CA1221360A - Monoazo compounds, processes for their preparation, and their use as dyestuffs - Google Patents
Monoazo compounds, processes for their preparation, and their use as dyestuffsInfo
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- CA1221360A CA1221360A CA000427942A CA427942A CA1221360A CA 1221360 A CA1221360 A CA 1221360A CA 000427942 A CA000427942 A CA 000427942A CA 427942 A CA427942 A CA 427942A CA 1221360 A CA1221360 A CA 1221360A
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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
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/24—Monoazo dyes prepared by diazotising and coupling from coupling components containing both hydroxyl and amino directing groups
- C09B29/28—Amino naphthols
- C09B29/30—Amino naphtholsulfonic acid
-
- 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
- C09B62/4401—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 with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system
- C09B62/4403—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 with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system the heterocyclic system being a triazine ring
- C09B62/4411—Azo dyes
- C09B62/4413—Non-metallized monoazo dyes
-
- 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
- C09B62/08—Azo dyes
- C09B62/085—Monoazo dyes
Abstract
Abstract of the disclosure:
Water-soluble monoazo compounds of the general formula (1) (1) in which M represents a hydrogen atom or the equivalent of a metal, D is a benzene nucleus or a naphthalene nucleus, R1 denotes a hydrogen atom or an alkyl group of 1 to 4 carbon atoms or a sulfo group, R2 is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, R3 represents a hydrogen atom, an alkyl group of 1 to 4 carbon atoms or an alkoxy group of 1 to 4 carbon atoms and R4 denotes a hydrogen atom or an alkyl group of 1 to 4 carbon atoms or an alkoxy group of 1 to 4 carbon atoms, where R1, R2, R3 and R4 can be identical to or different from one another, Y is a fluorine atom or a bromine atom or, preferably, a chlorine atom and X in each case denotes a .beta.-sulfatoethyl group or a .beta.-thio-sulfatoethyl group or a .beta.-chloroethyl group or a vinyl group, where the two Xs can be identical to or different from one another, and the group(s) of the formula -SO2-X are bonded in the benzene nucleus in meta- or para-position relative to the azo group or acylated amino group and can be bonded in the naphthalene nucleus in any position and the second group of the formula -SO3M in the radical of the aminonaphthol-disulfonic acid is bonded in meta- or para-position rela-tive to the acylated amino group.
These compounds of the formula (1) are prepared in analogy to known methods from the components evident from the formula (1) (the diazo component with the moiety D, cyanuric chloride, cyanuric bromide or cyanuric fluoride, the 1-amino-8-naphthol-3,6- or -4,6-disulfonic acid and the aniline compound with the group -SO2-X). They have very good fiber-reactive dyestuff properties and produce, for example on cellulose fiber materials, deep and fast dyeings and prints.
Water-soluble monoazo compounds of the general formula (1) (1) in which M represents a hydrogen atom or the equivalent of a metal, D is a benzene nucleus or a naphthalene nucleus, R1 denotes a hydrogen atom or an alkyl group of 1 to 4 carbon atoms or a sulfo group, R2 is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, R3 represents a hydrogen atom, an alkyl group of 1 to 4 carbon atoms or an alkoxy group of 1 to 4 carbon atoms and R4 denotes a hydrogen atom or an alkyl group of 1 to 4 carbon atoms or an alkoxy group of 1 to 4 carbon atoms, where R1, R2, R3 and R4 can be identical to or different from one another, Y is a fluorine atom or a bromine atom or, preferably, a chlorine atom and X in each case denotes a .beta.-sulfatoethyl group or a .beta.-thio-sulfatoethyl group or a .beta.-chloroethyl group or a vinyl group, where the two Xs can be identical to or different from one another, and the group(s) of the formula -SO2-X are bonded in the benzene nucleus in meta- or para-position relative to the azo group or acylated amino group and can be bonded in the naphthalene nucleus in any position and the second group of the formula -SO3M in the radical of the aminonaphthol-disulfonic acid is bonded in meta- or para-position rela-tive to the acylated amino group.
These compounds of the formula (1) are prepared in analogy to known methods from the components evident from the formula (1) (the diazo component with the moiety D, cyanuric chloride, cyanuric bromide or cyanuric fluoride, the 1-amino-8-naphthol-3,6- or -4,6-disulfonic acid and the aniline compound with the group -SO2-X). They have very good fiber-reactive dyestuff properties and produce, for example on cellulose fiber materials, deep and fast dyeings and prints.
Description
~2~36~
The invention relates to the technical field of fiber-reactive ago distaffs.
Specification No.
German Potent describes, in the Table on columns 15/16, a muons distaff which con-tarns a fiber reactive monochlorotr;azinyl radical and as further f;ber-reactive radicals a ~-~sulfatoethylsulfonyl group and a vinylsulfonyl group.
Jo have now found new, valuable, water-soluble ago compounds of the general formula to) I
A _ D - N - No NH ~s42 --X
X -- S02 3 S03M (1) on which M represents a hydrogen atom or the equivalent of a metal, such as, in particular, of an alkali or alkaline earth metal, such as, for example, of sodium potassium, lithium or calcium, is a Bunsen nucleus or a naphthalene nucleus, R1 denotes a hydrogen atom or an a~kyl group of 1 to I
carbon atoms, such as, for example, an ethyl group or in particular a methyl group, or a sulfa group owe the I
general formula -Sly where M has the a~ovementioned meaning), I is a hydrogen atom or an alkyd group of 1 to 4 carbon atoms, such as, for example an ethyl group or in part-cuter, a methyl group R3 represents a hydrogen atom, an alkyd group of 1 to 4 carbon atoms, such as, for example, an ethyl group or, in particular, a methyl group, or an alkoxy group of 1 to 4 carbon atoms, such as, for example, an ethics group or, in particular a methoxy group, and R4 denotes a hydrogen atom or an alkyd group of 1 to 4 carbon atoms, such as, for example, an ethyl group or, in particular, a methyl group, or an alkoxy group of 1 to 4 carbon atoms, such as, for example, an ethics group or, in particular, a methoxy group, where R1, R2~ R3 and R4 ran be identical to or different from one Arthur, Y is a fluorine atom or a brom;ne atom or preferably a chlorine atom and on X denotes in each case a B-sulfatoethyl group of the general formula -CH2-CH2-OS03M where M has the above-mentioned meaning) or a B-thiosulfatoethyl group (of the general formula -CHz~CH2-S-SO3~ where M has the above mentioned mooning or a B-chloroethyl group or a vinyl US group, where the two Us can be dental to or different from one another, and the group(s) of the formula -S02-X are in the Bunsen nucleus in mote- or para-position relative to the ago group or to the assaulted amino group or can be bonded in Lo the naphthalene nucleus on any positron, and the second group of the formula -S03M us bonded on the radical of the am;nonaphtholdisu'.fsn;c acid on mote- or para-pos;t;on relative to the assaulted amino group.
The new ago compounds can be in the form of an acid or in the form of their salts. whey are preferably in the form of their salts, on particular the salts of alkali or alkaline earth metals and they are also prefer-ably used on the form of these salts for coloring (under-dyeing and stood here and below in the general sense and as including printing) hydroxy- and/or carboxamide-containing mater-pals, in particular fiber materials.
The present invention also relates to processes for preparing the ago compounds of the general formula to) mentioned and defined above. They can be prepared in the manner of the invention by for example, reacting a come pound of the general formula I
R1 HO NH NO to) ` R2 - - D-- N = No X S2 ~503S S03M
.
on which D, R1~ R2, M, X and Y have the above mentioned meanings and the second group of the formula -S03M in the radical of the aminonaphtholdisulfonic acid us in the mote- or para-position relative to the assaulted amino group, with an aromatic amine of the general formula (3) ~L2~L3~0 Ho R4 S2~
in which R3, R4 and X have the above mentioned meanings and the group of the formula SIX us bonded on the Bunsen nucleus in mote- or para-posi~ion relative to the amino group, or by reacting an ago compound of the general formula to) R2 _ D - N = N
X - SO MOWS SIAM
in Shea D, R1, R2, X and M have the above mentioned meanings and the second group of the formula -S03M in the radical of the am;nonaphtholdisulfonic acid is bonded in mote- or para-posit;on relative to the amino group, with a dlhalogenotriazinyl compound of the general formula (5) N R
The invention relates to the technical field of fiber-reactive ago distaffs.
Specification No.
German Potent describes, in the Table on columns 15/16, a muons distaff which con-tarns a fiber reactive monochlorotr;azinyl radical and as further f;ber-reactive radicals a ~-~sulfatoethylsulfonyl group and a vinylsulfonyl group.
Jo have now found new, valuable, water-soluble ago compounds of the general formula to) I
A _ D - N - No NH ~s42 --X
X -- S02 3 S03M (1) on which M represents a hydrogen atom or the equivalent of a metal, such as, in particular, of an alkali or alkaline earth metal, such as, for example, of sodium potassium, lithium or calcium, is a Bunsen nucleus or a naphthalene nucleus, R1 denotes a hydrogen atom or an a~kyl group of 1 to I
carbon atoms, such as, for example, an ethyl group or in particular a methyl group, or a sulfa group owe the I
general formula -Sly where M has the a~ovementioned meaning), I is a hydrogen atom or an alkyd group of 1 to 4 carbon atoms, such as, for example an ethyl group or in part-cuter, a methyl group R3 represents a hydrogen atom, an alkyd group of 1 to 4 carbon atoms, such as, for example, an ethyl group or, in particular, a methyl group, or an alkoxy group of 1 to 4 carbon atoms, such as, for example, an ethics group or, in particular a methoxy group, and R4 denotes a hydrogen atom or an alkyd group of 1 to 4 carbon atoms, such as, for example, an ethyl group or, in particular, a methyl group, or an alkoxy group of 1 to 4 carbon atoms, such as, for example, an ethics group or, in particular, a methoxy group, where R1, R2~ R3 and R4 ran be identical to or different from one Arthur, Y is a fluorine atom or a brom;ne atom or preferably a chlorine atom and on X denotes in each case a B-sulfatoethyl group of the general formula -CH2-CH2-OS03M where M has the above-mentioned meaning) or a B-thiosulfatoethyl group (of the general formula -CHz~CH2-S-SO3~ where M has the above mentioned mooning or a B-chloroethyl group or a vinyl US group, where the two Us can be dental to or different from one another, and the group(s) of the formula -S02-X are in the Bunsen nucleus in mote- or para-position relative to the ago group or to the assaulted amino group or can be bonded in Lo the naphthalene nucleus on any positron, and the second group of the formula -S03M us bonded on the radical of the am;nonaphtholdisu'.fsn;c acid on mote- or para-pos;t;on relative to the assaulted amino group.
The new ago compounds can be in the form of an acid or in the form of their salts. whey are preferably in the form of their salts, on particular the salts of alkali or alkaline earth metals and they are also prefer-ably used on the form of these salts for coloring (under-dyeing and stood here and below in the general sense and as including printing) hydroxy- and/or carboxamide-containing mater-pals, in particular fiber materials.
The present invention also relates to processes for preparing the ago compounds of the general formula to) mentioned and defined above. They can be prepared in the manner of the invention by for example, reacting a come pound of the general formula I
R1 HO NH NO to) ` R2 - - D-- N = No X S2 ~503S S03M
.
on which D, R1~ R2, M, X and Y have the above mentioned meanings and the second group of the formula -S03M in the radical of the aminonaphtholdisulfonic acid us in the mote- or para-position relative to the assaulted amino group, with an aromatic amine of the general formula (3) ~L2~L3~0 Ho R4 S2~
in which R3, R4 and X have the above mentioned meanings and the group of the formula SIX us bonded on the Bunsen nucleus in mote- or para-posi~ion relative to the amino group, or by reacting an ago compound of the general formula to) R2 _ D - N = N
X - SO MOWS SIAM
in Shea D, R1, R2, X and M have the above mentioned meanings and the second group of the formula -S03M in the radical of the am;nonaphtholdisulfonic acid is bonded in mote- or para-posit;on relative to the amino group, with a dlhalogenotriazinyl compound of the general formula (5) N R
2 in which Y, R3~ R4 and X have the abovementloned meanings and the group of the formula -S02-X is bonded in the Bunsen nucleus in mote- or para-position relative to the assaulted amino group.
~L~22~36~
The dihalogenotriazinylamino compounds of the general formula to) can be prepared in analogy to known Moe by coupling the diazonium salt of an amino compound of the general formula ~63 2 \
R --D--NH2 (63 X So on which D, R1, R2 and X have the above mentioned meanings and the group of the formula -S02X is bonded in the Bunyan nucleus on mote- or para-pos;tion relative to the amino group, with 1-(2',4'-dihalo~eno-1',3',5'-triazin-6'-yl)-amino-8-hydroxynaphthalene-3,6- or -4r6-disulfonic acid.
The reaction of dihalogenotri3z;nyL compounds of the general formulae (2) and (5) with the corresponding amino compounds can also be carried out on analogy to a known method. These reactions are described for example, in WIFE Beech Fibre-reactive Dyes, London 1970~ pages 148 et seq. The abovement;oned coupling reaction is preferably carried out within a pi range between 4 and 7 at a tempera-lure between 0C and 30C. The condensation reactions of the dihalogenotriazinyl compounds with the amino come pounds are generally carried out in an aqueous medium, of appropriate in the presence of an organic solvent, at a temperature between 0C and 70C~ preferably between 20C and 70C, and preferably at a pH-value of from 4 to 7.
The process according to the invention can thus be carried out by reacting the diazonium salt of the amino 36g~
compound of the general formula I and the aniline come pound of the general formula to) in any order with 1-(2',4'-dihalogeno-1l,3',5'-triazin-6'-yl)-amino-8--naphthol-
~L~22~36~
The dihalogenotriazinylamino compounds of the general formula to) can be prepared in analogy to known Moe by coupling the diazonium salt of an amino compound of the general formula ~63 2 \
R --D--NH2 (63 X So on which D, R1, R2 and X have the above mentioned meanings and the group of the formula -S02X is bonded in the Bunyan nucleus on mote- or para-pos;tion relative to the amino group, with 1-(2',4'-dihalo~eno-1',3',5'-triazin-6'-yl)-amino-8-hydroxynaphthalene-3,6- or -4r6-disulfonic acid.
The reaction of dihalogenotri3z;nyL compounds of the general formulae (2) and (5) with the corresponding amino compounds can also be carried out on analogy to a known method. These reactions are described for example, in WIFE Beech Fibre-reactive Dyes, London 1970~ pages 148 et seq. The abovement;oned coupling reaction is preferably carried out within a pi range between 4 and 7 at a tempera-lure between 0C and 30C. The condensation reactions of the dihalogenotriazinyl compounds with the amino come pounds are generally carried out in an aqueous medium, of appropriate in the presence of an organic solvent, at a temperature between 0C and 70C~ preferably between 20C and 70C, and preferably at a pH-value of from 4 to 7.
The process according to the invention can thus be carried out by reacting the diazonium salt of the amino 36g~
compound of the general formula I and the aniline come pound of the general formula to) in any order with 1-(2',4'-dihalogeno-1l,3',5'-triazin-6'-yl)-amino-8--naphthol-
3,6- or -4,~-disulfonic acid.
The hydraulic acid liberated in the course of the condensation reactions us bound by means of ac;d-b;nd;ng agents such as, for example, sodium hydroxide, potassium hydro~;de, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate sodium acetate or a basic sodium phosphate.
Examples of amino compounds of the general formula (3) which can be used as starting compounds for preparing the muons compounds of the invention are I sulfite-ethylsulfonyl)-ani!ine, 2-methoxy-5-~-sulfatoethylsulfon-yl)-aniline, 2,5-dimethoxy-4-~-sulfatoethylsulfonyL)-aniline, 2-methoxy-4-t~-sulfatoethylsulfonyl)-aniline, 4-methoxy-5-(~-sulfatoethylsulfonyl)-aniline, 2,4-d;methoxy-I sulfatoethylsulfonyl~-an;l;ne, 2-methoxy-5-methyl-4-(~-sulfatoethylsulfonyl)-aniline, 2-methyl-5-(~-sulfato-ethylsulfonyl)-an;l;ne, 2,5-dimethyl-4-(~-sulfatoethyl-sulfonyl)-an;l;ne, 2~6-d;methyl-4-t~-sulfatoethylsulfonyl)-aniline, 4-methyl-3-t~-sulfatoethylsulfonyl)-aniline and on particular 4-~-sulfatoethylsulfonyl)-an;l;ne and those derivatives of these aniline compounds in which the -sulfatoethylsulfonyl group has been replaced by a vinyl-sulfonyl, a ~-th;osulfatoethylsulfonyl or a chloroethyl-suifonyl group.
Examples of amino compounds of the general formula 16) which can be used as starting compounds in the proper I
lion of the ago compounds of the invention are I
suLfatoethylsulfonyl)-an;l;ne, methyl sulfatoethyl-sulfonyl)-aniline, 4-methyl-3-(~-sulfatoethylsulfonyl)-aniline, 2,5-d;methyl-4-(~-sulfatoethylsulfonyl)-aniline, 2~6-dimethyl-4-(~-sulfatoethylsulfonyl~-aniline, I
sulfatoethylsulfonyl)-aniline-2-sulfonic acid, 6 (I-sulfatoethylsulfonyl)-2-aminonaphthalene-1-sulfonito acid, 8-(~-sulfatoethylsulfonyl)-2-aminonaphthalenY, So sulfatoethylsulfonyl)-2-am;nonaphthaleneO sulfite-ethylsulfonyl)-2-aminonaphthalene-6-sulfon;c acid and in particular 4-(~-sulfatoethylsulfonyl)-an;line and those derivatives of these aniline and naphthylamine compounds in which the ~-sulfatoethylsulfonyl group has been no-placed by a vinylsulfonyl, ~-thiosulfatoethylsulfonyl or ~-chloroethylsulfonyl group.
Of the ago compounds of the invention those are particularly noteworthy which have the general formula (1) on which D denotes a Bunsen nucleus and R1, R2, R3 and R4 each represent a hydrogen atom or in which D denotes a naphthalene nucleus, R1 us a hydrogen atom or a sulfa group, and R2, R3 and R4 each represent a hydrogen atom.
Of the ago compounds of the invention, those are also preferred in which the X groups represent a vinyl group or, on particular, a ~-sulfatoethyl group.
Other noteworthy ago compounds of the invention are those described in Examples 1, I 7, 16, 30, 42 and 49.
The formula I compounds prepared in the manner of the invention can be separated from the synthesis soul-lion by generally known methods, for example either by 3122~L36~
precipitating them from the reaction medium by means of electrolytes such as, for example, sodium chloride or potassium chloride, or by evaporating the reaction soul-lion, for example by spray drying where a buffer substance can be added to thus reaction solution.
The ago compounds of the invention have valuable distaff properties. because of the two fiber-react;ve groups of the vinylsulfonyl series and because of the halogenotriaz;nyl radical, they have fiber-react;ve pro-purities The new compounds are preferably used for coloring in the general sense defined earlier) hydroxy- and/or ~arboxam;de-contain;ng materials, for example on the form of sheet-Like structures, such as paper or leather or films, such as, for example, those made of polyamide, or in the unshaped state, sushi as, for example, polyamide or polyurethane, but on particular these materials in fiber form The solutions of these ago compounds obtained in the synthesis of compounds of the invention can also be used directly in dyeing as Cody compositions/ of approp-rate after a buffer substance has been added or the soul-ton has been concentrated or diluted. The present invent lion therefore also relates to the use of compounds of the general formula (1) coloring yin the above sense) these materials or rather to processes for coloring such materials on a completely conventional manner in which a compound of the general formula I is used as colorant.
The materials are preferably used in the fornl of fiber materials, on particular on the form of textile fibers, such as yarns, packages or fabrics.
~L2~2~L3~C~
Hydroxy - containing materials are those of natural or synthetic organ, such as, for example, cellulosic fiber materials or their regenerated products and polyvinyl alcohols. Cellulosic fiber materials are preferably S cotton, but also other vegetable fibers, such as linen, hemp, jute or Rome fibers; examples of regenerated cell-logic fibers are viscose staple and filament viscose.
Examples of carboxam;de-conta;n;ng materials are synthetic and natural polyamides and polyurethane, in particular in the form of fibers, for example wool and other animal hairs, silk, leather, nylon-6,6, Nolan nylon-11 and Nolan The novel compounds of the general formula (1) can be applied and fixed to said substrates, in particular said fiber materials, by the application techniques known for water-soluble distaffs, in particular those known for ~ater-solubler f;ber-reactive distaffs.
For instance, applied to cellulose fibers by exhaust methods from a long liquor using various acid-2Q binding agents and, if appropriate, neutral salts, swishes sodium chloride or sodium sulfate, they give very good color yields and excellent color buildup Dyeing is preferably carried out in an aqueous bath at temperatures between 60 and 105C, if appropriate at temperatures of up to SKYE under pressure, and, if appropriate, in the presence of customary dyeing auxiliaries. The dyeing can be carried out by introducing the material into a warm bath and gradually raising the temperature of this bath to the desired dyeing temperature and completing the 36~
dyeing process at thus temperature Neutral salts which accelerate the exhaustion of the distaff can be added to the bath, of desired only after the actual dyeing topper-lure has been reached.
The padding method also gives excellent color yields and a very good color build-up on cellulosic fibers, with toe aid of an acid-bînding agent on which the dyes can be foxed on a customary mannerly material padded with the dye liquor, leaving the to stand at room temperature or Elena-ted temperatures, for example up to about 60C~ by steaming or by means of dry heat Strong prints having well-del;neated contours and a clear white ground are also obtained in customary print-no methods for cellulose fibers, which can be carried out in one step - for example by printing with a print paste containing sodium bicarbonate or a different acid-binding agent and then steaming at Tao 103C - or in two steps, for example by printing with a neutral or weekly acid print paste and then fixing either by passing the printed goods through a hot electrolyte-containing alga-line bath or by over padding with an alkaline electrolyte-containing paid jug liquor and then leaving the over padded material to stand or steaming it or treating it with dry heat. The outcome of the prints varies only little Thea changing fixing cond;t;ons.
In dry heat fixing by customary thermof;x;ng methods, hot air at 120 to 200C us used. In addition to customary steam at 101 to 103C, it is also possible to use superheated steam or saturated steam at temperatures of us to 160C.
36~
Examples of agents which bond acid and effect the fixation of the compound of the formula I on cellulosic fibers are ~ater-soluble basic salts of alkali metals and also alkaline earth metals Thea inorganic or organic acids, or compounds which liberate alkali when heated. The alkali metal hydroxides and alkali metal salts of weak to medium inorganic or organic acids are particularly note-worthy, the sodium and putts compounds in particular being intended among the alkali metal compounds. Examples 1Q of such acid-binding agents are sodium hydroxide, poles-slum hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium format, sodium dihydrogen-phosphate, sodium hydroge~phosphate, sodium trichloro-acetate, sodium silicate and trisodium phosphate.
The treatment of compounds of the invention with an acid-b;nding agent, if appropriate under heat, chemically bonds the compounds of the invention (distaffs) to the cellulose fiber; applied on dyeing and printing methods, they are distinguished on these fiber materials by a high degree of fixation. The cellulose dyeings have excellent wet fastness properties after the customary after treatment whereby unfixed distaff is removed by rinsing, in portico-far since the unfixed distaff can be readily washed out thanks to the fact that it is readily soluble on cold water.
Dyeings and prints prepared with the novel come pounds of the general formula (1) are distinguished by very bright shades. The dyeings and prints on cellulosic fiber materials, in particular, have a good light fastness and very good wet fastness properties, such as washing, :
I
milling, water, seawater, crusading and acid as well as alkaline perspiration fastness properties, and also a Good pleating vastness, hot pressing fastness and rubbing fastness.
Moreover, the novel compounds of the general for-mute (1) can also be used for the fiber-reactive dyeing of wool. It us possible to dye, with very good fastness properties even wool finished to be non-felting or low-felting of for example H. Rat, Lehrbuch don Textile chemise textbook of Textile Chemistry, published by Springer, 3rd edition (1972), pages 295 - 299, in portico-far the finish by the Hercosett process (page 2~8); and J.Soc. Dyers and Colorists 1972, 93 - 99, and 1975, 33 -44)~
The wool is dyed in a customary known manner from an acidic medium. Thus, acetic acid andlor ammon;um sulk fate or acetic acid and ammonium acetate or sodium acetate, for example, are added to the dye bath to obtain the desired phi To ensure acceptable levelness it is advisable to add customary leveling auxiliaries such as, for example, those based on a reaction product of cyan uric chloride with 3-times the molar amount of an aminobenzene-sulfon;c acid and/or of an aminonaphthalenesulfonic acid or those based on a reaction product of for example, stearylamine with ethylene oxide Thus for example, the compound of the general formula (1) us subjected to phi controlled exhaustion, preferably first from an acid dye-bath with a pi of about 3.5 to 5.5, and toward the end of the dyeing tome the pi us then shifted into the neutral 2~3~) or possibly weakly alkaline range as far as a pi value of 8.5 to bring about the full reactive bond between the come pound of the formula to) and the fiber, in particular for obtaining deep shades The unfixed distaff is dissolved away at the same tome.
The dyeing method described here us also applique-able to preparing dyeings on fiber materials made of other natural polyamides or of synthetic polyamides and polyp urethanes. The maternal to be dyed is generally introduced unto the dye bath at a temperature of about 43C and agitated thereon for some tome, the dye bath is then adjusted to the desired weakly acid preferably weakly acetic acid, phi and the actual dyeing is carried out at a temperature bet-wren I and 98C~ However, the dyeings can also be carried out at the boil or on sealed dyeing machines at temperatures of up to 106C. Since compounds of the general formula (1) are very readily soluble in water, they can with advantage also be used on customary continue-out dyeing methods The t;nctor;al strength of the novel pa compounds of the general formula to) is very high.
The ago compounds of the invention produce very bright yellowish to bluish red dyeings on the materials mentioned, preferably fiber materials.
The examples, which follow, serve to illustrate the invention. The parts are parts by weight and the per-cent ages are percentages by weight, unless otherwise stated Parts by weight relate to parts by volume as the kilogram relates to the liter.
The compounds described on the examples by formula ~j2~3~) are given in the form of the free acid; they are generally prepared and isolated on the form of their salts, prefer-ably sodium or potassium salts, and are used for dyeing on the form of their salts. Similarly, the starting come S pounds mentioned on the following examples, in particular tabled examples, in the form of the free acid can be used in the synthesis in the form of the acid or in the form of their salts, preferably alkali metal salts, such as sodium or potassium salts Example 1 a) A suspension of 225.2 parts of 1-amino-8-naphthol-
The hydraulic acid liberated in the course of the condensation reactions us bound by means of ac;d-b;nd;ng agents such as, for example, sodium hydroxide, potassium hydro~;de, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate sodium acetate or a basic sodium phosphate.
Examples of amino compounds of the general formula (3) which can be used as starting compounds for preparing the muons compounds of the invention are I sulfite-ethylsulfonyl)-ani!ine, 2-methoxy-5-~-sulfatoethylsulfon-yl)-aniline, 2,5-dimethoxy-4-~-sulfatoethylsulfonyL)-aniline, 2-methoxy-4-t~-sulfatoethylsulfonyl)-aniline, 4-methoxy-5-(~-sulfatoethylsulfonyl)-aniline, 2,4-d;methoxy-I sulfatoethylsulfonyl~-an;l;ne, 2-methoxy-5-methyl-4-(~-sulfatoethylsulfonyl)-aniline, 2-methyl-5-(~-sulfato-ethylsulfonyl)-an;l;ne, 2,5-dimethyl-4-(~-sulfatoethyl-sulfonyl)-an;l;ne, 2~6-d;methyl-4-t~-sulfatoethylsulfonyl)-aniline, 4-methyl-3-t~-sulfatoethylsulfonyl)-aniline and on particular 4-~-sulfatoethylsulfonyl)-an;l;ne and those derivatives of these aniline compounds in which the -sulfatoethylsulfonyl group has been replaced by a vinyl-sulfonyl, a ~-th;osulfatoethylsulfonyl or a chloroethyl-suifonyl group.
Examples of amino compounds of the general formula 16) which can be used as starting compounds in the proper I
lion of the ago compounds of the invention are I
suLfatoethylsulfonyl)-an;l;ne, methyl sulfatoethyl-sulfonyl)-aniline, 4-methyl-3-(~-sulfatoethylsulfonyl)-aniline, 2,5-d;methyl-4-(~-sulfatoethylsulfonyl)-aniline, 2~6-dimethyl-4-(~-sulfatoethylsulfonyl~-aniline, I
sulfatoethylsulfonyl)-aniline-2-sulfonic acid, 6 (I-sulfatoethylsulfonyl)-2-aminonaphthalene-1-sulfonito acid, 8-(~-sulfatoethylsulfonyl)-2-aminonaphthalenY, So sulfatoethylsulfonyl)-2-am;nonaphthaleneO sulfite-ethylsulfonyl)-2-aminonaphthalene-6-sulfon;c acid and in particular 4-(~-sulfatoethylsulfonyl)-an;line and those derivatives of these aniline and naphthylamine compounds in which the ~-sulfatoethylsulfonyl group has been no-placed by a vinylsulfonyl, ~-thiosulfatoethylsulfonyl or ~-chloroethylsulfonyl group.
Of the ago compounds of the invention those are particularly noteworthy which have the general formula (1) on which D denotes a Bunsen nucleus and R1, R2, R3 and R4 each represent a hydrogen atom or in which D denotes a naphthalene nucleus, R1 us a hydrogen atom or a sulfa group, and R2, R3 and R4 each represent a hydrogen atom.
Of the ago compounds of the invention, those are also preferred in which the X groups represent a vinyl group or, on particular, a ~-sulfatoethyl group.
Other noteworthy ago compounds of the invention are those described in Examples 1, I 7, 16, 30, 42 and 49.
The formula I compounds prepared in the manner of the invention can be separated from the synthesis soul-lion by generally known methods, for example either by 3122~L36~
precipitating them from the reaction medium by means of electrolytes such as, for example, sodium chloride or potassium chloride, or by evaporating the reaction soul-lion, for example by spray drying where a buffer substance can be added to thus reaction solution.
The ago compounds of the invention have valuable distaff properties. because of the two fiber-react;ve groups of the vinylsulfonyl series and because of the halogenotriaz;nyl radical, they have fiber-react;ve pro-purities The new compounds are preferably used for coloring in the general sense defined earlier) hydroxy- and/or ~arboxam;de-contain;ng materials, for example on the form of sheet-Like structures, such as paper or leather or films, such as, for example, those made of polyamide, or in the unshaped state, sushi as, for example, polyamide or polyurethane, but on particular these materials in fiber form The solutions of these ago compounds obtained in the synthesis of compounds of the invention can also be used directly in dyeing as Cody compositions/ of approp-rate after a buffer substance has been added or the soul-ton has been concentrated or diluted. The present invent lion therefore also relates to the use of compounds of the general formula (1) coloring yin the above sense) these materials or rather to processes for coloring such materials on a completely conventional manner in which a compound of the general formula I is used as colorant.
The materials are preferably used in the fornl of fiber materials, on particular on the form of textile fibers, such as yarns, packages or fabrics.
~L2~2~L3~C~
Hydroxy - containing materials are those of natural or synthetic organ, such as, for example, cellulosic fiber materials or their regenerated products and polyvinyl alcohols. Cellulosic fiber materials are preferably S cotton, but also other vegetable fibers, such as linen, hemp, jute or Rome fibers; examples of regenerated cell-logic fibers are viscose staple and filament viscose.
Examples of carboxam;de-conta;n;ng materials are synthetic and natural polyamides and polyurethane, in particular in the form of fibers, for example wool and other animal hairs, silk, leather, nylon-6,6, Nolan nylon-11 and Nolan The novel compounds of the general formula (1) can be applied and fixed to said substrates, in particular said fiber materials, by the application techniques known for water-soluble distaffs, in particular those known for ~ater-solubler f;ber-reactive distaffs.
For instance, applied to cellulose fibers by exhaust methods from a long liquor using various acid-2Q binding agents and, if appropriate, neutral salts, swishes sodium chloride or sodium sulfate, they give very good color yields and excellent color buildup Dyeing is preferably carried out in an aqueous bath at temperatures between 60 and 105C, if appropriate at temperatures of up to SKYE under pressure, and, if appropriate, in the presence of customary dyeing auxiliaries. The dyeing can be carried out by introducing the material into a warm bath and gradually raising the temperature of this bath to the desired dyeing temperature and completing the 36~
dyeing process at thus temperature Neutral salts which accelerate the exhaustion of the distaff can be added to the bath, of desired only after the actual dyeing topper-lure has been reached.
The padding method also gives excellent color yields and a very good color build-up on cellulosic fibers, with toe aid of an acid-bînding agent on which the dyes can be foxed on a customary mannerly material padded with the dye liquor, leaving the to stand at room temperature or Elena-ted temperatures, for example up to about 60C~ by steaming or by means of dry heat Strong prints having well-del;neated contours and a clear white ground are also obtained in customary print-no methods for cellulose fibers, which can be carried out in one step - for example by printing with a print paste containing sodium bicarbonate or a different acid-binding agent and then steaming at Tao 103C - or in two steps, for example by printing with a neutral or weekly acid print paste and then fixing either by passing the printed goods through a hot electrolyte-containing alga-line bath or by over padding with an alkaline electrolyte-containing paid jug liquor and then leaving the over padded material to stand or steaming it or treating it with dry heat. The outcome of the prints varies only little Thea changing fixing cond;t;ons.
In dry heat fixing by customary thermof;x;ng methods, hot air at 120 to 200C us used. In addition to customary steam at 101 to 103C, it is also possible to use superheated steam or saturated steam at temperatures of us to 160C.
36~
Examples of agents which bond acid and effect the fixation of the compound of the formula I on cellulosic fibers are ~ater-soluble basic salts of alkali metals and also alkaline earth metals Thea inorganic or organic acids, or compounds which liberate alkali when heated. The alkali metal hydroxides and alkali metal salts of weak to medium inorganic or organic acids are particularly note-worthy, the sodium and putts compounds in particular being intended among the alkali metal compounds. Examples 1Q of such acid-binding agents are sodium hydroxide, poles-slum hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium format, sodium dihydrogen-phosphate, sodium hydroge~phosphate, sodium trichloro-acetate, sodium silicate and trisodium phosphate.
The treatment of compounds of the invention with an acid-b;nding agent, if appropriate under heat, chemically bonds the compounds of the invention (distaffs) to the cellulose fiber; applied on dyeing and printing methods, they are distinguished on these fiber materials by a high degree of fixation. The cellulose dyeings have excellent wet fastness properties after the customary after treatment whereby unfixed distaff is removed by rinsing, in portico-far since the unfixed distaff can be readily washed out thanks to the fact that it is readily soluble on cold water.
Dyeings and prints prepared with the novel come pounds of the general formula (1) are distinguished by very bright shades. The dyeings and prints on cellulosic fiber materials, in particular, have a good light fastness and very good wet fastness properties, such as washing, :
I
milling, water, seawater, crusading and acid as well as alkaline perspiration fastness properties, and also a Good pleating vastness, hot pressing fastness and rubbing fastness.
Moreover, the novel compounds of the general for-mute (1) can also be used for the fiber-reactive dyeing of wool. It us possible to dye, with very good fastness properties even wool finished to be non-felting or low-felting of for example H. Rat, Lehrbuch don Textile chemise textbook of Textile Chemistry, published by Springer, 3rd edition (1972), pages 295 - 299, in portico-far the finish by the Hercosett process (page 2~8); and J.Soc. Dyers and Colorists 1972, 93 - 99, and 1975, 33 -44)~
The wool is dyed in a customary known manner from an acidic medium. Thus, acetic acid andlor ammon;um sulk fate or acetic acid and ammonium acetate or sodium acetate, for example, are added to the dye bath to obtain the desired phi To ensure acceptable levelness it is advisable to add customary leveling auxiliaries such as, for example, those based on a reaction product of cyan uric chloride with 3-times the molar amount of an aminobenzene-sulfon;c acid and/or of an aminonaphthalenesulfonic acid or those based on a reaction product of for example, stearylamine with ethylene oxide Thus for example, the compound of the general formula (1) us subjected to phi controlled exhaustion, preferably first from an acid dye-bath with a pi of about 3.5 to 5.5, and toward the end of the dyeing tome the pi us then shifted into the neutral 2~3~) or possibly weakly alkaline range as far as a pi value of 8.5 to bring about the full reactive bond between the come pound of the formula to) and the fiber, in particular for obtaining deep shades The unfixed distaff is dissolved away at the same tome.
The dyeing method described here us also applique-able to preparing dyeings on fiber materials made of other natural polyamides or of synthetic polyamides and polyp urethanes. The maternal to be dyed is generally introduced unto the dye bath at a temperature of about 43C and agitated thereon for some tome, the dye bath is then adjusted to the desired weakly acid preferably weakly acetic acid, phi and the actual dyeing is carried out at a temperature bet-wren I and 98C~ However, the dyeings can also be carried out at the boil or on sealed dyeing machines at temperatures of up to 106C. Since compounds of the general formula (1) are very readily soluble in water, they can with advantage also be used on customary continue-out dyeing methods The t;nctor;al strength of the novel pa compounds of the general formula to) is very high.
The ago compounds of the invention produce very bright yellowish to bluish red dyeings on the materials mentioned, preferably fiber materials.
The examples, which follow, serve to illustrate the invention. The parts are parts by weight and the per-cent ages are percentages by weight, unless otherwise stated Parts by weight relate to parts by volume as the kilogram relates to the liter.
The compounds described on the examples by formula ~j2~3~) are given in the form of the free acid; they are generally prepared and isolated on the form of their salts, prefer-ably sodium or potassium salts, and are used for dyeing on the form of their salts. Similarly, the starting come S pounds mentioned on the following examples, in particular tabled examples, in the form of the free acid can be used in the synthesis in the form of the acid or in the form of their salts, preferably alkali metal salts, such as sodium or potassium salts Example 1 a) A suspension of 225.2 parts of 1-amino-8-naphthol-
4,6-disuLfonic acid in 1,440 parts of water and 720 parts of ice us admixed by efficient stirring with 155.Z parts of cyan uric chloride; the reaction batch is stirred at a temperature battalion 3 and 5C and pi 1.7 Tao, maintained by means of sodium bicarbonate, for 4 hours.
b) The diazonium salt of the dyes component is pro-pared in a separate operation: a solution at pi 6.7t~ 6.8 of 224.8 parts of 4-B-sulfatoethylsulfonylaniline in 640 parts of water is admixed with 105 parts by volume of a 40%
strength aqueous sodium nitrite solution. This mixture is alloyed to slow with efficient stirring into a mixture of 800 parts of crushed ice and 70 parts by volume of 95%
strength aqueous sulfuric acid. The resulting mixture is stirred at 0C t~5C for one hour, and, as customary, excess nitrous acid is then destroyed with a little amino-sulfonic acid c) The primary condensation product prepared in this example under a), from cyanur;c chloride and an amino-naphtholdisulfon;c acid us combined with the d;azon;umsalt solution described in this example under b). To start the coupling reaction the strongly acid reaction mixture is adjusted at a temperature of about 5C to pi 4.0 - 4.5 by means of calcium carbonate and the tempera-lure is raised to 15 - 20C. Stirring us continued at this pi and this temperature for some hours, until the coupling has ended.
d) The solution of the muons compound of c) us come brined with a solution, having a pi 5.5 Jo 6.0, of 247.3 parts of~-~-sulfatoethylsulfonylanil;ne in 640 parts of water.
The pi us maintained at about 5, and the reaction mixture is heated to a temperature of 60 to 65C on the course of two hours. The mixture is then wrought to a pi of 6.0 to 6.5 by means of calcium carbonate, and the precipitated calcium sulfate us filtered off loath suction after 15 minutes and washed with water. The combined filtrate and wash-water is freed from calcium ions by adding sodium oxalate, the calcium oxalate is filtered off with suction, 2Q and the filtrate is spray-dried.
The product comprises about 1~120 parts of a pow don which contains electrolyte salts predominantly sodium chloride and sodium sulfate) and 7û% of the sodium salt of the compound of the formula ~22~L~6~
Of N N
Ho NH N - NH Sly S2 ~03S OOZE
fH2 S03H
CHIHUAHUAS
Thus compound has very good distaff properties and on application by the application and fixing methods custom-cry on industry for fiber-reactive distaffs produces, on the materials mentioned in the descriptive section, such as cellulosic fiber materials, in particular cotton, strong red dyeings and prints having very good fastness properties, of which the most noteworthy are the very good washing, light, alkali acid, water, seawater, perspire-lion and rubbing fastness properties. The dyeings Aurelius distinguished by their high degree of fixation on the cellulose materials.
Example 2 __ 19.4 parts of cyanur;c chloride and 31.9 parts of 1-amino-~-naphthol-3,6-disulfon;c acid are rapidly added with efficient stirring to a mixture of 330 parts of water and 40 parts of ice. The mixture is stirred eta pi of 1.5 to 2.0 and a temperature between 10 and 15C for about 3~5 hours. The solution of this primary condensation product us then clarified by means of kieselguhr and it ltration.
This solution is combined with a conventionally sodium nitrite and sulfuric acid d;azotized aqueous sup-~2~6~
pension of the diazon;um salt of 41.1 parts of I
sulfatoethylsulfonyl)-2-aminonaphthalene-1-sulfonito acid and the strongly acid coupling mixture is then brought to pi 4.0 - US by means of calcium carbonate at a tempera lure of about 10C and is stirred at 10 to 14C and within this pi range for a few hours.
A solution (at pi 5) of 29.5 parts of 4 -I-sulfatoethylsuLfonylaniline in 100 parts of water is then added, and the batch is stirred at 18 to 22C for two to three hours, us then heated to 50 to 55C and us held at thus temperature for 30 minutes while the pi is kept at a constant value of 4.0 to 4.5 by means of calcium carbonate.
The batch us then stirred at 18 to 20C for a few hours, the calcium sulfate is filtered off with suction and US washed with water, and on thus combined filtrate and wash water the calcium ions are precipitated by means of sodium oxalate at pi 4.5 - 5.0 and 30C. The mixture us filtered after one hour of stirring, and the muons come pound of the invention is isolated from the filtrate by Z0 spray-drying.
The product comprises 155.6 parts of a dark red powder Shea, in addition to electrolyte salts, contains about 73% of the sodium salt of the compound of the formula Sue HO . NH ~N~NH kiwi Do N _ No 1 2 CH2-CH2-0S03~ .
2;~36~
This muons compound of the invention has very good fiber reactive distaff properties and on application by the printing and dyeing methods customary in industry for f;ber-reactive distaffs produces, for example, on cell-logic fiber materials strong red dyeings and prints of very good manufacturing and end-use fastness properties, of which the most noteworthy are the light fastness, the Nash, persp;rat;on, water and seawater fastness properties and the resistance to chlorinated tap water. The degree of fixation of this muons compound of the invention on cellulosic fiber materials is very high Examples to 72 The tabled examples which follow describe further muons compounds of the invention, with the aid
b) The diazonium salt of the dyes component is pro-pared in a separate operation: a solution at pi 6.7t~ 6.8 of 224.8 parts of 4-B-sulfatoethylsulfonylaniline in 640 parts of water is admixed with 105 parts by volume of a 40%
strength aqueous sodium nitrite solution. This mixture is alloyed to slow with efficient stirring into a mixture of 800 parts of crushed ice and 70 parts by volume of 95%
strength aqueous sulfuric acid. The resulting mixture is stirred at 0C t~5C for one hour, and, as customary, excess nitrous acid is then destroyed with a little amino-sulfonic acid c) The primary condensation product prepared in this example under a), from cyanur;c chloride and an amino-naphtholdisulfon;c acid us combined with the d;azon;umsalt solution described in this example under b). To start the coupling reaction the strongly acid reaction mixture is adjusted at a temperature of about 5C to pi 4.0 - 4.5 by means of calcium carbonate and the tempera-lure is raised to 15 - 20C. Stirring us continued at this pi and this temperature for some hours, until the coupling has ended.
d) The solution of the muons compound of c) us come brined with a solution, having a pi 5.5 Jo 6.0, of 247.3 parts of~-~-sulfatoethylsulfonylanil;ne in 640 parts of water.
The pi us maintained at about 5, and the reaction mixture is heated to a temperature of 60 to 65C on the course of two hours. The mixture is then wrought to a pi of 6.0 to 6.5 by means of calcium carbonate, and the precipitated calcium sulfate us filtered off loath suction after 15 minutes and washed with water. The combined filtrate and wash-water is freed from calcium ions by adding sodium oxalate, the calcium oxalate is filtered off with suction, 2Q and the filtrate is spray-dried.
The product comprises about 1~120 parts of a pow don which contains electrolyte salts predominantly sodium chloride and sodium sulfate) and 7û% of the sodium salt of the compound of the formula ~22~L~6~
Of N N
Ho NH N - NH Sly S2 ~03S OOZE
fH2 S03H
CHIHUAHUAS
Thus compound has very good distaff properties and on application by the application and fixing methods custom-cry on industry for fiber-reactive distaffs produces, on the materials mentioned in the descriptive section, such as cellulosic fiber materials, in particular cotton, strong red dyeings and prints having very good fastness properties, of which the most noteworthy are the very good washing, light, alkali acid, water, seawater, perspire-lion and rubbing fastness properties. The dyeings Aurelius distinguished by their high degree of fixation on the cellulose materials.
Example 2 __ 19.4 parts of cyanur;c chloride and 31.9 parts of 1-amino-~-naphthol-3,6-disulfon;c acid are rapidly added with efficient stirring to a mixture of 330 parts of water and 40 parts of ice. The mixture is stirred eta pi of 1.5 to 2.0 and a temperature between 10 and 15C for about 3~5 hours. The solution of this primary condensation product us then clarified by means of kieselguhr and it ltration.
This solution is combined with a conventionally sodium nitrite and sulfuric acid d;azotized aqueous sup-~2~6~
pension of the diazon;um salt of 41.1 parts of I
sulfatoethylsulfonyl)-2-aminonaphthalene-1-sulfonito acid and the strongly acid coupling mixture is then brought to pi 4.0 - US by means of calcium carbonate at a tempera lure of about 10C and is stirred at 10 to 14C and within this pi range for a few hours.
A solution (at pi 5) of 29.5 parts of 4 -I-sulfatoethylsuLfonylaniline in 100 parts of water is then added, and the batch is stirred at 18 to 22C for two to three hours, us then heated to 50 to 55C and us held at thus temperature for 30 minutes while the pi is kept at a constant value of 4.0 to 4.5 by means of calcium carbonate.
The batch us then stirred at 18 to 20C for a few hours, the calcium sulfate is filtered off with suction and US washed with water, and on thus combined filtrate and wash water the calcium ions are precipitated by means of sodium oxalate at pi 4.5 - 5.0 and 30C. The mixture us filtered after one hour of stirring, and the muons come pound of the invention is isolated from the filtrate by Z0 spray-drying.
The product comprises 155.6 parts of a dark red powder Shea, in addition to electrolyte salts, contains about 73% of the sodium salt of the compound of the formula Sue HO . NH ~N~NH kiwi Do N _ No 1 2 CH2-CH2-0S03~ .
2;~36~
This muons compound of the invention has very good fiber reactive distaff properties and on application by the printing and dyeing methods customary in industry for f;ber-reactive distaffs produces, for example, on cell-logic fiber materials strong red dyeings and prints of very good manufacturing and end-use fastness properties, of which the most noteworthy are the light fastness, the Nash, persp;rat;on, water and seawater fastness properties and the resistance to chlorinated tap water. The degree of fixation of this muons compound of the invention on cellulosic fiber materials is very high Examples to 72 The tabled examples which follow describe further muons compounds of the invention, with the aid
5 of their components, by the general formula aye or N N
Ho NH N
Do ON - N aye) ~03S S03~
They can be prepared in a manner of the invention, for example in analogy to one of the above illustrative examples, from their components (cyan uric chloride, cyan-arc bromide or cyanur;c fluoride, the amino compound D1-NH2, corresponding to formula to) as dyes component, I
amino naphthol-3,6- or -4,6-disulfonic acid as coupling component (which us characterized in the particular tabled :~22~3~
examples by the position of one of the sulfa groups relative Jo the amino group) and the amiss compound ANN correspond-in to formula (3)). They have very good f;ber-reactive distaff properties and on application by the application methods customary in the dyeing and printing industry, preferably by the application and fixing methods customary in industry for fiber-reactive distaffs, produce, on the materials mentioned on the descriptive section, such as, on particular, cellulose fiber materials, strong dyeings and prints having good fastness properties and the shade indicated in the particular tabled example.
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Claims (17)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A water-soluble azo compound of the formula (1) (1) in which M represents a hydrogen atom or the equivalent of a metal, D is a benzene nucleus or a naphthalene nucleus, R1 denotes a hydrogen atom or an alkyl group of 1 to 4 carbon atoms or a sulfo group, R2 is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, R3 represents a hydrogen atom, an alkyl group of 1 to 4 carbon atoms or an alkoxy group of 1 to 4 carbon atoms and R4 denotes a hydrogen atom or an alkyl group of 1 to 4 carbon atoms or an alkoxy group of 1 to 4 carbon atoms, where R1, R2, R3 and R4 can be identical to or different from one another, Y is a fluorine atom or a bromine atom or a chlorine atom and X in each case denotes a .beta.-sulfatoethyl group or a .beta.-thio-sulfatoethyl group or a .beta.-chloroethyl group or a vinyl group, where the two X can be identical to or different from one another, and the group(s) of the formula -SO2-X are bonded in the benzene nucleus in meta- or para-position relative to the azo group or acylated amino group and can be bonded in the naphthalene nucleus in any position, and the second group of the formula -SO3M in the radical of the aminonaphtholdisulfonic acid is bonded in meta- or para-position relative to the acylated amino group.
2. A compound as claimed in claim 1 of the formula (1), in which D denotes a benzene nucleus and R1, R2, R3 and R4 each represent a hydrogen atom.
3. A compound as claimed in claim 1 of the formula (1), in which D denotes a naphthalene nucleus, R2 is a hydrogen atom or a sulfo group and R2, R3 and R4 each represent a hydrogen atom.
4. A compound as claimed in claims 1, 2 or 3 wherein Y is a chlorine atom.
5. A compound as claimed in claims 1, 2 or 3, in which X
represents a vinyl or .beta.-sulfatoethyl group.
represents a vinyl or .beta.-sulfatoethyl group.
6. A compound as claimed in claims 1, 2 or 3, in which X
in each case is a .beta.-sulfatoethyl group.
in each case is a .beta.-sulfatoethyl group.
7. A compound as claimed in claims 1, 2 or 3 in which the moieties -SO2-X are bonded in the benzene nucleus in para-position relative to the azo group or acylated amino group.
8. A compound as claimed in claims 1, 2 or 3 in which the moieties -SO2-X are bonded in the benzene nucleus in para-position relative to the azo group or acylated amino group and X represents a vinyl or .beta.-sulfatoethyl group.
9. A compound as claimed in claims 1, 2 or 3 in which the moieties -SO2-X are bonded in the benzene nucleus in para-position relative to the azo group or acylated amino group and each X represents a .beta.-sulfatoethyl group.
10. A compound as claimed in claim 1 in which M denotes hydrogen, sodium or potassium.
11. A compound as claimed in claims 1, 2 or 3, in which X
represents a vinyl or .beta.-sulfatoethyl group and M denotes hydrogen, sodium or potassium.
represents a vinyl or .beta.-sulfatoethyl group and M denotes hydrogen, sodium or potassium.
12. A compound as claimed in claims 1, 2 or 3 in which the moieties -SO2-X are bonded in the benzene nucleus in para-position relative to the azo group or acylated amino group and M denotes hydrogen, sodium or potassium.
13. A compound as claimed in claims 1, 2 or 3 in which the moieties -SO2-X are bonded in the benzene nucleus in para-position relative to the azo group or acylated amino group and each X represents a .beta.-sulfatoethyl group and M denotes hydrogen, sodium or potassium.
14. Process for preparing an azo compound of formula (1) mentioned and defined in claim 1, which comprises reacting a com-pound of the formula (2) (2) in which D, R1, R2, M, X and Y have the meanings mentioned in claim 1 and the second group of the formula -SO3M in the radical of the aminonaphtholdisulfonic acid is bonded in meta- or para-position relative to the acylated amino group, with an aromatic amine of the formula (3) (3) in which R3, R4 and X have the meanings mentioned in claim 1 and the group of the formula -SO2-X is bonded in the benzene nucleus in meta- or para-position relative to the amino group, or reacting an azo compound of the formula (4) (4) in which D, R1, R2, X and M have the meanings mentioned in claim 1 and the second group of the formula -SO3M in the radical of the aminonaphtholdisulfonic acid is bonded in meta- or para-position relative to the amino group, with a dihalogenotriazinyl compound of the formula (5) (5) in which Y, R3, R4 and X have the meanings mentioned in claim l and the group of the formula -SO2-X is bonded in the benzene nucleus in meta- or para-position relative to the acylated amino group.
15. A process for dyeing hydroxyl- and/or carboxamide-con-taining material in which a dyestuff is applied onto or into the material and fixed, if appropriate under heat and/or in the presence of an acid-binding agent, which comprises using as dye-stuff a compound of the formula (1) mentioned and defined in claim 1.
16. A process for the preparation of an azo compound of formula (1) defined in claim 1, which comprises reacting a dia-zonium salt of an amino compound of the formula (6) wherein D is a benzene nucleus or a naphthalene nucleus, R1 denotes a hydrogen atom or an alkyl group of 1 to 4 carbon atoms or a sulfo group, R2 denotes a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, X denotes a .beta.-sulfatoethyl group or a.beta.-thiosulfatoethyl group or a.beta.-chloroethyl group or a vinyl group, and the group of the formula -SO2-X is bonded in the benzene nucleus in meta- or para-position relative to the amino group, and aniline compound of the formula (3) wherein R3 represents a hydrogen atom, an alkyl group of 1 to 4 carbon atoms or an alkoxy group of 1 to 4 carbon atoms, R4 represents a hydrogen atom, an alkyl group of 1 to 4 carbon atoms or an alkoxy group of 1 to 4 carbon atoms, X denotes a .beta.-sulfatoethyl group or a .beta.-thiosulfatoethyl group or a.beta.-chloroethyl group of a vinyl group, and the group of the formula -SO2-X is bonded in the benzene nucleus in meta- or para-position relative to the amino group, in any order with 1-(2',4'-dihalogeno-1',3',5'-triazin-6'yl)-amino-8-naphthol-3,6- or -4,6-disulfonic acid.
17. A composition for dyeing (coloring) a material, char-acterized by a content of an azo compound defined in claim 1, of 20 to 70 % by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3217812.3 | 1982-05-12 | ||
| DE19823217812 DE3217812A1 (en) | 1982-05-12 | 1982-05-12 | MONOAZO COMPOUNDS, METHOD FOR THEIR PRODUCTION AND THEIR USE AS DYES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1221360A true CA1221360A (en) | 1987-05-05 |
Family
ID=6163351
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000427942A Expired CA1221360A (en) | 1982-05-12 | 1983-05-11 | Monoazo compounds, processes for their preparation, and their use as dyestuffs |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0094055B1 (en) |
| JP (1) | JPS58204051A (en) |
| KR (1) | KR910006960B1 (en) |
| AR (1) | AR241411A1 (en) |
| BR (1) | BR8302503A (en) |
| CA (1) | CA1221360A (en) |
| DE (2) | DE3217812A1 (en) |
| IN (1) | IN157455B (en) |
| MX (1) | MX156077A (en) |
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| US5980590A (en) * | 1995-12-28 | 1999-11-09 | Dystar Texilfarben Gmbh & Co. Deutschland Kg | Dyestuff mixtures of water-soluble fiber-reactive azo dyestuffs, processes for their preparation and their use |
| US6136045A (en) * | 1998-08-13 | 2000-10-24 | Dystar Textilfarben Gmbh & Co. Deutschland Kg | Dye mixture comprising water-soluble fiber-reactive azo dyes, preparation thereof and use thereof |
| US6624291B2 (en) | 2000-07-25 | 2003-09-23 | Dystar Textilfarben Gmbh & Co. Deutschland Kg | Yellow-reactive monoazo dyes containing a tertiary or a quarternary nitrogen group, methods for their preparation and use thereof for dyeing hydroxy-and/or carboxamido-containing fiber material |
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| CN101914302A (en) * | 2010-07-17 | 2010-12-15 | 青岛大学 | K-type active light-resistant red azo dye and preparation method thereof |
| CN104262998A (en) * | 2014-09-03 | 2015-01-07 | 蓬莱嘉信染料化工股份有限公司 | Red reactive dye for dyeing at normal-moderate temperature and compound mixture thereof |
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|---|---|---|---|---|
| EP0141367B1 (en) * | 1983-10-26 | 1988-03-30 | Ciba-Geigy Ag | Reactive dyes, their preparation and their use |
| EP0177445B1 (en) * | 1984-09-26 | 1990-05-23 | Ciba-Geigy Ag | Reactive dyes, their preparation and their use |
| DE3510179A1 (en) * | 1985-03-21 | 1986-09-25 | Hoechst Ag, 6230 Frankfurt | WATER-SOLUBLE MONO AND DISAZO COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS DYES |
| DE3510180A1 (en) * | 1985-03-21 | 1986-09-25 | Hoechst Ag, 6230 Frankfurt | WATER-SOLUBLE AZO COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS DYES |
| DE3624136A1 (en) * | 1985-09-30 | 1987-04-09 | Hoechst Ag | WATER-SOLUBLE AZO COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS DYES |
| US5003053A (en) * | 1987-02-14 | 1991-03-26 | Hoechst Aktiengesellschaft | Water-soluble monoazo compounds containing a p-aminophenylamino- and chloro- or fluoro-substituted triazinylamino group and a fiber-reactive group selected from the vinylsulfone series, suitable as dyestuffs |
| DE3704660A1 (en) * | 1987-02-14 | 1988-08-25 | Hoechst Ag | WATER-SOLUBLE AZO COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS DYES |
| US5037965A (en) * | 1987-12-01 | 1991-08-06 | Sumitomo Chemical Company, Limited | Monoazo red dye compound having vinylsulfone type fiber reactive groups |
| JP2674154B2 (en) * | 1988-01-20 | 1997-11-12 | 住友化学工業株式会社 | Monoazo compound and method for dyeing or printing fiber material using the same |
| US5243034A (en) * | 1988-12-21 | 1993-09-07 | Hoechst Aktiengesellschaft | Disazo dyestuffs having a triazine moiety and a fiberreactive group of vinylsulfone series |
| GB9025018D0 (en) * | 1990-11-16 | 1991-01-02 | Ici Plc | Reactive dyes |
| MX9102026A (en) * | 1990-11-16 | 1992-06-01 | Ici Plc | REACTIVE DYES |
| GB9111427D0 (en) * | 1991-05-28 | 1991-07-17 | Ici Plc | Reactive dyes |
| US5428141A (en) * | 1991-12-05 | 1995-06-27 | Bayer Aktiengesellschaft | Azo dyestuffs containing fluorotriazinyl and vinylsulfonylmethyl-type reactive groups |
| US5330539A (en) * | 1991-12-18 | 1994-07-19 | Hoechst Celanese Corporation | Fiber reactive dyes - applications with low salt |
| DE4214740A1 (en) * | 1992-05-04 | 1993-11-11 | Bayer Ag | Reactive dyes, their manufacture and use |
| DE4417719A1 (en) * | 1994-05-20 | 1995-11-23 | Hoechst Ag | Reactive dyes useful for dyeing and printing e.g. cellulose, polyamide or polyester |
| US5514717A (en) * | 1994-10-26 | 1996-05-07 | Monsanto Company | Fluoroalkenyl compounds and their use as pest control agents |
| DE4438544A1 (en) * | 1994-10-28 | 1996-05-02 | Bayer Ag | Process for dyeing and printing materials containing hydroxyl and / or carbonamide groups |
| DE4447276C2 (en) * | 1994-12-30 | 1998-08-27 | Dystar Textilfarben Gmbh & Co | Dye mixture of water-soluble fiber-reactive azo dyes, process for their preparation and their use |
| DE19510135A1 (en) * | 1995-03-21 | 1996-09-26 | Bayer Ag | Monoazoreactive dyes |
| DE19511688C2 (en) * | 1995-03-30 | 1999-07-22 | Dystar Textilfarben Gmbh & Co | Dye mixtures of fiber-reactive azo dyes and their use for dyeing fiber material containing hydroxyl and / or carbonamide groups |
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| DE10017555A1 (en) | 2000-04-08 | 2001-10-11 | Dystar Textilfarben Gmbh & Co | Dye mixture of water-soluble fiber-reactive azo dyes, process for their preparation and their use |
| EP1247841B1 (en) * | 2001-04-03 | 2012-09-26 | Huntsman Advanced Materials (Switzerland) GmbH | Reactive dyes, process for their preparation and the use thereof |
| BR112012020225B8 (en) * | 2010-02-18 | 2023-05-16 | Huntsman Adv Mat Switzerland | FIBER-REACTIVE DYE MIXTURES, AND METHODS FOR DYEING OR TRICHROME PRINTING |
| CN102277011A (en) * | 2011-06-17 | 2011-12-14 | 上海雅运纺织化工有限公司 | Red reactive dye composition and application thereof to fiber dyeing |
| CN103554976A (en) * | 2013-09-29 | 2014-02-05 | 天津德凯化工股份有限公司 | Red reactive dye and preparation method thereof |
| CN103554980A (en) * | 2013-09-29 | 2014-02-05 | 天津德凯化工股份有限公司 | Red reactive dye and preparation method thereof |
| CN103554981A (en) * | 2013-09-29 | 2014-02-05 | 天津德凯化工股份有限公司 | Red reactive dye |
| KR20180006943A (en) | 2015-05-12 | 2018-01-19 | 훈츠만 어드밴스트 머티리얼스(스위처랜드) 게엠베하 | Reactive dye mixtures, and uses thereof in dyeing or printing methods of textile fiber materials |
| US20230167304A1 (en) | 2020-04-27 | 2023-06-01 | Huntsman Advanced Materials (Switzerland) Gmbh | Mixture Of Reactive Dyes And Their Use For The Dyeing Or Printing Of Textile Fibre Materials |
| TW202340390A (en) | 2022-01-25 | 2023-10-16 | 瑞士商亨斯邁紡織染化（瑞士）有限公司 | Isomeric mixture of reactive dyes and their use for the dyeing or printing of textile fibre materials |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1265698C2 (en) * | 1961-05-06 | 1968-11-07 | Hoechst Ag | Process for the production of wetfast colorations and prints |
| CH627206A5 (en) * | 1978-07-06 | 1981-12-31 | Ciba Geigy Ag |
-
1982
- 1982-05-12 DE DE19823217812 patent/DE3217812A1/en not_active Withdrawn
-
1983
- 1983-03-10 AR AR83292979A patent/AR241411A1/en active
- 1983-05-05 IN IN561/CAL/83A patent/IN157455B/en unknown
- 1983-05-06 EP EP83104470A patent/EP0094055B1/en not_active Expired
- 1983-05-06 DE DE8383104470T patent/DE3368074D1/en not_active Expired
- 1983-05-10 KR KR1019830002010A patent/KR910006960B1/en not_active IP Right Cessation
- 1983-05-11 MX MX197242A patent/MX156077A/en unknown
- 1983-05-11 CA CA000427942A patent/CA1221360A/en not_active Expired
- 1983-05-11 JP JP58081053A patent/JPS58204051A/en active Granted
- 1983-05-12 BR BR8302503A patent/BR8302503A/en not_active IP Right Cessation
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5980590A (en) * | 1995-12-28 | 1999-11-09 | Dystar Texilfarben Gmbh & Co. Deutschland Kg | Dyestuff mixtures of water-soluble fiber-reactive azo dyestuffs, processes for their preparation and their use |
| US6136045A (en) * | 1998-08-13 | 2000-10-24 | Dystar Textilfarben Gmbh & Co. Deutschland Kg | Dye mixture comprising water-soluble fiber-reactive azo dyes, preparation thereof and use thereof |
| US6624291B2 (en) | 2000-07-25 | 2003-09-23 | Dystar Textilfarben Gmbh & Co. Deutschland Kg | Yellow-reactive monoazo dyes containing a tertiary or a quarternary nitrogen group, methods for their preparation and use thereof for dyeing hydroxy-and/or carboxamido-containing fiber material |
| US7091328B2 (en) | 2001-04-20 | 2006-08-15 | Clariant Finance (Bvi) Limited | Fiber-reactive mono-azo dyes |
| CN101914302A (en) * | 2010-07-17 | 2010-12-15 | 青岛大学 | K-type active light-resistant red azo dye and preparation method thereof |
| CN104262998A (en) * | 2014-09-03 | 2015-01-07 | 蓬莱嘉信染料化工股份有限公司 | Red reactive dye for dyeing at normal-moderate temperature and compound mixture thereof |
| CN116004032A (en) * | 2022-12-30 | 2023-04-25 | 上海雅运新材料有限公司 | Red dye compound and synthetic method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3217812A1 (en) | 1983-11-17 |
| AR241411A1 (en) | 1992-07-31 |
| EP0094055B1 (en) | 1986-12-03 |
| BR8302503A (en) | 1984-01-17 |
| IN157455B (en) | 1986-04-05 |
| KR910006960B1 (en) | 1991-09-14 |
| KR840004766A (en) | 1984-10-24 |
| DE3368074D1 (en) | 1987-01-15 |
| JPH0513993B2 (en) | 1993-02-23 |
| JPS58204051A (en) | 1983-11-28 |
| EP0094055A1 (en) | 1983-11-16 |
| MX156077A (en) | 1988-06-14 |
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