bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synthesis of porphyrin nitrogen mustards with potential anti‐tumor activities in chemotherapy and photodynamic therapy
Authors: Zhi‐Long Chen , Jing‐Rong Chen , Wei‐Qin Wan , De‐Yu Xu 
Published: September 2010

Abstract2,7,12,18‐Tetramethyl‐13,17‐di[3′‐N, N‐di(2″‐chloroethyl)aminopropyl]porphin and its 3,8‐di(1′‐alkyloxyethyl)‐analogous or porphyrin‐nitrogen mustards were synthesized for the first time. Their structures were determined by spectroscopies and elemental analyses. Most of the compounds possess both the chemotherapeutic and photodynamic effects on tumor and deserve further investigation.
Samarium diiodide induced asymmetric synthesis of γ‐butyrolactone using chiral auxiliaries derived from isosorbide and isomannide
Authors: Ming‐Hua Xu , Gue‐Qiang Lin , Li‐Jun Xia 
Published: September 2010

AbstractThe asymmetric reductive coupling reaction of various acrylates derived from D‐isosorbide and D‐isomannide with acetophenone mediated by samarium diiodide to give both enantiomers of the optically active γ‐butyrolactone was described. The best enantiomeric excess of the products was 60%.
Synthesis and ferromagnetic interaction in oxamido‐bridged heterodinuclear copper(II)‐chromium (III) complexes
Authors: Li Yan‐Tuan , Yan Cui‐Wei , Liao Dai‐Zheng 
Published: September 2010

AbstractFour μ‐ oxamido heterodinuclear complexes, [Cu (oxae) Cr (L)2 ] (NO3) 3, where oxae denotes the N, N'bis (2‐aminoethyl) oxamido dianion and L represents 1,10‐phenanthroline (phen); 5‐nitro‐1,10‐phenanthroline (NO2‐phen); 5‐methyl‐1, 10‐phenanthroline (Me‐phen) and 2, 2′‐bipyridine (bpy), have been synthesized and characterized by elemental analyses, magnetic moments (at room temperature) and molar conductivity measurements and spectroscopy. It is proposed that these complexes have extended oxamido‐bridged structures consisting of a copper (II) ion and a chromium (III) ion, which have a square planar environment and octahedral environment, respectively. The cryomagnetic properties of the [Cu(oxae)Cr(bpy)2(NO3)3(1) and [Cu(oxae)Cr(phen)2](NO3)3(2) complexes have been measured over the range of 4.2–300 K. The leastsquares fit of the experimental data based on the spin Hamiltonian, Ĥ = ‐ 2JŜ1·Ŝ2, the exchange integrals (J) were evaluated as +36.9 cm−1 for 1 and +35.8 cm−1 for 2. The reds have connived that the spin coupling between the adjacent copper (II) and chromium (III) ions through oxamido‐bridge in both 1 and 2 is ferromagnetic.
Synthesis and crystal structure of dinuclear nickel (II) complex
Authors: Liu Sheng‐Hua , Chen Liao‐Rong , Fu En‐Qin , Wu Cheng‐Tai 
Published: September 2010

AbstractThe crystal structure of Ni (II) complex with 3‐hydroxyl‐1,5‐diazacycloheptane‐N, N′‐diacetate was determined by X‐ray diffraction method. Crystal data for Ni2 (C9H14 N2O5 )2·2H2O: monoclinic, space group P21/n, a =1.1717(5), b =0.9794(3), c = 1. 2971(2) nm, β=96.62(3), V = 1. 4786(7) nm3, Dc = 1. 377 g/cm3, Z = 2, μ =13.321 cm−1 (Mo‐Ka), F (000) = 640. The final R and Rω are 0.075 and 0.089 respectively. The Ni(II) ion forms 2:2 complex with ligand. Two ligands are bridged by two Ni(II) atoms which are bridged by two 0 atom. Every Ni(II) is coordinated by two N atoms and four O atoms The coordination polyhedron of the Ni(II) ion is a distorted octahedron.
Rational synthesis structural characterization and the third‐order nonlinear optical properties of two new M‐Cu‐S (M = Mo or W) clusters
Authors: Yu Rong‐Min , Lu Shao‐Fang , Chen Hong‐Bing , Huang Xiao‐Ying , Huang Jian‐Quan , Wu Bo‐Chang , Si Jin‐Hai 
Published: September 2010

AbstractBy the additional reaction of binuclear compounds (Me4N)2M2S4 (TDT)2 (M = Mo, W; H2TDT= H2CH3GH3S2) with mononuclear cuprous complex, two new M‐Cu‐S clusters Mo2 Cu2 S4 (TDT)2‐(PPh3)2CH3CH2OH (1) and W2Cu2S4 (TDT)2 (PPh3 )2 · 0. 5CH3 CH2 OH·0. 5H2O (2) have been prepared and characterized by IR, UV‐Vis, 31P NMR spectroscopy, cyclic voltammetry and single crystal X‐ray structure analysis. Both compounds crystallize in space group P 21/ n with lattice parameters a = 1.0956(3), b = 2. 2072(3), c =2.4340(3) nm, β=100.36(2)°, V= 5.790(3) nm3 and Z = 4 for 1 and a = 1.0965(9), b = 2.2135(3), c = 2.4317(4) nm, β = 99. 63(8)°, V = 5.819(8) nm3 and Z = 4 for 2. Both molecular structures contain a cubane‐like cluster core [M2Cu2S4] (M= Mo, W) and their skeletons are almost the same except for M atoms. The syntheses, structures and spectrum characterizations of these two clusters are discussed. The third‐order nonlinear optical (NLO) property of the two clusters was studied by the technique of forward degenerate four‐wave mixing (DFWM) for the first time and these clusters exhibited relatively large nonlinear optical coefficients.
Trans‐cis isomerization of 4‐(2‐(9‐anthryl)vinyl)pyridine. Molecular structures and 1H NMR kinetic studies
Authors: Choi Ya‐Yin , Wong Wai‐Yeung , Wong Wing‐Tak 
Published: September 2010

AbstractBoth cis‐ and trans‐isomers of 4‐(2‐(9‐anthryl) vinyl) pyridine were isolated and their molecular structures established by X‐ray crystallographic method. Variable temperature 1H NMR spectroscopy was used to study the trans to cis isomerization of the title compound. The kinetic study of the reaction was based on the ratio of the NMR integration heights in toluene‐d8 of the double doublet due to the cis‐isomer at δ 8.51 to that of the multiplet at δ 8. 15 which was kept constant during the whole experiment. The isomerization process was found to be first order and the Arrhenius activation parameters E8, ln A, Δ H≠ and ΔS≠ were calculated as 27.84 kJ/mol, 6.71, 25.23 kJ/mol and −197.89 J/(K·mol), respectively. Besides, conformational analyses of both compounds based on molecular modeling were carried out and the results were used to compare with the experimental data.
Influence of bond valence on bond covalency in calcium doped lanthanum chromite
Authors: Wu Zhi‐Jian , Meng Quig‐Bo , Zhang Si‐Yuan 
Published: September 2010

AbstractThe influence of bond valence on bond covalence in Lal‐xCaxCrO3(x = 0.0, 0.1, 0.2, 0.3) has been studied by using semi empirical method. This method is the extortion of the dialectic description theory proposed by Phillips, Van Vetches, Levine and Tanaka (PVLT). In the calculation of bond valence, two schemes were adopted. The first is the equal‐valence scheme, and the second is Bond Valence Sums (BVS) scheme. Bath schemes suggest that for the title compound bond covalence be mainly influenced by bond valence, and insensitive to the Ca doping level. Generally speaking, larger bond valences usually result in higher bond covalence's.
Study on the energy transfer between UO2+2 and Eu3+ in sol‐gel derived titania matrix by luminescence spectroscopy
Authors: Fu Lan‐She , Zhang Hong‐Jie , Wang Shu‐Bin , Meng Qing‐Guo , Yang Kui‐Yue , Ni Jia‐Zuan 
Published: September 2010

AbstractThe TiO2 gel doped with UO2+2 and Eu3+ has been prepared by a sol‐gel method. The quenching of the UO2+2 emission by Eu3 + and the energy transfer from the excited state of UO2+2 to the ground state of Eu3+ have been investigated. The energy transfer has been studied by the measurement of luminescence lifetime τ, calculation of energy transfer efficiency WET and energy transfer rate ηET. The experimental results indicated that the quenching is combined static and dynamic mechanism, but the static mechanism is dominant.
Anodic synthesis and XPS analysis of La1‐x.NaxCu2O4
Authors: Zhao Liang‐Zheng , Zhang Jin‐Riao , Xu Cui‐Ying , Liu Shi‐Hong 
Published: September 2010

AbstractThe single phase La1‐xNaxCu2O4 crystals were synthesized by an electrochemical method from molten KOH/NaOH/KNO3 at 280–300°C while La2‐y NayCuO4 were prepared by precipitation from the same molten salt. The resulting crystals were characterized by using SEM, XRD, EDX and XPS. XPS analysis revealed that the La3d satellite structures of La1‐x NaxCu2O4 were quite different from those of La2‐y NayCuO4. These differences have been attributed tyo the changes in crystal structures, bond lengths and covalent character of the metal‐ligand bonds.
Synthesis and characterization of chromia‐pillared layered tetratitanate
Authors: Hou Wen‐Hua , Chen Ya‐Shao , Guo Can‐Xiong , Yan Qi‐Jie , Chen Yi , Chen Jing 
Published: September 2010

AbstractThe first chromia‐pillared layered tetratitanate was prepared by the reaction of layered tetramethylammonium tetratitanate with chromium (III) acetate [Cr(OAc)3] aqueous solution and subsequent calcination of the resultant solid product in air at 400°C. The obtained chromia‐pillared layered tetratitanate has an interlayer distance of 1.06 nm and a high thermal stability up to 600°C. It was also found that calcination in N2 led to the chromia‐pillared layered tetratitanate with relatively higher Brunauer‐Emmett‐Teller (BET) specific surface area (93.9 m2·g−1) and smaller average pore diameter (4.44 nm) than that in air (82.0 m2·g−1, 7.61 nm). Both Brönsted and Lewis acid sites (mainly Lewis type) are present on the chromia‐Pillared layered tetratitanate (500°C, N2, 8 h) and strong enough to still remain a small proportion of pyridine upon outgassing at 250°C. Moreover, ammonia temperature‐programmed desorption (NH3‐TPD) result showed that there were three NH3 desorption peaks at 160, 200 and 315°C, respectively. The corresponding acid amount is 41.3, 73.9 and 290.7 μmol·g−1. The total acid amount is 405.9 μmol·g−1.
Comparison of spline wavelet and orthogonal wavelet in processing analytical chemistry signals
Authors: Zheng Xiao‐Ping , Mo Jin‐Yuan 
Published: September 2010

AbstractSpline wavelet and orthogonal wavelet are two widely used wavelet methods. In this paper, comparison of these two methods has been made, including their algorithm, properties and results of signal processing in analytical chemistry signals. It is found that spline wavelet is more effective than orthogonal wavelet in processing high noise signals. The curves obtained from spline wavelet are closer to the theoretical ones than those obtained from orthogonal wavelet and the errors of spline wavelet are smaller than those of orthogonal wavelet.
Mechanism of reduction of benzylidenemalononitrile by 1‐benzyl‐1,4‐dihydronicotinamide
Authors: Wang Hong‐Yi , Liu You‐Cheng , Zhu Xiao‐Qing , Guo Qing‐Xiang 
Published: September 2010

AbstractThe reduction of benzylidenemdononitrile by 1‐benzyl‐1,4‐dihydronicotinamide undergoes via a one‐step hydride transfer mechanism rather than a multistep mechanism involving initial electron transfer.
A highly enantioselective synthesis of 5‐(l‐menthyloxy )‐4‐substituted‐3‐chloro‐2(5H )‐furanones
Authors: Geng Zhe† , Huang Bin , Chen Qing‐Hua 
Published: September 2010

AbstractIn this paper, stereocontrolled tandem Michael addition‐elimination reaction of the novel chiral source, 5‐(l‐menthyloxy)‐3,4‐dichloro‐2(5H)‐furanone, with various thiols and amines has been investigated. A series of new enantiomerically pure compounds, 5–(l‐menthyloxy)‐4‐substituted‐3‐chloro‐2(5H)‐furanones, were obtained in good yields with d. e. ⩾ 98% under mild conditions.
A simple and versatile method for the synthesis of soluble C60‐based polystyrene derivatives
Authors: Xiao L‐Xiang , Chen Yu , Shen Jian‐Zhong , Cai Rui‐Fang , Huang Zu‐Enxs 
Published: September 2010

AbstractA new simple and useful method for the synthesis of soluble C60‐styrene copolymer is demonstrated Covalent attachment of C60 onto the polystyrene backbone has been confirmed by UV‐VIS absorption spectra, 13C NMR and SEM.
New spectroscopic methods for environmental measurement and monitoring
Authors: Steinfeid Jeffirey I. 
Published: September 2010

AbstractThe ability to monitor a broad range of chemical species in the atmosphere, geosphere, and hydrosphere is a key technology for addressing global environmental issues. This report surveys several high sensitivity spectroscopic techniques for this purpose, including Frequency‐Modulation‐Enhanced Remote Sensing, Intra Cavity Laser Absorption Spectroscopy, Cavity Ring Down Spectroscopy, and Raman Spectroscopy.
Solubility of stearic acid in supercritical CO2‐acetonitrile mixtures
Authors: Mao Can , Lu Jie , Han Bu‐Xing , Yan Hai‐Ke 
Published: September 2010

AbstractThe solubility of stearic acid in supercritical CO2with acetonitrile (CH3CN) cosolvent was measured at 318. 15 K in the pressure range hm 9.5 to 16.5 MPa, and the cosolvent concentration ranges from 0. 0 to 5.5 mol%. The solubility increases with acetonitrile concentration and pressure, and it also increases with the apparent density of CO2d1(moles of CO2in per liter of fluid) at higher co solvent concentrations. At lower d1, however, the solubility of the acid at lower acetonitrile concentrations is lower than that in pure CO2provided that d1is fixed, which is discussed qualitatively based on the clustering of the components in the system.
From pharmacophore to leads: Bioactive compound discovery via computer‐aided techniques
Authors: Yuan Shen‐Gang , Luo Shi‐Wei , Chai Ge‐Qing , Yao Jian‐Hua , Chen Hai‐Feng , Zheng Chong‐Zhi 
Published: September 2010

AbstractBased on the concept of Green Chemistry, a new procedure of finding bioactive compounds and their synthetic routes by computer‐aided techniques was proposed. The procedure consists of pharmacopoeia search against a 3D structural database of natural products for lead discovery and computer‐aided synthesis design for avoiding un useful synthetic experiments. This work demonstrated that computer aided drug design and synthesis design would help us to make the consideration of environmental concerns systematically, rather than having to deal later with the unnecessary waste chemicals. Thus, it is shown that chemical computer‐aided design (CAD) is an indispensable part of Green Chemistry.
An undecanuclear iron (III) oxo‐hydroxo aggregate with near nanometer size: Synthesis and crystal structure of [Fe11O6(OH)6(O2CPh)3(O2CPhMe‐p)12]
Authors: Wei Yong‐Ge , Zhang Shi‐Wei , Liu Ye‐Qi , Shao Mei‐Cheng 
Published: September 2010

AbstractThe title compound is formed by controlled hydrolytic polymerization in nonaqueous solution of simple oxo‐bridged binuclear ferric salts under the presence of carboxylate ligands. The rhombohedral crystalline form of the cluster with six imidazole molecules, which has crystallographically required C3y symmetry, will be reported. The largest Fe—Fe distance in the undecairon oxo‐hydroxo cluster is about 0.68 nm and the cluster has a diameter near 2 nm, which implies that this cluster reach‐ a nanometer‐sized dimension.
Synthesis, structure and characterization of the trinuclear copper (I) complex [Cu3(μ3‐Br)2(dppm)3]Br
Authors: Yang Rui‐Na , Sun Yu‐An , Hu Xiao‐Yuan , Jin Dou‐Man 
Published: September 2010

AbstractThe novel trinuclear copper(I) complex [Cu3(μ3,‐Br)2(dppm)3]Br has been obtained by reaction of bis(diphenyl‐phosphino)methane (dppm) with cupric bromide. The title complex was characterized by single‐crystal X‐ray analysis, elemental analysis, molecular weight determination, 31P NMR and its conductivity was also measured. The [ Cu3 (dppm)3 Br2 ]+ cation consists of a triangular array of copper atoms, with dppm ligands (Ph2 PCH2 PPh2) bridging each edge of the triangle and two triply bridging Br groups bound to the two faces of the Cu3 unit. Crystallographic data: monoclinic, space group P21/c, a = 1.4739(4), b = l.7708(5), c = 2.8395(8) nm, β= 97.16(3)°, V = 7.353nm3, Z = 4, F(000)= 3296, Dcalc, = 1.472 g/cm3, μ = 26.478 cm−1, R=0.06, RW = 0.08, 4654 reflections observed with I3≥(I).
Structure and base properties of calcined hydrotalcites
Authors: Liu Hai‐Chao , Yang Xi‐Yao , Ran Guo‐Peng , Min En‐Ze , Liu Jian‐Ke , Ying Pin‐Liang , Xin Qin , Li Can 
Published: September 2010

AbstractFive hydrotalcites with Mg/Al molar ratio range of 3–15 were prepared. The structure and basicity of Mg‐Al mixed oxides (Mg(Al)O) transformed from hydrotalcites were investigated by TPD, XPS, XRD, FT‐IR and NMR techniques. The results of elemental analysis and XPS indicate that Al is enriched in the surface regions of Mg(Al)O, and its amount increases with the Mg/Al molar do and the Calcination temperature. 27Al‐MAS‐NMR results show that Al exists in two chemical environments: tetrahedral aluminium (Al(t)) and octahedral aluminium (Al(o)) in Mg(Al)O. The amount of Al(t) increases with the Mg/Al molar ratio and the calcination temperature. It is assumed that A(t) may be mainly from the surface Al. Temperature‐programmed desorption (IPD) of CO2 shows that the number of basic sites of Mg(Al)0 samples increases with the Mg/Al molar ratio, and the maximum number of basic sites is obtained for hydrotalcite calcined at 773 K. Infrared spectra of adsorbed CO2 and B(OCH3)3 reveal that there are two kinds of basic sites: weak basic OH− sites and strong basic O2 sites on the Mg(Al)0 samples, the base strength depends on the Mg/Al molar do and calcination temperature.
LCAC‐SW quantum scattering dynamic study on the ion‐pair formation process
Authors: Ma Wan‐Yong , Feng Da‐Cheng , Cai Zheng‐Ting , Deng Cong‐Hao 
Published: September 2010

AbstractLCAC‐SW method has been extended to study the reaction dynamics for ion‐pair formation processes. M+ X2→Mt + X2 reaction system involves two potential energy surfaces, i.e., the covalence state (M + X2) and the ionic state (M + X2) and their crossing effect. The working equations for calculating state‐to‐state probability have been derived based on the above two‐state model, Satisfied results d collinear state‐to‐state probabilities for K+ I2 → K+ + I2 ion‐pair formation system have been obtained.
Synthesis and structure of catena cadmium complex with 2‐hydroxo‐1‐naphthaldehyde thiosemicarbazono tetradentate ligand
Authors: Zhang Wen‐Xing , Li Jian , Si Shu‐Feng , Li Jim‐Jun , Ma Chang‐Qin , Jiang De‐Hua 
Published: September 2010

AbstractThe title ligand (H2L) and its complex [CdL(py)2]py (L= C12H9N3OS dianionic) have been synthesized and characterized. The complex structure determination indicates that Cd( II ) atom has a distorted octahedral coordination geometry. As an unusual tetradentate ligand, one L2 chelates one Cd( II ) atom using the O, S atoms and one N atom of the hydrazino group while its another N atom links to the neighbouring Cd atom. The bridging hydrazono groups extend the compound into a catena chain. The naphthoxy rings of each neighboring unit are alternatively arranged at opposite sides of the chain, and the ring planes on the same side are parallel.
A novel heteropolymetalate containing Fe4(OH)4 segment: Crystal structure of [Me4N]10[Fe4(OH)4(PW10O37)2]15H2O
Authors: Wu Jin‐Chuan , Chen Min‐Qin , Li Ming‐Xing , Xie Gao‐Yang , Jin Song‐Lin 
Published: September 2010

Abstract[Me4N]10[Fe4(OH)4(PW10O37)2] 15H2O was synthesized by the reaction of FeCl3 6HzO, with A‐Na8HPW9O34 and Me4NBr. Crystal data: M = 6225.75, space group P21/c with he monoclinic parameters: a = 1.3228(5), b=3.5634(3), c = 1.5226(2) nm, β = 94.20(2), V = 7.1576nm3, Z = 2,Dc = 2.888 g/cm3, Mo Ka radiation (λ = 0.071069 nm), μ = 168.534 cm−1, F(000) = 5576, final R = 0.0428 and Rw = 0.1204 for 7086 observed reflections with I 2s̀(I). The structure of the title compound is the first structurally characterized heteropolymetalate with hydroxo‐bridging metal aggregation Fe4(OH)4 encapsulated in the dimer of Keggin polyoxoanion.
Enthalpy‐entropy compensation effect in gas chromatographic enantiomeric separation
Authors: Zhou Liang‐Mo , Nie Meng‐Yan , Wang Qing‐Hai , Zhu Dao‐Qian , Shen He‐Qing 
Published: September 2010

AbstractIn this paper, the enthalpy‐entropy compensation effect in the enantiomeric separation by modified cyclodextrins (CD) and diamide chiral stationary phase (GP) gas chromatography was investigated using the method of plotting Δ( ΔH) versus Δ(ΔG) 7hm combined with t‐test statistic analysis. The investigated racemates cover α‐phenylethylamine and its analogs, 2‐alkylamines, chiral acyclic alcohols, halogenated arylethanediol‐1, 2‐diperfluoropropionates, amino acid and its analogs, and two series of compounds containing chloro and bromo substituents. From the compensation analysis results, the effects of the diluent composition in the investigated chiral stationary phases, the size and the died pups on investigated cyclodextrins, the derivatization methods and the groups attached to the stereocenters on enantiomeric separation mechanisms were all discussed.
Syntheses of imidazolium‐bridged cyclodextrin dimers and their catalytic properties in the hydrolytic cleavage of p‐nitrophenyl alkanoates
Authors: Luo Mei‐Ming , Xie Ru‐Gang , Yuan De‐Qi , Lu Wei , Xia Ping‐Fang , Zhao Hua‐Ming 
Published: September 2010

AbstractTwo imidazolium‐bridged cyclodextrin dimers 3a and 3b were prepared by reacting 6‐deoxy‐6‐N‐imidazolyl‐β‐CD (2) with bis(bromomethyl) benzene. The catalytic properties of 2, 3a and 3b in the hydrolytic cleavage of p‐nitrophenyl alkanoates, in the form of acetate (PNPA), butanoate (PNPB), hexanoate (WH) and octanoate ( PNPO), were examined. CD dimers showed middling rate enhancements around neutrality. Catalytic rate constants ( kc) in the presence of 3a or 3b did not vary much with chain length of esters. In contrast, dissociation constants (Kd) and selectivity factors (kc/Kd) for “long‐chain” esters were much smaller and significantly larger than those for “short‐chain” ones respectively, indicating CD dimers 3a and 3b have good dimensional recognition ability and substrate selectivity in the hydrolytic cleavage of p‐nitrophenyl alkanoate. Their kinetic consequences are briefly interpreted.
Use of 3–(2′‐formyl‐1′‐chlorovinyl)coumarin in the syntheses of pyrazol, salicylaldazine and pyrimidine derivatives
Authors: El‐Deen Ibrahim M. 
Published: September 2010

Abstract3–(Pyrazol‐5‐yl)coumarin (3) was prepared from condensation of 3–(2′‐formyl‐l‐chlorovinyl)‐coumarin (1) with hydrazine hydrate at room temperature, followed by cyclyzation with base. Salicylaldazine was prepared from methoxylation of 1 to give acetal7, followed by condensation of 7 with hydrazine hydrate at 80°C: Treatment of acetal 7 with thiourea yielded the corresponding 4‐substituted‐2‐thioxo‐2H‐pyrimidine[3, 4‐b]‐coumarin (12).
Convenient one‐pot synthesis of functionalized cyclopentene via Sm/TMSCI/t‐BuOH system mediated hydrodimerization cyclization of gem‐diactivated alkene
Authors: Wang Lei , Zhang Yong‐Min 
Published: September 2010

AbstractFunctionalized cyclopentenes could be prepared through Sm/TMSCl/t‐BuOH mediated hydrodimerization cyclization of gem‐diactivated alkene in one‐pot at room temperature. The trans‐ or trans, transform isomer is in the majority and the major product was isolated from its stereoisomers through the fractional crystallization method.
Allyl chloride/AIC13/ether cationic initiating systems for polymerization of 1,3‐pentadiene
Authors: Peng  , Yuan Wu. , Liu Jia‐Lin , Zhang Wen‐Chuan 
Published: September 2010

AbstractVarious ethers were used to mediate the polymerization of 1,3‐pentadiene (PD) initiated by AlCl3 and by allyl chloride (AllyCl)/AlCl3. The introduction of the ethers exert considerable effects on polymer yield and molecular weight due to its interaction with the propagating carbocation. The carbocation reactivity is reduced by this interaction which is subject to the ether's nucleophilicity determined by the steric hindrance of groups adjacent to oxygen. The reduction of carbocation reactivity gives rise to a decrease of polymer yield owing to inhibition of propagation but results in an augmentation of molecular weight due to suppression of various side reactions such as terminations. By using suitably nucleophilic ethers such as diphenyl ether, the polymerization can be mediated to give an high molecular weight polymer in high yield.