Diethyl Malonate → Diethyl 2-vinylcyclopropane-1,1-dicarboxylate

93.4 g (583 mmol) of malonic acid diethyl ester and 1000 mL of toluene were added into a four-necked flask (2 L), and thereafter, 223 mL (569 mmol) of a 20% sodium ethoxide ethanol solution was added thereto as a base. The obtained mixture was stirred at room temperature for 1.5 hours, and 59.4 g of trans-1,4-dibromo-2-butene (278 mmol; a reagent manufactured by Sigma-Aldrich) was then added to the reaction solution. The obtained mixture was stirred at room temperature for 2 hours, and 109 mL (278 mmol) of a 20% sodium ethoxide ethanol solution was then added to the reaction solution. The obtained mixture was stirred at room temperature for 1 hour, and 29.1 g of trans-1,4-dibromo-2-butene (136 mmol; a reagent manufactured by Sigma-Aldrich) was then added to the reaction solution. The mixture was stirred at room temperature for 4 hours, and 347 mL of a 1 M sodium hydroxide aqueous solution was then added to the reaction solution. The mixture was stirred for 14 hours, and an organic layer was then separated. Subsequently, the organic layer was washed with 132 mL of water twice, and was then dried over anhydrous sodium sulfate. The resultant was filtrated, and the obtained filtrate was concentrated at 40° C. under reduced pressure, so as to obtain 99.3 g of 1,1-di-ethoxycarbonyl-2-vinylcyclopropane in the form of a crude product of a light yellow oily substance. This crude product contained 83.2 g of 1,1-di-ethoxycarbonyl-2-vinylcyclopropane (yield: 94.9%). However, this crude product did not contain a malonic diethyl ester.

1. additionwas then added to the reaction solution
2. stirringThe obtained mixture was stirred at room temperature for 2 hours
3. stirringThe obtained mixture was stirred at room temperature for 1 hour
4. additionwas then added to the reaction solution
5. stirringThe mixture was stirred at room temperature for 4 hours
6. stirringThe mixture was stirred for 14 hours
7. customan organic layer was then separated
8. washSubsequently, the organic layer was washed with 132 mL of water twice
9. dry with materialwas then dried over anhydrous sodium sulfate
10. filtrationThe resultant was filtrated
11. concentrationthe obtained filtrate was concentrated at 40° C. under reduced pressure

ORD-Eintrag

ord-9bc3aed611464d5e9b0f04a3de987e13

Quelldatensatz

uspto-grants-2015_05

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US09029107B2