The synthesis of silyl- and germyldiazoalkanes via tosylhydrazones

Abstract

Tosylhydrazones have been prepared from acylsilanes and -germanes. These may be converted in excellent yield by 11-butyllithium to the metalloidal diazoalkanes tinder milder conditions than are required for the analogous carbon compounds. The diazoalkanes are far more stable than their carbon counterparts. These results, together with spectral shifts noted for the silyl and germyl compounds, are interpreted in terms of dn-pn bonding between the diazo group and the metalloid atom.

Radical Cyclizations of Acylgermane Oxime Ethers and Hydrazones: Direct Routes to Cyclic Hydrazones and Oximes

“…Condensation reactions of simple ketones with various nitrogen-nucleophiles are well-known and have been used for a long time. In contrast, acylgermanes have rarely been used in condensation reactions . In 1993, Ahlbrecht and Baumann accomplished the condensation of primary amines with acylstannanes.…”

Diastereoselective syntheses and oxygenation of silyl fulleroids

“…Because of the instability of silyldiazo compounds except 1d, they were used as ether solution without further purification. (Me 3 Si) 2 CN 2 (4a) and Me 3 SiCN 2 SiMe 2 SiMe 3 (4b) were prepared using 1a or phenyldiazomethane followed by coupling with Me 3 SiCl, Me 3 SiCN 2 Ph (4c), Me 3 SiMe 3 SiCl [7,12,13] .…”

“…For 3c: 1 H NMR (500 MHz, C 6 D 6 : CS 2 = 1:1) d 0.62 (s, 6H), 2.69 (m, 1H), 3.59 (s, 3H), 3.64 (s, 3H), 6.72 (d, 1H), 7.07 (s, 1H), 7.16 (d, 1H); 13 C NMR (125 MHz, C 6 D 6 : CS 2 = 1:1) d À1.48 (q), 40.65 (d), 55.40 (q), 55.92 (q), 112.30 (d), 116.02 (d), 126.64, 128.30, 132.94, 136.17 (s), 136.66 (s), 137.48, 137.62 (s), 137.94, 138.53, 139.88, 140.05, 141.43, 142.05, 142.94, 143.05, 143.11, 143.13, 143.22, 143.28, 143.46, 143.48, 143.50, 143.61, 143.69, 143.74, 143.78, 143.89, 143.98, 144.26, 144.29, 145.22, 145.25, 148.52, 149.64 (s) …”

“…13 C NMR (top) and gated decoupled 13 C NMR (bottom) of the fullerene region of 3c. X denotes 13 C-1 H long couplings.…”

Gas-phase pyrolysis of phenyltrimethylsilyldiazomethane. Intramolecular chemistry of phenyltrimethylsilylcarbene

“…Brook and Jones report the preparation of the tosylhydrazone in hot glacial acetic acid. 10 Lithium Salt of Phenyl Trimethylsilyl Ketone Tosylhydrazone. A solution of 5.57 g of phenyl trimethylsilyl ketone tosylhydrazone was dissolved in 6.8 mL of distilled tetrahydrofuran and cooled in a dry ice/acetone bath to -78 °C.…”