CN108178737A - 4’-(4-溴萘-1-基)[1,1’-联苯基]-4-腈及其合成方法 - Google Patents
4’-(4-溴萘-1-基)[1,1’-联苯基]-4-腈及其合成方法 Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
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- 238000003786 synthesis reaction Methods 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 3
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- 230000015572 biosynthetic process Effects 0.000 claims description 18
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- 238000001514 detection method Methods 0.000 claims description 12
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- 229910052763 palladium Inorganic materials 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 5
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- 239000012074 organic phase Substances 0.000 claims description 4
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- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 claims description 3
- -1 dry Substances 0.000 claims description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 3
- 239000012044 organic layer Substances 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims 2
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- 238000006069 Suzuki reaction reaction Methods 0.000 abstract description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052794 bromium Inorganic materials 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000005893 bromination reaction Methods 0.000 abstract description 2
- 238000005401 electroluminescence Methods 0.000 abstract description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract 2
- 150000002825 nitriles Chemical class 0.000 abstract 2
- 239000002994 raw material Substances 0.000 abstract 2
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- KYLUAQBYONVMCP-UHFFFAOYSA-N (2-methylphenyl)phosphane Chemical class CC1=CC=CC=C1P KYLUAQBYONVMCP-UHFFFAOYSA-N 0.000 description 4
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
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- 239000011368 organic material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- 125000002560 nitrile group Chemical group 0.000 description 2
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QNEFNFIKZWUAEQ-UHFFFAOYSA-N carbonic acid;potassium Chemical compound [K].OC(O)=O QNEFNFIKZWUAEQ-UHFFFAOYSA-N 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000002027 dichloromethane extract Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
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- 229920006351 engineering plastic Polymers 0.000 description 1
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- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000012485 toluene extract Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/52—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of six-membered aromatic rings being part of condensed ring systems
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Abstract
本发明公开了4’‑(4‑溴萘‑1‑基)[1,1’‑联苯基]‑4‑腈及其合成方法,属有机合成领域。通过如下方法实现:以4‑溴苯腈为原料经过与双(频哪醇合)二硼硼化反应、Suzuki偶联反应合成4‑溴‑4‑腈基联苯;以4‑溴‑4‑腈基联苯和1‑萘硼酸为原料通过Suzuki偶联反应合成4’‑(萘‑1‑基)[1,1’‑联苯基]‑4‑腈,最后经溴化反应合成目标化合物。合成方法简单,收率高,适用于工业化生产,化合物适用于有机电致发光器件的发光材料中主客体掺杂材料。
Description
技术领域
本发明涉及联苯基修饰的1,4-二取代基萘化合物及其合成方法,具体涉及4’-(4-溴萘-1-基)[1,1’-联苯基]-4-腈及其合成方法,属有机合成领域。
背景技术
联苯是一类重要的有机化工原料,被广泛用于医药、农药、染料、液晶材料等领域。可用于合成增塑剂、防腐剂,还可用于制造燃料、工程塑料和高能燃料等。研究表明,含腈基联苯衍生物中的共轭π电子能够赋予它卓越的光电性能,使其具有良好的空穴传输能力和高发光能力。含腈基联苯衍生物大体积的芳香基团可抑制分子的紧密堆积和复合物的生成,这样使化合物具有很好的热稳定性和发光效率。
有机掺杂材料可以促成具有优越电子传输性能及发光特性的主体材料与各种高荧光效率的客体材料的有效结合,得到高效发光效率和各种不同的光色。此外,可以将电激发产生的电激子转移到高荧光效率及稳定的掺杂材料中发光,以提高器件的稳定性,促使器件由于非发光能量衰退的概率降至最低。因此,研究、合成有机掺杂材料十分必要,有利于开发有机掺杂材料,提高其性能。
发明内容
针对目前有机电致发光材料现状,本发明目的在于提供一种有机电致发光材料4’-(4-溴萘-1-基)[1,1’-联苯基]-4-腈及其合成方法。
为实现本发明目的,具体技术方案如下:
本发明以4-溴苯腈为原料合成4’-(4-溴萘-1-基)[1,1’-联苯基]-4-腈。所述的4’-(4-溴萘-1-基)[1,1’-联苯基]-4-腈化学结构如下:
合成路线如下:
合成步骤如下:以4-溴苯腈为原料合成4-腈基苯硼酸频哪醇酯;然后与1,4-二溴苯反应合成了4-溴-4’-腈基联苯;4-溴-4’-腈基联苯与1-萘硼酸反应后合成4’-(萘-1-基)[1,1’-联苯基]-4-腈,最后经过溴化反应合成目标化合物4’-(4-溴萘-1-基)[1,1’-联苯基]-4-腈。
具体步骤如下:
(1)4-腈基苯硼酸频哪醇酯(a)的合成
惰性气体保护下,依次加入4-溴苯腈,乙酸钠,二乙二醇二甲醚和双(频哪醇合)二硼,控制反应温度120-150℃,加入催化剂1,1'-双(二环己基基膦)二茂铁氯化钯,高效液相色谱(HPLC)检测反应结束。水淬灭,经萃取,合并有机相,干燥,减压回收溶剂,精馏得到4-腈基苯硼酸频哪醇酯。
(2)4-溴-4’-腈基联苯(b)的合成
惰性气体保护下,依次加入1,4-二溴苯,4-腈基苯硼酸频哪醇酯,三水合磷酸钾,三(间甲苯基)膦,四氢呋喃,加入三(二亚苄基丙酮)二钯(Pd2(dba)3),控制反应温度50-60℃,HPLC检测反应结束,向反应液中加入水,经萃取,干燥,减压回收溶剂,精馏得到4-溴-4’-腈基联苯。
(3)4’-(萘-1-基)[1,1’-联苯基]-4-腈(c)的合成
惰性气体保护下,将4-溴-4’-腈基联苯,1-萘硼酸,碳酸钾,甲苯依次投入到反应瓶中。搅拌均匀后,向反应瓶中加入醋酸钯和三(间甲苯基)膦(TPTP),控制反应温度80-90℃反应,HPLC检测反应结束。加入水结束反应,抽滤,有机层水洗,干燥,脱色,抽滤,减压回收溶剂得到4’-(萘-1-基)[1,1’-联苯基]-4-腈。
(4)4’-(4-溴萘-1-基)[1,1’-联苯基]-4-腈(d)的合成
依次加入4’-(萘-1-基)[1,1’-联苯基]-4-腈,1,2-二溴乙烷,控制反应温度-20-0℃。缓慢滴加二溴海因的1,2-二溴乙烷溶液,HPLC检测反应完全。将反应液冷却后,经萃取,干燥,抽滤,重结晶得到目标化合物。
本发明化合物4’-(4-溴萘-1-基)[1,1’-联苯基]-4-腈是一种重要的有机电致发光材料中主客体掺杂材料,其含量达到99.9%以上,具有较高的分解温度,5%失重温度是287.7℃,良好的热稳定性能确保材料能够耐受器件制备和运行过程中的高温;该化合物在二氯甲烷溶剂中的荧光发射光谱显示最大发射波长为426nm。4’-(4-溴萘-1-基)[1,1’-联苯基]-4-腈作为主客体掺杂材料应用到有机电致发光材料中可以提高器件的稳定性和发光性能。此外,其萘结构1,4-位引入不同取代基后,特别是4-位溴为活性位,可以参与Suzuki偶联反应、Buchwald偶联反应等化学修饰直接应用到其他有机材料的合成等方面。本发明合成方法简单,总收率达到76%以上,适用于工业化生产。
附图说明
图1为本发明化合物热重图谱。
图2为本发明化合物在二氯甲烷溶剂中的荧光发射光谱。
具体实施方式
为对本发明进行更好地说明,举实例如下:
实施例1
(1)4-腈基苯硼酸频哪醇酯(a)的合成
氩气保护下,依次加入4-溴苯腈91.1g(0.5mol),乙酸钠98.4g(1.2mol),二乙二醇二甲醚800mL和双(频哪醇合)二硼152.4g(0.6mol),控制反应温度140℃,加入催化剂1,1'-双(二环己基基膦)二茂铁氯化钯375.5mg(0.5mmol),反应14h后,高效液相色谱(HPLC)检测反应结束。600mL水淬灭,300mL甲苯萃取3次,合并有机相,无水硫酸镁干燥,过滤,减压回收溶剂,得到棕色固体,使用4L油泵蒸馏得到4-腈基苯硼酸频哪醇酯111.4g。含量99.5%(GC),收率97.2%,熔点93.6-94.5℃。
1H NMR(400MHz,CDCl3),δ:1.35(12H,s),7.61(2H,J=8.2Hz;d),7.87(2H,J=8.2Hz;d)。
13C NMR(100MHz,CDCl3),δ:24.86,84.49,114.56,118.89,131.13,135.08.
(2)4-溴-4’-腈基联苯(b)的合成.
氩气保护下,依次加入1,4-二溴苯117.9g(0.5mol),4-腈基苯硼酸频哪醇酯91.6g(0.4mol),三水合磷酸钾213.1g(0.8mol),三(间甲苯基)膦0.3g(1mmol),四氢呋喃500mL,加入三(二亚苄基丙酮)二钯(Pd2(dba)3183.1mg(0.2mmol),控制反应温度60℃,HPLC检测反应结束,向反应液中加入700mL水,300mL二氯甲烷萃取3次,合并有机相,无水硫酸镁干燥,过滤,减压回收溶剂,得到淡黄色固体,干燥后98.3g,纯度99.1%(HPLC),收率95.3%,熔点:222.8-224.9℃。
1H NMR(400MHz,CDCl3),δ:7.45(2H,J=8.4Hz;d),7.62(2H,J=8.4Hz;d),7.67(2H,J=8.4Hz;d),7.74(2H,J=8.4Hz;d);
13C NMR(100MHz,CDCl3),δ:111.52,118.94,123.36,127.75,128.91,132.42,132.95,138.27,144.63.
(3)4’-(萘-1-基)[1,1’-联苯基]-4-腈(c)的合成
氩气保护下,将4-溴-4’-腈基联苯51.6g(0.2mol),1-萘硼酸34.4g(0.2mol),碳酸钾69.1g(0.5mol),甲苯500mL依次投入到反应瓶中。搅拌均匀后,向反应瓶中加入醋酸钯44.9mg和三(间甲苯基)膦35.6mg,控制反应温度90℃反应,HPLC检测反应结束。加入400mL水结束反应,抽滤,有机层水洗,无水硫酸钠干燥,抽滤,滤液减压回收部分甲苯后加入正己烷,冷却后抽滤,干燥得到类白色固体57.8g,含量99.3%(HPLC),收率94.6%。产品熔点:158.1-160.4℃。
1H NMR(400MHz,CDCl3),δ:7.38-7.57(8H,m),7.69-7.94(7H,m).
13C NMR(100MHz,CDCl3),δ:111.37,119.24,125.74,126.13,126.25,126.53,127.34,127.42,128.01,128.46,128.77,131.13,131.86,133.06,134.26,138.3,139.62,141.68,146.63.
(4)4’-(4-溴萘-1-基)[1,1’-联苯基]-4-腈(d)的合成
依次加入4’-(萘-1-基)[1,1’-联苯基]-4-腈30.5g(0.1mol),1,2-二溴乙烷200mL。将二溴海因14.3g(0.05mol)溶解于100mL 1,2-二溴乙烷中,然后控制反应温度-10℃缓慢滴加到反应体系,HPLC检测反应完全。滴加亚硫酸氢钠水溶液终止反应,200mL水洗至中性,无水硫酸钠干燥,抽虑,1,2-二溴乙烷-甲醇混合溶剂重结晶2次得到淡黄色固体33.6g,含量99.9%,收率87.7%。熔点:197.1-199.9℃。
1H NMR(400MHz,CDCl3),δ:8.35(1H,J=8.2Hz;d),7.91(1H,J=8.36Hz;d),7.85(1H,J=7.64Hz;d),7.77-7.71(6H,m),7.65-7.61(1H,m),7.58-7.56(2H,m),7.53-7.491(1H,m),7.29(1H,J=7.64Hz;d)。
13C NMR(100MHz,CDCl3),δ:145.13,140.44,139.46,138.36,132.75,132.17,130.79,129.54,127.71,127.65,127.39,127.25,127.03,126.44,122.77,118.95,111.13。
Claims (2)
1.4’-(4-溴萘-1-基)[1,1’-联苯基]-4-腈,其特征在于,其结构式如下:
。
2.合成如权利要求1所述的4’-(4-溴萘-1-基)[1,1’-联苯基]-4-腈方法,其特征在于,通过如下步骤实现:
(1)4-腈基苯硼酸频哪醇酯(a)的合成
惰性气体保护下,依次加入4-溴苯腈,乙酸钠,二乙二醇二甲醚和双(频哪醇合)二硼,控制反应温度120-150 ℃,加入催化剂1,1'-双(二环己基基膦)二茂铁氯化钯,高效液相色谱(HPLC)检测反应结束;水淬灭,经萃取,合并有机相,干燥,减压回收溶剂,精馏得到4-腈基苯硼酸频哪醇酯;
(2)4-溴-4’-腈基联苯(b)的合成
惰性气体保护下,依次加入1,4-二溴苯,4-腈基苯硼酸频哪醇酯,三水合磷酸钾,三(间甲苯基)膦,四氢呋喃,加入三(二亚苄基丙酮)二钯(Pd2(dba)3),控制反应温度50-60℃,HPLC检测反应结束,向反应液中加入水,经萃取,干燥,减压回收溶剂,精馏得到4-溴-4’-腈基联苯;
(3)4’-(萘-1-基)[1,1’-联苯基]-4-腈(c)的合成
惰性气体保护下,将4-溴-4’-腈基联苯,1-萘硼酸,碳酸钾,甲苯依次投入到反应瓶中,搅拌均匀后,向反应瓶中加入醋酸钯和三(间甲苯基)膦,控制反应温度80-90℃反应,HPLC检测反应结束;加入水结束反应,抽滤,有机层水洗,干燥,脱色,抽滤,减压回收溶剂得到4’-(萘-1-基)[1,1’-联苯基]-4-腈;
(4)4’-(4-溴萘-1-基)[1,1’-联苯基]-4-腈(d)的合成
依次加入4’-(萘-1-基)[1,1’-联苯基]-4-腈,1,2-二溴乙烷,控制反应温度-20-0℃,缓慢滴加二溴海因的1,2-二溴乙烷溶液,HPLC检测反应完全;将反应液冷却后,经萃取,干燥,抽滤,重结晶得到目标化合物。
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