Dimethylcarbamoyl Chloride → 4-(Tert-butyl-dimethyl-silanyloxymethyl)-6-methyl-pyridine-2-carbonitrile

HRID 426246Notes

Reaction equation

HRID 426246 reaction equation
[C:1]([SiH2:5][O:6][C:7]([CH3:17])([CH3:16])[C:8]1[CH:13]=[CH:12][N+:11]([O-])=[C:10]([CH3:15])[CH:9]=1)([CH3:4])([CH3:3])[CH3:2].C[Si]([C:22]#[N:23])(C)C.CN(C)C(Cl)=O.C(=O)(O)[O-].[Na+]>ClCCl>[C:1]([SiH2:5][O:6][C:7]([CH3:17])([CH3:16])[C:8]1[CH:9]=[C:10]([CH3:15])[N:11]=[C:12]([C:22]#[N:23])[CH:13]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 6598Dimethylcarbamoyl ChlorideHCID 82115Trimethylsilyl cyanideHCID 516892Sodium BicarbonateHCID 1317294304-(Tert-butyl-dimethyl-silanyloxymethyl)-2-methyl-pyridine 1-oxide

Product 1

HCID 1317294314-(Tert-butyl-dimethyl-silanyloxymethyl)-6-methyl-pyridine-2-carbonitrileYield 76.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of 4-(tert-butyl-dimethyl-silanyloxymethyl)-2-methyl-pyridine 1-oxide (11.2 g, 44 mmol) in dichloromethane (100 ml) at room temperature, was added trimethylsilyl cyanide (7.1 ml, 53.2 mmol). After 15 min., dimethylcarbamyl chloride (4.8 ml, 53.2 mmol) was added and the stirring was continued for 24 hr. The mixture was then cooled in an ice bath and saturated aqueous sodium bicarbonate solution (100 ml) was added. After 1 hr., organic layer was separated, dried with anhydrous magnesium sulfate, filtered, and evaporated in vacuo. The residue was purified by silica gel column chromatography (eluent, ether:hexane (1:1)) to afford 8.8 g (76%) of 4-(tert-butyl-dimethyl-silanyloxymethyl)-6-methyl-pyridine-2-carbonitrile as a white solid. 1H NMR (200 MHz, CDCl3) δ 0.11 (6H, s), 0.94 (9H, s), (3H, s), 2.52 (3H, s), 4.67 (2H, s), 6.97 (1H, d, J=6.7 Hz), 7.08 (1H, s), 8.10 (1H, d, J=6.7 Hz).

Workup

  1. waitthe stirring was continued for 24 hr
  2. temperatureThe mixture was then cooled in an ice bath
  3. waitAfter 1 hr
  4. custom, organic layer was separated
  5. dry with materialdried with anhydrous magnesium sulfate
  6. filtrationfiltered
  7. customevaporated in vacuo
  8. customThe residue was purified by silica gel column chromatography (eluent, ether:hexane (1:1))

Sources & evidence

ORD record
ord-e6b26c5bee5a4b0e828743aa7332cae5
Source dataset
uspto-grants-2012_01
Patent number
US08106064B2

Reaction notes

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