Phenol → Benzenepropanoic acid, phenyl ester

HRID 2360961Notes

Reaction equation

HRID 2360961 reaction equation
[Li+].[Cl-].[CH3:3][C:4]1C=CC(S(O)(=O)=[O:11])=CC=1.[OH:14][CH:15]1[O:23][CH2:22][C@@H:20](O)[C@H:18](O)[C@H:16]1O.[CH2:24]1[C:35]2[CH:36]=[CH:37][C:32](=[C:33](P(C3C=CC=CC=3)C3C=CC=CC=3)[CH:34]=2)[CH2:31][CH2:30][C:29]2[CH:51]=[CH:52][C:26](=[C:27](P(C3C=CC=CC=3)C3C=CC=CC=3)[CH:28]=2)[CH2:25]1.C=CC1C=CC=CC=1.[C:74]1([OH:80])[CH:79]=[CH:78][CH:77]=[CH:76][CH:75]=1>CC(=O)CC>[C:26]1([CH:25]([CH3:24])[C:15]([O:23][C:22]2[CH:20]=[CH:18][CH:16]=[CH:4][CH:3]=2)=[O:14])[CH:52]=[CH:51][CH:29]=[CH:28][CH:27]=1.[C:32]1([CH2:31][CH2:30][C:29]([O:80][C:74]2[CH:79]=[CH:78][CH:77]=[CH:76][CH:75]=2)=[O:11])[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=1

Participants

8

Reactant 5

HCID 996PhenolHCID 6101p-Toluenesulfonic acidHCID 7501StyreneHCID 433294Lithium ChlorideHCID 131731285HCID 131731285, compound

Product 2

HCID 530835Benzenepropanoic acid, phenyl esterHCID 11447475HCID 11447475, compound

Reagents, catalysts & solvents 1

HCID 6569Methyl Ethyl KetoneSolvent

Conditions

Temperature
75 °C

Procedure

LiCl (8.4 mg, 0.20 mmol, 20%), p-TsOH (34.4 mg, 0.20 mmol, 20%) and [Pd2(Xyl-Phanephos)Cl4] (10.3 mg, 0.01 mmol, 1%) were weighed into a 5 ml sealable vial. A stirring bar was placed inside and vial sealed with a crimp cap and put under inert atmosphere using a needle connected to vacuum line. Styrene (114 μl, 1 mmol, 100%), PhOH (94.1 mg, 1 mmol, 100%) and 2-butanone (1.5 ml) were added. The caps were pierced with two needles and placed in the autoclave which was quickly sealed. The autoclave was purged three times with CO and then pressurized to 30 bar and heated in a preheated oil bath to 75° C. for 24 hours. After this time, the autoclave was cooled to room temperature and the pressure released slowly. The mixture was then analysed by filtration through silica, removal of solvent, diluting with CDCl3 and obtaining a 1H NMR spectrum (84% conversion to the carboxylic ester product as a 0.76:1 ratio of phenyl 2-phenylpropanoate (‘branched’) and phenyl 3-phenylpropanoate (‘linear’). GCMS shows the expected linear and branched esters: MS EI+: m/z 226.0 (M+ requires 226.2).

Workup

  1. customA stirring bar was placed
  2. custominside and vial sealed with a crimp
  3. customcap
  4. customwas quickly sealed
  5. customThe autoclave was purged three times with CO
  6. temperatureAfter this time, the autoclave was cooled to room temperature
  7. filtrationThe mixture was then analysed by filtration through silica, removal of solvent
  8. additiondiluting with CDCl3

Sources & evidence

ORD record
ord-cb29e4973b184d049b9a316de6338786
Source dataset
uspto-grants-2014_04
Patent number
US08686183B2

Reaction notes

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