Photochemistry of beta-Methyl-beta-Nitrostyrene & Its Derivatives

• Main Author: Tang, Donald
• Format: Others
• Published: TopSCHOLAR® 1974
• Subjects: Chemistry; Physical Sciences and Mathematics
• Online Access: https://digitalcommons.wku.edu/theses/2891; https://digitalcommons.wku.edu/cgi/viewcontent.cgi?article=3906&context=theses

A series of β- methyl-β-nitrostyrenes have been synthesized and subjected to ultraviolet irradiation. A new technique has been developed for synthesis of 1-phenyl-1,2-propanedione-1-oxime and its derivatives by irradiation of the corresponding styrene. The yields of the oximes were almost quantitative [except 1-(p-nitrophynyl)-1,2-propanedione-1-oxime and 1-(m-nitrophenyl)-1,2-propanedione-1-oxime]. It has been found that irradiation of the appropriate styrene is a very simple, efficient, and general procedure for the synthesis of 1-phenyl-1,2-propanedione-1-oxime and a number of its derivatives. A number of derivatives of β- methyl-β-nitrostyrene (p-CH3, p-Ch30, p-Cl, p-No2, and m-NO2) were irradiated. It was found that the substituent effects on the rearrangement of the styrene to the oxime were fairly small. The nitro group attached at the para or meta position of the phenyl ring appeared to inhibit the rearrangement and seemed to promote the fragmentation to form the corresponding acid and aldehyde. Kinetics studies also indicated that the p-nitro and m-nitro-β- methyl-β-nitrostyrene showed a slower rate of disappearance of unsaturated nitro group during irradiation than any of the other substituents studied.