Tosylmethyl isocyanide → HCID 178442249, compound

HRID 216356Notes

Reaction equation

HRID 216356 reaction equation
C1C=[CH:3][NH+:4]=[CH:5]C=1.[O-][Cr](Cl)(=O)=O.[CH3:12][C:13]([C:19]([F:22])([F:21])[F:20])([CH:17]=[CH2:18])[CH2:14][CH2:15]O.CC1C=CC(S(C[N+:34]#[C-])(=O)=O)=CC=1.CC(C)([O-])C.[K+]>C(Cl)Cl.O1CCCC1>[CH3:12][C:13]([C:19]([F:22])([F:21])[F:20])([CH:17]=[CH2:18])[CH2:14][C:15]1[N:34]=[CH:3][NH:4][CH:5]=1

Participants

7

Reactant 4

HCID 161915Tosylmethyl isocyanideHCID 23665647Potassium tert-butoxideHCID 866377903-Methyl-3-(trifluoromethyl)pent-4-en-1-olHCID 178418287HCID 178418287, compound

Product 1

HCID 178442249HCID 178442249, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

PCC (15.4 g, 71.4 mmol) was added to an ambient temperature solution of 3-methyl-3-(trifluoromethyl)pent-4-en-1-ol (4.0 g, 23.8 mmol) in methylene chloride (100 mL). After stirring at ambient temperature for 1.5 h, celite was added and the reaction stirred vigorously for 10 min. The reaction mixture was filtered through celite and concentrated in vacuo. TosMIC (9.3 g, 47.6 mmol) followed by potassium tert-butoxide (cat.) were added to a solution of crude residue in tetrahydrofuran (50 mL). After stirring at ambient temperature for 2 h, the reaction mixture was concentrated in vacuo. Ammonia (7 N in methanol) (50 mL) was added to the crude residue. After stirring at 100° C. overnight, the reaction mixture was cooled and concentrated in vacuo. The residue was partitioned between 10% aqueous sodium hydroxide and methylene chloride. The aqueous phase was extracted with methylene chloride. The combined organic extracts were dried (magnesium sulfate) and concentrated in vacuo. Chromatography over silica eluting with 0-100% acetone/methylene chloride afforded 4-[2-methyl-2-(trifluoromethyl)but-3-en-1-yl]-1H-imidazole.

Workup

  1. additioncelite was added
  2. stirringthe reaction stirred vigorously for 10 min
  3. filtrationThe reaction mixture was filtered through celite and
  4. concentrationconcentrated in vacuo
  5. stirringAfter stirring at ambient temperature for 2 h
  6. concentrationthe reaction mixture was concentrated in vacuo
  7. additionAmmonia (7 N in methanol) (50 mL) was added to the crude residue
  8. stirringAfter stirring at 100° C. overnight
  9. temperaturethe reaction mixture was cooled
  10. concentrationconcentrated in vacuo
  11. customThe residue was partitioned between 10% aqueous sodium hydroxide and methylene chloride
  12. extractionThe aqueous phase was extracted with methylene chloride
  13. dry with materialThe combined organic extracts were dried (magnesium sulfate)
  14. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-69d3c596d35746ecb9d80822f000c242
Source dataset
uspto-grants-2012_06
Patent number
US08193228B2

Reaction notes

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