摘要
基于Heck反应与一锅合成法的优点，近年来，如何利用这两种手段来合成吲哚衍生物得到极大的关注，也获得了很大的成果。但是如何由邻卤苯胺与非环酮经Heck反应一锅法合成吲哚衍生物仍然鲜有报道，在此我们研究了以邻溴苯胺与非环酮乙酰乙酸乙酯为反应原料，利用Heck反应一锅合成了目标产物3-乙氧羰基-2-甲基吲哚。当以Pd(OAc)_2为钯源时我们尝试了PPh_3、p(o-tol)_3、dppe和卡宾(1)、卡宾(2)和其它的催化体系。经研究发现，Pd(OAc)_2为钯源时，非膦配体卡宾(1)、卡宾(2)的催化作用不如有机膦配体，而双齿膦配体dppe效果不如单齿配体PPh_3、p(o-tol)_3，其中p(o-tol)_3的催化反应效果最好，且发现在Heck一锅法合成吲哚的催化反应条件中溶剂DMF，碱K_3PO_4对反应的促进作用最好。当以PdCl_2为钯源催化剂时，以CTAB作助剂，我们找到了一种较好的通过Heck反应一锅法合成目标吲哚的方法，产率可以达到52％。
本部分以对甲基苯磺酰氯为起始原料，合成了三个对甲基苯磺酰衍生物，得到了化合物的单晶，并对其进行了单晶衍射表征。我们采用荧光发射光谱法测定了主体对客体离子的识别性能。经实验发现化合物(1)、(2)、(3)均对Fe~(3+)均具有很强的识别能力，且化合物(1)还对Cu~(2+)具有较强的识别的能力。这三种化合物对阴离子不具有识别作用。并且我们讨论了三种化合物对离子的识别作用机理。根据“锁-钥匙”理论，从得到的数据及分析讨论可以看出在分子识别中主—客体间空间大小、形状匹配起着重要且主要的作用。从计算出的包结常数可以看出，化合物(1)(K_(Fe)=1.0764×10~4 L／mol、K_(Cu)=2.98×10~3L／mol)与化合物(3)(K_(Fe)=8.103×10~3 L／mol)对Fe~(3+)的络合常数相近，说明两者的类分子钳结构空腔大小可能相近，并且化合物(1)的类分子钳与Fe~(3+)更匹配一些，两者均与Fe~(3+)形成1：1型的配合物：化合物(3)没有象化合物(1)(K_(Cu)=2.98×10~3L／mol)一样对Cu~(2+)产生识别，这个可能是由于Cu~(2+)的电荷作用力不如Fe~(3+)与化合物(1)的大，加上类分子钳的不匹配而导致化合物(3)对Cu~(2+)不识别：对于化合物(2)，其与Fe~(3+)形成的配合物的络合常数达到K_(Fe)=1.98×10~8 L／mol，化合物(2)与Fe~(3+)的络合比为1：2，经我们分析，该络合结构可能是一种奇特的夹心三明治结构。
Because of the great virtue of Heck reaction and one-pot reaction, It is attractmany attention that how to synthesis indoles by the two methods. And It had gainedmany progress. But It is still a problem that how to synthesis indoles through one-potreaction with o-haloaniline and open-chain ketone. Hereon, we synthesised3-ethoxycarbonyl-2-methylindole through one-pot Heck reaction with o-bromoanilineand open-chain ketone ethyl acetoacetate. When use Pd(OAc)_2 as catalyst. We tryseveral ligands in the catalytic system: Phosphine ligands such as PPh_3、p(o-tol)_3、dppeand Non-phosphine ligands such as cabene(1) and cabene(2). We find when we usePd(OAc)_2 as catalyst. The Non-phosphine ligands cabene(1) and cabene(2) are worsethan Phosphine ligand. And Monodentate ligands PPh_3、p(o-tol)_3 are better thanBidentate ligand dppe. And we find that the solvent of DMF and alkali K_3PO_4 isbetter than other solvent and alkali in the Heck reaction.When use PdCl_2 as catalyst,CTAB as additive, we find a better catalytic system to synthsis indoles throughone-pot heck reaction with o-bromoaniline and open-chain ketone ethyl acetoacetate.
We synthesis three toluene-4-sulfonate derivations and get their crystals. Theinclusion interaction of Host with Guest are tested by Fluorimetric Method. The resultof molecular recognition test of compounds (1),(2),(3) shows that all of the Hostmoleculars have strong complexation to Fe~(3+). Also compound(1) has complexationto Cu~(2+). We discuss the mechanism of recognition of the compounds. As the"key-lock" theory, we find that the room size and shape matching betweenHost-Guest plays an important and key role. We find compound(1) and compound(3)has similar cavity structure for their similar complex constant of compound(1) andcompound(3) with Fe(Ⅲ)(K_(Fe)~1=1.0764×10~4 L/mol, K_(Fe)~3=8.103×10~3 L/mol). Bothof them form stable 1: 1 type complexes with Fe~(3+); compound(2) can form stable 1: 2type complexe with Fe~(3+). and the complex constant can reach 1.98×10~8 L/mol, wethink compound(2) and Fe~(3+) form a stange sandwich structure.
引文
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