碘催化亚胺与二氢呋喃反应合成四氢喹啉衍生物

1、2010年第18卷合成化学V o.l 18,2010第1期,110112Ch i nese Journa l o f Synthe tic Che m istry N o .1,110112研究简报碘催化亚胺与二氢呋喃反应合成四氢喹啉衍生物*赵伟杰,闫凤美(黄淮学院化学化工系,河南驻马店 463000摘要:碘催化N 苯基苄基亚胺与二氢呋喃反应合成了四氢喹啉衍生物,其结构经1H NMR,13C NM R 和HR M S表征。关 键 词:四氢喹啉;亚胺;二氢呋喃;碘;合成中图分类号:O 626.32文献标识码:A文章编号:1005 1511(201001 0110 03Synt hesis of

2、Tetrahydroqui noli nes by the Reactionof Im ino wit h Dihydrof uran U si ng Iodi ne as a CatalystZ HAO W ei jie , YAN Feng me i(D epart m ent o f Chem istry and Chem ica lEng i neeri ng ,H uanghua i Co lleg e ,Zhu m adian 463000,ChinaA bstract :Tetrahydr oquino li n es w ere synthesized by the D ie

3、ls A lder reacti o n o f N ary li m i n e w ith d i hydro f u ran using i o dine as a catalys.t The str uctures w ere characterized by 1H NMR,13C NMR andHR M S .K eywords :tetrahydroqu i n oline ;i m i n e ;d i h ydr o furan ;iod i n e ;syn t h esis 四氢喹啉衍生物广泛存在于天然产物中,具有多种的生物活性13 ,如抑制精神活性、抗变活性、抗干扰活性等

4、,而且吡喃喹啉的衍生物还经常用于药物合成。对四氢喹啉衍生物的合成,应用最广泛和最有效的方法是氮芳基亚胺与富电子烯烃的aza D iels A l d er 反应4,该反应可以被众多的催化剂所催化。本文报道碘催化N 苯基苄基亚胺(1a1c 与二氢呋喃(2反应合成四氢喹啉衍生物(3a3c ,Sc he m e 1的新方法,其结构经1H NMR ,13C NMR 和HR M S 表征。1实验部分Sch e m e 11.1 仪器与试剂W C 1型显微熔点测定仪(温度计未校正;V arian I nova 400型核磁共振仪(CDC l 3为溶剂,T M S 为内标;OA TOF 型高分辨质谱仪。按文

5、献5方法合成1a1c ,N 苯基苄基亚胺(1a ,产率80%;1H N MR :8.46(s ,1H ,7.927.88(m ,2H ,7.48(,t J =3.2H z ,3H ,7.277.22(m,2H ,6.956.93(m ,2H 。其余所用试剂均为化学纯或分析纯;正己烷在钠 二苯*收稿日期:2009 10 12基金项目:驻马店市科技攻关资助项目(068005作者简介:赵伟杰(1979-,女,汉族,河南驻马店人,硕士,讲师,主要从事有机合成的教学与研究。E ma i :l z hao w eijie78ch i na .co 乙酮回流下重蒸;二氯甲烷经氢化钙处理后使用。1.2 3的合

6、成(以3a为例在反应瓶中加入1a1mm o l和I20.15mm o l 的C H2C l2(10m L溶液,搅拌下滴加22mm o,l滴毕,于室温反应12h。分液,有机层依次用5% N a2S2O3溶液、饱和食盐水洗涤,无水M gSO4干燥,旋蒸除去溶剂,残余物经柱层析洗脱剂:V (乙酸乙酯 V(石油醚=1 10分离得3a,产率74%n(cis n(trans=32 68。用类似方法合成3b产率65%,n(cis n (trans=47 53和3c产率54%,n(cis n (trans=21 79。H z,1H,6.79(,t J=7.8H z,1H,6.62(d,J=8.0H z,1H,

7、4.59(d,J=5.1H z,1H,4.08(m, 1H,3.85(m,3H,2.45(m,1H,2.01(m, 1H,1.72(m,1H;13C NMR :145.3,141.7, 131.1,128.8,128.6,128.2,128.0,120.0, 118.2,114.6,76.1,65.0,57.6,43.3,28.7。18H19NO2 (M+281.1416,found281.1411。2 结果与讨论以1a与2反应为模型,考察了I2用量和溶剂种类对反应的影响,结果见表1和表2。由表1可见,在没有I2的情况下反应不能发生;I2用量为15m o%l时,产率最高;I2用量进一步增加时,

8、收率开始下降。可能是过量的I2引起了氧化等副反应所致。从表2可以看出,所有被测试的溶剂都能较好的得到产物,溶剂对反应的影响不是很大。即使使用含水的混合溶剂,反应也能发生,但收率有所下降。表1 I2用量对1a与2反应的影响*Tab le1 E ffect of I2a m ount on the reacion o f1a w ith2I2/mo%l0510152550收率/%05861745434*以C H2C l2为溶剂,其余反应条件同1.2111第1期 赵伟杰等:碘催化亚胺与二氢呋喃反应合成四氢喹啉衍生物表2 溶剂种类对1a与2反应的影响*Tab le2 E ffect of so lve

9、nts on the reaction o f1a w ith2溶剂收率/%cis/transV(hexane V(C H2C l2=3 16373/27T o l uene6264/36C H2C l27432/68CH3C N6643/57V(Et OH V(H2O=4 14744/56*I215mo%l,其余反应条件同1.2参考文献1 Johnson J V,R auck m an S,Baccanar i P D,et al.2,4 dia m i no5 benzy l pyr i m idi nes and ana logues as antibacter i a l ag ent

10、s:A na logues w ith hi gh acti v ity and specificity for bacte rial dihydro folate reductaseJ.JM edChem,1989,32:1942-1945.2 Car li ng R W,Leeson P D,M ose l ey A M,et al.2Carboxy tetrahydroqu i no li nes.Confor m ati ona l and stereochem i ca l requ irements for antagon i s m of the g lyc i nesite o

11、n t he NM DA receptorJ.J M ed Che m,1992,35:1942-1946.3 Y am ada N K ado w ak,i S T akahashiK,Um ezu K.MY1250,a m a j or m etabo lite o f the anti a ll erg i c drug rep iri nas,t induces phosphory l a tion o f a78 kD a prote i n i nrat m ast ce llsJ.B ioche m P har m aca,l1992,44:1211-1214.4 Povarov

12、 L S.E leectrode kine ti c aspects o f the kobe lreactionJ.Russ Che m R ev,1967,36:656-661. 5 Bowm an R K,Johnson J S.L ew is ac i d ca talyzed dipol ar cycloadditions of an ac tivated I m i dateJ.J O rgChe m,2004,69:8537-8540.(上接第15页5 H orro cks A R,K ando la B K,D av i es P J,et al.D eve l op m en

13、ts i n fla m e re tardant tex til e a rev i ewJ.Po ly m D egrad Stab,2005,88(1:3-12.6 Feng G,T ong L F,Fang Z P.Effect of nove l phosphorous n itrogen conta i n i ng int umescent fla m e retardanton t he fire retardancy and the t her m a l behav i our o f po ly(bu t y lene te rephthalateJ.Po l ym D

14、eg rad Stab,2006,91(6:1295-1299.7 Q iang L,Ji ang P K,W e i P.Syn t hesis,characteristicand applica ti on o f ne w fla m e retardant conta i n i ng phosphorus,nitrogen and s ili conJ.Po ly m Eng Sc,i2006,46(3:344-350.8 Serge iV L evch i k,Ed w ard D W e i.l A rev i w o f recentprogress in phosphorus

15、 based fla m e retardantsJ.JF i re Sc,i2006,24(5:345-364.9 Cong ranh N guyen,Ji nhwan K i m.T her m al stabilitiesand fla m e retardancies o f n itrogen phospo rus fl am e reta rdants based on b i sphospho ra m i datesJ.Po l ym D egrad Stab,2008,93(6:1037-1043.10 邵阿娟,王海云,张幼珠.膨胀型阻燃剂整理棉织物的阻燃及热裂解性能J.印染

16、助剂,2007,24(11:39-43.11 L i u Y,W ang D Y,W ang J S et al.A nove l int umescent fla m e retardant LDPE syste m and its thermo ox ida ti ve deg radati on and fl ame re tardan t m echanis m sJ.Po l ym A dv T echno,l2008,19(11:1566-1575.12 W ang D Y,G e X G,W ang Y Z,et al.A nove l phospho rus containi

17、ng po ly(et hy l ene tereph t ha l a tenanocomposite w ith bo th fla m e re tardancy and an ti dripp i ng effec tsJ.M acrom olM ate r Eng,2006,291(6:638-645.13 G rabhofe r H,L ittard C,M u ller H,et al.Pentaery t hrito l pho spho ric ac i d este r sens itize rs f o r pho tog raph ice m ulsi onsP.U S

18、3169863.14 R a tz R,Swee ting O J.Some che m i ca l reactions o f3,9 dich l o ro 2,4,8,10 tetraoxa 3,9 di phosphasp iro5,5undecane3,9 diox ideJ.J O rg Chem,1963,28(3:1608-1612.15 刘畅,禇劲松,邵传强,等.2,4,8,10 四氧杂 3,9二磷杂螺环5,5十一烷 3,9 二氧 3,9 二取代苯甲醛腙的合成及其阻燃性能J.应用化学,2007,24(7:818-822.16 Chen D Q,W ang Y Z,H u X P,et a l.F la m e retardant and anti dri ppi ng e ffects o f a nove l char