Sulfuric Acid → HCID 13603942, compound

HRID 638254Notes

Reaction equation

HRID 638254 reaction equation
S(=O)(=O)(O)O.N[C:7]1[CH:12]=[CH:11][C:10]([CH:13]([CH3:21])[CH2:14][CH2:15][C:16]([O:18][CH2:19][CH3:20])=[O:17])=[CH:9][CH:8]=1.N([O-])=[O:23].[Na+]>O.S([O-])([O-])(=O)=O.[Cu+2]>[OH:23][C:7]1[CH:12]=[CH:11][C:10]([CH:13]([CH3:21])[CH2:14][CH2:15][C:16]([O:18][CH2:19][CH3:20])=[O:17])=[CH:9][CH:8]=1

Participants

6

Reactant 3

HCID 1118Sulfuric AcidHCID 12561714HCID 12561714, compoundHCID 23668193Sodium Nitrite

Product 1

HCID 13603942HCID 13603942, compoundYield 53%

Reagents, catalysts & solvents 2

HCID 24462Copper SulfateCatalystHCID 962WaterSolvent4×

Procedure

To a solution of 350 g of concentrated sulfuric acid and 350 ml of water cooled to 0° C., 40 g of ethyl 4-(4-aminophenyl)pentanoate was added dropwise, maintaining the temperature at 0°-2° C. The mixture was then treated dropwise with 13.66 g of sodium nitrite in 25 ml of water at such a rate that the temperature did not exceed 2° C. The resultant solution was added dropwise to a refluxing solution of 387 g of copper sulfate in 600 ml of water over a period of approximately 30 minutes. The mixture was refluxed an additional 10 minutes, cooled to room temperature, and 800 ml of water was added. The mixture was extracted thrice with dichloromethane (additional water was needed to dissolve the salts). The organic phase was washed with water, dried over anhydrous sodium sulfate, filtered and evaporated to give an oil. The oil was distilled at 0.6 mm to give 21.05 g (53%) of product, b.p. 129° C., which crystallized on cooling, m.p. 32°-34° C.

Workup

  1. temperaturemaintaining the temperature at 0°-2° C
  2. customdid not exceed 2° C
  3. temperatureThe mixture was refluxed an additional 10 minutes
  4. extractionThe mixture was extracted thrice with dichloromethane (additional water
  5. dissolutionto dissolve the salts)
  6. washThe organic phase was washed with water
  7. dry with materialdried over anhydrous sodium sulfate
  8. filtrationfiltered
  9. customevaporated
  10. customto give an oil
  11. distillationThe oil was distilled at 0.6 mm

Sources & evidence

ORD record
ord-c3e793340c27471aa76f9358a9454aa8
Source dataset
uspto-grants-1985_12
Patent number
US04560701

Reaction notes

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