四氢键二聚体和分子组装

介绍了最近几年新的四氢键有机二聚体研究的进展及其在分子自组装和分子聚 集体化学研究中的应用。     

In search of 1,3-disila/germa/stannabicyclo[1.1.1]pentanes with short bridgehead-bridgehead distances and low ring strain energies

The strain energies and through-space distances between the two bridgehead E atoms of a selection of 1,3-dimethyl-1,3-ditetrelbicyclo[1.1.1]pentanes (tetrel E = Si, Ge or Sn) were examined by quantum chemical calculations at MP2 and B3LYP levels. The aim is to identify which bridges lead to short through-space E,E distances, and simultaneously, to as low strain as possible. A short E,E distance should improve through-space interaction, and a low strain should promote the thermal stability and possibly also facilitate their synthesis. The bridges examined included CH₂, CMe₂, CtBu₂, C(CH₂)n (n = 2–4), O, NMe, S, PMe, SiMe₂, GeMe₂, and SnMe₂. The calculations indicate that the phospha bridge is a good compromise providing reasonably low strain as well as E,E through-space distances which are only longer than normal E–E single bonds by factors of 1.06–1.10. This paper is dedicated to Professor Mitsuo Kira in recognition of his stimulating Si chemistry and his 2005 Wacker Award.     

Structure and Magnetic Properties of Ce3Ge0.66In4.34 and Ce11Ge4.74In5.26

New indides Ce₃Ge_0.66In_4.34 and Ce₁₁Ge_4.74In_5.26 were synthesized from the elements by arc‐melting and subsequent annealing at 870 K. Single crystals were grown through special annealing procedures in sealed tantalum tubes in a high‐frequency furnace. Both compounds were investigated on the basis of X‐ray powder and single crystal data: I4/mcm, La₃GeIn₄ type, a = 848.8(1), c = 1192.0(2) pm, Z = 4, wR2 = 0.0453, 499 F² values, 17 variables for Ce₃Ge_0.66In_4.34 and I4/mmm, Sm₁₁Ge₄In₆ type (ordered version of the Ho₁₁Ge₁₀ type), a = 1199.3(2), c = 1662.0(3) pm, wR2 = 0.0507, 1217 F² values, 41 variables for Ce₁₁Ge_4.74In_5.26. The Ce₃Ge_0.66In_4.34 structure shows a mixed Ge/In occupancy on the 4c Wyckoff position. This site is octahedrally coordinated by cerium atoms. These octahedra share all edges, leading to a three‐dimensional network. The latter is penetrated by a two‐dimensional indium substructure which consists of flattened tetrahedra at In–In distances of 291 and 300 pm. The Ce₁₁Ge_4.74In_5.26 structure contains three crystallographically independent germanium sites. The latter are coordinated by eight or nine cerium neighbors. These CN8 and CN9 polyhedra are condensed to a complex network which is penetrated by a three‐dimensional indium network with In–In distances of 301–314 pm. The 16m site shows a mixed In/Ge occupancy. Chemical bonding in both compounds is dominated by the p elements. Both ternaries studied exhibit localized magnetism due to the presence of Ce³⁺ ions. The compound Ce₃GeIn₄ remains paramagnetic down to 1.72 K, whereas Ce₁₁Ge₄In₆ orders ferromagnetically at T_C = 7.5 K.     

光学活性化合物的工业合成

本文介绍了光学活性化合物研究现状及发展趋势。并从技术和经济角度论述了工业合成光学活性化合物的可能性     

New PVC materials for medical applications—the release profile of PVC/polycaprolactone–polycarbonate aged in aqueous environments

Medical grade PVC plasticised with polycaprolactone–polycarbonate (PCL–PC) was subjected to aqueous environments at different temperatures. The release profile during ageing was determined by solid phase microextraction (SPME) and GC–MS. At the same time changes in the surface composition due to, for example, migration of PCL–PC from the blend were followed by FTIR. Almost no changes in the material or its surface composition were observed during 98 days at 37 °C in water or phosphate buffer. Only trace amount of 6-hydroxyhexanoic acid the final hydrolysis product of PCL–PC was detected in the GC–MS chromatograms and the weight loss was negligible. Even when the ageing temperature was raised to 70 °C only minor increase in the amount of 6-hydroxyhexanoic acid was observed and the weight loss after 98 days was under 1%. Changes in the FTIR spectra indicating migration of PCL–PC towards the surface of the PVC/PCL–PC tubing were observed first after 70 days at 70 °C. Large increase in the hydrolysis rate of PCL–PC and almost complete depletion of PCL–PC from the blend was observed when the ageing temperature was raised to 100 °C.     

Solid state reactions of nitrogenous heterocyclic compounds(Ⅰ)——Solid state reactions of 3-methyl-l-phenyl-5-pyrazolone with carbonyl compounds

The solid state reaction of 3-methyl-1-phenyl-5-pyrazolone (MPP) with aromatic aldehydes and ke-tones benzil derivatives and imides,and the solid state Michael addition reaction of MPP with 4-arylidene-3-methyl-1-phenyl-5-pyrnzolone 2 were investigated.Some new solid state reactions between the reactants were found,from which a series of new compounds were obtained The structures of the products were identified by IR,1H NMR,MS,elemental analyses and also by X-ray crystal analysis,and the reaction mechanism of MPP with aromatic aldehydes and ketones was proposed     

An Infrared Spectroscopic Study on the Hofmann- and en-Td-type Clathrates: Mn(NH3)2Zn(CN)4 .2benzene and Mn(ethylenediamine)Zn(CN)4.2benzene

Infrared spectra of Mn(NH₃)₂Zn(CN)₄.2C₆H₆ andMn(ethylenediamine)Zn(CN)₄.2C₆H₆ are reported. The spectral data suggest that these compounds are similar in structure toHofmann-T_d-type and the en-T_d-type clathrates,respectively. There is good evidence for H-bonding from ammoniaN–H to benzene as a to H-bond.     

Synthesis,molecular and crystal structures,and characteristic features of electronic structures of salicylamide-based B,Si-containing chelates

The reaction of 4-(2-hydroxybenzoyl)-2,2,6,6-tetramethyl-2,6-disilamorpholine with BF₃Et₂O afforded (O-B)-chelate 4-[2-(difluoroboroxy)benzoyl]-2,2,6,6-tetramethyl-2,6-disilamorpholine. Treatment of the latter with BF₃Et₂O or SOCl₂ gave rise to products of the disilamorpholine ring opening, viz., (O-B) chelate 2-(difluoroboroxy)-N,N-bis(dimethylfluorosilylmethyl)benzamide or 2-(difluoroboroxy)-N, N-bis(dimethylchlorosilylmethyl)benzamide, respectively. The structures of the compounds synthesized were confirmed by X-ray diffraction analysis and ¹H, ¹³C, and ²⁹Si NMR spectroscopy. High-precision X-ray diffraction study and quantum-chemical calculations demonstrated that the coordination OSi bond is absent in the two last-mentioned compounds.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1846–1853, September, 2004.     

分子内环加成的甾体全合成

近年来,分子内环加成反应已广泛用于甾体化合物全合成,其主要一步是由取代的苯并环丁烯热裂而成的5,6-二亚甲基-1,3-环己二烯发生区域专一和立体选择性的环加成反应,构成甾体骨架。现在用此法已合成了一系列消旋和光学活性的甾体化合物。