Dimethyl malonate → 2-Vinylcyclopropane-1,1-dicarboxylic acid monomethyl ester

HRID 369415

반응식

HRID 369415 반응식
[Cl-].[Cl-].[Ca+2].[CH3:4][O:5][C:6]([C:8]1([C:13]([O:15]C)=[O:14])[CH2:10][CH:9]1[CH:11]=[CH2:12])=[O:7].COC(=O)CC(OC)=O.BrC/C=C/CBr.[OH-].[K+]>CO>[CH3:4][O:5][C:6]([C:8]1([C:13]([OH:15])=[O:14])[CH2:10][CH:9]1[CH:11]=[CH2:12])=[O:7]

참가 물질

7

반응물 5

HCID 7943Dimethyl malonateHCID 14797Potassium HydroxideHCID 641245trans-1,4-Dibromo-2-buteneHCID 5284359Calcium ChlorideHCID 104649921,1-Dimethyl 2-ethenylcyclopropane-1,1-dicarboxylate

생성물 1

HCID 108559152-Vinylcyclopropane-1,1-dicarboxylic acid monomethyl ester수율 83%

시약·촉매·용매 1

HCID 887Methanol용매

실험 절차

In a 100-ml two-necked flask with thermometer, magnet stirrer and CaCl2 tube, 36.8 g (0.2 mole) of 2-vinylcyclopropane-1,1-dicarboxylic acid dimethyl ester, which is accessible from malonic acid dimethyl ester and trans-1,4-dibromobut-2-ene (cf. U.S. Pat. No. 4,713,478 and U.S. Pat. No. 4,713,479) were dissolved in 65 ml of methanol and cooled to ca. 5° C. with ice water. 13.3 g (0.2 mole) of KOH were added portionwise to the mixture, so that the temperature did not rise above 15° C. To complete the reaction, stirring was carried out for a further 12 h and the mixture was then concentrated at a rotation evaporator in vacuum (50 mbar) at 50° C. The obtained oil (ca. 43 g) was dissolved in 50 ml of water and adjusted to about pH 2-3 with conc. hydrochloric acid accompanied by cooling. The organic phase was taken up in 100 ml of diethyl ether, the aqueous phase extracted twice more each time with 100 ml of diethyl ether and the combined ether phases dried over anhydrous Na2SO4. The solution was stabilized with 0.01 g of hydroquinone monomethyl ether, concentrated in vacuum and dried in fine vacuum. 28.2 g (83% yield) of a colourless liquid were obtained.

후처리

  1. customdid not rise above 15° C
  2. customthe reaction
  3. concentrationthe mixture was then concentrated at a rotation evaporator in vacuum (50 mbar) at 50° C
  4. dissolutionThe obtained oil (ca. 43 g) was dissolved in 50 ml of water
  5. temperatureby cooling
  6. extractionthe aqueous phase extracted twice more each time with 100 ml of diethyl ether
  7. dry with materialthe combined ether phases dried over anhydrous Na2SO4
  8. concentrationconcentrated in vacuum
  9. customdried in fine vacuum

출처 및 근거

ORD 기록
ord-5533d752745a40d9b7bfc435e358d05b
출처 데이터셋
uspto-grants-2000_10
특허 번호
US06136887

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