Thionyl Chloride → Ethyl chloro[(3-methoxy-4-nitrophenyl) methyl]phosphinate

HRID 2279915노트

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HRID 2279915 반응식
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:15]=[CH:16][C:17]=1[N+:18]([O-:20])=[O:19])[CH2:6][P:7](=O)([O:11]CC)[O:8][CH2:9][CH3:10].S(Cl)([Cl:23])=O>CN(C=O)C>[Cl:23][P:7]([CH2:6][C:5]1[CH:15]=[CH:16][C:17]([N+:18]([O-:20])=[O:19])=[C:3]([O:2][CH3:1])[CH:4]=1)(=[O:11])[O:8][CH2:9][CH3:10]

참가 물질

4

반응물 2

HCID 24386Thionyl ChlorideHCID 86654016Diethyl (3-methoxy-4-nitrobenzyl)phosphonate2회

생성물 1

HCID 86697855Ethyl chloro[(3-methoxy-4-nitrophenyl) methyl]phosphinate

시약·촉매·용매 1

HCID 6228Dimethylformamide용매

실험 절차

A solution of diethyl (3-methoxy-4-nitrobenzyl)phosphonate (Compound 1G, 5 g, 15.5 mmol) in thionyl chloride (50 mL, 690 mmol) was treated with catalytic amount of DMF and heated to reflux under nitrogen for 6 h. The mixture was concentrated under reduced pressure and co-evaporated with dichloroethane (50 mL) to give crude (ethyl chloro[(3-methoxy-4-nitrophenyl) methyl]phosphinate). This material was taken up in DCM (20 mL) and added to a solution of 2-propanol (4 mL, 52 mmol) and DIPEA (6 mL, 34.5 mmol) in DCM (20 mL). The resulting mixture was stirred at rt for 24 hrs. The solvents were evaporated and the residue was purified by column chromatography (SiO2, 5% methanol in dichloromethane) to give 3 g of the desired product as a light-yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.8 2(d, J=8.4 Hz, 1H), 7.1 (s, 1H), 6.92 (d, J=8.5 Hz, 1H), 4.6-4.4.75 (m, 1H), 4.05-4.08 (m, 2H), 3.93 (s, 3H), 3.18 (d, J=20 Hz, 2H), 1.18-1.25 (m, 9H).

후처리

  1. temperatureheated
  2. temperatureto reflux under nitrogen for 6 h
  3. concentrationThe mixture was concentrated under reduced pressure and co-evaporated with dichloroethane (50 mL)

출처 및 근거

ORD 기록
ord-3a2291bb1e3f4a8e8ab979e7684030bc
출처 데이터셋
uspto-grants-2015_09
특허 번호
US09133224B2

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