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Patented Dec. 17, 1946 \
2,412,816
UNITED STATES PATENT OFFICE
2,412,816
POLYMETHINE DYESTUFFS
John David Kendall and Harry Derek Edwards,
Ilford, England, assign ors to Ilford Limited,
l'lford, England, a British company
.
__1
No Drawing.
Application December 1'7, '1943,
Serial No. 514,668. In Great Britain January
1, 1943
11 Claims. (Cl. 260-240)
2
This invention relates to polymethine dyestuffs
and particularly to the production of dicarbo
" 01' by treating with an
cyanine and similar dyestuifs which serve as op
tical sensitisers for silver halide photographic
emulsions.
In co-pending application serial No. 514,669, ;
?led December 17, 1943, corresponding to British
speci?cation No. 15/43, there is described the
alkyl mercaptan in the
presence of a basic condensing agent under pres
sure, a compound of Formula B.
Compounds of the general Formula B may be
obtained by brominating acrolein and treating
the product with an alkyl mercaptan followed
by heating with an alkali to remove bromine.
Compounds of the general Formula C may be
preparation of compounds of the general For
converted to compounds of general Formula E
mula I:
10 by treating them with a sodium alkyl mercaptide
and an alkyl mercaptan under pressure.
(I)
The most convenient compound of general For
mula A to prepare is that in which the groups R
are ethyl groups since ethyl mercaptan is the
where R1 is an alkyl group, R2 is a hydrogen atom
most convenient of the alkyl mercaptans to em
or an alkyl or aralkyl group, and R3 is an alkyl
ploy. In using the compounds of general For
or aralkyl group (including unsaturated groups
mula A as dyestu? intermediates the condensa
of this type such as the allyl group and substi
tion to produce dyestuffs may eliminate all the
tuted groups of this type such as hydroxyalkyl
—SR groups so that the nature of the R group
groups), A is an acid radicle, D1 is the residue
of a heterccyclic nucleus, and n is an integer less 20 is not then of importance.
The acid condensing agent maybe any strong
than 3. In general it is preferred that the groups
ly acidic substance; sulphuric acid and zinc chlo
R1, R2 (if not hydrogen) and R3 should be lower
ride have been found very suitable.
alkyl groups, e. g. methyl and ethyl, and for
According to the present invention, a compound
convenience in preparing the compounds the group
R1 is preferably ethyl. The group A in the fore
of the general Formula A is converted to a val
uable dyestuff intermediate by condensing it in
going formula represents an acid radicle, e. g.
acid conditions with an alkyl, substituted alkyl,
chloride, bromide, iodide, alkyl sulphate, p-tolu
ene sulphonate and perchlorate.
aralkyl or substituted aralkyl quaternary salt of
a heterocyclic nitrogen base containing a. reac
In our copending application ‘Serial No. 514,666,
?led December 17, 1943, corresponding to Brit~ 30 tive methylene group (including a methyl or
ish application No. 14/43, there are described the
mono-substituted-methyl group) in the alpha or
production of compounds of the general For
mula A:
.
/XR,
R1s-c'H=cH—oH
35
(A)
XRI
gamma position to the heterocyclic quaternary
nitrogen atom.
The condensation is preferably effected by heat
ing the reactants together in the presence of a
solvent for the reactants and in the presence of
a compound capable of reacting with mercaptan
or alcohol split off during the reaction. It is
where the groups R1 are alkyl groups and the
groups X are both oxygen atoms or both sulphur
that acetic anhydride is particularly suit
atoms.
40 found
able in serving both purposes.
Compounds of the type wherein X is S can
The course of the reaction is believed to be as
be prepared as disclosed in aforesaid applications
follows:
‘
by treating with an alkyl mercaptan, in the pres
ence of an acid condensing agent, a compound of
one of the Formulae B, C, D, or E:
4.5
SR
. GHECH~CI/I
(B)
SR
0R
CH-ECH-C?
50
(c)
0R
OR
ao-0n=on~c€
(D)
D1 in the foregoing formula is the residue of
a heterocyclic nitrogen compound. Examples of
suitable heterocyclic nitrogen compounds are sub
oa
on
Rs—cH=cH-o§
(E)
OR
60
stituted and unsubstituted thiazoles, thiaz'olines,
; oxazoles, oxazolines, selena’zoles, selenazolines,
pyridine, quinoline, lepidine, indolenine, diazlnes
(e. g. pyrimidine and the diazines described in
2,412,816
4
British patent speci?cation No. 425,609), thio-
or an alkyl, aryl or aralkyl group. ‘ Examples are
diazoles and q'uinazoline and the corresponding
substituted and unsubstituted polycyclic come
pounds such as the benzthiazoles, naphthathiazoles and anthrathiazoles and the corresponding 5
rhodanio acid (2-thio-4-lreto-tetrahydro thia
tz‘ole),oxarhodanic acid (Z-thio-‘i-keto-tetrahydro
polycyclic oXazoles and selenazole's. Suchhetero-
'zoleé5-ones. hydantoin, thiohydantoin, ip-hydan
cyclic compounds may contain 'substitiient groups
toinand gl/—'thio-hydantoin.
droXy and alkoxy groups or halogen'atoms. V
methylene group, e. g. 1.3-indane-dione and the
oxazole), and the N-alkyl, N-aryl and N-aralkyl
derivatives of such compounds, oxindoles, pyra
in the benzene nuclei, e. g. alkyl, aryl, amino, hy-
'(c) Carbo'cycli'c compounds containing a ketc
According to the present invention polymethin'e 10 hydrindones.
dyestuffs are obtained by condensing a compound
((1) Compounds of the general type (b) above,
‘of general Formula I with a compound containbut which contain a substituent
ing a reactive methylene group or a ‘reactive
} R
amino group._ More speci?cally the invention is
__G/
‘concerned with compounds which contain ineth- 15
'
ylene groups which are external to a ring system
-
and rendered reactive by the character of the
ring System, including such external groups as
methyl and mono-substituted methyl which may
_ \ CH3
I
v
grouping (B. being hydrogen or an alkyl, aryl
'or aralkyl group) described in U. S. P. No.
2,213,986.
_
, be written as -—CH2R where R is a hydrogen atom 20
(e) Hydrazines and substituted hydra‘z'ine's.
"or an a1ky1, aryl or aralkyl group, and also meth~
When employing compounds of type (a) the
vlene groups which form part of a ring system
products obtained are dicarhccyanine dyes. By
and are rendered reactive by'theparticular 'enarusing a compound of type (a) in ‘which the het
acter of the ring system. Speci?c general classes
erocyclic nucleus is the same as that present in
of compound c'd?’t'ai?iilg such reactive methylene 25 the intermediate of general Formula I, symmet
and amino groups are;
’
rica} dicarbocyanine dyes may be obtained, but
(a) Quaternary salts of hetero‘cyclic nitrogen
the present invention presents the important ad
compounds containing a substituent methylene,
vantage that it affords a simple and practical 7
‘methyl or mono-substituted methyl group or an
method of obtaining the unsymmetrical dicarbO
amino group in the or or 'Y position to the ouate'r- 30 c'yanine dyes. The reaction with a compound of
‘nary nitrogen atom. Examples of compounds of
class (a) ‘is typi?ed by the following general
this type are those of the character ‘defined in
Equation E1:
which the heterocyclic nucleus is any or those
Where the compound of class (a) contains a
listed above in connection with the general For- 45 reactive NHz group instead of the CHzR group
‘mula I. The acid radicle 0f the quaternary ‘Salt
the product contains an =N-— atominstead of the
may be any of those listed above in connection
with the group A in Formula I.
g R
(b) Five-membered ring compounds of ‘theigeneral Formula II:
_(l3_
50
fn'n‘ul
§——'O o-orn
R
(II)
—
group shown above.
The reaction with a compound of class (D) is
typi?ed by the following general Equation E2:
{GI-13"‘: ‘
1'” '“'““D“"'“i
11lI—o
o-ém -+ ‘R1s-oH=c‘H-on=o4c=(c1r—c11),.-171<I\
R
Ra
A
:—--D-—-:
I'M :"_—'-"-Di-"--"-:
.
FIT-o0-o=oH-c11=oH-o=o-(o'H-o11)"4:1?
+ ruse + HA
R
'
Ra
where D is the residue of a heterocyclic nitrogen
ketomethylene ring and R is a hydrogen atom
The reaction with a compound of class (0) is
typi?ed by the following general Equation E3:
F"D"l
1?‘ i'"“""D“'_“:
B3 A
(30-bit, + R1s-o11=oH-o11=o;o=(on-o11)mink
1
re?ll-'1
(E2)
R: r''— - -—-D1— ---——'
,
2,412,816
In the above formulae and equations R, R1,
On cooling, ‘the dye crystallised and was ?ltered
R2, R3, D1, A, and X have the same values given 25 off,‘
and'washed well with ethyl alcohol, water
in Formula I and D2 has the same values as D1.
and ether. It had a melting point of 263°C. with
When employing compounds of type (b) such
decomposition. This dyestu? when incorporated
as‘ rhodanic acid Or oxarhodanic acid or the corin a gelatino silver iodobromide emulsion imparts
responding N-substituted compounds, the result- .30 a 'band of sensitivity with a, maximum at 6900A.
ing product contains a thio group and can be ‘
further reacted in a manner analogous to that
‘
~
r
'
‘
described in U, s. application No. 136,251, cor--
'
EXAMPLE m 1
‘
Preparation of IZ-methyl 1'-ethyl thia(2')quino
responding to B. P. No. 489,335.
dicarbocyanine iodide
The condensation may conveniently be e?’ected 3,.
L
'
_- __
_
‘
-
i n
_
by heating the reagents together in the presence ‘ thiaggleglglsetlggdlid‘z eggglticfl 21132112331558
of a ‘base, for example’ an Organic base Such as
ethiodide were boiled gently under re?ux until
pyridine or triethwamine?r an inqrganic base”
mostly dissolved in .150 cos. of ethyl alcohol. 2.1
Such as an a¥c°h°11¢ 50mm,“ M “alum Wet“?-
cc's. of triethylamine were added ‘and‘the‘heat
. The followmg examples Illustrate the mven‘ 40 ing continued for 12‘ minutes. The dye crystal
tlon- The process of Examples I to V, VII t3 1 lised from thesolution and after cooling was ?l
XI’
an‘? XV proceeds m accordance Wi?
tered off. ‘Recrystallisation from methyl alcohol
310133211305kitglgqgitg?aglgethg goggixip112
_
Y
_
ifrlielded the dyezaég green igygtals withta gold re
‘
‘ex melting at
‘‘ C. Wi
ecomposi ion. ‘ This
XII procgeds acwrdme t°_Equat1_°n E1 as P1051‘ 45 ~dyestui’f when incorporated in a gelatin‘o silver
‘Equation
treatises
E3; that ofiri?iii‘lif‘it‘ltriiiii'
Example XV'in accordance
tit
,tlvlty “2th: emu-eon
ma’Flmu-in'tt
We
‘715pa
with Equation E4 and that of Example xvn in
mg t° 7 0°
'accordance with Equation E5.
- y
‘
-
andeextend."
EXAMPLE IV
EXAMPLE I
l
11" Preparation of Z-methyl1':3':3'-trimethyl mm
_
_
‘
. d we r
.
.d
Preparationof
Z-methyZ-P-p-hydromyethyl thia,
m
0 z a bocyan."f6 wdz
e_ t
'
(4') quino dicarbocyanine
iodide
_
_
‘
'
..
th_1-931gmS-t£_f.
d1_';1w‘eth3('114131?°
butadflegyé 35:1?“
iazoe me 1013,31’).
.
gmso H: :gr
-"
?
droxy ethiodide were warmed into solution in‘70
“hlO:
.
hllh.
C.
uflcgglzlic solgtcfonegfydnaiggrgus 501151; :0:
PCS- ethyl alcohol’ 2-1 cos; of triethylamine were
tate was added and the heating continued for 12
added‘and the Whole boned gently under re?ux
minutes. on allowing to cool, the dye crystal
23ftltt‘tiiiiiithtiliini°tiit‘2.553211122252235;6o “$533111: $331563; 051-’.- 13213;}? gggg?ggg:
mittlté‘riittf’lififtitié‘iéttft?iififit; £33311;1iggdngg?ggggéfgégggbggeggiigzg$1
hol‘, water: ‘ethyl alcohol again, and ?nallyietlfer-
with decomposition.‘ 'This dyestu? when incor:
??'fiiilt?iti’t.£5,232.22‘:£§‘Zt12fc??‘tts§t%5“é§? tutti‘; i:tttztz.ittttstislzmitt:
with decomposition.
This dyestuff when incor-
at 6850 A and extendinplt'o 7400 A
porated in a gelatino silver iodo-bromide emulsion
,
imparts a band of sensitivity ‘with a maximum at
rmoo A.
,
" .
i
cyan M w z e l‘
>‘
' ‘
°
. EXAMPLE V
"
I
Preparation‘ of zlethyz-“rnmemyr omkzoqum
P’emmtm
. .7
»
of z-z'gmet'éig
EXAM?“ II thmowwwe , "701
7 -
v _
‘
.
;
. 1.93 gins. of l-w-ethyl-thio butadienyl *benz-
10. cos. ‘ of.
‘f dicizrbocyanme
a. solution ‘ofI-Qrethyl-thiQ‘I'butaQ
iodide , _
di‘enyll benzoxazole ,ethyl-p-toluene sulphonate
_' (prepared as in Example IV of (to-pending Appli
vthiazoleimethiodide...andt2.'75~-gms. .of.,1-methy1 :7'5 .cation-‘L‘Serial No. 514,669 corresponding to Brit
2,412,816
‘crystals; M. pt. 221° C. with decomposition. This
dyestu'? when incorporated in a gelatin'o silver
ish' speci?cation No. 15/43») and. .71. gm.~ of
quinald-ine'methiodide were warmed togethero'n
iodo-bromide emulsion imparts aband of sensi
tivity with a maximum at 7050 A and extending to
the water bath, 0.7 cc. of triethylamine was added.
and the reaction mixture boiled gently under
7400 A.
re?ux for 12 minutes. On cooling, the dye crys
tallised and was ?ltered off. Recrystallisation
from methyl alcohol yielded the dye as pale
greenish-gold crystals.
'
'
'
EXAMPLE IX
Preparation of‘ 2-rnethyl-2'-ethyl thiaselenodi
carbocyanine iodide
M. pt. 175° 0. with de-_ ‘
composition vand previous sintering. This dye
-~6 gins. of w-ethyl-thio butadienyl benzselen
stuff when incorporated in a gelatirio silver iodoe 10 azole ethiodide and 4.8 gms. l-methyl Lbenz
bromide emulsion imparts a band of sensitivity
thiazole methiodide were warmed,.till mainly in
with a.v maximum at 6900 A. and extending to
7000 A.
solution, with IOOcc’s. alcohol‘. 4.6 cos; of tri
ethylamine were added and the reaction mixture
EXAMPLE VI
15 boiled gently under reflux for ten minutes. The
dye-began to crystallise from the-solution, which
Preparation of 3-methyZ-2-thio-4-lceto-5-w-(N
ethyl dihydro benzozcazolylidene) butenylidene
was diluted with a little water and cooled. The
dye was ?ltered oil and thus obtained as green
rhlodanine
crystals. M. pt. 216° C. With decomposition.
10 ‘cos. of a solution of l-w-ethyl-thio buta
This dyestuff when incorporated in a gelatino
silver iod-o-bromide emulsion imparts a band of
dienyl 'benzoxazole ethyl-p‘e-toluene sulphonate
- (prepared as in‘Example. IV'of co-pending appli
sensitivity with a maximum at 7050 A and ex
cation Serial No. 514,669 corresponding to British
‘speci?cation No. 15/43.) and 0.37 gm. of N
‘methyl r-hodanic acid were’ warmed together on
tending to 7400 A.
was. ?ltered off, after cooling. the reaction mix
ture, recrystallised from methyl alcohol in which
it is. di?i-cultly soluble, and thus obtained as blue
55 gms. of w-ethyl-thio butadienyl benzselen
azole ethiodide, 4.6 gms. of 213-23-trimethy1. in
EXAMPLE X
the water bath. 0.4 cc. tri‘ethyl'amine was added 25 Preparation of Z-ethgl 1’-3’-3’-trimeth;yl selerio
and. the whole refluxed‘ for 10 minutes. The dye
"
indodicarbocyanine perchlorate
needles.
M‘. pt. 215° C.
dolenine methiodide and 100 ads. of ethyl alcohol
were warmedv together and 4- cos. ortriethylami'ne
This dyestuff when in
corporated in a gelatino silver’iodobromide emul
~ then added. After boiling gently under'reiiux
for 10 minutes the hot solution was poured-- into
sion imparts a band. of‘ sensitivity with a maxi
mum of 6500 A. and. extending to‘v 7000 A.
.
a warm aqueous solution of potassium. perchlo
rate.- The liquors were clari?ed, with acetone; and
the dye crystallised from the solution. Recrys
tallisatiorr of. the dyestuff» from methyl alcohol
gave dark blue crystals. M. pt. 197° C.» withde
composition. A second crop from the: recrystal
lisation had M. pt.- 204" C. with‘ decomposition.
This dyestufi when incorporated in a gelatino
silver iodo-bromide emulsion imparts a, band of
sensitivity with a-maximum at 6875 A and/ex
EXAMPLE? VII
Preparation of zieth'yl 1’:3’:3'-t‘rz'methyl 0.71am
dodicarbocyanine perchlorate
10‘ccs. of a- solution of e-ethyl-thio butadienyl
'benzoxazole ethyl-p-toluene sulphonate (pre
pared: as in Example IVv of co-pending applica
tion‘ [Serial No. 514,669 corresponding to British
speci?cation No. 15/43) and‘ 0.75 gm.’ of 2:3:3
trimethyl indolenine methiodide were warmed
together 'oni the water bath.
tending to 7000 A.
0.7; cc. of triethy-l
amine was added and. the; reaction mixture boiled
gently under re?ux for 12. minutes. The dye was
precipitated on cooling by dilution. with. water,
alcohol and ether, and had a M. pt. of 158°‘ C.
with decomposition. It'was’ converted to the per
chlorate‘ salt‘by dissolving‘: it in IO‘mcs. of~ methyl
V
:30
at 100° C. for one hour. The quaternary salt was
6: cos of triethylamine was added andthe reac
ti'on mixture boiled gently under reflux- for 1-0
with decomposition... This dyestu?‘ whenincor
porated. in. agelatino silver iodo-bromide emul
dic'arbocyanine' iodide».
‘
.816- gins... of l-lw-ethyllth‘io- butadienyl. benz
minutes. The dye bumped o'utfof' solution; The
reaction mixture was diluted with ethyl-ea-lcohol
and water; and cooled. By ?ltration‘the'dye was '
60 obtained: as bright green crystals. M. pt. 227° C.
with decomposition. This dyestufi when! incor
porated in a‘ gelatinosilver io'do-bromide- emul
sion imparts a band of sensitivity'with a maxi
mum‘ at 6200 A. Used-in larger quantity'it gives
65 amaximumi sensitivity at 6850 A.
thiazole methiodide and 7.1 gins‘. of l-methyl '
benzthiazolea?ihydroxyv 'ethiodiole ' were
boiled
methyl-p-toluene sulphonate. were fused together
then warmed, partly into solution, with 7‘ gins." of
2-w-ethyl thio b‘utadienyl l‘t3't3-trimethyl' in
dolenium perchlorate and-50 cos. of ethyl alcohol.
dye crystallised out- and was?ltered off. After
Preparation
'
7
zoZi'no-indo dicarbocyanin'e. perchlorate
crystallisation from methyl. alcohol solution, it
was obtained as violetcrystals. M. pt. 140° C.
-
-
.
2 gms. of ,a-methyl thia'zoline and 3.5" g'ms. of
aqueous solution- of potassium perchlorate. The
EXAMPLE VIII ‘
XI
Preparation 0 1‘! '3 -methyl 1.’ :3’ :3"-trime'ihyl'f ma
alcohol and-?ltering the‘ hot- solution into a hot
sionl imparts a ;band. of sensitivity with a maxi
mum‘ at.6400 A.
.
EXAMPLE
EXAMPLE
Preparation 0]" 2E2’-dimet7iyl17-az;tiii¢n time '
gently together under-re?uxin 150 cos. of ethyl
cyam'ne iodide
I
alcohols. 7. cos. ‘of. triethylaminewas added to the
hot solution and the heating. continued‘ for 12 70
0.3
gm.
of,
l-amino.
benzthiazole
and
lngm.
of
minutes. At this stage the dye began to crystal
methylép-toluene
sulphonate‘were'
fused‘
together
*lis'e: from the. solution. Therea'ctionimixtureiwas
at 100° C. for 1/2 hour‘. The solid quaternary salt
-'poure'd:into a‘ little water, cooledandth'e dye?l
thus‘ formed: was dissolved: in- 60 ccs.- of: pyridine
teredi off'; A'fter recrystallisation". from; methyl
alcohol the‘ dyev wasobtained aszshininggreen 76 and. 1.6; gm. of l-w-ethyhthioibutadienyL-benzi
23412316
10
thiazole methiodide was added. The reaction
?ltered hot from a little tarry residue, and
mixture was heated on a water bath for 15 min
utes. Dyestu? recrystallised from the solution,
and after dilution with ethyl alcohol and cooling,
it was ?ltered off and washed with ethyl alcohol
and ether. The dye was thus obtained as silver
poured. into anaqueous solution of potassium
iodide. The dye precipitated and was ?ltered off.
After recrystallisation from methyl alcohol it was
obtained as crystals. M. pt. 210° C. with de
blue crystals. M. pt. 240° C. with decomposition.
EXAMPLE XIII
in a silver iodo-bromide emulsion, imparts a band
of sensitivity with a maximum at about 70005.
Preparation of '[1-methyl-dihyctroquinolylidene~
2] -butenyZidene-1 ’ : 3 ' -dilceto-hydrindene
composition. This dyestulf, when incorporated
EXAMPLE XVII
10
Preparation 0; the‘ dz'hydriodide of 6-(1-methyl
0.18 gm. of 2-(w-ethyl-thio-butadienyl) -quin
dihydrobenzthiaeolylidene) -crotonaldazine
oline methyl perchlorate and 0.08 gm. of 1:3 in
dandione were boiled gently under re?ux with 7
0.13 gm. of powdered hydrazine hydrochloride
cos. of a 2% ethyl alcoholic solution of sodium 15 was boiled gently under re?ux with 40 cos. of a
2% solution of sodium acetate in ethyl alcohol.
acetate for one hour. The reaction mixture was
1.0 gm. of 1-(w-ethyl-thio-butadienyl) -benzthia
cooled and diluted with a little water. The pre
zole ethiodide was added and the heating con
cipitated dycstu? was ?ltered off and washed with
tinued for 30 minutes. A red colour rapidly ap
ethyl alcohol, water and ethyl alcohol again.
The dye was puri?ed by boiling out with methyl 20 peared, and at the end of the heating period the
dye solution was ?ltered hot. On dilution of the
alcohol and ?ltering hot, when the sparingly solu
?ltrate the dye was obtained as dark purple
ble dyestuff remained as brown crystals. M. pt.
crystals, M. pt. 204° C. with decomposition.
268° C. with decomposition.
Recrystallisation from‘methyl alcohol yielded the
EXAMPLE XIV
dye as dark brown crystals, M. pt. 208° C. with
25
Preparation
of
Z-methyZ-I’-ethyZ-5'.6'-benz
decomposition.
thia(4')quino dicarbocyanz'ne iodide
‘
What we claim is:
0.19 gm. 1-(w-ethyl-thio-butadienyl) -benz -
thiazole methiodide, 0.18 gm.of 5.6-,benz lepidine
ethiodide and 10 cos. of ethyl alcohol were boiled 30
gently into ‘solution under re?ux. 0.14. cc. of tri
ethylamine was added and the heating continued
for 3 minutes. The reaction mixture was then
.
1. Process for the production of polymethine
dyestuffs which comprises condensing a com
pound of the general formula:
allowed to stand overnight, when the dyestu??
crystallised out. It was ?ltered off and washed
with water, ethyl alcohol and ether. Recrystal
lisation from methyl alcohol yielded the dye as
green crystals. M. pt. 180° C. with decomposition.
‘
EXAMPLE XV '
Preparation of 7- [1 emethylll .Z-dihydroquinolyi
R3
A
where R1 is an alkyl group, R2 is selected from
the class consisting of the hydrogen atom and
alkyl and aralkyl groups, R: is selected from the
class consisting of alkyl, aralkyl, allyl and
40 hydroxyalkyl, D is the residue of a heterocyclic
nitrogen nucleus usual in the cyanine .dye art,
z'dene - 2] - 2 - [I -‘ phenz/Z - 3 - methZIl-5-keto
Ais an acid radicle and n is an integer less than
three, with a compound containing a reactive
0.35 gm. of 2(-w-ethyl-thio-butadienyl) -quino
line methyl perchlorate, 0.228 gm. of l-phenyl-B
45 active methylene groups and reactive amino
4.S-dihil/dropt/raeolylidene-4l-3.5-heptadiene
methyl - 4 - isopropylidenepyrazole-5-one and 20
group selected from the class ‘consisting of re
groups.‘
..
'
.
.
‘
2. ‘Process for the production of polymethine
dyestuffs which comprises condensing av com
pound of the general formula:
cos. of a 0.5% alcoholic solution of sodium acetate
were boiled gently together under re?ux for
,1/2 hour. The reaction mixture was cooled and
diluted, and the precipitate ?ltered o? and 60
’ ‘
‘
1'12 :-————D--——-—-:
washed with ethyl alcohol. , By benzene extrac
tion the dye was obtained as blue crystals, M. pt.
‘
‘
R:
A
215° C., which gave a blue solution in benzene.
This dyestu?, when incorporated in a silver iodo
where R1 is ‘an
_ alkyl group, R2 is selected from
of the hydrogen atom and
‘bromide emulsion, imparts a band of sensitivity 55 the class consisting
‘ alkyl and aralkyl groups, R: is selected from the
with a maximum at about 7600 A.
R.s-cH=oH—oH=c-o=(on-ommjn
EXAMPLE XVI
Preparation of Z-o-acetoryethyl-Z’-p-hydroa:y
ethyl-thiadicarbocyanine iodide
1.6 gm. of 1-methyl benzthiazole e-hydroxy
ethyl iodide and 25 cos. of acetic anhydride were
class consisting of alkyl, aralkyl, allyl and
hydroxyalkyl, D is the residue of a heterocyclic
nitrogen nucleus usual in the cyanine dye art,
60 A is an acid radicle and n is an integer less than
three, with a cyclic compound containing a
methylene group rendered reactive by the ring
system.
»
'
‘
boiled gently under re?ux until the solid passed
into solution. 2 cos. of ?-ethyl-thio-acrolein 65 > r 3. Process for the production of polymethine
dyestu?s which comprises condensing a com
acetal were added and the reaction mixture
pound of the general formula:
1
heated for a further 10 minutes. The excess
acetic anhydride was then distilled‘off under re
duced pressure, and the residue was washed with
petroleum ether and ether. ‘ This intermediate 70
was further reacted with 1.6 gm. of 1-methy1
A
benzthiazole-c-hydroxyethyl iodide by heating
‘with 20 cos. of ethyl alcohol and
‘the class ‘consisting of the hydrogen atom and
1.4 cc. of triethylamine for 5‘ minutes. 'More
‘alcohol was added and the dye solution was 75 alkyl and aralkyl groups, R3 is selected from the
class consisting of alkyl, aralkyl, allyl ‘and
2,912,811.13
11?
hydreryelkyl, D is the residue er a heterecyelie
nitrogen nueleus usual in the eyanihe dye art,
A. is
eid rediele and h is. an integer less than
three; . th
Quaternary salt of a heteroeyclic
where R1 is an alkyl group, He is selected from
the class consisting of the hydrogen atom’ and
alkyl and aralkyl groups, R3 is selected from the
class consisting of alkyl, aralkyl allyl and hy
nitrogen eemnehhsi containing a substitueht
group selected from the class consisting of
Is
rlehe and amine greens in one of the e and 7
P95! ens-t9 the, hetereerelie ehleternery nitrogen
atom.
droxyalhylhDi is the residue of a heterocyclic ni
pound of ‘the general formula:
with a eompeuhd of the general formula:
4. Process for the production of polymethine 10 trogen nucleus usual in the‘ cyanine dye art,_A is
an acid radicle and nis an integer less ‘than three,
dyestuffs which comprises condensing av com
Rls-—cH;oH-cn=.o-o;(on-o11),_1=N
.15
Ra’ ‘NA
i
where R4 is an alkyl group, R2 is selected from
wherein D2 is the residue of a heterocyclic nitro
gen ketomethylene. ring and R is selected from
the class consisting of the hydrogen atom and
a_lkyl and aralkyl groups, is selected ‘from the
class consisting oi‘ a_lhyl, aralkyl allyl and by
dro‘zryalkyl, ‘D1 is’ the‘residue of a heterocyclic
nitrogen nucleus usual in the cyanine dye arty,v A
the mess eeheietihe ef. the hydrogen atom and
hydrocarbon gITQQPS:
_8. Process for the production of polymethine
dyestuffs which comprises condensing a 6,011.1
pound of the general formula:
is eh'e-eisi reeliele and h 1e an integer less than
three, with?» eemheehel 9f the general iermulw
xiii-o o-on,
R
wherein D2 is the residue of a heterocyclic nitro
where R1 is an alkyl group, R2 is selected from
gen ketomethylene ring and R. is selected from the 30 the‘ class consisting of the hydrogen atom and
class consisting of the hydrogen atom and hy
alkyl and aralkyl groups, R; is selected from the
class consisting of all‘ryl, aralkyl 'allyl and hy
drocarbon groups.
5. Process for the production of polymethine
dyestu?s which comprises condensing, in the
droxyalkyl, D is the residue of a heterocyclic ni
trogen nucleus usual in the cyanine dye art, A
is an acid radicle and n is an ‘integer less than
three, with a compound selected from the class
Presence of e base, e eempouhd 0f the general
formula:
'
consisting of hydrazines and substituted hydra
'- zines.
40
A
9. Process for the preduetion of polymethine
dyestuffs which comprises condensing a__ com
pound of the general. thrmula:
where R1 is an alkyl group‘, R-z is selected from
‘
'
the class consisting of the hydrogen atom and
alkyl and aralkyl groups, R3 is selected from the
class consisting of alkyl, aralkyl allyl and by
droxyalkyl, D is the residue of a heterocyclic m't-.
rogen nucleus usual in the cyanine dye art, A is
where the groups R1 and R3 are lower alkyl groups
an acid radicle and n is an integer less than three,
with a cyclic compound containing a methylene
and the group R2 is ‘a group of the structure
.——.(CH2-)-a:_-1—.-H where a: is an integer less thanA,
D is the residue of a heterocyclic nitrogen nu
group rendered reactive by the ring system.
6. Process for the production of polymethine
dyestuffs which comprises condensing, in the
cleus usual in the cyanine dye art, .A is an acid
radicle and n is an integer less than three, with
presence of a base, a compound of the general
a cyclic compound containingla methylene group
formula:
55 rendered reactive’ by the ring system.
10. Process forv the production of polymethine
dyestuffs which comprises condensing a com
pound of the generalfgrrnula;
Where R1 is an alkyl 8.101113,’ R215 seleeted £10m
the-class consisting of the hydrogen atom and
alkyl and aralkyl groups, R; is selected from the
class consisting of; alkyl, aralkyl allyl and hy
60
T'Ra.
droxyalkyl, D is the residue of a heterocyclic ni
trogeh nucleus usual in. the eyamne dye art. A
A
Where the groups R1. ehdRi ere lower allsyl greens
and the grout? B2 is e group of the structure
is an acid radicle and n, is an integer less than 65 -~(ICH2_)¢-1.-.H where .r- is an integer less thanili,
three, with a quaternary salt of a heterocyclic
Die the residue of e hetereeyel'ie nitrogen nucleus
nitrogen compound containing a substituent
usual; the eyehine dye
A is an acid; vesicle .
group selected from‘ the class consisting of
and n is
integer less than three. , ‘t
methylene and amino groups in one of the cc and
rt’ salt. ef; a hetereerelie hitree, 1
1; positions to the heterocyclic quaternary nitro
nine eeuhstitheht. emu Se eted
gen atom.
T. Ereeeee for theprQdhetien of nelymethihe
dyeetufis which comprises condensing. in the
preeehee of. a. base, a. eqrhpenhd Qt. the general
formula:
-
'
'
-
r
I
ielasecehsistine; of methylene
one oi the send 1 positions to. thehetereerelie
emi
quaternary"
11.- Proeess
nitrogen
for the etch.
production,
‘
of
' polymethine
_
-
‘2,412,816
13
dyestu?s which comprises condensing a com
pound of the general formula:
nls~on=on-on=e-o=(on-cn)Min
R:
A
where the groups R1 and R3 are lower alkyl
groups and the group R2 is a group of the struc
ture —(CH2)a:-1——H1 where :1: is an integer less
than 4, D1 is the'residue of a. heterocyclic nitro
gen nucleus usual in the cyanine dye art, A is an
acid radicle and n is an integer less than three,
with a. compound of the general formula:
‘r
14
wherein D2 is the residue of a heterocyclic nitro
gen ketomethylene ring and R is selected from
the cIass consisting of the hydrogen atom and
hydrocarbon groups.
JOHN DAVID KENDALL.
HARRY DEREK EDWARDS.
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