Oxygen → HCID 86754406, compound

HRID 1585382Notes

Reaction equation

HRID 1585382 reaction equation
C(S[CH:4]=[CH2:5])=C.CN(C1C=CC2N=C3C(=CC(C=C3)=[N+](C)C)SC=2C=1)C.O=O.ClN1C(=[O:34])CCC1=O.[C:36]([CH2:38][CH2:39][OH:40])#[N:37].CCCC[N+]([CH2:54][CH2:55][CH2:56][CH3:57])(CCCC)CCCC.[F-].C(S[C:62]1(C2C=CC=C(O)C=2)[C:65]2([CH:72]3[CH2:73][CH:68]4[CH2:69][CH:70]([CH2:74][CH:66]2[CH2:67]4)[CH2:71]3)[O:64][O:63]1)C.O1CCO1>C(Cl)Cl.CCCCCC.CS(C)=O.C(OCC)(=O)C>[C:36]([CH2:38][CH2:39][O:40][C:62]1([C:5]2[CH:4]=[CH:54][CH:55]=[C:56]([OH:34])[CH:57]=2)[C:65]2([CH:72]3[CH2:73][CH:68]4[CH2:69][CH:70]([CH2:74][CH:66]2[CH2:67]4)[CH2:71]3)[O:64][O:63]1)#[N:37]

Participants

13

Reactant 8

HCID 977OxygenHCID 4139Methylene blue cationHCID 8011HydracrylonitrileHCID 12321Divinyl sulfideHCID 31398ChlorosuccinimideHCID 1220291,2-DioxetaneHCID 2724141Tetrabutylammonium FluorideHCID 86754405HCID 86754405, compound

Product 1

HCID 86754406HCID 86754406, compound

Reagents, catalysts & solvents 4

HCID 679Dimethyl SulfoxideSolventHCID 6344DichloromethaneSolvent2×HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-78 °C

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).

Workup

  1. customfor 10 min
  2. temperaturethe solution warmed to room temperature
  3. temperaturewas heated
  4. concentrationThe solution was concentrated to dryness
  5. dissolutionthe residue dissolved in a minimal amount of CH2CL2
  6. custompurified by prep

Sources & evidence

ORD record
ord-7b62c15ebbca49cd8cf0ccfd42ccf61d
Source dataset
uspto-grants-1999_08
Patent number
US05936101

Reaction notes

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