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Patent US4686285 - Basic azo and non-azo compounds having one or two disubstituted 1,3,5 ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatents(i) Metal-free compounds of the formula ##STR1## (ii) tautomers thereof, (iii) 1:1 and 1:2 metal complexes of (i) and (ii), (iv) salts of (i), (ii), and (iii), and (v) mixtures of (i), (ii), (iii), and (iv), wherein the symbols are as defined in the Specification, are useful as dyes for, for example,...http://www.google.com/patents/US4686285?utm_source=gb-gplus-sharePatent US4686285 - Basic azo and non-azo compounds having one or two disubstituted 1,3,5-triazine rings each of which is linked through a bridging radical to the 1-position of a pyrazole ringAdvanced Patent SearchTry the new Google Patents, with machine-classified Google Scholar results, and Japanese and South Korean patents.Publication numberUS4686285 APublication typeGrantApplication numberUS 06/699,916Publication dateAug 11, 1987Filing dateFeb 8, 1985Priority dateFeb 10, 1984Fee statusLapsedPublication number06699916, 699916, US 4686285 A, US 4686285A, US-A-4686285, US4686285 A, US4686285AInventorsReinhard PedrazziOriginal AssigneeSandoz Ltd.Export CitationBiBTeX, EndNote, RefManPatent Citations (7), Referenced by (38), Classifications (34), Legal Events (7) External Links: USPTO, USPTO Assignment, EspacenetBasic azo and non-azo compounds having one or two disubstituted 1,3,5-triazine rings each of which is linked through a bridging radical to the 1-position of a pyrazole ring
US 4686285 AAbstract
(i) Metal-free compounds of the formula ##STR1## (ii) tautomers thereof, (iii) 1:1 and 1:2 metal complexes of (i) and (ii),
1. A metal-free compound of the formula ##STR171## a 1:1 or 1:2 metal complex of a metallizable metal-free azo compound of said formula or a salt or acid addition salt of a metal-free compound of said formula or of a 1:1 or 1:2 metal complex of a metallizable metal-free azo compound of said formula,wherein Ro is R or --N═N--T--N═N--,wherein T is the radical of a tetrazo component, each Y is independently hydroxy; C1-4 alkoxy; phenoxy; amino; an aliphatic, cycloaliphatic, aromatic or heterocyclic amino group; Z or ##STR172## and p is 1 when Ro is R and is 2 when Ro is --N═N--T--N═N--,wherein each A is independently phenylene; naphthylene; phenylene-phenylene; or phenylene, naphthylene or phenylene-phenylene each aromatic ring of which is substituted by 1 or 2 substituents selected from halo, nitro, C1-4 alkyl, C1-4 alkoxy, carboxy and sulfo, each R is independently hydrogen or D--N═N--, wherein D is the radical of a diazo component, each R1 is independently O, NH or S, each R2 is independently C1-4 alkyl, C1-4 alkoxy, --COOR3, --CONR4 R5 or --CO--Z,wherein R3 is hydrogen, C1-4 alkyl, phenyl or cyclohexyl,each of R4 and R5 is independently hydrogen; C1-4 alkyl; C2-4 alkyl monosubstituted in other than the the 1-position by hydroxy; or monosubstituted by cyano or chloro; phenyl; phenyl substituted by 1 or 2 substituents selected from methyl, ethyl, methoxy and ethoxy; phenyl(C1-4 alkyl) or phenyl(C1-4 alkyl) the phenyl group of which is substituted by 1 or 2 substituents selected from methyl, ethyl, methoxy and ethoxy; or cyclohexyl, and Z is as defined below, each W is independently --NR6 -- or ##STR173## wherein R6 is hydrogen; C1-4 alkyl; C2-4 alkyl monosubstituted in other than the 1-position by hydroxy or monosubstituted by cyano, chloro or C1-4 alkoxy; phenyl(C1-4 alkyl) or cyclohexyl, each X is independently linear or branched C1-6 alkylene, --*CONH-linear or branched C1-6 alkylene- or --*SO2 NH-linear or branched C1-6 alkylene, wherein the * denotes the atom attached to the --(A)a -- radical, each Z is independently an N-bonded organic radical containing 1 to 5 nitrogen atoms at least one of which has basic character or forms an ammonium cation,each a is independently 0 or 1, each x is independently 0 or 1, with the proviso that the sum of each adjacent a and x is 1 or 2, and each halo is independently fluoro, chloro, bromo or iodo,or a mixture thereof. 2. A metal-free compound, a 1:1 or 1:2 metal complex or a salt or acid addition salt according to claim 1wherein each Y is independently hydroxy; C1-4 alkoxy; phenoxy; --NRa Ra ; C5-6 cycloalkylamino; C5-6 cycloalkylamino the cycloalkyl ring of which is substituted by 1 or C1-2 alkyl groups; anilino; anilino the phenyl ring of which is substituted by 1 or 2 substitutents selected from halo, C1-4 alkyl, C1-4 alkoxy, hydroxy and phenoxy; morpholino; piperidino; Z or ##STR174## 10 wherein each Ra is independently hydrogen; C1-4 alkyl; C1-4 alkyl monosubstituted by halo or C2-4 alkyl monosubstituted in other than the 1-position by hydroxy, and each Z is independently ##STR175## wherein Q1 is linear or branched C2-8 alkylene, linear or branched C1-6 alkylene-C6 or C10 arylene, C6 or C10 arylene or --*NHCO--CH2 --, wherein the * denotes the atom attached to the --NR7 -- radical, Q2 is linear or branched C2-8 alkylene, linear or branched C1-6 alkylene-C6 or C10 arylene or C6 or C10 arylene, Q3 is linear or branched C2-8 alkylene, Each R7 is independently hydrogen or C1-4 alkyl, each of R8 and R9 is independently hydrogen; C1-6 alkyl; C2-6 alkyl monosubstituted in other than the 1-position by hydroxy or monosubstituted by cyano; phenyl(C1-3 alkyl); phenyl(C1-3 alkyl) the phenyl group of which is substituted by 1 to 3 substituents selected from chloro, C1-4 alkyl and C1-4 alkoxy; C5-6 cycloalkyl or C5-6 cycloalkyl substituted by 1 to 3 C1-4 alkyl groups, or --NR8 R9 is pyrrolidino, piperidino morpholino, piperazino or N-methylpiperazino, each of R10 and R11 is independently C1-6 alkyl; C2-6 alkyl monosubstituted in other than the 1-position by hydroxy or monosubstituted by cyano; phenyl(C1-3 alkyl); phenyl(C1-3 alkyl) the phenyl group of which is substituted by 1 to 3 substituents selected from chloro, C1-4 alkyl and C1-4 alkoxy; C5-6 cycloalkyl or C5-6 cycloalkyl substituted by 1 to 3 C1-4 alkyl groups, and R12 is C1-4 alkyl or benzyl, or --N.sup.⊕ R10 R11 R12 is pyridinium, pyridinium substituted by 1 or 2 methyl groups, ##STR176## wherein R12 is as defined above, R13 is hydrogen, C1-6 alkyl or C1-6 alkyl monosubstituted in other than the 1-position by hydroxy or monosubstituted by cyano, chloro or phenyl, R14 is C1-6 alkyl or C1-6 alkyl substituted in other than the 1-position by hydroxy or substituted by cyano or chloro, each An.sup.⊖ is a non-chromophoric anion, m is 0, 1, 2 or 3, and m1 is 1, 2, or 3. 3. A metal-free compound, a 1:1 or 1:2 metal complex or a salt or acid addition salt according to claim 2wherein each R1 is independently O or NH, and each R2 is independently methyl, carboxy, methoxycarbonyl, carbamoyl or --CO--Zd, whereinZd is --NH--Q1c --NR8c R9c or ##STR177## wherein Q1c is ethylene or 1,3-propylene, and each of R8c, R9c, R10c and R11c is independently methyl or ethyl. 4. A metal-free compound, a 1:1 or 1:2 metal complex or a salt or acid addition salt according to claim 3wherein each R1 is O, and each R2 is methyl. 5. A metal-free compound, a 1:1 or 1:2 metal complex or a salt or acid addition salt according to claim 2wherein each A is independently 1,3-phenylene or 1,4-phenylene, each W is independently is --NH--, --NCH3 -- or ##STR178## each a is 1, and each x is 0. 6. A metal-free compound, a 1:1 or 1:2 metal complex or a salt or acid addition salt according to claim 2wherein each z is independently --NR7a --Q1b --NR8b R9b, --NR7a --Q1b --N.sup.⊕ R10b R11b R12a An.sup.⊖, ##STR179## wherein Q1b is linear C2-6 alkylene,Q3c is ethylene or 1,3-propylene, R7a is hydrogen or methyl, each of R8b and R9b is independently hydrogen, C1-4 alkyl or 2-hydroxyethyl, or --NR8b R9b is morpholino, piperidino, piperazino or N-methylpiperazino, each of R10b and R11b is independently C1-4 alkyl or 2-hydroxyethyl, each of R10c and R11c is independently methyl or ethyl, R12a is methyl, ethyl or benzyl, or --N.sup.⊕ R10b R11b R12a is pyridinium, R13b is hydrogen, methyl or ethyl, and R14b is methyl, ethyl or 2-hydroxyethyl. 7. A metal-free non-azo compound according to claim 2,or a salt or acid addition salt thereof, wherein R0 is hydrogen, and p is 1. 8. A metal-free non-azo compound according to claim 7 having the formula ##STR180## or a salt or acid addition salt thereof, whereinR2b is methyl, carboxy, methoxycarbonyl, carbamoyl or --CO--Zd,wherein Zd is --NH--Q1c --NR8c R9c or ##STR181## wherein Q1c is ethylene or 1,3-propylene, andeach of R8c, R9c, R10c and R11c is independently methyl or ethyl, Ya is hydroxy, methoxy, phenoxy, amino, C1-4 alkylamino, C2-4 hydroxyalkylamino the hydroxy group of which is in other than the 1-position, di-(C1-2 alkyl)amino, di-(C2-4 hydroxyalkyl)amino each hydroxy group of which is in other than the 1-position, anilino, morpholino, piperidino, Zb or ##STR182## wherein R2b is as defined above, and the pyrazolone ring is in the 3- or 4-position of Ring B, and the --NH-- radical is in the 3- or 4-position of Ring A,wherein each Zb is independently --NR7a --Q1b --NR8b R9b, --NR7a --Q1b --N.sup.⊕ R10b R11b R12a An.sup.⊖, ##STR183## wherein Q1b is linear C2-6 alkylene,Q3c is ethylene or 1,3-propylene R7a is hydrogen or methyl, each of R8b and R9b is independently hydrogen, C1-4 alkyl or 2-hydroxyethyl, or --NR8b R9b is morpholino, piperidino, piperazino or N-methylpiperazino, each of R10b and R11b is independently C1-4 -alkyl or 2-hydroxyethyl, each of R10c and R11c is independently methyl or ethyl, R12a is methyl, ethyl or benzyl, or --N.sup.⊕ R10b R11b R12a is pyridinium, R13b is hydrogen, methyl or ethyl, and R14b is methyl, ethyl or 2-hydroxyethyl,wherein each An.sup.⊖ is a non-chromophoric anion 9. A metal-free non-azo compound according to claim 8,or a salt or acid addition salt thereof, wherein R2b is methyl, Ya is Zd, and Zb is Zd. 10. A metal-free azo compound according to claim 2 having the formula ##STR184## a 1:1 or 1:2 metal complex of a metallizable metal-free azo compound of said formula or a salt or acid addition salt of a metal-free azo compound of said formula or of a 1:1 or 1:2 metal complex of a metallizable metal-free azo compound of said formula,wherein Ro ' is D--N═N-- or --N═N--T--N═N--, and p is 1 when Ro ' is D--N═N-- and is 2 when R0 ' is --N═N--T--N═N--. 11. A metal-free azo compound according to claim 10 having the formula ##STR185## a 1:1 or 1:2 metal complex of a metallizable metal-free azo compound of said formula or a salt or acid addition salt of a metal-free azo compound of said formula or of a 1:1 or 1:2 metal complex of a metallizable metal-free azo compound of said formula,wherein D1 is --At --N═N--Kt, Dt1 --N═N--Dt2 --N═N--Dt3 --, ##STR186## wherein At is the radical of a tetrazo component, Dt1 is ##STR187## each of Dt2 and Dt3 is independently 1,4-phenylene; 1,4-phenylene monosubstituted by methyl, methoxy, acetamido, ureido or trimethylammoniumacetamido An.sup.⊖ ; or 1,4-phenylene substituted by two methyl groups, by two methoxy groups or by one methyl group and one methoxy group, and Kt is ##STR188## wherein Ek is hydrogen, cyano, --COOR15, --CONR16 R17, sulfo, --CH2 R18, ##STR189## Mk is hydrogen; --NR23 R24 ; C1-6 alkyl; C2-4 hydroxyalkyl the hydroxy group of which is in other than the 1-position; (C1-4 alkoxy)C1-4 alkyl; sulfo(C1-4 alkyl); C5-6 cycloalkyl; C5-6 cycloalkyl substituted by 1 to 3 C1-4 alkyl groups; phenyl; phenyl substituted by 1 to 3 substituents selected from C1-4 alkyl, C1-4 alkoxy and halo; phenyl(C1-3 alkyl); phenyl(C1-3 alkyl) the phenyl group of which is substituted by 1 to 3 substituents selected from C1-4 alkyl, C1-4 alkoxy and halo; --V1 --NR25 R26 or --V2 --N.sup.⊕ R25 R26 R27 An.sup.⊖, Rk is hydrogen; C1-4 alkyl; sulfomethyl; C5-6 cycloalkyl; phenyl; phenyl substituted by 1 or 2 substituents selected from methyl, ethyl, methoxy, ethoxy and chloro; benzyl; phenylethyl; benzyl or phenylethyl the phenyl group of which is substituted by 1 or 2 substituents selected from methyl, ethyl, methoxy, ethoxy and chloro; C1-4 alkylamino or benzothiazolyl-2, R35 is hydrogen or acetamido, R36 is sulfonaphthyl-1 or ##STR190## R37 is hydroxy or amino, R38 is methyl, phenyl, carboxy, carboxymethyl or methoxycarbonyl, and R39 is hydrogen, allyl, ##STR191## wherein R15 is C1-6 alkyl or phenyl(C1-3 alkyl), R18 is sulfo or --NR16 R17, each R19 is independently hydrogen, C1-4 alkyl, --NR16 R17 or --CONR16 R17, R20 is C1-4 alkyl, R21 is --S--, --O-- or --NR16 --, R22 is hydrogen or C1-4 alkyl, each of R23, R24, R25 and R26 is independently hydrogen; C1-6 alkyl; C2-6 alkyl monosubstituted in other than the 1-position by hydroxy or monosubstituted by cyano or halo; phenyl; phenyl substituted by 1 to 3 substituents selected from chloro, C1-4 alkyl and C1-4 alkoxy; phenyl(C1-3 alkyl); phenyl(C1-3 alkyl) the phenyl group of which is substituted by 1 to 3 substituents selected from chloro, C1-4 alkyl and C1-4 alkoxy; C5-6 cycloalkyl or C5-6 cycloalkyl substituted by 1 to 3 C1-4 alkyl groups, with the proviso that at least one of R25 and R26 in the group of the formula --V1 --NR25 R26 is other than hydrogen, or --NR23 R24 is an unsubstituted 5- or 6-membered saturated ring containing 1 to 3 hetero atoms or a 5- or 6-membered saturated ring containing 1 to 3 hetero atoms which is substituted by 1 to 3 C1-4 alkyl groups, or -NR25 R26 is an unsubstituted 5- or 6-membered saturated ring containing 1 to 3 hetero atoms or a 5- or 6-membered saturated ring containing 1 to 3 herero atoms which is substituted by 1 to 3 C1-4 alkyl groups, R27 is C1-4 alkyl or phenyl(C1-3 alkyl), or --N.sup.⊕ R25 R26 R27 is pyridinium; pyridinium substituted by 1 to 3 C1-4 alkyl groups; an unsubstituted 5- or 6-membered partially unsaturated ring containing 1 to 3 hetero atoms or a 5- or 6-membered partially unsaturated ring containing 1 to 3 hetero atoms which is substituted by 1 to 3 C1-4 alkyl groups, R28 is hydrogen, C1-2 alkyl, C1-2 alkoxy, acetamido, carboxy, sulfo, trimethylammonium An.sup.⊖ or trimethylammoniummethyl An.sup.⊖, R29 is hydrogen or C1-2 alkyl, R30 is sulfo, sulfamoyl, aminomethyl or trimethylammoniummethyl An.sup.⊖, R31 is hydrogen, C1-2 alkyl or C1-2 alkoxy, R32 is hydrogen, C1-2 alkyl, C1-2 alkoxy, acetamido, ureido or trimethylammoniumacetamido An.sup.⊖, R40 is hydrogen or methoxy, R41 is hydrogen, trimethylammoniummethyl An.sup.⊖, --CONH--Q3c --NR8b R9b, --SO2 NH--Q3c --NR8b R9b or ##STR192## wherein Yb is hydroxy, amino, C1-2 alkylamino, C2-4 hydroxyalkylamino the hydroxy group of which is in other than the 1-position, di-(C2-4 hydroxyalkyl)amino each hydroxy group of which is in other than the 1-position or Zc, R42 is hydrogen, halo, C1-2 alkyl, C1-2 alkoxy, sulfo, trimethylammoniumacetamido An.sup.⊖, trimethylammonium An.sup.⊖, trimethylammoniummethyl An.sup.⊖ or --CH2 --NR8b R9b, R43 is hydrogen or halo, V1 is linear or branched C1-6 alkylene or linear or branched C2-6 alkenylene, V2 is linear or branched C2-6 alkylene or linear or branched C2-6 alkenylene, and b is 0 or 1,wherein each R16 and R17 is independently hydrogen or C1-4 alkyl, and each Zc is independently --NH--Q1c --NR8b R9b, --NH--Q1c --N.sup.⊕ R10b R11b R12a An.sup.⊖ or ##STR193## wherein each Q1c and Q3c is independently ethylene or 1,3-propylene, each R8b and R9b is independently hydrogen, C1-4 alkyl or 2-hydroxyethyl, or --NR8b R9b is morpholino, piperidino, piperazino or N-methylpiperazino, each R10b and R11b is independently C1-4 alkyl or 2-hydroxyethyl, R12a is methyl, ethyl or benzyl, or --N.sup.⊕ R10b R11b R12a is pyridinium, and each An.sup.⊖ is a non-chromophoric anion. 12. A metal free azo compound according to claim 11 having the formula ##STR194## a 1:1 or 1:2 metal complex of a metallizable metal-free azo compound of said formula or a salt or acid addition salt of a metal-free azo compound of said formula or of a 1:1 or 1:2 metal complex of a metallizable metal-free azo compound of said formula,wherein R2b is methyl, carboxy, methoxycarbonyl, carbamoyl or --CO--Zd, whereinZd is ##STR195## wherein Q1c is ethylene or 1,3-propylene, and each of R8c, R9c, R10c and R11c is independently methyl or ethyl, Ya is hydroxy, methoxy, phenoxy, amino, C1-4 alkylamino, C2-4 hydroxyalkylamino the hydroxy group of which is in other than the 1-position, di-(C1-2 alkyl)amino, di-(C2-4 hydroxyalkyl)amino each hydroxy group of which is in other than the 1-position, anilino, morpholino, piperidino, Zb or ##STR196## wherein R2b is as defined above, and the pyrazolone ring is in the 3- or 4-position of Ring B, and the --NH-- radical is in the 3- or 4-position of Ring A,wherein each Zb is independently --NR7a --Q1b --NR8b R9b, --NR7a --Q1b --N.sup.⊕ R10b R11b R12a An.sup.⊖, ##STR197## wherein Q1b is linear C2-6 alkylene,Q3c is ethylene or 1,3-propylene, R7a is hydrogen or methyl, each of R8b and R9b is independently hydrogen, C1-4 alkyl or 2-hydroxyethyl, or --NR8b R9b is morpholino, piperidino, piperazino or N-methylpiperazino, each of R10b and R11b is independently C1-4 alkyl or 2-hydroxyethyl, each of R10c and R11c is independently methyl or ethyl, R12a is methyl, ethyl or benzyl, or --N.sup.⊕ R10b R11b R12a is pyridinium, R13b is hydrogen, methyl or ethyl, and R14b is methyl, ethyl or 2-hydroxyethyl,wherein each An.sup.⊖ is a non-chromophoric anion. 13. A metal-free azo compound, a 1:1 or 1:2 metal complex or a salt or acid addition salt according to claim 12wherein D1 is ##STR198## 14. The compound according to claim 13 having the formula ##STR199## or an acid addition salt thereof.
Diazotization and coupling reactions may be effected in conventional manner. Advantageously, coupling is carried out in aqueous medium at a temperature from 0° to 50° C., preferably from 0° to 30° C., and at a pH range of 2 to 9, preferably at pH 3 to 6.
The preferred 1:1 metallization is carried out in accordance with known methods. Suitably, the preferred 1:1 copper complexes are prepared either by oxidative coppering, preferably at 40°-70° C. and at pH 4-7 in the presence of copper(II) salts or using copper powder in the presence of hydrogen peroxide or other conventional oxidizing agents; or preferably by demethylation coppering, preferably at pH 3-4 and at elevated to boiling temperature in the presence of copper(II) salts.
0-500 parts of a solubilizing agent (e.g., glycols such as diethylene glycol, triethylene glycol and hexylene glycol; glycol ethers such as Methyl Cellosolve®, Methyl Carbitol®, butylpolyglycol; urea; formamide and dimethylformamide).
91 Parts of cyanuric chloride are suspended in 240 parts ice water and 133 parts of 3-N,N-diethylaminopropylamine are added dropwise at 5°-10°. After stirring for three hours 75 parts of 4'-amino-3-methyl-1-phenyl-5-pyrazolone are added. The temperature is elevated to 90° and the pH is kept at 2-3 by the addition of sodium acetate. A solution is obtained containing the coupling component of the formula ##STR35##
EXAMPLES 1b TO 1h
According to the method described in Example 1a further coupling components may be prepared by using the corresponding amount of an analogous compound instead of 75 parts of the above pyrazolone compound. The resulting compounds correspond to the formula ##STR36## and are listed in the following Table 1.
In a similar manner to the method of Example 1a but using the compound of formula ##STR37## as starting material, a solution of the coupling component of the formula ##STR38## is obtained which can be used directly without further isolation.
22 Parts of the compound of the formula ##STR39## are dissolved in 140 parts water and 20 parts 30% hydrochloric acid and cooled to 0°. 13 Parts 4N sodium nitrite solution are added and diazotization is effected in conventional manner. Subsequently, 9.7 parts of acetylsuccinic acid dimethyl ester are added. At pH 6 adjusted by the addition of sodium carbonate the coupling to a yellow dye solution takes place. Then 7 parts 30% sodium hydroxide solution are added. The mixture is warmed to 70°, the resulting solution is practically colourless. To discolour the solution completely 10 parts of sodium dithionite 85% are added and stirring is effected for a further hour at 90°. After cooling, a solution containing the coupling component of the formula ##STR40##
To an aqueous suspension of 92 parts cyanuric chloride 119 parts of 4'-amino-1-phenyl-5-pyrazolone-3-carboxylic acid ethylester are added and are reacted at 0°-5° and at pH 4-5. The thus obtained condensation product filtered by suction and thoroughly pressed is added to 500 parts of 3-N,N-dimethylaminopropylamine. The temperature of the resulting viscous mass rises to 70° and is elevated to 95°-100°. Stirring is effected at this temperature for 16 hours. After cooling to room temperature, 400 parts water are added, and the oil which precipitates is separated and stirred into a mixture of water and acetic acid until the solution containing a coupling component of the formula ##STR41##
44 Parts of the compound of the formula ##STR42## are dissolved in 200 parts water and 20 parts 30% hydrochloric acid. To the solution 100 parts ice are added and diazotization is carried out in conventional manner in the presence of 7 parts 4N sodium nitrite. After the addition of 60 parts 40% bisulphite solution the mixture is stirred for one hour at 30°. When a diazo compound is no longer detectable 50 parts 30% hydrochloric acid are added.
The reaction mixture is heated to 95° and kept at this temperature until the amount of sulphur dioxide has evaporated quantitatively. Subsequently, 10 parts of 3-aminocrotononitrile are added at pH 1. The temperature rises to 40° and is kept during one hour. The resulting solution contains a coupling component of the formula ##STR43##
EXAMPLES 5a TO 5t
According to the method described in Examples 1 to 4 further coupling components may be obtained which correspond to the formula ##STR44## and are listed in the following Table 2.
2.4 Parts of 2-(4'-aminophenyl)-6-methylbenzthiazole (component I) is diazotized at 0°-5° in the presence of hydrochloric acid in conventional manner and is then coupled to 6 parts of the coupling component of Example 1a at pH 4-5 in the presence of sodium acetate. From the obtained dark yellow solution the dyestuff is precipitated by the addition of sodium hydroxide solution and is filtered and dried. The thus obtained dyestuff corresponding to the formula ##STR47## is a yellow powder; the dyestuff, in acid addition salt form, dyes paper in clear yellow shades.
In a similar manner to the method of Example 6 a compound which, in the free acid form, corresponds to the formula ##STR48## may be obtained using 3.2 parts 2-(4'-aminophenyl)-6-methylbenzthiazole-7-sulphonic acid instead of 2.4 parts of component I. The dyestuff (in form of an acid addition salt) dyes paper a yellow tone.
When 4 parts of 2-(4'-aminophenyl)-6-methylbenzthiazole-3',7-disulphonic acid are used instead of 2.4 parts of component I, and the reaction is carried out according to the method described in Example 6, a dyestuff of the formula (defined in the free acid form) ##STR49## is obtained which dyes paper a yellow tone.
When 2 parts 4-amino-1,1'-azobenzene are used in Example 6 instead of the component I a dyestuff corresponding to the formula ##STR50## is obtained which in form of an acid addition salt dyes paper a yellow shade.
When in Example 6 a hydrochloric acid solution containing 2.5 parts 2-aminonaphthalene-5-methyl-trimethylammonium chloride is used instead of the component I a dyestuff of the formula ##STR51## is prepared which, in weakly acid solution, dyes paper a golden-yellow tone.
When in Example 9 4.7 parts of a compound of the formula ##STR52## are used instead of 4-amino-1,1'-azobenzene the dyestuff of the formula ##STR53## is obtained which in form of an acid addition salt dyes paper a brown tone.
When according to the method of Example 11 4.2 parts of the compound of the formula ##STR54## are used the corresponding dyestuff is obtained which dyes paper a brown shade.
When using 2 parts 2-aminonaphthalene-6-sulphonic acid instead of component I according to the method give in Example 6 a dyestuff corresponding to the formula ##STR55## is obtained which in the acid addition salt form dyes paper a reddish-yellow tone.
When instead of the coupling component KK1 according to the method of Example 9 6 parts of the coupling component of with Example 1b are used the dyestuff of the formula ##STR56## is obtained which (in acid addition salt form) dyes paper a yellow tone.
2 Parts of 4,4'-diaminodiphenylmethane are diazotized with respect to both amino groups at 0°-5° in diluted hydrochloric acid solution according to a conventional manner and are coupled with 12.5 parts of the coupling component of Example 1a. After one hour the coupling which is effected at pH 6 to 6.5 in the presence of sodium carbonate is completed. A dark reddish-yellow solution containing the dyestuff is obtained; it is precipitated, filtered by suction and then dried. It corresponds to the formula ##STR57## The dyestuff in form of an acid addition salt dyes paper a neutral-yellow tone. The resulting paper dyeings show good light and wet fastness properties.
EXAMPLES 16 TO 59
By a method in accordance with Example 15 further dyes may be prepared which are listed in the following Table 3. These dyestuffs correspond to the general formula ##STR58## In the last column of Table 3 the dye shade on paper is given whereby a=yellow; b=yellowish-orange; c=orange; d=brown-orange and e=brown.
When using the tetrazo component of the formula ##STR63## instead of 4,4'-diaminodiphenylmethane in accordance with the method of Example 15 the dyestuff of the formula ##STR64## is obtained which (in an acid addition salt form) dyes paper a yellow tone.
When a tetrazo component of the formula ##STR65## is used in accordance with the method of Example 60 the dyestuff having the formula ##STR66## is obtained; it has dyeing properties similar to those of the dye of Example 60.
When using according to the method of Example 60 a compound of the formula ##STR67## the dyestuff corresponding to the formula ##STR68## is obtained. The dyeing properties are similar to those of the dyes of Examples 60 and 61.
2.3 Parts of 4,4'-diaminobenzanilide are diazotized at 0°-5° in a conventional manner. A hydrochloric acid solution containing 6 parts of the coupling component of Example 1a is added. Within one hour the pH is gradually adjusted to 5 by the addition of sodium carbonate. When coupling on one side has been completed 2.4 parts of 6-hydroxy-4-methylpyridone-3-yl-pyridinium betaine are added. The pH is adjusted to 6.5. After two hours the second coupling is completed. The obtained dyestuff is salted out, filtered and dried. It corresponds to the formula ##STR69## and is an orange powder. The dyestuff which is well soluble in organic acids such as acetic or lactic acid dyes paper in yellow-orange shades. The paper dyeings have good light and wet fastness properties.
When according to the method given in Example 63 the sequence of the coupling steps is changed, i.e. using for the first coupling the pyridone component and for the second one the coupling component of Example 1a, a dyestuff is obtained the structure of which is given in the following Table which dyes paper a yellow-orange shade. This paper dyeing is somewhat more yellow than that made with the dye of Example 63.
EXAMPLES 64 TO 151
According to the method described in Examples 63 and 64 further dyestuffs may be prepared which correspond to the general formula ##STR70## and are listed in the following Table 4. Any starred carbon or nitrogen atom in the definition of the bridging group --B4 -- is bound to the phenyl group attached to the KKf --N═N-- group. The coupling components under the column KK are defined as given in Examples 1 to 5.
4.5 Parts of 4-aminoacetanilide are conventionally diazotized at 0°-5° in a diluted hydrochloric acid medium. Subsequently, 17.5 parts of the coupling component of Example 1a are added and a yellow solution is obtained. After coupling having been completed 50 parts 30% hydrochloric acid are added. The mixture is stirred at 95° for two hours to split off the acetyl protecting group. After the acidic hydrolysis is completed a dyestuff corresponding to the formula ##STR161## is obtained in solution, which dyes paper a yellow shade.
The dye solution prepared according to Example 152 is carefully neutralized up to pH 5 to 6 by the addition of sodium carbonate. To this solution which is cooled to 0° with ice 5.5 parts cyanuric chloride are added. During the reaction the pH is kept at 5 to 6 by the addition of sodium carbonate. After condensation is completed 11 parts of a compound of the formula ##STR162## are added. Stirring is effected at 25° to 35° and pH 6 to 7 until the second condensation is completed to form a dyestuff which is precipitated by the addition of sodium hydroxide solution, then filtered and dried. The dyestuff corresponding to the formula ##STR163## is obtained in form of a yellow powder which in acid addition salt form dyes paper a neutral-yellow shade. Light and wet fastness properties of the paper dyeings are remarkably good.
EXAMPLES 154-165
In the following Table 5 some dyestuffs of this series where a chlorine atom is present on the triazine ring or may be replaced are listed. They correspond to the general formula ##STR164## the coupling components KK are as defined in Examples 1 to 5. These dyestuffs (in acid addition salt form) dye paper a yellow shade.
When the dyestuff solution obtained in Example 152 is diazotized in accordance with conventional methods and reacted with the coupling component of Example 1a a dyestuff having the formula ##STR166## is obtained which dyes paper a clear orange shade.
12 Parts of 4,4'-diamino-3,3'-dimethoxy-1,1'-diphenyl are diazotized according to conventional methods and are coupled at pH 8 to 9 to 110 parts of the coupling component of Example 1a. An orange dyestuff is formed which is precipitated by the addition of sodium hydroxide solution and filtered. The wet paste obtained is stirred in 400 parts water; to this acetic acid is added in such an amount that the pH is adjusted to 4. The dyestuff goes into solution. 60 Parts sodium acetate and then 55 parts copper sulphate.pentahydrate are added. The resulting mixture is heated to 97° and stirred at this temperature for 20 hours. After this time coppering is complete. The mixture is cooled to 20° and the formed dyestuff is precipitated by the addition of sodium hydroxide solution. Subsequently, it is filtered and dried. The 1:1 copper complex of the disazo dye having the formula ##STR167## is obtained which in acid addition salt form dyes paper a orange-brown shade. These paper dyeings show perfect light and wet fastnesses.
27.9 Parts 2-amino-1-hydroxybenzene-4-sulphonic acid-4'-aminophenylamide are dissolved in 150 parts 10% hydrochloric acid and are diazotized (on both amino groups) at 0°-5° with 13.8 parts sodium nitrite in conventional manner. A yellow-brown suspension is formed to which 110 parts of the coupling component of Example 1b are added. Coupling is effected at pH 7 to 8. The resulting dyestuff is precipitated by the addition of sodium hydroxide solution and filtered. The wet presscake is redissolved in 400 parts dimethylformamide. 14.1 Parts CoSO4.7H2 O (dissolved in 100 parts water) are added keeping the pH at 10 by the addition of 30% sodium hydroxide solution. Subsequently, 9 parts 10% hydrogen peroxide solution are added dropwise. After metallization is completed the dyestuff is precipitated by diluting the reaction mixture with water and adding sodium hydroxide solution and is then filtered and dried in vacuo at 80°. The thus obtained 1:2 cobalt complex of the compound having the formula ##STR168## dyes leather a yellow shade. These dyeings have notable light fastness.
27.9 Parts 2-amino-1-hydroxybenzene-4-sulphonic acid-4'-aminophenylamide are diazotized on both amino groups in conventional manner. To the diazo suspension 52.4 parts of the coupling component described in Example 1a are added. Coupling is effected at one side adjusting to pH 4 which is kept by the addition of sodium acetate. After the first coupling is completed, 17.4 parts of 3-methyl-1-phenyl-5-pyrazolone dissolved in 120 parts 5% sodium hydroxide solution are added. By further addition of sodium hydroxide solution the pH is adjusted to 10. The formed disazo dyestuff precipitates completely and is filtered. The wet presscake is suspended in 400 parts water, the pH of the suspension is adjusted to 4 by the addition of acetic acid upon which the dyestuff goes into solution. To this solution 11.5 parts of chromium (III) acetate is added. The solution is refluxed for some hours until metallization is complete. The reaction mixture is cooled to 20° and the dyestuff is precipitated by the addition of sodium hydroxide solution, then filtered and dried. The thus obtained 1:2 chromium complex of the dyestuff having the formula ##STR169## dyes leather in orange-red shades. The dyeings have good light fastness.
12.6 Parts of the dyestuff powder of Example 15 are stirred into 300 parts of water and then the mixture is acidified with 2.4 parts glacial acetic acid. The dyestuff dissolves completely. Subsequently, the dyestuff solution is evaporated to dryness. A dyestuff in acid addition salt form having the formula ##STR170## is obtained in powder form which has good solubility in cold water.
60 parts of the dyestuff salt of Example 170 are added at room temperature to a solution of 20 parts dextrin, 20 parts glacial acetic acid and 400 parts water and are stirred to a homogeneous suspension. By spray drying yellow granulates are obtained which are well soluble in water and dye paper in neutral-yellow shades.
20 parts of the dyestuff powder of Example 15 are added to a solvent mixture of 75 parts water and 13 parts glacial acetic acid and are dissolved by heating to 60°. The dyestuff solution is then clear-filtered (employing kieselgur or Hyflo). The filtrate is cooled to room temperature and is adjusted to 120 parts by adding water. A ready-to-use dyestuff solution is obtained which is stable to storage for several months and which neither under warm nor cold conditions allows the dyestuff to be deposited. This dyestuff solution may be used directly (or thinned with water) in dyeing paper whereby paper dyeings of neutral-yellow shades are obtained.
70 Parts of chemically bleached sulphite cellulose obtained from pinewood and 30 parts of chemically bleached sulphite cellulose obtained from birchwood are ground in 2000 parts of water in a Hollander. 0.5 Parts of the dyestuff from Example 15 (as an acid addition salt, e.g. according to Example 170) are sprinkled into this pulp. Paper is produced from this pulp after mixing for 20 minutes. The absorbent paper which is obtained in this manner is dyed in a neutral-yellow tone. The waste water is practically colourless.
0.5 Parts of the dyestuff from Example 15 (as an acid addition salt, e.g. according to Example 170) are dissolved in 100 parts of hot water and cooled to room temperature. This solution is added to 100 parts of chemically bleached sulphite cellulose which have been ground in a Hollander with 2000 parts of water. Sizing takes place after thorough mixing for 15 minutes. The paper which is produced from this material has a neutral-yellow shade and good light- and wet-fastnesses.
100 Parts freshly tanned and neutralized chrome leather are agitated for 30 minutes in a vessel with a liquor consisting of 250 parts water at 55° and 0.5 parts of the dyestuff of Examples 63, 168 and 169, respectively, in acid addition salt form, and then treated in the same bath for 30 minutes with 2 parts of an anionic fatty licker based on sulphonated train oil. The leather is then dried and prepared in the normal way, giving a leather evenly dyed in a yellow-orange (yellow and orange-red, respectively) shades.
2 Parts of the dyestuff of Example 63 in acid addition salt form are dissolved in 4000 parts demineralized water at 40°. 100 Parts of a pre-wetted cotton textile substrate are added, and the bath is raised to boiling point over 30 minutes and held at the boil for one hour. Any water which evaporates during dyeing is replaced continuously. After rinsing and drying, a yellow-orange dyeing is obtained having good light- and wet-fastnesses. The dye exhausts practically totally, and the waste water is almost colourless.
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2009Smithkline Beecham Corporation And Glaxo Group LimitedThrombopoietin mimeticsUS20090291995 *May 27, 2009Nov 26, 2009Smithkline Beecham Corporation3'-[(2z)-[1-(3,4-dimethylphenyl)-1,5-dihydro-3-methyl-5-oxo-4h-pyrazol-4-ylidene]hydrazino]-2'-hydroxy-[1,1'-biphenyl]-3-carboxylic acid bis-(monoethanolamine)US20100040684 *Oct 28, 2009Feb 18, 2010Smithkline Beecham Corporation3'-[(2Z)-[1-(3,4-dimethylphenyl)-1,5-dihydro-3-methyl-5-oxo-4H-pyrazol-4-ylidene]hydrazino]-2'-hydroxy-[1,1'-biphenyl]-3-carboxylic acid bis-(monoethanolamine)US20100047346 *Oct 28, 2009Feb 25, 2010Smithkline Beecham Corporation3'-[(2Z)-[1-(3,4-dimethylphenyl)-1,5-dihydro-3-methyl-5-oxo-4H-pyrazol-4-ylidene]hydrazino]-2'-hydroxy-[1,1'-biphenyl]-3-carboxylic acid bis-(monoethanolamine)US20100047347 *Oct 28, 2009Feb 25, 2010Smithkline Beecham Corporation3'-[(2Z)-[1-(3,4-dimethylphenyl)-1,5-dihydro-3-methyl-5-oxo-4H-pyrazol-4-ylidene]hydrazino]-2'-hydroxy-[1,1'-biphenyl]-3-carboxylic acid bis-(monoethanolamine)US20100047348 *Oct 28, 2009Feb 25, 2010Smithkline Beecham Corporation3'-[(2Z)-[1-(3,4-dimethylphenyl)-1,5-dihydro-3-methyl-5-oxo-4H-pyrazol-4-ylidene]hydrazino]-2'-hydroxy-[1,1'-biphenyl]-3-carboxylic acid bis-(monoethanolamine)US20100129352 *Aug 1, 2007May 27, 2010Muller Francis XNovel pharmaceutical compositionUS20110081312 *Sep 1, 2010Apr 7, 2011Glaxosmithkline Llc3'-[(2z)-[1-(3,4-dimethylphenyl)-1,5-dihydro-3-methyl-5-oxo-4h-pyrazol-4-ylidene]hydrazino]-2'-hydroxy-[1,1'-biphenyl]-3-carboxylic acid bis-(monoethanolamine)US20110212054 *Aug 3, 2010Sep 1, 2011Glaxosmithkline Llc.Thrombopoietin mimetics* Cited by examinerClassifications U.S. Classification534/606, 544/198, 534/710, 534/728, 534/582, 162/162, 534/772, 534/608, 534/756, 534/775, 534/760, 534/612, 544/181, 534/604, 534/764, 534/740, 534/602, 534/567, 534/776International ClassificationC09B31/143, C09B44/02, C09B35/48, C09B44/08, C09B29/50, C09B35/03, C09B35/34, C09B29/36, C09B33/12, C09B31/28, C07D403/12Cooperative ClassificationC09B44/02, C07D403/12European ClassificationC09B44/02, C07D403/12Legal EventsDateCodeEventDescriptionJan 5, 1987ASAssignmentOwner name: SANDOZ LTD. (ALSO KNOWN AS SANDOZ AG), 4002 BASLE,Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:PEDRAZZI, REINHARD;REEL/FRAME:004652/0838Effective date: 19850130Owner name: SANDOZ LTD. (ALSO KNOWN AS SANDOZ AG), SWITZERLANDFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:PEDRAZZI, REINHARD;REEL/FRAME:004652/0838Effective date: 19850130Feb 4, 1991ASAssignmentOwner name: FIRST FIDELITY BANK FORMERLY KNOWN AS FIDELITY UNIFree format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:SANDOZ LTD.;REEL/FRAME:005587/0793Effective date: 19851112Feb 11, 1991FPAYFee paymentYear of fee payment: 4Feb 13, 1995FPAYFee paymentYear of fee payment: 8Mar 2, 1999REMIMaintenance fee reminder mailedAug 8, 1999LAPSLapse for failure to pay maintenance feesOct 19, 1999FPExpired due to failure to pay maintenance feeEffective date: 19990811RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services