HRID1970806

反应详情

EQUATION

反应方程式

HRID 1970806 的结构方程式

AUXILIARIES

试剂、催化剂与溶剂

1

CONDITIONS

反应条件

温度
0 °C

PROCEDURE

实验过程

Under an argon atmosphere, 5-(4-acetoxyphenyl)-2-amino-3-benzylpyrazine (c-19) (681 mg, 2.13 mmol) was dissolved in anhydrous dichloromethane (40 mL), and to this was added triethylamine (1.20 mL, 8.53 mmol), and cooled to 0° C. To this was added 4-iodobenzylsulfonyl chloride (prepared by the method described in Liu, S. et al., Org. Lett., 3, 1571-1574 (2001)) (2.70 g, 8.53 mmol), and heated to reflux for 26 h after warming to room temperature. After cooling to room temperature, to this were added 2 M hydrochloric acid and dichloromethane and after separating the aqueous layer and organic layer, the organic layer was washed once with water and once with saturated brine, and dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the filtrate was concentrated under reduced pressure with a rotary evaporator. The residue was purified by silica gel column chromatography (100 g, n-hexane/ethyl acetate=4/1), to the obtained product was added dichloromethane, and filtered to remove insolubles. After this procedure was repeated 5 times, the filtrate was concentrated under reduced pressure with a rotary evaporator. The residue was recrystallized from ethyl acetate to give 5-(4-acetoxyphenyl)-3-benzyl-2-bis(4-iodobenzylsulfonyl)aminopyrazine (c-46) as a colorless solid (597 mg, 31.8%). Rf=0.21 (n-hexane/ethyl acetate=4/1). Mp. 166-167° C. 1H NMR. (400 MHz, DMSO-d6) δ 2.30 (s, 3H), 3.89 (s, 2H), 5.00 (d, 2H, J=13.6 Hz), 5.19 (d, 2H, J=13.6 Hz), 7.11-7.17 (AA′BB′, 2H), 7.19-7.34 (m, 9H), 7.78-7.83 (AA′BB′, 4H), 8.07-8.15 (AA′BB′, 2H), 9.19 (s, 1H). 13C NMR (67.8 MHz, DMSO-d6) δ 20.9, 37.5, 60.5 (2C), 96.3, 126.4, 126.5 (2C), 128.1 (2C), 128.5 (2C), 129.5 (2C), 132.0, 133.6 (4C), 137.4, 137.7 (4C), 139.2, 140.9, 151.2, 152.5, 155.5, 168.9. IR (KBr, cm−1) 519, 575, 627, 704, 775, 835, 912, 1013, 1057, 1159, 1200, 1254, 1356, 1377, 1483, 1601, 1757. Anal. Calcd. For C33H27I2N3O6S2: C, 45.06; H, 3.09; N, 4.78. Found: C, 45.18; H, 3.24; N, 4.78.

WORKUP

后处理

  1. customprepared by the method
  2. temperature, 3, 1571-1574 (2001)) (2.70 g, 8.53 mmol), and heated
  3. temperatureto reflux for 26 h
  4. temperatureafter warming to room temperature
  5. temperatureAfter cooling to room temperature
  6. customafter separating the aqueous layer and organic layer
  7. washthe organic layer was washed once with water and once with saturated brine
  8. dry with materialdried over anhydrous sodium sulfate
  9. customAfter removing anhydrous sodium sulfate
  10. filtrationby filtration
  11. concentrationthe filtrate was concentrated under reduced pressure with a rotary evaporator
  12. customThe residue was purified by silica gel column chromatography (100 g, n-hexane/ethyl acetate=4/1), to the obtained product
  13. additionwas added dichloromethane
  14. filtrationfiltered
  15. customto remove insolubles
  16. concentrationthe filtrate was concentrated under reduced pressure with a rotary evaporator
  17. customThe residue was recrystallized from ethyl acetate