تفاعل #1277474

ord-e86246616aae4c7c8905c7fa95645193

معادلة التفاعل

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
المردود 57.0%

المذيبات

ظروف التفاعل

درجة الحرارة
95°CELSIUS
الظروف التفصيلية
See reaction.notes.procedure_details.

المعالجة

  1. 1
    workup.ADDITIONwas added
  2. 2
    استخلاصthe mixture extracted with 1:1 EtOAc/THF solution (×2)
  3. 3
    غسيلwashed with brine
  4. 4
    تجفيفdried (Na2SO4)
  5. 5
    تركيزconcentrated in vacuo
  6. 6
    workup.ADDITIONThe resulting solid was added to DMF (50 mL)
  7. 7
    درجة الحرارةto cool to RT
  8. 8
    استخلاصextracted with EtOAc
  9. 9
    غسيلwashed with water
  10. 10
    تجفيفThe organic layer was dried (Na2SO4)
  11. 11
    تركيزconcentrated in vacuo
  12. 12
    أخرىThe resultant residue was purified by flash chromatography (SiO2, gradient 0-50% EtOAc in cyclohexane)

الإجراء التجريبي

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

المصدر

DOI: 10.6084/m9.figshare.5104873.v1براءة الاختراع: US08673952B2uspto-grants-2014_03