2-甲基-2-丁烯 → 4-Amino-3-chloro-6-propyl-5-fluoropicolinic acid

HRID 508561

反应方程式

HRID 508561 反应方程式
[NH2:1][C:2]1[C:7]([F:8])=[C:6]([CH2:9][CH2:10][CH3:11])[N:5]=[C:4]([CH:12]=[O:13])[C:3]=1[Cl:14].CC(=CC)C.P([O-])([O-])(O)=[O:21].[Na+].[Na+].Cl([O-])=O.[Na+]>O.C(O)(C)(C)C>[NH2:1][C:2]1[C:7]([F:8])=[C:6]([CH2:9][CH2:10][CH3:11])[N:5]=[C:4]([C:12]([OH:21])=[O:13])[C:3]=1[Cl:14]

参与物

7

反应物 4

HCID 105532-甲基-2-丁烯HCID 24203十二水合磷酸氢二钠HCID 23668197亚氯酸钠HCID 867234004-Amino-3-chloro-5-fluoro-6-propylpicolinaldehyde

产物 1

HCID 867234094-Amino-3-chloro-6-propyl-5-fluoropicolinic acid

试剂、催化剂与溶剂 2

HCID 962聚[6-[4-(4-氰基苯基)苯氧基]己基甲基丙烯酸酯]溶剂HCID 6386叔丁醇溶剂

反应条件

温度
85 °C

实验过程

A microwave vial equipped with a magnetic stir bar was charged with 4-amino-3-chloro-6-propyl-5-fluoropicolinaldehyde (15.9 mg, 0.072 mmol) and t-butanol (1.0 mL). The mixture was treated with H2O (0.40 mL), 2-methylbut-2-ene (100 μL, 0.10 mmol), sodium hydrogenphosphate (21.6 mg, 0.100 mmol), and finally sodium chlorite (19.28 mg, 0.206 mmol) was added in one portion. The mixture was heated to 85° C. for 16 h. An aliquot of the reaction mixture was analyzed by LC-MS. LC-MS analysis showed one major product with the correct mass for the desired product. The reaction mixture was evaporated to dryness under N2. Purification via reverse phase chromatography yielded 4-amino-3-chloro-6-propyl-5-fluoropicolinic acid (4.7 mg, 27.9%): 1H NMR (400 MHz, CDCl3) δ 11.60 (s, 1H), 4.98 (m, 2H), 2.76 (m, 2H), 1.75 (m, 2H), 0.99 (m, 3H); 19F NMR (376 MHz, CDCl3) δ−139.98; ESIMS m/z 231.2 ([M−H]−).

后处理

  1. customA microwave vial equipped with a magnetic stir bar
  2. additionwas added in one portion

来源与证据

ORD记录
ord-f9257669cadb40fd971834e6b1dc1621
来源数据集
uspto-grants-2015_08
专利号
US09096526B2

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