Complexation du chlorure de vinyle par le tetrahydrofuranne et le n-butyraldéhyde: Étude par résonance magnétique nucléaire haute résolution

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.     

Précisions apportées au mécanisme de la polymérisation du chlorure de vinyle par le chlorure de tertiobutyle-magnésium en milieu tétrahydrofurannique. Etude par résonance magnétique nucléaire

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.     

Lewis base catalyzed aldol additions of chiral trichlorosilyl enolates and silyl enol ethers

[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.     

Serre's Theorem on the Cohomology Algebra of a p-Group

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, ..., x_m H¹ (G, Z/p) such that with ß the Bockstein homomorphism. Denote by m_G thesmallest integer m satisfying the above property. The theoremwas originally proved by Serre [5], without any bound on m_G.Later, in [2], Kroll showed that m_G p^k – 1, with k =dim_Z/pH¹ (G, Z/p). Serre, in [6], also showed that m_G (p^k –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 m_G (p + 1)p^k–2. However, m_G can be sharpenedfurther, as we see below. For convenience, write H^*(G, Z/p) = H^*(G). For every x_i H¹(G),set 1991 Mathematics SubjectClassification 20J06.     

A method for solving d.c. programming problems. Application to fuel mixture nonconvex optimization problem

We present a numerical method for solving the d.c. programming problem

A near-infrared dye for multichannel imaging

A large Stokes shift dye, composed of water-solubility and near-infrared feature, was developed for multichannel imaging applications.     

Competitive isomerization and dimerization in co-crystals of 1,1,6,6-tetraphenyl-2,4-hexadiyne-1,6-diol and sorbic acid: a new look at stereochemical requirements for [2+2] dimerization

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.