取代肉桂酰甘氨酸酯的合成

在N-甲基吡咯烷酮(NMP)促进下,取代肉桂酸(1a^1g)与二氯亚砜(SOCl2)在20℃酰氯化反应0.5 h,再加入甘氨酸乙酯盐酸盐,在40℃下酰胺化反应4 h,n(取代肉桂酸)/n(SOCl2)/n(甘氨酸乙酯盐酸盐)=1.0/1.2/1.4,合成了一系列取代肉桂酰甘氨酸乙酯(2a^2g),其结构经1H NMR、13C NMR、IR和MS(EI)确证。并探讨了NMP促进取代肉桂酰甘氨酸乙酯反应可能的机理。     

Neue acetonylsubstituierte Azole II. 3-Acetonyl-1,2,4-oxadiazole, 2-Acetonyl-1,3,4-oxadiazole und 5-Acetonyl-1,2,4-thiadiazole

3-Acetonyl-1,2,4-oxadiazoles and 2-acetonyl-1,3,4-oxadiazoles are accessible starting with the ketal of acetoacetamide oxime and the ketal of acetoacetic acid hydrazide, respectively. 5-Acetonyl-1,2,4-thiadiazoles are obtained from 5-chloro-1,2,4-thiadiazoles andtert.-butyl acetoacetate. These Acetonyl-azoles are starting materials for three series of azolylvinyl phosphates and phosphonates.

Herrn Prof. Dr.Klaus Weissermel zu seinem 60. Geburtstag.     

Carboxylic Acids from <Emphasis Type="Italic">Phyllanthus urinaria</Emphasis>

Five compounds, terephthalic acid mono-[2-(4-carboxy-phenoxycarbonyl)-vinyl] ester (1), (E)-3-(5′-hydroperoxy-2,2′-dihydroxy[1,1′-biphenyl]-4-yl)-2-propenoic acid (2), 3,4,5-trihydroxybenzoic acid (3), succinic acid (or butanedioic acid) (4), and 2,3,4,5,6-pentahydroxybenzoic acid (5), were isolated from Phyllanthus urinaria. The structures of these compounds were elucidated by means of spectral techniques including IR, MS, and 1D/2D NMR. 1 and 2 are new compounds.__________Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 14–17, January–February, 2005.     

树枝状十二酯的合成

以乙二胺和丙烯酸十二酯为原料，甲醇为溶剂，采用迈克尔加成反应合成了低代的树枝状十二酯。探讨了反应条件对树枝状十二酯收率的影响。乙二胺2mL(30mmol)，n(乙二胺)：n(丙烯酸十二酯)=1：6，甲醇占反应液总体积的50％，反应温度40℃，反应时间48h，产率54．9％。     

Controlled synthesis of poly(acetone oxime acrylate) as a new reactive polymer: Stimuli-responsive reactive copolymers

Acetone oxime acrylate has been synthesized as a new active ester monomer. Free radical polymerization yielded a reactive polymer soluble in various organic solvents, such as chloroform, dioxane, DMSO, acetone, methanol, dichloromethane, DMF, and ethanol. Controlled radical polymerization of acetone oxime acrylate was successfully conducted using the RAFT, NMP and Iniferter method. Partly polymer analogous reaction with N-isopropylamine resulted in the reactive copolymer poly(N-isopropylacrylamide-co-acetone oxime acrylate), which featured a lower critical solution temperature (LCST) of 61 °C in water. Further, the reactivity of the copolymer was exemplary proven by complete reaction with ammonia yielding poly(N-isopropylacrylamide-co-acrylamide), which does not possess a LCST.     

蔗糖酯示波极谱分析法的研究

蔗糖酯分子在碱性条件下，加热水解为蔗糖和硬酯酸，在ｐＨ＞１０的ＮＨ＿３·Ｎ＿２Ｏ－（ＮＨ＿３）＿３Ｃ＿６Ｈ＿５Ｏ＿７体系中，于示波极谱仪上，峰电位─０．９１Ｖ处出现一灵敏度高和稳定性好的极谱图，其浓度从０．０２～０．２８ｍｇ／ｍＬ与峰电流呈线性关系，最低检出限为０．００４ｍｇ／ｍＬ，相对标准偏差为１．３％。     

二元酸茄呢醇乳糖和麦芽糖酯合成及生是活性测试研究

七个二元酸茄呢基单酯分别与溴代乙酰乳糖和溴代乙酰麦芽糖在四丁基溴化铵 催化下反应生成对应的糖酯，制得的十四个化合物均为新化合物，其结构经过了元 素分析、IR，~1H NMR和MS确证。并对六个化合物做了KB（人口腔上皮癌细胞）、 Bel-7402（人肝癌细胞）、HCT-8（人结肠癌细胞）三种癌细胞初步生理活性测试。     

Thermal characterization and thermal degradation of poly(norbornene-2,3-dicarboxylic acid dialkyl esters) synthesized by vinyl addition polymerization

The thermal properties and degradation behaviors of poly(norbornene-2,3-dicarboxylic acid dialkyl esters) (PNB-dialkyl esters) (alkyl = Me (PNB-Me), Et (PNB-Et), Pr (PNB-Pr), and Bu (PNB-Bu)) were investigated by thermogravimetric analysis (TGA) in dynamic conditions and by infrared (IR) spectroscopy. The PNB-dialkyl esters show good thermal stability up to 350 °C, and the thermal stability decreases in the order Me > Et > Pr > Bu with the increase in size of side chain. The effect of side-chain size on the thermal degradation behaviors of PNB-dialkyl esters is evidenced by one-step thermal degradation profile for PNB-Me while two-step thermal degradation profile for PNB-Et, PNB-Pr, and PNB-Bu. Transformation is deduced to undergo β-hydrogen elimination and formation of anhydride group in the first stage of thermal degradation reaction according to TGA and IR results for PNB-Et, PNB-Pr, and PNB-Bu. The apparent activation energy and thermal degradation model of PNB-dialkyl esters are estimated by means of Ozawa-Flynn-wall method and Phadnis-Deshpande method, respectively.     

Zur Synthese von fungizid wirksamen Isocamphanderivaten: Synthesen in der Isocamphanreihe, 34. Mitt.

Summary Some esters of isocamphenilanic acid (4) have been prepared and tested for their fungicidal and insecticidal activity. Esters of various acids with isocamphanyl ethylalcohol (5) have also been synthesized and included in the fungicidal/acaricidal/insecticidal screening programme. All esters bear a geminal dimethyl group at C-3 of the bicyclus which is important because of its shielding effect.

     

Carbon-bromine cleavage by dimethyl sulfoxide: the key step of C(5) functionalization of push-pull 2-alkylidene-4-oxothiazolidine vinyl bromides

Push-pull 2-alkylidene-4-oxothiazolidine vinyl bromides undergo efficient C(5) functionalization through DMSO-assisted carbon-bromine cleavage, followed by a bromine transfer-substitution (or elimination) sequence. A mechanism for this novel transformation is proposed.