富勒烯氮丙環(huán)與羰基化合物、磺酰胺脒和脲的反應(yīng)研究

InvestigationonReactionofAziridinofullereneswithCarbonyl mpounds，Sulfamides，AmidinesandUreasADissertationSubmitted XingMengLeiOrganicChemistryDissertationSupervisor:YangHai-富勒烯的化學(xué)修飾對(duì)于合成具有獨(dú)特物理、化學(xué)性質(zhì)的富勒烯衍生應(yīng)是最早研究的也是最重要的一類反應(yīng)。但是有一些富勒烯衍生物無(wú)法簡(jiǎn)易的由C60主要圍繞由N磺?；焕障┑h(huán)轉(zhuǎn)化生成其他新的富勒烯衍生物的方法研究展開(kāi)，主要包括以下三個(gè)部分：研究了在BF3Et2O作用下富勒烯氮丙環(huán)與羰基化合物進(jìn)行[3+2]環(huán)加成反應(yīng)，生成了一系列新型的富勒烯并噁唑烷衍生物。通過(guò)溫研究了B32O或MP催化下的富勒烯氮丙環(huán)分別與磺酰胺類或脒類化合物發(fā)生的雙親核取代反應(yīng)，合成一系列富勒烯并1,2二胺環(huán)戊烷衍生物。通過(guò)溶劑、路易斯酸和堿來(lái)優(yōu)化該步反應(yīng)以達(dá)到最佳條件。研究了路易斯堿催化下的富勒烯氮丙環(huán)與脲類化合物發(fā)生親核取代反應(yīng)，合成一系列富勒烯并咪唑烷酮類衍生物。通過(guò)不同路易斯堿、反應(yīng)溫度來(lái)優(yōu)化該步反應(yīng)以達(dá)到最佳條件。富勒烯氮丙環(huán)3+2]環(huán)加成;親核取代;轉(zhuǎn)Chemicalmodificationoffullereneisstillattractiveresearchfieldsfordesigningmorefullerenederivativeswithuniquephysicalandchemicalproperties.Amongthosefunctionalizedreactions,cycloaddtionreactionsareoneoftheearlieststudiedandmostimportantreactions.ButsomeofderivativescannotbeeasilysynthesizeddirectlyfromC60throughone-stepreation.Thus,theinvestigationofthefurthertransformationstartingfromeasilyavailablefullerenederivativesremainsunderdevelopment.ThisdissertationfocusesontheexplorationofnewtransformationofN-tosylatedazaridinofullereneforthepreparationofnewclassoffullerenederivatives.Themainworksofthedissertationincludsthreeparts:WereportedtheBF3·Et2O-catalyzedtheformal[3+2]reactionofaziridinofullereneswithcarbonylcompoundsfortheeasypreparationofaseriesofoxazolidine-fusedfullerenederivatives.DifferentsolventsandvariouscommonlyusedLewisacidswerescreenedtooptimizethereactioncondition.Furthermore,thistransformationcanbeconductedinsimpleandgentlewaywithlowcosts.WereportedtheBF3·Et2O-orDMAP-catalyzeddoublenucleophilicsubstitutionreactionofaziridinofullereneswithsulfamidesoramidinesandprovidenewroutestocyclic1,2-diaminated[60]fullerenes.DifferentsolventsandvariouscommonlyusedLewisacidsandbaseswerescreenedtooptimizethereactioncondition.WereportedtheLewisbase-catalyzedreactionofaziridinofullerenewithureasforthepreparationoffulleroimidazolidinonederivatives.ReactiontemperatureandvariousLewisbaseswerescreenedtooptimizethereaction:aziridinofullerene;[3+2]cycloaddition;nucleophilicsubstitution;transformation;引 近年來(lái)富勒烯單加成領(lǐng)域研究進(jìn) 近年來(lái)氮丙環(huán)的研領(lǐng)域究進(jìn) 富勒烯氮丙 研究背 研究意 研究進(jìn) 研究目的和研究?jī)?nèi) 主要儀器和試 結(jié)果和討 實(shí)驗(yàn)條件篩選及優(yōu) 實(shí)驗(yàn)結(jié) 實(shí)驗(yàn)部 化合物表 本章小 BF3Et2O-或DMAP催化下的[6,6]富勒烯氮丙環(huán)與磺酰胺或脒的雙親核取代反 主要儀器和試 結(jié)果與討 實(shí)驗(yàn)條件的篩選和優(yōu) 實(shí)驗(yàn)結(jié) 實(shí)驗(yàn)部 化合物表 本章小 路易斯堿催化下的[6,6]富勒烯氮丙環(huán)與脲的反 主要儀器和試 結(jié)果和討 實(shí)驗(yàn)條件篩選及優(yōu) 實(shí)驗(yàn)結(jié) 實(shí)驗(yàn)部 原料的富勒烯產(chǎn)物4-6的化合物表 本章小 全文總 參考文 攻 期間研究成 引富勒烯（Fullerene)是單質(zhì)碳的第三種同素異形體。任何由碳一種元素組成，以C601990年，Kriiser等人[2]首次了大量合成C60的方法，這使得C60的研究工作全面的在不同科學(xué)領(lǐng)域被賦予有實(shí)用價(jià)值的潛在應(yīng)用[5]。C60的分子結(jié)構(gòu)模 Scheme1-尤其近二十年來(lái)，科學(xué)界對(duì)關(guān)于富勒烯三維立體結(jié)構(gòu)的、綜述和書籍的報(bào)導(dǎo)同時(shí)，有機(jī)能電池(OSC)[8]裝置近年來(lái)受到人們的關(guān)注，尤其是最近一篇關(guān)于能量轉(zhuǎn)化效率超過(guò)10%的文章后[9]。而在OSC中，富勒烯衍生物已被證明是近年來(lái)富勒烯單加成領(lǐng)域研究進(jìn)近些年來(lái)，C60與各種功能材料的功能化為生物、光纖個(gè)電子器件領(lǐng)域提供了豐2014年課題組利用芐氯和C60反應(yīng)生成了富勒烯吡咯烷[11]（Scheme1-aArCH部分來(lái)自相應(yīng)的芐氯中的C-Cl的斷裂，并且用PhCl/DMSO代替PhCl以提高反應(yīng)產(chǎn)率。同年該課題組還用溴代活性亞甲基化合物和C60在氨基酸和DMSO并且沒(méi)有使用任何催化劑的條件下，合成了一系列富勒烯b敏的底物。2014年Martín課題組對(duì)手性的富勒烯吡咯烷進(jìn)行了探究，在不同的催化系統(tǒng)中，C60與不同的N-金屬化的亞甲胺內(nèi)鎓鹽發(fā)生1,3-偶極環(huán)加成反應(yīng)生成具有高度選擇性的富勒烯吡咯烷衍生物[13]（Scheme1-2,。同年，該課題組也了通成光學(xué)活性[3,4:1,2]富勒烯吡咯烷[14]（Scheme1-2,d。Scheme1-Scheme1-014年，李法寶在F(lO4)3催化的加熱條件下用60與異酸酯或硫異酸酯反應(yīng)生成了一系列富勒烯惡唑烷酮或噻唑烷酮類衍生物[15（Shme1-60Fl3PhI(F3)2u-O鍵并雜環(huán)化合成了一系列[4,5:,2]富勒烯惡唑烷酮衍生物[16]（Shme1-b。富勒烯惡唑啉作為另一種富勒烯五元環(huán)同樣引起了人們的。2012年課題組利用C60HO-b[20]cDABCO的催化條件下，于均相和非均相溶液中都得到了富勒烯異惡唑啉產(chǎn)物dScheme1-有：2013年，Tuktarov團(tuán)隊(duì)利用Pd(acac)2-PPh3-Et3Al催化條件下，用重氮酰胺和C60反應(yīng)生成富勒烯吡唑啉衍生物[22]（Scheme1-5,a，2013年張貴生團(tuán)隊(duì)則在Cu(OAc)2條件下用C60和N-磺酸化的o-氨基-芳香甲基酮或O-烷基肟經(jīng)歷C-C/C-N斷裂，發(fā)生N-雜環(huán)化反應(yīng)生成了新穎的并且稀有的富勒四氫氮雜環(huán)庚戊酮或四氫氮雜環(huán)庚戊亞胺[23]（Scheme1-5b。2013年，金鐵男則在CoCl2dppe催化下，C60和富勒烯[60]碳環(huán)[24]（Scheme1-5c，實(shí)驗(yàn)結(jié)果清晰表明，相應(yīng)的產(chǎn)物是經(jīng)歷自由基而不是通過(guò)氫化的富勒烯產(chǎn)物形成的二步過(guò)程，并且混有Mn還原劑和水試劑的Co鹽催化劑是該反應(yīng)成功的關(guān)鍵?；谥巴豕傥湔n題組曾利用Fe(ClO4)3·6H2O作為催化劑從C601,3-二氧戊環(huán)衍生物的研究成果[25]，2014年，課題組使用LiClO4·3H2O作為催化劑，C60與不同氟代苯反應(yīng)1,3-二氧戊環(huán)衍生物[26]（Scheme1-5,d，并深入探究了苯環(huán)Scheme1-2013a，他們發(fā)現(xiàn)了由FeCl3的N-二苯甲基磺酰胺和C60在高速振動(dòng)研磨的條件下合成富[28]b-二苯甲基磺酰胺的-N201460Pb()41,3-[29（Shme1-,而其帶有的羥團(tuán)可以進(jìn)一步反應(yīng)生成脂和謎有趣的是制得1,3-1,4-1,3-環(huán)。2014Pb()2--O60發(fā)生環(huán)加成反應(yīng)富勒烯并異色滿衍生物[30]（Shme1-d。Scheme1-本近年來(lái)對(duì)富勒烯衍生物也進(jìn)行了深入的研究，并取得了一定的進(jìn)展。2013年，了以P作用下orit-yli-lman()產(chǎn)物與60在2存在下進(jìn)行[32]和[42]hme1-7）[31]。同年關(guān)于了照條件下，酰胺類化合物與60在PhI()2I2hme1-8）[32]。之后研究了烷氧基/酰氧基/酚氧基酮肟與60在堿的作用下發(fā)生的反應(yīng)。酮肟可以發(fā)生不同尋常的-和-鍵斷裂，從而得到一系列富勒烯異惡唑啉和二氫噁嗪衍生物（Shme1-）[33]。之后又深入研究了有無(wú)丁炔二酸二甲脂存在下的ul2催化的60與胺反應(yīng)分別生成富勒烯吡咯啉和氮丙環(huán)的反應(yīng)（Scheme1-10）[34]。以及在CuI的催化下，空氣中O2作為氧化劑，探究出了一種新反應(yīng)同樣適用于利用C60和酰胺富勒烯惡唑啉衍生物（Scheme1-11）[35]。Scheme1-Scheme1-Scheme1-Scheme1-Scheme1-近年來(lái)氮丙環(huán)的研領(lǐng)域究進(jìn)次了依從Woodward–Hoffmann規(guī)則發(fā)生順旋C-C的鍵的斷裂產(chǎn)生亞胺內(nèi)鎓鹽的Scheme1-Scheme1-Scheme1-而對(duì)于芳基親核試劑的報(bào)導(dǎo)卻很少，2007年，MilanBera和SujitRoy發(fā)現(xiàn)了N-氮丙環(huán)與芳基親核試劑的反應(yīng)[54]Scheme1-Scheme1-王梅祥課題組于2008年發(fā)現(xiàn)了一種新穎的1-芳基氮丙環(huán)-2-甲酸甲酯與-2-溴甲烷-三氟乙酰胺合成1,4-苯二氮衍生物的法該反應(yīng)歷程經(jīng)過(guò)-芐化作用和氮環(huán)的高度選擇性開(kāi)環(huán)隨之還有Et3的化物與酰胺氮原子之間的分子內(nèi)親核取代反應(yīng)[56]。Scheme1-Scheme1-2010年ns等人提出了一個(gè)手性拆分和非對(duì)映性選擇的路易斯酸催化的由氮丙環(huán)與活性亞甲基碳親核試劑發(fā)生SN2環(huán)加成反應(yīng)生成手性-內(nèi)酰胺的合成方法[58]。Scheme1-，2011年課題組的溫航提出了一種條件溫和有效地，在Ni(ClO4)2的催化下通過(guò)斷開(kāi)使得-Ts氮丙環(huán)與芳香醛發(fā)生歷經(jīng)高度非對(duì)映立體選擇性和區(qū)域選，Scheme1-Scheme1-Scheme1-[65]Scheme1-富勒烯氮丙富勒烯氮丙環(huán)因其具有不穩(wěn)定的氮丙環(huán)使其成為高效區(qū)域選擇性合成富勒烯籠狀結(jié)構(gòu)的有效如與芳基化合物的1,4雙加成反應(yīng)[66]和炔烴的[32]環(huán)加成反應(yīng)[67]。迄今為止，通過(guò)C60的[6,6]鍵與疊氮化物發(fā)生1,3-偶極環(huán)加成和光催化脫氮反應(yīng)常用的富勒烯氮丙環(huán)的合成方法[68]而隨著三唑啉的脫去N2能得到[5,6]開(kāi)環(huán)富勒Scheme1-富勒烯的化學(xué)修飾仍舊是設(shè)計(jì)具有獨(dú)特化學(xué)物理和生物性質(zhì)富勒烯衍生物的熱門領(lǐng)域。而在已有的富勒烯功能化的方法中，大多數(shù)衍生物都是直接從C60直接得到的。然而并不是所有的富勒烯衍生物都能從C60一步法制得。因此從通過(guò)轉(zhuǎn)化其他富勒烯衍生物的研究仍在開(kāi)發(fā)中氮丙環(huán)作為不穩(wěn)定的氮三元環(huán)是一C-CC-N1,3-1,3-偶極子，可發(fā)生環(huán)加成C-CC-N斷裂。C60與疊氮化物[72]、氯胺[73]、硫亞胺[74]TsN=IPh[75]和N,N-雙鹵代磺酰胺[76]反應(yīng)生成本同樣也了一種用胺和高價(jià)碘試劑[6,6]閉環(huán)富勒烯氮丙環(huán)的方法[77]。[5,6]開(kāi)環(huán)富勒烯氮丙環(huán)被廣泛應(yīng)用于開(kāi)環(huán)結(jié)構(gòu)的富勒烯衍生物或C59N[78]，但是關(guān)于[6,6]閉環(huán)富勒烯Minakata和Itami課題組以[6,6]閉環(huán)富勒烯氮丙環(huán)為平臺(tái)通過(guò)它與炔烴化合物和單/雙親核試劑在酸條件下一系列富勒烯衍生物[66,75]在這個(gè)轉(zhuǎn)化過(guò)程中隨著產(chǎn)Scheme1-Scheme1-Scheme1-本主要圍繞[6,6]閉環(huán)富勒烯氮丙環(huán)的轉(zhuǎn)化研究，探索更加新穎、高效、綠色N-RC-N生成的標(biāo)記烯惡唑啉產(chǎn)物。然而我們知道C60作為一個(gè)吸電子是不利于碳正離子的形成。Scheme1-根據(jù)前人的研究成果[35,65,80]N-Ts基團(tuán)的情況下，我們想用[6,6]閉環(huán)1,3-二元胺反應(yīng)，生成新的富勒烯衍生物。 Scheme1-基于Minakata課題組的研究成果[79]，他們并沒(méi)有出取代基為烷基的富勒Scheme1-主要儀器和試本實(shí)驗(yàn)過(guò)程中所用主要實(shí)驗(yàn)儀器和試劑見(jiàn)Table2-1和Table2-2名 規(guī)格型-核磁儀

400MHz、BrukerARX 島津FT/IR苯國(guó)藥化學(xué)試劑國(guó)藥化學(xué)試劑國(guó)藥化學(xué)試劑國(guó)藥化學(xué)試劑2-呋喃2-噻吩3-吡啶國(guó)藥化學(xué)試劑國(guó)藥化學(xué)試劑對(duì)國(guó)藥化學(xué)試劑對(duì)氯苯國(guó)藥化學(xué)試劑國(guó)藥化學(xué)試劑國(guó)藥化學(xué)試劑多聚國(guó)藥化學(xué)試劑 分析 安耐吉化 分析 安耐吉化 分析 安耐吉化 分析 安耐吉化 分析 國(guó)藥化學(xué)試劑 分析 國(guó)藥化學(xué)試劑 分析 國(guó)藥化學(xué)試劑 國(guó)藥化學(xué)試劑丙 分析 國(guó)藥化學(xué)試劑 分析 安耐吉化 分析 安耐吉化對(duì)磺酰 分析 安耐吉化各種試劑均為市售產(chǎn)品。需要，則視反應(yīng)具體的要求按標(biāo)準(zhǔn)進(jìn)行干燥或純結(jié)果和討首先我們把N-Ts[6,6]富勒烯氮丙環(huán)1a和苯作為底物模型來(lái)測(cè)試[3+2]環(huán)加常用的路易斯酸都被用來(lái)測(cè)試，例如Sc(OTf)3、Cu(OTf)2、Zn(OTf)2、Sn(OTf)2、Cu(ClO4)2、Cu(acac)2、Ni(acac)2、AgClO4BF3·Et2OSc(OTf)3、Cu(OTf)2和Zn(OTf)2被說(shuō)能催化2-芳基-N-Ts氮丙啶與醛和酮之間的反應(yīng)[82]，但是本實(shí)驗(yàn)中BF3·Et2O是唯一的能有效催化該反應(yīng)，并得到目標(biāo)產(chǎn)物富勒烯惡唑烷3aa的催化劑（Table2-3,entry9BF3·Et2O的用量從1.5提到5equiv能15min88%3aa（Table2-3,entry10。Table2-3ScreeningoftheReactionLewisLewisyield1240224032404240524062407240824099015notification,reactionswereout0.02mmolof1aadditivesin2.5mLofdrychlorobenzeneatroomtemperature.bIsolatedF3E2O-s富勒烯氮丙環(huán)1a與各種羰基化合物的普通[32]ble2-52g1a與1.5quiv對(duì)2c和.5quiv對(duì)甲氧基苯2d的混合物在5quivF3E2O的存在下反應(yīng)時(shí)，3a:3ad1:3。雜原子醛同樣也被拿來(lái)測(cè)試（ble24,ntries57。盡管2噻吩2e的產(chǎn)物3ae有一個(gè)相當(dāng)不錯(cuò)的產(chǎn)率93%但是2呋喃2f的產(chǎn)物3af卻只有56%的產(chǎn)率而且3吡啶2g沒(méi)有顯示出反應(yīng)活性。,不飽和醛和脂肪醛同樣也能被拿來(lái)當(dāng)做親偶極體反應(yīng)得到相應(yīng)的（ble24,ntries81215quiv（ble24,ntries13nd14Table2-4SubstrateScopefortheBF3Et2O-CatalyzedFormal[3+2] time yield 3ae 3af 3aj 3ak 3al 3an aUnlessnotification,thereactionswerecarriedoutwiththemolarratioof1a(17.8mg)/2/BF3Et2O=1:1.5:5in2.5mLofdrychlorobenzeneatroomtemperature.bIsolatedyield.c1a/2/BF3Et2O=1:3:5.d1a/paraformaldehyde/BF3Et2O=1:5:5.e=1:4:15.f1a/2n/BF3Et2O=5高的反應(yīng)活性。N-2d90%3dbTable2-5StudyoftheReactionScopebyVariationof time yield

aThereactionswerecarriedoutwiththemolarratioof1(0.02mmol):2b:BF3Et2O=1:1.5:5in2.5mLofdrychlorobenzeneatroomtemperature.bIsolatedyield.32]H的正TLCR3ao4的生成(3ao:489:1)。Scheme2-1ReactionofN-Tosylaziridinofullerene2awithPropionaldehyde3equiv2o4（3ao/457/431與羰基化合物的[3+2]3aj2d4BF3Et2O1與羰基化合物的[3+2]3ao4計(jì)了1a1.5equiv(E)-2甲基-2-戊烯醛在5equivBF3Et2O存在下的反應(yīng)。以95%的4。盡管氮丙環(huán)與羰基化合物的[32]反應(yīng)前人已經(jīng)有了充分的研究[83]，但是另外一些具有羰團(tuán)的化合物卻從未被提及列如F1-甲基-2吡咯烷酮甲酸乙酯、F1-甲基-2吡咯烷酮和碳酸二甲脂在標(biāo)準(zhǔn)反應(yīng)條件下沒(méi)顯示出任何51a:5F3Et21:10:20實(shí)施反應(yīng)時(shí)，出人意料的產(chǎn)物6出現(xiàn)了盡管有不少文獻(xiàn)過(guò)富勒烯惡唑烷的合成方法但卻從未制62--H修飾中生成新的-(X=,,O,orS)[84]。Scheme2-2ReactionofN-Tosylaziridinofullerene1awithEthylFormate實(shí)驗(yàn)部Scheme2-3Thecompetitivereactionbetween4-nitrobenzaldehyde(2c)and4-mmolmmol2（4.1mmol（0.1mmol）加入到溶液中，室溫下攪拌，TLC監(jiān)測(cè)反應(yīng)直至1a的，在旋轉(zhuǎn)蒸3adScheme2-4Thereactionbetween3ajand2dinthepresenceof將富勒烯產(chǎn)物3aj（0.02mmol）和對(duì)甲氧基苯2d（8.2mg,0.06mmol）加入2.5mLBF3Et2O（0.1mmol4h，TLC監(jiān)測(cè)反應(yīng)。1a的合成操作步驟：100mL的單口瓶中加入C60（360.0mg,0.5mmol，和50mL80oCul(10.1mg,0.1mmo)，lutidine（22.2m,.2mol，PhI（322m,1.0mmol，和2（171.2mg,1.0mmol。室溫下反應(yīng)至LC無(wú)變化即停止反應(yīng)，先通過(guò)柱層析脫去ul，再在真空旋轉(zhuǎn)蒸發(fā)儀上除去氯苯，最后將瓶中剩余殘?jiān)?，通過(guò)硅膠60/1a。（for2a–l,0.1mmol,12μL;for2mand2n,0.3mmol,37μL;）加入到溶液中，室溫下攪拌，TLC監(jiān)測(cè)反應(yīng)直至1a的，在旋轉(zhuǎn)蒸發(fā)儀上除去溶劑，得到的混合物用色譜分離（淋洗劑為CS2/甲苯）得到33ao的合成操作步驟：稱取[6,6]富勒烯氮丙環(huán)1a（17.8mg,0.02mmol）和正丙2o（0.06or0.3mmol）2.5mLBF3Et2O（0.1mmol,12除去溶劑得到的混合物用硅色譜分（淋洗劑為CS2/甲苯得到3ao和4（when1a/2o/BF3·Et2O1:3:516.8mg883ao/489:11;when1a/2o/BF3·Et2O1:15:5,57:436的合成操作步驟：N-Ts[6,6]1a（17.8mg,0.02mmol）和5（14.8mg,0.2mmol2.5mLBF3Et2O（0.449μL）加入到混合液中，室溫下攪拌，TLC監(jiān)測(cè)反應(yīng)直至1a的，在旋蒸發(fā)儀上除去溶劑，得到的混合物用硅色譜分離（淋洗劑為CS2/甲苯）得到6?；衔?aa(brownsolid,17.6mg,88%,mp>300C):1HNMR(500MHz,CDCl3-CS2)δ8.13-8.15(m,2H),7.95(d,J=8.3Hz,2H),7.681H),7.44-7.50(m,3H),7.34(d,J=8.1Hz,2H),2.48(s,3H);13CNMR(125MHz,CDCl3-CS2)δ150.36,148.36,148.14,147.99,147.92,146.62,146.50,146.34(2C),146.19(3C),146.15,146.09,146.01,145.80(2C),145.31,145.16,145.03(2C),144.96,144.89,144.79,144.58(2C),144.52,144.43,144.29,144.04,142.80(2C),142.76,142.71,142.68,142.65,142.51,142.50,142.29,142.25,142.04,141.98,141.87,141.40,141.11(2C),141.08,139.85,139.43,138.53,138.11,138.09,137.42,137.39,137.01,136.71,129.74(arylC),129.71(2C,arylC),128.57(2C,arylC),128.31(2C,arylC),128.07(2C,arylC),98.68(sp3-CofC60),92.88(NCO),79.17(sp3-CofC60),21.82;UV-Vis(CHCl3)λmax/nm257,318,453,684;HRMS(MALDI-TOFMS)m/z[M+Na]+calcdforC74H13NNaO3S1018.0514,found3ab(brownsolid,18.9mg,92%,mp>300C):1HNMR(500MHz,CDCl3-CS2)δ8.08(d,J=8.3Hz,2H),7.94(d,J=8.4Hz,2H),(s,1H),7.45(d,J=8.5Hz,2H),7.35(d,J=8.1Hz,2H),2.49(s,3H);13CNMR(125MHz,CDCl3-CS2)δ150.17,148.23,148.08(2C),147.70,146.57,146.56,146.46,146.44,146.28(3C),146.24,146.18,146.10,145.92,145.37(2C),145.25,145.12,145.05(2C),144.88,144.83,144.63(2C),144.56,144.43,144.23,144.02,142.89,142.87,142.84,142.81,142.75,142.72,142.58,142.39,142.35,142.30,142.10,142.07,141.96,141.42,141.26,141.23,141.12,139.65,139.55,138.32(arylC),138.20,138.14,137.45,137.41,136.59,136.06(aryl135.68(arylC),130.01(2C,arylC),129.82(2C,arylC),128.63(2C,arylC),128.09(2C,arylC),98.81(sp3-CofC60),92.26(NCO),79.22(sp3-CofC60),21.85;UV-(CHCl3)λmax/nm257,319,453,683;HRMS(MALDI-TOFMS)m/z[M+Na]+calcdC74H12ClNNaO3S1052.0124,found3ac(brownsolid,15.4mg,74%,mp>300C):1HNMR(500MHz,CDCl3-CS2)δ8.40(d,J=9.0Hz,2H),8.36(d,J=8.9Hz,2H),7.97J=8.3Hz,2H),7.71(s,1H),7.38(d,J=8.2Hz,2H),2.50(s,3H);NMR(125,CDCl3-CS2)δ150.01,148.95,148.25,147.60,147.29,146.31(2C),146.30,146.25,146.21,146.12,145.13,145.05,144.96,144.93,144.79,144.60143.63,142.93,142.88,142.85(2C),142.76,142.37,142.33,142.27,142.11,142.08,141.97,141.37,141.18,141.06,139.94,139.70,139.69,138.25,138.15,138.08,137.41,137.15,136.14,129.93(2C,arylC),129.56(2C,arylC),128.10(2C,arylC),123.58(2C,arylC),99.09(sp3-Cof91.85(NCO),79.10(sp3-CofC60),21.87;UV-Vis(CHCl3)λmax/nm257,319,453,683;HRMS(MALDI-TOFMS)m/z[M+Na]+calcdforC74H12N2NaO5S1063.0365,found3ad(brownsolid,18.4mg,90%,mp>300C):1HNMR(500MHz,CDCl3-CS2)δ7.99(d,J=8.4Hz,2H),7.90(d,J=8.4Hz,2H),(s,1H),7.32(d,J=8.3Hz,2H),6.94(d,J=8.6Hz,2H),3.86(s,3H),2.48(s,3H);13CNMR(125MHz,CDCl3-CS2)δ160.75(arylC),150.29,148.11,148.00,147.97,146.65,146.54,146.48,146.33(2C),146.16(3C),146.06,145.99,145.79,145.77,145.34,145.25,145.13,145.05(2C),145.01,144.77,144.66,144.57(2C),144.52,144.38,144.10(2C),142.77(2C),142.74,142.66,142.63,142.51,142.48,142.30,142.27,142.23,142.00,141.98,141.86,141.22,141.18,141.08,139.84,139.53,139.33,138.55(arylC),138.07,138.01,137.38,136.77,129.95(2C,arylC),129.61(2C,arylC),128.72(arylC),128.02(2C,arylC),113.64(2C,arylC),98.47(sp3-CofC60),92.68(NCO),79.19(sp3-CofC60),55.18,21.79;UV-Vis(CHCl3)λmax/nm257,319,453,683;HRMS(MALDI-TOFMS)m/z[M+Na]+calcdforC75H15NNaO4S1048.0619,found3ae(brownsolid,18.6mg,93%,mp>300C):1HNMR(500MHz,CDCl3-CS2)δ7.95(d,J=8.3Hz,2H),7.81(s,1H),7.77(d,J=Hz,1H),7.46(d,J=4.9Hz,1H),7.34(d,J=8.2Hz,2H),7.11J=4.9,3.4Hz,1H),2.49(s,3H);13CNMR(125MHz,CDCl3-CS2)δ150.39,148.08,147.94,147.75,146.51,146.49,146.45,146.32,146.28,146.17,146.14146.07,146.03,145.96,145.82,145.73,145.33,145.23,145.09,144.98,144.91,144.78,144.71,144.53,144.50,144.41,144.32,144.25,144.23,144.05,142.74142.72,142.67,142.65,142.62,142.44(2C),142.32,142.27,142.21,142.01,141.78,141.51,141.33,141.16,141.12,141.03,139.78,139.51,139.33,138.33,137.99,137.36,137.13,136.78,129.72(2C,arylC),129.43(thienylC),128.12C),128.02(2C,arylC),126.85(thienylC),99.07(sp3-CofC60),90.17(NCO),(sp3-CofC60),21.82;UV-Vis(CHCl3)λmax/nm256,319,454,684;HRMS(MALDI-TOFMS)m/z[M+Na]+calcdforC72H11NNaO3S21024.0078,found1024.0111.3af(brownsolid,11.0mg,56%,mp>300C):1HNMR(500CDCl3-CS2)δ7.91(d,J=8.3Hz,2H),7.57(br,1H),7.55(s,7.33(d,J=8.3Hz,2H),7.12(d,J=3.4Hz,1H),6.55(dd,J=1.9Hz,1H),2.47(s,3H);13CNMR(125MHz,CDCl3-CS2)δ150.06(furylC),148.19,148.06,147.94,147.84,146.58,146.55,146.47,146.40,146.26(2C),146.18,146.14,146.09,146.04,145.85,145.43,145.28,145.17,145.14,145.03144.88,144.83,144.75,144.65,144.61,144.54,144.49,144.38,144.36,143.98C),143.15,142.85,142.84(2C),142.80,142.72,142.71,142.54,142.50,142.45,142.33,142.09,142.05,141.91,141.45(2C),141.38,141.24,139.87,139.67,138.23,138.00,137.92,137.88,137.20(2C),129.77(2C,arylC),128.12(2C,aryl112.65(furylC),110.95(furylC),99.27(sp3-CofC60),87.09(NCO),78.80(sp3-CC60),21.82;UV-Vis(CHCl3)λmax/nm256,319,453,683;HRMS(MALDI-TOFMS)m/z[M+Na]+calcdforC72H11NNaO4S1008.0306,found1008.0294.3ah(brownsolid,17.5mg,86%,mp>300C):1HNMR(500CDCl3-CS2)δ7.91(d,J=8.3Hz,2H),7.46(d,J=7.2Hz,2H),(d,J=15.8Hz,1H),7.35(t,J=7.4Hz,2H),7.30(t,J=7.2Hz,7.29(d,J=8.3Hz,2H),7.02(dd,J=5.2,1.2Hz,1H),6.85(dd,J=15.8,5.2Hz,2.45(s,3H);13CNMR(125MHz,CDCl3-CS2)δ150.22,148.70,148.09,147.94,146.50,146.45,146.39(2C),146.32,146.17,146.11,146.10(2C),146.05,145.98145.86,145.33,145.31,145.19,145.17,145.09,145.03,145.02,144.96,144.71,144.50,144.40(3C),144.08,142.79,142.74(2C),142.72,142.62,142.60,142.45,142.30,142.26,142.22,142.07,141.96,141.87,141.49,141.39,141.36,139.83,139.70,139.19,138.31(arylC),138.11,137.70,137.62,137.32,136.51,136.39(CH=CH),135.47(arylC),129.57(2C,arylC),128.79(2C,arylC),128.76(aryl128.19(2C,arylC),127.34(2C,arylC),125.02(CH=CH),98.65(sp3-CofC60),(NCO),78.84(sp3-CofC60),21.75;UV-Vis(CHCl3)λmax/nm256,318,453,683;HRMS(MALDI-TOFMS)m/z[M+Na]+calcdforC76H15NNaO3S1044.0670,found3ai(brownsolid,18.0mg,94%,mp>300C):1HNMR(500MHz,CDCl3-CS2)δ7.90(d,J=8.3Hz,2H),7.33(d,J=8.1Hz,2H),(d,J=5.4Hz,1H),6.52-6.61(m,1H),6.30-6.35(m,1H),2.47(s,3H),1.97(d,J=6.6Hz,3H);13CNMR(125MHz,CDCl3-CS2)150.45,148.93,148.11,147.97,147.95,146.50,146.46,146.42,146.35(2C),146.14,146.08(2C),146.07,146.02(2C),145.91,145.36,145.34,145.18,145.10,145.05,145.02,144.98,144.75,144.56,144.55,144.46,144.42,144.40,142.79,142.75(2C),142.73,142.68,142.63,142.47,142.45,142.30,142.27,142.08,141.97,141.87,141.49,141.40,141.37,141.30,139.83,139.68,139.20,(arylC),138.10,137.68,137.62,137.27,136.53,133.67(CH=CH),129.54(2C,aryl128.12(2C,arylC),127.64(CH=CH),98.55(sp3-CofC60),92.69(NCO),78.68(sp3-ofC60),21.78,17.80;UV-Vis(CHCl3)λmax/nm256,318,453,683;HRMSTOFMS)m/z[M+Na]+calcdforC71H13NNaO3S982.0514,found3aj(brownsolid,17.6mg,90%,mp>300C):1HNMR(500MHz,CDCl3-CS2)δ7.87(d,J=8.3Hz,2H),7.27(d,J=8.3Hz,2H),(s,1H),2.44(s,3H),1.66(s,9H);13CNMR(125MHz,CDCl3-δ151.05,149.22,148.57,148.10,147.98,146.44,146.39,(2C),146.09(3C),146.06,146.02,145.94,145.93,145.72,145.65,145.34,145.08,145.02,144.99,144.88,144.69,144.65,144.57,144.52,144.36,144.16,143.90,143.88,142.80,142.78,142.76,142.68,142.62,142.60,142.51,142.39,142.22,142.21,142.08(2C),141.74,141.36,141.15,140.91,140.47(2C),139.50,139.31,138.55,137.89,137.24,137.09,136.54,129.75(2C,arylC),127.61arylC),102.68(NCO),99.28(sp3-CofC60),80.25(sp3-CofC60),38.88,28.0621.77;UV-Vis(CHCl3)λmax/nm257,319,454,684;HRMS(MALDI-TOFMS)m/z[M+Na]+calcdforC72H17NNaO3S998.0827,found998.0834.3ak(brownsolid,17.7mg,92%,mp>300C):1HNMR(500CDCl3-CS2)δ7.94(d,J=8.2Hz,2H),7.33(d,J=8.2Hz,2H),(d,J=9.5Hz,2H),3.53-3.62(m,1H),2.46(s,3H),1.57(d,J=6.8Hz,3H),1.52(d,J=6.6Hz,3H);13CNMR(125MHz,CDCl3-δ151.93,149.54,148.19,148.05(2C),146.56,146.48,146.41(2C),146.29,146.19,146.18,146.16,146.08,146.03(3C),145.40,145.30,145.19,145.10,144.83(3C),144.62,144.57(2C),144.40,144.33,144.24(arylC),143.67,142.80,142.77(2C),142.73,142.69,142.52,142.48,142.27,142.25(2C),142.05,141.96,141.41,141.35,141.31,140.64,139.90,139.75,139.64,139.14(aryl138.09,137.86,137.38,137.29,136.21,129.72(2C,arylC),128.02(2C,arylC),(NCO),98.43(sp3-CofC60),79.13(sp3-CofC60),33.63,21.81,19.61,18.97;UV-(CHCl3)λmax/nm257,319,452,683;HRMS(MALDI-TOFMS)m/z[M+Na]+calcdC71H15NNaO3S984.0670,found3al(brownsolid,12.9mg,70%,mp>300C):1HNMR(500MHz,CDCl3-CS2)δ7.99(d,J=8.3Hz,2H),7.37(d,J=8.3Hz,2H),6.25(s,2H),2.48(s,3H);13CNMR(125MHz,CDCl3-CS2)(all2Cunlessindicated)δ148.26(1C),148.09(1C),146.99,146.88,146.60,146.28,146.24,146.21,146.09,145.52,145.26(4C),145.23,144.68,144.63,144.57(1C,arylC),142.88,142.86,142.75,142.52,142.33,142.30,142.08,141.44,139.89,139.12,138.02,137.50,137.39(1C,arylC),129.75(arylC),128.47(arylC),98.51(1C,sp3-CofC60),80.12(1C,NCO),78.74(1C,sp3-CofC60),21.83(1C);UV-Vis(CHCl3)λmax/nm257,319,453,684;HRMS(MALDI-TOFMS)[M+Na]+calcdforC68H9NNaO3S942.0201,found3am(brownsolid,15.7mg,83%,mp>300C):1HNMR(500MHz,CDCl3-CS2)δ7.89(d,J=8.3Hz,2H),7.28(d,J=8.3Hz,2H),2.45(s,3H),2.44(s,6H);13CNMR(125MHz,CDCl3-CS2)(all2Cunlessindicated)δ149.63,148.96,148.01(1C),147.92(1C),146.39(4C),146.15,145.98,145.96(4C),145.21,144.99,144.97,144.56,144.34,143.39(1C,arylC),142.73,142.69,142.58,142.46,142.20,142.18,141.63,141.37,139.79(3C),137.94,136.94,136.69,129.35(arylC),127.79(aryl99.38(1C,NCO),96.87(1C,sp3-CofC60),80.06(1C,sp3-CofC60),28.47,21.66UV-Vis(CHCl3)λmax/nm257,319,452,684;HRMS(MALDI-TOFMS)m/zcalcdforC70H13NNaO3S970.0514,found3an(brownsolid,15.1mg,76%,mp>300C):1HNMR(500MHz,CDCl3-CS2)δ7.92(d,J=8.3Hz,2H),7.29(d,J=8.3Hz,2H),2.93(m,4H),2.45(s,3H),1.87-2.17(m,5H),1.51-1.64(m,1H);NMR(125MHz,CDCl3-CS2)(all2Cunlessindicated)δ149.81,149.24,148.21(1C),148.12(1C),146.66,146.62,146.56,146.34,146.15,146.14145.40,145.19,145.16,144.74,144.72,144.65,143.63(1C,arylC),142.90,142.75,142.65,142.38,142.34,141.91,141.79,141.52,140.29(1C,arylC),138.10,137.15,136.97,129.56(arylC),127.77(arylC),101.76(1C,NCO),96.94sp3-CofC60),80.54(1C,sp3-CofC60),36.89,25.17(1C),24.37,21.72(1C);UV-(CHCl3)λmax/nm257,319,452,683;HRMS(MALDI-TOFMS)m/z[M+Na]+calcdC73H17NNaO3S1010.0827,found4:(brownsolid,18.8mg,95%,mp>300C):1HNMR(500MHz,CDCl3-CS2)δ7.90(d,J=8.3Hz,2H),7.33(d,J=8.2Hz,2H),(s,1H),6.49(t,J=7.2Hz,1H),2.48(s,3H),2.27-2.36(m,2H),(s,3H),1.18(t,J=7.6Hz,3H);13CNMR(125MHz,CDCl3-CS2)δ150.31,148.55,148.23,148.12,147.99,146.58,146.52,146.48(2C),146.40,146.22,146.16,146.06(3C),146.03,145.97,145.47,145.44,145.22,145.14,145.07,145.04,144.92,144.79,144.62,144.56(2C),144.47,144.42,144.17,142.79(3C),142.71,142.64,142.52,142.51,142.31,142.29,142.25,142.10,142.02,141.86,141.33,141.31,141.22,139.88,139.69,139.18,138.01,137.90,137.84,137.22135.18,130.00,129.50(2C,arylC),128.35(2C,arylC),97.94(sp3-CofC60),(NCO),79.29(sp3-CofC60),29.96,21.84,13.55,12.35;UV-Vis(CHCl3)λmax/nm256,318,453,684;HRMS(MALDI-TOFMS)m/z[M+Na]+calcdfor1010.0827,found3bb(brownsolid,17.1mg,82%,mp>300C):1HNMR(500MHz,CDCl3-CS2)δ8.04(d,J=8.3Hz,2H),7.91(d,J=8.8Hz,2H),(s,1H),7.42(d,J=8.3Hz,2H),6.97(d,J=8.8Hz,2H),3.89(s,3H);13CNMR(125MHz,CDCl3-CS2)δ163.39(arylC),150.08,148.05,147.96,147.61,146.48,146.44,146.42,146.29,146.28,146.11,146.08(3C),146.02,145.78,145.75,145.19(2C),145.09,144.96,144.93,144.88,144.85,144.68,144.41,144.38(2C),144.30,143.92,142.74,142.72,142.69,142.65,142.61,142.44,142.40,142.23,142.21,142.15,141.95,141.92,141.79,141.29,141.15,141.08,139.78,139.50,139.35,138.01,137.86,137.29,137.26,136.39,135.95(aryl135.49(arylC),132.66(arylC),130.06(2C,arylC),129.88(2C,arylC),128.48(2C,arylC),114.14(2C,arylC),98.55(sp3-CofC60),92.05(NCO),79.01(sp3-Cof55.48;UV-Vis(CHCl3)λmax/nm257,319,453,683;HRMS(MALDI-TOFMS)[M+Na]+calcdforC74H12ClNNaO4S1068.0073,found3cb(brownsolid,19.9mg,94%,mp>300C):1HNMR(500MHz,CDCl3-CS2)δ8.36(d,J=8.9Hz,2H),8.19(d,J=8.8Hz,2H),(d,J=8.4Hz,2H),7.56(s,1H),7.43(d,J=8.4Hz,2H);13CNMR(125MHz,CDCl3-CS2)δ150.30,148.92,148.19,148.09,147.55,147.36,146.65,146.64,146.47,146.46,146.41,146.30(2C),146.28,146.26,146.18,145.98,145.96,145.36,145.22,145.20,145.10(2C),144.92,144.71(2C),144.57,144.29,144.21,143.82,143.54,142.94,142.90,142.87,142.84,142.74142.49,142.46,142.41,142.33,142.31,142.10,142.08,141.91,141.34,141.20,140.85,140.10,139.73,139.46,138.30,138.02,137.27,136.87,136.81,136.57(aryl134.59(arylC),130.03(2C,arylC),128.95(2C,arylC),128.73(2C,arylC),124.21(2C,arylC),98.80(sp3-CofC60),92.02(NCO),79.17(sp3-CofC60);UV-Visλmax/nm257,319,452,683;HRMS(MALDI-TOFMS)m/z[M+Na]+calcdC73H9ClN2NaO5S1082.9818,found3db(brownsolid,17.1mg,90%,mp>300C):1HNMR(500MHz,CDCl3-CS2)δ8.10(d,J=8.3Hz,2H),7.47(d,J=8.4Hz,2H),7.37(s,1H),3.56(s,3H);13CNMR(125MHz,CDCl3-CS2)δ148.17,148.02,147.81(2C),146.71,146.61,146.58,146.42,146.36(2C),146.23,146.22,146.14,146.08,145.83,145.75,145.37,145.23,145.16,145.09,144.99,144.95,144.76,144.52(2C),144.48,144.35,144.23,143.84,142.88,(2C),142.75(2C),142.65,142.51(2C),142.42,142.27,142.24,142.11,141.96,141.62,141.60,141.09,141.05,140.05,139.61,139.60,138.43,137.33,137.27,136.37,136.22(arylC),135.30(arylC),129.82(2C,arylC),128.65(2C,arylC),98.50(sp3-CofC60),91.74(NCO),79.67(sp3-CofC60),40.96;UV-Vis(CHCl3)λmax/nm257,319,453,683;HRMS(MALDI-TOFMS)m/zM+calcdforC68H8ClNO3S952.9913,found3ao(brownsolid,mp>300C):1HNMR(500MHz,CDCl3-CS2)7.93(d,J=8.3Hz,2H),7.33(d,J=8.2Hz,2H),6.49(dd,J=4.6Hz,1H),3.01-3.10(m,1H),2.78-2.87(m,1H),2.47(s,3H),1.49(t,J=7.4Hz,3H);13CNMR(125MHz,CDCl3-CS2)δ151.60,149.53,148.23,148.12,148.08,146.59,146.53(2C),146.44,146.42,146.28,146.23,(2C),146.16(2C),146.12,146.04,145.46,145.29,145.21,145.13,145.10,144.96,144.87,144.64,144.61,144.51,144.50,144.45,144.43,144.25(arylC),142.83(2C),142.80(2C),142.70,142.54,142.51,142.36,142.33,142.29,142.07,141.96,141.59,141.48(2C),141.20,139.84,139.74,139.61,138.70(aryl138.04,137.91,137.34,137.21,136.13,129.76(2C,arylC),127.85(2C,arylC),(sp3-CofC60),95.80(NCO),78.63(sp3-CofC60),30.35,21.80,10.17;UV-Visλmax/nm256,319,453,683;HRMS(MALDI-TOFMS)m/z[M+Na]+calcdC70H13NNaO3S970.0514,found6(brownsolid,11.9mg,78%,mp>300C):1HNMR(500MHz,CDCl3-CS2)δ8.03(s,1H);13CNMR(125MHz,CDCl3-CS2)(all2Cunlessindicated)δ156.50(1C,N=CO),148.27(1C),147.86(1C),147.16,146.48(4C),146.36,146.18,146.13,145.90,145.57,145.31,145.21,144.82,144.58,144.29,142.89,142.83(4C),142.78,142.43,142.26,142.18,142.05,141.96,140.52,139.79,137.72,136.22,96.55(1C,sp3-Cof90.96(1C,sp3-CofC60);UV-Vis(CHCl3)λmax/nm256,317,454,611,684;HRMS(MALDI-TOFMS)m/zM+calcdforC61HNO763.0058,found763.0049.本章小BF3Et2O的催化下[6,6]富勒烯氮丙環(huán)與各種各樣羰基化合物到理想產(chǎn)物。但是對(duì)于2o丙醛參與反應(yīng)時(shí)，卻出現(xiàn)了異常情況，在5equivBF3Et2O3equiv2o3ao。此外，甲酸BF3Et2O-DMAP催化下的[6,6]富勒烯氮丙環(huán)與磺酰胺或脒的主要儀器和試2.1國(guó)藥化學(xué)試劑國(guó)藥化學(xué)試劑國(guó)藥化學(xué)試劑國(guó)藥化學(xué)試劑國(guó)藥化學(xué)試劑氯磺酰異酸對(duì)國(guó)藥化學(xué)試劑國(guó)藥化學(xué)試劑對(duì)國(guó)藥化學(xué)試劑甲磺酸吡 分析 國(guó)藥化學(xué)試劑 分析 安耐吉化三乙 分析 國(guó)藥化學(xué)試劑 分析 安耐吉化結(jié)果與討首先我們選用N-Ts[6,6]富勒烯氮丙環(huán)1和N,N′-二丁基磺酰胺2a作為實(shí)驗(yàn)的反應(yīng)模型，根據(jù)前一章的1與羰基化合物的研究成果[85]，選用最有效的路易斯酸BF3Et2O5equivBF3Et2O的存在下，12a65min76%3a。Scheme3-1BF3Et2O-CatalyzedReactionofAziridinofullerene1withN,N'-Dibutylsulfamide1N-Ts[6,6]富勒烯甲苯基)-4-4a5equivBF3Et2O的存在下進(jìn)行反應(yīng)，并1，同樣其他常用的路易斯酸也沒(méi)有起作用，例如Zn(OTf)2、Sc(OTf)3、三氟甲磺酸(TfOH)(MSATable3-2,entries2-5)。在室溫條件下TfOH100oC條件下MSA存在下，大多數(shù)1轉(zhuǎn)化成C60，而使用Zn(OTf)2、Sc(OTf)3作為催化劑時(shí)，沒(méi)有任何反應(yīng)。之后使用Sc(OT