nmbk-1393-2-7-10-12-57Solutions Kalman

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited Solutions Manual December 2007 1

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited 1 5 BrCH2 CH2Br 9 OH OH 13 Cl2CH CH3 O CH3 C C CH3 1,2-dibromoethane CH3 CH3 1,1-dichloroethane 2-butanone C2H4Br2 C2H4Cl2 C4H8O pinacol 6O C6H14O2 14 CH3 CH3 2 CH3CH2 OH CH3 10 O O H OH O CH3 propionic acid C3H6O2 O 3O 1,2-butanedione 1,4-cyclohexanedione 2-propanol (biacetyl) C6H8O2 C3H8O CH2CH3 C4H6O2 CH3 O 11 O 15 CH3 CH3 7 CH2C N ethyl acetate H Br C4H8O2 CH2C N 4 CH3O CH2CH3 succinonitrile cyclopentanone 2-bromopropane C4H4N2 C5H8O2 C3H7Br O 8 CH3 CH3 12 CH3CH2 I 16 Cl methyl propionate Cl C4H8O2 CH3 C C CH3 iodoethane CH3 CH3 C2H5I 1,4-dichlorobutane December 2007 C4H8Cl2 2,2,3,3-tetramethylbutane C8H18 2

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited 17 Br Br 21 H2N COOH 25 CH2C N 29 1,3-dibromopropane 4-aminobutyric acid 26 benzyl cyanide C3H6Br2 C4H9NO2 C8H7N CH2 C CH3 O 18 Br Cl 22 CH2NH2 benzyl methyl ketone OCH3 C9H10O 30 O 1-bromo-3-chloropropane 23 anisole 27 benzylamine propiophenone C3H6BrCl C7H8O C7H9N C9H10O 19 Br C N CH2OH OH 31 CH3 4-bromobutyronitrile benzyl alcohol 2-phenylethanol CH C H C7H8O C8H10O O C4H6NBr CH2Br OH 2-phenylpropionaldehyde 28 H C9H10O CH3 20 + 24 32 O NH3 1-phenylethanol C8H10O butyrophenone CH3 H COO - C10H12O alanine benzyl bromide C3H7NO2 C7H7Br December 2007 3

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited 33 O O 37 N OO 45 CH3 O O CH3 O CH3 H 41 C C O H CH3 O t-butyl acetoacetate O C8H14O3 dibenzylamine propionic anhydride 1,1-diacetoxyethane 34 CH3CH2 O C H C14H15N C6H10O3 C6H10O4 O 38 CH3 42 O 46 CH3OOC COOCH3 ethyl formate N CH3 OC C O H CH3 C3H6O2 CH3 N O 35 O CH3 diethyl oxalate O N,N,N,N-tetramethyl-1,2- C6H10O4 dimethyl methylmalonate ethanediamine benzil C6H16N2 C6H10O4 C14H10O2 36 39 O 43 O 47 O CH3 1,2-diphenylethane CH3 O O CH3 CH3 O C OCH3 C14H14 O O O December 2007 2,5-hexanedione ethylene glycol diacetate methyl acetyllactate C6H10O2 C6H10O4 C6H10O4 40 O 44 O 48 O CH3CH2O OCH2CH3 CH3O OCH3 O C O C O O diethyl carbonate dimethyl succinate diethyl succinate C5H10O3 C6H10O4 C8H14O4 4

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited O H3C CH3 49 O 53 57 OCH3 61 O CHCl2 OCH3 H3C CH3 O OCH3 α,α-dichlorotoluene ethylene glycol dipropionate C7H6Cl2 1,2,3-trimethoxybenzene durene C8H14O4 54 OCH3 C9H12O3 C10H14 50 O O CH CH3 CH3 CH3 CC OCH3 O 58 62 CH3 CH3 CH3 CH3 butyric anhydride benzaldehyde dimethylacetal mesitylene 1,2,3,4-tetramethylbenzene C8H14O3 C9H12O2 C9H12 C10H14 51 55 OH 59 CH3 63 CH3 CH3 Br Br COOH CH3 CH3 CH3 1,2,3-trimethylbenzene CH3 C9H12 1,4-dibromobenzene benzilic acid 1,2,3,5-tetramethylbenzene C6H4Br2 C14H12O3 C10H14 56 OH 52 Br 60 CH3 64 CH3 CH3 OH CH3 Br CH3 CH3 CH3 CH3 CH3 4,4'-dibromobiphenyl catechol 1,2,4-trimethylbenzene hexamethylbenzene C12H8Br2 C6H6O2 C9H12 C12H18 December 2007 5

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited 65 CH3 CH3 69 OH 73 OH 77 HOOC COOH 70 CH3 CH3 CH3 CH3 CH3 CH3 O CH3 CH3 CH3 H CH3 1,2,3,4,5,- 3-hydroxybutanone 2-methyl-2-butanol 3,3-dimethylglutaric acid pentamethylcyclopentadiene (acetoin) (t-amyl alcohol) C7H12O4 C4H8O2 C5H12O C10H16 HO 74 NH2 66 CH3 NH2 78 HOOC COOH O O acetamide 4-hydroxy-4-methyl-2- hexylamine 2,2-dimethylpentanedioc C2H5NO pentanone C6H15N acid C6H12O2 67 O C7H12O4 71 HO 75 O 79 CH3 CH3 O O CH3 O CH3CH2 O CH3 NN isobutyl acetate Br CH3 CH3 C6H12O2 O 72 COOH ethyl glycolate ethyl 2-bromopropionate tetramethylurea C4H8O3 C5H9O2Br C5H12N2O 68 O 76 OCH3 80 O O CH3CH2O CN O OCH3 ethyl cyanoacetate 3,3-dimethylbutyric acid 4,4-dimethoxy-2-butanone 1,3-dioxan C5H7NO2 C6H12O2 C6H12O3 C4H8O2 December 2007 6

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited 81 O 85 Br 89 93 O O OH HO CH2 OH dibutyl ether 1,4-dioxan C8H18O C4H8O2 2-bromohexanoic acid 2-methylbut-3-en-2-ol C6H11O2Br C5H10O 94 82 O O 86 CN 90 H NH3+ butylbenzene OO C O- C10H14 OO CN CH3 95 18-crown-6 H OH O C12H24O6 C(CH3)3 2-ethylmalononitrile 91 threonine 83 H2C C CH2Cl C5H6N2 C4H9NO3 Cl 87 Br CN 2,3-dichloropropene 3-methylbutyronitrile 1-bromo-3-phenylpropane t-butylbenzene C3H4Cl2 C5H9N C9H11Br C10H14 84 O 88 H2N C CH 92 NO2 96 sec-butylbenzene O CH3 C10H14 Cl 4-chlorobutyl acetate 5-amino-1-pentyne 1-nitropropane C6H11O2Cl C5H9N C3H7NO2 December 2007 7

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited 97 101 O 105 O 109 Cl C CH3O C HO CH2OCH3 CH3 CH3 C(CH3)3 neopentylbenzene p-chloroacetophenone 4-methoxyacetophenone 4-methoxymethylphenol C11H16 C8H7OCl C9H10O2 C8H10O2 98 102 O 106 O 110 CH3 N CH2Cl CH3 C CH3 O C CH3 NC CH3 Cl 4-(n-butyl)-α-chlorotoluene p-toluyl chloride p-cresyl acetate 4-dimethylaminobenzonitrile C8H7OCl C9H10O2 C9H10N2 C11H15Cl 103 CH3O COOH 107 O 111 CH3 99 H3C C N Br O OCH3 CH3 4-methyl-4-phenyl-2-pentanone p-anisic acid methyl p-toluate p-bromo-N,N-dimethylaniline C12H16O C8H8O3 C9H10O2 C8H10NBr 100 O 104 CH2O C CH3 108 CH3O CH2OH 112 O O Br C CH3O C CH3 C(CH3)3 p-bromoacetophenone benzyl acetate p-methoxybenzyl alcohol p-anisyl t-butyl ketone C8H7OBr C9H10O2 C8H10O2 C12H16O2 December 2007 8

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited 113 O 117 O 121 CH3CH2O C NH2 125 H O C CH3 O 126 N CH3 (H3C)3C H NO2 C CH3CH2O O o-nitrobenzaldehyde 4-t-butylphenyl acetate C7H5NO3 ethyl p-aminobenzoate p-ethoxyacetanilide C12H16O2 C9H11NO2 (phenacetin) C10H13NO2 114 (CH3)3C C OCH3 118 OCH3 122 CH3CH2O C NH2 H O O HO N C CH3 HC O O methyl 4-t-butylbenzoate 4-methoxybenzaldehyde p-ethoxybenzamide p-hydroxyacetanilide C12H16O2 C8H8O2 C9H11NO2 (paracetamol) C8H9NO2 115 CH3O NO2 119 C CH 123 O 127 O NH C CH3 C O2N CH3 O O p-nitroanisole 4-nitrophenylacetylene 4-methylacetanilide ethyl p-ethoxybenzoate C7H7NO3 C8H5NO2 C8H9NO C11H14O3 116 NO2 120 O 124 O 128 C HC O CH3 C NH2 CH3O O OCH3 O C OH H3C O p-nitrobenzaldehyde 4-acetoxybenzoic acid 4-aminoacetophenone methyl (p-methoxyphenyl)- C7H5NO3 C8H9NO propionionate C9H8O4 C11H14O3 December 2007 9

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited 129 H 133 O 137 O O OO 141 H N C C CH3 O C O O O N-isopropylbenzylamine hydroquinone dipropionate 1,3-dihydroxyphenyl cyclopropyl methyl ketone C12H14O4 dipropionate C5H8O C10H15N C12H14O4 130 OCH3 134 O O 138 142 H O CH3 CC CH3O C C OCH3 OH C O OO OO O methyl 2-methoxy-2- diethyl terephthalate dimethyl o-phthalate cyclopropane carboxylic acid phenylacetate C10H10O4 C4H6O2 C10H12O3 C12H14O4 135 139 O 143 H 131 136 O 140 C C NCO O O phenyl isocyanate CO cycloheptanone benzoylcylopropane C7H5NO O C7H12O C10H10O diethyl o-phthalate CH2 C12H14O4 132 OCH3 O O 144 H OCH3 C C C OCH2CH3 O H O O phenylacetaldehyde diethyl isophthalate cycloheptatriene ethyl cyclobutanecarboxylate dimethyl acetal C12H14O4 C7H8 C7H12O2 C10H14O2 December 2007 10

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited 145 O C(CH3)3 149 153 CH3 157 (CH3)3C 158 O C NEt2 OH O O N,N-diethyl-m-toluamide 4-t-butylcyclohexanone benzyl benzoate C12H17NO (CH3)3C C10H18O C14H12O2 154 Br 3,5-di-t-butylphenol OH C14H22O 146 O H 150 CH3 Br H3C N O CH3 O N-methylacetamide (p-cresyl)methyl phenyl 2-bromophenol Br C3H7NO ketone C6H5OBr 3,5-dibromocumene C15H14O2 C9H10Br2 147 H2N NH2 151 O CH3 155 O 159 Br O O C CH3 COOH COOH 1,4-diaminobutane p-cresyl phenylacetate acetylsalicylic acid 3-bromo-5-isopropylbenzoic C4H12N2 C15H14O2 (aspirin) acid C9H8O4 C10H11O2Br 148 H2N NH2 152 Cl3C CCl3 156 NH2 Br Br 160 O 1,5-diaminopentane 1,3-bis(trichloromethyl)- 2,6-dibromoaniline O C5H14N2 benzene C6H5NBr2 H C8H4Cl6 O piperonal C8H6O3 December 2007 11

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited 161 CH3 165 O 169 NO2 173 O CH3 3-nitro-o-xylene 2-cyclohexene-1-one indane α-tetralone C8H9NO2 C6H8O C9H10 C10H10O 170 162 Cl CH3 166 O 174 O Cl Cl OH β-tetralone C10H10O 2,4,5-trichlorotoluene 2-hydroxycyclohex- O C7H5Cl3 1-en-3-one H CH3 C6H8O2 3,3-dimethylindan-1-one C11H12O 9-methylfluorene 163 Cl NH2 167 O 175 C14H12 Cl Cl C CH3 171 O O 2,4,5-trichloroaniline 1-acetyl-1-cylohexene 1-indanone C6H4NCl3 C8H12O C9H8O fluorenone C13H8O 164 CH3O OCH3 168 CH3 172 O 176 I I CH3 O 2-indanone C9H8O CH3 4,6-diiodo-1,3- 4-methylpent-3-en-2-one dimethoxybenzene (mesityl oxide) C6H10O C8H8O2I2 December 2007 12

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited 177 CH3 181 CH3CH2 CH3 185 H H 189 Br 178 O OCH3 179 CH3 O C CH3 CH2Br 180 O C ONO H H CH3 H (Z)-1-methoxybut- 1,2-dibromopropane 2,4,6-trimethyl- 1-en-4-yne C3H6Br2 1,3,5-trioxane 4-ethyl-4-methyl-2,6- C5H6O piperidinedione C6H12O3 C8H13NO2 O 182 186 CH3 190 H OH CH3 C C C CH2CH3 191 CH3 CH3 CH3 COOH O CH3 CH3 OH CH3 N CH3H CH3 O 1,2,2,6,6-pentamethyl- 3-methyl-1-phenylpent- 2-hydroxy-3-methylbutyric 3,3-dimethylglutaric piperidine 1-yn-3-ol acid anhydride C10H21N C12H14O C7H10O3 C5H10O3 CH3 183 CH3 CH3 187 C C C C CH3 CH2 CH CH2 HO C C C C OH OH OH OH CH3 OOO CH3 CH3 2,2-dimethylglutaric 2,5-dimethyl-3-hexyne- 1-phenyl-1,3-pentadiyne glycerol anhydride 2,5-diol C11H8 C3H8O3 C7H10O3 C8H14O2 COOCH3 CH3 OH 184 CH3 H 188 192 OH OO C O CH3 CH3 C H H mevalonic lactone H C C HC NH2 CH C6H10O3 (Z)-3-methylpent-2- methyl 4-amino-3,5- 2-butanol en-4-ynal diethynylbenzoate C4H10O C6H6O C12H9NO2 December 2007 13

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited 193 O 197 O 201 O 205 198 Cl S 199 H NH2 S NH2 O O dibenzyl sulfoxide p-amino- vinyl 2-chloroethyl ether cinnamaldehyde C14H14OS benzenesulfonamide C4H7OCl C9H8O 194 S C6H8N2O2S 202 O 206 COOH N CH3 O O CH2OH S N-(p-tolyl)succinimide O C11H11NO2 (E)-3-(phenylthio)acrylic divinyl sulfone cinnamyl alcohol acid C4H6O2S C9H10O C9H8O2S 195 O S 203 O 207 H Cl S OCH2CH3 CH2 CH CH3 O CH3O H O C(CH3)3 H ethyl p-toluenesulfonate allyl p-anisyl thioether phenylacetaldeyde (E)-3-chloro-4,4-dimethyl-1- C9H12O3S ethylene glycol acetal phenyl-1-pentene C10H12OS C13H17Cl C10H12O2 196 O 200 O O 204 208 H S CH3 S CH2CH2O O CH(CH3)2 CH3 S H O 4O O Br CH3 CH3 p-tolyl methyl sulfoxide tetraethylene glycol (E)-1-phenyl-4-methyl-1- (Z)-β-bromostyrene C8H10OS ditosylate penten-3-one C8H7Br C22H30O9S2 C12H14O December 2007 14

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited 209 H 213 H 217 O 221 CH3O OCH3 CH3 OCH2CH3 Br NO2 Cl C Cl OCH3 OCH3 H CH3 OCH2CH3 CCl3 O (E)-p-nitro-β-bromostyrene 1,1-di-(p-chlorophenyl)-2,2,2- diethyl isopropylidene- malonaldehyde dimethyl C8H6BrNO2 trichloroethane (DDT) malonate acetal C14H9Cl5 C10H16O4 C7H16O4 210 O OH 214 Cl Cl 218 H 222 OCH2CH3 COOH O Cl CN OCH2CH3 Cl O 3-benzyloxy-1-propanol 2,4,5-trichlorophenoxy- 4-cyano-2,2- 2-chloroacetaldehyde C10H14O2 acetic acid (2,4,5-T) dimethylbutyraldehyde diethylacetal C8H5O3Cl3 C6H13O2Cl COOH C7H11NO COOH CH2 O CH2 211 215 O2N Br 219 CH3 H 223 HO C H O 224 H OCH3 CH2 O CH2 Br OCH3 O 1,3-dibenzylglycerol homophthallic acid methyl 2,3-dibromo-3- methyl (E)-3-methylacrylate C17H20O3 C9H8O4 (p-nitrophenyl)propionate C5H8O2 N C10H9NO4Br2 220 pyridine 212 CH3O O 216 CH3O CH3 C5H5N CH3O O 5,6-dimethoxy-2- CN 2,5-dimethyl-2,4-hexadiene coumaranone OCH3 C8H14 C10H10O4 2,3-di-(p-anisyl)butyronitrile C18H19NO2 December 2007 15

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited O 225 H3C N 229 O 233 CH3 C C 237 CH(CH3)2 O C O2N S O C HC O N CH(CH3)2 O 4-picoline isopropyl nicotinate citraconic anhydride 2-(5-nitrothienyl) isopropyl C6H7N ketone C9H11NO2 C5H4O3 C8H9NO3S 226 CH3 230 234 238 HN CH3 N CH3 N NH2 O COOH N 2-picoline 2-methyl-6-aminopyridine 2-furoic acid 4-methylimidazole C6H7N C6H8N2 C5H4O3 C4H6N2 227 CH3 231 N 235 O C(CH3)3 239 O H3C N S N 3-picoline 4-methylpyrimidine 2-furyl t-butyl ketone benzothiophene C6H7N C5H6N2 C9H12O2 C8H6S 228 O 232 H 236 O2N 240 S NO2 C O N CH3 2,4-dinitrothiophene H styrene epoxide C4H2N2O4S N C8H8O 2,3,4,9-tetrahydrocarbazole C12H13N 3-acetylpyridine C7H7NO December 2007 16

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited 241 245 249 O N CH3 253 OH HO N(CH3)2 CH3 O O α-angelicalactone octahydroanthracene N-methylmorpholine N,N-dimethyl-2,3-dihydroxy- C5H6O2 C5H11NO 1-propylamine C14H18 C5H13NO2 O 250 OH H O N 242 O CH3 246 254 CH3 H cyclopentanone oxime N O C5H9NO CH3 anthraquinone 251 OH OH C14H8O2 2-methyl- N pseudoephedrine tetrahydrofuran-3-one 247 C10H15NO C5H8O2 H 243 255 ON OO C(CH3)3 H butyrolactone dodecahydrotriphenylene cyclohexanone oxime t-butylformamide C4H6O2 C18H24 C6H11NO C5H11NO 244 O 248 252 O 256 N H CH3 CH3 HS CH2 CH N C CH3 H CH3 CH3 COOH O ε-caprolactam O C6H11NO tetramethyl-1,3- triphenylene N-acetylcysteine cyclobutanedione C18H12 C5H9NO3S C8H12O2 December 2007 17

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited 257 HO OH 261 O 265 OH CH3 269 O O CH CH2NH CH3 H 266 CH3 C H HO H HO CH3 OH OH N CH3 H O adrenalin 3-methylbutyraldehyde 2-methyl-2,4-pentanediol N-acetylglutamic acid C5H10O C6H14O2 C9H13NO3 C7H11NO5 258 CH2 CH COO- 262 OCH2CH3 OCH3 270 O 259 N NH3+ 263 CH OH H 260 H 264 CH2 CH OCH2CH3 OCH2CH3 tryptophan N CH3 HO C11H12N2O2 H H N CH3 O C acrolein diethyl acetal eugenol N-acetyltyrosine ethyl ester O C7H14O2 SO C10H12O2 C13H17NO4 N-acetylhomocysteine NH2 267 H Cl 271 thiolactone C C6H9NO2S C O C H HO C CH2CH2 CH COOH O NH2 C (CH3)3C allylamine E -1-chloro-4-(4-t- 2,5-dihydrofuran C3H7N butylphenyl)but-1-en-3-yne C4H6O C14H15Cl 272 268 O O HO H glutamic acid adamantine 2,3-dihydrofuran C5H9NO4 C10H16 OH C4H6O O N CH3 H O N-acetylaspartic acid C6H9NO5 December 2007 18

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited 273 COOH 277 Cl 281 O COOH O NC O CH2CH3 2,3-naphthalene- 2-chloronaphthalene ethyl 4-piperidone-N- dicarboxylic acid C10H7Cl carboxylate C8H13NO3 C12H8O4 278 274 OCH3 282 COOH CH3 NC HO NO2 sec-butylbenzene N-acetyl-2-amino-4-phenyl- C10H14 (E)-but-2-enoic acid 1-methoxy-4-nitro- C12H13NO3 naphthalene CH3 O C11H9NO3 279 N 283 CH3O O H 275 CH3 CH3 N-(1-methyl-1-phenylethyl)- CH3 butyramide OH C12H17NO OCH3 1,5-dimethylnaphthalene C12H12 3-hydroxy-3-methyl-5,8- dimethoxy-1-coumarinone 276 CH3 C13H16O4 CH3 280 O 1,3-dimethylnaphthalene OCH2CH3 C12H12 OCH2CH3 O diethyl 2-(1,1- dimethylheptyl)malonate C16H30O4 December 2007 19

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited Chapter 9.2 – The Analysis of MixturesProblem 284 Problem 286 Mole % Problem 284 Compound 24 benzene 59 Compound Mole % 17 ethanol 57 Mole % 41 ethyl acetate 59 bromoethane 43 dioxane Problem 285 Mole % Problem 287 Compound 15 benzene 46 Compound 39 ethanol diethyl ether bromoethane dichoromethane December 2007 20

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited Problem 288 Problem 290 Mole % Compound Mole % Compound 75 benzene 13 fluorene 25 diethyl ether 22 fluorenone Mole % 38 dichoromethane 65 62 Problem 289 Problem 291 Compound Compound Mole % benzene 23 4-nitroanisole 51 2-nitroanisole ethyl acetate 26 dioxane December 2007 21

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited Chapter 9.3 – Problems in 2D NMR Problem 294 isobutanol Problem 292 1-propanol Chemical Shift (δ) in ppm Proton Chemical Shift (δ) Carbon 64.0 in ppm 25.5 H1 3.49 C1 9.9 H2 1.50 C2 H3 0.85 C3 H4 2.95 Problem 293 1-iodobutane December 2007 22

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited Problem 295 1 2 34 5 6 7 Problem 297 432 1 3-heptanone 1-bromobutane CH3 CH2 C CH2 CH2 CH2 CH3 CH3 CH2 CH2 CH2 Br O Proton Chemical Shift (δ) in ppm Proton Chemical Shift (δ) Carbon Chemical Shift (δ) H1 0.91 in ppm in ppm H2 1.94 H1 3.39 C1 33.4 H2 C2 H4 1.97 H3 1.82 C3 34.7 H5 1.44 H4 C4 H6 1.14 1.45 21.4 H7 0.79 0.91 13.2 Problem 298 1 23 4 56 78 3-octanone CH3 CH2 C CH2 CH2 CH2 CH2 CH3 O 3 Proton Problem 296 42 H1 Chemical Shift Carbon Chemical Shift δ-valerolactone H2 1 (δ) in ppm (δ) in ppm 5 H4 H5 0.92 C1 7.8 OO H6 H7 Proton Chemical Shift Carbon Chemical Shift H8 1.92 C2 35.4 (δ) in ppm (δ) in ppm H2 C1 170.0 C3 209.0 H3 2.08 C2 H4 1.16 C3 29.9 1.94 C4 42.1 H5 1.08 C4 3.71 C5 22.2 1.47 C5 23.7 19.0 1.11 C6 31.7 68.8 1.19 C7 22.7 0.82 C8 14.0 December 2007 23

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited Problem 299 c ba Problem 300 ab cdef diethyl diethylmalonate butyl ethyl ether COOCH2CH3 CH3 CH2 O CH2 CH2 CH2 CH3 de f gh CH3CH2 C CH2CH3 COOCH2CH3 Proton Chemical Carbon Chemical Shift Shift (δ) (δ) i jk Ha in ppm Ca Hb Cb in ppm Proton Chemical Shift Carbon Chemical Shift Hc 1.11 Cc 15.0 (δ) (δ) Hd Cd Ha Ca He 3.29 Ce 66.0 Hb in ppm Cb in ppm Hf Cf 1.19 Cc 14.0 3.27 70.1 Cd 60.8 4.13 Ce 171.9 1.52 32.1 Cf 8.1 Cg 24.5 1.36 19.4 Ch 58.0 Ci 24.5 0.87 13.5 Cj 8.1 Hd 0.76 Ck 171.9 He 1.88 60.8 14.0 Hg 1.88 Hh 0.76 Hj 4.13 Hk 1.19 December 2007 24

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited Problem 301 Problem 302 432 1 butyl butyrate 1-iodobutane 1-butanol CH3 CH2 CH2 CH2 I Proton Chemical Carbon Chemical Shift (δ) Shift (δ) 432 1 Ha in ppm Ca in ppm Hb Cb CH3 CH2 CH2 CH2 OH Hc 0.75 Cc 13.9 Hd Cd 1-iodobutane 1H Chemical 1-butanol 1H Chemical 1.19 Ce 19.5 Shift (δ) Shift (δ) Cf H1 in ppm H1 in ppm 1.40 Cg 31.2 H2 2.70 H2 3.41 Ch H3 H3 3.97 64.0 H4 1.40 H4 1.27 -OH Hf 2.08 172.8 1.08 1.39 Hg 1.52 Hh 0.79 36.2 0.64 0.84 19.0 1.95 13.9 December 2007 25

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited Problem 303 Problem 304 (E)- and (Z)-2-butene CH3 H (Z)-3-methyl-2-penten-4-ynol C C C CH2OH C H H Br Problem 305 H8 NO2 C C H7 H2 1-nitronaphthalene CH3 CH3 H6 H3 Proton H5 H4 H CH3 H2 C C H3 Chemical Shift (δ) in ppm H4 8.22 CH3 Br H5 7.53 H6 8.10 H7 7.95 H8 7.62 7.71 8.56 December 2007 26

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited Problem 306 COOCH2CH3 Problem 309 CH3 CH3 ethyl diethylmalonate CH3CH2 C H geraniol H COOCH2CH3 CH3 HOCH2 H Problem 307 butyl CH3 CH2 CH2 CH2 O C CH2 CH2 CH2 CH3 valerate O Problem 308 CH3 CH3 nerol H December 2007 CH3 H CH2OH 27

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited Chapter 9.4 – Analysis of NMR Spectra Problem 310 Problem 311 Structure Number of 1H Number of 13C Chemical Shifts δA = 300 Hz / 60 MHz = 5.0 ppm environments environments Problem 312 δM = 240 Hz / 60 MHz = 4.0 ppm CH3 CO CH2CH2CH3 δX = 120 Hz / 60 MHz = 2.0 ppm CH3CH2 CO CH2CH3 4 5 2 3 CH2 CHCH2CH3 5 4 cis- CH3CH CHCH3 2 2 trans-CH3CH CHCH3 2 2 1 1 Cl Br 3 4 Br Cl Cl 2 3 Br Br 3 4 1 2 Br Cl 2 4 Cl OCH3 5 7 slow chair- 2 1 Chemical Shifts δA = 180 Hz / 200 MHz = 0.90 ppm chair 1 1 δM = 220 Hz / 200 MHz = 1.22 ppm 7 4 δX = 300 Hz / 200 MHz = 1.50 ppm fast chair- chair H rigid Cl December 2007 28

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited Problem 313 Problem 314 Spin System A2X3 Chemical Shifts δA = 150 Hz / 400 MHz = 0.375 ppm δX = 300 Hz / 400 MHz = 0.750 ppm Chemical Shifts δA = 3.36 ppm = 3.36 x 60 = 202 Hz from TMS δX = 1.11 ppm = 1.11 x 60 = 67 Hz from TMS 1st Order Analysis ΔνAX = νA - νX = 202 - 67 = 135 Hz ΔνAX / JAX = 135 / 7 = 19.3 This ratio is much greater than 3 so a 1st order analysis is justified. December 2007 29

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited Problem 315 Spin System AMX Problem 316 Spin System AMX Chemical Shifts δA = 501 Hz / 100 MHz = 5.01 ppm δM = 439 Hz / 100 MHz = 4.39 ppm δX = 408 Hz / 100 MHz = 4.08 ppm Chemical Shifts δA = 460 Hz / 60 MHz = 7.67 ppm δX = 442 Hz / 60 MHz = 7.37 ppm Coupling constants JAM = 3.1 Hz δM = 394 Hz / 60 MHz = 6.57ppm JAX = 20.1 Hz JMX = 1.1 Hz Coupling constants JAM = 1.70 Hz JAX = 0.85 Hz 1st Order Analysis ΔνΑΜ = νA - νM = 501 - 439 = 62 Hz JMX = 3.65 Hz ΔνΑΞ = νA - νX = 501 - 408 = 93 Hz ΔνΜΞ = νM - νX = 439 - 408 = 31Hz 1st Order Analysis ΔνΑΜ = νA - νM = 460 - 394 = 66 Hz ΔνΑΜ / JAM = 62 / 3.1 = 20.0 ΔνΑΞ = νA - νX = 460 - 442 = 18 Hz ΔνΑΞ / JAX = 93 / 20.1 = 4.6 ΔνΜΞ = νM - νX = 442 - 394 = 48 Hz ΔνΜΞ / JMX = 31 / 2.1 = 14.7 ΔνΑΜ / JAM = 66 / 1.7 = 38.8 ΔνΑΞ / JAX = 18 / 0.85 = 21.2 All ratios are greater than 3 so a 1st order analysis is justified. ΔνΜΞ / JMX = 48 / 3.65 = 13.2 All ratios are greater than 3 so a 1st order analysis is justified. December 2007 30

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited Problem 317 Spin System AMX Problem 318 Spin System AMX Chemical Shifts δ3 = 673 Hz / 100 MHz = 6.73 ppm Chemical Shifts δA = 628 Hz / 100 MHz = 6.28 ppm Coupling constants δ4 = 719 Hz / 100 MHz = 7.19 ppm δB = 527 Hz / 100 MHz = 5.27 ppm δ6 = 777 Hz / 100 MHz = 7.77ppm Coupling constants δC = 592 Hz / 100 MHz = 5.92 ppm 1st Order Analysis 3J34 = 8.8 Hz JAB = 2.1 Hz; JAC = 17.5 Hz; JBC = 9.9 Hz 4J46 = 2.3 Hz 5J36 not resolved (< 1Hz) ΔνAB = νA - νB = 628 - 527 = 101 Hz ΔνAC = νA - νC = 628 - 592 = 36 Hz 1st Order Analysis Δν34 = ν4 - ν3 = 719 - 673 = 46 Hz ΔνBC = νC - νB = 592 - 527 = 65 Hz Δν46 = ν6 - ν4 = 777 - 719 = 58 Hz ΔνAB / JAB = 101 / 2.1 = 48.1 Δν36 = ν6 - ν3 = 777 - 673 = 104 Hz ΔνAC / JAC = 36 / 17.5 = 2.1 Δν34 / J34 = 46 / 8.8 = 5.2 ΔνBC / JBC = 65 / 9.9 = 6.6 Δν46 / J46 = 58 / 2.3 = 25.2 Δν36 / J36 = 104 / <1 = >104 All ratios are greater than 3 so a 1st order analysis is justified. 2 out of 3 ratios are greater than 3 so this is borderline 1st order. The main deviation from 1st order is that intensities are severely distorted - a 1st order spectrum would have all lines of equal intensity. JAC = 17.5 Hz indicates that HA and HC must be trans. JBC = 9.9 Hz indicates HA and HC are cis. December 2007 31

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited Problem 319 Spin System AX3 Problem 320 Spin System AX3 Chemical Shifts δA = 160 Hz / 60 MHz = 2.67 ppm δX = 280 Hz / 60 MHz = 4.67 ppm Chemical Shifts δA = 199 Hz / 100 MHz = 1.99 ppm δX = 99 Hz / 100 MHz = 0.99 ppm Coupling constants JAX = 5 Hz 1st Order Analysis ΔνAX = νA - νX = 199 - 99 = 100 Hz ΔνAX / JAX = 100 / 5 = 20.0 ΔνAX / JAX is much greater than 3 so a 1st order analysis is justified. December 2007 32

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited Problem 321 4 Spin System AMX2 Problem 322 4 Spin System AM2X Chemical Shifts δA = 340 Hz / 60 MHz = 5.67 ppm Chemical Shifts δA = 110 Hz / 60 MHz = 1.83ppm δM = 240 Hz / 60 MHz = 4.00 ppm δM = 200 Hz / 60 MHz = 3.33 ppm δX = 100 Hz / 60 MHz = 1.67 ppm δX = 290 Hz / 60 MHz = 4.83 ppm December 2007 33

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited Problem 323 4 Spin System AM2X Problem 324 4 Spin System A2MX Chemical Shifts δA = 646 Hz / 100 MHz = 6.46 ppm δM = 510 Hz / 100 MHz = 5.10 ppm δX = 395 Hz / 100 MHz = 3.95 ppm Chemical Shifts δA = 279 Hz / 100 MHz = 2.79 ppm δM = 149 Hz / 100 MHz = 1.49 ppm Coupling constants JAM = 3 Hz; JAX = 16 Hz; JMX = 5 Hz; δX = 39 Hz / 100 MHz = 0.39 ppm 1st Order Analysis ΔνAX = νA - νX = 646 - 395 = 251 Hz Coupling constants JAM = 4.5 Hz; JAX = 7.5 Hz; JMX = 11.0 Hz; ΔνAM = νA - νM = 646 - 510 = 136 Hz 1st Order Analysis ΔνMX = νM - νX = 510 - 395 = 115 Hz ΔνAX = νA - νX = 279 - 39 = 240 Hz ΔνAM = νA - νM = 279 - 149 = 130 Hz ΔνAX / JAX = 251 / 16 = 15.7 ΔνMX = νM - νX = 149 - 39 = 110 Hz ΔνAM / JAM = 136 / 3 = 45.3 ΔνMX / JMX = 115 / 5 = 23.0 ΔνAX / JAX = 240 / 7.5 = 32.0 ΔνAM / JAM = 130 / 4.5 = 28.9 All ratios are significantly greater than 3 so a 1st order analysis is justified. ΔνMX / JMX = 110 / 11 = 10.0 All ratios are significantly greater than 3 so a 1st order analysis is justified. December 2007 34

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited Problem 325 4 Spin System AMX2 Problem 326 5 Spin System A2M2X Chemical Shifts δA = 302 Hz / 100 MHz = 3.02 ppm δM = 160 Hz / 100 MHz = 1.60 ppm δX = 37 Hz / 100 MHz = 0.37 ppm Chemical Shifts δA = 1000 Hz / 200 MHz = 5.0 ppm δM = 500 Hz / 200 MHz = 2.5 ppm Coupling constants JAM = 12.0 Hz; JAX = 5.0 Hz; JMX = 8.0 Hz; δX = 100 Hz / 200 MHz = 0.5 ppm 1st Order Analysis ΔνAX = νA - νX = 302 - 37 = 265 Hz Coupling constants JAM = 3.0 Hz; JAX = 7.0 Hz; JMX = 10.0 Hz; ΔνAM = νA - νM = 302 - 160 = 142 Hz 1st Order Analysis ΔνMX = νM - νX = 160 - 37 = 123 Hz ΔνAX = νA - νX = 1000 - 100 = 900 Hz ΔνAM = νA - νM = 1000 - 500 = 500 Hz ΔνAX / JAX = 265 / 5.0 = 53.0 ΔνMX = νM - νX = 500 - 100 = 400 Hz ΔνAM / JAM = 142 / 12.0 = 11.8 ΔνMX / JMX = 123 / 8.0 = 15.4 ΔνAX / JAX = 900 / 7.0 = 128.6 ΔνAM / JAM = 500 / 3.0 = 166.7 All ratios are significantly greater than 3 so a 1st order analysis is justified. ΔνMX / JMX = 400 / 10.0 = 40.0 All ratios are significantly greater than 3 so a 1st order analysis is justified. December 2007 35

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited Problem 327 5 Spin System AMX3 Chemical Shifts δA = 710 Hz / 100 MHz = 7.10 ppm δM = 585 Hz / 100 MHz = 5.85 ppm δX = 192 Hz / 100 MHz = 1.92 ppm Coupling constants JAM = 15.3 Hz; JAX = 6.9 Hz; JMX = 1.6 Hz; 1st Order Analysis ΔνAX = νA - νX = 710 - 192 = 518 Hz ΔνAM = νA - νM = 710 - 585 = 125 Hz ΔνMX = νM - νX = 585 - 192 = 393 Hz ΔνAX / JAX = 518 / 6.9 = 84.7 ΔνAM / JAM = 125 / 15.3 = 8.2 ΔνMX / JMX = 393 / 1.6 = 245.6 All ratios are significantly greater than 3 so a 1st order analysis is justified. JAM = 15.3 Hz is typical of a coupling between vinylic protons which are trans to each other (see Section 5.7) December 2007 36

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited Problem 328 5 Spin System ADMX3 1st Order Analysis ΔνAD = νA - νD = 956 - 695 = 261 Hz ΔνAM = νA - νM = 956 - 619 = 337 Hz ΔνAX = νA - νX = 956 - 205 = 751 Hz ΔνDM = νD - νM = 695 - 619 = 76 Hz ΔνDX = νD - νX = 695 - 205 = 490 Hz ΔνMX = νM- νX = 619 - 205 = 414 Hz ΔνAD / JAD = 261 / <1 = >261 ΔνAM / JAM = 337 / 8.2 = 41.1 ΔνAX / JAX = 751 / <1 = >751 ΔνDM / JDM = 76 / 15.8 = 4.8 ΔνDX / JDX = 490 / 6.9 = 71.0 ΔνMX / JMX = 414 / 1.6 = 258.8 All ratios are significantly greater than 3 so a 1st order analysis is justified. The critical coupling constant is JDM = 15.8 Hz which is typical of a coupling between vinylic protons which are trans to each other (see Section 5.7). The compound is: Chemical Shifts δA = 956 Hz / 100 MHz = 9.56 ppm; O D δD = 695 Hz / 100 MHz = 6.95 ppm; H δM = 619 Hz / 100 MHz = 6.19 ppm; AC δX = 205 Hz / 100 MHz = 2.05 ppm; H C C H CH3 M X Coupling constants JAD= < 1 Hz; JAM = 8.2 Hz; JAX = < 1 Hz; JDM = 15.8 Hz; JDX = 6.9 Hz; JMX = 1.6Hz; December 2007 37

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited Problem 329 5 Spin System AMX3 Problem 330 3 Spin System A2X Chemical Shifts δA = 80 Hz / 60 MHz = 1.33 ppm δM = 220 Hz / 60 MHz = 3.67 ppm δX = 320 Hz / 60 MHz = 5.33 ppm Of the 6 isomeric anilines, only compounds 4 and 6 have the correct symmetry to give a spectrum with only two chemical shifts in the aromatic region, in the ratio 2:1. Both 4 and 6 would give A2X spin NH2 systems. The measured coupling Br Br constant is 7.7 Hz which is in the range for protons which are ortho to HA HA each other. Compound 4 is the HX correct answer. December 2007 38

Please Keep Absolutely ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION Copyright: Copying or duplicating Confidential L D Field, S Sternhell and J R Kalman these solutions in any form is strictly prohibited Problem 331 Problem 332 All of the protons in the 1H spectrum 1,5-dichoronaphthalene have protons The spectrum is obtained after D2O exchange so the carboxylic acid and which are ortho to them. This means that every proton must have at least phenolic protons will not be present and the spectrum only contains the one large (>7 Hz) ortho coupling. The spectrum has one proton (at δ 7.1) aromatic and vinylic protons. which has only a small coupling so this cannot be the spectrum of 1,5-dichloronaphthalene. The spectrum shows 6 distinct resonances therefore compounds 5 and 6 can be eliminated because they would each have only 4 resonances (on The spectrum is an AMX spectrum with couplings between A and X of symmetry grounds). about 8.3 Hz (typical of an ortho coupling) and coupling between M and X of about 2.7 Hz (typical of a meta coupling). Two possible structure are The proton at about δ 7.1 shows no large coupling (> 7 Hz), this means given below. that it has no protons ortho to it. This eliminates compounds 1 and 2 since all protons in these compounds will have at least one large ortho coupling. Compounds 3 and 4 differ by the stereochemistry at the double bond. The proton at δ 6.4 is clearly one of the vinylic protons and it is coupled to the other vinylic proton at δ 7.6. The coupling constant is 16 Hz and this characteristic of vinylic protons which are trans to each other. The correct answer is compound 3. OH COOH HM HM HA HM Cl Cl HX Cl HX HX Cl HX HA HA HM HA 2,7-dichloronaphthalene 2,6-dichloronaphthalene December 2007 39