The Vespiary
The Hive => Methods Discourse => Topic started by: PEYOTE on October 17, 2001, 07:14:00 PM
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Hi guyz.
I think this Mn(OAc)3 it's more interesting than someone would expect.
From Advanced Organic Chemistry, J. March, 4th edition, page 835-6, section 5-45
The conversion of olefines to gamma-lactones (Addition of Oxygen, Carbon)
Global rxn:
>C=C< + Mn(OAc)3 =(HOAc)=> 3,4-(substituted)gamma-lactone
Olefins react with manganese (III) acetate to give gamma-lactones(1). The mechanism is probably free-radical, involving addition of .CH2COOH to the double bond. Lactone formation has also been accomplished by treatment of olefins with lead tetraacetate(2), with a alpha-bromocarboxylic acids in the presence of benzoyl peroxide as catalyst(3), and with dialkyl malonates and iron (III) perchlorate Fe(ClO4)3.9H2(4). Olefins can also be converted to gamma-lactone by indirect routes(4).
So, if you use ethylene, acetic acid and the magic Mn(OAc)3, you can product GBL and then GHB!
Refs:
(1) JACS 90:5903(1968), 90:5905(1968), 96:7977(1974)
JCS, Perkin Trans 2 1537(1984)
Tetrahedron 47:831(1991)
Tetrahedron Lett. 26:3761(1985), 26:4291(1985)
(2) JACS 90:2706(1968)
(3) Bull. Chem. Soc. Jpn. 60:1049(1987)
Tetrahedron Lett. 25:3939(1984)
(4) Synlett 42:(1990)
(5) Chem. Ber. 102:4157(1969)
Helv. Chem. Acta 55:2198(1972)
Tetrahedron Lett. 29:6925(1988)
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The alkene you would use for GBL would be ethene... Not easy to handle, as it is a gas. But it is probably of more use for substituted GBL's.
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yes, however, of ethene was cleaveged in situ, and the
manganese (III) acetate was deposited as a catalytic
stack of mesh, and the ethene passed through this stack,
would this be an appropriate method for converting the
olefin in the vapour phase?
Don't mind me. I'm mentally ill.