清华大学有机化学李艳梅老师课件第二章说课材料.ppt

,单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,Modern Spectrometry,第二章,现代仪器分析方法及应用,Organic Chemistry A(1),By Prof.Li Yan-Mei,Tsinghua University,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,Content,引言,第一部分 核磁共振谱(NMR),第二部分 红外光谱法(IR),第三部分 质谱法(MS),第四部分 紫外可见光谱法(UV-Vis),Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,引 言,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,分析未知化合物的步骤,?,C,H,O,C%H%O%,C,m,H,n,O,y,2.1,引言,利用其各种化学反应性质推测可能结构,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,分子的不同层次运动,Different motion,Translation,Rotation,far-infrared,Vibration,infrared,Motion of the electron,ultraviolet&visible,Motion of the nuclear,microwave,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,各种光谱分析方法,X ray,Ultraviolet,Visual,Infrared,Micro,wave,Radio,wave,RFID,Electron Spectroscopy,Ultraviolet,Visual,Infrared,NMR,200400 nm,400800 nm,2.515,1n5n,wavelength,short,long,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,第一部分 核磁共振谱(NMR),Nuclear Magnetic Resonance,2.2 核磁共振的基本原理,2.3,1,H-NMR(核磁共振氢谱),2.4,13,C-NMR(核磁共振碳谱),Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,2.2 核磁共振的基本原理,750 MHz NMR,600 MHz NMR,800 MHz NMR,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,NMR仪器的基本组成,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,I=2,m=-1,m=1,m=0,I=1,m=-1,m=1,原子核的磁矩和磁共振,原子核的自旋运动和自旋量子数,I,相关。,核自旋量子数：,I,原子核置于磁场中，将有：,2,I,1,个取向,I=1/2,m=-1/2,m=1/2,m=0,m=2,m=-2,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,以I=1/2的核为例:,当外部给予的能量恰为,E时，,原子核则可吸收该能量，从低能级运动方式跃迁到高能级运动方式，即发生“,核磁共振,”,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,答：,I=0,的原子核没有核磁信号。,1,H，,13,C，,31,P，,15,N，,19,F I=1/2,12,C，,14,N，,18,F I=0,1,H-NMR,13,C-NMR,31,P-NMR,15,N-NMR,19,F-NMR,问：是否所有的原子核都有核磁信号？,因为：,I=0,时 2I,1 1,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,E=,hH,0,/2,：,磁旋比（为各种核的特征常数）,h：plank,常数,H,0,：,外加磁场强度,问：跃迁（“核磁共振”）时所需要吸收的能量E为多少？,核磁共振时,E=,hH,0,/2=h,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,E=,hH,有效,/2,H,有效,=H,0,-H,感应,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,处于不同化学环境中的质子,外层电子分布,情况不同,产生的感应磁场也不同,E=,hH,有效,/2,H,有效,=H,0,-H,感应,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,信号的裂分：,偶合常数,信号的位置：,化学位移,信号的强度：,积分曲线,2.3,1,H-NMR(核磁共振氢谱),Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,2.3.1 信号的位置:化学位移,单位（,）：,ppm,零点：,TMS,相对于一个基准物的相对值,样品,标准,仪器,低场,高场,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,原则1：等价的质子化学位移相同,E=,hH,有效,/2,H,有效,=H,0,-H,感应,化学环境相同,替代原则,C,H,4,C,H,3,C,H,3,C,H,3,a,C,H,2,b,C,H,3,a,C,H,3,a,C,H,2,b,C,H,2,c,Cl,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,影响化学位移的因素：,原子核外电子云的分布：电负性,原子核所受的额外磁场：各向异性效应,原则2：不等价的质子化学位移不同,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,E=,hH,有效,/2,H,有效,=H,0,-H,感应,电负性的影响：,邻近基团电负性 质子上电子云密度,H,感应,H,有效,CC,H,3,NC,H,3,OC,H,3,2.5,3.0,3.5,=,0.77-1.88,=,2.12-3.10,=,3.24-4.02,C,H,3,Cl C,H,2,Cl,2,C,H,Cl,3,=3.05 =5.30 =7.27,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,C,H,3,a,C,H,2,b,C,H,2,c,Cl,H,H,H,H,H,思考,！,例如：,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,各向异性效应的影响：,=4.5-5.9,=7.2,=2.8,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,=2.8,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,表示法：,J 单位：Hz,m,J,n,m：表示两个偶合核之,间间隔键的数目,n：其它信息,2.3.2 信号的裂分:偶合常数,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,1）偶合的产生：自旋自旋偶合,屏蔽,B与外磁场反平行,去屏蔽,B与外磁场平行,R,1,C,A,C,B,R,4,R,2,R,3,H,A,H,B,+1/2,R,1,C,A,C,B,R,4,R,2,R,3,H,A,H,B,-1/2,B不存在时，A的化学位移,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,偶合常数,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,2）裂分规律,相隔三根,单键,以上，一般J 0,等价质子（磁等价）互不裂分,具有沿共价键的意味,n+1,规律,C,H,4,C,H,3,C,H,3,C,H,3,C,H,2,Cl,J,ac,J,ad,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,n+1 规律：一组化学等价的质子被一组数目为n的等价质子裂分时，那么其吸收峰数目为n+1，峰强比例符合二项式。,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,H,H,1,2,1,1,3,3,1,外磁场方向,H,被两个等价的,H,裂分为叁重峰，叁重峰的峰强比为1:2:1,H,被三个等价的,H,裂分为四重峰，四重峰的峰强比为1:3:3:1,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,如果一组化学等价的质子被两组数目分别为n和n的等价质子裂分时，那么其吸收峰数目为(n+1)(n+1)，,H被裂分为：,(2+1)(3+1)重峰,注：s:,单重峰,d:,二重峰,t:,叁重峰,q:,四重峰,m:,多重峰,J,ab,J,ba,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,2.3.3 信号的强度:积分曲线,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,简单谱图分析：,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,Solvent,1,H Chemical Shift(multiplicity),J,HD,(Hz),HOD in solvent(approx.),13,C Chemical Shift(multiplicity),J,CD,(Hz),B.P.(,o,C),M.P.(,o,C),Acetic Acid-d4,11.652.04,15,-2.2,11.5,178.9920.0,17,-20,118,17,Acetone-d6,2.05,5,2.2,2.8,206.6829.92,137,0.919.4,57,-94,提示1：测试NMR谱图时采用什么溶剂？,氘代试剂 D:,I,=0 注意未完全氘代的溶剂峰,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,Solvent,1,H Chemical Shift(multiplicity),J,HD,(Hz),HOD in solvent(approx.),13,C Chemical Shift(multiplicity),J,CD,(Hz),B.P.(,o,C),M.P.(,o,C),Deuterium Oxide,4.80(DSS),1,-,4.8,-,-,-,101.4,3.8,N,N-Dimethyl-formamide,8.032.922.75,155,-1.91.9,3.5,163.1534.8929.76,377,29.421.021.1,153,-61,Dimethyl Sulfoxide-d6,2.50,5,1.9,3.3,39.51,7,21.0,189,18,p-Dioxane-d6,3.53,m,-,2.4,66.66,5,21.9,101,12,Ethanol-d6,5.293.561.11,11m,-,5.3,-56.9617.31,-57,-2219,79,2260-2100 1680-1600,于指纹区,C,sp,H,C,sp2,H,C,sp3,H,3320-3310 3090-3010 3000-2800,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,3、影响峰位变化的因素,诱导效应：,吸电子基团使吸收峰向高波数方向移动（蓝移）,反之向低波数方向移动（红移）,R-COCl C=O 1800cm,-1,R-COF C=O 1920cm,-1,+,-,+,-,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,共轭效应,共轭效应使吸收峰的波数减小，向低波数方向移动约30cm,-1,。,空间效应,场效应；空间位阻；环张力,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,4、氢键的影响：,(分子内、分子间氢键)对峰位，峰强产生极明显影响，使伸缩振动频率向低波数方向移动，峰变宽、变强。,分子间氢键对OH伸缩吸收峰影响：,游离伯醇：,3640 cm,-1,双分子缔合：,3550-3450 cm,-1,多分子缔合：,3400-3200 cm,-1,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,第三部分 质谱法(MS),2.7 质谱的基本原理,2.8 典型质谱图,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,2.7 质谱的基本原理,补电子运动图,M +e,-,M,+,+2 e,-,分子离子,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,质谱仪器的构造,进样系统,离子源,质量,分析器,检测器,1，气体扩散,2，直接进样,3，气相色谱,1，EI,2，CI,3，ESI,4，MALDI,1，单聚焦,2，双聚焦,3，飞行时间,4，四极杆,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,电子电离源-单聚焦质谱,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,气相（液相）色谱质谱,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,2.8 典型质谱图,“柱状图”,相对丰度,质荷比,分子离子峰,分子量,基峰,丰度最大的峰,同位素峰,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,各类有机物分子离子裂解成碎片具有一定规律,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,第四部分 紫外可见光谱法(UV-Vis),2.9 紫外可见光谱法的基本原理,2.10 紫外可见光谱与分子结构的关系,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,100-200 nm 远紫外,（真空紫外）,200-400 nm 近紫外,400-800 nm 可见光谱,价电子跃迁吸收或放出的能量落于紫外区,2.9 紫外可见光谱法的基本原理,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,信号的强度：,由样品性质决定,与浓度成正比，可用于,定量分析,A=,c l Lambert-Beer,定律,信号的位置：,由跃迁方式决定,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,*,*,n,n,*,*,n ,*,*,*,*,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,2.10 紫外可见光谱与分子结构的关系,n,*,*,n ,*,*,1、饱和化合物,引入O，N，X等原子或含有这些原子的基团,这些原子具有n电子，,n,*跃迁,能级降低，可能落于近紫外区,只有,电子，,*跃迁 远紫外,在近紫外和可见光区域一般无吸收,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,2、不饱和化合物,有,、电子，,*、*跃迁,可能落于近紫外区,共轭后,*,跃迁能级差减小,可能落于可见光区；,共轭效果越好，能级差越小，吸收光的波长越长,与C=O,N=O,C=S,N=N等基团共轭,增加了能级更低的n,*跃迁方式,n,*,*,n ,*,*,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,3、芳香族化合物,I带：,max,=184 nm (=47000),很强，真空紫外,II带：,max,=204 nm (=6900),强，近紫外,III带：,max,=255 nm (=230),中强，近紫外,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,Evaluation only.,Created with Aspose.Slides for.NET 3.5 Client Profile 5.2.0.0.,Copyright 2004-2011 Aspose Pty Ltd.,