Ethanol → HCID 14501375, compound

HRID 1904604Notes

Reaction equation

HRID 1904604 reaction equation
[N:1]([C:4]1[C:5]([F:24])=[CH:6][C:7]2[C:17](=[O:18])[C:16]([C:19]([O:21][CH2:22][CH3:23])=[O:20])=[CH:15][N:9]3[C@@H:10]([CH3:14])[CH2:11][O:12][C:13]=1[C:8]=23)=[N+]=[N-].C(O)C>CN(C)C=O.[Pd]>[NH2:1][C:4]1[C:5]([F:24])=[CH:6][C:7]2[C:17](=[O:18])[C:16]([C:19]([O:21][CH2:22][CH3:23])=[O:20])=[CH:15][N:9]3[C@@H:10]([CH3:14])[CH2:11][O:12][C:13]=1[C:8]=23

Participants

5

Reactant 2

HCID 702EthanolHCID 14501373HCID 14501373, compound

Product 1

HCID 14501375HCID 14501375, compoundYield 78.6%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 6228DimethylformamideSolvent2×

Conditions

Temperature
0 °C

Procedure

A slurry of 701 g of ethyl (S)-10-azido-9-fluoro-2,3-dihydro-3-methyl-7-oxo-7H-pyrido[1,2,3-de][1,4]benzoxazine-6-carboxylate in 6.0 of dimethylformamide was charged to the five gallon autoclave. After placing the vessel under nitrogen, a slurry of 45 g of 10% palladium-on-carbon in 700 ml of dimethylformamide was added. The mixture was hydrogenated at 48-50 psi and 600 RPM. A 10° C. rise in temperature was observed during the first thirty minutes of reaction. The reaction mixture was filtered and washed with 2×3 L of dimethylformamide. Concentration of the filtrate under aspirator pressure gave a very thick, dark residue (volume~700 ml). Ethanol (1.2 L) was added and the suspension was refluxed briefly. After cooling to 0° C., the product was collected, washed with 3×300 ml of cold ethanol and dried for eighteen hours at 80° C. in vacuo to give 508 g of product which was shown to be 97.6% pure by HPLC.

Workup

  1. customA 10° C. rise in temperature was observed during the first thirty minutes of reaction
  2. filtrationThe reaction mixture was filtered
  3. washwashed with 2×3 L of dimethylformamide
  4. customConcentration of the filtrate under aspirator pressure gave a very thick, dark residue (volume~700 ml)
  5. temperaturethe suspension was refluxed briefly
  6. customthe product was collected
  7. washwashed with 3×300 ml of cold ethanol
  8. customdried for eighteen hours at 80° C. in vacuo

Sources & evidence

ORD record
ord-48a5012d54354b92816be28611a5e6ce
Source dataset
uspto-grants-1989_06
Patent number
US04839355

Reaction notes

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