4'-磺酰腙苯并-15-冠-5的合成及阴离子识别研究

由苯并-15-冠-5经磺酰化、肼解两步合成了4’-磺酰肼苯并-15-冠-5(2).后者与芳香醛在室温下发生缩合制得了一系列未见文献报道的冠醚化磺酰腙类化合物3a～3h,产物经元素分析,IR,1H NMR,13C NMR,MS确证了其结构.利用紫外-可见吸收光谱考查了其对不同阴离子的识别作用,结果表明,化合物3d,3e,3h对碱性较强的阴离子有较强的选择性识别作用.     

A study of sulphonated and oxidized coals by thermal analysis

Earthy and xylytic brown coals from Poland have been sulphonated with 98% sulfuric acid at temperatures of 60°, 90° and 140°C. The main exothemic peak shifts to higher temperatures with increase in sulphonation reaction temperature whereas overall weight loss to 1000°C decreases. DTA curves of earthy and xylytic coals sulphonated at higher temperatures are similar, even though DTA curves of the unmodified coals differ appreciably. Thermal decomposition of earthy coal oxidized by nitric acid follows a different pattern. Nitric acid causes oxidation and depolymerization of the organic components and this is reflected in the shapes of DTA and TG curves of oxidized coals. As the nitric acid concentration and reaction temperature increase, the main exothermic peak shifts to lower temperatures (from 330°C for basic coal to 270°C for coal oxidized with 30 and 50% nitric acid). The weight loss is higher for oxidized coal than for coal unmodified by nitric acid.     

PHOSPHINES SULFONEES ASYMETRIQUES V.ACINETIQUE DE SULFONATION DES PHOSPHINES

Abstract

La sulfonation de diphosphines de type-1,2, 1–3 et 1–4 (dppe, dppp, dppb) est ttudite. II est montré que la sulfonation est plus rapide pour les diphosphines-1,4 que pour les diphosphines-1,3 et 1,2. Les conditions permettant d'accéder à la tétrasulfonation sont précisées, ainsi que celles conduisant à un mélange riche en phosphées disulfoées. Cette étude a été étendue aux diphosphines chirales (Cyclobutanediop. BDPP, Chiraphos).

The sulfonation of 1,2, -1,3 and -1,4 diphosphines (dppe, dppp, dppb) is studied. It is shown that the sulfonation is faster for 1,4-diphosphines than for -1,3 and -1,2 diphosphines. The conditions affording the tetrasulfonation are described, and also those allowing the obtention of a mixture containing large amounts of disulfonated diphosphines. This study is extended to chiral diphosphines (Cyclobutanediop, BDPP, Chiraphos).     

4'-磺酰腙苯并-15-冠-5的合成及阴离子识别研究

由苯并-15-冠-5经磺酰化、肼解两步合成了4'-磺酰肼苯并-15-冠-5 (2). 后者与芳香醛在室温下发生缩合制得了一系列未见文献报道的冠醚化磺酰腙类化合物3a～3h, 产物经元素分析, IR, ¹H NMR, ¹³C NMR, MS确证了其结构. 利用紫外－可见吸收光谱考查了其对不同阴离子的识别作用, 结果表明, 化合物3d, 3e, 3h对碱性较强的阴离子有较强的选择性识别作用.     

3-氨基-4-氨甲基苯磺酸钠的合成与表征

以邻硝基甲苯为原料,经磺化,光氯化,Holfmann氨化及水合肼还原合成了未见文献报道的3-氨基4-氨甲基苯磺酸钠,其结构经^1H NMR,IR,MS及元素分析表征。纯度达99．2％（HPLC）,总收率62．8％。     

Preparation,Characterization and Anticoagulant Activity of Guar Gum Sulphate

Guar gum was chemically modified by sulphonation using chlorosulphonic acid (ClSO₃H) as a reagent. Effects of molar ratio of ClSO₃H to glucopyranosic unit (ClSO₃H/GU), reaction time and reaction temperature on the degree of sulphonation (DS) and molecular weight (Mw) of products were studied. The structures of guar gum sulphate were investigated by GPC, FT‐IR and UV‐Visible spectroscopy. Activated partial thromboplastin time (APTT) assay showed that the guar gum sulphate could inhibit the intrinsic coagulant pathway. The anticoagulant activity strongly depended on the DS and Mw of polysaccharides. DS>0.56 was essential for anticoagulant activity. The guar gum sulphate with the DS of 0.85 and the Mw of 3.40×10⁴ had the best blood anticoagulant activity.     

Sulphonated poly(ether ether ketone): synthesis and characterisation

The paper describes the sulphonation of commercially available poly(ether ether ketone) PEEK (GATONE^TM, Gharda Chemicals Limited, India and VICTREX^®, ICI Limited, UK) by using concentrated sulphuric acid. The concentration of GATONE in conc. H₂SO₄ was varied from 4-10% (w/v) whereas in VICTREX^® the concentration was 4% (w/v). The temperature was varied from 35-55°C and the duration of reaction was 3-7 h. Structural characterisation of sulphonated polymers was done by elemental analysis, FT-IR and ¹H-NMR spectroscopy. On the basis of elemental analysis, the extent of sulphonation of GATONE was found to be 57-75%. The extent of sulphonation as determined by ¹H-NMR in case of GATONE was in the range of 53-80% and for VICTREX 58-87%. Thermal analysis, proton conductivity and water uptake of these samples were also studied. Proton conductivity of the films was comparable to the perflourinated polymer (Nafion).