Rearrangement during cyclisation of some 3-(2-pyrrolyl) propionic acids and related compounds

Cyclisation of the title compounds leads to mixtures of the expected 4H-cyclopental[b]pyrrol-4-ones (1), the corresponding 6-ones (3) by a single rearrangement, and the cyclopenta[c]pyrrol-4-ones (4) by a double rearrangement, the proportions depending upon the substituents.The ¹H NMR spectra of 2-methyl-4H-cyctopenta[b]thiophen-6-one (3f) shows 6J long range $\text{CH}{}_3\text{CH}{}_2$ coupling, but this is absent in the corresponding pyrroles (3c,d). The ¹³C spectra of 1 and 3 cannot be interpreted on the basis of substituent chemical shifts in pyrroles and thiophens, and are clearly -CH = CH-X (X = NMe, NPh, S) bridged derivatives of cyclopent-2-enone.     

一种新的质子泵抑制剂苯并咪唑衍生物的合成与表征

以2-巯基苯并咪唑为原料,在碱性条件下与自制的盐酸2-氯甲基-4-(3-甲氧基丙氧基)-3-甲基吡啶缩合得2-{[4-(3-甲氧基丙氧基)-3-甲基吡啶-2-基]甲基硫}-1H-苯并咪唑,再经氧化、成盐反应生成产物2-{[4-(3-甲氧基丙氧基)-3-甲基吡啶-2-基]甲基亚硫酰基}-1H-苯并咪唑钠,总收率66%.此产物通过红外光谱、核磁共振、质谱表征加以确认.     

Calculation of harmonic force constants,vibrational frequencies and integrated intensities of some organic molecules using the MINDO—Forces method

The harmonic force constants, vibrational frequencies and integrated intensity ratios of CH₂, H₂O, CH₂O, C₂H₂, CO₂, HCN, CH₃, CH₄, and C₂H₄ have been calculated using the MINDO—FORCES program and the Pulay method for the calculation of the molecular force constants. The results obtained are in general quite satisfactory when compared with available literature values. The results are, however, not as satisfactory in case of molecules containing heteroatoms, due to the neglect of some dipolar repulsion integrals for the heteroatoms by the MINDO/3 method. Calculated integrated intensities for CH₃ and C₂H₄ agree well with experimental results. The calculated integrated intensities for other molecules are obtained for the first time and no comparison with published data is therefore possible.Part of the M.Sc. Thesis of K. H. A. 1978.     

有机分子与聚电解质静电吸附成膜特性研究

选取多种有机分子及聚电解质，采用静电吸附自组装法制备了聚电解质，聚电解质、聚电解质，有机分子、有机分子，有机分子的复合薄膜，讨论了这些体系的静电吸附成膜特性及其成膜机理．     

Physico-chemical and thermochemical studies of the hydrolytic conversion of amorphous tricalcium phosphate into apatite

The conversion of amorphous tricalcium phosphate with different hydration ratio into apatite in water at 25 °C has been studied by microcalorimetry and several physical-chemical methods. The hydrolytic transformation was dominated by two strong exothermic events. A fast, relatively weak, wetting process and a very slow but strong heat release assigned to a slow internal rehydration and the crystallization of the amorphous phase into an apatite. The exothermic phenomenon related to the rehydration exceeded the crystalline transformation enthalpy. Rehydration occurred before the conversion of the amorphous phase into apatite and determined the advancement of the hydrolytic reaction. The apatitic phases formed evolved slightly with time after their formation. The crystallinity increased whereas the amount of HPO₄²⁻ ion decreased. These data allow a better understanding of the behavior of biomaterials involving amorphous phases such as hydroxyapatite plasma-sprayed coatings.     

Practical synthesis of 1-deoxy-d-xylulose and 1-deoxy-d-xylulose 5-phosphate allowing deuterium labelling

An optimised gram scale synthesis allows the production of 1-deoxy-d-xylulose and 1-deoxy-d-xylulose 5-phosphate with possible deuterium labelling at C-5. Such substrates are required for investigations on the mevalonate-independent 2-C-methyl-d-erythritol 4-phosphate pathway for isoprenoid biosynthesis in bacteria and chloroplasts of phototrophic eukaryotes and for the biosynthesis of vitamins B₁ (thiamine diphosphate) and B₆ (pyridoxol phosphate) in bacteria.     

1,3,3—三甲基—2—[β—（5—取代苯基—2—呋喃基）乙烯基]—3H—吲哚盐的合成

1,3,3- 三甲基-2-[β-(4-取代苯基)乙烯基]-3H-吲哚盐是熟知的聚甲川型染料,常由费歇尔碱与芳香醛制备,也可由该碱的季铵盐一步合成。但这些方法往往需要使用较昂贵的溶剂,有的尚未分出染料纯品.近年来这类染料获得许多新的用途,如作光敏电照相记录材料和电照相增感剂等.本文考察了碘化1,2,3,3-四甲基-3H-吲哚(Ⅰ)与5-取     

NADH Electrooxidation Using Bis(1,10-phenanthroline-5,6-dione) (2,2'-bipyridine)ruthenium(II)-Exchanged Zirconium Phosphate Modified Carbon Paste Electrodes

We present a carbon paste electrode (CPE) modified using the electron mediator bis(1,10‐phenanthroline‐5,6‐dione)(2,2′‐bipyridine)ruthenium(II) ([Ru(phend)₂bpy]²⁺) exchanged into the inorganic layered material zirconium phosphate (ZrP). X‐Ray powder diffraction showed that the interlayer distance of ZrP increases upon [Ru(phend)₂bpy]²⁺ intercalation from 10.3 Å to 14.2 Å. The UV‐vis and IR spectroscopies results showed the characteristic peaks expected for [Ru(phend)₂bpy]²⁺. The UV‐vis spectrophotometric results indicate that the [Ru(phend)₂bpy]²⁺ concentration inside the ZrP layers increased as a function of the loading level. The exchanged [Ru(phend)₂bpy]²⁺ exhibited luminescence even at low concentration. Modified CPEs were constructed and analyzed using cyclic voltammetry. The intercalated mediator remained electroactive within the layers (E°′=–38.5 mV vs. Ag/AgCl, 3.5 M NaCl) and electrocatalysis of NADH oxidation was observed. The kinetics of the modified CPE shows a Michaelis–Menten behavior. This CPE was used for the oxidation of NADH in the presence of Bakers' yeast alcohol dehydrogenase. A calibration plot for ethanol is presented.     

The effect of calcining conditions on the rehydration of dead burnt magnesium oxide using magnesium acetate as a hydrating agent

Summary Magnesium oxide was produced through calcination of magnesite ore. A rehydration percentage of MgO to Mg(OH)₂ of higher than 60% is obtained using calcination temperatures of 1000°C and below. At these temperatures medium reactive MgO was formed. The extend to which dead burnt MgO (obtained after calcination at 1200°C and higher) may be rehydrated is dependent on the calcination time, but even after 1 h and using magnesium acetate as a hydrating agent only 40% of the initial product has rehydrated to Mg(OH)₂. After 4 and more hours of calcinations at 1200°C, a maximum of approximately 14% of the initial MgO is rehydrated back to Mg(OH)₂. Thermogravimetric analysis was performed on the various compounds to determine the amounts of Mg(OH)₂ that formed.     

醇体系中新型晶体磷酸锆的合成和表征

醇体系中新型晶体磷酸锆的合成和表征赵玉娥，宋天佑，徐家宁，徐如人（吉林大学化学系，长春，１３００２３）关键词磷酸锆，合成，表征自１９６４年首次合成磷酸锆晶体［１］以来，人们又合成出多种磷酸锆晶体［２～４］。但在非水体系中合成磷酸锆的工作尚未见报道。本...