CN114213633B - 4CzIPN型有机聚合物的制备方法及其在光催化合成中的应用 - Google Patents
4CzIPN型有机聚合物的制备方法及其在光催化合成中的应用 Download PDFInfo
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- PRWATGACIORDEL-UHFFFAOYSA-N 2,4,5,6-tetra(carbazol-9-yl)benzene-1,3-dicarbonitrile Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=C(C#N)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C(N2C3=CC=CC=C3C3=CC=CC=C32)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C1C#N PRWATGACIORDEL-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229920000620 organic polymer Polymers 0.000 title claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 title abstract description 9
- 230000015572 biosynthetic process Effects 0.000 title abstract description 7
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 230000001699 photocatalysis Effects 0.000 title abstract description 4
- 239000011941 photocatalyst Substances 0.000 claims abstract description 21
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 15
- UWYZHKAOTLEWKK-UHFFFAOYSA-N 1,2,3,4-tetrahydroisoquinoline Chemical compound C1=CC=C2CNCCC2=C1 UWYZHKAOTLEWKK-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 150000001345 alkine derivatives Chemical group 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- IQHSSYROJYPFDV-UHFFFAOYSA-N 2-bromo-1,3-dichloro-5-(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC(Cl)=C(Br)C(Cl)=C1 IQHSSYROJYPFDV-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 125000005647 linker group Chemical group 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 2
- 239000012038 nucleophile Substances 0.000 claims description 2
- 239000012434 nucleophilic reagent Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims description 2
- FIHILUSWISKVSR-UHFFFAOYSA-N 3,6-dibromo-9h-carbazole Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC=C3NC2=C1 FIHILUSWISKVSR-UHFFFAOYSA-N 0.000 abstract description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 12
- 229920000642 polymer Polymers 0.000 abstract description 11
- 239000000178 monomer Substances 0.000 abstract description 6
- 229920006391 phthalonitrile polymer Polymers 0.000 abstract description 5
- 238000010534 nucleophilic substitution reaction Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- -1 9H-carbazole-9-yl Chemical group 0.000 abstract description 2
- 238000006552 photochemical reaction Methods 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- 201000009813 cataract 31 multiple types Diseases 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
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- 239000002638 heterogeneous catalyst Substances 0.000 description 3
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WVHMPQKZPHOCRD-UHFFFAOYSA-N 2,4,5,6-tetrafluorobenzene-1,3-dicarbonitrile Chemical compound FC1=C(F)C(C#N)=C(F)C(C#N)=C1F WVHMPQKZPHOCRD-UHFFFAOYSA-N 0.000 description 1
- ONQBUHWENXKHHP-UHFFFAOYSA-N 2-phenyl-3,4-dihydro-1h-isoquinoline Chemical compound C1CC2=CC=CC=C2CN1C1=CC=CC=C1 ONQBUHWENXKHHP-UHFFFAOYSA-N 0.000 description 1
- HXOBCWWZMWUVFN-UHFFFAOYSA-N 3,5-dibromo-9h-carbazole Chemical compound C1=CC(Br)=C2C3=CC(Br)=CC=C3NC2=C1 HXOBCWWZMWUVFN-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- FXORZKOZOQWVMQ-UHFFFAOYSA-L dichloropalladium;triphenylphosphane Chemical compound Cl[Pd]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FXORZKOZOQWVMQ-UHFFFAOYSA-L 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000009935 nitrosation Effects 0.000 description 1
- 238000007034 nitrosation reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 231100000683 possible toxicity Toxicity 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
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Abstract
本发明涉及一种4CzIPN型有机聚合物的制备方法及其在光催化合成中的应用，提供一种基于2,4,5,6‑四(9H‑咔唑‑9‑基)间苯二腈(4CzIPN)荧光分子的4CzIPN型有机聚合物的制备方法，本法以2,4,5,6‑四氟间苯二腈和3,6‑二溴‑9H‑咔唑或3,6‑二溴‑9H‑咔唑为起始原料，通过亲核取代反应，一步生成溴代4CzIPN单体，再通过钯催化的Sonogashira‑Hagihara偶联反应，使其分别与1,4‑苯二炔、1,3,5‑苯三炔或1,2,4,5‑苯四炔反应，依次构建六种不同骨架的聚合物，所合成的上述聚合物可作为非均相光催化剂催化可见光诱导的C(sp3)–H键官能团化反应，兼具条件温和，底物适用范围广、绿色可持续等诸多优势，证明了其在有机光化学反应的巨大应用前景。
Description
技术领域
本发明属于材料化学领域，涉及有机合成技术，尤其是一种4CzIPN型有机聚合物的制备方法及其在光催化合成中的应用。
背景技术
可见光诱导的合成反应是目前最为绿色的合成手段之一，然而遗憾的是大多数有机化合物在可见光区没有吸收，无法直接利用可见光实现光能到化学能的转化，外加的光催化剂可充当吸收可见光的媒介，从基态跃迁到激发态，进而促进后续反应的进行。按照在反应体系中的分散状态，光催化剂可分为均相和异相，均相光催化剂又可分为：过渡金属配合物和有机染料。过渡金属配合物尽管拥有优异的光学性能，但重金属残留、潜在毒性、价格昂贵等固有缺陷极大地限制其在医药化工领域的应该用，有机染料尽管价格低廉，但结构稳定性差，催化反应时容易光漂白。
近年来，通过聚合策略构建新型异相光催化剂逐步兴起，国内外课题组相继合成一系列基于过渡金属配合物或有机染料的聚合物，并以此作为异相光催化剂，催化多种化学反应的进行。这类新型光催化剂对比传统光催化剂具有以下优势：(1)既保留了均相光催化剂的效率，兼具异相催化剂的可回收性；(2)结构稳定，不易失活；(3)结构内存在大共轭结构，缩小了带隙能，确保在可见光区相应。考虑到过渡金属配合的价格和毒性，有机染料聚合物无疑是更为绿色、可持续、环境友好的理想光催化剂。
现有技术中公开的咔唑基二腈基苯(CDCB)荧光平台为有机染料光催化剂的合成提供新的思路，对比(杂)蒽荧光平台，该平台具有合成简便、结构多样、HOMO-LUMO能级/氧化还原电位可调节等优势，尤其是其中的“明星分子”4CzIPN，在染料/金属双催化偶联反应、光致亚胺烷基化反应、二氧化碳羧化反应、自由基串联反应等多个领域崭露头角。
发明内容
本发明的目的在于克服现有技术的不足之处，提供一种基于2,4,5,6-四(9H-咔唑-9-基)间苯二腈(4CzIPN)荧光分子的4CzIPN型有机聚合物的制备方法，本法以2,4,5,6-四氟间苯二腈和3,6-二溴-9H-咔唑或3,6-二溴-9H-咔唑为起始原料，通过亲核取代反应，一步生成溴代4CzIPN单体，再通过钯催化的Sonogashira-Hagihara偶联反应，使其分别与1,4-苯二炔、1,3,5-苯三炔或1,2,4,5-苯四炔反应，依次构建六种不同骨架的聚合物，所合成的上述聚合物可作为非均相光催化剂催化可见光诱导的C(sp3)–H键官能团化反应。
本发明解决其技术问题是采取以下技术方案实现的：
一种4CzIPN型有机聚合物，其合成方法为：
其中，A代表电子供体，D代表电子供体，L代表链接物，CPP代表共轭聚合光催化剂。
上述具体方法步骤包括：通过亲核取代反应将电子供体2,4,5,6-四氟间苯二腈与电子受体3,6-二溴-9H-咔唑或3,6-二溴-9H-咔唑相连接，形成溴代4CzIPN单体，使用端炔1,4-苯二炔、1,3,5-苯三炔或1,2,4,5-苯四炔作为连接物，再通过Sonogashira-Hagihara偶联反应，使单体与炔烃相互交联，进而生成目标聚合物CPP1-6。
而且，所述目标聚合物CPP1-6嵌段结构特征如下：
一种4CzIPN型有机聚合物的应用，将其应用于催化可见光诱导的C(sp3)–H键官能团化反应，所述反应方程式如下：
其中NuH代表亲核试剂，包括H-亚磷酸酯、硝基甲烷、活泼亚甲基化合物、端炔、丙酮，取代基R1包括6,7-甲氧基、6-溴、7-溴，取代基R2包括4-甲基、4-甲氧基、4-苯基、4-氟、4-氯、4-溴、4-三氟甲基。
上述反应条件包括：以四氢异喹啉和亲核试剂为起始原料，4CzIPN有机聚合物作为光催化剂，在室温条件下，空气或氧气氛围中，460nm LED蓝光照射，待反应完全后，分离纯化即得一系列C(sp3)–H键官能团化产物，其中聚合物光催化剂均可通过过滤或离心进行分离，并可重复使用。
本发明的优点和积极效果是：
本发明使用4CzIPN聚合物作为新型异相光催化剂，打破均相与异相催化剂的界限，既保留了异相催化剂可循环这一突出优势，又赋予其均相催化剂高效的催化效率，同时克服了传统均相光催化剂价格昂贵、重金属残留、结构不稳定，难以回收等诸多缺陷。该聚合物可用于多种C(sp3)–H键官能团化反应，兼具条件温和，底物适用范围广、绿色可持续等诸多优势，证明了其在有机光化学反应的巨大应用前景。
具体实施方式
下面通过具体实施例对本发明作进一步详述，以下实施例只是描述性的，不是限定性的，不能以此限定本发明的保护范围。
一种4CzIPN聚合物CPP3的制备方法，步骤如下：
在氮气氛围中，向60毫升干燥的四氢呋喃中加入9.5克3,5-二溴咔唑，待完全溶解后，缓慢加入1.0克氢化钠。搅拌30分钟后，向反应体系中加入130毫克2,4,5,6-四氟间苯二腈，并在室温下持续搅拌12小时。随后加入2毫升水淬灭反应，旋干溶剂后，残余物用正己烷/二氯甲烷进行重结晶，即得3,6-溴代4CzIPN黄色固体。将564毫克的3,6-溴代4CzIPN、12毫克双三苯基膦二氯化钯、6毫克碘化亚酮依次加入到5毫升三乙胺和5毫升N,N-二甲基甲酰胺的混合溶液中，该混合溶液在氮气氛围中加热至90摄氏度，保持24小时。待反应结束后，过滤即可分离得到CPP3粗产品，然后通过甲醇/二氯甲烷溶液对粗产品进行索氏提取，最终得到CPP3纯品。
CPP3作为光催化剂剂催化可见光诱导的C(sp3)–H键官能团化反应，具体实例如下：
向10毫升Schlenk管中，分别加入0.2毫摩尔的N-苯基-四氢异喹啉1a、2.0毫摩尔的H-亚磷酸二乙酯2a、2.0毫克CPP以及2.0毫升乙二醇，该混合物在室温条件下，氧气气氛中搅拌，并用3瓦蓝色LED(460nm)持续照射6小时。待底物1a消耗完全后，加入5.0毫升水淬灭反应，并用5.0毫升乙酸乙酯萃取三次，合并有机相，加入无水硫酸钠干燥，过滤后旋去有机溶剂。残余物使用石油醚/乙酸乙酯体系作为洗脱液，中性氧化铝为固定相，通过柱层析色谱纯化后，得到目标产物3aa。
产物3aa的表征数据如下：
White solid(56.6mg,82％yield)；m.p.69.8–70.4℃；1H NMR(400MHz,Chloroform-d)δ7.41(d,J＝6.6Hz,1H),7.34–7.09(m,5H),7.01(d,J＝8.3Hz,2H),6.82(t,J＝7.3Hz,1H),5.23(d,J＝20.0Hz,1H),4.43–3.80(m,5H),3.69–3.63(m,1H),3.37–2.90(m,2H),1.28(t,J＝7.1Hz,3H),1.17(t,J＝7.1Hz,3H).13C NMR(101MHz,Chloroform-d)δ149.4(d,J＝5.8Hz),136.5(d,J＝5.6Hz),130.7,129.2,128.8(d,J＝2.6Hz),128.1(d,J＝4.7Hz),127.5(d,J＝3.6Hz),125.9(d,J＝2.8Hz),118.5,114.8,63.3(d,J＝7.2Hz),62.3(d,J＝7.7Hz),58.8(d,J＝159.2Hz),43.5,26.8,16.5(d,J＝5.5Hz),16.4(d,J＝5.8Hz).31P NMR(162MHz,Chloroform-d)δ22.17.HRMS(ESI-TOF)m/z:[M+Na]+calcd forC19H24NNaO3P 368.1386,found 368.1390.
尽管为说明目的公开了本发明的实施例，但是本领域的技术人员可以理解：在不脱离本发明及所附权利要求的精神和范围内，各种替换、变化和修改都是可能的，因此，本发明的范围不局限于实施例所公开的内容。
Claims (3)
1.一种4CzIPN型有机聚合物，其特征在于：其合成方法为：
其中，A代表电子受体，D代表电子供体，L代表链接物，CPP代表共轭聚合光催化剂。
2.一种如权利要求1所述的4CzIPN型有机聚合物的应用，其特征在于：将其应用于催化可见光诱导的C(sp3)–H键官能团化反应，所述反应方程式如下：
其中NuH代表亲核试剂，包括H-亚磷酸酯、硝基甲烷、活泼亚甲基化合物、端炔、丙酮，取代基R1包括6,7-甲氧基、6-溴、7-溴，取代基R2包括4-甲基、4-甲氧基、4-苯基、4-氟、4-氯、4-溴、4-三氟甲基。
3.根据权利要求2所述的一种4CzIPN型有机聚合物的应用，其特征在于：反应条件包括：以四氢异喹啉和亲核试剂为起始原料，4CzIPN有机聚合物作为光催化剂，在室温条件下，空气或氧气氛围中，460nm LED蓝光照射，待反应完全后，分离纯化即得一系列C(sp3)–H键官能团化产物，其中聚合物光催化剂均可通过过滤或离心进行分离，并可重复使用。
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