Diphenylamine → 4-(diphenylamino)benzonitrile

HRID 1871012Notes

Reaction equation

HRID 1871012 reaction equation
Br[C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][CH:3]=1.[C:10]1([NH:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=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:6]([C:5]1[CH:8]=[CH:9][C:2]([N:16]([C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=2)[C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)=[CH:3][CH:4]=1)#[N:7]

Participants

6

Reactant 3

HCID 11487DiphenylamineHCID 12162Benzonitrile, 4-bromo-HCID 83681Tris(1,1-dimethylethyl)phosphine

Product 1

HCID 98602394-(diphenylamino)benzonitrileYield 97.3%

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 4-bromobenzonitrile (188 mg, 1.03 mmol) and diphenylamine (169 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 50% toluene/hexanes to give 263 mg (97%) of N-(4-cyanophenyl)diphenylamine as a white solid. 1H NMR (500 MHz, C6D6) δ 6.97 (t, J=8 Hz, 4H), 6.92 (d, J=8.9 Hz, 2H), 6.86-6.83 (m, 6H), 6.56 (d, J=8.7 Hz, 2H). 13C NMR (125 MHz, C6D6) δ 151.3, 146.6, 133.2, 129.9, 126.1, 124.9, 120.5, 119.4, 104.0.

Workup

  1. customchromatographed with 50% toluene/hexanes

Sources & evidence

ORD record
ord-abb3262a6ab54d13a96e7e0db22c477a
Source dataset
uspto-grants-2000_08
Patent number
US06100398

Reaction notes

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