Diethyl Ether → HCID 10444388, compound

HRID 973778Notes

Reaction equation

HRID 973778 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Br:20]Br.[N+:22]([C:25]1[CH:34]=[CH:33][C:28]([CH:29]=[CH:30][CH2:31]O)=[CH:27][CH:26]=1)([O-:24])=[O:23].CCOCC>C(#N)C>[N+:22]([C:25]1[CH:34]=[CH:33][C:28](/[CH:29]=[CH:30]/[CH2:31][Br:20])=[CH:27][CH:26]=1)([O-:24])=[O:23]

Participants

6

Reactant 4

HCID 3283Diethyl EtherHCID 11776TriphenylphosphineHCID 24408BromineHCID 739253-(4-Nitrophenyl)prop-2-en-1-ol

Product 1

HCID 10444388HCID 10444388, compoundYield 86%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Conditions

Temperature
60 °C

Procedure

In 35 mL of dry acetonitrile under nitrogen atmosphere was added 7.3 g (27.9 mmole) of triphenylphosphine. To the solution was added dropwise over 15 minutes 4.31 g of bromine (27.0 mmole) while cooling the reaction mixture to maintain the temperature between 0°-10° C. The solution was allowed to warm to room temperature (about 22°-25° C.) and 5.0 g (27.9 mmole) of p-nitrocinnamyl alcohol (Pfaultz & Bauer Chemical Co.) was added as a slurry in 50 mL of acetonitrile which caused an exothermic reaction, temperature about 45° C. The resulting dark red solution was heated for one hour at 60° C. with stirring and then poured into 500 mL of ether. Triphenylphosphine oxide precipitated from the solution after standing overnight (about 16 hours). The solution was filtered and 15 g of flash silica gel was added to the solution, followed by solvent removal. The resulting powder matrix was applied to a 3 in.×8 in. (7.6 cm×20.3 cm) flash column and the desired product was eluted with hexane, followed by 20% ethyl acetate in hexane to yield 5.8 g (23.9 mmole) of the desired pure trans product in 86% yield (MP=75°-76° C., Rf =0.81, 60:40 ethyl acetate:n-hexane) and was further characterized by:

Workup

  1. temperaturewhile cooling the reaction mixture
  2. temperatureto maintain the temperature between 0°-10° C
  3. customan exothermic reaction, temperature about 45° C
  4. customTriphenylphosphine oxide precipitated from the solution
  5. custom(about 16 hours)
  6. filtrationThe solution was filtered
  7. addition15 g of flash silica gel was added to the solution
  8. customfollowed by solvent removal
  9. wash(7.6 cm×20.3 cm) flash column and the desired product was eluted with hexane
  10. customto yield 5.8 g (23.9 mmole) of the desired pure trans product in 86% yield (MP=75°-76° C., Rf =0.81, 60:40 ethyl acetate:n-hexane)

Sources & evidence

ORD record
ord-daf907be68634ae18e6277d712c1e914
Source dataset
uspto-grants-1991_11
Patent number
US05064956

Reaction notes

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