譜圖解析NMR Stucture Elucidation

1、譜圖解析NMR的主要參數(shù)NMR與化學(xué)結(jié)構(gòu)譜峰指認(rèn)、圖譜解析核磁共振的參數(shù)核磁共振的參數(shù)化合物的分子結(jié)構(gòu)化合物的分子結(jié)構(gòu)化學(xué)位移化學(xué)位移偶合裂分偶合裂分譜峰強(qiáng)度譜峰強(qiáng)度弛豫時間弛豫時間NOE作用作用偶極作用偶極作用1H、13C一維譜同核二維譜異核二維、三維譜原子與原子的連接原子與原子的連接原子之間的空間取向原子之間的空間取向化學(xué)結(jié)構(gòu)的動態(tài)平衡化學(xué)結(jié)構(gòu)的動態(tài)平衡化學(xué)位移（Chemical shift）B0Be原子核實(shí)際感受到的磁場: Beff = (1-s s) B0 （s: 屏蔽常數(shù)）實(shí)際的共振頻率： =(1-)B0同種原子核在不同的化學(xué)環(huán)境中，有不同的屏蔽常數(shù)，產(chǎn)生不同的共振頻率：A、B，二者

2、的絕對頻率差別： A B(A-B) B0 （與外磁場強(qiáng)度B0有關(guān)）相對頻率差別： （通常10-6, 用ppm值表示）(A )/ B0= A-B （與外磁場強(qiáng)度B0無關(guān)）化學(xué)位移（Chemical shift）誘導(dǎo)效應(yīng)(對飽和烷烴的影響)與質(zhì)子相連的碳原子上,如果接有電負(fù)性強(qiáng)的基團(tuán),則由于吸電子誘導(dǎo)效應(yīng),使質(zhì)子周圍的電子云密度減弱,使屏蔽作用減弱,質(zhì)子共振吸收移向低場,電負(fù)性越強(qiáng),化學(xué)位移值越大.R=Cl, F, Br,-NCORCH2=4.5-5.5R=NH2, -COR,-ArCH2=3.5-S-P雜化從sp3（碳碳單鍵）到sp2（碳碳雙鍵）s電子的成分從25%增加到33%，鍵電子更靠近碳原

3、子，因而對相連的氫原子有去屏蔽作用，即共振位移移向低場。（芳環(huán)與烯烴比飽和烷烴的化學(xué)位移低場的原因）磁各向異性HaHaHbHb18-環(huán) 稀Ha=8.9ppmHb=1.8ppm磁各向異性鹵素與不飽和烷烴連接時同時有共軛作用和誘導(dǎo)作用：F的共軛作用大于誘導(dǎo)作用，所以鄰位的氫譜和碳譜都移向高場；Cl的共軛作用和誘導(dǎo)作用相互抵消所以影響很??；Br到I共軛作用小于誘導(dǎo)作用所以相比鄰位氫明顯偏向低場。共軛作用和誘導(dǎo)作用（對不飽和烷烴影響）介質(zhì)因素（溶劑、pH值等）成鹽后氮旁邊的CH2低場偏移 =0.5氫鍵的影響對活潑氫的影響很大。氫鍵形成，氫鍵中質(zhì)子信號明顯移向低場，對分子內(nèi)氫的化學(xué)位移也有影響。樣品分子

4、間氫鍵和濃度有關(guān)，樣品的分子內(nèi)氫鍵和濃度無關(guān)。樣品分子還會與溶劑分子成氫鍵。其它因素重水交換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交換的變化交換的變化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上兩個氫的化學(xué)位移化學(xué)位移（Chemical shift）0TMS2107515AliphaticAlcohols, protons ato ketonesOlefinsAromaticsAmidesAcidsAldehydes1H譜： 15 ppm:化學(xué)位移（Chemical shift）ppm5015010080210Aliphatic CH3,CH2, CHCarbons adjacent toalcohols, ketonesOlefinsAromatics,conjugated alkenesC=O of Acids,aldehydes, esters0TMS

7、C=O inketones13C譜： 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與兩面角與兩面角的關(guān)系的關(guān)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)順式 (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 鍵鍵e 鍵鍵核

9、Overhauser效應(yīng)（NOE） C C HaHbVC*r -6, 常用的核磁共振（NMR）實(shí)驗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 (化學(xué)建上相鄰氫原子的識別化學(xué)建上相鄰氫原子的識別) )1 1H H1 1H TOCSY (H TOCSY (結(jié)構(gòu)片斷的識別結(jié)構(gòu)片斷的識別) )1 1H H1 1H NOESY (H NOESY (空間上相近的氫原子的識別空間上相近

10、的氫原子的識別) )1 1H H1313C (HSQC, HMQC) (C (HSQC, HMQC) (碳?xì)渲苯酉嚓P(guān)（碳?xì)湓又苯酉噙B）碳?xì)渲苯酉嚓P(guān)（碳?xì)湓又苯酉噙B）) )1 1H H1313C HMBC (C HMBC (碳?xì)溥h(yuǎn)程相關(guān)（碳?xì)湓佣?、三、四鍵偶合）碳?xì)溥h(yuǎn)程相關(guān)（碳?xì)湓佣?、三、四鍵偶合）) )1H 譜譜13C 譜譜13C DEPT-9013C DEPT-13513CDEPT 譜譜僅出現(xiàn)CHC不出現(xiàn)，CH、CH3 ， CH2 1H-1H COSY有沒有相關(guān)峰，只取決于有沒有J偶合，并不在乎相隔的化學(xué)鍵多少1H-1H COSY1H-1H TOCSY一個自旋體系中，原子核之間有J偶

11、合存在，稱為直接偶合，沒有J偶合的，稱為間接偶合。間接偶合相關(guān)峰1H-1H TOCSY1H-1H NOESY1H 13C HSQC1H 13C HSQC1H-13C HMBC分子結(jié)構(gòu)可以看成是由帶氫的碳（氮）原子連結(jié)形成的片斷，由季碳或雜原子將這些片斷連接而成。HMBC實(shí)驗是確定這種片斷連接的最好方式。1H-13C HMBCA 和和 B 兩種化合物兩種化合物(分子量、元素組成相同分子量、元素組成相同)1H譜譜（A）（B）OH3COH13C譜譜（A）（B）OH3COH12345678(A) 13C譜譜(A) 13CDEPT135oOH3COH12345678(B)OH3COH1234567812

12、327888453467335666CH351S.P.CH3 (S.P.)starting point1H-1HCOSYOH3COH123456782174883 356 6CH31H-13C HSQCOH3COH123456781H譜譜21784833656CH321748853366CH3(A)(B)OH3COH1234567813C譜譜（A）（B）214783 65CH321478563CH3OH3COH123456782178833656666NOESY4(A)OH3COH12345678（B）21748853366CH3NOESY未知物結(jié)構(gòu)解析的過程未知物結(jié)構(gòu)解析的過程結(jié)構(gòu)解析實(shí)例（

13、一）結(jié)構(gòu)解析實(shí)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活潑氫活潑氫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活潑

16、氫活潑氫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部分結(jié)果i c, h, j, k, ld c, e, fh g, i, jg h, je d, fa c, j, k ROESY部分結(jié)果結(jié)構(gòu)解析實(shí)例（二）結(jié)構(gòu)解析實(shí)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芍藥苷: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