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Organic(Structure(Elucidation(1(A((Workbook(of(Unknowns( ( www.nd.edu/~smithgrp/structure/workbook.html6 ( Answers(and(Spectroscopic(Assignments( ( ( Carleton(G.(Collins,(( Department(of(Chemistry(and(Biochemistry,( University(of(Notre(Dame,(IN(46556,(USA( ( ©Copyright(2012( 6 6 Acknowledgement:(This(answer(book(was(prepared(with(funding(support( from(the(National(Science(Foundation((CHE(1058699).(

Spectroscopic Technique

Signal/Information

Comments

C3H5BrO 2, UN=1

1 double bond

Mass Spectrum (m/z)

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

IR (cm-1)

3067 (broad) 1717

COOH C=O stretch (acid)

1H

>9 (exchanges) 3.45 (t) 3.0 (t)

COOH H3 H2

178 (s) 24.3 (t) 38.6 (t)

C1 C3 C2

C8H14O4, UN=2

2 double bonds

174 (M) 146 129 (M-45) 101 (M-73)

M–CH2=CH2 (McLafferty Rgt) M–OCH2CH3 M–COOCH2CH3

IR (cm-1)

2986 1749

C(sp3)-H stretch C=O stretch (ester)

1H

4.17 (m) 3.39 (q) 1.39 (d) 1.24 (t)

H2 (diastereotopic) H4 H5 H1

170 61 46 13.9, 13.5

C3 C2 C4 C1 C5

Problem 1 Formula

NMR (ppm)

13C

NMR (ppm)

Problem 2 Formula

Mass Spectrum (m/z)

NMR (ppm)

13C

NMR (ppm)

2

Problem 3 Formula

C9H12 UN=4

Phenyl ring

120 (M+) 105 (M-15) 91 (M-29)

M–CH3 M–CH2CH3 (tropylium ion)

IR (cm-1)

3027, 3062 2865, 2900

C(sp2)-H stretch (aryl) C(sp3)-H stretch (alkyl)

1H

7.35 (m) 2.64 (t) 1.71 (sextet) 1.02 (t)

H1, H2, H3 H5 H6 H7

142.6 128.4, 128.1 125.5 38.0 24.5 13.8

C4 C2, C3 C1 C5 C6 C7

C7H13Br UN=1

1 ring

Mass Spectrum (m/z)

176, 178 (M+, [M+2]+) 97 (M-79) 83 (M-93)

Br present (1:1) M–Br M–CH2Br (cyclohexyl ring)

IR (cm-1)

2938, 2849 1445

C(sp3)-H stretches (alkyl) CH2 bend

1H

3.27 (d) 1.86 - 1.63 (m) 1.25 - 0.98 (m)

H5 H1-H4 H1-H4

40.8, 40.0 31.7, 26.1, 25.8

C4, C5 C1, C2, C3

C5H8O, UN=2

1 ring and 1 double bond

84 (M+) 55 (M-29) 28 (M-56)

M–C2H5 (Retro Diels-Alder) Ethene cation (Retro Diels-Alder)

3063 2860, 2937

C(sp2 )-H stretch C(sp 3)-H stretches

Mass Spectrum (m/z)

NMR (ppm)

13C

NMR (ppm)

Problem 4 Formula

NMR (ppm)

13C

NMR (ppm)

Problem 5 Formula Mass Spectrum (m/z)

IR (cm -1)

3

1644 1070, 1238

C=C stretch C-O stretches

6.35 (dt) 4.66 (m) 3.97 (t) 1.98 (q) 1.84

H1 H2 H5 H3 H4

144.0 101.7 65.7 22.7, 19.4

C1 C2 C5 C3, C4

C9H13NO UN=4

Aryl ring

152 (MH+) 120 (M-31) 91 (M-60) 60 (M-91)

M–CH2OH M–CH2CH(NH2)CH2OH (tropylium ion) M–PhCH3

IR (cm-1)

3352, 3298 2800-3100 3075 2823 1581

Amine N-H stretches OH stretch C(sp2)-H stretch C(sp3)-H stretch Amine N-H bend

1H

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

138.6 129.1, 128.3 126.3 66.2 54.1 40.8

C4 C2, C3 C1 C7 C6 C5

1H

NMR (ppm)

13C

NMR (ppm)

Problem 6 Formula Mass Spectrum (m/z)

NMR (ppm)

13C

NMR (ppm)

4

Problem 7 Formula

C6H10, UN = 2

1 ring and 1 double bond

82 (M+) 67 (M-15) 54 (M-28) 28 (M-54)

M–CH3 (Rearrangement) M–ethene (Retro Diels-Alder) M–1,3-butadiene (Retro Diels-Alder)

IR (cm-1)

3064 2780, 2985 1692

C(sp2)-H stretch C(sp3)-H stretches C=C stretch

1H

5.66 (s) 1.99 (m) 1.61 (quintet)

H1 H2 H3

127 25.1 22.6

C1 C2 C3

C8H11NO, UN =4

Phenyl ring

138 (MH+) 120 (M-18) 107 (M-31) 77 (M-61) 30 (M-108)

M–H2O M–CH3NH2 (hydroxyl tropylium ion) M–CH2(OH)CH2NH2 M–PhCH2OH [CH2NH2+]

IR (cm-1)

2500-3500 3358 1598

O--H--N stretch Amine N-H stretch Amine N-H bend

1H

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

142.7 128.3, 125.8 127.4 74.1 49.2

C4 C2, C3 C1 C5 C6

Problem 9 Formula

C10H7Br, UN=7

Naphthyl ring

Mass Spectrum (m/z)

206, 208 (M+, [M+2]+)

Br present (1:1)

Mass Spectrum (m/z)

NMR (ppm)

13C

NMR (ppm)

Problem 8 Formula Mass Spectrum (m/z)

NMR (ppm)

13C

NMR (ppm)

5

127 (M-79) 101, 103

M–Br M2+

IR (cm-1)

3054 1486, 1573

C(sp2)-H stretch Aromatic C=C stretches

1H

7.78 7.57, 7.51 7.47 (d) 7.31 (dd) 7.25 (m)

H1 H9, H6 H4 H3 H7, H8

134.4 131.7 129.8, 129.4, 129.1 127.8 126.9, 126.8 126.2 119.4

C5 C10 C1, C3, C4 C6 C8, C9 C7 C2

C14H19NO4, UN=6

1 aryl ring and 2 double bonds

265 (M+) 209 (M-56) 148 (M-117) 91 (M-174) 57 (M-208)

M–CH2=C(CH3)2 (McLafferty Rgt) M–NH2COOC(CH3)3 M–CH2-C6H5 (tropylium ion) C(CH3)3+

IR (cm-1)

3318 2400-3000 1711 1652

Amide N-H stretch (secondary) COOH C=O stretch (acid) C=O stretch (amide)

1H

10 7.2 5.0, 6.8 4.40, 4.63 3.0 1.3, 1.4

COOH Aromatic H4 (carbamate rotation) H5 H8 H1

176, 177 155, 157 127, 129, 130, 136, 138 80, 82 54, 56 38, 40 27, 28

C6 C3 Aromatic C2 C5 C8 C1

NMR (ppm)

13C

NMR (ppm)

Problem 10 Formula Mass Spectrum (m/z)

NMR (ppm)

13C

NMR (ppm)

6

Problem 11 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+

3279, 3378 2862, 2935

2 OH stretches C(sp3)-H stretches

3.3 3.0 1.9, 1.6 1.2

H1, H2 OH H3, H6 H4, H5

75.7 32.8 24.2

C1, C2 C3, C6 C4, C5

C7H5NO4, UN=6

1 aryl ring and 2 double bond

167 (M+) 150 (M-17) 137 (M-30) 120 (M-47) 109 (M-58)

M–OH M–NO M–NO2H M–NO, CO

IR (cm-1)

3114 2500-3100 1673 1520

C(sp2)-H stretch OH C=O stretch (aldehyde) -NO2 stretch

1H

11.4 (s) 10.3 (s) 8.11 (d) 7.12 (dd) 7.06 (d)

OH H7 H3 H4 H6

190.2 163.0 140.5 134.8 127.6 119.1, 114.7

C7 C5 C2 C1 C3 C4, C6

Mass Spectrum (m/z)

IR (cm-1)

1H

NMR (ppm)

13C

NMR (ppm)

Problem 12 Formula Mass Spectrum (m/z)

NMR (ppm)

13C

NMR (ppm)

7

Problem 13 Formula

C5H10O4, UN=1

1 double bond

135 (MH+) 117 (M-18) 104 (M-31) 86 (M-49)

M–H2O M–CH2OH M–CH2OH, H2O

IR (cm-1)

3226, 3372 2500-3000 1691

OH stretches COOH C=O stretch (acid)

1H

~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+

IR (cm-1)

2698 1693

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

1H

10.2 (s) 8.0 (s)

CHO H3

191.4 139.9 130.0

C1 C2 C3

Mass Spectrum (m/z)

NMR (ppm)

13C

NMR (ppm)

Problem 14 Formula Mass Spectrum (m/z)

NMR (ppm)

13C

NMR (ppm)

8

Problem 15 Formula

C13H10O3, UN=9

2 aryl rings and 1 double bond

214 (M+) 121 (M-93) 93 (M-121)

M–OPh M–CO2Ph

IR (cm-1)

3186 1683 1480

OH stretch C=O stretch (ester) Aromatic C=C stretch

1H

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

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

Mass Spectrum (m/z)

NMR (ppm)

13C

NMR (ppm)

9

Problem 16 Formula

C7H6O2, UN=5

1 aryl ring and 1 double bond

122 (M+) 121 (M-1) 104 (M-18) 93 (M-29) 76 (M-46)

M–H M–H2O M–CHO M–CO, H2O

IR (cm-1)

3239 2849 1665

OH stretch Aldehyde C-H stretch C=O stretch (aldehyde)

1H

~11 (exchanges) 9.8 (s) 7.51 (m) 6.98 (m)

OH H7 H4, H6 H3, H5

117.5, 119.7 120.5, small 133.6, 136.7 161.5, small 196.5

C2, C4 C6 C1, C3 C5 C7

C9H10O3, UN=5

1 aryl ring and 1 double bond

166 (M+) 121 (M-45) 91 (M-75) 77 (M-89)

M–COOH M–CH2COOH, CH4 M–OCH3, CH-COOH

IR (cm-1)

2500-3300 2961 1701 1022, 1243

COOH C(sp3)-H stretch C=O stetch (acid) Aryl ether stretch

1H

11.8 (exchanges) 7.20 (m) 6.86 (m) 3.8 (s) 3.6 (s)

COOH H4 H5 H7 H2

178.1 158.8 130.3 125.2 114.0 55.2 40.0

C1 C6 C4 C3 C5 C7 C2

Mass Spectrum (m/z)

NMR (ppm)

13C

NMR (ppm)

Problem 17 Formula Mass Spectrum (m/z)

NMR (ppm)

13C

NMR (ppm)

10

Problem 18 Formula

C7H10O4, UN=3

2 rings and 1 double bond

158 (M+) 143 (M-15) 115 (M-43) 83 (M-75)

M–CH3 M–CH3CO M–(CH3)2CO2H

IR (cm-1)

2940, 2995 1771 1202

C(sp3)-H stretches C=O stretch (ester) C-O stretch

1H

4.85 (dd) 4.75 (d) 4.42 (m) 1.47 (s), 1.38 (s)

H2 H3 H1 H6, H7

174.1 113.9 74.5, 75.4 70.1 25.5, 26.7

C4 C5 C2, C3 C1 C6, C7

C7H10O4, UN=3

2 rings and 1 double bond

158 (M+) 143 (M-15) 115 (M-43) 83 (M-75)

M–CH3 M–CH3CO M–(CH3)2CO2H

IR (cm-1)

2940, 2995 1771 1202

C(sp3)-H stretches C=O stretch (ester) C-O stretch

1H

4.85 (dd) 4.75 (d) 4.42 (m) 1.47 (s), 1.38 (s)

H2 H3 H1 H6, H7

174.1 113.9 74.5, 75.4 70.1 25.5, 26.7

C4 C5 C2, C3 C1 C6, C7

C9H7NO4, UN= 7

1 aryl ring and 3 double bonds

Mass Spectrum (m/z)

NMR (ppm)

13C

NMR (ppm)

Problem 18 Formula Mass Spectrum (m/z)

NMR (ppm)

13C

NMR (ppm)

Problem 19 Formula

11

Mass Spectrum (m/z)

193 (M+) 176 (M-17) 146 (M-47) 91 (M-102)

M–OH M–NO2H M–NO2, COOH (tropylium ion)

IR (cm-1)

2400-3000 2942 1691 1341

COOH C(sp3)-H stretch C=O stretch (acid) -NO2 stretch (sym)

1H

12.0 (exchanges) 7.73 (d) 7.46 (d) 7.19 (d) 6.25 (d)

COOH H2 H3 H5 H6

167.0 147.9 141.3 140.7 129.3 123.9 123.5

C7 C1 C5 C4 C3 C2 C6

C8H9NO2, UN=5

1 aryl ring and 1 double bond

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

1H

7.21(t) 6.92 (t) 6.81 (d) 6.48 (exchanges) 6.19 (exchanges) 4.3 (s)

H2 H1 H3 NH NH H5

171.2 157.0 129.7 122.1

C6 C4 C2 C1

NMR (ppm)

13C

NMR (ppm)

Problem 20 Formula Mass Spectrum (m/z)

NMR (ppm)

13C

NMR (ppm)

12

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

7.17 (m) 6.85 (m) 6.79 (m) 3.99 (quin) 3.91 (m) 3.63 (dd), 3.72 (dd) 2.59 (exchanges)

H2 H1 H3 H6 H5 (diastereotopic) H7 (diastereotopic) OH

158.3 129.5 121.2 114.4 70.4 68.9 63.6

C4 C2 C1 C3 C6 C5 C7

C9H12N2O, UN=5

1 aryl ring and 1 double bond

164 (MH+) 120 (M-44) 103 (M-61) 91 (M-73) 77 (M-87)

M–CONH2 M–HNH2CONH2 M–CHNH2CONH2 (tropylium ion) C6H5+

IR (cm-1)

3306, 3352 3034 1678 1605

NH2 stretches C(sp2)-H stretch C=O stretch (amide) NH2 bend

1H

6.87 (exchanges) 6.72-6.82 (m)

NH2 (amide) H1-H3

Problem 21 Formula Mass Spectrum (m/z)

IR (cm-1)

1H

NMR (ppm)

13C

NMR (ppm)

Problem 22 Formula Mass Spectrum (m/z)

NMR (ppm)

13

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+

IR (cm-1)

2600-3400 3047 1718 1235

COOH C(sp2)-H stretch C=O stretch (acid) C-O stretch

1H

12 (exchanges) 7.15 (t) 6.83 (t) 6.78 (d) 4.12 (t) 2.75 (t)

COOH H2 H1 H3 H5 H6

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

166 (M+) 135 (M-31) 122 (M-44) 77 (M-89)

M–OCH3 M–CHO, CH3 C6H5 +

13C

NMR (ppm)

Problem 23 Formula Mass Spectrum (m/z)

NMR (ppm)

13C

NMR (ppm)

Problem 24 Formula Mass Spectrum (m/z)

14

IR (cm-1)

3074 2948 2836 1705 1156, 1301

C(sp 2)-H stretch C(sp3 )-H stretch Aldehyde C-H stretch C=O stretch (aldehyde) C-O stretches

1H

9.90 (s) 6.99 (d) 6.69 (t) 3.90 (s)

CHO H3 H5 H6

191.9 161.1 138.3 107.0, 107.1 55.5

C1 C4 C2 C3, C5 C6

C14H14NO3, UN=8

2 aryl rings

214 (M+) 199 (M-15) 171 (M-43) 128 (M-86)

M–CH3 M–CO, CH3 M–2CO, 2CH3

IR (cm-1)

2955 1248 825

C(sp3)-H stretch C-O stretch 1,4-disubstituted aromatic

1H

7.50 (d) 6.97 (d) 3.91 (s)

H2 H3 H5

158.6 133.4 127.6 114.1 55.2

C4 C1 C2 C3 C5

C7H11BrO 4, UN=2

2 double bonds

238, 240 (M+, [M+2]+) 193, 195 (M-45) 166, 168 (M-72) 138, 140 (M-100) 29 (M-209)

Br present (1:1) M–OCH2CH3 M–CO2CH2CH3 CH2BrCOOH+ CH3CH2 +

NMR (ppm)

13C

NMR (ppm)

Problem 25 Formula Mass Spectrum (m/z)

NMR (ppm)

13C

NMR (ppm)

Problem 26 Formula Mass Spectrum (m/z)

15

IR (cm-1)

2986 1743 1149

C(sp 3)-H stretch C=O stretch (ester) C-O stretch

1H

4.82 (s) 4.28 (q) 1.30 (t)

H4 H2 H1

164.5 63.2 42.3 13.8

C3 C2 C4 C1

C8H19N, UN=0

Fully saturated

129 (M+) 86 (M-43) 44 (M-85)

M–CH2CH2CH3 CH3NH=CH2+ (McLafferty Rgt)

IR (cm-1)

3410 2928 1461 1132

NH stretch C(sp3)-H stretch CH2 and CH3 bend C-N stretch

1H

2.57 (t) 1.45 (pent) 1.31 (sextet) 1.10 (exchanges) 0.90 (t)

H4 H3 H2 NH H1

49.8 32.3 20.4 13.9

C4 C3 C2 C1

C6H12O2Cl2, UN=0

Fully saturated

187 (M+) 137, 139 (M-49) 107, 109 (M-79) 93, 95 (M-93) 63, 65 (M-79) 28 (M-158)

M–CH2Cl M–OCH2CH2Cl M–CH2OCH2CH2Cl ClCH2CH2+ M–2(OCH2CH2Cl)

2873 1127 665

C(sp3)-H stretch C-O stretch C-Cl stretch

NMR (ppm)

13C

NMR (ppm)

Problem 27 Formula Mass Spectrum (m/z)

NMR (ppm)

13C

NMR (ppm)

Problem 28 Formula Mass Spectrum (m/z)

IR (cm-1)

16

3.77 (t) 3.69 (s) 3.64 (t)

H2 H3 H1

71.3 70.6 42.7

C2 C3 C1

C3H7OCl, UN=0

Fully saturated

Mass Spectrum (m/z)

94, 96 (M+, [M+2]+) 63 (M-31) 45 (M-49) 28 (M-66)

Cl present (1:3) M–OCH3 M–CH2Cl M–OCH3, Cl

IR (cm-1)

2887 1125 671

C(sp3)-H stretch C-O stretch (ether) C-Cl stretch

1H

3.59-3.65 (m) 3.38 (s)

H1, H2 H3

72.4 58.8 42.6

C2 C3 C1

C6H6O2, UN=4

1 aryl ring

110 (M+) 92 (M-18) 81 (M-29) 64 (M-46)

M–H2O M–CHO M–CH2O2

IR (cm-1)

3325 (broad) 1518 1188 743

OH stretch Aromatic C=C stretch C-O stretch 1,2-disubstituted aromatic

1H

8.8 (exchanges) 6.72 (dd) 6.59 (dd)

OH H3 H2

145.2 119.2 115.6

C1 C3 C2

1H

NMR (ppm)

13C

NMR (ppm)

Problem 29 Formula

NMR (ppm)

13C

NMR (ppm)

Problem 30 Formula Mass Spectrum (m/z)

NMR (ppm)

13C

NMR (ppm)

17

Problem 31 Formula

C6H7NO, UN=4

1 aryl ring

109 (M+) 80 (M-29) 28 (M-81) 18 (M-91)

M–COH M–C4H3NO M–C6H5N

IR (cm-1)

3296, 3361 2500-3100 1593 1259 1180 907

NH2 stretches OH stretch NH2 bend C-N stretch C-O stretch NH2 bend

1H

8.8 (exchanges) 6.75 (t) 5.99 (s) 5.95 (dd), 5.98 (dd) 4.9 (exchanges)

OH H5 H2 H4, H6 NH2

157.9 149.6 129.2 105.3 103.2 100.9

C1 C3 C5 C4 C6 C2

C7H6NF3 , UN=4

1 aryl ring

161 (M+) 142 (M-19) 114 (M-47) 92 (M-69)

M–F M–CH2NF M–CF3

IR (cm-1)

3385 1630 1343 1123

NH2 stretch NH2 bend C-F stretch C-O stretch

...