RU 25591 → HCID 131711660, compound

HRID 1447655Notes

Reaction equation

HRID 1447655 reaction equation
N(C(OCC)=O)=NC(OCC)=O.[CH3:13][N:14](C)[C@@H:15]1[CH2:21][CH2:20][C:19]2[CH:22]=[CH:23][CH:24]=[CH:25][C:18]=2[C@H:17]([O:26][C:27]2[CH:32]=[CH:31][C:30]([N+:33]([O-:35])=[O:34])=[CH:29][CH:28]=2)[CH2:16]1>CC(C)=O>[CH3:13][NH:14][C@@H:15]1[CH2:21][CH2:20][C:19]2[CH:22]=[CH:23][CH:24]=[CH:25][C:18]=2[C@H:17]([O:26][C:27]2[CH:28]=[CH:29][C:30]([N+:33]([O-:35])=[O:34])=[CH:31][CH:32]=2)[CH2:16]1

Participants

4

Reactant 2

HCID 182578RU 25591HCID 220568ethyl N-ethoxycarbonyliminocarbamate

Product 1

HCID 131711660HCID 131711660, compoundYield 64.1%

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

348 mg of diethyl azocarboxylate were added to a mixture of 652 mg of cis N,N-dimethyl-5-[4-nitrophenoxy]-6,7,8,9-tetrahydro-5H-benzocyclohepten-7-amine in 10 ml of acetone and the mixture was refluxed for 31/2 hours. The acetone was distilled under reduced pressure and 5 ml of N hydrochloric acid were added to the residue. The mixture was stirred at room temperature for 26 hours and was then made alkaline with ammonium hydroxide. The mixture was extracted with methylene chloride and the organic phase was washed with water, dried over magnesium sulfate and filtered. The filtrate was evaporated to dryness under reduced pressure to obtain 1.1 g of raw product which was chromatographed over silica gel. Elution with a 7-3 chloroform-methanol mixture yielded 400 mg of cis N-methyl-5-[4-nitrophenoxy]-6,7,8,9-tetrahydro-5H-benzocyclohepten-7-amine. The said product was dissolved in ethyl acetate containing gaseous hydrogen chloride and 380 mg of the hydrochloride of the cis compound melting at 265° C. was recovered therefrom.

Workup

  1. temperaturethe mixture was refluxed for 31/2 hours
  2. distillationThe acetone was distilled under reduced pressure and 5 ml of N hydrochloric acid
  3. additionwere added to the residue
  4. extractionThe mixture was extracted with methylene chloride
  5. washthe organic phase was washed with water
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. customThe filtrate was evaporated to dryness under reduced pressure
  9. customto obtain 1.1 g of raw product which
  10. customwas chromatographed over silica gel
  11. washElution with a 7-3 chloroform-methanol mixture

Sources & evidence

ORD record
ord-4bd5f7802bc949ca8699b97d8b8e815e
Source dataset
uspto-grants-1979_12
Patent number
US04177292

Reaction notes

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