Heterogeneous asymmetric reactions. 23. Enantioselective hydrogenation of ethyl pyruvate over cinchonine- and α-isocinchonine-modified platinum catalysts

The enantioselective hydrogenation of ethyl pyruvate to (S)-ethyl lactate over cinchonine- and -isocinchonine-modified Pt/Al₂O₃ catalysts was studied as a function of modifier concentration and reaction temperature. The maximum enantioselectivities obtained under the applied mild conditions were 89% ee using cinchonine (0.014 mmoldm^–3, 1 bar H₂, 23°C, 6% AcOH in toluene), and 76% ee in the case of -isocinchonine (0.14 mmoldm^–3, 1 bar H₂, –10°C, 6% AcOH in toluene). Since -isocinchonine of rigid structure exists only in anti-open conformation these data provide additional experimental evidence to support the former suggestion concerning the dominating role of anti-open conformation in these cinchona-modified enantioselective hydrogenations.     

纤维素LiCl/DMAc溶液流变性能研究

本文研究了9％LICI／DMAC纤维素溶液的流变性能。在该体系中纤维素溶液是非牛顿流体，属于假塑性流体，具有典型的幂律性。通过幂律方程拟合计算，其稠度系数为60～135，流动特性指数为0.62～0．70。随着浓度增大，稠度系数增大和流动特性指数降低；温度的变化对流动特性指数的影响不大，温度升高，流动特性指数略有减小，而稠度系数相对增大。溶液的粘度随着剪切速率的增大，开始时粘度迅速降低，后趋于稳定，这可能与纤维素分子在溶液中的取向有关。在不同剪切速率下，其流动活化能为23～30kJ．     

Effect of partial replacement of di(2‐ethyl hexyl)phthalate,by a polymeric plasticizer,on the permeability and leaching properties of poly(vinyl chloride)

Acrylonitrile butadiene rubber (NBR) was used as a polymeric plasticizer in poly(vinyl chloride) (PVC) for the partial replacement of di(2‐ethyl hexyl)phthalate (DEHP). The effect of this partial replacement on DEHP leaching from the PVC was evaluated at 10, 25, and 40°C. The study shows that the incorporation of NBR reduces the rate of DEHP leaching, the reduction being prominent at lower temperatures. Gas permeability of the NBR‐modified samples was also evaluated at the above temperatures using oxygen and carbon dioxide. A reduction in gas permeability is observed in NBR‐modified samples compared to the PVC plasticized with DEHP alone particularly in the case of carbon dioxide. Water vapor transmission rates of the NBR‐modified samples are higher than that of the control sample. The NBR‐modified PVC sample was found to be noncytotoxic in the in vitro cytotoxic evaluation both by direct contact and test on extract methods. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:4720–4727, 2006     

2—（2—氨基噻唑—4—基）—2—甲氧基亚氨基乙酸乙酯的合成

以乙酰乙酸乙酯为起始原料,经肟化、甲基化、溴化和缩合四步反应合成2-(2-氨基噻唑-4-基)-2-甲氧基亚氨基乙酸乙酯,总收率63.14％,高于文献报道。     

过氧化甲乙酮合成研究

研究了在酸性催化剂存在下，以邻苯二甲酸二丁酯作溶剂，由双氧水和甲乙酮作用制取过氧化甲乙酮溶液的工艺，并得到最佳工艺条件。结果表明，产品性能优良。     

Recoverable shear strain of liquid crystal‐forming concentrated hydroxypropyl cellulose solutions

The recoverable shear strain (S_R) for the liquid crystal‐forming hydroxypropyl cellulose solutions was determined by means of a concentric cylinder rotational apparatus as functions of shear stress prior to recovery and concentration of the solutions at 30°C. S_R greatly depended on shear stress and concentration; the phase of the solution (the single phase or biphase) governed the dependences of S_R on stress and concentration. S_R increased with increasing stress for the single phase and decreased for the biphase. S_R seemed to be related to the die swell (B): S_R ∝ Bⁿ. S_R exhibited a maximum and a minimum with respect to concentration. S_R for the cellulosic cholesteric liquid crystalline solutions was greater than that for the isotropic solutions. A model was proposed for explaining the greater S_R. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 865–872, 2002     

N－氰基乙亚胺酸乙酯含量的气相色谱分析

采用GC-900气相色谱仪、3%PEG-12000/Chromosorb880AWDMCS填充柱和FID检测器,以水杨酸甲酯为内标物测定N-氰基乙亚胺酸乙酯含量,回收率在98.5%—101.8%之间,标准偏差为0.27%,变异系数为0.27%。     

Physical agglomeration behavior in preparation of cellulose‐N‐methyl morpholine N‐oxide hydrate solutions by simple mixing

The different melting temperatures of N‐methyl morpholine N‐oxide (NMMO) hydrates in the cellulose–NMMO hydrate solution may be explained by the rather different crystal structures of NMMO hydrates, which are determined by the amount of the hydrates. The preparative process of cellulose–NMMO hydrate solution may result in cellulose structural change from cellulose I to cellulose II, depending on the amount of the hydrate. Mixtures of cellulose and NMMO hydrate in a blender was changed from the granules to slurry with increasing mixing time at 60–70°C, which is below the melting point of the NMMO hydrate. In the case of 15 wt % cellulose–NMMO hydrate granules, which were made by mixing for 20 min, the melting points of various NMMO hydrates were obtained as 77.8°C (n = 0.83), 70.2°C (n = 0.97), and 69.7°C (n = 1.23), respectively, depending on the hydrate number. However, the melting points of cellulose–NMMO hydrate slurry and solution were shifted lower than those of cellulose granules, while the mixing time of slurry and solution are 25 and 35 min, respectively. These melting behaviors indicate instantaneous liquefaction of the NMMO hydrate and the diffusion of the NMMO hydrate into cellulose during mixing in a blender. When cellulose was completely dissolved in NMMO hydrate, the crystal structure of cellulose showed only cellulose II structure. In the cellulose–NMMO products of granules or slurry obtained by high‐speed mixing, which is a new preparation method, they still retained the original cellulose I structure. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1687–1697, 2004     

Analysis of saturated free fatty acids from pollen by HPLC with fluorescence detection

A sensitive method for the determination of free fatty acids using 2‐(2‐(anthracen‐10‐yl)‐1H‐naphtho[2,3‐d]imidazol‐1‐yl) ethyl‐p‐toluenesulfonate (ANITS) as tagging reagent with fluorescence detection has been developed. ANITS could easily and quickly label fatty acids in the presence of the K₂CO₃ catalyst at 90 °C for 40 min in N,N‐dimethylformamide solvent. From the extracts of rape bee pollen samples, 20 free fatty acids were sensitively determined. Fatty acid derivatives were separated on a reversed‐phase Eclipse XDB‐C₈ column by HPLC in conjunction with gradient elution. The corresponding derivatives were identified by post‐column APCI/MS in positive‐ion detection mode. ANITS‐fatty acid derivatives gave an intense molecular ion peak at m/z [M+H]⁺; with MS/MS analysis, the collision‐induced dissociation spectra of m/z [M+H]⁺ produced the specific fragment ions at m/z [M–345]⁺ and m/z 345.0 (here, m/z 345 is the core structural moiety of the ANITS molecule). The fluorescence excitation and emission wavelengths of the derivatives were λ_ex = 250 nm and λ_em = 512 nm, respectively. Linear correlation coefficients for all fatty acid derivatives are >0.9999. Detection limits, at a signal‐to‐noise ratio of 3 : 1, are 24.76–98.79 fmol for the labeled fatty acids.     

乙酸乙酯与乙酸正丙酯的切换式连续生产

作者在对乙酸乙酯、乙酸异丙酯、乙酸正丙酯和乙酸丁酯的现有生产工艺进行分析后,以乙酸乙酯和乙酸正丙酯为研究对象,在以往对两者研究的基础上,提出了乙酸乙酯与乙酸正丙酯切换式连续生产的工艺流程,并且通过模拟计算和小试验证证明,在同样的生产装置上,可以分别连续生产乙酸乙酯和乙酸正丙酯,采用该工艺生产乙酸乙酯能耗低于传统工艺12%,生产乙酸正丙酯比原有工艺可以提高收率2%。