Aniline → Diphenylamine

HRID 412771Notes

Reaction equation

HRID 412771 reaction equation
Cl[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.CC(C)([O-])C.[Na+]>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 7964ChlorobenzeneHCID 23676156Sodium t-butoxide

Product 1

HCID 11487DiphenylamineYield 86.3%

Reagents, catalysts & solvents 2

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

Procedure

According to general procedure B, chlorobenzene (57 mg, 0.50 mmol) reacted with aniline (48 mg, 0.50 mmol) using 1 mol % of Pd(dba)2, 2 mol % of Ph5FcP(t-Bu)2, and sodium tert-butoxide (59 mg, 0.60 mmol) in toluene at 70° C. to give the title compound (73 mg, 86%) as a white solid. The coupling reaction of bromobenzene (158 mg, 1.00 mmol) with aniline (93 mg, 1.00mmol) occurred at room temperature over 4 h using 1 mol % of Pd(dba)2/Ph5FcP(t-Bu)2 to give the title compound (166 mg, 98%): 1H-NMR (400 MHz, CDCl3): δ 7.34 (t, 4H, J=7.8 Hz and 7.5 Hz), 7.14 (d, 4H, J=8.7 Hz), 7.00 (t, 2H, J=7.2 and 7.5 Hz), 5.74 (bs, 1H). 13C{1H}-NMR (100 MHz, CDCl3): δ 143.09, 129.32, 120.97, 117.78. GC/MS(EI): m/z 169 (M+).

Workup

  1. customat 70° C.

Sources & evidence

ORD record
ord-eb5239318f8047529c00e7e396d59f11
Source dataset
uspto-grants-2003_05
Patent number
US06562989B2

Reaction notes

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