ethenylsulfanylethene

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The vinyl sulfide of Example 4(a) (0.051 g) was irradiated in 20 mL of CH3OH containing ca. 1 mg of Rose Bengal with continuous oxygen bubbling at -78° C. using a 1000 W Na lamp. When the alkene was shown by TLC to be completely consumed, iodine (0.096 g) and 1 mL of 30% H2O2 were added and the mixture warmed to room temperature. Progress of the reaction was monitored by the disappearance of dioxetane 4 by TLC (20% ethyl acetate in hexane) and the appearance of new bands 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 4 was gradually replaced by the blue emission of dioxetane 20 over a period of two hours. The solution was concentrated to 1-2 mL and separated on preparative TLC with 5% ethyl acetate in hexane. The band containing dioxetane 20 was collected and desorbed and evaporated to yield the product as a slightly yellow oil: 1H NMR (CDCl3) δ1.02 (m, 1H), 1.28 (m, 1H), 1.375 (s, 9H), 1.45-1.94 (m, 10H), 2.17 (br s, 1H), 3.04 (br s, 1H), 3.232 (s, 3H), 7.07-7.49 (m, 4H). to be completely consumed iodine (0.096 g) and 1 mL of 30% H2O2 were added was heated reacted with 0.1 M TBAF in DMSO The solution was concentrated to 1-2 mL separated on preparative TLC with 5% ethyl acetate in hexane The band containing dioxetane 20 was collected evaporated to yield the product as a slightly yellow oil

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The vinyl sulfide of Example 2(b) (0.100 g) was irradiated for 10 min in 20 mL of CH2Cl2 containing 2 mg of methylene blue with continuous oxygen bubbling at -40° C. using a 1000 W Na lamp. NCS (44.7 mg, 1 eq.) was added followed after 15 min by 100 mg (2.3 eq.) of 2,6-difluorophenol in 3 mL of CH2Cl2. The solution was allowed to warm to room temperature. After an hour, TLC showed a new material which emitted blue-green light when the plate was heated. The solution was evaporated, redissolved in a small amount of CH2Cl2 and the product isolated by two successive preparative TLC purifications first using 5-20% ethyl acetate in hexane and then using CH2Cl2 on a second plate yielding 11.2 mg of the product as a slightly yellow oil; 1H NMR (CDCl3) δ1.29-2.24 (m, 13H), 3.31 (br s, 1H), 5.00 (m, 1H), 6.68-7.6 (m, 7H). After an hour was heated The solution was evaporated redissolved in a small amount of CH2Cl2 the product isolated by two successive preparative TLC purifications

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 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. was consumed N-Chlorosuccinimide (0.047 g) was added Phenol (83 mg) was added the solution warmed to room temperature was heated reacted with 0.1 M TBAF in DMSO The solution was concentrated the residue chromatographed on a silica prep The major band was isolated

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The vinyl sulfide of Example 1(b) (0.099 g) was irradiated for 11.5 min in 15 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 (0.044 g) was added and the mixture maintained at -78° C. for 15 minutes. Ethylene glycol (37 uL) 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 10 over a period of an hour. The solution was concentrated to dryness and the residue extracted with ether. The ether was evaporated and the resulting residue chromatographed on a silica prep. TLC plate with 40% ethyl acetate in hexane. The major band contained 18 mg of dioxetane 10. was consumed N-Chlorosuccinimide (0.044 g) was added Ethylene glycol (37 uL) was added the solution warmed to room temperature was heated reacted with 0.1 M TBAF in DMSO The solution was concentrated to dryness the residue extracted with ether The ether was evaporated the resulting residue chromatographed on a silica prep

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 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). for 10 min the solution warmed to room temperature was heated The solution was concentrated to dryness the residue dissolved in a minimal amount of CH2CL2 purified by prep

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The vinyl sulfide of Example 1(b) (0.100 g) was irradiated 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 after 10 min. N-Chlorosuccinimide (0.0446 g) was added and the mixture maintained at -78° C. for 15 minutes. Allyl alcohol (50 uL) 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 8. The solution was concentrated to dryness and the residue extracted with ether. The ether was evaporated and the resulting residue chromatographed on a silica prep. TLC plate with 20% ethyl acetate in hexane. The major band contained 47 mg of dioxetane 8: 1H NMR (CDCl3) δ1.09 (m, 1H), 1.26 (m, 1H), 1.471 (dq, 1H), 1.51-1.96 (m, 9H), 2.195 (br s, 1H), 3.127 (br s, 1H), 3.72-3.82 (m, 1H), 4.02-4.12 (m, 1H), 5.14-5.22 (m, 1H), 5.32-5.44 (m, 2H, vinylic H and phenolic-OH), 5.90-6.03 (m, 1H), 6.86-6.93 (m, 1H), 7.19 (br s, 2H), 7.26-7.34 (m, 1H). was consumed after 10 min N-Chlorosuccinimide (0.0446 g) was added Allyl alcohol (50 uL) was added the solution warmed to room temperature was heated reacted with 0.1 M TBAF in DMSO The solution was concentrated to dryness the residue extracted with ether The ether was evaporated the resulting residue chromatographed on a silica prep

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The vinyl sulfide of Example 1(b) (0.113 g) was irradiated for 15 min in 20 mL of methanol containing a few crystals (<1 mg) of methylene blue with continuous oxygen bubbling at -78° C. using a 1000 W Na lamp. Iodine (0.096 g) and 1 mL of 30% H2O2 were added and the mixture warmed to room temperature. Progress of the reaction was monitored by the disappearance of starting material by TLC (20% ethyl acetate in hexane) and the appearance of new bands 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 6 over a period of several hours. The solution was concentrated to 1-2 mL and separated on preparative TLC with 10% ethyl acetate in hexane. The band containing dioxetane 6 was collected, desorbed and evaporated yielding 77 mg. was heated The solution was concentrated to 1-2 mL separated on preparative TLC with 10% ethyl acetate in hexane The band containing dioxetane 6 was collected evaporated yielding 77 mg