Oxygen → HCID 86754407, compound

HRID 1585383Notes

Reaction equation

HRID 1585383 reaction equation
C(SC=C)=C.CN(C1C=CC2N=C3C(=CC(C=C3)=[N+](C)C)SC=2C=1)C.O=O.C(S[C:31]1([C:44]2[CH:49]=[CH:48][CH:47]=[C:46]([OH:50])[CH:45]=2)[C:34]2([CH:41]3[CH2:42][CH:37]4[CH2:38][CH:39]([CH2:43][CH:35]2[CH2:36]4)[CH2:40]3)[O:33][O:32]1)C.[O:51]1[CH2:54][CH2:53][O:52]1>C(Cl)Cl>[OH:51][CH2:54][CH2:53][O:52][C:31]1([C:44]2[CH:49]=[CH:48][CH:47]=[C:46]([OH:50])[CH:45]=2)[C:34]2([CH:41]3[CH2:40][CH:39]4[CH2:38][CH:37]([CH2:36][CH:35]2[CH2:43]4)[CH2:42]3)[O:33][O:32]1

Participants

7

Reactant 5

HCID 977OxygenHCID 4139Methylene blue cationHCID 12321Divinyl sulfide2×HCID 1220291,2-DioxetaneHCID 86754405HCID 86754405, compound

Product 1

HCID 86754407HCID 86754407, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
-78 °C

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.

Workup

  1. customwas consumed
  2. additionN-Chlorosuccinimide (0.044 g) was added
  3. additionEthylene glycol (37 uL) was added
  4. temperaturethe solution warmed to room temperature
  5. temperaturewas heated
  6. customreacted with 0.1 M TBAF in DMSO
  7. concentrationThe solution was concentrated to dryness
  8. extractionthe residue extracted with ether
  9. customThe ether was evaporated
  10. customthe resulting residue chromatographed on a silica prep

Sources & evidence

ORD record
ord-1cf18de5e21e478388eec35b560c143b
Source dataset
uspto-grants-1999_08
Patent number
US05936101

Reaction notes

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