Solutions Manual: Organic Structures From Spectra - 4Th Edition

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Please Keep Absolutely these solutions in any form is

Confidential ORGANIC STRUCTURES FROM SPECTRA 4th EDITION strictly prohibited
L D Field, S Sternhell and J R Kalman
Solutions Manual
December 2007 1
1 5 BrCH2 CH2Br 9 OH OH 13 Cl2CH CH3

O CH3 C C CH3
CH3 CH3
2-butanone 1,2-dibromoethane pinacol 1,1-dichloroethane
C4H8O C2H4Br2 C6H14O2 C2H4Cl2
2 CH3CH2 OH 6 O 10 O O
14 CH3 CH3
CH3
O CH3 H OH
O
propionic acid 1,2-butanedione 1,4-cyclohexanedione 2-propanol

(biacetyl)
C3H6O2 C4H6O2 C6H8O2 C3H8O
3 O 7 CH2C N 11 O 15 CH3 CH3

CH2CH3
CH3 O CH2C N H Br
ethyl acetate succinonitrile cyclopentanone 2-bromopropane
C4H8O2 C4H4N2 C5H8O2 C3H7Br
4 CH3O CH2CH3 8 CH3 CH3 12 CH3CH2 I 16 Cl

Cl
O CH3 C C CH3
CH3 CH3
methyl propionate 2,2,3,3-tetramethylbutane iodoethane 1,4-dichlorobutane
C4H8O2 C8H18 C2H5I C4H8Cl2
December 2007 2
17 Br Br 21 H2N COOH 25 29
CH2C N CH2 C CH3
O
1,3-dibromopropane 4-aminobutyric acid benzyl cyanide benzyl methyl ketone
C3H6Br2 C4H9NO2 C8H7N C9H10O
18 Br Cl 22 26 30 O
OCH3 CH2NH2
1-bromo-3-chloropropane anisole benzylamine propiophenone
C3H6BrCl C7H8O C7H9N C9H10O
19 Br C N 23 27 OH 31 CH3
CH2OH
CH C H
O
4-bromobutyronitrile benzyl alcohol 2-phenylethanol 2-phenylpropionaldehyde
C4H6NBr C7H8O C8H10O C9H10O

28
20 + 24 OH 32 O
NH3 CH2Br
H
-
CH3 COO CH3
H
alanine benzyl bromide 1-phenylethanol butyrophenone
C3H7NO2 C7H7Br C8H10O C10H12O
December 2007 3
O O
33 O O 37 N 41 C C 45 CH3 O O CH3
O
O CH3 H O H CH3 O
t-butyl acetoacetate dibenzylamine propionic anhydride 1,1-diacetoxyethane
C8H14O3 C14H15N C6H10O3 C6H10O4
34 CH3CH2 O C H 38 CH3 42 O 46 CH3OOC COOCH3

O N CH3 O C H CH3
CH3 N C O
CH3 O
ethyl formate N,N,N,N-tetramethyl-1,2- diethyl oxalate dimethyl methylmalonate

ethanediamine
C3H6O2 C6H16N2 C6H10O4 C6H10O4
35 O 39 O 43 O 47 O CH3
CH3 O OCH3
O CH3 CH3 O C
O O O O
benzil 2,5-hexanedione ethylene glycol diacetate methyl acetyllactate
C14H10O2 C6H10O2 C6H10O4 C6H10O4
36 40 O 44 O 48 O
CH3O O C
CH3CH2O OCH2CH3 OCH3 C O
O
O
1,2-diphenylethane diethyl carbonate dimethyl succinate diethyl succinate
C14H14 C5H10O3 C6H10O4 C8H14O4
December 2007 4
O H3C CH3
49 O
O 53 57 OCH3 61
CHCl2
H3C CH3
O OCH3
OCH3
ethylene glycol dipropionate ,-dichlorotoluene 1,2,3-trimethoxybenzene durene
C8H14O4 C7H6Cl2 C9H12O3 C10H14

CH3 CH3 CH3
50 O O 54 OCH3 58 62
CH3 CH3 CH3
C C C H
O
OCH3 CH3
butyric anhydride benzaldehyde dimethylacetal mesitylene 1,2,3,4-tetramethylbenzene
C8H14O3 C9H12O2 C9H12 C10H14
51 55 OH 59 CH3 63 CH3
Br Br
COOH CH3 CH3 CH3
CH3 CH3
1,4-dibromobenzene benzilic acid 1,2,3-trimethylbenzene 1,2,3,5-tetramethylbenzene
C6H4Br2 C14H12O3 C9H12 C10H14
52 56 OH 60 CH3 64 CH3 CH3

Br Br
OH CH3 CH3 CH3 CH3
CH3 CH3
4,4'-dibromobiphenyl catechol 1,2,4-trimethylbenzene hexamethylbenzene
C12H8Br2 C6H6O2 C9H12 C12H18
December 2007 5
65 CH3 CH3 69 OH 73 OH 77 HOOC COOH

CH3 CH3 CH3 CH3
CH3 CH3
CH3 CH3
O CH3
H CH3
1,2,3,4,5,- 3-hydroxybutanone 2-methyl-2-butanol 3,3-dimethylglutaric acid

pentamethylcyclopentadiene (acetoin) (t-amyl alcohol)
C10H16 C4H8O2 C5H12O C7H12O4
66 CH3 NH2 70 HO 74 NH2 78 HOOC COOH
O O
acetamide 4-hydroxy-4-methyl-2- hexylamine 2,2-dimethylpentanedioc

pentanone acid
C2H5NO C6H12O2 C6H15N C7H12O4
67 O 71 75 O 79 CH3 CH3
O CH3 CH3CH2
HO CH3
O O N N
O CH3 CH3
Br
O
ethyl glycolate isobutyl acetate ethyl 2-bromopropionate tetramethylurea
C4H8O3 C6H12O2 C5H9O2Br C5H12N2O
68 O 72 COOH 76 OCH3 80 O O
C N
CH3CH2O O OCH3
ethyl cyanoacetate 3,3-dimethylbutyric acid 4,4-dimethoxy-2-butanone 1,3-dioxan
C5H7NO2 C6H12O2 C6H12O3 C4H8O2
December 2007 6
81 O 85 Br 89 93 O
CH2
OH HO
O H
O
1,4-dioxan 2-bromohexanoic acid 2-methylbut-3-en-2-ol dibutyl ether
C4H8O2 C6H11O2Br C5H10O C8H18O
+
82 O O 86 CN 90 H NH3 94
CH3 -
CN C O
O O
H OH O
O O
18-crown-6 2-ethylmalononitrile threonine butylbenzene
C12H24O6 C5H6N2 C4H9NO3 C10H14
83 H2C C
CH2Cl 87 91 Br
95
CN C(CH3)3
Cl
2,3-dichloropropene 3-methylbutyronitrile 1-bromo-3-phenylpropane t-butylbenzene
C3H4Cl2 C5H9N C9H11Br C10H14
84 O 88 H2N C C H 92 NO2 96
Cl
O CH3
4-chlorobutyl acetate 5-amino-1-pentyne 1-nitropropane sec-butylbenzene
C6H11O2Cl C5H9N C3H7NO2 C10H14
December 2007 7
97 101 O 105 O 109

HO CH2OCH3
C(CH3)3 Cl C CH3O C
CH3 CH3
neopentylbenzene p-chloroacetophenone 4-methoxyacetophenone 4-methoxymethylphenol
C11H16 C8H7OCl C9H10O2 C8H10O2
98 102 O 106 O 110 CH3

CH2Cl
CH3 C CH3 O C CH3 N C N
Cl CH3
4-(n-butyl)--chlorotoluene p-toluyl chloride p-cresyl acetate 4-dimethylaminobenzonitrile
C11H15Cl C8H7OCl C9H10O2 C9H10N2
99 103 107 O 111 CH3

O CH3O COOH
H3C C Br N
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 104 108 112 O

CH2O C CH3 CH3O CH2OH
Br C CH3O C
CH3 O C(CH3)3
p-bromoacetophenone benzyl acetate p-methoxybenzyl alcohol p-anisyl t-butyl ketone
C8H7OBr C9H10O2 C8H10O2 C12H16O2
December 2007 8
113 O 117 O 121 125 H

CH3CH2O C NH2
N CH3
(H3C)3C O C CH3 H O C
CH3CH2O O
NO2
4-t-butylphenyl acetate o-nitrobenzaldehyde ethyl p-aminobenzoate p-ethoxyacetanilide

(phenacetin)
C12H16O2 C7H5NO3 C9H11NO2 C10H13NO2
H
114 118 122 126
(CH3)3C C OCH3 H C OCH3 CH3CH2O C NH2 HO N C CH3
O O O O
methyl 4-t-butylbenzoate 4-methoxybenzaldehyde p-ethoxybenzamide p-hydroxyacetanilide

(paracetamol)
C12H16O2 C8H8O2 C9H11NO2 C8H9NO2
115 119 123 O 127 O

CH3O NO2 O 2N C C H
CH3 NH C CH3 C
O
p-nitroanisole 4-nitrophenylacetylene 4-methylacetanilide ethyl p-ethoxybenzoate
C7H7NO3 C8H5NO2 C8H9NO C11H14O3
116 120 O 124 O 128

H C NO2
O C
O OH CH3 C NH2 CH3O O OCH3
C
H3C O
p-nitrobenzaldehyde 4-acetoxybenzoic acid 4-aminoacetophenone methyl (p-methoxyphenyl)-

propionionate
C7H5NO3 C9H8O4 C8H9NO C11H14O3
December 2007 9
129 H 133 O 137 O O O O 141 H

N O C C CH3
O C
O
O
N-isopropylbenzylamine hydroquinone dipropionate 1,3-dihydroxyphenyl cyclopropyl methyl ketone

dipropionate
C10H15N C12H14O4 C12H14O4 C5H8O
130 OCH3 134 O O 138 142 H

O C C CH3O OCH3 OH
CH3 C C C
O O
O O O
O
methyl 2-methoxy-2- diethyl terephthalate dimethyl o-phthalate cyclopropane carboxylic acid

phenylacetate
C10H12O3 C12H14O4 C10H10O4 C4H6O2
O
131 135 139 143 H
NCO C O
O
C
O
C O
O
phenyl isocyanate diethyl o-phthalate cycloheptanone benzoylcylopropane
C7H5NO C12H14O4 C7H12O C10H10O
132 OCH3 136 O O 140 144 H

OCH3 CH2 OCH2CH3
C C
O O C
H
O
phenylacetaldehyde diethyl isophthalate cycloheptatriene ethyl cyclobutanecarboxylate

dimethyl acetal
C10H14O2 C12H14O4 C7H8 C7H12O2
December 2007 10
145 O C(CH3)3
149 153 CH3 157 (CH3)3C
O
OH
O NEt2
C
(CH3)3C
O
4-t-butylcyclohexanone benzyl benzoate N,N-diethyl-m-toluamide 3,5-di-t-butylphenol
C10H18O C14H12O2 C12H17NO C14H22O
146 O
H 150 CH3 154 Br 158 Br
N
H3C O OH
CH3
O
Br
N-methylacetamide (p-cresyl)methyl phenyl 2-bromophenol 3,5-dibromocumene

ketone
C3H7NO C15H14O2 C6H5OBr C9H10Br2
147 H2N 151 O

CH3 155 O 159 Br
NH2
O C CH3
O
COOH
COOH
1,4-diaminobutane p-cresyl phenylacetate acetylsalicylic acid 3-bromo-5-isopropylbenzoic

(aspirin) acid
C4H12N2 C15H14O2 C9H8O4 C10H11O2Br
148 H2N NH2 152 Cl3C CCl3 156 NH2 160 O

Br Br O
H
1,5-diaminopentane 1,3-bis(trichloromethyl)- 2,6-dibromoaniline piperonal

benzene
C5H14N2 C8H4Cl6 C6H5NBr2 C8H6O3
December 2007 11
161 CH3 165 O

169 173 O
CH3 NO2
3-nitro-o-xylene 2-cyclohexene-1-one indane -tetralone
C8H9NO2 C6H8O C9H10 C10H10O
162 Cl CH3 166 O

170 174 O
Cl Cl OH
O
2,4,5-trichlorotoluene 2-hydroxycyclohex- 3,3-dimethylindan-1-one -tetralone

1-en-3-one
C7H5Cl3 C6H8O2 C11H12O C10H10O
163 Cl NH2 167 O 171 O 175

C CH3
Cl Cl
H CH3
2,4,5-trichloroaniline 1-acetyl-1-cylohexene 1-indanone 9-methylfluorene
C6H4NCl3 C8H12O C9H8O C14H12
164 CH3O OCH3 168 CH3 172 176

O
I I CH3 O
CH3 O
4,6-diiodo-1,3- 4-methylpent-3-en-2-one 2-indanone fluorenone

dimethoxybenzene (mesityl oxide)
C8H8O2I2 C6H10O C9H8O C13H8O
December 2007 12
177 CH3 181 CH3CH2 CH3 185 H H 189 Br

O
CH3 O C OCH3 CH3 CH2Br
O O N O C H
CH3 H
H
2,4,6-trimethyl- 4-ethyl-4-methyl-2,6- (Z)-1-methoxybut- 1,2-dibromopropane
1,3,5-trioxane piperidinedione 1-en-4-yne
C6H12O3 C8H13NO2 C5H6O C3H6Br2
178 O 182 186 CH3 190 H OH

CH3 CH3 CH3 C C C CH2CH3 CH3
O COOH
CH3 CH3 N CH3 H
OH CH3
O CH3
3,3-dimethylglutaric 1,2,2,6,6-pentamethyl- 3-methyl-1-phenylpent- 2-hydroxy-3-methylbutyric

anhydride piperidine 1-yn-3-ol acid
C7H10O3 C10H21N C12H14O C5H10O3
179 CH3 183 CH3 CH3 187 191 CH2 CH CH2

C C C C CH3
CH3 HO C C C C OH OH OH OH
O O O CH3 CH3
2,2-dimethylglutaric 2,5-dimethyl-3-hexyne- 1-phenyl-1,3-pentadiyne glycerol

anhydride 2,5-diol
C7H10O3 C8H14O2 C11H8 C3H8O3
COOCH3
180 CH3 OH 184 CH3 H 188 192 OH
C
CH3
O CH3
C H C C H
O O H HC NH2 CH
mevalonic lactone (Z)-3-methylpent-2- methyl 4-amino-3,5- 2-butanol

en-4-ynal diethynylbenzoate
C6H10O3 C6H6O C12H9NO2 C4H10O
December 2007 13
193 O 197 O 201 O

Cl
205 H
S NH2 S NH2
O
O
dibenzyl sulfoxide p-amino- vinyl 2-chloroethyl ether cinnamaldehyde

benzenesulfonamide
C14H14OS C6H8N2O2S C4H7OCl C9H8O
198
194 O 202 O 206
S S
N CH3 CH2OH
COOH O
(E)-3-(phenylthio)acrylic divinyl sulfone N-(p-tolyl)succinimide cinnamyl alcohol

acid
C9H8O2S C4H6O2S C11H11NO2 C9H10O
195 O 199 S 203 O 207 H Cl

CH3 S OCH2CH3 CH2 CH H
CH3O C(CH3)3
O O
H
ethyl p-toluenesulfonate allyl p-anisyl thioether phenylacetaldeyde (E)-3-chloro-4,4-dimethyl-1-

ethylene glycol acetal phenyl-1-pentene
C9H12O3S C10H12OS C10H12O2 C13H17Cl
O O
S CH2CH2O O
196 O 200 O 204 CH(CH3)2
208 H
S
4 H
CH3 S CH3 O
O Br
CH3
CH3
p-tolyl methyl sulfoxide tetraethylene glycol (E)-1-phenyl-4-methyl-1- (Z)--bromostyrene

ditosylate penten-3-one
C8H10OS C22H30O9S2 C12H14O C8H7Br
December 2007 14
209 H 213 H 217 O 221 CH3O OCH3

NO2 CH3 OCH2CH3
Br Cl C Cl OCH3 OCH3
H CCl3 CH3 OCH2CH3
O
(E)-p-nitro--bromostyrene 1,1-di-(p-chlorophenyl)-2,2,2- diethyl isopropylidene- malonaldehyde dimethyl

trichloroethane (DDT) malonate acetal
C8H6BrNO2 C14H9Cl5 C10H16O4 C7H16O4
210 O OH 214 Cl Cl
COOH
218 H
222 OCH2CH3
CN Cl
OCH2CH3
Cl O O
3-benzyloxy-1-propanol 2,4,5-trichlorophenoxy- 4-cyano-2,2- 2-chloroacetaldehyde

acetic acid (2,4,5-T) dimethylbutyraldehyde diethylacetal
C10H14O2 C8H5O3Cl3 C7H11NO C6H13O2Cl
211 COOH 215 O2N

Br
219 CH3 H 223 CH2 O CH2
COOH O H OCH3 HO C H
Br OCH3 O CH2 O CH2
homophthallic acid methyl 2,3-dibromo-3- methyl (E)-3-methylacrylate 1,3-dibenzylglycerol

(p-nitrophenyl)propionate
C9H8O4 C10H9NO4Br2 C5H8O2 C17H20O3
212 O 216 CH3O 220 224

CH3O CH3
O N
CH3O CN
OCH3
5,6-dimethoxy-2- 2,3-di-(p-anisyl)butyronitrile 2,5-dimethyl-2,4-hexadiene pyridine

coumaranone
C10H10O4 C18H19NO2 C8H14 C5H5N
December 2007 15
O
225 229 O 233 CH3 C 237
H3C N C O2N CH(CH3)2
C S
O O
O
C
N CH(CH3)2 H C
O
4-picoline isopropyl nicotinate citraconic anhydride 2-(5-nitrothienyl) isopropyl
ketone
C6H7N C9H11NO2 C5H4O3 C8H9NO3S
226 CH3 230 234 238 H

N CH3
O COOH N
N CH3 N NH2
2-picoline 2-methyl-6-aminopyridine 2-furoic acid 4-methylimidazole
C6H7N C6H8N2 C5H4O3 C4H6N2
227 CH3 231 N 235 239

H3C N C(CH3)3
O S
N O
3-picoline 4-methylpyrimidine 2-furyl t-butyl ketone benzothiophene
C6H7N C5H6N2 C9H12O2 C8H6S
228 O 232 H 236 O2N 240

C O
CH3 N
S NO2
N H
3-acetylpyridine styrene epoxide 2,4-dinitrothiophene 2,3,4,9-tetrahydrocarbazole
C7H7NO C8H8O C4H2N2O4S C12H13N
December 2007 16
241 245 249 O N CH3

253 OH
CH3 O O HO N(CH3)2
-angelicalactone octahydroanthracene N-methylmorpholine N,N-dimethyl-2,3-dihydroxy-

1-propylamine
C5H6O2 C14H18 C5H11NO C5H13NO2
O
242 O 246 250 OH 254 CH3 H
N N
H
CH3
O CH3 O OH
2-methyl- anthraquinone cyclopentanone oxime pseudoephedrine

tetrahydrofuran-3-one
C5H8O2 C14H8O2 C5H9NO C10H15NO
243 247 251 OH 255 H

O O N O N
C(CH3)3
H
butyrolactone dodecahydrotriphenylene cyclohexanone oxime t-butylformamide
C4H6O2 C18H24 C6H11NO C5H11NO
244 O 248 252 O 256 H

CH3 CH3
N HS CH2 CH N C CH3
H COOH O
CH3 CH3
O
tetramethyl-1,3- triphenylene -caprolactam N-acetylcysteine

cyclobutanedione
C8H12O2 C18H12 C6H11NO C5H9NO3S
December 2007 17
257 HO
OH 261 O 265 OH 269 O O
CH3 CH3 H
H C
HO CH CH2NH CH3 H HO OH
CH3 OH N CH3
H
O
adrenalin 3-methylbutyraldehyde 2-methyl-2,4-pentanediol N-acetylglutamic acid
C9H13NO3 C5H10O C6H14O2 C7H11NO5
258 CH2 CH COO- 262 OCH2CH3 266 OCH3 270 H

O
+
NH3 CH2 CH CH OCH2CH3
N OH HO
H OCH2CH3 N CH3
H
O
tryptophan acrolein diethyl acetal eugenol N-acetyltyrosine ethyl ester
C11H12N2O2 C7H14O2 C10H12O2 C13H17NO4
H Cl
259 H 263 NH2 267 C C 271
C H
N CH3 C O
C
O (CH3)3C
S O
N-acetylhomocysteine allylamine E -1-chloro-4-(4-t- 2,5-dihydrofuran

thiolactone butylphenyl)but-1-en-3-yne
C6H9NO2S C3H7N C14H15Cl C4H6O
260 HO C CH2CH2 CH COOH 264 268 H

O 272
O HO
NH2 OH O
O N CH3
H
O
glutamic acid adamantine N-acetylaspartic acid 2,3-dihydrofuran
C5H9NO4 C10H16 C6H9NO5 C4H6O
December 2007 18
273 COOH 277 Cl 281 O

O N C
COOH O CH2CH3
2,3-naphthalene- 2-chloronaphthalene ethyl 4-piperidone-N-

dicarboxylic acid carboxylate
C12H8O4 C10H7Cl C8H13NO3
274 OCH3 278 282 COOH

CH3
N C
H O
NO2
1-methoxy-4-nitro- sec-butylbenzene N-acetyl-2-amino-4-phenyl-
naphthalene (E)-but-2-enoic acid
C11H9NO3 C10H14 C12H13NO3
CH3
275 279 CH3 O 283 CH3O O
N
H CH3
OH
CH3 OCH3
1,5-dimethylnaphthalene N-(1-methyl-1-phenylethyl)- 3-hydroxy-3-methyl-5,8-
butyramide dimethoxy-1-coumarinone
C12H12 C12H17NO C13H16O4
276 CH3 280 O

OCH2CH3
OCH2CH3
CH3
O
1,3-dimethylnaphthalene diethyl 2-(1,1-

dimethylheptyl)malonate
C12H12 C16H30O4
December 2007 19
Chapter 9.2 The Analysis of MixturesProblem 284 Problem 286
Problem 284 Compound Mole %
Compound Mole % benzene 24
ethanol 57
ethyl acetate 59
bromoethane 43
dioxane 17
Problem 285
Compound Mole %
Problem 287
benzene 15
Compound Mole %
ethanol 41
diethyl ether 46
bromoethane 59
dichoromethane 39
December 2007 20
Problem 288 Problem 290
Compound Mole % Compound Mole %
benzene 13 fluorene 75
diethyl ether 22 fluorenone 25
dichoromethane 65
Problem 291
Problem 289 Compound Mole %
Compound Mole % 4-nitroanisole 38
benzene 23
2-nitroanisole 62
ethyl acetate 51
dioxane 26
December 2007 21
Chapter 9.3 Problems in 2D NMR Problem 294 isobutanol
Problem 292 1-propanol
Proton Chemical Shift () Carbon Chemical Shift ()

in ppm in ppm
H1 3.49 C1 64.0
H2 1.50 C2 25.5
H3 0.85 C3 9.9
H4 2.95
Problem 293 1-iodobutane
December 2007 22

1 2 3 4 5 6 7 4 3 2 1
3-heptanone CH3 CH2 C CH2 CH2 CH2 CH3 1-bromobutane CH3 CH2 CH2 CH2 Br
O
Proton Chemical Shift () Carbon Chemical Shift ()
Proton Chemical Shift () in ppm in ppm in ppm
H1 0.91 H1 3.39 C1 33.4
H2 1.94 H2 1.82 C2 34.7
H3 1.45 C3 21.4
H4 1.97 H4 0.91 C4 13.2
H5 1.44
H6 1.14 Problem 298
1 2 3 4 5 6 7 8
H7 0.79 CH3 CH2 C CH2 CH2 CH2 CH2 CH3
3-octanone
O
3
4 2 Proton Chemical Shift Carbon Chemical Shift
Problem 296
5
1 () in ppm () in ppm
-valerolactone O O H1 0.92 C1 7.8
H2 1.92 C2 35.4
Proton Chemical Shift Carbon Chemical Shift
() in ppm () in ppm C3 209.0
C1 170.0
H4 1.94 C4 42.1
H2 2.08 C2 29.9
H5 1.47 C5 23.7
H3 1.16 C3 22.2
H6 1.11 C6 31.7
H4 1.08 C4 19.0
H7 1.19 C7 22.7
H5 3.71 C5 68.8
H8 0.82 C8 14.0
December 2007 23

c b a a b c d e f
COOCH2CH3 CH3 CH2 O CH2 CH2 CH2 CH3
butyl ethyl ether
d e f g h
diethyl diethylmalonate CH3CH2 C CH2CH3
Proton Chemical Carbon Chemical Shift

COOCH2CH3
i j k
Shift () ()
in ppm in ppm
Ha 1.11 Ca 15.0
Proton Chemical Shift Carbon Chemical Shift Hb 3.29 Cb 66.0
() ()
in ppm in ppm Hc 3.27 Cc 70.1
Ha 1.19 Ca 14.0 Hd 1.52 Cd 32.1
Hb 4.13 Cb 60.8 He 1.36 Ce 19.4
Cc 171.9 Hf 0.87 Cf 13.5
Hd 0.76 Cd 8.1
He 1.88 Ce 24.5
Cf 58.0
Hg 1.88 Cg 24.5
Hh 0.76 Ch 8.1
Ci 171.9
Hj 4.13 Cj 60.8
Hk 1.19 Ck 14.0
December 2007 24
4 3 2 1
butyl butyrate 1-iodobutane CH3 CH2 CH2 CH2 I
4 3 2 1
Proton Chemical Carbon Chemical 1-butanol CH3 CH2 CH2 CH2 OH
Shift () Shift ()
in ppm in ppm
Ha 0.75 Ca 13.9 1-iodobutane 1
H Chemical 1-butanol 1
H Chemical
Hb 1.19 Cb 19.5 Shift () Shift ()
in ppm in ppm
Hc 1.40 Cc 31.2
H1 2.70 H1 3.41
Hd 3.97 Cd 64.0
H2 1.40 H2 1.27
Ce 172.8
H3 1.08 H3 1.39
Hf 2.08 Cf 36.2
H4 0.64 H4 0.84
Hg 1.52 Cg 19.0
-OH 1.95
Hh 0.79 Ch 13.9
December 2007 25

CH3 H
(E)- and (Z)-2-butene (Z)-3-methyl-2-penten-4-ynol C C
C CH2OH
C
H
Problem 305
H Br
C C
CH3 CH3 H8 NO2
H7 H2
1-nitronaphthalene
H6 H3
H5 H4
Proton Chemical Shift () in ppm

H2 8.22
H3 7.53
H CH3
C C H4 8.10
CH3 Br
H5 7.95
H6 7.62
H7 7.71
H8 8.56
December 2007 26

COOCH2CH3
CH3 CH3
ethyl diethylmalonate
CH3CH2 C H
geraniol H
COOCH2CH3
CH3
HOCH2 H
Problem 307
CH3 CH2 CH2 CH2 O C CH2 CH2 CH2 CH3

butyl
valerate O
Problem 308
CH3 CH3
nerol H
CH3
H CH2OH
December 2007 27
Chapter 9.4 Analysis of NMR Spectra
Structure Number of 1H Number of 13C

environments environments
CH3 CO CH2CH2CH3 4 5
CH3CH2 CO CH2CH3 2 3
CH2 CHCH2CH3 5 4
cis- CH3CH CHCH3 2 2
trans-CH3CH CHCH3 2 2
1 1
3 4 Chemical Shifts A = 300 Hz / 60 MHz = 5.0 ppm

Cl M = 240 Hz / 60 MHz = 4.0 ppm
Br 2 3 X = 120 Hz / 60 MHz = 2.0 ppm
Br
Cl Cl 3 4
Problem 312
1 2
Br Br
2 4
Br Cl
Cl OCH3 5 7
slow chair- 2 1
chair
fast chair- 1 1
chair Chemical Shifts A = 180 Hz / 200 MHz = 0.90 ppm
rigid M = 220 Hz / 200 MHz = 1.22 ppm
H 7 4
Cl X = 300 Hz / 200 MHz = 1.50 ppm
December 2007 28
Spin System A2X3
Chemical Shifts A = 150 Hz / 400 MHz = 0.375 ppm

X = 300 Hz / 400 MHz = 0.750 ppm
Chemical Shifts A = 3.36 ppm = 3.36 x 60 = 202 Hz from TMS

X = 1.11 ppm = 1.11 x 60 = 67 Hz from TMS
1st Order Analysis AX = A - X = 202 - 67 = 135 Hz
AX / JAX = 135 / 7 = 19.3
This ratio is much greater than 3 so a 1st order analysis is justified.
December 2007 29
Problem 315 Spin System AMX Problem 316 Spin System AMX

M = 439 Hz / 100 MHz = 4.39 ppm Chemical Shifts A = 460 Hz / 60 MHz = 7.67 ppm
X = 408 Hz / 100 MHz = 4.08 ppm X = 442 Hz / 60 MHz = 7.37 ppm
M = 394 Hz / 60 MHz = 6.57ppm
Coupling constants JAM = 3.1 Hz
JAX = 20.1 Hz Coupling constants JAM = 1.70 Hz
JMX = 1.1 Hz JAX = 0.85 Hz
JMX = 3.65 Hz
1st Order Analysis = A - M = 501 - 439 = 62 Hz
= A - X = 501 - 408 = 93 Hz 1st Order Analysis = A - M = 460 - 394 = 66 Hz
= M - X = 439 - 408 = 31Hz = A - X = 460 - 442 = 18 Hz
/ JAM = 62 / 3.1 = 20.0 = M - X = 442 - 394 = 48 Hz
/ JAX = 93 / 20.1 = 4.6 / JAM = 66 / 1.7 = 38.8
/ JMX = 31 / 2.1 = 14.7 / JAX = 18 / 0.85 = 21.2
/ JMX = 48 / 3.65 = 13.2
All ratios are greater than 3 so a 1st order analysis is justified.
December 2007 30
Problem 317 Spin System AMX Problem 318 Spin System AMX
Chemical Shifts 3 = 673 Hz / 100 MHz = 6.73 ppm

4 = 719 Hz / 100 MHz = 7.19 ppm
6 = 777 Hz / 100 MHz = 7.77ppm
Coupling constants 3
J34 = 8.8 Hz Chemical Shifts A = 628 Hz / 100 MHz = 6.28 ppm
4
J46 = 2.3 Hz B = 527 Hz / 100 MHz = 5.27 ppm
5
J36 not resolved (< 1Hz) C = 592 Hz / 100 MHz = 5.92 ppm
Coupling constants JAB = 2.1 Hz; JAC = 17.5 Hz; JBC = 9.9 Hz
1st Order Analysis 34 = 4 - 3 = 719 - 673 = 46 Hz
46 = 6 - 4 = 777 - 719 = 58 Hz 1st Order Analysis AB = A - B = 628 - 527 = 101 Hz
36 = 6 - 3 = 777 - 673 = 104 Hz AC = A - C = 628 - 592 = 36 Hz
34 / J34 = 46 / 8.8 = 5.2 BC = C - B = 592 - 527 = 65 Hz
46 / J46 = 58 / 2.3 = 25.2 AB / JAB = 101 / 2.1 = 48.1
36 / J36 = 104 / <1 = >104 AC / JAC = 36 / 17.5 = 2.1
BC / JBC = 65 / 9.9 = 6.6
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
Problem 319 Spin System AX3 Problem 320 Spin System AX3

X = 280 Hz / 60 MHz = 4.67 ppm

X = 99 Hz / 100 MHz = 0.99 ppm
Coupling constants JAX = 5 Hz

AX / JAX = 100 / 5 = 20.0
AX / JAX is much greater than 3 so a 1st order analysis is justified.
December 2007 32
Problem 321 4 Spin System AMX2 Problem 322 4 Spin System AM2X
Chemical Shifts A = 340 Hz / 60 MHz = 5.67 ppm Chemical Shifts A = 110 Hz / 60 MHz = 1.83ppm
M = 240 Hz / 60 MHz = 4.00 ppm M = 200 Hz / 60 MHz = 3.33 ppm
X = 100 Hz / 60 MHz = 1.67 ppm X = 290 Hz / 60 MHz = 4.83 ppm
December 2007 33
Problem 323 4 Spin System AM2X Problem 324 4 Spin System A2MX

M = 510 Hz / 100 MHz = 5.10 ppm
X = 395 Hz / 100 MHz = 3.95 ppm Chemical Shifts A = 279 Hz / 100 MHz = 2.79 ppm
M = 149 Hz / 100 MHz = 1.49 ppm
Coupling constants JAM = 3 Hz; JAX = 16 Hz; JMX = 5 Hz; X = 39 Hz / 100 MHz = 0.39 ppm
1st Order Analysis AX = A - X = 646 - 395 = 251 Hz Coupling constants JAM = 4.5 Hz; JAX = 7.5 Hz; JMX = 11.0 Hz;
AM = A - M = 646 - 510 = 136 Hz
MX = M - X = 510 - 395 = 115 Hz 1st Order Analysis AX = A - X = 279 - 39 = 240 Hz
AM = A - M = 279 - 149 = 130 Hz
AX / JAX = 251 / 16 = 15.7 MX = M - X = 149 - 39 = 110 Hz
AM / JAM = 136 / 3 = 45.3
MX / JMX = 115 / 5 = 23.0 AX / JAX = 240 / 7.5 = 32.0
AM / JAM = 130 / 4.5 = 28.9
All ratios are significantly greater than 3 so a 1st order analysis is justified. MX / JMX = 110 / 11 = 10.0
All ratios are significantly greater than 3 so a 1st order analysis is justified.
December 2007 34
Problem 325 4 Spin System AMX2 Problem 326 5 Spin System A2M2X

M = 160 Hz / 100 MHz = 1.60 ppm
X = 37 Hz / 100 MHz = 0.37 ppm Chemical Shifts A = 1000 Hz / 200 MHz = 5.0 ppm
M = 500 Hz / 200 MHz = 2.5 ppm
Coupling constants JAM = 12.0 Hz; JAX = 5.0 Hz; JMX = 8.0 Hz;
X = 100 Hz / 200 MHz = 0.5 ppm
AM = A - M = 302 - 160 = 142 Hz
MX = M - X = 160 - 37 = 123 Hz 1st Order Analysis AX = A - X = 1000 - 100 = 900 Hz
AM = A - M = 1000 - 500 = 500 Hz
AX / JAX = 265 / 5.0 = 53.0 MX = M - X = 500 - 100 = 400 Hz
AM / JAM = 142 / 12.0 = 11.8
MX / JMX = 123 / 8.0 = 15.4 AX / JAX = 900 / 7.0 = 128.6
AM / JAM = 500 / 3.0 = 166.7
MX / JMX = 400 / 10.0 = 40.0
December 2007 35
Problem 327 5 Spin System AMX3

M = 585 Hz / 100 MHz = 5.85 ppm
X = 192 Hz / 100 MHz = 1.92 ppm

AM = A - M = 710 - 585 = 125 Hz
MX = M - X = 585 - 192 = 393 Hz
AX / JAX = 518 / 6.9 = 84.7

AM / JAM = 125 / 15.3 = 8.2
MX / JMX = 393 / 1.6 = 245.6
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
Problem 328 5 Spin System ADMX3

1st Order Analysis AD = A - D = 956 - 695 = 261 Hz
AM = A - M = 956 - 619 = 337 Hz
AX = A - X = 956 - 205 = 751 Hz
DM = D - M = 695 - 619 = 76 Hz
DX = D - X = 695 - 205 = 490 Hz
MX = M- X = 619 - 205 = 414 Hz
AD / JAD = 261 / <1 = >261

AM / JAM = 337 / 8.2 = 41.1
AX / JAX = 751 / <1 = >751
DM / JDM = 76 / 15.8 = 4.8
DX / JDX = 490 / 6.9 = 71.0
MX / JMX = 414 / 1.6 = 258.8
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:

O
D
A C H
H
C C
Chemical Shifts A = 956 Hz / 100 MHz = 9.56 ppm; H CH3
D = 695 Hz / 100 MHz = 6.95 ppm; M X
M = 619 Hz / 100 MHz = 6.19 ppm;
X = 205 Hz / 100 MHz = 2.05 ppm;
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
Problem 329 5 Spin System AMX3 Problem 330 3 Spin System A2X

M = 220 Hz / 60 MHz = 3.67 ppm
X = 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
each other. Compound 4 is the HA HA
correct answer. HX
December 2007 38

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
aromatic and vinylic protons. one large (>7 Hz) ortho coupling. The spectrum has one proton (at 7.1)
which has only a small coupling so this cannot be the spectrum of
The spectrum shows 6 distinct resonances therefore compounds 5 and 6 1,5-dichloronaphthalene.
can be eliminated because they would each have only 4 resonances (on
symmetry grounds). The spectrum is an AMX spectrum with couplings between A and X of
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 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 6.4 is clearly one of the vinylic protons and it is coupled to the
other vinylic proton at 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

Solutions Manual: Organic Structures From Spectra - 4Th Edition

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1 5 BrCH2 CH2Br 9 OH OH 13 Cl2CH CH3

2-butanone 1,2-dibromoethane pinacol 1,1-dichloroethane

C4H8O C2H4Br2 C6H14O2 C2H4Cl2

propionic acid 1,2-butanedione 1,4-cyclohexanedione 2-propanol

3 O 7 CH2C N 11 O 15 CH3 CH3

ethyl acetate succinonitrile cyclopentanone 2-bromopropane

C4H8O2 C4H4N2 C5H8O2 C3H7Br

4 CH3O CH2CH3 8 CH3 CH3 12 CH3CH2 I 16 Cl

methyl propionate 2,2,3,3-tetramethylbutane iodoethane 1,4-dichlorobutane

C4H8O2 C8H18 C2H5I C4H8Cl2

1,3-dibromopropane 4-aminobutyric acid benzyl cyanide benzyl methyl ketone

C3H6Br2 C4H9NO2 C8H7N C9H10O

1-bromo-3-chloropropane anisole benzylamine propiophenone

C3H6BrCl C7H8O C7H9N C9H10O

4-bromobutyronitrile benzyl alcohol 2-phenylethanol 2-phenylpropionaldehyde

C4H6NBr C7H8O C8H10O C9H10O

alanine benzyl bromide 1-phenylethanol butyrophenone

C3H7NO2 C7H7Br C8H10O C10H12O

t-butyl acetoacetate dibenzylamine propionic anhydride 1,1-diacetoxyethane

C8H14O3 C14H15N C6H10O3 C6H10O4

34 CH3CH2 O C H 38 CH3 42 O 46 CH3OOC COOCH3

ethyl formate N,N,N,N-tetramethyl-1,2- diethyl oxalate dimethyl methylmalonate

benzil 2,5-hexanedione ethylene glycol diacetate methyl acetyllactate

C14H10O2 C6H10O2 C6H10O4 C6H10O4

1,2-diphenylethane diethyl carbonate dimethyl succinate diethyl succinate

C14H14 C5H10O3 C6H10O4 C8H14O4

ethylene glycol dipropionate ,-dichlorotoluene 1,2,3-trimethoxybenzene durene

C8H14O4 C7H6Cl2 C9H12O3 C10H14

butyric anhydride benzaldehyde dimethylacetal mesitylene 1,2,3,4-tetramethylbenzene

C8H14O3 C9H12O2 C9H12 C10H14

1,4-dibromobenzene benzilic acid 1,2,3-trimethylbenzene 1,2,3,5-tetramethylbenzene

C6H4Br2 C14H12O3 C9H12 C10H14

52 56 OH 60 CH3 64 CH3 CH3

OH CH3 CH3 CH3 CH3

4,4'-dibromobiphenyl catechol 1,2,4-trimethylbenzene hexamethylbenzene

C12H8Br2 C6H6O2 C9H12 C12H18

65 CH3 CH3 69 OH 73 OH 77 HOOC COOH

1,2,3,4,5,- 3-hydroxybutanone 2-methyl-2-butanol 3,3-dimethylglutaric acid

66 CH3 NH2 70 HO 74 NH2 78 HOOC COOH

acetamide 4-hydroxy-4-methyl-2- hexylamine 2,2-dimethylpentanedioc

ethyl glycolate isobutyl acetate ethyl 2-bromopropionate tetramethylurea

C4H8O3 C6H12O2 C5H9O2Br C5H12N2O

ethyl cyanoacetate 3,3-dimethylbutyric acid 4,4-dimethoxy-2-butanone 1,3-dioxan

C5H7NO2 C6H12O2 C6H12O3 C4H8O2

1,4-dioxan 2-bromohexanoic acid 2-methylbut-3-en-2-ol dibutyl ether

C4H8O2 C6H11O2Br C5H10O C8H18O

18-crown-6 2-ethylmalononitrile threonine butylbenzene

C12H24O6 C5H6N2 C4H9NO3 C10H14

2,3-dichloropropene 3-methylbutyronitrile 1-bromo-3-phenylpropane t-butylbenzene

C3H4Cl2 C5H9N C9H11Br C10H14

4-chlorobutyl acetate 5-amino-1-pentyne 1-nitropropane sec-butylbenzene

C6H11O2Cl C5H9N C3H7NO2 C10H14

97 101 O 105 O 109

neopentylbenzene p-chloroacetophenone 4-methoxyacetophenone 4-methoxymethylphenol

C11H16 C8H7OCl C9H10O2 C8H10O2

98 102 O 106 O 110 CH3

4-(n-butyl)--chlorotoluene p-toluyl chloride p-cresyl acetate 4-dimethylaminobenzonitrile

C11H15Cl C8H7OCl C9H10O2 C9H10N2

99 103 107 O 111 CH3

4-methyl-4-phenyl-2-pentanone p-anisic acid methyl p-toluate p-bromo-N,N-dimethylaniline

100 O 104 108 112 O