- Utility of Ketonic Mannich Bases in Synthesis of Some New Functionalized 2-Pyrazolines
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The styryl ketonic Mannich base 2 has been used as a precursor in the synthesis of 2-pyrazolines having a basic side chain at C-3 and a phenolic Mannich base at C-5. Treatment of the bis(styryl ketonic bases) 6a and 8a with phenylhydrazine affords the bis(3-functionalized 2-pyrazolines) 7 and 9. The transamination between the styryl keto base 10 and 4-aminoantipyrine leads to 12, which reacts with piperazine to give 13. N-Nitrosation of the sec-Mannich bases 15a–d followed by reductive cyclization affords 2-pyrazolines 17a–d. The keto base 14b has been used for the synthesis of 2-pyrazolines having a phenolic Mannich base at C-3 and its reaction with 3,5-dimethyl-1H-pyrazole affords 23. The alkylation of 3-methyl-1-phenyl-2-pyrazolin-5-one with the bis(Mannich base) 25 was investigated.
- Afsah, Elsayed M.,Keshk, Eman M.,Abdel-Rahman, Abdel-Rahman H.,Jomah, Najla F.
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p. 326 - 334
(2017/12/26)
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- A novel methodology for synthesis of dihydropyrazole derivatives as potential anticancer agents
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A novel, simple, and efficient method for the synthesis of 4,5-dihydropyrazole derivatives has been developed. The reaction proceeded through the base-induced isomerization of easily accessible propargyl alcohols followed by cyclization of α,β-unsaturated hydrazones. Furthermore, selected compounds 3ab and 3ac exhibited good activities against Bel-7404 (human hepatoma cancer), HepG2 (human liver cancer), NCI-H460 (human lung cancer) and SKOV3 (human ovarian cancer) cell lines with IC50 in the range of 22-46 μmol L-1.
- Wang, Xu,Pan, Ying-Ming,Huang, Xiao-Chao,Mao, Zhong-Yuan,Wang, Heng-Shan
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supporting information
p. 2028 - 2032
(2014/03/21)
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- Practical synthesis of pyrazoles via a copper-catalyzed relay oxidation strategy
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Various 1,3- and 1,3,4-substituted pyrazoles are smoothly formed via copper-catalyzed cascade reactions of oxime acetates, amines and aldehydes. This relay oxidative process involves copper-promoted N-O bond cleavage and C-C/C-N/N-N bond formations to furnish pyrazolines, and sequential Cu-O2 system-involved oxidative dehydrogenation of pyrazolines to afford pyrazoles. This transformation provides a novel and versatile approach for the synthesis of pyrazoles, with an inexpensive copper catalyst and green oxidants. It is atom- and step-economical, and possesses a good functional group tolerance, as well as operational simplicity. This journal is
- Tang, Xiaodong,Huang, Liangbin,Yang, Jidan,Xu, Yanli,Wu, Wanqing,Jiang, Huanfeng
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supporting information
p. 14793 - 14796
(2014/12/11)
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- Metal-organic frameworks (MOFs) as heterogeneous catalysts for the chemoselective reduction of carbon-carbon multiple bonds with hydrazine
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The as-synthesized metal-organic frameworks (MOFs), particularly that based on aluminium coordinated with benzenedicarboxylic acid, constitute selective catalysts for the reduction of carbon-carbon multiple bonds in alkenes, alkynes and α,β-unsaturated esters with hydrazine hydrate in acetonitrile under mild conditions. The present protocol enjoys advantages such as convenient reaction conditions and benign, reusable and cost effective catalyst.
- Dhakshinamoorthy, Amarajothi,Alvaro, Mercedes,Garcia, Hermenegildo
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scheme or table
p. 2271 - 2276
(2009/12/26)
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- Mannich bases as synthetic intermediates: Alkylation of amines and diamines with bis-ketonic Mannich bases
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The bis-ketonic Mannich base, N,N-bis(β-benzoylethyl)methylamine hydrochloride (1) reacts with primary arylamines and diamines to give ketonic sec-arylamines 3a-e and 4. The piperidines 7a-c were obtained from 1 and primary alkylamines, whereas the 1,4-diazepine derivative 10 was obtained from 1 and ethylenediamine. Treatment of the bis-base l,4-di[β-(N-morpholino) propionyl]benzene bis(hydrochloride) (11) with primary arylamines gave the corresponding bis-(sec-arylamines) 12a - b, whereas its reaction with o-phenylenediamine afforded the bis[1,5-benzodiazepine] ring system 14. The synthesis of the diazacyclophane ring system 15 has been achieved by treating 11 with piperazine. Attempted synthesis of 4-aza-[7]-paracyclophane (16) from 11 and benzylamine led to 17. The reaction of 1 or 11 with phenylhydrazine gave the 2-pyrazolines 18 and 19. Treatment of 3 or 4 with phenylhydrazine and formaldehyde afforded the 2H-1,2,4-triazepines 20a-c and the bis[2H-1,2,4-triazepine] ring system 21.
- Afsah, Elsayed M.,Hammouda, Metwally,Khalifa, Mona M.,Al-shahaby, Essam H.
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experimental part
p. 577 - 584
(2009/02/03)
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- Conversion of 3-benzoyl-1-methyl-4-phenyl-γ-piperidol by arylamines and arylhydrazines. Synthesis of 3-arylamino-1-oxo-1-phenylpropanes and 1,3-diarylpyrazoles and their fragmentation under electron impact
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It has been established that on heating, 3-benzoyl-4-hydroxy-1-methyl-4- phenylpiperidine is ring-opened in the presence of arylamines by a type of retroaldol reaction, with subsequent transamination of the intermediate Mannich base and the formation of 3-arylamino-1-oxo-1-phenylpropanes. When using arylhydrazines this γ-piperidol is recyclized with the formation of 1,3-diarylpyrazoles and their 4,5-dihydro derivatives. The mass spectral behavior of a series of 3-arylamino-substituted 1-phenylpropanones has been studied.
- Volkov,Kutyakov,Levov,Polyakova,An, Le Tuan,Soldatova,Terentiev,Soldatenkov
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p. 1260 - 1268
(2008/09/19)
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- Reaction of 3-benzoyl-1-methyl-4-phenyl-γ-piperidol with arylamines and arylhydrazines. Synthesis of 3-arylamino-1-oxo-1-phenylpropanes and 1,3 diarylpyrazoles and their fragmentation under electron impact
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Upon heating in the presence of arylamines 3-benzoyl-4-hydroxy-1-methyl-4- phenylpiperidine decyclizes via a retroaldol type reaction with subsequent transamination of the intermediate Mannich base to give 3-arylamino-1-oxo-1- phenylpropanes. In the case of the use of arylhydrazines this γ-piperidol recyclizes to give 1,3-diarylpyrazoles and their 4,5-dihydro derivatives. The mass spectroscopic behavior of a series of 3-arylamino-substituted 1-phenylpropanones has been studied.
- Volkov,Kutyakov,Levov,Polyakova,Anh, Le Tuan,Soldatova,Terentiev,Soldatenkov
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p. 445 - 453
(2008/12/20)
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- Transformations of mono- and bisphenylhydrazones of aliphatic-aromatic 1,5-diketones under the conditions of the fischer reaction
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The mono- and bisphenylhydrazones of 3-R-1,5-diphenylpentane-1,5-diones were obtained, and their transformations in the Fischer indole synthesis under various conditions were studied. It was shown that 4-R-2,6-diphenylpyridines, 2-phenylindole, and 5-R-1,-3-diphenyl-Δ2-pyrazolines are formed as the main products in addition to the 3-R-1-phenyl-3-(2-phenyl-3-indolyl)propan-1-ones or their phenylhydrazones produced as a result of indolization. The ways of formation of these compounds are discussed. Some transformations of the obtained ketones were studied.
- Moskovkina
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p. 1190 - 1199
(2007/10/03)
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- Addition Products of Hydrazine Derivatives to Azo-Alkenes, Part V: The Reaction of α-(1-Phenylhydrazino)alkanone Phenylhydrazones with Acids and Acid Derivatives
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The bifunctional title compounds 2 react with acylating, carbamoylating and sulfonylating reagents mostly at the primary amino group of the hydrazine function.Both functional groups of 2 are attacked by N,N'-carbonyldiimidazole converting it into 1H-1,2,4
- Schantl, J. G.,Prean, M.
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p. 299 - 308
(2007/10/02)
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- Oxidative Cyclization of β-Stannyl Hydrazones
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Oxidation of β-stannyl hydrazones gave the corresponding azocyclopropanes in high yields.Homolytic cyclization involving hydrazonyl radicals (?-iminamino radicals) was postulated.
- Nishiyama, Hisao,Arai, Hiroyuki,Kanai, Yuki,Kawashima, Hiroyuki,Itoh, Kenji
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p. 361 - 364
(2007/10/02)
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