CN104356001A - 一种用硫脲还原硝基化合物得到胺类物质的方法 - Google Patents
一种用硫脲还原硝基化合物得到胺类物质的方法 Download PDFInfo
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Abstract
本发明公开了用硫脲还原硝基化合物得到胺类物质的方法。以硫脲作为氢源，以硝基化合物为原料，在碱性条件下发生反应，经萃取分离后得到胺类化合物。与本发明相比其显著的优点：(1)硫脲作为氢源，与氢气、氢化铝锂、硼氢化钠等氢源相比，反应条件温和，价格低廉，来源广泛。(2)合成条件简单，后处理容易。(3)本反应不需要过渡金属作为催化剂，对环境危害降到最低，降低合成成本。
Description
技术领域
本发明属于有机合成领域，具体涉及到硝基类化合物还原成氨基类物质的合成方法。
背景技术
芳香伯胺是具有活性的天然产物的重要中间体，在农药，染料，制药和感光材料中都有应用；在有机合成中，特别是在交叉偶联反应中是重要的合成原料。芳香胺类化合物一般是由硝基化合物通过还原得到，一般是在H2或者是其它的还原剂在金属的催化下得到。已经报道的硝基还原成氨基的方法有用9，10-二氢蒽，富勒烯/H2，还原氧化石墨烯/水合肼，活性碳/水合肼，(2-吡啶基)苯甲醇，葡萄糖，鸭嘴花碱等作为氢源和催化剂下由硝基的还原直接得到胺类化合物。其中具有代表的：在硝基类物质中加入硫化钠，硫代硫酸钠溶解在水中，加热得到胺类化合物(刘天军，武莉，苗博龙等含有硝基苯基的化合物中硝基还原成氨基的方法申请号：200710059886.7)；有以铂纳米线为催化剂还原加氢硝基类化合物从而得到目标产物(顾宏伟曹雪琴等硝基化合物催化还原制备氨基化合物的方法申请号：201110006899.4)；有以双氧水处理的活性炭为催化剂，在溶剂中于0—100℃，1—10个大气压下滴加水合肼，将硝基化合物中的硝基还原为氨基化合物(姜玉钦，任保齐等一种催化还原硝基化合物制备氨基化合物的方法申请号：201310383904.2)；在已经报道的方法中要么需要引入气体的装备，要么需要昂贵的金属催化剂，因此急需寻找出无毒非气体的物质作为氢源来催化还原硝基类物质得到胺类化合物。
发明内容
本发明的目的在于合成一系列胺类化合物。利用硫脲作为氢源，在碱性条件下，以芳香类的硝基化合物为原料，得到对应的胺类化合物。
实现本发明目的的技术解决方案为：一种用硫脲还原硝基化合物得到胺类物质的方法，以硫脲作为氢源，以如下结构的硝基化合物为原料，在碱性条件下发生反应，经萃取分离后得到胺类化合物，
其中，R选自H、2-CH3、3-CH3、4-CH3、4-CH3CH2、2,4-二氟、2-氟-3-氯、3-F、4-Br、2-NH2、3-NH2、4-NH2、3-F-4-NH2或4-CH3CO。
进一步，碱性条件中的碱选自氢氧化钾、氢氧化钠或叔丁醇钾，其用量为硝基化合物的3-5当量。
进一步，反应温度为70～120℃，反应时间为8-24h。
进一步，反应的溶剂为甲醇、乙醇或水。
进一步，硫脲用量为硝基化合物的2-5当量。
本发明与现有技术相比，其显著优点是：
1.在整个反应中，不需要加入气体，不需要过渡金属作为催化剂，只需要硫脲作为氢源即可，降低设备的要求和合成的成本。
2.在反应中，不需要高压，只需在常压下即可进行反应。
3.反应结束后，只需要萃取即可得到产物，后处理简单。
下面结合附图对本发明作进一步详细描述。
附图说明
图1本发明合成方法的原理示意图。
具体实施方式
图1中，硫脲经过加热后分解生产氨气和硫化氢气体，这些气体即充当了反应中的氢源又起到了催化的作用，这些气体活化了硝基，在氢源的参与下，还原成为胺类化合物。
本发明的合成路线如下：
R选自H、2-CH3、3-CH3、4-CH3、4-CH3CH2、2,4-二氟、2-氟-3-氯、3-F、4-Br、2-NH2、3-NH2、4-NH2、3-F-4-NH2或4-CH3CO。
在反应中，以对甲基硝基苯为模板反应，探索反应的最佳条件得到对甲基苯胺，结果如表1所示。
表1反应条件的探索
具体步骤为：
取0.5mmol(68.5mg)的对甲基硝基苯，2.0mmol(152.0mg)的硫脲，1.5mmol(168.0mg)的叔丁醇钾在耐压管中，加入2ml的乙醇，在80℃的油浴中，反应24h后停止反应，蒸干除去反应溶剂，加入酸性的食盐水洗涤至中性，乙酸乙酯萃取，取上层有机相得到对甲基苯胺38.2mg。
实施例1
分别取0.5mmol(68.5mg)的邻、间、对甲基硝基苯，2.0mmol(152.0mg)的硫脲，1.5mmol(168.0mg)的叔丁醇钾在耐压管中，加入2ml的乙醇，在80℃的油浴中，反应8h后停止反应，蒸干除去反应溶剂，加入酸性的食盐水洗涤至中性，乙酸乙酯萃取，取上层有机相分别得到邻、间、对甲基苯胺38.9mg，38.2mg，37.4mg。
实施例2
分别取0.5mmol的对乙基硝基苯(75.5mg)、对氯硝基苯(78.5mg)、对溴硝基苯(100.5mg)、对乙酰基硝基苯(82.5mg)，2.0mmol(152.0mg)的硫脲，1.5mmol(168.0mg)的叔丁醇钾在耐压管中，加入2ml的乙醇，在80℃的油浴中，反应10h后停止反应，旋干反应物质，加入酸性的食盐水洗涤至中性，乙酸乙酯萃取，取上层有机相得到对乙基苯胺(58.3mg)、对氯苯胺(30.5mg)、对溴苯胺(34.2mg)。
实施例3
分别取0.5mmol(69.0mg)的邻间对硝基苯胺，2.0mmol(152.0mg)的硫脲，1.5mmol(168.0mg)的叔丁醇钾在耐压管中，加入2ml的乙醇，在80℃的油浴中，反应12h后停止反应，旋干反应物质，加入酸性的食盐水洗涤至中性，乙酸乙酯萃取，取上层有机相分别得到1,2-苯二胺(45.3mg)，1,3-苯二胺(40.5mg)，1,4-苯二胺(34.2mg)。
实施例4
分别取0.5mmol的2,4-二氟硝基苯(79.5mg)、2-氟-3-氯-硝基苯(87.5mg)、3-氟-4-氨基-硝基苯(78.0mg)，2.0mmol(152.0mg)的硫脲，1.5mmol(168.0mg)的叔丁醇钾在耐压管中，加入2ml的乙醇，在120℃的油浴中，反应24h后停止反应，旋干反应物质，加入酸性的食盐水洗涤至中性，乙酸乙酯萃取，取上层有机相得到对2,4-二氟苯胺(133.5mg)、2-氟-3-氯-苯胺(43.5mg)、3-氟-4-氨基-苯胺(37.5mg)。
Claims (5)
1.一种用硫脲还原硝基化合物得到胺类物质的方法，其特征在于，以硫脲作为氢源，以如下结构的硝基化合物为原料，在碱性条件下发生反应，经萃取分离后得到胺类化合物，
其中，R选自H、2-CH3、3-CH3、4-CH3、4-CH3CH2、2,4-二氟、2-氟- 3-氯、3-F、4-Br、2-NH2、3-NH2、4-NH2、3- F-4-NH2或4-CH3CO。
2.如权利要求1所述的用硫脲还原硝基化合物得到胺类物质的方法，其特征在于，碱性条件中的碱选自氢氧化钾、氢氧化钠或叔丁醇钾，其用量为硝基化合物的3-5当量。
3.如权利要求1所述的用硫脲还原硝基化合物得到胺类物质的方法，其特征在于，反应温度为70~120℃，反应时间为8-24h。
4.如权利要求1所述的用硫脲还原硝基化合物得到胺类物质的方法，其特征在于，反应的溶剂为甲醇、乙醇或水。
5.如权利要求1所述的用硫脲还原硝基化合物得到胺类物质的方法，其特征在于，硫脲用量为硝基化合物的2-5当量。
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| CN106478426A (zh) * | 2015-08-26 | 2017-03-08 | 盐城市瓯华化学工业有限公司 | 一种烟酸法制备硫化碱的芳香族硝基化合物的方法 |
| CN115433124A (zh) * | 2022-10-17 | 2022-12-06 | 常州佳德医药科技有限公司 | 一种4-氯-6-甲氧基-7-苄氧基喹啉的制备方法 |
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| CN115433124A (zh) * | 2022-10-17 | 2022-12-06 | 常州佳德医药科技有限公司 | 一种4-氯-6-甲氧基-7-苄氧基喹啉的制备方法 |
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