Aniline → Diphenylamine

HRID 1955321Notes

Reaction equation

HRID 1955321 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 1 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): δ 7.18 (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-cf40a51fec354b1eb5a4cbdc16be7108
Source dataset
uspto-grants-2000_09
Patent number
US06124462

Reaction notes

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