1-Chloro-4-nitrobenzene → Methyl 5-chloro-2-nitrobenzeneacetate

HRID 542997Notes

Reaction equation

HRID 542997 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=1.CN([S+](N(C)C)N(C)C)C.C[Si-](F)(F)(C)C.BrBr.S(=O)(O)[O-:30].[Na+].C1[CH2:38][O:37][CH2:36][CH2:35]1>C(#N)C>[N+:8]([C:5]1[CH:6]=[CH:7][C:2]([Cl:1])=[CH:3][C:4]=1[CH2:35][C:36]([O:37][CH3:38])=[O:30])([O-:10])=[O:9]

Participants

7

Reactant 5

HCID 74741-Chloro-4-nitrobenzeneHCID 8028TetrahydrofuranHCID 24408BromineHCID 9795567Tris(dimethylamino)sulfonium difluorotrimethylsilicateHCID 23665763Sodium Bisulfite

Product 1

HCID 13265167Methyl 5-chloro-2-nitrobenzeneacetate

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution of 1.576 g (10 mmol) of 4-chloronitrobenzene and 1.68 mL (10.22 mmol) of carbomethyloxymethyltrimethylsilane in anhydrous THF was added 2.751 g (10 mmol) of TASF in 5 mL of acetonitrile at -78° C. The mixture was stirred for 7 hrs at that temperature, and 0.50 mL (9.70 mmol) of bromine was added dropwise. Stirring was continued for 1 hr, and saturated sodium bisulfite was added. The product was extracted into ether and isolated by chromatography on silica using 30% ether/hexane as solvent. The yield was 1.15 g (50%) product, which was an oil. The product was analyzed by infrared spectroscopy and nuclear magnetic resonance spectroscopy.

Workup

  1. additionwas added dropwise
  2. extractionThe product was extracted into ether
  3. customisolated by chromatography on silica using 30% ether/hexane as solvent

Sources & evidence

ORD record
ord-f024009273a449ee935b37cd2adf8c09
Source dataset
uspto-grants-1987_04
Patent number
US04659862

Reaction notes

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