US3872133A - 3-amino-1h-pyrazolo(3,4-b)pyridines - Google Patents

3-amino-1h-pyrazolo(3,4-b)pyridines Download PDF

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Publication number
US3872133A
US3872133A US373766A US37376673A US3872133A US 3872133 A US3872133 A US 3872133A US 373766 A US373766 A US 373766A US 37376673 A US37376673 A US 37376673A US 3872133 A US3872133 A US 3872133A
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Prior art keywords
alkylamino
hydroxy
alkyl
lower alkyl
amino
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US373766A
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English (en)
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Erwin Fleckenstein
Reinhard Mohr
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Hoechst AG
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • 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
    • C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
    • C09B29/0029—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing only nitrogen as heteroatom
    • 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
    • C09B44/00—Azo dyes containing onium groups
    • C09B44/10—Azo dyes containing onium groups containing cyclammonium groups attached to an azo group by a carbon atom of the ring system
    • C09B44/14—1,2-Diazoles or hydrogenated 1,2-diazoles ; Pyrazolium; Indazolium

Definitions

  • phenyl, chlorophenyl, furyl, pyridyl-methyl and Z is hydrogen or lower alkyl and lower means groups with one to four carbon atoms.
  • dyestuffs especially of azo dyestuffs of the in which Z stands for an optionally substituted alkyl or aralkyl group, K for the radical of a coupling component and A for an anion, and X, Y and Z are defined as further above.
  • Z stands for an optionally substituted alkyl or aralkyl group
  • K for the radical of a coupling component
  • A for an anion
  • X, Y and Z are defined as further above.
  • the present invention relates to novel 3-amino-1H- pyrazolo-[3,4,-b] pyridines of the formula 1 x N N/ Hal 1 in which Y is defined as above and Hal stands for a chlorine or bromine atom, with ammonia, a primary or secondary amine, a hydrazine, a hydroxylamine, a hydroxy or thio compound and condensing the soobtained compound of the formula [11 X Hal in which X, Y and Hal are defined as above, with a hydrazine of the formula IV 1 Z NHNH IV.
  • the compounds of the formula 11 are reacted with the amines, hydrazines, hydroxylamines, hydroxy or thio compounds at about to 100C, preferably at about 60 to 80C, advantageously in an inert solvent, for example in a lower aliphatic alcohol having 1 to 4 carbon atoms.
  • the reaction may also be carried out in an excess amount ofthe amine, hydrazine or hydroxylamine or of the hydroxy or thio compound as a solvent.
  • the exchange of the halogen atom in 6 position is ascertained by the analysis of the NMR spectrum of the compounds of the formula 111.
  • the compounds of the formula 111 are condensed with hydrazine at about 70 to 150C, preferably at about 100 to 130C, in an aqueous or aqueousalcoholic medium.
  • the novel compounds may be prepared in a two-step process or also without intermediate'isolation.
  • the compounds of the formula 1 may also be available in their tautomeric formulae, for example as compounds ofthe formulae V, VI or V11 phenoxy-ethylamine, n-
  • the 2,6-dihalogeno-3-cyano-pyridines of the formula 11, usedas starting compounds may be obtained according to known methods, for example by reacting the corresponding 2,6-dihydroxy-3-cyano-pyridines with halogenating agents, such as phosphoroxy chloride, phosphorus pentachloride or phosphorus pentabromide (cf. J. org. Chem. 25, 560/1960) or by reacting the corresponding l-alkyl-2-hydroxy-6-pyridones with halogenating agents (cf. German Offenlegungsschrift No. 2,049,831).
  • halogenating agents such as phosphoroxy chloride, phosphorus pentachloride or phosphorus pentabromide
  • 2,6-dichloroor 2,6-dibron1o-3- cyano-pyridines which may carry, in 4 position, an optionally substituted alkyl group, for example the methyl, ethyl, propyl, butyl, hexyl, 2-dialkylaminoethyl, 2-morpholino-ethyl, 2-aryloxy-ethyl, 3-alkoxypropyl, benzyl or pyridyl-methyl group, or an optionally substituted aryl group, for example the phenyl, halogeno-phenyl, alkyl-phenyl or alkoxy-phenyl group,
  • a cycloalkyl group for example the cyclohexyl group
  • heterocyclic radical for example the pyridyl, thiazolyl or furyl radical.
  • primary and secondary amines there are mentioned aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic amines.
  • Suitable primary amines are, for example, ammonia, methylamine, ethylamine, 2- hydroxy-ethylamine, 2-methoxy-ethylamine, 3- and iso-propylamine, 3- hydroxy-, 3-methoxyand 3-isopropoxy-propylamine, 3-cyanopropylamine, allylamine, lor 2-methyl allylamine, n-, iso-, sec.- and tert:-butylamine, 2-amino- 2-methyl-propanol-( 1), crotylamine, 3-amino-pentane, nand iso-amylamine, aniline, methyland methoxyanilines, dimethyl-anilines, amino-naphthalenes, N,N- diethyl-ethylene diamine, N,N-dimethylor N,
  • secondary amines there are, for example, mentioned dimethylamine, diethylamine, N-(2-cyano-ethyl)-N-(2-hydroxy-ethyl)- amine, N-di-(2-hydroxyethyl)-amine N-di-(2-cyanoethyl)-amine, N-methyl-, N-isopropyl-, N-n-butyl-, N- cyclohexyland N-benzyl-(Z-hydroxyethyl)-amine, di-nand di-iso-propylamine, di-nand diisobutylamine, di-n-amyland di-n-hexylamine, morpholine, pyrrolidine, piperidine, N-methyl-piperazine, N-methyland N-ethyl-cyclohexyl-amine, N-methylbenzylamine, N-methyl-3-methyl-benzylamine, N-
  • hydroxylamino compounds there are, for example, mentioned hydroxylamine, hydroxylamino-methyl ether, hydroxylamino-ethyl ether, hydroxylaminopropyl ether or hydroxyaminobutyl ether and the N- alkyl derivatives thereof.
  • hydroxy or thio compounds there are used aliphatic, araliphatic, cycloaliphatic, aromatic and heterocyclic compounds, for example aliphatic alcohols having 1 to 8 carbon atoms, alkylene glycols and the ethers thereof, cyclohexanols, phenylalkyl alcohols, phenols, dihydroxy-benzenes and the monoethers thereof, naphthols, aliphatic mercaptans, thiophenols and heterocyclic hydroxy compounds.
  • hydrazines of the formula N there are used bydrazine and monoalkyl-hydrazine, such as N-methyl-, N-ethylor N-propyl-hydrazine.
  • the compounds of the invention are valuable intermediate products for the preparation of dyestuffs, especially of azo dyestuffs of the formula Vlll (VIII)
  • EXAMPLE 1 93.5 Parts of 2,6-dichloro-3-cyano-4-methyl-pyridine were heated at the boil in 300 parts by volume of ethanol and, within 1 hour, 80 parts of diethylamine were added. The temperature was maintained for 2 hours, the solution was cooled, the colorless crystallized precipitate was suction-filtered, thoroughly washed with water and the moist product was then placed in a flask having a capacity of 500 parts by volume. After addition of 150 parts of glycol and 50 parts of hydrazine hydrate (of 80% strength), the contents were refluxed for 3 hours.
  • EXAMPLE 2 93.5 Parts of 2,6-dichloro-3-cyano-4-methyl-pyridine were dissolved in 400 parts of methanol and 27 parts of sodium methylate in 200 parts of methanol were added .in such a manner that the temperature did not exceed 50C. After this addition, stirring was continued for 6 hours at 50C, the mixture was cooled, ice water was added to the solution and the precipitate was suction-filtered. The moist product was dissolved in 150 parts of ethylene glycol, 50 parts of hydrazine hydrate were added and the mixture was heated at the boil for 3 hours. Subsequently, the mixture was cooled, ice water was added, the crystallized precipitate was suction-filtered, thoroughly washed with water and dried. The compound of the formula (IJHa OTENH: orno- N Nfi was obtained in a high yield and could be recrystallized from ethanol. 1
  • EXAMPLE 6 5 37.4 Parts of 2,6-dichloro-3cyano-4-methyl-pyridine 37.4 Parts of2,6-dichloro-3-cyano-4-methyl-pyridine were heated to 100C for 12 hours in an autoclave in were dissolved in 200 parts of methanol and a solution 200 parts of alcohol and 20 parts of methylamine. The of 18 parts of n-butyl-mercaptan and 10.8 parts of somixture was stirred onto ice water, the precipitate was dium methylate in 100 parts of methanol was added in suction-filtered, thorougly washed with water ahd such a manner that the temperature did not exceed 0 heated at the boil for 2 hours with 100 parts ofhydra- 40C.
  • N1-r oom a 6 0 7 -NH CH3 II (3131 l'laNs 29. 3 28. .l

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Pyridine Compounds (AREA)
US373766A 1972-06-30 1973-06-26 3-amino-1h-pyrazolo(3,4-b)pyridines Expired - Lifetime US3872133A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2232038A DE2232038A1 (de) 1972-06-30 1972-06-30 3-amino-1h-pyrazolo eckige klammer auf 3,4-b eckige klammer zu pyridine, ihre herstellung und verwendung

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US (1) US3872133A (tr)
JP (1) JPS4949991A (tr)
AT (1) AT333758B (tr)
BE (1) BE801795A (tr)
CH (1) CH590279A5 (tr)
DE (1) DE2232038A1 (tr)
FR (1) FR2190824B1 (tr)
GB (1) GB1391244A (tr)
NL (1) NL7308793A (tr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4020072A (en) * 1976-05-04 1977-04-26 E. R. Squibb & Sons, Inc. 5-Aminomethyl-1H-pyrazolo[3,4-b]pyridines
US4182887A (en) * 1976-09-29 1980-01-08 Boehringer Ingelheim Gmbh 3-Amino-4-phenyl-1H-pyrazolo[3,4-b]pyridines and salts thereof
US4264603A (en) * 1980-03-17 1981-04-28 Sterling Drug Inc. 5-(Pyridinyl)-1H-pyrazolo[3,4-b]pyridine-3-amines, their use as cardiotonics and their preparation
US4361568A (en) * 1981-04-28 1982-11-30 Sterling Drug Inc. 5-(Pyridinyl)-1H-pyrazolo[3,4-b]pyridin-3-amines and their cardiotonic use
US20070054915A1 (en) * 2005-08-25 2007-03-08 Roche Palo Alto Llc p38 MAP kinase inhibitors and methods for using the same
US8742106B2 (en) 2009-12-21 2014-06-03 Novartis Ag Disubstituted heteroaryl-fused pyridines

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5163193A (ja) * 1974-11-26 1976-06-01 Yoshitomi Pharmaceutical Tetorahidoropirazoropirijinkagobutsuno seizoho
IL62306A0 (en) * 1980-03-17 1981-05-20 Sterling Drug Inc Pyrazolopyridinones and pyridinylnicotinates,their preparation and pharmaceutical compositions containing them
EP2789615B1 (en) 2009-08-11 2017-05-03 Bristol-Myers Squibb Company Azaindazoles as Btk kinase modulators and use thereof
AU2019264078A1 (en) * 2018-05-02 2020-12-17 Jw Pharmaceutical Corporation Novel heterocycle derivative

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3733328A (en) * 1971-11-04 1973-05-15 Squibb & Sons Inc Pyrazolo(3,4-b)pyridine-5-carboxamides

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3733328A (en) * 1971-11-04 1973-05-15 Squibb & Sons Inc Pyrazolo(3,4-b)pyridine-5-carboxamides

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4020072A (en) * 1976-05-04 1977-04-26 E. R. Squibb & Sons, Inc. 5-Aminomethyl-1H-pyrazolo[3,4-b]pyridines
US4182887A (en) * 1976-09-29 1980-01-08 Boehringer Ingelheim Gmbh 3-Amino-4-phenyl-1H-pyrazolo[3,4-b]pyridines and salts thereof
US4224322A (en) * 1976-09-29 1980-09-23 Boehringer Ingelheim Gmbh 3-Amino-4-phenyl-6-thiomorpholino-1H-pyrazolo-[3,4-b]pyridines and salts thereof
US4260621A (en) * 1976-09-29 1981-04-07 Boehringer Ingelheim Gmbh 3-Amino-4-phenyl-6-piperidino-1H-pyrazolo[3,4-b]-pyridines and salts thereof
US4264603A (en) * 1980-03-17 1981-04-28 Sterling Drug Inc. 5-(Pyridinyl)-1H-pyrazolo[3,4-b]pyridine-3-amines, their use as cardiotonics and their preparation
US4361568A (en) * 1981-04-28 1982-11-30 Sterling Drug Inc. 5-(Pyridinyl)-1H-pyrazolo[3,4-b]pyridin-3-amines and their cardiotonic use
US20070054915A1 (en) * 2005-08-25 2007-03-08 Roche Palo Alto Llc p38 MAP kinase inhibitors and methods for using the same
US7601726B2 (en) 2005-08-25 2009-10-13 Roche Palo Alto Llc Substituted pyrazolo[3,4-d]pyrimidines as p38 MAP kinase inhibitors
US8742106B2 (en) 2009-12-21 2014-06-03 Novartis Ag Disubstituted heteroaryl-fused pyridines

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Publication number Publication date
NL7308793A (tr) 1974-01-02
GB1391244A (en) 1975-04-16
AT333758B (de) 1976-12-10
CH590279A5 (tr) 1977-07-29
DE2232038A1 (de) 1974-01-10
FR2190824B1 (tr) 1976-11-12
FR2190824A1 (tr) 1974-02-01
ATA568373A (de) 1976-04-15
JPS4949991A (tr) 1974-05-15
BE801795A (fr) 1974-01-02

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