2848-62-6Relevant academic research and scientific papers
Reactivity of N-(chlorodimethylgermyl)methyl and N-(chlorodimethylsilyl) methyl derivatives of lactams and amides toward Grignard reagents
Bylikin,Shipov,Kramarova,Artamkina,Negrebetskii,Baukov
, p. 1356 - 1358 (2004)
N-[(Chlorodimethylgermyl)methyl]lactams and -amides containing a five-coordinate germanium atom react with Grignard reagents chemoselectively by the Ge-Cl bond to form four-coordinate germanium compounds. The method of competitive reactions was used to es
Carbanions as intermediates in the formation of Grignard reagents
Van Klink, Gerard P.M.,De Boer, Henricus J.R.,Schat, Gerrit,Akkerman, Otto S.,Bickelhaupt, Friedrich,Spek, Anthony L.
, p. 2119 - 2135 (2008/10/08)
The formation of reactive carbanions in Grignard reagents was discussed. Inter- and/or intramolecular migrations of organotin and organosilicon groups were also studied. Results showed that the high percentage of rearrangement reactions proves that the anionic species are not located on a minor pathway.
Photochemical Reactions of Vinyl-, Styryl- and Benzyl-Substituted Digermanes
Mochida, Kunio,Kikkawa, Haruhiko,Nakadaira, Yasuhiro
, p. 2772 - 2777 (2007/10/02)
Photochemical reactions of vinyl-, styryl- and benzyl-substituted digermanes by chemical trapping experiments.Photolysis of vinylpentamethyldigermane afforded 1-trimethyl-2-(pentamethyldigermyl)ethane as a major product, and styrylpentamethyldigermanes gave mainly styryltrimethylgermane.On the other hand, photolysis of benzyl-substituted digermanes (benzylpentamethyldigermane and 1,2-dibenzyltetramethyldigermane) gave hydrogermanes and hydrodigermanes as main products, respectively.These products were derived from germyl radicals generated by photoinduced homolysis of the germanium-germanium bond.In carbon tetra chloride (CCl4), these germyl radicals were converted to the corresponding chlorogermanes by abstraction of a chlorine atom.Germylene species were also to be evolved from such photolyses.
Chemistry of heavy carbene analogues R2M (M = Si, Ge, Sn). 12. Concerted and nonconcerted insertion reactions of the germylene Me2Ge into the carbon-halogen bond
K?cher, Jürgen,Lehnig, Manfred,Neumann, Wilhelm P.
, p. 1201 - 1207 (2008/10/08)
During the reaction of Me2Ge with CCl3X (X = Cl, Br), PhCH2X (X = Br, I), and Ph2CHCl, 1H CIDNP is observed in the products of net insertion of Me2Ge into the carbon-halogen bond and in Me2GeX2 (X = Cl, Br). It is concluded that a two-step radical reaction takes place by an abstraction-recombination mechanism. No reaction takes place with alkyl halides that have a C-X bond dissociation energy of more than about 70 kcal/mol. Me2Ge is generated thermally at 70-95°C or photochemically from the 7-germabenzonorbornadiene 1 and reacts in both cases in the singlet state. The activation energy for forming Me2Ge from 1 is 19 kcal/mol for the reaction with CCl4. Insertion products are also formed with the alkenyl halides CH2=CHCH2X, PhCH=CHX (X = Cl, Br), and 2-bromobut-2-ene, but without showing CIDNP effects. Since Me2GeX2 was not found either, Me2Ge reacts in these cases in a nonradical manner. It does not react with 1-chlorocyclohexene, but it does react with Me2GeX2 under formation of digermanes and/or oligogermanes without CIDNP.
1,n-TRIORGANOSILYL MIGRATIONS IN THE REARRANGEMENTS OF SILYL-SUBSTITUTED ORGANOLITHIUM COMPOUNDS
Eisch, John J.,Tsai, Miin-Rong
, p. 5 - 24 (2007/10/02)
Under the agency of the potent lithiating agent, n-butyllithium in TMEDA, an array of organosilanes was found to undergo 1,n-silyl rearangements via carbanionic intermediates.Unambiguous 1,2-, 1,3- and 1,4-silyl shifts were unconvered in 1-trimethylsilyl-
