Triphenylphosphine → 5-(1-Allyloxypent-4-enyl)-1-methyl-4-nitro-pyrazole

HRID 521834

Reaction equation

HRID 521834 reaction equation
[CH3:1][N:2]1[CH:6]=[C:5]([N+:7]([O-:9])=[O:8])[CH:4]=[N:3]1.[CH:10](=[O:15])[CH2:11][CH2:12][CH:13]=[CH2:14].[Li+].C[Si]([N-][Si](C)(C)C)(C)C.C(=O)(OCC=C)O[CH2:28][CH:29]=[CH2:30].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1COCC1.O1CCOCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH2:30]([O:15][CH:10]([C:6]1[N:2]([CH3:1])[N:3]=[CH:4][C:5]=1[N+:7]([O-:9])=[O:8])[CH2:11][CH2:12][CH:13]=[CH2:14])[CH:29]=[CH2:28]

Participants

9

Reactant 5

HCID 11776TriphenylphosphineHCID 164184-PentenalHCID 198951-methyl-4-nitro-1H-pyrazoleHCID 84764Carbonic acid, di-2-propen-1-yl esterHCID 2733832Lithium Hexamethyldisilazide

Product 1

HCID 867137765-(1-Allyloxypent-4-enyl)-1-methyl-4-nitro-pyrazole

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8028TetrahydrofuranSolvent2×HCID 312751,4-DioxaneSolvent

Conditions

Temperature
-40 °C

Procedure

To a solution of 1-methyl-4-nitro-pyrazole (9.7 g, 76.7 mmol) and pent-4-enal (10.0 g, 84.4 mmol) in THF (250 mL) at −78° C. was added dropwise a solution of LiHMDS in THF (1 M, 192 mL, 191.7 mmol). The reaction mixture was allowed to warm to −40° C. and stirred for 4 hr. The reaction was quenched with a saturated solution of ammonium chloride (100 mL), warmed to room temperature and the solvents removed under reduced pressure. The residue was dissolved in EtOAc (100 mL) and washed with water (30 mL). The organic layer was separated, dried over MgSO4 and concentrated under reduced pressure. Purification via silica gel column chromatography (0-30% EtOAc/isohexane) gave a clear oil. This oil (7.1 g, 33.6 mmol), diallyl carbonate (14.33 g, 100.9 mmol) and triphenylphosphine (880 mg, 3.35 mmol) were dissolved in dioxane (236 mL) under nitrogen before tris(dibenzylideneacetone)-dipalladium(0) (780 mg, 0.84 mmol) was added. The reaction mixture was heated at 50° C. for 1 hr and the solvent removed under reduced pressure. Purification via silica gel column chromatography (0-40% EtOAc/isohexane) gave 5-(1-allyloxypent-4-enyl)-1-methyl-4-nitro-pyrazole as a yellow oil (8.35 g, 43% over two steps). 1H NMR (400 MHz, CDCl3) δ 8.06 (s, 1H), 5.90-5.73 (m, 2H), 5.46 (dd, J=8.8, 5.1 Hz, 1H), 5.29-5.16 (m, 2H), 5.10-5.00 (m, 2H), 4.04 (s, 3H), 3.92 (d, J=5.8 Hz, 2H), 2.37-2.25 (m, 1H), 2.22-2.09 (m, 1H), 2.09-1.96 (m, 1H), 1.84 (dddd, J=13.7, 9.2, 6.9, 5.1 Hz, 1H).

Workup

  1. customThe reaction was quenched with a saturated solution of ammonium chloride (100 mL)
  2. temperaturewarmed to room temperature
  3. customthe solvents removed under reduced pressure
  4. dissolutionThe residue was dissolved in EtOAc (100 mL)
  5. washwashed with water (30 mL)
  6. customThe organic layer was separated
  7. dry with materialdried over MgSO4
  8. concentrationconcentrated under reduced pressure
  9. customPurification via silica gel column chromatography (0-30% EtOAc/isohexane)
  10. customgave a clear oil
  11. additionwas added
  12. temperatureThe reaction mixture was heated at 50° C. for 1 hr
  13. customthe solvent removed under reduced pressure
  14. customPurification via silica gel column chromatography (0-40% EtOAc/isohexane)

Sources & evidence

ORD record
ord-514d850461a14c5ba5089010dc5216fd
Source dataset
uspto-grants-2016_05
Patent number
US09328106B2

Linked notes

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