烷基膦酸单酯的合成

用烷基膦酸二酯催化水解合成了相应的酸性单酯。首次建立了用叔丁基氯制成的Grignard试剂与亚磷酸二酯反应、继而用Todd碱性氧化法合成高位阻叔丁基膦酸单酯的新的合成路线, 这一合成路线比用Clay反应、继而醇解和水解的方法得率高。     

相转移催化合成苯基烷氧羰基甲基次膦酸酯和二苯基烷氧羰基甲基氧化叔膦

液-液相转移催化 P-烷基化反应的研究工作还不多。Kem 等曾用亚磷酸二烷基酯或二烷基氧化膦与氯代的取代乙酰胺通过液-液相转移法合成了取代胺基羰基与甲基膦酸酯及氧化叔膦。我们曾研究了亚膦酸二烷基酯与氯     

有机磷化合物的研究XXIII:烷基膦酸二烷基酯的取代基结构参数与其水解速率常数的相关分析

为研究烷基膦酸酯在水解反应中的结构效应,合成了具有不同结构的烷基膦酸二烷基酯,并测得它们在不同温度时的碱性水解速率常数.     

有机磷化合物的研究 ⅠⅣ.合成烷基膦酸单酯衍生物的新方法

Atherton与Todd等1945年就用亚磷酸二烷基酯在四氯化碳中与有机胺反应得到二烷基磷酰胺.我们曾成功地由二烷基亚磷(膦)酸在四氯化碳存在下与多种亲核试剂反应合成二烷基磷(膦)酸酯及其衍生物.实验表明二烷基亚膦酸的反应性和亚磷酸二烷基酯有很大差别,为进一步考察不同的三配位磷化合物在该反应中的反应性能,我们合成了己基亚膦酸单烷基酯并在四氯化碳中与各种亲核试剂进行氧化膦酰化反应,制得了相应的己基膦酸单酯衍生物,得率良好,为合成烷基膦酸单酯衍生物的新方法.     

Wittig-Horner 反应合成维A酸酯的改进方法

改进了Wittig-Horner反应合成维A酸酯的方法,利用3-甲基5-(2,6,6-三甲基-1-环已烯-1-基)-1,3(或1,4)-戊二烯膦酸二烷基酯直接与五碳醛反应合成目标产物,省掉了碱催化下的双键重排反应。将含有C^1末端双键的膦酸二烷基酯直接用于wittig-Horner反应。     

改进的亚磷酸二乙酯法合成亚甲基二膦酸四乙酯

改进的亚磷酸二乙酯法合成亚甲基二膦酸四乙酯刘国正（北京师范大学化学系北京１００８７５）关键词亚甲基二膦酸四烷基脂，亚磷酸二乙酯，合成ＭＤＰ（ＭｅｔｈｙｌｅｎｅＤｉｐｈｏｓｐｈｏｎａｔｅｓ）的四烷基酯是颇具实用价值的化合物，它与活泼金属反应可生成盐，可...     

Arbuzov重排反应合成烷基膦酸酯的研究进展

膦酸烷基酯是一类具有多种生物活性的有机磷化合物,在农业和医药化工领域具有广泛的应用。本文介绍了Michaelis-Arbuzov重排反应构建P-C键合成膦酸烷基酯类化合物的方法,着重阐述了通过催化剂、微波、超声波等促进的绿色环保的Arbuzov重排反应。特别是在连续流动条件下通过微反应进行的无溶剂Arbuzov重排反应,能够缩短反应时间,提高反应效率,使膦酸烷基酯的合成具有更广阔的应用前景。     

N－烷基吡咯烷酮的合成

Ｎ－烷基吡咯烷酮的合成王锡臣，张颂培，祝钧（北京轻工业学院化工系北京１０００３７）关键词烷基吡咯烷酮，固－液相转移催化，合成Ｎ－烷基吡咯烷酮可用作香波增稠剂，染发烫发调理剂，啤酒、葡萄酒中多酚洁净化剂和洗涤去渍剂等［１］，其合成一般采用吡咯烷酮Ｎ－烷...     

有机磷化合物的研究(LVII)——二苯(氧)基氯膦对肟基的自由基加成——合成1-氨基取代三烷基氧化膦及烷基膦酸酯的新途径

二苯基氯膦或二苯氧基氯膦对醛(酮)肟的反应可作为合成1-氨基烷基二苯基氧化膦或1-氨基烷基膦酸二苯酯的新方法,具有条件温和、操作方便及得率高的优点。EPR研究结果揭示了这类反应属自由基机理。     

异烷基膦酸单烷基酯萃取分离稀土的研究

研究了异烷基膦酸单烷基酯系列萃取剂色层分离稀土的性能。结果表明,以八碳异烷基膦酸-1-甲基庚基酯分离稀土的性能最佳,体系酸度均较目前使用的萃取剂低,用1.73 mol/L HNO_3可将Tm、Yb、Lu完全分离,用它制成的负载树脂分离稀土,其柱效高,动力学性能好。另外,对萃取反应机理作了一些探讨。     

Synthesis of dialkyl esters of arylamino(2-pyridyl)methyl-phosphonic acids

Crystalline dialkyl esters of arylamino(2-pyridyl)methylphosphonic acids have been synthesized by the reaction of 1-pyridylazomethines with dialkyl phosphites in the presence of sodium alkoxides. When -pyridinealdehyde was condensed with dialkyl phosphites in the presence of sodium alkoxides, dialkyl esters of hydroxy(2-pyridyl) methylphosphonic acids were obtained in the form of viscous liquids. These compounds were identified in the form of the crystalline methiodides.     

Rhodium-catalyzed organothio exchange reaction of α-organothioketones with disulfides

RhH(PPh(3))(4) and 1,2-bis(diphenylphosphino)ethane (dppe) catalyzed the organothio exchange reaction of α-organothioketones and organic disulfides. The reaction was affected by the structure of the substrate: α-phenylthio and α-alkylthio aryl ketones reacted effectively with diaryl and dialkyl disulfides; α-phenylthio dialkyl ketones reacted with diaryl disulfides but not with dialkyl disulfides; diaryl disulfides with electron-donating p-substituents were more reactive than those with electron-withdrawing p-substituents.     

Organosilicon compounds XVII. Introduction of the dialkyl phosphonate and dialkyl thiophosphonate moieties on an organosilicon substituted heterocyclic system

A number of new dialkyl 2-(5-trisubstitutedsilyl)thienylphosphonates and thiophosphonates as well as dialkyl 2-(5-trisubstitutedsilyl)furylphosphonates and thiophosphonates were prepared via reaction of the 5-(trisubstitutedsilyl)-2-lithiothiophenes and furans with dialkyl chloro-phosphate and dialkyl chlorothiophosphate. Moreover, some diethyl 2-[5-(trisubstitutedsiIyl)-2-thienyl] ethyl thiophosphates are reported.     

Ligand Exchange Gas Chromatography on PTFE Open Tubular Columns

Two kinds of capillary columns were prepared and tested as the stationary phases of ligand exchange gas chromatographic separation of dialkyl sulfides. The PTFE column wall-coated with silane-DTC-Cu but without the addition of silicone exhibits significantly better selectivity towards dialkyl sulfides than a column wall-coated with 10% silane-DTC-Cu in silicone. With the first column connected to a microsample injection valve and a microsample loop, the quantitative determination of dialkyl sulfides can be performed. The column also shows great promise for the separation of dialkyl sulfide-hydrocarbon mixtures.     

Synthesis and Reactions of Azomethines Containing a m-Phenoxyphenyl Group: II. Chemical Transformations >of N-Aryl-m-phenoxyphenylmethanimines and Arylhydrazones of m-Phenoxybenzaldehyde

Chemical transformations of N-aryl-m-phenoxyphenylmethanimines and m-phenoxybenzaldehyde arylhydrazones were studied by examples of reduction thereof with complex metal hydrides and reactions with dialkyl phosphates and dialkyl phosphites.     

Microwave Irradiation Technique for Synthesis of Dialkyl Dithiophosphoric Acids

Microwave heating technique was applied to the preparation of dialkyl dithiophosphoric acids from the reaction of alcohol with phosphorus pentasulphide. A microwave oven (CEM-MDS 2000) was utilized to determine the preparation conditions for the best yield of dialkyl dithiophosphoric acids under atmospheric pressure at various times and power. Six different (C 4 -C 9 ) chain-length of dialkyl dithiophosphoric acids were studied. All experiments were performed in an open Teflon (poly-tetrafluoroethylene) vessel. The results obtained showed that the reaction of dialkyl dithiophosphoric acids can be achieved more rapidly using microwave heating than using conventional procedures.     

Synthesis of fluorine-containing quinoline-2,3-dicarboxylates from products of vicarious nucleophilic substitution of hydrogen in 3-fluoronitroarenes

The reactions of 3-fluoro-4-R-6-phenylsulfonylmethylnitrobenzenes with dimethyl fumarate or diethyl maleate in acetonitrile in the presence of an excess of K₂CO³ and a catalytic amount of 18-crown-6 afforded mixtures of dialkyl 6-R-7-fluoro- and dialkyl 6-R-7-phenylsulfonylquinoline-2,3-carboxylate N-oxides, as well as dialkyl 6-R-7-fiuoro- quinoline-2,3-carboxylates (alkyl is methyl or ethyl), which were resolved by column chromatography and identified by ¹H NMR spectroscopy and X-ray diffraction.     

Mutual optical resolution of 2,2′-dihydroxy-1,1′-binaphthyl and alkyl aryl or dialkyl sulfoxides by complex formation

By complexation with optically active 2, 2′-dihydroxy-1, 1′-binaphthyl, alkyl aryl and dialkyl sulfoxides were resolved very efficiently. Reversely, by complexation with optically active alkyl aryl or dialkyl sulfoxides, 2, 2′- dihydoxy-l,l′-binaphthyl was resolved very efficiently, In all cases, 100% optically pure (+)- and (?)-enantiomers were obtained in good yields.     

Stereoretentive conversion of dialkyl [18O]-phosphoranilidates into dialkyl hydrogen [18O]-phosphates

Conversion of P-chiral dialkyl phosphoranilidates into corresponding dialkyl hydrogen phosphates by means of isoamyl nitrite proceeds with retention of configuration at phosphorus.     

THE REACTION OF ACETYLACETONE WITH DIALKYLPHOSPHITES: Synthesis of Dialkyl 1-methyl-3-oxo-1-butenyl-phosphonates

Abstract

Acetylacetone and its related compounds were transformed into the dialkyl 1-methyl-1-trimethylsiloxyl-3-oxo-butylphosphonates, which after treatment with trifluoroacetic acid were converted into the dialkyl 1-methyl-3-oxo-1-butenylphosphonates.