GB1596542A

GB1596542A - Pyridone containing azo dyestuffs

Info

Publication number: GB1596542A
Application number: GB4914377A
Authority: GB
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1976-11-30
Filing date: 1977-11-25
Publication date: 1981-08-26
Also published as: FR2381806B1; JPS5369227A; DE2752282A1; IT1090597B; FR2381806A1

Description

(54) PYRIDONE CONTAINING AZO DYESTUFFS (71) We, SANDOZ LTD., of 35 Lichtstrasse, 4002, Basle, Switzerland a Swiss Body Corporate, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The invention relates to basic azo compounds.

The invention provides compounds of formula I,

wherein R is hydrogen or unsubstituted C1-4alkyl, T1 is a radical of formula II,

where R1 and R2, independently, are hydrogen or unsubstituted C1~4alkyl, and As is an anion, T2 is hydrogen, CN, CONR3R4 or-COOR5, where R3 and R4, independently are hydrogen or unsubstituted C1-4 alkyl, and R5 is an unsubstituted C1-4 alkyl, Q1 is hydrogen or unsubstituted C1-20 alkyl, Q2 is hydrogen; C14 alkyl, unsubstituted or mono-substituted by C1~4alkoxy;; or a radical of formula III or IV -(CH2)g-#K1 A# III -(CH2)g-#K2 A# IV wherein AQ is as defined above, g is 2, 3 or 4, and K1 and K2 are as hereinafter defined, n is 1 or 2, and D, in case a), i.e. when n is 1, is D1, where D1, in case aa) is a radical of formula Ia, Ib, Ic or Id,

where a, b, c, e and f, each independently, are integers 1 or 2, d is 0 or 1, ring B bears 0, 1, 2 or 3 substituents, each R6, independently, is hydrogen or unsubstituted C1-4 alkyl, each R7, independently, is hydrogen, halogen or unsubstituted C1-4 alkoxy, each R8, independently, is hydrogen, halogen, NO2, CN or CF3, each R9, independently, is hydrogen, CH3 or C2H5, each R10, independently, is hydrogen, -COOCH3, or-COOC2H5, R12 is hydrogen, halogen, NO2 or unsubstituted C1-4 alkyl, R11 is hydrogen, -OCH3, -OC2H5, -COCH3, -SO2CH3, -SO2C2H5, -CONR13R14, -NHCOR15, -NHCOOR16, -NHCONHR17, -NR18SO2R19 or a radical of formula

where R6 and R8 are as defined above, X is -CO-, -COO- or -SO2-, R13 is hydrogen, CH3 or C2H5, R14 is hydrogen, unsubstituted C1-3 alkyl or a radical (a)

where R6 and R8 are as defined above, R15 and R19 are CH3, C2H5 or a radical (a), above, R16 is CH3 or C2H5, R17 is unsubstituted C1-4 alkyl or a radical (a), above, R18 is C1-4 alkyl, unsubstituted or monosubstituted by phenyl, h is 1 or 2, and i is 3 or 4, and D1, in case ab), is a radical of formula Ix,

where either R20 is hydrogen or unsubstituted C1-20 alkyl, and R21 is hydrogen, unsubstituted C1-20 alkyl, benzyl or phenyl, or R20 and R21, together with the nitrogen atom to which they are attached, form a 5 or 6-membered heterocyclic ring, and each R22, independently, is hydrogen or halogen, with the provisos, in case aa), that Q1 is unsubstituted C5-20 alkyl; and in case ab), that, when R20 and R21 do not form a ring together, the total of non-ring-bound carbon atoms in Q1, R20 and R2, is from 6 to 20 and that at least one Q1, R20 or R21 contains at least 5 carbon atoms, and that, when R20 and R2, form a ring together, then Q1 is unsubstituted C 20 alkyl, or D, in case b), i.e. when n is 2, is D2, D3 or D4, being in case ba), i.e.

when Q2 is a radical of formula III, D2, i.e. a radical of formula Ie,

where R8, a, b and c are as defined above, each R23, independently, is hydrogen or unsubstituted C1-20, alkyl, each R24, independently, is hydrogen or-COOR33, where R33 is unsubstituted C5-20 alkyl, R25 is hydrogen, -OR33, -COR33, -CON(R33)2, -SO2N(R33)2, -SO2R33, -N(Ro)COR34, -NHCOOR35,-NHCONHR36, -N(Ro)SO2R37,

where R8, h and each R33, independently, are as defined above, Y is -O-, -CO-, -COO-, -SO2-, or -CONH-, R34, R35, R36 and R37, independently, being unsubstituted C5-20 alkyl, and Ro being hydrogen or unsubstituted C1-4 alkyl, with the provisos:: i) that ring B1 bears 1, 2 or 3 substituents; ii) that at least one of the R23's, R24s and R25 is other than hydrogen; iii) that, where the R24's and R25 are all hydrogens, then at least one of the R23's is unsubstituted C5-20 alkyl, and iv) that the total sum of carbon atoms in the R23.s, R24.s and R33.s to R37, together, is from 6 to 28, Et, in the radical of formula III, being of formula If, Ig, Ih, Ii or 1k,

wherein each R26, independently, is hydrogen or unsubstituted C1-4 alkyl, k is 0, 1 or 2, R27 and R28, independently are unsubstituted C1-4 alkyl, R29 and R32 are hydrogen or substituted or unsubstituted C1-4 alkyl, either R30 and R31, independently, are hydrogen or substituted or unsubstituted C14 alkyl, or R30 and R31, together with the nitrogen atom to which they are attached, form a heterocyclic ring, in case bb), i.e. when Q2 is a radical of formula IV, D being D3, i.e a radical Il, Im or In

where a, b, c, d, R5 and R,2 are as defined above, each R38, independently is hydrogen or unsubstituted C14 alkyl, each R39, independently, is hydrogen or-COOR44, where R44 is unsubstituted C1-4 alkyl, R40 is hydrogen, -OR44, -COR44, -CON(R44)2, -SO2N(R44)2, -SO2R44, -N(R48)COR45, -NHCOOR45, -NHCONHR45, -N(R48)SO2R45,

where each R44 and R38, independently, h and i are as defined above, each R46, independently, is hydrogen, halogen or unsubstituted C1-4 alkyl, Z is -CO-, -COO-, -CONH- or -SO2-, k is 0, 1 or 2, R47 is hydrogen, Cl or Br, R48 is hydrogen or unsubstituted C1-4 alkyl, R45 is unsubstituted C1-4 alkyl or a radical of formula

where each R38 and R47, independently, and c are as defined above, ring B2 bearing 0, 1, 2 or 3 substituents, K2# in the radical of formula IV, being of formula Io,

where R41, is hydrogen or unsubstituted C1-4 alkyl, each R42 and R43, independently being unsubstituted C1-20 alkyl, at least one of R42 and R43 containing at least 6 carbon atoms, with the proviso that up to a maximum of 25 carbon atoms, in total are contained in R41 to R43, in case bc), i.e. when Q2 is hydrogen or C14 alkyl, unsubstituted or mono-substituted by C14 alkoxy, D being D4, i.e. a radical Ip

where R49 is hydrogen, halogen, NO2, CN, unsubstituted C14 alkoxy or an unsubstituted or substituted C1-4 alkyl, R50 and R51, independently, are unsubstituted or substituted C1-20alkyl, R52 is hydrogen or unsubstituted C1-4 alkyl, and L is a direct bond, or a bridging group of formula *-(CH2)p-OC *-(CH2)m-N(R62)-SO2or *-(CH2)p-CON(R62) m is 1, 2, 3 or 4, p is 1, 2, 3 or 4, R62 is hydrogen or unsubstituted C1-4 alkyl, the asterisk indicates the bond attached to the N# atom, with the proviso that the total number of non-ring-bound carbon atoms in R50, R51 and R52, together, is at least 10 and at most 30, which compounds are free from sulphonic acid groups.

In the compounds of formula I, where R20 and R21, together with the nitrogen atom to which they were attached, form a 5- or 6-membered heterocyclic ring, such ring is preferably a morpholine, pyrrolidine or piperidine ring. Similarly, where R30 and R31 form a ring, such is preferably a morpholine, piperidine or Nmethylpiperazine ring.

Of the unsubstituted or substituted C1-4 alkyls as R29, R32, R49, R30 and R31, the unsubstituted C1-4 alkyls are preferred.

Where R30 or R31, signify substituted C1-4 alkyl, the preferred substituents are phenyl or methyl-, ethyl- or phenyl-carbonyl, mono-substitution being preferred and where the alkyl is substituted by any of the latter three named substituents, the alkyl group is preferably methyl.

Where R50 and R51 signify substituted C1-20 alkyl, the preferred substituent is phenyl, the preferred substituted alkyl as R50 or R51 being benzyl.

Any halogen in the compounds of formula I is preferably chlorine or bromine.

Any alkyl radical or moiety in the compounds of formula I or of any formula hereinafter appearing may be straight or branched chain, unless otherwise stated.

Preferred compounds of the invention are those of formula I'

wherein T1 and n are as defined above, Ra is unsubstituted C1-4 alkyl, Q1' is hydrogen or unsubstituted C1-16 alkyl, Q2' is hydrogen; C1-4 alkyl unsubstituted or mono-substituted by C1-4 alkoxy; or a radical of formula III' or IV' -(CH2)g'-K1#' A# III' -(CH2)g'-K2#' A# IV' where K1'# and K2'# are as hereinafter defined, A# is as above defined, and g' is 2 or 3, and D', in case a), i.e. when n is 1, is D1', where D1', in case aa), is a radical of formula Ia', Ib', Ic' or Id',

where a, b, c, e, R9 and R10 are as defined above, R6a is hydrogen, CH3 or C2H5, R7a is hydrogen, OCH3, OC2H5 or chlorine, R8a is hydrogen, Cl, Br, NO2, CN or CF3, R11a is hydrogen, OCH3, OC2H5, methylcarbonyl, phenylcarbonyl, benzyl, phenoxycarbonyl, -CON R14a R13,-NHCOR15a, -NHCOOR16, -NHCONHR17a, -N(R18a)SO2R19a or radical

where R13 and R16 are as defined above, R14a is hydrogen, CH3, C2H5, phenyl or monochlorophenyl, R15a and R17a are CH3, C2H5, phenyl or monochlorophenyl, R18a is CH3, C2H5 or benzyl, R19a is CH3, C2H5 or phenyl, and ring B1 bears 0, 1, 2 or 3 substituents, and D1', in case ab), is a radical of formula Ix'

where either R20a is hydrogen or unsubstituted C1-16 alkyl, and R21a is hydrogen, unsubstituted C1-16 alkyl, phenyl or benzyl or R20a and R21a, together with the nitrogen atom to which they are attached, form a morpholine, pyrrolidine or piperidine ring, and R22a is hydrogen or chlorine, with the provisos, in case aa), that Q1 is unsubstituted C5-16 alkyl; and in case ab), that, when R20a and R21a do not form a ring with the nitrogen to which they are attached, the total of non-ring-bound carbon atoms in Q1', R20a, and R21a is from 6 to 20 and that at least one of Q1', R20a and R21a is unsubstituted alkyl of at least 5 carbon atoms, and that when R20a and R21a form a ring with said nitrogen, then Q1' is unsubstituted C5-16 alkyl, or D', in case b), i.e. when n is 2, is D2', D3' or D4', being, in case ba), i.e. when Q2' is a radical of formula III', D2', i.e. a radical of formula Ie',

where a, b, c and each R8a, independently, are as defined above, each R23a, independently, is hydrogen or unsubstituted C1-18 alkyl, each R24a, independently, is hydrogen or -COOR33a, where R33a is unsubstituted C5-18 alkyl, R25a is hydrogen, -OR33a, -COR33a, -CON(R33a)2, -SO2N(R33a)2, -N(Ro')COR33a, -NHCOOR33a, -N(Ro')RO2R33a,

where h, R47 and each R33a, independently, are as defined above, Ro' is hydrogen, CH3 C2H5 or n-C3H7, Y' is -O-, -CO-, -COO- or -CONH- with the provisos that ring B1' bears 1, 2 or 3 substituents, that at least one of the R23a's, R24a's and R25a is other than hydrogen, that where the R24a's and R25a are hydrogen, then at least one of the R23a's is unsubstituted C5-18 alkyl, and that the total sum of carbon atoms in the R23a's, R24a's and the R33a's is from 6 to 24.

K1'#, in the radical of formula III', being of formula If', Ig', Ih' or Ii',

where k is as defined above, each R26a, independently, R29a and R32a are hydrogen or unsubstituted C1-4 alkyl, either R30a and R31a, independently, are C1-4 alkyl, unsubstituted or monosubstituted by phenyl; or -CH2-CO-R53, where R53 is CH3, C2H5 or phenyl, or R30a and R31a, together with the nitrogen atom to which they are attached, form a morpholine, piperidine or N-methylpiperazine ring, in case bb), i.e. when Q2' is a radical of formula IV', D' being D3', i.e. a radical of formula Il', Im' or In'.

a, b, c and R8a being as defined above, each R38a, independently, is hydrogen, CH3, C2H5, iso- or n-C3H7, each R38a, independently, is hydrogen or -COOR44a, where R44a is CH3, C2H5, iso- or n-C3H7, R40a is hydrogen, -OR44a, -COR44a, -CON(R44a)2, -SO2N(R44a)2, -N(R48a)COR45a, -NHCOOR45a, -N(R48a)SO2R45a,

where each Ra, independently, R38,,, h, k and i are as defined above, Z' is -COO-- or -CONM-, each R46a, independently, is H, Cl, Br, CH3 or C2Hs, R47a is H or Cl, R45a is CH3, C2H5, iso-C3H7, n-C3H7

where R38a and R47a are as defined above, and R48a is H, CH3 or C2H5, ring B2' bearing 0, 1, 2 or 3 substituents, K2#', in the radical of formula IV', being of formula Io',

where R41a is hydrogen or unsubstituted C1-4 alkyl, R42a and R43a, independently, being unsubstituted C1-20 alkyl, at least one of R42a and R43a containing at least 6 carbon atoms, with the proviso that up to a maximum of 25 carbon atoms, in total, are contained in R41a to R43a, in case bc), i.e.

when Q2' is hydrogen or C1-4 alkyl, unsubstitutend or mono-substituted by C1-4 alkoxy, D' being D4' i.e. a radical Ip',

where R49a is hydrogen, Cl, Br, NO2 or unsubstituted C1-4 alkyl or C1-4alkoxy, R50a and R51a, independently, are unsubstituted C1-20 alkyl or benzyl, R52a is hydrogen or unsubstituted C1-4 alkyl, L1 is a direct bond or a bridging group of formula *-(CH2)p'-OC *-(CH2)m'-N(R62a)SO2or *-(CH2)p'-CONHwhere p' is 1 or 2, m' is 2 or 3, the asterisk indicates the bond attached to the N#, and R62a is hydrogen or unsubstituted C1-4 alkyl, with the proviso that the total number of non-ring-bound carbon atoms in R50a, R51a, and R52a, together, is at least 10 and at most 25.

More preferred compounds of the invention are the compounds of formula I",

where n is as defined above, Rb is CH3, C2H5 or iso-C3H7, Q1" is hydrogen or unsubstituted C1-4 alkyl, Q2" is hydrogen, CH3, C2H5, n- or iso-C3H7, n-C4H9, methoxy-n-propyl or a radical III" or IV", -(CH2)g,-K1#" A# III" -(CH2)g,-K1#" A# IV" where g' and A# are as defined above, and K1#" and K2#" are as defined hereinafter, T1' is a radical of formula II'

where Ao is as defined above, and Ria and R2a, independently, are H, CH3 or C2Hs, and D" in case a), i.e. when n is 1, is D1", where D1", in case aa), is unsubstituted 4-phenylazo-phenyl, unsubstituted naphthyl or, preferably, a radical Ib",

where a, b, c and each R9 and R10, independently, are as defined above, each R8b, independently, is H, Cl, NO2, CN or CF3, R11b is H, OCH3, OC2H5, CONR13R14b, NHCOR15a, -NHCOOR16 or

where R,3, R158 and R16 are as defined above, and R14b is H, CH3, C2H6, or phenyl, and ring B1" bears 0, 1 or 2 substituents and D1", in case ab) is a radical of formula Ix"

where R20b and R21b, independently, are unsubstituted C1-4 alkyl, with the provisos, in case aa), that Q1" is unsubstituted C5-12 alkyl and, in case ab), that the total of carbon atoms in Q1", R20b and R21b is from 6 to 20 and that at least one of the radicals Q1", R20b and R21b contains at least 5 carbon atoms, or D", in case b), i.e.

when n is 2, is D2", D3" or D4", being, in case ba), i.e. when Q2" is a radical of formula III", D2", i.e. a radical of formula Ie",

where a, b, c and each R5 independently, are as defined above, ring Ba" bears 1 or 2 substituents, each R23b, independently, is hydrogen or unsubstituted C1-16 alkyl, each R24b is, independently, hydrogen or -COOR33b, where R33b is unsubstituted C5-16 alkyl, R25b is hydrogen, -OR33b, -CON(R33b)2, -N(Ro")COR33b, -N(Ro")SO2R33b, -SO2N(R33b)2,

where Ro" is hydrogen, CH3 or C2Hs, and each R33b, in dependently, is as defined above, with the provisos, that at least one of the R23b's, R24b's and R25b is other than hydrogen, that where the R24b's and R25b are hydrogen, then at least one of the R23b's is unsubstituted C5-16 alkyl, and that the total sum of carbon atoms in the R23b's, r24b's and the R33b's is from 6 to 24.

K1#" in the radical of formula III", being of formula If" or

where k isas defined above, R29b is H, CH3 or C2H5, and R30b and R31b, independently, are CH3, C2H5, C3H7 or benzyl, in case bb), i.e.

when Q2" is a radical of formula IV", D" being D3" i.e. a radical of formula Il",

where a, b, c and each R8b independently, are as defined above, each R38b, independently, is H, CH3 or C2H5, each R38b, independently, is H or -COOR44b, where R44b is methyl or ethyl, R40b is hydrogen, -OR44b, -CON(R44b)2, -SO2N(R44b)2, -N(R48a)COR45b, -N(R48a)SO2R45b, unsubstituted phenylazo, unsubstituted phenylaminocarbonyl, or a radical

where k, R35a, R47a, R48a, and each R44b, independently, are as defined above, R45b is CH3, C2Hs, C3H7 or phenyl, R46b is hydrogen, Cl or CH3, and ring Bb" bears 0, 1, 2 or 3 substituents, K2#", in the radical of formula IV" being of formula lo"

where R41b is H, CH3 or C2H5, and R42b and R43b, independently, are unsubstituted C1-20 alkyl, at least one of R42b and R43b containing at least 6 carbon atoms, with the proviso that up to a maximum of 18 carbon atoms are contained in R41b to R43b, in case bc), i.e. when Q2" is H, CH3, C2H5, n or iso-C3H7, n-C4H9 or methoxy-n-propyl, D" being D4", i.e. a radical of formula Ip",

where R49b is H or Cl, Raob and Rs1b, independently, are unsubstituted C1-18 alkyl, L2 is a direct bond or a bridging group of formula *-(CH2)p'OCor *-(CH2)m,-NHSO2-, the asterisk, p' and m' being as above defined, and R52b is H or CH3, with the proviso that the total number of carbon atoms in R50b, R51b and R52b is at least 10 and at most 25.

Of the case aa) compounds are particularly preferred the compounds of formula XII,

wherein R9 and A# are as defined above, R1b and R2b, independently, are hydrogen or methyl, Q1'" is an unsubstituted C6-10 alkyl, R8c is hydrogen, NO2, Cl or CF3, R11c is hydrogen or -NHCOR15b, where R15b is methyl, ethyl or phenyl, and ring B3 bears 0, 1 or 2 substituents.

Of the case ab) compounds are particularly preferred, the compounds of formulae XIII, XIV and XV,

where A#, R1b and R2b are as defined above, R20c and R21c, independently, are unsubstituted C4-10 alkyl, with the proviso that at least one of R20c and R21c contains at least 5 carbon atoms,

wherein R1b, R2b and A# are as defined above, and Q1iv is unsubstituted C8-14 alkyl,

wherein R1b, R2b and R# are as defined above, R20e and R21e, independently, are unsubstituted C2-5 alkyl, and Q1v is unsubstituted C4-8 alkyl, with the proviso that at least one of Q1v, R20e and R21e contains at least 5 carbon atoms.

Of the case ba) compounds are particularly preferred the compounds of formula XVI,

where A#, Rac and c are as defined above, ring B1'" bears 1 or 2 substituents, R23c is H or unsubstituted C1-12 alkyl, each R24c, independently, is H or -COOR33c, where R33c is unsubstituted C5-12alkyl, R25c is H, -OR33c, -CON(R33c)2, -SO2N(R33c)2, -N(Ro'")COR33c or -N(Ro'")-SO2R33c, where each R33c, independently, is as defined above, Ro'" is H or CH3, with the provisos that at least one of R23c, the R24c's and R25c is other than hydrogen, that when the R24c's and R25c are hydrogen then R23c contains at least 5 carbon atoms, and that the total sum of carbon atoms in R23c, the R24c's and R25c is from 6 to 20.

Of the case bb) compounds are particularly preferred the compounds of formula XVII,

where A#, R8c and c are as defined above, ring B2"' bears 0, 1 or 2 substituents, R38c is H or CH3, each R39c, independently, is H or -COOCH3, R40c is hydrogen, unsubstituted phenylazo, -CON(CH3)2 or - SO2N(CH3)2, R41c is H or CH3, R42c and R43c, independently are unsubstituted C1-16 alkyl, at least one of R42c and R43c containing at least 6 carbon atoms, with the proviso that the total number of carbon atoms in R41c, R42c and R43c is at most 18.

Of the case bc) compounds are particularly preferred the compounds of formula XVIII,

where A#, R50b, R51b and R52b are as defined above, and Q2"' is CH3, C2H5, n- or iso-C3H7, n-C4H9 or 3-methoxy-n-propyl, with the proviso that the total number of carbon atoms in R50b, R51b and R52b, together, is from 16 to 25.

In the compounds of the invention, the exact nature of the anion AO is not critical and it may be any conventional in the basic dye art. The anion is, however, preferably non-chromophoric. It may be organic or inorganic and as examples may be given the halide, e.g. chloride or bromide, sulphate, bisulphate, methylsulphate, aminosulphonate, perchlorate, benzenesulphonate, oxalate, maleinate, acetate, propionate, lactate, succinate, tartrate, malate, methanesulphonate and benzoate anions, complex anions such as those of zinc chloride double salts, and the anions of the following acids, boric, citric glycolic, diglycolic and adipic and of addition products of ortho-boric acid and polyols, e.g. cis polyols.

In the compounds of formula I, the following, each independently of the others, are the preferred significances of the substituents, the symbol > meaning preferably, meaning more preferably and > most preferably.

R > Ra > > Rb > > > CH3. T1 > T1' > > a radical II' where R1a is R1b and R2a is R2b.

R1 > R1a > > R1b. R2 > R2a > > R2b. g > g' > > 3. R6 > R6a > > H. R7 > R7a > > H.

R8 > R8a > > R8b > > > R8c. R11 > R11a > > R11b > > > R11c. R12 > H. R14 > R14a > > R14b.

R15 > R15a. R17 > R17a. R18 > R18a. R19 > R19a. R20 > R20a > > R20b > > > R20c.

R21 > R21a > > R21b > > > R21c. R22 > R22a > > H. R23 > R23a > > R23b > > > R23c.

R24 > R24a > > 24b > > > R24c. R25 > R25a > > R25b > > > R25c. R26 > R26a > > CH3. R27 > CH3.

R28 > CH3. R29 > R29a > > R29b > > > CH3. R330 > R30a > > R30b > > > CH3.

R31 > R31a > > R31b > > > CH3. R32 > R32a. R33 > R33a > > R33b > > > R33c.

Ro > Ro' > > Ro" > > > Ro"'. R38 > R38a > > R38b > > > R38c. R39 > R39a > > R39b > > > R39c.

R40 > R40a > > R40b > > > 40c. R41 > R41a > > R41b > > > R41c. R42 > R42a > > R42b > > > R42c.

R43 > R43a > > 43b > > > R43c. R45 > R45a > > R45b. R46 > R46a > > R46b. R47 > R47a > > H.

R48 > R48a. R49 > R49a > > R49b > > > H. R50 > R50a > > R50b. R51 > 51a > > R51b.

R52 > R52a > > R52b. R62 > R62a > > H. a > 1. d > 0. e > 1. f > 1. h > 1. i > 3. p > p' > > one. m > m'.

k1 > k1' > > k1" > > > N(CH3)3. K2 > K2' > > K2" > > > NR41cR42cR43c.

Where R is alkyl, it is preferably CH3, C2H5 or n-C3H7, particularly CH3.

Where R1 and R2 are alkyl, they are preferably CH3 or C2H5, particularly CH3.

Where R5 is alkyl, it is preferably CH3 or C2Hs.

Where R7 is halogen, it is preferably chlorine.

Where R7 is alkoxy, it is preferably OCH3 or OC2Hs.

Where R5 is halogen, it is preferably chlorine or bromine, particularly chlorine.

Where R14, R17 or R18 are alkyl they are preferably methyl or ethyl.

Where R18 is substituted alkyl, it is preferably benzyl.

Where R20 and R21 are alkyl, they are preferably C1-16 alkyl more preferably C1-14 alkyl, and most preferably C4-10 alkyl, C2-5 alkyl or methyl.

Where R22 is halogen, it is preferably chlorine.

Where R23 is alkyl, it is preferably C1-18, more preferably C1-16, and most preferably C1-12, alkyl.

Where R26, R27 and R28 are alkyl, they are preferably methyl.

Where R29 is alkyl, it is preferably CH3 or C2H5, more preferably CH3.

Where R30 and R31 are unsubstituted alkyl, they are preferably CH3, C2H5 or C3H7, more preferably CH3.

Where R30 and R31 are substituted alkyl, they are preferably CH2COCH3, CH2COC2H5, phenylcarbonylmethyl or benzyl, more preferably benzyl.

Where R33 is alkyl, it is preferably C5-18, more preferably C5-16 and most preferably C5-12 alkyl.

Where Ro is alkyl it is preferably CH3, C2H5 or n-C3H7, more preferably CH3 or C2H5 and most preferably CH3.

Where R38 or R44 is alkyl, it is preferably CH3, C2H5, iso-C3H7 or n-C3H7, more preferably CH3 or C2H5 and most preferably CH3.

Where R41 is alkyl, it is preferably CH3 or C2H5, more preferably CH3.

Where R42 and R43 are alkyl, they are preferably C1-20, more preferably C1-16, alkyl.

Where R45 is alkyl, it is preferably CH3, C2H5, iso- or n-C3H7.

Where R46 is alkyl, it is preferably CH3, or C2H5, more preferably CH3.

Where R48 is alkyl, it is preferably CH3, or C2H5.

Where R50 and R51 are unsubstituted alkyl, they are preferably C1-18 alkyl.

Where R50 and R51 are substituted alkyl, they are preferably benzyl.

Where R52 is alkyl, it is preferably methyl.

Where Q1 is alkyl, it is preferably C1-16 alkyl, more preferably C1-14alkyl, especially C6-10, C8-14 or C4-8 alkyl.

Where Q2 is unsubstituted alkyl, it is preferably CH3, C2H5, n- or iso-C3H7 or n C4H9.

Where Q2 is alkoxyalkyl, it is preferably 3-methoxy-n-propyl.

D1, in case aa), is preferably of formula Ia', Ib', Ic' or Id', more preferably unsubstituted 4-phenylazo-phenyl, unsubstituted naphthyl, or a radical Ib", most preferably the diazo component radical given in formula XII.

D1, in case ab), is preferably a radical of formula Ix', more preferably a radical of formula Ix" and most preferably one of the diazo component radicals given in formula XIII, XIV or XV.

D2, in case ba), is preferably D2,, more preferably D2" and most preferably the diazo component radical given in formula XVI.

D3, in case bb), is preferably D3,, more preferably D3,, and most preferably the diazo component radical given in formula XVII.

D4, in case bc), is preferably D4,, more preferably D4,, and most preferably the diazo component radical given in formula XVIII.

The invention also provides a process for the production of compounds of formula I, stated above, comprising coupling a diazo derivative of an amine of formula D-NH2, where D is as defined above, with a coupling component of formula XIX,

The process may be carried out in conventional manner, e.g. in aqueous or aqueous/organic, acid, neutral or alkaline medium at a temperature from -10 C to room temperature, optionally in the presence of a coupling accelerator, e.g.

pyridine or urea.

The amines D-NH2 and the compounds of formula XIX are either known or may be obtained from available starting materials in analogous manner to the known compounds.

The resulting compounds of formula I may be isolated and purified in conventional manner, optionally any anion As present in the compound resulting from the reaction being exchanged for another anion, as desired, in conventional manner, e.g. using an ion exchanger or by treatment with acids or salts.

The compounds of the invention are basic dyestuffs and are useful for the dyeing or printing of cationic dyeable substrates, e.g. substrates of homo and mixed polymers of acrylonitrile or asymmetric dicyanoethylene, acid modified synthetic polyamide (e.g. as described in Belgian Patent Specification No. 706,104), acid modified polyester (e.g. as described in U.S.P. 3,379,723), plastics in the mass, leather and paper.

The compounds, if desired, can be formulated into dye preparations, e.g.

stable liquid or solid preparations, in conventional manner, e.g. by grinding or granulating with optional dissolution in solvents, optionally employing assistants, e.g. stabilisers or solubility aids such as urea. Such preparations can, for example, be produced as described in French Patents 1,572,030 and 1,581,900 or in German Published Specification Nos. 2,001,748 and 2,001,816.

The dyeing or printing may be carried out in conventional manner, e.g. the dyeing of textiles advantageously in aqueous, neutral or acid media at from 600C to boiling point or at temperatures over 100"C under pressure. Dyeing from organic media, e.g. as described in German Published Specification No. 2,437,549, may also be carried out.

The dyeings obtained have notably good light fastness. The dyes are well combinable with other basic dyes, the Combination Value (K-value) of the compounds depending on the number of carbon atoms in the alkyl radicals contained therein, enabling appropriate choice of compound for combination with other basic dyes.

The dyes exhaust well and the dyeings have notable fastness to washing, sublimation, perspiration, pleating, decatising, ironing, water, sea water, dry cleaning, overdyeing and to solvents. The dyes show resistance to hydrolysis, have good water-solubility and give deep even dyeings.

The invention is further illustrated by the following Examples in which all parts and percentages are by weight and the temperatures are in degrees centigrade.

Example 1 17 parts of 2-nitro-4-methoxy-aniline are diazotised at 05 with sodium nitrite by a known process, in an aqueous hydrochloric acid solution. The excess nitrous acid is decomposed using amidosulphonic acid. The clear-filtered diazonium chloride solution is added dropwise over the course of half an hour at 05 to a suspension of 39 parts of N-decyl-6-hydroxy-4-methyl-pyridonyl-(3)-pyridinium chloride in 300 parts of water. The dyestuff suspension is set at a pH value of 10.5 using caustic soda, and the precipitated dyestuff is filtered off, washed with water and dried. The dyestuff thus obtained corresponds in the salt form to formula

and from an acetic acid solution dyes polyacrylonitrile in fast yellow shades.

Dyeing Formula A 20 parts of the dyestuff described in Example 1 and 80 parts of dextrin are ground for 4 hours in a powder mill. The same dyestuff mixture is similarly obtained by making a paste with 100 parts of water, followed by spray-drying. 1 part of the preparation thus obtained is made into a paste with 1 part of 40% acetic acid, the pul,F(is covered by 200 parts of demineralised water and boiled for a short time.

There is dilution with 7000 parts of demineralised water, then 2 parts of glacial acetic acid are added, and the solution is entered into the bath at 600, together with 100 parts of polyacrylonitrile fabric. The material may be pre-treated for 1W15 minutes at 600 in a bath containing 8000 parts of water and 2 parts of glacial acetic acid.

Heating takes place over the course of 30 minutes to 98100 , then boiling for 1+ hours and rinsing. A yellow dyeing is obtained with good light fastness and good wet fastness.

10 parts of the dyestuff mentioned in Example 1 may also be dissolved in 60 parts of glacial acetic acid and 30 parts of water. A stable, concentrated solution of the dyestuff is obtained with a dyestuff content of about 10 ,o, which may be used in accordance with the above dyeing formula for dyeing polyacrylonitrile.

Dyeing Formula B 20 parts of the dyestuff from Example 1 are mixed in -a ball mill for 48 hours with 80 parts of dextrin; 1 part of the preparation thus obtained is made into a paste with I part of 40% acetic acid, the pulp is covered with 200 parts of demineralised water and boiled for a short time. Dyeing takes place as follows using this stem solution: a) It is diluted with 7000 parts of demineralised water, then 21 parts of calcined sodium sulphate are added, as well as 14 parts of ammonium sulphate, 14 parts of formic acid and 15 parts of a carrier based on the reaction products of ethylene oxide with dichlorophenols, and the solution is entered into the bath at 60 with 100 parts of polyester fabric which is modified by acid groups.The material may be pretreated for 1015 minutes at 60 in a bath containing 8000 parts of water and 2 parts of glacial acetic acid.

The bath is heated over the course of 30 minutes to 98100 , then boiled for one hour and rinsed. An even, yellow dyeing is obtained with good wet fastness.

b) It is diluted with 3000 parts of demineralised water, then 18 parts of calcined sodium sulphate are added, as well as 6 parts each of ammonium sulphate and formic acid, and the solution is entered into the bath at 600 with 100 parts of polyester fabric which is modified by acid groups. This is heated in a closed container over the course of 45 minutes to 1100, this temperature is maintained with shaking for 1 hour, it is then cooled over the course of 25 minutes to 600, and the dyed goods are rinsed. An even yellow dyeing is obtained with good wet fastness.

c) The procedure is as for b), but the closed container is heated for 1 hour at 1200.

Dyeing Formula C 20 parts of the dyestuff from example 1 are mixed in a ball mill for 48 hours with 80 parts of dextrin.

1 part of the preparation thus obtained is made into a paste with 1 part of 400o acetic acid, the pulp is covered with 200 parts of demineralised water and boiled for a short time. This solution is added to the dye liquor which is prepared as follows.

The solution is diluted with 700 parts of demineralised water, then 21 parts of calcined sodium sulphate are added. as well as 14 parts of ammonium sulphate, 14 parts of formic acid and 15 parts of a carrier based on the reaction product of ethylene oxide with dichlorophenols, and the liquor is buffered to a pH of 6 with an acidic buffering solution, and then 100 arts of polyamide fabric which is modified by anionic groups are entered at 250 with this solution into the bath, in a liquor ratio of 1:80. The bath is heated over the course of 45 minutes to 980, boiled for one hour and rinsed in running water at 7080 and then in cold water. The fabric may be centrifuged so as to dry it. and then ironed. A yellow dyeing is obtained with good fastness properties.

In the following Table I is given the structure of further dyestuffs. which may be obtained as described in Example 1. They correspond to formula

wherein D, R, R1, R2 and Q, have the definitions given in the columns. The numbers given in the definition of R1 and R2 indicate the positions of the radicals R1 and R2 in the pyridinium ring. The symbol X given in the Q1 column represents corresponding examples with Q1 defined as in Examples 2-9.

The anion As may be those listed in the description.

Table I

Ex. D R R1 R2 Q1 No. 2 ~ CH3H H CloH21 3 do. do. H H C12I125 4 do. do. H H C141 29 5 do. do. H H CgH17 6 do. do. H H CgHl9 X 7 do. do H H CllH23 8 do. do. H H C13H27 9 do. do. H H -CHZ-CH-(CH2)3CH3 C2H5 10 do. do. H 4 -CH3 C, OI21 11 do. do. H 2-CH3 do. 12 do. do. 2-C133 4 -CH3 C8H17 13 do. C2H5 H H do. 14 do. C3H7 H H do. 15 do. C113 4-tert. H do. Butyl 16 do. do. 3-Cu3 4-CH3 do. 17 do. do. do. 5-CEl3 do. po, 3 18 > do. H H X 19 do. do. H li H C16H33 20 do. do. H H C18 H37 21 do. do. H H C6H13

Table I (contd.)

Ex.

No. D R R1 R2 C-- I L 1 22 t CH3 H H C7 H15 23 do. do. H 2-CH3 C121125 24 do. do. Ii 4 -CH3 do.

25 do. C3 H7 H H C10H21 26 do. CH3 H H C20H41 27 02b- do. H H X 28 Q2Ne do. H H X 2 29 C1 do. H H X 30 > do. H H X 31 C1 do. H H X 32 do. do. 4 -CH3 H CloH Cl 33 C14 do. do. H do.

34 do. do. H H X 35 do. do. H H C7H15 36 do. do. H H C61113 37 do. H H x C1 38 do. do. 4-Cl'4 H C81117 Cm cm 39 do. H 11 do.

I C1 40 Cl | C1 CH3 H H X Table I (contd.)

Ex.

No. D R R1 R2 Q1 41 C do. H H cur17 42 C1 C1 do. H H C7H15 43 do, do, H H r R ~6"13 CF3 44 Cl do. H H X 45 BreN do. H H CioH21 46 S do. H H X 47 do. H. H C12H25 48 NC do. H H do.

49 F3 do. B H x CF, I so do do. H H X 51 F3C do. H H do.

NO2 52 Cll do . H H X 53 02N4Cl do. H I H X 54 Cl 55 t CH3 H H C1OHZ1 do. do. H H C8 1117 56 L) 02N C1 do . H H CloH2 1 Table I (contd.)

D R R1 R2 Q1 D R R1 I R, O 57 do. do. H H C8H1 8 17 H r7 do. H H X 58 8 H13l3CcOoX do 59 do do. H H X OCH 60 3 0 do. H H X NO2 61 H3COO do. H H X except 62 H C10H21 62 25 H do. H H X 63 H5C2 do. H H X CN 64 C14 do . H H C10ll21 65 H3Ce do. H H X do. do. 4-CH3 H C12 H25 66 H3C 67 do do. H H C101321 68 CH3 o do. H H do.

69 5 2 do. H 11 do.

Cl 70 H3CWH3 CH3 H H x 71 CH3 C 1402 do. H H X N02 72 H3C do. H H X 02N 73 H3Cb do. H H X 7 4 2 b do. H B X C133 Table I (contd.)

D h. R R1 R2 NO 2 75 do. H H C10H21 CH CM3 76 - do. H H do.

NO, 1 COOCH3 77 OOCH3 do. H H X 78 COOC2H5 do. H H x H COOC 79 3 t > ~ do, H H C1oH21 H3COOC do. H H x 80 81 H5C200Ce do . H H X 82 COUCH do. I H H x COOCH, I 6cC0082H5 83 do. do . H H C8H17 COOC H 84 H3COC CH3 H H X 85 bOCe do. H H C6H13 86 CH2 do. H H X 87 do do. II H C6H13 88 do. do . H H X 89 do. do. H H C51311 90 do. do. H H C6H13 91 CleO-COe do. H H do.

9 2 eO-COe do . H H do. Table I (contd.)

r D D R R1 R2 93 CU300C ~ do. > do. H H X CH,OOC H5C200C 94 > do. H H X H5C200C 95 W do. H H X 96 do. H H X 97 > do. H H X 98 OO-N=N -N---N &commat; do. H H X CH 99 N--N 4 do. H H C6H13 CII 100 3XN-Co &commat; do. H H X C113 101 b S 2 b do. H H X 102 CH; S020 CH3 H H X 103 do. do. H H C16H33 104 oN-S02 1 do. H H do.

CH3 105 do. do. H H X 106 v NH-CO e do. H H X 107 3xN~so + do. H H C12H25 CH3 Cl 108 CH3-CO-NH do. H H x 109 H3-0-CO-NH &commat; do. H H C12H25 110 H3 -NH-C0-NII do. H H do. Table I (contd.)

D :x. R | R1 R2 2 Q No. 1 111 SSO2 N do. H H C6H13 CH2 112 SO2-N do. H H C8H17 CH3 113 C1H2-CH do. H B X CH2-C 0 SO2-N0 do. H H C5H11 114 CH2 115 (C10II21)2N-SO2 CH-3 H H H 116 (C5H11)2N-SO2 do. do. H H H C1 117 ( 5 11)2 2 + do. H / H H 118 do. do. H H C6H13 do. do. H H C8H17 120 (C5Hll)2N S02 e do. H H CioH21 121 (C2H5)2N-SO2 do. H H C12H25 122 IJ SO do. H H C6H13 123 09 -SO &commat; do. H H C8H17 124 H13C6-N- SO2 do. H H C5H11 4 2 Example 125 26.5 parts of 2-nitro-4-(2'-ethyl)-hexyloxy-aniline are diazotised as usual at 0 to 5 by a sodium nitrite solution, in an aqueous, hydrochloric acid solution, with glacial acetic acid being added. The excess nitrous acid is decomposed with amidosulphonic acid. The clear-filtered, cold diazonium chloride solution is added in drops over the course of one hour at 0 to 50 to a solution of 38 parts of I - (3' N'N'N' - trimethylammonium - propyl) - 2 - keto - 3 - cyano - 4 - methyl - 6 hydroxy - 1,2 - dihydropyridine - methylsulphate in 500 parts of water. After coupling has ended, the dyestuff is precipitated with sodium chloride, washed and dried.The dyestuff obtained corresponds to formula

and dyes polyacrylonitrile fabric in fast, yellow shades, from an acetic acid solution.

In the following Table II is given the structure of further dyestuffs, which may be obtained as described in Example 1. They correspond to formula

wherein D, R, T2, Ks and g have the definitions given in Table II. The anion AO may be those listed in the description. The symbol K# may represent any of the significances given for K# in Table A.

K# may represent the symbols K1 to K15, whereby K1 to K15 signify the following groups:

T a b l e II

No. D R T2 g C52H5 NO2 126 CH3-(CH2)3-CH-CH2-O CH3 CN 3 2-12,13,15 127 do. do. do. 2 1,2,4,5,10 14 128 do. C2H5 do. 3 1 129 do. CH3 CONH2 3 4 NO2 130 CloH21-O do. CN 3 1,2 NO2 131 C12H25-O do. do. 3 1,9 NO 2 132 C8H17-O do. do. 3 1-5 133 do. do. do. 2 1-5 NO2 134 Cm 19 4 do. do. 3 10 NO2 135 C5H11 4 do. do. 3 4 136 Clo 21 C10H21-O do. do. 3 1,2 137 CioH21-OFC1 do. do. 3 1,2,4,5 138 C10H21-O do. do. 3 2 C1 C52H5 NO2 139 CH3- (CH2) 3-CH-CH2O do. do. 3 1,2 140 C12H25 &commat; CH3 CN 3 1 NO 2 141 C12H25 4 do. do. 3 1,2 Table II (contd.)

Ex. D R | T2 g No. K C 12 25 142 do. do. 0 C00C,qH29 143 H29 143 J do. do. 2 1 144 C10H2100C do. do. do. 3 2,4 145 ClOH21OOC e do. do. 3 1,2,3,5,6,12 146 C14 29 or C14H29OOC do. do. 3 2 147 C8H17OOC do. do. 3 1 COOC5Hll 148 + do. do. 3 1,2,3,5,6, COOC5Hll 9,12 5 11 149 > do. do. 3 1,2,3,5,6,12 COOC6H13 13 COOC H 150 + OOC8H17 do. do. 3 1,2 COOC8H17 151 8 17 e C8H170 do. do. 3 1,2,3 152 8 17 CSH17- 9 CH3 CN 3 1,2,3 153 12 25 cho C12H25-CO do. do. 3 1,2,8 154 C8H17 e OC do. do. 3 1,2 155 C8H17 > NCO do. do. 3 1,2,4 C8H17 Table II (contd.)

Ex.

No. D | R T2 g K C10H21 156 C10H21 do. do, 3 1,2,4 C10H21 157 C12H25-S 2 do. do. 3 1,2 Cl 158 uN-SO2 + do. do. 3 1,2 C5H Cl 11 H13C6 0OC 159 > do. do. 3 1,2,3,5, H13C60OC 6,12 H17CO 160 > do. do. 3 1,2,3,5, H17C8 C 6,12 161 do. do. do. 2 1,2,3,5, 6.12 162 C8H17 no &commat; do. do. 3 1,2,4 163 CsH1,-CO-N do. do. 3 1,2,4 CH3 164 C10H21-C0-1c}{ do. do. 3 1,2,4 165 C10H21-O-C0-NH do. do. do. 3 1,4 166 C12H25 -NH-CO-NH CH3 CN 3 4 167 C10H21-SO2-NH do. do. 3 1,4 168 C10H21- SO2-N, do. do. 3 1,4 CH3 Example 169 14 parts of 2-nitroaniline are diazotised with sodium nitrite as usual at 0-5 in aqueous, hydrochloric form. The excess nitrous acid is decomposed with amidosulphonic acid and the diazonium salt solution is filtered until clear. The clear, yellow solution thus obtained is added in drops at 0-5 over the course of 60 minutes to a yellow solution of 50 parts of 1 - (3' - N' - methyl - N',N' - dioctyl ammonium - propyl) - 2 - keto - 3 - cyano - 4 - methyl - 6 - hydroxy - 1,2 dihydropyridine - chloride in 600 parts of 25 ó aqueous acetic acid. After coupling, the dyestuff is salted out with sodium chloride, filtered, washed with water and vacuum dried. The dyestuff obtained corresponds to formula

and dyes polyacrylonitrile fabric in fast, yellow shades.

In the following Table III is given the structure of further dyestuffs, which may be obtained as described in Example 171. They correspond to formula

wherein D, R, T2, K# and g have the definitions given in Table III. The anion A# may be those listed in the description. The symbol K# may represent any of the significances given for K# in Table B.

K# may represent the symbols K1 to K12, whereby K1 to K12 signify the following groups: TABLE B

CH3 CH3 K, is --ONN-C,H,, K7 do. --ONN-C,H,, CaM17 C7H,s CH3 CH3 K2 do. sNCroH21 K8 do. eNC,8H33 C10H2, CH3 CH3 H K3 do. -N-CaMi3 K8 do. NCi2H28 Cams3 CH3 H CH3 K4 do. --ONN-C,H,, K10 do. -N-C5H17 C8H17 CH3 H CH3 K5 do. sNC10H2' K11 is NC 14H29 C10H21 C3M5 H H Ka do. sNC12H25 K12 do. NC20H41 C12H2s CH3 T a b l e III

Ex. D R T2 g No.

CH3 CH3 CN 3 1 - 11 do. do. do. 2 9 NO2 do. do. 3 2 - 11 C1 do. do. 3 2 - 11 C1 3 W 1 do. do. 3 1,3,6,9,10, Cl do. do. 3 1,2,3,4,9 C1 CN ss C2H5 do. 3 3,5 (i CH3 CON(CH3)2 3 2 COOCH3 do. CN 3 1 - 5 COUCH do. do. 3 1,4 COOCH3 CH3-C0 do. do. do. 3 4,5 CH2 CH2 &commat; do. do. 3 1,3 do. do. 3 3 (CH3)2N-C &commat; do. do. 3 8,9 (CH3)2N-S02- do. do. do. 3 2,8 CH3-SO2 do. do. 3 2,12 CH3 2 CH3 CN 3 1,2,4,5,6,11 NO do, do, 2 P do do. 3 do.

NO do. do. 2 H3C do. do. 3 1,2,4,5,6,9,10 Table III (contd.)

- Ex. D R T2 g K No.

CH3-CO-NH &commat; do. do. 3 1,2,3 CH3O-CO-NH < - do. do. 3 2 CH3-NH-cO-IMH &commat; do do. 3 1,2,3 SO,-N-( S 2 N e do. do. 3 3 CH2 CH2CH2\ I -CO / N(O)- do. do. 3 1,2,3 CH2-CO do. do. 3 1,2,3 do. do. 33 CH3-S02-N8 do. do. 3 1,2 CH3 Example 197 42.5 parts of 4' - amino - - dioctylmethylammonium acetophenonchloride are diazotised at W5 with sodium nitrite, in an aqueous, hydrochloric acid solution.The excess nitrous acid is decomposed with amidosulphonic acid and the solution is filtered until clear. The diazonium salt solution is added in drops over the course of 45 minutes to a solution of 18.5 parts of 1 - ethyl - 2 - keto - 3 - cyano - 4 - methyl - 6 - hydroxy - 1,2 dihydropyridine in aqueous acetic acid. After coupling, the dyestuff is precipitated with sodium chloride, filtered off, washed and vacuum dried. The dyestuff obtained corresponds to formula

and dyes polyacrylonitrile fabric in fast yellow shades.

In the following Table IV is given the structure of further dyestuffs, which may be obtained as described in Example 197. They correspond to formula

wherein R, T2, Q2, R49 Z# and Y have the definitions given in Table IV. The anion A# may be those listed in the description. The number in brackets given in column Y represents the position of Y in ring B. The symbol Z# may represent any of the significances given for Z# in Table C.

Table C

Table D In the following Table D the Y's in formula (a) are specified.

No. 1 -CH2-CO No. 2 CH2 -CO-NH No. 3 -CH2-CH2-NH-SO2 No. 4 -(-CH2)3-NH-SO2 No. 5 -CH2-CH2-CO- No. 6 a direct bond No. 7 -(CH2)2-CO-NH

Ex.

No. R T2 | Q2 R49 Y-Nr Z#-Nr 198 CH3 CN C2H5 H (4)1 2-10 199 do. do. do. Cl (4)1 1-10 200 do. do. do. Br (4)1 4 201 C3H9 do. do. H (4)1 3 202 CH3 CONH2 H Cl (4)1 2 203 do. CN C2H5 H (4)5 1,2 204 do. do. do. H (4)2 2 205 do. do. do. H (4)3 3 206 do. do. do. Cl (5)3 3 207 do. do. do. do. (4)4 1 208 do. do. do. H (3)6 1 209 do. do. do. H (4)7 1 The dyestuffs of Examples 2 to 209 dye polyacrylonitrile in greenish-yellow to reddish-yellow shades.

WHAT WE CLAIM IS: 1. A compound of formula I,

wherein R is hydrogen or unsubstituted C14 alkyl, T1 is a radical of formula II,

where R1 and R2, independently, are hydrogen or unsubstituted C1-4 alkyl, and As is an anion, T2 is hydrogen, CN, CONR3R4 or -COOR5, where R3 and R4, independently, are hydrogen or unsubstituted C1-4 alkyl, and R5 is an unsubstituted C1-4 alkyl, Q, is hydrogen or unsubstituted C1-20 alkyl, Q2 is hydrogen; C1-4 alkyl, unsubstituted or monosubstituted by C1-4 alkoxy; or a radical of formula III or IV -(CH2)g-#K1 A# III -(CH2)g-#K2 A# IV

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. Table D In the following Table D the Y's in formula (a) are specified. No. 1 -CH2-CO No. 2 CH2 -CO-NH No. 3 -CH2-CH2-NH-SO2 No. 4 -(-CH2)3-NH-SO2 No. 5 -CH2-CH2-CO- No. 6 a direct bond No. 7 -(CH2)2-CO-NH Ex. No. R T2 | Q2 R49 Y-Nr Z#-Nr 198 CH3 CN C2H5 H (4)1 2-10 199 do. do. do. Cl (4)1 1-10 200 do. do. do. Br (4)1 4 201 C3H9 do. do. H (4)1 3 202 CH3 CONH2 H Cl (4)1 2 203 do. CN C2H5 H (4)5 1,2 204 do. do. do. H (4)2 2 205 do. do. do. H (4)3 3 206 do. do. do. Cl (5)3 3 207 do. do. do. do. (4)4 1 208 do. do. do. H (3)6 1 209 do. do. do. H (4)7 1 The dyestuffs of Examples 2 to 209 dye polyacrylonitrile in greenish-yellow to reddish-yellow shades. WHAT WE CLAIM IS:

1. A compound of formula I,

wherein As is as defined above, g is 2, 3 or 4, and K1 and K3 are as hereinafter defined, n is 1 or 2, and D, in case a), i.e. when n is l, is D1, where D1, in case aa) is a radical of formula Ia, Ib, Ic or Id,

where a, b, c, e and f, each independently, are integers 1 or 2, d is 0 or 1, ring B bears 0, 1, 2 or 3 substituents, each R6, independently, is hydrogen or unsubstituted C1-4 alkyl, each R7, independently, is hydrogen, halogen or unsubstituted C1-4 alkoxy, each R8, independently, is hydrogen, halogen NO2, CN or CF3, each R9, independently, is hydrogen, CH3 or C2Hs, each R10, independently, is hydrogen, -COOCH3 or -COOC2H5, R12 is hydrogen, halogen, NO2 or unsubstituted C1~4 alkyl, R11 is hydrogen, -OCH3, -OC2H5, -COCH3, -SO2CH3, -SO2C2H5, -CONR13R14, -NHCOR15, -NHCOOR16, -NHCONHR17, -NR18SO2R19 or a radical of formula

where R6 and R5 are as defined above, X is -CO-, -COO- or -SO2-, R13 is hydrogen, CH3 or C2H5, R14 is hydrogen, unsubstituted C1-3 alkyl or a radical (a)

where R5 and R5 are as defined above, R15 and R19 are CH3, C2H5, or a radical (a), above, R.6 is CH3 or C2H5, R,7 is unsubstituted C1-4 alkyl or a radical (a) above, R18 is C1-4 alkyl, unsubstituted or monosubstituted by phenyl, h is 1 or 2, and i is 3 or 4, and D1, in case ab), is a radical of formula Ix,

where either R20 is hydrogen or unsubstituted C1~20 alkyl, and R21 is hydrogen, unsubstituted C1~20 alkyl, benzyl or phenyl, or R20 and R21, together with the nitrogen atom to which they are attached, form a 5 or 6-membered heterocyclic ring, and each R22, independently, is hydrogen or halogen, with the provisos, in case aa), that Q1 is unsubstituted C5-20 alkyl; and in case ab) that, when R20 and R21 do not form a ring togther, the total of non-ring-bound carbon atoms in Q1, R20 and R21 is from 6 to 20 and that at least one of Q1, R20 or R21, contains at least 5 carbon atoms, and that, when R20 and R21 form a ring together, then Q1 is unsubstituted C5-20 alkyl, or D, in case b), i.e. when n is 2, is D2, D3 or D4, being, in case ba), i.e. when Q2 is a radical of formula III, D2, i.e. a radical of formula Ie,

where R8, a, b and c are as defined above, each R23, independently, is hydrogen or unsubstituted C1-20 alkyl, each R24, independently, is hydrogen or -COOR33, where R33 is unsubstituted C5-20 alkyl, R25 is hydrogen, -OR33, -COR33, -CON(R33)2, -SO2N(R33)2, -SO2R33, -N(Ro)COR34, -NHCOOR35, -NHCONHR36, -N(Ro)SO2R37,

where R8, h and each R33, independently, are as defined above, Y is -O-, -CO-, -COO-, -SO2-, or -CONH-, R34, R35, R36 and R37, independently, being unsubstituted C5-20 alkyl, and Ro being hydrogen or unsubstituted C1-4 alkyl, with the provisos:: i) that ring B1 bears 1, 2 or 3 substituents; ii) that at least one of the R23.s, R24.s and R25 is other than hydrogen; iii) that, where the R24's and R25 are all hydrogen, then at least one of the R23's is unsubstituted C5-20 alkyl, and iv) that the total sum of carbon atoms in the R23's, R24's and R33's to R37, together, is from 6 to 28, K#1, in the radical of formula III, being of formula If, Ig, Ih, Ii or Ik,

wherein each R26, independently, is hydrogen or unsubstituted C1-4 alkyl, k is 0, 1 or 2, R27 and R28, independently, are unsubstituted C1-4 alkyl, R29 and R32 are hydrogen or substituted or unsubstituted C1-4 alkyl, either R30 and R31, independently, are hydrogen or substituted or @@tituted @ @ll@@l @@ unsubstituted C14 alkyl, or R30 and R31, together with the nitrogen atom to which they are attached, form a heterocyclic ring, in case bb), i.e. when Q2 is a radical of formula IV, D being D3, i.e. a radical Il, Im or In

where a, b, c, d, R8 and R12 are as defined above, each R38, independently, is hydrogen or unsubstituted C1-4 alkyl, each R39, independently, is hydrogen or -COOR44, where R44 is unsubstituted C1-4 alkyl, R40 is hydrogen, -OR44,-COR44, -CON(R44)2, -SO2N(R44)2, -SO2R44, -N(R48)COR45, -NHCOOR45, -NHCONHR45, -N(R48)SO2R45,

where R41 is hydrogen, or unsubstituted C1-4 alkyl, each R42 and R43, independently being unsubstituted C1-20 alkyl, at least one of R42 and R43 containing at least 6 carbon atoms, with the proviso that up to a maximum of 25 carbon atoms, in total, are contained in R41 to R43, in case bc), i.e.

when Q2 is hydrogen or C1~4 alkyl, unsubstituted or mono-substituted by C14 alkoxy, D being D4, i.e. a radical Ip

where R49 is hydrogen, halogen, NO2, CN, unsubstituted C14 alkoxy or an unsubstituted or substituted C1-4 alkyl, R50 and R51, independently, are unsubstituted or substituted C1-20 alkyl, R52 is hydrogen or unsubstituted C14 alkyl, and L is a direct bond, or a bridging group of formula *-(CH2)p-OC *-(CH2)m-N(R62)-SO2or *-(CH2)p-CON(R62) m is 1, 2, 3 or 4, p is 1, 2, 3 or 4, R62 is hydrogen or unsubstituted C1-4 alkyl, the asterisk indicates the bond attached to the N# atom, with the proviso that the total number of non-ring-bound carbon atoms in R50, R51 and R52, together, is at least 10 and at most 30, which compound is free from sulphonic acid groups.

2. A compound of Claim 1, of formula I',

wherein T1 and n are as defined in Claim 1, Ra is unsubstituted C1-4 alkyl, Q1' is hydrogen or unsubstituted C1-16 alkyl, Q2' is hydrogen; C14 alkyl unsubstituted or mono-substituted by 1-4 alkoxy; or a radical of formula III' or IV' -(CH2)g'-K1#' A# III' -(CH2)g'-K2#' A# IV' where K1'# and K2'# are as hereinafter defined, A# is as above defined, and g' is 2 or 3, and D', in case a), i.e. when n is 1, is D1,, where D1,, in case aa), is a radical of formula Ia', Ib', Ic' or Id',

where a, b, c, e, R9 and R10 are as defined in Claim 1, R6a is hydrogen, CH3 or C2H5, R7a is hydrogen, OCH3, OC2H5 or chlorine, R8a is hydrogen, Cl, Br, NO2, CN or CF3, R11a is hydrogen, OCH3, OC2H5, methylcarbonyl, phenylcarbonyl, benzyl, phenoxycarbonyl, -CON R14a, R13, -NHCOR15a, -NHCOOR16, -NHCONHR17a, -N(R18a)SO2R19a or a radical

where R13 and R16 are as defined in Claim 1, R14a is hydrogen, CH3, C2H5, phenyl or monochlorophenyl, R15a and R17a are CH3, C2H5, phenyl or monochlorophenyl, R18a is CH3, C2H5 or benzyl, R19a is CH3, C2M5 or phenyl, and ring B1 bears 0, 1, 2 or 3 substituents, and D;;, in case ab), is a radical of formula Ix'

where either R20a hydrogen or unsubstituted C1-16 alkyl, and R21a is hydrogen, unsubstituted C1-16 alkyl, phenyl or benzyl, or R20a and R21a, together with the nitrogen atom to which they are attached, form a morpholine, pyrrolidine or piperidine ring, and R22a is hydrogen or chlorine, with the provisos, in case aa), that Q1 is unsubstituted C5-16 alkyl; and, in case ab), that, when R20a and R21a, do not form a ring with the nitrogen to which they are attached, the total of non-ring-bound carbon atoms in Q1', R20a and R21a is from 6 to 20 and that at least one of Q1', R20a and R21a is unsubstituted alkyl of at least 5 carbon atoms, and that, when R20a and R21a form a ring with said nitrogen, then Q1' is unsubstituted C5-16 alkyl, or D', in case b), i.e. when n is 2, is D2', D3' or D4', being, in case ba), i.e. when Q2' is a radical of formula III', D2, i.e. a radical of formula Ie',

where a, b, c and each R8a, independently, are as defined above, each R23a, independently, is hydrogen or unsubstituted C1-18 alkyl, each R24a, independently, is hydrogen or -COOR33a, where R33a is unsubstituted C5-18 alkyl, R25a is hydrogen, -OR33a, -COR33a, -CON(R33a)2, -SO2N(R33a)2, -N(Ro')COR33a, -NHCOOR33a, -N(Ro')SO2R33a,

where h and R47 are as defined in Claim 1 and each R33a, independently, is as defined above, Ro' is hydrogen, CH3, C2H5 or n-C3H7, Y' is -O-, -CO-, -COO- or -CONH- with the provisos that ring B1' bears 1, 2 or 3 substituents, that at least one of the R23.s, R24a.s and R25a is other than hydrogen, that where the R24a.s and K2sa are hydrogen, then at least one of the R23a.s is unsubstituted C5-18 alkyl, and that the total sum of carbon atoms in the R23a.s, R24a.s and the R33a's is from 6 to 24.

K1'#, in the radical of formula III', being of formula If', Ig', Ih' or Ii',

where k is as defined in Claim 1, each R26a, independently, R29a and R32a are hydrogen or unsubstituted C1-4 alkyl, either R30a and R31a, independently, are C1-4 alkyl, unsubstituted or monosubstituted by phenyl; or -CH2-CO-R53, where R53 is CH3, C2H5 or phenyl, or R30a and R31a, together with the nitrogen atom to which they are attached, form a morpholine, piperidine or N-methylpiperidine ring, in case bb), i.e. when Q2' is a radical of formula IV', D' being D3', i.e. a radical of formula Il', Im' or In'.

where a, b and c are as defined in Claim 1, R5a being as defined above, each R36a, independently, is hydrogen, CH3, C2H5, iso- or n-C3H7, each R39a, independently, is hydrogen or -COOR44a, where R44a is CH3, C2H5, iso- or n-C3H7, R40a is hydrogen, -OR44a, -COR44a, -CON(R44a)2, -SO2N(R44a)2, -N(R48a)COR45a, -NHCOOR45a,

where each R44a, independently, and R38a, are as defined above, and h, k and i are as defined in Claim 1, Z' is -COO- or -CONM-, each R45a in dependently, is H, Cl, Br, CH3 or C2Hs.

R47a is H or Cl, R45a is CH3, C2H5, iso-C3H7, n-C3H7

r where R38a and R47a are as defined above, and R48a is H, CH3 or C2H5, ring B2' bearing 0, 1, 2 or 3 substituents, K2#', in the radical of formula IV', being of formula Io',

where R41a is hydrogen or unsubstituted C14 alkyl, R42a and R43a, independently, being unsubstituted C1-20 alkyl, at least one of R42a and R43a containing at least 6 carbon atoms, with the proviso that up to a maximum of 25 carbon atoms, in total, are contained in R4 to R43a, in case bc), i.e.

when Q2' is hydrogen or C1-4 alkyl, unsubstituted or mono-substituted by C1-4 alkoxy, D' being D4, i.e. a radical Ip',

where R49a is hydrogen, Cl, Br, NO2 or unsubstituted C1-4 alkyl or C1-4 alkoxy, R50a and R51a, independently, are unsubstituted C1-20 alkyl or benzyl, R52a is hydrogen or unsubstituted C1-4 alkyl, L1 is a direct bond or a bridging group of formula *-(CH2)p'-OC *-(CH2)m'-N(R62a)SO2or *-(CH2)p'-CONHwhere p' is 1 or 2, m' is 2 or 3, the asterisk indicates the bond attached to the N#, and R62a, is hydrogen or unsubstituted C1-4 alkyl, with the proviso that the total number of non-ring-bound carbon atoms in R50a, R51a and R52a, together, is at least 10 and at most 25.

3. A compound of Claim 2, of formula I",

where n is as defined in Claim 1, Rb is CH3, C2H5 or iso-C3H7, Q1" is hydrogen or unsubstituted C1-14 alkyl, Q2" is hydrogen, CH3, C2H5, n- or iso-C3H7, n-C4H9, methoxy-n-propyl or a radical III" or IV", -(CH2)g'-K1#" A# III" -(CH2)g'-K1#" A# IV" where g' is as defined in Claim 2 and A# is as defined in Claim 1, and K1#" and K2#" are as defined hereinafter, T1' is a radical of formula II'

where A# is as defined in Claim 1, and R1a and R2a, independently, are H, CH3 or C2H5, and D", in case a), i.e. when n is 1, is D1", where D1", in case aa), is unsubstituted 4-phenylazo-phenyl, unsubstituted naphthyl or, preferably, a radical Ib",

where a, b, c and each R9 and R10, independently, are as defined in Claim 1, each R8b, independently, is H, Cl, NO2, CN or CF3, R11b is H, OCH3, OC2H5, CONR13R14b, NHCOR15a, -NHCOOR16 or

where R13 and R16 are as defined in Claim 1 and R15a is as defined in Claim 2, and R14b is H, CH3, C2H5 or phenyl, and ring B1" bears 0, 1 or 2 substituents and D1", in case ab) is a radical of formula Ix"

where R20b and R21b, independently, are unsubstituted C1-14 alkyl, with the provisos, in case aa), that Q1" is unsubstituted C5-12 alkyl and, in case ab), that the total of carbon atoms in Q1", R20b and R21b is from 6 to 20 and that at least one of the radicals Q1", R20b and R21b contains at least 5 carbon atoms, or D", in case b), i.e.

where a, b and c are as defined in Claim 1 and each R8b, independently, is as defined above, ring Ba" bears 1 or 2 substituents, each R23b, independently, is hydrogen or unsubstituted C1-16 alkyl, each R24b is, independently, hydrogen or -COOR33b, where R33b is unsubstituted C5-16 alkyl, R25b is hydrogen, -OR33b, -CON(R33b)2, -N(Ro")COR33b, -N(Ro")SO2R33b, -SO2N(R33b)2,

where Ro" is hydrogen, CH3 or C2H5, and each R33b independently, is as defined above, with the provisos, that at least one of the R23b's, R24b's and R25b is other than hydrogen, that where the R24b's and R25b are hydrogen, then at least one of the R23b's is unsubstituted C5-16 alkyl, and that the total sum of carbon atoms in the R23b's, R24b's and the R33b's is from 6 to 24.

K1#" in the radical of formula III", being of formula If" or

where k is as defined in Claim 1, R29b is H, CH3 or C2H5, and R30b and R31b, independently, are CH3, C2H5, C3H7 or benzyl, in case bb), i.e.

when Q2" is a radical of formula IV", D" being D" being D3" i.e. a radical of formula Il",

where a, b and c are as defined in Claim 1, and each R8b, independently, is as defined above, each R38b, independently, is H, CH3 or C2H5, each R39b, independently, is H or -COOR44b, where R44b is methyl or ethyl, R40b is hydrogen, -OR44b, -CON(R44b)2, -SO2N(R44b)2, -N(R48a)COR45b, -N(R48a)SO2R45b, unsubstituted phenylazo, unsubstituted phenylaminocarbonyl, or a radical

where k is as defined in Claim 1, R38a, R47a and R48a are as defined in Claim 2, and each R44b, independently, is as defined above, R45b is CH3, C2H5, C3H7 or phenyl, R46b is hydrogen, Cl or CH3, and ring Bb" bears 0, 1, 2 or 3 substituents, K2#", in the radical of formula IV" being of formula Io"

where R41b is H, CH3 or C2H5, and R42b and R43b, independently, are unsubstituted C1-20 alkyl, at least one of R42b and R43b containing at least 6 carbon atoms, with the proviso that up to a maximum of 18 carbon atoms are contained in R41b to R43b, in case bc), i.e. when Q2" is H, CH3, C2H5, n or iso-C3H7, n-C4H8 or methoxy-n-propyl, D" being D4", i.e. a radical of formula Ip",

where R49b is H or Cl, Raob and Rain, independently, are unsubstituted C1-18 alkyl, L2 is a direct bond or a bridging group of formula *-(CH2)n'OCor *-(CH2)m'-NHSO2the asterisk, p' and m' being as defined in Claim 2, and R52b is H or CH3, with the proviso that the total number of carbon atoms in R50b, R51b and R52b is at least 10 and at most 25.

4. A compound of Claim 3, of formula XII,

wherein R9 and A# are as defined in Claim 1, Rib and R2b, independently, are hydrogen or methyl, Q1"' is an unsubstituted C6-10 alkyl, R8c is hydrogen, NO2, Cl or CF3, R11c is hydrogen or -NHCOR15b, where R15b is methyl, ethyl or phenyl, and ring B3 bears 0, 1 or 2 substituents.

5. A compound of Claim 3, of formula XIII,

where AO is as defined in Claim 1, and Rib and R2b are as defined in Claim 4, R20c and R21c, independently, are unsubstituted C4-10 alkyl, with the proviso that at least one of R20c and R21c contains at least 5 carbon atoms.

6. A compound of Claim 3, of formula XIV,

wherein R1b and R2b are as defined in Claim 4, and A# is as defined in Claim 1, and Q1iv is unsubstituted C8-14 alkyl.

7. A compound of Claim 3, of formula XV,

wherein R1b and R2b are as defined in Claim 4, and A# is as defined in Claim 1, R20e and R21e, independently, are unsubstituted C2-5 alkyl, and Q1v is unsubstituted C4-8 alkyl, with the proviso that at least one of Q1v, R20e and R21e contains at least 5 carbon atoms.

8. A compound of Claim 3, of formula XVI,

where A# and c are as defined in Claim 1, and Rac is as defined in Claim 4, ring B1"' bears l or 2 substituents, R23c is H or unsubstituted C1-12 alkyl, each R24c, independently, is H or -COOR33c, where R33c is unsubstituted C5-12 alkyl, R25c is H, -OR33c, -CON(R33c)2, -SO2N(R33c)2, -N(Ro'")COR33c, or -N(Ro'")-SO2R33c, where each R33c, independently, is as defined above, Ro"' is H or CH3, with the provisos that at least one of R23c, the R24c's and R25c is other than hydrogen, that when the R24c's and R25c are hydrogen then R23c contains at least 5 carbon atoms, and that the total sum of carbon atoms in 23c, the R24c's and R25c is from 6 to 20.

9. A compound of Claim 3, of formula XVII.

where A# and c are as defined in Claim 1, R8c is as defined in Claim 4, ring B2"' bears 0, 1 or 2 substituents,R38c is H or CH3, each R35c independently, is H or -COOCH3, R40c is hydrogen, unsubstituted phenylazo, -CON(CH3)2 or -SO2N(CH3)2, R41c is H or CH3, R42c and R43c, independently, are unsubstituted C1-16 alkyl, at least one of R42c and R43c containing at least 6 carbon atoms, with the proviso that the total number of carbon atoms in R41c, R42c and R43c is at most 18.

10. A compound of Claim 3, of formula XVII I,

where A'= is as defined in Claim 1, and R50b, Rs,b and R52b are as defined in Claim 3, and Q2"' is CH3, C2H5, n- or iso-C3H7, n-C4H9 or 3-methoxy-n-propyl, with the proviso that the total number of carbon atoms in R50b, R51b, and R52b, together, is from 16 to 25.

11. A compound of Claim 1, as set forth in any one of the foregoing Examples 1 to 211.

12. A process for the production of a compound of formula I, stated in Claim 1, comprising coupling a diazo derivative of an amine of formula D-NH2, where D is as defined in Claim 1, with a coupling component of formula XIX,

where R, T1, T2, n, Q1 and Q2 are as defined in Claim 1.

13. A process substantially as hereinbefore described, with reference to any one of the foregoing Examples 1 to 209.

14. A compound of formula I, stated in Claim 1, whenever produced by a process according to Claim 12 or 13.

15. A process for dyeing or printing a basic dyeable substrate comprising applying thereto a dyeing or printing medium comprising a compound of any one of Claims 1 to 11 or 14.

16. A compound of formula

according to Claim 1 (case aa) wherein R and T1 are as defined in Claim 1, Q1 is unsubstituted C5-20 alkyl, D is a radical of formula Ib or Ic as defined in Claim 1, in which R8, R9, R10, a, b, c and ring B are as defined in Claim 1, R11 is hydrogen, -OCH3, -OC2H5, -COCH3, -SO2CH3, -SO2'C2H5, -CONR13R14, where R13 is hydrogen, CH3 or C2H5 and R4 is hydrogen or unsubstituted C1-3 alkyl;

where R6 is hydrogen or unsubstituted C1~4 alkyl and R5 is hydrogen, halogen, NO2, CN or CF3;

where X is -CO-, -COO- or -SO2- and Ra and Ra are as defined above; or

where h is l or 2 and Ra is as defined above, and R12 is hydrogen, halogen or unsubstituted C1~4 alkyl, or D is a radical of formula

where d is 0 or 1.

17. A compound of formula

according to Claim 1 (case ab) wherein R and T, are as defined in Claim 1, Q1 is hydrogen or unsubstituted C1-4 alkyl and D is a radical of formula

where each R22, independently, is hydrogen or halogen and R20 is unsubstituted C5-20 alkyl, with the proviso that the total of non-ringbound carbon atoms in Q1 and the radicals R20 is up to a maximum of 20.

18. A compound of formula

according to Claim 1 (case ba) wherein R and T2 are as defined in Claim 1, Q2 is a radical of formula -(CH2)g-K#1 A# where g is 2, 3 or 4, A# is an anion and K1# is a radical of formula If, Ig, Ih, Ii or Ik as defined in Claim 1, and D is a radical of formula Ie as defined in Claim 1, in which R8, R23, R24, a, b and c are as defined in Claim 1, R25 is hydrogen, -OR33, -COR33, -CON(R33)2, -SO2N(R33)2, -SO2R33,

where Ra is hydrogen, halogen, NO2, CN or CF3, each R33, independently, is unsubstituted C5-20 alkyl, Y is -O-, -OO-, -COO- or -SO2- and h is 1 or 2, with the provisos:: i) that ring B1 bears 1, 2 or 3 substituents; ii) that at least one of the R23's, R24's and R25 is other than hydrogen; iii) that, where the R24's and R25 are all hydrogen, then at least one of the R23's contains at least 5 carbon atoms; and iv) that the total sum of carbon atoms in the R23.s, R24.s and R33.a, together, is up to a maximum of 28.

19. A compound of formula

according to Claim 1 (case bb) wherein R and T3 are as defined in Claim 1, Q3 is a radical of formula -(CH2)g-K2# A# where g is 2, 3 or 4, A# is an anion and K2# is a radical of fromula Io as defined in Claim 1, and D is a radical of formula Ib as defined in Claim 1, in which R8, R38, $39, a, b and c are as defined in Claim 1, R40 is hydrogen, -OR44, -COR44, -CON(R44)2,

each R44, independently, is unsubstituted C1-4 alkyl, each R38, independently, is hydrogen or unsubstituted C1-4 alkyl, R47 is hydrogen, Cl or Br and h is 1 or 2, or D is a radical of formula

20. A compound of formula

according to Claim I (case bc) wherein R and T2 are as defined in Claim 1, Q2 is hydrogen or C1-4 alkyl, unsubstituted or monosubstituted by C1-4 alkoxy and D is a radical of formula Ip as defined in Claim 1.

Reference has been directed in pursuance of section 9, subsection (1) of the Patents Act 1949, to patent No. 1332477 and 1277090.