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 Signal/Information Comments
Technique

Problem 1
Formula C3H5BrO2, UN=1 1 double bond

Mass Spectrum (m/z) 152, 154 (M+, [M+2]+) Br present (1:1)

135, 137 (M-17) M–OH
107, 109 (M-45) M–COOH
73 (M-79) M–Br

IR (cm-1) 3067 (broad) COOH

1717 C=O stretch (acid)

1H NMR (ppm) >9 (exchanges) COOH

3.45 (t) H3
3.0 (t) H2

13C NMR (ppm) 178 (s) C1

24.3 (t) C3
38.6 (t) C2

Problem 2
Formula C8H14O4, UN=2 2 double bonds

Mass Spectrum (m/z) 174 (M)

146 M–CH2=CH2 (McLafferty Rgt)
129 (M-45) M–OCH2CH3
101 (M-73) M–COOCH2CH3

IR (cm-1) 2986 C(sp3)-H stretch

1749 C=O stretch (ester)

1H NMR (ppm) 4.17 (m) H2 (diastereotopic)

3.39 (q) H4
1.39 (d) H5
1.24 (t) H1

13C NMR (ppm) 170 C3

61 C2
46 C4
13.9, 13.5 C1
C5

2
Problem 3
Formula C9H12 UN=4 Phenyl ring

Mass Spectrum (m/z) 120 (M+)

105 (M-15) M–CH3
91 (M-29) M–CH2CH3 (tropylium ion)

IR (cm-1) 3027, 3062 C(sp2)-H stretch (aryl)

2865, 2900 C(sp3)-H stretch (alkyl)

1H NMR (ppm) 7.35 (m) H1, H2, H3

2.64 (t) H5
1.71 (sextet) H6
1.02 (t) H7

13C NMR (ppm) 142.6 C4

128.4, 128.1 C2, C3
125.5 C1
38.0 C5
24.5 C6
13.8 C7

Problem 4
Formula C7H13Br UN=1 1 ring

Mass Spectrum (m/z) 176, 178 (M+, [M+2]+) Br present (1:1)

97 (M-79) M–Br
83 (M-93) M–CH2Br (cyclohexyl ring)

IR (cm-1) 2938, 2849 C(sp3)-H stretches (alkyl)

1445 CH2 bend

1H NMR (ppm) 3.27 (d) H5

1.86 - 1.63 (m) H1-H4
1.25 - 0.98 (m) H1-H4

13C NMR (ppm) 40.8, 40.0 C4, C5

31.7, 26.1, 25.8 C1, C2, C3

Problem 5
Formula C5H8O, UN=2 1 ring and 1 double bond

Mass Spectrum (m/z) 84 (M+)

55 (M-29) M–C2H5 (Retro Diels-Alder)
28 (M-56) Ethene cation (Retro Diels-Alder)

IR (cm-1) 3063 C(sp2)-H stretch

2860, 2937 C(sp3)-H stretches

3
 1644 C=C stretch
1070, 1238 C-O stretches

1H NMR (ppm) 6.35 (dt) H1

4.66 (m) H2
3.97 (t) H5
1.98 (q) H3
1.84 H4

13C NMR (ppm) 144.0 C1

101.7 C2
65.7 C5
22.7, 19.4 C3, C4

Problem 6
Formula C9H13NO UN=4 Aryl ring

Mass Spectrum (m/z) 152 (MH+)

120 (M-31) M–CH2OH
91 (M-60) M–CH2CH(NH2)CH2OH (tropylium ion)
60 (M-91) M–PhCH3

IR (cm-1) 3352, 3298 Amine N-H stretches

2800-3100 OH stretch
3075 C(sp2)-H stretch
2823 C(sp3)-H stretch
1581 Amine N-H bend

1H NMR (ppm) 7.37-7.25 (m) H1- H3

5.2 (1H, exchanges) OH
3.69 (dd), 3.47 (dd) H7 (diastereotopic)
3.18 (sp) H6
2.85 (dd), 2.58 (dd) H5 (diastereotopic)
2.1 (2H, exchanges) NH2

13C NMR (ppm) 138.6 C4

129.1, 128.3 C2, C3
126.3 C1
66.2 C7
54.1 C6
40.8 C5

4
Problem 7
Formula C6H10, UN = 2 1 ring and 1 double bond

Mass Spectrum (m/z) 82 (M+)

67 (M-15) M–CH3 (Rearrangement)
54 (M-28) M–ethene (Retro Diels-Alder)
28 (M-54) M–1,3-butadiene (Retro Diels-Alder)

IR (cm-1) 3064 C(sp2)-H stretch

2780, 2985 C(sp3)-H stretches
1692 C=C stretch

1H NMR (ppm) 5.66 (s) H1

1.99 (m) H2
1.61 (quintet) H3

13C NMR (ppm) 127 C1

25.1 C2
22.6 C3

Problem 8
Formula C8H11NO, UN =4 Phenyl ring

Mass Spectrum (m/z) 138 (MH+)

120 (M-18) M–H2O
107 (M-31) M–CH3NH2 (hydroxyl tropylium ion)
77 (M-61) M–CH2(OH)CH2NH2
30 (M-108) M–PhCH2OH [CH2NH2+]

IR (cm-1) 2500-3500 O--H--N stretch

3358 Amine N-H stretch
1598 Amine N-H bend

1H NMR (ppm) 7.36 (m) H1-H3

5.2 (exchanges) OH
4.35 (dd) H5
2.59 (dd), 2.51 (dd) H6 (diastereotopic)
1.3 (broad) NH2

13C NMR (ppm) 142.7 C4

128.3, 125.8 C2, C3
127.4 C1
74.1 C5
49.2 C6

Problem 9
Formula C10H7Br, UN=7 Naphthyl ring

Mass Spectrum (m/z) 206, 208 (M+, [M+2]+) Br present (1:1)

5
 127 (M-79) M–Br
101, 103 M2+

IR (cm-1) 3054 C(sp2)-H stretch

1486, 1573 Aromatic C=C stretches

1H NMR (ppm) 7.78 H1

7.57, 7.51 H9, H6
7.47 (d) H4
7.31 (dd) H3
7.25 (m) H7, H8

13C NMR (ppm) 134.4 C5

131.7 C10
129.8, 129.4, 129.1 C1, C3, C4
127.8 C6
126.9, 126.8 C8, C9
126.2 C7
119.4 C2

Problem 10
Formula C14H19NO4, UN=6 1 aryl ring and 2 double bonds

Mass Spectrum (m/z) 265 (M+)

209 (M-56) M–CH2=C(CH3)2 (McLafferty Rgt)
148 (M-117) M–NH2COOC(CH3)3
91 (M-174) M–CH2-C6H5 (tropylium ion)
57 (M-208) C(CH3)3+

IR (cm-1) 3318 Amide N-H stretch (secondary)

2400-3000 COOH
1711 C=O stretch (acid)
1652 C=O stretch (amide)

1H NMR (ppm) 10 COOH

7.2 Aromatic
5.0, 6.8 H4 (carbamate rotation)
4.40, 4.63 H5
3.0 H8
1.3, 1.4 H1

13C NMR (ppm) 176, 177 C6

155, 157 C3
127, 129, 130, 136, 138 Aromatic
80, 82 C2
54, 56 C5
38, 40 C8
27, 28 C1

6
Problem 11
Formula C6H12O2, UN=1 1 ring

Mass Spectrum (m/z) 116 (M)

98 (M-18) M–H2O
70 (M-46) M–CH2CH2, H2O (McLafferty Rgt)
57 (M-59) C3H5O+

IR (cm-1) 3279, 3378 2 OH stretches

2862, 2935 C(sp3)-H stretches

3.3 H1, H2
1H NMR (ppm) 3.0 OH
1.9, 1.6 H3, H6
1.2 H4, H5

75.7 C1, C2
13C NMR (ppm) 32.8 C3, C6
24.2 C4, C5

Problem 12
Formula C7H5NO4, UN=6 1 aryl ring and 2 double bond

Mass Spectrum (m/z) 167 (M+)

150 (M-17) M–OH
137 (M-30) M–NO
120 (M-47) M–NO2H
109 (M-58) M–NO, CO

IR (cm-1) 3114 C(sp2)-H stretch

2500-3100 OH
1673 C=O stretch (aldehyde)
1520 -NO2 stretch

1H NMR (ppm) 11.4 (s) OH

10.3 (s) H7
8.11 (d) H3
7.12 (dd) H4
7.06 (d) H6

13C NMR (ppm) 190.2 C7

163.0 C5
140.5 C2
134.8 C1
127.6 C3
119.1, 114.7 C4, C6

7
Problem 13
Formula C5H10O4, UN=1 1 double bond

Mass Spectrum (m/z) 135 (MH+)

117 (M-18) M–H2O
104 (M-31) M–CH2OH
86 (M-49) M–CH2OH, H2O

IR (cm-1) 3226, 3372 OH stretches

2500-3000 COOH
1691 C=O stretch (acid)

1H NMR (ppm) ~11 (br, exchanges) COOH

4.5 (exchanges) OH
3.4 (q) H4
1.0 (s) H1

13C NMR (ppm) 176.6 C3

63.8 C4
49.5 C2
17.0 C1

Problem 14
Formula C8H6O2, UN=6 1 aryl ring and 2 double bonds

Mass Spectrum (m/z) 134 (M+)

135 (M-1) M–H
105 (M-29) M–CHO
77 (M-57) C6H5+

IR (cm-1) 2698 Aldehyde C-H stretch

1693 C=O stretch (aldehyde)

1H NMR (ppm) 10.2 (s) CHO

8.0 (s) H3

13C NMR (ppm) 191.4 C1

139.9 C2
130.0 C3

8
Problem 15
Formula C13H10O3, UN=9 2 aryl rings and 1 double bond

Mass Spectrum (m/z) 214 (M+)

121 (M-93) M–OPh
93 (M-121) M–CO2Ph

IR (cm-1) 3186 OH stretch

1683 C=O stretch (ester)
1480 Aromatic C=C stretch

1H NMR (ppm) 10.5 (exchanges) OH

8.0 (dd) H6
7.45 (td) H4
7.35 (m) H10
7.21 (m) H11
7.11 (m) H9
6.97 (d) H3
6.95 (t) H5

13C NMR (ppm) 168.9 C7

162.1 C2
150.0 C8
136.4 C4
129.6, 130.3 C6, C10
126.3 C11
121.6 C9
117.7, 119.4 C3, C5
111.7 C1

9
Problem 16
Formula C7H6O2, UN=5 1 aryl ring and 1 double bond

Mass Spectrum (m/z) 122 (M+)

121 (M-1) M–H
104 (M-18) M–H2O
93 (M-29) M–CHO
76 (M-46) M–CO, H2O

IR (cm-1) 3239 OH stretch

2849 Aldehyde C-H stretch
1665 C=O stretch (aldehyde)

1H NMR (ppm) ~11 (exchanges) OH

9.8 (s) H7
7.51 (m) H4, H6
6.98 (m) H3, H5

13C NMR (ppm) 117.5, 119.7 C2, C4

120.5, small C6
133.6, 136.7 C1, C3
161.5, small C5
196.5 C7

Problem 17
Formula C9H10O3, UN=5 1 aryl ring and 1 double bond

Mass Spectrum (m/z) 166 (M+)

121 (M-45) M–COOH
91 (M-75) M–CH2COOH, CH4
77 (M-89) M–OCH3, CH-COOH

IR (cm-1) 2500-3300 COOH

2961 C(sp3)-H stretch
1701 C=O stetch (acid)
1022, 1243 Aryl ether stretch

1H NMR (ppm) 11.8 (exchanges) COOH

7.20 (m) H4
6.86 (m) H5
3.8 (s) H7
3.6 (s) H2

13C NMR (ppm) 178.1 C1

158.8 C6
130.3 C4
125.2 C3
114.0 C5
55.2 C7
40.0 C2

10
Problem 18
Formula C7H10O4, UN=3 2 rings and 1 double bond

Mass Spectrum (m/z) 158 (M+)

143 (M-15) M–CH3
115 (M-43) M–CH3CO
83 (M-75) M–(CH3)2CO2H

IR (cm-1) 2940, 2995 C(sp3)-H stretches

1771 C=O stretch (ester)
1202 C-O stretch

1H NMR (ppm) 4.85 (dd) H2

4.75 (d) H3
4.42 (m) H1
1.47 (s), 1.38 (s) H6, H7

13C NMR (ppm) 174.1 C4

113.9 C5
74.5, 75.4 C2, C3
70.1 C1
25.5, 26.7 C6, C7

Problem 18
Formula C7H10O4, UN=3 2 rings and 1 double bond

Mass Spectrum (m/z) 158 (M+)

143 (M-15) M–CH3
115 (M-43) M–CH3CO
83 (M-75) M–(CH3)2CO2H

IR (cm-1) 2940, 2995 C(sp3)-H stretches

1771 C=O stretch (ester)
1202 C-O stretch

1H NMR (ppm) 4.85 (dd) H2

4.75 (d) H3
4.42 (m) H1
1.47 (s), 1.38 (s) H6, H7

13C NMR (ppm) 174.1 C4

113.9 C5
74.5, 75.4 C2, C3
70.1 C1
25.5, 26.7 C6, C7

Problem 19
Formula C9H7NO4, UN= 7 1 aryl ring and 3 double bonds

11
Mass Spectrum (m/z) 193 (M+)
176 (M-17) M–OH
146 (M-47) M–NO2H
91 (M-102) M–NO2, COOH (tropylium ion)

IR (cm-1) 2400-3000 COOH

2942 C(sp3)-H stretch
1691 C=O stretch (acid)
1341 -NO2 stretch (sym)

1H NMR (ppm) 12.0 (exchanges) COOH

7.73 (d) H2
7.46 (d) H3
7.19 (d) H5
6.25 (d) H6

13C NMR (ppm) 167.0 C7

147.9 C1
141.3 C5
140.7 C4
129.3 C3
123.9 C2
123.5 C6

Problem 20
Formula C8H9NO2, UN=5 1 aryl ring and 1 double bond

Mass Spectrum (m/z) 151 (M+)

107 (M-44) M–CONH2
94 (M-57) M–CHCONH2 (phenol cation)
77 (M-74) C6H5+

IR (cm-1) 3358, 3464 NH stretches

2922 C(sp3)-H stretch
1698 C=O stretch (amide)
1248 C-O stretch

1H NMR (ppm) 7.21(t) H2

6.92 (t) H1
6.81 (d) H3
6.48 (exchanges) NH
6.19 (exchanges) NH
4.3 (s) H5

13C NMR (ppm) 171.2 C6

157.0 C4
129.7 C2
122.1 C1

12
 114.5 C3
67.0 C5

Problem 21
Formula C9H12O3, UN=4 1 aryl ring

Mass Spectrum (m/z) 168 (M+)

151 (M-17) M–OH
119 (M-49) M–OH, CH2OH
107 (M-61) M–CH(OH)CH2OH
94 (M-74) M–CHCH(OH)CH2OH (phenol cation)
77 (M-91) C6H5+
IR (cm-1)
3292 OH stretch
2935 C(sp3)-H stretch
1050, 1242 C-O stretches

1H NMR (ppm) 7.17 (m) H2

6.85 (m) H1
6.79 (m) H3
3.99 (quin) H6
3.91 (m) H5 (diastereotopic)
3.63 (dd), 3.72 (dd) H7 (diastereotopic)
2.59 (exchanges) OH

13C NMR (ppm) 158.3 C4

129.5 C2
121.2 C1
114.4 C3
70.4 C6
68.9 C5
63.6 C7

Problem 22
Formula C9H12N2O, UN=5 1 aryl ring and 1 double bond

Mass Spectrum (m/z) 164 (MH+)

120 (M-44) M–CONH2
103 (M-61) M–HNH2CONH2
91 (M-73) M–CHNH2CONH2 (tropylium ion)
77 (M-87) C6H5+

IR (cm-1) 3306, 3352 NH2 stretches

3034 C(sp2)-H stretch
1678 C=O stretch (amide)
1605 NH2 bend

1H NMR (ppm) 6.87 (exchanges) NH2 (amide)

6.72-6.82 (m) H1-H3

13
 6.5 (exchanges) NH2 (amide)
2.88 (dd) H6
2.12 (dd), 2.46 (dd) H5 (diastereotopic)
1.12 (exchanges) NH2 (amine)

13C NMR (ppm) 176.7 C7

138.9 C4
128.0, 129.3 C2, C3
126.0 C1
56.2 C6
41.2 C5

Problem 23
Formula C9H10O3, UN=5 1 aryl ring and 1 double bond

Mass Spectrum (m/z) 166 (M+)

149 (M-17) M–OH
94 (M-72) M–CHCH2COOH
77 (M-89) C6H5+

IR (cm-1) 2600-3400 COOH

3047 C(sp2)-H stretch
1718 C=O stretch (acid)
1235 C-O stretch

1H NMR (ppm) 12 (exchanges) COOH

7.15 (t) H2
6.83 (t) H1
6.78 (d) H3
4.12 (t) H5
2.75 (t) H6

13C NMR (ppm) 177.3 C7

158.3 C4
129.4 C2
121.1 C1
114.5 C3
62.8 C5
34.3 C6

Problem 24
Formula C9H10O3, UN=5 1 aryl ring and 1 double bond

Mass Spectrum (m/z) 166 (M+)

135 (M-31) M–OCH3
122 (M-44) M–CHO, CH3
77 (M-89) C6H5+

14
IR (cm-1) 3074 C(sp2)-H stretch
2948 C(sp3)-H stretch
2836 Aldehyde C-H stretch
1705 C=O stretch (aldehyde)
1156, 1301 C-O stretches

1H NMR (ppm) 9.90 (s) CHO

6.99 (d) H3
6.69 (t) H5
3.90 (s) H6

13C NMR (ppm) 191.9 C1

161.1 C4
138.3 C2
107.0, 107.1 C3, C5
55.5 C6

Problem 25
Formula C14H14NO3, UN=8 2 aryl rings

Mass Spectrum (m/z) 214 (M+)

199 (M-15) M–CH3
171 (M-43) M–CO, CH3
128 (M-86) M–2CO, 2CH3

IR (cm-1) 2955 C(sp3)-H stretch

1248 C-O stretch
825 1,4-disubstituted aromatic

1H NMR (ppm) 7.50 (d) H2

6.97 (d) H3
3.91 (s) H5

13C NMR (ppm) 158.6 C4

133.4 C1
127.6 C2
114.1 C3
55.2 C5

Problem 26
Formula C7H11BrO4, UN=2 2 double bonds

Mass Spectrum (m/z) 238, 240 (M+, [M+2]+) Br present (1:1)

193, 195 (M-45) M–OCH2CH3
166, 168 (M-72) M–CO2CH2CH3
138, 140 (M-100) CH2BrCOOH+
29 (M-209) CH3CH2+

15
IR (cm-1) 2986 C(sp3)-H stretch
1743 C=O stretch (ester)
1149 C-O stretch

1H NMR (ppm) 4.82 (s) H4

4.28 (q) H2
1.30 (t) H1

13C NMR (ppm) 164.5 C3

63.2 C2
42.3 C4
13.8 C1

Problem 27
Formula C8H19N, UN=0 Fully saturated

Mass Spectrum (m/z) 129 (M+)

86 (M-43) M–CH2CH2CH3
44 (M-85) CH3NH=CH2+ (McLafferty Rgt)

IR (cm-1) 3410 NH stretch

2928 C(sp3)-H stretch
1461 CH2 and CH3 bend
1132 C-N stretch

1H NMR (ppm) 2.57 (t) H4

1.45 (pent) H3
1.31 (sextet) H2
1.10 (exchanges) NH
0.90 (t) H1

13C NMR (ppm) 49.8 C4

32.3 C3
20.4 C2
13.9 C1

Problem 28
Formula C6H12O2Cl2, UN=0 Fully saturated

Mass Spectrum (m/z) 187 (M+)

137, 139 (M-49) M–CH2Cl
107, 109 (M-79) M–OCH2CH2Cl
93, 95 (M-93) M–CH2OCH2CH2Cl
63, 65 (M-79) ClCH2CH2+
28 (M-158) M–2(OCH2CH2Cl)

IR (cm-1) 2873 C(sp3)-H stretch

1127 C-O stretch
665 C-Cl stretch

16
1H NMR (ppm) 3.77 (t) H2
3.69 (s) H3
3.64 (t) H1

13C NMR (ppm) 71.3 C2

70.6 C3
42.7 C1

Problem 29
Formula C3H7OCl, UN=0 Fully saturated

Mass Spectrum (m/z) 94, 96 (M+, [M+2]+) Cl present (1:3)

63 (M-31) M–OCH3
45 (M-49) M–CH2Cl
28 (M-66) M–OCH3, Cl

IR (cm-1) 2887 C(sp3)-H stretch

1125 C-O stretch (ether)
671 C-Cl stretch

1H NMR (ppm) 3.59-3.65 (m) H1, H2

3.38 (s) H3

13C NMR (ppm) 72.4 C2

58.8 C3
42.6 C1

Problem 30
Formula C6H6O2, UN=4 1 aryl ring

Mass Spectrum (m/z) 110 (M+)

92 (M-18) M–H2O
81 (M-29) M–CHO
64 (M-46) M–CH2O2

IR (cm-1) 3325 (broad) OH stretch

1518 Aromatic C=C stretch
1188 C-O stretch
743 1,2-disubstituted aromatic

1H NMR (ppm) 8.8 (exchanges) OH

6.72 (dd) H3
6.59 (dd) H2

13C NMR (ppm) 145.2 C1

119.2 C3
115.6 C2

17
Problem 31
Formula C6H7NO, UN=4 1 aryl ring

Mass Spectrum (m/z) 109 (M+)

80 (M-29) M–COH
28 (M-81) M–C4H3NO
18 (M-91) M–C6H5N

IR (cm-1) 3296, 3361 NH2 stretches

2500-3100 OH stretch
1593 NH2 bend
1259 C-N stretch
1180 C-O stretch
907 NH2 bend

1H NMR (ppm) 8.8 (exchanges) OH

6.75 (t) H5
5.99 (s) H2
5.95 (dd), 5.98 (dd) H4, H6
4.9 (exchanges) NH2

13C NMR (ppm) 157.9 C1

149.6 C3
129.2 C5
105.3 C4
103.2 C6
100.9 C2

Problem 32
Formula C7H6NF3, UN=4 1 aryl ring

Mass Spectrum (m/z) 161 (M+)

142 (M-19) M–F
114 (M-47) M–CH2NF
92 (M-69) M–CF3

IR (cm-1) 3385 NH2 stretch

1630 NH2 bend
1343 C-F stretch
1123 C-O stretch

1H NMR (ppm) 7.24 (t) H5

6.99 (dd) H4
6.89 (s) H2
6.82 (dd) H6
3.9 (exchanges) NH2

13C NMR (ppm) 146.6 C1

129.6 C4

18
 123.0 (q) C7
117.9 C6
114.9 C4
111.2 C2

Problem 33
Formula C6H4Cl2, UN=4 1 aryl ring

Mass Spectrum (m/z) 146, 148, 150 2 Cl present

(M+, [M+2]+, [M+4]+) (10:6.6:1)
111 (M-35) M–Cl

IR (cm-1) 3067 C(sp2)-H stretch

1458 Aromatic C=C stretch
746 1,2-disubstituted aromatic

1H NMR (ppm) 7.43 (m) H2

7.19 (m) H3

13C NMR (ppm) 132.5 C1

130.5 C2
127.7 C3

Problem 34
Formula C6H5NO3, UN=5 1 aryl ring and 1 double bond

Mass Spectrum (m/z) 139 (M+)

122 (M-17) M–OH
93 (M-46) M–NO2

IR (cm-1) 3477 OH stretch

3108 C(sp2)-H stretch
1312, 1535 NO2 stretches
1177 C-O stretch

1H NMR (ppm) >9 (exchanges) OH

8.17 (dd) H3
7.59 (td) H5
7.18 (dd) H6
7.00 (td) H4

13C NMR (ppm) 155.1 C2

137.5 C5
133.5 C1
125.0 C3
119.9, 120.2 C4, C6

19
Problem 35
Formula C6H5NO3, UN=5 1 aryl ring and 1 double bond

Mass Spectrum (m/z) 139 (M+)

93 (M-46) M–NO2
81 (M-74) M–CNO2
65(M-74) M–CNO3

IR (cm-1) 3398 OH stretch

3114 C(sp2)-H stretch
1354, 1534 NO2 stretches
1213 C-O stretch

1H NMR (ppm) 7.81 (dd) H4

7.70 (t) H2
7.41 (t) H5
7.18 (dd) H6
5.7 (exchanges) OH

13C NMR (ppm) 155.8 C3

149.1 C1
130.2 C5
121.9 C6
115.8 C4
110.5 C2

Problem 36
Formula C4H4N2, UN=4 1 aryl ring

Mass Spectrum (m/z) 80 (M+)

52 (M-28) M–C2H4
26(M-54) M–C2H2N2

IR (cm-1) 3050 C(sp2)-H stretch

1H NMR (ppm) 8.5 H1

13C NMR (ppm) 145.1 C1

Problem 37
Formula C6H7PO3, UN=4 1 aryl ring

Mass Spectrum (m/z) 158 (M+)

141 (M-17) M–OH
94 (M-64) M–PO2H (phenol cation)
77 (M-81) C6H5+

IR (cm-1) 2756 (broad) PO-H stretch

20
1H NMR (ppm) 7.68 (dd) H3
7.48-7.53 (m) H1
7.43-7.47 (m) H2
5.5 (exchanges) OH

13C NMR (ppm) 134.1 (d) C4

130.9 (d) C1
130.6 (d) C3
128.1 (d) C2

Problem 38
Formula C9H8N2, UN=7 2 aryl rings

Mass Spectrum (m/z) 144 (M+)

117 (M-27) M–HCN
90 (M-54) M–C2H3N2
77 (M-67) C6H5+

IR (cm-1) 3392 (broad) N-H stretch

3115 C(sp2)-H stretch
1514 Aromatic C=C stretch
1308 C-N stretch

1H NMR (ppm) 10.5 (exchanges) NH

7.76 (d) H3
7.72 (s) H7
7.38-7.42 (m) H2, H6
7.28 (t) H1

13C NMR (ppm) 138.9 C4

135.9 C7
133.1 C5
128.9 C2
127.2 C1
125.1 C3
115.7 C6

Problem 39
Formula C5H6O3, UN=3 1 ring and 2 double bonds

Mass Spectrum (m/z) 114 (M+)

86 (M-28) M–CO
73 (M-41) M–C2H3O
60 (M-54) M–C3H5O
55 (M-59) M–C2H3O2

IR (cm-1) 2981 C(sp3)-H stretch

1758, 1830 Anhydride stretches
1230 C-O stretch

21
1H NMR (ppm) 2.43 (t) H2
1.96 (pent) H3

13C NMR (ppm) 177.5 C1

32.9 C2
19.6 C3

Problem 40
Formula C16H35N, UN=0 Fully saturated

Mass Spectrum (m/z) 241 (M+)

142 (M-99) M–C7H15

IR (cm-1) 3277 N-H stretch

2854, 2929 C(sp3)-H stretches
1100 C-N stretch

1H NMR (ppm) 2.57 (t) H1

2.17 (s) NH
1.45 (m) H2
1.21-1.32 (m) H3-H7
0.87 (t) H8

13C NMR (ppm) 50.1 C1

30.1, 31.8 C2, C6
27.4, 29.5, 29.8 C3, C4, C5
22.6 C7
14.0 C8

Problem 41
Formula C6H12O5, UN=1 1 ring

Mass Spectrum (m/z) 164 (M+)

146 (M-18) M–H2O
133 (M-31) M–OCH3
73 (M-91) M–C2H3O3
60 (M-104) M–C3H6O3

IR (cm-1) 3252, 3339 OH stretches

2946 C(sp3)-H stretch
1464 CH2 bend, OH bend

1H NMR (ppm) 4.5 (exchanges) OH

4.45 (d) H5
3.66 (d) H2
3.55 (dd) H1
3.54 (m) H3, H5
3.41 (dd) H1

22
 3.34 (exchanges) OH
3.25 (s) H6

13C NMR (ppm) 100.6 C5

69.0 C4
68.6 C3
68.2 C2
62.9 C1
54.8 C6

Problem 42
Formula C13H9NO3, UN=10 2 aryl rings and 2 double bonds

Mass Spectrum (m/z) 227 (M+)

150 (M-77) M–C6H5
105(M-122) M–C7H4NO2
77 (M-150) M–C7H4NO3

IR (cm-1) 3101 C(sp2)-H stretch

1651 C=O stretch (ketone)
1512 NO2 stretch

1H NMR (ppm) 8.34 (d) H8

7.93 (d) H7
7.80 (d) H3
7.65 (t) H1
7.53 (t) H2

13C NMR (ppm) 194.8 C5

149.7 C9
142.8 C6
136.2 C4
133.4 C1
128.2, 130.0, 130.8 C2, C3, C7
123.5 C8

Problem 43
Formula C7H6BrF, UN=4 1 aryl ring

Mass Spectrum (m/z) 188, 190 (M+, [M+2]+) Br present (1:1)

142, 144 (M-46) M–C2H3F
109 (M-79) M–Br
77 (M-111) C6H5+

IR (cm-1) 3074 C(sp2)-H stretch

2925, 2984 C(sp3)-H stretches
1473 Aromatic C=C stretch

1H NMR (ppm) 7.48 (dd) H3

23
 6.97 (dd) H6
6.78 (td) H4
2.3 (s) H7

13C NMR (ppm) 161.7 (d) C5

139.9 C1
133.3 C3
118.9 C2
117.7 (d) C6
114.4 (d) C4
23.0 C7

Problem 44
Formula C13H10 UN=9 2 aryl rings and 1 ring

Mass Spectrum (m/z) 166, 167 (M+)

165 (M-1) M–H

IR (cm-1) 3028 C(sp2)-H stretch

1446 Aromatic C=C stretch

1H NMR (ppm) 7.80 (d) H2

7.56 (d) H5
7.32 (t), 7.38 (t) H3, H4
3.91 (s) H7

13C NMR (ppm) 143.1 C6

141.6 C1
126.6, 126.8 C3, C4
125.0 C5
119.8 C2
36.8 C7

Problem 45
Formula C10H11NO3, UN=6 1 aryl ring and 1 triple bond

Mass Spectrum (m/z) 117 (M+)

162 (M-15) M–CH3
107 (M-70) M–CN, OCH3, CH3

IR (cm-1) 2934 C(sp2)-H stretch

2241 C≡N stretch
1518 Aromatic C=C stretch
1025, 1262 C-O stretches (ether)

1H NMR (ppm) 6.83 (m) H2, H5, H6

3.87 (s), 3.89 (s) H7
3.70 (s) H8

24
13C NMR (ppm) 148.7, 149.3 C3, C4
122.0 C1
120.1 C6
118.1 C9
110.8, 111.4 C2, C5
55.9 C7
23.1 C8

Problem 46
Formula C5H12O2, UN=2 2 double bonds or rings

Mass Spectrum (m/z) 104 (M+) M

73 (M-31) M–OCH3

IR (cm-1) 2948, 2993 C(sp3)-H stretches

1375 CH3 bending
1084 C-O stretching

1H NMR (ppm) 3.19 (s) H3

1.35 (s) H1

13C NMR (ppm) 99.8 C2

48.3 C3
23.8 C1

Problem 47
Formula C6H12O3, UN=2 2 double bonds and/or rings

Mass Spectrum (m/z) 131 ([M-1]+)

115 (M-17) M–CH4
101 (M-31) M–OCH3
72 (M-60) C4H8O+

IR (cm-1) 2906, 2958, 2996 C(sp3)-H stretches

1026, 1218 C-O stretches

1H NMR (ppm) 5.09 (m) H2

3.42 (s), 3.36 (s) H1
1.82, 2.10 (m) H3

13C NMR (ppm) 106.1 C2

55.3 C1
(2 sets of peaks) 30.9 C3

Problem 48
Formula C10H20O, UN=2 2 double bonds or rings

Mass Spectrum (m/z) 156 (M+)

138 (M-18) M–H2O

25
IR (cm-1) 3252 OH stretch
2927 C(sp3)-H stretch
1456 CH2 bend
1045 C-O stretch

1H NMR (ppm) 3.41 (td) H4

2.15 (heptet of doublets) H8
1.92-2.00 (m) H3 (1H, diastereotopic)
1.58-1.70 (m) H6, H7 (1H, diastereotopic)
1.37-1.48 (m) H2
1.32 (exchanges) OH
0.90-0.95 (m) H3 (1H), H5, H7 (1H), H9 (6H)
0.81 (d) H1

13C NMR (ppm) 71.5 C4

50.1 C5
45.0 C3
34.5 C7
31.6 C2
25.8 C8
23.1 C6
22.2 C1
16.0, 20.1 C9

Problem 49
Formula C9H16O5, UN=2 2 double bonds

Mass Spectrum (m/z) 205 (MH+)

159 (M-45) M–OC2H5 (α-cleavage)
141 (M-63) M–OC2H5, H2O
130 (M-74) M–OC2H5, C2H5
113 (M-91) M–OC2H5, CO, H2O

IR (cm-1) 3511 OH stretch

2983, 2939 C(sp3)-H stretches
1740 C=O stretch (ester)
1372 CH3 bend
1024, 1189 C-O stretches

1H NMR (ppm) 4.43-4.48 (m) H5

4.18 (q) H2
3.45 (exchanges) OH
2.53-2.58 (m) H4 (diastereotopic)
1.28 (t) H1

13C NMR (ppm) 171.8 C3

64.7 C5
60.7 C2

26
 40.6 C4
14.1 C1

Problem 50
Formula C3H7OCl, UN=0 Fully saturated

Mass Spectrum (m/z) 93, 95 (M-1+, [M+2]-1+) Cl present (1:3), ClCH2CH2CH2O+

78 (M-16) M–OH
58 (M-36) CH2=CHCH2OH+

IR (cm-1) 3352 OH stretch

2889, 2961 C(sp3)-H stretch
1448 OH, CH2 bends
1054 C-O stretch
721 C-Cl stretch

1H NMR (ppm) 3.83 (t) H3

3.68 (t) H1
2.1 (q) H2
1.52 (exchanges) OH

13C NMR (ppm) 59.4 C3

41.7 C1
34.8 C2

Problem 51
Formula C8H6O3, UN=6 1 aryl ring, 1 ring, and 1 double bond

Mass Spectrum (m/z) 150 (M+)

122 (M-28) M–CO
94 (M-56) M–2CO (phenol cation)
66 (M-84) M–3CO (cyclopentadiene cation)

IR (cm-1) 3332 OH stretch

2923 C(sp3)-H stretch
1760 C=O stretch (lactone)
1476 OH, CH2 bends
1078, 1152 C-O stretches

1H NMR (ppm) 9.2 (exchanges) OH

6.96 (d) H3
6.76 (m) H6
6.67 (dd) H4
3.90 (s) H7

13C NMR (ppm) 174.7 C8

153.7 C5
146.6 C2
124.9 C1

27
 110.3, 111.7, 114.1 C3, C4, C6
33.1 C7

Problem 52
Formula C9H10O2, UN=5 1 aryl ring and 1 double bond

Mass Spectrum (m/z) 150 (M+)

132 (M-18) M–H2O
104 (M-46) M–CO, H2O
77 (M-73) C6H5+

IR (cm-1) 2200-3200 COOH

3068 C(sp2)-H stretch
2967 C(sp3)-H stretch
1692 C=O stretch (acid)
1304 OH bend

1H NMR (ppm) > 9 (exchanges) COOH

7.23 (t) H4
7.07 (d) H3
2.4 (s) H5

13C NMR (ppm) 174.9 C6

135.6 C2
132.2 C1
129.9 C4
127.8 C3
20.1 C5

Problem 53
Formula C6H8O2, UN=3 1 ring and 2 double bonds

Mass Spectrum (m/z) 112 (M+)

83 (M-29) M–CO
56 (M-42) M2+

IR (cm-1) 2912, 2965 C(sp3)-H stretches

1711 C=O stretch (ketone)
1H NMR (ppm) 2.8 (s) H2
13C NMR (ppm) 208.3 C1
36.6 C2

Problem 54
Formula C5H7NO3, UN=3 1 ring and 2 double bonds

Mass Spectrum (m/z) 129 (M+)

114 (M-15) M–CH3
86 (M-43) M–CH3CO

28
 70 (M-59) M–O=C-OCH3
43 (M-86) CH3C=O
28 (M-101) CH=NH
15 (M-114) CH3

IR (cm-1) 3266 NH stretch

1783 C=O stretch (amide)
1043, 1246 C-O stretches

1H NMR (ppm) 6.8 (exchanges) NH

5.82 (dd) H3
3.25 (dd), 3.28 (dd) H2
2.1 (s) H5

13C NMR (ppm) 171.1 C4

165.2 C1
72.9 C3
44.8 C2
20.7 C5

Problem 55
Formula C8H8O2, UN=5 1 aryl ring and 1 double bond

Mass Spectrum (m/z) 136 (M+)

135 (M-1) M–H
107(M-29) M–CHO (anisole cation)
77(M-59) C6H5+

IR (cm-1) 3010 C(sp2)-H stretch

2934 C(sp3)-H stretch
2743, 2839 Aldehyde C-H stretches
1684 C=O stretch (aldehyde)
1261 C-O stretch

1H NMR (ppm) ~10 (s) CHO

7.85 (d) H4
7.00 (d) H3
3.90 (s) H1

13C NMR (ppm) 190.8 C6

164.5 C2
131.9 C4
129.9 C5
114.2 C3
55.5 C1

Problem 56
Formula C7H11NO2, UN=3 1 double bond and 1 triple bond

29
Mass Spectrum (m/z) 141 (M+)
126(M-15) M–CH3
57 (M-84) C4H9+ (t-Bu cation)

IR (cm-1) 2936, 2983 C(sp3)-H stretches

2262 C≡N stretch
1744 C=O stretch

1H NMR (ppm) 3.3(s) H2

1.5(s) H5

13C NMR (ppm) 161.8 C3

113.4 C1
84.3 C4
27.7 C5
25.8 C2

Problem 57
Formula C6H5O2SCl, UN=4 4 double bonds/ring (likely aromatic)

Mass Spectrum (m/z) 176, 178 (M+, [M+2]+) Cl present (1:3)

141 (M-35) M–Cl
77 (M-99) C6H5+

IR (cm-1) 3069 C(sp2)-H stretch

1377, 1185 S=O stretches

1H NMR (ppm) 8.05 (dd) H3

7.76 (tt) H1
7.63 (t) H2

13C NMR (ppm) 144.3 C4

135.2 C1
129.6, 126.9 C2, C3

Problem 58
Formula C10H13N5O4, UN=7 1 aryl ring, 2 rings, 1 double bond

Mass Spectrum (m/z) 267 (M+)

178 (M-89) M–C3H5O3
164 (M-103) M–C4H7O3
135 (M-132) M–C5H8O4 (adenine cation)

IR (cm-1) 3170, 3334 OH, NH2 stretches

1664 NH2 bend
1042, 1300 C-O stretches

1H NMR (ppm) 8.38 (s) H4

8.16(s) H1

30
 7.39 (exchanges) NH2
5.87 (d) H6
5.45 (exchanges) OH (connected to C7, C8)
5.19 (exchanges) OH (connected to C10)
4.59-4.64 (m) H7
4.12-4.15 (m) H8
3.95 (q) H9
3.50-3.70 (dd’s) H10 (diastereotopic)

13C NMR (ppm) 156.1 C3

152.3 C4
149.0 C5
139.9 C1
119.3 C2
87.9 C6
85.9 C9
73.4 C7
70.6 C8
61.6 C10

Problem 59
Formula C14H12O2, UN=9 2 aryl rings and 1 double bond

Mass Spectrum (m/z) 212 (M+)

211 (M-1) M–H
91 (M-121) C7H7+ (tropylium ion)
77 (M-135) C6H5+

IR (cm-1) 3056 C(sp2)-H stretch

2743, 2827 Aldehyde C-H stretches
1688 C=O stretch (aldehyde)
1021, 1255 C-O stretches

1H NMR (ppm) ~10 (s) CHO

7.85 (d) H8
7.35-7.45 (m) H1-H3
6.90 (d) H7
5.1 (s) H5

13C NMR (ppm) 190.8 C10

163.7 C6
135.8 C4
131.9 C8
130.0 C9
127.4, 128.3, 128.7 C1, C2, C3
115.1 C7
70.2 C5

31
Problem 60
Formula C4HO3Br UN=4 1 ring and 3 double bonds

Mass Spectrum (m/z) 176, 178 (M+, [M+2]+) Br present (1:1)

132 (M-44) M–CO2
104 (M-72) M–CO2, CO

IR (cm-1) 3121, 3182 C(sp2)-H stretches

1781 C=O stretch (anhydride)
1597 C=C stretch
1225 C-O stretch

1H NMR (ppm) 7.17 (s) H3

13C NMR (ppm) 160.2, 161.7 C1, C2

133.7 C3
133.4 C4

Problem 61
Formula C8H14O3, UN=2 2 double bonds

Mass Spectrum (m/z) 158 (M+)

103 (M-55) M–C3H3O
85 (M-73) M–OC(CH3)3
57 (M-101) C4H9+ (t-Bu cation)

IR (cm-1) 2935, 2981 C(sp3)-H stretches

1718 C=O stretch
1023, 1149 C-O stretches

1H NMR (ppm) 3.3(s) H3

2.3(s) H1
1.5(s) H6

13C NMR (ppm) 201.2 C2

166.3 C4
81.9 C5
51.5 C3
30.0 C1
27.9 C6

Problem 62
Formula C6H11O2Br, UN=1 1 double bond

Mass Spectrum (m/z) 194, 196 (M+, [M+2]+) Br present (1:1)

177, 179 (M-17) M–OH
115 (M-79) M–Br
97 (M-97) M–Br, H2O
60 (M-134) M-CH2=CHCH2CH2Br

32
IR (cm-1) 2500-3500 COOH
2942 C(sp3)-H stretch
1711 C=O stretch
1195 C-O stretch

1H NMR (ppm) ~10 (exchanges) COOH

3.40 (t) H1
2.39 (t) H5
1.82-1.87 (m) H2
1.65 (pent) H4
1.55 (pent) H3

13C NMR (ppm) 179.3 C6

33.4, 33.6 C1, C5
23.7, 27.5, 32.3 C2, C3, C4

Problem 63
Formula C14H12O2, UN=9 2 aryl rings and 1 double bond

Mass Spectrum (m/z) 212 (M+)

195 (M-17) M–OH
105 (M-107) C7H5O+
77 (M-135) C6H5+

IR (cm-1) 3378 OH stretch

1677 C=O stretch (ketone)

1H NMR (ppm) 7.91 (dd) H3

7.52 (tt) H1
7.40 (t) H9
7.28-7.36 (m) H2, H8, H10
5.98 (d) H6
4.59 (exchanges) OH

13C NMR (ppm) 198.8 C5

138.9 C4
133.9 C1
133.4 C7
127.2-129.1 (5 signals) C2-C3, C8-C10
76.1 C6

Problem 64
Formula C10H12O, UN=5 1 aryl ring and 1 double bond

Mass Spectrum (m/z) 148 (M+)

120 (M-28) M–CH2=CH2 (McLafferty Rgt)
105 (M-43) M– CH2CH2CH3
77 (M-71) C6H5+

33
IR (cm-1) 3060 C(sp2)-H stretch
2874, 2962 C(sp3)-H stretches
1680 C=O stretch (ketone)
1450 CH2, CH3 bends

1H NMR (ppm) 7.95 (d) H2

7.55 (t) H1
7.47 (t) H3
2.95 (t) H6
1.79 (sextet) H7
1.00 (t) H8

13C NMR (ppm) 200.4 C5

137.0 C4
132.8 C1
128.0, 128.5 C2, C3
40.4 C6
17.7 C7
13.8 C8

34