Dimethyl Sulfoxide → Ethyl 2-(4-bromo-2-methoxyphenyl)acetate

HRID 1054722Notes

Reaction equation

HRID 1054722 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8](C(OCC)=O)[C:9]([O:11][CH2:12][CH3:13])=[O:10])=[C:4]([O:19][CH3:20])[CH:3]=1.[Cl-].[Li+].CS(C)=O>O>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10])=[C:4]([O:19][CH3:20])[CH:3]=1

Participants

5

Reactant 3

HCID 679Dimethyl SulfoxideHCID 433294Lithium ChlorideHCID 86698720Diethyl 2-(4-bromo-2-methoxyphenyl)malonate

Product 1

HCID 86698721Ethyl 2-(4-bromo-2-methoxyphenyl)acetateYield 42.4%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
120 °C

Procedure

A mixture of diethyl 2-(4-bromo-2-methoxyphenyl)malonate (1213 mg, 3.500 mmol), lithium chloride (620 mg, 14.6 mmol), and DMSO (6 ml) was stirred at 120° C. for 20 hours, then at 150° C. for 4 hours, and again at 120° C. for 20 hours. The reaction was cooled to room temperature, diluted with 25 mL of water, and extracted with ethyl acetate-heptane mixture (1:1). The extract was washed with brine (2 times), dried over magnesium sulfate, and loaded on silica gel. Chromatography on a silica gel column, eluting with a gradient from 0% to 30% of ethyl acetate in heptane gave the title compound (405 mg, 42% yield over two steps). GCMS (ES+) 272 (M+).

Workup

  1. waitat 150° C. for 4 hours
  2. waitagain at 120° C. for 20 hours
  3. temperatureThe reaction was cooled to room temperature
  4. extractionextracted with ethyl acetate-heptane mixture (1:1)
  5. washThe extract was washed with brine (2 times)
  6. dry with materialdried over magnesium sulfate
  7. washChromatography on a silica gel column, eluting with a gradient from 0% to 30% of ethyl acetate in heptane

Sources & evidence

ORD record
ord-e71bdd3c68504c9d9a8b45e702c214ce
Source dataset
uspto-grants-2016_07
Patent number
US09394285B2

Reaction notes

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