Regioselective carbon-oxygen bond cleavage reactions of aromatic ethers and esters with potassium metal/18-crown-6/THF as the electron-transfer reagent

Journal Article · Fri Oct 28 00:00:00 EDT 1988 · J. Org. Chem.; (United States)

DOI:https://doi.org/10.1021/jo00257a007· OSTI ID:6299116

Fish, R H; Dupon, J W

The facile carbon-oxygen bond cleavage reactions of a variety of aromatic ethers and esters were studied with an electron-transfer reagent that consisted of potassium metal and 18-crown-6 in tetrahydrofuran (THF). The relative rates of carbon-oxygen bond cleavage, with these aromatic ethers and esters under electron-transfer conditions, was studied in competition with the standard, diphenyl ether. The order of relative reactivities was as follows: phenyl 2-hydroxybenzoate (10) (>2.0); phenyl 2-methoxybenzoate (11) (>2.0); phenyl 4-methoxybenzoate (12) (>2.0); 2-methoxyphenyl benzoate (13) (>2.0); 4-methoxyphenyl benzoate (14) (>2.0); 4-hydroxyphenyl benzoate (15) (1.6); benzyl benzoate (9) (1.3); 4-methoxyphenyl phenyl ether (5) (1.15); phenyl benzoate (8) (1.04); diphenyl ether (1) (1.0); dibenzyl ether (2) (0.98); 2-methoxyphenyl phenyl ether (6) (0.97); benzyl phenyl ether (3) (0.96); phenethyl phenyl ether (7) (0.77); and 4-hydroxyphenyl phenyl ether (4) (<0.1). From these relative rates, it is clear that electron-donating groups increase the relative rates of C-O bond cleavage in aromatic esters. Conversely, a methoxyl group has no apparent effect on the relative rates of aromatic ether C-O bond cleavage, while a hydroxyl group dramatically decreases the rate. Proton donors, tert-butyl alcohol and hydroquinone, decreased the rate of diphenyl ether cleavage. The regioselectivity for C-O bond cleavage of esters 8-15, i.e., carbonyl-oxygen versus carboxyl-carbon cleavage, showed selective carbonyl-oxygen bond cleavage.

• Research Organization: Lawrence Berkeley Lab., CA (USA)
• DOE Contract Number: AC03-76SF00098
• OSTI ID: 6299116
• Journal Information: J. Org. Chem.; (United States), Vol. 53:22
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
01 COAL, LIGNITE, AND PEAT
POLYETHYLENE GLYCOLS
ELECTRON TRANSFER
POTASSIUM COMPLEXES
EXPERIMENTAL DATA
TETRAHYDROFURAN
ALCOHOLS
ALKALI METAL COMPLEXES
COMPLEXES
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FURANS
GLYCOLS
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HYDROXY COMPOUNDS
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ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANIC POLYMERS
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400201* - Chemical &amp; Physicochemical Properties
010600 - Coal
Lignite
&amp; Peat- Properties &amp; Composition