Syntheses of Some 3—[1′（1′H）—Substituent—pyrazol—5′—yl] benzo [5,6] coumarins

3-[1′(1′H)-Substituent-pyrazol-5′-yl]benzo[5,6]coumarins and 3-(1′,2′-oxazol-5′-yl)benzo[5,6]coumarin were prepared via condensation of 3-(2′-formyl-1′-chlorovinyl)benzo[5,6] coumarin with hydrazine derivatives or hydroxylamine.Reaction of 3-[1′(1′H)-pyrazol-5′-yl]benzo[5,6]coumarin with alkyl halides,olefinic compunds or acid chlorides are described.     

Effects of the structure and morphology of zinc glutarate on the fixation of carbon dioxide into polymer

Zinc glutarates were synthesized from zinc oxides with varying purities via different stirring routes. The particle size and structure of these zinc glutarates were determined by wide‐angle X‐ray diffraction, transmission electron microscopy, and the laser particle size analyzer technique. The results demonstrated that the crystallinity and crystalline perfectness of zinc glutarate are the crucial factors that affect the catalytic activity for the copolymerization of carbon dioxide (CO₂) and propylene oxide (PO). Additionally, the catalyst with a small particle size dramatically increased the yield of the copolymerization between CO₂ and PO. High‐molecular‐weight and regular molecular structure poly(propylene carbonate)s (PPC)s were obtained from CO₂ and PO with the synthesized zinc glutarates. Very high catalytic activity of 160.4 g polymer/g catalyst was afforded. The NMR technique revealed that the PPC copolymer exhibits an exact alternating copolymer structure. The relationships between the crystallinity and the particle size of catalyst with the catalytic activity are correlated and discussed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3579–3591, 2002     

一种新的16金属笼状物[HN(C_2H_5)_3]_4-[Mo_3~VMo_6~(VI)V_7~(IV)O_(40)(PO_4)]·2[N(C_2H_5)_3]的水热合成和结构

报道了一种新的杂多化合物[HN(C_2H_5)_3]_4-[Mo_3~VMo_6~(VI)V_7~(IV)O_(40)(PO_4)]·2[N(C_2H_5)_3]的合成,并用元素分析、EPR、IR谱、及X--射线单晶衍射等手段进行了表征。结果表明,该杂多酸盐属于单斜晶系,空间群P21/n,a=14.0841(3),b=14.2505(3),c=19.6089(3)?b=94.213(1),V=3925.0(1)?,Z=2,Dc=2.171g/cm3,Mr=2566.18,m=2.284mm-1,F(000)=2516,R=0.0477,wR=0.0945.杂多阴离子是1个16金属笼状物,笼中心包含1个PO4四面体客体。     

含八齿苦味酸根的超分子苦味酸钾的合成和结构

A supramolecular complex， [Kpic]_n (pic^- is picratol， (NO₂)₃C₆H₂O^-)， has been synthesized unexpectedly in acetone solution， and characterized by elemental analysis， IR and X-ray crystallography. In the complex， the K⁺∶pic^- is 1∶1， and one K(Ⅰ) ion is surrounded by six picrate anions， one picrate anion can coordinate to six K(Ⅰ) ions. The coordination number of every potassium atom is eight. Interestingly， the picratol adopts an eight-coordinated ideal mode unreported. CCDC: 630627.     

碳糖苷合成的新进展

本文介绍了近几年来有关碳糖苷合成的最新进展, 包括亲电取代、亲核糖取代、过渡金属催化、异头碳自由基反应、重排和环加成反应以及糖环形成反应等。     

Polymerizability,copolymerizability, and properties of cyanoacrylate‐telechelic polyisobutylenes I: three‐arm star cyanoacrylate‐telechelic polyisobutylene

This series of papers concern new materials for possible biological applications created by combining the chemistry of highly reactive cyanoacrylates (CAs) with polyisobutylene (PIB) rubbers. First, a new strategy for the synthesis of CA–telechelic PIBs is described. Subsequently, the strategy is employed for the synthesis of low viscosity (syringible) CA–telechelic three‐arm star PIB [Ø(PIB–CA)₃]. The intermediates of the synthesis route are characterized by ¹H NMR spectroscopy. Injecting liquid Ø(PIB–CA)₃ into living tissue (fresh chicken egg) produces a bolus of crosslinked PIB rubber. The spectacular oxidative resistance of this rubber is documented by its resistance to concentrated HNO₃. A structural model of the crosslinked rubber obtained upon contacting Ø(PIB–CA)₃ with proteinaceous tissue is proposed. Copyright © 2007 John Wiley & Sons, Ltd.     

Enantioselective syntheses of no-carrier-added (n.c.a.) (s)-4-chloro-2-[f] fluorophenylalanine and (s)-(α-methyl) -4-chloro-2-[f]fluorophenylalanine

(S)-4-Chloro-2-fluorophenylalanine and (S)-(α-methy)-4-chloro-2-fluorophenylalanine were synthesized and labeled with no carrier added (n.c.a.) fluorine-18 through a radiochemical synthesis relying on the highly enantioselective reaction between 4-chloro-2-[¹⁸F]fluorobenzyl iodide and the lithium enolate of (2S)-1-(tert-butyloxycarbonyl)-2-(tert-butyl)-3-methyl-1,3-imidazolidine-4-one for (S)-4-chloro-2-[¹⁸F]fluorophenylalanine and (2S,5S)-1-(tert-butyloxycarbonyl)-2-(tert-butyl)-3,5-dimethyl-1,3-imidazolidine-4-one for (S)-(α-methyl) -4-chloro-2-[¹⁸F] fluorophenylalanine. Quantities of about 20–25 mCi were obtained at the end of sy nthesi s, ready for injection after hydrolysis and high performance liquid chromatography (HPLC) purification, with a radiochemical yield of 17%–20% corrected to the end of bombardment after a total synthesis time of 90–105 min from [¹⁸F] fluoride. The enantiomeric excesses were shown to be 97% or more for both molecules without chiral separation and the radiochemical and chemical purities were 98% or better.     

Building three-dimensional metal phosphites from the corner-shared four-membered rings chain

Three new compounds, a one-dimensional (1D) zinc phosphite, (C₄H₈N₂H₄)[Zn(HPO₃)₂] (I), two three-dimensional (3D) metal phosphites (C₄H₈N₂H₄)[Zn₃(HPO₃)₄] (II) and (C₄H₈N₂H₄)[Zn_(3−x)Co_x(HPO₃)₄(H₂O)₂] (x≈0.83) (III) have been synthesized under hydrothermal conditions templated by piperazine and characterized by single-crystal X-ray diffraction, XRD, IR, UV-vis spectra and SQUID magnetometer. Compound I displays 1D chain-like structure, containing corner-shared (cs) four-membered rings. Interestingly, the structures of II and III show 1D chains similar to those observed in I. It is noteworthy that III represents the first cobalt-substituted zinc-phosphite. Crystal data: I, monoclinic, C2/c, a=17.748(2) Å, b=7.428(9) Å, c=8.8071(11) Å, β=105.345(3)°, V=1091.9 Å³, Z=4. II, Monoclinic P2₁/c, a=9.9435(4) Å, b=10.1438(3) Å, c=17.8164(5) Å, β=95.665(2)°, V=1788.27 Å³, Z=4, and III, Monoclinic P2₁/c, a=7.2338(2) Å, b=15.0238(5) Å, c=9.2153(3) Å, β=107.741(2)°, V=953.88(5) Å³, Z=2.     

β-内酰胺类抗生素酶促合成新进展

β-内酰胺类抗生素的合成在制药工业中占据重要的地位, 相关的酶促合成方法研究备受关注; 酶促合成显著提高合成效率, 减少三废的排放, 是实现绿色合成的有效方法. 综述了近年来β-内酰胺类抗生素酶促合成研究的新进展, 包括一锅合成法、原位产物排出法、介质技术和酶固定化方法.     

Formation,preservation, and cleavage of the disulfide bond by vanadium

Reaction of the disulfide [HpicanS](2) (HpicanS is the carboxamide based on picolinate (pic) and o-mercaptoaniline (anS); the [] brackets are used to denote disulfides) with [VOCl(2)(thf)(2)] leads to reductive scission of the disulfide bond and formation of the mixed-valence (V(IV)/V(V)) complex anion [(OVpicanS)(2)mu-O](-) (1), with the dianionic ligand coordinating through the pyridine-N atom, the deprotonated amide-N atom, and thiophenolate-S atom. Reductive cleavage of the SbondS bond is also observed as [VCl(2)(tmeda)(2)] (tmeda=tetramethylethylenediamine) is treated with the disulfides [HsalanS](2) or [HvananS](2) (HsalanS and HvananS are the Schiff bases formed between o-mercaptoaniline and salicylaldehyde (Hsal) or vanillin (Hvan), respectively), yielding the V(III) complexes [VCl(tmeda)(salanS)] (2 a), or [VCl(tmeda)(vananS)] (2 b). The disulfide bond remains intact in the aerial reaction between [HsalanS](2) and [VCl(3)(thf)(3)] to yield the V(V) complex [VOCl[salanS](2)] (3), where (salanS)(2-) coordinates through the two phenolate and one of the imine functions. The S-S bond is also preserved as [VO(van)(2)] or [VO(nap)(2)] (Hnap=2-hydroxynaphthalene-1-carbaldehyde) is treated with bis(2-aminophenyl)disulfide, [anS](2), a reaction which is accompanied by condensation of the aldehyde and the diamine, and complexation of the resulting bis(Schiff bases) [HvananS](2) or [HnapanS](2) to form the complexes [VO[vananS](2)] (4 a) or [VO[napanS](2)] (4 b). In 4 a and 4 b, the phenolate and imine functions, and presumably also one of the disulfide-S atoms, coordinate to V(IV). 2-Mercaptophenyl-2'-pyridinecarboxamide (H(2)picanS) retains its identity in the presence of V(III); reaction between [VCl(3)(thf)(3)] and H(2)picanS yields [V[picanS](2)](-) (5). The dithiophenolate 2,6-bis(mercaptophenylthio)dimethylpyridine (6 a) is oxidized, mediated by VO(2+), to the bis(disulfide) octathiadiaza-cyclo-hexaeicosane 6 b. The relevance of these reactions for the speciation of vanadium under physiological conditions is addressed. [HNEt(3)]-1.0.5 NEt(3,) 3.3 CH(2)Cl(2), [HsalanS](2), [HNEt(3)]-5, and 6 b.4 THF have been characterized by X-ray diffraction analysis.