78375-55-0Relevant academic research and scientific papers
The chemical behavior of the silaoxine C22H34OSi3 and silaazetidine C25H43NSi4 towards CO2
S?nger, Inge,Bolte, Michael,Lerner, Hans-Wolfram
, p. 1219 - 1224 (2016/12/09)
When 4,4a-dihydro-3,3-dimethyl-1-phenyl-4,4-bis(trimethylsilyl)-3H-2-oxa-3-sila-naphthaline (silaoxine C22H34OSi3 (3); orthorhombic, space group Pna21, Z=4) was thermolized in a CO2 atmosphere, the co
Reactivity of the Silaethene Ph2Si=C(SiMe3)2
Wilberg, Nils,Link, Matthias
, p. 1231 - 1240 (2007/10/03)
Silaethene Ph2Si=C(SiMe3)2 (3), generated as a reaction intermediate by the thermal elimination of LiX from Ph2SiX-CLi(SiMe3)2 (X = Br, F) or by the thermal cycloreversion of the cycloadduct of 3 and Ph2C=NSiMe3, forms adducts 3*donor, the stability of which increases in the order of donor = Et2O according to an ene reaction, with a=b (e.g.CH2=CHOMe; Ph2C=NSiMe3) or a=b=c (e.g. (t-Bu)2RSiN3, R = Me, t-Bu) or a=b-c=d with or or cycloaddition.The following order of relative reactivity of trapping reagents for Ph2Si=C(SiMe3)2 was found: Ph2CO > (t-Bu)2MeSiN3 > butadiene > 2,3-dimethylbutadiene > Ph2CNSiMe3 > (t-Bu)3SiN3 > anthracene.Summing up, it may be said that going from Me2Si=C(SiMe3)2 to Ph2Si=C(SiMe3)2 there is only a gradual but not principal change of silaethene reactivity.This change is due to increasing polarity and overcrowding of the double bond, that is increasing Lewis acidity and steric hindrance of the unsaturated silicon atom.Certainly, the former silaethene stabilizes thermally by dimerization, the latter by isomerization. - Keywords: Adduct formations, insertions, ene reactions, -, -, -cycloadditions of Ph2Si=C(SiMe3)2 ; Reactivity order of traps ; Reactivity of Me2Si=C(SiMe3)2 and Ph2Si=C(SiMe3)2
Storing of the Labile Silaethene Me2Si=C(SiMe3)2 with Benzophenone
Wiberg, Nils,Preiner, Gerhard,Schurz, Klaus,Fischer, Gerd
, p. 1468 - 1474 (2007/10/02)
Benzophenone Ph2C=O is able to "store" the silaethene Me2Si=C(SiMe3)2 (1), produced from Me2SiX-CLi(SiMe3)2 (X = F, Br, Ph2PO4), under formation of a cycloadduct (2b).At about 100 deg C, 2b by way of 1 transfers into the cycloadduct of 1 and Ph2C=O (3b), which in the course of transformation decomposes visibly (in the absence of Me3SiCl) or only by traces (in the presence of Me3SiCl) to secondary products.In the presence of ROH (R = H, Me, tBu, MeCO) or PhN=NSiMe3 or RN3 (R = tBu, Me3Si) or 2,3-dimethylbutadiene (dmb) about 100 deg C 2b and 3b form by way of 1 insertion products of 1 into the OH bond of ROH or a cycloadduct of 1 and PhN=NSiMe3 or cycloadducts of 1 and RN3 or cycloadduct and an ene reaction product of 1 and dmb.The rate constants/half lives of the first order transformation of 2b into 3b or of the first order decomposition of 2b or of 3b in the presence of reactive traps for 1 (ROH, Me3SiN3; benzene as solvent) are in the order of 0.3E-4 s-1/τ1/2 = 7 h (2b --> 3b; 90 deg C) 3E-4 s-1/τ1/2 = 3/4 h (2b + traps; 90 deg C), 0.4E-4 s-1/τ1/2 = 5 h (3b + traps, 110 deg C). - Keywords: Silaethene Me2Si=C(SiMe3)2, Insertions, Cycloadditions, Kinetic Studies
Reaktivitaet des Silaethens Me2Si=C(SiMe3)2: Thermolyse von (Me3Si)2(Me2XSi)CLi (X z. B. (PhO)2PO2) in Anwesenheit von Silaethen-Faengern
Wiberg, Nils,Preiner, Gerhard,Schieda, Oswald
, p. 3518 - 3532 (2007/10/02)
Silaethene Me2Si=C(SiMe3)2 (1), generated as a reaction intermediate by the thermal elimination of LiX from Me2XSi-CLi(SiMe3)2, combines with the reactants a - b (e. g.Me3Si-Cl, Me3Si-OMe) with insertion in the a - b bond, with a = b - c - H (e. g.CH2=CMe
The Reactions of Tris(trimethylsilyl)methyl-lithium with Some Carbon Electrophiles
Fleming, Ian,Floyd, Christopher D.
, p. 969 - 976 (2007/10/02)
Tris(trimethylsilyl)methyl-lithium (1) reacts with non-enolisable aldehydes, ketones, and acid chlorides, and with some epoxides, with the formation of carbon-carbon bonds.This method of preparing functionalized silanes is limited by the readiness with which (1) abstracts a proton, if one is available, rather than attack at carbon.In the reaction with epoxides, the product alkoxide can transfer a silyl group from carbon to oxygen, and in one case the intermediate so formed reacts to give a cyclopropane (32) in what is a homologue of the Peterson reaction.The 1,4-transfer of a silyl group occurs in other systems when the resulting carbanion is stabilised by such groups as phenylthio and diphenylphosphinoyl.
