Oxygen → HCID 11784003, compound

HRID 1585386Notes

Reaction equation

HRID 1585386 reaction equation
C(SC=C)=C.C1C(I)=[C:10]([OH:13])C(I)=C2OC3C(C4(OC(=O)C5C(Cl)=C(Cl)C(Cl)=C(Cl)C4=5)C=12)=CC(I)=C(O)C=3I.O=O.FC1C=CC(S[C:49]2([C:62]3[CH:67]=[CH:66][CH:65]=[C:64]([O:68][C:69](=[O:74])[C:70]([CH3:73])([CH3:72])[CH3:71])[CH:63]=3)[C:52]3([CH:59]4[CH2:60][CH:55]5[CH2:56][CH:57]([CH2:61][CH:53]3[CH2:54]5)[CH2:58]4)[O:51][O:50]2)=CC=1.O1CCO1>CO>[CH3:10][O:13][C:49]1([C:62]2[CH:67]=[CH:66][CH:65]=[C:64]([O:68][C:69](=[O:74])[C:70]([CH3:73])([CH3:71])[CH3:72])[CH:63]=2)[C:52]2([CH:53]3[CH2:54][CH:55]4[CH2:56][CH:57]([CH2:58][CH:59]2[CH2:60]4)[CH2:61]3)[O:51][O:50]1

Participants

7

Reactant 5

HCID 977OxygenHCID 12321Divinyl sulfideHCID 69439Rose Bengal LactoneHCID 1220291,2-DioxetaneHCID 15327848HCID 15327848, compound

Product 1

HCID 11784003HCID 11784003, compound

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

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).

Workup

  1. customto be completely consumed
  2. additioniodine (0.096 g) and 1 mL of 30% H2O2 were added
  3. temperaturewas heated
  4. customreacted with 0.1 M TBAF in DMSO
  5. concentrationThe solution was concentrated to 1-2 mL
  6. customseparated on preparative TLC with 5% ethyl acetate in hexane
  7. additionThe band containing dioxetane 20
  8. customwas collected
  9. customevaporated
  10. customto yield the product as a slightly yellow oil

Sources & evidence

ORD record
ord-1a2a24e3a13b4dc5afaafb9ee55f82e4
Source dataset
uspto-grants-1999_08
Patent number
US05936101

Reaction notes

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