Toluene → HCID 19070359, compound

HRID 1955499Notes

Reaction equation

HRID 1955499 reaction equation
[CH2:1]([C:8]([N:25]([CH3:27])[CH3:26])([CH2:23][CH3:24])[C:9]([C:11]1[CH:16]=[CH:15][C:14]([N:17]2[CH2:22][CH2:21][O:20][CH2:19][CH2:18]2)=[CH:13][CH:12]=1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH2:28]([Si:31]([O:36][CH3:37])([O:34][CH3:35])[O:32][CH3:33])[CH:29]=C.[C:38]1(C)C=CC=CC=1>>[CH2:1]([C:8]([N:25]([CH3:27])[CH3:26])([CH2:23][CH3:24])[C:9]([C:11]1[CH:16]=[CH:15][C:14]([N:17]2[CH2:18][CH2:19][O:20][CH2:21][CH2:22]2)=[CH:13][C:12]=1[CH2:29][CH:28]([Si:31]([O:36][CH3:37])([O:34][CH3:35])[O:32][CH3:33])[CH3:38])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

4

Reactant 3

HCID 1140TolueneHCID 75698AllyltrimethoxysilaneHCID 861712-Benzyl-2-(dimethylamino)-1-(4-(morpholin-4-yl)phenyl)butan-1-one

Product 1

HCID 19070359HCID 19070359, compoundYield 4%

Procedure

5.49 g (15 mmol) of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 275 mg (0.3 mmol) of RuH2 (CO) (PPh3)3 and 5 g (30 mmol) of allyltrimethoxysilane were dissolved in 20 ml of toluene and degased with argon. After heating for 5 hours at reflux with stirring, the mixture was left to stand overnight, stirred at reflux for a further 9 hours, and again left to stand at room temperature. 280 mg (0.3 mmol) of RuH2 (CO) (PPh3)3 were added and the mixture was boiled for 9 hours; it was then again left to stand overnight, 260 mg (0.3 mmol) of RuH2 (CO)(PPh3)3 were added, and the whole mixture was boiled again for 9 hours. After the solvent had been distilled off, the product was chromatographed (silica gel, heptane/CH2Cl2 /ethyl acetate) and finally, by means of gel permeation chromatography (Sephadex LH-20, methanol) a pure fraction of 0.33 g (4%) of (11) was obtained as a yellow oil. 1H-NMR (CDCl3): 0.68 ppm (3H, t, Bu-H4, 3 JH,H =7.2 Hz); 0.77 ppm (mc, 2H, Prop-H3); 1.64-1.96 ppm (4H, m, Bu-H3 and Prop-H2); 2.38 ppm (6H, s, N(CH3)2); 2.64 ppm (2H, mc, Prop-H1); 3.16 ppm (2H, mc, CH2 -Ph); 3.24 ppm (4H, mc, morpholine-N --CH2); 3.57 ppm (9H, s, Si(OCH3)3); 3.85 ppm (4H, mc morpholine-O-CH2); 6.61 ppm (1H, dd, Ph-H5, 3 JH5H,6 =8.6 Hz); 6.72 ppm (1H, d, Ph-H3, 4JH3,H5 =2.4 Hz); 7.13-7.25 ppm (5H, m, Ph'-H); 8.38 ppm (1H, d, Ph-H6).

Workup

  1. customdegased with argon
  2. temperatureAfter heating for 5 hours
  3. temperatureat reflux
  4. waitthe mixture was left
  5. stirringstirred
  6. temperatureat reflux for a further 9 hours
  7. waitagain left
  8. customto stand at room temperature
  9. waitthe mixture was boiled for 9 hours
  10. waitit was then again left
  11. waitto stand overnight
  12. waitthe whole mixture was boiled again for 9 hours
  13. distillationAfter the solvent had been distilled off
  14. customthe product was chromatographed (silica gel, heptane/CH2Cl2 /ethyl acetate)

Sources & evidence

ORD record
ord-aa38039c1d4743c5a7c6eadcb9ab7622
Source dataset
uspto-grants-1998_07
Patent number
US05776658

Reaction notes

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