IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOUNDS

Abstract: A monoazo or disazo compound in metal-free form or in 1:1 or 1:2 metal complex form which in the metal-free form corresponds to formula (I): CH2=CH-SO2-W1-D - N = N - K-(W2-Z)n in which D is the radical of a diazo component, K is the radical of a coupling component, W1 is a direct bond or a divalent bridging group, W2 is a divalent bridging group, n is an integer 1 to 4, Z is a water solubilising protonable amine group, a quaternary ammonium group, a hydrazinium group or a ternary sulphonium group, which compound is in free basic, salt form or acid addition salt form formed by the addition of dilute aqueous organic or mineral acids, can be used for dyeing or printing fibers, threads or textile material particularly containing or consisting of natural or synthetic polyamides, cotton, polyacrylonitrile, leather or fibre blends such as cotton-polyester, polyester-wool and polyacrylonitrile-wool.

Description: IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOUNDS The invention relates to water soluble azo compounds which contain basic groups and are free from suiphonic acid groups which compounds are metal-free or are in the 1:1 or 1:2 metal complex form. These compounds are suitable for use as dyestuffs. According to the invention there is provided a moπoazo or disazo compound in the metal-free form or in the 1:1 or 1:2 metal complex form which in the metal-free form corresponds to formula I CH z =CH-S0 2 -W 1 -D - N = N - K-(W 2 -Z) n I in which D is the radical of a diazo component of the benzene, naph¬ thalene or tetrahydronaphthalene series, K is the radical of a coupling component of the benzene, naph¬ thalene, pyrazol-2-one, pyridine, pyridone, barbituric acid, quinoline, isoquinoline, benzene- or naphthalene- or tetra- hydronaphthalene-azo-benzene or -azo-naphthalene, or of the acetoacetamide series, _ is a direct bond or a divalent bridging group, each fø, independently, is a divalent bridging group, n is an integer 1 to 4, each Z, independently, is a water solubilising protonable amine group, a quaternary ammonium group, a hydraziπiu group or a ternary sulphonium group, with the proviso that any Z containing a quaternary N direct ¬ ly bound to the carbon atom of a triazine or pyrimidine group which therefore constitutes part of a fibre-reactive grouping is excluded; which compound is in free basic form, salt form or acid addition salt form formed by the addition of dilute aqueous organic or mineral acids, and mixtures of compounds of formula I. Preferably, D is the radical of a diazo component of the benzene or naphthalene series in which the group - ]_-Sθ2CH=CH2 is preferably bound in the 3- or 4-position of any phenyl group; in any naphthyl group -W]_-S02CH=CH2 is particularly preferred in the 4-position. D is further unsubstituted or may contain one or two further substituents conventional in the chemistry of fibre-reac¬ tive azo compounds (with the exception of suiphonic acid groups) including any metallisable substituent in the ortho position to a carbon atom bound to the azo group, such as a hydroxy, amiπe, substituted a ine, methoxy or carboxy group. K is preferably the radical of a coupling component of the a inobenzene, phenol, aminophenol, a inonaphthalene, naphthol or aminonaphthol series or of the naphthalene series containing any other substituent enabling the coupling; of the l-arylpyrazol-5-one, aminopyridine, hydroxypyridone, barbituric acid, N-alkyl or N-aryl substituted acetoaceta ide, benzene- or naphtha!ene-azo-benzene, benzene-azo-naphthalene or tetrahydronaphthalene-azo-benzene series. Additionally to the n groups - 2-Z K is further unsubstitu¬ ted or may contain one or two further substituents conventional in the chemistry of basic azo compounds including those substituents which enable the metallisation and therefore are in the ortho position to a carbon atom bound to the azo group. n is preferably 1 or 2. W]_ is preferably a direct bond; a C^alkylene or C _6alke- nylene group which groups are straight chain or branched, unsub- stituted or onosubstituted by hydroxy, halogen, cyaπo, C^alkox or phenyl and in which the carbon chains may be interrupted by one or two hetero atoms; -C0NH-X-, -C0-X-, -S0 2 NH-X-, -NHC0-X-, -NH-X or -NHNHC0-X-, in which X is Cι_6alkylene or C _6*3 ' * ! <eπyl ne and which groups are bound to the -SO2 group by a carbon atom of X; -CH2CONHCH2- or -CH 2 NHC0CH 2 -. Each W " 2, independently, has preferably one of the signifi¬ cances of w " ι except a direct bond where Z is attached to a carbon atom of X. Each Z, independently, is preferably a water solubiusing protonable amine group or a quaternary ammonium group; preferably Z is a primary amine group, a secondary or tertiary aliphatic, cycloaliphatic, aromatic or saturated or partially unsaturated heterocyclic amine group in which latter group the N-atom or a carbon atom is attached to ?; or a quaternary ammonium group corresponding to the above. In the specification any halogen means fluorine, chlorine, bromine or iodine preferably chlorine or bromine. The term "basic groups" includes also quaternary ammonum groups, hydraziniu groμps and ternary sulphonium groups. Any alkyl, alkylene or alkenylene present may be linear or branched unless indicated otherwise. The alkyl group of any alkoxy group is linear or branched unless indicated to the contrary. In any hydroxy substituted alkyl, alkylene or alkenylene group which is attached to a nitrogen atom the hydroxy group is bound to a carbon atom other than to the C^-atom. Any aliphatic amine group as Z is preferably a mono-Cι.4- alkyl- or a di-(Cι_4a1kyl )-amine group. The alkyl group may be mono-substituted by halogen, hydroxy, cyano, C^alkoxy or phenyl. Any cycloaliphatic amine group is preferably C5_6cyclo- alkylamino, the cycloalkyl group of which may be substituted by one or two C]._2alky1 groups. ■ Any aromatic amine group is preferably phenyl amino, the phenyl ring of which is unsubstituted or substituted by one or two groups selected from halogen, C^alkyl, C^alkoxy, hydroxy and phenoxy. Any heterocyclic amine group as Z in which the N-atom or a carbon atom is attached to - is preferably a saturated, unsaturated or partially unsaturated 5- or 6-membered ring which contains one or two hetero atoms and may be further substituted by one or two C, .alkyl groups. * 1:1 or 1:2 metal complexes of compounds of formula I according to the invention preferably, in the 1:1 metal complex form, correspond to formula II or III H 2 C — 2 —Z) n II in which W]_, W 2 , 0, Z and n are as defined above, Me is copper, chromium, cobalt, nickel or iron for 1:1 metal complexes (Me is preferably copper in this case) or Me is chromium or cobalt for 1:2 metal complexes, Y]_ is -0- or -C00-, each of Y2 and Y3, independently, is -0-, -NH- or -N^ , D^ is the radical of a diazo component like D, K|< is the radical of a coupling component like K and Kj is the radical of a coupling component of the benzene or naphthalene series, where each of D^, K k and K^ is a group containing in an ortho position to the carbon atom attached to the azo group either hydrogen or a metal usable group resulting in Y]_ (-0- or -COO) and Y 2 /Y 3 (-0-, -NH- or -N ), respectively, K 0 is the radical of a coupling/diazo component of the benzene, naphthalene or tetrahydronaphthalene series containing in an ortho position to the carbon atom attached to the group -N=N- either hydrogen or a metal!isable group resulting in Y 2 , the n groups - 2 -Z are bound to K 0 and/or to K . Preferred compounds or complexes according to the invention correspond in the metal-free form to formula la, Da - N = N - Ka la in which Da is a group (a) or (b) , (a) (b) in which each of R and R 2 , independently, is hydrogen, halogen, hydroxy, cyano, nitro, trifluoro ethyl , carboxy, C^alkyl, Cχ_4a!koxy, phenoxy, the phen l ring of which is unsubsti¬ tuted or substituted by up to three halogen atoms; sulphonamido, -S0 2 NHCι_4alky! , -S0 2 N(C]__4a!kyl ) , -S0 2 C]__4alky! , -NHC0C]__4a!kyl , benzamido or phenyl amino, R3 is hydrogen, halogen, hydroxy, amino, C-^alkyl, C-^alkoxy, phenoxy, phenyl amino, -NHC-^alkyl , -N(C ] __4alkyl ) , -NHCOC j ^alkyl or benzamido, W]_ a is a direct bond, a C^galkylene or C _galkenylene group which groups are unsubstituted or monosubstituted by halogen, hydroxy, C^al oxy or phenyl, and in which the -C-C- chains may be interrupted by an N, 0 or S atom; -NH-Xa■ -C0NH-X a -, -NHC0-X a -, -C0-X a -, -S0 2 NH-X a -, -NHNHC0-X a -, -CH 2 C0NHCH 2 - or -CH-jNHCOCH-?-, X j is Ch l y! ene or C 2 -.4 alkenylene, provided that *A\ a is attached to the SO2 group by a carbon atom of X a , Ka is a group K containing at least one group - 2 > Z which corresponds to a group (c) to (i) : - in which R4 is hydrogen, halogen, hydroxy, Cχ_4alkyl, C^alkoxy, -N_.COC1_4a.lcyl, -NHC0NH 2 , -SO2NH2, -S0 NHq_4alkyl , -S0 2 N(C 1 . 4 alkyl)2, -NHC0(CH 2 ) 1 _ 4 -Z 1 or R5 is hydrogen, Chal !,. C]_>4_a!koxy, halogen or hydroxy, R5 is hydrogen, unsubstituted Ci.galkyl, substituted C^galkyl by one or two hydroxy groups or by a phenyl group, halogen or cyaπo; -(CH2)ι_4-NHC0(CH2)ι_4-Zι or C _galkyleπe-Z] > , in which the alkylene group may be substituted by one or two hydroxy groups, R7 is hydrogen, unsubstituted Chalky! , Chalk ! substituted by one or two hydroxy groups or by a phenyl group, halogen or cyano; -COCH2-Z1, Chalky!ene-Z * L in which the alkylene group may be substituted by one or two hydroxy groups and in which the alkylene chain may be interrupted by atom groups, such as, -NH-, -NCH3-, -S-, -0- each Z- j , independently, Q and Q, are (d) is a group of formulae (ά ) to (d$) , where (ύ ) to (d 3 ) are naphthol groups of the formulae in which R8 is -C0NH(CH 2 ) 1 . 4 -Zι, -CONH or -CONH -@ NH - A R 8b is -NHC0(CH 2 )i_4-Zι, -S0 2 NH(CH 2 )i-4-Zι or R 8c is -NH(CH 2 )ι_4-Z 1 or and Q, Qi defined below; (d4) is an aminonaphthyl group of the formulae in whic and (ds) is a naphthyl group of the formula in which one of the R3_' s is hydrogen and the other is -C0NH(CH 2 )ι_ 4 -Zι, -NHC0(CH 2 )ι_4-Zι, -Sθ2NH(CH 2 ) -Zi, t is 0 or 1 and Q, Q and Z^ are as defined below; (e) is a group of the formula in which Rg is C1_.4a.kyl, COOH or COOC1_.4a.ky., each of-Rn and R12, independently, is hydrogen, halogen, nitro, amino, cyano, hydroxy, Chal ! or a as one o e s gn cances of w " ι a defined above except a di¬ rect bond, where Z, is attached to a carbon atom of X a , and Zi, Q, Qi and A® are as defined below; (f) is a group of the formula in which Rl is hydrogen, C^al yl ,* phenyl , benzyl or cyclohexyl, Rl5 is hydrogen, cyano, -C0NH 2 , -S0 2 NH 2 , -N A© or Rl6 , Chalky! unsubstituted or alogen or C^alkoxy; - CH 2 ) 1 . 4 -NHC0-tCH 2 ) 1 . 4 -Z 1 or t is 0 or 1, and Q, Qi, Zi and A® are as defined below; (g) is a group of the formula in which R 17 1S R ll > R 12 ar, d ^13 are as defined above and Zi is as defined below; (h) is a group of the formula R 1 in which Rχ4 is as defined above, Rχ8 is hydrogen, cyano or -C0NH 2 , each of Rig, independently, is hydrogen, a Chalky! group which is unsubstituted or monosubstituted by hydroxy or Cι_4a1koxy; or C _galky1ene-Zι, and Z is as defined below; A® is an equivalent of a non-chromophoric anion; Q is a group -NH(CH 2 ) _g-Z , Q is halogen, hydroxy, amino, C^al oxy, phenoxy, phenylamino, cyclohexyl amino, Cι_4alky1amino, di(C _4alky1) amino or Q; Zi is a protonable amine group -NR 2 QR 2 I or a quaternary ammonium group - R 2 R 3R2 A ®» or Z forms a protonable or quaternary 5- or 6-membered saturated heterocyclic ring of the formula -C H N-R25 or -C H N = (R 26 ) 2 A© or a corresponding protonable or quaternary 5- or 6-membered unsaturated or partially unsaturated heterocyclic ring, each of R20 and R21_ independently, is hydrogen, Chal y! , C2-4a1ky1 monosubstituted by hydroxy, Cι_4alkoxy, halogen or cyano; phenyl-Chal y!, the phenyl group of which is unsubstituted or substituted by one to three groups selected from chlorine, Chalky! and or Cs-δcycloalkyl, or R20 and R2 , together with the N-atom to which they are attached, form a heterocyclic ring of the formula in which U is the direct bond, -CH -, -0-, -S-, -S0 -, -SO-, -NH-, -N(Cι_ 4 alkyl)- or - (Cι_ 4 alky1) 2 - A®, each of R22 and R 23 has independently one of the cyclic or non-cyclic significances of R 2 Q and R 2 χ except hydrogen, and *R 2 4 is Cι_4alky1 or phenyl-Chalky! , or R 22 , 23 and R24, together with the N-atom to which they are * attached, form a pyridiniu group unsubstituted or substituted by one or two methyl- groups, or a ring of the formula in which R24, U and fβ are as defined above, R25 is hydrogen or Chalky! and each of R25, independently, is (i) is a group of formulae χ) to (1 * 4) or Z 1 , in which each of R4 and R5, independently, is as defined above and Rg, R7, Q, Q- and Zi are as defined above. More preferred are compounds or complexes according to the invention containing one or two protonable amine groups or quaternary ammonium groups as defined above which correspond in the metal-free form to formula lb or Ic in t is 0 or 1 , R 3a is ^d ogen or hydroxy Kc is a group of the formula Rla 1S hydrogen, halogen, Chalky! , Ci^al oxy, OH, COOH, CN, phenoxy, the phenyl group of which may be substituted by one to three chlorine atoms, -SO2NH2, -S02 HC _ a1 yl , -S0 2 N(Cι_ alky1) , -NHC0CH 3 or phenylamino, ^2a is hydrogen, halogen, Cι_ 2 alkyl or Cι_ 2 alkoxy; Kb is a group ( ); ( ι a ), (d 2a ), (d 3a ), (d 5a ); (e ), (f^, (gi), (i 2a ), (i a ) or (i 4a ), (c,) in which R4 a is hydrogen, chlorine, Cι„ a1kyl, Cι. a1koxy, -NHC0C _ 2 alky1, -NHC0NH 2 or -NHC0(CH 2 ) _4-Z 2 , R5 a is hydrogen, chlorine, Cι. 2 a1ky1 or Cι_ 2 alkoxy, R6 a is hydrogen, Cι_ 2 alky1, benzyl, C2H4OH, C 2 H 4 CN, C 2 H 4 C1 , Ci-4a1kylene-Z 2 , -CH 2 CH(OH)CH 2 -Z 2 or-(CH 2 ) . 3 -NHC0CH 2 -Z2, R7 a is hydrogen, Cι„2 alkyl, benzyl, C 2 H4θH, C2H4CI , C2H4CN, Cι_4alkylene-Z 2 , -CH 2 CH(OH)CH 2 -Z 2 , -( H2)2-3-0CH2CH(0H)CH2-Z 2> -(CH 2 )2-3-NHC0CH2-Z 2 , -C0CH 2 -Z 2 , - ( CH 2 ) 2- 3 -< > > la _ 4 -Z 2 , -S0 2 NH(CH 2 ) 2 _ 3 -Z 2 or 'la R 8 ^ is -NHC0(CH 2 ) 2 _ 3 -Z 2 , - H(CH 2 ) 2 _ 3 -Z 2! ■ ne of the groups Rβd' is hydrogen and the other is each of Rn a and Ri2a » independently, is hydrogen, chlorine, methyl or methoxy, Rl 3a is -NHC0CH 2 -Z 2 , -C0NH(CH 2 ) 2 . 3 -Z2 or in which R 14a is hydrogen, methyl, ethyl or benzyl, R 5a is hydrogen, -C0NH 2 or -CH 2 NHC0CH 2 -Z2, Rlδa is hydrogen, Cι„ 2 alkyl, (CH 2)l . 4 -Z 2 -(CH 2 ) 1 . 4 -NHC0(CH 2 ) 1 _ 4 -Z 2 or C0CH 3 -CH-CONH-R 17a (9-) in and n > R 12a and R 13a are as defined above; in which Ma is R 4a> R 5a» R 6a and R 7a are as defined above and Z2 is as defined below; Q a is a group -NH(CH )ι_4~Z and Qι a is chlorine, OH, H2, phenoxy, phenylamino or Z 2 a group - 20 a 21a or " NR 22a R 23a R 24a A<Ξ> > t@ is an equivalent of a non-chromophoric anion, each of 2 θa and 2la » independently, is hydrogen, Ci^alkyl, unbranched hydroxy-C2> alkyl or benzyl or both R2Qa and 21a» together with the N-atom to which they are attached, form a pyrrol idine, piperidine, morpholiπe, piperazine or N-methylpiperazine group, each of R22a ar *d 23a as independently one of the non-cyclic or cyclic significances of R20a and R2i a except hydrogen, and 24a is me hyl , ethyl or benzyl, or 22a' R 23a an d 24a» together with the N-atom to which they are attached, form a pyridinium group unsubstituted or substituted by one or two methyl groups. In a compound of formula lb the positions for Rι a , R2 a and the group -(CH2)*t SO2CH = CH2 ( - R) preferably are as follows: (i) la = R 2a = H: R can be in any positions 2 to 6 of the phenyl group; more preferably, it is in the 3- or 4-positioπ; (11) one of Rι a and R 2a ■■ ? H, the other = H: R la ( R 2a) 1S in th e 2-position, R is in the 4- or 5-position; Rl a and R2 a are in the 2- and 6-positions, R is in the 4-position. Most preferred are compounds or complexes according to the invention which, in the metal-free form, correspond to formula Id, in which t is 0 or 1, Rib is hydrogen, chlorine, bromine, cyano, methyl or 2b is hydrogen, chlorine or bromine; Kd is a group (02), (dι b ), (d 2b ), ( b) or (f2), in which R b is hydrogen, methyl, -NHCOCH3 or -NHC0CH 2 -Z 3 , 5b is hydrogen or Cι_ 2 alkoxy, R 6b is hydrogen, Chalky! , C H4OH, C 2 H 4 CN, - ^2)2-3^3, -CH 2 CH(OH)CH 2 -Z 3 or-C 2 H4NHC0CH2- 3 , R 7b is -(CH 2 ) 2 _ 3 -Z 3 , -CH 2 CH(0H)CH 2 -Z 3 , -C 2 H 4 -Q, f .C2H 0CH 2 CH(0H)CH2-Z 3 , ■ C H4NHCOCH2-Z2 or -C0CH 2 -Z 2 ; < d l b) ( d 2b) < d 3b> in which R is hydrogen or hydroxy, in which R 5b is hydrogen, CONH-? or -CH 2 NHC0CH 2 -Z 3 , Rl 6b is hydrogen, -(CH 2 ) 2 -3- z 3 or A© is an equivalent of a παn-chro ophoric anion, each Q and Qib, independently, is a group -NH(CH2)2-3~Z3, _B Z 3 is a group -NR 2 0b R 21b or " N 22b R 23b R 24b * each of R20 ar| d 21b is methyl or ethyl or both R20 b aπd R 21 b ' together with the N-atom to which they are attached, form a piperidine, morpholine, piperazine or N-methylpiperazine ring; each of R22b and R2 3 is methyl or ethyl or both R22 and R2 3 b» together with the N-atom to which they are attached, has one of the cyclic significances of R20b aπ d R 21b> 24b is methyl or ethyl or R 22b» 23b ar *d R 24 b » together with the N-atom to which they are attached, form a pyridinium group unsubstituted or substituted by one or two methyl groups. In a compound of formula Id the group -(CH2)t-S02CH=CH2 is preferably (i) in the 3- or 4-position when R^ ~ 2b = hydrogen; (ii) in the 4- or 5-position when one of Ri and R b is hydrogen and the other is other than hydrogen; (iii) in the 4-position when R^ and R2b are both other than hydrogen; more preferably t is 0. In the compounds of formula I the anions fβ can be any non-chromophoric anions such as those conventional in basic dyestuff chemistry. Suitable anions include chloride, bromide, sulphate, bisulphate, methylsulphate, aminosulphonate, perchlorate, benzenesulphonate, oxalate, maleate, acetate, propionate, lactate, succinate, tartrate, malate, methane sulphonate aπd benzoate as well as complex anions, for example zinc chloride double salts and anions of boric acid, citric acid, glycolic acid, diglycolic acid and adipic acid or addition products of ortho boric acids with polyalcohols with at least one cis diol group present. These anions can be exchanged for each other by ion exchange resins or on reaction with acids or salts (for example via the hydroxide or bicarbonate) or according to the method given in German Offenlegungsschrift 2001 748 or 20 01 816. Compounds of formula I can be prepared by reacting a diazotised compound of formula IV with a compound of formula V H-K-(W 2 -Z) n V and optionally converting the obtained metal-free compound of formula I into the corresponding 1:1 or 1:2 metal complex. Diazotisation and coupling reactions may be effected in conventional manner. The conditions of any coupling reaction e.g., temperature and pH, depend on each particular coupling component used in the preparation process. A compound of .formula I can also be prepared by splitting off a compound H-8 from a compound of formula VI, B-CH2-CH 2 -Sθ2-W -0-N=N- -(W2-Z) n ' VI in which B is a group which under the reaction conditions is split off, such as -0S0 H, -0P0 3 H 2 , halogen, -0C0CH 3 , -SS0 3 H, amino, lower alkyl substituted amino or a lower alkyl substituted quater¬ nary ammonium group. This reaction is carried out in accordance with known methods. Advantageously, splitting off is effected in an aqueous alkaline medium in the presence of a basic compound such as sodium hydroxide, where the pH is in the range of 6 to 13, especially 10 to 11. The starting compounds of formula IV, V and VI are either known or may be prepared in accordance with known methods from available starting materials. Compounds of formula I containing metallisable groups in an ortho position to the carbon atom attached to the azo group may be converted into metal complexes by reacting the metal-free compound of formula I with a metal donating compound which is employed in such an amount to provide at least one equivalent of metal per equivalent of monoazo compound to be metallised. Metallisation is carried out in accordance with known methods. For example, metal complexes of formula II or III can be prepared by reacting a compound of formula Ha or Ilia in which Yl a is H, OH, Cι. 4 alkoxy or COOH, Ϊ2a is OH, NH 2 or substituted amino, Y a is H, OH, NH2, substituted amino or C, .alkoxy, and each of Y, , Y 2a and Y_ is in an ortho position to the azo group, with a metal donating compound in such an amount to provide at least one equivalent of metal per equivalent of monoazo compound to be metallised to obtain a 1:1 or 1:2 metal complex. Preferred is the 1:1 metallisation and more preferred the preparation of 1:1 copper complexes. Suitably, the preferred 1:1 copper complexes are prepared either by oxidative coppering, preferably at 40-70°C and at pH 4-7 in the presence of copper(II) salts or using copper powder in the presence of hydrogen peroxide or other conventional oxidising agents; or preferably by demethylation coppering, preferably at pH 3-4 and at elevated to boiling temperature in the presence of copper(II) salts. The compounds of formula I in the metal-free form or in the 1:1 or 1:2 metal complex form may be isolated in accordance with known methods. Those compounds of formula I containing basic groups may be converted into water soluble salts by reacting with at least stoichiometri ' c amounts of an inorganic mineral acid such as hydrochloric acid, sulphuric acid, phosphoric acid or preferably an organic acid such as formic acid, acetic acid, lactic acid, citric acid, glycolic acid or methane suiphonic acid. The metal-free compounds of formula I and 1:1 or 1:2 metal complexes thereof in their acid addition salt form or as quater¬ nary ammonium salt (hereinafter referred to as the dyes of formula I) are useful as dyestuffs for dyeing and printing fibres, threads or textile materials particularly natural or synthetic polyamide materials, for example wool, silk, nylon etc. which preferably can be dyed .by exhaustion using a long or short liquor at room to boiling temperature. Printing can be " carried out by impregnation with a printing paste which can be prepared by. known methods. Furthermore, the dyes of formula I can be used for dyeing or printing cotton, polyacrylonitrile or fibre blends, such as cotton-polyester, polyester-wool or polyacrylonitrile-wool fibre ' blends. The dyes of formula I are also well suited for dyeing or printing leather including low affinity vegetable-tanned leather, in accordance with known methods. The resulting dyeings and prints on the different substrates show good fastness properties. The dyes of formula I have good solubility properties in particular good cold water solubility. They build-up well, migrate well and have notable equalising properties particularly on wool or synthetic polyamide substrate even without using any levelling agent; they give high exhaust and fixation yields. The portion of unfixed dyestuff can be easily washed off the substrate. The resulting dyeings and prints are brilliant and show notably good light fastness properties; on exposure to light for a long time the shade of the dyeing fades tone in tone. Furthermore, the dyeings made with the dyestuffs according to the invention have good wet fastness properties. Any aftertreatment with ammonia usually carried out for fibre-reactive dyeings on wool to improve the wet fastnesses is unnecessary. The dyeing process therefore is gentle on the wool-fibres. The dyes of formula I are also well suited for dyeing in combination. The thus obtained dyeings have good fastness properties. The following Examples further serve to illustrate the invention. In the Examples all parts and percentages are by weight or volume and the temperatures given are in degrees centigrade unless indicated to the contrary. Example 1 21.8 Parts of l-amino-2-chloro-4-viny1sulphonylbenzene are dissolved in 500 parts of glacial acetic acid at 70". To this solution 38 parts of 30% hydrochloric acid and then a solution of 6.9 parts of sodium nitrite in 25 parts of water are added whilst cooling with ice. After one ' hour any excess of nitrous acid is decomposed by the addition of 0.5 parts of sulphamic acid. The. resulting suspension is added dropwise to a solution consisting of 27.6 parts of the coupling component of the formula in 1200 parts of water within one hour. The pH of the coupling mixture is kept at 3.0 to 3.5 by the addition of sodium acetate. After three hours the dark-red solution is adjusted to a volume of 2.5 litres. The thus obtained dyeing solution containing the dye¬ stuff of the formula dyes wool a red shade. This dyestuff has notably good levelling properties. The resulting wool dyeings have good light and wet fastness properties. Example 2 31.6 Parts of l-amino-2-chloro-4-(2'-su1phatoethyl)sulpho- nylbenzene (which is prepared in accordance with known methods) are dissolved in 800 parts of water and 35 parts of a 30% hydro¬ chloric acid solution and are diazotised at 0 β to 5 * by the addition of 6.9 parts of sodium nitrite in 25 parts of water. After one hour any excess of nitrous acid is decomposed by the addition of 0.5 parts of sulphamic acid. The clear solution of the diazonium salt is added to a solution containing 27.6 parts of the coupling component of the formula in 1000 parts of water. The pH of the coupling mixture is kept at 3.0 to 3.5 by the addition of solid sodium acetate. After three hours the dark-orange solution containing the dyestuff correspon¬ ding to the formula in which A© is the anion of the reaction medium, is adjusted to a volume of 2.5 -litres by the addition of water. Adjusting the pH of this solution at 10 to 11 by the addition of sodium hydroxide solution the dyestuff corresponding to the formula in which A© is as defined above, is obtained which dyes wool as well as silk a brilliant orange shade. These dyeings show good fastness properties. In the intermediate monoazo compound of Example 2 any further group to be split off can be used instead of the group -0S0 3 H, for example, a chlorine, bromine, tosyl or ammonium group. Example 3 When using an equimolar amount of the diazoπium salt of 1-amino- 2-methyl-4-vinylsulphonylbenzene (prepared in accordance with the method given in Example 1) which is coupled with a solution of 26 parts of the coupling component of the formula dissolved in 500 parts of water and 100 parts of glacial acetic acid an orange mixture is obtained. After a short time the dye¬ stuff precipitates and is filtered from the suspension and dried. The dyestuff having the formula is obtained in form of the acid addition salt with acetic acid which dyes polyester as well as polyester/cotton fibre blends or synthetic polyamides a scarlet shade. The.dyeings have good fast¬ ness properties. Examples 4 to 77 Further compounds according to the invention and correspon¬ ding to formula (1) in which the symbols are defined in Table 1 below can be prepared by a method analogous to that of Examples 1 to 3 from appropriate starting compounds. In the last column of this Table 1 and also of all the following Tables 2 to 9 the shade of the dyeings on natural or synthetic polyamide fibres is given whereby a is greenish-yellow f is red k is reddish-brown b is yellow g is bordeaux 1 is violet c is golden-yellow h is ruby m is brown d is orange i is blue n is ol ive e is scarlet j is reddish-blue 0 is grey. Generally, in the Tables any f@ is the anion of the reaction medium or is one of the anions indicated in the description above. Likewise, any basic groups may be in free base form or in form of the acid addition salt with those acids of the medium used in the preparation process. Table 1 / compounds of formula (1) Table 1 (continued) Table 1 (continued) Table 1 (continued) Examples 78 to 97 By a method analogous to that of Examples 1 to 3 further compounds corresponding to formula (2) in which the symbols are listed in Table 2 below may be prepared using appropriate-starting compounds. Table 2 / compounds of formula (2) Table 2 (continued) o Example 98 When an equi olar amount of the diazonium salt prepared as described i*n Example 1 is coupled at pH 8 with 33 parts of a compound of the formula in ' 300 parts of water an orange dyestuff is obtained corresponding to the formula in form of an acid addition salt (depending on the reaction medium) which dyes wool as well as polyester/cotton fibre blends a brilliant orange shade. Example 99 An equimolar amount of the diazonium salt solution of l-amino-4-vinylsulphonylbenzene prepared by a method analogous to that described in Example 1 is added dropwise to 27.2 parts of a compound of the formula dissolved in 300 parts of acetic acid and 700 parts of water within 45 minutes whilst cooling with ice. Coupling is effected at pH 3.0 to 3.5 which is kept by the addition of sodium acetate. After three hours the resulting dark-blue solution is adjusted to a volume of 2.5 litres by adding the corresponding amount of water. This solution contains the dyestuff corresponding to the formula in form of an acid addition salt which dyes wool a reddi sh-blue shade. Examples 100 to 146 By a method analogous to that of Examples 1 to 3 and 99 further compounds according to the invention may be prepared from appropriate starting compounds. These dyestuffs correspond (i) to formula (3) in which the symbols are defined in Table 3 below; (i i ) to formul a (4) in which the symbols are defined in Table 4 below; (iii) to formula (5) in which the symbols are defined in Table 5 below. The groups Z t] _ and Z^2 used in Tables 3 to 5 are defined as follows: - Z tl is a group -NHC 3 H 6 N(C 2 H 5 )2 and ∑t2 is a group -NHC 3 H N(CH 3 )2 Table 3 / compounds of formula (3) Table 4 / compounds of formula (4) Table 4 (continued) Table 5 / compounds of formula (5) Example 147 18.3 Parts of l-amino-3-vinylsulphonylbenzene are stirred into 300 parts glacial acetic acid at 20". To this mixture 35 parts of 30% hydrochloric acid are added. Diazotisation is effec¬ ted employing 6.9 parts of sodium nitrite in 25 parts of water and cooling with ice. After one hour any excess of nitrous acid is decomposed by the addition of a small amount of sulphamic acid. The coupling reaction is carried out in accordance with conven¬ tional methods at pH 3 to 4 using a compound of the formula The resulting dyestuff which coresponds to the formula in form of an acid addition salt dyes wool a yellow shade. The dyeings show good light and wet fastness properties. Examples 148 to 166 By a method according to Examples 1 to 3 and 147 further dyestuffs may be prepared from appropriate starting compounds. They correspond to formula (6) in which the symbols are as defined in Table 6 below. In Table 6 -Z t i is a group -NHC 3 H 6 (C2H5) 2 . Table 6 / compounds, of formula (6) Example 167 An equimolar amount of the diazonium salt as described in Example 147 is coupled with a solution of 55 parts of a compound having the formula in 500 parts of water. The dyestuff obtained which corresponds to the formula in form of an acid addition salt dyes wool in greenish-yellow shades. Examples 168 to 185 By a method according to that of Examples 1 to 3 and 167 further dyestuffs may be prepared from appropriate starting compounds which are listed in Table 7 below. They correspond to formula (7) in which the symbols are defined in Table 7. Table 7 / compounds of formula (7) Example 186 When the diazonium salt as described in Example 1 is coupled with a compound of the formula a dyestuff is obtained having the formula in form of an acid addition salt which dyes polyacrylonitrile a greenish-yellow shade. Examples 187 to 233 By a method analogous to that of Examples 1 to 3 and 186 further compounds may be prepared from appropriate starting compounds. The resulting dyestuffs correspond to formula (8) in which e sym o s are e ne n a e below. In this Table 8 Z t ι is a group and Z t is a group -NHC 3 H 6 N(CH 3 ) 2 . Table 8 / compounds of formula (8) Table 8 (continued) The coupling compounds used for the preparation of the dyestuffs of Examples 210 to 233 in Table 8 can be obtained by reacting a halogen containing compound of Example 1 of OE-OS 2237006 with a secondary or tertiary amine such as dimethyl- or diethylamine, morpholine or trimethylamine in accordance with known methods. Example 234 20 Parts of l-amino-3-(2 ' -hydroxyethy1 ) su1phonylbenzene are di azoti sed i n accordance wi th the method described in Exampl e 1. Thi s di azoni um salt i s coupl ed with 27 parts of a compound of the formul a in 200 parts of water and 30 parts of glacial acetic acid. A compound having the formula is obtained which precipitates in alkaline medium, and is separa- ted by filtration and dried. The product is added to 250 parts of concentrated sulphuric acid at 0" to 5 * whilst stirring vigor¬ ously. The temperature is allowed to rise slowly to 20 * . Subse¬ quently, the dark reaction mixture is poured onto 100 parts of ice. The pH is adjusted to ca. 10 with the addition of a 30% sodium hydroxide solution, the dyestuff precipitates increasingly and is separated by filtration after two hours. A dyestuff having the formula in form of an acid addition salt is obtained which dyes natural and synthetic polyamide fibres a bright golden-yellow shade. By a method analogous to that described in Example 234 the vinylsulphony1 group can be introduced into any diazo component disclosed in the Examples hereinbefore. Example 235 The diazonium salt solution prepared in Example 99 is added • dropwise at 0 β to 5" to a solution of 15.3 parts of 2,5-dimethoxy- aniline in 50 parts of glacial acetic acid and 150 parts of water within 30 minutes. The product which precipitates is filtered, washed with water and dried. 3.8 Parts of the above product are suspended in 50 parts of warm acetic acid and 5.8 parts of a 30% hydrochloric acid are added. To the resulting red solution a solution of 0.69 parts of sodium nitrite in 10 parts of water is added dropwise. The suspen¬ sion is stirred for one hour at 0 β to 5 β . Subsequently, any excess of nitrous acid is decomposed by the addition of a small amount of sulphamic acid. The diazonium suspension is then added to a mix¬ ture containing 2.9 parts of a compound of the formula in 60 parts of methanol and 40 parts of water. Stirring is effec¬ ted for a further two hours. The pH is kept at ca. 3 during coup¬ ling by the addition of sodium acetate and is subsequently adjus¬ ted to 4.5. The resulting disazo dyestuff which precipitates is filtered, washed and dried. It corresponds to the formula in form of an acid addition salt and dyes wool a reddish-blue shade. Examples 236 to 249 By a method analogous to that of Example 235 further disazo compounds may be prepared from appropriate starting compounds. They correspond to formula (9) in which the symbols are defined in Table 9 below. In any middle component I* *) denotes the carbon atom bound to -N=N-KK. In the following examples the application of the dyestuffs of this invention is illustrated. Application Example A To a dyebath of 25 β containing in 1000 parts of water 0.2 parts of the dyestuff of Example 1 20 parts of wool-gaberdine are added. The pH of the bath is adjusted to 4-5. The dyebath is heated to 98" within 60 minutes, and dyeing is effected at this , temperature for 60 minutes. The water that evaporates during dyeing is continuously replaced. Subsequently, the dyed wool fabric is removed from the liquor and is added to a fresh bath containing in 1000 parts of water 5 parts of acetic acid (100%). The bath is heated at the boil for 30 minutes. After rinsing and drying a red wool dyeing is obtained showing a high degree of levelness and having good light and wet fastness properties. Application Example B To a dyebath of 25° containing in 1000 parts of water 0.4 parts of the dyestuff of Example 3 20 parts of synthetic polyamide fabric, for example nylon 66 yarn, are added. Oyeiπg is effected in analogous manner to the method described in Application Example A. After rinsing and drying a level scarlet polyamide dyeing is obtained having good wet fastness properties. Application Example C To a dyebath of 25" containing in 1000 parts of water 0.1 parts of the dyestuff of Example 4 20 parts of unloaded natural silk fabric are added. Dyeing is effected in accordance with the method described in Application Example A with the exception that the silk dyeing is treated only for 15 minutes in the fresh bath. After rinsing and drying an orange dyeing is obtained having good wet fastness properties. Appl ication Exampl e D A polyester-cotton fibre blend (50:50) is padded with a liquor consisting of:- 15 parts of the dyestuff of Example 3 100 parts urea aπd 885 parts water at 25". The fabric is squeezed to reduce the total pick-up to ca. 80%, is dried at 100" and is then treated for 90 seconds at 210° for fixation. Subsequently, the dyeing is ' treated with a bath containing in 1000 parts aqueous liquor 200 parts sodium chloride 150 parts sodium carbonate (calcined) and 20 parts sodium hydroxide solution (36 β Be) at 85 * . In order to remove any excess of dyestuff the dyeing is rinsed with cold water and is then treated with an aqueous solution of 90° containing in 1000 parts 1 part of a non-ionic soaping agent and 1 part acetic acid (100%) for 5 minutes. Finally, the dyeing is rinsed with cold water. An orange dyeing is obtained having good light and wet fastness properties. In this dyeing both fibre portions are dyed on-tone having the same depth. Any one of the dyestuffs of Examples 2 and 5 to 249 which are in acid addition salt form or in quaternary ammonium salt form may be used in place of the dyestuffs of Examples 1, 3 and 4 in any one of Application Examples A to D. • - 52a - List of maximum absorption wavelengths ( , ηax i π nanometer nm) avai l able for the dyestuffs of Exampl es 1 to 249. Measurement was carri ed out i n demineral ised water. 2 452 51 488 . 99 587 205 420 3 495 52 483 114 463 206 422 7 470 53 478 115 478 * 234 438 8 476 54 496 117 560 235 604 9 473 55 491 .118 538 236 575 11 439 56 497 125 488 237 598 12 428 57 497 127 522- 238 597. 13 426 58 499 129 554 242 553 14 443 59 495 137 524 243 567 16 472 60 498 141 538 244 560 17 361 61 472 143 568 245 575 19 433 64 515 147 402 246 579 20 438 65 516 148 393 247 559 21 468 66 516 154 396 248 569 22 465 69 490 157 395 249 573 23 372 70 491 159 398 24 454 71 489 160 398 25 495 72 490 165 396 28 472 73 491 167 379 29 468 74 489 183 414 30 468 75 378 187 419 33 454 76 371 193 441 34 452 77 372 195 413 35 442 79 460 196 413 36 438 88 465 197 432 37 452 89 461 198 415 38 463 90 537 199 417 39 465 91 564 200 418 44 465 92 564 202 414 45 462 93 510 203 408

Claims: AMENDED CLAIMS [received by the Internationa] Bureau on ]4 Januar. 1986 (14.01.86); original claims, 1 ,4 and 5 amended ; remaining claims unchanged (5 pages)] 1. A onoazo or disazo compound in the metal-free form or in the 1:1 or 1:2 metal complex form which in the metal-free form corresponds to formula I CH =CH-S0 -Wχ-D - N = N - K-(W 2 -Z) n I in which D is the radical of a diazo component of the benzene, naphthalene or tetrahydronaphthalene series, K is the radical of a coupling component of the benzene, naphthalene, pyridine, pyridone, barbituric acid, quinoline, isoquinoline, benzene- or naphthalene- or tetrahydronaphtha- lene-azo-benzene or -azo-naphthalene, or of the acetoacet- a ide series, w " χ is a direct bond or a divalent bridging group, each w " , independently, is a divalent bridging group, n is an integer 1 to 4, each Z, independently, is a water solubilising protonable amine group, a quaternary ammonium group, a hydrazinium group or a ternary sulphonium group, with the proviso that any Z containing a quaternary t- di- rectly bound to the carbon atom of a triazine or pyri idine group which therefore constitutes part of a fibre-reactive grouping is excluded; which compound is in free basic form, salt form or acid addition salt form formed by the addition of dilute aqueous organic or mineral acids, and mixtures of compounds of formula I. 71 R 8 is -NHC0(CH 2 )ι_4-Zι, -S0 2 NH(CH 2 )i-4-Zι or R 8c is -NH(CH 2 )i_4-Zι or and Q, Qi and Z are as defined below; (d4) is an aminonaphthyl group of the formulae in whic and (d ζ ) is a naphthyl group of the formula in which one of the RQ-' S is hydrogen and the other is -C0NH(CH 2 )ι_4-Zι, -NHC0(CH 2 )ι_ -Zι, -S0 2 NH(CH 2 ) -Zi, t is 0 or 1 and Q, Qi and Z are as defined below; (f) is a group of the formula in which Rχ4 is hydrogen, Cχ_4alkyl, phenyl, benzyl or cyclohexyl, Rχ 5 is hydrogen, cyano, -C0NH 2 , -S0 2 NH 2 , -iζ A© or -CH 2 NHCOCH -Zχ, Rχ5 is hydrogen, -NH 2 , , ' Cχ_4alkyl unsubstituted or monosubstituted by OH, CN, halogen or Cχ_4a1koxy; *« eCH 2 ) 1 _ 4 -NHC0 -CH 2 ) 1 _ 4 -Z 1 or ) 1 _ 4 -Z ] 5. A compound or complex according to Claim 4 containing one or two protonable amine groups or quaternary ammonium groups as Z which compound or complex, in the metal-free form, corresponds to formula lb or Ic, in which t is 0 or 1, R 3a 1S n *yd ogen or hydroxy Kc is a group of the formula l< is hydrogen, halogen, Cχ-_2alkyl, Cχ. 2 lkoxy, OH, COOH, CN, phenoxy, the phenyl group of which may be substituted by one to three chlorine atoms, -S0 2 NH 2 , -S0 NHCχ_ alkyl , -Sθ2N(Cχ_2 lky1)2, -NHC0CH or phenylamino, a is hydrogen, halogen, C * χ_ a1kyl or Kb is a group ( ); (d la ), (d 2a ), (d 3a ), (d 5a ); (f_), (9l). (i2a)> (i3a) or ( a)» one of the groups Rg d ' is hydrogen and the other is -C0NH(CH 2 ) 1 _ 4 -Z 2 , -NHC0(CH 2 ) 1 _ 4 -Z £ , -NH(CH 2 ). | _ 4 -Z 2 or in which R-- is hydrogen, methyl, ethyl or benzyl, R- 5a is hydrogen, -C0NH 2 or -CHgNHCOCHg-Zg, R ]6a is hydrogen, C-_ 2 a1kyl, (CH 2 )-,_ 4 -Z 2 , ~(^ ( CH 2)l-4 "Z 2

Inventors: BAUMANN WERNER, EICHENBERGER HERBERT, OPPLIGER MAX, VAN DIEST JOSEPH, BAUMANN, WERNER, EICHENBERGER, HERBERT, OPPLIGER, MAX, VAN DIEST, JOSEPH
Applicants: SANDOZ AG
Application year: 1985
Main classification: C09B62
IPC codes: C09B62, D06P1