CN111559971B 一种由烯烃与碘及二甲基亚砜构建碘代烯基硫醚的方法 （新疆普禾粟新型环保材料有限公司）

司蒙古自治州巴州库尔勒市上库综合产276.一种由烯烃与碘及二甲基亚砜构建碘代烯本发明公开了一种由烯烃与碘及二甲基亚2所述(Z)α碘代烯基硫醚衍生物具有式1结构：2.根据权利要求1所述的一种由烯烃与碘及二甲基亚砜构建碘代烯基硫醚的方法，其3[0002]卤代烯基硫化物是一种具有重要合成价值的化合物，其分子中含有多个反应位广大科学家的研究兴趣(WangBW,JiangK,LiJX,etal.1,1_DiphenylvinylsulfideasaFunctionalAIEgenDerivedfromtheAggregation_Caused_QuenchingMolecule1,1_DiphenylethenethroughSimpleThioetherification.AngewandteChemieInternationalEdition,2020,59(6):2338_2343；GuX_X,XieM_H,ZhaoX_Y,etal.AnEfficientSynthesisofPolysubstituted1,3_Enynesfrom(E)_β_IodovinylSulfonesandTerminalAlkynes.ChineseJournalofChemistry,2008,26(9):1625_1629；LiX,ShiX,FangM,etal.Ironhalide_mediatedhalosulfonylationofterminalalkyneswithsulfonylhydrazides:synthesisof(E)_beta_chloroandbromovinylsulfones.TheJournalofOrganicChemistry,2013,78(18):9499_9504；andstereoselectiveadditionofsulfenylchloridestoalkynesbyaradicalpathway.AngewandteChemieInternationalEdition,2014,53(50):13880_13884；IwasakiM,FujiiT,YamamotoA,etal.Palladium_catalyzedregio_andstereoselectivechlorothiolationofterminalalkyneswithsulfenyl中被其他基团所取代或者发生自身氧化还原转化(EttariR,NiziE,DiFrancescoME,etal.Developmentofpeptidomimeticswithavinylsulfonewarheadasirreversiblefalcipain_2inhibitors.JournalofMedicinalChemistry,2008,51(4):988_996；PalmerJT,RasnickD,KlausJL,etal.Vinylsulfonesasmechanism_basedcysteineproteaseinhibitors.JournalofMedicinalChemistry,1995,38onbiologicalactivityofvinylsulfonesasinhibitorsofHIV_1.Bioorganic4[0003]在过去的数十年中，合成这类碘代烯基硫化物的方法是通过炔烃的碘代_硫烷基al.StereoselectiveZ_halosulfonylationofterminalalkynesusingsulfonohydrazidesandCuX(X＝Cl,Br,I).RSCAdvances,2016,6(77):73132_73135；YangL,HuD,WeiL,etal.KIasiodinesourceforthessulfonesviametal_freeiodosulfonylationofterminalalkynes.Phosphorus,Sulfur,andSiliconandtheRelatedElements,2L,HuH,etal.Iodinepromotediodosulfonylationofalkyneswithsulfonylhydrazidesinanaqueousmedium:highlystereoselectivesynthesisof(E)_β_iodovinylsulfones.NewJournalofChemistry,2018,42(11):8752_8755；MaY,WangK,ZhangD,etal.SolventControlledTransformationbetweenSulfonylHydrazidesandAlkynes:DivergentSynthesisofBenzo[b]thiophene_1,1_dioxidesand(E)_b_Y,WuW,HuangY,etal.NBS_promotedhalosulfonylationofterminalalkynes:highlyregio_andstereoselectivesynthesisof(E)_β_halovinylsulfones.Organicof(E)_β_iodovinylsulfonesviaiodine_promotediodosulfonylationofalkyneswithsodiumsulfinatesinanaqueousmediumatroomtemperature.Green2[0009]Pan和Liu等人利用二甲亚砜(DMSO)这种热门的合成子提供硫源，与H2O形成混合溶剂与炔烃、单质碘I2反应也能得到β_HO:AMetal_FreeCombinationSystemfortheOxidativeAdditionofAlkynesto2Access(E)_alpha_Iodo_beta_methylsulfonylalkenes.TheJournalofOrganic化合物与烷基磺酰肼、I2反应，经过去氧化制备β_碘代烯基硫醚的方法(BaoY,YangX,5ZhouQ,etal.Iodine_PromotedDeoxygenativeIodization/Olefination/SulfenylationofKetoneswithSulfonylHydrazides:Accesstobeta_Iodoalkenyl[0014]α_碘代烯基硫化合物比碘和硫原子分别位于两个碳原子上的β_碘代烯基硫化合物更容易发生取代反应，因而是具有更好反应性能和生物性能的一类碘代烯基硫化物。α_碘代烯基硫醚的方法(BaoY,YangX,ZhouQ,etal.Iodine_PromotedDeoxygenativeIodization/Olefination/SulfenylationofKetoneswithSulfonylHydrazides:Accesstobeta_IodoalkeS,LiY,etal.Design,synthesis,andbiologicalactivitiesofnovel2_cyanoacrylatescontainingoxazole,oxadiazole,orquinolinemoieties.Journalof一种金属烯基硫醚中间体(YangWS,ShimadaK,DelvaD,etal.IdentificationofSimpleCompoundswithMicrotubule_BindingActivityThatInhibitCancerCellGrowthwithHighPotency.ACSMedicinalChemicalLetters,2012,36[0022]另外在2006年，Cai等人报道了利用锡烷取代的烯基硫醚化合物为底物与单质碘发生碘代脱锡基化反应来合成α一碘代烯基硫醚类化合物的方法(TurchiIJ,DewarMJ718循环作用。[0054]1)本发明提出的由烯烃与碘及二甲基亚砜构建碘代烯基硫醚的方法所采用的原[0055]2)本发明提出的一种由烯烃与碘及二甲基亚砜构建碘代烯基硫醚的方法无需使[0056]3)本发明提出的一种由烯烃与碘及二甲基亚砜构建碘代烯基硫醚的方法采用一[0057]4)本发明提出的一种由烯烃与碘及二甲基亚砜构建碘代烯基硫醚的方法对底物[0058]以下实施例旨在进一步说明本发明内容，而不是限制本发明权利要求的保护范9参考氘代氯仿在77.0ppm三重态的中心线或参考氘代DMSO在39.52pp2苯乙烯)(甲基)硫醚[0073]在上述最佳条件下能以86％的收率得到a，接着尝试继续加入某种添加剂来促进2CO3[0082]经上述优化以后得到的标准反应过程如下：在25mlSchlenk管中入5ml左右乙酸乙酯，将混合物转移至分液漏斗。加入10ml饱和食盐水和适量硫代硫酸钠Na2S2O3移到烧杯加入无水Na2SO4干燥，最后真空旋干溶剂。旋干后的样品通过硅胶柱层析进行分C{1H}NMR(101MHz,CDCl3)δ141.61,137.50,128.31,127.92,127.85,CDCl3)δ141.66,137.48,128.32,127.87,125.67,96.99.GC_MS(m/z)＝279.1.32(s,12H).13C{1H}NMR(101MHz,CDCl3)δ151.034.51,31.22,16.61.GC_MS(m/z)＝332..13C{1H}NMR(101MHz,CDCl3)δ162.35(d,J＝248.4Hz),138.01(d,J＝3.2Hz).13C{1H}NMR(101MHz,CDCl3)δ140.13,138.33,133.75,129.01,128.40,95.07,16.65.GC_MSC{1H}16.67.GC_MS(m/z)＝310.16.67.GC_MS(m/z)＝310..13C{1H}NMR(101MHz,CDCl3)δ140.56,138.42,[0130]黄色油状物，产率5786mg，洗脱剂比例：石油醚/乙酸乙酯＝100/1。1HNMR128.83,128.28,127.57,127.42,126.15,125.33,97.36,28.74,16.63,15.53.GC_M=304.138.77,137.96,133.10,132.85,128.14,127.88,127.50,127.23,126.59,126.34,125.39,97.26,16.71.GC_MS(m/z)＝326.19.19,18.42,14.06.GC_MS(m/z)＝284.29.29,28.22,22.68,18.07,16.28,14.10,13.70.GC_MS(m/z)＝368.[0142]黄色油状物，产率4853mg，洗脱剂比例：石油醚/乙酸乙酯＝100/1