A Novel Rearrangement of Hydroxamic Acids Using Sulfonyl Chlorides

Abstract

Direct rearrangement of monohydroxamic acids without the necessity of isolating a dihydroxamic acid occurs on reaction of the monohydroxamic salts with arenesulfonyl chlorides. The product from benzohydroxamic acid is benzo-(phenylcarbamylhydroxamic) acid, that from hydrocinnamohydroxamic acid is hydrocinnamo-(phenethylcarbamylhydroxamic) acid, and that from succinohydroxamic acid (with benzenesulfonyl chloride) is 3-benzenesulfonoxy-5,6-dihydrouracil. The steps leading to the formation of these substances are discussed, and certain of their reactions are developed.The Lossen rearrangement of a hydroxamic acid as usually performed involves acylation and heating a salt of the acyl derivative RCONHOH -RCONHOCOR' -*--R'COONa H20RCONNaOCOR'-->-RNCO -> RNHCONHR (or RNH2)

Hydroxamic acids and N-hydroxyimides related to pyridine, pyrazine, and quinoxaline

“…Beckwith and Hick-man4 report mp 217-219°for 3, recrystallization solvent unspecified. Our compound possessed the same four ir bands which they reported (Nujol mull,3.18,3.25,5.42,5.65 µ) and our spectrum (KBr) showed these additional bands: 5.70, 6.20, 6.55 (w), 7.00, 7.40, 7.80 (m), 8.10 (m), 9.70, 10.10, 10.75 (m), 12.00 (w), 12.70, 13.30, 14.00, 14.60 (w), 15.00 (m) µ. Our product was insoluble in benzene, ethyl acetate, or chloroform; attempted recrystallizations were unsuccessful.…”

“…(1) Abbott Fellow, 1962Fellow, -1963Lubrizol Fellow, 1963-1965 (2) C. D. Hurd, C. M. Buess, and L. Bauer, J. Org. Chem., 17, 865 (1952);19, 1140(1954.…”

Thermal decomposition of matrix metalloproteinase inhibitors: Evidence of solid state dimerization

“…Supplemental data from TGA-FTIR, LC-MS-MS and NMR suggested the formation of a dimeric species through a Lossen Rearrangement in the case of Comopund II. This type of rearrangement reaction has been reported for hydroxamic acids in solution [15,16]; however to our knowledge the Lossen Rearrangement in the solid state has not been previously described. Based on TGA-FTIR data for Compound III and the propensity for hydroxamic acids to degrade via the Lossen Rearrangement, it likely undergoes the same type of degradation to form the urea linked dimeric species proposed in Fig.…”

Fully Renewable Non‐Isocyanate Polyurethanes via the Lossen Rearrangement

“…[ 34 ] Very recently, different polymers bearing hydroxamate groups have been synthesized, possessing desirable chelating properties and biocompatibility for medical purposes, surface coatings, and material science. [ 35 ] For the Lossen rearrangement, it was assumed that an activating group such as O‐acylating, [ 36 ] O‐silylating, [ 37,38 ] or O‐phosphorylating [ 39 ] agent was necessary for the rearrangement to occur. In 1974, it was commonly known that a hydroxamic acid could rearrange in strongly alkaline solution.…”