of 2-methyl-1-propionyl
35 methylene-benzothiazoline and 1.28 g. (1 mol.) of
4-chloro-l-methylbenzothiazole etho-p-toluene
_ sulfonate (made by heating equimolecular propor
tions of 4-chlor0-l-methylbenzothiazole and
ethyl-p-tolu'enesulfonate for 7 days at 100° C.
40 and grinding the resulting product with acetone)
were re?uxed for ?fteen minutes with 10 cc. of
acetic anhydride. The dye was isolated as in Ex
ample 1 and obtained as reddish brown needles
with
double green and blue re?ex upon recrystal
45
lization from methyl alcohol. Sensitized gela
tine-silver~bromide emulsion to 680 millimicrons
with maximum sensitivity at 635.
EXAMPLE 5.—2,8-Diethyl-2t-methyl-SA-benzo
thiacarbocyanine iodide
~
0.73 g. (1 mol.) of 2-methyl-l-propionyl-meth
ylene-benzothiazoline and 1.33 g. (1 mol.) of 2
methyl-p-naphthothiazole
15
2.47 g. (1 mol.) of 1-propionylmethylene-2-n
naphthoxazole metho-p-toluenesulfonate were re
?uxed for 20 minutes in 10 cc. of acetic anhydride.
20 The reaction mixture was cooled and the dye
precipitated with ether. The residue was dis
50
sensitized a 10
gelatino-silver-bromide emulsion to 710 milli
microns with maximum sensitivity at 640 and 550.
etho~p-toluenesulfo
55 nate were re?uxed for 15 minutes in 10 cc. of
acetic anhydride. The dye was isolated as in Ex
ample 1 and obtained as greenish crystals upon
recrystallization from methyl alcohol. sensitized
gelatino-silver-bromide emulsion to 700 millimi
crons with maximum sensitivity at 650.
EXAMPLE 6.-2 , 8 - Diethyl-Z'-methyloxathiacar
bocyanine iodide
0.73 g. (1 mol.)~ of Z-methyl-l-propionyl
65 methylene-benzothiazoline and 2.89-g. (1 mol.) of
1~methylbenzoxazole ethiodide were re?uxed for
?fteen minutes in 10 cc. of acetic anhydride. The
reaction mixture was cooled, ether added, chilled
and the solvent portion decanted. The residue
was boiled ‘with acetone, chilled, ?ltered and
m washed
and dried. Recrystallization was e?’ected
from ethyl alcohol (95%). The dye was obtained
as reddish orange powder. sensitized photo
graphic emulsion to 600 millimicrons with maxi
75 mum sensitivity at 545.
was isolated as in Example 1. Following recrys
tallization from methyl alcohol, the dye was ob
tained as dark green crystals. sensitized a gel
35
atino-silver-bromide emulsion to 710 millimicrons
with maximum sensitivity at 540 and 655.
EXAMPLE 10.—4'-C'hloro-2,2’,8-triethyl-3,4—benzo
,
40
thiacarbocyanine iodide
2.83 g. (1 mol.) of 1-ethyl-2-propionylmethyl
ene-B-naphthothiazoline and 3.84 g. (1 mol.) 4
chloro-l-methylbenzothiazole etho-p-toluenesul
fonate were re?uxed for ?fteen minutes in 10 cc.
of acetic anhydride. The crude product was iso
45
lated as in Example 1. The dye, of course, has
the properties of the dye in Example 9.
EXAMPLE 11.—2,2'-Diethyl-8-methyZ-3,4,3',4’-di
50
benzothiacarbocyanine bromide
1.35 g. (1 mol.) of 2-acetylmethylene-l-ethyl
B-naphthothiazoline and 2 g. (1 mol.) of 2-meth
yl-p-naphthothiazole
etho-p - toluenesulfonate 55
were re?uxed for thirty minutes in 15 cc. of acetic
anhydride. The crude dye was isolated as in Ex
ample 1, except that the dye was precipitated as
the bromide with potassium bromide. Following
recrystallization from methyl alcohol, the dye was 60
obtained as green crystals. The sensitizing eiIect
of this dye on gelatino-silver-bromide emulsions
is well known.
EXAMPLE 12.—-2,2'-Diethyl-8,9-dimethyl-3,4-ben
zothiacarbocyanine iodide
65
2.69 g. (1 mol.) of 2-acetylmethylene-l-ethyl
p-naphthothiazoline and 3.19 ,g. (1 mol.) of 1
ethylbenzothiazole ethiodide were re?uxed for
?fteen minutes in 20 cc. of acetic anhydride. The 70
dye was isolated as in Example 6. Following re
crystallization from methyl alcohol, the dye was
obtained as reddish coppery crystals. Sensitlzed
a gelatino~silver-bromide emulsion to 605 milli
microns with maximum sensitivity at 530.
75
3
2,112,140
EXAMPLE 13.--2,2’-Dieth1!l-8-methyl-3',4'
benzoselenathiacarbocyanine iodide
Exaurnr: 19.—2,2',-Diethul-8-phenulthiaoarboc11
1.35 g. (1 mol.) of 2-acetylmethylene-1-ethyl
?-naphthothiazoline and 1.76 g. (1 mol.) of 1
methylbenzoselenazole ethiodide were re?uxed in
25 cc. of acetic anhydride for thirty minutes.
The dye was isolated as in Example 6. Following
1.4 g. (1 mol.) of 1-benzoylmethylene-2-ethyl
benzothiazoline, 1.5 g. (1 mol.) of l-methylbenzo
anine iodide
recrystallization from methyl alcohol, the dye was
obtained as reddish coppery‘crystals. sensitized
10 a gelatino-silver-bromide emulsion to 690 milli
microns with maximum sensitivity at 610 and 550.
EXAMPLE 14.—2,2'-Diethyl-8-methyl-3',4’
benzoxathiacarbocvanine iodide
15
2.69 g. (1 mol.) of2-acetylmethylene-1-ethyl—
,e-naphthothiazoline and 2.89 g. (1 mol.) of 1
methylbenzoxazole ethiodide were re?uxed for
?fteen minutes in 20 cc. of‘ acetic anhydride. The
20 dye was isolated as in Example 6. Following re
crystallization from methyl alcohol, the dye was
obtained as purplish needles with a blue re?ex.
Sensitized gelatino-silver-bromide emulsion to
620 millimicrons with maximum‘ sensitivity at 555.
25
EXAMPLE 15.—-2,2’,8-Triethyl-3,4-benzothia
carbocyanine iodide
‘
‘ 2.83. g. (1 mol.) of 1-ethyl-2-propionylmeth
ylene-p-naphthothiazoline and 3.05 g. (1 mol.)
30 of l-methylbenzothiazole ethiodide were re?uxed
for ?fteen minutes in 15 cc. of acetic anhydride.
The dye was isolated as in Example 6. Following
recrystallization from‘ methyl alcohol,v the dye
was obtained as green crystals.
sensitized a
35 gelatlno-silver-bromide emulsion to 680 .milli
crons with‘maximum sensitivity at 620 and 550.
EXAMPLE 16.—2,2',8-Triethul-3'4'-benzoselena
40
From these examples, it is apparent that a
large number of symmetrical and unsymmetrical
carbocyanines, containing a substituent attached
to the central carbon atom of the trim'ethenyl 15
chain can be prepared by our improved proce
dure. All of these dyes are useful for improving
and extending the sensitivity of photographic
gelatino-silver-bromide emulsions.
The ketones employed in our new process de 20
scribed herein can be prepared as set forth in
our copending application Serial No. 29,916, ?led
July 5, 1935, by reacting the appropriate cyclam
monium alkyl quaternary salt containing a re
active methyl group with an acyl halide, in the’ 25
presence of an acid-binding agent, e. g. pyridine.
Typical ketones set forth in our copending appli
cation are, for example, 1-acetylmethylene-2
ethylbenzothiazoline, 1-ethyl-2-propionylmethyl
ene-p-naphthothiazoline, 2-ethyl - 1 - propionyl
methylenebenzoselenazoline,
ene-2-ethyl-benzothiazoline, >2-ethyl-1-lauroyl
methylenebenzothiazoline, 2-ethyl-1-furoylmeth
ylenebenzothiazoline and the like.
‘
What we claim as our invention and desire to 35
be secured by Letters Patent of the United States
is‘
lected from the group consisting of benzothiazole,
heat, a cyclammonium alkyl quaternary salt se- . 40
naphthothiazole,
benzoselenazole,
benzoxazole
and naphthoxazole alkyl quaternary salts con
for ?fteen minutes in 15 cc. of acetic anhydride.
The dye was isolated as in Example 6. Follow
taining a reactive methyl group, with a compound
ing recrystallization from methyl alcohol, the dye
of the following formula:
and 540.
.
EXAMPLE 17.—2,2',8-Triethyl-3'4',-benzomathia
2.83 g. (1 moL) of l-ethyl-2-propionylmethyl
ene-p-naphthothiazoline and 2.89 g. (1 mol.) of
l-methylbenzoxaaole ethiodide were re?uxed for
?fteen minutes in 10 cc. of acetic anhydride. The
dye was isolated as in Example 6. Following re
crystallization fromethyl alcohol (95%) the dye
Sensi
ized a gelatino-silver-bromide emulsion to 640
illimicrons with maximum sensitivity at 588.
lillgamrnn 18.--2,8-Diethyl-2’-meth1ll~3',4'-beneo
selenuthiacarbocyanine iodide
0.93 g. (1 mol.) of 2-ethyl-l-propionylmethyl
enebenzoselenazoline and 1.28 g. (1 mol.) of 2
methyl-p-naphthothiazole metho-p-toluene-sul
Y
45
__a'
A/ \c=cn-(':=o
\N/
i.
50
wherein A represents an organic group selected
from the group consisting of phenylene and
naphthylene groups, Y represents an atom select
ed from the group consisting of sulfur and se 55
lenium, R represents an alkyl group and R’ rep
resents a group selected from the group consist
ing of alkyl, aralkyl, and aryl groups.
2. A process for preparing a carbocyanine dye
comprising condensing, under the in?uence of 60
heat and in the presence of a water-binding
agent, a cyclammonium allwl quaternary salt
selected from the group consisting of benzo
thiazole, naphthothiazole, benzoselenazole, benz
oxazole and naphthoxazole alkyl quaternary salts 65
containing a reactive methyl group, with a com
pound of the following formula:
fonate were re?uxed‘ for ?fteen minutes in 10 cc.
of acetic anhydride. The dye was isolated as in
Example 6.‘ ' Following recrystallization from
methyl alcohol, the dye was obtained as‘ dull
greenish crystals. sensitized a gelatino-silver
bromide emulsion to 720 millimicrons, with maxi
mum sensitivity at 640 and 540.
30
1 - benzoylmethyl
2.83 g. (1 mol.) of I-ethyl-Z-propionyl-methy
lene-p-naphthothiazoline and 3.52 g. (1 mol.) of
l-methylbenzoselenazole ethiodide were re?uxed
60 was obtained as dull brownish crystals.
65
isolated as in Example 6. Eollowing recrystalli
zation from methyl alcohol, the ‘dye was obtained
as shiny green crystals. sensitized a gelatino~
silver-bromide-emulsion to 650 millimicrons, 10
with maximum sensitivity at 620.
1. A process for preparing a carbocyanine dye
comprising condensing, under the in?uence of
carbocyanine iodide
55
thiazole ethiodide were re?uxed for ?fteen min
utes in 15 cc. of acetic anhydrlde. The dye was
thiacarbocilanine iodide
was obtained as minute dark green crystals. Sen
sitized a gelatino-silver-bromide emulsion to 710
. millimicrons with maximum sensitivity at 650
50
‘
70
wherein A represents an organic group selected
from the group consisting of phenylene and 75
4
2,112,140
naphthylene groups, Y represents an atom se
lected from the group consisting of sulfur and
nary salts containing a reactive methyl group
with a compound of the following formula:
selenium, R represents an alkyl group and It’
represents a group selected from the group con
sisting of allqrl, aralkyl and aryl groups.
3. A process for preparing a carbocyanine dye ‘
comprising condensing, in the presence of a
water-‘binding agent, a cyclammonium alkyl‘ qua
ternary salt selected from the group consisting
of benzothiazole, naphthothiazole, benzoselenaz
ole, benzoxazole and naphthoxazole alkyl quater
nary salts containing a reactive methyl group,
with a compound of the following formula:
i
wherein A represents an organic group selected
from the group consisting of phenylene and
naphthylene groups, Y represents an atom se 10
lected from the group consisting of sulfur and
selenium and R and. R’ represent alkyl groups.
7. A process for preparing a carbocyanine dye
comprising condensing, in the presence of an
organic acid anhydride, a cyclammonium alkyl 15
quaternary salt selected from the group consist
16
ing of benzothiazole, naphthothiazole, benzo
selenazole, benzoxazole, and naphthoxazole alkyl
wherein A represents an organic group selected
from the group consisting‘ of phenylene and
naphthylene groups, Y represents an atom se
lected from the group consisting of sulfur and
25 selenium, R represents an alkyl group and R’
represents a group selected from the group con
sisting of allwl, aralkyl and aryl groups.
4. A process for preparing a carbocyanine dye
comprising condensing, in the presence of a fatty
80 acid anhydride, a cyclammonium alkyl quater
nary salt selected from the group consisting of
benzothiazole, naphthothiazole, benzoselenazole,
benzoxazole and naphthoxazole alkyl quaternary
salts containing a reactive methyl group, with
a. compound of the following formula:
‘
quaternary salts containing a reactive methyl
group with a compound of the following for 20
mula:
‘
Y
A/ \
\ /
25
i
wherein A represents an organic group selected
from the group consisting of phenylene and
naphthylene groups, Y represents an atom se
30
lected from the group consisting of sulfur and
selenium and R and R’ represent alkyl groups.
8. A process for preparing a carbocyanine dye
comprising condensing, in the presence of a fatty
acid anhydride, a cyclammonium alkyl quater 35
nary salt selected from the group consisting of
benzothiazole, naphthothiazole, benzoselenazole.
benoxazole, and naphthoxazole alkyl quaternary
i
salts containing a reactive methyl group with a
compound of the following formula:
wherein ‘A represents an organic group selected
from the group consisting of phenylene and
naphthylene groups, Y represents an atom se
lected from the group consisting of sulfur and
selenium, R represents an alkyl group and R’
represents a group selected from the group con
wherein A represents an organic group selected
sisting of alkyl, aralkyl and aryl groups.
from the group consisting of phenylene and naph
5. A process for preparing a carbocyanine dye
comprising condensing, in the presence of acetic
anhydrlde, a cyclammonium alkyl quaternary salt
selected from the group consisting of benzothi
azole, naphthothiazole, benzoselenazole, benz
oxazoie and naphthoxazole alkyl quaternary salts
65 containing a reactive methyl group, with a com
pound of the following formula:
i
40
45
thylene groups, Y represents an atom selected
from the group consisting of sulfur and selenium‘
and R and R’ represent alkyl groups.
9. A process for preparing a carbocyanine dye
comprising condensing, in the presence of acetic
anhydride, a cyclammonium alkyl quaternary
salt selected from the group consisting of benzo
thiazole, naphthothiazole, benzoselenazole, benz
oxazole and naphthoxazole alkyl quarternary
salts containing a reactive methyl group with a
compound of the following formula:
60
i
wherein A represents an organic group selected
from the group consisting of phenylene and
naphthylene groups, Y represents an atom se
lected from the group consisting of sulfur and
selenium, R represents an alkyl group and R’
represents a group selected from the group con
sisting of alkyl, aralkyl and aryl groups.
70
6. A process for preparing a carbocyanine dye
comprising condensing, in the presence of a
water-binding agent, a cyclammonium alkyl qua
ternary salt selected from the group consisting
of benzothiazole, naphthothiazole, benzoselenaz
75 ole, benzoxazole and naphthoxazole alkyl quater
wherein A represents an organic group selected 65
from the group consisting of phenylene and naph
thylene groups, Y represents an atom selected
from the group consisting of sulfur and selenium
and R and R’ represent alkyl groups.
10. A process for preparing a carbocyanine dye
comprising condensing, in the presence of a fatty
acid anhydride, a cyclammonium alkyl quater
nary salt selected from the group consisting
of. benzothiazole, naphthothiazole, benzoxazole,
naphthoxazole and benzoselenazole alkyl quarter
5
2,112,140
‘nary salts containing a reactive methyl group
with a compound of the following formula:
wherein A represents a phenylene group and R
and Bi represent alkyl groups.
,
17. A process for preparing a carbocyanine dye
comprising condensing, in the presence of a fatty
acid anhydride, a naphthothiazole aikyl quater
nary salt containing a reactive methyl group with
wherein A represents a phenylene group and R
and R’ represent alkyl groups.
10
11. A process for preparing a carbocyanine dye
comprising condensing, in the presence of acetic
anhydride, a cyclammonium alkyl quarternary
salt selected from the group consisting of benzo
thiazole, naphthothiazole, benzoxazole, naph
15
thoxazole and benzoselenazole alkyl quaternary
salts containing a reactive methyl group with a
compound of the following formula:
a 1-alky1-2-propionylmethylenebenzoselenazoline.
18. A process for preparing a carbocyanine dye
comprising condensing, in the presence of acetic
anhydride, a p-naphthothiazole alkiodide con
taining a reactive methyl group with a l-alkyl-2
10
propionylmethylenebenzoselenazoline.
19. A process for preparing a carbocyanine dye
comprising condensing, in the presence of acetic
anhydride, Z-methyl-p-naphthothiazole ethiodide 15
with 1-ethyl-2-propionylmethylenebenzoselenaz
ole.
20. A process for preparing a carbocyanine dye
comprising condensing, in the presence of a fatty
acid anhydride, a cyclammonium alkyl quater 20
nary salt selected from the group consisting of
20
i
wherein A represents a phenylene group and R
and R’ represent alkyl groups.
12. A process for preparing a carbocyanine dye
- comprising condensing, in the presence of a fatty
benzothiazole,
naphthothiazole,
benzoxazole,
naphthoxazole, and benzoselenazole alkyl quater
nary salts containing a reactive methyl group
with a compound of ‘the following formula:
25
acid anhydride, a benzothiazole alkyl quaternary_
salt containing a reactive methyl group with a
l-alkyl - 2 - propionylmethylene-p-naphthothiazo
line.
13. A process for preparing a carbocyanine dye
comprising condensing, in the presence of a fatty
i acid anhydride, a benzothiazole alkiodide con
taining a reactive methyl group with a l-alkyl
2-propionylmethylene-p-naphthothiazoline.
14. A process for preparing a carbocyanine dye
comprising condensing, in the presence of acetic
anhydride, l-methylbenzothiazole ethiodide with
l-ethyl - 2 - propionylmethylene-p-naphthothiazo
40
line.
~
15. A process for preparing a carbocyanine dye
comprising condensing, in the presence of a fatty
30
wherein A represents a naphthylene group and
R and R’ represent alkyl groups.
'21. A process for preparing a carbocyanine dye
comprising condensing, in the presence of acetic 35
anhydride, a cyclammonium alkyl quaternary
salt selected from the group consisting of heme
thiazole, naphthothiazole, benzoxazole, naph
thoxazole and benzoselenazole alkyl quaternary
salts containing a reactive methyl group with a 40
compound of the following formula:
acid anhydride, a cyclammonium alkyl quater
nary salt selected from the group consisting
45
of benzothiazole, naphthothiazole, benzoxazole,
naphthoxazole and benzoselenazole alkyl quater
45
i
nary salts containing a reactive methyl group
with a compound of the following formula:
50
i
wherein‘ A represents a phenylene group and R
55 and R’ represent alkyl groups.
16. A process for preparing a carbocyanine dye
comprising condensing, in the presence of acetic
anhydride, a cyclammonium alkyl quaternary
salt selected from the group consisting of benzo
thiazole, naphthothiazole, benzoxazole, naphthox
wherein A represents a naphthylene group and R
and R’ represent alkyl groups.
22. A process for preparing a carbocyanine dye
comprising condensing, in the presence of a fatty
acid anhydride, a benzoxazole alkyl quaternary
salt containing a reactive methyl group with a
1- alky1-2-propionylmethylene - p - naphthothiazo
line.
23. A process for preparing a carbocyanine dye
comprising condensing, in the presence of acetic
anhydride, a benzoxazole alkiodide gcontainlng a
reactive methyl group with a l-alkyl-z-propio 60
azole and benzoselenazole alkyl quaternary salts
nylmethylene-p-naphthothiazoline.
containing a reactive methyl group with a com
24. A process for preparing a carbocyanine dye
comprising condensing, in the presence of acetic
pound of the following formula:
anhydride, l-methylbenzoxazole ethiodide with
65
l-ethyl-Z-propionylmethylene - p - naphthothiazo
line.
.
N
t
55
-
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