Pyridine → tert-Butyl (6-(chloromethyl)pyridin-2-yl)carbamate

HRID 332142노트

반응식

HRID 332142 반응식
O[CH2:2][C:3]1[N:8]=[C:7]([NH:9][C:10](=[O:16])[O:11][C:12]([CH3:15])([CH3:14])[CH3:13])[CH:6]=[CH:5][CH:4]=1.N1C=CC=CC=1.O=S(Cl)[Cl:25]>C(Cl)Cl>[Cl:25][CH2:2][C:3]1[N:8]=[C:7]([NH:9][C:10](=[O:16])[O:11][C:12]([CH3:15])([CH3:14])[CH3:13])[CH:6]=[CH:5][CH:4]=1

참가 물질

5

반응물 3

HCID 1049PyridineHCID 24386Thionyl ChlorideHCID 19349090Tert-butyl (6-(hydroxymethyl)pyridin-2-yl)carbamate

생성물 1

HCID 21851761tert-Butyl (6-(chloromethyl)pyridin-2-yl)carbamate수율 50%

시약·촉매·용매 1

HCID 6344Dichloromethane용매

실험 절차

To a solution of ethyl 6-[(tert-butoxycarbonyl)amino]pyridine-2-carboxylate (456 mg, 1.71 mmol) in anhydrous ethanol (20 ml) was added pulverized CaCl2 (395 mg, 3.42 mmol). The suspension was stirred and cooled to 0° C. and NaBH4 (325 mg, 8.55 mmol) was added slowly. The reaction was stirred at 0° C. for 2 h, quenched with water, and extracted with CHCl3 (×3). The combined organic layer was dried over Na2SO4 and concentrated. The residue was purified by column chromatography on silica gel (30→50% ethyl acetate in hexane) to yield a colorless syrup (308 mg) as a mixture containing tert-butyl [6-(hydroxymethyl)pyridin-2-yl]carbamate as the major component (˜4:1 ratio). To a solution of the above mixture in CH2Cl2 (10 ml) was added pyridine (144 μl, 1.79 mmol) and SOCl2 (120 μl, 1.65 mmol). The reaction was stirred at room temperature for 4 h, quenched with water and saturated Na2CO3, and extracted with CHCl3. The combined organic layer was dried over Na2SO4 and concentrated. The residue was purified by column chromatography on silica gel (10% ethyl acetate in hexane) to yield the title compound as a colorless syrup (208 mg, 50% over 2 steps).

후처리

  1. customquenched with water and saturated Na2CO3
  2. extractionextracted with CHCl3
  3. dry with materialThe combined organic layer was dried over Na2SO4
  4. concentrationconcentrated
  5. customThe residue was purified by column chromatography on silica gel (10% ethyl acetate in hexane)

출처 및 근거

ORD 기록
ord-0459703941dc48b0966c48d9ffdeaf34
출처 데이터셋
uspto-grants-2014_11
특허 번호
US08877804B2

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