Triphenylphosphine → HCID 58071855, compound

HRID 870522Notes

Reaction equation

HRID 870522 reaction equation
[OH:1][C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][C:3]=1[O:10][CH3:11].[CH3:12][N:13]1[CH2:18][CH2:17][CH:16](O)[CH2:15][CH2:14]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(OC(/N=N/C(OC(C)(C)C)=O)=O)(C)C>O1CCCC1.C(OCC)(=O)C.O>[CH3:11][O:10][C:3]1[CH:4]=[C:5]([CH:8]=[CH:9][C:2]=1[O:1][CH:16]1[CH2:17][CH2:18][N:13]([CH3:12])[CH2:14][CH2:15]1)[C:6]#[N:7]

Participants

8

Reactant 4

HCID 11776Triphenylphosphine2×HCID 660484-Piperidinol, 1-methyl-2×HCID 781354-Hydroxy-3-methoxybenzonitrileHCID 6034084Di-tert-butyl diazene-1,2-dicarboxylate2×

Product 1

HCID 58071855HCID 58071855, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

2.04 g 4-Hydroxy-3-methoxy-benzonitrile, 1.57 g 1-methyl-piperidine-4-ol and 7.17 g triphenylphosphine were placed in 125 mL tetrahydrofuran at 0° C. before 6.30 g di-tert-butylazodicarboxylate (DBAD) as a solution in 125 mL tetrahydrofuran was added over 15 min. The reaction was stirred for 5 min at 0° C. and then warmed to ambient temperature where it was maintained overnight. After this time additional 0.31 g 1-methyl-piperidine-4-ol, 1.79 g triphenylphosphine and 1.58 g di-tert-butylazodicarboxylate (DBAD) were added and the reaction was stirred for a further 3 h at ambient temperature. The mixture was then diluted with ethyl acetate and water and the organic phase was separated, washed with 1N sodium hydroxide (×2), water, saturated sodium chloride solution, dried over sodium sulfate, filtered and the filtrate was concentrated under reduced pressure. The material that remained was dissolved in tert-butyl dimethyl ether and washed with 3N hydrochloric acid. The aqueous phase was then made basic with 5N sodium hydroxide and extracted with ethyl acetate (×3). The combined organic fractions were washed water, saturated sodium chloride solution, dried over sodium sulfate, filtered and the filtrate was concentrated under reduced pressure. Purification on silica gel chromatography (SiO2: dichloromethane/methanol 5% then dichloromethane/7N ammonia in methanol 5%) provided the title compound.

Workup

  1. additionwas added over 15 min
  2. temperaturewarmed to ambient temperature where it
  3. temperaturewas maintained overnight
  4. stirringthe reaction was stirred for a further 3 h at ambient temperature
  5. customthe organic phase was separated
  6. washwashed with 1N sodium hydroxide (×2), water, saturated sodium chloride solution
  7. dry with materialdried over sodium sulfate
  8. filtrationfiltered
  9. concentrationthe filtrate was concentrated under reduced pressure
  10. dissolutionThe material that remained was dissolved in tert-butyl dimethyl ether
  11. washwashed with 3N hydrochloric acid
  12. extractionextracted with ethyl acetate (×3)
  13. washThe combined organic fractions were washed water, saturated sodium chloride solution
  14. dry with materialdried over sodium sulfate
  15. filtrationfiltered
  16. concentrationthe filtrate was concentrated under reduced pressure
  17. customPurification on silica gel chromatography (SiO2

Sources & evidence

ORD record
ord-2a35578d8db74edd8b26e2457598bfee
Source dataset
uspto-grants-2015_03
Patent number
US08969568B2

Reaction notes

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