CN114146731A - 寡聚双核MOFs类环氧氯丙烷动力学拆分催化剂及其合成方法 - Google Patents
寡聚双核MOFs类环氧氯丙烷动力学拆分催化剂及其合成方法 Download PDFInfo
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- CN114146731A CN114146731A CN202111439091.5A CN202111439091A CN114146731A CN 114146731 A CN114146731 A CN 114146731A CN 202111439091 A CN202111439091 A CN 202111439091A CN 114146731 A CN114146731 A CN 114146731A
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- binuclear
- kinetic resolution
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- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 5
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- VZHHNBNSMNNUAD-UHFFFAOYSA-N cobalt 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound [Co].OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VZHHNBNSMNNUAD-UHFFFAOYSA-N 0.000 description 1
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- WXEICPMZIKLINJ-UHFFFAOYSA-L iron(2+) diacetate tetrahydrate Chemical compound O.O.O.O.[Fe+2].CC([O-])=O.CC([O-])=O WXEICPMZIKLINJ-UHFFFAOYSA-L 0.000 description 1
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Images
Classifications
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/32—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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Abstract
本发明提供了寡聚双核MOFs类环氧氯丙烷动力学拆分催化剂及其合成方法，该类寡聚的双核MOFs通过分子内的双分子协同催化提高动力学拆分的活性，大大降低催化剂的使用量，约为单核SalenM催化剂用量的3‑4%，同时由于具有MOFs多孔三维结构，具有多相催化剂的结果特点，反应后通过简单的处理，过滤后即可重复多次使用。
Description
技术领域
本发明提供一种寡聚双核MOFs类环氧氯丙烷动力学拆分催化剂及其合成方法。属于医药化工技术领域。
背景技术
手性环氧氯丙烷是一种非常重要的手性药物合成中间体，可用于制备降血脂类药物阿伐他汀、芳氧丙胺醇类β-肾上腺素阻断剂、减肥药左旋肉碱、抗生素海藻唑啉等多种药物，在医药、农药和精细化工等领域有极为广泛的应用。外消旋的环氧氯丙烷水解动力学拆分是一种高效合成手性环氧氯丙烷和1,2-手性二醇的化合物的方法。1997年，JACOBSEN（US5929232,US2003073855A1）首次成功的进行了末端环氧的动力学拆分。2002年，KURESHYRI［Journal of Molecular Catalysis A：Chemical，2002，179（1-2）：73-77.］制备了一种亚甲基桥链的双聚体形式的salenCo(III)催化剂，提高了动力学拆分的活性。2006年丁奎岭（CN101967165A）公开了一种寡聚的双核salenCo（III）催化剂，由于双核金属在分子内协同催化，符合动力学拆分的机理，大大降低了催化剂的使用量。但所使用的催化剂仍然存在着价格昂贵、用量高、重复性不理想等问题。固载化的salenCo（III）催化剂(CN105618141A)或低聚物形式的salenCo（III）催化剂(WHITEDE，Tetrahedron：Asymmetry，2003，14（22）：3633-3638)，虽然催化剂方便回收，但存在选择性低的缺点。
金属-有机框架材料(MOFs)是近十年来发展迅速的一种配位聚合物，具有三维的孔结构，在催化、储能和分离中都有广泛应用。蒋成君（CN1876640A）公开了一种双核MOFs（salenCo（III）-ZnCl2）首次用于环氧氯丙烷动力学拆分。崔勇（Journal of the AmericanChemical Society,2012,134,8058）使用salenCo（III）与硝酸镉反应得到的双核MOFs(Cd4-salenCo（III）)，也能很好的进行环氧氯丙烷的动力学拆分。同年，林文斌（Chem.Commun.,2012,48,8766–8768）对MOFs的催化机理提出了解释，认为不同于均相的SalenCo的单核催化机理，而是类似于双核催化机理。2017年，崔勇（Journal of theAmerican Chemical Society,2017,139,8259）又进一步使用多种席夫碱合成了多元金属-有机框架化合物（MTV-MOFs）(Zn4-salenCu-salenCo（III）)，除了可以进行动力学拆分外，还可以催化其它多种反应。总的来说，MOFs催化剂虽然回收起来相对容易，但其动力学拆分的催化活性还需要提高，催化剂使用量仍偏大。
发明内容
针对上述现有催化剂的不足之处，本发明提供了寡聚双核MOFs类环氧氯丙烷动力学拆分催化剂及其合成方法，该类寡聚的双核MOFs通过分子内的双分子协同催化提高动力学拆分的活性，大大降低催化剂的使用量，约为单核SalenM催化剂用量的3-4%，同时由于具有MOFs多孔三维结构，具有多相催化剂的结果特点，反应后通过简单的处理，过滤后即可重复多次使用。
本发明提供的寡聚双核MOFs类环氧氯丙烷动力学拆分催化剂及其合成方法，该催化剂首先通过二醇经酯键做桥链链接可双配位的席夫碱中心，然后再与醋酸盐反应得到寡聚的SalenM型化合物，寡聚的SalenM型化合物再与盐反应，得到的寡聚双核MOFs型催化剂。
作为优选，寡聚的双核MOFs型催化剂通式为S4(ML4)(DMF)4.4H2O，其中S为代表骨架金属，M为活性中心金属，L为通过二醇经酯键做桥链链接的环己二胺衍生的席夫碱类配体。
作为优选，寡聚的双核MOFs型催化剂中L席夫碱配体中所使用的二醇为1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,8-辛二醇、1,4-环己二醇、对苯二酚中的一种，优选1,4-环己二醇。
作为优选，寡聚的双核MOFs型催化剂中L席夫碱配体中所使用的水杨醛为水杨醛、2-叔丁基水杨醛、2，3-二叔丁基水杨醛、2-甲基水杨醛、3,5-二甲基水杨醛、5-甲氧基水杨醛中的一种，优选3,5-二叔丁基水杨醛。
作为优选，寡聚的双核MOFs型催化剂中S为金属锌或镉，锌来源于硝酸锌、醋酸锌、草酸锌、氯化锌。优选硝酸锌中的一种，镉来源于硝酸镉。
作为优选，寡聚的双核MOFs型催化剂中M为金属铜、镍、钴、锰、铁等金属的一种或几种，优选钴或钴锰混合金属。
本发明提供的一种寡聚的双核MOFs催化剂，通过以下步骤合成：3-叔丁基-4-羟基-5-醛基苯甲酸在脱水剂作用下，和1,4-环己二醇脱水成酯，得到中间体MOFs-1。一分子的2,3-二叔丁基水杨醛和1,2-二胺基环己烷缩合，得到单席夫碱中间体MOFs-2。将MOFs-1和MOFs-2反应得到配体L。配体L合成路线如附图1所示。
将配体L和金属M的醋酸盐在甲醇中回流，降温到室温过滤。得到寡聚SalenM席夫碱类化合物。合成路线如附图2所示。
将SalenM席夫碱类化合物溶解到N,N-二甲基甲酰胺，加入硝酸锌或硝酸镉，加热到一定温度，得到黑红色晶体。合成路线如附图3所示。
其中的SalenM可以为单一金属的席夫碱，也可以是两种或两种金属以上的席夫碱的混合物。
附图说明
图1为配体L合成路线示意图；
图2为寡聚SalenM席夫碱类化合物成路线示意图；
图3为寡聚SalenM席夫碱类化合物合成寡聚的双核MOFs型催化剂路线示意图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
寡聚双核SalenCo-环C6的合成：
MOFs-1合成：
在氮气保护下，向250mL 三口烧瓶中加入8.89g2-羟基-3-叔丁基-5-羧基苯甲醛（40mmol）、2.32g1,4-环己二醇（20mmol）和0.49g4-二甲氨基吡啶（DMAP,4mmol），加入80mL二氯乙烷及少量N,N-二甲基甲酰胺。搅拌10分钟后冷却到0℃，加入5.3gN,N-二异丙基碳化二亚胺（DIC,42mmol）。搅拌10分钟后，升温到室温搅拌24小时。HPLC跟踪2-羟基-3-叔丁基-5羧基苯甲醛反应小于1%时，向其中加入10%的盐酸（20mL）洗涤一次，用10%碳酸氢钠洗涤至水层pH=7。减压浓缩，向其中加入甲醇50mL，得到MOFs-1的甲醇溶液；
MOFs-2合成：
9.47g3,5-二叔丁基水杨醛（40mmol）溶于20g甲醇溶液中，冷却到10℃。将4.57g（R,R）-1,2-环己二胺（40mmol）的溶于15g甲醇，搅拌溶清后，滴加到3,5二叔丁基水杨醛的甲醇溶液中。缓慢升温到室温搅拌24小时。HPLC跟踪3,5-二叔丁基水杨醛小于0.5%时，得到MOFs-2的甲醇溶液；
L配体合成：
将MOFs-1的甲醇溶液升温到60℃，将MOFs-2溶液滴加到MOFs-1溶液中，在60-65℃回流反应5小时。HPLC跟踪MOFs-1含量小于1%时，降温到50-55℃，得到L配体的甲醇溶液；
寡聚双核SalenCo合成：
将9.96g四水合醋酸钴（40mmol）溶于100g甲醇中，然后在50-55℃滴加到L配体的甲醇溶液中。升温到60-65℃回流5小时。HPLC跟踪L配体反应完全后，减压回收甲醇至粘稠状液体。滴加200mL水，搅拌降温到15℃以下，过滤，得到紫红色晶状固体。将紫红色晶状固体在200mL的水中，在60℃水中打浆两次，除去游离的钴离子。过滤干燥，得到21.5g寡聚双核的SalenCo催化剂。记作SalenCo-环C6，总收率85%以上。
实施例2
寡聚双核SalenCo-C3的合成：
以1,3-丙二醇代替1,4-环己二醇，其它条件同实施例1。得到寡聚双核SalenCo-C3。
实施例3
寡聚双核SalenCo-C4的合成：
以1,4-丁二醇代替1,4-环己二醇，其它条件同实施例1。得到寡聚双核SalenCo-C4。
实施例4
寡聚双核SalenCo-C6的合成：
以1,6-己二醇代替1,4-环己二醇，其它条件同实施例1。得到寡聚双核SalenCo-C6。
实施例5
寡聚双核SalenCu-环C6的合成：
以一水合醋酸铜代替四水合醋酸钴，其它条件同实施例1。得到寡聚的双核SalenCu-环C6。
实施例6
寡聚双核SalenFe-环C6的合成：
以四水合醋酸亚铁代替四水合醋酸钴，其它条件同实施例1。得到寡聚的双核SalenFe-环C6。
实施例7
寡聚双核SalenNi-环C6的合成：
以四水合醋酸镍代替四水合醋酸钴，其它条件同实施例1。得到寡聚的双核SalenNi-环C6。
实施例8
寡聚双核SalenMn-环C6的合成：
以四水合醋酸锰（II）代替四水合醋酸钴。回流2小时后，加入1.69g LiCl(40mmol)回流反应2小时。其它条件同实施例1。得到寡聚的双核SalenMn-环C6。
实施例9
Zn4(CoL)4(DMF)4.4H2O的合成：
氮气氛下，将2.97gZn(NO3)2·6H2O (10mmol), 17.11g salenCo-环C6(20mmol), 12mL DMF, 6mL乙醇, 6mL异丙醇升温到80℃，反应24小时。降温到室温，过滤，得到黑色晶状固体。收率大于95%。
实施例10
Zn4(CuL)4(DMF)4.4H2O的合成：
以SalenCu-C6代替salenCo-C6，其它条件同例9，得到Zn4(CuL)4(DMF)4.4H2O。
实施例11
Zn4(NiL)4(DMF)4.4H2O的合成：
以SalenNi-C6代替salenCo-C6，其它条件同例9，得到Zn4(NiL)4(DMF)4.4H2O。
实施例12
Zn4(FeL)4(DMF)4.4H2O的合成：
以SalenFe-C6代替salenCo-C6，其它条件同例9，得到Zn4(FeL)4(DMF)4.4H2O。
实施例13
Zn4(MnL)4(DMF)4.4H2O的合成：
以SalenMn-C6代替salenCo-C6，其它条件同例9，得到Zn4(MnL)4(DMF)4.4H2O。
实施例14
Cd4(CoL)4(DMF)4.4H2O的合成：
以Cd(NO3)2.4H20代替Zn(NO3)2·6H2O,其它条件同例9，得到Cd4(CoL)4(DMF)4.4H2O。
实施例15
Zn4(CoL)2(MnL)2(DMF)4.4H2O的合成：
氮气氛下，将2.97g Zn(NO3)2·6H2O (10mmol), 17.11 g SalenCo-环C6(10mmol), 13.28g SalenMn-环C6(10mmol)，12mL DMF, 6mL乙醇, 6mL 异丙醇升温到80℃，反应24小时。降温到室温，过滤，得到黑色晶状固体。收率大于95%。
实施例16
环氧动力学拆分评价1
称量0.1 g寡聚SalenCo-环C6催化剂加入400g环氧氯丙烷中，加入0.9g醋酸，搅拌。室温鼓空气两小时，得到活化的催化剂浆状悬浮液。升温到20-25℃，慢慢滴加110g水，约滴加5小时。反应5小时后，每两小时取样分析样品的e.e.值。当e.e.值大于99%时停止反应，反应约9小时。过滤回收催化剂。母液浓缩。减压条件下，在55-58℃下蒸馏得到S-环氧氯丙烷194g，收率48.5%。釜残为副产物R-1,2-氯丙二醇。不同桥链醇种类的催化剂的催化活性见表下表：
| 实施例 | 桥链醇种类 | 反应时间（h） | e.e.（%） | 收率（%） |
| 1 | 1,4-环己二醇 | 9 | 99.3 | 48.5 |
| 2 | 1,3-丙二醇 | 11 | 99.0 | 47.1 |
| 3 | 1,4-丁二醇 | 12 | 99.0 | 46.1 |
| 4 | 1,6-己二醇 | >12 | 99.0 | 45.1 |
由上表可以看出，寡聚双核SalenCo的催化活性，相对于SalenM来说，催化剂用量大大降低，约为其用量的3.3%。另外不同桥链的寡聚双核SalenCo 的催化活性有较大的差别，1,4-环己二醇做桥链时，空间结构较稳定，进行环氧氯丙烷动力学拆分的选择性最高，反应液e.e.值达到99%的时间最短，收率最高。1,4-对苯二酚做桥链时结果同1,4-环己二醇做桥链的结果差不多。1,6-己二醇由于空间扭曲性大，反应液e.e.值达到99%的时间最长，收率最低。
不同活性中心金属的寡聚双核SalenM-环C6的催化活性见下表：评价过程同环氧动力学拆分评价1，
| 实施例 | M金属 | 反应时间（h） | e.e.（%） | 收率（%） |
| 1 | Co | 9 | 99.3 | 48.5 |
| 8 | Mn | 10 | 99.0 | 47.3 |
| 5 | Cu | 12 | 99.0 | 46.5 |
| 6 | Fe | >12 | 99.0 | 45.7 |
| 7 | Ni | >12 | 99.0 | 44.1 |
由上表可以看出，Co金属作为活性中心时催化活性最好，反应液e.e.值达到99%的时间最短，收率最高。而Ni金属的催化活性最差。
环氧动力学拆分评价2
称量0.07g加入400g环氧氯丙烷中，加入0.9g醋酸，搅拌，室温鼓空气两小时，得到活化的催化剂浆状悬浮液。升温到20-25℃，慢慢滴加110g水，约滴加5小时。反应5小时后，每两小时取样分析样品的e.e.值。当e.e.值大于99%时，停止反应。反应9.5小时。过滤回收催化剂，母液浓缩。减压条件下，在55-58℃下蒸馏得到S-环氧氯丙烷196g，收率49%。釜残为副产物R-1,2-氯丙二醇。不同金属中心的催化剂的催化活性见下表：
| 实施例 | S/M | 反应时间（h） | e.e.（%） | 收率（%）） |
| 9 | Zn/Co | 9.5 | 99.2 | 49.0 |
| 10 | Zn/Cu | 12 | 99.0 | 46.4 |
| 11 | Zn/Ni | >12 | 99.0 | 44.1 |
| 12 | Zn/Fe | >12 | 99.0 | 45.7 |
| 13 | Zn/Mn | 10 | 99.0 | 47.3 |
| 15 | Zn/Co/Mn | 7 | 99.3 | 48.2 |
| 14 | Cd/Co | 10 | 99.0 | 48.0 |
由上表可以看出，MOFsM型催化剂能进一步降低催化剂的使用量，活性也有一定程度的提高。其中Zn/Co/Mn型的MOFs催化剂只需0.07g，反应7个小时，反应液e.e.值就达到99%。
对比例
称量3g SalenCo加入400g环氧氯丙烷中，加入0.9g醋酸，搅拌。室温鼓空气两小时，得到活化的催化剂溶液。升温到18-22℃，慢慢滴加110g水，约滴加5小时。反应5小时后，每两小时取样分析样品的e.e.值，当e.e.值大于99%，停止反应，反应约12小时。浓缩蒸馏得到S-环氧氯丙烷179.1 g，收率44.7%。
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。
Claims (6)
1.寡聚双核MOFs类环氧氯丙烷动力学拆分催化剂及其合成方法，其特征在于：该催化剂首先通过二醇经酯键做桥链链接可双配位的席夫碱中心，然后再与醋酸盐反应得到寡聚的SalenM型化合物，寡聚的SalenM型化合物再与盐反应，得到寡聚的双核MOFs型催化剂。
2.根据权利要求书1所述的寡聚双核MOFs类环氧氯丙烷动力学拆分催化剂及其合成方法，其特征在于：所述寡聚的双核MOFs型催化剂通式为S4(ML4)(DMF)4.4H2O，其中S为代表骨架金属，M为活性中心金属，L为通过二醇经酯键做桥链链接的席夫碱类配体。
3.根据权利要求书2所述的寡聚双核MOFs类环氧氯丙烷动力学拆分催化剂及其合成方法，其特征在于：所述寡聚的双核MOFs型催化剂中L席夫碱配体中所使用的二醇为1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,8-辛二醇、1,4-环己二醇、对苯二酚中的一种，优选1,4-环己二醇。
4.根据权利要求书2所述的寡聚双核MOFs类环氧氯丙烷动力学拆分催化剂及其合成方法，其特征在于：所述寡聚的双核MOFs型催化剂中L席夫碱配体中所使用的水杨醛为水杨醛、2-叔丁基水杨醛、2，3-二叔丁基水杨醛、2-甲基水杨醛、3,5-二甲基水杨醛、5-甲氧基水杨醛中的一种，优选3,5-二叔丁基水杨醛。
5.根据权利要求书2所述的寡聚双核MOFs类环氧氯丙烷动力学拆分催化剂及其合成方法，其特征在于：所述寡聚的双核MOFs型催化剂中S为金属锌或镉，锌来源于硝酸锌、醋酸锌、草酸锌、氯化锌中的一种，优选硝酸锌，镉来源于硝酸镉。
6.根据权利要求书2所述的寡聚双核MOFs类环氧氯丙烷动力学拆分催化剂及其合成方法，其特征在于：所述寡聚的双核MOFs型催化剂中M为金属铜、镍、钴、锰、铁等金属的一种或几种，优选钴或钴锰混合金属。
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