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US 4,673,735 AGranted
Azo compounds having at least one 6-hydroxypyrid-2-one coupling component radical metal complexes thereof and intermediates therefor
AssigneeSandoz Ltd.
InventorsHelmut Moser, Manfred Greve, Reinhard Pedrazzi, Roland Wald
Life of this patent
Estimating the term…
Abstract
A compound of formula I ##STR1## in metal-free; 1:1 or 1:2 metal complex form and, when an acid group is present, in free acid or acid addition salt form, in which R.sub.1 is hydrogen or --N.dbd.N--D where D is a diazo component and R, T and B are organic radicals defined in the text.
Claims13
A metal-free compound of the formula ##STR275## or a 1:1 or 1:2 metal complex thereof, or an acid addition salt of a metal-free compound of said formula or a 1:1 or 1:2 metal complex thereof,
- wherein
- B is hydrogen;
- C.sub.1-4 alkyl;
- C.sub.1-4 alkyl monosubstituted by C.sub.1-4 alkoxy;
- C.sub.2-4 alkyl substituted by hydroxy;
- C.sub.5-6 cycloalkyl;
- C.sub.5-6 cycloalkyl substituted by 1 to 3 C.sub.1-4 alkyl groups;
- phenyl(C.sub.1-3 alkyl);
- phenyl(C.sub.1-3 alkyl) the phenyl group of which is substituted by 1 to 3 substituents selected from C.sub.1-4 alkyl, C.sub.1-4 alkoxy and halo;
- --A--NH--R.sub.2 ;
- --A.sub.4 '--N(R.sub.7).sub.2 ;
- --A.sub.4 --N.sup..sym. (R.sub.8).sub.2 R.sub.9 A.sup..crclbar. or --N(R.sub.7).sub.2,
- wherein
- A is linear or branched C.sub.2-8 alkylene;
- linear or branched C.sub.2-8 alkylene interrupted by 1 or 2 hetero atoms;
- linear or branched C.sub.2-8 alkenylene;
- linear or branched C.sub.2-8 alkenylene interrupted by 1 or 2 hetero atoms;
- phenylene or cyclohexylene,
- A.sub.4 is linear or branched C.sub.2-8 alkylene or linear or branched C.sub.2-8 alkenylene,
- A.sub.4 ' is linear or branched C.sub.1-8 alkylene or linear or branched C.sub.2-8 alkenylene, and
- R.sub.2 is ##STR276## wherein R.sub.11 is hydrogen, halo, nitro, C.sub.1-4 alkyl or C.sub.1-4 alkoxy, and
- R.sub.12 is --CO--(CH.sub.2).sub.a --Z or ##STR277## wherein Z is --N(R.sub.7).sub.2 or --N.sup..sym. (R.sub.8).sub.2 R.sub.9 A.sup..crclbar., and a is 1, 2 or 3,
- R is hydrogen;
- C.sub.1-4 alkyl;
- C.sub.5-6 cycloalkyl;
- C.sub.5-6 cycloalkyl substituted by 1 or 2 C.sub.1-4 alkyl groups;
- phenyl;
- phenyl substituted by 1 or 2 substituents selected from methyl, ethyl, methoxy and ethoxy;
- benzyl;
- phenylethyl;
- or benzyl or phenylethyl the phenyl group of which is substituted by 1 or 2 substituents selected from methyl, ethyl, methoxy and ethoxy,
- R.sub.1 is hydrogen or --N.dbd.N--D,
- wherein D is a diazo component radical, with the proviso that R.sub.1 must be ##STR278## when B is other than --A--NH--R.sub.2, wherein
- A.sub.1 is a tetrazo component radical,
- R.sub.17 is hydrogen, --N.dbd.N--K.sub.1, --N.dbd.N--A.sub.10 --N.dbd.N--K.sub.1, ##STR279## wherein A.sub.10 is a tetrazo component radical or a coupling/diazo component radical,
- K.sub.1 is a diazo component radical or a coupling component radical,
- R.sub.20 is --(NR.sub.5).sub.q --Q.sub.1 --N(R.sub.7).sub.2, --(NR.sub.5).sub.q --Q.sub.2 --N.sup..sym. (R.sub.8).sub.2 R.sub.9 A.sup..crclbar. or ##STR280## wherein Q.sub.1 is linear or branched C.sub.2-6 alkylene, --CH.sub.2 C*O-- or --CH.sub.2 --CON*H--, wherein the * denotes the atom attached to the --(NR.sub.5).sub.q -- radical, and
- Q.sub.2 is linear or branched C.sub.2-6 alkylene, --CH.sub.2 C*O--, --CH.sub.2 CON*H-- or --CH.sub.2 CONHC*O--, wherein the * denotes the atom attached to the --(NR.sub.5).sub.q -- radical,
- X.sub.o is a bridging radical,
- R.sub.19 is hydrogen;
- hydroxy;
- amino;
- (C.sub.1-4 alkyl)carbonylamino;
- benzoylamino;
- phenylamino;
- or benzoylamino or phenylamino the phenyl group of which is substituted by 1 or 2 substituents selected from halo, nitro, amino, C.sub.1-4 alkyl and C.sub.1-4 alkoxy, with the proviso that R.sub.19 must be hydrogen when R.sub.17 is other than --N.dbd.N--K.sub.1 and --N.dbd.N--A.sub.10 --N.dbd.N--K.sub.1, and
- R.sub.60 is hydroxy or amino, and
- R.sub.60a is hydrogen, hydroxy or amino, with the proviso that R.sub.60a is hydrogen or amino when R.sub.60 is hydroxy and is hydroxy when R.sub.60 is amino, and
- T is hydrogen, cyano, --COOR.sub.4, --CO--N(R.sub.5).sub.2, --SO.sub.2 --N(R.sub.5).sub.2, ##STR281## wherein each R.sub.3 is independently hydrogen, C.sub.1-4 alkyl, --N(R.sub.5).sub.2 or --CO--N(R.sub.5).sub.2,
- R.sub.4 is C.sub.1-6 alkyl or phenyl(C.sub.1-3 alkyl),
- R.sub.6 is C.sub.1-4 alkyl, and
- X.sub.a is --O--, --NR.sub.5 -- or --S--,
- wherein
- each R.sub.5 is independently hydrogen or C.sub.1-4 alkyl or, when two R.sub.5 's are attached to a nitrogen atom, both R.sub.5 's taken together and with the nitrogen atom may form a saturated ring containing 1 to 3 hetero atoms,
- each R.sub.7 is independently hydrogen;
- C.sub.1-6 alkyl;
- C.sub.2-6 alkyl monosubstituted by halo, hydroxy or cyano;
- phenyl(C.sub.1-3 alkyl);
- phenyl(C.sub.1-3 alkyl) the phenyl group of which is substituted by 1 to 3 substituents selected from halo, C.sub.1-4 alkyl and C.sub.1-4 alkoxy;
- C.sub.5-6 cycloalkyl or C.sub.5-6 cycloalkyl substituted by 1 or 3 C.sub.1-4 alkyl groups, or both R.sub.7 's taken together and with the nitrogen atom to which they are attached form a 5- or 6-membered saturated ring containing 1 to 3 hetero atoms,
- each R.sub.8 is independently C.sub.1-6 alkyl;
- C.sub.2-6 alkyl monosubstituted by halo, hydroxy or cyano;
- phenyl(C.sub.1-3 alkyl);
- phenyl(C.sub.1-3 alkyl) the phenyl group of which is substituted by 1 to 3 substituents selected from halo, C.sub.1-4 alkyl and C.sub.1-4 alkoxy;
- C.sub.5-6 cycloalkyl or C.sub.5-6 cycloalkyl substituted by 1 or 3 C.sub.1-4 alkyl groups,
- each R.sub.9 is independently C.sub.1-4 alkyl or C.sub.1-4 alkyl substituted by phenyl or both R.sub.8 's and R.sub.9 taken together and with the nitrogen atom to which they are attached are pyridinium;
- pyridinium substituted by 1 or 2 C.sub.1-4 alkyl groups;
- or a 5- or 6-membered saturated ring containing 1 to 3 hetero atoms,
- each R.sub.13 is independently amino;
- an aliphatic, cycloaliphatic, aromatic or heterocyclic amino group the nitrogen atom of which is attached to the 1,3,5-triazine ring;
- halo;
- hydroxy;
- C.sub.1-4 alkoxy;
- phenyl or ##STR282## wherein A.sub.2 is linear or branched C.sub.2-6 alkylene or --N*HCOCH.sub.2 --,
- wherein the * denotes the atom attached to the --NR.sub.5 -- radical, and R, R.sub.1, R.sub.5 and T are as defined above,
- each R.sub.14 is independently an aliphatic, cycloaliphatic, aromatic or heterocyclic amino group the nitrogen atom of which is attached to the 1,3,5-triazine ring,
- each n is independently 0, 1 or 2,
- each q is independently 0 or 1, and
- each A.sup..crclbar. is independently a non-chromophoric anion,
- with the provisos that (i) when the compound of Formula I is a monoazo compound free of sulfo groups, it contains at least one water-solubilizing basic or cationic group, (ii) when the compound of Formula I is free of sulfo groups and is other than a monoazo compound, it contains at least two water-solubilizing groups, and (iii) when the compound of Formula I contains one or more sulfo groups, the total number of basic and cationic groups exceeds the number of sulfo groups by at least one.
77 more elements
A metal-free compound according to claim 1 having the formula ##STR348## or a 1:1 or 1:2 metal complex thereof, or an acid addition salt of a metal-free compound of said formula or an acid addition salt thereof,
- wherein
- A" is 1,2-ethylene, 1,3-propylene, 1,3-phenylene or 1,4-phenylene,
- R.sub.1.sup.iv is hydrogen or --N.dbd.N--D"',
- wherein
- D"' is ##STR349## wherein R.sub.26 ' is hydrogen, nitro, chloro, methyl, methoxy or chlorophenoxy,
- each R.sub.26a is independently nitro, chloro, methyl or methoxy,
- each R.sub.27a is independently hydrogen, chloro, methyl or methoxy, and
- R.sub.27b is hydrogen, methyl or methoxy,
- R.sub.2 " is ##STR350## wherein R.sub.12 " is --CO--CH.sub.2 --Z" or ##STR351## wherein R.sub.13 " is --NR.sub.5 "R.sub.21 ', ##STR352## R.sub.14 " is --NR.sub.5 "R.sub.21 ', ##STR353## and Z" is --N(R.sub.7 ").sub.2 or --N.sup..sym. (R.sub.8 ").sub.2 R.sub.9 "A.sup..crclbar., and
- T" is cyano or ##STR354## wherein R.sub.3 " is hydrogen or methyl, wherein
- A.sub.1 ' is ##STR355## wherein R.sub.51 is hydrogen, halo, C.sub.1-4 alkyl or C.sub.1-4 alkoxy,
- R.sub.52 is hydrogen, hydroxy, halo, cyano, --CONH.sub.2, (C.sub.1-4 alkyl)carbonylamino, --NHCONH.sub.2, carboxy, sulfo, C.sub.1-4 alkyl or C.sub.1-4 alkoxy,
- each R.sub.53 is independently hydrogen, halo, cyano, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, carboxy, sulfo or hydroxy, and
- Yo is a direct bond, --(CH.sub.2).sub.a --, --O--, --S--, --SO.sub.2 --, --NHCO--, --NHCONH--, --NHCO--(CH.sub.2).sub.b --CONH--, --CONH--(CH.sub.2).sub.b --NHCO--, --O--(CH.sub.2).sub.b --O--, --N.dbd.N-- or --CH.dbd.CH--CO--CH.dbd.CH--,
- K.sub.a " is ##STR356## wherein K.sub.b ' is ##STR357## X", when both R.sub.27a 's and R.sub.27b are hydrogen, is a direct bond, --S--, --O--, --CH.dbd.CH--, --NH--, --NHCO--, ##STR358## or --CONH--(CH.sub.2).sub.2 --NHCO--, wherein
- R.sub.42a is hydrogen, chloro, methyl or methoxy,
- R.sub.43 is linear or branched C.sub.1-4 alkylene,
- R.sub.45a is chloro, 2-hydroxyethylamino, methoxy, ethoxy, hydroxy, amino, N,N-di-(2-hydroxyethyl)amino, 3-diethylaminopropylamino, N-methyl-N-phenylamino, N-cyclohexyl-N-methylamino or piperidino, and
- g is 1, 2, 3 or 4, and
- wherein
- B' is hydrogen, methyl, ethyl, hydroxyethyl, cyclohexyl, benzyl, --(CH.sub.2).sub.a --N(R.sub.7 ').sub.2, --(CH.sub.2).sub.b --N.sup..sym. (R.sub.8 ').sub.2 R.sub.9 'A.sup..crclbar. or --A'--NH--R.sub.2 ',
- wherein
- A' is linear or branched C.sub.2-8 alkylene or phenylene,
- R.sub.2 ' is ##STR359## wherein R.sub.11 ' is hydrogen, chloro, nitro, methyl or methoxy, and
- R.sub.12 ' is --CO--(CH.sub.2).sub.t --Z' or ##STR360## wherein R.sub.13 ' is chloro, hydroxy, amino, N,N-di-(C.sub.2-4 -hydroxyalkyl)amino, --NR.sub.5 'R.sub.21, ##STR361## wherein R.sub.11 ' is as defined above, R.sub.14 ' is --NR.sub.5 'R.sub.21, ##STR362## and Z' is --N(R.sub.7 ').sub.2 or --N.sup..sym. (R.sub.8 ').sub.2 R.sub.9 'A.sup..crclbar.,
- R' is methyl, ethyl, phenyl, benzyl or cyclohexyl, R.sub.21 ' is --(CH.sub.2).sub.b --N(R.sub.7 ")--(CH.sub.2).sub.b --NR.sub.7 "R.sub.6 ', --(CH.sub.2).sub.b --N.sup..sym. (R.sub.8 ").sub.2 --(CH.sub.2).sub.b --N(R.sub.8 ").sub.2 R.sub.6 '2A.sup..crclbar., --(CH.sub.2).sub.b --N(R.sub.7 ")--C.sub.2 H.sub.5, --(CH.sub.2).sub.b --N.sup..sym. (R.sub.8 ").sub.2 --C.sub.2 H.sub.5 A.sup..crclbar., --NHCO--CH.sub.2 --Z", --CH.sub.2 --CONH--Y.sub.2 '--Z", ##STR363## wherein R.sub.6 ' is methyl or ethyl,
- R.sub.24 is --N(R.sub.7 ').sub.2, --N.sup..sym. (R.sub.8 ').sub.2 R.sub.9 'A.sup..crclbar., --CO--Y.sub.2 --Z', --NHCO--Y.sub.2 --Z', --CONH--Y.sub.2 --Z'--SO.sub.2 NH--Y.sub.2 --Z', --Y.sub.2 --Z' or --NHNHCO--CH.sub.2 --Z',
- wherein Z' is as defined above,
- Y.sub.2 ' is linear or branched C.sub.1-4 alkylene, and
- Z" is as defined above,
- each R.sub.28 is independently hydrogen, halo, C.sub.1-4 alkyl or C.sub.1-4 alkoxy,
- R.sub.29 ' is --(CH.sub.2).sub.m' --Z', ##STR364## wherein R.sub.46 ' is hydrogen, --NHCO--(CH.sub.2).sub.b --Z', --SO.sub.2 NH--(CH.sub.2).sub.b --Z' or ##STR365## wherein R.sub.13 ", R.sub.14 " and Z' are as defined above, each R.sub.47 ' is independently hydrogen, chloro, bromo, methyl, ethyl, methoxy, ethoxy, nitro or cyano, and
- R.sub.48 ' is methoxy or ethoxy, and
- each R.sub.33 ' is independently hydrogen, 2-hydroxyethyl, 3-methoxypropyl, --(CH.sub.2).sub.b --N(CH.sub.3).sub.2 or --(CH.sub.2).sub.b --N.sup..sym. (CH.sub.3).sub.3 A.sup..crclbar.,
- R.sub.34 is hydroxy or amino,
- R.sub.36 ' is hydrogen, ##STR366## wherein R.sub.49 ' is hydrogen, --CONH--(CH.sub.2).sub.m' --Z', --NHCO--(CH.sub.2).sub.b --Z' or ##STR367## wherein R.sub.13 ', R.sub.14 ' and Z' are as defined above, and each R.sub.50 ' is independently hydrogen, chloro, methyl or methoxy,
- R.sub.37 ' is ##STR368## wherein R.sub.13 " and R.sub.14 " are as defined above, R.sub.38 ' is methyl, ethyl, 2-cyanoethyl or benzyl,
- R.sub.39 ' is methyl, ethyl or --(CH.sub.2).sub.m' --Z,
- R.sub.40 is independently hydrogen, C.sub.1-4 alkyl or C.sub.1-4 alkoxy, and
- each T' is independently hydrogen, cyano, --CO--N(R.sub.5 ').sub.2 or ##STR369## wherein each R.sub.3 ' is independently hydrogen, methyl, ethyl, amino or dimethylamino,
- wherein
- each R.sub.7 ' is independently hydrogen, C.sub.1-6 alkyl, n-hydroxy(C.sub.2-3 alkyl), benzyl or 2-cyanoethyl or
- --N(R.sub.7 ').sub.2 is pyrrolidino, piperidino, morpholino, piperazino or N'-methylpiperazino,
- each R.sub.7 " is independently hydrogen, methyl, ethyl or 2-hydroxyethyl or
- --N(R.sub.7 ").sub.2 is morpholino, piperidino, piperazino or N'-methylpiperazino,
- each R.sub.8 ' is independently C.sub.1-6 alkyl, n-hydroxy(C.sub.2-3 alkyl), benzyl or 2-cyanoethyl, and
- each R.sub.9 ' is independently methyl, ethyl, propyl or benzyl or
- --N.sup..sym. (R.sub.8 ').sub.2 R.sub.9 ' is pyridinium, pyridinium substituted by 1 or 2 methyl groups or ##STR370## wherein Zo is a direct bond, --CH.sub.2 --, --O--, --S--, --SO--, --SO.sub.2 --, --NH--, --NR.sub.6 -- or --N.sup..sym. (R.sub.6).sub.2 --A.sup..crclbar., and
- R.sub.9 ' is as defined above,
- each R.sub.8 " is independently methyl, ethyl or 2-hydroxyethyl, and each R.sub.9 " is independently methyl, ethyl or benzyl or
- --N.sup..sym. (R.sub.8 ").sub.2 R.sub.9 " is pyridinium, pyridinium substituted by 1 or 2 methyl groups or ##STR371## wherein R.sub.9 ' and Zo are as defined above, each R.sub.13 ' and R.sub.14 ' is independently as defined above,
- R.sub.21 is C.sub.1-12 alkyl;
- C.sub.2-12 alkyl substituted by hydroxy;
- C.sub.3-12 alkyl interrupted by 1 to 3 radicals selected from --NR.sub.7 -- and --N.sup..sym. (R.sub.8).sub.2 --A.sup..crclbar. ;
- --NHCO--CH.sub.2 --Z;
- --CH.sub.2 --CONH--Y.sub.1 --Z;
- --Y.sub.1 --Z;
- ##STR372## wherein R.sub.23 is halo, hydroxy, nitro, C.sub.1-4 alkyl or C.sub.1-4 alkoxy, and
- R.sub.24 and Z' are as defined above,
- wherein
- each R.sub.5 ' is independently hydrogen, methyl or ethyl,
- each R.sub.5 " is independently hydrogen or methyl,
- each R.sub.5a is independently hydrogen or C.sub.1-4 alkyl,
- each R.sub.6 is independently C.sub.1-4 alkyl,
- each Y.sub.1 is independently linear or branched C.sub.1-8 alkylene or linear or branched C.sub.3-8 alkenylene,
- each Y.sub.2 is independently linear or branched C.sub.1-8 alkylene,
- R.sub.7, R.sub.8, R.sub.17, R.sub.19 and Z as defined in claim 18,
- each a is independently 1, 2 or 3,
- each b is independently 2 or 3,
- each m' is independently 2, 3 or 4,
- each n is independently 0, 1 or 2,
- each q is independently 0 or 1,
- each t is independently 1 or 2, and
- each A.sup..crclbar. is independently a non-chromophoric anion,
- with the proviso that when R.sub.1.sup.iv is hydrogen, the compound is in metal-free form.
72 more elements
Dependencies are inferred from the claim text.