四氧化硫 → [2-(4-Chlorophenylsulfanyl)phenyl]-3-methylpiperazine

HRID 445009笔记

反应方程式

HRID 445009 反应方程式
[CH3:1][CH:2]1[NH:7][CH2:6][CH2:5][N:4]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=2N)[CH2:3]1.S(=O)(=O)(O)O.N([O-])=O.[Na+].C([O-])(=O)C.[Na+].[Cl:29][C:30]1[CH:35]=[CH:34][C:33]([SH:36])=[CH:32][CH:31]=1>O.[OH-].[Na+].[Cu].C(OCC)(=O)C>[Cl:29][C:30]1[CH:35]=[CH:34][C:33]([S:36][C:9]2[CH:10]=[CH:11][CH:12]=[CH:13][C:8]=2[N:4]2[CH2:5][CH2:6][NH:7][CH:2]([CH3:1])[CH2:3]2)=[CH:32][CH:31]=1

参与物

10

反应物 5

HCID 1118四氧化硫HCID 78154-氯苯硫酚HCID 517045醋酸钠HCID 218649222-(3-Methylpiperazin-1-YL)anilineHCID 23668193亚硝酸钠

产物 1

HCID 21864889[2-(4-Chlorophenylsulfanyl)phenyl]-3-methylpiperazine

试剂、催化剂与溶剂 4

HCID 23978铜催化剂HCID 962聚[6-[4-(4-氰基苯基)苯氧基]己基甲基丙烯酸酯]溶剂HCID 8857乙酸乙酯溶剂HCID 14798氢氧化钠溶剂

反应条件

温度
0 °C

实验过程

2-(3-Methylpiperazin-1-yl)phenylamine (0.96 g, 5 mmol) was dissolved in 30 mL water containing sulfuric acid (0.28 mL, 5.2 mmol) and the solution was cooled to 0° C. and sodium nitrite (0.36 g, 5.2 mmol) was added. The reaction was stirred for 30 minutes before the pH of the reaction was adjusted to pH 7 with sodium acetate. The diazonium salt solution was then added dropwise to a solution of 4-chlorothiophenol in a suspension of copper (0.3 g, 5 mmol) in 2 M NaOH (4 mL). After addition, the reaction mixture was heated to 60° C. for 30 minutes before being allowed to cool to room temperature and ethyl acetate (10 mL) was added. The reaction mixture was filtered and the layers were separated. The aqueous layer was extracted with ethyl acetate (2×10 mL). The combined organic phases were dried (MgSO4) and volatile solvents evaporated in vacuo. The crude product was purified by flash chromatography using silica gel, eluting with ethyl acetate/methanol/ammonia 96:3:1. The pure product was isolated as a colourless oil. Yield (0.18 g, 11%) 1H NMR (CDCl3, 500 MHz) 1.12 (d, 3H); 2.6-2.72 (br m, 2H); 3.0-3.15 (m, 5H); 6.9 (m, 2H); 7.08 (d, 1H); 7.15 (m, 1H); 7.25-7.35 (m, 4H); MS (MH+) 319.1.

后处理

  1. additionAfter addition
  2. temperaturethe reaction mixture was heated to 60° C. for 30 minutes
  3. temperatureto cool to room temperature
  4. filtrationThe reaction mixture was filtered
  5. customthe layers were separated
  6. extractionThe aqueous layer was extracted with ethyl acetate (2×10 mL)
  7. dry with materialThe combined organic phases were dried (MgSO4) and volatile solvents
  8. customevaporated in vacuo
  9. customThe crude product was purified by flash chromatography
  10. washeluting with ethyl acetate/methanol/ammonia 96:3:1
  11. customThe pure product was isolated as a colourless oil
  12. customYield (0.18 g, 11%) 1H NMR (CDCl3, 500 MHz) 1.12 (d, 3H); 2.6-2.72 (br m, 2H); 3.0-3.15 (m, 5H); 6.9 (m, 2H); 7.08 (d, 1H); 7.15 (m, 1H); 7.25-7.35 (m, 4H)

来源与证据

ORD记录
ord-fd238575c24b42da8349b618fd3da682
来源数据集
uspto-grants-2013_07
专利号
US08476279B2

反应笔记

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