70590-03-3Relevant academic research and scientific papers
STERICALLY-HINDERED ORGANOSILICON PERCHLORATES
Dua, Sujan S.,Eaborn, Colin
, p. 21 - 26 (1981)
The prechlorates (Me3Si)3C(SiMe2OClO3) and (Me3Si)2C(SiPh2Me)(SiMe2ClO3) have been obtained by treatment of the iodides (Me3Si)3C(SiMe2I) and (Me3Si)3C(SiPh2I), respectively, with AgClO4 in CH2Cl2.The perchlorates react with MeOH to give the methoxides (M
The Methanolysis of the Highly Sterically Hindered Organosilicon Compounds (Me3Si)3CSiMe2X with X=OSO2CF3, OCN or OClO3. A Mechanistic Enigma
El-Kaddar, Yousef Y.,Eaborn, Colin,Lickiss, Paul D.,Reed, David E.
, p. 1753 - 1759 (2007/10/02)
Rates of solvolysis have been determined for the compounds (Me3Si)3CSiMe2X with X=OSO2CF3, 3, or OCN, 6, (Me3Si)3CSiMe(OMe)OSO2CF3, 5, and (Me3Si)2C(SiMePh2)(SiMe2OSO2CF3), 4, in MeOH alone or containing water or NaOMe.The methanolyses of the trifluoromet
Photoinduced Ionic and Free-radical Reactions of Some Organosilicon Iodides
Eaborn, Colin,Safa, Kazem D.,Ritter, Alfred,Binder, Werner
, p. 1397 - 1402 (2007/10/02)
U.v. irradiation (medium-pressure Hg lamp) induces reaction of TsiSiPh2I (1a) 3Si)3C> with methanol to give both the unrearranged and rearranged methoxides TsiSiPh2OMe and (Me3Si)2C(SiPh2Me)(SiMe2OMe); in the presence of LiNO3 some (Me3Si)2C(SiPh2Me)(SiMe2ONO2) is also formed.The analogous solvolysis in PhNH2 gives the rearranged anilide (Me3Si)2C(SiPh2Me)(SiMe2NHPh).These reactions are thought to involve the intermediate formation of a silico-cation.On the other hand the exclusive formation of the unrearranged chloride TsiSiPh2Cl upon irradiation in CCl4 appears to involve a free-radical process.The photoinduced rearrangement of (1a) to (Me3Si)2C(SiPh2Me)(SiMe2I) in n-C5H12, n-C6H14, Et2O, and PhOMe may involve a cationic intermediate, but a free radical rearrangement cannot be ruled out; the subsequent formation of a disilaindane derivative (6) in PhOMe probably involves cyclization of a free radical.The iodide TsiSiPhMeI also undergoes rearrangement to (Me3Si)2C(SiPhMe2)(SiMe2I) upon irradiation in n-C5H12.The methanolysis of TsiSiMe2I is also photo-catalysed, though less effectively than that of (1a).
Photo-induced Reactions of an Organosilicon Iodide
Eaborn, Colin,Safa, Kazem D.,Ritter, Alfred,Binder, Werner
, p. 175 - 176 (2007/10/02)
The results of u.v. irradiation of (Me3Si)3CSiPh2I in MeOH, n-C6H14, CCl4, Et2O, and PhOMe are interpreted in terms of the formation of cationic as well as free-radical organosilicon intermediates.
Unimolecular Solvolysis of Some Organosilicon Perchlorates and Iodides
Eaborn, Colin,Mahmoud, Foad M. S.
, p. 1309 - 1315 (2007/10/02)
Kinetic studies have been made of the solvolysis (mainly the methanolysis) of the highly sterically hindered compounds TsiSiMe2OClO3 , (Me3Si)2(Ph2MeSi)CSiMe2OClO3, TsiSiHPhX (X=I, Br, ONO2), and TsiSiHMeI.The rate of methanolysis of TSiMe2OClO3 is increased by only ca.20percent upon addition of 0.1 M-NaOMe, and further additions of base have smaller effects.Additions of LiCl or LiNO3 cause even smaller rate increases, but in the presence of LiNO3 substantial amounts of TsiSiMe2ONO2 are formed, the amounts being greater than would correspond to the rate increases.Water has a very large accelerating effect, and even with only 1 vol percent of water present the product is very predominantly TsiSiMe2OH.The solvolysis is slower in EtOH and i-PrOH, and occurs only very slowly, if at all, in CF3CH2OH.The methanolysis of (Me3Si)2(Ph2MeSi)CSiMe2OClO3 is slower than that of TsiMe2OClO3.The methanolysis of TsiSiHPhI and TsiHMeI are also accelerated only to a small extent by NaOMe.The above results are interpreted in terms of an SN1 mechanism involving anchimerically assisted ionization of the Si-OClO3 or Si-I bond to give a methyl-bridged cation with unusual solvation requirements.In contrast, the methanolyses of TsiSiHPhX (X = Br or ONO2) are markedly accelerated by base, and it seems that, at least in the presence of base, attack by the nucleophile is involved in the rate-determining step in these cases.
THE REACTIONS OF SILICON HALIDES AND HYDRIDES WITH ELECTROPHILIC REAGENTS
Eaborn, Colin,Happer, Duncan A. R.,Hopper, Steven P.,Safa, Kazem D.
, p. 179 - 192 (2007/10/02)
A study has been made of the reactions of compounds of the type (Me3Si)3CSiR2X (e.g.X = I, R2 = Me2, Ph2, PhMe, Et2, or EtMe; X = H, R2 = Me2, Et2) with electrophilic reagents such as AgNO3, AgOAc, AgO2CCF3, Hg(NO3)2, Hg(OAc)2, HgCl2 and HgBr2, in alcohol
