Organic Structure Elucidation -­‐ A Workbook of Unknowns www.nd.edu/~smithgrp/structure/workbook.html Answers and Spectroscopic Assignments Carleton G. Collins, Department of Chemistry and Biochemistry, University of Notre Dame, IN 46556, USA ©Copyright 2012 Acknowledgement: This answer book was prepared with funding support from the National Science Foundation (CHE 1058699). Spectroscopic
Technique
Problem 1
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 2
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Signal/Information
Comments
C3H5BrO2, UN=1
1 double bond
3067 (broad)
1717
COOH
C=O stretch (acid)
152, 154 (M+, [M+2]+)
135, 137 (M-17)
107, 109 (M-45)
73 (M-79)
Br present (1:1)
M–OH
M–COOH
M–Br
>9 (exchanges)
3.45 (t)
3.0 (t)
COOH
H3
H2
C8H14O4, UN=2
2 double bonds
174 (M)
146
129 (M-45)
101 (M-73)
M–CH2=CH2 (McLafferty Rgt)
M–OCH2CH3
M–COOCH2CH3
178 (s)
24.3 (t)
38.6 (t)
C1
C3
C2
2986
1749
C(sp3)-H stretch
C=O stretch (ester)
170
61
46
13.9, 13.5
C3
C2
C4
C1
C5
4.17 (m)
3.39 (q)
1.39 (d)
1.24 (t)
H2 (diastereotopic)
H4
H5
H1
2
Problem 3
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 4
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 5
Formula
Mass Spectrum (m/z)
IR (cm-1)
C9H12 UN=4
120 (M+)
105 (M-15)
91 (M-29)
Phenyl ring
M–CH3
M–CH2CH3 (tropylium ion)
3027, 3062
2865, 2900
C(sp2)-H stretch (aryl)
C(sp3)-H stretch (alkyl)
142.6
128.4, 128.1
125.5
38.0
24.5
13.8
C4
C2, C3
C1
C5
C6
C7
7.35 (m)
2.64 (t)
1.71 (sextet)
1.02 (t)
H1, H2, H3
H5
H6
H7
C7H13Br UN=1
1 ring
2938, 2849
1445
C(sp3)-H stretches (alkyl)
CH2 bend
40.8, 40.0
31.7, 26.1, 25.8
C4, C5
C1, C2, C3
C5H8O, UN=2
1 ring and 1 double bond
176, 178 (M+, [M+2]+)
97 (M-79)
83 (M-93)
3.27 (d)
1.86 - 1.63 (m)
1.25 - 0.98 (m)
84 (M+)
55 (M-29)
28 (M-56)
3063
2860, 2937
Br present (1:1)
M–Br
M–CH2Br (cyclohexyl ring)
H5
H1-H4
H1-H4
M–C2H5 (Retro Diels-Alder)
Ethene cation (Retro Diels-Alder)
C(sp2)-H stretch
C(sp3)-H stretches
3
1H
NMR (ppm)
13C
NMR (ppm)
Problem 6
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
1644
1070, 1238
C=C stretch
C-O stretches
144.0
101.7
65.7
22.7, 19.4
C1
C2
C5
C3, C4
6.35 (dt)
4.66 (m)
3.97 (t)
1.98 (q)
1.84
C9H13NO UN=4
H1
H2
H5
H3
H4
Aryl ring
152 (MH+)
120 (M-31)
91 (M-60)
60 (M-91)
M–CH2OH
M–CH2CH(NH2)CH2OH (tropylium ion)
M–PhCH3
7.37-7.25 (m)
5.2 (1H, exchanges)
3.69 (dd), 3.47 (dd)
3.18 (sp)
2.85 (dd), 2.58 (dd)
2.1 (2H, exchanges)
H1- H3
OH
H7 (diastereotopic)
H6
H5 (diastereotopic)
NH2
3352, 3298
2800-3100
3075
2823
1581
138.6
129.1, 128.3
126.3
66.2
54.1
40.8
Amine N-H stretches
OH stretch
C(sp2)-H stretch
C(sp3)-H stretch
Amine N-H bend
C4
C2, C3
C1
C7
C6
C5
4
Problem 7
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 8
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 9
Formula
Mass Spectrum (m/z)
C6H10, UN = 2
82 (M+)
67 (M-15)
54 (M-28)
28 (M-54)
1 ring and 1 double bond
M–CH3 (Rearrangement)
M–ethene (Retro Diels-Alder)
M–1,3-butadiene (Retro Diels-Alder)
3064
2780, 2985
1692
C(sp2)-H stretch
C(sp3)-H stretches
C=C stretch
127
25.1
22.6
C1
C2
C3
5.66 (s)
1.99 (m)
1.61 (quintet)
C8H11NO, UN =4
138 (MH+)
120 (M-18)
107 (M-31)
77 (M-61)
30 (M-108)
2500-3500
3358
1598
H1
H2
H3
Phenyl ring
M–H2O
M–CH3NH2 (hydroxyl tropylium ion)
M–CH2(OH)CH2NH2
M–PhCH2OH [CH2NH2+]
O--H--N stretch
Amine N-H stretch
Amine N-H bend
7.36 (m)
5.2 (exchanges)
4.35 (dd)
2.59 (dd), 2.51 (dd)
1.3 (broad)
H1-H3
OH
H5
H6 (diastereotopic)
NH2
C10H7Br, UN=7
Naphthyl ring
142.7
128.3, 125.8
127.4
74.1
49.2
206, 208 (M+, [M+2]+)
C4
C2, C3
C1
C5
C6
Br present (1:1)
5
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 10
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
127 (M-79)
101, 103
3054
1486, 1573
M–Br
M2+
C(sp2)-H stretch
Aromatic C=C stretches
7.78
7.57, 7.51
7.47 (d)
7.31 (dd)
7.25 (m)
H1
H9, H6
H4
H3
H7, H8
C14H19NO4, UN=6
1 aryl ring and 2 double bonds
134.4
131.7
129.8, 129.4, 129.1
127.8
126.9, 126.8
126.2
119.4
265 (M+)
209 (M-56)
148 (M-117)
91 (M-174)
57 (M-208)
3318
2400-3000
1711
1652
10
7.2
5.0, 6.8
4.40, 4.63
3.0
1.3, 1.4
176, 177
155, 157
127, 129, 130, 136, 138
80, 82
54, 56
38, 40
27, 28
C5
C10
C1, C3, C4
C6
C8, C9
C7
C2
M–CH2=C(CH3)2 (McLafferty Rgt)
M–NH2COOC(CH3)3
M–CH2-C6H5 (tropylium ion)
C(CH3)3+
Amide N-H stretch (secondary)
COOH
C=O stretch (acid)
C=O stretch (amide)
COOH
Aromatic
H4 (carbamate rotation)
H5
H8
H1
C6
C3
Aromatic
C2
C5
C8
C1
6
Problem 11
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 12
Formula
C6H12O2, UN=1
1 ring
116 (M)
98 (M-18)
70 (M-46)
57 (M-59)
M–H2O
M–CH2CH2, H2O (McLafferty Rgt)
C3H5O+
3.3
3.0
1.9, 1.6
1.2
H1, H2
OH
H3, H6
H4, H5
C7H5NO4, UN=6
1 aryl ring and 2 double bond
3279, 3378
2862, 2935
75.7
32.8
24.2
2 OH stretches
C(sp3)-H stretches
C1, C2
C3, C6
C4, C5
Mass Spectrum (m/z)
167 (M+)
150 (M-17)
137 (M-30)
120 (M-47)
109 (M-58)
IR (cm-1)
3114
2500-3100
1673
1520
C(sp2)-H stretch
OH
C=O stretch (aldehyde)
-NO2 stretch
190.2
163.0
140.5
134.8
127.6
119.1, 114.7
C7
C5
C2
C1
C3
C4, C6
1H
NMR (ppm)
13C
NMR (ppm)
11.4 (s)
10.3 (s)
8.11 (d)
7.12 (dd)
7.06 (d)
M–OH
M–NO
M–NO2H
M–NO, CO
OH
H7
H3
H4
H6
7
Problem 13
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 14
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
C5H10O4, UN=1
135 (MH+)
117 (M-18)
104 (M-31)
86 (M-49)
3226, 3372
2500-3000
1691
1 double bond
M–H2O
M–CH2OH
M–CH2OH, H2O
OH stretches
COOH
C=O stretch (acid)
~11 (br, exchanges)
4.5 (exchanges)
3.4 (q)
1.0 (s)
COOH
OH
H4
H1
176.6
63.8
49.5
17.0
C3
C4
C2
C1
C8H6O2, UN=6
1 aryl ring and 2 double bonds
134 (M+)
135 (M-1)
105 (M-29)
77 (M-57)
M–H
M–CHO
C6H5+
2698
1693
Aldehyde C-H stretch
C=O stretch (aldehyde)
191.4
139.9
130.0
C1
C2
C3
10.2 (s)
8.0 (s)
CHO
H3
8
Problem 15
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
C13H10O3, UN=9
214 (M+)
121 (M-93)
93 (M-121)
2 aryl rings and 1 double bond
M–OPh
M–CO2Ph
3186
1683
1480
OH stretch
C=O stretch (ester)
Aromatic C=C stretch
168.9
162.1
150.0
136.4
129.6, 130.3
126.3
121.6
117.7, 119.4
111.7
C7
C2
C8
C4
C6, C10
C11
C9
C3, C5
C1
10.5 (exchanges)
8.0 (dd)
7.45 (td)
7.35 (m)
7.21 (m)
7.11 (m)
6.97 (d)
6.95 (t)
OH
H6
H4
H10
H11
H9
H3
H5
9
Problem 16
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 17
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
C7H6O2, UN=5
122 (M+)
121 (M-1)
104 (M-18)
93 (M-29)
76 (M-46)
3239
2849
1665
1 aryl ring and 1 double bond
M–H
M–H2O
M–CHO
M–CO, H2O
OH stretch
Aldehyde C-H stretch
C=O stretch (aldehyde)
~11 (exchanges)
9.8 (s)
7.51 (m)
6.98 (m)
OH
H7
H4, H6
H3, H5
C9H10O3, UN=5
1 aryl ring and 1 double bond
117.5, 119.7
120.5, small
133.6, 136.7
161.5, small
196.5
166 (M+)
121 (M-45)
91 (M-75)
77 (M-89)
C2, C4
C6
C1, C3
C5
C7
M–COOH
M–CH2COOH, CH4
M–OCH3, CH-COOH
2500-3300
2961
1701
1022, 1243
COOH
C(sp3)-H stretch
C=O stetch (acid)
Aryl ether stretch
178.1
158.8
130.3
125.2
114.0
55.2
40.0
C1
C6
C4
C3
C5
C7
C2
11.8 (exchanges)
7.20 (m)
6.86 (m)
3.8 (s)
3.6 (s)
COOH
H4
H5
H7
H2
10
Problem 18
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 18
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 19
Formula
C7H10O4, UN=3
158 (M+)
143 (M-15)
115 (M-43)
83 (M-75)
2 rings and 1 double bond
M–CH3
M–CH3CO
M–(CH3)2CO2H
2940, 2995
1771
1202
C(sp3)-H stretches
C=O stretch (ester)
C-O stretch
174.1
113.9
74.5, 75.4
70.1
25.5, 26.7
C4
C5
C2, C3
C1
C6, C7
4.85 (dd)
4.75 (d)
4.42 (m)
1.47 (s), 1.38 (s)
C7H10O4, UN=3
158 (M+)
143 (M-15)
115 (M-43)
83 (M-75)
H2
H3
H1
H6, H7
2 rings and 1 double bond
M–CH3
M–CH3CO
M–(CH3)2CO2H
2940, 2995
1771
1202
C(sp3)-H stretches
C=O stretch (ester)
C-O stretch
174.1
113.9
74.5, 75.4
70.1
25.5, 26.7
C4
C5
C2, C3
C1
C6, C7
4.85 (dd)
4.75 (d)
4.42 (m)
1.47 (s), 1.38 (s)
C9H7NO4, UN= 7
H2
H3
H1
H6, H7
1 aryl ring and 3 double bonds
11
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 20
Formula
193 (M+)
176 (M-17)
146 (M-47)
91 (M-102)
2400-3000
2942
1691
1341
M–OH
M–NO2H
M–NO2, COOH (tropylium ion)
COOH
C(sp3)-H stretch
C=O stretch (acid)
-NO2 stretch (sym)
12.0 (exchanges)
7.73 (d)
7.46 (d)
7.19 (d)
6.25 (d)
COOH
H2
H3
H5
H6
C8H9NO2, UN=5
1 aryl ring and 1 double bond
167.0
147.9
141.3
140.7
129.3
123.9
123.5
C7
C1
C5
C4
C3
C2
C6
Mass Spectrum (m/z)
151 (M+)
107 (M-44)
94 (M-57)
77 (M-74)
M–CONH2
M–CHCONH2 (phenol cation)
C6H5+
IR (cm-1)
3358, 3464
2922
1698
1248
NH stretches
C(sp3)-H stretch
C=O stretch (amide)
C-O stretch
171.2
157.0
129.7
122.1
C6
C4
C2
C1
1H
NMR (ppm)
13C
NMR (ppm)
7.21(t)
6.92 (t)
6.81 (d)
6.48 (exchanges)
6.19 (exchanges)
4.3 (s)
H2
H1
H3
NH
NH
H5
12
Problem 21
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 22
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
114.5
67.0
C3
C5
C9H12O3, UN=4
1 aryl ring
168 (M+)
151 (M-17)
119 (M-49)
107 (M-61)
94 (M-74)
77 (M-91)
M–OH
M–OH, CH2OH
M–CH(OH)CH2OH
M–CHCH(OH)CH2OH (phenol cation)
C6H5+
3292
2935
1050, 1242
OH stretch
C(sp3)-H stretch
C-O stretches
158.3
129.5
121.2
114.4
70.4
68.9
63.6
C4
C2
C1
C3
C6
C5
C7
7.17 (m)
6.85 (m)
6.79 (m)
3.99 (quin)
3.91 (m)
3.63 (dd), 3.72 (dd)
2.59 (exchanges)
C9H12N2O, UN=5
164 (MH+)
120 (M-44)
103 (M-61)
91 (M-73)
77 (M-87)
3306, 3352
3034
1678
1605
6.87 (exchanges)
6.72-6.82 (m)
H2
H1
H3
H6
H5 (diastereotopic)
H7 (diastereotopic)
OH
1 aryl ring and 1 double bond
M–CONH2
M–HNH2CONH2
M–CHNH2CONH2 (tropylium ion)
C6H5+
NH2 stretches
C(sp2)-H stretch
C=O stretch (amide)
NH2 bend
NH2 (amide)
H1-H3
13
13C
NMR (ppm)
Problem 23
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 24
Formula
Mass Spectrum (m/z)
6.5 (exchanges)
2.88 (dd)
2.12 (dd), 2.46 (dd)
1.12 (exchanges)
NH2 (amide)
H6
H5 (diastereotopic)
NH2 (amine)
176.7
138.9
128.0, 129.3
126.0
56.2
41.2
C7
C4
C2, C3
C1
C6
C5
C9H10O3, UN=5
1 aryl ring and 1 double bond
166 (M+)
149 (M-17)
94 (M-72)
77 (M-89)
M–OH
M–CHCH2COOH
C6H5+
2600-3400
3047
1718
1235
COOH
C(sp2)-H stretch
C=O stretch (acid)
C-O stretch
177.3
158.3
129.4
121.1
114.5
62.8
34.3
C7
C4
C2
C1
C3
C5
C6
C9H10O3, UN=5
1 aryl ring and 1 double bond
12 (exchanges)
7.15 (t)
6.83 (t)
6.78 (d)
4.12 (t)
2.75 (t)
166 (M+)
135 (M-31)
122 (M-44)
77 (M-89)
COOH
H2
H1
H3
H5
H6
M–OCH3
M–CHO, CH3
C6H5+
14
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 25
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 26
Formula
Mass Spectrum (m/z)
3074
2948
2836
1705
1156, 1301
C(sp2)-H stretch
C(sp3)-H stretch
Aldehyde C-H stretch
C=O stretch (aldehyde)
C-O stretches
191.9
161.1
138.3
107.0, 107.1
55.5
C1
C4
C2
C3, C5
C6
9.90 (s)
6.99 (d)
6.69 (t)
3.90 (s)
C14H14NO3, UN=8
214 (M+)
199 (M-15)
171 (M-43)
128 (M-86)
CHO
H3
H5
H6
2 aryl rings
M–CH3
M–CO, CH3
M–2CO, 2CH3
2955
1248
825
C(sp3)-H stretch
C-O stretch
1,4-disubstituted aromatic
158.6
133.4
127.6
114.1
55.2
C4
C1
C2
C3
C5
C7H11BrO4, UN=2
2 double bonds
7.50 (d)
6.97 (d)
3.91 (s)
238, 240 (M+, [M+2]+)
193, 195 (M-45)
166, 168 (M-72)
138, 140 (M-100)
29 (M-209)
H2
H3
H5
Br present (1:1)
M–OCH2CH3
M–CO2CH2CH3
CH2BrCOOH+
CH3CH2+
15
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 27
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 28
Formula
Mass Spectrum (m/z)
IR (cm-1)
2986
1743
1149
C(sp3)-H stretch
C=O stretch (ester)
C-O stretch
164.5
63.2
42.3
13.8
C3
C2
C4
C1
4.82 (s)
4.28 (q)
1.30 (t)
C8H19N, UN=0
129 (M+)
86 (M-43)
44 (M-85)
3410
2928
1461
1132
H4
H2
H1
Fully saturated
M–CH2CH2CH3
CH3NH=CH2+ (McLafferty Rgt)
NH stretch
C(sp3)-H stretch
CH2 and CH3 bend
C-N stretch
2.57 (t)
1.45 (pent)
1.31 (sextet)
1.10 (exchanges)
0.90 (t)
H4
H3
H2
NH
H1
C6H12O2Cl2, UN=0
Fully saturated
49.8
32.3
20.4
13.9
187 (M+)
137, 139 (M-49)
107, 109 (M-79)
93, 95 (M-93)
63, 65 (M-79)
28 (M-158)
2873
1127
665
C4
C3
C2
C1
M–CH2Cl
M–OCH2CH2Cl
M–CH2OCH2CH2Cl
ClCH2CH2+
M–2(OCH2CH2Cl)
C(sp3)-H stretch
C-O stretch
C-Cl stretch
16
1H
NMR (ppm)
13C
NMR (ppm)
Problem 29
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 30
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
3.77 (t)
3.69 (s)
3.64 (t)
H2
H3
H1
C3H7OCl, UN=0
Fully saturated
2887
1125
671
C(sp3)-H stretch
C-O stretch (ether)
C-Cl stretch
72.4
58.8
42.6
C2
C3
C1
71.3
70.6
42.7
94, 96 (M+, [M+2]+)
63 (M-31)
45 (M-49)
28 (M-66)
3.59-3.65 (m)
3.38 (s)
C6H6O2, UN=4
110 (M+)
92 (M-18)
81 (M-29)
64 (M-46)
C2
C3
C1
Cl present (1:3)
M–OCH3
M–CH2Cl
M–OCH3, Cl
H1, H2
H3
1 aryl ring
M–H2O
M–CHO
M–CH2O2
3325 (broad)
1518
1188
743
OH stretch
Aromatic C=C stretch
C-O stretch
1,2-disubstituted aromatic
145.2
119.2
115.6
C1
C3
C2
8.8 (exchanges)
6.72 (dd)
6.59 (dd)
OH
H3
H2
17
Problem 31
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 32
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
C6H7NO, UN=4
109 (M+)
80 (M-29)
28 (M-81)
18 (M-91)
1 aryl ring
M–COH
M–C4H3NO
M–C6H5N
3296, 3361
2500-3100
1593
1259
1180
907
NH2 stretches
OH stretch
NH2 bend
C-N stretch
C-O stretch
NH2 bend
157.9
149.6
129.2
105.3
103.2
100.9
C1
C3
C5
C4
C6
C2
8.8 (exchanges)
6.75 (t)
5.99 (s)
5.95 (dd), 5.98 (dd)
4.9 (exchanges)
C7H6NF3, UN=4
161 (M+)
142 (M-19)
114 (M-47)
92 (M-69)
OH
H5
H2
H4, H6
NH2
1 aryl ring
M–F
M–CH2NF
M–CF3
3385
1630
1343
1123
NH2 stretch
NH2 bend
C-F stretch
C-O stretch
146.6
129.6
C1
C4
7.24 (t)
6.99 (dd)
6.89 (s)
6.82 (dd)
3.9 (exchanges)
H5
H4
H2
H6
NH2
18
Problem 33
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 34
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
123.0 (q)
117.9
114.9
111.2
C7
C6
C4
C2
C6H4Cl2, UN=4
1 aryl ring
3067
1458
746
C(sp2)-H stretch
Aromatic C=C stretch
1,2-disubstituted aromatic
132.5
130.5
127.7
C1
C2
C3
146, 148, 150
(M+, [M+2]+, [M+4]+)
111 (M-35)
7.43 (m)
7.19 (m)
C6H5NO3, UN=5
139 (M+)
122 (M-17)
93 (M-46)
2 Cl present
(10:6.6:1)
M–Cl
H2
H3
1 aryl ring and 1 double bond
M–OH
M–NO2
3477
3108
1312, 1535
1177
OH stretch
C(sp2)-H stretch
NO2 stretches
C-O stretch
155.1
137.5
133.5
125.0
119.9, 120.2
C2
C5
C1
C3
C4, C6
>9 (exchanges)
8.17 (dd)
7.59 (td)
7.18 (dd)
7.00 (td)
OH
H3
H5
H6
H4
19
Problem 35
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 36
Formula
Mass Spectrum (m/z)
C6H5NO3, UN=5
139 (M+)
93 (M-46)
81 (M-74)
65(M-74)
OH stretch
C(sp2)-H stretch
NO2 stretches
C-O stretch
155.8
149.1
130.2
121.9
115.8
110.5
C3
C1
C5
C6
C4
C2
7.81 (dd)
7.70 (t)
7.41 (t)
7.18 (dd)
5.7 (exchanges)
C4H4N2, UN=4
80 (M+)
52 (M-28)
26(M-54)
3050
13C
145.1
NMR (ppm)
NMR (ppm)
Problem 37
Formula
Mass Spectrum (m/z)
IR (cm-1)
M–NO2
M–CNO2
M–CNO3
3398
3114
1354, 1534
1213
IR (cm-1)
1H
1 aryl ring and 1 double bond
H4
H2
H5
H6
OH
1 aryl ring
M–C2H4
M–C2H2N2
C(sp2)-H stretch
8.5
H1
C6H7PO3, UN=4
1 aryl ring
158 (M+)
141 (M-17)
94 (M-64)
77 (M-81)
2756 (broad)
C1
M–OH
M–PO2H (phenol cation)
C6H5+
PO-H stretch
20
1H
NMR (ppm)
13C
NMR (ppm)
Problem 38
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 39
Formula
Mass Spectrum (m/z)
IR (cm-1)
7.68 (dd)
7.48-7.53 (m)
7.43-7.47 (m)
5.5 (exchanges)
H3
H1
H2
OH
C9H8N2, UN=7
2 aryl rings
134.1 (d)
130.9 (d)
130.6 (d)
128.1 (d)
144 (M+)
117 (M-27)
90 (M-54)
77 (M-67)
3392 (broad)
3115
1514
1308
C4
C1
C3
C2
M–HCN
M–C2H3N2
C6H5+
N-H stretch
C(sp2)-H stretch
Aromatic C=C stretch
C-N stretch
10.5 (exchanges)
7.76 (d)
7.72 (s)
7.38-7.42 (m)
7.28 (t)
NH
H3
H7
H2, H6
H1
C5H6O3, UN=3
1 ring and 2 double bonds
138.9
135.9
133.1
128.9
127.2
125.1
115.7
114 (M+)
86 (M-28)
73 (M-41)
60 (M-54)
55 (M-59)
2981
1758, 1830
1230
C4
C7
C5
C2
C1
C3
C6
M–CO
M–C2H3O
M–C3H5O
M–C2H3O2
C(sp3)-H stretch
Anhydride stretches
C-O stretch
21
1H
NMR (ppm)
13C
NMR (ppm)
Problem 40
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 41
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
2.43 (t)
1.96 (pent)
H2
H3
C16H35N, UN=0
Fully saturated
177.5
32.9
19.6
241 (M+)
142 (M-99)
3277
2854, 2929
1100
C1
C2
C3
M–C7H15
N-H stretch
C(sp3)-H stretches
C-N stretch
2.57 (t)
2.17 (s)
1.45 (m)
1.21-1.32 (m)
0.87 (t)
H1
NH
H2
H3-H7
H8
C6H12O5, UN=1
1 ring
50.1
30.1, 31.8
27.4, 29.5, 29.8
22.6
14.0
164 (M+)
146 (M-18)
133 (M-31)
73 (M-91)
60 (M-104)
3252, 3339
2946
1464
4.5 (exchanges)
4.45 (d)
3.66 (d)
3.55 (dd)
3.54 (m)
3.41 (dd)
C1
C2, C6
C3, C4, C5
C7
C8
M–H2O
M–OCH3
M–C2H3O3
M–C3H6O3
OH stretches
C(sp3)-H stretch
CH2 bend, OH bend
OH
H5
H2
H1
H3, H5
H1
22
13C
NMR (ppm)
Problem 42
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 43
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
3.34 (exchanges)
3.25 (s)
OH
H6
C13H9NO3, UN=10
2 aryl rings and 2 double bonds
100.6
69.0
68.6
68.2
62.9
54.8
227 (M+)
150 (M-77)
105(M-122)
77 (M-150)
C5
C4
C3
C2
C1
C6
M–C6H5
M–C7H4NO2
M–C7H4NO3
3101
1651
1512
C(sp2)-H stretch
C=O stretch (ketone)
NO2 stretch
194.8
149.7
142.8
136.2
133.4
128.2, 130.0, 130.8
123.5
C5
C9
C6
C4
C1
C2, C3, C7
C8
8.34 (d)
7.93 (d)
7.80 (d)
7.65 (t)
7.53 (t)
C7H6BrF, UN=4
188, 190 (M+, [M+2]+)
142, 144 (M-46)
109 (M-79)
77 (M-111)
3074
2925, 2984
1473
7.48 (dd)
H8
H7
H3
H1
H2
1 aryl ring
Br present (1:1)
M–C2H3F
M–Br
C6H5+
C(sp2)-H stretch
C(sp3)-H stretches
Aromatic C=C stretch
H3
23
13C
NMR (ppm)
Problem 44
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 45
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
6.97 (dd)
6.78 (td)
2.3 (s)
H6
H4
H7
C13H10 UN=9
2 aryl rings and 1 ring
161.7 (d)
139.9
133.3
118.9
117.7 (d)
114.4 (d)
23.0
166, 167 (M+)
165 (M-1)
3028
1446
C5
C1
C3
C2
C6
C4
C7
M–H
C(sp2)-H stretch
Aromatic C=C stretch
7.80 (d)
7.56 (d)
7.32 (t), 7.38 (t)
3.91 (s)
H2
H5
H3, H4
H7
C10H11NO3, UN=6
1 aryl ring and 1 triple bond
143.1
141.6
126.6, 126.8
125.0
119.8
36.8
117 (M+)
162 (M-15)
107 (M-70)
2934
2241
1518
1025, 1262
6.83 (m)
3.87 (s), 3.89 (s)
3.70 (s)
C6
C1
C3, C4
C5
C2
C7
M–CH3
M–CN, OCH3, CH3
C(sp2)-H stretch
C≡N stretch
Aromatic C=C stretch
C-O stretches (ether)
H2, H5, H6
H7
H8
24
13C
NMR (ppm)
Problem 46
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 47
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
(2 sets of peaks)
Problem 48
Formula
Mass Spectrum (m/z)
148.7, 149.3
122.0
120.1
118.1
110.8, 111.4
55.9
23.1
C3, C4
C1
C6
C9
C2, C5
C7
C8
C5H12O2, UN=2
2 double bonds or rings
2948, 2993
1375
1084
C(sp3)-H stretches
CH3 bending
C-O stretching
99.8
48.3
23.8
C2
C3
C1
C6H12O3, UN=2
2 double bonds and/or rings
104 (M+)
73 (M-31)
3.19 (s)
1.35 (s)
131 ([M-1]+)
115 (M-17)
101 (M-31)
72 (M-60)
M
M–OCH3
H3
H1
M–CH4
M–OCH3
C4H8O+
2906, 2958, 2996
1026, 1218
C(sp3)-H stretches
C-O stretches
106.1
55.3
30.9
C2
C1
C3
C10H20O, UN=2
2 double bonds or rings
5.09 (m)
3.42 (s), 3.36 (s)
1.82, 2.10 (m)
156 (M+)
138 (M-18)
H2
H1
H3
M–H2O
25
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 49
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
3252
2927
1456
1045
OH stretch
C(sp3)-H stretch
CH2 bend
C-O stretch
71.5
50.1
45.0
34.5
31.6
25.8
23.1
22.2
16.0, 20.1
C4
C5
C3
C7
C2
C8
C6
C1
C9
3.41 (td)
2.15 (heptet of doublets)
1.92-2.00 (m)
1.58-1.70 (m)
1.37-1.48 (m)
1.32 (exchanges)
0.90-0.95 (m)
0.81 (d)
C9H16O5, UN=2
205 (MH+)
159 (M-45)
141 (M-63)
130 (M-74)
113 (M-91)
H4
H8
H3 (1H, diastereotopic)
H6, H7 (1H, diastereotopic)
H2
OH
H3 (1H), H5, H7 (1H), H9 (6H)
H1
2 double bonds
M–OC2H5 (α-cleavage)
M–OC2H5, H2O
M–OC2H5, C2H5
M–OC2H5, CO, H2O
3511
2983, 2939
1740
1372
1024, 1189
OH stretch
C(sp3)-H stretches
C=O stretch (ester)
CH3 bend
C-O stretches
171.8
64.7
60.7
C3
C5
C2
4.43-4.48 (m)
4.18 (q)
3.45 (exchanges)
2.53-2.58 (m)
1.28 (t)
H5
H2
OH
H4 (diastereotopic)
H1
26
Problem 50
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 51
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
40.6
14.1
C4
C1
C3H7OCl, UN=0
Fully saturated
93, 95 (M-1+, [M+2]-1+)
78 (M-16)
58 (M-36)
3352
2889, 2961
1448
1054
721
Cl present (1:3), ClCH2CH2CH2O+
M–OH
CH2=CHCH2OH+
OH stretch
C(sp3)-H stretch
OH, CH2 bends
C-O stretch
C-Cl stretch
3.83 (t)
3.68 (t)
2.1 (q)
1.52 (exchanges)
H3
H1
H2
OH
C8H6O3, UN=6
1 aryl ring, 1 ring, and 1 double bond
59.4
41.7
34.8
150 (M+)
122 (M-28)
94 (M-56)
66 (M-84)
C3
C1
C2
M–CO
M–2CO (phenol cation)
M–3CO (cyclopentadiene cation)
3332
2923
1760
1476
1078, 1152
OH stretch
C(sp3)-H stretch
C=O stretch (lactone)
OH, CH2 bends
C-O stretches
174.7
153.7
146.6
124.9
C8
C5
C2
C1
9.2 (exchanges)
6.96 (d)
6.76 (m)
6.67 (dd)
3.90 (s)
OH
H3
H6
H4
H7
27
Problem 52
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 53
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 54
Formula
Mass Spectrum (m/z)
110.3, 111.7, 114.1
33.1
C3, C4, C6
C7
C9H10O2, UN=5
1 aryl ring and 1 double bond
150 (M+)
132 (M-18)
104 (M-46)
77 (M-73)
M–H2O
M–CO, H2O
C6H5+
2200-3200
3068
2967
1692
1304
COOH
C(sp2)-H stretch
C(sp3)-H stretch
C=O stretch (acid)
OH bend
174.9
135.6
132.2
129.9
127.8
20.1
C6
C2
C1
C4
C3
C5
> 9 (exchanges)
7.23 (t)
7.07 (d)
2.4 (s)
C6H8O2, UN=3
112 (M+)
83 (M-29)
56 (M-42)
2912, 2965
1711
2.8 (s)
208.3
36.6
C5H7NO3, UN=3
129 (M+)
114 (M-15)
86 (M-43)
COOH
H4
H3
H5
1 ring and 2 double bonds
M–CO
M2+
C(sp3)-H stretches
C=O stretch (ketone)
H2
C1
C2
1 ring and 2 double bonds
M–CH3
M–CH3CO
28
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 55
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 56
Formula
70 (M-59)
43 (M-86)
28 (M-101)
15 (M-114)
M–O=C-OCH3
CH3C=O
CH=NH
CH3
3266
1783
1043, 1246
NH stretch
C=O stretch (amide)
C-O stretches
171.1
165.2
72.9
44.8
20.7
C4
C1
C3
C2
C5
6.8 (exchanges)
5.82 (dd)
3.25 (dd), 3.28 (dd)
2.1 (s)
C8H8O2, UN=5
136 (M+)
135 (M-1)
107(M-29)
77(M-59)
NH
H3
H2
H5
1 aryl ring and 1 double bond
M–H
M–CHO (anisole cation)
C6H5+
3010
2934
2743, 2839
1684
1261
C(sp2)-H stretch
C(sp3)-H stretch
Aldehyde C-H stretches
C=O stretch (aldehyde)
C-O stretch
190.8
164.5
131.9
129.9
114.2
55.5
C6
C2
C4
C5
C3
C1
~10 (s)
7.85 (d)
7.00 (d)
3.90 (s)
C7H11NO2, UN=3
CHO
H4
H3
H1
1 double bond and 1 triple bond
29
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 57
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 58
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
141 (M+)
126(M-15)
57 (M-84)
M–CH3
C4H9+ (t-Bu cation)
2936, 2983
2262
1744
C(sp3)-H stretches
C≡N stretch
C=O stretch
161.8
113.4
84.3
27.7
25.8
C3
C1
C4
C5
C2
3.3(s)
1.5(s)
H2
H5
C6H5O2SCl, UN=4
4 double bonds/ring (likely aromatic)
3069
1377, 1185
C(sp2)-H stretch
S=O stretches
144.3
135.2
129.6, 126.9
C4
C1
C2, C3
176, 178 (M+, [M+2]+)
141 (M-35)
77 (M-99)
8.05 (dd)
7.76 (tt)
7.63 (t)
C10H13N5O4, UN=7
267 (M+)
178 (M-89)
164 (M-103)
135 (M-132)
3170, 3334
1664
1042, 1300
8.38 (s)
8.16(s)
Cl present (1:3)
M–Cl
C6H5+
H3
H1
H2
1 aryl ring, 2 rings, 1 double bond
M–C3H5O3
M–C4H7O3
M–C5H8O4 (adenine cation)
OH, NH2 stretches
NH2 bend
C-O stretches
H4
H1
30
13C
NMR (ppm)
Problem 59
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
7.39 (exchanges)
5.87 (d)
5.45 (exchanges)
5.19 (exchanges)
4.59-4.64 (m)
4.12-4.15 (m)
3.95 (q)
3.50-3.70 (dd’s)
NH2
H6
OH (connected to C7, C8)
OH (connected to C10)
H7
H8
H9
H10 (diastereotopic)
156.1
152.3
149.0
139.9
119.3
87.9
85.9
73.4
70.6
61.6
C3
C4
C5
C1
C2
C6
C9
C7
C8
C10
C14H12O2, UN=9
2 aryl rings and 1 double bond
212 (M+)
211 (M-1)
91 (M-121)
77 (M-135)
M–H
C7H7+ (tropylium ion)
C6H5+
3056
2743, 2827
1688
1021, 1255
C(sp2)-H stretch
Aldehyde C-H stretches
C=O stretch (aldehyde)
C-O stretches
190.8
163.7
135.8
131.9
130.0
127.4, 128.3, 128.7
115.1
70.2
C10
C6
C4
C8
C9
C1, C2, C3
C7
C5
~10 (s)
7.85 (d)
7.35-7.45 (m)
6.90 (d)
5.1 (s)
CHO
H8
H1-H3
H7
H5
31
Problem 60
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 61
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 62
Formula
Mass Spectrum (m/z)
C4HO3Br UN=4
176, 178 (M+, [M+2]+)
132 (M-44)
104 (M-72)
1 ring and 3 double bonds
Br present (1:1)
M–CO2
M–CO2, CO
3121, 3182
1781
1597
1225
C(sp2)-H stretches
C=O stretch (anhydride)
C=C stretch
C-O stretch
160.2, 161.7
133.7
133.4
C1, C2
C3
C4
7.17 (s)
C8H14O3, UN=2
158 (M+)
103 (M-55)
85 (M-73)
57 (M-101)
H3
2 double bonds
M–C3H3O
M–OC(CH3)3
C4H9+ (t-Bu cation)
2935, 2981
1718
1023, 1149
C(sp3)-H stretches
C=O stretch
C-O stretches
201.2
166.3
81.9
51.5
30.0
27.9
C2
C4
C5
C3
C1
C6
3.3(s)
2.3(s)
1.5(s)
C6H11O2Br, UN=1
194, 196 (M+, [M+2]+)
177, 179 (M-17)
115 (M-79)
97 (M-97)
60 (M-134)
H3
H1
H6
1 double bond
Br present (1:1)
M–OH
M–Br
M–Br, H2O
M-CH2=CHCH2CH2Br
32
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 63
Formula
Mass Spectrum (m/z)
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
Problem 64
Formula
Mass Spectrum (m/z)
2500-3500
2942
1711
1195
COOH
C(sp3)-H stretch
C=O stretch
C-O stretch
179.3
33.4, 33.6
23.7, 27.5, 32.3
C6
C1, C5
C2, C3, C4
C14H12O2, UN=9
2 aryl rings and 1 double bond
~10 (exchanges)
3.40 (t)
2.39 (t)
1.82-1.87 (m)
1.65 (pent)
1.55 (pent)
COOH
H1
H5
H2
H4
H3
212 (M+)
195 (M-17)
105 (M-107)
77 (M-135)
M–OH
C7H5O+
C6H5+
7.91 (dd)
7.52 (tt)
7.40 (t)
7.28-7.36 (m)
5.98 (d)
4.59 (exchanges)
H3
H1
H9
H2, H8, H10
H6
OH
3378
1677
OH stretch
C=O stretch (ketone)
198.8
138.9
133.9
133.4
127.2-129.1 (5 signals)
76.1
C5
C4
C1
C7
C2-C3, C8-C10
C6
C10H12O, UN=5
1 aryl ring and 1 double bond
148 (M+)
120 (M-28)
105 (M-43)
77 (M-71)
M–CH2=CH2 (McLafferty Rgt)
M– CH2CH2CH3
C6H5+
33
IR (cm-1)
1H
NMR (ppm)
13C
NMR (ppm)
3060
2874, 2962
1680
1450
C(sp2)-H stretch
C(sp3)-H stretches
C=O stretch (ketone)
CH2, CH3 bends
200.4
137.0
132.8
128.0, 128.5
40.4
17.7
13.8
C5
C4
C1
C2, C3
C6
C7
C8
7.95 (d)
7.55 (t)
7.47 (t)
2.95 (t)
1.79 (sextet)
1.00 (t)
H2
H1
H3
H6
H7
H8
34