Ethylene Glycol → Diethyl 2-methyl-4-(2-nitrophenyl)-6-ethylenedioxymethyl-1,4-dihydropyridine-3,5-dicarboxylate

HRID 1759096ノート

反応式

HRID 1759096 の反応式
C[C:2]1[NH:3][C:4]([CH:27]=O)=[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].[CH2:29]([OH:32])[CH2:30][OH:31].[C:33]1(C)C=CC(S(O)(=O)=O)=CC=1>C1C=CC=CC=1>[CH3:27][C:4]1[N:3]2[O:32][CH2:29][CH2:30][O:31][C:2]2=[C:7]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[C:6]([CH3:33])([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=2[N+:19]([O-:21])=[O:20])[C:5]=1[C:22]([O:24][CH2:25][CH3:26])=[O:23]

参加物

5

反応物 3

HCID 174Ethylene GlycolHCID 6101p-Toluenesulfonic acidHCID 13388352Diethyl 2-methyl-4-(2-nitrophenyl)-6-formyl-1,4-dihydropyridine-3,5-dicarboxylate

生成物 1

HCID 70071585Diethyl 2-methyl-4-(2-nitrophenyl)-6-ethylenedioxymethyl-1,4-dihydropyridine-3,5-dicarboxylate

試薬・触媒・溶媒 1

HCID 241Benzene溶媒

実験手順

A mixture of diethyl 2-methyl-4-(2-nitrophenyl)-6-formyl-1,4-dihydropyridine-3,5-dicarboxylate (388.37 mg), ethylene glycol (186.21 mg) and p-toluenesulfonic acid (catalytic amount) in absolute benzene. (5 ml) was refluxed for 45 minutes under azeotropic dehydration. The reaction mixture was allowed to stand and washed twice with an aqueous solution of sodium bicarbonate. After removal of the solvent, the residue immediately turned into crystals. Thus obtained crystals were recrystallized from a mixture of ethanol and diisopropyl ether to give yellow pure crystals (0.32 g) of diethyl 2-methyl-4-(2-nitrophenyl)-6-ethylenedioxymethyl-1,4-dihydropyridine-3,5-dicarboxylate, m.p 152° to 153.5° C. (7) A mixture of diethyl 2-methyl-4-(2-nitrophenyl)-6-hydroxymethyl-1,4-dihydropyridine-3,5-dicarboxylate (1.9518 g) and triphenylphosphine (1.4425 g) in carbon tetrachloride (20 ml) was refluxed for 5 hours. After removal of the solvent, the residue was added to water and extracted with ethyl acetate. The extract was washed with water and dried. Removal of the solvent gave an orange-yellow oil (3.63 g). This oil was subjected to column chromatography on silica gel with an eluent (benzene:ethyl acetate=5:2) to give an oil (517 mg) of diethyl 2-methyl-4-(2-nitrophenyl)-6-chloromethyl-1,4-dihydropyridine-3,5-dicarboxylate.

後処理

  1. temperature(5 ml) was refluxed for 45 minutes under azeotropic dehydration
  2. washwashed twice with an aqueous solution of sodium bicarbonate
  3. customAfter removal of the solvent
  4. customThus obtained crystals were recrystallized from a mixture of ethanol and diisopropyl ether

出典と根拠

ORDレコード
ord-fa25d8ec634c4314ac60d153bab12675
出典データセット
uspto-grants-1982_07
特許番号
US04338322

反応ノート

読み込み中…