CA1052777A - Tetrareactive disazo dyestuffs, their manufacture and their use - Google Patents
Tetrareactive disazo dyestuffs, their manufacture and their useInfo
- Publication number
- CA1052777A CA1052777A CA243,439A CA243439A CA1052777A CA 1052777 A CA1052777 A CA 1052777A CA 243439 A CA243439 A CA 243439A CA 1052777 A CA1052777 A CA 1052777A
- Authority
- CA
- Canada
- Prior art keywords
- formula
- acid
- amino
- naphthol
- sulphonic 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
- C09B62/04—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 triazine ring
- C09B62/043—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 triazine ring containing two or more triazine rings linked together by a non-chromophoric link
Abstract
Abstract of the Disclosure Tetrareactive disazo dyestuffs of the formula (1) wherein D represents a benzene radical containing at least one sulpho group; K represents a radical of l-amino (or aminobenzoylamino)-8-naphthol-3,6-disulphonic acid, of l-amino(or aminobenzoylamino)-8-naphthol-4,6-disulphonic acid, of 2-amino(or aminobenzoylamino)-5-naphthol-7-sulphonic acid, of 2-amino(or aminobenzoylamino)-8-naphthol-6-sulphonic acid, of 2-amino(or aminobenzoylamino)-5-naphthol-1,7-disulphonic acid, or of 2-amino(or amino-benzoylamino)-8-naphthol-3,6-disulphonic acid; B represents an aliphatic or aromatic radical; R1, R2 and R3 each independently represent hydrogen or alkyl having 1 to 6 carbon atoms; X represents chlorine, bromine or fluorine;
and Y represents hydrogen, low-molecular alkyl or alkoxy, acetylamino, halogen, carboxy or sulpho.
and Y represents hydrogen, low-molecular alkyl or alkoxy, acetylamino, halogen, carboxy or sulpho.
Description
~L~5~77~
The present invention relates to tetrareactive disazo dyestuffs of the formula SO H ....
11 _C~N~~--N~--~N=N--K--NH--C~N`I--N{~
N~ N . N~C--N R (1) wherein D represents a benzene radical containing at least one sulpho group; K represents a radical of l-amino (or aminobenzoylamino)-8-naphthol-3,6-disulphonic acid, of l-amino(or aminobenzoylamino)-8-naphthol-4,6-disulphonic acid, of 2-amino(or aminobenzoylamino)-5 naphthol-7-sulphonic acid, of 2-amino(or aminobenzoylamino)-$-naphthol-6 sulphonic acid, of 2-amino(or aminobenzoylamino)-S-naphthol-1,7-disulphonic acid, or of 2-amino(or amino-benzoylamino)-8-naphthol-3,6-disulphonic acid; B represents - an aliphatic or aromatic radical; Rl, R2 and R3 each independently represent hydrogen or alkyl having 1 to 6 carbon atoms; X represents chlorine, bromine or fluorine;
and Y represents hydrogen, low-molecular alkyl or alkoxy, ~.
acetylamino, halogen, carboxy or sulpho.
The benzene radical D can contain, besides sulphonic acid groups, further substituents, these are in particular:
, ~
.~ .
:; `
~ 6~5~77'~
alkyl groups such as methyl, ethyl, isopropyl or butyl, alkoxy groups such as methoxy, ethoxy, ethoxyethoxy or isopropoxypropoxy, acyl groups such as acetyl, acylamino groups such as acetylamino or benzoylamino, the ureido S and carboxy group, and halogen atoms such as chlorine or bromine.
The aliphatic or aromatic radical B is derived from an aliphatic or aromatic diamine. Thus B can be a long (e.g. having 10 or more carbon atoms) or shorter, straight-chain or branched chain alkylene radical; it can be in particular an alkylene radical having 1 to 6 carbon atoms, e.g. ethylene, propylene, butylene, hexylene or cyclohexylene. Preferably B is an aromatic radical, e.g.
a naphthylene radical, the radical of diphenyl or stilbene, or especially a phenylene radical. This can contain further substituents, e.gO halogen atoms, low-molecular alkyl and alkoxy groups, amino, acylamino, ureido, hydroxy, carboxy and sulpho groups. Preferably B is a phenylene radical.
Alkyl radical denoted by Rl, R2 and R3 having 1 to 6 c?rbon atoms are, e.g., methyl, ethyl, propyl, isopropyl, butyl or cyclohexyl. Suitable as substituents Y are alkyl groups such as methyl, ethyl, isopropyl or butyl, alkoxy groups such as methoxy or ethoxy, halogen atoms such as ~ 3 --:,j ~5'~7~7 chlorine or bromine, the carboxy group and, in particular, . the sulpho group.
. The halogen atoms X on the s-triazine radicals of ^. the tetrareactive disazo dyestuffs of the formula (1) can be identical or diffexent.
` Preferred are tetrareactive disazo dyestuffs wherein D represents the radical of 1,3-diaminobenzene-4-sulphonic acid, K represents the radical of l-amino-8-naphthol-3,6-disulphonic acid or the radical of 2-amino-5-naphthol-7-sulphonic acid, B represents an aromatic radical, Rl, R2 and R3 represent hydrogen, X represents chlorine, and . Y represents hydrogen, sulpho, chlorine, methyl or carboxy,with the sulpho group, or Y if Y is a substituent other than the sulpho group, in the terminal benzene radical being in the or~ho-position with respect to the -N-group~ :
~3 By virtue of the presence of four halogen atoms X, which can be split off, in the four s-triazine radicals of . the disazo dyestuffs of the formula (1), these dyestuffs are fibre(tetra)reactive.
By fibre-reactive compounds are meant those that are able to react with the hydroxy groups of the cellulose, or with the amino groups of natural or synthetic polyamides a . ~ . .
S27 ~7 to form covalent chemical bonds.
The tetrareactive disazo dyestuffs of the formula (1) are manufactured by a process in which diazo components of the formula H2N-D-NH2 (2), coupling components of the formula K-NH2 (3), : trihalogeno-s-triazines of the formula X--C~N~C--X
N~ N
X ,, aminobenzenesulphonic acids of the formula HIN ~ y (5 . 3 and aliphatic or aromatic diamines of the formula Rll - B ~ ~R2 (6) . H H
are combined by means of coupling and condensation to give ~etrareac~ive disazo dyestuffs of the formula (1).
10 ~ ;7 ~ ince the individual steps of the process can be performed in varying sequence, optionally in some cases also simultaneously~ various modifications of the process are possible. The starting materials to be used for each partial reaction are embraced by the formula (1).
Important methods of procedure for manufacturing the tetrareactive disazo dyestuffs of the formula (1) are .' as follows:
a) A diazo component of the formula (2) is condensed with a trihalogeno-s-triazine of the formula (4). The condénsation product is diazotised and the product obtained is then coupled to the secondary condensation product from a trihalogeno-s-triazine of the formula (4), a coupling ' component of the formula (3~ and an aminobenzenesulphonic , 15 acid of the formula (5), The resulting monoazo compound is condensed in the final stage with an aliphatic or aromatic diamine of the formula (6) in the molar ratio of 2:1.
b) 2 moles of a trihalogeno-s-triazine of the formula (4) are condensed with 2 moles of a diazo component of the formula (2) and with 1 mole of an aliphatic or aromatic diamine of the formula (6). The condensation product is diazotised and the product obtained is coupled to the -- 6 -- .
' .
7~7 condensation product from a trihalogeno-s-triazine of the formula (4) and a coupling component of the formula (3).
The resulting product is subsequently condensed with
The present invention relates to tetrareactive disazo dyestuffs of the formula SO H ....
11 _C~N~~--N~--~N=N--K--NH--C~N`I--N{~
N~ N . N~C--N R (1) wherein D represents a benzene radical containing at least one sulpho group; K represents a radical of l-amino (or aminobenzoylamino)-8-naphthol-3,6-disulphonic acid, of l-amino(or aminobenzoylamino)-8-naphthol-4,6-disulphonic acid, of 2-amino(or aminobenzoylamino)-5 naphthol-7-sulphonic acid, of 2-amino(or aminobenzoylamino)-$-naphthol-6 sulphonic acid, of 2-amino(or aminobenzoylamino)-S-naphthol-1,7-disulphonic acid, or of 2-amino(or amino-benzoylamino)-8-naphthol-3,6-disulphonic acid; B represents - an aliphatic or aromatic radical; Rl, R2 and R3 each independently represent hydrogen or alkyl having 1 to 6 carbon atoms; X represents chlorine, bromine or fluorine;
and Y represents hydrogen, low-molecular alkyl or alkoxy, ~.
acetylamino, halogen, carboxy or sulpho.
The benzene radical D can contain, besides sulphonic acid groups, further substituents, these are in particular:
, ~
.~ .
:; `
~ 6~5~77'~
alkyl groups such as methyl, ethyl, isopropyl or butyl, alkoxy groups such as methoxy, ethoxy, ethoxyethoxy or isopropoxypropoxy, acyl groups such as acetyl, acylamino groups such as acetylamino or benzoylamino, the ureido S and carboxy group, and halogen atoms such as chlorine or bromine.
The aliphatic or aromatic radical B is derived from an aliphatic or aromatic diamine. Thus B can be a long (e.g. having 10 or more carbon atoms) or shorter, straight-chain or branched chain alkylene radical; it can be in particular an alkylene radical having 1 to 6 carbon atoms, e.g. ethylene, propylene, butylene, hexylene or cyclohexylene. Preferably B is an aromatic radical, e.g.
a naphthylene radical, the radical of diphenyl or stilbene, or especially a phenylene radical. This can contain further substituents, e.gO halogen atoms, low-molecular alkyl and alkoxy groups, amino, acylamino, ureido, hydroxy, carboxy and sulpho groups. Preferably B is a phenylene radical.
Alkyl radical denoted by Rl, R2 and R3 having 1 to 6 c?rbon atoms are, e.g., methyl, ethyl, propyl, isopropyl, butyl or cyclohexyl. Suitable as substituents Y are alkyl groups such as methyl, ethyl, isopropyl or butyl, alkoxy groups such as methoxy or ethoxy, halogen atoms such as ~ 3 --:,j ~5'~7~7 chlorine or bromine, the carboxy group and, in particular, . the sulpho group.
. The halogen atoms X on the s-triazine radicals of ^. the tetrareactive disazo dyestuffs of the formula (1) can be identical or diffexent.
` Preferred are tetrareactive disazo dyestuffs wherein D represents the radical of 1,3-diaminobenzene-4-sulphonic acid, K represents the radical of l-amino-8-naphthol-3,6-disulphonic acid or the radical of 2-amino-5-naphthol-7-sulphonic acid, B represents an aromatic radical, Rl, R2 and R3 represent hydrogen, X represents chlorine, and . Y represents hydrogen, sulpho, chlorine, methyl or carboxy,with the sulpho group, or Y if Y is a substituent other than the sulpho group, in the terminal benzene radical being in the or~ho-position with respect to the -N-group~ :
~3 By virtue of the presence of four halogen atoms X, which can be split off, in the four s-triazine radicals of . the disazo dyestuffs of the formula (1), these dyestuffs are fibre(tetra)reactive.
By fibre-reactive compounds are meant those that are able to react with the hydroxy groups of the cellulose, or with the amino groups of natural or synthetic polyamides a . ~ . .
S27 ~7 to form covalent chemical bonds.
The tetrareactive disazo dyestuffs of the formula (1) are manufactured by a process in which diazo components of the formula H2N-D-NH2 (2), coupling components of the formula K-NH2 (3), : trihalogeno-s-triazines of the formula X--C~N~C--X
N~ N
X ,, aminobenzenesulphonic acids of the formula HIN ~ y (5 . 3 and aliphatic or aromatic diamines of the formula Rll - B ~ ~R2 (6) . H H
are combined by means of coupling and condensation to give ~etrareac~ive disazo dyestuffs of the formula (1).
10 ~ ;7 ~ ince the individual steps of the process can be performed in varying sequence, optionally in some cases also simultaneously~ various modifications of the process are possible. The starting materials to be used for each partial reaction are embraced by the formula (1).
Important methods of procedure for manufacturing the tetrareactive disazo dyestuffs of the formula (1) are .' as follows:
a) A diazo component of the formula (2) is condensed with a trihalogeno-s-triazine of the formula (4). The condénsation product is diazotised and the product obtained is then coupled to the secondary condensation product from a trihalogeno-s-triazine of the formula (4), a coupling ' component of the formula (3~ and an aminobenzenesulphonic , 15 acid of the formula (5), The resulting monoazo compound is condensed in the final stage with an aliphatic or aromatic diamine of the formula (6) in the molar ratio of 2:1.
b) 2 moles of a trihalogeno-s-triazine of the formula (4) are condensed with 2 moles of a diazo component of the formula (2) and with 1 mole of an aliphatic or aromatic diamine of the formula (6). The condensation product is diazotised and the product obtained is coupled to the -- 6 -- .
' .
7~7 condensation product from a trihalogeno-s-triazine of the formula (4) and a coupling component of the formula (3).
The resulting product is subsequently condensed with
2 moles of an aminobenzenesulphonic acid of the formula (5).
c) The procedure is carried out as under b) except that : in the final stage the product obtained is coupled to the secondary condensation product from a trihalogeno-s-triazine of the formula ~4), a coupling component of the formula (3) and an aminobenzenesulphonic acid of the formula (5).
d) 2 moles of a trihalogeno-s~triazine of the formula (4) are condensed with 1 mole of an aliphatic or aromatic diamine of the formula (6); and the condensation product is condensed with 2 moles of a diazo component of the formula ~2). The formed disecondary condensation product is tetrazotised9 and the product obtained is coupled to 2 moles of a coupling component of the formula (3). The resulting disazo compound is condensed with 2 moles of a trihalogeno-s triazine of the formula (4); and the conden-sation product obtained therefrom is condensed finally with2 moles of an aminobenzenesulphonic acid of the formula (5).
In the case of the process variants b) and c)~ the 7~f7 ,;
condensation of the trihalogeno-s-triazine of the . formula (4) with the diazo component of the formula (23 may be performed first and with the aliphatic or aromatic diamine of the formula (6) second, or vice versa.
In the process variant d), it is also possible to condense 2 moles of trihalogeno-s-triazine of the formula ~4) firstly with 2 moles of a diazo component of the formwla (2) and subsequently with 1 mole of an aliphatic or aromatic diamine of the formula (6), and to then proceed as described. It is furthermore possible in process variant d) to combine the condensations performed in the penultimate stage and final stage with 2 moles of tri-halogeno-s triazine of the formula (4) and 2 moles of an aminobenzenesulphonic acid of the formula (5), respectively, j 15 and to condense with 2 moles of the primary condensation product from a trihalogeno-s-triazine of the formula (4) and an aminobenzenesulphonic acid of the formula (5).
The variant a) is the preferred procedure for the ,~ ~ manufacture of the tetrareactive disazo dyestuffs of the formula (1).
As starting materials there are preferably used:
as diazo component of the formula (2) 1,3-diami.nobenzene-4-sulphonic acid; as coupling oomponent of the formula (3) ~ .
~ ~S'~7~ 7 l-amino-8-naphthol-3,6-disulphonic acid or 2-amino-5-- naphthol-7-sulphonic acid, a trihalogeno-s triazine of ~- the formula (4) wherein X is chlorine, an aminobenzene-- sulphonic acid of the formula ~S) wherein R3 is hydrogen, and Y represents hydrogen or a sulpho group, with the sulpho group or Y being in the ortho-position with respect to the HN-group, and an aromatic diamine of the formula (6) wherein Rl and R2 represent hydrogen.
Diazotisation of the diazo components of the formula (2) is performed by methods known per se, e.g. with the aid of hydrochloric acid and sodium nitrite. Coupling with `~ the coupling components of the formula (3) is likewise : performed by methods known per se in an aqueous, acid or alkaline medium.
Condensation with trihalogeno-s-triazines, diazo components of the formula (2), coupling components of the { ormula (3), aminobenzenesulphonic acids of the formula (5) and aliphatic or aromatic diamines of the formula (6) is performed advantageously with the use of acid-binding agents, such as sodium carbonate or sodium hydroxide, and under such conditions that in the finished tetrareactive disazo dyestuEf of the formula (1) there still remains one ' J
:
5~ ~7 halogen atom per s-triazine ring, i.e. in organic . solvents or at relatively low temperature in an aqueous medium.
:
, The following may be mentioned as starting materials for manufacturlng the fibre-reactive disazo compounds of the formula (1):
; Diazo components ~ 1,3-diaminobenzene-4-sulphonic acid, - 1,4-diaminobenzene-2-sulphonic acid, ii 10 1,4-diaminobenzene-2,6-disulphonic acid, ;;
1,4-diaminobenzene-2,5-disulphonic acid, ~i 1,4-diamino-2-chlorobenzene-5-sulphonic acid, ~, 1,4-diamino-2-methylbenzene-5-sulphonic acid,
c) The procedure is carried out as under b) except that : in the final stage the product obtained is coupled to the secondary condensation product from a trihalogeno-s-triazine of the formula ~4), a coupling component of the formula (3) and an aminobenzenesulphonic acid of the formula (5).
d) 2 moles of a trihalogeno-s~triazine of the formula (4) are condensed with 1 mole of an aliphatic or aromatic diamine of the formula (6); and the condensation product is condensed with 2 moles of a diazo component of the formula ~2). The formed disecondary condensation product is tetrazotised9 and the product obtained is coupled to 2 moles of a coupling component of the formula (3). The resulting disazo compound is condensed with 2 moles of a trihalogeno-s triazine of the formula (4); and the conden-sation product obtained therefrom is condensed finally with2 moles of an aminobenzenesulphonic acid of the formula (5).
In the case of the process variants b) and c)~ the 7~f7 ,;
condensation of the trihalogeno-s-triazine of the . formula (4) with the diazo component of the formula (23 may be performed first and with the aliphatic or aromatic diamine of the formula (6) second, or vice versa.
In the process variant d), it is also possible to condense 2 moles of trihalogeno-s-triazine of the formula ~4) firstly with 2 moles of a diazo component of the formwla (2) and subsequently with 1 mole of an aliphatic or aromatic diamine of the formula (6), and to then proceed as described. It is furthermore possible in process variant d) to combine the condensations performed in the penultimate stage and final stage with 2 moles of tri-halogeno-s triazine of the formula (4) and 2 moles of an aminobenzenesulphonic acid of the formula (5), respectively, j 15 and to condense with 2 moles of the primary condensation product from a trihalogeno-s-triazine of the formula (4) and an aminobenzenesulphonic acid of the formula (5).
The variant a) is the preferred procedure for the ,~ ~ manufacture of the tetrareactive disazo dyestuffs of the formula (1).
As starting materials there are preferably used:
as diazo component of the formula (2) 1,3-diami.nobenzene-4-sulphonic acid; as coupling oomponent of the formula (3) ~ .
~ ~S'~7~ 7 l-amino-8-naphthol-3,6-disulphonic acid or 2-amino-5-- naphthol-7-sulphonic acid, a trihalogeno-s triazine of ~- the formula (4) wherein X is chlorine, an aminobenzene-- sulphonic acid of the formula ~S) wherein R3 is hydrogen, and Y represents hydrogen or a sulpho group, with the sulpho group or Y being in the ortho-position with respect to the HN-group, and an aromatic diamine of the formula (6) wherein Rl and R2 represent hydrogen.
Diazotisation of the diazo components of the formula (2) is performed by methods known per se, e.g. with the aid of hydrochloric acid and sodium nitrite. Coupling with `~ the coupling components of the formula (3) is likewise : performed by methods known per se in an aqueous, acid or alkaline medium.
Condensation with trihalogeno-s-triazines, diazo components of the formula (2), coupling components of the { ormula (3), aminobenzenesulphonic acids of the formula (5) and aliphatic or aromatic diamines of the formula (6) is performed advantageously with the use of acid-binding agents, such as sodium carbonate or sodium hydroxide, and under such conditions that in the finished tetrareactive disazo dyestuEf of the formula (1) there still remains one ' J
:
5~ ~7 halogen atom per s-triazine ring, i.e. in organic . solvents or at relatively low temperature in an aqueous medium.
:
, The following may be mentioned as starting materials for manufacturlng the fibre-reactive disazo compounds of the formula (1):
; Diazo components ~ 1,3-diaminobenzene-4-sulphonic acid, - 1,4-diaminobenzene-2-sulphonic acid, ii 10 1,4-diaminobenzene-2,6-disulphonic acid, ;;
1,4-diaminobenzene-2,5-disulphonic acid, ~i 1,4-diamino-2-chlorobenzene-5-sulphonic acid, ~, 1,4-diamino-2-methylbenzene-5-sulphonic acid,
3-(3'-or 4'-aminobenzoylamino)-1-aminobenzene-6-sulphonic acid, 1-t4'-amlnobenzoylamino)-4-aminobenzene-2,5-disulphonic acid.
' Coupll~G~L5l9~5~
, l-amino-8-naphthol-3,6-disulphonic acid, l-amino-8-naphthol-4~6-disulphonic acid, 2-amino-5-naphthol-7-sulphonic acid, 2Q 2-amino-8-naphthol~6-sulphonic acid, ¦ 2~amino-8-naph~hol-3,6~disulphonic acid, 2-amino-5-naphthol-1,7-disulphonic acid, .1 .
~ , . ... .. , . , .. .. ., ., . ~ . . , : , ... . . . . .
` ~S ~77~
1-(3'- or 4'-aminobenzoylamino~-8-naphthol-3,6-disulphoni.c acid, 1-(3l- or 4'-aminobenzoylamino)-8-naphthol-4,6-disulphonic . acid, 2-(3'- or 4'-aminobenzoylamino)-5-naphthol-7-sulphonic acid, 2-(3'- or 4'-aminobenzoy~amino)-8-naphthol~6-sulphonic acid, ~ 5 2-(3'- or 4'-aminobenzoylamino)-8-naphthol-3,6-disulphonic acid, 2-(3'- or 4'-aminobenzoylamino)-5-naphthol 1,7 disulphonic acid.
Triha~ 3L _ triaz nes cyanuric chloride, cyanuric bromide or cyanuric fluoride.
.~ .
Aliphatic and aromatic diamines ethylenediamine, ' .
'f n-propylenediamine, n-butylenediamine, ` l-methyl-n-propylenediamine, n-hexylenediamine s 2-ethyl-n butylenediamine, 1,4-cyclohexane-bis-(methylamine), 1,3-diaminobenzene, 1,4-diaminobenæene, 1,3-diamino-4-chlorobenzene, 1,3-diamino-4-methylbenzene, 1,3-diamino-4-ethylbenzene, 7~7 1,3-diamino-4-methoxybenzene~
, .
1,3-diamino-4-ethoxybenzene, 2,6-diamino-naphthalene, 1,3-diamino-2,4,6-trimethylbenzene, 5 1,4-diamino 2,3,5,6-tetramethylbenzene, . .
` 1,3-diamino-4-nitrobenzene,
' Coupll~G~L5l9~5~
, l-amino-8-naphthol-3,6-disulphonic acid, l-amino-8-naphthol-4~6-disulphonic acid, 2-amino-5-naphthol-7-sulphonic acid, 2Q 2-amino-8-naphthol~6-sulphonic acid, ¦ 2~amino-8-naph~hol-3,6~disulphonic acid, 2-amino-5-naphthol-1,7-disulphonic acid, .1 .
~ , . ... .. , . , .. .. ., ., . ~ . . , : , ... . . . . .
` ~S ~77~
1-(3'- or 4'-aminobenzoylamino~-8-naphthol-3,6-disulphoni.c acid, 1-(3l- or 4'-aminobenzoylamino)-8-naphthol-4,6-disulphonic . acid, 2-(3'- or 4'-aminobenzoylamino)-5-naphthol-7-sulphonic acid, 2-(3'- or 4'-aminobenzoy~amino)-8-naphthol~6-sulphonic acid, ~ 5 2-(3'- or 4'-aminobenzoylamino)-8-naphthol-3,6-disulphonic acid, 2-(3'- or 4'-aminobenzoylamino)-5-naphthol 1,7 disulphonic acid.
Triha~ 3L _ triaz nes cyanuric chloride, cyanuric bromide or cyanuric fluoride.
.~ .
Aliphatic and aromatic diamines ethylenediamine, ' .
'f n-propylenediamine, n-butylenediamine, ` l-methyl-n-propylenediamine, n-hexylenediamine s 2-ethyl-n butylenediamine, 1,4-cyclohexane-bis-(methylamine), 1,3-diaminobenzene, 1,4-diaminobenæene, 1,3-diamino-4-chlorobenzene, 1,3-diamino-4-methylbenzene, 1,3-diamino-4-ethylbenzene, 7~7 1,3-diamino-4-methoxybenzene~
, .
1,3-diamino-4-ethoxybenzene, 2,6-diamino-naphthalene, 1,3-diamino-2,4,6-trimethylbenzene, 5 1,4-diamino 2,3,5,6-tetramethylbenzene, . .
` 1,3-diamino-4-nitrobenzene,
4,4' diaminos~ilbene, 4,4'-diaminodiphenylmethane, - 4,4'-diaminodiphenyl (benzidine), 3,3'-dimethylbenzidine, . 3,3'-dimethoxybenzidine, 3,3'-dichlorobenzidine, 3,3'-dicarboxybenzidine, ~ 3,3'-dicarboxymethoxy-benzidine, ^. 15 2,2'-dimethylbe~zidine, 4,2'-diaminodiphenyl (diphenyline), 2,6-diaminonaphthalene-4,8-disulphonic acid, 1,4-diaminobenzene-2-sulphonic acid, 1,4-diaminobenzene-2,5-disulphonic acid, 1,4-diaminobenzene-2,6-disul.phonic acida 1,3-diaminobenzene~4-sulphonic acid, 1,3-diaminobenzene-4,6-disulphonic acid, 1,4-diaminobenzene-2-carboxylic acid .: ,; , ~ : ,. . . . . . . .
: .. : .. : , . ~ . . ........... ,:.. . : , . . , ~:
~ ~5'~77'7 1,3-diaminobenzene-4-carboxylic acid 1,4-diamino-2-methylbenzene, 4,4'-diaminodiphenyl oxide, 4,4'-diaminodiphenylurea-2,2'-disulphonic acid,
: .. : .. : , . ~ . . ........... ,:.. . : , . . , ~:
~ ~5'~77'7 1,3-diaminobenzene-4-carboxylic acid 1,4-diamino-2-methylbenzene, 4,4'-diaminodiphenyl oxide, 4,4'-diaminodiphenylurea-2,2'-disulphonic acid,
5 4,4'-diaminodiphenyloxyethane-2,2'-disulphonic acid~
4~4'-diaminostilbene-2,2'-disulphonic acid, 4,4'-diaminodiphenylethane-2,2'-disulphonic acid, piperazine.
The new tetrareactive disazo dyestuffs of the formula (1) can be isolated and processed into suitable dry dyestuff preparations. Isolation is effected preferably at the lowest poss;ble temperature by salting out and filtration. The filtered dyestuffs can be dried optionally after the addition of diluents and/or buffer agents~
e.g. after the addition of a mixture of equal parts of mono- and disodium phosphate; drying is pre~erably performed at not too high a temperature and under reduced pressuraO By spray drying of the whole of the produced mixture it is possible in certain cases to obtain the dry preparations according to the invention direct, i.e.
without intermediate isolation of the dyestuffs.
; The dyestuffs are suitable for the dyeing and printing of the widest variety of materials, such as silk~ leather, ', .
`' ' " ' . ' ' . ~ . . ', " ' , . i ' ' , ' ' , . . ' ', .' " ': ' .
5~7"~
,:.
wool, superpolyamide fibres and superpolyurethanes, ,, .
especially, however, cellulose-containing materials of fibrous structure, such as linen, cellulose, regenera~ed cellulose and, in particular, cotton. They are especially suitable for dyeing by the exhaust process from a long liquor, from an aqueous alkaline bath having if required a high salt content; and by the pad-dyeing process, wherein the material is impregnated with aqueous, optionally salt-containing dyestuff solutions, and, after an alkali treatment or in the presence of alkali, the dyestuffs are fixed, if necessary by the action of heat.
The dyestuffs are suitable also for printing, especially on cotton; also for printing of nitrogen-containing fibres, e.g. of wool, silk or wool-containing lS mixed fabrics. They are characterised, in particular, by an enhanced reactivity and by a good affinity, and hence by a high degree of fixing. They have the advantage also that unfixed constituents can be readily washed out.
The dyeings and printings obtained have a high depth of coLour and have good fastness to light as well as very good fastness to wet processing, such as good fastness to washing.
~or the purpose of improving fastness to wet processing, .
~ S'~ 7 it is recommended that the dyeings and printings be : subjected to a thorough rinsing with cold water and hot water, optionally with the addition of an agent having a dispersing action and promoting the diffusion of the unfixed constituents.
Except where otherwise stated in the following Examples, 'parts' denote parts by weight, percentages are given as per cent by weight, and temperature values . are expressed in degrees Centigrade. Between parts by .
weight and parts by volume there exists the same relationship as between gram and cubic cen~imetre.
.
l` :
Example 1 18.8 parts of 1,3~diaminobenzene-6-sulphonic acid are dissolved in 200 parts of water, with the addition of sodium carbonate, at pH 6 to 7. The solution is added to an ice-cold aqueous suspension of 18.5 parts of - S cyanuric chloride; and the mixture is neutralised, with ice-cooling in the course of 30 minutes, with a diluted sodium hydroxide solution. After completion of condensation, 30 parts of concentrated hydrochloric acid are added and diazotisation is performed with a solution of 6.9 parts of sodium nitrite. The excess of nitrous acid is decomposed with sulphamic acid, and the diazo compound is added to a neutral aqueous solution of 60 parts of the secondary condensation product from cyanuric chloride, 1,8-amino-` naphthol-3,6-disulphonic acid and 1-aminobenzene-3-sulphonic acid, ~ith the pH-value being maintained between 6 and 7.5 by the addition of sodium carbonate. After coupling is completed, there is added a solution of 5.4 parts of 1,4-diaminobenzene; the temperature is gradually raised to 35 and condensation is performed at this temperature, whilst the pH-value of the soluti~n is kept between 6 and 7 with a diluted sodium hydroxide solution. After completion of the reaction, the dyestuff solution is concentrated in vacuo .. , . ~ ~ i ~a!S;~7'~7 to dryness. The tetrareactive disazo dyestuff obtained dyes cellulose fibres in the exhaust process, in the presence of electrolyte and alkali, in red shades.
~` If there is used in this Example~ instead of S cyanuric chloride, a corresponding amount of cyanuric bromide, then there is obtained a tetrareactive disazo dyestuff having similar properties.
The following Table contains a number of further examples that can be obtained by the procedure given in Example 1.
.
;
.' a) n) ~ ~
r........... ~ ~ ~
,/ ~ ~ ' 0~' 0 0 ~ ~ __ ._ _ _ .. , ...... _ ___ .__ . _._.__ ' '::
O O O O ~: ^ C~
,,~ ~ rl ~rl a.) .~ ~ 0 ~ r ~
~rl I N I N I N i N ~
, ~ ~ ~ rl .. ... . _ ~ . .. _ __ _ _ . ._ ,., ~ , a) ~
. ~ I ~rl ~., ~-rl ~ ~ .,.
.' t~ S~ ~ 1 0 u ~ O t~
~, ~ ~0~:: ~0~ ~0~
'i O ~ ~ ,1 ~ ,1 ~ ~ rl ~n i, n u ~ tJ ~ L) c~ rl ~ ~rl :' O C~ ~ C~
.~ ~ rl ~ ~il U t~ ~I t.) _O t) U') ~C ~ ~ g ~ O O ~
~i ~ U~ ~ J~ O~ 0~1 1 0 i :j .,1 ~ ~,) rl ~ ~1 ~rl,5: ~1 0 ,~ a .~ ,~ a) ~ ~1 e .~ ~ ~ e ! .
o o ~ ~ o~
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A ~
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.` . :, ` , .`
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- - ,~
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.~ .. __ ._ ._ . ... , ~ ~ _ o o o o ~i o ~ b ~1 ~ ri ~ ~ri ~ I ri 1~3 ri ~: ri ~ ri ~ ri ~ C~ ri ~ rl ~ _ rl I N I N I N I N t:~ I N ~ I N
n ~ ~ o ~ ~
^ q~ rlrl ~ a) .. . - . - - .. ~
~i u ~ ~
~) i r C~i '~ C~i ~ C~
o ~a ~ a ~ a a ~ a a ~ ~i e ~ a ~ ~,-i u ~ ~ ~ ~ 'c~ u a .,i u ~ c~
O rl t.) ~4 V t~ ~ ~ri r_i _ U ~
~ O ~ U
Vl~ri O CJ U~ O C~ O C) ~rl O t,)~
c o ~3 i ' ~3 a ' e 8 ~ ~ a ~ ~ -~ u~ u r~ -" ~ - -. _ . . _ . . ~
a I a ~ a N U ri ~ rl O ~ ~ O
r O ~ ~ ~ ~ ~ ~ O
, i ~ ~i ta ~ t~ ta - - -- - ~--- - - - - - -- -- -- -., 0~ o~
- - -- ~---- -- --,' ~ .~ ' , ', , . ; , ' ; . ' , ', ' , i _ _ ~5~7~7 u~¦ ~ d _ c) " d .~ , ~, ~q ,Q
~ - - d d d ~ ~ , d :i IC~ I N I N I N I N ~ ~ I N
: . - ~ ~ .. . ~.. --_ S~ ~
J
~', t~ td ~ ~ ~ ~ 'O rl ~ ~ ~
.: ~ ~ ~ t~ ~ ^ ~-rl ): Cl~-~-l Qt O
~ O ~ ~ ~ O ~d td ~ ~
S ~ ~ . a~ o : a o ~ d ~ ~ O rl 1 0 rl ~ Sd~ ~d O g ~ U r~ ) ~ ~ rl ~ O ~-1 ~ O ~
,~ t~ ~ ~ ~ ~
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d P U~ O ~ 0 C.) r~
~-1 ~ ~ O I I O I T--( O
a ~ ~ ~ ~ ~ ~ ~ o~
;i o o :~ I a~ e ~, ~ t~ t~ ~ ~ U~
.j ~ to c~ ~ ~n o '~' ~ ~ ~ ~ ~ C`l i` . __ . . ~
I t~
~ I I O r3 ~1 ;' ' I ~ ,~
,~ o-,l o a~ , ~i g rl ~ ~ ~ I
1, ~
~ t) a~ ~ o ~ o u~
. . FNd, ~ 1~ ~ N N ~ N
L ~:J
E~ ~
J O O d O ~ O t~i O t~l O tl~
C~ :~ ~ ) d d d C) rl N rl N rl C ) rl C.l ;i C) N ~3 ~ d ~ d ~ rl ~ rl ~ rl ~d O ~ I ,~ I ,D rl O r~ O rl O
.~_1 51 d ~ O ~ O ~ ~ ~ ~
a ~ ~ ~ ~ ~ ~ ~ , a~ I a~ I Od ~-~ ~~-r~ ~
l ~
. . : -- ---- ----- - ... . _ . ~ r~ O ~ C~l ~-.. . . . .
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..
1~5~7 ,, . __ . _ .: ,' :' ~1 . ~1 5 . U~
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. . .
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~: ~ t~ h~
O ~4 O t~
Q t:l ,1 S~ .
O O h O ~ ~ 1 rO a~
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Example 25 A neutral solution (sodium salt) of 40.2 parts of 4,4l-diaminodiphenylurea-2,2'-disulphonic acid is introduced ,.
into a fine ice-cold suspension of 37 parts of cyanuric ; chlor;de, and stirring is maintained at a temperature of 5 until no further amino group is detectable, with ~he pH-value being kept between 5 and 6 by the dropwise addition of a diluted sodium hydroxide solution. There is then added a solution of 42 parts of sodium salt of 1,3-diaminobenzene-4-sulphonic acid, and the mixture is allowed to react for 1 to 2 hours at 20 to 30. The reaction mixture is subsequently neutralised with a sodium hydroxide solution;
it is acidified with 60 parts of 30% hydrochloric acid, and diazotised with a solution of 14 parts of sodium nitrite at 20. The tetrazo compound is combined with ~he neutral lS solution of 120 parts of the secondary condensation product from cyanuric chloride, 1,8-aminonaphthol-3,6-disulphonic acid and orthanilic acid. Coupling is completed by the addition o 40 parts of bicarbonate. The dyestuff obtained is salted out, filtered off and dried. It dyes cellulose fibres in ~0 very fast red shadesO
I~ there is used in this Example, instead of 1,3-diamlno-benzene-4-sulphonic acid, the same amount of 1,4-diamino-: :l 7~
.
.,;`, .
;~ benzene-2-sulphonic acid to produce the diazo component, then a dyestuff is obtained which dyes cellulose in ~- intensely bluish-red shades.
If instead of diamino-diphenylureadiswlphonic acid there is used the corresponding amount of 1,4-diamino-benzene-2,5-disulphonic acid, with the procedure otherwise ; being as described in the Example, then a similar dyestuff is obtained.
xample 26 .
The tetrazo compo~md obtained by the procedure of , 10 Example 25 is combined with a neutral solution of 94 parts of the condensation product from cyanuric chloride and 1,&-aminonaphthol-3,6-disulphonic acid at 5 to 10. The pH-value is raised to 7 by the careful dropwise addition of a diluted sodium hydroxide solution. After completion of coupling, a solution of 2-carboxyaniline-4-sulphonic ' acid is added, and condensation is performed at 30 to 40 , at a pH-value of 6 to 7. The tetrareactive dyestuff is then isolated by concentration of the solution by evapor-ation. The dyestuff obtained dyes cotton in red shades.
.
', .
"
:
~ L~5'~7~7 Example_27 ^ The tetrazo compound obtained by the procedure given in Example 25 is added to an ice-cold solution prepared by dissolving 64 parts of 1,~-aminonaphthol-3,6-di-` sulphonic acid and 60 parts of sodium carbonate in water.
~fter completion of coupling, the reaction mixture is neutralised with hydrochloric acid, and an addi~ion is then made at 5 of a solution of 37 parts of cyanuric chloride in 200 parts of acetone. The reaction mixture is slowly neutralised with a diluted sodium hydroxide solution. After completion of the reaction, there is added a solution of 34.6 parts of metanilic acid; the temperature is raised to 40, and the mixture is allowed to react for 2 hours at this temperature, with the pH-value being maintained at between 6 and 7 by the dropwise addition of a sodium hydroxide solution. The dyestuff is subsequently salted out, filtered off and dried. It dyes cotton in red shades.
.
To a neutral aqueous solution of 24.1 parts of the disodium salt of l-(4'-aminobenzoylamino)-8-naphthol-3,6-disulphonic acid there are added dropwise at 0 S parts by volume of 2,4?6-trifluoro-1,3,5~triazine, with a pH value ." ,...... . .. .. .
~ Z~7 ., .
-I of 5 to 6 being maintained by the simultaneous addition of diluted sodium hydroxide solution. After completion of condensation, there are added 9.75 parts of sodium -~ sulphanilate; the reaction mixture is allowed to warm up to room temperature and the hydrogen fluoride released during condensation is neutralised by the dropwise addition of diluted sodium hydroxide solution. To the solution of the coupling component thus obtained there is - then added a diazo suspension obtained according to the procedure of Example 1 by condensation of 9.4 parts of 1,3~diaminobenzene-6-sulphonic acid and 9.25 parts of cyanuric chloride and subsequent diazotisation, and the pH-value is held during coupling at between 6 and 7.5 by the addition of sodium carbonate After coupling is completed th~re is added a solu~ion of 3.05 parts of 2,4-diamino-toluene in warm water, and condensation is performed at 35 ; at a pH-value of 6 to 7. A~ter completion of condensation, there are added 2 parts of a mixture of mono- and disodium phosphate in the molar ratio of 1 : 1.2, and the water is evaporated off in vacuo. The dyestuff obtained dissolves ; in water to give a red colour, and dyes cotton in fast red shades.
Similar red dyestuffs are obtained if there are used, :',1 5~777 instead of 2,4-diaminotoluene, equivalent amounts of ,~ 1,6-diaminohexane, 2,6-diaminonaphthalene-4,8-disulphonic -acid or 1~3-diaminobenzene-4-carboxylic acid.
Example 29 By the procedure given in Example 25 there are condensed 40.2 parts of 4,4'-diarninodiphenylurea-2,2'-disulphonic acid with 37 parts of cyanuric chloride and subsequently with 42 parts of the disodium salt of 1,3-diaminobenzene-4-sulphonic acid, and diazotisation is then performed. The tetrazo compound is combined with a neutral suspension of n llo parts of the secondary condensation product from 2-aminobenzene-l-sulphonic acid, 2,4,6-trifluoro-1,3,5-triazine and 6-amino-1-naphthol-3-sulphonic acid (disodium salt), and coupling is completed by the addition of sodium bicarbonate li at pH 7. The resulting dyestuff is salted out, filtered off and dried. I~ dyes cellulose fibres in fast orange shades.
If there are used, instead of 37 parts of cyanuric chloride, 28 parts of 2,4,6-trifluoro-1,3,5-triazine, then ~ . there is obtained the corresponding dyestuff containing i four reactive fluorine atoms, which dyestuff has similar dyeing properties.
. .. , . . . , , , :, . . ... . . . .. . . .
~L~5~7~ ~
.1 Dyein~, Instruction I
2 parts of the ~etrareactive disazo dyestuff obtained according to Example 1 are dissolved, with the addition of 0.5 part of the sodi~ salt of m-nitrobenzenesulphonic acid, in 100 parts of water. The solution obtained is used to impregnate a cotton fabric in such a manner that `' its weight increases by 75%; the impregnated fabric is subsequently dried.
The fabric is afterwards impregnated with a solution at 20 containing per litre 5 grams of sodium hydroxide and 300 grams of sodium chloride, and is subsequently squeezed out to 75% increase in weight; the dyeing is ~hen steamed for one minute at 100 to 101, rinsed, soaped for quarter of an hour in a boiling 0.3% solution of an ion-free detergent, rinsed and dried. There is obtained a red dyeing having fastness to washing and to light.
Dyein~ Instruction II
2 parts of the tetrareactive disazo dyestuff obtained according to Example 1 are dissolved in 100 parts of water.
The solution is added to 3900 parts of cold water; 80 parts of sodium chloride are added, and there are then ` ~ ~5~7';'~
., introduced into this dyeing bath 100 parts of a cotton fabric. The temperature is raised in 45 minutes to 90, with additions being made after 30 minutes of 40 parts of trisodium phosphate and of a further 80 parts of .~
` 5 sodium chloride. The temperature is maintained at 90 for 30 minutes; the dyeing is subsequently rinsed and then soaped fox 15 minutes in a boiling 0.3% solution of an ion-free detergent. There is obtained a red dyeing having fastness to washing and to light.
Printin~ Instruction 2 parts of the tetrareactive disazo dyestuff obtained according to Example 1 are sprinkled, with rapid stirring, ;~ into 100 parts of a stock thickening containing 45 parts of a 5% sodium alginate thickening, 32 parts of water, 20 , 15 parts of urea, 1 part of the sodium salt of m-nitrobenzene-sulphonic acid as well as 2 parts of sodium bicarbonate.
With the printing paste thus obtained there is printed a cotton fabric on a roller printing machine, and the resulting printed material is steamed for 8 minutes at 100 in saturated steam. The printed fabric is then thoroughly rinsed in cold and hot water, with the constituents not ¦ chemical fixed being very easily removable from the fibres, and the rinsed fabric is subsequently dried.
, .
4~4'-diaminostilbene-2,2'-disulphonic acid, 4,4'-diaminodiphenylethane-2,2'-disulphonic acid, piperazine.
The new tetrareactive disazo dyestuffs of the formula (1) can be isolated and processed into suitable dry dyestuff preparations. Isolation is effected preferably at the lowest poss;ble temperature by salting out and filtration. The filtered dyestuffs can be dried optionally after the addition of diluents and/or buffer agents~
e.g. after the addition of a mixture of equal parts of mono- and disodium phosphate; drying is pre~erably performed at not too high a temperature and under reduced pressuraO By spray drying of the whole of the produced mixture it is possible in certain cases to obtain the dry preparations according to the invention direct, i.e.
without intermediate isolation of the dyestuffs.
; The dyestuffs are suitable for the dyeing and printing of the widest variety of materials, such as silk~ leather, ', .
`' ' " ' . ' ' . ~ . . ', " ' , . i ' ' , ' ' , . . ' ', .' " ': ' .
5~7"~
,:.
wool, superpolyamide fibres and superpolyurethanes, ,, .
especially, however, cellulose-containing materials of fibrous structure, such as linen, cellulose, regenera~ed cellulose and, in particular, cotton. They are especially suitable for dyeing by the exhaust process from a long liquor, from an aqueous alkaline bath having if required a high salt content; and by the pad-dyeing process, wherein the material is impregnated with aqueous, optionally salt-containing dyestuff solutions, and, after an alkali treatment or in the presence of alkali, the dyestuffs are fixed, if necessary by the action of heat.
The dyestuffs are suitable also for printing, especially on cotton; also for printing of nitrogen-containing fibres, e.g. of wool, silk or wool-containing lS mixed fabrics. They are characterised, in particular, by an enhanced reactivity and by a good affinity, and hence by a high degree of fixing. They have the advantage also that unfixed constituents can be readily washed out.
The dyeings and printings obtained have a high depth of coLour and have good fastness to light as well as very good fastness to wet processing, such as good fastness to washing.
~or the purpose of improving fastness to wet processing, .
~ S'~ 7 it is recommended that the dyeings and printings be : subjected to a thorough rinsing with cold water and hot water, optionally with the addition of an agent having a dispersing action and promoting the diffusion of the unfixed constituents.
Except where otherwise stated in the following Examples, 'parts' denote parts by weight, percentages are given as per cent by weight, and temperature values . are expressed in degrees Centigrade. Between parts by .
weight and parts by volume there exists the same relationship as between gram and cubic cen~imetre.
.
l` :
Example 1 18.8 parts of 1,3~diaminobenzene-6-sulphonic acid are dissolved in 200 parts of water, with the addition of sodium carbonate, at pH 6 to 7. The solution is added to an ice-cold aqueous suspension of 18.5 parts of - S cyanuric chloride; and the mixture is neutralised, with ice-cooling in the course of 30 minutes, with a diluted sodium hydroxide solution. After completion of condensation, 30 parts of concentrated hydrochloric acid are added and diazotisation is performed with a solution of 6.9 parts of sodium nitrite. The excess of nitrous acid is decomposed with sulphamic acid, and the diazo compound is added to a neutral aqueous solution of 60 parts of the secondary condensation product from cyanuric chloride, 1,8-amino-` naphthol-3,6-disulphonic acid and 1-aminobenzene-3-sulphonic acid, ~ith the pH-value being maintained between 6 and 7.5 by the addition of sodium carbonate. After coupling is completed, there is added a solution of 5.4 parts of 1,4-diaminobenzene; the temperature is gradually raised to 35 and condensation is performed at this temperature, whilst the pH-value of the soluti~n is kept between 6 and 7 with a diluted sodium hydroxide solution. After completion of the reaction, the dyestuff solution is concentrated in vacuo .. , . ~ ~ i ~a!S;~7'~7 to dryness. The tetrareactive disazo dyestuff obtained dyes cellulose fibres in the exhaust process, in the presence of electrolyte and alkali, in red shades.
~` If there is used in this Example~ instead of S cyanuric chloride, a corresponding amount of cyanuric bromide, then there is obtained a tetrareactive disazo dyestuff having similar properties.
The following Table contains a number of further examples that can be obtained by the procedure given in Example 1.
.
;
.' a) n) ~ ~
r........... ~ ~ ~
,/ ~ ~ ' 0~' 0 0 ~ ~ __ ._ _ _ .. , ...... _ ___ .__ . _._.__ ' '::
O O O O ~: ^ C~
,,~ ~ rl ~rl a.) .~ ~ 0 ~ r ~
~rl I N I N I N i N ~
, ~ ~ ~ rl .. ... . _ ~ . .. _ __ _ _ . ._ ,., ~ , a) ~
. ~ I ~rl ~., ~-rl ~ ~ .,.
.' t~ S~ ~ 1 0 u ~ O t~
~, ~ ~0~:: ~0~ ~0~
'i O ~ ~ ,1 ~ ,1 ~ ~ rl ~n i, n u ~ tJ ~ L) c~ rl ~ ~rl :' O C~ ~ C~
.~ ~ rl ~ ~il U t~ ~I t.) _O t) U') ~C ~ ~ g ~ O O ~
~i ~ U~ ~ J~ O~ 0~1 1 0 i :j .,1 ~ ~,) rl ~ ~1 ~rl,5: ~1 0 ,~ a .~ ,~ a) ~ ~1 e .~ ~ ~ e ! .
o o ~ ~ o~
~ o ~ ~
i ~ ~ Ei ~ ~ O N 1~ ~3 td . ... _ _ ... __ ... ___ . ....
i! ~ . f ~j ~ ~D
A ~
C,t P~ .~ ~ .
O ~
I . ~ ~ O ~ ~ ~
... _ ~. ... , .. _ . _ . .
,' ~
_ .. - 18 - ~ ~- -~--. . .
i . ' : , ' , ' , , : !;' ! ~ `
.` . :, ` , .`
_ .. _ . _ . .. .. . _ ~_ , s~
- - ,~
U~
.~ .. __ ._ ._ . ... , ~ ~ _ o o o o ~i o ~ b ~1 ~ ri ~ ~ri ~ I ri 1~3 ri ~: ri ~ ri ~ ri ~ C~ ri ~ rl ~ _ rl I N I N I N I N t:~ I N ~ I N
n ~ ~ o ~ ~
^ q~ rlrl ~ a) .. . - . - - .. ~
~i u ~ ~
~) i r C~i '~ C~i ~ C~
o ~a ~ a ~ a a ~ a a ~ ~i e ~ a ~ ~,-i u ~ ~ ~ ~ 'c~ u a .,i u ~ c~
O rl t.) ~4 V t~ ~ ~ri r_i _ U ~
~ O ~ U
Vl~ri O CJ U~ O C~ O C) ~rl O t,)~
c o ~3 i ' ~3 a ' e 8 ~ ~ a ~ ~ -~ u~ u r~ -" ~ - -. _ . . _ . . ~
a I a ~ a N U ri ~ rl O ~ ~ O
r O ~ ~ ~ ~ ~ ~ O
, i ~ ~i ta ~ t~ ta - - -- - ~--- - - - - - -- -- -- -., 0~ o~
- - -- ~---- -- --,' ~ .~ ' , ', , . ; , ' ; . ' , ', ' , i _ _ ~5~7~7 u~¦ ~ d _ c) " d .~ , ~, ~q ,Q
~ - - d d d ~ ~ , d :i IC~ I N I N I N I N ~ ~ I N
: . - ~ ~ .. . ~.. --_ S~ ~
J
~', t~ td ~ ~ ~ ~ 'O rl ~ ~ ~
.: ~ ~ ~ t~ ~ ^ ~-rl ): Cl~-~-l Qt O
~ O ~ ~ ~ O ~d td ~ ~
S ~ ~ . a~ o : a o ~ d ~ ~ O rl 1 0 rl ~ Sd~ ~d O g ~ U r~ ) ~ ~ rl ~ O ~-1 ~ O ~
,~ t~ ~ ~ ~ ~
~ ~ ~ ~ ~. u I ~ ~r, I ~ ~
d P U~ O ~ 0 C.) r~
~-1 ~ ~ O I I O I T--( O
a ~ ~ ~ ~ ~ ~ ~ o~
;i o o :~ I a~ e ~, ~ t~ t~ ~ ~ U~
.j ~ to c~ ~ ~n o '~' ~ ~ ~ ~ ~ C`l i` . __ . . ~
I t~
~ I I O r3 ~1 ;' ' I ~ ,~
,~ o-,l o a~ , ~i g rl ~ ~ ~ I
1, ~
~ t) a~ ~ o ~ o u~
. . FNd, ~ 1~ ~ N N ~ N
L ~:J
E~ ~
J O O d O ~ O t~i O t~l O tl~
C~ :~ ~ ) d d d C) rl N rl N rl C ) rl C.l ;i C) N ~3 ~ d ~ d ~ rl ~ rl ~ rl ~d O ~ I ,~ I ,D rl O r~ O rl O
.~_1 51 d ~ O ~ O ~ ~ ~ ~
a ~ ~ ~ ~ ~ ~ ~ , a~ I a~ I Od ~-~ ~~-r~ ~
l ~
. . : -- ---- ----- - ... . _ . ~ r~ O ~ C~l ~-.. . . . .
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1~5~7 ,, . __ . _ .: ,' :' ~1 . ~1 5 . U~
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. . .
'd O ~ C~ ,~
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.
, , ~ , . . :.,, . . - ., ; , . :, ~, ', :
;.~ ' . , ~ ' . ,, ~ , , ' ; . . .
Example 25 A neutral solution (sodium salt) of 40.2 parts of 4,4l-diaminodiphenylurea-2,2'-disulphonic acid is introduced ,.
into a fine ice-cold suspension of 37 parts of cyanuric ; chlor;de, and stirring is maintained at a temperature of 5 until no further amino group is detectable, with ~he pH-value being kept between 5 and 6 by the dropwise addition of a diluted sodium hydroxide solution. There is then added a solution of 42 parts of sodium salt of 1,3-diaminobenzene-4-sulphonic acid, and the mixture is allowed to react for 1 to 2 hours at 20 to 30. The reaction mixture is subsequently neutralised with a sodium hydroxide solution;
it is acidified with 60 parts of 30% hydrochloric acid, and diazotised with a solution of 14 parts of sodium nitrite at 20. The tetrazo compound is combined with ~he neutral lS solution of 120 parts of the secondary condensation product from cyanuric chloride, 1,8-aminonaphthol-3,6-disulphonic acid and orthanilic acid. Coupling is completed by the addition o 40 parts of bicarbonate. The dyestuff obtained is salted out, filtered off and dried. It dyes cellulose fibres in ~0 very fast red shadesO
I~ there is used in this Example, instead of 1,3-diamlno-benzene-4-sulphonic acid, the same amount of 1,4-diamino-: :l 7~
.
.,;`, .
;~ benzene-2-sulphonic acid to produce the diazo component, then a dyestuff is obtained which dyes cellulose in ~- intensely bluish-red shades.
If instead of diamino-diphenylureadiswlphonic acid there is used the corresponding amount of 1,4-diamino-benzene-2,5-disulphonic acid, with the procedure otherwise ; being as described in the Example, then a similar dyestuff is obtained.
xample 26 .
The tetrazo compo~md obtained by the procedure of , 10 Example 25 is combined with a neutral solution of 94 parts of the condensation product from cyanuric chloride and 1,&-aminonaphthol-3,6-disulphonic acid at 5 to 10. The pH-value is raised to 7 by the careful dropwise addition of a diluted sodium hydroxide solution. After completion of coupling, a solution of 2-carboxyaniline-4-sulphonic ' acid is added, and condensation is performed at 30 to 40 , at a pH-value of 6 to 7. The tetrareactive dyestuff is then isolated by concentration of the solution by evapor-ation. The dyestuff obtained dyes cotton in red shades.
.
', .
"
:
~ L~5'~7~7 Example_27 ^ The tetrazo compound obtained by the procedure given in Example 25 is added to an ice-cold solution prepared by dissolving 64 parts of 1,~-aminonaphthol-3,6-di-` sulphonic acid and 60 parts of sodium carbonate in water.
~fter completion of coupling, the reaction mixture is neutralised with hydrochloric acid, and an addi~ion is then made at 5 of a solution of 37 parts of cyanuric chloride in 200 parts of acetone. The reaction mixture is slowly neutralised with a diluted sodium hydroxide solution. After completion of the reaction, there is added a solution of 34.6 parts of metanilic acid; the temperature is raised to 40, and the mixture is allowed to react for 2 hours at this temperature, with the pH-value being maintained at between 6 and 7 by the dropwise addition of a sodium hydroxide solution. The dyestuff is subsequently salted out, filtered off and dried. It dyes cotton in red shades.
.
To a neutral aqueous solution of 24.1 parts of the disodium salt of l-(4'-aminobenzoylamino)-8-naphthol-3,6-disulphonic acid there are added dropwise at 0 S parts by volume of 2,4?6-trifluoro-1,3,5~triazine, with a pH value ." ,...... . .. .. .
~ Z~7 ., .
-I of 5 to 6 being maintained by the simultaneous addition of diluted sodium hydroxide solution. After completion of condensation, there are added 9.75 parts of sodium -~ sulphanilate; the reaction mixture is allowed to warm up to room temperature and the hydrogen fluoride released during condensation is neutralised by the dropwise addition of diluted sodium hydroxide solution. To the solution of the coupling component thus obtained there is - then added a diazo suspension obtained according to the procedure of Example 1 by condensation of 9.4 parts of 1,3~diaminobenzene-6-sulphonic acid and 9.25 parts of cyanuric chloride and subsequent diazotisation, and the pH-value is held during coupling at between 6 and 7.5 by the addition of sodium carbonate After coupling is completed th~re is added a solu~ion of 3.05 parts of 2,4-diamino-toluene in warm water, and condensation is performed at 35 ; at a pH-value of 6 to 7. A~ter completion of condensation, there are added 2 parts of a mixture of mono- and disodium phosphate in the molar ratio of 1 : 1.2, and the water is evaporated off in vacuo. The dyestuff obtained dissolves ; in water to give a red colour, and dyes cotton in fast red shades.
Similar red dyestuffs are obtained if there are used, :',1 5~777 instead of 2,4-diaminotoluene, equivalent amounts of ,~ 1,6-diaminohexane, 2,6-diaminonaphthalene-4,8-disulphonic -acid or 1~3-diaminobenzene-4-carboxylic acid.
Example 29 By the procedure given in Example 25 there are condensed 40.2 parts of 4,4'-diarninodiphenylurea-2,2'-disulphonic acid with 37 parts of cyanuric chloride and subsequently with 42 parts of the disodium salt of 1,3-diaminobenzene-4-sulphonic acid, and diazotisation is then performed. The tetrazo compound is combined with a neutral suspension of n llo parts of the secondary condensation product from 2-aminobenzene-l-sulphonic acid, 2,4,6-trifluoro-1,3,5-triazine and 6-amino-1-naphthol-3-sulphonic acid (disodium salt), and coupling is completed by the addition of sodium bicarbonate li at pH 7. The resulting dyestuff is salted out, filtered off and dried. I~ dyes cellulose fibres in fast orange shades.
If there are used, instead of 37 parts of cyanuric chloride, 28 parts of 2,4,6-trifluoro-1,3,5-triazine, then ~ . there is obtained the corresponding dyestuff containing i four reactive fluorine atoms, which dyestuff has similar dyeing properties.
. .. , . . . , , , :, . . ... . . . .. . . .
~L~5~7~ ~
.1 Dyein~, Instruction I
2 parts of the ~etrareactive disazo dyestuff obtained according to Example 1 are dissolved, with the addition of 0.5 part of the sodi~ salt of m-nitrobenzenesulphonic acid, in 100 parts of water. The solution obtained is used to impregnate a cotton fabric in such a manner that `' its weight increases by 75%; the impregnated fabric is subsequently dried.
The fabric is afterwards impregnated with a solution at 20 containing per litre 5 grams of sodium hydroxide and 300 grams of sodium chloride, and is subsequently squeezed out to 75% increase in weight; the dyeing is ~hen steamed for one minute at 100 to 101, rinsed, soaped for quarter of an hour in a boiling 0.3% solution of an ion-free detergent, rinsed and dried. There is obtained a red dyeing having fastness to washing and to light.
Dyein~ Instruction II
2 parts of the tetrareactive disazo dyestuff obtained according to Example 1 are dissolved in 100 parts of water.
The solution is added to 3900 parts of cold water; 80 parts of sodium chloride are added, and there are then ` ~ ~5~7';'~
., introduced into this dyeing bath 100 parts of a cotton fabric. The temperature is raised in 45 minutes to 90, with additions being made after 30 minutes of 40 parts of trisodium phosphate and of a further 80 parts of .~
` 5 sodium chloride. The temperature is maintained at 90 for 30 minutes; the dyeing is subsequently rinsed and then soaped fox 15 minutes in a boiling 0.3% solution of an ion-free detergent. There is obtained a red dyeing having fastness to washing and to light.
Printin~ Instruction 2 parts of the tetrareactive disazo dyestuff obtained according to Example 1 are sprinkled, with rapid stirring, ;~ into 100 parts of a stock thickening containing 45 parts of a 5% sodium alginate thickening, 32 parts of water, 20 , 15 parts of urea, 1 part of the sodium salt of m-nitrobenzene-sulphonic acid as well as 2 parts of sodium bicarbonate.
With the printing paste thus obtained there is printed a cotton fabric on a roller printing machine, and the resulting printed material is steamed for 8 minutes at 100 in saturated steam. The printed fabric is then thoroughly rinsed in cold and hot water, with the constituents not ¦ chemical fixed being very easily removable from the fibres, and the rinsed fabric is subsequently dried.
, .
Claims (17)
1. Tetrareactive disazo dyestuffs of the formula (1) wherein D represents a benzene radical containing at least one sulpho group; K represents a radical of l-amino (or aminobenzoylamino)-8-naphthol-3,6-disulphonic acid, of l-amino(or aminobenzoylamino)-8 naphthol-4,6 disulphonic acid, of 2-amino(or aminobenzoylamino)-5-naphthol-7-sulphonic acid, of 2-amino(or aminobenzoylamino)-8-naphthol-6-sulphonic acid, of 2-amino(or aminobenzoylamino)-5-naphthol-1,7-disulphonic acid, or of 2-amino(or amino-benzoylamino)-8-naphthol-3,6-disulphonic acid; B represents an aliphatic or aromatic radical; R1, R2 and R3 each independently represent hydrogen or alkyl having 1 to 6 carbon atoms; X represents chlorine, bromine or fluorine;
and Y represents hydrogen, low-molecular alkyl or alkoxy, acetylamino, halogen, carboxy or sulpho.
and Y represents hydrogen, low-molecular alkyl or alkoxy, acetylamino, halogen, carboxy or sulpho.
2. Tetrareactive disazo dyestuffs according to Claim 1, wherein D represents the radical of 1,3-diaminobenzene-4-sulphonic acid; K represents the radical of 1-amino-8-naphthol-3,6-disulphonic acid or the radical of 2-amino-5-naphthol-7-sulphonic acid; B represents an aromatic radical; R1, R2 and R3 represent hydrogen; X represents chlorine; and Y represents hydrogen, sulpho, chloro, methyl or carboxy, with the sulpho group, or Y if Y is a substituent other than the sulpho group, in the terminal benzene radical being in the ortho position with respect to the .
3. Tetrareactive disazo dyestuff according to Claim 2 of the formula .
4. Tetrareactive disazo dyestuf according to Claim 2 of the formula
5. Process for the manufacture of tetrareactive disazo dyestuffs according to Claim 1, wherein diazo components of the formula H2N-D-NH2 (2), coupling components of the formula K-NH2 (3), trihalogeno-s-triazines of the formula (4), aminobenzenesulphonic acids of the formula (5) and aliphatic or aromatic diamines of the formula (6) are combined by means of coupling and condensation to give tetrareactive disazo dyestuffs of the formula (1).
6. Process according to Claim 5, wherein a diazo component of the formula (2) is condensed with a trihalogeno-s-triazine of the formula (4); the condensation product is diazotised and coupled to the secondary condensation product from a trihalogeno-s-triazine of the formula (4), a coupling component of the formula (3) and an aminobenzene-sulphonic acid of the formula (5); and the monoazo compound obtained is condensed in the final stage with an aliphatic or aromatic diamine of the formula (6) in the molar ratio of 2:1 to give a tetrareactive disazo dyestuff of the formula (1).
7. Process according to Claim 5, wherein 2 moles of a trihalogeno-s-triazine of the formula (4) are condensed with 2 moles of a diazo component of the formula (2) and with 1 mole of an aliphatic or aromatic diamine of the formula (6); the condensation product is diazotised and the product obtained is coupled to the condensation product from a trihalogeno-s-triazine of the formula (4) and a coupling component of the formula (3); and the resulting disazo compound is condensed with 2 moles of an amino-benzenesulphonic acid of the formula (5) to a tetra-reactive disazo dyestuff of the formula (1).
8. Process according to Claim 5, wherein 2 moles of a trihalogeno-s-triazine of the formula (4) are condensed with 2 moles of a diazo component of the formula (2) and with 1 mole of an aliphatic or aromatic diamine of the formula (6); the condensation product is tetrazotised and the product obtained is coupled to the secondary condensation product from a trihalogeno-s-triazine of the formula (4), a coupling component of the formula (3) and an aminobenzene-sulphonic acid of the formula (5), in the molar ratio of 1:2, to give a tetrareactive disazo dyestuff of the formula (1).
9. Process according to Claîm 5, wherein 2 moles of a trihalogeno-s-triazine of the formula (4) are condensed with 1 mole of an aliphatic or aromatic diamine of the formula (6); the resulting condensation product is condensed with 2 moles of a diazo component of the formula (2); the formed disecondary condensation product is tetrazotised and the product obtained is coupled to 2 moles of a coupling component of the formula (3); the disazo compound obtained therefrom is condensed with 2 moles of a trihalogeno-s-triazine of the formula (4); and the condensation product is condensed with 2 moles of an aminobenzenesulphonic acid of the formula (5) to a tetra-reactive disazo dyestuff of the formula (1).
10. Process according to Claim 5, wherein as starting materials there are used: as diazo component of the formula (2) 1,3-diaminobenzene-4-sulphonic acid; as coupling component of the formula (3) l-amino-8-naphthol-3,6-disulphonic acid or 2-amino-5-naphthol-7-sulphonic acid, a trihalogeno-s-triazine of the formula (4) wherein X is chlorine, an aminobenzenesulphonic acid of the formula (5) wherein R3 represents hydrogen, and Y represents hydrogen, sulpho, chlorine, methyl or carboxy, with the sulpho group, or Y if Y is a substituent other than the sulpho group, being in the ortho position with respect to the HN-group, ¦
and an aromatic diamine of the formula (6) wherein R1 and R2 represent hydrogen.
and an aromatic diamine of the formula (6) wherein R1 and R2 represent hydrogen.
11. Process according to Claim 10, wherein 1,3-diamino-benzene-4-sulphonic acid is condensed with cyanuric chloride to l-(dichloro-s-triazinylamino)-3-aminobenzene-4-sulphonic acid; the condensation product is diazotised and the product obtained is coupled to the secondary condensation product from cyanuric chloride, l-amino-8-naphthol-3,6-disulphonic acid and an aminobenzenesulphonic acid of the formula (5) wherein R3 represents hydrogen, and Y represents hydrogen or a sulpho group, with the sulpho group or Y being in the ortho-position with respect to the HN-group; and the resulting azo compound of the ¦
formula is condensed with an aromatic diamine of the formula (6), wherein R1 and R2 are hydrogen, in the molar ratio of 2:1.
formula is condensed with an aromatic diamine of the formula (6), wherein R1 and R2 are hydrogen, in the molar ratio of 2:1.
12. Process according to Claim 10, wherein 1,3-diamino-benzene-4-sulphonic acid is condensed with cyanuric chloride to 1-(dichloro-s-triazinylamino)-3-aminobenzene-4-sulphonic acid; this is diazotised and the product obtained is coupled to the secondary condensation product from cyanuric chloride, 2-amino-5-naphthol-7-sulphonic acid and an aminobenzenesulphonic acid of the formula (5) wherein R3 represents hydrogen, and Y represents hydrogen or a sulpho group, with the sulpho group or Y being in the ortho-position with respect to the ; and the resulting azo compound of the formula is condensed with an aromatic diamine of the formula (6), wherein R1 and R2 are hydrogen, in the molar ratio of 2:1.
13. Process according to Claim 11, wherein the starting materials used are 1,3-diaminobenzene-4-sulphonic acid, cyanuric chloride, 1-amino-8-naphthol-3,6-disulphonic acid, orthanilic acid and p-phenylenediamine.
14. Process according to Claim 12, wherein the starting materials used are 1-3-diaminobenzene-4-sulphonic acid, cyanuric chloride, 2-amino-5-naphthol-7-sulphonic acid, aniline-2,5-disulphonic acid and p-phenylene-diamine.
15. Process for dyeing and printing with the use of the fibre-reactive disazo dyestuffs according to Claim 1.
16. Process according to Claim 15 for the dyeing of cellulose fibres.
17. The dyed or printed material obtained according to the Claim 15 or 16.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH47175A CH606347A5 (en) | 1975-01-15 | 1975-01-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1052777A true CA1052777A (en) | 1979-04-17 |
Family
ID=4187756
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA243,439A Expired CA1052777A (en) | 1975-01-15 | 1976-01-13 | Tetrareactive disazo dyestuffs, their manufacture and their use |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US4066389A (en) |
| JP (1) | JPS5196825A (en) |
| AR (1) | AR207803A1 (en) |
| BE (1) | BE837547A (en) |
| BR (1) | BR7600208A (en) |
| CA (1) | CA1052777A (en) |
| CH (1) | CH606347A5 (en) |
| CS (1) | CS190510B2 (en) |
| DE (1) | DE2601043A1 (en) |
| ES (1) | ES444486A1 (en) |
| FR (1) | FR2297899A1 (en) |
| GB (1) | GB1519874A (en) |
| MX (1) | MX143639A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH626650A5 (en) * | 1974-12-18 | 1981-11-30 | Ciba Geigy Ag | |
| IT1121683B (en) * | 1975-11-06 | 1986-04-10 | Ciba Geigy Ag | REACTIVE DYES FOR FIBER DE PROCEDURE FOR THEIR PRODUCTION AND APPLICATION |
| GB1577498A (en) * | 1977-06-29 | 1980-10-22 | Bayer Ag | Fluorotriazinyl-azo reactive dyestuffs |
| DE2901547A1 (en) * | 1979-01-16 | 1980-07-24 | Bayer Ag | REACTIVE DYES |
| EP0041919B1 (en) * | 1980-05-30 | 1985-08-21 | Ciba-Geigy Ag | Process for the preparation of amino-fluor-s-triazine dyestuffs |
| DE3476218D1 (en) * | 1983-02-24 | 1989-02-23 | Ciba Geigy Ag | Reactive dyes, their preparation and their use |
| US4808193A (en) * | 1985-12-28 | 1989-02-28 | Hoechst Aktiengesellschaft | Process for dyeing hydroxy-containing fiber material with water-soluble dis-azo reactive dye compound |
| DE3604858A1 (en) * | 1985-12-28 | 1987-07-02 | Hoechst Ag | WATER-SOLUBLE AZO COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS DYES |
| DE4021727A1 (en) * | 1990-07-07 | 1992-01-09 | Basf Ag | DOUBLE REACTIVE DYES WITH FOUR HALOGENTRIAZINE ANCHORS |
| EP0624629B1 (en) * | 1993-05-14 | 1999-03-24 | Ciba SC Holding AG | Fibre reactive dyes, their production and their use |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2768158A (en) * | 1953-03-30 | 1956-10-23 | Gen Aniline & Film Corp | Triazine dyes |
| US3117957A (en) * | 1958-12-19 | 1964-01-14 | Du Pont | Reactive polymeric dyes containing triazine |
| CH385375A (en) * | 1959-04-30 | 1964-12-15 | Geigy Ag J R | Process for the preparation of reactive dyes |
| US3261825A (en) * | 1963-03-11 | 1966-07-19 | Martin Marietta Corp | Azo-disulfide triazine dyestuffs |
| US3497494A (en) * | 1965-03-29 | 1970-02-24 | Ici Ltd | Reactive monoazo dyestuffs containing two triazine groups |
| US3639662A (en) * | 1968-03-07 | 1972-02-01 | Ici Ltd | Azo dyes of the triazine series |
| GB1243263A (en) * | 1968-03-08 | 1971-08-18 | Ici Ltd | New water-soluble reactive dyestuffs containing chlorotriazine residues |
| GB1259610A (en) * | 1968-12-31 | 1972-01-05 | ||
| GB1283771A (en) * | 1969-01-16 | 1972-08-02 | Ici Ltd | New reactive disazo dyestuffs |
| GB1272291A (en) * | 1969-01-16 | 1972-04-26 | Ici Ltd | New reactive metallised disazo dyestuffs |
| US3966705A (en) * | 1974-01-04 | 1976-06-29 | Ciba-Geigy Corporation | Disulfo naphthalene containing fiber-reactive tetrazo dyes |
-
1975
- 1975-01-15 CH CH47175A patent/CH606347A5/xx not_active IP Right Cessation
-
1976
- 1976-01-01 AR AR261916A patent/AR207803A1/en active
- 1976-01-09 US US05/647,846 patent/US4066389A/en not_active Expired - Lifetime
- 1976-01-13 MX MX163035A patent/MX143639A/en unknown
- 1976-01-13 DE DE19762601043 patent/DE2601043A1/en not_active Withdrawn
- 1976-01-13 CA CA243,439A patent/CA1052777A/en not_active Expired
- 1976-01-13 FR FR7600675A patent/FR2297899A1/en active Granted
- 1976-01-14 BE BE163495A patent/BE837547A/en unknown
- 1976-01-14 JP JP51002914A patent/JPS5196825A/en active Pending
- 1976-01-14 BR BR7600208A patent/BR7600208A/en unknown
- 1976-01-14 GB GB1387/76A patent/GB1519874A/en not_active Expired
- 1976-01-14 ES ES444486A patent/ES444486A1/en not_active Expired
- 1976-01-15 CS CS76272A patent/CS190510B2/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS190510B2 (en) | 1979-05-31 |
| ES444486A1 (en) | 1977-05-16 |
| BR7600208A (en) | 1976-08-31 |
| FR2297899A1 (en) | 1976-08-13 |
| DE2601043A1 (en) | 1976-07-22 |
| AR207803A1 (en) | 1976-10-29 |
| US4066389A (en) | 1978-01-03 |
| FR2297899B1 (en) | 1978-11-10 |
| CH606347A5 (en) | 1978-10-31 |
| BE837547A (en) | 1976-07-14 |
| GB1519874A (en) | 1978-08-02 |
| MX143639A (en) | 1981-06-17 |
| JPS5196825A (en) | 1976-08-25 |
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