CN114874342A - Dac-binap生物基手性配体制备方法与不对称催化氢化应用 - Google Patents
Dac-binap生物基手性配体制备方法与不对称催化氢化应用 Download PDFInfo
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Abstract
本发明公开了DAC‑BINAP生物基手性配体的制备方法与不对称催化氢化中的应用,以纤维素为原料,通过选择性氧化制备双醛基纤维素,再以醛基纤维素和5,5’‑二氨‑BINAP为原料,通过席夫碱反应制备DAC‑5,5’‑二氨‑BINAP手性配体,最后以铑催化剂和DAC‑5,5’‑二氨‑BINAP手性配体为原料,通过络合反应络合,应用于不对称催化氢化反应。在催化氢化过程中,无需加入任何其他催化剂,在温和的实验条件下即可得到较高的反应转化率和对应选择性,也能得到较好的立体选择性。双醛基纤维素的利用首次实现了将生物基材料引入手性配体中,使得此手性配体可以回收利用,并且多次循环仍然表现出较高的催化活性,从而节约了资源,降低反应成本。
Description
技术领域
本发明属于生物材料技术和催化剂应用领域,具体涉及一种DAC-BINAP生物基手性配体的制备方法与不对称催化氢化中的应用。
背景技术
这里的陈述仅提供与本发明相关的背景技术,而不必然地构成现有技术。
以氢气作为氢源的不对称氢化反应,是高效合成手性化合物最具有原子经济性和环境友好的合成方法之一,在手性药物、食品添加剂、农药等生产过程中都有广泛的应用。过渡金属与手性配体催化不对称催化氢化的反应中,因均相催化剂的活性中心高度分散在反应体系中,通常表现出非常高的催化活性在。但在均相催化反应体系中,催化剂与配体容易泄露到环境中,不仅浪费资源,还会给环境带来污染。此外,通过不对称催化氢化得到具有生物活性的手性中间体,应用于药物合成路线中是高效合成手性药物的重要方向之一,而均相催化剂给药物中间体的纯化分离带来了困难。针对上述问题,科学家们提出均相催化剂多相化的策略。目前应用最广泛、最有效的就是利用物理或化学的方法,将均相催化剂固定到固体载体表面,制备成负载型催化剂
发明内容
在均相催化剂多相化研究中广泛使用的负载型催化剂载体材料为有机高分子材料和无机材料。这些材料制备的多相催化剂虽然解决了催化剂回收困难的问题,也具有很好的催化活性,但是非可再生资源。在世界经济快速发展的今天,天然气、煤炭、石油等化石能源高速消耗,导致生态环境不断恶化,严重威胁着人类社会的可持续发展,这一现状迫使人们寻找以绿色方法开发新型环境友好型功能材料。针对现有技术存在的不足,本发明的目的是使用醛基纤维素作为载体,提供DAC-BINAP生物基手性配体及其制备方法与不对称催化氢化中的应用。
为了实现上述目的,本发明是通过如下的技术方案来实现:
第一方面,本发明提供一种双醛基纤维素的制备方法,包括如下步骤:纤维素和高碘酸钠在氯化锂的催化作用下反应,氯化锂作为催化剂,有促进和活化作用,催化高碘酸钠将纤维素的羟基氧化成醛基,制得。
第二方面,本发明提供DAC-BINAP生物基手性配体的制备方法,以双醛基纤维素和5,5’-二氨-BINAP为原料,通过席夫碱反应制备而成。
第三方面,本发明提供制备所得DAC-BINAP生物基手性配体负载金属铑在不对称催化氢化催化剂中的应用。
本发明的以上一种或多种实施方式取得的有益效果如下:
首先,本发明以纤维素为原料,通过高碘酸钠作为氧化剂选择性氧化制备双醛基纤维素,再以醛基纤维素和5,5’-二氨-BINAP为原料,通过席夫碱反应制备DAC-BINAP手性配体,最后以铑和DAC-BINAP通过络合制备纤维素作为载体的不对称催化氢化催化剂,应用于不对称催化氢化反应。
其次,在催化氢化过程中,无需加入任何其他催化剂,以氢气作为氢源,在温和的实验条件下即可得到较高的反应转化率和对应选择性。双醛基纤维素的利用实现了将生物基材料引入不对称催化氢化反应中,使得此催化剂可以回收利用,并且6次循环仍然表现出较高的催化活性,从而节约了资源,降低反应成本。
附图说明
构成本发明的一部分的说明书附图用来提供对本发明的进一步理解,本发明的示意性实施例及其说明用于解释本发明,并不构成对本发明的不当限定。
图1是本发明实施例1中制备的MCC、DAC和DAC-5,5’-二氨-BINAP的XRD曲线图;
图2是本发明实施例1制备的MCC、DAC和DAC-5,5’-二氨-BINAP手性配体的红外曲线图。
具体实施方式
应该指出,以下详细说明都是例示性的,旨在对本发明提供进一步的说明。除非另有指明,本发明使用的所有技术和科学术语具有与本发明所属技术领域的普通技术人员通常理解的相同含义。
第一方面,本发明提供一种双醛基纤维素的制备方法,包括如下步骤:纤维素和高碘酸钠在氯化锂的催化作用下反应,将纤维素的羟基氧化成醛基,即得。
在一些实施例中,纤维素、高碘酸钠和氯化锂的质量比为5:10-15:5-8。
在一些实施例中,反应温度为50-60℃,反应时间为2-4h,优选的,反应温度为55℃,反应时间为3h。
在一些实施例中,反应完毕后,包括对反应产物洗涤和干燥的步骤。
进一步的,采用去离子水和无水乙醇交替抽滤洗涤。
进一步的,所述干燥为在55-65℃下真空干燥。
第二方面,本发明提供DAC-BINAP生物基手性配体的制备方法,为以双醛基纤维素和5,5’-二氨-BINAP为原料,通过席夫碱反应制备而成。
在一些实施例中,所述5,5’-二氨-BINAP的制备方法,包括如下步骤:
以(R)-BINAP为原料,氧化制备BINAPO;
对BINAPO进行催化硝化;
将硝化产物溶于乙醇水溶液中,在SnCl2-HCl的还原作用下部分还原;
将部分还原的硝化产物溶于NEt3的甲苯溶液中,以HSiCl3为还原剂,还原得到目标物。
进一步的,对BINAPO进行催化硝化的方法为:以硝酸和醋酸酐为硝化剂,以硫酸为催化剂,进行催化硝化。
进一步的,所述乙醇水溶液中乙醇与水的体积比为8-10:1。
在一些实施例中,DAC-BINAP生物基手性配体的制备方法具体为:
将双醛基纤维素加入至N,N-二甲基甲酰胺中,惰性气体保护下升温,可以避免副反应并且可以保护后面加入的5-5’-二氨-BINAP,向其中加入硝酸铈铵和过硫酸铵,可以活化胺基基团,使胺基有较高能量去发生缩合,反应设定时间后,加入5-5’-二氨-BINAP,继续反应,制得。
在一些实施例中,所述惰性气体为氮气或氩气。
在一些实施例中,升温后的温度为45-55℃。
进一步的,向其中加入硝酸铈铵和过硫酸铵后的反应时间为8-10min。
进一步的,加入5-5’-二氨-BINAP后,继续反应的时间为2-4h。
在一些实施例中,反应完毕后,还包括对反应产物进行洗涤和干燥的步骤。
进一步的,采用去离子水和无水乙醇对DAC-BINAP生物基手性配体进行洗涤。
进一步的,所述干燥为真空干燥,真空干燥的温度为60-70℃。
第三方面,本发明提供所述DAC-BINAP生物基手性配体负载金属铑在不对称催化氢化催化剂中的具体应用。
下面结合附图和具体实施例对本发明作进一步说明。
实施例1
步骤1:取5g纤维素和12.3g高碘酸钠加入到含7.2g氯化锂和400ml去离子水的棕色三口烧瓶中混合,在55℃的温度下充分搅拌3h,反应结束后降至室温,用去离子水和无水乙醇(1:9)多次抽滤洗涤,然后在60℃下真空干燥,通过羟胺盐酸盐-甲醇溶液与醛基定量反应,确定氧化纤维素的醛基含量为8.4mmol/g。
步骤2:取市售(R)-BINAP为原料,以30%H2O2氧化剂,在THF中反应,通过氧化反应定量制备氧化产物BINAPO。以硝酸和醋酸酐为硝化剂,在少量硫酸的催化下成功进行了BINAPO的后续硝化。以SnCl2-HCl作为还原剂,还原乙醇-水中的硝基(9:1,V/V)。最后,以HSiCl3为还原剂,在甲苯中NEt3存在下获得目标配体5,5’-二氨-BINAP,最终得到目标产物的产率为69%。
步骤3:取上述DAC 0.012g加入含有6ml N,N-二甲基甲酰胺的耐压瓶中,在氮气保护下,升温至50℃,加入0.01g硝酸铈铵和0.01g过硫酸铵,9分钟以后,加入0.033g BINAP,继续反应3h,反应结束后依次用去离子水和无水乙醇洗涤,然后在65℃下真空干燥,得到DAC-5,5’-二氨-BINAP手性配体;
DAC、MCC和DAC-5,5’-二氨-BINAP手性配体的XRD曲线和红外曲线图如图1和图2所示。
步骤4:取4.06mg铑催化剂和7.172mgDAC-BINAP手性配体加入含有1ml二氯甲烷的反应瓶中络合30分钟。各称取0.1mmol(z)-2-乙酰氨基-3-苯基丙烯酸甲酯于6个装有1mlCH2Cl2的安瓿瓶中,取适量钯炭催化剂于一个装有2ml二氯甲烷的安瓿瓶中,在真空环境下各取0.1ml络合好的铑/DAC-BINAP依次加入上述6个安瓿瓶中,再各取1ml四氢呋喃、N,N-二甲基甲酰胺、异丙醇、甲醇、乙腈、二氯甲烷加入上述6个安瓿瓶中,将7个安瓿瓶全部转入高压反应釜,釜中的气体用氢气置换三次后,充入2bar氢气,在25℃下反应12h,将反应釜缓慢放气后反应产物过短硅胶柱,TLC监测反应情况,核磁确定产物的结构和转化率,确定氢化产物为目标产物后,使用HPLC确定对映选择性。
步骤5:取催化反应完后的滤渣,用甲醇洗涤三次,随后在40℃下真空干燥5小时即得回收手性配体,回收的手性配体可以直接用于不对称催化氢化中,且其催化活性基本不变。
实施例2
步骤1,2,3,5同实施例1;
步骤4:取4.06mg铑催化剂和7.172mg DAC-BINAP手性配体加入含有1ml二氯甲烷的反应瓶中络合30分钟。各称取0.1mmolα-四氢萘酮于8个装有1mlCH2Cl2的安瓿瓶中,取适量钯炭催化剂于一个装有2ml二氯甲烷的安瓿瓶中,在真空环境下各取0.1ml络合好的铑/DAC-5,5’-二氨-BINAP依次加入上述8个安瓿瓶中,再各取1ml四氢呋喃、N,N-二甲基甲酰胺、异丙醇、甲醇、乙腈、二氯甲烷、正己烷、N,N-二甲基乙酰胺加入上述8个安瓿瓶中,将9个安瓿瓶全部转入高压反应釜,釜中的气体用氢气置换三次后,充入1MPa氢气,在25℃下反应12h,将反应釜缓慢放气后反应产物过短硅胶柱,TLC监测反应情况,核磁确定产物的结构和转化率,确定氢化产物为目标产物后,使用HPLC确定对映选择性。
实施例3
步骤1,2,3,5同实施例1;
步骤4:取4.06mg铑催化剂和7.172mgDAC-BINAP手性配体加入含有1ml二氯甲烷的反应瓶中络合30分钟。各称取0.1mmol(z)-2-乙酰氨基-3-苯基丙烯酸甲酯于8个装有1mlCH2Cl2的安瓿瓶中,取适量钯炭催化剂于一个装有2ml二氯甲烷的安瓿瓶中,在真空环境下各取0.1ml络合好的铑/DAC-5,5’-二氨-BINAP依次加入上述8个安瓿瓶中,再各取1ml四氢呋喃、N,N-二甲基甲酰胺、异丙醇、甲醇、乙腈、二氯甲烷、正己烷、N,N-二甲基乙酰胺加入上述8个安瓿瓶中,将9个安瓿瓶全部转入高压反应釜,釜中的气体用氢气置换三次后,充入1MPa氢气,在25℃下反应12h,将反应釜缓慢放气后反应产物过短硅胶柱,TLC监测反应情况,核磁确定产物的结构和转化率,确定氢化产物为目标产物后,使用HPLC确定对映选择性。
以上所述仅为本发明的优选实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种双醛基纤维素的制备方法,其特征在于:包括如下步骤:纤维素和高碘酸钠在氯化锂的催化作用下反应,将纤维素的羟基氧化成醛基,即得。
2.根据权利要求1所述的双醛基纤维素的制备方法,其特征在于:纤维素、高碘酸钠和氯化锂的质量比为5:10-15:5-8;
在一些实施例中,反应温度为50-60℃,反应时间为2-4h,优选的,反应温度为55℃,反应时间为3h;
在一些实施例中,反应完毕后,包括对反应产物洗涤和干燥的步骤;
进一步的,采用去离子水和无水乙醇交替抽滤洗涤;
进一步的,所述干燥为在55-65℃下真空干燥。
3.双醛基纤维素在制备生物基手性配体中的应用。
4.DAC-BINAP生物基手性配体的制备方法,其特征在于:为以双醛基纤维素和5,5’-二氨-BINAP为原料,通过席夫碱反应制备而成。
5.根据权利要求4所述的DAC-BINAP生物基手性配体的制备方法,其特征在于:所述5,5’-二氨-BINAP的制备方法,包括如下步骤:
以(R)-BINAP为原料,氧化制备BINAPO;
对BINAPO进行催化硝化;
将硝化产物溶于乙醇水溶液中,在SnCl2-HCl的还原作用下部分还原;
将部分还原的硝化产物溶于NEt3的甲苯溶液中,以HSiCl3为还原剂,还原得到目标物;
进一步的,对BINAPO进行催化硝化的方法为:以硝酸和醋酸酐为硝化剂,以硫酸为催化剂,进行催化硝化;
进一步的,所述乙醇水溶液中乙醇与水的体积比为8-10:1;
在一些实施例中,DAC-BINAP生物基手性配体的制备方法具体为:
将双醛基纤维素加入至N,N-二甲基甲酰胺中,惰性气体保护下升温,可以避免副反应并且可以保护后面加入的5-5’-二氨-BINAP,向其中加入硝酸铈铵和过硫酸铵,可以活化胺基基团,使胺基有较高能量去发生缩合,反应设定时间后,加入5,5’-二氨-BINAP,继续反应,制得;
进一步的,所述惰性气体为氮气或氩气;
进一步的,升温后的温度为45-55℃;
进一步的,向其中加入硝酸铈铵和过硫酸铵后的反应时间为8-10min;
进一步的,加入5,5’-二氨-BINAP后,继续反应的时间为2-4h。
6.根据权利要求4所述的DAC-BINAP生物基手性配体的制备方法,其特征在于:反应完毕后,还包括对反应产物进行洗涤和干燥的步骤。
7.根据权利要求6所述的DAC-5,5’-二氨-BINAP生物基手性配体的制备方法,其特征在于:采用去离子水和无水乙醇对DAC-5,5’-二氨-BINAP生物基手性配体进行洗涤。
8.根据权利要求7所述的DAC-5,5’-二氨-BINAP生物基手性配体的制备方法,其特征在于:所述干燥为真空干燥,真空干燥的温度为60-70℃。
9.一种DAC-BINAP生物基手性配体,由权利要求4-8任一所述制备方法制备而成。
10.权利要求9所述DAC-BINAP生物基手性配体作为载体负载金属铑后在不对称催化氢化催化剂中的应用。
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CN116041553B (zh) * | 2023-01-30 | 2024-05-31 | 陕西科技大学 | 稀土配合物调控纳米纤维素手性的制备方法 |
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