Lithium Carbonate → HCID 22620209, compound

HRID 840667Notes

Reaction equation

HRID 840667 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][CH3:20])=[O:7])([CH3:4])([CH3:3])[CH3:2].C(=O)([O-])[O-].[Li+].[Li+].[H][H]>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][CH3:20])=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 3

HCID 11125Lithium CarbonateHCID 22620189HCID 22620189, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 22620209HCID 22620209, compoundYield 98%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Procedure

To a stirred solution of 1-(tert-Butoxycarbonyl)-4-chloro-6-methyl-2-n-pentyl-1,2-dihydropyridine (3.48 g, 11.61 mmol) in 220 mL of MeOH at 0° C. was added of lithium carbonate 0.857 g, 11.61 mmol) followed by 5% Pd/C. The mixture was placed under a positive pressure of hydrogen gas from a balloon, and the reaction progress was monitored by removing aliquots with a syringe, concentrating the aliquot in vacuo, and examining its 1H NMR spectrum. Upon completion, the mixture was filtered through Celite and evaporated. The residue was dissolved in ether (100 mL) and water (50 mL) was added, and the aqueous phase was extracted twice with ether. The combined organic extracts were washed with 1M NaOH and brine. The organic phase was dried with potassium carbonate, filtered through Celite, and concentrated in vacuo to give the crude product. Purification by column chromatography (silica gel, 5% EtOAc in hexanes) afforded 3.04 g (98%) of the product which was homogeneous by TLC analysis. 1H NMR (300 MHz) d 4.86 (br s, 1 H), 4.39-4.31 (m, 1 H), 2.02 (s, 3 H), 1.98-1.92 (m, 2 H), 1.91-1.28 (m, 21 H), 0.9-0.85 (t, 3 H); 13C NMR (75 MHz) 153.8 (s), 132.5 (s), 110.9 (s), 79.9 (s), 51.9 (s), 31.7 (s), 29.4 (s), 28.3 (s), 26.0 (s), 25.8 (s), 23.1 (s), 22.6 (s), 19.5 (s), 13.9 (s) ppm. FT-IR (neat) 2956, 2927, 2856, 1693, 1658, 1454, 1349, 1253, 1169, 1124, 1072 cm−1.

Workup

  1. customby removing aliquots with a syringe
  2. concentrationconcentrating the aliquot in vacuo
  3. filtrationUpon completion, the mixture was filtered through Celite
  4. customevaporated
  5. dissolutionThe residue was dissolved in ether (100 mL)
  6. additionwater (50 mL) was added
  7. extractionthe aqueous phase was extracted twice with ether
  8. washThe combined organic extracts were washed with 1M NaOH and brine
  9. dry with materialThe organic phase was dried with potassium carbonate
  10. filtrationfiltered through Celite
  11. concentrationconcentrated in vacuo
  12. customto give the crude product
  13. customPurification by column chromatography (silica gel, 5% EtOAc in hexanes)

Sources & evidence

ORD record
ord-099f8c707b6c41de8f9d60fc0e1f25ea
Source dataset
uspto-grants-2002_04
Patent number
US06369078B1

Reaction notes

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