Methanol → HCID 54324456, compound

HRID 262532Notes

Reaction equation

HRID 262532 reaction equation
N(OS(=O)(=O)O)=O.N[C:9]1[CH:10]=[CH:11][C:12]2[CH2:18][CH2:17][CH:16]([NH:19][CH3:20])[CH:15]=[CH:14][C:13]=2[CH:21]=1.[CH3:22][OH:23]>C(O)(=O)C>[CH3:22][O:23][C:9]1[CH:10]=[CH:11][C:12]2[CH2:18][CH2:17][CH:16]([NH:19][CH3:20])[CH:15]=[CH:14][C:13]=2[CH:21]=1

Participants

5

Reactant 3

HCID 887MethanolHCID 82157Nitrosylsulfuric acidHCID 53946840HCID 53946840, compound

Product 1

HCID 54324456HCID 54324456, compound

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

5.1 g of nitrosyl sulfuric acid were added over 10 minutes at 20° C. to a mixture of 6 g of 2-amino-7-methylamino-6,7-dihydro [5H] benzocycloheptene in 60 ml of acetic acid and the mixture was stirred 2 hours at room temperature. The resulting brown solution was poured into 300 ml of methanol and the mixture was refluxed for 45 minutes and was evaporated to dryness under reduced pressure. The residue was added to 150 ml of water and the neutral fraction was removed by extraction twice with 100 ml of ether. The mixture was alkalinized at 10° C. by addition of sodium hydroxide and was extracted with methylene chloride. The organic phase was washed with water, dried over magnesium sulfate, filtered and evaporated to dryness under reduced pressure to obtain 3.7 g of raw product. The latter was chromatographed over silica gel and was eluted with a 7-2-1 chloroform-methanol-triethylamine mixture to obtain a homogenous fraction of 3.4 g of 2-methoxy-7-methylamino-6,7-dihydro [5H] benzocycloheptene in the form of a yellow oil.

Workup

  1. temperaturethe mixture was refluxed for 45 minutes
  2. customwas evaporated to dryness under reduced pressure
  3. additionThe residue was added to 150 ml of water
  4. customthe neutral fraction was removed by extraction twice with 100 ml of ether
  5. additionThe mixture was alkalinized at 10° C. by addition of sodium hydroxide
  6. extractionwas extracted with methylene chloride
  7. washThe organic phase was washed with water
  8. dry with materialdried over magnesium sulfate
  9. filtrationfiltered
  10. customevaporated to dryness under reduced pressure
  11. customto obtain 3.7 g of raw product
  12. customThe latter was chromatographed over silica gel
  13. washwas eluted with a 7-2-1 chloroform-methanol-triethylamine mixture

Sources & evidence

ORD record
ord-596f950a8a8d4d458da4441005345120
Source dataset
uspto-grants-1979_05
Patent number
US04154852

Reaction notes

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