반응 #9878

반응 방정식

HCl

benzylmalonic acid

paraformaldehyde

diethylamine

→

compound 17

수율 90.0%

2-methylene-3-phenylpropanoic acid

수율 90.0%

용매

water

ethyl acetate

반응 조건

후처리

1. 1
   기타the reaction temperature below 20° C. (see FIG. 6)
2. 2
   온도The reaction was then warmed
3. 3
   온도to reflux for 90 min
4. 4
   온도cooled again on ice
5. 5
   기타the reaction temperature below 10° C
6. 6
   기타The phases were then separated
7. 7
   세척The organic layer was washed with brine (100 mL)
8. 8
   건조dried over sodium sulfate
9. 9
   여과filtered
10. 10
    농축the filtrate concentrated under vacuum

실험 절차

A solution of benzylmalonic acid (20.0 g, 0.103 mol, 1 eq) and paraformaldehyde (4.94 g, 0.164 mol, 1.6 eq) in ethyl acetate (150 mL) was cooled (0° C.) and treated with diethylamine (10.65 mL, 0.103 mol, 1 eq) drop wise, keeping the reaction temperature below 20° C. (see FIG. 6). The reaction was then warmed to reflux for 90 min and cooled again on ice. The homogeneous solution was treated with water (20 mL) and concentrated aqueous HCl (12N) (9.0 mL, 0.108 mol) drop wise, keeping the reaction temperature below 10° C. The phases were then separated. The organic layer was washed with brine (100 mL), dried over sodium sulfate, filtered, and the filtrate concentrated under vacuum giving compound 17 as a white solid (15 g, 90%). Rf 0.46 (hexane/EtOAc=7:3). 1H NMR (300 MHz, CDCl3) δ 7.28 (m, 5H), 6.42 (s, 1H), 5.62 (s, 1H), 3.67 (s, 2H). [M−H]− 161.0: tR=2.53 min; purity: 99%.

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