Methyl chloroformate → HCID 15614951, compound

HRID 620356Notes

Reaction equation

HRID 620356 reaction equation
[Br:1][C:2]1[CH:11]=[CH:10][C:9]2[C:4](=[CH:5][CH:6]=[C:7]([O:16][CH3:17])[C:8]=2[C:12]([F:15])([F:14])[F:13])[C:3]=1[C:18]([NH2:20])=[O:19].[H-].[Na+].Cl[C:24]([O:26][CH3:27])=[O:25].[NH4+].[Cl-]>C1COCC1.O>[Br:1][C:2]1[CH:11]=[CH:10][C:9]2[C:4](=[CH:5][CH:6]=[C:7]([O:16][CH3:17])[C:8]=2[C:12]([F:14])([F:15])[F:13])[C:3]=1[C:18]([NH:20][C:24](=[O:25])[O:26][CH3:27])=[O:19]

Participants

7

Reactant 4

HCID 6586Methyl chloroformateHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 15614937HCID 15614937, compound

Product 1

HCID 15614951HCID 15614951, compoundYield 56%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

2-Bromo-6-methoxy-5-(trifluoromethyl)-1-naphthalenecarboxamide (4.18 g, 12.01 mmol) was added to a stirred suspension of sodium hydride (50% dispersion in mineral oil, 632 mg, 1.1 eq) in anhydrous THF (110 mL) precooled in an ice bath under a dry N2 atmosphere. The ice bath was removed and the suspension was stirred at ambient temperature for 30 minutes, warmed to 40° C. and stirred an additional 20 minutes. The reaction mixture was cooled to room temperature and methyl chloroformate (0.93 mL, 1.0 eq) in THF (25 mL) was added dropwise over a 10 minute period. After an additional 20 minutes, saturated aqueous NH4Cl (35 mL) was added. The reaction mixture was added to water (400 mL) and extracted with ether (2×300 mL). The combined ether extracts were washed with saturated aqueous NaCl (300 mL). Silica gel (25 mL) was added to the ether solution and the solvent was removed. The silica absorbate was flash chromatographed (3:2 petroleum ether:ethyl acetate, silica) to provide the title compound as a white solid (2.71 g, 56%) m.p. 180°-182° C.

Workup

  1. customprecooled in an ice bath under a dry N2 atmosphere
  2. customThe ice bath was removed
  3. temperaturewarmed to 40° C.
  4. stirringstirred an additional 20 minutes
  5. temperatureThe reaction mixture was cooled to room temperature
  6. waitAfter an additional 20 minutes
  7. extractionextracted with ether (2×300 mL)
  8. washThe combined ether extracts were washed with saturated aqueous NaCl (300 mL)
  9. additionSilica gel (25 mL) was added to the ether solution
  10. customthe solvent was removed
  11. customchromatographed (3:2 petroleum ether:ethyl acetate, silica)

Sources & evidence

ORD record
ord-55347a9f3fe246d69fe4c61d60a79420
Source dataset
uspto-grants-1989_04
Patent number
US04820727

Reaction notes

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