Novel α-methyl(benzyl)deoxyvasicinones

A method was developed to prepare -methyl(benzyl)deoxyvasicinones by alkylation of -hydroxy- methylidenedeoxyvasicinone. It has been shown that the reaction proceeds anomalously through a deformylation step.Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 407–409, September–October, 2004.     

Synthesis of Novel Bis(mesocyclic) polyamines

介绍了带羟基桥连双－（中环多胺）的合成。首先利用Ｎ－对甲苯磺酰基－３－羟基－１，５－二氮杂环庚烷与５种双官能基化合物在Ｎ２气氛下于无水乙腈中反应，得到５种带对甲苯磺酰基的中环多胺，然后利用ＨＢｒ／ＨＯＡｃ脱去保护基团，得到桥连双－（中环多胺）的氢溴酸盐。所有新化合物的结构均经ＩＲ、１ＨＮＭＲ、ＭＳ或元素分析证实。     

A Novel Total Synthesis of (±)Shikonin

Shikonin 1 was a key component isolated from the traditional Chinese herbal medicine, Zicao(Lithospermum erythrorhizon Sieb.et Zucc), which possesses multiple biological activities1. There have been many synthetic routes to shikonin, however, all these ro…     

Novel pH responsive luminescent poly(oxyethylene phosphate) tris(β-diketonate) europium (III) complexes

The paper reports on the dependence of the absorbance and luminescent intensity from pH of novel poly(oxyethylene phosphate) tris(β-diketonate) europium (III) complexes. The photophysical data obtained allow some preliminary assumptions about the nature of this phenomenon. Increase in luminescent efficiency is a consequence of enhanced efficiency of energy transfer caused by structural changes in complexes after water deprotonation. Remarkable change has been observed in photophysical properties of the polymer complexes by studying the fluorescent emission and excitation spectra and absorption recorded at various pH both in solution and in the solid state. Some of the complexes derivative of the dibenzoylmethane (DBM) show more than hundred times increase in the luminescence after alkalization. The pH value, at which the maximum luminescent efficiency appears, depends on the type of the fourth ligand. The difference between luminescent efficiency of the complexes in alkaline and neutral environment depends on the β-diketonate ligands and on polymer type as well.      

Synthesis of Novel (p‐Substituted Styryl) Spirobenzopyrans

A series of (p‐substituted styryl) spirobenzopyrans were synthesized by the Wittig reaction of Fisher's bases with 5‐(p‐substituted styryl) salicylaldehyde derivatives. The final spirobenzopyrans were characterized by the ¹H NMR, IR, UV, and GC‐MS analyses.     

A Novel Stereoseletive Approach to (E)-Vinylic Selenides

Vinylicselenidesareimportantintermediatesinorganicsynthesis.andtheirpromisingpotentialcouldbeanticipatedbythecombinationofthespecialreactivityofseleniumandthereactivit}'associatedwithcarbon-carbondoublebond.particularly'the}'areextremely"set'ulinhighlystereoselectiveC-Cbondformationprocess'.Variouspreparationsofthesecompoundshavebeenreported,butmostofthesemethodsinvolvedthedisposalofhighlytoxicselenides,suchasRSeX,RSeSeRandRSeH.Futhermore,manyofthesemethodsarenotstereocontrolledandgivemixt…     

Novel thermogelling poly(ε-caprolactone-co-lactide)-poly(ethylene glycol)-poly(ε-caprolactone-co-lactide) aqueous solutions

The aqueous solutions of poly(e-caprolactone-co-lactide)-poly(ethylene glycol)poly(e-caprolactone-co-lactide) undergoing sol-gel transition as the temperature increases from 20 to 50℃were successfully prepared. The thermogelling triblock copolymers were synthesized by subtle tuning of the chemical composition and the hydrophilicity/hydrophobicity balance. The sol-gel transition was studied focusing on structure-property relationship. The amphiphilic copolymer formed micelles in aqueous solutions. It is believed to have potential applications in drug delivery and tissue engineering.     

Novel (η-arene)-ruthenium(II) complexes containing bis(iminophosphorano)methanide and methandiide ligands

The novel bis(iminophosphorano)methanes CH₂[P{NP(S)(OR)₂}Ph₂]₂ (R = Ph (1a), Et (1b)) have been obtained by oxydation of dppm with the corresponding thiophosphorylated azides (RO)₂P(S)N₃. Deprotonation of 1a,b with KH generates the methanide species KCH[P{NP(S)(OR)₂}Ph₂]₂ (R = Ph (2a), Et (2b)). The ruthenium(II) dimer [{Ru(η⁶-p-cymene)(μ-Cl)Cl}₂] reacts with 2a,b to afford the cationic complexes [Ru(η⁶-p-cymene)(κ³-C,N,S-CH[P{NP(S)(OR)₂}Ph₂]₂)]⁺ (R = Ph (3a), Et (3b)), via selective κ³-C,N,S-coordination of the bis(iminophosphorano)methanide anions to ruthenium. The structure of [Ru(η⁶-p-cymene)(κ³-C,N,S-CH[P{NP(S)(OEt)₂}Ph₂]₂)][PF₆] (3b) has been confirmed by single-crystal X-ray crystallography. Deprotonation of complexes 3a,b with NaH leads to the neutral carbene derivatives [Ru(η⁶-p-cymene)(κ²-C,N-C[P{NP(S)(OR)₂}Ph₂]₂)] (R = Ph (4a), Et (4b)).     

Novel Ba_(0.5)Sr_(0.5)Fe_(0.8)Zn_(0.2)O_(3-δ) membranes for POM

A novel cobalt-free perovskite based on Ba_(0.5)Sr_(0.5)Fe_(0.8)Zn_(0.2)O_(3-δ)(BSFZ)were prepared by EDTA-citric acid method.The lattice constants of the BSFZ perovskite were characterized by in situ high-temperature X-ray diffraction(HTXRD).The thermal expansion coefficient of BSFZ is 10.5×10~(-6)K~(-1),which is lower than that of cobalt-based perovskite materials.The BSFZ membrane was also used to construct reactors for the partial oxidation of methane(POM)to syngas.Results show that the BSFZ membrane...     

Novel SrCe_(0.75)Zr_(0.20)Tm_(0.05)O_(3-δ) membrane for hydrogen separation

<正>Dense ceramic membranes with protonic and electronic conductivity have attracted considerable interest in recent years.In this paper,the powders of SrCe_(0.75)Zr_(0.20)Tm_(0.05)O_(3-δ) were synthesized via the liquid citrate method,and the membranes of SrCe_(0.75)Zr_(0.20)Tm_(0.05)O_(3-δ) were prepared by pressing followed by sintering.X-ray diffraction(XRD) was used to characterize the phase structure of both the powder and sintered membrane.The microstructure of the sintered membranes was studied by scanning electron microscopy(SEM).Hydrogen permeation through the SrCe_(0.75)Zr_(0.20)Tm_(0.05)O_(3-δ) membranes was carried out using gas permeation setup at 900℃.Hydrogen permeation flux of SrCe_(0.75)Zr_(0.20)Tm_(0.05)O_(3-δ) membrane reaches up to 0.042 mL/ min cm~2 at H_2 partial pressure of 0.4 atm.The hydrogen permeation fluxes obtained in this paper are similar to that of SrCe_(0.95)Tm_(0.05)O_(3-δ),and Zr doping can increase mechanical strength of SrCe_(0.75)Zr_(0.20)Tm_(0.05)O_(3-δ) membranes and the resistance to reducing circumstance.     

Off-on-off Luminescent Switching of a Novel Ru(II) Complex

There has been explosive interest in the synthesis and applications of novel Ru(II) polypyridyl complexes with respect to molecular sensors1,2, switches3, and sensitizers of Gr鋞zel solar cells based on nanocrystalline TiO24. Here we report a novel Ru(II) complex, which can serve as pH-induced remarkable off-on-off luminescent switch. Scheme 1 The acid-base equilibria of the complex UV-vis absorption and emission spectroscopic pH titration experiments of the Ru complex wit…     

Synthesis of Novel Benzoylphenylurea Chitin Inhibitors From Chlorothalonil ( Ⅱ )

Six novel benzoylphenylurea chitin inhibitor derivatives were synthesized in the yields of 30%-50%from the readily available starting material chlorothalonil 1 via sequential fluorine exchange, aminolysis, hydrolysis and acylation reactions.     

Synthesis of Novel Benzoylphenylurea Chitin Inhibitors From Chlorothalonil(Ⅱ)

IntroductionThe insecticidal activity of benzoylphenylurea( BPU ) analogues,discovered in the early1 970′s[1_ 4] ,is connected with the process ofmoult-ing and appears to affect the chitin synthesis of in-sects. The benzoylphenylurea class of insectgrowth regulators( IGRs) ,interfere with chitinsynthesis in target pests,causing death or abortivedevelopment and are considered to be the fourthgeneration of insecticides or novel materials for in-sect control.Benzoylphenylurea type insecticides…     

Novel Highly Branched Polyester Nanoparticles(I)──Light-Scattering Characterization

ＮｏｖｅｌＨｉｇｈｌｙＢｒａｎｃｈｅｄＰｏｌｙｅｓｔｅｒＮａｎｏｐａｒｔｉｃｌｅｓ（Ｉ）──Ｌｉｇｈｔ－ＳｃａｔｔｅｒｉｎｇＣｈａｒａｃｔｅｒｉｚａｔｉｏｎＭＡＲｏｎｇ－Ｊｉｕ（ＰｏｌｙｍｅｒＩｎｓｔｉｔｕｔｅ,ＪｉｌｉｎＵｎｉｖｅｒｓｉｔｙ,Ｃｈａ...     

Electrochemical Behavior of Novel Bis(β-diketonate)phthalocyanine Complexes of Zr(IV) and Hf(IV)

We have used cyclic voltammetry to study the electrochemical properties of novel bis(-diketonate)phthalocyanine complexes of Zr(IV) and Hf(IV) in dichloromethane. We found three waves for the studied complexes that can be attributed to one-electron processes MPc(L)^0/1– ₂, MPc(L)^1+/0 ₂ and MPc(L)^2+/1+ ₂. We have shown that the electrochemical behavior of the complexes depends on the nature of the substituents in axial ligands and does not depend on the nature of the metals. We have analyzed the stability of the one-electron oxidation products of the complexes relative to disproportionation.     

Studies on Macrocyclic Diterpenoids (Ⅵ)——A Novel Synthetic Route to (±)-Cembrene-A

The total synthesis of(土)-cembrene-A, a termite pheromone, was achieved from geranylacetone and geraniol as starting materials. The key steps were the phase transfer catalyzed coupling reaction of sulphone (6) with chloride (9) and the intramolecular macrocyclization of dicarbonyl precursor (12) induced by low valent titanium. The synthetic route was short with anoverall yield of 17%.     

Polymerization of styrene by Novel Ni(Ⅱ)- and Pd(Ⅱ)-based complexes

The catalytic activities of nine neutral nickel and palladium a-acetylide complexes [M=(C=CR)2(PR'3)2)M=Ni,Pd; R=Ph,CH2OH,CH2OOCH3,CH2OOCPh,CH2OOCPhOH-o; R'=Ph,Bu] are compared.Among them,Ni(Cs=CPh)2-(PBuj)2 shows the highest catalytic activity and gives the polystyrene with high molecular weight(Mw=188800)and a syndio-rich microstructure.The catalytic behavior of transition metal acetylides is related to metal,phosphine,and alkynyl ligands bonded to the metal atoms.     

Novel Synthesis of Haloaromatic Tertiary Alcohols Using (η6-Fluoroarene)tricarbonylchromium(0) Complexes

Regioselective synthesis of haloaromatic tertiary alcohols can be achieved by ortho deprotonation/electrophilic reactions of (η⁶- fluoroarene)Cr(CO)₃ complexes with halobenzophenones and metal removal. The coexistence of different halogens in the aromatic rings of these molecules make them unique within the group of tertiary alcohols.