A synthesis of C18‐methyl‐β‐ionone (8) and C18‐methyl‐β‐ionylidenemalononitrile (13) is reported. Photoreaction of C18‐methyl‐β‐ionylidenemalononitrile resulted in a reversible 7‐cis and 7‐trans isomerization which eventually underwent 1,5‐Hydrogen shift to give the irreversible photoproduct, C18‐methyl‐y‐retro‐ionylidenemalononitrile (14).
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