Hydroxyalkylation with. cap alpha. -hydroperoxydiazenes. Alcohols from olefins and carbonyl compounds from enol ethers
Journal Article
·
· J. Org. Chem.; (United States)
Alkyl(1-hydroperoxy-1-methylethyl)diazenes 2a-C((CH/sub 3/)/sup 2/C(OOH)N=NR: a,R =CH/sub 2/CH/sub 2/CN; c,R = CH/sub 2/CH(CH/sub 3/)CN; d,R = CH/sub 2/CH/sub 2/OCH/sub 3/; e,r =CH/sub 2/CH/sub 2/OC/sub 6/H/sub 5/; f,R = CH/sub 2/CH/sub 2/CH/sub 2/OC/sub 6/H/sub 5/)) were prepared in solution by autoxidation of the corresponding hydrazones of acetone. Thermolysis of the diazenes at 50-80/sup 0/C in alkenes leads to alcohols. For example, 2b decomposes in 1,1-diphenylethene to afford 5-hydroxy-5,5-yield. Thermolysis of a diazene 2 in an enol ether solvent leads to an aldehyde or a ketone. Thus, 2a decomposes in 1-ethoxyethene and in 2-methoxypropene to afford, respective, 4,4,4-trifluorobutanol and 5,5,5-trifluoro-intermediates and radical chain hydroxyalkylation of alkene double bonds. In one chain-propagating step, R., generated from 2, adds to the alkene. The adduct radical so formed propagates by inducing decomposition of 2 by attack at hydroxyl oxygen. According to this mechanism, inital products from enol ethers are hemiacetals or hemiketals which do not survive the reaction conditions but decompose to the corresponding carbonyl compounds. Preliminary evidence for this mechanism is presented.
- OSTI ID:
- 6313497
- Journal Information:
- J. Org. Chem.; (United States), Journal Name: J. Org. Chem.; (United States) Vol. 49:2; ISSN JOCEA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
090121 -- Hydrocarbon Fuels-- Chemical Synthesis-- (1976-1989)
10 SYNTHETIC FUELS
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALCOHOLS
ALDEHYDES
ALKANES
ALKENES
AROMATICS
AZINES
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
DATA
ENOLS
ETHERS
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
HYDROXY COMPOUNDS
INFORMATION
KETONES
KINETICS
NITRILES
NMR SPECTRA
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
REACTION INTERMEDIATES
REACTION KINETICS
SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
THERMOCHEMICAL PROCESSES
YIELDS
10 SYNTHETIC FUELS
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALCOHOLS
ALDEHYDES
ALKANES
ALKENES
AROMATICS
AZINES
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
DATA
ENOLS
ETHERS
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
HYDROXY COMPOUNDS
INFORMATION
KETONES
KINETICS
NITRILES
NMR SPECTRA
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
REACTION INTERMEDIATES
REACTION KINETICS
SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
THERMOCHEMICAL PROCESSES
YIELDS