تفاعل #2286385

ord-534eff04a8394a7ab5e03bf1f632bebc

معادلة التفاعل

CSCCN
2-(methylthio)ethanamine
CNc1cnc(-c2cncc(F)c2)s1
[2-(5-fluoropyridin-3-yl)-thiazol-5-yl]-methyl-amine
O=C(Cl)Cl
phosgene
CSCCNC(=O)N(C)c1cnc(-c2cncc(F)c2)s1
desired product
المردود 81.0%
CSCCNC(=O)N(C)c1cnc(-c2cncc(F)c2)s1
[2-(5-fluoropyridin-3-yl)-thiazol-5-yl]-1-methyl-3-(2-methylsulfanyl-ethyl)urea
المردود 81.0%

المذيبات

ظروف التفاعل

الظروف التفصيلية
See reaction.notes.procedure_details.

المعالجة

  1. 1
    أخرىthe ice bath was removed
  2. 2
    workup.WAITAfter another 5 min
  3. 3
    درجة الحرارةthe mixture was heated
  4. 4
    درجة الحرارةto reflux
  5. 5
    أخرىThe reaction was capped
  6. 6
    درجة الحرارةheated at 80° C. overnight
  7. 7
    أخرىThe reaction was quenched upon addition of ethyl acetate and 0.1 N HCl
  8. 8
    أخرىThe layers were separated
  9. 9
    غسيلthe organic layer was washed separately with saturated aqueous NaHCO3 and brine
  10. 10
    تجفيفThe ethyl acetate layer was dried over MgSO4
  11. 11
    ترشيحfiltered
  12. 12
    تركيزconcentrated under reduced pressure
  13. 13
    أخرىThe crude product was purified by silica gel column chromatography (0 to 100% ethyl acetate/hexanes)

الإجراء التجريبي

To a solution of [2-(5-fluoropyridin-3-yl)-thiazol-5-yl]-methyl-amine (0.4 g, 1.91 mmol) in DCE (5 mL) at 0° C. was added phosgene (1.3 mL, 2.5 mmol, 20 wt % solution in toluene). After 5 min, DMAP (0.5 g, 4.1 mmol) was added in one portion and the ice bath was removed. After another 5 min, the mixture was heated to reflux and stirred for 20 min. The reaction was cooled to ambient temperature and half of the solution was transferred to a vial and to this was added 2-(methylthio)ethanamine (0.183 g, 2.0 mmol) and DMAP (0.244 g, 2.0 mmol). The reaction was capped and heated at 80° C. overnight. The reaction was quenched upon addition of ethyl acetate and 0.1 N HCl. The layers were separated, and the organic layer was washed separately with saturated aqueous NaHCO3 and brine. The ethyl acetate layer was dried over MgSO4, filtered and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (0 to 100% ethyl acetate/hexanes) to give the desired product as an off-white solid (0.253 g, 81%): mp 117-119° C.; 1H NMR (300 MHz, CDCl3) δ 8.94 (br s, 1H), 8.50 (d, J=2.7 Hz, 1H), 7.99-7.94 (m, 1H), 7.54 (s, 1H), 5.37 (m, 1H), 3.53 (q, J=11.8, 5.5 Hz, 2H), 3.43 (s, 3H), 2.72 (app t, J=6.6 Hz, 2H), 2.13 (s, 3H); ESIMS m/z 327.1 (M+H); m/z 325.0 (M−1).

المصدر

DOI: 10.6084/m9.figshare.5104873.v1براءة الاختراع: US09357780B2uspto-grants-2016_06