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

HRID 1461404

Reaction equation

HRID 1461404 reaction equation
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

Participants

6

Reactant 3

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

Product 1

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

Reagents, catalysts & solvents 2

HCID 84716Hexadecyltributylphosphonium bromideCatalystHCID 962WaterSolvent2×

Conditions

Temperature
70 °C

Procedure

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.

Workup

  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)

Sources & evidence

ORD record
ord-2bb48a4ac5f44c5cb188937735ddc4c4
Source dataset
uspto-grants-1991_12
Patent number
US05075324

Linked notes

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