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Патент USA US2131864

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Patented Oct. 4, 1938
2,131,864 1'
. 2,13
1,864
PROCESS“ OF; ‘ MAKING
'
_-
HEPTAMETHINE
'DYES
-
Walter Zeh,‘JDes_sau in Anhalt, Germany, assign- ,
orv ‘to Agi-‘a ; Ansco Corporation,“ Binghamton,
N.~Y.>, a corporation» of New-York‘
‘
NoQDrawing. ~ ‘Applicati on May 11, 1934, Serial
, , .No..725;,214. In Germany May. 18, 1933
5 Claims‘. ~
(
My present-inventionrrelates to ‘dyes ‘of the
. polymethine series. »,
'
creasing amount of condensing agent promotes
the formation of symmetrical dye from which
‘
one?ofwitsp-objects. is to i provide, -a .process: of ‘
the intermediate product must be separated,’ _
producing; dyes from the :polymethineseries; An-.
usually by physical means (crystallization, decoct
5 ,tother object are thedyesfoftthevpolymethine se-~ ing). The most suitable-amount to be used of"
ries: which haverproved-to be valuable sensitizers. ( each Jcondensing agent can easily be determined
Further: objects will ;be seen from the detailed? by experiment. Condensing Iagents whichlmay
speci?cation-‘following hereafter.‘
casually be applied in excess so that nevertheless
the formation of intermediate ‘product occurs
' 'I'hensymmetrical;rheptamethinecyanines have
10 “already. beentproposed:‘aswzsensitizers for ‘the ~
are'the amines.~ In-case of ‘using-pyridine. or
condensing agents of - similar action which si
rangeofqwavevlengths ‘between 650,411 and 1090M.
According to this. inventiontI have found, that
the 1 unsymmetrical'l "heptamethinecyanines
multaneously are usedas solvents, there maybe
are
used an excess for obvious reasons. Of the above,
wellxsuited fol-sensitizing» a silver halide emulsion
15,23,501: this range-oi wave-lengths. vThe progress in
volvedvbyiithe.newisensitizers resides not only in
anilido ‘compounds the N-methyl compounds
have proved particularly suitable insome cases.
It is advisable to use an amount of the anilido
compound substantially exceeding the quantity
‘ thexfacttthata an extraordinary great number of -
' suitableudyes is now available, ‘but also in‘ the
equivalent'to that of the base; preferably‘ there
fact, that .by» suitably/,zcombiningrdifferent vqua
is used a more than 10 per cent excess-in order
to avoid as. far as possible the undesired forma-.
zm-zgternary“ iammonium-s ~ salts -:of “heterocyclic. bases
containing in M'IJOSitiOH to the nitrogen atom a
methylrigroup capable?of reaction nearly any‘ ‘de;
sired maximum ‘of sensitization may be obtained
‘tion of symmetrical dye.
‘
l
>
When .using, for example, benzothiazole as the .
heterocyclic ‘base, the reaction between2~methyl~
in ‘theiinfraqed‘. portionigofithe'spectrum. ‘ Thus ..
benzothiazole iodo alkylate and e-PhBIlYlil’l'lidO-ae
5, ‘it is possible to adjust the sensitivity of :the emul-.. 1
phenylamido-(ml-pentadienehydrobromide prob
‘Vision according to requirement.
25
ably- takes place according to the following for
For: the..._preparation of the unsymmetrical" .mula;
heptacarbocyanines. there is ?rst made an vinter
mediate product by condensing in the presence
8 30 p‘ of an alkaline condensing agent equivalentpor-
1'
‘ tions of a quaternary ammonium salt of a heter.ocyclic base containing in oc-IJOSitiOI‘l to the nitro-
/H,
30.;
,33-6‘H3+OaH5—NH-CH=CH—CH=CH-CH=N~CeHs
../N<v'
‘
‘
\Br
gen atom a methyl group capable of reaction and
RY
I
1
35
.
6\4/\1%}—oH=0H~0H=0H~0H=0H~NH~O6H5+oa115NHz+HBr
/ \
I
40‘ ,of .‘a ..s-phenylimidow-zyr-pentadiene .7 ‘hydrohaloe,
.
In ‘this mannerthe intermediate hexamethine
genide... As alkaline...condens_ing . agent . I have
dyestuff corresponding with the above formula is‘.
found suitable, for instance, primary, ‘secondary . formed, which is then converted with the qua
and tertiary amines, suchas methylamine, di
ternary ammonium salt of' another heterocyclic
ethylamine, trimethylamine, triethylamine, )pi-"K
4:5ttperidine, pyridine, or sodium ethylate, or ethan
base-containing a reactive. methyl group, as for
‘ example‘quinaldine iodo alkylate, in the presence
olamines. 'Theamount of condensing agent used
of .-an alkaline condensing agent, according to the
is preferably a quantity at most equivalent to,
following formula:
5
4
3
50'.
2
I.
55
60.,i-that1tofnthe ibase-twhichl is. ‘used, ,because. angina
Thisprocess may be carried outwith all hetero-. 60
2
2,131,864
cyclic bases containing a reactive methyl group,
in particular with mono- and polynuclear thia
zoles, selenazoles, 2- and 4-methylquinolines.
and Rs linked to the nitrogen atoms of the hetero
cyclic rings linked together by the heptamethenyl
chain represent alkyl. X represents an anion,
for instance those disclosed above.
The dyes are obtainable according to the de
alkylamines and sodium ethylate are suitable al
sired solubility in form of the bromide, iodide,
kaline condensing agents.
The heptamethinecyanine dyestuffs obtained perchlorate etc. and are used in a quantity such
as is usual for the known sensitizing dyes. This
according to the present invention have the fol
quantity may amount to about 0.5 to 2 milli
lowing general formula, from which the com
10 prehensive application of this new process may grams per 1 kg. of emulsion ready for being cast 1O
which contains about 9 per cent of gelatin, 4.5
be recognized:
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 suit
able amount will in each case be found by a 15
15
For example pyridine, piperidine ethanolamines,
few comparative experiments.
20 Y and Z are S, Se, —CH=CI-I
R1, R2, R3, R4 represent hydrogen, alkyl or aryl,
25
or, if desired, R1Rz and R3R4 in combination
represent unsubstituted or substituted phenyl
ene, naphthylene or other polynuclear arylene
groups. (Alkyl, aryl, alkoxy, thioalkyl, seleno
alkyl, substituted or unsubstituted amino
groups belong to the substituents contem
plated.)
'
.
For the unsymmetrical character of the dye
30
it is necessary, that Y and Z or R1, R2 and R3,
R4 are different from each other.
R5 and R6 represent alkyl,
1
X represents an anion for'instance, Cl, Br, I,
C104, CH3—-C6H4—-SO3, CH3—SO1, C2H5--SO4.
The quinoline nucleus which results in case of
Y being —CI-I=CH-- may be linked to the poly
methenyl chain in 2 or 4 position. The hydro
gen atoms of the heptamethine chain may be
substituted by alkyl groups, as for example
40 methyl or ethyl.
In the general formula Y and Z may represent
sulfur, selenium or the vinyl group CH=CH.
In the case of dyes in which, for instance, a
thiazole nucleus and a selenazole nucleus are
45 linked together by a heptamethenyl chain R1, R2,
R3 and R1 may represent hydrogen, or they may
represent alkyl, or aryl or carbethoxy. In com
bination RIR2 and R3R4 may represent phenylene,
or naphthylene or a polynuclear arylene group,
50 for instance, the corresponding radical of anthra
cene, chrysene, ?uorene or acetnaphthene. In
the case of Y being sulfur, Z being selenium,
R1R2 and R311; being phenylene, the dye is a
[benzthiazole- (2) l] - [benzselenazole- (2!) ] --hep1ta -
v55
methinecyanine. If Y is selenium, Z is sulfur,
R1R2 is phenylene, and R3 and‘R4 are hydrogen
the dye is a [benzselenazole-(Z) l-[thiazole-(2) ]
The dyes may
be added to the emulsion in form of solutions.
Suitable solvents are the alcohols, for instance,
methyl or ethyl alcohol which may be used an
hydrous or diluted with water. The dyes are 20
applied to the emulsion during any stage of its
production, however, they are preferably added
to the ?nished emulsion before casting.
The dyes may likewise be added to the emul
sion by bathing the ?nished photographic ma 25
terial in a bath in which the dye is dissolved.
Such a treatment may be as follows:
The pho
tographic material to be sensitized is bathed in
a solution containing 1 milligram of [ZS-ethyl
benzselenazole-(2)l - [1 - ethyl-quinoline - (4) l
30
heptamethinecyanine iodide in 500 to 1000 cc. of
an aqueous solution of methanol of 50 per cent
strength for about 5 minutes. The material is
then dried, whereupon it is ready for use.
The following examples serve to illustrate the 35
invention.
'
Example 1.—In order to obtain [3-ethyl-benz
thiazole- (2) ]— [3 - ethyl-{naphtho - 1’.2': ‘LS-thia
zole}-“(2)vl-heptamethinecyanine iodide having
the formula:
02135
‘
I
C2115
15 grams of 2-methylbenzthiazole ethiodide are
boiled with 20 grams of e—phenylimido-a-phenyl
amido-a, y-pentadienehydrobromide in 50 cc. of
alcohol and then mixed with 1.5 cc. of piperidine;
the mixture is boiled for further 30 minutes and
then cooled. By adding 50 cc. of a solution of
potassium iodide of about 2 per cent strength,
the dyestuff (intermediate product) correspond
ing probably with the formula:
heptamethinecyanine. This not only illustrates,
the dyes which are contemplated by the inven
60 tion but also the nomenclature.
—S
60
In the case of
Y being CH=CI-I, Z being sulfur and‘ R1,R2,R3,R4
being hydrogen, there result dyes in which a
pyridine nucleus is linked together with a thia
zole nucleus by a heptamethenyl chain. If Y is
65 CI-IzCI-I, Z is sulfur, R1R2'is phenylene, R3 and
R4 are hydrogen, there results a dye in which a
H
C2115
I
separates in green ?occules. Recrystallization 65
from alcohol yields green needles. The alco
quinoline nucleus is linked together with a thia
zole nucleus by a heptamethenyl chain and is
called a [quinolinel-[thiazole~(2)l-heptameth
inecyanine. The quinoline nucleus may be linked
in 2 or 4 position. The benzene rings and so
on fused on the heterocyclic rings containing a
nitrogen atom may be substituted for instance
holic solution has an absorption maximum at
by alkyl, alkoxy, aryl, halogen, substituted or
tained. On cooling, [3-ethyl-benzthiazole-(2)l
unsubstituted amino groups.
[3-ethyl-{naphtho- 1’.2"»:4.5-thiazo1e}-(2‘)‘l-hep - 75
The radicals R5
about 6251111.
1.8 grams of this dyestuff (intermediate prod
uct) and 1.2 grams of 2-methyl-[naphtho
70
1'.2':4.5-thiazole]-diethylsulfate are dissolved
in 10 cc. of diethylamine. This mixture is main
tained boiling until a dark blue coloration is ob
2,131,864‘
tamethinecyanine iodide separates on addition of
, about 5 cc. of a 5 per cent solution of potassium
iodide; brownish green little rods crystallize ‘from
alcohol.’
Incorporated in a silver bromide emulsion con
3 .
coholic solution have an absorption maximum at‘
about 638,114!“
4 grams of this intermediate product, 2.5 grams
of 2,4-dimethylthiazole ethiodide and 2 cc. of
diethylamine are boiled in 10 cc. of alcohol until
taining about 4 per cent of silver iodide the dye 7 the mixture assumes an intense blue color. After
imparts to it a range of sensitivity from about cooling, the dyestu? is precipitated by adding 3
65°[LM to 930m). with a maximum of about 830ml.
' Example -
2. -- [3-ethyl-benzthiazole- (2) l-[3
ethyl - 5.6 - dimethyl '- benzselenazole ‘- (2) l - hepta
methinecyanine iodide having, the‘ formula:
cc. of a 10 per cent solution of sodium per
chlorate.
Druses of green crystals are obtained
by recrystallizing from alcohol.
10
Incorporated in a silver bromide emulsion con
taining about 2 per cent of silver iodide ‘the dye
imparts to ita range of sensitivity from> about
600W to 880/L/L with a maximum at about 785%.
Example 5.-—In order to obtain [3-ethyl-benz
15
selenazole-‘(2.)'l-[1-ethyl-quinoline-(4) l - :heplta
is obtained according to Example 1 from the in
termediate product speci?ed therein and, the
20 equivalent amount of 2,5,6-trimethylbenzselena
zole ethiodide. The dyestuifcrystallizes in green
crystals. during the reaction.
methinecyanine iodide corresponding with the
following formula:
7
———~Se
l“5
1
_
<Z>
5
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
650% to 900W with a maximum of about 825/14},
- Example ~ 3.-- [3-ethyl-benzthiazole-(2) l-[l
ethyl-quinoline- (4) l-heptamethinecyanine
chlorate having the formula:
per‘
4,5 grams of 2~methylbenzselenazole ethiodide
and 5 grams of e-N-methylphenylimido-a-N
methylphenylamido-u wmentadienehydrobromide
are boiled for 30 minutes in 25 cc. of alcohol,
while adding 1 cc. of triethanolamine. On cool 3O
30
ing, the hexamethine dye corresponding prob
ably with the formula:
Calls
is obtained by heating'LS grams of phenylamido
l-ethyl benzthiohexamethine iodide (interme
diate product), obtained according to Example 1,
a
in 10 cc. of alcohol together with 1 gram of lepi
dine ethiodide until the whole is dissolved and,
after adding -1 cc. of diethylamine, boiled until
the reaction mixture assumes a dark green color.
By the addition of 5 cc. of a 10 per cent aqueous
solution of sodium perchlorate, the dye sepa
rates.’ It crystallizes from“ alcohol in small
brownish red plates.
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
‘ 650,1l/L to 920/”). with a maximum of about 825ml.
‘ Example -4.—'In order to produce the dyestu?‘
corresponding with ‘the forumla:
.7 ——Se
i
6
G104
>
,
2‘ grams of the dyestuff (intermediate product)
thus obtained and 1.5 grams of lepidine iodo
ethylate are dissolved in 20 cc. of alcohol in the 45
vwarmth and boiled after the addition of 1 cc.
of triethylamine until the separation of [Ii-ethyl
benzselenazole - (2) ]-[1 - ethyl-quinoline - (4) l
heptamethinecyanine iodide commences. The
dyestuff crystallizes from alcohol in brown
crystals.
Incorporated in a silver bromide emulsion con
l
‘ 01135
at about 610/.LIL.
taining about 2 per cent of silver iodide the dye
imparts to it a range of sensitivity from about
5
660% to, 930W with a maximum at about 825HM.
vExample 6.—In order to produce [3-ethyle5
5
/
separates in green needles. The alcoholic solu 40
tion of the dyestuiT has an absorption maximum
I?C 2115
m e t h o x y-benzselenazole—(2) l-[3-ethyl-5-di
60‘a 17.5 grams of 2-lmethylbenzselenazole ethiodide
ethylamino - benzthiazole - (2)] - heptamethine -
cyanine iodide having the following formula:
7
1
Swc
.
and 20 grams of e~phenylimido-u-phenylamido~a,
'y-pentadiene hydrobromide' are dissolved in 50
cc. of alcohol in the warmth, mixed with 1.5 cc.
of piperidine and boiled for half an hour. After
C2115
the intermediate dyestu?” corresponding probably
with the following. formula:
cooling, the, resulting vphenylamido-l-ethylbenz
selenohexamethine iodide is precipitated by the
addition of 50' cc. of a 5 per cent aqueous solu
‘tion of potassium iodide. Recrystallization from
l‘ alcohol yields dark green crystals which in al
is produced from 2-methyl-5-methoxybenzselen
2,131,864
azole ethiodide according to Example 5 and has
an absorption maximum of about 615/14‘.
2 grams oi’ this dyestuff are dissolved with 1.5
grams of 2-methyl-5-diethylaminobenzthiazole
(2) l-heptamethinecyanine iodide having the fol
lowing formula:
HaC- 6
5
4
3
ethiodide in 10 cc. of hot alcohol and gradually
mixed with 4 cc. of an alcoholic solution of so
dium ethylate (containing 3 per cent
and kept boiling, until the mixture
bluish green color. The dye which
tated on cooling crystallizes from
of sodium)
assumes a
is precipi
alcohol in
copper-brown crystals.
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
‘700W to 900W with a maximum at about 855%.
Example 7.—In order to obtain [3-ethyl-benz
thiazole-(Z) l-[3-e t h y 1-{naphtho-2’.1’:4.5-thi
azo1e}- (2) l-a-methyl-heptamethinecyanine
io
C2115 I
(IJZHB
a mixture of 4 grams of toluquinaldine iodo
ethylate and 5 grams of e-N-methylphenylimido
a-N-methylphenylamido-a-'y-pentadiene hydro
10
bromide are boiled in 25 cc. of alcohol and, after
the addition of 1 cc. of diethylamine kept for
about 5 hours on the steam bath. After cooling,
the reaction product which separates is recrys
tallized from alcohol. The dye (intermediate
product) obtained corresponds probably with the
formula:
HaC
dide corresponding with the formula:
N/ CH=CH—CH=OH—CH=CH—III
czHs/ \I
CH8
and forms green crystals, the alcoholic solution 25
of which has an absorption maximum at about
605;:44.
2 grams of the dye (intermediate product) thus
4 grams of Z-methylbenzthiazole ethiodide are
boiled with 5 grams of e—phenylimido-a-phenyl
a m i d o-'y-methyl-u,'y-pentadiene hydrobromide
(obtained from aniline, 'y-picoline and cyanogen
bromide analogously to the unsubstituted com
35 pound, according to the process described by
Konig, in Journ. f. prakt. Chemie, 69, p. 105) in
20 cc. of alcohol, mixed with 0.8 cc. of piperidine
and heated for 30 minutes on the steam bath.
After cooling the dark blue mixture, 20 cc. of a
5 per cent aqueous solution of potassium iodide
are added, and the hexamethine dye (interme
diate product) formed and corresponding with
the following formula:
obtained are dissolved with 1.5 grams of Z-meth
ylbenzthiazole ethiodide in 10 cc. of boiling alco
hol and gradually mixed, while boiling, with
30
about 3 cc. of a 3 per cent solution of sodium
ethylate. Boiling is continued until the mixture
assumes a greenish blue color. The dye crystal
lizes from alcohol in green needles.
35
Incorporated in a silver bromide emulsion
containing about 2 per cent of silver iodide the
dye imparts to it a range of sensitivity from
about 630a,“. to 930/.L/L with a maximum at about
828,14”.
_
Example 9.—In order to produce the dyestuff
having the formula:
~
40
'
'
45
0.5 cc. of triethanolamine is added to a boiling
solution of 4 grams of 2,5,6-trimethylbenzthi
azole ethiodide and 5 grams of e-N-methyl
is ?ltered off. The dyestuff crystallizes from al
phenylirnido - a - N-methylphenylamidoway-pen
cohol in blue needles. The alcoholic solution has
an absorption maximum at about 620M.
1 gram of the intermediate product and 0.8
boiling continued for one hour.
gram of 2-methyl-[n.aphtho-2’.l':4.5-thiazolel
ethiodide are dissolved in 10 cc. of boiling alcohol
and kept boiling for 10 minutes, while adding
0.7 cc. of diethylamine. The resulting [3-ethyl
benzthiazole- (2) l .- [3'— ethyl-(naphtho-2’.1': 4.5
thiazole) - (2) ] - 6 — methyl - heptamethinecyanine
iodide is recrystallized from alcohol thereby yield
ing druses of dark brown crystals.
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
630% to 920/.LM with a maximum at about 84:0,LLIL.
Example 8.—In order to produce [3-ethyl-6
In e t h y l-quinoline-(2) l-[3-ethyl-benzthiazole
70
50
tadienehydrobromide in 25 cc. of alcohol, and
On cooling, the
intermediate dyestuff separates in form of bluish
green needles. 1 gram of this dyestuff is heated
for 10 minutes with 1 gram of 2.4-dimethylthi
azole ethiodide in 10 cc. of alcohol, while adding
1 cc. of diethylamine, until the mixture assumes
a bluish green color. On cooling, the dyestuff
crystallizes in brownish green crystals.
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
600W to 910W. with a maximum at about 800%.
Example 10.--In order to produce [3-ethyl-5
65
diethylamino-benzthiazole-(2) l-[3-ethyl-q u i n
o l i n e-(4) l-heptamethinecyanine perchlorate
corresponding with the following formula:
< > 0 IHI
70
lN/
75
75,
2,131,864 "
': ‘i,_.grams-rof ‘ >2.-methyl1-5adiethylamidobenzthiazole
i
.-..methine-N-methylanilido iodide, as obtained ac
. cording-to ‘Example 6, and 1 gram of 2~methyl
.- ethiodide. are boiled with?gramsofr (N-methyl
,»..phenylimido) )1 a: - (Nrmethylphenylamido) -ra,'y~
.fl-phenylthiazole methiodide. are boiled for about
,apentadiene.hydroebromidein 20 “cc. of alcohol,
5~minuteain 10cc. of alcohol, while adding 1 cc.
l,“ 5 while adding “about,1_.cc. of .triethanolamine, - of an alcoholic solutionof trimethylamine of~50 ._
until the mixture ‘assumes a dark blue color. _ “per ‘ cent . strength. a The dyeseparates in form of‘
The resulting hexamethine dyestuffiinterme ; green crystals.
a’
diate product) corresponding probably with the . I: Incorporated ‘in a‘silver vbromide emulsion con
’..taining} about. ,2- per cent of .silver‘ iodide 'the
.dye impartsto it» a'rangeyofsensitivity from‘ l0.
formula:
'
.
.Emwmple, 13.-;In. order- to-produce [3-ethyl- v
benzs'elenazole-(2)1-[3-ethyl-pyridine-(2) l-hep
tamethinecyanineperchlorate corresponding prob-v
is I precipitated in green ?occules, while adding“ . ably with the formula:
10 cc. ‘of an aqueous solution of sodium perchlo
rate of 10 per cent strength. The alcoholic so
lution of the product has an absorption maxi
$1320
mum at about 635%.
"
-
20
In order to obtain [3-ethyl-5-diethylamino
benzthiazole-(Z) l-.[3.-.et,hyl,-q ui n o1 in e-(4)’]
I'heptamethinecyanine perchlorate,‘ 1.5 grams ‘of ‘ TV‘CzHs
the intermediate product are‘ heated with ‘2.5
C104,
(52H!)
1 gram ‘of "“N-ethylbenzsele‘nohexamethinelN
5-»:grams-oflepidiné ethiodide in'lO cc. of ‘alcohol, _ methylanilido iodide (made according .to Ex
while gradually ‘adding about . 1" cc. ‘ 1‘of diethyl
ample5) and 1 gram of uepicoline ethiodide are
carefully boiled in 5 cc.,of pyridine, until the
1~:amine,1until.the mixture assumesa greenish blue
,icolor; The dyestuff separates in dark ?occules
on'the addition 0f11Q cc. ofya, solution 'of sodium
$26130, perchlorate.
;.A bluish-black crystalline powder
.is .obtainedvby recrystallization from alcohol.
‘ ‘
mixture .assumes a dark blue color. When add
. ing 5 ‘cc. of an aqueous solution of sodium per
{chlorate of “10 per cent strength, the dye is’ 30
precipitated in ‘blue ‘floccules.
Incorporated in a silver bromide emulsion. con
‘incorporated in a silver bromide emulsion con
taining about ‘2 per cent of ‘silver iodide the dye
imparts to it a range ofsensitivity from about
taining'about? per cent of silver iodide‘the‘ dye
imparts to it‘ a range of sensitivity from about
3335. “650w
to 1000p.” with a maximum at ab0ll13>365mm ‘550ml. liq 81.01114; Wi’tha maximum at about 740,044.
Example LIL-Theintermediate product 0b
"Example 14.—.-In- [order to obtain [3-ethyl-5
ntained-according.toExample 10 may be converted _‘e'thoxy - 6 — methyl '- benzthiazole -(2) 1-[3-ethyl
.‘according ‘to- the manner speci?ed therein-by 5.fiédimethylubenzselenaZole-i(2) ]- heptamethine
,means ,;“0f .2.‘lfdimethylthiazole;methiodide ~:_into
,‘[3,-¢e :t hy- l-5.-.diethylaminorbenzthiazole-.(2) ]- [3-
cyanine iodide probably havingv the following for
m‘ula;
Hao~6/7\—-s
- ’
se—- 7 6
0113
I l i
I1 l
H50,0—\4/>1§I<—o1a_o11 (DH-CH CH_OH CH'—\I?‘I/\1/ CH3}?
5"
‘ $545
>2.
_
__
_
_'_'
_.._Z
CzHs I
5_
45
CQHQ
ethy1-4-m e t h y l-thiazvole-(2) l-heptamethine- ~ ll;._-~grams of . 2.6edimethyl-5-ethoxybenzthiazole
“r0 cyanine perchlorate corresponding probably with ~.ethiodide and 5 grams of E-N-methyl-phenyli
" ‘°
the formula:
'
midoim-N-methyl - Dheny1amido-a,'y - pentadiene
_._-S
-
.
":4
>
-
v
..
S_'_CB
till...
(H5C:)2N— 4 \lg/~0H=<JH—0H=0H~011=o11—011=\l§I/ ~
5: CgH5/ \C104
7
(I311:
Recrystallization from alcohol yieldsbronze col“.50 ored crystals.
‘
‘
50
_
3
'
N55
v
‘
‘
hydro-bromide-are heated with 15 cc. of pyridine
‘for about 1 'hour onthe steam bath, or the mix-
Incorporated in a silver bromide emulsion con-
I ture-is boiled for- a-short time, say 3 to 5 minutes. 60
taining about 2 per cent of silver iodide the dye ' Thel‘separationliof, the intermediate product may
'~ imparts to it 'a‘l’range of~~sensitivity ‘from about ~be'completed by the-addition‘of about 10 cc. of
" 600,1tuto‘920pu wltha maximum at about 820W‘. vsaysolution ‘of potassium‘ iodide.» P The intermedi
‘,.,G5‘
'
Example ‘~12.—In order yto‘l-obtain‘ [3\-ethyl-'5-
ate dyestuff having the following formula:
methoxy-benzselenazole- (2) ]- [3-ethy1-4-phenyl-
H30
thiazole-(2) l-heptamethinecyanine iodide corre--
.65
—s
sponding probably with the following formula:
W70
‘E
7
Se
6
1
H300 54
S_OH
_
I1
5
féfcmc?-(lH=OH-CE=CH"CH=<§T}C_O0H‘
/ \ .
. GsHt -
l I
(5
‘H3
#5“ 1 l3 gram \ 40f IlN-ethyl-Gemethoxybenaselenohexa
‘
H6020
‘
g
\ / CH=OH——CH=OH——CH=CH—N—O&H5
./N<
._
(LJHS
C2H5
I
,
_
.70
crystallizes from alcohol in form of a blackish
green crystal powder. The alcoholic solution of
rtheicompound has .an. absorption maximum at
about 610%.. 1 gram of the resulting'interme
75
2,131,864
6
mediate product in admixture with the same ‘ mido-my-pentadienehydrobromide are boiled with
amount of 2.5.6-trimethylbenzselenazole ethio- ’ 2 gram of triethanolamine for 2 hours In 20 cc.
of alcohol.
On cooling'the dark blue mixture,
dide is boiled in 10 cc. of alcohol while adding
0.5 cc. of triethanolamine, until the dyestuff is
the intermediate dyestuff corresponding probably
precipitated in green crystals.
with the following formula:
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
750W to QOOIL/L with a maximum at about 840%.
..10
Example 15.-In order to obtain [3-ethyl
10
CH3
benztliiazole- (2) ]- [3-ethyl - 5 - carbethoxy-thia
zole-(2)l-heptamethinecyanine iodide corre
sponding probably with the following formula:
is precipitated in form of green crystals.
The
15
021-15
20
OH:
alcoholic solution thereof has an absorption max
-imum at about 655%.
benzthiazole iodo ethylate and e-N-methyh
1 gram of this intermediate product and 1 gram 25
25 phenylimido-a-N-methylphenylamido bromide in
of 2-methyl~6-methoxybenzthiazole ethiodide are
alcoholic solution analogously to the method de
heated, until dissolution occurs, and then mixed
scribed in Example 10 and‘ 0.7 gram of 2.4-di
with 2 cc. of an alcoholic solution of trimethyl
methyl-5-carbethoxythiazole methiodide are dis
amine of about 50 per cent strength, whereby the 30
solved in 10 cc. of alcohol in the warmth and
color changes to green. After cooling [l-methyl
30 boiled for about 5 minutes after the addition of
quinoline- (4) ]- [3-ethyl-S-methoxy-benzthiazole
about 1 cc. of diethylamine. On cooling the dye
(2)l-heptamethinecyanine iodide. is precipitated
stuff separates’ in form of a bluish black crystal
as a bluish black crystalline powder.
_
line powder.
Incorporated in a silver bromide emulsion con
Incorporated in a silver bromide emulsion con~' 35
35 taining about 2 per cent of silver iodide, the dye
taining about 2 per cent of silver iodide, the dye
imparts to it a range of sensitivity from about imparts to it a range of sensitivity from about
650% to 900W. with a maximum at about 800/141“ 650W. to 950/”1. with a maximum at about 830%.
1 gram of N-ethylbenzthiohexamethine-N-meth
ylanilido iodide as obtainable from 2-methyl
Example 16.—[3-ethyl - benzthiazole- (2) l- [3
ethyl - {tetrahydronaphtho - 2'.l' :45 - thiazole}
40
(2)1-heptamethinecyanine iodide corresponding
Example 18.—In order to obtain [1-ethy1—quin~ 40
oline -<2)1-[3.5 - dimethyl - thiazole-(Z) l-hepta
with the following formula:
45
50
50
is obtained in the manner described in Example
15, from Z-methyl-tetrahydronaphtho-2’.1’:4=.5
thiazole
ethiodide
methinecyanine iodide corresponding probably
with the following formula:
55
and V N-ethyl-benzthiohexa
methine anilido iodide.
_ 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
60 670% to 880,114}. with a maximum at about 615%.
Example 17.—In order to obtain [l-methyl
quinoline- (4) l- [3-ethyl-6-methoxy-benzthiazole
(2)1-heptamethinecyanine iodide corresponding
probably with the following formula:
60
5 grams of quinaldine ethiodide together with 4
grams of e-N~methylphenylimido-a-N-methyl
phenylamido-ow-pentadiene hydrobromide are 65
65
6
5
70
4
70'
C 1115
4 grams of lepidine methiodide and 5 grams of
75
e-N—methyl-phenylimido - a - N - methylphenyla
boiled for ‘2 hours in 20 cc. of alcohol while adding
» 2 cc. of triethanolamine.
On cooling, N-ethyl» 76
2,131,864
quinohexamethine-anilide iodide is’ precipitated
7 .
diate product corresponding probably with the
in green needles; the alcoholic solution has an
absorption maximum at about 610W. '
formula:
“ In order‘to produce the unsymmetrical cyanine
,S
dyestu? havingv the above formula, 1 gram of the
intermediate dyestu? is boiled with 2.4-di
methylthiazolelmethiodide in ‘10 cc. of alcohol,
mixed with about 1 cc. of diethylamine and kept
boiling, until the mixture assumes a dark blue
10 color. “On cooling, the dye is precipitated in
green ‘needles.
V
..
>
OzH5\I
OH.
‘
a
separates in form of blue-black ?akes. Recrys
1
tallization from alcohol yields steel blue little
‘‘ Incorporated in a silver bromide emulsion con
taining' about 2 per cent‘ of silver iodide, the dye
rods. "The alcoholicgsolution of the compound
15 VOOWto- 900% with a maximum ‘at about 84IO/L/L.
,1 gram of the intermediate product is boiled’
imparts to it a‘range of sensitivity from about . has an absorption maximum at about 605%.
with 0.8 gram of 2-methyl-5.6-methylene-dioxy- ‘
' Example 19.-—The dye [3-ethyl-5-ethoxy-benz
benzthiazole ethiodide in 10 cc. of alcohol while
‘selenazole ‘-(2) l-[3'-ethyl-5-chloro - 6 - methoxy
adding about 1 cc. of diethylamine, and boiling
benzthiazole —(2)‘]- heptamethinecyanine ‘ iodide
is continued for about 10 minutes. The dye
separates in form of green crystals.
corresponding to the‘ formula:
20
76
1
25
“
"
c6191
;
‘
~
‘
20
OOH:
I
-
CaHa
may be produced as follows:
4 grams of Z-methyl-5-ethoxy-benzselenazole
ethiodide» are dissolved with 5 grams of e-N
30 methyl-phenylfimido~wN-methyl-phenylamido -
wry-pentadiene hydro-bromide in 30 cc. of alcohol.
After the addition of 0.7 cc. of benzylamine the
mixture is heated to 100° C. for about 3 hours.
On cooling the intermediate product separates in
.35
40
‘
‘ 02135
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
GOO/1,,“ to 90011.,“ with a maximum at about 825/.LIL. .?
Example 21.—-The dye [3-ethyl-5-ethoxy-6
methyl - benzthiazole —(2)'l - [3-ethyl ~{acenaph
theno-5’.4’ :4.5-'thiaz'ole}- (2) l-heptamethinecya
nine iodide corresponding with the formula:
I
40
form of green crystals‘. Recrystallization‘ from
alcohol yields green leaves.
‘
45 r ‘ 1.1 grams of the intermediate product,10.8 gram
of ,‘2- methyl-5-chloro-6-1methoxy - benzthiazole
ethiodide and 10 cc. of alcohol are heated, while
adding 2 cc. of an alcoholic solution of trimethyl
amine of 50 percent strength, until the dye sepa
50 rates in form of crystals. ‘Recrystallization from
methanol yields brownish green crystals.
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
55
670 to 900w, with a maximum at about 830%.
may be prepared as follows:
.
.
V
r
2 grams of 2.6-diethyl-5eethoxy-benzthiazole
ethiodide. are heated with 2.5 grams of e-N
methyl-phenylimidoéwwpentadiene ‘ hydro-bro
mide in 20 cc. of alcohol until dissolution occurs,
and then there are added 2.5 cc. of an alcoholic
solution of sodium ethylate of 5 per cent strength.
The yellow red solution changes its color imme
diately to blue-red and the intermediate ‘product
corresponding probablylwith the following ‘for
mula:
‘
r
7
55
Example 20.--The dye [3-ethyl-benzthiazole
(‘2)l-[3-e1thy1-5.6 - methylene - .dioxy - benzthia -
zole-(2) l-heptamethinecyanine
60
iodide
‘ corre-'
sponding with the following formula:
separates in form of green crystals. Heating is
65
is obtained by heating 4 grams of 2-methylbenz- V
continued for a short period and the product is
thiazole ethiodide with 5 grams of e-N-methyl
?ltered off. The alcoholic solution of the com
phenylimido-a-N-methyl - phenylamido-wy-pen
70 tadiene hydro-bromide in 20 cc. of alcohol to 100° pound has an absorption maximum at about
610,411,,
7
70
C. until the mixture assumes a dark blue color
1 gram of the intermediate product and 1 gram
(about 3 hours), while adding 2 cc. of an alcoholic of Z-methyl — acenaphthenethiazole ethiodide
‘ solution of trimethylamine of 50 per cent'
strength. 0n addition of about 5 cc. of a 5 per when heated in 15 cc. of alcohol with theaddition
75 cent solution ‘of potassium iodide the interme
of 1 cc. of diethylamine yield the above dye which
separates in form of crystals on the wall of the re 75
2,131,864
8
2. The processor producing an unsymmetrical
action vessel. Recrystallization from alcohol
yields green crystals.
heptamethinecyanine which comprises reacting
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
heterocyclic base selected from the class consist
690 to 930% with a maximum at about 850114!“
with an amount of e-phenylimido-a-phenylami
Example 22.—The dye [3-ethyl-benzthiazole
(2) l-[3-ethyl-{anthraceno - 1’_.2' :45 - thiazole}
(2) l-heptamethinecyanine iodide corresponding
10 with the formula:
6 7
S
I
ing of oc-Ill?thYl-thlELZOlGS, a-methyl-selenazoles,
a-Il'lBthYl-Qllll'lOlll’lES
and
y-methyl-quinolines
do-wy-pentadiene hydrohalide substantially sur
passing the quantity equivalent to that of the
base in the presence of an amount of alkaline
condensing agent not greater than the quantity
equivalent to that of the base, and. condensing the
S
I
CaHs
on a quaternary ammonium salt of a nitrogenous
CZHB
intermediate product thus obtained with another
quaternary ammonium salt of a nitrogenous het
erocyclic base selected from the class consisting .15
of a-methyl-thiazoles, a-methyTl-selenazoles, a.
methyl-quinolines, and 'y-methyl-quinolines in
the presence of an alkaline condensing agent."
3. The process of producing [3-ethyl-benzse
lenazole- (2)'lj- [3-ethy1-4-methyil - thiazole-(2) ]
20
may be obtained by making the intermediate
product as disclosed in Example 20 and using 1
cc. of monomethylamine as condensing agent. 1
gram of the intermediate product, 1 gram of 2
25
e-PhEl’lYl-il’flldO - a - phenylamido-axy -pentadiene
hydrobromide in the presence of an amount of
piperidine not greater than the quantity equiva
methyl- [anthraceno- 1'.2' 24.5-thiazole-p-toluene
lent to that of said base, and condensing the in
sulfo ethylate (2-methyl-anthrathiazole p-tolu
termediate product thus obtained with 2.4-di
methylthiazole ethiodide in the presence of di
enesulfo ethylate) , and 1 cc. of diethylamine are
boiled in 10 cc. of alcohol for about 10 minutes.
On cooling the dye separates in form of greenish
brown crystals. From alcohol the dye crystallizes
in form of a copper colored crystal powder.
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
85 700ml to 900W with a maximum at about 835”.
What I claim is:
1. The process of producing an unsymmetrical
ethylamine.
4. The process of producing [3-ethyl-benzse
methinecyanine iodide which comprises reacting
on Z-methyl-benzselenazole ethiodide with e-N
methylphenylimido-u-N-methylphenylamido-a.-y
pentadiene hydrobromide in the presence of an ,
heptamethinecyanine which comprises reacting
on a quaternary ammonium salt of a nitrog
triethylamine.
consisting of w-methyl-thiazoles, a-methyl-selen
azoles, m-methyL-quinolines and 'y-methyl-quino
lines with an e—phenylimido-a-phenylamido-axy
pentadiene hydrohalide in the presence of an
amount of alkaline condensing agent not greater
than the quantity equivalent to that of the base,
and condensing the intermediate product thus
obtained with another quaternary ammonium
salt of a nitrogenous heterocyclic base selected
from the class consisting of ao-methyl-thiazoles,
a-methyl-selenazoles, a-methyl-quinolines and "y
methyl-quinolines in the presence of an alkaline
condensing agent.
3.9
lenazole - (2) 1- [1 - ethyl-quinoline-(4) l-hepta
amount of triethanolamine not greater than the
quantity equivalent to that of said base, and con
densing the intermediate product thus obtained
with lepidine iodo ethylate in the presence of
enous heterocyclic base selected from the class
.20
heptamethinecyanine iodide which comprises re
acting on Z-methyl-benzselenazole ethiodide with
40
5. The process of producing [3-ethy1-benzthi
azole- (2) l—[3-ethyl—{naphtho-2'.1’:4.5-thiazole}
(2) I] -5-methyl—heptamethinecyanine iodide which
comprises reacting on 2-methylbenzthiazole eth
iodide with e-phenyl-imido a-phenylamido-y
methyl-axy-pentadiene hydrobromide in the pres
ence of an amount of piperidine not greater than
the quantity equivalent to said base and con
densing the intermediate product thus obtained
with 2-methyl- {naphtha-2 ’ .1’ :4 .B-thiazole} -eth 50
iodide in the presence'of diethylamine.
WALTER ZEH.
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