The Synthesis and Mechanistic Considerations of a Series of Ammonium Monosubstituted H-Phosphonate Salts

A series of ammonium monosubstituted H-phosphonate salts were synthesized by combining H-phosphonate diesters with amines in the absence of solvent at 80 °C. Variation of the ester substituent and amine produced a range of ionic liquids with low melting points. The products and by-products were analyzed by spectroscopic and spectrometric techniques in order to get a better mechanistic picture of the dealkylation and formal dearylation observed. For dialkyl H-phosphonate diesters, (RO)₂P(O)H (R=alkyl), the reaction proceeds via direct dealkylation with the reactivity increasing in the order R=iPr<Et<Me corresponding to DFT calculated activation enthalpies of 22.6, 20.8, and 17.9 kcal mol⁻¹. For the diphenyl H-phosphonate diesters, (PhO)₂P(O)H, the dearylation was found to proceed via phenol-assisted formation of a 5-coordinate intermediate, (PhO)₃PH(OH), from which P(OPh)₃ and water were eliminated. The presence of an equivalent of water then facilitated the formation of P(OH)₂OPh and the amine, R'NH₂, subsequently abstracted a proton from it to yield [(PhO)PH(O)O]^-[R'NH₃]⁺.     

Ionic Polymerization of α, α -Disubstituted Vinyl Monomers

Alkyl α-chloroacrylates and p-substituted α-methylstyrenes were investigated for the effect of polymerization conditions on tacticity, molecular weight, and distribution, and for the relationship between tacticity, glass temperature, and crystalline properties.     

Palladium-Catalyzed Cross-Coupling of Organozirconium Compounds with Diaryliodonium Salts

The palladium-catalyzed cross-coupling reaction of diaryliodonium salts with organozirconium compounds was achieved for about 1–1.5 hrs at room temperature and the reaction proceeded with retention of configuration to provide a new convenient method for the synthesis of (E)-disubstituted alkenes.     

Amine Salt–Catalyzed Synthesis of 5-Substituted 1H-Tetrazoles from Nitriles

The [3 + 2] cycloaddition reaction between sodium azide and various organic nitriles proceeds smoothly in the presence of amine salts as catalyst in dimethylformamide. The corresponding 5-substituted 1-H tetrazoles were obtained under mild condition in good to excellent yields. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.     

基于PLC的三维调整机同步控制系统设计与实现

针对三维调整机难以实现多台同步工作，设计了基于PLC的同步控制方案。在同步控制系统方案中，采用西门子PLC通过工业无线以太网进行同步控制，由各维度油缸的位移传感器来保证同步控制的精确性。经实验，证实了此系统的精度满足设计要求，实现了同步控制的效果。     

Stereoselective Synthesis of Alkenyl Alcohols Using Dissolving Metal (Ca,Na) Reduction

Use of the calcium-ethylenediamine and sodium-liquid ammonia reduction systems for the ring opening of dihydropyran derivatives was studied. (Z)-Alkenyl alcohols and (E)-alkenyl alcohols were stereoselectively synthesized respectively.     

Water inclusion as a trigger for modulation of anthracene arrangement and fluorescence emission of organic salt

An organic salt composed 9,10-bis(4-aminophenyl)anthracene and hypophosphorous acid emits yellow-green fluorescence in the crystalline state. The salt also gives water inclusion crystal which provides blue-green fluorescence. Single X-ray crystal studies revealed that water molecules induced the fluorescence change resulting from reaggregation of molecular packing.     

Cross‐Coupling of Organolithium with Ethers or Aryl Ammonium Salts by C−O or C−N Bond Cleavage

Various aryl‐, alkenyl‐, and/or alkyllithium species reacted smoothly with aryl and/or benzyl ethers with cleavage of the inert C?O bond to afford cross‐coupled products, catalyzed by commercially available [Ni(cod)₂] (cod=1,5‐cyclooctadiene) catalysts with N‐heterocyclic carbene (NHC) ligands. Furthermore, the coupling reaction between the aryllithium compounds and aryl ammonium salts proceeded under mild conditions with C?N bond cleavage in the presence of a [Pd(PPh₃)₂Cl₂] catalyst. These methods enable selective sequential functionalizations of arenes having both C?N and C?O bonds in one pot.