Lithium Carbonate → HCID 14892358, compound

HRID 840663Notes

Reaction equation

HRID 840663 reaction equation
[C:1]([O:5][C:6]([N:8]1[C:13]([CH3:14])=[CH:12][C:11](Cl)=[CH:10][CH:9]1[CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH3:26])=[O:7])([CH3:4])([CH3:3])[CH3:2].C(=O)([O-])[O-].[Li+].[Li+]>CO.[Pd]>[C:1]([O:5][C:6]([N:8]1[C:13]([CH3:14])=[CH:12][CH2:11][CH2:10][CH:9]1[CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH3:26])=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 2

HCID 11125Lithium CarbonateHCID 14892337HCID 14892337, compound

Product 1

HCID 14892358HCID 14892358, compoundYield 70%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Procedure

To a stirred solution of 2.17g, (5.65 mmol) of 1-(tert-Butoxycarbonyl)-4-chloro-6-methyl-2-n-undecyl-1,2-dihydropyridine in 120 mL of MeOH at 0° C. was added 0.422 g (5.71 mmol) of lithium carbonate followed by of 5% Pd/C. The flask was evacuated and filled with hydrogen repeatedly. The system was placed under positive pressure from a balloon, and the reaction was monitored by removing aliquots with a syringe, concentrating the aliquot in vacuo, and examing its 1H NMR spectrum. Upon completion, the mixture was filtered through Celite, and concentrated by evaporation. The residue was dissolved in ether (20 mL), water(20 mL) was added, and the aqueous phase was extracted twice with ether(2×10 mL). The combined organic extracts were washed with 1M NaOH(2×20ml) and brine. The organic products were dried over K2CO3, filtered through Celite, and concentrated in vacuo to give the crude product. Purification by column chromatography, (silica gel, 10% ether in hexanes) afforded 1.35 g (70%) the product as a light yellow oil which was homogeneous by TLC analysis. 1H NMR (300 MHz) δ4.75 (br s, 1 H), 4.62 (m, 1 H), 2.21 (s, 3 H), 1.91-1.64 (m, 4 H), 1.52 (s, 9 H), 1.28 (br s, 20 H), 0.90 (t, 3H); 13C NMR (75 MHz) 154.1 (s), 133.5 (s), 110.4 (s), 79.6 (s), 52.1 (s), 32.3 (s), 30.1 (s), 30.0 (s), 29.9 (s), 28.5 (s), 26.7 (s), 23.5 (s), 23.2 (s), 19.8 (s), 14.4 (s) ppm. FT-IR (neat) 2928, 2860, 1694, 1457, 1368, 1352, 1168, 1124, 1095, 1073 cm−1.

Workup

  1. customThe flask was evacuated
  2. additionfilled with hydrogen repeatedly
  3. customby removing aliquots with a syringe
  4. concentrationconcentrating the aliquot in vacuo
  5. filtrationUpon completion, the mixture was filtered through Celite
  6. concentrationconcentrated by evaporation
  7. dissolutionThe residue was dissolved in ether (20 mL)
  8. additionwater(20 mL) was added
  9. extractionthe aqueous phase was extracted twice with ether(2×10 mL)
  10. washThe combined organic extracts were washed with 1M NaOH(2×20ml) and brine
  11. dry with materialThe organic products were dried over K2CO3
  12. filtrationfiltered through Celite
  13. concentrationconcentrated in vacuo
  14. customto give the crude product
  15. customPurification by column chromatography, (silica gel, 10% ether in hexanes)

Sources & evidence

ORD record
ord-05179f815e294a7c853ae88d32856d88
Source dataset
uspto-grants-2002_04
Patent number
US06369078B1

Reaction notes

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