[转帖]华东理工大学2004年硕士生入学有机化学试题
<P >华东理工大学<FONT face="Times New Roman">2004</FONT>年硕士生入学有机化学试题<p></p></P>
<P ><FONT face="Times New Roman">1</FONT>．名词解释并举例说明：（前<FONT face="Times New Roman">8</FONT>题中任选<FONT face="Times New Roman">4</FONT>题；<FONT face="Times New Roman">9</FONT>）、<FONT face="Times New Roman">10</FONT>）为必答题。<FONT face="Times New Roman">25</FONT>分）<p></p></P>
<P ><FONT face="Times New Roman">1</FONT>）极性非质子溶剂；<FONT face="Times New Roman">2</FONT>）<FONT face="Times New Roman">1</FONT>，<FONT face="Times New Roman">3-</FONT>张力；<FONT face="Times New Roman">3</FONT>）角张力；<FONT face="Times New Roman">4</FONT>）<FONT face="Times New Roman">Lewis</FONT>酸和<FONT face="Times New Roman">Bronsted</FONT>酸；<p></p></P>
<P ><FONT face="Times New Roman"> 5</FONT>）构象异构；<FONT face="Times New Roman">6</FONT>）前手性碳原子；<FONT face="Times New Roman">7</FONT>）<FONT face="Times New Roman">Aldol</FONT>反应；<FONT face="Times New Roman">8</FONT>）为何有机化合物数量庞大？<p></p></P>
<P ><FONT face="Times New Roman"> 9</FONT>）为何有机化合物的熔点一般不高？<FONT face="Times New Roman">10</FONT>）下列三个缩写词各代表什么含义：<FONT face="Times New Roman">ref.</FONT>；<FONT face="Times New Roman">r.t. </FONT>；<FONT face="Times New Roman">e.e.<p></p></FONT></P>
<P ><FONT face="Times New Roman">2</FONT>．解释下列现象；（<FONT face="Times New Roman">15</FONT>分）<FONT face="Times New Roman"> <p></p></FONT></P>
<P ><FONT face="Times New Roman"> </FONT>（<FONT face="Times New Roman">1</FONT>）（<FONT face="Times New Roman">R</FONT>）<FONT face="Times New Roman">-</FONT>或（<FONT face="Times New Roman">S</FONT>）<FONT face="Times New Roman">-2-</FONT>氯丁烷进行一氯代反应生成的<FONT face="Times New Roman">2</FONT>，<FONT face="Times New Roman">3-</FONT>二氯丁烷中含有<FONT face="Times New Roman">70%</FONT>的内消旋和<FONT face="Times New Roman">30%</FONT>的光活性的化合物。<p></p></P>
<P ><FONT face="Times New Roman"> </FONT>（<FONT face="Times New Roman">2</FONT>）酚中的<FONT face="Times New Roman">C</FONT>－<FONT face="Times New Roman">O</FONT>键长比醇中的<FONT face="Times New Roman">C</FONT>－<FONT face="Times New Roman">O</FONT>键长短。<p></p></P>
<P ><FONT face="Times New Roman">3</FONT>．给出<U><FONT face="Times New Roman">1</FONT></U>的命名和其他各个化合物的结构：（<FONT face="Times New Roman">10</FONT>分）<p></p></P>
<P align=center><v:shapetype><v:stroke joinstyle="miter"></v:stroke><v:formulas><v:f eqn="if lineDrawn pixelLineWidth 0"></v:f><v:f eqn="sum @0 1 0"></v:f><v:f eqn="sum 0 0 @1"></v:f><v:f eqn="prod @2 1 2"></v:f><v:f eqn="prod @3 21600 pixelWidth"></v:f><v:f eqn="prod @3 21600 pixelHeight"></v:f><v:f eqn="sum @0 0 1"></v:f><v:f eqn="prod @6 1 2"></v:f><v:f eqn="prod @7 21600 pixelWidth"></v:f><v:f eqn="sum @8 21600 0"></v:f><v:f eqn="prod @7 21600 pixelHeight"></v:f><v:f eqn="sum @10 21600 0"></v:f></v:formulas><v:path connecttype="rect" gradientshapeok="t" extrusionok="f"></v:path><lock aspectratio="t" v:ext="edit"></lock></v:shapetype><v:shape><v:imagedata></v:imagedata></v:shape><p></p></P>
<P ><FONT face="Times New Roman">4</FONT>．下列三个化合物中哪几个有手性？（<FONT face="Times New Roman">5</FONT>分）<p></p></P>
<P align=center><v:shape><v:imagedata></v:imagedata></v:shape><p></p></P>
<P ><FONT face="Times New Roman">5</FONT>．下列各个化合物分子中哪几个有芳香性？（<FONT face="Times New Roman">5</FONT>分）<p></p></P>
<P align=center><v:shape><v:imagedata></v:imagedata></v:shape><p></p></P>
<P ><FONT face="Times New Roman">6</FONT>．画出反<FONT face="Times New Roman">-4-</FONT>叔丁基氯代环已烷的椅式构象，并指出氯位于何种键上。（<FONT face="Times New Roman">5</FONT>分）<p></p></P>
<P ><FONT face="Times New Roman">7</FONT>．完成下列反应（如有立体专一性，需加以标注）：（<FONT face="Times New Roman">15</FONT>分）<p></p></P>
<P ><FONT face="Times New Roman"> </FONT><A><v:shape><v:imagedata><FONT face="Times New Roman"></FONT></v:imagedata></v:shape></A><p></p></P>
<P ><FONT face="Times New Roman">8</FONT>．以所给出的起始物为原料（其他化学试剂不限）完成下列合成：（<FONT face="Times New Roman">30</FONT>分）<p></p></P>
<P ><v:shape><v:imagedata></v:imagedata></v:shape><p></p></P>
<P ><FONT face="Times New Roman">9</FONT>．给出化合物<FONT face="Times New Roman">A</FONT>、<FONT face="Times New Roman">B</FONT>、<FONT face="Times New Roman">C</FONT>的结构和反应过程并对各个谱学数据的归属给以说明：（<FONT face="Times New Roman">10</FONT>分）<p></p></P>
<P ><FONT face="Times New Roman"> A</FONT>的分子式<FONT face="Times New Roman">C<SUB>10</SUB>H<SUB>16</SUB></FONT>，经酸性<FONT face="Times New Roman">KMnO<SUB>4</SUB></FONT>加热氧化后所得产物<FONT face="Times New Roman">B</FONT>再与重氮甲烷反应得<FONT face="Times New Roman">C</FONT>。<FONT face="Times New Roman">C</FONT>的光谱数据为<FONT face="Times New Roman"><SUP>1</SUP>HNMR</FONT>δ<FONT face="Times New Roman">(<SUP>1</SUP>H)3.68(6H,s)</FONT>，<FONT face="Times New Roman">1.90(4H</FONT>，<FONT face="Times New Roman">q</FONT>，<FONT face="Times New Roman">J=7Hz)</FONT>，<FONT face="Times New Roman">0.77(6H</FONT>，<FONT face="Times New Roman">t</FONT>，<FONT face="Times New Roman">J=7Hz)</FONT>；δ<FONT face="Times New Roman"><st1:chmetcnv w:st="on" TCSC="0" NumberType="1" Negative="False" HasSpace="False" SourceValue="13" UnitName="C"><SUP>13</SUP>C</st1:chmetcnv> NMR(<st1:chmetcnv w:st="on" TCSC="0" NumberType="1" Negative="False" HasSpace="False" SourceValue="13" UnitName="C"><SUP>13</SUP>c</st1:chmetcnv>)</FONT>：<FONT face="Times New Roman">8.1(q)</FONT>，<FONT face="Times New Roman">24.8(t)</FONT>，<FONT face="Times New Roman">51.7(q)</FONT>，<FONT face="Times New Roman">58.3(s)</FONT>，<FONT face="Times New Roman">171.7(s)</FONT>；<FONT face="Times New Roman">IR</FONT>：<FONT face="Times New Roman"><st1:chmetcnv w:st="on" TCSC="0" NumberType="1" Negative="False" HasSpace="False" SourceValue="1730" UnitName="cm">1730cm</st1:chmetcnv><SUP>-1<p></p></SUP></FONT></P>
<P ><FONT face="Times New Roman"> 10</FONT>．<U><FONT face="Times New Roman">2</FONT></U>的酸性比<U ><FONT face="Times New Roman">1</FONT></U>强？为什么？排出<U ><FONT face="Times New Roman">3</FONT></U>、<U><FONT face="Times New Roman">4</FONT></U>和<U><FONT face="Times New Roman">5</FONT></U>的碱性强弱次序。（<FONT face="Times New Roman">5</FONT>分）<p></p></P>
<P align=center><v:shape><v:imagedata></v:imagedata></v:shape><p></p></P>
<P ><FONT face="Times New Roman"> 11</FONT>．回答：（<FONT face="Times New Roman">10</FONT>分）<p></p></P>
<P ><FONT face="Times New Roman"> </FONT>（<FONT face="Times New Roman">1</FONT>）怎样用酒石酸来拆分外消旋α<FONT face="Times New Roman">-</FONT>苯乙胺<p></p></P>
<P >（<FONT face="Times New Roman">2</FONT>）用什么方法可以快速测知某未知化合物的结构，已知它是三个已知晶体化合物中的一个。<p></p></P>
<P ><FONT face="Times New Roman"> 12</FONT>．给出下列两个反应的机理过程。（<FONT face="Times New Roman">15</FONT>分）<p></p></P> <v:shape><v:imagedata></v:imagedata></v:shape>[attach]40076[/attach]
