Sulfuric Acid → 3-Azido-1,5,5-trimethyl-1-cyclohexene

HRID 2307091Notes

Reaction equation

HRID 2307091 reaction equation
[N-:1]=[N+:2]=[N-:3].[Na+].OS(O)(=O)=O.[CH3:10][CH:11]1[CH2:16][C:15]([CH3:18])([CH3:17])[CH2:14][CH2:13][CH:12]1O.[NH4+].[OH-]>C(Cl)Cl>[N:1]([CH:13]1[CH2:14][C:15]([CH3:18])([CH3:17])[CH2:16][C:11]([CH3:10])=[CH:12]1)=[N+:2]=[N-:3]

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 14923Ammonium HydroxideHCID 33557Sodium AzideHCID 12724549HCID 12724549, compound

Product 1

HCID 108882753-Azido-1,5,5-trimethyl-1-cyclohexeneYield 44.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a cooled (0° C.) suspension of sodium azide (0.81 g, 12.5 mmol) in CH2Cl2 (5 ml) was added dropwise 53% aqueous H2SO4 (8 ml). The mixture was stirred for 10 min, then a solution of 3,5,5-trimethyl-2-cyclohexanol (33) (0.70 g, 5 mmol) in CH2Cl2 (8 ml) was added. The mixture was stirred for 20 h, poured into ice water, neutralized with aqueous NH4OH and extracted with CH2Cl2. The extract was washed with brine and dried over MgSO4. Filtration and evaporation of the solvent keeping the temperature below 25° C. gave an oil which was separated by column chromatography on silica gel (light petroleum ether). A fraction with Rf 0.8 (hexane) was collected. Evaporation of the solvent gave 34 as a colorless oil (0.365 g, 44%). 1H NMR (CDCl3, TMS): 0.89 and 1.01 (total 6H, both s, 5,5-CH3); 1.34 (1H, m, c-4-CH); 1.55-1.95 (3H, m, 4-CH, 6-CH2); 1.71 (3H, s, 1-CH3); 3.90 (1H, m, 3-CH) and 5.39 ppm (1H, s, C═CH).

Workup

  1. temperatureTo a cooled
  2. stirringThe mixture was stirred for 20 h
  3. extractionextracted with CH2Cl2
  4. washThe extract was washed with brine
  5. dry with materialdried over MgSO4
  6. filtrationFiltration and evaporation of the solvent
  7. customthe temperature below 25° C.
  8. customgave an oil which
  9. customwas separated by column chromatography on silica gel (light petroleum ether)
  10. customA fraction with Rf 0.8 (hexane) was collected
  11. customEvaporation of the solvent

Sources & evidence

ORD record
ord-10b68e81c8fb4cc99689ca01e2f700f7
Source dataset
uspto-grants-2004_12
Patent number
US06828462B2

Reaction notes

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