Hydrochloric Acid → HCID 13671866, compound

HRID 1655329Notes

Reaction equation

HRID 1655329 reaction equation
[NH2:1][CH2:2][CH2:3][CH2:4][N:5]1[CH2:10][CH2:9][CH2:8][CH2:7][CH2:6]1.S(=O)(O)O.[CH3:15][CH:16]([CH3:29])[CH2:17][CH2:18][C:19](=O)[C:20]([C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)=[O:21].BrC(CCC(C)C)C(C1C=CC=CC=1)=O.[ClH:45]>CO.CCO.[Zn]>[ClH:45].[ClH:45].[CH3:15][CH:16]([CH3:29])[CH2:17][CH2:18][CH:19]([NH:1][CH2:2][CH2:3][CH2:4][N:5]1[CH2:10][CH2:9][CH2:8][CH2:7][CH2:6]1)[CH:20]([C:22]1[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=1)[OH:21]

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 1100Sulfurous Acid2×HCID 19049Piperidine-1-propylamineHCID 19791677HCID 19791677, compoundHCID 197916815-Methyl-1-phenylhexane-1,2-dione

Product 1

HCID 13671866HCID 13671866, compoundYield 31%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalyst2×HCID 702EthanolSolvent2×HCID 887MethanolSolvent3×

Procedure

To a refluxing mixture of 1-(3-aminopropyl)piperidine (284 mg, 2 mmol), sulfurous acid (6% SO2 aqueous solution) (1.1 ml) and zinc dust (200 mg) in methanol (2.5 ml) was added dropwise over a period of 1 hour a solution of 5-methyl-1-phenylhexane-1,2-dione [bp: 104°-107° C./2 mmHg; prepared from 2-bromo-5-methyl-1-phenylhexan-1-one by a known method {N. Kornblum and H. W. Frazier: J. Am. Chem. Soc., 88, 865 (1966)}] (275 mg, 1.35 mmol) in methanol (1.0 ml). Thereafter, 200 mg of zinc dust and 1.8 ml of sulfurous acid were freshly added to the mixture and the resulting mixture was refluxed for further 2 hours. After cooling, methanol was added to the mixture and insoluble material was removed by filtration. The filtrate was concentrated under reduced pressure and the residue was dissolved in 2N-HCl. The resulting solution was washed three times with ether and then basified with an aqueous sodium hydroxide solution, followed by extraction with ether. The combined ethereal extract was washed twice with water, dried over anhydrous sodium sulfate and evaporated under reduced pressure to give 0.43 g of oily matter. To an ethanol solution of the matter was added 6N-HCl in EtOH (0.64 ml) and the solution was allowed to stand. Precipitated crystals were collected by filtration and washed with ethanol to obtain 170 mg of the title compound as white crystals (yield: 31%).

Workup

  1. temperaturethe resulting mixture was refluxed for further 2 hours
  2. temperatureAfter cooling
  3. customwas removed by filtration
  4. concentrationThe filtrate was concentrated under reduced pressure
  5. dissolutionthe residue was dissolved in 2N-HCl
  6. washThe resulting solution was washed three times with ether
  7. extractionfollowed by extraction with ether
  8. extractionThe combined ethereal extract
  9. washwas washed twice with water
  10. dry with materialdried over anhydrous sodium sulfate
  11. customevaporated under reduced pressure
  12. customto give 0.43 g of oily matter
  13. customPrecipitated crystals
  14. filtrationwere collected by filtration
  15. washwashed with ethanol

Sources & evidence

ORD record
ord-a9e63b33ffd74546a18c8ad74d18c7f2
Source dataset
uspto-grants-1993_10
Patent number
US05250546

Reaction notes

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