3-甲基-1a-(4-甲氧基苯基)-1, 1-二氯-1, 1a, 2, 3-四氢-吖丙 啶并[1, 2-d] [1, 5]苯并硫氮杂卓的合成和晶体结构

通过2-甲基-4-(4-甲氧基苯基)-2,3-二氢-1,5-苯并硫氮杂卓与二氯卡宾的[2+1]环加成反应制备了标题化合物,用X射线单晶衍射测定了其晶体结构。分子式C~1~8H~1~7Cl~2NOS,分子量366.30,晶体属正交晶系,空间群P~b~c~a,晶胞参数:a=1.2246(3)nm,b=1.5219(4)nm,c=1.9272(9)nm,V=3.592(2)nm^3,Z=8,D~c=1.355g.cm^-^3。位于中心的1,5-硫氮杂卓环为扭曲的类船式构象,船头与苯环并合,船底与吖丙啶环并合。     

The reductive repair of 1, 3-dhnethylthymine bromohydrin into 1, 3-dimethylthymine by 1, 5-dihydro-5-deazaflavin or 1, 4-dihydroquinoline

The reductive conversion of 1, 3-dimethylthymine bromohydrin into 1, 3-dimethylthymine by 10-ethyl-3-methyl-1, 5-dihydro-5-deazaflavin or 1-benzyl-3-carbamoyl-1, 4-dihydroquinoline has been achieved in the presence of trifluoroacetic acid.     

[1+1+1] Cyclotrimerization for the Synthesis of Cyclopropanes

The synthesis of small rings by functionalization of C(sp³)?H bonds remains a great challenge. We report for the first time a copper‐catalyzed [1+1+1] cyclotrimerization of acetophenone derivatives under mild reaction conditions. The reaction has a broad scope for the stereoselective synthesis of cyclopropanes by trimerization of acetophenone. The developed transformation is based on an extraordinary copper‐catalyzed cascade process that allows saturated carbocycles to be obtained for the first time by cyclotrimerization through functionalization of C(sp³)?H bonds. The cascade of sixfold C(sp³)?H bond functionalization allows the synthesis of cyclopropanes in a highly stereoselective approach.     

1－甲氧基－1－锂乙烯的结构及其分解反应的DFT研究

用量子化学中的密度泛函DFT方法，在B3LYP／631G（d,p）水平上研究了－甲 氧基－1－锂乙烯的结构。结果表明，1－甲氧基－1－锂乙烯有4种平衡结构，其中 只有1种是稳定的。对稳定的平衡结构，找到了分解反应的过渡态。在得到分解反 应过渡态的基础上，根据Eyring过渡态理论，计算了不同温度下1-甲氧基－1-钾乙 烯分解反应的速率常数，并根据速率常数计算了其平均寿命τ，根据平均寿命τ讨 论这类物质的稳定性问题。     

Effect of Various Synthesis methods on the Electrochemical Properties of LiNi1/3Co1/3Mn1/3O2

Layered LiNi1/3Co1/3Mn1/3O2 has the isostructure of α-NaFeO2 and shows high rate capacity with stable cycleability. Furthermore, the thermal behavior of this material is milder than that of lithium nickel oxide and lithium cobalt oxide. In addition, it is expected to be stable at elevated temperatures. Therefore LiNi1/3Co1/3Mn1/3O2 may be the most promising cathode materials of lithium-ion secondary battery.In this research, LiNi1/3Co1/3Mn1/3O2 was prepared by solid-state reaction, sol-gel method and mixed hydroxide method. The influences of synthesis method on the physical and electrochemical properties of LiNi1/3Co1/3Mn1/3O2 were characterized by means of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), charge/discharge cycling cyclic voltammetry and differential scanning calorimetry (DSC). XPS studies show that the predominant oxidation states of Ni, Co and Mn in the LiNi1/3Co1/3Mn1/3O2 compound are 2+, 3+ and 4+. From the voltage profile and cyclic voltammetry, the redox processes occurring at ～3.8V and ～4.5V are assigned to the Ni2+/Ni3+ and Co3+/Co4+ couples, respectively. Different preparation methods result in the difference in morphology (shape, particle size and specific surface area) and electrochemical behaviors. A sample prepared by solid-state reaction has the worst electrochemical performance among these three methods. Sample synthesized by mixed hydroxide method displays the better rate capacity than that prepared by sol-gel method, while the capacity retention of sample prepared by sol-gel method is superior to that synthesized by mixed hydroxide method.     

钛硅分子筛（TS－1）的合成、结构表征及催化性能研究

在不同条件下成功地合成了钛硅分子筛ＴＳ－１，并利用ＩＣＰ－ＡＥＳ、ＸＲＤ、ＦＴ－ＩＲ、ＴＭＥ等手段对所获得的分子筛进行了表征，研究发现，ＴＳ－１分子筛中骨架钛与非骨架锐钛矿的相对含量、晶体结构、晶体粒子的大小、形貌特征等属性与分子筛的合成方法密切相关。并通过氯丙烯环氧化反应研究了获得的ＴＳ－１分子筛的催化活性与合成方法及其结构之间的相互关系。     

Copolymerization of 4-methyl-2-pentyne with 1-trimethylsilyl-1-propyne and 1-trimethylgermyl-1-propyne with Nb-containing catalysts

It has been shown that the copolymerization of 4-methyl-2-pentyne with 1-trimethylsilyl-1-propyne or 1-trimethylgermyl-1-propyne with the use of niobium pentachloride-based catalytic systems in the presence of Ph₃Bi, Et₃SiH, and Bu₄Sn as cocatalysts yields corresponding copolymers of various compositions. The technique of determining the composition of copolymers from their IR spectra has been developed. The reactivity ratios of the monomers have been estimated. It has been demonstrated that these values increase in a sequence 4-methyl-2-pentyne > 1-trimethylsilyl-1-propyne > 1-trimethylgermyl-1-propyne.     

X-ray Structure of a Pentacarbonyltungsten Complex of 1-Phosphaallene

The structure of a tungstenpentacarbonyl complex of 3, 3-dipheny1-1-(2,4,6-tri-t-butylpheny1)-1-phosphaallene has been determined by X-ray analysis.     

Efficient sulfonation of 1-phenylsulfonyl-1H-pyrroles and 1-phenylsulfonyl-1H-indoles using chlorosulfonic acid in acetonitrile

The sulfonation of various 1-phenylsulfonyl-1H-pyrroles and 1-phenylsulfonyl-1H-indoles using chlorosulfonic acid in acetonitrile has been studied, leading to the development of a clean and operationally simple protocol allowing direct synthesis of the corresponding 1-phenylsulfonyl-1H-pyrrole-3-sulfonyl chlorides and 1-phenylsulfonyl-1H-indole-3-sulfonyl chlorides, respectively, both of which may be easily converted to various sulfonamide derivatives by treatment with nitrogen nucleophiles. Efficient and selective removal of the phenylsulfonyl- or tosyl groups in the sulfonamide series may be achieved under mild conditions.     

A versatile route for the synthesis of 3-(1′, 1′-dimethyllallyl)coumarins

Synthesis of 3-(′, 1′-dimethylallyl)herniarin and 3-(′, 1′-dimethylallyl)desmothosyherniarin has been carried out by a versatile route.     

First synthesis of 1-aryl-4,4-dichlorobut-3-en-1-ones. The electrochemical reduction of 1-aryl-4,4,4-trichlorobut-2-en-1-ones as a key step

The first method for the synthesis of 1-aryl-4,4-dichlorobut-3-en-1-ones is reported. Treatment of acetophenones with anhydrous chloral leads to 1-aryl-4,4,4-trichloro-3-hydroxybutan-1-ones in near quantitative yields. These compounds were efficiently dehydrated with either sulfuric or p-toluenesulfonic acid to give 1-aryl-4,4,4-trichlorobut-2-en-1-ones, which were selectively converted to the title compounds in fair to quantitative yields by electrochemical reduction. The X-ray crystallographic structure of 4,4-dichloro-1-(4-methoxyphenyl)but-3-en-1-one has been determined. The preferential formation of β,γ-unsaturated ketones with total exclusion of the corresponding α,β-unsaturated isomers has been discussed with the aid of HF and B3LYP density functional theory methods.     

1-Tetrahydrofuranyl- and 1-tetrahydropyranyl-substituted 3-hydroxy-1,6-dihydropyridazin-6-ones

The reaction of 3,6-bis(trimethylsiloxy)pyridazine and its 4,5-dihalogen-substituted derivatives with 2-chlorotetrahydrofuran and 2-chlorotetrahydropyran has given 3-hydroxy-1-(tetrahydrofuranyl- and 3-hydroxy-1-(tetrahydropyranyl)-1,6-dihydropyridazin-6-ones, the structure of which as 1-substituted derivatives has been confirmed by an investigation of their IR spectra. On the basis of a study of ionization constants, the hypothesis has been put forward that these compounds exist in the hydroxy form.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1545–1547, November, 1973.     

NEXAFS study of a Pt-containing rod-like organometallic polymer (Pt-DEBP): molecular orientation onto HOPG, Au/Si(1 1 1), Cr/Si(1 1 1) and Si(1 1 1) surfaces

The influence of different substrates on the molecular orientation of organometallic polymer Pt-DEBP, [Pt(PBu₃)₂CCC₁₂H₈CC]_n, has been investigated by NEXAFS spectroscopy. Thin films were deposited on HOPG, Au/Si(1 1 1), Cr/Si(1 1 1), Si(1 1 1) and stainless steel. The assignment of the spectral features has been carried out on the basis of previous STEX calculations performed on phenylacetylene model molecule in gas phase and adsorbed on Pt(1 1 1) and Cu(1 0 0). Angular dependent analysis of the π* resonance occurring at 285.50 eV photon energy deriving by the benzene carbon orbitals showed a polarisation effect for all substrates. A preferential molecular orientation at nearly 40° to the surface normal was observed. This result might be explained by the strong interaction between sp and sp² carbons of the organic diethynylbiphenyl DEBP moiety contained in close chains, leading to polymer self-assembling.     

Polyfluoroalkylation and alkenylation of 1-benzyl-1H-indazol-3-ol

The polyfluoroalkylation and alkenylation of 1-benzyl-1H-indazol-3-ol by halopolyfluoroalkanes and fluorinated olefins has been studied. It was shown that only reactions proceeding with the participation of difluorocarbene lead to a mixture of N- and O-alkylation products. In all other cases, interaction with halopolyfluoroethanes and polyfluoroalkenes forms O-polyfluoroalkyl and alkenyl derivatives of indazolol.     

Conversion of 3-benzoyl-1-methyl-4-phenyl-γ-piperidol by arylamines and arylhydrazines. Synthesis of 3-arylamino-1-oxo-1-phenylpropanes and 1,3-diarylpyrazoles and their fragmentation under electron impact

It has been established that on heating, 3-benzoyl-4-hydroxy-1-methyl-4-phenylpiperidine is ring-opened in the presence of arylamines by a type of retroaldol reaction, with subsequent transamination of the intermediate Mannich base and the formation of 3-arylamino-1-oxo-1-phenylpropanes. When using arylhydrazines this γ-piperidol is recyclized with the formation of 1,3-diarylpyrazoles and their 4,5-dihydro derivatives. The mass spectral behavior of a series of 3-arylamino-substituted 1-phenylpropanones has been studied. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1486–1495, October, 2007.     

Synthesis and Crystal Structure of 2-(2-Ethyl-1H-imidazol-1-yl)-1-hydroxy-ethane-1,1-diyldiphosphonic Acid (EIHDP)

The crystal structure of the title compound (C7H14N2O7P2, Mr = 300.14) was determined by single-crystal X-ray diffraction. The crystal belongs to triclinic, space group P1 with a = 8.258(3), b = 8.886(3), c = 9.275(3) , α = 96.669(3), β = 115.706(3), γ = 104.467(3)°, V = 573.8(3) 3, Z = 2, Dc = 1.737 g/cm3, λ(MoKα) = 0.71073, F(000) = 720, μ(MoKα) = 0.41 mm-1, R = 0.030 and wR = 0.078. A total of 1970 unique reflections were collected, of which 1742 with I > 2σ(I) were observed. EIDHP has a structure similar to zoledronic acid (ZL). ZL is a potent bone antiresorptive bisphosphonate drug having significant activity against several parasitic protozoa. EIHDP has inner-salt character, consisting of a negatively charged PO3 group and a positively char- ged N(1) atom. The crystal structure is stabilized by intermolecular hydrogen bonds of O–H···O and N–H···O.     

Biosynthesis of aristeromycln: Evidence for the intermediacy of a 4β-hydroxymethyl-1α, 2α, 3α-trihydroxycyclopentanetriol.

Evidence for the intermediacy of a 4β-hydroxymethyl-1α, 2α, 3α-trihydroxycyclopentanetdol (5 or6) in the biosynthesis of the nucleoside antibiotic aristeromycin (1) has been obtained by administration of doubly-labeled forms of D-glucose to the fermentation broth ofStreptomyces citricolor followed by trapping of the tetrol5 using isotope dilution methods.     

gem-Silylborylation of an sp carbon: novel synthesis of 1-boryl-1-silylallenes

[reaction: see text] Novel synthesis of 1-boryl-1-silylallenes involving gem-silylborylation of 3-chloro- or 3-alkoxyalkyn-1-yllithiums with (dimethylphenylsilyl)(pinacolato)borane has been established. The reaction proceeds via 1,2-migration of the silyl group from the negatively charged boron atom of an intermediary borate complex to the terminal acetylenic carbon and is accelerated by the addition of chlorotrimethylsilane in the case that methanesulfonyloxy is employed as a leaving group. Furthermore, axially enantioenriched products could be prepared from mesylates of optically active propargylic alcohols.     

Stereoselective synthesis of 3-aminoindan-1-ones and subsequent incorporation into HIV-1 protease inhibitors

A new method for the stereoselective synthesis of 3-aminoindan-1-ones from triflates of salicylic sulfinyl imines and ethylene glycol vinyl ether has been developed. The reaction sequence starts with a regioselective Heck reaction followed by stereoselective Lewis acid mediated annulation. Acidic cleavage of the sulfinamides produced pure (R)- and (S)-3-aminoindan-1-ones, which were successfully isolated and incorporated into active HIV-1 protease inhibitors.