期刊
JOURNAL OF FLUORINE CHEMISTRY
卷 132, 期 10, 页码 815-828出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jfluchem.2011.05.034
关键词
Bromodifluoromethylphosphonates; Dibromofluoromethylphosphonates; Difluorocarbene; Michaelis-Arbuzov; Halo-F-methylphosphonates
资金
- Graduate College of the University of Iowa
The synthesis of a variety of new halo-F-methylphosphonates has been achieved by a Michaelis-Arbuzov type reaction between a halo-F-methane and a trialkyl phosphite. This synthesis has proved to be of wide scope and utility for the high yield preparation of a number of heretofore unknown compounds. The H-1, F-19, C-13 and P-31 NMR spectroscopic properties are reported in detail. The mechanism for the formation of bromodifluoromethylphosphonates has been shown to proceed through the intermediacy of difluorocarbene:CF2. The phosphonate products have been shown to react with a wide variety of reagents. Fluoride and alkoxide ions react by attack at phosphorus with cleavage of the carbon-phosphorus bond and formation of [:CF2] from the bromodifluoromethylphosphonates and the CFBr2- anion from the dibromofluoromethylphosphonates. Iodide ion and tertiary phosphines react by attack at the ester carbon to give stable phosphonate salts. Hydrolysis of the phosphonate esters with 50% aqueous HCl gives the expected phosphonic acids. Trimethylsilyl bromide attacks phosphoryl oxygen to afford the bis(trimethylsilyl) esters. (C) 2011 Elsevier B.V. All rights reserved.
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