Benzoic Acid → HCID 50900901, compound

HRID 577745Notes

Reaction equation

HRID 577745 reaction equation
[C:1]([OH:9])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:10]([O:14][CH2:15][CH3:16])(=[O:13])[C:11]#[CH:12]>C1(C)C=CC=CC=1.C(OCC)(=O)C.[Au+].ClP(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[C:1]([O:9]/[CH:12]=[CH:11]\[C:10]([O:14][CH2:15][CH3:16])=[O:13])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 2

HCID 243Benzoic AcidHCID 12182Ethyl propiolate

Product 1

HCID 50900901HCID 50900901, compoundYield 99.5%

Reagents, catalysts & solvents 3

HCID 178479805HCID 178479805, compoundCatalystHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
60 °C

Procedure

To a suspension of benzoic acid (24.4 g, 200 mmol), silver hexafluorophosphate(V) (253 mg, 1 mmol), chlorotriphenylphosphine gold(I) (495 mg, 1 mmol) in toluene (125 mL) was added ethyl prop-2-ynoate (5.1 mL, 50 mmol). The reaction mixture was stirred and heated at 60° C. for 16 hrs. The volatiles were removed to give a residue, which was dissolved in ethyl acetate (200 mL) with some trace insoluble material being removed by filtration. The filtrate was washed with saturated aqueous NaHCO3 (with gas evolved—CAUTION) until there was no further gas evolution, and evaporated to give a light brown oil. This oil was purified via flash chromatography (eluting with a gradient of 0%-100% EtOAc in heptanes) to give the title compound (10.96 g, 99% yield) as a colorless oil, which solidified to afford needle-liked crystals. 1H NMR (400 MHz, chloroform-d) δ ppm 8.24-8.32 (m, 2H) 7.85 (d, J=7.09 Hz, 1H) 7.63-7.72 (m, 1H) 7.48-7.58 (m, 2H) 5.44 (d, J=7.21 Hz, 1H) 4.29 (q, J=7.21 Hz, 2H) 1.38 (t, J=7.15 Hz, 3H). 13C NMR (101 MHz, chloroform-d) δ ppm 164.15 (s, 1C) 162.55 (s, 1C) 144.54 (s, 1C) 134.31 (s, 1C) 130.66 (s, 2C) 128.74 (s, 2C) 127.90 (s, 1C) 103.38 (s, 1C) 60.30 (s, 1C) 14.28 (s, 1C).

Workup

  1. customThe volatiles were removed
  2. customto give a residue, which
  3. custombeing removed by filtration
  4. washThe filtrate was washed with saturated aqueous NaHCO3 (with gas evolved—CAUTION) until there
  5. customevaporated
  6. customto give a light brown oil
  7. customThis oil was purified via flash chromatography (
  8. washeluting with a gradient of 0%-100% EtOAc in heptanes)

Sources & evidence

ORD record
ord-a6f36991c2c5410bb097636d19c7698b
Source dataset
uspto-grants-2015_05
Patent number
US09040547B2

Reaction notes

Loading…