4-Nitroaniline → HCID 86601710, compound

HRID 1867196Notes

Reaction equation

HRID 1867196 reaction equation
[N+:1](C1C=CC(N)=CC=1)([O-:3])=[O:2].[N:11]([O-:13])=[O:12].[Na+].[C:15]1([P:21](C2C=CC=CC=2)C2C=CC=CC=2)[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1>Cl.O.C([O-])(=O)C.[Na+].C(OCC)(=O)C>[N+:1]([O-:3])([O-:12])=[O:2].[N+:11]([C:18]1[CH:19]=[CH:20][C:15]([PH3+:21])=[CH:16][CH:17]=1)([O-:13])=[O:12]

Participants

8

Reactant 3

HCID 74754-NitroanilineHCID 11776TriphenylphosphineHCID 23668193Sodium Nitrite

Product 1

HCID 86601710HCID 86601710, compound

Reagents, catalysts & solvents 4

HCID 313Hydrochloric AcidSolventHCID 962WaterSolvent2×HCID 8857Ethyl AcetateSolventHCID 517045Sodium AcetateSolvent

Procedure

Non-radioactive standards and compounds used for radiolabeling were prepared by the method of Homer [Chem. Ber. 1958, 91, 45] and Rieke [J. Am. Chem. Soc. 1976, 98, 6872]. 4-Nitroaniline (2.8 g, 0.02 mol) and the molar equivalent of sodium nitrite were dissolved in 10 ml of concentrated HCl acid 10 ml of water at 0° C. Water (20 ml), in which was dissolved sodium acetate (5.6 g), was added. Triphenylphosphine (5.6 g) dissolved in ethyl acetate (80 ml) was added dropwise with stirring. After one hour, the resulting solution was acidified, the water layer separated from the ethyl acetate, and the aqueous portion extracted twice with ether. The ethyl acetate solution was extracted twice with water, the extracts were combined with the other aqueous fraction. Addition of an aqueous solution of sodium iodide precipitated the phosphonium iodide, mp 225-227° C. (Lit. 228.5° C.; Chem. Ber. 1958, 91, 45). 4-Nitrophenylphosphonium iodide was dissolved in 5 mL of ethanol treated with an aqueous solution of AgNO3. The silver iodide was removed by filtration and the solution was evaporated to dryness. Chromatography of the crude salt on silica gel (methylene chloride/methanol (90:10)) afforded pure 4-nitrophenylphosphonium nitrate; mp 215-127° C. Anal. calcd for C24H19N2O5P: C, 64.57; H, 4.29; Found: C, 64.49; H, 4.14.

Workup

  1. customwere prepared by the method of Homer [Chem. Ber. 1958, 91, 45] and Rieke [J. Am. Chem. Soc. 1976, 98, 6872]
  2. additionwas added
  3. additionwas added dropwise
  4. customthe water layer separated from the ethyl acetate
  5. extractionthe aqueous portion extracted twice with ether
  6. extractionThe ethyl acetate solution was extracted twice with water
  7. additionAddition of an aqueous solution of sodium iodide
  8. customprecipitated the phosphonium iodide, mp 225-227° C. (Lit. 228.5° C.; Chem. Ber. 1958, 91, 45)
  9. dissolution4-Nitrophenylphosphonium iodide was dissolved in 5 mL of ethanol
  10. additiontreated with an aqueous solution of AgNO3
  11. customThe silver iodide was removed by filtration
  12. customthe solution was evaporated to dryness

Sources & evidence

ORD record
ord-529ec4cabd2c4247b49629937605b5d7
Source dataset
uspto-grants-2009_12
Patent number
US07632485B2

Reaction notes

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