compounds of the formula I ##STR1## where X is fluorine, chlorine, bromine, SO2 E or unsubstituted or substituted hydroxyl or mercapto, E is alkyl, alkenyl, cycloalkyl, aralkyl, aryl, chlorine or unsubstituted or substituted hydroxyl or amino, Y is cyano, nitro, alkanoyl, aroyl, alkylsulfonyl, arylsulfonyl, carboxyl, a carboxylic ester group or unsubstituted or substituted carbamyl, T is hydrogen, c1 -c4 -alkyl, a radical which can be introduced by electrophilic substitution or a radical of the formula --CH═B, in which B is a radical of a methylene-active compound or of an amine, and K is a radical of a coupling component, are disclosed. They are useful for dyeing synthetic fibers or plastics.
|
1. A compound of the formula: ##STR536## wherein: X is fluorine; chlorine; bromine; SO2 E; --OH; --SH; c1-6 -alkoxy; benzyloxy; phenyloxy; methyl-substituted phenyloxy; chloro-substituted phenyloxy; --S--(c1-6 alkyl); benzylmercapto; --S--c2 H4 OH; --S--CH2 COOCH3 ; --S--CH2 COOC2 H5 ; phenylmercapto; or methyl-substituted phenylmercapto;
E is c1-8 -alkyl; alkenyl; cycloalkyl; c7 -c10 -aralkyl; aryl; chlorine; hydroxyl; amino; c1-4 -alkoxy; benzyloxy; c6 H5 --CH2 CH2 --O--; phenyloxy; chloro-substituted phenyloxy; methyl-substituted phenyloxy; c1-4 -alkyl-mono-substituted amino; c1-4 -alkyl-di-substituted amino; NHC6 H5 ; NHC6 H4 CH3 ; NHC6 H4 Cl; and N(CH3)c6 H4 ; Y is --COO--(CH1-8 -alkyl); --COOC2 H4 OH; --COOC3 H6 OH; --COOC2 H4 OCH3 ; --COOC2 H4 OC2 H5 ; --COOC2 H4 OC4 H9 ; --COOC6 H5 ; --COOC6 H4 CH3 ; --CONH2 ; --CONH(c1-8 -alkyl); --CON(CH3)2 ; --CON(c2 H5)2 ; --CON(c3 H7)2 ; --CON(c4 H9)2 ; --CON(CH3)c2 H5 ; ##STR537## T is hydrogen; c1-4 -alkyl; Cl; Br; NO; NO2 ; SO3 H; CHO; CN; CH3 CO; c2 H5 CO; c6 H5 CO; CH3 SO2 ; c2 H5 SO2 ; or c6 H5 SO2 ; or --CH═B; B is c(CN)(Z) where Z is cyano; nitro; alkanoyl; aroyl; alkylsulfonyl; arylsulfonyl; carboxyl; a carboxylic c1-4 alkyl or phenyl ester group; unsubstituted carbamyl; c1-2 alkyl substituted carbamyl; or a group of one of the formulae: ##STR538## and K is a radical of a coupling component.
2. The compound of
B2 is c1-6 -alkyl, or c1 -c6 -alkyl substituted by chlorine, bromine, hydroxyl, c1 -c8 -alkoxy, phenoxy, phenyl, cyano, carboxyl, c1 -c8 -alkanoyloxy, c1 -c8 -alkoxy-c1 -c4 -alkoxy, benzoyloxy, o-, m- or p-methylbenzoyloxy, o-, m- or p-chlorobenzoyloxy, c1 -c8 -alkoxyalkanoyloxy, phenoxyalkanoyloxy, c1 -c8 -alkoxycarbonyloxy, c1 -c8 -alkoxyalkoxycarbonyloxy, benzyloxycarbonyloxy, phenethoxycarbonyloxy, phenoxyethoxycarbonyloxy, c1 -c8 -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, c1 -c8 -alkoxycarbonyl, c1 -c8 -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-c1 -c4 -alkoxy or phenylethoxycarbonyl, or phenyl, or cyclohexyl; R2 is hydrogen or R3 : R3 is c1 -c6 -alkyl, c1 -c6 -alkyl substituted by chlorine, bromine, hydroxyl, c1 -c8 -alkoxy, phenoxy, cyano, carboxyl, c1 -c8 -alkanoyloxy, c1 -c8 -alkoxy-c1 -c4 -alkoxy, benzoyloxy, o-, m- and p-methylbenzoyloxy, o-, m- and p-chlorobenzoyloxy, c1 -c8 -alkoxyalkanoyloxy, phenoxyalkanoyloxy, c1 -c8 -alkoxycarbonyloxy, c1 -c8 -alkoxyalkoxycarbonyloxy, benzyloxycarbonyloxy, phenylethoxycarbonyloxy, phenoxyethoxycarbonyloxy, c1 -c8 -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, c1 -c8 -alkoxycarbonyl, c1 -c8 -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-c1 -c4 -alkoxy or phenylethoxycarbonyl, phenyl, benzyl, phenethyl, or cyclohexyl; R4 and R5, independently of one another, are hydrogen, methyl, ethyl, propyl, bromine, chlorine, methoxy, ethoxy, phenoxy, benzyloxy, or c1 -c4 -alkoxycarbonylamino, benzoylamino, c1 -c6 -alkanoylamino, or c1 -c6 -alkanoylamino substituted by chlorine, bromine, cyano, methoxy, ethoxy or phenoxy, c1 -c4 -alkylsulfonylamino or c1 -c4 -dialkylaminosulfonylamino; R6 is cyano; carbamyl; nitro; acetyl; or carbonalkoxy; and R7 is c1 -c10 -alkyl; c1 -c10 -alkoxy; phenoxy; benzyloxy; phenyl; chlorine; bromine; nitro; c1 -c4 -alkoxycarbonyl; c1 -c4 -mono- or dialkylamino; c1 -c4 -alkoxyethoxy; c1 -c4 -alkyl- or phenylmercapto; c1 -c5 -alkanoylamino; methyl or methoxy monosubstituted phenyl; c1 -c4 -alkyl; c1 -c4 -alkoxycarbonylmethyl, cyanomethyl; or benzyl.
3. The compound of
Z1 is cyano; a carboxylic c1-4 alkyl ester; or a c1-2 alkyl substituted carbamyl; Y1 is a carboxylic c1-8 alkyl ester; or a carboxylic phenyl or tolyl ester; or a carboxylic c1-2 alkyl ester substituted by --OH or --O--(c1-4 alkyl); or a c1-2 alkyl substituted carbamyl; T1 is formyl, nitro or cyano; and K1 is an aniline, thiazole, pyrazole, thiophene or pyridine coupling component radical.
4. The compound of
Y1 is a carboxylic c1-8 alkyl ester; or a carboxylic phenyl or tolyl ester; or a carboxylic c1-2 alkyl ester substituted by --OH or --O--(CH1-4 alkyl); or a c1-2 alkyl substituted carbamyl; T1 is formyl, nitro or cyano; B3 is hydrogen or B4 ; and B4 is c2 -c8 -alkyl; c2 -c8 alkyl interrupted by oxygen; c2 -c8 -alkyl interrupted by oxygen and Substituted by hydroxyl; c1 -c4 -alkanoyloxy; c1 -c4 -alkoxy; benzyloxy or phenoxy; or B4 is phenyl; or phenyl substituted by methyl or methoxy.
5. The compound of
B6 is hydrogen; methyl; methoxy; c1 -c4 -alkanoylamino, c1 -c4 -alkanoylamino substituted by methoxy, ethoxy, phenoxy, chlorine or cyano; B7 is hydrogen or B8 ; B8 is cyclohexyl; allyl; benzyl; phenyl; c1 -c6 -alkyl; c1 -c6 -alkyl substituted by hydroxyl, c1 -c4 -alkoxy, c1 -c4 -alkoxycarbonyl, c1 -c4 -alkanoyloxy or cyano; X1 is chlorine; bromine; hydroxyl; c1 -c4 -alkoxy; c1 -c4 -alkylthio, methylsulfonyl, phenylsulfonyl, phenoxy or phenylthio, Y1 is a carboxylic ester group; or a substituted carbamyl; and T1 is formyl, nitro or cyano.
6. The compound of
7. The compound of
8. The compound of
9. The compound of
X is chlorine, methoxy, ethoxy, phenylthio, methylsulfonyl or phenylsulfonyl; T is a radical of the formula CH═B, wherein B is ##STR543## and Z is hydrogen, cyano, carboxyl, a carboxylic c1-4 alkyl ester group, carbamyl; benzimidazolyl; benzoxazolyl; benthiozolyl; c1-2 alkyl substituted carbamyl.
10. The compound of
11. The compound of
12. The compound of
13. The compound of
15. The compound of
16. The compound of
the other of B3 and B4 is c2 H4 OC2 H4 OCOCH3, c3 H6 OC4 H8 OH, c3 H6 OC4 H8 OCHO, c3 H6 OC4 H8 OCOCH3, c3 H6 OC4 H8 OCOC2 H5, c3 H6 OC2 H4 OC4 H9, c3 H6 OC4 H8 OC2 H5, c3 H6 OC4 H8 OC4 H9 or c3 H6 OC2 H4 OC6 H5 ; or one of B3 and B4 is independently c2 H4 OH, c3 H6 OH, c2 H4 OCOCH3, c2 H4 OCOC2 H5, c3 H6 OCOCH3 or c3 H6 OCOC2 H5 ; and the other of B3 and B4 is c3 H6 OC2 H4 OCH3, c3 H6 OC2 H4 OC2 H5, c3 H6 OC2 H4 OC4 H9, c3 H6 OC4 H8 OC2 H5, c3 H6 OC4 H8 OC4 H9, c6 H4 OCH3 or c6 H5.
|
|||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
This is a division of application Ser. No. 860,573, filed May 7, 1986, now abandoned.
The present invention relates to compounds of the general formula I ##STR2## where X is fluorine, chlorine, bromine, SO2 E or unsubstituted or substituted hydroxyl or mercapto, E is alkyl, alkenyl, cycloalkyl, aralkyl, aryl, chlorine or unsubstituted or substituted hydroxyl or amino, Y is cyano, nitro, alkanoyl, aroyl, alkylsulfonyl, arylsulfonyl, carboxyl, a carboxylic ester group or unsubstituted or substituted carbamyl, T is hydrogen, C1 -C4 -alkyl, a radical which can be introduced by electrophilic substitution or a radical of the formula --CH═B, in which B is a radical of a methylene-active compound or of an amine, and K is a radical of a coupling component.
Examples of radicals X, in addition to those stated above, are alkoxy, cycloalkoxy, aralkoxy and aryloxy, as well as the corresponding mercapto radicals. Specific examples are OH, OCH3, OC2 H5, OC3 H7, OC4 H9, OCH2 C6 H5, OC6 H11, OC6 H5, OC6 H4 CH3, OC6 H4 Cl, SH, SCH3, SC2 H5, SC3 H7, SC4 H9, SCH2 C6 H5, SC2 H4 OH, SCH2 COOCH3, SCH2 COOC2 H5, SC6 H11, SC6 H5 and SC6 H4 CH3.
E is, for example, CH3, C2 H5, C3 H7, C4 H9, C6 H13, C6 H11, C6 H17, C6 H5 --CH2, C6 H5 --CH2 --CH2, C6 H5, Cl--C6 H4, C4 H9 --C6 H4, Cl, OH, CH3 O, C2 H5 O, C3 H7 O, C4 H9 O, C6 H5 --CH2 O, C6 H5 --CH2 --CH2 O, C6 H5 O, ClC6 H4 O, CH3 C6 H4 O, NH2, NHCH3, N(CH3)2, NHC2 H5, N(C2 H5)2, NHC4 H9, N(C4 H9)2, NHC6 H5, NHC6 H4 --CH3, NHC6 H4 Cl or N(CH3)C6 H4.
Specific examples of radicals Y, in addition to those stated above, are:
CH3 CO, C2 H5 CO, C3 H7 CO, C4 H9 CO, C5 H11 CO, C7 H15 CO, ##STR3## C6 H5 CO, CH3 C6 H4 CO, ClC6 H4 CO, (CH3)2 C6 H3 CO, H3 COC6 H4 CO, Cl2 C6 H3 CO, CH3 SO2, C2 H5 SO2, C4 H9 SO2, C6 H5 SO2, CH3 C6 H4 SO2, ClC6 H4 SO2, COOCH3, COOC2 H5, COOC3 H7, COOC4 H9, COOC6 H13, COOC6 H17, ##STR4## COOC2 H4 OH, COOC3 H6 OH, COOC2 H4 OCH3, COOC2 H4 OC2 H5, COOC2 H4 OC4 H9, COOC6 H5, COOC6 H4 CH3, CONH2, CONHCH3, CONHC2 H5, CONHC4 H9, CONHC6 H13, CONHC6 H17, CON(CH3)2, CON(C2 H5)2, CON(C3 H7)2, CON(C4 H9)2, ##STR5##
Examples of radicals T which can be introduced by electrophilic substitution are Cl, Br, NO, NO2, SO3 H, CHO, CN and acyl, where acyl is, for example CH3 CO, C2 H5 CO, C6 H5 CO, CH3 SO2, C2 H5 SO2 or C6 H5 SO2.
Methylene-active compounds of the formula H2 B are, for example, compounds of the formula ##STR6## where Z is cyano, nitro, alkanoyl, aroyl, alkylsulfonyl, arylsulfonyl, carboxyl, a carboxylic ester group or unsubstituted or substituted carbamyl or is a radical of a compound of the formula ##STR7##
Specific examples of important compounds of the formula ##STR8## are ##STR9##
Examples of amine radicals B are ═N--C6 H5,═N--C6 H4 CH3 or generally radicals of Schiff's bases of the amines.
Alkyl radicals T are, for example, CH3, C2 H5, C3 H7 or C4 H9.
The diazo components in which T is H or C1 -C4 -alkyl can be prepared by reacting a compound of the formula II ##STR10## with a sulfur donor. Radicals T may be introduced into the diazo components in which T is H by electrophilic substitution by a conventional method.
Furthermore, the diazo component in which T is H and X is OH may be prepared by reacting the compound of the formula
ClCH2 COCl
with malodinitrile and then reacting the product with a sulfide.
The preparation of the diazo components is described in detail in European Patent Application 86102603.7.
The coupling components of the formula HK are preferably derived from the aniline, α-naphthylamine, pyrazole, aminopyrazole, indole, thiazole, thiophene, phenol, naphthol, tetrahydroquinoline, pyridone or pyridine series, those of the aniline, pyrazole, pyridine, thiophene and thiazole series being preferred.
The coupling components HK are in particular of the general formula ##STR11## where B1 is hydrogen or B2, B2 is unsubstituted or substituted alkyl, cycloalkyl, alkenyl, aryl or acyl, R1 is hydrogen, alkyl, aralkyl or aryl, R2 is hydrogen or R3, R3 is unsubstituted or substituted alkyl, cycloalkyl, alkenyl, aralkyl or aryl, R4 and R5 independently of one another are each hydrogen, alkyl, alkoxy, phenoxy, halogen, alkylsulfonylamino, dialkylaminosulfonylamino or acylamino, R6 is cyano, carbamyl, nitro, acetyl or carbalkoxy and R7 is unsubstituted or substituted phenyl, alkyl, aralkyl, halogen, substituted hydroxyl or mercapto.
Examples of radicals B2, in addition to those stated above, are C1 -C6 -alkyl which may be substituted by chlorine, bromine, hydroxyl, C1 -C8 -alkoxy, phenoxy, phenyl, cyano, carboxyl, C1 -C8 -alkanoyloxy, C1 -C8 -alkoxy-C1 -C4 -alkoxy, benzoyloxy, o-, m- or p-methylbenzoyloxy, o-, m- or p-chlorobenzoyloxy, C1 -C8 -alkoxyalkanoyloxy, phenoxyalkanoyloxy, C1 -C8 -alkoxycarbonyloxy, C1 -C8 -alkoxyalkoxycarbonyloxy, benzyloxycarbonyloxy, phenethoxycarbonyloxy, phenoxyethoxycarbonyloxy, C1 -C8 -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C1 -C8 -alkoxycarbonyl, C1 -C8 -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C1 -C4 -alkoxy or phenylethoxycarbonyl, and phenyl and cyclohexyl.
Specific examples of radicals B2 are:
1. Unsubstituted or substituted alkyl, such as ##STR12##
2. Unsubstituted or substituted cycloalkyl: ##STR13##
3. Unsubstituted or substituted aralkyl: ##STR14##
4. Unsubstituted or substituted phenyl: C6 H5, C6 H4 CH3, C6 H3 (CH3)2, C6 H4 OCH3, C6 H3 (OCH3)2, C6 H4 Cl and C6 H2 (OCH3)2 Cl.
5. The radicals CH2 CH═CH2, CH2 COOCH3, (CH2)5 COOCH3, (CH2)5 COOC2 H5, ##STR15## where n is 2, 3, 4 or 6.
6. Acyloxy radicals: (CH2)2 OCHO, (CH2)2 OCO(CH2)n CH3, (C2 H4 O)2 CHO, (C2 H4 O)2 CO(CH2)n CH3, (CH2)3 O(CH2)2 OCHO, (CH2)3 O(CH2)2 OCO(CH2)n CH3, (CH2)2 O(CH2)4 OCHO and (CH2)2 O(CH2)4 OCO(CH2)n CH3, where n is 0 to 7, ##STR16## (CH2)2 OCOC6 H5, (CH2)2 OCOC6 H4 CH3, (CH2)2 OCOC6 H4 Cl, (CH2)2 OCONHCH3, (CH2)2 OCONHC4 H9, ##STR17## (CH2)2 OCONHC6 H5, and the corresponding radicals containing (CH2)3 or (CH2)4 instead of (CH2)2.
7. Acyl radicals: CHO and CH3 (CH2)n CO, where n is from 0 to 7, C6 H5 CO, CH3 C6 H4 CO, C6 H5 CH2 CO, C6 H5 OCH2 CO, CH3 SO2, C2 H5 SO2, C6 H5 SO2 and CH3 C6 H4 SO2.
Specific examples of radicals R1, in addition to those stated above, are methyl, ethyl, propyl, butyl, benzyl, phenethyl, phenyl, o-, m- and p-tolyl and o-, m- and p-chlorophenyl.
Examples of radicals R3, in addition to those mentioned above, are C1 -C6 -alkyl which may be substituted by chlorine, bromine, hydroxyl, C1 -C8 -alkoxy, phenoxy, cyano, carboxyl, C1 -C8 -alkanoyloxy, C1 -C8 -alkoxy-C1 -C4 -alkoxy, benzoyloxy, o-, m- and p-methylbenzoyloxy, o-, m- and p-chlorobenzoyloxy, C1 -C8 -alkoxyalkanoyloxy, phenoxyalkanoyloxy, C1 -C8 -alkoxycarbonyloxy, C1 -C8 -alkoxyalkoxycarbonyloxy, benzyloxycarbonyloxy, phenylethoxycarbonyloxy, phenoxyethoxycarbonyloxy, C1 -C8 -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C1 -C8 -alkoxycarbonyl, C1 -C8 -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C1 -C4 -alkoxy or phenylethoxycarbonyl, and phenyl, benzyl, phenethyl and cyclohexyl.
Specific examples of radicals R3 are methyl, ethyl, propyl, butyl, pentyl, hexyl, allyl, methallyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-hydroxyethyl, 2-phenyl-2-hydroxyethyl, 2,3-dihydroxypropyl, 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxy-3-phenoxypropyl, 2-hydroxy-3-methoxypropyl, 2-hydroxy-3-butoxypropyl, 3-hydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-phenoxyethyl, 2-phenoxypropyl, 2-acetoxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 2-isobutyryloxyethyl, 2-methoxymethylcarbonyloxyethyl, 2-ethoxymethylcarbonyloxyethyl, 2-phenoxymethylcarbonlyoxyethyl, 2-methoxycarbonyloxyethyl, 2-ethoxycarbonyloxyethyl, 2-propoxycarbonyloxyethy, 2-butoxycarbonyloxyethyl, 2-phenyloxycarbonyloxyethyl, 2-benzyloxycarbonyloxyethyl, 2-methoxyethoxycarbonyloxyethyl, 2-ethoxyethoxycarbonyloxyethyl, 2-propoxyethoxycarbonyloxyethyl, 2-butoxyethoxycarbonyloxyethyl, 2-methylaminocarbonyloxyethyl, 2-ethylaminocarbonyloxyethyl, 2-propylaminocarbonyloxyethyl, 2-butylaminocarbonyloxyethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-propoxycarbonylethyl, 2-butoxycarbonylethyl, 2-phenoxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-β-phenylethoxycarbonylethyl, 2-methoxyethoxycarbonylethyl, 2-ethoxyethoxycarbonylethyl, 2-propoxyethoxycarbonylethyl, 2-butoxyethoxycarbonylethyl, 2-phenoxyethoxycarbonylethyl and 2-benzoylethyl.
Examples of suitable radicals R4 and R5 are hydrogen, methyl, ethyl, propyl, bromine, chlorine, methoxy, ethoxy, phenoxy, benzyloxy and C1 -C4 -alkoxycarbonylamino, and benzoylamino or C1 -C6 -alkanoylamino which is unsubstituted or substituted by chlorine, bromine, cyano, methoxy, ethoxy or phenoxy, and C1 -C4 -alkylsulfonylamino or -dialkylaminosulfonylamino.
Examples of radicals R6 in addition to those mentioned above are aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, ethylaminocarbonyl, diethylaminocarbonyl, methoxycarbonyl, ethoxycarbonyl, n- and isopropoxycarbonyl, n-, iso- and sec.-butoxycarbonyl, methoxyethoxycarbonyl, ethoxyethoxycarbonyl, n- and isopropoxyethoxycarbonyl and n-, iso- and sec.-butoxyethoxycarbonyl.
Examples of radicals R7 are C1 -C10 -alkyl, C1 -C10 -alkoxy, phenoxy, benzyloxy, phenyl, chlorine, bromine, nitro, C1 -C4 -alkoxycarbonyl, C1 -C4 -mono- and dialkylamino, C1 -C4 -alkoxyethoxy, C1 -C4 -alkyl- or phenylmercapto, C1 -C5 -alkanoylamino, such as acetylamino, propionylamino, butyrylamino or valerylamino, monosubstituted or polysubstituted phenyl, C1 -C4 -alkyl, C1 -C4 -alkoxycarbonylmethyl, cyanomethyl and benzyl.
The compounds of the formula I have yellow to greenish blue hues and are particularly useful for dyeing polyesters, nylons, cellulose esters and blends of polyesters and cellulose fibers. As a rule, the dyeings obtained have good or very good fastness properties, particularly on polyesters.
Dyes having a suitable constitution are dischargeable under reduced conditions and/or under alkaline and reducing conditions.
Suitable discharging agents are the conventionally used ones, for example tin(II) chloride, sodium bisulfite, sodium dithionite or hydroxymethanesulfonic acid. The discharge process too can be carried out in a conventional manner.
Some of the compounds of the formula I are very useful for dyeing thermoplastics, such as polystyrene, polymethacrylates, polycarbonates, nylon and styrene/acrylic acid/butadiene copolymers, since they possess high color strength and good lightfastness and heat resistance. Furthermore, many novel dyes can be used for dyeing and/or printing polyester/cotton blends by the process described in German Patent 1,811,796, the resulting dyeings having good lightfastness and fastness to washing.
The compounds of the formula I can be prepared by a conventional method. Details are given in the Examples, in which parts and percentages are by weight, unless stated otherwise.
Of particular importance are compounds of the formulae I a ##STR18## and I b ##STR19## where X1 is chlorine, bromine, hydroxyl, C1 -C4 -alkoxy or -alkylthio, methylsulfonyl, phenylsulfonyl, phenoxy or phenylthio, Y1 and Z1 are each cyano, a carboxylic ester group or substituted carbamyl, T1 is formyl, nitro or cyano and K1 is a radical of a coupling component of the aniline, thiazole, pyrazole, thiophene or pyridine series.
Compounds of the formulae Ia and Ib in which X1 is chlorine, ethoxy or phenylmercapto, Y1 is cyano, T1 is formyl, Z1 is cyano, a carboxylic ester group or substituted carbamyl and K is a radical of a coupling component of the aniline, thiazole, thiophene or pyridine series, are particularly useful industrially.
Other particularly important dyes are those of the general formula IIa ##STR20## where X1, Y1 and T1 have the stated meanings, B3 is hydrogen or B4, and B4 is C2 -C8 -alkyl which may or may not be interrupted by oxygen and is unsubstituted or substituted by hydroxyl, C1 -C4 -alkanoyloxy, C1 -C4 -alkoxy, benzyloxy or phenoxy, or is phenyl which is unsubstituted or substituted by methyl or methoxy. Preferred carboxylic ester groups Y1 are COOCH3 and COOC2 H5.
Examples of particularly preferred radicals B3 and B4 are hydrogen and C2 H5, C3 H7, C4 H9, ##STR21## C6 H11, C6 H5, C6 H4 CH3, C6 H4 OCH3, C2 H4 OH, C3 H6 OH, C2 H4 OCH3, C3 H6 OCH3, C2 H4 OC2 H5, C2 H4 OC4 H9, C3 H6 OC2 H5, C2 H4 OC2 H4 OH, C3 H6 OC2 H4 OH, C3 H6 OC4 H8 OH, C3 H6 OC2 H4 OCH3, C3 H6 OC2 H4 OC2 H5, C3 H6 OC2 H4 OC4 H9, C3 H6 OC4 H8 OC2 H5, C3 H6 OC4 H8 OC4 H9, C2 H4 OC2 H4 OCO(CH2)m CH3, C3 H6 OC2 H4 OCO(CH2)m CH3, C3 H 6 OC4 H8 OCO(CH2)m CH3, C2 H4 OCO(CH2)m CH3, C3 H6 OCO(CH2)m CH3, C3 H6 OCH2 C6 H5 and C3 H6 OC2 H4 OC6 H5, where m is from 1 to 4.
Examples of particularly preferred combinations of B3 and B4 are hydrogen and C2 H4 OC2 H4 OCOCH3, C2 H4 OC2 H4 OCOC2 H5, C3 H6 OC4 H8 OH, C3 H6 OC4 H8 OCOCH3, C3 H6 OC4 H8 OCOC2 H5, C3 H6 OC2 H4 OCH3, C3 H6 OC2 H4 OC2 H5, C3 H6 OC2 H4 OC4 H9, C3 H6 OC4 H8 OC2 H5, C3 H6 OC4 H8 OC4 H9, C3 H6 OCH2 C6 H5, C3 H6 OC2 H4 OC6 H5 or C3 H6 OCH2 CH(C2 H5)C4 H9, and C2 H5, C2 H4 OCH3, C3 H6 OCH3, CH(CH3) 2 or C4 H9 in combination with C2 H4 OC2 H4 OCOCH3, C3 H6 OC4 H8 OH, C3 H6 OC4 H8 OCHO, C3 H6 OC4 H8 OCOCH3, C3 H6 OC4 H8 OCOC2 H5, C3 H6 OC2 H4 OC4 H9, C3 H6 OC4 H8 OC2 H5, C3 H6 OC4 H8 OC4 H9 or C3 H6 OC2 H4 OC6 H5 and furthermore C2 H4 OH, C3 H6 OH, C2 H4 OCOCH3, C2 H4 OCOC2 H5, C3 H6 OCOCH3 or C3 H6 OCOC2 H5 in combination with C3 H6 OC2 H4 OCH3, C3 H6 OC2 H4 OC2 H5, C3 H6 OC2 H4 OC4 H 9, C3 H6 OC4 H8 OC2 H5, C3 H6 OC4 H8 OC4 H9, C6 H4 OCH3 or C6 H5.
The process for the preparation of acyloxyalkyl-substituted or acyloxyalkoxyalkyl-substituted 2,6-diaminopyridines which are free of by-products is also particularly important.
Previously, azo dyes containing such coupling components had to be prepared by subsequent acylation of the corresponding hydroxyl-containing dyes in anhydrous organic solvents with acyl halides or anhydrides since the coupling components themselves preferentially undergo N-acylation under these conditions, and the N-acyl-2,6-diaminopyridines are not capable of coupling.
According to the invention, the coupling components are prepared by adding not less than an equivalent amount of sulfuric acid to a solution or suspension of the hydroxyl-containing substituted pyridine in the desired organic acid and stirring the mixture at from 20° to 100° C., preferably from 20° to 50°C The degree of acylation is dependent on the water content and reaches 100% in an anhydrous medium. However, the absence of water and 100% conversion are not essential in every case in order to achieve optimum dyeing properties. An adequate conversion in most cases is 70-90%, which does not require the absence of water and advantageously allows the acylation to be combined with the preparation of the hydroxyalkylaminopyridine.
4.7 parts of 2-amino-4-chloro-3-cyano-5-formylthiophene in 30 parts by volume of 85% strength sulfuric acid were stirred at no higher than 30°C, 8.3 parts of nitrosylsulfuric acid (11.5% of N2 O3) were added dropwise at 0°-5°C, and the mixture was then stirred for a further 4 hours at this temperature.
The resulting diazonium salt solution was slowly run, at 0°C, into a solution of 5.8 parts of N,N-diallyl-3-aminoacetanilide in a mixture of 25 parts by volume of dimethylformamide, 125 parts of water, 300 parts of ice, 20 parts by volume of 32% strength hydrochloric acid and 0.5 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried to give 9 parts of the dye of the formula ##STR22## which dyes polyester fibers in fast blue hues.
4.7 parts of 2-amino-4-chloro-3-cyano-5-formylthiophene were diazotized by a method similar to that described in Example 1. The diazonium salt solution was added dropwise at 0°C, to a solution of 8.8 parts of o-(bisacetoxyethyl)-amino-p-acetanisidine in a mixture of 125 parts of water, 350 parts of ice, 1 part of 96% strength sulfuric acid and 0.5 part of amidosulfonic acid. When coupling was complete, the dye was filtered under suction, washed until neutral and dried to give 9.5 parts of a greenish black powder of the formula ##STR23## which dyes polyester fabric in fast greenish blue hues.
The dyes characterized in the Table below are obtained similarly to Examples 1 and 2.
| __________________________________________________________________________ |
| ##STR24## |
| Example Dyeing on |
| No. T X Y K polyester |
| __________________________________________________________________________ |
| 3 CHO Cl |
| CN |
| ##STR25## blue |
| 4 CHO Cl |
| CN |
| ##STR26## bluish violet |
| 5 CHO Cl |
| CN |
| ##STR27## blue |
| 6 CHO Cl |
| CN |
| ##STR28## blue |
| 7 CHO Cl |
| CN |
| ##STR29## blue |
| 8 CHO Cl |
| CN |
| ##STR30## blue |
| 9 CHO Cl |
| CN |
| ##STR31## blue |
| 10 CHO Cl |
| CN |
| ##STR32## blue |
| 11 CHO Cl |
| CN |
| ##STR33## reddish blue |
| 12 CHO Cl |
| CN |
| ##STR34## reddish blue |
| 13 CHO Cl |
| CN |
| ##STR35## bluish violet |
| 14 CHO Cl |
| CN |
| ##STR36## violet |
| 15 CHO Cl |
| CN |
| ##STR37## greenish blue |
| 16 CHO Cl |
| CN |
| ##STR38## greenish blue |
| 17 CHO Cl |
| CN |
| ##STR39## greenish blue |
| 18 CHO Cl |
| CN |
| ##STR40## greenish blue |
| 19 CHO Cl |
| CN |
| ##STR41## greenish blue |
| 20 CHO Cl |
| CN |
| ##STR42## greenish blue |
| 21 CHO Cl |
| CN |
| ##STR43## greenish blue |
| 22 CHO Cl |
| CN |
| ##STR44## blue |
| 23 CHO Cl |
| CN |
| ##STR45## blue |
| 24 CHO Cl |
| CO2 C2 H5 |
| ##STR46## blue |
| 25 CHO Cl |
| CN |
| ##STR47## blue |
| 26 CHO Cl |
| CN |
| ##STR48## blue |
| 27 CHO Cl |
| CN |
| ##STR49## blue |
| 28 CHO Cl |
| CN |
| ##STR50## blue |
| 29 CHO Cl |
| CN |
| ##STR51## blue |
| 30 CHO Cl |
| CN |
| ##STR52## blue |
| 31 CHO Cl |
| COOCH3 |
| ##STR53## blue |
| 32 CHO Cl |
| SO2 CH3 |
| ##STR54## blue |
| 33 CHO Cl |
| CONH2 |
| ##STR55## reddish blue |
| 34 CHO Cl |
| CON(CH3)2 |
| ##STR56## blue |
| 35 CHO Cl |
| CO2 C2 H5 |
| ##STR57## blue |
| 36 CHO Cl |
| CO2 C2 H5 |
| ##STR58## bluish violet |
| 37 CHO Cl |
| CO2 C2 H5 |
| ##STR59## blue |
| 38 CHO Cl |
| CO2 C2 H5 |
| ##STR60## greenish blue |
| 39 CHO Br |
| CN |
| ##STR61## violet |
| 40 CHO Br |
| CN |
| ##STR62## bluish violet |
| 41 CHO Br |
| CN |
| ##STR63## blue |
| 42 CHO Br |
| CN |
| ##STR64## greenish blue |
| 43 CHO Br |
| CO2 C2 H5 |
| ##STR65## blue |
| 44 CHO F CN |
| ##STR66## blue |
| 45 CHO F CN |
| ##STR67## reddish blue |
| 46 CHO F CN |
| ##STR68## blue |
| 47 CHO F CO2 C2 H5 |
| ##STR69## reddish blue |
| 48 CHO Cl |
| CO2 C2 H5 |
| ##STR70## blue |
| 49 CHO Cl |
| CONH2 |
| ##STR71## blue |
| 50 CHO Cl |
| NO2 |
| ##STR72## blue |
| 51 CHO Cl |
| CON(CH3)2 |
| ##STR73## blue |
| 52 CHO Cl |
| SO2 CH3 |
| ##STR74## blue |
| 53 CHO Br |
| CO2 C2 H5 |
| ##STR75## blue |
| 54 CHO Cl |
| CN |
| ##STR76## blue |
| 55 CHO Cl |
| CN |
| ##STR77## blue |
| 56 CHO Br |
| CN |
| ##STR78## blue |
| 57 CHO Cl |
| CN |
| ##STR79## violet |
| 58 CHO Cl |
| CN |
| ##STR80## blue |
| 59 CHO Cl |
| CO2 C2 H 5 |
| ##STR81## blue |
| 60 CHO Cl |
| CN |
| ##STR82## yellowish brown |
| 61 CHO Cl |
| CN |
| ##STR83## red |
| 62 CHO Cl |
| CN |
| ##STR84## red |
| 63 CHO Cl |
| CN |
| ##STR85## blue |
| 64 CHO Cl |
| CN |
| ##STR86## blue |
| 65 CHO Cl |
| CN |
| ##STR87## blue |
| 66 CHO Cl |
| CN |
| ##STR88## blue |
| 67 CHO Cl |
| CN |
| ##STR89## violet |
| 68 CHO Cl |
| CN |
| ##STR90## red |
| 69 CHO Cl |
| CN |
| ##STR91## red |
| 70 CHO Cl |
| CN |
| ##STR92## blue |
| 71 CHO Cl |
| CN |
| ##STR93## blue |
| 72 H Cl |
| CN |
| ##STR94## red |
| 73 CH3 |
| Cl |
| CN |
| ##STR95## red |
| 74 CH3 |
| Cl |
| CN |
| ##STR96## red |
| 75 CH3 |
| Cl |
| CN |
| ##STR97## reddish violet |
| 76 C2 H5 |
| Cl |
| CN |
| ##STR98## red |
| 77 CH3 |
| Br |
| CN |
| ##STR99## red |
| 78 CN Cl |
| CN |
| ##STR100## blue |
| 79 CN Cl |
| CN |
| ##STR101## blue |
| 80 CN Cl |
| CN |
| ##STR102## greenish blue |
| 81 CN Br |
| CN |
| ##STR103## reddish blue |
| 82 CN Cl |
| CN |
| ##STR104## blue |
| 83 NO2 |
| Cl |
| CN |
| ##STR105## reddish blue |
| 84 NO2 |
| Cl |
| CN |
| ##STR106## blue |
| 85 NO2 |
| Cl |
| CN |
| ##STR107## greenish blue |
| 86 NO2 |
| Cl |
| CN |
| ##STR108## greenish blue |
| 87 |
| ##STR109## |
| Cl |
| CN |
| ##STR110## blue |
| 88 NO2 |
| Br |
| CN |
| ##STR111## blue |
| 89 NO2 |
| Cl |
| CN |
| ##STR112## greenish blue |
| 90 NO2 |
| Cl |
| CN |
| ##STR113## greenish blue |
| 91 Br Cl |
| CN |
| ##STR114## bluish red |
| 92 Br Cl |
| CN |
| ##STR115## bluish violet |
| 93 Br Cl |
| CN |
| ##STR116## red |
| 94 Br Cl |
| CN |
| ##STR117## red |
| 95 Br Cl |
| CN |
| ##STR118## bluish violet |
| 96 Cl Cl |
| CN |
| ##STR119## bluish red |
| 97 Cl Cl |
| CN |
| ##STR120## reddish blue |
| 98 Br Br |
| CN |
| ##STR121## reddish blue |
| __________________________________________________________________________ |
11.7 parts of 2-amino-3-cyano-4-ethoxy-5-formylthiophene in 200 parts by volume of a 3:1 glacial acetic acid/propionic acid mixture and 25 parts by volume of 96% strength sulfuric acid were stirred at no higher than 20°C 23 parts of nitrosylsulfuric acid (11.5% of N2 O3) were added dropwise at 0°-5°C, and the mixture was then stirred for 1 hour.
The resulting diazonium salt solution was added dropwise, at 0°C, to a solution of 21 parts of o-(bisacetoxyethyl)-amino-p-acetanisidine in a mixture of 100 parts by volume of dimethylformamide, 500 parts of water, 25 parts by volume of 18% strength hydrochloric acid, 250 parts of ice and 1 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried to give 25 parts of the dye of the formula ##STR122## which dyes polyester fibers in fast greenish blue hues.
The dyes shown in the Table below were obtained similarly to Example 99.
| __________________________________________________________________________ |
| ##STR123## |
| Example Dyeing on |
| No. T X Y K polyester |
| __________________________________________________________________________ |
| 100 CHO OC2 H5 |
| CN |
| ##STR124## blue |
| 101 CHO OC2 H5 |
| CN |
| ##STR125## bluish violet |
| 102 CHO OC2 H5 |
| CN |
| ##STR126## blue |
| 103 CHO OC2 H5 |
| CN |
| ##STR127## blue |
| 104 CHO OC2 H5 |
| CN |
| ##STR128## blue |
| 105 CHO OC2 H5 |
| CN |
| ##STR129## blue |
| 106 CHO OC2 H5 |
| CN |
| ##STR130## reddish blue |
| 107 CHO OC2 H5 |
| CN |
| ##STR131## reddish blue |
| 108 CHO OC2 H5 |
| CN |
| ##STR132## bluish violet |
| 109 CHO OC2 H5 |
| CN |
| ##STR133## violet |
| 110 CHO OC2 H5 |
| CN |
| ##STR134## greenish blue |
| 111 CHO OC2 H5 |
| CN |
| ##STR135## greenish blue |
| 112 CHO OC2 H5 |
| CN |
| ##STR136## greenish blue |
| 113 CHO OC2 H5 |
| CN |
| ##STR137## greenish blue |
| 114 CHO OC2 H5 |
| CN |
| ##STR138## blue |
| 115 CHO OC2 H5 |
| CO2 C2 H5 |
| ##STR139## blue |
| 116 CHO OC2 H5 |
| COOCH3 |
| ##STR140## blue |
| 117 CHO OC2 H5 |
| SO2 CH3 |
| ##STR141## blue |
| 118 CHO OC2 H5 |
| CONH2 |
| ##STR142## reddish blue |
| 119 CHO OC2 H5 |
| CON(CH3)2 |
| ##STR143## blue |
| 120 CHO OC2 H5 |
| CO2 C2 H5 |
| ##STR144## blue |
| 121 CHO OC2 H5 |
| CO2 C2 H5 |
| ##STR145## bluish violet |
| 122 CHO OC2 H 5 |
| CO2 C2 H5 |
| ##STR146## blue |
| 123 CHO OC2 H5 |
| CO2 C2 H5 |
| ##STR147## greenish blue |
| 124 CHO OCH3 |
| CN |
| ##STR148## violet |
| 125 CHO OCH3 |
| CN |
| ##STR149## bluish violet |
| 126 CHO OCH3 |
| CN |
| ##STR150## blue |
| 127 CHO OCH3 |
| CN |
| ##STR151## greenish blue |
| 128 CHO OCH3 |
| CO2 C2 H5 |
| ##STR152## blue |
| 129 CHO OC6 H5 |
| CN |
| ##STR153## blue |
| 130 CHO OC6 H5 |
| CN |
| ##STR154## bluish violet |
| 131 CHO SC6 H5 |
| CO2 C2 H5 |
| ##STR155## blue |
| 132 CHO SC2 H5 |
| CN |
| ##STR156## bluish violet |
| 133 CHO SC6 H5 |
| CN |
| ##STR157## blue |
| 134 CHO OC2 H5 |
| CN |
| ##STR158## blue |
| 135 CHO OC2 H5 |
| CN |
| ##STR159## blue |
| 136 CHO OC2 H5 |
| CN |
| ##STR160## blue |
| 137 CHO OC2 H5 |
| CN |
| ##STR161## reddish blue |
| 138 CHO OC2 H5 |
| CN |
| ##STR162## blue |
| 139 CHO OCH3 |
| CO2 C2 H5 |
| ##STR163## blue |
| 140 CHO OC2 H5 |
| CN |
| ##STR164## yellowish brown |
| 141 CHO OC2 H5 |
| CN |
| ##STR165## red |
| 142 CHO OC2 H5 |
| CN |
| ##STR166## red |
| 143 CHO OC2 H5 |
| CN |
| ##STR167## blue |
| 144 CHO OC2 H5 |
| CN |
| ##STR168## blue |
| 145 CHO OCH3 |
| CN |
| ##STR169## blue |
| 146 CHO OC6 H5 |
| CN |
| ##STR170## blue |
| 147 CH3 |
| OC2 H5 |
| CN |
| ##STR171## red |
| 148 CH3 |
| OC2 H5 |
| CN |
| ##STR172## red |
| 149 CH3 |
| OC2 H5 |
| CN |
| ##STR173## reddish violet |
| 150 C2 H5 |
| OC2 H5 |
| CN |
| ##STR174## red |
| 151 CH3 |
| OC2 H 5 |
| CN |
| ##STR175## red |
| 152 CN OC2 H5 |
| CN |
| ##STR176## blue |
| 153 CN OC2 H5 |
| CN |
| ##STR177## blue |
| 154 NO2 |
| OC2 H5 |
| CN |
| ##STR178## blue |
| __________________________________________________________________________ |
5.8 parts of the dye described in Example 12 were dissolved in 60 parts by volume of dioxane, 3.4 parts of ethyl cyanoacetate, 1 part of glacial acetic acid and 1 part of piperidine were added, and the mixture was stirred for 16 hours at room temperature, after which 50 parts of water and 50 parts of ice were added. Stirring was continued for 15 minutes, and the product was filtered off under suction, washed neutral and dried at 50°C under reduced pressure to give 6.6 parts of the dye of the formula ##STR179## which dyes polyester fibers in medium blue hues.
5.1 parts of the dye described in Example 13 were dissolved in 65 parts by volume of dioxane, 4.2 parts of butyl cyanoacetate, 1 part of glacial acetic acid and 1 part of piperidine were added and the mixture was stirred for 16 hours at room temperature. Thereafter, 50 parts of water and 50 parts of ice were added, stirring was continued for 1 hour and the product was filtered off under suction, washed neutral and dried to give 5.9 parts of the dye of the formula ##STR180## which dyes polyester in fast blue hues.
The dyes listed in the Table below were obtained similarly to Examples 155 and 156.
| __________________________________________________________________________ |
| ##STR181## |
| Ex- |
| am- Dyeing on |
| No. |
| X Y Y1 Y2 K polyester |
| __________________________________________________________________________ |
| 157 |
| Cl CN COOC2 H5 |
| COOC2 H5 |
| ##STR182## blue |
| 158 |
| Cl CN COOC2 H5 |
| COOC2 H5 |
| ##STR183## reddish blue |
| 159 |
| Cl CN COOC2 H5 |
| COOC2 H5 |
| ##STR184## blue |
| 160 |
| Cl CN COOC2 H5 |
| COOC2 H5 |
| ##STR185## blue |
| 161 |
| Cl CN CN CN |
| ##STR186## blue |
| 162 |
| Cl CN COCH3 COOC2 H5 |
| ##STR187## blue |
| 163 |
| Cl COOC2 H5 |
| CN COOC2 H5 |
| ##STR188## blue |
| 164 |
| Cl COOC2 H5 |
| CN COOC2 H5 |
| ##STR189## blue |
| 165 |
| Cl COOC2 H5 |
| CN COOC2 H5 |
| ##STR190## blue |
| 166 |
| Cl COOC2 H 5 |
| COOC2 H5 |
| COOC2 H5 |
| ##STR191## dark blue |
| 167 |
| Cl COOC2 H5 |
| COCH3 COOC2 H5 |
| ##STR192## dark blue |
| 168 |
| Cl COOC2 H5 |
| COCH3 COCH3 |
| ##STR193## blue |
| 169 |
| Cl COOC2 H5 |
| COCH3 CN |
| ##STR194## dark blue |
| 170 |
| Cl |
| ##STR195## |
| CN COOC2 H5 |
| ##STR196## dark blue |
| 171 |
| Cl |
| ##STR197## |
| CN COOC2 H5 |
| ##STR198## blue |
| 172 |
| Cl SO2 CH3 |
| CN COOC2 H5 |
| ##STR199## dark blue |
| 173 |
| Cl SO2 CH3 |
| CN COOC2 H5 |
| ##STR200## blue |
| 174 |
| Cl SO2 CH3 |
| CN COOC2 H5 |
| ##STR201## blue |
| 175 |
| Cl CN CN COOC2 H5 |
| ##STR202## reddish blue |
| 176 |
| Cl CN CN COOC2 H5 |
| ##STR203## dark blue |
| 177 |
| Cl CN CN COOC2 H5 |
| ##STR204## dark blue |
| 178 |
| Cl CN CN COOC2 H5 |
| ##STR205## dark blue |
| 179 |
| Cl CN CN COOC2 H5 |
| ##STR206## dark blue |
| 180 |
| Cl CN CN COOC2 H5 |
| ##STR207## dark blue |
| 181 |
| Cl CN CN COOC2 H5 |
| ##STR208## blue |
| 182 |
| Cl CN CN COOC2 H5 |
| ##STR209## blue |
| 183 |
| Cl CN CN COOC2 H5 |
| ##STR210## blue |
| 184 |
| Cl CN CN COOC2 H5 |
| ##STR211## blue |
| 185 |
| Cl CN CN COOC2 H5 |
| ##STR212## violet |
| 186 |
| Cl CN CN COOC2 H5 |
| ##STR213## violet |
| 187 |
| Cl CN CN COOC2 H5 |
| ##STR214## violet |
| 188 |
| Cl CN CN CONHCH3 |
| ##STR215## dark blue |
| 189 |
| Cl CN CN CONHC2 H5 |
| ##STR216## dark blue |
| 190 |
| Cl CN CN SO2 CH3 |
| ##STR217## dark blue |
| 191 |
| Cl CN CN COCH3 |
| ##STR218## dark blue |
| 192 |
| Cl CN CN COOCH3 |
| ##STR219## dark blue |
| 193 |
| Cl CN CN COOC4 H9 (n) |
| ##STR220## blue |
| 194 |
| Cl CN CN COOC4 H9 (n) |
| ##STR221## blue |
| 195 |
| Cl CN CN COOC4 H9 (n) |
| ##STR222## blue |
| 196 |
| Cl CN CN COOC4 H9 (n) |
| ##STR223## dark blue |
| 197 |
| Cl CN CN |
| ##STR224## |
| ##STR225## dark blue |
| 198 |
| Cl CN CN |
| ##STR226## |
| ##STR227## dark blue |
| 199 |
| Cl CN CN |
| ##STR228## |
| ##STR229## dark blue |
| 200 |
| Cl CN CN CONH2 |
| ##STR230## dark blue |
| 201 |
| Cl CN COOC2 H5 |
| COOC2 H5 |
| ##STR231## navy blue |
| 202 |
| Cl CN COCH3 COOC2 H5 |
| ##STR232## dark blue |
| 203 |
| Cl CN CN CONHCH3 |
| ##STR233## dark blue |
| 204 |
| Br CN CN COOC2 H5 |
| ##STR234## reddish blue |
| 205 |
| Br CN CN COOC2 H5 |
| ##STR235## reddish blue |
| 206 |
| Br CN CN COOC2 H5 |
| ##STR236## blue |
| 207 |
| Br CN CN COOC2 H5 |
| ##STR237## dark blue |
| 208 |
| Br CN CN COOC2 H5 |
| ##STR238## dark blue |
| 209 |
| Br CN CN COOC2 H5 |
| ##STR239## dark blue |
| 210 |
| Br CN CN COOC2 H5 |
| ##STR240## dark blue |
| 211 |
| Br CN CN COOC2 H5 |
| ##STR241## dark blue |
| 212 |
| Br CN CN COOC2 H5 |
| ##STR242## dark blue |
| 213 |
| Br CN CN COOC2 H5 |
| ##STR243## dark blue |
| 214 |
| Br COOC2 H5 |
| CN CN |
| ##STR244## blue |
| 215 |
| Br COOC2 H5 |
| CN COOC2 H5 |
| ##STR245## dark blue |
| 216 |
| Br COOC2 H5 |
| CN CON(CH3)2 |
| ##STR246## bluish violet |
| 217 |
| Br CONH2 |
| CN COOC2 H5 |
| ##STR247## dark blue |
| 218 |
| Br SO2 CH3 |
| CN COOC2 H5 |
| ##STR248## dark blue |
| 219 |
| Br CON(CH3)2 |
| CN COOC2 H5 |
| ##STR249## dark blue |
| 220 |
| Br CN CN COOC2 H5 |
| ##STR250## dark blue |
| 221 |
| Br CN CN COOC2 H5 |
| ##STR251## blue |
| 222 |
| Br CN CN COOCH3 |
| ##STR252## blue |
| 223 |
| Br CN CN COOCH3 |
| ##STR253## navy blue |
| 224 |
| Cl CN CN |
| ##STR254## |
| ##STR255## dark blue |
| 225 |
| F CN CN COOC2 H5 |
| ##STR256## dark blue |
| 226 |
| F CN CN COOC2 H5 |
| ##STR257## dark blue |
| 227 |
| F CN CN COOC2 H5 |
| ##STR258## dark blue |
| 228 |
| F COOC2 H5 |
| CN COOC2 H5 |
| ##STR259## dark blue |
| 229 |
| OC2 H5 |
| CN COOC2 H5 |
| COOC2 H5 |
| ##STR260## dark blue |
| 230 |
| OC2 H5 |
| CN COOC2 H5 |
| COOC2 H5 |
| ##STR261## blue |
| 231 |
| OC2 H5 |
| CN COOC2 H5 |
| COOC2 H5 |
| ##STR262## dark blue |
| 232 |
| OC2 H5 |
| CN COOC2 H5 |
| COOC2 H5 |
| ##STR263## blue |
| 233 |
| OC2 H5 |
| CN CN CN |
| ##STR264## dark blue |
| 234 |
| OC2 H5 |
| CN COCH3 COOC2 H5 |
| ##STR265## dark blue |
| 235 |
| OC2 H5 |
| COOC2 H5 |
| CN COOC2 H5 |
| ##STR266## blue |
| 236 |
| OC2 H5 |
| COOC2 H5 |
| CN COOC2 H5 |
| ##STR267## dark blue |
| 237 |
| OC2 H5 |
| COOC2 H5 |
| CN COOC2 H5 |
| ##STR268## blue |
| 238 |
| OC2 H5 |
| COOC2 H5 |
| COOC2 H5 |
| COOC2 H5 |
| ##STR269## dark blue |
| 239 |
| OC2 H5 |
| COOC2 H5 |
| COCH3 COOC2 H5 |
| ##STR270## dark blue |
| 240 |
| OC2 H5 |
| COOC2 H5 |
| COCH3 COCH3 |
| ##STR271## bluish violet |
| 241 |
| OC2 H5 |
| COOC2 H5 |
| COCH3 CN |
| ##STR272## dark blue |
| 242 |
| OC2 H5 |
| ##STR273## |
| CN COOC2 H5 |
| ##STR274## dark blue |
| 243 |
| OC2 H5 |
| ##STR275## |
| CN COOC2 H5 |
| ##STR276## blue |
| 244 |
| OC2 H5 |
| SO2 CH3 |
| CN COOC2 H5 |
| ##STR277## dark blue |
| 245 |
| OC2 H5 |
| SO2 CH3 |
| CN COOC2 H5 |
| ##STR278## dark blue |
| 246 |
| OC2 H5 |
| SO2 CH3 |
| CN COOC2 H5 |
| ##STR279## blue |
| 247 |
| OC2 H5 |
| CN CN CON(CH3)2 |
| ##STR280## reddish blue |
| 248 |
| OC2 H5 |
| CN CN COOC2 H5 |
| ##STR281## reddish blue |
| 249 |
| OC2 H5 |
| CN CN COOC2 H5 |
| ##STR282## dark blue |
| 250 |
| OC2 H5 |
| CN CN COOC2 H5 |
| ##STR283## dark blue |
| 251 |
| OC2 H5 |
| CN CN COOC2 H5 |
| ##STR284## dark blue |
| 252 |
| OC2 H5 |
| CN CN COOC2 H5 |
| ##STR285## dark blue |
| 253 |
| OC2 H5 |
| CN CN COOC2 H5 |
| ##STR286## dark blue |
| 254 |
| OC2 H5 |
| CN CN COOC2 H5 |
| ##STR287## blue |
| 255 |
| OC2 H5 |
| CN CN COOC2 H5 |
| ##STR288## blue |
| 256 |
| OC2 H5 |
| CN CN COOC2 H5 |
| ##STR289## blue |
| 257 |
| OC2 H5 |
| CN CN COOC4 H9 (n) |
| ##STR290## blue |
| 258 |
| OC2 H5 |
| CN CN COOC4 H9 (n) |
| ##STR291## blue |
| 259 |
| OC2 H5 |
| CN CN COOC4 H9 (n) |
| ##STR292## blue |
| 260 |
| OC2 H5 |
| CN CN COOC4 H9 (n) |
| ##STR293## dark blue |
| 261 |
| OC2 H5 |
| CN CN |
| ##STR294## |
| ##STR295## dark blue |
| 262 |
| OC2 H5 |
| CN CN |
| ##STR296## |
| ##STR297## dark blue |
| 263 |
| OC2 H5 |
| CN CN |
| ##STR298## |
| ##STR299## dark blue |
| 264 |
| OC2 H5 |
| CN CN CONH2 |
| ##STR300## dark blue |
| 265 |
| OC2 H5 |
| CN COOC2 H5 |
| COOC2 H5 |
| ##STR301## navy blue |
| 266 |
| OC2 H5 |
| CN COCH3 COOC2 H5 |
| ##STR302## dark blue |
| 267 |
| OC2 H5 |
| CN CN CONHCH3 |
| ##STR303## dark blue |
| 268 |
| OC2 H5 |
| CN CN COOC2 H5 |
| ##STR304## navy blue |
| 269 |
| OC2 H5 |
| CN CN COOC2 H5 |
| ##STR305## violet |
| 270 |
| OC2 H5 |
| CN CN COOC2 H5 |
| ##STR306## violet |
| 271 |
| OC2 H5 |
| CN CN COOC2 H5 |
| ##STR307## violet |
| 272 |
| OC2 H5 |
| CN CN CONHCH3 |
| ##STR308## dark blue |
| 273 |
| OC2 H5 |
| CN CN CONHC2 H5 |
| ##STR309## dark blue |
| 274 |
| OC2 H5 |
| CN CN SO2 CH3 |
| ##STR310## dark blue |
| 275 |
| OC2 H5 |
| CN CN COCH3 |
| ##STR311## dark blue |
| 276 |
| OC2 H5 |
| CN CN COOCH3 |
| ##STR312## dark blue |
| 277 |
| OCH3 |
| CN CN COOC2 H5 |
| ##STR313## bluish violet |
| 278 |
| OC6 H5 |
| CN CN COOC2 H5 |
| ##STR314## bluish violet |
| 279 |
| SC6 H5 |
| CN CN COOC2 H5 |
| ##STR315## bluish voilet |
| 280 |
| SC6 H5 |
| CN CN COOC2 H5 |
| ##STR316## dark blue |
| 281 |
| OCH3 |
| CN CN COOC2 H5 |
| ##STR317## dark blue |
| 282 |
| OCH3 |
| CN CN COOC2 H5 |
| ##STR318## blue |
| 283 |
| OCH3 |
| CN CN COOC4 H9 (n) |
| ##STR319## blue |
| 284 |
| OC6 H5 |
| CN CN COOC2 H5 |
| ##STR320## dark blue |
| 285 |
| SC6 H5 |
| CN CN COOC 2 H5 |
| ##STR321## dark blue |
| 286 |
| SC6 H5 |
| CN CN COOC2 H5 |
| ##STR322## dark blue |
| 287 |
| SC6 H5 |
| CN CN COOC2 H5 |
| ##STR323## dark blue |
| 288 |
| SC6 H5 |
| CN CN COOC2 H5 |
| ##STR324## dark blue |
| 289 |
| SC2 H5 |
| COOC2 H5 |
| CN COOC2 H5 |
| ##STR325## dark blue |
| __________________________________________________________________________ |
(a) 18.6 parts of 2-amino-4-chloro-3-cyano-5-formylthiophene were suspended in 140 parts by volume of ethanol, and 2 parts of glacial acetic acid and 2 parts of piperidine were added. Thereafter, 50 parts by volume of ethyl cyanoacetate were added dropwise at room temperature and the mixture was stirred for 7 hours at 60°C It was then introduced into 500 parts of an ice/water mixture, and the precipitate was filtered off under suction, washed with water and dried at 60°C under reduced pressure to give 20 parts of 2-amino-4-chloro-3-cyano-5-(β-cyano-β-carboethoxyvinyl)-thiophen e of the formula ##STR326## which was reacted without further purification.
(b) 14 parts of this product were suspended in 100 parts by volume of 85% strength phosphoric acid, and 16 parts of nitrosylsulfuric acid (11.5% of N2 O3) were added slowly at 0°-5°C After 2 hours at this temperature, the diazonium salt solution was run into a solution of 9.75 parts of N-cyanoethyl-N-ethyl-m-toluidine in a mixture of 125 parts of water, 500 parts of ice, 25 parts by volume of 32% strength hydrochloric acid and 1 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried under reduced pressure to give 20 parts of the dye described in Example 155, of the formula ##STR327## On polyesters, this dye gives dark blue dyeings having generally good fastness properties.
14.5 parts of 2-amino-3-cyano-4-ethoxy-5-(β-cyano-β-carboethoxyvinyl)-thiophen e were suspended in 160 parts by volume of 85% strength phosphoric acid and diazotized with 16 parts of nitrosylsulfuric acid (11.5% of N2 O3) at 0°-5°C After 2 hours at this temperature, the diazonium salt solution was reacted with 9.75 parts of N-cyanoethyl-N-ethyl-m-toluidine similarly to Example 290 to give 20 parts of the dye of the formula ##STR328## which, on polyesters, gives blue dyeings possessing good lightfastness and fastness to dry heat pleating and setting.
14 parts of 2-amino-4-chloro-3-cyano-5-(β-cyano-β-methylaminocarbonyl)-vinyl )-thiophene were suspended in 120 parts by volume of 85% strength phosphoric acid and reacted with 16 parts of nitrosylsulfuric acid at 0°-5°C, and the mixture was stirred for 2 hours at this temperature. The diazonium salt solution was run slowly into a mixture of 7.5 parts of N,N-diethylaniline, 100 parts of water, 300 parts of ice, 25 parts by volume of 32% strength hydrochloric acid and 1 part of amidosulfonic acid. When coupling was complete, the suspension was filtered and the residue was washed neutral and dried to give 16 parts of the dye of the formula ##STR329## which, on polyesters, gives dark blue dyeings possessing generally good fastness properties.
The compounds characterized in the Table below were obtained similarly to Examples 290-292.
| __________________________________________________________________________ |
| ##STR330## |
| Example |
| No. X Y Y1 |
| Y2 |
| K (*) |
| __________________________________________________________________________ |
| 293 Br CN CN COOCH3 |
| ##STR331## dark blue |
| 294 Br CN CN COOCH3 |
| ##STR332## dark blue |
| 295 Br CN CN COOCH3 |
| ##STR333## blue |
| 296 Br CN CN COOCH3 |
| ##STR334## blue |
| 297 Cl CN CN COOC2 H5 |
| ##STR335## dark blue |
| 298 Cl CN CN COOC2 H5 |
| ##STR336## dark blue |
| 299 Cl CN CN COOC2 H5 |
| ##STR337## dark blue |
| 300 Cl CN CN COOC2 H5 |
| ##STR338## dark blue |
| 301 Cl CN CN CONHCH3 |
| ##STR339## dark blue |
| 302 Cl COOCH3 |
| CN COOC2 H5 |
| ##STR340## dark blue |
| 303 Cl SO2 CH3 |
| CN COOC2 H5 |
| ##STR341## dark blue |
| 304 Cl CN CN COOC2 H5 |
| ##STR342## reddish blue |
| 305 F CN CN COOC2 H5 |
| ##STR343## dark blue |
| 306 F CN CN COOC2 H5 |
| ##STR344## dark blue |
| 307 F CN CN COOC2 H5 |
| ##STR345## blue |
| 308 Cl CN CN CN |
| ##STR346## blue |
| 309 OC2 H5 |
| CN CN COOCH3 |
| ##STR347## dark blue |
| 310 OC2 H5 |
| CN CN COOCH3 |
| ##STR348## blue |
| 311 OCH3 |
| CN CN COOC2 H5 |
| ##STR349## dark blue |
| 312 OC2 H5 |
| CN CN COOC2 H5 |
| ##STR350## dark blue |
| 313 SC6 H5 |
| CN CN COOC2 H5 |
| ##STR351## dark blue |
| 314 OC2 H5 |
| CN CN COOCH3 |
| ##STR352## dark blue |
| 315 SC6 H5 |
| CN CN COOC2 H5 |
| ##STR353## dark blue |
| __________________________________________________________________________ |
| (*) Dyeing on polyester |
The following dyes characterized by the substituents can also be prepared similarly to the methods described:
| __________________________________________________________________________ |
| Example Color on |
| No. T X Y K polyester |
| __________________________________________________________________________ |
| 316 CHO Cl CN |
| ##STR354## blue |
| 317 CHO Cl CN |
| ##STR355## greenish blue |
| 318 CHO Cl CN |
| ##STR356## blue |
| 319 CHO Cl CN |
| ##STR357## blue |
| 320 CHO Cl CN |
| ##STR358## blue |
| 321 CHO Cl CN |
| ##STR359## blue |
| 322 CHO Br CN |
| ##STR360## blue |
| 323 CHO Cl CN |
| ##STR361## blue |
| 324 CHO Cl CN |
| ##STR362## blue |
| 325 CHO Cl CN |
| ##STR363## reddish blue |
| 326 CHO Cl CN |
| ##STR364## blue |
| 327 CHO Cl CN |
| ##STR365## reddish blue |
| 328 CHO Cl CN |
| ##STR366## blue |
| 329 CHO Cl CN |
| ##STR367## blue |
| 330 CHO Cl CN |
| ##STR368## blue |
| 331 CHO Cl CN |
| ##STR369## blue |
| 332 CHO Cl CN |
| ##STR370## blue |
| 333 CN Cl CN |
| ##STR371## blue |
| 334 CN Cl CN |
| ##STR372## blue |
| 335 NO2 |
| Cl CN |
| ##STR373## greenish blue |
| 336 NO2 |
| Cl CN |
| ##STR374## blue |
| 337 NO2 |
| Cl CN |
| ##STR375## blue |
| 338 CN Cl CN |
| ##STR376## blue |
| 339 CN Cl CN |
| ##STR377## blue |
| 340 CN Cl CN |
| ##STR378## blue |
| 341 CHO Cl CN |
| ##STR379## blue |
| 342 CHO Cl CN |
| ##STR380## blue |
| 343 CHO Cl CN |
| ##STR381## reddish blue |
| 344 CHO Cl CN |
| ##STR382## blue |
| 345 CHO Cl CN |
| ##STR383## blue |
| 346 CHO Br CN |
| ##STR384## blue |
| 347 CHO Br CN |
| ##STR385## blue |
| 348 CHO C6 H5 S |
| CN |
| ##STR386## reddish blue |
| 349 CHO C6 H5 S |
| CN |
| ##STR387## greenish blue |
| 350 CHO OC2 H5 |
| CN |
| ##STR388## reddish blue |
| 351 CHO C6 H5 SO2 |
| CN |
| ##STR389## blue |
| 352 CHO C6 H5 SO2 |
| CN |
| ##STR390## blue |
| 353 CN Cl CN |
| ##STR391## reddish blue |
| 354 CN Cl CN |
| ##STR392## blue |
| __________________________________________________________________________ |
| __________________________________________________________________________ |
| Example Color on |
| No. T X Y K polyester |
| __________________________________________________________________________ |
| 355 H5 C2 O2 C(CN)CCH |
| Cl |
| CN |
| ##STR393## blue |
| __________________________________________________________________________ |
2 parts of the dye described in Example 3, in 30 parts by volume of dimethylformamide and 50 parts by volume of glacial acetic acid, were stirred and 0.7 part of aniline was added. Stirring was continued for 12 hours at room temperature and 500 parts of water were added and the mixture was filtered under suction to give 2.2 parts of a powder of the formula ##STR394## which dyes polyester fabric in fast blue hues.
A suspension of 4 parts of the dye described in Example 3 in 50 parts by volume of dimethylformamide and 2 drops of concentrated sulfuric acid were added to 1.1 parts of phenylhydrazine in 40 parts by volume of ethanol. The mixture was stirred for 12 hours at 25°C, after which 500 parts of water were added and the dye of the formula ##STR395## was filtered off under suction and dried. 5 parts of a black powder which dyes polyester fabric in fast blue hues were obtained.
2.3 parts of the dye described in Example 23 were stirred in 50 parts by volume of formic acid, 0.5 part of hydroxylamine hydrochloride and 0.5 part of sodium formate for 12 hours at room temperature. 400 parts of water were added, after which the mixture was filtered under suction to give 2.4 parts of the dye of the formula ##STR396## which dyes polyester fabric in fast blue hues.
18.7 parts of 2-amino-3-cyano-4-chloro-5-formylthiophene in 120 parts by volume of glacial acetic acid and 40 parts by volume of propionic acid were stirred for 1 hour at room temperature, after which the mixture was cooled to 0°-5°C, 31 parts of 42% strength nitrosylsulfuric acid were added and stirring was continued for about one hour at this temperature.
The coupling component employed was obtained as follows: a thoroughly stirred mixture of 17 parts (based on dry substance) of water-moist 2-chloro-3-cyano-4-methyl-6-aminopyridine (obtained, for example, by the process described in German Patent 2,260,827), 20 parts by volume of isobutanol, 18 parts of 3-aminopropyl 4-hydroxybutyl ether and 8 parts of sodium carbonate was heated under a descending condenser for 5 hours at 145°-150°C until a thin layer chromatogram showed that conversion was complete. The mixture was cooled to about 100°C, after which 35 parts of acetic acid were added dropwise and 15 parts of 96% strength sulfuric acid were introduced dropwise at 35°-40°C with further slight cooling. Stirring was continued for 3 hours, after which about 92% of the hydroxy compound were found to be acetylated. The solution of the diazonium salt was run into a thoroughly stirred mixture of 100 parts of the resulting coupling component, 300 parts of ice and 100 parts of water, and stirring was continued for about 2 hours at 0°-5°C until the diazonium salt solution had been consumed. Thereafter, the coupling mixture was filtered under suction and the residue was washed neutral and dried at 80°C The greenish black powder contains about 90% of the compound of the formula ##STR397## [λmax : 546 nm (9:1 dimethylformamide/acetic acid)] as well as about 10% of the non-acetylated hydroxy compound.
The dye mixture possesses very good tinctorial properties and, on polyester, gives very deep, brilliant, reddish violet dyes possessing very good lightfastness and fastness to plating.
When an equivalent amount of the coupling component described below was used under the preparation conditions of the above example, the reddish blue dye (λmax : 572 nm, 9:1 dimethylformamide/acetic acid) of the formula ##STR398## was obtained. The product still contained about 5% of the hydroxy compound.
The coupling component used was obtained as follows: 45 parts of 2-chloro-3-cyano-4-methyl-6-(3'-hydroxypropylamino)-pyridine (obtained as described in German Patent 2,260,827) were stirred in the presence of one part of p-toluenesulfonic acid in 37 parts of aniline for one hour at 125°C A total of 10 parts of sodium carbonate were added at 135°C in three portions at 10 minute intervals, and stirring was continued for about 4 hours at 145°C until a thin layer chromatogram showed that conversion was complete. Excess aniline was distilled off under reduced pressure, and the hot melt was discharged on to 200 parts by volume of hot water. The aqueous solution was decanted, and the remaining melt was stirred several times with hot water containing acetic acid and was separated off cold. After drying, 14.2 parts of the melt, consisting of 2-phenylamino-3-cyano-4-methyl-6-(3'-hydroxypropylamino)-pyridine, were dissolved in 50 parts by volume of glacial acetic acid, and 6 parts of 96% strength sulfuric acid were added dropwise. The mixture was stirred for 3 hours at 60°C, after which the solution was used directly in the coupling reaction decribed.
The dyes listed in Table I were also obtained in a similar manner, these dyes having a similar property spectrum. The λmax values were determined in a 9:1 mixture of dimethylformamide and acetic acid.
| TABLE 1 |
| __________________________________________________________________________ |
| ##STR399## |
| Exam- |
| ple λmax |
| No. X Y R1 R2 [nm] |
| __________________________________________________________________________ |
| 361 Cl CN H C3 H6 OC4 H8 OCOC2 |
| H5 545.5 |
| 362 Cl CN H C3 H6 OC2 H7 OC2 H5 |
| 547 |
| 363 Cl CN H C3 H6 OC2 H4 OC4 H9 |
| 546.8 |
| 364 Cl CN C2 H4 OCH3 |
| ##STR400## 565 |
| 365 Cl CN |
| ##STR401## |
| ##STR402## 567 |
| 366 Cl CN |
| ##STR403## |
| ##STR404## 573 |
| 367 OC2 H5 |
| CN H C3 H6 OC4 H8 OCOCH3 |
| 538 |
| 368 OC2 H5 |
| CN H C3 H6 OC2 H4 OC2 H5 |
| 540 |
| 369 OC2 H5 |
| CN C3 H6 OCOCH3 |
| ##STR405## 560.5 |
| 370 OC2 H5 |
| CN C3 H6 OH |
| ##STR406## 569 |
| 371 |
| ##STR407## |
| CN H C3 H6 OC4 H8 OCOCH3 |
| 540 |
| 372 |
| ##STR408## |
| CN H C3 H6 OC4 H8 OCOCH3 |
| 540 |
| __________________________________________________________________________ |
14.6 parts of 2-amino-3-cyano-4-ethoxy-5-(2'-cyano-2'-carbethoxyvinyl)-thiophene were diazotized similarly to the procedure described in Example 359 but using half the amount of reagents and assistants, and the product was coupled to 2-(4'-acetoxybutoxy)-3'-propylamino-3-cyano-4-methyl-6-aminopyridine. This gives a bluish black powder of the formula ##STR409## which still contains about 10% of the hydroxy compound and dyes polyester materials in medium blue hues which have very good lightfastness, fastness to washing and fastness to plating.
The diazo component was obtained as follows: 60 parts of 2-amino-3-cyano-4-ethoxythiophene-5-carbaldehyde in 200 parts by volume of dimethylformamide and 57 parts of ethyl cyanoacetate were stirred at room temperature. 10 parts by volume of a saturated aqueous sodium acetate solution were added dropwise, and stirring was continued for 2 hours at 40°C Precipitation was completed by adding 1,000 ml of ice-cold methanol, and the product was filtered off, washed first with ice-cold methanol and then with water, and dried at 60°C Yield: 60 parts (67.4%).
The procedure described in Example 359 was used, but with half the amount of reagents and assitants, and 14.1 parts of 2-amino-3-cyano-4-chloro-5-(2'-cyano-2'-carbethoxyvinyl)-thiophene were diazotized and the product coupled to 2-(4'-acetoxybutoxy)-3'-propylamino-3-cyano-4-methyl-6-(3'-acetoxypropylam ino)-pyridine.
This gives a black powder which consists of 90% of the compound of the formula ##STR410## (λmax =585.5 nm; acetone) and dyes polyester in medium blue hues which have very good lightfastness, fastness to washing and fastness to plating.
The diazo component was obtained by a method similar to that described in Example 373, and the coupling cOmponent was obtained as follows:
45 parts of 2-chloro-3-cyano-4-methyl-6-(3'-hydroxypropylamino)-pyridine (obtained as described in German Patent 2,260,827) were stirred for 5 hours at 145°C in the presence of 14 parts of sodium carbonate in 33 parts of 3-aminopropyl 4-hydroxybutyl ether, and the mixture was cooled to 100°C and discharged on to 120 parts by volume of glacial acetic acid. 41 g of 96% strength sulfuric acid were then added dropwise at 30°C The mixture was stirred for 3 hours at 40°C, after which a quarter of the solution was converted to the dye, as described above.
The dyes in Table 2, which have similar properties, were obtained in a similar manner. The λmax values were determined in acetone, except for those marked with *, which were measured in a 9:1 dimethylformamide/acetic acid mixture.
| TABLE 2 |
| __________________________________________________________________________ |
| ##STR411## |
| Example λmax |
| No. T X Y R1 R2 [nm] |
| __________________________________________________________________________ |
| 375 COOC2 H5 |
| OC2 H5 |
| CN H C3 H6 OCH3 |
| 583 |
| 376 COOC2 H5 |
| OC2 H5 |
| CN H |
| ##STR412## |
| 580.5 |
| 377 COOC2 H5 |
| OC2 H5 |
| CN H C3 H6 OC2 H4 OC2 |
| H5 594* |
| 378 COOC2 H5 |
| OC2 H5 |
| CN C3 H6 OCH3 |
| C3 H6 OC4 H8 OCOCH3 |
| 597* |
| 379 COOC2 H5 |
| OC2 H5 |
| CN C2 H4 OH |
| C3 H6 OC2 H4 OC2 |
| H5 602.3* |
| 380 COOC2 H5 |
| OC2 H5 |
| CN C3 H6 OC2 H4 OCH3 |
| C3 H4 OCOCH3 |
| 591.5 |
| 381 COOC2 H5 |
| OC2 H5 |
| CN C2 H4 OCOCH3 |
| C3 H6 OC2 H4 OC2 |
| H5 591.5 |
| 382 COOC2 H5 |
| OC2 H5 |
| CN C3 H6 OCOCH3 |
| C3 H6 OC4 H8 OCOCH3 |
| 594 |
| 383 COOC2 H5 |
| OC2 H5 |
| CN C3 H6 OC4 H8 OCOCH3 |
| C3 H6 OC4 H8 OCOCH3 |
| 594 |
| 384 CN OC2 H5 |
| CN H C3 H6 OC4 H8 OCOCH3 |
| 583 |
| 385 CN OC2 H5 |
| CN C3 H6 OCH3 |
| C3 H6 OC4 H8 OCOCH3 |
| 595 |
| 386 CN OC2 H5 |
| CN C3 H6 OCOCH3 |
| C3 H6 OC4 H8 OCOCH3 |
| 595 |
| 387 CN Cl CN C3 H6 OCOCH3 |
| ##STR413## |
| 613.5* |
| 388 CN Cl CN C3 H4 OH |
| C3 H6 OC2 H4 OC2 |
| H5 605.3* |
| 389 CN Cl CN H C3 H6 OC2 H4 OC2 |
| H5 578 |
| 390 COOCH3 |
| Cl CN H C3 H6 OC4 H8 OCOCH3 |
| 577 |
| 391 COOC2 H5 |
| Cl CN H C3 H6 OCH3 |
| 578 |
| 392 COOC2 H5 |
| Cl CN H |
| ##STR414## |
| 575.5 |
| 393 COOC2 H5 |
| Cl CN H |
| ##STR415## |
| 588 |
| 394 CN Cl CN C3 H6 OCOCH3 |
| C3 H6 OC4 H8 OCOCH3 |
| 586 |
| 395 COOC2 H5 |
| Cl CN C3 H6 OCH3 |
| C3 H6 OC2 H4 OC4 |
| H9 588 |
| 396 COOC2 H5 |
| Cl CN C3 H6 OCH3 |
| C3 H6 OC4 H8 OCOCH3 |
| 585.5 |
| 397 COOC 2 H5 |
| Cl CN C2 H4 OCOCH3 |
| C3 H6 OC2 H4 OC2 |
| H5 586 |
| 398 COOC2 H5 |
| Cl CN C3 H6 OC4 H8 OCOCH3 |
| ##STR416## |
| 612* |
| 399 CN Cl CN C3 H6 OC4 H8 OCOCH3 |
| C3 H6 OC4 H8 OCOCH3 |
| 586 |
| __________________________________________________________________________ |
7.3 parts of 2-amino-3-cyano-5-formyl-4-phenylsulfonylthiophene in 30 parts by volume of 85% strength sulfuric acid were stirred at no higher than 30°C 8.3 parts of nitrosylsulfuric acid (11.5% of N2 O3) were added dropwise at 0°-5°C, after which stirring was continued for 4 hours at this temperature.
This diazonium salt solution was diluted with 20 ml of concentrated sulfuric acid and then run slowly, at 0°C, into a solution of 6.6 parts of 3-[N,N-di-n-butylamino]acetanilide in a mixture of 25 parts by volume of dimethylformamide, 125 parts of water, 300 parts of ice and 0.5 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried, and 12 parts of the dye of the formula ##STR417## were obtained. This dye dyes polyester fibers in fast blue hues.
7.3 parts of 2-amino-3-cyano-5-formyl-4-phenylsulfonylthiophene were diazotized by a method similar to that described in the Example above.
The diazonium salt solution was added dropwise, at 0°C, to a solution of 5.2 parts of 3-(N,N-diethylamino)-acetanilide in a mixture of 125 parts of water, 350 parts of ice, 10 parts by volume of 32% strength hydrochloric acid and 0.5 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried, and 10.5 parts of a powder of the formula ##STR418## were obtained. This dye dyes polyester fabric in fast blue hues.
The dyes shown in the Table below were obtained in a similar manner.
| __________________________________________________________________________ |
| ##STR419## |
| Example Dyeing on |
| No. T X Y K polyester |
| __________________________________________________________________________ |
| 402 CHO C6 H5 SO2 |
| CN |
| ##STR420## greenish blue |
| 403 CHO C6 H5 SO2 |
| CN |
| ##STR421## bluish violet |
| 404 CHO C6 H5 SO2 |
| CN |
| ##STR422## blue |
| 405 CHO C6 H5 SO2 |
| CN |
| ##STR423## blue |
| 406 CHO C6 H5 SO2 |
| CN |
| ##STR424## blue |
| 407 CHO C6 H5 SO2 |
| CN |
| ##STR425## reddish blue |
| 408 CHO C6 H5 SO2 |
| CN |
| ##STR426## bluish violet |
| 409 CHO C6 H5 SO2 |
| CN |
| ##STR427## greenish blue |
| 410 CHO C6 H5 SO2 |
| CN |
| ##STR428## blue |
| 411 CHO C6 H5 SO2 |
| CN |
| ##STR429## blue |
| 412 CHO C6 H5 SO2 |
| CO2 C2 H5 |
| ##STR430## blue |
| 413 CHO C6 H5 SO2 |
| CN |
| ##STR431## blue |
| 414 CHO C6 H5 SO2 |
| CN |
| ##STR432## blue |
| 415 CHO C6 H5 SO2 |
| CN |
| ##STR433## blue |
| 416 CHO C6 H5 SO2 |
| CN |
| ##STR434## blue |
| 417 CHO C6 H5 SO2 |
| CN |
| ##STR435## blue |
| 418 CHO C6 H5 SO2 |
| CN |
| ##STR436## blue |
| 419 CHO |
| ##STR437## CO2 C2 H5 |
| ##STR438## reddish blue |
| 420 CHO C6 H5 SO2 |
| CO2 C2 H5 |
| ##STR439## blue |
| 421 CHO C6 H5 SO2 |
| CONH2 |
| ##STR440## blue |
| 422 CHO C6 H5 SO2 |
| NO2 |
| ##STR441## blue |
| 423 CHO C6 H5 SO2 |
| CON(CH3)2 |
| ##STR442## blue |
| 424 CHO C6 H5 SO2 |
| SO2 CH3 |
| ##STR443## blue |
| 425 CHO CH3 SO2 |
| CO2 C2 H5 |
| ##STR444## blue |
| 426 CHO C6 H5 SO2 |
| CN |
| ##STR445## blue |
| 427 CHO C6 H5 SO2 |
| CN |
| ##STR446## blue |
| 428 CHO CH3 SO2 |
| CN |
| ##STR447## blue |
| 429 CHO C6 H5 SO2 |
| CN |
| ##STR448## violet |
| 430 CHO C6 H5 SO2 |
| CN |
| ##STR449## blue |
| 431 CHO C6 H5 SO2 |
| CO2 C2 H5 |
| ##STR450## blue |
| 432 CHO C6 H5 SO2 |
| CN |
| ##STR451## yellowish brown |
| 433 CHO C6 H5 SO2 |
| CN |
| ##STR452## red |
| 434 CHO C6 H5 SO2 |
| CN |
| ##STR453## red |
| 435 CHO C6 H5 SO2 |
| CN |
| ##STR454## blue |
| 436 CHO C6 H5 SO2 |
| CN |
| ##STR455## blue |
| 437 CHO p-Cl-C6 H4 SO2 |
| CN |
| ##STR456## blue |
| 438 CHO C6 H5 SO2 |
| CN |
| ##STR457## blue |
| 439 CHO C 6 H5 SO2 |
| CN |
| ##STR458## violet |
| 440 CHO C6 H5 SO2 |
| CN |
| ##STR459## red |
| 441 CHO C6 H5 SO2 |
| CN |
| ##STR460## red |
| 442 CN C6 H5 SO2 |
| CN |
| ##STR461## blue |
| 443 CN C6 H5 SO2 |
| CN |
| ##STR462## blue |
| 444 CN C6 H5 SO2 |
| CN |
| ##STR463## greenish blue |
| 445 CN CH3 SO2 |
| CN |
| ##STR464## reddish blue |
| 446 CN C6 H5 SO2 |
| CN |
| ##STR465## blue |
| 447 NO2 |
| C6 H5 SO2 |
| CN |
| ##STR466## reddish blue |
| 448 NO2 |
| C6 H5 SO2 |
| CN |
| ##STR467## blue |
| 449 NO2 |
| C6 H5 SO2 |
| CN |
| ##STR468## blue |
| 450 NO2 |
| C6 H5 SO2 |
| CN |
| ##STR469## greenish blue |
| 451 |
| ##STR470## |
| C6 H5 SO2 |
| CN |
| ##STR471## blue |
| 452 Cl C6 H5 SO2 |
| CN |
| ##STR472## reddish blue |
| 453 Br CH3 SO2 |
| CN |
| ##STR473## reddish |
| __________________________________________________________________________ |
| blue |
1.2 parts of sodium phenylsulfinate were added to 2.3 parts of 4-chloro-3-cyano-5-formyl-2-(4'-N,N-dibutylamino-2'-acetylaminophenylazo)- thiophene in 50 parts by volume of dimethylformamide, and the mixture was stirred at room temperature. When the reaction was complete (thin layer chromatogram), the reaction mixture was poured on to 300 parts of water, and the dye formed was isolated. 2.4 parts of the dye of the formula ##STR474## were obtained. This dye dyes polyester fibers in fast blue hues.
The dyes shown in the Table below were obtained by a method similar to Example 454.
| __________________________________________________________________________ |
| ##STR475## |
| Example Dyeing on |
| No. T X Y K polyester |
| __________________________________________________________________________ |
| 455 CHO C6 H5 SO2 |
| CN |
| ##STR476## blue |
| 456 CHO C6 H5 SO2 |
| CN |
| ##STR477## bluish violet |
| 457 CHO C6 H5 SO2 |
| CN |
| ##STR478## blue |
| 458 CHO C6 H5 SO2 |
| CN |
| ##STR479## blue |
| 459 CHO C6 H5 SO2 |
| CN |
| ##STR480## blue |
| 460 CHO C6 H5 SO2 |
| CN |
| ##STR481## blue |
| 461 CHO C6 H5 SO2 |
| CN |
| ##STR482## reddish blue |
| 462 CHO C6 H5 SO2 |
| CN |
| ##STR483## reddish blue |
| 463 CHO C6 H5 SO2 |
| CO2 C2 H5 |
| ##STR484## blue |
| __________________________________________________________________________ |
2.6 parts of the dye described in Example 413 were dissolved in 80 parts by volume of dioxane, 1.1 parts of ethyl cyanoacetate, 0.4 part of glacial acetic acid and 0.4 part of piperidine were added, and the mixture was stirred for 16 hours at room temperature. 50 parts of water and 50 parts of ice were then added, stirring was continued for 15 minutes, and the product was filtered off under suction, washed neutral and dried at 50°C under reduced pressure to give 2.8 parts of the dye of the formula ##STR485## which dyes polyester fibers in fast blue hues.
2.3 parts of the dye described in Example 403 were dissolved in 70 parts by volume of dioxane, 1.4 parts of butyl cyanoacetate, 0.4 part of glacial acetic acid and 0.4 part of piperidine were added and the mixture was stirred for 16 hours at room temperature. 50 parts of water and 50 parts of ice were then added, stirring was continued for 1 hour and the product was filtered off under suction, washed neutral and dried to give 2.5 parts of the dye of the formula ##STR486## which dyes polyester fabric in fast blue hues.
The dyes shown in the Table below were obtained similarly to the above Examples.
| __________________________________________________________________________ |
| ##STR487## |
| Example Dyeing on |
| No. X Y Y2 |
| Y3 K polyester |
| __________________________________________________________________________ |
| 466 C6 H5 SO2 |
| CN CN CN |
| ##STR488## blue |
| 467 C6 H5 SO2 |
| CN COCH3 |
| COOC2 H5 |
| ##STR489## blue |
| 468 C6 H5 SO2 |
| COOC2 H5 |
| CN COOC2 H5 |
| ##STR490## blue |
| 469 C6 H5 SO2 |
| COOC2 H5 |
| CN COC2 H5 |
| ##STR491## blue |
| 470 C6 H5 SO2 |
| COOC2 H5 |
| CN COOC2 H5 |
| ##STR492## blue |
| 471 C6 H5 SO2 |
| CN CN COOC2 H5 |
| ##STR493## reddish blue |
| 472 C6 H5 SO2 |
| CN CN COOC2 H5 |
| ##STR494## blue |
| 473 C6 H5 SO2 |
| CN CN COOC2 H5 |
| ##STR495## blue |
| 474 C6 H5 SO2 |
| CN CN COOC2 H5 |
| ##STR496## blue |
| 475 C6 H5 SO2 |
| CN CN COOC2 H5 |
| ##STR497## blue |
| 476 C6 H5 SO2 |
| CN CN COOC2 H5 |
| ##STR498## violet |
| 477 C6 H5 SO2 |
| CN CN COOC2 H5 |
| ##STR499## violet |
| 478 C6 H5 SO2 |
| CN CN COOC2 H5 |
| ##STR500## violet |
| 479 C6 H 5 SO2 |
| CN CN CONHCH3 |
| ##STR501## blue |
| 480 C6 H5 SO2 |
| CN CN CONHC2 H5 |
| ##STR502## blue |
| 481 C6 H5 SO2 |
| CN CN SO2 CH3 |
| ##STR503## blue |
| 482 C6 H5 SO2 |
| CN CN COCH3 |
| ##STR504## blue |
| 483 C6 H5 SO2 |
| CN CN COOCH3 |
| ##STR505## blue |
| 484 C6 H5 SO2 |
| CN CN COOC4 H9 (n) |
| ##STR506## greenish blue |
| 485 C6 H5 SO2 |
| CN CN COOC4 H9 (n) |
| ##STR507## greenish blue |
| 486 C6 H5 SO2 |
| CN CN COOC4 H9 (n) |
| ##STR508## blue |
| 487 C6 H5 SO2 |
| CN CN COOC4 H9 (n) |
| ##STR509## blue |
| 488 C6 H5 SO2 |
| CN CN |
| ##STR510## |
| ##STR511## blue |
| 489 C6 H5 SO 2 |
| CN CN |
| ##STR512## |
| ##STR513## blue |
| 490 C6 H5 SO2 |
| CN CN |
| ##STR514## |
| ##STR515## blue |
| 491 C6 H5 SO2 |
| CN CN CONH2 |
| ##STR516## blue |
| 492 CH3 SO2 |
| CN CN COOC2 H5 |
| ##STR517## blue |
| 493 CH3 SO2 |
| CN CN COOC2 H5 |
| ##STR518## blue |
| 494 CH3 SO2 |
| CN CN COOC2 H5 |
| ##STR519## blue |
| 495 P-ClC6 H4 SO2 |
| CN CN |
| ##STR520## |
| ##STR521## blue |
| __________________________________________________________________________ |
(a) 14.6 parts of 2-amino-3-cyano-5-formyl-4-phenylsulfonylthiophene were suspended in 50 parts by volume of ethanol, and 1 part of glacial acetic acid and 1 part of piperidine were added. 13 parts by volume of ethyl cyanoacetate were then added dropwise at room temperature, and the mixture was stirred for 5 hours at 60°C The reaction mixture was poured on to 800 parts of water, and the precipitate was filtered off under suction, washed with water and dried at 50°C under reduced pressure to give 16 parts of 2-amino-3-cyano-4-phenylsulfonyl-5-(β-cyano-β-carboethoxyvinyl)- thiophene of the formula ##STR522## which was reacted without further purification.
(b) 3.9 parts of 2-amino-3-cyano-4-phenylsulfonyl-5-(β-cyano-β-carboethoxyvinyl)- thiophene in 35 parts by volume of a 3:1 glacial acetic acid/propionic acid mixture were stirred, and 3.5 parts of nitrosylsulfuric acid (11.5% of N2 O3) were slowly added at 0°-5°C After 2 hours at this temperature, the diazonium salt solution was run into a solution of 2 parts of N-cyanoethyl-N-ethyl-m-toluidine in a mixture of 25 parts of water, 100 parts of ice, 5 parts by volume of 32% strength hydrochloric acid and 0.2 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried under reduced pressure. 4.5 parts of the dye of the formula ##STR523## were obtained. On polyester fibers, this dye gives blue dyeings having in general very good fastness properties.
3.4 parts of 2-amino-3-cyano-4-phenylsulfonyl-5-(β,β-dicyanovinyl)-thiophene were suspended in 25 parts by volume of 85% strength phosphoric acid and slowly reacted with 3.5 parts of nitrosylsulfuric acid (11.5% of N2 O3) at 0°-5°C, and the mixture was stirred for 2 hours at this temperature. This diazonium salt solution was run slowly into a mixture of 1.5 parts of N,N-diethylaniline, 20 parts of water, 60 parts of ice, 5 parts by volume of 32% strength hydrochloric acid and 0.2 part of amidosulfonic acid. When coupling was complete, the suspension was filtered and the dye was washed neutral and dried. 4.2 parts of the dye of the formula ##STR524## were obtained. On polyesters, this dye gives blue dyeings having generally good fastness properties.
The compounds shown in the Table below were obtained in a similar manner.
| __________________________________________________________________________ |
| ##STR525## |
| Example Dyeing on |
| No. X Y Y2 |
| Y3 |
| K polyester |
| __________________________________________________________________________ |
| 498 CH3 SO2 |
| CN CN COOCH3 |
| ##STR526## blue |
| 499 C6 H5 SO2 |
| CN CN COOCH3 |
| ##STR527## blue |
| 500 C6 H5 SO2 |
| CN CN COOCH3 |
| ##STR528## greenish blue |
| 501 C6 H5 SO2 |
| CN CN COOCH3 |
| ##STR529## greenish blue |
| 502 C6 H5 SO2 |
| CN CN COOC2 H5 |
| ##STR530## blue |
| 503 C6 H5 SO2 |
| CN CN COOC2 H5 |
| ##STR531## blue |
| 504 C6 H5 SO2 |
| CN CN COOC2 H5 |
| ##STR532## blue |
| 505 C6 H5 SO2 |
| CN CN COOC2 H5 |
| ##STR533## greenish blue |
| 506 C6 H5 SO2 |
| CN CN CONHCH3 |
| ##STR534## blue |
| 507 C6 H5 SO2 |
| COOCH3 |
| CN COOC2 H5 |
| ##STR535## blue |
| __________________________________________________________________________ |
Examples of suitable dischargeable dyes are the compounds of Examples 21, 22, 113 and 114 and those of Examples 341-355.
Etzbach, Karl-Heinz, Hansen, Guenter, Schefczik, Ernst, Reichelt, Helmut, Loeffler, Hermann
| Patent | Priority | Assignee | Title |
| 5132411, | Aug 30 1984 | CLARIANT FINANCE BVI LIMITED | Azo compounds having 2,4-disubstituted-3-halothienyl-5-diazo component radicals, dyeing processes therewith and substrates dyed therewith |
| 5254674, | Nov 07 1991 | Osaka Gas Company, Limited | Diaminoazothiophene compound and a method for preparing the same |
| 5270456, | Jul 10 1990 | BASF Aktiengesellschaft | Azo dyes with A2-aminothiophene dye azo component and a coupling component and coupling component of the diphenylamine series |
| 5440024, | Jul 13 1992 | DYSTAR JAPAN LTD | 3-cyano-5-nitrothiophene type monoazo dyes and mixtures thereof |
| 5502170, | May 12 1992 | BASF Aktiengesellschaft | Azo dyes with an acetalized diazo component of the thiophene or thiazole series |
| 5760196, | Feb 20 1995 | Sumitomo Chemical Company, Limited | Monoazo blue disperse dye compounds and methods for dyeing or printing hydrophobic fiber materials using the same |
| Patent | Priority | Assignee | Title |
| 4092329, | Dec 01 1972 | Sandoz Ltd. | Process for the synthesis of certain 2-amino-5-cyanothiophenes |
| 4255326, | Mar 30 1979 | CIBA-GEIGY CORPORATION, A CORP OF NEW YORK | Nitrogen and/or sulfur containing heterocyclic azo dyes with aniline, tetrahydroquinoline and benzomorpholine couplers having sulfate group |
| 4264495, | May 15 1972 | CIBA-GEIGY CORPORATION, A CORP OF NEW YORK | 2-Thienyl azo dyestuff compounds |
| 4507407, | Jun 25 1984 | Milliken Research Corporation | Process for in situ coloration of thermosetting resins |
| GB1394364, | |||
| GB2011937, | |||
| GB2125424, | |||
| JP56143245, | |||
| JP59204658, | |||
| JP60166345, | |||
| JP60226556, |
| Executed on | Assignor | Assignee | Conveyance | Frame | Reel | Doc |
| Jul 27 1988 | Sandoz AG | (assignment on the face of the patent) | / |
| Date | Maintenance Fee Events |
| Date | Maintenance Schedule |
| Aug 28 1993 | 4 years fee payment window open |
| Feb 28 1994 | 6 months grace period start (w surcharge) |
| Aug 28 1994 | patent expiry (for year 4) |
| Aug 28 1996 | 2 years to revive unintentionally abandoned end. (for year 4) |
| Aug 28 1997 | 8 years fee payment window open |
| Feb 28 1998 | 6 months grace period start (w surcharge) |
| Aug 28 1998 | patent expiry (for year 8) |
| Aug 28 2000 | 2 years to revive unintentionally abandoned end. (for year 8) |
| Aug 28 2001 | 12 years fee payment window open |
| Feb 28 2002 | 6 months grace period start (w surcharge) |
| Aug 28 2002 | patent expiry (for year 12) |
| Aug 28 2004 | 2 years to revive unintentionally abandoned end. (for year 12) |