Spontaneous hydrolysis reactions of cis- and trans-beta-methyl-4-methoxystyrene oxides (Anethole oxides): buildup of trans-anethole oxide as an intermediate in the spontaneous reaction of cis-anethole oxide.
Rates and products of the reactions of trans- and cis-beta-methyl-4-methoxystyrene oxides (1 and 2) (anethole oxides) and beta,beta-dimethyl-4-methoxystyrene oxide (3) in water solutions in the pH range 4-12 have been determined. In the pH range ca. 8-12, each of these epoxides reacts by a spontaneous reaction. The spontaneous reaction of trans-anethole oxide (1) yields ca. 40% of (4-methoxyphenyl)acetone and 60% of 1-(4-methoxyphenyl)-1, 2-propanediols (erythro:threo ratio ca. 3:1). The spontaneous reaction of cis-anethole oxide is more complicated. The yields of diol and ketone products vary with pH in the pH range 8-11, even though there is not a corresponding change in rate. These results are interpreted by a mechanism in which 2 undergoes isomerization in part to the more reactive trans-anethole oxide (1), which subsequently reacts by acid-catalyzed and/or spontaneous reactions, depending on the pH, to yield diol and ketone products. The buildup of the intermediate trans-anethole oxide in the spontaneous reaction of cis-anethole oxide was detected by (1)H NMR analysis of the reaction mixture. Other primary products of the spontaneous reaction of 2 are (4-methoxyphenyl)acetone (73%) and threo-1-(4-methoxyphenyl)-1,2-propanediol (ca. 3%). The rates and products of the spontaneous reaction of 2 and its beta-deuterium-labeled derivative were determined, and the lack of significant kinetic and partitioning deuterium isotope effects indicates that the isomerization of 2 to ketone and to trans-anethole oxide must occur primarily by nonintersecting reaction pathways.
Mohan
R S
RS
Department of Chemistry, Illinois Wesleyan University, Bloomington, Illinois 61701, USA.
Gavardinas
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K
Kyere
S
S
Whalen
D L
DL
D000840:Anisoles / Q000737:chemistry* / Q000378:metabolism*; D003903:Deuterium; D004852:Epoxy Compounds / Q000737:chemistry* / Q000378:metabolism*; D006863:Hydrogen-Ion Concentration; D006868:Hydrolysis; D007536:Isomerism; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy; D010087:Oxides / Q000737:chemistry* / Q000378:metabolism*; D014867:Water / Q000378:metabolism
D000840:Anisoles; D004852:Epoxy Compounds; D010087:Oxides; D014867:Water; D003903:Deuterium; C120685:anethole oxide