Triphenylundecylphosphonium bromide → HCID 54242059, compound

HRID 2380498Notes

Reaction equation

HRID 2380498 reaction equation
[Li]CCCC.[Br-].[CH2:7]([P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH3:17].[CH:37]([C:39]1[CH:40]=[N:41][N:42]([CH:44]([C:50]2[CH:55]=[CH:54][CH:53]=[CH:52][CH:51]=2)[C:45]([O:47][CH2:48][CH3:49])=[O:46])[CH:43]=1)=O>C1COCC1>[CH:37]([C:39]1[CH:40]=[N:41][N:42]([CH:44]([C:50]2[CH:55]=[CH:54][CH:53]=[CH:52][CH:51]=2)[C:45]([O:47][CH2:48][CH3:49])=[O:46])[CH:43]=1)=[CH:17][CH2:16][CH2:15][CH2:14][CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][CH3:7]

Participants

5

Reactant 3

HCID 3085198Triphenylundecylphosphonium bromideHCID 10563150ethyl (+/-)-4-formyl-alpha-phenyl-1H-pyrazole-l-acetateHCID 178418339Butyllithium

Product 1

HCID 54242059HCID 54242059, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of n-BuLi (127 mL, 254 mmol, 2.0M in hexanes) was added dropwise to a suspension of n-undecyl-triphenylphosphonium bromide (121.6 g, 244 mmol, obtained from triphenylphosphine and undecylbromide) in 500 mL THF at -78° C. under an atmosphere of N2. The resulting orange solution was stirred for 1 hour before a solution of ethyl (±)-4-formyl-α-phenyl-1H-pyrazole-1-acetate in 250 mL THF was added dropwise. Warmed to room temperature and stirred for 16 hours. Quenched by adding 150 mL water and concentrating in vacuo. The residue was partitioned between water and dichloromethane. The organic layer was dried over MgSO4, filtered, and concentrated to give an oily tan solid. Triturated with boiling hexanes and filtered to remove triphenylphosphine oxide. The filtrate was concentrated and chromatographed (10% EtOAc/hexanes on silica) to give the title compound as a yellow oil, a 1:2 E/Z mixture (44.4 g, 50%).

Workup

  1. additionwas added dropwise
  2. customQuenched
  3. additionby adding 150 mL water
  4. concentrationconcentrating in vacuo
  5. customThe residue was partitioned between water and dichloromethane
  6. dry with materialThe organic layer was dried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customto give an oily tan solid
  10. customTriturated with boiling hexanes
  11. filtrationfiltered
  12. customto remove triphenylphosphine oxide
  13. concentrationThe filtrate was concentrated
  14. customchromatographed (10% EtOAc/hexanes on silica)

Sources & evidence

ORD record
ord-605d52e52f024185b04d4341091920d2
Source dataset
uspto-grants-1994_11
Patent number
US05366987

Reaction notes

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