Methyl vinyl ketone → HCID 86722476, compound

HRID 718861Notes

Reaction equation

HRID 718861 reaction equation
[Na].[CH3:2][O:3][C:4]1[N:9]=[CH:8][C:7]2[CH:10]([CH2:16][C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][N:18]=3)[C:11](=O)[CH2:12][CH2:13][CH2:14][C:6]=2[CH:5]=1.[O-]CC.[Na+].[CH3:27][C:28](=[O:31])[CH:29]=[CH2:30]>CCO>[CH3:2][O:3][C:4]1[N:9]=[CH:8][C:7]2[C:10]3([CH2:16][C:17]4[CH:22]=[CH:21][CH:20]=[CH:19][N:18]=4)[CH2:30][CH2:29][C:28](=[O:31])[CH:27]=[C:11]3[CH2:12][CH2:13][CH2:14][C:6]=2[CH:5]=1

Participants

6

Reactant 4

HCID 6570Methyl vinyl ketoneHCID 2723922Sodium ethoxideHCID 5360545SodiumHCID 86722475HCID 86722475, compound

Product 1

HCID 86722476HCID 86722476, compoundYield 60.1%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Conditions

Temperature
63 °C

Procedure

Sodium (2.21 g, 96 mmol) and EtOH (350 mL) were stirred until a solution was formed. 3-Methoxy-9-(pyridin-2-ylmethyl)-6,7-dihydro-5H-cyclohepta[c]pyridin-8 (9H)-one (128, R2=Pyridin-2-ylmethyl) (26.6 g, 94 mmol) was suspended in EtOH (220 mL) then treated with the sodium ethoxide solution. The mixture was warmed to an internal temperature of about 63° C. then but-3-en-2-one (9.76 mL, 118 mmol) was added over about 2 to 3 min. The mixture was stirred at an internal temperature of about 65-70° C. for about 45 min then the mixture was cooled to rt. The solvents were removed under reduced pressure then the material was stirred with EtOH (250 mL) for about 30 min. The solids were collected by filtration then washed with EtOH (25 mL). The material was dried to yield 3-methoxy-11a-(pyridin-2-ylmethyl)-6,7,11,11a-tetrahydro-5H-benzo[6,7]cyclohepta[1,2-c]pyridin-9(10H)-one (129, R2=Pyridin-2-ylmethyl) (18.89 g, 60.0%); LC/MS, method 3, Rt=1.12, 1.82 min, MS m/z 335 (M+H)+. 1H NMR (400 MHz, DMSO) δ 8.44 (s, 1H), 8.42-8.37 (m, 1H), 7.63-7.58 (m, 1H), 7.18-7.14 (m, 1H), 7.13-7.08 (m, 1H), 6.58 (s, 1H), 5.88 (s, 1H), 3.83 (s, 3H), 3.70 (d, J=13.4 Hz, 1H), 3.56 (d, J=13.4 Hz, 1H), 2.87-2.75 (m, 1H), 2.74-2.59 (m, 2H), 2.41-2.05 (m, 4H), 1.85-1.65 (m, 3H).

Workup

  1. customwas formed
  2. temperaturethe mixture was cooled to rt
  3. customThe solvents were removed under reduced pressure
  4. stirringthe material was stirred with EtOH (250 mL) for about 30 min
  5. filtrationThe solids were collected by filtration
  6. washthen washed with EtOH (25 mL)
  7. customThe material was dried

Sources & evidence

ORD record
ord-32d2bbc17ce3442c8096de8c90d82695
Source dataset
uspto-grants-2015_11
Patent number
US09193744B2

Reaction notes

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