Acetic Anhydride → 5-Bromo-4-methylpyridin-3-yl acetate

HRID 468711노트

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HRID 468711 반응식
B(F)(F)F.CCOCC.[Br:10][C:11]1[C:12]([CH3:18])=[C:13](N)[CH:14]=[N:15][CH:16]=1.COCCOC.N(OC(C)(C)C)=O.[C:32]([O:35]C(=O)C)(=[O:34])[CH3:33]>CCCCC>[C:32]([O:35][C:13]1[CH:14]=[N:15][CH:16]=[C:11]([Br:10])[C:12]=1[CH3:18])(=[O:34])[CH3:33]

참가 물질

7

반응물 5

HCID 7918Acetic AnhydrideHCID 8000Boron trifluoride etherateHCID 80711,2-DimethoxyethaneHCID 10906Tert-Butyl nitriteHCID 70606795-Bromo-4-methylpyridin-3-amine

생성물 1

HCID 679749105-Bromo-4-methylpyridin-3-yl acetate수율 38.4%

시약·촉매·용매 1

HCID 8003Pentane용매

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온도
-15 °C

실험 절차

To a flask containing boron trifluoride etherate (0.35 mL, 2.8 mmol) at −15° C. was added a solution of 5-bromo-4-methylpyridin-3-amine (249.0 mg, 1.331 mmol) in 1,2-dimethoxyethane (2.0 mL, 19 mmol). Tert-butyl nitrite (0.20 mL, 1.7 mmol) was then added dropwise and the reaction mixture stirred at −15° C. for one hour. 3 mL pentane was then added and the solid material collected by vacuum filtration. The solid material was dissolved in acetic anhydride (2.0 mL, 21 mmol) and stirred at 100° C. for one hour. The solvent was evaporated in vacuo, and the residue then suspended in 2M aqueous Na2CO3 and extracted twice with dichloromethane. The combined organic extracts were dried over MgSO4, filtered, and evaporated in vacuo. The crude product was purified via flash chromatography on silica gel (24 g silica, solvent gradient: 0-40% ethyl acetate in heptanes) to yield 117.7 mg (38%) of 5-bromo-4-methylpyridin-3-yl acetate. LCMS (ESI): M+H=230.2; 1H NMR (400 MHz, DMSO-d6) δ 8.61 (s, 1H), 8.35 (s, 1H), 2.37 (s, 3H), 2.23 (s, 3H).

후처리

  1. filtrationthe solid material collected by vacuum filtration
  2. stirringstirred at 100° C. for one hour
  3. customThe solvent was evaporated in vacuo
  4. extractionextracted twice with dichloromethane
  5. dry with materialThe combined organic extracts were dried over MgSO4
  6. filtrationfiltered
  7. customevaporated in vacuo
  8. customThe crude product was purified via flash chromatography on silica gel (24 g silica, solvent gradient: 0-40% ethyl acetate in heptanes)

출처 및 근거

ORD 기록
ord-acae4c8dd1154455a529b7437110f192
출처 데이터셋
uspto-grants-2014_01
특허 번호
US08623889B2

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