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Патент USA US2412815

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Patented Dec. 17,‘ 1946
r
2,412,815
a UNITED STATES PATENT’OFFICE
2,412,815
,
DICARBOCYANINE DYES
John David Kendall and Harry Derek Edwards,
Ilford, England, assignors to Ilford Limited,
Ilford, England, a British company
No Drawing.
Application Decemberv 17, 1943,
?e11~19a;l3No. 514,667. In Great Britain January
4 Claims.
1
(Cl. 260-240)
‘
2
This invention relates to the production of dicarbocyanine dyes and particularly to the pro-
‘
to compounds of general Formula D by treating
them with a sodium alkyl mercaptide and an
duction of symmetrical dicarbocyanine dyes
which are useful as optical sensitisers for silver
alkyl mercaptan under pressure.
.
Beta-alkyl-thio acrolein di-alkyl mercaptals
can be made by treating a compound of Formula
,
halide photographic emulsions.
5
In co-pending application Serial No. 514,666
A in which the groups R are alkyl groups with
?led December 17, 1943, corresponding to British
alkyl mercaptan in the presence of a basic con
application No. 14/43, there is described the production of compounds of the general Formula I:
densing ‘agent under pressure.
According to the present invention, symmetri
XRl
10 cal carbocyanine dyestuffs are obtained by con
densing a compound of general Formula I with
an alkyl or aralkyl quaternary salt of a hetero-.
XRl
cyclic nitrogen compound containing a reactive
where the groups R1 represent alkyl groups and
methylene group (which term includes a methyl
preferably ethyl groups, and the groups X are 15 or mono-substituted methyl group) substituted
R‘s_OH=CH_Cé
'
(I)
both oxygen atoms or both sulphur atoms. Com-
in the iii-position t0 the quaternary heterocyclic
pounds of the general Formula I can be made,
nitrogen atOm-
as described in the aforesaid application by treating with an alkyl mercaptan, in the presence of
The course of the reaction is believed to be as
follows:
V
‘
‘
-
I\
| \
IXRI \\ $2 FWD-n}
§“1'1“-'F'§1§i'~c11=on-c : + Etc-62
'
TDD“: lib/L4"""" '3
lXR /
R/ \A
N=~=é~Q
Rs
l
I :1
a
|
I /I
'5 """""""" ‘f
?e ...... lei
'
:"D"1 1,“
R2 r"D"1
N-—-(5=C-CH=CH—OH=C~—C
a
1'\I\+ HA + men + zitlxn
Re
(n)
A
an acid condensing agent, a compound of one of
In the foregoing formulae R2 and R3 represent
the Formulae A, B. C‘, 01‘ D:
"D alkyl or aralkyl groups, R3 may also be an une
SR
saturated aliphatic group, e. g. allyl, or a sub
OHzCEFC?
(A
*
stituted alkyl group, e. g. hydroxyalkyl, D rep
)
resents the residue of a heterocyclic nitrogen
nucleus and A represents an acid radicle.
SR
OR
-»
40
CH:CH_C?
—
(B)
0R
-
.
.
.
taming the necessary reactive methylene (or
methyl or mono-substituted methyl) group de
on
r rived from the following heterocyclic nitrogen
RO_CE=C;I_C§
(C 40 compounds: substituted and unsubstituted thia
)
OR
OR
RS_CH=CH_C§
_
.
.
.
zoles,th1azol1nes, oxazoles, oxazolmes, selenazoles,
selenazolines, pyridine, quinoline, indolenine, di
azines (e. g. pyrimidine and the diazines de
(D)
OR
‘
Examples of heterocyclic nitrogen compounds
which may be employed are quaternary salts con
_
or by treating with an alkyl mercaptan in the
presence of a baslc condensing agent under PresSure, a Compound of Formula A.
scribed in British patent speci?cation No. 425,
50 609), thiodiazoles and quinazoline and the cor
responding substituted and unsubstituted. poly
cyclic compounds such as the benzthiazoles,
'naphthathiazoles and anthrathiazoles and the
v__ corresponding polycyclic oxazoles and selenazoles.
C'qmpounds 0f the general Formula A may be M iSuch heterocyclic compounds‘ may contain sub
obtamed by brommatmg acrolein and treating
stituent groups in the benzene nuclei, e. g. alkyl,
the product with an alkyl mercaptan followed by
heating with an. alkali to remove bromine. Compounds of general Formula B may be converted‘
aryl, amino, hydroxy and alkoxy groups or halo
gen atoms.
The quaternary salts may be derived from vari
2,412,815
3
of triethylamine was then added, andlthe reac
ous organic or inorganic acids,vfor example, they
may be chlorides, bromides, iodides, alkyl sul
tion mixture stirred. The boiling was fooiotinued
for 5 minutes, and the reaction mixture was then
allowed to cool. The dye was precipitated from
solution by the addition of ether, and ?ltered o?.
phates, p-toluene sulphonates or perchlorates. '
In carrying out the condensation using a com—
pound of general Formula I where X is oxygen,
it is generally convenient to heat the reagents
together in the presence of albase and a solvent;
pyridine is excellent in serving both purposes.
When carrying out the condensation using a
compound of general Formula I where X is sul 10
phur, however, it is preferred to heat the re
agents together in the presence of a solvent and
Recrystallisation from methyl alcohol yielded the
dye as blue crystals with a bronze re?ex M. pt.
238° C. with decomposition. The dye had the
structural formula:
4
a substance which will combine with alkyl mer
captan split off during the reaction (a suitable
medium is acetic anhydride which serves both 15
purposes) and to ?nish oil the reaction by add
ing a‘ base and heating for a further period.
The following examples illustrate the inven
tion:
-
I
EXAMPLE IV
Preparation of 3:3'-dimethyl-thiazolino
'
20
dicarbocyanine iodide
EXAMPLE I
V1.12 gms. of 2-methyl thiazoline methiodide,
, : Preparation of 2':2'-diethyl thiadicar
‘
'
-
1.0 gm. of ,B-ethyl-thio-acrolein-mercaptal, and
bocyanine iodide
3.05 gms. of lemethylbenzthiazole ethiodide,
1.11 gms. of ?-ethyl-thio acrolein diethyl acetal
and_15 vccs. of pyridine were mixed and boiled
gently under re?ux for 15 minutes. The reaction
15 ccs. of acetic anhydride were‘ boiled gently
To the solution was added 0.35
r under re?ux.
' cc. of triethylamine and the heating continued
for six minutes. The reaction mixture was al
lowed to cool, lixiviated with petroleum ether, the
petroleum ether decanted off, and the residue
mixture was then poured into an aqueous solution
of potassium iodide. The dye was precipitated
and was ?ltered off, and washed with ethyl alco 30 diluted'with ether. The precipitated dyestu?
' was ‘filtered off and washed with ethyl alcohol,
hol and ether. Recrystallisation from methyl al
water, ethyl alcohol again and ?nally ether, and
cohol solution yielded the dye as green needles.
was obtained as silvery crystals. M. pt. 202? C.
M. pt. 248° C. with decomposition. The dye had
with decomposition. The dye had the structural
the structural formula:
35
S
S
N/
6.11.
'40
EXAMPLE II
As already stated, the dyestuffs obtained by
the process of this invention are valuable sensi
Preparation of 1 :1'-diethyl 2:2"-quinodi- '
carbocyanine iodide
45 ‘tisers for photographic silver halide emulsions.
Thus, for example, the dyestufi of Example IV
1.5 gms. of quinaldine ethiodide, 0.6 gm. of ,8
‘supra incorporated in a silver iodobromide emul
ethyl thio acrolein diethyl mercaptal and 10 cos.
sion, extends the sensitivity to about 6200 A. with
of acetic anhydride were boiled gently under re
?ux until partly in solution. 0.7 cc. of triethyl
amine was then added and the heating continued
for IO-minutes. The reaction mixture was cooled
a maximum sensitivity at about 5750 A.
What‘ we
and the dye precipitated by dilution with ether.
The . dye had the structural
formula: '
LCH—~CH=OH—CH=CH
\N
02115
v
I’
'
'
V
._
carbocyanine iodide
_
.
‘
XR1
where the groups R1 are alkyl groups and the
groups X are the same and selected from the
60 class consisting of oxygen and sulphur atoms,
with a compound selected from the class con
sisting of alkyl and aralkyl quaternary salts of
heterocyclic nitrogen compounds containing a re
active methylene group in a-position to the qua
ternary
heterocyclic‘ nitrogenatom of the type
65
usual in the cyanine dye art.
_ 2. Process for the production of dicarbocyanine
dyes which comprises condensing a compound or
EXAMPLE III
Preparation of 1 :1'-dimethyl-indodi
V
the general formula:
The liquors were decanted through a ?lter and
the residue lixiviated with water. The dye was
?ltered off and washed well with ethyl alcohol
and ether,’ being thus obtained as green crystals
with a bronze re?ex. M. pt. 245° C. (with de
composition), and giving a turquoise blue solu
tion in alcohol.
claim is:
1. Process for the production of dicarbocyanine
dyes which comprises condensing a compound of
the
general
formula:
'
-
-
'
70
> ‘1.5 gms. of 2:3:3 trimethyl indolenine methi
odide, 0.6 gm. of B-ethyl-thio-acrolein-mercaptal
and 10 ccs. of acetic anhydride were boiled gent
where the groups R1 are lower alkyl groups and.
ly under re?ux until partly in solution. 0.7 cc.
the groups X are the same and selected ‘from
5
2,412,815
the class consisting of oxygen and sulphur atoms,
with a compound selected from the class con
sisting of alkyl and aralkyl quaternary salts of
heterocyclic nitrogen compounds containing a re
active methylene group in a-position to the qua-.
ternary heterocyclic nitrogen atom of the type
usual in the cyanine dye art.
'
3. Process for the production of dicarbocyanine
dyes which comprises condensing ,B-ethyl-thio
6
4. Process for the production of dicarbocyanine
dyes which comprises condensing B-ethyl-thio
acrolein dialkyl mercaptal with a compound se
lected from the class consisting of alkyl and
aralkyl quarternary salts of heterocyclic nitro
gen compounds containing a reactive methylene
group in u-position to the quarternary hetero
cyclic nitrogen atom of the type usual in the
cyanine dye art, by heating the reagents to
acrolein dialkyl acetal, with a compound selected 10 gether in the presence of a solvent and a sub
from the class consisting of alkyl and aralkyl
stance which will combine with the alkyl mercap
quarternary salts of heterocyclic nitrogen com
tan
split oiT during the reaction, and then add
pounds containing a reactive methylene group in
ing a base and continuing to heat the reagents
a-IJOSitiOIl to the quaternary heterocyclic nitro
gen atom of the type usual in the cyanine dye
art, in the presence of a base and a solvent for
the reactants.
for a further period.
JOHN DAVID KENDALL.
HARRY DEREK EDWARDS.
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