Methyl Acrylate → 6'-Isobutoxyspiro[cyclohexane-1,2'-indene]-1',4(3'H)-dione

HRID 1467918

反応式

HRID 1467918 の反応式
Br[C:2]1[CH:10]=[C:9]2[C:5]([CH2:6][C:7]3([CH2:16][CH2:15][CH:14]([O:17]C)[CH2:13][CH2:12]3)[C:8]2=[O:11])=[CH:4][CH:3]=1.[C:19]([O:23]C)(=O)[CH:20]=[CH2:21].[CH3:25]C(C)([O-])C.[K+].[OH-].[K+]>[Cl-].[Na+].O.O>[CH2:19]([O:23][C:2]1[CH:10]=[C:9]2[C:5]([CH2:6][C:7]3([CH2:12][CH2:13][C:14](=[O:17])[CH2:15][CH2:16]3)[C:8]2=[O:11])=[CH:4][CH:3]=1)[CH:20]([CH3:21])[CH3:25]

参加物

7

反応物 4

HCID 7294Methyl AcrylateHCID 14797Potassium HydroxideHCID 23665647Potassium tert-butoxide2 回HCID 581972636'-bromo-4-methoxyspiro[cyclohexane-1,2'-inden]-1'(3'H)-one2 回

生成物 1

HCID 679793196'-Isobutoxyspiro[cyclohexane-1,2'-indene]-1',4(3'H)-dione収率 56.3%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 57417360Sodium chloride; water溶媒

反応条件

温度
0 °C

実験手順

To a mixture of 6-isobutoxy-2,3-dihydro-1H-inden-1-one (Intermediate 4, 17.4 g, 85 mmol) and methyl acrylate (16.9 mL, 187 mmol) in 2-Me THF (84 mL) cooled to 0° C. was added potassium tert-butoxide (11.8 g, 102 mmol) in portions over 3 min. After stirring at r.t. for 2.5 h more potassium tert-butoxide (2.95 g, 25.5 mmol) was added at 0° C. After stirring at r.t. for 2.5 h were water (126 mL) and potassium hydroxide (4.77 g, 85 mmol) added and the mixture was heated at reflux overnight. The mixture was allowed to cool to r.t. and brine was added. The layers were separated and the aqueous layer was re-extracted with EtOAc twice. The combined organic layers were dried over Na2SO4, filtered and evaporated to yield the title compound (13.7 g, 56% yield). 1H NMR (400 MHz, CDCl3) δ ppm 1.04 (m, 8 H) 1.86 (m, 2 H) 2.11 (dt, 1 H) 2.21 (m, 2 H) 2.47 (m, 3 H) 2.70 (m, 2 H) 3.15 (s, 2 H) 3.76 (m, 3 H) 7.20 (m, 1 H) 7.25 (m, 1 H) 7.38 (d, 1 H); MS (ES+) m/z 287 [M+H]+.

後処理

  1. additionwas added at 0° C
  2. additionadded
  3. temperaturethe mixture was heated
  4. temperatureat reflux overnight
  5. temperatureto cool to r.t.
  6. customThe layers were separated
  7. extractionthe aqueous layer was re-extracted with EtOAc twice
  8. dry with materialThe combined organic layers were dried over Na2SO4
  9. filtrationfiltered
  10. customevaporated

出典と根拠

ORDレコード
ord-a86c3bc729b4494fb698878e16cc1a46
出典データセット
uspto-grants-2015_04
特許番号
US09000182B2

関連ノート

読み込み中…