تفاعل #657338

ord-36df0272358943c2854b524581ebdd81

معادلة التفاعل

CN(C)C=C1Oc2ccc(CCc3cccc(F)c3)cc2N=C1Cl
{3-chloro-6-[2-(3-fluoro-phenyl)-ethyl]-benzo[1,4]oxazin-2-ylidenemethyl}-dimethyl-amine
CC(C)(C)OC(=O)NCCCN1CCC(NC(N)=O)CC1
[3-(4-ureido-piperidin-1-yl)-propyl]-carbamic acid tert-butyl ester
O=C([O-])[O-].[Cs+].[Cs+]
cesium carbonate
CN(C)C=C1Oc2ccc(CCc3cccc(F)c3)cc2N=C1NC(=O)NC1CCN(CCCNC(=O)OC(C)(C)C)CC1
title compound
المردود 36.0%
CN(C)C=C1Oc2ccc(CCc3cccc(F)c3)cc2N=C1NC(=O)NC1CCN(CCCNC(=O)OC(C)(C)C)CC1
{3-[4-(3-{2-Dimethylaminomethylene-6-[2-(3-fluoro-phenyl)-ethyl]-2H-benzo[1,4]oxazin-3-yl}-ureido)-piperidin-1-yl]-propyl}-carbamic acid tert-butyl ester
المردود 36.0%

المذيبات

ظروف التفاعل

درجة الحرارة
23°CELSIUS
الظروف التفصيلية
See reaction.notes.procedure_details.

المعالجة

  1. 1
    أخرىThe reaction mixture was sparged with argon
  2. 2
    أخرىthe reaction vessel sealed
  3. 3
    أخرى(screw cap)
  4. 4
    أخرىplaced in 100° C.
  5. 5
    أخرىpartitioned between ethyl acetate and water (100 mL each)
  6. 6
    أخرىThe organic layer was separated
  7. 7
    غسيلwashed with saturated brine solution (100 mL)
  8. 8
    تجفيفthen dried (MgSO4)
  9. 9
    ترشيحfiltered
  10. 10
    تركيزconcentrated
  11. 11
    أخرىThe product was purified
  12. 12
    غسيلthen eluted with 2 M ammonia in methanol in dichloromethane (0-8% 2 M ammonia in methanol linear gradient over 18 column volumes at a flow rate of 60 mL/min)

الإجراء التجريبي

To a solution of {3-chloro-6-[2-(3-fluoro-phenyl)-ethyl]-benzo[1,4]oxazin-2-ylidenemethyl}-dimethyl-amine (500 mg, 1.45 mmol, 1 equiv) and [3-(4-ureido-piperidin-1-yl)-propyl]-carbamic acid tert-butyl ester (435 mg, 1.45 mmol, 1 equiv) in dioxane (15 mL) was added palladium(II) acetate (3.2 mg, 0.0145 mmol, 0.01 equiv), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos, 17 mg, 0.029 mmol, 0.02 equiv) and cesium carbonate (709 mg, 2.18 mmol, 1.5 equiv). The reaction mixture was sparged with argon then the reaction vessel sealed (screw cap) and placed in 100° C. oil bath. After 14 h at 100° C. the reaction was cooled to 23° C., and then partitioned between ethyl acetate and water (100 mL each). The organic layer was separated and washed with saturated brine solution (100 mL) then dried (MgSO4), filtered and concentrated. The product was purified using an Isco CombiFlash automated chromatography system. The residue was loaded onto an 80 g silica gel column as a solution in dichloromethane (5 mL) then eluted with 2 M ammonia in methanol in dichloromethane (0-8% 2 M ammonia in methanol linear gradient over 18 column volumes at a flow rate of 60 mL/min) to give 313 mg (0.515 mmol, 36%) of the title compound as a yellow/brown solid.

المصدر

DOI: 10.6084/m9.figshare.5104873.v1براءة الاختراع: US09023843B2uspto-grants-2015_05