반응 #1951065

반응 방정식

phosphorochloridic acid diethyl ester

cyclopropylmagnesium bromide

NH4Cl

→

cyclopropylphosphonic acid diethyl ester

수율 51.0%

용매

THF

반응 조건

후처리

1. 1
   기타To a 200 mL round-bottom flask equipped with a magnetic stir-bar
2. 2
   온도to slowly warm to room temperature overnight
3. 3
   기타partitioned
4. 4
   추출The product was extracted from the aqueous layer with diethyl ether (1×100 mL)
5. 5
   건조dried over sodium sulfate
6. 6
   농축concentrated in vacuo
7. 7
   workup.DISTILLATIONThe resulting yellow oil was further purified by vacuum distillation (65-75° C. at 500 mTorr)

실험 절차

To a 200 mL round-bottom flask equipped with a magnetic stir-bar was added phosphorochloridic acid diethyl ester (17.25 mL, 120 mmole) and THF (200 mL). The mixture was cooled to −78° C. and a solution of cyclopropylmagnesium bromide (200 mL, 0.5 M in THF, 100 mmol) was added dropwise over 30 minutes using an addition funnel. The reaction was allowed to slowly warm to room temperature overnight. The resulting clear reaction mixture was poured into saturated NH4Cl (200 mL) and partitioned. The product was extracted from the aqueous layer with diethyl ether (1×100 mL). The organic fractions were combined, dried over sodium sulfate, and concentrated in vacuo. The resulting yellow oil was further purified by vacuum distillation (65-75° C. at 500 mTorr) to provide cyclopropylphosphonic acid diethyl ester (9.025 g, 51%) as a colorless oil. 1H NMR (400 MHz, CDCl3) δ 4.11-4.03 (m, 4H), 1.32-1.29 (m, 6H), 0.90-0.77 (m, 5H); 13C NMR (100 MHz, CDCl3) δ ppm 61.7 (d, J=5.3 Hz), 16.4 (d, J=6.1 Hz), 3.3 (d, J=196.3 Hz), 3.0 (d, J=4.6 Hz).

출처