112 CHAPTER 2 INFRARED SPECTROMETRY Problem 2.3 Spectrum A Problem 2.3 Spectrum B Problem 2.3 Spectrum C Problem 2.3 Problems 2.3 and 2.4 Problem 2.3 Spectrum D Problem 2.4 Spectrum E Problem 2.4 Spectrum F PROBLEMS 113 114 CHAPTER 2 INFRARED SPECTROMETRY Problem 2.4 Spectrum G Problem 2.4 Spectrum H Problem 2.4 Spectrum I Problem 2.4 Problem 2.5 Problem 2.5 Spectrum J Problem 2.5 Spectrum K Problem 2.5 Spectrum L PROBLEMS 115 116 CHAPTER 2 INFRARED SPECTROMETRY Problem 2.5 Spectrum M Problem 2.6 Spectrum N Problem 2.6 Spectrum O Problems 2.5 and 2.6 Problem 2.6 Problem 2.6 Spectrum P Problem 2.6 Spectrum Q Problem 2.6 Spectrum R PROBLEMS 117 118 CHAPTER 2 INFRARED SPECTROMETRY Problem 2.7 Spectrum S Problem 2.8 Spectrum T Problems 2.7 and 2.8 Chapter 8 Additional Problems 1 MASS 1 45 CI Reagent gas methane 169 100 89 50 IR 139 137 107 100 50 100 m/z 195 197 75 171 63 50 170 180 190 200 50 4.6 4.4 4.2 2000 Wavenumber (cm-1) 4.0 3.8 3.6 663 4.8 1126 1 NMR 300 MHz HHNMR 1304 1 3000 1458 4000 2877 3440 %Transmittance 100 1000 3.4 3.2 3.0 2.8 ppm 45 ppm 1313 C/DEPT C/DEPT NMR 75.5 MHz 75 70 65 60 55 50 Chapter 8 Additional Problems 2 % of Base Peak MASS 2 97 100 41 50 100 81 70 55 113 83 51 0 98 111 65 50 50 141 110 100 m/z CI Reagent gas methane 120 153 130 m/z 140 150 1712 2870 80 4000 3000 2000 Wavenumber (cm-1) 11 H HNMR NMR600 300MHz MHz 1880 1103 1149 1458 90 2931 2954 %Transmittance IR 100 1870 9 13 13C/DEPT Hz 1800 8 1790 7 Hz 680 Hz 670 6 5 120 100 440 1000 430 420 4 410 400 3 2 390 Hz ppm MHz C/DEPT NMR NMR150.9 75.5 MHz 180 160 140 80 60 40 20 ppm Chapter 8 Additional Problems 3A 3 MASS % of Base Peak 92 120 100 50 152 65 53 50 60 70 80 90 IR m/z 100 110 120 130 140 150 50 10.5 13 10.0 9.5 9.0 2000 Wavenumber (cm-1) 4460 8.5 8.0 1000 Hz 4200 4180 Hz 4120 7.5 6.5 5.5 7.0 702 760 4680 Hz 4700 1092 1215 1304 H NMR 600 MHz 1442 1 3000 1616 1678 4000 2954 3190 %Transmittance 100 6.0 Hz 5.0 4.5 ppm C/DEPT NMR 600 MHz 170 160 150 140 130 120 110 100 90 80 70 60 50 ppm Chapter 8 Additional Problems 3B ppm 11 F1 10 9 8 7 6 5 4 4 ppm 4 4 5 5 6 6 7 7 8 8 9 9 10 10 F2 HMQC 600 MHz ppm F1 60 60 80 80 100 100 120 120 140 140 160 160 11 10 9 8 7 F2 COSY 600 MHz 6 5 4 ppm Chapter 8 Additional Problems 4A % of Base Peak MASS 5 100 50 55 IR 149 77 65 50 60 70 103 91 80 90 121 100 m/z 110 120 131 130 140 150 160 50 2000 Wavenumber (cm-1) 791 856 1034 1153 1265 3000 1427 1512 1597 2850 2935 3016 3514 %Transmittance 100 4000 1 164 1000 H NMR 600 MHz 4140 4120 7.0 13 Hz 6.5 3820 6.0 3800 Hz 5.5 3660 5.0 1140 Hz 4.5 4.0 3.5 3.0 1120 2.5 2.0 Hz ppm C/DEPT NMR 150.9 MHz 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm Chapter 8 Additional Problems 4B ppm 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 F1 6 ppm 2 2 3 3 4 4 5 5 6 6 7 7 F2 HMQC 600 MHz ppm 20 20 40 40 60 60 F1 80 80 100 100 120 120 140 140 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 F2 COSY 600 MHz ppm Chapter 8 Additional Problems 4C 7 HMQC 600 MHz ppm 7.0 6.5 6.0 ppm 4.0 3.9 ppm 1.9 1.8 ppm 7.0 6.5 6.0 ppm 4.0 3.9 ppm 1.9 1.8 ppm 20 30 40 50 ppm 105 110 F1 115 120 125 130 135 140 145 150 F2 Chapter 8 Additional Problems 5A % of Base Peak MASS 41 55 70 83 100 97 111 50 125 50 IR 168 140 100 m/z 150 50 910 1466 3000 1643 2854 2924 3078 %Transmittance 100 4000 1 8 2000 Wavenumber (cm-1) 1000 H NMR 300 MHz 1760 6.0 1740 5.5 Hz Hz 1500 5.0 4.5 620 4.0 600 Hz 3.5 280 3.0 260 Hz 2.5 2.0 1.5 ppm 13 13 C/DEPT NMR 75.5 MHz C NMR 75.5 MHz 29.8 140 130 120 110 100 29.6 90 29.4 80 29.2 70 ppm 29.0 60 50 40 30 20 ppm Chapter 8 Additional Problems 5B 9 ppm 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm 1 1 2 2 3 3 4 4 5 5 6 6 COSY 300 MHz F1 F2 HETCO 300 MHz ppm 1 1 2 2 3 3 4 4 5 5 6 6 F1 140 120 100 80 F2 60 40 20 ppm Chapter 8 Additional Problems 6A % of Base Peak MASS 10 93 68 100 136 79 77 53 50 40 50 60 70 121 107 80 IR m/z 90 100 110 120 130 140 100 887 1442 %Transmittance 795 1373 2924 1 1643 3078 4000 3000 2000 Wavenumber (cm-1) 1000 H NMR 600 MHz 1050 1300 5.5 13 5.0 4.5 1000 950 1250 900 1200 4.0 3.5 Hz 850 1150 Hz 1100 3.0 2.5 2.0 ppm 30 20 ppm C/DEPT NMR 150.9 MHz 150 140 130 120 110 100 90 80 31.0 30.5 ppm 70 60 50 40 Chapter 8 Additional Problems 6B ppm 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 11 1.5 ppm COSY 600 MHz 1.5 2.0 2.0 ppm 2.5 2.5 1.6 3.0 3.0 1.8 F1 3.5 3.5 2.0 4.0 4.0 2.2 4.5 2.2 2.0 1.8 ppm 1.6 4.5 5.0 5.0 5.5 5.5 F2 HMQC 600 MHz ppm 20 20 40 40 ppm 20 60 60 25 F1 80 80 30 100 100 35 120 120 40 140 140 45 2.2 5.5 5.0 4.5 2.0 4.0 1.8 3.5 F2 ppm 1.6 3.0 2.5 2.0 1.5 ppm Chapter 8 Additional Problems 6C 12 HMBC 600 MHz ppm 5.6 5.4 5.2 5.0 4.8 ppm 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 ppm 5.6 5.4 5.2 5.0 4.8 ppm 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 ppm 20 25 30 35 40 F1 ppm 110 115 120 125 130 135 140 145 150 F2 Chapter 8 Additional Problems 7A MASS 13 % of Base Peak 81 67 100 152 109 41 53 50 50 IR 137 123 60 70 80 90 m/z 100 110 120 130 140 150 100 50 H NMR 600 MHz 1134 1211 1288 1373 1450 1 3000 1612 1682 2870 2924 4000 2000 Wavenumber (cm-1) 1000 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 ppm 13 13 C/DEPT MHz C/DEPT NMR NMR 150.9 600 MHz 200 180 160 140 120 100 80 60 40 ppm Chapter 8 Additional Problems 7B ppm 3.0 F1 2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0 14 ppm 1.0 1.0 1.2 1.2 1.4 1.4 1.6 1.6 1.8 1.8 2.0 2.0 2.2 2.2 2.4 2.4 2.6 2.6 2.8 2.8 F2 HMQC 600 MHz ppm 20 20 25 25 30 30 F1 35 35 40 40 45 45 50 50 3.0 2.8 2.6 2.4 2.2 COSY 600 MHz 2.0 F2 1.8 1.6 1.4 1.2 1.0 ppm Chapter 8 Additional Problems 7C 15 HMBC 600 MHz ppm 2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0 0.8 ppm 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0 0.8 ppm 21 22 23 24 25 26 F1 27 28 29 30 31 32 33 ppm 50 52 ppm 150 200 2.8 F2 Chapter 8 Additional Problems 8A 16 MASS % of Base Peak 109 100 124 50 43 40 53 81 50 60 70 80 m/z IR 90 100 110 120 50 6.5 6.0 Hz 3670 5.5 2000 Wavenumber (cm-1) 3660 5.0 Hz 1420 4.5 802 7.0 4220 1026 4230 1296 H NMR 600 MHz 1520 1 3000 1674 4000 2924 3124 %Transmittance 100 1000 1410 4.0 Hz 3.5 3.0 2.5 ppm 1313 C/DEPTNMR NMR 150.9 C/DEPT 600 MHzMHz 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 ppm Chapter 8 Additional Problems 8B ppm 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 17 ppm 2 2 3 3 4 4 5 5 6 6 7 7 COSY 600 MHz F1 F2 HMQC 600 MHz ppm 20 20 40 40 60 60 F1 80 80 100 100 120 120 140 140 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 F2 ppm Chapter 8 Additional Problems 8C 18 HMBC 600 MHz ppm 7.2 7.0 6.8 6.6 6.4 6.2 2.4 2.3 ppm 20 20 30 30 40 40 50 50 60 60 70 70 80 80 90 90 100 100 110 110 120 120 130 130 140 140 150 150 160 160 170 170 180 180 F1 7.2 7.0 6.8 6.6 6.4 6.2 ppm F2 2.4 2.3 ppm Chapter 8 Additional Problems 9A % of Base Peak MASS 19 121 100 198 50 65 77 105 93 50 100 150 m/z IR 200 90 80 70 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 702 7.9 2000 Wavenumber (cm-1) 1149 H NMR 600 MHz 1281 1 3000 1442 4000 1597 1635 3286 %Transmittance 100 1000 6.9 6.8 6.7 6.6 ppm 13 13 C/DEPT MHz C/DEPTNMR NMR600 150.9 MHz 130 129 ppm 195 190 185 180 175 170 165 160 155 150 145 140 135 130 125 120 ppm Chapter 8 Additional Problems 9B ppm 8.0 F1 7.8 7.6 7.4 7.2 7.0 6.8 6.6 20 ppm 6.6 6.6 6.8 6.8 7.0 7.0 7.2 7.2 7.4 7.4 7.6 7.6 7.8 7.8 F2 HMQC 600 MHz ppm 115 115 120 120 F1 125 125 130 130 135 135 140 140 ppm 8.0 7.8 7.6 7.4 7.2 F2 COSY 600 MHz 7.0 6.8 6.6 Chapter 8 Additional Problems 9C 21 HMBC 600 MHz ppm 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5 ppm 115 120 ppm 128 130 132 F1 134 136 138 ppm 180 200 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5 F2 ppm Chapter 8 Additional Problems 10A % of Base Peak MASS 22 43 97 100 50 55 40 50 140 69 60 79 70 80 IR m/z 90 100 110 120 130 140 50 2700 4.4 4.2 4.0 3.8 3.6 2680 Hz 3.4 3.2 2540 3.0 764 H NMR 600 MHz 2000 Wavenumber (cm-1) 1072 1 3000 1358 4000 1682 1720 2854 2924 %Transmittance 100 1000 2520 Hz 2.8 2.6 2.4 2.2 2.0 1.8 ppm 1313 C/DEPTNMR NMR 150.9 C/DEPT 600 MHzMHz 200 180 160 140 120 100 80 60 40 ppm Chapter 8 Additional Problems 10B ppm 4.5 4.0 3.5 3.0 2.5 2.0 2.0 23 ppm COSY 600 MHz 2.0 ppm 2.1 2.5 2.0 1.9 1.8 1.7 ppm 2.5 1.7 1.8 F1 3.0 3.0 1.9 3.5 3.5 2.0 4.0 4.0 4.5 4.5 F2 HMQC 600 MHz ppm 20 30 20 ppm 18 30 20 40 F1 40 22 50 24 50 60 26 60 70 28 2.2 2.0 70 ppm 1.8 80 80 90 90 4.5 4.0 3.5 3.0 F2 2.5 2.0 ppm Chapter 8 Additional Problems 10C 24 HMBC 600 MHz ppm 4.5 4.0 3.5 3.0 2.5 2.0 ppm 4.5 4.0 3.5 3.0 2.5 2.0 ppm 20 25 ppm 90 100 F1 110 120 130 140 150 ppm 210 215 F2 Chapter 8 Additional Problems 11A 25 83 IR 100 125 166 169 50 50 150 m/z 90 80 2000 Wavenumber (cm-1) 949 1188 H NMR 600 MHz 1404 3000 1705 1728 2962 3178 %Transmittance 100 4000 1 114 98 100 184 x 20 69 71 43 % of Base Peak MASS 1000 x64 13 12 11 10 9 ppm 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 13 ppm C/DEPT NMR 150.9 MHz 30.2 30.2 200 180 160 140 30.1 ppm 30.1 ppm 120 100 80 60 40 20 ppm Chapter 8 Additional Problems 11B ppm 3.0 F1 2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0 26 ppm 1.0 1.0 1.2 1.2 1.4 1.4 1.6 1.6 1.8 1.8 2.0 2.0 2.2 2.2 2.4 2.4 2.6 2.6 2.8 2.8 F2 HMQC 600 MHz ppm 15 15 20 20 25 25 30 30 F1 35 35 40 40 ppm 45 45 50 30.0 55 30.5 50 55 ppm 2.4 2.2 2.0 1.8 1.6 1.4 1.2 3.0 2.8 2.6 2.4 2.2 2.0 F2 COSY 600 MHz 1.8 1.6 1.4 1.2 1.0 ppm Chapter 8 Additional Problems 11C 27 HMBC 600 MHz ppm 3.2 3.0 2.8 2.6 2.4 2.2 3.0 2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0 0.8 ppm 2.0 1.8 1.6 1.4 1.2 1.0 0.8 ppm 20 25 30 35 F1 40 45 50 55 ppm 180 190 200 210 3.2 F2 Chapter 8 Additional Problems 12A % of Base Peak MASS 28 121 93 100 136 79 77 50 105 65 53 50 60 70 80 90 m/z IR 100 110 120 130 140 825 980 1.8 5.5 13 1134 3000 H NMR 600 MHz 1.9 1373 1450 2924 4000 1 2870 2993 %Transmittance 100 1.7 5.0 1.6 1.5 4.5 1.4 4.0 2000 Wavenumber (cm-1) 1.3 1.2 3.5 1.1 1.0 3.0 1000 0.9 2.5 ppm 2.0 1.5 ppm 30 20 ppm C/DEPT NMR 150.9 MHz 130 120 110 100 90 80 70 60 50 40 Chapter 8 Additional Problems 12B ppm 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 1 29 ppm 1 2 ppm 2.0 1.8 1.6 1.4 1.2 1.0 0.8 ppm 1.0 F1 3 2 3 1.5 4 4 5 5 F2 HMQC 600 MHz ppm 20 20 ppm 15 40 40 20 60 F1 80 COSY 600 MHz 60 25 80 30 2.5 2.0 1.5 1.0 ppm 100 100 120 120 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 F2 ppm Chapter 8 Additional Problems 12C 30 HMBC 600 MHz ppm 5.7 5.6 ppm 2.0 1.8 1.6 1.4 1.2 1.0 0.8 ppm ppm 2.0 1.8 1.6 1.4 1.2 1.0 0.8 ppm 16 18 20 22 24 F1 26 28 30 ppm 120 130 140 7 6 F2