CN106866348B - 一种多环芳烃化合物、合成方法及用途 - Google Patents

一种多环芳烃化合物、合成方法及用途 Download PDF

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CN106866348B
CN106866348B CN201710033935.3A CN201710033935A CN106866348B CN 106866348 B CN106866348 B CN 106866348B CN 201710033935 A CN201710033935 A CN 201710033935A CN 106866348 B CN106866348 B CN 106866348B
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余刘柱
施敏
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Shanghai Institute of Organic Chemistry of CAS
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Abstract

本发明涉及一种多环芳烃化合物、合成方法及应用，该化合物具有如下结构式的苯并蒽衍生物：

Description

一种多环芳烃化合物、合成方法及用途
技术领域
本发明涉及一种多环芳烃、合成方法以及用途，系使用多取代的3-芳基-2-萘乙醛在路易斯酸In(OTf)3催化作用下发生傅克关环/脱水过程合成多环芳烃(PAHs)的新方法。
背景技术
多环芳烃(PAHs)在石油工业中广泛存在和应用，而且是很多药物分子的基本骨架。但是由于合成具有高度官能团化以及稠环的多环化合物的方法一直有限，因此受到有机化学家的广泛关注。具有苯并蒽结构的化合物(见下图)一般广泛应用于光学材料以及电子器件中，许多经过修饰的多环芳烃也可以用来
作为半导体材料。更为重要的是，多环芳烃还可以用作潜在的抗癌抗菌药物[(a)Watson,M.D.；A.；Müllen,K.Chem.Rev.2001,101,1267.(b)Anthony,J.E.Chem.Rev.2006,106,5028.(c)Wu,J.；Pisula,W.；Müllen,K.Chem.Rev.2007,107,718.(d)Anthony,J.E.Angew.Chem.Int.Ed.2008,47,452.(d)Feng,X.；Pisula,W.；Müllen,K.Pure Appl.Chem.2009,81,2203；(e)Zhang,H.；Wu,D.；Hua,S.；Liu,H.；Yin,J.Curr.Org.Chem.2012,16,2124.(f)Kuninobu,Y.；Tatsuzaki,T.；Mastuki,T.；Takai,K.J.Org.Chem.2011,76,7005.(g)Segawa,Y.；Stephan,D.W.Chem.Commun.2012,48,11963.(h)Pérez,D.；D.；Guitián,E.Eur.J.Org.Chem.2013,5981.(i)Yu,J.；Yan,H.；Zhu,C.Angew.Chem.Int.Ed.2016,55,1143.(j)Dorel,R.；McGonigal,P.R.；Echavarren,A.M.Angew.Chem.Int.Ed.2016,55,11120.]。其中，当上述多环芳烃具有其他可以进一步官能团化的基团，这类化合物尤其受到人们的关注，因为此类化合物可以进一步转化成更为复杂的多环芳烃，也可以定向向一些具有药物或者生物活性的多环芳烃分子转化。苯并蒽作为其中的一种多环芳烃，也有重要的药学价值，比如以下2种化合物就具有抗癌活性[(a)Y.Zheng,C.Evelyn,WO 2016077793,2016.(b)J.N.Varghese,R.J.Simpson,R.L.Moritz,M.Lou,H.Ji,K.M.Branson,B.J.Smith,WO 2003025017,2003]。
目前关于合成多环芳烃的方法在文献中报导得并不多，大部分的合成都是基于分子内或者分子间的环化，其包括氧化光环化、Diels-Alder反应、过渡金属偶联或者环加成反应[(a)Floyd,A.J.；Dyke,S.F.；Ward,S.E.Chem.Rev.1976,76,509.(b)Pérez,D.；Guitián,E.Chem.Soc.Rev.2004,33,274.(c)Harvey,R.G.Curr.Org.Chem.2004,8,303.]。但是，这些传统的合成方法存在其不可跨越的局限性：底物合成一般都是经过多步合成，原料利用率低，而且过程繁琐，条件苛刻；其次，底物局限性与产物多样性有限：一般经过多步合成的底物对官能团的兼容性比较差，比较敏感的官能团如硝基，氰基，酯基难以适应多步合成方法，从而导致产物的多样性受到限制。另外，应用芳炔的环加成反应也可以合成多环芳烃，但是由于芳炔的活性太高，导致副反应增多，反应效率低，应用于合成工业上的价值并不大[(a)Tadross,P.M.；Stoltz,B.M.Chem.Rev.2012,112,3550.(b)Gampe,C.M.；Carreira,E.M.Angew.Chem.Int.Ed.2012,51,3766.(c)Pérez,D.；D.；Guitián,E.Eur.J.Org.Chem.2013,5981.]。
发明内容
本发明要解决的问题是提供一种多环芳烃化合物；
本发明还提供一种合成多环芳烃的方法，即采用非常简便的方法合成多取代的苯并蒽类衍生物；
本发明的另外一个目的是利用上述多环芳烃化合物用于制备药物。其中R1，R2和R3可以为各种活性基团或者氢原子，这为进一步转化成更为复杂的多环芳烃或者药物活性分子提供了可能。
本发明提供了一种多环芳烃化合物，该化合物是具有如下结构通式的苯并蒽衍生物：
式中，R1为H、杂芳基或C1-C10的烷基；
R2为各种各样的吸电子基团或给电子基团。如，R2可以为CF3、CH3SO2、CH3CH2SO2、PhCH2OCO、C1～C10烷氧基、OH、Me2NCH2CH2O、Et2NCH2CH2O,、NH2、芳基、杂芳基、C1-C10烷基；。
R3为氢、卤素、芳基、C1-C10的烷基、C1-C10的烷氧基、或者苯并芳基等。
上述的芳基为苯基、单取代或多取代的苯基，或萘基。苯基上的取代基可以是氢、C1-C10烷基、C1-C10烷氧基、卤素[F、Cl、Br或I]等，优选氢、C1-C10烷基、C1-C10烷氧基等；
上述的杂芳基为呋喃环、吡啶环或者噻吩环；
其中，当R1为H、R3为H时，R2不等于Ph。
推荐如下多环芳烃类衍生物：
所述的多环芳烃类化合物也可以进一步描述具有如下结构式：
其中，R1、R2和R3的定义如前所述。
本发明还提供了一种非常简便的方法合成上述的苯并蒽类衍生物,该方法包括R1为H、R3为H时，R2等于Ph的化合物。
本发明方法中，在底物3-芳基-2-萘乙醛中，只需要加入路易斯酸催化剂如In(OTf)3，Sc(OTf)3，FeCl3或[ReBr(CO)3(thf)]2，将反应混合物直接加热到30-80℃(R3为苯并芳基时，推荐加热到80℃)，对所考察的底物都以良好到优异的收率得到了相应的多取代的苯并蒽类衍生物。
具体的说本发明的方法如下：
在有机溶剂中和30-80℃下，底物3-芳基-2-萘乙醛和路易斯酸催化剂反应1-2小时获得；
所述的3-芳基-2-萘乙醛和路易斯酸催化剂的摩尔比为1:0.025-0.020；
所述的路易斯酸催化剂是In(OTf)3，Sc(OTf)3，FeCl3或[ReBr(CO)3(thf)]2；
所述的3-芳基-2-萘乙醛具有如下的结构式：
所述的多环芳烃化合物具有如下结构式的苯并蒽衍生物：
式中，R1为H、杂芳基或C1-C10的烷基；
R2为吸电子基团或给电子基团：CF3、CH3SO2、CH3CH2SO2、PhCH2OCO、C1～C6烷氧基、OH、Me2NCH2CH2O、Et2NCH2CH2O,、NH2、芳基、杂芳基、C1-C10烷基；
R3为氢、卤素、芳基、C1-C10的烷基、C1-C10的烷氧基、或者苯并芳基；
上述的芳基为苯基、单取代或多取代的苯基，或萘基；苯基上的取代基可以是氢、C1-C10烷基、C1-C10烷氧基、卤素；优选氢、C1-C10烷基、C1-C10烷氧基；
上述的杂芳基为呋喃基、吡啶基或者噻吩基。
本发明方法中所述的3-芳基-2-萘乙醛化合物的结构式可以如下：
所述的多环芳烃化合物的结构式可以如下：
采用本发明的方法实例子：在有机溶剂中，3-芳基-2-萘乙醛(1个当量)与催化量(2.5-20mol％)的路易斯酸催化剂(所述的路易斯酸催化剂推荐用In(OTf)3、[ReBr(CO)3(thf)]2)在加热条件下，如30-80℃，推荐在40-60℃，反应1-2小时，得到本发明的苯并蒽类衍生物。所述的有机溶剂推荐用二氯甲烷、二氯乙烷、二氧六环、苯、甲苯、二甲苯、乙腈、二甲基亚砜、二甲基甲酰胺。
反应式如下：
R1、R2和R3如前所述。
采用本发明的方法，首先用3-苯基-2-萘乙醛(1a)为底物，考察了催化剂、温度和时间对这个反应的影响。
表格一 催化剂、温度以及反应时间对反应的影响
a0.2mmol 1a和xmol％催化剂在2mL二氯乙烷中加热90/120分钟.b分离收率.
从上述表格中可以发现，反应效果最好的溶剂为二氯乙烷、反应温度为50℃，反应时间为2小时，能以89％的分离收率得到苯并蒽化合物2a。产物的2a结构是通过1H-NMR，13C-NMR，红外，质谱确定的。其中，化合物2a、2b的结构由X-ray单晶衍射进一步确认。
以下的实施例中就应用直接加热到50℃的方法，催化剂选用5mol％的路易斯酸催化剂In(OTf)3以及反应时间定为2小时，对反应的溶剂效应进行了考察。选用3-苯基-2-萘乙醛(1a)为底物，对一些常见溶剂进行考察，其中的一部分结果如下所示：
表格2溶剂效应对反应的影响
a0.2mmol1a和5mol％In(OTf)3在2mL溶剂中加热到50℃反应120分钟.b分离收率.
从上述表格可以发现，在所考察的各种溶剂中，这个反应都能顺利进行，得到苯并蒽类化合物。而最好两个溶剂是二氯乙烷和甲苯。
接下去对含各种取代基的底物1进行的普适性考察，结果如下表所示：
表格3对底物适用性的考察a，b
a0.2mmol 1和5mol％的催化剂In(OTf)3在2mL溶剂二氯乙烷中加热到50℃反应2小时.b分离收率.
从表3中可以发现：当R1、R2和R3为吸电子取代和推电子取代基反应都可以顺利的进行反应，取得理想的效果；当R1取代的苯环变为噻吩环时，该反应也同样能顺利地得到目标产物。
从上述结果同时可以看出，这个反应对考察的绝大部分2-萘乙醛都适应，在优化的条件下都可以顺利的得到相应的多取代的苯并蒽类衍生物。
将萘乙醛底物进一步拓展到3-苯基-2-蒽乙醛底物1l和3-萘基-2-萘乙醛底物1m，反应也能顺利进行，生成相应的五并环多环芳烃2l和2m，只是反应温度要相应的提高到80℃。
产物2h可以和吗啉在Buchwald-Hartwig氨基化反应条件下实现偶联，生成的偶联产物具有抗癌抗菌性能[Zheng,Y.；Evelyn,C.WO Patent 2016077793,2016]。
本发明是一种非常简单易行的、环境友好的用来制备多环芳烃苯并蒽衍生物的方法。此类产物中可以方便地引入各种活性官能团，这些官能团化的多环芳烃可以进一步转化成更加复杂的多环化合物，也可以进一步转化为一些具有药理活性的多环分子，可以用于制备抗癌抗菌的药物，具有潜在的应用价值和商业用途。
附图说明
图1与图2分别是由X-ray单晶衍射获得的化合物2a和2b的结构图。
具体实施方式
通过以下实施例有助于理解本发明，但并不限制于本发明的内容。
实施例1---化合物2的合成的一般操作步骤
多环芳烃苯并[α]蒽2合成：在25mL干净反应管中，加入3-芳基-2-萘乙醛(1，0.20mmol)，路易斯酸In(OTf)3(0.01mmol)，在DCE(二氯乙烷)中加热到50℃反应2小时。快速柱层析(SiO2,洗脱剂为石油醚)得到相应的产物2。
Compound 2a:54mg,89％,白色固体，熔点：189-191℃；IR(CH2Cl2):ν2955,2922,2851,1663,1495,1469,1453,1411,1360,1224,1031,821,747,702cm-1；1H NMR(400MHz,CDCl3,TMS):δ7.39-7.44(m,3H),7.47(s,2H),7.51-7.61(m,5H),7.64-7.80(m,2H),7.79(dd,1H,J1＝7.6Hz,J2＝0.8Hz),8.15(d,1H,J＝8.0Hz),8.87(d,1H,J＝8.4Hz),9.24(s,1H)；13C NMR(100MHz,CDCl3,TMS):δ121.6,123.0,125.5,125.6,125.7,126.7,126.8,126.9,127.1,127.4,128.4,128.47,128.51,128.56,128.63,130.4,130.8,131.2,131.47,131.52,137.5,138.9；MS(ESI)m/z:305.1(M+H+,100)；HRMS(ESI)计算值Calcd.for C24H17 +requires:305.1325,实测值Found:305.1326.
Compound 2b:56mg,88％,白色固体，熔点：194-196℃；IR(CH2Cl2):ν2959,2923,2853,1251,1228,1177,1030,825,669cm-1；1H NMR(400MHz,CD2Cl2,TMS):δ2.55(s,3H),7.38-7.44(m,5H),7.52-7.63(m,7H),8.16(d,1H,J＝8.4Hz),8.77(d,1H,J＝8.4Hz),9.22(s,1H)；13C NMR(100MHz,CD2Cl2,TMS):δ21.2,121.2,123.0,125.49,125.52,125.6,126.6,126.8,127.5,128.1,128.3,128.4,128.50,128.52,128.6,130.7,131.2,131.6,131.7,137.3,137.5,139.0；MS(ESI)m/z:319.1(M+H+,100)；HRMS(ESI)Calcd.for C25H19 +requires:319.1481,Found:319.1486.
Compound 2c:55mg,86％,白色固体，熔点：190-192℃；IR(CH2Cl2):ν2961,2932,2853,1252,1229,1178,1032,826,700cm-1；1H NMR(400MHz,CD2Cl2,TMS):δ2.54(s,3H),7.36(d,1H,J＝7.2Hz),7.35-7.42(m,4H),7.53-7.64(m,7H),8.14(d,1H,J＝8.0Hz),8.78(d,1H,J＝8.0Hz),9.20(s,1H)；13C NMR(100MHz,CD2Cl2,TMS):δ21.4,121.0,123.2,125.4,125.5,125.6,126.7,126.8,128.0,128.1,128.2,128.3,128.4,128.5,128.6,130.7,131.3,131.5,131.8,137.6,137.8,139.2；MS(ESI)m/z:319.1(M+H+,100)；HRMS(ESI)Calcd.for C25H19 +requires:319.1481,Found:319.1485.
Compound 2d:61mg,84％,白色固体，熔点：197-199℃；IR(CH2Cl2):ν2958,2923,2868,1362,1263,1021,882,845,821,805,768,747cm-1；1H NMR(400MHz,CD2Cl2,TMS):δ1.47(s,9H),7.35(d,2H,J＝8.0Hz),7.41(t,1H,J＝7.6Hz),7.47(d,1H,J＝9.2Hz),7.51-7.54(m,2H),7.57-7.61(m,3H),7.66-7.71(m,2H),7.79(d,1H,J＝7.2Hz),8.14(d,1H,J＝8.4Hz),8.88(d,1H,J＝8.0Hz),9.23(s,1H)；13C NMR(100MHz,CD2Cl2,TMS):δ31.5,34.7,121.4,123.1,125.2,125.4,125.6,125.8,126.7,126.8,126.9,127.1,128.45,128.53,128.8,130.5,130.8,131.0,131.5,131.6,135.7,137.7,150.2；MS(ESI)m/z:361.2(M+H+,100)；HRMS(ESI)Calcd.for C28H25 +requires:361.1951,Found:361.1953.
Compound 2e:54mg,84％,白色固体，10:1的异构体，熔点：190-192℃；IR(CH2Cl2):ν3053,3028,2914,1617,1597,1508,1442,1073,1019,878,845,836,782,752,742,700,686cm-1；1H NMR(400MHz,CDCl3,TMS):δ2.65(s,3H),2.68(s,0.3H),7.38-7.46(m,6.6H),7.50-7.59(m,4.4H),7.64(d,1.1H,J＝8.4Hz),7.68(d,1.1H,J＝8.0Hz),8.15(d,1H,J＝8.4Hz),8.23(d,0.1H,J＝8.4Hz),8.67(s,1H),8.77(d,0.1H,J＝8.0Hz),9.23(s,1H),9.25(s,0.1H)；13C NMR(100MHz,CDCl3,TMS):δ22.2,121.5,123.1,124.6,125.3,125.6,126.6,126.7,127.4,128.32,128.35,128.4,128.5,128.6,128.8,129.3,130.4,130.8,131.2,131.4,136.6,139.0；MS(ESI)m/z:319.1(M+H+,100)；HRMS(ESI)Calcd.for C25H19 +requires:319.1481,Found:319.1487.
Compound 2f:58mg,94％,白色固体，熔点：184-186℃；IR(CH2Cl2):ν2917,2847,1662,1597,1448,1418,1317,1242,929,882,815,757,701cm-1；1H NMR(400MHz,CD2Cl2,TMS):δ7.37(td,1H,J1＝7.2Hz,J2＝0.8Hz),7.43(dd,1H,J1＝8.4Hz,J2＝1.6Hz),7.49-7.56(m,3H),7.58-7.61(m,3H),7.65-7.69(m,2H),8.11(d,1H,J＝8.4Hz),8.18(d,1H,J＝5.2Hz),8.91(s,1H)；13C NMR(100MHz,CD2Cl2,TMS):δ120.3,121.8,122.8,124.0,125.2,125.5,125.6,126.9,127.47,127.55,128.1,128.2,128.4,131.1,131.5,135.5,136.5,137.9,139.1；MS(ESI)m/z:311.1(M+H+,100)；HRMS(ESI)Calcd.for C22H15S+requires:311.0889,Found:311.0892.
Compound 2g:69mg,94％,白色固体，熔点：187-189℃；IR(CH2Cl2):ν2959,2922,2850,1652,1635,1470,1076,1021,875,824,745,701cm-1；1H NMR(400MHz,CD2Cl2,TMS):δ7.26(d,2H,J＝8.0Hz),7.40-7.43(m,2H),7.50(d,1H,J＝8.4Hz),7.54(td,1H,J1＝8.0Hz,J2＝0.8Hz),7.56-7.60(m,2H),7.66-7.72(m,3H),7.80(d,1H,J＝7.6Hz),8.13(d,1H,J＝8.0Hz),8.86(d,1H,J＝8.0Hz),9.23(s,1H)；13C NMR(100MHz,CD2Cl2,TMS):δ121.7,121.9,123.0,125.1,125.6,126.0,126.3,127.0,127.19,127.23,128.47,128.52,128.53,128.7,130.3,130.6,131.39,131.42,131.6,132.9,135.9,137.8；MS(ESI)m/z:339.1(M+H+,100)；HRMS(ESI)Calcd.for C24H16Cl+requires:339.0936,Found:339.0938.
Compound 2h:69mg,90％,白色固体，熔点：185-187℃；IR(CH2Cl2):ν2958,2920,2851,1654,1633,1469,1075,1019,873,822,742,700cm-1；1H NMR(400MHz,CD2Cl2,TMS):δ7.28(d,2H,J＝8.4Hz),7.40-7.44(m,2H),7.49(d,1H,J＝8.8Hz),7.53(td,1H,J1＝8.0Hz,J2＝1.2Hz),7.58-7.62(m,2H),7.66-7.71(m,3H),7.79(d,1H,J＝7.6Hz),8.14(d,1H,J＝8.0Hz),8.86(d,1H,J＝8.0Hz),9.23(s,1H)；13C NMR(100MHz,CD2Cl2,TMS):δ121.7,121.9,123.0,125.1,125.6,126.0,126.3,127.0,127.19,127.23,128.47,128.52,128.53,128.7,130.3,130.6,131.39,131.42,131.6,132.9,135.9,137.8；MS(ESI)m/z:383.0(M+H+,100)；HRMS(ESI)Calcd.for C24H16Br+requires:383.0430,Found:383.0435.
Compound 2i:59mg,93％,白色固体，熔点：193-195℃；IR(CH2Cl2):ν2961,2924,2852,1252,1229,1179,1032,826,670cm-1；1H NMR(400MHz,CD2Cl2,TMS):δ2.53(s,3H),7.35-7.43(m,5H),7.51-7.62(m,7H),8.17(d,1H,J＝8.0Hz),8.76(d,1H,J＝8.0Hz),9.21(s,1H)；13C NMR(100MHz,CD2Cl2,TMS):δ21.3,121.1,123.2,125.5,125.62,125.64,126.7,126.8,127.6,128.2,128.3,128.4,128.5,128.6,128.8,130.9,131.2,131.6,131.8,137.2,137.4,139.0；MS(ESI)m/z:319.1(M+H+,100)；HRMS(ESI)Calcd.for C25H19 +requires:319.1481,Found:319.1484.
Compound 2j:61mg,91％,白色固体，熔点：190-192℃；IR(CH2Cl2):ν2955,2921,2851,1626,1506,1464,1423,1266,1227,1168,1033,880,844,821,744,703cm-1；1H NMR(400MHz,CD2Cl2,TMS):δ3.68(s,3H),6.84(s,1H),7.20(dd,1H,J1＝8.8Hz,J2＝2.0Hz),7.40-7.50(m,4H),7.52-7.58(m,4H),7.64(t,1H,J＝7.6Hz),7.76(d,1H,J＝7.6Hz),8.01(d,1H,J＝9.2Hz),8.80(d,1H,J＝8.4Hz),9.13(s,1H)；13C NMR(100MHz,CD2Cl2,TMS):δ55.0,103.5,119.5,121.4,122.7,125.4,126.6,126.7,126.8,126.9,127.4,127.7,128.4,128.5,129.0,130.2,130.6,131.10,131.14,131.9,135.8,139.2,157.4；MS(ESI)m/z:335.1(M+H+,100)；HRMS(ESI)Calcd.for C25H19O+requires:335.1430,Found:335.1428.
Compound 2k:73mg,92％,白色固体，熔点：205-207℃；IR(CH2Cl2):ν3042,2963,2864,1498,1465,1351,1201,1110,1076,958,946,872,843,823,742,699cm-1；1H NMR(400MHz,CD2Cl2,TMS):δ1.47(s,9H),7.30(d,2H,J＝8.4Hz),7.44(dd,1H,J1＝8.8Hz,J2＝2.0Hz),7.49(brs,2H),7.57-7.62(m,3H),7.66-7.70(m,2H),7.79(d,1H,J＝7.6Hz),8.05(d,1H,J＝8.8Hz),8.83(d,1H,J＝8.4Hz),9.17(s,1H)；13C NMR(100MHz,CD2Cl2,TMS):δ31.5,34.7,121.4,123.0,125.3,125.4,125.6,126.5,127.0,127.30,127.32,128.5,128.7,129.5,129.6,130.2,130.3,130.7,131.4,131.47,131.55,134.9,137.0,150.5；MS(ESI)m/z:395.2(M+H+,100)；HRMS(ESI)Calcd.for C28H24Cl+requires:395.1561,Found:395.1570.
产物2l:38mg,53％,白色固体，熔点:220-222℃.IR(CH2Cl2):ν3050,2923,2848,1660,1494,1455,1441,893,818,786,765,735,702cm-1；1H NMR(400MHz,CD2Cl2,TMS):δ7.36-7.46(m,4H),7.50(dd,2H,J1＝7.6Hz,J2＝2.0Hz),7.57-7.70(m,5H),7.75(d,1H,J＝8.4Hz),7.85(d,1H,J＝8.4Hz),8.06(d,1H,J＝8.4Hz),8.23(s,1H),8.77(s,1H),8.88(d,1H,J＝8.4Hz),9.40(s,1H)；13C NMR(100MHz,CD2Cl2,TMS):δ121.8,123.1,125.2,125.4,125.5,125.8,126.8,127.0,127.1,127.4,127.6,127.9,128.4,128.48,128.51,128.7,129.9,130.0,130.6,131.3,131.4,131.55,131.57,137.1,139.1；MS(ESI)m/z:355.1(M+H+,100)；HRMS(ESI)Calcd.for C28H19 +requires:355.1481,Found:355.1478.
产物2m.43mg,67％,白色固体，熔点:212-214℃.IR(CH2Cl2):ν3051,2956,2920,2848,1599,1505,1469,1435,1158,1016,833,773,749,702cm-1；1H NMR(400MHz,CD2Cl2,TMS):δ7.23-7.50(m,3H),7.54-7.66(m,7H),7.71-7.74(m,2H),7.76(d,1H,J＝8.4Hz),7.93(d,1H,J＝8.4Hz),8.04(d,1H,J＝8.4Hz),8.17(d,1H,J＝8.4Hz),9.28(d,1H,J＝8.4Hz),9.66(s,1H)；13C NMR(100MHz,CD2Cl2,TMS):δ125.4,125.7,125.8,126.1,126.45,126.50,126.7,126.8,127.2,127.5,127.7,127.9,128.3,128.4,128.69,128.73,130.0,130.2,130.3,130.6,131.1,131.4,133.7,136.8,139.1；MS(ESI)m/z:355.1(M+H+,100)；HRMS(ESI)Calcd.for C28H19 +requires:355.1481,Found:355.1481。
实施例2---化合物3的合成
抗癌试剂3的合成：在充满氩气的25mL干净反应管中，加入多环芳烃2h(0.2mmol)，催化剂Pd2(dba)3(0.01mmol),配体XantPhos(4,5-双二苯基膦-9,9-二甲基氧杂蒽,0.02mmol),碱Cs2CO3(0.4mmol),吗啉(0.4mmol),在甲苯中加热到100℃，反应4小时。快速柱层析(SiO2,洗脱剂为石油醚/乙酸乙酯＝10/1)得到相应的产物3。
Compound 3:49mg,63％,白色固体，熔点:218-220℃；IR(CH2Cl2):ν2962,2919,2848,2820,1645,1607,1515,1502,1446,1257,1234,1122,928,831,822,803,770,751cm-1；1H NMR(400MHz,CD2Cl2,TMS):δ3.03(t,4H,J＝4.0Hz),3.94(t,4H,J＝4.0Hz),7.09(d,2H,J＝7.6Hz),7.33(d,2H,J＝8.4Hz),7.42(t,1H,J＝7.6Hz),7.54(t,1H,J＝7.6Hz),7.58-7.62(m,3H),7.68(d,1H,J＝8.0Hz),7.73(t,1H,J＝8.4Hz),7.81(d,1H,J＝8.0Hz),8.15(d,1H,J＝8.4Hz),8.89(d,1H,J＝8.4Hz),9.23(s,1H)；13C NMR(100MHz,CD2Cl2,TMS):δ49.1,67.0,115.2,121.3,123.1,125.4,125.6,125.8,126.6,126.83,126.84,127.1,128.4,128.6,129.0,130.0,130.5,131.2,131.5,131.6,132.0,137.5,150.3；MS(ESI)m/z:390.2(M+H+,100)；HRMS(ESI)Calcd.for C28H24NO+requires:390.1852,Found:390.1854。
实施例3化合物1的合成
反应式如下：
3-芳基-2-萘乙醛1合成：在充满氩气的干净反应管中，加入亚甲基环丙烷取代的1,5-烯炔(1，0.20mmol)，3,5-二溴吡啶氮氧化合物(0.3mmol)，金催化剂JohnPhosAu(NCMe)SbF6(0.01mmol)，在甲苯中加热到95℃反应4小时。快速柱层析(SiO2,洗脱剂为石油醚/乙酸乙酯＝25:1)得到相应的产物1。R1、R2和R3同前所述。
Compound 1a(R1＝Ph,R2＝Ph,R3＝H):59mg,92％,白色固体,熔点：143-145℃；IR(CH2Cl2):ν3055,2954,2923,2826,1722,1488,1442,1382,1109,1028,892,751,703cm-1；1HNMR(400MHz,CDCl3,TMS):δ3.63(s,2H),7.26(d,2H,J＝7.2Hz),7.33-7.40(m,4H),7.42-7.49(m,7H),7.80(s,1H),7.85(d,1H,J＝8.4Hz),9.41(s,1H)；13C NMR(100MHz,CDCl3,TMS):δ47.1,126.10,126.13,126.6,127.2,127.4,127.6,127.8,128.3,128.58,128.61,129.3,130.0,132.3,139.2,140.7,140.8,141.5,199.7；MS(ESI)m/z:323.1(M+H+,100)；HRMS(ESI)计算值Calcd.for C24H19O+实测值requires:323.1430,Found:323.1442.
Compound 1b(R1＝4-Me-Ph,R2＝Ph,R3＝H):58mg,86％,白色固体，熔点：149-151℃；IR(CH2Cl2):ν3054,3020,2922,2852,1777,1723,1594,1512,1442,1382,1109,1023,819,750,704cm-1；1H NMR(400MHz,CDCl3,TMS):δ2.39(s,3H),3.63(s,2H),7.19-7.26(m,6H),7.30-7.34(m,2H),7.39-7.48(m,4H),7.78(s,1H),7.83(d,1H,J＝8.0Hz),9.40(s,1H)；13C NMR(100MHz,CDCl3,TMS):δ21.2,47.1,126.00,126.04,126.6,127.4,127.6,127.7,128.5,128.6,129.0,129.2,130.0,132.2,132.3,137.0,138.5,139.2,140.6,140.8,199.8；MS(ESI)m/z:319.1(M+H+-H2O,100)；HRMS(ESI)Calcd.for C25H19 +requires:319.1481,Found:319.1495.
Compound 1c(R1＝4-OMe-Ph,R2＝Ph,R3＝H):61mg,87％,白色固体，熔点：153-155℃；IR(CH2Cl2):ν3059,2954,2922,2848,1772,1720,1608,1512,1286,1247,1176,1031,832,752,704cm-1；1H NMR(400MHz,CDCl3,TMS):δ3.64(s,2H),3.84(s,3H),6.95(d,2H,J＝8.8Hz),7.24-7.27(m,4H),7.34(d,2H,J＝4.0Hz),7.43-7.49(m,4H),7.79(s,1H),7.84(d,1H,J＝8.0Hz),9.42(s,1H)；13C NMR(100MHz,CDCl3,TMS):δ47.1,55.3,113.7,126.0,126.1,126.6,127.58,127.63,127.7,128.6,128.8,130.0,130.4,132.2,132.4,133.8,139.3,140.5,140.6,158.9,199.8；MS(ESI)m/z:335.1(M+H+-H2O,100)；HRMS(ESI)Calcd.for C25H19O+requires:335.1430,Found:335.1440.
Compound 1d(R1＝4-Cl-Ph,R2＝Ph,R3＝H):61mg,85％,白色固体，熔点：156-158℃；IR(CH2Cl2):ν2956,2922,2851,1722,1714,1488,1385,1087,1015,894,831,824,758,746,705cm-1；1H NMR(400MHz,CDCl3,TMS):δ3.61(s,2H),7.24-7.29(m,4H),7.35-7.40(m,4H),7.44-7.50(m,4H),7.76(s,1H),7.85(d,1H,J＝8.0Hz),9.42(s,1H)；13C NMR(100MHz,CDCl3,TMS):δ47.1,126.27,126.30,126.7,127.0,127.7,127.8,128.5,128.62,128.65,129.9,130.7,132.3,132.4,133.6,139.1,139.6,140.0,140.9,199.5；MS(ESI)m/z:339.1(M+H+-H2O,100)；HRMS(ESI)Calcd.for C24H16Cl+requires:339.0935,Found:339.0946.
Compound 1e(R1＝3-Me-Ph,R2＝Ph,R3＝H):60mg,90％,白色固体，熔点：144-146℃；IR(CH2Cl2):ν3056,2956,2915,2868,1708,1598,1484,1382,1299,1261,1093,1018,800,787,748,702cm-1；1H NMR(400MHz,CDCl3,TMS):δ2.40(s,3H),3.63(s,2H),7.12-7.20(m,3H),7.24-7.27(m,3H),7.30-7.36(m,2H),7.43-7.50(m,4H),7.80(s,1H),7.85(d,1H,J＝8.0Hz),9.42(s,1H)；13C NMR(100MHz,CDCl3,TMS):δ21.4,47.0,126.00,126.04,126.3,126.6,127.3,127.6,127.7,128.08,128.11,128.51,128.54,129.98,130.01,132.2,132.3,137.9,139.2,140.7,141.0,141.4,199.7；MS(ESI)m/z:319.1(M+H+-H2O,100)；HRMS(ESI)Calcd.for C25H19 +requires:319.1481,Found:319.1496.
Compound 1f(R1＝3-F-Ph,R2＝Ph,R3＝H):55mg,81％,白色固体，熔点：145-147℃；IR(CH2Cl2):ν3059,2967,2815,2718,1720,1611,1580,1486,1442,1263,1028,878,789,749,701cm-1；1H NMR(400MHz,CDCl3,TMS):δ3.63(s,2H),7.06-7.12(m,3H),7.24-7.26(m,2H),7.34-7.40(m,3H),7.44-7.50(m,4H),7.79(s,1H),7.86(d,1H,J＝8.0Hz),9.42(s,1H)；13C NMR(100MHz,CDCl3,TMS):δ47.0,114.4(d,JC-F＝20.8Hz),116.4(d,JC-F＝21.6Hz),125.2(d,JC-F＝3.0Hz),126.27,126.33,126.6,126.9,127.7(d,JC-F＝8.2Hz),128.57,128.61,129.8(d,JC-F＝8.2Hz),129.9,132.2,132.5,139.0,139.5(d,JC-F＝2.2Hz),140.9,143.6,143.7,162.4(d,JC-F＝245.6Hz),199.4；19F NMR(376MHz,CDCl3,CFCl3):δ-112.7(ddd,1F,J1＝14.7Hz,J2＝9.0Hz,J3＝5.6Hz)；MS(ESI)m/z:341.1(M+H+,100)；HRMS(ESI)Calcd.for C24H18FO+requires:341.1336,Found:341.1352.
Compound 1g(R1＝2-Me-Ph,R2＝Ph,R3＝H):57mg,85％,白色固体，熔点：142-144℃；IR(CH2Cl2):ν3054,2974,2895,1721,1487,1442,1381,1087,1045,880,751,732,704cm-1；1H NMR(400MHz,CDCl3,TMS):δ2.10(s,3H),3.38(d,1H,J＝17.6Hz),3.55(d,1H,J＝17.6Hz),7.16-7.29(m,6H),7.33(d,1H,J＝7.6Hz),7.36-7.47(m,5H),7.71(s,1H),7.83(d,1H,J＝8.4Hz),9.30(s,1H)；13C NMR(100MHz,CDCl3,TMS):δ20.1,46.7,125.6,126.0,126.6,127.6,127.7,127.8,128.1,128.5,128.6,129.8,129.9,130.0,130.1,132.3,132.4,135.8,139.0,140.0,140.6,140.8,199.0；MS(ESI)m/z:319.1(M+H+-H2O,100)；HRMS(ESI)Calcd.for C25H19 +requires:319.1481,Found:319.1494.
Compound 1h(R1＝cyclopropyl,R2＝Ph,R3＝H):61mg,84％,白色固体，熔点：132-134℃；IR(CH2Cl2):ν3056,3001,2930,2832,1719,1489,1386,1208,1043,1025,920,890,750,703cm-1；1H NMR(400MHz,CDCl3,TMS):δ0.75-0.79(m,2H),0.95-0.99(m,2H),1.87-1.93(m,1H),3.89(s,2H),7.21-7.22(m,2H),7.24-7.30(m,2H),7.38-7.49(m,4H),7.61(s,1H),7.78(d,1H,J＝8.0Hz),9.67(s,1H)；13C NMR(100MHz,CDCl3,TMS):δ7.0,14.8,46.3,125.3,125.5,125.8,126.5,127.4,127.5,128.6,129.4,129.9,131.7,132.7,139.4,139.5,140.4,200.0；MS(ESI)m/z:287.1(M+H+,100)；HRMS(ESI)Calcd.for C21H19O+requires:287.1430,Found:287.1432.
Compound 1i(R1＝nbutyl,R2＝Ph,R3＝H):57mg,76％,白色固体，熔点：138-140℃；IR(CH2Cl2):ν3051,2955,2928,2870,1720,1490,1442,1380,1027,883,749,703cm-1；1HNMR(400MHz,CDCl3,TMS):δ0.98(t,3H,J＝7.6Hz),1.43-1.49(m,2H),1.63-1.71(m,2H),2.71(t,2H,J＝7.6Hz),3.72(s,2H),7.21-7.22(m,2H),7.27-7.28(m,2H),7.41-7.49(m,4H),7.73(s,1H),7.80(d,1H,J＝8.4Hz),9.61(s,1H)；13C NMR(100MHz,CDCl3,TMS):δ14.0,22.7,32.8,33.5,46.0,125.3,125.8,126.5,127.22,127.23,127.5,128.6,130.0,131.6,132.8,139.2,139.6,140.7,199.9；MS(ESI)m/z:303.2(M+H+,100)；HRMS(ESI)Calcd.forC22H23O+requires:303.1743,Found:303.1738.
Compound 1j(R1＝thienyl,R2＝Ph,R3＝H):54mg,83％,白色固体，熔点：146-148℃；IR(CH2Cl2):ν3101,3054,2967,2923,1720,1488,1380,1073,1046,1027,895,880,853,790,765,750,703cm-1；1H NMR(400MHz,CDCl3,TMS):δ3.66(s,2H),7.10(dd,1H,J1＝5.2Hz,J2＝1.2Hz),7.23-7.26(m,3H),7.34-7.35(m,2H),7.38-7.40(m,1H),7.43-7.50(m,4H),7.84-7.86(m,2H),9.46(s,1H)；13C NMR(100MHz,CDCl3,TMS):δ47.2,123.5,125.7,126.1,126.2,126.6,127.6,127.7,128.6,128.9,129.0,129.9,132.3,132.4,135.6,139.2,140.7,141.6,199.8；MS(ESI)m/z:329.1(M+H+,100)；HRMS(ESI)Calcd.for C22H17OS+requires:329.0994,Found:329.0999.
Compound 1k(R1＝naphthyl,R2＝Ph,R3＝H):64mg,86％,白色固体，熔点：162-164℃；IR(CH2Cl2):ν3051,2926,2829,1720,1446,1393,1381,1110,1018,803,780,751,703cm-1；1H NMR(400MHz,CDCl3,TMS):δ3.31(dd,1H,J1＝18.0Hz,J2＝0.8Hz),3.46(dd,1H,J1＝18.0Hz,J2＝0.8Hz),7.28(dd,1H,J1＝7.2Hz,J2＝0.8Hz),7.35-7.53(m,12H),7.84(d,2H,J＝6.8Hz),7.89(t,2H,J＝6.8Hz),9.23(s,1H)；13C NMR(100MHz,CDCl3,TMS):δ46.9,125.3,125.8,126.0,126.17,126.22,126.4,126.7,127.62,127.65,127.8,128.1,128.3,128.4,128.5,128.6,129.4,130.0,130.2,132.2,132.4,132.6,133.5,138.6,138.7,139.0,140.8,199.1；MS(ESI)m/z:355.1(M+H+-H2O,100)；HRMS(ESI)Calcd.for C28H19 +requires:355.1481,Found:355.1476.
Compound 1l(R1＝Ph,R2＝3-Me-Ph,R3＝H):58mg,86％,白色固体，熔点：147-149℃；IR(CH2Cl2):ν3056,2956,2922,2852,1722,1603,1495,1442,1380,1109,1029,892,763,752,704cm-1；1H NMR(400MHz,CDCl3,TMS):δ2.40(s,3H),3.63(s,2H),7.05-7.08(m,2H),7.24(d,1H,J＝7.6Hz),7.32-7.48(m,9H),7.79(s,1H),7.84(d,1H,J＝8.0Hz),9.41(s,1H)；13C NMR(100MHz,CDCl3,TMS):δ21.4,47.0,126.0,126.1,126.7,127.1,127.2,127.4,127.7,128.25,128.32,128.4,128.5,129.3,130.6,132.31,132.33,138.2,139.1,140.8,140.9,141.5,199.7；MS(ESI)m/z:319.1(M+H+-H2O,100)；HRMS(ESI)Calcd.for C25H19 +requires:319.1481,Found:319.1495.
Compound 1m(R1＝Ph,R2＝2-Me-Ph,R3＝H):57mg,85％,白色固体，熔点：143-145℃；IR(CH2Cl2):ν3056,3020,2923,2823,1722,1494,1484,1443,1380,1109,1027,892,751,729,703cm-1；1H NMR(400MHz,CDCl3,TMS):δ1.94(s,3H),3.48(d,1H,J＝17.6Hz),3.66(d,1H,J＝17.6Hz),7.14(d,1H,J＝7.6Hz),7.24(d,1H,J＝8.4Hz),7.27-7.31(m,1H),7.33-7.49(m,9H),7.81(s,1H),7.87(d,1H,J＝8.0Hz),9.36(s,1H)；13C NMR(100MHz,CDCl3,TMS):δ19.7,46.7,126.1,126.2,126.3,127.3,127.4,127.9,128.0,128.28,128.29,128.52,128.54,129.4,130.3,131.8,132.4,136.7,138.4,140.0,141.0,141.5,199.3；MS(ESI)m/z:319.1(M+H+-H2O,100)；HRMS(ESI)Calcd.for C25H19 +requires:319.1481,Found:319.1477.
Compound 1n’(R1＝Ph,R2＝4-Me-Ph,R3＝H,醛不稳定，还原成醇):49mg,73％,白色固体，熔点：145-147℃；IR(CH2Cl2):ν3054,3023,2923,2876,1513,1491,1467,1380,1036,892,773,750,703cm-1；1H NMR(400MHz,CDCl3,TMS):δ1.09(s,1H),2.44(s,3H),2.85(t,2H,J＝7.2Hz),3.30(t,2H,J＝7.2Hz),7.19-7.21(m,2H),7.28-7.42(m,10H),7.69(s,1H),7.78(d,1H,J＝8.0Hz)；13C NMR(100MHz,CDCl3,TMS):δ21.3,34.2,62.5,125.6,125.8,126.6,127.0,127.6,128.1,128.7,129.1,129.4,130.1,131.5,131.7,132.6,136.5,136.8,140.0,140.9,142.1；MS(ESI)m/z:321.2(M+H+-H2O,100)；HRMS(ESI)Calcd.forC25H21 +requires:321.1638,Found:321.1649.
Compound 1o’(R1＝Ph,R2＝4-tBu-Ph,R3＝H,醛不稳定，还原成醇):64mg,84％,白色固体，熔点：154-156℃；IR(CH2Cl2):ν3054,2960,2881,1490,1464,1390,1364,1056,1017,899,832,769,744,700cm-1；1H NMR(400MHz,CDCl3,TMS):δ1.03(s,1H),1.41(s,9H),2.88(t,2H,J＝7.6Hz),3.34(t,2H,J＝7.6Hz),7.25(d,2H,J＝8.0Hz),7.32(brs,2H),7.37-7.44(m,6H),7.50(d,2H,J＝8.0Hz),7.70(s,1H),7.80(d,1H,J＝8.4Hz)；13C NMR(100MHz,CDCl3,TMS):δ31.5,34.3,34.6,62.6,125.2,125.6,125.8,126.7,127.1,127.6,128.1,128.8,129.4,129.9,131.5,131.7,132.7,136.4,140.1,140.9,142.1,150.0；MS(ESI)m/z:363.2(M+H+-H2O,100)；HRMS(ESI)Calcd.for C28H27 +requires:363.2107,Found:363.2113.
Compound 1p’(R1＝Ph,R2＝4-OMe-Ph,R3＝H,醛不稳定，还原成醇):50mg,70％,白色固体，熔点：152-154℃；IR(CH2Cl2):ν3054,2954,2923,2851,1608,1513,1491,1462,1285,1245,1175,1031,835,750,704cm-1；1H NMR(400MHz,CDCl3,TMS):δ1.14(s,1H),2.87(t,2H,J＝7.6Hz),3.32(t,2H,J＝7.6Hz),3.87(s,3H),7.03(d,2H,J＝8.4Hz),7.24(d,2H,J＝8.4Hz),7.32-7.43(m,8H),7.70(s,1H),7.79(d,1H,J＝8.0Hz)；13C NMR(100MHz,CDCl3,TMS):δ34.3,55.2,62.5,113.8,125.6,125.8,126.6,127.0,127.6,128.1,128.7,129.4,131.3,131.6,131.7,131.8,132.9,139.7,141.0,142.1,158.7；MS(ESI)m/z:337.2(M+H+-H2O,100)；HRMS(ESI)Calcd.for C25H21O+requires:337.1587,Found:337.1600.
Compound 1q’(R1＝Ph,R2＝4-Cl-Ph,R3＝H,醛不稳定，还原成醇):52mg,72％,白色固体，熔点：154-156℃；IR(CH2Cl2):ν3059,2967,2873,1495,1487,1381,1088,1039,1016,895,833,777,703cm-1；1H NMR(400MHz,CDCl3,TMS):δ1.05(s,1H),2.84(t,2H,J＝7.6Hz),3.31(t,2H,J＝7.6Hz),7.26-7.28(m,3H),7.32-7.45(m,7H),7.48(d,2H,J＝8.0Hz),7.72(s,1H),7.81(d,1H,J＝8.0Hz)；13C NMR(100MHz,CDCl3,TMS):δ34.2,62.4,125.8,126.1,126.2,127.2,127.7,128.2,128.7,129.2,129.4,131.6,131.7,131.8,132.3,133.4,138.0,138.7,140.9,141.8；MS(ESI)m/z:341.1(M+H+-H2O,100)；HRMS(ESI)Calcd.for C24H18Cl+requires:341.1092,Found:341.1106.
Compound 1r’(R1＝Ph,R2＝4-Br-Ph,R3＝H,醛不稳定，还原成醇):64mg,79％,白色固体，熔点：158-160℃；IR(CH2Cl2):ν3053,3023,2914,1484,1442,1070,1011,878,835,747,700cm-1；1H NMR(400MHz,CDCl3,TMS):δ1.13(s,1H),2.82(t,2H,J＝7.6Hz),3.27(t,2H,J＝7.6Hz),7.20(d,2H,J＝8.4Hz),7.26(d,1H,J＝8.4Hz),7.31(d,1H,J＝7.2Hz),7.34-7.37(m,1H),7.40-7.44(m,5H),7.61(d,2H,J＝8.0Hz),7.71(s,1H),7.79(d,1H,J＝8.4Hz)；13C NMR(100MHz,CDCl3,TMS):δ34.1,62.3,121.5,125.8,126.07,126.14,127.1,127.7,128.2,129.2,129.3,131.5,131.6,131.7,132.0,132.2,138.5,138.6,140.8,141.8；MS(ESI)m/z:385.1(M+H+-H2O,100)；HRMS(ESI)Calcd.for C24H18Br+requires:385.0586,Found:385.0589.
Compound 1s’(R1＝Ph,R2＝4-CF3-Ph,R3＝H,醛不稳定，还原成醇):60mg,77％,白色固体，熔点：147-149℃；IR(CH2Cl2):ν3059,2945,2890,1491,1325,1160,1120,1106,1067,1055,1036,1019,856,750,701cm-1；1H NMR(400MHz,CDCl3,TMS):δ1.08(s,1H),2.82(t,2H,J＝7.6Hz),3.30(t,2H,J＝7.6Hz),7.18(d,1H,J＝8.4Hz),7.20-7.48(m,9H),7.75-7.76(m,2H),7.78(s,1H),7.82(d,1H,J＝8.0Hz)；13C NMR(100MHz,CDCl3,TMS):δ34.1,62.3,124.2(q,JC-F＝270.2Hz),125.4(q,JC-F＝3.7Hz),125.9,126.0,126.2,127.2,127.8,128.2,129.4,129.5,129.6(q,JC-F＝32.0Hz),130.8,131.4,131.8,132.0,138.5,140.9,141.7,143.6；19F NMR(376MHz,CDCl3,CFCl3):δ-62.3(s,3F)；MS(ESI)m/z:375.1(M+H+-H2O,100)；HRMS(ESI)Calcd.for C25H18F3 +requires:375.1355,Found:375.1365.
Compound 1t(R1＝Ph,R2＝Me,R3＝H):45mg,87％,白色固体，熔点：129-131℃；IR(CH2Cl2):ν3055,2925,2825,2718,1719,1495,1444,1381,1110,1022,888,777,764,747,703cm-1；1H NMR(400MHz,CDCl3,TMS):δ2.62(s,3H),3.91(s,2H),7.29(dd,1H,J1＝7.6Hz,J1＝1.2Hz),7.39-7.45(m,3H),7.48-7.57(m,2H),7.66(s,1H),7.82(d,1H,J＝7.6Hz),8.09(d,1H,J＝8.0Hz),9.69(s,1H)；13C NMR(100MHz,CDCl3,TMS):δ15.6,46.7,117.2,124.1,126.0,126.2,126.7,127.3,127.4,128.3,128.5,129.3,132.1,132.4,133.9,141.1,142.0,199.5；MS(ESI)m/z:243.1(M+H+-H2O,100)；HRMS(ESI)Calcd.for C19H15 +requires:243.1168,Found:243.1180.
Compound 1u’(R1＝Ph,R2＝thienyl,R3＝H,醛不稳定，还原成醇):24mg,36％,白色固体，熔点：150-152℃；IR(CH2Cl2):ν3101,3054,2967,2923,1486,1383,1074,1050,1029,896,880,855,766,750,703cm-1；1H NMR(400MHz,CDCl3,TMS):δ1.08(s,1H),2.99(t,2H,J＝7.6Hz),3.45(t,2H,J＝7.6Hz),7.07(brs,1H),7.21(t,1H,J＝4.0Hz),7.38-7.51(m,9H),7.75(s,1H)7.81(d,1H,J＝8.0Hz)；13C NMR(100MHz,CDCl3,TMS):δ34.7,63.0,125.9,126.2,126.28,126.33,127.1,127.2,127.6,128.2,128.6,129.4,130.1,131.7,131.9,133.7,134.4,139.8,140.8,141.7；MS(ESI)m/z:313.1(M+H+-H2O,100)；HRMS(ESI)Calcd.for C22H17S+requires:313.1045,Found:313.1052.
Compound 1v(R1＝Ph,R2＝Ph,R3＝5-Cl):62mg,87％,白色固体，熔点：155-157℃；IR(CH2Cl2):ν2961,2921,2850,1720,1654,1633,1489,1087,1046,1015,831,824,758,746,704,660cm-1；1H NMR(400MHz,CDCl3,TMS):δ3.62(s,2H),7.24(d,2H,J＝7.2Hz),7.31-7.33(m,2H),7.41-7.42(m,4H),7.48-7.50(m,3H),7.77(s,1H),7.79(d,1H,J＝8.8Hz),9.40(s,1H)；13C NMR(100MHz,CDCl3,TMS):δ47.2,125.5,127.1,127.6,128.0,128.35,128.40,128.6,128.8,129.2,129.4,129.9,130.6,132.0,133.0,138.5,140.0,141.1,141.2,199.3；MS(ESI)m/z:339.1(M+H+-H2O,100)；HRMS(ESI)Calcd.for C24H16Cl+requires:339.0935,Found:339.0940.
Compound 1w(R1＝Ph,R2＝Ph,R3＝5-OMe):62mg,88％,白色固体，熔点：151-153℃；IR(CH2Cl2):ν3054,2926,2826,2726,1721,1623,1592,1491,1395,1250,1227,1206,1029,890,756,703cm-1；1H NMR(400MHz,CDCl3,TMS):δ3.60(s,2H),3.64(s,3H),6.63(s,1H),7.14(dd,1H,J1＝8.8Hz,J2＝2.0Hz),7.26(d,2H,J＝6.8Hz),7.31-7.45(m,6H),7.48(d,2H,J＝6.8Hz),7.72(s,1H),7.74(d,2H,J＝8.8Hz),9.40(s,1H)；13C NMR(100MHz,CDCl3,TMS):δ47.1,55.0,105.2,118.5,127.2,127.61,127.62,127.9,128.2,128.3,128.7,129.3,129.4,129.9,133.5,138.6,139.4,139.5,141.6,157.7,199.7；MS(ESI)m/z:335.1(M+H+-H2O,100)；HRMS(ESI)Calcd.for C25H19O+requires:335.1430,Found:335.1438.
Compound 1x(R1＝Ph,R2＝Ph,R3＝4-Cl):61mg,85％,白色固体，熔点：158-160℃；IR(CH2Cl2):ν3059,3031,2920,2854,1722,1698,1495,1481,1380,1081,899,826,755,703cm-1；1H NMR(400MHz,CDCl3,TMS):δ3.61(s,2H),7.23-7.32(m,6H),7.37-7.50(m,6H),7.71(s,1H),7.83(s,1H),9.40(s,1H)；13C NMR(100MHz,CDCl3,TMS):δ47.1,126.3,126.9,127.6,127.67,127.75,127.9,128.37,128.43,128.7,129.2,129.9,130.6,132.0,133.0,138.7,140.8,141.1,142.1,199.4；MS(ESI)m/z:339.1(M+H+-H2O,100)；HRMS(ESI)Calcd.for C24H16Cl+requires:339.0935,Found:339.0939.
Compound 1y(R1＝Ph,R2＝4-tBu-Ph,R3＝5-Cl):67mg,81％,白色固体，熔点：165-167℃；IR(CH2Cl2):ν2961,2923,2864,1724,1587,1495,1481,1461,1444,1376,1269,1079,959,892,757,703cm-1；1H NMR(400MHz,CDCl3,TMS):δ1.40(s,9H),3.62(s,2H),7.15(d,2H,J＝8.0Hz),7.31(d,2H,J＝7.2Hz),7.37-7.43(m,5H),7.49(d,2H,J＝8.8Hz),7.75(s,1H),7.77(d,1H,J＝8.8Hz),9.40(s,1H)；13C NMR(100MHz,CDCl3,TMS):δ31.4,34.7,47.1,125.6,125.7,127.0,127.5,128.25,128.32,128.8,129.2,129.4,129.5,130.6,131.9,133.2,135.2,140.2,141.2,150.8,199.6；MS(ESI)m/z:395.2(M+H+-H2O,100)；HRMS(ESI)Calcd.for C28H24Cl+requires:395.1561,Found:395.1573.
Compound 1z(R1＝Ph,R2＝Ph,R3＝Ph):69mg,93％,白色固体，熔点：171-173℃；IR(CH2Cl2):ν3052,3020,2950,2924,1722,1599,1492,1441,1107,1023,901,889,770,744,703cm-1；1H NMR(400MHz,CDCl3,TMS):δ3.65(s,2H),7.32-7.45(m,9H),7.48-7.54(m,3H),7.77(d,1H,J＝8.8Hz),7.89(s,1H),7.94(s,1H),7.97(d,1H,J＝8.8Hz),8.40(s,1H),9.42(s,1H)；13C NMR(100MHz,CDCl3,TMS):δ47.3,125.3,125.67,125.68,126.1,127.0,127.4,127.7,128.3,128.62,128.64,128.7,129.4,130.1,130.6,131.1,131.67,131.72,139.3,140.3,140.6,141.5,199.6；MS(ESI)m/z:373.2(M+H+,100)；HRMS(ESI)Calcd.for C28H21O+requires:373.1587,Found:373.1585。

Claims (4)

1.一种多环芳烃化合物的合成方法，其特征是在有机溶剂中和30-80℃下，底物和路易斯酸催化剂反应1-2小时获得；
所述的底物和路易斯酸催化剂的摩尔比为1:0.025-0.020；
所述的路易斯酸催化剂是In(OTf)3，Sc(OTf)3，FeCl3或[ReBr(CO)3(thf)]2；
所述的底物具有如下的结构式：
所述的多环芳烃化合物具有如下的结构式：
式中，R1为H、杂芳基或C1-C10的烷基；
R2为芳基或杂芳基；
R3为氢、卤素、芳基、C1-C10的烷基或C1-C10的烷氧基；
上述的芳基为苯基、或者单取代或多取代的苯基；苯基上的取代基是氢、C1-C10烷基、C1-C10烷氧基、卤素；
上述的杂芳基为呋喃基、吡啶基或者噻吩基。
2.如权利要求1所述的方法，其特征是所述的底物的结构式为：
所述的多环芳烃化合物的结构式为：
所述的R1、R2和R3同权利要求1所述。
3.如权利要求1所述的方法，其特征是所述的有机溶剂为二氯甲烷、二氯乙烷、二氧六环、苯、甲苯、二甲苯、乙腈、二甲基亚砜、二甲基甲酰胺。
4.如权利要求1所述的方法，其特征是所述的产物经过快速柱层析纯化。
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