Sulfuric Acid → HCID 54397429, compound

HRID 1681303Notes

Reaction equation

HRID 1681303 reaction equation
Cl.[CH3:2][O:3][NH2:4].S(=O)(=O)(O)O.C(N(CC)[C:13]([C:21]1[CH:26]=[CH:25][C:24]([F:27])=[CH:23][C:22]=1[Cl:28])=[CH:14][C:15]1[CH:16]=[N:17][CH:18]=[CH:19][CH:20]=1)C.[OH-].[Na+]>O>[CH3:2][O:3][N:4]=[C:13]([C:21]1[CH:26]=[CH:25][C:24]([F:27])=[CH:23][C:22]=1[Cl:28])[CH2:14][C:15]1[CH:16]=[N:17][CH:18]=[CH:19][CH:20]=1

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 14798Sodium HydroxideHCID 521874O-Methylhydroxylamine hydrochlorideHCID 67915893HCID 67915893, compound

Product 1

HCID 54397429HCID 54397429, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

A solution of 1.2 g of O-methylhydroxylamine hydrochloride in 2.4 ml of distilled water is slowly treated with concentrated sulfuric acid with stirring in such a way that the reaction temperature does not rise above 60° C. 4.0 g of 3-[β-(diethylamino)-2-chloro-4-fluorostyryl]pyridine are then added rapidly in such a way that the internal temperature is exactly 70° C. at the end of the addition. The mixture is then stirred at 70° C. for 5 hours, cooled to room temperature and poured into ice-water. The aqueous phase is adjusted to pH=8.0 with sodium hydroxide solution and the mixture is extracted with diethyl ether. The organic phase is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. 2'-Chloro-4'-fluoro-2-(3-pyridyl)acetophenone O-methyloxime is obtained as an E/Z isomer mixture in the form of a brownish oil. Column chromatographic separation on silica gel using n-hexane/ethyl acetate (4:1) first gives the E isomer [1H-NMR (CDCl3, 200 MHz): 4.03 ppm (s, CH3O--N=)] and then the Z isomer [1H-NMR (CDCl3, 200 MHz): 3.84 ppm (s, CH3O--N=)].

Workup

  1. customdoes not rise above 60° C
  2. additionis exactly 70° C. at the end of the addition
  3. stirringThe mixture is then stirred at 70° C. for 5 hours
  4. extractionthe mixture is extracted with diethyl ether
  5. dry with materialThe organic phase is dried over anhydrous magnesium sulfate
  6. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-aad64f8c62bf4e14969ab16ece9a52b8
Source dataset
uspto-grants-1992_12
Patent number
US05171354

Reaction notes

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