CN114671850B - 一种共轭二烯化合物的制备方法 - Google Patents
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- 238000000034 method Methods 0.000 claims abstract description 13
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000009471 action Effects 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 83
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 27
- JKNHZOAONLKYQL-UHFFFAOYSA-K tribromoindigane Chemical compound Br[In](Br)Br JKNHZOAONLKYQL-UHFFFAOYSA-K 0.000 claims description 15
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 11
- 239000002841 Lewis acid Substances 0.000 claims description 5
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- 230000008569 process Effects 0.000 claims description 5
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims description 2
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 26
- 238000004440 column chromatography Methods 0.000 description 26
- 235000017557 sodium bicarbonate Nutrition 0.000 description 26
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 26
- 238000004809 thin layer chromatography Methods 0.000 description 26
- 150000001875 compounds Chemical class 0.000 description 25
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 25
- 239000000243 solution Substances 0.000 description 25
- 239000003039 volatile agent Substances 0.000 description 25
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical group COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 19
- 238000010791 quenching Methods 0.000 description 16
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 6
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- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 4
- OTWNHTGTCBAVGG-UHFFFAOYSA-N 1-methoxy-4-[1-(4-methoxyphenyl)ethenyl]benzene Chemical group C1=CC(OC)=CC=C1C(=C)C1=CC=C(OC)C=C1 OTWNHTGTCBAVGG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002820 allylidene group Chemical group [H]C(=[*])C([H])=C([H])[H] 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 125000003003 spiro group Chemical group 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000006880 cross-coupling reaction Methods 0.000 description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- 125000001424 substituent group Chemical group 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- DNXHEGUUPJUMQT-UHFFFAOYSA-N (+)-estrone Natural products OC1=CC=C2C3CCC(C)(C(CC4)=O)C4C3CCC2=C1 DNXHEGUUPJUMQT-UHFFFAOYSA-N 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical group CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
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- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- GPWHDDKQSYOYBF-UHFFFAOYSA-N ac1l2u0q Chemical compound Br[Br-]Br GPWHDDKQSYOYBF-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
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- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- XMSZANIMCDLNKA-UHFFFAOYSA-N methyl hypofluorite Chemical compound COF XMSZANIMCDLNKA-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
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- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
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- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- RMUKCGUDVKEQPL-UHFFFAOYSA-K triiodoindigane Chemical compound I[In](I)I RMUKCGUDVKEQPL-UHFFFAOYSA-K 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
- C07D339/08—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J33/00—Normal steroids having a sulfur-containing hetero ring spiro-condensed or not condensed with the cyclopenta(a)hydrophenanthrene skeleton
- C07J33/005—Normal steroids having a sulfur-containing hetero ring spiro-condensed or not condensed with the cyclopenta(a)hydrophenanthrene skeleton spiro-condensed
- C07J33/007—Cyclic thioketals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明属于有机化学领域,提供了一种共轭二烯化合物的制备方法。即以β‑卤代乙烯基‑1,3‑二噻烷衍生物和烯烃化合物为原料,在路易斯的作用下,发生两次硫迁移后得到共轭二烯化合物。本发明提供的方法是以廉价的路易斯作为催化剂,避免使用贵金属催化剂,同时反应条件温和、操作简单、底物适用性广,不需要无水无氧操作,具有很强的实用性及工业化应用的前景。本发明提供的方法可用于天然产物、药物分子和功能材料分子的合成和后期修饰。
Description
技术领域
本发明属于有机化学领域,具体涉及一种共轭二烯化合物的制备方法。
背景技术
共轭二烯化合物是一类重要的有机分子,它们存在于具有很好的生理、药理活性的天然产物和药物分子中(J.Am.Chem.Soc.2010,132,6663-6671.;Nat. Prod.Rep.2011,28,1790-1810.;J.Med.Chem.2012,55,3436-3451.;Molecules 2021,26,249.)。同时共轭二烯化合物也被广泛应用于功能材料中(J.Phys.Chem. C 2015,119,23890-23898.;Chem.Commun.,2014,50,6931-6934.)。此外,共轭二烯化合物由于其分子中存在不饱和双键,可以很容易地实现后期官能化。目前最简单最直接合成共轭二烯化合物的方法是通过两分子不同烯烃的交叉偶联来实现的。例如2009年,罗德平等人开发了一种钯催化的两分子烯烃的氧化偶联反应合成共轭二烯化合物的方法(J.Am.Chem.Soc.2009,131,1372–1373.)。2018 年,林国强小组发展了一种通过1,4-钯迁移串联Heck反应高立体选择性地合成了共轭二烯化合物的方法(Angew.Chem.Int.Ed.2018,57,5871–5875.)。2020 年,李亦菲课题组报道了一种可见光和金属协同催化两分子不同烯烃的交叉偶联来合成二烯化合物的方法(Org.Lett.2020,22,5,1692–1697.)。但是上述方法存在明显的局限性,比如要使用昂贵的贵金属催化剂钌、铑和钯;反应要在无水无氧的氛围中进行;要使用过量的氧化剂。因此开发一种非贵金属催化、条件温和、操作简单的合成共轭二烯化合物的方法是非常有价值的。
发明内容
本发明的目的是提供了一种共轭二烯化合物的制备方法,即在反应器中依次加入β-卤代乙烯基-1,3-二噻烷衍生物、烯烃化合物、合适的溶剂和路易斯,在合适的温度下反应得到一类共轭二烯化合物。该方法不需要贵金属催化、不需要无水无氧操作、条件温和、底物适用性广、立体选择性高、收率高。
本发明采用如下技术方案:在路易斯的作用下,β-卤代乙烯基-1,3-二噻烷衍生物和烯烃化合物溶解在有机溶剂中,在特定的温度下搅拌反应一段时间,待反应完全后分离纯化,得到共轭二烯化合物。所述技术方案的化学反应的方程式如下:
所述β-卤代乙烯基-1,3-二噻烷衍生物(I)中R1和R2为氢、亚甲基、C1- C6烷基、取代苯基(取代基选自氢、甲基、甲氧基、氟、氯、溴、三氟甲氧基、三氟甲基、硝基、苯基、甲酸甲酯、硼酸酯)、萘基、噻吩基、苯并噻吩基或雌酮衍生物;
n=0或者1;X为氯、溴或碘;
所述烯烃化合物(II)中R3和R4分别为取代苯基(取代基选自氢、甲基、甲氧基、氟、氯、溴、苄氧基、三氟甲氧基、炔丙氧基、2-甲-2-氧代丙炔酸异丙酯)、呋喃基、噻吩基或苯并噻吩基。
上述的技术方案中,所述路易斯酸为二氯化锌、二氯化铜、二氯化锡、三氯化铋、三氯化铁、三溴化铁、三氯化铟、三溴化铟、三碘化铟、三氟化硼乙醚中的一种或多种。
上述的技术方案中,所述有机溶剂为甲苯、氯苯、二氯甲烷、三氯甲烷、 1,2-二氯乙烷、1,2-二溴乙烷中的一种或多种。
上述的技术方案中,所述路易斯酸、β-卤代乙烯基-1,3-二噻烷衍生物、烯烃化合物的摩尔比为0.5~3.0:1.5:1。
上述的技术方案中,所述的反应具体步骤包括:反应瓶中依次加入β-氯代乙烯基-1,3-二噻烷衍生物、烯烃化合物、合适的溶剂和路易斯,在0~60℃下搅拌反应3~24小时,用薄层色谱法监测反应,待烯烃完全消耗完,反应体系中加入1摩尔/毫升的碳酸氢钠水溶液,并用二氯甲烷(15毫升)萃取三次,合并有机相,有机相用饱和食盐水(15毫升)洗涤三次,无水硫酸钠干燥,过滤,真空状态下除去挥发物,柱层析得产物。
具体实施方式
下面的实施例可以使本专业技术人员更全面的理解本发明,但不以任何方式限制本发明。本发明所用原料均为已知化合物,可由市场购得或采用本领域已知方法合成。
实施例1:化合物(E)-2-苯基-2-(4,4-二(4-甲氧基苯基)-1,3-丁二烯基)-1,3-二噻烷的制备:
在25毫升的圆底烧瓶中依次加入(Z)-2-(2-氯-2-苯基乙烯基)-1,3-二噻烷(77毫克,0.3毫摩尔)、1,1-二(4-甲氧基苯基)乙烯(48毫克,0.2毫摩尔)和6毫升1,2-二氯乙烷,加入三氟化硼乙醚(76微升,0.6毫摩尔)后在室温下搅拌,用薄层色谱法监测反应,反应结束后在反应体系中加入1摩尔/毫升的碳酸氢钠水溶液淬灭反应,并用二氯甲烷(15毫升)萃取三次,合并有机相,有机相用饱和食盐水(15毫升)洗涤三次,无水硫酸钠干燥,过滤,真空状态下除去挥发物后,柱层析得产物,收率69%。
在25毫升的圆底烧瓶中依次加入(Z)-2-(2-溴-2-苯基乙烯基)-1,3-二噻烷(90毫克,0.3毫摩尔)、1,1-二(4-甲氧基苯基)乙烯(48毫克,0.2毫摩尔)和6毫升1,2-二氯乙烷,加入三氟化硼乙醚(76微升,0.6毫摩尔)后在室温下搅拌,用薄层色谱法监测反应,反应结束后在反应体系中加入1摩尔/毫升的碳酸氢钠水溶液淬灭反应,并用二氯甲烷(15毫升)萃取三次,合并有机相,有机相用饱和食盐水(15毫升)洗涤三次,无水硫酸钠干燥,过滤,真空状态下除去挥发物后,柱层析得产物,收率71%。
实施例1所得产物(E)-2-苯基-2-(4,4-二(4-甲氧基苯基)-1,3-丁二烯基)-1,3-二噻烷的结构和核磁数据如下:
1H NMR(400MHz,Chloroform-d)δ7.81–7.74(m,2H),7.33(dd,J=8.3,6.8Hz,2H),7.27–7.21(m,3H),7.13–7.04(m,2H),6.88–6.79(m,4H),6.68(d,J=11.0 Hz,1H),6.45(dd,J=15.0,11.0Hz,1H),6.07(d,J=15.0Hz,1H),3.83(s,3H),3.80 (s,3H),2.94–2.81(m,2H),2.75–2.64(m,2H),2.09–1.86(m,2H).13C NMR(101 MHz,Chloroform-d)δ159.4,159.1,143.4,141.8,136.2,135.3,132.8,132.0,131.8, 129.2,128.6,128.5,127.9,124.9,113.7,113.6,59.3,55.43,55.39,28.7,24.7.
实施例2:化合物(E)-2-(4-甲基苯基)-2-(4,4-二(4-甲氧基苯基) -1,3-丁二烯基)-1,3-二噻烷的制备:
在25毫升的圆底烧瓶中依次加入(Z)-2-(2-氯-2-(4-甲基苯基)乙烯基)- 1,3-二噻烷(81毫克,0.3毫摩尔)、1,1-二(4-甲氧基苯基)乙烯(48毫克, 0.2毫摩尔)和6毫升1,2-二氯乙烷,加入三氟化硼乙醚(76微升,0.6毫摩尔) 后在室温下搅拌,用薄层色谱法监测反应,反应结束后在反应体系中加入1摩尔 /毫升的碳酸氢钠水溶液淬灭反应,并用二氯甲烷(15毫升)萃取三次,合并有机相,有机相用饱和食盐水(15毫升)洗涤三次,无水硫酸钠干燥,过滤,真空状态下除去挥发物后,柱层析得产物,收率72%。
实施例2所得产物(E)-2-(4-甲基苯基)-2-(4,4-二(4-甲氧基苯基) -1,3-丁二烯基)-1,3-二噻烷的结构和核磁数据如下:
1H NMR(400MHz,Chloroform-d)δ7.68–7.61(m,2H),7.24–7.19(m,2H),7.17–7.07(m,4H),6.89–6.78(m,4H),6.68(d,J=11.0Hz,1H),6.45(dd,J=15.0,11.0 Hz,1H),6.05(dd,J=15.0,0.6Hz,1H),3.83(s,3H),3.80(s,3H),2.95–2.80(m,2H), 2.79–2.62(m,2H),2.33(s,3H),2.08–1.98(m,1H),1.97–1.87(m,1H).13C NMR (101MHz,Chloroform-d)δ159.4,159.1,143.3,138.9,137.7,136.4,135.3,132.7, 132.1,131.8,129.2,129.1,128.4,124.9,113.7,113.6,59.1,55.44,55.38,28.8,24.8, 21.1.
实施例3:化合物(E)-2-(4-甲氧基苯基)-2-(4,4-二(4-甲氧基苯基) -1,3-丁二烯基)-1,3-二噻烷的制备:
在25毫升的圆底烧瓶中依次加入(Z)-2-(2-氯-2-(4-甲氧基苯基)乙烯基)-1,3-二噻烷(86毫克,0.3毫摩尔)、1,1-二(4-甲氧基苯基)乙烯(48毫克,0.2毫摩尔)和6毫升1,2-二氯乙烷,加入三氟化硼乙醚(76微升,0.6毫摩尔)后在室温下搅拌,用薄层色谱法监测反应,反应结束后在反应体系中加入1 摩尔/毫升的碳酸氢钠水溶液淬灭反应,并用二氯甲烷(15毫升)萃取三次,合并有机相,有机相用饱和食盐水(15毫升)洗涤三次,无水硫酸钠干燥,过滤,真空状态下除去挥发物后,柱层析得产物,收率76%。
实施例3所得产物(E)-2-(4-甲氧基苯基)-2-(4,4-二(4-甲氧基苯基)-1,3-丁二烯基)-1,3-二噻烷的结构和核磁数据如下:
1H NMR(400MHz,Chloroform-d)δ7.71–7.63(m,2H),7.25–7.19(m,2H),7.12–7.06(m,2H),6.89–6.79(m,6H),6.69(dd,J=11.1,0.7Hz,1H),6.43(dd,J=15.0, 11.0Hz,1H),6.05(dd,J=15.0,0.7Hz,1H),3.83(s,3H),3.80(s,3H),3.79(s,3H), 2.93–2.82(m,2H),2.73–2.63(m,2H),2.06–1.86(m,2H).13C NMR(101MHz, Chloroform-d)δ159.4,159.2,159.1,143.3,136.4,135.3,133.8,132.8,132.1,131.8, 129.9,129.1,124.9,113.8,113.7,113.6,58.8,55.44,55.41,55.36,28.9,24.8.
实施例4:化合物(E)-2-(4-氟苯基)-2-(4,4-二(4-甲氧基苯基)- 1,3-丁二烯基)-1,3-二噻烷的制备:
在25毫升的圆底烧瓶中依次加入(Z)-2-(2-氯-2-(4-氟苯基)乙烯基)- 1,3-二噻烷(82毫克,0.3毫摩尔)和1,1-二(4-甲氧基苯基)乙烯(48毫克, 0.2毫摩尔)和6毫升1,2-二氯乙烷,加入三溴化铟(106毫克,0.3毫摩尔)后在室温下搅拌,用薄层色谱法监测反应,反应结束后在反应体系中加入1摩尔/ 毫升的碳酸氢钠水溶液淬灭反应,并用二氯甲烷(15毫升)萃取三次,合并有机相,有机相用饱和食盐水(15毫升)洗涤三次,无水硫酸钠干燥,过滤,真空状态下除去挥发物后,柱层析得产物,收率58%。
实施例4所得产物(E)-2-(4-氟苯基)-2-(4,4-二(4-甲氧基苯基)- 1,3-丁二烯基)-1,3-二噻烷的结构和核磁数据如下:
1H NMR(400MHz,Chloroform-d)δ7.80–7.71(m,2H),7.25–7.18(m,2H),7.10–7.05(m,2H),7.03–6.96(m,2H),6.88–6.79(m,4H),6.67(dd,J=11.0,0.7Hz,1H), 6.37(dd,J=15.0,11.0Hz,1H),6.04(dd,J=15.1,0.8Hz,1H),3.83(s,3H),3.80(s, 3H),2.91–2.81(m,2H),2.72–2.64(m,2H),2.06–1.90(m,2H).13C NMR(101 MHz,Chloroform-d)δ162.3(d,J=247.6Hz),159.5,159.2,143.8,137.6(d,J=3.3 Hz),135.8,135.2,133.1,131.9,131.8,130.6(d,J=8.4Hz),129.2,124.6,115.3(d,J =21.6Hz)113.7,113.6,58.7,55.44,55.39,28.8,24.6.19F NMR(376MHz, Chloroform-d)δ-114.8.
实施例5:化合物(E)-2-(4-氯苯基)-2-(4,4-二(4-甲氧基苯基)- 1,3-丁二烯基)-1,3-二噻烷的制备:
在25毫升的圆底烧瓶中依次加入(Z)-2-(2-氯-2-(4-氯苯基)乙烯基)- 1,3-二噻烷(87毫克,0.3毫摩尔)和1,1-二(4-甲氧基苯基)乙烯(48毫克, 0.2毫摩尔)和6毫升1,2-二氯乙烷,加入三溴化铟(106毫克,0.3毫摩尔)后在室温下搅拌,用薄层色谱法监测反应,反应结束后在反应体系中加入1摩尔/ 毫升的碳酸氢钠水溶液淬灭反应,并用二氯甲烷(15毫升)萃取三次,合并有机相,有机相用饱和食盐水(15毫升)洗涤三次,无水硫酸钠干燥,过滤,真空状态下除去挥发物后,柱层析得产物,收率57%。
实施例5所得产物(E)-2-(4-氯苯基)-2-(4,4-二(4-甲氧基苯基)- 1,3-丁二烯基)-1,3-二噻烷的结构和核磁数据如下:
1H NMR(400MHz,Chloroform-d)δ7.77–7.69(m,2H),7.31–7.26(m,2H),7.23–7.18(m,2H),7.09–7.02(m,2H),6.89–6.78(m,4H),6.68–6.61(m,1H),6.33(dd, J=15.2,11.0Hz,1H),6.02(dd,J=15.1,0.8Hz,1H),3.84(s,3H),3.80(s,3H),2.89 –2.78(m,2H),2.74–2.62(m,2H),2.06–1.87(m,2H).13C NMR(101MHz, Chloroform-d)δ159.5,159.2,144.0,140.4,135.5,135.1,133.7,133.2,131.9,131.8, 130.3,129.2,128.6,124.5,113.7,113.5,58.8,55.43,55.41,28.7,24.5.
实施例6:化合物(E)-2-(4-溴苯基)-2-(4,4-二(4-甲氧基苯基)- 1,3-丁二烯基)-1,3-二噻烷的制备:
在25毫升的圆底烧瓶中依次加入(Z)-2-(2-氯-2-(4-溴苯基)乙烯基)- 1,3-二噻烷(100毫克,0.3毫摩尔)和1,1-二(4-甲氧基苯基)乙烯(48毫克, 0.2毫摩尔)和6毫升1,2-二氯乙烷,加入三溴化铟(106毫克,0.3毫摩尔)后在室温下搅拌,用薄层色谱法监测反应,反应结束后在反应体系中加入1摩尔/ 毫升的碳酸氢钠水溶液淬灭反应,并用二氯甲烷(15毫升)萃取三次,合并有机相,有机相用饱和食盐水(15毫升)洗涤三次,无水硫酸钠干燥,过滤,真空状态下除去挥发物后,柱层析得产物,收率55%。
实施例6所得产物(E)-2-(4-溴苯基)-2-(4,4-二(4-甲氧基苯基)- 1,3-丁二烯基)-1,3-二噻烷的结构和核磁数据如下:
1H NMR(400MHz,Chloroform-d)δ7.71–7.62(m,2H),7.47–7.41(m,2H),7.24–7.18(m,2H),7.09–7.02(m,2H),6.87–6.79(m,4H),6.64(dd,J=11.0,0.7Hz,1H), 6.32(dd,J=15.2,11.0Hz,1H),6.02(dd,J=15.0,0.7Hz,1H),3.84(s,3H),3.80(s, 3H),2.88–2.78(m,2H),2.74–2.63(m,2H),2.05–1.87(m,2H).13C NMR(101 MHz,Chloroform-d)δ159.5,159.2,144.0,141.0,135.4,135.1,133.2,131.8,131.7, 131.6,130.7,129.2,124.5,121.9,113.7,113.5,58.9,55.4,28.7,24.5.
实施例7:化合物(E)-2-(4-三氟甲氧基苯基)-2-(4,4-二(4-甲氧基苯基)-1,3-丁二烯基)-1,3-二噻烷的制备:
在25毫升的圆底烧瓶中依次加入(Z)-2-(2-氯-2-(4-三氟甲氧基苯基) 乙烯基)-1,3-二噻烷(102毫克,0.3毫摩尔)、1,1-二(4-甲氧基苯基)乙烯(48 毫克,0.2毫摩尔)和6毫升1,2-二氯乙烷,加入三氟化硼乙醚(76微升,0.6毫摩尔)后在室温下搅拌,用薄层色谱法监测反应,反应结束后在反应体系中加入 1摩尔/毫升的碳酸氢钠水溶液淬灭反应,并用二氯甲烷(15毫升)萃取三次,合并有机相,有机相用饱和食盐水(15毫升)洗涤三次,无水硫酸钠干燥,过滤,真空状态下除去挥发物后,柱层析得产物,收率60%。
实施例7所得产物(E)-2-(4-三氟甲氧基苯基)-2-(4,4-二(4-甲氧基苯基)-1,3-丁二烯基)-1,3-二噻烷的结构和核磁数据如下:
1H NMR(400MHz,Chloroform-d)δ7.87–7.79(m,2H),7.24–7.13(m,4H),7.10–7.04(m,2H),6.89–6.77(m,4H),6.66(d,J=11.0Hz,1H),6.34(dd,J=15.0,11.0 Hz,1H),6.04(d,J=15.0Hz,1H),3.82(s,3H),3.79(s,3H),2.91–2.79(m,2H),2.75 –2.64(m,2H),2.06–1.89(m,2H).13C NMR(101MHz,Chloroform-d)δ159.5,159.2, 148.7,144.0,140.4,135.5,135.1,133.2,131.8,131.7,130.4,129.2,124.5,120.7,120.6 (d,J=257.5Hz),113.7,113.5,58.7,55.4,55.3,28.7,24.5.19F NMR(376MHz, Chloroform-d)δ-57.7.
实施例8:化合物(E)-2-(4-三氟甲基苯基)-2-(4,4-二(4-甲氧基苯基)-1,3-丁二烯基)-1,3-二噻烷的制备:
在25毫升的圆底烧瓶中依次加入(Z)-2-(2-氯-2-(4-三氟甲基苯基)乙烯基)-1,3-二噻烷(97毫克,0.3毫摩尔)、1,1-二(4-甲氧基苯基)乙烯(48毫克,0.2毫摩尔)和6毫升1,2-二氯乙烷,加入三溴化铟(106毫克,0.3毫摩尔) 后在室温下搅拌,用薄层色谱法监测反应,反应结束后在反应体系中加入1摩尔 /毫升的碳酸氢钠水溶液淬灭反应,并用二氯甲烷(15毫升)萃取三次,合并有机相,有机相用饱和食盐水(15毫升)洗涤三次,无水硫酸钠干燥,过滤,真空状态下除去挥发物后,柱层析得产物,收率37%。
实施例8所得产物(E)-2-(4-三氟甲基苯基)-2-(4,4-二(4-甲氧基苯基)-1,3-丁二烯基)-1,3-二噻烷的结构和核磁数据如下:
1H NMR(400MHz,Chloroform-d)δ7.94(d,J=8.2Hz,2H),7.58(d,J=8.3Hz,2H),7.23–7.16(m,2H),7.06–6.99(m,2H),6.86–6.77(m,4H),6.63(d,J=10.8Hz, 1H),6.26(dd,J=15.2,11.0Hz,1H),6.04(dd,J=15.1,2.0Hz,1H),3.81(s,3H),3.79 (s,3H),2.88–2.77(m,2H),2.74–2.64(m,2H),2.06–1.87(m,2H).13C NMR(101 MHz,Chloroform-d)δ159.5,159.2,145.9(d,J=1.4Hz),144.3,135.1,135.0,133.3, 131.73,131.67,129.8(q,J=32.3Hz),129.4,129.2,125.4(q,J=3.9Hz),124.3,124.2 (q,J=272.2Hz),113.7,113.5,59.0,55.4,55.3,28.6,24.4.19F NMR(376MHz, Chloroform-d)δ-62.5.
实施例9:化合物(E)-2-(4-硝基苯基)-2-(4,4-二(4-甲氧基苯基) -1,3-丁二烯基)-1,3-二噻烷的制备:
在25毫升的圆底烧瓶中依次加入(Z)-2-(2-氯-2-(4-硝基苯基)乙烯基)- 1,3-二噻烷(90毫克,0.3毫摩尔)、1,1-二(4-甲氧基苯基)乙烯(48毫克, 0.2毫摩尔)和6毫升1,2-二氯乙烷,加入三溴化铟(106毫克,0.3毫摩尔)后在室温下搅拌,用薄层色谱法监测反应,反应结束后在反应体系中加入1摩尔/ 毫升的碳酸氢钠水溶液淬灭反应,并用二氯甲烷(15毫升)萃取三次,合并有机相,有机相用饱和食盐水(15毫升)洗涤三次,无水硫酸钠干燥,过滤,真空状态下除去挥发物后,柱层析得产物,收率28%。
实施例9所得产物(E)-2-(4-硝基苯基)-2-(4,4-二(4-甲氧基苯基) -1,3-丁二烯基)-1,3-二噻烷的结构和核磁数据如下:
1H NMR(400MHz,Chloroform-d)δ8.18(d,J=9.0Hz,2H),8.04–7.96(m,2H), 7.20(d,J=8.9Hz,2H),7.03(d,J=8.8Hz,2H),6.86–6.78(m,4H),6.64(d,J=10.9 Hz,1H),6.24(dd,J=15.2,10.9Hz,1H),6.02(d,J=15.2Hz,1H),3.81(s,3H),3.81 (s,3H),2.90–2.80(m,2H),2.75–2.61(m,2H),2.08–1.90(m,2H).13C NMR(101 MHz,Chloroform-d)δ159.6,159.2,149.3,147.2,144.7,134.8,134.4,133.8,131.7, 131.7,130.1,129.2,124.0,123.6,113.7,113.5,58.9,55.44,55.37,28.6,24.2.
实施例10:化合物(E)-2-(3-甲氧基苯基)-2-(4,4-二(4-甲氧基苯基)-1,3-丁二烯基)-1,3-二噻烷的制备:
在25毫升的圆底烧瓶中依次加入(Z)-2-(2-氯-2-(3-甲氧基苯基)乙烯基)-1,3-二噻烷(86毫克,0.3毫摩尔)、1,1-二(4-甲氧基苯基)乙烯(48毫克,0.2毫摩尔)和6毫升1,2-二氯乙烷,加入三氟化硼乙醚(76微升,0.6毫摩尔)后在室温下搅拌,用薄层色谱法监测反应,反应结束后在反应体系中加入1 摩尔/毫升的碳酸氢钠水溶液淬灭反应,并用二氯甲烷(15毫升)萃取三次,合并有机相,有机相用饱和食盐水(15毫升)洗涤三次,无水硫酸钠干燥,过滤,真空状态下除去挥发物后,柱层析得产物,收率70%。
实施例10所得产物(E)-2-(3-甲氧基苯基)-2-(4,4-二(4-甲氧基苯基)-1,3-丁二烯基)-1,3-二噻烷的结构和核磁数据如下:
1H NMR(400MHz,Chloroform-d)δ7.41–7.34(m,2H),7.25–7.19(m,3H),7.12–7.06(m,2H),6.88–6.76(m,5H),6.66(d,J=11.0Hz,1H),6.42(dd,J=15.0,11.0 Hz,1H),6.04(dd,J=15.0,0.7Hz,1H),3.83(s,3H),3.83–3.78(m,6H),2.91–2.80 (m,2H),2.76–2.66(m,2H),2.07–1.87(m,2H).13C NMR(101MHz,Chloroform- d)δ159.8,159.4,159.1,143.5,143.4,136.0,135.3,132.8,132.1,131.8,129.5,129.1, 124.8,121.0,114.5,113.7,113.5,113.3,59.3,55.43,55.39,28.8,24.7.
实施例11:化合物(E)-2-(3-氯苯基)-2-(4,4-二(4-甲氧基苯基) -1,3-丁二烯基)-1,3-二噻烷的制备:
在25毫升的圆底烧瓶中依次加入(Z)-2-(2-氯-2-(3-氯苯基)乙烯基)- 1,3-二噻烷(87毫克,0.3毫摩尔)、1,1-二(4-甲氧基苯基)乙烯(48毫克, 0.2毫摩尔)和6毫升1,2-二氯乙烷,加入三溴化铟(106毫克,0.3毫摩尔)后在室温下搅拌,用薄层色谱法监测反应,反应结束后在反应体系中加入1摩尔/ 毫升的碳酸氢钠水溶液淬灭反应,并用二氯甲烷(15毫升)萃取三次,合并有机相,有机相用饱和食盐水(15毫升)洗涤三次,无水硫酸钠干燥,过滤,真空状态下除去挥发物后,柱层析得产物,收率52%。
实施例11所得产物(E)-2-(3-氯苯基)-2-(4,4-二(4-甲氧基苯基) -1,3-丁二烯基)-1,3-二噻烷的结构和核磁数据如下:
1H NMR(400MHz,Chloroform-d)δ7.80(t,J=2.0Hz,1H),7.73–7.65(m,1H),7.26–7.18(m,4H),7.12–7.02(m,2H),6.90–6.78(m,4H),6.64(d,J=10.4Hz, 1H),6.30(dd,J=15.1,10.9Hz,1H),6.01(dd,J=15.1,0.7Hz,1H),3.84(s,3H),3.80 (s,3H),2.89–2.78(m,2H),2.74–2.64(m,2H),2.05–1.87(m,2H).13C NMR(101 MHz,Chloroform-d)δ159.5,159.2,144.1,143.9,135.2,135.1,134.5,133.2,131.9, 131.8,129.7,129.2,129.0,128.0,127.1,124.5,113.7,113.5,58.9,55.44,55.41,28.7, 24.5.
实施例12:化合物(E)-2-(4-苯基苯基)-2-(4,4-二(4-甲氧基苯基) -1,3-丁二烯基)-1,3-二噻烷的制备:
在25毫升的圆底烧瓶中依次加入(Z)-2-(2-氯-2-(4-苯基苯基)乙烯基)- 1,3-二噻烷(100毫克,0.3毫摩尔)、1,1-二(4-甲氧基苯基)乙烯(48毫克, 0.2毫摩尔)和6毫升1,2-二氯乙烷,加入三氟化硼乙醚(76微升,0.6毫摩尔) 后在室温下搅拌,用薄层色谱法监测反应,反应结束后在反应体系中加入1摩尔 /毫升的碳酸氢钠水溶液淬灭反应,并用二氯甲烷(15毫升)萃取三次,合并有机相,有机相用饱和食盐水(15毫升)洗涤三次,无水硫酸钠干燥,过滤,真空状态下除去挥发物后,柱层析得产物,收率68%。
实施例12所得产物(E)-2-(4-苯基苯基)-2-(4,4-二(4-甲氧基苯基) -1,3-丁二烯基)-1,3-二噻烷的结构和核磁数据如下:
1H NMR(400MHz,Chloroform-d)δ7.89–7.81(m,2H),7.61–7.52(m,4H),7.49–7.41(m,2H),7.38–7.31(m,1H),7.24–7.18(m,2H),7.12–7.04(m,2H),6.85– 6.76(m,4H),6.69(d,J=11.0Hz,1H),6.41(dd,J=15.1,11.1Hz,1H),6.10(dd,J= 15.0,0.6Hz,1H),3.80(s,3H),3.72(s,3H),2.95–2.84(m,2H),2.80–2.68(m,2H), 2.13–1.87(m,2H).13C NMR(101MHz,Chloroform-d)δ159.4,159.1,143.6,140.73, 140.70,136.0,135.2,133.0,131.9,131.8,129.2,128.9,127.5,127.2,124.7,113.7, 113.5,59.2,55.4,55.3,28.7,24.7.
实施例13:化合物(E)-2-(2-萘基)-2-(4,4-二(4-甲氧基苯基)-1, 3-丁二烯基)-1,3-二噻烷的制备:
在25毫升的圆底烧瓶中依次加入(Z)-2-(2-氯-2-(2-萘基)乙烯基)-1,3- 二噻烷(92毫克,0.3毫摩尔)、1,1-二(4-甲氧基苯基)乙烯(48毫克,0.2 毫摩尔)和6毫升1,2-二氯乙烷,加入三氟化硼乙醚(76微升,0.6毫摩尔)后在室温下搅拌,用薄层色谱法监测反应,反应结束后在反应体系中加入1摩尔/ 毫升的碳酸氢钠水溶液淬灭反应,并用二氯甲烷(15毫升)萃取三次,合并有机相,有机相用饱和食盐水(15毫升)洗涤三次,无水硫酸钠干燥,过滤,真空状态下除去挥发物后,柱层析得产物,收率67%。
实施例13所得产物(E)-2-(2-萘基)-2-(4,4-二(4-甲氧基苯基)-1, 3-丁二烯基)-1,3-二噻烷的结构和核磁数据如下:
1H NMR(400MHz,Chloroform-d)δ8.21(d,J=2.2Hz,1H),7.92(dd,J=8.7,2.0Hz,1H),7.89–7.78(m,3H),7.51–7.43(m,2H),7.24–7.17(m,2H),7.08–7.00(m, 2H),6.85–6.77(m,2H),6.76–6.64(m,3H),6.42(dd,J=15.0,11.0Hz,1H),6.20– 6.09(m,1H),3.79(s,3H),3.73(s,3H),2.93–2.83(m,2H),2.79–2.69(m,2H),2.09 –1.88(m,2H).13C NMR(101MHz,Chloroform-d)δ159.5,159.0,143.7,139.1,135.9, 135.2,133.3,133.0,132.9,131.9,131.7,129.2,128.5,128.2,127.9,127.5,126.6,126.4, 126.2,124.8,113.7,113.4,59.5,55.4,55.3,28.7,24.7.
实施例14:化合物(E)-2-(3,4-二甲氧基苯基)-2-(4,4-二(4-甲氧基苯基)-1,3-丁二烯基)-1,3-二噻烷的制备:
在25毫升的圆底烧瓶中依次加入(Z)-2-(2-氯-2-(3,4-二甲氧基苯基) 乙烯基)-1,3-二噻烷(95毫克,0.3毫摩尔)、1,1-二(4-甲氧基苯基)乙烯(48 毫克,0.2毫摩尔)和6毫升1,2-二氯乙烷,加入三溴化铟(106毫克,0.3毫摩尔)后在室温下搅拌,用薄层色谱法监测反应,反应结束后在反应体系中加入1 摩尔/毫升的碳酸氢钠水溶液淬灭反应,并用二氯甲烷(15毫升)萃取三次,合并有机相,有机相用饱和食盐水(15毫升)洗涤三次,无水硫酸钠干燥,过滤,真空状态下除去挥发物后,柱层析得产物,收率52%。
实施例14所得产物(E)-2-(3,4-二甲氧基苯基)-2-(4,4-二(4-甲氧基苯基)-1,3-丁二烯基)-1,3-二噻烷的结构和核磁数据如下:
1H NMR(600MHz,Chloroform-d)δ7.38(d,J=2.3Hz,1H),7.31–7.27(m,1H),7.23–7.19(m,2H),7.10–7.06(m,2H),6.87–6.77(m,5H),6.68(d,J=10.4Hz, 1H),6.40(dd,J=14.7,11.3Hz,1H),6.06(dd,J=15.1,0.9Hz,1H),3.89(s,3H),3.87 (s,3H),3.83(s,3H),3.80(s,3H),2.90–2.82(m,2H),2.75–2.68(m,2H),2.07–1.98 (m,1H),1.97–1.90(m,1H).13C NMR(151MHz,Chloroform-d)δ159.4,159.1,148.9, 148.7,143.4,136.2,135.2,134.1,132.8,132.0,131.8,129.1,124.7,121.1,113.7,113.5, 111.9,110.6,59.2,56.1,56.0,55.4,55.3,28.8,24.6.
实施例15:化合物(E)-2-(3,4,5-三甲氧基苯基)-2-(4,4-二(4- 甲氧基苯基)-1,3-丁二烯基)-1,3-二噻烷的制备:
在25毫升的圆底烧瓶中依次加入(Z)-2-(2-氯-2-(3,4,5-三甲氧基苯基)乙烯基)-1,3-二噻烷(104毫克,0.3毫摩尔)、1,1-二(4-甲氧基苯基)乙烯(48毫克,0.2毫摩尔)和6毫升1,2-二氯乙烷,加入三溴化铟(106毫克, 0.3毫摩尔)后在室温下搅拌,用薄层色谱法监测反应,反应结束后在反应体系中加入1摩尔/毫升的碳酸氢钠水溶液淬灭反应,并用二氯甲烷(15毫升)萃取三次,合并有机相,有机相用饱和食盐水(15毫升)洗涤三次,无水硫酸钠干燥,过滤,真空状态下除去挥发物后,柱层析得产物,收率32%。
实施例15所得产物(E)-2-(3,4,5-三甲氧基苯基)-2-(4,4-二(4- 甲氧基苯基)-1,3-丁二烯基)-1,3-二噻烷的结构和核磁数据如下:
1H NMR(600MHz,Chloroform-d)δ7.24–7.19(m,2H),7.10–7.04(m,4H),6.87–6.80(m,4H),6.66(d,J=11.0Hz,1H),6.40–6.30(m,1H),6.04(dd,J=15.1,0.9Hz, 1H),3.86(s,6H),3.84–3.82(m,6H),3.81(s,3H),2.88–2.80(m,2H),2.78–2.70 (m,2H),2.05–1.91(m,2H).13C NMR(151MHz,Chloroform-d)δ159.5,159.1,153.0, 143.7,137.5,137.1,135.8,135.1,132.9,131.9,131.7,129.1,124.6,113.7,113.5,106.1, 60.9,59.7,56.3,55.4,55.3,28.8,24.5.
实施例16:化合物(Z)-2-(4-甲基苯基)-2-(5,5-二(4-甲氧基苯基) -2,4-戊二烯基)-1,3-二噻烷的制备:
在25毫升的圆底烧瓶中依次加入(Z)-2-(2-氯-2-(4-甲氧基苯基)-2-丙烯基)-1,3-二噻烷(85毫克,0.3毫摩尔)、1,1-二(4-甲氧基苯基)乙烯(48毫克,0.2毫摩尔)和6毫升1,2-二氯乙烷,加入三溴化铟(106毫克,0.3毫摩尔) 后在室温下搅拌,用薄层色谱法监测反应,反应结束后在反应体系中加入1摩尔 /毫升的碳酸氢钠水溶液淬灭反应,并用二氯甲烷(15毫升)萃取三次,合并有机相,有机相用饱和食盐水(15毫升)洗涤三次,无水硫酸钠干燥,过滤,真空状态下除去挥发物后,柱层析得产物,收率43%。
实施例16所得产物(Z)-2-(4-甲基苯基)-2-(5,5-二(4-甲氧基苯基) -2,4-戊二烯基)-1,3-二噻烷的结构和核磁数据如下:
1H NMR(400MHz,Chloroform-d)δ7.60–7.46(m,2H),7.26–7.22(m,2H),7.19–7.08(m,4H),6.91–6.81(m,4H),6.79(d,J=11.2Hz,1H),6.68(d,J=11.2Hz,1H), 3.83(s,3H),3.81(s,3H),2.84–2.74(m,2H),2.67–2.59(m,2H),2.32(s,3H),2.03 –1.86(m,5H).13CNMR(101MHz,Chloroform-d)δ159.3,158.9,143.1,138.6,137.5, 137.3,135.9,132.4,131.9,129.5,129.25,129.15,128.5,122.5,113.7,113.5,65.0, 55.43,55.36,28.8,24.8,21.1,16.2.
实施例17:化合物(Z)-2-苯基-2-(4,4-二(4-甲氧基苯基)-1-苯基-1, 3-丁二烯基)-1,3-二噻烷的制备:
在25毫升的圆底烧瓶中依次加入2-(2-氯-1,2-二苯基乙烯基)-1,3-二噻烷(100毫克,0.3毫摩尔)、1,1-二(4-甲氧基苯基)乙烯(48毫克,0.2毫摩尔)和6毫升1,2-二氯乙烷,加入三溴化铟(106毫克,0.3毫摩尔)后在室温下搅拌,用薄层色谱法监测反应,反应结束后在反应体系中加入1摩尔/毫升的碳酸氢钠水溶液淬灭反应,并用二氯甲烷(15毫升)萃取三次,合并有机相,有机相用饱和食盐水(15毫升)洗涤三次,无水硫酸钠干燥,过滤,真空状态下除去挥发物后,柱层析得产物,收率38%。
实施例17所得产物(Z)-2-苯基-2-(4,4-二(4-甲氧基苯基)-1-苯基- 1,3-丁二烯基)-1,3-二噻烷的结构和核磁数据如下:
1H NMR(600MHz,Chloroform-d)δ7.81–7.74(m,2H),7.35–7.30(m,2H),7.26 (d,J=1.2Hz,1H),7.25–7.22(m,3H),7.11–7.07(m,2H),7.05–6.99(m,4H),6.89 –6.84(m,2H),6.80(d,J=11.1Hz,1H),6.73–6.69(m,2H),6.18(d,J=11.3Hz, 1H),3.87(s,3H),3.74(s,3H),2.78–2.71(m,2H),2.69–2.62(m,2H),1.97–1.89 (m,1H),1.89–1.82(m,1H).13C NMR(151MHz,Chloroform-d)δ159.3,159.1,144.2, 143.7,141.7,138.3,135.4,132.2,131.9,131.7,130.6,129.4,129.2,128.5,127.5,127.4, 127.3,123.4,113.6,113.5,63.8,55.42,55.36,29.0,24.5.
实施例18:化合物(E)-2-叔丁基-2-(4,4-二(4-甲氧基苯基)-1,3- 丁二烯基)-1,3-二噻烷的制备:
在25毫升的圆底烧瓶中依次加入(Z)-2-(2-氯-3,3-二甲基-1-丁烯基) -1,3-二噻烷(71毫克,0.3毫摩尔)、1,1-二(4-甲氧基苯基)乙烯(48毫克, 0.2毫摩尔)和6毫升1,2-二氯乙烷,加入三溴化铟(106毫克,0.3毫摩尔)后在室温下搅拌,用薄层色谱法监测反应,反应结束后在反应体系中加入1摩尔/ 毫升的碳酸氢钠水溶液淬灭反应,并用二氯甲烷(15毫升)萃取三次,合并有机相,有机相用饱和食盐水(15毫升)洗涤三次,无水硫酸钠干燥,过滤,真空状态下除去挥发物后,柱层析得产物,收率63%。
实施例18所得产物E)-2-叔丁基-2-(4,4-二(4-甲氧基苯基)-1,3-丁二烯基)-1,3-二噻烷的结构和核磁数据如下:
1H NMR(400MHz,Chloroform-d)δ7.25–7.20(m,2H),7.20–7.13(m,2H),6.93–6.87(m,2H),6.86–6.79(m,2H),6.73(d,J=11.0Hz,1H),6.56(dd,J=15.0,11.0 Hz,1H),5.95(d,J=15.0Hz,1H),3.85(s,3H),3.81(s,3H),2.86–2.77(m,2H),2.62 –2.55(m,2H),2.01–1.92(m,1H),1.79–1.68(m,1H),1.13(s,9H).13C NMR(101 MHz,Chloroform-d)δ159.3,159.1,142.0,135.8,135.5,134.2,132.3,131.8,129.0, 125.4,113.7,113.6,66.1,55.43,55.37,40.5,27.4,26.2,25.6.
实施例19:化合物(Z)-7-(3,3-二(4-甲氧基苯基)亚丙烯基)-1,5- 二硫代螺[5,5]十一烷的制备:
在25毫升的圆底烧瓶中依次加入(Z)-2-(2-氯环己烯)-1,3-二噻烷(70毫克,0.3毫摩尔)、1,1-二(4-甲氧基苯基)乙烯(48毫克,0.2毫摩尔)和6毫升1,2-二氯乙烷,加入三溴化铟(106毫克,0.3毫摩尔)后在室温下搅拌,用薄层色谱法监测反应,反应结束后在反应体系中加入1摩尔/毫升的碳酸氢钠水溶液淬灭反应,并用二氯甲烷(15毫升)萃取三次,合并有机相,有机相用饱和食盐水(15毫升)洗涤三次,无水硫酸钠干燥,过滤,真空状态下除去挥发物后,柱层析得产物,收率41%。
实施例19所得产物(Z)-7-(3,3-二(4-甲氧基苯基)亚丙烯基)-1, 5-二硫代螺[5,5]十一烷的结构和核磁数据如下:
1H NMR(400MHz,Chloroform-d)δ7.26–7.21(m,2H),7.21–7.16(m,2H),6.94–6.87(m,2H),6.85–6.78(m,3H),6.64(d,J=11.0Hz,1H),3.84(s,3H),3.81(s,3H), 2.75–2.62(m,4H),2.61–2.53(m,2H),2.05–2.00(m,2H),2.00–1.93(m,1H), 1.90–1.75(m,3H),1.65–1.58(m,2H).13C NMR(101MHz,Chloroform-d)δ159.2, 159.0,142.7,142.5,135.9,132.6,132.0,129.0,124.9,121.8,113.7,113.5,56.7,55.44, 55.42,41.7,27.9,27.3,26.0,25.7,22.2.
实施例20:化合物(E)-2-(2-噻吩基)-2-(4,4-二(4-甲氧基苯基) -1,3-丁二烯基)-1,3-二噻烷的制备:
在25毫升的圆底烧瓶中依次加入(Z)-2-(2-氯-2-噻吩基乙烯基)-1,3-二噻烷(79毫克,0.3毫摩尔)、1,1-二(4-甲氧基苯基)乙烯(48毫克,0.2毫摩尔)和6毫升1,2-二氯乙烷,加入三氟化硼乙醚(76微升,0.6毫摩尔)后在室温下搅拌,用薄层色谱法监测反应,反应结束后在反应体系中加入1摩尔/毫升的碳酸氢钠水溶液淬灭反应,并用二氯甲烷(15毫升)萃取三次,合并有机相,有机相用饱和食盐水(15毫升)洗涤三次,无水硫酸钠干燥,过滤,真空状态下除去挥发物后,柱层析得产物,收率64%。
实施例20所得产物(E)-2-(2-噻吩基)-2-(4,4-二(4-甲氧基苯基) -1,3-丁二烯基)-1,3-二噻烷的结构和核磁数据如下:
1H NMR(400MHz,Chloroform-d)δ7.26–7.24(m,1H),7.22–7.17(m,3H),7.08–7.03(m,2H),6.95–6.89(m,1H),6.88–6.76(m,4H),6.57(d,J=11.0Hz,1H),6.30 (dd,J=14.9,11.0Hz,1H),6.08(d,J=14.8Hz,1H),3.83(s,3H),3.80(s,3H),2.94 –2.85(m,2H),2.83–2.76(m,2H),2.02–1.91(m,2H).13C NMR(101MHz, Chloroform-d)δ159.4,159.0,148.3,144.2,135.7,135.2,132.3,131.8,129.3,128.2, 127.1,126.9,124.5,113.6,113.4,55.5,55.41,55.39,29.0,24.3.
实施例21:化合物(E)-2-(4-甲基苯基)-2-(4,4-二苯基-1,3-丁二烯基)-1,3-二噻烷的制备:
在25毫升的圆底烧瓶中依次加入(Z)-2-(2-氯-2-(4-甲氧基苯基)乙烯基)-1,3-二噻烷(86毫克,0.3毫摩尔)、1,1-二苯基乙烯(36毫克,0.2毫摩尔) 和6毫升1,2-二氯乙烷,加入三氟化硼乙醚(76微升,0.6毫摩尔)后在室温下搅拌,用薄层色谱法监测反应,反应结束后在反应体系中加入1摩尔/毫升的碳酸氢钠水溶液淬灭反应,并用二氯甲烷(15毫升)萃取三次,合并有机相,有机相用饱和食盐水(15毫升)洗涤三次,无水硫酸钠干燥,过滤,真空状态下除去挥发物后,柱层析得产物,收率62%。
实施例21所得产物(E)-2-(4-甲基苯基)-2-(4,4-二苯基-1,3-丁二烯基)-1,3-二噻烷的结构和核磁数据如下:
1H NMR(400MHz,Chloroform-d)δ7.69–7.61(m,2H),7.40–7.27(m,8H),7.21–7.16(m,2H),6.89–6.79(m,3H),6.45(dd,J=15.1,11.1Hz,1H),6.11(d,J=15.0 Hz,1H),3.79(s,3H),2.93–2.80(m,2H),2.73–2.64(m,2H),2.05–1.84(m,2H). 13C NMR(101MHz,Chloroform-d)δ159.3,144.0,142.3,139.5,137.6,133.6,132.3, 130.6,129.8,128.4,128.2,127.8,127.7,127.6,126.7,113.8,58.6,55.4,28.8,24.7.
实施例22:化合物(E)-2-(4-甲氧基苯基)-2-(4,4-二(4-甲基苯基) -1,3-丁二烯基)-1,3-二噻烷的制备:
在25毫升的圆底烧瓶中依次加入(Z)-2-(2-氯-2-(4-甲氧基苯基)乙烯基)-1,3-二噻烷(86毫克,0.3毫摩尔)、1,1-二(4-甲基苯基)乙烯(42毫克, 0.2毫摩尔)和6毫升1,2-二氯乙烷,加入三氟化硼乙醚(76微升,0.6毫摩尔) 后在室温下搅拌,用薄层色谱法监测反应,反应结束后在反应体系中加入1摩尔/毫升的碳酸氢钠水溶液淬灭反应,并用二氯甲烷(15毫升)萃取三次,合并有机相,有机相用饱和食盐水(15毫升)洗涤三次,无水硫酸钠干燥,过滤,真空状态下除去挥发物后,柱层析得产物,收率63%。
实施例22所得产物(E)-2-(4-甲基苯基)-2-(4,4-二(4-甲基苯基) -1,3-丁二烯基)-1,3-二噻烷的结构和核磁数据如下:
1H NMR(400MHz,Chloroform-d)δ7.70–7.62(m,2H),7.21–7.16(m,2H),7.15–7.04(m,6H),6.88–6.81(m,2H),6.77(d,J=11.0Hz,1H),6.47(dd,J=15.0,11.1 Hz,1H),6.07(dd,J=15.0,0.7Hz,1H),3.79(s,3H),2.95–2.82(m,2H),2.74–2.62 (m,2H),2.37(s,3H),2.34(s,3H),2.08–1.98(m,1H),1.96–1.86(m,1H).13C NMR (101MHz,Chloroform-d)δ159.2,143.9,139.7,137.5,137.2,136.9,136.7,133.7, 132.6,130.5,129.8,129.0,128.8,127.8,125.8,113.8,58.7,55.4,28.9,24.7,21.4,21.3.
实施例23:化合物(E)-2-(4-甲氧基苯基)-2-(4,4-二(4-丙炔氧基苯基)-1,3-丁二烯基)-1,3-二噻烷的制备:
在25毫升的圆底烧瓶中依次加入(Z)-2-(2-氯-2-(4-甲氧基苯基)乙烯基)-1,3-二噻烷(86毫克,0.3毫摩尔)、1,1-二(4-丙炔氧基苯基)乙烯(58毫克,0.2毫摩尔)和6毫升1,2-二氯乙烷,加入三氟化硼乙醚(76微升,0.6毫摩尔)后在室温下搅拌,用薄层色谱法监测反应,反应结束后在反应体系中加入1 摩尔/毫升的碳酸氢钠水溶液淬灭反应,并用二氯甲烷(15毫升)萃取三次,合并有机相,有机相用饱和食盐水(15毫升)洗涤三次,无水硫酸钠干燥,过滤,真空状态下除去挥发物后,柱层析得产物,收率70%。
实施例23所得产物(E)-2-(4-甲基苯基)-2-(4,4-二(4-丙炔氧基苯基)-1,3-丁二烯基)-1,3-二噻烷的结构和核磁数据如下:
1H NMR(600MHz,Chloroform-d)δ7.71–7.64(m,2H),7.25–7.21(m,2H),7.12–7.09(m,2H),6.94–6.88(m,4H),6.87–6.83(m,2H),6.70(d,J=11.1Hz,1H),6.39 (dd,J=14.7,11.1Hz,1H),6.07(dd,J=15.1,0.7Hz,1H),4.71(d,J=2.5Hz,2H), 4.69(d,J=2.3Hz,2H),3.80(s,3H),2.90–2.82(m,2H),2.73–2.66(m,2H),2.56 (s,1H),2.53(s,1H),2.06–1.98(m,1H),1.96–1.87(m,1H).13C NMR(151MHz, Chloroform-d)δ159.2,157.4,157.1,143.0,136.7,136.0,133.6,132.9,132.5,131.8, 129.9,129.1,125.3,114.7,114.5,113.8,78.7,78.6,75.8,58.8,56.0,55.4,28.8,24.7.
实施例24:化合物(8R,9S,13S,14S,Z)-16-(3,3-二(4-甲氧基)亚烯丙基)-13-甲基-6,7,8,9,11,12,13,14,15,16-十氢螺[环戊烷[a]菲-17, 2’-[1,3]-二硫代]-3-醇的制备:
在25毫升的圆底烧瓶中依次加入雌酮衍生的β-氯代烯基-1,3-二噻烷 (122毫克,0.3毫摩尔)、1,1-二(4-甲氧基苯基)乙烯(48毫克,0.2毫摩尔) 和6毫升1,2-二氯乙烷,加入三溴化铟(106毫克,0.3毫摩尔)后在室温下搅拌,用薄层色谱法监测反应,反应结束后在反应体系中加入1摩尔/毫升的碳酸氢钠水溶液淬灭反应,并用二氯甲烷(15毫升)萃取三次,合并有机相,有机相用饱和食盐水(15毫升)洗涤三次,无水硫酸钠干燥,过滤,真空状态下除去挥发物后,柱层析得产物,收率52%。
实施例24所得产物(8R,9S,13S,14S,Z)-16-(3,3-二(4-甲氧基)亚烯丙基)-13-甲基-6,7,8,9,11,12,13,14,15,16-十氢螺[环戊烷[a]菲-17, 2’-[1,3]-二硫代]-3-醇的结构和核磁数据如下:
(8R,9S,13S,14S,Z)-16-(3,3-二(4-甲氧基)亚烯丙基)-13-甲基-6,7,8, 9,11,12,13,14,15,16-十氢螺[环戊烷[a]菲-17,2’-[1,3]-二硫代]-3-醇1H NMR(400MHz,Chloroform-d)δ7.25–7.18(m,4H),7.15(d,J=8.6Hz,1H), 6.96–6.89(m,2H),6.87–6.80(m,2H),6.74(dt,J=11.4,2.3Hz,1H),6.63(dd,J= 8.4,2.8Hz,1H),6.56(dd,J=7.1,4.3Hz,2H),4.73(s,1H),3.85(s,3H),3.81(s,3H), 2.96–2.80(m,4H),2.81–2.67(m,3H),2.42–2.25(m,2H),2.25–2.05(m,3H), 2.00–1.87(m,4H),1.59–1.40(m,4H),0.97(s,3H).13C NMR(101MHz, Chloroform-d)δ159.2,159.0,153.5,148.3,141.8,138.3,136.0,132.7,132.5,132.1, 129.3,126.5,124.2,123.3,115.4,113.7,113.5,112.8,66.7,55.5,55.4,51.8,46.6,43.4, 39.3,33.9,29.9,29.7,27.9,27.5,26.7,24.6,17.1。
Claims (3)
2.根据权利要求1所述的一种共轭二烯化合物的制备方法,其特征在于:路易斯酸、β-氯代乙烯基-1,3-二噻烷衍生物(I)、烯烃化合物(II)的摩尔比为0.5~3.0:1.5:1。
3.根据权利要求1所述的一种共轭二烯化合物的制备方法,其特征在于:反应温度为0~60℃。
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