Aniline → Diphenylamine

HRID 1884175Notes

Reaction equation

HRID 1884175 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([O-])(C)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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[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 30.1%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Procedure

The general procedure from Example 1A was followed using chlorobenzene (135 mg, 1.2 mmol) and aniline (93 mg, 1.0 mmol) with Pd2(dba)3 (25 mg, 0.027 mmol) and (Me3C)2PH(O) (7.0 mg, 0.042 mmol) and NaOtBu (144 mg, 1.5 mmol) in 2.0 mL of toluene. After 24 h, the reaction mixture was chromatographed with 5% ethyl acetate/hexane to give 51 mg (30% yield) of diphenylamine. It was >95% pure by 1H NMR and GC/MS. 1H NMR (500 MHz, CDCl3): δ7.18 (m, 4H), 6.99 (d, J=7.68 Hz, 4H), 6.84 (t, J=7.34 Hz, 2H), 5.59 (br, 1H) ppm. 13C NMR (125 MHz, CDCl3): d 143.1, 129.3, 120.9, 117.8 ppm. MS: Calculated for C12H11N(M+): 169.1. Found: 170.3 (M++H).

Workup

  1. customthe reaction mixture was chromatographed with 5% ethyl acetate/hexane

Sources & evidence

ORD record
ord-2533462f77a24145bcac96635368d1d0
Source dataset
uspto-grants-2004_07
Patent number
US06762330B2

Reaction notes

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