谱图解析NMR Stucture Elucidation

1、谱图解析NMR的主要参数NMR与化学结构谱峰指认、图谱解析核磁共振的参数核磁共振的参数化合物的分子结构化合物的分子结构化学位移化学位移偶合裂分偶合裂分谱峰强度谱峰强度弛豫时间弛豫时间NOE作用作用偶极作用偶极作用1H、13C一维谱同核二维谱异核二维、三维谱原子与原子的连接原子与原子的连接原子之间的空间取向原子之间的空间取向化学结构的动态平衡化学结构的动态平衡化学位移（Chemical shift）B0Be原子核实际感受到的磁场: Beff = (1-s s) B0 （s: 屏蔽常数）实际的共振频率： =(1-)B0同种原子核在不同的化学环境中，有不同的屏蔽常数，产生不同的共振频率：A、B，二者

2、的绝对频率差别： A B(A-B) B0 （与外磁场强度B0有关）相对频率差别： （通常10-6, 用ppm值表示）(A )/ B0= A-B （与外磁场强度B0无关）化学位移（Chemical shift）诱导效应(对饱和烷烃的影响)与质子相连的碳原子上,如果接有电负性强的基团,则由于吸电子诱导效应,使质子周围的电子云密度减弱,使屏蔽作用减弱,质子共振吸收移向低场,电负性越强,化学位移值越大.R=Cl, F, Br,-NCORCH2=4.5-5.5R=NH2, -COR,-ArCH2=3.5-S-P杂化从sp3（碳碳单键）到sp2（碳碳双键）s电子的成分从25%增加到33%，键电子更靠近碳原

3、子，因而对相连的氢原子有去屏蔽作用，即共振位移移向低场。（芳环与烯烃比饱和烷烃的化学位移低场的原因）磁各向异性HaHaHbHb18-环 稀Ha=8.9ppmHb=1.8ppm磁各向异性卤素与不饱和烷烃连接时同时有共轭作用和诱导作用：F的共轭作用大于诱导作用，所以邻位的氢谱和碳谱都移向高场；Cl的共轭作用和诱导作用相互抵消所以影响很小；Br到I共轭作用小于诱导作用所以相比邻位氢明显偏向低场。共轭作用和诱导作用（对不饱和烷烃影响）介质因素（溶剂、pH值等）成盐后氮旁边的CH2低场偏移 =0.5氢键的影响对活泼氢的影响很大。氢键形成，氢键中质子信号明显移向低场，对分子内氢的化学位移也有影响。样品分子

4、间氢键和浓度有关，样品的分子内氢键和浓度无关。样品分子还会与溶剂分子成氢键。其它因素重水交换1.01.21.41.61.82.02.22.42.6ppm440.18447.02628.73651.18658.93666.65686.69787.48794.93802.35809.761247.761255.241262.511269.973.1633.382.222.00CH3(CH2)15CH2CH2SH1.01.21.41.61.82.02.22.42.6ppm471.24478.35485.11666.88687.14690.24694.82698.00705.73717.55724.6

5、4731.69832.94840.41847.821286.081293.481300.741308.293.1033.942.172.00D2O交换的变化交换的变化4.54.03.53.02.52.01.51.00.5ppm433.33440.43447.29631.53639.59650.37651.35688.43793.99801.33808.741243.551244.671245.771250.861251.911252.991257.991259.121260.243.0131.942.072.002.50ppmCH3(CH2)16CH2CH2SHCH3(CH2)15CH2CH2

6、SD前手性化合物中CH2上两个氢的化学位移化学位移（Chemical shift）0TMS2107515AliphaticAlcohols, protons ato ketonesOlefinsAromaticsAmidesAcidsAldehydes1H谱： 15 ppm:化学位移（Chemical shift）ppm5015010080210Aliphatic CH3,CH2, CHCarbons adjacent toalcohols, ketonesOlefinsAromatics,conjugated alkenesC=O of Acids,aldehydes, esters0TMS

7、C=O inketones13C谱： 220 ppm:自旋自旋偶合（J-Coupling）自旋自旋偶合（J-Coupling）Hb2Hb3HbHaHb1Hb2Hb3HaHb1Hb2HaHb1H自旋自旋偶合（J-Coupling）HaHcCCHbJab=16HzJac=12HzABCwAJabJ自旋自旋偶合（J-Coupling）自旋自旋偶合（J-Coupling）CHH3JHH与两面角与两面角的关系的关系 (Karplus公式公式)3J=J0cos2+C =0-90 3J=J180cos2+C =90-1803J=A+Bcos+Ccos2(A=7 B=-1 C=5)自旋自旋偶合（J-Coupl

8、ing）CCR1R2HaHbCCR1HaR2Hb反式 (trans)顺式 (cis)3Jab=14-18HzHaHb3Jab=10-14HzHaHb自旋自旋偶合（J-Coupling）自旋自旋偶合（J-Coupling）HbHcHaHd3Jab= 7-94Jac= 1-35Jad= 0.5R1HcHaHdR3R2HbHcHaR1R3R2R3HcHaR1HdR2HaHcHdHaHbHcHaHbH自旋自旋偶合（J-Coupling）H3H1H2H4R3R1R2R4R1R2R3R43J12=3Jaa=8-11Hz3J13=3J24=3Jae=2-5Hz3J34=3Jee=2-5Hza 键键e 键键核

9、Overhauser效应（NOE） C C HaHbVC*r -6, 常用的核磁共振（NMR）实验1 1H H1313C C1313C CDEPT 135DEPT 135o o ( CH ( CH CH CH3 3 , CH, CH2 2 ) )1313C CDEPT 90DEPT 90o o ( CH )( CH )1 1H H1 1H COSY (H COSY (化学建上相邻氢原子的识别化学建上相邻氢原子的识别) )1 1H H1 1H TOCSY (H TOCSY (结构片断的识别结构片断的识别) )1 1H H1 1H NOESY (H NOESY (空间上相近的氢原子的识别空间上相近

10、的氢原子的识别) )1 1H H1313C (HSQC, HMQC) (C (HSQC, HMQC) (碳氢直接相关（碳氢原子直接相连）碳氢直接相关（碳氢原子直接相连）) )1 1H H1313C HMBC (C HMBC (碳氢远程相关（碳氢原子二、三、四键偶合）碳氢远程相关（碳氢原子二、三、四键偶合）) )1H 谱谱13C 谱谱13C DEPT-9013C DEPT-13513CDEPT 谱谱仅出现CHC不出现，CH、CH3 ， CH2 1H-1H COSY有没有相关峰，只取决于有没有J偶合，并不在乎相隔的化学键多少1H-1H COSY1H-1H TOCSY一个自旋体系中，原子核之间有J偶

11、合存在，称为直接偶合，没有J偶合的，称为间接偶合。间接偶合相关峰1H-1H TOCSY1H-1H NOESY1H 13C HSQC1H 13C HSQC1H-13C HMBC分子结构可以看成是由带氢的碳（氮）原子连结形成的片断，由季碳或杂原子将这些片断连接而成。HMBC实验是确定这种片断连接的最好方式。1H-13C HMBCA 和和 B 两种化合物两种化合物(分子量、元素组成相同分子量、元素组成相同)1H谱谱（A）（B）OH3COH13C谱谱（A）（B）OH3COH12345678(A) 13C谱谱(A) 13CDEPT135oOH3COH12345678(B)OH3COH1234567812

12、327888453467335666CH351S.P.CH3 (S.P.)starting point1H-1HCOSYOH3COH123456782174883 356 6CH31H-13C HSQCOH3COH123456781H谱谱21784833656CH321748853366CH3(A)(B)OH3COH1234567813C谱谱（A）（B）214783 65CH321478563CH3OH3COH123456782178833656666NOESY4(A)OH3COH12345678（B）21748853366CH3NOESY未知物结构解析的过程未知物结构解析的过程结构解析实例（

13、一）结构解析实例（一）-11211109876543210ppm-0.04382.05062.48182.48542.48992.49432.49854.80717.18267.18377.20177.22027.34547.34817.36247.36637.36987.38417.38687.84787.86778.12218.14398.47851.0001.0561.0631.0471.0451.043活泼氢活泼氢7.27.37.47.57.67.77.87.98.08.18.28.38.48.5ppm1.0561.0631.0471.0451.04318017016015014013

14、01201101009080706050403020100ppm0.229520.145739.064039.273039.481739.690539.899340.107940.3160114.2146120.8235123.5132123.5383126.9324129.0285130.3189131.7226136.4162153.6141172.78861801701601501401301201101009080706050403020100ppmppm109876543210ppm1701601501401301201101009080706050403020100ppm7.17.

15、27.37.47.57.67.77.87.98.08.18.28.38.48.58.6ppm119120121122123124125126127128129130131132133134aaghihgi-11211109876543210ppm-0.04382.05062.48182.48542.48992.49432.49854.80717.18267.18377.20177.22027.34547.34817.36247.36637.36987.38417.38687.84787.86778.12218.14398.47851.0001.0561.0631.0471.0451.043活泼

16、氢活泼氢gahi1801701601501401301201101009080706050403020100ppm0.229520.145739.064039.273039.481739.690539.899340.107940.3160114.2146120.8235123.5132123.5383126.9324129.0285130.3189131.7226136.4162153.6141172.7886lppm9.08.58.07.57.06.56.05.55.04.54.03.53.02.52.01.51.00.50.0ppm9876543210ghgppm7.17.27.37.47

17、.57.67.77.87.98.08.18.28.38.48.5ppm7.07.27.47.67.88.08.28.48.6hg eddgehppm109876543210ppm180160140120100806040200a c,j,ki j,k,lppm7.07.17.27.37.47.57.67.77.87.98.08.18.28.38.48.58.68.78.8ppm118120122124126128130132134136138140eghdicdefghijppm9876543210ppm9876543210ppm5.05.56.06.57.07.58.08.5ppm5.05.

18、56.06.57.07.58.08.5dah g eiHMBC部分结果i c, h, j, k, ld c, e, fh g, i, jg h, je d, fa c, j, k ROESY部分结果结构解析实例（二）结构解析实例（二）1.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5ppm1.4151.6481.6961.9822.2702.2722.2962.3182.4542.4792.8702.8832.8912.9053.0553.0683.9023.9083.9143.9203.9263.9314.0064.0234.0394.1524.169

19、4.1804.1844.1974.2154.3034.3144.3264.3374.5154.5194.5384.5435.0905.1145.1445.1595.2115.2355.9255.9887.1907.2597.2677.2747.2837.2907.4217.4367.4517.5598.0958.0978.1118.7052.8121.8670.9290.9251.0941.0841.0122.2691.0931.0000.8980.8881.0630.9072.1270.9981.813Current Data ParametersNAME shydEXPNO 101PROC

20、NO 1F2 - Acquisition ParametersDate_ 20020515Time 2.38INSTRUM DRX500PROBHD 5 mm TXI 1H-1PULPROG zgprTD 32768SOLVENT PyrNS 8DS 2SWH 5482.456 HzFIDRES 0.167311 HzAQ 2.9884915 secRG 8DW 91.200 usecDE 6.00 usecTE 300.0 KD1 2.00000000 secd12 0.00002000 secd13 0.00000300 sec= CHANNEL f1 =NUC1 1HP1 4.00 us

21、ecPL1 0.00 dBPL9 60.00 dBSFO1 500.1327082 MHzF2 - Processing parametersSI 16384SF 500.1300000 MHzWDW noSSB 0LB 0.00 HzGB 0PC 1.00芍药苷:1H in Pyr-d52030405060708090100110120130140150160170ppm19.84223.51943.89144.77661.50462.82871.65471.70574.99478.45878.53486.01788.923100.526101.689105.982123.304123.50

22、2123.701123.790128.755129.880130.583133.267135.346135.544135.741135.834149.607149.822150.038166.575paeoniflorinadbcefghijklmnopqrstu2030405060708090100110120130140150160170180ppm1CH3(a)、4CH2(b,d,e,f)、12CH(c,h,i,j,k,n,o,q,r,t)和和6C(g,l,m,p,s,u)adbcefghijklmnopqrstuppm2.02.53.03.54.04.55.05.56.06.57.07

23、.58.0ppm2030405060708090100110120130140abbcdqrtdppm3.84.04.24.44.64.85.05.25.45.65.86.0ppm6065707580859095100105eeffhijknmppm2.02.53.03.54.04.55.05.56.06.57.07.58.0ppm1.52.02.53.03.54.04.55.05.56.06.57.07.58.0500MHz 2D gradient COSY of paeoniflorin in pyridine-d5adbefhiknojbefdcqrtppm7.17.27.37.47.57.67.77.87.98.08.18.2ppm7.17.27.37.47.57.67.77.87.98.08.18.28.3500MHz 2D gradient COSY of paeoniflorin in pyridine-d5qrtr q trqtppm2345678ppm1.52.02.53.03.54.04.55.05.56.06.57.07.58.0paeoniflorin qrtrqtr