Hydrochloric Acid → Diethyl 3-chloro-4-aminobenzylphosphonate

HRID 1947857Notes

Reaction equation

HRID 1947857 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:14]=[CH:15][C:16]=1[N+:17]([O-])=O)[CH2:5][P:6](=[O:13])([O:10][CH2:11][CH3:12])[O:7][CH2:8][CH3:9].Cl>CCO.[Fe]>[NH2:17][C:16]1[CH:15]=[CH:14][C:4]([CH2:5][P:6](=[O:13])([O:7][CH2:8][CH3:9])[O:10][CH2:11][CH3:12])=[CH:3][C:2]=1[Cl:1]

Participants

5

Reactant 2

HCID 313Hydrochloric AcidHCID 86654007Diethyl 3-chloro-4-nitrobenzylphosphonate2×

Product 1

HCID 19077629Diethyl 3-chloro-4-aminobenzylphosphonate

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 702EthanolSolvent

Procedure

A solution of diethyl (3-chloro-4-nitrobenzyl)phosphonate (Compound 104C, 0.500 g, 1.62 mmol) in EtOH (10 mL) was charged with iron (0.454 g, 8.12 mmol) and heated to reflux. When the reaction mixture reached reflux, it was charged with 0.1 N aq HCl (0.500 mL, 0.0812 mmol) and stirred for 10 min. The reaction mixture was filtered through a pad of celite and the filtrate was concentrated in vacuo. The compound was purified on an Isco Combiflash eluting with 40 to 90% EtOAc in heptane to afford the title compound. 1H NMR (400 MHz, chloroform-d) δ 7.19 (t, J=2.40 Hz, 1H), 7.01 (td, J=2.27, 8.08 Hz, 1H), 6.71 (dd, J=0.63, 8.21 Hz, 1H), 3.96-4.08 (m, 4H), 2.96-3.06 (m, 2H), 1.26 (t, J=7.07 Hz, 6H); MS (ES+): m/z: 278.0633 [MH+]. HPLC: tR=1.18 min (UPLC TOF MS: polar—3 min).

Workup

  1. temperatureheated to reflux
  2. temperatureWhen the reaction mixture reached reflux
  3. filtrationThe reaction mixture was filtered through a pad of celite
  4. concentrationthe filtrate was concentrated in vacuo
  5. customThe compound was purified on an Isco Combiflash
  6. washeluting with 40 to 90% EtOAc in heptane

Sources & evidence

ORD record
ord-e480df09971c4e2d8ac62d5f4c92cab0
Source dataset
uspto-grants-2013_03
Patent number
US08399433B2

Reaction notes

Loading…