反応 #657338

ord-36df0272358943c2854b524581ebdd81

反応方程式

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
収率 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
収率 36.0%

溶媒

反応条件

温度
23°CELSIUS
詳細条件
See reaction.notes.procedure_details.

後処理

  1. 1
    その他The reaction mixture was sparged with argon
  2. 2
    その他the reaction vessel sealed
  3. 3
    その他(screw cap)
  4. 4
    その他placed in 100° C.
  5. 5
    その他partitioned between ethyl acetate and water (100 mL each)
  6. 6
    その他The organic layer was separated
  7. 7
    洗浄washed with saturated brine solution (100 mL)
  8. 8
    乾燥then dried (MgSO4)
  9. 9
    ろ過filtered
  10. 10
    濃縮concentrated
  11. 11
    その他The product was purified
  12. 12
    洗浄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)

実験手順

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.

出典

DOI: 10.6084/m9.figshare.5104873.v1特許: US09023843B2uspto-grants-2015_05