Ammonium formate → HCID 86722342, compound

HRID 718763Notes

Reaction equation

HRID 718763 reaction equation
C1(C(C2C=CC=CC=2)=[N:8][C:9]2[CH:29]=[CH:28][C:12]3[C:13]4([CH2:26][CH3:27])[CH2:25][CH2:24][C:19]5([O:23][CH2:22][CH2:21][O:20]5)[CH2:18][CH:14]4[CH2:15][CH2:16][CH2:17][C:11]=3[CH:10]=2)C=CC=CC=1.C([O-])=O.[NH4+]>[Pd].CO>[CH2:26]([C:13]12[CH2:25][CH2:24][C:19]3([O:20][CH2:21][CH2:22][O:23]3)[CH2:18][CH:14]1[CH2:15][CH2:16][CH2:17][C:11]1[CH:10]=[C:9]([NH2:8])[CH:29]=[CH:28][C:12]=12)[CH3:27]

Participants

5

Reactant 2

HCID 2723923Ammonium formateHCID 86722341HCID 86722341, compound

Product 1

HCID 86722342HCID 86722342, compoundYield 97%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Conditions

Temperature
65 °C

Procedure

A flask with stir bar, condenser and nitrogen line was charged with rac-(4aR,11bS)—N-(diphenylmethylene)-11b-ethyl-1,2,4,4a,5,6,7,11b-octahydrospiro[dibenzo[a,c][7]annulene-3,2′-[1,3]dioxolan]-9-amine (21, R2=Ethyl) (0.550 g, 1.181 mmol), 10% Pd on carbon (0.094 g, 0.089 mmol) and MeOH (25 mL). Ammonium formate (1.12 g, 17.7 mmol) was added and the mixture was heated to about 65° C. After about 15 min the mixture was cooled to rt and filtered through a pad of Celite®. The pad was washed with MeOH (15 mL) then the filtrate was concentrated under reduced pressure. The residue was partitioned between EtOAc (20 mL), water (5 mL) and sat. aq. NaHCO3 (15 mL). The layers were separated and the aqueous layer was extracted with EtOAc (15 mL). The combined organic layers were dried over MgSO4, filtered and concentrated under reduced pressure to yield 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, 97%); LC/MS, method 3, Rt=2.50 min, MS m/z 302 (M+H)+. 1H NMR (400 MHz, DMSO) δ 6.83 (d, J=8.3 Hz, 1H), 6.36-6.28 (m, 2H), 4.75 (bs, 2H), 3.87-3.72 (m, 4H), 2.82-2.75 (m, 1H), 2.57-2.45 (m, 1H), 2.30-2.26 (m, 1H), 2.14-2.05 (m, 1H), 2.00-1.89 (m, 2H), 1.72-1.15 (m, 9H), 0.58 (t, J=7.4 Hz, 3H).

Workup

  1. temperatureAfter about 15 min the mixture was cooled to rt
  2. filtrationfiltered through a pad of Celite®
  3. washThe pad was washed with MeOH (15 mL)
  4. concentrationthe filtrate was concentrated under reduced pressure
  5. customThe residue was partitioned between EtOAc (20 mL), water (5 mL) and sat. aq. NaHCO3 (15 mL)
  6. customThe layers were separated
  7. extractionthe aqueous layer was extracted with EtOAc (15 mL)
  8. dry with materialThe combined organic layers were dried over MgSO4
  9. filtrationfiltered
  10. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-3f2f813c49bb49e987495e9ade7a23f8
Source dataset
uspto-grants-2015_11
Patent number
US09193744B2

Reaction notes

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