CA1051423A - Dyestuffs for synthetic textile material - Google Patents
Dyestuffs for synthetic textile materialInfo
- Publication number
- CA1051423A CA1051423A CA196,542A CA196542A CA1051423A CA 1051423 A CA1051423 A CA 1051423A CA 196542 A CA196542 A CA 196542A CA 1051423 A CA1051423 A CA 1051423A
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- Canada
- Prior art keywords
- groups
- ethyl
- methyl
- alkyl
- formula
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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
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/443—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being alternatively specified
- C09B62/447—Azo dyes
- C09B62/45—Monoazo dyes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
NEW DYESTUFFS FOR SYNTHETIC TEXTILE MATERIAL
A B S T R A C T
of the Disclosure Dyestuffs of the formula
A B S T R A C T
of the Disclosure Dyestuffs of the formula
Description
~C~Sl~'~3 The invention r~lates to temporarily water-soluble disperse dyestuffs, to their preparation, and to their use for the dyeing and printing of hydrophobic synthetic organic material, especially polyester material.
Hydrophobic synthetic organic material, particularly polyester material, is dyed, as is known, with disperse dyestuffs such as are described, for example, in the Colour Index. These are coloured organic compounds which are free from water-solubilising groups, such as sulphonic acid groups or ammonium groups, and which are soluble in water to the extent only ~f traces, and which are absorbed via a phase dissolved as a molecular dispersion onto the material. For this purpose, the disperse dyestuffs have to be ground very finely before the actual dyeing process, and to be then stabilised in the aqueous dye bath by the addition of large amounts of dispersing agents. The dyestuff during dyeing is not in the form of a solution but in the form of a dispersion. This factor often creates difficulties in practice, for these dyestuff dispersions are frequently unstable, with the dyestuff crystallising out, and uneven dyeings being obtained as a resu~t. In high-temperature dyeing in particular, an inadequate dispersion stability becomes evident from filtration phenomena in the case of dense material being dyed on, for instance, cheese-dyeing and beam-dyeing machines. Furthermore, dispersing agents lOSl~Z3 in large dyeing plants can give rise to the folmation of foam; and, since dispersing agents are in most cases toxic, they lead to an appreciable con-tamination of the waste-water. Difficulties also arise in the dyeing of nixed fabrics, this being due to the fact that water-soluble dyestuffs fre-quently have poor compatibility with the dispersing agents in the disperse dyestuffs.
Dyestuffs have now been found which enable these difficulties to be overcome in a process in which hydrophobic synthetic organic material is dyed in a slightly acid, neutral or ~lkaline solution of temporarily water-soluble disperse dyestuffs according to the invention, which dyestuffs con-tain a group that can be split off under the dyeing conditions, the said group containing at least one water-solubilising group.
The invention thus provides a dyestuff of the formula ~ 2 ~
H03S-O-C2H4 t ~ 3 ~-S02-N- J
R
and alkali metal salts thereof, wherein B is (a) ~ I N.N ) ~ R
~2N R
wherein Rl represents hydrogen, lower a~kyl, lower alkoxy, cyano, lower-alkoxy-carbonyl, carbamoyl, lower-alkoxy-lower-alkoxy-carbonyl, phenoxy or phenyl;
R2 represents hydrogen, hydroxyethyl, cyanoethyl, benzyl, O~ OH / 2 2 CH2CH-cH20c6Hs~ -CH2-CHC6H5 ~ cyclohexyl, -CH \
Hydrophobic synthetic organic material, particularly polyester material, is dyed, as is known, with disperse dyestuffs such as are described, for example, in the Colour Index. These are coloured organic compounds which are free from water-solubilising groups, such as sulphonic acid groups or ammonium groups, and which are soluble in water to the extent only ~f traces, and which are absorbed via a phase dissolved as a molecular dispersion onto the material. For this purpose, the disperse dyestuffs have to be ground very finely before the actual dyeing process, and to be then stabilised in the aqueous dye bath by the addition of large amounts of dispersing agents. The dyestuff during dyeing is not in the form of a solution but in the form of a dispersion. This factor often creates difficulties in practice, for these dyestuff dispersions are frequently unstable, with the dyestuff crystallising out, and uneven dyeings being obtained as a resu~t. In high-temperature dyeing in particular, an inadequate dispersion stability becomes evident from filtration phenomena in the case of dense material being dyed on, for instance, cheese-dyeing and beam-dyeing machines. Furthermore, dispersing agents lOSl~Z3 in large dyeing plants can give rise to the folmation of foam; and, since dispersing agents are in most cases toxic, they lead to an appreciable con-tamination of the waste-water. Difficulties also arise in the dyeing of nixed fabrics, this being due to the fact that water-soluble dyestuffs fre-quently have poor compatibility with the dispersing agents in the disperse dyestuffs.
Dyestuffs have now been found which enable these difficulties to be overcome in a process in which hydrophobic synthetic organic material is dyed in a slightly acid, neutral or ~lkaline solution of temporarily water-soluble disperse dyestuffs according to the invention, which dyestuffs con-tain a group that can be split off under the dyeing conditions, the said group containing at least one water-solubilising group.
The invention thus provides a dyestuff of the formula ~ 2 ~
H03S-O-C2H4 t ~ 3 ~-S02-N- J
R
and alkali metal salts thereof, wherein B is (a) ~ I N.N ) ~ R
~2N R
wherein Rl represents hydrogen, lower a~kyl, lower alkoxy, cyano, lower-alkoxy-carbonyl, carbamoyl, lower-alkoxy-lower-alkoxy-carbonyl, phenoxy or phenyl;
R2 represents hydrogen, hydroxyethyl, cyanoethyl, benzyl, O~ OH / 2 2 CH2CH-cH20c6Hs~ -CH2-CHC6H5 ~ cyclohexyl, -CH \
2 2 phenyl or phenyl substituted by chloro, b:romo, nitro, trifluoromethyl, meth-oxy, ethoxy, propoxy, butoxy, methylsulphonyl, ethylsulphonyl, phenoxysulphonyl, ~OSl~Z3 (methyl-, ethyl-, propyl-, butyl-) carbonylamino, benzoylamino, (methyl-, ethyl-, propyl-, butyl-) sulphonylamino, aminosulphonyl, N-(methyl-, ethyl-, propyl-, butyl-) aminos~phonyl, N,N-di(methyl-, ethyl-, propyl-, butyl-) amlnosulphonyl, -CH2-C~H5, -CH2CH2-C6H5~ -C6~ 1' -(CH2)1 6--C~(methYl~ ethyl~
propyl, butyl), -(CH2)1 3-NH-CO-(methyl, ethyl, propyl, butyl), hydroxy, methoxysulphonyl, formylamino or lower alkyl; the benzene ring A is unsubstitu-ted or substituted by chloro, bromo, methyl, ethyl, nltro, cyano, trifluoro-methyl, (methyl- or ethyl-) sulphonyl, N-(methyl-, ethyl-, propyl-, butyl- or cyanoethyl-) aminosulphonyl, N,N-bis-(methyl-, ethyl- or hydroxyethyl-)- amino-sulphonyl, (methoxy- or ethyoxy-)-carbonylamino, acetylamino or propionyl-amino; and R represents hydrogen, methyl, ethyl, propyl, isopropyl, butyl, benzyl, ~cyanoethyl, ~hydroxyethyl, ~chloroethyl or cyclohexyl;
Zl~ /CN
N~N ~ ~ Z2 z3 wherein two radicals Z represent groups of the formula -NR3R4 and one radical Z represents a group of the formula -NR3R4,-OR5 or -S-R5, whereby R3, R4 and R5 each represent hydrogen, an aryl, aralkyl or cycloall~l radicai or an ali-phatic radical, or R3 and R4 together form a 5- or 6-membered ring containing the amine nitrogen atom, and the radicals -NR3R4 can be identical to or differ-ent from each other; R6 ' ~
(c) ~ ~=N ~ Q2 7 wherein Q1 represents an N-bridge and the other Q's each independently repre-Rgsent an oxygen or sulphur atom or the -N~R9)-bridge, whereby Rg is l~wer alkyl .
~ J 4--lQ51~;~3 or a hydrogen atom, and R6, ~ and R8 are hydro~en atoms or hydrocarbon radi-cals selected from straight-chain or branched-chain a~yl groups having up to 8 carbon atoms, optionally substituted by hydroxyl or cyano groups, lower-alkoxy groups, lower-alkanoyloxy groups, or by primary, secondary or tertiary amino groups, or cyclohexyl groups or benzyl groups, and phenyl groups option-ally substituted by halogen atoms, nitro groups, acetyl groups, benzoyl groups, cyano groups, thiocyano groups, lower-alkyl groups, lower-alkoxy groups, tri-fluoromethyl groups, lower-alkylsulphonyl groups, phenoxysulphonyl groups, lower-alkylphenoxysulphonyl groups, p-toluenesulphonamido groups, lower-alkoxycarbonyl groups, lower-alkoxy-lower alkoxycarbonyl groups, benzoylamino groups or acetylamino groups, and A and R have the meanings previously defined;
N-N ~ X' Rlo~NI N N-R12 Rll R13 wherein X' represents cyano or carboxylic acid amide, Rlo represents hydrogen, alkyl having 1 to 8 carbon atoms, alkyl substituted by hydroxy, alkoxy having 1 to 8 carbon atoms or alkylamino having in all up to 8 carbon atoms, phenyl, phenyl substltuted by chlorine, methyl, ethyl, ~hydroxyethyl, methoxy or ethoxy, cyclohexyl, benzyl, phenylethyl or ~-N-pyrrolidonylalkyl having 2 or
propyl, butyl), -(CH2)1 3-NH-CO-(methyl, ethyl, propyl, butyl), hydroxy, methoxysulphonyl, formylamino or lower alkyl; the benzene ring A is unsubstitu-ted or substituted by chloro, bromo, methyl, ethyl, nltro, cyano, trifluoro-methyl, (methyl- or ethyl-) sulphonyl, N-(methyl-, ethyl-, propyl-, butyl- or cyanoethyl-) aminosulphonyl, N,N-bis-(methyl-, ethyl- or hydroxyethyl-)- amino-sulphonyl, (methoxy- or ethyoxy-)-carbonylamino, acetylamino or propionyl-amino; and R represents hydrogen, methyl, ethyl, propyl, isopropyl, butyl, benzyl, ~cyanoethyl, ~hydroxyethyl, ~chloroethyl or cyclohexyl;
Zl~ /CN
N~N ~ ~ Z2 z3 wherein two radicals Z represent groups of the formula -NR3R4 and one radical Z represents a group of the formula -NR3R4,-OR5 or -S-R5, whereby R3, R4 and R5 each represent hydrogen, an aryl, aralkyl or cycloall~l radicai or an ali-phatic radical, or R3 and R4 together form a 5- or 6-membered ring containing the amine nitrogen atom, and the radicals -NR3R4 can be identical to or differ-ent from each other; R6 ' ~
(c) ~ ~=N ~ Q2 7 wherein Q1 represents an N-bridge and the other Q's each independently repre-Rgsent an oxygen or sulphur atom or the -N~R9)-bridge, whereby Rg is l~wer alkyl .
~ J 4--lQ51~;~3 or a hydrogen atom, and R6, ~ and R8 are hydro~en atoms or hydrocarbon radi-cals selected from straight-chain or branched-chain a~yl groups having up to 8 carbon atoms, optionally substituted by hydroxyl or cyano groups, lower-alkoxy groups, lower-alkanoyloxy groups, or by primary, secondary or tertiary amino groups, or cyclohexyl groups or benzyl groups, and phenyl groups option-ally substituted by halogen atoms, nitro groups, acetyl groups, benzoyl groups, cyano groups, thiocyano groups, lower-alkyl groups, lower-alkoxy groups, tri-fluoromethyl groups, lower-alkylsulphonyl groups, phenoxysulphonyl groups, lower-alkylphenoxysulphonyl groups, p-toluenesulphonamido groups, lower-alkoxycarbonyl groups, lower-alkoxy-lower alkoxycarbonyl groups, benzoylamino groups or acetylamino groups, and A and R have the meanings previously defined;
N-N ~ X' Rlo~NI N N-R12 Rll R13 wherein X' represents cyano or carboxylic acid amide, Rlo represents hydrogen, alkyl having 1 to 8 carbon atoms, alkyl substituted by hydroxy, alkoxy having 1 to 8 carbon atoms or alkylamino having in all up to 8 carbon atoms, phenyl, phenyl substltuted by chlorine, methyl, ethyl, ~hydroxyethyl, methoxy or ethoxy, cyclohexyl, benzyl, phenylethyl or ~-N-pyrrolidonylalkyl having 2 or
3 carbon atoms in the alkyl radical, Rll represents hydrogen, alkyl having up to 8 carbon atoms, alkyl substituted by hydroxy, alkoxy having 1 to 8 car-; 20 bon atoms or alkylamino having in all 8 carbon atoms, or Rlo and Rll together with the nitrogen atom represent the radical of pyrrolidine, piperidine, mor-pholine, piperazine or N-methylpiperazine, ~hereby, independently of each other, R12 has the same meaning as Rlo, R13 the same meaning as Rll, and R12 and ~ 3 together have the same meaning as Rlo and Rll; or ~3 lQ~14'Z3 ~ 6 (e) ~ ~ \ ~ R15 o 7 o wherein R14 represents a hydrogen atom, or an aIkyl, aralkyl or aryl group, R15 represents a hydrogen atom, an optionally N-ethylated aminocarbonyl radi-cal, a loweralkoxycarbonyl radical, a lower-alkyl, aralkyl or phenyl radical, and R16 represents a hydrogen atom, or an alkyl, aralkyl or phenyl group.
The new dyestuffs are obtained by a process in which the diazonium compound of an amine of the formula ~ -S2- ~ ~ NH2 H03S-O-C2H4 t -S2-M- ~ (II) wherein R and A have the above-given meanings, is coupled with a coupling com-ponent of the dispersion series of the formula H-B, wherein B is an appropri-ate heterocycli.c radical containing in the ortho positlon with respect to the azo bridge a free or acylated primary or secondary amino group, and being free from water-solubilising groups. The dyestuffs of the invention may be re-presented by the formulae (III), (IV), (V), (VI) and (VII) as given below.
The dyestuffs (III) correspond to the formula ,~S~2- \
H03S O C2H4 ~ SO N ~ ~ 12N \ M /
wherein ~ ~ R2, A and R have the above-given meanings.
~The dyestuffs (IV) correspond to the formula - Zl ~CN
/ ~S2 ~ ~ -N ~ Z (IV) 2 ~ ~ N 2 R ~3 ~05~4Z3 wherein Zl~ Z2~ Z3~ A and R have the meanings gi~en above.
The dyestuffs (V) correspond to the formula R
Q
3 2 4 ~ ~ A ~ O2-R (V) wherein Ql' Q2' Q3, R, R6, R7, R8 and A have the meanings given above. Rg is-preferably a hydrogen atom.
The dyestuffs of formula VI are 2,6-diaminopyridine derivatives of the general formula H03S-O-C2H4 ~ ~ N=N ~ X' -S2-N-J 10 N ~ ,-R12 Rll R13 wherein X', R, Rlo, R11, R12, R13 and A have the meanings defined above.
; 10 Group X' is preferably cyano and Rll and R13 are preferably hydrogen atoms, and Rlo and R12 are preferably optionally substituted alkyl grouPs.
Also mentioned are dyestuffs of the formula H03S~C2H4~-S02-N-~A\r ,~
. - , '' R14 R14, R15, R16, R and A are as defined above The benzene ring A can contain, e.g. the following substituents not ; ~ producing an acid reaction on dissociation in water: chlorine or bromine atoms, methyl, ethyl, nitro, cyano trifluoromethyl, methyl or ethylsulphonyl, - N-(methyl-, ethyl-, propyl-, butyl- or cyanoethyl-) aminosulphonyl, N,N-bis-(methyl-, ethyl- or hydroxyethyl-)-aminosulphonyl, methoxy- or ethoxycarbonyl, acetyl~mino or propionyl-amino grouPs.
The radical R appearing in formulae I to VII is, e.g. a hydrog~n ~0514Z3 atom, an ethyl, propyl, butyl, benzyl, ~cyanoethyl, ~hydroxyethyl, ~chloro-ethyl or cyclohexyl group.
The radical R2 is, for example, a radical of the formula {~ ' wherein the ring B can, in addltion, be substituted by chlorine or bromine atoms, nltro, trifluoromethyl, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy, methylsulphonyl, ethylsulphonyl, phenoxysulphonyl, (methyl-, ethyl-, propyl-, butyl-)carbonylamino, benzoylamino, (methyl-, ethyl-, propyl-, butyl-)sulphonylamino, aminosulphonyl, N-(methyl-, ethyl-, propyl-, butyl-) . 10 aminosulphonyl or N,N-di(methyl-, ethyl-, propyl-, butyl-)aminosulphonyl, .2 6 5' CH2CH2 C6H5~ -C6Hll~ -(CH2)1_6~0-CO-(methyl, ethyl, propyl, butyl) -(CH2)1 3~ (nethyi, ethyl, propyl, b~y1) gr~up~.
"
~, .
~: , ~1.
. ~ .
:1 1 .
J
~0514;~
Preferred dyestuffs are those of the formula HO~S0 2 4 ~ so2ll-) ~ H2~
,~D
wherein Ri represents a lower alkyl radical, such as, e.g. a methyl, ethyl, propyl or butyl radical, and the S phenyl nucleus B can carry, in addition, a substituent from the group halogen, hydroxy, acylamino or lower alkyl, particularly chlorine or bromine atoms, hydroxy, lower-alkylcarbonylamino, (formylamino, acetylamino, propionyl-amino, butyrylamino), benzoyl amino, methyl, ethyl, propyl or butyl groups.
Examples of the radicals R3, R4 and R~ occurring in the dyestuffs of formula (V) are: methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, n-pentyl and octyl radicals, which can be interruped by oxygen atoms, and can be substituted by hydroxy, carboxyl, carbalkoxy-(having 2 - 6 carbon atoms), such as (methyl-, ethyl-, propyl-, butyl-) oxycarbonyl, alkoxy-(having 1 - 8 carbon atoms), such as, e.g. methoxy, ethoxy, propoxy, butoxy, hexyloxy or pentyl-j oxy, phenoxy, acyloxy-(having 1-10 carbon atoms), phenyl groups optionally substituted by halogen atoms, such as =i:
chlorine, bromine or fluorine atoms, propoxy, butoxy, ~ i ji methyl, ethyl, propyl, butyl, ~-hydroxyethyl, ethoxy-,, . g-. 1 .
i iO514'~3 carbonyl, methoxycarbonyl, propoxycarbonyl or butoxy-carbonyl groups, or benzyl or phenethyl or cyclohexyl groups, or the radicals R6 and R7 are together linked with a piperidine, pyrrolidine, morpholine, piperazine or methylpiperazine ring.
Preferred dyestuffs of formula (IV) are those of the formula 3\N/
3 C2H4~ (-S0 ~ $~ ~ 3 - R3 R4 4 (IVa) wherein R and A have the previously defined meanings, and R3 and R4 represent hydrogen atoms, and R3 and R4 are hydrogen atoms or methyl, ethyl, propyl and/or butyl groups.
Preferred dyestuffs of formula (IV) are furthermore ~: those of the formula RO~S-0-C~ 2 ~ ~ = N- ~ OR5 S0-N 2 (IVb) whereLn R and A have the meanings defined above, and R5 represents a methyl, ethyl, propyl, butyl, pentyl, ~, .
hexyl, cyclohexyl, phenyl, toluyl, chlorophenyl or acetamidophenyl group.
20 The radicals R6, R7 and R8 contained in the dyestuffs ~ .
.
iO5~4Z3 of formula V are, for example, straight-chain or branched-chain alkyl groups having up to 8 carbon atoms, optionally substituted by hydroxyl or cyano groups, lower-alkoxy groups, lower-alkanoyloxy groups, or by primray, secondary or tertiary amino groups, or cyclohexyl groups or benzyl groups, and phenyl groups optionally substituted by halogen atoms, nitro groups, acetyl groups, benzoyl groups cya~o groups, thiocyano groups, lower-alkyl groups, lower-alkoxy groups, trifluoromethyl groups, lower-alkylsulphonyl groups, phenoxysulphonyl groups, lower-alkylphenoxysulphonyl groups, p-toluenesulphonamido groups, lower-alkoxycarbonyl groups, lower-alkoxy-lower alkoxycarbonyl groups, benzoylamino groups or acetylamino groups. The radical R12 is a lower alkyl group, or preferably a hydrogen atom.
In the dyestuffs of formula V, two radicals Q
preferably represent -NRg-b~idges; then Ql and Q3 as a rule are each an -N-bridge.
A particular development of the invention are the pyrimidine dyestuffs of the formula H0~SCCI~2C;~2- ~ S0 ~ R7 tva) ~ I NH -R~
Suitable coupling components are, for example:
10 51 ~ ~ 3 2-ethylamino-3-cyano-4,6-diamino-pyridine, 2-cyclohexylamino-3-aminocarbonyl-4,6-diamino-pyridine, 2-phenoxy-3-cyano-4,6-diamino-pyridine (the last-mentioned coupling components are obtainable by reaction of 2-bromo-3-cyano-4,6-diamino-pyridine and ethylamine, cyclohexylamino or phenol/phenol/potassium carbonate, and in the case of the aminocarbonyl compound subsequent heating in sulphuric acid), 2,6-dihydroxy-3-cyano-4-methyl-pyridine, 1~ 2-diethylamino-3-cyano-4-methyl-6-(~-hydroxyethylamino)-pyridine, 2,6-dihydroxy-4-methyl-pyridine, and 2,6-bis-(~-hydroxyethylamino)-3-cyano-4-methyl-pyridine.
The coupling can be performed in a manner known per se, preferably in an acid medium, optionally in the presence of sodium acetate, or of similar buffer substances or catalysts influencing the rate of coupling, such as, e.g.
dimethylformamide or pyridine, and salts thereof.
The new dyestuffs are excellently suitable for the printing and, in particular, dyeing of semi-synthetic or, preferably, fully-synthetic materials, especially textile fibres.
Examples of substrates are materials such as poly-acrylonitrile, and mixed polymers made from acrylonitrile .
~)Sl~'~3 and other vinyl compounds, such as acrylic esters~
acrylamides, vinyl pyridine, vinyl chloride or vinylidene chloride, mixed polymers from dicyanoethylene and vinyl acetate, as well as from acrylonitrile block-copolymers, polyurethanes, synthetic polyamidessuch as poly(hexamethylene-adipic acid amide) or polyamide 6.6, poly((~-caprolactam) or polyamide 6, poly(hexamethylenesebacic acid amide) or polyamide 6.10, and poly(ll-aminoundecanoic acid or polyamide 11, preferably cellulose tri- and 2 1/2- acetate, and, in - particular, aromatic polyesters, such as those from terephthalic acid and ethylene glycol or 1,4-dimethylol-cyclohexane, and mixed polymers rom terephthalic and isophthalic acid with ethylene glycol and, optionally, lS 1,4-dimethylolcyclohéxane.
These materials can be in the most diverse stages of processing: for instance, they can be in the form of threads, knitwear, fabrics, yarns or fibres.
These materials are dyed.with the dyestuffs according to the invention under such conditions that the :~ dyestuffs of the formula H0 SOC ~ S2- ) ~ N=N-R
. --. . .. .R ..
are split as follows:
. .
~ - 13 -' .
iC~5~4Z;~
~I~C=~ ( S02N ) ~ N=~- K
~0303 By this reaction there is formed a water-insoluble disperse dyestuff, which is absorbed as such onto the material.
This is effected by a process in which the material is dyed at elevated temperature, e.g. at 80 to 130C~
optionally under pressure, in a slightly acid, neutral or alkaline bath, with a pH-value of ca. 3 to 8, preferably 5 to 7; to this dye bath are optionally added also buffer substances, such as disodium phosphate.
The said process has the advantage that it is extraordinarily simple to perform. Both the dyeing and the printing process can be carried out by the usual operating methods; no unusual substances are used along with the new dyestuff derivatives, no disproportionately ` large amoul~ts of auxiliaries are required, and no special equipment is necessary.
Compared with conventional disperse dyeing processes~
this process offers definite advantages, some of which have already been mentioned: namely, that the dyestufs do not have to be in dispersion form, a factor which eliminates the complicated grinding problems otherwise associated with disperse dyestufs. Furthermore, there ., . ' .
~' ' ' ' ' ' . . .
1(~514;~3 is no need for the application of dispersing agents, which contaminate the waste-water and which in most cases are toxic; and in this connection there is the further advantage that the troublesome problems arising as a result of oam in large dyeing apparatus do not exist in the case of the process according to the invention.
Where not otherwise stated, the term 'parts' in the following examples denotes parts by weight, percentages are expressed as per cent by weight, and temperatures are given in degrees Centigrade. Between . . part by weight and part by volume there is the same ratio as between gram and millilitre.
, - ' ,.
~' ' .
.
.
., , ~ .
~' ' .
, . . .
, . - 1~ .
.' . ', ' ' ' .~
, . .
: ' .' . ' ~ .
~)Sl~Z3 Example l j)CH2C~252 <3~=N~FC~3 SO~Na ~N ~' I
~ . .
0.1 Mole of aminophenyl-4(~-oxàethylsulphone) is introduced at 10C into 30 ml of concentrated sulphuric acid, and stirring maintained overnight at room temperature to obtain complete solution. The solution is then poured onto a minimum amount of ice, so that the temperature remains at 0C. The precipitation of the sulphato ester can be improved by saturation with salt.
After filtration, the rigorously pressed out paste is homogenised in 400 ml of ice water; an addition is made '~ of 0.15 mole of concentrated hydrochloric acid, and the whole titrimetically diazotised at 0-5C with 4N
sodium nitrite. Stirring is continued with a slight excess of nitrite for half an hour at ~he same temperature.
After destruction of the nitrite excess, neutralisation , is effected wlth 0.4 mole of sodium acetate.
An amount, corresponding to the nitrite consumption, of the coupling component (1-3-5-phenyl-methyl-imino-~^i} wrazole) is dissolved with 1 equivalent of hydrochloric acid in 150 ml of water; the resulting clear solution isthen poured at ice-temperature into the dia~o solution.
.~ .
i ~`
., ,~
io5~4~
Coupling occurs instantaneously. After stirring has been maintained overnîght, the dyestuff of formula I is salted out with brine, and subsequently filtered to give, after drying, SO g of a light-yellow dyestuff:
S this dyes with pH-values of between 4 and 7, under HT-conditions, in greenish-yellow shades. There is not the slightest need for any dispersing agent to be applied during dyeing. The dyeings obtained are distinguished by excellent fastness to light, sublimation, rubbing and washing.
The following dyestuffs can be obtained in an analogous manner:
.
!
.
~(~Sl~'~3 Tabl e _ .
No. Shade on poly-_ Cl ester fibres .
1 3 2 42 {~ ~ CH3 yellow H2N N~
H N/ N~
r<Cl CH3 3 3 OC2H4S02-NH ~ N = N ~ yellow C6H5 .
~ ' _ .1 4 35C2H4s2 CH3 ~ ¦ l H2N greenish-., . NH~ CN
6 o3S-O-C2H4 S2 ~ N=N ~ NHC3H7 yellowish-NH2 orange i - . ~ , 105~4Z3 No . Shade on poly-_ ester fibres 7 ~ ~ CN orange _ ~N02 N\HC~2~15 8~ 03S-O-C2H4 S2 ~ N=N ~ NHC6H5 scarlet - CH3 &
¦ 9 ¦35 C2H 502-N ~ N-N ~ C113 ~¦ gold-yellow _ H . .
¦ 10 (3 35~~ 2~14-52N ~ N=N ~ CH3¦ gold-yellow _ . 11 Q 03 -o-c2ll4-s 2-N ~ N=N ~ CH3~ gold-yellow : - ~ Cl 12 03S O C2H4 S2-N ~ N=N ~ CH3gold-yellow ~, . _,.
13 (~ 03S-O~C2H4 S02 ~ H2N ~ ~ greenish-,CH2~
_ H2C so2 , ; . - 19 -1051~Z3 The dyestuffs described below are obtained in an analogous manner:
Table 2 X
3 2 4S2 [N~ ~ N=N
n-l ~2 R2 _ _ ~hade on poly No. R n X Rl R2 'ster fibres l . .
1 CH3 2 ClCH3 C6H5 yellcw .
2 CH(CH3)2 2 H CH3 C6H5 greenish-3 C2N40~1 2 HC113 6 5 . do
The new dyestuffs are obtained by a process in which the diazonium compound of an amine of the formula ~ -S2- ~ ~ NH2 H03S-O-C2H4 t -S2-M- ~ (II) wherein R and A have the above-given meanings, is coupled with a coupling com-ponent of the dispersion series of the formula H-B, wherein B is an appropri-ate heterocycli.c radical containing in the ortho positlon with respect to the azo bridge a free or acylated primary or secondary amino group, and being free from water-solubilising groups. The dyestuffs of the invention may be re-presented by the formulae (III), (IV), (V), (VI) and (VII) as given below.
The dyestuffs (III) correspond to the formula ,~S~2- \
H03S O C2H4 ~ SO N ~ ~ 12N \ M /
wherein ~ ~ R2, A and R have the above-given meanings.
~The dyestuffs (IV) correspond to the formula - Zl ~CN
/ ~S2 ~ ~ -N ~ Z (IV) 2 ~ ~ N 2 R ~3 ~05~4Z3 wherein Zl~ Z2~ Z3~ A and R have the meanings gi~en above.
The dyestuffs (V) correspond to the formula R
Q
3 2 4 ~ ~ A ~ O2-R (V) wherein Ql' Q2' Q3, R, R6, R7, R8 and A have the meanings given above. Rg is-preferably a hydrogen atom.
The dyestuffs of formula VI are 2,6-diaminopyridine derivatives of the general formula H03S-O-C2H4 ~ ~ N=N ~ X' -S2-N-J 10 N ~ ,-R12 Rll R13 wherein X', R, Rlo, R11, R12, R13 and A have the meanings defined above.
; 10 Group X' is preferably cyano and Rll and R13 are preferably hydrogen atoms, and Rlo and R12 are preferably optionally substituted alkyl grouPs.
Also mentioned are dyestuffs of the formula H03S~C2H4~-S02-N-~A\r ,~
. - , '' R14 R14, R15, R16, R and A are as defined above The benzene ring A can contain, e.g. the following substituents not ; ~ producing an acid reaction on dissociation in water: chlorine or bromine atoms, methyl, ethyl, nitro, cyano trifluoromethyl, methyl or ethylsulphonyl, - N-(methyl-, ethyl-, propyl-, butyl- or cyanoethyl-) aminosulphonyl, N,N-bis-(methyl-, ethyl- or hydroxyethyl-)-aminosulphonyl, methoxy- or ethoxycarbonyl, acetyl~mino or propionyl-amino grouPs.
The radical R appearing in formulae I to VII is, e.g. a hydrog~n ~0514Z3 atom, an ethyl, propyl, butyl, benzyl, ~cyanoethyl, ~hydroxyethyl, ~chloro-ethyl or cyclohexyl group.
The radical R2 is, for example, a radical of the formula {~ ' wherein the ring B can, in addltion, be substituted by chlorine or bromine atoms, nltro, trifluoromethyl, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy, methylsulphonyl, ethylsulphonyl, phenoxysulphonyl, (methyl-, ethyl-, propyl-, butyl-)carbonylamino, benzoylamino, (methyl-, ethyl-, propyl-, butyl-)sulphonylamino, aminosulphonyl, N-(methyl-, ethyl-, propyl-, butyl-) . 10 aminosulphonyl or N,N-di(methyl-, ethyl-, propyl-, butyl-)aminosulphonyl, .2 6 5' CH2CH2 C6H5~ -C6Hll~ -(CH2)1_6~0-CO-(methyl, ethyl, propyl, butyl) -(CH2)1 3~ (nethyi, ethyl, propyl, b~y1) gr~up~.
"
~, .
~: , ~1.
. ~ .
:1 1 .
J
~0514;~
Preferred dyestuffs are those of the formula HO~S0 2 4 ~ so2ll-) ~ H2~
,~D
wherein Ri represents a lower alkyl radical, such as, e.g. a methyl, ethyl, propyl or butyl radical, and the S phenyl nucleus B can carry, in addition, a substituent from the group halogen, hydroxy, acylamino or lower alkyl, particularly chlorine or bromine atoms, hydroxy, lower-alkylcarbonylamino, (formylamino, acetylamino, propionyl-amino, butyrylamino), benzoyl amino, methyl, ethyl, propyl or butyl groups.
Examples of the radicals R3, R4 and R~ occurring in the dyestuffs of formula (V) are: methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, n-pentyl and octyl radicals, which can be interruped by oxygen atoms, and can be substituted by hydroxy, carboxyl, carbalkoxy-(having 2 - 6 carbon atoms), such as (methyl-, ethyl-, propyl-, butyl-) oxycarbonyl, alkoxy-(having 1 - 8 carbon atoms), such as, e.g. methoxy, ethoxy, propoxy, butoxy, hexyloxy or pentyl-j oxy, phenoxy, acyloxy-(having 1-10 carbon atoms), phenyl groups optionally substituted by halogen atoms, such as =i:
chlorine, bromine or fluorine atoms, propoxy, butoxy, ~ i ji methyl, ethyl, propyl, butyl, ~-hydroxyethyl, ethoxy-,, . g-. 1 .
i iO514'~3 carbonyl, methoxycarbonyl, propoxycarbonyl or butoxy-carbonyl groups, or benzyl or phenethyl or cyclohexyl groups, or the radicals R6 and R7 are together linked with a piperidine, pyrrolidine, morpholine, piperazine or methylpiperazine ring.
Preferred dyestuffs of formula (IV) are those of the formula 3\N/
3 C2H4~ (-S0 ~ $~ ~ 3 - R3 R4 4 (IVa) wherein R and A have the previously defined meanings, and R3 and R4 represent hydrogen atoms, and R3 and R4 are hydrogen atoms or methyl, ethyl, propyl and/or butyl groups.
Preferred dyestuffs of formula (IV) are furthermore ~: those of the formula RO~S-0-C~ 2 ~ ~ = N- ~ OR5 S0-N 2 (IVb) whereLn R and A have the meanings defined above, and R5 represents a methyl, ethyl, propyl, butyl, pentyl, ~, .
hexyl, cyclohexyl, phenyl, toluyl, chlorophenyl or acetamidophenyl group.
20 The radicals R6, R7 and R8 contained in the dyestuffs ~ .
.
iO5~4Z3 of formula V are, for example, straight-chain or branched-chain alkyl groups having up to 8 carbon atoms, optionally substituted by hydroxyl or cyano groups, lower-alkoxy groups, lower-alkanoyloxy groups, or by primray, secondary or tertiary amino groups, or cyclohexyl groups or benzyl groups, and phenyl groups optionally substituted by halogen atoms, nitro groups, acetyl groups, benzoyl groups cya~o groups, thiocyano groups, lower-alkyl groups, lower-alkoxy groups, trifluoromethyl groups, lower-alkylsulphonyl groups, phenoxysulphonyl groups, lower-alkylphenoxysulphonyl groups, p-toluenesulphonamido groups, lower-alkoxycarbonyl groups, lower-alkoxy-lower alkoxycarbonyl groups, benzoylamino groups or acetylamino groups. The radical R12 is a lower alkyl group, or preferably a hydrogen atom.
In the dyestuffs of formula V, two radicals Q
preferably represent -NRg-b~idges; then Ql and Q3 as a rule are each an -N-bridge.
A particular development of the invention are the pyrimidine dyestuffs of the formula H0~SCCI~2C;~2- ~ S0 ~ R7 tva) ~ I NH -R~
Suitable coupling components are, for example:
10 51 ~ ~ 3 2-ethylamino-3-cyano-4,6-diamino-pyridine, 2-cyclohexylamino-3-aminocarbonyl-4,6-diamino-pyridine, 2-phenoxy-3-cyano-4,6-diamino-pyridine (the last-mentioned coupling components are obtainable by reaction of 2-bromo-3-cyano-4,6-diamino-pyridine and ethylamine, cyclohexylamino or phenol/phenol/potassium carbonate, and in the case of the aminocarbonyl compound subsequent heating in sulphuric acid), 2,6-dihydroxy-3-cyano-4-methyl-pyridine, 1~ 2-diethylamino-3-cyano-4-methyl-6-(~-hydroxyethylamino)-pyridine, 2,6-dihydroxy-4-methyl-pyridine, and 2,6-bis-(~-hydroxyethylamino)-3-cyano-4-methyl-pyridine.
The coupling can be performed in a manner known per se, preferably in an acid medium, optionally in the presence of sodium acetate, or of similar buffer substances or catalysts influencing the rate of coupling, such as, e.g.
dimethylformamide or pyridine, and salts thereof.
The new dyestuffs are excellently suitable for the printing and, in particular, dyeing of semi-synthetic or, preferably, fully-synthetic materials, especially textile fibres.
Examples of substrates are materials such as poly-acrylonitrile, and mixed polymers made from acrylonitrile .
~)Sl~'~3 and other vinyl compounds, such as acrylic esters~
acrylamides, vinyl pyridine, vinyl chloride or vinylidene chloride, mixed polymers from dicyanoethylene and vinyl acetate, as well as from acrylonitrile block-copolymers, polyurethanes, synthetic polyamidessuch as poly(hexamethylene-adipic acid amide) or polyamide 6.6, poly((~-caprolactam) or polyamide 6, poly(hexamethylenesebacic acid amide) or polyamide 6.10, and poly(ll-aminoundecanoic acid or polyamide 11, preferably cellulose tri- and 2 1/2- acetate, and, in - particular, aromatic polyesters, such as those from terephthalic acid and ethylene glycol or 1,4-dimethylol-cyclohexane, and mixed polymers rom terephthalic and isophthalic acid with ethylene glycol and, optionally, lS 1,4-dimethylolcyclohéxane.
These materials can be in the most diverse stages of processing: for instance, they can be in the form of threads, knitwear, fabrics, yarns or fibres.
These materials are dyed.with the dyestuffs according to the invention under such conditions that the :~ dyestuffs of the formula H0 SOC ~ S2- ) ~ N=N-R
. --. . .. .R ..
are split as follows:
. .
~ - 13 -' .
iC~5~4Z;~
~I~C=~ ( S02N ) ~ N=~- K
~0303 By this reaction there is formed a water-insoluble disperse dyestuff, which is absorbed as such onto the material.
This is effected by a process in which the material is dyed at elevated temperature, e.g. at 80 to 130C~
optionally under pressure, in a slightly acid, neutral or alkaline bath, with a pH-value of ca. 3 to 8, preferably 5 to 7; to this dye bath are optionally added also buffer substances, such as disodium phosphate.
The said process has the advantage that it is extraordinarily simple to perform. Both the dyeing and the printing process can be carried out by the usual operating methods; no unusual substances are used along with the new dyestuff derivatives, no disproportionately ` large amoul~ts of auxiliaries are required, and no special equipment is necessary.
Compared with conventional disperse dyeing processes~
this process offers definite advantages, some of which have already been mentioned: namely, that the dyestufs do not have to be in dispersion form, a factor which eliminates the complicated grinding problems otherwise associated with disperse dyestufs. Furthermore, there ., . ' .
~' ' ' ' ' ' . . .
1(~514;~3 is no need for the application of dispersing agents, which contaminate the waste-water and which in most cases are toxic; and in this connection there is the further advantage that the troublesome problems arising as a result of oam in large dyeing apparatus do not exist in the case of the process according to the invention.
Where not otherwise stated, the term 'parts' in the following examples denotes parts by weight, percentages are expressed as per cent by weight, and temperatures are given in degrees Centigrade. Between . . part by weight and part by volume there is the same ratio as between gram and millilitre.
, - ' ,.
~' ' .
.
.
., , ~ .
~' ' .
, . . .
, . - 1~ .
.' . ', ' ' ' .~
, . .
: ' .' . ' ~ .
~)Sl~Z3 Example l j)CH2C~252 <3~=N~FC~3 SO~Na ~N ~' I
~ . .
0.1 Mole of aminophenyl-4(~-oxàethylsulphone) is introduced at 10C into 30 ml of concentrated sulphuric acid, and stirring maintained overnight at room temperature to obtain complete solution. The solution is then poured onto a minimum amount of ice, so that the temperature remains at 0C. The precipitation of the sulphato ester can be improved by saturation with salt.
After filtration, the rigorously pressed out paste is homogenised in 400 ml of ice water; an addition is made '~ of 0.15 mole of concentrated hydrochloric acid, and the whole titrimetically diazotised at 0-5C with 4N
sodium nitrite. Stirring is continued with a slight excess of nitrite for half an hour at ~he same temperature.
After destruction of the nitrite excess, neutralisation , is effected wlth 0.4 mole of sodium acetate.
An amount, corresponding to the nitrite consumption, of the coupling component (1-3-5-phenyl-methyl-imino-~^i} wrazole) is dissolved with 1 equivalent of hydrochloric acid in 150 ml of water; the resulting clear solution isthen poured at ice-temperature into the dia~o solution.
.~ .
i ~`
., ,~
io5~4~
Coupling occurs instantaneously. After stirring has been maintained overnîght, the dyestuff of formula I is salted out with brine, and subsequently filtered to give, after drying, SO g of a light-yellow dyestuff:
S this dyes with pH-values of between 4 and 7, under HT-conditions, in greenish-yellow shades. There is not the slightest need for any dispersing agent to be applied during dyeing. The dyeings obtained are distinguished by excellent fastness to light, sublimation, rubbing and washing.
The following dyestuffs can be obtained in an analogous manner:
.
!
.
~(~Sl~'~3 Tabl e _ .
No. Shade on poly-_ Cl ester fibres .
1 3 2 42 {~ ~ CH3 yellow H2N N~
H N/ N~
r<Cl CH3 3 3 OC2H4S02-NH ~ N = N ~ yellow C6H5 .
~ ' _ .1 4 35C2H4s2 CH3 ~ ¦ l H2N greenish-., . NH~ CN
6 o3S-O-C2H4 S2 ~ N=N ~ NHC3H7 yellowish-NH2 orange i - . ~ , 105~4Z3 No . Shade on poly-_ ester fibres 7 ~ ~ CN orange _ ~N02 N\HC~2~15 8~ 03S-O-C2H4 S2 ~ N=N ~ NHC6H5 scarlet - CH3 &
¦ 9 ¦35 C2H 502-N ~ N-N ~ C113 ~¦ gold-yellow _ H . .
¦ 10 (3 35~~ 2~14-52N ~ N=N ~ CH3¦ gold-yellow _ . 11 Q 03 -o-c2ll4-s 2-N ~ N=N ~ CH3~ gold-yellow : - ~ Cl 12 03S O C2H4 S2-N ~ N=N ~ CH3gold-yellow ~, . _,.
13 (~ 03S-O~C2H4 S02 ~ H2N ~ ~ greenish-,CH2~
_ H2C so2 , ; . - 19 -1051~Z3 The dyestuffs described below are obtained in an analogous manner:
Table 2 X
3 2 4S2 [N~ ~ N=N
n-l ~2 R2 _ _ ~hade on poly No. R n X Rl R2 'ster fibres l . .
1 CH3 2 ClCH3 C6H5 yellcw .
2 CH(CH3)2 2 H CH3 C6H5 greenish-3 C2N40~1 2 HC113 6 5 . do
4 C 2H 4C N 2 H CH3 C 6H5 do <~3 2 H CH3 C 6H5 do 6 . _ 1 HCHlCH3)2C6H5 do .~ 7 _ 1 HOCH3 C6H5 yellow 8 _ 1 H 6 5 C6H5 yellow 9 _ 1 BC6N5 C6H5 yellow _ 1 HCONH2 C6H5 greenish-~., 11 H 2 H CH3 H do . 12 H 2 H CH3 2 4 do `' 13 H 2 H CH3 C2H4CN do 14 H 2 HCH 3 CH2C 6H5 do ~ H CH3 CH2CH-CH~OC6H5 do ', . .
. - 20 -. -.- - . .
1(~5i4Z3 N o . R n . R R ~ Ihade on po l~ -__ __ 1 2 ~ ' ster fibres 16 _ 1 H CH3 OH ye 11 ow 17 _ 1 H CH3 ~ O do lô _ 1 }I CH3 Cl do 19 _ 1 H CH3~ 020CH3 do _ 1 H CH3O~ C2H5 do 21 _ 1 H CH3 ~ do . HCOCM3 L~L 1~ ~" I tlo .
~S14Z3 Likewise in an analogous manner there are obtained the dyestuffs listed in the following Table 3, which correspond to the below given formula:
Table 3 50C2~14S02 [N I ~ ~ R6 No . n x R R R $hade on pol!y_ _ _ 6 7 8 , ~ er fibre.
1 H 2 Cl H C6H5 H oran~e 2 Cil3 2 H C2H40H C6H5C2H5 ' ,o1d-ye11ow 3CH(CH3 )2 2 H C2H40CH3 ~CH3C2H40CH3 gold-yellow 4 _ 1 H CH3 CCH CH3 ~old-yellow _ 1 H C2H4CN ClC2H4CN gold-yellow 6 _ 1 H C2il4CN. 3C2H4Cl ~old-yellow ¦ c~l(C~13)2 ¦ C2 ~ ~ IC~3)2 ~old-~ellow¦
.. .
.
~ - ~2 -,
. - 20 -. -.- - . .
1(~5i4Z3 N o . R n . R R ~ Ihade on po l~ -__ __ 1 2 ~ ' ster fibres 16 _ 1 H CH3 OH ye 11 ow 17 _ 1 H CH3 ~ O do lô _ 1 }I CH3 Cl do 19 _ 1 H CH3~ 020CH3 do _ 1 H CH3O~ C2H5 do 21 _ 1 H CH3 ~ do . HCOCM3 L~L 1~ ~" I tlo .
~S14Z3 Likewise in an analogous manner there are obtained the dyestuffs listed in the following Table 3, which correspond to the below given formula:
Table 3 50C2~14S02 [N I ~ ~ R6 No . n x R R R $hade on pol!y_ _ _ 6 7 8 , ~ er fibre.
1 H 2 Cl H C6H5 H oran~e 2 Cil3 2 H C2H40H C6H5C2H5 ' ,o1d-ye11ow 3CH(CH3 )2 2 H C2H40CH3 ~CH3C2H40CH3 gold-yellow 4 _ 1 H CH3 CCH CH3 ~old-yellow _ 1 H C2H4CN ClC2H4CN gold-yellow 6 _ 1 H C2il4CN. 3C2H4Cl ~old-yellow ¦ c~l(C~13)2 ¦ C2 ~ ~ IC~3)2 ~old-~ellow¦
.. .
.
~ - ~2 -,
Claims (6)
1. A dyestuff of the formula and alkali metal salts thereof, wherein B is (a) wherein R1 represents hydrogen, lower alkyl, lower alkoxy, cyano, lower-alkoxycarbonyl, carbamoyl, lower-alkoxy-lower-alkoxy-carbonyl, phenoxy or phenyl;
R2 represents hydrogen, hydroxyethyl, cyanoethyl, benzyl, phenyl or phenyl substituted by chloro, bromo, nitro, tri-fluoromethyl, methoxy, ethoxy, propoxy, butoxy, methylsul-phonyl,ethylsulphonyl, phenoxysulphonyl, (methyl-, ethyl-, propyl-, butyl-) carbonylamino, benzoylamino, (methyl-, ethyl-, propyl-, butyl-) sulphonylamino, aminosulphonyl, N-(methyl-, ethyl-, propyl-, butyl-) aminosulphonyl, N,N-di-(methyl-, ethyl-, propyl-, butyl-) aminosul-phonyl, -CH2-C6H5, -CH2CH2-C6H5, -C6H11, -(CH2)1-6-O-CO-(methyl, ethyl, propyl, butyl), -(CH2)1-3-NH-CO-(methyl, ethyl, propyl, butyl), hydroxy, methoxysul-phonyl, formylamino or lower alkyl; the benzene ring A is unsubstituted or sub-stituted by chloro, bromo, methyl, ethyl, nitro, cyano, trifluoromethyl, (me-thyl- or ethyl-) sulphonyl, N-(methyl-, ethyl-, propyl-, butyl- or cyanoethyl-) aminosulphonyl, N,N-bis-(methyl-, ethyl- or hydroxyethyl-)- aminosulphonyl, (methoxy- or ethoxy-)-carbonylamino, acetylamino or propionylamino; and R re-presents hydrogen, methyl, ethyl, propyl, isopropyl, butyl, benzyl, .beta.-cyano-ethyl, .beta.-hydroxyethyl, .beta.-chloroethyl or cyclohexyl;
(b) wherein two radicals Z represent groups of the formula -NR3R4 and one radical Z represents a group of the formula -NR3R4, -OR5 or -S-R5, whereby R3, R4 and R5 each represent hydrogen, an aryl, aralkyl or cycloalkyl radical or an ali-phatic radical, or R3 and R4 together form a 5- or 6-membered ring containing the amine nitrogen atom, and the radicals -NR3R4 can be identical to or differ-ent from each other;
(c) wherein Q1 represents an -bridge and the other Q's each independently repre-sent an oxygen or sulphur atom or the -N(R9)-bridge, whereby R9 is lower alkyl or a hydrogen atom, and R6, R7 and R8 are hydrogen atoms or hydrocarbon radi-cals selected from straight-chain or branched-chain alkyl groups having up to 8 carbon atoms, optionally substituted by hydroxyl or cyano groups, lower-alkoxy groups, lower-alkanoyloxy groups, or by primary, secondary or tertiary amino groups, or cyclohexyl groups or benzyl groups, and phenyl groups option-ally substituted by halogen atoms, nitro groups, acetyl groups, benzoyl groups, cyano groups, thiocyano groups, lower-alkyl groups, lower-alkoxy groups, tri-fluoromethyl groups, lower-alkylsulphonyl groups, phenoxysulphonyl groups, lower-alkylphenoxysulphonyl groups, p-toluenesulphonamido groups, lower-alkoxycarbonyl groups, lower-alkoxy-lower alkoxycarbonyl groups, benzoylamino groups or acetylamino groups, and A and R have the meanings previously defined;
(d) wherein X' represents cyano or carboxylic acid amide, R10 represents hydrogen, alkyl having 1 to 8 carbon atoms, alkyl substituted by hydroxy, alkoxy having 1 to 8 carbon atoms or alkylamino having in all up to 8 carbon atoms, phenyl, phenyl substituted by chlorine, methyl, ethyl, .beta.-hydroxyethyl, methoxy or ethoxy, cyclohexyl, benzyl, phenylethyl or .omega.-N-pyrrolidonylalkyl having 2 or 3 carbon atoms in the alkyl radical, R11 represents hydrogen, alkyl having up to 8 carbon atoms, alkyl substituted by hydroxy, alkoxy having 1 to 8 carbon atoms or alkylamino having in all 8 carbon atoms, or R10 and R11 together with the nitrogen atom represent the radical of pyrrolidine, piperidine, mor-pholine, piperazine or N-methylpiperazine, whereby, independently of each other, R12 has the same meaning as R10, R13 the same meaning as R11, and R12 and R13 together have the same meaning as R10 and R11; or (e) wherein R14 represents a hydrogen atom, or an alkyl, aralkyl or aryl group, R15 represents a hydrogen atom, an optionally N-ethylated aminocarbonyl radi-cal, a loweralkoxycarbonyl radical, a lower-alkyl, aralkyl or phenyl radical, and R16 represents a hydrogen atom, or an alkyl, aralkyl or phenyl group.
R2 represents hydrogen, hydroxyethyl, cyanoethyl, benzyl, phenyl or phenyl substituted by chloro, bromo, nitro, tri-fluoromethyl, methoxy, ethoxy, propoxy, butoxy, methylsul-phonyl,ethylsulphonyl, phenoxysulphonyl, (methyl-, ethyl-, propyl-, butyl-) carbonylamino, benzoylamino, (methyl-, ethyl-, propyl-, butyl-) sulphonylamino, aminosulphonyl, N-(methyl-, ethyl-, propyl-, butyl-) aminosulphonyl, N,N-di-(methyl-, ethyl-, propyl-, butyl-) aminosul-phonyl, -CH2-C6H5, -CH2CH2-C6H5, -C6H11, -(CH2)1-6-O-CO-(methyl, ethyl, propyl, butyl), -(CH2)1-3-NH-CO-(methyl, ethyl, propyl, butyl), hydroxy, methoxysul-phonyl, formylamino or lower alkyl; the benzene ring A is unsubstituted or sub-stituted by chloro, bromo, methyl, ethyl, nitro, cyano, trifluoromethyl, (me-thyl- or ethyl-) sulphonyl, N-(methyl-, ethyl-, propyl-, butyl- or cyanoethyl-) aminosulphonyl, N,N-bis-(methyl-, ethyl- or hydroxyethyl-)- aminosulphonyl, (methoxy- or ethoxy-)-carbonylamino, acetylamino or propionylamino; and R re-presents hydrogen, methyl, ethyl, propyl, isopropyl, butyl, benzyl, .beta.-cyano-ethyl, .beta.-hydroxyethyl, .beta.-chloroethyl or cyclohexyl;
(b) wherein two radicals Z represent groups of the formula -NR3R4 and one radical Z represents a group of the formula -NR3R4, -OR5 or -S-R5, whereby R3, R4 and R5 each represent hydrogen, an aryl, aralkyl or cycloalkyl radical or an ali-phatic radical, or R3 and R4 together form a 5- or 6-membered ring containing the amine nitrogen atom, and the radicals -NR3R4 can be identical to or differ-ent from each other;
(c) wherein Q1 represents an -bridge and the other Q's each independently repre-sent an oxygen or sulphur atom or the -N(R9)-bridge, whereby R9 is lower alkyl or a hydrogen atom, and R6, R7 and R8 are hydrogen atoms or hydrocarbon radi-cals selected from straight-chain or branched-chain alkyl groups having up to 8 carbon atoms, optionally substituted by hydroxyl or cyano groups, lower-alkoxy groups, lower-alkanoyloxy groups, or by primary, secondary or tertiary amino groups, or cyclohexyl groups or benzyl groups, and phenyl groups option-ally substituted by halogen atoms, nitro groups, acetyl groups, benzoyl groups, cyano groups, thiocyano groups, lower-alkyl groups, lower-alkoxy groups, tri-fluoromethyl groups, lower-alkylsulphonyl groups, phenoxysulphonyl groups, lower-alkylphenoxysulphonyl groups, p-toluenesulphonamido groups, lower-alkoxycarbonyl groups, lower-alkoxy-lower alkoxycarbonyl groups, benzoylamino groups or acetylamino groups, and A and R have the meanings previously defined;
(d) wherein X' represents cyano or carboxylic acid amide, R10 represents hydrogen, alkyl having 1 to 8 carbon atoms, alkyl substituted by hydroxy, alkoxy having 1 to 8 carbon atoms or alkylamino having in all up to 8 carbon atoms, phenyl, phenyl substituted by chlorine, methyl, ethyl, .beta.-hydroxyethyl, methoxy or ethoxy, cyclohexyl, benzyl, phenylethyl or .omega.-N-pyrrolidonylalkyl having 2 or 3 carbon atoms in the alkyl radical, R11 represents hydrogen, alkyl having up to 8 carbon atoms, alkyl substituted by hydroxy, alkoxy having 1 to 8 carbon atoms or alkylamino having in all 8 carbon atoms, or R10 and R11 together with the nitrogen atom represent the radical of pyrrolidine, piperidine, mor-pholine, piperazine or N-methylpiperazine, whereby, independently of each other, R12 has the same meaning as R10, R13 the same meaning as R11, and R12 and R13 together have the same meaning as R10 and R11; or (e) wherein R14 represents a hydrogen atom, or an alkyl, aralkyl or aryl group, R15 represents a hydrogen atom, an optionally N-ethylated aminocarbonyl radi-cal, a loweralkoxycarbonyl radical, a lower-alkyl, aralkyl or phenyl radical, and R16 represents a hydrogen atom, or an alkyl, aralkyl or phenyl group.
2. A dyestuff according to claim 1 of the formula wherein the benzene ring B is unsubstituted or substituted by chloro, bromo, hydroxy, loweralkylcarbonylamino, benzoylamino or lower alkyl; R1 represents lower alkyl; and the benzene ring A, and R have the meanings defined in claim 1, and the sodium salt thereof.
3. A dyestuff according to claim 1 of the formula
4. A dyestuff according to claim 2 of the formula
5. A dyestuff according to claim 1 of the formula
6. A dyestuff according to claim 1 of the formula
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH479873A CH615937A5 (en) | 1973-04-04 | 1973-04-04 | Process for the preparation of novel dyestuffs for synthetic textile material |
| CH329174 | 1974-03-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1051423A true CA1051423A (en) | 1979-03-27 |
Family
ID=25692673
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA196,542A Expired CA1051423A (en) | 1973-04-04 | 1974-04-01 | Dyestuffs for synthetic textile material |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS49130920A (en) |
| AR (1) | AR201685A1 (en) |
| CA (1) | CA1051423A (en) |
| DE (1) | DE2416002A1 (en) |
| ES (1) | ES424894A1 (en) |
| FR (1) | FR2224525B1 (en) |
| GB (1) | GB1469453A (en) |
| IT (1) | IT1004075B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3025904A1 (en) * | 1980-07-09 | 1982-02-11 | Hoechst Ag, 6000 Frankfurt | WATER-SOLUBLE AZO COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS DYES |
| DE3643386A1 (en) * | 1986-12-19 | 1988-06-23 | Hoechst Ag | AZO COMPOUNDS CONTAINING CYAN GROUPS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS DYES |
| US4900813A (en) * | 1987-07-02 | 1990-02-13 | Ciba-Geigy Corporation | Fiber-reactive azo dyes having a 4,6-diaminopyridine coupling component |
| GB2272914B (en) * | 1992-11-27 | 1996-01-17 | Zeneca Ltd | Chemical compounds |
-
1974
- 1974-04-01 CA CA196,542A patent/CA1051423A/en not_active Expired
- 1974-04-02 DE DE19742416002 patent/DE2416002A1/en not_active Withdrawn
- 1974-04-02 AR AR25310974A patent/AR201685A1/en active
- 1974-04-03 ES ES424894A patent/ES424894A1/en not_active Expired
- 1974-04-03 FR FR7411763A patent/FR2224525B1/fr not_active Expired
- 1974-04-03 IT IT5001574A patent/IT1004075B/en active
- 1974-04-04 GB GB1503774A patent/GB1469453A/en not_active Expired
- 1974-04-04 JP JP3746674A patent/JPS49130920A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| IT1004075B (en) | 1976-07-10 |
| GB1469453A (en) | 1977-04-06 |
| AR201685A1 (en) | 1975-04-08 |
| JPS49130920A (en) | 1974-12-16 |
| DE2416002A1 (en) | 1974-10-24 |
| FR2224525B1 (en) | 1976-12-17 |
| ES424894A1 (en) | 1976-11-01 |
| FR2224525A1 (en) | 1974-10-31 |
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