Benzoyl Peroxide → 3-(Bromomethyl)-4-[(diphenylmethylidene)amino]-2-(trifluoromethyl)benzonitrile

HRID 1188487Notes

Reaction equation

HRID 1188487 reaction equation
[C:1]1([C:7](=[N:14][C:15]2[CH:22]=[CH:21][C:18]([C:19]#[N:20])=[C:17]([C:23]([F:26])([F:25])[F:24])[C:16]=2[CH3:27])[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C1C(=O)N([Br:35])C(=O)C1.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>C(Cl)(Cl)(Cl)Cl.C(Cl)Cl>[Br:35][CH2:27][C:16]1[C:17]([C:23]([F:24])([F:25])[F:26])=[C:18]([CH:21]=[CH:22][C:15]=1[N:14]=[C:7]([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1)[C:19]#[N:20]

Participants

6

Reactant 3

HCID 7187Benzoyl PeroxideHCID 67184N-bromobutanimideHCID 866206794-[(Diphenylmethylidene)amino]-3-methyl-2-(trifluoromethyl)benzonitrile

Product 1

HCID 866206803-(Bromomethyl)-4-[(diphenylmethylidene)amino]-2-(trifluoromethyl)benzonitrileYield 95%

Reagents, catalysts & solvents 2

HCID 5943Carbon TetrachlorideSolventHCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of the benzonitrile (3.53 g, 9.69 mmol) from step D in CCl4 (90 mL) was added NBS (1.98 g, 11.14 mmol) and benzoyl peroxide (70%, 0.352 g, 1.45 mmol). The mixture was heated at reflux for 3 h. After cooling to ambient temperature, the reaction was diluted with CH2Cl2 (100 mL), washed with 1N NaOH (100 mL), brine (100 mL), dried (MgSO4) and concentrated. Purification by SiO2 chromatography (10% EtOAc in hexanes) afforded 3-(bromomethyl)-4-[(diphenylmethylidene)amino]-2-(trifluoromethyl)benzonitrile (4.08 g, 95%) as a light yellow solid: 1H NMR (400 MHz, DMSO-d6): δ 7.78 (d, J=8.3 Hz, 1H), 7.78-7.11 (m, 10H), 6.91 (d, J=8.6 Hz, 1H), 4.78 (s, 2H).

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux for 3 h
  3. washwashed with 1N NaOH (100 mL), brine (100 mL)
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated
  6. customPurification by SiO2 chromatography (10% EtOAc in hexanes)

Sources & evidence

ORD record
ord-5d27059ee8b74390bb99d3fea87f3390
Source dataset
uspto-grants-2014_03
Patent number
US08673948B2

Reaction notes

Loading…