Organosilicon synthesis of isocyanates: II. Synthesis of aliphatic, carbocyclic, and fatty-aromatic isocyanates
作者:A. V. Lebedev、A. B. Lebedeva、V. D. Sheludyakov、S. N. Ovcharuk、E. A. Kovaleva、O. L. Ustinova
DOI:10.1134/s1070363206030182
日期:2006.3
Silylation of a series of aliphatic, carbocyclic, and fatty-aromatic amines gave the corresponding silyl derivatives whose yield depended on the electronic and steric structure of the substrate and the nature of the silylating agent. The yield of isocyanates obtained by phosgenation of the silyl derivatives under mild conditions decreased in going from aliphatic amines to benzylamines and rose as the length of the alkyl chain in fatty-aromatic amines extended. The most convenient procedure for the synthesis of low-boiling alkyl isocyanates was found to be based on the transformation of amines or ammonium salts into silyl or silyl silyl-carabamates. followed by pyrolysis of the latter in the presence of trichloro(phenyl)silane.
Synthesis, characterization and polymerization potential of unbridged and bridged half-sandwich complexes of zirconium containing N-donor ligands
作者:Helmut G Alt、Klaus Föttinger、Wolfgang Milius
DOI:10.1016/s0022-328x(98)00641-x
日期:1998.8
The synthesis of unbridged half-sandwich complexes of the type (C5H5)Zr[N(SiMe3)CH2CH2R]Cl2 (R=OMe, NMe2) and bridged half-sandwich complexes of the type (Cp#–SiMe2–NCH2CH2R)ZrCl2 (Cp#=C5H4, C9H6, C13H8) including intramolecular N-donor ligands is described. The complexes were characterized by 1H-, 13C-, and 29Si-NMR spectroscopy. The complexes (C5H5)Zr[N(SiMe3)CH2CH2NMe2]Cl2 (2) and (C5H4-SiMe2-NCH2CH2NMe2)ZrCl2
(C 5 H 5)Zr [N(SiMe 3)CH 2 CH 2 R] Cl 2(R = OMe,NMe 2)类型的未桥接半三明治复合物和((描述了包括分子内N-给体配体的Cp # -SiMe 2 -NCH 2 CH 2 R)ZrCl 2(Cp # = C 5 H 4,C 9 H 6,C 13 H 8)。配合物的特征是1 H-,13 C-和29 Si-NMR光谱。(C 5 H 5)Zr [N(SiMe 3)CH 2 CH 2 NMe 2 ] Cl 2(2)和(C 5 H 4 -SiMe 2 -NCH 2 CH 2 NMe 2)ZrCl 2(4)的络合物为通过X射线晶体结构测定进一步表征。在固态下,二甲基氨基的氮原子与锆原子配位。