Acetic Acid → HCID 13531649, compound

HRID 653104Notes

Reaction equation

HRID 653104 reaction equation
OC([C:5]1[C:13]2[O:12][CH:11]=[C:10]([C:14]3[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=3)[C:9]=2[CH:8]=[CH:7][CH:6]=1)C#N.CN.Cl.Cl.[CH3:24][NH:25]C(C1C2OC=C(C3C=CC=CC=3)C=2C=CC=1)C#N.[N+:44]([O-:49])([N+]([O-])=O)=[O:45].[C:50]([OH:53])(=[O:52])[CH3:51]>C1C=CC=CC=1.ClCCl>[CH3:24][NH:25][CH:51]([C:5]1[C:13]2[O:12][C:11]([N+:44]([O-:49])=[O:45])=[C:10]([C:14]3[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=3)[C:9]=2[CH:8]=[CH:7][CH:6]=1)[C:50]([OH:53])=[O:52]

Participants

9

Reactant 6

HCID 176Acetic Acid2×HCID 313Hydrochloric Acid2×HCID 6329MethylamineHCID 25352Nitrogen oxide (N2O4)HCID 20195510HCID 20195510, compoundHCID 70436678HCID 70436678, compound

Product 1

HCID 13531649HCID 13531649, compound

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
20 °C

Procedure

A mixture of 5 g. (0.02 mole) of α-hydroxy-3-phenylbenzofuran-7-acetonitrile and 2 g. of methylamine in 100 ml. of dichloromethane is heated to its reflux temperature, then stirred at 20° C. for 16 hours. The mixture is evaporated to provide a residue which is dissolved in benzene which has been previously saturated with hydrogen chloride. The mixture is heated for 15 minutes on a steam bath, then saturated with petroleum ether, whereupon a white precipitate of α-methylamino-3-phenylbenzofuran-7-acetonitrile hydrochloride forms. A 5 gram sample of this intermediate is suspended in 50 ml. of glacial acetic acid, 5 g. of dinitrogen tetraoxide is added, and the mixture is stirred for 24 hours at 20° C. The volatiles are removed by evaporation to provide a residue which is dissolved in 10 ml. of acetic acid, and the mixture is heated at its reflux temperature while adding 30 ml. of 12N hydrochloric acid. Refluxing is continued for 1 hour, then the mixture is cooled. A green solid is obtained which is recrystallized from glacial acetic acid to provide light green crystals of α-methylamino-2-nitro-3-phenylbenzofuran-7-acetic acid, m.p. 237° C. (dec.), having the structure

Workup

  1. additionA mixture of 5 g
  2. temperaturereflux temperature
  3. customThe mixture is evaporated
  4. customto provide a residue which
  5. temperatureThe mixture is heated for 15 minutes on a steam bath
  6. stirringthe mixture is stirred for 24 hours at 20° C
  7. customThe volatiles are removed by evaporation
  8. customto provide a residue which
  9. dissolutionis dissolved in 10 ml
  10. temperaturereflux temperature
  11. additionwhile adding 30 ml
  12. temperatureRefluxing
  13. waitis continued for 1 hour
  14. temperaturethe mixture is cooled
  15. customA green solid is obtained which
  16. customis recrystallized from glacial acetic acid

Sources & evidence

ORD record
ord-177b6c6eb9c14e4cba971b8a449e468e
Source dataset
uspto-grants-1987_06
Patent number
US04675320

Reaction notes

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