WO1981003179A1 - Ameliorations aux composes organiques - Google Patents

Ameliorations aux composes organiques 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
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Prior art keywords
group
hydrogen
alkyl
formula
metal complex
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PCT/EP1981/000041
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German (de)
English (en)
French (fr)
Inventor
P Doswald
H Moser
E Moriconi
H Schmid
Original Assignee
Sandoz Ag
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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/de
Publication of WO1981003179A1 publication Critical patent/WO1981003179A1/de

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B44/00—Azo dyes containing onium groups
    • C09B44/10—Azo dyes containing onium groups containing cyclammonium groups attached to an azo group by a carbon atom of the ring system
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B44/00—Azo dyes containing onium groups
    • C09B44/02—Azo dyes containing onium groups containing ammonium groups not directly attached to an azo group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B45/00—Complex metal compounds of azo dyes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP 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
    • D21H21/00—Non-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
    • D21H21/14—Non-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
    • D21H21/28—Colorants ; 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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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4543103A (en) * 1983-04-15 1985-09-24 Sandoz Ltd. Method of dyeing a glass substrate with a polycationic dyestuff
EP0141377A3 (en) * 1983-11-04 1987-05-27 Hodogaya Chemical Co., Ltd. Metal complexes
US6028179A (en) * 1996-04-03 2000-02-22 Basf Aktiengesellschaft Trisazo dyes
WO2004072361A1 (de) * 2003-02-13 2004-08-26 Basf Aktiengesellschaft Wasserverdünnbare formulierung von metallkomplexfarbstoffen

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3213826A1 (de) * 1982-04-15 1983-10-27 Sandoz-Patent-GmbH, 7850 Lörrach Basische und/oder kationische pyridonhaltige dis- oder polyazoverbindungen, ihre herstellung und verwendung

Citations (10)

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FR1211425A (fr) * 1957-07-12 1960-03-16 Sandoz Sa Procédé pour transformer des colorants azoïques métallifères en dérivés aminés quaternaires
GB883445A (en) * 1958-07-04 1961-11-29 Ciba Ltd Complex copper compounds of monoazodyestuffs containing quaternary ammonium groups and process for their manufacture
FR1533643A (fr) * 1966-08-05 1968-07-19 Durand & Huguenin Ag Colorants monoazoïques, cationiques, hydrosolubles, leur procédé de préparation et leurs applications
CH472486A (de) * 1962-10-03 1969-05-15 Hoechst Ag Verfahren zur Herstellung von Azofarbstoffen
GB1296857A (enrdf_load_stackoverflow) * 1968-11-12 1972-11-22
GB1299080A (en) * 1968-11-21 1972-12-06 Sterling Drug Inc Water-soluble quarternary ammonium salts of basic azo dyes
GB1338250A (en) * 1969-12-17 1973-11-21 Sandoz Ltd Basic azo dyes their production and use
US4103092A (en) * 1973-02-14 1978-07-25 Sterling Drug Inc. Water-soluble quaternary ammonium non-heterocyclic azo dyestuffs
GB1550830A (en) * 1975-12-17 1979-08-22 Ici Ltd Water soluble azo dyestuffs
US4206144A (en) * 1971-11-22 1980-06-03 Sterling Drug Inc. N,N-Dialkyl-N-aminoalkyl-N-(amino or nitro)phenylalkyl- and N-methyl-N-[3-(amino or nitro)phenoxy-2-hydroxy-1-propyl]-N,N-bis(3-aminopropyl)quaternary ammonium salts

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1211425A (fr) * 1957-07-12 1960-03-16 Sandoz Sa Procédé pour transformer des colorants azoïques métallifères en dérivés aminés quaternaires
GB883445A (en) * 1958-07-04 1961-11-29 Ciba Ltd Complex copper compounds of monoazodyestuffs containing quaternary ammonium groups and process for their manufacture
CH472486A (de) * 1962-10-03 1969-05-15 Hoechst Ag Verfahren zur Herstellung von Azofarbstoffen
FR1533643A (fr) * 1966-08-05 1968-07-19 Durand & Huguenin Ag Colorants monoazoïques, cationiques, hydrosolubles, leur procédé de préparation et leurs applications
GB1296857A (enrdf_load_stackoverflow) * 1968-11-12 1972-11-22
GB1299080A (en) * 1968-11-21 1972-12-06 Sterling Drug Inc Water-soluble quarternary ammonium salts of basic azo dyes
GB1338250A (en) * 1969-12-17 1973-11-21 Sandoz Ltd Basic azo dyes their production and use
US4206144A (en) * 1971-11-22 1980-06-03 Sterling Drug Inc. N,N-Dialkyl-N-aminoalkyl-N-(amino or nitro)phenylalkyl- and N-methyl-N-[3-(amino or nitro)phenoxy-2-hydroxy-1-propyl]-N,N-bis(3-aminopropyl)quaternary ammonium salts
US4103092A (en) * 1973-02-14 1978-07-25 Sterling Drug Inc. Water-soluble quaternary ammonium non-heterocyclic azo dyestuffs
GB1550830A (en) * 1975-12-17 1979-08-22 Ici Ltd Water soluble azo dyestuffs

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4543103A (en) * 1983-04-15 1985-09-24 Sandoz Ltd. Method of dyeing a glass substrate with a polycationic dyestuff
EP0141377A3 (en) * 1983-11-04 1987-05-27 Hodogaya Chemical Co., Ltd. Metal complexes
US6028179A (en) * 1996-04-03 2000-02-22 Basf Aktiengesellschaft Trisazo dyes
WO2004072361A1 (de) * 2003-02-13 2004-08-26 Basf Aktiengesellschaft Wasserverdünnbare formulierung von metallkomplexfarbstoffen

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