Pyridine → HCID 44231693, compound

HRID 2410083Notes

Reaction equation

HRID 2410083 reaction equation
[CH:1]1[C:6]([OH:7])=[CH:5][CH:4]=[C:3]([CH3:8])[CH:2]=1.[C:9](O)(=[O:13])[C:10]([CH3:12])=[O:11].N1C=CC=CC=1.COC(Cl)Cl>C(Cl)Cl>[C:9]([O:7][C:6]1[CH:5]=[CH:4][C:3]([CH3:8])=[CH:2][CH:1]=1)(=[O:13])[C:10]([CH3:12])=[O:11]

Participants

6

Reactant 4

HCID 1049PyridineHCID 1060Pyruvic AcidHCID 2879P-CresolHCID 21004Methane, dichloromethoxy-

Product 1

HCID 44231693HCID 44231693, compoundYield 50.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

p-Tolyl pyruvate was prepared as follows. p-cresol (540 mg, 5 mmol) and pyruvic acid (440 mg, 5 mmol) were dissolved in methylene chloride (30 mL) and cooled on an ice bath. Pyridine (790 mg. 1 mL, 12.4 mmol) was added, followed by addition of 1,1-dichloromethyl methyl ether (690 mg, 0.53 mL, 6 mmol). The reaction mixture was stirred for 1 h on an ice bath, warmed to room temperature and washed with 30 mL of 5% aqueous HCl and 30 mL of saturated aqueous NaHCO3. The organic layer was dried over anhydrous MgSO4, filtered and solvent removed on a rotary evaporator. The residue was purified by flash silica gel chromatography (20:1→15:1 hexanes-ethyl acetate) to give 450 mg of p-tolyl pyruvate as a clear oil. 1H NMR (400 MHZ, CDCl3) δ 7.21 (d, J=4 Hz, 2H), 7.05 (d, J=4 Hz, 2H), 2.59 (s, 3H), 2.36 (s, 2H). 13C NMR (100 MHZ, CDCl3) δ 191.3, 159.5, 148.1, 136.6, 130.4, 120.8, 27.0, 21.1. HRMS (ESI-12 Tesla FT-MS) [M+H]+ calcd. 179.0708, found 179.0709.

Workup

  1. customp-Tolyl pyruvate was prepared
  2. temperaturecooled on an ice bath
  3. washwashed with 30 mL of 5% aqueous HCl and 30 mL of saturated aqueous NaHCO3
  4. dry with materialThe organic layer was dried over anhydrous MgSO4
  5. filtrationfiltered
  6. customsolvent removed on a rotary evaporator
  7. customThe residue was purified by flash silica gel chromatography (20:1→15:1 hexanes-ethyl acetate)

Sources & evidence

ORD record
ord-33298a8cc5574033b29ad3cf47046af4
Source dataset
uspto-grants-2014_08
Patent number
US08815946B2

Reaction notes

Loading…