Sulfuric Acid → HCID 10822205, compound

HRID 2260360Notes

Reaction equation

HRID 2260360 reaction equation
OS(O)(=O)=O.[CH3:6][O:7][C:8]1[C:9](=[O:19])[C:10]2[CH2:11][CH2:12][CH2:13][CH2:14][C:15]=2[C:16](=[O:18])[CH:17]=1.[N-:20]=[N+]=[N-].[Na+]>CO>[CH3:6][O:7][C:8]1[C:9](=[O:19])[NH:20][C:10]2[CH2:11][CH2:12][CH2:13][CH2:14][C:15]=2[C:16](=[O:18])[CH:17]=1

Participants

5

Reactant 3

HCID 1118Sulfuric AcidHCID 33557Sodium AzideHCID 19710567HCID 19710567, compound

Product 1

HCID 10822205HCID 10822205, compoundYield 43.3%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To stirred, ice bath cold, concd H2SO4 (10 mL, Baker), there was added 2-methoxy-5,6,7,8-tetrahydronaphthalene-1,4-dione (600 mg, 3.12 mmol) in portions. A deep red solution resulted. To this cold solution, NaN3 (406 mg, 6.24 mmol, Aldrich) was added in portions. The reaction was allowed to slowly attain rt with stirring under N2. Gas evolution was noted. After 16 h, the reaction was judged complete by TLC analysis (10% MeOH/90% CHCl3). The reaction was added to crushed ice (100 mL) to give a yellow/brown solution. This was extracted with 30% MeOH/70% CHCl3 (4×30 mL) and CHCl3 (2×30 mL). The extract was washed with water (1×20 mL), saturated NaHCO3 (1×20 mL) and brine (1×20 mL), filtered through cotton and the solvent removed in vacuo to give a red solid (280 mg). An additional portion was obtained in exactly the same manner (350 mg). The combined solids were subjected to vacuum chromatography (silica gel, 2.5×25 cm, initial CHCl3 elution to remove mobile impurities, 2% EtOH/98% CHCl3 elution to remove product) to yield a pink solid. Crystallization from 95% EtOH (dissolved in 20 mL, hot filtered, concd to 8 mL, allowed to cool to rt) yielded a pink solid (242 mg, 19%, >95% pure by 1H NMR, mp 227.5°-228.5° C.). A sample was further purified by recrystallization from 95% EtOH (25 mg dissolved in 2 mL, allowed to cool to rt, yielded a pale pink solid, 14 mg, 56% recovery); mp 228.5°-229.5° C.; 1H NMR (DMSO-d6) δ1.55 (m, 4H), 2.28 (m, 2H), 2.43 (m, 2H), 3.72 (s, 3H), 6.23 (s, 1H), 10.57 (s, 1H); MS m/z 207 (M+, 85).

Workup

  1. customA deep red solution resulted
  2. customwas allowed to slowly attain rt
  3. stirringwith stirring under N2
  4. additionThe reaction was added
  5. customto give a yellow/brown solution
  6. extractionThis was extracted with 30% MeOH/70% CHCl3 (4×30 mL) and CHCl3 (2×30 mL)
  7. washThe extract was washed with water (1×20 mL), saturated NaHCO3 (1×20 mL) and brine (1×20 mL)
  8. filtrationfiltered through cotton
  9. customthe solvent removed in vacuo

Sources & evidence

ORD record
ord-e21244bb1234418687c03d2139585d3d
Source dataset
uspto-grants-1995_12
Patent number
US05476933

Reaction notes

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