phosphenous acid → 1-Bromo-3-methyl-5-nitrobenzene

HRID 1106749Notes

Reaction equation

HRID 1106749 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[C:5](N)=[C:4]([CH3:12])[CH:3]=1.N([O-])=O.[Na+].OP=O>S(=O)(=O)(O)O.O.[Cu-]=O>[Br:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[C:4]([CH3:12])[CH:3]=1

Participants

7

Reactant 3

HCID 22497phosphenous acidHCID 5226794-Bromo-2-methyl-6-nitroanilineHCID 23668193Sodium Nitrite

Product 1

HCID 1042131-Bromo-3-methyl-5-nitrobenzeneYield 82.7%

Reagents, catalysts & solvents 3

HCID 178419072HCID 178419072, compoundCatalystHCID 962WaterSolventHCID 1118Sulfuric AcidSolvent

Procedure

A solution of 10 g of 4-bromo-2-methyl-6-nitro-phenylamine in 100 ml of concentrated sulfuric acid in an ice bath was treated dropwise with 3.58 g of sodium nitrite in 10 ml of water keeping the temperature below 10° C. The mixture was then treated simultaneously over 1 hr with 6.81 g of copper (I) oxide and 31.4 ml of hypophosphorus acid. Poured into ice water, extracted with ether, washed with water, dried over magnesium sulfate, and evaporated to dryness. The residue was purified by flash column chromatography on silica gel eluting with ethyl acetate/hexane (1:9) giving 7.73 g of 1-bromo-3-methyl-5-nitrobenzene. ##STR152##

Workup

  1. extractionextracted with ether
  2. washwashed with water
  3. dry with materialdried over magnesium sulfate
  4. customevaporated to dryness
  5. customThe residue was purified by flash column chromatography on silica gel eluting with ethyl acetate/hexane (1:9)

Sources & evidence

ORD record
ord-abd6d41e2f63416d8238c2725de7171f
Source dataset
uspto-grants-2000_05
Patent number
US06057349

Reaction notes

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