HCID 178460558, compound → HCID 178511570, compound

HRID 1062541Notes

Reaction equation

HRID 1062541 reaction equation
C(OC([NH:8][C@@H:9]1[CH2:13][CH2:12][C@H:11]([CH2:14][PH:15](=[O:20])[O:16]C(C)C)[CH2:10]1)=O)(C)(C)C>Cl>[NH2:8][C@@H:9]1[CH2:13][CH2:12][C@H:11]([CH2:14][PH:15](=[O:16])[OH:20])[CH2:10]1

Participants

3

Reactant 1

HCID 178460558HCID 178460558, compound

Product 1

HCID 178511570HCID 178511570, compound

Reagents, catalysts & solvents 1

HCID 313Hydrochloric AcidSolvent

Procedure

(±)-cis-Isopropyl [3-(t-butyloxyamino)cyclopentanyl]methylphosphinate (10) (2.1 g, 9.6 mmol) was dissolved in aqueous HCl (6M, 40 cm3) and the solution heated at reflux for 30 h. After cooling, the solution was evaporated to dryness under reduced pressure. The residue was dissolved in water (10 cm3) and applied to an ion exchange column (Dowex 50, H+ form). The column was eluted with water until the eluate was colourless and pH neutral and then eluted with aqueous pyridine (1M). Ninhydrin positive fractions were combined and evaporated to dryness under reduced pressure. Residual traces of pyridine were removed by repeatedly redissolving the compound in water (20 cm3) and re-evaporating (3 times). Recrystallisation from ethanol/acetone and drying gave the title compound (11) as an off white solid (1 g, 46%): 1H NMR (300 MHz, D2O) δ 1.27 (3H, d, J=12.9 Hz, PCH3), 1.56-2.27 (7H, m, C(1)—H, C(2)—H, C(2)—H′, C(4)—H, C(4)—H′, C(5)—H and C(5)—H), 3.59 (1H, m, C(3)—H), 13C NMR (75.46 MHz, D2O) 13.02 (PCH3, d, JPC=92.0 Hz), 23.9 (C(5)), 30.50 (C(4), d, 3JPC=7.5 Hz), 31.55 (C(2)), 37.20 (C(1), d, JPC=97.3 Hz), 52.29 (C(3), d, 3JPC=9.3 Hz), 31P NMR (121 MHz, D2O) δ 45.9, MS (CI, CH4) m/z 164 (38%) (MH+), 147 (30), 105 (100). (ESI) 164.0822 (MH+-C6H15NO2P requires 164.0840).

Workup

  1. temperaturethe solution heated
  2. temperatureat reflux for 30 h
  3. temperatureAfter cooling
  4. customthe solution was evaporated to dryness under reduced pressure
  5. dissolutionThe residue was dissolved in water (10 cm3)
  6. washThe column was eluted with water until the eluate
  7. washpH neutral and then eluted with aqueous pyridine (1M)
  8. customevaporated to dryness under reduced pressure
  9. customwere removed
  10. dissolutionby repeatedly redissolving the compound in water (20 cm3)
  11. customre-evaporating (3 times)
  12. customRecrystallisation from ethanol/acetone
  13. customdrying

Sources & evidence

ORD record
ord-c8aa08c724a14c3d909e7dccd94e4c86
Source dataset
uspto-grants-2005_11
Patent number
US06962907B2

Reaction notes

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