Dimethylformamide → HCID 131724068, compound

HRID 1167343Notes

Reaction equation

HRID 1167343 reaction equation
Br[C:2]1[CH:7]=[C:6]([C:8]([CH3:16])([CH3:15])[O:9][SiH2:10][C:11]([CH3:14])([CH3:13])[CH3:12])[CH:5]=[C:4]([C:17]([CH3:25])([CH3:24])[O:18][SiH2:19][C:20]([CH3:23])([CH3:22])[CH3:21])[CH:3]=1.[CH3:26][N:27](C)C=O>C1(C)C=CC=CC=1.[C-]#N.[Zn+2].[C-]#N.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:20]([SiH2:19][O:18][C:17]([CH3:25])([CH3:24])[C:4]1[CH:3]=[C:2]([CH:7]=[C:6]([C:8]([CH3:16])([CH3:15])[O:9][SiH2:10][C:11]([CH3:14])([CH3:13])[CH3:12])[CH:5]=1)[C:26]#[N:27])([CH3:23])([CH3:22])[CH3:21]

Participants

6

Reactant 2

HCID 6228DimethylformamideHCID 131724069HCID 131724069, compound

Product 1

HCID 131724068HCID 131724068, compoundYield 82%

Reagents, catalysts & solvents 3

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of 1-bromo-3,5-bis-(tert-butyl-dimethyl-silanyloxymethyl)-benzene (2.05 g, 4.601 mmol, example 35) in dimethylformamide (8 mL) at room temperature was added zinc cyanide (324 mg, 2.761 mmol). The reaction mixture was degassed by passing argon through for 1 h before tetrakis(triphenylphosphine)palladium (319 mg, 0.276 mmol) was added. The reaction mixture was heated at 80° C. under argon for 12 h. The reaction mixture was taken up in toluene (40 mL) and washed with 2 N ammonium hydroxide (2×40 mL), brine and dried over anhydrous magnesium sulfate. The solid was then filtered off, and the filtrate was concentrated in vacuo. Purification of the crude residue by flash chromatography (Biotage system, KP-Sil™ 32-63 μm, 60 Å silica gel) eluting with 5% ethyl acetate in hexanes yielded 3,5-bis-(tert-butyl-dimethyl-silanyloxymethyl)-benzonitrile (1.47 g, 82%).

Workup

  1. customThe reaction mixture was degassed
  2. customthrough for 1 h
  3. additionwas added
  4. washwashed with 2 N ammonium hydroxide (2×40 mL), brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. filtrationThe solid was then filtered off
  7. concentrationthe filtrate was concentrated in vacuo
  8. customPurification of the crude residue by flash chromatography (Biotage system, KP-Sil™ 32-63 μm, 60 Å silica gel)
  9. washeluting with 5% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-317e3f10b79f4593abf439e135559318
Source dataset
uspto-grants-2003_09
Patent number
US06617346B1

Reaction notes

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