Triethylamine → Methyl 4-((tert-butoxycarbonyl)amino)-2,6-dichlorobenzoate

HRID 449869Notes

Reaction equation

HRID 449869 reaction equation
FC(F)(F)S(O[C:7]1[C:12]([Cl:13])=[CH:11][C:10]([NH:14][C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])=[CH:9][C:8]=1[Cl:22])(=O)=O.C1C=CC(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CCN(CC)CC>CO.CN(C=O)C.CC([O-])=O.CC([O-])=O.[Pd+2]>[C:18]([O:17][C:15]([NH:14][C:10]1[CH:11]=[C:12]([Cl:13])[C:7]([C:15]([O:17][CH3:18])=[O:16])=[C:8]([Cl:22])[CH:9]=1)=[O:16])([CH3:21])([CH3:20])[CH3:19]

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 812191,3-Bis(diphenylphosphino)propaneHCID 206100814-(Tert-butoxycarbonylamino)-2,6-dichlorophenyl trifluoromethanesulfonate

Product 1

HCID 20610066Methyl 4-((tert-butoxycarbonyl)amino)-2,6-dichlorobenzoateYield 119.4%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 887MethanolSolventHCID 6228DimethylformamideSolvent

Procedure

A mixture of 4-(tert-butoxycarbonylamino)-2,6-dichlorophenyl trifluoromethanesulfonate (14 g, 34 mmol), dppp (1.4 g, 3.4 mmol), Pd(OAc)2 (0.84 g, 3.4 mol) and Et3N (19.6 mL) in MeOH (112 mL) and DMF (224 mL) was refluxed under an atmosphere of carbon monoxide (10 atm) overnight. The reaction was concentrated under reduced pressure and the residue was purified by column chromatography on silica gel (petroleum ether/EtOAc 80:1) to give methyl 4-(tert-butoxy carbonylamino)-2,6-dichlorobenzoate (6.5 g, yield: 60%). 1H NMR (CDCl3, 400 MHz) δ 7.40 (s, 2H), 6.56 (brs, 1H), 3.94 (s, 3H), 1.51 (s, 9H).

Workup

  1. temperaturewas refluxed under an atmosphere of carbon monoxide (10 atm) overnight
  2. concentrationThe reaction was concentrated under reduced pressure
  3. customthe residue was purified by column chromatography on silica gel (petroleum ether/EtOAc 80:1)

Sources & evidence

ORD record
ord-119c8373af7844c090a699bc5e9cf13f
Source dataset
uspto-grants-2013_07
Patent number
US08486950B2

Reaction notes

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