Triphenylphosphine → HCID 22326841, compound

HRID 2117632Notes

Reaction equation

HRID 2117632 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([OH:12])[C:7]([O:10][CH3:11])=[CH:8][CH:9]=1)([O-:3])=[O:2].[CH:13]([N:15]1[CH2:20][CH2:19][CH:18](CO)[CH2:17][CH2:16]1)=[O:14].[C:23]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O>O1CCCC1.ClCCl.C(OCC)(=O)C>[CH:13]([N:15]1[CH2:20][CH2:19][CH:18]([CH2:11][O:10][C:7]2[CH:8]=[CH:9][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][C:6]=2[O:12][CH3:23])[CH2:17][CH2:16]1)=[O:14]

Participants

8

Reactant 4

HCID 11776TriphenylphosphineHCID 694712-Methoxy-5-nitrophenolHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 223268844-(Hydroxymethyl)piperidine-1-carbaldehyde

Product 1

HCID 22326841HCID 22326841, compound

Reagents, catalysts & solvents 3

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

4-Nitroguaiacol (2 g, 11.8 mmol), N-formyl 4-piperidinemethanol (1.13 g, 7.89 mmol) and polymer-supported triphenylphosphine (3 mmol/g, 3.94 g, 11.8 mmol) were dissolved in tetrahydrofuran (30 mL). The mixture was cooled to 0° C. and diisopropyl azodicarboxylate (2.33 mL, 11.8 mmol) was added dropwise. The mixture was stirred at 0° C. for 30 min then at 20° C. overnight. The resin was filtered off, washed with dichloromethane then methanol and the filtrate evaporated to give a deep orange oil. The oil was taken up in dichloromethane, washed with 2M NaOH, 2M HCl then brine, dried and evaporated giving a pale brown oil. This was taken up in 50:50 ethyl acetate : hexane, filtered through celite, filtrate evaporated, taken up in ethyl acetate and washed further with 1M NaOH. The organic layer was separated, dried over Na2SO4, the solvent removed under reduced pressure and the residue columned in 50:50 ethyl acetate: hexane to remove impurities. The product was then eluted with 9:1 dichloromethane : methanol to give a yellow oil, which crystallised on cooling. 1H NMR (400 MHz, CDCl3): 1.15-1.3 (2H, m); 1.85-1.9 (1H, m); 2.6-2.7 (1H, m); 3-3.1 (1H, m); 3.7-3.8 (1H, m); 4.0 (2H, d, J 7 Hz); 4.15-4.25 (1H, m); 7.2 (1H, d, J 8 Hz); 7.75 (1H, d, J 2 Hz); 7.9 (1H, dd, J 2 and 8 Hz); 8 (1H, s).

Workup

  1. customat 20° C.
  2. customovernight
  3. filtrationThe resin was filtered off
  4. washwashed with dichloromethane
  5. custommethanol and the filtrate evaporated
  6. customto give a deep orange oil
  7. washwashed with 2M NaOH, 2M HCl
  8. dry with materialbrine, dried
  9. customevaporated
  10. customgiving a pale brown oil
  11. filtrationhexane, filtered through celite, filtrate
  12. customevaporated
  13. washwashed further with 1M NaOH
  14. customThe organic layer was separated
  15. dry with materialdried over Na2SO4
  16. customthe solvent removed under reduced pressure
  17. customthe residue columned in 50:50 ethyl acetate: hexane to remove impurities
  18. washThe product was then eluted with 9:1 dichloromethane
  19. custommethanol to give a yellow oil, which
  20. customcrystallised
  21. temperatureon cooling

Sources & evidence

ORD record
ord-7e86be9c4073439f82d4a7645d9ce1bb
Source dataset
uspto-grants-2008_10
Patent number
US07442698B2

Reaction notes

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