Robert M Silverstein Francis X Webster David Kiemle Solutions Manual For Spectrometric Identification of Organic Compounds Wiley 2005 PDF

Answers for Student Exercises 1.1 to 1.
5 1
Atom Type # of Atoms Mass Total Mass

Hydrogen 22 1.00783 22.17226
a
Carbon 10 12.00000 120.00000
Nitrogen 0 14.0031 0.00000
3-ethyloctane Oxygen 0 15.9949 0.00000
C10H22
Sulfur 0 31.9721 0.00000
CnHmXxNyOz IHD Bromine 0 78.9183 0.00000
Index = (n) - (m/2) - (x/2) + (y/2) + 1 = 0 Exact Mass 142.17226
- (C2H5 )
Rule 3
- (C5H11 )
Rule 3
H - (CH2=CH2)
Rule 9
b Atom Type # of Atoms Mass Total Mass

Hydrogen 18 1.00783 18.14094
Carbon 10 12.00000 120.00000
Nitrogen 0 14.0031 0.00000
3-butylcyclohex-1-ene Oxygen 0 15.9949 0.00000
C10H18 Sulfur 0 31.9721 0.00000
or
- (C4H9 )
Rule 5 and 6
- (CH2=CH2)
Rule 6
- (C3H7 )
Rule 3
Answers for Student Exercises 1.1 to 1.5 2
O Atom Type # of Atoms Mass Total Mass

c Hydrogen 18 1.00783 18.14094
Carbon 13 12.00000 156.00000
Nitrogen 0 14.0031 0.00000
2-methyl-1-phenylhexan-1-one Oxygen 1 15.9949 15.99490
C13H18O
Sulfur 0 31.9721 0.00000
O O O
- (C6H13 )
Rule 8
O O
- (C6H5 )
Rule 8
H
O - (C4H8) O OH
Rule 9 H
O
- (CO)
Rule 8+9

d Hydrogen 22 1.00783 22.17226
Carbon 11 12.00000 132.00000
(E)-undec-3-ene
C11H22 Nitrogen 0 14.0031 0.00000
Oxygen 0 15.9949 0.00000
Sulfur 0 31.9721 0.00000
or
- (CH3)
Rule 5
- (C6H13)
Rule 5
H
- (C7H14)
Rule 9
e Hydrogen 18 1.00783 18.14094
Carbon 12 12.00000 144.00000
Nitrogen 0 14.0031 0.00000
1-(hexan-2-yl)benzene Oxygen 0 15.9949 0.00000
C12H18
Sulfur 0 31.9721 0.00000
- (CH3 )
Rule 7
- (C4H9 )
Rule 7
H H
- (C4H8 )
Rule 9
H
f Hydrogen 16 1.00783 16.12528
OH Carbon 7 12.00000 84.00000
Nitrogen 0 14.0031 0.00000
heptan-2-ol
C7H16O Oxygen 1 15.9949 15.99490
Sulfur 0 31.9721 0.00000
- (C5H11 )
OH
Rule 8 OH
- (CH3 )
OH OH
Rule 8
H - (H )
OH OH
Rule 8
H - (H2O)
OH
Rule 9

Hydrogen 22 1.00783 22.17226
g
COOH Carbon 11 12.00000 132.00000
Nitrogen 0 14.0031 0.00000
3,5,7-trimethyloctanoic acid
Oxygen 2 15.9949 31.98980
C11H22O2
Sulfur 0 31.9721 0.00000
O
C
O - (OH )
OH Rule 8
O
C
O
O O
- (C10H21 )
OH C C
Rule 8 OH OH
H
H - (C9H18) O OH
O
Rule 9 HO HO
HO
Hydrogen 14 1.00783 14.10962
h
OH Carbon 6 12.00000 72.00000
Nitrogen 0 14.0031 0.00000
hexan-1-ol
C6H14O Oxygen 1 15.9949 15.99490
Sulfur 0 31.9721 0.00000
H
O - (CH2=CH2 ) - (H2O)
H
Rule 9
- (C5H11 )
OH H 2C
OH
Rule 8
- (H )
OH OH
Rule 8

Hydrogen 18 1.00783 18.14094
i
Carbon 8 12.00000 96.00000
OH Nitrogen 0 14.0031 0.00000
2-methylheptan-2-ol Oxygen 1 15.9949 15.99490
C8H18O
Sulfur 0 31.9721 0.00000
- (C5H11 )
OH
Rule 8 OH
- (CH3 )
OH OH
Rule 8
H
O
H - (H2O) - (CH2=C(CH3)2)
Rule 8 Rule 8

j Hydrogen 16 1.00783 16.12528
S Carbon 7 12.00000 84.00000
butyl(propyl)sulfane Nitrogen 0 14.0031 0.00000
C7H16S Oxygen 0 15.9949 0.00000
Sulfur 1 31.9721 31.97210
- (C3H7 )
S S
Rule 8
S - (CH2=CH2)
SH
H Rule 9
- (C2H5 )
S S
Rule 8

k
OH Hydrogen 20 1.00783 20.15660
Carbon 13 12.00000 156.00000
Nitrogen 0 14.0031 0.00000
(2-hexylphenyl)methanol Oxygen 1 15.9949 15.99490
C13H20O Sulfur 0 31.9721 0.00000
OH OH
or
- (C5H11 ) OH
OH
Rule 7
CH2
- (OH ) CH2
OH
Rule 7
OH - (H2O)
H Rule 9

l Hydrogen 9 1.00783 9.07047
Carbon 13 12.00000 156.00000
NO2 Nitrogen 1 14.0031 14.00310
(4-nitrophenyl)(phenyl)methanone Oxygen 3 15.9949 47.98470
C13H9NO3
Sulfur 0 31.9721 0.00000
O O
- (C6H4NO2 )
Rule 7&8
NO2
O
- (CO)
Rule 8&9
O O
- (C6H5 )
Rule 7&8
NO2 NO2

m O
Hydrogen 22 1.00783 22.17226
Carbon 10 12.00000 120.00000
Nitrogen 0 14.0031 0.00000
Oxygen 1 15.9949 15.99490
3-(ethoxymethyl)heptane
C10H22O Sulfur 0 31.9721 0.00000
- (CH3 )
O O
Rule 8 CH2
- (C7H15 )
O O
Rule 8
- (C4H9)
O O
Rule 3

n Hydrogen 19 1.00783 19.14877
H Carbon 10 12.00000 120.00000
Br Nitrogen 0 14.0031 0.00000
2-bromodecanal Oxygen 1 15.9949 15.99490
C10H19BrO
Sulfur 0 31.9721 0.00000
O O
- (H )
H
Rule 8
Br Br
O
- (CO )
Br Rule 9
Br
H O H
H O
- (C8H16)
H
Rule 9 H
Br
Br
o Atom Type # of Atoms Mass Total Mass

O Hydrogen 14 1.00783 14.10962
Carbon 8 12.00000 96.00000
O Nitrogen 0 14.0031 0.00000
cyclohexyl acetate Oxygen 2 15.9949 31.98980
C8H14O2 Sulfur 0 31.9721 0.00000
O O - (C6H11O ) O
Rule 8
O O - (CH3 ) O O
Rule 8
O O O
- (CH2=C=O) H
H Rule 9
Molecular
A O Base Peak Ion Fragement Ion Fragment Loss Rearrangment
71 114 99 / C6H11O 15 / CH3
86 / C5H10 28 / C2H4 R
4-Heptanone
C7H14O 71 / C4H7O 43 / C3H7
Exact Mass: 114.1045 58 / C3H5O 56 / C4H8 R
IHD = 1, match with (k)
43 / C3H7 71 / C4H7O
Molecular
B
Base Peak Ion Fragement Ion Fragment Loss Rearrangment
OH
59 116 by CI 115 / C7H15O 1/H
98 / C7H14 18 / H2O R
3-Heptanol 87 / C5H11O 29 / C2H5
C7H16O 69 / C5H9 18 / H2O, 29 / C2H5 R
Exact Mass: 116.1201
IHD = 0, match with (m) 59 / C3H7O 57 / C4H9
45 / C2H5O 71 / C5H11
43 / C3H7 73 / C4H9O
41 / C4H5 18 / H2O, 57 / C4H9 R
C Molecular
Br Base Peak Ion Fragement Ion Fragment Loss Rearrangment
Tropylium
4-Bromotoluene 91 170 91 / C7H7 79 / Br Ion
C7H7Br 75 / C6H3 80 / HBr, 16 / CH4 R
IHD = 4, match with (v) 65 / C5H5 79 / Br, 26 / C2H2 R
50 / C4H2 120 / C7H5Br
39 / C3H2 131 / C4H5Br
D Br Molecular
2-Bromopentane 71 150 121 / C3H6Br 29 / C2H5

C5H11Br 107 / C2H4Br 43 / C3H7
IHD = 0, match with (r) 71 / C5H11 79 / Br
55 / C4H7 80 / HBr, 16 / CH4 R
43 / C3H7 C2H4Br
Molecular
E O Base Peak Ion Fragement Ion Fragment Loss Rearrangment
43 100 85 / C5H9O 15 / CH3
2-Hexanone 71 / C4H7O 29 / C2H5
C6H12O 58 / C4H10 42 / C2H2O R
IHD = 1, match with (h) 57 / C3H5O 43 / C3H7
43 / C3H7 57 / C3H5O
F O Molecular
OH 74 74 73 / C3H5O2 1/H
Propionic Acid
57 / C3H5O 17 / OH
C3H6O2
Exact Mass: 74.0368 56 / C3H4O 18 / H2O R
IHD = 1, match with(c) 45 / CHO2 29 / C2H5
Molecular
G Base Peak Ion Fragement Ion Fragment Loss Rearrangment
H2N 73 73 56 / C4H8 17 / NH3 R
butan-1-amine 55 / C4H7 18 / NH4 R

C4H11N 44 / C2H6N 29 / C2H5
Exact Mass: 73.0896
IHD = 0, match with (b) 43 / C3H7 30 / CH4N
H Molecular
OH Base Peak Ion Fragement Ion Fragment Loss Rearrangment
55 56 by CI 55 / C3H3O 1/H
prop-2-yn-1-ol
39 / C3H3 17 / OH
C3H4O
Exact Mass: 56.0264 38 / C3H2 18 / H2O
IHD = 2, match with (a)
Molecular
I O Base Peak Ion Fragement Ion Fragment Loss Rearrangment
+
N 43 89 by CI 90 / C3H8NO2 Addition of H
O-
72 / C3H6NO 17 / OH R
1-Nitropropane
C3H7NO2 43 / C3H7 46 / NO2
Exact Mass: 89.0477
IHD = 1, match with (d) 42 / C3H6 47 / HNO2 R
J
OH
Molecular
O 94 138 107 / C7H7O 31 / CH3O
2-Phenoxylethanol
94 / C6H5O 44 / C2H4O R
C8H10O2
Exact Mass: 138.0681 77 / C6H5 61 / C2H5O2
IHD = 4, match with (q) 66 / C5H6 72 C3H5O2 R
51 / C4H3 87 / C4H7O2
39 / C3H2 99 / C5H8O2
K
Molecular
O Base Peak Ion Fragement Ion Fragment Loss Rearrangment
94 122 94 / C6H5O 28 / C2H4 R
Phenetole
77 / C6H5 45 / C2H5O
C8H10O
Exact Mass: 122.0732 66 / C5H6 56 / C3H4O
IHD = 4, match with (o)
51 / C4H3 71 / C4H7O
39 / C3H2 83 / C5H8O
Molecular
L O Base Peak Ion Fragement Ion Fragment Loss Rearrangment
O 43 102 87 / C4H7O2 15 / CH3
74 / C3H5O2 28 / C2H4 R
Methyl Butyrate
C5H10O2 71 / C4H7O 31 / CH3O
Exact Mass: 102.0681 59 / C2H3O2 43 / C3H7
IHD = 1, match with (i)
43 / C3H7 59 / C2H3O2
M O Molecular
HN 113 113 85 / C5H11N 28 / CO R
84 / C5H10N 29 / CHO
56 / C4H8 57 / C2H3NO
Caprolactam
C6H11NO 55 / C4H7 58 / C2H4NO
IHD = 2, match with (j) 42 / C3H6 71 / C3H5NO R
N N
Molecular
N
94 94 67 / C4H5N 27 / CHN
2-methylpyrazine
53 / C3H3N 41 / C2H3N
C5H6N2
Exact Mass: 94.0531 42 / C2H4N 52 / C3H2N
IHD =4, match with (e) 41 / C2H3N 53 / C3H3N
40 / C2H2N 54 / C3H4N
Molecular
O HO Base Peak Ion Fragement Ion Fragment Loss Rearrangment
O 152 152 135 / C8H7O2 17 / OH
122 / C7H6O2 30 / CH2O R
O 107 / C7H7O 45 / CHO2 R
Methyl salicylate 105 / C7H5O 17 / OH, 30 / CH2O R
C8H8O3 92 / C6H4O 60 / C2H4O2 R
Exact Mass: 152.0473 17 / OH, 58 /
IHD = 5, match with (s) 77 / C6H5 C2H2O2
63 / C5H3 89 / C3H5O3
39 / C3H2 113 / C5H6O3
Molecular
P Base Peak Ion Fragement Ion Fragment Loss Rearrangment
O 141 /
N+ Cl 75 or 157 157 C6H4ClNO 16 / O
-
O 127 / C6H4O 30 / NO R
111 / C6H4Cl 46 / NO2
1-Chloro-4-Nitrobenzene
C6H4ClNO2 99 / C5H4Cl 58 / CNO2
IHD = 5, match with (t) 75 / C6H3 46 / NO2, 36 / HCl R
50 / C4H2 107 / C2H2ClNO2
Q Molecular
O Base Peak Ion Fragement Ion Fragment Loss Rearrangment
HO Br 60 208 by CI 191 / C7H12OBr 17 / OH
7-Bromo Heptanoic Acid 149 / C5H10Br 59 / C2H3O2
C7H13BrO2
Exact Mass: 208.0099 129 / C7H13O2 79 /Br
IHD = 1, match with (w)
111 / C7H11O 79 /Br, 18 / H2O R
83 / C6H11 125 / CH2BrO2 R
60 / C2H4O2 147 / C5H9Br R
R
Molecular
HO Base Peak Ion Fragement Ion Fragment Loss Rearrangment
5-Hexyn-1-ol 70 98 97 / C6H9O 1/H
C6H10O
Exact Mass: 98.0732 83 / C5H7O 15 / CH3
IHD = 2, mathc with (g)
79 / C6H7 19 / H3O
70 / C4H6O 28 / C2H4
Molecular
S O Base Peak Ion Fragement Ion Fragment Loss Rearrangment
43 126 111 / C7H11O 15 / CH3
6-Methyl-5-hepten-2-one 108 / C8H12 18 / H2O R

C8H14O 93 / C7H9 33 / CH5O R
IHD = 2, match with (p) 83 / C6H11 43 / C2H3O
69 / C5H9 57 / C3H5O
58 / C3H6O 68 / C5H8 R
55 / C4H7 71 C4H7O
43 / C2H3O 83 / C6H11
Molecular
T O Base Peak Ion Fragement Ion Fragment Loss Rearrangment
60 116 by CI 87 / C4H7O2 29 / C2H5
HO
73 / C3H5O2 43 / C3H7
Hexanoic acid
60 / C2H4O2 56 / C4H8 R
C6H12O2
Exact Mass: 116.0837 45 / CHO2 71 / C5H11
IHD = 1, match with (l)
Molecular
U Base Peak Ion Fragement Ion Fragment Loss Rearrangment
HO Cl
162 162 126 / C6H3OCl 36 / HCl R
98 / C5H3Cl 64 / CHOCl R
Cl
63 / C5H3 99 / CHOCl2
2,6-Dichlorophenol
C6H4Cl2O
IHD = 4, match with (u)
Molecular
V HO Base Peak Ion Fragement Ion Fragment Loss Rearrangment
122 122 121/C8H9O 1/H
107/C7H7O 15 / CH3
91 / C7H7 31 / CH3O
2,6-Dimethylphenol
C8H10O 77 / C6H5 45 / C2H5O
IHD = 4, match with (n) 65 / C5H5 57 / C3H5O
W O
Molecular
68 96 68 / C4H4O 28 / C2H4 R
55 / C3H3O 41 / C3H5
2-Cyclohexen-1-one
C6H8O 53 / C4H5 43 / C2H3O
Exact Mass: 96.0575 42 / C2H2O 54 / C4H6 R
IHD = 3, match with (f)
Answers for Student Exercise 2.1 2.9 1
2.1. Since the indicated carbon of phenylacetonitrile is sp3 hybridized, it is reasonable for this compound to
show CH stretching at less than 3000 cm-1 (2960-2940 cm-1). Where as benzonitrile has only aromatic
CH stretching which is typically between 3100 - 3000 cm-1 (page 87).
N
C C N
CH2
phenylacetonitrile benzonitrile
2.2.
O
O
S
N
H 2N O N+
O O O-
a. benzonitrile b. isobutylamine c. diphenyl sulfone d. dioxane e. 1-nitropropane
HO H 2N
HO O O O
f. formic acid g. biphenyl h. benzoic acid i. benzamide
2.3.
1,3-Cyclohexadiene Diphenylacetylene 1-Octene 2-Pentene

Spectrum B Spectrum A Spectrum D Spectrum C
2.4.
NH2 O O
O O
H 2N Na+
O HO C11H23 O-
Butyl acetate Butyramide Isobutylamine Lauric acid Sodium propionate
Spectrum E Spectrum H Spectrum I Spectrum F Spectrum G
2.5.
O HO
HO
O H O
Allyl phenyl ether Benzaldehyde o-Cresol m-Toluic acid
Spectrum L Spectrum M Spectrum K Spectrum J
2.6.
HO
N
N H 2N NH2 Cl
H 2N N
Dimethylamine
Aniline Azobenzene Benzophenone oxime Benzylamine hydrochloride
Spectrum Q Spectrum O Spectrum P Spectrum N Spectrum R
2.7. Methyl isothiocyanate CH3N=C=S
2.8. This diketone exists primarily (~ 90%) in enol form (in CCl4)
O O H
O O
enol
Enols such as this display broad, shallow OH stretching bands (here from 3400-2500 cm-1). The
strong band at ~1600 cm-1 is the enolic coupled C=COH band. (See pages 80, 94, and 98)
2.9.
O OH Br
Br
4-Heptanone 3-Heptanol 4-Bromotoluene 2-Bromopentane

A B C D
O O
OH
OH H 2N
2-Hexanone Propionic Acid Butylamine Propargyl alcohol
E F G H
OH
O O
N+ O O
O- O
1-Nitropropane 2-Phenoxylethanol Phenetole MethylHButyrate
I J K L
O HO
N O O
HN N+ Cl
N O -
O
Caprolactam 2-methylpyrazine Methyl salicylate 1-Chloro-4-Nitrobenzene
M N O P
O O
HO Br HO
7-Bromo Heptanoic Acid 5-Hexyn-1-ol 6-Methyl-5-hepten-2-one
Q R S
HO Cl HO O
O
Cl
HO
Hexanoic acid 2,6-Dichlorophenol 2,6-Dimethylphenol 2-Cyclohexen-1-one
T U V W
Answers for Student Exercise 3.1 to 3.3 1
3 1 Br
4 2
(a) 1-bromobutane
3.1(a) 1,2,3,4 are a spin system. Pople notation is A3M2S2X2. 1,2, and 3 are enantiotopic.
3.2 (a)
Spin Appr. Table Coupled with Multiplet (n+1) Integration
1 3.40 Appendix A, Chart A.1 2 Triplet 2
2 1.85 Appendix A, Chart A.2 1,3 Quintet 2
3 1.20 Appendix A, Chart A.1 3, 4 Sextet 2
3.3 (a)
1 2 3 4
5 6
4 1
7
O
3 2
O 8
9
(b) (cyclohex-2-enyl)methyl acetate
3.1 (b) 1,2,3,4,5,6,7 are one spin system, and 9 is the second. 4,4 ; 5,5 ; 6,6and 7,7 are
diastereotopic.
3.2 (b)
Spin Appr. Table or Calculation Coupled with Multiplet (n+1) Integration
1 2.80 Appendix A, Chart A.2 6,2,7 Sextet* 1
2 5.59 Appendix D, Chart D2 3,1 Triplet* 1
3 5.59 Appendix D, Chart D2 Quartet* 1
4 1.96 Appendix D, Chart D2 Quartet** 2
5 1.65 Appendix D, Chart D2 4,6 Quartet** 2
6 1.80 Appendix A, Chart A.2 1,5 Triplet** 2
7 4.05 Appendix A, Chart A.2 1 Doublet** 2
9 2.10 Appendix A, Chart A.1 none Singlet 3
* Coupling constants may not be the same, but make the assumption that they are.
**These are diastereotopic, and are coupled to diastereotopic protons, they would not be first order.
We will assume they are first order for the drawn spectrum.
3.3 (b)
2 and 3 7 1 9 4 6 5
O 9
2
1 8
3 7 OH
4 6
10
5
(c) 1-(cyclohexa-1,5-dienyl)-3-
hydroxy-2-methylpropan-1-one
3.1 (c) 2,3,4,5,6 are a spin system, and 8,9,10 another spin system. 3,3 ; 4,4 ; 9,9 are diastereotopic.
3.2 (c)

2 6.68 Appendix D, Chart D.1 3 Triplet 1
3 2.05 Appendix A, Chart A1 2,4 Quartet*** 2
4 2.05 Appendix A, Chart A1 3,5 Quartet*** 2
5 5.68 Appendix D, Chart D1 4,6 Quartet* 1
6 6.22 Appendix D, Chart D1 5 Doublet 1
8 2.65 Appendix A, Chart A.1 9,10 Sextet 1
9 3.20 Appendix A, Chart A.1 8 Doublet** 2
10 1.05 Appendix A, Chart A.2 8 Doublet 3
0.5-4.0 Appendix E 1
** These are diastereotopic, and are coupled to diastereotopic protons; they would not be first order.
We will assume they are first order for the drawn spectrum.
3.3 (c)
2 6 5 9 8 3,4 OH 10
4 H
5 3 2 1
(d) pent-1-yne
3.1 (d) 5,4,3 are a spin system and 1 is second. 5,4,3 is Pople notation is A3M2X2; may have long rang
coupling. 3+4 are enantiotopic.
3.2 (d)

4 1.50 Appendix A, Chart A2 3,5 Sextet 2
3 2.20 Appendix A, Chart A1 4 Triplet 2
1 1.80 Appendix D, Chart D3 none Singlet 1
3.3 (d)
3 1 4 5
O
1 3 5
2 4 6
(e) hex-3-en-2-one
3.1 (e) 3,4,5,6 are a spin system, and 1 is another spin system. Pople notation is A3G2MX. 5 is
enantiotopic.
3.2 (e)

1 1.86 Appendix D, Chart D.2 None Singlet 3
3 6.09 Appendix D, Chart D.1 4 Doublet 1
4 6.82 Appendix D, Chart D.1 3, 5 Quartet* 1
5 2.05 Appendix A, Chart A1 4, 6 Quintet* 2
3.3 (e)
4 3 5 1 6
1 O 2 4
5
3
(f) 1-methoxybut-1-ene
3.1 (f) 3,4,5,6 are a spin system, and 1 is another spin system. Pople notation is A3G2MX. 4 is
enantiotopic.
3.2 (f)

1 3.20 Appendix A, Chart A.1 None Singlet 3
3 4.63 Appendix D, Chart D.1 2, 4 Quartet* 1
4 2.05 Appendix A, Chart A1 3, 5 Quintet* 2
3.3 (f)
2 3 1 4 5
O
1
4
N 2 O 3 5
H
(g) propyl methylcarbamate
3.1 (g) 3,4,5 are a spin system, and 1 is another spin system. Pople notation is A3M2X2. 3 and 4 are
enantiotopic.
3.2 (g)

1 2.95 Appendix A, Chart A.1 None Singlet 3
3 4.10 Appendix D, Chart D.1 3 Triplet 2
4 1.60 Appendix A, Chart A.2 2, 4 Sextet 2
5 0.85 Appendix A, Chart A1 3, 5 Triplet 3
NH 4.5-7.5 Appendix E * Singlet 1
*See Section 3.6.2 for coupling between 1 and N-H.
3.3 (g)
NH 3 1 4 5
1
2 O 3 O
(h) diethoxymethane
3.1 (h) 1 and 2 are a spin system, and 3 is another spin system. Pople notation is A3X2. 2 are
enantiotopic.
3.2 (h)

2 3.40 Appendix A, Chart A.1 1 Quartet 2
3 4.95 Appendix B, Table B.1 none Singlet 2
3.3 (h)
3 2 1
1 6
3 5
2 4
HO
(i) 2-methylpentan-2-ol
3.1 (i) 3,4 and 5 is a spin system. 1 and 6 are enantiotopic to each other and 3 and 4 are also
enantiotopic. Pople notation is A3M2X2.
3.2 (i)

1 and 6 1.20 Appendix A, Chart A2 none Singlet 6
4 1.20 Appendix A, Chart A1 3,5 Sextet 2
0.5-4.0 Appendix E none Singlet 1
3.3 (i) 1 and 6

Large singlet
of 6 H
OH 3 1,6,4
1 S 2
3 S
(j) 1,4-bis(methylthio)butane
3.1 (j) Not First order (no Pople). See Section 3.11.2. Protons 2 and 3 are enantiotopic. Protons on
1,2,3 are Chemical Shift Equivalent.
3.2 (j)

1 2.10 Appendix A, Chart A1 none Singlet 6 or 3
2 2.60 Appendix A, Chart A1 3 Triplet* 4 or 2
3 1.60 Appendix A, Chart A2 2,3 Quintet* 4 or 2
* Would not be first order. We will assume they are first order for the drawn spectrum.
3.3 (j)
Actual spectrum would look like this!
2 1 0
PPM
O
2' 6
3' 1
5 N
4 2 7
8
3
(k) N,N,4-trimethylbenzamide
3.1 (k) 2,2; 3,3 are CSE but not ME. 6 and7 are diastereotopic. Pople notation for ring is AA XX
3.2 (k)

2, 2 7.80 Appendix D, Chart D1 none Doublet** 2
3, 3 7.25 Appendix D, Chart D1 3 Doublet** 2
6,7 2.95 Appendix A, Chart A1 none Singlet* 6*
8 2.25 Appendix A, Chart A1 none Singlet 3
* There will be two singlets because of the restricted rotation of the NR2
** These can not be first order. Not magnetically equivalent.
3.3 (k)
2,2 3,3 6,7 8

O
6
1 8
5 7
2
4
3 OH
(l) 1-(2-hydroxyphenyl)ethanone
3.1 (i) N.A.
3.2 (i)

3 6.85 Appendix D, Chart D.1 4 Doublet* 1
4 7.05 Appendix D, Chart D.1 3,5 Triplet* 1
5 7.25 Appendix D, Chart D.1 4,6 Triplet* 1
6 7.70 Appendix D, Chart D.1 5 Doublet* 1
8 2.40 Appendix A, Chart A1 none Singlet 3
OH 5.5-12.5 Appendix E none Singlet 1
* Will have long range coupling.
3.3 (i)
OH 6 5 4 3 8
2 H
Cl 1
O
(m) 2-chloroacetaldehyde
3.1(m) 1 and 2 is a spin system. Pople notation is A2X. 2 protons are enantiotopic.
3.2 (m)
Spin Appr. Table Coupled with Multiplet (n+1) Integration
Plus Appendix B, Table B.1*
extrapolation
Calc is based on Chart A1 3.45 for ClCH2 plus Table B.1 value of 1.50 for HC=O
3.3 (m)
2 1
2H
3
1 H
H
F
(n) fluoroethene
3.1(n) Charts are not available in text for this problem. Pople notation is AGMX, where X is F.
3.2 (n)
3.3 (n)
7 6 5 4 3 2 1 0
PPM
Protocol of the H-1 NMR Prediction:
Node Shift Base + Inc. Comment (ppm rel. to TMS)
H 4.85 5.25 1-ethylene

-0.40 1 -F cis
1.54 1 -F gem
-1.02 1 -F trans
2'
3' 1 O O
5
2 6
4
3
(o) cyclohexyl acetate
3.1 (o) 1,2,2,3,3, and 4 is a spin system, and 6 is another spin system. 2,2,;2,2;3,3;3,3;4,4 protons
are diastereotopic. 2 and 2 are CSE, also 3 and 3 are CSE.
3.2 (o)

1 4.95 Appendix A, Chart A.1 2,2 Quintet 1
2,2 1.60 Appendix A, Chart A.2 1,(3or3) Quartet* 4
3,3 1.44 Appendix C, Table C.1 (2 or 2),4 Quintet* 4
4 1.44 Appendix C, Table C.1 3,3 Quintet* 2
6 2.00 Appendix A, Chart A.1 none Singlet 3
* These are diastereotopic, and are coupled to diastereotopic protons; they would not be first order. We
will assume they are first order for the drawn spectrum.
3.3 (o)
1 6 2,2 3,3, and 4

Answers for Student Exercise 3.4 16
Problem
Problem 3.4
4.3 A
A C7H14O
O 1
1 3
2 4
3 4-Heptanone
2
2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.8 ppm
Problem 3.4
Problem B C7H16O
4.3 B
OH 1
1 OH
2 7
3 4 5 6
2
3 3-Heptanol 4
5
6 7
3.5 3.0 2.5 2.0 1.5 1.0 ppm

2 3
Problem 4.3 C C H Br
Problem 3.4 C 7 7 5 1 4
Br 5
4-Bromotoluene
3
2
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 ppm
1
Problem 3.4
4.3 D
D C5H11Br Br 5
Problem
1 3 5
2 4
2-Bromopentane
3 4
4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

1
Problem
Problem 3.4
4.3 E
E C6H12O O
1 3 5
2 4 6 6
2-Hexanone
3
4 5
2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.8 ppm
Problem 3.4
4.3 FF C3H6O2 O
Problem
2
x4 HO 1 3 3
OH Propionic Acid
12.0 11.5 ppm
3.5 3.0 2.5 2.0 1.5 ppm
Problem 3.4
Problem 4.3 G
G C4H11N
2 4
H2N 1 3
Butylamine 4
1
NH2
2 3
2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.8 ppm
Problem 33.4
Problem 4.3 HH C3H4O
1 2 OH
3
Propargyl alcohol
3 OH
1
4.4 4.2 4.0 3.8 3.6 3.4 3.2 3.0 2.8 2.6 2.4 2.2 2.0 ppm
Problem 3.4 I
Problem 4.3 I C3H7NO2 O
- N+ 1 3
O 2 3
1 1-Nitropropane 2
4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

3
Problem 3.4 J OH 5 6
Problem 4.3 J C8H10O24 2
6 2
3 1 5
4
O
2-Phenoxylethanol
2200 2150 2100 Hz 1250 1200 1150 Hz
OH
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 ppm
Problem
Problem 3.4
4.3 K
K C8H10O
6 2 3
5 1 6
4 5
O
2
3 4
Phenetole
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
Problem
Problem 3.4
4.3 L
L C5H10O2
O
4 4
5 O 1 2 3
5 2 3
Methyl Butyrate
3.5 3.0 2.5 2.0 1.5 1.0 ppm

2 4
Problem
Problem 3.4
4.3 M
M C6H11NO 5
6 3
O
HN 1 2
NH 6 3
5 4
Caprolactam
7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
3 4
N
Problem 3.4
Problem 4.3 N
N aCpyrazine
5H6N2 A pyrazine 2
7 5
3
6N 7
1
6 2-methylpyrazine
5
2520 2510 2500 2490 Hz
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 ppm
Problem
Problem 3.4
4.3 O
O C8H8O3 HO 4
1 6
1 proton (x32) 3 5 O
2 5 8
7 6
OH O 3 4
8
Methyl salicylate
13 12 ppm
2300 2250 2200 2150 Hz
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 ppm

Problem
Problem 3.4
4.3 PP C6H4ClNO2 3 2 2
3 O
1
N+ 4 Cl
-
O
8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 ppm
Problem 3.4 Q O
Problem 4.3 Q C7H13BrO2 Acid
2 4 6
HO 1 3 5 7 Br
OH
1 proton (x32) 7 7-Bromo Heptanoic Acid
2
6 3 5 4
12 11 ppm
4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm

6
Problem 4.3
3.4 R
R C6H10O Unsaturated alcohol
2 4
HO 1 3 5
6
5-Hexyn-1-ol
1 OH 4
2 3
3.6 3.4 3.2 3.0 2.8 2.6 2.4 2.2 2.0 1.8 1.6 ppm
Problem
Problem 3.4
4.3 SS Unsaturated ketone ketone
C8H14O Unsaturated 8 1
O
3 5
1 2 4 6 7
6-Methyl-5-hepten-2-one 78
3
4
5
1520 1510 1500 Hz
5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
Problem
Problem 3.4
4.3 T
T C6H12O2 O
2
2 4 6
HO 1 3 5
OH Hexanoic acid
4 5 6
3
13 12 ppm
2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0 ppm
Problem 4.3
3.4 U
U C6H4OCl2
3
OH
4 HO Cl
1 2
Cl 3
4
2,6-Dichlorophenol
7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5 6.4 6.3 6.2 6.1 6.0 5.9 5.8 5.7 ppm
5
3 HO
Problem 4.3
Problem V C8H10O
3.4 V 1 2
4 5
3
4
2,6-Dimethylphenol
2120 2100 2080 2060 Hz
OH
7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 ppm
Problem 4.3
3.4 W
W Unsaturated ketone ketone
C6H8O Unsaturated
4
6 5
O
1
6 2
3 2 5 4 3
2-Cyclohexen-1-one
7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 ppm
22
Answers for Student Exercise 3.5
3.5A. (1.58(300) 0.90(300))/7 = about 29; (2.36(300) 1.58(300))/7 = about 33
3.5E. (2.38(300) 1.52(300))/7 = about 37; (1.52(300) 1.38(300))/7 = about 6

(1.38(300) 0.87(300))/7 = about 22
3.5F. (2.38(300) 1.13(300))/7 = about 54
3.5G. (2.61(300) 1.35(300))/7 = about 54; (1.35(300) 1.29(300))/7 = about 2 to 3

(1.29(300) 0.84(300))/7 = about 19
3.5H. Long range coupling; cant measure coupling constant
3.5I. (4.33(300) 2.01(300))/7 = about 99; (2.01(300) 0.99(300))/7 = about 44
3.5K. (4.08(300) 1.44(300))/7 = about 113
3.5L. (2.26(300) 1.62(300))/7 = about 27; (1.62(300) 0.92(300))/7 = about 30
3.5Q. (3.39(300) 1.86(300))/7 = about 66; (2.36(300) 1.65(300))/7 = about 30

(1.86(300) 1.47(300))/7 = about 17; (1.65(300) 1.37(300))/7 = about 12
3.5U. (7.25(300) 6.81(300))/9 = about 15

Answers for Student Exercises 3.6 23
O
1 3
2 4
4-Heptanone
A
Pople Notation -- A3M2X2; 2 and 3 (and 5 and 6) are enantiotopic. 3 and 5, 2 and 6 are CSE.
1 OH
2 7
3 4 5 6
3-Heptanol
B
One spin system. 2,2; 4,4; 5,5, and 6,6 are diastereotopic.
2 3
5 1 4
Br
4-Bromotoluene
C
Two spin systems. Pople Notation -- AAXX. 2 and 2 are CSE but not magnetically equivalent as are
3 and 3.
Br
1 3 5
2 4
2-Bromopentane
D
One spin system. 3 and 3; 4 and 4 are diastereotopic.
O
1 3 5
2 4 6
2-Hexanone
E
Two spin systems. 3, 4, and 5 are enantiotopic.
O
2
HO 1 3
Propionic Acid
F
A3X2. Protons on two are enantiotopic.
2 4
H2N 1 3
Butylamine
G
Pople Notation A3G2M2X2One spin system. 1, 2, and 3 are enantiotopic.
1 2 OH
3
Propargyl alcohol
H
One spin system with long range coupling. Protons on 2 enantiotopic.
O
- N+ 1 3
O 2
1-Nitropropane
I
Pople Notation -- A3M2X2. 1 and 2 are enantiotopic.
3
4 2 OH
6
1 5
3'
2' O
2-Phenoxylethanol
J
Two spins systems; Pople Notation -- AAMMX and A2X2. 2 and 2are CSE but not magnetically
equivalent as are 3 and 3. 5 and 6 are enantiotopic.
6 2 3
5 1
O 4
2' 3'
Phenetole
K
Two spins systems; Pople Notation -- AAMMX and A3X2. 2 and 2are CSE but not magnetically
equivalent as are 3 and 3. 5 and 6 are enantiotopic.
O
4
O 1
5 2 3
Methyl Butyrate
L
Two spin systems; Pople Notation --A3M2X2. 2 and 3 are enantiotopic.
O
HN 1 2
6 3
5 4
Caprolactam
M
One spin system. 2,2; 3,3; 4,4; 5,5 and 6,6 are diastereotopic.
3 4
N
2
7 5
6 N
1
2-methylpyrazine
N
Pople Notation AB for 5 and 6. Three spins systems.
HO
1 6
O
2 5
7
O 3 4
8
Methyl salicylate
O
Two spin systems. Pople Notation AGMX.
3 2
O
1
N+ 4 Cl
-
O 3' 2'
P
One spin system. 2 and 2 are CSE but not magnetically equivalent as are 3 and 3.
O
2 4 6
HO 1 3 5 7 Br
7-Bromo Heptanoic Acid
Q
One spin system. 2, 3, 4, 5, 6, and 7 are enantiotopic.
6
2 4
HO 1 3 5
5-Hexyn-1-ol
R
One spin system with long range coupling. 1, 2, 3, and 4 are enantiotopic.
O 8
3 5
1 2 4 6 7
6-Methyl-5-hepten-2-one
S
At 2 spins systems (7 and 8 probably have long range coupling). 3 and 4 are enantiotopic.
O
2 4 6
HO 1 3 5
Hexanoic acid
T
One spin system. 2, 3, 4, and 5 are enantiotopic.
HO Cl
1 2
Cl 3
3' 4
2,6-Dichlorophenol
U
One spin system. 3 and 3 are CSE but not magnetically equivalent.
5
HO
1 2
6
3
3' 4
2,6-Dimethylphenol
V
One spin system. 3 and 3 are CSE but not magnetically equivalent. 5 and 6 are CSE.
O
1
6 2
5 4 3
2-Cyclohexen-1-one
W
One spin system. 4, 5, and 6 are enantiotopic.
A X
A X
JAX JXA
AX 1 1 1 1
JXA A2 X
JAX
1 1
A2X 1 1 1 2 1
X
JXA A3
1 1
JAX 1 2 1
A3X 1 1 1 3 3 1
JAX JXA A2 X2
1 1 1 1
A2X2 1 2 1 1 2 1
X2
JXA A3
JAX 1 1
1 1 1 2 1
A3X2 1 2 1 1 3 3 1
With the AMX systems A and X do not change; they are

represented as follows: JAM JMX
1 1 1 1
AMX JAM
1 1
A M X
1 2 1 JMX
JAM
A2 M X
1 1
1 2 1
A2MX 1 3 3 1 JMX
JAM
A3 M X
1 1
1 2 1
1 3 3 1
1 4 6 4 1 JMX
A3MX
29
Answers for Student Exercise 3.8 Continued
JAM A2 M X2
A2MX2
1 1
1 2 1
1 3 3 1 JMX
1 4 6 4 1
JAM
M
A2MX3 1 1
A2 X3
1 2 1
1 3 3 1 JMX
1 4 6 4 1
1 5 10 10 5 1
JAM
A3 M X3
1 1
A3MX3
1 2 1
1 3 3 1
JMX
1 4 6 4 1
1 5 10 10 5 1
1 6 15 20 15 6 1
30
With the AMX systems A and X do not change; they are

represented as follows: JAM
JMX
1 1 1 1
The following are for M:
JAM
AMX
1 1
1 1 1 1 JMX
A2MX
JAM
1 1
1 2 1
1 1 2 2 1 1 JMX
A3MX JAM
1 1
1 2 1
1 3 3 1
JMX
1 1 3 3 3 3 1 1
31
Answers for Student Exercise 3.9 Continued
A2MX2 JAM
1 1
1 2 1
1 1 2 2 1 1 JMX
1 2 3 4 3 2 1
A2MX3 JAM
1 1
1 2 1
1 2 JMX
1 2 1 1
1 2 3 4 3 2 1
1 3 5 7 7 5 3 1
JAM
A3MX3
1 1
1 2 1
1 3 3 1
JMX
1 1 3 3 3 3 1 1
1 2 4 6 6 6 4 2 1
1 3 6 10 12 12 10 6 3 1
32
Answers for Student Exercise 3.10A
Spin System ab2c3

Coupling
a-b 6 Hz
b-c 12Hz
a-c 3 Hz
1 1
(c) 1 2 1 Jcb
1 1 2 2 1 1 Jca
1 1
1 2 1
1 3 3 1 Jbc
(b)
1 1 3 3 3 3 1 1 Jba
1 1
Jab
1 2 1
1 1 2 2 1 1 Jac
(a) 1 2 3 4 3 2 1
1 3 5 7 7 5 3 1
33
Answers for Student Exercise 3.10B
Spin System ab2c3

Coupling
a-b 6 Hz
b-c 4Hz
1 1 Jca
a-c 9 Hz
1 1 1 1
(c) 1 2 1 1 2 1 Jcb
Jba
1 1
1 1 1 1 Jbc
1 2 1 1 2 1
(b) 1 3 1 3 3 1 3 1
1 1
1 2 1
(a) Jac
1 3 3 1
1 1 3 3 3 3 1 1 Jab
1 2 3 1 6 3 3 6 1 3 2 1
34
Answers for Student Exercise 3.10C
Spin System a2b2c2

Coupling 1 1 Jca
a-b 6 Hz
b-c 4Hz
a-c 9 Hz
1 2 1
(c) 1 1 2 2 1 1 Jcb
1 2 1 2 4 2 1 2 1
1 1
1 2 1 Jba
(b) 1 1 2 2 1 1 Jbc
1 2 2 1 4 1 2 2 1
1 1
1 2 1 Jac
(a) Jab
1 1 2 2 1 1
1 2 2 1 4 1 2 2 1
1
2 O
1 1
1 1 1 S 2 3
OH 2 O O 2 3 2 S
2'
1' c h j
O 2
2 1 OAc
1 N
2' 2
1' 1
k o
Answers for Student Exercise 4.2 - 3 (a)
a
3 1 Br
4 2
1-bromobutane
Atom Base Other Calc Shift Comments
C1 Methane 2 3 4 0 0 -Br The base and shifts
-2.5 9.1 9.4 -2.5 20 33.5 are from Table 4.4
C2 Methane 1,3 4 -Br Other is from table 4.6
-2.5 18.2 9.4 11 36.1
C3 Methane 4,2 1 -Br
-2.5 18.2 9.4 3 22.1
C4 Methane 3 2 1
-2.5 9.1 9.4 -2.5 13.5
45 40 35 30 25 20 15 10 5 ppm
Answers for Student Exercise 4.2 - 3 (b) 2
5 6
1
4
7
O
3 2
O 9
8
CH3
C1 Methane 2,6,7 OCOR,3,5 4 3(3(2)) The base and shifts
-2.5 3*9.1 6+9.4+9.4 -2.5 3*(-3.7) are from Table 4.4
value -2.5 27.3 24.8 -2.5 -11.1 36 Other is from table 4.6
C2 ethylene 1,4' 6,7,5' 5,6' -OCOR, Zcis
10.6+-7.9 7.2+7.2+-1.8 (-1.5)+(-1.5) (-3)+(-1.1)
123.3 2.7 12.6 -3 -4.1 131.5
C3 ethylene 4,1' 5,6',7' 6,5' Zcis
10.6+-7.9 7.2+2(-1.8) (-1.5)+(-1.5) -1.1
123.3 2.7 3.6 -3 -1.1 125.5
C4 Methane 3,5 6,2 1,1 7
2(9.1) 2(9.4) 2(-2.5) 0.3
-2.5 18.2 18.8 -5 0.3 29.8
C5 Methane 4,6 1,3 7,2,2
2(9.1) 2(9.4) 3(-2.5)
-2.5 18.2 18.8 -7.5 27
C6 Methane 1,5 2,4,7 2(3),OCOCH3 2(3)
2(9.1) 3(9.4) 2(-2.5)+(-3) -2.5
-2.5 18.2 28.2 -8 -2.5 33.4
C7 Table 4.12 1,OCOCH3 6,2 3,5 4 2(3)
-2.5 61 15.2 -4 0.3 -2.5 67.5
C8 Table 4.12
170.5 170.5 Table 4.12
C9 Table 4.12
20.7 20.7 Table 4.12
160 140 120 100 80 60 40 20 ppm

3
Answers for Student Exercise 4.2 - 3 (c)
O
1 6
5 7 OH
2 8
4
3
(c) 3-hydroxy-2-methyl-
1-phenylpropan-1-one
Atom Base from table 4.12 Other Calc Shift Comments

Table 4.12 These compare nicely
C1 128.5 7.8 136.3
C2 128.5 -0.4 128.1
C3 128.5 -0.4 128.1
C4 128.5 2.8 131.3
C5 From Table 4.19 the C=O is approximately 197.6 ppm, 198
Base Other Calc Shift Table 4.4 +
C6 methane 7,8,5 OH,Ph 3(2,3) Table 4.6
-2.5 2(9.1)+24 10+9 (-3.7)+(-9.5)
-2.5 42.2 19 -13.2 45.5
C7 methane OH, 6 8, 5 1 2(3)
-2.5 48+9.1 9.4+1 -2 -2.5
-2.5 57.1 10.4 -2 -2.5 60.5
C8 methane 6 7,5 OH,Ph 1(3)
-2.5 9.1 9.4+1 (-5)+(-2) -1.1
-2.5 9.1 10.4 -7 -1.1 8.9
200 180 160 140 120 100 80 60 40 20 ppm

Answers for Student Exercise 4.2-3 (d) 4
4 H
5 3 2 1
(d) pent-1-yne

C1 Table 4.11 The base and shifts
67.0-68.1 are from Table 4.11
67.6 67.6 Increments from table 4.6
C2 Table 4.11
84.7-84.5
84.6 84.6
C3 Methane 4,c 5,c
9.1+4.5 9.4+5.5 Base shifts Table 4.4
-2.5 13.6 13.9 25
C4 Methane 5,3 c
2(9.1) 5.5
-2.5 18.2 5.5 21.2
C5 Methane 4 3 -c
-2.5 9.1 9.4 -3.5
-2.5 9.1 9.4 -3.5 12.5
85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 ppm
Answers for Student Exercise 4.2-3 (e) 5
O
1 3 5
2 4 6
(e) hex-3-en-2-one

C1 methane 2 3 4 5 6 The base and shifts
-2.5 24 9.4 -2.5 0.3 0.1 are from Table 4.4
-2.5 24 9.4 -2.5 0.3 0.1 28.8 Increments from Table 4.6
C2 Table 4.10 1,3 3 4 6 Table 4.10
196.9 196.9 approximate
C3 ethylene 2,5' 6'
123.3 24+(-7.9) -1.8
123.3 16.1 -1.8 137.6
C4 ethylene 5,2' 6
123.3 10.6+1 7.2
123.3 11.6 7.2 142.1
C5 methane 6,4 3 2 1
-2.5 2(9.1) 9.4 -2 0.3
-2.5 18.2 9.4 -2 0.3 23.4
C6 methane 5 4 3 2 1
-2.5 9.1 9.4 -2.5
-2.5 9.1 9.4 -2.5 0.3 0.1 13.9
180 160 140 120 100 80 60 40 20 ppm

6
Answers for Student Exercise 4.2-3 (f)
1 O 2 4
5
3
(f) (1-methoxybut-1-ene

C1 methane O-R 2 3 4 5 The base and shifts
-2.5 51 9.4 -2.5 0.3 0.1 are from Table 4.4
-2.5 51 9.4 -2.5 0.3 0.1 55.8 Increments from table 4.6
C2 Table 4.10
153.2 4' 5' Table 4.10
153.2 -7.9 -1.8 143.5
C3 Table 4.10 4 5
84.2 10.6 7.2
84.2 10.6 7.2 102
C4 methane 5,3 2 -OR
-2.5 9.1+9.1 9.4 -2
-2.5 18.2 9.4 -2 23.1
C5 methane 4 3 2 1
-2.5 9.1 9.4 -2.5 0.1
-2.5 9.1 9.4 -2.5 0.1 13.6
140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

Answers for Student Exercise 4.2-3 (g)
7
O
1
4
N 2 O 3 5
H
(g) propyl methylcarbamate

C1 methane NH COO 3 4 5 The base and shifts
-2.5 31 2 -2.5 0.3 0.1 are from Table 4.4
-2.5 31 2 -2.5 0.3 0.1 28.4 Increments from table 4.6
C2 Table 4.20 Table 4.20
157.8 157.8
C3 methane 3,OCOR 5 NHR
-2.5 9.1+51 9.4 -4
-2.5 60.1 9.4 -4 63
C4 methane 5,3 OCOR
-2.5 9.1+9.1 5
-2.5 18.2 5 20.7
C5 methane 4 3 OCOR
-2.5 9.1 9.4 -3
-2.5 9.1 9.4 -3 13
150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

Answers for Student Exercise 4.2-3 (h) 8
1
2 O 3 O
(h) diethoxymethane

C1 methane 2 OCOR The base and shifts
-2.5 9.1 5 are from Table 4.4
-2.5 9.1 5 11.6 Increments from table 4.6
C2 methane 1,OCOR 3 See Table 4.15 for
-2.5 9.1+45 9.4 comparison
-2.5 54.1 9.4 61
C3 methane 2(OR) 2(2) 2(1)
-2.5 51(2) 9.4(2) 2(-2.5)
-2.5 102 18.8 -5 113.3
110 100 90 80 70 60 50 40 30 20 10 ppm

9
Answers for Student Exercise 4.2-3 (i)
1 6
3 5
2 4
HO
(i) 2-methylpentan-2-ol

C1 methane 2 6,3,OH 4 5 1(4) The base and shifts
-2.5 9.1 2(9.4)+10 -2.5 0.3 -3.4 are from Table 4.4
-2.5 9.1 28.8 -2.5 0.3 -3.4 29.8 Increments from table 4.6
C2 methane 1,6,3,OH 4 5 4(2(1)+2) See Table 4.14 for
-2.5 3(9.1)+48 9.4 -2.5 (2)(-1.5)+-8.4 comparison
-2.5 75.3 9.4 -2.5 -11.4 68.3
C3 methane 2,4 1,6,OH,5 2(4)
-2.5 9.1(2) 3(9.4)+10 -7.2
-2.5 18.2 38.2 -7.2 46.7
C4 methane 3,5 2 1,6,OH
-2.5 2(9.1) 9.4 2(-2.5)+(-5)
-2.5 18.2 9.4 -10 15.1
C5 methane 4 3 2 1,6
-2.5 9.1 9.4 -2.5 (2).3
-2.5 9.1 9.4 -2.5 0.6 14.1
C6 methane 2 6,3,OH 4 5 1(4)
-2.5 9.1 2(9.4)+10 -2.5 0.3 -3.4
-2.5 9.1 28.8 -2.5 0.3 -3.4 29.8
110 100 90 80 70 60 50 40 30 20 10 ppm

10
Answers for Student Exercise 4.2-3 (j)
1 S 2
3 S
(j) 1,4-bis(methylthio)butane

C1 methane SR The base and shifts
-2.5 20 are from Table 4.4
-2.5 20 17.5 Increments from table 4.6
C2 methane SR,3 3 2 SR See Table 4.18 for
-2.5 20+9.1 9.4 -2.5 0 Comparison
-2.5 29.1 9.4 -2.5 33.5
C3 methane 2,2 3,SR 2 SR
-2.5 2(9.1) 9.4+7 -2.5 0
-2.5 18.2 16.4 -2.5 29.6
45 40 35 30 25 20 15 10 5 ppm
11
Answers for Student Exercise 4.2-3 (k)
O
6
1
5 N
4 2 7
8
3
(k) N,N,4-trimethylbenzamide

Table 4.12 C=ONH2 CH3 Table 4.12
C1 128.5 5 -2.9 130.6
C2 128.5 -1.2 -0.1 127.2
C3 128.5 0 0.7 129.2
C4 128.5 3.4 9.3 141.2
C5 From Table 4.20 the C=O is approximately 171 ppm, 171
Base Other Calc Shift Table 4.4 +
C6 methane NR2 C=O Ph Table 4.6
-2.5 42 1 -2
-2.5 42 1 -2 38.5
C7 methane NR2 C=O Ph
-2.5 42 1 -2
-2.5 42 1 -2 38.5 Table 4.12
C8 Table 4.12 21.3
160 140 120 100 80 60 40 20 ppm

12
Answers for Student Exercise 4.2-3 (l)
O
6
1 8
5 7
2
4
3 OH
(l) 1-(2-hydroxyphenyl)ethanone

Table 4.12 C=OCH3 OH Table 4.12
C1 128.5 7.8 -12.7 123.6
C2 128.5 -0.4 26.6 154.7
C3 128.5 -0.4 -12.7 115.4
C4 128.5 2.8 1.6 132.9
C5 128.5 -0.4 -7.3 120.8
C6 128.5 -0.4 1.6 129.7
C7 From Table 4.19 the C=O is approximately 197.6 ppm, 197.6 Table 4.19
C8 From Table 4.19 the CH3 is approximately 26.3 ppm, 26.3
180 160 140 120 100 80 60 40 20 ppm

13
Answers for Student Exercise 4.2-3 (l)
2 H
Cl 1
O
(m) 2-chloroacetaldehyde

C1 methane Cl, CHO The base and shifts
-2.5 31+31 are from Table 4.4
-2.5 62 59.5 Increments from table 4.6
C2 Table 4.19 Cl See Table 4.18 for
199.7 Comparison
199.7 199.7
200 180 160 140 120 100 80 60 40 20 ppm

14
Answers for Student Exercise 4.2-3 (n)
H
2
H
H 1
F
(n) fluoroethene

C1 Ethylene F The base
123.2 68 are from Table 4.9
123.2 68 191.2 Increments from table 4.6
C2 Ethylene F See Table 4.9 for
123.2 9 Comparison
123.2 9 132.2
Note -- These are not close to observed values, but are the only answer from given tables.
19F couplings not shown
200 180 160 140 120 100 80 60 40 20 ppm

15
Answers for Student Exercise 4.2-3 (n)
1 O O
5
2 6
4
3
(o) cyclohexyl acetate

C1 Table 4.7 OCOR The base and shifts
26.9 51 are from Table 4.7
26.9 51 77.9 Increments from table 4.6
C2 Table 4.7 OCOR
26.9 6
26.9 6 32.9
C3 Table 4.7 OCOR
26.9 -3
26.9 -3 23.9
C4 Table 4.7 OCOR
26.9 0
26.9 0 26.9
C5 Table 4.20
Approx
168 168 Table 4.20
C6 methane COO 1 2,2 3,3 The base and shifts
-2.5 25 -2.5 2(.3) 2(.1) are from Table 4.4
-2.5 25 -2.5 0.6 0.2 20.8 Increments from table 4.6
160 140 120 100 80 60 40 20 ppm

Answers for Student Exercise 4.4 A-C
16
Problem O
Problem 5.7A
4.4 A
1 3
2 4
4-Heptanone
1
3
2
200 180 160 140 120 100 80 60 40 20 ppm

1 OH
2 7
Problem 5.7B
Problem 4.4 B 3 4 5 6
3-Heptanol
2 4 5 6 1 7
3
85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 ppm
2 3
Problem
Problem 5.7C
4.4 C 5 1 4
Br
4-Bromotoluene
2 3
5
1 4 131 ppm
140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

Answers for Student Exercise 4.4 D-F
17
Problem Br
Problem 5.7D
4.4 D
1 3 5
2 4
2-Bromopentane
2 3 1 4 5
95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 ppm
O
Problem 5.7E
Problem 4.4 E 1 3 5
2 4 6
2-Hexanone
6
3 4 5
200 180 160 140 120 100 80 60 40 20 ppm

O
Problem
Problem 5.7F
4.4 F 2
3
HO 1
Propionic Acid
3
2
1
180 160 140 120 100 80 60 40 20 ppm

Answers for Student Exercise 4.4 G-I
18
2 4
Problem
Problem 5.7G
4.4 G H2N 1 3
Butylamine
1 2 3 4
95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 ppm
1 2 OH
Problem 5.7H
Problem 4.4 H 3
Propargyl alcohol
1 3 Note that it is often the case that the DEPT

2 spectra are incorrect for alkynes. Intensities
of the CH are quite different than the C,
which is apparent here.
95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 ppm
O
Problem
Problem 5.7I
4.4 I - N+ 1 3
O 2
1-Nitropropane
1
3
2
77.5 77.0 ppm
95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 ppm
3
Answers for Student Exercise 4.4 J-L 4 2 OH 19
6
Problem
Problem 5.7J
4.4 J 1 5
O
2-Phenoxylethanol
3 2
4 5 6
170 160 150 140 130 120 110 100 90 80 70 60 ppm

6 2 3
Problem 5.7K
4.4 K 5 1
Problem O 4
Phenetole
3 2
4 5 6
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

O
4
Problem
Problem 5.7L
4.4 L O 1
5 2 3
Methyl Butyrate
2 3 4
5
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

O
Answers for Student Exercise 4.4 M-O 20
HN 1 2
Problem
Problem 5.7M
4.4 M 6 3
5 4
Caprolactam
6 2 53 4
180 160 140 120 100 80 60 40 20 ppm

3 4
Problem 5.7N
4.4 N N
Problem 2
5
7
N6
1
2-methylpyrazine
365
7
150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

HO
Problem
Problem 5.7O
4.4 O 1 6
O
2 5
7
O 3 4
8
Methyl salicylate
5 34 6 8
7 1 2
170 160 150 140 130 120 110 100 90 80 70 60 ppm

Answers for Student Exercise 4.4 P-R 21
Problem 5.7P
Problem 4.4 P
3 2
O
1
N+ 4 Cl
-
O
2 3
4 1 148 146 144 ppm
155 150 145 140 135 130 125 120 115 110 105 100 95 90 85 80 ppm
O
Problem
Problem 5.7Q
4.4 Q 2
3
4
5
6
7 Br
HO 1
7-Bromo Heptanoic Acid
276453
180 160 140 120 100 80 60 40 20 ppm

6
Problem 5.7R
Problem 4.4 R 2 4
HO 1 3 5
5-Hexyn-1-ol Note that it is often the case that the DEPT
spectra are incorrect for alkynes. Intensities
of the CH are quite different than the C,
which is apparent here.
1 2 3 4
6
85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 ppm
Answers for Student Exercise 4.4 S-U
O 8 22
Problem
Problem 5.7S
4.4 S 1 3 5
2 4 6 7
6-Methyl-5-hepten-2-one
7 4
5
3 1 8
6
2
200 180 160 140 120 100 80 60 40 20 ppm

O
Problem 5.7T
Problem 4.4 T 2 4 6
HO 1 3 5
Hexanoic acid
2 4 35 6
180 160 140 120 100 80 60 40 20 ppm

HO Cl
1 2
Problem
Problem 5.7U
4.4 U
Cl 3
4
2,6-Dichlorophenol
3 4 4
2
1
121.2 ppm
155 150 145 140 135 130 125 120 115 110 105 100 95 90 85 80 ppm
Answers for Student Exercise 4.4 V-W
23
Problem
Problem 5.7V
4.4 V
5
HO
1 2
3
4
2,6-Dimethylphenol
3
5
4
1 2
150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm
Problem
Problem 5.7W
4.4 W O
1
6 2
5 4 3
2-Cyclohexen-1-one
6 45
3 2
200 180 160 140 120 100 80 60 40 20 ppm

24
4.5
2nI +1 rule 1 Example
ID =1
1 1 1 CDCl3
1 2 3 2 1 CD2Cl2
1 3 6 7 6 3 1 CD3Cl
Answers for Student Exercise 4.6 A-C
25
Problem 5.6A
Problem 4.6A
C5H10Br2
2
Br 1 3 Br
1,5-dibromopentane 1 2
75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 ppm
Problem 5.6B
Problem 4.6B HO O
C8H8O2 7
1 8
2
6
5 3
4
2-methylbenzoic acid
4 6 3 5
8
7 2 1 132 130 128 ppm
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm
Problem 5.6C
4.6C H
Problem 2 4 6 N
1 3 5
C12H27N
dihexylamine
6 5 3 4 2 1
75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 ppm
Answers for Student Exercise 4.6 D-F
26
Problem 5.6D
Problem 4.6D
C16H22O4 O
2
1 6 8
3 4 O 5 7
O
3 2 dibutyl phthalate
5 7 8
4 1
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

7
Problem 5.6E
Problem 4.6E
C7H12O 1
2 4 6
3 5
O
5-methylhex-5-en-2-one
6
3 41 7
2
200 180 160 140 120 100 80 60 40 20 ppm
Problem 5.6F
Problem 4.6F OH
C8H14O 2 4 6 8
1 3 5 7
oct-3-yn-1-ol
1 6
5 8
27
4 82 80 78 ppm
3
85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 ppm
27
O
2
1 6
3 4 O 5
3 4 O 5 6
1
2
O
ortho-diethyl phthalate
There is one mirror image. There are 6 nonequivalent carbons, and there are 4 distinct proton
signals, 2,3,5,6 with a integration ratio of 2:2:4:6, or 1:1:2:3.
DEPT 90
DEPT 135
Carbon - 13
4 1,3,2 6
5
180 160 140 120 100 80 60 40 20 0

PPM
28
O O
4
7 7
6 O 51 1 5 O 6
2 2
3
meta-diethyl phthalate
There is one mirror image. There are 7 nonequivalent carbons, and there are 5 distinct proton
signals, 2,3,4,5,6 with a integration ratio of 2:1:1:4:6..
DEPT 90
DEPT 135
Carbon - 13
21 6 7
5
4
3
180 160 140 120 100 80 60 40 20 0

PPM
29
5 4 2 2 4 5
O O
3 3
1 1
O 2 2
O
para-diethyl phthalate
There are two mirror images. There are 5 nonequivalent carbons, and there are 3 distinct proton
signals, 2,4,5 with a integration ratio of 4:4:6, or 1:1:3.
DEPT 90
DEPT 135
Carbon - 13
2
3 1 4 5
180 160 140 120 100 80 60 40 20 0

PPM
3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm COSY

ppm
(a)
0.5 4 0.5
3 1 Br
1.0 3 1.0 4 2
1.5 1.5 (a) 1-bromobutane

2
Group # H C
F1 2.0 2.0 1 3.40 33.5
2 1.85 36.1
2.5 2.5 3 1.20 22.1
4 0.85 13.5
3.0 3.0
1
3.5 3.5
F2
ppm HMQC
5 5
10 10
15 15
20 20
F1 25 25
30 30
35 35
40 40
45 45
3.0 2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0 ppm
F2
ppm 1 3 4 HMBC
2
5 (a)
10
4 3 1 Br
4 2
15
(a) 1-bromobutane
20
3
F1 25 Group # H C
1 3.40 33.5
2 1.85 36.1
30
3 1.20 22.1
1
35 4 0.85 13.5
2
40
45
50
3.0 2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0 ppm
F2 INADEQUATE
Hz 2 1 3 4
Center
-3000 Frequency -3000
-2000 -2000
-1000 -1000
F1 0 0
1000 1000
2000 2000
3000 3000
45 40 35 30 25 20 15 10 5 ppm
F2
COSY
ppm 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
5 6
(b)
5
1.5 1.5 4 1 O
6 7
4 3 2
O 8
2.0 9 2.0 9

2.5 1 2.5
3.0 3.0 Group # H C

1 2.80 36.0
F1 3.5 3.5 2 5.59 131.5
3 5.59 125.5
7 4 1.96 29.8
4.0 4.0 5 1.65 27.0
6 1.80 33.4
4.5 4.5 7 4.05 67.5
8 NA 170.5
5.0 5.0 9 2.10 20.7
2
5.5 3 5.5
F2
ppm HMQC
20 9 20
1 5
4
6
40 40
60 60
7
7
F1
80 80
100 100
120 120
2
3
6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
F2
3 HMBC
2 7 1 9 46 5
ppm 5 6 (b)
9 41
4 1 O
56
7
O 8
40 3 2 9

60
7
Group # H C
1 2.80 36.0
80
2 5.59 131.5
F1 3 5.59 125.5
100 4 1.96 29.8
5 1.65 27.0
6 1.80 33.4
120 7 4.05 67.5
32
8 NA 170.5
140 9 2.10 20.7
160
8
180
6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
F2 Center INADEQUATE
Hz 8 2 3 Frequency 7 16 4 5 9
-10000 -10000
-5000 -5000
F1 0 0
5000 5000
10000 10000
180 160 140 120 100 80 60 40 20 ppm

F2
COSY
ppm 7 6 5 4 3 2 1 ppm
(c)
O 9 10
1 2 1
1 8
3 7 OH
34 Group # H C
2 4 6 OH 2 1 NA 143.2
10 2 6.68 150.0
5 8 3 2.05 28.3
9 4 2.05 30.7
3 3 5 5.68 122.1
F1 6 6.22 131.1
7 NA 206.7
4 4 8 2.65 45.5
9 3.20 60.5
10 1.05 8.9
OH 0.5-4 NA
5 5
5
6 6 6
2
F2
HMQC
ppm
10
20 20
3
4
40 8 40
9
60 60
F1 80 80
100 100
5
120 6 120
140 140
2
7 6 5 4 3 2 1 ppm
F2
4 HMBC
2 6 5 9 8 3 10
ppm (c)
10
O 9
20 2
1 8
3
34 8
7 OH
40
4 6
10
60 5
9
Group # H C
80 10 1.05 8.9
F1 3 2.05 28.3
100 4 2.05 30.7
8 2.65 45.5
120 9 3.20 60.5
56 1 2
5 5.68 122.1
140 6 6.22 131.1
1 NA 143.2
160 2 6.68 150.0
7 NA 206.7
OH 0.5-4 NA
180
200
7
7 6 5 4 3 2 1 ppm
7 2 1 6 5 Frequency 9 8 43 10
Hz
-10000 -10000
-5000 -5000
F1 0 0
5000 5000
10000 10000
15000 15000
200 180 160 140 120 100 80 60 40 20 Hz
F2
2.5 2.0 1.5 1.0 0.5 ppm COSY

ppm
(d)
4 H
5 3 2 1
0.5 0.5
5
Group # H C
1.0 1.0 1 1.80 67.6
2 NA 84.6
3 2.20 25.0
4 4 1.50 21.2
1.5 1.5 5 0.85 12.5
F1 1
2.0 2.0
3
2.5 2.5
F2
HMQC
ppm
10 5 10
4
20 3 20
30 30
40 40
F1
50 50
60 60
1
70 70
80 80
2.5 2.0 1.5 1.0 0.5 ppm

F2
HMBC
3 1 4 5
ppm (d)
10 5 4 H
5 3 2 1
20 4
3
30 Group # H C
1 1.80 67.6
F1 40 2 NA 84.6
3 2.20 25.0
4 1.50 21.2
50 5 0.85 12.5
60
1
70
80
2
90
2.5 2.0 1.5 1.0 0.5 ppm
1 2 Frequency 3 4 5
Hz
-4000 -4000
-2000 -2000
F1 0 0
2000 2000
4000 4000
6000 6000
90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 Hz
F2
COSY
ppm 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
6
(e)
1 1 O
1 1 3 5
5 2 4 6
2 2
Group # H C
3 3 1 1.86 28.8
2 NA 196.9
3 6.09 137.6
4 6.82 142.1
F1 4 4 5 2.05 23.4
6 1.00 13.9
5 5
3
6 6
4
F2
HMQC
ppm 6
20 5 20
1
40 40
60 60
F1
80 80
100 100
120 120
3
4
140 140
7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
F2
HMBC
4 3 5 1 6
ppm (e)
6
20 5 O
1
1 3 5
40 2 4 6
60 Group # H C
1 1.86 28.8
F1 80 2
3
NA
6.09
196.9
137.6
100 4 6.82 142.1
5 2.05 23.4
6 1.00 13.9
120
3
140 4
160
180
2
200
7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
2 4 3 Frequency 15 6
Hz
-10000 -10000
-5000 -5000
F1 0 0
5000 5000
10000 10000
15000 15000
200 180 160 140 120 100 80 60 40 20 Hz
F2
COSY
ppm 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
(f)
5
1 1 1 O 2 4
5
3
4
2 2 H C
Group #
1 3.20 55.8
2 6.14 143.5
3 1 3 3 4.63 102.0
4 2.05 23.1
F1 5 1.00 13.6
4 4
3
5 5
2
6 6
F2
HMQC
ppm
5
20 4 20
40 40
1
60 60
F1
80 80
3
100 100
120 120
2
140 140
7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
F2
HMBC
2 3 1 4 5
ppm (f)
5 1 O 2 4
5
20 3
4
40
Group # H C
1 1 3.20 55.8
F1 60 2 6.14 143.5
3 4.63 102.0
4 2.05 23.1
80 5 1.00 13.6
100 3
120
140
2
7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
2 3 Frequency 1 4 5
Hz
-5000 -5000
F1 0 0
5000 5000
10000 10000
150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 Hz

F2
COSY
ppm 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
5
O (g)
1 1 1
4
4 N 2 O 3 5
H
2 2
1 Group # H C
1 2.95 28.4
3 3 2 NA 157.8
F1 3 4.10 63.0
4 1.60 20.7
3 5 0.85 13.0
4 4 NH 4.5-7.5 NA
5 5
NH
6 6
F2
HMQC
ppm
5
20 4 20
1
40 40
60 3 60
F1
80 80
100 100
120 120
140 140
7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
F2
HMBC
3 1 4 5
ppm
(g)
5 O
20 1
4 4
N 2 O 3 5
40 H
1 Group # H C
60
F1 1 2.95 28.4
2 NA 157.8
3 4.10 63.0
80 4 1.60 20.7
5 0.85 13.0
NH 4.5-7.5 NA
100 3
120
140
2
7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
2 Frequency 3 1 4 5
Hz
-10000 -10000
-5000 -5000
F1 0 0
5000 5000
10000 10000
140 120 100 80 60 40 20 Hz

F2
COSY
ppm 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
1
2 O 3 O
1.0 1 1.0
(h)
1.5 1.5
Group # H C
2.0 2.0 1 1.20 11.6
2 3.40 61.0
2.5 2.5 3 4.95 113.3
F1 3.0 3.0
3.5 3.5
2
4.0 4.0
4.5 4.5
3
5.0 5.0
5.5 5.5
F2
HMQC
ppm
1
20 20
40 40
2
60 60
F1
80 80
100 100
3
120 120
6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
F2
HMBC
3 2 1
ppm
1
1 2 O 3 O
20
(h)
40 Group # H C
1 1.20 11.6
2 3.40 61.0
F1 3 4.95 113.3
60 2
80
100
3
120
6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
3 Frequency 1
Hz 2
-8000 -8000
-6000 -6000
-4000 -4000
-2000 -2000
F1 0 0
2000 2000
4000 4000
6000 6000
8000 8000
120 110 100 90 80 70 60 50 40 30 20 10 Hz

F2
COSY
ppm 2.0 1.8 1.6 1.4 1.2 1.0 0.8 0.6 ppm
(i)
0.6 0.6 1 6
3 5
0.8 5 0.8
2 4
HO
1.0 1.0 Group # H C

1 1.20 29.8
2 NA 68.3
F1 1.2 4 3 1.50 46.7
6 1 1.2
4 1.20 15.1
5 0.85 14.1
6 1.20 29.8
1.4 1.4 OH 0.5-4.0 NA
3
1.6 1.6
1.8 OH 1.8
F2
HMQC
ppm
10 5 10
4
20 20
30 6 1 30
F1 40 40
3
50 50
60 60
70 70
80 80
2.0 1.8 1.6 1.4 1.2 1.0 0.8 0.6 ppm
F2
6
4 HMBC
3 1 5
ppm
(i)
1 6
10 5
4 3
2 5
4
20 HO
16 Group # H C
30
1 1.20 29.8
F1 2 NA 68.3
40 3 1.50 46.7
4 1.20 15.1
3 5 0.85 14.1
50 6 1.20 29.8
OH 0.5-4.0 NA
60
2
70
2.0 1.8 1.6 1.4 1.2 1.0 0.8 ppm

2 3 Frequency 1,6 45
Hz
-4000 -4000
-2000 -2000
F1 0 0
2000 2000
4000 4000
6000 6000
75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 Hz
F2
COSY
ppm 3.0 2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 ppm
(j)
1.2 1.2 1 S 2
3 S
1.4 1.4
3 Group # H C
1 2.10 17.5
1.6 1.6
2 2.60 33.5
3 1.60 29.6
1.8 1.8
F1
2.0 1 2.0
2.2 2.2
2.4 2.4
2
2.6 2.6
2.8 2.8
F2
HMQC
ppm
15 15
1
20 20
F1 25 25
3
30 30
2
35 35
40 40
3.0 2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 ppm
F2
HMBC
2 1 3
ppm (j)
1 S 2
3 S
15
1 Group # H C
20 1 2.10 17.5
2 2.60 33.5
3 1.60 29.6
F1
25
3
30
2
35
40
3.0 2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 ppm
2 3 Frequency 1
Hz
-1500 -1500
-1000 -1000
-500 -500
F1 0 0
500 3 to 3' 500
1000 1000
1500 1500
2000 2000
40 38 36 34 32 30 28 26 24 22 20 18 16 14 12 Hz
F2
COSY
ppm 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 ppm
8 (k) O
6
6,7 1
5 N
3 3
4 2 7
8
3
4 4
Group # H C
1 NA 130.6
F1 2 7.80 127.2
5 5 3 7.25 129.2
4 NA 141.2
5 NA 171.0
6 2.95 38.5
6 6 7 2.95 38.5
8 2.25 21.3
7 3 7
F2
HMQC
ppm
8
40 40
6,7
60 60
F1
80 80
100 100
120 120
2 3
3.0 2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 ppm
F2
7 HMBC
2 3 6 8
ppm (k) O
8
6
1
5 N
40 67
4 2 7
8
60 3
F1 80 Group # H C
1 NA 130.6
2 7.80 127.2
100
3 7.25 129.2
4 NA 141.2
120 5 NA 171.0
23 6 2.95 38.5
1
7 2.95 38.5
140 4 8 2.25 21.3
160
5
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 ppm
7
5 4 13 2 Frequency 6 8
Hz
-10000 -10000
-5000 -5000
F1 0 0
5000 5000
10000 10000
160 140 120 100 80 60 40 20 Hz

F2
COSY
ppm 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 ppm
(l) O
6
1 8
3 3 5 7
2
4
3 OH
4 4
Group # H C
F1 1 NA 123.6
5 5 2 NA 154.7
3 6.85 115.4
4 7.05 132.9
5 7.25 120.8
6 6 6 7.70 129.7
7 NA 197.6
3 8 2.40 26.3
OH 5.5-12.5 NA
4
7 5 7
6
F2
HMQC
ppm
8
40 40
60 60
F1
80 80
100 100
3
5
120 120
6
4
3.0 2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 ppm
F2
HMBC
6 54 3 8
ppm (l)
8 O
6
40 1 8
5 7
60 2
4
3 OH
80
F1 100
Group # H C
1 NA 123.6
3
120 2 NA 154.7
51
3 6.85 115.4
64 4 7.05 132.9
140 5 7.25 120.8
6 7.70 129.7
2 7 NA 197.6
160
8 2.40 26.3
OH 5.5-12.5 NA
180
7
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 ppm
F2 INADEQUATE
Center
7 2 4 6 1 5 3 Frequency 8
Hz
-10000 -10000
-5000 -5000
F1 0 0
5000 5000
10000 10000
180 160 140 120 100 80 60 40 Hz

F2
COSY
ppm 11 10 9 8 7 6 5 ppm
(m)
1 2 H
5 5 Cl 1
O
6 6
Group # H C
1 4.95 59.5
F1 7 7 2 9.80 199.7
8 8
9 9
2
10 10
F2
HMQC
ppm
60 1 60
80 80
100 100
F1 120 120
140 140
160 160
180 180
2
200 200
11 10 9 8 7 6 5 ppm
F2
HMBC
2 1
ppm
(m)
60 1 2 H
Cl 1
80
O
100 Group # H C
F1 1 4.95 59.5
120 2 9.80 199.7
140
160
180
200 2
11 10 9 8 7 6 5 ppm
2 Frequency 1
Hz
-10000 -10000
-5000 -5000
F1 0 0
5000 5000
10000 10000
200 180 160 140 120 100 80 60 Hz

F2
COSY
ppm 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 ppm
1trans (n)
4.5 4.5 1cis
1cis H
5.0 5.0 H
H
1trans
2
5.5 5.5 F
F1
Group # H C
6.0 6.0
1cis 4.85 132.2
1trans 4.23 132.2
2 6.79 191.2
6.5 6.5
2
7.0 7.0
7.5 7.5
F2
HMQC
ppm
1
130 130
140 140
150 150
F1 160 160
170 170
180 180
2
190 190
200 200
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 ppm
F2
HMBC
2 1cis 1trans
ppm
(n) 1cis
130
1 H
140 H
H
1trans
2
150 F
F1
Group # H C
160 1cis 4.85 132.2
1trans 4.23 132.2
2 6.79 191.2
170
180
190
2
7.0 6.5 6.0 5.5 5.0 4.5 ppm

2 Frequency 1
Hz
-4000 -4000
-2000 -2000
F1 0 0
2000 2000
4000 4000
6000 6000
190 180 170 160 150 140 130 Hz
F2
COSY
ppm 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
(o)
33' 4 2'
1.5 22' 1.5
3' 1 O O
5
6
2.0 2.0 4 2 6
3
2.5 2.5
3.0 3.0 Group # H C

1 4.95 77.9
F1 2,2' 1.60 32.9
3.5 3.5 3,3' 1.44 23.9
4 1.44 26.9
4.0 4.0 5 NA 168.0
6 2.00 20.8
4.5 4.5
1
5.0 5.0
5.5 5.5
F2
HMQC
ppm
33'
6 4
40 22' 40
60 60
1
80 80
F1
100 100
120 120
140 140
160 160
6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
F2
33' HMBC
1 6 22' 4
ppm
6
(o)
3 3' 2'
4 1 O O
2
40 5
2 6
4
60 3
1 Group # H C
F1 80 1 4.95 77.9
2,2' 1.60 32.9
100 3,3' 1.44 23.9
4 1.44 26.9
5 NA 168.0
120 6 2.00 20.8
140
160
5
6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 ppm
F2 INADEQUATE
Center
5 Frequency 1 2 43 6
Hz
-10000 -10000
-5000 -5000
F1 0 0
5000 5000
10000 10000
160 140 120 100 80 60 40 20 Hz

F2
CH2
6
5 7
g= geminal H
4 8 CH2
v= vicinal HO 3 1
lr= long range CH3
H3C 2 CH3
1
CH2=
8 OH
7 4 5 5' 2 3 3'
ppm
0.5
v
1.0
v v g
1.5
v
2.0 v
lr v g
2.5
3.0
F1
3.5
4.0 v v
4.5
5.0 g
v lr
5.5
6.0
6.5 v
7.0
7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
F2
CH2
6
5 7
H
4 8 CH2
HO 3
H3C 2 CH3
1
Carbon 13 Signals
1 2 3 4 5 6 7 8 CH3 CH2=
1
H 1 Bonded
2 Bonded
S 3 Bonded
I 4 Bonded
g 5 Bonded
n 6
l 7 Bonded
a 8 Bonded
l CH3 Bonded
s CH2= Bonded
1
H NMR 600 MHz
4 6
5
3 2
5
1300 Hz 1250 Hz 1150 Hz

4 3
6
1050 1000 Hz 860 840 820 Hz 620 600 580 Hz
2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 ppm
13
C/DEPT 600 MHz
O
6
6 5 3 4
1
2 5
3 4 2
2-methylcyclopentanone
220 200 180 160 140 120 100 80 60 40 20 ppm

ppm 2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0 ppm COSY 600 MHz
1.0 1.0 6
1.2 1.2
O
1.4 1.4 3 6
1
2 5
F1
1.6 1.6 3 4
4 2-methylcyclopentanone
1.8 1.8
4
2.0 2.0 5
2
3
2.2 2.2 5
F2 6 HMQC 600 MHz

5 3 2 5 4 4 3
ppm
6
15 15
20 20 4
25 25
F1 30 30 3
35 35
5
40 40
2
45 45
2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0 ppm

F2
1
H NMR 600 MHz
9 7 8 6
4800 4750 Hz 4450 4400 Hz 4350 4300 Hz

2 4 3
2 4
1750 1700 Hz 1550 1500 Hz 1250 1200 Hz 3
9 7 8 6
O
9
10 1
8 2
7 3
5
6 4
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 ppm
13
C/DEPT 600 MHz
8 6 97
2 4 3
5
1 10
200 180 160 140 120 100 80 60 40 ppm

ppm 8 7 6 5 4 3 2 ppm COSY 600 MHz
2 2 3
4
3 3 2
ppm 8.0 7.5 7.0 ppm O
4 7.0 4 9
10
8 1 2
6
8
F1 7
5 5 7 5
3
7.5 6 4
6 6
8.0 9
7 7
8 8
F2 HMQC 600 MHz

ppm
3
4
40 40 2
ppm
125
60 7 60
9
6
130
80 80
8
F1 135
8.2 8.0 7.8 7.6 7.4 7.2 ppm
100 100
120 120
140 140
9 8 7 6 5 4 3 2 ppm
F2
1
H NMR 600 MHz 3
5
1
5480 5470 Hz 5200 5190 Hz 4910 4900 Hz

4 8
7 8
4370 4360 Hz 2590 2580 Hz 790 780 Hz

7
O
3
CH2 8
6 O 7 CH3
4 2
5 1
1 5 3 4 N
ethyl nicotinate
9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 ppm
13
13C/DEPT
C/DEPT600
NMRMHz
150.9 MHz
5 1
4 7
3
8
2
6
160 150 140 130 120 110 100 90 80 70 60 50 40 30 ppm

ppm 9 8 7 6 5 4 3 2 ppm COSY 600 MHz
8
O
2 2
3
CH2 8
6 O 7 CH3
3 4 2 3
5 1
N
4 4
ethyl nicotinate 7
F1 5 5
6 6
7 7
4
8 8 3
5
9 9 1
F2 8 HMQC 600 MHz

7
ppm 1 5 3 4
8
20 20
40 40
60 60 7
80 80
F1
100 100
120 120 4
2
3
140 140
1
5
160 160
6
9 8 7 6 5 4 3 2 ppm
F2
INADEQUATE
INADEQUATE 600
150.9 MHz
MHz
Hz
-25000 7 8 -25000
O
3
-20000 CH2 8 -20000
6 O 7 CH3
4 2
-15000 -15000
5 1
N
-10000 -10000
ethyl nicotinate
-5000 -5000
F1 0 0
5000 5000
10000 10000
15000 15000
20000 20000
25000 25000
160 140 120 100 80 60 40 20 ppm

5 F2
1 3 4
6 2
Hz
12000 12000
13000 13000
F1
14000 14000
15000 15000
16000 16000
17000 17000
165 160 155 150 145 140 135 130 125 ppm
F2
Answers for Student Exercises 5.7 INADEQUATE 150.9 MHz 40
13
8
Hz
-10000 -10000
15 3
H3C H 2 CH3
4 12
1
-5000 H3C
14
11
5 O
-5000
9
10 6
8 7
H
CH2
13
F1 0 8-7 0
8-9
5000 5000
8-13
10000 10000
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

14
5 1 9 10 3 11 67 2 15 12
4
Hz
-9000 11-15 -9000

11-14 C6-C7
3-2
-8000 -8000
4-12 10-11
F1-7000 1-2 -7000

1-11
5-6 9-10
-6000 -6000
4-3
-5000 1-9 -5000
-4000 -4000
5-4
65 60 55 50 45 40 35 30 25 20 15 ppm
F2
The following correlations can be found in the INADEQUATE spectrum of caryophyllene oxide
Carbon 1 correlates with carbons 2, 9, and 11

Carbon 2 correlates with carbons 1 and 3 15 3
H3C H 2 CH3
Carbon 3 correlates with carbons 2 and 4 4 12
Carbon 5 correlates with carbons 4, and 6 H3C 11 1
Carbon 6 correlates with carbons 5, and 7 14 5 O
Carbon 7 correlates with carbons 6, and 8 9
10 6
Carbon 9 correlates with carbons 1, 8, and 10 8 7
H
Carbon 10 correlates with carbons 9 and 11
Carbon 11 correlates with carbons 1, 10, 14, and 15 CH2
Carbon 12 correlates with carbons 4 13
Carbon 13 correlates with carbons 8
1
H NMR 600 MHz
2 1 1
6 OH
9
3500 3450 Hz 3050 3000 Hz 1400 1350 Hz

5 8 10 9 10
4 8
1200 1150 Hz 950 900 Hz 9 750 700 Hz

OH
1 6 1 4 3 2
2 5 4
5 6 1
OH
7
10 8
3,7-dimethylocta-1,6-dien-3-ol
5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
13
13 C/DEPT NMR 150.9 MHz
C/DEPT 600 MHz
9 5
1 4
2 6 8
7
3 10
150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

ppm 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm COSY 600 MHz
9
1.5 1.5 4 10
8
2.0 2.0 5
OH
9
2.5 OH 2.5
3 2
3.0 4 3.0
F1 5 6 1
3.5 3.5
4.0 7 4.0
10 8
4.5 3,7-dimethylocta-1,6-dien-3-ol 4.5
1
5.0 5.0 6
1
5.5 5.5
2
F2 8 10 9 HMQC 600 MHz

2 1,6,1 4
ppm 5
10 5
20 20
8
9
40 40 4
60 60
3
80 80
F1
100 100
1
120 120
6
7
140 140 2
6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
F2
Answers for Student Exercises 5.8 HMBC 600 MHz 44
10 9
8
2 161 4
OH 5
ppm
10 5
20 9 8
OH 9
40 4 3 2
4
5 6 1
60
7 3
10 8
80
F1 3,7-dimethylocta-1,6-dien-3-ol
100
1
120
6
7
140
2
160
6.0 5.5 5.0 4.5 4.0 F2 3.5 3.0 2.5 2.0 1.5 ppm
ppm ppm
20 20
40 40
60 60
F1
ppm ppm
120 120
140 140
6.0 5.9 5.8 ppm 5.2 5.0 ppm 2.0 1.5 ppm
F2
INADEQUATE 150.9
INADEQUATE 600MHz
MHz
2 6 1 3 4 9 85
10
7
Hz
9
OH
4 3 2
-15000 5 6 1 -15000
7
10 8
3,7-dimethylocta-1,6-dien-3-ol
-10000 -10000
-5000 -5000
F1
0 0
5000 5000
10000 10000
15000 15000
140 120 100 80 60 40 20 ppm

F2
5.2 5.0 4.8 4.6 4.4 4.2 4.0 3.8 3.6 3.4 TOCSY 600 MHz
ppm
2
3.4 3.4
G2
5
3.6 2 3 3.6
4 4
G3
G5
G6
3.8 3 6 3.8
6 6
G4
4.0 5 4.0
F1
4.2 4.2
4.4 4.4
G1
4.6 4.6
1
4.8 4.8
HDO
5.0 5.0
5.2 5.2 1
5.2 5.0 4.8 4.6 4.4 4.2 4.0 3.8 3.6 3.4 ppm
F1
Correlations from the three anomeric protons are drawn. These correlations show the ring protons
for the three monosaccharide residues of lactose. Correlations among the ring protons are difficult
to decipher due to overlap. Results from the 1D HOHAHA in Figure 5.26 agree with these
findings.
1
H NMR 600 6MHz
CH2OH
O
6
HO CH2OH
5 H
H
CH2 1 H
CH2OH
4
HO HO O H H 1 O
O H O
H CH52
H O H 2 CH2HOH HO 5H
HHO
3 H 2 H HO O
H H1 O
H H HO 4 H O H HO
HO HO H2 3 4 CH2OH
H HO
3 H 6
HO H HO O HO CH2OH
H
-Galactose H HO HO
-Glucose
Ring A Ring B -Fructose
A6 C1 Ring C
C3 C4 B5 A2 B3 C1
B6 A4 A5 C5 C6 C6 B6 B2 B4
A3
4.1 4.0 3.9 3.8 3.7 3.6 3.5 ppm
HDO C4
C3
B1 A1
5.4 5.3 5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6 ppm
13
13C/DEPT
C/DEPT NMR 150.9 MHz
600 MHz
C3 B3 B5 A5 A3 B4 A4 A2
B2
74.0 73.5 73.0 72.5 72.0 71.5 71.0 70.5 70.0 69.5 69.0 ppm
B1 C5
A1 C3 C4
C2 C6 C1A6
B6
100 95 90 85 80 75 70 65 ppm
Mixing time 300 ms 5.40 ppm irradiated 1-d TOCSY 600 MHz
B6
B6
Mixing time 80 ms
B5 B4
Mixing time 40 ms
B3
Mixing time 20 ms B2
4.05 4.00 3.95 3.90 3.85 3.80 3.75 3.70 3.65 3.60 3.55 3.50 ppm
Mixing time 300 ms 4.97 ppm irradiated 1-d TOCSY 600 MHz
A5 A6
Mixing time 80 ms
A4
Mixing time 40 ms A3
Mixing time 20 ms A2
1
H NMR 600 MHz
4.05 4.00 3.95 3.90 3.85 3.80 3.75 3.70 3.65 3.60 3.55 3.50 ppm
Mixing time 80 ms 1-d TOCSY 600 MHz

C6 C6
Mixing time 40 ms
C5
Mixing time 20 ms
C4
1
H NMR 600 MHz
4.05 4.00 3.95 3.90 3.85 3.80 3.75 3.70 3.65 3.60 3.55 3.50 ppm
6 CH2OH
O
6
HO 5 H
H
CH2 1 H
1 O CH2OH
4 HO H O H O
H 5
H H 1 2 H HO 5
3 2 HO H
H HO 4 O
HO
2 3 4 CH2OH
3 H 6
H HO HO
-Galactose
-Glucose
Ring A Ring B -Fructose
Ring C
5.4 5.2 5.0 4.8 4.6 4.4 4.2 4.0 3.8 3.6 ppm COSY 600 MHz
ppm
3.6 3.6
3.8 3.8
4.0 4.0
4.2 4.2 C3
F1
4.4 4.4
4.6 4.6 HDO

4.8 4.8
A1
5.0 5.0
5.2 5.2
5.4 5.4 B1
ppm COSY 600 MHz
3.5 B4
B2
3.6 C1
B6
3.7 A6
C6B3
C6 A2
3.8
F1 C5
A3
3.9 A5
A4
B6 B5
4.0 C4
4.1
C3
4.2
4.2 4.1 4.0 3.9 3.8 3.7 3.6 3.5 ppm
F2
ppm 5.4 5.2 5.0 4.8 4.6 4.4 4.2 4.0 3.8 3.6 ppm TOCSY 600 MHz
3.6 3.6
3.8 3.8
4.0 4.0
C3
4.2 4.2
F1
4.4 4.4
4.6 4.6 HDO

4.8 4.8
A1
5.0 5.0
5.2 5.2
B1
5.4 5.4
TOCSY 600 MHz

ppm
B4
3.5
B2
3.6 C1
B6
3.7 A6
C6B3
C6 A2
3.8
F1 C5
A3
3.9 A5
A4
B6 B5
4.0 C4
4.1
C3
4.2
4.2 4.1 4.0 3.9 3.8 3.7 3.6 3.5 ppm
F2
B1 A1 C1 HMQC 600 MHz
B5A4 A6
C3 C4 B6 C6 C6
A5 A3C5 A2 B3 B6 B2 B4
ppm 5.5 ppm 4.1 4.0 3.9 3.8 3.7 3.6 3.5 ppm
60
A6
F1 C1
C6
65
B6
ppm A2
69 A4
B4
A3
70
B2
71 A5
B5
72
B3
73
74 C4
F1
75
76
C3
77
78
79
80
81
C5
ppm B1
95
F1 A1
100
C2
105
5.5 ppm 4.1 4.0 3.9 3.8 3.7 3.6 3.5 ppm
F2
B1 A1 HMQC-TOCSY
C1 600 MHz
B5A4 A6
C3 C4 B6 C6 C6
A5 A3C5 A2 B3 B6 B2 B4
ppm 5.5 ppm 4.1 4.0 3.9 3.8 3.7 3.6 3.5 ppm
60
A6
F1 C1
C6
65
B6
ppm A2
69 A4
B4
A3
70
71 B2A5
B5
72
B3
73
74 C4
F1
75
76
C3
77
78
79
80
81
C5
ppm B1
95
F1 A1
100
C2
105
5.5 ppm 4.1 4.0 3.9 3.8 3.7 3.6 3.5 ppm
F2
B1 A1 C1 HMBC 600 MHz
B5A4 A6
C3 C4 B6 C6 C6
A5 A3C5 A2 B3 B6 B2 B4
ppm 5.5 ppm 4.1 4.0 3.9 3.8 3.7 3.6 3.5 ppm
60
A6
C1
F1 C6
65
B6
ppm A2
69 A4
B4
A3
70
B2A5
71 B5
72
B3
73
74 C4
F1
75
76
C3
77
78
79
80
81
C5
ppm B1
95
F1 A1
100
C2
105
5.5 ppm 4.1 4.0 3.9 3.8 3.7 3.6 3.5 ppm
F2
1
H NMR 600 MHz
6 22 12
23 3
4
20 7 1 16
3200 7,8,24,25
3100 Hz 2200 2100 Hz 1300 Hz 1100 1000 Hz
2 17 15 19
11 29 18
28 1 14 21
15 27 26
28 16 12 9
1000 900 Hz 700 600 Hz 600 500 Hz

29
21
22 28
CH3
19 11 12 CH3
18 27
1 CH
CH33 H CHCH 20 24
2 3 3 23 25
HO 3 13
HO 10 9 17 H
4 14 26
8 16
5 15
6 7 HH
5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
13
13 C/DEPT600
MHz
21
8 25 27 29
18
7 2 11 13 20
12
22 23 6 32.0 ppm 21.5 ppm 3 1417 9 24 4 15
1 16 28
5 10 19
26
140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

COSY 600 MHz
ppm 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
18
1 1 19
2 2
4
29
21
22 28
CH3
19 311 12 18 27
3
1 CH3 CH3 20 24
2 23 25
HO 3 13
4
10 9
14
17 26 4 2 2
3
8 16
5 15
4 4
6 7
5 20 24
5 23
22
4 7 7
6
ppm COSY 600 MHz
0.6 18
26 17
0.8 29
27
9 14
1.0 19
29 to 28 1 15 21
28 17
1.2 12
16
29 to 28
1.4 28
F1 2 11
7 8 24 25
1.6 27 26 to 25
15
16
15 16 17 15 15 to 14
1.8 7 21
2 1
8 7
2.0 12
7,11 20
17 21
2.2 7 2lr 7
4
2.4
2.4 2.2 2.0 1.8 1.6 1.4 1.27 1.0 0.8 7 0.6 ppm
F2
Answers for Student Exercises 5.11 8 57
25 21 29
22 3 711
HMQC
1927 26
600 MHz
6 23 242 12 2815 14
4 12 1 16 15 28 16 17 1 9
2 18
20 7
ppm 5.5 ppm 3.6 ppm 2.2 2.0 1.8 1.6 1.4 1.2 1.0 0.8 0.6 ppm
18
29
15
26
20 19
27
2111
15
25
28
16
30
2
725
8
35
10
F1 1
40 12
20
13
4
45
50 9
24
55 17
14
60
65 29
21
22 28
CH3
19 11 12 18 27
70
1 CH3 CH3 20 24
2 23 25 3
HO 3 13
10 9 17
4 14 26
8 16
5 15
ppm 6
6 7
130 23
22
140 5
5.5 ppm 3.6 ppm 2.2 2.0 1.8 1.6 1.4 1.2 1.0 0.8 0.6 ppm
F2
Answers for Student Exercises 5.11 8 58
25 21 HMBC 600 MHz
22 3 711 19272926
6 23 242 12 2815 14
4 12 1 16 15 28 16 17 1 9
2 18
20 7
ppm 5.5 ppm 3.6 ppm 2.2 2.0 1.8 1.6 1.4 1.2 1.0 0.8 0.6 ppm
12-18 17-18 14-18 18
24-29 28-29 28-29
29
15 13C Satellite peaks
23-26 24 25-26 27-26 26

6-19 19
1 19
20 22,23-21
28 2711
21
12-11 24+25-27 9-11 26-27
22,23-28 16-15 14-15 15
25
24 25-28 29-28
28
17 15 14-16
16
30 6-7 22,23-25 3-2 4-2 7-8 1-2 24,28-25 28-25 15-8 14,9-(7,8) 2
. 15-8 725
8
12-8 27 26-25
35 6-10
3-1
4-10 1,2-10 8,7,-10 119 9-10 10
F1 1
2-1 2-1 19 9-1
40
22,23-20 11-12 17-12 21-20 18-12 12
16-20 20
3-4 13
17-20 4
6-4 12-13 2-4 16-13 15,11-13 12,15,17-13 14-13 18-13
45
22,23-24 12-9, and 7-9 7,8,11 12 1-9 19-9

50 9
24
25-24 28-24 28-24 27,29,26-24
22,23-17
55 16-17 16 12 21 18-17 17
14
7-14 15 8-14 16 12 15-14 29 18-14
60 21
CH3 22 28
19 11 12 18 27
1 CH3 CH3 20 24
2 23 25
65 HO 3
10 9
13
17
4 14 26
8 16
5 15
70 6 7
6-3
3
4-3 1,2 -3 2-3 1-3
ppm 6
22-23 4-6 7-6 1-6(4b) 7-6
130 23
20-23 24,25 28-23 28-23 27 26-23(4b)
20-22 24-22 17-22 21-22
22
140 6-5 3-5
5
4-5 7-5 1-5 7-5 19-5
5.5 ppm 3.6 ppm 2.2 2.0 1.8 1.6 1.4 1.2 1.0 0.8 0.6 ppm
F2
1
H NMR 600 MHz
0o C in 5%/95% D2O/H2O KNH T2
S3
SNH
T3 K2
S2
5400 5300 5200 5100 Hz 2700 2600 2500 2400 Hz

T4
T4 Impurity
K6
K4
K5
K3 K3
K6
1800 Hz 1100 1000 900 800 Hz
KNH
SNH
1 1 2 # of protons 1 2 3 2 11 2 2 3
9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 ppm
Threonine (Thr) (T) Serine (Ser) (S)
13
Lysine (Lys) (K) TNH
C/DEPT 600 MHz
O O O
2 H 2 H 2 SNH
H2N CH C N CH C N CH C OH
3 1 1
3 CH2
1 KNH
HO CH 3 CH2
4 CH3 OH 4 CH2
5
CH2
6 CH
2
K1 S1 NH2
T1
T3 T2 K2
K4 T4
S3 K3 K5
S2 K6
175 170 ppm 70 65 60 55 50 45 40 35 30 25 ppm

COSY 600 MHz
ppm 9 8 7 6 5 4 3 2 1 ppm
1 1 T4
K5 K4
2 2 K3K3
K6
3 3
S3
K2 T3T2
4 4
F1 S2
5 5
6 6
7 7
TNH
8 8 KNH
SNH
ppm COSY 600 MHz
T4
1.0 1.0
K4
K5
1.5 1.5 K3K3
2.0 2.0
2.5 2.5
F1 K6
3.0 3.0
3.5 3.5 S3
T2
T3K2
4.0 4.0
S2
4.5 4.5
4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
F2
ppm 9 8 7 6 5 4 3 2 1 ppm TOCSY 600 MHz

1 1 T4
K5 K4
2 2 K3K3
K6
3 3
S3
4 4 K2 T3T2
F1 S2
5 5
6 TNH 6
7 7
KNH2
8 8 KNH
SNH
TOCSY 600 MHz

ppm
T4
1.0 1.0
K4
K5
1.5 1.5 K3K3
2.0 2.0
2.5 2.5
F1 K6
3.0 3.0
3.5 3.5 S3
T2
T3K2
4.0 4.0
S2
4.5 4.5
4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
F2
COSY 600 MHz TOCSY 600 MHz ROESY 600 MHz
SNH KNH SNH KNH SNH KNH
KNH2 KNH2 KNH2
ppm
T4
1.0
Threonine (Thr) (T) Serine (Ser) (S) Lysine (Lys) (K) K4
2
O
H 2
O
H 2
O K5
1.5 H2N CH C
1
N CH C
1
N CH C
1
OH K3
3
HO CH 3 CH2 3 CH2
4 CH3 OH 4 CH2
2.0 5
CH2
6 CH
2
2.5 NH2
K6
F1
3.0
3.5 S3
T2
K2
4.0 T3
S2
4.5
9.0 8.5 8.0 7.5 ppm 8.5 8.0 7.5 ppm 8.5 8.0 7.5 7.0 ppm
F2 F2 F2
HMQC 600 MHz
T4
T3 T2S3 K6 K5 K4
K2
S2 K3
ppm
T4
Threonine (Thr) (T) Serine (Ser) (S) Lysine (Lys) (K)
20 O O O
2 H 2 H 2 K4
3 1 1 1 K5
30 HO CH 3 CH2 3 CH2
K3
4 CH3 OH 4 CH2
40
5
CH2 K6
F1 6 CH
2
NH2
50
K2
S2T2
60
S3
T3
4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
F2
HMBC 600 MHz
ppm 9.0 8.5 8.0 ppm 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
T3 T2
20 K2 K6 K3 K5
T4
K4
K6 K3 K4
K5
KNH-K3 K2 K5 K4
30 K3
F1 K5 K4
40 K6
50
KNH-K2
K3 K3 K4 K2
S3 S2
T3 T4 T2
60 S3
S2
T2 T4
T3
F2
T4
K6 K5
KNH T2 K4
SNH KNH2 K2 S3
T3 K3
ppm S2
SNH-T1 S2-T1 T3-T1 T2-T1

168
T1
KNH-S1
S2-S1 K2-S1 T2,S3-S1
170
Threonine (Thr) (T) Serine (Ser) (S) Lysine (Lys) (K)
S1
O O O
F1 172
2 H 2 H 2
3 1 1 1
HO CH 3 CH2 3 CH2
174 4 CH3 OH 4 CH2

5
CH2
6 CH
176 2
NH2
KNH-K1
178 K2-K1 K3-K1
K1
180
9.0 8.5 8.0 ppm 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
F2
Answers for Student Exercise6.1 1
1 NOTE: The formula should be C5H10N2
H NMR 300 MHz
4
3 2
2.75 2.70 2.65 2.60 2.55 2.50 2.45 2.40 2.35 2.30 2.25 2.20 2.15 2.10 ppm
13
C/DEPT NMR 75.5 MHz
4 4
1 3
N
2 4 3
N 2
C5H10N2
Mol. Wt.: 98
3-(dimethylamino)propanenitrile
130 120 110 100 90 80 70 60 50 40 30 20 ppm

15
N NMR 30.4 MHz
N
N
240 220 200 180 160 140 120 100 80 60 40 20 ppm

1
H NMR 300 MHz
1 3
1
1 2 Si Cl 3
1 3
C6H15ClSi
Mol. Wt.: 151
tert-butylchlorodimethylsilane
1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 ppm
13
C/DEPT NMR 75.5 MHz
35 30 25 20 15 10 5 0 -5 ppm
29
Si NMR 59.6 MHz
55 50 45 40 35 30 25 20 15 10 5 ppm
Answers for Student Exercise 6.3 3 3
2 4
1 5
H NMR 300 MHz H3C 1
2 P
34 Br 5
C19H18BrP
Mol. Wt.: 357
2340 2320 2300 Hz
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 ppm
13
C/DEPT NMR 75.5 MHz
4 3
a b
10200 Hz 10000 Hz
2
3 1 5
2
c d e
4
9800 Hz 9000 8900 Hz 800 750 Hz 5
ab c d e
130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

31
P NMR 121.5 MHz, 1H Decoupled
28 26 24 22 20 18 16 14 12 10 8 6 4 2 ppm
MASS
105
175
% of Base Peak
100
244
77
50 127
205
50 100 150 200

m/z
IR
OH
100 F3C CF3
1 2 3
4
5' 5
%Transmittance
50 6' 6
7
C9H6F6O
Mol. Wt.: 244
3602
3548
3070
1504
1273
1219
1165
972
717
1,1,1,3,3,3-hexafluoro-
2-phenylpropan-2-ol
4000 3000 2000 1000
Wavenumber (cm-1)
1
H NMR 19
F NMR 282.4 MHz
6,6
See Table 6.2

7
5,5
OH
7.8 7.7 7.6 7.5 ppm
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 ppm -74.6 -74.7 ppm
Septet caused by 6 F two
13
C/DEPT bond coupling (JCCF) to
carbon 2
7 6,6 5,5 C1 and C3, with coupling to

3F, J value of 288 Hz
4
130 128 126 124 122 120 118 ppm 78 77 76 ppm

Answers for Student Exercise 7.7A 1
MASS
CI Reagent gas methane
x 30
% of Base Peak
57 103
100 100 85
72
43
50 85 50 143
131
40 50 60 70 80 90 100 100
m/z m/z
IR
100
1149
%Transmittance
1388
833
50
1458
2954
972
3417
1049
2870
4000 3000 2000 1000

1
Wavenumber (cm-1)
H NMR 600 MHz 6
OH
2680 2660 2640 2620 2600 2580 Hz 2140 2120 2100 2080 2060 2040 Hz
2 4
5 2 is closer to CH2OH in space, therefore is
OH more deshielded than 4. NOE experiments
would confirm this.
4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm

13
13
C/DEPT
C/DEPT NMR
NMR 150.9 MHz
600 MHz
3-methyl-3-oxetanemethanol
5 CH2OH
2 CH3
3
6
1O 4
24
C5H10O2
Mol. Wt.: 102
5 6
3
80 75 70 65 60 55 50 45 40 35 30 25 20 ppm
Answers for Student Exercise 7.7B 2
ppm 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm COSY 600 MHz
6
3-methyl-3-oxetanemethanol
1.5 1.5
5 CH2OH
2 CH3
2.0 3 2.0
6
1O 4
C5H10O2
2.5 Mol. Wt.: 102 2.5
F1
3.0 3.0
OH
3.5 3.5 5
4.0 4.0
2
4.5 4.5 4
2 4 F2 HMQC 600 MHz

5 OH 6
ppm
20 20 6
30 30
40 40 3
F1 50 50
60 60
5
70 70
2 4
80 80
4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm

F2
Answers for Student Exercise 7.8A 3
MASS
221
% of Base Peak
100
50 97 137
55 81
177 203 236
50 100 150 200

m/z
IR
100
910
1381
1458
%Transmittance
1003
2924
4000 3000 2000 1000

Wavenumber (cm-1)
1
H NMR 600 MHz
9 12 31
11 11 5
8 4 9 4
2350 2300 Hz 1200 1150 Hz 1050 1000 Hz 900 850 Hz

8 16 15
5 7 13 14
3
800 Hz 750 700 Hz 600 Hz 550 500 Hz
(-)-ambroxide 11 16
13
CH3 12
O
3 1 10
4 2
9
CH3
5 7 16
6
14 8
H3C 15CH3
C16H28O
Mol. Wt.: 236
4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

Answers for Student Exercise 7.8B 4
13
13 C/DEPT
NMR 600
MHz
3 9
11 14,16
7
15 12 8 4
1 5
13
10 2 6
80 75 70 65 60 55 50 45 40 35 30 25 20 15 ppm
16
HMQC 600 MHz
11 1513 14
12 51
11
9 43
8 4 9 8 5 3 7
ppm
13
4
20 8 16
14
12
30
6
15
2
F1 40
39
5
(-)-ambroxide 11
13
50 CH3 12
O
3 1 10
4 2
CH3
5 7 9 16 7
6 1
60
14 8
H3C 15CH3 11
4.0 ppm 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.8 ppm
F2
Answers for Student Exercise 7.8C 5
HMBC 600 MHZ
HMQC 600 MHz
11 11 12 16 1513 14
51
9 8 4 4 3 8 5 3 7
9
ppm 4.0 3.9 ppm 2.0 1.8 1.6 1.4 1.2 1.0 0.8 ppm
15 13
20 8
14,16
12
ppm
6
34 15
(-)-ambroxide 11
F1 13
36 CH3 12 2
O
3 1 10
4 2
38 9
CH3
5 7 16
6
14 8 9
40 H3C 15CH3 3
42
5
ppm
7
58
60 1
62
64
11
ppm
80 10
82
4.0 3.9 ppm 2.0 1.8 1.6 1.4 1.2 1.0 0.8 ppm
F2
Answers for Student Exercise 7.8D 6
INADEQUATE
INADEQUATE150.9 MHz
600 MHz
11 1416
1 7 539 15 12 8 4
10 2 6 13
Hz
(-)-ambroxide 11 2-13
-7000 13 6-14 or 15
-7000
CH3 12
O
3 1 10 3-4
4 2
-6000 9
CH3 9-8
-6000
5 7 16
6 5-4
14 8
-5000 H3C 15CH3 6-15 or 14 -5000
-4000 5-6
-4000
7-8 3-2
-3000 -3000
1-12
-2000 11-12 -2000

7-6
7-2
-1000 -1000
1-2
F1 0 10-8 0
1000 1000
2000 2000
10-9
3000 3000
4000 4000
5000 5000
10-1
6000 6000
7000 7000
80 75 70 65 60 55 50 45 40 35 30 25 20 15 ppm
F2
CHAPTER 8 ASSIGNED PROBLEMS
Problem 8.1
MASS
68
55
% of Base Peak 100
41 112
84
50
97
40 50 60 70 80 90 100 110
m/z
IR O
100
1 2
3
%Transmittance
4
50 Cycloheptanone
C7H12O
Mol. Wt.: 112
2927
2858
1701
1454
1342
1161
941
856
4000 3000 2000 1000
Wavenumber (cm-1)
11 4
HHNMR
NMR 300 MHz
2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 ppm
1313
C/DEPT NMR 75.5 MHz
C/DEPT
2 4 3
200 180 160 140 120 100 80 60 40 ppm

MASS Problem 8.2
124
% of Base Peak 100
94
50 95
81
53 66
50 60 70 80 90 100 110 120

m/z
IR
OH
100
3
4 2
%Transmittance
50 5 1
7
6 OCH3
m-Methoxyphenol
C 7H 8 O 2
3398
3005
2947
2839
1601
1493
1284
1149
1041
945
837
768
687
Mol. Wt.: 124
4000 3000 2000 1000

Wavenumber (cm-1)
11 7
H NMR
H NMR 300 MHz 2
5 6
4
2150 2140 Hz 1960 1950 Hz 1930 1920 Hz

OH
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 ppm
13
13
C/DEPT NMR 75.5 MHz
C/DEPT
4
3 2 7
1 5
3
1
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 ppm
Problem 8.3
MASS
55
% of Base Peak M-1
100
83
39 41
M
50 53 84
65 66
40 45 50 55 60 65 70 75 80 85
m/z
IR
100
%Transmittance
50
3332
2978
2939
2877
2291
2229
1454
1319
1227
1138
1014
741
4000 3000 2000 1000
Wavenumber (cm-1)
11
H
H NMR
NMR 300 MHz
5
1
4
1280 1260 Hz 680 660 Hz OH
4.0 3.5 3.0 2.5 2.0 1.5 ppm
13
13C/DEPT
C/DEPT NMR 75.5 MHz
HO
4
H 2C C C CH2
1 2 3
5 CH3
CDCl3 2-Pentyn-ol
3 C5 H 8 O 5
Mol. Wt.: 84
4
1
2 78.0 77.5 77.0 76.5 ppm
95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 ppm
Problem 8.4
MASS
75
% of Base Peak x 30
100 111
110
100 113
49 112 M 146
61 77 99 148
50 97 75 150
148 50
114 77 115
146 152
50 100 150 100 m/z 150

m/z
IR Cl
100
Cl 1 CH 3 Cl
CH2 2 CH2
90
%Transmittance
80
1,2,3-Trichloropropane
70 C3H5Cl3
Mol. Wt.: 146
3016
2962
1435
1288
1219
910
717
663
4000 3000 2000 1000
1 Wavenumber (cm-1) 1+3
1H
H NMR
NMR 300 MHz
4.35 4.30 4.25 4.20 4.15 4.10 4.05 4.00 3.95 3.90 3.85 3.80 ppm
13
13C/DEPT
C/DEPT NMR 75.5 MHz
1+3
75 70 65 60 55 50 45 ppm
Problem 8.5
MASS
m/z %M 111
126 (M) 100.0
% of Base Peak 100 127 (M+1) 8.2
128 (M+2) 4.9 126
50 39
43 83
49 57
40 50 60 70 80 90 100 110 120 130

IR m/z
100
%Transmittance
50
3089
1662
1415
1273
1061
933
856
725
590
4000 3000 2000 1000
Wavenumber (cm-1)
11
H
H NMR
NMR 300 MHz
3 1 6
2
2300 2280 Hz 2140 2120 Hz

4 5
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 ppm
13
13 C/DEPT
C/DEPT NMR 75.5 MHz 2 3
1
O
S 4
5
6 CH3
Ethanone, 1-(2-thienyl)-
2 2-Acetylthiophene
1 3
C6H6OS 6
Mol. Wt.: 126
5 4
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 ppm
Problem 8.6
MASS
% of Base Peak
105 x 10
100
186
184
50 51 77
50 100 150
IR m/z
100
90
%Transmittance
80
70
3032
2985
1496
1450
1211
964
764
694
594
4000 3000 2000 1000
1
Wavenumber (cm-1)
H NMR 300 MHz 2 6
3 4
1590 1580 1570 Hz
2260 2250 2240 2230 2220 2210 2200 Hz

5 640 630 620 Hz
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 ppm
13
C/DEPT NMR 75.5 MHz
H3C 5 Br
6
1
2
3
4
(1-Bromoethyl)benzene
4 C8H9Br
3 2 Mol. Wt.: 184
6
5
1
140 130 120 110 100 90 80 70 60 50 40 30 ppm

Problem 8.7
MASS
109
% of Base Peak 124
100 81
53
50
63
75
50 60 70 80 90 100 110 120

m/z
IR
100
%Transmittance
50
3348
2951
2835
1859
1701
1612
1512
1234
1034
825
733
513
4000 3000 2000 1000
Wavenumber (cm-1)
11
H
H NMR
NMR 300 MHz
5
2 3
OH
7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 ppm
13
13
C/DEPT OH
C/DEPT NMR 75.5 MHz
4
3
2
1
OCH3
5
3 2 p-Methoxyphenol
C 7H 8 O 2 5
Mol. Wt.: 124
1 4
150 140 130 120 110 100 90 80 70 60 50 ppm

Problem 8.8
MASS
128
% of Base Peak 100
64
130
50 92
73
50 60 70 80 90 100 110 120 130

m/z
IR
100
%Transmittance
50
3521
3464
3074
3039
1585
1481
1454
1338
1200
1030
748
679
4000 3000 2000 1000
1 Wavenumber (cm-1)
1H
H NMR
NMR 300 MHz OH
6 4 1
3 2 Cl
6
5
3 OH
5
4
o-Chlorophenol
C6H5ClO
Mol. Wt.: 128
7.4 7.2 7.0 6.8 6.6 6.4 6.2 6.0 5.8 5.6 5.4 ppm
13
13
C/DEPT
C/DEPT NMR 75.5 MHz
5 4
3 6
1 2
155 150 145 140 135 130 125 120 115 ppm
Problem 8.9
MASS
% of Base Peak 55 x 20
87 115
100 196
73 194
50 135 137 163 165
0
50 100 150
m/z
IR
100
%Transmittance
50 2954
1736
1435
1365
1203
748
4000 3000 2000 1000
1 Wavenumber (cm-1)
1H
H NMR
NMR 300 MHz
O
6 6
4
Br 5 3 1 O
2
5 Methyl 5-bromo valerate 2

C6H11BrO2
Mol. Wt.: 194 3
4
3.6 3.4 3.2 3.0 2.8 2.6 2.4 2.2 2.0 1.8 1.6 ppm
13
13
C/DEPT
C/DEPT NMR 75.5 MHz
5 2
4
3
6
1 33.0 32.5 32.0 ppm
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 ppm

Problem 8.10
MASS
54
% of Base Peak 100 67 84
93
50
111 126
50 60 70 80 90 100 110 120

m/z
IR
100
%Transmittance
3344
2958
2931
2873
1466
1331
1045
849
4000 8 3000 4 2000 1000
1 7 Wavenumber
5 2 1 OH
(cm-1)
1H 6
H NMR
NMR 300 MHz 3
8
3-Octyn-1-ol
C8H14O
Mol. Wt.: 126 6
1 7
2 5
OH
3.5 3.0 2.5 2.0 1.5 1.0 ppm
13
13C/DEPT
C/DEPT NMR 75.5 MHz
1 6
5 8
7
2
84 82 80 78 ppm
4 3
85 80 75 70 65 60 55 50 45 40 35 30 25 20 ppm
MASS Problem 8.11
162
% of Base Peak 100
164
63
98
50
73 126
128
50 60 70 80 90 100 110 120 130 140 150 160

m/z
IR
100
%Transmittance
50
3521
3097
1585
1477
1404
1277
1188
814
725
555
4000 3000 2000 1000
1 Wavenumber (cm-1)
1H
H NMR
NMR 300 MHz
3 OH
6
1
2 Cl
6
5
5 3
OH
4
Cl
2,4-Dichlorophenol
C6H4Cl2O
Mol. Wt.: 162
7.4 7.2 7.0 6.8 6.6 6.4 6.2 6.0 5.8 5.6 5.4 5.2 ppm
13
13C/DEPT
C/DEPT NMR 75.5 MHz
3 5 6
1
4 2
155 150 145 140 135 130 125 120 115 ppm
Problem 8.12
MASS 123
% of Base Peak
100 95
75
50 138
50 63
50 60 70 80 90 100 110 120 130 140

IR m/z
100
%Transmittance
50
3356
3074
3005
1685
1597
1358
1265
1157
960
841
567
4000 3000 2000 1000
Wavenumber (cm-1)
19
1
H NMR 300 MHz F NMR 282.4 MHz
1
2 3 H Coupled
6
1
H Decoupled
2400 2390 2380 Hz 2140 2130 Hz
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 ppm -104.4 -104.5 ppm
13 5 6
C/DEPT NMR 75.5 MHz COCH3
1
2
3
4
F
2 3 4-Fluoroacetophenone
C8H7FO 6
Mol. Wt.: 138
4 130 128 126 124 122 120 118 ppm
5
1
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 ppm
Problem 8.13
MASS
96
% of Base Peak 100
50 70
50 75 77
50 55 60 65 70 75 80 85 90 95
IR m/z
100 F
1
2
%Transmittance
3
4
95
Fluorobenzene
C 6H 5 F
3749
3062
1697
1604
1504
1234
756
Mol. Wt.: 96
4000 3000 2000 1000
Wavenumber (cm-1)
11HNMR 300 MHz 19
H NMR F NMR 282.4 MHz
1
H Coupled
2
3
4
7.4 7.3 7.2 7.1 ppm -80.1 -80.2 -80.3 ppm
13
13
C/DEPT
C/DEPT NMR 75.5 MHz
3 2
4
130 128 126 124 122 120 118 116 ppm
1
165 160 155 150 145 140 135 130 125 120 115 ppm
Problem 8.14
MASS
82
% of Base Peak 100
50 138
54
67 95
123
50 60 70 80 90 100 110 120 130 140

IR m/z
100
%Transmittance
50
2958
2870
1670
1381
1246
903
525
4000 3000 2000 1000
1 Wavenumber (cm-1)
1H
H NMR
NMR 300 MHz 6 89
7
4
1750 1740 Hz 640 Hz 570 560 Hz 300 290 Hz
6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
13
13
C/DEPT
C/DEPT NMR 75.5 MHz 7
CH3
3
4 2
9
H 3C 5 1
6 O
H3 C
8 89
Isophorone
C9H14O
2 6 4
Mol. Wt.: 138 7
1 3 5
200 180 160 140 120 100 80 60 40 ppm

Problem 8.15
MASS
54
% of Base Peak
50 68
149
81 147
107 109
79 93 95 119 121
50 60 70 80 90 100 110 120 130 140 150

m/z
IR
100
90
%Transmittance
80
70
2970
2245
1435
1250
756
4000 3000 2000 1000
Wavenumber (cm-1)
11
H
H NMR
NMR 300 MHz 2
4 3 1
Br 4 2
N 3
4-Bromobutanoyl nitrile
C4H6BrN
Mol. Wt.: 147
3.6 3.5 3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 ppm
13
13
C/DEPT
C/DEPT NMR 75.5 MHz
3 2
120 110 100 90 80 70 60 50 40 30 20 ppm

Problem 8.16
MASS
106
% of Base Peak 100
50 137
77
50 60 70 80 90 100 110 120 130 140

m/z
IR
100
%Transmittance
90
80
3348
3194
2931
1620
1512
1442
1049
825
4000 3000 2000 1000
1 Wavenumber (cm-1)
1H
H NMR
NMR 300 MHz
6
3
2 OH
5 4 3 2 ppm 5
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
13
13
C/DEPT OH
C/DEPT NMR 75.5 MHz
6
5
1
OH
2
3
2 3 4
NH2 6 5
p-Aminophenylethanol
C8H11NO
4 1 Mol. Wt.: 137
140 130 120 110 100 90 80 70 60 50 40 ppm

Problem 8.17
MASS
119
% of Base Peak 100
50 91
64
76
50 60 70 80 90 100 110 120

m/z
IR
100
90
%Transmittance
80
70
3309
2245
1589
1481
1342
787
671
4000 3000 2000 1000
1 Wavenumber (cm-1)
1H
H NMR
NMR 300 MHz
2 3
OH
7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5 6.4 6.3 6.2 ppm
13
13
C/DEPT
C/DEPT NMR 75.5 MHz
2 3
5 1 4
N C OH
p-Cyanophenol
C7H5NO
Mol. Wt.: 119 2 3
4 5 1
165 160 155 150 145 140 135 130 125 120 115 110 ppm
Problem 8.18
MASS
163
% of Base Peak 100
50 178
77 91 135
50 100 150
m/z
IR
100
%Transmittance
50
3572
2962
2870
1458
1203
1149
748
4000 3000 2000 1000
Wavenumber (cm-1)
11
H
H NMR
NMR 300 MHz 6
3 2150 2100 Hz 1000 950 Hz 450 400 Hz

4 OH
5
7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
13
13C/DEPT
C/DEPT NMR 75.5 MHz 6
OH
1 5
2
6
3
4
2,6-Diisopropyl phenol 6
C12H18O
3 Mol. Wt.: 178 5
4
1 2
150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

Problem 8.19
MASS
106
% of Base Peak 78 121
100
51
50
50 60 70 80 90 100 110 120

m/z
IR
100
%Transmittance
50
3363
3047
1689
1419
1273
957
702
4000 3000 2000 1000
1 Wavenumber (cm-1)
1H 4
H NMR
NMR 300 MHz 2 3
7
5
2720 2700 Hz 2600 2580 Hz 2440 2420 Hz 2200 2180 Hz
9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 ppm
13 3
13C/DEPT
C/DEPT NMR 75.5 MHz 4 2
7
5 1
6 CH3
N C
O
2-Acetylpyridine
5 4 3 2 C7H7NO 7
Mol. Wt.: 121
6 1
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 ppm
Problem 8.20
MASS
108
123
% of Base Peak 100
50 53 80
40 50 60 70 80 90 100 110 120

m/z
IR
100
%Transmittance
50
3109
2947
1651
1404
1095
741
633
4000 3000 2000 1000
1 Wavenumber (cm-1)
1H
H NMR
NMR 300 MHz 7
5
2060 Hz 2020 Hz 1820 Hz

4 3 2
7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 ppm
13
13
C/DEPT
C/DEPT NMR 75.5 MHz
3
2
4 7
1
6 CH3
N
H3C5 O
4 2 3
1-Methyl-2-acetylpyrrole 7
1 C7H9NO 5
Mol. Wt.: 123
6
180 160 140 120 100 80 60 40 ppm

Problem 8.21
MASS
% of Base Peak x 20
43 159
100 100
85
57 103 158
50 50
187
50 100 150 150 m/z

m/z
IR
100
%Transmittance
50
2962
1720
1651
1319
1149
1034
4000 3000 2000 1000
Wavenumber (cm-1)
11
H
H NMR
NMR 300 MHz
7
1
3
5
6
3.5 3.0 2.5 2.0 1.5 1.0 ppm
13
13C/DEPT
C/DEPT NMR 75.5 MHz
7
1 6
2 4 O 5
3 7
O O
Isobutylacetoacetate 7
C8H14O3 5 3 6
Mol. Wt.: 158 1
2 4
200 180 160 140 120 100 80 60 40 ppm

Problem 8.22
MASS
119
% of Base Peak 100
50 91
64
76
50 60 70 80 90 100 110 120

m/z
IR
100
90
%Transmittance
80
70
3309
2245
1589
1481
1342
787
671
4000 3000 2000 1000
11
Wavenumber (cm-1)
H NMR 600
300 MHz OH
42 3
4 2
5 6
1
5 7
C
6 N OH
m-Cyanophenol
C7H5NO
Mol. Wt.: 119
7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5 6.4 6.3 6.2 ppm
13
13 C/DEPT NMR 600
75.5MHz
MHz
C/DEPT NMR
6 4 2
5
3
1
7
155 150 145 140 135 130 125 120 115 ppm
Problem 8.23
MASS
x 20
183 185
% of Base Peak
264
100 262
200 224 226 260
198
75 155 157
50
100 150 200 250

IR m/z
100
%Transmittance
50
3356
3089
3059
2962
1685
1585
1485
1396
1223
1068
995
810
617
4000 3000 2000 1000
1 Wavenumber (cm-1)
1H
H NMR
NMR 300 MHz
6 8 5
3
2
7.9 7.8 7.7 7.6 ppm 3.6 3.4 3.2 3.0 2.8 2.6 2.4 ppm
13
13C/DEPT
C/DEPT NMR 75.5 MHz 5 6 7 8
COCH2CH2CH2Cl
1
2
3
4
3 2
Br 6 7 8
4Bromo-4-chlorobutyrophenone
5 C10H10BrClO
Mol. Wt.: 260
1 4
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 ppm
Problem 8.24
MASS 100
% of Base Peak
100 55 147
74
50 69
83 128 50
175 187
50 100 150 150 200

m/z
m/z
IR
100
%Transmittance
50
3039
2978
2669
1709
1466
1419
1277
1238
930
4000 3000 2000 1000
1 Wavenumber (cm-1)
1H
H NMR
NMR 300 MHz
4 6
2x OH
x64
3
2
12 11 ppm 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 ppm
13
13C/DEPT
C/DEPT NMR 75.5 MHz
O O
3
2 CH2 C 5
HO 1 CH CH2 OH
4
CH3
6
2 6
4 3
2-Methyl glutaric Acid
C6H10O4
15 Mol. Wt.: 146
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 ppm
Problem 8.25
MASS
91
% of Base Peak
92
93
100
66
100
50
51
50
50 60 70 80 90 80 90
m/z m/z
IR
100
90
%Transmittance
80
3055
2962
1720
1342
1065
802
725
4000 3000 2000 1000
Wavenumber (cm-1)
1
H NMR 300 MHz 3
2
1
2050 2040 Hz 1090 1080 Hz 615 610 605 Hz
7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 ppm
13
C/DEPT NMR 75.5 MHz
2 1
Bicyclo[2,2,1] hepta-2-5-diene 3
1 C7 H 8 2
Mol. Wt.: 92
140 130 120 110 100 90 80 70 60 50 ppm

Problem 8.26
MASS M
156
% of Base Peak 100
63 M+2
158
50
98 121
50 60 70 80 90 100 110 120 130 140 150 160

m/z
IR
100
586
%Transmittance
50 2900
933
802
1041
1234
1473
4000 3000 2000 1000
1
Wavenumber (cm-1)
H NMR 600 MHz
6
3 7
4
6.85 6.80 6.75 6.70 6.65 ppm 6.00 5.95 ppm

1313
C/DEPT
C/DEPTNMR
NMR600 MHz
150.9 MHz
3
2 O
4
7
5
1 O
Cl 6
5-chloro-1,3-benzodioxole
C7H5ClO2 4
Mol. Wt.: 156 36 7
1 2 5
155 150 145 140 135 130 125 120 115 110 105 ppm
Problem 8.27A
MASS
55
42
% of Base Peak 100
84
50 114
70
40 50 60 70 80 90 100 110
m/z
IR
100
%Transmittance
50
2931
1728
1442
1165
1057
856
571
4000 3000 2000 1000
Wavenumber (cm-1)
11
H
H NMR
NMR 300 MHz O
1
2
6 1 O 2
3 6 4
3 5
4 5
-Caprolactone
C6H10O2
Mol. Wt.: 114
4.0 3.5 3.0 2.5 2.0 1.5 ppm
13
13 C/DEPT
C/DEPT NMR 75.5 MHz
43
6 2 5
170 160 150 140 130 120 110 100 90 80 70 60 50 40 ppm

Problem 8.27B
ppm 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm COSY 300 MHz
1.5 1.5 4
1 2 3 4 5 6
5
O 3
2.0 2.0
2 1 O
2
2.5 3 6 2.5
F1
4 5
3.0 -Caprolactone 3.0
C6H10O2
Mol. Wt.: 114
3.5 3.5
4.0 4.0
6
F2 HETCOR 75.5MHz
MHz
4 3 HETCO 300
6 2 5
ppm
1.5 1.5
2.0 2.0
2.5 2.5
F1
3.0 3.0
3.5 3.5
4.0 4.0
4.5 4.5
65 60 55 50 45 40 35 30 25 ppm
F2
Problem 8.28A
MASS
% of Base Peak 55 x 10 137
69
100 120
82 90 118 5
50 92 139
50 m/z 100 130 140 150

m/z
IR
100
%Transmittance
50
3332
2939
2862
1458
1057
725
648
4000 3000 2000 1000
1
Wavenumber (cm-1)
H NMR 600 MHz
1 6
HO 1 3 5
2 4 6 Cl 2 4 3
5
1-Hexanol-6-chloro
C6H13ClO
Mol. Wt.: 136
OH
3.6 3.4 3.2 3.0 2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 ppm
1313
C/DEPT C/DEPTNMR
NMR600 MHz
150.9 MHz
5 2 4 3
1 6
60 55 50 45 40 35 30 25 ppm
Problem 8.28B
ppm 3.5 3.0 2.5 2.0 1.5 ppm COSY 600 MHz
1.5 1.5
2.0 2.0
HO 1 3 5
2 4 6 Cl
F1 1-Hexanol-6-chloro
2.5 C6H13ClO 2.5
Mol. Wt.: 136
3.0 3.0
3.5 3.5
1 6 F2 HMQC 600 MHz

OH 5 2 4 3
ppm
25 25 3
4
OH
30 30
35 35
40 5 2 40
F1 6
45 ppm 45
50 32 50
55 55
60 33 60
2.0 1.8 1.6 1.4 ppm 1
3.5 3.0 2.5 2.0 1.5 ppm

F2
Problem 8.29A
MASS
95
% of Base Peak 100
45 67 69
50 55 110 128
81 113
50 60 70 80 90 100 110 120 130

m/z
IR
100
%Transmittance
50
3344
2966
2924
1450
1377
1126
1041
825
4000 3000 2000 1000
Wavenumber (cm-1)
11
HNMR
H NMR 300 MHz 1
7 8
1540 Hz 1140 Hz 500 480 Hz 440 Hz 3

5 2 4 OH
5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
13
13
C/DEPT NMR 75.5 MHz
C/DEPT
7
OH
5 3
6 4 2 1
8 1 3 4
5 2 8
6-Methyl-5-hepten-2-ol
C8H16O 7
6 Mol. Wt.: 128
130 120 110 100 90 80 70 60 50 40 30 20 ppm

Problem 8.29B
ppm 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm COSY 300 MHz
1.0 1.0
1
1.5 1.5 3
7
OH 8
2.0 2.0 4
2.5 2.5
F1 3.0 3.0
3.5 3.5
2
4.0 4.0
4.5 4.5
5.0 5.0
5
5 F2 2 3 84 1 HETCOR300
75.5 MHz
7 HETCO MHz
ppm
1.0
7
1.5 OH
5 3
6 4 2
2.0 8 1
6-Methyl-5-hepten-2-ol
2.5 C8H16O
Mol. Wt.: 128
3.0
F1
3.5 OH
4.0
4.5
5.0
5.5
120 100 80 60 40 20 ppm
F2
Problem 8.30A
MASS
88
% of Base Peak 100
225
223
69 100
50
253
251
263
265
143 177 179
159 194
50
0
50 100 m/z 150 230 240 250 260
m/z
IR
100
%Transmittance
50
2939
2870
1736
1458
1188
1034
4000 3000 2000 1000
11 Wavenumber (cm-1)
H
H NMR
NMR 300
600 MHz
MHz 8
6
7 2
5 3 4
4.0 3.5 3.0 2.5 2.0 1.5 ppm

13
13 C/DEPTNMR 75.5
C/DEPT NMR 600 MHz
MHz
5 3 1 O 7
6 4 2 8 4 3
Br 2,6,5
O 7 8
Ethyl 6-Bromohexanoate
1 C8H15BrO2
Mol. Wt.: 222
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 ppm

Problem 8.30B
ppm 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm COSY 300 MHz
1.0 1.0
8
4
1.5 1.5 3
5
2.0 2.0
2
F1
2.5 2.5
1
1
3.0 3.0
6
3.5 3.5
4.0 4.0 7
7 F2 2 6 5 4 3 8 HETCOR
HETCO75.5
300MHz
MHz
ppm
1.0 1
1.0
5 3 O 7 8 8
Br 6 4 2
4
1.5 O 1.5 3
Ethyl 6-Bromohexanoate 5
C8H15BrO2
2.0 Mol. Wt.: 222 2.0
2
F1 2.5 2.5
3.0 3.0
6
3.5 3.5
4.0 4.0 7
60 55 50 45 40 35 30 25 20 15 ppm
F2
Problem 8.31A
MASS
134
% of Base Peak 100
41
94
119
50 65 91
77 105
40 50 60 70 80 90 100 110 120 130

m/z
IR
100
%Transmittance
50
3066
3032
2916
2866
1601
1496
1242
752
690
4000 3000 2000 1000
1
Wavenumber (cm-1)
H NMR 600 MHz
5
2
3
4 3680 3660 Hz 3300 3280 Hz 3220 3200 Hz 2760 2740 Hz

6 7
7.4 7.2 7.0 6.8 6.6 6.4 6.2 6.0 5.8 5.6 5.4 5.2 5.0 4.8 ppm
13
13
C/DEPT NMR
C/DEPT NMR 150.9
600 MHz
MHz
5 6 7
OCH2CH=CH2
1
2
3 2 3
4
4 Allylphenyl ether 5
7 C9H10O
6
1 Mol. Wt.: 134
160 150 140 130 120 110 100 90 80 70 ppm

Problem 8.31B
ppm 7.5 7.0 6.5 6.0 5.5 5.0 4.5 ppm COSY 600 MHz
4.5 4.5
5.0 5.0
5.5 5.5
F1
6.0 6.0
6.5 6.5
7.0 7.0
2
3 4 F2 5 HMQC 600 MHz
6 7
ppm
5 6 7
70 OCH2CH=CH2 70 5
1
80 2 80
3
90 90
4
Allylphenyl ether
100 C9H10O 100
Mol. Wt.: 134
F1 110 diastereotopic 110
2
7
120 120 4
130 130 3
6
140 140
150 150
1
7.5 7.0 6.5 6.0 5.5 5.0 4.5 ppm
F2
Problem 8.32A
MASS
% of Base Peak
95 x 20
100
110 139
50 55 67 154
109 121 136
50 60 70 80 90 100 110 120 130 140 150

m/z
IR
100
%Transmittance
50
3317
2951
2877
1712
1365
1227
1057
829
4000 3000 2000 1000
1
Wavenumber
3 (cm-1)
H NMR 600 MHz 8
9 10
OH
2400 Hz 1350 Hz 1150 Hz 1050 Hz 950 Hz 750 Hz 550 Hz 500 Hz

2 In the above insets each tick mark is 10 Hz 3 6 5 4 5 6 3
4.0 3.5 3.0 2.5 2.0 1.5 ppm

13
13
C/DEPT NMR
C/DEPT NMR 150.9
600 MHz
MHz
10 9
H 3C CH3
8
7
CH3
6
1 2
5 4 3 OH 3 5 6 9 10 8
Borneol 4
2
C10H18O
Mol. Wt.: 154
1 7
75 70 65 60 55 50 45 40 35 30 25 20 15 ppm
Problem 8.32B
7
ppm 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm COSY 600 MHz
9.10,8
1.0 1.0 3
6
5
1.5 1.5 OH
4
5
6
2.0 2.0
F1 3
10 9
2.5 H 3C CH3 2.5
8
7
CH3
3.0 6 3.0
1 2
5 4 3 OH
3.5 Borneol 3.5
C10H18O
Mol. Wt.: 154
4.0 4.0 2
F2 HMQC 600 MHz

ppm
ppm 8
10
20 20 9
15 6
30 30 5
20
40 diastereotopic 40 3
25
0.90 0.85 ppm
F1 7 4
50 50 1
60 60
70 70
2
4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

F2
Problem 8.33A
MASS
85
% of Base Peak 100
50 57 70
114
50 60 70 80 90 100 110
m/z
IR
100
656
2885
1358
1466
%Transmittance
972
50 2970
1180
1774
4000 3000 2000 1000
1
Wavenumber (cm-1)
H NMR 600 MHz 6
3 2
6
4 1
O 2
5 O
4 3 3 5 5
-Caprolactone
C6H10O2
Mol. Wt.: 114
4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

13
13
C/DEPT NMR
C/DEPT NMR 150.9
600 MHz
MHz
2 5 3
4 6
1 29 28 ppm
180 160 140 120 100 80 60 40 20 ppm

Problem 8.33B
ppm 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm COSY 600 MHz
1.0 1.0 6
1.5 1.5
5
3
2.0 2.0
3
2
F1 2.5 3 2
2.5
6
4 1
3.0 O 3.0
5 O
-Caprolactone
3.5 C6H10O2 3.5
Mol. Wt.: 114
4.0 4.0
F2 HMQC 600 MHz

ppm
10 10 6
20 20
30 30
diastereotopic
40 ppm 40
F1 50 3
50
28 5
2
60 60
30
2.5 2.0 1.5 ppm
70 70
80 80
4
4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

F2
Problem 8.34A
MASS
41
% of Base Peak 69
100
55 81
95
50 109 123
138 156
40 50 60 70 80 90 100 110 120 130 140 150 160

m/z
IR
100
%Transmittance
50
3332
2924
1450
1381
1057
833
4000 3000 2000 1000
1 10
Wavenumber 9
(cm-1)
1 HO CH3 CH3
H NMR 600 MHz 8
6
7 9
2 3
CH3 10
4 5 8
Citronellol
C10H20O
Mol. Wt.: 156
6 3
1 5 2 4
OH
5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
13
13
C/DEPT NMR
C/DEPT NMR 150.9
600 MHz
MHz
5
9 24 3 8
6 1
7 10
26 25 ppm
130 120 110 100 90 80 70 60 50 40 30 20 ppm

Problem 8.34B
ppm 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm COSY 600 MHz
10
1.0 1.0 4
2 3
1.5 1.5 8
OH 9
2.0 2.0 5
2.5 2.5
F1
3.0 3.0
3.5 3.5 1
4.0 4.0
4.5 4.5
5.0 5.0 6
F2 HMQC 600 MHz

ppm
1 10 9 10
HO 20 CH3 CH3 20 8
6 95
7 3
2 3
CH3 4
40 4 5 8 40 2
Citronellol
C10H20O
60 Wt.: 156
Mol. 60 1
ppm
F1 80 80
20
100 100
30
120 40 120
6
2.0 1.5 1.0 ppm 7
5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
F2
Problem 8.35A
MASS
95
81
% of Base Peak 100
41
55 69 108
50 152
137
50 60 70 80 90 100 110 120 130 140 150

m/z
IR 9 8
H3C 7 CH3
100
5 4
1273
748
3
%Transmittance
1450
2
1041
6 1
50 O
10CH3
2954
Camphor
1743
C10H16O
Mol. Wt.: 152
4000 3000 2000 1000
1
Wavenumber (cm-1)
H NMR 600 MHz 8 9 10
4 3
3 5
5 6 6
2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9 ppm
13
13
C/DEPT NMR
C/DEPT NMR 150.9
600 MHz
MHz
4 3 6 5 9 8 10
2
1 7
220 ppm 55 50 45 40 35 30 25 20 15 ppm

Problem 8.35B
ppm 2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0 0.8 0.6 ppm COSY 600 MHz
0.6 0.6
0.8 0.8 10
9
1.0 1.0
8
1.2 1.2
5
1.4 1.4
F1 6
1.6 1.6
6
1.8 1.8
3
5
2.0 2.0
4
2.2 2.2
3
2.4 2.4
F2 HMQC 600 MHz

ppm
10 10 10
8
20 20 9
5
30 9 8 30 6
H3C 7 CH3
F1
5 4
3
2
40 6 1 40
4
10CH3 O 3
7
Camphor
50 C10H16O 50
Mol. Wt.: 152
1
2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0 0.8 0.6 ppm
F2
Problem 8.35C
INADEQUATE
INADAQUATE150.9
150.9MHz
MHz
2 1 3
Hz
9 8
-20000 H3C 7 CH3 -20000
-15000 5 4 -15000
3
2
-10000 6 1 -10000
10CH3 O
-5000 -5000
Camphor
F1 0 C10H16O
Mol. Wt.: 152 0
5000 5000
10000 10000
220 200 180 160 140 120 100 80 60 40 20 ppm
F2
Hz
1 7 43 6 5 9 8 10
-25000 -25000
-24000 -24000
-23000 -23000
-22000 -22000
F1
-21000 -21000
-20000 -20000
-19000 -19000
-18000 -18000
-17000 -17000
65 60 55 50 45 40 35 30 25 20 15 10 5 ppm
F2
Problem 8.36A
MASS
100 70
50 55 130
115
40 50 60 70 80 90 100 110 120 130

m/z
IR
100
1466
%Transmittance
2877
1373
1041
2962
50
1242
1743
4000 3000 2000 1000
Wavenumber (cm-1) 7 is doublet
1
H NMR 600 MHz 1
6 is triplet
2350 Hz 2300 Hz 1000 Hz 850 Hz 700 Hz 550 Hz

In the above insets each tick mark is 10 Hz
3
4
5 5
3.5 3.0 2.5 2.0 1.5 ppm

13
13
C/DEPT NMR
C/DEPT NMR 150.9
600 MHz
MHz
O
3
4 6
H3C 2 O 5 CH3
1 3
7 CH3
5
7 6
2-Methylbuty acetate 4
C7H14O2 1
2
Mol. Wt.: 130
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

Problem 8.36B
ppm 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm COSY 600 MHz
6
1.0 1.0
5 7
5
1.5 1.5
4
2.0 2.0 1
F1
2.5 2.5
3.0 3.0
3.5 3.5
3
4.0 4.0
F2 HMQC 600 MHz

ppm
10 10 6
ppm
10
7
6
20 20 1
5
15
30 7 30
4
0.95 0.90 0.85 ppm
40 40
F1
O
50 3 50
4 6
H3C 2 O 5 CH3
1
60 7 CH3 60
2-Methylbuty acetate 3
70 C7H14O2
70
Mol. Wt.: 130
4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

F2
Problem 8.37A
MASS
111 m/z %M
151 (M-1) 37.5
% of Base Peak 100 152 (M) 100.0
153 (M+1) 12.7
154 (M+2) 5.2 152
50
69 83
50 60 70 80 90 100 110 120 130 140 150

m/z
IR
100
3008
3093
%Transmittance
1057
50
957
725
1419
1234
1651
4000 3000 2000 1000
1
Wavenumber (cm-1)
H NMR 600 MHz 7 and 8 are diastereotopic
78
4680 Hz 4560 Hz 4260 Hz 1520 Hz 740 720 Hz 600 Hz

3 1 2 6
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
13
13
C/DEPT NMR
C/DEPT NMR 150.9
600 MHz
MHz
O
S 4 C 6
5 7
1
3 8
2
7 8
cyclopropyl(thiophen-2-yl)methanone
3 C8H8OS
1 2 Mol. Wt.: 152 6
5 4
180 160 140 120 100 80 60 40 20 ppm

Problem 8.37B
ppm 8 7 6 5 4 3 2 1 ppm COSY 600 MHz
1 1 87
2 2
6
3 3
4 4
F1
5 5
6 6
7 7 2
1
8 8 3
F2 HMQC 600 MHz

ppm
78
20 20 6
O
S 4 C 6
5 7
40 1 40
3 8
2
60 cyclopropyl(thiophen-2-yl)methanone 60
C8H8OS
Mol. Wt.: 152
F1
80 80
100 100
120 120
2
3
1
8 7 6 5 4 3 2 1 ppm
F2
Problem 8.38A
MASS
121
% of Base Peak
164
100
103
77
91
136
50
149
65
60 70 80 90 100 110 120 130 140 150 160
m/z
IR
100
2870
663
%Transmittance
949
764
3201
2962
1412
1550
50
1265
1473
1612
4000 3000 2000 1000
Wavenumber (cm-1)
1 9 10
H NMR 600 MHz 8
7 5
3 6
3940 3920 Hz 3880 3860 Hz 3720 Hz 1280 Hz 320 300 Hz
OH
9 8 7 6 5 4 3 2 1 ppm
13
C/DEPT NMR 150.9 MHz O
7 1
2 OH
6
5 3
4
2 1 H 3C 8 CH3
10 9 9 10
6 537 -Thujaplicin
C10H12O2 8
171.5 171.0 ppm Mol. Wt.: 164
4
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 ppm

Problem 8.38B
ppm 7 6 5 4 3 2 1 ppm COSY 600 MHz
ppm 6.8 6.6 6.4 6.2 ppm 9 10

1 1
6.2 5 O
2 2 8
7 1
2 OH
6.4 6
7
3 3
6.6 36 5 3
F1 4
4 4
H 3C 8 CH3
10 9
-Thujaplicin
5 5
C10H12O2
Mol. Wt.: 164
6 6
7 7
F2 HMQC 600 MHz

ppm
20 20
9 10
40 ppm 40 8
7
125 3
60 60
5
130
F1 80 135
80
6
140
100 6.8 6.6 6.4 6.2 ppm
100
120 120 7
3
5
140 140 6
7 6 5 4 3 2 1 ppm
F2
Problem 8.38C
INADEQUATE 150.9 MHz

INADEQUATE 600 MHz
9
4 8 10
Hz
-20000 -20000
-15000 -15000
-10000 -10000
-5000 -5000
F1 0 0
5000 5000
10000 10000
15000 15000
20000 20000
160 140 120 100 80 60 40 20 ppm

F2
2 1 4 6 5 3 7
Hz
0 0
5000 5000
F1
10000 10000
15000 O 15000
7 1
2 OH
6
20000 20000
5 3
4
H C 8 CH3
175 170 165 160 155 150 3 10
145 140
9 135 130 125 120 115 ppm
F2
-Thujaplicin
C10H12O2
Mol. Wt.: 164
Problem 8.39A
MASS 123
% of Base Peak
100 83
151
41 55 232
50 69 95 230
110
50 100 150 200

m/z
IR
100
90
1219
1034
1365
1442
1473
%Transmittance
80
70 2954
1751
4000 3000 2000 1000
Wavenumber (cm-1)
1 10
H NMR 600 MHz
8 9
2800 Hz 1350 1300 1250 1200 1150 1100 1050 1000 950 900 850 Hz
3 4 5 5 6 6
4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm

9 8
13
C/DEPT NMR 150.9 MHz H3 C CH3
7
4
5 3
2
1 Br
6
CH3 O
10
8 9 3-Bromocamphor
C10H15BrO 6 5
Mol. Wt.: 230 4 10
3
2 20.0 19.9 19.8 ppm 1 7
200 180 160 140 120 100 80 60 40 20 ppm

Problem 8.39B
COSY 600 MHz

ppm 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
9
1.0 1.0 10
8
1.5 1.5 6
6
2.0 2.0 5
5
4
2.5 2.5
F1
3.0 3.0
3.5 3.5
4.0 4.0
4.5 4.5
3
F2 HMQC 600 MHz

ppm
9 8 10
10 H3 C CH3 10
7
4
5 3 89
20 20
2 5
1 Br
6
CH3 O
10
30 3-Bromocamphor 30 6
F1 C10H15BrO
Mol. Wt.: 230
40 40
7
50 50 4
3
1
60 60
5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
F2
Problem 8.39C
INADEQUATE 150.9
INADEQUATE 600MHz
MHz
2 13
Hz
-20000 -20000
-15000 -15000
-10000 -10000
F1
-5000 -5000
0 0
5000 5000
200 180 160 140 120 100 80 60 40 20 ppm

F2
1 3 4 7 6 5 10
Hz
-25000 -25000
-24000 -24000
-23000 -23000
-22000 -22000
9 8
F1 H3 C CH3
-21000 7 -21000
4
5 3
-20000 2 -20000
1 Br
6
-19000 CH3 O -19000
10
3-Bromocamphor
C10H15BrO
-18000 Mol. Wt.: 230 -18000
-17000 -17000
60 55 50 45 40 35 30 25 20 15 10 5 ppm
F2
Problem 8.40A
MASS
FM (found) = 154.1351 154
108
% of Base Peak 100 81
71 111 139
93
55
50
136
50 60 70 80 90 100 110 120 130 140 150

m/z
IR
100
841
%Transmittance
1466
1373
1080
1219
50
987
2970
4000 3000 2000 1000

1
Wavenumber (cm-1)
H NMR 600 MHz 8,9 10
4,6
3,7
3,7 4,6
2
2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 ppm
13
13
C/DEPT
C/DEPT NMR
NMR 150.9 MHz
600 MHz
6 10
7 CH3
4 5 O
1
3 2 CH3
8 8,9
9 CH3 4,6 3,77
Cineole
10
C10H18O 2
1 5 Mol. Wt.: 154
75 70 65 60 55 50 45 40 35 30 25 ppm
Problem 8.40B
ppm 2.2 2.0 1.8 1.6 1.4 1.2 1.0 ppm COSY 600 MHz
10
1.0 1.0
8,9
1.2 1.2
2
1.4 1.4
3,7 4,6
F1
1.6 1.6 4,6
1.8 1.8
2.0 2.0 3,7
1 4 5 6
F2 HMQC 600 MHz

ppm
22 22
3,7
24 7 10 24
6 CH3
5 1
26 O 26
2
3 CH3
4 10
8
F1 28 9 CH3 28
8,9
Cineole
30 C10H18O 30
Mol. Wt.: 154
4,6
32 32
2
34 34
2.2 2.0 1.8 1.6 1.4 1.2 1.0 ppm

F2
Problem 8.41A
MASS
82
% of Base Peak
67 CI Reagent gas methane
100 155
54 FM (found) = 155.0711 by CI
100
50
50 183 195
110
50 100 160 170 180 190

m/z m/z
IR
100
1450
%Transmittance
2862
50 2947
1859
1219
903
1790
4000 3000 2000 1000
1
Wavenumber (cm-1)
H NMR 600 MHz O
3 4
2
4 1
2 O
O 3
1,2-cyclohexanedicarb
oxylic acid anhydride
C8H10O3
Mol. Wt.: 154
3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 ppm
13
13
C/DEPT NMR
C/DEPT NMR 150.9
600 MHz
MHz
2
3 4
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 ppm

Problem 8.41B
ppm 3.4 3.2 3.0 2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 ppm COSY 600 MHz
1.5 1.5 4
3
2.0 2.0
F1
2.5 2.5
3.0 3.0
2
F2 HMQC 600 MHz

ppm
4
3
25 25
O
3
30 2 30
4 1
O
F1
35 O 35
1,2-cyclohexanedicarb
oxylic acid anhydride
C8H10O3
Mol. Wt.: 154
40 40 2
45 45
3.4 3.2 3.0 2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 ppm
F2
Problem 8.42A
MASS
% of Base Peak 104
100
121
50 77 91 131
65 164
146
50 60 70 80 90 100 110 120 130 140 150 160

m/z
IR 5
6
100 4 3
7 2
1
1720
9 OH
%Transmittance
8
50 10
2831 OCH3
1466
972
1350
1-methoxy-2-indanol
2939
748
3402
C10H12O2
1088
Mol. Wt.: 164
4000 3000 2000 1000

1
Wavenumber (cm-1)
H NMR 600 MHz
6 7 5 10
8
4400 4350 Hz 2750 2700 Hz 2000 1950 Hz 1650 1600 Hz
1 2 3 OH 3
7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 ppm
13
13
C/DEPT NMR
C/DEPT NMR 150.9
600 MHz
MHz
8 5
9 4 7 2
6 1 3
10
140 130 120 110 100 90 80 70 60 50 40 ppm

Problem 8.42B
ppm 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 ppm COSY 600 MHz
3
3.0 5 3.0 OH
6
4 3 3
3.5 2 3.5 10
7 1
9 OH
4.0 8 4.0
10
OCH3
2
4.5 1-methoxy-2-indanol 4.5
1
F1 C10H12O2
5.0 Mol. Wt.: 164 5.0
5.5 5.5
6.0 6.0
6.5 6.5
7.0 7.0
5 7
6
8
F2 HMQC 600 MHz
ppm
3
40 ppm 40
58
126
7 10
60 60
128
6
130
7.4 7.3 7.2 ppm 2
80 80
F1 1
100 100
120 120
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 ppm
F2
Problem 8.42C
8 7 5 10 HMBC 600 MHz
6
1
2 3 3
OH
7.5 7.4 7.3 7.2 7.1 ppm 4.5 4.0 3.5 3.0 ppm
ppm ppm
40 40 3
5
50 50
6
4 3
7 2 10
9 1
F160 8
OH 60
10
OCH3
70 1-methoxy-2-indanol 70
C10H12O2
Mol. Wt.: 164
2
80 80
1
90 90
F1
ppm ppm
125 125 5
8
7
6
130 130
135 135
140 140 94
145 145
7.5 7.4 7.3 7.2 7.1 ppm 4.5 4.0 3.5 3.0 ppm
F2
Problem 8.43A
MASS
100 131
85 109
95 182 185
50 200
50 100 150 200

m/z
IR
100
90
%Transmittance
80
70
HO 10
1 O
3518
2978
1728
1458
1373
1188
1034
887
2 9
H3C 3 C
11 4 O4000
5
3000 2000 1000
1
Wavenumber (cm-1)
H NMR
6 600 MHz
7 8 10 11
Ethyl 3-hydroxy-3,6-
dimethylhept-6-enoate 8
C11H20O3
Mol. Wt.: 200
9 1260 1240 Hz 780 760 740 Hz
2 4
7
OH 5
4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm

13
13
C/DEPT
C/DEPT NMR
NMR 150.9 MHz
600 MHz
7 9 2 4 5
3 8
10
1 6 11
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 ppm

Problem 8.40A
ppm 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm COSY 600 MHz
11
10
1.5 1.5
4
8
2.0 2.0 5
2
2.5 2.5
F1
3.0 3.0
6
3.5 3.5 OH
4.0 4.0
9
4.5 4.5
7
F2 HMQC 600 MHz

ppm
10
20 20 8
11 5
40 40 4
2
60 60 9
3
HO 10
80 1 O 9 80
2 C
H3C 3
F1 100 11 4 O 100
5 7
6
120 7 8
120
140 dimethylhept-6-enoate 140 6
C11H20O3
Mol. Wt.: 200
160 160
1
5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm

F2
Problem 8.43C
HMBC 600 MHz
8 10 11
9
7 OH 2 5 4
ppm
10
20
8
11
30 5
40 4
2
50
9
60
70 3
F180
F1
HO 10
90 1 O 9
2 C
H3C 3
11 4
100 5
O
6 7
110 7 8
120 dimethylhept-6-enoate
C11H20O3
Mol. Wt.: 200
130
140
6
150
160
170 1
5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm

F2
Problem 8.44A
MASS
121
% of Base Peak 100
136
50
65 93
149 178
50 100 150
m/z
IR
100
%Transmittance
50
3325
2962
1658
1597
1281
1211
1173
841
4000 3000 2000 1000
1
Wavenumber (cm-1)
H NMR 600 MHz
9
3
7
2 8
6
OH
8.0 7.8 7.6 7.4 7.2 7.0 6.8 ppm 3.0 2.5 2.0 1.5 ppm
13
13
C/DEPT
C/DEPT NMR
NMR 150.9 MHz
600 MHz 6 8
O
5 7 9
1
2
3
4
2 OH
3 4'-Hydroxy valerphenone 8
C11H14O2 6 9
5 4 1 Mol. Wt.: 178 7
200 180 160 140 120 100 80 60 40 ppm

Problem 8.44B
ppm 8 7 6 5 4 3 2 1 ppm COSY 600 MHz
1 1 9
6 8 8
O 7
2 5
2
7 9
1
2 6
3 3
3
4
4 4
F1 OH
C11H14O2
Mol. Wt.: 178
6 6
OH
7 7 3
2
8 8
F2 HMQC 600 MHz

ppm
9
20 20 8
7
6
40 40
60 60
F1 80 80
100 100
3
120 120
8 7 6 5 4 3 2 1 ppm
F2
Problem 8.44C
HMBC 600 MHz
3
2 7 9
6 8
OH
8.0 7.5 7.0 ppm 3.0 2.5 2.0 1.5 1.0 ppm
ppm ppm
9
15 15
6 8
O
5 7 9
20 20
1
F1 2
8
25 3 25
4
OH 7
C11H14O2
Mol. Wt.: 178
35 35
6
ppm ppm 3
120 120
130 130 1
2
140 140
150 150
160 160 4
170 170
180 180
190 190
200 200 5
210 210
8.0 7.5 7.0 ppm 3.0 2.5 2.0 1.5 1.0 ppm
F2
Problem 8.45A
MASS
68
% of Base Peak 100
108
53
50
79 93 125 153
151 168
0
50 100 150
m/z
IR
100
%Transmittance
50
3078
2962
2893
2669
1705
1442
1412
1242
933
887
3000 2000 1000
1
Wavenumber (cm-1)
H NMR 600 MHz 5,4
7 7 4 5
3
10
1
2900 2850 Hz 1600 1550 Hz 1200 1150 1100 1050 Hz

x64 9
OH
12 ppm 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm

13
13 9
C/DEPT
H2CNMR
600 MHz
H
3 4
1 2
7 6 5
8
CH3
HO 10
O
2-((1R,2S)-1-methyl-2-(prop-1-en-2-
yl)cyclobutyl)acetic acid 9 3 7 5 10 4
C10H16O2
Mol. Wt.: 168 1
8
6
2
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 ppm
Problem 8.45B
ppm 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm COSY 600 MHz
10
1.5 1.5
1
54
2.0 2.0 5,4
7
2.5 2.5 7
3
F1 3.0 3.0
3.5 3.5
4.0 4.0
4.5 4.5
9
5.0 5.0
F2 HMQC 600 MHz

ppm
20 9 20 4
H2C H 1 10
3 4 5
40 1 2
40 7
7 6 5
8
CH3 3
HO
60 10 60
O
2-((1R,2S)-1-methyl-2-(prop-1-en-2-
yl)cyclobutyl)acetic acid
80 C10H16O2 ppm 80
Mol. Wt.: 168
100 20 100
1 9
F1
10
120 30 120
140 140
40
160 160
50
180 180
3.0 2.5 2.0 1.5 ppm
5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm

F2
Problem 8.45C
HMBC 600 MHz
9 1 10
7 5,4
3 7 4 5
ppm 5.0 4.8 ppm 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 ppm
4
20
1
25
9 10
H2C H
30 3 4 5
1 2
7 6 5
8
CH3
HO 35 10
F1 O
2-((1R,2 S)-1-methyl-2-(prop-1-en-2-
yl)cyclobutyl)acetic acid 7
C10H16O2
40
Mol. Wt.: 168
6
45
50
3
ppm 9
2
150
5.0 4.8 ppm 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 ppm
F2
105 Problem 8.46A
MASS
% of Base Peak
100
50 91
77 122 151
53 65 133 166
148
50 60 70 80 90 100 110 120 130 140 150 160

m/z
IR
100
787
%Transmittance
1365
50
1466
3332
1049
2916
4000 3000 2000 1000

1 Wavenumber (cm-1)
H NMR 600 MHz
10
4 5 1
9 9
2180 2160 Hz 1440 1420 1400 1380 1360 1340 1320 1300 1280 1260 1240 1220 Hz
8
7
3 4
11 OH
5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
13
10 11
CH2CH2OH
2
1 3
7
8 6
9 4
9 4
5 11 5 10
3 Nopol 1
7 8
C11H18O
2 Mol. Wt.: 166 6
140 130 120 110 100 90 80 70 60 50 40 30 ppm

Problem 8.46B
ppm 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm COSY 600 MHz
8
1.0 1.0
4
1.5 1.5 7
2.0 2.0 5
10
2.5 2.5 4
9
F1 3.0 3.0
3.5 3.5 11
4.0 4.0
1 2
4.5 4.5
OH
5.0 5.0
3
5.5 5.5
F2 HMQC 600 MHz
ppm
20 10 11 20 8
CH2CH2OH
7
2
1 3 6
40 8 6
7 40
9 4 1
5
Nopol 11
60 60
C11H18O
ppm
Mol. Wt.: 166
F1
30 4
80 80
9
35
100 6 100
40
10
5
120 120 3
2.5 2.4 2.3 2.2 2.1 ppm
5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
2
F2
OH
Problem 8.46C
INADEQUATE 150.9600
INADEQUATE MHzMHz
2 3 11 1
Hz
-15000 -15000
-10000 -10000
10 11
-5000 CH2CH2OH -5000
2
F1 0 1 3 0
7
8 6
9 4
5000 5000
5
Nopol
10000 10000
C11H18O
Mol. Wt.: 166
15000 15000
140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

10 F2 7 8
1 5 6 9 4
Hz
-16000 -16000
-14000 -14000
-12000 -12000
-10000 -10000
-8000 -8000
-6000 -6000
F1
-4000 -4000
-2000 -2000
0 0
2000 2000
4000 4000
45 40 35 30 25 20 ppm
F2
Problem 8.47A
MASS 105
% of Base Peak
100 277
100 FM (found) = 277.1083 by CI
77 136
50
154 50 305 317
50 100 150 200 250 300

m/z m/z
IR
100
2877
2939
%Transmittance
3456
50
717
1072
1751
1281
1712
4000 3000 2000 1000
1
Wavenumber (cm-1)
H NMR 600 MHz
3 6 9
2 12 10
7
4 10
OH
4800 4700 4600 4500 Hz 3300 3200 3100 3000 Hz 1500 1400 1300 Hz
O 11 8 12
O 13
O 9
12
10 8
CO 6 O
7
O
C O CH2OH O
5 2250 2200 Hz 1750 1700 Hz
1 11
2
HOH2C
4 3
5-(Benzoyloxy)hexahydro-4-
(hydroxymethyl)
C15H16O5
Mol. Wt.: 276
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 ppm
Problem 8.47B
ppm 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 ppm COSY 600 MHZ
O 7
O 13
9
3 10
12 3
8
O 6
7
C O CH2OH 11
5
41 11 4
2
4 3
5 5
F1 5-(Benzoyloxy)hexahydro-4-
(hydroxymethyl)
9
C15H16O5 6
Mol. Wt.: 276
6 6
O
C O
7 O O 7
4 3
8 HOH2C 8 2
COSY 600 MHZ

ppm
7
10
2.5 2.5 10
12
12
3.0 3.0 8
3.5 3.5
11
F1
4.0 4.0
4.5 4.5
5.0 5.0 9
6
5.5 5.5
5.5 5.0 4.5 4.0 3.5 3.0 2.5 ppm
F2
Problem 8.47C
13
2 3
1 8 1012
4 9 6 11 7
130 129 ppm 77.5 77.0 ppm

13 5
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 ppm
2 3
4 HMQC 600 MHz
6 9 11
7
ppm
O 12
O
40 O 13 8 10
9 C O
12
10 8 13
50 O O
O 6
7
OH 7
C O CH2OH
60 5
HOH2C
1 11 11
2 13
70
4 3
6
F1805-(Benzoyloxy)hexahydro-4-
(hydroxymethyl)
C15H16O5 12 8 12 10 9
Mol. Wt.: 276 10
90 ppm
100 35
12
110 10
40 8
120
3.0 2.9 2.8 2.7 2.6 2.5 2.4 ppm 3
130
2
4
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 ppm
F2
Problem 8.47D
2 HMBC 600 MHz

3 10
4 6 11 12 8
9 7 OH
8.2 8.0 7.8 7.6 7.4 ppm 5.0 4.5 4.0 3.5 3.0 2.5 ppm
ppm
12
10
40 O 8
O 13
9
12
50 10 8
O 6
7
7
C CH2OH
5 O
11
60 1
2 11
4 3
70 5-(Benzoyloxy)hexahydro-4-
(hydroxymethyl)
C15H16O5
Mol. Wt.: 276 6
80
9
F1
ppm
1 3
130 2
4
140
150
160
5
170
13
180
8.2 8.0 7.8 7.6 7.4 ppm 5.0 4.5 4.0 3.5 3.0 2.5 ppm
F2

Robert M Silverstein Francis X Webster David Kiemle Solutions Manual For Spectrometric Identification of Organic Compounds Wiley 2005 PDF

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Robert M Silverstein Francis X Webster David Kiemle Solutions Manual For Spectrometric Identification of Organic Compounds Wiley 2005 PDF

Uploaded by

Copyright:

Available Formats

Answers for Student Exercises 1.1 to 1.

Atom Type # of Atoms Mass Total Mass

b Atom Type # of Atoms Mass Total Mass

O Atom Type # of Atoms Mass Total Mass

Atom Type # of Atoms Mass Total Mass

Atom Type # of Atoms Mass Total Mass

Atom Type # of Atoms Mass Total Mass

Atom Type # of Atoms Mass Total Mass

Atom Type # of Atoms Mass Total Mass

O Atom Type # of Atoms Mass Total Mass

Atom Type # of Atoms Mass Total Mass

O Atom Type # of Atoms Mass Total Mass

o Atom Type # of Atoms Mass Total Mass

2-Bromopentane 71 150 121 / C3H6Br 29 / C2H5

butan-1-amine 55 / C4H7 18 / NH4 R

6-Methyl-5-hepten-2-one 108 / C8H12 18 / H2O R

1,3-Cyclohexadiene Diphenylacetylene 1-Octene 2-Pentene

Spectrum E Spectrum H Spectrum I Spectrum F Spectrum G

Spectrum Q Spectrum O Spectrum P Spectrum N Spectrum R

2.7. Methyl isothiocyanate CH3N=C=S

4-Heptanone 3-Heptanol 4-Bromotoluene 2-Bromopentane

(b) (cyclohex-2-enyl)methyl acetate

Spin Appr. Table or Calculation Coupled with Multiplet (n+1) Integration

Spin Appr. Table or Calculation Coupled with Multiplet (n+1) Integration

Spin Appr. Table or Calculation Coupled with Multiplet (n+1) Integration

Spin Appr. Table or Calculation Coupled with Multiplet (n+1) Integration

Spin Appr. Table or Calculation Coupled with Multiplet (n+1) Integration

Spin Appr. Table or Calculation Coupled with Multiplet (n+1) Integration

Spin Appr. Table or Calculation Coupled with Multiplet (n+1) Integration

3.3 (i) 1 and 6

Spin Appr. Table or Calculation Coupled with Multiplet (n+1) Integration

Actual spectrum would look like this!

Spin Appr. Table or Calculation Coupled with Multiplet (n+1) Integration

2,2 3,3 6,7 8

3.1 (i) N.A.

Spin Appr. Table or Calculation Coupled with Multiplet (n+1) Integration

Protocol of the H-1 NMR Prediction:

Node Shift Base + Inc. Comment (ppm rel. to TMS)

H 4.85 5.25 1-ethylene

Spin Appr. Table or Calculation Coupled with Multiplet (n+1) Integration

1 6 2,2 3,3, and 4

3.5 3.0 2.5 2.0 1.5 1.0 ppm

4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

12.0 11.5 ppm

3.5 3.0 2.5 2.0 1.5 ppm

4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

2200 2150 2100 Hz 1250 1200 1150 Hz

3.5 3.0 2.5 2.0 1.5 1.0 ppm

2520 2510 2500 2490 Hz

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 ppm

4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm

5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm

2120 2100 2080 2060 Hz

3.5A. (1.58(300) 0.90(300))/7 = about 29; (2.36(300) 1.58(300))/7 = about 33

3.5E. (2.38(300) 1.52(300))/7 = about 37; (1.52(300) 1.38(300))/7 = about 6

3.5F. (2.38(300) 1.13(300))/7 = about 54

3.5G. (2.61(300) 1.35(300))/7 = about 54; (1.35(300) 1.29(300))/7 = about 2 to 3

3.5H. Long range coupling; cant measure coupling constant

3.5I. (4.33(300) 2.01(300))/7 = about 99; (2.01(300) 0.99(300))/7 = about 44

3.5K. (4.08(300) 1.44(300))/7 = about 113

3.5L. (2.26(300) 1.62(300))/7 = about 27; (1.62(300) 0.92(300))/7 = about 30

3.5Q. (3.39(300) 1.86(300))/7 = about 66; (2.36(300) 1.65(300))/7 = about 30

3.5U. (7.25(300) 6.81(300))/9 = about 15