Hydrogen Peroxide → HCID 11077506, compound

HRID 1585380Notes

Reaction equation

HRID 1585380 reaction equation
C(SC=C)=C.CN(C1C=CC2N=C3C(=CC(C=C3)=[N+](C)C)SC=2C=1)C.O=O.II.OO.CCCC[N+](CCCC)(CCCC)CCCC.[F-].C(S[C:53]1([C:66]2[CH:71]=[CH:70][CH:69]=[C:68]([OH:72])[CH:67]=2)[C:56]2([CH:63]3[CH2:64][CH:59]4[CH2:60][CH:61]([CH2:65][CH:57]2[CH2:58]4)[CH2:62]3)[O:55][O:54]1)C.[O:73]1[CH2:76]CO1>CO.CCCCCC.CS(C)=O.C(OCC)(=O)C>[OH:72][C:68]1[CH:67]=[C:66]([C:53]2([O:73][CH3:76])[C:56]3([CH:57]4[CH2:65][CH:61]5[CH2:60][CH:59]([CH2:64][CH:63]3[CH2:62]5)[CH2:58]4)[O:55][O:54]2)[CH:71]=[CH:70][CH:69]=1

Participants

13

Reactant 8

HCID 784Hydrogen PeroxideHCID 807IodineHCID 977OxygenHCID 4139Methylene blue cationHCID 12321Divinyl sulfideHCID 1220291,2-DioxetaneHCID 2724141Tetrabutylammonium FluorideHCID 86754405HCID 86754405, compound

Product 1

HCID 11077506HCID 11077506, compound

Reagents, catalysts & solvents 4

HCID 679Dimethyl SulfoxideSolventHCID 887MethanolSolventHCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

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.

Workup

  1. temperaturewas heated
  2. concentrationThe solution was concentrated to 1-2 mL
  3. customseparated on preparative TLC with 10% ethyl acetate in hexane
  4. additionThe band containing dioxetane 6
  5. customwas collected
  6. customevaporated
  7. customyielding 77 mg

Sources & evidence

ORD record
ord-c3c8ed172dc54fa0adee247fe312c514
Source dataset
uspto-grants-1999_08
Patent number
US05936101

Reaction notes

Loading…