반응 #795015

ord-6e0357c0239247ff868129bd225bbaa9

반응 방정식

CCN(C(C)C)C(C)C
diisopropylethylamine
CC(C)NN.Cl
isopropylhydrazine hydrochloride
[Na+].[OH-]
NaOH
O=C([O-])O.[Na+]
sodium bicarbonate
[Na+].[O-]Cl
NaOCl
O=C(O)c1nc2c(s1)CCOc1cc(Br)ccc1-2
8-bromo-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene-2-carboxylic acid
CCN(C(C)C)C(C)C
diisopropylethylamine
CN(C)C(On1nnc2cccnc21)=[N+](C)C.F[P-](F)(F)(F)(F)F
HATU
CSC(=N)NC(=O)OCc1ccccc1
1-benzyloxycarbonyl-2-methyl-isothiourea
CC(C)n1nc(NC(=O)OCc2ccccc2)nc1-c1nc2c(s1)CCOc1cc(Br)ccc1-2
[5-(8-Bromo-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulen-2-yl)-1-isopropyl-1H-[1,2,4]triazol-3-yl]-carbamic acid benzyl ester
수율 57.0%

용매

반응 조건

온도
95°CELSIUS
상세 조건
See reaction.notes.procedure_details.

후처리

  1. 1
    workup.ADDITIONwas added
  2. 2
    추출the mixture extracted with 1:1 EtOAc/THF solution (×2)
  3. 3
    세척washed with brine
  4. 4
    건조dried (Na2SO4)
  5. 5
    농축concentrated in vacuo
  6. 6
    workup.ADDITIONThe resulting solid was added to DMF (50 mL)
  7. 7
    온도to cool to RT
  8. 8
    추출extracted with EtOAc
  9. 9
    세척washed with water
  10. 10
    건조The organic layer was dried (Na2SO4)
  11. 11
    농축concentrated in vacuo
  12. 12
    기타The resultant residue was purified by flash chromatography (SiO2, gradient 0-50% EtOAc in cyclohexane)

실험 절차

To a suspension of 8-bromo-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene-2-carboxylic acid (1.86 g, 5.70 mmol) in anhydrous THF (75 mL) was added diisopropylethylamine (2 mL, 11.4 mmol), HATU (2.39 g, 6.27 mmol) and 1-benzyloxycarbonyl-2-methyl-isothiourea (1.47 g, 6.56 mmol) at RT. After stirring for 24 hours an aqueous saturated sodium bicarbonate solution was added and the mixture extracted with 1:1 EtOAc/THF solution (×2). The organic layers were combined, washed with brine, dried (Na2SO4) and concentrated in vacuo. The resulting solid was added to DMF (50 mL) and treated with diisopropylethylamine (4 mL, 22.8 mmol) and isopropylhydrazine hydrochloride (941 mg, 8.55 mmol). The mixture was heated to 95° C. and scrubbed with 1N NaOH solution and NaOCl solution. After 2 hours the mixture was allowed to cool to RT, extracted with EtOAc and washed with water. The organic layer was dried (Na2SO4) and concentrated in vacuo. The resultant residue was purified by flash chromatography (SiO2, gradient 0-50% EtOAc in cyclohexane) to afford [5-(8-Bromo-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulen-2-yl)-1-isopropyl-1H-[1,2,4]triazol-3-yl]-carbamic acid benzyl ester (1.75 g, 57%). LCMS: RT=5.11 min, [M+H]+=540/542

출처

DOI: 10.6084/m9.figshare.5104873.v1특허: US09175009B2uspto-grants-2015_11