Toluene → HCID 86617522, compound

HRID 2367139Notes

Reaction equation

HRID 2367139 reaction equation
CC([N:5]([C:9]1[CH:14]=[C:13]([Cl:15])[CH:12]=[C:11]([C:16]#[C:17]C(O)(C)C)[C:10]=1[CH3:22])[C:6](=[O:8])[O-:7])(C)C.C(=O)([O-])[O-].[K+].[K+].C1OCCOCCOCCOCCOCCOC1.[C:47]1([CH3:53])[CH:52]=CC=C[CH:48]=1>>[Cl:15][C:13]1[CH:12]=[C:11]([C:16]#[CH:17])[C:10]([CH3:22])=[C:9]([NH:5][C:6](=[O:8])[O:7][C:47]([CH3:53])([CH3:52])[CH3:48])[CH:14]=1

Participants

5

Reactant 4

HCID 1140TolueneHCID 11430Potassium CarbonateHCID 2855718-Crown-6HCID 86617523HCID 86617523, compound

Product 1

HCID 86617522HCID 86617522, compoundYield 58%

Procedure

To a solution of 1,1-dimethylethyl[5-chloro-3-(3-hydroxy-3-methylbut-1-yn-1-yl)-2-methylphenyl]carbamate (504 mg 1.56 mmol) in toluene (3 mL) was added potassium carbonate (215 mg, 1.56 mmol) and 18-crown-6 (82 mg, 0.31 mmol). The mixture was stirred at reflux for 5 hours, then was cooled to room temperature and partitioned between water and ethyl acetate. The aqueous portion was extracted twice with ethyl acetate. The combined organic portions were washed with brine, dried over sodium sulfate, filtered and concentrated in-vacuo to afford a brown residue which was purified by column chromatography (silica gel, 5% ethyl acetate in hexane). The product was collected to afford 242 mg, 0.91 mmol (58%) of 1,1-dimethylethyl (5-chloro-3-ethynyl-2-methylphenyl)carbamate as a tan solid. 1H NMR (400 MHz, CDCl3): 7.40 (d, 1H), 7.07 (d, 1H), 3.32 (s, 1H), 2.25 (s, 3H), 1.39 (s, 9H); MS (EI) for C14H16ClNO2: 266 (MH+).

Workup

  1. temperatureat reflux for 5 hours
  2. custompartitioned between water and ethyl acetate
  3. extractionThe aqueous portion was extracted twice with ethyl acetate
  4. washThe combined organic portions were washed with brine
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in-vacuo
  8. customto afford a brown residue which
  9. customwas purified by column chromatography (silica gel, 5% ethyl acetate in hexane)
  10. customThe product was collected

Sources & evidence

ORD record
ord-f5a9f935dc5f4daea0e6c47b72244a1b
Source dataset
uspto-grants-2014_04
Patent number
US08697737B2

Reaction notes

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