2,6-二氯-4-乙酰基苯基磷酸的合成

制备了酸性磷酸酶检测底物2，6-二氯-4-乙酰基苯基磷酸酯（DCAP-P）。以2，6-二氯苯酚为原料，经酰化反应、AlCl3催化F-C重排、碱化成盐、磷酯化、水解等5步反应，制备了DCAP-P，并对F-C重排、磷酯化条件进行了改进。     

Efficient Oxidation of Alcohols to Carbonyl Compounds by N,N‐Dichloro‐4‐Methylbenzenesulfonamide under Mild Conditions

A number of aldehydes and ketones were prepared by oxidation of alcohol by N,N‐dichloro‐4‐methylbenzenesulfonamide under mild and neutral conditions in good to high yield in dichloromethane at room temperature.     

2-(3,5-二氯-2-吡啶偶氮)-5-二甲氨基苯胺与铂(Ⅳ)显色反应的研究

研究了２－（３，５－二氯－２－吡啶偶氮）－５－二甲氨基苯胺（３，５－ｄｉＣｌ－ＰＡＤＭＡ）与铂（Ⅳ）的显色反应及铂配合物的质子化行为。结果表明，在０．０４～０．４８ｍｏｌ／Ｌ的Ｈ２ＳＯ４溶液中，于加热的条件下，试剂可与铂（Ⅳ）形成稳定的１∶２绿蓝色ＰｔＬ２Ｈ２＋２配合物，其最大吸收波长位于６３４ｎｍ，表观摩尔吸光系数为９．７３×１０４Ｌ·ｍｏｌ－１·ｃｍ－１，桑德尔灵敏度为０．００２μｇ·ｃｍ－２。铂配合物的三级质子化常数分别为：ｌｇＫａ１＝３．９１，ｌｇＫａ２＝－２．２１，ｌｇＫａ３＝－３．３７。较大量的常见金属离子及除钯、钌外的其它贵金属离子不干扰测定。利用Ｐｔ，Ｐｄ与试剂反应所需的温度差异，可以用差减法消除微量Ｐｄ的干扰．铂（Ⅳ）浓度在每１０ｍＬ０～７．５μｇ范围内符合比尔定律。所拟方法用于二次合金管理样－８８及催化剂中微量铂的测定，结果满意。     

Advances in Organophosphorus Chemistry Based on Dichloro(methyl)phosphane

Besides phosphorus trichloride and phosphane, dichloro(methyl)phosphane is gaining importance as a starting material for the synthesis of organophosphorus compounds. It provides ready access to phosphonic, phosphinic and phosphonous acid derivatives, as well as their secondary products. The synthetic and application potential of organophosphorus compounds—based on industrially produced dichloro(methyl)phosphane—is illustrated by means of numerous examples.     

From σ to π Coordination: Tetraisopropylcyclopentadienyl dichlorides [(C5HR4)ECl2] (R = CHMe2) of phosphorus,arsenic, antimony,and bismuth

[(C₅HR₄)PCl₂] ( 1a ), [(C₅HR₄)PBr₂] ( 1 b ), [(C₅HR₄)AsCl₂] ( 2 ), and [(C₅HR₄)SbCl₂] ( 3 ), have been obtained from the corresponding pnicogen trihalides and sodium tetraisopropylcyclopentadienide (R = CHMe₂). The molecular structures of 1, 2 , and 3 as well as the related structure of [(C₅HR₄)BiCl₂] ( 4 ) display increasing π character of hetero atom to cyclopentadienyl bonding with increasing metallic character of the hetero atom.     

Structures and Magnetic Properties of Two Copper(II) Complexes with 2,5‐Dichloro‐3,6‐Dihydroxy‐1,4‐Benzoquinone Dianionic and Tetrachloroquinone Ligand

The polynuclear copper(II) complex [Cu₂(Hdpa)₂(μ‐ClDHBQ)(ClO₄)₂]_n, 1 is bridged by ClDHBQ^?2 (2,5‐dichloro‐3,6‐dihydroxy‐1,4‐benzoquinone dianionic) and 2,2′‐dipyridylamine (Hdpa). In the axial position, Cu is connected with the oxygen atom of ClO. The perchlorate anion may be envisaged as a monodentate O‐bound ligand. Through the bond bridge of O–Cu … O–Cl, the binuclear compound [Cu₂(Hdpa)₂(μ‐ClDHBQ)(ClO₄)₂] is strung together into a long chain compound. Tetrachlorocatechol underwent partial oxidation/hydrolysis/dechlorination processes to produce ClDHBQ^?2. The other mononuclear complex [Cu(Hdpa)(TeCQ)](DMF), 2 , in which tetrachloroquinone (TeCQ) was produced by oxidation of tetrachlorocatechol (TeCC), therefore complex 2 is in the quinone form. The magnetic susceptibility measurements show antiferromagnetic coupling with J = ?11.9 cm^?1, θ = 2.6 K, and g = 2.05 for complex 1. Complex 2 exhibits the typical paramagnetic behavior of s = 1/2.     

测定气体水合物相平衡数据的高压 PVT装置

建立了一套用于研究气体水合物的高压流体PVT（压力－体积－温度）测试系统。分别利用低压和高压传感器在温度268－283．2K时,压力6－40．2kPa和4600－7200kPa范围内采用恒温试压法分别对1,1－dichloro-1-fluoroethane(1,1二氯－1－氟乙烷）和甲烷气体水合物相平衡点进行了测试;并将所得两组数据与文献值相比较。该装置温度、压力范围较宽,可用于气体水合物相平衡实验。     

Element—Element-Bindungen. VII. Intermolekulare Wechselwirkungen bei Dihalogen(phenyl)stibanen

Element—Element Bonds. VII. Intermolecular Interactions in Dihalogen(phenyl)stibanes In keeping with the literature dichloro(phenyl)stibane (1) may be obtained in a quantitative yield via a metathesis reaction between antimony(III) chloride and triphenylstibane; the dibromo (2) and diiodo (3) derivatives are synthesized by halogen exchange with phosphorus(III) bromide or sodium iodide, respectively. X-ray structure determinations at ?120±3°C (R = 0,044/0,041/0,024) show the series of compounds to crystallize isotypically in the triclinic space group P1 . The molecules are associated two-dimensionally by a moderately excentric η³-Sb··arene interaction and two Sb··halogen contacts each. Provided that the phenyl ligand is being substituted by its centre, the coordination geometry of the antimony atom may be described as a distorted octahedron. The crystal structure represents a variant (hettotype) of the bismuth(III) iodide type.     

Evidence for a nucleophilic anti-attack on the cleaved C(2)-oxygen bond in Cl2AlH-catalyzed ring-opening of 2-substituted 1,3-dioxolanes

The Cl₂AlH-mediated ring-opening of 2-substituted cis-4-methyl-5-trifluoromethyl-1,3-dioxolanes was found to occur with regioselective cleavage of the O1-C2 bond by attack of the aluminum hydride from the direction anti to the departing oxygen. This stereochemical outcome, which appears to be unprecedented in the reductive cleavage of chiral acetals by aluminum reagents, is interpreted on the basis of theoretical calculations.     

3，5－二氯－4－羟基苯甲醛的合成

通过正交设计和单因素分析对对甲苯酚氧化氯代法制３，５－二氯－４－羟基苯甲醛的合成条件进行了优化，在更为温和的条件下，目的产物的收率达９０～９２％。