CN115260026B - 一种4-氯丁酰氯的绿色合成方法 - Google Patents
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- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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Abstract
本申请公开一种4‑氯丁酰氯的合成方法，包括以下步骤：在反应器中加入γ‑丁内酯、三光气和负载型多功能化离子液体催化剂，反应；所述负载型多功能化离子液体催化剂的结构为：
Description
技术领域
本发明涉及一种4-氯丁酰氯的绿色合成方法。
背景技术
4-氯丁酰氯是一种重要的有机合成及医药农药中间体。
目前行业制备4-氯丁酰氯的方法有三种：1)氯化亚砜体系；2)光气体系；3)三光气体系。
氯化亚砜体系：牛宇岚等(《精细化工中间体杂志》)以氯化亚砜为开环试剂，氯化锌为催化剂，在55℃反应22h得到目标产物。此工艺原料成本较低，反应条件温和，但氯化亚砜对环境影响较大，处理成本较高，不符合目前绿色环保工艺的要求。
光气体系：FRNO.1080261/EPNO.253214/US5130478A等专利均报道了以光气为开环试剂，使用了铵盐、三苯基氧膦等催化剂，在120℃-140℃条件下得到目标产物4-氯丁酰氯。光气作为开环试剂，原料价格便宜且副产物对环境污染较小，但光气毒性较大，不利于操作。
三光气体系：CN1o1624340A报道了以三光气为氯化试剂，三苯基氧磷、氯化锌/氯化铝、DMF/三乙胺/三种催化剂，升温至90-120℃下，制备4-氯丁酰氯。CN108863767A报道了以三光气为氯化试剂，三聚磷酸二氢铝与有机胺的复合催化剂，在60-120℃下，反应0.5h-4h，得到4-氯丁酰氯。目前三光气体系工艺，反应温度较高，三光气分解不易控制，危险性较大，且催化剂回收较为困难，不利于工业化生产。
因此，研发出一种新型的制备4-氯丁酰氯方法具有重要的生产应用价值。
发明内容
本发明的目的是提供一种4-氯丁酰氯的绿色合成方法，具有反应效率较高的优点。
三光气室温下稳定、毒性低、可以准确计量，近年来受到广发关注，适合于工业化推广应用。但由于三光气在碱性条件下分解较快，反应过程容易失控。γ-丁内酯在光气/三光气中开环温度较高，加快了三光气的分解速率，反应过程容易失控。
本发明的上述技术目的是通过以下技术方案得以实现的：
一种4-氯丁酰氯的绿色合成方法，包括以下步骤：在反应器中加入γ-丁内酯、三光气和负载型多功能化离子液体催化剂，反应；
所述负载型多功能化离子液体催化剂的结构为：
进一步的，所述LewisAcid选自氯化锌、氯化铝或氯化铬。
进一步的，反应温度为0～60℃，反应时间为8-10h。
进一步的，γ-丁内酯、三光气和负载型多功能化离子液体催化剂的摩尔比为1∶0.34～0.38∶0.001～0.004。
进一步的，所述负载型多功能化离子液体催化剂的制备方法为：
向反应器中加入甲苯，γ-氯丙基三甲氧基硅烷，咪唑，升温至80℃，反应2h；向上述反应液中加入路易斯酸(氯化铝、氯化锌等)搅拌1h；80℃下向反应液中滴加3-丙磺酸内酯，滴毕，80℃下反应5h；向反应液中加入硅胶，混合均匀后，减压浓缩至干得到最终催化剂。
本发明技术效果主要体现在以下方面：
采用本申请的催化剂，控制三光气分解速率且降低γ-丁内酯开环温度，对生产工艺进行创新，以γ-丁内酯为原料、三光气为氯化剂，负载型功能化离子液体为催化剂，反应条件温和，催化剂可回收套用，设备装置简单，有利于工业化大生产。
具体实施方式
4-氯丁酰氯的测定方法：
1、仪器与用具
1.1气相色谱仪：配有FID检测器的Agilent7890或者相当仪器。
1.2色谱柱：SE-5430m×0.32mm×1um
1.3数据处理系统：色谱工作站。
2、色谱条件
进样口温度：250℃
检测器温度：280℃
载气(恒压模式)：氮气总压0.2MPa，柱前压0.1MPa
氢气：0.1MP
空气：0.1MPa
升温程序：80℃(2min)，20℃/min，250℃(5min)
3、供试品配制：
直接进样0.2uL。
4、进样顺序：
待仪器稳定后，进系统空白，正常后再注入供试品溶液并记录色谱图。
5、结果计算：
式中：
A：主峰或者各杂质峰面积；
∑Ai：所有组分峰面积之和。
负载型多功能化离子液体核磁表征方法：
BRUKER 400MHz，溶剂为DMSO。
负载型多功能化离子液体催化剂的制备：
向反应器中加入50g甲苯，19.8g(0.1mol)γ-氯丙基三甲氧基硅烷，6.8g(0.1mol)咪唑，升温至80℃，反应2h。向上述反应液中加入0.1mol路易斯酸(氯化铝、氯化锌等)搅拌1h。80℃下向反应液中滴加3-丙磺酸内酯12.2g(0.1mol)，滴毕，80℃下反应5h。向反应液中加入80g硅胶，混合均匀后，减压浓缩至干得到最终催化剂。1H-NMR(400MHz，DMSO)δ：0.55(m，2H)，1.23(m，2H)，2.0(m，2H)，3.55(m，2H)，3.65(s，9H)，4.27(m，2H)，5.05(m，2H)，7.85(m，1H)，7.95(m，1H)，8.5(s，1H)，8.92(s，1H)。
实施例1：向反应器中加入100gγ-丁内酯，110g三光气，0.1g催化剂(路易斯酸为氯化锌的负载型离子液体)，升温至45℃，反应8h，过滤回收催化剂，后处理得4-氯丁酰氯粗品157g，纯度97％。
实施例2：向反应器中加入100gγ-丁内酯，110g三光气，0.1g催化剂(路易斯酸为氯化铝的离子液体)，升温至30℃，反应6h，过滤回收催化剂，后处理得4-氯丁酰氯粗品151g，纯度98％。
实施例3：向反应器中加入100gγ-丁内酯，110g三光气，0.2g催化剂(路易斯酸为氯化铝的离子液体)，升温至30℃，反应5h，过滤回收催化剂，后处理得4-氯丁酰氯粗品155g，纯度98％。
实施例4：向反应器中加入100gγ-丁内酯，110g三光气，0.1g催化剂(路易斯酸为氯化铬的离子液体)，升温至60℃，反应3h，过滤回收催化剂，后处理得4-氯丁酰氯粗品153g，纯度95％。
实施例5：向反应器中加入100gγ-丁内酯，110g三光气固体，0.3g催化剂(路易斯酸为氯化铬的离子液体)，升温至60℃，反应2h，过滤回收催化剂，后处理得4-氯丁酰氯粗品154g，纯度96％。
实施例6：向反应器中加入100gγ-丁内酯，110g三光气固体，0.2g回收催化剂(路易斯酸为氯化铬的离子液体)，升温至50℃，反应6h，过滤回收催化剂，后处理得4-氯丁酰氯粗品153g，纯度97％。
实施例7：向反应器中加入100gγ-丁内酯，110g三光气固体，0.1g回收催化剂(路易斯酸为氯化锌的离子液体)，升温至50℃，反应6h，过滤回收催化剂，后处理得4-氯丁酰氯粗品153g，纯度97％。
当然，以上只是本发明的典型实例，除此之外，本发明还可以有其它多种具体实施方式，凡采用等同替换或等效变换形成的技术方案，均落在本发明要求保护的范围之内。
Claims (5)
1.一种4-氯丁酰氯的合成方法，其特征是，包括以下步骤：在反应器中加入γ-丁内酯、三光气和负载型多功能化离子液体催化剂，反应；
所述负载型多功能化离子液体催化剂的结构为：。
2. 根据权利要求1所述的一种4-氯丁酰氯的合成方法，其特征是，所述Lewis Acid选自氯化锌、氯化铝或氯化铬。
3.根据权利要求1所述的一种4-氯丁酰氯的合成方法，其特征是，反应温度为0~60℃，反应时间为2-10h。
4.根据权利要求1所述的一种4-氯丁酰氯的合成方法，其特征是，γ-丁内酯、三光气和负载型多功能化离子液体催化剂的摩尔比为1:0.34~0.38:0.001~0.004。
5. 根据权利要求1所述的一种4-氯丁酰氯的合成方法，其特征是，所述负载型多功能化离子液体催化剂的制备方法为：向反应器中加入甲苯，γ-氯丙基三甲氧基硅烷，咪唑，升温至80 ℃，反应2 h；然后加入路易斯酸搅拌1h； 80℃下向反应液中滴加3-丙磺酸内酯，滴毕，80℃下反应5h；向反应液中加入硅胶，混合均匀后，减压浓缩至干得到最终催化剂。
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