Ethyl Acetate → 3-Ethyl-2,3,9,10,11,12-hexahydro-1-methyl-1H-quino[4,3,2-ef][1,4]benzoxazepine fumarate

HRID 981940Notes

Reaction equation

HRID 981940 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].[Cl-].[Al+3].[Cl-].[Cl-].[CH2:11]([CH:13]1[C:19](=[O:20])[N:18]([CH3:21])[C:17]2=[C:22]3[C:27](=[N:28][C:29]4=[CH:30][CH:31]=[CH:32][C:15](=[C:16]24)[O:14]1)[CH2:26][CH2:25][CH2:24][CH2:23]3)[CH3:12].[OH-:33].[Na+].[C:35]([O:38]CC)(=[O:37])[CH3:36]>O1CCCC1>[C:19]([OH:20])(=[O:33])/[CH:13]=[CH:36]/[C:35]([OH:38])=[O:37].[CH2:11]([CH:13]1[CH2:19][N:18]([CH3:21])[C:17]2=[C:22]3[C:27](=[N:28][C:29]4=[CH:30][CH:31]=[CH:32][C:15](=[C:16]24)[O:14]1)[CH2:26][CH2:25][CH2:24][CH2:23]3)[CH3:12]

Participants

7

Reactant 5

HCID 8857Ethyl AcetateHCID 14798Sodium HydroxideHCID 6451240Aluminum(III) ChlorideHCID 21226445Aluminium lithium hydrideHCID 538029823-ethyl-1,3,9,10,11,12-hexahydro-1-methyl-2H-quino[4,3,2-ef][1,4]benzoxazepin-2-one

Product 1

HCID 677566033-Ethyl-2,3,9,10,11,12-hexahydro-1-methyl-1H-quino[4,3,2-ef][1,4]benzoxazepine fumarateYield 38%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of lithium aluminum hydride in tetrahydrofuran (1M, 11.99 ml) and dry tetrahydrofuran (30 ml) was added aluminum chloride (1.6 g) in portions, with stirring. After five mins, 3-ethyl-1,3,9,10,11,12-hexahydro-1-methyl-2H-quino[4,3,2-ef][1,4]benzoxazepin-2-one (3.55 g) was added, and stirring was continued for 0.5 hr. Ethyl acetate (200 ml) and 10% sodium hydroxide solution (200 ml) were added, the organic layer was separated, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was flash chromatographed (1.5% triethylamine/toluene). The appropriate fractions were concentrated and the residue was treated with fumaric acid followed by recrystallization from methanol to give 1.82 g (38%) of product, mp 243° C. (dec.).

Workup

  1. stirringstirring
  2. waitwas continued for 0.5 hr
  3. customthe organic layer was separated
  4. dry with materialdried over anhydrous magnesium sulfate
  5. filtrationfiltered
  6. concentrationthe filtrate was concentrated
  7. customchromatographed (1.5% triethylamine/toluene)
  8. concentrationThe appropriate fractions were concentrated
  9. additionthe residue was treated with fumaric acid
  10. customfollowed by recrystallization from methanol

Sources & evidence

ORD record
ord-76e287b6f2c34491a4397ed20cb2334f
Source dataset
uspto-grants-1991_02
Patent number
US04994452

Reaction notes

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