Myristyl bromide → 3-Hydroxy-5-(tetradecyloxy)benzoic acid methyl ester

HRID 1492859Notes

Reaction equation

HRID 1492859 reaction equation
[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[C:8]([OH:10])[CH:7]=[C:6]([OH:11])[CH:5]=1.Br[CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27].C(=O)([O-])[O-].[K+].[K+]>CC(C)=O.CN(C=O)C>[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:5]=[C:6]([O:11][CH2:27][CH2:26][CH2:25][CH2:24][CH2:23][CH2:22][CH2:21][CH2:20][CH2:19][CH2:18][CH2:17][CH2:16][CH2:15][CH3:14])[CH:7]=[C:8]([OH:10])[CH:9]=1

Participants

6

Reactant 3

HCID 8208Myristyl bromideHCID 11430Potassium CarbonateHCID 75076Methyl 3,5-Dihydroxybenzoate

Product 1

HCID 152334833-Hydroxy-5-(tetradecyloxy)benzoic acid methyl esterYield 34%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 6228DimethylformamideSolvent

Procedure

A mixture of 10 g (0.06 mol) of 3,5-dihydroxybenzoic acid methyl ester, 16.2 ml (0.06 mol) of 1-bromotetradecane and 8.2 g (0.06 mol) of potassium carbonate in 200 ml of acetone and 20 ml of DMF was stirred at reflux under argon for 24 hours, After the usual workup, the crude product was triturated with hot methylene chloride and filtered. The filtrate was concentrated at reduced pressure and the solid residue was recrystallized from methylene chloride-methanol to give the 3,5-dialkylated product. The filtrate was concentrated and the residue was purified by HPLC using 15% ethyl acetatehexane to give 7.3 g (34% yield, mp 92°-94°) of 3-hydroxy-5-(tetradecyloxy)benzoic acid methyl ester. The nmr spectra was consistent with the structure.

Workup

  1. temperatureat reflux under argon for 24 hours
  2. customAfter the usual workup, the crude product was triturated with hot methylene chloride
  3. filtrationfiltered
  4. concentrationThe filtrate was concentrated at reduced pressure
  5. customthe solid residue was recrystallized from methylene chloride-methanol
  6. customto give the 3,5-dialkylated product
  7. concentrationThe filtrate was concentrated
  8. customthe residue was purified by HPLC

Sources & evidence

ORD record
ord-3676cad415ec480b87c1d959f84609be
Source dataset
uspto-grants-1994_12
Patent number
US05374772

Reaction notes

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