58970-88-0Relevant academic research and scientific papers
Lithium and zinc complexes of C- and N-functionalized (2-pyridylmethyl) amines
Koch, Christian,Kahnes, Marcel,Schulz, Martin,Goerls, Helmar,Westerhausen, Matthias
experimental part, p. 1067 - 1077 (2009/02/05)
The addition reaction of benzophenone with lithium (2-pyridylmethyl)(tert- butyldimethylsilyl)amide yields dimeric 1-lithoxy-1,1-diphenyl-2-(2-pyridyl)-2- (trialkylsilylamino)ethane (1) with formation of a C-C bond. C-Functionalized 2-(pyridylmethyl)amines are accessible via the reaction of N-(2- pyridylmethylidene)phenylamine with diethylmalonate giving 2,2- bis(ethoxycarbonyl)-1-(phenylamino)-1-(2-pyridyl) ethane (2) which eliminates aniline upon heating yielding diethyl 2-(2-pyridylmethylidene)malonate (3). The addition of piperidine leads to the formation of the Michael type adduct 2,2-bis(ethoxycarbonyl)-1-piperidyl-1-(2-pyridyl)-ethane (4) which can be deprotonated with metal-organic reagents such as Zn[N(SiMe3) 2]2, Zn[CH(SiMe3)2]2, LiN-(SiMe3)2, and NaN(SiMe3)2 leading to 2,2-bis(ethoxycarbonyl)-1-piperidyl-1-(2-pyridyl)ethane-2-yl complexes of zinc (5 and 6), lithium (7), and sodium (8). N-Functionalization can be achieved via the reaction of (2-pyridylmethyl)(trialkylsilyl) amine with benzoyl chloride giving N-(2-pyridylmethyl) benzoylamine (9). Lithiation and subsequent salt metathesis reaction with another equivalent of benzoyl chloride yields N-(2-pyridylmethyl)dibenzoylamine (10). The addition reaction of ZnCl 2 with N-(2-pyridylmethyl)(diphenylmethylidene) amine (11) forms colorless crystalline [(Py-CH2N=CPh2)ZnCl2] (12). The addition of benzoyl chloride leads to N-(diphenylchloromethyl)-N-(2- pyridylmethyl)benzoylamine (13). Addition of ZnCl2 leads to the formation of solvent-separated [(2-pyridylmethyl)(benzoylamino) diphenylcarbonium] [(tetrahydrofuran)trichlorozincate] (14). The X-ray crystal structures of 1, 4 to 7, 9, 12, and 14 are discussed. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
