تفاعل #410527

ord-d89fd8746f344cdc9a54815184619c2f

ظروف التفاعل

الظروف التفصيلية
See reaction.notes.procedure_details.

المعالجة

  1. 1
    درجة الحرارةCool in an ice bath
  2. 2
    درجة الحرارةHeat to reflux
  3. 3
    workup.WAITAfter 18 hours
  4. 4
    درجة الحرارةcool
  5. 5
    درجة الحرارةagain heat to reflux
  6. 6
    workup.WAITAfter 24 hours
  7. 7
    درجة الحرارةcool in a dry-ice/acetone bath
  8. 8
    درجة الحرارةWarm to ambient temperature
  9. 9
    تركيزConcentrate in vacuo
  10. 10
    أخرىto remove most to the tetrahydrofuran
  11. 11
    استخلاصextract three times with ethyl acetate
  12. 12
    استخلاصExtract the combined organic layers with water
  13. 13
    تجفيفbrine, dry the organic layer over Na2SO4
  14. 14
    ترشيحfilter
  15. 15
    أخرىevaporate in vacuo
  16. 16
    أخرىto give a residue

الإجراء التجريبي

Combine (1H-benzimidazol-2-yl)(1-(t-butoxycarbonyl)piperidin-4-yl)amine (3.5 mmol) and tetrahydrofuran (45 mL) and dimethylformamide (5 mL). Cool in an ice bath and add sodium hydride (0.21 g, 60% in oil, 5.22 mmol). After 1 hour, add 5-chloropentan-2-one, ethylene ketal (0.79 mL, 5.22 mmol) and tetra-n-butylammonium bromide (112 mg, 0.35 mmol) and warm to ambient temperature. Heat to reflux. After 18 hours, cool, add sodium hydride (0.1 g) and 5-chloropentan-2-one, ethylene ketal (0.50 mL) and again heat to reflux. After 24 hours, cool in a dry-ice/acetone bath and add a saturated aqueous solution of ammonium chloride. Warm to ambient temperature and dilute the reaction mixture with a saturated aqueous solution of sodium bicarbonate. Concentrate in vacuo to remove most to the tetrahydrofuran and extract three times with ethyl acetate. Extract the combined organic layers with water and then brine, dry the organic layer over Na2SO4, filter, and evaporate in vacuo to give a residue. Chromatograph the residue on silica gel eluting with 5% methanol/dichloromethane/0.1% saturated aqueous ammonia solution to give (1-(4-oxopentyl)-1H-benzimidazol-2-yl)(1-(t-butoxycarbonyl)piperidin-4-yl)amine, ethylene ketal.

المصدر

DOI: 10.6084/m9.figshare.5104873.v1براءة الاختراع: US06211199B1uspto-grants-2001_04