Triethylamine → Benzyl [4-(4-iodophenyl)but-3-yn-1-yl]carbamate

HRID 910722ノート

反応式

HRID 910722 の反応式
C(N(CC)CC)C.I[C:9]1[CH:14]=[CH:13][C:12]([I:15])=[CH:11][CH:10]=1.[CH2:16]([O:23][C:24](=[O:30])[NH:25][CH2:26][CH2:27][C:28]#[CH:29])[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1>C1COCC1.[Cu]I.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>[CH2:16]([O:23][C:24](=[O:30])[NH:25][CH2:26][CH2:27][C:28]#[C:29][C:9]1[CH:14]=[CH:13][C:12]([I:15])=[CH:11][CH:10]=1)[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1

参加物

7

反応物 3

HCID 8471TriethylamineHCID 12208p-DiiodobenzeneHCID 21185506HCID 21185506、化合物

生成物 1

HCID 59750570Benzyl [4-(4-iodophenyl)but-3-yn-1-yl]carbamate収率 86%

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418476HCID 178418476、化合物触媒HCID 8028Tetrahydrofuran溶媒2 回

実験手順

To a mixture of anhydrous THF and triethylamine (24 mL, 2/1, v/v) were sequentially added 1,4-diiodobenzene (2.03 g, 6.15 mmol) and copper (I) iodide (0.094 g, 0.246 mmol). The mixture was stirred at room temperature for 15 min. The flask was then evacuated and re-filled with Argon. The procedure was repeated three more times to ensure no oxygen remained. The catalyst, dichlorobis(triphenylphosphine)palladium(II) (0.173 g, 0.246 mmol) was added into the mixture under Argon protection. The other starting material, but-3-ynylcarbamic acid benzyl ester (0.50 g, 2.46 mmol), dissolved in THF (8 mL) was added dropwise over 6 hours. The newly formed reaction mixture was further stirred at room temperature overnight. The solid in the reaction mixture was vacuum filtered. The filtrate was concentrated. The residue was re-dissolved in dichloromethane and purified by column chromatography, eluting with a mixture of ethyl acetate (0-12%) and hexanes (100-88%) to afford the product 22 (0.852 g, 86%) as an off-white solid. 1H NMR (300 MHz, CDCl3): δ 2.61 (t, J=6.4 Hz, 2H), 3.44 (t, J=6.4 Hz, 2H), 5.07 (br s, 1H), 5.12 (s, 2H), 7.10 (d, J=8.3 Hz, 2H), 7.35 (m, 5H), 7.63 (d, J=8.3 Hz, 2H). m/z (APCI) 405 [C18H16NO2+H]+.

後処理

  1. customThe flask was then evacuated
  2. additionre-filled with Argon
  3. additionwas added dropwise over 6 hours
  4. customThe newly formed reaction mixture
  5. stirringwas further stirred at room temperature overnight
  6. filtrationfiltered
  7. concentrationThe filtrate was concentrated
  8. dissolutionThe residue was re-dissolved in dichloromethane
  9. custompurified by column chromatography
  10. washeluting with a mixture of ethyl acetate (0-12%) and hexanes (100-88%)

出典と根拠

ORDレコード
ord-92662d4022c04809bb329babd56b8d65
出典データセット
uspto-grants-2011_09
特許番号
US08022210B2

反応ノート

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