Hydrochloric Acid → Methyl 2-(chlorosulfonyl)-6-fluorobenzoate

HRID 1086743Notes

Reaction equation

HRID 1086743 reaction equation
[F:1][C:2]1[CH:3]=[CH:4][CH:5]=[C:6](N)[C:7]=1[C:8]([O:10][CH3:11])=[O:9].N([O-])=O.[Na+].[ClH:17].ClCl.[S:20](=[O:22])=[O:21]>O.[Cu](Cl)Cl.ClCCCl>[Cl:17][S:20]([C:6]1[CH:5]=[CH:4][CH:3]=[C:2]([F:1])[C:7]=1[C:8]([O:10][CH3:11])=[O:9])(=[O:22])=[O:21]

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 1119Sulfur Dioxide2×HCID 24526ChlorineHCID 2818492Methyl 2-amino-6-fluorobenzoateHCID 23668193Sodium Nitrite

Product 1

HCID 14257491Methyl 2-(chlorosulfonyl)-6-fluorobenzoate

Reagents, catalysts & solvents 3

HCID 24014Cupric ChlorideCatalystHCID 111,2-DichloroethaneSolventHCID 962WaterSolvent2×

Conditions

Temperature
5 °C

Procedure

At 5° C. and while stirring, 108 g (0.64 mol) of methyl 6-fluoroanthranilate and 45 g (0.65 mol) of sodium nitrite in 106 ml of water were added separately but simultaneously over a period of 1 hour in such a manner to 250 ml of concentrated hydrochloric acid that the ester component was in an excess. After the reaction mixture had been stirred for 20 minutes at 5 to 8° C., it was poured all at once into a prepared solution of 53 g of sulfur dioxide, 1.7 g of copper (II) chloride in a small amount of water and 200 ml of 1,2-dichloroethane, and stirred for a further 10 minutes. The mixture was heated slowly to 50° C. and stirred for ninety minutes while passing in 46 g of sulfur dioxide. The mixture was then cooled to 20° C. and 5.5 g of chlorine was passed in over a 20-minute period while stirring. The organic phase was then separated, washed with water and dried. There was obtained 65% of theory of the title compound as a brownish oil.

Workup

  1. stirringAfter the reaction mixture had been stirred for 20 minutes at 5 to 8° C.
  2. stirringstirred for a further 10 minutes
  3. temperatureThe mixture was heated slowly to 50° C.
  4. stirringstirred for ninety minutes
  5. temperatureThe mixture was then cooled to 20° C.
  6. customwas passed in over a 20-minute period
  7. stirringwhile stirring
  8. customThe organic phase was then separated
  9. washwashed with water
  10. customdried

Sources & evidence

ORD record
ord-9031adb024a74cd8be24ca32b5eeb96e
Source dataset
uspto-grants-1991_07
Patent number
US05032167

Reaction notes

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