Hydrochloric Acid → Diethyl 3-chloro-4-aminobenzylphosphonate

HRID 2279772Notes

Reaction equation

HRID 2279772 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 24E, 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, 0.08 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 Teledyne Isco Combiflash® Rf system 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: 278.06 [MH+]. UPLC: tR=1.18 min (UPLC-TOF: 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 Teledyne Isco Combiflash® Rf system
  6. washeluting with 40 to 90% EtOAc in heptane

Sources & evidence

ORD record
ord-ae2cb123de1d40528e4a7bb4a1a92d67
Source dataset
uspto-grants-2015_09
Patent number
US09133224B2

Reaction notes

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