5764-67-0Relevant articles and documents
Synthesis and properties of a strained germacycle having a Ge-Ge bond, 3,4-benzo-1,1,2,2-tetraethyl-1,2-digermacyclobut-3-ene
Komoriya, Haruhiko,Kako, Masahiro,Nakadaira, Yasuhiro,Mochida, Kunio
, p. 2014 - 2018 (2008/10/08)
A new strained germacycle, 3,4-benzo-1,1,2,2-tetraethyl-1,2-digermacyclobut-3-ene (1), was prepared by treatment of 1,2-bis(chlorodiethylgermyl)benzene with sodium in toluene. At ambient temperature, 1 was gradually oxidized in air to give 3,4-benzo-1,3-digerma-2-oxacyclopent-4-ene (2), and in the presence of sulfur, 1 was converted to 3,4-benzo-1,3-digerma-2-thiacyclopent-4-ene (3), quantitatively under similar thermal conditions. The digermacyclobutene 1 was thermally labile and readily underwent ring-opening polymerization in toluene to give the corresponding polymer 4 (Mn = 4.4 × 105, Mw = 7.4 × 105, Mw/Mn = 1.7). On thermolysis at 160 °C for 20 h, 1 gave two products, 4,5-benzo-1,2,3-trigermacyclopent-4-ene (5) and 3,4:6,7-dibenzo-1,2,5-trigermacyclohepta-3,6-diene (6), in reasonable yields. On the other hand, the thermolysis of 1 in the presence of phenylacetylene gave 2,3-benzo-1,4-digerma-5-phenyl-cyclohexa-2,5-diene (7), quantitatively. Further, 1 was thermolyzed in CCl4 to give two chlorinated products, 1,2-bis(chlorodiethylgermyl)benzene (9) and 1-(chlorodiethylgermyl)-2-(diethyl(trichloromethyl)germyl)benzene (10), in reasonable yields. The reaction mechanisms for the polymerization and the thermolysis are discussed.
Photochemical Addition of Benzyltriethylgermane and Dibenzyldiethylgermane to Olefines
Kobayashi, Masanori,Yoshida, Masato,Kobayashi, Michio
, p. 3169 - 3174 (2007/10/02)
A novel photochemical addition of a germanyl radical to the olefinic double bond was discovered when benzyltriethylgermane or dibenzyldiethylgermane was irradiated with a medium-pressure mercury lamp in the presence of olefins.
DIOXA- ET DITHIAGERMOLES: SYNTHESE ET QUELQUES ASPECTS DE LEUR REACTIVITE
Lavayssiere, Helene,Dousse, Gabriel
, p. C17 - C22 (2007/10/02)
Synthetic methods to obtain new dioxagermoles and dithiagermoles are described.Dioxagermoles decompose to germylenes and α-diketone on thermolysis, and formation of cyclotrigermathianes (R2GeS)3 from dithiagermoles is observed at about 200 deg C via a R2Ge=S intermediate.Exchange reactions between dioxagermoles or dithiagermoles and thiophosgene give a dioxolethione and a dithiolethione, respectively.In the exchange reaction between dithia- and dioxa-germoles with GeCl2*dioxane, formation of new stable unsaturated germylenes is observed.
POLYGERMANES PRECURSEURS D'ESPECES DU GERMANIUM A COORDINNANCE NON USUELLE
Riviere, P.,Castel, A.,Satge, J.,Guyot, D.
, p. 193 - 206 (2007/10/02)
Several thermal or photochemical α-elimination reactions of functional polygermanes lead to germylenes, R2Ge.Photolysis of polygermanes, cyclopolygermanes and polygermylmercury compounds and also hydrogen abstraction from various organohydropolygermanes using t-BuO., lead to the formation of polymetallated chains containing one or two germanium-centered radicals.These polygermyl radicals give germylenes, R2Ge, germanium centered radicals Ge., α-digermyl diradicals (or digermenes) Ge.-Ge. or Ge=Ge> and β- or γ-polygermyl diradicals via ahomolytic monoelectronic α-elimination process.In some cases the formation of α-digermyl diradicals or digermenes can also be seen as occuring through dimerization of germylenes but with lower yields.All these intermediates have been characterized by several trapping reactions with dimethyl disulfide, 2,3-dimethylbutadiene or biacetyl.
