Methanol → HCID 54352100, compound

HRID 1656143Notes

Reaction equation

HRID 1656143 reaction equation
[CH2:1]([N:8]([C@@H:12]([CH3:15])[CH2:13]O)[CH2:9][C:10]#[N:11])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(Cl)(Cl)(Cl)Cl.C1(P([C:34]2[CH:39]=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C[OH:41]>C(Cl)Cl>[C:39]([NH:11][C@@H:10]1[CH2:9][N:8]([CH2:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)[C@@H:12]([CH3:15])[CH2:13]1)(=[O:41])[CH3:34]

Participants

6

Reactant 4

HCID 887MethanolHCID 5943Carbon TetrachlorideHCID 11776Triphenylphosphine2×HCID 10943601HCID 10943601, compound

Product 1

HCID 54352100HCID 54352100, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of 132.23 g (0.647 mol) of (S)-2-(N-Benzyl-N-cyanomethylamino)-1-propanol, from step 1b, in 500 mL of methylene chloride and 94 mL of anhydrous carbon tetrachloride under nitrogen and anhydrous conditions and at room temperature was added 170 g (0.648 mol) of triphenylphosphine. The mixture was stirred at room temperature, but soon the exothermic reaction raised the temperature to reflux temperature. The reaction was stirred for 22 hours, another 8.5 g (0.032 mol) of triphenylphosphine was added, and the reaction was stirred another 2.5 hours. Methanol was added to destroy the excess triphenylphosphine, and the mixture concentrated to dryness. The solid was triturated with ether and hexane, which were filtered and concentrated. The oil was redissolved in ether, hexane added, filtered, concentrated and chromatographed over a short silica gel column, eluting with 1:4 ethyl acetate:hexane to afford after removal of the solvent 112.31 g (77.9% yield) of the title product as a colorless liquid. MS M/Z: 223, 225 (M+H). NMR (CDCl3) d: 1.35 (3H, d, J=6 Hz), 3.21 (1H, sextet, J=6 Hz), 3.48 (2H, s), 3.52 (2H, s), 3.57 (1H, dd, J=6, J=12 Hz), 3.68 (1H, dd, J=5, J=12 Hz), 7.35 (5H, m).

Workup

  1. customsoon the exothermic reaction
  2. temperatureraised the temperature
  3. temperatureto reflux temperature
  4. stirringThe reaction was stirred for 22 hours
  5. stirringthe reaction was stirred another 2.5 hours
  6. customto destroy the excess triphenylphosphine
  7. concentrationthe mixture concentrated to dryness
  8. customThe solid was triturated with ether and hexane, which
  9. filtrationwere filtered
  10. concentrationconcentrated
  11. dissolutionThe oil was redissolved in ether
  12. additionhexane added
  13. filtrationfiltered
  14. concentrationconcentrated
  15. customchromatographed over a short silica gel column
  16. washeluting with 1:4 ethyl acetate
  17. customhexane to afford

Sources & evidence

ORD record
ord-7b3acc6edd254e29bb5c5052974751ea
Source dataset
uspto-grants-1993_10
Patent number
US05252747

Reaction notes

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