Hydrochloric Acid → HCID 58368604, compound

HRID 1192514Notes

Reaction equation

HRID 1192514 reaction equation
Cl.O.[Cl-].[NH4+].[Cl:5][C:6]1[CH:7]=[C:8]([C:28]([O:30][CH3:31])=[O:29])[C:9]([C:21]2[CH:26]=[CH:25][CH:24]=[C:23]([F:27])[CH:22]=2)=[C:10]([N+:18]([O-])=O)[C:11]=1[C:12]#[C:13][Si:14]([CH3:17])([CH3:16])[CH3:15]>CO.[Fe]>[NH2:18][C:10]1[C:11]([C:12]#[C:13][Si:14]([CH3:16])([CH3:15])[CH3:17])=[C:6]([Cl:5])[CH:7]=[C:8]([C:28]([O:30][CH3:31])=[O:29])[C:9]=1[C:21]1[CH:26]=[CH:25][CH:24]=[C:23]([F:27])[CH:22]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 962Water2×HCID 25517Ammonium ChlorideHCID 58368582HCID 58368582, compound

Product 1

HCID 58368604HCID 58368604, compoundYield 86%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 887MethanolSolvent

Conditions

Temperature
60 °C

Procedure

A suspension of iron (<10 micron) (1.6 g, 29 mmol) in methanol (24 mL) was treated with 6 M hydrogen chloride in water (0.4 mL, 2.4 mmol) and heated at 60° C. for 2 hours. The reaction mixture was treated with 5 M ammonium chloride in water (4.1 mL, 21 mmol) followed by methyl 4-chloro-3′-fluoro-6-nitro-5-[(trimethylsilyl)ethynyl]biphenyl-2-carboxylate (1.9 g, 4.8 mmol) and heated at 60° C. for 16 hours. The reaction mixture was filtered over celite, washed with methanol, and the filtrate was concentrated to a solid. The solid was diluted with ethyl acetate (200 mL) and saturated sodium bicarbonate (100 mL) and stirred for a few minutes. The organic layer was separated, washed with brine, dried with sodium sulfate, filtered, and concentrated to a crude residue. Purification by flash column chromatography using ethyl acetate in hexanes (0%-10%) gave the desired product (1.5 g, 86%). LCMS for C19H20ClFNO2Si (M+H)+: m/z=376.1; Found: 376.1.

Workup

  1. temperatureheated at 60° C. for 16 hours
  2. filtrationThe reaction mixture was filtered over celite
  3. washwashed with methanol
  4. concentrationthe filtrate was concentrated to a solid
  5. additionThe solid was diluted with ethyl acetate (200 mL) and saturated sodium bicarbonate (100 mL)
  6. customThe organic layer was separated
  7. washwashed with brine
  8. dry with materialdried with sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated to a crude residue
  11. customPurification by flash column chromatography

Sources & evidence

ORD record
ord-00e2709dda5c41098a6befb60b15a09a
Source dataset
uspto-grants-2014_03
Patent number
US08680108B2

Reaction notes

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