Diisopropylethylamine → 1-Bromo-3-isocyanato-2-methyl-benzene

HRID 523274Notes

Reaction equation

HRID 523274 reaction equation
ClC(Cl)(O[C:5](=[O:11])OC(Cl)(Cl)Cl)Cl.[Br:13][C:14]1[C:15]([CH3:21])=[C:16]([CH:18]=[CH:19][CH:20]=1)[NH2:17].CCN(C(C)C)C(C)C>C1(C)C=CC=CC=1>[Br:13][C:14]1[CH:20]=[CH:19][CH:18]=[C:16]([N:17]=[C:5]=[O:11])[C:15]=1[CH3:21]

Participants

5

Reactant 3

HCID 81531DiisopropylethylamineHCID 94429TriphosgeneHCID 1235383-Bromo-o-toluidine

Product 1

HCID 655423311-Bromo-3-isocyanato-2-methyl-benzeneYield 229%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

A solution of triphosgene (2.25 g, 7.58 mmol) in toluene (27 mL), cooled in an ice-water bath, was treated slowly with a solution of 3-bromo-2-methylaniline (3.00 g, 16.1 mmol) and DIEA (5.6 mL, 32.2 mmol) in toluene (5.4 mL). The resulting suspension was stirred at room temperature for 2 h. The precipitate was removed by filtration and washed with EtOAc. The combined filtrates were diluted with EtOAc, washed with brine, dried and concentrated to provide 1-bromo-3-isocyanato-2-methylbenzene as a brown oil (3.68 g, 98% yield), used without purification. 1H NMR (400 MHz, DMSO-d6) δ 7.49 (dd, J=8.1, 0.9 Hz, 1H), 7.31 (dd, J=7.9, 0.7 Hz, 1H), 7.15 (td, J=8.0, 0.7 Hz, 1H), 2.38 (s, 3H).

Workup

  1. customThe precipitate was removed by filtration
  2. washwashed with EtOAc
  3. additionThe combined filtrates were diluted with EtOAc
  4. washwashed with brine
  5. customdried
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-80aa8b1a961546129992fd756427e07d
Source dataset
uspto-grants-2016_05
Patent number
US09334290B2

Reaction notes

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