Lithium Chloride → Ethyl 5-[2-(acetylamino)pyridin-4-yl]-4-cyano-3-iodothiophene-2-carboxylate

HRID 2401972ノート

反応式

HRID 2401972 の反応式
[C:1]([C:3]1[C:4]([I:14])=[C:5]([C:9]([O:11][CH2:12][CH3:13])=[O:10])[S:6][C:7]=1I)#[N:2].C[Sn](C)(C)[C:17]1[CH:22]=[CH:21][N:20]=[C:19]([NH:23][C:24](=[O:26])[CH3:25])[CH:18]=1.[Cl-].[Li+]>O1CCOCC1.[Cu]I.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:24]([NH:23][C:19]1[CH:18]=[C:17]([C:7]2[S:6][C:5]([C:9]([O:11][CH2:12][CH3:13])=[O:10])=[C:4]([I:14])[C:3]=2[C:1]#[N:2])[CH:22]=[CH:21][N:20]=1)(=[O:26])[CH3:25]

参加物

7

反応物 3

HCID 433294Lithium ChlorideHCID 59529632N-(4-(trimethylstannyl)pyridin-2-yl)acetamideHCID 66748000Ethyl 4-cyano-3,5-diiodothiophene-2-carboxylate

生成物 1

HCID 66747307Ethyl 5-[2-(acetylamino)pyridin-4-yl]-4-cyano-3-iodothiophene-2-carboxylate収率 65%

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418397HCID 178418397、化合物触媒HCID 312751,4-Dioxane溶媒

反応条件

温度
110 °C

実験手順

To a solution of ethyl 4-cyano-3,5-diiodothiophene-2-carboxylate (0.473 g, 1.09 mmol) and N-[4-(trimethylstannyl)pyridin-2-yl]acetamide (0.392 g, 1.31 mmol) in dioxane (10.2 mL) was added lithium chloride (0.139 g, 3.28 mmol), copper(I) iodide (0.0624 g, 0.328 mmol), and tetrakis(triphenylphosphine)palladium(0) (0.0947 g, 0.0819 mmol). The reaction flask was evacuated and backfilled with argon, then the solution was heated at 110° C. for 2 hours. The mixture was cooled to room temperature and a mixture of dichloromethane and methanol was added until almost all solids had dissolved. The suspension was filtered through celite and the filtrate was evaporated. Column chromatography was performed to yield the title compound (0.312 g, 65%). LCMS: (FA) ES+ 442. 1H NMR (400 MHz, d6-DMSO) δ: 8.54-8.49 (m, 2H), 8.31 (s, 1H), 4.38-4.32 (m, 2H), 2.13 (s, 3H), 1.36-1.29 (m, 3H).

後処理

  1. customThe reaction flask was evacuated
  2. temperatureThe mixture was cooled to room temperature
  3. additiona mixture of dichloromethane and methanol
  4. additionwas added until almost all solids
  5. dissolutionhad dissolved
  6. filtrationThe suspension was filtered through celite
  7. customthe filtrate was evaporated

出典と根拠

ORDレコード
ord-71d69a61b54742efac7b8b09db7d0aa4
出典データセット
uspto-grants-2014_08
特許番号
US08796271B2

反応ノート

読み込み中…