CN116730907A - 一种含醛基的n-芳基化紫精类分子的合成方法 - Google Patents
一种含醛基的n-芳基化紫精类分子的合成方法 Download PDFInfo
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- 238000001308 synthesis method Methods 0.000 title abstract description 11
- 238000006254 arylation reaction Methods 0.000 title abstract description 5
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
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- 239000007810 chemical reaction solvent Substances 0.000 claims description 6
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 5
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- GTPNXFKONRIHRW-UHFFFAOYSA-N 2-iodo-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=C(I)C(C)=C1 GTPNXFKONRIHRW-UHFFFAOYSA-N 0.000 description 1
- BRUOAURMAFDGLP-UHFFFAOYSA-N 9,10-dibromoanthracene Chemical compound C1=CC=C2C(Br)=C(C=CC=C3)C3=C(Br)C2=C1 BRUOAURMAFDGLP-UHFFFAOYSA-N 0.000 description 1
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
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- OAEGRYMCJYIXQT-UHFFFAOYSA-N dithiooxamide Chemical compound NC(=S)C(N)=S OAEGRYMCJYIXQT-UHFFFAOYSA-N 0.000 description 1
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- QLULGIRFKAWHOJ-UHFFFAOYSA-N pyridin-4-ylboronic acid Chemical compound OB(O)C1=CC=NC=C1 QLULGIRFKAWHOJ-UHFFFAOYSA-N 0.000 description 1
- BGUWFUQJCDRPTL-UHFFFAOYSA-N pyridine-4-carbaldehyde Chemical compound O=CC1=CC=NC=C1 BGUWFUQJCDRPTL-UHFFFAOYSA-N 0.000 description 1
- GPHQHTOMRSGBNZ-UHFFFAOYSA-N pyridine-4-carbonitrile Chemical compound N#CC1=CC=NC=C1 GPHQHTOMRSGBNZ-UHFFFAOYSA-N 0.000 description 1
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- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
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- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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- C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
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Abstract
本发明公开了一种含醛基的N‑芳基化紫精类分子的合成方法，该方法采用Nesmeyanov反应，通过吡啶类化合物和含醛基的不对称碘鎓分子反应制备含醛基的N‑芳基化紫精类分子。本发明提供的合成方法工艺简单，易于纯化、收率高、通用性强。所制备的分子具有优异的电化学性能和电致变色性能。醛基的引入更进一步拓展了其可修饰化空间，为构建各种含紫精的功能材料提供了无限可能，有望应用于电/光致变色、能量存储、吸附、超分子化学、催化和传感等多个领域。
Description
技术领域
本发明属于有机功能材料合成技术领域，具体涉及一类含醛基的N-芳基化紫精类分子的合成方法。
背景技术
紫精类化合物是一类经典的n型半导体材料，具有优良的得电子能力，被广泛应用于电致变色、超分子组装、储能等领域。常见的改性方法主要是在两个吡啶单元之间引入共轭基团，以达到调控其光电性能的目的。但是该方法仅限于小分子的结构设计，无法实现更为复杂的功能体系构筑，例如聚合物和共价有机框架(COF)等。醛基是一种常见的化学基元，可以和氨基、羟基等多种单元反应。很多文献利用醛基和氨基创制了结构多样的COF材料，实现了光催化、气体吸附、能量存储以及电致变色等多方面的应用。因此，在刚性的紫精结构中引入醛基为新型功能材料的构筑提供了广泛的空间。
目前，文献报道的含醛基的N-芳基化紫精类分子仅有一例结构。其合成方法主要利用经典Zincke反应。该方法最大的缺点是：1)合成过程中涉及醛基的保护/脱保护、步骤繁多、总产率低(Angew.Chem.Int.Ed.2015,54,4028–4031)；2)适用范围窄，特别是对于强吸电子的体系不适用(J.Am.Chem.Soc.2015,137,11710-11717)。因此，开发一种简单的、适用面广的含醛基N-芳基化紫精类分子很有必要。
发明内容
为了解决Zincke反应路线的局限性，本发明通过Nesmeyanov反应，提供一种简单、适用面广的含醛基的N-芳基化紫精类分子的合成方法。
针对上述目的，本发明采用的技术方案为：在氮气气氛下，将式B化合物、式C或C′化合物、一水合醋酸铜加入反应溶剂中，反应混合物在80～150℃下反应时间12～72小时，反应结束后冷却至室温，加入乙醚沉淀后，过滤收集沉淀，并用乙醚洗涤，真空干燥后得到相应的目标化合物。反应方程式如下所示：
式中，L为连接单元，选自以下结构中任意一种：
X-代表阴离子，可以为BF4 -、PF6 -、ClO4 -、Cl-、Br-、I-等中任意一种；m代表阴离子的数量，取决于分子骨架中的正电荷数量，可以为2～4中任意整数；R1和R2各自独立的代表氢、C2～C9烷基、卤素、C2～C9烷氧基、硝基、酯基、氰基、苯环数目为1～5的芳香基团中任意一种。
上述合成方法中，优选式B化合物、式C或C′化合物、一水合醋酸铜的摩尔比为1:2～6:0.1～1。
上述合成方法中，优选在100～120℃下反应时间20～30小时。
上述合成方法中，优选反应溶剂为N,N-二甲基甲酰胺(DMF)、甲苯、1,4-二氧六环、二甲亚砜、四氢呋喃中任意一种。
本发明的有益效果如下：
本发明的合成方法工艺简单，易于纯化、收率高、通用性强，所得含醛基的N-芳基化紫精类分子具有优异的得电子能力和电致变色性能。醛基的引入更进一步拓展了其可修饰化空间，为构建各种含紫精的功能材料提供了无限可能，有望应用于电/光致变色、能量存储、吸附、超分子化学、催化和传感等多个领域。
附图说明
图1是式化合物B-1的核磁氢谱。
图2是实施例1制备目标化合物V-CHO的核磁氢谱。
图3是实施例2制备目标化合物BtV-CHO的核磁氢谱。
图4是实施例3制备目标化合物AnV-CHO的核磁氢谱。
图5是实施例4制备目标化合物TTzV-CHO的核磁氢谱。
图6是实施例5制备目标化合物TPTV-CHO的核磁氢谱。
图7是实施例1制备化合物V-CHO的循环伏安曲线。
图8是实施例2制备化合物BtV-CHO的循环伏安曲线。
图9是实施例3制备化合物AnV-CHO的循环伏安曲线。
图10是实施例4制备化合物TTzV-CHO的循环伏安曲线。
图11是实施例1制备化合物V-CHO在加电条件的紫外光谱变化。
具体实施方式
下面结合附图和实施例对本发明进一步详细说，但本发明的保护范围不仅限于这些实施例。凡在本发明的精神和原则下所做的任何修改、等同替换和改进等，均应在本发明的保护范围之内。
下面实施例中所采用的式化合物B-1参考文献“Chem.Commun.,2017,53,7022–7025”中方法合成，具体合成路线和合成方法如下：
将25g(102mmol)2,4,6-三甲基碘苯和25g(122mmol)间氯过氧苯甲酸(m-CPBA)在100mL醋酸中室温搅拌反应24h。反应结束后，抽滤得到固体，用石油醚洗涤，干燥后得到白色固体，即式A化合物，收率为90％。在0℃条件下，向50mL含1.2g(7.99mmol)对甲酰基苯硼酸的二氯甲烷溶液中加入2.96mL(23.97mmol)三氟化硼的乙醚溶液，拌15min之后，加入3.2g(8.79mmol)式A化合物，室温反应10h。反应结束后，加入40mL含2.1g四氟硼酸钠的水溶液，室温搅拌3小时之后用二氯甲烷萃取，合并有机相，无水硫酸镁干燥过滤后，加入20mL乙醚在室温搅拌30min，抽滤得到式B-1化合物，收率为90％。式B-1化合物的结构表征数据为(见图1)：1H NMR(600MHz,d6-DMSO):δ(ppm)＝10.00(s,1H；CHO),8.16(d,J＝8.4Hz,2H；ArH),7.96(d,J＝8.4Hz,2H；ArH),7.24(s,2H；ArH),2.60(s,6H；CH3),2.30(s,3H；CH3)。
下面实施例中的式C-1化合物参考文献“Synthesis.,2014,46,2976–2982”中方法合成，具体合成路线和合成方法如下：
向500mL干燥两口烧瓶中依次加入2.0g(6.17mmol)5,5’-二溴-2,2’-联二噻吩、1.67g(13.6mmol)4-吡啶硼酸、5.1g(37.0mmol)碳酸钾和357mg(0.31mmol)四三苯基膦钯，之后将整个体系抽真空鼓N2三次之后加入100mL甲苯、50mL甲醇和20mL水，在85℃搅拌反应48h。反应完后自然冷却，将反应溶剂在旋转蒸发仪中旋干，然后利用硅胶柱层析的方法进行提纯，淋洗液为体积比4:1的二氯甲烷和甲醇的混合溶液，得白色固体1.3g，即式C-1化合物，产率66％。
下面实施例中的式C-2化合物参考文献“Dalton Trans.,2021,50,7944–7948”中方法合成，具体合成路线和合成方法如下：
向500mL干燥两口烧瓶中依次加入1.01g(3mmol)9,10-二溴蒽、0.92g(7.5mmol)4-吡啶硼酸、4.15g(30.0mmol)碳酸钾和350mg(0.30mmol)四三苯基膦钯，之后将整个体系抽真空鼓N2三次之后加入150mL N,N-二甲基甲酰胺和15mL水，在氮气氛围下100℃搅拌并反应24h，反应冷却后，将反应溶剂在旋转蒸发仪中旋干，然后利用硅胶柱层析的方法进行提纯，得黄色固体816mg，即式C-2化合物，产率82％。
下面实施例中的式C-3化合物参考文献“Angew.Chem.Int.Ed.2018,57,231–235”中方法合成，具体合成路线和合成方法如下：
将20mL(216mmol)4-吡啶甲醛和10g(83.4mmol)二硫代草酰胺在DMF溶剂中回流搅拌24h。待反应冷却至室温后，抽滤，并将所得固体产物用水洗涤得到19.2g式C-3化合物，产率77％。
下面实施例中的式C-4化合物参考文献“Nat Commun.,2015,6,8348”中方法合成，具体合成路线和合成方法如下：
将10g(96mmol)4-氰基吡啶、1g(3.8mmol)18-冠醚-6、225mg(4.0mmol)氢氧化钾在十氢化萘中于200℃条件下反应3h。反应结束后，将所得固体用盐酸酸化溶解，随后将少量不溶物杂质过滤后，将滤液酸化，抽滤得固体产物7.4g，即式C-4化合物，产率74％。
实施例1
向25mL干燥两口烧瓶中依次加入156mg(1mmol)4,4’-联吡啶(式C′-1化合物)、1.3g(3mmol)式B-1化合物和18mg(0.1mmol)一水合醋酸铜，之后将整个体系抽真空鼓N2三次之后加入2mL分析纯DMF，升温至100℃搅拌并反应24h。反应结束后待冷却至室温，加入乙醚沉淀，过滤收集沉淀，并用乙醚洗涤，真空干燥后得到目标化合物V-CHO，产率为97％，结构表征数据为(见图2)：1HNMR(400MHz,d6-DMSO):δ(ppm)＝10.22(s,2H；CHO),9.77(d,J＝6.6Hz,4H；C5H4N),9.12(d,J＝6.6Hz,4H；C5H4N),8.32(d,J＝8.4Hz,4H；C6H4),8.20(d,J＝8.4Hz,4H；C6H4)。
实施例2
本实施例中，用等摩尔量的式C-1化合物替换实施例1中的4,4’-联吡啶(式C′-1化合物)，其他步骤与实施例1相同，得到BtV-CHO，其产率为94％，结构表征数据为(见图3)：1HNMR(400MHz,d6-DMSO):δ(ppm)＝10.19(s,2H；CHO),9.33(d,J＝7.2Hz,4H；C5H4N),8.57(m,6H；C5H4N and C4H2S),8.28(d,J＝8.8Hz,4H；C6H4),8.13(d,J＝8.8Hz,4H；C6H4),8.00(d,J＝4.0Hz,2H；C4H2S)。
实施例3
本实施例中，用等摩尔量的式C-2化合物替换实施例1中的4,4’-联吡啶(式C′-1化合物)，其他步骤与实施例1相同，得到AnV-CHO，其产率为95％，结构表征数据为(见图4)：1HNMR(400MHz,d6-DMSO):δ(ppm)＝10.25(s,2H；CHO),9.68(d,J＝6.4Hz,4H；C5H4N),8.55(d,J＝6.4Hz,4H；C5H4N),8.39(d,J＝8.4Hz,4H；C6H4),8.29(d,J＝8.4Hz,4H；C6H4),7.84(m,4H；anthracene ArH),7.70(m,4H；anthracene ArH)。
实施例4
本实施例中，用等摩尔量的式C-3化合物替换实施例1中的4,4’-联吡啶(式C′-1化合物)，其他步骤与实施例1相同，得到TTzV-CHO，其产率为99％，结构表征数据为(见图5)：1H NMR(400MHz,d6-DMSO):δ(ppm)＝10.21(s,2H；CHO),9.59(d,J＝6.4Hz,4H；C5H4N),8.96(d,J＝6.4Hz,4H；C5H4N),8.31(d,J＝8.0Hz,4H；C6H4),8.19(d,J＝8.0Hz,4H；C6H4)。
实施例5
本实施例中，用6.7mmol式C-4化合物替换实施例1中的10mmol 4,4’-联吡啶(式C′-1化合物)，其他步骤与实施例1相同，得到TPTV-VHO，其产率为99％，结构表征数据为(见图6)：1H NMR(400MHz,d6-DMSO):δ(ppm)＝10.25(s,3H；CHO),9.81(m,12H；C5H4N),8.37(d,J＝7.6Hz,6H；C6H4),8.28(d,J＝7.6Hz,6H；C6H4)。
对上述实施例1～5制备的目标产物进行了电化学性能表征，结果如图7～10所示。循环伏安曲线表明：所制备的目标产物具有优异的得电子能力，并且性能和分子骨架密切相关。如图7所示，V-CHO具有明显的两对、可逆的氧化还原峰(-0.63/-0.55V，-0.80/-0.72V)。如图8～10所示，中间有共轭单元连接的线性BtV-CHO、AnV-CHO和TTzV-CHO，均具有一步、两电子还原的反应过程，其氧化还原电位分别位于-0.99/-0.85V、-0.95/-0.74V和-0.68/-0.52V。
此外，所制备的目标产物具有优异的电致变色性能。图11是实施例1制备化合物V-CHO在加电条件的紫外光谱变化。在所加电压区间为0到-0.2V(vs.Ag/AgCl)时，分子由二价离子状态变成阳离子自由基状态，并伴随着在451nm、675nm和746nm处产生很强的吸收峰。继续加电压到-0.4V(vs.Ag/AgCl)，分子由阳离子自由基状态变成中性状态，675nm和746nm处的吸收峰逐步减弱，并且在500～600nm处出现新的吸收峰。
Claims (4)
1.一种含醛基的N-芳基化紫精类分子的合成方法，其特征在于：在氮气气氛下，将式B化合物、式C或C′化合物、一水合醋酸铜加入反应溶剂中，反应混合物在80～150℃下反应时间12～72小时，反应结束后冷却至室温，加入乙醚沉淀后，过滤收集沉淀，并用乙醚洗涤，真空干燥后得到相应的目标化合物；反应方程式如下所示：
式中，L为连接单元，选自以下结构中任意一种：
X-代表阴离子，选自BF4 -、PF6 -、ClO4 -、Cl-、Br-、I-中任意一种；m代表阴离子的数量，取决于分子骨架中的正电荷数量，选自2～4的整数；R1和R2各自独立的代表氢、C2～C9烷基、卤素、C2～C9烷氧基、硝基、酯基、氰基、苯环数目为1～5的芳香基团中任意一种。
2.根据权利要求1所述的含醛基的N-芳基化紫精类分子的合成方法，其特征在于：所述式B化合物、式C或C′化合物、一水合醋酸铜的摩尔比为1:2～6:0.1～1。
3.根据权利要求1所述的含醛基的N-芳基化紫精类分子的合成方法，其特征在于：在100～120℃下反应时间20～30小时。
4.根据权利要求1所述的含醛基的N-芳基化紫精类分子的合成方法，其特征在于：所述反应溶剂为N,N-二甲基甲酰胺、甲苯、1,4-二氧六环、二甲亚砜、四氢呋喃中任意一种。
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