Mechanism of methoxide ion substitution in the z and e isomers of o-methylbenzohydroximoyl halides.
Kinetics and stereochemical studies have been carried out on the reactions of the Z and E isomers of O-methylbenzohydroximoyl halides [1Z and 1E, ArC(X)=NOCH(3)] with sodium methoxide in 9:1 DMSO-methanol. The reactions of methoxide ion with hydroximoyl fluorides (X = F) are stereospecific. The reaction with 1Z (X = F) gives only the Z substitution product (1Z, X =OCH(3)). The reaction of methoxide ion with 1E (X = F) is less selective, giving ca. 85% E substitution product. The Hammett rho-values for the Z and E isomers (X = F) are +2.94 and +3.30, respectively. The element effects for 1Z (Ar = C(6)H(5)) are 2.21 (X = Br):1.00 (X = Cl):79.7 (X = F). The 1E element effects are (Ar = C(6)H(5)) 1.00 (X = Cl):18.3 (X = F) and (Ar = 4-CH(3)OC(6)H(4)) 1.97 (X = Br):1.00 (X = Cl):12.1 (X = F). The entropies of activation for these reactions are negative (for example, DeltaS() = -15 eu for 1Z and DeltaS() = -14 eu for 1E, Ar = 4-CH(3)OC(6)H(4), X = F). These experimental observations are consistent with a mechanism proceeding through a tetrahedral intermediate. Ab initio calculations were carried out to help explain the stereospecificity of these reactions. These calculations indicate that the tetrahedral intermediate from the Z isomer undergoes rapid elimination to the Z substitution product before stereomutation can take place. These calculations also show that the lowest barrier for rotation around the carbon-nitrogen single bond in the tetrahedral intermediate derived from 1E leads to an intermediate that eliminates fluoride ion to give E product.
Johnson
James E
JE
Department of Chemistry and Physics, Texas Woman's University, Denton, Texas 76204-5859, USA. jjohnson@twu.edu
Dolliver
Debra D
DD
Yu
Lonchun
L
Canseco
Diana C
DC
McAllister
Michael A
MA
Rowe
Jeffrey E
JE
D006846:Hydrocarbons, Halogenated / Q000737:chemistry*; D007700:Kinetics; D000432:Methanol / Q000737:chemistry*; D015394:Molecular Structure; D010091:Oximes / Q000138:chemical synthesis / Q000737:chemistry; D013237:Stereoisomerism
D006846:Hydrocarbons, Halogenated; D010091:Oximes; D000432:Methanol