P,P-Diphenylphosphinic azide → HCID 16244434, compound

HRID 1019681Notes

Reaction equation

HRID 1019681 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH:6]=[C:7]2[C:12](=[CH:13][CH:14]=1)[O:11][CH2:10][CH:9](C(O)=O)[CH2:8]2)=[O:4].C1(P([N:32]=[N+]=[N-])(C2C=CC=CC=2)=O)C=CC=CC=1>C(O)(C)(C)C>[CH3:1][O:2][C:3]([C:5]1[CH:6]=[C:7]2[C:12](=[CH:13][CH:14]=1)[O:11][CH2:10][CH:9]([NH2:32])[CH2:8]2)=[O:4]

Participants

4

Reactant 2

HCID 199401P,P-Diphenylphosphinic azideHCID 58164229HCID 58164229, compound

Product 1

HCID 16244434HCID 16244434, compoundYield 29%

Reagents, catalysts & solvents 1

HCID 6386tert-ButanolSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of XXXIII (1 g, 4.2 mmol) and TEA (1 mL) in 10 mL of tert-butylalcohol was added 1.15 g of diphenyl phosphoryl azide (4.2 mol). The reaction mixture was stirred at 80° C. for 12 h before concentrated in vacuo. The residue was dissolved in 20 mL of HCl/MeOH (1 N) and the mixture was stirred for at rt for 2 h. After solvent removal, the residue was partitioned between water and EtOAc. The aqueous layer was neutralized to pH 8 by addition of Na2CO3, and extracted with EtOAc. The organic phase was dried over Na2SO4 and concentrated to give 0.25 g of 3-amino-chroman-6-carboxylic acid methyl ester XXXIV (Yield 29%). MS: calc'd 208 (MH+), exp 208 (MH+).

Workup

  1. concentrationbefore concentrated in vacuo
  2. dissolutionThe residue was dissolved in 20 mL of HCl/MeOH (1 N)
  3. stirringthe mixture was stirred for at rt for 2 h
  4. customAfter solvent removal
  5. customthe residue was partitioned between water and EtOAc
  6. additionThe aqueous layer was neutralized to pH 8 by addition of Na2CO3
  7. extractionextracted with EtOAc
  8. dry with materialThe organic phase was dried over Na2SO4
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-3a9b249ceae24b3193257d23b84898f8
Source dataset
uspto-grants-2014_05
Patent number
US08716285B2

Reaction notes

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