各種的化學(xué)位移值經(jīng)驗(yàn)計(jì)算方法及常見氫核的化學(xué)位移

1、各種的化學(xué)位移值經(jīng)驗(yàn)計(jì)算方法及常見氫核的化學(xué)位移各種的化學(xué)位移值經(jīng)驗(yàn)計(jì)算方法及常見氫核的化學(xué)位移1.1.烷烴和取代烷烴中烷烴和取代烷烴中1H的化學(xué)位移的化學(xué)位移（1）可從表4－6直接查得取代基?碳上的質(zhì)子化學(xué)位移值。取代基對(duì)?碳上的質(zhì)子化學(xué)位移也有一定影響，在計(jì)算?碳上的質(zhì)子化學(xué)位移值時(shí)，應(yīng)將表4－7中?位的各種取代基影響值加到表4－6中的化學(xué)位移值上。表4－6不同取代基時(shí)CH3X、CH2X和CHX的質(zhì)子化學(xué)位移（?ppm）XCH3XC

2、H2XCHX－R0.91.31.5－CH＝CH21.71.92.6－CH＝CH－CH＝CH21.8CH2＝CH－C＝CH22.02.22.3－CH＝N－2.0－C?CH2.02.2－CO，－COOAr2.02.12.2－CN2.02.52.7－CONH2－CONR22.02.02.1－COOH2.12.32.6－C2.12.42.5－SH，－SR2.12.42.5－I2.23.14.2－NH2，－NR22.12.52.9－CHO2.22

3、.22.4－Ph2.32.62.9－Br2.63.34.1－NHC，－NRC2.93.33.5－Cl3.03.44.0－OC3.64.15.0－3.33.33.8－NR33.33.43.5－OH3.43.63.8－OAr3.73.94.0－OCOAr3.94.25.1－NO24.34.44.6注：表中R表示烷基，Ar表示芳香基。表4－7取代基X對(duì)?位CH3、CH2、CH質(zhì)子化學(xué)位移值的影響XCH3CXCH2CXCHCXXCH3CXCH2

4、CXCHCX－C＝C－0.10.10.1－Br0.80.60.25COOHCO0.20.20.2－NHC0.10.10.1－CN0.50.40.4－Cl0.60.40－CONH20.250.20.2OH0.30.20.2CCHO0.30.20.2－OC0.40.30.3SHSR0.450.30.2－OPh0.40.350.3－C?N0.230.780.58－Br1.040.400.55―C＝C－0.980.040.21－Cl1.000.

5、190.03C=C（共軛）1.260.080.01－F1.030.891.19－C＝O1.101.130.81－NR20.691.191.31C＝O（共軛）1.061.010.95－SR1.000.240.043.3.苯環(huán)上質(zhì)子的化學(xué)位移值苯環(huán)上質(zhì)子的化學(xué)位移值與烯氫化學(xué)位移值的計(jì)算類似，苯環(huán)上質(zhì)子的化學(xué)位移值可用以下公式計(jì)算：?＝7.26＋?Zi（4－23）式中，7.26是沒有取代的苯環(huán)上質(zhì)子的?值，?Zi是取代基對(duì)苯環(huán)上的剩余質(zhì)子化

6、學(xué)位移影響之和，Zi不僅與取代基的種類有關(guān)，而且與取代基的相對(duì)位置有關(guān)。各種取代基的Zi值列入表4－10中。表4－10取代基對(duì)苯環(huán)上質(zhì)子化學(xué)位移值的影響取代基Z2Z3Z4取代基Z2Z3Z4H000NHCH30.800.220.68CH30.200.120.22N(CH3)20.660.180.67CH2CH30.140.060.17NHNH20.600.080.55CH(CH3)20.130.080.18N=NPh0.670.200.2

7、0C(CH3)30.020.080.21NO0.580.310.37CF30.320.140.20NO20.950.260.38CCl30.640.130.10SH0.080.160.22CHCl2000SCH30.080.100.24CH2OH0.070.070.07SPh0.060.090.15CH＝CH20.060.030.10SO3CH30.600.260.33CH=CHPh0.150.010.16SO2Cl0.760.350.

8、45C?CH0.150.020.01CHO0.560.220.29C?CPh0.190.020COCH30.620.140.21Ph0.370.200.10COC(CH3)30.440.050.05F0.2600.20COPh0.470.130.22Cl0.030.020.09COOH0.850.180.27Br0.180.080.04COOCH30.710.110.21I0.390.210COOPh0.900.170.27OH0.56

9、0.120.45CONH20.610.100.17OCH30.480.090.44COCl0.840.220.36OPh0.290.050.23COBr0.800.210.37OCOCH30.250.030.13CH=NPh～0.6～0.2～0.2OCOPh0.090.090.08CN0.360.180.28OSO2CH30.050.070.01Si(CH3)30.220.020.02－NH20.750.250.65PO(OCH3)20