一种高亲核怀长链咪唑肟的合成与反应

报道了一种新的高亲核长链咪唑肟N-十四烷基咪唑-2-甲醛肟的设计与合成， 并比较了它及其他长链咪唑肟与有机磷酸酯二苯基、对硝基苯基磷酸酯（PNPDPP） 、对硫磷及V_x的反应活性。结果表明，该肟对PNPDPP、对硫磷等磷酸酯反应活性 很高，超过目前已报道的反应活性最强的肟基试剂5～10倍，可用于毒性高且难以 分解的磷酸酯消毒与防护。     

氯化苯甲醛肟的简便合成

以廉价的三氯异氰尿酸和取代的苯甲醛肟为原料合成了一系列的氯化苯甲醛肟,方法操作和后处理简便.并考察了反应条件对产物收率的影响,确定了最佳的反应条件:苯甲醛肟与三氯异氰尿酸的摩尔比为2∶1左右,溶剂为四氢呋喃,温度0～5℃,反应时间4～6 h,产物收率可达到90%以上.     

Calorimetric Determination of Phosphorylated Serum Cholinesterase and Its Reactivation by an Antidote

Abstract

Serum cholinesterase, inhibited in vitro up to 92% by 0, 0 dimethyl-2, 2-dichlorovinyl phosphate (4.52 × 10^?9 mole/ml of 40% serum), was reactivated up to 35% with 2-pyridine aldoxime methiodide (3.5 × 10^?6 mole/ml of 40% serum). Evaluation was based on the reaction rate between cholinesterase and acetylcholine chloride (2.2 × 10^?6 mole) measured with a microcalorimeter. It was thus possible to approximate the “normal” or pre-exposure level of serum cholinesterase, while simultaneously determining the extent of poisoning.     

Unusual transformation of trimethylsilyloxyisoxazolidines initiated by the fluoride ion

It was found that opening of the isoxazolidine ring of 6a-isopropenyl-1/-trimethylsilyloxy-3, 3a,4,5,6,6a-hexahydro-(1H)-cyclopent[c]isoxazoles by the F^– ion initially gives an intermediate, a tertiary nitrosocompound detected by UV and NMR spectroscopy. Its transformation, finally, into ,-unsaturated aldoximes probably involves an unprecedented allylic migration of the nitroso group.Deceased.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 461–464, March, 1994.     

Nitrile Synthesis with Aldoxime Dehydratases: A Biocatalytic Platform with Applications in Asymmetric Synthesis,Bulk Chemicals,and Biorefineries

Nitriles comprise a broad group of chemicals that are currently being industrially produced and used in fine chemicals and pharmaceuticals, as well as in bulk applications, polymer chemistry, solvents, etc. Aldoxime dehydratases catalyze the cyanide-free synthesis of nitriles starting from aldoximes under mild conditions, holding potential to become sustainable alternatives for industrial processes. Different aldoxime dehydratases accept a broad range of aldoximes with impressive high substrate loadings of up to >1 Kg L⁻¹ and can efficiently catalyze the reaction in aqueous media as well as in non-aqueous systems, such as organic solvents and solvent-free (neat substrates). This paper provides an overview of the recent developments in this field with emphasis on strategies that may be of relevance for industry and sustainability. When possible, potential links to biorefineries and to the use of biogenic raw materials are discussed.     

A Convenient Method for the Preparation of Nitriles from Aldehydes and Aldoximes

Nitriles were prepared from their corresponding aldehydes or aldoximes with the Vilsmeier reagent in a one-pot reaction or without another solvent at room temperature in 74-98% yields.     

Spectrophotometric Determination of Manganese with 4(5)-Imidazolealdoxime (Imalox)

Abstract

A method is described for the spectrophotometric determination of manganese by means of its complex with 4(5)-imidazolealdoxime, IMALOX, formed in alkaline medium. The colour system has its absorption maximum at 350 nm and obeys Beer's law over the range 0.8–8.0 μg of Mn per ml. The optimum range is 1–5 μg m^?1. The molar absorptivity is 7850 1 mol^?1 cm^?1. Relatively few ions interfere, and these can be masked with cyanide, tartrate and NTA. The experimental results have been critically analyzed and a comparison with the main spectrophotometric reagents for manganese is presented.     

SO3H-Functionalized Ionic Liquids: Green, Efficient and Reusable Catalysts for the Facile Dehydration of Aldoximes into Nitriles

Easily synthesized aldoximes have been converted to the corresponding nitriles under very mild conditions by a simple reaction using two halogen‐free SO₃H‐functionalized ionic liquids, 3‐methyl‐1‐(4‐sulfonic acid)butylimi‐ dazolium hydrogen sulfate [MIM(CH₂)₄SO₃H][HSO₄] and 1‐(4‐sulfonic acid)butylpyridinium hydrogen sulfate [PY(CH₂)₄SO₃H][HSO₄], as catalyst and reaction medium without any additional organic solvent. The method was equally effective for aromatic aldoximes bearing electron‐donating and electron‐withdrawing substituents. Taking into account environmental and economical consideration, the protocol presented here has the merits of environmentally friendly, simple operation, easy work‐up and very good yields. The catalysts could be recycled and reused for several times without noticeably decreasing in their catalytic activities.     

A Facile One-Pot Conversion of Aldehydes into Nitriles

A facile one-pot synthesis of nitriles starting with aldehydes has been developed employing hydroxylamine hydrochloride in dimethylsulfoxide at 100°C.     

聚合物负载苯亚硒酸试剂促进过氧化氢氧化肟转变成羧酸酯

在30％双氧水和醇组成体系中，聚合物负载的苯亚硒酸试剂可有效地促进过氧化氢氧化肟转变成羧酸酯；相应伯醇和仲醇的羧酸酯的产率中等到良好，但在含叔醇的体系中没有相应的羧酸酯生成，聚合物负载的苯亚硒酸试剂无需处理即可循环使用，其活性无明显下降。