Triphenylphosphine → Methyl 4-(4-hydroxybutyl)benzoate

HRID 330366Notes

Reaction equation

HRID 330366 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.Br[C:21]1[CH:30]=[CH:29][C:24]([C:25]([O:27][CH3:28])=[O:26])=[CH:23][CH:22]=1.[CH2:31]([OH:35])[CH2:32][C:33]#[CH:34]>C(NCC)C.[Pd](Cl)Cl.[Cu]I>[OH:35][CH2:31][CH2:32][CH2:33][CH2:34][C:21]1[CH:30]=[CH:29][C:24]([C:25]([O:27][CH3:28])=[O:26])=[CH:23][CH:22]=1

Participants

7

Reactant 3

HCID 11776TriphenylphosphineHCID 12081Methyl 4-bromobenzoateHCID 135663-Butyn-1-OL

Product 1

HCID 14603109Methyl 4-(4-hydroxybutyl)benzoateYield 75.8%

Reagents, catalysts & solvents 3

HCID 24290Palladium ChlorideCatalystHCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8021DiethylamineSolvent

Procedure

To a mixture of 0.082 g (0.005 eq) of palladium chloride, and 0.244 g (0.01 eq) of triphenylphosphine, and 20.00 g (1.0 eq) of methyl 4-bromobenzoate in diethylamine which is stirred under nitrogen is added 0.178 g (0.01 eq) of copper (I) iodide and 6.52 g (1.0 eq) of 3-butyn-1-ol. The reaction mixture is stirred under nitrogen at room temperature (about 25° C.) for eighteen hours. Diethylamine is then removed under reduced pressure, water is added, and the mixture extracted with benzene. The benzene extracts are filtered through silica to remove the metal residue and the filtrate concentrated under reduced pressure to yield methyl 4-(4-hydroxybut-1-yl)benzoate. Recrystallization from a mixture of benzene and hexane yields pure material in 75.8% yield, m.p. 95.5°-96.0° C.; IR (KBr) νmax 3310, 2955, 1718, 1604, 1433, 1275, 1177, 1108, 1040, 955, 852, and 769 cm-1 ; 1H NMR (CDCl3) delta 7.98 (d, J=8.3 Hz, 2H, Ar), 7.49 (d, J=8.3 Hz, 2H, Ar), 3.93 (s, 3H, --CH3), 3.87 (m, 2H, --CH2OH), 2.74 (t, J=6.2 Hz, 2H, --yl--CH2 --), 1.88 (m, 1H, --OH).

Workup

  1. stirringThe reaction mixture is stirred under nitrogen at room temperature (about 25° C.) for eighteen hours
  2. customDiethylamine is then removed under reduced pressure, water
  3. additionis added
  4. extractionthe mixture extracted with benzene
  5. filtrationThe benzene extracts are filtered through silica
  6. customto remove the metal residue
  7. concentrationthe filtrate concentrated under reduced pressure

Sources & evidence

ORD record
ord-084a113b894d47dbb31bb9ab30ca85ad
Source dataset
uspto-grants-1990_01
Patent number
US04895946

Reaction notes

Loading…