Note: Descriptions are shown in the official language in which they were submitted.
-- 1 --
The present inven-tion relates to new reactive dye-
stuffs of the general formula
C~s n
In this formulal
D denotes the radical of an organic dyestuffs,
Y denotes a direct bond or a bridge member to an
aromatic-carbocyclic or aromatic-heterocyclic C
atom of the chromophore,
R denotes hydrogen or Cl-C4-alkyl and
n denotes the number 1 or 2.
Preferred organic dyestuffs D are water-soluble azo
dyestuffs, anthraquinone dyestuffs, phthalocyanine dyestuffs
and formazone dyestuffs, Y preferably represents a direct
bond and n preferably represents the number 1.
; 15 Preferred azo dyestuffs correspond to the following
general formulae:
C~
SO~
N = N ~ ~ or C00
~ J
Rl r
A = 2-fluoro-5-chloro-6-methylpyrimidyl and
~ Rl = H, alkyl or aryl
: S~ 5
~ N = ~J ~ ~ - A III
R2 = H, alkyl, alkoxy or acylamino
,~
.
~. Le A 18 854
, `
:, . , .. : ~
. ~ , . . .
. .
,,, ~,
' . , .
: ,. ;
L ~
~ 2 --
SO
~N - N ~ ~
~=J IV
R
R
N-~ :
SOx ~ ~ /
.... ~ = N ~ V
0-2 '"' ~ S03 ~
: and metal complex dyestuffs with the following ligand
groupings~
R
HO N-~
,~, ` ~ = ~ ~ VI
0-3 ~S S ~ ~ y ~
R~ SO~ 5
R3 = H, halogen 9 -N02 or alkyl.
Preferred metal atoms are Cu (1:1 complexes) or Cr
and Co (1:2 complexes). Cr ~,omplexes and Co complexes
can contain one or two molecules of the azo compound:of the
. 10 formula VI, that isto saythey canbebuil-t up symmetrically
:, or unsymmetrically with any other desired ligand groupings,
S0~, ~I o_ 2 H~ NH2 S03 H 0 -2
. ~N = N~ VII
(R~ ~o-l--~ I l ~ )o_~
: . ~ H05 3
, . ~
'` ~ SO
R v
~- R4 = -N-A
The fused rings indicated by broken lines represent ~
~-~ 15 naphthalene systems, which are a possible alternative. :. --
Preferred anthraquinone dyestuffs correspond to the
general formula VIII:
:~ i
.
-- 3 --
O N~
SO3E ~ VIII
~~ ~ (CE~)o~ i~A
SO3~ 0~2 R
R5 = H, Cl-C4-alkyl or C1-C4-alkoxy,
Preferred phthalocyanine dyes-tuffs correspond to the
general formula IX
50 ~
C~O~ ~ ) 1-2
R6 and ~ ~ H or C1 C4-alkyl, or, together, C4-C5- ~
alkylene, optionally interrupted by N or 0. ~;
In this formula~
~ Pc represents the Cu phthalocyanine or Ni phthalo-
`~ 10 cyanine radical. ~ -
The total number of substituents on the Pc matrix is 4.
The alkyl, aryl and alkoxy radicals in the formulae
I - IX can optionally contain fur-ther customary substituents.
In general, the unsubstituted radicals and, within the alkyl
and alkoxy radicals those with 1-4 C atoms, are preferred.
Further suitable bridge members are N-alkylene
R
(C~z~o-~ CO ~ -N-SO
(R8 )0-Z(Ra )0 2 (R8 )0-2 and
,,
' ~ 58 ~ ~ :
(R8 )o~
; the phenylene radicals pre~erably being linked in the p-
position or m-position,
alkylene = Cl-C4-alkylene and
- R8 = S03H, COOH, Cl-C4-alkyl or C1-C4-alkoxy.
The new dyestuffs of the ~eneral formula I are
accessible by preparation processes customary for the
Le A 18 854
- . ~ ,. : , .
- , , :, . :., ~ :
,
, , ;: :
' ' , ;
-- 4 --
syn-thesis of reactive dyes-tuffs. Thus, for example, the
correspondlng dyestuffs of the formula
~ R )
1--~
a large number of which are known from the literature, can
be subJected to condensation reactions with 1 or 2 mols of
2,4-difluoro-5-chloro-6-methylpyrimidine. The conden-
sation reaction of the fluoropyrimidine with a dyestuff
precursor or intermediate product is also frequently first
carried out, which then follows the build-up of the dye-
s-tuff, for example by azo coupling.
The reaction with the pyrimidine is carried out in
aqueous or organic-aqueous media at 20-70 in the presence
of acid-binding agents, such as sodium carbonate, sodium
bicarbonate or dilute sodium hydroxide solution.
Other conversion reactions of the dyestuffs or pre-
cursors thereof, such as metallisation reactions, sulphona-
tions or introduction of acylamino groupings, can in
` general be carried out at any desired stages of the dyestuff
s
syntheses.
The synthesis of dyestuffs of the formula I with two `
~- reactive radicals A can be carried out completely analo-
,il gously, it being possible, for example, in azo dyestuffs
'; for the diazonium component and coupling component each to
contain a reactive radical A. Reactive dyestuffs which
carry, on the one hand, the radical A and further customary
reactive radicals, for example those of the triazine series
' or of the pyrimidine series, are, of course, also access-
ible by analogous processes.
From the large number of dyestuffs described by the
formulae I-IX, the following groups are very particularly
preferred:
Le A la B54
~ ...... .
: ~
:, : ~ .. ;.
, , . ,,, ~ . . ~ : . . , :
. .
: ~ . . . :,
.. ,", .
-- 5 --
B9 SO~, ~
N = ~ COOH
11 ~
~O~N~ X
~,R~
~ .' .
g
Rg = H, CH3 or Cl
, S
~ ~ ~ XI ;~
: S~3~
Rlo = H, CH3, OCH39 NHCOCH3 or NH-CONH2 ?
IIO3S _~SO~
N = N ~ ~ XII
~0~S'~'J`~ N~A
. ~ ~ 3
,~
S03 ~ ~ ~[q N~
N - N ~ XIII
SO_~ 5
. : ~
03H ~
~N = N
o5 ~ N~A XIV
HO3S ~ ~11
Rll = H, CH3, Cl-C4-alkoxy or acylamino, in parti-
cular -NHCO3 or -NHCOC6H5, ~;
~05~ O -Cu _ o : :
10EO~ I xv
~ Le A 18 854
. '"
:,
.
..
.. ~ . .. . ..
:, . . . .
~. ; . . :
-- 6 --
O Cu---O S03~
HO S '~ ~ N ~ 1~ XVI
- (OH)o ~ NEA
S~ ~ SO5H
.
N = ~ ~ NE~ 1 XVII
S~ HOSS' sos~ SO
O N~
~3~S~
XVIII
R, ~ SO5~_2- :
. ~ .
~ XIX
,'` Rl~C~3 .
" HOS S~ GE2 ~
: R :-
Ni/Cu-Pc(3) 53~-Z
808NH ~ NHA
COOHo_l .
The dyestuffs of these formulae are outstandingly
sui-table for printing and dyeing textile structures of
: natural and regenerated cellulose and of na-tural or syn-
thetic polypeptides.
The dyeings, obtainable in high yields, with these
; Le A 18 854
, _
- 7
dyestu~fs are distinguished by a high stability of the
fibre-dyestuff bond and by an ou-tstanding stability towards
oxidising agents, such as washing agents containing per-
oxide or chlorine. The ease of washing out the hydroly-
sis products formed during dyeing or printing is excellent.
150 ml of anhydrous HF are initially introduced into
a stirred autoclave made of V4A steel and fitted with a
reflux condenser, monometer and a pressure-release valve,
and 197.5 g of 2,4,5-trichloro-6-methyl-pyrimidine are
added dropwise at 0-5C. The autoclave is closed, N2
is forced in to a pressureof 5bars andthe autoclave is then
heated up~ From 80, an increase in pressure due to
the HCl formed can be observed, and is very rapid at about
100C. The pressure is adjusted to 18 bars via the
pressure-release valve. The autoclave is heated up to
165C at this pressure, at the rate at which HCl is
evolved. The mixture is allowed to a~ter-react at the
same temperature for 11 hours,andiscooled andthen distilled.
After first runnings of HF, 150 g of a crude distlllate and
11 g of distillation residue are obtained. The distil-
` late has the composition, according to gas chromatography,
of 76.5% of 2,4-di~luoro-5-chloro-6-methyl-pyrimidine, 19.4%
of 2,5- dichloro-4-fluoro-6-methyl-pyrimidine and 1.4% of
2,4,5-trichloro-6-methylpyrimidine.
Redistillation gives: 100 g of 2,4-difluoro 5-
chloro-6-methylpyrimidine as a liquid of boiling point:
158-159C and nD: 1.4778 and 25 g of 4-~luoro-2,5-di~
chloro-6-methylpyrimidine with the boiling poin-t: 86/ 20
mbars and nD: 1.5178.
~L
19 par-ts of 1,3-diaminobenzene-6-sulphonic acid are
stirred in 250 parts of water and are dissolved by adding
about 40 ml of a 20% strength sodium carbonate solution.
17 parts of 2,4-difluoro-5-chloro-6-methylpyrimi-
dine are added to this solution at about 30 and the
hydrofluoric acid liberated is neutralised at 30-50,
whilst stirring vigorously, by adding a sodium carbonate
solution dropwise until the pH value no longer changes ~rom
.~
,
- 8 _
6-7. The condensation produc-t thus obtained, of the
formula S03
N~
Cl~
C~ '~N ~ F
is diazotised directly, after adding ice and 7 parts of
sodium nitrite with 28 parts of hydrochloric acid.
30 parts by weight of 1-[2'-methyl-4'-sulpho-
phenyl]-3-carboxypyrazol-5-one are added to this suspension
of the diazonium compound and the coupling reaction is
brought to comple-tion by adding about 80 parts of a sodium
~ 0 carbonate solution (20% strength). After the coupling
:, reaction has ended, separating out of the dyestuff isi~ brought to completion by adding 200 parts of potassium
chloride or sodium chloride and the dyestuff is then iso-
lated by filtration and dried at 50-100. A yellow
powder which dyes or prints cotton in greenish-tinged
;~ yellow shades is obtained.
- The prints or dyeings thus obtained have outstand-
;~ ing fastness to wet processing.
If the coupling component 1-(2'-methyl-4'-sulpho-
phenyl)-3-carboxypyrazol-5-one in this example is replaced
by equimolar amounts of the pyrazoles listed in the table
which follows, yellow reactive dyestuffs are likewise
obtained.
~: ;
:~ :
. _ .
- ... .. , . .. . . .. ., . .
- 9
I r-~
I
o
Sl L~ N ~ ~ O O tq O
S~ r~ h r~
O O :~ h ~ rl I Lr\ I ~ ~
t~ O ~ U~ O O O O N
o h ,~ o
~ ,s: 5 ~ h
o I ~ I h I h I a~ I a~ I I
.~ v ~ ~ a
:
,:
i
...
~: .
:;
:~
~; ~ .
l ':
~ N - - _
:~ ~ ~ '~
,`: ,1 O
. .~
a~
~ ,~
: ~1 Q
:~.
C~ ..
:~ ~ ~
'
, .
a~
~ ~ ~ Lr,
Le A 18 854
- ,
",, , : -
. . , :,
, ': : :: ;'"' : : '. ~
: "'': ':' ' : ~ ~;
-- 10 --
Exam~e 10
A solution of 21 parts of 1,3~diamino-2~methyl-
benzene-5-sulphonic acid, in the form of the sodium salt,
in 300 parts of water is subjected to a condensation reac-
tion with 17 parts of 2,4-difluoro-5-chloro-6-methyl-
pyrimidine at 30-50, whilst stirring vigorously,
During -this reaction, the hydrofluoric acid liberated is
neutralised by adding a 20% strength sodium carbonate solu-
tion dropwise. When the condensation reaction has
:::! 10 ended, the reaction product is diazotised directly at 5-10
by adding ice, 7 parts of sodium nitrite and 28 parts of
hydrochloric acid and the diazotisation product is then
coupled, by adding 30 parts by weight of 1-(2'-me-thyl-4'-
sulphophenyl)-3-carboxypyrazol-5-one and about 80 parts of
a 20% strength sodium carbonate solution, to give the azo
dyestuff of the formula ~0 S
- ~ N = ~ ~ C00
.:~ CHs ~
N~ Gl ~CE5 ~ ' '
SO
Separating out of the dyestuff is brought to completion by
salting out with 150 parts of sodium chloride. The dye-
stuff is then isolated by filtration and dried at 50-100,
A yellow powder which is outstandingly suitable for print-
ing and dyeing cotton is obtained.
If the coupling component in this example is
replaced by the pyrazole derivatives indicated in examples
3-9, yellow reactive dyestuffs with very good coloristic
properties are likewise obtained.
Example 11
19 parts of 1,4~diaminobenzene-2-sulphonic acid are
dissolved, in the form of the sodium salt, in 250 parts of
water at 30 and are subjected to a selective condensation
reaction at -this temperature with 17 parts of 2,4-diXluoro-
5-chloro-6 methylpyrimidine. A pH value of 5,8-6 is
maintained during this reac-tion by adding 30 parts of a 20%
Le A 18 854
__
,~
.: . .. .
.,, ~
streng-th sodium carbonate solution.
When the condensation reaction has ended, the sus- r
pension iS diazotised directly by adding ice, 7 parts of
sodium nitrite and 28 par-ts of hydrochloric acid.
A solution of the sodium sal-t o~ 29 par-ts of 1-(4'-
sulphophenyl)-3-carboxypyrazol-5~one in 150 parts of water
is added to the suspension of the diazonium compound and the
; coupling reaction is brought to completion by adding 50
parts of a 20% strength sodium carbonate solution.
Thereafter, the dyestuff is salted out with 200 parts of
potassium chloride, isolated a~d dried. A yellow powder
which dyes cotton in golden yellow colour shades is thus
obtained. The dyestuff corresponds to the formula:
;
C~ 1 /S~ ~
N ~ N~ ~ N = N~ OOH
S03 ~I
Similar colour shades are obtained when the 1-(4'-
sulphophenyl)-3-carboxypyrazol-5-one in this example is
replaced by equimolar amounts of the pyrazoles indicated in
example 3-9.
17 parts of 2,4-difluoro-5-chloro~6-methylpyrimi-
dine are added dropwise to a solution of 0.1 mol of the
aminoazo dyestuff, prepared by customary methods, of the
formula
SO~H
25 in 1,000 parts of water at pH 7 and at about 50, and the
pH value is kept in the range of 6-8 during this addition
by adding dilute sodium hydroxide solution or a sodium
Le A 18 854
.
. .
' -,,. ;;
~ 12 -
carbonate solution.
When the condensation reaction has ended, the dye-
stuff is salted out, isolated and dried The dyestuff
of the formula
S~ H C\ /C~
~ = N ~'iH~
~: S03
'
which is obtained as a Yellow powder, dyes cotton in yellow
colour shades which are fas-t to light and chlorine.
; If the 2--aminonaphthalene-4,6,8-trisulphorlic acid
in this example is replaced by 2-aminonaphthalene-4,8~
disulphonic acid, 2-aminonaphthalene-6,8-disulphonic acid,
2-aminonaphthalene-3,6,8 trisulphonic acid, aminobenzene-
2 7 4-disulphonic acid or aminobenzene-2,5-disulphonic acid,
yellow reactive dyestuffs of outs-tanding fastness to :light
and wet processing are likewise obtained.
Ye].low reactive dyestu~fs of this type can be
obtained in an analogous manner when the aniline employed
as the coupling component in this example is replaced by
3-methylaniline, 2-methoxyaniline, 3-acetylaminoaniline,
3-ureidoaniline or 2-methoxy-5-methylaniline.
Exa_E~
0.1 mol of the condensation product, which can be
obtained according to example 2, o~ 19 parts of 1,3-
diaminobenzene-6-sulphonic acid and 17 parts of 2,4-
difluoro-5-chloro-6-methylpyrimidine are added to a solu-
tion of the diazonium compound which can be obtained, by
customary methods, from 0.1 mol of 2-aminonaphthalene-
4,6,8-trisulphonic acid, and the coupling reaction is
brought to completion by neutralising the mixture with a
dilute sodium carbonate solution.
After salting out, filtration and drying, the dye- .
stuff of the formula ~ ~ S~
N = N ~ N~ Cl C~
~03S ~ ` ~ ~
F
Le A 18 ~4
,~.
,
, :, :, :.
: :: , :: ~ : : .:
:, ,
, . . . . . .
- 13 ~
is obtained in the form of a yellow powder. It is
ou-tstandingly suitable for dyeing and printing cotton in
Golden yellow colour shades.
17 parts of 2,4-difluoro-5-chloro-6-methylpyrimidine
are added to a solution of 24 parts by weight of 2-amino-5-
hydroxynaphthalene-7-sulphonic acid in the form of the
sodium salt, in 200 parts of water at pH 6. The conden-
sation reaction can be brought to completion in the course
of one hour at 45~50, whilst simultaneously neutralising
the mixture with dilu-te sodium hydroxide solution or a 20%
strength sodium carbonate solution and whilst stirring
; vigorously.
The suspension of the condensation product is com
bined with a suspension, prepared by customary methods, of
a diazonium compound of 2-naphthylamine-1,5~disulphonic
acid and the coupling reaction is brought to completion by
adding 10 parts,of lithium carbonate. r'he orange-
coloured reactive dyestuff o~ the formula
~0 ~ 4
SO~H
is salted out, isolated and dried. An orange-coloured
powder which is outstandingly suitable for dyeing and
printing cotton by processes customary for reactive dye- -
stuffs is obtained.
If the condensation product of 2,4-difluoro-5-
chloro-6-methylpyrimidine and 2-amino-5-hydroxynaphthalene
7-sulphonic acid described in this example is coupled, by
methods which~are in themselves known, with the diazonium
compounds from the amines listed below, outstanding reac-
tive dyestuffs, with the colour shades indicated, are like-
wise obtained:
Le A 18 854
.
.: ` ' ': '
- 14 _ ~ ~3.~
Diazonium compound from: Colour shade
2~Aminonaphthalene-1,5,7~trisulphonic acid orange
Aniline-2-sulphonic acid orange
l-Amino-3-acetylaminobenzene-6-
5 sulphonic acid orange
l-Amino-3-triazinylaminobenzene-6-
sulphonic acid orange
l-Amino-4-methoxybenzene-2-sulphonic acid scarlet
l-Amino-4-methoxybenzene-2,5-disulphonic
acid scarlet
2-Aminonaphthalene-3,698-trisulphonic acid scarlet
l-Amino-~-acylaminobenzene-2-sulphonic acid scarlet
1-Amino-4-acylaminobenzene-2,5-disulphonic
acid scarlet
~
17 parts of 294~ifluloro-5-chloro-6-methylpyrimi-
dine are added dropwise to a solution of 32 parts by
weight of l-amino-8-hydroxynaphthalene 3,6 disulphonic
acid, in the form of the sodium salt, in ~00 parts of
water at 45-50, whilst stirring vigorously, and the acid
liberated is neutralised during this addition by means of
dilute sodium hydroxide solution or sodium carbonate solu-
tion. After about one hour under these conditions,
the condensation reaction has ended.
The condensation product thus obtained is then com-
bined with the diazonium compound, which can be obtained
by customary methods, from 0.1 mol of aniline-2-sulphonic
acid and the coupling reaction is brought to completion at
pH 7, After sal-ting out, isolating and drying, a dark
powder of the dyestuff of the formula
Cl /C~
so3~ ~Q H~ ~ N
N = ~ ~ N~ F
~S SO~H
which dissolves in water giving a red-coloured solution
and dyes cotton in brilliant red shades is obtained.
If the diazonium compound from aniline-2-sulphonic
acid in this e~ample is replaced by equimolar amounts of
Le A 18 854
,~ ,
. : .,
. :
.; i ,~
.: ,.... .
.:~
- 15 ~ i3
the diazonium compounds obtainable from the following
amines, brilliant red reactive dyestuffs are likewise
obtained: aniline, aniline~2,5-disulphonic acid, 4-me-thyl-
aniline-2-sulphonic acid, 4-methoxyaniline-2-sulphonic acid,
4-methoxyaniline-2,5-disulphonic acid, 3-pyrimidinylamino-
aniline-6-sulphonic acid, 4-triazinylaminoaniline-2-
sulphonic acid, 2-aminonaphthalene-1-sulphonic acid, 2-
aminonaphthalene-1,5-disulphonic acid and 2-aminonaphthalene-
: 1,5,7-trisulphonic acid.
10 ~
If 0.1 mol each of 2,4-difluoro-5-chloro-6-methyl-
pyrimidine and l-amino-8-hydroxynaphthalene-4,6-disulphonic
acid are subjected to a condensation reaction under the
conditions indicated in example 15 and the condensation
product is coupled, by analogous methods, with the diazonium
compound from aniline-2-sulphonic acid, after salting out,
isolating and drying, -t~e dyestuff of the formula
CH3
SOs~ ~ ~H ~ N
N - ~ ~ F
S~ :
is obtained as a dark powder whic~h dissolves in wa-ter
giving a yellowish-tinged red-coloured solution and is
outstandingly suitable for printing and dyeing cotton in
brilliant red colour shades.
If the diazonium compouncl from aniline-2-sulphonic
acid in this example is replaced hy equimolar amounts of
the diazonium compound from the amines listed in the table
in example 15, brilliant red reactive dyestuffs are like-
wise obtained.
E m~le 17
17 parts of 2,4-difluoro-5-chloro-6-methylpyrimi-
dine are added to a solution of the sodium salt of 32 partsby weight of l-amino-8-hydrox~naphthalene-3,6 disulphonic
acid in 200 parts of water at pH 5.5-6, as indicated in
example 15, and are subjected to a condensation reaction
at 45-50. The solution of the condensation product is
Le A 18 854
,
, .. ~ : : ..
,
16
then combined with the diazonium compound from 0 1 mol of
2-aminonaphthalene-4,6,8-trisulphonic acid in 200 parts of
water and the coupling reaction is carried out at pH 7 by
adding alkali.
When the coupling reaction has ended, 35 parts by
weight of copper sulphate are added to the red dyestuff
solution and a mixture o~ 50 parts of a 30% strength
hydrogen peroxide solution and 130 parts of a 20% strength
sodium acetate solution is added dropwise at 15 and at pH
4.6. The temperature is kept in the range of 10-15
during this addi-tion by adding about 200 g of ice. When
the oxidative coppering has ended, the copper complex dye-
stuff of the formula
Cl /C~
~IOS ~ O E~
N = ~ <F
~0~ ~ H05 ~ ~ S0
SO~ lI
15 is salted out, isolated and dried. A dark powder which
dissolves in water giving a blue-coloured solution and is
suitable for printing and dyeing cotton in navy blue colour
shades with good fastness to light is obtained.
The diazonium compound from 2-naphthylamine-4,6,8-
trisulphonic acid can be replaced in this example by thediazonium compounds from the amines in the table which
follows. The oxidative coppering is carried out ana-
logously.
Diazonium compound Colour shade
25 Aniline-4-sulphonic acid violet
Aniline-3,5-disulphonic acid violet
Aniline red-violet
2 Aminonaphthalene-4,8-disulphonic acid blue
2-Aminonaphthalene-6,8-disulphonic acid blue
2-Aminonaphthalene~1,5,7--trisulphonic acid blue
Example 18
A suspension of the diazonium compound from 0 1 mol
of 2-aminonaphthalene-4,6,8-trisulphonic acid in 250 parts
by volume of water is added to the solu-tion obtained by the
.
.. . ..... . .. . .
.
:, .
- ~
: .'' : ': ''
~ 17 ~ f~ ~
process described in example 14 for the preparation of the
condensation produc-t of 2~amino--5-hydroxynaphthalene-7-
sulphonic acid and 2,4-difluoro-5-chloro-6-methylpyrimidine,
and the coupling reaction is brought to completion by adding
20 parts of sodium bicarbonate. 250 parts of a 20%
strength sodium acetate solution and 500 parts of a 3%
strength hydrogen peroxide solution are added to the coupl-
ing solution thus ob-tained. Oxidative coppering is
then achieved by adding 250 parts of a 20% strength copper
sulphate solution dropwi.se. When the coppering has
ended, the dyestuff of the formula
EO~S ~ -~Cu - O
~h~N - N~"~q C~,C~[5
~03 ~ N~/ N
HO~S ~ F
is salted out with a mixture of 400 parts of sodium chloride
and 100 parts o~ potassium chloride and then isolated and
dried. A dark powder which dissolves in water giving a
violet-coloured solution and dyes cotton in clear blue-
violet colour shades is obtained.
If the diazonium compound from 2-aminonaphthalene-
4,6,8-trisulphonic acid in this example is replaced by
diazonium compounds from the fol~Lowing aromatic amines,
violet reactive dyestuffs are likewise obtained: aniline-
4-sulphonic acid, aniline-3-sulphonic acid, aniline-3,5-
disulphonic acid, 2-aminonaphthalene-4,8-disulphonic acid,
2-aminonaphthalene-6,8~disulphonic acid, l-aminonaphthalene-
4,6-disulphonic acid, 1-aminonaphthalene-4,7-disulphonic
acid and 2-aminonaphthalene-3,698-trisulphonic acid.
E mlæ~
0.1 mol of the aminoazo compound of the formula
~03S\ so3
HO3S ~ N = N'
O CU O
Le A 18 854
.:. - '. ., : ~ . , : ~ :: :
.. : ... . ..
i ", . ,: ..
. .
.
. : . ,
, : ~ '
.:
~3.~
which can be obtained by coupling 1-aminonaphthalene-4,6-
disulphonic acid wi-th 2-acetylamino-5-hydroxynaphthalene-
4,8-disulphonic acid, subsequent oxidative coppering, and
saponification of -the ace-tylamino group, are dissolved, at
pH 6.5, in 1,500 parts by volume of water, and 18 parts of
2,4-difluoro-5-chloro-6-methylpyrimidine are added in por-
tions at about 50, the acid liberated being neutralised
wi-th a sodium carbonate solu-tion in a manner such that a
pH of 6.5 is maintained during the condensation period of
about 2 hours.
When the reaction has ended, the dyestuff of the
formula
~0~ ~ SO~H C ~ /C~
~ ~ NH ~
HO~S ~ /~ N = ~ ~ F ;.
O~ O SS ~
is salted out, isolated. and dried at about 50 in vacuo.
A dark powder which dissolves in water giving a blue-
coloured solution and dyes cotton in reddish-tinged blue
colour shades is obtained. The same dyestuff can be
obtained by coupling the diazonium compound from l-amino-
naphthalene-4,6-disulphonic acid with the condensation pro~
duct of 2-amino-5~hydroxynaphtha:Lene-4,8-disulphonic acid
and 2,4-difluoro-5-chloro-6-methylpyrimidine and subse-
quent oxidative coppering of the product
Dyestuffs which dye cotton in similar reddish-
tinged blue colour shades can be obtained when the diazon-
ium compound from 1-aminonaphthalene-4,6-disulphonic acid
in this example is replaced by those from the following
amines: l~aminonaphthalene-4,7-disulphonic acid, 1-amino-
naphthalene-4-sulphonic acid, 2 aminonaphthalene-6,8-
: disulphonic acid, 2-aminonaphthalene 4,6,8-trisulphonic
acid, 2-aminonaphthalene-3,6-disulphonic acid and l-amino-
8 hydroxynaphthalene-4,6~disulphonic acid.
0 1 mol of the 1:2 chromium complex of the formula
, . ..
,
. ~.. ', ,
' '
.'
- 19 ~
~ ~S05H
02N ~ N = ~ 'J
0~ 0 N~
Cr
Oz~
~s SO
which can be obtained by coupling diazolised 5-nitro-2~
aminophenol with l-amino-8-hydroxynaphthalene-3,6-disul-
phonic acid and subsequent conversion of the coupling
product into the 1:2 Cr complex, are dissolved, at pH 7,
in 1,000 parts of water and subjected to a condensation
reaction with 34 parts of 2,4-difluoro-5-chloro-6-methyl-
pyrimidine at 60. The acid liberated is neutralised ~-
during the condensation reaction by adding a dilute sodium
carbonate solution dropwise When the condensation
reaction has ended, the dyestuff is salted out, isolated
and dried. It is obtained in the form of a dark powder
which dyes cotton in greenish-tinged grey colour shades.
If the pure chromium complex in this example is
replaced by a 1:1 mixture o~ the Cr complex and the corres-
ponding Co complex, a dyestuff mixture which dyes cotton in
neutral black or grey shades which are fast to light is
obtained. ~,
Example 21
0.1 mol of the Co complex of the formula
08~ ~ H~ S
~3 ~ C ~
; H03S 0 ~ 0
, _ ,
N ~
',: ' . , .
': . ,:' '' ,'' .
~ 20 ~are dissolved, at pH 6, in 800 parts by volume of water and
subjected to a condensation reac-tion with 34 parts of 2,4-
difluoro-5-chloro-6-methylpyrimidine a-t 50-60, whilst
stirring vigorously. The acid liberated is neutral-
ised by adding a 20% strength sodium carbonate solutiondropwise. When the condensation reaction has ended,
the resulting reactive dyestuff is salted out, isolated and
dried. It is obtained in the form of a dark powder
which dissolves in water giving a brown-coloured solu-tion
and dyes cotton in brown shades which are fast -to light.
0.1 mol of the 1:1 chromium complex of the dyestuff
obtained from 6-nitro-1-diazo-2-hydroxynaphthalene-4-sul-
phonic acid and 2-hydroxynaphthalene is added, at 70-80
and at a pH value of 8-9, to 0.1 mol of the dyestuff, in
300 parts of water, obtained by coupling diazotised 4-
chloro-2-amino-1-hydroxybenzene-6-sulphonic acid with 1-
amino-8-hydroxynaphthalene-3,6~disulphonic acid under
alkaline conditions. After a short time, a dark blue
solution has formed. The 1:2 Cr mixed complex thus
obtained is acylated with 20 parts of 2,4-difluoro-5-
chloro~6-methylpyrimidine at 50-60 and a-t a pH of 6.5-7.5
in the course of about 2 hours. The pH is kept constant
during this acylation by adding a 20% strength sodium
carbonate solution dropwise. The reactive dyestuff is
salted out with 20% of sodium chloride, isolated and dried.
The dyestuff of the formula2N
Ç~
~03S ~ N = N
: ~o // O
\Cr Cl C~s
~ ~ N
~s~ ~ N= ~ ~ F
~[s
Cl
dyes cotton in blue-green colour shades which are fast to
light,
Le A 18 854
: ~ .. , '. ' : . . : : '::.
:'' :.'; ' , ,": ' ~
,:,,,:,::
.: : : .. ~, :-
: , ,; ~
- 21 -
0.1 mol of the condensa-tion product of 1,3-diamino-
benzene-6-sulphonic acid and 2,4-difluoro-5-chloro-6-
methylpyrimidine is diazotised as described in example 2
and the suspension is coupled with 0.1 mol of 1-amino-8-
hydroxynaphthalene-3,6-disulphonic acid at pH 2-3.
When the coupling reaction has ended, a suspension of the
diazotisation product from aniline-2,5-disulphonic acid is
added to the dark red dyestuff solu-tion. For the
second coupling reaction, the pH value of the reaction mi.x-
ture is adjusted to 7-8 by adding a 20% strength sodium
carbonate solution dropwise. When the coupling reac-
tion has ended, the dyestuff of the formula
S0s~ ~ N o~ g
N = N ~ N = N ~
N ~5 S0sH So~sH
;~
NJ~C~
is salted out, isolated and dried. It is a dark powder
which dissolves in water giving a blue-coloured solution
and dyes cotton in dark blue to black colour shades.
Example 24
The coupling of 0.1 mol of the diazonium compound
from aniline-2,5-disulphonic acid with 0.1 mol of 1-amino-
8-hydroxynaphthalene-3,6 disulphonic acid carried out in a
weakly acid pH range leads to a dark red solution of the
monoazo dyestuff, which can be coupled with 0.1 mol of the
; diazonium compound from the condensation product of 1 J 3-
diaminobenzene-6-sulphonic acid and 2,4-difluoro-5-chloro-
6-me-thylpyrimidine at pH 6-7 to give a dark blue dyestuff.
After salting out, isolating and drying, the dyestuff of
the formula
SO3 ~ ' ~O~, S
N = ~ N = N ~ Cl CHs
S05H HO~S SOsH NH ~ N
N~F
Le A 18 854
, . ,
:, ; ' ' : , ,~,
~: ,
:: ~ , . ::
,, ,: ,,
- 22 -
is obtained as a dark powder which dissolves in water
giving a blue-coloured solu-tion and dyes cotton in dark
blue to black colour shades.
Ex mple 25
52 par-ts of l~amino-4-(4~-N-methylamino-methyl-
anilino)-an-thraquinone-2,2l~-disulphonic acid are dissolved
in 550 parts of water and the solu-tion is adjus-ted -to pH 6
with sodium hydroxide solution. 18 parts of 2,4-
difluoro-5-chloro-6-methylpyrimidine are then added drop-
wise at 40-50 and a pH value of 6 is maintained with 2N
sodium carbonate solution. The condensation product,
which precipitates out in blue needles when the condensation
reaction has ended, is filtered off and dried. The
resulting dyestuff of the formula
~8
~ C~ C C~
O E~ CH2 N~
dyes cotton in clear blue colour shades
0.1 mol of 1-amino-4-~3'-amino-anilino)-anthra-
quinone-2-sulphonic acid are dissolved in a mix-ture of 800
parts of water and 400 parts of d:ioxane, 5 parts of sodium
; carbonate being added, and subjected to a condensation
reaction at 40-50 with 0.1 mol o~ 2,4-difluoro-5-chloro-6-
methylpyrimidine. The pH value of 6-6.5 is maintained
during this condensation reaction, whilst stirring vigor-
ously, by adding a 2N sodium carbonate solution dropwise.
When the condensation reaction has ended, the dyes-tuff is
isolated, dried and then post-sulphonated in a sulphuric
acid,/oleum mixture by customary methods. After working
up the reaction mixture, a reactive dyestuff of the prob-
able formula
Le A 18 854
.,., .,, . ;.
: ~, '' ;;: :' ':,
',
~ 23
0 N~
S03H
~ ~ C~C~3
~H ~Y `~
~ F
which dyes cotton in clear blue colour shades which are
fast -to light and have good fastness to wet processing is
obtained.
~
0,1 mol of copper phthalocyanine tetrasulphochloride,
freshly prepared in the customary manner by the action of
chlorosulphonic acid and thionyl chloride on copper
ph-thalocyanine, are suspended, in the form of the moist,
thoroughly washed filter cake, in 1,000 parts of wa-ter and
500 parts of ice and reacted with 0.1 mol o:~ the condensa-
tion product of 1,3-diaminobenzene and of 2,4-difluoro-5- ,
chloro-6-methylpyrimidine at 15-20 and at pH 8-9. A pH
value o~ about 8.5 is maintained~during this reaction by
adding 20% strength sodium carbonate solution dropwise.
When the condensation reaction has ended, the reactive dye-
stu~ o~ the formula
'~` ( SO
~ (Cu phthalocyanine~
(SO2~ C~C~13 \
~ )
4- n
n = ~ 2-3
is salted out, washed and dried a-t 50-100 in vacuo,
It is a dark blue powder which dissolves in water giving a
blue-coloured solution and dyes cotton in clear greenish-
tinged blue colour shades.
Le A 18 854
:, ~", ,1~ " ,, ".~; ~, " .. ,,. ~, , ~
: ,., . ,.. :,. ~ .
: : :: ::, ., ,. . ,i~ - :
~, :,, ~ ., ,' ., .:; ,.
.: :: , . ,
: , .. . .
