Ethyl 2-cyanoethyl(diethoxymethyl)phosphinate → Phosphinic acid, (3-aminopropyl)(diethoxymethyl)-, ethyl ester

HRID 898211Notes

Reaction equation

HRID 898211 reaction equation
[C:1]([CH2:3][CH2:4][P:5]([CH:10]([O:14][CH2:15][CH3:16])[O:11][CH2:12][CH3:13])(=[O:9])[O:6][CH2:7][CH3:8])#[N:2]>N.CCO.[Ni]>[NH2:2][CH2:1][CH2:3][CH2:4][P:5]([CH:10]([O:14][CH2:15][CH3:16])[O:11][CH2:12][CH3:13])(=[O:9])[O:6][CH2:7][CH3:8]

Participants

5

Reactant 1

HCID 10037677Ethyl 2-cyanoethyl(diethoxymethyl)phosphinate

Product 1

HCID 10422382Phosphinic acid, (3-aminopropyl)(diethoxymethyl)-, ethyl esterYield 85%

Reagents, catalysts & solvents 3

HCID 935NickelCatalystHCID 222AmmoniaSolventHCID 702EthanolSolvent

Procedure

To a solution of 2.47 g (9.91 mmol) of ethyl 2-cyanoethyl (diethoxymethyl)phosphinate (from Step A) in 20 mL 2.0 M ammonia in EtOH was added 250 mg Raney Nickel. The mixture was subjected to hydrogenation conditions (H2, 40 psi, rt) for 16 hr. The reaction mixture was filtered over Celite and partitioned between CH2Cl2 and H2O. The aqueous phase was extracted twice with CH2Cl2. The organic layer and extractions were combined, dried, and concentrated to provide 2.13 g (85% yield) of the title compound: 1H NMR (500 MHz) δ 1.23 (dt, J1=7.1, J2=1.6 6H), 1.29 (t, J=7.1, 3H), 1.42 (s, br, 2H), 1.71-1.82 (m, 4H), 2.72-2.75 (m, 2H), 3.63-3.70 (m, 2H), 3.78-3.86 (m, 2H), 4.08-4.21 (m, 2H), 4.64 (d, J=6.7, 1H); ESI-MS 254 (M+H).

Workup

  1. filtrationThe reaction mixture was filtered over Celite
  2. custompartitioned between CH2Cl2 and H2O
  3. extractionThe aqueous phase was extracted twice with CH2Cl2
  4. extractionThe organic layer and extractions
  5. customdried
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-9dab21afb5be46bab29cb2a1e8c03417
Source dataset
uspto-grants-2008_04
Patent number
US07351725B2

Reaction notes

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