72443-53-9Relevant academic research and scientific papers
Application of 13C NMR Spectroscopy and 13C-Labeled Benzylammonium Salts to the Study of Rearrangements of Ammonium Benzylides
Zdrojewski, Tadeusz,Jończyk, Andrzej
, p. 452 - 457 (2007/10/03)
Ylides generated from N-(cyanomethyl)-N,N-dimethyl-N-[α-(trimethylsilyl)benzyl]ammonium chloride (4) and fluoride anion afford the products of [1,2] shift 11 and [2,3] shift 13. Formation of product 13 shows that, in the presence of water from TBAF, rearrangements and [1,3]H shift in ylide intermediates become competitive processes. The reaction of N-benzyl-N,N-dimethyl-N-[α-(trimethylsilyl)benzyl]ammonium bromide (5) and 13C labeled (at the benzyl carbon) salt 5* gave a mixture of 10, 14, and 15 as products of [1,4], [1,2], and [2,3] rearrangement, respectively. 13C NMR spectra of products derived from salt 5* exclude [1,3]H shift in ylide 9a+-. Rearrangement of ylides generated from N-benzyl-N,N-dimethyl-N-[(dimethylphenylsilyl)methyl]ammonium bromide (6*) (enriched in 13C at benzyl carbon) and n-BuLi reveals that N,N-dimethyl-2-[(dimeth-ylphenylsilyl)methyl]benzylamine (20*) is not formed by a [1,4] shift but instead, via a [2,3] shift in silylmethylide followed by subsequent [1,4]Si and [1,2]H shift, as previously suggested in the literature. This mechanism is unique to some silyl-substituted ylides.
Ylide Reactions of Benzyldimethylammonium Halides
Sato, Yoshiro,Yagi, Yoko,Koto, Masami
, p. 613 - 617 (2007/10/02)
Deprotonation of benzyldimethylammonium halides (10) with sodium amide or n-butyllithium afforded silylated ylide intermediates 11, which were rearranged into N,N-dimethyl-2-benzylamines (13) accompanied by the formation of Sommelet-Hauser and Stevens rearrangement products (12 and 22).The ylide formation by the cleavage of carbon-silicon bonds also is discussed in the reaction of 10 with sodium amide and lithium aluminum hydride.
