Sulfuric Acid → HCID 10657142, compound

HRID 2260376Notes

Reaction equation

HRID 2260376 reaction equation
OS(O)(=O)=O.[CH3:6][C:7]1[CH:16]=[C:15]([CH3:17])[CH:14]=[C:13]2[C:8]=1[C:9](=[O:21])[CH:10]=[C:11]([O:19][CH3:20])[C:12]2=[O:18].[N-:22]=[N+]=[N-].[Na+]>CO>[CH3:6][C:7]1[C:8]2[C:9](=[O:21])[CH:10]=[C:11]([O:19][CH3:20])[C:12](=[O:18])[NH:22][C:13]=2[CH:14]=[C:15]([CH3:17])[CH:16]=1

Participants

5

Reactant 3

HCID 1118Sulfuric AcidHCID 33557Sodium AzideHCID 10680230HCID 10680230, compound

Product 1

HCID 10657142HCID 10657142, compoundYield 93.4%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To stirred, ice bath cold, coned H2SO4 (14 mL, Baker), there was added 5,7-dimethyl-2-methoxynaphthalene-1,4-dione (1.00 g, 4.63 mmol) in portions. A deep red solution resulted. To this cold solution, NaN3 (601 mg, 9.24 mmol, Aldrich) was added in portions over one min. The ice bath was removed and the reaction was allowed to stir at rt for 18 h under N2. Nitrogen evolution was noted. The reaction was added to crushed ice (100 mL) to give a brown suspension. A solution of 30% MeOH/70% CHCl3 (90 mL) was added and vigorously stirred until all the solid had dissolved. The layers were separated and the aqueous portion was extracted with 30% MeOH/70% CHCl3 (2×30 mL). The combined red organic portion was washed with water (1×30 mL), saturated NaHCO3 (1×30 mL) and brine (1×30 mL), filtered through cotton and the solvent removed in vacuo to give a red solid (~1 g). Crystallization from 95% EtOH (dissolved in 40 mL, hot filtered, concd to 25 mL, allowed to cool to rt then in an ice bath) a gave colorless fluffy needles (678 mg, 63%, pure by 1H NMR); mp 237°-238° C.; 1H NMR (DMSO-d6) δ2.25 (s, 3H), 2.29 (s, 3H), 3.70 (s, 3H), 6.28 (s, 1H), 6.90 (s, 1H), 6.94 (s, 1H), 10.94 (s, 1H); 13C NMR (DMSO-d6) δ20.66, 56.04, 113.58, 118.69, 127.47, 128.10, 135.44, 137.45, 141.20, 153.83, 160.10, 190.53; IR (KBr) 3207 (m), 3003 (m), 2920 (m), 1682 (s), 1645 (s), 1619 (s), 1241 (m), 1224 (m), 855 (m); MS (m/z) 231 (M+, 100).

Workup

  1. customA deep red solution resulted
  2. customThe ice bath was removed
  3. stirringto stir at rt for 18 h under N2
  4. additionThe reaction was added
  5. customto crushed ice (100 mL)
  6. customto give a brown suspension
  7. stirringvigorously stirred until all the solid
  8. dissolutionhad dissolved
  9. customThe layers were separated
  10. extractionthe aqueous portion was extracted with 30% MeOH/70% CHCl3 (2×30 mL)
  11. washThe combined red organic portion was washed with water (1×30 mL), saturated NaHCO3 (1×30 mL) and brine (1×30 mL)
  12. filtrationfiltered through cotton
  13. customthe solvent removed in vacuo

Sources & evidence

ORD record
ord-9c71cf794f6844629af945288bf06b18
Source dataset
uspto-grants-1995_12
Patent number
US05476933

Reaction notes

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