Toluene → 2-(3-Phenyl-3-aminopropyl)-3-carboethoxy-5-carbomethoxy-6-methyl-4-(m-nitrophenyl)-1,4-dihydropyridine

HRID 1461404ノート

反応式

HRID 1461404 の反応式
C1(C)C=CC=CC=1.[BH4-].[Na+].[C:10]1([CH:16]([N:44]=[N+]=[N-])[CH2:17][CH2:18][C:19]2[NH:20][C:21]([CH3:43])=[C:22]([C:39]([O:41][CH3:42])=[O:40])[CH:23]([C:30]3[CH:35]=[CH:34][CH:33]=[C:32]([N+:36]([O-:38])=[O:37])[CH:31]=3)[C:24]=2[C:25]([O:27][CH2:28][CH3:29])=[O:26])[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1>[Br-].C([P+](CCCC)(CCCC)CCCC)CCCCCCCCCCCCCCC.O>[C:10]1([CH:16]([NH2:44])[CH2:17][CH2:18][C:19]2[NH:20][C:21]([CH3:43])=[C:22]([C:39]([O:41][CH3:42])=[O:40])[CH:23]([C:30]3[CH:35]=[CH:34][CH:33]=[C:32]([N+:36]([O-:38])=[O:37])[CH:31]=3)[C:24]=2[C:25]([O:27][CH2:28][CH3:29])=[O:26])[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1

参加物

6

反応物 3

HCID 1140TolueneHCID 4311764Sodium borohydrideHCID 199804232-(3-Phenyl-3-azidopropyl)-3-carboethoxy-5-carbomethoxy-6-methyl-4-(m-nitrophenyl)-1,4-dihydropyridine

生成物 1

HCID 199804762-(3-Phenyl-3-aminopropyl)-3-carboethoxy-5-carbomethoxy-6-methyl-4-(m-nitrophenyl)-1,4-dihydropyridine

試薬・触媒・溶媒 2

HCID 84716Hexadecyltributylphosphonium bromide触媒HCID 962Water溶媒2 回

反応条件

温度
70 °C

実験手順

120 ml of water are added to a toluene suspension (120 ml) of sodium borohydride (30 g), hexadecyl-tributylphosphonium bromide (2.27 g) and 15 g of the less polar diastereoisomer of 2-(3-phenyl-3-azidopropyl)-3-carboethoxy-5-carbomethoxy-6 -methyl-4-(m-nitrophenyl)-1,4-dihydropyridine. The mixture is stirred for 24 hours at 70° C., then cooled to room temperature, poured into water (200 ml), extracted with ethylacetate (200 ml), washed with water up to pH 7, dried and evaporated under vacuum. The crude oil (15 g) is purified by chromatography (silice 450 g eluent ethylacetate) to give 7.69 g of the less polar diastereoisomer of 2-(3-phenyl-3-aminopropyl)-3-carboethoxy-5-carbomethoxy-6-methyl-4-(m-nitrophenyl)-1,4-dihydropyridine as a glassy foam. It is dissolved in AcoEt (35 ml) and 1.87 g of maleic acid are added to give 8.2 g of the maleate salt C26H29O6N3 ·C4H4O4 (bright yellow crystal): p.f. 149-152° C.

後処理

  1. temperaturecooled to room temperature
  2. extractionextracted with ethylacetate (200 ml)
  3. washwashed with water up to pH 7
  4. customdried
  5. customevaporated under vacuum
  6. customThe crude oil (15 g) is purified by chromatography (silice 450 g eluent ethylacetate)

出典と根拠

ORDレコード
ord-2bb48a4ac5f44c5cb188937735ddc4c4
出典データセット
uspto-grants-1991_12
特許番号
US05075324

反応ノート

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