132775-06-5Relevant articles and documents
Addition of aldehydes to germenes: The influence of solvent
Allan, Christopher J.,Reinhold, Crispin R.W.,Pavelka, Laura C.,Baines, Kim M.
, p. 3010 - 3017 (2011/07/08)
The addition of trans-(2-phenylcyclopropyl) carboxaldehyde to dimesitylfluorenylidenegermane produced four diastereomers of a 1,2-oxagermin, 7a-d, 2,2,4,4- tetramesityl-1,3-dioxadigermetane (8), and fluorenylidene- (trans-2-phenylcyclopropyl)methane (9). The ratio of the products showed a strong dependence on the solvent: 7a-d were formed almost exclusively when ether or benzene was used as the solvent for the reaction, whereas 1,3-dioxadigermetane 8 and alkene 9 were the major products formed in THF. A mechanism is proposed to account for the observations.
Varied reactivity of the Germene Mes2Ge=CR2 toward nitriles
El Kettani, Sakina Ech-Cherif,Lazraq, Mohamed,Ranaivonjatovo, Henri,Escudie, Jean,Couret, Claude,Gornitzka, Heinz,Merceron, Nathalie
, p. 5062 - 5065 (2008/10/09)
The germene Mes2Ge=CR2 (1, CR2 = fluorenylidene) shows varied behavior toward nitriles. It reacts as a 1,2-dipole with t-BuCN giving a four-mepibered ring heterocycle, 2-aza-3-germacyclobut-1- ene, as a 1,4-dipole with PhCN, leading to a six-membered ring heterocycle, 3,4-dihydro-3-germaisoquinoline, and as a base, abstracting the α-H of R′CH2CN to give α-cyanogermanes (R′ = H, 2-thienyl, 2-FC6H4, 4-FC6H4).
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Riviere-Baudet, Monique,El Baz, Fatima,Satge, Jaques,Khallaayoun, Abdelhay,Ahra, Mohamed
, p. 203 - 217 (2007/10/03)
Germyl derivatives of N-2,4,6-trifluoroaniline were synthesized either by dehydrohalogenation between halogermanes and 2,4,6-trifluoroaniline over DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) or by elimination between halogermanes and 2,4,6-trifluoroanilinolithium. Dimesitylfluorogermyl N-2,4,6-trifluoroanilinolithium stabilized by THF slowly eliminated lithium fluoride leading to 2,4(2,4,6-trifluorophenyl)-1,3-tetramesitylcyclodigermazane, mainly through intermolecular elimination while in the presence of MgBr2 or tBuMgBr the corresponding germa-imine was formed. Dimesitylchlorogermyl-2,4,6-trifluoroanilino lithium also led to cyclodigermazane while the corresponding bromogermyl lithium or magnesium compound gave mainly the stable 2,4,6-trifluorophenyl dimesitylgerma-imine by intramolecular elimination. The same stable germa-imine was also obtained by exchange reaction between dichlorodimesitylgermane and N-bis(triethylgermyl)2,4,6-trifluoroaniline. Reactivities of monomeric germa-imine and its dimer cyclodigermazane are compared. The dimer is almost inert towards water and methanol and does not react with chloroform and N-tert-butylphenyl nitrone while the germa-imine leads to the corresponding adducts. The adduct with chloroform through α-elimination of dichlorocarbene gave N-dimesitylchlorogermyl trifluoroaniline. The electron withrawing effects of the trifluorophenyl group on nitrogen stabilize the germa-imine, preventing its dimerization, but also induce a decrease in reactivity of germanium nitrogen compounds within the series.
