Lithium Chloride → 2-Chloro-1,3-dimethyl-5-nitrobenzene

HRID 866017Notes

Reaction equation

HRID 866017 reaction equation
FC(F)(F)S(O[C:7]1[C:12]([CH3:13])=[CH:11][C:10]([N+:14]([O-:16])=[O:15])=[CH:9][C:8]=1[CH3:17])(=O)=O.[Cl-:20].[Li+]>CN1CCCC1=O.O>[Cl:20][C:7]1[C:12]([CH3:13])=[CH:11][C:10]([N+:14]([O-:16])=[O:15])=[CH:9][C:8]=1[CH3:17]

Participants

5

Reactant 2

HCID 433294Lithium ChlorideHCID 226621252,6-Dimethyl-4-nitrophenyl trifluoromethanesulfonate

Product 1

HCID 99205692-Chloro-1,3-dimethyl-5-nitrobenzene

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 13387N-methyl-2-pyrrolidoneSolvent

Procedure

4-Nitro-2,6-dimethylphenyl trifluoromethanesulfonate (4.06 kg, 13.6 mol) is dissolved in anhydrous N-methylpyrrolidinone (42 L) and to this solution is added anhydrous lithium chloride (900 g) all at once. The internal temperature is raised to 120° at which time the color changes to a dark golden brown. After 10 hours at this temperature the color of the solution is dark brown. The reaction is then cooled to 5° and diluted with cold water (5°, 21 L) at such a rate as to keep the temperature below 15°. After the addition is complete the mixture is stirred for 1 hour at 5°. The product is collected by filtration and washed with water (4×1 L). This dark brown solid is dissolved in t-butyl methyl ether (42 L) and stirred first with charcoal and then anhydrous magnesium sulfate (10 pounds). After filtration the solvents are removed in vacuo (40°, 3 Torr) to obtain a tan solid which is dried in vacuo (25°, 3 Torr) for 2 days to obtain 4-chloro-3,5-dimethylnitrobenzene, m.p. 101°-105°.

Workup

  1. temperatureThe internal temperature is raised to 120° at which time the color changes to a dark golden brown
  2. temperatureThe reaction is then cooled to 5°
  3. customthe temperature below 15°
  4. additionAfter the addition
  5. filtrationThe product is collected by filtration
  6. washwashed with water (4×1 L)
  7. dissolutionThis dark brown solid is dissolved in t-butyl methyl ether (42 L)
  8. stirringstirred first with charcoal
  9. filtrationAfter filtration the solvents
  10. customare removed in vacuo (40°, 3 Torr)
  11. customto obtain a tan solid which
  12. customis dried in vacuo (25°, 3 Torr) for 2 days

Sources & evidence

ORD record
ord-168472f3eb864b5482c7b5c67182e753
Source dataset
uspto-grants-1996_10
Patent number
US05569674

Reaction notes

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