CN102127039A - 外型纳迪克酸酐的制备方法 - Google Patents
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Abstract
本发明公开了一种生产外型纳迪克酸酐的新方法，属于有机化学合成领域。该方法以顺丁烯二酸酐和混合碳五为原料，在0-5℃下，用顺酐直接吸收环戊二烯反应生成内型纳迪克酸酐；然后以其为原料，以短链醇为溶剂，乌洛托品、过氧化苯甲酰和[Cu(dppm)(NO3)]2为催化剂，合成外型纳迪克酸酐。与现有技术相比本发明以廉价的乙烯副产物混合碳五为原料制备外型纳迪克酸酐，收率明显高于传统工艺，达96%以上，减小了溶剂污染，更适应于工业化生产。
Description
技术领域
本发明涉及一种化工产品的生产方法，尤其涉及外型纳迪克酸酐的一种生产方法，属于有机化学合成领域。
背景技术
外型纳迪克酸酐（cis-5-Norbornene-exo-2,3-dicarboxylic Anhydride），又称顺-5-降冰片烯-外-2,3-二羧酸酐，无色透明晶体，分子式C9H8O3，分子量164.16，微溶于石油醚，溶于苯、甲苯、丙酮、四氯化碳、氯仿、乙醇和乙酸乙酯等有机溶剂，是医药、农药、材料和树脂等合成的重要中间体之一。目前工业上应用纳迪克酸酐多为内型产物，纳迪克酸酐主要用作聚脂树脂、醇酸树脂和农药的原料以及脲醛树脂、三聚氰胺树脂、松脂等的改性剂、橡胶硫化调节剂、树脂增塑剂、纺织整理渗透剂等，此外，还广泛用于清漆、磁漆、醇酸树脂涂料等。纳迪克酸酐用于不饱和聚脂树脂时，其优点在于比用四氢苯酐树脂具有更好的气干性、耐热性、光洁度、电性能、耐腐蚀性能和机械强度。
外型纳迪克酸酐与内型产物相比，熔点相对更低一些，更适合于应用于树脂和材料行业，此外，使用外型纳迪克酸酐可以合成医药和农药行业的重要中间体顺-5-降冰片烯-外-2,3-二亚胺，内型产物却没有药理作用，而且可能存在副作用。因此，外型纳迪克酸酐的开发具有十分广阔的市场前景，经济效益和社会效益显著。
目前外型纳迪克酸酐的传统生产方法是以环戊二烯和顺酐经Diels-Alder反应制得的内型纳迪克酸酐作为原料，经过多次重结晶提纯得到外型纳迪克酸酐纯品(Journal of the American Chemical Society, 1967, 69:6897-6904)，或经高温加热后溶剂重复结晶得到目标产品(Organic Letters, 2010, 12(13):2904-2907)；以上方法收率均小于40%，而且需要溶剂反复结晶，产生大量废液，污染环境。在工业化实际生产中，急需探索一种环境污染小、收率高的外型纳迪克酸酐的生产方法。
发明内容
本发明目的在于提供一种环境污染小、收率高的直接以混合碳五为起始原料生产外型纳迪克酸酐的新方法。
为实现本发明的目的，本发明技术方案如下：
以顺丁烯二酸酐和混合碳五(其主要成分为环戊二烯、异戊二烯和间戊二烯)为原料，在0-5℃下，用顺丁烯二酸酐直接吸收环戊二烯生成内型纳迪克酸酐。然后，以内型纳迪克酸酐为原料，短链醇作为溶剂，乌洛托品(又称六亚甲基四胺)、过氧化苯甲酰和[Cu(dppm)(NO3)]2(合成方法参见Transition Metal Chemistry, 1997, 22(3): 254-259)作为催化剂，回流反应一定时间后，过滤除催化剂，减压回收溶剂，甲苯和丙酮混合溶剂结晶得到外型纳迪克酸酐纯品。
反应示意图
具体反应步骤如下：
向混合碳五中逐渐加入顺丁烯二酸酐，搅拌，控制反应温度在0-5℃，经气相色谱(GC)检测没有环戊二烯时停止反应，离心分离，液体经汽化、压缩、冷凝得到脱环碳五（其主要成分为异戊二烯和间戊二烯），固体即为内型纳迪克酸酐纯品，收率95%以上。然后，以内型纳迪克酸酐为原料，短链醇作为溶剂，乌洛托品、过氧化苯甲酰和[Cu(dppm)(NO3)]2作为催化剂，回流反应10-24h后，过滤除催化剂，减压回收溶剂，甲苯和丙酮混合溶剂结晶得到外型纳迪克酸酐纯品。
所述的短链醇为乙醇、异丙醇或丙醇。异构反应中使用的催化剂乌洛托品用量为原料内型纳迪克酸酐质量的10-30%；催化剂过氧化苯甲酰用量为原料内型纳迪克酸酐质量的0.03-0.08%；[Cu(dppm)(NO3)]2用量为原料内型纳迪克酸酐质量的4-10%。
以甲苯和丙酮混合溶剂结晶时甲苯和丙酮体积比为1∶1。
本发明有益效果在于：(1) 该方法直接以混合碳五为原料，合成了医药和农药的中间体外型纳迪克酸酐，不需要对原料混合碳五进行精制分离，降低了生产成本，加强了对混合碳五的深加工利用，极具现实意义；(2) 该工艺方法合成外型纳迪克酸酐收率明显高于传统工艺，收率96%以上，减小了溶剂污染，更适应于工业化生产。
附图说明
图为该方法工艺流程图。
具体实施方式
为更好地对本发明进行详细说明，举实施例如下：
实施例1
在0 ℃和搅拌条件下，向60 g混合碳五中逐渐加入顺丁烯二酸酐，经GC检测没有环戊二烯时停止反应，共加入20.9 g顺丁烯二酸酐，抽滤，得到33.2g内型纳迪克酸酐，熔点160-162 ℃，纯度98%(GC)，收率95%。1H NMR (300Hz, CDCl3),δ/ppm: 6.313(2H, t, J=1.778Hz, 5-H, 6-H), 3.571-3.611(2H, m, 2-H, 3-H), 3.496-3.528(2H, m, 1-H, 4-H), 1.765-1.806(1H, m, 7-H), 1.572-1.604(1H, dd, J1=0.51Hz, J2=9.0Hz, 7-H); 13C NMR (300Hz, CDCl3),δ/ppm: 171.4, 135.4, 52.7, 47.0, 46.0。
在反应釜中加入上述33.2 g内型纳迪克酸酐，200 mL乙醇作为溶剂，6.6 g的乌洛托品、16.6 mg的过氧化苯甲酰和2.3 g[Cu(dppm)(NO3)]2作为催化剂，回流反应10 h后，过滤除催化剂，减压回收溶剂，100 mL甲苯和100 mL丙酮混合溶剂结晶得到外型纳迪克酸酐纯品31.9 g，熔点140-142 ℃，纯度98%(GC)，收率96%。1H NMR (300Hz, CDCl3),δ/ppm: 6.339(2H, t, J=1.785Hz, 5-H, 6-H), 3.459(2H, t, J=1.645Hz, 2-H, 3-H), 3.101(2H, d, J=1.41Hz, 1-H, 4-H), 1.696-1.651(1H, m, 7-H), 1.447(1H, d, J=10.23Hz, 7-H); 13C NMR (300Hz, CDCl3),δ/ppm: 171.6, 137.9, 48.7, 46.8, 44.0; IR (KBr), ν/cm-1: 1860, 1777, 1218, 1086; Ms(m/z): 164.2(M+)。
实施例2
在2 ℃和搅拌条件下，向300 g混合碳五中逐渐加入顺丁烯二酸酐，经GC检测没有环戊二烯时停止反应，共加入105 g顺丁烯二酸酐，反应混合物离心分离，得到168 g内型纳迪克酸酐，熔点162-164℃，纯度99%(GC)，收率95%。
在反应釜中加入上述168 g内型纳迪克酸酐，800 mL异丙醇作为溶剂，16.8 g的乌洛托品，50.4 mg的过氧化苯甲酰和16.8 g[Cu(dppm)(NO3)]2作为催化剂，回流反应24 h后，过滤除催化剂，减压回收溶剂，400 mL甲苯和400 mL丙酮混合溶剂结晶得到外型纳迪克酸酐纯品163g，熔点140-142 ℃，纯度98%(GC)，收率97%。
实施例3
在5 ℃和搅拌条件下，向1800 g混合碳五中逐渐加入顺丁烯二酸酐，经GC检测没有环戊二烯时停止反应，共加入630 g顺丁烯二酸酐，反应混合物离心分离，得到1013 g内型纳迪克酸酐，熔点160-162 ℃，纯度98%(GC)，收率96%。
在反应釜中加入上述1013 g内型纳迪克酸酐，5 L丙醇作为溶剂，304 g的乌洛托品、0.81 g的过氧化苯甲酰和40.6 g [Cu(dppm)(NO3)]2作为催化剂，回流反应16h后，过滤除催化剂，减压回收溶剂，2 L甲苯和2 L丙酮混合溶剂重结晶得到外型纳迪克酸酐纯品973 g，熔点140-142 ℃，纯度98%(GC)，收率96%。
Claims (3)
1.一种生产外型纳迪克酸酐的方法，其特征在于，向混合碳五中逐渐加入顺丁烯二酸酐，搅拌，控制反应温度在0-5 ℃，经气相色谱检测没有环戊二烯时停止反应，离心分离，液体经汽化、压缩、冷凝得到脱环碳五，固体为内型纳迪克酸酐；然后，以内型纳迪克酸酐为原料，短链醇为溶剂，乌洛托品、过氧化苯甲酰和[Cu(dppm)(NO3)]2为催化剂，回流反应10-24 h后，过滤除催化剂，减压回收溶剂，甲苯和丙酮混合溶剂结晶得到外型纳迪克酸酐；所述混合碳五主要成分为环戊二烯、异戊二烯和间戊二烯；脱环碳五主要成分为异戊二烯和间戊二烯。
2.如权利要求1所述的生产外型纳迪克酸酐的方法，其特征在于，使用短链醇为乙醇、异丙醇或丙醇。
3.如权利要求1所述的生产外型纳迪克酸酐的方法，其特征在于，催化剂乌洛托品使用量为原料内型纳迪克酸酐质量的10-30%；催化剂过氧化苯甲酰使用量为原料内型纳迪克酸酐质量的0.03-0.08%；[Cu(dppm)(NO3)]2使用量为原料内型纳迪克酸酐质量的4-10%。
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| CN104496942A (zh) * | 2013-08-12 | 2015-04-08 | 成都科瑞德医药投资有限责任公司 | 外亚甲基四氢苯酐的纯化方法 |
| CN112239435A (zh) * | 2019-07-18 | 2021-01-19 | 郑州大学 | 外型纳迪克酸酐晶型及其制备方法 |
| CN113501797A (zh) * | 2021-08-16 | 2021-10-15 | 江苏百奥信康医药科技有限公司 | 一种外型纳迪克酸酐的制备方法 |
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| CN104370863A (zh) * | 2014-11-25 | 2015-02-25 | 南京工业大学 | 外型降冰片烯二酸酐的制备方法 |
| CN112239435A (zh) * | 2019-07-18 | 2021-01-19 | 郑州大学 | 外型纳迪克酸酐晶型及其制备方法 |
| CN113501797A (zh) * | 2021-08-16 | 2021-10-15 | 江苏百奥信康医药科技有限公司 | 一种外型纳迪克酸酐的制备方法 |
| CN113501797B (zh) * | 2021-08-16 | 2023-11-10 | 江苏百奥信康医药科技有限公司 | 一种外型纳迪克酸酐的制备方法 |
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