Mechanism of the acid-catalyzed hydrolysis of N-acylsulfamates

The kinetics of hydrolysis of a series of N-acylsulfamate esters p-XC₆H₄OSO₂NHCOR as models for more complex, biologically important compounds has been examined. Structure-reactivity, solvent-reactivity, thermodynamic data, etc. support a bimolecular mechanism involving water in the transition state (TS).     

Photoreduction de la benzophenone par des phtalimidines et des dihydro isoquinolones: Etude chimique par RMN PNIC

Benzophenone is photoreduced by pthalimidines and dihydro isoquinolones. The hydrogen atom α to the nitrogen atom is abstracted and radical coupling leads to adducts. CIDNP studies of these adducts show inversion of polarisation for the adduct on the N-alkyl chain when the nitrogen is bound to a benzylic methylene. This inversion is explained by considering that the radical on the N-alkyl chain derives from the radical on the ring.     

Action de O- et N-nucléophiles sur les sels de phényl-3 benzopyrylium-1

3-Phenyl-1-benzopyrylium percholorates 1a, 1i react exculusively at C-2 with ethanol and isopropyl alcohol, affording mixed acetals 2a, 3a, 3i . Aqueous ammonia gives symmetrical secondary amines 4a, 4b or bis(3-phenyl-2H-1-benzopyran-2-yl)amines, while with aqueous aliphatic amines (40%) bis-acetals 5a, 5b or 2,2′-oxy-bis(3-phenyl-2H-1-benzopyrans) are characterized. In some other acidic conditions, 5a and 5b are also obtained.     

Benzophenone photoreduction by heteroatom-containing donors

Nanosecond flash photolysis has been carried out on benzophenone solutions in benzene and acetonitrile in presence of oxygen- and sulfur-containing reductants such as anisole, thioanisole, dibutyl sulfide and methyl 2-octyl ether. The quantum yield of ketyl formation is compared to previous results on the quantum yields of the final benzophenone disappearance. This comparison is also related to previous data on benzophenone reduction by nitrogen-containing reductants such as amines and amides and suggests a general mechanism for benzophenone photoreduction by heteroatom-containing donors.     

Etude de la cristallinite de derives n-octadecyliques de l'alcool polyvinylique obtenus par greffage chimique

Differential scanning calorimetry has been used to study the heats of fusion and melting transitions of n-octadecyl derivatives of polyvinyl alcohol. These derivatives were obtained by grafting paraffinic chains on polyvinyl alcohol, at various proportions. The melting transitions are independent of the degree of substitution; the heats of fusion are proportional to the fraction of crystallizable units. Using Flory's equilibrium crystallization theory, it is possible to interpret these results assuming, as demonstrated previously, that the chemical grafting is sequential with two unreacted hydroxyl groups between two adjacent paraffinic side-chains.     

Synthesis of 2,6-Dihalo-4-nitro-N-alkylanilines by Aromatic Substitution of 2,6-Dihalo-4-nitro-arylethers

An aromatic nucleophilic substitution reaction of phenylethers with primary amines is described. This reaction, promoted by electron-attracting groups on the benzene ring, fast and simple to perform, leads to substituted anilines in high yields.     

Hydrosilylation Reactions Catalyzed by Rhenium

Hydrosilylation is an important process, not only in the silicon industry to produce silicon polymers, but also in fine chemistry. In this review, the development of rhenium-based catalysts for the hydrosilylation of unsaturated bonds in carbonyl-, cyano-, nitro-, carboxylic acid derivatives and alkenes is summarized. Mechanisms of rhenium-catalyzed hydrosilylation are discussed.     

Synthesis of 5α, 13α, 14α-Androstan-16-One and 5α, 13β, 14β—Androstan-16-One Using a Novel 17–16 Carbonyl Transposition

In the course of current work on the conformational analysis of cis-hydrindanones¹, we required 5α, 13α, 14α and 5α, 13β, 14β-androstan-16-one 5 and 10 the C and D rings of which provide rigid models of the two conformations of cis-hydrindan-2-one.