Triphenylphosphine → HCID 56948153, compound

HRID 573519Notes

Reaction equation

HRID 573519 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH2:20]([O:38][CH2:39][C@@H:40]([N:50]=[N+]=[N-])[CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][CH2:47][CH2:48][CH3:49])[CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27]/[CH:28]=[CH:29]\[CH2:30]/[CH:31]=[CH:32]\[CH2:33][CH2:34][CH2:35][CH2:36][CH3:37]>C1COCC1>[CH2:20]([O:38][CH2:39][C@@H:40]([NH2:50])[CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][CH2:47][CH2:48][CH3:49])[CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27]/[CH:28]=[CH:29]\[CH2:30]/[CH:31]=[CH:32]\[CH2:33][CH2:34][CH2:35][CH2:36][CH3:37]

Participants

4

Reactant 2

HCID 11776TriphenylphosphineHCID 86699450HCID 86699450, compound

Product 1

HCID 56948153HCID 56948153, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Triphenyl phosphine (4.54 g, 17.3 mmol) and the azide (8 g, 17.3 mmol) were dissolved in THF. The reaction mixture was split into 3 μw tubes and irradiated at 120° C. for 1 hour each. Considerable pressure built in each tube so care should be noted. LC indicated 100% conversion to phosphoimine intermediate. To each tube was added ˜3 mL of water and the reaction irradiated for 10 min at 120° C. The reaction mixtures were combined and concentrated to remove organic solvent. Hexane was added to precipitate phosphine oxides which were filtered through cintered glass funnel. The solvent was then removed in vacuo. The crude product was purified using HPLC with 30 min run and 60-100% water/acetonitrile gradient. The combined HPLC fractions were neutralized with sodium bicarbonate evaoporated in vacuo. The pure product was partitioned between water/hexanes. The organic layer was dried over sodium sulfate, filtered and evaporated in vacuo to afford (2S)-1-[(9Z,12Z)-octadeca-9,12-dien-1-yloxy]undecan-2-amine (2). 1H NMR (CDCl3, 300 mHz) δ 0.88-0.87 (m, 6H), 1.25-1.29 (s, 32H), 1.54-1.54 (m, 2H), 2.03-2.05 (m, 4H), 2.23 (s, 2H), 2.75-2.76 (m, 2H), 2.96 (m, 1H), 3.13-3.18 (m, 1H), 3.38-3.45 (m, 3H), 5.31-5.38 (m, 4H); LC/MS (m+1) 436.7.

Workup

  1. customThe reaction mixture was split into 3 μw tubes
  2. customirradiated at 120° C. for 1 hour each
  3. customConsiderable pressure built in each tube
  4. additionTo each tube was added ˜3 mL of water
  5. customthe reaction irradiated for 10 min at 120° C
  6. customThe reaction mixtures
  7. concentrationconcentrated
  8. customto remove organic solvent
  9. additionHexane was added
  10. customto precipitate phosphine oxides which
  11. filtrationwere filtered
  12. customThe solvent was then removed in vacuo
  13. customThe crude product was purified
  14. customwith 30 min
  15. customThe pure product was partitioned between water/hexanes
  16. dry with materialThe organic layer was dried over sodium sulfate
  17. filtrationfiltered
  18. customevaporated in vacuo

Sources & evidence

ORD record
ord-77f09bf8f627466ea25ac9c395adbebb
Source dataset
uspto-grants-2015_05
Patent number
US09029604B2

Reaction notes

Loading…