4-Nitroaniline → HCID 66914977, compound

HRID 880410Notes

Reaction equation

HRID 880410 reaction equation
B.CSC.[N+:5]([C:8]1[CH:14]=[CH:13][C:11]([NH2:12])=[CH:10][CH:9]=1)([O-])=O.F[C:16](F)(F)[C:17]([NH2:19])=O.FC(F)(F)C(O[C:27](=O)[C:28](F)(F)F)=O.[H-].[Na+].[Cl-].[NH4+:38]>C1COCC1.C(O)C.[Zn]>[CH3:10][C:9]1[CH:8]=[C:14]([CH3:13])[N:38]=[C:17]([NH:19][CH2:27][CH2:28][NH:5][C:8]2[CH:14]=[CH:13][C:11]([NH2:12])=[CH:10][CH:9]=2)[CH:16]=1

Participants

10

Reactant 6

HCID 74754-NitroanilineHCID 9845Trifluoroacetic anhydrideHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 67717TrifluoroacetamideHCID 12423031(Dimethyl sulfide)trihydroboron

Product 1

HCID 66914977HCID 66914977, compound

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 702EthanolSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

From 4-nitroaniline by treatment with ethyl oxalyl chloride in triethylamine and THF to give N-(4-nitro-phenyl)-oxalamic acid ethyl ester, followed by aminolysis with 2-amino-4,6-dimethylpyridine in triethylamine at reflux to afford N-(4,6-dimethyl-pyridin-2-yl)-N-(4-nitro-phenyl)-oxalamide. The amides are then reduced with borane-dimethylsulfide in THF at reflux, the free amine is protected as a trifluoroacetamide by treatment with trifluoroacetic anhydride and sodium hydride in THF then the nitro group is reduced with zinc powder in the presence of ammonium chloride in ethanol. Following coupling with the appropriately-selected acid chloride, a final treatment with lithium hydroxide in methanol removes the trifluoroacetamide to give the final compound described.

Workup

  1. temperatureat reflux
  2. customa final treatment with lithium hydroxide in methanol removes the trifluoroacetamide

Sources & evidence

ORD record
ord-8ff6ad3f5b54470c83dac3e177e6242b
Source dataset
uspto-grants-2015_03
Patent number
US08993574B2

Reaction notes

Loading…