Oxygen → HCID 86754406, compound

Participants

Reaction Conditions

Reaction Steps

The vinyl sulfide of Example 1(b) (0.052 g) was irradiated in 10 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 for 10 min. N-Chlorosuccinimide (0.0229 g) was added and the mixture maintained at -78° C. for 15 minutes. 2-Cyanoethanol (25.8 uL) in 3 mL of dry CH2Cl2 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 9 over a period of 45 min. The solution was concentrated to dryness and the residue dissolved in a minimal amount of CH2CL2 and purified by prep. TLC with 25% ethyl acetate in CH2Cl2 ; 1H NMR (CDCl3) δ1.01-1.11 (m, 1H), 1.23-1.32 (M, 1H), 1.45-1.94 (m, 10H), 2.23 (br s, 1H), 2.60-2.72 (m, 1H), 2.76-2.90 (m, 1H), 3.06 (br s, 1H), 3.49-3.60 (m, 1H), 3.69-3.81 (m, 1H), 5.93 (br s, 1H), 6.88-6.98 (m), 7.19 (br s, 2H), 7.325 (t, 1H).

Provenance & Evidence