Allyl Alcohol → N-(6-nitro-2,3-dihydro-1H-inden-5-yl)acetamide

HRID 1669087Notes

Reaction equation

HRID 1669087 reaction equation
IC1N=[N+:4]([O-:16])[C:5]2[CH:14]=[C:13]3[C:9]([CH2:10][CH:11](C)[CH2:12]3)=[CH:8][C:6]=2[N:7]=1.[CH2:17]([OH:20])[CH:18]=C.C([O-])(O)=[O:22].[Na+]>[N+](CCCC)(CCCC)(CCCC)CCCC.[Br-].CN(C=O)C.CC([O-])=O.CC([O-])=O.[Pd+2]>[N+:4]([C:5]1[CH:14]=[C:13]2[C:9]([CH2:10][CH2:11][CH2:12]2)=[CH:8][C:6]=1[NH:7][C:17](=[O:20])[CH3:18])([O-:16])=[O:22]

Participants

7

Reactant 3

HCID 7858Allyl AlcoholHCID 516892Sodium BicarbonateHCID 11952183HCID 11952183, compound

Product 1

HCID 10751392N-(6-nitro-2,3-dihydro-1H-inden-5-yl)acetamide

Reagents, catalysts & solvents 3

HCID 74236Tetrabutylammonium BromideCatalystHCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
50 °C

Procedure

Iodide 100 (1.53 g, 4.7 mmol) was added to a degassed solution of allyl alcohol (0.89 mL, 13.1 mmol), Pd(OAc)2 (52 mg, 0.23 mmol), nBu4NBr (1.35 g, 4.2 mmol) and NaHCO3 (0.86 g, 10.3 mmol) in DMF (40 mL) and the solution was stirred at 50° C. for 24 h under N2. The mixture was quenched with saturated aqueous NH4Cl solution (50 mL) and filtered. The filtrate was extracted with EtOAc (5×50 mL), dried and the solvent evaporated. The residue was purified by chromatography, eluting with a gradient (20-50%) of EtOAc/pet. ether, to give (i) starting material 100 (0.86 g, 56%) and (ii) aldehyde 101 as an orange gum: 1H NMR δ 9.93 (s, 1H, CHO), 8.21 (s, 1H, H-9), 7.69 (s, 1H, H-5), 3.35 (t, J=7.0 Hz, 2H, CH2), 3.20-3.27 (m, 2H, CH2), 3.19 (br dd, J=7.2, 6.7 Hz, 2H, CH2), 2.64-2.76 (m, 3H, H-7, CH2), 1.19 (d, J=6.4 Hz, 3H, CH3); 13C NMR δ 200.5, 163.9, 154.5, 148.7, 147.3, 132.4, 122.8, 114.4, 41.2, 40.9, 40.5, 35.0, 29.4, 20.2; MS (FAB+) m/z 258 (MH+, 60%), 242 (10); HRMS (FAB+) calcd for C14H16N3O2 (MH+) m/z 258.1243, found 258.1242.

Workup

  1. customThe mixture was quenched with saturated aqueous NH4Cl solution (50 mL)
  2. filtrationfiltered
  3. extractionThe filtrate was extracted with EtOAc (5×50 mL)
  4. customdried
  5. customthe solvent evaporated
  6. customThe residue was purified by chromatography
  7. washeluting with a gradient (20-50%) of EtOAc/pet. ether

Sources & evidence

ORD record
ord-e8c7a474aecc4f26b3cd83433d40adee
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

Loading…