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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).

2

Spectroscopic Technique

Signal/Information Comments

Problem 1 Formula Mass Spectrum (m/z) IR (cm-1)

1H NMR (ppm)

13C NMR (ppm)

C3H5BrO2, UN=1 152, 154 (M+, [M+2]+) 135, 137 (M-17) 107, 109 (M-45) 73 (M-79) 3067 (broad) 1717 >9 (exchanges) 3.45 (t) 3.0 (t) 178 (s) 24.3 (t) 38.6 (t)

1 double bond Br present (1:1) M–OH M–COOH M–Br COOH C=O stretch (acid) COOH H3 H2 C1 C3 C2


1H NMR (ppm)

13C NMR (ppm)

C8H14O4, UN=2 174 (M) 146 129 (M-45) 101 (M-73) 2986 1749 4.17 (m) 3.39 (q) 1.39 (d) 1.24 (t) 170 61 46 13.9, 13.5

2 double bonds M–CH2=CH2 (McLafferty Rgt) M–OCH2CH3 M–COOCH2CH3

C(sp3)-H stretch C=O stretch (ester) H2 (diastereotopic) H4 H5 H1 C3 C2 C4 C1 C5

3

Problem 3 Formula Mass Spectrum (m/z) IR (cm-1) 1H NMR (ppm)

13C NMR (ppm)

C9H12 UN=4 120 (M+) 105 (M-15) 91 (M-29) 3027, 3062 2865, 2900 7.35 (m) 2.64 (t) 1.71 (sextet) 1.02 (t) 142.6 128.4, 128.1 125.5 38.0 24.5 13.8

Phenyl ring M–CH3 M–CH2CH3 (tropylium ion)

C(sp2)-H stretch (aryl) C(sp3)-H stretch (alkyl) H1, H2, H3 H5

H6

H7

C4 C2, C3 C1 C5

C6

C7


13C NMR (ppm)

C7H13Br UN=1 176, 178 (M+, [M+2]+) 97 (M-79) 83 (M-93) 2938, 2849 1445 3.27 (d) 1.86 - 1.63 (m) 1.25 - 0.98 (m) 40.8, 40.0 31.7, 26.1, 25.8

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

C(sp3)-H stretches (alkyl) CH2 bend H5 H1-H4 H1-H4 C4, C5 C1, C2, C3


C5H8O, UN=2 84 (M+) 55 (M-29) 28 (M-56) 3063 2860, 2937

1 ring and 1 double bond M–C2H5 (Retro Diels-Alder) Ethene cation (Retro Diels-Alder) C(sp2)-H stretch C(sp3)-H stretches

4

1H NMR (ppm) 13C NMR (ppm)

1644 1070, 1238 6.35 (dt) 4.66 (m) 3.97 (t) 1.98 (q) 1.84 144.0 101.7 65.7 22.7, 19.4

C=C stretch C-O stretches H1 H2 H5 H3 H4 C1 C2 C5 C3, C4


13C NMR (ppm)

C9H13NO UN=4 152 (MH+) 120 (M-31) 91 (M-60) 60 (M-91) 3352, 3298 2800-3100 3075 2823 1581 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) 138.6 129.1, 128.3 126.3 66.2 54.1 40.8

Aryl ring M–CH2OH M–CH2CH(NH2)CH2OH (tropylium ion) M–PhCH3 Amine N-H stretches OH stretch C(sp2)-H stretch C(sp3)-H stretch Amine N-H bend H1- H3 OH H7 (diastereotopic) H6 H5 (diastereotopic) NH2

C4 C2, C3 C1 C7 C6 C5

5

Problem 7 Formula Mass Spectrum (m/z) IR (cm-1) 1H NMR (ppm) 13C NMR (ppm)

C6H10, UN = 2 82 (M+) 67 (M-15) 54 (M-28) 28 (M-54) 3064 2780, 2985 1692 5.66 (s) 1.99 (m) 1.61 (quintet) 127 25.1 22.6

1 ring and 1 double bond M–CH3 (Rearrangement) M–ethene (Retro Diels-Alder) M–1,3-butadiene (Retro Diels-Alder) C(sp2)-H stretch C(sp3)-H stretches C=C stretch H1 H2 H3 C1 C2 C3


C8H11NO, UN =4 138 (MH+) 120 (M-18) 107 (M-31) 77 (M-61) 30 (M-108) 2500-3500 3358 1598 7.36 (m) 5.2 (exchanges) 4.35 (dd) 2.59 (dd), 2.51 (dd) 1.3 (broad) 142.7 128.3, 125.8 127.4 74.1 49.2

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 H1-H3 OH H5

H6 (diastereotopic) NH2

C4 C2, C3 C1 C5 C6

Problem 9 Formula Mass Spectrum (m/z)

C10H7Br, UN=7 206, 208 (M+, [M+2]+)

Naphthyl ring Br present (1:1)

6

IR (cm-1) 1H NMR (ppm)

13C NMR (ppm)

127 (M-79) 101, 103 3054 1486, 1573 7.78 7.57, 7.51 7.47 (d) 7.31 (dd) 7.25 (m) 134.4 131.7 129.8, 129.4, 129.1 127.8 126.9, 126.8 126.2 119.4

M–Br M2+ C(sp2)-H stretch Aromatic C=C stretches H1 H9, H6 H4 H3 H7, H8 C5 C10 C1, C3, C4 C6 C8, C9 C7 C2


13C NMR (ppm)

C14H19NO4, UN=6 265 (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

1 aryl ring and 2 double bonds 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

7


1H NMR (ppm)

13C NMR (ppm)

C6H12O2, UN=1 116 (M) 98 (M-18) 70 (M-46) 57 (M-59) 3279, 3378 2862, 2935 3.3 3.0 1.9, 1.6 1.2 75.7 32.8 24.2

1 ring M–H2O M–CH2CH2, H2O (McLafferty Rgt) C3H5O+

2 OH stretches C(sp3)-H stretches H1, H2 OH H3, H6 H4, H5 C1, C2 C3, C6 C4, C5


1H NMR (ppm)

13C NMR (ppm)

C7H5NO4, UN=6 167 (M+) 150 (M-17) 137 (M-30) 120 (M-47) 109 (M-58) 3114 2500-3100 1673 1520 11.4 (s) 10.3 (s) 8.11 (d) 7.12 (dd) 7.06 (d) 190.2 163.0 140.5 134.8 127.6 119.1, 114.7

1 aryl ring and 2 double bond M–OH M–NO M–NO2H M–NO, CO

C(sp2)-H stretch OH C=O stretch (aldehyde) -NO2 stretch OH H7 H3 H4 H6 C7 C5 C2 C1 C3 C4, C6

8


13C NMR (ppm)

C5H10O4, UN=1 135 (MH+) 117 (M-18) 104 (M-31) 86 (M-49) 3226, 3372 2500-3000 1691 ~11 (br, exchanges) 4.5 (exchanges) 3.4 (q) 1.0 (s) 176.6 63.8 49.5 17.0

1 double bond M–H2O M–CH2OH M–CH2OH, H2O OH stretches COOH C=O stretch (acid) COOH OH H4 H1 C3 C4 C2 C1


1H NMR (ppm)

13C NMR (ppm)

C8H6O2, UN=6 134 (M+) 135 (M-1) 105 (M-29) 77 (M-57) 2698 1693 10.2 (s) 8.0 (s) 191.4 139.9 130.0

1 aryl ring and 2 double bonds M–H M–CHO C6H5+ Aldehyde C-H stretch C=O stretch (aldehyde) CHO H3 C1 C2 C3

9


13C NMR (ppm)

C13H10O3, UN=9 214 (M+) 121 (M-93) 93 (M-121) 3186 1683 1480 10.5 (exchanges) 8.0 (dd) 7.45 (td) 7.35 (m) 7.21 (m) 7.11 (m) 6.97 (d) 6.95 (t) 168.9 162.1 150.0 136.4 129.6, 130.3 126.3 121.6 117.7, 119.4 111.7

2 aryl rings and 1 double bond M–OPh M–CO2Ph

OH stretch C=O stretch (ester) Aromatic C=C stretch OH H6 H4 H10 H11 H9 H3 H5 C7 C2 C8 C4 C6, C10 C11 C9 C3, C5 C1

10


13C NMR (ppm)

C7H6O2, UN=5 122 (M+) 121 (M-1) 104 (M-18) 93 (M-29) 76 (M-46) 3239 2849 1665 ~11 (exchanges) 9.8 (s) 7.51 (m) 6.98 (m) 117.5, 119.7 120.5, small 133.6, 136.7 161.5, small 196.5

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) OH H7 H4, H6 H3, H5 C2, C4 C6 C1, C3 C5 C7


13C NMR (ppm)

C9H10O3, UN=5 166 (M+) 121 (M-45) 91 (M-75) 77 (M-89) 2500-3300 2961 1701 1022, 1243 11.8 (exchanges) 7.20 (m) 6.86 (m) 3.8 (s) 3.6 (s) 178.1 158.8 130.3 125.2 114.0 55.2 40.0

1 aryl ring and 1 double bond M–COOH M–CH2COOH, CH4 M–OCH3, CH-COOH COOH C(sp3)-H stretch C=O stetch (acid) Aryl ether stretch COOH H4 H5 H7 H2 C1 C6 C4 C3 C5 C7 C2

11


13C NMR (ppm)

C7H10O4, UN=3 158 (M+) 143 (M-15) 115 (M-43) 83 (M-75) 2940, 2995 1771 1202 4.85 (dd) 4.75 (d) 4.42 (m) 1.47 (s), 1.38 (s) 174.1 113.9 74.5, 75.4 70.1 25.5, 26.7

2 rings and 1 double bond M–CH3

M–CH3CO M–(CH3)2CO2H C(sp3)-H stretches C=O stretch (ester) C-O stretch H2 H3 H1 H6, H7 C4 C5 C2, C3 C1 C6, C7


13C NMR (ppm)

C7H10O4, UN=3 158 (M+) 143 (M-15) 115 (M-43) 83 (M-75) 2940, 2995 1771 1202 4.85 (dd) 4.75 (d) 4.42 (m) 1.47 (s), 1.38 (s) 174.1 113.9 74.5, 75.4 70.1 25.5, 26.7

2 rings and 1 double bond M–CH3

M–CH3CO M–(CH3)2CO2H C(sp3)-H stretches C=O stretch (ester) C-O stretch H2 H3 H1 H6, H7 C4 C5 C2, C3 C1 C6, C7

Problem 19 Formula

C9H7NO4, UN= 7

1 aryl ring and 3 double bonds

12

Mass Spectrum (m/z) IR (cm-1) 1H NMR (ppm)

13C NMR (ppm)

193 (M+) 176 (M-17) 146 (M-47) 91 (M-102) 2400-3000 2942 1691 1341 12.0 (exchanges) 7.73 (d) 7.46 (d) 7.19 (d) 6.25 (d) 167.0 147.9 141.3 140.7 129.3 123.9 123.5

M–OH M–NO2H M–NO2, COOH (tropylium ion) COOH C(sp3)-H stretch C=O stretch (acid) -NO2 stretch (sym) COOH H2 H3 H5 H6 C7 C1 C5 C4 C3 C2 C6


13C NMR (ppm)

C8H9NO2, UN=5 151 (M+) 107 (M-44) 94 (M-57) 77 (M-74) 3358, 3464 2922 1698 1248 7.21(t) 6.92 (t) 6.81 (d) 6.48 (exchanges) 6.19 (exchanges) 4.3 (s) 171.2 157.0 129.7 122.1

1 aryl ring and 1 double bond M–CONH2

M–CHCONH2 (phenol cation) C6H5+ NH stretches C(sp3)-H stretch C=O stretch (amide) C-O stretch H2 H1 H3 NH NH H5 C6 C4 C2 C1

13

114.5 67.0

C3 C5


13C NMR (ppm)

C9H12O3, UN=4 168 (M+) 151 (M-17) 119 (M-49) 107 (M-61) 94 (M-74) 77 (M-91) 3292 2935 1050, 1242 7.17 (m) 6.85 (m) 6.79 (m) 3.99 (quin) 3.91 (m) 3.63 (dd), 3.72 (dd) 2.59 (exchanges) 158.3 129.5 121.2 114.4 70.4 68.9 63.6

1 aryl ring M–OH M–OH, CH2OH M–CH(OH)CH2OH M–CHCH(OH)CH2OH (phenol cation) C6H5+ OH stretch C(sp3)-H stretch C-O stretches H2 H1 H3 H6 H5 (diastereotopic) H7 (diastereotopic) OH C4 C2 C1 C3 C6 C5 C7


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)

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

14

13C NMR (ppm)

6.5 (exchanges) 2.88 (dd) 2.12 (dd), 2.46 (dd) 1.12 (exchanges) 176.7 138.9 128.0, 129.3 126.0 56.2 41.2

NH2 (amide) H6 H5 (diastereotopic) NH2 (amine) C7 C4 C2, C3 C1 C6 C5


13C NMR (ppm)

C9H10O3, UN=5 166 (M+) 149 (M-17) 94 (M-72) 77 (M-89) 2600-3400 3047 1718 1235 12 (exchanges) 7.15 (t) 6.83 (t) 6.78 (d) 4.12 (t) 2.75 (t) 177.3 158.3 129.4 121.1 114.5 62.8 34.3

1 aryl ring and 1 double bond M–OH

M–CHCH2COOH

C6H5+ COOH C(sp2)-H stretch C=O stretch (acid) C-O stretch COOH H2 H1 H3 H5 H6 C7 C4 C2 C1 C3 C5 C6


C9H10O3, UN=5 166 (M+) 135 (M-31) 122 (M-44) 77 (M-89)

1 aryl ring and 1 double bond M–OCH3 M–CHO, CH3

C6H5+

15


13C NMR (ppm)

3074 2948 2836 1705 1156, 1301 9.90 (s) 6.99 (d) 6.69 (t) 3.90 (s) 191.9 161.1 138.3 107.0, 107.1 55.5

C(sp2)-H stretch C(sp3)-H stretch Aldehyde C-H stretch C=O stretch (aldehyde) C-O stretches CHO H3 H5 H6 C1 C4 C2 C3, C5 C6


13C NMR (ppm)

C14H14NO3, UN=8 214 (M+) 199 (M-15) 171 (M-43) 128 (M-86) 2955 1248 825 7.50 (d) 6.97 (d) 3.91 (s) 158.6 133.4 127.6 114.1 55.2

2 aryl rings M–CH3 M–CO, CH3

M–2CO, 2CH3 C(sp3)-H stretch C-O stretch 1,4-disubstituted aromatic H2 H3 H5 C4 C1 C2 C3 C5


C7H11BrO4, UN=2 238, 240 (M+, [M+2]+) 193, 195 (M-45) 166, 168 (M-72) 138, 140 (M-100) 29 (M-209)

2 double bonds Br present (1:1) M–OCH2CH3 M–CO2CH2CH3

CH2BrCOOH+

CH3CH2+

16


13C NMR (ppm)

2986 1743 1149 4.82 (s) 4.28 (q) 1.30 (t) 164.5 63.2 42.3 13.8

C(sp3)-H stretch C=O stretch (ester) C-O stretch H4 H2 H1 C3 C2 C4 C1


13C NMR (ppm)

C8H19N, UN=0 129 (M+) 86 (M-43) 44 (M-85) 3410 2928 1461 1132 2.57 (t) 1.45 (pent) 1.31 (sextet) 1.10 (exchanges) 0.90 (t) 49.8 32.3 20.4 13.9

Fully saturated M–CH2CH2CH3 CH3NH=CH2+ (McLafferty Rgt) NH stretch C(sp3)-H stretch CH2 and CH3 bend C-N stretch H4 H3 H2 NH H1 C4 C3 C2 C1


C6H12O2Cl2, UN=0 187 (M+) 137, 139 (M-49) 107, 109 (M-79) 93, 95 (M-93) 63, 65 (M-79) 28 (M-158) 2873 1127 665

Fully saturated M–CH2Cl M–OCH2CH2Cl M–CH2OCH2CH2Cl ClCH2CH2+ M–2(OCH2CH2Cl) C(sp3)-H stretch C-O stretch C-Cl stretch

17

1H NMR (ppm)

13C NMR (ppm)

3.77 (t) 3.69 (s) 3.64 (t) 71.3 70.6 42.7

H2 H3 H1 C2 C3 C1


13C NMR (ppm)

C3H7OCl, UN=0 94, 96 (M+, [M+2]+) 63 (M-31) 45 (M-49) 28 (M-66) 2887 1125 671 3.59-3.65 (m) 3.38 (s) 72.4 58.8 42.6

Fully saturated Cl present (1:3) M–OCH3

M–CH2Cl M–OCH3, Cl C(sp3)-H stretch C-O stretch (ether) C-Cl stretch H1, H2 H3

C2 C3 C1


13C NMR (ppm)

C6H6O2, UN=4 110 (M+) 92 (M-18) 81 (M-29) 64 (M-46) 3325 (broad) 1518 1188 743 8.8 (exchanges) 6.72 (dd) 6.59 (dd) 145.2 119.2 115.6

1 aryl ring M–H2O M–CHO M–CH2O2

OH stretch Aromatic C=C stretch C-O stretch 1,2-disubstituted aromatic OH H3 H2 C1 C3 C2

18


13C NMR (ppm)

C6H7NO, UN=4 109 (M+) 80 (M-29) 28 (M-81) 18 (M-91) 3296, 3361 2500-3100 1593 1259 1180 907 8.8 (exchanges) 6.75 (t) 5.99 (s) 5.95 (dd), 5.98 (dd) 4.9 (exchanges) 157.9 149.6 129.2 105.3 103.2 100.9

1 aryl ring M–COH M–C4H3NO M–C6H5N NH2 stretches OH stretch NH2 bend C-N stretch C-O stretch NH2 bend OH H5 H2 H4, H6 NH2 C1 C3 C5 C4 C6 C2


13C NMR (ppm)

C7H6NF3, UN=4 161 (M+) 142 (M-19) 114 (M-47) 92 (M-69) 3385 1630 1343 1123 7.24 (t) 6.99 (dd) 6.89 (s) 6.82 (dd) 3.9 (exchanges) 146.6 129.6

1 aryl ring M–F

M–CH2NF M–CF3

NH2 stretch NH2 bend C-F stretch C-O stretch H5 H4 H2 H6 NH2 C1 C4

19

123.0 (q) 117.9 114.9 111.2

C7 C6 C4 C2


13C NMR (ppm)

C6H4Cl2, UN=4 146, 148, 150 (M+, [M+2]+, [M+4]+) 111 (M-35) 3067 1458 746 7.43 (m) 7.19 (m) 132.5 130.5 127.7

1 aryl ring 2 Cl present (10:6.6:1) M–Cl C(sp2)-H stretch Aromatic C=C stretch 1,2-disubstituted aromatic H2 H3 C1 C2 C3


13C NMR (ppm)

C6H5NO3, UN=5 139 (M+) 122 (M-17) 93 (M-46) 3477 3108 1312, 1535 1177 >9 (exchanges) 8.17 (dd) 7.59 (td) 7.18 (dd) 7.00 (td) 155.1 137.5 133.5 125.0 119.9, 120.2

1 aryl ring and 1 double bond M–OH M–NO2

OH stretch C(sp2)-H stretch NO2 stretches C-O stretch OH H3 H5 H6 H4 C2 C5 C1 C3 C4, C6

20


13C NMR (ppm)

C6H5NO3, UN=5 139 (M+) 93 (M-46) 81 (M-74) 65(M-74) 3398 3114 1354, 1534 1213 7.81 (dd) 7.70 (t) 7.41 (t) 7.18 (dd) 5.7 (exchanges) 155.8 149.1 130.2 121.9 115.8 110.5

1 aryl ring and 1 double bond M–NO2

M–CNO2

M–CNO3 OH stretch C(sp2)-H stretch NO2 stretches C-O stretch H4 H2 H5 H6 OH C3 C1 C5 C6 C4 C2


13C NMR (ppm)

C4H4N2, UN=4 80 (M+) 52 (M-28) 26(M-54) 3050 8.5 145.1

1 aryl ring M–C2H4

M–C2H2N2 C(sp2)-H stretch H1 C1


C6H7PO3, UN=4 158 (M+) 141 (M-17) 94 (M-64) 77 (M-81) 2756 (broad)

1 aryl ring M–OH M–PO2H (phenol cation) C6H5+

PO-H stretch

21

1H NMR (ppm)

13C NMR (ppm)

7.68 (dd) 7.48-7.53 (m) 7.43-7.47 (m) 5.5 (exchanges) 134.1 (d) 130.9 (d) 130.6 (d) 128.1 (d)

H3 H1 H2 OH C4 C1 C3 C2


13C NMR (ppm)

C9H8N2, UN=7 144 (M+) 117 (M-27) 90 (M-54) 77 (M-67) 3392 (broad) 3115 1514 1308 10.5 (exchanges) 7.76 (d) 7.72 (s) 7.38-7.42 (m) 7.28 (t) 138.9 135.9 133.1 128.9 127.2 125.1 115.7

2 aryl rings M–HCN M–C2H3N2 C6H5+ N-H stretch C(sp2)-H stretch Aromatic C=C stretch C-N stretch NH H3 H7 H2, H6 H1 C4 C7 C5 C2 C1 C3 C6


C5H6O3, UN=3 114 (M+) 86 (M-28) 73 (M-41) 60 (M-54) 55 (M-59) 2981 1758, 1830 1230

1 ring and 2 double bonds M–CO M–C2H3O M–C3H5O M–C2H3O2 C(sp3)-H stretch Anhydride stretches C-O stretch

22

1H NMR (ppm)

13C NMR (ppm)

2.43 (t) 1.96 (pent) 177.5 32.9 19.6

H2 H3 C1 C2 C3


13C NMR (ppm)

C16H35N, UN=0 241 (M+) 142 (M-99) 3277 2854, 2929 1100 2.57 (t) 2.17 (s) 1.45 (m) 1.21-1.32 (m) 0.87 (t) 50.1 30.1, 31.8 27.4, 29.5, 29.8 22.6 14.0

Fully saturated M–C7H15

N-H stretch C(sp3)-H stretches C-N stretch H1 NH H2 H3-H7 H8 C1 C2, C6 C3, C4, C5 C7 C8


C6H12O5, UN=1 164 (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)

1 ring 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

23

13C NMR (ppm)

3.34 (exchanges) 3.25 (s) 100.6 69.0 68.6 68.2 62.9 54.8

OH H6 C5 C4 C3 C2 C1 C6


13C NMR (ppm)

C13H9NO3, UN=10 227 (M+) 150 (M-77) 105(M-122) 77 (M-150) 3101 1651 1512 8.34 (d) 7.93 (d) 7.80 (d) 7.65 (t) 7.53 (t) 194.8 149.7 142.8 136.2 133.4 128.2, 130.0, 130.8 123.5

2 aryl rings and 2 double bonds M–C6H5 M–C7H4NO2 M–C7H4NO3

C(sp2)-H stretch C=O stretch (ketone) NO2 stretch H8 H7 H3 H1 H2 C5 C9 C6 C4 C1 C2, C3, C7 C8


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)

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

24

13C NMR (ppm)

6.97 (dd) 6.78 (td) 2.3 (s) 161.7 (d) 139.9 133.3 118.9 117.7 (d) 114.4 (d) 23.0

H6 H4 H7

C5 C1 C3 C2 C6 C4 C7


13C NMR (ppm)

C13H10 UN=9 166, 167 (M+) 165 (M-1) 3028 1446 7.80 (d) 7.56 (d) 7.32 (t), 7.38 (t) 3.91 (s) 143.1 141.6 126.6, 126.8 125.0 119.8 36.8

2 aryl rings and 1 ring M–H C(sp2)-H stretch Aromatic C=C stretch H2 H5 H3, H4 H7 C6 C1 C3, C4 C5 C2 C7


C10H11NO3, UN=6 117 (M+) 162 (M-15) 107 (M-70) 2934 2241 1518 1025, 1262 6.83 (m) 3.87 (s), 3.89 (s) 3.70 (s)

1 aryl ring and 1 triple bond 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

25

13C NMR (ppm) 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


13C NMR (ppm)

C5H12O2, UN=2 104 (M+) 73 (M-31) 2948, 2993 1375 1084 3.19 (s) 1.35 (s) 99.8 48.3 23.8

2 double bonds or rings M M–OCH3 C(sp3)-H stretches CH3 bending C-O stretching H3 H1 C2 C3 C1


1H NMR (ppm) 13C NMR (ppm) (2 sets of peaks)

C6H12O3, UN=2 131 ([M-1]+) 115 (M-17) 101 (M-31) 72 (M-60) 2906, 2958, 2996 1026, 1218 5.09 (m) 3.42 (s), 3.36 (s) 1.82, 2.10 (m) 106.1 55.3 30.9

2 double bonds and/or rings M–CH4 M–OCH3 C4H8O+ C(sp3)-H stretches C-O stretches H2 H1 H3 C2 C1 C3


C10H20O, UN=2 156 (M+) 138 (M-18)

2 double bonds or rings M–H2O

26

IR (cm-1) 1H NMR (ppm) 13C NMR (ppm)

3252 2927 1456 1045 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) 71.5 50.1 45.0 34.5 31.6 25.8 23.1 22.2 16.0, 20.1

OH stretch C(sp3)-H stretch CH2 bend C-O stretch H4 H8 H3 (1H, diastereotopic) H6, H7 (1H, diastereotopic) H2 OH H3 (1H), H5, H7 (1H), H9 (6H) H1 C4 C5 C3 C7 C2 C8 C6 C1 C9


C9H16O5, UN=2 205 (MH+) 159 (M-45) 141 (M-63) 130 (M-74) 113 (M-91) 3511 2983, 2939 1740 1372 1024, 1189 4.43-4.48 (m) 4.18 (q) 3.45 (exchanges) 2.53-2.58 (m) 1.28 (t) 171.8 64.7 60.7

2 double bonds M–OC2H5 (α-cleavage) M–OC2H5, H2O M–OC2H5, C2H5 M–OC2H5, CO, H2O OH stretch C(sp3)-H stretches C=O stretch (ester) CH3 bend C-O stretches H5 H2 OH H4 (diastereotopic) H1 C3 C5 C2

27

40.6 14.1

C4 C1


C3H7OCl, UN=0 93, 95 (M-1+, [M+2]-1+) 78 (M-16) 58 (M-36) 3352 2889, 2961 1448 1054 721 3.83 (t) 3.68 (t) 2.1 (q) 1.52 (exchanges) 59.4 41.7 34.8

Fully saturated Cl present (1:3), ClCH2CH2CH2O+ M–OH CH2=CHCH2OH+

OH stretch C(sp3)-H stretch OH, CH2 bends C-O stretch C-Cl stretch H3 H1 H2 OH C3 C1 C2


C8H6O3, UN=6 150 (M+) 122 (M-28) 94 (M-56) 66 (M-84) 3332 2923 1760 1476 1078, 1152 9.2 (exchanges) 6.96 (d) 6.76 (m) 6.67 (dd) 3.90 (s) 174.7 153.7 146.6 124.9

1 aryl ring, 1 ring, and 1 double bond M–CO M–2CO (phenol cation) M–3CO (cyclopentadiene cation) OH stretch C(sp3)-H stretch C=O stretch (lactone) OH, CH2 bends C-O stretches OH H3 H6 H4 H7 C8 C5 C2 C1

28

110.3, 111.7, 114.1 33.1

C3, C4, C6 C7


C9H10O2, UN=5 150 (M+) 132 (M-18) 104 (M-46) 77 (M-73) 2200-3200 3068 2967 1692 1304 > 9 (exchanges) 7.23 (t) 7.07 (d) 2.4 (s) 174.9 135.6 132.2 129.9 127.8 20.1

1 aryl ring and 1 double bond M–H2O M–CO, H2O C6H5+ COOH C(sp2)-H stretch C(sp3)-H stretch C=O stretch (acid) OH bend COOH H4 H3 H5 C6 C2 C1 C4 C3 C5


C6H8O2, UN=3 112 (M+) 83 (M-29) 56 (M-42) 2912, 2965 1711 2.8 (s) 208.3 36.6

1 ring and 2 double bonds M–CO M2+ C(sp3)-H stretches C=O stretch (ketone) H2 C1 C2


C5H7NO3, UN=3 129 (M+) 114 (M-15) 86 (M-43)

1 ring and 2 double bonds M–CH3 M–CH3CO

29


70 (M-59) 43 (M-86) 28 (M-101) 15 (M-114) 3266 1783 1043, 1246 6.8 (exchanges) 5.82 (dd) 3.25 (dd), 3.28 (dd) 2.1 (s) 171.1 165.2 72.9 44.8 20.7

M–O=C-OCH3 CH3C=O CH=NH CH3 NH stretch C=O stretch (amide) C-O stretches NH H3 H2 H5 C4 C1 C3 C2 C5


13C NMR (ppm)

C8H8O2, UN=5 136 (M+) 135 (M-1) 107(M-29) 77(M-59) 3010 2934 2743, 2839 1684 1261 ~10 (s) 7.85 (d) 7.00 (d) 3.90 (s) 190.8 164.5 131.9 129.9 114.2 55.5

1 aryl ring and 1 double bond M–H M–CHO (anisole cation) C6H5+ C(sp2)-H stretch C(sp3)-H stretch Aldehyde C-H stretches C=O stretch (aldehyde) C-O stretch CHO H4 H3 H1 C6 C2 C4 C5 C3 C1

Problem 56 Formula

C7H11NO2, UN=3

1 double bond and 1 triple bond

30

Mass Spectrum (m/z) IR (cm-1) 1H NMR (ppm)

13C NMR (ppm)

141 (M+) 126(M-15) 57 (M-84) 2936, 2983 2262 1744 3.3(s) 1.5(s) 161.8 113.4 84.3 27.7 25.8

M–CH3 C4H9+ (t-Bu cation) C(sp3)-H stretches C≡N stretch C=O stretch H2 H5 C3 C1 C4 C5 C2


C6H5O2SCl, UN=4 176, 178 (M+, [M+2]+) 141 (M-35) 77 (M-99) 3069 1377, 1185 8.05 (dd) 7.76 (tt) 7.63 (t) 144.3 135.2 129.6, 126.9

4 double bonds/ring (likely aromatic) Cl present (1:3) M–Cl C6H5+ C(sp2)-H stretch S=O stretches H3 H1 H2 C4 C1 C2, C3


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)

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

31

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) 156.1 152.3 149.0 139.9 119.3 87.9 85.9 73.4 70.6 61.6

NH2 H6 OH (connected to C7, C8) OH (connected to C10) H7 H8 H9 H10 (diastereotopic) C3

C4 C5 C1 C2 C6 C9 C7 C8 C10


C14H12O2, UN=9 212 (M+) 211 (M-1) 91 (M-121) 77 (M-135) 3056 2743, 2827 1688 1021, 1255 ~10 (s) 7.85 (d) 7.35-7.45 (m) 6.90 (d) 5.1 (s) 190.8 163.7 135.8 131.9 130.0 127.4, 128.3, 128.7 115.1 70.2

2 aryl rings and 1 double bond M–H C7H7+ (tropylium ion) C6H5+

C(sp2)-H stretch Aldehyde C-H stretches C=O stretch (aldehyde) C-O stretches CHO H8 H1-H3 H7 H5 C10 C6 C4 C8 C9 C1, C2, C3 C7 C5

32


C4HO3Br UN=4 176, 178 (M+, [M+2]+) 132 (M-44) 104 (M-72) 3121, 3182 1781 1597 1225 7.17 (s) 160.2, 161.7 133.7 133.4

1 ring and 3 double bonds Br present (1:1) M–CO2 M–CO2, CO C(sp2)-H stretches C=O stretch (anhydride) C=C stretch C-O stretch H3 C1, C2 C3 C4


13C NMR (ppm)

C8H14O3, UN=2 158 (M+) 103 (M-55) 85 (M-73) 57 (M-101) 2935, 2981 1718 1023, 1149 3.3(s) 2.3(s) 1.5(s) 201.2 166.3 81.9 51.5 30.0 27.9

2 double bonds M–C3H3O M–OC(CH3)3 C4H9+ (t-Bu cation) C(sp3)-H stretches C=O stretch C-O stretches H3 H1 H6 C2 C4 C5 C3 C1

C6


C6H11O2Br, UN=1 194, 196 (M+, [M+2]+) 177, 179 (M-17) 115 (M-79) 97 (M-97) 60 (M-134)

1 double bond Br present (1:1) M–OH M–Br M–Br, H2O M-CH2=CHCH2CH2Br

33


13C NMR (ppm)

2500-3500 2942 1711 1195 ~10 (exchanges) 3.40 (t) 2.39 (t) 1.82-1.87 (m) 1.65 (pent) 1.55 (pent) 179.3 33.4, 33.6 23.7, 27.5, 32.3

COOH C(sp3)-H stretch C=O stretch C-O stretch COOH H1 H5 H2 H4 H3 C6 C1, C5 C2, C3, C4


C14H12O2, UN=9 212 (M+) 195 (M-17) 105 (M-107) 77 (M-135) 3378 1677 7.91 (dd) 7.52 (tt) 7.40 (t) 7.28-7.36 (m) 5.98 (d) 4.59 (exchanges) 198.8 138.9 133.9 133.4 127.2-129.1 (5 signals) 76.1

2 aryl rings and 1 double bond M–OH C7H5O+ C6H5+ OH stretch C=O stretch (ketone) H3 H1 H9 H2, H8, H10 H6 OH C5 C4 C1 C7 C2-C3, C8-C10 C6


C10H12O, UN=5 148 (M+) 120 (M-28) 105 (M-43) 77 (M-71)

1 aryl ring and 1 double bond M–CH2=CH2 (McLafferty Rgt) M– CH2CH2CH3 C6H5+

34


3060 2874, 2962 1680 1450 7.95 (d) 7.55 (t) 7.47 (t) 2.95 (t) 1.79 (sextet) 1.00 (t) 200.4 137.0 132.8 128.0, 128.5 40.4 17.7 13.8

C(sp2)-H stretch C(sp3)-H stretches C=O stretch (ketone) CH2, CH3 bends H2

H1 H3 H6 H7 H8 C5 C4 C1 C2, C3 C6 C7 C8

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