Ammonium Hydroxide → 6-Cyclopropyl-2,4-dimethyl-nicotinic acid ethyl ester

HRID 1711154노트

반응식

HRID 1711154 반응식
[CH3:1][C:2]1[C:7]([C:8]([O:10][CH2:11][CH3:12])=[O:9])=[C:6]([CH3:13])[CH:5]=[CH:4][N:3]=1.[CH:14]1(C(O)=O)[CH2:16][CH2:15]1.S(OOS([O-])(=O)=O)([O-])(=O)=O.[NH4+].[NH4+].[NH4+].[OH-]>OS(O)(=O)=O.O.[N+]([O-])([O-])=O.[Ag+]>[CH2:11]([O:10][C:8](=[O:9])[C:7]1[C:6]([CH3:13])=[CH:5][C:4]([CH:14]2[CH2:16][CH2:15]2)=[N:3][C:2]=1[CH3:1])[CH3:12]

참가 물질

8

반응물 4

HCID 14923Ammonium HydroxideHCID 15655Cyclopropanecarboxylic acidHCID 62648Ammonium PersulfateHCID 736245Ethyl 2,4-dimethylnicotinate

생성물 1

HCID 687768336-Cyclopropyl-2,4-dimethyl-nicotinic acid ethyl ester수율 18%

시약·촉매·용매 3

HCID 24470Silver Nitrate촉매HCID 962Water용매HCID 1118Sulfuric Acid용매

실험 절차

To a solution of ethyl 2,4-dimethylpyridine-3-carboxylate (0.59 g, 3.29 mmol) and cyclopropane carboxylic acid (1.2 ml (15.1 mmol) in 10% aqueous H2SO4 (3 ml) was added AgNO3 (154 mg, 0.91 mmol) followed by a solution of ammonium persulfate (1:541 g, 6.75 mmol) in water (6 ml) and the mixture stirred at room temperature overnight. The reaction was neutralized to pH 10 with saturated aqueous NH4OH (5 ml) and extracted with EtOAc (3×20 ml). The combined organic extracts were dried (Na2SO4), concentrated and purified by column chromatography on silica gel (Hexanes/EtOAc, 96:4 then 1:1 then 0:100) to afford desired 6-cyclopropyl-2,4-dimethyl-nicotinic acid ethyl ester (133 mg, 18%) as a clear oil along with recovered starting ethyl 2,4-dimethylpyridine-3-carboxylate (0.31 g). 1H NMR (CDCl3) δ 0.93-0.97 (m, 4H), 1.38 (t, 3H, J=6 Hz), 1.92-2.02 (m, 1H), 2.28 (s, 3H), 2.47 (s, 3H), 4.39 (q, 2H, J=6 Hz), 6.73 (s, 1H).

후처리

  1. extractionextracted with EtOAc (3×20 ml)
  2. dry with materialThe combined organic extracts were dried (Na2SO4)
  3. concentrationconcentrated
  4. custompurified by column chromatography on silica gel (Hexanes/EtOAc, 96:4

출처 및 근거

ORD 기록
ord-dd77f1aa9d69488f91bcb34894fc3b18
출처 데이터셋
uspto-grants-2010_09
특허 번호
US07790747B2

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