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ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman
Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited
Solutions Manual
December 2007 – last updated April 2013
1
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1
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ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 5
BrCH2 CH2Br
9
O
CH3
C
Cl2CH CH3
13
OH OH C
CH3
CH3 CH3
2
2-butanone
1,2-dibromoethane
pinacol
1,1-dichloroethane
C4H8O
C2H4Br2
C6H14O2
C2H4Cl2
CH3CH2
OH
6
10
O CH3
O
O
O
14
CH3 H
CH3
CH3 OH
O
propionic acid
1,2-butanedione (biacetyl) C4H6O2
C3H6O2 O
3 CH3
4
O
CH2CH3
7
CH2C
N
CH2C
N
11
1,4-cyclohexanedione
2-propanol
C6H8O2
C3H8O
O
15
CH3 H
CH3 Br
ethyl acetate
succinonitrile
cyclopentanone
2-bromopropane
C4H8O2
C4H4N2
C5H8O2
C3H7Br
CH3O
CH2CH3 O
8
12
CH3 CH3 CH3 C
C
CH3CH2 I
16
Cl
Cl
CH3
CH3 CH3
methyl propionate
2,2,3,3-tetramethylbutane
iodoethane
1,4-dichlorobutane
C4H8O2
C8H18
C2H5I
C4H8Cl2
December 2007 – last updated April 2013
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17
Br
ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 21
Br
Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited
H2N
25
COOH
N
CH2C
29
CH2 C CH3 O
1,3-dibromopropane
4-aminobutyric acid
benzyl cyanide
benzyl methyl ketone
C3H6Br2
C4H9NO2
C8H7N
C9H10O
18
19
Br
22
Cl
26
OCH3
CH2NH2
30
O
1-bromo-3-chloropropane
anisole
benzylamine
propiophenone
C3H6BrCl
C7H8O
C7H9N
C9H10O
Br
N
C
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
H
COO
24
OH
CH2Br
32
O
H CH3
-
alanine
benzyl bromide
1-phenylethanol
butyrophenone
C3H7NO2
C7H7Br
C8H10O
C10H12O
December 2007 – last updated April 2013
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ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman O
33
O O
34
37
O
Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited
41
N
CH3
O
C
O
45
C
O
CH3
CH3
H CH3 O
O
H
O
t-butyl acetoacetate
dibenzylamine
propionic anhydride
1,1-diacetoxyethane
C8H14O3
C14H15N
C6H10O3
C6H10O4
CH3CH2 O C H
38
42
CH3
O
N
N
CH3
CH3
O
N,N,N,N-tetramethyl-1,2ethanediamine C6H16N2
C3H6O2
35
O
O
39
H
O
COOCH3 CH3
diethyl oxalate
dimethyl methylmalonate
C6H10O4
C6H10O4 O
43 CH3
O
O
O
47
CH3 O
CH3
CH3
O
O
O
C C
CH3OOC
O
CH3
ethyl formate
46
O
C O
OCH3
benzil
2,5-hexanedione
ethylene glycol diacetate
methyl acetyllactate
C14H10O2
C6H10O2
C6H10O4
C6H10O4
36
O
40 CH3CH2O
44 CH3O
OCH2CH3
48
O OCH3 O
O O
C
C
O
O
1,2-diphenylethane
diethyl carbonate
dimethyl succinate
diethyl succinate
C14H14
C5H10O3
C6H10O4
C8H14O4
December 2007 – last updated April 2013
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ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman
O
49
O
O
53 O
57
CHCl2
H3C
CH3
H3C
CH3
61
OCH3 OCH3 OCH3
ethylene glycol dipropionate
α,α-dichlorotoluene
1,2,3-trimethoxybenzene
durene
C8H14O4
C7H6Cl2
C9H12O3
C10H14
CH3
50
51
O
O
C
C
O
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
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65
ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 69
CH3
CH3
CH3
1,2,3,4,5,pentamethylcyclopentadiene C10H16
66
CH3
CH3
NH2
3-hydroxybutanone (acetoin) C4H8O2
70
74
NH2
HOOC COOH CH3 CH3
3,3-dimethylglutaric acid C7H12O4
78
HOOC
COOH
O
acetamide
4-hydroxy-4-methyl-2pentanone C6H12O2
C2H5NO O HO
CH3 CH3
2-methyl-2-butanol (t-amyl alcohol) C5H12O
HO
O
67
77
OH CH3
O
CH3
H
73
OH CH3
CH3
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71 O
O
hexylamine
2,2-dimethylpentanedioc acid C7H12O4
C6H15N
75
CH3
O CH3CH2
O
CH3
O
79
CH3 CH3 CH3
Br
N
N CH3 O
ethyl glycolate
isobutyl acetate
ethyl 2-bromopropionate
tetramethylurea
C4H8O3
C6H12O2
C5H9O2Br
C5H12N2O
68
72
O CH3CH2O
C
N
OCH3
76
COOH
O
80
O
O
OCH3
ethyl cyanoacetate
3,3-dimethylbutyric acid
4,4-dimethoxy-2-butanone
1,3-dioxan
C5H7NO2
C6H12O2
C6H12O3
C4H8O2
December 2007 – last updated April 2013
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81
ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman Br
85
O
89 OH
O
93
CH2
HO
O
H
O
1,4-dioxan
2-bromohexanoic acid
2-methylbut-3-en-2-ol
dibutyl ether
C4H8O2
C6H11O2Br
C5H10O
C8H18O
82
O
CN
86
O
O
90
H
-
C H OH O
O
94
+
NH3
CH3
CN
O O
83
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O
18-crown-6
2-ethylmalononitrile
threonine
butylbenzene
C12H24O6
C5H6N2
C4H9NO3
C10H14
H2C C
CH2Cl
87
91
CN
Br
95
Cl
C(CH3)3
2,3-dichloropropene
3-methylbutyronitrile
1-bromo-3-phenylpropane
t-butylbenzene
C3H4Cl2
C5H9N
C9H11Br
C10H14
O
84 Cl
O
88
H2N
C
C
92
H
NO2
96
CH3
4-chlorobutyl acetate
5-amino-1-pentyne
1-nitropropane
sec-butylbenzene
C6H11O2Cl
C5H9N
C3H7NO2
C10H14
December 2007 – last updated April 2013
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ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 101
C(CH3)3
105
O Cl
C
109
O CH3O
C
CH3
HO
CH2OCH3
CH3
neopentylbenzene
p-chloroacetophenone
4-methoxyacetophenone
4-methoxymethylphenol
C11H16
C8H7OCl
C9H10O2
C8H10O2
98
CH2Cl
102
106
O CH3
CH3
C
110
O C
O
CH3
CH3 N C
N
Cl
CH3
4-(n-butyl)-α-chlorotoluene
p-toluyl chloride
p-cresyl acetate
4-dimethylaminobenzonitrile
C11H15Cl
C8H7OCl
C9H10O2
C9H10N2
99
O
103
CH3O
107
COOH
O H3C
111
C
CH3 Br
N CH3
OCH3
4-methyl-4-phenyl-2-pentanone C12H16O
100
O Br
C
104
p-anisic acid
methyl p-toluate
p-bromo-N,N-dimethylaniline
C8H8O3
C9H10O2
C8H10NBr
CH2O C
CH3
108
CH3O
CH2OH
O
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 – last updated April 2013
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113
O (H3C)3C
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ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 117
121
O
O C CH3
CH3CH2O
H
C
NH2
125
N
O
NO2
114
115
o-nitrobenzaldehyde
ethyl p-aminobenzoate
C12H16O2
C7H5NO3
C9H11NO2
(CH3)3C
C OCH3 O
H C
122
OCH3
CH3CH2O
C
O
NH2
p-ethoxybenzamide
C12H16O2
C8H8O2
C9H11NO2
119
p-ethoxyacetanilide (phenacetin) C10H13NO2 H
126 HO
N
C CH3 O
4-methoxybenzaldehyde
NO2
O2N
C
C
H
123
p-hydroxyacetanilide (paracetamol) C8H9NO2
127
O CH3 C
CH3
O
O
methyl 4-t-butylbenzoate
CH3O
C
CH3CH2O
4-t-butylphenyl acetate
118
H
O C
NH2
O
O
116
H
p-nitroanisole
4-nitrophenylacetylene
4-aminoacetophenone
ethyl p-ethoxybenzoate
C7H7NO3
C8H5NO2
C8H9NO
C11H14O3
C
NO2
120
124
O C
O
O
C H3C
OH
O CH3
NH C CH3
CH3O
O
OCH3
O
p-nitrobenzaldehyde
4-acetoxybenzoic acid
4-methylacetanilide
C7H5NO3
C9H8O4
C9H11NO
December 2007 – last updated April 2013
128
9
methyl (p-methoxyphenyl)propionionate C11H14O3
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129
H
N
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ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 133
O
O
137
O C
O
O
O C
141
H
O
O
CH3
C O
130
N-isopropylbenzylamine
hydroquinone dipropionate
C10H15N
C12H14O4
OCH3 O O
134
C
CH3
131
NCO
O
cyclopropyl methyl ketone C5H8O
142 CH3O
C
O
methyl 2-methoxy-2phenylacetate C10H12O3
138
O
O
1,3-dihydroxyphenyl dipropionate C12H14O4
C
C
H
OCH3
OH
C
O O
O
diethyl terephthalate
dimethyl o-phthalate
cyclopropane carboxylic acid
C12H14O4
C10H10O4
C4H6O2
O
135
C C
139
O
O O
143
H C O
O
132
phenyl isocyanate
diethyl o-phthalate
cycloheptanone
benzoylcylopropane
C7H5NO
C12H14O4
C7H12O
C10H10O
OCH3
136
O
OCH3 H
O
C
140
O C
144
H
CH2
C
O
OCH2CH3
O
phenylacetaldehyde dimethyl acetal C10H14O2
December 2007 – last updated April 2013
diethyl isophthalate
cycloheptatriene
ethyl cyclobutanecarboxylate
C12H14O4
C7H8
C7H12O2
10
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145
C(CH3)3
O
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ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 149
153
157
CH3
(CH3)3C
O
OH
O
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
H
O
CH3
154
158
Br
Br
N H3C
O
N-methylacetamide
H2N NH2
Br
(p-cresyl)methyl phenyl ketone C15H14O2
C3H7NO
147
OH
O
CH3
151
CH3
O
2-bromophenol
3,5-dibromocumene
C6H5OBr
C9H10Br2
155
159
O
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
H
O
1,5-diaminopentane ** C5H14N2
December 2007 – last updated April 2013
1,3-bis(trichloromethyl)benzene C8H4Cl6
11
2,6-dibromoaniline
piperonal
C6H5NBr2
C8H6O3
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161
162
ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 165
CH3 CH3
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169
O
NO2
173
O
3-nitro-o-xylene
2-cyclohexene-1-one
indane
α-tetralone
C8H9NO2
C6H8O
C9H10
C10H10O
Cl
CH3
Cl
Cl
166
170
O
174
O
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
β-tetralone
C11H12O
C10H10O
175
O
H
164
CH3
2,4,5-trichloroaniline
1-acetyl-1-cylohexene
1-indanone
9-methylfluorene
C6H4NCl3
C8H12O
C9H8O
C14H12
CH3O I
OCH3 I
168
172
CH3
176 O
CH3
O O
CH3
4,6-diiodo-1,3dimethoxybenzene C8H8O2I2
December 2007 – last updated April 2013
4-methylpent-3-en-2-one (mesityl oxide) C6H10O
12
2-indanone
fluorenone
C9H8O
C13H8O
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177
O CH3
CH3
ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 181
CH3CH2
O
O
O
183
N
CH3 HO
C
C
C
C6H10O3
December 2007 – last updated April 2013
CH3
C C C CH2CH3 OH
H
187
C
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
H
C
mevalonic lactone
C3H6Br2
CH2
CH CH2
OH
OH OH
CH3
CH3
184
O
1,2-dibromopropane
190
CH3
CH3
2,5-dimethyl-3-hexyne2,5-diol C8H14O2
C
O
(Z)-1-methoxybut1-en-4-yne C5H6O
CH3
CH3
O
OH
CH3
CH2Br
H
1,2,2,6,6-pentamethylpiperidine C10H21N
2,2-dimethylglutaric anhydride C7H10O3
180
CH3
CH3
CH3 O
Br
H
186 CH3 CH3
3,3-dimethylglutaric anhydride C7H10O3 CH3
O
182
O
179
OCH3
C
4-ethyl-4-methyl-2,6piperidinedione C8H13NO2
O
CH3
N
189
H
2,4,6-trimethyl1,3,5-trioxane C6H12O3
CH3
H
C
CH3
O
H
185
CH3
O
178
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H
1-phenyl-1,3-pentadiyne
glycerol
C11H8
C3H8O3
COOCH3
188
192
OH CH3
O
C
H
HC
(Z)-3-methylpent-2en-4-ynal C6H6O
C NH2
CH
methyl 4-amino-3,5diethynylbenzoate C12H9NO2
13
CH3 H
2-butanol C4H10O
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193
ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 197
O
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S
NH2
O
201
O S
Cl
205
H
NH2
O
O
p-aminobenzenesulfonamide C6H8N2O2S
dibenzyl sulfoxide C14H14OS
vinyl 2-chloroethyl ether
cinnamaldehyde
C4H7OCl
C9H8O
198 194
O
S
202
S
206
N
O
COOH
O
CH2OH
CH3
O
(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
H
H
CH
C(CH3)3
O
H
ethyl p-toluenesulfonate
allyl p-anisyl thioether
C9H12O3S O
200
O
(E)-3-chloro-4,4-dimethyl-1phenyl-1-pentene C13H17Cl
phenylacetaldeyde ethylene glycol acetal C10H12O2
C10H12OS O
CH3
O CH2
CH3O
O
196
203
S
O S
O
CH2CH2O 4
S CH3
204
S
CH(CH3)2
208
H H
O
O
CH3
Br
CH3
p-tolyl methyl sulfoxide C8H10OS
December 2007 – last updated April 2013
(E)-1-phenyl-4-methyl-1penten-3-one C12H14O
tetraethylene glycol ditosylate C22H30O9S2
14
(Z)-β-bromostyrene C8H7Br
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209
ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman H
213
H NO2
Br
217
C
Cl
Cl
1,1-di-(p-chlorophenyl)-2,2,2trichloroethane (DDT) C14H9Cl5
(E)-p-nitro-β-bromostyrene C8H6BrNO2 OH
O
Cl
214
Cl
3-benzyloxy-1-propanol
COOH
211
215
O2N
CH3O
O
219
Br Br
216
CH3O
5,6-dimethoxy-2coumaranone C10H10O4
December 2007 – last updated April 2013
malonaldehyde dimethyl acetal C7H16O4 OCH2CH3
222
H
CN
CH3
H
Cl
OCH2CH3
O
OCH3
O CH2
CH2 HO
OCH3
C
H
CH2 O CH2
methyl (E)-3-methylacrylate
1,3-dibenzylglycerol
C5H8O2
C17H20O3
220
CH3
2-chloroacetaldehyde diethylacetal C6H13O2Cl
223
224
O CH3O
OCH3
OCH2CH3
O
H
methyl 2,3-dibromo-3(p-nitrophenyl)propionate C10H9NO4Br2
C9H8O4
CH3O
OCH3 OCH3
4-cyano-2,2dimethylbutyraldehyde C7H11NO
O
homophthallic acid
221
O
COOH
212
218
COOH
2,4,5-trichlorophenoxyacetic acid (2,4,5-T) C8H5O3Cl3
C10H14O2
OCH2CH3
diethyl isopropylidenemalonate C10H16O4
O
Cl
O CH3 CH3
CCl3
H
210
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N CN
OCH3
2,3-di-(p-anisyl)butyronitrile
2,5-dimethyl-2,4-hexadiene
pyridine
C18H19NO2
C8H14
C5H5N
15
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ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman O
225
N
H3C
229
233
O
CH3
C
237
C O
O
C H
CH(CH3)2
N
C
O2N
CH(CH3)2
S
O
C O
4-picoline
isopropyl nicotinate
citraconic anhydride
C6H7N
C9H11NO2
C5H4O3
226
CH3
230
N
227
234 CH3
N
2-(5-nitrothienyl) isopropyl ketone C8H9NO3S
238 COOH
O
NH2
H
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
O
N
239 S
O
3-picoline
4-methylpyrimidine
2-furyl t-butyl ketone
benzothiophene
C6H7N
C5H6N2
C9H12O2
C8H6S
228
232
O C
236
H O
CH3
O2N
240 S
NO2
N
N H
3-acetylpyridine
styrene epoxide
2,4-dinitrothiophene
2,3,4,9-tetrahydrocarbazole
C7H7NO
C8H8O
C4H2N2O4S
C12H13N
December 2007 – last updated April 2013
16
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241
ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 245
CH3
249
O
O
Copyright: Copying, duplicating or distributing these solutions, in any form, is strictly prohibited
O
N CH3
α-angelicalactone
octahydroanthracene
N-methylmorpholine
C5H6O2
C14H18
C5H11NO
OH
253
N(CH3)2
HO
N,N-dimethyl-2,3-dihydroxy1-propylamine C5H13NO2
O
242
246
O
CH3
O
O
N OH
CH3
anthraquinone
cyclopentanone oxime
pseudoephedrine
C14H8O2
C5H9NO
C10H15NO
247
OH
251
H
255
N
O
N H
244
H
CH3
O
2-methyltetrahydrofuran-3-one C5H8O2
243
254
N
H O
OH
250
C(CH3)3
butyrolactone
dodecahydrotriphenylene
cyclohexanone oxime
t-butylformamide
C4H6O2
C18H24
C6H11NO
C5H11NO
CH3 CH3
O
O
CH3
248
N
CH3
tetramethyl-1,3cyclobutanedione C8H12O2
December 2007 – last updated April 2013
O
252
256
H HS CH2 CH
H
N
COOH
C O
triphenylene
ε-caprolactam
N-acetylcysteine
C18H12
C6H11NO
C5H9NO3S
17
CH3
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257
HO
ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman O
261
OH
265
269
OH CH3
CH3
H
CH CH2NH CH3
HO
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O HO
H OH
CH3
H
C
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 CH2 CH
OCH3
266
OCH2CH3 CH
270
OH
OCH2CH3
H HO
O OCH2CH3 CH3
N H O
tryptophan
acrolein diethyl acetal
eugenol
N-acetyltyrosine ethyl ester
C11H12N2O2
C7H14O2
C10H12O2
C13H17NO4
259
263
H N
S
O
C
C
H
271 O
C (CH3)3C
O
HO C CH2CH2 CH COOH O NH2
C
C
CH3
N-acetylhomocysteine thiolactone C6H9NO2S
260
Cl
H
267
NH2
E -1-chloro-4-(4-tbutylphenyl)but-1-en-3-yne C14H15Cl
allylamine C3H7N
264
268
H
HO O
OH CH3
N
C4H6O
272
O
H
2,5-dihydrofuran
O
O
glutamic acid
adamantine
N-acetylaspartic acid
2,3-dihydrofuran
C5H9NO4
C10H16
C6H9NO5
C4H6O
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COOH
273
ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 277
O
281
Cl
O
N C
COOH
O CH2CH3
2,3-naphthalenedicarboxylic acid C12H8O4
274
OCH3
ethyl 4-piperidone-Ncarboxylate C8H13NO3
2-chloronaphthalene C10H7Cl
278
COOH CH3 N C O H
282
NO2
sec-butylbenzene
1-methoxy-4-nitronaphthalene C11H9NO3 CH3
275
N-acetyl-2-amino-4-phenyl(E)-but-2-enoic acid C12H13NO3
C10H14
279
CH3 O
283
CH3O
O
N H
CH3
CH3
OCH3
N-(1-methyl-1-phenylethyl)butyramide C12H17NO
1,5-dimethylnaphthalene C12H12
276
CH3
280 CH3
1,3-dimethylnaphthalene C12H12
December 2007 – last updated April 2013
O OCH2CH3 O
OCH2CH3
diethyl 2-(1,1dimethylheptyl)malonate C16H30O4
19
OH
3-hydroxy-3-methyl-5,8dimethoxy-1-coumarinone C13H16O4
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ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman
Chapter 9.2 – The Analysis of MixturesProblem 284
Problem 286
Problem 284 Compound
Mole %
ethanol
57
bromoethane
Copyright: Copying, duplicating or distributing these solutions, in any form, is 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 – last updated April 2013
Problem 287
46
39
20
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ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman
Problem 288
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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 Compound
Mole %
benzene
23
ethyl acetate
51
dioxane
26
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ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman
Chapter 9.3 – Problems in 2D NMR Problem 292 Proton H1 H2 H3 H4
1-propanol
Chemical Shift (δ) in ppm 3.49 1.50 0.85 2.95
Problem 293
Problem 294
Carbon C1 C2 C3
Chemical Shift (δ) in ppm 64.0 25.5 9.9
1-iodobutane
December 2007 – last updated April 2013
22
isobutanol
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ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman
Problem 295
Problem 297 1
3-heptanone
CH3
2
3
4
5
CH2
C
CH2
CH2
6
CH2
4
7
1-bromobutane
CH3
3
CH3
2
CH2
1
CH2
CH2
Br
O
Proton
Chemical Shift (δ) in ppm
H1
0.91
H2
1.94
H4
1.97
H5
1.44
H6
1.14
H7
0.79
Proton
Carbon
H1
Chemical Shift (δ) in ppm 3.39
C1
Chemical Shift (δ) in ppm 33.4
H2
1.82
C2
34.7
H3
1.45
C3
21.4
H4
0.91
C4
13.2
Problem 298 1
3-octanone
2
CH3
CH2
3
C
4
5
CH2
CH2
6
CH2
7
CH2
8
CH3
O 3
5
δ-valerolactone
Proton
2
4
Problem 296
Chemical Shift (δ) in ppm
Proton
O
O
Carbon C1
Chemical Shift (δ) in ppm 170.0
H2
2.08
C2
29.9
H3
1.16
C3
19.0
H4
1.08
C4
22.2
H5
3.71
C5
68.8
December 2007 – last updated April 2013
Carbon
H1
Chemical Shift (δ) in ppm 0.92
C1
Chemical Shift (δ) in ppm 7.8
H2
1.92
C2
35.4
C3
209.0
1
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
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ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman
Problem 299
Problem 300 c
b
a
a
COOCH2CH3 d
diethyl diethylmalonate
e
f
g
CH3CH2 C
butyl ethyl ether
h
CH2
c
O
CH2
d
e
f
CH2 CH2
CH3
Ha
Chemical Shift (δ) in ppm 1.11
Hb
3.29
Cb
66.0
Hc
3.27
Cc
70.1
Ca
Chemical Shift (δ) 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
i
Carbon
Ha
Chemical Shift (δ) in ppm 1.19
Hb
4.13
Proton
j
k
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 – last updated April 2013
CH3
b
CH2CH3
COOCH2CH3
Proton
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24
Carbon
Ca
Chemical Shift (δ) in ppm 15.0
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ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman
Problem 301
Problem 302
1-iodobutane
butyl butyrate
Proton
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Carbon
Ha
Chemical Shift (δ) in ppm 0.75
Ca
Chemical Shift (δ) 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
Hf
2.08
Cf
36.2
Hg
1.52
Cg
19.0
Hh
0.79
Ch
13.9
December 2007 – last updated April 2013
1-butanol
1-iodobutane
25
1
4
3
2
1
CH3
CH2
CH2
CH2
4
3
2
1
CH3
CH2
CH2
CH2 OH
I
1
1-butanol
H1
H Chemical Shift (δ) in ppm 2.70
H1
H Chemical Shift (δ) 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
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ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman
Problem 303
Problem 304 CH3
(E)- and (Z)-2-butene
H C
(Z)-3-methyl-2-penten-4-ynol
C CH2OH
C C H
H
Problem 305
Br C
C CH3
CH3
H8
NO2 H2
H7
1-nitronaphthalene H3
H6 H5
H
CH3 C
CH3
December 2007 – last updated April 2013
C Br
26
H4
Proton
Chemical Shift (δ) in ppm
H2
8.22
H3
7.53
H4
8.10
H5
7.95
H6
7.62
H7
7.71
H8
8.56
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ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman
Problem 306
Problem 309 COOCH2CH3
CH3
ethyl diethylmalonate
CH3CH2 C
geraniol
COOCH2CH3
H CH3 HOCH2
Problem 307
butyl valerate
CH3 CH2 CH2 CH2
O
C
CH2
CH2
CH2
CH3
O
Problem 308 CH3
CH3
H
nerol
CH3 H
December 2007 – last updated April 2013
CH3
H
CH2OH
27
H
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ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman
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Chapter 9.4 – Analysis of NMR Spectra Problem 310
Problem 311
Structure
Number of 1H environments
Number of 13C environments
CO CH2CH2CH3
4
5
CH3CH2 CO CH2CH3
2
3
CH2 CHCH2CH3
5
4
cis- C H 3 C H C H C H 3
2
2
trans- CH3CH CHCH3
2
2
1
1
3
4
2
3
3
4
1
2
2
4
5
7
slow chairchair
2
1
fast chairchair
1
1
rigid
7
4
CH3
Cl
Chemical Shifts
Br
δA = 300 Hz / 60 MHz = 5.0 ppm δM = 240 Hz / 60 MHz = 4.0 ppm δX = 120 Hz / 60 MHz = 2.0 ppm
Br Cl
Cl
Br
Br
Br
Cl
Cl
Problem 312
OCH3
Chemical Shifts
H Cl
December 2007 – last updated April 2013
28
δA = 180 Hz / 200 MHz = 0.90 ppm δM = 220 Hz / 200 MHz = 1.10 ppm δX = 300 Hz / 200 MHz = 1.50 ppm
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ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman
Problem 313
Problem 314 Spin System
Chemical Shifts
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A2X3
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
∆νAX = νA - νX = 202 - 67 = 135 Hz ∆νAX / JAX = 135 / 7 = 19.3 st
This ratio is much greater than 3 so a 1 order analysis is justified.
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29
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Problem 315
Spin System
Chemical Shifts
Coupling constants
1st Order Analysis
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ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman AMX
Problem 316
Spin System
AMX
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
JAM = 3.1 Hz JAX = 20.1 Hz JMX = 1.1 Hz
δA = 460 Hz / 60 MHz = 7.67 ppm δX = 442 Hz / 60 MHz = 7.37 ppm δM = 394 Hz / 60 MHz = 6.57ppm
Coupling constants
JAM = 1.70 Hz JAX = 0.85 Hz JMX = 3.65 Hz
1st Order Analysis
∆νΑΜ = νA - νM = 460 - 394 = 66 Hz ∆νΑΞ = νA - νX = 460 - 442 = 18 Hz ∆νΜΞ = νM - νX = 442 - 394 = 48 Hz ∆νΑΜ / JAM = 66 / 1.7 = 38.8 ∆νΑΞ / JAX = 18 / 0.85 = 21.2 ∆νΜΞ / JMX = 48 / 3.65 = 13.2
∆νΑΜ = νA - νM = 501 - 439 = 62 Hz ∆νΑΞ = νA - νX = 501 - 408 = 93 Hz ∆νΜΞ = νM - νX = 439 - 408 = 31Hz ∆νΑΜ / JAM = 62 / 3.1 = 20.0 ∆νΑΞ / JAX = 93 / 20.1 = 4.6 ∆νΜΞ / JMX = 31 / 2.1 = 14.7 st
All ratios are greater than 3 so a 1 order analysis is justified.
st
All ratios are greater than 3 so a 1 order analysis is justified.
December 2007 – last updated April 2013
30
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Problem 317
Spin System
ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman
AMX
Chemical Shifts
δ3 = 673 Hz / 100 MHz = 6.73 ppm δ4 = 719 Hz / 100 MHz = 7.19 ppm δ6 = 777 Hz / 100 MHz = 7.77ppm
Coupling constants
3
1st Order Analysis
∆ν34 = ν4 - ν3 = 719 - 673 = 46 Hz ∆ν46 = ν6 - ν4 = 777 - 719 = 58 Hz ∆ν36 = ν6 - ν3 = 777 - 673 = 104 Hz ∆ν34 / J34 = 46 / 8.8 = 5.2 ∆ν46 / J46 = 58 / 2.3 = 25.2 ∆ν36 / J36 = 104 / <1 = >104
Problem 318
J34 = 8.8 Hz J46 = 2.3 Hz 5 J36 not resolved (< 1Hz)
Spin System
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AMX
Chemical Shifts
δA = 628 Hz / 100 MHz = 6.28 ppm δB = 527 Hz / 100 MHz = 5.27 ppm δC = 592 Hz / 100 MHz = 5.92 ppm
Coupling constants
JAB = 2.1 Hz; JAC = 17.5 Hz; JBC = 9.9 Hz
1st Order Analysis
∆νAB = νA - νB = 628 - 527 = 101 Hz ∆νAC = νA - νC = 628 - 592 = 36 Hz ∆νBC = νC - νB = 592 - 527 = 65 Hz ∆νAB / JAB = 101 / 2.1 = 48.1 ∆νAC / JAC = 36 / 17.5 = 2.1 ∆νBC / JBC = 65 / 9.9 = 6.6
4
st
All ratios are greater than 3 so a 1 order analysis is justified.
December 2007 – last updated April 2013
st
2 out of 3 ratios are greater than 3 so this is borderline 1 order. The main st st deviation from 1 order is that intensities are severely distorted - a 1 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
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Problem 319
Spin System
Chemical Shifts
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ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman AX3
Problem 320
Spin System
AX3
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
∆νAX = νA - νX = 199 - 99 = 100 Hz ∆νAX / JAX = 100 / 5 = 20.0
∆νAX / JAX is much greater than 3 so a 1 order analysis is justified. st
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Problem 321
ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman
4 Spin System AMX2
Chemical Shifts
Problem 322
δA = 340 Hz / 60 MHz = 5.67 ppm δM = 240 Hz / 60 MHz = 4.00 ppm δX = 100 Hz / 60 MHz = 1.67 ppm
December 2007 – last updated April 2013
4 Spin System AM2X
Chemical Shifts
33
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δA = 110 Hz / 60 MHz = 1.83ppm δM = 200 Hz / 60 MHz = 3.33 ppm δX = 290 Hz / 60 MHz = 4.83 ppm
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Problem 323 4 Spin System
Chemical Shifts
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ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman AM2X
Problem 324 4 Spin System
δA = 646 Hz / 100 MHz = 6.46 ppm δM = 510 Hz / 100 MHz = 5.10 ppm δX = 395 Hz / 100 MHz = 3.95 ppm
Coupling constants
JAM = 3 Hz; JAX = 16 Hz; JMX = 5 Hz;
1st Order Analysis
∆νAX = νA - νX = 646 - 395 = 251 Hz ∆νAM = νA - νM = 646 - 510 = 136 Hz ∆νMX = νM - νX = 510 - 395 = 115 Hz ∆νAX / JAX = 251 / 16 = 15.7 ∆νAM / JAM = 136 / 3 = 45.3 ∆νMX / JMX = 115 / 5 = 23.0
A2MX
Chemical Shifts
δA = 279 Hz / 100 MHz = 2.79 ppm δM = 149 Hz / 100 MHz = 1.49 ppm δX = 39 Hz / 100 MHz = 0.39 ppm
Coupling constants
JAM = 4.5 Hz; JAX = 7.5 Hz; JMX = 11.0 Hz;
1st Order Analysis
∆νAX = νA - νX = 279 - 39 = 240 Hz ∆νAM = νA - νM = 279 - 149 = 130 Hz ∆νMX = νM - νX = 149 - 39 = 110 Hz ∆νAX / JAX = 240 / 7.5 = 32.0 ∆νAM / JAM = 130 / 4.5 = 28.9 ∆νMX / JMX = 110 / 11 = 10.0
st
All ratios are significantly greater than 3 so a 1 order analysis is justified.
st
All ratios are significantly greater than 3 so a 1 order analysis is justified.
December 2007 – last updated April 2013
34
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Problem 325 4 Spin System
Chemical Shifts
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ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman AMX2
Problem 326 5 Spin System
δA = 302 Hz / 100 MHz = 3.02 ppm δM = 160 Hz / 100 MHz = 1.60 ppm δX = 37 Hz / 100 MHz = 0.37 ppm
Coupling constants
JAM = 12.0 Hz; JAX = 5.0 Hz; JMX = 8.0 Hz;
1st Order Analysis
∆νAX = νA - νX = 302 - 37 = 265 Hz ∆νAM = νA - νM = 302 - 160 = 142 Hz ∆νMX = νM - νX = 160 - 37 = 123 Hz ∆νAX / JAX = 265 / 5.0 = 53.0 ∆νAM / JAM = 142 / 12.0 = 11.8 ∆νMX / JMX = 123 / 8.0 = 15.4
A2M2X
Chemical Shifts
δA = 1000 Hz / 200 MHz = 5.0 ppm δM = 500 Hz / 200 MHz = 2.5 ppm δX = 100 Hz / 200 MHz = 0.5 ppm
Coupling constants
JAM = 3.0 Hz; JAX = 7.0 Hz; JMX = 10.0 Hz;
1st Order Analysis
∆νAX = νA - νX = 1000 - 100 = 900 Hz ∆νAM = νA - νM = 1000 - 500 = 500 Hz ∆νMX = νM - νX = 500 - 100 = 400 Hz ∆νAX / JAX = 900 / 7.0 = 128.6 ∆νAM / JAM = 500 / 3.0 = 166.7 ∆νMX / JMX = 400 / 10.0 = 40.0
st
All ratios are significantly greater than 3 so a 1 order analysis is justified.
st
All ratios are significantly greater than 3 so a 1 order analysis is justified.
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Problem 327 5 Spin System
ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman 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
∆νAX = νA - νX = 710 - 192 = 518 Hz ∆νAM = νA - νM = 710 - 585 = 125 Hz ∆νMX = νM - νX = 585 - 192 = 393 Hz ∆νAX / JAX = 518 / 6.9 = 84.7 ∆νAM / JAM = 125 / 15.3 = 8.2 ∆νMX / JMX = 393 / 1.6 = 245.6 st
All ratios are significantly greater than 3 so a 1 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 – last updated April 2013
36
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Problem 328 5 Spin System
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ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman ADMX3
1st Order Analysis
∆νAD = νA ∆νAM = νA ∆νAX = νA ∆νDM = νD ∆νDX = νD ∆νMX = νM-
νD = 956 - 695 = 261 Hz νM = 956 - 619 = 337 Hz νX = 956 - 205 = 751 Hz νM = 695 - 619 = 76 Hz νX = 695 - 205 = 490 Hz νX = 619 - 205 = 414 Hz
∆νAD / JAD = 261 / <1 = >261 ∆νAM / JAM = 337 / 8.2 = 41.1 ∆νAX / JAX = 751 / <1 = >751 ∆νDM / JDM = 76 / 15.8 = 4.8 ∆νDX / JDX = 490 / 6.9 = 71.0 ∆νMX / JMX = 414 / 1.6 = 258.8 st
All ratios are significantly greater than 3 so a 1 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: O H
Chemical Shifts
Coupling constants
δA = 956 Hz / 100 MHz = 9.56 ppm; δD = 695 Hz / 100 MHz = 6.95 ppm; δM = 619 Hz / 100 MHz = 6.19 ppm; δX = 205 Hz / 100 MHz = 2.05 ppm;
December 2007 – last updated April 2013
M
37
H C
H
JAD= < 1 Hz; JAM = 8.2 Hz; JAX = < 1 Hz; JDM = 15.8 Hz; JDX = 6.9 Hz; JMX = 1.6Hz;
D
C
A
C CH3 X
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Problem 329
ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman
5 Spin System AMX3
Chemical Shifts
Problem 330
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3 Spin System A2X
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 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 – last updated April 2013
38
NH2 Br
Br
HA
HA HX
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ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman
Problem 331
Problem 332 1
All of the protons in the H 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 δ 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 δ 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 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 is 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 – last updated April 2013
39
HM Cl HX
HM
HA
2,6-dichloronaphthalene
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ORGANIC STRUCTURES FROM SPECTRA – 4th EDITION L D Field, S Sternhell and J R Kalman
Notes and Errata 1
The H NMR spectra in Problem 147 and in Problem 148 have been referenced incorrectly. Spectra in the book are shifted by 0.6 to 0.8 ppm to higher field than they should be. Problem 147 has correct resonances at approximately δ 2.7 and δ 1.5 with a broad resonance at δ 1.4 ppm. Problem 148 has correct resonances at approximately δ 2.8, δ 1.6 and δ 1.5 with a broad resonance at δ 2.0 ppm. Problem 215 the molecular formula should be C10H9NO4Br2 instead of C8H9NO4Br2. (Corrected 21.4.13) Revision History The answer to problem 296 had the C13 shifts for C3 and C4 interchanged. Corrected 25.8.11.
December 2007 – last updated April 2013
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