海萝胶 → 5-Iodo-2-mercaptobenzoic acid

HRID 27449

反应方程式

HRID 27449 反应方程式
[I:1][C:2]1[CH:10]=[C:6]([C:7]([OH:9])=[O:8])[C:5](N)=[CH:4][CH:3]=1.[OH-].[Na+].N([O-])=O.[Na+].Cl.N([O-])=O.C([O-])(=O)C.[K+].O(CC)C([S-])=[S:29].[K+]>O>[I:1][C:2]1[CH:10]=[C:6]([C:7]([OH:9])=[O:8])[C:5]([SH:29])=[CH:4][CH:3]=1

参与物

9

反应物 7

HCID 313海萝胶2 次HCID 946NitriteHCID 14798二甲基对苯二胺二盐酸2 次HCID 729112-氨基-5-碘苯甲酸HCID 517044乙酸钾HCID 2735045乙基黄原酸钾HCID 23668193亚硝酸钠

产物 1

HCID 247733735-Iodo-2-mercaptobenzoic acid收率 80.5%

试剂、催化剂与溶剂 1

HCID 962聚[6-[4-(4-氰基苯基)苯氧基]己基甲基丙烯酸酯]溶剂2 次

实验过程

A solution of 5-iodoanthranilic acid (71.1 g; 0.272 mole), sodium hydroxide (11.5 g; 0.275 mole) and sodium nitrite (18.75 g; 0.275 mole) in water (325 ml) was added slowly with stirring to a mixture of concentrated hydrochloric acid (75 ml) and ice (100 g) while the temperature was maintained between 0° and 5° by external cooling and by the addition of ice. After completion of the addition of the nitrite solution, the mixture was stirred for an additional 30 minutes and adjusted to pH 7 with dilute sodium hydroxide solution and potassium acetate. The cold diazonium mixture was added to a vigorously stirred solution of potassium ethyl xanthate (125 g; 0.775 mole) in water (400 ml) preheated to 75°-80°. When the evolution of nitrogen ceased, the reaction mixture was cooled and acidified to pH 3 with concentrated hyrochloric acid. After decanting the aqueous phase, the resulting sludge was dissolved in 10 percent sodium hydroxide solution (200 ml) and heated on a steam bath for two hours. The solution was cooled, filtered, acidified to pH 4-5 with concentrated hydrochloric acid, and the solid collected, washed and dried. The resulting disulfide was refluxed for 16 hours with zinc dust (25 g) in glacial acetic acid (750 ml). The solid was collected, washed with cold water, digested with concentrated hydrochloric acid for 30 minutes, filtered, washed with water and dried to give 5-iodothiosalicyclic acid (61.3 g), m.p. 208°-210°. Treatment of 5-iodothiosalicyclic acid (60 g) with acetic anhydride (300 ml) and concentrated sulfuric acid (1 ml) at 100° for one hour yielded 5-iodoacetylthiosalicylic acid (35.1 g), m.p. 163°14 165°.

后处理

  1. temperaturewas maintained between 0° and 5°
  2. temperatureby external cooling and by the addition of ice
  3. custompreheated to 75°-80°
  4. temperaturethe reaction mixture was cooled
  5. customAfter decanting the aqueous phase
  6. dissolutionthe resulting sludge was dissolved in 10 percent sodium hydroxide solution (200 ml)
  7. temperatureheated on a steam bath for two hours
  8. temperatureThe solution was cooled
  9. filtrationfiltered
  10. customthe solid collected
  11. washwashed
  12. customdried
  13. temperatureThe resulting disulfide was refluxed for 16 hours with zinc dust (25 g) in glacial acetic acid (750 ml)
  14. customThe solid was collected
  15. washwashed with cold water
  16. waitdigested with concentrated hydrochloric acid for 30 minutes
  17. filtrationfiltered
  18. washwashed with water
  19. customdried

来源与证据

ORD记录
ord-3e5bf0f31f17404389ba2da23fd2371d
来源数据集
uspto-grants-1980_09
专利号
US04221800

关联笔记

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