Nitric Acid → HCID 22922925, compound

HRID 1077384Notes

Reaction equation

HRID 1077384 reaction equation
[C:1]([O:9][C:10]1[CH:15]=[CH:14][C:13]([C:16]2[CH:21]=[CH:20][C:19]([OH:22])=[CH:18][CH:17]=2)=[CH:12][CH:11]=1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[N+:23]([O-])([OH:25])=[O:24].O>C(O)(=O)C>[C:1]([O:9][C:10]1[CH:15]=[CH:14][C:13]([C:16]2[CH:17]=[CH:18][C:19]([OH:22])=[C:20]([N+:23]([O-:25])=[O:24])[CH:21]=2)=[CH:12][CH:11]=1)(=[O:8])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 962WaterHCID 229229204-Benzoyloxy-4'-hydroxybiphenyl

Product 1

HCID 22922925HCID 22922925, compound

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

To an argon-flushed flask containing a suspension 0.486 g (1.68 mmol) of 4'-hydroxy-4-biphenylyl benzoate in 10 ml of acetic acid at 10°-15° C., 0.345 ml of HNO3 (d: 1.41) was added dropwise (about a drop per min). Then the reaction mixture was vigorously stirred at the same temperature for 30 min. Water (40 ml ) was added and the mixture was again stirred for 30 min. The yellow precipitate was filtered, washed several times with water, dried and purified by flash chromatography on silica gel using dichloromethane/hexanes [65/35] as eluent to give 4'-hydroxy-3'-nitro-4-biphenylyl benzoate (compound 15, Scheme II) as a yellow solid (0:539 g, 96%). This material was recrystallized from ethanol to give product of mp. 163° C.; Rf [hexanes/dichloromethane 40/60]: 0.42; 1H NMR (300 MHz, CDCl3): δ7.25(d, 1H, J=8.7 Hz), 7.33(d, 2H, J=8.7 Hz), 7.50-7.70(m, 5H), 7.84(dd, 1H, J=2.7 Hz, J=8.7 Hz), 8.23 (d, 2H, J=7.2 Hz), 8.32(d, 1H, J=2.7 Hz), 10.60(s, 1H); 13C NMR (300 MHz, CDCl3): δ120.54, 122.45, 122.81, 127.85, 128.65, 129.33, 130.23, 133.04, 133.78 136.04, 136.22, 150.91, 154.44, 165.15; IR (CHCL3): 3250(broad), 3020, 1740, 1620, 1540, 1510, 1490, 1325, 1270, 1225, 1220, 1170, 1080, 1065, 1025, 1000, 850 cm-1 ; Mass spectrum, m/z(rel.intensity): 335(M+ 7), 105(100), 77(16).

Workup

  1. customTo an argon-flushed flask
  2. stirringthe mixture was again stirred for 30 min
  3. filtrationThe yellow precipitate was filtered
  4. washwashed several times with water
  5. customdried
  6. custompurified by flash chromatography on silica gel

Sources & evidence

ORD record
ord-70c039e8b95748c587108f72521f7358
Source dataset
uspto-grants-1996_08
Patent number
US05543078

Reaction notes

Loading…