Note: Descriptions are shown in the official language in which they were submitted.
107C~679
The present invention provides cationic azo dyes of formula
Z
I (C~-CH) ~ ; ~ N] ~ (I)
wherein Rl represents an alkyl radical optionally substituted by an aryl,
chloro, hydroxyl, cyano, ester or acyl group, n is O or 1, Z represents a
divalent radical which completes the ring A to form an azine or azole ring
that can contain a fused benzene ring, R represents an alkyl radical optionally~
substituted by halogen or phenyl or an aryl radical optionally substituted by
halogen, alkyl, alkoxy, nitro, alkylsulphonyl or sulphonamido, and X ~ repre-
sents an anion.
Rl is herein above all a low molecular alkyl radical of 1 to 4 car-
bon atoms which can be substituted. Possible substituents are: aryl radicals,
especially the phenyl radical, chlorine, hydroxyl or cyano groups, ester or
acyl groups, in particular carbalkoxy and alkanoyl groups each of 1 to 4 carbon
; atoms.
R is a low molecular alkyl group which can be substituted, for exam-
ple, by halogen or phenyl, or is an aryl radical of the benzene or naphthalene
series. Where R represents a phenyl or naphthyl radical, such a radical is pre-
ferably unsubsituted or is substituted by chlorine, bromine, alkyl of 1 to 4
carbon
-2-
A
. .. ... . . ~. . . ~ ~ .
. - . . . . . .. . .
... .
.~ . . . . . ~ ... .. .. . . .
.
... .. .. . .. . . .
. . . . . -
. ~o7067g
atoms, alkoxy of 1 to 4 carbon atoms, as well as by nitro
groups, alkylsulphonyl groups of 1 to 4 carbon atoms or by
sulphonamido groups. Where R represents a low molecular,
substituted or unsubstituted alkyl radical, such a radical is
above all a propyl, isopropyl, butyl~ benzyl or ~-chloroethyl
radical.
The ring A is preferably one of the following hetero
cyclic radicals which contain a quaternised nitrogen atom:
thiazolium, isothiazolium, isoxazolium, thiadiazolium,
triazolium, pyrazolium, pyridinium, indazolium, benzthiazolium,
benzisothiazolium, quinolinium or isoquinoliniu~.
The anion X ~ is derived from a strong organic acid, and
is for example a chloride, bromide, iodide, nitrate, sulphate,
especially a hydrogensulphate, and a phosphate, in particular
a dihydrogen phosphate. However, anions of organic acids are
also possible, by which are meant aryl- and alkylsulphonates
and aryl- and alkylcarbonates, in particular benzenesulphonate
and the derivatives thereof which are substituted by nitro
groups, chlorine, bromine, alkyl groups of 1 to 4 carbon
atoms and alkoxy groups of 1 to 4 carbon atoms; alkylsulph-
onates of 1 to 4 carbon atoms, anions of aliphatic carboxylic
acids of 1 to 4 carbon atoms, and benzoates, wherein the
benzene ring can contain the same substituents as those of
the benzenesulphonates. Especially preferred anions are those
.... .. .. .. ....... . . ....
.
1070 67 9
of low molecular alkylsulphuric acid half esters which contain
1 to 4 carbon atoms. The dyes can also be in the form of
; double salts with heavy metal halides, in particular with
zinc and cadmium halides.
Examples of such anions are: benzenesulphonate,
p-~oluenesulphonate, p-methoxybenzenesulphonate, methane-
sulphonate, ethanesulphonate, formiate, acetate, chloroacetate,
propionatP, lactate, tartrate, benzoate, methylbenzoate,
methylsulphate, ethyl sulphate, ZnC13 Q and CdC13 ~
The novel dyes are manufactured as a rule by coupling
a heterocycli~ nitrogen-containing diazo component to a
5-aminopyrazole which is substituted in l-position and
quaternising or alkylating the resultant azo dye. In individual
cases, the quaternising can be effected at the diazo compon-
lS ent, i.e. before the diazotisation and coupling. This applies,
for example, to the diazo components of the pyridine class.
The quaternising of the 2-aminopyridines must be carried out
before the diazotisation and coupling, whereas that of the 3-
or 4-aminopyridines can be effected in any desired sequence.
The invention therefore provides a process for the
manufacture of dyes of formula (1), wherein an azo dye of
formula
N A ~ - N = N ~ (2)
~CH-CH)n H2~
R
-- 4 --
- ' . .: . . . :
. . . .
: ~ - . . . .
.... : , . . . .
-
1070679
wherein Z, R and n are as defined in formula (1), but the
ring A may not be pyridyl-(2) or quinolinyl-(2), is reacted
with an alkylating or quaternising agent that affords the
radical Rl.
The following compounds of formula
,Rl-X
are suitable alkylating agents with which the azo compounds
of formula (2) are reacted to give cycloammonium salts of
; formula (1): substituted or unsubstituted, low molecular alkylesters or aralkyl esters of a hydrogen halide, for example
the methyl, ethyl, n-propyl, n-butyl, ~-cyanoethyl, ~-carbamoyl-
ethyl or benzyl ester of hydrogen chloride, hydrogen bromide
or hydrogPn iodidei low molecular dialkylsulphates, for example
dimethyl or diethyl sulphate; alkyl esters of 1 to 4 carbon
atoms of an organic sulphonic acid, for example the methyl,
~-chloroethyl, ethyl, propyl and butyl ester of benzensulphonic
acid, of _- or p-tol~lenesulphonic acid, of 4-chlorobenzene-
sulphonic acid or of 4-nitrobenzenesulphonic acidi also the
bromoacetic or chloroacetic acid alkyl esters with 1 to 4
carbon atoms in the alkyl moiety.
Further alkylating agents are alkenes and epoxy
compounds. These may be understood as meaning primary products
of alkanol esters of the type Rl-X. They are reacted in the
presence of acids, for example HCl, HBr, formic acid or glacial
-- 5 --
1070679
acetic acid, with the nitrogen compounds to be quat:ernised.
Examples of such alkylating agents are the reagents listed
in the firs~ column of the following table which in eaeh case
introduce into the nitrogen compound the radical Rl listed
in the second column:
.. , R
. . .... :
CH2 = CH - C~ - CH2 - CH2 - CN
C~2 ~ CH - COOCH3 2 CH2 - COOCH3
CH2 = CH - COOC2H5 - CH2 - CH2 - CC2H5
CH2 - CH2
~O/ - CH2 - CH2 - OH
C~ - CU - CH - CH2 - CH - CH3
The alkylation is effected advantageously by heating
in an inert organic solvent, for example a hydrocarbon, such
as benzene, toluene or xylene, a halogenated hydrocarbon,
for example carbon tetrachloride, tetrachloroethane, chloro-
benzene, o-dichlorobenzene, or nitrohydrocarbons, such as
nitromethane, nitrobenzene or nitronapthalene. Acid anhydrides,
acid amides or nitriles, for example acetic anhydride,
dimethyl formamide or acetonitrile or-dimethyl sulphoxide
can also be used as.solvents in the alkylation. Instead of a
- - .. ~- ... .
- . .. .
' .. . ' . . . ~ ,' , -- ,.. ' ' ~'
~ . . .. , . - .
: ~
. -
.
1070679
solvent, it is also possible to use a large excess ofalkylating agent. In most cases, especially in the presence of
an organic solvent. it is necessary to heat the reaction
mixture externally in order to initiate the reaction. In some
S cases, the alkylation can also be carried out in aqueous
medium or with an alcohol, if required in the presence of
small amounts of potassium iodide.
The invention also comprises a modification of the above
described process for the manufacture of dyes of formula (1~
wherein A is a pyridinium radical. This modification consists
in diazotising a diazo component of formula
rR~
L ~(cH-cH) ~ ~ X ~ (3)
wherein Rl, n and X ~ are as defined in formula (1) and Z
completes the ring A to form a pyridinium or quinolinium rir.g,
and coupling the diazonium compound to a 5-aminopyrazole of
formula
H2 , (4)
wherein R has the meaning assigned to it in formula (1).
The diazotisation of the 2-aminopyridinium or 2-amino-
: ' :
1070679
quinoliniu~t salts is advantageously effected with nitrosyl-
sulphuric acid in a concentrated organic carboxylic acid, for
example formic acid, acetic acid, propionic acid, or in
sulphuric acid.
As examples of suitable 2~aminopyridine and 2-amino-
quinoline derivatives there may be cited: 2-aminopyridine,
2-amino-3-, -4-, -5 or -6-methylpyridine, 2-amino-4,6-
dimethylpyridine, 2-amino-5-chloropyridine, 2-amino-5-
ethoxypyridine, 2-aminoquinoline, 2-amino-4-methylquinoline,
2-amino-6-chloroquinoline or 2-amino-8-ethoxyquinoline.
The coupling of the diazonium compound of a 2-amino-
pyridinium or 2-aminoquinolinium salt to a 2-aminopyrazole
compound which couples in 4-position is advantàgeously carried
out in organic-acid medium and at low temperatures.
Examples of suitable coupling components of formula (4)
are: l-methyl-5-aminopyrazole, 1-isopropyl-5-aminopyrazole,
l-~-chloroethyl-5-aminopyrazole, 1-butyl-5-aminopyrazole,
l-phenyl-5-aminopyrazole, 1-p-methylphenyl-5-aminopyrazole,
l-~-methoxyphenyl-5-aminopyrazole, l-o-, nt- or p-chloro- or
-bromophenyl-3-methyl-5-aminopyrazole, l-benzyl-5-aminopyrazole
or l-~-naphthyl-5-aminopyrazole.
The compounds of formula (2) are obtained in conventional
manner by diazotising a heterocyclic amine and coupling it to
a 5-aminopyrazole of formula (4). Examples of suitable
-- 8 --
., .~ ~ .. .. . . . . . . , . , . .... .. ... ., ~ .,
::
.
10 70 67 9
heterocyclic amines are: 2-amino-thiazole, 2-amino-4- or
-5-methyl-thiazole, 2-amino-4-n-butyl-thiazole, 2-amino-4
tri~luoromethyl-thiazole, 2-amino-4-chloromethyl-thiazole,
2-amino-4- or -5-phenyl-thiazole, 2-amino-4-(3'-nitro)-phenyl-
thiazole, 2-amino-4-(4'-nitro-phenyl-thiazole, 2-amino-4-(4'-
; methoxy)-phenyl-thiazole, 2-amino-4-(4'-bromo- or -chloroj-
phenyl-thiazole, 2-amino-4- or -5-methoxy-thiazole, 2-amino-4--
hydroxymethyl-thiazole, 2-amino-4- or -5-acetyl-thiazole,
2-amino-4-acetylamino-thiazole, 2-amino-4-dimethylaminomethyl-
thi.azole, 2-amino-4- or -5-ethoxycarbonyl-thiazole, 2-amino-4-
or -5-cyano-thiazole, 2-amino-5-nitro-thiazole, 2-amino-5-
methylsulphonyl-thiazole, 2-amino-5-methyl-mercàpto-thiazole,
2-amino-5-phenoxycarbonyl-thiazole, 2-amino-5-bromo- or -chloro-
; thiaæole, 2-amino-5-thiocyano-thiazole, 2-amino-4,5-dimethyl-
thiazole, 2-amino-4-bromo-5-phenyl-thiazole, 3-amino-isothiazole,
3-amino-5-nitro-isothiazole, 3-amino-4,5-dimethyl-isothiazole,
; 3-amino-5-phenyl-isothiazole, 5-amino-3-methyl-isothiazole~
5-amino-3,4-dimethyl-isothiazole, 5-amino-3-phenyl-isothiazole,
5-amino-3-methyl-4-cyano-isothiazole, 5-amino-3-phenyl-4-
methyl-isothiazole, 5-amino-3-methyl-4-carbomethoxy-isothiazole,
5-amino-4-methyl-isothiazole, 5-amino-isoxazole, 5-amino-3,4-
dimethy-isoxazole, 3-amino-isoxaæole, 2-amino-1,3,4-thiadiazole,
2-amino-5-methyl-1,3,4-thiadiazole, 2-amino-5-phenyl-1,3,4-
thiadiazole, 2-amino-5-methoxy-1,3,4-thiadiazole, 2-amino-5-
-- , .
1~ 7~ 67 9
methylmercapto-1,3,4-thiadiazole, 2-amino-5-(ethoxycarbonyl.-
methylthio ~ -1, 3, 4- tniadiazoie, 2-amino-5 -methylsulphonyl- 1, 3, ~t-
thiadiazole, 5~ nino-1,2,4-thiadiazole, 5-amino-3-methyl-1,2,4
thiadiazole, 5-amino-3-phenyl-1,2,4-thiadiazole, 5-amino-3-
chlor o- 1, 2, 4- thiadiaz ol e, 5 - amino~ 3- me thoxy- or - ethoxy- 1, 2, 4-
thiadiazole, S-amino3-benzyloxy-1,2,4-thiadiazole, 5-amillo-3-
methylmercapto-1,2,4 thiadiazole, 3 amino-1,2,4-t.riazole,
3-amino-5-methyl- or ethyl-1,2,4-triazole, 3-amino-5-cyclo-
hexyl-1,2,4-triazole, 3-a;nino-5-phenyl. 1,2,4~triazolP, 3-amino-
5-(3'-methylp'nenyl)-1,2,4-tri~zole, 3-amino-5-(4'-nitrophenyl)-
1,2,4-triazole, 3--amino-5-benzyl-1,2,4-~riazole, 1-methyl-3-
amino-l, 2 ,4-triazole, 1-benzyl-3-amino-1, 2 ,4~triaæole, l-phenyl-
3-amino- 1, ~, 4- triazole, 1-benzyl-5-methyl- 3-amino- 1, 2, 4- triazole 7
1,5-dibenzyl-3-amino-1,2,4~triazole, 1-ethyl-5-phenyl 3-ami~o-
1, 2, 4-triazole, 4-phenyl-5-ami.no-pyra201e, 4-methyl-5-amino-
pyrazole, 4-cyano-5-amino-pyrazole ? 4-nitro-5-amino-pyrazole ~
l-phenyl-5- amino-pyrazole, 3-amino-pyrazole, 1-phenyl-3-amino-
pyrazole, 3-amino-4-cyano-pyrazole, 3-arnino-4-nitro-pyrazole,
3-amino-4-ethyl-pyrazole, 3-amino-4-e~hoxycarbonyl-pyrazole,
3-amino-2-phenyl-4-methoxycarbonyl-pyrazole, 1 ,4-diphenyl-
5-amino-pyrazole, 1, 4-dimethyl-5-amino-pyrazcle, 1-ethyl-4-
methyl-5-amino-pyrazole, 1-n-butyl-4-methyl-5-amino-pyrazole,
1-(3'-methylphenyl)- 3-methyl 5-amino pyrazole, 1-(4'-methyl-
phenyl)-3-methyl-5-amino-pyrazole, 1- (3 ' -chlorophenyl)-3-
' - 10 -
.... .. . . .. . . . ..
-- . , . . . ~ .
,
,
.
.', ' ~
1070679
methyl-5-amino-pyrazole, 1-(3'-methoxyphenyl)-3~methyl-5-
amino-pyrazole, 1-(3'-methylsulphonylphenyl)-3-methyl-5-amino-
pyrazole, 1-(4'-nitrophenyl)-3-methyl-5-amino-pyrazole, 3-
amino-pyridine, 3-amino-4-methyl-pyridine, 3-amino-5-chloro
pyridine, 4-amino-pyridine, 4-amino-2- or -3-methyl-pyridine
3-amino-indazole, 3-amino-4-, -5- or -6-methyl-indazole,
3-amino-4-, -5- or -6-methoxy-indazole, 3-amino-4-, -5- or
-6-chloro- or -bromo-indazole, 3-amino-5- or -6-indazole,
3-amino-5- or -6-trifluoromethyl-indazole- 3-amino-6-cyano-
indazole, 3-~amino-5-methylsulphonyl-indazole, 6-amino-indazole ?
l-methyl-6-amino-indazole, 2-amino-benzthiazole, 2-amino-6-
methoxy-benzthiazole, 2-amino-6-ethoxy-benzthiazole, 2-amino-6-
phenyloxy-benzthiazole, 2-amino-6-chloro- or -bromo-benzthiazole,
2-amino-6-methyl- or -ethyl-benzthiazole, 2-amino-6-acetyl-
amino-benzthiazole, 2-amino-6-carbomethoxy- or -ethoxy-benz-
thiazole, 2-amino-6-phenylamino-benzthiazole, 2-amino-6-
methylsulphonyl-benzthiazole, 2-amino-6-nitro-benzthiazole, 2-
amino-6-methylthio-benzthiazole, 2-amino-6-cyano-benzthiazole,
2-amino-6-cyano-benzthiazole, 2-amino-6-sulphamoyl-benzthiazole,
2-amino-6-dimethylsulphamoyl-benzthiazole, 2-amino~6-thiacyano-
benzthiazole, 2-amino-6-carbamoyl-benzthiazole, 2-amino-6-~-
hydroxyethyl-benzthiazole, 2-amino-6-trifluoromethyl-benzthia-
zole, 2-amino-6-acetyl-benzthiazole, 2-amino-~-methyl-benzthia-
zole, 2-amino-4-methylsulphonyl-benzthiazole, 2-amino-5-methyl-
,:
.,
~070679
benzthi~zole, 2-ar.lino-5,6-dimethyl- or dimethoxy-benzthiazvle,
2-amino-4,6-dimethyl-benzthiazole, 2-amino-4,7-dimethoxy-
benzthiazole, 2-amino-4,6-dichloro-benzthiaæole, 2 amino-
naphtho-11,2-d]-thiazole, 3-amino-2,1-benzisothiazole, 3-amino-
4,7-dimethyl-2,1-benzisothiazole, 3-amino-6,7-dichloro-2,1-
benzisothiazole, 3-amino-6-cyano-2,1-benzisothiazole, 3-amino-
5-(N,N-dimethylsulphonamido)-2,1-benzisothiazole, 4-amino-
: quinol.ine, 4-amino-quinaldine, l-ami.no-i.soquinoline and 4-amino-
isoquinoli.n~.
Among the cited diazo components, particular mention ..
is to be made of the following preferred groups,
-thiazoles of formula
C - NH2
~, R2
; wherein R2 is hydrogen, alkyl of 1 to 4 carbon atoms, phenyl,
chlorine, bromine, alkoxycarbonyl of 1 to 4 carbon atoms or
alkanoyl of 1 ~o 4 carbon atoms;
-triazoles which in one of their possible tautomeric forms
. have the formula
. N
R ~
. . , -- -- .
. . . . . . .
.. '' ' . ' . .. .. ..
.
.' ~ .
~070 67 9
wherein R3 is hydrogen or an alkyl group of 1 to 4 carbon
atoms, a benzyl or phenyl groupi
-thiadiazoles of formula
. N - N
R4 ~S ~ 2
wherein R4 is hydrogen, alkyl of 1 to 4 carbon atoms or phenyl:
-isothiazoles of formula
N~5 ~ ~H2
wherein R5 is alkyl of 1 to 4 carbon atoms or phenyl;
-pyrazoles of formula
R8 ~ 7
N~ ~ NH2
R6
wherein R6 is alkyl of 1 to 4 carbon atoms, phenyl or phenyl
which is substituted by chlorine, bromine, alkyl of 1 to 4
carbon atoms or alkoxy of 1 to 4 carbon atoms, and each of R7
and R~ is hydrogen or an alkyl radical of 1 to 4 carbon atoms;
-pyridines of formula
R
H~
~ ' .
- 13 -
,
" ~ ' .
1~7`()679
wherein R~ is hydrogan, alkyl of 1 to 4 carbon atoms or
chlorine; and also
-benzthiazoles of formula
Rlo ~ N ~ 2
, .
wherein Rlo is an alkyl or alkoxy group each of 1 to 4 carbon
atoms.
The cationic dyes of formula (1) are obtained as salts
of ~he acids of the alkanol or aralkanol esters Rl-X used
for their manufacture, i.e. as salts of inorganic or organic
acids. They are therefore primarily halides, such as chlorides,
bromides or iodides, alkylsulphates, such as methosulphates
and ethosulphates, benzenesulphonates or p-toluenesulphonates.
; If desired, it is also possible to manufacture salts of other
acids by double reaction in a suitable polar solvent, for
example oxalates by addition of oxalic acid. ~ouble sal~s
can also be manufactllred, for example with the dyestuf
halides and corresponding zinc halides.
The precipitation of the resultant dye salts is desixably
brought to completion by adding sodium chloride and/or zinc
chloride in aqueous acid solution and they are then isolated
by filtration.
- 14 -
~70679
The dyes obtained according to the invention are
suitable for dyeing and printing materials of polyacryloni~rile
or polyvinylidene cyanide as well as other acid-modified
synthetic fibres, such as acid-modified polyamide or acid-
modified polyester.
. .
By polyacrylonitrile is meant above all polymers
which contain more than 85%, for example 85 to 100%,of
acrylonitrile; in addition they contain 0 to 15% of vinyl
; acetate, vinyl pyridine, vinyl chlorine, vinylidene chloride,
acrylic acid, acrylic ester, methacrylic acid, methacrylic
ester etc.
The novel dyes effect on these fibres, which can also
be dyed in admixture with each other, strong and level dyeings
of good light fastness and good general fastness properties,
in particular good fastness to washing, persipiration,
sublimation, creasing, decatising, ironing, rubbing, carbonising,
water, chlorinated water, sea water, dry cleaning, cross-
dyeing and solvents. The dyes of the present invention also
have, inter alia, good stability in a substantial p~ range and
a good affinity e.g. in aqueous solutions of different pH
values.
The good migration capacity of the novel dyes, especially
of those which contain a mononuclear heterocycle as diazo
component, is also to be especially highlighted. It is possible
~5
.. , ~
.
- ', . '
- .
- . -- .. . . . - .
,
.... . .. . ...
1~70679.
to obtain level dyeings with these novel dyes even under
critical dyeing conditions, for example when the dyebath is
heated rapidly, and without the use of retarders. These novel
dyec are also suitable for virtually all commercially available
acrylic fibres and give level dyeings both on rapidly and on
slowly exhausting types. As examples of suitable acrylic
fibres there may be mentioned the commercial products which
are sold under the following registered trademarks: Acrilan,
Creslan, Crylo, Courtelle, Dynel, ~olan, Euroacril, Exlan,
Orlon, Velicren, Vonnel, Verel, Wolcrylon and Zefran.
The following Examples illustrate the invention, the
parts and percentages being by weight and the relationship
between parts by weight and parts by volume being the same
as that between the gram and the cubic centimetre.
~ - 16 ~ -
,,
' ~ . ' '~
.,.. , ' . , .
'
1070679
Example 1
4.4 parts of 1-methyl-2-aminopyridinium methosulphate
are dissolved in a mixture of 10 parts by volume of glacial
acetic acid and 10 parts by volume of propionic acid. To this
solution are added dropwise in ~he course of 15 minutes 3.5
parts by volume of nitrosylsulphuric acid (corresponding to
1.38 g of sodium nitrite). The resultant solution of the
diazonium salt is subsequently treated with a solution of
3.15 parts of 1-phenyl-5-aminopyrazole in 30 parts by volume
of glacial acetic acid. After it has been briefly stirred,
the reaction mixture is poured onto 300 parts of ice and the
pH is adjusted to 4 with sodium acetate. The dye of formula
L ~ H2w ~ ~ zncl4
is precipitated by addition of sodium chloride and zinc chloride,
lS filtered off with suction, washed with sodium chloride solution
and dried. This dye dyes polyacrylonitrile fibres from a
weakly acid dyebath in reddish yellow shades of complete
levelness and outstanding fastness to light and decatising.
~ ' '
- 17 -
.. . . . . .. . .
- - . . : ., ,, . . :
-- . . .. - . .. - ~, . , , , - ~:
.. . . .
.- ~ , . . . .
.. .
~o~7~ti79
Example 2
5.4 par~s of the dye of formula
N
--N = N~
u2~ ~
are stirred in 150 parts by volume of chloroform at 50C.
Then 2.5 parts by volume of dimethyl sulphate are added
dropwise and the reaction mixture is refluxed for 2 hours.
The solvent is then distilled off quantitatively as far as
possible. The residue is taken up in 100 parts by volume of
warm water and the dye solution is riltere~. The dye of
formula
CH3
~S ~ N = N l il
H2~J~N_N
is precipitated from the filtrate. From a weakly acid bath
this dye salt dyes polyacrylonitrile, acid-modified polyamide
or acid~modified polyester fibres in orange yellow shades of
absolute levelness and very good fastness to light and
decatising.
- 18 -
. ' . ~ ' ~ '
..
.
" ' " ~,
1~7()679
- Example 3
5.1 parts of the dye of formula
Q ~
¢~
obtained by conventional means by diazotising 3-amino-1,2,4-
triazole and coupling the diazonium salt to 1-phenyl-5-amino-
pyrazole, are suspended in 75 parts by volume of water together
with 1 part of magnesium o~ide. Then 5.5 parts by volume of
dimethyl sulphate are added dropwise at 25 to 30C and the
reaction mixture is kept for 3 hours at 30C. The dye sol-
ution is then filtered and the dye of formula
~(CH ) ~ ~ _ N - N
is salted out by addition of sodium chloride and zinc chloride.
This dye salt dyes polyacrylonitrile from a weakly acid bath
in a yellow shade of good fastness to light and decatising.
- 19 -
.:: . . . .. .
.. , ~ . . .
.
. .
-
10'70 67 9
..
Example 4
6.4 parts of the dye of formula
: ~ N
H2
., , ~,
.'' '
are dissolved at 90-100C in 150 parts by volume of chloro~
benzene and 10 parts by volume of dimethyl formamide, and then
2.9 parts by volume of dimethyl sulphate are added dropwise a~.
this tempera.ture. The batch is kept for 3 hours at 90 to
100C, allo~ed to cool, and the dye of formula
C~
= N ~ . 3
' . H2N~N-N
,; ' ~
..' ~
is filtered off with suction.
. The dyes of formula
: ' _ _
^ . D--N-N - ~---CH X~
. 2 \N
_' ~_
~ 20 -
- . .
. . .
- . . . . . .
.
-:. . . - . ,
~70679
. ' .
listed in ~he ~ollowing tabl.e are obtained by treating the
corresponding non quaternised compo~mds with dimethyl sulpha~e.
_ _ Shade on PAC
_. ___
greenish yellow
HC - CH
ll ll greenish yellow
; H C-N C-
3 0 ~l/
CH3
H3C C - CH greenish yellow
3 ~ \~/
i - CH3
- 21 -
:,, . : ' ~' '~: ' '. . ', :
:' .' ~ ' ' ' ~ '' ' ::
: -
1070679
_ __ . .~
D Shade on PAC
N--NO ~
3 \N/ yellow
IH3 .
CH ~
N--~ ~) . .
11 11 yellow
-C2H5--C C-- -
CH3 .
CH~;
N N ~)
~N/ yellow
CH~ .
il3C--C N--C 3 ¦ ereenish yellow
. ICH3
H~ N~3 reddish yellow
\S~ l I
- 22 -
.
-:
- 1~70679
~ . Shade on PAC
N ~
. 11 11 reddish yellow
~S/ .
H C-N ~- orange
3 ~ ~S/
C - CH orange
N reddish yellow
I /N~-CH3 .
CH3
. ~ ~ orange
- 23 -
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~070679
Printir.l~ ~ir~.~ction
5 p~r~s vf the dried dye obtained according to Example
4, 10 parts of thiodiglycol, 25 par~s of 40% acetic acid,
225 parts of a 12V/o solution of carob bean meal derivative and
235 parts by volume of boiling water are processed to a
printing paste. A polyacrylonitrile fabric is prin~ed with
this paste and the print is fi~ished in the manner conventionally
employed in actual practice.
An orange red print with very good fastness properties
is obtained.
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