Ethyl Acetate → HCID 86722343, compound

HRID 718764Notes

Reaction equation

HRID 718764 reaction equation
[CH2:1]([C:3]12[CH2:22][CH2:21][C:16]3([O:20][CH2:19][CH2:18][O:17]3)[CH2:15][CH:4]1[CH2:5][CH2:6][CH2:7][C:8]1[CH:13]=[C:12]([NH2:14])[CH:11]=[CH:10][C:9]=12)[CH3:2].C1C(=O)N([Br:30])C(=O)C1.C([O-])(O)=O.[Na+].CCOC(C)=O>C1COCC1>[Br:30][C:11]1[C:12]([NH2:14])=[CH:13][C:8]2[CH2:7][CH2:6][CH2:5][CH:4]3[CH2:15][C:16]4([CH2:21][CH2:22][C:3]3([CH2:1][CH3:2])[C:9]=2[CH:10]=1)[O:17][CH2:18][CH2:19][O:20]4

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 67184N-bromobutanimideHCID 516892Sodium BicarbonateHCID 86722342HCID 86722342, compound

Product 1

HCID 86722343HCID 86722343, compoundYield 59%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

rac-(4aR,11bS)-11b-ethyl-1,2,4,4a,5,6,7,11b-octahydrospiro[dibenzo[a,c][7]annulene-3,2′-[1,3]dioxolan]-9-amine (22, R2=Ethyl) (0.345 g, 1.145 mmol) in THF (8 mL) was cooled to about 0° C. then NBS (0.204 g, 1.145 mmol) was added. After about 10 min, sat. aq. NaHCO3 (20 mL) and EtOAc (25 mL) were added. The mixture was warmed to rt and the layers were separated. The aqueous layer was extracted with EtOAc (15 mL). The combined organic layers were dried over MgSO4, filtered and concentrated under reduced pressure. The residue was purified on silica gel (12 g) using a gradient of 0-10% EtOAc in DCM. Product fractions were combined and concentrated under reduced pressure to yield rac-(4aR,11bS)-10-bromo-11b-ethyl-1,2,4,4a,5,6,7,11b-octahydrospiro[dibenzo[a,c][7]annulene-3,2′-[1,3]dioxolan]-9-amine (23, R2=Ethyl) (0.255 g, 59%); LC/MS, method 3, Rt=2.85 min, MS m/z 380, 382 (M+H)+. 1H NMR (400 MHz, DMSO) δ 7.03 (s, 1H), 6.55 (s, 1H), 5.04 (s, 2H), 3.89-3.73 (m, 4H), 2.80-2.73 (m, 1H), 2.58-2.46 (m, 1H), 2.26-2.19 (m, 1H), 2.14-2.05 (m, 1H), 2.02-1.88 (m, 2H), 1.72-1.45 (m, 4H), 1.43-1.18 (m, 5H), 0.60 (t, J=7.4 Hz, 3H).

Workup

  1. customthe layers were separated
  2. extractionThe aqueous layer was extracted with EtOAc (15 mL)
  3. dry with materialThe combined organic layers were dried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was purified on silica gel (12 g)
  7. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-87f5d4b9fdc646c49de674ad6f54a743
Source dataset
uspto-grants-2015_11
Patent number
US09193744B2

Reaction notes

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