3440-02-6Relevant articles and documents
Scrambling of substituents between dimethylsilicon and various methylphosphorus moieties
Moedritzer, Kurt,Van Wazer, John R.
, p. 2856 - 2859 (1973)
Equilibrium constants have been measured for the scrambling of pairs of substituents between the (CH3)2Si3P3P(O)3P(S)a phenoxyl or dimethylamino group, the chlorine is preferentially bonded to the silicon in the case of the CH3P(O)3P(S)3P moiety. The quantitative equilibrium data are discussed, as are the kinetics of exchange of chlorine and bromine between the dimethylsilicon and the methylthiophosphonyl moieties.
N,N-Bis[ethoxy(methyl)silylmethyl]methylamines MeN[CH2SiMem(OEt)3-m]2 (m = 0 - 2). Synthesis and reactions with phenol
Lazareva,Brodskaya
, p. 201 - 205 (2007/10/03)
Previously unknown N,N-bis[ethoxy(methyl)silylmethyl]amines MeN[CH2SiMem(OEt)3-m]2 (m = 0-2) were synthesized. According to UV spectral data, only MeN[CH2SiMe2(OEt)]2 form hydrogen bond with phenol in a heptane solution. The amines with m = 0 and 1 fail to forms hydrogen bond with phenol [under the same conditions, N-(triethoxysilylmethyl)dimethylamine Me2NCH2Si(OEt)3 forms a strong hydrogen bond with phenol]. All the amines (m = 0 - 2) enter transetherification with phenol to give compounds of the general formula MeN[CH2SiMem(OPh)n(OEt)3-m-n]2 (m = 0 - 2, n = 1 - 3). Refluxing of N,N-bis[ethoxy(methyl) silylmethyl]amines with excess phenol results in cleavage of the Si-C bond by phenol, providing phenoxysilanes MemSi(OPh)4-m (m = 0 - 2) and trimethylamine.
The modification of reactivity at silicon centre by a remote phosphorus group
Kowalski, Jozef,Chojnowski, Julian
, p. 285 - 296 (2007/10/02)
The compounds X(CH2)nSiMe2(OPh) (X = H, n = 2, 3; X = PPh2, n = 1, 2, 3; X = P(O)Ph2, n = 2, 3; X = P(S)Ph2, n = 1, 2, 3) having silicon and phosphorus bridged by carbon chains, have been synthesized.The kinetics of acid- and basecatalysed solvolytic cleavage of phenoxyl group from these compounds in methanol have been investigated.The kinetic results obtained in the presence of bases can be interpreted in terms of polar and steric effects alone, but there was an unexpected enhancement of the reactivity in the case of the P=O-containing substrates in the acidic media.The solvent kinetic isotope effects are best interpreted in terms of participation by the P=O group as a base rather than as a nucleophile attacking the silicon centre.
O-SILYLATED KETENE ACETAL CHEMISTRY; DIVINYLOXYSILANE DERIVATIVES AS NOVEL AND USEFUL BIFUNCTIONAL PROTECTING AGENTS FOR H-ACIDIC MATERIALS
Kita, Yasuyuki,Yasuda, Hitoshi,Sugiyama, Yoshie,Fukata, Fumio,Haruta, Jun-ichi,Yasumitsu, Tamura
, p. 1273 - 1276 (2007/10/02)
Novel reagents, bis(1-methoxy-2-methyl-1-propenyloxy)silanes (2a-d) have been shown to be very useful bifunctional protecting agents for various types of H-acidic materials, such as diols, dithiols, diacids and their combined materials.The reaction proceeds rapidly under mild conditions to give the corresponding silylene derivatives in almost quantitative yields.
LE PROBLEME DE LA CONJUGAISON A TRAVERS UN ATOME DE SILICIUM ?-LIE DANS LES SYSTEMES SILA-2 BUTADIENIQUES
Bertrand, G.,Manuel, G.,Mazerolles, P.,Trinquier, G.
, p. 2875 - 2880 (2007/10/02)
The chemical behaviour of sila-2 butadienes, formed as transient intermediates either by thermolysis or by photolysis of various 1-vinylsilacyclobutanes, was studied with respect to hydroxylated compounds of different pKa values.Two mechanisms can explain the nature of the products obtained on the co-thermolysis of the cyclic compounds with phenol, one with 1-silacyclobut-1-ene intermediate and the other involving an allylic silicenium cation.In both hypothetical mechanisms, the 2-silabutadienes behave as a conjugated system since they lead either to cycloaddition or to (1,2)- and (1,4)-electrophilic addition.This evidence for a conjugation phenomenon through a silicon atom is supported by the calculation of the delocalisation energies of butadiene and 2-silabutadiene.
