Nitric Acid → 1-[(3-methoxy-4-nitrophenyl)methyl]-1H-imidazole

HRID 2166052Notes

Reaction equation

HRID 2166052 reaction equation
S(=O)(=O)(O)O.[N+:6]([O-:9])(O)=[O:7].[CH3:10][O:11][C:12]1[CH:13]=[C:14]([CH2:18][N:19]2[CH:23]=[CH:22][N:21]=[CH:20]2)[CH:15]=[CH:16][CH:17]=1.[N+]([O-])(O)=O.[OH-].[NH4+]>>[CH3:10][O:11][C:12]1[CH:13]=[C:14]([CH2:18][N:19]2[CH:23]=[CH:22][N:21]=[CH:20]2)[CH:15]=[CH:16][C:17]=1[N+:6]([O-:9])=[O:7]

Participants

5

Reactant 4

HCID 944Nitric AcidHCID 1118Sulfuric AcidHCID 14923Ammonium HydroxideHCID 678680831-[(3-methoxyphenyl)methyl]-1H-imidazole mononitrate

Product 1

HCID 149907011-[(3-methoxy-4-nitrophenyl)methyl]-1H-imidazoleYield 40.3%

Procedure

To 184 parts of cold (10° C., ice bath) concentrated sulfuric acid were added portionwise 75 parts of 1-[(3-methoxyphenyl)methyl]-1H-imidazole mononitrate during 1 hour. Upon complete addition, stirring was continued for 30 minutes at 10° C. 15 Parts of concentrated nitric acid were added dropwise during 30 minutes at 15° C. Upon completion, the whole was stirred for 30 minutes at 10° C. The reaction mixture was poured into 1500 parts of crushed ice and the whole was treated with an ammonium hydroxide solution. The product was extracted with dichloromethane. The extract was dried, filtered and evaporated. The residue was purified by column chromatography over silica gel using a mixture of ethyl acetate, methanol and methanol, saturated with ammonia, (95:2.5:2.5 by volume) as eluent. The pure fractions were collected and the eluent was evaporated in vacuo. The residue was stirred in 45 parts of ethyl acetate. The precipitated product was filtered off, washed with 2,2'-oxybispropane and dried, yielding 28.2 parts (40.3%) of 1-[(3-methoxy-4-nitrophenyl)methyl]-1H-imidazole (int. 145).

Workup

  1. additionUpon complete addition
  2. stirringUpon completion, the whole was stirred for 30 minutes at 10° C
  3. additionThe reaction mixture was poured into 1500 parts of crushed ice
  4. extractionThe product was extracted with dichloromethane
  5. customThe extract was dried
  6. filtrationfiltered
  7. customevaporated
  8. customThe residue was purified by column chromatography over silica gel using
  9. additiona mixture of ethyl acetate, methanol and methanol
  10. customThe pure fractions were collected
  11. customthe eluent was evaporated in vacuo
  12. stirringThe residue was stirred in 45 parts of ethyl acetate
  13. filtrationThe precipitated product was filtered off
  14. washwashed with 2,2'-oxybispropane
  15. customdried

Sources & evidence

ORD record
ord-2e0202063ddb497080a327021aaf402c
Source dataset
uspto-grants-1990_07
Patent number
US04943574

Reaction notes

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