Organic Structures From Spectra-Edition 4-Solutions Manual-Libre

Please Keep Absolutely
Confidential
ORGANIC STRUCTURES FROM SPECTRA 4th EDITION

L D Field, S Sternhell and J R Kalman
Copyright: Copying or duplicating

these solutions in any form is
strictly prohibited
Solutions Manual
December 2007

Confidential

5

strictly prohibited
BrCH2 CH2Br
13
OH OH
CH3
Cl2CH CH3
CH3
CH3 CH3
2-butanone
1,2-dibromoethane
pinacol
1,1-dichloroethane
C4H8O
C2H4Br2
C6H14O2
C2H4Cl2
CH3CH2
OH
10
O
CH3
14
CH3
H
CH3
CH3
OH
propionic acid
1,2-butanedione
(biacetyl)
C4H6O2
C3H6O2
O
CH2CH3
CH3
CH2C
CH2C
11
1,4-cyclohexanedione
2-propanol
C6H8O2
C3H8O
15
CH3
H
CH3
Br
ethyl acetate
succinonitrile
cyclopentanone
2-bromopropane
C4H8O2
C4H4N2
C5H8O2
C3H7Br
CH3O
CH2CH3
O
12
CH3 CH3
CH3 C
CH3CH2 I
16
Cl
Cl
CH3
CH3 CH3
December 2007
methyl propionate
2,2,3,3-tetramethylbutane
iodoethane
1,4-dichlorobutane
C4H8O2
C8H18
C2H5I
C4H8Cl2

Confidential
17
Br

21
Br

strictly prohibited
H2N
25
COOH
CH2C
29
CH2 C CH3
O
1,3-dibromopropane
4-aminobutyric acid
benzyl cyanide
benzyl methyl ketone
C3H6Br2
C4H9NO2
C8H7N
C9H10O
18
Br
22
Cl
26
OCH3
CH2NH2
30
1-bromo-3-chloropropane
anisole
benzylamine
propiophenone
C3H6BrCl
C7H8O
C7H9N
C9H10O
19
Br
23
27
CH2OH
OH
31
CH3
CH C H
O
4-bromobutyronitrile
benzyl alcohol
2-phenylethanol
2-phenylpropionaldehyde
C4H6NBr
C7H8O
C8H10O
C9H10O
28
+
NH3
20
CH3
December 2007
COO
24
OH
CH2Br
32
H
CH3
alanine
benzyl bromide
1-phenylethanol
butyrophenone
C3H7NO2
C7H7Br
C8H10O
C10H12O

Confidential

O
33
O
O
34
37
41
CH3
45
CH3
CH3
H CH3 O
t-butyl acetoacetate
dibenzylamine
propionic anhydride
1,1-diacetoxyethane
C8H14O3
C14H15N
C6H10O3
C6H10O4
CH3CH2 O C H
38
42
CH3
CH3
ethyl formate
CH3
35
39
COOCH3
CH3
diethyl oxalate
dimethyl methylmalonate
C6H10O4
C6H10O4
43
47
O
CH3
O
CH3
CH3
CH3
O
CH3OOC
N,N,N,N-tetramethyl-1,2ethanediamine
C6H16N2
C3H6O2
46
CH3
C
O
OCH3
benzil
2,5-hexanedione
ethylene glycol diacetate
methyl acetyllactate
C14H10O2
C6H10O2
C6H10O4
C6H10O4
36
40
44
O
CH3CH2O
OCH2CH3
48
O
CH3O
OCH3
O
December 2007

strictly prohibited
O
O
1,2-diphenylethane
diethyl carbonate
dimethyl succinate
diethyl succinate
C14H14
C5H10O3
C6H10O4
C8H14O4

Confidential

strictly prohibited

49
53
57
CHCl2
H3C
CH3
H3C
CH3
61
OCH3
OCH3
OCH3
ethylene glycol dipropionate
,-dichlorotoluene
1,2,3-trimethoxybenzene
durene
C8H14O4
C7H6Cl2
C9H12O3
C10H14
CH3
50
51
54
58
OCH3
C
H
OCH3
CH3
62
CH3
CH3
CH3
CH3
butyric anhydride
benzaldehyde dimethylacetal
mesitylene
1,2,3,4-tetramethylbenzene
C8H14O3
C9H12O2
C9H12
C10H14
Br
55
Br
59
OH
63
CH3
COOH
CH3
CH3
CH3
CH3
CH3
52
CH3
CH3
1,4-dibromobenzene
benzilic acid
1,2,3-trimethylbenzene
1,2,3,5-tetramethylbenzene
C6H4Br2
C14H12O3
C9H12
C10H14
Br
Br
56
60
OH
CH3
CH3
OH
CH3
64
CH3
CH3
CH3
CH3
CH3
CH3
4,4'-dibromobiphenyl
catechol
1,2,4-trimethylbenzene
hexamethylbenzene
C12H8Br2
C6H6O2
C9H12
C12H18
December 2007

Confidential
65
CH3

69
CH3
CH3
1,2,3,4,5,pentamethylcyclopentadiene
C10H16
66
CH3
CH3
3-hydroxybutanone
(acetoin)
C4H8O2
70
NH2
74
4-hydroxy-4-methyl-2pentanone
C6H12O2
C2H5NO
71
O
O
3,3-dimethylglutaric acid
C7H12O4
78
HOOC
COOH
hexylamine
2,2-dimethylpentanedioc
acid
C7H12O4
C6H15N
75
CH3
79
O
CH3CH2
CH3 CH3
CH3
CH3
Br
N
CH3
O
ethyl glycolate
isobutyl acetate
ethyl 2-bromopropionate
tetramethylurea
C4H8O3
C6H12O2
C5H9O2Br
C5H12N2O
68
72
O
CH3CH2O
December 2007
NH2
HOOC
COOH
CH3 CH3
acetamide
HO
CH3
CH3
2-methyl-2-butanol
(t-amyl alcohol)
C5H12O
HO
67
77
OH
CH3
CH3
73
OH
CH3
CH3

strictly prohibited
76
COOH
OCH3
O
80
OCH3
ethyl cyanoacetate
3,3-dimethylbutyric acid
4,4-dimethoxy-2-butanone
1,3-dioxan
C5H7NO2
C6H12O2
C6H12O3
C4H8O2

Confidential
81

85
89
Br
OH
93
CH2
HO
1,4-dioxan
2-bromohexanoic acid
2-methylbut-3-en-2-ol
dibutyl ether
C4H8O2
C6H11O2Br
C5H10O
C8H18O
82
86
90
CN
+
-
C
H OH O
94
NH3
CH3
CN
O
O
83

strictly prohibited
18-crown-6
2-ethylmalononitrile
threonine
butylbenzene
C12H24O6
C5H6N2
C4H9NO3
C10H14
H2C C
87
CH2Cl
91
CN
Br
95
C(CH3)3
Cl
2,3-dichloropropene
3-methylbutyronitrile
1-bromo-3-phenylpropane
t-butylbenzene
C3H4Cl2
C5H9N
C9H11Br
C10H14
84
88
O
Cl
H2N
92
NO2
96
CH3
4-chlorobutyl acetate
5-amino-1-pentyne
1-nitropropane
sec-butylbenzene
C6H11O2Cl
C5H9N
C3H7NO2
C10H14
December 2007

Confidential

101
97

strictly prohibited
Cl
C(CH3)3
105
O
C
109
O
CH3O
CH3
HO
CH2OCH3
CH3
neopentylbenzene
p-chloroacetophenone
4-methoxyacetophenone
4-methoxymethylphenol
C11H16
C8H7OCl
C9H10O2
C8H10O2
98
CH2Cl
102
CH3
106
CH3
110
CH3
CH3
N C
N
CH3
Cl
4-(n-butyl)--chlorotoluene
p-toluyl chloride
p-cresyl acetate
4-dimethylaminobenzonitrile
C11H15Cl
C8H7OCl
C9H10O2
C9H10N2
99
103
O
CH3O
107
COOH
O
H3C
111
CH3
Br
N
CH3
OCH3
4-methyl-4-phenyl-2-pentanone
C12H16O
100
O
Br
104
p-anisic acid
methyl p-toluate
p-bromo-N,N-dimethylaniline
C8H8O3
C9H10O2
C8H10NBr
CH2O C
CH3
108
CH3O
CH2OH
CH3
112
O
CH3O
C
C(CH3)3
p-bromoacetophenone
benzyl acetate
p-methoxybenzyl alcohol
p-anisyl t-butyl ketone
C8H7OBr
C9H10O2
C8H10O2
C12H16O2
December 2007

Confidential
113
O
(H3C)3C

strictly prohibited

117
121
O C CH3
CH3CH2O C
NH2
125
4-t-butylphenyl acetate
o-nitrobenzaldehyde
ethyl p-aminobenzoate
C12H16O2
C7H5NO3
C9H11NO2
(CH3)3C
C OCH3
O
118
H C
122
OCH3
CH3CH2O
NH2
p-ethoxybenzamide
C12H16O2
C8H8O2
C9H11NO2
NO2
119
p-ethoxyacetanilide
(phenacetin)
C10H13NO2
H
126
HO
C CH3
O
4-methoxybenzaldehyde
CH3O
O 2N
123
p-hydroxyacetanilide
(paracetamol)
C8H9NO2
127
O
CH3
CH3
methyl 4-t-butylbenzoate
115
CH3CH2O
NO2
114
O
C
NH C CH3
116
p-nitroanisole
4-nitrophenylacetylene
4-methylacetanilide
ethyl p-ethoxybenzoate
C7H7NO3
C8H5NO2
C8H9NO
C11H14O3
H C
NO2
120
124
O
C
C
H3C
OH
128
O
CH3 C
NH2
OCH3
p-nitrobenzaldehyde
4-acetoxybenzoic acid
4-aminoacetophenone
C7H5NO3
C9H8O4
C8H9NO
December 2007
CH3O
methyl (p-methoxyphenyl)propionionate
C11H14O3

Confidential
129

strictly prohibited

133
137
O
C
O
C
141
CH3
C
O
N-isopropylbenzylamine
hydroquinone dipropionate
C10H15N
C12H14O4
130
134
OCH3
O
CH3
methyl 2-methoxy-2phenylacetate
C10H12O3
131
NCO
cyclopropyl methyl ketone

C5H8O
142
CH3O
138
1,3-dihydroxyphenyl
dipropionate
C12H14O4
OCH3
OH
O O
diethyl terephthalate
dimethyl o-phthalate
cyclopropane carboxylic acid
C12H14O4
C10H10O4
C4H6O2
135
C
C
139
O
O
143
H
C
O
132
phenyl isocyanate
diethyl o-phthalate
cycloheptanone
benzoylcylopropane
C7H5NO
C12H14O4
C7H12O
C10H10O
OCH3
136
OCH3
H
140
O
C
144
CH2
C
OCH2CH3
phenylacetaldehyde
dimethyl acetal
C10H14O2
December 2007
diethyl isophthalate
cycloheptatriene
ethyl cyclobutanecarboxylate
C12H14O4
C7H8
C7H12O2
10

Confidential
145
C(CH3)3

strictly prohibited

149
153
157
CH3
(CH3)3C
OH
C
O
NEt2
(CH3)3C
4-t-butylcyclohexanone
benzyl benzoate
N,N-diethyl-m-toluamide
3,5-di-t-butylphenol
C10H18O
C14H12O2
C12H17NO
C14H22O
146
150
CH3
154
158
Br
Br
N
H3C
N-methylacetamide
H2N
NH2
Br
(p-cresyl)methyl phenyl
ketone
C15H14O2
C3H7NO
147
OH
CH3
151
CH3
2-bromophenol
3,5-dibromocumene
C6H5OBr
C9H10Br2
155
159
Br
O C CH3
O
COOH
148
1,4-diaminobutane
p-cresyl phenylacetate
C4H12N2
C15H14O2
H2N
NH2
152
Cl3C
COOH
acetylsalicylic acid
(aspirin)
C9H8O4
156
CCl3
160
NH2
Br
3-bromo-5-isopropylbenzoic
acid
C10H11O2Br
Br
O
O
1,5-diaminopentane
C5H14N2
December 2007
1,3-bis(trichloromethyl)benzene
C8H4Cl6
11
2,6-dibromoaniline
piperonal
C6H5NBr2
C8H6O3

Confidential
161
162

165
CH3
CH3

strictly prohibited
169
NO2
173
3-nitro-o-xylene
2-cyclohexene-1-one
indane
-tetralone
C8H9NO2
C6H8O
C9H10
C10H10O
Cl
CH3
Cl
Cl
166
170
174
OH
O
2,4,5-trichlorotoluene
2-hydroxycyclohex1-en-3-one
C6H8O2
C7H5Cl3
163
Cl
NH2
Cl
Cl
167
171
O
C CH3
3,3-dimethylindan-1-one
-tetralone
C11H12O
C10H10O
175
164
2,4,5-trichloroaniline
1-acetyl-1-cylohexene
1-indanone
9-methylfluorene
C6H4NCl3
C8H12O
C9H8O
C14H12
CH3O
I
OCH3
I
168
172
CH3
CH3
4,6-diiodo-1,3dimethoxybenzene
C8H8O2I2
176
O
O
CH3
December 2007
CH3
4-methylpent-3-en-2-one
(mesityl oxide)
C6H10O
12
2-indanone
fluorenone
C9H8O
C13H8O

Confidential
177
CH3

181
CH3CH2
185
CH3
O
CH3
O
CH3
CH3
CH3
183
CH3
HO
mevalonic lactone
C6H10O3
December 2007
C C C CH2CH3
OH
187
C C
OH
CH3
COOH
H
CH3
3-methyl-1-phenylpent1-yn-3-ol
C12H14O
C C CH3
2-hydroxy-3-methylbutyric
acid
C5H10O3
191
OH
CH2
CH CH2
OH
OH OH
1-phenyl-1,3-pentadiyne
glycerol
C11H8
C3H8O3
COOCH3
188
C3H6Br2
CH3
CH3
C
CH3
2,5-dimethyl-3-hexyne2,5-diol
C8H14O2
184
OH
1,2-dibromopropane
190
CH3
CH3
CH3
CH3
2,2-dimethylglutaric
anhydride
C7H10O3
CH3
(Z)-1-methoxybut1-en-4-yne
C5H6O
1,2,2,6,6-pentamethylpiperidine
C10H21N
CH3
180
CH3
3,3-dimethylglutaric
anhydride
C7H10O3
CH2Br
H
186
182
CH3
CH3
4-ethyl-4-methyl-2,6piperidinedione
C8H13NO2
CH3
179
OCH3
Br
2,4,6-trimethyl1,3,5-trioxane
C6H12O3
CH3
189
178

strictly prohibited
192
OH
CH3
O
H
C
HC
(Z)-3-methylpent-2en-4-ynal
C6H6O
C
NH2
CH
methyl 4-amino-3,5diethynylbenzoate
C12H9NO2
13
CH3
H
2-butanol
C4H10O

Confidential
193

197

strictly prohibited
201
O
NH2
Cl
205
NH2
O
dibenzyl sulfoxide
p-aminobenzenesulfonamide
C6H8N2O2S
C14H14OS
vinyl 2-chloroethyl ether
cinnamaldehyde
C4H7OCl
C9H8O
198
194
202
206
COOH
CH2OH
CH3
(E)-3-(phenylthio)acrylic
acid
C9H8O2S
195
N-(p-tolyl)succinimide
cinnamyl alcohol
C4H6O2S
C11H11NO2
C9H10O
199
O
CH3
divinyl sulfone
S OCH2CH3
207
Cl
CH
C(CH3)3
O
H
ethyl p-toluenesulfonate
allyl p-anisyl thioether
C9H12O3S
O
phenylacetaldeyde
ethylene glycol acetal
C10H12O2
C10H12OS
O
CH3
O
CH2
CH3O
196
203
200
(E)-3-chloro-4,4-dimethyl-1phenyl-1-pentene
C13H17Cl
O
S
CH2CH2O
4
S CH3
204
CH(CH3)2
208
H
H
CH3
Br
CH3
p-tolyl methyl sulfoxide

C8H10OS
December 2007
tetraethylene glycol
ditosylate
C22H30O9S2
(E)-1-phenyl-4-methyl-1penten-3-one
C12H14O
14
(Z)--bromostyrene
C8H7Br

Confidential
209

213
H
NO2
Br
217
H
Cl
Cl
OH
214
Cl
Cl
Cl
3-benzyloxy-1-propanol
211
215
COOH
CH3O
219
Br
CH3O
222
CH3
5,6-dimethoxy-2coumaranone
C10H10O4
December 2007
Cl
OCH2CH3
2-chloroacetaldehyde
diethylacetal
C6H13O2Cl
223
OCH3
CH2 O CH2
methyl (E)-3-methylacrylate
1,3-dibenzylglycerol
C5H8O2
C17H20O3
220
CH3
O CH2
CH2
HO
OCH3
O
224
O
CH3O
OCH2CH3
CN
methyl 2,3-dibromo-3(p-nitrophenyl)propionate
C10H9NO4Br2
216
malonaldehyde dimethyl
acetal
C7H16O4
4-cyano-2,2dimethylbutyraldehyde
C7H11NO
C9H8O4
OCH2CH3
Br
212
218
COOH
COOH
homophthallic acid
OCH3 OCH3
diethyl isopropylidenemalonate
C10H16O4
O2N
OCH3
2,4,5-trichlorophenoxyacetic acid (2,4,5-T)

C8H5O3Cl3
C10H14O2
CH3O
OCH2CH3
CH3
1,1-di-(p-chlorophenyl)-2,2,2trichloroethane (DDT)
C14H9Cl5
C8H6BrNO2
221
O
CH3
CCl3
(E)-p-nitro--bromostyrene
210

strictly prohibited
N
CN
OCH3
2,3-di-(p-anisyl)butyronitrile
2,5-dimethyl-2,4-hexadiene
pyridine
C18H19NO2
C8H14
C5H5N
15

Confidential

strictly prohibited

O
225
H3C
229
233
CH3
237
O2N
C
H
CH(CH3)2
CH(CH3)2
S
O
C
O
4-picoline
isopropyl nicotinate
citraconic anhydride
C6H7N
C9H11NO2
C5H4O3
226
CH3
230
227
234
CH3
238
COOH
NH2
CH3
N
N
2-picoline
2-methyl-6-aminopyridine
2-furoic acid
4-methylimidazole
C6H7N
C6H8N2
C5H4O3
C4H6N2
231
CH3
235
N
N
H3C
C(CH3)3
239
S
3-picoline
4-methylpyrimidine
2-furyl t-butyl ketone
benzothiophene
C6H7N
C5H6N2
C9H12O2
C8H6S
228
232
O
C
236
H
O
CH3
240
O2N
S
NO2
December 2007
2-(5-nitrothienyl) isopropyl
ketone
C8H9NO3S
N
H
3-acetylpyridine
styrene epoxide
2,4-dinitrothiophene
2,3,4,9-tetrahydrocarbazole
C7H7NO
C8H8O
C4H2N2O4S
C12H13N
16

Confidential

245
241
CH3
249

strictly prohibited
N CH3
-angelicalactone
octahydroanthracene
N-methylmorpholine
C5H6O2
C14H18
C5H11NO
253
OH
HO
N(CH3)2
N,N-dimethyl-2,3-dihydroxy1-propylamine
C5H13NO2
O
O
242
246
250
H
CH3
N
CH3
anthraquinone
cyclopentanone oxime
pseudoephedrine
C14H8O2
C5H9NO
C10H15NO
247
251
OH
255
H
O
N
C(CH3)3
butyrolactone
dodecahydrotriphenylene
cyclohexanone oxime
t-butylformamide
C4H6O2
C18H24
C6H11NO
C5H11NO
244
248
252
CH3
CH3
CH3
O
256
H
HS CH2 CH
N
H
CH3
tetramethyl-1,3cyclobutanedione
C8H12O2
December 2007
CH3
OH
254
2-methyltetrahydrofuran-3-one
C5H8O2
243
OH
N
COOH
C
O
triphenylene
-caprolactam
N-acetylcysteine
C18H12
C6H11NO
C5H9NO3S
17
CH3

Confidential
257
HO
HO

261
OH

strictly prohibited
265
O
H
CH CH2NH CH3
269
OH
CH3
CH3
O
HO
H
OH
CH3
O
OH
CH3
N
H
O
adrenalin
3-methylbutyraldehyde
2-methyl-2,4-pentanediol
N-acetylglutamic acid
C9H13NO3
C5H10O
C6H14O2
C7H11NO5
258
N
H
CH2 CH COO+
NH3
262
266
OCH2CH3
CH2 CH
270
OCH3
CH
OH
OCH2CH3
HO
OCH2CH3
CH3
N
H
O
tryptophan
acrolein diethyl acetal
eugenol
N-acetyltyrosine ethyl ester
C11H12N2O2
C7H14O2
C10H12O2
C13H17NO4
259
263
H
N
271
O
C
(CH3)3C
HO C CH2CH2 CH COOH
O
NH2
CH3
N-acetylhomocysteine
thiolactone
C6H9NO2S
260
Cl
267
NH2
allylamine
E -1-chloro-4-(4-tbutylphenyl)but-1-en-3-yne
C14H15Cl
C3H7N
264
268
HO
O
OH
CH3
C4H6O
272
2,5-dihydrofuran
December 2007
glutamic acid
adamantine
N-acetylaspartic acid
2,3-dihydrofuran
C5H9NO4
C10H16
C6H9NO5
C4H6O
18

Confidential
273
COOH

277
281
Cl
O
O
N C
COOH
O CH2CH3
2,3-naphthalenedicarboxylic acid
C12H8O4
274
OCH3
2-chloronaphthalene
ethyl 4-piperidone-Ncarboxylate
C8H13NO3
C10H7Cl
278
282
COOH
CH3
N C
O
H
NO2
1-methoxy-4-nitronaphthalene
C11H9NO3
CH3
275
sec-butylbenzene
N-acetyl-2-amino-4-phenyl(E)-but-2-enoic acid
C12H13NO3
C10H14
279
283
CH3 O
CH3O
N
H
CH3
CH3
OCH3
1,5-dimethylnaphthalene
N-(1-methyl-1-phenylethyl)butyramide
C12H17NO
C12H12
276
280
CH3
O
OCH2CH3
CH3
1,3-dimethylnaphthalene
C12H12
December 2007
OCH2CH3
O
diethyl 2-(1,1dimethylheptyl)malonate
C16H30O4
19
OH
3-hydroxy-3-methyl-5,8dimethoxy-1-coumarinone
C13H16O4

strictly prohibited

Confidential

Chapter 9.2 The Analysis of MixturesProblem 284
Problem 286
Problem 284
Compound
Mole %
ethanol
57
bromoethane

strictly prohibited
Compound
Mole %
benzene
24
ethyl acetate
59
dioxane
17
Compound
Mole %
ethanol
41
bromoethane
59
43
Problem 285
Compound
Mole %
benzene
15
diethyl ether
dichoromethane
December 2007
Problem 287
46
39
20

Confidential

Problem 288

strictly prohibited
Problem 290
Compound
Mole %
Compound
Mole %
benzene
13
fluorene
75
diethyl ether
22
fluorenone
25
dichoromethane
65
Compound
Mole %
4-nitroanisole
38
2-nitroanisole
62
Problem 291
Problem 289
December 2007
Compound
Mole %
benzene
23
ethyl acetate
51
dioxane
26
21

Confidential

Problem 294
Chapter 9.3 Problems in 2D NMR

Problem 292
Proton
H1
H2
H3
H4
1-propanol
Chemical Shift ()
in ppm
3.49
1.50
0.85
2.95
Problem 293
December 2007
Carbon
C1
C2
C3
Chemical Shift ()
in ppm
64.0
25.5
9.9
1-iodobutane
22
isobutanol

strictly prohibited

Confidential

strictly prohibited

Problem 295
Problem 297
1
3-heptanone
CH3
CH2
CH2
CH2
CH2
1-bromobutane
CH3
CH3
CH2
CH2
CH2
Br
Proton
Chemical Shift () in ppm
H1
0.91
H2
1.94
H4
1.97
H5
1.44
H6
1.14
H7
0.79
Carbon
H1
Chemical Shift ()
in ppm
3.39
C1
Chemical Shift ()
in ppm
33.4
H2
1.82
C2
34.7
H3
1.45
C3
21.4
H4
0.91
C4
13.2
Proton
Problem 298
1
3-octanone
CH3
CH2
-valerolactone
Proton
4
5
Chemical Shift
() in ppm
Proton
Carbon
C1
Chemical Shift
() in ppm
170.0
H2
2.08
C2
29.9
H3
1.16
C3
22.2
H4
1.08
C4
19.0
H5
3.71
C5
68.8
December 2007
CH2
CH2
CH2
CH2
CH3
Carbon
H1
Chemical Shift
() in ppm
0.92
C1
Chemical Shift
() in ppm
7.8
H2
1.92
C2
35.4
C3
209.0
Problem 296
23
H4
1.94
C4
42.1
H5
1.47
C5
23.7
H6
1.11
C6
31.7
H7
1.19
C7
22.7
H8
0.82
C8
14.0

Confidential

Problem 299
Problem 300
c
COOCH2CH3
d
diethyl diethylmalonate
CH3CH2 C
butyl ethyl ether
CH2
CH2 CH2 CH2 CH3
Ha
Chemical
Shift ()
in ppm
1.11
Hb
3.29
Cb
66.0
Hc
3.27
Cc
70.1
Ca
Chemical Shift
()
in ppm
14.0
Hd
1.52
Cd
32.1
Cb
60.8
He
1.36
Ce
19.4
Cc
171.9
Hf
0.87
Cf
13.5
Carbon
Ha
Chemical Shift
()
in ppm
1.19
Hb
4.13
Proton
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
CH3
CH2CH3
COOCH2CH3
Proton

strictly prohibited
24
Carbon
Ca
Chemical Shift
()
in ppm
15.0

Confidential

Problem 301
Problem 302
1-iodobutane
butyl butyrate
Carbon
Ha
Chemical
Shift ()
in ppm
0.75
Ca
Chemical
Shift ()
in ppm
13.9
Hb
1.19
Cb
19.5
Hc
1.40
Cc
31.2
Hd
3.97
Cd
64.0
Ce
172.8
Proton
Hf
2.08
Cf
36.2
Hg
1.52
Cg
19.0
Hh
0.79
Ch
13.9
December 2007

strictly prohibited
1-butanol
1-iodobutane
25
CH3
CH2
CH2
CH2
CH3
CH2
CH2
CH2 OH
1-butanol
H1
H Chemical
Shift ()
in ppm
2.70
H1
H Chemical
Shift ()
in ppm
3.41
H2
1.40
H2
1.27
H3
1.08
H3
1.39
H4
0.64
H4
0.84
-OH
1.95

Confidential

strictly prohibited

Problem 303
Problem 304
CH3
(E)- and (Z)-2-butene
H
C
(Z)-3-methyl-2-penten-4-ynol
C
CH2OH
C
C
H
Problem 305
Br
C
C
CH3
CH3
H8
NO2
H7
H2
H6
H3
1-nitronaphthalene
H5
CH3
C
CH3
December 2007
C
Br
26
H4
Proton
Chemical Shift () in ppm
H2
8.22
H3
7.53
H4
8.10
H5
7.95
H6
7.62
H7
7.71
H8
8.56

Confidential

strictly prohibited

Problem 306
Problem 309
COOCH2CH3
ethyl diethylmalonate
CH3
CH3CH2 C
geraniol
COOCH2CH3
H
CH3
HOCH2
Problem 307
butyl
valerate
CH3 CH2 CH2 CH2
CH2
CH2
CH2
CH3
Problem 308
CH3
nerol
CH3
H
CH3
H
December 2007
CH3
CH2OH
27

Confidential


strictly prohibited
Chapter 9.4 Analysis of NMR Spectra

Problem 310
Problem 311
Structure
Number of 1H
environments
Number of 13C
environments
CO CH2CH2CH3
CH3CH2 CO CH2CH3
CH2 CHCH2CH3
cis- CH3CH CHCH3
trans-CH3CH CHCH3
slow chairchair
fast chairchair
rigid
CH3
Cl
Br
Chemical Shifts
A = 300 Hz / 60 MHz = 5.0 ppm

M = 240 Hz / 60 MHz = 4.0 ppm
X = 120 Hz / 60 MHz = 2.0 ppm
Br
Cl
Cl
Br
Br
Br
Cl
Cl
OCH3
Problem 312
Chemical Shifts
4
Cl
December 2007
28
A = 180 Hz / 200 MHz = 0.90 ppm

M = 220 Hz / 200 MHz = 1.22 ppm
X = 300 Hz / 200 MHz = 1.50 ppm

Confidential

Problem 313
Problem 314
Spin System
Chemical Shifts

strictly prohibited
A2X3
A = 150 Hz / 400 MHz = 0.375 ppm

X = 300 Hz / 400 MHz = 0.750 ppm
Chemical Shifts
1st Order Analysis
A = 3.36 ppm = 3.36 x 60 = 202 Hz from TMS

X = 1.11 ppm = 1.11 x 60 = 67 Hz from TMS
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

Confidential
Problem 315
Spin System
Chemical Shifts
Coupling constants
1st Order Analysis

strictly prohibited

AMX
Problem 316
A = 501 Hz / 100 MHz = 5.01 ppm

M = 439 Hz / 100 MHz = 4.39 ppm
X = 408 Hz / 100 MHz = 4.08 ppm
Spin System
Chemical Shifts
JAM = 3.1 Hz
JAX = 20.1 Hz
JMX = 1.1 Hz
Coupling constants
= A - M = 501 - 439 = 62 Hz
= A - X = 501 - 408 = 93 Hz
= M - X = 439 - 408 = 31Hz
/ JAM = 62 / 3.1 = 20.0
/ JAX = 93 / 20.1 = 4.6
/ JMX = 31 / 2.1 = 14.7
1st Order Analysis
All ratios are greater than 3 so a 1st order analysis is justified.
AMX
A = 460 Hz / 60 MHz = 7.67 ppm

X = 442 Hz / 60 MHz = 7.37 ppm
M = 394 Hz / 60 MHz = 6.57ppm
JAM = 1.70 Hz
JAX = 0.85 Hz
JMX = 3.65 Hz
= A - M = 460 - 394 = 66 Hz
= A - X = 460 - 442 = 18 Hz
= M - X = 442 - 394 = 48 Hz
/ JAM = 66 / 1.7 = 38.8
/ JAX = 18 / 0.85 = 21.2
/ JMX = 48 / 3.65 = 13.2
December 2007
30

Confidential
Problem 317
Spin System
Chemical Shifts
Coupling constants
1st Order Analysis

AMX
Problem 318
Spin System
3 = 673 Hz / 100 MHz = 6.73 ppm

4 = 719 Hz / 100 MHz = 7.19 ppm
6 = 777 Hz / 100 MHz = 7.77ppm
Chemical Shifts
J34 = 8.8 Hz
J46 = 2.3 Hz
5
J36 not resolved (< 1Hz)
34 = 4 - 3 = 719 - 673 = 46 Hz
46 = 6 - 4 = 777 - 719 = 58 Hz
36 = 6 - 3 = 777 - 673 = 104 Hz
34 / J34 = 46 / 8.8 = 5.2
46 / J46 = 58 / 2.3 = 25.2
36 / J36 = 104 / <1 = >104
Coupling constants
1st Order Analysis
December 2007

strictly prohibited
AMX
A = 628 Hz / 100 MHz = 6.28 ppm

B = 527 Hz / 100 MHz = 5.27 ppm
C = 592 Hz / 100 MHz = 5.92 ppm
JAB = 2.1 Hz; JAC = 17.5 Hz; JBC = 9.9 Hz
AB = A - B = 628 - 527 = 101 Hz
AC = A - C = 628 - 592 = 36 Hz
BC = C - B = 592 - 527 = 65 Hz
AB / JAB = 101 / 2.1 = 48.1
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.
31

Confidential
Problem 319
Spin System
Chemical Shifts

strictly prohibited

AX3
Problem 320
Spin System
AX3
A = 160 Hz / 60 MHz = 2.67 ppm

X = 280 Hz / 60 MHz = 4.67 ppm
Chemical Shifts
A = 199 Hz / 100 MHz = 1.99 ppm

X = 99 Hz / 100 MHz = 0.99 ppm
Coupling constants
JAX = 5 Hz
1st Order Analysis
AX = A - X = 199 - 99 = 100 Hz
AX / JAX = 100 / 5 = 20.0
AX / JAX is much greater than 3 so a 1st order analysis is justified.
December 2007
32

Confidential
Problem 321
4 Spin System AMX2
Chemical Shifts
December 2007

Problem 322
A = 340 Hz / 60 MHz = 5.67 ppm

M = 240 Hz / 60 MHz = 4.00 ppm
X = 100 Hz / 60 MHz = 1.67 ppm
4 Spin System AM2X
Chemical Shifts
33

strictly prohibited
A = 110 Hz / 60 MHz = 1.83ppm

M = 200 Hz / 60 MHz = 3.33 ppm
X = 290 Hz / 60 MHz = 4.83 ppm

Confidential
Problem 323 4 Spin System
Chemical Shifts
Coupling constants
1st Order Analysis

strictly prohibited

AM2X
A = 646 Hz / 100 MHz = 6.46 ppm

M = 510 Hz / 100 MHz = 5.10 ppm
X = 395 Hz / 100 MHz = 3.95 ppm
Chemical Shifts
JAM = 3 Hz; JAX = 16 Hz; JMX = 5 Hz;
AX = A - X = 646 - 395 = 251 Hz

AM = A - M = 646 - 510 = 136 Hz
MX = M - X = 510 - 395 = 115 Hz
Coupling constants
1st Order Analysis
AX / JAX = 251 / 16 = 15.7

AM / JAM = 136 / 3 = 45.3
MX / JMX = 115 / 5 = 23.0
A2MX
A = 279 Hz / 100 MHz = 2.79 ppm

M = 149 Hz / 100 MHz = 1.49 ppm
X = 39 Hz / 100 MHz = 0.39 ppm
JAM = 4.5 Hz; JAX = 7.5 Hz; JMX = 11.0 Hz;
AX = A - X = 279 - 39 = 240 Hz
AM = A - M = 279 - 149 = 130 Hz
MX = M - X = 149 - 39 = 110 Hz
AX / JAX = 240 / 7.5 = 32.0

AM / JAM = 130 / 4.5 = 28.9
MX / JMX = 110 / 11 = 10.0
All ratios are significantly greater than 3 so a 1st order analysis is justified.
December 2007
34

Confidential
Chemical Shifts
Coupling constants
1st Order Analysis

strictly prohibited

AMX2
A = 302 Hz / 100 MHz = 3.02 ppm

M = 160 Hz / 100 MHz = 1.60 ppm
X = 37 Hz / 100 MHz = 0.37 ppm
Chemical Shifts

AX = A - X = 302 - 37 = 265 Hz
AM = A - M = 302 - 160 = 142 Hz
MX = M - X = 160 - 37 = 123 Hz
Coupling constants
1st Order Analysis
AX / JAX = 265 / 5.0 = 53.0

AM / JAM = 142 / 12.0 = 11.8
MX / JMX = 123 / 8.0 = 15.4
A2M2X
A = 1000 Hz / 200 MHz = 5.0 ppm

M = 500 Hz / 200 MHz = 2.5 ppm
X = 100 Hz / 200 MHz = 0.5 ppm
AX = A - X = 1000 - 100 = 900 Hz
AM = A - M = 1000 - 500 = 500 Hz
MX = M - X = 500 - 100 = 400 Hz
AX / JAX = 900 / 7.0 = 128.6

AM / JAM = 500 / 3.0 = 166.7
MX / JMX = 400 / 10.0 = 40.0
December 2007
35

Confidential
Chemical Shifts
Coupling constants
1st Order Analysis

AMX3
A = 710 Hz / 100 MHz = 7.10 ppm

M = 585 Hz / 100 MHz = 5.85 ppm
X = 192 Hz / 100 MHz = 1.92 ppm
AX = A - X = 710 - 192 = 518 Hz
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

strictly prohibited

Confidential

strictly prohibited

ADMX3
1st Order Analysis
AD = A AM = A AX = A DM = D DX = D MX = M-
D = 956 - 695 = 261 Hz

M = 956 - 619 = 337 Hz
X = 956 - 205 = 751 Hz
M = 695 - 619 = 76 Hz
X = 695 - 205 = 490 Hz
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
H
Chemical Shifts
Coupling constants
December 2007
A = 956 Hz / 100 MHz = 9.56 ppm;

D = 695 Hz / 100 MHz = 6.95 ppm;
M = 619 Hz / 100 MHz = 6.19 ppm;
X = 205 Hz / 100 MHz = 2.05 ppm;
37
H
C
JAD= < 1 Hz; JAM = 8.2 Hz; JAX = < 1 Hz;

JDM = 15.8 Hz; JDX = 6.9 Hz; JMX = 1.6Hz;
C
CH3
X

Confidential
Problem 329

5 Spin System AMX3
Chemical Shifts
Problem 330

strictly prohibited
3 Spin System A2X
A = 80 Hz / 60 MHz = 1.33 ppm

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
systems. The measured coupling
constant is 7.7 Hz which is in the
range for protons which are ortho to
each other. Compound 4 is the
correct answer.
December 2007
38
NH2
Br
Br
HA
HA
HX

Confidential

strictly prohibited

Problem 331
Problem 332
All of the protons in the 1H spectrum 1,5-dichoronaphthalene have protons
which are ortho to them. This means that every proton must have at least
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
1,5-dichloronaphthalene.
The spectrum is obtained after D2O exchange so the carboxylic acid and
phenolic protons will not be present and the spectrum only contains the
aromatic and vinylic protons.
The spectrum shows 6 distinct resonances therefore compounds 5 and 6
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
given below.
The proton at about 7.1 shows no large coupling (> 7 Hz), this means
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
Cl
HX
HA
HA
Cl
HX
HX
Cl
HA
2,7-dichloronaphthalene
December 2007
39
HM
Cl
HX
HM
HA
2,6-dichloronaphthalene

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benzyl methyl ketone

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ethylene glycol diacetate

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ethylene glycol dipropionate

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p-anisyl t-butyl ketone

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cyclopropyl methyl ketone

cyclopropane carboxylic acid

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vinyl 2-chloroethyl ether

allyl p-anisyl thioether

p-tolyl methyl sulfoxide

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2,4,5-trichlorophenoxyacetic acid (2,4,5-T)

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2-furyl t-butyl ketone

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