Benzoyl chloride → Diethyl 2-methyl-4-(2-nitrophenyl)-6-benzoyloxymethyl-1,4-dihydropyridine-3,5-dicarboxylate

HRID 614620Notes

Reaction equation

HRID 614620 reaction equation
[CH3:1][C:2]1[NH:3][C:4]([CH2:27][OH:28])=[C:5]([C:22]([O:24][CH2:25][CH3:26])=[O:23])[CH:6]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=2[N+:19]([O-:21])=[O:20])[C:7]=1[C:8]([O:10][CH2:11][CH3:12])=[O:9].[C:29](Cl)(=[O:36])[C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1>N1C=CC=CC=1.C(Cl)Cl>[CH3:1][C:2]1[NH:3][C:4]([CH2:27][O:28][C:29](=[O:36])[C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)=[C:5]([C:22]([O:24][CH2:25][CH3:26])=[O:23])[CH:6]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=2[N+:19]([O-:21])=[O:20])[C:7]=1[C:8]([O:10][CH2:11][CH3:12])=[O:9]

Participants

5

Reactant 2

HCID 7412Benzoyl chlorideHCID 133883402-Hydroxymethyl-6-methyl-4-(nitrophenyl)-3,5-diethoxycarbonyl-1,4-dihydropyridine

Product 1

HCID 13469475Diethyl 2-methyl-4-(2-nitrophenyl)-6-benzoyloxymethyl-1,4-dihydropyridine-3,5-dicarboxylate

Reagents, catalysts & solvents 2

HCID 1049PyridineSolvent2×HCID 6344DichloromethaneSolvent

Procedure

to a solution of diethyl 2-methyl-4-(2-nitrophenyl)-6-hydroxymethyl-1,4-dihydropyridine-3,5-dicarboxylate (1.95 g) in pyridine (25 ml) was dropwise added a solution of benzoyl chloride (2.0 g) in methylene chloride (5 ml) over 5 minutes at 5° to 6° C. with stirring. The resultant mixture was stirred for 15 minutes at the same temperature and then at room temperature for 2 hours, and followed by stirring at 50° C. for an hour and a half. After the reaction was over, the pyridine was distilled off and to the residue was added ethyl acetate and water. The ethyl acetate layer was separated, washed with dil. hydrochloric acid twice and then aqueous solution of sodium bicarbonate, and dried over magnesium sulfate. The solvent was removed and the residue was soon crystallized by treating with diethyl ether and collected by filtration. These crude crystals were washed with a mixture of diethyl ether and a small amount of ethyl acetate to give crystals, which was recrystallized from ethyl acetate (25 ml) to give powders of diethyl 2-methyl-4-(2-nitrophenyl)-6-benzoyloxymethyl-1,4-dihydropyridine-3,5-dicarboxylate, m.p. 156° to 157° C.

Workup

  1. stirringby stirring at 50° C. for an hour
  2. distillationwas distilled off and to the residue
  3. additionwas added ethyl acetate and water
  4. customThe ethyl acetate layer was separated
  5. washwashed with dil. hydrochloric acid twice
  6. dry with materialaqueous solution of sodium bicarbonate, and dried over magnesium sulfate
  7. customThe solvent was removed
  8. customthe residue was soon crystallized
  9. additionby treating with diethyl ether
  10. filtrationcollected by filtration
  11. washThese crude crystals were washed with a mixture of diethyl ether
  12. customa small amount of ethyl acetate to give crystals, which
  13. customwas recrystallized from ethyl acetate (25 ml)

Sources & evidence

ORD record
ord-b3c9a57210164d259e10ea04dace27d4
Source dataset
uspto-grants-1979_03
Patent number
US04145432

Reaction notes

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