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

HRID 245291ノート

反応式

HRID 245291 の反応式
[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]

参加物

5

反応物 2

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 178418476HCID 178418476、化合物触媒HCID 6342Acetonitrile溶媒

反応条件

温度
110 °C

実験手順

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).

後処理

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

出典と根拠

ORDレコード
ord-440acf443d5244e2aa737f221d95a784
出典データセット
uspto-grants-2014_02
特許番号
US08658791B2

反応ノート

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