Polymerizable Tautomers. VII. Radical Copolymerization of Ethyl 3-oxo-4-Pentenoate and Ethyl 4-Methyl-3-oxo-4-Pentenoate with Methyl Methacrylate

Abstract

Ethyl 3-oxo-4-pentenoate (EAA) and ethyl 4-methyl-3-oxo-4-pentenoate (EMAA) exhibit the coexistence of the ketonic and enolic forms in most organic solvents. Radical copolymerizations of EAA and EMAA with methyl methacrylate (MMA) were carried out at 60 °C in various solvents, and monomer reactivity ratios were estimated. There are minor solvent effects on monomer reactivity ratios r_MMA in both EAA/MAA and EM A A/MM A systems. On the other hand, r_EAA and r_MMA values greatly change with the solvent: The values decrease with an increase in the ketonic fraction of the polymerizable tautomers (EAA and EMAA). Regression analysis of the monomer reactivity ratios with the solvatochromic parameters reveals that polarity of the solvent is the major factor governing the relative reactivity.     

2-氧代-3-芳基-丁二酸酯的合成与表征

在复杂的天然产物合成和生物合成中,醇醛缩合反应是一类重要的碳-碳键形成反应.不对称催化直接Aldol反应由于其原子经济性,操作简捷,符合绿色化学的要求等,成为近年来不对称合成研究的热点之一.     

Electrochemical oxidation of ethyl 3-oxo-3-phenyl-2-phenylhydrazonopropionate

The electrochemical oxidation of ethyl 3-oxo-3-phenyl-2-phenylhydrazonopropionate has been studied in the pH range 3.0–11.0 at a pyrolytic graphite electrode by linear and cyclic sweep voltammetry, coulometry and spectral studies. The results indicate that the 2 e⁻, 2 H⁺ oxidation of this compound gives phenol and ethyl 3-phenyl-2,3-dioxopropionate as the major products of electrooxidation.     

3-oxo-3-phosphapentopyranoses

Addition of methyl phosphinate to 2(R)-methoxy 3-oxapentanedial gives all eight possible diastereoisomeric 3-phosphapentopyranoses in very poor yield. Structures and stereochemistry are assigned on the basis of ¹H, ³¹P, NMR, and mass spectroscopy of their acetates. © 1996 John Wiley & Sons, Inc.     

Structure of 3-chloromethyl-3-oxo-2H-1,4, 3-benzoxa2aphosphorine

The six-membered heterocycle in the compressed bicyclic structure of 3-chloromethyl-3-oxo-2H-1,4,3-benzoxazaphosphorine has distorted C² -sofa conformation with a gauche C1-C-P=O fragment. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2357–2359, October, 1989.     

Structure of 2-chloromethyl-2-oxo-3H-1,4,2-benzoxazaphosphorine

The compressed bicyclic structure of 2-chloromethyl-2-oxo-3H-1,4,2-benzoxaza-phosphorine features a sixmembered heterocycle with P ²,C³ -half-chair with axial equatorial orientation of the P=O group and axial orientation of the CH₂Clgroup. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2355–2357, October, 1989.     

Synthesis of ethyl cis 2-[(Diethoxyphosphoryl)methyl]-7-oxo-3-phenyl-6-phthalimido-l-azabicyclo[3.2.0]hept-3-ene-2-carboxylate and Methyl cis-2-Bromo-3-methyl-8-oxo-7-phthalimido-4-oxa-1-azabicyclo[4.2.0]octane-2-carboxylate

The synthesis of a Δ¹-carbapenem and two β-lactams possessing a Br-atom at the N-substituting center not involved in the lactam ring and bearing the carboxyl group is described. The β-lactams having this kind of Br-substitution are more susceptible to nucleophilic attack than those having a conjugated double bond with the N-atom of the β-lactam ring. DBU is found to be an excellent reagent for the elimination of the silyloxy function. Moreover, a simple method for the addition of diethyl phosphite to an α, β-unsaturated double bond using a catalytic amount of NaH is described.