Piperidine → HCID 131717169, compound

HRID 1534428Notes

Reaction equation

HRID 1534428 reaction equation
[C:1]12[CH:10]=[C:4]([CH2:5][C:6]=1[C:7](O)=O)[C:3]1[CH:11]=[CH:12][CH:13]=[CH:14][C:2]2=1.[NH:15]1[CH2:20][CH2:19][CH2:18][CH2:17][CH2:16]1.C(OP(C#N)(=O)OCC)C.C(N(CC)CC)C>O.CN(C)C=O>[C:1]12[CH2:10][C:4](=[CH:5][C:6]=1[CH2:7][N:15]1[CH2:20][CH2:19][CH2:18][CH2:17][CH2:16]1)[C:3]1[CH:11]=[CH:12][CH:13]=[CH:14][C:2]2=1

Participants

7

Reactant 4

HCID 8082PiperidineHCID 8471TriethylamineHCID 76257Diethyl cyanophosphonateHCID 131717170HCID 131717170, compound

Product 1

HCID 131717169HCID 131717169, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

2-Benzobicyclo[2.2.1]heptenecarboxylic acid (0.4 g) was combined with piperidine (1 ml), diethylcyanophosphonate (1 ml), triethylamine (2 ml) and dimethylformamide (10 ml) and stirred for 2 hours at room temperature. Water (15 ml) was added and the mixture was extracted with ether (3×15 ml). The combined ether solutions were washed with water (2×25 ml) and the ether solution was dried over magnesium sulfate and the ether removed on a rotary evaporator. The residue was combined with tetrahydrofuran (25 ml) and lithium aluminum hydride (0.2 g) and heated to reflux for 12 hours. The mixture was cooled in an ice bath, treated with ethanol (1 ml) and water (0.5 ml) and the solids were removed by filtration. The filtrate was concentrated on a rotary evaporator and the residue was dissolved in 6N HCl (20 ml). The acidic solution was washed with ether (2×25 ml) and the aqueous solution was made basic with 50% sodium hydroxide solution. The mixture was extracted with ether (3×25 ml) and the combined ether solutions were dried over magnesium sulfate and the ether removed on a rotary evaporator. The residue was distilled on a Kugelrohr apparatus (80° C. at 0.05 mm Hg) to provide the product as a colorless oil. Analytical data are reported in Table I.

Workup

  1. extractionthe mixture was extracted with ether (3×15 ml)
  2. washThe combined ether solutions were washed with water (2×25 ml)
  3. dry with materialthe ether solution was dried over magnesium sulfate
  4. customthe ether removed on a rotary evaporator
  5. temperatureheated
  6. temperatureto reflux for 12 hours
  7. temperatureThe mixture was cooled in an ice bath
  8. additiontreated with ethanol (1 ml) and water (0.5 ml)
  9. customthe solids were removed by filtration
  10. concentrationThe filtrate was concentrated on a rotary evaporator
  11. dissolutionthe residue was dissolved in 6N HCl (20 ml)
  12. washThe acidic solution was washed with ether (2×25 ml)
  13. extractionThe mixture was extracted with ether (3×25 ml)
  14. dry with materialthe combined ether solutions were dried over magnesium sulfate
  15. customthe ether removed on a rotary evaporator
  16. distillationThe residue was distilled on a Kugelrohr apparatus (80° C. at 0.05 mm Hg)

Sources & evidence

ORD record
ord-10bf71eeaad548b8965d122b37e7f41c
Source dataset
uspto-grants-1992_02
Patent number
US05089506

Reaction notes

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