Dimethylcarbamoyl Chloride → 4-Chloro-6-methylpyridine-2-carbonitrile

HRID 1525837노트

반응식

HRID 1525837 반응식
[Cl:1][C:2]1[CH:7]=[CH:6][N+:5]([O-])=[C:4]([CH3:9])[CH:3]=1.[Si]([C:14]#[N:15])(C)(C)C.CN(C)C(Cl)=O.C([O-])([O-])=O.[K+].[K+]>C(Cl)Cl>[Cl:1][C:2]1[CH:3]=[C:4]([CH3:9])[N:5]=[C:6]([C:14]#[N:15])[CH:7]=1

참가 물질

6

반응물 4

HCID 6598Dimethylcarbamoyl Chloride2회HCID 11430Potassium CarbonateHCID 82115Trimethylsilyl cyanide2회HCID 122118014-Chloro-2-methyl-1-oxo-1lambda~5~-pyridine

생성물 1

HCID 185052494-Chloro-6-methylpyridine-2-carbonitrile수율 75.5%

시약·촉매·용매 1

HCID 6344Dichloromethane용매2회

실험 절차

4-chloro-2-methylpyridine-N-oxide (8.97 g, 62.5 mmol, 1.00 eq) was dissolved in CH2Cl2 and dried over MgSO4. The solution was added to a flame-dried round-bottom flask and CH2Cl2 was added to give a total volume of 188 mL. TMS-cyanide (10 mL, 75 mmol, 1.2 eq) was added and the reaction stirred for 15 minutes. Dimethylcarbamyl chloride (6.9 mL, 75 mmol, 1.2 eq) was added dropwise over 20 minutes, and the reaction was stirred for 24 hours. An additional one equivalent each of TMS-cyanide and dimethylcarbamyl chloride were added and the reaction was stirred for another 72 hours. The reaction was made basic with 10% K2CO3 and extraxcted with CH2Cl2 (3×). The combined organics were dried (MgSO4), filtered and concentrated in vacuo. Purification by flash chromatography on silica gel afforded 7.2 g (75%) of the title compound as a white solid. 1H NMR (400 MHz, DMSO-d6) δ 8.13 (d, J=1.6 Hz, 1H), 7.82 (d, J=1.7 Hz, 1H), 2.52 (s, 3H); ES-MS [M+1]+: 153.2.

후처리

  1. dry with materialdried over MgSO4
  2. additionThe solution was added to a flame-dried round-bottom flask
  3. additionCH2Cl2 was added
  4. customto give a total volume of 188 mL
  5. stirringthe reaction was stirred for 24 hours
  6. stirringthe reaction was stirred for another 72 hours
  7. dry with materialThe combined organics were dried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customPurification by flash chromatography on silica gel

출처 및 근거

ORD 기록
ord-b57f386ffed44bba8ec76527868ada1d
출처 데이터셋
uspto-grants-2015_07
특허 번호
US09085562B2

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