4-Toluenesulfonyl chloride → HCID 13388351, compound

HRID 894697Notes

Reaction equation

HRID 894697 reaction equation
[CH3:1][C:2]1[NH:3][C:4]([CH2:25][OH:26])=[C:5]([C:20]([O:22][CH2:23][CH3:24])=[O:21])[CH:6]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=2[Cl:19])[C:7]=1[C:8]([O:10][CH2:11][CH3:12])=[O:9].C1(C)C=CC(S(Cl)(=O)=O)=CC=1>N1C=CC=CC=1>[CH3:1][C:2]1[NH:3][C:4]([CH:25]=[O:26])=[C:5]([C:20]([O:22][CH2:23][CH3:24])=[O:21])[CH:6]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=2[Cl:19])[C:7]=1[C:8]([O:10][CH2:11][CH3:12])=[O:9]

Participants

4

Reactant 2

HCID 73974-Toluenesulfonyl chlorideHCID 13388338HCID 13388338, compound

Product 1

HCID 13388351HCID 13388351, compoundYield 17%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent2×

Conditions

Temperature
80 °C

Procedure

Stirring a solution of diethyl 2-methyl-4-(2-chlorophenyl)-6-hydroxymethyl-1,4-dihydropyridine-3,5-dicarboxylate (1.1395 g) in dried pyridine (10 ml) at room temperature, a solution of p-toluenesulfonyl chloride (629.1 mg) in dried pyridine (10 ml) was dropwise added gradually thereto. The resultant mixture was stirred at room temperature for 1.5 hours and then heated at 80° C. for 4.5 hours with stirring. After removal of the pyridine, water was added to the residue and the resultant aqueous mixture was acidified with dil. hydrochloric acid and extracted twice with ethyl acetate. The extract was washed with dil. hydrochloric acid and then water, and dried. The resultant brown viscous oil was purified by column chromatography on silica-gel using an eluent (benzene:diethyl ether=1:1) to give an orange oil, which was crystallized by treating with diethyl ether. The resultant crystals were collected by filtration and recrystallized from a mixture of diethyl ether and n-hexane to give orange-yellowish prisms (0.1926 g) of diethyl 2-methyl-4-(2-chlorophenyl)-6-formyl-1,4-dihydropyridine-3,5-dicarboxylate, m.p. 87° to 88° C., which was identified with an authentic sample.

Workup

  1. customAfter removal of the pyridine, water
  2. additionwas added to the residue
  3. extractionextracted twice with ethyl acetate
  4. washThe extract was washed with dil. hydrochloric acid
  5. dry with materialwater, and dried
  6. customThe resultant brown viscous oil was purified by column chromatography on silica-gel
  7. customto give an orange oil, which
  8. customwas crystallized
  9. additionby treating with diethyl ether
  10. filtrationThe resultant crystals were collected by filtration
  11. customrecrystallized from a mixture of diethyl ether and n-hexane

Sources & evidence

ORD record
ord-99a170ab946442f380dacca00a57f531
Source dataset
uspto-grants-1981_08
Patent number
US04284634

Reaction notes

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