Über α‐halogenierte Amine, VIII. Über die Spaltung von Aminalen und α‐Dialkylamino‐äthern mit Carbonsäurehalogeniden

Böhme, Horst; Hartke, Klaus

doi:10.1002/cber.19600930610

Cited by 189 publications

(21 citation statements)

References 7 publications

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“…Reactions between the appropriate Mannich reagent 36 and (1a -h) or (1a,f) led to the formation of the compounds in series (2) and (3), respectively. Compound (4) was prepared from dimethylamine hydrochloride, paraformaldehyde and cyclohexanone.…”

Section: Resultsmentioning

confidence: 99%

Cytotoxic and Topographical Properties of 6-Arylidene-2-dimethylaminomethylcyclohexanone Hydrochlorides and Related Compounds

Dimmock

Chamankhah

Das

et al. 2004

Journal of Enzyme Inhibition and Medicinal Chemistry

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A number of 2-arylidenecyclohexanones (1a-h) were converted into the corresponding Mannich bases (2a-h) and (3a,f). Evaluation against murine L1210 cells as well as human Molt 4/C8 and CEM T-lymphocytes revealed the marked cytotoxicity of the Mannich bases and also the fact that almost invariably these compounds were more potent than the precursor enones (1a-h). Further evaluation of most of the Mannich bases towards a panel of nearly 60 human tumour cell lines confirmed their utility as potent cytotoxins. In this assay, the compounds showed growth-inhibiting properties greater than the anticancer alkylator melphalan. QSAR studies revealed that in some cell lines compounds possessing small electron-attracting aryl substituents showed the greatest potencies. Molecular modeling and X-ray crystallography demonstrated that various interatomic distances and torsion angles correlated with cytotoxicity. A representative compound (2a) demonstrated weak inhibiting properties towards human N-myristoyltransferase and stimulated a tyrosine protein kinase. A single dose of 100 mg/kg of most of the compounds did not prove to be lethal in mice.

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Section: Resultsmentioning

confidence: 99%

Cytotoxic and Topographical Properties of 6-Arylidene-2-dimethylaminomethylcyclohexanone Hydrochlorides and Related Compounds

Dimmock

Chamankhah

Das

et al. 2004

Journal of Enzyme Inhibition and Medicinal Chemistry

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“…The hydrazones of higher aliphatic aldehydes 32 did not provide isolable compounds in aqueous solution. However, with Böhme reagent 33 [37] in anhydrous DMF, 1-piperidinoalkan-2-one hydrazones 34 were formed. [16] Whereas the Böhme reagent was too mild in the reaction with the benzaldehyde N,N-tetramethylene hydrazones, both furan-2-carbaldehyde and thiophene-2-carbaldehyde N,N-tetramethylene hydrazones 35 provided 36 in good to very good yields.…”

Section: Aminomethylations With the Mannich Reagentmentioning

confidence: 99%

Aldehyde N,N‐Dialkylhydrazones as Neutral Acyl Anion Equivalents: Umpolung of the Imine Reactivity

et al. 2007

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The isoelectronic replacement of the α‐carbon of enamines by nitrogen leads to the corresponding hydrazones, and thus, they can be termed “aza‐enamines”. Hence, aldehyde N,N‐dialkylhydrazones enable analogous electrophilic substitutions at the imine carbon that corresponds to the β‐carbon of enamines. In addition, after hydrolysis of the product hydrazones to the parent ketones or aldehydes, these reactions constitute an umpolung of the classical carbonyl reactivity and overall a nucleophilic acylation or formylation. This review covers the aza‐enamine chemistry from its very beginning in the late 1960s up to this year. In the first part, reactions of aromatic, aliphatic, and heterocyclic aldehyde N,N‐dialkylhydrazones with highly reactive substrates such as the Vilsmeier and Mannich reagents, sulfonyl isocyanates, perfluoroacetic anhydride, and inorganic electrophiles such as halogens and phosphorus tribromide are described. The hydrazones of α,β‐unsaturated aldehydes react as vinylogous aza‐enamines at the terminal carbon providing unsaturated aldehydes. As electron‐rich dienes and dienophiles, they also form Diels–Alder adducts and thus interesting N‐heterocycles. The second part covers carbon–carbon bond formations of the sterically less‐demanding formaldehyde N,N‐dialkylhydrazones with synthetically very useful electrophiles such as various Michael acceptors and carbonyl compounds. Formaldehyde SAMP‐hydrazone and related derivatives generally give excellent asymmetric inductions. Finally, first organocatalytic versions of the aza‐enamine chemistry are presented. In summary, the rich chemistry of aldehyde N,N‐dialkylhydrazones as neutral acyl anion, formyl anion, and cyanide equivalents is demonstrated. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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“…To a solution of 54.4 g (0.312 mol) of diethyl methylmalonate in dry DMF (200 ml) was added portionwise NaH (a 60% suspension in mineral oil, 18.74 g, 0.468 mol) at O°C over 15 min. After the mixture had been stirred for 30min at this temperature, 43.83 g (0.468 mol) of dimethylmethyleneammonium chloride 22 ) was added over l5min at 15°C, and the mixture was stirred for I h at room temperature. The precipitates were filtered off with a Celite pad, and the filtrate was concentrated.…”

Section: -(Dimethylaminomethyl)-4-methyl-12-dithiolane (7)mentioning

confidence: 99%

Synthesis and Biological Activity of 1,2-Dithiolanes and 1,2-Dithianes Bearing a Nitrogen-containing Substituent

Uneme

Mitsudera

Kamikado

et al. 1992

Bioscience, Biotechnology, and Biochemistry

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Über α‐halogenierte Amine, VIII. Über die Spaltung von Aminalen und α‐Dialkylamino‐äthern mit Carbonsäurehalogeniden

Abstract: Durch Umsetzung von Aminalen oder α‐Dialkylamino‐äthern mit Carbonsäurehalogeniden in indifferenten Lösungsmitteln bei Raumtemperatur erhält man α‐halogenierte Amine in meist ausgezeichneter Ausbeute und hervorragender Reinheit.

Cited by 189 publications

References 7 publications

Cytotoxic and Topographical Properties of 6-Arylidene-2-dimethylaminomethylcyclohexanone Hydrochlorides and Related Compounds

Cytotoxic and Topographical Properties of 6-Arylidene-2-dimethylaminomethylcyclohexanone Hydrochlorides and Related Compounds

Aldehyde N,N‐Dialkylhydrazones as Neutral Acyl Anion Equivalents: Umpolung of the Imine Reactivity

Synthesis and Biological Activity of 1,2-Dithiolanes and 1,2-Dithianes Bearing a Nitrogen-containing Substituent

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