Allyl bromide → HCID 13338340, compound

HRID 2417562Notes

Reaction equation

HRID 2417562 reaction equation
CN(P(N(C)C)N(C)C)C.[Cl:11][C:12]1[C:22]2[CH2:21][CH2:20][N:19]([CH3:23])[CH2:18][CH2:17][C:16]=2[CH:15]=[CH:14][CH:13]=1.C[S-:25].[Na+].[CH2:27](Br)[CH:28]=[CH2:29]>[Cl-].[Na+].O>[ClH:11].[CH2:27]([S:25][C:12]1[C:22]2[CH2:21][CH2:20][N:19]([CH3:23])[CH2:18][CH2:17][C:16]=2[CH:15]=[CH:14][CH:13]=1)[CH:28]=[CH2:29]

Participants

6

Reactant 4

HCID 7841Allyl bromideHCID 15355Hexamethylphosphorous triamideHCID 123981BenalfocinHCID 4378561Sodium methanethiolate

Product 1

HCID 13338340HCID 13338340, compound

Reagents, catalysts & solvents 1

HCID 57417360Sodium chloride; waterSolvent

Procedure

Into 10 ml of hexamethylphosphorus triamide was dissolved 784 mg (4 mmol) of 6-chloro-2,3,4,5-tetrahydro-3-methyl-1H-3-benzazepine and 840 mg (12 mmol) of sodium thiomethoxide. The reaction was heated to 125° for 4 hours, cooled to ice-bath temperature and 968 mg (18 mmol) of allyl bromide was added in one portion. The mixture was warmed to room temperature and stirred overnight. It was poured into 75 ml of brine and extracted with three 75 ml portions of ether. The combined extracts were washed with three 50 ml portions of water, dried over magnesium sulfate and treated with excess ethereal hydrogen chloride. The solvent was reduced to 10 ml and decanted from an insoluble oil. The oil was triturated with 10 ml ether which was removed and discarded. The residue was taken up in hot ethanol, diluted with ether and allowed to crystallize. The precipitate was removed and recrystallized from acetonitrile to give 6-allylthio-3-methyl-2,3,4,5-tetrahydro-1H-3-benzazepine hydrochloride, as white crystals, m.p. 158°-160°.

Workup

  1. temperatureThe reaction was heated to 125° for 4 hours
  2. additionwas added in one portion
  3. extractionextracted with three 75 ml portions of ether
  4. washThe combined extracts were washed with three 50 ml portions of water
  5. dry with materialdried over magnesium sulfate
  6. additiontreated with excess ethereal hydrogen chloride
  7. customdecanted from an insoluble oil
  8. customThe oil was triturated with 10 ml ether which
  9. customwas removed
  10. additiondiluted with ether
  11. customto crystallize
  12. customThe precipitate was removed
  13. customrecrystallized from acetonitrile

Sources & evidence

ORD record
ord-eabd6f5678e24512b027abaf2d19aaff
Source dataset
uspto-grants-1984_09
Patent number
US04469634

Reaction notes

Loading…