ホームMCPワークベンチSkills
ホームワークベンチ通知マイページ
llms.txt · MCPガイドプライバシーポリシー · 利用規約 · サポートv1.8.0
  1. ホーム
  2. /反応

Diisopropylamine → 3-Ethoxy-6-(3-t-butyldimethylsilyloxypropyl)cyclohex-2-enone

HRID 77269
ノート
印刷プレビュー

反応式

HRID 77269 の反応式
C([N-]C(C)C)(C)C.[Li+].C(NC(C)C)(C)C.[Li]CCCC.[CH2:21]([O:23][C:24]1[CH2:29][CH2:28][CH2:27][C:26](=[O:30])[CH:25]=1)[CH3:22].CN(C)P(N(C)C)(N(C)C)=O.I[CH2:43][CH2:44][CH2:45][O:46][Si:47]([C:50]([CH3:53])([CH3:52])[CH3:51])([CH3:49])[CH3:48]>O1CCCC1>[CH2:21]([O:23][C:24]1[CH2:29][CH2:28][CH:27]([CH2:43][CH2:44][CH2:45][O:46][Si:47]([C:50]([CH3:51])([CH3:53])[CH3:52])([CH3:48])[CH3:49])[C:26](=[O:30])[CH:25]=1)[CH3:22]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

8

反応物 6

HCID 7912DiisopropylamineHCID 12679HexamethylphosphoramideHCID 792163-Ethoxycyclohex-2-ene-1-oneHCID 2724682Lithium diisopropylamideHCID 11022956Tert-butyl-(3-iodopropoxy)-dimethylsilaneHCID 178418339Butyllithium

生成物 1

HCID 68514498
3-Ethoxy-6-(3-t-butyldimethylsilyloxypropyl)cyclohex-2-enone
収率 51.9%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒3 回

反応条件

温度
-78 °C

実験手順

To a lithium diisopropylamide (LDA) solution [prepared from diisopropylamine (3.82 mL, 27 mmol) and nBuLi (7.26 mL of a 2.5M solution in hexanes, 18 mmol) in tetrahydrofuran (THF, 12 mL) at 0° C.] at −78° C. was added 3-ethoxy-2-cyclohexen-1-one (2.64 mL, 18 mmol) in THF (6 mL), dropwise, over 40 min. After stirring for an additional 30 min at −78° C., hexamethyl phosphoramide (HMPA, 3.16 mL, 18 mmol) was added followed by the dropwise addition of 3-iodo-1-tert -butyldimethylsiloxypropane (5.45 g, 18 mmol) in THF (8 mL). The resultant mixture was allowed to warm to rt, stirred for 6 h and then quenched by the addition of water (10 mL). The reaction mixture was then partitioned between dichloromethane (DCM, 100 mL) and sat. NH4Cl (40 mL). The aqueous phase was extracted with DCM (3×50 mL), the organic phases combined and washed with brine (50 mL), dried over anhydrous MgSO4 and reduced to dryness. The resultant syrup was purified by flash column chromatography (hexanes/EtOAc 8/2) to yield 2 as a pale yellow oil (2.92 g, 51.2%). Rf 0.21 (hexanes/EtOAc 8/2); 1H NMR (300 MHz, CDCl3) δ 5.26 (1H, s), 3.83 (2H, q, J=7.0 Hz), 3.59 (1H, t, J=6.5 Hz), 3.58 (H, t, J=6.5 Hz), 2.38 (2H, t, J=6.2 Hz), 2.20-1.99 (2H, m), 1.85-1.35 (5H, m), 1.31 (3H, t, J=7.0 Hz), 0.84 (s, 9H), 0.00 (s, 6H); 13C NMR (75 MHz, CDCl3) δ 201.6, 176.7, 102.3, 64.2, 63.4, 45.0, 30.5, 28.0, 26.4, 26.0 (×2), 18.4, 14.2, −5.2.

後処理

  1. temperatureto warm to rt
  2. stirringstirred for 6 h
  3. customquenched by the addition of water (10 mL)
  4. customThe reaction mixture was then partitioned between dichloromethane (DCM, 100 mL) and sat. NH4Cl (40 mL)
  5. extractionThe aqueous phase was extracted with DCM (3×50 mL)
  6. washwashed with brine (50 mL)
  7. dry with materialdried over anhydrous MgSO4
  8. customThe resultant syrup was purified by flash column chromatography (hexanes/EtOAc 8/2)

出典と根拠

ORDレコード
ord-ea0940c9c5cd45cb84f4f322a50fa094
出典データセット
uspto-grants-2014_09
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08841132B2

反応ノート

読み込み中…

このページの内容参加物反応条件実験手順後処理出典と根拠反応ノート