Propyne → (3-Prop-1-ynylpyridin-4-yl)carbamic acid tert-butyl ester

HRID 400608ノート

反応式

HRID 400608 の反応式
[CH:1]#[C:2][CH3:3].[C:4]([O:8][C:9](=[O:18])[NH:10][C:11]1[CH:16]=[CH:15][N:14]=[CH:13][C:12]=1I)([CH3:7])([CH3:6])[CH3:5].C(OCC)(=O)C.[Cl-].[NH4+]>CN(C=O)C.C(N(CC)CC)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.[Cu]I>[C:4]([O:8][C:9](=[O:18])[NH:10][C:11]1[CH:16]=[CH:15][N:14]=[CH:13][C:12]=1[C:1]#[C:2][CH3:3])([CH3:7])([CH3:6])[CH3:5]

参加物

9

反応物 4

HCID 6335PropyneHCID 8857Ethyl AcetateHCID 25517Ammonium ChlorideHCID 10903275(3-Iodo-pyridin-4-yl)-carbamic acid tert-butyl ester

生成物 1

HCID 11031741(3-Prop-1-ynylpyridin-4-yl)carbamic acid tert-butyl ester収率 98%

試薬・触媒・溶媒 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418476HCID 178418476、化合物触媒HCID 6228Dimethylformamide溶媒HCID 8471Triethylamine溶媒

実験手順

Propyne (6.3 mL, 124 mmol) was condensed in a pressure tube at −78° C. A solution of (3-iodopyridin-4-yl)carbamic acid tert-butyl ester (7.98 g, 24.9 mmol) in 15 mL of DMF, 60 mL of triethylamine, dichlorobis(triphenylphosphine)palladium (II) (877 mg, 1.25 mmol), and CuI (472 mg, 2.49 mmol) were added, and the tube was sealed and stirred at room temperature overnight. 200 mL of ethyl acetate and 100 mL of saturated aqueous ammonium chloride solution were added, the phases were separated and the aqueous layer was extracted with three 100 mL portions of ethyl acetate. The combined organic layers were dried over magnesium sulfate, filtered, and concentrated in vacuo. Chromatography on SiO2 (25% to 40% ethyl acetate in hexanes, gradient) afforded 5.65 g of (3-prop-1-ynylpyridin-4-yl)carbamic acid tert-butyl ester (98% yield).

後処理

  1. customcondensed in a pressure tube at −78° C
  2. customthe tube was sealed
  3. customthe phases were separated
  4. extractionthe aqueous layer was extracted with three 100 mL portions of ethyl acetate
  5. dry with materialThe combined organic layers were dried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-1651c747b4ee4cd181fbb69cce7c9731
出典データセット
uspto-grants-2014_06
特許番号
US08741897B2

反応ノート

読み込み中…