Tributylvinyltin → 4-Amino-6-(4-chlorophenyl)-5-fluoro-3-vinylpyridine-2-carboxylic acid methyl ester

HRID 245291노트

반응식

HRID 245291 반응식
[CH3:1][O:2][C:3]([C:5]1[C:10](Cl)=[C:9]([NH2:12])[C:8]([F:13])=[C:7]([C:14]2[CH:19]=[CH:18][C:17]([Cl:20])=[CH:16][CH:15]=2)[N:6]=1)=[O:4].[CH2:21]([Sn](CCCC)(CCCC)C=C)[CH2:22]CC>C(#N)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH3:1][O:2][C:3]([C:5]1[C:10]([CH:21]=[CH2:22])=[C:9]([NH2:12])[C:8]([F:13])=[C:7]([C:14]2[CH:19]=[CH:18][C:17]([Cl:20])=[CH:16][CH:15]=2)[N:6]=1)=[O:4]

참가 물질

5

반응물 2

HCID 81998TributylvinyltinHCID 22677303Methyl 4-amino-5-fluoro-3-chloro-6-(4-chlorophenyl)picolinate

생성물 1

HCID 594321004-Amino-6-(4-chlorophenyl)-5-fluoro-3-vinylpyridine-2-carboxylic acid methyl ester수율 9.4%

시약·촉매·용매 2

HCID 178418476HCID 178418476, 화합물촉매HCID 6342Acetonitrile용매

반응 조건

온도
110 °C

실험 절차

4-Amino-3-chloro-6-(4-chlorophenyl)-5-fluoropyridine-2-carboxylic acid methyl ester (0.5 g, 1.59 mmol), tributyl(vinyl)tin (1.01 g, 3.17 mmol), bis(triphenylphosphine)palladium(II) dichloride (0.111 g, 0.159 mmol), and tetrabutylammonium triphenyldifluorosilicate (1.71 g, 3.17 mmol) were combined in acetonitrile (3 ml) and heated to 110° C. for 15 min in a CEM microwave reactor. The cooled reaction mixture was concentrated onto silica gel and purified by flash chromatography on silica gel (hexane/ethyl acetate gradient) twice to yield the title compound (46 mg, 5% yield) as an off-white solid, mp 81-83° C. 1H NMR (CDCl3) δ 7.9 (m, 1H), 7.43 (m, 1H), 6.89 (dd, 1H), 5.7 (dd, 1H), 5.57 (dd, 1H), 4.72 (br s, 2H), 3.93 (s, 3H).

후처리

  1. customThe cooled reaction mixture
  2. concentrationwas concentrated onto silica gel
  3. custompurified by flash chromatography on silica gel (hexane/ethyl acetate gradient) twice

출처 및 근거

ORD 기록
ord-440acf443d5244e2aa737f221d95a784
출처 데이터셋
uspto-grants-2014_02
특허 번호
US08658791B2

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