Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science

Synthesis of Dimethylbutatrienone, (CH3)2C=C=C=C=O, by a Rearrangement-Fragmentation Process and by Direct Elimination

RFC Brown, KJ Coulston, FW Eastwood and MJ Irvine

Australian Journal of Chemistry 44(1) 87 - 101
Published: 1991


4-Methylpenta-1,2,3-trien-1-one ( dimethylbutatrienone , Me2C=C=C=C=O) was generated by flash vacuum pyrolysis of precursors derived from 4,4-dimethyl-2-oxotetrahydrofuran-3-ylideneacetic acid (6) and from 4-methylpenta-2,3-dienoic acid (14). Pyrolysis of the mixed trifluoroacetic anhydride and of the acid chloride of (6) and, in poorer yield, of (14) gave 4-methylpenta-1,2,3-trien-1-one which was detected by argon matrix infrared spectroscopy (Vmax 2224, 2216 cm-1) and by reaction with methanol to form methyl 4-methylpenta-2,3-dienoate. The fragmentation pathway for the derivatives of (6) was established by detection of the initially formed propadienone, 4,4-dimethyl-2-oxotetrahydrofuran-3-ylideneethenone, and also by pyrolysis of the trifluoroacetic mixed anhydride (7.L) and the acid chloride (8-L) of 4,4-dimethyl-2-oxotetrahydro(2-13C)furan-3-ylideneacetic acid. The argon matrix spectra of pyrolysates from (7-L) and (8-L) showed bands at 2182 and 2177cm-1 attributed to 4-methyl(1-13C)penta-1,2,3-trien-1-one.

4,4-Dimethyl-3-methylenedihydrofuran-2-one was prepared in 67% yield by flash vacuum pyrolysis of the acid (6).

© CSIRO 1991

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