Reactions of Peracids. VI. The Reaction of Acetylcyclanes with Perbenzoic Acid¹

Microbial growth on 2-bromobutane

“…These pathway does, however, contain an enzyme which converts methyl ethyl ketone to ethyl acetate by the addition of one oxygen atom. This process is analogous to the Baeyer-Villiger rearrangement (Friess and Pinson, 1952) due to oxidation by a peracid. We are investigating this enzyme at the present time.…”

Functionalised carbocycles from carbohydrates. Part 4. The synthesis of the epoxy lactone prostaglandin intermediate via bicyclo[3.2.0]heptane derivatives. X-Ray crystal structure of (1R)-5-endo-acetyl-2-exo,3-endo-dibenzoyloxybicyclo[2.2.1]heptane

“…( 1 S,7S)-5-endo-Acetyl-2-exo,3-endo-dibenzoyloxy-7-phenylthiobicycZo[2.2.1 Iheptane (1 2).-The ketone (3) (0.2 g) was stirred for 15 h in N,N-dimethylformamide in the presence of sodium benzenethiolate (0.27 g) and the three products formed were isolated by p.1.c. The most mobile (53 mg) was apparently a product of aldol condensation, the slowest (21 mg) was not characterised, and the intermediate, main compound (71 mg, 40%) was the phenylthiotrinorbornane (12) which was crystallised from methanol, m.p. 143-144 "C; The compound was also produced by treatment of the tricyclic ketone (4) (40 mg) with sodium benzenethiolate (14 mg) in N,N-dimethylformamide (1 ml) for .6 h at 20 "C. Isolated by p.l.c., the product (33 mg, 64%) had the same 'H n.m.r.…”

“…In particular, there were ring proton resonances in the region 6 1.6-2.1 which were not present in the spectrum of compound (3). This same product was then observed to result from analogous treatment of the tricyclic ketone (4) (which is therefore assumed to have been formed as an intermediate) and the product was thus assigned the bicyclo[2.2.l]heptane structure (12).…”

Kinetic studies of Dakin oxidation of o- and p-hydroxyacetophenones

“…180 labelling of the car-bony1 carbon in the substrate 5 gives ''0 in the carbonyl of the ester 8 (14,15). A migration cage 9 has been proposed for the group R (16), with a highly negative AS* of -30 to -45 eu (5,(17)(18)(19), and it is accepted that no free (electron deficient) oxygen species or carbonium ion is formed during the rearrangement process (16,20). The collapse of 8 to products is acidcatalyzed and is the rate-determining step of the process (6).…”