1-Phenyl-1-halo-1-silacyclohexanes

The approaches to synthesis of 1-phenyl-1-halo-1-silacyclohexanes C₅H₁₀Si(Ph)X (X = F, Cl, Br) have been examined. 1-Phenyl-1-chloro-1-silacyclohexane has been prepared via the known reaction of phenyltrichlorosilane with dimagnesium derivative of 1,5-dibromopentane; up to 20% of 1-bromo-1-phenyl-1-silacyclohexane admixture is formed along with the target product. The minor product formation has been prevented using an alternative method of chlorination of 1-phenyl-1-silacyclohexane with N-chlorosuccinimide. 1-Phenyl-1-fluoro-1-silacyclohexane has been obtained in close to quantitative yield via the reaction of 1-phenyl-1-chloro-1-silacyclohexane with SbF₃ and in 70% yield via its reaction with HF. The synthesis of 1-phenyl-1-bromo-1-silacyclohexane via bromination of 1-phenyl-1-chloro-1-silacyclohexane with N-bromosuccinimide has given the target product as a minor one, the major product being disiloxane formed due to hydrolysis of the Si–Br bond.     

1-乙酰胺基丙叉-1,1-二膦酸和1-丙酰胺基乙叉-1,1-二膦酸与碱土金属离子的螯合作用

用pH电位法研究了1-乙酰胺基丙叉-1,1-二膦酸(S-186)和1-丙酰胺基乙叉-1,1-二膦酸(S-106)与碱土金属的螯合作用(30±O.1℃).当金属离子与配体的摩尔浓度比为10∶1、1∶1和1∶2时,在水溶液中形成了MHL、ML、ML_2和M_2L等几种类型的配合物.分别测定了它们的稳定常数,其中S-186配合物稍高于S-106,说明配合物稳定性与螯合剂的碱度有平行关系.值得注意的是,这两种螯合剂与Sr~(2 )形成的双核配合物的稳定性均较其它碱土金属离子的为高.     

1-Chlor-1-phosphirane

The title compounds are prepared by reaction of disubstituted diazomethanes with 1-chloro-2-phenyl-2-trimethylsilyl-1-phosphaalkene. The chemistry of the 1-chloro-1-phosphiranes is described.     

1:1 alternating copolymers of 1-bicyclobutanecarbonitrile with styrene

High molecular weight, 1:1 alternating copolymers of 1-bicyclobutanecarbonitrile with styrene were prepared in tetramethylenesulfone solution by complexing the electron-poor bicyclobutane monomer with zinc chloride. Methyl 1-bicyclobutanecarboxylate under these conditions gave copolymers containing a slight excess of styrene units (ratio 1:1.3 to 1:1.8). High molecular weight homopolymers of 1-bicyclobutanecarbonitrile and of methyl 1-bicyclobutanecarboxylate were prepared similarly. The tendency of the bicyclobutane nitrile to form 1:1 alternating copolymers is as great as that of its vinyl analog, acrylonitrile, and the synthesis of other alternating copolymers from this monomer should be possible.     

Nuclear-substituted 1-phenyl-1-methyl-1-silacyclobutane derivatives

Conclusions The synthesis of some nuclear-substituted derivatives of 1-phenyl-1-methyl-1-silacyclobutane by the reaction of 1-methyl-1-chloro-1-silacyclobutane with the appropriate arylmagnesium bromides was described.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1686–1688, July, 1978.     

1-Trimethylsilyl-, 1-Trimethylgermyl- und 1-Trimethylstannyl-3,4-dimethylphospholen

1-Trimethylsilyl-, 1-Trimethylgermyl-, and 1-Trimethylstannyl-3,4-dimethylphospholene 1-Lithium-3,4-dimethylphospholen reacts with Me₃SiCl and Me₃GeCl yielding 1-trimethylsilyl-3,4-dimethylphospholene ( 1 ) and 1-trimethylgermyl-3,4-dimethylphospholene ( 2 ) respectively. 2 and 1-trimethylstannyl-3,4-dimethylphospholene ( 3 ) are formed using the reaction of 1 with Me₃GeCl and Me₃SnCl respectively. The ¹H, ¹³C and ³¹PNMR-spectra as well as the mass spectra of the new compounds are discussed.     

The vibrational structure of the X 1A1 - A 1B1 and A 1B1 - B 1A1 band systems of GeH2/GeD2 based on global potential energy surfaces

Transition probabilities were evaluated for the X (1)A(1)-A (1)B(1) and A (1)B(1)-B (1)A(1) systems of GeH(2) and GeD(2) to analyze the X-->A-->B photoexcitation. Franck-Condon factors (FCFs) and Einstein's B coefficients were computed by quantum vibrational calculations using the three-dimensional potential energy surfaces (PESs) of the X (1)A(1), A (1)B(1), and B (1)A(1) electronic states and the transition dipole moments for the X-A and A-B systems. The global PESs were determined by the multireference configuration interaction calculations with the Davidson correction and the interpolant moving least squares method combined with the Shepard [Proceedings of the 1968 23rd ACM National Conference (ACM, New York, 1968)] interpolation. The barriers to linearity correcting the spin-orbit interaction are evaluated to be 22,000 cm(-1) for the X state, 6300 cm(-1) for the A state, and 560 cm(-1) for the B state. The obtained FCFs for the X-A and A-B systems indicate that the bending mode is strongly enhanced in the excitation since the equilibrium bond angle greatly varies within the three states. The photoexcitation and fluorescence spectra calculated for the X-A system agree well with the observed spectra. The theoretical lifetimes for lower vibrational levels of the A and B states were calculated from the fluorescence decay rates for the A-X, B-A, and B-X emissions, and the lifetimes for the A state are in good agreement with the observed values except those affected by predissociation.     

Transsilylation of disilazanes with 1-chloro-1-methyl-1-silacyclobutane and other triorganylchlorosilanes

The first stage of the reaction of hexamethyldisilazane with 1-chloro-1-methyl-1-silacyclotmtane gives 1,3,3,3-tetramethyl-1,1-trimethylenedisilazane, and after that 1,3-dimethyl-1,3-bis(trimethylene)disilazane is formed. The latter reacts with 1-chloro-1-methyl-1-silacyclobutane to give tris[methyl(trimethylene)silyl] amine. From a large number of examples it is shown that transsilylation of disilazanes with chlorosilanes is a general reaction.     

1, 1-Difluoro-1H-cyclopropa[a]naphthalene

1, 1-Difluorocyclopropa[a]naphthalene ( 1b ) is prepared in three steps from 4-bromo-1,2-dihydronaphthalene ( 7 ) via carbene addition, benzylic bromination and bidehydrohalogenation. Structural evidence for formation of 1b is based on ¹H- and ¹⁹F-NMR spectroscopy. Compound 1b is stable in solution at ?30°. Upon reaction with MeOH/H⁺ it is converted to a 1:2 mixture of 1- and 2-methylnaphthoate ( 10 and 11 , respectively).     

1-甲基-1-乙氧基-1-烷硫基甲烷类化合物的合成研究

本文以乙缩醛和烷基硫醇为原料,在30－35℃于四氯化碳中反应20min左右,分别合成1－甲基－1－乙氧基－1－烷硫基甲烷,经红外光谱,质谱以及核磁共振谱检测,确证了产物结构。     

Synthesis of Ethyl 1-Phenyl- and 1-Alkyl-1-Indene-2-Carboxylates

The ethyl 1-phenyl and 1-alkyl-1-indene-2-carboxylates 2g and 2a-2f respectively were prepared in 68 - 83% yield by the reaction of phenyl- and alkylmagnesium halides with ethyl 1-methoxy-1-indene-2-carboxylate (1c).     

Epimeric 1-hydroxy-1-substituted indolizidines

Epimeric mixtures of 1-hydroxy-1-phenylindolizidines and 1-hydroxy-1-methylindolizidines were obtained from the reaction of 1-ketoindolizidine with the appropriate Grignard reagent. The resulting alcohols were separated by chromatographic and distillation techniques. Infrared data and physical constants were utilized for the elucidation of the structures. Structural assignments of the indolizidinium iodides were made on the basis of nmr data.     

Synthesis of 5-substituted 1-aryl-1H-pyrazole-4-acetonitriles, 4-methyl-1-phenyl-1H-pyrazole-3-carbonitriles and pharmacologically active 1-aryl-1H-pyrazole-4-acetic acids

Lithium aluminum hydride reduction of 5-substituted or unsubstituted ethyl or methyl 1-aryl-1H-pyrazole-4-carboxylates gave, generally in excellent yields, 5-substituted or unsubstituted 1-aryl-1H-pyrazole-4-methanols which afforded the corresponding 1-aryl-4-(bromomethyl)-1H-pyrazoles with hydrobromic acid in acetic acid solution. These crude intermediates gave by reaction with potassium cyanide in dimethylsulfoxide solution 1-aryl-1H-pyrazole-4-acetonitriles only in the case of 5-unsubstituted compounds, otherwise mixtures of 5-substituted 1-aryl-1H-pyrazole-4-acetonitriles and 4-methyl-1-phenyl-1H-pyrazole-3-carbonitriles were generally obtained. Acetonitriles IIIa,b,i,l gave in excellent yields the corresponding 1-aryl-1H-pyrazole-4-acetic acids Va,b,i,l by alkaline hydrolysis. Compounds Vb,i,l showed in the writhing test appreciable analgesic properties, associated with low acute toxicity; moreover, compound VI exhibited a statistically significant antiinflammatory activity in the carrageenan-induced edema assay.     

Cytochrome P450 1A1 (CYP1A1) polymorphisms and breast cancer risk in Korean women

Cytochrome P450 1A1 (CYP1A1) is involved in the 2-hydroxylation of estrogen, the hormone that plays a critical role in the etiology of breast carcinoma. We evaluated the associations between two CYP1A1 polymorphisms [MspI (rs4646903); Ile462Val (rs1048943)] and breast cancer in a multicenter case-control study of 513 breast cancer cases and 447 controls in Korea. Women carrying the T allele of the CYP1A1 MspI polymorphism were found to have a 1.72-fold (95% CI 1.11-2.68) greater risk of developing breast cancer. No association was found between any CYP1A1 Ile462Val polymorphism and breast cancer. Haplotype analysis of the two loci showed that the CA haplotype was associated with the lowest risk of breast cancer, and CA/CA diplotypes were associated with a lower risk of breast cancer [OR=0.28 (0.13-0.61)] than others/others diplotypes. Moreover, this reduced risk was more pronounced among women with a lower body mass index (BMI) [OR=0.18 (0.06-0.58)] or with a shorter lifetime exposure to estrogen [OR=0.23 (0.07-0.81)]. The results obtained suggest that the CYP1A1 MspI polymorphisms could affect susceptibility to breast cancer.     

Oxidation of 1-benzyldihydroisoquinolines or 1-benzyltetrahydroisoquinolines with dioxygen to 1-benzoylisoquinolines

An environmental-benign methodology to synthesize 1-benzoylisoquinolines from 1-benzyl-3, 4-dihydroisoquinolines or 1-benzyl-1,2,3,4-tetrahydroisoquinolines using dioxygen as an oxidant was developed. This methodology in combination with Bischler-Napieralski reaction leads to a facile synthesis of 1-benzoylisoquinolines from phenylacetic acids and phenylethanamines.     

Synthesis of 2,4-diphenyl-1H-pyrrol-1-amine derivatives

The direction of the reaction of 4-bromo-1,3-diphenyl-2-buten-1-one (γ-bromodypnone) with hydrazines depends on the nature of the substituent they contain. Reaction with 1-methylhydrazinium hydrosulfate gives 1-methyl-3,5-diphenylpyridazin-1-ium bromide but carboxylic acid hydrazides give N-(2,4-diphenyl-1H-pyrrol-1-yl)carboxylic acid amides. γ-Bromodypnone and phenylhydrazine give both 1,3,5-triphenyl-1,4-dihydropyridazine and N,2,4-triphenyl-1H-pyrrol-1-amine (15%). 1-(2,4-Dinitrophenyl)hydrazine gives the 2,4-dinitrophenylhydrazone of (Z)-4-bromo-1,3-diphenyl-2-buten-1-one. Condensation of 2,4-diphenyl-1H-pyrrol-1-amine with aromatic aldehydes readily leads to N-(arylmethylidene)-2,4-diphenyl-1H-pyrrol-1-amines and alkylation with methyl iodide gives N,N-dimethyl-2,4-diphenyl-1H-pyrrol-1-amine. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 404–414, March, 2009.     

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.     

Fluorocarbon derivatives of nitrogen. Part IV [1]. Perfluoro-1-azacyclohex-1-ylcaesium

Caesium fluoride combined with perfluoro-1-azacyclohexene in acetonitrile to yield perfluoro-1-azacyclohex-1-ylcaesium (1), which was characterised by ¹⁹F n.m.r. spectroscopy and by treatment with iodomethane to give 2,2,3,3,4,4,5,5,6,6-decafluoro-1-methyl-1-azacyclohexane (2). Attempts to derivatize the caesium salt with chlorotrimethylsilane provided fluorotrimethylsilane, perfluoro-[1-(1-azacyclohex-1-en-2-yl)-1-azacyclohexane] (4), and 2-chloro-3,3,4,4,5,5,6,6-octafluoro-1-azacyclohexene (5); information on the course of this reaction was obtained through experiments in which perfluoro-1-azacyclohexene was shown to undergo conversion into its chloro-analogue (5) and its dimer (4) $\text{via}$ treatment with chlorotrimethylsilane and fluoride ion, respectively. Aluminium chloride also converts perfluoro-1-azacyclohexene into its chloro-analogue (5).     

The X˜1A1, a˜3B1, a˜1B˜1, and B˜1A1 electronic states of SiH2

Four electronically low-lying states of silylene (SiH₂) have been studied systematically using high level ab initio electronic structure theory. Self-consistent field (SCF), two-configuration (TC) SCF, complete active space (CAS) SCF, configuration interaction with single and double excitations (CISD), and CASSCF second-order (SO) CI levels of theory were employed with eight distinct basis sets. The zeroth-order wave functions of the ground (X˜ ¹A₁ or 1 ¹A₁) and B˜ ¹A₁ (or 2 ¹A₁) excited states are appropriately described by the first and second eigenvectors of the TCSCF secular equations. The TCSCF-CISD, CASSCF, and CASSCF-SOCI wave functions for the B˜ ¹A₁ (or 2 ¹A₁) state were obtained by following the second root of the CISD, CASSCF, and SOCI Hamiltonian matrices. At the highest level of theory, the CASSCF-SOCI method with the triple zeta plus triple polarization augmented with two sets of higher angular momentum functions and two sets of diffuse functions basis set [TZ3P(2f,2d)+2diff], the energy separation (T₀) between the ground (X˜ ¹A₁) and first excited (a˜ ³B₁) states is determined to be 20.5 kcal/mol (0.890eV,7180cm⁻¹), which is in excellent agreement with the experimental T₀ value of 21.0 kcal/mol (0.910eV,7340cm⁻¹). With the same method the T₀ value for the a˜ ¹B₁−X˜ ¹A₁ separation is predicted to be 45.1 kcal/mol (1.957 eV,15780 cm⁻¹), which is also in fine agreement with the experimental value of 44.4 kcal/mol (1.925 eV,15530 cm⁻¹). The T₀ value for the B˜ ¹A₁−X˜ ¹A₁ separation is determined to be 79.6 kcal/mol (3.452 eV,27 840 cm⁻¹). After comparison of theoretical and experimental T₀ values for the a˜ ³B₁ and a˜ ¹B₁ states and previous studies, error bars for the B˜ ¹A₁ state are estimated to be ±1.5 kcal/mol (±525 cm⁻¹). The predicted geometry of the B˜ ¹A₁ state is r_e(SiH)=1.458 and θ_e=162.3^∘. The physical properties including harmonic vibrational frequencies of the B˜ ¹A₁ state are newly determined. Received: 10 March 1997 / Accepted: 2 April 1997     

2 1 1At-tellurium colloid and Na2 1 1At injections,and their radiobiological effects

Na^{2 1 1}At and^{2 1 1}At–Te colloid injections were prepared. By comparison with tissue distribution of Na^{2 1 1}At and^{2 1 1}At–Te colloid injections it has been demonstrated that the^{2 1 1}At–Te colloid is stable in vivo. It has been shown that the radiohalogen,^{2 1 1}At, has huge and extensive radiobiological effects in studying on the changes in histopathology, enzyme histochemistry, chromosome aberration, micronucleus frequency of bone-marrow polychromatic erythrocytes and the injury effect of^{2 1 1}At on experimental Ehrlich ascites cells.