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1.
含硫化合物在有机合成、药物化学以及材料化学等领域具有重要的作用.到目前为止,科学家已经在C-S键的构建领域进行了很多工作.在构建C-S键的众多方法中,金属催化的C-S键合成反应是一类很重要的反应,但是此方法存在着催化剂对空气敏感、环境不友好等问题.因此,发展无金属催化的C-S键构建反应受到了人们越来越多的重视.基于我们在碘催化相关反应方面的研究,本文报道了一种碘催化的硫化吡唑啉酮类化合物的合成方法.我们选用3-甲基-1-苯基-2-吡唑啉-5-酮与二苯二硫醚为底物进行条件筛选实验,发现I2(10%)为催化剂,二氧六环为溶剂,H2O2为氧化剂为最优化的实验条件,目标产物硫化吡唑啉酮最高产率为88%.在最优化的反应条件下,我们尝试了带有不同官能团(NO2,Cl,OH等)的吡唑啉酮与二硫醚的反应,均能以较高产率得到目标产物.当含有杂环的二硫醚(2,2'-二硫二吡啶)作为反应底物时,也能以中等以上的产率得到相应的目标产物.另外还进行了对比试验,例如在反应体系中加入自由基捕获剂TEMPO,反应产率会大大降低,说明反应中应该有自由基中间体生成;如果反应体系中不加碘,则反应产率为零;如果反应体系中不加H2O2,则反应产率由88%降低至48%,说明碘和H2O2在反应中都起到了重要作用.通过以上对比试验,提出了可能的反应机理:首先,二硫醚发生均裂反应生成苯硫基自由基,然后苯硫基自由基与碘反应生成亲电的PhSI活性中间体,PhSI与异构化的吡唑啉酮发生亲电取代反应,生成目标产物硫化吡唑啉酮和HI,HI可以被H2O2氧化生成I2继续参与下一轮催化反应.以3-甲基-1-苯基-2-吡唑啉-5-酮与二苯二硫醚为底物,我们对此反应进行了放大试验,结果显示反应产率几乎没有降低,这为此反应的大规模应用奠定了基础.在此,我们发展了一种简单高效的合成硫化吡唑啉酮的反应,此方法无需金属催化剂,利用常见的碘为催化剂就可以以较高的产率得到目标产物.为合成含硫化合物提供了一种新的方法. 相似文献
2.
An iodine-catalyzed aerobic-oxidative C-H functionalization of o-alkylazoarenes to afford 2H-indazoles has been developed. CuI was found to be an effective additive to accelerate the regeneration of iodine in the catalytic cycle. This catalytic system is suitable for both electron-rich and electron-deficient azoarenes and tolerates a variety of functional groups with high yields. A gram-scale reaction was successfully conducted, proving the scalability of this reaction. 相似文献
3.
Some novel functionalized indeno[1,2-b]furans were synthesized from the reaction of indandione/indanone and aldehydes at room temperature followed by the reaction of the Knoevenagel condendensed intermediate with 4-hydroxycoumarins in the presence of iodine as catalyst in dimethyl sulfoxide (DMSO) under thermal conditions. The reaction involved in a condensation and Michael addition followed by lactone ring opening and intramolecular cyclization process to afford the product in high yield in easy work-up procedure. 相似文献
4.
Luana Bettanin Sumbal Saba Fábio Z. Galetto Gustavo A. Mike Jamal Rafique Antonio L. Braga 《Tetrahedron letters》2017,58(50):4713-4716
We describe herein a simple, fast and inexpensive protocol for the oxidative coupling of thiols employing a stoichiometric amount of DMSO and iodine as the catalyst. Various aromatic disulfides were obtained in good to excellent yields in short reaction times at room temperature, while aliphatic disulfides were achieved in good yields when the reactions were conducted under microwave irradiation. 相似文献
5.
《Tetrahedron》2019,75(39):130537
A simple and general method for direct thiolation of 4-quinolones with disulfides or thiols under I2/K2S2O8 system has been developed. Under the optimal conditions, the C–S bond coupling can take place effectively with good to decent yields and excellent regioselectivity of the S-linked products. The established metal-free site-selective approach was also applicable to transform a range of uracil substrates to the thio-substituted products under mild conditions. Further transformation to the sulfone derivatives can be conveniently performed in one-pot. These easy-to-handle protocols represent a useful and interesting synthetic alternative with good substrate scope and functional group compatibility. 相似文献
6.
7.
An efficient strategy enabling the construction of polysubstituted 1,2-dihydroquinoline derivatives mediated by the commercially available, economical, and environmentally benign iodine (3 mol %) under mild conditions was developed. Various arylamines and α-ketoesters could participate in this cascade reaction, and the desired products were obtained in excellent yields up to 98%. 相似文献
8.
An efficient method to synthesize isatins based on indoles by using inorganic hypervalent I2O5 has been explored in good yields, which successfully realized the transformation from indoles to isatins under metal-free, mild condition with broad substrate scope. 相似文献
9.
An I2–DMSO promoted novel and efficient method is described for the synthesis of isatins from 2-aminoaryl methyl ketone. A series of alkyl or aryl isatin derivatives were successfully synthesized under the optimized reaction conditions. 相似文献
10.
A mild,efficient and simple method for the preparation of acyl azides from carboxylic acids using chlorodiphenylphosphine in the presence of molecular iodine and sodium azide is described. 相似文献