秋蘭姆參與的氮-硫鍵構(gòu)建反應(yīng)

引言秋蘭姆是一種廉價(jià)的商用有機(jī)硫化合物ADDINEN.CITE<EndNote><Cite><Author>Debnath</Author><Year>1996</Year><RecNum>206</RecNum><DisplayText><styleface="superscript">1</style></DisplayText><record><rec-number>206</rec-number><foreign-keys><keyapp="EN"db-id="s5ttfsrrmetp5xepwp2vff54e229r5ezwvte"timestamp="1680874568">206</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Debnath,SubhasChandra</author><author>Basu,DipakKumar</author></authors></contributors><titles><title>StudiesontheeffectofthiuramdisulfideonNRvulcanizationacceleratedbythiazole-basedacceleratorsystems</title><secondary-title>JournalofAppliedPolymerScience</secondary-title></titles><periodical><full-title>JournalofAppliedPolymerScience</full-title><abbr-1>J.Appl.Polym.Sci.</abbr-1><abbr-2>JApplPolymSci</abbr-2></periodical><pages>845-855</pages><volume>60</volume><number>6</number><dates><year>1996</year><pub-dates><date>1996/05/09</date></pub-dates></dates><publisher>JohnWiley&Sons,Ltd</publisher><isbn>0021-8995</isbn><work-type>/10.1002/(SICI)1097-4628(19960509)60:6<845::AID-APP7>3.0.CO;2-J</work-type><urls><related-urls><url>/10.1002/(SICI)1097-4628(19960509)60:6<845::AID-APP7>3.0.CO;2-J</url></related-urls></urls><electronic-resource-num>/10.1002/(SICI)1097-4628(19960509)60:6<845::AID-APP7>3.0.CO;2-J</electronic-resource-num><access-date>2023/04/07</access-date></record></Cite></EndNote>1，主要用作殺菌劑、殺蟲劑、防霉劑ADDINEN.CITE<EndNote><Cite><Author>González</Author><Year>2002</Year><RecNum>208</RecNum><DisplayText><styleface="superscript">2</style></DisplayText><record><rec-number>208</rec-number><foreign-keys><keyapp="EN"db-id="s5ttfsrrmetp5xepwp2vff54e229r5ezwvte"timestamp="1680874871">208</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>González,L.</author><author>Rodríguez,A.</author><author>DelCampo,A.</author><author>Marcos-Fernández,A.</author></authors></contributors><titles><title>Crosslinkreactionofnaturalrubberwiththiuramsulphurdonorsinthepresenceofathiurammonosulfide</title><secondary-title>JournalofAppliedPolymerScience</secondary-title></titles><periodical><full-title>JournalofAppliedPolymerScience</full-title><abbr-1>J.Appl.Polym.Sci.</abbr-1><abbr-2>JApplPolymSci</abbr-2></periodical><pages>491-499</pages><volume>85</volume><number>3</number><keywords><keyword>rubber</keyword><keyword>crosslinking</keyword><keyword>networks</keyword><keyword>mechanicalproperties</keyword></keywords><dates><year>2002</year><pub-dates><date>2002/07/18</date></pub-dates></dates><publisher>JohnWiley&Sons,Ltd</publisher><isbn>0021-8995</isbn><work-type>/10.1002/app.10438</work-type><urls><related-urls><url>/10.1002/app.10438</url></related-urls></urls><electronic-resource-num>/10.1002/app.10438</electronic-resource-num><access-date>2023/04/07</access-date></record></Cite></EndNote>2、丁腈橡膠等膠黏劑的促進(jìn)劑、潤(rùn)滑油添加劑ADDINEN.CITE<EndNote><Cite><Author>Li</Author><Year>2018</Year><RecNum>209</RecNum><DisplayText><styleface="superscript">3</style></DisplayText><record><rec-number>209</rec-number><foreign-keys><keyapp="EN"db-id="s5ttfsrrmetp5xepwp2vff54e229r5ezwvte"timestamp="1680874984">209</key></foreign-keys><ref-typename="ElectronicArticle">43</ref-type><contributors><authors><author>Li,Wenyan</author><author>Lu,Shengchang</author><author>Zhao,Mengchan</author><author>Lin,Xinxing</author><author>Zhang,Min</author><author>Xiao,He</author><author>Liu,Kai</author><author>Huang,Liulian</author><author>Chen,Lihui</author><author>Ouyang,Xinhua</author><author>Ni,Yonghao</author><author>Wu,Hui</author></authors></contributors><titles><title>Self-HealingCelluloseNanocrystals-ContainingGelsviaReshufflingofThiuramDisulfideBonds</title><secondary-title>Polymers</secondary-title></titles><periodical><full-title>Polymers</full-title></periodical><volume>10</volume><number>12</number><keywords><keyword>cellulose</keyword><keyword>disulfide</keyword><keyword>gel</keyword><keyword>self-healing</keyword></keywords><dates><year>2018</year></dates><isbn>2073-4360</isbn><urls></urls><electronic-resource-num>10.3390/polym10121392</electronic-resource-num></record></Cite></EndNote>3、香皂的抑菌劑和除臭劑ADDINEN.CITEADDINEN.CITE.DATA4。研究表明，秋蘭姆類促進(jìn)劑屬于酸性超促進(jìn)劑，是一種效果較強(qiáng)的硫化促進(jìn)劑，一般被用作為第二促進(jìn)劑，它的活性處于二硫代氨基甲酸鹽和噻唑類促進(jìn)劑中間，可提高噻唑類和次磺酰胺類促進(jìn)劑的硫化速度和硫化度ADDINEN.CITE<EndNote><Cite><Author>Aalto-Korte</Author><Year>2016</Year><RecNum>207</RecNum><DisplayText><styleface="superscript">5</style></DisplayText><record><rec-number>207</rec-number><foreign-keys><keyapp="EN"db-id="s5ttfsrrmetp5xepwp2vff54e229r5ezwvte"timestamp="1680874729">207</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Aalto-Korte,Kristiina</author><author>Pesonen,Maria</author></authors></contributors><titles><title>Patternsofsimultaneouspatchtestreactionstothiuramsanddithiocarbamatesin164patients</title><secondary-title>ContactDermatitis</secondary-title></titles><periodical><full-title>ContactDermatitis</full-title><abbr-1>ContactDermatitis</abbr-1><abbr-2>ContactDermatitis</abbr-2></periodical><pages>353-357</pages><volume>75</volume><number>6</number><keywords><keyword>1,3-diphenylguanidine</keyword><keyword>contactallergy</keyword><keyword>screening</keyword><keyword>thiurammix</keyword><keyword>zincdibutyldithiocarbamate</keyword><keyword>zincdiethyldithiocarbamate</keyword><keyword>zincdimethyldithiocarbamate</keyword></keywords><dates><year>2016</year><pub-dates><date>2016/12/01</date></pub-dates></dates><publisher>JohnWiley&Sons,Ltd</publisher><isbn>0105-1873</isbn><work-type>/10.1111/cod.12687</work-type><urls><related-urls><url>/10.1111/cod.12687</url></related-urls></urls><electronic-resource-num>/10.1111/cod.12687</electronic-resource-num><access-date>2023/04/07</access-date></record></Cite></EndNote>5。二硫化和多硫化秋蘭姆在標(biāo)準(zhǔn)硫化溫度下能釋放出活性硫，作為硫給予體可用于硫化體系A(chǔ)DDINEN.CITEADDINEN.CITE.DATA6。其品種主要有一硫化四甲基秋蘭姆（TMTM）、二硫化四甲基秋蘭姆（TMTD）、二硫化四乙基秋蘭姆（TETD）、四硫化雙（1,5-亞戊基）秋蘭姆（DPTT）等。2秋蘭姆參與的C-X鍵的構(gòu)建2.1二硫化秋蘭姆試劑合成烷基二硫代氨基甲酸酯Cheng及其同事們使用氯丁烷和四甲基二硫化秋蘭姆作為模板反應(yīng)。他們分別對(duì)反應(yīng)溶劑、催化劑、堿和溫度進(jìn)行了優(yōu)化。先廣泛對(duì)銅、鐵、鈷、鎳等催化劑進(jìn)行了篩選，發(fā)現(xiàn)了Co(acac)2為最佳催化劑。他們同時(shí)發(fā)現(xiàn)在沒(méi)有Co(acac)2的情況下產(chǎn)品依舊有一個(gè)很可觀的產(chǎn)量，這表明催化劑對(duì)反應(yīng)不起關(guān)鍵作用。進(jìn)一步篩選溶劑后顯示二甲基亞砜是最合適的溶劑。然后篩選了K2CO3、tBuOK、KOH、NaOH和CH3ONa，結(jié)果表明以Cs2CO3作為堿是反應(yīng)效果最優(yōu)。實(shí)驗(yàn)中他們發(fā)現(xiàn)，減少堿的量會(huì)大大降低產(chǎn)量，同時(shí)增加堿的量對(duì)產(chǎn)量沒(méi)有幫助。最后，篩選溫度結(jié)果表明反應(yīng)應(yīng)在60℃進(jìn)行。通過(guò)反復(fù)實(shí)驗(yàn)，他們提出了一種簡(jiǎn)單有效的方法來(lái)進(jìn)行烷基二硫代氨基甲酸酯的制備，產(chǎn)品經(jīng)處理可獲得優(yōu)良或極好的產(chǎn)量，該方法具有高效、無(wú)過(guò)渡金屬、產(chǎn)率好、操作簡(jiǎn)便等特點(diǎn)，對(duì)方便制備一些具有潛在生物活性的金屬具有實(shí)用的合成價(jià)值A(chǔ)DDINEN.CITE<EndNote><Cite><Author>Cheng</Author><Year>2019</Year><RecNum>197</RecNum><DisplayText><styleface="superscript">7</style></DisplayText><record><rec-number>197</rec-number><foreign-keys><keyapp="EN"db-id="s5ttfsrrmetp5xepwp2vff54e229r5ezwvte"timestamp="1680873058">197</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Cheng,Yu</author><author>Peng,Han-Ying</author><author>Dong,Zhi-Bing</author></authors></contributors><titles><title>Synthesisofalkyldithiocarbamatesbyusingthiuramdisulfidereagents:Ametal-freeC(sp3)-Sbondformation</title><secondary-title>TetrahedronLetters</secondary-title></titles><periodical><full-title>TetrahedronLetters</full-title><abbr-1>TetrahedronLett.</abbr-1><abbr-2>TetrahedronLett</abbr-2></periodical><pages>617-620</pages><volume>60</volume><number>8</number><keywords><keyword>Alkyl</keyword><keyword>Dithiocarbamate</keyword><keyword>C-Scoupling</keyword><keyword>Synthesis</keyword><keyword>Metal-free</keyword></keywords><dates><year>2019</year><pub-dates><date>2019/02/21/</date></pub-dates></dates><isbn>0040-4039</isbn><urls><related-urls><url>/science/article/pii/S004040391930070X</url></related-urls></urls><electronic-resource-num>/10.1016/j.tetlet.2019.01.044</electronic-resource-num></record></Cite></EndNote>7。2.2簡(jiǎn)單條件下肉桂酸與四烷基二硫化秋蘭姆酰胺化反應(yīng)合成肉桂酸酯Lai及其同事們選擇肉桂酸二硫化四甲基秋蘭姆為模型進(jìn)行反應(yīng)，為了提高收率，他們進(jìn)行了一些路易斯酸堿進(jìn)行了篩選，結(jié)果表明，PPh3明顯優(yōu)于其他。并且他們發(fā)現(xiàn)，當(dāng)反應(yīng)在堿下進(jìn)行時(shí)，肉桂酸的收率進(jìn)一步提高。進(jìn)一步篩選后發(fā)現(xiàn)反應(yīng)的最佳溶劑為1,2二氯乙烷，最佳反應(yīng)溫度和時(shí)間為100℃，48h。該反應(yīng)的主要特征包括容易獲得的試劑，操作簡(jiǎn)單，官能團(tuán)相容性好，適于克級(jí)合成ADDINEN.CITE<EndNote><Cite><Author>Lai</Author><Year>2020</Year><RecNum>198</RecNum><DisplayText><styleface="superscript">8</style></DisplayText><record><rec-number>198</rec-number><foreign-keys><keyapp="EN"db-id="s5ttfsrrmetp5xepwp2vff54e229r5ezwvte"timestamp="1680873258">198</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Lai,Miao</author><author>Wu,Zhiyong</author><author>Su,Fangyao</author><author>Yu,Yujian</author><author>Jing,Yanqiu</author><author>Kong,Jinmin</author><author>Wang,Zhenteng</author><author>Wang,Shuai</author><author>Zhao,Mingqin</author></authors></contributors><titles><title>SynthesisofCinnamidesviaAmidationReactionofCinnamicAcidswithTetraalkylthiuramDisulfidesUnderSimpleCondition</title><secondary-title>EuropeanJournalofOrganicChemistry</secondary-title></titles><periodical><full-title>EuropeanJournalofOrganicChemistry</full-title><abbr-1>Eur.J.Org.Chem.</abbr-1><abbr-2>EurJOrgChem</abbr-2></periodical><pages>198-208</pages><volume>2020</volume><number>2</number><keywords><keyword>Cinnamides</keyword><keyword>Cinnamicacids</keyword><keyword>Tetraalkylthiuramdisulfides</keyword><keyword>C–Ncrosscoupling</keyword><keyword>Syntheticmethods</keyword></keywords><dates><year>2020</year><pub-dates><date>2020/01/16</date></pub-dates></dates><publisher>JohnWiley&Sons,Ltd</publisher><isbn>1434-193X</isbn><work-type>/10.1002/ejoc.201901630</work-type><urls><related-urls><url>/10.1002/ejoc.201901630</url></related-urls></urls><electronic-resource-num>/10.1002/ejoc.201901630</electronic-resource-num><access-date>2023/04/07</access-date></record></Cite></EndNote>8。2.3水中無(wú)過(guò)渡金屬C(sp3)?S偶聯(lián):以二硫化秋蘭姆為有機(jī)硫源合成二硫代氨基甲酸芐酯Peng等人選擇氯化芐和四烷基二硫化秋蘭姆(TMTD)作為模型在水中進(jìn)行反應(yīng)，篩選得到100℃為最佳反應(yīng)溫度的實(shí)驗(yàn)結(jié)論。且他們發(fā)現(xiàn)，在反應(yīng)中加入堿后，產(chǎn)率顯著提高。因此，他們對(duì)不同的堿進(jìn)行篩選，選擇K2CO3為堿反應(yīng)最佳。在上述優(yōu)化條件下，他們接著進(jìn)行了四烷基二硫化秋蘭姆與不同鹵化芐反應(yīng)的研究，結(jié)果表明，對(duì)于四甲基二硫化秋蘭姆(TMTD)，溴化芐的反應(yīng)活性優(yōu)于氯化芐ADDINEN.CITE<EndNote><Cite><Author>Peng</Author><Year>2019</Year><RecNum>199</RecNum><DisplayText><styleface="superscript">9</style></DisplayText><record><rec-number>199</rec-number><foreign-keys><keyapp="EN"db-id="s5ttfsrrmetp5xepwp2vff54e229r5ezwvte"timestamp="1680873514">199</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Peng,Han-Ying</author><author>Dong,Zhi-Bing</author></authors></contributors><titles><title>Transition-Metal-FreeC(sp3)–SCouplinginWater:SynthesisofBenzylDithiocarbamatesUsingThiuramDisulfidesasanOrganosulfurSource</title><secondary-title>EuropeanJournalofOrganicChemistry</secondary-title></titles><periodical><full-title>EuropeanJournalofOrganicChemistry</full-title><abbr-1>Eur.J.Org.Chem.</abbr-1><abbr-2>EurJOrgChem</abbr-2></periodical><pages>949-956</pages><volume>2019</volume><number>5</number><keywords><keyword>Metal-free</keyword><keyword>Coupling</keyword><keyword>Water</keyword><keyword>Dithiocarbamate</keyword><keyword>Synthesis</keyword></keywords><dates><year>2019</year><pub-dates><date>2019/02/07</date></pub-dates></dates><publisher>JohnWiley&Sons,Ltd</publisher><isbn>1434-193X</isbn><work-type>/10.1002/ejoc.201801520</work-type><urls><related-urls><url>/10.1002/ejoc.201801520</url></related-urls></urls><electronic-resource-num>/10.1002/ejoc.201801520</electronic-resource-num><access-date>2023/04/07</access-date></record></Cite></EndNote>9。綜上所述，他們開(kāi)發(fā)了一種簡(jiǎn)單、高效的合成二硫代氨基甲酸芐酯的方法。該方法具有實(shí)驗(yàn)簡(jiǎn)單、以水為溶劑、不含過(guò)渡金屬、功能相容性好、產(chǎn)率好到優(yōu)良等優(yōu)點(diǎn)，在一些潛在生物活性化合物的方便制備中具有潛在的合成價(jià)值。2.4在KIO3和TEMPO存在下鄰羥基苯胺酮與四烷基二硫化秋蘭姆反應(yīng)合成3-二硫代氨基色酮Wan等人對(duì)烯胺酮與四甲基秋蘭姆的反應(yīng)進(jìn)行了優(yōu)化研究，在不同的碘催化劑，包括n-碘丁二酰亞胺(NIS)、二乙酰氧基碘苯（PhI(OAc)2）和高碘酸鉀（KIO3）的存在下進(jìn)行該反應(yīng)，發(fā)現(xiàn)使用2個(gè)當(dāng)量的高碘酸鉀作為催化劑時(shí)反應(yīng)效果最佳。隨后，將反應(yīng)介質(zhì)改變?yōu)椴煌挠袡C(jī)溶劑或水，結(jié)果表明二甲基亞砜為最佳的反應(yīng)溶劑。使用了幾種不同的氧化劑作為添加劑，發(fā)現(xiàn)TEMPO可以明顯提高反應(yīng)產(chǎn)率。此外，反應(yīng)在110℃下反應(yīng)4h的效果最好ADDINEN.CITE<EndNote><Cite><Author>Zhang</Author><Year>2021</Year><RecNum>200</RecNum><DisplayText><styleface="superscript">10</style></DisplayText><record><rec-number>200</rec-number><foreign-keys><keyapp="EN"db-id="s5ttfsrrmetp5xepwp2vff54e229r5ezwvte"timestamp="1680873711">200</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Zhang,Tao</author><author>Yao,Weijun</author><author>Wan,Jie-Ping</author><author>Liu,Yunyun</author></authors></contributors><titles><title>Transition-Metal-FreeC(sp2)-HDithiocarbamationandChromoneAnnulationCascadefor3-DithiocarbamylChromoneSynthesis</title><secondary-title>AdvancedSynthesis&Catalysis</secondary-title></titles><periodical><full-title>AdvancedSynthesis&Catalysis</full-title><abbr-1>Adv.Synth.Catal.</abbr-1><abbr-2>AdvSynthCatal</abbr-2></periodical><pages>4811-4816</pages><volume>363</volume><number>20</number><keywords><keyword>Enaminone</keyword><keyword>Thiuram</keyword><keyword>C?HDithiocarbamation</keyword><keyword>Chromoneannulation</keyword><keyword>Transitionmetal-free</keyword></keywords><dates><year>2021</year><pub-dates><date>2021/10/19</date></pub-dates></dates><publisher>JohnWiley&Sons,Ltd</publisher><isbn>1615-4150</isbn><work-type>/10.1002/adsc.202100617</work-type><urls><related-urls><url>/10.1002/adsc.202100617</url></related-urls></urls><electronic-resource-num>/10.1002/adsc.202100617</electronic-resource-num><access-date>2023/04/07</access-date></record></Cite></EndNote>10。2.5銅催化的C(sp2)?S偶聯(lián)反應(yīng)與秋蘭姆類試劑合成芳基二硫代氨基甲酸酯Dong等人開(kāi)發(fā)了一種銅催化交叉偶聯(lián)合成芳基二硫代氨基甲酸酯的方法，反應(yīng)在Cs2CO3做為堿，Cu2O作催化劑，溶劑為二甲基亞砜的條件下，80℃反應(yīng)48h時(shí)產(chǎn)率最高。該方法使用了價(jià)格低廉、環(huán)境友好的二硫化秋蘭姆試劑，底物實(shí)用性廣泛，從而得到相應(yīng)的高產(chǎn)率產(chǎn)品。催化體系來(lái)源于現(xiàn)成的試劑(Cu2O和Cs2CO3)，不需要額外的配體。他們還進(jìn)行了放大反應(yīng)以證實(shí)該工藝的實(shí)用性ADDINEN.CITE<EndNote><Cite><Author>Dong</Author><Year>2017</Year><RecNum>201</RecNum><DisplayText><styleface="superscript">11</style></DisplayText><record><rec-number>201</rec-number><foreign-keys><keyapp="EN"db-id="s5ttfsrrmetp5xepwp2vff54e229r5ezwvte"timestamp="1680873836">201</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Dong,Zhi-Bing</author><author>Liu,Xing</author><author>Bolm,Carsten</author></authors></contributors><titles><title>Copper-CatalyzedC(sp2)–SCouplingReactionsfortheSynthesisofArylDithiocarbamateswithThiuramDisulfideReagents</title><secondary-title>OrganicLetters</secondary-title></titles><periodical><full-title>OrganicLetters</full-title><abbr-1>Org.Lett.</abbr-1><abbr-2>OrgLett</abbr-2></periodical><pages>5916-5919</pages><volume>19</volume><number>21</number><dates><year>2017</year><pub-dates><date>2017/11/03</date></pub-dates></dates><publisher>AmericanChemicalSociety</publisher><isbn>1523-7060</isbn><urls><related-urls><url>/10.1021/lett.7b02911</url></related-urls></urls><electronic-resource-num>10.1021/lett.7b02911</electronic-resource-num></record></Cite></EndNote>11。2.6苯甲酸和四烷基二硫化秋蘭姆在銅鹽催化下生成相應(yīng)的芳基甲酰胺化合物Zeng課題組研究了以四烷基二硫化秋蘭姆為新的胺源在一階銅鹽催化下生成相應(yīng)的芳基甲酰胺化合物的反應(yīng)過(guò)程。在比較了不同的一階和二階銅鹽作為催化劑的產(chǎn)率后，結(jié)果表明一階銅鹽相較于二階銅鹽的催化效果更好。同時(shí)還發(fā)現(xiàn)苯甲酸上無(wú)論是帶吸電子基還是給電子基，抑或兩者同時(shí)存在，都不會(huì)對(duì)產(chǎn)物的產(chǎn)率產(chǎn)生很大的影響，都能以較為可觀的產(chǎn)率得到產(chǎn)物。該方法不會(huì)受到N-取代烷基空間位阻的影響，底物的適應(yīng)性較好，且原料易得，操作簡(jiǎn)單ADDINEN.CITE<EndNote><Cite><Author>Wu</Author><Year>2018</Year><RecNum>203</RecNum><DisplayText><styleface="superscript">12</style></DisplayText><record><rec-number>203</rec-number><foreign-keys><keyapp="EN"db-id="s5ttfsrrmetp5xepwp2vff54e229r5ezwvte"timestamp="1680874118">203</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Wu,Zhiyong</author><author>Cheng,Chuance</author><author>Tang,Xiangting</author><author>Liu,Shi</author><author>Xi,Gaolei</author><author>Zhao,Mingqin</author><author>Liu,Pengfei</author></authors></contributors><titles><title>Phosphine-PromotedAmideBondFormationReactionsfromCarboxylicAcidsandTetraalkylthiuramDisulfides</title><secondary-title>ChemistrySelect</secondary-title></titles><periodical><full-title>ChemistrySelect</full-title></periodical><pages>13038-13041</pages><volume>3</volume><number>46</number><keywords><keyword>2-nitrobenzoicacid</keyword><keyword>phosphine-promoted</keyword><keyword>cross-coupling</keyword><keyword>amidebondformation</keyword><keyword>N-substitutedbenzamides</keyword></keywords><dates><year>2018</year><pub-dates><date>2018/12/13</date></pub-dates></dates><publisher>JohnWiley&Sons,Ltd</publisher><isbn>2365-6549</isbn><work-type>/10.1002/slct.201803311</work-type><urls><related-urls><url>/10.1002/slct.201803311</url></related-urls></urls><electronic-resource-num>/10.1002/slct.201803311</electronic-resource-num><access-date>2023/04/07</access-date></record></Cite></EndNote>12。2.72–氨基苯酚、TMTM和丙烯基溴反應(yīng)生成2–(烯丙基硫基)苯并[d]惡唑Wang等人選用2–氨基苯酚、TMTM(二硫化四甲基秋蘭姆)和丙烯基溴作為起始底物進(jìn)行反應(yīng)，對(duì)反應(yīng)底物比例進(jìn)行篩選后發(fā)現(xiàn)，增加一硫化四甲基秋蘭姆的量無(wú)法提高產(chǎn)率，但是增加丙烯基溴的量產(chǎn)率會(huì)得到有效的提升，碳酸鈉對(duì)提升反應(yīng)產(chǎn)率有很大的作用。反應(yīng)需分兩步，第一步為2–氨基苯酚，二硫化四甲基秋蘭姆，碳酸鈉在120℃下反應(yīng)，第二步在第一步反應(yīng)2h后加入丙烯基溴，在60℃的溫度下繼續(xù)反應(yīng)ADDINEN.CITE<EndNote><Cite><Author>Jiao</Author><Year>2022</Year><RecNum>204</RecNum><DisplayText><styleface="superscript">13</style></DisplayText><record><rec-number>204</rec-number><foreign-keys><keyapp="EN"db-id="s5ttfsrrmetp5xepwp2vff54e229r5ezwvte"timestamp="1680874294">204</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Jiao,Jing</author><author>Xiao,Fangtao</author><author>Wang,Cheng</author><author>Zhang,Zhipeng</author></authors></contributors><titles><title>Iodine-PromotedMetal-FreeCyclizationandO/SExchangeofAcrylamideswithThiuram:One-StepSynthesisofQuinolino-2-thiones</title><secondary-title>TheJournalofOrganicChemistry</secondary-title></titles><periodical><full-title>TheJournalofOrganicChemistry</full-title><abbr-1>J.Org.Chem.</abbr-1></periodical><pages>4965-4970</pages><volume>87</volume><number>7</number><dates><year>2022</year><pub-dates><date>2022/04/01</date></pub-dates></dates><publisher>AmericanChemicalSociety</publisher><isbn>0022-3263</isbn><urls><related-urls><url>/10.1021/acs.joc.1c03030</url></related-urls></urls><electronic-resource-num>10.1021/acs.joc.1c03030</electronic-resource-num></record></Cite></EndNote>13。2.8苯酚和TMTD反應(yīng)生成O-苯基N,N-二甲基硫代氨基甲酸酯Wang等人使用苯酚和二硫化四甲基秋蘭姆為底物模板反應(yīng)，篩選條件時(shí)發(fā)現(xiàn)堿性越強(qiáng)產(chǎn)率越高，于是選用NaH作為反應(yīng)用的堿。對(duì)比不同溶劑后發(fā)現(xiàn)N,N-二甲基甲酰胺為最佳溶劑，在此條件下篩選出最佳溫度為80℃，且金屬催化劑對(duì)反應(yīng)無(wú)明顯促進(jìn)作用。此方法不僅可以用于酚類的硫代酰胺化，同樣也適用于脂肪醇的硫代酰胺化，顯示出良好的底物適應(yīng)性ADDINEN.CITEADDINEN.CITE.DATA14。3實(shí)驗(yàn)部分3.1儀器試劑柱層析硅膠采用200-300目硅膠，薄層層析使用的是GF254高效硅膠板，檢測(cè)方法為紫外燈顯色(254nm)。核磁共振譜通過(guò)BrukeAvance

III

(400

MHz)

核磁共振儀測(cè)定。1HNMR以TMS(d=0

ppm)為內(nèi)標(biāo)，13C

NMR以CDCl3為內(nèi)標(biāo)(d

=

77.0ppm)，峰的標(biāo)定以s表示單峰，d表示雙峰，t表示三重峰，br表示寬峰，m表示多重峰。所有試劑和藥品未經(jīng)說(shuō)明，均是購(gòu)買后直接使用。3.2制備過(guò)程向15ml密封管中加入0.2mmol8-氨基喹啉，0.22mmol四甲基二硫化秋蘭姆，0.5ml水，1.5ml無(wú)水乙醇，用聚四氟乙烯蓋密封后放入沙浴鍋中在80℃下反應(yīng)24h。待反應(yīng)結(jié)束，將其冷卻至室溫，再加入5mL水，用乙酸乙酯(30mL)提取得到的混合物，使用分液漏斗收集管內(nèi)上層有機(jī)相，用少量水沖洗萃取三次。使用旋轉(zhuǎn)蒸發(fā)儀，在減壓條件下除去所得溶液中的溶劑。將得到的殘?jiān)褂弥鶎游龇ǚ蛛x，用混合石油醚和乙酸乙酯(v/v=3:1~8:1)洗脫得到純產(chǎn)物。使用旋轉(zhuǎn)蒸發(fā)儀旋干后得到產(chǎn)物，收集稱重后計(jì)算產(chǎn)率。3.3化合物表征數(shù)據(jù)N,N-Dimethyl-1-((quinolin-7-ylamino)thio)-1-thioxomethanamine(3a).Yield:63%;yellowsolid;1HNMR(400MHz,CDCl3)δ:10.3(s,1H),9.4(d,J=7.7Hz,1H),8.8(d,J=4.1Hz,1H),8.2(d,J=8.2Hz,1H),7.6(t,J=8.0Hz,1H),7.5–7.4(m,2H),3.5(s,6H).13CNMR(100MHz,CDCl3)δ179.0,147.8,139.3,136.6,136.0,128.0,127.0,121.5,121.1,116.8,41.0.N,N-Dimethyl-1-((phenylamino)thio)-1-thioxomethanamine(3b).Yield:70%;whitesolid;1HNMR(400MHz,CDCl3)δ:7.3(t,J=7.7Hz,2H),7.2(d,J=7.7Hz,2H),7.2(t,J=7.3Hz,1H),7.1(s,1H),3.3(s,6H).13CNMR(100MHz,CDCl3)δ182.7,139.8,128.8,125.5,124.7,41.5.1-(((4-Bromophenyl)amino)thio)-N,N-dimethyl-1-thioxomethanamine(3c).Yield:67%;whitesolid;1HNMR(400MHz,CDCl3)δ:7.4(d,J=8.6Hz,2H),7.2(d,J=8.5Hz,2H),7.1(s,1H),3.3(s,6H).13CNMR(100MHz,CDCl3)δ182.2,138.9,131.8,126.6,118.7,41.4.N,N-Bimethyl-1-(((4-methylbenzyl)amino)thio)-1-thioxomethanamine(3d).Yield:70%;whitesolid;1HNMR(400MHz,CDCl3)δ:7.2(d,J=7.8Hz,2H),7.1(d,J=7.7Hz,2H),5.5(s,1H),4.8(d,J=4.7Hz,2H),3.2(s,6H),2.3(s,3H).13CNMR(100MHz,CDCl3)δ181.9,137.4,135.1,129.4,128.0,50.2,40.5,21.1.N-Ethyl-N-(((quinolin-7-ylamino)thio)carbonothioyl)ethanamine(3e).Yield:55%;yellowsolid;1HNMR(400MHz,CDCl3)δ:10.3(s,1H),9.5(d,J=7.6Hz,1H),8.8(s,1H),8.1(d,J=8.1Hz,1H),7.8–7.4(m,3H),3.9(s,4H),1.4(s,6H).13CNMR(100MHz,CDCl3)δ:177.4,147.8,139.3,136.5,136.1,127.9,126.9,121.5,120.9,116.7,45.6,12.74結(jié)果與討論4.1條件的優(yōu)化我們以8-氨基喹啉和四甲基二硫化秋蘭姆為反應(yīng)物對(duì)反應(yīng)溶劑、溫度和反應(yīng)時(shí)間及添加劑進(jìn)行篩選。首先，對(duì)反應(yīng)溶劑進(jìn)行優(yōu)化，發(fā)現(xiàn)當(dāng)乙醇和水配比為1.5比0.5時(shí)，反應(yīng)效果最佳（表1，條目1-7）。隨后，我們升高溫度或者降低溫度發(fā)現(xiàn)產(chǎn)率降低（表1，條目8-9）。然后，對(duì)反應(yīng)時(shí)間進(jìn)行了優(yōu)化發(fā)現(xiàn)反應(yīng)時(shí)間為24h反應(yīng)效果最佳（表1，條目10-11）。我們?cè)诜磻?yīng)中添加了酸和堿作為添加劑時(shí)產(chǎn)率并沒(méi)有升高。（表1，條目12-13）。最后，我們確定反應(yīng)的最優(yōu)條件為：以乙醇和水作為混合溶劑、反應(yīng)溫度為80℃、反應(yīng)時(shí)間為24h可以以63%的產(chǎn)率得到目標(biāo)產(chǎn)物。EntryT(℃)SolventTime(h)Yield(%)b180EtOH2436280H2O2412380EL24trace480MeOH24315c80EtOH:H2O24426d80EtOH:H2O24637e80EtOH:H2O24578d70EtOH:H2O24589d90EtOH:H2O246010d80EtOH:H2O225111d80EtOH:H2O265812d,f80EtOH:H2O243213d,g80EtOH:H2O24traceaGeneralconditions:1a(0.25mmol),2a(0.3mmol)andsolvent(2ml),stirredat80℃for24h.bYieldofisolatedproductbasedon1a.cEtOH:H2O=1:1,dEtOH:H2O=1.5:0.5,eEtOH:H2O=1.8:0.2,f1equivNa2CO3asadditive,g1equiv37%HClasadditive4.2底物的拓展在確定最優(yōu)反應(yīng)條件后，我們選用不同的含氨基的芳香化合物來(lái)探究該反應(yīng)的普適性。我們用苯胺和對(duì)溴苯胺能以良好的產(chǎn)率得到目標(biāo)產(chǎn)物3b和3c。同時(shí)，令人驚喜的是芐胺和四甲基秋蘭姆反應(yīng)也能以良好的產(chǎn)率得到的相應(yīng)的目標(biāo)產(chǎn)物3d。當(dāng)我們將四甲基二硫化秋蘭姆換成四乙基二硫化秋蘭姆進(jìn)行反應(yīng)也能以中等產(chǎn)率得到目標(biāo)產(chǎn)物3e。如表2所示，產(chǎn)物的結(jié)構(gòu)基本都符合我們的推斷和預(yù)期。所合成的產(chǎn)物通過(guò)核磁共振測(cè)試，并結(jié)合文獻(xiàn)結(jié)果確認(rèn)了結(jié)構(gòu)。aGeneralconditions:1(0.2mmol),2(0.22mmol),andsolvent(2ml),stirredat80℃for24h5結(jié)論與展望秋蘭姆是一類用途廣泛的促進(jìn)劑，在橡膠工業(yè)中占據(jù)了十分重要的地位。在此之前已有許多學(xué)者對(duì)秋蘭姆類化合物的合成做了許多的研究與探討，也在此基礎(chǔ)上發(fā)展了多種合成方法。本文針對(duì)近幾十年報(bào)道的相關(guān)合成方法進(jìn)行了總結(jié)，在這些相關(guān)文獻(xiàn)的合成基礎(chǔ)上，本文重點(diǎn)研究了含氨基的芳香化合物與秋蘭姆合成形成含氮硫鍵的化合物的合成，通過(guò)對(duì)反應(yīng)條件的優(yōu)化，我們得到了一個(gè)最優(yōu)的反應(yīng)條件：以四甲基二硫化秋蘭姆（0.3mmol）和8-氨基喹啉（0.25mmol）為原料，以乙醇和水作為混合溶劑，在80℃的溫度下反應(yīng)24h，最終以63%的產(chǎn)率得到產(chǎn)物。這種方法操作簡(jiǎn)單，且不需要催化劑，使用的溶劑也是綠色溶劑，對(duì)環(huán)境友好，為合成含氮硫鍵的化合物提供了一個(gè)方案。參考文獻(xiàn)ADDINEN.REFLIST1. Debnath,S.C.;Basu,D.K.,StudiesontheeffectofthiuramdisulfideonNRvulcanizationacceleratedbythiazole-basedacceleratorsystems.J.Appl.Polym.Sci.1996,60,845-855.2. González,L.;Rodríguez,A.;DelCampo,A.;Marcos-Fernández,A.,Crosslinkreactionofnaturalrubberwiththiuramsulphurdonorsinthepresenceofathiurammonosulfide.J.Appl.Polym.Sci.2002,85,491-499.3. Li,W.;Lu,S.;Zhao,M.;Lin,X.;Zhang,M.;Xiao,H.;Liu,K.;Huang,L.;Chen,L.;Ouyang,X.;Ni,Y.;Wu,H.,Self-HealingCelluloseNanocrystals-ContainingGelsviaReshufflingofThiuramDisulfideBonds.InPolymers2018;Vol.10.4. (a)Enders,D.;Rembiak,A.;Liebich,J.X.,DirectOrganocatalyticα-SulfenylationofAldehydesandKetoneswithTetramethylthiuramDisulfide.Synthesis2011,2011,281-286;(b)Schnell,B.;Kappe,T.,Sulfenylationofheterocyclic1,3-dicarbonylsystems:4-Hydroxy-2-pyrones,6-hydroxy-4-pyrimidones,4-hydroxy-2-pyridones,4-hydroxy-6-pyridazinones,and5-hydroxy-3-pyrazolones.J.Heterocycl.Chem.2000,37,911-919.5. Aalto-Korte,K.;Pesonen,M.,Patternsofsimultan