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Diethyl (ethoxymethylene)malonate → HCID 86613888, 화합물

HRID 598106
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HRID 598106 반응식
C(NC(C)C)(C)C.C([Li])CCC.[C:13]1([CH3:30])[CH:18]=[C:17]([CH3:19])[CH:16]=[C:15]([CH3:20])[C:14]=1[C:21]1[N:26]=[C:25]([CH2:27][C:28]#[N:29])[CH:24]=[CH:23][CH:22]=1.C([O:33][CH:34]=[C:35]([C:41](OCC)=O)[C:36]([O:38][CH2:39][CH3:40])=[O:37])C>O1CCCC1.C(O)(=O)C>[C:28]([C:27]1[CH:41]=[C:35]([C:36]([O:38][CH2:39][CH3:40])=[O:37])[C:34](=[O:33])[N:26]2[C:25]=1[CH:24]=[CH:23][CH:22]=[C:21]2[C:14]1[C:15]([CH3:20])=[CH:16][C:17]([CH3:19])=[CH:18][C:13]=1[CH3:30])#[N:29]
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참가 물질

7

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HCID 6871Diethyl (ethoxymethylene)malonateHCID 7912DiisopropylamineHCID 672670006-(2,4,6-Trimethylphenyl)-2-pyridineacetonitrileHCID 178418339Butyllithium

생성물 1

HCID 86613888HCID 86613888, 화합물수율 84.3%

시약·촉매·용매 2

HCID 176Acetic Acid
용매
HCID 8028Tetrahydrofuran용매2회

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온도
-20 °C

실험 절차

Diisopropylamine (1.6 mL, 11.6 mmol) in tetrahydrofuran (15 mL) was charged with n-butyllithium (2.5M, 4.6 mL, 11.6 mmol) at 0° C. The reaction stirred for 0.5 h. The solution was cooled to −20° C. and (6-mesitylpyridin-2-yl)acetonitrile (2.49 g, 10.5 mmol) was added drop wise (as a solution in 5 mL tetrahydrofuran). After 0.5 h, the solution was cooled to −78° C. and diethyl ethoxymethylenemalonate (2.1 mL, 10.5 mmol) was added. The reaction stirred for 0.5 h and was then cooled to room temperature. The reaction was quenched with water and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, filtered and concentrated to give an orange residue. The material was dissolved in acetic acid (20 mL) and heated at 100° C. for 4 h. The solution was cooled and poured into an Erlenmeyer flask and washed with water. The solution was neutralized with saturated sodium bicarbonate. The solution was extracted with ethyl acetate (3 times), dried, and concentrated. Flash chromatography (25% ethyl acetate/hexanes) gave 3.19 g (84% yield) of the title compound as a yellow solid.

후처리

  1. waitAfter 0.5 h
  2. temperaturethe solution was cooled to −78° C.
  3. stirringThe reaction stirred for 0.5 h
  4. temperaturewas then cooled to room temperature
  5. customThe reaction was quenched with water
  6. extractionextracted with ethyl acetate
  7. dry with materialThe organic layer was dried over magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customto give an orange residue
  11. temperatureheated at 100° C. for 4 h
  12. temperatureThe solution was cooled
  13. additionpoured into an Erlenmeyer flask
  14. washwashed with water
  15. extractionThe solution was extracted with ethyl acetate (3 times)
  16. customdried
  17. concentrationconcentrated

출처 및 근거

ORD 기록
ord-80cd84f48efa4ab0a310ed7675d60ed9
출처 데이터셋
uspto-grants-2011_03
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US07897607B2

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