Phosphorus oxychloride → HCID 19043054, compound

HRID 1683195Notes

Reaction equation

HRID 1683195 reaction equation
C(NCC[C:6]1[C:11]2[CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][C:10]=2[CH:9]=[CH:8][CH:7]=1)=O.P(Cl)(Cl)(Cl)=O.[CH3:22][O:23][C:24]1[CH:29]=[CH:28][C:27]([S:30]([CH2:33][CH3:34])(=[O:32])=[O:31])=[CH:26][C:25]=1[C:35]1[NH:36][CH:37]=[CH:38][CH:39]=1.[BH4-].[Na+]>ClCCCl.O.CO>[C:6]1([N:36]([CH2:37][C:37]2[NH:36][C:35]([C:25]3[CH:26]=[C:27]([S:30]([CH2:33][CH3:34])(=[O:31])=[O:32])[CH:28]=[CH:29][C:24]=3[O:23][CH3:22])=[CH:39][CH:38]=2)[CH2:35][CH3:25])[C:11]2[CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][C:10]=2[CH:9]=[CH:8][CH:7]=1

Participants

8

Reactant 4

HCID 24813Phosphorus oxychlorideHCID 4311764Sodium borohydrideHCID 139003532-[5-(Ethanesulfonyl)-2-methoxyphenyl]-1H-pyrroleHCID 86750935HCID 86750935, compound

Product 1

HCID 19043054HCID 19043054, compoundYield 207.2%

Reagents, catalysts & solvents 3

HCID 111,2-DichloroethaneSolvent2×HCID 887MethanolSolventHCID 962WaterSolvent2×

Procedure

N-Formyl-N-(benzocycloheptan-1-yl)ethylamine (0.39 g, 1.81 mmol) was treated with phosphorus oxychloride (0.17 ml, 1.81 mmol) at room temperature under argon. After 30 minutes, 1,2-dichloroethane (1.2 ml) was added at 0° C. followed by a solution of 2-(2-methoxy-5-ethylsulfonylphenyl)-1H-pyrrole (0.4 g, 1.51 mmol) in 1,2-dichloroethane (4 ml). The mixture was allowed to warm to room temperature and stirred for 16 h at 25° C. and then for 6 h at 40° C. Sodium borohydride (0.55 g, 14.5 mmol) was then added at 0° C., and the reaction mixture was warmed to room temperature and stirred for 3 h. Water (2.4 ml) and then methanol (2.4 ml) were added dropwise. More water (30 ml) was added and the borane complex was extracted with dichloromethane (3×30 ml). The combined organics were dried (Na2SO4) and evaporated to an oil which was then treated with methanol (4.8 ml) and conc. HCl (2.4 ml) at room temperature for 16 h. The mixture was diluted with water (25 ml) and basified with 40% aqueous NaOH. Extraction into dichloromethane (3×30 ml), followed by drying (Na2SO4) and evaporation of the organic extracts gave an orange oil (0.73 g). The crude material was purified by chromatography on silica eluting with ethyl acetate (20-50%)--hexane, to give the title compound as an orange oil (0.31 g, 44%)

Workup

  1. waitfor 6 h at 40° C
  2. temperaturethe reaction mixture was warmed to room temperature
  3. stirringstirred for 3 h
  4. extractionthe borane complex was extracted with dichloromethane (3×30 ml)
  5. dry with materialThe combined organics were dried (Na2SO4)
  6. customevaporated to an oil which
  7. additionwas then treated with methanol (4.8 ml) and conc. HCl (2.4 ml) at room temperature for 16 h
  8. additionThe mixture was diluted with water (25 ml)
  9. extractionExtraction into dichloromethane (3×30 ml)
  10. customby drying
  11. custom(Na2SO4) and evaporation of the organic extracts

Sources & evidence

ORD record
ord-edaa01d2f61948dd80950de85b8fcbc5
Source dataset
uspto-grants-1997_06
Patent number
US05637609

Reaction notes

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