Tetrahydrofuran → Ethyl 3-(acetylthio)-3-cyanopropanoate

HRID 882673

反応式

HRID 882673 の反応式
[C:1](/[CH:3]=[CH:4]\[C:5]([O:7][CH2:8][CH3:9])=[O:6])#[N:2].[S:10]1C=CC=C1CC(O)=O.CCN(C(C)C)C(C)C.C1C[O:31][CH2:30][CH2:29]1>>[C:30]([S:10][CH:3]([C:1]#[N:2])[CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6])(=[O:31])[CH3:29]

参加物

5

反応物 4

HCID 8028Tetrahydrofuran2 回HCID 159702-Thiopheneacetic acidHCID 81531DiisopropylethylamineHCID 15577688Ethyl (2Z)-3-cyanoprop-2-enoate

生成物 1

HCID 53248108Ethyl 3-(acetylthio)-3-cyanopropanoate収率 65%

実験手順

(Z)-ethyl 3-cyanoacrylate (5.01 g, 40.00 mmol) in 80 ml of THF at −20° C. was added the solution of thiol acetic acid (5.0 ml, 70.15 mmol) and DIPEA (16.0 ml, 92.03 mmol) in 20 ml of THF in 30 min. The reaction was kept at −20° C. for 4 hr then room temperature overnight. The mixture was concentrated, diluted with CH2Cl2, washed with saturated NaHCO3, dried over MgSO4, filtered, evaporated and purified by SiO2 chromatography (1:4 EtAC/Hexane) to afford 5.22 g (65%) of the title compound. Rf=0.25 (1:4 EtAC/Hexane); 1H NMR (CDCl3), 4.44 (m, 1H), 4.11 (dd, 2H, J=7.1, 14.3 Hz), 3.38 (m, 1H), 3.15 (m, 1H), 2.17 (s, 3H), 1.19 (t, 3H, J=7.2 Hz); 13C NMR 194.12, 173.21, 119.82, 61.35, 33.52, 30.08, 14.62; MS m/z+ 225.9 (MW+Na), m/z− 201.7 (MW−H).

後処理

  1. customroom temperature overnight
  2. concentrationThe mixture was concentrated
  3. additiondiluted with CH2Cl2
  4. washwashed with saturated NaHCO3
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. customevaporated
  8. custompurified by SiO2 chromatography (1:4 EtAC/Hexane)

出典と根拠

ORDレコード
ord-ba6cdf2b3bb44480aa7b805b882d90d0
出典データセット
uspto-grants-2012_08
特許番号
US08236319B2

関連ノート

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