CN113831340B - 一种杯[n]二氢吖啶大环及其制备方法 - Google Patents
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- -1 dihydroacridine macrocycle Chemical class 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 claims description 2
- 230000000274 adsorptive effect Effects 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
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- 125000001424 substituent group Chemical group 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 7
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- 238000001228 spectrum Methods 0.000 description 13
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- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical class COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 1
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- 238000001819 mass spectrum Methods 0.000 description 1
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- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
- C07D471/18—Bridged systems
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D15/08—Selective adsorption, e.g. chromatography
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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Abstract
本发明公开了一种杯[n]二氢吖啶大环及其制备方法。所述杯[n]二氢吖啶大环的结构式如式TM所示,式TM中,R1和R2独立地选自氢和C1~C10的烷基;R3选自氢、C1~C10的烷基、苄基和C6~C10的芳基;R4选自氢、C1~C10的烷基和C6~C10的芳基;n表示重复单元数,为1~10之间的自然数。本发明提供的杯[n]二氢吖啶大环具有尺寸合适的空腔大小,可用于包结客体,且在固态下具有良好的晶态,可用于吸附分离;具有优越的光物理性质(例如延迟荧光),可用于基于荧光材料的有机发光二极管。可以预见,本发明提供的杯[n]二氢吖啶大环在超分子化学和材料化学等领域具有非常广阔的应用前景。
Description
技术领域
本发明涉及一种杯[n]二氢吖啶大环及其制备方法,属于有机超分子化学领域。
背景技术
超分子化学的一个重要研究内容就是设计与合成新型的大环主体分子,并进一步构筑具有特殊结构和功能的组装体。在过去的半个世纪里,除了冠醚、杯芳烃、葫芦脲和柱芳烃等经典的大环主体外,一些由新型结构基元形成的大环主体也被合成与报道。这些大环分子结构多种多样,并不断在分子识别与自组装、材料化学和生物医药等方面得到广泛应用。然而,大环的合成一直是一个挑战。因此,能够从简单的原料出发以高产率得到具有新颖结构的大环分子具有重要意义。这不仅能够丰富大环化合物的种类,促进大环化学的发展,还能够为材料化学和生命科学等领域提供新的物质基础。基于此,本发明提供设计并合成了一类新型的杯[n]二氢吖啶大环。
发明内容
本发明的目的是提供一种杯[n]二氢吖啶大环及其制备方法,制备方法简单、原料易得、产物产率高、容易分离纯化。
本发明所提供的杯[n]二氢吖啶大环的结构式如式TM所示,
式TM中,R1和R2独立地选自氢和C1~C10的烷基;R3选自氢、C1~C10的烷基、苄基和C6~C10的芳基;R4选自氢、C1~C10的烷基和C6~C10的芳基;
n表示重复单元数,为1~10之间的自然数,优选3~6、3~5、3或4。
具体地,R1和R2均选自氢和C1~C3的烷基,优选自氢和甲基;R3选自氢、C1~C3 的烷基、苄基、吡啶基、取代或未取代的苯基、取代或未取代的联苯基、4-(4,6-二苯基-1,3,5-三嗪基)苯基、4-(9,10-二氢-9-硼基)苯基、4-(苯磺酰基)苯基,C1~C3 的烷基优选为甲基,所述苯基的取代基优选为C1~C3的烷氧基、卤素、氰基或醛基; R4选自氢和C1~C3的烷基,优选自氢和甲基。
本发明杯[n]二氢吖啶大环的结构式为下述中任一种:
本发明还提供了所述杯[n]二氢吖啶大环的制备方法,包括如下步骤:
在催化剂存在的条件下,式A所示化合物与醛类化合物进行反应,得到式TM所示杯[n]二氢吖啶大环;
式A中,R1、R2、R3的定义同式TM;
式TM中的R4来自于所述醛类化合物;
所述醛类化合物为多聚甲醛、乙醛、丙醛、丁醛或苯甲醛;
式A所示化合物与所述醛类化合物的摩尔比为1:3~10,优选1:3~5,更优选1: 3;
式A所示化合物与所述催化剂的摩尔比为1:0.1~0.5,优选1:0.1~0.3,更优选1:0.1。
上述的制备方法中,所述催化剂为路易斯酸;
所述路易斯酸可为三氟化硼乙醚、三氯化铝、三氯化铁、六水合三氯化铁、四氯化锡、三氟乙酸、甲磺酸或三氟甲磺酸。
上述的制备方法中,所述反应采用的溶剂为二氯甲烷、氯仿、1,2-二氯乙烷、四氢呋喃、丙酮、乙腈、1,4-二氧六环、邻二氯苯、甲苯或二甲苯。
上述的制备方法中,所述反应的温度为0~30℃,时间为2~24小时。
本发明方法还包括对得到的所述杯[n]二氢吖啶大环进行纯化的步骤,如采用重结晶、柱色谱法和升华中的至少一种。
本发明提供的杯[n]二氢吖啶大环的制备方法简单、原料易得、产物产率高、容易分离纯化。本发明提供的杯[n]二氢吖啶大环具有尺寸合适的空腔大小,可用于包结客体,且在固态下具有良好的晶态,可用于吸附分离;具有优越的光物理性质(例如延迟荧光),可用于基于荧光材料的有机发光二极管。可以预见,本发明提供的杯[n]二氢吖啶大环在超分子化学和材料化学等领域具有非常广阔的应用前景。
附图说明
图1为本发明实施例1制备所得化合物B1的核磁氢谱。
图2为本发明实施例1制备所得化合物B1的核磁碳谱。
图3为本发明实施例2制备所得化合物B2的核磁氢谱。
图4为本发明实施例2制备所得化合物B2的核磁碳谱。
图5为本发明实施例2制备所得化合物B3的核磁氢谱。
图6为本发明实施例2制备所得化合物B3的核磁碳谱。
图7为本发明实施例3制备所得化合物B4的核磁氢谱。
图8为本发明实施例3制备所得化合物B4的核磁碳谱。
图9为本发明应用例1中化合物B1包结各种客体分子的单晶示意图。
图10为本发明应用例1中化合物B1选择性吸附分离4-甲基吡啶的核磁氢谱。
图11为本发明应用例2中化合物B4在稀溶液条件下的紫外可见吸收光谱和荧光光谱。
图12为本发明应用例2中化合物B4在稀溶液条件下的瞬态光谱。
具体实施方式
下述实施例中所使用的实验方法如无特殊说明,均为常规方法。
下述实施例中所用的材料、试剂等,如无特殊说明,均可从商业途径得到。
实施例1、制备B1所示化合物
反应流程图如下式所示。
具体步骤如下:
在1000mL圆底烧瓶中依次加入A1(2.0g,9.0mmol,1equiv.)、多聚甲醛(0.8g,27.0mmol,3equiv.)和300mL二氯甲烷,室温搅拌10分钟,再加入三氯化铁(240mg,0.9mmol,0.1equiv.)反应6小时,向反应体系加入300mL饱和碳酸氢钠溶液,剧烈搅拌2小时,分液,干燥,浓缩,柱层析色谱分离(流动相为石油醚:二氯甲烷=2:1),得到1.90g白色固体粉末即为化合物B1,产率为90%。
如图1和图2所示,该化合物B1的核磁氢谱、碳谱和质谱分析结果如下:
1H NMR(400MHz,CDCl3,298K):δ7.11(d,6H),6.97(s,6H),6.80(d,6H),3.90(s,6H),3.38(s,9H),1.26(s,18H).13C NMR(100MHz,CDCl3,298K):δ140.7,133.6,133.0,126.7,123.6,111.6,41.1,36.6,33.3,26.9.HRMS(ESI):m/z[M+H]+=706.4157(calcd.706.4156for C51H52N3 +).
由上述检测结果确证,化合物B1的结构正确。
实施例2、制备B2、B3所示化合物
反应流程图如下式所示。
具体步骤如下:
在1000mL圆底烧瓶中依次加入A2(2.0g,7.0mmol,1equiv.)、多聚甲醛(0.63g,21.0mmol,3equiv.)和300mL二氯甲烷,室温搅拌10分钟,再加入三氯化铁(189mg,0.7mmol,0.1equiv.)反应8小时,向反应体系加入300mL饱和碳酸氢钠溶液,剧烈搅拌2小时,分液,干燥,浓缩,柱层析色谱分离(流动相为石油醚:二氯甲烷=2:1),得到白色固体粉末,即为化合物B2(1.0g)和B3(0.31g),产率分别为50%和15%。
如图3和图4所示,该化合物B2的结构确证结果如下:
1H NMR(400MHz,CDCl3,298K):δ7.60(t,6H),7.49(t,3H),7.39–7.32(m,6H), 7.26(s,6H),7.12(d,6H),6.86(dd,6H),6.23(d,6H),3.86(s,6H),1.45(s,16H).13C NMR(100MHz,CDCl3,298K):δ141.4,140.0,133.9,131.4,130.6,130.6,128.0,126.5,124.3,113.6,40.8,36.2,29.1.HRMS(ESI):m/z[M+H]+=892.4627(calcd.892.4625for C66H58N3 +).
如图5和图6所示,该化合物B3的结构确证结果如下:
1H NMR(400MHz,CDCl3,298K):δ7.59(t,8H),7.47(t,4H),7.34–7.27(m,8H), 7.17(d,8H),6.80(dd,8H),6.12(d,8H),3.81(s,8H),1.56(s,24H).13C NMR(100MHz, CDCl3,298K):δ141.6,139.0,133.2,131.4,130.8,129.8,128.0,126.8,125.7,113.8,40.7,36.0,32.1.HRMS(ESI):m/z[M+H]+=1189.6149(calcd.1189.6143for C88H77N4 +).
由上述检测结果确证,化合物B2和B3的结构正确。
实施例3、制备B4所示化合物
反应流程图下式所示。
具体步骤如下:
在1000mL圆底烧瓶中依次加入A3(2.0g,3.9mmol,1equiv.)、多聚甲醛(349ng,11.7mmol,3equiv.)和300mL二氯甲烷,室温搅拌10分钟,再加入三氯化铁(105mg,0.4mmol,0.1equiv.)反应12小时,向反应体系加入300mL饱和碳酸氢钠溶液,剧烈搅拌2小时,分液,干燥,浓缩,柱层析色谱分离(流动相为石油醚:二氯甲烷=2:1),得到黄色固体粉末614mg。所述黄色固体为化合物B4,产率为30%。
如图7和图8所示,该化合物B4的结构确证结果如下:
1H NMR(400MHz,CDCl3,298K):δ9.01(d,6H),8.85–8.80(m,12H),7.65–7.58 (m,24H),7.19(d,6H),6.94(dd,6H),6.42(d,6H),3.91(s,5H),1.51(s,18H).13C NMR (100MHz,CDCl3,298K):δ171.8,171.2,145.6,139.7,136.1,135.7,134.3,132.7,131.3, 131.3,131.1,129.0,128.7,126.7,124.5,114.2,40.8,36.3,29.2.HRMS(ESI):m/z[M+H]+=1585.7026(calcd.1585.7015for C88H77N4 +).
由上述检测结果确证,化合物B4的结构正确。
应用例1、
以本发明实施例1制备得到的杯[3]二氢吖啶大环B1为例说明本发明大环在主客体化学以及吸附分离中的应用。
(一)通过在不同溶剂体系(环己烷、丙酮、甲苯、四氢呋喃、1,4-二氧六环、) 中缓慢挥发B1的饱和溶液,可以得到B1包结各种客体分子的单晶,通过X-射线衍射分析可以得到这些主客体复合物的晶体结构,如图9所示。
(二)制备所得的B1可用于4-甲基吡啶的选择性吸附分离。吸附分离实验操作如下:将20mg干燥的B1粉末放置于等摩尔比的甲基吡啶(2-甲基吡啶、3-甲基吡啶、 4-甲基吡啶)混合蒸汽氛围中。8小时后取固体粉末用核磁氢谱进行表征(如图10所示)。结果发现B1选择性地吸附4-甲基吡啶,选择性高达94%。
应用例2、
以本发明实施例3制备得到的杯[3]二氢吖啶大环B4为例说明这类大环在有机发光材料中的应用。
将所制备的B4溶于色谱纯甲苯中配成10-5mol/L的稀溶液,并测试该溶液的紫外可见吸收光谱和荧光发射光谱(如图11所示)。结果显示B4最大吸收波长为380nm,最大发射波长为528nm。其瞬态光谱(如图12所示)显示其具有微秒级(1.2μs)的延迟发光寿命,并且除氧后的荧光量子产率为80%,表明杯[3]二氢吖啶大环B4是一种延迟荧光材料,可用于基于荧光材料的有机发光二极管。
Claims (3)
3.权利要求1或2所述杯[n]二氢吖啶大环在吸附分离或作为有机发光材料在有机发光二极管中的应用。
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