WO1981003179A1 - Improvements in or relating to organic compounds - Google Patents
Improvements in or relating to organic compounds Download PDFInfo
- 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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- WIPO (PCT)
- Prior art keywords
- group
- hydrogen
- alkyl
- formula
- metal complex
- Prior art date
Links
- 0 C*N=C(*C(CN*(C)=C)N)N(C)C(C)NC Chemical compound C*N=C(*C(CN*(C)=C)N)N(C)C(C)NC 0.000 description 20
- XDTMQSROBMDMFD-UHFFFAOYSA-N C1CCCCC1 Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- TTWPZMKRYOLRFU-URXQNVNOSA-N C/N=C\C=C(\C1=C)/C1=C\C=C Chemical compound C/N=C\C=C(\C1=C)/C1=C\C=C TTWPZMKRYOLRFU-URXQNVNOSA-N 0.000 description 1
- VIDBPDAIRPUEOU-UHFFFAOYSA-N CNC(N1)NC(NC)[IH]C2(CC2)C1I Chemical compound CNC(N1)NC(NC)[IH]C2(CC2)C1I VIDBPDAIRPUEOU-UHFFFAOYSA-N 0.000 description 1
- HCPJEHJGFKWRFM-UHFFFAOYSA-N Cc(cc1O)ccc1N Chemical compound Cc(cc1O)ccc1N HCPJEHJGFKWRFM-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
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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
- C09B44/02—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
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- 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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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
Ra is a group of the formula Ia - IcRa is a group of the formula Ia - Ic
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; 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
- 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
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
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 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
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 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
where each Ro independently is methyl, ethyl, ß-hydroxyethyl, benzyl, -CH2COCH3 or
provided that not more than one benzyl, -CH2COCH3 where 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
or is attached or not more than two
ß-hydroxyethyl groups are attached to a nitrogen atom,or is attached or not more than two 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 '
where Z2, a, W, b, c, D, A1, A2, A3 , d' and rings B and C are above defined; 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
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 ';
(C1-4) alkyl, (C1_4)alkoxy
Alkoxy alkyl (C1-4), (C 1 _ 4)
- 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
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
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
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 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
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 -
X50 - O - (CH2)q- O -
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 - 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
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, 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
R21 is hydrogen, -NO2, -NH-CO (CH2)s-Z2 , -CH2-Z2, -SO2-NH-(CH2)s- Z2, -SO2-NH2, -CO-CH2~Z2, 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
R22 is hydrogen, -NO2, -SO2-NH2, -SO2-N (R22a)2 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
R23 is hydrogen or -CH3 R 23 is hydrogen or -CH 3
where R35 is hydrogen, (C1-4) alkyl or -CH2-COO-R35a where R 35a is (C1-4)alkyl 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;
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 ; 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;
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
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; 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
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 ,
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
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 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
where R71 is hydrogen, -OH, (C1-4) alkoxy,
-NH-CO-(CH2)p-Z2, -CO-NH- (CH2)p-Z2 , 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
and R72 is hydrogen or -(CH2)p-Z2 ; R69 is (C1-4) alkyl or-(CH2)p-Z2 where p and Z2 are above defined 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
where each R65 independently, is hydrogen, (C1-4) alkyl or (C1_4) alkoxy; and X' is as defined above; with the provisos 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
where each R2a independently is hydrogen, -NO2, -SO2NH2, -SO2-NH-CH3, -SO2-N(CH3)2 , where each R 2a is independently hydrogen, -NO 2 , -SO 2 NH 2 , -SO 2 -NH-CH 3 , -SO 2 -N (CH 3 ) 2 ,
-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,
-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 , -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,
-CO-NH- (CH 2 ) p -Z 2 , -CH 3 , -OCH 3 , -SO 2 -NΗ- (CH 2 ) p -Z 2 ,
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
n0' is an average number between 1.0 and 1.7 K1' is n 0 'is an average number between 1.0 and 1.7 K 1 ' is
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
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
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-,
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 -,
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-,
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-,
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
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 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
-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
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. 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
in which Rt v is hydrogen,
Mec is copper , cobalt or chromium preferably copper in which R t v is hydrogen, 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 ,
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
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. 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
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 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
in which D1 , A1' , R3a, R4 a , Mea, and Xa are above defined; 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
in which R3e is hydrogen, -CH3, -NO2, -SO2-NH2, -CH2-Z3, in which R 3e is hydrogen, -CH 3 , -NO 2 , -SO 2 -NH 2 , -CH 2 -Z 3 ,
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:
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
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 ,
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
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' , 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 ',
-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
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
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
and the other symbols are above defined with the provisos 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
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
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
and where all the other symbols are above defined, with the proviso that R34 and R35 are not both NO2. 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
R22d is hydrogen, -CH2-Z3, -SO2 -N (CH3)22 , -NO2, R 22d is hydrogen, -CH 2 -Z 3 , -SO 2 -N (CH 3 ) 22 , -NO 2 ,
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 ;
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,
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
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
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 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
in which R21a is hydrogen, -CH2-Z2, -NH-CO-(CH2)a-Z2, 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
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
and the other symbols are defined above ; with the provisos i) that in ring E the azo bridge is in the 3- or 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
in which R21b and R22b are independently hydrogen, -CH2-Z3 , -NO2 ,-SO2-NH2,-NH-CO-CH2-Z3, 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
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 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
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
and all the other symbols are as defined above with the proviso that R21c and R22c are not both -NO2. 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
-K5-O- is one of the following formulae Illba to Illbf
-K 5 -O- is one of the following formula Illba to Illbf
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
in which -O-K6- is
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 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
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 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
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
in which each Tx" independently is
in which all the other symbols aro as defined above with the proviso that R21c and R22c are not both -NO2. in which 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 .
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
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
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 .
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
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 ,
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 ,
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 ;
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
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
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
-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
K 7 ' is one of the groups IVba
K 7 'is one of the groups IVba
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
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
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
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
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 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, -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
all other symbols are as above defined, with the provisos 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
in which each R 65b independently , is -CH3 or -OCH3, in which each R 65b independently, is -CH 3 or -OCH 3 ,
all the other symbols are as above defined, and the same provisos apply as to compounds of formula IVc. 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
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. 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
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 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
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 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
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
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
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 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
More preferred compounds of formula IVl are of the formula IVmMore preferred compounds of formula IVl are of the formula IVm
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
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 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
and R3a is preferably R3b, more preferably R3c, and R3c preferably hydrogen, -NO2, -SO2NH2, -SO2NH (CH2) 3N (CH3) 2 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
R64a is hydrogen.R 64a is hydrogen.
Preferably in compounds of formula IIIPreferably in compounds of formula III
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
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. 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)
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)
which dyes leather a red/orange colour. c) 40.4 Parts mole) of the dyestuff b)
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) 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)
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
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
of sodium nitrite are dissolved in 250 parts of water. At a temperature of 10°C, 17.2 parts mole) of the
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 4of sodium nitrite are dissolved in 250 parts of water. At a temperature of 10 ° C, 17.2 parts mole) of the 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
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
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 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 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)
The dyestuff dyes leather a red brown colour with good fastness properties. The dyestuff dyes leather a red brown color with good fastness properties.
By substituting 7 parts cobalt sulphate mole
or 6.8 parts of FeCl3 6H2O mole) for 12.5 parts of
KCr(SO4)2 12H2O the corresponding 1:1 cobalt and iron complexes respectively can be produced. Example 5By substituting 7 parts cobalt sulphate mole or 6.8 parts of FeCl 3 6H 2 O mole) for 12.5 parts of 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
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)
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)
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)
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)
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-
nitrobenzol are coupled with 11 parts of resorcinol to give a compound of the formula VIaExample 6 a) 15. 4 parts mole) of 1-hydroxy-2-amino-4- nitrobenzene are coupled with 11 parts of resorcinol to give a compound of the formula VIa
b) 24 Parts mole) of 2 (4'-aminophenyl)-6-
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 VIbb) 24 parts mole) of 2 (4'-aminophenyl) -6- 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
results . c) 15.4 Parts ( mole) of the dyestuff of
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 VIcresults. c) 15.4 Parts (mole) of the dyestuff of 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
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
Examples 7 - 1;Examples 7 - 1;
The following Examples are compounds of the formulaThe following examples are compounds of the formula
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. 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 -
The following Examples are of compounds of the formulaThe following examples are of compounds of the formula
and in 1:1 metal complex and 1:2 metal complex form. and in 1: 1 metal complex and 1: 2 metal complex form.
The following Examples are compounds of the formulaThe following examples are compounds of the formula
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 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
R400 is -SO2-NH-(CH2)3-N(CH3)2
R 400 is -SO 2 -NH- (CH 2 ) 3 -N (CH 3 ) 2
Examples 59 to 72 The following Examples are compounds of the formulaExamples 59 to 72 The following examples are compounds of the formula
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. 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 .
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
EE
Examples 84 to 104Examples 84 to 104
The following Examples are compounds of the formulaThe following examples are compounds of the formula
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. 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.
Examples 104 to 129Examples 104 to 129
The following Examples are of formulaThe following examples are of formula
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.
The following Examples are of formula
in which Z 1 is -N(C2H5)2 and Z2 is -N(CH3)2.The following examples are of formula 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
Examples 130-160Examples 130-160
The following Examples are of the formulaThe following examples are of the formula
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. 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.
In the following ExamplesIn the following examples
Examples 161 - 166Examples 161-166
The following Examples of the formulaThe following examples of the formula
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.
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.
Examples 167-172Examples 167-172
The following Examples are of the formulaThe following examples are of the formula
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.
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.
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.
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:
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.
Claims
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
Ra is a group of the formula ia - IcRa is a group of the formula ia - Ic
is a substituted pyrazolone-5, a substituted 5-aminopyrazole, a substituted 4-alkyl-2-pyridone or a substituted ß-hydroxynaphthalene group; 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
- 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
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
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 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
where D, X, W, a, b, and rings B and C are defined in 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
where each R independently is methyl, ethyl, ß-hydroxyethyl, benzyl, -CH2COCH3 or provided that not more than one benzyl -CH2COCH3 or is attached to a nitrogen atom, where each R is independently methyl, ethyl, ß-hydroxyethyl, benzyl, -CH 2 COCH 3 or provided that not more than one benzyl -CH 2 COCH 3 or is attached to a nitrogen atom,
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
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,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 R 3 is hydrogen, NO 2 , -SO 2 NH 2 , -SO 2 NH-R 1 -SO 2
(C1-4) alkyl, (C1-4) alkoxy(C 1-4 ) alkyl, (C 1-4 ) alkoxy
- 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
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
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 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 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
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 -
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 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
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
where R9 is -CH3 or -COOH and yo is OH or NH2, R20 is hydrogen or -NO2, 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
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
where R22 a is (C1-4) alkyl ; R 23 is hydrogen or -CH3 ; where R 22 a is (C 1-4 ) alkyl; R 23 is hydrogen or -CH 3 ;
where R35 is hydrogen, (C1-4) alkyl or -CH2-COO-R35a where R35a is (C1-4) alkyl; where R 35 is hydrogen, (C 1-4 ) alkyl or -CH 2 -COO-R 35a where R 35a is (C 1-4 ) alkyl;
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, 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, 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;
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
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 , 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 ,
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 ,
_ 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 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 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
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
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 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
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
where each R65 independently, is hydrogen, (C1-4) alkyl or (C1-4) alkoxy; and X' is as defined above; with the provisos 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
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. 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.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56501662A JPH0335339B2 (en) | 1981-05-06 | 1981-05-06 | |
PCT/EP1981/000041 WO1981003179A1 (en) | 1980-05-13 | 1981-05-06 | Improvements in or relating to organic compounds |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH3737/80 | 1980-05-13 | ||
PCT/EP1981/000041 WO1981003179A1 (en) | 1980-05-13 | 1981-05-06 | Improvements in or relating to organic compounds |
Publications (1)
Publication Number | Publication Date |
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WO1981003179A1 true WO1981003179A1 (en) | 1981-11-12 |
Family
ID=8164820
Family Applications (1)
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PCT/EP1981/000041 WO1981003179A1 (en) | 1980-05-13 | 1981-05-06 | Improvements in or relating to organic compounds |
Country Status (2)
Country | Link |
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JP (1) | JPH0335339B2 (en) |
WO (1) | WO1981003179A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0141377A2 (en) * | 1983-11-04 | 1985-05-15 | Hodogaya Chemical Co., Ltd. | Metal complexes |
US4543103A (en) * | 1983-04-15 | 1985-09-24 | Sandoz Ltd. | Method of dyeing a glass substrate with a polycationic dyestuff |
US6028179A (en) * | 1996-04-03 | 2000-02-22 | Basf Aktiengesellschaft | Trisazo dyes |
WO2004072361A1 (en) * | 2003-02-13 | 2004-08-26 | Basf Aktiengesellschaft | Water-dilutable metallized dye formulation |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3213826A1 (en) * | 1982-04-15 | 1983-10-27 | Sandoz-Patent-GmbH, 7850 Lörrach | Basic and/or cationic pyridone-containing dis- or polyazo compounds, their preparation and use |
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FR1211425A (en) * | 1957-07-12 | 1960-03-16 | Sandoz Sa | Process for converting metalliferous azo dyes into quaternary amine derivatives |
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 (en) * | 1966-08-05 | 1968-07-19 | Durand & Huguenin Ag | Monoazo, cationic, water-soluble dyes, their preparation process and applications |
CH472486A (en) * | 1962-10-03 | 1969-05-15 | Hoechst Ag | Process for the production of azo dyes |
GB1296857A (en) * | 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 |
-
1981
- 1981-05-06 JP JP56501662A patent/JPH0335339B2/ja not_active Expired
- 1981-05-06 WO PCT/EP1981/000041 patent/WO1981003179A1/en unknown
Patent Citations (10)
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FR1211425A (en) * | 1957-07-12 | 1960-03-16 | Sandoz Sa | Process for converting metalliferous azo dyes into quaternary amine derivatives |
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 (en) * | 1962-10-03 | 1969-05-15 | Hoechst Ag | Process for the production of azo dyes |
FR1533643A (en) * | 1966-08-05 | 1968-07-19 | Durand & Huguenin Ag | Monoazo, cationic, water-soluble dyes, their preparation process and applications |
GB1296857A (en) * | 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 (5)
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 |
EP0141377A2 (en) * | 1983-11-04 | 1985-05-15 | Hodogaya Chemical Co., Ltd. | Metal complexes |
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 (en) * | 2003-02-13 | 2004-08-26 | Basf Aktiengesellschaft | Water-dilutable metallized dye formulation |
Also Published As
Publication number | Publication date |
---|---|
JPS57500473A (en) | 1982-03-18 |
JPH0335339B2 (en) | 1991-05-27 |
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