CN110183298A - 一种二苯并戊烯衍生物的制备方法 - Google Patents

一种二苯并戊烯衍生物的制备方法 Download PDF

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CN110183298A
CN110183298A CN201910389938.XA CN201910389938A CN110183298A CN 110183298 A CN110183298 A CN 110183298A CN 201910389938 A CN201910389938 A CN 201910389938A CN 110183298 A CN110183298 A CN 110183298A
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任红军
缪茂众
宋金钰
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Taizhou University
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Abstract

本发明公开了一种苯并戊烯衍生物的制备方法，包括如下步骤：将茚并茚酮衍生物溶于有机溶剂中，在还原剂作用下还原为茚并茚满醇衍生物。随后，在酸作用并加热的条件下，茚并茚满醇衍生物发生重排反应，经后处理得到相应的二苯并戊烯衍生物。该制备方法步骤简单，原料廉价易得，且反应无需在无水无氧条件下进行，另外也无需用到重金属作为催化剂，还可以通过设计合成出不同取代位置多样化取代的二苯并戊烯衍生物，便于操作的同时拓宽了此方法的应用性。

Description

一种二苯并戊烯衍生物的制备方法
技术领域
本发明属于有机合成领域，尤其涉及一种二苯并戊烯衍生物的制备方法。
背景技术
二苯并戊二烯作为一个独特的4n电子稳定的平面结构，已经被发现100多年了。由于一些特殊有趣的性质，如环戊二烯接受一个电子芳构化倾向的高电子亲和性，最近引起了有机化学家和材料化学家的极大兴趣。但是其合成的难度，特别是非对称的二苯并戊二烯的合成，仍然是一个挑战。尽管构建二苯并戊二烯是一个挑战，由Youngs等首先报道的过渡金属催化的方法在合成二苯并戊二烯结构上取得了很大的进展。Kawase,Tilley和Itami课题组相继报道了镍或钯催化的邻炔基溴苯和芳基的自偶联反应合成二苯并戊二烯结构的方法。Jin等也报道了邻炔基芳基氯和二芳基炔在过渡金属催化下交叉环合形成二苯并戊二烯结构的反应。
发明内容
本发明提供了一种合成二苯并戊二烯的制备方法，该制备方法步骤简单，原料使用茚并茚酮，经过简单还原生成茚并茚满醇，经过【1，2】重排后得到所述二苯并戊二烯衍生物。该操作过程简单，同时避免了使用贵重金属催化剂，便于操作和应用；此方法还可以轻易的扩大至百克级，为工业上大规模生产应用提供了可能。
一种二苯并戊烯衍生物的制备方法，包括如下步骤：
(1)将茚并茚酮衍生物溶于有机溶剂中，在还原剂作用下还原为茚并茚满醇衍生物；
(2)在酸作用并加热的条件下，茚并茚满醇衍生物发生重排反应，经后处理得到所述的二苯并戊烯衍生物；
所述的二苯并戊二烯的结构如式如(I)所示：
所述茚并茚满醇的结构如(II)所示：
所述的茚并茚酮衍生物的结构如式(III)所示：
反应式如下：
反应经历了羰基还原和酸性条件下碳正离子【1，2】迁移重排过程。在还原试剂的作用下，茚并茚酮的羰基被立体选择性的还原成相应的茚并茚满醇。该茚并茚满醇在酸性条件下，发生碳正离子重排后形成相应的二苯并戊二烯的结构。
本发明中，可选用的后处理过程包括：过滤，硅胶拌样，最后经过柱层析纯化得到相应的茚并茚满醇和二苯并戊烯衍生物，采用柱层析纯化为本领域常用的技术手段。
作为优选，R1、R2、R4各自独立地选自H、甲基、甲氧基、三氟甲基、Br或Cl。
作为优选，R3为甲基、乙基、丙基、丁基、异丙基、邻位或对位或间位取代的苯基、吡啶基、噻吩基或呋喃基。
上述的苯基上可以有各种取代基，例如甲基、甲氧基、F、Cl或Br等。
作为优选，所述的还原反应的时间为1～8小时，酸重排反应时间越2～24小时，反应时间过长过短都会影响反应的产率。
本发明中，能将原料充分溶解的有机溶剂都能使反应发生，但反应效率差别较大，优选为非质子性溶剂，非质子性溶剂能够有效地促进反应的进行；作为优选，还原反应所述的有机溶剂为乙腈，DMF，DCM或者二氧六环；作为进一步的优选，所述的有机溶剂为DCM，此时，各种原料都能以较高的转化率转化成产物。重排反应所述的有机溶剂为乙腈，DMF，DCM，DCE或者二氧六环；作为进一步的优选，所述的有机溶剂为DCE，此时，各种原料都能以较高的转化率转化成产物。
所述的有机溶剂的用量能将原料较好的溶解即可，1mmol的茚并茚酮衍生物或茚并茚满醇使用的有机溶剂的量约为3～5mL。
作为优选，所述的还原剂包括硼氢化钠、氢化铝锂、异丙基铝、氰基氢化铝锂和DIBAL-H等；作为进一步优选，还原剂为DIBAL-H，使用该还原剂，茚并茚酮能够高立体选择性高产率的转化为相应的茚并茚满醇。
作为优选，所述的酸包括HCl，H2SO4，HNO3,H3PO4，HOAc,CF3COOH，TsOH·H2O等。作为进一步优选，酸为TsOH·H2O，使用该酸，茚并茚满醇能够高产率的转化为相应的苯并戊二烯衍生物。
作为进一步的优选，所述的苯并戊二烯衍生物为式(I-1)-式(I-6)所示化合物中的一种：
上述制备方法中，所述的还原试剂DIBAL-H和酸TsOH·H2O都是工业化产品，都能从市场上方便地得到。所述的茚并茚酮衍生物可由相应的多取代芳基联烯酮经过简便快捷的方法制备得到。具体过程可参见实施例2的详细过程，反应式如下：
同现有技术相比，本发明的有益效果体现在：该制备方法无贵重过渡金属催化，这样不会出现残留的过渡金属对所得的苯并戊二烯衍生物的光电性质产生影响的现象，反应易于操作，后处理简便；反应原料廉价易得，反应底物可设计性强，底物官能团兼容性好，可根据实际需要设计合成出各种不同取代的非对称的苯并戊二烯衍生物，实用性较强。
具体实施方式
下面结合具体实施例对本发明做进一步的描述。
实施例1
零下78℃氮气保护下，往茚并茚酮1.1(409.8mg,1.0mmol)的干燥DCM溶液(5mL)滴加DIBAL-H(1.5M甲苯溶液,1.05mmol,1.05equiv)。滴加完后，在此温度下继续反应1.0小时后，往反应体系里加入10毫升水淬灭反应。DCM萃取(3×20mL)后合并有机层并用无水硫酸钠干燥，减压旋去有机溶剂后硅胶柱分离得相应的茚满醇1.2(342.0mg,85％)。白色固体，熔点：176-177℃(Petroleum ether/EtOAc)；Rf＝0.20(Petroleum ether/EtOAc＝5/1)；1HNMR(400MHz,CDCl3):δ7.85-7.83(m,1H),7.65-7.63(m,2H),7.57-7.50(m,5H)7.46-7.42(m,1H),7.36-7.35(m,2H),7.31-7.26(m,2H),7.24-7.18(m,4H),5.12(d,J＝11.2Hz,1H),2.06-2.03(m,1H)；13C NMR(100MHz,CDCl3):δ152.6,150.3,148.4,146.7,137.5,136.4,135.4,134.1,133.3,130.4,129.3,128.52,128.48,128.4,128.2,127.6,125.7,124.4,124.1,121.9,121.6,77.2,74.2；HRMS(ES+-TOF)calcd for C28H20ClO([M+H]+):407.1197,found 407.1184.
上一步所得的茚满醇1.2(123.3mg,0.3mmol,1.0equiv)溶于DCE(3mL)中，加入TsOH.H2O(114mg,0.6mmol,2.0equiv)后在80℃下反应12h。反应完成后，冷却后往反应体系里加入10毫升水淬灭反应。DCM萃取(3×20mL)后合并有机层并用无水硫酸钠干燥，减压旋去有机溶剂后硅胶柱分离得最终的产物二苯并戊烯1.3(106.7mg,85％)。红色固体，熔点：219-222℃(Petroleum ether/EtOAc)；Rf＝0.30(Petroleum ether/EtOAc＝20/1)；1H NMR(400MHz,CDCl3):δ7.64(d,J＝7.2Hz,2H),7.58(d,J＝8.4Hz,2H),7.52-7.42(m,5H),7.19(d,J＝6.8Hz,1H),7.14(d,J＝8.8Hz,1H),7.01(d,J＝7.2Hz,1H),6.94(d,J＝7.2Hz,1H),6.89(t,J＝7.2Hz,2H),6.83(d,J＝7.0Hz,2H)；13C NMR(100MHz,CDCl3):δ149.7,149.3,143.5,143.0,141.1,139.1,135.0,134.9,134.5,133.7,132.4,129.8,129.0,128.9,128.7,128.5,128.0,127.8,127.6,122.6,122.1,122.0,121.8；HRMS(ES+-TOF)calcd forC28H17ClNa([M+Na]+):411.0911,found411.0898.
实施例2
零下78℃氮气保护下，往茚并茚酮2.1(442.5mg,1.0mmol)的干燥DCM溶液(5mL)滴加DIBAL-H(1.5M甲苯溶液,1.05mmol,1.05equiv)。滴加完后，在此温度下继续反应1.0小时后，往反应体系里加入10毫升水淬灭反应。DCM萃取(3×20mL)后合并有机层并用无水硫酸钠干燥，减压旋去有机溶剂后硅胶柱分离得相应的茚满醇2.2(404.0mg,90％)。白色固体，熔点：92-95℃(Petroleum ether/EtOAc)；Rf＝0.25(Petroleum ether/EtOAc＝5/1)；1HNMR(400MHz,CDCl3):δ7.91-7.89(m,1H),7.79(s,1H),7.6-7.64(m,2H),7.58-7.53(m,4H),7.48-7.44(m,3H),7.39-7.37(m,1H),7.32-7.24(m,4H),7.23-7.17(m,1H),5.11(d,J＝12.0Hz,1H),2.22(d,J＝12.0Hz,1H)；13C NMR(100MHz,CDCl3):δ156.3,148.7,146.3,138.2,138.1,136.2,133.6,130.9,130.6,129.2,129.0,128.63,128.58,127.7,127.6,126.1,125.4,124.94,124.91,124.6,124.5,122.7,121.9,118.3,77.1,74.8；HRMS(ES+-TOF)calcd for C29H20F3O([M+H]+):441.1461,found 441.1448.
上一步所得的茚满醇2.2(133.4mg,0.3mmol,1.0equiv)溶于DCE(3mL)中，加入TsOH·H2O(114mg,0.6mmol,2.0equiv)后在80℃下反应12h。反应完成后，冷却后往反应体系里加入10毫升水淬灭反应。DCM萃取(3×20mL)后合并有机层并用无水硫酸钠干燥，减压旋去有机溶剂后硅胶柱分离得最终的产物二苯并戊烯2.3(96.0mg,72％)。红色固体，熔点：207-210℃(Petroleum ether/EtOAc)；Rf＝0.30(Petroleum ether/EtOAc＝20/1)；1H NMR(400MHz,CDCl3):δ7.67-7.64(m,4H),7.57-7.47(m,6H),7.38(s,1H),7.22(d,J＝7.2Hz,1H),7.10(d,J＝8.0Hz,1H),7.11-7.05(m,2H),6.96-6.92(m,1H),6.90-6.86(m,1H)；13CNMR(100MHz,CDCl3):δ152.7,149.4,145.3,142.8,141.6,139.3,135.5,134.9,133.3(q,JCF＝2.4Hz),129.4,129.1,128.9,128.8,128.4,128.0,125.6,124.9(q,JCF＝2.4Hz),123.1,122.9,121.9,118.1,118.1；HRMS(ES+-TOF)calcd for C29H17F3Na([M+Na]+):445.1175,found 445.1186.
其中，原料的制备方法如下：
将联烯酮(88.1mg,0.2mmol,1.0equiv)置于封管中并加入2毫升DCM溶解，随后加入FeCl3(65mg,0.4mmol,2.0equiv)并在50度下反应12h。反应结束，冷却后加入10毫升水并用乙酸乙酯萃取(3×10mL)。合并有机层，无水硫酸钠干燥后减压旋去有机溶剂，硅胶柱分离后得到黄色茚并茚酮(74.0mg,83％)，固体，熔点：214-216℃(Petroleum ether/EtOAc)；Rf＝0.40(Petroleum ether/EtOAc＝10/1)；1H NMR(400MHz,CDCl3):δ7.87-7.82(m,2H),7.76-7.71(m,3H),7.65(d,J＝8.0Hz,2H),7.60(t,J＝7.4Hz,2H),7.55-7.48(m,2H),7.44-7.42(m,1H),7.32-7.21(m,5H)；13C NMR(100MHz,CDCl3):δ194.1,146.9,145.2,144.6,144.2,141.1,139.0,136.0(q,JC-F＝90.9Hz),133.2,129.4,129.3,129.1,128.8,128.0,127.5,126.2,125.4,124.86,124.85,124.7,122.4,122.0,119.5,74.6；HRMS(ES+-TOF)calcd for C29H18F3O([M+H]+):439.1304,found439.1311.
反应式如下：
其他原料的制备方法可参考该实施例2。
实施例3
零下78℃氮气保护下，往茚并茚酮3.1(420.5mg,1.0mmol)的干燥DCM溶液(5mL)滴加DIBAL-H(1.5M甲苯溶液,1.05mmol,1.05equiv)。滴加完后，在此温度下继续反应1.0小时后，往反应体系里加入10毫升水淬灭反应。DCM萃取(3×20mL)后合并有机层并用无水硫酸钠干燥，减压旋去有机溶剂后硅胶柱分离得相应的茚满醇3.2(336.0mg,80％)。白色固体，熔点：207-208℃(Petroleum ether/EtOAc)；Rf＝0.25(Petroleum ether/EtOAc＝5/1)；1HNMR(400MHz,CDCl3):δ7.81-7.76(m,2H),7.52(d,J＝8.4Hz,1H),7.38(d,J＝8.4Hz,1H),7.30(t,J＝7.4Hz,1H),7.23-7.12(m,6H),7.05-6.96(m,4H),6.93-6.90(m,2H),6.86-6.73(m,2H),5.68-5.64(m,1H),4.48(d,J＝6.4Hz,1H),13.4(d,J＝11.6Hz,1H)；13C NMR(100MHz,CDCl3):δ145.1,143.7,142.5,139.7,138.9,138.1,137.8,133.9,130.3,130.1,129.5,128.7,128.2,127.7,127.3,127.03,126.99,126.8,126.5,125.3,125.1,121.8,76.5,64.6；HRMS(ES+-TOF)calcd for C32H23O([M+H]+):423.1743,found 423.1746.
上一步所得的茚满醇3.2(126.8mg,0.3mmol,1.0equiv)溶于DCE(3mL)中，加入TsOH·H2O(114mg,0.6mmol,2.0equiv)后在80℃下反应12h。反应完成后，冷却后往反应体系里加入10毫升水淬灭反应。DCM萃取(3×20mL)后合并有机层并用无水硫酸钠干燥，减压旋去有机溶剂后硅胶柱分离得最终的产物二苯并戊烯3.3(103.9mg,82％)。红色固体，熔点：218-220℃(Petroleum ether/EtOAc)；Rf＝0.30(Petroleum ether/EtOAc＝20/1)；1HNMR(400MHz,CDCl3):δ7.72-7.62(m,5H),7.45-7.31(m,8H),7.25-7.17(m,4H),7.07(t,J＝7.4Hz,1H),6.75(t,J＝7.6Hz,1H),6.50(s,1H)；13C NMR(100MHz,CDCl3):δ149.6,143.5,142.6,142.4,141.6,136.0,133.2,132.7,132.6,131.8,131.4,129.3,129.2,128.9,128.8,128.7,128.6,128.5,128.4,128.3,128.12,128.06,127.7,127.5,126.2,124.9,123.5,119.5；HRMS(ES+-TOF)calcd forC32H21([M+H]+):405.1638,found 405.1643.
实施例4
零下78℃氮气保护下，往茚并茚酮4.1(444.5mg,1.0mmol)的干燥DCM溶液(5mL)滴加DIBAL-H(1.5M甲苯溶液,1.05mmol,1.05equiv)。滴加完后，在此温度下继续反应1.0小时后，往反应体系里加入10毫升水淬灭反应。DCM萃取(3×20mL)后合并有机层并用无水硫酸钠干燥，减压旋去有机溶剂后硅胶柱分离得相应的茚满醇4.2(414.0mg,93％)。白色固体，熔点：168-170℃(Petroleum ether/EtOAc)；Rf＝0.25(Petroleum ether/EtOAc＝20/1)；1H NMR(400MHz,CDCl3):δ7.83-7.81(m,1H),7.64(d,J＝7.2Hz,2H),7.53(t,J＝7.6Hz,2H),7.47-7.42(m,3H),7.36-7.32(m,4H),7.29-7.26(m,2H),7.24-7.22(m,1H),7.03(d,J＝7.6Hz,1H),5.08(d,J＝11.6Hz,1H),2.30(s,3H),2.01-1.97(m,1H)；13C NMR(100MHz,CDCl3):δ150.3,149.9,148.3,146.7,138.4,138.2,136.0,135.5,134.2,131.3,130.8,129.4,129.1,128.5,128.2,127.6,125.6,124.3,123.8,122.5,121.5,121.4,74.4,21.6；HRMS(ES+-TOF)calcd for C29H21BrNaO([M+Na]+):487.0668,found 487.0666.
上一步所得的茚满醇4.2(133.8mg,0.3mmol,1.0equiv)溶于DCE(3mL)中，加入TsOH·H2O(114mg,0.6mmol,2.0equiv)后在80℃下反应12h。反应完成后，冷却后往反应体系里加入10毫升水淬灭反应。DCM萃取(3×20mL)后合并有机层并用无水硫酸钠干燥，减压旋去有机溶剂后硅胶柱分离得最终的产物二苯并戊烯4.3(84.8mg,63％)。红色固体，熔点：197-199℃(Petroleum ether/EtOAc)；Rf＝0.30(Petroleum ether/EtOAc＝20/1)；1H NMR(400MHz,CDCl3):δ7.66-7.63(m,4H),7.54-7.51(m,4H),7.45(t,J＝7.2Hz,1H),7.14(d,J＝6.8Hz,1H),7.01(d,J＝6.8Hz,2H),6.91-6.82(m,3H),6.70(d,J＝7.6Hz,1H),2.16(s,3H)；13C NMR(100MHz,CDCl3):δ149.6,146.6,143.0,142.9,140.7,139.5,137.6,135.3,135.0,133.9,133.0.131.9,130.1,128.8,128.7,128.5,128.2,127.8,127.4,123.2,122.7,122.5,122.0,121.7,21.4；HRMS(ES+-TOF)calcd for C29H20Br([M+H]+):447.0743,found 447.0753.
实施例5
零下78℃氮气保护下，往茚并茚酮5.1(476.5mg,1.0mmol)的干燥DCM溶液(5mL)滴加DIBAL-H(1.5M甲苯溶液,1.05mmol,1.05equiv)。滴加完后，在此温度下继续反应1.0小时后，往反应体系里加入10毫升水淬灭反应。DCM萃取(3×20mL)后合并有机层并用无水硫酸钠干燥，减压旋去有机溶剂后硅胶柱分离得相应的茚满醇5.2(444.0mg,93％)。白色固体，熔点：226-228℃(Petroleum ether/EtOAc)；Rf＝0.25(Petroleum ether/EtOAc＝5/1)；1HNMR(400MHz,CDCl3):δ7.70-7.68(m,2H),7.57(d,J＝7.2Hz,2H),7.51(d,J＝8.0Hz,2H),7.34(d,J＝7.6Hz,2H),7.29-7.24(m,4H),7.20-7.16(m,2H),7.09(d,J＝7.6Hz,1H),5.01(d,J＝8.0Hz,1H),2.46(s,3H),2.43(s,3H),2.06(d,J＝12.0Hz,1H)；13C NMR(100MHz,CDCl3):δ151.5,148.9,147.5,143.9,138.6,138.3,137.8,137.7,135.8,130.9,130.5,129.3,129.2,129.0,128.5,128.2,127.4,126.4,125.52,125.49,124.5,122.3,121.5,74.3,21.7,21.4；HRMS(ES+-TOF)calcd forC30H24BrO([M+H]+):479.1005,found 479.0992.
上一步所得的茚满醇5.2(143.5mg,0.3mmol,1.0equiv)溶于DCE(3mL)中，加入TsOH·H2O(114mg,0.6mmol,2.0equiv)后在80℃下反应12h。反应完成后，冷却后往反应体系里加入10毫升水淬灭反应。DCM萃取(3×20mL)后合并有机层并用无水硫酸钠干燥，减压旋去有机溶剂后硅胶柱分离得最终的产物二苯并戊烯5.3(107.6mg,75％)。红色固体，熔点：227-229℃(Petroleum ether/EtOAc)；Rf＝0.30(Petroleum ether/EtOAc＝20/1)；1HNMR(400MHz,CDCl3):δ7.62(d,J＝7.2Hz,2H),7.54-7.50(m,4H),7.44(t,J＝7.8Hz,1H),7.35-7.43(m,3H),7.01-7.00(m,2H),6.91(d,J＝7.6Hz,1H),6.85(d,J＝7.6Hz,1H),6.71(d,J＝7.6Hz,1H),2.46(s,3H),2.16(s,3H)；13C NMR(100MHz,CDCl3):δ148.3,146.7,143.3,142.8,140.7,139.3,139.2,137.9,137.2,135.5,133.7,130.6,129.8,129.5,128.8,128.7,128.4,128.31,128.27,124.6,123.20,123.16,122.7,121.4,21.5,21.4；HRMS(ES+-TOF)calcd for C30H22Br([M+H]+):461.0899,found 461.0885.
实施例6
零下78℃氮气保护下，往茚并茚酮6.1(400.5mg,1.0mmol)的干燥DCM溶液(5mL)滴加DIBAL-H(1.5M甲苯溶液,1.05mmol,1.05equiv)。滴加完后，在此温度下继续反应1.0小时后，往反应体系里加入10毫升水淬灭反应。DCM萃取(3×20mL)后合并有机层并用无水硫酸钠干燥，减压旋去有机溶剂后硅胶柱分离得相应的茚满醇6.2(352.0mg,88％)。白色固体，熔点：153-156℃(Petroleum ether/EtOAc)；Rf＝0.25(Petroleum ether/EtOAc＝5/1)；1HNMR(400MHz,CDCl3):δ7.99-7.97(m,1H),7.72(d,J＝7.2Hz,1H),7.54-7.50(m,2H),7.37(d,J＝7.6Hz,1H),7.28-7.10(m,10H),7.03(d,J＝7.6Hz,1H),5.12(s,1H),3.07-2.96(m,4H),2.11-2.03(m,1H)；13C NMR(100MHz,CDCl3):δ143.6,142.6,142.5,139.3,138.0,136.2,133.9,129.3,129.2,129.0,128.7,128.6,128.3,128.2,127.1,125.6,124.92,124.89,124.1,122.0,121.95,121.94,121.87,121.8,77.2,34.13,34.06；HRMS(ES+-TOF)calcd for C30H23O([M+H]+):399.1743,found399.1740.
上一步所得的茚满醇6.2(119.6mg,0.3mmol,1.0equiv)溶于DCE(3mL)中，加入TsOH·H2O(114mg,0.6mmol,2.0equiv)后在80℃下反应12h。反应完成后，冷却后往反应体系里加入10毫升水淬灭反应。DCM萃取(3×20mL)后合并有机层并用无水硫酸钠干燥，减压旋去有机溶剂后硅胶柱分离得最终的产物二苯并戊烯6.3(108.0mg,91％)。红色固体，熔点：185-186℃(Petroleum ether/EtOAc)；Rf＝0.30(Petroleum ether/EtOAc＝20/1)；1HNMR(400MHz,CDCl3):δ7.96-7.93(m,1H),7.64-7.63(m,2H),7.51-7.39(m,4H),7.32-7.30(m,2H),7.22-7.20(m,1H),7.05-7.00(m,2H),6.89-6.81(m,2H),6.75-6.63(m,2H),3.29-3.13(m,2H),2.86-2.83(m,2H)；13C NMR(100MHz,CDCl3):δ149.9,146.5,143.2,142.6,142.2,139.8,139.1,135.6,135.4,134.0,133.7,131.3,129.6,129.5,129.4,128.6,127.6,127.4,127.0,126.0,125.5,123.8,122.4,121.7,120.4,119.6,35.6,33.4；HRMS(ES+-TOF)calcd for C30H21([M+H]+):381.1638,found 381.1627。

Claims (10)

1.一种二苯并戊烯衍生物的制备方法，其特征在于，包括如下步骤：
(1)将茚并茚酮衍生物溶于有机溶剂中，在还原剂作用下进行还原反应得到茚并茚满醇衍生物；
(2)在酸作用并加热的条件下，茚并茚满醇衍生物发生重排反应，经后处理得到所述的二苯并戊烯衍生物；
所述的茚并茚酮衍生物的结构如式(III)所示：
所述的茚并茚满醇衍生物结构如式(II)所示：
所述的二苯并戊烯衍生物结构如式(I)所示：
在通式(I)、(II)和(III)中：
R1、R2、R4各自独立地选自H、C1-C5烷基、C1-C5烷氧基、三氟甲基、卤素中的一个或者多个；
R3选自H、卤素、C1-C5烷基和取代或者未取代的芳基。
2.根据权利要求1所述的二苯并戊烯衍生物的制备方法，其特征在于，R1为H、甲基、甲氧基、三氟甲基、Br或Cl。
3.根据权利要求1所述的二苯并戊烯衍生物的制备方法，其特征在于，R2为H、甲基、甲氧基、三氟甲基、Br或Cl。
4.根据权利要求1所述的二苯并戊烯衍生物的制备方法，其特征在于，R3为甲基、乙基、丙基、丁基、异丙基、邻位或对位或间位取代的苯基、吡啶基、噻吩基或呋喃基；
所述的苯基上的取代基可以为甲基、甲氧基、F、Cl或Br。
5.根据权利要求1所述的二苯并戊烯衍生物的制备方法，其特征在于，R4为H、甲基、甲氧基、三氟甲基、Br或Cl。
6.根据权利要求1所述的二苯并戊烯衍生物的制备方法，其特征在于，步骤(1)中，所述的还原剂为硼氢化钠、氢化铝锂、异丙基铝、氰基氢化铝锂或DIBAL-H。
7.根据权利要求1所述的二苯并戊烯衍生物的制备方法，其特征在于，还原反应的时间为1～8小时，重排反应的时间为2～24小时。
8.根据权利要求1所述的二苯并戊烯衍生物的制备方法，其特征在于，还原反应所用的溶剂为乙腈，DMF，DCM或者二氧六环；
重排反应所用的溶剂为乙腈，DMF，DCM，DCE或者二氧六环。
9.根据权利要求1所述的二苯并戊烯衍生物的制备方法，其特征在于，步骤(2)中，所述的酸为HCl、H2SO4、HNO3、H3PO4、HOAc、CF3COOH或TsOH·H2O。
10.根据权利要求1所述的二苯并戊烯衍生物的制备方法，其特征在于，所述的二苯并戊烯衍生物为式(I-1)-式(I-6)所示化合物中的一种：
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