Dichloromethane → 9-Nitro-2,5-dihydrobenzo[b]oxepine

HRID 1041144Notes

Reaction equation

HRID 1041144 reaction equation
[CH2:1]([C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([N+:10]([O-:12])=[O:11])[C:5]=1[O:13][CH2:14][CH:15]=[CH2:16])C=C.C(Cl)Cl>C1CCC(P(C2CCCCC2)C2CCCCC2)CC1.C1CCC(P(C2CCCCC2)C2CCCCC2)CC1.C1C=CC(C=[Ru](Cl)Cl)=CC=1>[N+:10]([C:6]1[C:5]2[O:13][CH2:14][CH:15]=[CH:16][CH2:1][C:4]=2[CH:9]=[CH:8][CH:7]=1)([O-:12])=[O:11]

Participants

4

Reactant 2

HCID 6344DichloromethaneHCID 112182621-Allyl-2-allyloxy-3-nitrobenzene

Product 1

HCID 232472469-Nitro-2,5-dihydrobenzo[b]oxepine

Reagents, catalysts & solvents 1

HCID 11967259Benzylidenebis(tricyclohexylphosphine)dichlororutheniumCatalyst

Procedure

To a stirred solution of 1-allyl-2-allyloxy-3-nitrobenzene (100 mg, 0.0004 mol) in methylene chloride (6 mL, 0.09 mol) at room temperature was added benzylidene-bis(tricyclohexylphosphine)dichlororuthenium (20 mg, 0.00002 mol). The reaction mixture was stirred at room temperature overnight. The reaction solvent was removed in vacuo leaving a dark solid which was purified by ISCO column chromatography on silica gel using hexane-methyl-t-butyl ether (3:1). The fractions corresponding to product were combined and concentrated in vacuo to give 9-nitro-2,5-dihydrobenzo[b]oxepine as a dark solid which was further purified to give product as an off-white solid (80 mg, 90%). 1H NMR (CDCl3, 400 MHz) δ 7.66 (d, 1H, J=8.09 Hz), 7.33 (d, 1H, J=7.32 Hz), 7.11 (dd, 1H, J=7.58, 8.09 Hz), 5.86 (m, 1H), 5.54 (d, 1H, J=11 Hz), 4.79 (s, 2H), 3.54 (s, 2H);

Workup

  1. customThe reaction solvent was removed in vacuo
  2. customleaving a dark solid which
  3. customwas purified by ISCO column chromatography on silica gel
  4. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-0c5eca73cb2949d1a8a7e5d1ca931a23
Source dataset
uspto-grants-2013_10
Patent number
US08552186B2

Reaction notes

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