CN108503657A - 含五元杂环的硼氮掺杂稠环芳香烃及其合成方法及应用 - Google Patents
含五元杂环的硼氮掺杂稠环芳香烃及其合成方法及应用 Download PDFInfo
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- CN108503657A CN108503657A CN201711386656.1A CN201711386656A CN108503657A CN 108503657 A CN108503657 A CN 108503657A CN 201711386656 A CN201711386656 A CN 201711386656A CN 108503657 A CN108503657 A CN 108503657A
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- boron
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- aromatic hydrocarbon
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- 125000000623 heterocyclic group Chemical group 0.000 title claims abstract description 27
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 title claims abstract description 25
- 238000010189 synthetic method Methods 0.000 title abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 229910052796 boron Inorganic materials 0.000 claims abstract description 21
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 108
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 42
- 238000003786 synthesis reaction Methods 0.000 claims description 40
- 230000015572 biosynthetic process Effects 0.000 claims description 39
- 238000004440 column chromatography Methods 0.000 claims description 36
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 33
- 239000012266 salt solution Substances 0.000 claims description 30
- 229920006395 saturated elastomer Polymers 0.000 claims description 30
- 238000001914 filtration Methods 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 150000003233 pyrroles Chemical class 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- VIMMECPCYZXUCI-MIMFYIINSA-N (4s,6r)-6-[(1e)-4,4-bis(4-fluorophenyl)-3-(1-methyltetrazol-5-yl)buta-1,3-dienyl]-4-hydroxyoxan-2-one Chemical compound CN1N=NN=C1C(\C=C\[C@@H]1OC(=O)C[C@@H](O)C1)=C(C=1C=CC(F)=CC=1)C1=CC=C(F)C=C1 VIMMECPCYZXUCI-MIMFYIINSA-N 0.000 claims description 10
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 10
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 10
- 229940126142 compound 16 Drugs 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 125000005842 heteroatom Chemical group 0.000 claims description 10
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 claims description 9
- 229940126657 Compound 17 Drugs 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
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- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 9
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 8
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 8
- 125000004429 atom Chemical group 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910000085 borane Inorganic materials 0.000 claims description 7
- 150000004816 dichlorobenzenes Chemical class 0.000 claims description 7
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- LNUFLCYMSVYYNW-ZPJMAFJPSA-N [(2r,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[[(3s,5s,8r,9s,10s,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-disulfo Chemical compound O([C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1C[C@@H]2CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)[C@H]1O[C@H](COS(O)(=O)=O)[C@@H](OS(O)(=O)=O)[C@H](OS(O)(=O)=O)[C@H]1OS(O)(=O)=O LNUFLCYMSVYYNW-ZPJMAFJPSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 5
- VUDZSIYXZUYWSC-DBRKOABJSA-N (4r)-1-[(2r,4r,5r)-3,3-difluoro-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-4-hydroxy-1,3-diazinan-2-one Chemical compound FC1(F)[C@H](O)[C@@H](CO)O[C@H]1N1C(=O)N[C@H](O)CC1 VUDZSIYXZUYWSC-DBRKOABJSA-N 0.000 claims description 4
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 claims description 4
- 150000001454 anthracenes Chemical class 0.000 claims description 4
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000002220 fluorenes Chemical class 0.000 claims description 4
- 150000002240 furans Chemical class 0.000 claims description 4
- 150000002469 indenes Chemical class 0.000 claims description 4
- 150000002790 naphthalenes Chemical class 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- WHLUQAYNVOGZST-UHFFFAOYSA-N tifenamil Chemical group C=1C=CC=CC=1C(C(=O)SCCN(CC)CC)C1=CC=CC=C1 WHLUQAYNVOGZST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 3
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 3
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical group BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- QSQIGGCOCHABAP-UHFFFAOYSA-N hexacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC6=CC=CC=C6C=C5C=C4C=C3C=C21 QSQIGGCOCHABAP-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
本发明涉及一种含五元杂环的硼氮掺杂稠环芳香烃及其合成方法及应用,并对其进行光电物理性质的测试,进一步研究该类有机材料在有机电化学方面的潜在应用价值,本发明采用改进的合成方法使得反应原料价低易得,反应过程避免使用有毒试剂,合成方法简单易行,化合物在有机发光二极管、有机太阳能电池、有机场效应晶体管、有机激光器、有机传感器、分子开关、生物成像以及毒素检测等领域具有广泛的应用。
Description
技术领域
本发明涉及含硼多环芳香杂环有机化合物及其合成方法,以及光电物理性质的基础研究,合成方法涉及亲电取代、亲核取代、Suzuki偶联反应、金属化反应及催化反应等,光电物理性质研究设计吸收、发射以及CV测试。
背景技术
近年来,由于多环芳烃(PAHs)及其衍生物的模块化合成以及特殊的光电物理性质使得它们在有机光电材料方面受到越来越多的关注(Wang,C.;Dong,H.;Hu,W.;Liu,Y.;Zhu,D.Chem.Rev.2012,112,2208-2267.),该类化合物的应用广泛,可用于发光材料,像有机发光二极管(OLED)(Sato,Y.;Ichinosawa,S.;Kanai,H.Operation Characteristicsand Degradation of Organic Electroluminescent Devices.IEEE Journal ofSelected Topics in Quantum Electronics 4:1998,40-48.)、薄膜晶体管,也可用于有机太阳能电池(OPVs)(Dou,L.;You,J.;Hong,Z.;Xu,Z.;Li,G.;Street,R.A.;Yang,Y.25thAnniversary Article:A Decade of Organic/Polymeric PhotovoltaicResearch.Adv.Mater.2013,25,6642-6671.)。在多环芳烃衍生物的研究当中,对于B-N/C=C这对等电子体的研究较为广泛。实验中,将B-N键引入代替C=C键合成带有硼氮掺杂的多环芳烃类衍生物。BN键的引入几乎保留了全碳化合物空间构象,但其光物理性质发生明显的变化(Bosdet,M.J.D.;Piers,W.E.Can.J.Chem.2009,87,8-29.)。因此,在多环芳烃内引入杂原子,会对分子的能级和光物理性质产生影响。同时也为我们调节多环芳烃的光电物理性质提供了一种简便高效的方法。(Bunz,U.H.F.;Egelhart,J.U.;Lindner,B.D.;Schaffroth,M.Large N-Heteroacenes:New Tricks for Very Old DogsAngew.Chem.Int.Ed.2013,52,3810-3821.)常见掺杂到多环芳香烃中的杂原子有:氮、硫、磷、氧和硅等原子。杂原子的引入不仅可以改变多环芳香烃的物理性质,也可以有效的改变其化学性质(Gu,P.;Zhou,F.;Gao,J.;Li,G.;Wang,C.;Xu,Q.;Zhang,Q.;Lu,J.Synthesis,Characterization,and Nonvolatile Ternary Memory Behavior of a LargerHeteroacene with Nine Linearly Fused Rings and Two DifferentHeteroatoms.J.Am.Chem.Soc.,2013,135,14086–14089.)。
近些年,研究者们不断创新,在前人的基础上,从将一种杂原子引入到共轭芳烃体系中发展到现在将两种或两种以上不同的杂原子掺杂到共轭芳烃体系中。各种掺有杂原子的共轭芳烃层出不穷。在掺杂的杂原子中,硼原子由于是唯一一个缺电子的原子而比较特殊。众所周知,硼原子有一个空的p轨道,这使得硼原子可以与其他富电子的杂原子结合,能够在分子内产生电荷的移动。因此,就会产生与全碳的共轭体系完全不同的光电物理性质。这也使得研究者为进一步研究它们的产生兴趣。但是硼原子不稳定,它的空的p轨道也极易受到亲核试剂的进攻,因此,再设计合成硼类的共轭芳烃时,常常引入空间位阻较大的基团来稳定硼原子。化合物Ullazine就是合成的一种多环芳烃,通过Ullazine及其衍生物的合成,探究其光电物理性质,并对其应用进行探索。
2013年,Burkhard课题组探究了以Ullazine为母体合成的化合物在生物制药及有机材料方面的应用,文章介绍了含氮稠和杂环在生物制药和有机材料方面存在着巨大的潜在应用
(G.W.Gribble,inComprehensive Heterocyclic Chemi-stry II,Pergamon,2ndedn.,1996,pp.207.、A.Facchetti,Chem.Mater.,2011,23,73),像吡咯并[1,2-a]喹啉,吡唑[1,5-a]喹啉在抗菌(K.Tsuji,H.Tsubouchi and H.Ishikawa,Chem.Pharm.Bull.,1995,43,1678.)和抗肿瘤(A.Carbone,M.Pennat-i,B.Parrino,A.Lopergolo,P.Barraja,A.Montalbano,V.Spanò,S.Sbarr a,V.Doldi,M.De Cesare,G.Cirrincione,P.Diana andN.Zaffaroni,J.Med.Chem.,2013,56,7060.)方面存在着巨大的潜能,他们能够激活半胱天冬酶或诱导其凋亡,也可用作半导体材料,在光电子方面,可作为太阳能电池的敏化剂,展现了很好的电子运输功能。
2014年,S.Ito及K.Nozaki课题组通过不饱和的1,3-偶极环加成反应得到五元杂环化合物。文章通过开发一种新型的与各种烯烃、炔烃发生1,3-偶极环加成反应合成甲亚胺叶立德的方法,探究了合成具有稠合吡咯结构形成多环芳烃的方法。
2015年,Li ze sheng组论述了含氮杂环Ullazine作为16-π电子体,由于其强的分子内电荷转移在DSCs应用方面有很大的前景,在1991年,由课题组首次合成并将其应用到DSCs光电材料之后(O’Regan,B.;Gratzel,M.A Low-Cost,High-Efficiency SolarCell Based on Dye-Sensitized Colloidal TiO2 Films.Nature 1991,353,737-740.),对于Ullazine及其衍生物的研究受到越来越多的关注,Li课题组认为,相对于平面几何结构,JD染料中的Ullazine单元可能会不利于染料在半导体表面聚集(W.Ma,Y.Jiao andS.Meng,J.Phys.Chem.C,2014,118,16447-16457./J.Feng,Y.Jiao,W.Ma,M.K.Nazeeruddin,M.and S.Meng,J.Phys.Chem.C,2013,117,3772-3778.),因此,Li课题组设计了一系列以JD21为骨架的含硅的类似物,通过在ullazine和氰基丙烯酸基团的基础上引入三个经典π共轭单元(环戊二烯并苯(CPDT)(M.Zhang,Y.Wang,M.Xu,W.Ma,R.Liand P.Wang,Energy Environ.Sci.,2013,6,2944-2949./J.Zhang,Z.Yao,Y.Cai,L.Yang,M.Xu,R.Li,M.Zhang,X.Dong and P.Wang,Energy Environ.Sci.,2013,6,1604-1614),双噻吩并咯(DTS)(W.Zeng,Y.Cao,Y.Bai,Y.Wang,Y.Shi,M.Zhang,F.Wang,C.Pan andP.Wang,Chem.Mater.,2010,22,1915-1925.)和双噻吩并吡咯(DTP)(N.Cai,J.Zhang,M.Xu,M.Zhang and P.Wang,Adv.Funct.Mater.,2013,23,3539-3547.)。新设计的染料从Y1、Y2、Y3分别命名,系统的研究表明含Y2的染料(DST)显示了惊人的捕光能力,良好的热力学性能,良好的动力学参数,并对Y2/(TiO2)吸附系统有高稳定性。因此,该材料可应用到数码相机的制作方面。
2016年You课题组通过钯催化1-(2,6-二溴苯基)-1H-吡咯与炔烃反应,开发建立了各种π-共轭Ullazine类衍生物,通过性质检测,表明其在有机光电材料方面有巨大潜能。
综上所述,有机硼化合物在有机中有广泛的应用前景:储氢材料,有机合成,催化,光电材料,传感器,探头和生物活性分子。通过构建掺杂了硼氮原子直接相连的含有吡咯五元环的芘类化合物,对其光电物理性质进行测试,并对其可能应用的领域进行探索。
发明内容
本发明目的在于,提供一类化学结构新颖、包括含硼多元杂环芳香化合物,同时提供该化合物的设计合成方法及应用,以期为有机发光材料、有机太阳能电池、有机光电材料等领域做出贡献。
为了达到上述目的,本发明采用的技术方案是:
一种含有多取代基的杂环含硼芳香化合物,该化合物的结构式为:
A,B,C,Ar1,Ar2,Ar3,Ar4,Ar5,Ar6,Ar7,Ar8分别是独立的,为取代或非取代单个芳香环体系,或取代或非取代的多个芳香环体系;
R1,R2,R3,R4基团为独立的取代或非取代的芳基或者杂芳基;
X1,X5,X9为C,N原子之一;
X2,X7,X12为C,N,S原子之一;
X3,X8,X11为C,N,S原子之一;
X4,X13,X14为C或N原子。
而且,其中的A,B,C,Ar1,Ar2,Ar3,Ar4,Ar5,Ar6,Ar7,Ar8每一个由4到30个芳香环原子构成,为一个,两个,三个,四个芳香环或者杂环,或在4到30个芳香环原子构成的环中用N,O,S,Se等原子代替碳原子。
而且,其中A,B,C,Ar1,Ar2,Ar3,Ar4,Ar5,Ar6,Ar7,Ar8是苯环、噻吩环、呋喃环、吡咯、吡啶、苯并噻吩、苯并呋喃、苯并吡咯、苯并吡啶、萘环、蒽环、非那烯、并四苯、芘、线性或者有角度的并五苯、并六、茚、芴。
而且,其中R1,R2,R3,R4为单个原子Cl、Br、I;
或者,为三元环、四元环、五元环或杂原子取代的多元环;
或者,为五元芳香环、噻吩环、呋喃环、吡咯环;
或者,为六元芳香环的苯环、吡啶环、吡喃环;
或者,为稠合的多环中苯并噻吩、苯并呋喃、苯并吡咯、苯并吡啶、萘环、蒽环、非那烯、并四苯、芘、并五苯、并六苯、茚、芴。
一种含有多取代基的杂环含硼芳香化合物的合成方法,包括以下合成路线及步骤:
式四 化合物4a/4b的合成路线
⑴化合物2的合成:称取2-硝基苯胺,用冰乙酸将其充分溶解,在氮气保护下加热回流1h,然后冷却至室温,加入少量水,溶液变为棕绿色固体,然后进行抽滤,得滤饼,再将滤饼用乙酸乙酯与水洗,滤液萃取,用无水硫酸镁干燥,过滤,旋干,柱层析得化合物2。
⑵化合物3的合成:将化合物2用乙醇溶解,称取碱缓慢的加入,溶液由淡黄色变为棕黑色,并有气体产生,待反应平稳后拿至常温搅拌2h,然后将乙醇旋干,用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物3。
⑶化合物4b的合成:将化合物3抽干,并用氮气保护,用无水四氢呋喃溶解,放置在-78℃搅拌30min,然后抽取正丁基锂缓慢加入到反应瓶中,搅拌1h,然后加入溴己烷,并转移至常温,然后加热搅拌(75℃)4h,然后用乙酸乙酯和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物4b。
式五 化合物5a/5b的合成路线
⑷化合物5a的合成:将化合物4a用甲苯溶解,加入三氯化硼,加热搅拌(110℃),反应24h,然后加入米基格氏试剂,常温搅拌过夜,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物5a。
⑸化合物5b的合成:将化合物4b用甲苯溶解,加入三氯化硼,加热搅拌(110℃),反应24h,然后加入米基格氏试剂,常温搅拌过夜,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物5b。
一种含有多取代基的杂环含硼芳香化合物的合成方法,包括以下合成路线及步骤:
式六 化合物7a/7b的合成路线
⑴化合物7a的合成:将化合物4a用甲苯溶解,加入二氯苯硼烷,加热搅拌(110℃),反应24h,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物7a。
⑵化合物7b的合成:将化合物4b用甲苯溶解,加入二氯苯硼烷,加热搅拌(110℃),反应24h,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物7b。
一种含有多取代基的杂环含硼芳香化合物的合成方法,包括以下合成路线及步骤:
式七 化合物8a/8b的合成路线
⑴化合物8a的合成:将化合物4a用甲苯溶解,加入三氯化硼,加热搅拌(110℃),反应24h,加入甲基格氏试剂,常温搅拌过夜,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物8a.。
⑵化合物8b的合成:将化合物4b用甲苯溶解,加入三氯化硼,加热搅拌(110℃),反应24h,加入甲基格氏试剂,常温搅拌过夜,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物8b。
一种含有多取代基的杂环含硼芳香化合物的合成方法,包括以下合成路线及步骤:
式八 化合物12a/12b的合成路线
⑴化合物10的合成:称取2,6-二硝基苯胺,用冰乙酸将其充分溶解,在氮气保护下加热回流24h,然后冷却至室温,加入少量水,溶液变为棕绿色固体,然后进行抽滤,得滤饼,再将滤饼用乙酸乙酯与水洗,滤液萃取,用无水硫酸镁干燥,过滤,旋干,柱层析得化合物10;
⑵化合物11的合成:将化合物10用乙醇溶解,在0℃下,称取碱缓慢的加入,溶液由淡黄色变为棕黑色,并有气体产生,待反应平稳后拿至常温搅拌过夜,然后将乙醇旋干,用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物11。
⑶化合物12b的合成:将化合物11抽干,并用氮气保护,用无水四氢呋喃溶解,放置在-78℃搅拌30min,然后抽取正丁基锂缓慢加入到反应瓶中,搅拌1h,然后加入溴己烷,并转移至常温,然后加热搅拌(75℃)4h,然后用乙酸乙酯和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物12b。
式九 化合物13a/13b的合成路线
⑷化合物13a的合成:将化合物12a用甲苯溶解,加入三氯化硼,加热搅拌(110℃),反应24h,加入米基格氏试剂,常温搅拌过夜,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物13a。
⑸化合物13b的合成:将化合物12b用甲苯溶解,加入三氯化硼加热搅拌(110℃),反应24h,加入米基格氏试剂,常温搅拌过夜,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物13b。
一种含有多取代基的杂环含硼芳香化合物的合成方法,包括以下合成路线及步骤:
式十 化合物14a/14b的合成路线
⑴化合物14a的合成:将化合物12a用甲苯溶解,加入二氯苯硼烷,加热搅拌(110℃),反应24h,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物14a。
⑵化合物14b的合成:将化合物12b用甲苯溶解,加入二氯苯硼烷,加热搅拌(110℃),反应24h,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物14b。
一种含有多取代基的杂环含硼芳香化合物的合成方法,包括以下合成路线及步骤:
式十一 化合物15a/15b的合成路线
⑴化合物15a的合成:将化合物12a用甲苯溶解,加入三氯化硼,加热搅拌(110℃),反应24h,然后加入甲基格氏试剂,常温搅拌过夜,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物15a。
⑵化合物15b的合成:将化合物12b用甲苯溶解,加入三氯化硼,加热搅拌(110℃),反应24h,然后再加入甲基格氏试剂,常温搅拌过夜,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物15b。
一种含有多取代基的杂环含硼芳香化合物的合成方法,包括以下合成路线及步骤:
式十二 化合物16的合成路线
⑴化合物16的合成:在反应管内称取化合物11、邻溴碘苯、金属钯催化剂以及碱,用氮气保护,加热搅拌(100℃)24h,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物16.
式十三 化合物17,18的合成路线
⑴化合物17的合成:称取化合物16,碱和苯硼酸以及Pd(PPh3)4,加入1,4-二氧六环和水(4:1),加热搅拌12h,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物17。
⑵化合物18的合成:称取化合物17并用甲苯溶解,加入三乙胺、三溴化硼加热搅拌(100℃)24h,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物18。
式十四 化合物19,20的合成路线
⑴化合物19的合成:称取化合物16,碳酸钾和2-噻吩硼酸以及Pd(PPh3)4,加入1,4-二氧六环和水(4:1),加热搅拌12h,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物19。
⑵化合物20的合成:称取化合物19并用甲苯溶解,加入三乙胺、三溴化硼,加热搅拌24h,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物20。
式十三 化合物21,22的合成路线
⑴化合物21的合成:称取化合物16,碳酸钾和3-噻吩硼酸以及Pd(PPh3)4,加入1,4-二氧六环和水(4:1),加热搅拌12h,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物21。
⑵化合物22的合成:称取化合物21并用甲苯溶解,加入三乙胺、三溴化硼,加热搅拌24h,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物22。
一种含有多取代基的杂环含硼芳香化合物的用途,用于太阳能电池、电致发光设备、传感器制备。
本发明提供的含五元杂环的硼氮掺杂稠环芳香烃,结构如下
本发明的有益效果是:
本发明采用改进的合成方法使得反应原料价低易得,反应过程避免使用有毒试剂,合成方法简单易行,化合物在有机发光二极管、有机太阳能电池、有机场效应晶体管、有机激光器、有机传感器、分子开关、生物成像以及毒素检测等领域具有广泛的应用。
附图说明
图1为化合物4a的核磁图。
图2为化合物5a的核磁图氢谱。
图3为化合物5a的核磁图碳谱。
图4为化合物12a的核磁图氢谱。
图5为化合物14a的核磁图氢谱。
图6为化合物14a的核磁图碳谱。
具体实施方式
以下实例有助于理解本发明,但不限于本发明的内容。
本发明提供的含五元杂环的硼氮掺杂稠环芳香烃及其合成方法及应用,已完成部分化合物的合成及测试。具体的合成方法如下:
式十四 吡咯稠和的BN菲类化合物的合成路线
式十五 吡咯稠和的BN芘类化合物的合成路线
式十四 吡咯稠和BN化合物的合成路线
对上述部分化合物进行举例,具体内容如下:
实施例1:
式十五 吡咯稠和的BN菲类化合物的合成路线
化合物4a的合成:称取N-(2-硝基苯基)吡咯(1.9g,9.90mmol,1.00equiv)溶解在120ml乙醇中,并放置在0℃下搅拌30min,然后称取碱缓慢加入溶液中,溶液由淡黄色变为黑色,并伴有气体产生,待反应平稳后,拿至常温搅拌过夜,然后过滤,将滤液中的乙醇旋干,旋干后的固体用乙酸乙酯和饱和食盐水萃取,无水硫酸镁干燥,进行柱层析(PE:EA=10:1),得白色固体4a(1.2g,76%)。
1H NMR(400MHz,CDCl3):δ7.21–7.12(m,2H,Ar),6.84(t,J=2.4Hz,2H,Ar),6.76–6.83(m,2H,Ar),6.35(t,J=2.0Hz,2H,Ar),3.71(br,2H,NH2)。
化合物5a的合成:称取N-(2-氨基苯基)吡咯(500mg,3.20mmol,1.00equiv),溶于10ml甲苯中,量取二氯苯硼烷(623ul,4.80mmol,1.50equiv),加热搅拌(110℃)24h,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物5a(348mg,45%).
1H NMR(400MHz,CDCl3):δ7.95(dd,J1=6.8Hz,J2=2.4Hz,3H,Ar),7.84-7.77(m,1H,Ar),7.51(t,J=3.2Hz,3H,Ar),7.25-7.15(m,4H,Ar),7.08(br,1H,NH),6.76(t,J=3.2Hz,1H,Ar)。
实施例2
式十六 吡咯稠和的BN芘类化合物的合成路线
⑴化合物12a的合成:称取N-(2,6-二硝基苯基)吡咯(1.4g,5.8mmol,1.0equiv)溶解在120ml乙醇中,并放置在0℃下搅拌30min,然后称取碱缓慢加入溶液中,溶液由淡黄色变为黑色,并伴有气体产生,待反应平稳后,拿至常温搅拌过夜,然后过滤,将滤液中的乙醇旋干,旋干后的固体用乙酸乙酯和饱和食盐水萃取,无水硫酸镁干燥,进行柱层析(PE:EA=4:1),得白色固体12a(811.7mg,81%)。
1H NMR(400MHz,CDCl3):δ6.96(t,J=8.0Hz,1H,Ar),6.70(t,J=2.1Hz,2H,Ar),6.39(t,J=2.1Hz,2H,Ar),6.20(d,J=8.0Hz,2H,Ar),3.48(br,4H,NH)。
⑵化合物14a的合成:称取N-(2,6-二氨基苯基)吡咯(105mg,0.61mmol,1.00equiv),溶于10ml氯苯中,量取二氯苯硼烷(242.2mg,1.53mmol,1.50equiv),加热搅拌(110℃)24h,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物14a(136mg,65%)。
1H NMR(400MHz,CDCl3):δ8.05-8.01(m,4H,Ar),7.57-7.52(m,6H,Ar),7.52(s,2H,Ar),7.33(br,2H,NH),7.20(t,J=8.0Hz,1H,Ar),6.91(d,J=8.0Hz,2H,Ar)。
实施例3
式十七 吡咯稠和的BN多环芳烃化合物的合成
⑴化合物17的合成:称取化合物16(44mg,0.09mmol,1.00equiv),碳酸钠(48mg,0.01mmol,0.46equiv)和苯硼酸(28mg,0.23mmol,2.5equiv),称取Pd(PPh3)4(10.5mg,0.01mmol,0.10equiv),加入1,4-二氧六环和水(4:1),加热搅拌12h,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物17(38mg,87%)。
⑵化合物18的合成:称取化合物17(37mg,0.08mmol,1.00equiv)并用甲苯(2ml)溶解,加入三乙胺(33ul,0.24mmol,3.00equiv)、三溴化硼(22ul,0.24mmol,3.0equiv)加热搅拌(110℃)24h,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物18。
为了进一步研究该类化合物的光电物理性质,我们对该类化合物进行了紫外吸收、荧光发射测试、电化学性质测试及单晶衍射结构表征。
需要说明的是,以上所述仅为本发明优选实施例,仅仅是解释本发明,并非因此限制本发明专利范围。对属于本发明技术构思而仅仅显而易见的改动,同样在本发明保护范围之内。
基于本发明化合物的潜在应用举例1:
有机发光二极管
我们对化合物5a进行了紫外荧光测试,发现化合物5a在365波长照射下具有很强的蓝紫色荧光。说明化合物5a具有很强的荧光特性。根据这一发光特性,化合物5a可应用到有机发光二极管。
有机发光材料。
硼原子作为一个缺电子原子,它可以与其他富电子的原子结合,在分子内形成电荷的移动,因此会显示出与其他化合物不同的光电物理特性。我们对化合物14a进行了吸收发射的测试,在365nm波长照射下化合物14a显示蓝紫色荧光,说明化合物14a具有一定的发光特性,可以应用于制作发光材料。
基于本发明化合物的潜在应用举例2:
氟离子探针。
与氟离子的络合能力是检测三价硼的关键功能特性。发现加入过量的四丁基氟化铵到化合物18的溶液中会导致18的紫外吸收谱式和荧光发射谱式急剧变化。由于加入过量的TBAF,导致18的吸收波长带完全被抑制。同时,发射波长也完全消失。这些现象清楚地表明,硼原子的路易斯酸性在18中仍然保持不变。
Claims (9)
1.含五元杂环的硼氮掺杂稠环芳香烃,其特征在于:其结构为如下结构式之一:
A,B,C,Ar1,Ar2,Ar3,Ar4,Ar5,Ar6,Ar7,Ar8分别是独立的,为取代或非取代单个芳香环体系,或取代或非取代的多个芳香环体系;
R1,R2,R3,R4基团为独立的取代或非取代的芳基或者杂芳基;
X1,X5,X9为C,N原子之一;
X2,X7,X12为C,N,S原子之一;
X3,X8,X11为C,N,S原子之一;
X4,X13,X14为C或N原子。
2.根据权利要求1所述的含五元杂环的硼氮掺杂稠环芳香烃,其特征在于:其中的A,B,C,Ar1,Ar2,Ar3,Ar4,Ar5,Ar6,Ar7,Ar8每一个由4到30个芳香环原子构成,为一个,两个,三个,四个芳香环或者杂环,或在4到30个芳香环原子构成的环中用N,O,S,Se等原子代替碳原子。
3.根据权利要求2所述的含五元杂环的硼氮掺杂稠环芳香烃,其特征在于:其中A,B,C,Ar1,Ar2,Ar3,Ar4,Ar5,Ar6,Ar7,Ar8是苯环、噻吩环、呋喃环、吡咯、吡啶、苯并噻吩、苯并呋喃、苯并吡咯、苯并吡啶、萘环、蒽环、非那烯、并四苯、芘、线性或者有角度的并五苯、并六、茚、芴。
4.根据权利要求1所述的含五元杂环的硼氮掺杂稠环芳香烃,其特征在于:其中R1,R2,R3,R4为单个原子Cl、Br、I;
或者,为三元环、四元环、五元环或杂原子取代的多元环;
或者,为五元芳香环、噻吩环、呋喃环、吡咯环;
或者,为六元芳香环的苯环、吡啶环、吡喃环;
或者,为稠合的多环中苯并噻吩、苯并呋喃、苯并吡咯、苯并吡啶、萘环、蒽环、非那烯、并四苯、芘、并五苯、并六苯、茚、芴。
5.一种权利要求1所述的含五元杂环的硼氮掺杂稠环芳香烃,其特征在于:包括以下合成路线及步骤:
⑴化合物4a的合成:将化合物N-(2-硝基苯基)吡咯用乙醇溶解,加入碱,溶液由淡黄色变为棕黑色,并有气体产生,待反应平稳后拿至常温搅拌2h,然后将乙醇旋干,用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物4a;
⑵化合物7a的合成:将化合物4a用甲苯将化合物4a溶解,加入二氯苯硼烷,加热110℃,搅拌反应24h,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物7a。
6.根据权利要求1所述的含五元杂环的硼氮掺杂稠环芳香烃,其特征是:对合成的硼氮杂类化合物进行后期的官能团化,步骤如下:
7.一种权利要求1所述的含五元杂环的硼氮掺杂稠环芳香烃,其特征是:包括以下合成路线及步骤:
⑴化合物16的合成:在反应管内称取化合物11、邻溴碘苯、金属钯催化剂以及碱,用氮气保护,加热100℃,搅拌24h,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物16;
⑵化合物17的合成:称取化合物16,碱和苯硼酸以及Pd(PPh3)4,加入1,4-二氧六环:水=4:1体积比,加热搅拌12h,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物17;
⑶化合物18的合成:称取化合物17并用甲苯溶解,加入三乙胺、三溴化硼加热100℃,搅拌24h,然后用乙酸乙酯与饱和食盐水萃取,无水硫酸镁干燥,过滤,旋干,柱层析得化合物18。
8.一种权利要求1所述的的含五元杂环的硼氮掺杂稠环芳香烃用于制备光电材料、制备太阳能电池、制备电致发光设备或制备传感器制备的用途。
9.含五元杂环的硼氮掺杂稠环芳香烃,其特征在于:结构如下
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