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Патент USA US3186994

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United States Patent 0 " ,. C6
3,136,979
Patented June 1, 1965
3
2
3,186,979
hydroxy lower alkylamino groups represented by Q there
may be mentioned N-(hydroxy lower alkyDamino and
NzN-di-(hydroxy lower alkyl)amino groups such as N-(B
REACTIVE DYESTUFFS HAVING A DETHIQCAR
BAMYLSUBSTITUTED TRIAZEJE REQIG SUE~
STITUENT
Frank Hall and Ian Durham Rattee, Manchester, England,
assignors to Imperial Chemical Industries Limited,
London, England, a corporation or‘ Great Britain
hydroxyethyl)amino and N:N-di(B-hydroxyethyl)amino
groups.
As examples of the sulphophenylamino, carboxyphenyl
amino, disulphophenylamino and carboxysulphophenyl
No Drawing. Filed Dec. 19, 1962, Ser. No. 245,650
Claims priority, application Great Britain, Mar. 11, 1959,
8,36G/S9; May 21, 1959, 17,394/5d; July 2, 1959,
22,761/59
9 Claims. (Cl. 260-153)
amino groups represented by Q there may be mentioned
2-, 3- or 4-sulphophenylamino, 2e, 3- or 4-carboxyphenyl
10 amino, 225-, 3:5- or 2:4~disulphophenylamino and 4- or
S-sulpho-2-carboxyphenylamino groups.
As examples of the N~phenyl~N~lower alkylamino, N
This application is a continuation-in-part application of
sulphophenyl-N-lower alkylamino, N-carboxyphenyl-N
our application Serial No. 9,199, which was ?led on Feb
ruary 17, 1960, now abandoned.
This invention relates to new dyestuifs and more partic
ularly it relates to new dyestulls which are valuable for
lower alkylamino, N-disulphophenyl-N-lower alkylamino
and
N - (carboxysulphophenyl) - N~ lower
alkylamino
groups represented by Q there may be mentioned N
phenyl-N-rnethylamino, N-phenyl-N-ethylamino, N-phen
colouring natural and arti?cial textile materials, in par
ticular cellulose textile materials.
According to the invention there are provided the dye
yl-N-n-propylamino, N-(2-, 3- or 4-sulphophenyD-N
methylarnino, N-(Z, 3, or 4-carboxyphenyl)-N-methyl
amino, N-(2:5-, 3:5- or 2:4=disulphophenyl)-N-methyl~
amino and N-(4- or S-sulpho-Z-carboxyphenyDeN-meth
stutls of the formula:
lyamino groups.
As examples of the lower alkyl radicals representedby each of Z’ and Z" there may be mentioned methyl, ethyl,
propyl and butyl radicals; and as an example of a phenyl
lower alkyl radical represented by each of Z’ and Z" there
may be mentioned the benzyl radical.
Each of the groups of the formula:
wherein K represents the radical of a dyestuilv selected
from the class consisting of azo, anthraquinone, nitro and 30
phthalocyanine dyestu?s radicals.
R represents a number selected from the class consist
ing of hydrogen and lower alkyl;
12 is a positive integer not exceeding 2;
Q is a member selected from the class consisting of
chlorine, bromine, lower alkyl, phenyl, lower alkoxy, sul~
phonic acid, phenoxy, amino, lower alkylamino, hydroxy
present in the dyestulfs of the invention is attached to a
carbon atom present in the dyestuif radical represented
40 by K. The said carbon atom may form part of an aryl
phophenyl - N - lower alkylamino, carboxysulphophenyl
lower alkylamino, phenylamino, sulphophenylamino, car
boxyphenylamino, N-phenyl-N-lower alkylamino, N-sul
ring, in particular a benzene or naphthalene ring, present
in K or may form part of an alkyl chain which is directly
or indirectly attached to an aryl ring present in K.
It is preferred that the dyestuli radical represented by
amino, 'N-(carboxyssulphophenyl)-N-lower alkylamino,
N-carboxyphenyl-N - lower alkylamino, disulphophenyl
amino, N-disulphophenyl-N-lower alkylamino, cyclohex
ylamiuo, morpholino, piperidyl and
K contains at least one Water-solubilising group‘ such as a
carboxylic acid, sulphonamide, lower alkylsulphone, and,
above all, a sulphonic acid group. If desired the dyestutlc
radical represented by K may also contain a coordinately
bound metal atom such as a coordinately bound copper,
chromium or cobalt atom.
and Z’ and Z” are independently selected from the class
The dystu?s of the invention may be obtained by react
consisting of lower alkyl, phenyl lower alkyl, cyclohexyi
ing a dyestuif compound of the formula: I
and phenyl, and taken together Z’ and Z" form with the
nitrogen atom N a heterocyclic ring selected from the class
consisting of piperidyl and morpholino.
' As examples of the lower alkyl radicals represented by
each of R and Q thereymay be mentioned alkyl radicals
containing from 1 to 4 carbon atoms, in particular the
methyl radical.
As examples of the lower alkoxy radicals represented 60
by Q there may be mentioned alkoxy radicals containing
from 1 to 4 carbon atoms, in particular the methoxy radi
cal.
As examples of the lower alkylamino groups repre
Formula II
wherein K, R and n have the meanings stated, T represents
a chlorine or a bromine atom and Q’ represents chlorine,
lower alkyl represents an alkyl radical of from 1 to 4 car~
bon atoms, and as examples of such groups there may be
mentioned methylamino, ethylamino, propylamino, di
and N-methyl-N-ethylamino groups. As examples of the
11
bromine, lower alkyl, phenyl, lower alkoxy, sulphonic
acid, phenoxy, amino, lower alkylamino, hydroxy lower
sented by Q there may be mentioned N-(lower alky1)
amino and N:N-di(lower alkyl)amino groups, wherein
methylamino, diethylamino, dipropylamino, dibutylamino
it’
70
alkylamino, phenylamino, sulphophenylamino, carboxyl~
amino, N—ph-enyl-N-lower alkylamino, N-sulphophenyl
N-lower alkylamino, carboxysulphophenylamino, N-(car
boxysulphophenyl)~N-lower alkylamino, N-carboxyphen
yl-N-lower alkylamino, disulphophenylamino, N-disul
phophenyl-N-lower alkylamino, cyclohexylamino, mor
3,186,979
pholino or piperidyl, with a sulphur compound of the
formula:
s v.
As example of such 1:3:5-triazines there may be men
tioned cyanuric chloride, cyanuric bromide, 2-methyl
4: 6-dichloro-1 :3 : S-triazine, 2-methoxy-4: 6-dichloro-1 :3:
z’
D~S.i|l.N/ ’
\Z/I
5 -triazine, .2-phenyl-4: 6-dichloro-1 :3 : S-triazine, 2-phen
oxy-4:6~dichloro-1 :3 :S-triazine,
’
chloro-lz3z5-triazine,
Z-methylamino - 4: 6-di
2-ethylamino-4:-6-dichloro - 113:5
triazine, 2-N : N-diethylamino-4: 6-dichloro-1 :3 : S-triazine,
Formula III
wherein Z’ or Z" have the meanings stated above, and D
represents a'metal atom, which is preferably an alkali
metal atom such as sodium or potassium.
2,-phenylamino-4:6-dichloro h 1:3 :5 - triazine,
2 - phenyl
10 phophenylamino ) -4 :6-dichloro-1 :3 : 5 -triazine and 2-( 3':
’~disulphophenylamino ) -4: 6-dichloro-1 :3 :S-triazine.
Each of the --NHR groups present in the said dyestuif
This reaction may be conveniently brought about by
adding a ‘solution of the dyestu? compound of Formula
II in water or in an organic liquid, which is preferably a
compounds is directly attached'to a'carbon atom of an
' .aryl residue present in the dyestuif compound or each of
Water-soluble organic liquid such as acetone, or in a mix-.
the -—NHR groups is attachedtoa carbon atom of an
15
ture of water and a water-soluble organic liquid, to an
alkyl radical which is directly attached to an aryl residue
aqueous solution of the, sulphur compound of Formula
III, stirring the mixture, preferably at a temperature below
present in the dyestulf compound or which is attached‘ to
an aryl residue through a bridgingiatom or group. - As ,7
50° C., for example at a temperature between 20° C. and
examples of such bridging atoms or groups there may be
30° C., if necessary adding sodium carbonate to maintain
mentioned -——O—, —S—, —NH—-, -—'N-alkyl, —'SO2—',
the pH of the mixture between 5 and 10, ?ltering off the 20 —SO2NH—-,
—-CONH—- and -—SO2N-alkyl. The said
dyestuif which is precipitated. If necessary water and/ or
dyestuff compounds of the formula K{-NHR)n may be obi
sodium chloride, can be added to ensure complete precip
tained by’ any of the methods known for preparing dye- ,
itation of all the dyestuif.
’
‘
stu?s containing amino or substituted‘ amino groups.
WhenT and Q’ each represent chlorine or bromine
atoms then it is possible by suitable choic of the reaction
Thus, ‘for example, an azo compound containing one or
two —NHR groups, where Rp‘has the meaning stated
above, may be obtained’ by coupling a diazotised amine
with a coupling component, the amine and coupling com
ponent being'so chosen that the resulting azo dyestuff
conditions to react one orrboth of the chlorine or bromine
atoms with the sulphur compound. In general it is found
that by carrying out the reaction at a temperature between '
7 0°- and 10° C.,,only one of the said chlorine or bromine 30 contains one or two —NHR groups, or contains one or
atoms reacts with the ‘sulphur compound,v whereas at,
higher temperatures both of the chlorine or bromine
two groups, for example one or two -NR.COCH3 groups,
which are readily convertible to --NHR groups.
atoms react with the sulphur compoundl '
. V
>
As' examples of the said dyestutf compounds of'the
The sulphur compounds of Formula III may them
formula K{-NHR)n, as hereinbefore de?ned, there may
selves be obtained by reaction a secondary amine of the 35 be
mentioned, the dyestu? compounds of the'follo'wing
formula:
1
'
I
.
‘
classes without, however, limiting the classes to those
'
Z,
speci?cally described.
HN/
‘
_
'
"
'
'
'
'
'
(l) Dyestu?’ compounds of the formula:
OH
40,
2!!
wherein Z" and ,2” have the meanings stated above, with
carbon disulphide in Water in the presence of, an alkali
metal hydroxide, at a temperature between0° and 30° C.
2
drying it ata temperature below 45° C.
" '
'
As examples of the ‘sulphur compounds of‘ Formula
III there may be mentioned sodium diethyldithiocarba
mate, sodium pentamethylenedithiocarbamate, sodium di
methyldithiocarbamate, potassium ; dipropyldithiocarbaé
'
a
and at pH above 12, adding sodium chloride, ?ltering off
the precipitated compound, washing it with toluene and 45
NHR : V
6
'
S 0 SEEN
“
wherein Dlvrepre'sents a phenyl or a 'naphthyl radical
which may contain further substituents, and the --NHR
group is preferably attached to the 6- or 7-position of the‘
naphthalene nucleus.
50
mate, . sodium“ N-methyl-N-propyldithiocarbamate, so‘
dium N-methyl-N-ethyldithiocarbamate, sodium diphen
yldithiocarbamate, sodium N-phenyl-N-methyldithiocar
bamate, sodium dicyclohexyldithiocarbamate, potassium
'
r
‘
V
V
,
Particularly '~ valuable dyestuff compounds are those
wherein'Dl'represents a phenyl radical which contains an
—SO3H group'in ortho position to the azo link and, if
desired, the phenyl radical may be'further substituted by,
for example, halogen atoms such as chlorine, alkyl radi
~ di-n~butyldithiocanbamate, sodium 4-morpholinodithiotar» 55 cals such as methyl, acylamino- groups such as acetylami
Vbamate, sodium"diiso-butyldithiocarbarnate,' sodium N-i
methyl-N-cyclohexyldithiocarbamate and sodium N-ben
zyl-N-ethyldithiocarbamate. ,Such compounds may if de
sired be used in the form of their hydrates with water.
The dyestu? compounds of Formula 11 may themselves
be obtained by‘ reacting a dyestu?’ compound of the
formula K—(NHR),,, wherein K, R and n have the
meanings stated above, with a 1:3:5-triazine of the 'for
mula:'.
'
"
V
no, alkoxy radicals such as methoxy, and sulphonic acid
groups, and those wherein D1 represents'a. 1-sulpho-2
naphthyl radical.
'
Also in this class are'the dyestuff compounds wherein
D1 represents a radical of the'azobenzene, azonaphthalene ' V
orphenylazonaphthalene series.
'
'
I (2) Dyestu?’ compounds of the'formulaz I
V (lust 1111111
'
wherein D1 has the meaning stated above and the naph
.
,
Formula IV‘
V
wherein T and Q'» have the meanings stated, one molecua
_1-ar proportion of the said 1:3:5-triazine being used'for‘ '
each --NHR group present in the dyestutf compound. 75
thalene ‘nucleus contains a sulphonic acid group in either
the 3- orthe 4-position. D1 is preferablya phenyl radical
which contains a sulphonic acid group which is preferably
in an 'ortho positionto the --N==N— link, or Dr is a. 1_
spulpho-pZ-naphth‘yl rfadical.
3,186,979
5
7-met-hylamino-2-(4'-methoxy~2’-sulphophenylazo)~1
(3) Dyestu? compounds of the formula:
hydroxynaiphthaleneé-sulphonic acid,
8-( 3 '-aminobenzoylamino) -1-hydroXy-2—(2’-su1pho
phenylazo )naphthalene-3 : 6-disulphonic acid,
wherein D2 stands for a phenyl or naphthyl radical which
may contain further substituents and is preferably a di
C11
sulphonaphthylene radical, and the benzene nucleus may
contain further substituents such as halogen atoms, alkyl
radicals, alkoxy radicals and acylamino groups.
(4) Dyestuff compounds of the formula:
8-amino- l-hydroxy-Z :2'-azonaphthalene-1' : 3 :5 ’ : 6-tetra
sulphonic acid,
S-amiuo-l-hydroxy-Z: 2'-azonaphthalene-1’ : 3 :5 '-trisul~
phonic acid,
G-amino- l-hydroxy-Z : 2'-azonapl1thalene-1' : 3 : 5’-trisul
10
phonic acid,
7-aminoal -hydroXy-2:Z-azonaphthalene-d ’ :3 -disul
phonic acid,
8-amino-1-hydroxy-2- (4'-hydroxy-3 '-carboxyphenyl
wherein D3 represents an arylene radical which may con
tain further substituents and V represents the residue of a
naphthol sulphonic acid which may contain further sub
stituents, or the residue of a ketomethylene compound
such as the residue of an acetoacetarylide or a S-pyrazo
azo)naphthalene-3 : ?-disulphonic acid,
G-amino- i-hydroxy-Z- (4'-hydroxy-3'-carboxyphenyl
azo)naphthalene-3 :S-disulphonic acid.
8-amino~1-hydroxy-2- [4'- (2”-sulphophenyl~az-o ) -2’-meth
lone. D3 preferably represents a sulphophenylcne radi
:oXy- ’-methylpheny1azo] naphthalene-3 : o-disulphon‘ic
cal.
(5 ) Dyestuif compounds of the formula:
20
acid,
8-amino~1-hydroXy-2- [4'- ( 4"-methoxyphenylazo ) -2’
carboXy-phenylazo] naphthalene-3 : 6-disulphonic acid,
S-amino-l-hydroxy-Z- [4’-( ”-hydroXy-3 " : 6"-disulpho
1"-naphthylazo ) -2’- carboxyphenylazo] naphthalene
3 :6-disulphonic acid,
wherein D4 represents an aryl radical, preferably a phenyl
or naphthyl radical, which may contain further substitu
ents such as a sulphonic acid group and/ or an azo group
and K2 represents the residue of a coupling component
6-amino-1-hydroxy-2- [4’- (2"-sulphophenylazo) -2’
which contains a ——CO.CH2 group, such as an acetoacet
arylide or a 5-pyrazolone.
metho xy-S '-methylphenylazo] naphthalene-3 :S-disul
phonic acid.
2- (4'-amino-2'-methylphenylazo ) naphthalene-4: 8~disul
(6) The metal complexes, in particular the copper,
chromium or cobalt complexes, of the dyestuf‘f compounds
of classes 1, 2, 4 and 5 which contain a metallisable group,
phonic acid,
in particular a hydroxy, carboxy or lower alkoxy group,
attached to D1, D3 or D, in ortho position to the azo
2- (4'-amino-2"-acetylaminophenylazo ) naphthalene-S : 7- '
disulphonic acid,
4-nitro-4'- (4"-methylaminophenylazo) stilbene-2: 2'
disuiphonic acid,
group.
(7) Dyestuff compounds of the formula:
4—nitro-4'-(4"-arnino-2”~methyl-5”-methoxyphenylazo)
stilbeneQzW-disulphonic acid,
4-amino-4'- ( 4"-methyloxypheny1azo ) stilb ene-Z : 2’-disul
phonic acid,
4-amino-2-methylazobenzene-Z' : S’-disulphonic acid.
1-(2':5'-dichloro-4'-sulphophenyl)-3-methyl-4-(3"
(Ii) I1TH-—Y—NHR
amino-4"-sulphophenylazo) -5-pyrazolone,
wherein the anthraquinone nucleus may contain an addi
tional sulphonic acid group in the 5-, 6-, 7- or 8-p0sition
and Y represents a bridging group which is preferably a
phenylene radical which may contain further substituents
1- (4'-sulphophenyl ) -3-carboxy-4- (4"-amino-3"-sulpho
phcnylazo) ~5-pyrazolone,
1- (2'-methyl-5'-su1phophenyl) -3-methyl-4- (4"-amino
3 "- sulphophenylazo ) -5-pyrazolone,
l- (2'-sulphop'henyl) -3 -methy1-<4-( 3 "-amin o~‘4”-sulph-o
such as a sulphonic acid group.
(8) Dyestuif compounds of the formula:
phenylazo ) ~5-pyrazolone,
4- amino -4'- ( ”-methyl-1 "-phenyl-4"-pyrazol-5 ”-onyl
azo) stilbene-Z: 2'-disulphonic acid,
(5 0P1») 1:
Pc
4-amino-4"- (2."-hydroXy-3 " :6”-disulpho-1"-naphthy1
(S OzNH-Y-NHR) 111
azo ) stilbene-Z : 2'-disulphonic acid,
'
8-acetylamino-l-hydroxy-Z- (3 ’-amino-4'-sulphophenyl
wherein 'Pc represents a phthalocyanine radical and is
preferably a copper phthalocyanine radical, w represents
-—()H and/or ——NH2, Y represents a bridging group,
azo) naphthalene-3 : 6~disulphonic acid,
7- (3 '~sulphophenylamino)-1-hydroxy-2- (4'-amino-2’
carb oxyphenylazo )naphthalene-3 -sulphonic acid,
preferably an aliphatic, cycloaliphatic or aromatic bridg
ing group, p and In each represent 1, 2 or 3 and may be
the same or diiferent provided that p+m is not greater
60
than 4.
8-phenylamino-l ~hydroxy-2- (4’-amino—2'rsulphophenyl
azo) naphthalene-3 : 6-disul phonic acid,
G-acetylamino- l-hydroxy-Z- (5 '-arniuo-2’-sulphopheny1
azo)-naphthalene-3-sulphonic acid.
As speci?c examples of the said dyestuii? compounds of
the formula: IKH‘JILIRL.A there may be mentioned:
1- (3 '-arninophenyl) -3-methyl-4-(2' : 5 '-disulphophenyl
6-amino-l-hydroxy-Z-(2'-sulphophenylazo)napthalene
azo ) -5-pyrazolone,
S-sulphonic acid,
6-methylamino- l -hydroxy-2- (4’-acetylamino-2’-su1pho—
phenylazo)naphthalene-3-sulphonic acid,
_
’
1-( 3 ’-amin0phenyl) -3-carb oxy-4- ( 2’-carb oXy-4'-su1pho
phenylazo )-5-py1'azolone,
4-amino-4’- [3 "-methyl-4”- (2"' : ?m-disulphophenylazo ) -
S-amino- l-hydroxy-Z- (2.’-sulphophenylazo ) -naphthal
1"-pyrazol-5"-onyl] stilbene-Z : 2’-disulphonic acid,
cue-3 : G-disulphonic acid,
8-amino~l-hydroxy-Z-(4'-chloro-2’-su1phophenylazo)
naphthalene-3 :S-disulphonic acid,
70
7~amino-2- (2' : S’-disulphophenylazo ) -1-hydroxy-naph
The copper complex of 8-amino-1-hydroXy-2-(2'-hydroxy
thalene-El-sulphonic acid,
5'-sulphophenylazo)naphthalene-3 :6-disul phonic acid,
7-methylamino-2-(2’-sulphophenylazo)-l--hydroxy
naphthalene-S-sulphonic acid,
The copper complex of 6-amino-1~hydroXy-2-(2'-hydroxy
KT
5'-sulphophenylazo)naphthalene-B-sulphonic acid,
3,186,979
The copper complex of 6-amino-1-hydroxy-2-(2’-hydr0xy
571,523, 571,893, 571,942, 572,491, 572,833, 572,967
5 ’-sulphophenylazo )Vnaphthalene-3 : 5,-disulphonic acid,
3'-chloro-5f-sulphophenylazo ) naphthalene-3 : 6-disul
and 581,401, in Italian‘ speci?cations Nos. 577,309,
582,676, 584,124 and 594,999, and in United States speci?~
cations wNos. 2,258,977,_2,680,129, 2,860,128, 2,873,269,
phonic acid,
2,891,941 and 2,910,464.
‘ The copper complex of 8-amino-l-hydroxy-2-(2'-hydroxy
‘
,
The copper, complex of 6-methylamino-Lhydroxy-Z-GZT
carboxy-5’-sulphophenylazo)naphthalene-3-sulphonic
acid, ,
'
7
Alternatively the new dyestulfs, as hereinbefore de?ned,
can be ‘obtained by reacting a dyestu? compound of the
formula: K{—NHR),,€wherein.K, R and n have the mean
'
' The copper complexiof 8-amino-1-hydroxy-2-[4'J(2"-sul~
ings stated above, with a 1:3 :S-triazine of the formula:
phophenylazo ) -2'-methoxy-5 '-methylphenylazo] naph 10
thalene-3:6-disulphonic acid;
,
The copper-complex of 6-amino-1-hydroxy-2[4'-(2":5"
disulphophenylazo) -2',-met-hoxy-i5 ’-methy-lpheny-lazo] naphthalene-3:S-disulphonic acid,
7
.
l
The copper complex’ of p1-(3'-amino-4-sulphophenyl)-3
methyl-4- [4"- (2"’ : 5"’-disulphophenylazo ) -2"-me-'
15
thoxy-5"-methylphenylazo]-5-pyrazolone,
The copper complex of 7-(4'—amino-3’-sulphoanilino)~1
hydroxy-Z- [4"- (2"' : 5"’-disulphophenylazo ) -2"-me
wherein T,» Q, Z’ and Z” have the meanings stated, one
molecular proportion of the said 1:3:5-triazine being used
for each —NHR group present in the dyestu? compound.
This alternative method may be,conveniently' brought
about by adding a solution of the said dyestutf compound
th-oXy-S "qmet-hylphenyl azo] naphthalene-3-sulplronic
acid,
'9
i
'
.
>
The copper complex of 6-(4'-amino-3’-sulphoanilino)-1
hydroxy-2-(2”-carboxyphenylazo)-rraphthaIene-B
in water or in a‘water-soluble organic liquid or in a mix‘
ture of water and a water-soluble organic liquid, to a solu
The 1:2-chromium complex "of 7-amino-6'-nitro-1:2'-di; 25 tion or suspension of the said triaz'ine in water and/or a
sulphonic acid,
'
hydroxy-Z: 1’-azonaphthalene-3' : 4'-disulphonic acid,
The 1:2-chromium complex of 6-amino-1-hydroxy-2-(2'
water-miscible ‘organic liquid, ‘stirring the mixture, pref-~
er-ably at a temperature between ‘0° C. and 30° C.,'adding
sodium carbonate to maintain the pH‘ of the mixture be
carboxyphenylazo)naphthalene-3-sulphonic acid, '
The 1:2-chromium complex of 8-amino-1-hydroxy-2-(4'
nitro-2'-,hydroxyphenylazo) naphthalene-3 :6-,disul-_ ,
phonic acid,
'
tween 5 and 10,v ?ltering o?the dyestu? which is precipi
tated.
j ,The 1:2-cobalt complex of 6-(4'-amino-3{-sulphoanilino)
, The 1:3:5-triazines of Formula V'may themselvesbe‘
l-hydroxy-Z-(5"-chloro-2"-hydroxyphenylazo)naph
thalene-3-sulphonic
acid,
,
,
‘
,
1
obtained by reacting a 1:3:5-triazine of FormulalV with
,
a sulphur compound of Formula 111.,
'
YThe 1":2-'chromium complex of 1- ( 3.'-ami,n0-s4'>-rsulpho
35
'
»
Alternatively the vdyestuffs wherein K represents the
phenyl)-3-methy1-4-(2"-hydroxy-4"1sulpho-1"-naph- 7,
radical of an azo dyestulf may be obtained by coupling a
thylazo) -5-pyrazolone,
diazotised amine with a coupling component, theamine
and coupling component together containing one or two
groups of Formula I. This may be conveniently brought
about by adding sodium nitrite to a solution or suspension
of the amine, which may be an aminoazo compound, in an
aqueous solution of hydrochloric acid and adding the so
obtained solution or suspension of the diazo compound to
a solution of the coupling component and isolating, by
,
,
The 1:2-chromium complex of 7-(4'-sulphoanilino)-sl
hydroxy-2-(4"-amino-2”-carboxyphenylazo)naph
thalene-3-sulphonic acid,
,
r
»
a‘
p
.
' '40
,_
,»
The 1:2-chromium complex of 1-(3'-aminophenyl)-3
, methyl-4% "-nitro—2"-carboxyphenylazo}S-pyraZQlone'.l
1-amino-4-_( 3 “amino-4'*sulphoanilino ) anthraquinone
2-sulphonic acid,
'
I
5
V
‘
conventional methods,'the azo dyestuff, which is formed.
1-amino-4- (4'-amino-3’-sulphoanilino) anth'raquinone
2:5-disulphonic acid,
a
>
1
' The amines and coupling components containing at least
one group of Formula I may themselves be obtained by'
treating the corresponding primary amine or coupling com
,
1-arnino-4- [4'- (4"-amino-’3"-sulphophenyl ) anilino ] anthraquinone-Z:S-disulphonic acid,
,
,
ponent containing at least one ——NHR group with (a) a
1-amino-4_- [4’f-amino-2"-sulphophenylazo )anilino] - anthraquinQne-ZfS-disulphonic acid,
'
lz3z5-tria'zine of Formula V, ori(b)_> ta 1:3:5-triazine of
>
Formula 1V and then with a sulphur compound of Formu
1-amino-4- (4'-methylamino-3 '-su_lpho anilino) anthra
quinone-2—sulplionic acids,
‘
,
‘
la III.
,
3-(3’-amino-4’-sulphophenyl)sulphamyl copper phthalol
iDi-4-(3’-amino-4'-sulphophenyl)sulphamyl copper ph'thal- ,
cyanine-tri—3-sulphonic acid,
‘
ocyanine-di-4-sulphonic ‘ acid,
i
"
'
'
' 3-(3'-aminophenylsulphamyl)13-sulpharnyl-copper phthal;
ocyanine-di-3-sulphonicpacid,
and
V '
V
‘
4-amino-2'-nitr0¢[email protected] :4'-disulpl1onic acid. 4 V
i Dyestu? compounds of Formula I, as hereinbeforendey
?ned, which-can be used 'to obtain the dyestuffs of the
', invention are described in British speci?cations Nos.
'
pAlternatively the dyestuffs, as ,hereinbefore de?ned,
wherein Q represents lower alkoxy,jsulphonic acid, pheni '
55
:7
Copper phthalocyanine 3~sulphon-N-(3'-amino-4’-sulpho;
phenyl)amide 3-sulphonamide 3-sulphonic acid,
Copper phthalocyanine' 3-sulphon-N-(4'-amino-3’-sulpho¥
pheny1)amide 3-sulphonamide 3-su1phonic acid.’
~
If necessary water and/or sodium'chloride can be
added'tojensure complete precipitation of all the'dyestuif.
'
oxy, amino, lower alkylamino, hydroxy'lower alkylamino,’
phenylamino, sulphophenylamino, carboxYphenylamino,
N-phenyl-N-lower lalkylamino, N-sulph-ophenyl-N-lower
alkylamino,lN-(carboxy-sulphophenyl)-N-lower a'lkylami
no, N-carboxy-phe‘nyl-N-lower alkylamino,‘disulphophen
60 ,ylamino,
N-disulphophenyl-N-lower alkyl-amino, cyc1o-'
hexylamino, morpholino 'and piperidyl, may be ‘obtained
>
by reacting a dyestuff as hereinbefore de?ned wherein Q‘
representschlorine or bromine, with a compound of the
formula: 'P-p-G wherein P represents ahydrogen or a
675 metal atom-and G represents lower. alkoxy, sulphonic acid,
phenoxy, amino, lowersalkylamino, hydroxylower alkyl
, amino, phenylamino, sulphophenylamino, vcarboxyphenyla
amino, N-phenyl - N ; lowersalkrylamino, N - sulphophenl
yl-Nflower alkylamino, N - (carboxy- sulphophenyl)-,N~,
209,723, 298,494, 467,815, 503,609, "772,030, 774,925,
775,308, 780,591, 781,930, 784,221,'785,120, 785,222, 370 lower alkylamino, N-carboxyphenyl -'N - lower alkyl4
amino, disulphophenylamino, .N - disulphophenyl - ,N -,
805,562, 812,957, 825,377 and 826,405, in Belgian speci?f
cations Nos. 556,092, 558,390, 558,801, 558,816, 558,817,
lower alkylamino, ‘cyclohex'ylamino, morpholino and"
558,884, 558,957, 559,782, ‘559,945, 560,791, 560,792,
This process may be ‘conveniently, brought, about by‘
560,793, 560,794, 560,795, 560,839, 563,439, 563,862,
568,297,v568,832, 569,115, 570,122, 570,343, 571,238, 75 stirring a mixture of the compound of the formula: 'P-G
8,186,979
lb
and the new dyestui‘r', as hereinbefore de?ned, in water,
chlorine or bromine atoms attached to the triazine ring
instead of
or in a water-miscible organic liquid, or in a mixture of
water and a water-miscible organic liquid, preferably at
a temperature between 0° and 100° 0., adding sodium
carbonate to maintain the pH of the mixture between 5
and 10, and ?ltering oi’r' the dyestu? which is precipitated.
If necessary water and/ or sodium chloride can be added
to ensure complete precipitation of all the dyestu?’.
As examples of compounds of the formula: P—G which
may be used there may be mentioned methanol, phenol,
ammonia, methylamine, diethylarnine, aniline, metanilic
acid, sodium sulphite, ,B-hydroxyethylamine, di(;3—hydroxy~
ethylarnine), cyclohexylamine, morpholinc, N-methylani
groups.
The new dyestu?s which contain water-solubilising
groups, for example sulphonic acid and carboxylic acid
10 groups, which render them soluble in water are particu
larly valuable for colouring cellulose textile materials.
For this purpose the dyestuffs are preferably applied to
the cellulose textile material in conjunction with a treat
ment with an acid-binding agent, for example sodium
carbonate, sodium metasilica-te, trisodium phosphate or
sodium hydroxide, which may be applied to the cellulose
textile material before, during ‘or after the application of
the dyestuif. Alternatively when the dyed textile material
line, sulphanilic acid, aniline-2:4-, 2:5- or 3:5-disulphonic
acid and 4- or S-sulphoanthranilic acid.
If desired the new dyestuffs, as hereinbefore de?ned,
can be isolated from the medium in which they have been
formed and/or subsequently dried in the presence of a
buffering agent. As examples of buit'ering agents which
is to be subsequently heated or steamed a substancetsuch
can be used for this purpose there may be mentioned 20 as sodium bicarbonate or sodium trichloroacetate, which
on heating or steaming liberates an acid-binding agent,
buffering agents derived from phosphates such as sodium
dihydrogen phosphate and disodium hydrogen phosphate,
can be used.
citrates such as sodium citrate, borates and dialltylmet
auilic acid such as sodium diethylmetanilate, which is pref
'
For example the cellulose textile material can be
coloured by treating the cellulose textile material with
an aqueous solution or suspension of the acid-binding
erably used in conjunction with sodium hydrogen sulphate.
Preferred classes of dyestuds of the invention are the
dyestuffs which are represented by the formulae
agent and then immersing the so-treated cellulose textile
material in a dyebath comprising a solution or disper
sion of one or more of the new dyestuffs, as herein
before de?ned, at a temperature of between 0° and 100°
30
C., removing the dyed cellulose textile material from
the dyebath and if desired subjecting the dyed cellulose
textile material to a treatment in a hot aqueous solution
of soap.
If desired the cellulose textile material which has been
treated with an aqueous solution or suspension of the
acid-binding agent may be passed between rollers to re
move excess aqueous solution or suspension of the acid
binding agent and/ or dried before being treated with the
aqueous solution or dispersion of the said dyestuffs.
ill)
Alternatively the aqueous solution or dispersion of the
dyestu? may be applied by padding to the cellulose
textile material which has been treated with the acid-bind
ing agent and the cellulose textile material then passed
through rollers and subsequently subjected to the action
In these preferred classes it is further preferred that K
is a radical of a dyestuii selected from the class consisting
of heat or steam. Alternatively the cellulose textile ma
terial can be padded with an aqueous solution or disper
sion of one or more of the new dyestuffs, as hereinbefore
de?ned, which also contains an acid-binding agent, pass
ing the so-treated cellulose textile material through
of azo, antbraquinone and phthalocyanine dyestulf radi 50 rollers, then if desired drying the cellulose textile mate
cals which, preferably, contains at least one water-solubil
rial at a suitable temperature, for example 70° C., and
ising group selected from the class consisting of sulphonic
then subjecting the cellulose textile material to the action
acid and carboxylic acid groups, that R is a hydrogen
atom, and that Z’ and Z" each represent lower allryl radi
cals, in particular ethyl radicals.
The new dyestuffs, as hereinbefore de?ned, are valuable
for colouring natural and arti?cial textile materials for
example textile materials comprising cotton, viscose ray
on, regenerated cellulose, wool, silk, cellulose acetate,
polyamides, polyacrylonitriie, modi?ed polyacrylonitrile
and aromatic polyester ?bres. For this purpose the dye
stutl’s can be applied to the textile materials by dyeing,
padding or printing using printing pastes containing the
conventional thickening agents or oil-in-water emulsions
or water-in-oil emulsions, whereby the textile materials
are coloured in bright shades possessing excellent fast-r.
ness to light and to wet treatments such as washing.
It
is also found that the dyestuffs build-up well to give heavy
depths of shade on textile materials.
of heat or steam.
Alternatively the cellulose textile ma
terial can be dyed by immersing it in a dyebath compris
ing an aqueous solution or dispersion of the one or more
of the said dyestuffs which also contains an acid-binding
agent, at a suitable temperature for example between
0° and 100° C., and thereafter removing the cellulose
textile material from the dyebath, if desired subjecting
60 it to a treatment in a hot aqueous solution of soap and
?nally drying the dyed cellulose textile material. Alter
natively the aqueous solution or dispersion of one or
more of the said dyestuffs can be applied to the cellulose
textile material by a dyeing or a padding method and
the coloured cellulose textile material subsequently im
mersed in an aqueous solution or suspension of the acid
binding agent, preferably at a temperature between 50°
C. and 100° C., or alternatively the coloured cellulose
The dyestuffs of the invention have excellent stability
textile material may be padded with an aqueous solution
to storage, that is to say the dyestuffs undergo little or
no loss in strength when stored either at normal tem
peratures for example at 20° C., or at elevated tempera
terial dried and then subjected to the action of heat or
steam. Alternatively the cellulose textile material can
tures, for example at 60° C.; and in this respect they are
aqueous solution or dispersion of one or more of the
or suspension of the acid-binding agent, the textile ma
be dyed by immersing it in a dyebath comprising an
superior to the corresponding known dyestuffs having 75 said dyestuffs, preferably at a temperature between 20°’
3,186,979
11
7
and» 100° C., and, after the textile material has'absorbed
some or all of the dyestuffs, adding an acid-binding agent
and proceeding with the dyeing at'the same or a different
temperature.
1
l2
,
surface-active materials with or without protective col
loids such as dextrin, British gum and water-soluble'pro
teins. If desired the aqueous paste of the dyestuffs so
obtained may be dried to form a re-dispersible powder
which may be converted to a nonedusting powder by any
-
The concentration'of the acid-binding agent present
of the processes known for forming'non-dusting powders,
in the aqueous solution or suspension or in the aqueous
dispersion of the dyestuffs is not critical but it is pre
ferred to use between,0.1% and 10% of the acid-binding
agent based on the total weight of the aqueous solution
or suspension. Ifdesired the aqueous solution or sus 10
The new dyestu?s, as hereinbefore de?ned, can be
applied to nitrogen-containing textile materials such as‘
wool and polyamide textile materials, ‘from a mildly alka
line, neutral or acid dyebath. The dyeing process can be
pension of the acid binding agent may also contain fur
ther substances, for example electrolytes such as sodium
carried out at a constantror substantially constant pH,
materials, for example sodium chloride, sodium sulphate,
ing may be started at a dyebath pH of about 3.5 to 5.5
that is'to say the pH of the dyebath remains constant
chloride and sodium sulphate.
'
or substantially constant during the dyeing process, or
The aqueous solution or dispersion of the one or more
if desired the pH‘ of the dyebath can'belaltered at any
of thesaid dyestuffs may also contain substances which 15' stage of the dyeing process by the addition of acids or
are known to assist the application of dyestuffs to textile
acid salts or alkalis or alkalinesalts. For example dye
urea, ‘dispersing agents, surface active agents, sodium
and raised during the dyeing process to about 6.5 to 7.5
alginate or-an emulsion of an organic liquid, for ex
or higher if desired. The dyebath may also contain
ample, trichloroethylene in water.
20 substances which are commonly used in the dyeing of
Alternatively the cellulose textile materials can be
printed with a printing paste containing one or more of
nitrogen-containing textile ‘materials.
the new dyestuffs of the invention.
acetate, sodium sulphate, ethyl tartrate, non-ionic dispers—
ing a'gents’su-ch as condensates of. ethylene oxide with
amines, fatty alcohols or phenols, surface active cationic
This may be conveniently brought about by applying
' a printing paste containing one or more of the said dye
As examples of
such substances there may be' mentioned ammonium
25
stuffs, to a cellulose textile material which has been
agents such as quaternary ammonium salts for example
impregnated with ‘an acid-binding agent and thereafter
subjecting the printed cellulose textile material to the
bromide and organic liquids such as n-butanol and benzyl
action of heat or steam. Alternatively a printing‘ paste
containing one or more of the said dyestuffs and con
taining an acid-binding agent can be applied to the cellu
.lose textile material and the printed cellulose textile ma
terial subsequently subjected to the action of heat or
cetyl trimethylammonium bromide and cetyl pyridinium
alcohol;
'30
,
'
'
r
'
.7
We are aware of British'speci?cation No. 363,690
. which relates to a manufacture of triazine derivatives
containing sulphur, by causing a compound of the gen
eral
formula:
7
'
r
steam.“ Alternativelyfa printing paste containing one or
more of the said dyestuifs can be applied to the cellulose
textile material which is subsequently immersed in a hot
a
V
)5
0
aqueous solution or suspension of the acid-binding agent
or alternatively the printed textile. material is impreg
a;
nated with an aqueous solution or suspension of-theacid
binding agent and subsequently subjected to the action of 40
heat or steam.
'
in which X is a halogen atom or any desired residue and
in which there is still present at least one halogen atom
capable of exchange, to react with one, two or three
'7 After applying the printing‘paste to the cellulose tex- V
tile'material the printed textile material may, if desired,
be dried, for example'ata temperature between 20°
and 100° C., before the printed textile material is sub
45
jected to the action of heat or steam.
molecular proportions of a sulphur compound, in which
at least one sulphur atom is united on the one hand
to a metal and on the other hand to arresidue capable
The cellulose textile material may be printed with the
of being split oif, and causing the product thus obtained,’ '
printing paste by any of the commonly'known methods
so far as it still contains reactive halogen atoms, to react
of applying printing pastes to textile materials, for ex
a compound having hydrogen atoms that can be
ample by'means' of roller printing, screen printing, block 50 with
exchanged and, if necessary, converting the condensation
printing, ‘spray printing, or stencil printing. The print
product thus obtained into the mercapto t-riazine by treat
. ing pastes may also contain the commonly used adjuvants,
'ment'with a saponifying
or reducing agent. There is
'
for example urea, thickening agents, for example methyl
cellulose, starch, locust bean gum, sodium alginate, water
in-oil emulsion, oil-in-water emulsion, surface active
agents, sodium m-m'trobenzene sulphonate, and organic
liquids,
for
example
ethanol.
.
.
"
p
_
no disclosure in the speci?cation that X can be the resi
due of a dyestutf molecule and that the sulphur com
55 pound can be a. compound of the Formula III, as de?ned
in the present application.
t
7
' '
‘
The invention is illustrated but not limited by the fol-'
' At the conclusion of the dyeing and/or printing proc
esses it is preferred to subject the sic-coloured cellulose
lowing examples in which the parts and percentages are
by weight:
7
'
textile materials to’ a '“soa-ping” treatment, which may 60
l
.
Example 1
be carried out by immersing the coloured cellulose textile
materialsrfor a short time, for example 15 minutes, in a
A solution of 22 parts of sodium rdiethyldithiocarbra~
hot- aqueous solution of soap and/ or detergent, andsube
mate trihyd-rate in 50 parts of water is added with stirring
sequently rinsing the coloured cellulose textile material in
to a solution of 18 parts of the trisodium salt of 7-(2’
water.v before drying it.
'
I
65 sulphophenylalzo)-1-(4":6"-dicl1loro - 1":3":5" - triaziné
- Those newdyestu?s which do not contain water-solu
bilising groups for example'sulphonic acid, carboxylic
acid, sulphonamide and acylsulphonamide groups are, in
general, applied to textile materials in the form of an
aqueous dispersion which may beobtained by gravel 70
‘ milling’ the dyestulf with water in the presence of a dis
persingt agent, for example the sodium salt of sulpho- ' '3
2"-ylamin-o)-8-naphthol-3 :6-disulphonic acid (which may
be obtained as described ‘in Example 1 of British speci
?cation No. 785,222): in 1000 parts of water and the
resulting mixture is stirred for 3 hours at a temperature
between 20? and.22° C.
150 parts of potassium chloride ' V
are then added an'dthe dyestuff which is precipitated is .
?ltered off and dried at a temperature of 40° C. On
nated naphthalene formaldehyde condensation products,
analysis the dyestulf isfound to contain 7 sulphur atom
sulphosuccinic acid esters, 'Turkey red oil, alkyl phenol/
ethylene‘ oxide condensation products, soap and similar’ 75
for each molecule of the dyestuff.
.
' .
When applied to cellulose textile ‘materials in con-7
3,186,979
13
function with a treatment with an acid-binding agent the
dyestu?f yields red shades possessing excellent fastness
amino) - 2' - methylphenylazo] - naphthalene - 4:8 - di
to washing.
sulphonic acid (which may be obtained as described in
Example 2
Example 1 of British speci?cation No. 774,925) in 500
A solution of 22 pants of sodium diethyldithiocarba
mate t-rihydrate in 100 parts of water is added with stir
ring to a solution of 15.3 parts of the disodium salt of
parts of water. The mixture is then stirred .for 10 hours
at a temperature of 20° C. and then for 10 hours at .a
temperature between 30° C. and 35° C. 70 parts of so
dium chloride are then added. and the precipitated dye
2-[4'-(4":.6"-dichloro - 1”:3":5" - triazin - 2”-ylamino)
2’-methylphenylazo]~naphthalene - 4:8 - disulphonic
Istulf is ?litered oil° and dried at 40° C.
acid
When applied to cellulose textile materials in conjunc
(which may be obtained as described in Example 1 of 10
tion with a treatment with an acid-binding agent the dye
British speci?cation No. 774,925) in 1000 parts of Water.
stu?” yields bright yellow shades possessing excellent fast
The mixture is then stirred for 20 hours at a temperature
ness to washing.
of 20° C. 130 parts of sodium chloride are then added
Example 7 V
and the precipitated dyestu?" is ?ltered oil and dried at
40° C. On analysis the dyestuff is found to contain 5.3
A solution of 49.5 parts of sodium diethyldithiocar
atoms of sulphur for each molecule of the dyestuff.
bamate t-rihydrate in 400 parts of Water is added during
When applied to cellulose textile materials in con
15 minutes to a solution of 51.1 parts of the disodium
junction with a treatment with an acid-binding agent the
salt of 1-(4':6'-dichloro-l’:3':5'-triaain-2'-ylamino)~8
dyestuff yields bright yellow shades possessing excellent
20 naphthol-3,6-disulphonic acid in 1200 parts of Water, the
fastness to washing.
temperature of the mixture ‘being maintained between
Example 3
20° C. and 25° C. during and subsequent to the addition.
A mixture of 8.58 parts of sodium hydrogen phosphate
A solution of 34 parts of sodium diethyldithiocarba
and 16.42 parts of potassium dihydrogen phosphate are
mate trihydrate in 100 parts of water is added with stir
ring to a solution of 29.3 parts of the trisodium salt of
then added and after 20 hours 400 parts of potassium
chloride are added. The dipotassium salt of 1-[4’:6’-bis
l-amino - 4 - [4'-(4":6"-dichloro - 1":3”:5” '- niacin-2”
ylamino)anilino] anthraquinone-2z3’z5 - trisulphonic acid
(which may be obtained as described in Example 1 of
British speci?cation No. 781,930) in a mixture of 650
parts of water and 50 parts of acetone. The mixture
is then stirred for 20 hours at a temperature of 20° C.
and a 10% aqueous solution of hydrochloric acid is
(diethyldithiocarbamyl) - 1':3’:5' - tr-iazin-i2’-ylamino]-8
naphthol-3:6—disulphonic acid which is precipitated is
-
1 - [41:16’ - bis(diethyldithiooarbamyl) - 1’:3':?5’ - triazin
2'-ylamino]-8-naphthol-3:6-disulphonic acid in 200 parts
added until the pH of the mixture has fallen to 7.5.
30 parts of sodium chloride are then added and the dye
stufr‘ which is precipitated is ?ltered oil, and dried at
40° C. On analysis the dyestull is found to contain
7 sulphur atoms for each molecule of dyestutl’.
When applied to cellulose textile materials in con
junction with a treatment with an acid-binding agent the
dyestutl yields bright blue shades possessing excellent
fastness to Washing.
?ltered off,'washed with ethanol and dried at 20° C.
To a solution of 19.2 parts of the dipotassium salt of
of water, which has been previously cooled to a tempera
ture ‘between 5° C. and 10° C., there is gradually added
an aqueous solution obtained by diazotising 4.88 parts of
40
the sodium salt of aniline-Z-sulphonic acid, the pH of the
reaction mixture ‘being maintained between 7 and 8 by ‘the
addition of sodium carbonate. The solution is then stirred
for 2 hours, 30 parts of potassium chloride are added
and the precipitated dyestuff is ?ltered off. The ?lter cake
so obtained is mixed with 1.03 parts of sodium hydrogen
Example 4
phosphate and 1.97 parts of potassium dihydrogen phos—
In place of the 34 parts of sodium diethyldithiocarba
mate trihydrate used in Example 3 there are used 21
phate and dried at 20° C.
When applied to cellulose textile materials in conjunc
tion with a treatment with an acid-binding agent, with or
without the application of heat, bluish~red shades are ob
tained ‘which are fast to Washing.
parts of sodium dimethyldithiocarbamate.
()n analysis
the dyestutf so obtained is found to contain 6.7 sulphur
atoms for each molecule of dyestuff.
When applied to cellulose textile materials in con
junction with a treatment with an acid-binding agent the
dyestuif yields bright blue shades possessing excellent
fastness to washing.
Example 5
A solution of 5.03 parts of sodium pentamethylene
dithiocarbamate in 60 parts of water is added with stir
ring to a solution of 8.95 parts of the trisodiumsalt of
7-(2’-sulphophenylazo) - 1 - 4":6” - dichloro - 1”:3":5"—
Example 8
‘A solution of 5.62 parts of sodium diethyldithiocar
'bamate trihydrate in 50 parts of water is added with stir
ring to a solution of 17.9 parts of the trisodium salt of
7 - (2’ - sulphophenylazo) - 1 - (4":6" - dichloro - 1":3":
5" - triazin - 2" - ylamino) - 8 - naPhthol-B‘zG-disulphonic
acid (which may be obtained as described in Example 1
of British speci?cation No. 785,222) in 400 parts of‘
water and the resulting mixture is stirred for 3 hours at
acid
a temperature between 20° C. and 22° C. :100 parts of
(which may be obtained as described in Example 1 of
sodium chloride are then added and the dyestulf which is
British speci?cation No. 785,222) in 250 parts of water 00 precipitated is ?ltered off. The ?lter cake so obtained is
and the resulting mixture is stirred for 2 hours at a tem
mixed with 0.99 part of disodium hydrogen phosphate and
perature between 20° and 22° C. and then for 2 hours
2.01 parts of potassium dihydrogen phosphate and the
triazin-2”-ylamino) - 8 - naphthol - 3:6 - disulphonic
at a temperature between 30° and 35° C.
80 parts of
‘ potassium chloride are then added and the dyestu? which
is precipitated is ?ltered oh” and dried at a temperature
of 40° C. On analysis the dyetuff is found to contain
7 sulphur atoms for each molecule of the dyestuff.
When applied to cellulose textile materials in conjunc
mixture is dried at a temperature between 20° and 25° C.
On analysis the dyestulf is found to contain 5 sulphur
atoms and v1 organically bound chlorine atom vfor each
‘molecule of dyestuff.
When applied to cellulose textile materials in con
junction with a treatment with an acid-binding agent the
tion with a treatment with an acid-binding agent the dye
yields red shades possessing excellent fas'tness to
stuff yields red ‘shades possessing excellent fastness to 70 dyestuif
washing.
washing.
The following table gives further examples of the new
Example 6
A solution of 5.03 parts of sodium pentamethylene
dithiocarbamate in 60 parts of Water is added with stir
ring to ,a solution of 7.164 parts of the disodium salt of
dyestuffs of the invention which are obtained in the man
ner described in Examples 1 to ‘6 by condensing the di
thiocarbamic acid derivative listed in the third column
of the table with the dichlorotriazinylamino compound
3,186,979
15
'7
i6 ‘
the table with the. dichlorotri azinylarnino
compound which‘
Which is-i-tself obtained by condehsing cyanuric chloride ,
with the aminoazo compound listed in the second column
is itself obtained by condensing cyanuric chloride With
of the table.
the amlnoazo compound llsted '1n the second column of '
a
Example
Aminoazo compound
Dithiocarbamic acid derivative
Shade on cellulose
‘
textile materials
l-amino-S-hydroxy-2’:7-azonaphthalene-l’13:6-trisulphonic acid _____ __ Sodium diethyl dithiocarbamatd...
.Bluish~red.
1-amino-7-[4'-(phenylazo)-2’-methoxy-5’-methyl-phcnylazo]~8-
___. do ___________________ ._
Blue.
_ _ _ _ J1 n
Yellow
hydroxynaphthalene-3:2” :G-trlsulphonic acid.
1- (3’-aminophenyl) -3'-carboxy-4-(1” :5"-disolphonaphthyl-2”-azo)-5pyrazolone.
"
‘
'
‘
2-meiéhylamin0-5-hydroxy-6:2’-az onaphthalene-7:1’:5'-trisulphonic
aci
‘
Sodium di-n-propyl-dlthiocarb amate. _ _
.
Orange.
Y
' 1-(2’:5’-dich1orophenyl)-3-methyl-4-(8”-aminopheny1azo)~5-
r
Sodium dicyelohexyl-dithiocarbamatc..
Yellow.
2-(4’-amino-2’-methylphcnylazo)naphthalene-4:8-disulphonic ae1d____ Sodium dimethyl-dithiocarbamate.
1-amin0-8:2’-d.ihydroxy-7-(phenylazo)-naphthalene-3:5’ :G-tri-
;Do. '
Sodium diethyl-dithiocarbamate- _ .
Blue.
sulphonic acid.
l-amino-S:2’-dihydroxy-7-(3’-nitrophenylazo)naphthalene-3:5’26disulphonie acid.
2-aruino-6-[2’-methoxy-5’-mcthyl-4’-(2”:5”-disulphophenylazo)
phenylazol-E-naphthol-l:7-disulpl1onie acid.
'Do.
Bluish-violet.
1:2-cobalt complex of 1-(3’-amino-4’-sulph0pheuyl) 3-methyl-4-(2’carboxyphenylazo)-5-pyraz olone.
_
.
________ __
_
_
l-berlizgylaminocii (3 ’-aminophenylazo) -8-naphthol~3:6:6’-tnsu p
omc aci
.
_
Yellow.
_
.
Sodium drphenyl dithiocarbamate_ _ . _ _
_
V
Red.
'
'
1:2-chromium complex of 2-amino-5-hydroxy-6-(2’-carboxyphenyl-
Sodium pcntamethylenc dlthiocarbamate- _ _ Brown.
azo)naphthalene-7-sulphonic acid.
The following table gives further examples of the new 25 the table. The fourth column of the'table indicates the
dyestuffs of the invention which are obtained by the
.shades obtained when the dyestuffs are‘ applied to cellu¢
method described by Example 8 by condensing the di
thiocarbamic acid derivative listed in the third column of
lose textile materials in conjunction’ with a treatment with,
an acid-binding agent.
'
Shade obtained on
Example
Aminoazo compound
Dithiocarbamie acid derivative
.
21 _________ ._ 1-amino-7-(2’-sulphophenylazo)~8-naphthol-3:G-disulphonic acid ____ __ Soé’iiumt
.
22
23
r
r
.____do
-._-_dn
cellulose telxtile
.
-
ama
‘
____
____ _.
ma eria s
N -methyl-N7cyclohexyldithiocare.
.
.
-
'
Do.
Do.
ma e.
1-?m?no-7-(pheny1azo)-8—naphthol-3:G-disulphonie acid _____________ -_
.
Sodium diethyldithiocarbamate ______ __
___
2-(4'-amino-2'-methylphenylazo)~naphthalene-4z8-disulphonic acld.__ __--_do _____________________________________ _.
2-amino-6-(2'-sulphophenylazo)-5-naphthol-7-sulphonic acid
_
Red.
Sodium N-ethyléN-benzyldithiocarbamate__
Sodiutm
N-methyl-N-phenyldithioearba-
Do.
Yellow..
Orange.
2-amino-7-(2’-su1ph0phenylazo)-8-naphtho176'sulph0nic acid ________ ._
Do.
1 - (2’:5’ - dichloro-‘i’ - sulphophenyl) - 3 - methyl - 4 - (3” - amino-6"
sulphophenylazo)-5-pyrazolone.
_
1 - (2’ - chloro - 5’ - sulphophenyl) - 3 - methyl - 4 - (3" - 2 - amino -6”-
Yellow.
2 - amino - 6 - (2’ - sulpho - 4’ - methoxyphcnylazo) - 5 - naphthol - 7-
Scarlet. V
D0.
sulphophenylazo)-5-pyrazolone.
sulphonic acid.
'
2 - amino - 7 - (2’ - sulpho - 4’ - methoxyphenylazo) - 8 - naphthol - 6-
sulphonic acid.
32 ________ __
33 _________ __
34 ......... __
Red.
‘
2 - methylamino - 7 - (2’ - sulpho - 4’ - mcthoxyphenylazo) - 8 - naph-
D0.
thol-?-sulphonic acid.
.
_
2-amino-5-hydroxy-6:2’-azonaphthalene-7:1’:5'-trisulphonic acid ____ -_
2 - methylamino - 5 - hydroxy - 6:2’ - axonaphthalene - 7:1'z5’ - trisulphonic acid. .
Orange.
Do.
'
35'. ________ _. 1:2-chromium complex of 2-amino-6-(2’-carboxy-phenylazo)-5—naph-
Brown.
thol-7-sulphom'c acid.
»
36 ______________ __do____.
_
Sodimn N:N-pentamethylene dithiocarba-
'
mate.
37
.____do
38
_____do
‘
____ __
Sodium
»
'
~
4 - gitro - 4_’((i4’ - N - methylaminophenylaz'o)stilbene - 2:2’ - dlsulp
omc aci
.
.
Do. . v
7
Sodium dimethyldithiocarbamate__ T ______ __
.
mate.
Do.
N-methyl-N-phenyldlthlocarba'
.
Do.
-
Sodium diethyldithiocarbamate ____ __, ____ _.
.
Reddrsh-yellow.
.
1;2-chromium complex of G-amino-l:2’-dihydroxy-6'~nitro-2:1’-azo-
Black
Reddlsh-orange. '
Orange.
Red.
Scarlet.
Do. .
Violet.
Reddishforange. '
2‘amirio-8-hydroxy-7:2’-azonaphthalenc-6:4’:8’-trisulphonic acid _ _ _'__ _
‘Do.
Z-amiuoS-hydroxy?:2’-azonaphthalenc-6:1’:5’-trisulphonic acid
1-amino-7-(3’-sulph0phenylazo)-8-naphthol-3z?-disulphenic acid ____ __ _
1-amidn0-7-(2’-sulpho-4'-chlorophenylazo)-8-naphthol-3:G-disulphonic
’
8C1
.
'
V
r»
Do.
Rubine.
‘
l-amidno?-(3’-amino~6'-su1phophenylazo)-8-naphth0l-3:6-disu1phonic
.
Bluish-red.
.
1-amin0-7-(2'-sulpho-4’-methoxyphenylazo)-8-naphth0l-3:6-di- '
sulphonic acid.
,
aci
,Red.
'
Bluish-red. f
>
1-amino-7-(2’-sulphophenylazo)-8-naphthol-4:?-disulphonic acid-..“
Red. '
1-amino-8-hydroxy-7:2’-azonaphthalene-3:6:1’-trisulphonic acid
1-amino—7-(4’-sulpl1ophenylazo)-8-naphthol-416~disulphonic acid
Bluish-red.
Rubine. .
2-(W?cetylamino-4’-aminophenylazo)naphthaleneé:8-disulphonic
ac
.
>
disulphonic acid.
1-(2'-sulphophenyl)-3-methyl-4-(3" -amino-6" -sulphophcnylazo)-5
pyrazolone.
Reddish-yellow.
~ '
V
'2-(2’-niethyl-4’-aminophenylazo)naphthalene-5:7-disu1phonic acid____
V
.
Do.
V
Brownish-orange.
Yellow.
'
' I
Do.
i
3,186,979
Example
Aminoazo compound
Shade obtained on
Dithiocarbamic acid derivative
cellulose textile
materials
62 _________ __ 1-(4'-aminophenyl)-3»methyl-4-(1’ :5’ -disuJph0naphthyl-2' »azo)-5-
Sodium diethyldithiocarbamate ___________ _- Yellow
yrnzolone.
63 ......... -_ 1-g?amino-et’-sulphophenyl)-3-rnethyl-4-(l"-sulphonaphtl1yl-2"azo)-5-pyrazolone.
_____do _____________________________________ __
sulphophenylazo)-5-pyrazolone.
_
.__-_do
Do.
_
l-(3’-am.ino-6’~sulphophenylazo)-2-naphthol-6-sulphomc acid
_
Do.
_
1- (4':8'-disulphonaphth~2’-yl)-3-methyl-4—(3' amino-6" _
______dn
_
Orange.
1-(3’-aminoh’sulphophenylazo)-2-naphthol-GzS-disulphomc acid ________ .__do____________ ___. __._ ____________________ __
2-(3harmno-o’-sulphophenylazo)-l-naphthol-3>sulphonic acid _______ _- Sodium dlmethyldithiocarbamate_________ __
Do.
Do.
2~(3'—umino-6’- ulphophenylazo)-l:S-dihydroxynaphthalene-Bz?disulphonic acid.
do
___ Blu1sh~red.
_
1-(3'-amino-6’-sulphophenylaz0)-2-amino~8-nephthol-6sulphomc
_____dn
Red.
acid.
1-acetylamino—7-(3’-amino-6’-sulphophenylazo)-8~naphth0l-3:6disulphonic acid.
_____rl?
Do.
1-acetylamin0-7-(3'-aminc-6'-sulphophenylazo)-S-naphthol-4:G-
__-__do _____________________________________ __
Do.
disulphonic acid.
l-benzoylamino-7-(3'-amino-d-sulphophenylazo)-8~naphthol-3:6-
_____do _____________________________________ __
disulphonic acid.
2-propionylamino-6-(3’-amino-6’-sulphophenylazo)-5-naphthol-7-
.____rln
sul honic acid.
2<benlizoylaminod(3'-amino-6'-sulphophenylazo)-5-napl1thol-7sulphonic acid.
.
Do.
Yellowish-red.
Potassium diethyldlthiocarbamatc _______ ._
Do.
‘
2~amin0-7-(3’-amino-6'-sulphophenylaz0)-8-naphthol-6-sulphomc
____-do _____________________________________ __
Do.
acid.
1-(4’-qmino-2’-sulphophenylazo)-2-naphthol-8~sulphonic acid ____________ _-_do__-___ ____________ __. __________________ _.
Red.
2-acetylamino-6-(4’-amino-2’-sulphophenylazo)-5-naphthol-7-
Yellowish-rcd.
Sodium di-n-propylditluocarbamate ______ -_
sul honic acid.
_
7
2-aceEylamino-7- (4’-amino-2'-sulphophenylazo)-8enaphthol-?-
._ ___dn
Red
sulphonic acid.
-
1-(4'-arnino-2’-sulphophenylazo)-2—aminodnaphthol-?-sulphonic
_____d0 _____________________________________ ..
_
Blnish-red.
acid.
Lacetylamirao-‘I-(4’-a1n_ino-2’-sulpl1ophenylazo)-S~naphth0l-3:6-disu lhonic aci .
Liienzoylamino?-(4’-amino-2’-sulphopl1enylazo)~8-napht-h0l<4:6-
.____d0 _____________________________________ __ Violet.
____-do _____________________________________ _. Bordeaux.
disulphonic acid.
l-(3’-aminophenyl)-3-metl1yl~4—(2”:5"-disulphophenylazo)-5-
_____do _____________________________________ __
pyrazolone.
Yellow.
'
1-(3"aminobenzoylamino)-7- (2”-sulphophenylazo)-8-naphthol<3:6disulphonic acid.
__-__do _____________________________________ __
Red.
i-(4'-a.minosulphonaphth<l’-ylazo)-4-(8"1sulph0naphth-W-ylazo)
__--_do _____________________________________ __
Reddish-brown.
‘
naphthalene sulphonic acid.
l
l-amino-2-(4"-aminophenylazo)-7-(4"-sulphophenylazo)-8‘naphthol~
.__.-do _____________________________________ __
Green.
1~(4’-aminobenzoylamh1o)-7-(2”-snlphophenylazo)-8-naphthol-3:G-
_____do
Red.
3:6-disulphonic acid.
disulphonic acid.‘
_
_
_
1-ami110—7 -(2’-sulphophenylaz0)-8-naphthol-3z?~disulphonic acid ____ __
an
>
_
.
‘
_
Sodium é-morpholinoditlnocarbornate .... __
Do.
Sodium N-methyl-N-phenyldithiocarba-
Do.
me e.
89
____‘rln
90 _________ _-
1-
. Sodium N:N-di-isobutyldithiocarhamate-___
‘ 0-7-(2'sulphophenylazo)~8-naphth0l-3:6~disulpl1onic acid ______ _.
Sodiutm N:N-pcntamethylenedithioearba-
Do.
Do,
ma e.
91 _________ __
2amino-(H2'-methoxy-5’-methyl-4’-(2":5"-disulphophenylazo)
phenylazo1-5-naphthold:7-disulphonic acid.
Example 92
Sodium diethyldithiocarbamat-e ___________ _-
Bluish-violet.
Example 94
In place of the 18 parts of the trisodium salt of the 45
azo compound used in Example 1 there are used 14.5
In place of the 19.6 parts of the trisodium salt used
in Example 93 there are used 17.0 parts of the disodium
parts of the disodium salt of 4- (4":6"-dichloro-1":3":5"
salt of 1 - amino-4-[3’-(4":6"-dichloro—s-triazin-2"-yl)
triazin - 2" - ylamino)—2'-nitrodiphcnylaminc-3:4’-disul—
amino] anilinoanthraquinone-Z:4’-disulph0nic acid (which
phonic acid (which may be obtained by condensing cya
may be obtained as described in Example 2 of Belgian
num'c chloride with 4-amino-2’-nitro-diphenyl-amine-3:4’ 50 speci?cation No. 556,092).
disnlphonic acid).
When applied to cellulose textile materials in conjunc
The dyestu? so obtained when applied to cellulose tex
tile materials in conjunction with a treatment with an acid
tion with a treatment with an acid-binding agent the dye
binding agent yields yellow shades possessing excellent
excellent fastness to wet treatments.
fastness to wet treatments.
Example 93
A solution of 19.6 parts of the trisodium salt of l-amino
4 - [4’ - (4":6"-dichloro-1":3":5"-triazin-2"-ylamino]
stutf so obtained yields reddish-blue shades possessing
55
Example 95
The dihalogenotriazinylamino derivatives of metal
phthalocyanines obtained as described in Examples 1,
2, 3, 8 and 14 of British speci?cation No. 805,562 are re
anilinoanthraquinone-2z3’:5-trisulphonic acid (which may
60 acted with sodium diethyldithiocarbamate by the method
be obtained as described in Example 1 of British speci
?cation No. 781,930) in 400 parts of water is stirred at
diethyldithiocarbamate for each dihalogcnotriazinylamino
of Example 8 using one molecular proportion of sodium
group present in the metal phthalocyanines. The dye
thiocarbamate trihydrate in 50 parts of water is added 65 stuffs so obtained when applied to cellulose textile mate
during 15 minutes. The mixture is stirred at 20° C. until
rials in conjunction with a treatment with an acid-binding
reaction is complete and sodium chloride is then added.
agent yield respectively greenish-blue, turquoise-blue,
20° C. and a solution of 563 parts of sodium diethyldi
The precipitated dyestutt is then ‘?ltered oil, Washed with
greenish-blue, greenish-blue and greenish-blue shades
brine solution and dried at 20° C.
On analysis the dyestulf so obtained is found to contain
1.1 atoms of organically bound chlorine and 4.9 atoms of
which possess excellent fastness to wet treatments.
‘sulphur per molecule of dyestu?. When applied to cellu
lose textile materials in conjunction ‘with a treatment
Example 96
A solution of 10.1 parts of cyanuric chloride in 40
parts of acetone is slowly added with stirring to a mixture
with an acid-binding agent the dyestuif yields blue shades
of 16.8 parts of 4'-amino-2-nitrodiphenylamine-4-sulphon
possessing excellent fastness to wet treatmentsl
75 dimethylamide, 8.4 parts of sodium bicarbonate, 30 parts
3,186,979
19
~
,
of water and 360 parts of acetone, the temperature of the ,
acid-binding agent the dyestulf yields red shades'which
resulting mixture being maintained between 15° and 25° '
possess excellent fastness to wet treatments.
7
I A similar dyestuif is obtained when the 1.5 parts of
C., and the pH of the mixture being maintained at 6.4 by
the addition of an 8% aqueous solution of sodium bicar
aniline usedin the above example are replaced?rby 128
bonate. The mixture is stirred for 1 hour at the above
parts of ‘sodium phenate.
temperature. The mixture is ?ltered and the residual .
solid is then washed with 100 parts of acetone. The com
bined ?ltrates are cooled to a temperature of 5° C. and
.}
'
; 5° and 10° C. and the pH of the mixture being main
tained at 8 byrthe addition of an aqueous solution of sodi
um carbonate. The mixture is then stirred for 1 hour and
the solution so obtained is poured into 3000 parts of water 15
, at a temperature of 1° C. The precipitated dyestufl is
7 n
bonate and 100 parts of dioxan is stirred at the boil under
a re?ux condenser for 8 hours. The mixture is then added
to ‘200 parts of a 10% aqueous-solution of brine and'the
dyestu? which is precipitated is ?ltered 101T, washed 'with
water and dried.
‘
.
V_
The dyestuii so obtained, when dispersed in' aqueous
medium, dyes wool and p'olyarnide textile materials in 7
then, ?ltered o?“, washed with water and dried.
On analysis the dyestuff so obtained is found'to con
yellow shades which possess excellent fastness towashing. '
The 2-chloro-4- (N : N-diethylthiocarb amylthio) -6-phen
yl-1:3:5-triaz'ine used in the above example‘ may be'ob
tain latom of organically bound chlorine and 3 atoms
20
_
q
zene, 4.06 parts of 2-chloro-4-(N:N-diethylthiooarbamyl
thio)-6-phenyl-1:3z5-triazine, 1.26 parts of sodium bicar
a solution of 13.4 parts of sodium diethyldithiocarbamate _
V
i
A mixture of 2.11 ipa-rts'of4-aminoQ-methylazoben
trihydrate in 50 parts of water is then slowly added, the
temperature of the mixture being ,maintained between
of sulphur per molecule of dyestuff.
'
Example 100
When dispersed in aqueous medium the dyestulf colours
tained as follows:
'
,
.
i
‘ '
A solution ofr5.6 parts of ‘sodium diethyldithiocarba
wool and polyamide textile materials in bright yellow"
mate trihydrate in 100 parts of water is added over 1 hour
shades which possess excellent fastness to wet treatments.
with stirring'to a ‘suspension of 5.6 parts of 2:4-d‘ichlo-ro
6-phenyl-1 :3 : S-triazine in a mixture ‘of 30‘ parts ofgacetone
and 200 part-sot water, the temperature of the mixture
being maintained at 15° C. The mixture is then‘ stir-red
Example 97‘
A solution of 27.6 parts of sodium diethyldithiocar
bamate trihydrate in a mixture of 200 parts of water and ‘ > for -a further 45, minutes at 15 ° C., and the precipitate is
1200 parts of dioxan is added with stirring to a solution of
then ?ltered off, washed with water and dried. ‘After
36.3 parts of 2-hydroxy-4’-(4":6"-dichloro-1":3":5"-tri
azin-2”-ylamino)-5-rnethylazobenzener (which may be ob
tained in condensing cyanuric chloride with 2-hydroxy
4'-amino-5-methylazobenzene)-in 1600 parts of dioxan,
and the mixture so obtained is then stirred for 45 hours
at a temperature between 20° and 30° C. The mixture is
then poured into 8000 parts of a 5% aqueous solution’of
sodium chloride and the dyestutf which is precipitated is
?ltered on" and dried.
.
30
crystallisation from a light petroleum .ether (boiling point,
60° to 80° C.) the 2-chloro-4-(N:N-diethylthiocarbamyl
thio)-6~phenyl-'113:5-triazine melts at 767° to 68 ‘11C.’ vOn
analysis the product is found .to contain 49.6% of carbon,
. 4.7% of hydrogen, 16.6% of nitrogen, 11.2% of chlorine
35 and 17.7% of sulphur. (C14H15N4O1S2 requires
of carbon, 4.45% of hydrogen, 16.6% ofnitrogen, 10.6%
' of chlorine and 178.9% of sulphur.)
'
I
'
'
7
Example 101
On analysis the dystu?' so obtained is found to contain 1' H
atom of organically bound chlorine and 2 atoms of sul-v 40
A mixture of 9.6 parts of the dyestu? of Example 15,
phur per molecule of dyestuff. When dispersed in aque- . 3 parts of coppers-ulphate pentahydrate and 130 parts of
‘ous medium thev dyestufr” colours polyamide textile mate
water is stirred for 4 hours at a temperature between
rials in bright greenish-yellow shades of excellent fastness
to light.
I Example 98
A mixture of 618 parts‘ of sodium diethyldithiocar;
bamate trihydrate, 3.4 parts of 1-arnino-4-[4’-(4":6”-di- e‘
chloro - 1" : 3" : 5"-triazin-2”-ylamino ) -anilino] anthraqui
none and 165 parts of dioxan is stirred for 24 hours at a
25° and 30° C., the pH of thermixture being maintained
between 6.0 and 6.5 by the gradualaddition of ‘an aqueous
solution of sodium carbonate. An‘ aqueous solution of
sodium carbonate is then added until the pH of the mix
ture is~7 ‘and the ‘mixture is ?ltered. 40 parts of sodium
chloride are added to the ?ltrate which is obtained and
.the dyestuif which is precipitated is ?ltered off.
The
temperature of 25° C. The mixture is then ?ltered and 50 ?lter-cake so obtained is mixed with 0.99 vpart of di
the ?ltrate so obtained is added to 400 parts of a 10%
. aqeuous solution of sodium chloride. The dyestutf which
is precipitated is then ?ltered oil, Washed with water and
dried.
.
~
.
‘
On analysis the dyestufr“ so obtained is found to con
tain 0.9 atom of organically bound chlorine and 2.1 atoms
of sulphur per molecule of dyestu?.
'
'
sodium hydrogen phosphate and 2.011 parts of potassium
dihyd-rogen phosphate and the mixture is then dried.
On analysis the dyestult so obtained is found to contain
1 atom of copper and 7 atoms of sulphur per molecule
of vdyestui‘f. When ‘applied to cellulose. textile'materials
in conjunction with a treatment with an acid-binding agent
the dyestut‘r' yields violet shades possessing excellent fast
ness to
washing.
.
,
.
V
.
~
When dispersed in aqueous medium the dyestuif colours
In place of the 9.6 parts of the dyestutf of Example 15
polyamide textile materials in blue shades possessing ex 60 used
in ' the above example there are used “equivalent
cellent fastness to wet treatments.
‘ amounts of the dyestuiis of Examples 16, 17 and 91 where
Example ‘99
A mixture of 1.5 ‘parts of aniline, 8.3 parts of the dye
stu? of Example 8, 10 parts of acetone and 200- parts
of water'is stirred at a temperature between 35° and 40°
by c'opperrcontaining dyestuffs are obtained which .when
applied to cellulose textile materials in conjunction with
‘ a treatment with an acid-binding agent'yield violet, navy
blue and navy-“blue shades'respective'ly which possess ex;
cellent fastness to washing.
_
.
' _ V
C. for 2 hours, the pH of the mixture beingmaintained be
' tween 7 and 8‘by thegradual addition of a 10% aqueous
v
Example 102
I
7
d
.
solution of sodium carbonate. '12 parts of sodium chlo-"
100 parts of bleachedcottonfabric are padded through
riderare then added and the dyestu? which is precipitated 70 an aqueous solution containing 2% of the dyestu?? of Ex- ‘
in ?ltered 0E and dried.
ample 1, 1% of sodium bicarbonate and 0.2% of an alkyl
.On analysis the dyestu? so obtained is found to contain
ated phenol/ethylene oxide condensate, at a temperature
7 5 sulphur atoms, but'no atom of organically bound chloof 18° C. and the cotton fabric is then squeezed between
rine per molecule‘ of dyestuff. When applied to cellulose
rollers until its weight‘ is 200‘ parts; The cotton fabric is
textile materials in conjunction with a treatment with an 75 dried'at 70° C. and is then exposed to ‘steam at a tempera
3,186,979
21
22‘
ture of 102° C. for 1 minute. The coloured cotton fabric
is then rinsed in water, immersed for 15 minutes in a
0.2% aqueous ‘solution of soap, rinsed :again in water and
cetyltrimethylammonium bromide and 1.0 part of :a con
den-sate of ethylene oxide with a fatty alcohol in 5000
parts of Water, and dyeing is carried out for 1 hour at
a temperature of 100° C. The dyed woollen cloth is then
removed from the dyebath, rinsed in water and dried. The
woollen cloth is dyed a scarlet shade possessing excellent
?nally dried.
The cotton fabric is thereby coloured a bright red shade
possessing excellent fastness to washing.
In place of the 2% of the dyestufi of Example 1 used in
the above example there is used 2% of the dyestufr’ of
fastness to washing.
Example 106
Example 2 or 2% of the dyestu? of Example 3 or 2% of
the dyestuff of Example 5 or 2% of the dyestuff of Ex 10
A print paste comprising:
ample 8 whereby the cotton fabric is coloured in bright
Parts
yellow, bright blue, bright red and bright red shades re
spectively, which possess excellent tastness to washing.
The dyestu? of Example 92 _________________ __
3
Urea
Example 103
‘Water ____________________________________ _.
15
v100 parts of ‘bleached cotton yarn are immersed in a
Sodium bicarbonate ________________________ .._
4% aqueous solution of sodium alginate ______ __
dyebath comprising 2 parts ‘of the dyestu? of Example 3
and 90 parts of sodium chloride dissolved in 3000 parts
1.5
35
100
of water and dyeing is carried out {or 30 minutes at a
temperature of 20° C. 15 parts of sodium carbonate are 20 is applied to unmerceri'sed cotton cloth by machine print
then added and dyeing is continued for 60 minutes at
ing. The printed cotton cloth is dried at a temperature
20° C. The dyed cotton yarn is then removed from the
of 70° C. and is then steamed ‘for 6 minutes at a tempera
dyebath, rinsed in water, ‘immersed for 5 minutes in a
ture of 100° C. The printed cotton cloth ‘is then rinsed
0.2% aqueous solution of a synthetic detergent at a tem
in water, immersed for 10 minutes in ‘a 0.3% aqueous
perature of 100° C., rinsed again in water ‘and ?nally dried.
solution ‘of a synthetic detergent at a temperature of 100°
The cotton yarn is dyed a brilliant blue shade which is
C., rinsed again in water and ?nally dried.
fast to washing.
The cotton cloth is thereby printed a brown shade
In place of the 2 parts of the dyestut‘f of Example 3 used
which possesses excellent fastness to Wet treatments.
in the above example there are used 2 parts of the dyestuff 30
In place of the unmercerised cotton cloth used in the
of Example 1, or 2 parts of the dyestu? of Example 33
above example there may be used mercerised sateen cloth
or 2 parts of the dyestutf of Example 60 whereby the cot
or viscose rayon cloth when brown prints are also obtained
ton yarn is dyed in bright red, bright orange and bright
which possess excellent fastness to wet treatments.
yellow shades respectively, which possess excellent fast
In place of the 3 parts of the dyestutf of Example 92
35 used in the above example there are used 3 parts of the
ness to washing.
Example 104
dyestutf of Example 1, or 3 parts of the dyestu? of
Example 3 or 3 parts of the dyestu? of Example 24 or 3
parts of the dyestuif of Example 93 or 3 parts of the
second dyestuif of Example 99 whereby there are obtained
100 parts of bleached cotton ?abric are padded through
an aqueous solution containing 0.2% of the dyestu? of
Example 1 and 2% of sodium carbonate and the cotton 40
red, blue, red, blue and red prints respectively which
fabric is then passed between rollers until its weight is
possess excellent fastness to washing.
200 parts. The cotton fabric is then rolled up and stored
The following table gives further examples of dye
for 4 hours at ‘a temperature of 20° C. The cotton fabric
is then rinsed in water, immersed for 5 minutes in a 0.2%
stuffs of the invention which are obtained when the
1.5 parts of aniline used in Example A99 are replaced by
equivalent amounts of the compounds listed in the second
column of the table, and/ or the 8.3 parts of the dyestuff
of Example 8 used in Example 99 are replaced by equiv
fastness to washing.
alent amounts of the dyestuits listed in the third column
Example 105
50 of the table. The fourth column of the table indicates
the shades obtained whenthe dyestuffs are applied to
100 parts of woollen cloth are immersed in a dyebath
cellulose textile materials in conjunction with a treat—
comprising a solution of 1.5 parts of the dyestutf of Ex
ment with an acid-binding agent.
ample 30, 3.0 parts of ‘ammonium acetate, 0.5 part of
aqueous solution of a synthetic detergent at a temperature
of 100° C., rinsed again in water ‘and dried. The cotton
fabric is coloured a bright red shade possessing excellent
Compound
Example
Dyestu?
Ammonium hydroxide ____________ .._ Dyestu? of Example 8---- Red.
Methylamine-
do
Ethylaminc
Dimethylamine
'
do
B-Hydroxyethylamins
Di(?-hydroxyethyl) amine
Do:
do
Do.
Sodium sulphite..
Oyclohexylamine _______________________ __do ___________________ __
Do:
Mornh at i n a
P iperidine- _ _
N igliethylaniline ___________________ -.
o
Sulphanilic avid
3:5-disulphoaniline _______ __
o
_____ -_
Dyestinft of Example 30___ Scarlet.
Dyestu? of Example 35
_
_____do _________________
__
____ Dyegtu? of Example 8- ___
2:5-disulphoaniline_ _
_
.
Dyegtu? of Example 25--- Yggbw.
_____
m-Aminobenzoic acid. _ _
s-snlpho-N-methylaniline
5-sulpho-anthranilic acid.
.___-do ___________________ __
_____
o
_____
o ___________________ _.
3:5-disulpho-N-methylaniline _ _ _____
3-methy1amino-benzoie acid _______ __
5-sulpho-2-methylaminobenzoic acid.
Ammonium hydroxide ____________ __
.
Dyestu? of Example 36-“ Brown.
_
3,186,979’.
23"
.24
Example .130
,
sulponic acid, phenoxy, amino, lower alkylamino, hy- ' '
:droxy lower alkylamino, phenylamino; sulphophen
ylamino, Ecanboxyphenylamino; N-phenyLN-lower
alkylarnino, N-sulphophenyl-N-lower ‘alkylamino,
lcanboxy-sulphophenylamino, N-(canboxysulphophen
yl)-N-lo\ver alkylamino, N-carboxyphenyl-N-lower
lalkylamino, disulphophenylamino, N-disulphophenyl
N—lower iavlkylamino, cyclohexylamino, morpholino,
parts of the trisodium salt of 7-(2'-sulphophenylazo)-1
(4":\6"-dibromo-1":3":5"-triazin-2"-ylamino) - 8 - naph
thol-3z6-disulphonic acid (which may be obtained as
‘ described in the example of British speci?cation 'No.
838,343) when a similar red dyestuif is obtained which,
on analysis is found to contain. 5 sulphur atoms and one
organically bound bromine atom per molecule of dyestutf.‘ 10
7
r
chlorine, ‘bromine, lower alkyl; phenyl, lower ‘alkoxy,
In place of the 17.9 parts of the trisodium salt of the
' azo compound used in Example 8 there are used 19.9
'
'
' Q is a member selected from the/class consisting of
piperidyl and
I
Example 131
e
a
I
In place of the 4.06parts of.2-chloro-4-(NzN-diethyl
thiocarbarnylthio)-6-phenyl-123:5-triazine used in Exam
15
ple 100 there are used 6.16 parts ofg2-chloro-4-(NzN-di
and Z’ and Z" are independently selected from the
ethylthiocarbamylthio) - 6 - (3’:5'-disulphophenylamino)
‘class ‘consisting of lower alkyl, phenyl lower alkyl,
,lz3z5-triazine or 3.5 parts of 2-chloro-4-(NzN-diethyl
lcyclohexyl and phenyl, and taken together Z’ and
.Z" tfOI‘lTl with the nitrogen atom N a heterocyclic ring
selected from the class consisting of piperidyl and
.. thiocarbamylthio)-6-meth0Xy-1:3:5-triazine or 3.34 parts
of 2-chloro-4- (N : N-diethylthiocarbarnylthio ) ~6-amino-1 :
3:5-triazin'e. or 5.38 parts of 2-chloro-4-(NzN-diethyl 20
thiocarb amylthio ) -6-(N-m-sulphophenyl-N-methylamino)
morpholino.
.
thiocarbamylthio)-6-methyl-1z3z5-triazine when similar
yellow dyestuffs are vobtained. _
V
i
'
2. Dyestu?'s of the formula:
1:3:5-triazine or 3.34 parts of 2-chloro-4~(N:N-diethyl
N >
a
s
'
'\c- s-iirNzz
It:
The triazine derivatives used in the above example 25
may themselves be obtained by the method described in
Example 100 for the preparation of 2-chloro-4-(NzN-di
ethylthiocarbamylthio)~6-phenyl-1 :3 :S-triazine except that
the 5.6 parts of 2:4-dichloro-6-phenyl-1z3z5-triazine are
replaced by equivalent amounts of
0 »
s
l
wherein K’ is an azo dyestu? radical, and Zv is alower ’
2 : 4-dichloro-6-(3' : 5’-disulphophenylamino)-l :3 : S-triazine,
2 : 4-diChloro-6-methoxy-1 :3 : S-triazine,
.
2 : 4-dichloro-6-amino-1 :3 :S-triazine,
2: 4-dichloro-6-(N-m-sulphophenyl-N¢methylamine)-1 :3 :
'
- S-triazine or
35
'
' 2:4-dichloro'-6'-.methyl-1 :3 :SQtriaZine respectively;
Example‘132
1
A solution of 3.0 parts of sodium dimethyldithio
vcarbamate in 15 parts of Wateris added to a solution of
wherein K2 is an lanthraquinone dyestuff ‘radical, and Z
3.0 parts of the disodium salt of 1-(4':<6'-dichloro-1':3’:5'-.
triazin-2'-amino) -7-phenylazo-*8-naphthol-3 :6 - disulphonic
. is a lower alkyl radical.
‘
'
'
‘4. Dyestu?s of the formula:
acid (which is obtained as'described in Example ,1 of
United States patent speci?cation No. 1,667,312) in 710
parts of Water, and'the resulting mixture is stirred for
16 hours at 20° C. The mixture is then ?ltered and 18
parts of sodium chloride are added to the resulting ?ltrate.
The dyestutf which is precipitated is then ?ltered Off,
washed with a 20% aqueous solution of sodium chloride 50
and dried.
'
On analysis the dyestuff is found to contain 6 sulfur .
wherein K3 is a phthalocyanine dyestuff radical, and Z is
atoms per molecular of dyestuif. When applied to cellu
a lower ‘alkyl radical.
'
lose textile materials in'conjunction with a treatment with
5. Dyestuifs of the tformula:
‘an acidabinding agent the dyestuif yields red shade-s pos 55
sessing excellent fastness to light and to wet treatments.
The dyestuff also-possesses excellent stability to storage
'and this is superior to the stability to storage oft-he ?rst
. dyestuif of Example 1 of United States patent speci?ca?
tion No. 71,667,312.
What we claim is;
7
.
>
7
60
H
.
J1. Dyestuffs of the ‘formula:
-wherein K1 is an lazo dyestu?f radical, and Zris a lower
_ alkyl radical.
-
wherein
.
H
.
'
*
'
.
Y6‘; Dyestuffs of the formula:
'
3K represent-s the radical of a dyestu?? selected from the
class consisting of ‘ azo, anthraquinone, nitro and
phthalocyanine dyestu? radicals;
V
,
,- , . i
R represents a member'selected from the class consist
ing of hydrogen and lower alkyl; ' “A '
n is a‘ positive integer not exceeding 2;
'
'~
i-fwherein K2 is an anthraquinone dyestufi radical, ‘and Z is.’
"75*
a lower alkyl radical. '
.
3,1 86,979
25
7. The dyestu? which, in ‘the form of the free acid, is
the formula
of 'the formula:
10
8. The 'dyestu? which, in the form of free acid, is of
References Cited by the Examiner
UNITED STATES PATENTS
the ‘formula
15
1,667,312
2,061,520
2,892,671
2,979,498
4/ 28
-1 1/ 36
6/59
Fritzsche et a1 ________ __ 260-153
Orthner et a1 _______ .__ 260—249.5
Alsberg et a1. _______ __ 260—.153
4/61
Andrew et a1. _______ __ 260-11513
FOREIGN PATENTS
20
9. The dyestuff which, in the form of ‘free acid, is of
570,524
2/59 Belgium.
CHARLES B, PARKER, Primary Examiner.
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