Aniline → Diphenylamine

HRID 1871015Notes

Reaction equation

HRID 1871015 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[NH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd]>[C:2]1([NH:8][C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 3

HCID 6115AnilineHCID 7961BromobenzeneHCID 83681Tris(1,1-dimethylethyl)phosphine

Product 1

HCID 11487DiphenylamineYield 86%

Reagents, catalysts & solvents 2

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 1140TolueneSolvent

Procedure

The above general procedure was followed using bromobenzene (157 mg, 1.00 mmol) and aniline (93 mg, 1.00 mmol) with 1 mol % Pd(dba)2 and 0.8 mol % tri-t-butylphosphine in 1.5 mL of toluene. After one hour, the reaction mixture was adsorbed onto silica gel and chromatographed with 5% ethyl acetate/hexanes to give 145 mg (86%) of diphenylamine as a grey solid. 1H NMR (500 MHz, C6D6) δ 7.11-7.08 (m, 4H), 6.85-6.80 (m, 6H), 4.97 (br s, 1H). 13C NMR (125 MHz, C6D6) δ 143.6, 129.5, 121.1, 118.2. In addition, 21 mg (8%) of triphenylamine was isolated.

Workup

  1. customchromatographed with 5% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-3115883701cc443999b8aa5a59b08207
Source dataset
uspto-grants-2000_08
Patent number
US06100398

Reaction notes

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