Methanol → HCID 10488953, compound

HRID 2260373Notes

Reaction equation

HRID 2260373 reaction equation
OS(O)(=O)=O.[CH3:6][O:7][C:8]1[C:9](=[O:20])[C:10]2[C:15]([C:16](=[O:18])[CH:17]=1)=[C:14]([CH3:19])[CH:13]=[CH:12][CH:11]=2.[N-:21]=[N+]=[N-].[Na+].CO>O>[CH3:6][O:7][C:8]1[C:9](=[O:20])[NH:21][C:10]2[CH:11]=[CH:12][CH:13]=[C:14]([CH3:19])[C:15]=2[C:16](=[O:18])[CH:17]=1

Participants

6

Reactant 4

HCID 887MethanolHCID 1118Sulfuric AcidHCID 33557Sodium AzideHCID 10584244HCID 10584244, compound

Product 1

HCID 10488953HCID 10488953, compoundYield 93%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To stirred, ice bath cold, concd H2SO4 (12 mL, Baker), there was added 2-methoxy-5-methylnaphthalene-1,4-dione (800 mg, 3.96 mmol) in portions. A deep red solution resulted. To this cold solution, NaN3 (515 mg, 7.92 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 (50 mL) to give a thick green suspension. This was diluted with H2O (30 mL) and vigorously stirred with 30% MeOH/70% CHCl3 (60 mL) 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 (800 mg). Crystallization from 95% EtOH (dissolved in 30 mL, hot filtered, concd to 20 mL, allowed to cool to rt then in an ice bath) a gave colorless fluffy needles (564 mg, 66%, pure by 1H NMR); mp 215.5° -217° C.; 1H NMR (DMSO-d6) δ2.32 (s, 3H), 3.71 (s, 3H), 6.32 (s, 1H), 7.08 (d, J=7.5 Hz, 1H), 7.15 (d, J=8.1 Hz, 1H), 7.36 (t, J=7.8 Hz, 1H), 11.00 (s, 1H); IR (KBr) 3195 (m), 3134 (m), δ3061 (m), 2999 (m), 2967 (m), 2939 (m), 1691 (s), 1649 (s), 1616 (s), 1212 (m), 834 (m), 783 (m); MS (m/z) 217 (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 (50 mL)
  6. customto give a thick green suspension
  7. dissolutionhad dissolved
  8. customThe layers were separated
  9. extractionthe aqueous portion was extracted with 30% MeOH/70% CHCl3 (2×30 mL)
  10. washThe combined red organic portion was washed with water (1×30 mL), saturated NaHCO3 (1×30 mL) and brine (1×30 mL)
  11. filtrationfiltered through cotton
  12. customthe solvent removed in vacuo

Sources & evidence

ORD record
ord-f333f89db01d4a68b739274e597956bb
Source dataset
uspto-grants-1995_12
Patent number
US05476933

Reaction notes

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