Hydrogen Peroxide → Methyl 3-chloro-2-nitrobenzoate

HRID 1470703Notes

Reaction equation

HRID 1470703 reaction equation
S(=O)(=O)(O)O.[NH2:6][C:7]1[C:16]([Cl:17])=[CH:15][CH:14]=[CH:13][C:8]=1[C:9]([O:11][CH3:12])=[O:10].OO.[OH-:20].[Na+].C(=O)([O-])O.[Na+].[OH2:27]>[Br-].C([N+](C)(C)C)CCCCCCCCCCCCC.C1(C)C=CC=CC=1.O[W](O)(=O)=O>[Cl:17][C:16]1[C:7]([N+:6]([O-:27])=[O:20])=[C:8]([CH:13]=[CH:14][CH:15]=1)[C:9]([O:11][CH3:12])=[O:10]

Participants

10

Reactant 6

HCID 784Hydrogen Peroxide2×HCID 962WaterHCID 1118Sulfuric AcidHCID 14798Sodium HydroxideHCID 516892Sodium BicarbonateHCID 11030511Benzoic acid, 2-amino-3-chloro-, methyl ester2×

Product 1

HCID 12187125Methyl 3-chloro-2-nitrobenzoateYield 72%

Reagents, catalysts & solvents 3

HCID 1152Tungstic acidCatalystHCID 14250Tetradecyltrimethylammonium bromideCatalystHCID 1140TolueneSolvent2×

Conditions

Temperature
47 °C

Procedure

A solution of 7.1 g (28.5 mmol) of tungstic acid, 4.9 g (48.5 mmol) of concentrated sulfuric acid, 35.6 g (190 mmol) of methyl 2-amino-3-chlorobenzoate, and 5.84 g (20 mmol) of myristyltrimethylammonium bromide in 74 ml of toluene was heated to 47° C., and 50 ml (570 mmol) of a 35% hydrogen peroxide solution was added dropwise over 10 hours. The pH value at this time was 0.3. After the completion of the dropwise addition, the mixture was stirred at 47° C. for 4 hours. After the disappearance of the methyl 2-amino-3-chlorobenzoate was confirmed by HPLC analysis (area percentage method), 189.4 g (2.06 mol) of toluene and 19 g (150 mmol) of a 25% aqueous sodium hydroxide solution were added. The pH value at this time was 7.5. The reaction liquid was separated at 75° C., and 91 g of the aqueous layer was removed. Then, the obtained organic layer was cooled to 60° C. or less. 5.2 g (61.9 mmol) of sodium hydrogen carbonate and 5.2 ml of water were added, and 25 ml (285 mmol) of a 35% hydrogen peroxide solution was added dropwise while the reaction temperature was adjusted to 60° C. or less. After the completion of the dropwise addition, the mixture was stirred at 60° C. for 2 hours, and the reaction was completed. The reaction liquid was separated at room temperature. The obtained organic layer was analyzed by HPLC by the absolute calibration method, and as a result, the yield was 72%.

Workup

  1. additionAfter the completion of the dropwise addition
  2. additionwere added
  3. customThe reaction liquid
  4. customwas separated at 75° C.
  5. custom91 g of the aqueous layer was removed
  6. temperatureThen, the obtained organic layer was cooled to 60° C. or less
  7. customwas adjusted to 60° C. or less
  8. additionAfter the completion of the dropwise addition
  9. stirringthe mixture was stirred at 60° C. for 2 hours
  10. customThe reaction liquid
  11. customwas separated at room temperature

Sources & evidence

ORD record
ord-a0aa4fa263c84d4a9cd54b74665fdcf4
Source dataset
uspto-grants-2015_04
Patent number
US09006477B2

Reaction notes

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