CN110981850B - 一种绿色制备硫代酰胺的方法 - Google Patents

一种绿色制备硫代酰胺的方法 Download PDF

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CN110981850B
CN110981850B CN201911280169.6A CN201911280169A CN110981850B CN 110981850 B CN110981850 B CN 110981850B CN 201911280169 A CN201911280169 A CN 201911280169A CN 110981850 B CN110981850 B CN 110981850B
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汤日元
黄卓斌
徐莉
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Abstract

本发明公开了一种绿色制备硫代酰胺的方法。所述方法是在氧化剂和碘试剂的存在下，通过含有氰基的杂环、芳烃化合物与单质硫或者秋兰姆在反应溶剂中进行反应，制得硫代酰胺化合物，本发明同时适用于其他含sp3碳上的氰基化合物。本发明方法一步反应合成，操作简单，同时反应条件温和、广谱、对环境友好、原料廉价易得，具有良好的市场应用前景。本发明方法解决了含有氰基的吡啶类化合物、以及其它含有氰基的杂环、芳环化合物直接进行硫代酰胺化的技术难题，此方法可用于各种含有氰基的农药的改造，如氟虫腈、乙虫腈等等。

Description

一种绿色制备硫代酰胺的方法
技术领域
本发明属于硫代酰胺制备技术领域，具体涉及一种绿色制备硫代酰胺的方法。
背景技术
硫代酰胺是一类重要的有机化合物，广泛地存在于具有生物活性分子中，如目前临床用于治疗甲亢的硫酰胺类药物他巴唑(MMI)、甲亢平(CMZ)、丙基硫脲吡啶(PTU)和甲基硫脲吡啶。另一方面，硫代酰胺在有机合成中也是一类重要的合成子，许多有机化合物包括腈、酰胺、脒和含硫杂环(例如噻唑、噻唑啉、噻吩和噻二唑等)都可用硫代酰胺为原料进行合成。
合成硫代酰胺有多种方法。传统方法是用相应的酰胺和硫化试剂进行硫化的反应。常用的硫化试剂为P2O5或其芳烃衍生物(称Laweson试剂)。该方法的缺点是：制备此类硫化试剂会产生大量废水，硫的原子利用率不高且价格昂贵。其次常用的硫化剂如H2S、NaHS的使用不符合绿色化学的要求。如H2S属于有毒气体，要在封闭系统中使用，不利于日常的生产，存在安全隐患；硫氢化钠在参与反应时需要金属盐的产生(如MgCl2)。而单质硫在自然界中简单易得，是一种无毒、稳定、便宜易操作的试剂，且参与反应时原子利用率高是一种绿色的硫化剂；秋兰姆被广泛用于农药以及橡胶制备之中也是一种绿色的硫化剂。但是目前都没有把单质硫与秋兰姆作为硫化剂制备硫代酰胺的办法。
因此，开拓出一种绿色广谱、对环境友好、操作简单的制备硫代酰胺的方法是环保的需要，这是目前该领域研究的热点和重点之一。
发明内容
为解决现有技术的缺点和不足之处，本发明的首要目的在于提供一种绿色、广谱制备硫代酰胺的技术方法，解决含有氰基的吡啶类化合物、以及其它含有氰基的杂环、芳环化合物直接进行硫代酰胺化的技术难题，同时本发明也适用于其它含有氰基的芳香烃以及烷烃。在预期此方法可用于各种含有氰基的农药的改造，如氟虫清、乙虫腈等等。
本发明的另一目的在于提供一类由上述方法制得的硫代酰胺。
上述制备硫代酰胺的技术方法还可以用于氟虫腈、乙虫腈杀虫剂的改造。
本发明目的通过以下技术方案实现：
一种绿色制备硫代酰胺的方法，所述硫代酰胺包括杂环-硫代酰胺和芳环-硫代酰胺，该方法包括以下步骤：在氧化剂和碘试剂的存在下，通过化合物Ⅱ与相应的硫化剂Ⅲ或Ⅳ在反应溶剂中进行反应，从而制得式Ⅰ的杂环或芳环-硫代酰胺化合物；其合成路线如式(1)或式(2)所示：
Figure BDA0002316521210000021
式I、Ⅱ中的Ar是带有取代基的芳环或芳杂环，n＝0或1；
其中当n＝0时：
带有取代基的芳环选自以下结构：
Figure BDA0002316521210000022
R1选自H、C1-C6烷基、卤素、C1-C6烷氧基、羟基、酯基，
带有取代基的芳杂环则选自以下几类：带有取代基的含N六元杂环、带有取代基的苯并杂环类、带有取代基的五元杂环、带有取代基的吡唑酮环、N-取代吡唑杂环；
其中当n＝1时：
带有取代基的芳环选自以下结构：
Figure BDA0002316521210000031
R1选自H、C1-C6烷基、卤素、C1-C6烷氧基、羟基、酯基，
带有取代基的芳杂环为吡啶甲基
Figure BDA0002316521210000032
式Ⅳ中的R4选自C1-C6烷基。
优选的，当n＝0时，带有取代基的芳杂环选自带有取代基的吡啶、嘧啶、异喹啉、咪唑并吡啶、吲哚环、吲唑、苯并噻吩、呋喃、噻吩、噻唑、吡咯等，具体选自以下结构：
Figure BDA0002316521210000033
其中，R1选自H、C1-C6烷基、卤素、C1-C6烷氧基、羟基、酯基；
R2选自H、C1-C6烷基；
R3选自H、三氟甲基亚磺酰基、乙磺酰基。
所述的C1-C6烷基的含义是指具有1-6个碳原子的直链或支链烷基，非限定性地例如可为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、异戊基、正己基或烷己基等。
所述的C1-C6烷氧基是指上述C1-C6烷基与O原子相连后的基团。
所述的卤素的含义是指卤族元素，非限定地例如可为F、Cl、Br或I。
在本发明的所述合成方法中，化合物Ⅱ与硫化剂Ⅲ的摩尔比为1:1-4，非限定性地例如可以为1:1、1:1.2、1:1.5、1:2.0、1:3.0或1:4.0。
在本发明的所述合成方法中，化合物Ⅱ与硫化剂Ⅳ的摩尔比为1:1-4，非限定性地例如可以为1:1、1:1.2、1:1.5、1:2.0、1:3.0或1:4.0。
在本发明的所述合成方法中，化合物Ⅱ与碘试剂的摩尔比为1:0.05-2，非限定性地例如可以为1:0.05、1:0.1、1:0.2、1:1或1:2。
在本发明的所述合成方法中，化合物Ⅱ与氧化剂的摩尔比为1:0.5-3，非限定性地例如可以为1:0.5、1:1.5、1:2.0、1:2.5或1:3.0。
在本发明的所述合成方法中，所述碘试剂为碘化钠、碘化钾或碘单质。
在本发明的所述合成方法中，所述氧化剂为过硫酸钾、过氧单磺酸钾、二叔丁基过氧化物、叔丁基过氧化氢、过氧化氢、双(过氧化叔丁基)丁烷、过氧化二异丙苯或苯醌。
在本发明的所述合成方法中化合物Ⅱ与硫化剂Ⅲ、化合物Ⅱ与硫化剂Ⅳ进行反应时的反应溶剂为有机溶剂或有机溶剂与水混合物，例如非限定性地可以是N,N-二甲基甲酰胺(DMF)与水混合物、乙腈与水混合物、乙醇与水混合物、二甲基亚砜(DMSO)与水混合物、四氢呋喃与水混合物、1,2-二氯乙烷、氯仿、二氯甲烷、甲苯、乙腈、N,N-二甲基甲酰胺(DMF)、乙醇、甲醇、二甲基亚砜(DMSO)、四氢呋喃、四氯化碳、正己烷、正丙醇、异丙醇、丁醇、戊醇、丙酮、2-丁酮等中的任意一种或两种以上的组合，最优选为N,N-二甲基甲酰胺(DMF)与水混合物。
在本发明的所述合成方法中，N,N-二甲基甲酰胺(DMF)与水混合物中DMF与水体积比例为1:0.1-2，非限定地例如可以为1:0.1、1:0.2、1:0.5、1:1或1:2。
在本发明的所述合成方法中，反应温度为70-140℃，非限定地例如可以为70℃、80℃、90℃、100℃、120℃、130℃或140℃。
在本发明的所述合成方法中，反应结束后的后处理可以采用有机合成领域中的任何公知的常规处理手段，例如结晶、柱层析提纯、萃取等中的任何一种处理手段或多种处理手段的组合。作为一种例举性的后处理手段，例如可以为：反应完毕后，用旋转蒸发仪从反应结束后得到的混合物中除去溶剂，残留物用300-400目硅胶柱层析提纯得到目标产物，柱层析过程可以用TLC跟踪监控而确定合适的洗脱终点。
本发明通过使用含有氰基吡啶类化合物、以及其它含有氰基的杂环、芳环化合物为原料，通过使用单质硫或者秋兰姆为硫化剂，通过使用氧化剂和碘试剂作为催化剂以及其它工艺参数的合适选择和组合，而一步得到了杂环、芳环-硫代酰胺化合物。
本发明所述方法可制得的硫代酰胺包括以下结构式所示的化合物：
Figure BDA0002316521210000051
Figure BDA0002316521210000061
为了开发出新型的制备技术并得到上述化合物，发明人进行了深入的研究，在付出了大量的创造性劳动后，研究发现在KI/K2S2O8体系的催化下，可以选择性地把杂环、芳环Ar上或者sp3碳上的氰基选择性地反应转化为硫代酰胺。此方法原料易得，操作简单，反应条件对环境友好，与多种杂环或者官能团兼容，产率中等至优，是一种有效制备杂环-硫代酰胺的方法。
与现有技术相比，本发明具有以下优点及有益效果：
本发明制备方法反应条件温和对环境友好、反应时间短、原料廉价易得、产物收率和纯度高等诸多优点，为新型杂环、芳环-硫代酰胺化合物的制备提供了有效的合成方法，具有良好的研究价值和应用前景。
具体实施方式
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1.3-甲苯基硫代甲酰胺(I-1)的合成。
合成路线为：
Figure BDA0002316521210000071
合成路线(1)的步骤：将上式化合物(Ⅱ-1)、原料(Ⅲ)、过硫酸钾、碘化钾按摩尔比为1:3:2:0.2加入反应容器，其中式(Ⅱ-1)化合物为2mmol；将反应体系在120℃下搅拌反应12小时。反应结束后冷却，加入适量乙酸乙酯，用水萃取，有机相干燥、抽滤，滤液旋蒸，除去溶剂，剩余物用硅胶柱层析，石油醚淋洗，TLC检测，合并含有产物的流出液，旋转蒸发仪蒸馏除去溶剂，真空干燥得到黄色固体的目标产物，产率为90％，纯度为99.4％(HPLC)。
合成路线(2)的步骤：将上式化合物(Ⅱ-1)、化合物(Ⅳ)、过硫酸钾、碘化钾按摩尔比为1:1.5:2:0.2加入反应容器，其中式(Ⅱ-1)化合物为2mmol；将反应体系在120℃下搅拌反应12小时。反应结束后冷却，加入适量乙酸乙酯，用水萃取，有机相干燥、抽滤，滤液旋蒸，除去溶剂，剩余物用硅胶柱层析，石油醚淋洗，TLC检测，合并含有产物的流出液，旋转蒸发仪蒸馏除去溶剂，真空干燥得到黄色固体的目标产物，产率为87％，纯度为99.4％(HPLC)。
本实施例制得的3-甲苯基硫代甲酰胺的核磁共振氢谱，核磁共振碳谱和红外光谱的检测数据如下：
1H NMR(600MHz,DMSO-d6)δ9.76(s,1H),9.40(s,1H),7.83(d,J＝8.2Hz,2H),7.21(d,J＝8.0Hz,2H),2.32(s,3H).13C NMR(151MHz,DMSO-d6)δ200.2,141.7,137.0,128.9,127.9,21.4.
IR(KBr,cm-1):3379,3278,3161,1624,1415,1325,1272,881,823,794,713.
实施例2.吡啶-2-硫代酰胺(I-4)的合成。
合成路线为：
Figure BDA0002316521210000081
合成路线(1)的步骤：将上式化合物(II-4)、原料(Ⅲ)、过硫酸钾、碘化钾按摩尔比为1:3:2:0.2加入反应容器，其中式(II-4)化合物为2mmol。将反应体系在120℃下搅拌反应12小时。反应结束后冷却，加入适量乙酸乙酯，用水萃取，有机相干燥、抽滤，滤液旋蒸，除去溶剂，剩余物用硅胶柱层析，石油醚淋洗，TLC检测，合并含有产物的流出液，旋转蒸发仪蒸馏除去溶剂，真空干燥得到黄色固体的目标产物，产率为88％，纯度为99.5％(HPLC)。
合成路线(2)的步骤：将上式化合物(II-4)、化合物(Ⅳ)、过硫酸钾、碘化钾按摩尔比为1:1.5:2:0.2加入反应容器，其中式(II-4)化合物为2mmol。将反应体系在100℃下搅拌反应12小时。反应结束后冷却，加入适量乙酸乙酯，用水萃取，有机相干燥、抽滤，滤液旋蒸，除去溶剂，剩余物用硅胶柱层析，石油醚淋洗，TLC检测，合并含有产物的流出液，旋转蒸发仪蒸馏除去溶剂，真空干燥得到黄色固体的目标产物，产率为94％，纯度为99.5％(HPLC)。
本实施例制得的吡啶-2-硫代酰胺的核磁共振氢谱，核磁共振碳谱和红外光谱的检测数据如下：
1H NMR(600MHz,Chloroform-d)δ9.53(s,1H),8.69(d,J＝7.9Hz,1H),8.51(ddd,J＝4.7,1.8,0.9Hz,1H),7.98(s,1H),7.83(td,J＝7.8,1.8Hz,1H),7.44(ddd,J＝7.6,4.7,1.2Hz,1H).
13C NMR(151MHz,Chloroform-d)δ195.8,150.5,147.2,137.1,126.3,125.0.
IR(KBr,cm-1):3350,3241,3155,1602,1584,1567,1445,1308,1278,1259,1051,903,796,728.
实施例3.异喹啉-1-硫代酰胺(I-12)的合成。
合成路线为：
Figure BDA0002316521210000091
合成路线(1)的步骤：将上式化合物(II-12)、原料(Ⅲ)、过硫酸钾、碘化钾按摩尔比为1:3:2:0.2加入反应容器，其中式(II-12)化合物为2mmol。将反应体系在120℃下搅拌反应12小时。反应结束后冷却，加入适量乙酸乙酯，用水萃取，有机相干燥、抽滤，滤液旋蒸，除去溶剂，剩余物用硅胶柱层析，石油醚淋洗，TLC检测，合并含有产物的流出液，旋转蒸发仪蒸馏除去溶剂，真空干燥得到黄色固体的目标产物，产率为24％，纯度为99.6％(HPLC)。
合成路线(2)的步骤：将上式化合物(II-12)、化合物(Ⅳ)、过硫酸钾、碘化钾按摩尔比为1:1.5:2:0.2加入反应容器，其中式(II-12)化合物为2mmol。将反应体系在100℃下搅拌反应12小时。反应结束后冷却，加入适量乙酸乙酯，用水萃取，有机相干燥、抽滤，滤液旋蒸，除去溶剂，剩余物用硅胶柱层析，石油醚淋洗，TLC检测，合并含有产物的流出液，旋转蒸发仪蒸馏除去溶剂，真空干燥得到黄色固体的目标产物，产率为77％，纯度为99.6％(HPLC)。
本实施例制得的异喹啉-1-硫代酰胺的核磁共振氢谱，核磁共振碳谱和红外光谱的检测数据如下：
1H NMR(600MHz,DMSO-d6)δ10.46(s,1H),10.04(s,1H),8.45(d,J＝5.6Hz,1H),8.30(d,J＝8.4Hz,1H),8.01(d,J＝8.2Hz,1H),7.86(d,J＝5.7Hz,1H),7.81(t,J＝7.5Hz,1H),7.71(t,J＝7.6Hz,1H).
13C NMR(151MHz,DMSO-d6)δ200.5,159.8,141.6,136.5,131.1,128.1,127.3,126.7,124.1,121.3.
IR(KBr,cm-1):3348,3228,3049,1649,1620,1562,1423,1380,1292,928,873,830,756.
实施例4.呋喃-2-硫代酰胺(I-18)的合成。
合成路线为：
Figure BDA0002316521210000101
合成路线(1)的步骤：将上式化合物(II-18)、原料(Ⅲ)、过硫酸钾、碘化钾按摩尔比为1:3:2:0.2加入反应容器，其中化合物(II-18)为2mmol。将反应体系在120℃下搅拌反应12小时。反应结束后冷却，加入适量乙酸乙酯，用水萃取，有机相干燥、抽滤，滤液旋蒸，除去溶剂，剩余物用硅胶柱层析，石油醚淋洗，TLC检测，合并含有产物的流出液，旋转蒸发仪蒸馏除去溶剂，真空干燥得到黄色固体的目标产物，产率为62％，纯度为99.6％(HPLC)。
合成路线(2)的步骤：将上式化合物(II-18)、化合物(Ⅳ)、过硫酸钾、碘化钾按摩尔比为1:1.5:2:0.2加入反应容器，其中式(II-18)化合物为2mmol。将反应体系在120℃下搅拌反应12小时。反应结束后冷却，加入适量乙酸乙酯，用水萃取，有机相干燥、抽滤，滤液旋蒸，除去溶剂，剩余物用硅胶柱层析，石油醚淋洗，TLC检测，合并含有产物的流出液，旋转蒸发仪蒸馏除去溶剂，真空干燥得到黄色固体的目标产物，产率为96％，纯度为99.6％(HPLC)。
本实施例制得的呋喃-2-硫代酰胺的核磁共振氢谱，核磁共振碳谱和红外光谱的检测数据如下：
1H NMR(600MHz,DMSO-d6)δ9.59(s,1H),9.28(s,1H),7.86(d,J＝1.7Hz,1H),7.25(d,J＝3.5Hz,1H),6.61(dd,J＝3.5,1.7Hz,1H).
13C NMR(151MHz,DMSO-d6)δ184.8,152.3,146.1,117.3,113.4.
IR(KBr,cm-1):3373,3275,3163,1624,1577,1478,1410,1392,1335,1162,1013,935,852,767.
实施例5.2-氧代-1,2-二氢吡啶-3-硫代酰胺(I-22)的合成。
合成路线为：
Figure BDA0002316521210000111
合成路线(1)的步骤：将上式化合物(II-22)、原料(Ⅲ)、过硫酸钾、碘化钾按摩尔比为1:3:2:0.2加入反应容器，其中式(II-22)化合物为2mmol。将反应体系在120℃下搅拌反应12小时。反应结束后冷却，加入适量乙酸乙酯，用水萃取，有机相干燥、抽滤，滤液旋蒸，除去溶剂，剩余物用硅胶柱层析，石油醚淋洗，TLC检测，合并含有产物的流出液，旋转蒸发仪蒸馏除去溶剂，真空干燥得到黄色固体的目标产物，产率为66％，纯度为99.2％(HPLC)。
合成路线(2)的步骤：将上式化合物(II-22)、化合物(Ⅳ)、过硫酸钾、碘化钾按摩尔比为1:1.5:2:0.2加入反应容器，其中式(II-22)化合物为2mmol。将反应体系在120℃下搅拌反应12小时。反应结束后冷却，加入适量乙酸乙酯，用水萃取，有机相干燥、抽滤，滤液旋蒸，除去溶剂，剩余物用硅胶柱层析，石油醚淋洗，TLC检测，合并含有产物的流出液，旋转蒸发仪蒸馏除去溶剂，真空干燥得到黄色固体的目标产物，产率为74％，纯度为99.2％(HPLC)。
本实施例制得的2-氧代-1,2-二氢吡啶-3-硫代酰胺的核磁共振氢谱，核磁共振碳谱和红外光谱的检测数据如下：
1H NMR(600MHz,DMSO-d6)δ12.63(s,1H),11.33(s,1H),9.99(s,1H),8.94(dd,J＝7.4,2.2Hz,1H),7.77(dd,J＝6.2,2.3Hz,1H),6.53(dd,J＝7.5,6.2Hz,1H).
13C NMR(151MHz,DMSO-d6)δ194.6,162.2,149.3,140.8,123.3,107.1.
IR(KBr,cm-1):3345,3199,2922,1640,1609,1541,1481,1346,1280,1242,1070,838,770.
实施例6.5-氨基-1-(2,6-二氯-4-(三氟甲基)苯基)-1H-吡唑-3-硫代酰胺(I-23)的合成。
合成路线为：
Figure BDA0002316521210000121
Figure BDA0002316521210000131
合成路线(1)的步骤：将上式化合物(II-23)、原料(Ⅲ)、过硫酸钾、碘化钾按摩尔比为1:3:2:0.2加入反应容器，其中式(II-23)化合物为2mmol。将反应体系在120℃下搅拌反应12小时。反应结束后冷却，加入适量乙酸乙酯，用水萃取，有机相干燥、抽滤，滤液旋蒸，除去溶剂，剩余物用硅胶柱层析，石油醚淋洗，TLC检测，合并含有产物的流出液，旋转蒸发仪蒸馏除去溶剂，真空干燥得到黄色固体的目标产物，产率为55％，纯度为99.3％(HPLC)。
合成路线(2)的步骤：将上式化合物(II-23)、化合物(Ⅳ)、过硫酸钾、碘化钾按摩尔比为1:1.5:2:0.2加入反应容器，其中式(II-23)化合物为2mmol。将反应体系在120℃下搅拌反应12小时。反应结束后冷却，加入适量乙酸乙酯，用水萃取，有机相干燥、抽滤，滤液旋蒸，除去溶剂，剩余物用硅胶柱层析，石油醚淋洗，TLC检测，合并含有产物的流出液，旋转蒸发仪蒸馏除去溶剂，真空干燥得到黄色固体的目标产物，产率为77％，纯度为99.3％(HPLC)。
本实施例制得的5-氨基-1-(2,6-二氯-4-(三氟甲基)苯基)-1H-吡唑-3-硫代酰胺的核磁共振氢谱，核磁共振碳谱和红外光谱的检测数据如下：
1H NMR(600MHz,Chloroform-d)δ8.11(s,1H),7.77(s,2H),7.39(s,1H),6.46(s,1H),3.67(s,2H).
13C NMR(151MHz,Chloroform-d)δ191.7,151.5,147.2,136.6,136.1,134.0(JC-F＝34.5Hz),126.1(JC-F＝3.7Hz),122.0(JC-F＝273.9Hz),94.1.
IR(KBr,cm-1):3300,3172,1620,1564,1506,1447,1394,1319,1290,1208,1178,1142,1101,1070,881,853,816.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (7)

1.一种绿色制备硫代酰胺的方法，所述硫代酰胺包括杂环-硫代酰胺化合物和芳环-硫代酰胺化合物，其特征在于，所述方法包括以下步骤：在氧化剂和碘试剂的存在下，通过化合物Ⅱ与相应的硫化剂Ⅲ或Ⅳ在反应溶剂中进行反应，从而制得式Ⅰ的杂环或芳环-硫代酰胺化合物；所述碘试剂为碘化钠、碘化钾中的一种以上，所述氧化剂为过硫酸钾；其合成路线如式(1)或式(2)所示：
Figure FDA0002666395210000011
式I、Ⅱ中的Ar是带有取代基的芳环或芳杂环或
Figure FDA0002666395210000012
带有取代基的芳环选自以下结构：
Figure FDA0002666395210000013
R1选自H、C1-C6烷基、卤素、C1-C6烷氧基、羟基、酯基，
带有取代基的芳杂环选自以下结构：
Figure FDA0002666395210000014
Figure FDA0002666395210000021
其中，R1选自H、C1-C6烷基、卤素、C1-C6烷氧基、羟基、酯基；
R2选自H、C1-C6烷基；
R3选自H、三氟甲基亚磺酰基、乙磺酰基。
2.根据权利要求1所述的一种绿色制备硫代酰胺的方法，其特征在于，化合物Ⅱ与硫化剂Ⅲ的摩尔比为1:1-4；化合物Ⅱ与硫化剂Ⅳ的摩尔比为1:1-4；反应温度为70-140℃。
3.根据权利要求1所述的一种绿色制备硫代酰胺的方法，其特征在于，化合物Ⅱ与硫化剂Ⅲ的摩尔比为1:1、1:1.2、1:1.5、1:2.0、1:3.0或1:4.0；
化合物Ⅱ与硫化剂Ⅳ的摩尔比为1:1、1:1.2、1:1.5、1:2.0、1:3.0或1:4.0；
反应温度为70℃、80℃、90℃、100℃、120℃、130℃或140℃。
4.根据权利要求1所述的一种绿色制备硫代酰胺的方法，其特征在于，化合物Ⅱ与碘试剂的摩尔比为1:0.05-2；化合物Ⅱ与氧化剂的摩尔比为1:0.5-3。
5.根据权利要求1所述的一种绿色制备硫代酰胺的方法，其特征在于，化合物Ⅱ与碘试剂的摩尔比为1:0.05、1:0.1、1:0.2、1:1或1:2；
化合物Ⅱ与氧化剂的摩尔比为1:0.5、1:1.5、1:2.0、1:2.5或1:3.0。
6.根据权利要求1所述的一种绿色制备硫代酰胺的方法，其特征在于，
所述反应溶剂为N,N-二甲基甲酰胺与水混合物、乙腈与水混合物、乙醇与水混合物、二甲基亚砜与水混合物、四氢呋喃与水混合物、1,2-二氯乙烷、氯仿、二氯甲烷、甲苯、乙腈、N,N-二甲基甲酰胺、乙醇、甲醇、二甲基亚砜、四氢呋喃、四氯化碳、正己烷、正丙醇、异丙醇、丁醇、戊醇、丙酮、2-丁酮中的任意一种或两种以上的组合。
7.根据权利要求1所述的一种绿色制备硫代酰胺的方法，其特征在于，所述反应溶剂为N,N-二甲基甲酰胺与水混合物，N,N-二甲基甲酰胺与水的体积比为1：0.1-2。
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