HCID 57365541, compound → HCID 14350178, compound

HRID 1598793Notes

Reaction equation

HRID 1598793 reaction equation
[N:1]1([CH:6]2[CH2:11][CH2:10][CH2:9][CH2:8][C:7]2=[N:12]O)[CH2:5][CH2:4][CH2:3][CH2:2]1>CC(OCC1C2C(=CC=CC=2)C(COC(C)=O)=C2C=1C=CC=C2)=O.O=[Pt]=O>[N:1]1([C@H:6]2[CH2:11][CH2:10][CH2:9][CH2:8][C@H:7]2[NH2:12])[CH2:2][CH2:3][CH2:4][CH2:5]1

Participants

4

Reactant 1

HCID 57365541HCID 57365541, compound

Product 1

HCID 14350178HCID 14350178, compound

Reagents, catalysts & solvents 2

HCID 345198Adams' catalystCatalystHCID 613145Acetic acid 10-acetoxymethyl-anthracen-9-ylmethyl esterSolvent

Procedure

2-(1-pyrrolidinyl)cyclohexanone oxime (c) (22.95 g, 0.105 mol) was dissolved in glacial acetic: acid (120 mL), PtO2 (1 g) was added and the mixture was hydrogenated at 45 psi for 96 hours. During this time, the catalyst was filtered and renewed every 24 hours. The reaction was followed by gas chromatography. The PtO2 was removed by filtration of the reaction mixture through celite and excess concentrated HCl was added. The solvent was removed in vacuo at 40°-50° C. and the resulting hydrochloride salt was dissolved in 100 mL of water. This aqueous solution was carefully basified to 30% w/v with pellets of NaOH and extracted with CHCl3 (5×50 mL). The organic layer was dried (Na2SO4), and the solvent was removed in vacuo. The crude amine was distilled under high vacuum to yield 13.7 g of (±)-(78%) as a colorless unstable oil. bp: 94° C./0.05 mmHg. Ir (film): 3380, 3300, 2940, 1590, 1440, 1125, 835 cm-1. (±)-d.HCl crystallized slowly from 2-propanol as small conglomerates: mp 263°-265° C. 1H-NMR (free base) (CDCl3): d 1.00-1.18 (m, 1H), 1.20-1.40 (m, 5H), 1.50-1.68 (m, 6H), 1.74 (t, J=3.5 Hz, 1H), 1.78 (t, J=3.5 Hz, 1H), 2.30-2.48 (m, 4H), 3.08 (br s, 2H). EIms (m/z, rel. int.): 168 (31, M+), 110 (100), 97 (42), 84 (92), 70 (33). Anal. Calcd. for C10 H22N2Cl2 : C 49.79, H 9.19, N 11.62; Found: C 49.82, H 9.19, N 11.67.

Workup

  1. filtrationDuring this time, the catalyst was filtered
  2. waitrenewed every 24 hours
  3. customThe PtO2 was removed by filtration of the reaction mixture through celite and excess concentrated HCl
  4. additionwas added
  5. customThe solvent was removed in vacuo at 40°-50° C.
  6. dissolutionthe resulting hydrochloride salt was dissolved in 100 mL of water
  7. extractionextracted with CHCl3 (5×50 mL)
  8. dry with materialThe organic layer was dried (Na2SO4)
  9. customthe solvent was removed in vacuo
  10. distillationThe crude amine was distilled under high vacuum
  11. customto yield 13.7 g of (±)-(78%) as a colorless unstable oil
  12. customHCl crystallized slowly from 2-propanol as small conglomerates

Sources & evidence

ORD record
ord-c1544d25bad844f5a9fd0f3448f29752
Source dataset
uspto-grants-1998_04
Patent number
US05739158

Reaction notes

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