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WO1981003179A1 - Improvements in or relating to organic compounds - Google Patents

Improvements in or relating to organic compounds Download PDF

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Publication number
WO1981003179A1
WO1981003179A1 PCT/EP1981/000041 EP8100041W WO8103179A1 WO 1981003179 A1 WO1981003179 A1 WO 1981003179A1 EP 8100041 W EP8100041 W EP 8100041W WO 8103179 A1 WO8103179 A1 WO 8103179A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
hydrogen
alkyl
formula
metal complex
Prior art date
Application number
PCT/EP1981/000041
Other languages
German (de)
French (fr)
Inventor
P Doswald
H Moser
E Moriconi
H Schmid
Original Assignee
Sandoz Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sandoz Ag filed Critical Sandoz Ag
Priority to JP56501662A priority Critical patent/JPH0335339B2/ja
Priority to PCT/EP1981/000041 priority patent/WO1981003179A1/en
Publication of WO1981003179A1 publication Critical patent/WO1981003179A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B44/00Azo dyes containing onium groups
    • C09B44/10Azo dyes containing onium groups containing cyclammonium groups attached to an azo group by a carbon atom of the ring system
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B44/00Azo dyes containing onium groups
    • C09B44/02Azo dyes containing onium groups containing ammonium groups not directly attached to an azo group
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B45/00Complex metal compounds of azo dyes
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/28Colorants ; Pigments or opacifying agents

Definitions

  • the invention relates to sulpho — free azo compounds, in metal-free, 1: 1 metal complex or 1: 2 metal complex form, which are useful for dyeing paper and leather.
  • each molecule of the complex has 1 metal atom bonded to 1 dyestuff molecule or has 2 metal atoms bonded to two dyestuff units, which dyestuff units are joined together by a direct bond or a conventional bridging group; and what is meant by a “1: 2 metal complex” is that the complex has 1 atom of metal bonded to two dyestuff units, which dyestuff units can be the same or different but which dyestuff units are part of two separate dyestuff molecules.
  • the invention provides sulfo — free azo compounds in metal-free, 1: 1 metal complex or 1: 2 metal complex forms having at least on average 1.3 preferably 2 water solubilizing basic groups, the compounds being of formula I
  • Ra is a group of the formula Ia - Ic
  • yo is OH or NH 2
  • R b is a (C 1-4 ) alkyl group or a substituted (C 1 _ 3 ) alkyl group
  • R c is -NH 2 , a substituted alkyl group, a substituted alkylamino group, a substituted phenylamino group, an unsubstituted or substituted naphthylamino group, an unsubstituted or substituted benzthiazolamino group, an unsubstituted or substituted benzoxazolamino group an unsubstituted or substituted benzimidazolamino group; x and y independently are hydrogen, -OH, (C 1-4 ) alkyl, -NH 2 or COOH or
  • x and yo form the group -NH-Me-O-, -NH-Me-NH- or -O-Me-O-
  • Me is a metal capable of either forming a 1: 1 metal complex or a 1 : 2 metal complex; or capable of forming both a 1: 1 and a 1: 2 metal complex
  • n is 1 or 2
  • d is 0, 1 or 2;
  • D is a diazo component
  • W is a direct bond or a conventional bridging group
  • B 1 is phenylene, naphthalenes, tetrahydro naphthalenes or a group of the formula
  • Z is a basic amino or a quaternary ammonium group; a is 1 or 2; b is a number between 1 and 2;
  • K is a coupling component of the series 4-alkyl-2-pyridones, ß-hydroxynaphthalenes, anilines, pyrazole-5 or acetoacyl, the coupling component being substituted by at least one water solu bilising basic group;
  • Y is a direct bond or a conventional bridging group
  • X is a direct bond or a conventional bridging group
  • R is a group of the formula Ih
  • rings B, C and D can be each substituted independently by up to two further substitutes to give up to three substitutes in total and ring F can be substituted by up to three substitents in total, with the proviso that
  • n 2 and when Ra is a group of formula Ia, x and y may not both be selected from hydrogen and C 1-4 alkoxy;
  • 1 metal complex form Me is copper, chromium, cobalt, iron, nickel or manganese, more preferably copper, chromium or cobalt, most preferably copper.
  • copper is Cu 2+ ; chromium is Cr 2+ ; cobalt is Co 2+ ; iron is Fe 2+ ; nickel is Ni 2+ and manganese is Mn 2+ .
  • Me is chromium, cobalt, iron or nickel, more preferably chromium, cobalt or iron, most preferably iron.
  • chromium is Cr; cobalt is
  • the invention provides sulpho-free azo compounds, in metal-free, 1: 1 metal complex or 1: 2 metal complex form having on average at least 1.3 preferably 2, water solubilizing basic groups, the compounds being of the formula II
  • D, X, W, a, b, and rings B and C are above defined; c is 1 or 2; d 'is 0 or 1; A 1 is -OH or -NH 2 ; A 3 is hydrogen or -OH or
  • a 1 and A 3 form the group -NH-Me-O- or -O-Me-O- where Me is either a metal capable of either forming a 1: 1 metal complex or a 1: 2 metal complex or capable of forming both a 1: 1 metal complex and a 1: 2 metal complex;
  • Me is either a metal capable of either forming a 1: 1 metal complex or a 1: 2 metal complex or capable of forming both a 1: 1 metal complex and a 1: 2 metal complex;
  • a 2 is -OH or -NH 2 ;
  • R t ' is a group of the formula If defined above
  • Z 2 is a group of the formula
  • each R o is independently methyl, ethyl, ß-hydroxyethyl, benzyl, -CH 2 COCH 3 or provided that not more than one benzyl, -CH 2 COCH 3
  • R 127 is methyl or ethyl, m is 0, 1 or 2 and A ⁇ is defined above with the proviso that each of the azo bridges in ring B is ortho to A 1 or A 2 or to both A 1 and A 2 .
  • R " t is a group of the formula ⁇ or ⁇ ß
  • R 1 is C 1-4 alkyl, -C 2 H 4 OH or - (CH 2 ) p -N- (R 1a ) 2 where
  • R 1a is propyl or butyl
  • R 6 is C 1-4 alkyl, -C 2 H 4 OH or (CH 2 ) p -N- (R 6 ') 2 where R 6 ' is (C 1-4 ) alkyl and R 6a is (C 1 _ 4 ) alkyl, -C 2 H 4 OH, - (CH 2 ) p -N- (R 6 ') 2 or C 2 H 4 OR 6 ';
  • R 3 is hydrogen, NO 2 , -SO 2 NH 2 , -SO 2 NH-R 1
  • Alkoxy alkyl (C1-4), (C 1 _ 4)
  • R 5 is hydrogen, (C 1-4 ) alkyl or (C 1-4 ) alkoxy;
  • R 5 ' is C 1-4 alkyl; no is a number between 1 and 2 and the group
  • R 7 is hydrogen, -OH, (C 1-4 ) alkyl, (C 1-4 ) alkoxy -NH - CO - NH 2 or -NH - CO - CH 3 ;
  • R 8 is hydrogen, -NH - CO - (CH 2 ) p - Z 2 or
  • R 4 is hydrogen, -NO 2 , (C 1 _ 4 ) alkyl or (C 1 _ 4 ) alkoxy; K 1 is a group of the formula
  • R 25 is (C 1-4 ) alkyl, -COO- (R 2 5a ) or -COOH where
  • R 25a is (C 1-4 ) alkyl
  • R 26 is hydrogen, halogen, C 1-4 ) alkyl or (C 1-4 ) alkoxy;
  • R 124 is (C 1-4 ) alkyl or - (CH 2 ) p -Z 2 ;
  • Y a is hydrogen, (C 1-4) alkyl, -C 2 H 4 OH or (CH 2) p -Z 2;
  • R 9 is (C 1-4 ) alkyl, or - (CH 2 ) p -Z 2 ;
  • R 10 is hydrogen, (C 1-4 ) alkyl, C 1-4 ) alkoxy,
  • R 125 is - (CH 2 ) p -Z 2 , -NH- (CH 2 ) p -Z or where R 126 is hydrogen, -OH, (C 1-4 ) alkoxy,
  • R 127 is hydrogen or - (CH 2 ) p -Z 2;
  • X ' is one of the groups X 1 to X 53 below:
  • X 1 is a direct bond
  • X 2 a straight or branched chain alkylene group of (C 1-4 ) carbon atoms, X 3 -CO -
  • R 11 is halogen, (C 1-4 ) alkyl or (C 1 _ 4 ) alkoxy
  • R 12 is hydrogen or (C 1 _ 4 ) alkyl
  • R 13 is halogen, -NH-CH 2 -CH 2 -OH or
  • R 14 is a straight or branched chain (C 1-4 ) _ alkylene group and q is 1, 2, 3 or 4 with the provisos that i) the diazo bridges in ring B are ortho each to A 1 or A 2 or to both A 1 and A 2 ; ii) when c is 2, X 'is attached to R t "when R t " is the group ⁇ or to ring C; iii) when d 'is 1 ring C can be substituted by one or more of halogen, hydroxy, (C 1-4 ) alkyl, (C 1-4 ) - alkoxy and -NH-CO-NH 2 .
  • the invention provides sulpho-free azo compounds, in metal-free, 1: 1 metal complex or 1: 2 metal complex form having an average of at least 1,3 water solubilizing basic groups per dyestuff unit, the compounds being of the formula III
  • a 4 is hydrogen, -OH, -NH 2 , (C 1-4 ) alkoxy or COOH or A 4 and a hydroxy or amino group on K 2 together form the group -NH-Me-O-, -NH- Me-NH-, -NH-Me-OOC-, -O-Me-O- or -O-Me-OOC- where Me is a metal capable of either forming a 1: 1 metal complex or a 1: 2 metal complex or capable of forming both a 1: 1 and a 1: 2 metal complex,
  • K 2 is one of the groups of the formula
  • R 21 is hydrogen, -NO 2 , -NH-CO (CH 2 ) s -Z 2 , -CH 2 -Z 2 , -SO 2 -NH- (CH 2 ) s - Z 2 , -SO 2 -NH 2 , -CO-CH 2 ⁇ Z 2 ,
  • R 22 is hydrogen, -NO 2 , -SO 2 -NH 2 , -SO 2 -N (R 22a ) 2
  • R 22a is (C 1--4 ) alkyl
  • R 23 is hydrogen or -CH 3
  • R 35 is hydrogen, (C 1-4 ) alkyl or -CH 2 -COO-R 35a where R 35a is (C 1-4 ) alkyl
  • R 24 is hydrogen, (C 1-4 ) alkyl, -C 2 H 4 OH, - (CH 2 ) p -Z 2 , benzyl,, - (CH 2 ) 3 OCH 3 ; where R 24a is (C 1-4 ) alkyl, preferably -CH 3 ;
  • R 25 is (C 1-4 ) alkyl, -COO- (R 25a ) or COOH where
  • R 25a is (C 1-4 ) alkyl; it is 1, 2, 3, 4, 5 or 6.
  • R 28 is hydrogen, (C 1-4 ) alkyl, (C 1-4 ) alkoxy or halogen
  • R 29 is hydrogen, (C 1-4 ) alkyl, (C 1-4 ) alkoxy, halogen, -NH- ( CH 2 ) s -Z 2 or -NH- C 2 H 4 OH
  • each R 30 is independently hydrogen or (C 1-4 ) alkyl
  • R 33 is hydrogen, halogen, (C 1-4 ) alkyl, (C 1-4 ) alkoxy, -SO 2 NH 2 or -SO 2 N (CH 3 ) 2 ; with the provisos that i) R 20 and R 21 cannot both be -NO 2 , ii) R 21 and R 22 cannot be the same group unless R 21 and R 22 are both hydrogen, iii) when R 21 and R 22 are both hydrogen R 20 cannot be -NO 2 and iv) R 20 cannot be -NO 2 when R 21 , R 22 an R 23 lare hydrogen. Still further the invention provides sulpho-free azo compounds in metal-free, 1: 1 metal complex or 1: 2 metal complex form having at least 1.3 preferably 2 water solubilizing basic groups, the compounds being of the formula IV
  • a 1 is -OH or -NH 2 and A 5 is -OH, (C 1-4 ) alkoxy or -COOH or A 1 and A 5 together form the group -NH-Me-NH, -NH-Me- OOC-, -NH-Me-O-, -O-Me-O, -O-Me-OOC
  • Me is a metal capable of either forming a 1: 1 metal complex or a 1: 2 metal complex or capable of forming both a 1: 1 metal complex and a 1: 2 metal complex
  • e is 0 or 1
  • R 60 is hydrogen or -NO 2 ;
  • R 61 and R 62 independently, are hydrogen, -NO 2 ,
  • R 6 ' 2 is (C 1-4 ) alkyl
  • R 63 is -SO 2 -NH- (CH 2 ) p -Z 2 , -CO-NH- (CH 2 ) p -Z 2 ,
  • R 64 is hydrogen or (C 1-4 ) alkoxy each R 65 is independently hydrogen (C 1-4 ) alkyl or C 1-4 - alkoxy; p is 1, 2 or 3; q 'is 1 or 2 with the proviso that when R 63 is -CO-NH- (CH 2 ) p -Z 2 q' is 2; K 3 is one of the following groups where R 9 , R 10 R 25 and Z 2 are defined above,
  • R 66 is hydrogen, (C 1-4 ) alkyl, -C 2 H 4 OH or
  • R 6 ' 6 is (C 1-4 ) alkyl
  • Ta is a group of the formula
  • R 71 is hydrogen, -OH, (C 1-4 ) alkoxy, -NH-CO- (CH 2 ) p -Z 2 , -CO-NH- (CH 2 ) p -Z 2 ,
  • R 72 is hydrogen or - (CH 2 ) p -Z 2 ;
  • R 69 is (C 1-4 ) alkyl or- (CH 2 ) p -Z 2 where p and Z 2 are above defined
  • each R 65 is independently, is hydrogen, (C 1-4 ) alkyl or (C 1 _ 4 ) alkoxy; and X 'is as defined above; with the provisos
  • each azo bridge in ring B is in an ortho position either to A 1 or A 2 or to both A 1 and A 2 .
  • a group of preferred metal-free azo compounds of formula II ' are those of formula Ila
  • each R 2a is independently hydrogen, -NO 2 , -SO 2 NH 2 , -SO 2 -NH-CH 3 , -SO 2 -N (CH 3 ) 2 ,
  • each R 3a is independently hydrogen, -NO 2 , -SO 2 NH 2 ,
  • R 7a is hydrogen, -OH, -CH 3 , -OCH 3 , -NHCOCH 3 or -NHCONH 2 ;
  • R 8a is hydrogen, -NHCO- (CH 2 ) -Z 2 or
  • n 0 ' is an average number between 1.0 and 1.7 K 1 '
  • R 9a is -CH 3 or C 2 H 5 ,
  • R 10a is hydrogen, -CH 3 , -OCH 3 , -NH-CO-CH 3 or
  • R 9 ' is hydrogen, -CH 3 , -C 2 H 5 , nC 3 H 7 , nC 4 H 9 , iC 3 H 7 , iC 4 H 9 , -C 2 H 4 OH or - (CH 2 ) p - Z 2 ;
  • R 4a is hydrogen, -NO 2 , -CH 3 or -OCH 3 ;
  • R 15 is hydrogen, -OH, -OCH 3 , -CH 3 or Cl
  • R 16 is hydrogen or -CH 3
  • q 0 is 2 to 5, preferably 2 or 3
  • all the other symbols are as defined above.
  • a further group of preferred metal-free azo compounds of formula II ' are those of formula Ilb
  • R 2d is hydrogen, -OH, -CH 3 or -OCH 3 ;
  • each ring C independently can be substituted in a position ortho to its azo bridge by chlorine and / or -CH 3 and / or -OCH 3 and the group X a is in a meta- or para-position to the azo bridge of ring C and each azo bridge, in ring B is ortho to A 1 or A 2 or to both A 1 and A 2 ;
  • X a is X 1 , X 5 , X 6 , X 7 , X 10 , X 11 , X 12 , X 16 , X 17 , X 22 ,
  • R 11a is hydrogen, -Cl, -CH 3 or -OCH 3 ;
  • R 13a is -Cl, -NH-CH 2 -CH 2 -OH or -N (CH 2 ⁇ CH 2 -OH) 2 ; and all the other symbols have been defined above.
  • Preferred compounds of formula Ilb are of the same
  • Xb is X 1 , X 11 , X 12 , X 17 , X 27 , X 49 , X 2 "X '14 , X 1 ' 9 , X 1 " 9 , X 1 ''' 9 , X 2 ' 0 , X 2 " 0 , X 3 ' 2 , X 3 ' 4 , X 3 iv 4 , X v 34 or
  • Preferred compounds of the formula Ild are of the formula Ile
  • R t v is hydrogen
  • Me c is copper
  • cobalt or chromium preferably copper
  • R 2b is hydrogen, -NO 2 or -SO 2 -NH 2 ,
  • R 3b is hydrogen, -NO 2 , -CH 3 , -OCH 3 , -SO 2 NH 2 ,
  • n o is from 1.3 to 1.5
  • R 4b is hydrogen or -NO 2 , and all the other symbols are as defined above.
  • Alternatively preferred compounds of formula II 'in 1: 1 metal complex form where c 2 are of the formula Ilf
  • Preferred compounds of formula Ilf are of the formula IIg
  • R 70 is hydrogen, chlorine, methyl or methoxy; a the group Xa is attached in meta or para position in ring F to the azo group and each azo bridge in ring B is in ortho position to A 1 or A 2 or to both A 1 and A 2 .
  • R 3e is hydrogen, -CH 3 , -NO 2 , -SO 2 -NH 2 , -CH 2 -Z 3 ,
  • R 4e is hydrogen or -NO 2 and all the other symbols are as defined above and Xb is attached in the ortho- or meta-position to the azo group.
  • Preferred 1 2 metal complex azo compounds of formula II 'where c is 1 and are one of the formula IIj to IIm below:
  • Me g is cobalt, iron or chromium, (CH 2) p -Z 2, -NH- (CH 2) preferably iron R 42 is- p -Z 2 or
  • R 43 is -CH 3 , C 2 H 5 or (CH 2 ) p -Z 2 ;
  • R 44 is hydrogen, -OH, (C 1-4 ) alkoxy,
  • R 45 is hydrogen or - (CH 2 ) p -Z 2 ;
  • R 2 ' a has the significances of R 2 a and may also be -OH or. -NH 2 ; and the other symbols are as defined above.
  • Preferred compounds of formula IIj are Symmetric and are of the formula Iln
  • R v t i has the additional significance of
  • azo bridge in ring B is in the 3 or 4 position; (ii) that R 34 and R 35 are not both -NO 2 ; and (iii) that the compounds of formula III contain at least two water solubilizing basic groups.
  • Preferred azo compounds of formula III are of the formula Illb
  • R 24 is hydrogen, -CH 3 , -C 2 H 5 , -C 2 H 4 OH or
  • R 22d is hydrogen, -CH 2 -Z 3 , -SO 2 -N (CH 3 ) 22 , -NO 2 ,
  • Rg ''' is hydrogen, CH 3 , -C 2 , H 5 , iC 3 H 7 , iC 4 H 9 , nC 3 H 7 , nC 4 H 9 , -C 2 H 4 OH, - (CH 2 ) q -Z 3 ;
  • R 50 is hydrogen, -Cl, -Br, -CH 3 or OCH 3 ;
  • R 52 is hydrogen, -Cl, -Br, -CH 3 or -OCH 3 ;
  • R 53 is hydrogen, -NH- (CH 2 ) q -Z 3 , -NH-C 2 H 4 OH, -Cl,
  • R 54 is hydrogen
  • R 55 is hydrogen, -Cl, -Br, -CH 3 , -OCH 3 , -SO 2 NH 2 or
  • R 21d and R 22d are not both the same unless both are hydrogen; (ii) that R 20 and R 21d are not both NO 2 ; (iii) that the starred carbon atoms are not attached to the N-atom of the basic or quaternary ammonium group; an (iv) that R 20 is not NO 2 when R 21d or R 22d are both hydrogen.
  • Preferred compounds of formula Illd are of the formula Ille
  • R 22e is hydrogen, -CH 2 -Z 5 ,
  • R 21a is hydrogen, -CH 2 -Z 2 , -NH-CO- (CH 2 ) a -Z 2 ,
  • R22a is hydrogen, -NO 2 , -SO 2 -NH 2 ,
  • R 21b and R 22b are independently hydrogen, -CH 2 -Z 3 , -NO 2 , -SO 2 -NH 2 , -NH-CO-CH 2 -Z 3 ,
  • R 21c and R 22c independently are hydrogen
  • Preferred compounds of formula IIIi or IIIj in 1: 1 metal complex form are of the formula IIIk or IIIl
  • Me g is iron.
  • Preferred azo compounds of formula III in 1: 2 metal complex form are symmetric or asymmetric and are of the formula IIIm
  • each T x independently, is
  • Me g is chromium, iron or cobalt: preferably iron and all the other symbols are as defined above with the provisos i) that in ring E the azo bridge is in the 3- or
  • Preferred azo compounds of formula IIIm are of the formula IIIn
  • More preferred azo compounds of formula IIIm are of the formula IIIo
  • each T x "independently is in which all the other symbols aro as defined above with the proviso that R21c and R 22c are not both -NO 2 .
  • azo compounds in 1: 2 metal complex form are of the formula IIIp or IIIq
  • More preferred azo compounds of formula IIIp or IIIq are of the formula Illr or IIIs
  • K 5 '-O- has the significances of Illba, Illbb or Illbc of K 5 -O- above and all the other symbols are as defined above.
  • Preferred azo compounds of formula IV in metal free form are of the formula IVa
  • R 61a is hydrogen, -NO 2 , -CH 2 -Z 2 , -SO 2 -NH- (CH 2 ) p -Z 2 ,
  • R 62a is hydrogen, -NO 2 , -CH 2 -Z 2 , -SO 2 -NH 2 , -SO 2 -NH- (CH 2 ) p -Z 2 , -CO-NH- (CH 2 ) p -Z 2 , -NH-CO- (CH 2 ) p -Z 2 ,
  • K 7 is one of groups IVaa to IVaf below
  • R 9a is -CH 3 , -C 2 H 5 . or -C 2 H 4 -Z 2 ;
  • R 10a is hydrogen, -CH 3 , -OCH 3 , -NH-CO-CH 3 or
  • R 66a is hydrogen, -CH 3 , -C 2 H 5 , nC 3 H 7 , nC 4 H g , iC 3 H 7 , iC 4 H 9 , -C 2 H 4 OH or - (CH 2 ) p -Z 2 ;
  • R 68a is - (CH 2 ) p -Z 2 , -NH- (CH 2 ) p -Z 2 or
  • R 69a is -CH 3 , -C 2 H 5 or - (CH 2 ) p -Z 2 ;
  • R 71a is hydrogen, -OH, -OCH 3 , -NH-CO- (CH 2 ) p -Z 2 ,
  • R 72a is hydrogen or - (CH 2 ) p -Z 2 ; and where all the other symbols are as defined above: with the provisos
  • each azo bridge in B is in an ortho position to A 1 or A 2 or to both A 1 and A 2 ;
  • R 61b is hydrogen, -NO 2 , -CH 2 -Z 3 , -SO 2 -NH- (CH 2 ) -Z 3 ,
  • R 62b is hydrogen, -NO 2 , -CH 2 -Z 3 , -SO 2 -NH 2 ,
  • R 9b is -CH 3 , -C 2 H 5 or -C 2 H 4 ⁇ Z 3 ;
  • R 66b is hydrogen, -CH 3 , -C 2 H 5 , -C 2 H 4 OH or - (CH 2 ) m ' -Z 3 ;
  • R 70b is hydrogen, -OH, -OCH 3 , -NH-CO- (CH 2 ) a -Z 3 -,
  • R 71b is hydrogen or - (CH 2 ) m ' -Z 3 ; and all the other symbols are as defined above, with. the provisos that (i) R 61b and R 62b cannot both be the same group unless both are hydrogen (ii) that R 60 and R 61b are not both NO 2 ; and (iii) R 60 is not -NO 2 when R 61b and R 62b are both hydrogen.
  • R 63a is -SO 2 -NH- (CH 2 ) m ' -Z 2 , -CO-NH- (CH 2 ) m' -Z 2 ,
  • each R 65a independently, is -CH 3 , -C 2 H 5 , -OCH 3 or -OC 2 H 5 ;
  • R 64a is hydrogen or -OCH 3 ;
  • k is 1 or 2, but only 2 when R 63a is the group -CO-NH- (CH 2 ) m ' -Z 2 ;
  • R 61a ' is hydrogen, -NO 2 , -NH-CO- (CH 2 ) a -Z 2 or
  • R 62 ' is hydrogen, -NO 2 , -SO 2 -NH 2 , -SO 2 -N (CH 3 ) 2 ,
  • each R 65b independently, is -CH 3 or -OCH 3 ,
  • Preferred azo compounds of formula IV in 1: 1 metal complex form are of the formula IVe
  • R 6 ' 1a and R 6 ' 2a are not both the same and iii) that R 60 is not -NO 2 when R 6 ' 1a and R 6 ' 2a are both hydrogen.
  • Preferred compounds of formula IVg are of the formula IVh
  • Preferred azo compounds of formula IV in 1: 2 metal complex form are of the formula IVi
  • Me is chromium, iron or cobalt and all the other symbols are as above defined, with the provisos i) that R 61a and R 62a are not both the same unless both are hydrogen a ii) that R 60 and R 61b are not both -NO 2 ; and iii) that R 60 is not -NO 2 when R 61a and R 62a are both hydrogen.
  • Preferred azo compounds of formula IVi are of the formula IVj
  • R 60 is not -NO 2 when R 61b and R 62b are both hydrogen.
  • X is preferably Xa defined above, more preferably Xb.
  • Z is preferably Z 2 , more preferably Z 3 most preferably Z 5 .
  • R 3a is preferably R 3b , more preferably R 3c , and R 3c preferably hydrogen, -NO 2 , -SO 2 NH 2 , -SO 2 NH (CH 2 ) 3 N (CH 3 ) 2
  • R 64a is hydrogen
  • one of R 2 and R 3 or one of R 21 and R 22 or one of R 61 and R 62 respectively is hydrogen.
  • the azo compounds of formula I in metal free form can be prepared by coupling a diazotised amine of formula ⁇
  • n 'and da have the significances of n and d above with the proviso that n + n' is not greater than 2 and d and da is not greater than 2 and in the case of the metal complexes metallizing with a metal capable of forming a 1: 1 or 1: 2 metal complex or capable of forming both a 1: 1 and 1: 2 metal complex.
  • the azo compounds of formula I in metal free form can be formed by diazotising a corresponding arylamine and coupling with the requisite coupling component by conventional methods.
  • the azo compounds of formula I in 1: 1 metal complex form may be prepared by metallizing compounds of formula I in metal free form with a metal selected from copper, cobalt, iron, nickel, manganese, chromium or zinc.
  • the azo compounds of formula I in 1: 2 metal complex form may be prepared by metallizing compounds of formula I in metal free form with a metal selected from chromium, nickel, cobalt or iron.
  • a further method for the preparation of an azo compound of formula I in 1: 2 metal complex form is bonding an azo compound of formula I in metal free form with an azo compound 1: 1 metal complex form when the metal is chromium, nickel, cobalt or iron.
  • the metallization process to form a 1: 1 metal complex is carried carried out by treating 1 mole of azo compounds with a metallizing agent containing
  • Metallization is carried out by known methods possible in aqueous medium or a mixture of water and a water-miscible organic solvent for example acetone, lower alkyl alcohols, dimethylformamide formamide, glycols or acetic acid at a pH range from 1.0 to 8.0, preferably pH 2 to 7.
  • the metallization process may be carried out at a temperature from room temperature to the boiling point of the reaction medium.
  • metallization may be effected in a wholly organic medium (for example dimethylformamide).
  • cobaltization may be carried out in the presence of an inorganic nitrite such as lithium, sodium, ammonium or potassium nitrite in the ratio of
  • Suitable anions include such as chloride and bromide, sulphate, bisulphate,
  • the compounds according to the invention are suitably worked up into a solid or liquid preparation for example by granulation or by dissolving in a suitable solvent.
  • the compounds of the invention are suitable for dyeing, padding or printing on fibers, threads or textile materials particularly natural or Suitable cobalt-yielding compounds are for example cobalt (II) or Co (III) sulphate, acetate, formate or chloride.
  • Copper-yielding compounds are for example cupric sulphate, cupric formate, cupric acetate or cupric chloride.
  • the nickel-yielding compounds are Ni (II) or Ni (III) compounds, such as nickel formate, nickel acetate or nickel sulphate.
  • Preferred manganese yielding compounds are Mn (II) compounds and iron yielding compounds are Fe (II) or Fe (III) compounds. Examples of these and zinc-yielding compounds are manganese, iron or zinc formate, acetate or sulphate.
  • chromium yielding compounds are Cr (II) or Cr (III) formate, acetate or sulfate.
  • the starting compounds of formula ⁇ and ⁇ are for the most part known or can be prepared aecording to known methods.
  • the coupling can be carried out aecording to known methods.
  • Advantageously coupling is carried out in aqueous, acid, neutral or alkali medium at a temperature from -10oC to room temperature, if necessary in the presence of a coupling accelerator such as pyridine or urea.
  • a coupling accelerator such as pyridine or urea.
  • coupling may be effected in a mixture of solvents for example water and an organic solvent.
  • regenerated cellulose materials for example cotton, synthetic polyamides or synthetic polyesters in which the acid groups have been modified.
  • Such polyamide is described in Belgian Patent 706,104 and such synthetic polyester is described in US Patent 3,379,723.
  • the new compounds are also used for dyeing, pad-dyeing or printing fibers, threads or textiles produced therefrom, which consist of or contain homo- or mixed polymers of acrylonitrile or of asymmetrical dicyanoethylene.
  • the textile material is dyed, printed or pad-dyed in aecordance with known methods.
  • Acid modified-polyamide is dyed particularly advantageously in an aqueous, neutral or acid medium, at temperatures of 60 ° C to boiling point or at temperatures of above 100 ° C under pressure.
  • the textile material may also be dyed by the compounds of formula I in organic solvents, e.g. in agreement with the directions given in German DOS 2 437 549.
  • Cellulose material is mainly dyed by the exhaust process, eg from a long or short bath, at room temperature to boiling temperature, optionally under pressure, whereby the ratio of the bath is from 1: 1 to 1: 100, and preferably from 1: 20 to 1:50. If dyeing is effected from a short bath, then the liquor ratio is 1: 5 to 1:15, and the pH value of the dye baths varies between 3 and 10. Dyeing preferably takes place in the presence of electrolytes.
  • Printing may be effected by impregnation with a printing paste produced by known methods.
  • the dyestuffs are also suitable for dyeing or printing paper, e.g. for the production of bulk-dyed, sized and unsized paper.
  • the dyestuffs may similarly be used for dyeing paper by the dipping process.
  • the dyeing of paper is effected by known methods.
  • the new dyestuffs are also suitable for dyeing or printing leather by known methods. Dyeings with good fastness are obtained both on paper and on leather.
  • Dyeings made from the new compounds on leather have good light fastness properties, good diffusion properties with PVC, good water, wash and sweat properties, good fastness to dry cleaning, good fastness to drops of water, good fastness to hard water.
  • Dyeings made from the new compounds on paper have good build-up, good light fastness, good fastness to water, milk, fruit juice, sweetened mineral water and alcoholic drinks, good fastness to 1% sodium chloride, washing powder solution, good sulphite reduetive or oxidative (with hypo-chlorite) clearanee and good fastness to hard water.
  • Dyeings made from mixtures of the new dyestuffs remain tone-in-tone and the nuance stability of dyeings made from the dyestuffs is good.
  • dyestuffs of the invention do not run after dyeing on paper nor on the whole are they pH sensitive.
  • the new compounds may be converted into dyeing preparations.
  • the processing into stable, liquid or solid dyeing preparations may take place in a generally known manner.
  • Advantageously by grinding or granulating, or by dissolving in suitable solvents, optionally adding an assistant, e.g. a stabilizer or dissolving inter mediary, such as urea.
  • an assistant e.g. a stabilizer or dissolving inter mediary, such as urea.
  • Such preparations may be obtained for example as described in French Patent Specifications 1,572,030 and 1,581,900 or in accordance with German DOS 2,001,748 and 2,001,816.
  • Liquid preparations of the compounds of formula I preferably comprise 10-30% by weight of a compound of formula I and to 30% of a solubilizing agent such as urea, lactic acid or acetic acid the rest of the composition being water.
  • Solid preparations preferably comprising 20-80% dyestuff, 80-20% solubilizing agent such as urea or Na 2 SO 4 and 2-5% water.
  • a strongly acid solution of the monoazo dyestuff is made up with a 30% solution of hydrochloric acid and then diazotised with 6.9 parts of sodium nitrite according to known methods. Over a period of 15 minutes the solution is added, dropwise, to 32.4 parts (0.1 mole) of 6-hydroxy-4-methyl-1-dimethyl-aminopropyl-pyridonyl- (3) -pyridinium chloride dissolved in 250 parts of water. The pH of the solution is then brought to 6.5 using a sodium hydroxide solution and the reaction mixture concentrated by evaporation under vacuum.
  • the resultant dyestuff is of formula b)
  • Example 2 is produced which dyes leather a red-brown tone and has good fastness properties.
  • the dyestuff dyes leather a red brown color with good fastness properties.
  • R312 is -NH-CO- (CH 2 ) -Z
  • R313 is -SO 2 -NH- (CH 2 ) 3 -Z
  • Example 1 can be prepared following the method of Example 1 (and Example 5 where 1: 2 metallization has been carried out), with suitable choice of starting materials.
  • Example 5 where 1: 2 metallization has been carried out
  • R 400 is -SO 2 -NH- (CH 2 ) 3 -N (CH 3 ) 2
  • Example 2 which can be made according to Example 1 and where 1: 2 metallization is neeessary according to Example 5 using a suitable choice of starting materials.
  • Z is N (C 2 H 5 ) 2 and Z B is N (CH 3 ) 2 .
  • R 323 is -NH-CO- (CH 2 ) -N (CH 3 ) 2
  • Example 5 which may be prepared by following the method of Example 1 (and where 1: 2 metallization is carried out Example 5) with suitable choice of starting material.
  • Z. is -N (C 2 H 5 ) 2 and Z 2 is -N (CH 3 ).
  • Example 5 These compounds can be made by following the method of Example 1 (and where 1: 2 metallization is carried out Example 5) using suitable choice of starting materials.
  • Example 1 can be made by the following the method of Example 1 (and where 1: 2 metallization occurs.
  • Example 2 can be prepared by following the method of Example 1 (and where 1: 2 metallization is carried out of Example 5) using a suitable choice of starting materials.
  • Ba is a group of the formula
  • Bb is a group of the formula
  • Example 5 which can be prepared according to Example 1 (or when 1: 2 metallization is carried out Example 5) by the suitable choice of starting materials.
  • Example 5 can be prepared according to Example 1 (or where 1: 2 metallization is carried out Example 5) by the suitable choice of starting materials.
  • Example 1 or where 1: 2 metallization is carried out according to Example 5
  • suitable choice of starting materials can be made according to Example 1 (or where 1: 2 metallization is carried out according to Example 5) by suitable choice of starting materials.
  • Example 184 1: 2 Cr-complex from Example 175.
  • Example 185 1: 2 Co-complex from Example 174.
  • Example 185 1: 2 Co-complex from Example 174.
  • Calf suede leather, chrome-vegetable tanned sheep- skin and box cowhide leather can also be dyed by known methods.
  • Application Example B
  • Examples 1 to 5 is dissolved in 100 parts of hot water and cooled to room temperature. The solution is added to

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Abstract

Sulpho-free azo compound in metal free, 1:1 complex or 1:2 complex form having at least an average of 1.3 water solubilising basic groups of the formula I (FORMULA) in which Ra is an aromatic or acetoacyl group including a metallisable group, x is a metallisable group, R<ut>u is a diazo component, n is 1 or 2, X is a direct bond or bridging group, and R is the group, (FORMULA) when n is 2 with the provisos as given in the specification. The new compounds are useful as dyes for leather and paper.

Description

IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOUNDS IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOUNDS
The invention relates to sulpho—free azo compounds, in metal-free, 1:1 metal complex or 1:2 metal complex form, which are useful for dyeing paper and leather.The invention relates to sulpho — free azo compounds, in metal-free, 1: 1 metal complex or 1: 2 metal complex form, which are useful for dyeing paper and leather.
What is meant by a "1:1 metal complex" is that each molecule of the complex has 1 metal atom bonded to 1 dyestuff molecule or has 2 metal atoms bonded to two dyestuff units, which dyestuff units are joined together by a direct bond or a conventional bridging group; and what is meant by a "1:2 metal complex" is that the complex has 1 atom of metal bonded to two dyestuff units, which dyestuff units can be the same or different but which dyestuff units are part of two separate dyestuff molecules.What is meant by a "1: 1 metal complex" is that each molecule of the complex has 1 metal atom bonded to 1 dyestuff molecule or has 2 metal atoms bonded to two dyestuff units, which dyestuff units are joined together by a direct bond or a conventional bridging group; and what is meant by a "1: 2 metal complex" is that the complex has 1 atom of metal bonded to two dyestuff units, which dyestuff units can be the same or different but which dyestuff units are part of two separate dyestuff molecules.
The invention provides sulpho—free azo compounds in metal-free, 1:1 metal complex or 1:2 metal complex forms having at least on average 1.3 preferably 2 water solubilising basic groups, the compounds being of formula IThe invention provides sulfo — free azo compounds in metal-free, 1: 1 metal complex or 1: 2 metal complex forms having at least on average 1.3 preferably 2 water solubilizing basic groups, the compounds being of formula I
Figure imgf000004_0001
in which
Figure imgf000004_0001
in which
Ra is a group of the formula Ia - IcRa is a group of the formula Ia - Ic
Figure imgf000004_0002
Figure imgf000004_0003
Figure imgf000004_0004
where the group
Figure imgf000004_0002
Figure imgf000004_0003
Figure imgf000004_0004
where the group
Figure imgf000004_0005
is a substituted pyrazolone-5, a substituted 5-aminopyrazole, a substituted 2-pyridone or an unsubstituted or substituted ß-hydroxynaphthalene group; in which yo is OH or NH2; Rb is a (C1-4) alkyl group or a substituted (C1_3) alkyl group;
Figure imgf000004_0005
is a substituted pyrazolone-5, a substituted 5-aminopyrazole, a substituted 2-pyridone or an unsubstituted or substituted ß-hydroxynaphthalene group; in which yo is OH or NH 2 ; R b is a (C 1-4 ) alkyl group or a substituted (C 1 _ 3 ) alkyl group;
Rc is -NH2, a substituted alkyl group, a substituted alkylamino group, a substituted phenylamino group, an unsubstituted or substituted naphthylamino group, an unsubstituted or substituted benzthiazolamino group, an unsubstituted or substituted benzoxazolamino group an unsubstituted or substituted benzimidazolamino group; x and y independently are hydrogen, -OH, (C1-4)- alkyl, -NH2 or COOH orR c is -NH 2 , a substituted alkyl group, a substituted alkylamino group, a substituted phenylamino group, an unsubstituted or substituted naphthylamino group, an unsubstituted or substituted benzthiazolamino group, an unsubstituted or substituted benzoxazolamino group an unsubstituted or substituted benzimidazolamino group; x and y independently are hydrogen, -OH, (C 1-4 ) alkyl, -NH 2 or COOH or
(i) x and y form the group -NH-Me-O-, -NH-Me-OOC-,(i) x and y form the group -NH-Me-O-, -NH-Me-OOC-,
-O-Me-O-, -O-Me-OOC- or -NH-Me-NH- , or-O-Me-O-, -O-Me-OOC- or -NH-Me-NH-, or
(ii) x and yo form the group -NH-Me-O-, -NH-Me-NH- or -O-Me-O- where Me is a metal capable of either forming a 1:1 metal complex or a 1:2 metal complex; or capable of forming both a 1:1 and a 1:2 metal complex; n is 1 or 2; d is 0, 1 or 2;(ii) x and yo form the group -NH-Me-O-, -NH-Me-NH- or -O-Me-O- where Me is a metal capable of either forming a 1: 1 metal complex or a 1 : 2 metal complex; or capable of forming both a 1: 1 and a 1: 2 metal complex; n is 1 or 2; d is 0, 1 or 2;
Rt is one or more of the groups of formula Id to Ig below — N = N - D - [ W ( Z )a ] IdR t is one or more of the groups of formula Id to Ig below - N = N - D - [W (Z) a ] Id
N = N - B1- N = N - K IeN = N - B 1 - N = N - K Ie
Figure imgf000006_0001
Figure imgf000006_0001
- Y - Z Ig- Y - Z Ig
where D is a diazo component ;where D is a diazo component;
W is a direct bond or a conventional bridging group ; B1 is phenylene, naphthalene, tetrahydro naphthalene or a group of the formulaW is a direct bond or a conventional bridging group; B 1 is phenylene, naphthalenes, tetrahydro naphthalenes or a group of the formula
Figure imgf000006_0002
Figure imgf000006_0002
Z is a basic amino or a quaternary ammonium group ; a is 1 or 2 ; b is a number between 1 and 2;Z is a basic amino or a quaternary ammonium group; a is 1 or 2; b is a number between 1 and 2;
K is a coupling component of the series 4-alkyl-2- pyridone, ß-hydroxynaphthalene, aniline, pyrazole-5 or acetoacyl, the coupling component being substituted by at least one water solu bilising basic group;K is a coupling component of the series 4-alkyl-2-pyridones, ß-hydroxynaphthalenes, anilines, pyrazole-5 or acetoacyl, the coupling component being substituted by at least one water solu bilising basic group;
Y is a direct bond or a conventional bridging group; X is a direct bond or a conventional bridging group R is a group of the formula IhY is a direct bond or a conventional bridging group; X is a direct bond or a conventional bridging group R is a group of the formula Ih
Figure imgf000007_0001
where x, Ra, Rt and d are above defined and the rings B, C and D can be each substituted independently by up to two further substituents to give up to three substituents in total and ring F can be substituted by up to three substituents in total , with the proviso that
Figure imgf000007_0001
where x, Ra, R t and d are above defined and the rings B, C and D can be each substituted independently by up to two further substitutes to give up to three substitutes in total and ring F can be substituted by up to three substitents in total, with the proviso that
1) when Ra is the group Ic,Rt is the group Ig;1) when Ra is the group Ic, R t is the group Ig;
2) when Rt is the group Ig, Ra is the group Ia and when n = 2 , the group -X-R is attached to the group2) when R t is the group Ig, Ra is the group Ia and when n = 2, the group -XR is attached to the group
Ra or Rt ,Ra or R t ,
3) when n=2 and when Ra is a group of formula Ia, x and y may not both be selected from hydrogen and C1-4 alkoxy;3) when n = 2 and when Ra is a group of formula Ia, x and y may not both be selected from hydrogen and C 1-4 alkoxy;
and AΘ a non-chromophoric conventional anion.and A Θ a non-chromophoric conventional anion.
Preferably when the compounds of the invention are in 1:1 metal complex form Me is copper, chromium, cobalt, iron, nickel or manganese, more preferably copper, chromium or cobalt, most preferably copper. Preferably copper is Cu2+; chromium is Cr2+ ; cobalt is Co2+ ; iron is Fe2+ ; nickel is Ni2+ and manganese is Mn2+.Preferably when the compounds of the invention are in 1: 1 metal complex form Me is copper, chromium, cobalt, iron, nickel or manganese, more preferably copper, chromium or cobalt, most preferably copper. Preferably copper is Cu 2+ ; chromium is Cr 2+ ; cobalt is Co 2+ ; iron is Fe 2+ ; nickel is Ni 2+ and manganese is Mn 2+ .
Preferably when the compounds of the invention are in 1:2 metal complex form, Me is chromium, cobalt, iron or nickel, more preferably chromium, cobalt or iron, most preferably iron. Preferably chromium is Cr ; cobalt isPreferably when the compounds of the invention are in 1: 2 metal complex form, Me is chromium, cobalt, iron or nickel, more preferably chromium, cobalt or iron, most preferably iron. Preferably chromium is Cr; cobalt is
Co3+, iron is Fe3+ and, nickel is Ni3+.Co 3+ , iron is Fe 3+ and, nickel is Ni 3+ .
Preferably the compounds of the invention when in 1:2 metal complex form and/or in metal free form when n = 2, are symmetrie, i.e. both dyestuff molecules bonded to the metal ion are the same.Preferably the compounds of the invention when in 1: 2 metal complex form and / or in metal free form when n = 2, are symmetry, i.e. both dyestuff molecules bonded to the metal ion are the same.
Further the invention provides sulpho-free azo compounds, in metal-free, 1:1 metal complex or 1:2 metal complex form having on average at least 1.3 preferably 2, water solubilising basic groups, the compounds being of the formula IIFurther the invention provides sulpho-free azo compounds, in metal-free, 1: 1 metal complex or 1: 2 metal complex form having on average at least 1.3 preferably 2, water solubilizing basic groups, the compounds being of the formula II
Figure imgf000008_0001
where D, X, W, a, b, and rings B and C are above defined; c is 1 or 2 ; d' is 0 or 1 ; A1 is -OH or -NH2 ; A3 is hydrogen or -OH or
Figure imgf000008_0001
where D, X, W, a, b, and rings B and C are above defined; c is 1 or 2; d 'is 0 or 1; A 1 is -OH or -NH 2 ; A 3 is hydrogen or -OH or
A1 and A3 form the group -NH-Me-O- or -O-Me-O- where Me is either a metal capable of either forming a 1 : 1 metal complex or a 1:2 metal complex or capable of forming both a 1:1 metal complex and a 1:2 metal complex; A2 is -OH or -NH2 ;A 1 and A 3 form the group -NH-Me-O- or -O-Me-O- where Me is either a metal capable of either forming a 1: 1 metal complex or a 1: 2 metal complex or capable of forming both a 1: 1 metal complex and a 1: 2 metal complex; A 2 is -OH or -NH 2 ;
Rt' is a group of the formula If defined aboveR t 'is a group of the formula If defined above
Z2 is a group of the formulaZ 2 is a group of the formula
Figure imgf000009_0004
where each Ro independently is methyl, ethyl, ß-hydroxyethyl, benzyl, -CH2COCH3 or
Figure imgf000009_0003
provided that not more than one benzyl, -CH2COCH3
Figure imgf000009_0004
where each R o is independently methyl, ethyl, ß-hydroxyethyl, benzyl, -CH 2 COCH 3 or
Figure imgf000009_0003
provided that not more than one benzyl, -CH 2 COCH 3
or is attached or not more than two
Figure imgf000009_0002
ß-hydroxyethyl groups are attached to a nitrogen atom,
or is attached or not more than two
Figure imgf000009_0002
ß-hydroxyethyl groups are attached to a nitrogen atom,
R127 is methyl or ethyl, m is 0 , 1 or 2 and AΘ is defined above with the proviso that each of the azo bridges in ring B is ortho to A1 or A2 or to both A1 and A2. R 127 is methyl or ethyl, m is 0, 1 or 2 and A Θ is defined above with the proviso that each of the azo bridges in ring B is ortho to A 1 or A 2 or to both A 1 and A 2 .
Preferably compounds of formula II are of formula II'Preferably compounds of formula II are of formula II '
Figure imgf000009_0001
where Z2, a, W, b, c, D, A1, A2, A3 , d' and rings B and C are above defined;
Figure imgf000009_0001
where Z 2 , a, W, b, c, D, A 1 , A 2 , A 3 , d 'and rings B and C are above defined;
R"t is a group of the formula αα or αßR " t is a group of the formula αα or αß
Figure imgf000010_0001
Figure imgf000010_0001
SO2-NH-{CH2)p-Z2, (C1-4) alkyl or (C1-4) alkoxy,SO 2 -NH- {CH 2 ) p -Z 2 , (C 1-4 ) alkyl or (C 1-4 ) alkoxy,
where p is 1, 2 or 3, R1 is C1-4alkyl, -C2H4OH or -(CH2)p-N-(R1a)2 wherewhere p is 1, 2 or 3, R 1 is C 1-4 alkyl, -C 2 H 4 OH or - (CH 2 ) p -N- (R 1a ) 2 where
R1a is propyl or butyl, R6 is C1-4alkyl, -C2H4OH or (CH2)p-N- (R6') 2 where R6' is (C1-4) alkyl and R6a is (C1_4) alkyl, -C2H4OH, -(CH2)p-N-(R6')2 or C2H4O-R6' ;R 1a is propyl or butyl, R 6 is C 1-4 alkyl, -C 2 H 4 OH or (CH 2 ) p -N- (R 6 ') 2 where R 6 ' is (C 1-4 ) alkyl and R 6a is (C 1 _ 4 ) alkyl, -C 2 H 4 OH, - (CH 2 ) p -N- (R 6 ') 2 or C 2 H 4 OR 6 ';
R 3 is hydrogen, NO2 , -SO2NH2, -SO2NH-R1
Figure imgf000010_0002
R 3 is hydrogen, NO 2 , -SO 2 NH 2 , -SO 2 NH-R 1
Figure imgf000010_0002
(C1-4) alkyl, (C1_4)alkoxy Alkoxy alkyl (C1-4), (C 1 _ 4)
Figure imgf000011_0001
Figure imgf000011_0002
Figure imgf000011_0003
Figure imgf000011_0004
Figure imgf000011_0001
Figure imgf000011_0002
Figure imgf000011_0003
Figure imgf000011_0004
- CO - NH - (CH2)p - Z2, - NH - CO - (CH2)p - Z2,- CO - NH - (CH 2 ) p - Z 2 , - NH - CO - (CH 2 ) p - Z 2 ,
- SO2 - NH - (CH2)p - Z2 or - CH2 - Z2, where R5 is hydrogen, (C1-4) alkyl or (C1-4)alkoxy;- SO 2 - NH - (CH 2 ) p - Z 2 or - CH 2 - Z 2 , where R 5 is hydrogen, (C 1-4 ) alkyl or (C 1-4 ) alkoxy;
R5' is C1-4alkyl; no is a number between 1 and 2 and the groupR 5 'is C 1-4 alkyl; no is a number between 1 and 2 and the group
(CH2-Z2) is attached to either of phenyl groups J or K(CH 2 -Z 2 ) is attached to either of phenyl groups J or K
R7 is hydrogen, -OH, (C1-4) alkyl, (C1-4) alkoxy -NH - CO - NH2 or -NH - CO - CH3;R 7 is hydrogen, -OH, (C 1-4 ) alkyl, (C 1-4 ) alkoxy -NH - CO - NH 2 or -NH - CO - CH 3 ;
R8 is hydrogen, -NH - CO - (CH2)p - Z2 orR 8 is hydrogen, -NH - CO - (CH 2 ) p - Z 2 or
Figure imgf000012_0005
Figure imgf000012_0005
R4 is hydrogen, -NO2, (C1_4) alkyl or (C1_4)alkoxy ; K1 is a group of the formulaR 4 is hydrogen, -NO 2 , (C 1 _ 4 ) alkyl or (C 1 _ 4 ) alkoxy; K 1 is a group of the formula
Figure imgf000012_0001
Figure imgf000012_0002
Figure imgf000012_0003
Figure imgf000012_0004
Figure imgf000012_0001
Figure imgf000012_0002
Figure imgf000012_0003
Figure imgf000012_0004
Figure imgf000013_0001
Figure imgf000013_0001
Figure imgf000013_0002
Figure imgf000013_0002
C atom is attached to the N atom of the groupC atom is attached to the N atom of the group
Z2 defined above, R25 is (C1-4) alkyl, -COO- (R2 5a ) or -COOH whereZ 2 defined above, R 25 is (C 1-4 ) alkyl, -COO- (R 2 5a ) or -COOH where
R25a is (C1-4) alkyl; R26 is hydrogen, halogen, C1-4) alkyl or (C1-4) alkoxy;R 25a is (C 1-4 ) alkyl; R 26 is hydrogen, halogen, C 1-4 ) alkyl or (C 1-4 ) alkoxy;
R124 is (C1-4) alkyl or -(CH2)p-Z2;R 124 is (C 1-4 ) alkyl or - (CH 2 ) p -Z 2 ;
Ya is hydrogen, (C1-4)alkyl, -C2H4OH or (CH2)p-Z2;Y a is hydrogen, (C 1-4) alkyl, -C 2 H 4 OH or (CH 2) p -Z 2;
Ya' is (C1-4) alkyl, preferably -CH3;Y a 'is (C 1-4 ) alkyl, preferably -CH 3 ;
R9 is (C1-4) alkyl, or -(CH2)p-Z2;R 9 is (C 1-4 ) alkyl, or - (CH 2 ) p -Z 2 ;
R10 is hydrogen, (C1-4)alkyl, C1-4) alkoxy,R 10 is hydrogen, (C 1-4 ) alkyl, C 1-4 ) alkoxy,
-NH-CO-CH3 or -NH-CO-NH2; d' is 0 or 1; R125 is -(CH2)p-Z2, -NH-(CH2)p-Z or
Figure imgf000013_0003
where R126 is hydrogen, -OH, (C1-4)alkoxy ,
-NH-CO-CH 3 or -NH-CO-NH 2 ; d 'is 0 or 1; R 125 is - (CH 2 ) p -Z 2 , -NH- (CH 2 ) p -Z or
Figure imgf000013_0003
where R 126 is hydrogen, -OH, (C 1-4 ) alkoxy,
-NH-CO-(CH2)p-Z2, -CO-NH-(CH2)p-Z2,-NH-CO- (CH 2 ) p -Z 2 , -CO-NH- (CH 2 ) p -Z 2 ,
-SO2-NH-(CH2)p-Z2, -(CH2)p-Z2 or -SO 2 -NH- (CH 2 ) p -Z 2 , - (CH 2 ) p -Z 2 or
Figure imgf000014_0001
and R127 is hydrogen or -(CH2)p-Z2;
Figure imgf000014_0001
and R 127 is hydrogen or - (CH 2 ) p -Z 2;
X' is one of the groups X1 to X53 below:X 'is one of the groups X 1 to X 53 below:
X1 is a direct bond,X 1 is a direct bond,
X2 a straight or branched chain alkylene group of (C1-4) carbon atoms, X3 -CO -X 2 a straight or branched chain alkylene group of (C 1-4 ) carbon atoms, X 3 -CO -
Figure imgf000014_0002
Figure imgf000014_0002
Figure imgf000015_0001
X49 - NH- CO - NH-,
Figure imgf000015_0001
X 49 - NH- CO - NH-,
X50 - O - (CH2)q- O -
Figure imgf000016_0001
Figure imgf000016_0002
Figure imgf000016_0003
where R11 is halogen, (C1-4) alkyl or (C1_4) alkoxy R12 is hydrogen or (C1_4) alkyl; R13 is halogen, -NH-CH2-CH2-OH or
X 50 - O - (CH 2 ) q - O -
Figure imgf000016_0001
Figure imgf000016_0002
Figure imgf000016_0003
where R 11 is halogen, (C 1-4 ) alkyl or (C 1 _ 4 ) alkoxy R 12 is hydrogen or (C 1 _ 4 ) alkyl; R 13 is halogen, -NH-CH 2 -CH 2 -OH or
-N (CH2-CH2OH) 2 ; R14 is a straight or branched chain (C1-4)_ alkylene group and q is 1, 2, 3 or 4 with the provisos that i) the diazo bridges in ring B are ortho each to A1 or A2 or to both A1 and A2 ; ii) when c is 2, X' is attached to Rt" when Rt" is the group αα or to ring C; iii) when d' is 1 ring C can be substituted by one or more of halogen, hydroxy, (C1-4) alkyl, (C1-4)- alkoxy and -NH-CO-NH2.-N (CH 2 -CH 2 OH) 2 ; R 14 is a straight or branched chain (C 1-4 ) _ alkylene group and q is 1, 2, 3 or 4 with the provisos that i) the diazo bridges in ring B are ortho each to A 1 or A 2 or to both A 1 and A 2 ; ii) when c is 2, X 'is attached to R t "when R t " is the group αα or to ring C; iii) when d 'is 1 ring C can be substituted by one or more of halogen, hydroxy, (C 1-4 ) alkyl, (C 1-4 ) - alkoxy and -NH-CO-NH 2 .
Still further the invention provides sulpho-free azo compounds, in metal-free, 1:1 metal complex or 1:2 metal complex form having an average of at least 1,3 water solubilising basic groups per dyestuff unit, the compounds being of the formula III Still further the invention provides sulpho-free azo compounds, in metal-free, 1: 1 metal complex or 1: 2 metal complex form having an average of at least 1,3 water solubilizing basic groups per dyestuff unit, the compounds being of the formula III
Figure imgf000017_0001
in which A4 is hydrogen, -OH, -NH2, (C1-4)alkoxy or COOH or A4 and a hydroxy or amino group on K2 together form the group -NH-Me-O-, -NH-Me-NH-, -NH-Me-OOC-, -O-Me-O- or -O-Me-OOC- where Me is a metal capable of either forming a 1:1 metal complex or a 1:2 metal complex or capable of forming both a 1:1 and a 1:2 metal complex,
Figure imgf000017_0001
in which A 4 is hydrogen, -OH, -NH 2 , (C 1-4 ) alkoxy or COOH or A 4 and a hydroxy or amino group on K 2 together form the group -NH-Me-O-, -NH- Me-NH-, -NH-Me-OOC-, -O-Me-O- or -O-Me-OOC- where Me is a metal capable of either forming a 1: 1 metal complex or a 1: 2 metal complex or capable of forming both a 1: 1 and a 1: 2 metal complex,
K2 is one of the groups of the formulaK 2 is one of the groups of the formula
Figure imgf000017_0002
Figure imgf000017_0003
Figure imgf000018_0001
R21 is hydrogen, -NO2, -NH-CO (CH2)s-Z2 , -CH2-Z2, -SO2-NH-(CH2)s- Z2, -SO2-NH2, -CO-CH2~Z2,
Figure imgf000017_0002
Figure imgf000017_0003
Figure imgf000018_0001
R 21 is hydrogen, -NO 2 , -NH-CO (CH 2 ) s -Z 2 , -CH 2 -Z 2 , -SO 2 -NH- (CH 2 ) s - Z 2 , -SO 2 -NH 2 , -CO-CH 2 ~ Z 2 ,
-CO-NH-(CH2)s-Z2 or-CO-NH- (CH 2 ) s -Z 2 or
Figure imgf000019_0001
R22 is hydrogen, -NO2, -SO2-NH2, -SO2-N (R22a)2
Figure imgf000019_0001
R 22 is hydrogen, -NO 2 , -SO 2 -NH 2 , -SO 2 -N (R 22a ) 2
-SO2-NH-(CH2)s-OH, -CH2-Z2 , -SO2-NH- (CH2)s-Z2, -CO-NH- (CH2)s-Z2, -NH-CO-(CH2)s-Z2 or-SO 2 -NH- (CH 2 ) s -OH, -CH 2 -Z 2 , -SO 2 -NH- (CH 2 ) s -Z 2 , -CO-NH- (CH 2 ) s -Z 2 , -NH-CO- (CH 2 ) s -Z 2 or
Figure imgf000019_0002
where R22a is (C1--4)alkyl;
Figure imgf000019_0002
where R 22a is (C 1--4 ) alkyl;
R23 is hydrogen or -CH3 R 23 is hydrogen or -CH 3
Figure imgf000019_0003
Figure imgf000019_0003
Figure imgf000019_0004
where R35 is hydrogen, (C1-4) alkyl or -CH2-COO-R35a where R 35a is (C1-4)alkyl
Figure imgf000019_0004
where R 35 is hydrogen, (C 1-4 ) alkyl or -CH 2 -COO-R 35a where R 35a is (C 1-4 ) alkyl
R 24 is hydrogen, (C1-4)alkyl, -C2H4OH, - (CH2)p-Z2, benzyl, , -(CH2)3OCH3;
Figure imgf000019_0005
Figure imgf000020_0001
where R24a is (C1-4) alkyl, preferably -CH3 ;
R 24 is hydrogen, (C 1-4 ) alkyl, -C 2 H 4 OH, - (CH 2 ) p -Z 2 , benzyl,, - (CH 2 ) 3 OCH 3 ;
Figure imgf000019_0005
Figure imgf000020_0001
where R 24a is (C 1-4 ) alkyl, preferably -CH 3 ;
R25 is (C1-4) alkyl, -COO- (R25a) or COOH whereR 25 is (C 1-4 ) alkyl, -COO- (R 25a ) or COOH where
R25a is (C1-4)alkyl; s is 1, 2, 3, 4, 5 or 6.R 25a is (C 1-4 ) alkyl; it is 1, 2, 3, 4, 5 or 6.
R28 is hydrogen, (C1-4) alkyl, (C1-4) alkoxy or halogen, R29 is hydrogen, (C1-4) alkyl, (C1-4) alkoxy, halogen, -NH- (CH2)s-Z2 or -NH- C2H4OH; each R30 independently is hydrogen or (C1-4)alkyl;R 28 is hydrogen, (C 1-4 ) alkyl, (C 1-4 ) alkoxy or halogen, R 29 is hydrogen, (C 1-4 ) alkyl, (C 1-4 ) alkoxy, halogen, -NH- ( CH 2 ) s -Z 2 or -NH- C 2 H 4 OH; each R 30 is independently hydrogen or (C 1-4 ) alkyl;
Figure imgf000020_0002
Figure imgf000020_0003
Figure imgf000020_0004
where d', Zo , Wa and R5 are defined above;
Figure imgf000020_0002
Figure imgf000020_0003
Figure imgf000020_0004
where d ', Z o , Wa and R 5 are defined above;
R33 is hydrogen, halogen, (C1-4)alkyl, (C1-4)- alkoxy, -SO2NH2 or -SO2N(CH3)2; with the provisos that i) R20 and R21 cannot both be -NO2 , ii) R21 and R22 cannot be the same group unless R21 and R22 are both hydrogen, iii) when R21 and R22 are both hydrogen R20 cannot be -NO2 and iv) R20 cannot be -NO2 when R21 , R22 an R23 lare hydrogen. Still further the invention provides sulpho-free azo compounds in metal-free, 1:1 metal complex or 1:2 metal complex form having at least 1.3 preferably 2 water solubilising basic groups, the compounds being of the formula IVR 33 is hydrogen, halogen, (C 1-4 ) alkyl, (C 1-4 ) alkoxy, -SO 2 NH 2 or -SO 2 N (CH 3 ) 2 ; with the provisos that i) R 20 and R 21 cannot both be -NO 2 , ii) R 21 and R 22 cannot be the same group unless R 21 and R 22 are both hydrogen, iii) when R 21 and R 22 are both hydrogen R 20 cannot be -NO 2 and iv) R 20 cannot be -NO 2 when R 21 , R 22 an R 23 lare hydrogen. Still further the invention provides sulpho-free azo compounds in metal-free, 1: 1 metal complex or 1: 2 metal complex form having at least 1.3 preferably 2 water solubilizing basic groups, the compounds being of the formula IV
Figure imgf000021_0001
in which A1 is -OH or -NH2 and A5 is -OH, (C1-4) alkoxy or -COOH or A1 and A5 together form the group -NH-Me-NH, -NH-Me-OOC-, -NH-Me-O-, -O-Me-O, -O-Me-OOC where Me is a metal capable of either forming a 1:1 metal complex or a 1:2 metal complex or capable of forming both a 1:1 metal complex and a 1:2 metal complex; e is 0 or 1; R60 is hydrogen or -NO2;
Figure imgf000021_0001
in which A 1 is -OH or -NH 2 and A 5 is -OH, (C 1-4 ) alkoxy or -COOH or A 1 and A 5 together form the group -NH-Me-NH, -NH-Me- OOC-, -NH-Me-O-, -O-Me-O, -O-Me-OOC where Me is a metal capable of either forming a 1: 1 metal complex or a 1: 2 metal complex or capable of forming both a 1: 1 metal complex and a 1: 2 metal complex; e is 0 or 1; R 60 is hydrogen or -NO 2 ;
R61 and R62, independently, are hydrogen, -NO2,R 61 and R 62 , independently, are hydrogen, -NO 2 ,
-CH2-Z2, -SO2-NH2, -SO2-NH-(CH2)p-Z2, -SO2 -NH-C2H4OH, -SO2-N-(R6'2 )2, -CO-NH-(CH2)p-Z2, -NH-CO-(CH2)p-Z2 -CH 2 -Z 2 , -SO 2 -NH 2 , -SO 2 -NH- (CH 2 ) p -Z 2 , -SO 2 -NH-C 2 H 4 OH, -SO 2 -N- (R 6 ' 2 ) 2 , -CO-NH- (CH 2 ) p -Z 2 , -NH-CO- (CH 2 ) p -Z 2
Figure imgf000022_0001
Figure imgf000022_0002
Figure imgf000022_0001
Figure imgf000022_0002
where R6'2 is (C1-4) alkyl,where R 6 ' 2 is (C 1-4 ) alkyl,
R63 is -SO2-NH-(CH2)p-Z2, -CO-NH-(CH2)p-Z2,R 63 is -SO 2 -NH- (CH 2 ) p -Z 2 , -CO-NH- (CH 2 ) p -Z 2 ,
-NH-CO-(CH2)p-Z2 ,-NH-CO- (CH 2 ) p -Z 2 ,
or -CH2-Z2;
Figure imgf000022_0003
or -CH 2 -Z 2 ;
Figure imgf000022_0003
R64 is hydrogen or (C1-4) alkoxy each R65 independently is hydrogen (C1-4) alkyl or C1-4- alkoxy ; p is 1, 2 or 3 ; q' is 1 or 2 with the proviso that when R63 is -CO-NH- (CH2)p-Z2 q' is 2; K3 is one of the following groups
Figure imgf000023_0001
Figure imgf000023_0002
Figure imgf000023_0003
Figure imgf000023_0004
Figure imgf000024_0004
where R9, R10 R25 and Z 2 are above defined,
R 64 is hydrogen or (C 1-4 ) alkoxy each R 65 is independently hydrogen (C 1-4 ) alkyl or C 1-4 - alkoxy; p is 1, 2 or 3; q 'is 1 or 2 with the proviso that when R 63 is -CO-NH- (CH 2 ) p -Z 2 q' is 2; K 3 is one of the following groups
Figure imgf000023_0001
Figure imgf000023_0002
Figure imgf000023_0003
Figure imgf000023_0004
Figure imgf000024_0004
where R 9 , R 10 R 25 and Z 2 are defined above,
R66 is hydrogen, (C1-4) alkyl, -C2H4OH orR 66 is hydrogen, (C 1-4 ) alkyl, -C 2 H 4 OH or
- (CH2 ) p-Z2 ;- (CH 2 ) p -Z 2 ;
R6'6 is (C1-4) alkyl,R 6 ' 6 is (C 1-4 ) alkyl,
Ta is a group of the formulaTa is a group of the formula
Figure imgf000024_0001
Figure imgf000024_0001
Figure imgf000024_0002
Figure imgf000024_0002
where d, R127 and AΘ are defined above
Figure imgf000024_0005
where d, R127 and A Θ are defined above
Figure imgf000024_0005
Figure imgf000024_0003
where R71 is hydrogen, -OH, (C1-4) alkoxy, -NH-CO-(CH2)p-Z2, -CO-NH- (CH2)p-Z2 ,
Figure imgf000024_0003
where R 71 is hydrogen, -OH, (C 1-4 ) alkoxy, -NH-CO- (CH 2 ) p -Z 2 , -CO-NH- (CH 2 ) p -Z 2 ,
-SO2-NH-(CH2)p-Z2, -(CH2)p-Z2 or-SO 2 -NH- (CH 2 ) p -Z 2 , - (CH 2 ) p -Z 2 or
Figure imgf000025_0001
and R72 is hydrogen or -(CH2)p-Z2 ; R69 is (C1-4) alkyl or-(CH2)p-Z2 where p and Z2 are above defined
Figure imgf000025_0001
and R 72 is hydrogen or - (CH 2 ) p -Z 2 ; R 69 is (C 1-4 ) alkyl or- (CH 2 ) p -Z 2 where p and Z 2 are above defined
Figure imgf000025_0002
Figure imgf000025_0003
where each R65 independently, is hydrogen, (C1-4) alkyl or (C1_4) alkoxy; and X' is as defined above; with the provisos
Figure imgf000025_0002
Figure imgf000025_0003
where each R 65 is independently, is hydrogen, (C 1-4 ) alkyl or (C 1 _ 4 ) alkoxy; and X 'is as defined above; with the provisos
(i) that R60 and R61 cannot both be -NO2,(i) that R 60 and R 61 cannot both be -NO 2 ,
(ii) that when R61 and R62 are both hydrogen, R60 cannot be -NO2 ,(ii) that when R 61 and R 62 are both hydrogen, R 60 cannot be -NO 2 ,
(iii) that R61 and R62 are not the same group unless both are hydrogen, and(iii) that R 61 and R 62 are not the same group unless both are hydrogen, and
(iv) that each azo bridge in ring B is in an ortho position either to A1 or A2 or to both A1 and A2. A group of preferred metal-free azo compounds of formula II' are those of formula Ila(iv) that each azo bridge in ring B is in an ortho position either to A 1 or A 2 or to both A 1 and A 2 . A group of preferred metal-free azo compounds of formula II 'are those of formula Ila
Figure imgf000026_0001
Figure imgf000026_0001
Figure imgf000026_0005
or
Figure imgf000026_0005
or
Figure imgf000026_0002
where each R2a independently is hydrogen, -NO2, -SO2NH2, -SO2-NH-CH3, -SO2-N(CH3)2 ,
Figure imgf000026_0002
where each R 2a is independently hydrogen, -NO 2 , -SO 2 NH 2 , -SO 2 -NH-CH 3 , -SO 2 -N (CH 3 ) 2 ,
,-SO2NH-C2H4OH,
Figure imgf000026_0003
, -SO 2 NH-C 2 H 4 OH,
Figure imgf000026_0003
-SO2-N(C2H4OH)2, -SO2-N[C2H4-N(CH3)2]2 or -SO2-NH- (CH2) 3-Z2 ; each R3a independently is hydrogen, -NO2, -SO2NH2,-SO 2 -N (C 2 H 4 OH) 2 , -SO 2 -N [C 2 H 4 -N (CH 3 ) 2 ] 2 or -SO 2 -NH- (CH 2 ) 3 -Z 2 ; each R 3a is independently hydrogen, -NO 2 , -SO 2 NH 2 ,
-SO2-NH-CH3 , -SO2-N(CH3)2,
Figure imgf000026_0004
-SO2-NH-C2H4OH,-SO2-N(C2 H4 OH)2 , -NH-CO-(CH2)p -Z2.
-SO 2 -NH-CH 3 , -SO 2 -N (CH 3 ) 2 ,
Figure imgf000026_0004
-SO 2 -NH-C 2 H 4 OH, -SO 2 -N (C 2 H 4 OH) 2 , -NH-CO- (CH 2 ) p -Z 2 .
-CO-NH-(CH2)p -Z2, -CH3, -OCH3, -SO2 -NΗ-(CH2)p -Z2,
Figure imgf000027_0001
-CO-NH- (CH 2 ) p -Z 2 , -CH 3 , -OCH 3 , -SO 2 -NΗ- (CH 2 ) p -Z 2 ,
Figure imgf000027_0001
in which R7a is hydrogen, -OH, -CH3 , -OCH3 , -NHCOCH3 or -NHCONH2; R8a is hydrogen, -NHCO- ( CH2) -Z2 orin which R 7a is hydrogen, -OH, -CH 3 , -OCH 3 , -NHCOCH 3 or -NHCONH 2 ; R 8a is hydrogen, -NHCO- (CH 2 ) -Z 2 or
Figure imgf000027_0002
n0' is an average number between 1.0 and 1.7 K1' is
Figure imgf000027_0002
n 0 'is an average number between 1.0 and 1.7 K 1 ' is
Figure imgf000027_0003
Figure imgf000027_0003
Figure imgf000027_0004
in which R9a is -CH3 or C2H5,
Figure imgf000027_0004
in which R 9a is -CH 3 or C 2 H 5 ,
R 10a is hydrogen, -CH3 , -OCH3 , -NH-CO-CH3 orR 10a is hydrogen, -CH 3 , -OCH 3 , -NH-CO-CH 3 or
-NH-CO-NH2 ;and-NH-CO-NH 2 ; and
R9' is hydrogen, -CH3 , -C2H5 , n-C3H7, n-C4H9 , i-C3H7, i-C4H9, -C2H4OH or -(CH2)p -Z2; R4a is hydrogen, -NO2 , -CH3 or -OCH3;R 9 'is hydrogen, -CH 3 , -C 2 H 5 , nC 3 H 7 , nC 4 H 9 , iC 3 H 7 , iC 4 H 9 , -C 2 H 4 OH or - (CH 2 ) p - Z 2 ; R 4a is hydrogen, -NO 2 , -CH 3 or -OCH 3 ;
-D1-Z2 is-D 1 -Z 2 is
Figure imgf000028_0001
Figure imgf000028_0001
R15 is hydrogen, -OH, -OCH3 , -CH3 or Cl, R16 is hydrogen or -CH3; q0 is 2 to 5, preferably 2 or 3; and all the other symbols are as defined above. A further group of preferred metal-free azo compounds of formula II' are those of formula IlbR 15 is hydrogen, -OH, -OCH 3 , -CH 3 or Cl, R 16 is hydrogen or -CH 3 ; q 0 is 2 to 5, preferably 2 or 3; and all the other symbols are as defined above. A further group of preferred metal-free azo compounds of formula II 'are those of formula Ilb
in which Rt iv is in which R t iv is
Figure imgf000029_0002
Figure imgf000029_0003
where R2d is hydrogen, -OH, -CH3 or -OCH3 ;
Figure imgf000029_0002
Figure imgf000029_0003
where R 2d is hydrogen, -OH, -CH 3 or -OCH 3 ;
and each ring C independently can be substituted in a position ortho to its azo bridge by chlorine and/or -CH3 and/or -OCH3 and the group Xa is in a meta- or para-position to the azo bridge of ring C and each azo bridge, in ring B is ortho to A1 or A2 or to both A1and A2 ;and each ring C independently can be substituted in a position ortho to its azo bridge by chlorine and / or -CH 3 and / or -OCH 3 and the group X a is in a meta- or para-position to the azo bridge of ring C and each azo bridge, in ring B is ortho to A 1 or A 2 or to both A 1 and A 2 ;
Xa is X1 , X5 , X6 , X7 , X10 , X11, X12 , X16 , X17, X22,X a is X 1 , X 5 , X 6 , X 7 , X 10 , X 11 , X 12 , X 16 , X 17 , X 22 ,
X25, X26, X27, X30, X31, X49 or the following groups X2' -CH2-, X2" -(CH2)2-, X'2'' -(CH2) 3-,
Figure imgf000030_0001
X 25 , X 26 , X 27 , X 30 , X 31 , X 49 or the following groups X 2 '-CH 2 -, X 2 "- (CH 2 ) 2 -, X' 2 '' - (CH 2 ) 3 -,
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000031_0001
X3'5 -CO-NH- (CH2) 2-O- (CH2) 2-NH-CO-, X3"5 -CO-NH- (CH2) 2-O- (CH2) 2-O- (CH2) 2"NH-CO- , X 3 ' 5 -CO-NH- (CH 2 ) 2 -O- (CH 2 ) 2 -NH-CO-, X3 " 5 -CO-NH- (CH 2 ) 2 -O- (CH 2 ) 2 - O- (CH 2 ) 2 "NH-CO-,
X3'6 -CO-NH- (CH2) 2-NH- (CH2) 2-NH-CO- , X 3 ' 6 -CO-NH- (CH 2 ) 2 -NH- (CH 2 ) 2 -NH-CO-,
Figure imgf000032_0002
Figure imgf000032_0003
X5'0 -O-CH2-CH2-O-
Figure imgf000032_0002
Figure imgf000032_0003
X 5 ' 0 -O-CH 2 -CH 2 -O-
X5"0 -O-(CH2)-O- X5'1 -CH=CH-CO-NH- ,X 5 " 0 -O- (CH 2 ) -O- X 5 ' 1 -CH = CH-CO-NH-,
Figure imgf000032_0004
Figure imgf000032_0005
X5'3 -CH2-CH2-CO-NH- ,
Figure imgf000032_0004
Figure imgf000032_0005
X 5 ' 3 -CH 2 -CH 2 -CO-NH-,
Figure imgf000032_0006
where R11a is hydrogen, -Cl, -CH3 or -OCH3;
Figure imgf000032_0006
where R 11a is hydrogen, -Cl, -CH 3 or -OCH 3 ;
R13a is -Cl, -NH-CH2-CH2-OH or -N (CH2~CH2-OH)2; and all the other symbols have been defined above.R 13a is -Cl, -NH-CH 2 -CH 2 -OH or -N (CH 2 ~ CH 2 -OH) 2 ; and all the other symbols have been defined above.
Preferred compounds of formula Ilb are of thePreferred compounds of formula Ilb are of the
Figure imgf000032_0001
in which Xb is X1 , X11, X12 , X17 , X27, X49, X2" X'14, X1'9, X1"9, X1'''9, X2'0, X2"0, X3'2 , X3'4 , X3 iv 4, Xv 34 or
Figure imgf000032_0001
in which Xb is X 1 , X 11 , X 12 , X 17 , X 27 , X 49 , X 2 "X '14 , X 1 ' 9 , X 1 " 9 , X 1 ''' 9 , X 2 ' 0 , X 2 " 0 , X 3 ' 2 , X 3 ' 4 , X 3 iv 4 , X v 34 or
Figure imgf000033_0002
where -D1-Z3 has the significances of
Figure imgf000033_0002
where -D 1 -Z 3 has the significant of
-D1-Z2 except Z2 is replaced by Z3 with the proviso that in ring C the group Xb is in a meta- or para-position to its azo bridge.-D 1 -Z 2 except Z 2 is replaced by Z 3 with the proviso that in ring C the group X b is in a meta or para-position to its azo bridge.
Preferred azo compounds of formula II' when inPreferred azo compounds of formula II 'when in
1:1 metal complex form and when c = 1 are of the formula Ild1: 1 metal complex form and when c = 1 are of the formula Ild
Figure imgf000033_0001
in which Z2-D1 , Rt" , A2, , R2a and R3a are defined above and A1' is -NH- or -O- with the proviso that in ring B each azo bridge to the ring C is ortho to A1 or both A1 and A2 and Me is copper, cobalt, iron or chromium.
Figure imgf000033_0001
in which Z 2 -D 1 , R t ", A 2 ,, R 2a and R 3a are defined above and A 1 'is -NH- or -O- with the proviso that in ring B each azo bridge to the ring C is ortho to A 1 or both A 1 and A 2 and Me is copper, cobalt, iron or chromium.
Preferred compounds of the formula Ild are of the formula Ile Preferred compounds of the formula Ild are of the formula Ile
Figure imgf000034_0001
in which Rt v is hydrogen,
Figure imgf000034_0002
Mec is copper , cobalt or chromium preferably copper
Figure imgf000034_0001
in which R t v is hydrogen,
Figure imgf000034_0002
Me c is copper, cobalt or chromium preferably copper
R2b is hydrogen, -NO2 or -SO2-NH2,R 2b is hydrogen, -NO 2 or -SO 2 -NH 2 ,
R3b is hydrogen, -NO2 , -CH3 , -OCH3 , -SO2NH2,R 3b is hydrogen, -NO 2 , -CH 3 , -OCH 3 , -SO 2 NH 2 ,
-NH-CO- (CH2) -Z3, -CH2-Z3, - SO2NH (CH2)pZ3 ,-NH-CO- (CH 2 ) -Z 3 , -CH 2 -Z 3 , - SO 2 NH (CH 2 ) p Z 3 ,
Figure imgf000034_0003
no" is from 1.3 to 1.5
Figure imgf000034_0003
n o "is from 1.3 to 1.5
R 4b is hydrogen or -NO2, and all the other symbols are as defined above. Alternatively preferred compounds of formula II' in 1:1 metal complex form where c = 2 are of the formula IlfR 4b is hydrogen or -NO 2 , and all the other symbols are as defined above. Alternatively preferred compounds of formula II 'in 1: 1 metal complex form where c = 2 are of the formula Ilf
Figure imgf000035_0001
in which the symbols are above defined and the group Xa is attached to each ring C in the meta- or para-position with respect to the azo bridge and the rings C carry no furt85r substituents.
Figure imgf000035_0001
in which the symbols are above defined and the group Xa is attached to each ring C in the meta- or para-position with respect to the azo bridge and the rings C carry no furt85r substituents.
Preferred compounds of formula Ilf are of the formula IIgPreferred compounds of formula Ilf are of the formula IIg
Figure imgf000035_0002
in which the symbols are as above defined, and with the proviso that Xb is in a meta- or para-position to the azo bridge. A further group of preferred compounds of formula II ' in 1 : 1 metal complex form are of formula Ilh
Figure imgf000035_0002
in which the symbols are as defined above, and with the proviso that Xb is in a meta or para-position to the azo bridge. A further group of preferred compounds of formula II 'in 1: 1 metal complex form are of formula Ilh
Figure imgf000036_0001
in which D1 , A1' , R3a, R4 a , Mea, and Xa are above defined;
Figure imgf000036_0001
in which D 1 , A 1 ', R 3a , R 4 a , Me a , and Xa are defined above;
R70 is hydrogen, chlorine, methyl or methoxy; a the group Xa is attached in meta- or para- position in ring F to the azo group and each azo bridge in ring B is in ortho position to A1 or A2 or to both A1 and A2.R 70 is hydrogen, chlorine, methyl or methoxy; a the group Xa is attached in meta or para position in ring F to the azo group and each azo bridge in ring B is in ortho position to A 1 or A 2 or to both A 1 and A 2 .
More preferred compounds of formula Ilh are of the formula IliMore preferred compounds of formula Ilh are of the formula Ili
Figure imgf000036_0002
in which R3e is hydrogen, -CH3, -NO2, -SO2-NH2, -CH2-Z3,
Figure imgf000036_0002
in which R 3e is hydrogen, -CH 3 , -NO 2 , -SO 2 -NH 2 , -CH 2 -Z 3 ,
Figure imgf000037_0001
Figure imgf000037_0001
R4e is hydrogen or -NO2 and all the other symbols are as defined above and Xb is attached in the ortho- or meta-position to the azo group. Preferred 1:2 metal complex azo compounds of formula II' where c is 1 and are one of the formulae IIj to IIm below:R 4e is hydrogen or -NO 2 and all the other symbols are as defined above and Xb is attached in the ortho- or meta-position to the azo group. Preferred 1: 2 metal complex azo compounds of formula II 'where c is 1 and are one of the formula IIj to IIm below:
Figure imgf000037_0002
Figure imgf000038_0001
Figure imgf000038_0002
Figure imgf000038_0003
in which R40 is hydrogen or Z2-D1-N=N-;
Figure imgf000037_0002
Figure imgf000038_0001
Figure imgf000038_0002
Figure imgf000038_0003
in which R 40 is hydrogen or Z 2 -D 1 -N = N-;
Meg is cobalt, iron or chromium, preferably iron R42 is-(CH2)p-Z2, -NH-(CH2)p-Z2 orMe g is cobalt, iron or chromium, (CH 2) p -Z 2, -NH- (CH 2) preferably iron R 42 is- p -Z 2 or
Figure imgf000039_0001
Figure imgf000039_0001
R43 is -CH3, C2H5 or (CH2)p-Z2 ; R44 is hydrogen, -OH, (C1-4) alkoxy,R 43 is -CH 3 , C 2 H 5 or (CH 2 ) p -Z 2 ; R 44 is hydrogen, -OH, (C 1-4 ) alkoxy,
-NH-CO- (CH2)p-Z2, -CO-NH- (CH2)p-Z2,-NH-CO- (CH 2 ) p -Z 2 , -CO-NH- (CH 2 ) p -Z 2 ,
-SO2,-NH-(CH2)p-Z2,
Figure imgf000039_0002
or "(CH2)p-Z2 ;
-SO 2 , -NH- (CH 2 ) p -Z 2 ,
Figure imgf000039_0002
or "(CH 2 ) p -Z 2 ;
R 45 is hydrogen or -(CH2)p-Z2 ;R 45 is hydrogen or - (CH 2 ) p -Z 2 ;
R2'a has the significances of R2 aand may also be -OH or . -NH2 ; and the other symbols are as defined above. Preferred compounds of formula IIj are Symmetric and are of the formula IlnR 2 ' a has the significances of R 2 a and may also be -OH or. -NH 2 ; and the other symbols are as defined above. Preferred compounds of formula IIj are Symmetric and are of the formula Iln
Figure imgf000039_0003
in which R3c is hydrogen, -NO2, -CH3 , -OCH3, -SO2-NH2, -SO2NH(CH2)3N(CH3)2, -SO2NHC2H4OH , -NH-CO- (CH2)p-Z3, -CH2-Z3, -N=N-K1' ,
Figure imgf000039_0003
in which R 3c is hydrogen, -NO 2 , -CH 3 , -OCH 3 , -SO 2 -NH 2 , -SO 2 NH (CH 2 ) 3 N (CH 3 ) 2 , -SO 2 NHC 2 H 4 OH , -NH-CO- (CH 2 ) p -Z 3 , -CH 2 -Z 3 , -N = NK 1 ',
Figure imgf000040_0001
Figure imgf000040_0001
-SO2NH (CH2) pN (CH3) 2 -SO 2 NH (CH 2 ) p N (CH 3 ) 2
and Rv t i is hydrogen and, where the group Z3-D1-N=N- has the significanceand R v t i is hydrogen and, where the group Z 3 -D 1 -N = N- has the significance
Figure imgf000040_0002
then Rv t ihas the additional significance of
Figure imgf000040_0002
then R v t i has the additional significance of
Figure imgf000040_0003
Figure imgf000040_0003
and the other symbols are defined above, and where the azo bridges in ring B are ortho to the -O- or -OH group. Preferred azo compounds of formula III in metal free form have the formula lIla
Figure imgf000041_0001
Figure imgf000041_0002
Figure imgf000041_0003
and the other symbols are defined above, and where the azo bridges in ring B are ortho to the -O- or -OH group. Preferred azo compounds of formula III in metal free form have the formula III
Figure imgf000041_0001
Figure imgf000041_0002
Figure imgf000041_0003
Figure imgf000042_0001
and the other symbols are above defined with the provisos
Figure imgf000042_0001
and the other symbols are above defined with the provisos
(i) that the azo bridge in ring B is in the 3 or 4 position; (ii) that R34 and R35 are not both -NO2 ; and (iii) that the compounds of formula lIla contain at least two water solubilising basic groups. Preferred azo compounds of formula lIla are of the formula Illb(i) that the azo bridge in ring B is in the 3 or 4 position; (ii) that R 34 and R 35 are not both -NO 2 ; and (iii) that the compounds of formula III contain at least two water solubilizing basic groups. Preferred azo compounds of formula III are of the formula Illb
Figure imgf000042_0002
Figure imgf000042_0002
in which R24 is hydrogen, -CH3, -C2H5, -C2H4OH orin which R 24 is hydrogen, -CH 3 , -C 2 H 5 , -C 2 H 4 OH or
Figure imgf000042_0003
Figure imgf000042_0003
Figure imgf000043_0001
Figure imgf000043_0001
and all the other symbols are above defined , with the proviso that R34 and R35 are not both -NO2. Most preferred azo compounds of formula lIla are of formula IIIcand all the other symbols are above defined, with the proviso that R 34 and R 35 are not both -NO 2 . Most preferred azo compounds of formula III are of formula IIIc
Figure imgf000043_0002
Figure imgf000043_0003
Figure imgf000044_0001
Figure imgf000044_0002
and where all the other symbols are above defined, with the proviso that R34 and R35 are not both NO2.
Figure imgf000043_0002
Figure imgf000043_0003
Figure imgf000044_0001
Figure imgf000044_0002
and where all the other symbols are defined above, with the proviso that R 34 and R 35 are not both NO 2 .
Alternatively preferred compounds of formula III in metal free form are of the formula IlldAlternatively preferred compounds of formula III in metal free form are of the formula Illd
Figure imgf000044_0003
Figure imgf000044_0004
R22d is hydrogen, -CH2-Z3, -SO2 -N (CH3)22 , -NO2,
Figure imgf000044_0003
Figure imgf000044_0004
R 22d is hydrogen, -CH 2 -Z 3 , -SO 2 -N (CH 3 ) 22 , -NO 2 ,
-SO2-NH-(CH2)q-OH,
Figure imgf000045_0001
-SO 2 -NH- (CH 2 ) q -OH,
Figure imgf000045_0001
-CO-NH-(CH2)q-Z3 or -NH-CO- (CH2)q-Z3,
Figure imgf000045_0002
Figure imgf000045_0003
Figure imgf000045_0004
Figure imgf000045_0005
-CO-NH- (CH 2 ) q -Z 3 or -NH-CO- (CH 2 ) q -Z 3 ,
Figure imgf000045_0002
Figure imgf000045_0003
Figure imgf000045_0004
Figure imgf000045_0005
Figure imgf000046_0001
Figure imgf000046_0001
Figure imgf000046_0002
Figure imgf000046_0002
Rg''' is hydrogen, CH3, -C 2,H5, i-C3H7, i-C4H9, n-C3H7, n-C4H9, -C2H4OH, -(CH2)q-Z3;Rg '''is hydrogen, CH 3 , -C 2 , H 5 , iC 3 H 7 , iC 4 H 9 , nC 3 H 7 , nC 4 H 9 , -C 2 H 4 OH, - (CH 2 ) q -Z 3 ;
R50 is hydrogen, -Cl, -Br, -CH3 or OCH3;R 50 is hydrogen, -Cl, -Br, -CH 3 or OCH 3 ;
Figure imgf000046_0003
Figure imgf000046_0003
R52 is hydrogen, -Cl, -Br, -CH3 or -OCH3;R 52 is hydrogen, -Cl, -Br, -CH 3 or -OCH 3 ;
R53 is hydrogen, -NH-(CH2)q-Z3, -NH-C2H4OH, -Cl,R 53 is hydrogen, -NH- (CH 2 ) q -Z 3 , -NH-C 2 H 4 OH, -Cl,
-Br, -CH3 or -OCH3; R54 is hydrogen,
Figure imgf000046_0004
-Br, -CH 3 or -OCH 3 ; R 54 is hydrogen,
Figure imgf000046_0004
R55 is hydrogen, -Cl, -Br, -CH3,-OCH3, -SO2NH2 orR 55 is hydrogen, -Cl, -Br, -CH 3 , -OCH 3 , -SO 2 NH 2 or
-SO2-N(CH3)2 with the provisos-SO 2 -N (CH 3 ) 2 with the provisos
(i) that R21d and R22d are not both the same unless both are hydrogen; (ii) that R20 and R21d are not both NO2; (iii) that the starred carbon atoms are not attached to the N-atom of the basic or quaternary ammonium group; an (iv) that R20 is not NO2 when R21d or R22d are both hydrogen. Preferred compounds of formula Illd are of the formula Ille(i) that R 21d and R 22d are not both the same unless both are hydrogen; (ii) that R 20 and R 21d are not both NO 2 ; (iii) that the starred carbon atoms are not attached to the N-atom of the basic or quaternary ammonium group; an (iv) that R 20 is not NO 2 when R 21d or R 22d are both hydrogen. Preferred compounds of formula Illd are of the formula Ille
Figure imgf000047_0001
Figure imgf000047_0001
in which R22e is hydrogen, -CH2-Z5,in which R 22e is hydrogen, -CH 2 -Z 5 ,
-SO2-NH-(CH2)m' Z5, -CO-NH- (CH2)m'-Z5, -NO2,-SO 2 -NH- (CH 2 ) m 'Z 5 , -CO-NH- (CH 2 ) m ' -Z 5 , -NO 2 ,
-NH-CO- (CH2)a -Z5 or-NH-CO- (CH 2 ) a -Z 5 or
Figure imgf000047_0002
m' is 2 or 3;
Figure imgf000047_0002
m 'is 2 or 3;
Figure imgf000047_0003
Figure imgf000047_0004
Figure imgf000047_0005
Figure imgf000047_0006
Figure imgf000047_0007
Figure imgf000048_0001
where p" is 2 or 3 and the starred C atoms are attached to the Z5 group and all the other symbols are as above defined. Preferred azo compounds of formula III in 1:1 metal complex form are of the formula IIlf
Figure imgf000047_0003
Figure imgf000047_0004
Figure imgf000047_0005
Figure imgf000047_0006
Figure imgf000047_0007
Figure imgf000048_0001
where p "is 2 or 3 and the starred C atoms are attached to the Z 5 group and all the other symbols are as defined above. Preferred azo compounds of formula III in 1: 1 metal complex form are of the formula IIlf
Figure imgf000048_0002
in which R21a is hydrogen, -CH2-Z2, -NH-CO-(CH2)a-Z2,
Figure imgf000048_0002
in which R 21a is hydrogen, -CH 2 -Z 2 , -NH-CO- (CH 2 ) a -Z 2 ,
-CO-CH2-Z2,-NO2, -SO2-NH2, -CO-NH-(CH2)m'-Z2, -SO2-NH-(CH2)m'-Z2 or-CO-CH 2 -Z 2 , -NO 2 , -SO 2 -NH 2 , -CO-NH- (CH 2 ) m ' -Z 2 , -SO 2 -NH- (CH 2 ) m' -Z 2 or
Figure imgf000048_0003
Figure imgf000048_0003
R22a is hydrogen, -NO2, -SO2-NH2,R22a is hydrogen, -NO 2 , -SO 2 -NH 2 ,
-SO2-NH-(CH2)2-OH, -CH2-Z2, -NH-CO-(CH2)a-Z2, -SO2-NH-(CH2)m'-Z2 or-SO 2 -NH- (CH 2 ) 2 -OH, -CH 2 -Z 2 , -NH-CO- (CH 2 ) a -Z 2 , -SO 2 -NH- (CH 2 ) m ' -Z 2 or
Figure imgf000048_0004
and the other symbols are defined above ; with the provisos i) that in ring E the azo bridge is in the 3- or
Figure imgf000048_0004
and the other symbols are defined above; with the provisos i) that in ring E the azo bridge is in the 3- or
4-position; and4-position; and
ii) that R21a and R22a are not both -NO2. Preferred azo compounds of formula IIlf are of the ii) that R 21a and R 22a are not both -NO 2 . Preferred azo compounds of formula II are of the
Figure imgf000049_0001
in which R21b and R22b are independently hydrogen, -CH2-Z3 , -NO2 ,-SO2-NH2,-NH-CO-CH2-Z3,
Figure imgf000049_0001
in which R 21b and R 22b are independently hydrogen, -CH 2 -Z 3 , -NO 2 , -SO 2 -NH 2 , -NH-CO-CH 2 -Z 3 ,
-SO2-NH-(CH2)m,-Z3 or-SO 2 -NH- (CH 2 ) m , -Z 3 or
Figure imgf000049_0002
and the other symbols are as defined above with the proviso that R21b and R22b are not both -NO2. More preferred azo compounds of formula Illf are of the formula Illh
Figure imgf000049_0002
and the other symbols are as defined above with the proviso that R 21b and R 22b are not both -NO 2 . More preferred azo compounds of formula Illf are of the formula Illh
Figure imgf000049_0003
in which
Figure imgf000049_0003
in which
R21c and R22c independently are hydrogen,R 21c and R 22c independently are hydrogen,
-CH2-Z5, -NO2, -SO2-NH2, -NH-CO-CH2-Z5, -SO2-NH- (CH2 ) m ' -Z5 or-CH 2 -Z 5 , -NO 2 , -SO 2 -NH 2 , -NH-CO-CH 2 -Z 5 , -SO 2 -NH- (CH 2 ) m ' -Z 5 or
Figure imgf000050_0001
Figure imgf000050_0002
and all the other symbols are as defined above with the proviso that R21c and R22c are not both -NO2.
Figure imgf000050_0001
Figure imgf000050_0002
and all the other symbols are as defined above with the proviso that R 21c and R 22c are not both -NO 2 .
Alternatively preferred compounds of formula III in 1:1 metal complex form are of the formula IIli or IIIjAlternatively preferred compounds of formula III in 1: 1 metal complex form are of the formula IIli or IIIj
Figure imgf000050_0003
Figure imgf000050_0004
in which A4" is -O- or -COO-,
Figure imgf000050_0003
Figure imgf000050_0004
in which A 4 "is -O- or -COO-,
-K5-O- is one of the following formulae Illba to Illbf
Figure imgf000051_0001
Figure imgf000051_0002
Figure imgf000051_0003
Figure imgf000051_0004
-K 5 -O- is one of the following formula Illba to Illbf
Figure imgf000051_0001
Figure imgf000051_0002
Figure imgf000051_0003
Figure imgf000051_0004
Figure imgf000051_0005
Figure imgf000051_0006
and the other symbols are as defined above.
Figure imgf000051_0005
Figure imgf000051_0006
and the other symbols are as defined above.
Preferred compounds of formula IIIi or IIIj in 1:1 metal complex form are of the formula IIIk or IIIlPreferred compounds of formula IIIi or IIIj in 1: 1 metal complex form are of the formula IIIk or IIIl
Figure imgf000052_0001
Figure imgf000052_0001
Figure imgf000052_0002
Figure imgf000052_0002
in which -O-K6- is
Figure imgf000052_0003
or groups Illbb or Illbc above defined where Rg iv is hydrogen,-CH3 or -(CH2)z-Z5 and the other symbols are as defined above.
in which -OK 6 - is
Figure imgf000052_0003
or groups Illbb or Illbc above defined where R g iv is hydrogen, -CH 3 or - (CH 2 ) z -Z 5 and the other symbols are as defined above.
Preferably Meg is iron. Preferred azo compounds of formula III in 1:2 metal complex form are symmetric or asymmetric and are of the formula IIImPreferably Me g is iron. Preferred azo compounds of formula III in 1: 2 metal complex form are symmetric or asymmetric and are of the formula IIIm
Figure imgf000053_0001
in which each Tx, independently, is
Figure imgf000053_0001
in which each T x , independently, is
Figure imgf000053_0002
in which Meg is chromium, iron or cobalt: preferably iron and all the other symbols are as defined above with the provisos i) that in ring E the azo bridge is in the 3- or
Figure imgf000053_0002
in which Me g is chromium, iron or cobalt: preferably iron and all the other symbols are as defined above with the provisos i) that in ring E the azo bridge is in the 3- or
4-position and ii) that R2 1a and R22a are not both -NO2.4-position and ii) that R 2 1a and R 22a are not both -NO 2 .
Preferred azo compounds of formula IIIm are of the formula IIIn Preferred azo compounds of formula IIIm are of the formula IIIn
Figure imgf000054_0001
in which each Tx' independently is
Figure imgf000054_0001
in which each T x 'independently is
Figure imgf000054_0002
Figure imgf000054_0002
and all the other symbols are as defined above with the proviso that R21b and R22b are not both -NO2.and all the other symbols are as defined above with the proviso that R 21b and R 22b are not both -NO 2 .
More preferred azo compounds of formula IIIm are of the formula IIIoMore preferred azo compounds of formula IIIm are of the formula IIIo
Figure imgf000054_0003
in which each Tx" independently is
Figure imgf000055_0001
in which all the other symbols aro as defined above with the proviso that R21c and R22c are not both -NO2.
Figure imgf000054_0003
in which each T x "independently is
Figure imgf000055_0001
in which all the other symbols aro as defined above with the proviso that R21c and R 22c are not both -NO 2 .
Alternatively preferred azo compounds in 1:2 metal complex form are of the formula IIIp or IIIqAlternatively preferred azo compounds in 1: 2 metal complex form are of the formula IIIp or IIIq
Figure imgf000055_0002
Figure imgf000055_0002
Figure imgf000056_0001
in which all the symbols are as defined above.
Figure imgf000056_0001
in which all the symbols are as defined above.
More preferred azo compounds of formula IIIp or IIIq are of the formula Illr or IIIsMore preferred azo compounds of formula IIIp or IIIq are of the formula Illr or IIIs
Figure imgf000056_0002
Figure imgf000056_0002
Figure imgf000057_0001
in which K5'-O- has the significances of Illba, Illbb or Illbc of K5-O- above and all the other symbols are as defined above .
Figure imgf000057_0001
in which K 5 '-O- has the significances of Illba, Illbb or Illbc of K 5 -O- above and all the other symbols are as defined above.
Preferred azo compounds of formula IV in metal free form are of the formula IVaPreferred azo compounds of formula IV in metal free form are of the formula IVa
Figure imgf000058_0003
Figure imgf000058_0003
in which A5' is -OH or -OCH3 ,in which A 5 'is -OH or -OCH 3 ,
R61a is hydrogen, -NO2, -CH2-Z2, -SO2-NH-(CH2)p-Z2,R 61a is hydrogen, -NO 2 , -CH 2 -Z 2 , -SO 2 -NH- (CH 2 ) p -Z 2 ,
-NH-CO-(CH2)p-Z2
Figure imgf000058_0002
-NH-CO- (CH 2 ) p -Z 2
Figure imgf000058_0002
R62a is hydrogen, -NO2, -CH2-Z2, -SO2-NH2 , -SO2-NH-(CH2)p-Z2, -CO-NH- (CH2)p-Z2, -NH-CO- (CH2)p-Z2 ,R 62a is hydrogen, -NO 2 , -CH 2 -Z 2 , -SO 2 -NH 2 , -SO 2 -NH- (CH 2 ) p -Z 2 , -CO-NH- (CH 2 ) p -Z 2 , -NH-CO- (CH 2 ) p -Z 2 ,
Figure imgf000058_0001
Figure imgf000058_0001
Figure imgf000059_0006
Figure imgf000059_0007
Figure imgf000059_0006
Figure imgf000059_0007
K7 is one of groups IVaa to IVaf below
Figure imgf000059_0001
Figure imgf000059_0002
Figure imgf000059_0003
Figure imgf000059_0004
Figure imgf000059_0005
K 7 is one of groups IVaa to IVaf below
Figure imgf000059_0001
Figure imgf000059_0002
Figure imgf000059_0003
Figure imgf000059_0004
Figure imgf000059_0005
Figure imgf000060_0001
Figure imgf000060_0002
Figure imgf000060_0001
Figure imgf000060_0002
in which R9a is -CH3, -C2H5. or -C2H4-Z2;in which R 9a is -CH 3 , -C 2 H 5 . or -C 2 H 4 -Z 2 ;
R10a is hydrogen, -CH3 , -OCH3, -NH-CO-CH3 orR 10a is hydrogen, -CH 3 , -OCH 3 , -NH-CO-CH 3 or
-NH-CO-NH2; R66a is hydrogen, -CH3, -C2H5, n-C3H7 , n-C4Hg , i-C3H7, i-C4H9 , -C2H4OH or -(CH2)p-Z2;-NH-CO-NH 2 ; R 66a is hydrogen, -CH 3 , -C 2 H 5 , nC 3 H 7 , nC 4 H g , iC 3 H 7 , iC 4 H 9 , -C 2 H 4 OH or - (CH 2 ) p -Z 2 ;
R68a is -(CH2)p-Z2, -NH-(CH2)p-Z2 or
Figure imgf000060_0003
R 68a is - (CH 2 ) p -Z 2 , -NH- (CH 2 ) p -Z 2 or
Figure imgf000060_0003
R69a is -CH3, -C2H5 or -(CH2)p-Z2;R 69a is -CH 3 , -C 2 H 5 or - (CH 2 ) p -Z 2 ;
R71a is hydrogen, -OH, -OCH3 , -NH-CO- (CH2)p-Z2 ,R 71a is hydrogen, -OH, -OCH 3 , -NH-CO- (CH 2 ) p -Z 2 ,
-CO-NH-(CH2)p-Z2, -SO2-NH-(CH2)p-Z2 or-CO-NH- (CH 2 ) p -Z 2 , -SO 2 -NH- (CH 2 ) p -Z 2 or
Figure imgf000060_0004
Figure imgf000060_0004
R72a is hydrogen or -(CH2)p-Z2 ; and where all the other symbols are as defined above: with the provisosR 72a is hydrogen or - (CH 2 ) p -Z 2 ; and where all the other symbols are as defined above: with the provisos
(i) that each azo bridge in B is in an ortho position to A1 or A2 or to both A1 and A2;(i) that each azo bridge in B is in an ortho position to A 1 or A 2 or to both A 1 and A 2 ;
(ii) that R61a and R62a cannot both be the same group, unless both are hydrogen;(ii) that R 61a and R 62a cannot both be the same group, unless both are hydrogen;
(iii) that R60 and R61a are not both -NO2 ; and(iii) that R 60 and R 61a are not both -NO 2 ; and
(iv) that R60 cannot be -NO2, when R61a and R62a are hydrogen. Preferred azo compounds of formula IVa are of formula IVb(iv) that R 60 cannot be -NO 2 when R 61a and R 62a are hydrogen. Preferred azo compounds of formula IVa are of formula IVb
Figure imgf000061_0001
in which R60 is above defined,
Figure imgf000061_0001
in which R 60 is defined above,
R 61b is hydrogen, -NO2 , -CH2-Z3, -SO2-NH-(CH2) -Z3,R 61b is hydrogen, -NO 2 , -CH 2 -Z 3 , -SO 2 -NH- (CH 2 ) -Z 3 ,
-NH-CO- (CH2)a -Z3 or-NH-CO- (CH 2 ) a -Z 3 or
Figure imgf000061_0002
R62b is hydrogen, -NO2, -CH2-Z3, -SO2-NH2,
Figure imgf000061_0002
R 62b is hydrogen, -NO 2 , -CH 2 -Z 3 , -SO 2 -NH 2 ,
-SO2-NH-(CH2)m'-Z3 , -CO-NH- (CH2)m ' -Z3 -SO 2 -NH- (CH 2 ) m ' -Z 3 , -CO-NH- (CH 2 ) m ' -Z 3
-NH-CO-(CH2) a -Z3 or-NH-CO- (CH 2 ) a -Z 3 or
Figure imgf000061_0003
Figure imgf000061_0004
Figure imgf000061_0003
Figure imgf000061_0004
K 7 ' is one of the groups IVba K 7 'is one of the groups IVba
Figure imgf000062_0001
Figure imgf000062_0002
Figure imgf000062_0003
Figure imgf000062_0004
Figure imgf000062_0005
Figure imgf000062_0006
where R9b is -CH3 , -C2H5 or -C2H4~Z3;
Figure imgf000062_0001
Figure imgf000062_0002
Figure imgf000062_0003
Figure imgf000062_0004
Figure imgf000062_0005
Figure imgf000062_0006
where R 9b is -CH 3 , -C 2 H 5 or -C 2 H 4 ~ Z 3 ;
R 66b is hyάrogen, -CH3, -C2H5, -C2H4 OH or -(CH2)m' -Z3 ;R 66b is hydrogen, -CH 3 , -C 2 H 5 , -C 2 H 4 OH or - (CH 2 ) m ' -Z 3 ;
R67b (CH2)m'-Z3, -NH-(CH2)m'-Z3 orR 67b (CH 2 ) m ' -Z 3 , -NH- (CH 2) m' -Z 3 or
Figure imgf000063_0001
Figure imgf000063_0001
R 70b is hydrogen, -OH, -OCH3, -NH-CO- (CH2)a -Z3-,R 70b is hydrogen, -OH, -OCH 3 , -NH-CO- (CH 2 ) a -Z 3 -,
-CO-NH- (CH2)m'-Z3, -SO2-NH-(CH2)m'-Z3 or-CO-NH- (CH 2 ) m ' -Z 3 , -SO 2 -NH- (CH 2 ) m' -Z 3 or
Figure imgf000063_0002
Figure imgf000063_0002
R71b is hydrogen or - (CH2)m'-Z3; and all the other symbols are as defined above, with. the provisos that (i) R61b and R62b cannot both be the same group unless both are hydrogen (ii) that R60 and R61b are not both NO2; and (iii) R60 is not -NO2 when R61b and R62b are both hydrogen.R 71b is hydrogen or - (CH 2 ) m ' -Z 3 ; and all the other symbols are as defined above, with. the provisos that (i) R 61b and R 62b cannot both be the same group unless both are hydrogen (ii) that R 60 and R 61b are not both NO 2 ; and (iii) R 60 is not -NO 2 when R 61b and R 62b are both hydrogen.
Alternatively preferred azo compounds of formula IV in metal-free form are of formula IVcAlternatively preferred azo compounds of formula IV in metal-free form are of formula IVc
Figure imgf000063_0003
Figure imgf000063_0003
in which R63a is -SO2-NH-(CH2)m'-Z2 , -CO-NH-(CH2)m'-Z2,in which R 63a is -SO 2 -NH- (CH 2 ) m ' -Z 2 , -CO-NH- (CH 2 ) m' -Z 2 ,
-NH-CO- (CH2)a -Z2, -CH2-Z2 or -NH-CO- (CH 2 ) a -Z 2 , -CH 2 -Z 2 or
Figure imgf000064_0001
each R65a independently, is -CH3, -C2H5, -OCH3 or -OC2H5; R64a is hydrogen or -OCH3; k is 1 or 2, but only 2 when R63a is the group -CO-NH- (CH2)m'-Z2; R61a' is hydrogen, -NO2, -NH-CO- (CH2) a-Z2 or
Figure imgf000064_0001
each R 65a independently, is -CH 3 , -C 2 H 5 , -OCH 3 or -OC 2 H 5 ; R 64a is hydrogen or -OCH 3 ; k is 1 or 2, but only 2 when R 63a is the group -CO-NH- (CH 2 ) m ' -Z 2 ; R 61a 'is hydrogen, -NO 2 , -NH-CO- (CH 2 ) a -Z 2 or
Figure imgf000064_0002
Figure imgf000064_0002
R 62'is hydrogen, -NO2 , -SO2-NH2, -SO2-N(CH3) 2 ,R 62 'is hydrogen, -NO 2 , -SO 2 -NH 2 , -SO 2 -N (CH 3 ) 2 ,
-SO2-N(C2H5)2, -SO2-NH-C2H4OH, -SO2-NH- (CH2)-m' Z2, or when R60 and R61a' are hydrogen additionally -CO-NH- (CH2)a -Z2, -NH-CO- (CH2)a -Z2 or-SO 2 -N (C 2 H 5 ) 2 , -SO 2 -NH-C 2 H 4 OH, -SO 2 -NH- (CH 2 ) - m ' Z 2 , or when R 60 and R 61a ' are hydrogen additionally -CO-NH- (CH 2 ) a -Z 2 , -NH-CO- (CH 2 ) a -Z 2 or
Figure imgf000064_0003
all other symbols are as above defined, with the provisos
Figure imgf000064_0003
all other symbols are as defined above, with the provisos
(i) that R60 and R61a' are not both -NO2; (ii) that R61a' and R62a' cannot both be the same group unless both are hydrogen: and(i) that R 60 and R 61a 'are not both -NO 2 ; (ii) that R 61a 'and R 62a ' cannot both be the same group unless both are hydrogen: and
(iii) that R60 is not -NO2 when R61a' and R62a' are both hydrogen. Preferred azo compounds of formula IVc are of the formula IVd (iii) that R 60 is not -NO 2 when R 61a 'and R 62a ' are both hydrogen. Preferred azo compounds of formula IVc are of the formula IVd
Figure imgf000065_0002
in which each R 65b independently , is -CH3 or -OCH3,
Figure imgf000065_0002
in which each R 65b independently, is -CH 3 or -OCH 3 ,
Figure imgf000065_0003
Figure imgf000065_0004
all the other symbols are as above defined, and the same provisos apply as to compounds of formula IVc.
Figure imgf000065_0003
Figure imgf000065_0004
all the other symbols are as defined above, and the same provisos apply as to compounds of formula IVc.
Preferred azo compounds of formula IV in 1:1 metal complex form are of the formula IVePreferred azo compounds of formula IV in 1: 1 metal complex form are of the formula IVe
Figure imgf000065_0001
and all other symbols are defined above, with the provisos i) that R61a and R62a cannot both be the same group unless both are hydrogen and ii) that R60 and R61a are not both -NO2; and iii) that R60 is not -NO2 when R6la and R62a are both hydrogen.
Figure imgf000065_0001
and all other symbols are defined above, with the provisos i) that R 61a and R 62a cannot both be the same group unless both are hydrogen and ii) that R 60 and R 61a are not both -NO 2 ; and iii) that R 60 is not -NO 2 when R 6la and R 62a are both hydrogen.
Most preferred azo compounds of formula IVe are of the formula IVfMost preferred azo compounds of formula IVe are of the formula IVf
Figure imgf000066_0002
in which all the symbols are as defined above with the provisos i) that R61b and R61b cannot both be.the same group unless both are hydrogen and ii) that R60 and R61b are not both -NO2. Preferably Mec is copper; and iii) that R60 is not -NO2, when R61b and R62b are both hydrogen. Alternatively preferred azo compounds of formula IV in 1:1 metal complex form are of the formula IVg
Figure imgf000066_0002
in which all the symbols are as defined above with the provisos i) that R 61b and R 61b cannot both be.the same group unless both are hydrogen and ii) that R 60 and R 61b are not both -NO 2 . Preferably Me c is copper; and iii) that R 60 is not -NO 2 , when R 61b and R 62b are both hydrogen. Alternatively preferred azo compounds of formula IV in 1: 1 metal complex form are of the formula IVg
Figure imgf000066_0001
in which all the symbols are as above defined, with the provisos i) that R 60 and R6'1a are not both -NO2; ii) that
Figure imgf000066_0001
in which all the symbols are as defined above, with the provisos i) that R 60 and R 6 ' 1a are not both -NO 2 ; ii) that
R6'1a and R6'2a are not both the same and iii) that R60 is not -NO2 when R6 ' 1a and R6'2a are both hydrogen.R 6 ' 1a and R 6 ' 2a are not both the same and iii) that R 60 is not -NO 2 when R 6 ' 1a and R 6 ' 2a are both hydrogen.
Preferred compounds of formula IVg are of the formula IVhPreferred compounds of formula IVg are of the formula IVh
Figure imgf000067_0001
Figure imgf000067_0001
in which all the symbols are above defined.in which all the symbols are defined above.
Preferred azo compounds of formula IV in 1:2 metal complex form are of the formula IViPreferred azo compounds of formula IV in 1: 2 metal complex form are of the formula IVi
Figure imgf000067_0002
Figure imgf000067_0002
in which Me is chromium, iron or cobalt and all the other symbols are as above defined, with the provisos i) that R61a and R62a are not both the same unless both are hydrogen a ii) that R60 and R61b are not both -NO2; and iii) that R60 is not -NO2 when R61a and R62a are both hydrogen. Preferred azo compounds of formula IVi are of the formula IVjin which Me is chromium, iron or cobalt and all the other symbols are as above defined, with the provisos i) that R 61a and R 62a are not both the same unless both are hydrogen a ii) that R 60 and R 61b are not both -NO 2 ; and iii) that R 60 is not -NO 2 when R 61a and R 62a are both hydrogen. Preferred azo compounds of formula IVi are of the formula IVj
Figure imgf000068_0002
in which all the symbols are as above defined with the provisos i) that R61b and R62b are not both the same unles both are hydrogen -, ii) that R60 and R61b are not both
Figure imgf000068_0002
in which all the symbols are as defined above with the provisos i) that R 61b and R 62b are not both the same unles both are hydrogen -, ii) that R 60 and R 61b are not both
-NO2; and iii) that R60 is not -NO2 when R61b and R62b are both hydrogen.-NO 2 ; and iii) that R 60 is not -NO 2 when R 61b and R 62b are both hydrogen.
Alternatively preferred compounds of formula IV in 1:2 metal complex form are of the formula IVlAlternatively preferred compounds of formula IV in 1: 2 metal complex form are of the formula IVl
Figure imgf000068_0001
in which all the symbols are above defined.
Figure imgf000068_0001
in which all the symbols are defined above.
More preferred compounds of formula IVl are of the formula IVmMore preferred compounds of formula IVl are of the formula IVm
Figure imgf000069_0001
in which all the symbols are above defined.
Figure imgf000069_0001
in which all the symbols are defined above.
In the azo compounds of formula I or II, X is preferably Xa defined above, more preferably Xb.In the azo compounds of formula I or II, X is preferably Xa defined above, more preferably Xb.
In the azo compounds of formula I, II, III or IV Z is preferably Z2, more preferably Z3 most preferably Z5.In the azo compounds of formula I, II, III or IV Z is preferably Z 2 , more preferably Z 3 most preferably Z 5 .
In the production of compounds of formula II chloro methylation of the groupIn the production of compounds of formula II chloro methylation of the group
Figure imgf000069_0002
tends to give a mixture of compounds rather than a single compound and accordingly the average number of basic water solubilising groups formed by subsequent reaction with amines has been found to be at least 1.3. In formulae IIa, IIe and Iln -D1-Z3 is preferably
Figure imgf000069_0002
tends to give a mixture of compounds rather than a single compound and accordingly the average number of basic water solubilizing groups formed by subsequent reaction with amines has been found to be at least 1.3. In formulas IIa, IIe and Iln -D 1 -Z 3 is preferably
Figure imgf000070_0001
and R3a is preferably R3b, more preferably R3c, and R3c preferably hydrogen, -NO2, -SO2NH2, -SO2NH (CH2) 3N (CH3) 2
Figure imgf000070_0001
and R 3a is preferably R 3b , more preferably R 3c , and R 3c preferably hydrogen, -NO 2 , -SO 2 NH 2 , -SO 2 NH (CH 2 ) 3 N (CH 3 ) 2
-SO2NHC2H4OH.-SO 2 NHC 2 H 4 OH.
Preferably in compounds of formulae IVd, IVh andPreferably in compounds of formula IVd, IVh and
Figure imgf000070_0002
Figure imgf000070_0002
R64a is hydrogen.R 64a is hydrogen.
Preferably in compounds of formula IIIPreferably in compounds of formula III
Figure imgf000070_0003
Figure imgf000070_0003
Preferably in formulae II, III and IV one of R2 and R3 or one of R21 and R22 or one of R61 and R62 respectively is hydrogen. The azo compounds of formula I in metal free form can be prepared by coupling a diazotised amine of formula γPreferably in formulas II, III and IV one of R 2 and R 3 or one of R 21 and R 22 or one of R 61 and R 62 respectively is hydrogen. The azo compounds of formula I in metal free form can be prepared by coupling a diazotised amine of formula γ
Figure imgf000071_0001
with a coupling component of the formula δ
Figure imgf000071_0001
with a coupling component of the formula δ
Figure imgf000071_0002
where n' and da have the significances of n and d above with the proviso that n + n' is not greater than 2 and d and da is not greater than 2 and in the case of the metal complexes metallising with a metal capable of forming a 1:1 or 1:2 metal complex or capable of forming both a 1:1 and 1:2 metal complex. For example the azo compounds of formula I in metal free form can be formed by diazotising a corresponding arylamine and coupling with the requisite coupling component by conventional methods.
Figure imgf000071_0002
where n 'and da have the significances of n and d above with the proviso that n + n' is not greater than 2 and d and da is not greater than 2 and in the case of the metal complexes metallizing with a metal capable of forming a 1: 1 or 1: 2 metal complex or capable of forming both a 1: 1 and 1: 2 metal complex. For example the azo compounds of formula I in metal free form can be formed by diazotising a corresponding arylamine and coupling with the requisite coupling component by conventional methods.
The azo compounds of formula I in 1:1 metal complex form may be prepared by metallising compounds of formula I in metal free form with a metal selected from copper, cobalt, iron, nickel, manganese, chromium or zinc. The azo compounds of formula I in 1:2 metal complex form may be prepared by metallising compounds of formula I in metal free form with a metal selected from chromium, nickel, cobalt or iron.The azo compounds of formula I in 1: 1 metal complex form may be prepared by metallizing compounds of formula I in metal free form with a metal selected from copper, cobalt, iron, nickel, manganese, chromium or zinc. The azo compounds of formula I in 1: 2 metal complex form may be prepared by metallizing compounds of formula I in metal free form with a metal selected from chromium, nickel, cobalt or iron.
A further method for the preparation of an azo compound of formula I in 1:2 metal complex form is bonding an azo compound of formula I in metal free form with an azo compound 1:1 metal complex form when the metal is chromium, nickel, cobalt or iron.A further method for the preparation of an azo compound of formula I in 1: 2 metal complex form is bonding an azo compound of formula I in metal free form with an azo compound 1: 1 metal complex form when the metal is chromium, nickel, cobalt or iron.
The metallisation process to form a 1:1 metal complex is advantageously carried out by treating 1 mole of azo compounds with a metallising agent containingThe metallization process to form a 1: 1 metal complex is carried carried out by treating 1 mole of azo compounds with a metallizing agent containing
1 equivalent of metal.1 equivalent of metal.
Metallisation is carried out by known methods advantageously in aqueous medium or a mixture of water and a water-miscible organic solvent for example acetone, lower alkyl alcohols, dimethylformamide formamide, glycols or acetic acid at a pH range from 1.0 to 8.0, preferably pH 2 to 7. The metallisation process may be carried out at a temperature from room temperature to the boiling point of the reaction medium.Metallization is carried out by known methods possible in aqueous medium or a mixture of water and a water-miscible organic solvent for example acetone, lower alkyl alcohols, dimethylformamide formamide, glycols or acetic acid at a pH range from 1.0 to 8.0, preferably pH 2 to 7. The metallization process may be carried out at a temperature from room temperature to the boiling point of the reaction medium.
Alternatively metallisation may be effected in a wholly organic medium (for example dimethylformamide). Advantageously for instance cobaltisation may be carried out in the presence of an inorganic nitrite such as lithium, sodium, ammonium or potassium nitrite in the ratio ofAlternatively metallization may be effected in a wholly organic medium (for example dimethylformamide). Advantageously for instance cobaltization may be carried out in the presence of an inorganic nitrite such as lithium, sodium, ammonium or potassium nitrite in the ratio of
2 to 6 moles of nitrite per gram atom of cobalt. In the compounds of the invention the anion AΘ 2 to 6 moles of nitrite per gram atom of cobalt. In the compounds of the invention the anion A Θ
can be any non-chromophoric anion conventional in basic dyestuff chemistry. Suitable anions include such as chloride and bromide , sulphate , bisulphate,can be any non-chromophoric anion conventional in basic dyestuff chemistry. Suitable anions include such as chloride and bromide, sulphate, bisulphate,
methylsulphate, aminosulphonate, perchlorate, benzo sulphonate, oxalate, maleinate, acetate, propionate, lactate, succinate, tartrate, malate, methanesulphonate and benzoate, as well as complex anions for example zinc chloride double salts and anions of boric acid, citric acid, glycollic acid, diglycollic acid and adipic acid or of addition products of orthoboric acid with polyalcohols with at least an eis diol group present. These anions can be exchanged for each other by ion exchange resins or by reaction with aeids or salts ( for example via the hydroxide or bicarbonate or according to German Offenlegungsschrift 2 001 748 or 2 001 816) .methylsulphate, aminosulphonate, perchlorate, benzo sulphonate, oxalate, maleinate, acetate, propionate, lactate, succinate, tartrate, malate, methanesulphonate and benzoate, as well as complex anions for example zinc chloride double salts and anions of boric acid, citric acid, glycollic acid, diglycollic acid and adipic acid or of addition products of orthoboric acid with polyalcohols with at least an eis diol group present. These anions can be exchanged for each other by ion exchange resins or by reaction with aeids or salts (for example via the hydroxide or bicarbonate or according to German Offenlegungsschrift 2 001 748 or 2 001 816).
The compounds according to the invention are suitably worked up into a solid or liquid preparation for example by granulation or by dissolving in a suitable solvent. The compounds of the invention are suitable for dyeing, padding or printing on fibres, threads or textile materials particularly natural or Suitable cobalt-yielding compounds are for example cobalt (II) or Co (III) sulphate , acetate , formate or chloride.The compounds according to the invention are suitably worked up into a solid or liquid preparation for example by granulation or by dissolving in a suitable solvent. The compounds of the invention are suitable for dyeing, padding or printing on fibers, threads or textile materials particularly natural or Suitable cobalt-yielding compounds are for example cobalt (II) or Co (III) sulphate, acetate, formate or chloride.
Copper-yielding compounds are for example cupric sulphate, cupric formate, cupric acetate or cupric chloride.Copper-yielding compounds are for example cupric sulphate, cupric formate, cupric acetate or cupric chloride.
The nickel-yielding compounds are Ni (II) or Ni(III) compounds, such as nickel formate, nickel acetate or nickel sulphate.The nickel-yielding compounds are Ni (II) or Ni (III) compounds, such as nickel formate, nickel acetate or nickel sulphate.
Preferred manganese yielding compounds are Mn (II) compounds and iron yielding compounds are Fe (II) or Fe (III) compounds. Examples of these and zinc-yielding compounds are manganese-, iron- or zinc formate, acetate or sulphate.Preferred manganese yielding compounds are Mn (II) compounds and iron yielding compounds are Fe (II) or Fe (III) compounds. Examples of these and zinc-yielding compounds are manganese, iron or zinc formate, acetate or sulphate.
Preferred chromium yielding compounds are Cr (II) or Cr(III) formate, acetate or sulphate.Preferred chromium yielding compounds are Cr (II) or Cr (III) formate, acetate or sulfate.
The starting compounds of formula γ and δ are for the most part known or can be prepared aecording to known methods.The starting compounds of formula γ and δ are for the most part known or can be prepared aecording to known methods.
The coupling can be carried out aecording to known methods. Advantageously coupling is carried out in aqueous, acid, neutral or alkali medium at a temperature from -10ºC to room temperature, if necessary in the presence of a coupling accelerator such as pyridine or urea. Alternatively, coupling may be effected in a mixture of solvents for example water and an organic solvent. regenerated cellulose materials for example cotton, synthetic polyamides or synthetic polyesters in which the acid groups have been modified. Such polyamide is described in Belgian Patent 706,104 and such synthetic polyester is described in US Patent 3 379 723.The coupling can be carried out aecording to known methods. Advantageously coupling is carried out in aqueous, acid, neutral or alkali medium at a temperature from -10ºC to room temperature, if necessary in the presence of a coupling accelerator such as pyridine or urea. Alternatively, coupling may be effected in a mixture of solvents for example water and an organic solvent. regenerated cellulose materials for example cotton, synthetic polyamides or synthetic polyesters in which the acid groups have been modified. Such polyamide is described in Belgian Patent 706,104 and such synthetic polyester is described in US Patent 3,379,723.
The new compounds are also used for dyeing, pad-dyeing or printing fibres, threads or textiles produced therefrom, which consist of or contain homo- or mixed polymers of acrylonitrile or of asymmetrical dicyanoethylene .The new compounds are also used for dyeing, pad-dyeing or printing fibers, threads or textiles produced therefrom, which consist of or contain homo- or mixed polymers of acrylonitrile or of asymmetrical dicyanoethylene.
The textile material is dyed, printed or pad-dyed in aecordance with known methods. Acid modified-polyamide is dyed particularly advantageously in an aqueous , neutral or acid medium, at temperatures of 60 °C to boiling point or at temperatures of above 100°C under pressure.The textile material is dyed, printed or pad-dyed in aecordance with known methods. Acid modified-polyamide is dyed particularly advantageously in an aqueous, neutral or acid medium, at temperatures of 60 ° C to boiling point or at temperatures of above 100 ° C under pressure.
The textile material may also be dyed by the compounds of formula I in organic solvents, e.g. in aecordance with the directions given in German DOS 2 437 549.The textile material may also be dyed by the compounds of formula I in organic solvents, e.g. in agreement with the directions given in German DOS 2 437 549.
Cellulose material is mainly dyed by the exhaust process, e.g. from a long or short bath, at room temperature to boiling temperature, optionally under pressure, whereby the ratio of the bath is from 1:1 to 1:100, and preferably from 1:20 to 1:50. If dyeing is effected from a short bath, then the liquor ratio is 1:5 to 1:15, and the pH value of the dye baths varies between 3 and 10. Dyeing preferably takes place in the presence of electrolytes.Cellulose material is mainly dyed by the exhaust process, eg from a long or short bath, at room temperature to boiling temperature, optionally under pressure, whereby the ratio of the bath is from 1: 1 to 1: 100, and preferably from 1: 20 to 1:50. If dyeing is effected from a short bath, then the liquor ratio is 1: 5 to 1:15, and the pH value of the dye baths varies between 3 and 10. Dyeing preferably takes place in the presence of electrolytes.
Printing may be effected by impregnation with a printing paste produced by known methods .Printing may be effected by impregnation with a printing paste produced by known methods.
The dyestuffs are also suitable for dyeing or printing paper, e.g. for the produetion of bulk-dyed, sized and unsized paper. The dyestuffs may similarly be used for dyeing paper by the dipping process. The dyeing of paper is effected by known methods.The dyestuffs are also suitable for dyeing or printing paper, e.g. for the production of bulk-dyed, sized and unsized paper. The dyestuffs may similarly be used for dyeing paper by the dipping process. The dyeing of paper is effected by known methods.
The new dyestuffs are also suitable for dyeing or printing leather by known methods. Dyeings with good fastness are obtained both on paper and on leather.The new dyestuffs are also suitable for dyeing or printing leather by known methods. Dyeings with good fastness are obtained both on paper and on leather.
Dyeings made from the new compounds on leather have good light fastness properties, good diffusion properties with PVC, good water-, wash- and sweat properties, good fastness to dry cleaning, good fastness to drops of water, good fastness to hard water.Dyeings made from the new compounds on leather have good light fastness properties, good diffusion properties with PVC, good water, wash and sweat properties, good fastness to dry cleaning, good fastness to drops of water, good fastness to hard water.
Dyeings made from the new compounds on paper have good build-up, good light fastness, good fastness to water, milk, fruit juice, sweetened mineral water and alcoholic drinks, good fastness to 1% sodium chloride, washing powder solution, good sulphite reduetive or oxidative (with hypo-chlorite) clearanee and good fastness to hard water. Dyeings made from mixtures of the new dyestuffs remain tone-in- tone and the nuance stability of dyeings made from the dyestuffs is good.Dyeings made from the new compounds on paper have good build-up, good light fastness, good fastness to water, milk, fruit juice, sweetened mineral water and alcoholic drinks, good fastness to 1% sodium chloride, washing powder solution, good sulphite reduetive or oxidative (with hypo-chlorite) clearanee and good fastness to hard water. Dyeings made from mixtures of the new dyestuffs remain tone-in-tone and the nuance stability of dyeings made from the dyestuffs is good.
Further the dyestuffs of the invention do not run after dyeing on paper nor on the whole are they pH sensitive.Further the dyestuffs of the invention do not run after dyeing on paper nor on the whole are they pH sensitive.
The new compounds may be converted into dyeing preparations. The processing into stable, liquid or solid dyeing preparations may take place in a generally known manner. Advantageously by grinding or granulating, or by dissolving in suitable solvents, optionally adding an assistant, e.g. a stabiliser or dissolving inter mediary, such as urea. Such preparations may be obtained for example as described in French Patent Specifications 1.572.030 and 1.581.900 or in accordance with German DOS 2.001.748 and 2.001.816.The new compounds may be converted into dyeing preparations. The processing into stable, liquid or solid dyeing preparations may take place in a generally known manner. Advantageously by grinding or granulating, or by dissolving in suitable solvents, optionally adding an assistant, e.g. a stabilizer or dissolving inter mediary, such as urea. Such preparations may be obtained for example as described in French Patent Specifications 1,572,030 and 1,581,900 or in accordance with German DOS 2,001,748 and 2,001,816.
Liquid preparations of the compounds of formula I preferably comprise 10-30% by weight of a compound of formula I and to 30% of a solubilising agent such as urea, lactic acid or acetic acid the rest of the composition being water. Solid preparations preferably comprising 20-80% dyestuff, 80-20% solubilising agent such as urea or Na2SO4 and 2-5% water.Liquid preparations of the compounds of formula I preferably comprise 10-30% by weight of a compound of formula I and to 30% of a solubilizing agent such as urea, lactic acid or acetic acid the rest of the composition being water. Solid preparations preferably comprising 20-80% dyestuff, 80-20% solubilizing agent such as urea or Na 2 SO 4 and 2-5% water.
In the following examples all parts and per centages given are by weight and the temperatures given are in degrees centigrade unless indicated to the contrary. Example 1 a) 27.3 Parts (0.1 mole) of 1-hydroxy-2-amino-benzol-4-sulphonic acid dimethylaminopropylamide is diazotised at 0-5° in 150 parts of water, 32 parts of 30% hydrochloric acid with 6.9 parts (0.1 mole) sodium nitrite (according to known methods) . Over an hour the darkly coloured diazonium solution is added,dropwise, to 18.9 parts (0.1 mole) 4-aminophenyl-3-methyl pyrazolone dissolved in 105 parts of water and 25 parts of 30% hydrochloric acid. The mixture is slowly brought to a pH of 4.0 by the addition of 30% sodium hydroxide. The dyestuff so produced is of the formula a)In the following examples all parts and per centages given are by weight and the temperatures given are in degrees centigrade unless indicated to the contrary. Example 1 a) 27.3 Parts (0.1 mole) of 1-hydroxy-2-amino-benzene-4-sulphonic acid dimethylaminopropylamide is diazotized at 0-5 ° in 150 parts of water, 32 parts of 30% hydrochloric acid with 6.9 parts ( 0.1 mole) sodium nitrite (according to known methods). Over an hour the darkly colored diazonium solution is added, dropwise, to 18.9 parts (0.1 mole) 4-aminophenyl-3-methyl pyrazolone dissolved in 105 parts of water and 25 parts of 30% hydrochloric acid. The mixture is slowly brought to a pH of 4.0 by the addition of 30% sodium hydroxide. The dyestuff so produced is of the formula a)
Figure imgf000078_0001
Figure imgf000078_0001
which produces dyeings of a yellow shade. b) A strongly acid solution of the monoazo dyestuff is made up with a 30% solution of hydrochloric acid and then diazotised with 6.9 parts of sodium nitrite according to known methods. Over a period of 15 minutes the solution is added, dropwise, to 32.4 parts (0.1 mole) of 6-hydroxy-4-methyl-1-dimethyl-aminopropyl-pyridonyl-(3)-pyridinium chloride dissolved in 250 parts of water. The pH of the solution is then brought to 6.5 using a sodium hydroxide solution and the reaction mixture concentrated by evaporation under vacuum. The resultant dyestuff is of formula b)which produces dyeings of a yellow shade. b) A strongly acid solution of the monoazo dyestuff is made up with a 30% solution of hydrochloric acid and then diazotised with 6.9 parts of sodium nitrite according to known methods. Over a period of 15 minutes the solution is added, dropwise, to 32.4 parts (0.1 mole) of 6-hydroxy-4-methyl-1-dimethyl-aminopropyl-pyridonyl- (3) -pyridinium chloride dissolved in 250 parts of water. The pH of the solution is then brought to 6.5 using a sodium hydroxide solution and the reaction mixture concentrated by evaporation under vacuum. The resultant dyestuff is of formula b)
Figure imgf000079_0001
Figure imgf000079_0001
which dyes leather a red/orange colour. c) 40.4 Parts mole) of the dyestuff b)
Figure imgf000079_0003
above is dissolved in 200 parts of water at 65 °C and the solution is made up with 8 parts of sodium acetate. A solution of 12.5 parts of copper sulphate in water is added dropwise to the solution and the resulting solution has a pH of 4.5 to 5. After 30 minutes stirring at 60 °C the reaction mixture is concentrated by evaporation under vacuum. A 1:1 copper complex of formula c)
which dyes leather a red / orange color. c) 40.4 Parts mole) of the dyestuff b)
Figure imgf000079_0003
above is dissolved in 200 parts of water at 65 ° C and the solution is made up with 8 parts of sodium acetate. A solution of 12.5 parts of copper sulphate in water is added dropwise to the solution and the resulting solution has a pH of 4.5 to 5. After 30 minutes stirring at 60 ° C the reaction mixture is concentrated by evaporation under vacuum. A 1: 1 copper complex of formula c)
Figure imgf000079_0002
Figure imgf000079_0002
is produced which dyes leather a red-brown tone and has good fastness properties. Example 2is produced which dyes leather a red-brown tone and has good fastness properties. Example 2
103.2 Parts (0.15 mole) of a dyestuff of formula103.2 Parts (0.15 moles) of a dyestuff of formula
Figure imgf000080_0001
Figure imgf000080_0001
and 82.7 parts of KCr(SO4)2 12H2O are autoclaved with 1500 parts of water. The mixture is brought to a pH of 2 by the addition of sulphuric acid. The mixture is heated for 2 hours at a temperature of 130°C and the 1:1 chromium complex is formed under pressure. The so- formed complex dyes leather a brown shade and has good fastness properties. Example 3and 82.7 parts of KCr (SO 4 ) 2 12H 2 O are autoclaved with 1500 parts of water. The mixture is brought to a pH of 2 by the addition of sulfuric acid. The mixture is heated for 2 hours at a temperature of 130 ° C and the 1: 1 chromium complex is formed under pressure. The so-formed complex dyes leather a brown shade and has good fastness properties. Example 3
7 Parts of CoSO4 7H2O m
Figure imgf000080_0002
ole) and 10.5 parts
7 parts of CoSO 4 7H 2 O m
Figure imgf000080_0002
ole) and 10.5 parts
of sodium nitrite are dissolved in 250 parts of water. At a temperature of 10°C, 17.2 parts mole) of the
Figure imgf000080_0003
dyestuff of formula d) above is added to the solution. To improve the solubility of the dyestuff 50 parts of dimethylformamide is added to the reaction mixture. The pH of the reaction solution is brought to 5.0 - 5.5 by the addition of hydrochloric acid. After about 3 hours cobaltisation is substantially completed and a 1:1 cobalt complex of the compound of formula d) above is formed and is isolated using acetone. Example 4
of sodium nitrite are dissolved in 250 parts of water. At a temperature of 10 ° C, 17.2 parts mole) of the
Figure imgf000080_0003
dyestuff of formula d) above is added to the solution. To improve the solubility of the dyestuff 50 parts of dimethylformamide is added to the reaction mixture. The pH of the reaction solution is brought to 5.0 - 5.5 by the addition of hydrochloric acid. After about 3 hours cobaltization is substantially completed and a 1: 1 cobalt complex of the compound of formula d) above is formed and is isolated using acetone. Example 4
40.4 Parts mole) of the dyestuff of formula
Figure imgf000081_0004
b) [of Example 1] is dissolved in 500 parts of water. The solution is heated to 60 °C and 35 parts of sodium acetate and 12.5 parts mole) of KCr(SO4)2 12H2O is
Figure imgf000081_0005
added to the solution. The pH of the reaction mixture is about 4.5. The temperature of the reaction mixture is raised to 90-95°C and after 1 hour metalisation is substantially completed. The reaction mixture is cooled to 20 °C and the product is isolated in acetone after which the product is filtered and dried. The product is a dyestuff of the formula e)
40.4 Parts mole) of the dyestuff of formula
Figure imgf000081_0004
b) [of Example 1] is dissolved in 500 parts of water. The solution is heated to 60 ° C and 35 parts of sodium acetate and 12.5 parts mole) of KCr (SO 4 ) 2 12H 2 O is
Figure imgf000081_0005
added to the solution. The pH of the reaction mixture is about 4.5. The temperature of the reaction mixture is raised to 90-95 ° C and after 1 hour metalization is substantially completed. The reaction mixture is cooled to 20 ° C and the product is isolated in acetone after which the product is filtered and dried. The product is a dyestuff of the formula e)
Figure imgf000081_0001
Figure imgf000081_0001
Figure imgf000081_0002
Figure imgf000081_0002
Figure imgf000081_0003
The dyestuff dyes leather a red brown colour with good fastness properties.
Figure imgf000081_0003
The dyestuff dyes leather a red brown color with good fastness properties.
By substituting 7 parts cobalt sulphate mole
Figure imgf000082_0005
or 6.8 parts of FeCl3 6H2O mole) for 12.5 parts of
Figure imgf000082_0004
KCr(SO4)2 12H2O the corresponding 1:1 cobalt and iron complexes respectively can be produced. Example 5
By substituting 7 parts cobalt sulphate mole
Figure imgf000082_0005
or 6.8 parts of FeCl 3 6H 2 O mole) for 12.5 parts of
Figure imgf000082_0004
KCr (SO 4 ) 2 12H 2 O the corresponding 1: 1 cobalt and iron complexes respectively can be produced. Example 5
According to the method of Example 1a) and 1b) and with subsequent cobaltisation (with cobalt sulphate) a compound of formula f) is producedAccording to the method of Example 1a) and 1b) and with subsequent cobaltization (with cobalt sulphate) a compound of formula f) is produced
Figure imgf000082_0001
Figure imgf000082_0001
8.3 parts of the above dyestuff f) in 150 parts of water is heated to 85°C. 8 Parts of a dyestuff of the formula g) mole)
Figure imgf000082_0003
8.3 parts of the above dyestuff f) in 150 parts of water is heated to 85 ° C. 8 parts of a dyestuff of the formula g) mole)
Figure imgf000082_0003
Figure imgf000082_0002
is added gradually. The pH of the reaction is held a 9 by the addition of aqueous sodium hydroxide solution. After 3 hours an asymmetric 1:2 cobalt complex dyestuff of formula h)
Figure imgf000082_0002
is added gradually. The pH of the reaction is held a 9 by the addition of aqueous sodium hydroxide solution. After 3 hours an asymmetric 1: 2 cobalt complex dyestuff of formula h)
Figure imgf000083_0001
Figure imgf000083_0001
is produced which is isolated in acetone , washed and vacuum dried . This dyestuff of formula h) dyes leather a red brown colour .is produced which is isolated in acetone, washed and vacuum dried. This dyestuff of formula h) dyes leather a red brown color.
Example 6 a) 15 . 4 Parts mole) of 1-hydroxy-2-amino-4-
Figure imgf000083_0003
nitrobenzol are coupled with 11 parts of resorcinol to give a compound of the formula VIa
Example 6 a) 15. 4 parts mole) of 1-hydroxy-2-amino-4-
Figure imgf000083_0003
nitrobenzene are coupled with 11 parts of resorcinol to give a compound of the formula VIa
Figure imgf000083_0002
Figure imgf000083_0002
b) 24 Parts mole) of 2 (4'-aminophenyl)-6-
Figure imgf000083_0004
methylbenzthiazole was chloromethylated according to the method of German Offenlegungsschrift No. 1 965 993 and then quaternised with 50 parts or a solution of trimethylamine in water at 40-45°. The resulting trimethyl ammonium compound is dissolved at 0-10° in dilute hydrochloric acid solution and is diazotised with 6.9 parts of sodium nitrite and the dyestuff suspension of the compound of formula VIa is dropwise added. A compound of the formula VIb
b) 24 parts mole) of 2 (4'-aminophenyl) -6-
Figure imgf000083_0004
methylbenzthiazole was chloromethylated according to the method of German Offenlegungsschrift No. 1 965 993 and then quaternized with 50 parts or a solution of trimethylamine in water at 40-45 °. The resulting trimethyl ammonium compound is dissolved at 0-10 ° in dilute hydrochloric acid solution and is diazotised with 6.9 parts of sodium nitrite and the dyestuff suspension of the compound of formula VIa is dropwise added. A compound of the formula VIb
Figure imgf000084_0001
Figure imgf000084_0001
results . c) 15.4 Parts ( mole) of the dyestuff of
Figure imgf000084_0003
formula b) is dissolved in 500 parts formamide. The solution is warmed to 60° to give a solution of 35 parts sodium acetate and 35 parts of KCr(SO4)2 12H2O is acdeα and the temperature is raised to 90-35°. After about 60 minutes metallisation is ended. The reaction mixture is cooled to 20° and is precipitated in acetone to give a 1:2 chromium complex of the formula VIc
results. c) 15.4 Parts (mole) of the dyestuff of
Figure imgf000084_0003
formula b) is dissolved in 500 parts of formamide. The solution is warmed to 60 ° to give a solution of 35 parts sodium acetate and 35 parts of KCr (SO 4 ) 2 12H 2 O is acdeα and the temperature is raised to 90-35 °. After about 60 minutes metallization has ended. The reaction mixture is cooled to 20 ° and is precipitated in acetone to give a 1: 2 chromium complex of the formula VIc
Figure imgf000084_0002
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000086_0002
Figure imgf000086_0003
Figure imgf000086_0004
Figure imgf000084_0002
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000086_0002
Figure imgf000086_0003
Figure imgf000086_0004
Figure imgf000086_0005
Figure imgf000086_0006
Figure imgf000086_0007
Figure imgf000086_0005
Figure imgf000086_0006
Figure imgf000086_0007
Figure imgf000087_0001
Figure imgf000087_0002
Figure imgf000087_0001
Figure imgf000087_0002
R312 is -NH-CO- (CH2) -ZR312 is -NH-CO- (CH 2 ) -Z
R313 is -SO2-NH-(CH2)3 -ZR313 is -SO 2 -NH- (CH 2 ) 3 -Z
Figure imgf000087_0003
Figure imgf000087_0003
Examples 7 - 1;Examples 7 - 1;
The following Examples are compounds of the formulaThe following examples are compounds of the formula
Figure imgf000087_0004
or in 1:1 metal complex or 1:2 metal complex form. These compounds can be prepared according to the method of Example 6 with suitable choice of starting materials.
Figure imgf000087_0004
or in 1: 1 metal complex or 1: 2 metal complex form. These compounds can be prepared according to the method of Example 6 with suitable choice of starting materials.
Each Z referred to in a specific Example has the same significance in that Example whenever it appears.Each Z referred to in a specific Example has the same significance in that Example whenever it appears.
Each Z referred to in a specific Example has the same significance in that Example wherever it appears. Each Z referred to in a specific Example has the same significance in that Example wherever it appears.
- 86 -- 86 -
Figure imgf000089_0001
Examples 17 - 43
Figure imgf000089_0001
Examples 17-43
The following Examples are of compounds of the formulaThe following examples are of compounds of the formula
Figure imgf000090_0001
and in 1:1 metal complex and 1:2 metal complex form.
Figure imgf000090_0001
and in 1: 1 metal complex and 1: 2 metal complex form.
Figure imgf000090_0002
Figure imgf000091_0001
Examples 44 to 58
Figure imgf000090_0002
Figure imgf000091_0001
Examples 44 to 58
The following Examples are compounds of the formulaThe following examples are compounds of the formula
Figure imgf000092_0002
and can be prepared following the method of Example 1 (and Example 5 where 1:2 metallisation has been carried out),with suitable choice of starting materials. In these Examples
Figure imgf000092_0002
and can be prepared following the method of Example 1 (and Example 5 where 1: 2 metallization has been carried out), with suitable choice of starting materials. In these Examples
Figure imgf000092_0001
Figure imgf000092_0001
R400 is -SO2-NH-(CH2)3-N(CH3)2 R 400 is -SO 2 -NH- (CH 2 ) 3 -N (CH 3 ) 2
Figure imgf000093_0002
Figure imgf000093_0002
Examples 59 to 72 The following Examples are compounds of the formulaExamples 59 to 72 The following examples are compounds of the formula
Figure imgf000093_0001
which can be made according to Example 1 and where 1 : 2 metallisation is neeessary according to Example 5 using a suitable choice of starting materials. Z is N(C2H5)2 and ZB is N(CH3)2.
Figure imgf000093_0001
which can be made according to Example 1 and where 1: 2 metallization is neeessary according to Example 5 using a suitable choice of starting materials. Z is N (C 2 H 5 ) 2 and Z B is N (CH 3 ) 2 .
Figure imgf000094_0001
Figure imgf000094_0001
__ the following Examples
Figure imgf000095_0001
Figure imgf000095_0002
Figure imgf000095_0003
Figure imgf000095_0004
Figure imgf000095_0005
Figure imgf000095_0006
Figure imgf000096_0001
Figure imgf000096_0002
Figure imgf000096_0003
Figure imgf000096_0004
Figure imgf000096_0005
Figure imgf000096_0006
Figure imgf000096_0007
Figure imgf000096_0008
__ the following examples
Figure imgf000095_0001
Figure imgf000095_0002
Figure imgf000095_0003
Figure imgf000095_0004
Figure imgf000095_0005
Figure imgf000095_0006
Figure imgf000096_0001
Figure imgf000096_0002
Figure imgf000096_0003
Figure imgf000096_0004
Figure imgf000096_0005
Figure imgf000096_0006
Figure imgf000096_0007
Figure imgf000096_0008
Figure imgf000097_0001
Figure imgf000097_0002
R322 -CH2 N(CH3)3 A Θ
Figure imgf000097_0001
Figure imgf000097_0002
R 322 -CH 2 N (CH 3 ) 3 A Θ
R323 is -NH-CO- (CH2) -N(CH3)2 R 323 is -NH-CO- (CH 2 ) -N (CH 3 ) 2
Examples 73 to 83Examples 73 to 83
The following Examples are compounds of the formula IIIThe following examples are compounds of the formula III
Figure imgf000097_0003
Figure imgf000097_0003
EE
Figure imgf000097_0004
Figure imgf000098_0002
Figure imgf000097_0004
Figure imgf000098_0002
Examples 84 to 104Examples 84 to 104
The following Examples are compounds of the formulaThe following examples are compounds of the formula
Figure imgf000098_0001
which may be prepared by following the method of Example 1 (and where 1:2 metallisation is carried out Example 5) with suitable choice of starting material.
Figure imgf000098_0001
which may be prepared by following the method of Example 1 (and where 1: 2 metallization is carried out Example 5) with suitable choice of starting material.
Figure imgf000098_0003
Figure imgf000099_0002
Figure imgf000098_0003
Figure imgf000099_0002
Examples 104 to 129Examples 104 to 129
The following Examples are of formulaThe following examples are of formula
Figure imgf000099_0001
where Z. is -N(C2H5)2 and Z2 is -N(CH3).
Figure imgf000099_0001
where Z. is -N (C 2 H 5 ) 2 and Z 2 is -N (CH 3 ).
These compounds can be made by following the method of Example 1 (and where 1:2 metallisation is carried out Example 5) using suitable choice of starting materials .These compounds can be made by following the method of Example 1 (and where 1: 2 metallization is carried out Example 5) using suitable choice of starting materials.
Figure imgf000100_0002
Figure imgf000100_0002
The following Examples are of formula
Figure imgf000100_0001
in which Z 1 is -N(C2H5)2 and Z2 is -N(CH3)2.
The following examples are of formula
Figure imgf000100_0001
in which Z 1 is -N (C 2 H 5 ) 2 and Z 2 is -N (CH 3 ) 2 .
These compounds can be made by following the method of Example 1 (and where 1:2 metallisation occurs ExampleThese compounds can be made by the following the method of Example 1 (and where 1: 2 metallization occurs Example
5) using suitable choice of starting materials,
Figure imgf000101_0001
Figure imgf000102_0001
5) using suitable choice of starting materials,
Figure imgf000101_0001
Figure imgf000102_0001
Examples 130-160Examples 130-160
The following Examples are of the formulaThe following examples are of the formula
Figure imgf000103_0001
and can be prepared by following the method of Example 1 (and where 1:2 metallisation is carried out of Example 5) using a suitable choice of starting materials.
Figure imgf000103_0001
and can be prepared by following the method of Example 1 (and where 1: 2 metallization is carried out of Example 5) using a suitable choice of starting materials.
Figure imgf000103_0002
Figure imgf000104_0001
Figure imgf000105_0001
Figure imgf000103_0002
Figure imgf000104_0001
Figure imgf000105_0001
In the following ExamplesIn the following examples
Ba is a group of the formula
Figure imgf000106_0001
Ba is a group of the formula
Figure imgf000106_0001
Bb is a group of the formula
Figure imgf000106_0002
Bb is a group of the formula
Figure imgf000106_0002
Bc is
Figure imgf000106_0003
Bc is
Figure imgf000106_0003
Bd is and
Figure imgf000106_0004
Bd is and
Figure imgf000106_0004
Be is
Figure imgf000106_0005
By S
Figure imgf000106_0005
Examples 161 - 166Examples 161-166
The following Examples of the formulaThe following examples of the formula
Figure imgf000106_0006
Figure imgf000106_0006
which can be prepared according to Example 1 (or when 1:2 metallisation is carried out Example 5) by the suitable choice of starting materials.
Figure imgf000107_0002
which can be prepared according to Example 1 (or when 1: 2 metallization is carried out Example 5) by the suitable choice of starting materials.
Figure imgf000107_0002
Examples 167-172Examples 167-172
The following Examples are of the formulaThe following examples are of the formula
Figure imgf000107_0001
Figure imgf000107_0001
and can be prepared according to Example 1 (or where 1:2 metallisation is carried out Example 5) by the suitable choice of starting materials. and can be prepared according to Example 1 (or where 1: 2 metallization is carried out Example 5) by the suitable choice of starting materials.
E
Figure imgf000108_0003
E
Figure imgf000108_0003
Examples 173- 185Examples 173-185
The following compounds can be made according to Example 1 (or where 1:2 metallisation is carried out according to Example 5) by suitable choice of starting materials.The following compounds can be made according to Example 1 (or where 1: 2 metallization is carried out according to Example 5) by suitable choice of starting materials.
Figure imgf000108_0001
Figure imgf000108_0002
Figure imgf000108_0001
Figure imgf000108_0002
Figure imgf000109_0001
Figure imgf000109_0002
Figure imgf000109_0001
Figure imgf000109_0002
Example 177Example 177
1:1 Cu-complex from Example 174.1: 1 Cu complex from Example 174.
Example 178Example 178
1:1 Cu-complex from Example 175.1: 1 Cu complex from Example 175.
Figure imgf000109_0003
Figure imgf000109_0003
Example 180Example 180
1:2 Fe-complex from Example 174.1: 2 Fe-complex from Example 174.
Example 181Example 181
1:2 Fe-complex from Example 175. Example 1821: 2 Fe-complex from Example 175. Example 182
1:2 Fe-complex from Example 174. Example 1831: 2 Fe-complex from Example 174. Example 183
1:2 Cr-complex from Example 175. Example 1841: 2 Cr-complex from Example 175. Example 184
1:2 Co-complex from Example 174. Example 1851: 2 Co-complex from Example 174. Example 185
1:2 Co-complex from Example 175. 1: 2 Co-complex from Example 175.
Application Example AApplication Example A
100 Parts of freshly tanned and neutralised chrome grain leather are soaked in a bath at 55°C of 250 parts water and 0.5 parts of a dyestuff of any one of Example 1 to 5 for 30 minutes, then treated for 30 minutes in the same bath with 2 parts of an anionic fat liquor based on sulphonated train oil and then dried and finished in conventional manner. The colour of the dyed leather is given below:100 parts of freshly tanned and neutralized chrome grain leather are soaked in a bath at 55 ° C of 250 parts water and 0.5 parts of a dyestuff of any one of Example 1 to 5 for 30 minutes, then treated for 30 minutes in the same bath with 2 parts of an anionic fat liquor based on sulphonated train oil and then dried and finished in conventional manner. The color of the dyed leather is given below:
Figure imgf000111_0001
Figure imgf000111_0001
Figure imgf000112_0001
Figure imgf000112_0001
Calf suede leather, chrome-vegetable tanned sheep- skin and box cowhide leather can also be dyed by known methods. Application Example BCalf suede leather, chrome-vegetable tanned sheep- skin and box cowhide leather can also be dyed by known methods. Application Example B
70 Parts of a chemically bleached sulphite cellulose70 parts of a chemically bleached sulphite cellulose
(from conifer wood) and 30 parts of a chemically bleached sulphite cellulose (from birch wood) is ground in a(from conifer wood) and 30 parts of a chemically bleached sulphite cellulose (from birch wood) is ground in a
Hollander of 2000 parts water. 0.2 Part of a dyestuff of any one of those listed in Application Example A ofHollander of 2000 parts water. 0.2 Part of a dyestuff of any one of those listed in Application Example A of
Examples 1 to 5 above is added to the mass. After 20 minutes of mixing, paper is produced from the mass. The absorbent paper so produced has the same colour as the leather dyed with the dyestuffs as given in Application Example A above and the backwaters are colourless. Application Example CExamples 1 to 5 above is added to the mass. After 20 minutes of mixing, paper is produced from the mass. The absorbent paper so produced has the same color as the leather dyed with the dyestuffs as given in Application Example A above and the backwaters are colorless. Application Example C
0.5 Part of a dyestuff of any one of those of0.5 Part of a dyestuff of any one of those of
Examples 1 to 5 is dissolved in 100 parts of hot water and cooled to room temperature. The solution is added toExamples 1 to 5 is dissolved in 100 parts of hot water and cooled to room temperature. The solution is added to
100 parts of chemically bleached sulphite cellulose which has been ground in a Hollander with 2000 parts of water. After 15 minutes mixing the mixture is sized. Paper produeed from this mass has the same colour as the leather dyed with the dyestuffs as given in Application Example A and is of medium intensity with good wet fastness properties. Application Example D100 parts of chemically bleached sulphite cellulose which has been ground in a Hollander with 2000 parts of water. After 15 minutes mixing the mixture is sized. Paper produeed from this mass has the same color as the leather dyed with the dyestuffs as given in Application Example A and is of medium intensity with good wet fastness properties. Application Example D
An absorbent paper web of unsized paper is drawn through a dyestuff solution of the following constitution:An absorbent paper web of unsized paper is drawn through a dyestuff solution of the following constitution:
0.5 parts of a dyestuff of Examples 1 to 50.5 parts of a dyestuff of Examples 1 to 5
0.5 parts starch 99.0 parts of water.0.5 parts starch 99.0 parts of water.
Excess dyestuff solution is squeezed out by pressing between two rollers. The dried paper web has the same colour as the leather dyed with the dyestuffs as given in Application Example A.Excess dyestuff solution is squeezed out by pressing between two rollers. The dried paper web has the same color as the leather dyed with the dyestuffs as given in Application Example A.
Similar good paper dyeings can be obtained by using equivalent quantities of a liquid preparation or a granular preparation of the dyestuff for the pure dyestuff in the above Application Examples A to D. Similar good paper dyeings can be obtained by using equivalent quantities of a liquid preparation or a granular preparation of the dyestuff for the pure dyestuff in the above Application Examples A to D.
Figure imgf000114_0001
Figure imgf000115_0001
Figure imgf000116_0001
Figure imgf000114_0001
Figure imgf000115_0001
Figure imgf000116_0001

Claims

WHAT IS CLAIMED IS: WHAT IS CLAIMED IS:
1. A sulpho-free azo compound in metal free, 1:1 metal comples or 1:2 metal complex from having at least on average 1.3 water solubilising groups the compound being of formula -I1. A sulpho-free azo compound in metal free, 1: 1 metal comples or 1: 2 metal complex from having at least on average 1.3 water solubilizing groups the compound being of formula -I
Figure imgf000117_0005
in which
Figure imgf000117_0005
in which
Ra is a group of the formula ia - IcRa is a group of the formula ia - Ic
Figure imgf000117_0004
Figure imgf000117_0003
Figure imgf000117_0002
where the group
Figure imgf000117_0004
Figure imgf000117_0003
Figure imgf000117_0002
where the group
Figure imgf000117_0001
is a substituted pyrazolone-5, a substituted 5-aminopyrazole, a substituted 4-alkyl-2-pyridone or a substituted ß-hydroxynaphthalene group;
Figure imgf000117_0001
is a substituted pyrazolone-5, a substituted 5-aminopyrazole, a substituted 4-alkyl-2-pyridone or a substituted ß-hydroxynaphthalene group;
in which yo is OH or NH2;in which yo is OH or NH 2 ;
Rb is a (C1-4) alkyl group or a substituteR b is a (C 1-4 ) alkyl group or a substitute
(C1_3) alkyl group;(C 1 _ 3) alkyl group;
R is -NH2 , a substituted alkyl group, a substituted alkylamino group, a substituted phenyl amino group, an unsubstituted or substituted naphthyl amino group, an unsubstituted or substituted benzthiazol amino group, an unsubstituted or substituted benzoxazol amino group an unsubstituted or substituted benzimida- zolamino group; x and y independently are hydrogen, -OH, (C1-4)- alkyl, -NH2 or COOH orR is -NH 2 , a substituted alkyl group, a substituted alkylamino group, a substituted phenyl amino group, an unsubstituted or substituted naphthyl amino group, an unsubstituted or substituted benzothiazole amino group, an unsubstituted or substituted benzoxazole amino group an unsubstituted or substituted benzimida - zolamino group; x and y independently are hydrogen, -OH, (C 1-4 ) alkyl, -NH 2 or COOH or
(i) x and y form the group -NH-Me-O-, -NH-Me-OOC-,(i) x and y form the group -NH-Me-O-, -NH-Me-OOC-,
-O-Me-O-, -O-Me-OOC- or -NH-Me-NH-, or-O-Me-O-, -O-Me-OOC- or -NH-Me-NH-, or
(ii) x and yo form the group -NH-Me-O-, -NH-Me-NH- or -O-Me-O- where Me is a metal capable of either forming a 1:1 metal complex or a 1:2 metal complex; or capable of forming both a 1:1 and a 1:2 metal complex; n is 1 or 2;. d is 0, 1 or 2;(ii) x and yo form the group -NH-Me-O-, -NH-Me-NH- or -O-Me-O- where Me is a metal capable of either forming a 1: 1 metal complex or a 1 : 2 metal complex; or capable of forming both a 1: 1 and a 1: 2 metal complex; n is 1 or 2 ;. d is 0, 1 or 2;
Rt is one or more of the groups of formula Id to lg below - N = N - D - [ W - ( Z ) a ] b IdR t is one or more of the groups of formula Id to lg below - N = N - D - [W - (Z) a ] b Id
N = N - B 1- N = N - K IeN = N - B 1 - N = N - K Ie
Figure imgf000119_0001
Figure imgf000119_0001
- Y - Z Ig- Y - Z Ig
where D is a diazo component ;where D is a diazo component;
W is a direct bond or a conventional bridging group ; B1 is phenylene, naphthalene, tetrahydro- naphthalene or a group of the formulaW is a direct bond or a conventional bridging group; B 1 is phenylene, naphthalenes, tetrahydronaphthalenes or a group of the formula
Figure imgf000119_0002
Figure imgf000119_0002
Z is a basic amino or a quaternary ammonium group ; a is 1 or 2 ; b is a numbor between 1 and 2;. Z is a basic amino or a quaternary ammonium group ; a is 1 or 2; b is a numbor between 1 and 2; .
K is a coupling component of the series 4-alkyl-2- pyridone, ß-hydroxynaphthalene, aniline, pyrazole-5 or acetoacyl, the coupling component being substituted by at least one water solubilising basic group;K is a coupling component of the series 4-alkyl-2-pyridones, ß-hydroxynaphthalenes, anilines, pyrazole-5 or acetoacyl, the coupling component being substituted by at least one water solubilizing basic group;
Y is a direct bond or a conventional bridging group; X is a direct bond or a conventional bridging group R is a group of the formula IhY is a direct bond or a conventional bridging group; X is a direct bond or a conventional bridging group R is a group of the formula Ih
Figure imgf000120_0001
where x, Ra, Rt and d are above defined and the rings B, C and D can be each substituted independent by up to two further substituents to give up to three substituents in total and ring F can be substituted by up to three substituents in total, with the proviso that
Figure imgf000120_0001
where x, Ra, R t and d are above defined and the rings B, C and D can be each substituted independent by up to two further substitutes to give up to three substitutes in total and ring F can be substituted by up to three substitents in total, with the proviso that
1) when Ra is the group Ic,Rt is the group Ig;1) when Ra is the group Ic, R t is the group Ig;
2) when Rt is the group Ig, Ra is the group Ia and when n = 2, the group -X-R is attached to the group2) when R t is the group Ig, Ra is the group Ia and when n = 2, the group -XR is attached to the group
Ra or Rt,Ra or R t ,
3) when n=2 and when Ra is a group of formula Ia, x and y may not both be selected frorn hydrog -en and C1-4. alkoxy; and AΘis a non-chromophoric conventional anion.3) when n = 2 and when Ra is a group of formula Ia, x and y may not both be selected frorn hydrog -en and C 1-4 . alkoxy; and A Θ is a non-chromophoric conventional anion.
2. An azo compounds according to Claim 1, in metal-free, 1:1 metal complex or 1:2 metal complex from having on average at least 1.3 water solubilising basic groups, the compound being of the formula II 2. An azo compounds according to Claim 1, in metal-free, 1: 1 metal complex or 1: 2 metal complex from having on average at least 1.3 water solubilizing basic groups, the compound being of the formula II
Figure imgf000121_0001
where D, X, W, a, b, and rings B and C are defined in
Figure imgf000121_0001
where D, X, W, a, b, and rings B and C are defined in
Claim 1; c is 1 or 2 ; d' is 0 or 1;Claim 1; c is 1 or 2; d 'is 0 or 1;
A1 is -OH or -NH2 ;A 1 is -OH or -NH 2 ;
A3 is hydrogen or -OH orA 3 is hydrogen or -OH or
A1 and A3 form the group -NH-Me-O- or -O-Me-O- where Me is either a metal capable of either forming a.1:1 metal complex or a 1:2 metal complex or capable of forming both a 1:1 metal complex and a 1:2 metal complex;A 1 and A 3 form the group -NH-Me-O- or -O-Me-O- where Me is either a metal capable of either forming a.1: 1 metal complex or a 1: 2 metal complex or capable of forming both a 1: 1 metal complex and a 1: 2 metal complex;
A2 is -OH or -NH2;A 2 is -OH or -NH 2 ;
Rt' is a group of the formula If defined aboveR t 'is a group of the formula If defined above
z2 is a group of the formulaz 2 is a group of the formula
Figure imgf000121_0002
Figure imgf000121_0003
where each R independently is methyl, ethyl, ß-hydroxyethyl, benzyl, -CH2COCH3 or
Figure imgf000122_0003
provided that not more than one benzyl -CH2COCH3 or is attached to a nitrogen atom,
Figure imgf000122_0002
Figure imgf000121_0002
Figure imgf000121_0003
where each R is independently methyl, ethyl, ß-hydroxyethyl, benzyl, -CH 2 COCH 3 or
Figure imgf000122_0003
provided that not more than one benzyl -CH 2 COCH 3 or is attached to a nitrogen atom,
Figure imgf000122_0002
R127 is methyl or ethyl, m is 0, 1 or 2 and AΘ is defined aboveR 127 is methyl or ethyl, m is 0, 1 or 2 and A Θ is defined above
W is a direct bond or a conventional bridging group, d' is 0 or 1, c is 1 or 2W is a direct bond or a conventional bridging group, d 'is 0 or 1, c is 1 or 2
with the proviso that each of the azo bridges in ring B is ortho to A1 or A2 or to both A1 and A2.with the proviso that each of the azo bridges in ring B is ortho to A 1 or A 2 or to both A 1 and A 2 .
3. An azo compound according to Claim 2 of formula II'3. An azo compound according to Claim 2 of formula II '
where Z , a, W, b, c, D, A1 , A2 , A3, d' and rings B and C are above in Claim 1 or Claim 2where Z, a, W, b, c, D, A 1 , A 2 , A 3 , d 'and rings B and C are above in Claim 1 or Claim 2
Rt" is a group of the formula R t "is a group of the formula
Figure imgf000123_0001
SO2-NH-(CH2)p-Z2, (C1-4) alkyl or (C1-4) alkoxy,
Figure imgf000123_0001
SO 2 -NH- (CH 2 ) p -Z 2 , (C 1-4 ) alkyl or (C 1-4 ) alkoxy,
where p is 1, 2 or 3,where p is 1, 2 or 3,
R1 is C1-4alkyl, -C2H4OH or -(-CH2)p-N- (R1a)2 whereR 1 is C 1-4 alkyl, -C 2 H 4 OH or - (- CH 2 ) p -N- (R 1a ) 2 where
R1a is proply or butyl, R6 is C1-4alkyl, -C2H4OH or (CH2)p-N-(R6')2 where R6' is (C1_4) alkyl and R6a is (C1-4) alkyl, -C2H4OH, -(CH2) p-N-(R6')2 or C2H4O-R6';R 1a is proply or butyl, R 6 is C 1-4 alkyl, -C 2 H 4 OH or (CH 2 ) p -N- (R 6 ') 2 where R 6 ' is (C 1 _ 4 ) alkyl and R 6a is (C 1-4 ) alkyl, -C 2 H 4 OH, - (CH 2 ) p -N- (R 6 ') 2 or C 2 H 4 OR 6 ';
R3 is hydrogen, NO2, -SO2NH2, -SO2NH-R1 -SO2
Figure imgf000123_0003
R 3 is hydrogen, NO 2 , -SO 2 NH 2 , -SO 2 NH-R 1 -SO 2
Figure imgf000123_0003
(C1-4) alkyl, (C1-4) alkoxy(C 1-4 ) alkyl, (C 1-4 ) alkoxy
Figure imgf000123_0002
Figure imgf000123_0002
Figure imgf000124_0001
Figure imgf000124_0002
Figure imgf000124_0003
Figure imgf000124_0001
Figure imgf000124_0002
Figure imgf000124_0003
- CO - NH - (CH2)p - Z2 , - NH - CO - (CH2)p- Z2,- CO - NH - (CH 2 ) p - Z 2 , - NH - CO - (CH 2 ) p - Z 2 ,
- SO2 - NH - (CH2)p- Z or CH2 - Z2,- SO 2 - NH - (CH 2 ) p - Z or CH 2 - Z 2 ,
where R5 is hydrogen, (C1-4) alkyl or (C1-4) alkoxy ;where R 5 is hydrogen, (C 1-4 ) alkyl or (C 1-4 ) alkoxy;
R5' is C1-4alkyl ; no is 1 or 2 and the group (CH2- Z2) is attached to either of phenyl groups J or KR 5 'is C 1-4 alkyl; n o is 1 or 2 and the group (CH 2 - Z 2 ) is attached to either of phenyl groups J or K
R7 is hydrogen, -OH, (C1-4) alkyl, (C1-4) alkoxyR 7 is hydrogen, -OH, (C 1-4 ) alkyl, (C 1-4 ) alkoxy
-NH - CO - NH2 or -NH - CO - CH3 ; R8 is hydrogen , -NH - CO - (CH2) p - Z2 , or -NH - CO - NH 2 or -NH - CO - CH 3 ; R 8 is hydrogen, -NH - CO - (CH 2 ) p - Z 2 , or
Figure imgf000125_0001
Figure imgf000125_0001
R4 is hydrogen, -NO2, (C1-4) alkyl or (C1-4) alkoxy ; K1 is a group of the formulaR 4 is hydrogen, -NO 2 , (C 1-4 ) alkyl or (C 1-4 ) alkoxy; K 1 is a group of the formula
Figure imgf000125_0002
Figure imgf000125_0003
Figure imgf000125_0004
Figure imgf000125_0005
Figure imgf000125_0002
Figure imgf000125_0003
Figure imgf000125_0004
Figure imgf000125_0005
Figure imgf000126_0001
Figure imgf000126_0001
Figure imgf000126_0002
Figure imgf000126_0003
Figure imgf000126_0004
Figure imgf000126_0005
Figure imgf000126_0002
Figure imgf000126_0003
Figure imgf000126_0004
Figure imgf000126_0005
C atom is attached to the N atom of the groupC atom is attached to the N atom of the group
Z2 defined above,Z 2 defined above,
R25 is (C1-4) alkyl, -COO-(R25a) or -COOH whereR 25 is (C 1-4 ) alkyl, -COO- (R 25a ) or -COOH where
R25a is (C1-4) alkyl;R 25a is (C 1-4 ) alkyl;
R26 is hydrogen, halogen, C1-4) alkyl or (C1-4) alkoxy;R 26 is hydrogen, halogen, C 1-4 ) alkyl or (C 1-4 ) alkoxy;
R124 is (C1-4)alkyl or -(CH2)p-Z2; is hydrogen, (C1-4) alkyl, -C2H4OH or (CH2)p-Z2;R 124 is (C 1-4 ) alkyl or - (CH 2 ) p -Z 2 ; is hydrogen, (C 1-4 ) alkyl, -C 2 H 4 OH or (CH 2 ) p -Z 2 ;
Ya' is (C1-4) alkyl, preferably -CH3; is (C1-4) alkyl, or -(CH2)p-Z2; R10 is hydrogen, (C1-4) alkyl, C1-4) alkoxy.Y a 'is (C 1-4 ) alkyl, preferably -CH 3 ; is (C 1-4 ) alkyl, or - (CH 2 ) p -Z 2 ; R 10 is hydrogen, (C 1-4 ) alkyl, C 1-4 ) alkoxy.
-NH-CO-CH3 or -NH-CO-NH2; d' is 0 or 1; R125 is -(CH2)p-Z2, -NH-(CH2)p-Z or
Figure imgf000126_0006
where R126 is hydrogen, -OH, (C1-4) alkoxy,
-NH-CO-CH 3 or -NH-CO-NH 2 ; d 'is 0 or 1; R 125 is - (CH 2 ) p -Z 2 , -NH- (CH 2 ) p -Z or
Figure imgf000126_0006
where R 126 is hydrogen, -OH, (C 1-4 ) alkoxy,
-NH-CO- (CH2)p-Z2 , -CO-NH- (CH2)p-Z2 ,-NH-CO- (CH 2 ) p -Z 2 , -CO-NH- (CH 2 ) p -Z2,
-SO2-NH-(CH2)p-Z2, -(CH2)p-Z2 or -SO 2 -NH- (CH 2 ) p -Z 2 , - (CH 2 ) p -Z 2 or
Figure imgf000127_0001
Figure imgf000127_0001
and R127 is hydrogen or -(CH2)p-Z2; X' is one of the groups X, to X 53 below:and R 127 is hydrogen or - (CH 2 ) p -Z 2; X 'is one of the groups X, to X 53 below:
X1 is a direct bond.X 1 is a direct bond.
X2 a straight or branched chain alkylene group of (C1-4) carbon atoms, X3 -CO -X 2 a straight or branched chain alkylene group of (C 1-4 ) carbon atoms, X 3 -CO -
Figure imgf000127_0002
Figure imgf000128_0001
where R11 is halogen, (C1-4) alkyl or (C1-4) alkoxy R12 is hydrogen or (C1-4) alkyl; R13 is halogen, -NH-CH2-CH2-OH or
Figure imgf000127_0002
Figure imgf000128_0001
where R 11 is halogen, (C 1-4 ) alkyl or (C 1-4 ) alkoxy R 12 is hydrogen or (C 1-4 ) alkyl; R 13 is halogen, -NH-CH 2 -CH 2 -OH or
-N(CH2-CH2OH)2 ; R14 is a straight or branched chain (C1-4)- alkylene group and q is 1, 2, 3 or 4 with the proviso that i) the diazo bridges in ring B are ortho each to-N (CH 2 -CH 2 OH) 2 ; R 14 is a straight or branched chain (C 1-4 ) - alkylene group and q is 1, 2, 3 or 4 with the proviso that i) the diazo bridges in ring B are ortho each to
A1 or A2 or to both A1 and A2 ; ii) when c is 2, X' is attached to Rt" when Rt" is the group αα or to ring C; iii) when d' is 1 ring C can be substituted by one or more of halogen, hydroxy, (C1-4) alkyl, (C1-4) alkoxy and -NH-CO-NH2. 4. An azo compound according to Claim 1 in metal-free, 1:1 metal complex or 1:2 metal complex from having an average of at least 1.3 water solubilising basic groups per dyestuff unit, the compound being of the formula IIIA 1 or A 2 or to both A 1 and A 2 ; ii) when c is 2, X 'is attached to R t "when R t " is the group αα or to ring C; iii) when d 'is 1 ring C can be substituted by one or more of halogen, hydroxy, (C 1-4 ) alkyl, (C 1-4 ) alkoxy and -NH-CO-NH 2 . 4. An azo compound according to Claim 1 in metal-free, 1: 1 metal complex or 1: 2 metal complex from having an average of at least 1.3 water solubilizing basic groups per dyestuff unit, the compound being of the formula III
Figure imgf000129_0001
Figure imgf000129_0001
in which A4 is hydrogen, -OH, -NH2, (C1-4) alkoxy or COOH or A4 and a hydroxy or amino group on K2 together form the group -NH-Me-O-, -NH-Me-NH-,in which A 4 is hydrogen, -OH, -NH 2 , (C 1-4 ) alkoxy or COOH or A 4 and a hydroxy or amino group on K 2 together form the group -NH-Me-O-, -NH-Me-NH-,
-NH-Me-OOC-, -O-Me-O- or -O-Me-OOC- where Me is a metal capable of either forming a 1:1 metal complex or a 1:2 metal complex or capable of forming both a 1:1 and a 1:2 metal complex,-NH-Me-OOC-, -O-Me-O- or -O-Me-OOC- where Me is a metal capable of either forming a 1: 1 metal complex or a 1: 2 metal complex or capable of forming both a 1: 1 and a 1: 2 metal complex,
K2 is one of the groups of the formulaK 2 is one of the groups of the formula
Figure imgf000130_0001
Figure imgf000130_0001
Figure imgf000130_0002
Figure imgf000130_0002
Figure imgf000131_0001
Figure imgf000131_0001
Figure imgf000131_0002
Figure imgf000131_0003
where R9 is -CH3 or -COOH and yo is OH or NH2, R20 is hydrogen or -NO2,
Figure imgf000131_0002
Figure imgf000131_0003
where R 9 is -CH 3 or -COOH and yo is OH or NH 2 , R 20 is hydrogen or -NO 2 ,
R21 is hydrogen, -NO2, -NH- (CH2) s-Z2, -CH2-Z2, -SO2-NH-(CH2)s- Z2, -SO2-NH2, -CO-CH2-Z2, -CO-NH- (CH2)s-Z2 orR 21 is hydrogen, -NO 2 , -NH- (CH 2 ) s -Z 2 , -CH 2 -Z 2 , -SO 2 -NH- (CH 2 ) s - Z 2 , -SO 2 -NH 2 , -CO-CH 2 -Z 2 , -CO-NH- (CH 2 ) s -Z 2 or
Figure imgf000131_0004
Figure imgf000131_0004
R22 is hydrogen, -NO2, -SO2-NH2, -SO2-N(R22a)R 22 is hydrogen, -NO 2 , -SO 2 -NH 2 , -SO 2 -N (R 22a )
-SO2-NH-(CH2)s-OH, -CH2-Z2, -SO2-NH-(CH2)s-Z2, -CO-NH- (CH2)s-Z2, -NH-CO- (CH2)s-Z2 or -SO 2 -NH- (CH 2 ) s -OH, -CH 2 -Z 2 , -SO 2 -NH- (CH 2 ) s -Z 2 , -CO-NH- (CH 2 ) s -Z 2 , -NH-CO- (CH 2 ) s -Z 2 or
Figure imgf000132_0001
where R22 a is (C1-4) alkyl ; R 23 is hydrogen or -CH3 ;
Figure imgf000132_0001
where R 22 a is (C 1-4 ) alkyl; R 23 is hydrogen or -CH 3 ;
Figure imgf000132_0002
Figure imgf000132_0003
where R35 is hydrogen, (C1-4) alkyl or -CH2-COO-R35a where R35a is (C1-4) alkyl;
Figure imgf000132_0002
Figure imgf000132_0003
where R 35 is hydrogen, (C 1-4 ) alkyl or -CH 2 -COO-R 35a where R 35a is (C 1-4 ) alkyl;
Figure imgf000132_0004
Figure imgf000132_0005
where R24a is (C1-4) alkyl, preferably -CH3;
Figure imgf000132_0004
Figure imgf000132_0005
where R 24a is (C 1-4 ) alkyl, preferably -CH 3 ;
R25 is (C1-4) alkyl, -COO- (R25a)or COOH whereR 25 is (C 1-4 ) alkyl, -COO- (R 25a ) or COOH where
R25a is (C1-4)alkyl; R26 is hydrogen, halogen, (C1-4) alkyl or (C1-4)- alkoxy,
Figure imgf000133_0001
C atom is attached to the N atom of the group Z2 defined above, s is 1, 2 , 3 ,
R 25a is (C 1-4 ) alkyl; R 26 is hydrogen, halogen, (C 1-4 ) alkyl or (C 1-4 ) alkoxy,
Figure imgf000133_0001
C atom is attached to the N atom of the group Z 2 defined above, s is 1, 2, 3,
4 , 5 or 6.4, 5 or 6.
R28 is hydrogen, (C1-4) alkyl, (C1-4) alkoxy or halogen,R 28 is hydrogen, (C 1-4 ) alkyl, (C 1-4 ) alkoxy or halogen,
R29 is hydrogen, (C1-4) alkyl, (C1-4) alkoxy, halogen, -NH- (CH2)s-Z2 or -NH- C2H4OH; each R30 independently is hydrogen or (C1-4) alkyl;R 29 is hydrogen, (C 1-4 ) alkyl, (C 1-4 ) alkoxy, halogen, -NH- (CH 2 ) s -Z 2 or -NH- C 2 H 4 OH; each R 30 is independently hydrogen or (C 1-4 ) alkyl;
Figure imgf000133_0002
Figure imgf000133_0003
Figure imgf000133_0004
where d' , Zo , Wa and R5' are defined above;
Figure imgf000133_0002
Figure imgf000133_0003
Figure imgf000133_0004
where d ', Z o , Wa and R 5 ' are defined above;
R33 is hydrogen, halogen, (C1-4) alkyl, (C1-4)- alkoxy, -SO2NH2 or -SO2N(CH3)2; with the provisos that i) R20 and R21 cannot both be -NO2 , ü) R21 and R22 cannot be the same group unless R21 and R22 are both hydrogen, iii) when R21 and R22 are both hydrogen R20 cannot be -NO2 and iv) R20 cannot be -NO2 when R21 R22 and R23 are hydrogen. R 33 is hydrogen, halogen, (C 1-4 ) alkyl, (C 1-4 ) alkoxy, -SO 2 NH 2 or -SO 2 N (CH 3 ) 2 ; with the provisos that i) R 20 and R 21 cannot both be -NO 2 , ü) R 21 and R 22 cannot be the same group unless R 21 and R 22 are both hydrogen, iii) when R 21 and R 22 are both hydrogen R 20 cannot be -NO 2 and iv) R 20 cannot be -NO 2 when R 21 R 22 and R 23 are hydrogen.
5. An azo compound according to Claim 1 in metal- free, 1:1 metal complex or 1:2 metal complex form having at least 1.3 water solubilising basic groups, the compound being of the formula IV5. An azo compound according to Claim 1 in metal-free, 1: 1 metal complex or 1: 2 metal complex form having at least 1.3 water solubilizing basic groups, the compound being of the formula IV
Figure imgf000134_0001
in which A1 is -OH or -NH2 and A5 is -OH, (C1-4) alkoxy or -COOH or A1 and A5 form the group -NH-Me-NH-, -NH-Me-OOC-, -NH-Me-O-, -O-Me-O-, -O-Me-OOC- where Me is a metal capable of either forming a 1:1 metal complex or a 1:2 metal complex or capable of forming both a 1:1 metal complex and a 1:2 metal complex ; e is 0 or 1 ; R60 is hydrogen or -NO2 ; R61 and R62, independently, are hydrogen, -NO2 ,
Figure imgf000134_0001
in which A 1 is -OH or -NH 2 and A 5 is -OH, (C 1-4 ) alkoxy or -COOH or A 1 and A 5 form the group -NH-Me-NH-, -NH-Me- OOC-, -NH-Me-O-, -O-Me-O-, -O-Me-OOC- where Me is a metal capable of either forming a 1: 1 metal complex or a 1: 2 metal complex or capable of forming both a 1: 1 metal complex and a 1: 2 metal complex; e is 0 or 1; R 60 is hydrogen or -NO 2 ; R 61 and R 62 , independently, are hydrogen, -NO 2 ,
-CH2-Z2, -SO2-NH2, -SO2-NH-(CH2)p -Z2,-CH 2 -Z 2 , -SO 2 -NH 2 , -SO 2 -NH- (CH 2 ) p -Z 2 ,
-SO2-NH-C2H4OH, -SO2-N-(R6'2 )2,-SO 2 -NH-C 2 H 4 OH, -SO 2 -N- (R 6 ' 2 ) 2 ,
-CO-NH- (CH 2) p -Z 2, -NH-CO- (CH 2) p -Z 2 ,-CO-NH- (CH 2 ) p -Z 2 , -NH-CO- (CH 2 ) p -Z 2 ,
Figure imgf000135_0001
Figure imgf000135_0001
Figure imgf000135_0002
where R6'2 is (C1-4) alkyl,
Figure imgf000135_0002
where R 6 ' 2 is (C 1-4 ) alkyl,
R63 is -SO2-NH-(CH2)p-Z2, -CO-NH- (CH2)p-Z2,R 63 is -SO 2 -NH- (CH 2 ) p -Z 2 , -CO-NH- (CH 2 ) p -Z 2 ,
-NH-CO-(CH2)p-Z2 or
Figure imgf000135_0003
-NH-CO- (CH 2 ) p -Z 2 or
Figure imgf000135_0003
_ R64 is hydrogen or (C1-4) alkoxy; each R65 independently is hydrogen (C1-4) alkyl or C1-4- alkoxy; p is 1, 2 or 3; q' is 1 or 2 with the proviso that when R63 is -CO-NH- (CH2)p-Z2 q' is 2; K3 is one of the following groups
Figure imgf000136_0001
Figure imgf000136_0002
Figure imgf000136_0003
Figure imgf000136_0004
Figure imgf000136_0005
Figure imgf000136_0006
Figure imgf000137_0001
where R9, R10 , R12 and Z2 are defined in Claim 2;
R 64 is hydrogen or (C 1-4 ) alkoxy; each R 65 is independently hydrogen (C 1-4 ) alkyl or C 1-4 alkoxy; p is 1, 2 or 3; q 'is 1 or 2 with the proviso that when R 63 is -CO-NH- (CH 2 ) p -Z 2 q' is 2; K 3 is one of the following groups
Figure imgf000136_0001
Figure imgf000136_0002
Figure imgf000136_0003
Figure imgf000136_0004
Figure imgf000136_0005
Figure imgf000136_0006
Figure imgf000137_0001
where R 9 , R 10 , R 12 and Z 2 are defined in Claim 2;
R66 is hydrogen, (C1-4) alkyl, -C2H4OH orR 66 is hydrogen, (C 1-4 ) alkyl, -C 2 H 4 OH or
-(CH2)p-Z2 ;- (CH 2 ) p -Z 2 ;
R6'6 is (C1-4) alkyl,R 6 ' 6 is (C 1-4 ) alkyl,
Ta is a group of the formulaTa is a group of the formula
Figure imgf000137_0002
Figure imgf000137_0003
Figure imgf000137_0002
Figure imgf000137_0003
where d and AΘ are in Claim 1, R127 is defined in Claim 2 and R25 is defined in Claim 3; T1a is -CN or -CO-NH2;where d and A Θ are in Claim 1, R 127 is defined in Claim 2 and R 25 is defined in Claim 3; T 1a is -CN or -CO-NH 2 ;
R67 is -N(CH3)2 or-N(CH3)3 AΘ ; R 68 is-(-CH2)p-Z2, -NH-(CH2)p-Z2 orR 67 is -N (CH 3 ) 2 or -N (CH 3 ) 3 A Θ ; R 68 is - (- CH 2 ) p -Z 2 , -NH- (CH 2 ) p -Z 2 or
Figure imgf000137_0004
where R71 is hydrogen, -OH, (C1-4) alkoxy, -NH-CO- (CH2)p-Z2, -CO-NH- (CH2)p-Z2, -SO2-NH-(CH2)p-Z2, -(CH2)p-Z2 or
Figure imgf000137_0004
where R 71 is hydrogen, -OH, (C 1-4 ) alkoxy, -NH-CO- (CH 2 ) p -Z 2 , -CO-NH- (CH 2 ) p -Z 2 , -SO 2 -NH- (CH 2 ) p -Z 2 , - (CH 2 ) p - Z 2 or
Figure imgf000138_0001
and R72 is hydrogen or - (CH2)p-Z2;
Figure imgf000138_0001
and R 72 is hydrogen or - (CH 2 ) p -Z 2 ;
R69 is (C1-4) alkyl or (CH2 ) p-Z2 where p and Z2, are above definedR 69 is (C 1-4 ) alkyl or (CH 2 ) p -Z 2 where p and Z 2 , are above defined
Figure imgf000138_0002
Figure imgf000138_0003
where each R65 independently, is hydrogen, (C1-4) alkyl or (C1-4) alkoxy; and X' is as defined above; with the provisos
Figure imgf000138_0002
Figure imgf000138_0003
where each R 65 is independently, is hydrogen, (C 1-4 ) alkyl or (C 1-4 ) alkoxy; and X 'is as defined above; with the provisos
(i) that R60 and R61 cannot both be -NO2,(i) that R 60 and R 61 cannot both be -NO 2 ,
(ii) that when R61 and R62 are both hydrogen, R60 cannot be -NO2 ,(ii) that when R 61 and R 62 are both hydrogen, R 60 cannot be -NO 2 ,
(iii) that R61 and R62 are not the same group unless both are hydrogen, and(iii) that R 61 and R 62 are not the same group unless both are hydrogen, and
(iv) that each azo bridges in ring B is in an ortho position either to A1 or A2 or to both A1 and A2. (iv) that each azo bridges in ring B is in an ortho position either to A 1 or A 2 or to both A 1 and A 2 .
6. A method for dyeing a substrate comprising applying to that substrate a compound of formula I as defined in Claim 1.6. A method for dyeing a substrate comprising applying to that substrate a compound of formula I as defined in Claim 1.
7. Leather or paper when dyed by a method according to Claim 6.7. Leather or paper when dyed by a method according to Claim 6.
8. A process for the produetion of azo compounds of formula I according to Claim 1, which comprises coupling a diazotised amine of formula γ8. A process for the production of azo compounds of formula I according to Claim 1, which comprises coupling a diazotised amine of formula γ
Figure imgf000139_0001
with a coupling component of the formula δ
Figure imgf000139_0001
with a coupling component of the formula δ
Figure imgf000139_0002
where n' and da have the significances of n and d above with the proviso that n + n' is not greater than 2 and d and da is not greater than 2 and in the case of the metal complexes metallising with a metal capable of forming a 1:1 or 1:2 metal complex or capable of forming both a 1:1 and 1:2 metal complex.
Figure imgf000139_0002
where n 'and da have the significances of n and d above with the proviso that n + n' is not greater than 2 and d and da is not greater than 2 and in the case of the metal complexes metallizing with a metal capable of forming a 1: 1 or 1: 2 metal complex or capable of forming both a 1: 1 and 1: 2 metal complex.
PCT/EP1981/000041 1980-05-13 1981-05-06 Improvements in or relating to organic compounds WO1981003179A1 (en)

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