- Synthesis and characterization of diacylgermanes: persistent derivatives with superior photoreactivity
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Acylgermanes are known as highly efficient photoinitiators. In this contribution, we present the synthesis of new diacylgermanes4a-eviaa multiple silyl abstraction methodology. The method outperforms the state-of-the-art approach (Corey-Seebach reaction)
- Fischer, Roland C.,Frühwirt, Philipp,Gescheidt, Georg,Griesser, Thomas,Haas, Michael,Kelterer, Anne-Marie,Müller, Stefanie M.,Püschmann, Sabrina D.,Torvisco, Ana,Wagner, Stefan H.
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The lithiation of Mes2GeH2 with nBuLi in a 1:2 molar ratio at low temperature gives an aggregate 1 of the parent germyllithiated derivative, unreacted nBuLi and ether in a 1:1:1 ratio. Compound 1 was characterized by 1H, 13C and 7Li NMR. Reactions of 1 with D2O and Me3SiCl afford exclusively the monosubstituted derivatives. With PhCHO, we observe the formation of the germylated alcohol 5 and PhCHOHBu. Reaction with Mel is more complex and leads to the dimethylated compound 6 through a single electron transfer mechanism. Transient radical species are detected by an ESR study.
- Cosledan,Castel,Riviere
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- 3-Alkylidenethiagermiranes
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Dimethyl- and diphenylgermylenes react with di-tert-butylthioketene to give 4-alkylidene-1,2,3-thiadigermetanes 2 and 4, the products of the insertion of germylenes into 3-alkylidenethiagermiranes. Dimesitylgermylene generated by the thermolysis of hexamesitylcyclotrigermane (12) at 80°C reacts with di-tert-butylthioketene to produce a stable 3-alkylidenethiagermirane, 13. Photolysis of 13 produces dimesitylgermylene and di-tert-butylthioketene via germathiocarbonyl ylide 17, which is intensely blue in color with a maximum band at 580 nm. 13 reacts with dimethylgermylene to yield the corresponding 4-alkylidene-1,2,3-thiadigermetane 22. Oxidation of 13 by m-chloroperbenzoic acid gives 3-alkylidene-1,2,4-oxathiagermetane S-oxide 23.
- Ando, Wataru,Tsumuraya, Takeshi
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p. 1467 - 1472
(2008/10/08)
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