(E)-α,β-不饱和硝基烯烃的高度区域选择性合成方法

浙江大学学报(理学版)第39卷第3期.Journal of Zhejiang University( Science Edition)Vol: 39 No,3htp://www. journals. zju. edu. cn/sci2012年5月DOI: 10. 3785/j. issn, 1008-9497. 2012.03. 015(E)-a,β-不饱和硝基烯烃的高度区域选择性合成方法谢隽毅'，张斌”， 陈仁尔'，周其忠",徐土根'，叶余原'，蒋华江'(1.台州学院化学系，浙江台州317000 2.浙江工业大学药学院，浙江杭州310014;3.杭州师范大学材料与化学化工学院，浙江杭州310036)摘戛:醛和硝基甲炕在甲醇和NaOH水溶液的混合溶液中在0 C反应,随后用稀盐酸处理,生威(E)-a,f不饱和硝基烯烃单一化合物,反应有高度的区域选择性,牧率较高(76%~95%).合成方法便捷、高效、清洁,属于绿色合咸.关键词:脏;硝基甲烷;(E)-a,月不饱和硝基烯烃中图分类号:0622.1文献标志码:A文章编号:1008 -9497(2012)03-308-05XIE Juny4 , 2HANG Bin', CHEN Ren-er' , ZHOU Qi- zhong'，XU Tugen', YE Yu yuan'，JIANG Hua jiang'(1. Department of Chemistry, Taizhou University, Taizhou 317000, Zhejiang Province, China; 2. College ofPharmacy. Zhejiang University of Techmology, Hangzhou 310014, China; 3. College of Material，Chemistryand Chemical Engineer, Hangzhou Normal Uniuersity, Hangzhou 310036. China)Noel syothesis of (E)-a.f umaturated railknss Journal of Dhejiang UriesritfScene Editin), 2012,39(3):308- -312Abstract; Aldechydes reacted with nitromethane in a mixed solution of methanol and aqueous NaOH at0心，fllowed bytreatment with dilute hydrochloric acid to aford only (E)-a ,funsaturated nitralkeses in good to excllet yields (76-95%) without its corresponding Z isomer. The reaction is simple, eficient clean, which belongs to green syntheisKey Words: aldehyde; nitromethane; (E) ~a ,funsaturated ntralkenes不饱和的硝基脂肪酸是一类新的内源性抗炎介基的Michael加成[2 -1;有机金属化合物与硝基烯质[1.不饱和硝基油酸能防止鼠肾缺血和再灌注损烃间的不对称共轭加成[5]以及具有旋光活性的伤50].当然,硝基烯烃也还有其他生物活性.(E)-硝基烯烃的立体选择性氮杂环丙化8。.最近,(E)-a,f-不饱和硝基烯烃被广泛用于一烯烃经-氧化氮硝化可得到收率不错的(E)-a.些反应中的Michael受体,如氢键介导的具有高度ρ不饱和硝基烯烃["7- 81.但许多烯烃-般不易制得，立体选择性的Michael-Michael 串联反应[);醛、酮而且一氧化氮是有毒气体.醛和1-硝基烯烃在喊性与硝基烯烃的不对称Michael反应[-1] ;吲哚、吡咯AlO,和超临界的CO2的条件下反应可制得(E)-a,与硝基烯烃的立体选择性的Friedel-Crafts烷基化β不饱和硝基烯烃,但此法收率不是很高[(0];不饱和反应([-10);硝基烯烃与硝基烷烃之间的不对称羧酸在硝酸和催化量的AIBN作用下硝化和脱羧基Michal加成["9-川;有硝基烷烃参与的串联催化的后可制得收率不错的硝基苯乙烯和硝基芳香烃(1]..不对称Friedel-Crafts/Henry 反应[};硝基烯烃的硝基甲烷与相应的醛通过Henry缩合可得到β硝基不对称生物还原(=-53] ;多米诺硝基-Michael/Henry醇F硝基醇再经DCC/CuCl或三氟乙酸酐/三乙胺反应e,2];不对称多组分串联反应[820;不对称硝脱水(2.2 ,或者也可以经MsC/EtN..5l或P,Of#]收稱日期:2011-07-11.基金项目:国家自然科学基金资助项日21172166)1浙江省自然科学基金资助项目(4100783):浙江省教育厅科研计划资助项目.(20061048).作者简介:谢隽教(1990-),男,主要从事有机化学研究.●通信作者.E mail; qizhongchou@yahoo. com;jbj@txc. edu. cn.第3期谢隽毅,等:(E)-a.A-不饱和硝基烯烃的高度区域选挥性合成方法309脱水得到(E)-a,F不饱和硝基烯烃,反应需2步,收p.77~79 C;' H NMR(CDCl ,300 MHz):7. 99(d,率不是很高. BrCH2NO2与醛在碘化钠的催化下很容J = 13.6 Hz,1H),7. 52(dd,J=13.7 Hz,J:=8.2易就制得1-澳-1-硝基烷-2-醇,1-溴-1-硝基烷-2-醇再Hz,3H),7. 28(d,J=8.1 Hz,2H),2. 70(q,J=7. 6经二碘化钐β-消除制得(E) -a,f不饱和硝基烯烃;此Hz,2H),1.26(t,J=7. 6 Hz, 3H);"C NMR法收率一般,但E式产物占98%以上[47]. F-硝基醇酰(CDCl,75 MHz):149. 5, 139. 4, 136.5, 129. 5,化后在回流的苯溶液中用碳酸钠处理可得到收率不129. 2,127. 7,29.1,15.3.错的(E)-a,#不饱和硝基烯烃,但反应需要3步,总反式4-甲氧基-β-硝基苯乙烯(2c):黄色固体，收率不是很高[48].m. p. 86~88 C;'H NMR(CDCI]; . 300 MHz):7.97因此,笔者希望醛和硝基甲烷通过- -步反应就(d,J= 13.6 Hz,1H),7. 51(dd,J1=6.7 Hz,J2=能得到收率较高的(E) -a,β-不饱和硝基烯烃.1.9 Hz,3H),6. 96(d,J=8. 8 Hz,2H),3. 87(s,3H);"C NMR (CDC12,75 MHz):163. 1,139. 2,1实验部分135. 2,131.4,122.7,115.1,55.72-[(E)-2- 硝基乙烯基]呋哺(2d):黄色固体,m p.1.1主要 仪器与试剂72~75 C;'H NMR(CDCl, 300 MHz):7. 78(d,J=所有的化学品以及溶剂都是直接从供应商处买.13.2 Hz,1H) ,7.50~7. 60(m,2H),6. 90(d,J=3.5 Hz, .来的,没有经过进-一步的纯化,测得的熔点值未经校1H),6. 58(q,J=1. 8 Hz, 1H);I C NMR(CDCl,75.准.'HNMR在Bruker300MHz核磁共振仪上测MHz) :147.0,146.8,135.1,125. 6,120. 2,113. 5.试,"C NMR在Bruker 75 MHz核磁共振仪上测试.ar[(E)-2-硝基乙烯基]萘(2e);黄色固体,m.1.2化合物 2a-2m(2e,2f和2g除外)的合成p.87~89 C;' H NMR(CDCI, ,300 MHz) :8. 79(d,在甲醇(1 mL)溶液中加入醛(1 mmol) 和J=13.4 Hz,1H),7. 89~8. 11(m,3H),7. 47~CH3NO2(67. 1 mg,1. 1 mmol),搅拌,温度控制为7. 73(m,5H);"C NMR (CDCI3 ,75 MHz):138. 6,0 C,再取NaOH(2.00 mmol, 80.0 mg)溶于H2O 136. 3,133. 9,132. 7.131. 7,129. 2,127. 9,127. 1,(1mL)中,将所配得的NaOH溶液逐滴滴到反应液127. 0,126.6,125. 6,123. 1.中,约20 min.加完后,再搅拌6h.之后加入1 mol的反式-4-三氟甲基-β-硝基苯乙烯(20):黄色固HCl中和反应液.然后用二氣甲烷(3X2 mL)对反应液体,m. p.63~66 C;'H NMR(CDCl; ,300 MHz) :进行萃取,将合并后的有机相进行浓缩.将浓缩液过色8.03(d,J=13. 7 Hz,1H),7. 61~7. 74(m,5H);谐柱,淋洗剂选为正己烷/乙酸乙酯(40 : 1)或正己烷/1C NMR(CDCl; ,75 MHz):139. 1,137. 3,133. 8,二氯甲烷(4: 1),最后得到黄色液体或黄色固体.133. 7,133. 4,129. 5,126.5,125. 5,121.9.1.3 化合物2e,2f和2g的合成反式4-硝基-β硝基苯乙烯(2g);黄色固体，m.在甲醇(2 mL)溶液中加人醛(1 mmol)溶液和p.106~108 C;' H NMR(DMSO,300 MHz);8. 11CH,NO2(67.1 mg,1. 1 mmol),搅拌,温度控制为~8.41(m,6H) ;"C NMR(DMSO,75 MHz):148. 9,0 C ,再取NaOH(4.00 mmol,80, 0 mg)溶于H2O141. 0,136. 8,136. 5,130. 8,124. 0. .(2mL)中,将所配得的NaOH溶液逐滴滴到反应液(E)-1-硝基-4-苯基-1-丁烯(2h):黄色液体,'H中,约20 min,加完后,再搅拌6 h,之后加入1 molNMR( CDCl, 300 MHz):7. 15~7. 34 (m, 6H),的HCl中和反应液,然后用二氯甲烷(3X2 mL)对6. 94(dt,J1=13.4 Hz,J2=1.4 Hz,1H),2. 82(t,J反应液进行萃取,将合并后的有机相进行浓缩.将浓=7.4 Hz,2H),2.54~2. 62 (m,2H);"C NMR缩液过色谱柱,淋洗剂选为正己烷/二氯甲烷(4 :(CDCIs ,75 MHz):141. 6,140. 2,139.7,128. 9,128. 5,1),最后得到黄色固体.126.8,34.1,30. 3.1.4产物分析(1E)-3-乙基-1-硝基-1-戊烯(2i):黄色液体,H反式β-硝基苯乙烯(2a):黄色固体,m. p. 55~NMR(CDCl,300 MHz):6. 94~7.11( m,2H),58 C;' H NMR (CDCl,300 MHz):8. 01(d,J= .2. 03~2.19(m,1H),1. 35~1.66(m,4H) ,0.89(t, .13.7 Hz,1H),7, 42~7.61 (m, 6H);" C NMRJ=7.4 Hz,6H);"C NMR(CDCIs ,75 MHz):146. 6, .(CDCls, 75 MHz): 139. 3, 137.3, 132. 3,130. 3,139. 7,42. 8,26.8,11.7.129. 6,129. 3.[(E)-2-硝基乙烯基]环己烷(2j):黄色液体,H .反式-4-乙基β-硝基苯乙烯(2b):黄色固体,m.NMR(CDCl, ,300 MHz):7. 22(dd,J1=7.2 Hz,J,310断江大学学报(理学版)第39卷=7.2 Hz,1H),6. 93(dd,J=1.2 Hz,J:=1. 2表1在甲醇和 NaOH水溶液中于0心时Hz,1H),2. 21~2.28(m,1H),1.70~1.83 (m,各种醛和硝基甲烷的反应中5H),1.15~1. 40( m, 5H);8 C NMR (CDC1; ,75Table 1 Reaction of various aldehydes with nitromethaneMHz):147. 5,138. 4,37.7,31.6,25.8,25.6.in a solution of methanol and aqueous Na(H at 0 C(1E)-1-硝基-1-庚烯(2k):黄色液体,' H NMREntrysubstrateproductYield(CDCl3 ,300 MHz) ;7.24~7.33(m, 1H) ,6.98(dt,(2a) 88J;=13.4 Hz,J:=1.4 Hz,1H),2. 23~2.31(m,2H),1. 48~1.57(m,2H),1. 26~1.37(m,4H),0.91(i,J =6.9 Hz, 3H);' C NMR ( CDCl, 75MHz) :143. 0,139. 7,31.4,28.6,27.6,22. 5,14.0.着。(2b) 90(1E)-1-硝基-1-己烯(2I):黄色液体,' H NMR(CDCI; ,300 MHz):7. 24~7.33(m, 1H),6.98(dt,上。(2c) 92J;=13.4 Hz,J2=1.4 Hz,1H),2. 24~2.32(m, .2H),1. 32~1.56(m,4H),0. 94(t,J=7.3 Hz,3H);"C NMR(CDCl],75 MHz):143. 0,139. 7,~(2d) 9429. 9,28.2,22.3,13.8.(1E)-1-硝基-1-戊烯(2m):黄色液体,H NMR(CDCl, ,300 MHz):7. 23~7.33(m,1H),6. 99(d,J(2e) 95=13. 4 Hz,1H) ,2.22~2.30(m,2H),1. 50~1.60(m,2H),0.98(t,J=7. 4 Hz,3H);"C NMR(CDCl3,75 MHz):142. 7,139. 8,30. 5,21. 2,13.7.是(21) 772结果与讨论初步研究了在0C时苯甲醛与硝基甲烷在甲醇(2g) 76和氢氧化钠溶液中的反应(如图1和表1所示).在甲醇(1 mL)溶液中加入醛(1 mmol)溶液和CH;NO2(1.1 mmol),搅拌,温度控制为0 C,再取NaOH .(2h) 89(2. 00 mmol,80. 0 mg)溶于H20(1 mL)中,将所配得的NaOH溶液逐滴滴入反应液中,约20 min,加完后，用TLC跟踪反应进程.搅拌6 bh后,发现苯甲醛巳经(2D) 91基本反应完毕,随后用稀HCI中和,再点样爬板,在TCL板上只出现了1个不同于原料的新的圆点.令人欣喜的是反式的β-硝基苯乙烯产物达到了88%产率02j) 94在这个反应中,并没有发现有Z式异构体的生成,反应具有高度的区城选择性.1) NaOHMeOH美。(2k) 92273 Kk H+ CH,NO, 2HC图1 (E)=a.f 不饱和硝基烯烃的合成2(21) 91Fig 1 Synthesis of(E) a ,β unsaturated nitroalkenes当有了优化的实验条件后,接着研究不同的醛与硝基甲烷的反应,见表1.有供电子基团和没有供3Mo(2m) 91电子基团的芳香醛和脂肪醛的收率都在88% ~95%,即使是有吸电子基团的芳香醛也有不错的收①AII of the reaction were carried out on a scale of 1 mmol of率(见化合物2[和2g).aldehydes:②Isolated yields第3期谢隽毅,等;(E)-a,B-不饱和硝基烯烃的高度区域选择性合成方法311该合成方法一步完成,简单便捷,具有原子经济1160.性,属于绿色合成，相较于文献报道的已知方法,产[9] BONNE D. 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