Synthesis of the ethyl ester of the mononitrile of malonic acid by the catalytic carbonylation of benzenesulfonyloxyacetonitrile

A new method has been developed for the synthesis of the ethyl ester of the mononitrile of malonic acid by the carbonylation of benzenesulfonyloxyacetonitrile in absolute ethanol in the presence of cobalt carbonyl. The yield of the desired product was 30% with 60–90% conversion of the starting compound. The effects of temperature, pressure, and reaction time were studied.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. S. M. Kirov Urals Polytechnical Institute, Ekaterinburg. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 215–216, January, 1992.     

Macromolecular synthesis from saccharic lactones. Ring-opening polyaddition of D-glucaro- and D-mannaro-1,4:6,3-dilactones with alkylenediamines

Ring-opening polyaddition of a saccharic acid dilactone prepared from D-glucose, D-glucaro-1,4 : 6,3-dilactone, with several alkylenediamines proceeded at room temperature with no catalyst. The resulting new polyamides carrying many pendant hydroxyl groups, poly(alkylene D-glucaramide)s, were more amorphous and hydrophilic than the corresponding nylons having no hydroxyl groups, and were hydrolyzed more easily than the latter in an acidic condition. The ring-opening ability of D-mannaro-1,4:6,3-dilactone, which was another saccharic acid dilactone obtained from D-mannitol, was found to be lower than that of the D-glucaric analogue. © 1993 John Wiley & Sons, Inc.     

Thermal Behavior of Urea-(D) Tartaric Acid and Urea-(DL) Tartaric Acid Crystals

The thermal behavior of two new non-linear optical (NLO) materials, urea-(D) tartaric acid (UDT) and urea-(DL) tartaric acid (UDLT) were studied by using DSC, TG and TMA. The results show that: 1) The two crystals have different melting points but similar decomposition temperatures due to the influences of intermolecular forces, which is attributed to the stereo effects of (D)-tartaric and (DL)-tartaric acid molecules; 2) There was only thermal expansion and no thermal contraction when the UDT and UDLT crystals were heated; 3) There was no phase transition within the measured temperature range; 4) The thermal expansion of the UDT and UDLT crystals shows a small anisotropy; 5) The specific heats of UDT and UDLT change linearly with temperature in the measured temperature range and the value for UDT is 1.321 J g-1 K-1 at 320 K while the specific heat of UDLT is 1.357 J g-1 K-1 at the same temperature. This revised version was published online in July 2006 with corrections to the Cover Date.     

Synthesis and Crystal Structure of a Ternary Complex: [Ni(phen)2(pmal)]·8H2O

A new ternary complex [Ni(phen)(pmal)]·8H2O (phen = 1,10-phenanthroline,pmal2- = phenethyl malonic acid) has been synthesized by the reaction of nickel acetate, phen and phenethyl malonic acid. Elemental analysis, IR spectra and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure. Crystal data for this complex: triclinic system, space group P1, a = 10.387(5), b = 13.112(6), c = 14.229(6) (A), α = 76.176(7), β =83.778(8), y = 71.770(6)°, C35H42N4O12Ni, Mr= 769.44, Z = 2, F(000) = 808, V = 1786.1 (A)3, Dc =1.431 g/cm3, μ = 0.612 mm-1, the final R = 0.0653 and wR = 0.1033 for 9379 (Rint = 0.0244)independent reflections and 4730 observed reflections (I ＞ 2σ(I)). Structural analysis shows that the coordination geometry of Ni(Ⅱ) is a distorted octahedron. A novel two-dimensional structure is constructed from (H2O)4 and (H2O)12 water clusters, and the complex forms a 3-D network supramolecular structure by hydrogen bonds and π-π stacking of neighboring phens.     

化学发光分析法测定绿原酸

本文基于碱性介质中绿原酸对鲁米诺-铁氰化钾化学发光体系的抑制作用,首次建立了绿原酸的化学发光分析法,并探讨了其作用机理。方便简便、迅速、重复性好、灵敏度高。采用该法可测定1.0×10-8g/ml～1.0×10-5g/ml范围内的绿原酸,其检出限达到5.2×10-9g/ml,回收率为104%.     

Influence of humic substances on sorption and methylation processes of inorganic- and organo-tin species

The influence of humic substances on sorption and methylation processes for inorganic- and organotin species is presented. Four sediment samples from different locations of the Rivers Elbe, Mulde and Spittelwasser, Germany, with different organotin and humic contents were selected to extract the humic and fulvic acids. The various fractions—the original sediment, the humic acid, the fulvic acid and the residual sediment—were analysed for their organotin content. The individual buyltin species show quite different distribution patterns. Monobutyltin is found mostly associated with humic acids. Dibutyltin shows a nonunique behaviour. At low total organotin content, dibutyltin is found bonded to humic and fulvic acids, whereas at high organotin content dibutyltin is distributed more with the residual sediment. Most of the tributyltin remains in the sediment unextracted; only small quantities of it are in the fulvic acid fraction. Tetrabutyltin is only in the humic acid fraction when it binds to humic matter; it mostly remains in the sediment. General observations indicate that ionic butyltin species bind to fulvic acids whereas the non-polar tetrabutyltin is not found in the fulvic acid fractions in any of the samples. The appearance of monomethyl- and dimethyl-tin species in the humic and fulvic acid fractions after the alkaline extraction was surprising. There is a correlation between the humic content of the sample and the formation of methyltin species. Evidence is provided by experiments that humic substances act as methylation agents.     

聚丙烯酸接枝聚甲基丙烯酸甲酯共聚物的表面性质及粘度性质的研究

聚丙烯酸接枝聚甲基丙烯酸甲酯共聚物的表面有其特殊性质:水滴在其表面上形成的接触角基本上与其组成无关,而丙烯酸——甲基丙烯酸甲酯无规共聚物的表面接触角却与其组成有密切关系;接枝共聚物在DMF溶液中,其粘度表现出有趣的现象,说明了接枝共聚物在溶液中有微区现象和聚电解质性质     

Response to high acidity and basicity at a platinum electrode in chronopotentiometry

A simple and rapid method is developed to determine the high acidity and the basicity of solutions by chronopotentiometry with a platinum working electrode. The acidity range from 5.0 mol/l H⁺ to 1.0 mol/l OH⁻ can be measured by the adjustment of deposition potential and time. The response mechanism to acidity and basicity has been explored. The transition potential plateau in chronopotentiograms is caused from the oxidation of hydrogen adsorbed on electrode surface.     

原子吸收法在有机分析中的应用（Ⅵ）香烟中氢氰酸的分析

原子吸收法在有机分析中的应用（Ⅵ）香烟中氢氰酸的分析谢志海，郎惠云，高云（西北大学化学系，西安，７１００６９）关键词：氢氰酸，测定，原子吸收光谱香烟中的尼古丁，烟焦油等含氮有机物燃烧后将产生氢氰酸，吸入人体后极为有害。国外在这方面的研究始于七十年代，...     

乳清酸的2.5次微分示波极谱法测定

拟定了乳清酸的2.5次微分示波极谱测定新方法.结果表明在0.8 mol/L HCl介质中,乳清酸产生一灵敏的极谱还原波,峰电位Ep =-0.77 V(vs.SCE);其2.5次微分极谱峰峰电流ep″与乳清酸浓度在4.0×10-8～4.0×10-5 mol/L范围内呈良好线性关系(r=0.999 6,n=9),检测限为1.0×10-8 mol/L;13次平行测量4.0×10-7 mol/L乳清酸的峰电流,所得RSD为1.8%.该方法可直接用于测定牛奶中乳清酸的含量.