HCID 3615705, compound → HCID 54133208, compound

HRID 1493634Notes

Reaction equation

HRID 1493634 reaction equation
[CH3:1][O:2][C:3](=[O:19])[CH2:4][NH:5][C:6]1[CH:11]=[CH:10][C:9]([O:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)=[CH:8][CH:7]=1.[N:20]([O-])=O.[Na+]>C(O)(=O)C.O.[Zn]>[O:12]([C:9]1[CH:10]=[CH:11][C:6]([N:5]([CH2:4][C:3]([O:2][CH3:1])=[O:19])[NH2:20])=[CH:7][CH:8]=1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

6

Reactant 2

HCID 3615705HCID 3615705, compound2×HCID 23668193Sodium Nitrite

Product 1

HCID 54133208HCID 54133208, compound

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 176Acetic AcidSolventHCID 962WaterSolvent3×

Procedure

N-(4-Phenoxyphenyl)glycine methylester (Intermediate 75, 13.5 g, 0.0525 mol) was dissolved in a mixture of acetic acid (90 ml) and water (5 ml) and the solution was cooled to ~5° C. To this was added a solution of sodium nitrite (3,8 g, 0.55 mol) in water (10 ml) over 15 minutes. Stirring was continued for 2 hours and the reaction was cooled to ~0° C. Zinc dust (13.4 g, 0.2048 mol) was added over 30 minutes and the reaction stirred at 0°-5° C. for 2 hours before being poured into water (200 ml) and extracted with ethyl acetate (2×150 ml). The organic extract was washed with 8% sodium bicarbonate solution until effervescence had ceased, dried (MgSO4) and evaporated to give a brown semi-solid. This was triturated with ether/hexane (1:1) to recover starting material (6.5 g, 48%). The liquors were evaporated and purified by flash column chromatography on silica (Merck 9385; 250 g) eluting with ether-hexane (1:1) to give the title compound (Intermediate 76) as an off white solid (1.25 g, 9%) m.p 71°-73° C.

Workup

  1. temperaturethe solution was cooled to ~5° C
  2. temperaturethe reaction was cooled to ~0° C
  3. stirringthe reaction stirred at 0°-5° C. for 2 hours
  4. extractionextracted with ethyl acetate (2×150 ml)
  5. extractionThe organic extract
  6. washwas washed with 8% sodium bicarbonate solution until effervescence
  7. dry with materialdried (MgSO4)
  8. customevaporated
  9. customto give a brown semi-solid
  10. customThis was triturated with ether/hexane (1:1)
  11. customto recover
  12. customThe liquors were evaporated
  13. custompurified by flash column chromatography on silica (Merck 9385; 250 g)
  14. washeluting with ether-hexane (1:1)

Sources & evidence

ORD record
ord-118eeaabf17b4d3c818f6867d19d6630
Source dataset
uspto-grants-1991_06
Patent number
US05023255

Reaction notes

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