CN116273188A - 一种负载金属的多孔有机框架材料在催化Pictet-Spengler反应中的应用 - Google Patents
一种负载金属的多孔有机框架材料在催化Pictet-Spengler反应中的应用 Download PDFInfo
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- CN116273188A CN116273188A CN202310272236.XA CN202310272236A CN116273188A CN 116273188 A CN116273188 A CN 116273188A CN 202310272236 A CN202310272236 A CN 202310272236A CN 116273188 A CN116273188 A CN 116273188A
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
本发明提供了一种负载金属的多孔有机框架材料在催化Pictet‑Spengler反应中的应用。本发明负载金属的多孔有机框架材料,作为非均相催化色胺类化合物与靛红类化合物的Pictet–Spengler反应制备得到螺环四氢‑β‑咔啉化合物的催化物,催化活性高,催化效果显著,稳定性高,催化循环7次产率几乎没有下降,且易从反应体系中分离出来,适合批量生产和实际应用。
Description
技术领域
本发明属于非均相催化技术领域。更具体地,涉及一种负载金属的多孔有机框架材料在催化Pictet-Spengler反应中的应用。
背景技术
螺环四氢-β-咔啉化合物存在于很多重要的天然产物和药物分子中,如抗疟药物NITD609和天然产物Komavine,具有抗病毒、杀真菌、抗疟疾、抗利什曼病、抗血栓、抗癌等多种药理活性,具有巨大的应用价值,但从天然产物中提取含相关骨架化合物的产量低、难度大。
目前,Pictet–Spengler反应是合成四氢-β-咔啉化合物最重要的方法,但螺环四氢-β-咔啉化合物通常是在化学计量的酸或过渡金属分子复合物等均相催化条件下合成的,反应耗时长,催化剂不可循环利用,产物分离耗时耗能(Science,2010,329,1175-1180)。
发明内容
本发明针对现有技术的不足,提供一种负载金属的多孔有机框架材料,作为Pictet–Spengler反应制备螺环四氢-β-咔啉化合物的催化物,能循环利用,显著提高反应效率,且得到的产物易分离。
本发明的第一目的是提供一种负载金属的多孔有机框架材料。
本发明的第二目的是提供上述负载金属的多孔有机框架材料的制备方法。
本发明的第三目的是提供上述负载金属的多孔有机框架材料在催化Pictet-Spengler反应中的应用。
本发明的第四目的是提供一种螺环四氢-β-咔啉化合物的制备方法。
本发明的第五目的是提供上述方法制备得到的螺环四氢-β-咔啉化合物。
本发明的第六目的是提供上述螺环四氢-β-咔啉化合物在制备抗病毒产品、抗真菌产品、抗疟疾药物、抗利什曼病药物或抗血栓药物中的应用。
本发明上述目的通过以下技术方案实现:
本发明提供了一种负载金属的多孔有机框架材料(POF-M),具有如下式所示的结构式:
其中,M为Cr3+、Fe3+、Fe2+、Co2+、Mn2+、Cu2+、Cd2+或Ni2+。
本发明还提供了上述负载金属的多孔有机框架材料的制备方法,具体为:对苯二甲醛与三聚氰胺反应后,负载金属即得。
优选地,所述对苯二甲醛与三聚氰胺的摩尔比为1:0.3~1.6。
优选地,所述反应在有机溶剂中进行,所述有机溶剂包括但不限于二甲亚砜。
进一步优选地,所述对苯二甲醛在有机溶剂中的浓度为0.1~1.0mol/L。
优选地,所述反应还加入催化剂,所述催化剂包括但不限于乙酸。
进一步优选地,所述催化剂与对苯二甲醛的摩尔比为0~0.5:1,
优选地,所述反应为在100~180℃下反应10~72h。
优选地,所述负载金属的方法为:将所述反应得到的产物(多孔有机框架材料)加入到含金属盐的有机溶液中,反应5~24h。
进一步优选地,所述金属盐为金属的硝酸盐、硝酸盐水合物、醋酸盐、醋酸盐水合物、盐酸盐或盐酸盐水合物。
进一步优选地,所述金属盐与多孔有机框架材料的用量比为1~30mmol/g。
本发明负载金属的多孔有机框架材料,作为非均相催化色胺类化合物与靛红类化合物的Pictet–Spengler反应制备得到螺环四氢-β-咔啉化合物的催化物,催化活性高,催化效果显著,稳定性高,催化循环7次产率几乎没有下降,且易从反应体系中分离出来,适合批量生产和实际应用。因此,上述负载金属的多孔有机框架材料在催化Pictet-Spengler反应中的应用也应在本发明的保护范围之内。
优选地,所述Pictet-Spengler反应为色胺类化合物与靛红类化合物的反应。
优选地,所述色胺类化合物具有如下式所示的结构式:
其中,R1、R2独立地选自氢、烷基、烷氧基、芳基、卤素或硝基,如甲基、乙基、苯基、苄基、甲氧基、氟、氯、溴等。
优选地,所述靛红类化合物具有如下式所示的结构式:
其中,R3、R4独立地选自氢、烷基、烷氧基、芳基、卤素或硝基,如甲基、乙基、苯基、苄基、甲氧基、氟、氯、溴等。
此外,本发明还提供了一种螺环四氢-β-咔啉化合物的制备方法,所述螺环四氢-β-咔啉化合物由色胺类化合物与靛红类化合物在上述负载金属的多孔有机框架材料的催化下反应得到。
其中,R1、R2、R3、R4独立地选自氢、烷基、烷氧基、芳基、卤素或硝基,如甲基、乙基、苯基、苄基、甲氧基、氟、氯、溴等。
优选地,所述色胺类化合物与负载金属的多孔有机框架材料的用量比为1mol:7.5~200g。
优选地,所述色胺类化合物与靛红类化合物的摩尔比为1~5:1~5。
优选地,所述反应在有机溶剂中进行,如乙腈、四氢呋喃、乙醇、甲醇、甲苯、二氯甲烷或氯仿等。
进一步优选地,所述色胺类化合物在有机溶剂中的浓度为0.1~10mol/L。
优选地,所述反应为在25~130℃下反应1~10h。
进一步地,本发明还提供了上述方法制备得到的螺环四氢-β-咔啉化合物,以及上述螺环四氢-β-咔啉化合物在制备抗病毒产品、抗真菌产品、抗疟疾药物、抗利什曼病药物或抗血栓药物中的应用。
优选地,所述螺环四氢-β-咔啉化合物具有如下式所示的结构式:
其中,R1、R2、R3、R4独立地选自氢、、烷基、烷氧基、芳基、卤素或硝基,如甲基、乙基、苯基、苄基、甲氧基、氟、氯、溴等。
本发明具有以下有益效果:
1.本发明负载金属的多孔有机框架材料,作为非均相催化色胺类化合物与靛红类化合物的Pictet–Spengler反应制备得到螺环四氢-β-咔啉化合物的催化物,催化活性高,催化效果显著(螺环四氢-β-咔啉化合物的产率为86%~99%),官能团耐受性好,稳定性高,催化循环7次产率几乎没有下降,且易从反应体系中分离出来。
2.本发明负载金属的多孔有机框架材料制备简单、原料来源广泛、成本低廉、反应条件温和,环境友好,适合批量生产和实际应用。
附图说明
图1为对苯二甲醛、三聚氰胺、实施例1所得POF和POF-Cr3+的红外波谱图。
图2为实施例1所得POF和POF-Cr3+的XRD谱图。
图3为实施例1所得POF和POF-Cr3+的氮气等温吸脱附谱图。
图4为实施例1所得POF和POF-Cr3+的SEM谱图。
图5为螺环四氢-β-咔啉化合物TM1的氢核磁波谱图。
图6为螺环四氢-β-咔啉化合物TM2的氢核磁波谱图。
图7为螺环四氢-β-咔啉化合物TM3的氢核磁波谱图。
图8为螺环四氢-β-咔啉化合物TM4的氢核磁波谱图。
图9为螺环四氢-β-咔啉化合物TM5的氢核磁波谱图。
图10为螺环四氢-β-咔啉化合物TM6的氢核磁波谱图。
图11为螺环四氢-β-咔啉化合物TM7的氢核磁波谱图。
图12为螺环四氢-β-咔啉化合物TM8的氢核磁波谱图。
图13为螺环四氢-β-咔啉化合物TM9的氢核磁波谱图。
图14为螺环四氢-β-咔啉化合物TM10的氢核磁波谱图。
图15为催化剂的催化循环图。
具体实施方式
以下结合说明书附图和具体实施例来进一步说明本发明,但实施例并不对本发明做任何形式的限定。除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
除非特别说明,以下实施例所用试剂和材料均为市购。
实施例1一种负载金属的多孔有机框架材料的制备
S1.将0.56mol对苯二甲醛、0.37mol三聚氰胺与0.05mol乙酸加入到2.3L二甲亚砜中,在氮气氛围、140℃的条件下加热反应40h后,自然冷却至25℃,离心除去溶剂,再依次用丙酮、四氢呋喃、甲醇、二氯甲烷洗涤,60℃下真空干燥得到浅白色的多孔有机框架材料,记为POF,结构式如下所示:
S2.将2.0g S1所得POF加入到含4mmol CrCl3的乙醇溶液中,搅拌反应12h后,离心并用乙醇洗涤4次,真空干燥得到负载金属的多孔有机框架材料,记为POF-Cr3+,结构式如下所示:
实施例2一种负载金属的多孔有机框架材料的制备
S1.将0.56mol对苯二甲醛、0.75mol三聚氰胺与0.25mol乙酸加入到5.6L二甲亚砜中,在氮气氛围、100℃的条件下加热反应72h后,自然冷却至20℃,过滤除去溶剂,再依次用丙酮、四氢呋喃、甲醇、二氯甲烷洗涤,60℃下真空干燥得到浅白色的多孔有机框架材料,记为POF。
S2.将4.0g S1所得POF加入到含15mmol FeCl3·6H2O的乙醇溶液中,搅拌反应18h后,过滤并用乙醇洗涤3次,真空干燥得到负载金属的多孔有机框架材料,记为POF-Fe3+,结构式如下所示:
实施例3一种负载金属的多孔有机框架材料的制备
S1.将0.56mol对苯二甲醛、0.56mol三聚氰胺与0.1mol乙酸加入到1L二甲亚砜中,在氩气氛围、180℃的条件下加热反应10h后,自然冷却至30℃,离心除去溶剂,再依次用丙酮、四氢呋喃、甲醇、二氯甲烷洗涤,60℃下真空干燥得到浅白色的多孔有机框架材料,记为POF。
S2.将2.0g S1所得POF加入到含40mmol Mn(NO3)2的乙醇溶液中,搅拌反应20h后,离心并用乙醇洗涤5次,真空干燥得到负载金属的多孔有机框架材料,记为POF-Mn2+,结构式如下所示:
实施例4一种负载金属的多孔有机框架材料的制备
同实施例1,区别在于,将CrCl3替换为Cu(NO3)2,产物记为POF-Cu2+,结构式如下所示:
实施例5结构鉴定
采用Bruker Equinox 55波谱仪分别对对苯二甲醛、三聚氰胺、实施例1所得POF和POF-Cr3+进行傅里叶红外波谱分析(KBr压片,波数范围为400~4000cm-1),并采用ESCALAB250Xi衍射仪、NOVA4000e表面分析仪、LEO1430VP扫描电镜仪分别对实施例1所得POF和POF-Cr3+进行粉末X射线衍射(XRD)、氮气等温吸脱附分析和扫描电镜(SEM)分析,进而确认POF和POF-Cr3+的结构。
结果如图1~4所示,其中,图1为对苯二甲醛、三聚氰胺、实施例1所得POF和POF-Cr3+的红外波谱图,图2为实施例1所得POF和POF-Cr3+的XRD谱图,图3为实施例1所得POF和POF-Cr3+的氮气等温吸脱附谱图,图4为实施例1所得POF和POF-Cr3+的SEM谱图。
由图1可知,对苯二甲醛的红外波谱图中有与醛基相关的2864cm-1(C-H拉伸振动)和1693cm-1(C=O拉伸振动)的振动峰。三聚氰胺的红外波谱图中有与伯胺基相关的3469cm-1、3419cm-1和1653cm-1(NH2拉伸和变形振动)的振动峰。实施例1所得POF的红外波谱图中没有出现前述与醛基、伯胺基相关的振动峰,或相关振动峰显著减弱;与三嗪环相对应的1549cm-1和1477cm-1的波峰在POF的波谱中出现,表明三聚氰胺成功地融入到聚合物网络中;在POF的波谱中也没有发现可能归因于亚胺(-C=N-)连接的吸收峰,如1600cm-1左右的C=N拉伸振动,说明对苯二甲醛和三聚氰胺确实发生反应形成POF材料,并且以C-N形式连接;实施例1所得POF-Cr3+与POF相比,负载金属离子后,红外波谱图变化不大,说明负载金属离子的数量较少。
由图2可知,实施例1所得POF的XRD谱图中没有明显的信号峰,表明POF属于非晶材料;实施例1所得POF-Cr3+的XRD谱图中出现一个尖锐的信号峰,表明金属离子被吸附到POF材料中。
由图3可知,实施例1所得POF的比表面积为551m2·g-1,实施例1所得POF-Cr3+的比表面积下降至469m2·g-1。
由图4可知,实施例1所得POF与POF-Cr3+均为粒径约20nm的不规则粒子。
采用同样的仪器分别对实施例2所得POF与POF-Fe3+、实施例3所得POF与POF-Mn2+、实施例4所得POF与POF-Cu2+进行傅里叶红外波谱分析、粉末X射线衍射、氮气等温吸脱附分析和扫描电镜分析,确认实施例2~4的POF结构与实施例1相同,且POF-M均成功将金属离子吸附到POF中。
实施例6螺环四氢-β-咔啉化合物TM1的合成
将5mg实施例1所得POF-Cr3+、0.2mmol色胺、0.4mmol靛红和0.5mL乙腈加入反应管中,在100℃下搅拌反应6h后,进行色谱分离和纯化(流动相石油醚:乙酸乙酯(v/v)=2:1~8梯度淋洗),产物经核磁共振(谱图如图5所示)确认为结构式如下式所示的螺环四氢-β-咔啉化合物TM1,产率99%。
实施例7螺环四氢-β-咔啉化合物TM2的合成
将3mg实施例3所得POF-Mn2+、0.2mmol色胺、0.3mmol 5-氟靛红和0.5mL四氢呋喃加入反应管中,在80℃下搅拌反应8h后,进行色谱分离和纯化(流动相石油醚:乙酸乙酯(v/v)=2:1~8梯度淋洗),产物经核磁共振(谱图如图6所示)确认为结构式如下式所示的螺环四氢-β-咔啉化合物TM2,产率97%。
实施例8螺环四氢-β-咔啉化合物TM3的合成
将10mg实施例2所得POF-Fe3+、0.2mmol色胺、0.2mmol 5-氯靛红和1.0mL乙醇加入反应管中,在80℃下搅拌反应5h后,进行色谱分离和纯化(流动相石油醚:乙酸乙酯(v/v)=2:1~8梯度淋洗),产物经核磁共振(谱图如图7所示)确认为结构式如下式所示的螺环四氢-β-咔啉化合物TM3,产率86%。
实施例9螺环四氢-β-咔啉化合物TM4的合成
将3mg实施例4所得POF-Cu2+、0.4mmol色胺、0.2mmol 5-溴靛红和0.5mL甲醇加入反应管中,在100℃下搅拌反应5h后,进行色谱分离和纯化(流动相石油醚:乙酸乙酯(v/v)=2:1~8梯度淋洗),产物经核磁共振(谱图如图8所示)确认为结构式如下式所示的螺环四氢-β-咔啉化合物TM4,产率99%。
实施例10螺环四氢-β-咔啉化合物TM5的合成
将5mg实施例3所得POF-Mn2+、0.3mmol色胺、0.2mmol 5-硝基靛红和1.5mL甲苯加入反应管中,在100℃下搅拌反应8h后,进行色谱分离和纯化(流动相石油醚:乙酸乙酯(v/v)=2:1~8梯度淋洗),产物经核磁共振(谱图如图9所示)确认为结构式如下式所示的螺环四氢-β-咔啉化合物TM5,产率90%。
实施例11螺环四氢-β-咔啉化合物TM6的合成
将10mg实施例1所得POF-Cr3+、0.2mmol色胺、0.3mmol 5-甲基靛红和0.5mL二氯甲烷加入反应管中,在100℃下搅拌反应4h后,进行色谱分离和纯化(流动相石油醚:乙酸乙酯(v/v)=2:1~8梯度淋洗),产物经核磁共振(谱图如图10所示)确认为结构式如下式所示的螺环四氢-β-咔啉化合物TM6,产率90%。
实施例12螺环四氢-β-咔啉化合物TM7的合成
将15mg实施例1所得POF-Cr3+、0.2mmol色胺、0.4mmol 5-甲氧基靛红和1.5mL乙腈加入反应管中,在120℃下搅拌反应2h后,进行色谱分离和纯化(流动相石油醚:乙酸乙酯(v/v)=2:1~8梯度淋洗),产物经核磁共振(谱图如图11所示)确认为结构式如下式所示的螺环四氢-β-咔啉化合物TM7,产率87%。
实施例13螺环四氢-β-咔啉化合物TM8的合成
将20mg实施例1所得POF-Cr3+、0.2mmol色胺、0.6mmol 7-溴靛红和2.0mL乙腈加入反应管中,在110℃下搅拌反应3h后,进行色谱分离和纯化(流动相石油醚:乙酸乙酯(v/v)=2:1~8梯度淋洗),产物经核磁共振(谱图如图12所示)确认为结构式如下式所示的螺环四氢-β-咔啉化合物TM8,产率95%。
实施例14螺环四氢-β-咔啉化合物TM9的合成
将10mg实施例1所得POF-Cr3+、0.2mmol色胺、0.3mmol 7-甲基靛红和0.5mL氯仿加入反应管中,在60℃下搅拌反应8h后,进行色谱分离和纯化(流动相石油醚:乙酸乙酯(v/v)=2:1~8梯度淋洗),产物经核磁共振(谱图如图13所示)确认为结构式如下式所示的螺环四氢-β-咔啉化合物TM9,产率86%。
实施例15螺环四氢-β-咔啉化合物TM10的合成
将5mg实施例1所得POF-Cr3+、0.2mmol色胺、0.2mmol 6-溴靛红和0.3mL乙腈加入反应管中,在40℃下搅拌反应10h后,进行色谱分离和纯化(流动相石油醚:乙酸乙酯(v/v)=2:1~8梯度淋洗),产物经核磁共振(谱图如图14所示)确认为结构式如下式所示的螺环四氢-β-咔啉化合物TM10,产率93%。
实施例16催化循环实验
将25mg实施例1所得POF-Cr3+、1.0mmol色胺、2.0mmol靛红和2.5mL乙腈加入反应管中,在80℃下搅拌反应6h。反应结束后,将催化剂POF-Cr3+依次进行离心分离、乙腈和甲醇洗涤、60℃真空干燥12h,并于相同反应条件下用于下一次催化反应,每次催化反应结束后均将反应液旋蒸浓缩,利用色谱(流动相石油醚:乙酸乙酯(v/v)=2:1~8梯度淋洗)进行分离纯化,计算螺环四氢-β-咔啉化合物的产率,经7次催化循环得到如图15所示的催化循环图。可见,催化剂的活性几乎没有下降。
此外,本实施例的实验同时也是实施例6的克级放大实验,螺环四氢-β-咔啉化合物的产率依然很高,表明本发明的方法具有较高的实用性,可利于批量生产。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
2.权利要求1所述负载金属的多孔有机框架材料的制备方法,其特征在于,对苯二甲醛与三聚氰胺反应后,负载金属即得。
3.权利要求1所述负载金属的多孔有机框架材料在催化Pictet-Spengler反应中的应用。
4.根据权利要求3所述应用,其特征在于,所述Pictet-Spengler反应为色胺类化合物与靛红类化合物的反应。
7.一种螺环四氢-β-咔啉化合物的制备方法,其特征在于,由色胺类化合物与靛红类化合物在权利要求1所述负载金属的多孔有机框架材料的催化下反应得到。
8.权利要求7所述方法制备得到的螺环四氢-β-咔啉化合物。
10.权利要求8所述螺环四氢-β-咔啉化合物在制备抗病毒产品、抗真菌产品、抗疟疾药物、抗利什曼病药物或抗血栓药物中的应用。
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