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

HRID 1467918

반응식

HRID 1467918 반응식
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]

참가 물질

7

반응물 4

HCID 7294Methyl AcrylateHCID 14797Potassium HydroxideHCID 23665647Potassium tert-butoxide2회HCID 581972636'-bromo-4-methoxyspiro[cyclohexane-1,2'-inden]-1'(3'H)-one2회

생성물 1

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

시약·촉매·용매 2

HCID 962Water용매HCID 57417360Sodium chloride; water용매

반응 조건

온도
0 °C

실험 절차

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]+.

후처리

  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

출처 및 근거

ORD 기록
ord-a86c3bc729b4494fb698878e16cc1a46
출처 데이터셋
uspto-grants-2015_04
특허 번호
US09000182B2

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