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

HRID 2279915ノート

反応式

HRID 2279915 の反応式
[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]

参加物

4

反応物 2

HCID 24386Thionyl ChlorideHCID 86654016Diethyl (3-methoxy-4-nitrobenzyl)phosphonate2 回

生成物 1

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

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

実験手順

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).

後処理

  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)

出典と根拠

ORDレコード
ord-3a2291bb1e3f4a8e8ab979e7684030bc
出典データセット
uspto-grants-2015_09
特許番号
US09133224B2

反応ノート

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