N-硝基苯基吡咯酰胺对阴离子识别研究

合成了2个N-硝基苯基吡咯酰胺阴离子识别主体. 通过X射线单晶衍射确定了间位硝基取代物的结构, 氢键及π-π相互作用在该化合物的组装过程中起到了决定性的作用. 利用UV-Vis光谱研究了这两个主体对常见无机阴离子的识别, 结果表明， 它们不仅对F-和H2PO4-离子有比较强的识别能力, 而且在识别发生时还伴随着显著的颜色变化, 因此这两个化合物都可作为阴离子的比色传感器.     

含2-N,N-二甲氨基嘧啶环与噻吩环结构的共轭聚合物的合成及其性能

合成了一种新型单体2-N,N-二甲氨基-4,6-二氯嘧啶(ADNP).以二氯-1,3-双(二苯基磷)丙烷基镍(Ⅱ)作催化剂,通过2,5-二溴噻吩格氏试剂与该单体共聚得到了一种新型共轭聚合物,聚[(2-N,N-二甲胺基嘧啶-4,6-二)-2,5-噻吩](PThPm).采用FT-IR、1H-NMR等测试手段对新型单体与共聚物的结构进行了表征,并用UV-Vis、荧光光谱、X射线衍射、循环伏安、热重分析(TGA)等测试方法对单体和共聚物进行了性能分析.结果表明:共聚物在420 nm处出现UV-Vis吸收峰,在528 nm处出现荧光发射峰;共聚物的DMF溶液存在酸致变色现象,加入CF3COOH和CH3SO3H后,溶液由淡绿黄色转变为淡红色,UV-Vis吸收峰发生红移;PThPm共聚物有一定的结晶性和热稳定性;在-1.8～ 1.8 V之间出现电致变色现象,电极周围的溶液颜色从深蓝色变成深红色.     

Simultaneous micro-determination of nicotinamide and its major metabolites, N1-methyl-2-pyridone-5-carboxamide and N1-methyl-4-pyridone-3-carboxamide, by high-performance liquid chromatography

A simultaneous micro-determination of nicotinamide and its major metabolites, N1-methyl-2-pyridone-5-carboxamide (2-py) and N1-methyl-4-pyridone-3-carboxamide (4-py) by high-performance liquid chromatography is described. The method employs a 7-ODS-L (250 mm X 4.6 mm I.D., particle size 7 microns) column eluted with 10 mM potassium dihydrogenphosphate-acetonitrile (96:4, v/v; pH adjusted to 3.0 by the addition of concentrated phosphoric acid) at a flow-rate of 1.0 ml/min. The UV detector was set at 260 nm. The detection limits for nicotinamide, 2-py and 4-py were 10 pmol (1.22 ng), 2 pmol (304 pg) and 2 pmol (304 pg), respectively, at a signal-to-noise ratio 5:1. Isonicotinamide was used as an internal standard. The technique was applied to the analysis of rat and human urines. The total analysis time was ca. 15 min.     

3—N,N—二甲基—1,3—丙二胺／冰醋酸催化下的Knoevenagel缩合反应

对硝基苯磺酰基乙腈与芳香醛在３－Ｎ，Ｎ－二甲基－１，３－丙二胺（ＤＰＡ）／冰醋酸催化下可顺利地发生Ｋｎｏｅｖｅｎａｇｅｌ缩合反应，生成２－（４－硝基苯磺酰基肉桂腈类化合物，产率８３％～９８％。但与水杨醛反应生成的产物是六元环丙酯，其结构经元素分析，ＩＲ，ＨＮＭＲ和ＭＳ确证。     

3－N，N－二甲基－1，3－丙二胺／冰醋酸催化下的Knoevenagel缩合反应

对硝基苯磺酰基乙腈与芳香醛在３－Ｎ，Ｎ－二甲基－１，３－丙二胺（ＤＰＡ）／冰醋酸催化下可顺利地发生Ｋｎｏｅｖｅｎａｇｅｌ缩合反应，生成２－（４－硝基苯磺酰基肉桂腈类化合物，产率８３％～９８％。但与水杨醛反应生成的产物是六元环内酯，其结构经元素分析、ＩＲ、￣１ＨＮＭＲ和ＭＳ确证。     

N,N-Dimethyl-2-Mercaptoethylammoniumchlorid als Thiolkomponente der OPA-Methode in der Analytik von Milchprodukten

Ohne Zusammenfassung

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N,N-Dimethyl-2-mercaptoethylammonium chloride used as thiol component in the OPA-method for the analysis of milk products

     

Aminomethylation of Thioureas with N,N-Dimethyl-1-(triethylsiloxy)methanamine,Involving Amino Group Exchange

The O-triethylsilylated hemiaminal Et₃SiOCH₂NMe₂ readily transfers the Me₂NCH₂-group to various thioureas under mild conditions and without catalysts or co-reagents. In the reaction with PhNHC(=S)·NHPh, the initially formed mono-substituted derivative PhNHC(=S)NPhCH₂NMe₂ readily rearranges to produce the unsymmetrical thiourea PhNHC(=S)NMe₂ and hexahydro-1,3,5-triphenyl-1,3,5-triazine.

     

A Convenient Synthesis of Diversely Substituted N,N-Dimethyl-4-oxo-2-(E)-alkenamides

An efficient synthesis of diversely substituted N,N-dimethyl-4-oxo-2-(E)-alkenamides is reported. These derivatives were obtained in three steps from I,4benzodioxin with fair to good yields     

Photochemistry of 2-Allyl-3-oxo-2,3-dihydro-1H-pyrrole-2-carboxyalates

On acetone-sensitized irradiation the title compounds 3a–c are converted to 2-allyl-3-hydroxy-1H-pyrrole-2-carboxylates 4 in reasonable yields.     

一锅法N,N-二甲基-4-氨基吡啶催化合成蒎酮酸酯

以天然产物松节油的主要成分a-蒎烯和醇为原料,二氯甲烷为溶剂,N,N-二甲基-4-氨基吡啶(DMAP)催化下经臭氧化分解反应,一锅法合成了6种蒎酮酸酯类化合物,反应温度为40℃,反应时间为4h,6种蒎酮酸酯产率均在60％以上.该方法操作简便,条件温和,且产率较高,是合成蒎酮酸酯类化合物的一种简易可行的方法.采用1H NMR,IR,MS对6种化合物的结构进行了表征.     

Polymerization of 5-(1-adamantyloxy)-2H-pyrrole-2-one

5-(1-Adamantyloxy)-2H-pyrrole-2 one has been homopolymerized and copolymerized with a variety of comonomers. Polymerization was conducted in chloroform solutions with α,α′-azobisisobutyronitrile initiator. Evidence of polymerization was achieved through infrared and NMR spectra and elemental analysis. Moderate molecular weights were achieved as determined by inherent viscosity measurements and gel-permeation chromatography. Photolysis of the polymers with ultraviolet radiation induces a photochemical rearrangement resulting in the formation of isocyanate functions. A proposed mechanism suggests α-cleavage of the carbonyl to give a 1,5-diradical which rearranges to a 1,3-diradical with subsequent ring closure to give a polymer with cyclopropyl isocyanate moieties in the backbone. DSC data show all polymers to display intense exothermic activity at temperatures near 200°C on initial heating and glass transition temperatures between 194 and 245.5°C on subsequent heating. Thermolysis of the homopolymer causes rearrangement to poly[N-(1-adamantyl) maleimide]. Reactivity ratios were determined for the systems styrene (M₁) and 5-(1-adamantyloxy)-2H-pyrrole-2-one (M₂) (r₁ = 0.06, r₂ = 0.07) and methyl methacrylate (M₁) and 5-(1-adamantyloxy)-2H-pyrrole-2-one(M₂) (r₁ = 0.35, r₂ = 0.70). Q and e values for 5-(1-adamantyloxy)-2H-pyrrole-2-one are 3.40 and 1.59, respectively.