Triphenylphosphine → [1,1'-Biphenyl]-4-amine, 3-nitro-

HRID 964608Notes

Reaction equation

HRID 964608 reaction equation
Br[C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[C:4]([N+:9]([O-:11])=[O:10])[CH:3]=1.C([Sn](CCCC)(CCCC)[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)CCC.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>CN(C=O)C.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl>[C:17]1([C:2]2[CH:8]=[CH:7][C:5]([NH2:6])=[C:4]([N+:9]([O-:11])=[O:10])[CH:3]=2)[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1

Participants

6

Reactant 3

HCID 11776TriphenylphosphineHCID 701324-Bromo-2-nitroanilineHCID 607632Tributylphenyltin

Product 1

HCID 77705[1,1'-Biphenyl]-4-amine, 3-nitro-Yield 75.2%

Reagents, catalysts & solvents 2

HCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 6228DimethylformamideSolvent

Procedure

A solution of 4-bromo-2-nitroaniline 17 (1.0 g, 4.67 mmol), tributylphenyl tin (2.2 g, 6.07 mmol), bis(triphenylphosphine)palladium (II) chloride (164 mg, 0.234 mmol), and triphenylphosphine (613 mg, 2.34 mmol) in DMF (15 ml) was heated under N2 at 120° C. overnight. After the solution was cooled to room temperature, the reaction mixture was directly chromatographed on silica gel eluting with 2-5% EtOAc/Hexane to give 752 mg (75%) of 5 as a yellow solid: mp 169°-171° C.; IR (CHCl3) 3517, 3398, 3022, 1635, 1525, 1250; 1H NMR δ8.38 (1H, d, J=2.2), 7.66 (1H, dd, J=8.7, 2.2), 7.59-7.54 (2H, m), 7.49-7.34 (3H, m), 6.90 (1H, d, J=8.8), 6.13 (NH, brs); 13C NMR δ144.2, 139.3, 135.0, 130.9, 129.5, 127.8, 126.8, 124.4, 119.8, 112.8; Anal. Calcd for C12H10N2O2 : C, 67.28; H, 4.70; N, 13.08. Found: C, 67.38, H, 4.76; N, 13.01.

Workup

  1. customthe reaction mixture was directly chromatographed on silica gel eluting with 2-5% EtOAc/Hexane

Sources & evidence

ORD record
ord-3af166c8f280429db0dd9eeaf90cec32
Source dataset
uspto-grants-1998_06
Patent number
US05770617

Reaction notes

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