Oxygen → HCID 86754408, compound

Participants

Reaction Conditions

Reaction Steps

The vinyl sulfide of Example 1(b) (0.106 g) was irradiated for 10 min in 20 mL of CH2Cl2 containing a few crystals (<1 mg) of methylene blue with continuous oxygen bubbling at -78° C. using a 1000 W Na lamp. TLC indicated that the vinyl sulfide was consumed. N-Chlorosuccinimide (0.047 g) was added and the mixture maintained at -78° C. for 15 minutes. Phenol (83 mg) was added and the solution warmed to room temperature. Progress of the reaction was monitored by the appearance of a new material by TLC (20% ethyl acetate in hexane) which emitted blue light when the plate was heated and by observing the color of chemiluminescence from an aliquot of the reaction solution reacted with 0.1 M TBAF in DMSO. The yellow emission of dioxetane 1 was gradually replaced by the blue emission of dioxetane 11 over a period of an hour. The solution was concentrated and the residue chromatographed on a silica prep. TLC plate with 20% ethyl acetate in hexane. The major band was isolated and found to contain a mixture of phenol, ca. 60 mg of dioxetane 11 and ca. 5 mg of adamantanone. Dioxetane 11: 1H NMR (CDCl3) δ1.09-1.19 (m), 1.25-1.35 (m), 1.45-1.54 (m), 1.56-2.14 (m), 2.26 (br s), 3.28 (br s), aromatic peaks could not be resolved from residual phenol.

Provenance & Evidence