Ethyl Acetate → HCID 136101881, compound

HRID 1091734Notes

Reaction equation

HRID 1091734 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:18]=[CH:19][CH:20]=1)[CH2:5][C:6]1[C:7]2[C:8](=[C:13]([CH3:17])[NH:14][C:15]=2[CH3:16])[C:9](=[O:12])[NH:10][N:11]=1.C(N(C(C)C)C(C)C)C.CC[O:32][C:33](C)=[O:34]>CN(C)C1C=CN=CC=1.O1CCOCC1.O.[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[Mo].C(O[Pd]CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C)(=O)C>[CH3:16][C:15]1[NH:14][C:13]([CH3:17])=[C:8]2[C:7]=1[C:6]([CH2:5][C:4]1[CH:3]=[C:2]([CH:20]=[CH:19][CH:18]=1)[C:33]([OH:34])=[O:32])=[N:11][NH:10][C:9]2=[O:12]

Participants

9

Reactant 3

HCID 8857Ethyl AcetateHCID 81531DiisopropylethylamineHCID 1361018774-(3-bromobenzyl)-5,7-dimethyl-2,6-dihydro-1H-pyrrolo[3,4-d]pyridazin-1-one

Product 1

HCID 136101881HCID 136101881, compoundYield 100%

Reagents, catalysts & solvents 5

HCID 142844-(Dimethylamino)pyridineCatalystHCID 98885Molybdenum carbonyl (Mo(CO)6)CatalystHCID 178476741HCID 178476741, compoundCatalystHCID 962WaterSolvent2×HCID 312751,4-DioxaneSolvent

Conditions

Temperature
150 °C

Procedure

4-(3-Bromobenzyl)-5,7-dimethyl-2,6-dihydro-1H-pyrrolo[3,4-d]pyridazin-1-one (50) (0.188 g, 0.57 mmol), molybdenum hexacarbonyl (0.224 g, 0.85 mmol), N,N-dimethylpyridin-4-amine (0.138 g, 1.13 mmol), N-ethyl-N-isopropylpropan-2-amine (0.197 mL, 1.13 mmol) and acetoxy(2-(dio-tolylphosphino)benzyl)palladium (0.027 g, 0.03 mmol) were suspended in a mixture of dioxane (2.0 mL) and water (2.0 mL) and sealed into a microwave tube. The reaction was heated to 150° C. for 30 minutes in the microwave reactor and cooled to room temperature. The reaction mixture was diluted with water (50 mL) and EtOAc (50 mL). The mixture was filtered through celite. The layers were separated and the aqueous was adjusted to pH2 with 2M HCl. The resulting precipitate was collected by filtration, washed with water (50 mL), Et2O (50 mL) and dried under vacuum to afford the desired material as a brown solid (0.200 g, >100% yield), which was used without further purification. 1H NMR (400.132 MHz, DMSO) δ 2.26 (3H, s), 2.51 (3H, s), 4.13 (2H, s), 7.39-7.48 (2H, m), 7.78 (2H, m), 11.08 (1H, s), 11.93 (1H, s), 12.86 (1H, s); m/z (LC-MS, ESI+), RT=1.41 min (M+H=298.08).

Workup

  1. customsealed into a microwave tube
  2. temperaturecooled to room temperature
  3. filtrationThe mixture was filtered through celite
  4. customThe layers were separated
  5. filtrationThe resulting precipitate was collected by filtration
  6. washwashed with water (50 mL), Et2O (50 mL)
  7. customdried under vacuum

Sources & evidence

ORD record
ord-2ea4038461644a488fb7a6c2de2bd87d
Source dataset
uspto-grants-2012_03
Patent number
US08129380B2

Reaction notes

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