USRE29640E - Certain substituted 2,6-diamino-4-methyl-nicotinitriles the corresponding nicotinamides and derivatives thereof - Google Patents
Certain substituted 2,6-diamino-4-methyl-nicotinitriles the corresponding nicotinamides and derivatives thereof Download PDFInfo
- Publication number
- USRE29640E USRE29640E US05/711,863 US71186376A USRE29640E US RE29640 E USRE29640 E US RE29640E US 71186376 A US71186376 A US 71186376A US RE29640 E USRE29640 E US RE29640E
- Authority
- US
- United States
- Prior art keywords
- sub
- och
- red
- formula
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/76—Nitrogen atoms to which a second hetero atom is attached
- C07D213/77—Hydrazine radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
- C07D213/82—Amides; Imides in position 3
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/84—Nitriles
- C07D213/85—Nitriles in position 3
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
- C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
- C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
- C09B29/3617—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom
- C09B29/3621—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring
- C09B29/3639—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring from a pyridine ring containing one or more amino groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
- C09B31/02—Disazo dyes
- C09B31/12—Disazo dyes from other coupling components "C"
- C09B31/14—Heterocyclic components
- C09B31/153—Heterocyclic components containing a six-membered ring with one nitrogen atom as the only ring hetero-atom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/78—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with other reactive groups
- C09B62/82—Azo dyes
Definitions
- This invention relates to compounds of the formula: ##STR1## where R 1 is hyrogen, alkyl of one to seven carbon atoms or phenyl, the radicals Z independently of one another mean hydrogen or an unsubstituted or substituted aliphatic, cycloaliphatic, araliphatic or aromatic radical and
- X is cyano or carbamoyl.
- the invention relates to compounds of the formula (Ia): ##STR2##
- R 1 is hydrogen, alkyl of one to seven carbon atoms or phenyl,
- X is carbamoyl or cyano and the radicals
- R independently of one another are unsubstituted or substituted aliphatic, cycloaliphatic, araliphatic or aromatic radicals and one of the radicals R may be hydrogen and at least one of the radicals R contains an oxygen atom.
- alkyl radicals R 1 are ethyl, n-propyl, isopropyl, butyl, pentyl, ⁇ -ethylpentyl and preferably methyl.
- radicals Z or R are alkyl of one to eight carbon atoms which may be interrupted by oxyten atoms and which may bear hydroxy, alkoxy, cyano, cycloalkoxy, aralkoxy or aroxy as substituents, cycloalkyl and polycycloalkyl which may bear hydroxy, chloro, hydroxyalkyl, chloroalkyl or alkyl as substituents, aralkyl of seven to fifteen carbon atoms, phenyl which may bear chloro, hydroxy, alkoxy, alkyl, hydroxyalkoxy or hyroxyalkyl as substituents, or alkenyl, pyrrolidonylalkyl or carboxyalkyl.
- CH 2 CH CH 2 , (CH 2 ) 2 COOH, (CH 2 ) 5 COOH and ##STR13## in which n is 2, 3, 4, or 6.
- reaction conditions which affect the exchange of the chlorine atom(s) include the temperature, the amine component, the molar ratio of the reactants and any diluent or solvent or acid-binding agent used. Amines of low boiling point may of course be reacted under superatmospheric pressure.
- the reaction with the amine is conveniently carried out at elevated temperature, a temperature of from about 0° to 110° C being adequate for the exchange of the first chlorine atom depending on the basicity of the amine, while temperatures in the range from about 60° to 180° C being advantageous for exchange of the second chlorine atom.
- Amines of high basicity react more rapidly than those of low basicity; when exchanging the second chlorine atom it is advantageous to use an excess of amine (more than 10 percent), whereas the first chlorine atom reacts immediately with a molar amount of amine.
- suitable diluents or solvents which may be added are alcohols such as methanol, ethanol or isopropanol, glycols and glycol ethers such as methyl glycol, ethyl glycol or butyl glycol, hydrocarbons and halohydrocarbons such as benzene, toluene, ethylene chloride, chloroform, trichloroethylene or chlorobenzene, and also acetone, tetrahydrofuran, dimethylformamide, N-methylpyrrolidone or dimethylsulphoxide. The presence of water does not cause any disturbance.
- acid-binding agents are advantageous because then the total amount of amine to be reacted is available for the exchange.
- Substances which do not themselves react with the chloropyridine derivatives are suitable as acid-binding agents; for example tertiary amines such as triethylamine, tributylamine, triethanolamine, ethyldiisopropylamine, caustic soda solution, sodium carbonate, magnesium oxide or calcium carbonate are suitable.
- tertiary amines such as triethylamine, tributylamine, triethanolamine, ethyldiisopropylamine, caustic soda solution, sodium carbonate, magnesium oxide or calcium carbonate are suitable.
- an excess of the amine to be reacted may also serve as acid-binding agent.
- ch 2 ch 2 och 3 , ch 2 ch 2 oc 2 h 5 , ch 2 ch 2 oc 4 h 9 , (ch 2 ) 3 och 3 , (ch 2 ) 3 oc 2 h 5 , (ch 2 ) 3 oc 3 h 7 , (ch 2 ) 3 oc 4 h 9 , (ch 2 ) 3 oc 6 h 13 , (ch 2 ) 3 oc 8 h 17 , ##
- Examples of preferred oxygen-free radicals which are preferably used in combination with an oxygen-containing radical R are besides H:
- the new coupling components are outstandingly suitable for the production of azo dyes by reaction with diazotized amines.
- the dyes which can be obtained in this way are distinguished by excellent fastness properties and by unusual brightness for azo dyes.
- a suspension of 50 parts by volume of methanol, 22 parts of norbornylamine, 37 parts of 2,6-dichloro-3-cyano-4-methylpyridine and 25 parts of triethylamine is stirred for six hours at 40° to 50° C. Then about 200 parts by volume of ice-water is added, the whole acidified to pH 1, and the precipitated product of the formula ##STR26## (which still contains a small proportion of 2-chloro-3-cyano-4-methyl-6-norbornylaminopyridine isomers) is filtered off, washed with water and dried. About 45 parts of a colorless powder is obtained which melts at 110° to 112° C.
- a mixture of 300 parts by volume of N-methylpyrrolidone, 150 parts of 2,6-dichloro-3-cyano-4-methylpyridine, 115 parts of p-anisidine and 90 parts of triethylamine is stirred for from six to 7 hours at 70° C. It is then poured while stirring onto 1500 parts of ice-water and acidified with hydrochloric acid to pH 1. About 220 parts of a colorless product of the formula: ##STR29## is obtained which is isolated by filtration, washing with water and drying. The powder contains a minor amount of a product of the formula: ##STR30## The mixture melts at 147° to 150° C.
- reaction mixture is precipitated at pH from 6 to 7, a mixture of the two isomers is obtained which has a melting point of about 143° C.
- 300 parts of 2,6-dichloro-3-cyano-4-methylpyridine is mixed with about 500 parts by volume of liquid ammonia and treated in an autoclave for 2 hours at approx. 80° C. Excess ammonia is allowed to evaporate, the residue is diluted with approx. 2500 parts by volume of water, and the pH is adjusted to 0 to 1 with hydrochloric acid. The insoluble residue is filtered off, washed with water and dried. Approx. 260 parts of a colorless powder of the formula ##STR200## which contains a minor amount of the isomeric 2-chloro-3-cyano-4-methyl-6-aminopyridine and melts at 210° C is obtained.
- a greenish yellow dye may be obtained by coupling with diazotized 2-aminobenzonitrile.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
2,3,6- AND PREFERABLY ALSO 4-SUBSTITUTED PYRIDINE DERIVATIVES BEARING THE RADICAL OF AMMONIA OR A PRIMARY AMINE IN THE 2- AND 6-POSITIONS. The compounds are eminently suitable as coupling components for the production of azo dyes, the coupling taking place in the 5-position.
Description
.Iadd.
This application is a reissue application of U.S. Pat. No. 3,853,895 issued December 10, 1974, from U.S. Application Ser. No. 328,459, filed January 31, 1973, which in turn is a continuation-in-part of U.S. Application Ser. No. 209,431, filed December 17, 1971 (now abandoned). .Iaddend.
This invention relates to compounds of the formula: ##STR1## where R1 is hyrogen, alkyl of one to seven carbon atoms or phenyl, the radicals Z independently of one another mean hydrogen or an unsubstituted or substituted aliphatic, cycloaliphatic, araliphatic or aromatic radical and
X is cyano or carbamoyl.
More particularly, the invention relates to compounds of the formula (Ia): ##STR2## IN WHICH R1 is hydrogen, alkyl of one to seven carbon atoms or phenyl,
X is carbamoyl or cyano and the radicals
R independently of one another are unsubstituted or substituted aliphatic, cycloaliphatic, araliphatic or aromatic radicals and one of the radicals R may be hydrogen and at least one of the radicals R contains an oxygen atom.
Examples of alkyl radicals R1 are ethyl, n-propyl, isopropyl, butyl, pentyl, α-ethylpentyl and preferably methyl.
Examples of radicals Z or R are alkyl of one to eight carbon atoms which may be interrupted by oxyten atoms and which may bear hydroxy, alkoxy, cyano, cycloalkoxy, aralkoxy or aroxy as substituents, cycloalkyl and polycycloalkyl which may bear hydroxy, chloro, hydroxyalkyl, chloroalkyl or alkyl as substituents, aralkyl of seven to fifteen carbon atoms, phenyl which may bear chloro, hydroxy, alkoxy, alkyl, hydroxyalkoxy or hyroxyalkyl as substituents, or alkenyl, pyrrolidonylalkyl or carboxyalkyl.
Examples of individual radicals Z or R are:
1. UNSUBSTITUTED OR SUBSTITUTED ALKYL:
Ch3, c2 h5, n-C3 H7, i-C3 H7, n-C4 H9, i-C4 H9, C6 H13, ##STR3## CH2 CH2 OH, (CH2)3 OH, ##STR4## (CH2)4 OH, (CH2)6 OH, ##STR5## (CH2)2 O(CH2)2 OH, (CH2)3 O(CH2)4 OH, (CH2)3 OC2 H4 OH, (CH2)3 OC2 H4 OCH3, (CH2)3 OC2 H4 OC2 H5, (CH2)3 OC2 H4 OCH(CH3)2, (CH2)3 OC2 H4 OC4 H9, (CH2)3 OC2 H4 OCH2 C6 H5, (CH2)3 OC2 H4 OC2 H4 C6 H5, ##STR6## (CH2)3 OC2 H4 OC6 H5, ##STR7## corresponding radicals in which the groupings ##STR8## are present twice, three times or four times, CH2 CH2 OCH3, CH2 CH2 OC2 H5, CH2 C2 OC3 H7, CH2 CH2 OC4 H9, CH2 CH2 OC6 H5, (CH2)3 OCH3, (CH2)3 OC2 H5, (CH2)3 OC3 H7, (CH2)3 OC4 H9, ##STR9## (CH2)3 OCH2 C6 H5, (CH2)3 OC2 H4 C6 H5, (CH2)3 OC6 H5, ##STR10## (CH2)2 CN, (CH2)5 CN, (CH2)6 CN, (CH2)7 ON or (CH2)3 OC8 H17 and C6 H4 CH3 instead of C6 H5
2. unsubstituted or substituted cycloalkyl or polycycloalkyl: ##STR11##
3. aralkyl: ##STR12## and C6 H4 CH3 instead of C6 H5.
4. unsubstituted or substituted phenyl:
C6 h5, c6 h4 ch3, c6 h3 (ch3)2, c6 h4 och3, c6 h4 oc2 h5, c6 h4 oh, c6 h4 och2 ch2 oh or C6 H4 Cl,
5. CH2 CH=CH2, (CH2)2 COOH, (CH2)5 COOH and ##STR13## in which n is 2, 3, 4, or 6.
For the production of compounds of formula (I), compounds of formula (II): ##STR14## in which Y is chloro or a radical of the formula NHR, and
X, r and R1 have the meanings given above may be reacted with an amine of the formula:
reaction conditions which affect the exchange of the chlorine atom(s) include the temperature, the amine component, the molar ratio of the reactants and any diluent or solvent or acid-binding agent used. Amines of low boiling point may of course be reacted under superatmospheric pressure. The reaction with the amine is conveniently carried out at elevated temperature, a temperature of from about 0° to 110° C being adequate for the exchange of the first chlorine atom depending on the basicity of the amine, while temperatures in the range from about 60° to 180° C being advantageous for exchange of the second chlorine atom.
Amines of high basicity react more rapidly than those of low basicity; when exchanging the second chlorine atom it is advantageous to use an excess of amine (more than 10 percent), whereas the first chlorine atom reacts immediately with a molar amount of amine. Examples of suitable diluents or solvents which may be added are alcohols such as methanol, ethanol or isopropanol, glycols and glycol ethers such as methyl glycol, ethyl glycol or butyl glycol, hydrocarbons and halohydrocarbons such as benzene, toluene, ethylene chloride, chloroform, trichloroethylene or chlorobenzene, and also acetone, tetrahydrofuran, dimethylformamide, N-methylpyrrolidone or dimethylsulphoxide. The presence of water does not cause any disturbance.
The addition of acid-binding agents is advantageous because then the total amount of amine to be reacted is available for the exchange. Substances which do not themselves react with the chloropyridine derivatives are suitable as acid-binding agents; for example tertiary amines such as triethylamine, tributylamine, triethanolamine, ethyldiisopropylamine, caustic soda solution, sodium carbonate, magnesium oxide or calcium carbonate are suitable. In the case of inexpensive amines, an excess of the amine to be reacted may also serve as acid-binding agent.
Compounds of the formula (Ib); ##STR15## in which R has the meanings given above are of particular industrial significance.
Examples of preferred radicals R containing oxygen are:
Ch2 ch2 oh, ch2 ch2 ch2 oh, ##STR16## (ch2)3 o(ch2)2 oh, (ch2)3 o(ch2)4 oh, (ch2)3 o(ch2)6 oh, (ch2)4 oh, (ch2)6 oh, (ch2)2 o(ch2)2 oh, ##STR17## ch2 ch2 och3, ch2 ch2 oc2 h5, ch2 ch2 oc4 h9, (ch2)3 och3, (ch2)3 oc2 h5, (ch2)3 oc3 h7, (ch2)3 oc4 h9, (ch2)3 oc6 h13, (ch2)3 oc8 h17, ##STR18## (ch2)3 oc2 h4 och3, (ch2)3 oc2 h4 oc4 h9, ##STR19## and (CH2)3 OC2 H4 OC6 H5.
Examples of preferred oxygen-free radicals which are preferably used in combination with an oxygen-containing radical R are besides H:
C2 h5, c3 h7, c4 h9, ##STR20## ch2 c6 h5, c2 h4 c6 h5, c3 h7 c6 h5, ##STR21## c6 h5, c6 h4 ch3, c6 h4 och3.
the new coupling components are outstandingly suitable for the production of azo dyes by reaction with diazotized amines. The dyes which can be obtained in this way are distinguished by excellent fastness properties and by unusual brightness for azo dyes.
The following Examples illustrate the invention. Parts and percentages referred to are by weight unless otherwise stated.
187 parts of 2,6-dichloro-3-cyano-4-methylpyridine is suspended in 500 parts by volume of methanol. 80 parts of 2-hydroxyethylamine is then added at 40° to 45° C followed by 100 parts of triethylamine. The mixture is stirred for five to six hours at 45° to 50° C, about 250 parts by volume of methanol is distilled off and the residue is diluted with 1000 parts by volume of water. After acidification with 50 parts of concentrated hydrochloric acid, the whole is stirred for 1 hour, the deposited precipitate is filtered off, washed with water until neutral and dried. About 210 parts of a colorless powder of the formula: ##STR22## is obtained. The powder contains a minor amount of a product of the formula: ##STR23## The mixture melts at 115° to 120° C.
125 parts of this powder is stirred with 300 parts by volume of methoxyethylamine for six hours under reflux.
Excess methoxyethylamine is then extensively distilled off so that the temperature may rise to 130° C and the whole is then diluted with 500 parts of water. The mixture is stirred for one hour at 0° to 10° C and the deposited precipitate is filtered off, washed with water and dried. The main product has the formula: ##STR24## and there is a minor amount of a product having the formula: ##STR25## The product is colorless and melts at 75° to 78° C.
A suspension of 50 parts by volume of methanol, 22 parts of norbornylamine, 37 parts of 2,6-dichloro-3-cyano-4-methylpyridine and 25 parts of triethylamine is stirred for six hours at 40° to 50° C. Then about 200 parts by volume of ice-water is added, the whole acidified to pH 1, and the precipitated product of the formula ##STR26## (which still contains a small proportion of 2-chloro-3-cyano-4-methyl-6-norbornylaminopyridine isomers) is filtered off, washed with water and dried. About 45 parts of a colorless powder is obtained which melts at 110° to 112° C.
45 parts of the moist powder is heated at 130° C to 140° C with 50 parts of the amine of the formula:
the water being allowed to evaporate. After stirring for 5 hours at 130° to 140° C the reaction is completed. The whole is allowed to cool and is acidified with 130 parts by volume of acetic acid. A solution of the coupling component mixture of the formulae: ##STR27## and ##STR28## is obtained, the amount of the product of formula (II) being small.
When the mixture thus obtained is coupled with p-nitroaniline a dye is obtained which dissolves in dimethylformamide to give an orange solution.
A mixture of 300 parts by volume of N-methylpyrrolidone, 150 parts of 2,6-dichloro-3-cyano-4-methylpyridine, 115 parts of p-anisidine and 90 parts of triethylamine is stirred for from six to 7 hours at 70° C. It is then poured while stirring onto 1500 parts of ice-water and acidified with hydrochloric acid to pH 1. About 220 parts of a colorless product of the formula: ##STR29## is obtained which is isolated by filtration, washing with water and drying. The powder contains a minor amount of a product of the formula: ##STR30## The mixture melts at 147° to 150° C.
50 parts of 2,6-dichloro-3-carbamoyl-4-methylpyridine is stirred with 75 parts of propanolamine-1,3 for 10 hours at 90° C. The mixture is precipitated with water and acidified to pH <O. The insoluble residue is filtered off, washed with water and dried. The colourless powder melts at 210° C and probably has the formula (I): ##STR31## The filtrate has caustic soda solution added to it until the pH is from 5 to 6. A crystalline precipitate is thrown down which probably has the formula (II) ##STR32## This is filtered off, washed with water and dried. The product (II) thus obtained also contains traces of the product of the formula (I) and melts at 150° to 160° C.
If the reaction mixture is precipitated at pH from 6 to 7, a mixture of the two isomers is obtained which has a melting point of about 143° C.
When 2,6-dichloro-3-carbamoyl-4-methylpyridine is treated analogously to the method described in Example 4, mixtures of substituted 2-aminopyridines and 6-aminopyridines are obtained, the amount of 2-amino-3-carbamoyl-4-methyl-6-chloropyridine derivatives being only slightly greater than that of the 6-aminopyridine isomers in question.
The physical properties given in Table 1 relate to mixtures.
TABLE 1
______________________________________
##STR33##
Melting
point,
Number R.sup.1 ° C.
______________________________________
##STR34## 115-199
6 (CH.sub.2).sub.3 OC.sub.2 H.sub.5
120
7 C.sub.4 H.sub.9 (n)
121-122
8 C.sub.6 H.sub.13 (n)
89-90
9
##STR35## 140-145
10
##STR36## 180-190
11 (CH.sub.2).sub.3 OCH.sub.3
105
12 C.sub.3 H.sub.7 (n)
124
13 CH.sub.2 CH.sub.2 OH
130
14 (CH.sub.2 CH.sub.2 O).sub.2 H
110
15 CH.sub.3 >150
16 C.sub.2 H.sub.5 143
17
##STR37## 190
______________________________________
When 2,6-dichloro-3-cyano-4-methylpyridine is treated by a method analogous to those described in Examples 1 to 3, there are obtained (by exchange of one chlorine atom) mixtures of 2-amino-3-cyano-4-methyl-6-chloropyridine and 2-chloro-3-cyano-4-methyl-6-aminopyridine derivatives, the proportion of the 2-chloro-3-cyano-4-methyl-6-amino isomers being clearly less.
TABLE 2
______________________________________
##STR38##
Melting
point,
Number R.sup.1 ° C.
______________________________________
18 (CH.sub.2).sub.5 COONa
85 - 91
19 (CH.sub.2).sub.5CH.sub.3
40 - 47
20 (CH.sub.2 CH.sub.2 O).sub.2 H
79 - 83
21 (CH.sub.2).sub.2 OCH.sub.3
90 - 100
22 C.sub.4 H.sub.9 (n) 50 - 60
23 C.sub.3 H.sub.7 (i) 95 - 105
24 (CH.sub.2).sub.3 OCH.sub.3
75 - 85
25
##STR39## .sup.1
26 (CH.sub.2).sub.3 OH 110 - 114
27 (CH.sub.2).sub.2 OH 125
28
##STR40## 145 - 154
29
##STR41## 147 - 149
30 H 225 - 230
31
##STR42## 165 - 175
32
##STR43## 103 - 105
33
##STR44## Tar
34
##STR45## 103
35
##STR46## 90 - 92
36 (CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5
.sup.2
37
##STR47## 105 - 110
38
##STR48## 170 - 185
39
##STR49## 147
40
##STR50## 120 - 128
41
##STR51## 170
42
##STR52## 107 - 110
43
##STR53## .sup.3
44
##STR54## 185
45 CH.sub.2 CH.sub.2 COOH
170
46 C.sub.14 H.sub.29 62
47
##STR55## 130 - 140
48
##STR56## 160
49 CH.sub.3 140
50
##STR57## 80
51 (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
75 - 80
52 (CH.sub.2).sub.3 OC.sub.3 H.sub.7 (i)
Oil
53 CH.sub.2 CH.sub.2C.sub.6 H.sub.5
118 - 123
54 (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5
Oil
55
##STR58## 172
56
##STR59## Oil
57
##STR60## 115
______________________________________
.sup.1 Greasy product.
.sup.2 Tar becoming solid on prolonged standing.
.sup.3 Viscous oil.
When the products set out in Tables 1 and 2 are treated with aliphatic or aromatic amines at temperatures above 100° or 80° C respectively, the corresponding coupling products are obtained.
In the case of pyridine derivatives which contain a carbamoyl group the reaction has to be carried out however at the lowest possible temperature because otherwise hyrolysis and/or decarboxylation of the --CONH2 group may take place.
TABLE 3
__________________________________________________________________________
##STR61##
Number
R.sup.1 R.sup.2 Melting point, °
__________________________________________________________________________
C.
58 CH.sub.2 CH.sub.2 OH
CH.sub.3 125 - 130.
59 CH.sub.2 CH.sub.2 OH
(CH.sub.2).sub.3 OH 47 - 50.
60 CH.sub.2 CH.sub.2 OH
(CH.sub.2).sub.3 OCH.sub.3
104 - 105.
61 CH.sub.2 CH.sub.2 OH
CH.sub.2 CH.sub.2 OH 156.
62 (CH.sub.2).sub.3 OH
CH.sub.3 215 (hydrochloride).
63
##STR62## (CH.sub.2).sub.3 OH 220 - 223.
64 (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH
H Viscous oil.
65 (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH
(CH.sub.2).sub.3 OH "
66 (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH
(CH.sub.2).sub.3 OCH.sub.3
"
67 (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH
(CH.sub.2).sub.2 OCH.sub.3
"
68 (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH
(CH.sub.2).sub.2 OCH.sub.3
"
69 (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH
(CH.sub.2).sub.3 OH "
70 (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH
(CH.sub.2).sub.2 OH "
71 (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH
(CH.sub.2).sub.3 OH "
72 CH.sub.2 CH.sub.2 OCH.sub.3
CH.sub.2 CH.sub.2 OCH.sub.3
75 - 76.
73 CH.sub.2 CH.sub.2 OCH.sub.3
CH.sub.2 CH.sub.2 OH 108 - 111.
74 CH.sub.2 CH.sub.2 OCH.sub.3
C.sub.6 H.sub.13 (n) Oil which has green
fluorescence.
75 CH.sub.2 CH.sub.2 OCH.sub.3
H 108.
76 (CH.sub.2).sub.3OCH.sub.3
H 95 - 98.
77 (CH.sub.2).sub.3 OH
(CH.sub.2).sub.3 OH 84 - 87.
78
##STR63## H 215 - 220.
79 " CH.sub.2 CH.sub.2 OH 137.
80 " CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
125 - 130.
81
##STR64## (CH.sub.2).sub.3 OH 170.
82 " (CH.sub.2 CH.sub.2 O).sub.2 H
175 - 180.
83
##STR65## (CH.sub.2).sub.3 OH 169 - 170.
84
##STR66## CH.sub.2 CH.sub.2 OH 155 - 158.
85 C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 CH.sub.2 OH
150 (hydrochloride).
86
##STR67## CH.sub.2 CH.sub.2 OH 173.
87
##STR68## CH.sub.2 CH.sub.2 OH 136 - 140.
88 " CH.sub.2 CH.sub.2 OCH.sub.3
134 - 138.
89
##STR69## CH.sub.2 CH.sub.2 OH 90 - 95 esterified with
acetic acid.
90 " CH.sub.2 CH.sub.2 OCH.sub.3
105.
91 CH.sub.2 CH.sub.2C.sub.6 H.sub.5
CH.sub.2 CH.sub.2 OCH.sub.3
60.
92 CH.sub.2 CH.sub.2C.sub.6 H.sub.5
CH.sub.2 CH.sub.2 OH 167 - 170.
93 C.sub.4 H.sub.9 (n)
CH.sub.2 CH.sub.2 OH Oil having green
fluorescence.
94 C.sub.4 H.sub.9 (n)
CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
"
95 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
"
96 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5
CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
"
97 (CH.sub.2).sub.5 CH.sub.3
CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
"
98 (CH.sub.2).sub.3OCH.sub.2 CH(CH.sub.3).sub.2
CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
"
99 H (CH.sub.2).sub.3O(CH.sub.2).sub.4 OH
Viscous oil
100 H (CH.sub.2).sub.3O(CH.sub.2).sub.6 OH
"
101 H (CH.sub.2).sub.3O(CH.sub.2).sub.2 OH
"
102 H (CH.sub.2).sub.3OCH.sub.2C.sub.6 H.sub.5
"
103 H (CH.sub.2).sub.3OCH.sub.2 CH.sub.2 OC.sub.6
H.sub.5 "
104 H (CH.sub.2).sub.3OCH.sub.2 CH.sub.2C.sub.6 H.sub.5
"
105 H (CH.sub.2).sub.3O CH.sub.2 CH.sub.2OCH.sub.3
"
106 H
##STR70## "
107 H (CH.sub.2).sub.3OCH.sub.2 CH.sub.2 OC.sub.4
H.sub.9 "
108 H
##STR71## "
109 H
##STR72## "
110 H
##STR73## "
111 H (CH.sub.2).sub.3 O(CH.sub.2 CH.sub.2 O).sub.2
CH.sub.3 "
112 H
##STR74## "
113
##STR75## H "
114 H (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
"
115 H (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH
"
116 H (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH
"
117 H (CH.sub.2).sub.6 OH "
118 H (CH.sub.2).sub.3OC.sub.2 H.sub.4OC.sub.3 H.sub.7
"
Shade on coupling with
##STR76##
__________________________________________________________________________
119 (CH.sub.2).sub.3 OC.sub.6 H.sub.5
CH.sub.2 CH.sub.2 OH Orange.
120 (CH.sub.2).sub.3 OC.sub.6 H.sub.5
CH.sub.2 CH.sub.2 CH.sub.2 OH
"
121 (CH.sub.2).sub.3 OC.sub.6 H.sub.5
CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
"
122 (CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5
CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
"
123 (CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5
(CH.sub.2).sub.3 OH "
124 (CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5
CH.sub.2 CH.sub.2 OH "
125
##STR77## CH.sub.2 CH.sub.2 OH "
126
##STR78## (CH.sub.2).sub.3 OH "
127 (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 C.sub.6 H.sub.5
CH.sub.2 CH.sub.2 OH "
128 (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 C.sub.6 H.sub.5
(CH.sub.2).sub.3 OH "
129 (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5
(CH.sub.2).sub.3 OH "
130 (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5
CH.sub.2 CH.sub.2 OH "
131 (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5
CH.sub.2 CH.sub.2 OCH.sub.3
"
132 (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5
CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3
"
133
##STR79## CH.sub.2 CH.sub.2 OH "
134 " (CH.sub.2).sub.3 OH "
135 " (CH.sub.2 CH.sub.2 O).sub.2 H
"
136
##STR80## CH.sub.2 CH.sub.2 OH "
137
##STR81## (CH.sub.2).sub.3 OH "
138
##STR82## CH.sub.2 CH.sub.2 OH "
139 " (CH.sub.2).sub.3 OH "
140 " (CH.sub.2 CH.sub.2 O).sub.2 H
"
Melting point, °
__________________________________________________________________________
C.
141
##STR83##
##STR84## Viscous oil.
142
##STR85## (CH.sub.2).sub.3 OH "
143
##STR86## (CH.sub.2 CH.sub.2 O).sub.2 H
"
144
##STR87## (CH.sub.2).sub.2 OCH.sub.3
"
145
##STR88## (CH.sub.2).sub.3 OCH.sub.3
"
146
##STR89##
##STR90## "
147 (CH.sub.2).sub.6 OH
##STR91## "
148
##STR92##
##STR93## "
149 (CH.sub.2 CH.sub.2 O).sub.2 H
##STR94## "
150
##STR95##
##STR96## "
151 (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
(CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
"
152 (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH
(CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH
"
153 (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH
(CH.sub. 2).sub.3 O(CH.sub.2).sub.6 OH
"
154
##STR97## CH.sub.2 CH.sub.2 OH "
155
##STR98## (CH.sub.2).sub.3 OH "
156
##STR99##
##STR100## "
157
##STR101## (CH.sub.2 CH.sub.2 O).sub.2 H
"
158
##STR102## (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
"
159
##STR103## (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH
"
160
##STR104## (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH
"
161 (CH.sub.2).sub.3 OH
(CH.sub.2).sub.3 OH 84° bis 87°
C.
162 (CH.sub.2 CH.sub.2 O).sub.2 H
(CH.sub.2 CH.sub.2 O).sub.2 H
Viscous oil.
163
##STR105## (CH.sub.2).sub.2 OCH.sub.3
"
164
##STR106## (CH.sub.2).sub.3 OCH.sub.3
"
165
##STR107## (CH.sub.2).sub.3OC.sub.3 H.sub.7
"
166 (CH.sub.2 CH.sub.2 O).sub.2 H
##STR108## "
167 (CH.sub.2).sub.2 OH
##STR109## "
168 (CH.sub.2).sub.3 OH
##STR110## "
169
##STR111##
##STR112## "
170
##STR113##
##STR114## "
171
##STR115##
##STR116## "
172 (CH.sub.2).sub.3 OH
(CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
"
173 (CH.sub.2).sub.3 OH
(CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH
"
174 (CH.sub.2).sub.3 OH
(CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH
"
175 (CH.sub.2 CH.sub.2 OH
(CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH
"
176 (CH.sub.2 CH.sub.2 OH
(CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH
"
177 CH.sub.2 CH.sub.2 OH
(CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
"
178 CH.sub.2 CH.sub.2 OCH.sub.3
(CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
"
179 CH.sub.2 CH.sub.2 OCH.sub.3
(CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
"
180 (CH.sub.2).sub.3 OCH.sub.3
(CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
"
181 (CH.sub.2).sub.3 OC.sub.3 H.sub.7
(CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
"
182 (CH.sub.2).sub.2 OCH.sub.3
(CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH
"
183 (CH.sub.2).sub.3 OCH.sub.3
(CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH
"
184 (CH.sub.2).sub.3 OCH.sub.3
(CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
"
__________________________________________________________________________
Shade on coupling with
##STR117##
__________________________________________________________________________
185 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
CH.sub.3 Orange.
186 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub. 2 OH
C.sub.2 H.sub.5 "
187 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
C.sub.3 H.sub.7 "
188 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
C.sub.4 H.sub.9 "
189 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
C.sub.5 H.sub.11 "
190 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
C.sub.6 H.sub.13 "
191 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
##STR118## "
192 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
CH.sub.2 CH.sub.2 OH "
193 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
(CH.sub.2).sub.3 OH "
194 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
##STR119## "
195 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
(CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
"
196 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
##STR120## "
197 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
##STR121## "
198 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
(CH.sub.2).sub.2 OCH.sub.3
"
199 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
(CH.sub.2).sub.3 OCH.sub.3
"
200 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
(CH.sub.2).sub.3 OC.sub.2 H.sub.5
"
201 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
(CH.sub.2).sub.3 OC.sub.3 H.sub.7 (n)
"
202 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
(CH.sub.2).sub.3 OC.sub.3 H.sub.7 (i)
"
203 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
(CH.sub.2).sub.3 OCH.sub.2 CH(CH.sub.3).sub.2
"
204 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH
##STR122## "
__________________________________________________________________________
Melting point, °
__________________________________________________________________________
C.
205 CH.sub.2 CH.sub.2 OCH.sub.3
##STR123## 116-117.
206 CH.sub.2CH.sub.2 OH
##STR124## 188-189.
207 CH.sub.2CH.sub.2 OH
H >150.
208 (CH.sub.2).sub.3COOH
##STR125## 185-188.
209 (CH.sub.2).sub.3O(CH.sub.2).sub.2 OH
C.sub.2 H.sub.5 Viscous oil.
210 (CH.sub.2).sub.3O(CH.sub.2).sub.2 OH
C.sub.3 H.sub.7 (n) "
211 (CH.sub.2).sub.3O(CH.sub.2).sub.2 OH
C.sub.4 H.sub.9 (n) "
212 (CH.sub.2).sub.3O(CH.sub.2).sub.2 OH
C.sub.5 H.sub.11 (n) "
213 (CH.sub.2).sub.3O(CH.sub.2).sub.2 OH
C.sub.6 H.sub.13 (n) "
214 (CH.sub.2).sub.3O(CH.sub.2).sub.2 OH
##STR126## "
215 (CH.sub.2).sub.3O(CH.sub.2).sub.2 OH
##STR127## "
216 (CH.sub.2).sub.3O(CH.sub.2).sub.2 OH
##STR128## "
217 (CH.sub.2).sub.3O(CH.sub.2).sub.2 OH
##STR129## "
218 (CH.sub.2).sub.3O(CH.sub.2).sub.2 OH
##STR130## "
219
##STR131## CH.sub.2 CH.sub.2 OH "
220 " (CH.sub.2).sub.3 OH "
221 " (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
"
222
##STR132## (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
"
223 " (CH.sub.2 O(CH.sub.2).sub.2 OH
"
224
##STR133## (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
"
225 " (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
"
226
##STR134## (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
"
227 " (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
"
228
##STR135## CH.sub.2 CH.sub.2 OH "
229 " (CH.sub.2).sub.2 OH "
230 " (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
"
231
##STR136## (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
"
232 " (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
"
233
##STR137## (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
"
234
##STR138## (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
"
235 " (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
"
236
##STR139## (CH.sub.2).sub.2 O(CH.sub.2 ).sub.2 OH
"
237
##STR140## CH.sub.2 CH.sub.2 OH "
238 CH.sub.2 CHCH.sub.2
(CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
"
239 CH.sub.2 CHCH.sub.2
(CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
"
__________________________________________________________________________
Shade on coupling with
##STR141##
__________________________________________________________________________
240
##STR142## C.sub.2 H.sub.5 Orange.
241 " C.sub.3 H.sub.7 (n) "
242 " C.sub.4 H.sub.9 (n) "
243 " C.sub.6 H.sub.13 (n) "
244 " (CH.sub.2).sub.3 OH "
245 " (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
"
246 " (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
"
247 " (CH.sub.2).sub.3 O(CH.sub. 2).sub.4 OH
"
248
##STR143## C.sub.2 H.sub.5 "
249 " C.sub.3 H.sub.7 (n) "
250 " C.sub.4 H.sub.9 (n) "
251 " C.sub.6 H.sub.13 (n) "
252 " (CH.sub.2).sub.2 OH "
253 " (CH.sub.2).sub.3 OH "
254 " (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
"
255 " (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
"
256 " (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH
"
257
##STR144## C.sub.2 H.sub.5 "
258 " C.sub.3 H.sub.7 "
259 " C.sub.4 H.sub.9 "
260 " CH.sub.2 CH.sub.2 OH "
261 " (CH.sub.2).sub.3 OH "
262 " (CH.sub.2).sub.2 O(CH.sub.2 ).sub.3 OH
"
263 " (CH.sub.2).sub.2 OCH.sub.3
"
264 " (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
"
265 " (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH
"
266
##STR145## C.sub.2 H.sub.5 "
267 " C.sub.3 H.sub.7 (n) "
268 " C.sub.4 H.sub.9 (n) "
269 " C.sub.6 H.sub.13 (n) "
270 H
##STR146## Golden yellow.
271
##STR147## CH.sub.2 CH.sub.2 OH Orange.
272 " (CH.sub.2).sub.3 OH "
273 " (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
"
274 " (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
"
275 " (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH
"
276 " (CH.sub.2).sub.2 OCH.sub.4
"
277 " (CH.sub.2).sub.3 OCH.sub.3
"
278
##STR148## (CH.sub.2).sub.3 OCH.sub.3
Orange.
279 " (CH.sub.2).sub.2 OCH.sub.3
"
280
##STR149## (CH.sub.2).sub.2 OCH.sub.3
"
281 " (CH.sub.2).sub.3 OCH.sub.3
"
__________________________________________________________________________
TABLE 4
__________________________________________________________________________
##STR150##
Shade coupling with
Number
R.sup.1
R.sup.2 R.sup.3
##STR151##
__________________________________________________________________________
282 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5
CH.sub.2 CH.sub.2 OH
H Orange.
283 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5
CH.sub.2 CH.sub.2 OH
C.sub.2 H.sub.3
"
284 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5
(CH.sub.2).sub.3 OH
C.sub.2 H.sub.5
"
285 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5
(CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
H "
286 CH.sub.2 CH.sub.2 C.sub.5 H.sub.5
(CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
C.sub.2 H.sub.5
"
287 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5
CH.sub.2 CH.sub.2 OH
C.sub.3 H.sub.7 (n)
"
288
##STR152##
CH.sub.2 CH.sub.2 OH
H 41
289
##STR153##
CH.sub.2 CH.sub.2 OH
C.sub.3 H.sub.7 (n)
"
290
##STR154##
(CH.sub.2).sub.3 OH
C.sub.3 H.sub.7 (n)
"
291
##STR155##
(CH.sub.2).sub.3 OH
H "
292
##STR156##
(CH.sub.2).sub.3 OH
C.sub.2 H.sub.5
"
293 CH.sub.2 CH.sub.2 OH
CH.sub.2 CH.sub.2 OH
##STR157##
"
294 CH.sub.2 CH.sub.2 OH
CH.sub.2 CH.sub.2 OH
C.sub.5 H.sub.11 (n)
"
295 CH.sub.2 CH.sub.2 OCH.sub.3
(CH.sub.2 CH.sub.2 O).sub.2 H
C.sub.6 H.sub.5
"
296 (CH.sub.2).sub.3 OCH.sub.3
(CH.sub.2 CH.sub.2 O).sub.2 H
C.sub.6 H.sub.5
"
297 H
##STR158##
H Golden yellow.
298 H
##STR159##
C.sub.3 H.sub.7 (n)
"
299 H (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH
H "
300 H (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
H "
__________________________________________________________________________
TABLE 5
__________________________________________________________________________
##STR160##
Shade after coupling with
Number
R.sup.1 R.sup.2
##STR161##
__________________________________________________________________________
301 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3
(CH.sub.2).sub.3 OH
Red.
302 CH.sub.2 CH.sub.2C.sub.6 H.sub.5
CH.sub.2 CH.sub.2 OH
Red.
303 CH.sub.2 CH.sub.2C.sub.6 H.sub.5
(CH.sub.2).sub.3 OH
Red.
304
##STR162## (CH.sub.2).sub.3 OH
Red.
305
##STR163## (CH.sub.2).sub.2 OH
Red.
306 (CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5
(CH.sub.2).sub.2 OH
Red.
307 (CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5
(CH.sub.2).sub.3 OH
Red.
308 (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5
(CH.sub.2).sub.3 OH
Red.
309 (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5
(CH.sub.2).sub.2 OH
Red.
310 (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
(CH.sub.2).sub.2 OCH.sub.3
Red.
311 (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
(CH.sub.2).sub.3 OCH.sub.3
Red.
312 (CH.sub.2).sub.2 OCH.sub.3
(CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
Red.
313 (CH.sub.2).sub.3 OCH.sub.3
(CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
Red.
314 H (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
Yellowish red.
315 H (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
"
316 H (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH
"
317 CH.sub.2CH.sub.2 OH
CH.sub.2 CH.sub.2C.sub.6 H.sub.5
Red.
318 (CH.sub.2).sub.3 OH
CH.sub.2 CH.sub.2C.sub.6 H.sub.5
Red.
319 (CH.sub.2).sub.3 OCH.sub.3
CH.sub.2 CH.sub.2C.sub.6 H.sub.5
Red.
320 CH.sub.2CH.sub.2C.sub.6 H.sub.5
(CH.sub.2).sub.3 OCH.sub.3
Red.
321
##STR164## CH.sub.2 CH.sub.2 OH
Red.
322
##STR165## (CH.sub.2).sub.3 OH
Red.
323
##STR166## (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
Red.
324
##STR167## CH.sub.2CH.sub.2 OH
Red.
325 " (CH.sub.2).sub.3 OH
Red.
326 " (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
Red.
327 " (CH.sub.2).sub.3O(CH.sub.2).sub.2 OH
Red.
328 C.sub.4 H.sub.9 (n)
(CH.sub.2).sub.3O(CH.sub.2).sub.2 OH
Red.
329 C.sub.4 H.sub.9 (n)
(CH.sub.2).sub.2 O(CH.sub.2 ).sub.2 OH
Red.
330 (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
C.sub.4 H.sub.9 (n)
Red.
331 (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
##STR168## Red.
332
##STR169## (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
Red.
333
##STR170## (CH.sub.2).sub.3 OH
Red.
334
##STR171## (CH.sub.2).sub.3 OH
Red.
335 H (CH.sub.2).sub.2 OH
Red.
336
##STR172## (CH.sub.2).sub.2 OH
Bluish red.
337 " (CH.sub.2).sub.3 OH
"
338 " (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
"
339
##STR173## (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
"
340 (CH.sub.2).sub.2 OH
(CH.sub.2).sub.2 OH
Red.
341 (CH.sub.2).sub.3 OH
(CH.sub. 2).sub.3 OH
Red.
342 (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH
(CH.sub.2).sub.3 OH
Red.
343 (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
(CH.sub.2).sub.2 OCH.sub.3
Red.
344 (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
(CH.sub.2).sub.3 OCH.sub.3
Red.
345 (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH
(CH.sub.2).sub.3 OCH.sub.3
Red.
346 H (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
Yellowish red.
347
##STR174## CH.sub.2CH.sub.2OH
Red.
348 " (CH.sub.2).sub.3 OH
Red.
349 " (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
Red.
350
##STR175## (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
Red.
351 " (CH.sub.2).sub.2 OH
Red.
352 " (CH.sub.2).sub.3 OH
Red.
353
##STR176## (CH.sub.2).sub.3 OH
Red.
354
##STR177## (CH.sub.2).sub.2 OH
Red.
355
##STR178## (CH.sub.2).sub.2O(CH.sub.2).sub.2 OH
Red.
356
##STR179## CH.sub.2CH.sub.2OH
Red.
__________________________________________________________________________
The Examples described in the above Tables are prepared by always first introducing the radical R1.
25 parts of the coupling component of the formula: ##STR180## is stirred with 75 parts of 90 percent sulphuric acid for six to eight hours at 80° to 100° C. The reaction mixture is then precipitated on 500 parts of ice, adjusted to pH 4 to 6 by adding caustic soda solution and extracted with ethyl acetate. After the extractant has been evaporated about 20 parts of the coupling component of the formula: ##STR181## is obtained as a dark oil. A red dye is obtained therefrom after coupling with diazotized p-nitroaniline
30 parts of 2,6-diamino-3-cyano-4-methylpyridine is stirred with 200 parts by volume of concentrated sulphuric acid for ten hours at 50° C. The whole is then allowed to cool, 250 parts of ice is added and it is left overnight. The deposited precipitate is filtered off and washed witht acetone. After drying, 36 parts of a colourless powder of the formula: ##STR182## is obtained which melts at 250° C with decomposition.
The free base of the formula: ##STR183## is obtained from the salt by a conventional method.
TABLE 6
__________________________________________________________________________
##STR184##
Melting
Number
R.sup.1 R.sup.2 point, ° C.
__________________________________________________________________________
359 C.sub.6 H.sub.5
C.sub.6 H.sub.5
128-130
360
##STR185##
##STR186## 178
361 CH.sub.3 CH.sub.3 140-150
362 CH(CH.sub.2).sub.2
CH(CH.sub.3).sub.2
118-120
363 C.sub.3 H.sub.7 (n)
C.sub.3 H.sub.7 (n)
122-123
364 CH.sub.2CHCH.sub.2
CH.sub.2CHCH.sub.2
77
365 C.sub.4 H.sub.9 (n)
C.sub.4 H.sub.9 (n)
97
366 C.sub.6 H.sub.13 (n)
C.sub.6 H.sub.13 (n)
Oil
367
##STR187##
##STR188## 193
368 H H 225
369
##STR189##
##STR190## 175
370 CH.sub.2 C.sub.6 H.sub.5
CH.sub.2C.sub.6 H.sub.5
170
371 CH.sub.2CH.sub.2C.sub.6 H.sub.5
CH.sub.2CH.sub.2C.sub.6 H.sub.5
110
372 C.sub.2 H.sub.5
C.sub.2 H.sub.5
.sup.1 205
373 C.sub.6 H.sub.5
C.sub.4 H.sub.9 (n)
115
374 C.sub.6 H.sub.5
H (.sup.2)
375 C.sub.4 H.sub.9 (n)
H 100
376 C.sub.2 H.sub.5
C.sub.6 H.sub.5
218-220
377 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5
H 100
378
##STR191##
##STR192## Ca.60
379 H CH.sub.2CH.sub.2C.sub.6 H.sub.5
Ca.100,.sup.1 188
380 C.sub.8 H.sub.17 (n)
H Oil
381 C.sub.14 H.sub.29
H Ca.90-105
382 H
##STR193## Tar
383
##STR194## H Tar
384 CH.sub.2CH.sub.2CN
CH.sub.2CH.sub.2CN
170-176
385 CH.sub.2CH.sub.2CN
CH.sub.2CH.sub.2C.sub.6 H.sub.5
Ca.120
386 H (CH.sub.2).sub.5 CN
142
__________________________________________________________________________
.sup.1 Hydrochloride.
.sup.2 Tarry: becomes solid after prolonged standing.
Table 7
______________________________________
##STR195##
Shade when
coupled with
Ex. X R.sup.1 R.sup.2
##STR196##
______________________________________
387 CH.sub.3
H CH.sub.2 CH.sub.2 OH
Yellowish red.
388 CH.sub.3
H (CH.sub.2).sub.3 OH
"
389 CH.sub.3
H
##STR197## "
390 CH.sub.3
H CH.sub.2 CH.sub.2 C.sub.6 H.sub.5
"
391 C.sub.3 H.sub.7
C.sub.6 H.sub.5
CH.sub.2 CH.sub.2 OH
Bluish red.
392 C.sub.3 H.sub.7
C.sub.6 H.sub.5
(CH.sub.2).sub.3 OH
"
393 C.sub.3 H.sub.7
C.sub.6 H.sub.5
(CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
"
394 C.sub.3 H.sub.7
##STR198##
(CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH
"
395 C.sub.3 H.sub.7
" CH.sub.2 CH.sub.2 OH
"
396 C.sub.3 H.sub.7
" (CH.sub.2).sub.3 OH
"
397 H C.sub.6 H.sub.5
(CH.sub.2).sub.3 OH
"
______________________________________
190 parts of 2,6-dichloro-3-cyano-4-methylpyridine, 750 parts of isopropanol and approx. 300 parts of ammonia are stirred in an autoclave for 15 hours at 180° C. The mixture is allowed to cool, excess ammonia is evaporated and 450 parts by volume of isopropanol is distilled off. The residue is mixed with approx. 600 parts of water, the pH is adjusted to approx. 0 with concentrated hyrochloric acid and the solution filtered. Then 50 percent caustic soda solution is added until the pH of the mixture is approx. 9, the mixture allowed to cool to 0°-10° C and then filtered, and the residue is washed with water and dried. 130 to 145 parts of a colorless powder of the formula ##STR199## is obtained which melts at 225° C.
300 parts of 2,6-dichloro-3-cyano-4-methylpyridine is mixed with about 500 parts by volume of liquid ammonia and treated in an autoclave for 2 hours at approx. 80° C. Excess ammonia is allowed to evaporate, the residue is diluted with approx. 2500 parts by volume of water, and the pH is adjusted to 0 to 1 with hydrochloric acid. The insoluble residue is filtered off, washed with water and dried. Approx. 260 parts of a colorless powder of the formula ##STR200## which contains a minor amount of the isomeric 2-chloro-3-cyano-4-methyl-6-aminopyridine and melts at 210° C is obtained.
168 parts of this powder is mixed with about 170 parts of β-hydroxyethylamine and 170 parts by volume of isopropanol. The mixture is heated for 7 to 10 hours under reflux, the solvent is distilled off, the residue is diluted with about 400 parts of water, and the pH is adjusted to 1 to 2. A deep-colored solution of about 192 parts of the coupling component of the formula ##STR201## is obtained, a minor portion of which consists of 2-amino-4-methyl-5-cyano-6-β-hydroxyethylaminopyridine.
A greenish yellow dye may be obtained by coupling with diazotized 2-aminobenzonitrile.
TABLE 8
__________________________________________________________________________
##STR202##
Shade when coupled with
No.
R.sup.1 R.sup.2 X
##STR203##
__________________________________________________________________________
400
H CH.sub.3 CN Golden yellow.
401
H C.sub.2 H.sub.5
CN "
402
H C.sub.3 H.sub.7
CN "
403
H C.sub.2 H.sub.4 OCH.sub.3
CN "
404
H C.sub.2 H.sub.4 OCH.sub.3
CONH.sub.2
Yellowish red.
405
H C.sub.3 H.sub.6 OCH.sub.3
CONH.sub.2
"
406
H C.sub.3 H.sub.6 OCH.sub.3
CN Golden Yellow.
407
H C.sub.4 H.sub.9 (n)
CN Yellow orange.
408
H C.sub.4 H.sub.9 (n)
CONH.sub.2
Yellowish red.
409
H CH.sub.2 CHCH.sub.2
CN Golden yellow.
410
H
##STR204##
CONH.sub.2
Yellowish red.
411
H
##STR205##
CN Orange.
412
H
##STR206##
CONH.sub.2
Red.
413
##STR207##
CH.sub.2 CH.sub.2 OH
CONH.sub.2
Red.
414
##STR208##
(CH.sub.2).sub.3 OH
CONH.sub.2
Red.
415
CH.sub.2 CH.sub.2 OH
##STR209##
CONH.sub.2
Red.
416
##STR210##
CH.sub.2 CH.sub.2 OH
CONH.sub.2
Red. (M.P. 150-153° C.)
__________________________________________________________________________
Claims (6)
1. A compound of the formula ##STR211## in which: R1 is hydrogen, alkyl of one to seven carbon atoms or phenyl;
X is cyano or carbamoyl; and
each Z, independently of one another, is hydrogen, alkyl of one to eight carbon atoms, hydroxyalkyl of two to eight carbon atoms, cyanoalkyl of two to seven carbon atoms, alkoxyalkyl of two or three carbon atoms in the alkyl and one to eight carbon atoms in the alkoxy, cyclohexoxypropyl, benzyloxypropyl, β-phenyl-ethoxypropyl, phenoxypropyl, tolyloxypropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, hydroxycyclohexyl, β-hydroxyethoxycyclohexyl, norbornyl, hydroxynorbornyl, hydroxymethylnorbornyl, chloromethylnorbornyl, β-hydroxyethylnorbornyl, bicyclooctyl, phenylalkyl or tolylalkyl of one to four carbon atoms in the alkyl, phenyl, phenyl substituted by methyl, methoxy, ethoxy, hydroxy, chloro or β-hydroxyethoxy, allyl, carboxyethyl, carboxypentyl, ω-pyrrolidonylalkyl of two to six carbon atoms in the alkyl, ##STR212## --(CH2)2 O(CH2)2 OH, --(CH2)3 O(CH2)4 OH, --(CH2)3 O(CH2)6 OH, ##STR213## or --(CH2)3 (OC2 H4)n OT, n being 1, 2, 3 or 4, and
T being hydrogen, alkyl of one to four carbon atoms, benzyl, phenylethyl, cyclohexyl, phenyl or tolyl.
2. A compound as claimed in claim 1 of the formula ##STR214## in which: Z1 is an oxygen-containing radical selected from the group consisting of --CH2 CH2 OH, --CH2 CH2 Ch.sub. 2 OH, ##STR215## --(CH2)3 O(CH2)2 OH, --(CH2)3 O(CH2)4 OH, --(CH2)3 O(CH2)6 OH, --(CH2)4 OH, --(CH2)6 OH, --(CH2)2 O(CH2)2 OH, ##STR216## --CH2 CH2 OCH3, --CH2 CH2 OC2 H5, --CH2 CH2 OC4 H9, --(CH2)3 OCH3, --(CH2)3 OC2 H5, --(CH2)3 OC4 H9, --(CH2)3 OC3 H7, --(CH2)3 OC6 H13, --(CH2)3 OC8 H17, ##STR217## --(CH2)3 OC2 H4 OCH3, --(CH2)3 OC2 H4 OC4 H9, ##STR218## and --(CH2)3 OC2 H4 OC6 H5 ; and
Z2 is hydrogen, an oxygen-containing radical as defined for Z1 or an oxygen-free radical selected from the group consisting of
--C2 H5, --C3 H7, --C4 H9, ##STR219## --CH2 C6 H5, --C2 H4 C6 H5, --C3 H7 C6 H5, ##STR220## --C6 H5, --C6 H4 CH3 and --C6 H4 OCH3.
3. the compound of the formula ##STR221##
4. The compound of the formula ##STR222##
5. The compound of the formula ##STR223##
6. The compound of the formula ##STR224##
Applications Claiming Priority (29)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19702062717 DE2062717C3 (en) | 1970-12-19 | 1970-12-19 | Azo dyes from 2,6-diaminopyridine derivatives, process for their preparation and use |
| DT2062717 | 1970-12-19 | ||
| DT2156545 | 1971-11-15 | ||
| DE19712156545 DE2156545A1 (en) | 1971-11-15 | 1971-11-15 | Azo dyes - from 2,6-diaminopyridine derivatives |
| DT2211663 | 1972-03-10 | ||
| DE19722211663 DE2211663C3 (en) | 1972-03-10 | 1972-03-10 | Azo dyes with 2,6-diaminopyrfdines as coupling components, process for their production and dye preparations |
| DE19722216570 DE2216570C3 (en) | 1972-04-06 | 1972-04-06 | Water-soluble azo dyes of the 2,6-diaminopyridine series, process for their preparation and use |
| DT2216570 | 1972-04-06 | ||
| DT2226933 | 1972-06-02 | ||
| DE19722226933 DE2226933C3 (en) | 1972-06-02 | 1972-06-02 | Azo dyes with 2,6 diaminopyridines as coupling components, process for their preparation and their use |
| DE2251719A DE2251719A1 (en) | 1972-10-21 | 1972-10-21 | DISPERSION DYES OF THE 2,6 DIAMINOPYRIDINE SERIES |
| DE19722251702 DE2251702B2 (en) | 1972-10-21 | 1972-10-21 | Dispersion azo dyes of the 2,6-diamino pyridine series, process for their manufacture and their use |
| DT2251702 | 1972-10-21 | ||
| DT2251719 | 1972-10-21 | ||
| DE19722258823 DE2258823A1 (en) | 1972-12-01 | 1972-12-01 | 2,6-DIAMINOPYRIDINE DYES |
| DT2258823 | 1972-12-01 | ||
| DE19722259103 DE2259103C3 (en) | 1972-12-02 | 2,6-Diaminopyridinazo dyes, process for their preparation and their use | |
| DT2259103 | 1972-12-02 | ||
| DE19722259684 DE2259684A1 (en) | 1972-12-06 | 1972-12-06 | Azo dyes - using 2,6-diaminopyridine deriv coupling component |
| DT2259684 | 1972-12-06 | ||
| DT2260827 | 1972-12-13 | ||
| GB5744272 | 1972-12-13 | ||
| UK57442/72 | 1972-12-13 | ||
| DE2260827A DE2260827C3 (en) | 1972-12-13 | 1972-12-13 | 2,6-Diaminopyridines, process for their preparation and their use as coupling components for azo dyes |
| JA47-125836 | 1972-12-16 | ||
| JP12583672A JPS5246230B2 (en) | 1972-12-16 | 1972-12-16 | |
| DE2263458A DE2263458A1 (en) | 1972-12-27 | 1972-12-27 | 2,6-DIAMINOPYRIDINE DYES |
| DT2263458 | 1972-12-27 | ||
| US00328459A US3853895A (en) | 1972-12-13 | 1973-01-31 | Certain substituted 2,6-diamino-4-methyl-nicotinonitriles the corresponding nicotinamides and derivatives thereof |
Related Parent Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US20943171A Continuation-In-Part | 1970-12-19 | 1971-12-17 | |
| US00328459A Reissue US3853895A (en) | 1970-12-19 | 1973-01-31 | Certain substituted 2,6-diamino-4-methyl-nicotinonitriles the corresponding nicotinamides and derivatives thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE29640E true USRE29640E (en) | 1978-05-23 |
Family
ID=27585152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/711,863 Expired - Lifetime USRE29640E (en) | 1970-12-19 | 1976-08-05 | Certain substituted 2,6-diamino-4-methyl-nicotinitriles the corresponding nicotinamides and derivatives thereof |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USRE29640E (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4210583A (en) | 1977-08-03 | 1980-07-01 | Basf Aktiengesellschaft | Azo dyes of the 2,6-di(substituted) amino pyridine series |
| US4354969A (en) | 1979-07-23 | 1982-10-19 | Basf Aktiengesellschaft | Dye mixtures |
| US4855412A (en) | 1986-05-03 | 1989-08-08 | Basf Aktiengesellschaft | Diaminopyridine azo dyes having acyloxy radicals substituted on the diaminopyridine |
| US5149789A (en) * | 1989-04-01 | 1992-09-22 | Basf Aktiengesellschaft | Reactive dyes with two or three nitrogen-containing haloheterocycles as reactive system |
| US5210187A (en) * | 1988-07-28 | 1993-05-11 | Basf Aktiengesellschaft | Double attachment reactive dyes having alkyl- or alkenylsulfonyl and alkyl- or alkenylsulfonylalkyl groups |
| US5330543A (en) * | 1991-11-23 | 1994-07-19 | Basf Aktiengesellschaft | Thiopheneazo dyes with a coupling component of the diaminopyridine series |
| US5929217A (en) * | 1995-03-24 | 1999-07-27 | Basf Aktiengesellschaft | Reactive dyes with a benzo-fused heterocycle as anchor |
| US6489344B1 (en) | 1998-06-19 | 2002-12-03 | Chiron Corporation | Inhibitors of glycogen synthase kinase 3 |
| US20060089369A1 (en) * | 1998-06-19 | 2006-04-27 | Chiron Corporation | Inhibitors of glycogen synthase kinase 3 |
| US7893042B2 (en) | 2008-12-19 | 2011-02-22 | Pinnacle Pharmaceuticals, Inc. | Phenazopyridine compounds |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3433795A (en) * | 1966-08-12 | 1969-03-18 | Nepera Chem Co Inc | Tricyclic ester derivatives of pyridine carboxylates and process for their production |
| US3664996A (en) * | 1968-06-27 | 1972-05-23 | Ici Ltd | Mono azo dyestuffs containing a pyridyl group |
-
1976
- 1976-08-05 US US05/711,863 patent/USRE29640E/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3433795A (en) * | 1966-08-12 | 1969-03-18 | Nepera Chem Co Inc | Tricyclic ester derivatives of pyridine carboxylates and process for their production |
| US3664996A (en) * | 1968-06-27 | 1972-05-23 | Ici Ltd | Mono azo dyestuffs containing a pyridyl group |
Non-Patent Citations (2)
| Title |
|---|
| Chemical and Engineering News, p. 18, Apr. 3, 1972. * |
| Karrer, Organic Chemistry, 4th Englsh Edition, p. 928, Elsevier Pub. Co., (NY), 1950. * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4210583A (en) | 1977-08-03 | 1980-07-01 | Basf Aktiengesellschaft | Azo dyes of the 2,6-di(substituted) amino pyridine series |
| US4354969A (en) | 1979-07-23 | 1982-10-19 | Basf Aktiengesellschaft | Dye mixtures |
| US4855412A (en) | 1986-05-03 | 1989-08-08 | Basf Aktiengesellschaft | Diaminopyridine azo dyes having acyloxy radicals substituted on the diaminopyridine |
| US5210187A (en) * | 1988-07-28 | 1993-05-11 | Basf Aktiengesellschaft | Double attachment reactive dyes having alkyl- or alkenylsulfonyl and alkyl- or alkenylsulfonylalkyl groups |
| US5149789A (en) * | 1989-04-01 | 1992-09-22 | Basf Aktiengesellschaft | Reactive dyes with two or three nitrogen-containing haloheterocycles as reactive system |
| US5330543A (en) * | 1991-11-23 | 1994-07-19 | Basf Aktiengesellschaft | Thiopheneazo dyes with a coupling component of the diaminopyridine series |
| US5929217A (en) * | 1995-03-24 | 1999-07-27 | Basf Aktiengesellschaft | Reactive dyes with a benzo-fused heterocycle as anchor |
| US6489344B1 (en) | 1998-06-19 | 2002-12-03 | Chiron Corporation | Inhibitors of glycogen synthase kinase 3 |
| US20060089369A1 (en) * | 1998-06-19 | 2006-04-27 | Chiron Corporation | Inhibitors of glycogen synthase kinase 3 |
| US7037918B2 (en) | 1998-06-19 | 2006-05-02 | Chiron Corporation | Inhibitors of glycogen synthase kinase 3 |
| US7045519B2 (en) | 1998-06-19 | 2006-05-16 | Chiron Corporation | Inhibitors of glycogen synthase kinase 3 |
| US7425557B2 (en) | 1998-06-19 | 2008-09-16 | Novartis Vaccines And Diagnostics, Inc. | Inhibitors of glycogen synthase kinase 3 |
| US7893042B2 (en) | 2008-12-19 | 2011-02-22 | Pinnacle Pharmaceuticals, Inc. | Phenazopyridine compounds |
| US8288365B2 (en) | 2008-12-19 | 2012-10-16 | Pinnacle Pharmaceuticals, Inc. | Phenazopyridine compounds |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4396764A (en) | Cyanoguanidine derivatives | |
| USRE29640E (en) | Certain substituted 2,6-diamino-4-methyl-nicotinitriles the corresponding nicotinamides and derivatives thereof | |
| US4774324A (en) | Isothiazolylazo dyes | |
| US4247456A (en) | Water-insoluble monoazo pyridone dye | |
| US4045458A (en) | Process for preparing triarylmethane derivatives | |
| US5424455A (en) | Heterocyclic compounds for making red disperse dyes | |
| US5663309A (en) | Diazo dyes having a phenylene group as the middle component and a naphthalene group as the terminal diazo component | |
| US4201710A (en) | Azo dyes of the pyridone series useful for flowable printing inks | |
| US4652633A (en) | Sulfo-containing halophenylazodiamino, cyano pyridine compounds | |
| US4743595A (en) | Process for preparing 2-amino-5-nitrophenol derivatives | |
| US4046502A (en) | Basic disazo dyes having two 2-hydroxy-3-substituted carbamoylnaphthyl-1-azophenyl groups for dyeing paper | |
| US4619992A (en) | 3-(β-aminoethyl)-4-cyano-isothiazolylazo dyes | |
| US4263431A (en) | Cationic fluorescent whitening agents | |
| US4734218A (en) | Dichroic azo dyestuffs and liquid crystal composition containing said dyestuffs | |
| US4042591A (en) | Naphthoquinone compounds | |
| US5545236A (en) | Red reactive dyes, their compositions and dyeing method employing them | |
| US4764600A (en) | Isothiazolylazo dyes having aminophenyl and aminonaphthyl components | |
| US4578469A (en) | Benzo[de]pyrano[3,2-g]isoquinoline derivatives useful as dyestuffs | |
| US4448719A (en) | Trifluoromethyl-substituted monoazo disperse dyes | |
| US4764599A (en) | Disazo compounds containing an N,N-bis(2-amino-benzoyl)piperazine derivative as the diazo component | |
| US4391606A (en) | Azo polyether dyestuffs, formulations of these dyestuffs, their preparation and their use | |
| US5120872A (en) | Compounds containing a 3-sulfoalkanoylamino or 3-sulfoalylsulfonylaminoaniline coupling component | |
| US4072672A (en) | Cationic dyes containing an aryloxy group linked through a bridging radical to a quaternized nitrogen atom | |
| US4397651A (en) | Polymeric dyes derived from bis-reactive methylene compounds and aromatic di-aldehydes for paper | |
| US4249010A (en) | Naphthostyril dyestuffs |