Triphenylphosphine → 4-(4-Hydroxy-1-Butynyl)benzoic Acid Methyl Ester

HRID 2259443Notes

Reaction equation

HRID 2259443 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][C:33]#[C: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 146031084-(4-Hydroxy-1-Butynyl)benzoic Acid Methyl EsterYield 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-yn-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) ν max 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-97b9f3d4e0d3457f936c8de9ae085e0f
Source dataset
uspto-grants-1995_12
Patent number
US05473071

Reaction notes

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