反应 #531830

ord-e18181eb71b54f078bce9bcb1cda816b

反应方程式

CS(=O)(=O)Cl
methanesulfonyl chloride
O=C(O)c1cc(Cl)nn1-c1ncccc1Cl
3-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid
O=C(O)c1cc(Cl)nn1-c1ncccc1Cl
carboxylic acid
O=C(O)c1cc(Cl)nn1-c1ncccc1Cl
3-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid
CCN(CC)CC
triethylamine
Nc1c(Cl)cc(I)cc1C(=O)O
2-amino-3-chloro-5-iodobenzoic acid
CCN(CC)CC
triethylamine
CS(=O)(=O)Cl
methanesulfonyl chloride
O=c1oc(-c2cc(Cl)nn2-c2ncccc2Cl)nc2c(Cl)cc(I)cc12
title compound
O=c1oc(-c2cc(Cl)nn2-c2ncccc2Cl)nc2c(Cl)cc(I)cc12
8-chloro-2-[3-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-iodo-4H-3,1-benzoxazin-4-one

反应条件

温度
0°CELSIUS
详细条件
See reaction.notes.procedure_details.

后处理

  1. 1
    workup.STIRRINGstirring
  2. 2
    workup.WAITwas continued for an additional 5 minutes
  3. 3
    其他the temperature below 5° C
  4. 4
    workup.STIRRINGThe reaction mixture was stirred 40 minutes at 0° C.
  5. 5
    温度The reaction mixture was then warmed to room temperature
  6. 6
    workup.STIRRINGstirred overnight
  7. 7
    萃取extracted with ethyl acetate (3×50 mL)
  8. 8
    洗涤The combined ethyl acetate extracts were washed successively with 10% aqueous sodium bicarbonate (1×20 mL) and brine (1×20 mL)
  9. 9
    干燥dried (MgSO4)
  10. 10
    浓缩concentrated under reduced pressure
  11. 11
    其他The residual solid was purified by chromatography on silica gel

实验过程

To a solution of methanesulfonyl chloride (0.31 mL, 4.07 mmol) in acetonitrile (10 mL) was added dropwise a mixture of 3-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid (i.e. the carboxylic acid product of Example 3, Step D) (1.0 g, 3.87 mmol) and triethylamine (0.54 mL, 3.87 mmol) in acetonitrile (5 mL) at 0° C. The reaction mixture was then stirred for 15 minutes at 0° C. Then, 2-amino-3-chloro-5-iodobenzoic acid (i.e. the product from Step A) (1.15 g, 3.87 mmol) was added, and stirring was continued for an additional 5 minutes. A solution of triethylamine (1.08 mL, 7.74 mmol) in acetonitrile (5 mL) was then added dropwise while keeping the temperature below 5° C. The reaction mixture was stirred 40 minutes at 0° C., and then methanesulfonyl chloride (0.31 mL, 4.07 mmol) was added. The reaction mixture was then warmed to room temperature and stirred overnight. The reaction mixture was then diluted with water (50 mL) and extracted with ethyl acetate (3×50 mL). The combined ethyl acetate extracts were washed successively with 10% aqueous sodium bicarbonate (1×20 mL) and brine (1×20 mL), dried (MgSO4) and concentrated under reduced pressure. The residual solid was purified by chromatography on silica gel to afford 575 mg of the title compound as a crude yellow solid.

来源

DOI: 10.6084/m9.figshare.5104873.v1专利: US08475819B2uspto-grants-2013_07