CN108623635A - 一种1,3-氮杂磷杂环戊二烯类化合物及其合成方法 - Google Patents
一种1,3-氮杂磷杂环戊二烯类化合物及其合成方法 Download PDFInfo
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- -1 Aryl phosphorus dichloride Chemical compound 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- 238000005292 vacuum distillation Methods 0.000 claims description 7
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- 230000015572 biosynthetic process Effects 0.000 claims description 5
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 3
- 229960002163 hydrogen peroxide Drugs 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
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- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 206010034962 Photopsia Diseases 0.000 abstract description 5
- 229910000065 phosphene Inorganic materials 0.000 abstract description 5
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- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 76
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 238000004679 31P NMR spectroscopy Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 6
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- 229910001868 water Inorganic materials 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WZVDACBKJRRYBN-UHFFFAOYSA-N 9,10-dibromophenanthrene Chemical compound C1=CC=C2C(Br)=C(Br)C3=CC=CC=C3C2=C1 WZVDACBKJRRYBN-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- XLIQPEZVRBALDD-UHFFFAOYSA-N pyrrolo[1,2-a]quinoline Chemical class C1=CC2=CC=CC=C2N2C1=CC=C2 XLIQPEZVRBALDD-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
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- 238000007740 vapor deposition Methods 0.000 description 2
- SFHYNDMGZXWXBU-LIMNOBDPSA-N 6-amino-2-[[(e)-(3-formylphenyl)methylideneamino]carbamoylamino]-1,3-dioxobenzo[de]isoquinoline-5,8-disulfonic acid Chemical compound O=C1C(C2=3)=CC(S(O)(=O)=O)=CC=3C(N)=C(S(O)(=O)=O)C=C2C(=O)N1NC(=O)N\N=C\C1=CC=CC(C=O)=C1 SFHYNDMGZXWXBU-LIMNOBDPSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 230000005525 hole transport Effects 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
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- 239000013067 intermediate product Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LBBMOAOCCQOIAQ-UHFFFAOYSA-N methoxy(phenyl)borinic acid Chemical compound COB(O)C1=CC=CC=C1 LBBMOAOCCQOIAQ-UHFFFAOYSA-N 0.000 description 1
- ZGWSRQNDLJAPSO-UHFFFAOYSA-N n-(9h-fluoren-2-yl)-3-methylfluoren-9-imine Chemical compound C12=CC=CC=C2C2=CC(C)=CC=C2C1=NC1=CC=C2C3=CC=CC=C3CC2=C1 ZGWSRQNDLJAPSO-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/6584—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having one phosphorus atom as ring hetero atom
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Abstract
本发明属于有机化学合成领域,具体涉及一种在材料方面具有应用价值的1,3‑氮杂磷杂环戊二烯及其合成方法。其具有如下结构通式:其结合了吡咯并[1,2‑a]喹啉骨架和1,3‑氮杂磷杂环戊二烯,其独特的物理性质和光学性质,在有机功能材料方面有着良好的应用前景。
Description
技术领域
本发明属于有机化学合成领域,具体涉及一种在材料方面具有应用价值的1,3-氮杂磷杂环戊二烯及其合成方法。
背景技术
吡咯并[1,2-a]喹啉类化合物作为一种重要的有机共轭分子,广泛应用于功能材料、生物、医药等领域。磷杂环戊二烯类化合物在有机光电材料、生物成像、荧光探针、光控开关等方面具有广泛的应用。磷原子丰富的可修饰性,使其成为调控分子电子结构、物理性质的有力工具。
目前为止,将磷原子嵌入吡咯并[1,2-a]喹啉骨架得到一类新型1,3-氮杂磷杂环戊二烯化合物的研究未见报道。
发明内容
针对目前的技术现状,本发明目的在于提供一种新型的1,3-氮杂磷杂环戊二烯类化合物;另一目的在于提供其合成方法。
为实现本发明目的,所述方法以吡咯并[1,2-a]喹啉类化合物为中间产物,通过双锂化反应生成1,3-氮杂磷杂环戊二烯类化合物。
方案路线如下:
具体结构如下列表所述:
分别取式I-a~I-e化合物原料于Schlenk瓶中,抽真空,充入氮气,加入无水四氢呋喃,加入N,N,N',N'-四甲基乙二胺,随后将体系控温至0~-5℃,逐滴加入n-BuLi,将体系于0~-5℃下反应。反应完毕后加入芳基二氯化磷,将体系恢复至室温反应。反应结束,向反应体系中加入质量百分含量30%过氧化氢溶液或硫粉反应。经萃取,合并有机相,减压蒸馏,柱层析色谱分离,分别得到系列目标物II。
所述芳基二氯化磷优选苯基二氯化磷或含有咔唑基团的苯基二氯化磷。
本发明优点在于:1、合成方法简单、可行,收率较高;2、目标物II作为一类结构新颖的化合物,结合了吡咯并[1,2-a]喹啉骨架和1,3-氮杂磷杂环戊二烯,将其应用于发光层制备器件,器件发射波长在绿光范围内,具有高电流效率、高能量转换效率和高外量子效率的特点,其独特的物理性质和光学性质,在有机功能材料方面有着良好的应用前景。
附图说明
图1为本发明化合物II-cO的热重分析图;
图2为本发明化合物作为应用器件的结构示意图。
具体实施方式
为对本发明进行更好地说明,举实施例下:以下所用原料均为市售品。
实施例1化合物I-c至I-e的合成方法,步骤如下:
a)合成化合物I-c
取式A1化合物原料3.4mmol于100mL schlenk瓶中,抽真空换氮气三次,加入无水四氢呋喃30mL,随后将体系降温至-78℃,逐滴加入n-BuLi 3.4mmol,将体系于-78℃反应0.5h。然后加入9,10-二溴菲3.4mmol,反应自行恢复至室温,并反应0.5h。反应结束,用乙酸乙酯与水萃取,合并有机相,减压蒸馏后,以石油醚:二氯甲烷=15:1为洗脱剂,进行柱层析色谱分离,得到化合物A2。
A2产率:68%,黄色固体,同时回收14%的9,10-二溴菲,1H NMR(300MHz,CDCl3)δ=5.85-5.86(m,2H),6.59-6.60(m,2H),7.33-7.68(m,9H),8.42-8.45(m,1H),8.61-8.65(m,2H)ppm;13C NMR(75MHz,CDCl3):δ=108.9(2CH),121.7(2CH),122.7(CH),122.9(CH),124.9(C),125.9(CH),127.0(CH),127.1(CH),127.2(CH),127.3(CH),127.7(CH),127.8(CH),129.0(CH),129.4(CH),129.7(C),130.3(C),131.1(C),132.2(C),132.3(CH),135.4(C),137.0(C),140.3(C)ppm;HRMS(ESI)calcd.forC24H17BrN[M+H]+398.0539,found 398.0536.
取式A2化合物原料3.8mmol于100mL schlenk瓶中,加入三苯基磷0.76mmol,加入碳酸钾7.6mmol,加入二(三苯基磷)二氯化钯0.19mmol(5mol%),抽真空换氮气三次,加入N,N-二甲基甲酰胺30mL,随后将体系升温至125℃,反应10h。反应结束,恢复至室温,以饱和氯化铵溶液中和,用乙酸乙酯与水萃取,合并有机相,减压蒸馏后,以石油醚:二氯甲烷=10:1为洗脱剂,进行柱层析色谱分离,得到化合物I-c。
I-c产率:84%,黄色固体,1H NMR(300MHz,CDCl3)δ=6.87(dd,J1=3.6Hz,J1=3.0Hz,1H),7.32-7.41(m,2H),7.53-7.71(m,5H),7.89-7.95(m,2H),8.50(d,J1=8.1Hz,1H),8.59-8.72(m,3H),8.99-9.02(m,1H)ppm;13C NMR(75MHz,CDCl3):δ=107.0(CH),113.1(CH),113.5(CH),115.8(CH),121.6(C),122.1(C),123.3(2CH),123.4(C),123.6(CH),125.9(CH),126.5(CH),126.6(CH),127.1(CH),127.2(CH),128.0(2CH),128.4(C),128.9(C),129.8(CH),130.1(C),130.6(C),133.5(C)ppm,one C missing due to overlap;HRMS(ESI)calcd.forC24H16N[M+H]+318.1277,found318.1264.
b)合成化合物I-d
取式A3化合物原料5.5mmol于100mL schlenk瓶中,加入对甲基苯硼酸6.6mmol,加入碳酸钾22mmol,加入四(三苯基磷)钯0.3mmol(5mol%),抽真空换氮气三次,加入甲苯50mL,水10mL,随后将体系升温至90℃,反应30h。反应结束,恢复至室温,以饱和氯化铵溶液中和,用乙酸乙酯与水萃取,合并有机相,减压蒸馏后,以石油醚:乙酸乙酯=10:1为洗脱剂,进行柱层析色谱分离,得到化合物I-d。
I-d产率:95%,黄色固体,1H NMR(300MHz,CDCl3)δ=2.29(s,3H),2.32(s,3H),6.21-6.24(m,1H),6.73-6.77(m,1H),7.01-7.05(m,6H),7.12-7.33(m,3H),7.38-7.42(m,1H),7.44-7.49(m,1H),7.91-7.94(m,2H)ppm,13C NMR(75MHz,CDCl3):δ=21.3(2CH),104.2(CH),112.1(CH),112.8(CH),114.0(CH),123.3(CH),125.1(C),127.4(CH),128.2(CH),128.3(C),128.5(2CH),128.6(2CH),130.1(2CH),130.8(C),131.3(2CH),132.3(C),132.7(C),134.7(C),134.9(C),136.1(C),136.4(C)ppm;HRMS(ESI)Calcd.forC26H22N[M+H]+348.1747,found348.1749;Anal.Calcd.for C26H21N:C,89.88;H,6.09;N,4.03.Found:C,89.35;H,6.07;N,3.72.
c)合成化合物I-e
取式A3化合物原料2.6mmol于100mL schlenk瓶中,加入四(三苯基磷)钯0.13mmol(5mol%),抽真空换氮气三次,加入三正丁基苯乙炔基锡3.9mmol,加入1,4-二氧六环15mL,随后将体系升温至100℃,反应48h。反应结束,恢复至室温,用乙酸乙酯与水萃取,合并有机相,减压蒸馏后,以石油醚:二氯甲烷=10:1为洗脱剂,进行柱层析色谱分离,得到化合物I-e。
I-e产率:88%,黄色固体,1H NMR(300MHz,CDCl3)δ=2.47(s,3H),6.45-6.46(m,1H),6.76-6.79(m,1H),7.27-7.38(m,7H),7.39-7.45(m,1H),7.50-7.56(m,1H),7.62-7.66(m,2H),7.87-7.92(m,2H),8.35(d,1H,J1=8.1Hz)ppm;13C NMR(75MHz,CDCl3):δ=21.5(CH),86.9(C),96.6(C),106.1(CH),109.5(C),113.5(CH),113.7(CH),114.1(CH),123.4(C),123.7(C),124.0(CH),127.9(CH),127.9(CH),128.0(CH),128.3(2CH),128.7(2CH),130.0(2CH),131.3(2CH),131.5(C),132.3(C),134.5(C),136.3(CH),138.0(C)ppm;HRMS(ESI)calcd.for C27H20N[M+H]+358.1590,found 358.1591;Anal.Calcd.for C27H19N:C,90.72;H,5.36;N,3.92.Found:C,90.37;H,5.33;N,3.74.
实施例2化合物II-a至II-e的合成方法,步骤如下:
分别取系列化合物I原料2mmol于Schlenk瓶中,抽真空换氮气三次,加入无水四氢呋喃20mL,加入N,N,N',N'-四甲基乙二胺4mmol,随后将体系控温至0℃,逐滴加入n-BuLi4mmol,将体系于0℃下反应1h。反应完毕后加入苯基二氯化磷2mmol,0℃下反应10分钟后将体系恢复至室温反应。反应结束,向体系中加入质量百分含量30%过氧化氢溶液或硫粉反应。经萃取,合并有机相,减压蒸馏,柱层析色谱分离,得到系列目标物II。
II-aO产率:42%,黄色固体,31P NMR(121MHz,CDCl3):δ=21.1ppm;1H NMR(300MHz,CDCl3):δ=6.53(dd,JHH=3.6Hz,JHP=3.0Hz,1H),7.09(dd,JHH=3.6Hz,JHP=1.2Hz,1H),7.17(dd,JHP=9.6Hz,JHH=1.5Hz,1H),7.32-7.40(m,2H),7.41-7.48(m,2H),7.51-7.57(m,1H),7.70-7.79(m,4H)ppm;13C NMR(75MHz,CDCl3):δ=106.66(d,JCP=8.3Hz,CH),116.40(d,JCP=135.8Hz,C),119.21(d,JCP=11.6Hz,CH),119.45(CH),119.60(d,JCP=6.5Hz,C),120.21(CH),125.24(d,JCP=106.0Hz,C),125.87(d,JCP=11.6Hz,CH),128.84(d,JCP=13.5Hz,2CH),129.09(d,JCP=6.4Hz,CH),130.55(d,JCP=6.6Hz,CH),131.16(d,JCP=11.8Hz,2CH),131.26(d,JCP=3.1Hz,CH),131.44(d,JCP=115.7Hz,C),132.50(d,JCP=3.1Hz,CH),134.93(d,JCP=11.0Hz,C)ppm;HRMS(ESI)Calcd.for C18H13NOP[M+H]+290.0729,found 290.0735.
II-aS产率:40%,黄色固体,31P NMR(121MHz,CDCl3):δ=30.4ppm;1H NMR(300MHz,CDCl3):δ=6.54(dd,JHH=3.3Hz,JHP=3.3Hz,1H),7.06(dd,JHH=3.8Hz,JHP=1.2Hz,1H),7.12(dd,JHP=9.6Hz,JHH=1.5Hz,1H),7.29-7.48(m,5H),7.67-7.73(m,2H),7.75-7.78(m,1H),7.80-7.83(m,1H)ppm;13C NMR(75MHz,CDCl3):δ=106.78(d,JCP=8.7Hz,CH),117.83(d,JCP=11.2Hz,CH),117.89(d,JCP=115.4Hz,C),119.66(d,JCP=1.4Hz,CH),120.02(CH),120.06(d,JCP=6.4Hz,C),126.11(d,JCP=12.1Hz,CH),128.58(d,JCP=88.0Hz,C),128.72(d,JCP=5.0Hz,C),128.81(d,JCP=13.9Hz,2CH),129.39(d,JCP=7.1Hz,CH),130.33(d,JCP=2.8Hz,CH),130.99(d,JCP=12.8Hz,2CH),132.18(d,JCP=3.2Hz,CH),132.39(d,JCP=90.1Hz,C),134.42(d,JCP=8.6Hz,C)ppm;HRMS(ESI)Calcd.forC18H13NSP[M+H+]306.0501,found 306.0502;Anal.Calcd.for C18H12NPS:C,70.81;H,3.96;N,4.59;S,10.50.Found:C,70.56;H,3.89;N,4.25;S,10.16.
II-bO产率:42%,黄色固体,31P NMR(121MHz,CDCl3):δ=21.5ppm;1H NMR(300MHz,CDCl3):δ=6.79-6.81(m,1H),7.02-7.04(m,1H),7.35-7.50(m,6H),7.66-7.78(m,3H),7.86-7.90(m,1H),8.14-8.09(m,2H)ppm;13C NMR(75MHz,CDCl3):δ=106.35(d,JCP=8.6Hz,CH),117.53(d,JCP=135.2Hz,C),118.87(d,JCP=8.5Hz,C),119.00(d,JCP=11.7Hz,CH),123.51(CH),124.20(CH),125.57(d,JCP=106.1Hz,C),125.80(C),125.98(C),126.06(d,JCP=11.6Hz,CH),127.26(d,JCP=2.2Hz,CH),127.35(CH),128.45(d,JCP=6.4Hz,C),128.81(CH),128.83(d,JCP=13.5Hz,2CH),130.11(d,JCP=6.8Hz,CH),131.18(d,JCP=11.7Hz,2CH),131.42(d,JCP=116.0Hz,C),132.48(d,JCP=3.1Hz,CH),134.61(d,JCP=11.3Hz,C)ppm;HRMS(ESI)Calcd.for C22H15NOP[M+H+]340.0886,found 340.0887;Anal.Calcd.for C22H14NOP:C,77.87;H,4.16;N,4.13.Found:C,78.31;H,3.98;N,3.66.
II-cO产率:66%,黄色固体,31P NMR(121MHz,CDCl3):δ=19.9ppm;1H NMR(300MHz,CDCl3):δ=7.26-7.28(m,1H),7.36(m,1H),7.44-7.58(m,4H),7.61-7.87(m,7H),8.58-8.71(m,4H),8.92-8.95(m,1H)ppm;13C NMR(75MHz,CDCl3):δ=111.18(d,JCP=8.2Hz,CH),117.67(d,JCP=135.1Hz,C),118.39(d,JCP=6.5Hz,C),119.84(d,JCP=11.1Hz,CH),122.96(CH),123.07(C),123.31(CH),123.49(C),125.22(d,JCP=11.8Hz,CH),125.77(CH),125.80(d,JCP=105.8Hz,C),126.56(CH),126.73(CH),127.30(CH),127.60(d,JCP=6.6Hz,C),127.64(CH),128.01(CH),128.30(C),128.52(C),128.90(d,JCP=13.5Hz,2CH),130.10(d,JCP=7.2Hz,CH),130.15(C),130.31(C),131.28(d,JCP=11.6Hz,2CH),131.48(d,JCP=117.2Hz,C),132.54(d,JCP=2.7Hz,CH),133.06(CH),135.12(d,JCP=11.1Hz,C)ppm;HRMS(ESI)Calcd.forC30H19NOP[M+H+]440.1199,found 440.1203;Anal.Calcd.ForC30H18NOP:C,81.99;H,4.13;N,3.19,Found:C,81.74;H,4.15;N,3.07.
II-cS产率:55%,黄色固体,31P NMR(121MHz,CDCl3):δ=28.2ppm;1H NMR(300MHz,CDCl3):δ=7.23-7.27(m,2H),7.41-7.65(m,8H),7.77(dd,JHH=8.6Hz,JHH=8.4Hz,1H),7.84-7.92(m,2H),8.39-8.55(m,4H),8.80(d,JHH=5.4Hz,1H)ppm;13C NMR(75MHz,CDCl3):δ=111.38(d,JCP=8.3Hz,CH),118.71(d,JCP=11.3Hz,CH),118.83(d,JCP=6.8Hz,C),119.25(d,JCP=115.4Hz,C),123.08(CH),123.17(C),123.45(CH),123.80(C),125.56(d,JCP=12.8Hz,CH),125.97(CH),126.70(CH),126.85(CH),127.33(d,JCP=5.3Hz,C),127.44(CH),127.76(CH),127.92(CH),128.48(C),128.76(C),128.85(d,JCP=13.8Hz,2CH),129.00(d,JCP=87.5Hz,C),129.29(d,JCP=7.5Hz,C),130.33(C),130.41(C),131.08(d,JCP=12.8Hz,2CH),132.22(d,JCP=3.8Hz,CH),132.34(d,JCP=2.3Hz,CH),132.41(d,JCP=90.5Hz,CH),134.71(d,JCP=8.3Hz,C)ppm;HRMS(ESI)Calcd.forC30H19NPS[M+H+]456.0970,found 456.0976.
II-dO产率:56%,黄色固体,31P NMR(121MHz,CDCl3):δ=21.8ppm;1H NMR(300MHz,CDCl3):δ=2.31(s,3H),2.34(s,3H),6.36(dd,JHH=3.6Hz,JHP=3.0Hz,1H),7.04-7.09(m,7H),7.16-7.18(m,2H),7.24-7.31(m,1H),7.43-7.48(m,2H),7.51-7.54(m,2H),7.72-7.85(m,3H)ppm;13C NMR(75MHz,CDCl3):δ=21.30(CH3),21.32(CH3),107.86(d,JCP=8.2Hz,CH),116.52(d,JCP=135.4Hz,C),119.39(d,JCP=11.4Hz,CH),121.41(d,JCP=6.4Hz,C),125.10(d,JCP=106.0Hz,C),125.84(d,JCP=11.6Hz,CH),128.82(2CH),128.85(d,JCP=13.4Hz,2CH),128.90(CH),129.78(2CH),130.17(d,JCP=6.7Hz,CH),130.45(C),130.65(d,JCP=5.9Hz,C),130.80(CH),131.12(d,JCP=1.4Hz,C),131.22(CH),131.30(d,JCP=11.8Hz,2CH),131.38(CH),131.60(d,JCP=116.0Hz,C),132.47(d,JCP=3.0Hz,CH),133.02(C),133.60(C),134.15(d,JCP=11.1Hz,C),136.89(C),137.21(C)ppm,one CHmissing due to overlap;HRMS(ESI)Calcd.for C32H25NOP[M+H+]470.1668,found470.1668;Anal.Calcd.for C32H24NOP:C,81.86;H,5.15;N,2.98,Found:C,81.71;H,5.08;N,2.70.
II-dS产率:54%,黄色固体,31P NMR(121MHz,CDCl3):δ=30.5ppm;1H NMR(300MHz,CDCl3):δ=2.32(s,3H),2.35(s,3H),6.39(dd,JHH=3.6Hz,JHP=3.3Hz,1H),7.05-7.13(m,7H),7.16-7.19(m,2H),7.26-7.32(m,1H),7.42-7.52(m,4H),7.70(dd,1H,J1=9.0Hz,J1=7.5Hz,),7.84-7.92(m,2H)ppm;13C NMR(75MHz,CDCl3):δ=21.32(CH3),21.33(CH3),107.98(d,JCP=8.4Hz,CH),117.96(d,JCP=115.1Hz,C),117.98(d,JCP=11.0Hz,CH),121.83(d,JCP=5.9Hz,C),126.05(d,JCP=12.1Hz,CH),128.34(d,JCP=74.2Hz,C),128.80(d,JCP=13.9Hz,2CH),128.84(2CH),128.93(CH),128.98(d,JCP=6.7Hz,CH),129.79(2CH),130.24(d,JCP=4.0Hz,C),130.27(C),130.43(d,JCP=2.7Hz,CH),130.81(CH),131.12(d,JCP=12.8Hz,2CH),131.20(CH),131.30(d,JCP=1.3Hz,C),132.15(d,JCP=3.2Hz,CH),132.50(d,JCP=90.4Hz,C),133.10(C),133.58(d,JCP=8.7Hz,C),133.61(C),136.89(C),137.22(C)ppm,one CH missing due to overlap;HRMS(ESI)Calcd.forC32H25NSP[M+H+]486.1440,found 486.1436;Anal.Calcd.ForC32H24NSP:C,79.15;H,4.98;N,2.88;S,6.60,Found:C,79.03;H,5.14;N,2.48;S,6.18.
II-eO产率:57%,黄色固体,31P NMR(121MHz,CDCl3):δ=22.3ppm;1H NMR(300MHz,CDCl3):δ=2.48(s,3H),6.53(dd,JHH=3.3Hz,JHP=3.3Hz,1H),7.08(d,JHH=3.6Hz,1H),7.32-7.37(m,5H),7.41-7.55(m,6H),7.74-7.81(m,5H),8.22(d,JHH=8.1Hz,1H)ppm;13C NMR(75MHz,CDCl3):δ=21.58(CH3),85.56(C),97.59(C),109.27(d,JCP=8.0Hz,CH),111.32(C),118.18(d,JCP=133.4Hz,C),119.65(d,JCP=11.2Hz,CH),120.56(d,JCP=6.5Hz,C),123.00(C),124.90(d,JCP=106.1Hz,C),126.38(d,JCP=11.5Hz,CH),128.42(2CH),128.59(CH),128.95(d,JCP=13.7Hz,2CH),128.97(2CH),129.51(2CH),129.69(d,JCP=5.7Hz,C),130.68(d,JCP=6.7Hz,CH),130.99(d,JCP=2.1Hz,CH),131.19(d,JCP=116.0Hz,C),131.22(d,JCP=11.8Hz,2CH),131.42(2CH),132.67(d,JCP=3.0Hz,CH),133.18(C),133.80(d,JCP=11.3Hz,C),136.41(d,JCP=0.9Hz,C),138.95(C)ppm;HRMS(ESI)Calcd.for C33H23NOP[M+H+]480,1512,found 480.1509;Anal.Calcd.for C33H22NOP:C,82.66;H,4.62;N,2.92,Found:C,82.27;H,4.49;N,2.60.
II-eS产率:54%,黄色固体,31P NMR(121MHz,CDCl3):δ=30.6ppm;1H NMR(300MHz,CDCl3):δ=2.49(s,3H),6.56(dd,JHH=3.3Hz,JHP=3.3Hz,1H),7.07(d,JHH=3.9Hz,1H),7.32-7.38(m,5H),7.40-7.53(m,6H),7.73-7.82(m,4H),7.86(d,JHH=7.5Hz,1H),8.19ppm(d,JHH=8.1Hz,1H);13C NMR(75MHz,CDCl3):δ=21.57(CH3),85.61(C),97.43(C),109.39(d,JCP=8.5Hz,CH),111.09(C),118.26(d,JCP=11.0Hz,CH),119.78(d,JCP=113.0Hz,C),120.94(d,JCP=6.1Hz,C),123.09(C),126.56(d,JCP=12.2Hz,CH),128.24(d,JCP=88.0Hz,C),128.43(2CH),128.55(CH),128.87(d,JCP=14.2Hz,2CH),128.97(2CH),129.28(d,JCP=4.6Hz,C),129.48(d,JCP=6.0Hz,CH),129.52(2CH),130.05(d,JCP=2.6Hz,CH),131.05(d,JCP=12.9Hz,2CH),131.46(2CH),132.07(d,JCP=91.3Hz,C),132.30(d,JCP=3.2Hz,CH),133.19(C),133.25(d,JCP=8.6Hz,C),136.56(d,JCP=1.4Hz,C),138.95ppm(C);HRMS(ESI)Calcd.for C33H23NPS[M+H+]:496.1283,found 496.1278;Anal.Calcd.forC33H22NPS:C,79.98;H,4.47;N,2.83;S,6.47,Found:C,79.44;H,4.67;N,2.62;S,6.31.
实施例3化合物II-fO的合成方法,步骤如下:
取镁粉2.2mmol于Schlenk瓶中,抽真空换氮气三次,加入无水四氢呋喃10mL,加入一粒碘,随后将体系升温至60℃。20分钟后,加入式A4化合物2mmol,至反应完全(体系1)。
另取一Schlenk瓶,抽真空换氮气三次,加入无水四氢呋喃10mL,加入三氯化磷2mmol,随后将体系降温至-78℃(体系2)。用注射器将体系1中物料逐滴加入体系2中,30分钟后,反应得到含有咔唑基团的芳基二氯化磷A5,将体系恢复至室温(体系3)。
取化合物I-d原料1mmol于另一Schlenk瓶中,抽真空换氮气三次,加入无水四氢呋喃10mL,加入N,N,N',N'-四甲基乙二胺2mmol,随后将体系控温至0℃,逐滴加入n-BuLi2mmol,将体系于0℃下反应1h(体系4)。反应完毕后,用注射器将体系3中物料A5逐滴加入体系4中,反应10分钟后将体系恢复至室温。反应结束,向体系中加入质量百分含量30%过氧化氢溶液。经萃取,合并有机相,减压蒸馏,柱层析色谱分离,得到系列目标物II-fO。
II-fO产率:20%(由I-d计算),黄色固体,31P NMR(121MHz,CDCl3):δ=21.1ppm;1HNMR(300MHz,CDCl3):δ=6.40(dd,JHH=3.3Hz,JHP=3.3Hz,1H),7.05-7.19(m,9H),7.24-7.45(m,7H),7.57(d,JHH=8.1Hz,1H),7.67-7.70(m,2H),7.85(dd,JHH=8.0Hz,JHH=7.8Hz,1H),8.00-8.12(m,4H)ppm;13C NMR(75MHz,CDCl3):δ=21.32(CH3),21.34(CH3),108.08(d,JCP=8.2Hz,CH),109.72(2CH),116.25(d,JCP=137.6Hz,C),119.69(d,JCP=11.5Hz,CH),120.45(2CH),120.61(2CH),121.56(d,JCP=6.3Hz,C),123.78(2C),124.86(d,JCP=107.7Hz,C),126.00(d,JCP=11.7Hz,CH),126.19(2CH),126.91(d,JCP=14.1Hz,2CH),128.83(CH),128.87(2CH),128.94(CH),129.79(2CH),130.25(d,JCP=117.6Hz,C),130.36(d,JCP=6.7Hz,CH),130.63(C),130.84(CH),130.88(d,JCP=6.1Hz,C),131.26(CH),131.26(C),131.65(d,JCP=2.0Hz,CH),132.98(C),133.13(d,JCP=12.5Hz,2CH),133.56(C),134.22(d,JCP=11.5Hz,C),136.98(C),137.30(C),140.16(2C),141.70(d,JCP=3.3Hz,C)ppm;HRMS(ESI)Calcd.forC44H32N2OP[M+H+]635.2247,found 635.2252;Anal.Calcd.ForC44H31N2OP:C,83.26;H,4.92;N,4.41,Found:C,83.24;H,5.01;N,4.21.
下面是本发明化合物的应用
应用例1
应用本发明化合物II-fO作为OLED器件中的发光材料进行光电性能测定,实施的器件结构如下:
ITO/MoO3(1nm)/NPB(25nm)/II-fO(10nm)/TPBi(30nm)/LiF(1nm)/Al(100nm)所用一些材料的结构式如下:
方法:氧化铟锡(ITO)玻璃基片(中国南玻集团股份有限公司)采用超声清洗器,依次用洗涤剂,去离子水,丙酮,异丙醇超声清洗15min,之后在纯净干燥的氮气流下吹干。然后,基板转移到真空热蒸发室进一步除去表面污渍。真空蒸镀MoO3,形成1nm厚的空穴注入层。蒸镀NPB,形成25nm厚的空穴传输层。在空穴传输层上蒸镀10nm厚的发光层(化合物II-fO)。在发光层上蒸镀30nm厚的TPBi作为电子传输层。最后,蒸镀1nm LiF为电子注入层和100nm Al作为器件阴极。
电流密度-电压-亮度(J-V-L)特性由软件控制的Keithley2400source meter和Topcon BM-7ALuminance Colorimeter测定,电致发光光谱由Lab sphere CDS-610测定。器件电致发光光谱由Lab sphere CDS-610测定。器件的光电性能如下:
表1:器件的光电性质
从以上图表可以看出,应用本发明化合物II-fO于发光层制备器件,电流密度200mAcm-2时效率最高,电流效率为17.98cd/A,能量转换效率为13.82lm/W,外量子效率为6.28%。器件发射波长在绿光范围内,具有高电流效率、高能量转换效率和高外量子效率的特点。因此可以看出,本发明的化合物可以有效应用于有机电致发光器件的发光层。
Claims (3)
1.1,3-氮杂磷杂环戊二烯类化合物,其特征在于,选如下化合物:
。
2.合成如权利要求1所述的1,3-氮杂磷杂环戊二烯类化合物的方法,其特征在于,通过如下步骤实现:
分别取式I-a~I-e化合物原料于Schlenk瓶中,抽真空,充入氮气,加入无水四氢呋喃,加入N,N,N',N'-四甲基乙二胺,随后将体系控温至0~-5oC,逐滴加入n-BuLi,将体系于0~-5oC下反应;反应完毕后加入芳基二氯化磷,将体系恢复至室温反应;反应结束,向反应体系中加入质量百分含量30% 过氧化氢溶液或硫粉反应,经萃取,合并有机相,减压蒸馏,柱层析色谱分离,分别得到系列目标物II。
3.如权利要求1所述的1,3-氮杂磷杂环戊二烯类化合物的合成方法,其特征在于,所述芳基二氯化磷选苯基二氯化磷或含有咔唑基团的苯基二氯化磷。
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CN113999264A (zh) * | 2021-11-25 | 2022-02-01 | 郑州大学 | 一种卤代磷杂苊类化合物及其制备方法 |
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