Imidazole → tert-Butyl-[2-chloro-5-(2-nitro-vinyl)-benzyloxy]-dimethyl-silane

HRID 1715411Notes

Reaction equation

HRID 1715411 reaction equation
C([SiH2][O:6][C:7](C)(C)[C:8]1[CH:9]=[C:10]([CH:13]=[CH:14][C:15]=1[Cl:16])[CH:11]=O)(C)(C)C.C([O-])(=O)C.[NH4+].[N+:24]([CH3:27])([O-:26])=[O:25].N1C=CN=C1.[CH3:33][C:34]([Si:37](Cl)([CH3:39])[CH3:38])([CH3:36])[CH3:35].[NH4+].[Cl-]>CC(O)=O>[C:34]([Si:37]([O:6][CH2:7][C:8]1[CH:9]=[C:10]([CH:11]=[CH:27][N+:24]([O-:26])=[O:25])[CH:13]=[CH:14][C:15]=1[Cl:16])([CH3:39])[CH3:38])([CH3:36])([CH3:35])[CH3:33]

Participants

8

Reactant 6

HCID 795ImidazoleHCID 6375NitromethaneHCID 25517Ammonium ChlorideHCID 28928tert-Butyldimethylsilyl chlorideHCID 517165Ammonium AcetateHCID 1373299173-(tert-Butyl-dimethyl-silanyloxymethyl)-4-chloro-benzaldehyde

Product 1

HCID 67148453tert-Butyl-[2-chloro-5-(2-nitro-vinyl)-benzyloxy]-dimethyl-silaneYield 59%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

A mixture of 3-(tert-butyl-dimethyl-silanyloxymethyl)-4-chloro-benzaldehyde (14.0 g, 49.1 mmol) and ammonium acetate (3.79 g, 49.1 mmol) in nitromethane (8.19 mL, 152 mmol) and AcOH (39 mL) was heated to reflux for 3 h. The mixture was allowed to cool to rt, and was poured onto water. The resulting mixture was extracted several times with EtOAc. The combined org. extracts were washed with water and aq. sat. NaHCO3 several times. The org. layer was dried over MgSO4, filtered, and the solvents were removed under reduced pressure. The residue was dried under high vacuum overnight, and was dissolved in DMF (217 mL). The sol. was cooled to 0° C., and imidazole (8.36 g, 123 mmol) and TBDMS-Cl (8.84 g, 58.6 mmol) were added. The mixture was stirred for 2 h at 0° C., and was poured onto aq. sat. NH4Cl. The resulting mixture was extracted with EtOAc several times. The combined org. extracts were washed with water and brine. The org. layer was dried over MgSO4, filtered, and the solvents were removed under reduced pressure. Purification of the crude by FC (EtOAc/heptane 2:8) yielded the title compound (9.50 g, 59%). LC-MS: tR=1.18 min.

Workup

  1. temperaturewas heated
  2. temperatureto reflux for 3 h
  3. additionwas poured onto water
  4. extractionThe resulting mixture was extracted several times with EtOAc
  5. washextracts were washed with water and aq. sat. NaHCO3 several times
  6. dry with materiallayer was dried over MgSO4
  7. filtrationfiltered
  8. customthe solvents were removed under reduced pressure
  9. customThe residue was dried under high vacuum overnight
  10. dissolutionwas dissolved in DMF (217 mL)
  11. temperatureThe sol. was cooled to 0° C.
  12. extractionThe resulting mixture was extracted with EtOAc several times
  13. washextracts were washed with water and brine
  14. dry with materiallayer was dried over MgSO4
  15. filtrationfiltered
  16. customthe solvents were removed under reduced pressure
  17. customPurification of the crude by FC (EtOAc/heptane 2:8)

Sources & evidence

ORD record
ord-6792f23eee2a48f3b2c02b9c109b92ba
Source dataset
uspto-grants-2010_09
Patent number
US07799805B2

Reaction notes

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