取代硫脲的制备工艺及应用研究
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摘要
本文采用不同的方法合成了一系列对称及不对称取代硫脲,并对其合成应用进行了探讨,主要包括：(1)以取代硫脲为原料,在羟基对甲苯磺酰碘苯的作用下,脱硫生成碳二亚胺；(2)以邻氯苯基硫脲为原料,合成草除灵乙酯。
研究了三种对称与不对称取代硫脲的合成方法：(1)胺和CS2在DMAP的催化下合成7种对称硫脲,以苯胺为底物,通过对反应影响因素的探讨,得到最佳反应条件为：物质的量比n(胺)：n(CS2)=1：1.6,DMAP用量为2.5mmol,加热回流,产率达到93%；并进行底物拓展,产品收率在60%-96%之间。(2)用胺和异硫氰酸酯为原料,物质的量比n(胺)：n(异硫氰酸酯)=1.05：1,室温下搅拌2.5h,即可得到对称与不对称取代硫脲,收率均74%-100%之间。(3)用二苯基硫脲和胺为原料,物质的量比n(二苯基硫脲)：n(胺)=1：1.2,加热回流3h,合成了6不对称硫脲,收率在60%-98%之间。
研究了离子液体作溶剂合成取代硫脲的工艺。异硫氰酸酯和胺在离子液体[Bmim][BF4]中反应生成对称及不对称取代硫脲。以异硫氰酸苯酯和对甲苯胺为底物,通过对反应影响因素的探讨,得到最佳反应条件为：物质的量比n(胺)：n(异硫氰酸酯)=1：1,室温反应15min,产率达90%,离子液体循环使用4次后,产率仍达87%；并进行底物拓展,产品收率在89%-99%之间。胺和二硫化碳在离子液体中反应生成对称硫脲,以对甲苯胺为底物,通过对反应影响因素的探讨,得到最佳反应条件是n(CS2)：n(胺)=1.2：1,反应温度为55℃,反应3h,产率达到85%以上,离子液体循环使用5次后,产率仍达70%；但该方法仅对芳香族的胺选择性好,脂肪胺参与反应产率较低。
对称和不对称取代硫脲在羟基对甲苯磺酰碘苯(HTIB)的作用下,脱硫生成碳二亚胺。以二苯基硫脲为底物,通过对反应影响因素的探讨,得到最佳反应条件为：物质的量比n(取代硫脲):n(HTIB):n(Et3N)=1:1:2,乙酸乙酯为溶剂,HTIB分批加入,冰浴下反应5h,产品收率达到85%；并进行底物拓展,产率均在63%-90%之间。
以邻氯苯基硫脲为原料,经中间体2-氨基-4-氯苯并噻唑,2-羟基-4-氯苯并噻唑合成了草除灵乙酯,对反应条件的进行优化,反应总收率为43%。
Different synthetic methods and applications of symmetric and unsymmetric thioureas were studied in this dissertation. The applications contained two aspects, one is preparation of corresponding carbodiimides from symmetrical and unsymmetrical thioureas via dehydrosul--furisation using HTIB; the other is synthsis of benazolin-ethyl with 1-(2-Chlorophenyl)-2-thiourea as raw material.
Symmetrical and unsymmetrical thioureas were synthesized by three methods. Reaction of amine and carbon disulfide using DMAP as catalyst gave 7 symmetrical thioureas, the optimized conditions (aniline as the substrate) is refluxing with molar ratio of amine and carbon disulfide 1:1.6 in the presence of 2.5mmol DMAP. Under these conditions the yields of 7 symmetrical thioureas were at the range of 60% to 96%; Reaction of amine with isothiocyanates at room temperature for 2.5 hours with molar ratio of amine and isothiocyanates 1.05:1, gave symmetric and unsymmetric thioureas. The yields were between 74% and 100%; Reaction of amine and N,N'-diphenyl thiourea under reflux for 3 hours with molar ratio of amine and N,N'-diphenyl thiourea 1.2:1, gave 6 unsymmetric thioureas in yields of 60%-98%.
Reaction of amine and isothiocyanates in ionic liquids, [Bmim][BF4], at room temperature for 15 minutes with molar ratio of amine and isothiocyanates 1:1 gave symmetric and unsymmetric thioureas. With phenylisothiocyanate and p-toluidine as the substrates the yields of thioureas were 89% to 99%; the yield of the products was up to 87% after recycling ionic liquids 4 times. Reaction of amine and carbon disulfide in ionic liquids, [Bmim][BF4], at 55℃for 3 hours with molar ratio of amine and carbon disulfide 1.2:1, gave symmetric thioureas in more than 85%yields. The yield of the products was 70% after recycling ionic liquids 5 times.
Dehydrosulfurisation of symmetrical and unsymmetrical thioureas using HTIB gave corresponding carbodiimides. Under optimized conditions the yields of symmetrical and unsymmetrical carbodiimides were between 63% and 90%.
Benazolin-ethyl was synthesized by using 1-(2-Chlorophenyl)-2-thiourea as raw material via intermediates of 2-amino-4-chlorbenzothiazole and 2-hydroxy-4-chlorbenzothiazole. The overall yield of the product was 43%.
研究了三种对称与不对称取代硫脲的合成方法：(1)胺和CS2在DMAP的催化下合成7种对称硫脲,以苯胺为底物,通过对反应影响因素的探讨,得到最佳反应条件为：物质的量比n(胺)：n(CS2)=1：1.6,DMAP用量为2.5mmol,加热回流,产率达到93%；并进行底物拓展,产品收率在60%-96%之间。(2)用胺和异硫氰酸酯为原料,物质的量比n(胺)：n(异硫氰酸酯)=1.05：1,室温下搅拌2.5h,即可得到对称与不对称取代硫脲,收率均74%-100%之间。(3)用二苯基硫脲和胺为原料,物质的量比n(二苯基硫脲)：n(胺)=1：1.2,加热回流3h,合成了6不对称硫脲,收率在60%-98%之间。
研究了离子液体作溶剂合成取代硫脲的工艺。异硫氰酸酯和胺在离子液体[Bmim][BF4]中反应生成对称及不对称取代硫脲。以异硫氰酸苯酯和对甲苯胺为底物,通过对反应影响因素的探讨,得到最佳反应条件为：物质的量比n(胺)：n(异硫氰酸酯)=1：1,室温反应15min,产率达90%,离子液体循环使用4次后,产率仍达87%；并进行底物拓展,产品收率在89%-99%之间。胺和二硫化碳在离子液体中反应生成对称硫脲,以对甲苯胺为底物,通过对反应影响因素的探讨,得到最佳反应条件是n(CS2)：n(胺)=1.2：1,反应温度为55℃,反应3h,产率达到85%以上,离子液体循环使用5次后,产率仍达70%；但该方法仅对芳香族的胺选择性好,脂肪胺参与反应产率较低。
对称和不对称取代硫脲在羟基对甲苯磺酰碘苯(HTIB)的作用下,脱硫生成碳二亚胺。以二苯基硫脲为底物,通过对反应影响因素的探讨,得到最佳反应条件为：物质的量比n(取代硫脲):n(HTIB):n(Et3N)=1:1:2,乙酸乙酯为溶剂,HTIB分批加入,冰浴下反应5h,产品收率达到85%；并进行底物拓展,产率均在63%-90%之间。
以邻氯苯基硫脲为原料,经中间体2-氨基-4-氯苯并噻唑,2-羟基-4-氯苯并噻唑合成了草除灵乙酯,对反应条件的进行优化,反应总收率为43%。
Different synthetic methods and applications of symmetric and unsymmetric thioureas were studied in this dissertation. The applications contained two aspects, one is preparation of corresponding carbodiimides from symmetrical and unsymmetrical thioureas via dehydrosul--furisation using HTIB; the other is synthsis of benazolin-ethyl with 1-(2-Chlorophenyl)-2-thiourea as raw material.
Symmetrical and unsymmetrical thioureas were synthesized by three methods. Reaction of amine and carbon disulfide using DMAP as catalyst gave 7 symmetrical thioureas, the optimized conditions (aniline as the substrate) is refluxing with molar ratio of amine and carbon disulfide 1:1.6 in the presence of 2.5mmol DMAP. Under these conditions the yields of 7 symmetrical thioureas were at the range of 60% to 96%; Reaction of amine with isothiocyanates at room temperature for 2.5 hours with molar ratio of amine and isothiocyanates 1.05:1, gave symmetric and unsymmetric thioureas. The yields were between 74% and 100%; Reaction of amine and N,N'-diphenyl thiourea under reflux for 3 hours with molar ratio of amine and N,N'-diphenyl thiourea 1.2:1, gave 6 unsymmetric thioureas in yields of 60%-98%.
Reaction of amine and isothiocyanates in ionic liquids, [Bmim][BF4], at room temperature for 15 minutes with molar ratio of amine and isothiocyanates 1:1 gave symmetric and unsymmetric thioureas. With phenylisothiocyanate and p-toluidine as the substrates the yields of thioureas were 89% to 99%; the yield of the products was up to 87% after recycling ionic liquids 4 times. Reaction of amine and carbon disulfide in ionic liquids, [Bmim][BF4], at 55℃for 3 hours with molar ratio of amine and carbon disulfide 1.2:1, gave symmetric thioureas in more than 85%yields. The yield of the products was 70% after recycling ionic liquids 5 times.
Dehydrosulfurisation of symmetrical and unsymmetrical thioureas using HTIB gave corresponding carbodiimides. Under optimized conditions the yields of symmetrical and unsymmetrical carbodiimides were between 63% and 90%.
Benazolin-ethyl was synthesized by using 1-(2-Chlorophenyl)-2-thiourea as raw material via intermediates of 2-amino-4-chlorbenzothiazole and 2-hydroxy-4-chlorbenzothiazole. The overall yield of the product was 43%.
引文
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