681856-02-0Relevant articles and documents
Intermolecular electrophilic O-amination of alcohols
Hassner, Alfred,Patchornik, Guy,Pradhan, Tarun K.,Kumareswaran
, p. 658 - 661 (2007)
We report the first examples of an intermolecular electrophilic O-amination of aliphatic alcohols. Thus, the new reagents, fluorenone oxime tosylate, 5a, or mesylate, 5b, permit O-amination of diverse alcohols in the presence of NaH under mild conditions. By following the formation of the resulting oxime ethers, 6, the reaction was shown to be sensitive to steric effects in the alcohol. Furthermore, the presence of an aromatic ring or of a double bond in the alcohol molecule (benzyl, allyl) was found to increase the reaction rate.
Thermal decomposition of O-benzyl ketoximes; role of reverse radical disproportionation
Blake, Jessie A.,Ingold, Keith U.,Lin, Shuqiong,Mulder, Peter,Pratt, Derek A.,Sheeller, Brad,Walton, John C.
, p. 415 - 420 (2007/10/03)
Thermolyses of seven dialkyl, two alkyl-aryl and two diaryl O-benzyl ketoxime ethers, R1R2C=NOCH2Ph, have been examined in three hydrogen donor solvents: tetralin, 9,10-dihydrophenanthrene, and 9,10-dihydroanthracene. All the oxime ethers gave the products expected from homolytic scission of both the O-C bond (viz., R1R2C=NOH and PhCH3) and N-O bond (viz., R1R2C=NH and PhCH2OH). The yields of these products depended on which solvent was used and the rates of decomposition of the O-benzyl oxime ethers were greater in 9,10-dihydrophenanthrene and 9,10-dihydroanthracene than in tetralin. These results indicated that a reverse radical disproportionation reaction in which a hydrogen atom was transferred from the solvent to the oxime ether, followed by β-scission of the resultant aminoalkyl radical, must be important in the latter two solvents. Benzaldehyde was found to be an additional product from thermolyses conducted in tetralin. This, and other evidence, indicated that another induced decomposition mode involving abstraction of a benzylic hydrogen atom, followed by β-scission of the resulting benzyl radical, became important for some substrates. Participation by minor amounts of enamine tautomers of the oxime ethers was shown to be negligible by comparison of thermolysis data for the O-benzyloxime of bicyclo[3.3.1]nonan-9-one, which cannot give an enamine tautomer, with that of the O-benzyloxime of cyclohexanone.
