Answers for Student Exercises 1.1 to 1.5 a 3-ethyloctane C10H22 CnHmXxNyOz Index = (n) - (m/2) - (x/2) + (y/2) + = IHD Atom Type Hydrogen Carbon Nitrogen Oxygen Sulfur Bromine # of Atoms Mass 1.00783 22 10 12.00000 14.0031 15.9949 31.9721 78.9183 Exact Mass Total Mass 22.17226 120.00000 0.00000 0.00000 0.00000 0.00000 142.17226 - (C2H5 ) Rule - (C5H11 ) Rule H - (CH2=CH2) Rule b 3-butylcyclohex-1-ene C10H18 CnHmXxNyOz Index = (n) - (m/2) - (x/2) + (y/2) + = IHD Atom Type Hydrogen Carbon Nitrogen Oxygen Sulfur Bromine or - (C4H9 ) Rule and - (CH2=CH2) Rule - (C3H7 ) Rule # of Atoms Mass 1.00783 18 10 12.00000 14.0031 15.9949 31.9721 78.9183 Exact Mass Total Mass 18.14094 120.00000 0.00000 0.00000 0.00000 0.00000 138.14094 Answers for Student Exercises 1.1 to 1.5 Atom Type Hydrogen Carbon Nitrogen Oxygen Sulfur Bromine O c 2-methyl-1-phenylhexan-1-one C13H18O CnHmXxNyOz Index = (n) - (m/2) - (x/2) + (y/2) + = IHD # of Atoms Mass 1.00783 18 13 12.00000 14.0031 15.9949 31.9721 78.9183 Exact Mass O O Total Mass 18.14094 156.00000 0.00000 15.99490 0.00000 0.00000 190.13584 O - (C6H13 ) Rule O O - (C6H5 ) Rule O H O - (C4H8) OH H Rule O - (CO) Rule 8+9 Atom Type Hydrogen Carbon Nitrogen Oxygen Sulfur Bromine d (E)-undec-3-ene C11H22 CnHmXxNyOz Index = (n) - (m/2) - (x/2) + (y/2) + = IHD or - (CH3) Rule - (C6H13) Rule H - (C7H14) Rule # of Atoms Mass 1.00783 22 11 12.00000 14.0031 15.9949 31.9721 78.9183 Exact Mass Total Mass 22.17226 132.00000 0.00000 0.00000 0.00000 0.00000 154.17226 Answers for Student Exercises 1.1 to 1.5 e 1-(hexan-2-yl)benzene C12H18 CnHmXxNyOz Index = (n) - (m/2) - (x/2) + (y/2) + = IHD Atom Type Hydrogen Carbon Nitrogen Oxygen Sulfur Bromine # of Atoms Mass 1.00783 18 12 12.00000 14.0031 15.9949 31.9721 78.9183 Exact Mass Total Mass 18.14094 144.00000 0.00000 0.00000 0.00000 0.00000 162.14094 - (CH3 ) Rule - (C4H9 ) Rule - (C4H8 ) H H Rule H f OH heptan-2-ol C7H16O CnHmXxNyOz Index = (n) - (m/2) - (x/2) + (y/2) + = OH OH H OH H OH IHD Atom Type Hydrogen Carbon Nitrogen Oxygen Sulfur Bromine # of Atoms Mass 1.00783 16 12.00000 14.0031 15.9949 31.9721 78.9183 Exact Mass Total Mass 16.12528 84.00000 0.00000 15.99490 0.00000 0.00000 116.12018 - (C5H11 ) Rule OH - (CH3 ) Rule OH - (H ) Rule - (H2O) Rule OH Answers for Student Exercises 1.1 to 1.5 g COOH 3,5,7-trimethyloctanoic acid C11H22O2 CnHmXxNyOz IHD Index = (n) - (m/2) - (x/2) + (y/2) + = Atom Type Hydrogen Carbon Nitrogen Oxygen Sulfur Bromine # of Atoms Mass 1.00783 22 11 12.00000 14.0031 15.9949 31.9721 78.9183 Exact Mass Total Mass 22.17226 132.00000 0.00000 31.98980 0.00000 0.00000 186.16206 O C O - (OH ) OH Rule O C O OH H O O - (C10H21 ) C Rule O - (C9H18) Rule HO h OH hexan-1-ol C6H14O CnHmXxNyOz Index = (n) - (m/2) - (x/2) + (y/2) + = IHD Atom Type Hydrogen Carbon Nitrogen Oxygen Sulfur Bromine O C OH H OH OH HO HO # of Atoms Mass 1.00783 14 12.00000 14.0031 15.9949 31.9721 78.9183 Exact Mass Total Mass 14.10962 72.00000 0.00000 15.99490 0.00000 0.00000 102.10452 H H O - (CH2=CH2 ) - (H2O) Rule OH - (C5H11 ) Rule H 2C OH - (H ) OH Rule OH Answers for Student Exercises 1.1 to 1.5 i OH 2-methylheptan-2-ol C8H18O CnHmXxNyOz IHD Index = (n) - (m/2) - (x/2) + (y/2) + = Atom Type Hydrogen Carbon Nitrogen Oxygen Sulfur Bromine # of Atoms Mass 1.00783 18 12.00000 14.0031 15.9949 31.9721 78.9183 Exact Mass Total Mass 18.14094 96.00000 0.00000 15.99490 0.00000 0.00000 130.13584 - (C5H11 ) OH OH Rule - (CH3 ) OH OH Rule H H O - (H2O) - (CH2=C(CH3)2) Rule Rule j S butyl(propyl)sulfane C7H16S CnHmXxNyOz Index = (n) - (m/2) - (x/2) + (y/2) + = S IHD Atom Type Hydrogen Carbon Nitrogen Oxygen Sulfur Bromine # of Atoms Mass 1.00783 16 12.00000 14.0031 15.9949 31.9721 78.9183 Exact Mass - (C3H7 ) Rule - (CH2=CH2) S Rule H S Total Mass 16.12528 84.00000 0.00000 0.00000 31.97210 0.00000 132.09738 - (C2H5 ) Rule S SH S Answers for Student Exercises 1.1 to 1.5 k OH (2-hexylphenyl)methanol C13H20O CnHmXxNyOz IHD Index = (n) - (m/2) - (x/2) + (y/2) + = OH Atom Type Hydrogen Carbon Nitrogen Oxygen Sulfur Bromine # of Atoms Mass 1.00783 20 13 12.00000 14.0031 15.9949 31.9721 78.9183 Exact Mass OH or - (C5H11 ) OH OH Rule CH2 CH2 - (OH ) OH Total Mass 20.15660 156.00000 0.00000 15.99490 0.00000 0.00000 192.15150 Rule OH - (H2O) H Rule O l NO2 (4-nitrophenyl)(phenyl)methanone C13H9NO3 CnHmXxNyOz IHD 10 Index = (n) - (m/2) - (x/2) + (y/2) + = Atom Type Hydrogen Carbon Nitrogen Oxygen Sulfur Bromine # of Atoms Mass 1.00783 13 12.00000 14.0031 15.9949 31.9721 78.9183 Exact Mass Total Mass 9.07047 156.00000 14.00310 47.98470 0.00000 0.00000 227.05827 O O - (C6H4NO2 ) NO2 O Rule 7&8 - (CO) Rule 8&9 O O - (C6H5 ) NO2 Rule 7&8 NO2 Answers for Student Exercises 1.1 to 1.5 m O 3-(ethoxymethyl)heptane C10H22O CnHmXxNyOz IHD Index = (n) - (m/2) - (x/2) + (y/2) + = Atom Type Hydrogen Carbon Nitrogen Oxygen Sulfur Bromine # of Atoms Mass 1.00783 22 10 12.00000 14.0031 15.9949 31.9721 78.9183 Exact Mass - (CH3 ) O O CH2 Rule - (C7H15 ) O Total Mass 22.17226 120.00000 0.00000 15.99490 0.00000 0.00000 158.16716 O Rule - (C4H9) O O Rule O n H Br 2-bromodecanal C10H19BrO CnHmXxNyOz IHD Index = (n) - (m/2) - (x/2) + (y/2) + = O Atom Type Hydrogen Carbon Nitrogen Oxygen Sulfur Bromine # of Atoms Mass 1.00783 19 10 12.00000 14.0031 15.9949 31.9721 78.9183 Exact Mass Total Mass 19.14877 120.00000 0.00000 15.99490 0.00000 78.91830 234.06197 O - (H ) H Br Rule Br O - (CO ) Rule Br Br H H O H Br - (C8H16) Rule O H H Br Answers for Student Exercises 1.1 to 1.5 o O O cyclohexyl acetate C8H14O2 CnHmXxNyOz Index = (n) - (m/2) - (x/2) + (y/2) + = O O IHD Atom Type Hydrogen Carbon Nitrogen Oxygen Sulfur Bromine - (C6H11O ) # of Atoms Mass 1.00783 14 12.00000 14.0031 15.9949 31.9721 78.9183 Exact Mass Total Mass 14.10962 96.00000 0.00000 31.98980 0.00000 0.00000 142.09942 O Rule O O - (CH3 ) O O Rule O H O - (CH2=C=O) Rule O H Answers for Student Exercises 1.6 to 1.11 A O Base Peak Molecular Ion Fragement Ion Fragment Loss 71 114 99 / C6H11O 15 / CH3 86 / C5H10 28 / C2H4 71 / C4H7O 43 / C3H7 58 / C3H5O 56 / C4H8 43 / C3H7 71 / C4H7O 4-Heptanone C7H14O Exact Mass: 114.1045 IHD = 1, match with (k) B OH 4-Bromotoluene C7H7Br Exact Mass: 169.9731 IHD = 4, match with (v) D Fragement Ion Fragment Loss 59 116 by CI 115 / C7H15O 1/H 98 / C7H14 18 / H2O 87 / C5H11O 29 / C2H5 69 / C5H9 18 / H2O, 29 / C2H5 59 / C3H7O 57 / C4H9 45 / C2H5O 71 / C5H11 43 / C3H7 73 / C4H9O 41 / C4H5 18 / H2O, 57 / C4H9 R Rearrangment R R Base Peak Molecular Ion Fragement Ion Fragment Loss 91 170 91 / C7H7 79 / Br Rearrangment Tropylium Ion 75 / C6H3 80 / HBr, 16 / CH4 R 65 / C5H5 79 / Br, 26 / C2H2 R 50 / C4H2 120 / C7H5Br 39 / C3H2 131 / C4H5Br Br 2-Bromopentane C5H11Br Exact Mass: 150.0044 IHD = 0, match with (r) R Molecular Ion C7H16O Exact Mass: 116.1201 IHD = 0, match with (m) Br R Base Peak 3-Heptanol C Rearrangment Base Peak Molecular Ion Fragement Ion Fragment Loss 71 150 121 / C3H6Br 29 / C2H5 107 / C2H4Br 43 / C3H7 71 / C5H11 79 / Br 55 / C4H7 80 / HBr, 16 / CH4 43 / C3H7 C2H4Br Rearrangment R Answers for Student Exercises 1.6 to 1.11 O E 10 Base Peak Molecular Ion Fragement Ion Fragment Loss 43 100 85 / C5H9O 15 / CH3 71 / C4H7O 29 / C2H5 58 / C4H10 42 / C2H2O 57 / C3H5O 43 / C3H7 43 / C3H7 57 / C3H5O 2-Hexanone C6H12O Exact Mass: 100.0888 IHD = 1, match with (h) O F OH Propionic Acid Base Peak Molecular Ion Fragement Ion Fragment Loss 74 74 73 / C3H5O2 1/H 57 / C3H5O 17 / OH 56 / C3H4O 18 / H2O 45 / CHO2 29 / C2H5 C3H6O2 Exact Mass: 74.0368 IHD = 1, match with(c) G H2N OH prop-2-yn-1-ol C3H4O Exact Mass: 56.0264 IHD = 2, match with (a) R Rearrangment R Base Peak Molecular Ion Fragement Ion Fragment Loss Rearrangment 73 73 56 / C4H8 17 / NH3 R 55 / C4H7 18 / NH4 R 44 / C2H6N 29 / C2H5 43 / C3H7 30 / CH4N butan-1-amine C4H11N Exact Mass: 73.0896 IHD = 0, match with (b) H Rearrangment Base Peak Molecular Ion Fragement Ion Fragment Loss 55 56 by CI 55 / C3H3O 1/H 39 / C3H3 17 / OH 38 / C3H2 18 / H2O Rearrangment CHAPTER ASSIGNED PROBLEMS Problem 8.40A ppm 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.5 F1 ppm 1.5 2.0 2.0 2.5 2.5 3.0 3.0 3.5 3.5 4.0 COSY 600 MHz 11 10 OH 4.0 4.5 4.5 F2 HMQC 600 MHz ppm 10 20 20 11 40 40 60 60 H3C 11 F1 100 C O 10 O 80 120 Ethyl 3-hydroxy-3,6dimethylhept-6-enoate C11H20O3 Mol Wt.: 200 140 100 120 160 140 160 5.0 4.5 4.0 3.5 3.0 F2 HO 80 2.5 2.0 1.5 ppm CHAPTER ASSIGNED PROBLEMS Problem 8.43C HMBC 600 MHz OH 10 11 ppm 10 20 11 30 40 50 60 70 F180 F1 HO 90 H3C 11 100 C O 10 O 110 Ethyl 3-hydroxy-3,6dimethylhept-6-enoate C11H20O3 Mol Wt.: 200 120 130 140 150 160 170 5.0 4.5 4.0 3.5 F2 3.0 2.5 2.0 1.5 ppm CHAPTER ASSIGNED PROBLEMS Problem 8.44A MASS % of Base Peak 121 100 136 50 93 65 178 149 50 100 IR 150 m/z 50 H NMR 600 MHz 2000 Wavenumber (cm-1) 841 3000 1173 1211 1281 4000 1597 1658 2962 3325 %Transmittance 100 1000 OH 8.0 7.8 7.6 7.4 7.2 7.0 6.8 ppm 3.0 2.5 2.0 ppm 1.5 13 13 C/DEPT MHz C/DEPT NMR NMR 150.9 600 MHz O 200 180 160 140 120 OH 4'-Hydroxy valerphenone C11H14O2 Mol Wt.: 178 100 80 60 40 ppm CHAPTER ASSIGNED PROBLEMS Problem 8.44B ppm 1 ppm COSY 600 MHz O 8 7 3 F1 4 OH 4'-Hydroxy valerphenone C11H14O2 Mol Wt.: 178 5 6 OH 7 8 F2 HMQC 600 MHz ppm 20 20 40 40 60 60 F1 80 80 100 100 120 120 F2 ppm CHAPTER ASSIGNED PROBLEMS Problem 8.44C HMBC 600 MHz OH ppm 8.0 7.5 7.0 ppm 3.0 2.5 2.0 1.5 1.0 15 ppm ppm 15 O 20 20 F1 25 25 30 OH 4'-Hydroxy valerphenone C11H14O2 Mol Wt.: 178 30 35 35 ppm ppm 120 120 130 130 140 140 150 150 160 160 170 170 180 180 190 190 200 200 210 210 ppm 8.0 7.5 7.0 ppm F2 3.0 2.5 2.0 1.5 1.0 CHAPTER ASSIGNED PROBLEMS Problem 8.45A MASS % of Base Peak 68 100 108 53 50 79 50 153 151 125 93 100 m/z IR 168 150 50 887 933 H NMR 600 MHz 1242 2000 Wavenumber (cm-1) 5,4 1412 1442 1705 3000 2669 2893 2962 3078 %Transmittance 100 1000 10 2900 Hz 2850 1600 1550 x64 Hz 1200 1150 1100 Hz 1050 OH ppm 12 4.5 4.0 3.5 3.0 2.5 2.0 1.5 10 ppm C/DEPT MHz C/DEPT NMR 150.9 600 MHz H2CNMR 13 13 H HO CH3 10 O 2-((1R,2S)-1-methyl-2-(prop-1-en-2yl)cyclobutyl)acetic acid C10H16O2 Mol Wt.: 168 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 ppm CHAPTER ASSIGNED PROBLEMS Problem 8.45B 5.0 ppm 4.5 4.0 3.5 3.0 2.5 2.0 1.5 COSY 600 MHz ppm 10 1.5 1.5 2.0 2.0 2.5 2.5 54 5,4 7 F1 3.0 3.0 3.5 3.5 4.0 4.0 4.5 4.5 5.0 5.0 F2 HMQC 600 MHz ppm 20 H2C 40 20 H HO 60 40 CH3 60 10 O 2-((1R,2S)-1-methyl-2-(prop-1-en-2yl)cyclobutyl)acetic acid ppm 80 C10H16O2 Mol Wt.: 168 F1 100 20 120 30 140 80 10 100 120 140 40 160 160 50 180 180 3.0 5.0 4.5 10 4.0 3.5 2.5 3.0 F2 2.0 2.5 1.5 2.0 ppm 1.5 ppm CHAPTER ASSIGNED PROBLEMS Problem 8.45C HMBC 600 MHz 5.0 ppm 4.8 ppm 2.6 2.4 2.2 5,4 2.0 1.8 10 1.6 1.4 1.2 ppm 20 25 H2C 30 10 H HO 35 CH3 10 O F1 2-((1R,2 S)-1-methyl-2-(prop-1-en-2yl)cyclobutyl)acetic acid C10H16O2 40 Mol Wt.: 168 45 50 ppm 150 5.0 4.8 ppm 2.6 2.4 F2 2.2 2.0 1.8 1.6 1.4 1.2 ppm CHAPTER ASSIGNED PROBLEMS % of Base Peak 100 50 53 IR 91 77 122 65 50 60 70 80 90 100 110 m/z 120 151 148 133 130 140 166 150 160 787 1365 1466 %Transmittance 100 50 2916 1049 3332 4000 Problem 8.46A 105 MASS 3000 H NMR 600 MHz 2000 Wavenumber (cm-1) 1000 10 2180 2160 Hz 1440 1420 1400 1380 1360 1340 1320 1300 1280 1260 1240 1220 Hz 11 5.0 13 4.5 4.0 OH 3.5 3.0 2.5 2.0 1.5 ppm 1.0 C/DEPT NMR 150.9 MHz 10 11 CH2CH2OH 130 120 Nopol C11H18O Mol Wt.: 166 140 11 110 100 90 80 10 70 60 50 40 30 ppm CHAPTER ASSIGNED PROBLEMS Problem 8.46B ppm 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 COSY 600 MHz ppm 1.0 1.0 1.5 1.5 2.0 2.0 10 2.5 2.5 F1 3.0 3.0 3.5 3.5 4.0 4.5 4.0 5.0 5.0 5.5 5.5 OH 11 4.5 F2 HMQC 600 MHz ppm 10 11 20 20 CH2CH2OH 40 40 Nopol C11H18O Mol Wt.: 166 60 F1 ppm 30 80 11 60 80 10 100 35 100 40 120 2.5 5.5 OH 5.0 4.5 4.0 3.5 2.4 3.0 F2 2.3 2.2 2.5 2.0 2.1 1.5 ppm 1.0 120 ppm CHAPTER ASSIGNED PROBLEMS Problem 8.46C INADEQUATE MHz INADEQUATE 150.9600 MHz 11 Hz -15000 -15000 -10000 -10000 10 11 -5000 -5000 CH2CH2OH F1 5000 5000 Nopol C11H18O Mol Wt.: 166 10000 10000 15000 15000 140 130 120 110 10 100 90 F2 80 70 60 50 40 30 20 ppm Hz -16000 -16000 -14000 -14000 -12000 -12000 -10000 -10000 -8000 -8000 -6000 -6000 F1 -4000 -4000 -2000 -2000 0 2000 2000 4000 4000 45 40 35 F2 30 25 20 ppm CHAPTER ASSIGNED PROBLEMS Problem 8.47A % of Base Peak MASS 105 CI Reagent gas methane 100 277 100 77 50 136 154 50 FM (found) = 277.1083 by CI 100 150 IR 50 200 m/z 305 250 m/z 317 300 2877 2939 3000 H NMR 600 MHz 1281 1712 1751 4000 2000 Wavenumber (cm-1) 1000 12 10 4800 4700 4600 717 50 1072 3456 %Transmittance 100 10 OH 4500 Hz 3300 3200 O 3100 3000 Hz 1500 11 1400 Hz 1300 12 O 13 O 10 CO 12 O C O O O CH2OH 11 2200 Hz 2250 1750 1700 Hz 3.0 2.5 HOH 2C 5-(Benzoyloxy)hexahydro-4(hydroxymethyl) C15H16O5 Mol Wt.: 276 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 ppm CHAPTER ASSIGNED PROBLEMS Problem 8.47B ppm 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 ppm COSY 600 MHZ O O 13 10 O C O 41 12 11 CH2OH 11 5 F1 5-(Benzoyloxy)hexahydro-4(hydroxymethyl) C15H16O5 Mol Wt.: 276 6 O C O O O HOH2C 8 COSY 600 MHZ ppm 2.5 2.5 3.0 3.0 3.5 3.5 10 12 10 12 11 F1 4.0 4.0 4.5 4.5 5.0 5.0 5.5 5.5 5.5 5.0 4.5 4.0 3.5 F2 3.0 2.5 ppm CHAPTER ASSIGNED PROBLEMS Problem 8.47C 13 C/DEPT NMR 150.9 MHz 13 180 170 160 129 ppm 130 150 140 77.5 130 11 1012 ppm 77.0 120 110 100 90 80 70 40 ppm 50 HMQC 600 MHz 11 60 ppm O 40 O 13 10 50 C O 60 O 12 O 13 O OH HOH2C CH2OH 11 11 13 70 C O 12 10 O F1805-(Benzoyloxy)hexahydro-4(hydroxymethyl) C15H16O5 Mol Wt.: 276 12 90 ppm 100 35 12 10 10 12 10 110 40 120 3.0 2.9 2.8 2.7 2.6 2.5 2.4 ppm 130 8.0 7.5 7.0 6.5 6.0 5.5 5.0 F2 4.5 4.0 3.5 3.0 2.5 ppm CHAPTER ASSIGNED PROBLEMS Problem 8.47D HMBC 600 MHz ppm 8.2 8.0 7.8 7.6 40 7.4 ppm 11 5.0 4.5 4.0 12 3.5 3.0 10 OH 2.5 ppm 12 10 O O 13 10 50 O C O 60 12 7 CH2OH 11 11 70 5-(Benzoyloxy)hexahydro-4(hydroxymethyl) C15H16O5 Mol Wt.: 276 80 F1 ppm 130 140 150 160 170 13 180 8.2 8.0 7.8 7.6 7.4 ppm 5.0 F2 4.5 4.0 3.5 3.0 2.5 ppm ... A1 3.45 for ClCH2 plus Table B.1 value of 1.50 for HC=O 3.3 (m) Integration Answers for Student Exercise 3.1 to 3.3 14 2H H H F (n) fluoroethene 3.1(n) Charts are not available in text for this... be two singlets because of the restricted rotation of the NR2 ** These can not be first order Not magnetically equivalent 3.3 (k) 2,2’ 3,3’ 6,7 Integration 2 6* Answers for Student Exercise 3.1... C2H3O 42 / C2H2O 54 / C4H6 R Answers for Student Exercise 2.1 – 2.9 2.1 Since the indicated carbon of phenylacetonitrile is sp3 hybridized, it is reasonable for this compound to show C−H stretching