Examination of the HR-NMR spectra of vinyl chloride in the presence of tetrahydrofuran and n-butyraldehyde suggests the formation of donor-acceptor type complexes. The equilibrium quotients and NMR constants were estimated by using the Benesi-Hildebrand method. The existence of these complexes would explain the anomalies observed: first, in the anionic polymerization of vinyl chloride initiated by tert-butylmagnesium chloride is tetrahydrofuran. The initiation step seems to be governed by this complexation phenomenon; second, in the radical polymerization of the same monomer in n-butylaldehyde the obtained poly(vinyl chloride) is more syndiotactic than the radical polymer prepared in bulk by the usual methods. 相似文献
NMR analysis of the low molecular weight poly(vinyl chloride) obtained from polymerizations initiated by t-BuMgCl in THF solution suggests that all the polymer chains have the structure: Enhanced signal/noise ratio by NMR spectrum accumulation confirms this structure in products of higher molecular weights. Examination of the NMR spectrum of vinyl chloride monomer in THF solution reveals the formation of a monomer–THF complex; it seems that the initiation step of the polymerization is governed by this complexation phenomenon. 相似文献
[structures: see text] The consequences of double diastereodifferentiation in chiral Lewis base catalyzed aldol additions using chiral enoxysilanes derived from lactate, 3-hydroxyisobutyrate, and 3-hydroxybutyrate have been investigated. Trichlorosilyl enolates derived from the chiral methyl and ethyl ketones were subjected to aldolization in the presence of phosphoramides, and the intrinsic selectivity of these enolates and the external stereoinduction from chiral catalyst were studied. In the reactions with the lactate derived enolate, the strong internal stereoinduction dominated the stereochemical outcome of the aldol addition. For the 3-hydroxyisobutyrate- and 3-hydroxybutyrate derived enolates, the catalyst-controlled diastereoselectivities were observed, and the resident stereogenic centers exerted marginal influence. The corresponding trimethylsilyl enol ethers were employed in SiCl4/bisphosphoramide catalyzed aldol additions, and the effect of double diastereodifferentiation was also investigated. The overall diastereoselection of the process was again controlled by the strong external influence of the catalyst. 相似文献
The purpose of this note is to give a proof of a theorem ofSerre, which states that if G is a p-group which is not elementaryabelian, then there exist an integer m and non-zero elementsx1, ..., xmH1 (G, Z/p) such that
with ß the Bockstein homomorphism. Denote by mG thesmallest integer m satisfying the above property. The theoremwas originally proved by Serre [5], without any bound on mG.Later, in [2], Kroll showed that mGpk 1, with k =dimZ/pH1 (G, Z/p). Serre, in [6], also showed that mG (pk 1)/(p 1). In [3], using the Evens norm map, Okuyamaand Sasaki gave a proof with a slight improvement on Serre'sbound; it follows from their proof (see, for example, [1, Theorem4.7.3]) that mG (p + 1)pk2. However, mG can be sharpenedfurther, as we see below. For convenience, write H*(G, Z/p) = H*(G). For every xiH1(G),set
1991 Mathematics SubjectClassification 20J06. 相似文献
Competitive [2+2] photodimerization and E-->Z isomerization reactions occur in a co-crystal of 1,1,6,6-tetraphenyl-2,4-hexadiyne-1,6-diol upon irradiation with 325 nm light. At 90 K both reactions are observed, whereas at 280 K the dimerization reaction is very fast and inhibits isomerization as the nature of the chromophore is affected by the reaction. The temperature dependence of the stereospecificity of the dimerization reaction is related to the large sliding motion required to bring the reacting molecules into juxtaposition. The progress of the reactions has been monitored by photocrystallographic methods. 相似文献