3-Bromobenzonitrile → HCID 69705742, compound

HRID 1359601Notes

Reaction equation

HRID 1359601 reaction equation
Br[C:2]1[CH:31]=[CH:30][C:5]([CH2:6][CH2:7][Si:8]([O:14][Si:15]([CH2:21][CH2:22][C:23]2[CH:28]=[CH:27][C:26](Br)=[CH:25][CH:24]=2)([CH3:20])[C:16]([CH3:19])([CH3:18])[CH3:17])([C:10]([CH3:13])([CH3:12])[CH3:11])[CH3:9])=[CH:4][CH:3]=1.Br[C:33]1[CH:34]=[C:35]([CH:38]=[CH:39][CH:40]=1)[C:36]#[N:37]>C1COCC1.CCOCC.[Cl-].[Cl-].[Zn+2].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:36]([C:35]1[CH:34]=[C:33]([C:2]2[CH:3]=[CH:4][C:5]([CH2:6][CH2:7][Si:8]([O:14][Si:15]([CH2:21][CH2:22][C:23]3[CH:28]=[CH:27][C:26]([C:33]4[CH:40]=[CH:39][CH:38]=[C:35]([C:36]#[N:37])[CH:34]=4)=[CH:25][CH:24]=3)([CH3:20])[C:16]([CH3:19])([CH3:18])[CH3:17])([C:10]([CH3:11])([CH3:12])[CH3:13])[CH3:9])=[CH:30][CH:31]=2)[CH:40]=[CH:39][CH:38]=1)#[N:37]

Participants

7

Reactant 2

HCID 233813-BromobenzonitrileHCID 67543403HCID 67543403, compound

Product 1

HCID 69705742HCID 69705742, compoundYield 63.6%

Reagents, catalysts & solvents 4

HCID 3007855ZincchlorideCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
65 °C

Procedure

To a cooled (−78° C.) solution of 4-bromo-benzyl-(t-butyldimethylsilyl)-ether (2.73 g, 9 mmol) (reference example 10) in THF (40 mL) was added, dropwise, n-buLi (4.4 mL, 2.5M in hexanes). On complete addition, the resulting solution was stirred for 10 min then ZnCl2 (10 mL, 0.5M in THF) was added. The cold bath was removed and stirring continued for 10 min. To this solution was added a solution comprised of 3-bromo-benzonitrile (1.82 g, 10 mmol) (Aldrich), (Ph3P)4Pd (410 mg, 0.35 mmol) in THF (5 mL). The resulting mixture was heated to 65° C. and stirred at this temperature for 20 min. The reaction mixture was allowed to cool to room temperature then diluted with ether, washed, sequentially, with sat. ammonium chloride solution and brine, dried over MgSO4 and concentrated. The residue was purified by flash chromatography (eluting with 5% EtOAc in hexanes) to give 2.0 g of the title compound. 1H NMR (CDCl3) d 0.15 (s, 6H), 1.00 (s, 9H), 4.80 (s, 2H), 7.43 (d, J=8 Hz, 2H), 7.45-7.65 (m, 4H), 7.80 (m, 1H), 7.85 (bs, 1). MS (ion spray) m/z 324 (M+H)+.

Workup

  1. additionwas added
  2. additionOn complete addition
  3. customThe cold bath was removed
  4. stirringstirring
  5. waitcontinued for 10 min
  6. additionTo this solution was added a solution
  7. stirringstirred at this temperature for 20 min
  8. temperatureto cool to room temperature
  9. washwashed
  10. dry with materialsequentially, with sat. ammonium chloride solution and brine, dried over MgSO4
  11. concentrationconcentrated
  12. customThe residue was purified by flash chromatography (eluting with 5% EtOAc in hexanes)

Sources & evidence

ORD record
ord-f6d85359d0894c0c93037be73df4c1d1
Source dataset
uspto-grants-2003_07
Patent number
US06599918B2

Reaction notes

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