CN114891231B - 一种用于惰性c-h键选择性氧化的双功能金属-有机框架的合成方法及应用 - Google Patents
一种用于惰性c-h键选择性氧化的双功能金属-有机框架的合成方法及应用 Download PDFInfo
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- CN114891231B CN114891231B CN202210290893.2A CN202210290893A CN114891231B CN 114891231 B CN114891231 B CN 114891231B CN 202210290893 A CN202210290893 A CN 202210290893A CN 114891231 B CN114891231 B CN 114891231B
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Abstract
本发明属于光催化材料技术领域，一种用于惰性C‑H键选择性氧化的双功能金属‑有机框架的合成方法及应用，其中合成方法，是以二羧基蒽醌配体H2AQ，与以金属钴盐中的Co2+作为金属节点，采用高温溶剂热法合成用于惰性C‑H键选择性氧化的双功能金属‑有机框架材料。本发明制备的用于惰性C‑H键选择性氧化的双功能金属‑有机框架易合成，能够在温和的条件下实现苄基C(sp3)‑H键类化合物C(sp3)‑H的选择性氧化，并同时实现氧气的活化，从而提高了C(sp3)‑H键的活化和氧化的效率，TON值高达1920。光催化剂Co‑AQ作为一种非均相催化剂，催化剂易于分离，可多次回收循环使用。
Description
技术领域
本发明涉及一种用于惰性C-H键选择性氧化的双功能金属-有机框架的合成方法及应用，属于光催化材料技术领域。
背景技术
C-H键功能化被视为有机化学领域的“圣杯”，其中惰性C-H键选择性氧化策略可以将饱和烷烃直接转化为功能有机砌块，并从而直接获得高附加值的精细化学品和药物分子，成为一种潜力巨大的高效合成策略。羰基衍生物是一类重要的化工原料及合成中间体，其已被广泛应用于有机功能分子、催化剂、医药和天然产品等领域，如咪唑[1,2-a]并吲哚-9-酮衍生物可以用于癌症治疗、吡托非农可以治疗心肌梗塞及6,7-二氢-5H-环戊基[b]吡啶基-5-酮衍生物被用于抗焦虑和抗HIV病毒治疗。目前，过渡金属介导的惰性C-H键选择性氧化仍是一种重要的方法之一，但其过程中通常涉及苛刻的反应条件、当量副产物及重金属残留等，从而导致原子经济性低和环境污染。近年来，光催化剂诱导氢原子转移(HAT)方法快速发展为C(sp3)-H键选择性氧化提供了新的机遇。此外，氧气作为一种廉价绿色的氧化剂，亦可被光催化剂活化生成活性氧物种 (ROS)进而氧化惰性C(sp3)-H键。但均相体系内激发态光催化剂同时诱导 HAT过程活化C(sp3)-H键与活化氧气产生ROS仍存在很大的挑战，如光催化剂自淬灭、光漂白及催化效率不足等问题。
发明内容
为了解决现有技术中存在的问题，本发明目的是提供一种用于惰性C-H 键选择性氧化的双功能金属-有机框架的合成方法及应用。合成的双功能光活性蒽醌基金属-有机框架通过光诱导HAT和能量转移(EnT)过程同时实现有机化合物C(sp3)-H键选择性氧化，提高C(sp3)-H键氧化的效率。本发明解决其技术问题通过合成得到的光活性二羧基蒽醌配体H2AQ修饰到到金属-有机框架内，这不仅保留了蒽醌作为光诱导氢原子转移的催化位点能够实现对于 C(sp3)-H键的活化，同时还增强了金属-有机框架上的蒽醌光活性更加有利于活化氧气产生单线态氧作为绿色的末端氧化剂。蒽醌的双功能在金属-有机框架上得到很好的协同，提升了C(sp3)-H键选择性氧化效率。此外，双功能光活性蒽醌基金属-有机框架材料解决了C(sp3)-H键选择性氧化过程中可能发生的蒽醌自聚和自淬灭的问题。光催化反应条件温和，催化剂易于分离，可多次回收循环使用。
为了实现上述发明目的，解决已有技术中所存在的难点和问题，本发明采用技术方案是：一种用于惰性C-H键选择性氧化的双功能金属-有机框架的合成方法，是将光活性二羧基蒽醌配体H2AQ与金属钴盐中的Co2+作为金属节点，在N,N-二甲基乙酰胺/乙醇混合溶剂中超声溶解，通过溶剂热法合成得到一种用于惰性C-H键选择性氧化的双功能金属-有机框架，其合成路线如下：
H2AQ+Co2+→Co-AQ；
所述金属钴盐选自Co(NO3)2·6H2O、Co(ClO4)2·6H2O或Co(CH3COO)2·4H2O 中的一种；
所述光活性二羧基蒽醌配体H2AQ，具有如下(A)分子结构式，
所述合成方法，包括以下步骤：
步骤1、将苯甲醇与甲苯按照1：14～17质量比混合均匀，再将混合物温度降至0℃后，在1～2小时内，向混合物中加入无水AlCl3 8～12次，每次加入10～16g，苯甲醇与无水AlCl3的质量比为1：3～4，当无水AlCl3添加完毕后，将温度升至105～125℃，反应3～4小时，再将反应温度冷却至20～30℃后，将溶液倒入碎冰、去离子水与盐酸的混合物中，静置析出黄色沉淀，真空抽滤，并用去离子水、乙酸乙酯、饱和碳酸氢钠溶液和去离子水依次洗涤滤饼，干燥得到浅黄色固体，然后用冰乙酸重结晶得到浅黄色粉末，即2,7-二甲基蒽；
步骤2、将三氧化铬与去离子水按照1：1～1.5的质量比超声溶解配制成4～6 mL第一种溶液，将步骤1制得的2,7-二甲基蒽与冰乙酸按照1：140～150质量比配制成400～430mL悬浊液，再将悬浊液加热到130～140℃，直至完全固体溶解，配置成第二种溶液，将第一种溶液缓慢滴加至第二种溶液中，然后在 130～140℃下反应30～50分钟后溶液变为墨绿色，反应停止；再将反应温度冷却到20～30℃后，将溶液倒入800～1200mL去离子水中，静置析出白色沉淀，真空抽滤，并用200～400mL去离子水洗涤滤饼，真空干燥得到白色固体，即 2,7-二甲基蒽醌；
步骤3、将浓硫酸，醋酸酐和冰乙酸按照1：3～4：70～80质量比配制成溶液并置于0℃下，然后将步骤2制得的2,7-二甲基蒽醌与三氧化铬按1：12～14 的摩尔比缓慢加入到上述溶液中，然后将反应温度升至110～130℃，持续搅拌 5～6小时，反应停止；反应温度冷却到20～30℃后，将溶液倒入400～600mL 去离子水中，静置析出黄色沉淀，真空抽滤，并用200～300mL去离子水洗涤滤饼，真空干燥得到亮黄色固体，即配体H2AQ；
步骤4、将步骤3制得的配体H2AQ与金属钴盐按1：0.9～1.1摩尔比加入到4～8mLN,N-二甲基乙酰胺和1～2mL乙醇的混合溶液中，然后超声震荡使其完全溶解后向其澄清溶液加入0.2～0.4mL有机酸，置于高压反应釜中，经过 2～4小时升温至100～120℃，保温120～132小时，之后8～12小时降至20～30℃，得到深紫色块状晶体，过滤收集，使用3～5mL N,N-二甲基乙酰胺洗涤，干燥，得到目标化合物，即光催化剂Co-AQ，所述有机酸选自三氟乙酸或冰乙酸中的一种。
所述方法合成的光催化剂Co-AQ在惰性C-H键氧化和氧气活化中的应用。
本发明有益效果是：一种用于惰性C-H键选择性氧化的双功能金属-有机框架的合成方法及应用，其中合成方法，是将光活性二羧基蒽醌配体H2AQ与金属钴盐中的Co2+作为金属节点，在N,N-二甲基乙酰胺/乙醇混合溶剂中超声溶解，通过溶剂热法合成得到一种用于惰性C-H键选择性氧化的双功能金属- 有机框架，其合成路线如下：H2AQ+Co2+→Co-AQ；所述金属钴盐选自六水合硝酸钴Co(NO3)2·6H2O、六水合高氯酸钴Co(ClO4)2·6H2O及四水合乙酸钴 Co(CH3COO)2·4H2O中的一种；与已有技术相比，本发明的一种用于惰性C-H 键选择性氧化的双功能金属-有机框架容易构筑，能够在温和的条件下实现苄基C(sp3)-H键类化合物C-H键选择性氧化，并同时实现氧气的活化，从而提高了C(sp3)-H键选择性氧化的效率。光催化剂Co-AQ作为一种非均相催化剂，催化剂易于分离，可多次回收循环使用。此外，空气或氧气作为一种廉价绿色易得的氧化剂对于环境友好，因此光催化剂Co-AQ有望成为一种绿色高效的非均相催化剂实现惰性C-H键选择性氧化。
附图说明
图1是实施例1目标光催化剂Co-AQ的晶体结构图。
图2是实施例1目标光催化剂Co-AQ的PXRD图。
图3是实施例6目标光催化剂Co-AQ的苯甲醇的氧化反应转化数(TON) 随时间的变化图。
具体实施方式
下面结合实施例对本发明作进一步说明。
实施例1
将苯甲醇42.0g与甲苯630g混合均匀，并将混合物温度降至0℃后，在1.5小时内，向混合物中加入无水AlCl3 10次，每次加入13.5g，当无水AlCl3添加完毕后，将反应温度升至120℃，在该温度下反应3小时。反应结束，反应温度冷却到25℃后，将溶液倒入碎冰、去离子水与盐酸的混合物中，静置析出黄色沉淀，真空抽滤，并用去离子水、乙酸乙酯、饱和碳酸氢钠溶液和去离子水依次洗涤滤饼，干燥得到浅黄色固体，然后用冰乙酸重结晶得到浅黄色粉末17.4g，产率为21％(基于苯甲醇的摩尔质量)，即2,7-二甲基蒽。1H NMR (600MHz,CDCl3,ppm):δ8.36-8.16(m,2H),7.88(d,J＝8.6Hz,2H),7.72(s, 2H),7.31-7.26(m,4H),2.54(s,6H).
将三氧化铬4.0g与去离子水4.0g超声溶解配制成4mL第一种溶液；称取2,7-二甲基蒽3.0g,与冰乙酸430.0g配制成410mL悬浊液，再将悬浊液加热到135℃，直至完全固体溶解，配置成第二种溶液。将第一种溶液缓慢滴加至第二种溶液中，然后在130℃下反应45分钟后溶液变为墨绿色。反应停止，反应温度冷却到25℃后，将溶液倒入1000mL去离子水中，静置析出白色沉淀，真空抽滤，并用300mL去离子水洗涤滤饼，真空干燥得到白色固体3.0g，产率为87％，即2,7-二甲基蒽醌。1H NMR(600MHz,CDCl3,ppm):δ8.19(d,J＝ 7.9Hz,2H),8.08(d,J＝1.6Hz,2H),7.58(dd,J＝7.8,2.0Hz,2H),2.53(s,6H).
将浓硫酸0.55g，醋酸酐1.96g和冰乙酸42.00g配制成溶液并置于0℃下，然后称取2,7-二甲基蒽醌(1.3g,5.4mmol)与三氧化铬(6.6g,65.5mmol) 缓慢加入到上述溶液中，然后将反应温度升至120℃，持续搅拌5小时。反应停止，反应温度冷却到25℃后，将溶液倒入500mL去离子水中，静置析出黄色沉淀，真空抽滤，并用300mL去离子水洗涤滤饼，真空干燥得到亮黄色固体1.4g，产率87％，即配体H2AQ；1H NMR(600MHz,DMSO-d6,ppm):δ 13.75(brs,1H),8.69(d,J＝1.5Hz,2H),8.43(d,J＝8.0Hz,2H),8.34(dd,J＝7.9, 3.2Hz,2H).
称取配体H2AQ(29.6mg,0.1mmol)与Co(NO3)2·6H2O(29.0mg,0.1mmol) 加入到6mLN,N-二甲基乙酰胺和1mL乙醇的混合溶液中，然后超声震荡使其完全溶解后向其澄清溶液加入0.2mL三氟乙酸，置于高压反应釜中，经过4 小时升温至100℃，保温120小时，之后10小时降至25℃，得到深紫色块状晶体，过滤收集，使用5mL N,N-二甲基乙酰胺洗涤，干燥，得到目标化合物，即光催化剂Co-AQ，产率12％(基于配体H2AQ的摩尔质量)，光催化剂Co-AQ 晶体结构图，如图1所示，PXRD图，如图2所示。
实施例2
称取配体H2AQ(29.6mg,0.1mmol)与Co(ClO4)2·6H2O(36.6mg,0.1mmol) 加入到5mL N,N-二甲基乙酰胺和1mL乙醇的混合溶液中，然后超声震荡使其完全溶解后向其澄清溶液加入0.2mL冰乙酸，置于高压反应釜中，经过4小时升温至100℃，保温120小时，之后12小时降至25℃，得到深紫色块状晶体，过滤收集，使用5mL N,N-二甲基乙酰胺洗涤，干燥，得到目标化合物，即光催化剂Co-AQ，产率15％(基于配体H2AQ的摩尔质量)。
实施例3
称取配体H2AQ(29.6mg,0.1mmol)与Co(CH3COO)2·4H2O(24.9mg,0.1 mmol)加入到8mL N,N-二甲基乙酰胺和2mL乙醇的混合溶液中，然后超声震荡使其完全溶解后向其澄清溶液加入0.3mL三氟乙酸，置于高压反应釜中，经过4小时升温至110℃，保温120小时，之后12小时降至25℃，得到深紫色块状晶体，过滤收集，使用4mL N,N-二甲基乙酰胺洗涤，干燥，得到目标化合物，即光催化剂Co-AQ，产率18％(基于配体H2AQ的摩尔质量)。
实施例4
称取苄醇类底物(0.4mmol)、乙腈溶剂(5mL)和构筑得到的催化剂 Co-AQ(4.1mg,6.0μmol)加入到石英光反应管中，在25℃下，空气下持续搅拌，在420nm LED照射下反应12小时。反应结束后，过滤掉催化剂Co-AQ 保留滤液，减压蒸馏，向其加入67.3mg的1,3,5-三甲氧基苯作为内标计算反应产率。该催化反应体系不同取代基苄醇底物进行拓展，如表1所示。
表1
实施例5
称取苄基C(sp3)-H键底物(0.4mmol)、乙腈溶剂(5mL)和构筑得到的催化剂Co-AQ(4.1mg,6.0μmol)加入到石英光反应管中，在25℃下，氧气下持续搅拌，在420nm LED照射下反应18小时。反应结束后，过滤掉光催化剂Co-AQ保留滤液，减压蒸馏，向其加入67.3mg的1,3,5-三甲氧基苯作为内标计算反应产率。该催化反应体系不同苄基C(sp3)-H键底物进行拓展，如表2 所示。
表2
实施例6
称取苯甲醇(2.16g,20.0mmol)、乙腈溶剂(5mL)和构筑得到的光催化剂Co-AQ(1.4mg,2.0μmol)加入到石英光反应管中，在25℃下，空气下持续搅拌，在420nm LED照射下反应72小时。反应结束，过滤掉催化剂Co-AQ 保留滤液，减压蒸馏，向其加入168.19mg的1,3,5-三甲氧基苯作为内标计算反应TON值，TON值高达1920。光催化剂Co-AQ催化苯甲醇的氧化反应TON 值随时间的变化图，如图3所示。
Claims (1)
1.一种光催化剂Co-AQ在惰性C-H键选择性氧化中的应用，其特征在于：将光活性二羧基蒽醌配体H2AQ与金属钴盐中的Co2+作为金属节点，在N,N-二甲基乙酰胺/乙醇混合溶剂中超声溶解，通过溶剂热法合成得到一种用于惰性C-H键选择性氧化的双功能金属-有机框架，其合成路线如下：
H2AQ+Co2+→Co-AQ；
所述金属钴盐选自Co(NO3)2·6H2O、Co(ClO4)2·6H2O或Co(CH3COO)2·4H2O中的一种；
所述光活性二羧基蒽醌配体H2AQ，具有如下(A)分子结构式，
合成方法，包括以下步骤：
步骤1、将苯甲醇与甲苯按照1：14～17质量比混合均匀，再将混合物温度降至0℃后，在1～2小时内，向混合物中加入无水AlCl3 8～12次，每次加入10～16g，苯甲醇与无水AlCl3的质量比为1：3～4，当无水AlCl3添加完毕后，将温度升至105～125℃，反应3～4小时，再将反应温度冷却至20～30℃后，将溶液倒入碎冰、去离子水与盐酸的混合物中，静置析出黄色沉淀，真空抽滤，并用去离子水、乙酸乙酯、饱和碳酸氢钠溶液和去离子水依次洗涤滤饼，干燥得到浅黄色固体，然后用冰乙酸重结晶得到浅黄色粉末，即2,7-二甲基蒽；
步骤2、将三氧化铬与去离子水按照1：1～1.5的质量比超声溶解配制成4～6mL第一种溶液，将步骤1制得的2,7-二甲基蒽与冰乙酸按照1：140～150质量比配制成400～430mL悬浊液，再将悬浊液加热到130～140℃，直至完全固体溶解，配置成第二种溶液，将第一种溶液缓慢滴加至第二种溶液中，然后在130～140℃下反应30～50分钟后溶液变为墨绿色，反应停止；再将反应温度冷却到20～30℃后，将溶液倒入800～1200mL去离子水中，静置析出白色沉淀，真空抽滤，并用200～400mL去离子水洗涤滤饼，真空干燥得到白色固体，即2,7-二甲基蒽醌；
步骤3、将浓硫酸，醋酸酐和冰乙酸按照1：3～4：70～80质量比配制成溶液并置于0℃下，然后将步骤2制得的2,7-二甲基蒽醌与三氧化铬按1：12～14的摩尔比缓慢加入到上述溶液中，然后将反应温度升至110～130℃，持续搅拌5～6小时，反应停止；反应温度冷却到20～30℃后，将溶液倒入400～600mL去离子水中，静置析出黄色沉淀，真空抽滤，并用200～300mL去离子水洗涤滤饼，真空干燥得到亮黄色固体，即配体H2AQ；
步骤4、将步骤3制得的配体H2AQ与金属钴盐按1：0.9～1.1摩尔比加入到4～8mL N,N-二甲基乙酰胺和1～2mL乙醇的混合溶液中，然后超声震荡使其完全溶解后向其澄清溶液加入0.2～0.4mL有机酸，置于高压反应釜中，经过2～4小时升温至100～120℃，保温120～132小时，之后8～12小时降至20～30℃，得到深紫色块状晶体，过滤收集，使用3～5m剂CL N,N-二甲基乙酰胺洗涤，干燥，得到目标化合物，即光催化剂Co-AQ，所述有机酸选自三氟乙酸或冰乙酸中的一种。
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