A new reaction of phosphorylated N-sulfonylimines with hydrophosphoryl agents involving C → N transfer of phosphoryl groups

Hydrophosphoryl nucleophilic agents add to the CN bond of N-sulfonyltrichloroacetimidoylphosphonates to give unstable C,C-diphosphorylated adducts, which undergo competitive 1,2-C → N phosphorotropic rearrangement and dehydrochlorination with the formation of aza-Perkow reaction products, C,N-diphosphorylated dichlorovinylsulfonamides. This is the first reliably identified case of an aza-Perkow transformation for acid phosphites and their initial nucleophilic attack at the C atom of the azomethine bond in the aza-substrates.     

Direct vinylation of glucose derivatives with acetylene

Vinyl ethers, promising chiral carbohydrate synthons, have been synthesized by the addition of glucose acetals (1,2:5,6-di-O-isopropylidene-α-d-glucofuranose, methyl 4,6-O-benzylidene-α-d-glucopyranoside, 1,2-O-cyclohexylidene-α-d-glucofuranose, methyl α-d-glucopyranoside) to acetylene under atmospheric and elevated pressures in an autoclave in the presence of superbase catalytic systems (KOH-DMSO, t-BuOK-DMSO). The complete vinylation of 1,2:5,6-di-O-isopropylidene-α-d-glucofuranose and methyl α-d-glucopyranoside has been realized under elevated pressure of acetylene in the system KOH-THF as well.     

Facile syntheses of unsolvated UI3 and tetramethylcyclopentadienyl uranium halides

In the course of comparing the reaction chemistry of (C5Me5)3U, 1, and its slightly less crowded analogue (C5Me4H)3U, 2, new syntheses of UI3, (C5Me4H)3U, (C5Me4H)3UCl, 3, and (C5Me5)3UCl, 4, have been developed. Additionally, (C5Me4H)3UI, 5, and (C5Me4H)2UCl2, 6, have been identified for the first time. A facile synthesis of unsolvated UI3 is reported that proceeds in high yield with inexpensive equipment from iodine and hot uranium turnings. Both UI3 and UI3(THF)4 react with KC5Me4H in toluene to make unsolvated (C5Me4H)3U in higher yield than in previous reports that involve reduction of tetravalent (C5Me4H)3UCl, 3. A more atom-efficient synthesis of complex 3 is also reported that proceeds from reduction of t-BuCl, PhCl, or HgCl2 by 2. Similarly, (C5Me4H)3U reacts with PhI or HgI2 to generate (C5Me4H)3UI. These studies also provided a basis to improve the synthesis of (C5Me5)3UCl from 1 by employing t-BuCl or HgCl2 as the halide source. Like (C5Me5)3UCl, the (C5Me4H)3UCl complex reacts with HgCl2 to form (C5Me4H)2 and (C5Me4H)2UCl2, 6, but unlike (C5Me5)3UX (X = Cl or I), the less substituted (C5Me4H)3UX complexes do not reduce t-BuCl or PhX. The synthesis of 6 from (C5Me4H)MgCl x THF and UCl4 is also included.     

Stereoselective electrocatalytic transformation of arylidene- or alkylidenemalononitriles and malonate into alkyl (1R,5R,6R)* 6-substituted 5-cyano-4,4-dialkoxy-2-oxo-3-azabicyclo[3.1.0]hexane-1-carboxylates

Electrolysis of arylidene- or alkylidenemalononitriles and malonate in alcohol in an undivided cell in the presence of sodium halide as mediator results in the stereoselective formation of alkyl (1R,5R,6R)* 6-substituted 5-cyano-4,4-dialkoxy-2-oxo-3-azabicyclo[3.1.0]hexan-1-carboxylates in 50-70% yields.     

Vinylation of cellulose in superbase catalytic systems: towards new biodegradable polymer materials

Diverse celluloses including non-mercerized and mercerized ones have been successfully vinylated with acetylene in the superbase catalytic systems MOH/DMSO and MOH/THF (M = Na, K) at 85–140 °C. Depending on the reaction conditions, degree of substitution of the hydroxyl groups by highly reactive polymerazable vinyloxy groups ranges 0.11–1.22, the yields of vinylated celluloses (insoluble in water, but soluble in DMSO) being 41–89 %. Vinylated celluloses are easily decomposed under the action of white rot fungi: Phanerochaete chrysosporium, Trametes versicolor and Trametes hirsutus, and can constitute a basis for the preparation of biodegradable polymer materials (due to polymerization or polyaddition at the vinyloxy group).     

Synthesis of spiro[imidazole-4,3'-thiochroman]ones from [2-(benzylsulfanyl)benzylidene]imidazolones

Chemistry of Heterocyclic Compounds - A methodology was developed for the synthesis of phenylspiro[imidazole-4,3'-thiochroman]ones by treatment of [2-(benzylsulfanyl)-benzylidene]imidazolones...     

The solvent effect in obtaining of acid–base multicomponent systems: thermal,structural and luminescence study

Journal of Thermal Analysis and Calorimetry - Acid–base multicomponent systems based on active pharmaceutical ingredients 2-chloro-5-nitrobenzoic acid (2Cl5NBH) and monoethanolamine were...     

Addition of secondary phosphines to a vinyl ether of diacetone-d-glucose: a new approach to optically active phosphines and their derivatives

Secondary phosphines react readily with a vinyl ether of diacetone-d-glucose under radical initiation conditions to give, in high yield, anti-Markovnikov adducts, diorganyl{2-[3-O-(1,2:5,6-di-O-isopropylidene)-d-glucofuranosyloxy]ethyl}phosphines, which oxidize almost quantitatively upon reacting with air oxygen or elemental sulfur to form the corresponding optically active phosphine oxides or sulfides.