Ethyl Glycolate → Ethyl 2-((5-bromo-3-nitropyridin-2-yl)oxy)acetate

HRID 1660845Notes

Reaction equation

[H-].[Na+].[C:3]([O:7][CH2:8][CH3:9])(=[O:6])[CH2:4][OH:5].[Br:10][C:11]1[CH:12]=[C:13]([N+:18]([O-:20])=[O:19])[C:14](Cl)=[N:15][CH:16]=1.C(=O)([O-])O.[Na+]>O1CCOCC1>[CH2:8]([O:7][C:3](=[O:6])[CH2:4][O:5][C:14]1[C:13]([N+:18]([O-:20])=[O:19])=[CH:12][C:11]([Br:10])=[CH:16][N:15]=1)[CH3:9]

Participants

Conditions

Temperature: 70 °C

Procedure

Sodium hydride (55% dispersion in mineral oil, 603 mg, 13.8 mmol) was added to a solution of ethyl glycolate (1.43 g, 13.8 mmol) in 1,4-dioxane, and the reaction mixture was heated at 70° C. for 1 h, then 5-bromo-2-chloro-3-nitropyridine (Eur. Pat. Appl. EP 122109 (1984); 1.64 g, 6.91 mmol) was added, and stirring was continued at 70° C. for 1 h and at room temperature for 16 h. The reaction mixture was then neutralized with sat. aq. sodium hydrogencarbonate solution and extracted three times with dichloromethane. The organic layers were pooled, dried (Na2SO4), and evaporated. Chromatography (SiO2, hexane-ethyl acetate gradient) furnished (5-bromo-3-nitropyridin-2-yloxy)-acetic acid ethyl ester (1.03 g, 49%). Light yellow liquid, MS (ISP)=305.1 (M+H)+.

Workup

extractionextracted three times with dichloromethane
dry with materialdried (Na2SO4)
customevaporated

Sources & evidence

ORD record: ord-df051183d45d46b5bddba4adb468e53d
Source dataset: uspto-grants-2011_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08030308B2

Reaction notes

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