Methane → 4-(4-fluorophenyl)-2,6-diisopropyl-3,5-di(methoxy-carbonyl)-pyridine

HRID 1709656Notes

Reaction equation

HRID 1709656 reaction equation
[C:1]([C:5]1[CH:10]([C:11]2[CH:16]=[CH:15][C:14]([F:17])=[CH:13][CH:12]=2)[C:9]([C:18]([O:20][CH3:21])=[O:19])=[C:8]([CH:22]([CH3:24])[CH3:23])[NH:7][C:6]=1[CH:25]([CH3:27])[CH3:26])([O:3][CH3:4])=[O:2].[S].S.C>C1(C)C(C)=CC=CC=1.C(OCC)(=O)C>[C:1]([C:5]1[C:6]([CH:25]([CH3:27])[CH3:26])=[N:7][C:8]([CH:22]([CH3:23])[CH3:24])=[C:9]([C:18]([O:20][CH3:21])=[O:19])[C:10]=1[C:11]1[CH:12]=[CH:13][C:14]([F:17])=[CH:15][CH:16]=1)([O:3][CH3:4])=[O:2]

Participants

7

Reactant 4

HCID 297MethaneHCID 402Hydrogen SulfideHCID 5362487SulfurHCID 11199700DIMETHYL 1,4-DIHYDRO-2,6-DIISOPROPYL-4-(4-FLUOROPHENYL)-PYRIDINE-3,5-DICARBOXYLATE

Product 1

HCID 99695674-(4-fluorophenyl)-2,6-diisopropyl-3,5-di(methoxy-carbonyl)-pyridine

Reagents, catalysts & solvents 2

HCID 7237O-XyleneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 300 g dihydropyridine of Step 1 and 2 g freshly sublimed sulfur in 100 ml xylene was heated to 200°-210° C. for 30 minutes. When the development of hydrogen sulfide had subsided, the reaction mixture was cooled to room temperature, and ca. 100 g of Charcoal plus 1000 ml of ethyl acetate was added. This mixture was heated to reflux for 6 hours and then filtered through Celite filter aid. The filtrate was concentrated under vacuum and the residue was chromatographed on silica-gel, eluting with ethyl acetate/hexane to yield 78 g of the Step 2 title product.

Workup

  1. temperaturewas heated to 200°-210° C. for 30 minutes
  2. temperatureThis mixture was heated
  3. temperatureto reflux for 6 hours
  4. filtrationfiltered through Celite
  5. filtrationfilter aid
  6. concentrationThe filtrate was concentrated under vacuum
  7. customthe residue was chromatographed on silica-gel
  8. washeluting with ethyl acetate/hexane

Sources & evidence

ORD record
ord-7c3a1fd9776e4afb9750100289b2cbb6
Source dataset
uspto-grants-1990_08
Patent number
US04950675

Reaction notes

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