(E)-α,β-不飽和硝基烯烴的高度區域選擇性合成方法

浙江大學(xué)學(xué)報(理學(xué)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-不飽和硝基烯烴的高度區域選擇性合成方法謝雋毅'，張斌”， 陳仁爾'，周其忠",徐土根'，葉余原'，蔣華江'(1.臺州學(xué)院化學(xué)系，浙江臺州317000 2.浙江工業(yè)大學(xué)藥學(xué)院，浙江杭州310014;3.杭州師范大學(xué)材料與化學(xué)化工學(xué)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反應,隨后用稀鹽酸處理,生威(E)-a,f不飽和硝基烯烴單一化合物,反應有高度的區域選擇性,牧率較高(76%~95%).合成方法便捷、高效、清潔,屬于綠色合咸.關(guān)鍵詞:臟;硝基甲烷;(E)-a,月不飽和硝基烯烴中圖分類(lèi)號:0622.1文獻標志碼:A文章編號: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不飽和的硝基脂肪酸是一類(lèi)新的內源性抗炎介基的Michael加成[2 -1;有機金屬化合物與硝基烯質(zhì)[1.不飽和硝基油酸能防止鼠腎缺血和再灌注損烴間的不對稱(chēng)共軛加成[5]以及具有旋光活性的傷50].當然,硝基烯烴也還有其他生物活性.(E)-硝基烯烴的立體選擇性氮雜環(huán)丙化8。.最近,(E)-a,f-不飽和硝基烯烴被廣泛用于一烯烴經(jīng)-氧化氮硝化可得到收率不錯的(E)-a.些反應中的Michael受體,如氫鍵介導的具有高度ρ不飽和硝基烯烴["7- 81.但許多烯烴-般不易制得，立體選擇性的Michael-Michael 串聯(lián)反應[);醛、酮而且一氧化氮是有毒氣體.醛和1-硝基烯烴在喊性與硝基烯烴的不對稱(chēng)Michael反應[-1] ;吲哚、吡咯AlO,和超臨界的CO2的條件下反應可制得(E)-a,與硝基烯烴的立體選擇性的Friedel-Crafts烷基化β不飽和硝基烯烴,但此法收率不是很高[(0];不飽和反應([-10);硝基烯烴與硝基烷烴之間的不對稱(chēng)羧酸在硝酸和催化量的AIBN作用下硝化和脫羧基Michal加成["9-川;有硝基烷烴參與的串聯(lián)催化的后可制得收率不錯的硝基苯乙烯和硝基芳香烴(1]..不對稱(chēng)Friedel-Crafts/Henry 反應[};硝基烯烴的硝基甲烷與相應的醛通過(guò)Henry縮合可得到β硝基不對稱(chēng)生物還原(=-53] ;多米諾硝基-Michael/Henry醇F硝基醇再經(jīng)DCC/CuCl或三氟乙酸酐/三乙胺反應e,2];不對稱(chēng)多組分串聯(lián)反應[820;不對稱(chēng)硝脫水(2.2 ,或者也可以經(jīng)MsC/EtN..5l或P,Of#]收稱(chēng)日期:2011-07-11.基金項目:國家自然科學(xué)基金資助項日21172166)1浙江省自然科學(xué)基金資助項目(4100783):浙江省教育廳科研計劃資助項目.(20061048).作者簡(jiǎn)介:謝雋教(1990-),男,主要從事有機化學(xué)研究.●通信作者.E mail; qizhongchou@yahoo. com;jbj@txc. edu. cn.第3期謝雋毅,等:(E)-a.A-不飽和硝基烯烴的高度區域選揮性合成方法309脫水得到(E)-a,F不飽和硝基烯烴,反應需2步,收p.77~79 C;' H NMR(CDCl ,300 MHz):7. 99(d,率不是很高. BrCH2NO2與醛在碘化鈉的催化下很容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經(jīng)二碘化釤β-消除制得(E) -a,f不飽和硝基烯烴;此Hz,2H),1.26(t,J=7. 6 Hz, 3H);"C NMR法收率一般,但E式產(chǎn)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鈉處理可得到收率不129. 2,127. 7,29.1,15.3.錯的(E)-a,#不飽和硝基烯烴,但反應需要3步,總反式4-甲氧基-β-硝基苯乙烯(2c):黃色固體，收率不是很高[48].m. p. 86~88 C;'H NMR(CDCI]; . 300 MHz):7.97因此,筆者希望醛和硝基甲烷通過(guò)- -步反應就(d,J= 13.6 Hz,1H),7. 51(dd,J1=6.7 Hz,J2=能得到收率較高的(E) -a,β-不飽和硝基烯烴.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實(shí)驗部分135. 2,131.4,122.7,115.1,55.72-[(E)-2- 硝基乙烯基]呋哺(2d):黃色固體,m p.1.1主要 儀器與試劑72~75 C;'H NMR(CDCl, 300 MHz):7. 78(d,J=所有的化學(xué)品以及溶劑都是直接從供應商處買(mǎi).13.2 Hz,1H) ,7.50~7. 60(m,2H),6. 90(d,J=3.5 Hz, .來(lái)的,沒(méi)有經(jīng)過(guò)進(jìn)-一步的純化,測得的熔點(diǎn)值未經(jīng)校1H),6. 58(q,J=1. 8 Hz, 1H);I C NMR(CDCl,75.準.'HNMR在Bruker300MHz核磁共振儀上測MHz) :147.0,146.8,135.1,125. 6,120. 2,113. 5.試,"C NMR在Bruker 75 MHz核磁共振儀上測試.ar[(E)-2-硝基乙烯基]萘(2e);黃色固體,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),攪拌,溫度控制為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,將所配得的NaOH溶液逐滴滴到反應液127. 0,126.6,125. 6,123. 1.中,約20 min.加完后,再攪拌6h.之后加入1 mol的反式-4-三氟甲基-β-硝基苯乙烯(20):黃色固HCl中和反應液.然后用二氣甲烷(3X2 mL)對反應液體,m. p.63~66 C;'H NMR(CDCl; ,300 MHz) :進(jìn)行萃取,將合并后的有機相進(jìn)行濃縮.將濃縮液過(guò)色8.03(d,J=13. 7 Hz,1H),7. 61~7. 74(m,5H);諧柱,淋洗劑選為正己烷/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),最后得到黃色液體或黃色固體.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);黃色固體，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),攪拌,溫度控制為~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,將所配得的NaOH溶液逐滴滴到反應液(E)-1-硝基-4-苯基-1-丁烯(2h):黃色液體,'H中,約20 min,加完后,再攪拌6 h,之后加入1 molNMR( CDCl, 300 MHz):7. 15~7. 34 (m, 6H),的HCl中和反應液,然后用二氯甲烷(3X2 mL)對6. 94(dt,J1=13.4 Hz,J2=1.4 Hz,1H),2. 82(t,J反應液進(jìn)行萃取,將合并后的有機相進(jìn)行濃縮.將濃=7.4 Hz,2H),2.54~2. 62 (m,2H);"C NMR縮液過(guò)色譜柱,淋洗劑選為正己烷/二氯甲烷(4 :(CDCIs ,75 MHz):141. 6,140. 2,139.7,128. 9,128. 5,1),最后得到黃色固體.126.8,34.1,30. 3.1.4產(chǎn)物分析(1E)-3-乙基-1-硝基-1-戊烯(2i):黃色液體,H反式β-硝基苯乙烯(2a):黃色固體,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]環(huán)己烷(2j):黃色液體,H .反式-4-乙基β-硝基苯乙烯(2b):黃色固體,m.NMR(CDCl, ,300 MHz):7. 22(dd,J1=7.2 Hz,J,310斷江大學(xué)學(xué)報(理學(xué)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心時(shí)Hz,1H),2. 21~2.28(m,1H),1.70~1.83 (m,各種醛和硝基甲烷的反應中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):黃色液體,' 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.著(zhù)。(2b) 90(1E)-1-硝基-1-己烯(2I):黃色液體,' 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):黃色液體,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結果與討論初步研究了在0C時(shí)苯甲醛與硝基甲烷在甲醇(2g) 76和氫氧化鈉溶液中的反應(如圖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),攪拌,溫度控制為0 C,再取NaOH .(2h) 89(2. 00 mmol,80. 0 mg)溶于H20(1 mL)中,將所配得的NaOH溶液逐滴滴入反應液中,約20 min,加完后，用TLC跟蹤反應進(jìn)程.攪拌6 bh后,發(fā)現苯甲醛巳經(jīng)(2D) 91基本反應完畢,隨后用稀HCI中和,再點(diǎn)樣爬板,在TCL板上只出現了1個(gè)不同于原料的新的圓點(diǎn).令人欣喜的是反式的β-硝基苯乙烯產(chǎn)物達到了88%產(chǎn)率02j) 94在這個(gè)反應中,并沒(méi)有發(fā)現有Z式異構體的生成,反應具有高度的區城選擇性.1) NaOHMeOH美。(2k) 92273 Kk H+ CH,NO, 2HC圖1 (E)=a.f 不飽和硝基烯烴的合成2(21) 91Fig 1 Synthesis of(E) a ,β unsaturated nitroalkenes當有了優(yōu)化的實(shí)驗條件后,接著(zhù)研究不同的醛與硝基甲烷的反應,見(jiàn)表1.有供電子基團和沒(méi)有供3Mo(2m) 91電子基團的芳香醛和脂肪醛的收率都在88% ~95%,即使是有吸電子基團的芳香醛也有不錯的收①AII of the reaction were carried out on a scale of 1 mmol of率(見(jiàn)化合物2[和2g).aldehydes:②Isolated yields第3期謝雋毅,等;(E)-a,B-不飽和硝基烯烴的高度區域選擇性合成方法311該合成方法一步完成,簡(jiǎn)單便捷,具有原子經(jīng)濟1160.性,屬于綠色合成，相較于文獻報道的已知方法,產(chǎn)[9] BONNE D. SALAT L. DUCEREJ.etal. J Sequen率高、操作更簡(jiǎn)便,具有很大的優(yōu)越性.tial orgenocatalyzed Michael addition/[3+ 2]-heterocy-clization for the stereoselective synthesis of fused-isox-3結論azoline precursors of enantiopure cyclopentanoids[J].Organic Letters, 2008,10:5409- 5412.[10] JIANG x. ZHANG Y, CHANASC, etal Salarins A提供了一種通過(guò)一步反應制備(E)-a,β-不飽and B and Tuleain A: new cytotoxic sponge derived ma-和硝基烯烴的方法,反應有高度的區域選擇性,而且crolides[J]. Onganic Ltter,2008, 10153- 156.收率好.此反應方法便捷、干凈.高效、簡(jiǎn)單,可用這[11] VARELAMC. DIXON s M，LAM K S, et al.種方法制備大量(E)-a,β不飽和硝基烯烴,因此可Asymmetric epoxidation, michael addition, and triple以用于工業(yè)化生產(chǎn).cascade reaction using polymer-supported prolinol-based auxiliaries[J]. Tetrahedron, 2008, 64: 10087 -參考文獻(References):10090.[12] LV G, JIN R, MAI w. et al. 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