Reaction of Malonic Acid Derivatives with Acetylenic Diphosphonates

The primary addition products in the reactions of malonic esters, cyanoacetic esters, and malononitrile with acetylenediphosphonates in acetonitrile in the presence of anhydrous potassium carbonate are potassium derivatives, viz. esters and nitriles of the corresponding 2-alkoxycarbonyl(or 2-cyano) -3,4-bis(di-alkoxyphosphinoyl)-2-potassiobut-3-enoic acid. Further hydrogen replacement for potassium in the nitriles is accompanied by isomerization involving double-bond shift and geometry change. (E)- and (Z)-3,4-bis(dial-koxyphosphinoyl)-2-cyano-2-potassiobut-3-enenitriles (the alkoxy groups are CH₃O and C₂H₅O) are crystalline compounds; they were isolated and characterized.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 1, 2005, pp. 11–20.Original Russian Text Copyright © 2005 by Shekhadeh, Didkovskii, Dogadina, Ionin.     

Microwave Heating in Organic Synthesis: Decarboxylation of Malonic Acid Derivatives in Water

Microwave heating permits rapid decarboxylation (15 min, 80–98% isolated yields) of malonic acids in water when employing a microwave autoclave mode and high reaction temperature and power (190°C; 800 Watts).     

Reformatsky Reaction of Methyl α-Bromoisobutyrate with 2-Arylmethylidenemalonic Acid Derivatives

Reformatsky reagent obtained by treatment of methyl α-bromoisobutyrate with zinc reacts with dimethyl 2-arylmethylidenemalonates to give trimethyl 2-aryl-3-methylbutane-1,1,3-tricarboxylates. The reaction of the same compound with ethyl 3-aryl-2-(4-methylphenylcarbamoyl)acrylates yields cyclic products, ethyl 4-aryl-5,5-dimethyl-1-(4-methylphenyl)-2,6-dioxopiperidine-3-carboxylates. Treatment of the latter with morpholine and phenylhydrazine leads to the corresponding 4-aryl-5,5-dimethyl-1-(4-methylphenyl)-2,6-dioxopiperidine-3-carboxylic acid morpholides and phenylhydrazides. The products are formed as a single diastereoisomer.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 7, 2005, pp. 1034–1038.Original Russian Text Copyright © 2005 by Shchepin, Fotin.     

氨基酸衍生物催化的不对称Reformastky反应

首次使用侧链上带有配位基因的氨基酸组成的线二肽、环二肽及氨基酸酯作手性配体催化不对称的Reformatsky反应。考察了配体结构、反应底物结构以及反应条件等因素对反应产物ee值的影响。同其它两类配体相比,环肽具有更好的不对称催化效果,其中具有C2对称性的环肽3a效果最好,产物的ee值达到了64％。     

The Heat Effects of Malonic Acid Dissociation

The heat effects of malonic acid dissociation at 298.15 K and several ionic strength values in the presence of NaClO₄ were determined calorimetrically. The thermodynamic characteristics of dissociation at fixed ionic strength values and at I = 0 were calculated.     

Malonic to Acetic Ester Transformation by Boric Acid

One of our synthetic projects involves a step of removing a carbalkoxy group from a substituted malonic ester. For accomplishing that goal, Krapcho's method¹ was deemed unsuitable, because the malonic ester contains an allylic halogen which is liable to attack by dimethyl sulfoxide (Kornblum reaction). Our recent work on using iodotrimethylsilane² to achieve decarbal-koxylation of such esters was partly impelled by that need; however, the prohibitive economics associated with even a medium-scale preparation forced us to develop a less expensive alternative.     

3-甲基犬尿喹啉酸衍生物的合成

报道了六个具有潜在生物活性 3 甲基犬尿喹啉酸衍生物的合成 .它们以取代苯胺和 3 甲基 2 酮丁二酸二乙酯为起始原料 ,经加成脱水 ,环化而得到 .其中三个新的含氟化合物的结构分别经IR ,1 HNMR ,MS ,元素分析等表征     

Synthesis of oxo-Phosphoranylidene Aminobenzoic Acid Derivatives by a Multicomponent Reaction

2-Aminobenzoic acids or 4-aminobenzoic acid react with dimethyl acetylenedicarboxylate/triphenylphosphine in less than 20 min at 15–25°C to produce new organic phosphorus compounds in good to excellent yields. The conversion occurs with selective N- over O-alkylation of the amino group and isolation of the products is accomplished simply by filtration.     

氨基-3-氰基丙酸衍生物的合成

以廉价易得的2,5-二溴吡啶为原料,经取代、氧化、R-(+)-叔丁基亚磺酰胺手性诱导、氨基化、氨基酸缩合等反应,合成了氨基-3-氰基丙酸衍生物,其结构经¹H-NMR, ¹³C-NMR和LC-MS确证。同时对吡啶环5位取代反应机理进行探讨,并且采用ELISA法研究了氨基-3-氰基丙酸衍生物对炎症细胞（BMDM）Caspase-1活性的影响。结果表明：经11步合成的氨基-3-氰基丙酸衍生物结构新颖,并且对Caspase-1的抑制活性具有剂量依赖性。      

Supramolecular Motifs in Metal Complexes of Malonic Acid Dihydrazide: Copper(II) and Zinc(II) Assisted Assembly of Malonic Acid Dihydrazide with Melamine

One pot condensation of malonic acid dihydrazide (MADH) in the presence of metal salts (CuCl₂·H₂O and ZnCl₂) with melamine (TAT) has been achieved. The solids Cu(MADH)₂Cl₂·2TAT·9H₂O and Zn(MADH)₂Cl₂·TAT·1/2H₂O thus obtained were characterized by elemental analysis, FAB mass, i.r., n.m.r., u.v.–visible and e.p.r. spectral data together with their powder X-ray diffraction, optical microscopy, scanning electron microscopy (SEM) and atomic force microscopy (AFM)(Zn complex only). Variable temperature solid slate conductance measurements have also been made.     

Reaction of Lithium Derivatives of 4-Alkyl-3-morpholinones with Azomethine Compounds

Lithium derivatives of some 4-substituted 3-morpholinones react with azomethine compounds to afford 4-alkyl-2-[aryl(phenylamino)methyl]-3-morpholinones with good yields.     

Reaction of 3-Benzoyl-2,3-dibromopropionic Acid with Substituted ortho-Phenylenediamines

3-Benzoyl-2,3-dibromopropionic acid reacts with 4-substituted o-phenylenediamines to give 3-aryl-2-carboxymethylene-1,2-dihydroquinoxalines.     

甘草次酸3位氨基酸衍生物的合成及其抑菌活性

以甘草次酸(1)为原料,将其11位羰基还原、30位羧基酯化得11-脱氧甘草次酸-30-乙酯(3)。再以四氢呋喃为溶剂,N,N’-二环己基碳二亚胺(DCC)/4-二甲基氨基吡啶(DMAP)为偶合剂,选用Fmoc保护氨基酸对11-脱氧甘草次酸-30-乙酯的3位羟基进行酯化,得到11-脱氧甘草次酸-30-乙酯-3位氨基酸酯衍生物(4a～4d)。化合物4a～4d在V(CHCl2)∶V(Et2NH)=1∶1溶液中脱去Fmoc保护基得到最终产物(5a～5d),产率80%～87%。化合物5a～5d用1H NMR、EI-MS进行了表征。活性实验结果表明,化合物5a～5d对在高浓度二甲基甲酰胺下生长的枯草芽孢杆菌、大肠杆菌和酵母菌具有保护作用。     

Microwave Enhanced Knoevenagel Condensation of Malonic Acid on Basic Alumina

Abstract: An improved Knoevenagel condensation of malonic acid and aldehydes can be achieved by microwave irradiation over alumina. A number of diacids were prepared in good yields in very short reaction times.