CA1112640A - Reactive dyestuffs - Google Patents
Reactive dyestuffsInfo
- Publication number
- CA1112640A CA1112640A CA325,980A CA325980A CA1112640A CA 1112640 A CA1112640 A CA 1112640A CA 325980 A CA325980 A CA 325980A CA 1112640 A CA1112640 A CA 1112640A
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- CA
- Canada
- Prior art keywords
- alkyl
- chloro
- parts
- formula
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
- C09B62/20—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a pyrimidine ring
Abstract
Abstract Reactive dyestuffs of the formula
Description
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 .
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 - . ~ ,. : , .
- , , :, . :., ~ :
, , , ;: :
' ' , ;
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
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 .
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 - . ~ ,. : , .
- , , :, . :., ~ :
, , , ;: :
' ' , ;
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 ~ ...... .
: ~
:, : ~ .. ;.
, , . ,,, ~ . . ~ : . . , :
. .
: ~ . . . :, .. ,", .
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 . '"
:, .
..
.. ~ . .. . ..
:, . . . .
~. ; . . :
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 , _ 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.
~: ;
:~ :
. _ .
- ... .. , . .. . . .. ., . .
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 - , ",, , : -. . , :, , ': : :: ;'"' : : '. ~
: "'': ':' ' : ~ ~;
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
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 ~ ...... .
: ~
:, : ~ .. ;.
, , . ,,, ~ . . ~ : . . , :
. .
: ~ . . . :, .. ,", .
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 . '"
:, .
..
.. ~ . .. . ..
:, . . . .
~. ; . . :
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 , _ 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.
~: ;
:~ :
. _ .
- ... .. , . .. . . .. ., . .
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 - , ",, , : -. . , :, , ': : :: ;'"' : : '. ~
: "'': ':' ' : ~ ~;
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-
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-
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 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 , , .. ~ : : ..
, 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 : ~ .. , '. ' : . . : : '::.
:'' :.'; ' , ,": ' ~
,:,,,:,::
.: : : .. ~, :-: , ,; ~
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-
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 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 , , .. ~ : : ..
, 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 : ~ .. , '. ' : . . : : '::.
:'' :.'; ' , ,": ' ~
,:,,,:,::
.: : : .. ~, :-: , ,; ~
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 , . , :, ; ' ' : , ,~, ~: , :: ~ , . ::
,, ,: ,, 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~
~ ~ 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~ - :
~, :,, ~ ., ,' ., .:; ,.
.: :: , . , : , .. . .
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 , . , :, ; ' ' : , ,~, ~: , :: ~ , . ::
,, ,: ,, 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~
~ ~ 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~ - :
~, :,, ~ ., ,' ., .:; ,.
.: :: , . , : , .. . .
Claims (13)
1. Reactive dyestuffs of the general formula wherein D denotes the radical of an organic dyestuff, 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 C1-C4-alkyl and n denotes 1 or 2.
atom of the chromophore, R denotes hydrogen or C1-C4-alkyl and n denotes 1 or 2.
2. Reactive dyestuffs of the formula wherein A = 2-fluoro-5-chloro-6-methylpyrimidyl, R = H or C1-C4-alkyl and R1 = H, alkyl or aryl.
3. Reactive dyestuffs of the formula wherein R = H or C1-C4-alkyl, R2 = H, alkyl, alkoxy or acylamino and A = 2-fluoro-5-chloro-6-methylpyrimidyl.
4. Reactive dyestuffs of the formula and wherein R = H or C1-C4-alkyl, R2 = H, alkyl, alkoxy or acylamino and A = 2-fluoro-5-chloro-6-methylpyrimidyl.
5. Reactive metal complex dyestuffs based on at least one dyestuff of the formula wherein R3 = H, halogen, -NO2 or alkyl, R = H or C1-C4-alkyl and A = 2-fluoro-5-chloro-6-methylpyrimidyl.
6. 1:1 Copper complexes of the metal-free dyestuffs of Claim 5.
7. 1:2 Cr or Co complexes of metal-free dyestuffs of Claim 5.
8. 1:2 Cr or Co complexes which contain two molecules of a metal-free dyestuff of Claim 5.
9. 1:2 Cr or Co complexes which contain one molecule of a metal-free dyestuff of Claim 5.
10. Reactive dyestuffs of the formula wherein R4 = -?-A, R = H or C1-C4-alkyl and A = 2-fluoro-5-chloro-6-methylpyrimidyl.
11. Reactive dyestuffs of the formula wherein A = 2-fluoro-5-chloro-6-methylpyrimidyl, R - H or C1-C4-alkyl and R5 = H, C1-C4-alkyl or C1-C4-alkoxy.
12. Reactive dyestuffs of the formula wherein R6 and R7 = H or C1-C4-alkyl, or together C4-C5-alkylene, optionally interrupted by N or O, A = 2-fluoro-5-chloro-6-methylpyrimidyl and R = H or C1-C4-alkyl.
13. Reactive dyestuffs of the formulae wherein A = 2-fluoro-5-chloro-6-methylpyrimidyl, R5 = H, C1-C4-alkyl or C1-C4-alkoxy, R9 = H, CH3 or C1, R10 = H, CH3, OCH3, NHCOCH3 or NHCOMH2 and R11 = H, CH3, C1-C4-alkoxy or acylamino.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2817780A DE2817780C2 (en) | 1978-04-22 | 1978-04-22 | Reactive dyes |
| DEP2817780.2 | 1978-05-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1112640A true CA1112640A (en) | 1981-11-17 |
Family
ID=6037795
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA325,980A Expired CA1112640A (en) | 1978-04-22 | 1979-04-20 | Reactive dyestuffs |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS54139931A (en) |
| BE (1) | BE875726A (en) |
| BR (1) | BR7902455A (en) |
| CA (1) | CA1112640A (en) |
| CH (1) | CH640557A5 (en) |
| DE (1) | DE2817780C2 (en) |
| ES (1) | ES479771A1 (en) |
| FR (1) | FR2423520B1 (en) |
| GB (1) | GB2019867B (en) |
| IN (1) | IN151463B (en) |
| IT (1) | IT1113356B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3010161A1 (en) * | 1980-03-17 | 1981-09-24 | Bayer Ag, 5090 Leverkusen | DYES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR COLORING MATERIALS CONTAINING HYDROXYL GROUPS OR NITROGEN |
| DE3400412A1 (en) * | 1984-01-07 | 1985-07-18 | Bayer Ag, 5090 Leverkusen | STORAGE SOLUTIONS OF REACTIVE DYES |
| DE3406232A1 (en) * | 1984-02-21 | 1985-08-29 | Bayer Ag, 5090 Leverkusen | FIBER REACTIVE MOLD DYE |
| DE4125754A1 (en) * | 1991-08-03 | 1993-02-04 | Bayer Ag | FLUORPYRIMIDINE REACTIVE DYES |
| EP0568876B1 (en) | 1992-05-04 | 1996-08-28 | Bayer Ag | Reactive dyes, their preparation and their use |
| CA2448867C (en) | 2001-10-08 | 2010-06-01 | Clariant Finance (Bvi) Limited | Fibre-reactive trisazo dyes |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1290915B (en) * | 1966-02-17 | 1969-03-20 | Bayer Ag | Process for dyeing and printing fiber materials made from aromatic polyesters and cellulose acetates |
| CH499604A (en) * | 1966-04-22 | 1970-11-30 | Ciba Geigy Ag | Process for the production of fiber-reactive formazanazo dyes containing heavy metals |
| CH501713A (en) * | 1968-01-29 | 1971-01-15 | Ciba Geigy Ag | Process for the production of fiber-reactive, heavy metal-containing formazan dyes |
| DE1644171A1 (en) * | 1966-09-10 | 1970-07-30 | Bayer Ag | Reactive dyes and processes for their preparation |
| CH501712A (en) * | 1968-01-12 | 1971-01-15 | Bayer Ag | Process for the preparation of phthalocyanine reactive dyes |
| CH501714A (en) * | 1968-01-29 | 1971-01-15 | Ciba Geigy Ag | Process for the production of fiber-reactive, heavy metal-containing formazan dyes |
| DE1809388A1 (en) * | 1968-11-16 | 1970-06-11 | Bayer Ag | Reactive azo dyestuffs containing fluorine, - for cellulosic and nitrogenous fabrics |
| DE2634497C2 (en) * | 1976-07-31 | 1986-09-25 | Bayer Ag, 5090 Leverkusen | Reactive dyes and their use |
-
1978
- 1978-04-22 DE DE2817780A patent/DE2817780C2/en not_active Expired
-
1979
- 1979-03-21 IN IN187/DEL/79A patent/IN151463B/en unknown
- 1979-04-18 GB GB7913440A patent/GB2019867B/en not_active Expired
- 1979-04-19 IT IT22019/79A patent/IT1113356B/en active
- 1979-04-20 CA CA325,980A patent/CA1112640A/en not_active Expired
- 1979-04-20 JP JP4808779A patent/JPS54139931A/en active Granted
- 1979-04-20 BE BE0/194728A patent/BE875726A/en not_active IP Right Cessation
- 1979-04-20 ES ES479771A patent/ES479771A1/en not_active Expired
- 1979-04-20 FR FR7910005A patent/FR2423520B1/en not_active Expired
- 1979-04-20 BR BR7902455A patent/BR7902455A/en unknown
- 1979-04-20 CH CH377179A patent/CH640557A5/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DE2817780C2 (en) | 1984-09-20 |
| CH640557A5 (en) | 1984-01-13 |
| GB2019867A (en) | 1979-11-07 |
| IT7922019A0 (en) | 1979-04-19 |
| BR7902455A (en) | 1979-10-30 |
| JPS54139931A (en) | 1979-10-30 |
| FR2423520B1 (en) | 1986-05-02 |
| ES479771A1 (en) | 1980-10-01 |
| FR2423520A1 (en) | 1979-11-16 |
| IT1113356B (en) | 1986-01-20 |
| IN151463B (en) | 1983-04-23 |
| GB2019867B (en) | 1982-09-02 |
| DE2817780A1 (en) | 1979-11-08 |
| BE875726A (en) | 1979-10-22 |
| JPS614422B2 (en) | 1986-02-10 |
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