írans-Di-tert-butylcyclopropanone (1) has been prepared by reaction of potassium iert-butoxide with a-bromodineopentyl ketone. Partial resolution has been effected by reaction with d-amphetamine and with diisopinylcampheylborane. Reaction of 1 with water affords the hydrate (rates and equilibrium constants are reported in Table I). Reaction of 1 with alcohols affords the hemiketals, isolable for primary alcohols (relative rates of formation of hemiketals in alcohol solution at 25°follow: methanol, 90; ethanol, 20; isopropyl alcohol, 1; tert-butyl alcohol, 0). The rate of reversion of the methanol hemiketal to 1 in methanol has been determined by use of deuterium-labeled hemiketal. Under basic conditions the hemiketals are converted to the ring-opened Favorskii ester 2, under acidic conditions to -alkoxy ketone 3. Reaction of 1 with potassium iert-butoxide in terf-butyl alcohol-O-d affords ester 3 of deuterium content da 3%, di 50%, d2 31%, d3 16%, pointing to some attack at a hydrogen. The cyclopropanone is stable to oxygen; the hydrate and hemiketals are not.
Aus Brom‐neopentylketon (I) erhält man mit definierten Mengen an tert.‐Butylat das trans‐1,2‐Di‐tert.‐butyl‐cyclopropanon (II), das mit weiterem tert.‐Butylat zum Ester (III) gespalten wird.
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