CN107417480A - 一种合成三亚苯类化合物的方法 - Google Patents

一种合成三亚苯类化合物的方法 Download PDF

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CN107417480A
CN107417480A CN201710307362.9A CN201710307362A CN107417480A CN 107417480 A CN107417480 A CN 107417480A CN 201710307362 A CN201710307362 A CN 201710307362A CN 107417480 A CN107417480 A CN 107417480A
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张逢质
杨帅
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Zhejiang University of Technology ZJUT
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Abstract

本发明提供了一种合成式(III)所示三亚苯类化合物的方法,所述的方法为:将式(I)所示苯甲酸类化合物、式(II)所示环状碘鎓盐、醋酸钯、碳酸钾溶解在N‑甲基吡咯烷酮中,升温至110~145℃搅拌反应6~17h,之后反应液经后处理,得到所述的三亚苯类化合物;本发明反应体系简单,原料特别是苯甲酸类化合物容易得到,底物无需多步制备,因此本发明反应的收率较高,本发明的创新点在于苯甲酸类化合物与环状碘鎓盐反应一步就能得到三亚苯,使得反应路线大大缩短,所得的相应三亚苯类化合物的收率最高为93%;

Description

一种合成三亚苯类化合物的方法
(一)技术领域
本发明涉及一种合成三亚苯类化合物的方法,具体涉及一种通过苯甲酸类化合物与环状碘鎓盐反应,高效合成三亚苯类化合物的方法。
(二)背景技术
三亚苯类化合物(也称为多环芳烃)广泛应用于有机合成,也可以作为盘状液晶材料,有特殊的光电性能,是一种新型的光电材料,可用于光电器件,光学数据储存装置,光伏太阳能电池和发光二极管。因此在材料方面有很大的开发与利用价值(Angew.Chem.Int.Ed.2007,46,4832-4887;Chemical Reviews,2001,101,5;Science.2001,293)。
目前,该类化合物的合成大多通过三联苯或联苯的氧化环加成而得到(J.Mater.Chem.,2001,11,1618;J.Chem.Soc.,Chem.Commun.,1994,465),或者通过苯炔的三聚化得到(Angew.Chem.Int.Ed.,1998,37,2659),对于有取代基的苯炔中间体,往往得到同分异构体的混合物,分离难度大。
从合成的角度上讲,以上合成方法中所用到的底物需要多步才能合成,因此造成总的收率普遍较低,如果能用苯甲酸类化合物与环状碘鎓盐来一步合成三亚苯,无论是从原料的易得性、原子的经济性还是从合成方法的角度上来讲,都是对以往合成方法的一个比较大的突破;由于本合成方法的简洁高效性,因此具有一定的应用价值。
(三)发明内容
本发明的目的是提供一种通过苯甲酸类化合物与环状碘鎓盐反应一步合成三亚苯类化合物的方法,与以往合成三亚苯需要经过繁琐的步骤相比,本发明更加简洁高效。
本发明的技术方案如下:
一种合成式(III)所示三亚苯类化合物的方法,所述的方法为:
将式(I)所示苯甲酸类化合物、式(II)所示环状碘鎓盐、醋酸钯、碳酸钾溶解在NMP(N-甲基吡咯烷酮)中,升温至110~145℃搅拌反应6~17h,之后反应液经后处理,得到所述的三亚苯类化合物;
所述式(I)所示苯甲酸类化合物、式(II)所示环状碘鎓盐、醋酸钯、碳酸钾的投料物质的量之比为1:1~2:0.025~0.1:0.8~3;
所述NMP的体积用量以式(I)所示苯甲酸类化合物的质量计为10~50mL/g;
所述反应液的后处理方法为:反应结束后,冷却至室温(20~30℃,下同),反应液用乙酸乙酯萃取,萃取液经无水硫酸钠干燥,过滤,浓缩后进行快速柱层析,以石油醚与乙酸乙酯体积比100~6:1的混合溶剂为洗脱剂,收集含目标化合物的洗脱液,蒸除溶剂并干燥,得到所述的三亚苯类化合物。
本发明涉及的反应式如下:
式(I)、(II)或(III)中,
R1为氢或者所在环上的一个取代基,所述的取代基为C1~C3烷基(优选甲基)、卤素(优选F或Cl)、C1~C3烷氧基(优选甲氧基)、硝基、甲基磺酰基、氨基或苯基,或者R1与其所在环共同形成萘基;
R2为氢或者所在苯环上的一个取代基,所述的取代基为C1~C3烷基(优选甲基)、卤素(优选F或Cl)、C1~C3烷氧基(优选甲氧基)、叔丁基、乙氧基羰基或苯基;
R3的定义与R2相同;
X为氯、溴或氢;
Y、Z各自独立为C或N,并且Y和Z不同时为N。
本发明具有以下优点:
反应体系简单,原料特别是苯甲酸类化合物容易得到;底物无需多步制备,因此本发明反应的收率较高。本发明的创新点在于苯甲酸类化合物与环状碘鎓盐反应一步就能得到三亚苯,使得反应路线大大缩短。所得的相应三亚苯类化合物的收率最高为93%。
(四)具体实施方式
下面通过具体实施例对本发明作进一步的说明,但本发明的保护范围并不仅限于此。
实施例1
将邻氯苯甲酸(78mg,0.5mmol),碘鎓盐(236mg,0.55mmol),醋酸钯(2.8mg,0.0125mmol),碳酸钾(152mg,1.1mmol)溶解在3mL的NMP溶剂中,加热到110℃搅拌反应17小时,冷却至室温用乙酸乙酯萃取,饱和氯化钠溶液洗涤,无水硫酸钠干燥,过滤,浓缩,柱层析,得到产物三亚苯92mg,收率为80%,产物为白色固体。m.p.:195-197℃1H NMR(500MHz,CDCl3)δ8.7-8.67(m,6H),7.7-7.67(m,6H)ppm.13C NMR(126MHz,CDCl3)δ129.81,127.22,123.31ppm.
实施例2
按实施例1所述的方法,不同的是所用底物为:2-氯-5-甲基苯甲酸(85mg,0.5mmol),得产物2-甲基三亚苯91mg,收率为75%,产物为白色固体。m.p.:101-102℃1HNMR(500MHz,CDCl3)δ8.69-8.63(m,4H),8.56(d,J=8.4Hz,1H),8.47(s,1H),7.68-7.65(m,4H),7.51(dd,J=8.3,1.4Hz,1H),2.64(s,3H)ppm.13C NMR(126MHz,CDCl3)δ136.89,129.92,129.78,129.7,129.43,128.7,127.5,127.17,127.1,127.08,126.78,123.32,123.3,123.27,123.09,21.85ppm.
实施例3
按实施例1所述的方法,不同的是所用底物为:2-氯-4-氟苯甲酸(87mg,0.5mmol),反应时间为12小时,得产物2-氟三亚苯100mg,收率为81%,产物为白色固体。m.p.:183-184℃1H NMR(500MHz,CDCl3)δ8.66-8.6(m,3H),8.57-8.55(m,1H),8.52-8.5(m,1H),8.26(dd,J=11.1,2.6Hz,1H),7.7-7.65(m,4H),7.39(ddd,J=9.1,7.8,2.6Hz,1H)ppm.13C NMR(126MHz,CDCl3)δ162.20(d,JC-F=245.6Hz),131.78(d,JC-F=8Hz),130.20,129.33,129.27,129.01(d,JC-F=3.3Hz),128.99,127.83,127.42,127.30,126.29(d,JC-F=2.2Hz),125.55(d,JC-F=8.8Hz),123.48,123.38,123.37,123.11,115.42(d,JC-F=23.0Hz),108.75(d,JC-F=22.4Hz)
实施例4
按实施例1所述的方法,不同的是所用底物为:2-氯-4-甲氧基苯甲酸(93mg,0.5mmol),得产物2-甲氧基三亚苯110mg,收率为85%,产物为白色固体。m.p.:101-103℃1HNMR(500MHz,CDCl3)δ8.65-8.61(m,2H),8.58-8.56(m,1H),8.52-8.50(m,2H),8.03(d,J=2.6Hz,1H),7.68-7.60(m,4H),7.25(dd,J=9.0,2.6Hz)ppm.13C NMR(126MHz,CDCl3)δ158.75,130.09,129.81,129.36,128.63,127.17,127.11,126.89,126.11,124.80,123.65,123.26,123.19,123.15,122.66,115.62,105.65,55.28ppm.
实施例5
按实施例1所述的方法,不同的是:所用底物为3-氯吡啶-4-甲酸(79mg,0.5mmol);温度为:145℃。得产物二苯并[f,h]异喹啉104mg,收率为90%,产物为白色固体。m.p.:162-164℃1H NMR(500MHz,CDCl3)δ9.76(s,1H),8.66(d,J=5.5Hz,1H),8.54-8.50(m,1H),8.45-8.39(m,2H),8.37(d,J=8.1Hz,1H),8.12(d,J=5.4Hz,1H),7.65-7.59(m,1H),7.59-7.52(m,3H)ppm.13C NMR(126MHz,CDCl3)δ146.46,146.02,134.78,130.92,129.57,129.03,128.63,127.74,127.71,127.54,127.23,127.12,124.20,123.43,123.10,12.27,116.00ppm.
实施例6
按实施例1所述的方法,不同的是所用底物为:2-氯-4-硝基苯甲酸(101mg,0.5mmol),碘鎓盐(257mg,0.60mmol),醋酸钯(5.6mg,0.0250mmol),得产物2-硝基苯甲酸96mg,收率为70%,产物为白色固体。m.p.:155-157℃1H NMR(500MHz,CDCl3)δ9.09(d,J=2.2Hz,1H),8.46(t,J=9.2Hz,2H),8.36-8.32(m,3H),8.13(dd,J=9.0,2.3Hz,1H),7.70-7.57(m,4H)ppm.13C NMR(126MHz,CDCl3)δ146.06,133.96,130.74,129.86,129.61,128.99,128.38,128.34,127.84,127.68,127.57,124.07,124.00,123.31,123.28,123.18,120.57,118.77ppm.
实施例7
按实施例1所述的方法,不同的是所用底物为:2-氯-4-甲砜基苯甲酸(117.3mg,0.5mmol),3,7-二氯碘鎓盐(274mg,0.55mmol),溶剂NMP为2mL,得产物2,7-二氯-11-甲砜基三亚苯144mg,收率为77%,产物为黄色固体。m.p.:275-277℃1H NMR(500MHz,DMSO)δ9.30(d,J=1.7Hz,1H),9.13(d,J=8.8Hz,1H),9.00(d,J=2.0Hz,1H),8.96(d,J=2.0Hz,1H),8.85(dd,J=9.0,2.2Hz,2H),8.18(dd,J=8.7,1.8Hz,1H),7.83(ddd,J=8.8,6.7,2.1Hz,2H),3.48(s,3H)ppm.13C NMR(126MHz,DMSO)δ140.38,133.49,131.96,129.60,129.23,128.80,127.63,126.13,125.56,125.14,124.08,123.62,123.40,43.39ppm.HRMS m/z(ESI):calcd for C19H12Cl2NaO2S[M+Na]+396.9827,found:396.9832.
实施例8
按实施例1所述的方法,不同的是所用底物为:3-甲基-7-甲氧基碘鎓盐(256mg,0.55mmol),得产物2-甲基-7-甲氧基三亚苯62mg,收率为46%,产物为白色固体。m.p.:75-76℃1H NMR(500MHz,CDCl3)δ8.68–8.64(m,1H),8.60–8.56(m,1H),8.51(d,J=9.0Hz,1H),8.44–8.41(m,2H),8.05(d,J=2.6Hz,1H),7.69–7.63(m,2H),7.46(dd,J=8.4,1.2Hz,1H),7.26(dd,J=9.0,2.7Hz,1H),4.03(s,3H),2.62(s,3H)ppm.13C NMR(126MHz,CDCl3)δ158.54,135.73,130.79,130.10,129.57,128.69,128.67,127.58,127.13,126.84,124.65,123.90,123.30,123.26,123.21,122.68,115.70,105.72,55.40,21.74ppm.HRMS m/z(ESI):calcd for C20H17O[M]+273.1274,found:273.1274.
实施例9
按实施例1所述的方法,不同的是所用底物为:2-氯-4-甲氧基苯甲酸(93mg,0.5mmol),2,7-二氯碘鎓盐(274mg,0.55mmol),得产物2,7-二氯-11-甲氧基三亚苯108mg,收率为66%,产物为白色固体。m.p.:155-157℃1H NMR(500MHz,CDCl3)δ8.21–8.16(m,5H),7.62(d,J=2.5Hz,1H),7.45(dd,J=8.8,2.1Hz,1H),7.40(dd,J=8.7,2.1Hz,1H),7.15(dd,J=9.0,2.6Hz,1H),3.99(s,3H)ppm.13C NMR(126MHz,CDCl3)δ159.20,133.43,133.15,130.89,130.41,130.20,127.61,127.42,126.36,126.13,124.80,124.56,124.45,122.79,122.65,122.29,116.57,105.27,55.45.HRMS m/z(ESI):calcd for C19H12Cl2O[M]+327.0338,found:327.0338.
实施例10
按实施例1所述的方法,不同的是所用底物为:2,7-二甲基碘鎓盐(251mg,0.55mmol),得产物2,7-二甲基三亚苯79mg,收率为61%,产物为白色固体。m.p.:108-109℃1H NMR(500MHz,CDCl3)δ8.68(dd,J=6.2,3.4Hz,2H),8.51(d,J=8.3Hz,2H),8.46(s,2H),7.67(dd,J=6.2,3.3Hz,2H),7.48(dd,J=8.3,1.3Hz,2H),2.64(s,6H)ppm.13C NMR(126MHz,CDCl3)δ136.35,129.85,129.40,128.62,127.61,126.94,123.26,123.03,21.86ppm.HRMS m/z(ESI):calcd forC20H17[M+H]+257.1325,found:257.1321.
实施例11
按实施例1所述的方法,不同的是所用底物为:2-叔丁基碘鎓盐(266mg,0.55mmol),得产物2-叔丁基三亚苯91mg,收率为64%,产物为油状液体。1H NMR(500MHz,CDCl3)δ8.84-8.78(m,2H),8.74–8.67(m,3H),8.64(d,J=8.7Hz,1H),7.83–7.68(m,5H),1.64(s,9H)ppm.13C NMR(126MHz,CDCl3)δ149.80,130.04,129.90,129.76,129.46,129.31,127.46,127.07,127.00,126.94,126.74,125.16,123.32,123.19,123.10,119.16,35.02,31.46ppm.HRMS m/z(ESI):calcd for C22H20Na[M+Na]+307.1457,found:307.1458.
实施例12
按实施例1所述的方法,不同的是所用底物为:2-乙氧羰基碘鎓盐(275mg,0.55mmol),反应时间为12小时,得产物2-乙氧羰基三亚苯112mg,收率为74%,产物为白色固体。m.p.:128-130℃1H NMR(500MHz,CDCl3)δ9.23(s,1H),8.63(d,J=7.3Hz,1H),8.55-8.48(m,4H),8.16(d,J=8.5Hz,1H),7.67–7.58(m,4H),4.52(q,J=7.1Hz,2H),1.53(t,J=7.1Hz,3H)ppm.13C NMR(126MHz,CDCl3)δ166.63,132.91,130.45,129.69,129.29,129.25,128.80,128.49,128.03,127.51,127.32,127.19,127.05,125.14,123.78,123.37,123.20,123.17,123.11,61.10,14.44ppm.
实施例13
按实施例1所述的方法,不同的是所用底物为:2-苯基碘鎓盐(178mg,0.55mmol),溶剂NMP为4mL,得产物2-苯基三亚苯118mg,收率为77%,产物为黄色固体。m.p.:174-175℃1H NMR(500MHz,CDCl3)δ8.87(d,J=1.7Hz,1H),8.78–8.74(m,1H),8.71–8.65(m,4H),7.90(dd,J=8.5,1.8Hz,1H),7.85-7.82(m,2H),7.72–7.66(m,4H),7.58(t,J=7.7Hz,2H),7.47(t,J=7.4Hz,1H)ppm.13C NMR(126MHz,CDCl3)δ141.18,139.86,130.08,130.04,129.81,129.79,129.61,128.95,128.91,127.53,127.43,127.35,127.30,127.25,127.23,127.05,126.35,123.88,123.39,123.35,123.33,121.78ppm
实施例14
按实施例1所述的方法,不同的是所用底物为:1-溴-2-萘甲酸(125mg,0.5mmol),反应时间为8小时,得产物苯并[g]94mg,收率为67%,产物为白色固体。1H NMR(500MHz,CDCl3)δ8.99(d,J=8.3Hz,1H),8.94(d,J=8.2Hz,1H),8.76-8.72(m,2H),8.68–8.63(m,1H),8.61(d,J=8.9Hz,1H),8.06–7.98(m,2H),7.76–7.61(m,6H)ppm.13C NMR(126MHz,CDCl3)δ133.52,130.84,130.18,129.93,129.74,129.42,129.35,128.40,128.11,128.01,127.63,127.27,127.08,126.59,126.02,125.94,125.81,123.69,123.43,123.08,120.70ppm
实施例15
按实施例1所述的方法,不同的是:所用底物为2-氯吡啶-3-甲酸(79mg,0.5mmol),碘鎓盐(342mg,0.80mmol),温度为:145℃。得产物二苯并[f,h]喹啉57mg,收率为50%,产物为白色固体。m.p.:170-173℃1H NMR(500MHz,CDCl3)δ9.37-9.33(m,1H),8.97(dd,J=4.3,1.6Hz,1H),8.80(dd,J=8.3,1.5Hz,1H),8.65-8.57(m,2H),8.52-8.50(m,1H),7.77-7.73(m,2H),7.66(tdd,J=14.8,7.1,1.4Hz,2H),7.54(dd,J=8.2,4.4Hz,1H)ppm.13C NMR(126MHz,CDCl3)δ148.76,146.41,131.25,130.79,130.74,129.73,128.80,128.63,127.80,127.45,127.28,125.34,124.42,123.35,123.17,122.51,122.06ppm
实施例16
按实施例1所述的方法,不同的是所用底物为:2-氯-4-甲砜基苯甲酸(117mg,0.5mmol),醋酸钯(5.6mg,0.0250mmol),得产物2-甲砜基三亚苯143mg,收率为93%,产物为白色固体。m.p.:185-186℃1H NMR(500MHz,CDCl3)δ9.16(d,J=1.8Hz,1H),8.72(d,J=8.7Hz,1H),8.65–8.56(m,4H),8.09(dd,J=8.6,1.9Hz,1H),7.75–7.65(m,4H),3.19(s,3H)ppm.13C NMR(126MHz,CDCl3)δ138.43,133.52,130.78,130.05,129.99,128.85,128.58,128.39,128.20,127.74,127.63,124.66,124.37,123.98,123.51,123.45,123.36,123.28,44.77ppm.HRMS m/z(ESI):calcd for C19H15O2S[M+H]+307.0787,found:307.0788
实施例17
按实施例1所述的方法,不同的是所用底物为:苯甲酸(61mg,0.5mmol),醋酸钯(11.2mg,0.05mmol),得产物三亚苯15mg,收率为15%,产物为白色固体。结构信息同实施例1。
实施例18
按实施例1所述的方法,不同的是所用底物为:2-溴苯甲酸(100mg,0.5mmol),碳酸钾(104mg,0.75mmol),得产物三亚苯64mg,收率为56%,产物为白色固体。结构信息同实施例1。
实施例19
按实施例1所述的方法,不同的是所用底物为:2-氨基-6-氯苯甲酸(86mg,0.5mmol),得产物1-氨基三亚苯80mg,收率为65%,产物为黄色固体。m.p.:75-77℃1H NMR(500MHz,CDCl3)δ9.28-9.17(m,1H),8.66-8.62(m,1H),8.61-8.55(m,2H),8.12(d,J=8.1Hz,1H),7.69-7.56(m,4H),7.44(t,J=7.9Hz,1H),6.98(d,J=7.5Hz,1H),4.35(s,2H)ppm.13C NMR(126MHz,CDCl3)δ145.05,132.06,130.32,130.27,130.11,127.22,127.14,126.20,126.16,123.84,123.54,122.98,118.68,115.84,114.06,112.22,107.28ppm.HRMSm/z(ESI):calcd for C18H14N[M+H]+244.1121,found:244.1120
实施例20
按实施例1所述的方法,不同的是所用底物为:2,6-二氯苯甲酸(96mg,0.5mmol),碘鎓盐(342mg,0.80mmol),得产物1-氯三亚苯54mg,收率为41%,产物为白色固体。m.p.:92-94℃1HNMR(500MHz,CDCl3)δ9.60(dd,J=8.4,1.2Hz,1H),8.69-8.66(m,1H),8.62-8.52(m,3H),7.74-7.61(m,5H),7.52-7.47(m,1H)ppm.13C NMR(126MHz,CDCl3)δ133.05,131.76,130.96,130.17,129.77,129.36,128.26,127.81,127.65,127.44,127.18,126.72,125.69,123.62,123.27,123.14,123.07,122.02ppm.HRMS m/z(ESI):calcd for C18H11ClNa[M+Na]+285.0441,found:285.0443

Claims (5)

1.一种合成式(III)所示三亚苯类化合物的方法,其特征在于,所述的方法为:
将式(I)所示苯甲酸类化合物、式(II)所示环状碘鎓盐、醋酸钯、碳酸钾溶解在N-甲基吡咯烷酮中,升温至110~145℃搅拌反应6~17h,之后反应液经后处理,得到所述的三亚苯类化合物;
所述式(I)所示苯甲酸类化合物、式(II)所示环状碘鎓盐、醋酸钯、碳酸钾的投料物质的量之比为1:1~2:0.025~0.1:0.8~3;
式(I)、(II)或(III)中,
R1为氢或者所在环上的一个取代基,所述的取代基为C1~C3烷基、卤素、C1~C3烷氧基、硝基、甲基磺酰基、氨基或苯基,或者R1与其所在环共同形成萘基;
R2为氢或者所在苯环上的一个取代基,所述的取代基为C1~C3烷基、卤素、C1~C3烷氧基、叔丁基、乙氧基羰基或苯基;
R3的定义与R2相同;
X为氯、溴或氢;
Y、Z各自独立为C或N,并且Y和Z不同时为N。
2.如权利要求1所述的合成式(III)所示三亚苯类化合物的方法,其特征在于,R1为氢或者所在环上的一个取代基,所述的取代基为甲基、F、Cl、甲氧基、硝基、甲基磺酰基、氨基或苯基,或者R1与其所在环共同形成萘基。
3.如权利要求1所述的合成式(III)所示三亚苯类化合物的方法,其特征在于,R2为氢或者所在苯环上的一个取代基,所述的取代基为甲基、F、Cl、甲氧基、叔丁基、乙氧基羰基或苯基。
4.如权利要求1所述的合成式(III)所示三亚苯类化合物的方法,其特征在于,所述N-甲基吡咯烷酮的体积用量以式(I)所示苯甲酸类化合物的质量计为10~50mL/g。
5.如权利要求1所述的合成式(III)所示三亚苯类化合物的方法,其特征在于,所述反应液的后处理方法为:反应结束后,冷却至室温,反应液用乙酸乙酯萃取,萃取液经无水硫酸钠干燥,过滤,浓缩后进行快速柱层析,以石油醚与乙酸乙酯体积比100~6:1的混合溶剂为洗脱剂,收集含目标化合物的洗脱液,蒸除溶剂并干燥,得到所述的三亚苯类化合物。
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* Cited by examiner, † Cited by third party
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CN109942361A (zh) * 2018-04-10 2019-06-28 南京大学 一种芳基取代的三亚苯类化合物的制备方法及其应用
CN114716319A (zh) * 2022-04-28 2022-07-08 浙江工业大学 一种联芳氧基烯酸酯类化合物的合成方法
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CN109942361A (zh) * 2018-04-10 2019-06-28 南京大学 一种芳基取代的三亚苯类化合物的制备方法及其应用
CN109942361B (zh) * 2018-04-10 2022-03-15 南京大学 一种芳基取代的三亚苯类化合物的制备方法及其应用
CN114716319A (zh) * 2022-04-28 2022-07-08 浙江工业大学 一种联芳氧基烯酸酯类化合物的合成方法
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