Acetic Acid → Diethyl 2-methylidenecyclopropane-1,1-dicarboxylate

HRID 746473노트

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HRID 746473 반응식
Br[CH2:2][C:3](=[C:5]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[C:6]([O:8][CH2:9][CH3:10])=[O:7])[CH3:4].CC(C)([O-])C.[K+].C(O)(=O)C>C(O)(C)(C)C>[CH2:2]=[C:3]1[CH2:4][C:5]1([C:11]([O:13][CH2:14][CH3:15])=[O:12])[C:6]([O:8][CH2:9][CH3:10])=[O:7]

참가 물질

5

반응물 3

HCID 176Acetic AcidHCID 11254458Propanedioic acid, (2-bromo-1-methylethylidene)-, diethyl esterHCID 23665647Potassium tert-butoxide

생성물 1

HCID 29923459Diethyl 2-methylidenecyclopropane-1,1-dicarboxylate수율 23.6%

시약·촉매·용매 1

HCID 6386tert-Butanol용매

실험 절차

Compound 5 (43.4 g, 0.156 mol) from Example 1 was added to a vigorously stirred refluxing solution of potassium tert-butoxide (17.5 g, 0.156 mol) in tert-butyl alcohol (500 mL) under nitrogen. The stirring was continued for 15 min. and the mixture was immediately cooled in an ice bath. Acetic acid was then added, the solid portion was filtered off and thoroughly washed with ether. The filtrate was concentrated in vacuo, diluted with ether and the organic layer was washed several times with water. After drying with magnesium sulfate, the solution was evaporated in vacuo and the residue was distilled, bp. 99-93° C./0.3 torr, yield 14.8 g (47%) of a 1:1 mixture of 4+6. This mixture was chromatographed on a silica gel column using first hexanes-ether (40:1) and then (20:1) to give product 6 (7.3 g, 23%) as a colorless liquid.

후처리

  1. temperaturethe mixture was immediately cooled in an ice bath
  2. filtrationthe solid portion was filtered off
  3. washthoroughly washed with ether
  4. concentrationThe filtrate was concentrated in vacuo
  5. additiondiluted with ether
  6. washthe organic layer was washed several times with water
  7. dry with materialAfter drying with magnesium sulfate
  8. customthe solution was evaporated in vacuo
  9. distillationthe residue was distilled
  10. additionbp. 99-93° C./0.3 torr, yield 14.8 g (47%) of a 1:1 mixture of 4+6
  11. customThis mixture was chromatographed on a silica gel column

출처 및 근거

ORD 기록
ord-3152f0a46d17451181eb33a077f7c5ca
출처 데이터셋
uspto-grants-2008_07
특허 번호
US07393855B2

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