Benzyl Chloride → Ethyl 2-benzyl-1,3-dithiane-2-carboxylate

HRID 1379350

反応式

HRID 1379350 の反応式
[CH2:1]([O:3][C:4]([CH:6]1[S:11][CH2:10][CH2:9][CH2:8][S:7]1)=[O:5])[CH3:2].C([Li])CCC.[CH2:17](Cl)[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1>O1CCCC1>[CH2:17]([C:6]1([C:4]([O:3][CH2:1][CH3:2])=[O:5])[S:7][CH2:8][CH2:9][CH2:10][S:11]1)[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1

参加物

5

反応物 3

HCID 7503Benzyl ChlorideHCID 88552Ethyl 1,3-dithiane-2-carboxylateHCID 178418339Butyllithium

生成物 1

HCID 303709Ethyl 2-benzyl-1,3-dithiane-2-carboxylate収率 88.5%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-25 °C

実験手順

A solution of 3.0 g (15.6 mmol) of 2-ethoxycarbonyl-1,3-dithiane in 40 ml of dry tetrahydrofuran was cooled under inert atmosphere to -78° C. and treated with 7.5 ml (15.6 mmol) of n-butyllithium. The resulting solution was warmed to -25° C., stirred for 20 min, recooled to -78° C., treated with 1.8 ml (15.6 mmol) of benzyl chloride, and stirred at ambient temperature for 16 h. After quenching with aqueous ammonium chloride, the mixture was extracted with ether, washed sequentially with water, aqueous sodium thiosulfate, and brine, dried over MgSO4, and concentrated in vacuo. Flash chromatography using 5% ethyl acetate in hexane gave 3.9 g (88%) of the desired compound. 1H NMR (CDCl3) δ 1.33 (t, J=7 Hz, 3H), 1.85 (qt, J=14, 3 Hz, 1H), 2.11 (dm, J=14 Hz, 1H), 2.69 (dt, J=14, 4 Hz, 2 H), 3.23 (ddd, J=14, 12, 3 Hz, 2H), 3.38 (s, 2H), 4.27 (q, J=7 Hz, 2H), 7.25-7.35 (m, 5H). Mass spectrum (M+NH4)+ =300.

後処理

  1. customrecooled to -78° C.
  2. stirringstirred at ambient temperature for 16 h
  3. customAfter quenching with aqueous ammonium chloride
  4. extractionthe mixture was extracted with ether
  5. washwashed sequentially with water, aqueous sodium thiosulfate, and brine
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-702a12b08c19450ea39ebd6aabd4e4d8
出典データセット
uspto-grants-1997_09
特許番号
US05670675

関連ノート

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