Sodium Hydroxide → 3-(4-Amino-3-methoxy-phenyl)-3-(3,4,5-trimethoxy-phenyl)-acrylonitrile

HRID 971004Notes

Reaction equation

HRID 971004 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([C:12]([C:16]2[CH:21]=[C:20]([O:22][CH3:23])[C:19]([O:24][CH3:25])=[C:18]([O:26][CH3:27])[CH:17]=2)=[CH:13][C:14]#[N:15])[CH:6]=[CH:7][C:8]=1[N+:9]([O-])=O.O.O.[Sn](Cl)(Cl)(Cl)Cl.[OH-].[Na+]>C(O)C>[NH2:9][C:8]1[CH:7]=[CH:6][C:5]([C:12]([C:16]2[CH:21]=[C:20]([O:22][CH3:23])[C:19]([O:24][CH3:25])=[C:18]([O:26][CH3:27])[CH:17]=2)=[CH:13][C:14]#[N:15])=[CH:4][C:3]=1[O:2][CH3:1]

Participants

5

Reactant 3

HCID 14798Sodium HydroxideHCID 692040173-(3-Methoxy-4-nitro-phenyl)-3-(3,4,5-trimethoxy-phenyl)-acrylonitrileHCID 85782573Tin tetrachloride dihydrate

Product 1

HCID 692050643-(4-Amino-3-methoxy-phenyl)-3-(3,4,5-trimethoxy-phenyl)-acrylonitrileYield 49%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
70 °C

Procedure

A suspension of 3-(3-methoxy-4-nitro-phenyl)-3-(3,4,5-trimethoxy-phenyl)-acrylonitrile (0.9 g, 2.4 mmol) and tin chloride dihydrate (4.0 g, 17.7 mmol) in ethanol (25 mL) was heated at 70° C. for 1 h. The mixture was cooled and poured into ice (200 mL). The pH was made strongly alkaline by the addition of ION NaOH. The mixture was extracted with EtOAc (5×50 mL) and the combined organic extracts were washed with water (40 mL), brine (40 mL), and dried (MgSO4). Solvent was removed and the residue was purified by flash chromatography (silica gel, Hexane:EtOAc 1:1) to afford mixture isomers of 3-(4-amino-3-methoxy-phenyl)-3-(3,4,5-trimethoxy-phenyl)-acrylonitrile (0.4 g, 42%) as a yellow solid: mp 123-125° C.; 1H NMR (CDCl3) δ 7.05-6.53 (m, 5H), 5.56(5.43) (s, 1H), 4.12 (s, 2H), 3.91-3.81 (m, 12H); 13C NMR (CDCl3) δ 163.19, 163.09, 152.99, 152.93, 146.63, 139.82, 138.74, 135.43, 132.66, 128.33, 126.35, 124.12, 118.96, 113.76, 113.74, 111.99, 110.22, 107.35, 106.42, 91.14, 90.52, 60.94, 56.28, 56.25, 55.74, 55.59; Anal Calcd for C19H20N2O4: C, 67.05; H, 5.92; N, 8.23. Found: c, 66.92; H, 5.76; N, 8.10.

Workup

  1. temperatureThe mixture was cooled
  2. extractionThe mixture was extracted with EtOAc (5×50 mL)
  3. washthe combined organic extracts were washed with water (40 mL), brine (40 mL)
  4. dry with materialdried (MgSO4)
  5. customSolvent was removed
  6. customthe residue was purified by flash chromatography (silica gel, Hexane:EtOAc 1:1)

Sources & evidence

ORD record
ord-03ffd68ae94048cc973ac7bebc7b15dc
Source dataset
uspto-grants-2007_12
Patent number
US07312241B2

Reaction notes

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