有机化学 ›› 2019, Vol. 39 ›› Issue (9): 2616-2624.DOI: 10.6023/cjoc201901053 上一篇    下一篇

研究论文

樟脑磺酸噻唑腙类化合物的设计、合成及抗氧化应用

张强健a, 王芸芸a, 赵雨珣a, 马崇慧a, 徐徐a,c, 谷文a,c, 杨益琴b,c, 王石发a,c   

  1. a 南京林业大学化学工程学院 南京 210037;
    b 南京林业大学轻工与食品学院 南京 210037;
    c 南京林业大学林业资源高效加工利用协同创新中心 南京 210037
  • 收稿日期:2019-01-30 修回日期:2019-03-17 出版日期:2019-09-25 发布日期:2019-04-11
  • 通讯作者: 王石发 E-mail:wangshifa65@163.com
  • 基金资助:

    国家自然科学基金(No.31470592)资助项目.

Design, Synthesis and Antioxidant Application of Camphorsulfonic Acid Thiazolylhydrazone Derivatives

Zhang Qiangjiana, Wang Yunyuna, Zhao Yuxuna, Ma Chonghuia, Xu Xua,c, Gu Wena,c, Yang Yiqingb,c, Wang Shifaa,c   

  1. a College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037;
    b College of Light Industry and Food, Nanjing Forestry University, Nanjing 210037;
    c Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037
  • Received:2019-01-30 Revised:2019-03-17 Online:2019-09-25 Published:2019-04-11
  • Contact: 10.6023/cjoc201901053 E-mail:wangshifa65@163.com
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 31470592).

以樟脑衍生物樟脑磺酸为原料,经缩合、环化等反应,合成了22个樟脑磺酸噻唑腙类化合物,采用1H NMR、13C NMR、HR-MS等方法对产物的结构进行表征,并研究了它们的抗氧化活性.结果表明,不同取代基的樟脑磺酸噻唑腙类化合物表现出不同的抗氧化活性,其中(2-(2-(4-(4-氰基苯基)噻唑-2-基)亚肼基)-7,7-二甲基双环[2.2.1]庚-1-基)甲磺酸(Q19)消除1,1-二苯基-2-三硝基苯肼(DPPH)自由基的IC50值可达到176 μmol/L,(2-(2-(4-(4-氟苯基)噻唑-2-基)亚肼基)-7,7-二甲基双环[2.2.1]庚-1-基)甲磺酸(Q3)消除2,2-联氮-二(3-乙基-苯并噻唑-6-磺酸)二铵盐(ABTS)自由基的IC50值可达到20.6 μmol/L,(E)-(7,7-二甲基-2-(2-(4-(3-甲苯基)噻唑-2-基)亚肼基)双环[2.2.1]庚-1-基)甲磺酸(Q8)对羟基自由基的消除率可达到66.2%,(2-(2-(4-(4-联苯基)噻唑-2-基)亚肼基)-7,7-二甲基双环[2.2.1]庚-1-基)甲磺酸(Q20)消除过氧自由基的IC50值可达到20.7 μmol/L,均远超过阳性对照trolox的抗氧化活性.(2-(2-(4-(2-羟基苯基)噻唑-2-基)亚肼基)-7,7-二甲基双环[2.2.1]庚-1-基)甲磺酸(Q16)抑制酪氨酸酶的IC50值可达154.9 μmol/L,也优于阳性对照曲酸.对樟脑磺酸基噻唑腙类化合物的抗氧化机理进行了探索.

关键词: 樟脑磺酸, 噻唑腙, 抗氧化活性

A series of camphorsulfonic acid thiazolylhydrazone derivatives were synthesized by using camphorsulfonic acid derivated from natural camphor as the starting material in three steps, including condensation with aminothiourea and cyclization with bromoacetophenone. Their structures were characterized by 1H NMR, 13C NMR and HR-MS, and their antioxidant activities were also investigated. The results showed that these compounds had good antioxidant activities compared with the positive control trolox. Among of them, (2-(2-(4-(4-cyanophenyl)thiazol-2-yl)indenyl)-7,7-dimethylbicyclo-[2.2.1]hept-1-yl)methanesulfonic acid (Q19) exhibited the relatively strong 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging activity with IC50 value of 176 μmol/L, (2-(2-(4-(4-fluorophenyl)thiazol-2-yl)hydrazino)-7,7-dimethylbicyclo-[2.2.1]hept-1-yl)methanesulfonic acid (Q3) exhibited the relatively strong diammonium 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) radical scavenging activity with IC50 value of 20.6 μmol/L, (E)-(7,7-dimethyl-2-(2-(4-(3-methyl)-thiazol-2-yl)indenyl)bicyclo[2.2.1]hept-1-yl)-sulfonic acid (Q8) exhibited the strong hydroxyl radical scavenging activity with scavenge rate 66.2%, (2-(2-(4-(4-biphenyl)thiazol-2-yl)indenyl)-7,7-dimethylbicyclo[2.2.1]hept-1-yl)methane-sulfonic acid (Q20) exhibited the relatively strong superoxide radical scavenging activity with IC50 value of 20.7 μmol/L. Compared with the positive control kojic acid, (2-(2-(4-(2-hydroxyphenyl)thiazol-2-yl)arylene)-7,7-dimethylbicyclo[2.2.1]hept-1-yl)methanesulfonic acid (Q16) exhibited remarkable tyrosinase inhibitory activity with IC50 value of 154.9 μmol/L. It was known from the structure-activity relationship that the structure of R gave great influence on the activities of thiazolylhydrazone derivatives.

Key words: camphorsulfonic acid, thiazolylhydrazone, antioxidant activity