对称性硫脲的绿色合成工艺  

Green synthesis of symmetric thiourea compounds

作　　者：李合平 常帅军 宋士杰 刘俊勇 苏琼 LI Heping;CHANG Shuaijun;SONG Shijie;LIU Junyong;SU Qiong(Henan Engineering and Technology Research Center of Non-tire Rubber Auxiliaries,Hebi 458030,Henan,China;Henan Yijiaolian New Material Research Institute Co.,Ltd.,Hebi 458030,Henan,China)

机构地区：[1]河南省非轮胎类橡胶助剂工程技术研究中心,河南鹤壁458030 [2]河南易交联新材料研究院有限公司,河南鹤壁458030

出　　处：《精细化工》2023年第6期1386-1392,共7页Fine Chemicals

摘　　要：以乙二胺、CS_(2)为原料、水为溶剂,一锅合成了亚乙基硫脲(ETU),收率和HPLC纯度均达到99%以上。利用NMR、FTIR对产物结构进行了确证。考察了CS_(2)滴加温度、乙二胺与CS_(2)物质的量比、回流反应温度、回流反应升温速率及NaOH反应段NaOH用量对ETU收率、HPLC纯度的影响。结果表明,ETU的最佳合成工艺条件为CS_(2)滴加温度25~30℃、n(乙二胺)∶n(CS_(2))=1∶1.20、回流反应温度65~70℃、回流反应升温速率0.17℃/min、NaOH反应段NaOH用量为乙二胺质量的3.0%。以此工艺为模板,合成了1,3-二乙基硫脲(DETU)和四氢-2(1H)-嘧啶硫酮(PUR)。中试实验表明,该工艺稳定可靠,产品收率、HPLC纯度均达到99%以上,母液可循环套用。Ethylene thiourea(ETU),with both yield and HPLC purity over 99%,was synthesized with ethylenediamine and CS_(2) as raw materials and water as solvent in one pot,and characterized by NMR and FTIR.The effects of CS_(2) dropping temperature,molar ratio of ethylenediamine to CS_(2),reflux reaction temperature,reflux heating rate,and NaOH dosage in NaOH reaction section on the yield and purity of ETU were then investigated.The results showed that the optimum synthesis conditions were as follows:CS_(2) dropping temperature of 25~30℃,n(ethylenediamine)∶n(CS_(2))=1∶1.20,reflux reaction temperature of 65~70℃,reflux heating rate of 0.17℃/min,and NaOH dosage in NaOH reaction section being 3.0%of the mass of ethylenediamine.1,3-diethylthiourea(DETU)and tetrahydro-2(1H)-pyrimidine thioketone(PUR)were then synthesized under the optimized process conditions,and the pilot test indicated that the process was stable and reliable with the yield and HPLC purity of products obtained>99%,and the mother liquor could be recycled.

关 键 词：对称性硫脲 亚乙基硫脲 1 3-二乙基硫脲 四氢-2(1H)-嘧啶硫酮 异硫氰酸酯 精细化工中间体 

分 类 号：TQ218[化学工程—有机化工]