Hydrochloric Acid → HCID 10947021, compound

HRID 1069426Notes

Reaction equation

HRID 1069426 reaction equation
Cl[Si](C)(C)C.[C:6]1([CH2:12]Br)[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.[Cu]C#N.[Cl-].[Li+].[CH3:19][C:20]1[N:25]([CH2:26][C:27]([O:29][CH3:30])=[O:28])[C:24](=[O:31])[C:23]([N+:32]([O-:34])=[O:33])=[C:22](OS(C(F)(F)F)(=O)=O)[CH:21]=1.Cl>O1CCCC1.[Zn].ClCCl>[CH3:19][C:20]1[N:25]([CH2:26][C:27]([O:29][CH3:30])=[O:28])[C:24](=[O:31])[C:23]([N+:32]([O-:34])=[O:33])=[C:22]([CH2:12][C:6]2[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=2)[CH:21]=1

Participants

10

Reactant 6

HCID 313Hydrochloric AcidHCID 6397ChlorotrimethylsilaneHCID 7498Benzyl BromideHCID 433294Lithium ChlorideHCID 11079278Methyl 6-methyl-3-nitro-2-oxo-4-[[(trifluoromethyl)sulphonyl]oxy]-1,2-dihydropyridine-1-acetateHCID 178418546HCID 178418546, compound

Product 1

HCID 10947021HCID 10947021, compound

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent3×

Procedure

200 μl of chlorotrimethylsilane are added at room temperature to 2 g (30.6 mmol) of zinc in suspension in 50 ml of tetrahydrofuran, the mixture is kept stirred for 0.5 hour at room temperature and then it is cooled to 0° C. 4.5 g (26.3 mmol) of phenylmethyl bromide in solution in 20 ml of tetrahydrofuran are then added dropwise and then the reaction medium is kept stirred for 2 hours at this temperature. Next, the mixture is transferred to a three-necked flask containing 2.24 g (25 mmol) of copper(I) cyanide and 2.12 g (50 mmol) of lithium chloride at −10° C., the mixture is stirred at this temperature for 5 minutes and then cooled to −70° C. 7.3 g (19.5 mmol) of methyl 6-methyl-3-nitro-2-oxo-4-[[(trifluoromethyl)sulphonyl]oxy]-1,2-dihydropyridine-1-acetate in solution in 50 ml of tetrahydrofuran are then added dropwise, the temperature of the reaction medium is allowed to return to 0° C. and the stirring is maintained for 1 hour at this temperature. The mixture is then poured over 100 ml of a 1 N hydrochloric acid solution and 200 ml of dichloromethane are added. The precipitate is filtered, the filtrate is allowed to settle out and the aqueous phase is extracted with dichloromethane. The organic phases are combined, they are dried over magnesium sulphate and evaporated to dryness. The residue is purified by chromatography on a silica gel column, eluting with a dichloro-methane:methanol (98:2) mixture.

Workup

  1. temperatureit is cooled to 0° C
  2. stirringthe reaction medium is kept stirred for 2 hours at this temperature
  3. stirringthe mixture is stirred at this temperature for 5 minutes
  4. temperaturecooled to −70° C
  5. customto return to 0° C.
  6. temperaturethe stirring is maintained for 1 hour at this temperature
  7. additionare added
  8. filtrationThe precipitate is filtered
  9. extractionthe aqueous phase is extracted with dichloromethane
  10. dry with materialthey are dried over magnesium sulphate
  11. customevaporated to dryness
  12. customThe residue is purified by chromatography on a silica gel column
  13. washeluting with a dichloro-methane:methanol (98:2) mixture

Sources & evidence

ORD record
ord-260d0b04e5484c0f94c29666e4c006dc
Source dataset
uspto-grants-2001_06
Patent number
US06252082B1

Reaction notes

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