Dimethylcarbamoyl Chloride → 6-Chloro-4-nitro-2-pyridinecarbonitrile

HRID 1875133Notes

Reaction equation

HRID 1875133 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][N+:3]=1[O-].[Si]([C:16]#[N:17])(C)(C)C.CN(C)C(Cl)=O.C([O-])(O)=O.[Na+]>ClCCCl>[Cl:1][C:2]1[N:3]=[C:4]([C:16]#[N:17])[CH:5]=[C:6]([N+:8]([O-:10])=[O:9])[CH:7]=1

Participants

6

Reactant 4

HCID 6598Dimethylcarbamoyl ChlorideHCID 82115Trimethylsilyl cyanideHCID 844332-Chloro-4-nitropyridine 1-oxideHCID 516892Sodium Bicarbonate

Product 1

HCID 866449356-Chloro-4-nitro-2-pyridinecarbonitrileYield 42%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

2-chloro-4-nitropyridine 1-oxide (1.8 g, 10.31 mmol) was slowly added to a solution of TMS-CN (4.98 ml, 37.1 mmol) in 1,2-dichloroethane (25 ml) at RT under N2 and dimethylcarbamic chloride (3.41 ml, 37.1 mmol) was then slowly added. The mixture was stirred for at RT overnight then heated to 85° C. for 5 days. The reaction was cooled RT and sat. NaHCO3 was added and then extracted with CH2Cl2. The organic was dried over Na2SO4, filtered and concentrated. The residue was purified by chromatography on silica gel eluted with 0-10% EtOAC in hexane to give the product as a white solid (0.79 g, 42%). 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 7.63 (1H, d) 7.59 (1H, d).

Workup

  1. temperaturethen heated to 85° C. for 5 days
  2. temperatureThe reaction was cooled RT
  3. extractionextracted with CH2Cl2
  4. dry with materialThe organic was dried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe residue was purified by chromatography on silica gel
  8. washeluted with 0-10% EtOAC in hexane

Sources & evidence

ORD record
ord-5e500fe8fb84411eabe5129e0be607b3
Source dataset
uspto-grants-2012_11
Patent number
US08304419B2

Reaction notes

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