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Патент USA US2131853

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Patented Oct. 4, 1938
2,131,8531
UNITED STATES PATENT OFFICE
is?
2,131,853
SUBSTITUTED HEPTA- AND‘ PENTA-METH
INECYANINES
I Walter Dieterle, D‘essau-Ziebigk, ‘ and‘ Walter
Zeh, Dessau, Germany, assignors to Agfa
,Ansco Corporation, Bingh‘amton,‘ N. Y., a cor
‘ poration of New?York
No Drawingu Application September 12,‘ 1933,
Serial No. 689,122. In Germany September 14,
1932
1 Claim.
(01. 260—240) '
“Ourl'present, invention relates to; dyeslof the
polymethine series. .
._
)1
'
1
The dyes are obtainable according to the de-?
sired solubility inform of the bromide, iodide,
perchlorate etc. A silver halide emulsion is sensi
I
‘ Oneof its objects are the hereinafter described
dyes of the polymethiné ‘series which are .valu-y tized by incorporation ‘of the dyes. Thus, a solu
: able h ‘sensitiz'ers ‘for photographic ‘emulsions.
tion of the dye in a‘ suitable solvent may be added
Furthernobjects will‘be seen‘ from the detailed,
to an emulsion ready for being cast, or a ?nished
silver halide emulsion layer‘may be bathed in a
speci?cationjfollowing hereafter.‘
V
‘ i
It is- already known to' sensitize silver halide
solution of the-dye.
emulsions, by means of trimethinecyanines which‘
are‘ substituted ‘in the benzene ‘nucleus. ‘ These
The
dyes
methods.
are
‘
V
.
made‘ according
to ' kno
The pentamethinecyanines are ob
tained by condensing the ‘quaternary ammonium
10
dyes when suitably selecting the substituents dis
tingu‘i‘sh-rbver the non-substituted dyes‘by an iri
salt of a ‘heterocyclic base disubstituted in the
creased sensitizing power.
para positions to the carbon atoms ‘common to .
.
the benzenepringand the‘heterocyclic ring the
latter containing a methyl group‘capable 'ofreg
cyanines symmetrically disub-stituted in the para- . action, with ?-‘ethoxyacroleinacetal .or. ,B—ethoxy—
This invention is based on the discovery that
; g the ' penta-methinecyanines ' ‘and hepta-methine
Dosi-tionsfto ‘the; carbon atomsjcommonv to the
benzenej'ring ‘and the heterocyclic ring have a
superior‘ ‘sensitizing effect on silver halide emul
sions than have’ emulsions sensitized by pentaor'hepta-rnethinecyanines which are not sub
acroleinacetal substituted in a- and/ or e-position.
The heptamethinecyanines are prepared accord,
ing to the methods disclosed by Ottmar Wahl in
U. ‘S. Patent Nos. 1,863,679 and 1,878,557 by con
densing the heterocyclic baseszwith the salt of a
stituted or substituted only‘in the 5 and 5' posi-:‘ pentamethenyl-dianilide~ or a pentamethenyl
25
tions or Band 6’ positions respectively.
.
"The‘edyestu?s‘suitable for the purpose of this
dianilide substituted in ‘the polymethine chain.
The bases serving as a starting‘materiafmay
invention correspond with the’ general formula"
be prepared as it has been described in the co
pending application Ser. No. 667,712 ?led by Zeh
et a1.
7
l
'
The following examples serve tovillustrate our.
invention.
‘
‘Example ,1 .T-The dye blS-[3-8thY1r5?-dl?1?t -
so
oxy - 'benzthiazole - (2)] - pentamethinecyanine
30
iodide corresponding with the formula
7
12.1 landfRz‘
stand for alkyl, alkoxy, alkyltmo,
I
'
'alkylseleno;
arylparyloxy,
1
I
.
v
>
35
_
,
x stands for 01, Br, J, ‘304C113; C104 or another
40
"suitable acid‘radical," _
1!; stands‘ for v2 andl3.
‘
_
p
The hydrogen atom .of the central carbon atom
and/or of. the lateral carbon atoms ‘of the poly
methenyl chain can be substituted byan alkyl
- group.
Instead of two alkoxy groups for the
substitution in‘the 5 ‘and ‘6 positions,;and 5" and 6'
positions respectively‘ there may be ‘introduced a
CB/E[B\L
52115
is obtainable ‘by boiling for about '1/2 hour a
mixture of 2' grams of 2-methyl-5».6-dimethoxy
benzothiazole ethiodide, 1 gram of ,3-ethoXy
acroleinacetal and 5 cc. of pyridine. On the
addition of 10 cc. of water the dye is precipitated
from the, dark green solution in form of green
crystals.
‘
v
The alcoholic solution of ‘the dye has an absorp
tion maximum at a wave length of about 685%.
dioxymethylene group or a dioxyethylene group‘;
‘ Incorporated in a silver bromide emulsion con
in theLSa/mefmanner two aryloxy groups may
tainingabout 1 per‘ cent of silver iodide the dye
imparts to it a range of sensitivity from about
be replaced by a dioXyphenylene group. i
40
45
2
2,131,853
600W to 830% with a maximum at a Wave length
of about 745,LL[L.
Example 2.—The dye bis- [3-ethyl-5-ethoxy
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
G-methyl-benzthiazole- (2) l-pentamethine - cya -
650 to 950/141. with a maximum at a wave length
nine iodide corresponding with the formula
of about 865/L/L.
H3067
s
oxy-benzthiazole- (2) l-v-methyl-penta-methine -
lHHHHHll
2
10
Example 6.—The dye bis-[3-ethyl-5.6-dimeth
s_7
cyanine iodide corresponding with the formula
__
02/11:. I
H3oo~67 —-s
(EzHt
is obtained when Working according to the method
described in the preceding example but starting
from the 2.6-dimethyl-S-ethoxybenzothiazole.
15 The dye crystallizes from alcohol in bright green
crystals.
The alcoholic solution of the dye has an absorp
tion maximum at a wave length of about 675%.
Incorporated in a silver bromide emulsion con
20 taining about 4 per cent of silver iodide the dye
imparts to it a range of sensitivity‘from about
600;”; to 810mm with a maximum at a wave length
of about 735a,“.
Example 3.—The dye bis-[3-ethyl-5.6-dimeth
25 oxy-benzthiazole- (2) l-heptamethinecyanine io
dide corresponding with the formula
S
S_
00113
I'HHHHHHH
‘
s— 76-0021:
l'lillilgHsl-illgg ‘ 5
gfaqg y__g ‘jg/W
4
2
_
_
_
(Dz/H5 I
__
_
_
10
OOH:
(‘ma
may be obtained by heating 2 grams of Z-methyl 15
5.6-dimethoxybenzothiazole ethiodide in 10 cc. of
pyridine with 1 gram of ?-ethoxy—a—methyl
acroleinacetal for about 30 minutes to 130° C.
On the addition of about 10 cc. of water the dye
separates in form of bluish green ?akes. The dye 20
crystallizes from alcohol in green felted needles.
The alcoholic solution of the dye has an ab
sorption maximum at a wave length of about
685M»;
‘
Incorporated in a silver bromide emulsion con 25
taining about 4 per cent of silver iodide the dye
imparts to it a range of sensitivity from about
600W to 830M,“ with a maximum at a wave length
0f about 745/14!“
' Example 7 .--The dye bis-[3-ethyl-5.fi§diethoxy-v 30
2
“3.0
H300
s
benzthiazole - (2) l- 6 -methyl - heptamethinecya
may be obtained by dissolving 2 grams of 2
methyl-5.6-dimethoxybenzothiazole ethiodide and
gram of e-phenylimido-e-phenylamido-axy
35 1
nine iodide corresponding with the formula .
mono-I6 7
35
pentadiene-hydrobromide in 10 cc. of hot alcohol
and this mixture is boiled for about 10 minutes
with the addition of 0.5 cc. of diethylamin. The
dye separates in form of green crystals.
40'
45'
Incorporated in a silver bromide emulsion con
taining about 4 per cent of silver iodide the dye
may be obtained by boiling 2 grams of Z-methyl
5.6-diethoxy-benzothiazole ethiodide with 1 gram
imparts to it a range of sensitivity from about
600% to 930% with a maximum at a Wave length
of E-phenylimido - or - phenylamido-'y-methyl-axy
of about 845%.
methyl-5.6-diethoxybenzothiazole ethiodide, there
is obtained the dye bis-[3-ethyl-5.6-diethoxy
benzthiazole- (2) l-heptamethinecyanine iodide.
comes green. After cooling the dye separates in
form of green crystals.
Incorporated in a silver bromide emulsion con 45..
taining about 4 per cent of silver iodide the dye
imparts to it a range of sensitivity from about
600% to 930M,“ with a maximum at a wave length
The dye crystallizes from methanol in green
of about 845/141“
Example 4.—When working as described in the
preceding example, but starting from the 2
little rods.
'
.
Incorporated in a silver bromide emulsion con
taining about 1 per cent of silver iodide the dye
imparts to it a range of sensitivity from about
40
pentadiene hydrobromide until the mixture be
Example
8.—The
‘
dye
50
bis-[3-ethyl-5.6-di
methyl - benzselenazole - (2) l - 6 — methyl-hepta
methinecyanine iodide corresponding with the
660m‘ to 920;“; with a maximum ata wave length
of about 845%.
5.5..
Example 5.—The dye bis-[3-ethyl—5.6—diethoxy
benzselenazole- (2) l-heptamethinecyanine iodide
corresponding with the formula
60
may be obtained when working according to the
preceding example, but startingfrom the 2.5.6
trimethylbenzoselenazole ethiodide.
/
65
02115
I
' is obtained by boiling 2 grams of 2-methyl-5.6
The dye
crystallizes from alcohol in light green crystals.
Incorporated in a silver bromide emulsion con
a-(n-methyl-phenylimino)-a.~/- pentadiene hy
taining about 1 per cent of silver iodide the dye
imparts to it a range of sensitivity from about
700W to 910,“!!- with a maximum at a wave length
Of about 850/L/L
drobromide, adding 1 cc. of an alcoholic solution
of trimethylamine of 50 per cent strength and
Bis- [3-ethyl — 5.6 - diethoxy-benzthiazole-(2) ]
diethoxy-benzoselenazole ethiodide in 10 cc. of
alcohol with 1 gram of e (n-methyl-phenylimino) -
continuing boiling until the dye begins to sepa
rate. The dye which has been precipitated by
cooling is recrystallized from methanol and forms
75. then blackish green little rods.
What we claim is:
1
65
70
heptamethinecyanine iodide.
WALTER DIE'I'ERLE.
WALTER ZEH.
'
-
75
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