Organic Structure Elucidation - A Workbook of Unknowns www.nd.edu/~smithgrp/structure/workbook.html Answers and Spectroscopic Assignments Carleton G. Collins, Department of Chemistry and Biochemistry, University of Notre Dame, IN 46556, USA Copyright 2012 Acknowledgement: This answer book was prepared with funding support from the National Science Foundation (CHE 1058699).
Spectroscopic Technique Signal/Information Comments Problem 1 C 3H 5BrO 2, UN=1 152, 154 (M, [M2] ) 135, 137 (M-17) 107, 109 (M-45) 73 (M-79) 3067 (broad) 1717 >9 (exchanges) 3.45 (t) 3.0 (t) 178 (s) 24.3 (t) 38.6 (t) 1 double bond Br present (1:1) M M CO M Br CO C=O stretch (acid) CO Problem 2 C 8H 14O 4, UN=2 2 double bonds 174 (M) 146 129 (M-45) 101 (M-73) 2986 1749 4.17 (m) 3.39 (q) 1.39 (d) 1.24 (t) 170 61 46 13.9, 13.5 M CH 2=CH 2 (McLafferty Rgt) M OCH 2CH 3 M COOCH 2CH 3 C=O stretch (ester) (diastereotopic) 2
Problem 3 Problem 4 C 9H 12 UN=4 120 (M ) 105 (M-15) 91 (M-29) 3027, 3062 2865, 2900 7.35 (m) 2.64 (t) 1.71 (sextet) 1.02 (t) 142.6 128.4, 128.1 125.5 38.0 24.5 13.8 C 7H 13Br UN=1 176, 178 (M, [M2] ) 97 (M-79) 83 (M-93) 2938, 2849 1445 3.27 (d) 1.86-1.63 (m) 1.25-0.98 (m) Phenyl ring M CH 3 M CH 2CH 3 (tropylium ion) (aryl) (alkyl),, H7, 1 ring Br present (1:1) M Br M CH 2Br (cyclohexyl ring) es (alkyl) CH 2 bend - - Problem 5 40.8, 40.0 31.7, 26.1, 25.8 C 5H 8O, UN=2 84 (M ) 55 (M-29) 28 (M-56) 3063 2860, 2937,,, 1 ring and 1 double bond M C 2H 5 (Retro Diels-Alder) Ethene cation (Retro Diels-Alder) es 3
Problem 6 1644 1070, 1238 6.35 (dt) 4.66 (m) 3.97 (t) 1.98 (q) 1.84 144.0 101.7 65.7 22.7, 19.4 C 9H 13NO UN=4 152 (MH ) 120 (M-31) 91 (M-60) 60 (M-91) 3352, 3298 2800-3100 3075 2823 1581 7.37-7.25 (m) 5.2 (1H, exchanges) 3.69 (dd), 3.47 (dd) 3.18 (sp) 2.85 (dd), 2.58 (dd) 2.1 (2H, exchanges) 138.6 129.1, 128.3 126.3 66.2 54.1 40.8 C=C stretch es, Aryl ring M CH 2 M CH 2CH(NH 2)CH 2 (tropylium ion) M PhCH 3 Amine N-H stretches stretch Amine N-H bend - H7 (diastereotopic) (diastereotopic) NH 2, 4
Problem 7 Problem 8 Problem 9 C 6H 10, UN = 2 82 (M ) 67 (M-15) 54 (M-28) 28 (M-54) 3064 2780, 2985 1692 5.66 (s) 1.99 (m) 1.61 (quintet) 127 25.1 22.6 C 8H 11NO, UN =4 138 (MH ) 120 (M-18) 107 (M-31) 77 (M-61) 30 (M-108) 2500-3500 3358 1598 7.36 (m) 5.2 (exchanges) 4.35 (dd) 2.59 (dd), 2.51 (dd) 1.3 (broad) 142.7 128.3, 125.8 127.4 74.1 49.2 C 10H 7Br, UN=7 206, 208 (M, [M2] ) 1 ring and 1 double bond M CH 3 (Rearrangement) M ethene (Retro Diels-Alder) M 1,3-butadiene (Retro Diels-Alder) es C=C stretch Phenyl ring M H 2O M CH 3NH 2 (hydroxyl tropylium ion) M CH 2()CH 2NH 2 M PhCH 2 [CH 2NH 2 ] O--H--N stretch Amine N-H stretch Amine N-H bend - (diastereotopic) NH 2, Naphthyl ring Br present (1:1) 5
Problem 10 127 (M-79) 101, 103 3054 1486, 1573 7.78 7.57, 7.51 7.47 (d) 7.31 (dd) 7.25 (m) 134.4 131.7 129.8, 129.4, 129.1 127.8 126.9, 126.8 126.2 119.4 C 14H 19NO 4, UN=6 265 (M ) 209 (M-56) 148 (M-117) 91 (M-174) 57 (M-208) 3318 2400-3000 1711 1652 10 7.2 5.0, 6.8 4.40, 4.63 3.0 1.3, 1.4 176, 177 155, 157 127, 129, 130, 136, 138 80, 82 54, 56 38, 40 27, 28 M Br M 2 Aromatic C=C stretches H9, H7, H8 0,, C8, C9 1 aryl ring and 2 double bonds M CH 2=C(CH 3) 2 (McLafferty Rgt) M NH 2COOC(CH 3) 3 M CH 2-C 6H 5 (tropylium ion) C(CH 3) 3 Amide N-H stretch (secondary) CO C=O stretch (acid) C=O stretch (amide) CO Aromatic (carbamate rotation) H8 Aromatic C8 6
Problem 11 Problem 12 C 6H 12O 2, UN=1 116 (M) 98 (M-18) 70 (M-46) 57 (M-59) 3279, 3378 2862, 2935 3.3 3.0 1.9, 1.6 1.2 75.7 32.8 24.2 C 7H 5NO 4, UN=6 167 (M ) 150 (M-17) 137 (M-30) 120 (M-47) 109 (M-58) 1 ring M H 2O M CH 2CH 2, H 2O (McLafferty Rgt) C 3H 5O 2 stretches es,,,,,, 1 aryl ring and 2 double bond M M NO M NO 2H M NO, CO 3114 2500-3100 1673 1520 11.4 (s) 10.3 (s) 8.11 (d) 7.12 (dd) 7.06 (d) 190.2 163.0 140.5 134.8 127.6 119.1, 114.7 C=O stretch (aldehyde) -NO 2 stretch H7, 7
Problem 13 C 5H 10O 4, UN=1 135 (MH ) 117 (M-18) 104 (M-31) 86 (M-49) 3226, 3372 2500-3000 1691 ~11 (br, exchanges) 4.5 (exchanges) 3.4 (q) 1.0 (s) 1 double bond M H 2O M CH 2 M CH 2, H 2O stretches CO C=O stretch (acid) CO Problem 14 176.6 63.8 49.5 17.0 C 8H 6O 2, UN=6 134 (M ) 135 (M-1) 105 (M-29) 77 (M-57) 2698 1693 10.2 (s) 8.0 (s) 191.4 139.9 130.0 1 aryl ring and 2 double bonds M H M CHO C 6H 5 Aldehyde C-H stretch C=O stretch (aldehyde) CHO 8
Problem 15 C 13H 10O 3, UN=9 214 (M ) 121 (M-93) 93 (M-121) 3186 1683 1480 10.5 (exchanges) 8.0 (dd) 7.45 (td) 7.35 (m) 7.21 (m) 7.11 (m) 6.97 (d) 6.95 (t) 168.9 162.1 150.0 136.4 129.6, 130.3 126.3 121.6 117.7, 119.4 111.7 2 aryl rings and 1 double bond M OPh M CO 2Ph stretch C=O stretch (ester) Aromatic C=C stretch 0 1 H9 C8, 0 1 C9, 9
Problem 16 Problem 17 C 7H 6O 2, UN=5 122 (M ) 121 (M-1) 104 (M-18) 93 (M-29) 76 (M-46) 3239 2849 1665 ~11 (exchanges) 9.8 (s) 7.51 (m) 6.98 (m) 117.5, 119.7 120.5, small 133.6, 136.7 161.5, small 196.5 C 9H 10O 3, UN=5 166 (M ) 121 (M-45) 91 (M-75) 77 (M-89) 2500-3300 2961 1701 1022, 1243 11.8 (exchanges) 7.20 (m) 6.86 (m) 3.8 (s) 3.6 (s) 178.1 158.8 130.3 125.2 114.0 55.2 40.0 1 aryl ring and 1 double bond M H M H 2O M CHO M CO, H 2O stretch Aldehyde C-H stretch C=O stretch (aldehyde) H7,,,, 1 aryl ring and 1 double bond M CO M CH 2CO, CH 4 M OCH 3, CH-CO CO C=O stetch (acid) Aryl ether stretch CO H7 10
Problem 18 Problem 18 C 7H 10O 4, UN=3 158 (M ) 143 (M-15) 115 (M-43) 83 (M-75) 2940, 2995 1771 1202 4.85 (dd) 4.75 (d) 4.42 (m) 1.47 (s), 1.38 (s) 174.1 113.9 74.5, 75.4 70.1 25.5, 26.7 C 7H 10O 4, UN=3 158 (M ) 143 (M-15) 115 (M-43) 83 (M-75) 2940, 2995 1771 1202 4.85 (dd) 4.75 (d) 4.42 (m) 1.47 (s), 1.38 (s) 174.1 113.9 74.5, 75.4 70.1 25.5, 26.7 2 rings and 1 double bond M CH 3 M CH 3CO M (CH 3) 2CO 2H es C=O stretch (ester), H7,, 2 rings and 1 double bond M CH 3 M CH 3CO M (CH 3) 2CO 2H es C=O stretch (ester), H7,, Problem 19 C 9H 7NO 4, UN= 7 1 aryl ring and 3 double bonds 11
Problem 20 193 (M ) 176 (M-17) 146 (M-47) 91 (M-102) 2400-3000 2942 1691 1341 12.0 (exchanges) 7.73 (d) 7.46 (d) 7.19 (d) 6.25 (d) 167.0 147.9 141.3 140.7 129.3 123.9 123.5 C 8H 9NO 2, UN=5 151 (M ) 107 (M-44) 94 (M-57) 77 (M-74) M M NO 2H M NO 2, CO (tropylium ion) CO C=O stretch (acid) -NO 2 stretch (sym) CO 1 aryl ring and 1 double bond M CONH 2 M CHCONH 2 (phenol cation) C 6H 5 3358, 3464 2922 1698 1248 7.21(t) 6.92 (t) 6.81 (d) 6.48 (exchanges) 6.19 (exchanges) 4.3 (s) 171.2 157.0 129.7 122.1 NH stretches C=O stretch (amide) NH NH 12
Problem 21 Problem 22 114.5 67.0 C 9H 12O 3, UN=4 168 (M ) 151 (M-17) 119 (M-49) 107 (M-61) 94 (M-74) 77 (M-91) 3292 2935 1050, 1242 7.17 (m) 6.85 (m) 6.79 (m) 3.99 (quin) 3.91 (m) 3.63 (dd), 3.72 (dd) 2.59 (exchanges) 158.3 129.5 121.2 114.4 70.4 68.9 63.6 C 9H 12N 2O, UN=5 164 (MH ) 120 (M-44) 103 (M-61) 91 (M-73) 77 (M-87) 3306, 3352 3034 1678 1605 6.87 (exchanges) 6.72-6.82 (m) 1 aryl ring M M, CH 2 M CH()CH 2 M CHCH()CH 2 (phenol cation) C 6H 5 stretch es (diastereotopic) H7 (diastereotopic) 1 aryl ring and 1 double bond M CONH 2 M HNH 2CONH 2 M CHNH 2CONH 2 (tropylium ion) C 6H 5 NH 2 stretches C=O stretch (amide) NH 2 bend NH 2 (amide) - 13
Problem 23 6.5 (exchanges) 2.88 (dd) 2.12 (dd), 2.46 (dd) 1.12 (exchanges) 176.7 138.9 128.0, 129.3 126.0 56.2 41.2 C 9H 10O 3, UN=5 166 (M ) 149 (M-17) 94 (M-72) 77 (M-89) 2600-3400 3047 1718 1235 12 (exchanges) 7.15 (t) 6.83 (t) 6.78 (d) 4.12 (t) 2.75 (t) NH 2 (amide) (diastereotopic) NH 2 (amine), 1 aryl ring and 1 double bond M M CHCH 2CO C 6H 5 CO C=O stretch (acid) CO Problem 24 177.3 158.3 129.4 121.1 114.5 62.8 34.3 C 9H 10O 3, UN=5 166 (M ) 135 (M-31) 122 (M-44) 77 (M-89) 1 aryl ring and 1 double bond M OCH 3 M CHO, CH 3 C 6H 5 14
Problem 25 3074 2948 2836 1705 1156, 1301 9.90 (s) 6.99 (d) 6.69 (t) 3.90 (s) 191.9 161.1 138.3 107.0, 107.1 55.5 C 14H 14NO 3, UN=8 214 (M ) 199 (M-15) 171 (M-43) 128 (M-86) 2955 1248 825 7.50 (d) 6.97 (d) 3.91 (s) Aldehyde C-H stretch C=O stretch (aldehyde) es CHO, 2 aryl rings M CH 3 M CO, CH 3 M 2CO, 2CH 3 1,4-disubstituted aromatic Problem 26 158.6 133.4 127.6 114.1 55.2 C 7H 11BrO 4, UN=2 238, 240 (M, [M2] ) 193, 195 (M-45) 166, 168 (M-72) 138, 140 (M-100) 29 (M-209) 2 double bonds Br present (1:1) M OCH 2CH 3 M CO 2CH 2CH 3 CH 2BrCO CH 3CH 2 15
Problem 27 Problem 28 2986 1743 1149 4.82 (s) 4.28 (q) 1.30 (t) 164.5 63.2 42.3 13.8 C 8H 19N, UN=0 129 (M ) 86 (M-43) 44 (M-85) 3410 2928 1461 1132 2.57 (t) 1.45 (pent) 1.31 (sextet) 1.10 (exchanges) 0.90 (t) 49.8 32.3 20.4 13.9 C 6H 12O 2Cl 2, UN=0 187 (M ) 137, 139 (M-49) 107, 109 (M-79) 93, 95 (M-93) 63, 65 (M-79) 28 (M-158) 2873 1127 665 C=O stretch (ester) Fully saturated M CH 2CH 2CH 3 CH 3NH=CH 2 (McLafferty Rgt) NH stretch CH 2 and CH 3 bend C-N stretch NH Fully saturated M CH 2Cl M OCH 2CH 2Cl M CH 2OCH 2CH 2Cl ClCH 2CH 2 M 2(OCH 2CH 2Cl) C-Cl stretch 16
Problem 29 Problem 30 3.77 (t) 3.69 (s) 3.64 (t) 71.3 70.6 42.7 C 3H 7OCl, UN=0 94, 96 (M, [M2] ) 63 (M-31) 45 (M-49) 28 (M-66) 2887 1125 671 3.59-3.65 (m) 3.38 (s) 72.4 58.8 42.6 C 6H 6O 2, UN=4 110 (M ) 92 (M-18) 81 (M-29) 64 (M-46) 3325 (broad) 1518 1188 743 8.8 (exchanges) 6.72 (dd) 6.59 (dd) 145.2 119.2 115.6 Fully saturated Cl present (1:3) M OCH 3 M CH 2Cl M OCH 3, Cl (ether) C-Cl stretch, 1 aryl ring M H 2O M CHO M CH 2O 2 stretch Aromatic C=C stretch 1,2-disubstituted aromatic 17
Problem 31 Problem 32 C 6H 7NO, UN=4 109 (M ) 80 (M-29) 28 (M-81) 18 (M-91) 3296, 3361 2500-3100 1593 1259 1180 907 8.8 (exchanges) 6.75 (t) 5.99 (s) 5.95 (dd), 5.98 (dd) 4.9 (exchanges) 157.9 149.6 129.2 105.3 103.2 100.9 C 7H 6NF 3, UN=4 161 (M ) 142 (M-19) 114 (M-47) 92 (M-69) 3385 1630 1343 1123 7.24 (t) 6.99 (dd) 6.89 (s) 6.82 (dd) 3.9 (exchanges) 146.6 129.6 1 aryl ring M C M C 4H 3NO M C 6H 5N NH 2 stretches stretch NH 2 bend C-N stretch NH 2 bend, NH 2 1 aryl ring M F M CH 2NF M CF 3 NH 2 stretch NH 2 bend C-F stretch NH 2 18
Problem 33 Problem 34 123.0 (q) 117.9 114.9 111.2 C 6H 4Cl 2, UN=4 146, 148, 150 (M, [M2], [M4] ) 111 (M-35) 3067 1458 746 7.43 (m) 7.19 (m) 132.5 130.5 127.7 C 6H 5NO 3, UN=5 139 (M ) 122 (M-17) 93 (M-46) 3477 3108 1312, 1535 1177 >9 (exchanges) 8.17 (dd) 7.59 (td) 7.18 (dd) 7.00 (td) 155.1 137.5 133.5 125.0 119.9, 120.2 1 aryl ring 2 Cl present (10:6.6:1) M Cl Aromatic C=C stretch 1,2-disubstituted aromatic 1 aryl ring and 1 double bond M M NO 2 stretch NO 2 stretches, 19
Problem 35 Problem 36 Problem 37 C 6H 5NO 3, UN=5 139 (M ) 93 (M-46) 81 (M-74) 65(M-74) 3398 3114 1354, 1534 1213 7.81 (dd) 7.70 (t) 7.41 (t) 7.18 (dd) 5.7 (exchanges) 155.8 149.1 130.2 121.9 115.8 110.5 C 4H 4N 2, UN=4 80 (M ) 52 (M-28) 26(M-54) 3050 8.5 145.1 C 6H 7PO 3, UN=4 158 (M ) 141 (M-17) 94 (M-64) 77 (M-81) 2756 (broad) 1 aryl ring and 1 double bond M NO 2 M CNO 2 M CNO 3 stretch NO 2 stretches 1 aryl ring M C 2H 4 M C 2H 2N 2 1 aryl ring M M PO 2H (phenol cation) C 6H 5 PO-H stretch 20
Problem 38 Problem 39 7.68 (dd) 7.48-7.53 (m) 7.43-7.47 (m) 5.5 (exchanges) 134.1 (d) 130.9 (d) 130.6 (d) 128.1 (d) C 9H 8N 2, UN=7 144 (M ) 117 (M-27) 90 (M-54) 77 (M-67) 3392 (broad) 3115 1514 1308 10.5 (exchanges) 7.76 (d) 7.72 (s) 7.38-7.42 (m) 7.28 (t) 138.9 135.9 133.1 128.9 127.2 125.1 115.7 C 5H 6O 3, UN=3 114 (M ) 86 (M-28) 73 (M-41) 60 (M-54) 55 (M-59) 2981 1758, 1830 1230 2 aryl rings M HCN M C 2H 3N 2 C 6H 5 N-H stretch Aromatic C=C stretch C-N stretch NH H7, 1 ring and 2 double bonds M CO M C 2H 3O M C 3H 5O M C 2H 3O 2 Anhydride stretches 21
Problem 40 Problem 41 2.43 (t) 1.96 (pent) 177.5 32.9 19.6 C 16H 35N, UN=0 241 (M ) 142 (M-99) 3277 2854, 2929 1100 2.57 (t) 2.17 (s) 1.45 (m) 1.21-1.32 (m) 0.87 (t) 50.1 30.1, 31.8 27.4, 29.5, 29.8 22.6 14.0 C 6H 12O 5, UN=1 164 (M ) 146 (M-18) 133 (M-31) 73 (M-91) 60 (M-104) 3252, 3339 2946 1464 4.5 (exchanges) 4.45 (d) 3.66 (d) 3.55 (dd) 3.54 (m) 3.41 (dd) Fully saturated M C 7H 15 N-H stretch es C-N stretch NH -H7 H8,,, C8 1 ring M H 2O M OCH 3 M C 2H 3O 3 M C 3H 6O 3 stretches CH 2 bend, bend, 22
Problem 42 Problem 43 3.34 (exchanges) 3.25 (s) 100.6 69.0 68.6 68.2 62.9 54.8 C 13H 9NO 3, UN=10 227 (M ) 150 (M-77) 105(M-122) 77 (M-150) 3101 1651 1512 8.34 (d) 7.93 (d) 7.80 (d) 7.65 (t) 7.53 (t) 194.8 149.7 142.8 136.2 133.4 128.2, 130.0, 130.8 123.5 C 7H 6BrF, UN=4 188, 190 (M, [M2] ) 142, 144 (M-46) 109 (M-79) 77 (M-111) 3074 2925, 2984 1473 7.48 (dd) 2 aryl rings and 2 double bonds M C 6H 5 M C 7H 4NO 2 M C 7H 4NO 3 C=O stretch (ketone) NO 2 stretch H8 H7 C9,, C8 1 aryl ring Br present (1:1) M C 2H 3F M Br C 6H 5 es Aromatic C=C stretch 23
Problem 44 Problem 45 6.97 (dd) 6.78 (td) 2.3 (s) 161.7 (d) 139.9 133.3 118.9 117.7 (d) 114.4 (d) 23.0 C 13H 10 UN=9 166, 167 (M ) 165 (M-1) 3028 1446 7.80 (d) 7.56 (d) 7.32 (t), 7.38 (t) 3.91 (s) 143.1 141.6 126.6, 126.8 125.0 119.8 36.8 C 10H 11NO 3, UN=6 117 (M ) 162 (M-15) 107 (M-70) 2934 2241 1518 1025, 1262 6.83 (m) 3.87 (s), 3.89 (s) 3.70 (s) H7 2 aryl rings and 1 ring M H Aromatic C=C stretch, H7, 1 aryl ring and 1 triple bond M CH 3 M CN, OCH 3, CH 3 C N stretch Aromatic C=C stretch es (ether),, H7 H8 24
148.7, 149.3 122.0 120.1 118.1 110.8, 111.4 55.9 23.1, C9, C8 Problem 46 Problem 47 (2 sets of peaks) Problem 48 C 5H 12O 2, UN=2 104 (M ) 73 (M-31) 2948, 2993 1375 1084 3.19 (s) 1.35 (s) 99.8 48.3 23.8 C 6H 12O 3, UN=2 131 ([M-1] ) 115 (M-17) 101 (M-31) 72 (M-60) 2906, 2958, 2996 1026, 1218 5.09 (m) 3.42 (s), 3.36 (s) 1.82, 2.10 (m) 106.1 55.3 30.9 C 10H 20O, UN=2 156 (M ) 138 (M-18) 2 double bonds or rings M M OCH 3 es CH 3 bending ing 2 double bonds and/or rings M CH 4 M OCH 3 C 4H 8O es es 2 double bonds or rings M H 2O 25
Problem 49 3252 2927 1456 1045 3.41 (td) 2.15 (heptet of doublets) 1.92-2.00 (m) 1.58-1.70 (m) 1.37-1.48 (m) 1.32 (exchanges) 0.90-0.95 (m) 0.81 (d) 71.5 50.1 45.0 34.5 31.6 25.8 23.1 22.2 16.0, 20.1 C 9H 16O 5, UN=2 205 (MH ) 159 (M-45) 141 (M-63) 130 (M-74) 113 (M-91) 3511 2983, 2939 1740 1372 1024, 1189 4.43-4.48 (m) 4.18 (q) 3.45 (exchanges) 2.53-2.58 (m) 1.28 (t) 171.8 64.7 60.7 stretch CH 2 bend H8 (1H, diastereotopic), H7 (1H, diastereotopic) (1H),, H7 (1H), H9 (6H) C8 C9 2 double bonds M OC 2H 5 (α-cleavage) M OC 2H 5, H 2O M OC 2H 5, C 2H 5 M OC 2H 5, CO, H 2O stretch es C=O stretch (ester) CH 3 bend es (diastereotopic) 26
Problem 50 Problem 51 40.6 14.1 C 3H 7OCl, UN=0 93, 95 (M-1, [M2]-1 ) 78 (M-16) 58 (M-36) 3352 2889, 2961 1448 1054 721 3.83 (t) 3.68 (t) 2.1 (q) 1.52 (exchanges) 59.4 41.7 34.8 C 8H 6O 3, UN=6 150 (M ) 122 (M-28) 94 (M-56) 66 (M-84) 3332 2923 1760 1476 1078, 1152 9.2 (exchanges) 6.96 (d) 6.76 (m) 6.67 (dd) 3.90 (s) 174.7 153.7 146.6 124.9 Fully saturated Cl present (1:3), ClCH 2CH 2CH 2O M CH 2=CHCH 2 stretch, CH 2 bends C-Cl stretch 1 aryl ring, 1 ring, and 1 double bond M CO M 2CO (phenol cation) M 3CO (cyclopentadiene cation) stretch C=O stretch (lactone), CH 2 bends es H7 C8 27
Problem 52 Problem 53 1 H NMR (ppm) 13 C NMR (ppm) Problem 54 110.3, 111.7, 114.1 33.1 C 9H 10O 2, UN=5 150 (M ) 132 (M-18) 104 (M-46) 77 (M-73) 2200-3200 3068 2967 1692 1304 > 9 (exchanges) 7.23 (t) 7.07 (d) 2.4 (s) 174.9 135.6 132.2 129.9 127.8 20.1 C 6H 8O 2, UN=3 112 (M ) 83 (M-29) 56 (M-42) 2912, 2965 1711 2.8 (s) 208.3 36.6 C 5H 7NO 3, UN=3 129 (M ) 114 (M-15) 86 (M-43),, 1 aryl ring and 1 double bond M H 2O M CO, H 2O C 6H 5 CO C=O stretch (acid) bend CO 1 ring and 2 double bonds M CO M 2 es C=O stretch (ketone) 1 ring and 2 double bonds M CH 3 M CH 3CO 28
Problem 55 70 (M-59) 43 (M-86) 28 (M-101) 15 (M-114) 3266 1783 1043, 1246 6.8 (exchanges) 5.82 (dd) 3.25 (dd), 3.28 (dd) 2.1 (s) 171.1 165.2 72.9 44.8 20.7 C 8H 8O 2, UN=5 136 (M ) 135 (M-1) 107(M-29) 77(M-59) 3010 2934 2743, 2839 1684 1261 ~10 (s) 7.85 (d) 7.00 (d) 3.90 (s) 190.8 164.5 131.9 129.9 114.2 55.5 M O=C-OCH 3 CH 3C=O CH=NH CH 3 NH stretch C=O stretch (amide) es NH 1 aryl ring and 1 double bond M H M CHO (anisole cation) C 6H 5 Aldehyde C-H stretches C=O stretch (aldehyde) CHO Problem 56 C 7H 11NO 2, UN=3 1 double bond and 1 triple bond 29
Problem 57 Problem 58 141 (M ) 126(M-15) 57 (M-84) 2936, 2983 2262 1744 3.3(s) 1.5(s) 161.8 113.4 84.3 27.7 25.8 C 6H 5O 2SCl, UN=4 176, 178 (M, [M2] ) 141 (M-35) 77 (M-99) 3069 1377, 1185 8.05 (dd) 7.76 (tt) 7.63 (t) 144.3 135.2 129.6, 126.9 C 10H 13N 5O 4, UN=7 267 (M ) 178 (M-89) 164 (M-103) 135 (M-132) 3170, 3334 1664 1042, 1300 8.38 (s) 8.16(s) M CH 3 C 4H 9 (t-bu cation) es C N stretch C=O stretch 4 double bonds/ring (likely aromatic) Cl present (1:3) M Cl C 6H 5 S=O stretches, 1 aryl ring, 2 rings, 1 double bond M C 3H 5O 3 M C 4H 7O 3 M C 5H 8O 4 (adenine cation), NH 2 stretches NH 2 bend es 30
Problem 59 7.39 (exchanges) 5.87 (d) 5.45 (exchanges) 5.19 (exchanges) 4.59-4.64 (m) 4.12-4.15 (m) 3.95 (q) 3.50-3.70 (dd s) 156.1 152.3 149.0 139.9 119.3 87.9 85.9 73.4 70.6 61.6 C 14H 12O 2, UN=9 212 (M ) 211 (M-1) 91 (M-121) 77 (M-135) 3056 2743, 2827 1688 1021, 1255 ~10 (s) 7.85 (d) 7.35-7.45 (m) 6.90 (d) 5.1 (s) 190.8 163.7 135.8 131.9 130.0 127.4, 128.3, 128.7 115.1 70.2 NH 2 (connected to, C8) (connected to 0) H7 H8 H9 0 (diastereotopic) C9 C8 0 2 aryl rings and 1 double bond M H C 7H 7 (tropylium ion) C 6H 5 Aldehyde C-H stretches C=O stretch (aldehyde) es CHO H8 - H7 0 C8 C9,, 31
Problem 60 Problem 61 Problem 62 C 4HO 3Br UN=4 176, 178 (M, [M2] ) 132 (M-44) 104 (M-72) 3121, 3182 1781 1597 1225 7.17 (s) 160.2, 161.7 133.7 133.4 C 8H 14O 3, UN=2 158 (M ) 103 (M-55) 85 (M-73) 57 (M-101) 2935, 2981 1718 1023, 1149 3.3(s) 2.3(s) 1.5(s) 201.2 166.3 81.9 51.5 30.0 27.9 C 6H 11O 2Br, UN=1 194, 196 (M, [M2] ) 177, 179 (M-17) 115 (M-79) 97 (M-97) 60 (M-134) 1 ring and 3 double bonds Br present (1:1) M CO 2 M CO 2, CO es C=O stretch (anhydride) C=C stretch, 2 double bonds M C 3H 3O M OC(CH 3) 3 C 4H 9 (t-bu cation) es C=O stretch es 1 double bond Br present (1:1) M M Br M Br, H 2O M-CH 2=CHCCBr 32
Problem 63 Problem 64 2500-3500 2942 1711 1195 ~10 (exchanges) 3.40 (t) 2.39 (t) 1.82-1.87 (m) 1.65 (pent) 1.55 (pent) 179.3 33.4, 33.6 23.7, 27.5, 32.3 C 14H 12O 2, UN=9 212 (M) 195 (M-17) 105 (M-107) 77 (M-135) 3378 1677 7.91 (dd) 7.52 (tt) 7.40 (t) 7.28-7.36 (m) 5.98 (d) 4.59 (exchanges) 198.8 138.9 133.9 133.4 127.2-129.1 (5 signals) 76.1 C 10H 12O, UN=5 148 (M) 120 (M-28) 105 (M-43) 77 (M-71) CO C=O stretch CO,,, 2 aryl rings and 1 double bond M C 7H 5O C 6H 5 stretch C=O stretch (ketone) H9, H8, 0 -, C8-0 1 aryl ring and 1 double bond M CH 2=CH 2 (McLafferty Rgt) M CH 2CH 2CH 3 C 6H 5 33
3060 2874, 2962 1680 1450 7.95 (d) 7.55 (t) 7.47 (t) 2.95 (t) 1.79 (sextet) 1.00 (t) 200.4 137.0 132.8 128.0, 128.5 40.4 17.7 13.8 es C=O stretch (ketone) CH 2, CH 3 bends H7 H8, C8 34