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.     

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-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。     

Dispersed fluorescence spectroscopy of the CBr2A1B1-X1A1 transition

Dispersed fluorescence spectra following the excitation of the CBr2A1B1-X1A1 2 and 2 bands at visible wavelengths were acquired in a discharge supersonic free jet expansion using an intensified charge-coupled device (ICCD) detector. The dispersed fluorescence spectra show signal-to-noise ratios of up to 60 and extend out to a maximum red shift frequency of 6000 cm(-1). Complete and detailed vibrational structure of the ground singlet state (X1A1) was observed. Vibrational parameters including fundamental frequencies, anharmonicities, and coupling constants were determined for the CBr2 X1A1 state. Additional vibrational structure starting at approximately 3650 cm(-1) was observed and this indicates the singlet-triplet energy gap to be >10 kcal mol(-1).     

1-Methyl-1-phenyl-3,3-dimethyl-3-dimethylamino-1-propanol synthesis

Summary A new tertiary amino alcohol, 1-methyl-1-phenyl-3,3-dimethyl-3-dimethylamino-1-propanol,was prepared; it failed to enter the esterification reaction.The present work was begun during the life of I. N. Nazarov as a small part of a systematic study suggested by him.     

GAS PERMEABILITY OF COPOLY(1-TRIMETHYL-SILYL-1-PROPYNE-PENTAMETHYL-DISILYL-1-PROPYNE) MEMBRANE

The permeability of copoly (1-trimethylsilyl-1-propyne-pentamethyldisilyl-1-propyne) membrane for twelve gases (0_2, N_2, CO_2, H_2, D_2, He, At, CH_4, C_2H_4, C_2H_6, C_3H_6 and C_3H_8) was examined. The basic laws of solution and diffusion of the gases in the membrane were expounded preliminarily. It was found that a linear relationship between logarithm of diffusion coefficient (D) and critical molar volume (V_c) of the gases. The permeation characteristics of the gases in the copoly (1-trimethylsilyl-1-propyne-pentamethyldisilyl-1-propyne) membrane was also discussed.     

Temperature dependence of adlayers on Pt(1 1 1) and Au(1 1 1) in a sulfuric acid solution studied by in situ IRAS

Temperature dependence studies of adsorption of sulfuric acid species on Pt(1 1 1) and Au(1 1 1) electrodes were carried out using in situ infrared reflection absorption spectroscopy. A temperature-dependent shift of the interconversion potential between HSO₄⁻/H₃O⁺ and H₂SO₄ on a Pt(111) electrode was observed. A temperature-dependent frequency shift of the absorption bands of HSO₄⁻ was also observed on both Pt(1 1 1) and Au(1 1 1) electrodes in the potential region where a √3×√7 structure evolved. Modelling experiments in ultrahigh vacuum revealed that ordering of the overlayer water molecules played an important role in the frequency of the absorption bands of HSO₄⁻.     

Packing Effect on Mixed-Valence States of 1′,1′′′-Dialkyl- and 1′,1′′′-Bis(Methylbenzyl)Biferrocenium Triiodides

Abstract

A remarkable packing effect on the mixed-valence state was observed in 1′, 1′′′-diisobutylbiferrocenium triiodide. The effect was also observed for a series of 1′,1′′′-dialkyl- and 1′,1′′′-bis(methylbenzyl)biferrocenium triiodides by means of ESR spectroscopy.     

1,1,1-三氟-2-甲基-2-丙醇合成工艺研究

以氯甲烷(2)为原料制备甲基氯化镁格氏试剂;以三氯化镓为催化剂,甲基氯化镁与1,1,1-三氟丙酮(3)反应,经水解制得1,1,1-三氟-2-甲基-2-丙醇(1).产物结构经1 H-NMR、13 C-NMR、19 F-NMR及MS表征;通过单因素、正交实验和放大重复性实验确定了最佳反应条件:溶剂为正丁醚、格氏试剂浓度3 ...     

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).     

Gas permeability and stability of poly(1-trimethylsilyl-1-propyne-co-1-phenyl-1-propyne) membranes

A significant reduction in the gas permeability of the poly(1-trimethylsilyl-1-propyne) (PMSP) membrane was investigated in terms of the membrane thickness and the storage environment. The effects of physical aging were observed with thinner membranes and under vacuum conditions compared with storage in air. The decrease in the permeability coefficient was dependent on the decrease in the hole saturation constant of Langmuir adsorption (C'_H), which is related to the volume of the microvoids. Physical aging in the PMSP membrane affected not only the glassy domain but also the rubbery one. To stabilize the permeability of the PMSP membrane, a poly(1-trimethylsilyl-1-propyne-co-1-phenyl-1-propyne) [poly(TMSP-co-PP)] membrane was prepared. Poly(TMSP-co-PP) has the same unit of poly(1-phenyl-1-propyne), which membrane has stable permeability. The poly(TMSP-co-PP) with less than 20 mol % PP content was estimated to be a random copolymer based on theoretical gas permeation analysis. In the poly(TMSP-co-PP) membrane, the relation between the PP content and C'_H was similar to the relation between the PP content and the gas permeability. The stability of the permeability was dependent on the PP content. The poly(TMSP-co-PP) membrane containing 10 mol % PP had both high permeability and good stability under some of the aging conditions performed in this work. © 1995 John Wiley & Sons, Inc.     

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.     

Thermolysis of 1-(1-aryl-1-bromomethyl)cyclopropyl bromides: a reinvestigation

Two compounds, the (Z)- and (E)-isomers of 2,4-dibromo-1-p-tolyl-1-butene 2a and 3a, respectively, were isolated in 65% total yield when 1-(1-bromo-1-p-tolylmethyl)cyclopropyl bromide (1a) was heated at 150 degrees C for 1 h. 1,1-Dibromo-2-p-tolylcyclobutane (4a), previously reported to be the only product in this reaction, was not detected. The phenyl analogue of 1a reacted similarly and gave the (Z)- and (E)-isomers of 2,4-dibromo-1-phenyl-1-butene 2b and 3b, respectively, in 60% yield. A rationale for the reaction is presented.     

Palladium-catalyzed synthesis of 1-alkylphosphonium salts from 1-alkenes

A palladium(0) complex catalyzes the addition reaction of a triarylphosphine and a protic acid to a 1-alkene, giving a 1-alkylphosphonium salt. The treatment of atmospheric ethylene, triphenylphosphine, and (CF3SO2)2NH in the presence of Pd2(dba)3.CHCl3 (dba = dibenzylideneacetone) (0.1 mol %) in chlorobenzene at 65 degrees C for 5 h gave ethylphosphonium salt in 98% isolated yield. The anti-Markovnikov adduct 1-propylphosphonium salt was obtained by the reaction of atmospheric propene in 95% yield. 1-Butene was converted to 1-butylphosphonium salt in 92% yield in the presence of 1 mol % catalyst. This reaction competed with olefin isomerization, and a mixture of 2-butene and 1-butene (>20:1) was recovered. The reactions of 1-pentene and 1-hexene with triphenylphosphine gave modest yields of the products. The less reactive 1-alkenes, however, reacted effectively with tris(p-chlorophenyl)phosphine. The inner olefins, 2- and 3-pentene also gave a 1-pentylphosphonium salt in high yields via rapid olefin migration.     

Synthesis of 3,4-benzo-1-chloro-1-methyl-1-silacyclohexane and some of its derivatives

Conclusions 3,4-Benzo-1-chloro-1-methyl-1-silacyclohexane was synthesized by intramolecular cyclization of vinylbenzylmethylchlorosilane; its structure was demonstrated, and the properties of some of its derivatives were investigated.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2733–2737, December, 1969.     

Phase behavior of 1-alkylpyridinium octane-1-sulfonates. effect of the 1-alkylpyridinium counterion size

The temperature-versus-composition phase diagrams of eight different 1-alkylpyridinium octane-1-sulfonates (APOSs) in water were studied by 1H NMR, 2H NMR, pulsed gradient spin-echo NMR, small-angle X-ray diffraction, differential scanning calorimetry, surface tension and conductivity measurements, and polarizing microscopy. The number of carbons (n(c)) in the hydrocarbon chain of the pyridinium counterions was varied from n(c) = 1 to n(c) = 8 to study how the phase behavior of the APOS/2H2O systems was affected by a change in the chain length of the counterion. The sodium octane-1-sulfonate (NaOS)/water system was used as a reference. This system formed an isotropic micellar solution (L1) phase and a normal hexagonal (H(I)) phase. All APOSs were readily soluble in water and formed L1 phases. The surface tension above the critical micelle concentration for n(c) between 1 and 3 was higher than that for NaOS, and it decreased steadily for the different APOSs with increasing chain length. The area per molecule at the air/solution interfaces was rather constant at 68 A2 for n(c) between 1 and 7. For 1-octylpyridinium octane-1-sulfonate (OPOS), it was about 5 A2 smaller, which was just outside the estimated error. However, the smallest area was obtained for NaOS. At higher surfactant concentrations, liquid crystalline phases formed. Both cubic and H(I) phases were found for n(c) = 1 and 2, while for n(c) between 3 and 5 only an H(I) phase was observed. H(I) and lamellar liquid crystalline (Lalpha) phases formed for n(c) = 6 and 7. The only liquid crystalline phase found in the OPOS system was a Lalpha phase. The NaOS H(I) phase was the only liquid crystalline phase that showed a linear relation between the 2H2O NMR quadrupolar splitting (deltaW) and Xsurf/X(W), where Xsurf and X(W) are the mole fractions of surfactant and water. The OPOS lamellae were found to be much thinner than expected, indicating a defect lamellar structure. This was further supported by the behavior of the quadrupolar splitting ofdeuterated OPOS. The anomalous behaviors of the 2H2O NMR quadrupolar splitting observed in the Lalpha phases of 1-heptylpyridinium octane-1-sulfonate and OPOS were interpreted in terms of changes in the population of the water molecules residing in different sites combined with a continuous rearrangement of the lamellae surface with the possible development of holes. The appearances of the phase diagrams were discussed in terms of surfactant molecular geometry and the packing of the amphiphiles in the aggregates formed.     

以1-甲基-1-甲氧基乙基为保护基的一锅法合成5-芳香二酮-1H-四氮唑

报道了5-芳香二酮-1H-四氮唑(2)的一锅合成法,并且首次报道了1-甲基-1-甲氧基乙基作为四氮唑氮原子的保护基团,保护与脱保护反应条件温和,操作简便,收率高,为该类化合物的合成提供了一条捷径.采用该方法共合成6个未见文献报道的5-芳香二酮-1H-四氮唑类新化合物,以用于药理活性筛选.     

1-羟基-1-甲基-3-氧-异吲哚类衍生物的合成

邻苯二甲酸酐与丙二酸反应合成邻乙酰基苯甲酸(1);1经酰氯化反应得邻乙酰基苯甲酰氯(2);2与伯胺反应合成了3个1-羟基-1-甲基-3-氧-异吲哚化合物,总收率65.0%～76.8%,其结构经1H NMR, 13C NMR, IR和MS表征.     

Rearrangements of 1-(1-methylprop-1-en-1-yl)-1,2-dimethylacenaphtyylenonium ions

It was discovered by means of dynamic NMR that the 1-(cis-1-methylprop-1-en-1-yl)-1,2-dimethylacenaphthylenonium ion generated under conditions of “long life” for carbocations underwent fast (ΔG^#35.8 kJ mol^?1 at ?103°C) degenerate 1,2-shift of the cis-dimethylvinyl group. Quantum-chemical calculations by DFT method predict lower rate of 1,2-shift for the trans-dimethylvinyl group compared to cis-dimethylvinyl group and dependence on the cations conformation of the rates of these processes and of the rearrangement mechanism into the ions of phenalenyl type.