Sodium Chloride → HCID 13338336, compound

HRID 2417559Notes

Reaction equation

HRID 2417559 reaction equation
C([N:4]1[CH2:10][CH2:9][C:8]2[CH:11]=[CH:12][C:13]([Cl:15])=[CH:14][C:7]=2[CH2:6][CH2:5]1)(=O)C.C[S-:17].[Na+].[CH2:19](Br)[CH:20]=[CH2:21].[Cl-].[Na+].[OH-].[Na+]>CN(P(N(C)C)N(C)C)C.C(O)C.CCOCC>[ClH:15].[CH2:19]([S:17][C:13]1[CH:12]=[CH:11][C:8]2[CH2:9][CH2:10][NH:4][CH2:5][CH2:6][C:7]=2[CH:14]=1)[CH:20]=[CH2:21]

Participants

9

Reactant 5

HCID 5234Sodium ChlorideHCID 7841Allyl bromideHCID 14798Sodium HydroxideHCID 4378561Sodium methanethiolateHCID 21822928HCID 21822928, compound

Product 1

HCID 13338336HCID 13338336, compound

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 3283Diethyl EtherSolventHCID 15355Hexamethylphosphorous triamideSolvent

Procedure

A solution of 4.02 g [0.018 mol, B. Pecherer et. al., J. Het. Chem. 8, 779 (1971)] of 3-acetyl-7-chloro-2,3,4,5-tetrahydro-1H-3-benzazepine and 3.78 g (0.054 mol) of sodium thiomethoxide in 37.5 ml of hexamethylphosphorus triamide was heated to 125° for 4 hours. The mixture was cooled in an ice bath and treated with 4.36 g (0.036 mol) of allyl bromide. The mixture was allowed to warm to room temperature and stirred overnight. It was poured into 375 ml of saturated sodium chloride and extracted with ether. The combined ether extracts were washed with water (3×100 ml), dried over anhydrous sodium sulfate and concentrated. The residue was chromatographed over silica gel, eluting with ethyl acetate, to give a solid which was recrystallized from cyclohexane to give off-white crystals; m.p. 73°-74°. This was dissolved in ethanol and aqueous 20% sodium hydroxide and heated at reflux for 24 hours. The solution was poured into ice-water and extracted with methylene chloride. The methylene chloride was dried and evaporated to leave a residue which was taken up in ether and precipitated by the addition of ethereal hydrogen chloride. The resulting salt was removed by filtration and, then, recrystallized from isopropanol to give white crystals of 7-allylthio-2,3,4,5-tetrahydro-1H-3-benzazepine hydrochloride; m.p. 150°-151°.

Workup

  1. temperatureThe mixture was cooled in an ice bath
  2. extractionextracted with ether
  3. washThe combined ether extracts were washed with water (3×100 ml)
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationconcentrated
  6. customThe residue was chromatographed over silica gel
  7. washeluting with ethyl acetate
  8. customto give a solid which
  9. customwas recrystallized from cyclohexane
  10. customto give off-white crystals
  11. temperatureat reflux for 24 hours
  12. extractionextracted with methylene chloride
  13. dry with materialThe methylene chloride was dried
  14. customevaporated
  15. customto leave a residue which
  16. customprecipitated by the addition of ethereal hydrogen chloride
  17. customThe resulting salt was removed by filtration
  18. customrecrystallized from isopropanol

Sources & evidence

ORD record
ord-db3d9c0d809b49a3b964a45712930f3e
Source dataset
uspto-grants-1984_09
Patent number
US04469634

Reaction notes

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