Acetic Acid → HCID 14994783, compound

HRID 344660Notes

Reaction equation

HRID 344660 reaction equation
[F:1][C:2]1[CH:8]=[CH:7][C:6]([CH2:9][CH2:10][CH3:11])=[CH:5][C:3]=1N.N([O-])=O.[Na+].C(O)(=[O:18])C.[S:20](=[O:22])=[O:21]>S(=O)(=O)(O)O.O.[Cu](Cl)Cl>[F:1][C:2]1[CH:8]=[CH:7][C:6]([CH2:9][CH2:10][CH3:11])=[CH:5][C:3]=1[S:20]([OH:18])(=[O:22])=[O:21]

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 1119Sulfur DioxideHCID 14994782HCID 14994782, compoundHCID 23668193Sodium Nitrite2×

Product 1

HCID 14994783HCID 14994783, compoundYield 39.9%

Reagents, catalysts & solvents 3

HCID 24014Cupric ChlorideCatalystHCID 962WaterSolvent3×HCID 1118Sulfuric AcidSolvent

Conditions

Temperature
-10 °C

Procedure

A solution of 12.53 g of 2-fluoro-5-n-propylaniline dissolved in a mixed solution of 73 ml of conc. sulfuric acid and 120 ml of water was cooled to -10° C. and an aqueous sodium nitrite solution containing 6.15 g of sodium nitrite dissolved in 15 ml of water was added dropwise thereinto at a temperature of -5° C. or lower, followed by stirring at this temperature for 25 minutes to prepare a diazonium salt solution. The diazonium salt solution was added dropwise into a mixed solution of 120 ml of acetic acid saturated with sulfur dioxide and 2.92 ml of copper chloride dissolved in 20 ml of water at a temperature of -20° C., and after stirred at -10° C. for 30 minutes and further at 0° C. for one hour, the oily substance separated was extracted with ethyl acetate. Ethyl acetate was evaporated under reduced pressure from the extract, and to the residue were added 90 ml of 2 N sodium hydroxide solution and 200 ml of dioxane. After the mixture was heated at 100° C. for 5 minutes, it was neutralized with acetic acid and the reaction product was purified by silica gel chromatography (eluant:chloroform:methanol:acetic acid =500:50:6) to give 7.13 g (yield: 39.9%) of the above title compound as a paste.

Workup

  1. additionwas added dropwise
  2. customat a temperature of -5° C.
  3. stirringafter stirred at -10° C. for 30 minutes and further at 0° C. for one hour
  4. customthe oily substance separated
  5. extractionwas extracted with ethyl acetate
  6. customEthyl acetate was evaporated under reduced pressure from the extract
  7. additionto the residue were added 90 ml of 2 N sodium hydroxide solution and 200 ml of dioxane
  8. temperatureAfter the mixture was heated at 100° C. for 5 minutes
  9. customthe reaction product was purified by silica gel chromatography (eluant:chloroform:methanol:acetic acid =500:50:6)

Sources & evidence

ORD record
ord-00f404b750d5470a954f7100a0bcdbea
Source dataset
uspto-grants-1991_10
Patent number
US05053409

Reaction notes

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