Phenol → Phosphonium, triphenyl(2-(1-pyrrolidinyl)ethyl)-, bromide (1:1)

HRID 2250420Notes

Reaction equation

HRID 2250420 reaction equation
O(CC[Br:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:11]1([P:17]([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[CH:16]=CC=CC=1.C1(O)C=CC=CC=1.[NH:37]1[CH2:41][CH2:40][CH2:39][CH2:38]1>CS(C)=O>[Br-:10].[N:37]1([CH2:16][CH2:11][P+:17]([C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)([C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=2)[C:24]2[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=2)[CH2:41][CH2:40][CH2:39][CH2:38]1

Participants

6

Reactant 4

HCID 996PhenolHCID 11776TriphenylphosphineHCID 31268PyrrolidineHCID 68526Benzene, (2-bromoethoxy)-

Product 1

HCID 19085441Phosphonium, triphenyl(2-(1-pyrrolidinyl)ethyl)-, bromide (1:1)

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
110.5 °C

Procedure

A mixture of 2-phenoxyethyl bromide (90.6 g, 0.45 mol), triphenylphosphine (119.2 g, 0.45 mol), and phenol (854 g) was heated to a melt and then stirred over a hot oil bath (107-114° C.) for ˜24 h. The reaction mixture was extracted with 6:1 heptane/EtOAc (3×2 L), 9:1 heptane/EtOAc (3×0.5 L), and heptane (300 mL) to give an oil that solidified. After dissolving the reaction mixture in DMSO, the mixture was warmed, treated with pyrrolidine (150 mL), and stirred over a hot oil bath (50-55° C.) for 1.5 h. The reaction mixture was cooled to room temperature, seeded for crystallization, and treated slowly and intermittently with increasing amounts of t-butyl methyl ether (TBME) until it was evident that crystallization was complete. The solid was filtered, washed with TBME and then with heptane, and vacuum dried to give 90.27 g of the desired product. The structure was confirmed by 1H NMR.

Workup

  1. temperaturewas heated to a melt
  2. extractionThe reaction mixture was extracted with 6:1 heptane/EtOAc (3×2 L), 9:1 heptane/EtOAc (3×0.5 L), and heptane (300 mL)
  3. customto give an oil that solidified
  4. temperaturethe mixture was warmed
  5. stirringstirred over a hot oil bath (50-55° C.) for 1.5 h
  6. temperatureThe reaction mixture was cooled to room temperature
  7. customseeded for crystallization
  8. additiontreated slowly and intermittently with increasing amounts of t-butyl methyl ether (TBME) until it
  9. customwas evident that crystallization
  10. filtrationThe solid was filtered
  11. washwashed with TBME
  12. dry with materialwith heptane, and vacuum dried

Sources & evidence

ORD record
ord-7480e5faf97c4385b03e02492651a031
Source dataset
uspto-grants-2008_01
Patent number
US07317026B2

Reaction notes

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