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Dimethyl Sulfoxide → Methyl 2-(2-chloro-4-nitrophenyl)acetate

HRID 1019730
Notes
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Reaction equation

HRID 1019730 reaction equation
[CH3:1][O:2][C:3](=[O:19])[CH:4]([C:9]1[CH:14]=[CH:13][C:12]([N+:15]([O-:17])=[O:16])=[CH:11][C:10]=1[Cl:18])C(OC)=O.[Cl-].[Na+].CS(C)=O.O>CCOC(C)=O>[CH3:1][O:2][C:3](=[O:19])[CH2:4][C:9]1[CH:14]=[CH:13][C:12]([N+:15]([O-:17])=[O:16])=[CH:11][C:10]=1[Cl:18]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 962Water2×HCID 5234Sodium ChlorideHCID 11414995Dimethyl 2-(2-chloro-4-nitrophenyl)malonate

Product 1

HCID 21876245Methyl 2-(2-chloro-4-nitrophenyl)acetateYield 60.4%

Reagents, catalysts & solvents 1

HCID 8857
Ethyl Acetate
Solvent

Conditions

Temperature
110 °C

Procedure

2-(2-Chloro-4-nitro-phenyl)-malonic acid dimethyl ester (6.0 g, 20.9 mmol) and sodium chloride (2.2 g, 37.6 mmol) were added to a mixture of DMSO (100 mL) and water (0.38 mL, 20.9 mmol) and the reaction mixture was heated for 8 hours at 110° C. The reaction mixture was cooled to RT and poured into water (500 mL). EtOAc (200 mL) was added to the mixture which was then stirred for 15 minutes. The separated aqueous phase was extracted with EtOAc (100 mL). The combined organic extracts were washed with brine (100 mL), dried (Na2SO4) and the solvents removed under reduced pressure. The residue was purified by column chromatography on neutral silica gel using 3-6% EtOAc in hexane to give the title compound (2.9 g, 60%).

Workup

  1. temperatureThe reaction mixture was cooled to RT
  2. extractionThe separated aqueous phase was extracted with EtOAc (100 mL)
  3. washThe combined organic extracts were washed with brine (100 mL)
  4. dry with materialdried (Na2SO4)
  5. customthe solvents removed under reduced pressure
  6. customThe residue was purified by column chromatography on neutral silica gel using 3-6% EtOAc in hexane

Sources & evidence

ORD record
ord-4966bc27cb0843529b9b5968715d6a69
Source dataset
uspto-grants-2014_05
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08716287B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes