Three New Lanostane Triterpenoids from Inonotus obliquus

Three new lanostane‐type triterpenoids, inonotsulides A, B, and C ( 1 – 3 , resp.) were isolated from the sclerotia of Inonotus obliquus (Pers .: Fr.) (Japanese name: Kabanoanatake; Russian name: Chaga). Their structures were determined to be (20R,24S)‐3β,25‐dihydroxylanost‐8‐en‐20,24‐olide ( 1 ), (20R,24R)‐3β,25‐dihydroxylanost‐8‐en‐20,24‐olide ( 2 ), and (20R,24S)‐3β,25‐dihydroxylanosta‐7,9(11)‐dien‐20,24‐olide ( 3 ) on the basis of chemical transformation, NMR spectroscopy including 1D and 2D (¹H,¹H‐COSY, NOESY, HMQC, HMBC), EI‐MS, and single‐crystal X‐ray analysis.     

Synthesis of a Novel Type of Phosphates of Puerarin

A novel type of phosphated puerarin derivatives were synthesized through a simplified Atheron‐Todd reaction for the first time. The structure of these compounds were elucidated by IR, ESI‐MS and NMR. Moreover, the reason the dialkylphophite reagent had different chemselectivities toward different hydroxys on the puerarin was discussed.     

Method for Visible Light‐Induced Photocatalytic Degradation of Methylparaben in Water Using Nanostructured Ag/AgBr@m‐WO3

An efficient method of photocatalytic degradation of methylparaben in water using Ag nanoparticles (NPs) loaded AgBr‐mesoporous‐WO₃ composite photocatalyst (Ag/AgBr@m‐WO₃), under visible light is presented. In this process, quantification of methylparaben in water was carried out by high‐performance liquid chromatography (HPLC) and the HPLC results showed a significant reduction of methylparaben in water due to the enhanced of photocatalytic degradation efficiency of Ag/AgBr@m‐WO₃. For the material synthesis, highly ordered mesoporous‐WO₃ (m‐WO₃) was initially synthesized by sol–gel method and AgBr nanoparticles (NPs) were subsequently introduced in the pores of m‐WO₃, and finally, the Ag nanoparticles were introduced by light irradiation. The enhanced photocatalytic degradation of methylparaben in water is attributed to the formation of surface plasmonic resonance (SPR) due to the introduction of Ag NPs on the surface of the catalyst. Also, the formation of heterojunction between AgBr and mesoporous‐WO₃ in Ag/AgBr@m‐WO₃ significantly inhibited the recombination of light‐induced electron‐hole pairs in the semiconductor composite. The morphological and optical characterizations of the synthesized photocatalysts (Ag/AgBr@m‐WO₃) were carried out using SEM, TEM, XDR, N₂ adsorption–desorption, UV‐VIS diffuse reflectance spectroscopy (DRS). Also, the photocatalytic studies using radical scavengers were carried out and the results indicated that ${\text{O}}_2^{·-}$ is the main reactive species.     

A Mild Isomerization Reaction for β,γ‐Unsaturated Ketone to α,β‐Unsaturated Ketone

A series of β,γ‐unsaturated ketones were isomerized to their corresponding α,β‐unsaturated ketones by the introduction of DABCO in iPrOH at room temperature. The endo‐cyclic double bond (β,γ‐position) on ketone was rearranged to exo‐cyclic double bond (α,β‐position) under the reaction conditions.     

纳秒强激光场中苯电离产生高价离子的研究

用25 ns脉冲Nd-YAG 532 nm的激光，在1010～1011 W•cm－2的光场强度下，利用飞行时间质谱对He、 N2、Ar载气条件下苯的激光电离过程进行了研究.发现当利用氩作为载气时，除观察到C2＋、C2H2+、C3H3+、C6H6+离子外，还观察到很强的Cq＋(q=1～3)高价离子.这些离子都有很高的平动能， C2＋的最可几平动能为12.9 eV， C3＋为37.5 eV.通过改变载气种类和压力及在不同光场强度条件下的实验，可以认为这些高价离子来源于含苯团簇的库仑爆炸过程.     

One—Pot Synthese of 3,4—Dihydropyrimidine—2（1H）—thiones Catalyzed by La（OTf）3

A general and practical procedure for the syntheses of 3,4-di-hydropyrimidine-2(1H)-thiones by a one-pot condensation of aldehyde,β-ketoester or β-diketone and thiourea using La(OTf)3 as the catalyst is described.Mild reaction conditions,excellent yields as well as the environmentally friendly character of La(OTf)3 make it an important alternative to the classic acid-catalyzed Biginelli‘s reaction.     

Synthesis of comb‐shaped poly(methyl methacrylate)‐b‐poly(polytetrahydrofuran acrylate) under 60Co γ‐ray irradiation

Comb‐shaped graft copolymers with poly(methyl methacrylate) as a handle were synthesized by the macromonomer technique in two steps. First, polytetrahydrofuran acrylate (A‐PTHF), prepared by the living cationic ring‐opening polymerization of tetrahydrofuran, underwent homopolymerization with 1‐(ethoxycarbonyl)prop‐1‐yl dithiobenzoate as an initiator under ⁶⁰Co γ irradiation at room temperature; Second, the handle of the comb‐shaped copolymers was prepared by the block copolymerization of methyl methacrylate with P(A‐PTHF) as a macroinitiator under ⁶⁰Co γ irradiation. The two‐step polymerizations were proved to be controlled with the following evidence: the straight line of ln[M]₀/[M] versus the polymerization time, the linear increase in the number‐average molecular weight with the conversion, and the relatively narrow molecular weight distribution. The structures of the P(A‐PTHF) and final comb‐shaped copolymers were characterized by ¹H NMR spectroscopy and gel permeation chromatography. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3367–3378, 2002     

The effect of molecular planarity on crystal non‐centrosymmetry in benzyl­idene–aniline derivatives

In the title compound, N‐(2‐methoxy­phenyl)‐4‐nitro­benzyli­deneamine, C₁₄H₁₂N₂O₃, the two phenyl rings make a dihedral angle of 48.0 (2)° and the nitro group is at an angle of 6.5 (1)° with respect to its attached phenyl ring. In the crystal structure, mol­ecules are related as centrosymmetric pairs through π–π interactions and are further connected through strong C—H?O hydrogen bonds [C?O 3.4259 (17) Å and C—H?O 167°], forming molecular stacks along [100]. These stacks associate further through longer C—H?O interactions, forming two‐dimensional networks. In the c direction, there are only weak van der Waals interactions. The relationship between the molecular planarity and its centrosymmetry is also briefly described.     

Terpenoids from the Roots of Ligularia muliensis

Three new eremophilane‐type sesquiterpenes, (6β,8α)‐6‐(acetyloxy)‐8‐hydroxyeremophil‐7(11)‐en‐12,8‐olide ( 1 ), (6α,8α)‐6‐hydroxyeremophil‐7(11)‐en‐12,8‐olide ( 2 ), and (6α,8α)‐6‐(acetyloxy)eremophil‐7(11)‐en‐12,8‐olide ( 3 ) ((8α)‐eremophil‐7(11)‐en‐12,8‐olide = (4aR,5S,8aR,9aS)‐4a,5,6,7,8,8a,9,9a‐octahydro‐3,4a,5‐trimethylnaphtho[2,3‐b]furan‐2(4H)‐one), besides the recently elucidated eremoligularin ( 4 ) and bieremoligularolide ( 5 ), as well as a new highly oxygenated monoterpene, rel‐(1R,2R,3R,4S,5S)‐p‐menthane‐1,2,3,5‐tetrol ( 12 ), together with six known constituents, i.e., the sesquiterpenes 6 and 7 , the norsesquiterpenes 8 – 10 , and the monoterpene 13 , were isolated from the roots of Ligularia muliensis. In addition, an attempt to dimerize 1 to a bieremophilenolide (Scheme) resulted in the generation of the new derivative (6β,8β)‐6‐(acetyloxy)‐8‐chloroeremophil‐7(11)‐en‐12,8‐olide ( 11 ). The new structures were established by means of detailed spectroscopic analysis (IR, FAB‐, EI‐, or HR‐ESI‐MS as well as 1D‐ and 2D‐NMR experiments). Compounds 4 and 5 were evaluated for their antitumor effects in vitro (Table 3).     

Theoretical study of initiated reaction mechanism of polymerization of maleic anhydride catalyzed by OH−1 anion

A theoretical study of the polymerization reaction mechanism of maleic anhydride (MA) initiated by hydrate is presented. The reaction pathway has been studied with the density functional theory (DFT) method at the B3LYP/6‐311G** level. The geometrical parameters of transition states (TS) are optimized; intrinsic reaction coordinate (IRC) calculations have also been performed to obtain further credible features. Frequency analyses of all the stationary points are calculated at the same basis sets. The total energies of all geometries are corrected at second‐order Møller–Plesset (MP2)/6‐311G**. Calculation results reveal that the reaction mechanism is attributable to anion polymerization. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006