4-二甲氨基吡啶催化合成含氟苯甲酸糖酯

以4－二甲氨基吡啶为催化剂由含氟苯甲酸与溴代乙酰糖催化酯化合成了4个新的含氟苯甲酸糖酯。其结构经IR，^1H NMR和MS确认，多数还作了^13C NMR测定。     

Oxidation of bridging groups by carboxylate coordinated ligands in palladium clusters

Thermolysis of tetranuclear palladium clusters Pd₄(-Q)₄ Pd₄(-Q)₄(-O₂CR)₄ (Q=CPh₂ or CO;R=Me, CMe₃, Ph, CH₂Cl or CF₃) has been found to involve innersphere oxidation of carbene or carbonyl ligands during which an oxygen atom transfer occurs from the carboxylate group to the carbene or carbonyl ligand. The thermolysis of the carbonyl clusters gives rise to the products of CO₂ insertion into the C–H bond of benzene or toluene used as solvents forming benzoic acid from benzene and a mixture of phenylacetic and toluic acids from toluene. The reaction of [Pd(OAc)₂(PPh₃)]₂ with HCO₂H includes the transfer of an O atom from formate ligand to the P atom and cleavage of the P-Ph bond accompanied by transfer of the Ph group from PPh₃ ligand to the palladium atom. The structure of the complex formed, [Pd(-O₂PPh₂)(C₆H₅)(PPh₃)]₂, has been resolved by X-ray analysis.     

A convenient preparative method for anionic tris(substituted pyrazolyl)methane ligands

The synthesis of tris[3-(6-carboxypyridin-2-yl)pyrazol-1-yl]methane is described in a linear multi-step protocol. The pyridyl-pyrazolyl arms are first constructed before being condensed with chloroform. Careful study of the condensation reaction shows the presence of an isomeric form of the tris(pyrazolyl)methane derivative in which one of the pyrazolyl substituents is linked through the nitrogen atom at the 2 position of the pyrazol. After acid-catalysed isomerisation to the desired isomer, the intermediate compound was subjected to a carboalkoxylation reaction and a subsequent hydrolysis. These are some rare examples of reactions directly occurring on the tris(pyrazolyl)methane platforms.     

Synthetic receptors based on calix[4]arene functionalized at the lower rim in molecular recognition of dicarboxylic, α-hydroxycarboxylic,and α-amino acids

New calix[4]arenes, di- and tetrasubstituted at the lower rim, with different functional groups were synthesized. They were studied as carriers of a series of dicarboxylic and -hydroxycarboxylic acids through a liquid impregnated membrane. The calix[4]arenes under study are capable of molecular recognition of oxalic acid in the series of structurally similar dicarboxylic and -hydroxycarboxylic acids. The regularities found make it possible to change purposefully the receptor ability of 1,3-disubstituted calix[4]arenes by variation of the nature of substituents.     

Synthesis, Crystal Structure and Properties of [Co(1,3- bdoaH)_2·4H_2O]·4H_2O with Benzene-1,3-dioxyacetate Ligand

1INTRODUCTIONTheorganicaromaticcarboxylatemetalcom-plexeshavearousedmuchattentionandbeenwidelyinvestigated.However,thestrategyofdesignandsynthesisofthesecomplexesismostlyfocusedonrigidligands,suchasterephthalicacidandbenzenetricarboxylicacid,etc.[1～5].Theassemblyofcom-plexesbyusingflexiblearomaticcarboxylateli-gandsisfarlessdeveloped[6,.Phenylenedioxydia-7]ceticacids(bdoaH2)withbiologicalactivitiesandwideapplicationsinagriculture[8]areafamilyofmultidentateflexibleligandswithversatilebind…     

Theoretical studies of molecular conformation. II: Application of the SIBFA procedure to molecules containing carbonyl and carboxylate oxygens and amide nitrogens

The SIBFA procedure (Sum of Interactions Between Fragments computedAb initio, Ref [1]) is extended to the study of the conformational behavior of representative molecules containing amide nitrogens and carbonyl and carboxylate oxygens. The molecules studied are C- and N-ethylammonium formamide, C- and N-ethanol-formamide, ethylammonium formate and ethanolformate. The cases investigated include interactions of the types which occur between functional groups in proteins or ionophores. The accuracy of the procedure, assessed by comparing the results to those of correspondingab initio SCF computations, is very satisfactory. An application of the procedure to study the conformation of the glycyl and alanyl dipeptides as a function of the backbone torsional angles and is presented.     

含杂环羧酸基二苄基锡(Ⅳ)配合物的合成与表征

以二苄基二氯化锡和杂环羧酸钠为原料合成了十种新的有机锡配合物(PhCH₂)₂Sn(O₂CR)_nCl_2-n(n=1或2，R=杂环)。用元素分析、IR、 ¹H NMR和TG表征了配合物的组成和结构。     

Syntheses and Crystal Structures of Some CCo3 Clusters Containing PPh3 or dppm Ligands

Molecular structural determinations are reported for six Co₃C carbonyl cluster complexes containing tertiary phosphines, which have been isolated as by-products from a variety of reactions. Structural features are similar to those of related complexes already reported. Some discussion of apparent orientational preferences of the CH₂ group of dppm ligands, which appear to enter into H-bonding interactions with amido or carboxylate substituents, is given. Appropriate comparisons are made with unsubstituted analogues.     

The formation of clathrate-like hydrates of tetrabutylammonium halogenated carboxylates

The solid-liquid phase diagrams of binary mixtures of tetrabutylammonium halogenated carboxylates with water were examined in order to confirm the formation of clathrate-like hydrates. It was found that, among thirteen carboxylates examined, four carboxylates having CH₂FCOO^–, CHF₂COO^–, CF₃COO^–, and CH₂ClCOO^–, formed a hydrate with hydration numbers around 30 and seven carboxylates having CHCl₂COO^–, CCl₃COO^–, CH₂BrCOO^–, CHBr₂COO^–, CBr₃COO^–, CH₃CHClCOO^–, and CH₃CHBrCOO^– formed a hydrate with hydration numbers around 23. The latter hydrate has not been reported earlier. The melting points of these newly found hydrates were fairly high: they lie between 10 and 16°C. The effect of Cl and Br atoms attached to the carbon atom of the-position of a carboxylate anion both on the type of hydrate formed and on its stability was greatly different from that of a CH₃ group attached to the same position of the carboxylate anion.Dedicated to Dr D. W. Davidson in honor of his great contributions to the sciences of inclusion phenomena.     

Optimized POCl3-assisted synthesis of 2-amino-1,3,4-thiadiazole/1,3,4-oxadiazole derivatives as anti-influenza agents

Although recent decades have witnessed the synthesis of 1,3,4-thiadiazoles via phosphorus POCl₃-promoted cyclization reaction, simultaneous access to 2-amino-1,3,4-thiadiazole and 2-amino-1,3,4-oxadiazole analogs remains unexpected and elusive. Herein, a detailed regiocontrolled synthesis of 2-amino-1,3,4-thiadiazoles in good to high yields with good regioselectivities from readily available thiosemicarbazides using POCl₃ was disclosed. Meantime, to establish a comprehensive structure–activity relationship, 2-amino-1,3,4-oxadiazole derivatives as single regioisomers were prepared via EDCI·HCl-triggered cyclization of the thiosemicarbazide intermediates. The in vitro anti-influenza assays proved that the selected compounds with the pyrazine/pyridine ring exhibited certain inhibitory activities against influenza A virus strains A/HK/68 (H3N2) and A/PR/8/34 (H1N1) in MDCK cells. Among them, N-(adamantan-1-yl)-5-(5-(azepan-1-yl)pyrazin-2-yl)-1,3,4-thiadiazol-2-amine (4j) was the most active compound, and exhibited favorable activity with EC₅₀ values of 3.5 μM and 7.5 μM, respectively. In addition, the molecular docking results explained the reason why compound 4j had dual inhibitory activity and revealed the reasonable binding mode of this compound with the M2-S31N and M2-WT ion channels. This compound had the potential to be further developed as an anti-influenza drug.