CA1320949C - Water-soluble azo compounds, preparation and use thereof as dyes - Google Patents
Water-soluble azo compounds, preparation and use thereof as dyesInfo
- Publication number
- CA1320949C CA1320949C CA000588031A CA588031A CA1320949C CA 1320949 C CA1320949 C CA 1320949C CA 000588031 A CA000588031 A CA 000588031A CA 588031 A CA588031 A CA 588031A CA 1320949 C CA1320949 C CA 1320949C
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- Prior art keywords
- carbon atoms
- compound
- substituted
- group
- sulfo
- Prior art date
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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
- C09B62/4401—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
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- Organic Chemistry (AREA)
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Abstract
ABSTRACT:
Water-soluble azo compounds, preparation and use thereof as dyes Azo compounds which conform to the general formula (1) and are used as fiber-reactive dyes (1) where D is a carboxy- or sulfo-substituted phenylene or naphthylene radical, R is hydrogen or substituted or unsubstituted alkyl, M is hydrogen or a salt-forming metal, such as an alkali metal, is a group of the general formula (2) (2) where Y is halogen, such as fluorine or chlorine, R1 is hydrogen or substituted or unsubstituted alkyl and R2 is hydrogen or substituted or unsubstituted alkyl or a substituted or unsubstituted phenyl or naphthyl group or R1 and R2 together with the nitrogen atom form a hetero-cyclic radical.
The compounds of the formula (1) are suitable for dyeing carboxamido- and/or hydroxy-containing materials, in particular fiber materials, such as wool, synthetic polyamide, in particular cellulose fibers. If applied to the materials using in particular the application and fixing methods customary for fiber-reactive dyes they produce strong fast dyeings in predominantly orange to red shades.
Water-soluble azo compounds, preparation and use thereof as dyes Azo compounds which conform to the general formula (1) and are used as fiber-reactive dyes (1) where D is a carboxy- or sulfo-substituted phenylene or naphthylene radical, R is hydrogen or substituted or unsubstituted alkyl, M is hydrogen or a salt-forming metal, such as an alkali metal, is a group of the general formula (2) (2) where Y is halogen, such as fluorine or chlorine, R1 is hydrogen or substituted or unsubstituted alkyl and R2 is hydrogen or substituted or unsubstituted alkyl or a substituted or unsubstituted phenyl or naphthyl group or R1 and R2 together with the nitrogen atom form a hetero-cyclic radical.
The compounds of the formula (1) are suitable for dyeing carboxamido- and/or hydroxy-containing materials, in particular fiber materials, such as wool, synthetic polyamide, in particular cellulose fibers. If applied to the materials using in particular the application and fixing methods customary for fiber-reactive dyes they produce strong fast dyeings in predominantly orange to red shades.
Description
-~ 3 ~
Description ~ater-~oluble azo cGmpound~t preparation and use thereof ~ dyes S The present inv~ntion relates to fiber-reactive dye~.
The present invention provides novel, u~eful fi~er-reactive monoazo compound~ which po~e~s fiber-reactive dye propertieg and conform to the general formula (1) OH
X N - D -N ~ N ~
R ~ (1) COOM
where the variables have the fDllowing ~eanin~:
D i~ a para- or meta-phenylene group which can be ~ubstitut0d by 1 carboxy group or 1 to 2 sulfo group6, or i~ ~ naphthylene group which contains the azo group bonded in the 1- or 2-position and to which the grouping X-~(R)- i8 bonded in the 5- or 6-po~ition and which can be substituted by one car-boxy group or 1 or 2 ~ulfo group~, R i8 a hydrogen ~tom or an alkyl group of 1 to 4 carbon atoms, such a~ methyl or ethyl, or i~ a hydroxy-, cyano-, carboxy-, sulfo-, sulfato- or phosphato- or phenyl- or ~ulfophenyl-~ubstituted alkyl group of 1 to 4 carbon atoms, ~u~h a8, for example, a benzyl, phenethyl, ~-cyanosthyl ~-carboxyethyl; A-sul~oethyl~ B-~ulf2toethyl/ ~-phosphatoethyl or ~ulfomethyl group, of which preferably hydro~en or me~hyl~
i~ a hydro~en atom or an alkali metal or one ~guivalent of a dival~nt ~etal, a of an alkaline earth metal, a~ for example of calcium, but prefer-ably hydrogen or an alkali m~talt such a~ ~odium or i .
~, , .
Description ~ater-~oluble azo cGmpound~t preparation and use thereof ~ dyes S The present inv~ntion relates to fiber-reactive dye~.
The present invention provides novel, u~eful fi~er-reactive monoazo compound~ which po~e~s fiber-reactive dye propertieg and conform to the general formula (1) OH
X N - D -N ~ N ~
R ~ (1) COOM
where the variables have the fDllowing ~eanin~:
D i~ a para- or meta-phenylene group which can be ~ubstitut0d by 1 carboxy group or 1 to 2 sulfo group6, or i~ ~ naphthylene group which contains the azo group bonded in the 1- or 2-position and to which the grouping X-~(R)- i8 bonded in the 5- or 6-po~ition and which can be substituted by one car-boxy group or 1 or 2 ~ulfo group~, R i8 a hydrogen ~tom or an alkyl group of 1 to 4 carbon atoms, such a~ methyl or ethyl, or i~ a hydroxy-, cyano-, carboxy-, sulfo-, sulfato- or phosphato- or phenyl- or ~ulfophenyl-~ubstituted alkyl group of 1 to 4 carbon atoms, ~u~h a8, for example, a benzyl, phenethyl, ~-cyanosthyl ~-carboxyethyl; A-sul~oethyl~ B-~ulf2toethyl/ ~-phosphatoethyl or ~ulfomethyl group, of which preferably hydro~en or me~hyl~
i~ a hydro~en atom or an alkali metal or one ~guivalent of a dival~nt ~etal, a of an alkaline earth metal, a~ for example of calcium, but prefer-ably hydrogen or an alkali m~talt such a~ ~odium or i .
~, , .
- 2 - ~32~
pc~ta~si~m or l ithi~m, a group of th0 general formula ~ 2 ) Rl N~N
R2~NJ~N~ (~) where Y is halogen, ~uch a~ fluorine and in particular ehlorine, Rl i~ a hydrogen ~tom or an alkyl group Df 1 to 4 earbon atom6, 6uch as ethyl or methyl, or i6 an allsyl group of 1 to 4 carbon atoms which i8 8ub-~tituted by a sulfo, earbo~y, pho~phato, sulfato, hydroxy or eyano ~roup and/or by a phenyl or naph-thyl radieal whieh may lbe substituted by 8ulfo, c:arboxy ,, alkyl of 1 to 4 earbon atoms, alkoxy of to 4 carbon atoms, ehlorine and/or nitro and R2 is ~ hydroslen ~tom or ~n allcyl group of 1 to 4 earbon atom6, ~ueh as ethyl ox ~ethyl, or i~ an alkyl group c)f 1 to 4 earbo~ atoDIs which i~ ~ub-st~tuted by sulfo, earboxy, pho~phato, ~ulfato, hydro~ yano or by a ph~nyl or naphthyl raclieal which ~ay b~ substituted by ~ulfo, earboxy, ~llyl of 1 to 4 earbon atoms, alkoxy of 1 to 4 earbon ~tom~, ehlorine ~nd/or nitro, or denotes a phenyl radieal which ean b~ substituted by 1 " 2 or 3 511b~;t;itUent8 selec~ed from the ~roup consisting of the following ~ tituent~: 2 alkyls of 1 to 4 ~arbon ~toms " ~uch as ~thyl and in particular methyl, 2 ~lkoxi~ of 1 to 9, carbon atoms, 8UC~ as ethoxy and ~e~hoxy, 1 bromine, 2 chlorinQs, 3 sulfos, 2 carboxys, 1 nitro, 1 alkylsulfonyl of 1 to 4 caxbon a~om~ which may be ~ tituted by hydroxy ( such a~, fr: r ea~ample, fl-hydroxyethylsul -iEonyl ), 1 alkyla~aino of 1 to 4 carbon atoms and alkylamino of 1 to 4 car~on at~ms which may be sub~titut~3d ~ n the alkyl radical by hy~oxy, - 3 ~
~ulfato, ~ulfot phosphato, alkanoyloxy o~ 2 to 5 carbon atoms or by carboxy -substituted alkanoyl-amido of 1 to 4 carbon ~toms in the alkylene radical ~uch as ~uccinamido, or R2 denotes a monosulfo-, disulfo~ ox trisulfo-n~phthyl radical, R1 and R2 being identical o or different from each other, or R' and ~2 togekher with the nitrogen atom form a h~tero-cyclic radical composed of an ~lkylene radical composed of 3 to 8 carbon atoms, preferably of 4 to 6 carbon atoms, ~r a further heteroatom, such us a nitrogen atom or oxygen atom, and two alkylene radical~ of 1 to 4 carbon atoms, ~uch as 9 for example, a piperidino, pipera2ino ~r morpholino radical~ .
Substituted alkylamino ~ubstituents in a phenyl ra~ical R2 are ~or example ~-~ulfo~thyl~mino and B-~uccinamido-ethylamino.
Of th~ azo compounds of the general formula (1) according to the invention, e~pecially preferred one~ are tho~e where R ~tands for hydrogen~ tho6e where D i8 a met~- or para-phenylene group each substituted by 1 or 2 ~ulfo groups, those where R1 i8 hydrogen and R2 i~ phenyl which ifi ~ubfitituted by a sulfo group and ~ay additionally be 6ub~tituted by a further ~ulfo group or a ~ethoxy group.
~ulfo groups are gxoups conforming to the general formula -SO3M, carboxy group~ are ~roup~ conforming to the ~eneral formula -COOM, ~ul~ato group~ are groups conorm-ing to the general f~nmul~ -OS03M and phosphato qroup~
are group~ confoxming ~o the general formula ~OPO3M2, in each of which M ha~ one of the ~bovementioned ~eanings.
~he novel azo compound~ can be present in acid form and in the form of their 6alt8. Prefexably they are in ~he form of their salts, in par~icular alkali and slkaline ~arth metal Raltfi, and are preerably al~o used in the ~.
:
~32~
pc~ta~si~m or l ithi~m, a group of th0 general formula ~ 2 ) Rl N~N
R2~NJ~N~ (~) where Y is halogen, ~uch a~ fluorine and in particular ehlorine, Rl i~ a hydrogen ~tom or an alkyl group Df 1 to 4 earbon atom6, 6uch as ethyl or methyl, or i6 an allsyl group of 1 to 4 carbon atoms which i8 8ub-~tituted by a sulfo, earbo~y, pho~phato, sulfato, hydroxy or eyano ~roup and/or by a phenyl or naph-thyl radieal whieh may lbe substituted by 8ulfo, c:arboxy ,, alkyl of 1 to 4 earbon atoms, alkoxy of to 4 carbon atoms, ehlorine and/or nitro and R2 is ~ hydroslen ~tom or ~n allcyl group of 1 to 4 earbon atom6, ~ueh as ethyl ox ~ethyl, or i~ an alkyl group c)f 1 to 4 earbo~ atoDIs which i~ ~ub-st~tuted by sulfo, earboxy, pho~phato, ~ulfato, hydro~ yano or by a ph~nyl or naphthyl raclieal which ~ay b~ substituted by ~ulfo, earboxy, ~llyl of 1 to 4 earbon atoms, alkoxy of 1 to 4 earbon ~tom~, ehlorine ~nd/or nitro, or denotes a phenyl radieal which ean b~ substituted by 1 " 2 or 3 511b~;t;itUent8 selec~ed from the ~roup consisting of the following ~ tituent~: 2 alkyls of 1 to 4 ~arbon ~toms " ~uch as ~thyl and in particular methyl, 2 ~lkoxi~ of 1 to 9, carbon atoms, 8UC~ as ethoxy and ~e~hoxy, 1 bromine, 2 chlorinQs, 3 sulfos, 2 carboxys, 1 nitro, 1 alkylsulfonyl of 1 to 4 caxbon a~om~ which may be ~ tituted by hydroxy ( such a~, fr: r ea~ample, fl-hydroxyethylsul -iEonyl ), 1 alkyla~aino of 1 to 4 carbon atoms and alkylamino of 1 to 4 car~on at~ms which may be sub~titut~3d ~ n the alkyl radical by hy~oxy, - 3 ~
~ulfato, ~ulfot phosphato, alkanoyloxy o~ 2 to 5 carbon atoms or by carboxy -substituted alkanoyl-amido of 1 to 4 carbon ~toms in the alkylene radical ~uch as ~uccinamido, or R2 denotes a monosulfo-, disulfo~ ox trisulfo-n~phthyl radical, R1 and R2 being identical o or different from each other, or R' and ~2 togekher with the nitrogen atom form a h~tero-cyclic radical composed of an ~lkylene radical composed of 3 to 8 carbon atoms, preferably of 4 to 6 carbon atoms, ~r a further heteroatom, such us a nitrogen atom or oxygen atom, and two alkylene radical~ of 1 to 4 carbon atoms, ~uch as 9 for example, a piperidino, pipera2ino ~r morpholino radical~ .
Substituted alkylamino ~ubstituents in a phenyl ra~ical R2 are ~or example ~-~ulfo~thyl~mino and B-~uccinamido-ethylamino.
Of th~ azo compounds of the general formula (1) according to the invention, e~pecially preferred one~ are tho~e where R ~tands for hydrogen~ tho6e where D i8 a met~- or para-phenylene group each substituted by 1 or 2 ~ulfo groups, those where R1 i8 hydrogen and R2 i~ phenyl which ifi ~ubfitituted by a sulfo group and ~ay additionally be 6ub~tituted by a further ~ulfo group or a ~ethoxy group.
~ulfo groups are gxoups conforming to the general formula -SO3M, carboxy group~ are ~roup~ conforming to the ~eneral formula -COOM, ~ul~ato group~ are groups conorm-ing to the general f~nmul~ -OS03M and phosphato qroup~
are group~ confoxming ~o the general formula ~OPO3M2, in each of which M ha~ one of the ~bovementioned ~eanings.
~he novel azo compound~ can be present in acid form and in the form of their 6alt8. Prefexably they are in ~he form of their salts, in par~icular alkali and slkaline ~arth metal Raltfi, and are preerably al~o used in the ~.
:
~32~
form of the~e ~alt~ for dyeing (to be under~tood here and hereinafter in the general ~en~e snd a~ including print-ing~ hydro~y- and/or carboxamido-containing materials, in particular fiber material~.
The present invention further relateB to proc~se~ for preparing the compounds of the g~neral formula (1), which compri~e a) reacting ~ compound of the ~eneral f~xmula (3) OH
H N D - N ~ N ~
R ~ (3) COOM
where R, D and M have the ~bo~mention0d ~eanings, ln a conventional manner with a c~pound of the general formula (4) X - Y (~
where ~ and Y ha~e the abovementioned ~eanings 15 or b) dia~oti~ng an ~romatic amino ~ompound of the general formula (5) X - ~ - D - NH2 ~5) where ~, R and D have the abovementioned meanings, and coupling the diazonium salt with 2~naphthol-6-carboxylic acid ~r a salt of this carboxylic acid, or c) reacting a compound of the general formula (6) ~32~
Y--~N~N--D--N = N ~ (6) ~ OOM
where ~he two ~ and also R~ D and M have ~he abo~rementioned ~eanings, wi~h an ~nino compound of the general forJnula HNR1R2 with Rl and R2 of the abovementioned ~eaning.
~he r~action conditi~ns o proce~e~ a ) and c ) ar~
analogou~ to known proce~se~ of reactin~ amino compounds with dihalotriazinylamirlo compounds, iEor in~tance in an ~queous or aqueous organic medium (where the t)rs~anic lû ss~lvent component i~ a preferably water-so~ e ~ol~ent which i~ inert under the reaction condition~, for example acetone, di~nethylformamide or dimethyl ~ulfoaside), at a pH bs~ween 1 and 7, in paxticular be~ween 2 and 6, and at a te~nperature of between - 1 0C and ~80C, in particular -lODC and ~53C. In the same way, the diazotization and coupling ri~a~tion of proce~s variant b) is carried out in c:onventional ~anner/ for instanc~ the diazotization at a t~mp@rature of ~etween -5~ ~nd ~20C at a pH of 2 or le~ than 2 and the coupling reaction ~t a tempera~ure of between 5 find 2SC and at a pH b~tween 4 and 8, prefer-~bly between 5 and 7, each preferably in an agueous medium.
The ~tarting compound~ ~f the general ~onmula ~3~ are easily preparable ~nalogou~ly to known pxoce~e~ by coupling the dia~otized ~mine ~R~N~D NH2 with D and R of tbe abovementioned meaning with 2-hydrox~naphthalene-6-carboxylic acid or a ~alt of this carboxyl~c ~cid in accordance with the above reaction conditions for diazo-tization and coupling~ Not ~nly ~he~e diamino compounds but al~o 2-naphthol 6-carboxylic acid axe generally known . .
. , - . . -.~ .
; ' ', ' ,~ ! ' ' ' , ' ' ` . , , ' - 6 -- ~32~l.;13 and described in the literature.
Similarly, the starting amino compound~ of the general formula (5) containing the ~iber-reactive radical ~ or the dihalotri~zine radical are generally known; they can be pr~pared by reacting the corresponding di~mino com pound of the general formula H(R~N-D-NH2 with D ~nd R of the abovementioned meaning with an aminohalotriaæine compound conforming to the general formula (4~ or with cyanuric chloride or cyanuric fluoride. Similarly, the starting compounds of the general formula (6) are prepar-able analogously to other azo compound~ which contain a dihalotriazinylamino radical in bonded form by reacting an aminoazo compound conforming to the general formula 13) with cyanuric chloride or cyanuric fluoride. Process conditions for such reactions are generally known and e~sentLally conform to the process conditions ~pecified hereinafter for the rea~tions between starting compounds (3) and (4) or Qtarting c~mpounds ~6) and amino c~mp~und NHRlR2 To neutralize the hydrogen halide freed in the cour~e of condensation reactions, u~e i~ ~enerally made of alkali and alkaline earth me~al carbonates, alkali and alkaline earth m~tal hydrogencarbonates or alkali or alkaline earth metal hydrox~des or else alkali metal a~e ates, the alkali and alkaline earth metals preferably bPing sodium, potas~ium and calcium; acid-binding agents are al~o tertiary amines, for e~ample pyridine sr triethylamine or quinoline.
~ he reaction according to the in~ention between aminoazo compound~ of ~he general ~ormula (3) and an aminodihalo-triazine compound of the general formula (4) ~enerally take~ place, if Y i~ chlorine, 8t a pH between 4 and 7, preferably ~etween 5 and 6, and at ~ temperature between 0 ~nd 50C, preferably between 10 and 40~C, particularly prefer~bly between 10 and 30C, and if ~ ifi fluorine, at a pH between 4 and 7, preferably between ~ and 6~ and at _ 7 _ ~ ~ 2 ~
a temperature betwean -10C and +40C, preferably between -10C and ~30C, particularly prefexably between 0C and +10C.
The reaction according to the in~ention b~twe~n dihalo-triazinylaminoazo ~smpound~ conforminq to the generalformula (6) and n amino compound of the gen~ral formula RlR2NH with Rl and R2 of the ~bovem2ntioned mea~ing gener-ally takes place, if ~ i~ chlorine, at a pH between 4 and 7, prefer~bly between 5 and 6, ~nd at a temperature between 0 and 50C, pr~ferably between 10 and 40C, particularly preerably between 10 and 30C, ~nd if ~ is fluorine, at a pH between 4 and 7, preferably between 5 and 6, and at a temperature between 10C and +40C, prefersbly between -lO~C and ~30C, particularly prefer-ably between 0C and +10C.
Amino startin~ compounds conformin~ to the general formula R1R2NH axe for ex~mple 2-~ulfsaniline, 3-~ulfo-aniline, 4-sulfoaniline, 2,4-di~ulfoaniline, 2,5-di~ul-foaniline, 5-~ulfo-2-methoxyaniline, 4-~ulfo-2-methoxy-aniline~ 5-sulfo-2-methylaniline, 4-~ulfo-2-methylani-line, 3-~ulfo-4-methoxyaniline, 4-sulfo-2-methoxy-5-methylaniline/4 ~ulfo-2,5-dLmethoxyaniline,5~ulfo-2,4-dimethoxyaniline, 4-sulfo 5-methoxy-2-methyl-aniline, 5-~ulfo-2-chloroanilin~t 3-~ulfo-4-chloro-2-methylaniline, 4-sulfo-5-chloro-2-methoxyanillne, 5- or 6-sulfo-2-amino-naphthalene, 6,8 disulfo-2-aminonaphthalene, 3,~,8-tri-~ulfo-Z-aminonaphthalene, 8-sulfo-2-amino-naphthalene, ~,6,8-tri~ulf~-2-aminonaphthalene, 1,5- or 1,6-disulfo-2-aminonaphthalene, 4,8-di~ulfo-2-amin~naphthalene, 6,7-di~ulfo-2-aminonaphthalene, 5,7-disulfD-2~amin~naphtha lene, S- or 6-~ulfo l~aminonaphthalene, 7 ~ulfo-1-amino-naphthalene, l-~ulfo 2-aminonaphthalene, 3,6 or 4,6- or 4,8-di~ulfo-1-a~inonaphthalene, ~-~ulfoethylsmineJ ~-hydroxyethyl~m~ne, ~ mekhyl-N-(B-~ulfakoethyl)amine, ~ethylethyl~mine, dimethylamine, diethylaminey fl-carboxy-e~hylamine, 4-~ulfobenzylamine, 4-sul~phenethylamine, b4nzylamine, 2-methylaniline, aniline, 4-chloroaniline, .
~ ':. : - .
~ ."
.~ .. .
: "
- 8 _ ~ 32~
N~ hydroxyethyl)aniline, N-e~hylaniline, N methylani-line, ~mmonia, morpholine, piperidine and piperazine~
Diamino starting compou~d~ conforming to the ~eneral formula H(R)N-D-NH2 are ox example 4,6-disulfo-1,3-di-~mi~oben2ene, 2,5-disulfo-1 4-diaminobenzene, 4 ~ulfo-1,3-diaminobenzene, 2-~ulfo-1,4-diamino~enzene, 4-ear-b~xy-1,3-diaminobenzene, 2-carboxy-1,4-diaminobenzene, 2-~ulfo-4-(methylamino)aniline, 4-~ulfo-3 ~methylamino)-aniline,2-sulfo-4-(ethylamino)aniline,4-~ul~o-3-(ethyl-aminoJaniline, 4-N-( ~-BUl foethyl~aminoaniline, 4,8-di-~ulfo-l 7 6-diaminonaphthalene~nd4,8-di~ulfo-2~6-di~mino naphthalene.
The compounds of the general formula ~1) prepared accor-ding to the invention can ~e preciplt~ted or isolated from the synthesis ~olution~ by generally known methods, for example either by precipitating them from the reac-tion medium by mean~ of ~lectrolyt~s, for example sodium chloride or pota~ium chloride, or by evaporating the reaction solution, for example by ~pray d~ying, in which c~e a buffer ~ubstance can be added to the reaction ~lutio~.
The azo compound~ of the general formula (1) ~ccording to the invention - hereinafter referred to as compounds (1~
- have fiber-reacti~e prop~rties and po~ses~ very good dye propertle6v as alre~dy ~entioned. ~hey can therefore ~e u~ed for dyeing (including prin~ing) hydro~y -contain-~ng and/or carboxamido-containing material6, in particu-lar fiber materials. It i8 ~180 possible to use the ~olu-tiOn obtained in the synthesi~ of the compounds accsr~
ding to the invention, with or without addition of a buffer xubstance and with or without conce~trating, directly in dyeing as liquid formulations.
The present inventîon therefore al~o provide~ ~h~ u~e of compounds (1~ fox ~yeiny (including printing) hydroxy-and/or carboxamido-containing materials, or proces~e~ for , :
9 ~ 3 ~ ~
and/or carboxamido-containing materials, or processe~ for their application to the~e ~ub~trate~. Preferahly the materials are employed for applica~ion in the form ~f fiber materials, in particular in the form of textile fibers, ~uch as y~rns, wound package6 snd fabrics. Thi~
application can be caxried out analogou~ly to known process~s .
~ydroxy -containing materials are tho~e of a natural or ~ynthetic origin, ~or example cellulose fiber materials or regenerated product~ thereof, and polyvinyl alcohols.
Cellulo~e fiber materials are preferably cotton but other vegetable fiber~ a~ well, ~uch a~ linen, hemp, ~u~e ~nd ramie fiber~; re~enerated cellulo~e fiber6 are for ~xample ~taple and filament vi8c06e .
Carboxamido-contsining materials are for example ~yn-thetic and natural polyamides and polyurethanes, in particular in the form of fiber~, for example wool and other anLmal hair, silk, leather, nylon-6,6, nylon~6, nylon-ll and nylon-4.
The compounds can be applied to and fixed on the ~ub~
~trate~ ~entioned in accordance with the use accordin~ to the invention, in particular the fiber material~ men-tîoned~ by the application techniques known for water-~vluble dyes, in particular fiber-reactive dye~, for example by applying a ~ompound (1) in dissolved form to ~he ~ubs~rate or incorporating it therein and fixing it ~hereon or therein with or without heating and/or with or without the action of an alkalin~ agen~. Such dyeing and fixing methods are nwmerously de~cribed in th~ patent literature, ~or example in European Patent ~pplication publication No. 0,181,585A.
U6ing compounds (1) it i8 p~s~ible not only ~n carbox-~mido-containing material~, in particular on wool, but al~o on hydroxy -containing material, in particular cellulo~e fi~ex ma~exial, ~o produce yellowish to blui~h :
~2~
red dyeings and print~ of high color yield and good color buildup, in which the brillian~ hue i~ retained even in deep ~hades. The dye~ngs and prints have good fa6tness propertiPs, such as good light and wet fa6tnecs proper-5 ties and good pleating fa~tness, hot pres~ fa~tness andcrock fastness.
Of the dyeings and print~ on carboxamîdo-containing material, in par~icular on wool, the light, wa~h and wet li~ht fastne~ properties can be singled out, even if an otherwi6e cu~tomary ammoniacal aftertreatment of the dyed material $~ dispen~ed with. They are hi~hly compatible with other fiber-reactiYe wool dye~t which permit~ level dyeing of the f~er. Similarly, it i~ po~sible to obtain level dyeing~ on material made ~f wool fibers of dif-ferent provenience~ with compounds (1), in which case acugto~ary leYeling a~si~tant, for e~ample N-methyltaur-ine, may be added to Lmprove the leveling properties.
Preferably, compound6 (1) are used for dyeing cellulose fiber material~. Of the good fa~tne~s properties ob-tainable thereof, in particular the good wash fa~tnesspropertie~ at 60 to 95C, even in the presence of per-borates, the acid ulling, cross-dyeing and per~piration fagtne~s propertie~, the high steam re~i~tance and good acid, water ~nd seawater fastness propertie~ should be men~ioned.
The Examples belo~ serve to illustrate the invention.
Parts and percenta~e~ are by weight, unle~s otherwise 8tated. Part~ by weight bear the ~ame relation to p~rt by volume as the kilogram to the liter.
The compound~ described below in the Exampl88 in terms of ~ormulae are shown ln the form ~f the free ~cid~; in general, they are prep~red and isolated in the form of their ~odium or pota 6ium BaltS And are used or dyeing in ~he form of th~ir 8alts. It is ~imilarly p~sible to u~e in the synthesis the 5 arting compound& and :
, 11 ~ 32~
componPnts mentioned in the orm of the free acid in the examples below, in particular the Table Examples, as 6uch or in th2 form of their 8alt6, preferably alkali metal salt~, such as sodium or pota~ium ~al~.
The ab~orption max~ma (~5~ values) given for the visible region were determined at 20C on the alkali ~etal salts thereof in aqueous ~olution.
pl~
a) A ~olution of 91 parts of aniline-4-~ulfonic arid in 500 parts of water st pH 6 i~ ~tirred into a su~pen~ion of lO0 part~ of cyanuric c~loride and 3 parts of a commercially ~vailable wetting agent in 800 part6 of ice and water. Stirring iB continued for ~ome time at a temperature be~ween 0 and 5C
while the pH i8 maintained between 3.5 and 4.5 by mean~ of ~odium bicarbonate. ~he ~onversion of the acylation reaction i~ 99% or higher.
b) The reaction batch prepared under a) is stirred into a ~olution of 134 part~ of 1,3-diaminobenzene-4,6-disulfonic acid in about 600 parts of water at a pH
between ~ and 7; the reactivn mixture ~ 8 heated ts 40C, and ~tirring i~ continued at a temperature between 40 and 45C while the pH i6 ~aintained between 5 and 6 by mean~ of ~odium bicarbonate, until the diamino compound is virtually no longer detectable.
c) ~he batch obtained from the ~econd acylation reac-tion under b) is admi~ed with 1000 parts of ice and 150 parts by volume of aqueous 31% strength hydro-chloric acid and diazotized with an aqueous solution ~f 35 parts o~ ~odium nitrik~. The diazotization mixture obtained i~ added wi~h 8tirrin~ to ~ 801u-~ion of 94 parts of 2-naphthol-~-carboxylic acid in about 1100 part~ o wa~er at a pH be~ween 6 and 6.5, after which the pH i~ ad~usted to about 5 and is maintained at between 4.5 and 6 by means of sodium bicarbonate througho~ the entire coupling reaction.
Stirring i~ continued fox ~ome tLmQ until the , . . . . .
_ 12 - ~32 couplin~ has ended.
~he novel m~noazo compound thus prepared i~ i~olated in a conventional manner, for example by evaporating or spray-drying the neutral ~ynthesi~ ~olution or by ~alting out with sodium chloride or pota6sium chloride. An ~lectrolyte-containing orange powder i~ obtained of thP
~lkali metal salt of the compound of the formula Cl OH
N ~ N I -3S ~ H03S N - N ~
OOH
( ~ax ~ 478 nm) which shows very qood fiber-reactive dye propertie~ and applied to the material6 ~entioned in the de6cription, in particular cellulo~e-fiber material~, for ~xample cotton, by the ~pplication ~nd fixing methods customary in the art, in particular by the applica~ion ~ondi~lons des-cribed and employed for fiber-reactive dyes, produce~
~trong clear orange-colored dyeing~ and print~ h~ing good light fastne~s properties and good wet fastne~s properties, in particular good wash~ ~ulling, perspira-tion and cross-dyeing fastne~ properties.
~ample 2 a) A solution of 39 part6 of cyanuric chloride in 150 part~ ~y volume o~ acetone is added with ~tirring to 3~0 part~ of ice; about lODO parts by volu~e of an agueous cold, le~s than 10C, neutral ~olutio~ of 108 part6 of an aminoazo compound con~tru~ted from 4 r 6~di~ulfo-1,3~diaminobenzene as diazo ~omponent and 2-naphthol-6-carboxylic acid ~ coupling com-ponent ~re added with Btirring to the ~uspension.
~he batch i~ ~uh~equently ~tirred at O to 10C for about 4 ~ore hours ~t a pH maintained between 4 and . . . ~
.
; ~
: ~ :
. . ~ , .
~ 3 2 ~
5 until amine i5 virtually no longer detectable.
b) 400 parts by volume of an aqueous neutr~l ~olution of 37 part~ of 3-~ulfoaniline are ~tirred int~ the reaction batch prepared under a). Thereafter the reaction mixture i8 rai6ed to a temp~rature o~ 40 to 45C in the cnur~e of 2 hour~ snd s~irred at 40 to 50C for about a further 12 hour6 while a pH between 4.5 and 5 until the acylation reaction has ended.
The novel azo compound of the formula N ~ N L
3O35 SO;H ~
COOH
( ~ ~ 479 ~m) isolated in the form of th~ alkali ~tal salt a~ an electrolyte-containing orange powder. It has very good fiber-reactive dye properties and applied to the mat~ri-al8 m~ntioned in the description, in particular ~ellulose fibers, for example cotton, by the application and fixing ~ethods custo~ary in th~ art, in particular the applica-tion conditions de~cribed and employed ~or fiber-reactive dye~, produces ~trong elear orange-~olored dyeings and print~ having good l~ght fastn~ss properti~s and good wet fa~tne~ propertie~, ~uch a8 in part~cular good wa~h, fullin0, p~r~piration and ~ro~s-dyeing fastn~ss proper-ties.
~ ple 3 Aniline-4-~ulfonîe acid îs reacked with cyanuric chloride by the procedure o ~xample la~, and the ~nthesi~ batch obtained i~ added with ~tirring to a ~olution of 98 parts of 1,3 diamino~enzene~4-~ulfonic acid in ~bout 600 part~
of water at a pH betwe~n 6 and 7; the reaction mixture i~
heat~d to 40~, and ~tirrin~ i~ contlnu~d at a tempera-..
:
. . .
- . : , , :: .: . - .
- 14 _ ~32~
ture between 40 and 45C while the pH is maintained between 5 and 6 by maan~ of ~odium bicarbonate until the diamino compound i8 virtually no longer detectable.
The batch obtained from this ~econd acylation reaction i~
a*mixed with 1000 parts of ice and 150 part~ by Yolume of aqueou~ 31~ strength hydrochloric acid and diazotized ~ith an aqueous ~olution of 35 parts of sodium nitrite.
Th~ diazotization mixture i~ then added with ~tirri~g t~
a ~olu~ion of 94 part~ of 2-naphthol-6-carboxylic ac d in about llOO parts of water and 45 part~ of aqueous ~odium hydroxid solution at a pH between 6 and 6.5, the pH
being maintained between 4.5 and 6 throughout the entire coupling reaction by means of ~odium bicarbonate. Stir--- ring i8 continued for ~ome tLme until the coupling haæ
ended.
The monoazo compound according to the ~n~ention i8 isolated in a conventi~nal manner, for example by evapor-ating or ~pray-drying the neutral Yynthesi~ solution or by 3alting out with an electrolyte salt, for example potas~ium chloride. ~n electrolyte-containing red powder i~ obtained of an alkali metal ~alt, for example pota~-~ium salt, of the compound of the formula Cl OH
5 ~ NH ~ N ~ NH ~ N N ~
COOH
(~max ~ 501 ~m) whlc~ ha~ very good fiber-r~active dye properti~ and applied to the material~ mentioned i~ the description, in particular cellulose ~ r material~, ~uch as cotton, by the applicati~n method~ cu~tomary in the art, produse~
~trong bri~ht red d~eings and prin~ having good light fastne~ propertl~B and good wet a~tne~ pr~per~ies, in - 15 ~ 3 2 ~
particular good washing, milling, per~piration and cro~s-dyeing ~astne~s properties.
~sample 4 a) Fir~t the twofold conden~ation product i~ prepared from cyanuric fluoride with 2~4-di~ulfoaniline and 4-~ulfo-1,3-diaminobenzene: 13.6 partæ of cyanuric chloride ~r~ gradually added in the cour~e ~f 5 to 10 minutes with thorough ~tirring to a ~olution at 0C of the ~odium salt of 25.3 parts of 2,4-di~ul-foaniline in 150 parts of water while maintaining a p~ between 5 and 5.5. Stirring i~ then continued at that temperature and that pH ~or a further 5 to 10 minutes until diazotizable amine is no l~nger detect~ble. The cold ~olution of thi~ monocondensa-tion product is then added with horough stirring to a 601ution at 15 to 20C of the sodium salt of 19 p~rts of 1,3-diaminobPnzene-4-sulfonic acid in 200 part~ of water in the course of 15 to 20 minutes.
~he batch i~ subsequently stirred at a temperature ~etween 15 and 25C and at a pH between 5 and 6 for a further hour.
~he tw~fold conden~atio~ produs~ i~ diazotized and coupled with 2-naphthol-6-carboxylic acid in accor-dance with the directions of ~xample lc~ and iso-lated. The pota&~iumf60dium ~alt i~ obtained of the compound of the formula F OH
S03H N ~ N L
~ ~ NH ~ N ~ NH ~ N N ~/
H03S ~ S03H
COO~I
( ~ax ' 504 nm).
This ~o compound accoxding ~o the invention ha~ very .
.
16 ~ ~ e~
good fiber-reactive dye properties and dye~ the materials mentioned in the description, in particular wool, includ-ing wool with a low-felting fini~h, in brilliant red ~hades with good color buildup and good fastn~ proper-ties.
~amples 5 to 229 The Table E x~mple~ below describe further novel monoazo compound~ conforming to the general formula (A) I pH
N~N ~
N ~ N - D* N = N ~ ~A) COOH
in terms of their component~. They c~n ~e prPpared in a manner according to the invention, for example by one of the procedure~ de~cribed ln ~xample~ 1 to ~, from he corresponding~tarting compounds (2-naphthol-6-carboxylic acid a~ coupling component, the diamino ~pound of the general formula H(R)N-D-NH2, cyanuric chloride or cyan uric fluorid~ and an amino compound conforming to the formula R~-H). They have ~ery goQd dye properties and produce on the material~ mentioned in the de~cription, in particular cellulose fiber materials, for example cotton, ~nd likewise on wool, ~trong dyeing~ and prints having good fa~tne~ propertie~ in the hue indicated in the phrticular Table Ex~mple for dyeing~ on cot~on.
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The present invention further relateB to proc~se~ for preparing the compounds of the g~neral formula (1), which compri~e a) reacting ~ compound of the ~eneral f~xmula (3) OH
H N D - N ~ N ~
R ~ (3) COOM
where R, D and M have the ~bo~mention0d ~eanings, ln a conventional manner with a c~pound of the general formula (4) X - Y (~
where ~ and Y ha~e the abovementioned ~eanings 15 or b) dia~oti~ng an ~romatic amino ~ompound of the general formula (5) X - ~ - D - NH2 ~5) where ~, R and D have the abovementioned meanings, and coupling the diazonium salt with 2~naphthol-6-carboxylic acid ~r a salt of this carboxylic acid, or c) reacting a compound of the general formula (6) ~32~
Y--~N~N--D--N = N ~ (6) ~ OOM
where ~he two ~ and also R~ D and M have ~he abo~rementioned ~eanings, wi~h an ~nino compound of the general forJnula HNR1R2 with Rl and R2 of the abovementioned ~eaning.
~he r~action conditi~ns o proce~e~ a ) and c ) ar~
analogou~ to known proce~se~ of reactin~ amino compounds with dihalotriazinylamirlo compounds, iEor in~tance in an ~queous or aqueous organic medium (where the t)rs~anic lû ss~lvent component i~ a preferably water-so~ e ~ol~ent which i~ inert under the reaction condition~, for example acetone, di~nethylformamide or dimethyl ~ulfoaside), at a pH bs~ween 1 and 7, in paxticular be~ween 2 and 6, and at a te~nperature of between - 1 0C and ~80C, in particular -lODC and ~53C. In the same way, the diazotization and coupling ri~a~tion of proce~s variant b) is carried out in c:onventional ~anner/ for instanc~ the diazotization at a t~mp@rature of ~etween -5~ ~nd ~20C at a pH of 2 or le~ than 2 and the coupling reaction ~t a tempera~ure of between 5 find 2SC and at a pH b~tween 4 and 8, prefer-~bly between 5 and 7, each preferably in an agueous medium.
The ~tarting compound~ ~f the general ~onmula ~3~ are easily preparable ~nalogou~ly to known pxoce~e~ by coupling the dia~otized ~mine ~R~N~D NH2 with D and R of tbe abovementioned meaning with 2-hydrox~naphthalene-6-carboxylic acid or a ~alt of this carboxyl~c ~cid in accordance with the above reaction conditions for diazo-tization and coupling~ Not ~nly ~he~e diamino compounds but al~o 2-naphthol 6-carboxylic acid axe generally known . .
. , - . . -.~ .
; ' ', ' ,~ ! ' ' ' , ' ' ` . , , ' - 6 -- ~32~l.;13 and described in the literature.
Similarly, the starting amino compound~ of the general formula (5) containing the ~iber-reactive radical ~ or the dihalotri~zine radical are generally known; they can be pr~pared by reacting the corresponding di~mino com pound of the general formula H(R~N-D-NH2 with D ~nd R of the abovementioned meaning with an aminohalotriaæine compound conforming to the general formula (4~ or with cyanuric chloride or cyanuric fluoride. Similarly, the starting compounds of the general formula (6) are prepar-able analogously to other azo compound~ which contain a dihalotriazinylamino radical in bonded form by reacting an aminoazo compound conforming to the general formula 13) with cyanuric chloride or cyanuric fluoride. Process conditions for such reactions are generally known and e~sentLally conform to the process conditions ~pecified hereinafter for the rea~tions between starting compounds (3) and (4) or Qtarting c~mpounds ~6) and amino c~mp~und NHRlR2 To neutralize the hydrogen halide freed in the cour~e of condensation reactions, u~e i~ ~enerally made of alkali and alkaline earth me~al carbonates, alkali and alkaline earth m~tal hydrogencarbonates or alkali or alkaline earth metal hydrox~des or else alkali metal a~e ates, the alkali and alkaline earth metals preferably bPing sodium, potas~ium and calcium; acid-binding agents are al~o tertiary amines, for e~ample pyridine sr triethylamine or quinoline.
~ he reaction according to the in~ention between aminoazo compound~ of ~he general ~ormula (3) and an aminodihalo-triazine compound of the general formula (4) ~enerally take~ place, if Y i~ chlorine, 8t a pH between 4 and 7, preferably ~etween 5 and 6, and at ~ temperature between 0 ~nd 50C, preferably between 10 and 40~C, particularly prefer~bly between 10 and 30C, and if ~ ifi fluorine, at a pH between 4 and 7, preferably between ~ and 6~ and at _ 7 _ ~ ~ 2 ~
a temperature betwean -10C and +40C, preferably between -10C and ~30C, particularly prefexably between 0C and +10C.
The reaction according to the in~ention b~twe~n dihalo-triazinylaminoazo ~smpound~ conforminq to the generalformula (6) and n amino compound of the gen~ral formula RlR2NH with Rl and R2 of the ~bovem2ntioned mea~ing gener-ally takes place, if ~ i~ chlorine, at a pH between 4 and 7, prefer~bly between 5 and 6, ~nd at a temperature between 0 and 50C, pr~ferably between 10 and 40C, particularly preerably between 10 and 30C, ~nd if ~ is fluorine, at a pH between 4 and 7, preferably between 5 and 6, and at a temperature between 10C and +40C, prefersbly between -lO~C and ~30C, particularly prefer-ably between 0C and +10C.
Amino startin~ compounds conformin~ to the general formula R1R2NH axe for ex~mple 2-~ulfsaniline, 3-~ulfo-aniline, 4-sulfoaniline, 2,4-di~ulfoaniline, 2,5-di~ul-foaniline, 5-~ulfo-2-methoxyaniline, 4-~ulfo-2-methoxy-aniline~ 5-sulfo-2-methylaniline, 4-~ulfo-2-methylani-line, 3-~ulfo-4-methoxyaniline, 4-sulfo-2-methoxy-5-methylaniline/4 ~ulfo-2,5-dLmethoxyaniline,5~ulfo-2,4-dimethoxyaniline, 4-sulfo 5-methoxy-2-methyl-aniline, 5-~ulfo-2-chloroanilin~t 3-~ulfo-4-chloro-2-methylaniline, 4-sulfo-5-chloro-2-methoxyanillne, 5- or 6-sulfo-2-amino-naphthalene, 6,8 disulfo-2-aminonaphthalene, 3,~,8-tri-~ulfo-Z-aminonaphthalene, 8-sulfo-2-amino-naphthalene, ~,6,8-tri~ulf~-2-aminonaphthalene, 1,5- or 1,6-disulfo-2-aminonaphthalene, 4,8-di~ulfo-2-amin~naphthalene, 6,7-di~ulfo-2-aminonaphthalene, 5,7-disulfD-2~amin~naphtha lene, S- or 6-~ulfo l~aminonaphthalene, 7 ~ulfo-1-amino-naphthalene, l-~ulfo 2-aminonaphthalene, 3,6 or 4,6- or 4,8-di~ulfo-1-a~inonaphthalene, ~-~ulfoethylsmineJ ~-hydroxyethyl~m~ne, ~ mekhyl-N-(B-~ulfakoethyl)amine, ~ethylethyl~mine, dimethylamine, diethylaminey fl-carboxy-e~hylamine, 4-~ulfobenzylamine, 4-sul~phenethylamine, b4nzylamine, 2-methylaniline, aniline, 4-chloroaniline, .
~ ':. : - .
~ ."
.~ .. .
: "
- 8 _ ~ 32~
N~ hydroxyethyl)aniline, N-e~hylaniline, N methylani-line, ~mmonia, morpholine, piperidine and piperazine~
Diamino starting compou~d~ conforming to the ~eneral formula H(R)N-D-NH2 are ox example 4,6-disulfo-1,3-di-~mi~oben2ene, 2,5-disulfo-1 4-diaminobenzene, 4 ~ulfo-1,3-diaminobenzene, 2-~ulfo-1,4-diamino~enzene, 4-ear-b~xy-1,3-diaminobenzene, 2-carboxy-1,4-diaminobenzene, 2-~ulfo-4-(methylamino)aniline, 4-~ulfo-3 ~methylamino)-aniline,2-sulfo-4-(ethylamino)aniline,4-~ul~o-3-(ethyl-aminoJaniline, 4-N-( ~-BUl foethyl~aminoaniline, 4,8-di-~ulfo-l 7 6-diaminonaphthalene~nd4,8-di~ulfo-2~6-di~mino naphthalene.
The compounds of the general formula ~1) prepared accor-ding to the invention can ~e preciplt~ted or isolated from the synthesis ~olution~ by generally known methods, for example either by precipitating them from the reac-tion medium by mean~ of ~lectrolyt~s, for example sodium chloride or pota~ium chloride, or by evaporating the reaction solution, for example by ~pray d~ying, in which c~e a buffer ~ubstance can be added to the reaction ~lutio~.
The azo compound~ of the general formula (1) ~ccording to the invention - hereinafter referred to as compounds (1~
- have fiber-reacti~e prop~rties and po~ses~ very good dye propertle6v as alre~dy ~entioned. ~hey can therefore ~e u~ed for dyeing (including prin~ing) hydro~y -contain-~ng and/or carboxamido-containing material6, in particu-lar fiber materials. It i8 ~180 possible to use the ~olu-tiOn obtained in the synthesi~ of the compounds accsr~
ding to the invention, with or without addition of a buffer xubstance and with or without conce~trating, directly in dyeing as liquid formulations.
The present inventîon therefore al~o provide~ ~h~ u~e of compounds (1~ fox ~yeiny (including printing) hydroxy-and/or carboxamido-containing materials, or proces~e~ for , :
9 ~ 3 ~ ~
and/or carboxamido-containing materials, or processe~ for their application to the~e ~ub~trate~. Preferahly the materials are employed for applica~ion in the form ~f fiber materials, in particular in the form of textile fibers, ~uch as y~rns, wound package6 snd fabrics. Thi~
application can be caxried out analogou~ly to known process~s .
~ydroxy -containing materials are tho~e of a natural or ~ynthetic origin, ~or example cellulose fiber materials or regenerated product~ thereof, and polyvinyl alcohols.
Cellulo~e fiber materials are preferably cotton but other vegetable fiber~ a~ well, ~uch a~ linen, hemp, ~u~e ~nd ramie fiber~; re~enerated cellulo~e fiber6 are for ~xample ~taple and filament vi8c06e .
Carboxamido-contsining materials are for example ~yn-thetic and natural polyamides and polyurethanes, in particular in the form of fiber~, for example wool and other anLmal hair, silk, leather, nylon-6,6, nylon~6, nylon-ll and nylon-4.
The compounds can be applied to and fixed on the ~ub~
~trate~ ~entioned in accordance with the use accordin~ to the invention, in particular the fiber material~ men-tîoned~ by the application techniques known for water-~vluble dyes, in particular fiber-reactive dye~, for example by applying a ~ompound (1) in dissolved form to ~he ~ubs~rate or incorporating it therein and fixing it ~hereon or therein with or without heating and/or with or without the action of an alkalin~ agen~. Such dyeing and fixing methods are nwmerously de~cribed in th~ patent literature, ~or example in European Patent ~pplication publication No. 0,181,585A.
U6ing compounds (1) it i8 p~s~ible not only ~n carbox-~mido-containing material~, in particular on wool, but al~o on hydroxy -containing material, in particular cellulo~e fi~ex ma~exial, ~o produce yellowish to blui~h :
~2~
red dyeings and print~ of high color yield and good color buildup, in which the brillian~ hue i~ retained even in deep ~hades. The dye~ngs and prints have good fa6tness propertiPs, such as good light and wet fa6tnecs proper-5 ties and good pleating fa~tness, hot pres~ fa~tness andcrock fastness.
Of the dyeings and print~ on carboxamîdo-containing material, in par~icular on wool, the light, wa~h and wet li~ht fastne~ properties can be singled out, even if an otherwi6e cu~tomary ammoniacal aftertreatment of the dyed material $~ dispen~ed with. They are hi~hly compatible with other fiber-reactiYe wool dye~t which permit~ level dyeing of the f~er. Similarly, it i~ po~sible to obtain level dyeing~ on material made ~f wool fibers of dif-ferent provenience~ with compounds (1), in which case acugto~ary leYeling a~si~tant, for e~ample N-methyltaur-ine, may be added to Lmprove the leveling properties.
Preferably, compound6 (1) are used for dyeing cellulose fiber material~. Of the good fa~tne~s properties ob-tainable thereof, in particular the good wash fa~tnesspropertie~ at 60 to 95C, even in the presence of per-borates, the acid ulling, cross-dyeing and per~piration fagtne~s propertie~, the high steam re~i~tance and good acid, water ~nd seawater fastness propertie~ should be men~ioned.
The Examples belo~ serve to illustrate the invention.
Parts and percenta~e~ are by weight, unle~s otherwise 8tated. Part~ by weight bear the ~ame relation to p~rt by volume as the kilogram to the liter.
The compound~ described below in the Exampl88 in terms of ~ormulae are shown ln the form ~f the free ~cid~; in general, they are prep~red and isolated in the form of their ~odium or pota 6ium BaltS And are used or dyeing in ~he form of th~ir 8alts. It is ~imilarly p~sible to u~e in the synthesis the 5 arting compound& and :
, 11 ~ 32~
componPnts mentioned in the orm of the free acid in the examples below, in particular the Table Examples, as 6uch or in th2 form of their 8alt6, preferably alkali metal salt~, such as sodium or pota~ium ~al~.
The ab~orption max~ma (~5~ values) given for the visible region were determined at 20C on the alkali ~etal salts thereof in aqueous ~olution.
pl~
a) A ~olution of 91 parts of aniline-4-~ulfonic arid in 500 parts of water st pH 6 i~ ~tirred into a su~pen~ion of lO0 part~ of cyanuric c~loride and 3 parts of a commercially ~vailable wetting agent in 800 part6 of ice and water. Stirring iB continued for ~ome time at a temperature be~ween 0 and 5C
while the pH i8 maintained between 3.5 and 4.5 by mean~ of ~odium bicarbonate. ~he ~onversion of the acylation reaction i~ 99% or higher.
b) The reaction batch prepared under a) is stirred into a ~olution of 134 part~ of 1,3-diaminobenzene-4,6-disulfonic acid in about 600 parts of water at a pH
between ~ and 7; the reactivn mixture ~ 8 heated ts 40C, and ~tirring i~ continued at a temperature between 40 and 45C while the pH i6 ~aintained between 5 and 6 by mean~ of ~odium bicarbonate, until the diamino compound is virtually no longer detectable.
c) ~he batch obtained from the ~econd acylation reac-tion under b) is admi~ed with 1000 parts of ice and 150 parts by volume of aqueous 31% strength hydro-chloric acid and diazotized with an aqueous solution ~f 35 parts o~ ~odium nitrik~. The diazotization mixture obtained i~ added wi~h 8tirrin~ to ~ 801u-~ion of 94 parts of 2-naphthol-~-carboxylic acid in about 1100 part~ o wa~er at a pH be~ween 6 and 6.5, after which the pH i~ ad~usted to about 5 and is maintained at between 4.5 and 6 by means of sodium bicarbonate througho~ the entire coupling reaction.
Stirring i~ continued fox ~ome tLmQ until the , . . . . .
_ 12 - ~32 couplin~ has ended.
~he novel m~noazo compound thus prepared i~ i~olated in a conventional manner, for example by evaporating or spray-drying the neutral ~ynthesi~ ~olution or by ~alting out with sodium chloride or pota6sium chloride. An ~lectrolyte-containing orange powder i~ obtained of thP
~lkali metal salt of the compound of the formula Cl OH
N ~ N I -3S ~ H03S N - N ~
OOH
( ~ax ~ 478 nm) which shows very qood fiber-reactive dye propertie~ and applied to the material6 ~entioned in the de6cription, in particular cellulo~e-fiber material~, for ~xample cotton, by the ~pplication ~nd fixing methods customary in the art, in particular by the applica~ion ~ondi~lons des-cribed and employed for fiber-reactive dyes, produce~
~trong clear orange-colored dyeing~ and print~ h~ing good light fastne~s properties and good wet fastne~s properties, in particular good wash~ ~ulling, perspira-tion and cross-dyeing fastne~ properties.
~ample 2 a) A solution of 39 part6 of cyanuric chloride in 150 part~ ~y volume o~ acetone is added with ~tirring to 3~0 part~ of ice; about lODO parts by volu~e of an agueous cold, le~s than 10C, neutral ~olutio~ of 108 part6 of an aminoazo compound con~tru~ted from 4 r 6~di~ulfo-1,3~diaminobenzene as diazo ~omponent and 2-naphthol-6-carboxylic acid ~ coupling com-ponent ~re added with Btirring to the ~uspension.
~he batch i~ ~uh~equently ~tirred at O to 10C for about 4 ~ore hours ~t a pH maintained between 4 and . . . ~
.
; ~
: ~ :
. . ~ , .
~ 3 2 ~
5 until amine i5 virtually no longer detectable.
b) 400 parts by volume of an aqueous neutr~l ~olution of 37 part~ of 3-~ulfoaniline are ~tirred int~ the reaction batch prepared under a). Thereafter the reaction mixture i8 rai6ed to a temp~rature o~ 40 to 45C in the cnur~e of 2 hour~ snd s~irred at 40 to 50C for about a further 12 hour6 while a pH between 4.5 and 5 until the acylation reaction has ended.
The novel azo compound of the formula N ~ N L
3O35 SO;H ~
COOH
( ~ ~ 479 ~m) isolated in the form of th~ alkali ~tal salt a~ an electrolyte-containing orange powder. It has very good fiber-reactive dye properties and applied to the mat~ri-al8 m~ntioned in the description, in particular ~ellulose fibers, for example cotton, by the application and fixing ~ethods custo~ary in th~ art, in particular the applica-tion conditions de~cribed and employed ~or fiber-reactive dye~, produces ~trong elear orange-~olored dyeings and print~ having good l~ght fastn~ss properti~s and good wet fa~tne~ propertie~, ~uch a8 in part~cular good wa~h, fullin0, p~r~piration and ~ro~s-dyeing fastn~ss proper-ties.
~ ple 3 Aniline-4-~ulfonîe acid îs reacked with cyanuric chloride by the procedure o ~xample la~, and the ~nthesi~ batch obtained i~ added with ~tirring to a ~olution of 98 parts of 1,3 diamino~enzene~4-~ulfonic acid in ~bout 600 part~
of water at a pH betwe~n 6 and 7; the reaction mixture i~
heat~d to 40~, and ~tirrin~ i~ contlnu~d at a tempera-..
:
. . .
- . : , , :: .: . - .
- 14 _ ~32~
ture between 40 and 45C while the pH is maintained between 5 and 6 by maan~ of ~odium bicarbonate until the diamino compound i8 virtually no longer detectable.
The batch obtained from this ~econd acylation reaction i~
a*mixed with 1000 parts of ice and 150 part~ by Yolume of aqueou~ 31~ strength hydrochloric acid and diazotized ~ith an aqueous ~olution of 35 parts of sodium nitrite.
Th~ diazotization mixture i~ then added with ~tirri~g t~
a ~olu~ion of 94 part~ of 2-naphthol-6-carboxylic ac d in about llOO parts of water and 45 part~ of aqueous ~odium hydroxid solution at a pH between 6 and 6.5, the pH
being maintained between 4.5 and 6 throughout the entire coupling reaction by means of ~odium bicarbonate. Stir--- ring i8 continued for ~ome tLme until the coupling haæ
ended.
The monoazo compound according to the ~n~ention i8 isolated in a conventi~nal manner, for example by evapor-ating or ~pray-drying the neutral Yynthesi~ solution or by 3alting out with an electrolyte salt, for example potas~ium chloride. ~n electrolyte-containing red powder i~ obtained of an alkali metal ~alt, for example pota~-~ium salt, of the compound of the formula Cl OH
5 ~ NH ~ N ~ NH ~ N N ~
COOH
(~max ~ 501 ~m) whlc~ ha~ very good fiber-r~active dye properti~ and applied to the material~ mentioned i~ the description, in particular cellulose ~ r material~, ~uch as cotton, by the applicati~n method~ cu~tomary in the art, produse~
~trong bri~ht red d~eings and prin~ having good light fastne~ propertl~B and good wet a~tne~ pr~per~ies, in - 15 ~ 3 2 ~
particular good washing, milling, per~piration and cro~s-dyeing ~astne~s properties.
~sample 4 a) Fir~t the twofold conden~ation product i~ prepared from cyanuric fluoride with 2~4-di~ulfoaniline and 4-~ulfo-1,3-diaminobenzene: 13.6 partæ of cyanuric chloride ~r~ gradually added in the cour~e ~f 5 to 10 minutes with thorough ~tirring to a ~olution at 0C of the ~odium salt of 25.3 parts of 2,4-di~ul-foaniline in 150 parts of water while maintaining a p~ between 5 and 5.5. Stirring i~ then continued at that temperature and that pH ~or a further 5 to 10 minutes until diazotizable amine is no l~nger detect~ble. The cold ~olution of thi~ monocondensa-tion product is then added with horough stirring to a 601ution at 15 to 20C of the sodium salt of 19 p~rts of 1,3-diaminobPnzene-4-sulfonic acid in 200 part~ of water in the course of 15 to 20 minutes.
~he batch i~ subsequently stirred at a temperature ~etween 15 and 25C and at a pH between 5 and 6 for a further hour.
~he tw~fold conden~atio~ produs~ i~ diazotized and coupled with 2-naphthol-6-carboxylic acid in accor-dance with the directions of ~xample lc~ and iso-lated. The pota&~iumf60dium ~alt i~ obtained of the compound of the formula F OH
S03H N ~ N L
~ ~ NH ~ N ~ NH ~ N N ~/
H03S ~ S03H
COO~I
( ~ax ' 504 nm).
This ~o compound accoxding ~o the invention ha~ very .
.
16 ~ ~ e~
good fiber-reactive dye properties and dye~ the materials mentioned in the description, in particular wool, includ-ing wool with a low-felting fini~h, in brilliant red ~hades with good color buildup and good fastn~ proper-ties.
~amples 5 to 229 The Table E x~mple~ below describe further novel monoazo compound~ conforming to the general formula (A) I pH
N~N ~
N ~ N - D* N = N ~ ~A) COOH
in terms of their component~. They c~n ~e prPpared in a manner according to the invention, for example by one of the procedure~ de~cribed ln ~xample~ 1 to ~, from he corresponding~tarting compounds (2-naphthol-6-carboxylic acid a~ coupling component, the diamino ~pound of the general formula H(R)N-D-NH2, cyanuric chloride or cyan uric fluorid~ and an amino compound conforming to the formula R~-H). They have ~ery goQd dye properties and produce on the material~ mentioned in the de~cription, in particular cellulose fiber materials, for example cotton, ~nd likewise on wool, ~trong dyeing~ and prints having good fa~tne~ propertie~ in the hue indicated in the phrticular Table Ex~mple for dyeing~ on cot~on.
.
:~ .
.
-- 17 ._ ~ 3 2 ~
P: ~ ~ .
, , ._ j ~o~ ~o~
O d'~
t~ N t`d ~ d' ~ '~P ~ ~P ~ 1 ' ~ . . -': " ~ ' . :
~32 o B B B B B B B
~ I N N ~ ~ ~ N ~
: ~ :
- 19 - ~2~
~ ~ ~ t ~ ~ B
~, ~ .
o , Q
Z ~
a ~D r- f" ~ ~ ~
r~ o _I ~ ~ ~ ~ ~D t~ W ~ O ~1 ' - ;20 :L3 _ ~
~, _, 3 ~ ~
3~D~
, ~ .
.~. .; .. ; ~
.~ ...... .~ ~. ..
, ., , ..
.; . .
. ~ .
~ 1 3 2 o 1~
~ D~
~ ~ o --l ~ n :~
-- ;~2 --~2~
~, ~P
N
~32~
d ~ I ~n~
~ ~ ~ @ ~
1~ D ~
. ~ . ~
~ , ~ . ~
~ 0 m ~
:
,; ,' :
- 24 ~
~ ;~ ~ , ~ ~1 ~ ~ ~ 3DD~DD
3 ~ ~ 3; ~ ~ ~ N ~ t`~
~ ~ ~s~ ~ O e~
- 25 - ~32~
3~ ~3~
~ ll D
~ ~ D
~ ~ 4 o 8 ~ ~ ~
- 2 6 ~- ~ 3 2 ~
~ ~ B
o ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
~ , ~
,_ . ~ , a .~
~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ 'U
.~
~ 3 ~
o ~
t~ ~ N N
~ $~$~ ~ ~ a ~
. ~ ~ ~ un ~ O
r~
. ; . .
~32~
~ ~ ~ ~W~
; ,, 8 ~ ~
I ~ 7 l ~
D
~ .~ $~
U~ 0 ~I r~
";.
-~, , .. . ~ . ... .i . ..
-. ~.
. ~. . ~ . . ,~ . . .. .
- 29, ~L3?~
~ ~ ~ ~ D ~
.~ , A~ ~i ~ a ~
,, , ., ` I
3 ~ ~ 2 ~
~4 :: ~
~n ~
D
~ ~ ~ ~D D
. o ~ ~ ~ ` CO n o ~
: ~:
.- 31 - ~32~ 3 8 ~ 8 ~ 8 r;4 ~i ~, N ~ N ~ 5~ N 3 ~ ~ ~
~ ~ $ ~
~ ~ ~ ~ ~ ~ o ~ ~ ~ ~ ~ ~ ~
' ~ ~ , . ` .
~` . . .
.
~ 3 2 ~ J ~ ~
. ~ ~, ' g ~ ~
o ~ ~ 8 ~ Q
D D ~ D fi D N
. ~ o ~ ~ cn o P~ 0~ l ~D O O C:> O~ C~
~ ;' ' , ~ , ` ' ;, :
~ 3~ 32~
~ 11 ~
-l l :o~ 5~, 0 ~3 1~ C~ t~ ~ ~ t~ N N S~
.
.
. ~ , ; , ' - 3~ D 3~L~I~
,1:
~ ~ ~ . ~ ~
' i ~
G~
O ~ O ~ O
1~
:~ t~ h. ~ 1~ ~ h h i ~
r~
J~ N ~ ~ ~ N
., , : : , .: , .
.. ..
Claims (12)
1. A monoazo compound conforming to the general formula (1) (1) where the variables have the following meanings:
D is a para- or meta-phenylene group which can be sub-stituted by 1 carboxy group or 1 to 2 sulfo groups, or is a naphthylene group which contains the azo group bonded in the 1- or 2-position and to which the grouping X-N(R)- is bonded in the 5- or 6 position and which can be substituted by 1 carboxy group or 1 or 2 sulfo groups, R is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, or is a hydroxy-, cyano-, carboxy-, sulfo-, sulfato- or phosphato- or phenyl- or sul-fophenyl-substituted alkyl group of 1 to 4 carbon atoms, M is a hydrogen atom or an alkali metal or equivalent of a divalent metal, X is a group of the formula (2) (2) where Y is halogen, R1 is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, or is an alkyl group of 1 to 4 carbon atoms which is substituted by a sulfo, carboxy, phosphato, sulfato, hydroxy or cyano group and/or by a phenyl or naphthyl radical which may be sub-stituted by sulfo, carboxy, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and/or nitro and R2 is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, which is substituted by sulfo, car-boxy, phosphato, sulfato, hydroxy or cyano, or by a phenyl or naphthyl radical which may be substituted by sulfo, carboxy, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and/or nitro, or denotes a phenyl radical which can be substituted by 1, 2 or 3 substituents selected from the group consisting of the following substituents
D is a para- or meta-phenylene group which can be sub-stituted by 1 carboxy group or 1 to 2 sulfo groups, or is a naphthylene group which contains the azo group bonded in the 1- or 2-position and to which the grouping X-N(R)- is bonded in the 5- or 6 position and which can be substituted by 1 carboxy group or 1 or 2 sulfo groups, R is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, or is a hydroxy-, cyano-, carboxy-, sulfo-, sulfato- or phosphato- or phenyl- or sul-fophenyl-substituted alkyl group of 1 to 4 carbon atoms, M is a hydrogen atom or an alkali metal or equivalent of a divalent metal, X is a group of the formula (2) (2) where Y is halogen, R1 is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, or is an alkyl group of 1 to 4 carbon atoms which is substituted by a sulfo, carboxy, phosphato, sulfato, hydroxy or cyano group and/or by a phenyl or naphthyl radical which may be sub-stituted by sulfo, carboxy, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and/or nitro and R2 is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, which is substituted by sulfo, car-boxy, phosphato, sulfato, hydroxy or cyano, or by a phenyl or naphthyl radical which may be substituted by sulfo, carboxy, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and/or nitro, or denotes a phenyl radical which can be substituted by 1, 2 or 3 substituents selected from the group consisting of the following substituents
2 alkyls of 1 to 4 carbon atoms, 2 alkoxies of 1 to 4 carbon atoms, 1 bromine, 2 chlorines, 3 sulfos, 2 carboxys, 1 nitro, 1 alkylsulfonyl of 1 to 4 carbon atoms which may be substituted by hydroxy, 1 alkyl-amino of 1 to 4 carbon atoms and 1 alkylamino of 1 to 4 carbon atoms which may be substituted in the alkyl radical by hydroxy, sulfato, sulfo, phos-phato, alkanoyloxy of 2 to 5 carbon atoms or by carboxy -substituted alkanoylamido of 1 to 4 carbon atoms in the alkylene radical, or R2 denotes a monosulfo-, disulfo- or trisulfo-naphthyl radical, R1 and R2 being identical to or different from each other, or R1 and R2 together with the nitrogen atom form a hetero-cyclic radical composed of an alkylene radical of 3 to 8 carbon atoms, or a further heteroatom and two alkylene radicals of 1 to 4 carbon atoms.
2. A compounds claimed in claim 1, wherein Y is a chlorine atom.
2. A compounds claimed in claim 1, wherein Y is a chlorine atom.
3. A compound as claimed in claim 1 or 2, wherein R1 is a hydrogen atom and R2 is a phenyl radical which is substituted by a sulfo group and may additionally be substituted by a further sulfo group or a methoxy group.
4. A compound as claimed in claim 1 or 2, wherein R is a methyl group.
5. A compound as claimed in claim 1 or 2, wherein D is a meta- or para-phenylene group which in either case is substituted by 1 or 2 sulfo groups.
6. A compound as claimed in claim 1 or 2, wherein M is a hydrogen atom or an alkali metal.
7. A process for preparing a compound of the general formula (1) according to claim 1, which process comprises:
a) reacting a compound of the general formula (3) (3) where R, D and M are as defined in claim 1, with a compound of the general formula (4) X - Y (4) where X and Y are as defined in claim 1, or b) diazotizing an aromatic amino compound of the general formula (5) (5) where X, R and D are as defined in claim 1, and coupling the diazonium compound with 2-naphthol-6-carboxylic acid or a salt of this carboxylic acid, or c) reacting a compound of the general formula (6) (6) where the two Ys and also R, D and M are as defined in claim 1, with an amino compound of the general formula HNR1R2 with R1 and R2 of the meaning mentioned in claim 1.
a) reacting a compound of the general formula (3) (3) where R, D and M are as defined in claim 1, with a compound of the general formula (4) X - Y (4) where X and Y are as defined in claim 1, or b) diazotizing an aromatic amino compound of the general formula (5) (5) where X, R and D are as defined in claim 1, and coupling the diazonium compound with 2-naphthol-6-carboxylic acid or a salt of this carboxylic acid, or c) reacting a compound of the general formula (6) (6) where the two Ys and also R, D and M are as defined in claim 1, with an amino compound of the general formula HNR1R2 with R1 and R2 of the meaning mentioned in claim 1.
8. Use of a compound according to the formula (1) as claimed in claim 1 or 2, for dyeing hydroxy- and/or carboxamido-containing material.
9. A process for dyeing hydroxy- and/or carboxamido-containing material, in which a dye is applied to or introduced into the material and fixed by means of heat and/or means of an acid-binding compound, which process comprises using as the dye a compound according to the formula (1) as claimed in claim 1 or 2.
10. A compound as claimed in claim 1 or 2, wherein R is a hydrogen atom.
11. Use according to claim 8 for dyeing fiber material.
12. A process according to claim 9 for dyeing fiber material.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3800692A DE3800692A1 (en) | 1988-01-13 | 1988-01-13 | WATER-SOLUBLE AZO COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS DYES |
| DEP3800692.8 | 1988-01-13 | ||
| IN490CA1991 IN172429B (en) | 1988-01-13 | 1991-06-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1320949C true CA1320949C (en) | 1993-08-03 |
Family
ID=25863896
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000588031A Expired - Fee Related CA1320949C (en) | 1988-01-13 | 1989-01-12 | Water-soluble azo compounds, preparation and use thereof as dyes |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0324373B1 (en) |
| JP (1) | JPH01215862A (en) |
| CA (1) | CA1320949C (en) |
| DE (1) | DE3800692A1 (en) |
| ES (1) | ES2048217T3 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3943286A1 (en) * | 1989-12-29 | 1991-07-04 | Hoechst Ag | AZO COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A DYE |
| DE3943287A1 (en) * | 1989-12-29 | 1991-07-04 | Hoechst Ag | AZO COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS DYES |
| KR100511483B1 (en) * | 1997-08-28 | 2005-08-31 | 가부시키가이샤 우에노 세이야꾸 오요 겡뀨조 | Water-soluble azo compounds and process for preparing the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR641816A (en) * | 1926-10-05 | 1928-08-11 | Ig Farbenindustrie Ag | Process for the production of new azo dyes |
| DE965902C (en) * | 1949-07-19 | 1957-09-19 | Hoechst Ag | Process for fixing water-soluble organic compounds on substrates with a fibrous structure |
| DE3738831A1 (en) * | 1987-11-16 | 1989-05-24 | Hoechst Ag | WATER-SOLUBLE AZO COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS DYES |
-
1988
- 1988-01-13 DE DE3800692A patent/DE3800692A1/en not_active Withdrawn
-
1989
- 1989-01-05 ES ES89100121T patent/ES2048217T3/en not_active Expired - Lifetime
- 1989-01-05 EP EP89100121A patent/EP0324373B1/en not_active Expired - Lifetime
- 1989-01-12 JP JP1003880A patent/JPH01215862A/en active Granted
- 1989-01-12 CA CA000588031A patent/CA1320949C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE3800692A1 (en) | 1989-07-27 |
| ES2048217T3 (en) | 1994-03-16 |
| EP0324373A3 (en) | 1990-03-07 |
| EP0324373B1 (en) | 1993-12-08 |
| EP0324373A2 (en) | 1989-07-19 |
| JPH01215862A (en) | 1989-08-29 |
| JPH0588909B2 (en) | 1993-12-24 |
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