三(对乙酰基苯基)甲烷的合成及表征

以三苯甲烷（TPM）和乙酰氯为原料,以无水三氯化铝为催化剂,二氯乙烷为溶剂,经过乙酰化反应得到三（对乙酰基苯基）甲烷（TAcPM）．讨论了原料配比、溶剂、温度和后处理等因素对产率的影响,并采用红外、核磁及元素分析对TAcPM的结构进行了表征．     

Synthesis of 1,1-bis(silyl)-1-alkene derivatives bearing Si-H functional groups via Peterson protocol

Various aromatic aldehydes were converted to one-carbon elongate 1,1-bis(silyl)-1-alkene derivatives bearing Si-H functional and reactive groups in a convenient one-pot operation via the Peterson protocol. Then poly(styrene) and poly(α-methylstyrene) (?&II) random homopolymers were synthesized by solution free radical polymerization at 70(±1) °C using α,α′-azobis(isobutyronitrile) (AIBN) as an initiator. The aldehyde group is introduced by direct electrophilic substitution of polymers ? and II. This formylation reaction was conducted in two different solvents: dichloromethane (CH₂Cl₂) and nitrobenzene (PhNO₂). The results indicate that PhNO₂ appeared to be a more suitable solvent for such an aldehyde functionalization of the polymers. The formylated polymers (I_CHO, II_CHO) were then converted to Si-H functionalized polymers (I_Si-H, II_Si-H) via reaction with tris(dimethylsilyl)methyllithium, (HMe₂Si)₃CLi.     

Synthesis of Pharmacologically Active Bis(indolyl) and Tris(indolyl) Derivatives Using Chlorotrimethylsilane

Chlorotrimethylsilane is found to be a comparatively fast and efficient catalyst for carrying out electrophilic substitution reactions of indoles with various aldehydes/ketones/triethylorthoformate, yielding excellent amount of bis(indolyl)methanes/tris(indolyl)methanes. The merits of this protocol are avoidance of any external energy source, minimal reaction time, simple and easy procedure and high yield under solvent free room temperature condition. The versatility of this method has been tested with various aldehydes/ketones and received satisfactory results.     

Kinetics and mechanism of the formation of poly[(1,1,3,3-tetramethyldisiloxanyl)ethylene] and poly(methyldecylsiloxane) by hydrosilylation

The kinetics of the formation of poly(carbosiloxane), as well as of alkyl-substituted poly(siloxane), by Karstedt's catalyst catalyzed hydrosilylation were investigated. Linear poly(carbosiloxane), poly[(1,1,3,3-tetramethyldisiloxanyl)ethylene], (PTMDSE), was obtained by hydrosilylation of 1,3-divinyltetramethyldisiloxane (DVTMDS) and 1,1,3,3-tetramethyldisiloxane (TMDS), while alkyl-substituted poly(siloxane), poly(methyldecylsiloxane), (PMDS), was synthesized by hydrosilylation of poly(methylhydrosiloxane) (PMHS) and 1-decene. To investigate the kinetics of PTMDSE formation, two series of experiments were performed at reaction temperatures ranging from 25 to 56 °C and with catalyst concentrations ranging from 7.0 × 10⁻⁶ to 3.1 × 10⁻⁵ mol Pt/mol CHCH₂. A series of experiments was performed at reaction temperatures ranging from 28 to 48 °C, with catalyst concentrations of 7.0 ×10⁻⁶ mol of Pt per mol of CHCH₂, when kinetics of PMDS formation was investigated. All reactions were carried out in bulk, with equimolar amounts of the reacting Si H and CHCH₂ groups. The course of the reactions was monitored by following the disappearance of the Si H bands using quantitative infrared spectroscopy. The results obtained showed typical first order kinetics for the PTMDSE formation, consistent with the proposed reaction mechanism. In the case of PMDS an induction period occurred at lower reaction temperatures, but disappeared at 44 °C and the rate of Si H conversion also started to follow the first-order kinetics. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2246–2258, 2007     

Synthesis of tetrakis(2-pyridyl)methane: the first tetrapyridylmethane

Tetrakis(2-pyridyl)methane has been synthesized as the first member of tetrapyridylmethane family by nucleophilic aromatic substitution of 2-chloropyridine with tris(2-pyridyl)methyl anion in refluxing aromatic hydrocarbons; the use of 2-bromopyridine resulted in electron transfer giving rearranged dimer of tris(2-pyridyl)methyl radical.     

Molecular structure of (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine oxide. Synthesis of (3,5-diallylisocyanuratomethyl)phosphine sulfides

X-Ray study of the (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine oxide showed that the phosphorylmethyl group is bonded to the nitrogen atom of the cycle. Reaction of the tris(chloromethyl)phosphine sulfide with sodium diallylisocyanurate gave (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine sulfide, and treatment of the tris(3,5-diallylisocyanuratomethyl)phosphine oxide with phosphorus pentasulfide gave a tris(3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine sulfide.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1446–1448, August, 1993.     

无溶剂条件下方便、有效的方法合成3-氰基-2-吡啶酮衍生物

芳醛、丙酮和氰乙酰胺为原料,氢氧化钠为催化剂,在无溶剂条件下加热反应有效地合成2-吡啶酮衍生物,本方法具有反应时间短、条件温和、处理简单和环境友好等优点.     

三草酸合铁(Ⅲ)酸钾合成方法的改进

三草酸合铁(III)酸钾具有工业生产价值,其合成作为化学专业本科生的经典实验项目,按教材实验的效果却不尽人意。本文在严谨的化学平衡理论分析基础上,首次提出提高合成产率的关键是严格控制草酸和草酸钾的用量,改进后的合成条件为：氧化步骤H2O2的浓度为6%,水浴温度为40°C;充分氧化后,微沸2分钟;酸溶步骤中草酸稍微过量,草酸钾过量10%;结晶时做到充分冷却。经此改进,可简化操作,节约原料,实验室平均产率达87%,教学中学生实验平均产率超过70%。     

Synthesis and spectroscopic characterization of tris{(diphenylphosphino) dimethylsilyl}methane complexes of cr(0) and w(0)

Treatment of M(CO)₆ (M?=?Cr, W) with (Ph₂PMe₂Si)₃CH in toluene at elevated temperatures resulted in the isolation of pale green [Cr(CO)₃{(Ph₂PMe₂Si)₃CH}] and pale brown [W(CO)₃{(Ph₂PMe₂Si)₃CH}] in high yield. These complexes have been characterized by elemental analysis, conductivity measurements, TGA, mass spectrometry, and IR, electronic, ¹H and ³¹P{¹H} NMR spectroscopy. The complexes have pseudo octahedral geometry around the metal atom with tridentate coordination of the multidentate ligand. The six-membered MPSiCSiP metallacycles are shown to have high fluxionality at room temperature on the NMR time scale.     

微波作用下合成双(苯并咪唑-2-基)甲烷衍生物

在无溶剂、无催化剂存在条件下, 用微波促进5-取代-1H-苯并咪唑-2-乙酸乙酯和4-取代-1,2-邻苯二胺反应, 合成了取代双(苯并咪唑-2-基)甲烷衍生物, 产率均在80%以上. 产物结构经IR, ¹H NMR, MS等进行了表征.     

Ytterbium(III) Triflate as an Efficient Catalyst for the Synthesis of Perimidine Derivatives under Mild Conditions

Various biologically important perimidine derivatives have been efficiently synthesized in excellent yields using naphthalene‐1,8‐diamine with various ketones in the presence of a catalytic amount of Yb(OTf)₃. The influence of the loading of Yb(OTf)₃, reaction solvent, the structure of ketones was studied. This method is a very easy, simple and high yielding reaction for the synthesis of perimidine derivatives.     

Ring-opening Polymerization of ε-Caprolactone Using Lanthanide Tris（4-tert-butylphenolate）s as a Single-component Initiator

The ring-opening polymerization of ε-caprolactone (CL) initiated by novel singlelanthanide tris(4-tert-butylphenolate)s [Ln(OTBP)3] is reported. Single-component La(OTBP)3can effectively prepare polycaprolactone (PCL) with over 90% yield and viscosity averagemolecular weight about 60 × 103 under quite mild conditions: molar ratio of CL to initiator is 1000,60 ℃, 2 h in toluene. Mechanism study indicates that the monomer inserts into the growing chainvia the break of acyl-oxygen bond of CL.     

三(4-乙酰氨基苯基)甲烷的合成

以三苯甲烷为原料,经硝化、还原和乙酰化反应合成了一种新型三芳基甲烷——三(4-乙酰氨基苯基)甲烷,纯度99.74,总收率50.6%,其结构经1H NMR,FT-IR和元素分析表征。     

甲基丙烯酸[三-(二氟苯基)]甲酯的"一锅法"合成及甲醇溶剂解

螺旋手性聚合物在生物与制药领域具有广泛的应用,其中聚甲基丙烯酸三苯甲酯(PTrMA)是一种能分离对映体特别是含芳香环烃对映体的螺旋手性聚合物,其作为高效液相色谱(HPLC)的固定相已得到应用[1~2]。但PTrMA在使用时易被HPLC的流动相甲醇溶剂解而影响使用寿命,因此,合成耐甲醇溶     

NaHSO4.H2O Catalyzed Multicomponent Synthesis of 1-(Benzothiazolylamino) Methyl-2-Naphthols Under Solvent-Free Conditions

A one-pot, efficient three-component condensation of aldehydes, 2-naphthol, and 2-aminobenzothiazole in the presence of sodium hydrogen sulfate as an effective catalyst for the synthesis of 1-(benzothiazolylamino)methyl-2-naphthol derivatives under thermal and solvent-free conditions is described. These products involve two biologically active parts, Betti's base and benzothiazole. The present methodology offers several advantages, such as good yields, short reaction times, and easy work-up.     

Preparation of Highly Fluorinated Poly(ether sulfone)s under Mild Polycondensation Conditions Using Molecular Sieves

Highly fluorinated poly(ether sulfone)s were prepared by a modified polycondensation technique, using a molecular sieve dehydrating apparatus in order to efficiently remove water under mild conditions. Consequently, side reactions were minimized, which resulted in the formation of polymers free of microgels. This reaction was also used to introduce pentafluorostyrene moieties into the polymer to provide crosslinking functionalities.     

Synthesis and desilylation of some bis(trimethylsilyl)alkenes and polymers bearing bis(silyl)alkenyl groups

The synthesis of various vinylbis(silanes) from some aryl and heteroaryl aldehydes and (Me₃Si)₃CLi in Et₂O is described. Friedel-Crafts reaction of 1,1-bis(trimethylsilyl)-2-(2-naphthyl)ethene with various acyl chlorides (RCOCl, R = Me, Et, i-Pr, i-Bu, n-pent) gave the corresponding α-silyl-α,β-unsaturated enones with high E steroselectivity. Moreover, poly(styrene)-co-[2,2-bis(trimethylsilyl)ethenyl(styrene)] obtained via the reaction of polymers bearing pendant enone functions and (Me₃Si)₃CLi, reacts with the same acyl chlorides in the presence of catalytic amount of AlCl₃ to give the new macromolecules bearing α-silyl-α,β-unsaturated enones and α,β-unsaturated enones.     

三(对溴苯甲酰基)纤维素的合成及其分离性能的考察

采用超声方法合成了三(对溴苯甲酰基)纤维素[CTBB]，并用红外光谱、元素分析对此衍生物的结构进行了表征。将等量微品纤维素(MC)与三(对溴苯甲酰基)纤维素混合制成一种新型的手性薄层板。结合展开剂系统的优化，6种手性药物对映体获得了良好的分离，分离因子α≥1．30。此固定相适用于正相和反相液相色谱。     

三(邻甲基苄基)锡和二(间氟苄基)锡硫代水杨酸酯配合物的合成、结构及性质

合成了三(邻甲基苄基)锡硫代水杨酸酯配合物(1)和一维链状二(间氟苄基)锡硫代水杨酸酯配合物(2),经元素分析、IR、NMR、X射线衍射等技术手段表征了其结构。配合物1属三斜晶系,空间群Pī,晶体学参数a=1.00221(5)nm,b=1.48934(8)nm,c=1.71789(9)nm,α=78.3120(10)°,β=85.6560(10)°,γ=80.2580(10)°,V=2.4725(2)nm~3,Z=2,Dc=1.371 g/cm~3,μ(Mo Kα)=10.91 cm~(-1),F(000)=1040,R_1=0.0439,wR_2=0.1119。配合物2属单斜晶系,空间群为P21/n,晶体学参数:a=1.17827(5)nm,b=2.11945(9)nm,c=1.55970(7)nm,β=93.4510(10)°,V=3.8880(3)nm~3,Z=4,Dc=1.671 g/cm~3,μ(Mo Kα)=14.53 cm~(-1),F(000)=1936,R1=0.0323,wR2=0.0927。配合物1中锡原子呈四配位畸变四面体构型,配合物2中锡原子呈五配位畸变三角双锥构型。配合物1和2分别在152和195℃下稳定,电化学性质不可逆,对人体癌细胞Colo205、Hep G2、MCF-7、Hela和NCI-H460具有体外抗癌活性,配合物2的抗癌活性远大于配合物1。     

Synthesis and characterization of phthalazinone containing poly(arylene ether)s via a novel N–C coupling reaction

High‐molecular‐weight poly(phthalazinone)s with very high glass‐transition temperatures (T_g's) were synthesized via a novel N–C coupling reaction. New bisphthalazinone monomers ( 7a–e ) were synthesized from 2‐(4‐chlorobenzoyl) phthalic acid in two steps. Poly(phthalazinone)s, having inherent viscosities in the range of 0.34–0.91 dL/g, were prepared by the reaction of the bis(phthalazinone) monomers with an activated aryl halide in a dipolar aprotic solvent in the presence of potassium carbonate. The poly(phthalazinone)s exhibited T_g's greater than 230 °C. polymer 8b synthesized from diphenyl biphenol and bis(4‐flurophenyl) sulfone demonstrated the highest T_g of 297 °C. Thermal stabilities of the poly(phthalazinone)s were determined by thermogravimetric analysis. All the poly(phthalazinone)s showed a similar pattern of decomposition with no weight loss below 450 °C in nitrogen. The temperatures of 5% weight loss were observed to be about 500 °C. The poly(phthalazinone)s containing 4,4′‐isopropylidenediphenol and 4,4′‐(hexafluoroisopropylidene) diphenol and diphenyl ether linkage were soluble in chlorinated solvents such as chloroform. Other poly‐(phthalazinone)s were soluble in dipolar aprotic solvents such as N,N′‐dimethylacetamide. The soluble poly(phthalazinone)s can be cast as flexible films from solution. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2481–2490, 2003