Dimethylformamide → HCID 22996249, compound

HRID 1167337Notes

Reaction equation

HRID 1167337 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:14]=[C:15]([CH2:17][O:18][CH3:19])[CH:16]=1)[CH2:5][O:6][Si:7]([C:10]([CH3:13])([CH3:12])[CH3:11])([CH3:9])[CH3:8].[CH3:20][N:21](C)C=O>C(OCC)C.[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>[Si:7]([O:6][CH2:5][C:4]1[CH:3]=[C:2]([CH:16]=[C:15]([CH2:17][O:18][CH3:19])[CH:14]=1)[C:20]#[N:21])([C:10]([CH3:13])([CH3:12])[CH3:11])([CH3:9])[CH3:8]

Participants

6

Reactant 2

HCID 6228DimethylformamideHCID 22996216HCID 22996216, compound

Product 1

HCID 22996249HCID 22996249, compoundYield 79%

Reagents, catalysts & solvents 3

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 3283Diethyl EtherSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of (3-bromo-5-methoxymethyl-benzyloxy)-tert-butyl-dimethylsilane (2.1 g, 6.081 mmol) in dimethylformamide (10 mL) at room temperature was added zinc cyanide (428.4 mg, 3.649 mmol). The reaction mixture was degassed by passing argon through for 2 h before tetrakis(triphenylphosphine)palladium (422 mg, 0.365 mmol) was added. The reaction mixture was heated at 80° C. under argon for 8 h. The reaction mixture was taken up in diethyl ether and washed with ammonium hydroxide, brine and dried over anhydrous sodium 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 5-10% ethyl acetate in hexanes yielded 3-(tert-butyl-dimethylsilanyloxymethyl)-5-methoxymethyl-benzonitrile (1.402 g, 79%).

Workup

  1. customThe reaction mixture was degassed
  2. customthrough for 2 h
  3. additionwas added
  4. washwashed with ammonium hydroxide, brine
  5. dry with materialdried over anhydrous sodium 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 5-10% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-b614c43bc36e4da3bc98a931bc7a6d39
Source dataset
uspto-grants-2003_09
Patent number
US06617346B1

Reaction notes

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