Oxygen → HCID 86754408, compound

HRID 1585384Notes

Reaction equation

HRID 1585384 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.O1CCO1.[C:55]1([OH:61])[CH:60]=[CH:59][CH:58]=[CH:57][CH:56]=1.C12CC3CC(CC(C3)C1=O)C2>C(Cl)Cl>[OH:50][C:46]1[CH:45]=[C:44]([C:31]2([O:61][C:55]3[CH:60]=[CH:59][CH:58]=[CH:57][CH:56]=3)[C:34]3([CH:41]4[CH2:40][CH:39]5[CH2:38][CH:37]([CH2:36][CH:35]3[CH2:43]5)[CH2:42]4)[O:33][O:32]2)[CH:49]=[CH:48][CH:47]=1

Participants

9

Reactant 7

HCID 977OxygenHCID 996Phenol2×HCID 4139Methylene blue cationHCID 12321Divinyl sulfide2×HCID 64151AdamantanoneHCID 1220291,2-Dioxetane3×HCID 86754405HCID 86754405, compound

Product 1

HCID 86754408HCID 86754408, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
-78 °C

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.

Workup

  1. customwas consumed
  2. additionN-Chlorosuccinimide (0.047 g) was added
  3. additionPhenol (83 mg) 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
  8. customthe residue chromatographed on a silica prep
  9. customThe major band was isolated

Sources & evidence

ORD record
ord-5602636ecca94b058e8c5bfa2de965b5
Source dataset
uspto-grants-1999_08
Patent number
US05936101

Reaction notes

Loading…