Nitric Acid → HCID 22457557, compound

HRID 1604262Notes

Reaction equation

HRID 1604262 reaction equation
[C:1]([O:4][CH2:5][CH2:6][C:7]1[CH:8]=[C:9]([S:18]([Cl:21])(=[O:20])=[O:19])[C:10]2[C:15]([C:16]=1[Br:17])=[CH:14][CH:13]=[CH:12][CH:11]=2)(=[O:3])[CH3:2].S(=O)(=O)(O)O.[N+:27]([O-])([OH:29])=[O:28]>FC(F)(F)C(O)=O>[C:1]([O:4][CH2:5][CH2:6][C:7]1[CH:8]=[C:9]([S:18]([Cl:21])(=[O:19])=[O:20])[C:10]2[C:15]([C:16]=1[Br:17])=[CH:14][CH:13]=[CH:12][C:11]=2[N+:27]([O-:29])=[O:28])(=[O:3])[CH3:2]

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 1118Sulfuric AcidHCID 22457529HCID 22457529, compound

Product 1

HCID 22457557HCID 22457557, compoundYield 41.2%

Reagents, catalysts & solvents 1

HCID 6422Trifluoroacetic acidSolvent

Procedure

An ice-cold, stirred solution of 3-(2-acetoxy-ethyl)-4-bromo-naphthalene-1-sulfonyl chloride (17.66 g, 45.1 mmol) in trifluoroacetic acid (150 mL) was treated with 96% sulfuric acid (12.5 mL, 225 mmol) and with 90% nitric acid (2.65 mL, 56.4 mmol) added dropwise over 3 minutes. The reaction mixture was removed from the ice bath, stirred at room temperature for 15 minutes, re-cooled in an ice bath, and treated with water (850 mL) added dropwise. The resulting mixture was filtered through a celite pad to collect the solid which was washed with water (100 mL) and dissolved in methylene chloride (350 mL). The methylene chloride solution was washed with water (500 mL) containing brine (100 mL), dried over magnesium sulfate, and evaporated under vacuum to an oil (21.23 g). This material was shown to be a 42:58 mixture of the 5-NO2 to 8-NO2 products by 1H NMR). The crude product was mixed with ethyl acetate (20 mL) and sonicated to provide a crystalline precipitate. This material was collected, washed with ethyl acetate, and dried under vacuum to afford the title compound (8.11 g) as an off-white solid. The mother liquors yielded an additional 1.47 g of the title compound following flash chromatography on silica gel (eluting with 30-35% ethyl acetate in hexane) and crystallization from diethyl ether.

Workup

  1. additionadded dropwise over 3 minutes
  2. customThe reaction mixture was removed from the ice bath
  3. temperaturere-cooled in an ice bath
  4. additiontreated with water (850 mL)
  5. additionadded dropwise
  6. filtrationThe resulting mixture was filtered through a celite pad
  7. customto collect the solid which
  8. washwas washed with water (100 mL)
  9. dissolutiondissolved in methylene chloride (350 mL)
  10. washThe methylene chloride solution was washed with water (500 mL)
  11. additioncontaining brine (100 mL)
  12. dry with materialdried over magnesium sulfate
  13. customevaporated under vacuum to an oil (21.23 g)
  14. additiona 42:58 mixture of the 5-NO2 to 8-NO2 products by 1H NMR)
  15. additionThe crude product was mixed with ethyl acetate (20 mL)
  16. customsonicated
  17. customto provide a crystalline precipitate
  18. customThis material was collected
  19. washwashed with ethyl acetate
  20. customdried under vacuum

Sources & evidence

ORD record
ord-d536cd3ca463464aaecd012d058d6829
Source dataset
uspto-grants-1999_11
Patent number
US05994345

Reaction notes

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