Acetonitrile → HCID 86747806, compound

HRID 1032925Notes

Reaction equation

HRID 1032925 reaction equation
Br[C:2]1[C:3]([F:22])=[CH:4][C:5]2[C:15](=[O:16])[C:14]([C:17]([O:19][CH2:20][CH3:21])=[O:18])=[CH:13][N:7]3[C@@H:8]([CH3:12])[CH2:9][O:10][C:11]=1[C:6]=23.C[Sn](C)(C)[C:25]1[CH:30]=[CH:29][N:28]=[CH:27][CH:26]=1.C(#N)C>C(O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[N:28]1[CH:29]=[CH:30][C:25]([C:2]2[C:3]([F:22])=[CH:4][C:5]3[C:15](=[O:16])[C:14]([C:17]([O:19][CH2:20][CH3:21])=[O:18])=[CH:13][N:7]4[C@@H:8]([CH3:12])[CH2:9][O:10][C:11]=2[C:6]=34)=[CH:26][CH:27]=1

Participants

6

Reactant 3

HCID 6342AcetonitrileHCID 11128458Pyridine, 4-(trimethylstannyl)-HCID 13732848HCID 13732848, compound

Product 1

HCID 86747806HCID 86747806, compound

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 702EthanolSolvent

Conditions

Temperature
150 °C

Procedure

Ethyl (S)-10-bromo-9-fluoro-2,3-dihydro-3-methyl-7-oxo-7H-pyrido[1,2,3-de][1,4]benzoxazine-6-carboxylate (U.S. Pat. No. 4,839,355, Example 5f) (3.50 g), 2.97 g of 4-(trimethylstannyl)pyridine and 0.155 g of dichlorobis(triphenylphosphine)palladium were combined in a Parr apparatus in 200 ml of absolute ethyl alcohol and the mixture under nitrogen was heated at 150° C. for 41/2 hours, allowed to cool slowly and concentrated in vacuo. The concentrate was taken up in chloroform and residues were removed by filtration. The filtrate was extracted with sufficient 1M hydrochloric acid to extract all the product and the aqueous extract was poured onto ice and saturated sodium acetate was added. The resulting mixture was extracted with chloroform and the chloroform extract was washed with brine followed by sodium bicarbonate, dried over magnesium sulfate and concentrated to give, after recrystallization from acetonitrile, 2.56 g of a mixture of the title compound with its corresponding 6-carboxylic acid (73.5% yield); m.p. 249°-252° C. This was combined with 100 mg of the same product obtained previously by an analogous procedure.

Workup

  1. temperatureto cool slowly
  2. concentrationconcentrated in vacuo
  3. customresidues were removed by filtration
  4. extractionThe filtrate was extracted with sufficient 1M hydrochloric acid
  5. extractionto extract all the product
  6. extractionthe aqueous extract
  7. additionwas poured onto ice and saturated sodium acetate
  8. additionwas added
  9. extractionThe resulting mixture was extracted with chloroform
  10. extractionthe chloroform extract
  11. washwas washed with brine
  12. dry with materialdried over magnesium sulfate
  13. concentrationconcentrated
  14. customto give

Sources & evidence

ORD record
ord-b5629539ddf84cda8ae4b71c4d95b74c
Source dataset
uspto-grants-1994_05
Patent number
US05308843

Reaction notes

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