Bis(trimethylsilyl)diimine: Preparation,Structure, and Reactivity

The highly reactive compound bis(trimethylsilyl)diimine (BSD), which was first prepared by oxidation of lithium tris(trimethylsilyl)hydrazide, is light blue, sensitive to thermolysis and hydrolysis, and ignites spontaneously in air. On the basis of electron transfer, acid-base, or free-radical reactions, it acts in particular as a (preparatively useful) redox system and as an agent for the introduction of azo groups. Redox reactions lead by oxidation or reduction of the other reactant through two oxidation stages to hydrazine derivatives or molecular nitrogen, and in the case of electrochemical reduction, to BSD radical-anions. Azo-group transfers, on the other hand, yield new inorganic azo compounds with no change in the oxidation state of the diimine group.     

Lipophilicity determination of some new crown ethers by reversed-phase thin-layer chromatography

Summary The lipophilicity of 28 modified crown ether derivatives was determined by reversed-phase thin-layer chromatography (RPTLC) using various organic phases and supports. The lipophilicity values determined in different RPTLC systems showed good correlations, however the quality of the organic phase (methanol, acetone, acetonitrile) and the support characteristics influenced to a small extent the determination.     

Synthesis and antiangiogenic activities of 5-amino-1,3-dihydro-1, 3-dioxo-2H-isoindole-2-propanoic acid derivatives

Based on the structure-activity relationships and antiangiogenic mechanism of RGD-containing peptides,a series of 5-amino- 1,3-dihydro-1,3-dioxo-2H-isoindole derivatives were synthesized.The structures were characterized by ~1H NMR,MS and elementary analysis.There ability to inhibit angiogenesis were evaluated by chick embryo chorioallantoic membrane assay at 10~(-5) mol/L.Compounds 7a and 7b displayed obvious antiangiogenic activity.     

Cadinene Derivatives from Eupatorium adenophorum

A new norsesquiterpene named eupatorone (= (4S,4aR,6R)‐1‐acetyl‐6‐(acetyloxy)‐4,4a,5,6‐tetrahydro‐4,7‐dimethylnaphthalen‐2(3H)‐one; 1 ) and a new sesquiterpene derivative named 2‐deoxo‐2‐(acetyloxy)‐9‐oxoageraphorone (= (1R,4S,4aR,6R,8aS)‐6‐(acetyloxy)‐3,4,4a,5,6,8a‐hexahydro‐4,7‐dimethyl‐1‐(1‐methylethyl)naphthalen‐2(1H)‐one; 2 ), together with the five known cadinene derivatives 3 – 7 were isolated from the flower of Eupatorium adenophorum (Spreng. ). Their structures were established by extensive NMR experiments, including 1D and 2D NMR.     

Synthesis of Tetrahydrofuran and Tetrahydropyran Derivatives Catalyzed by Tungstophosphoric Acid in Ionic Liquid

Synthesis of tetrahydrofuran and tetrahydropyran derivatives catalyzed by tungstophosphoric acid （H3PW12040） were conveniently performed with high yield from the corresponding unsaturated alcohols in ionic liquid. Sufuric acid （H2SO4）, trifluoromathanesulfonic acid （TfOH） and p-toluenesulfonic acid （TsOH） were also explored for preparing these products in ionic liquid. The catalysts and ionic liquid can be easily recovered and reused.     

1—二茂铁甲酰基—4—芳基氨基硫脲的合成及光谱性质研究

通过二茂铁基甲酸肼与芳基异硫氰酸酯的加成反应合成了一系列1-二茂铁甲酰基-4-芳基氨基硫脲,产物结构经元素分析和红外光谱及核磁共振氢谱予以确认.     

Utility of N‐[4‐(N‐Substituted Sulfamoyl)Phenyl] Cyanothioformamides in the Synthesis of Heterocyclic Compounds

The novel cyanothioformamides 2a‐d were prepared by treatment of isothiocyanatosulfonamides 1a‐d with potassium cyanide at room temperature. Cyclocondensation of compounds 2b,c with phenyl isocyanate as electrophile furnished the corresponding imidazolidines 3a,b . The reactivity of compound 3a towards some nitrogen nucleophiles was investigated. Thus, the thiosemicarbazone 4 and imidazo[4,5‐b]quinoxaline 6 were synthesized by condensation of compound 3a with thiosemicarbazide and o‐phenylenediamine, respectively. Treatment of 3a with hydrochloric acid afforded compound 7 . Our investigation was extended to include the reactivity of cyanothioformamide 2 towards o‐aminophenol, anthranilic acid, and o‐phenylenediamine and yielded the corresponding heterocycles 9 , 11 and 13 derivatives, respectively. Structures of the synthesized compounds were established by their elemental analysis and spectral data.     

Synthesis of porous vinylnaphthalene/divinylnaphthalene copolymers and their sorptive properties towards phenol and its derivatives

Four porous vinylnaphthalene/divinylnaphthalene (VN/DVN) polymers having three different nominal crosslinking degrees (60, 80 and 100 wt.%) have been synthesized using the suspension polymerization method in the presence of toluene and decane.The use of various crosslinking levels and inert diluents was aimed at changing the extent of polymeric network-diluent interactions. The resultant polymers have specific surface area in the range 450-700 m²/g depending on the DVN content. Two sets of pores were detected in all resins: one with the diameter of ≈2 nm and the second one in the range of 30-40 nm. Their sorptive properties have been studied using dilute (0.5 mmol/l) solutions of phenol and its derivatives (o-chlorophenol, 2-methylphenol, o-nitrophenol, m-nitrophenol and p-nitrophenol). It has been found that sorption, at low equilibrium concentration, follows the order: o-nitrophenol > o-chlorophenol > m-nitrophenol > o-methylphenol > p-nitrophenol > phenol. Full characteristics of the porous structure of resultant polymers was obtained by nitrogen adsorption at 77 K and their surface properties analyzed using Inverse Gas Chromatography.     

C-Glycosylidene derivatives (exo-glycals): their synthesis by reaction of protected sugar lactones with tributylphosphonium ylids, conformational analysis and stereoselective reduction

Stabilised tributylphosphonium ylids Bu₃PCHCH(EWG), where EWG is CO₂Me, CO₂^tBu or CN, react with protected sugar lactones under mild conditions to give high yields of glycosylidene derivatives (4 and 5) with good Z/E selectivity. X-Ray crystallography shows that in the solid state the tetra-O-benzyl protected (Z)-glucosylideneacetonitrile (Z)-4c adopts a conformation intermediate between a boat and a twist-boat, whereas the isomeric galactose derivative (Z)-5c exists as a distorted chair. NMR data suggest that in solution chair-like conformations are again more favoured for galactosylidene derivatives than for their glucosylidene analogues. Solution phase NMR studies and molecular modelling show that the (E)-double bond geometry disfavours the chair-like geometry of the ring, even in the galactose series; this is consistent with the avoidance of allylic 1,3-strain. Reduction of the glycosylidene double bond to give stereoselective formation of β-C-glycoside derivatives may be achieved by using Et₃SiH-CF₃CO₂H or Et₃SiH-BF₃·Et₂O.     

Photochromic dihetarylethenes. 18. New approach to the synthesis of dithienothiophene and preparation of its photochromic derivative

A new approach to the synthesis of dithienothiophene was developed, and 1,2-bis(2,6-dimethyldithieno[3,2-b;2",3"-d]thiophen-3-yl)hexafluorocyclopent-1-ene was prepared. The latter compound is the first representative of photochromic dihetarylethenes with the fused tricyclic fragments linked through the perfluorocyclene bridge.