Dimethyl Sulfoxide → 5H-Benzocyclohepten-7-amine, 6,7,8,9-tetrahydro-2-chloro-N,N-dimethyl-9-(4-nitrophenoxy)-, monohydrochloride, trans-

HRID 1447659Notes

Reaction equation

HRID 1447659 reaction equation
CS(C)=O.[H-].[Na+].[Cl:7][C:8]1[CH:22]=[CH:21][C:11]2[CH2:12][CH2:13][C@H:14]([N:18]([CH3:20])[CH3:19])[CH2:15][C@@H:16]([OH:17])[C:10]=2[CH:9]=1.Cl[C:24]1[CH:29]=[CH:28][C:27]([N+:30]([O-:32])=[O:31])=[CH:26][CH:25]=1>O>[ClH:7].[CH3:20][N:18]([CH3:19])[C@H:14]1[CH2:13][CH2:12][C:11]2[CH:21]=[CH:22][C:8]([Cl:7])=[CH:9][C:10]=2[C@H:16]([O:17][C:24]2[CH:29]=[CH:28][C:27]([N+:30]([O-:32])=[O:31])=[CH:26][CH:25]=2)[CH2:15]1

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 74741-Chloro-4-nitrobenzeneHCID 24758Sodium hydrideHCID 53733877HCID 53733877, compound

Product 1

HCID 30555475H-Benzocyclohepten-7-amine, 6,7,8,9-tetrahydro-2-chloro-N,N-dimethyl-9-(4-nitrophenoxy)-, monohydrochloride, trans-Yield 183.5%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
60 °C

Procedure

12 ml of anhydrous dimethylsulfoxide were added under nitrogen to 1.2 g of sodium hydride as a 50% oil dispersion and the mixture was stirred at 60° C. for 30 minutes and was then cooled to 25° C. 4.8 g of trans 3-chloro-7-dimethylamino-6,7,8,9-tetrahydro-5H-benzocyclohepten-5-ol were added thereto and the mixture was stirred for 15 minutes at 25° C. after which 6.3 g of p-chloronitrobenzene were added thereto. The mixture was stirred for one hour and 500 ml of water were added thereto. The mixture was extracted with methylene chloride and the organic phase was dried over magnesium sulfate and was evaporated to dryness under reduced pressure. The residue was taken up in 130 ml of N hydrochloric acid and after standing for 20 minutes, the mixture was vacuum filtered. The recovered product was washed with ether, then water and dried under vacuum to obtain 7.3 g of product which was crystallized from methanol and ethyl acetate to obtain 5 g of trans N,N-dimethyl-3-chloro-5-[4-nitrophenoxy]-6,7,8,9-tetrahydro-5H-benzocyclohepten-7-amino hydrochloride in the form of colorless crystals melting at 230° C.

Workup

  1. temperaturewas then cooled to 25° C
  2. additionwere added
  3. stirringThe mixture was stirred for one hour
  4. extractionThe mixture was extracted with methylene chloride
  5. dry with materialthe organic phase was dried over magnesium sulfate
  6. customwas evaporated to dryness under reduced pressure
  7. waitafter standing for 20 minutes
  8. filtrationfiltered
  9. washThe recovered product was washed with ether
  10. dry with materialwater and dried under vacuum

Sources & evidence

ORD record
ord-b4be42e86b804d779028d7ba1486ded3
Source dataset
uspto-grants-1979_12
Patent number
US04177292

Reaction notes

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