Ethyl pyruvate → HCID 62214851, compound

HRID 1777480Notes

Reaction equation

HRID 1777480 reaction equation
I[C:2]1[CH:7]=[CH:6][N:5]=[CH:4][CH:3]=1.C([Mg]Br)C.[O:12]=[C:13]([CH3:19])[C:14]([O:16][CH2:17][CH3:18])=[O:15].CO.C(Cl)Cl>C1COCC1>[OH:12][C:13]([C:2]1[CH:7]=[CH:6][N:5]=[CH:4][CH:3]=1)([CH3:19])[C:14]([O:16][CH2:17][CH3:18])=[O:15]

Participants

6

Reactant 4

HCID 12041Ethyl pyruvateHCID 6094924-IodopyridineHCID 21226129Dichloromethane methanolHCID 178418443HCID 178418443, compound

Product 1

HCID 62214851HCID 62214851, compoundYield 49.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

4-Iodopyridine (15.0 g, 73 mmol) was taken up in dry THF (600 mL) and cooled to 0° C. and then ethylmagnesium bromide (3M solution in THF, 41.8 mL) was gradually added, maintaining the temperature at 0° C. over the period of 30 mins. To the above reaction mixture was then added a solution of ethyl 2-oxopropanoate (12.13 g, 104 mmol) in THF (100 mL). The reaction mixture was stirred at 0° C. for 1 hr. The reaction progress was monitored by TLC using solvent system MeOH:DCM (5:95). After completion of reaction, the reaction mixture was quenched with ice-cold water and extracted with EtOAc (3×1 Lit). The combined organic layers were dried over Na2SO4, and concentrated under vacuum. The crude product residue was combined with a batch of crude product obtained from a second reaction carried out at the same scale, and was purified by column chromatography using silica (100-200 mesh) and solvent system EtOAc:Hexane (4:6) to obtain 7 g (25%) of ethyl 2-hydroxy-2-(pyridin-4-yl)propanoate as a yellow solid. 1H NMR (400 MHz, DMSO-d6): δ 8.52 (d, 2H, J=6 Hz), 7.44 (d, 2H, J=6 Hz), 6.2 (s, 1H), 4.08 (q, 2H, J=7.2 Hz), 1.60 (s, 1H), 1.12 (t, 3H, J=7.2 Hz); LC-MS m/z calculated for [M+H]+ 196.09. found 196.2.

Workup

  1. temperaturemaintaining the temperature at 0° C. over the period of 30 mins
  2. customAfter completion of reaction
  3. customthe reaction mixture was quenched with ice-cold water
  4. extractionextracted with EtOAc (3×1 Lit)
  5. dry with materialThe combined organic layers were dried over Na2SO4
  6. concentrationconcentrated under vacuum
  7. customobtained from a second reaction
  8. customwas purified by column chromatography

Sources & evidence

ORD record
ord-21b5c852c48943629a4bfa98c1530815
Source dataset
uspto-grants-2016_02
Patent number
US09266873B2

Reaction notes

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