Triphenylphosphine → HCID 11140657, compound

HRID 2257225Notes

Reaction equation

HRID 2257225 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Br:20]Br.[CH2:22](O)[CH2:23][CH:24]=[CH:25][CH2:26][CH:27]=[CH:28][CH2:29][CH:30]=[CH:31][CH2:32][CH2:33][CH2:34][CH2:35][CH3:36]>C(#N)C>[Br:20][CH2:22][CH2:23]/[CH:24]=[CH:25]\[CH2:26]/[CH:27]=[CH:28]\[CH2:29]/[CH:30]=[CH:31]\[CH2:32][CH2:33][CH2:34][CH2:35][CH3:36]

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 24408BromineHCID 54274210HCID 54274210, compound

Product 1

HCID 11140657HCID 11140657, compoundYield 90%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent3×

Procedure

To a 250 mL three-necked round bottom flask was added under nitrogen 9.46 g (36.1 mmol) of triphenylphosphine dissolved in 150 mL of anhydrous acetonitrile. After cooling to 0° C. (ice-salt bath), bromine (5.77 g, 36.1 mmol) was added dropwise with stirring. The mixture was warmed to room temperature and stirred for 30 minutes. 3,6,9-Pentadecatrienol (6.16 g, 27.75 mmol); dissolved in 50 mL of anhydrous acetonitrile, was added dropwise (15 minutes) and stirred for approximately 4 hours. Upon reaction completion acetonitrile was removed in vacuo and the residue was dissolved in 75 mL of ether. Hexanes were utilized to precipitate the triphenylphosphorane side product which was removed by filtration. The crude residue, obtained after concentration of the filtrate in vacuo, was purified over silica gel using ethyl acetate:hexanes (1:9) as eluant. The product 7.0 g (90%) was obtained as a light yellow oil. IR (neat,cm-1) 2958, 2927, 1652, 1267, 723;1H NMR (CDCl3) δ 5.69-5.28 (m, 6H), 3.38 (t, J=7.1 Hz, 2H), 2.89-2.75 (m, 4H), 2.75-2.52 (m, 2H), 2.12-1.93 (m, 2H), 1.49-1.31 (m, 6H), 0.89 (t, J=6.8 Hz, 3H); 13C NMR (CDCl3) δ 131.0, 130.6, 128.9, 127.4 (2C), 126.3, 32.2, 31.5, 30.9, 29.3, 27.3, 25.8, 25.7, 22.6, 14.0; HRMS calculated for C15H25Br (M+) 284.1139, found 284.1101.

Workup

  1. additionwas added dropwise
  2. stirringstirred for 30 minutes
  3. additionwas added dropwise (15 minutes)
  4. stirringstirred for approximately 4 hours
  5. customwas removed in vacuo
  6. dissolutionthe residue was dissolved in 75 mL of ether
  7. customto precipitate the triphenylphosphorane side product which
  8. customwas removed by filtration
  9. customThe crude residue, obtained after concentration of the filtrate in vacuo
  10. customwas purified over silica gel

Sources & evidence

ORD record
ord-0337431161b54aba8182dfeeb94fdd99
Source dataset
uspto-grants-1997_08
Patent number
US05656662

Reaction notes

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