Imidazole → 2-[2-(Tert-butyl-dimethyl-silanyloxy)-ethoxy]-6-chloro-3-nitro-pyridin-4-ylamine

HRID 570233Notes

Reaction equation

HRID 570233 reaction equation
[NH2:1][C:2]1[CH:7]=[C:6]([Cl:8])[N:5]=[C:4]([O:9][CH2:10][CH2:11][OH:12])[C:3]=1[N+:13]([O-:15])=[O:14].[C:16]([Si:20](Cl)([CH3:22])[CH3:21])([CH3:19])([CH3:18])[CH3:17].N1C=CN=C1.[NH4+].[Cl-]>C(Cl)Cl>[C:16]([Si:20]([CH3:22])([CH3:21])[O:12][CH2:11][CH2:10][O:9][C:4]1[C:3]([N+:13]([O-:15])=[O:14])=[C:2]([NH2:1])[CH:7]=[C:6]([Cl:8])[N:5]=1)([CH3:19])([CH3:18])[CH3:17]

Participants

6

Reactant 4

HCID 795ImidazoleHCID 25517Ammonium ChlorideHCID 28928tert-Butyldimethylsilyl chlorideHCID 866574142-(4-Amino-6-chloro-3-nitro-pyridin-2-yloxy)-ethanol

Product 1

HCID 866574152-[2-(Tert-butyl-dimethyl-silanyloxy)-ethoxy]-6-chloro-3-nitro-pyridin-4-ylamine

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a mixture of 2-(4-amino-6-chloro-3-nitro-pyridin-2-yloxy)-ethanol (4.40 g, 18.8 mmol, prepared as described in the previous step) and tert-butyl-chloro-dimethyl-silane (3.12 g, 20.7 mmol) in DCM (50 mL) was added imidazole (1.80 g, 26.4 mmol). After stirring at room temperature for 2 h, the resulting mixture was treated with saturated NH4Cl (50 mL) and extracted with EtOAc (3×50 mL). The combined organic layers were washed with H2O (3×50 mL), brine (50 mL), and dried over Na2SO4. The solvent was removed in vacuo and the residue was purified by flash chromatography on silica gel (0:100-20:80 EtOAc/hexane) to yield 2-[2-(tert-butyl-dimethyl-silanyloxy)-ethoxy]-6-chloro-3-nitro-pyridin-4-ylamine as a light yellow solid. 1H-NMR (400 MHz, CDCl3) δ: 6.35 (s, 1H), 6.17 (br. s., 2H), 4.49 (t, J=5.1 Hz, 2H), 3.96 (t, J=5.1 Hz, 2H), 0.88 (s, 9H), 0.08 (s, 6H).

Workup

  1. customprepared
  2. extractionextracted with EtOAc (3×50 mL)
  3. washThe combined organic layers were washed with H2O (3×50 mL), brine (50 mL)
  4. dry with materialdried over Na2SO4
  5. customThe solvent was removed in vacuo
  6. customthe residue was purified by flash chromatography on silica gel (0:100-20:80 EtOAc/hexane)

Sources & evidence

ORD record
ord-23912975686f47ae960587bbc5853d3a
Source dataset
uspto-grants-2015_05
Patent number
US09023846B2

Reaction notes

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