Pyridine → Ethyl (2-Azidoethoxy)aceto-2-(2-chlorophenylmethlene)acetate

HRID 1374684Notes

Reaction equation

[CH2:1]([O:3][C:4](=[O:15])[CH2:5][C:6](=[O:14])[CH2:7][O:8][CH2:9][CH2:10][N:11]=[N+:12]=[N-:13])[CH3:2].[Cl:16][C:17]1[CH:24]=[CH:23][CH:22]=[CH:21][C:18]=1[CH:19]=O.N1C=CC=CC=1>CCO>[CH2:1]([O:3][C:4](=[O:15])[C:5]([C:6](=[O:14])[CH2:7][O:8][CH2:9][CH2:10][N:11]=[N+:12]=[N-:13])=[CH:19][C:18]1[CH:21]=[CH:22][CH:23]=[CH:24][C:17]=1[Cl:16])[CH3:2]

Participants

Conditions

Temperature: 60 °C

Procedure

A mixture of 4-(2-azido-ethoxy)-3-oxo-butyric acid ethyl ester (3 g, 13.94 mmol), 2-chlorobenzaldehyde (3 g, 21.34 mmol) and pyridine (1.5 mL, 1.47 g, 18.55 mmol) in EtOH (14 mL) was heated to 60° C. and maintained at this temperature for 3 h. The mixture was concentrated in vacuo. The concentrate was taken up in EtOAc (100 mL), washed successively with 1N HCl (25 mL) and brine (25 mL), dried (Na2SO4), filtered, concentrated in vacuo. The crude product was purified by chromatography using the ISCO Combiflash SQ16× (120 gram Redisep silica gel column, 0 to 60% EtOAc in hexanes for 30 min at 40 mL/min) to afford 2.00 g of 2-[2-(2-azido-ethoxy)-acetyl]-3-(2-chloro-phenyl)-acrylic acid ethyl ester (mixture of E/Z isomers) and 1.01 g of recovered starting material.

Workup

temperaturemaintained at this temperature for 3 h
concentrationThe mixture was concentrated in vacuo
washwashed successively with 1N HCl (25 mL) and brine (25 mL)
dry with materialdried (Na2SO4)
filtrationfiltered
concentrationconcentrated in vacuo
customThe crude product was purified by chromatography

Sources & evidence

ORD record: ord-d761410f56434816b019b794e0c13c65
Source dataset: uspto-grants-2007_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07166603B2

Reaction notes

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