Dichloromethane → Ethyl 2-cyano-3-[3-(methyloxy)phenyl]-2-butenoate

HRID 573563

반응식

HRID 573563 반응식
C[Si](C)(C)N[Si](C)(C)C.[CH3:10][O:11][C:12]1[CH:13]=[C:14]([C:18](=O)[CH3:19])[CH:15]=[CH:16][CH:17]=1.[C:21]([CH2:23][C:24]([O:26][CH2:27][CH3:28])=[O:25])#[N:22].C(Cl)Cl>C(O)(=O)C.O>[C:21]([C:23](=[C:18]([C:14]1[CH:15]=[CH:16][CH:17]=[C:12]([O:11][CH3:10])[CH:13]=1)[CH3:19])[C:24]([O:26][CH2:27][CH3:28])=[O:25])#[N:22]

참가 물질

7

반응물 4

HCID 6344DichloromethaneHCID 7764Ethyl cyanoacetateHCID 114603-MethoxyacetophenoneHCID 13838Hexamethyldisilazane

생성물 1

HCID 4115002Ethyl 2-cyano-3-[3-(methyloxy)phenyl]-2-butenoate수율 86.3%

시약·촉매·용매 2

HCID 176Acetic Acid용매2회HCID 962Water용매

실험 절차

Hexamethyldisilazane (17.45 mL, 83 mmol) was added dropwise to acetic acid (38.1 mL, 666 mmol) (caution exothermic, maintain below 70° C.) stirred under an atmosphere of nitrogen. The resulting mixture was added to a solution of 1-[3-(methyloxy)phenyl]ethanone (9.14 mL, 66.6 mmol) and ethyl cyanoacetate (11.75 mL, 110 mmol) in acetic acid (16 mL), which was then stirred at 70° C. for 18 h. The mixture was then allowed to cool to RT and DCM (350 mL) and water (125 mL) were added. The organic layer was then separated and washed with additional water (125 mL) and dried with anhydrous MgSO4, filtered and evaporated to dryness. The residue was purified on silica, eluting with a gradient of 0-30% ethyl acetate in isohexane and further purified on silica, eluting with a gradient of 0-25% ethyl acetate in isohexane, to afford the title compound (14.1 g). LCMS (A) m/z: 246 [M+1]+, Rt 1.28 min (basic).

후처리

  1. stirringwas then stirred at 70° C. for 18 h
  2. customThe organic layer was then separated
  3. washwashed with additional water (125 mL)
  4. dry with materialdried with anhydrous MgSO4
  5. filtrationfiltered
  6. customevaporated to dryness
  7. customThe residue was purified on silica
  8. washeluting with a gradient of 0-30% ethyl acetate in isohexane
  9. customfurther purified on silica
  10. washeluting with a gradient of 0-25% ethyl acetate in isohexane

출처 및 근거

ORD 기록
ord-02851e9ff45a4b3ca21cb5998be3404f
출처 데이터셋
uspto-grants-2015_05
특허 번호
US09029545B2

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