有機光譜Ch5~9習題

Problems 277
*6. The chemical shifts of the methyl groups of three related molecules, pinane, a-pinene, and
b-pinene, follow.
CH3 CH3 CH3 CH3 CH3 CH3

CH3 CH3 CH2
1.17 1.27 1.23
ppm 0.99 ppm 1.63 ppm
ppm ppm
1.01 ppm 0.85 ppm 0.72 ppm

Pinane ␣ -Pinene ␤ -Pinene
Build models of these three compounds and then explain why the two circled methyl groups
have such small chemical shifts.
*8. Make a three-dimensional drawing illustrating the magnetic anisotropy in 15,16-dihydro-15,

16-dimethylpyrene, and explain why the methyl groups are observed at −4.2 ppm in the 1H
NMR spectrum.
CH3 CH3
15,16-Dihydro-15,16-dimethylpyrene
Copyright 2013 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part.
Problems 279
*15. The following compound is a monosubstituted aromatic hydrocarbon with the formula C9H12.
Give its structure and assign the chemical shift values.
1000 800 600 400 200 0 CPS

500 1H NMR 400 300 200 100 0 CPS
250 200 150 100 50 0
60 MHz
100 80 60 40 20 0
50 40 30 20 10 0
Integral = 5 Integral = 6
Integral = 1
C9H12
8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0 PPM
*16. The following compound is a carboxylic acid that contains a bromine atom: C4H7O2Br. The
peak at 10.97 ppm was moved onto the chart (which runs only from 0 to 8 ppm) for clarity.
What is the structure of the compound?
1000 800 600 400 200 0 CPS

500 400 300 200 100 0 CPS
250
1H NMR 200 150 100 50 0
100 60 MHz 80 60 40 20 0
50 40 30 20 10
Integral = 3 0
C4H7O2Br
Integral = 1
Integral = 1
Integral = 2
8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0 PPM
280 Nuclear Magnetic Resonance Spectroscopy • Part One: Basic Concepts
*17. The compound that gives the following NMR spectrum has the formula C3H6Br2. Draw the
structure.
1
H NMR C3H6Br2
300 MHz
4.12 2.03
4.0 3.5 3.0 2.5 2.0 1.5
*18. Draw the structure of an ether with formula C5H12O2 that fits the following NMR spectrum:
1
H NMR
300 MHz
C5H12O2
4.09 3.97
4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0
Problems 281
*19. Following are the NMR spectra of three isomeric esters with the formula C7H14O2, all derived
from propanoic acid. Provide a structure for each.
1H NMR C7H14O2
300 MHz
2.00 1.95 1.90 1.85
1.97 1.92 1.04 2.89 5.85
4.0 3.5 3.0 2.5 2.0 1.5 1.0
(a)
C7H14O2
1
H NMR
300 MHz
1.98 8.60 2.97
4.0 3.5 3.0 2.5 2.0 1.5 1.0
(b)
282 Nuclear Magnetic Resonance Spectroscopy • Part One: Basic Concepts
1
H NMR C7H14O2
300 MHz
1.33 1.30 1.31 1.35 1.87 1.94
4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5
(c)
*20. The two isomeric compounds with the formula C10H14 have NMR spectra shown below. Make
no attempt to interpret the aromatic proton area between 7.1 and 7.3 ppm except to determine
the number of protons attached to the aromatic ring. Draw the structures of the isomers.
C10H14
5.10
7.5 7.0
1.10 2.15 3.04 2.94
4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5
(a)
Problems 283
C10 H14
5.10
7.5 7.0
2.14 2.06 2.06 2.98
4.0 3.5 3.0 2.5 2.0 1.5 1.0
(b)
*21. The compound with the formula C8H11N has the NMR spectra shown. The infrared spectrum
shows a doublet at about 3350 cm–1. Make no attempt to interpret the aromatic proton area
between 7.1 and 7.3 ppm except to determine the number of protons attached to the aromatic
ring. Draw the structure of the compound.
C8H11N
4.93
7.5 7.0
2.04 2.02 2.06

4.0 3.5 3.0 2.5 2.0 1.5 1.0
Problems 327
*4. The following spectrum is of an ester with formula C5H8O2. Multiplicities are indicated. Draw
the structure of the compound and assign each peak.
s
s
CDCI 3
(solvent)
200 150 100 50 0
*5. Following are the 1H and 13C spectra for each of four isomeric bromoalkanes with formula
C4H9Br. Assign a structure to each pair of spectra.
Carbon spectrum C4H9Br

A
CDCl3
(solvent)
85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0
328 Nuclear Magnetic Resonance Spectroscopy • Part Two: Carbon-13 Spectra
Proton spectrum C4H9Br

A
4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0

B
CDCl3
85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0
Proton spectrum C4H9Br

B
0.89 1.78 2.52 2.59
4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0
Problems 329

C
CDCl3
85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0
Proton spectrum
C
C4H9Br
1.80 1.83 1.87 2.64
4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0
Carbon spectrum
D C4H9Br
CDCl3
85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0
Proton spectrum
D C4H9Br
2.1 2.0 1.9
1.82 0.93 5.37
4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0
*6. Following are the 1H and 13C spectra for each of three isomeric ketones with formula C7H14O.
Assign a structure to each pair of spectra.
44.79
17.39
Carbon spectrum
A
13.78
C7H14O
CDCl3
211.04
200 150 100 50 0
Problems 331
Proton spectrum
A C7H14O
1.96 2.00 2.91
3.0 2.5 2.0 1.5 1.0 0.5 0.0
18.55
Carbon spectrum
B
C7H14O
38.85
218.40
CDCl3
200 150 100 50 0
Proton spectrum C7H14O

B
2.9 2.8 2.7
1.04 6.18
3.0 2.5 2.0 1.5 1.0 0.5 0.0
29.73
29.73
Carbon spectrum C7H14O

C
32.27
30.88
55.98
CDCl3
32.27
218.31
(solvent)
30
200 150 100 50 0
Problems 333

C
1.95 2.98 8.91
3.0 2.5 2.0 1.5 1.0 0.5 0.0
12. The proton NMR spectrum for a compound with formula C10H12O2 is shown below. The in-
frared spectrum has a strong band at 1711 cm−1. The normal carbon-13 NMR spectral results
are tabulated along with the DEPT-135 and DEPT-90 information. Draw the structure of this
compound.
Normal Carbon DEPT-135 DEPT-90
29 ppm Positive No peak

50 Negative No peak
55 Positive No peak
114 Positive Positive
126 No peak No peak
159 No peak No peak
207 No peak No peak
Proton C10H12O2
1.91 2.01 3.13 2.15 3.01
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 0.0
Problems 339
15. The proton NMR spectrum of a compound with formula C5H10O is shown. The normal
carbon-13 and the DEPT experimental results are tabulated. The infrared spectrum shows
a broad peak at about 3340 cm–1 and a medium-sized peak at about 1651cm–1. Draw the
structure of this compound.
22.2 ppm Positive No peak

40.9 Negative No peak
142.3 No peak No peak
2.11 2.13 1.97 1.22 2.99
5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5
Problems 341
17. The proton NMR spectrum of a compound with formula C6H5NCl2 is shown. The normal
carbon-13 and the DEPT experimental results are tabulated. The infrared spectrum shows
peaks at 3432 and 3313 cm–1 and a series of medium-sized peaks between 1618 and
1466 cm–1. Draw the structure of this compound.
118.0 ppm Positive Positive

128.0 Positive Positive
Proton spectrum
C6H5NCl2
1.96 0.99 2.13
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0
426 Nuclear Magnetic Resonance Spectroscopy • Part Three: Spin–Spin Coupling
*4. The proton NMR spectrum shown in this problem is of trans-4-hexen-3-one. Expansions are
shown for each of the five unique types of protons in this compound. Determine the coupling
constants. Draw tree diagrams for each of the protons shown in the expansions and label them
with the appropriate coupling constants. Also determine which of the coupling constants are 3J
and which are 4J. Assign the protons to the structure using the letters a, b, c, d, and e. Hertz
values are shown above each of the peaks in the expansions.
e d
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 1.5 1.0 0.5 0.0
(ppm)
Problems 427
2016.57
2009.75
2002.94
2000.86
1996.12
1994.05
1987.24
1980.42
1787.54
1785.91
1784.28
1782.50
1771.83
1770.06
1768.43
1766.80
719.42
712.02
704.76
697.35
e d c
6.72 6.68 6.64 6.60 5.96 5.92 5.88 2.40 2.36 2.32
(ppm) (ppm) (ppm)

513.06
511.43
506.24
504.61
271.14
263.88
256.47
b a
1.72 1.68 0.92 0.88 0.84
(ppm) (ppm)
*5. The proton NMR spectrum shown in this problem is of trans-2-pentenal. Expansions are shown
for each of the five unique types of protons in this compound. Determine the coupling
constants. Draw tree diagrams for each of the protons shown in the expansions and label them
with the appropriate coupling constants. Also determine which of the coupling constants are
3
J and which are 4J. Assign the protons to the structure using the letters a, b, c, d, and e. Hertz
values are shown above each of the peaks in the expansions.
a
3H
O
H C H
C C
CH3 CH2 H
e b
1H 2H
d
1H
c
1H
9.5 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 1.5 1.0 0.5 0.0
(ppm)
Problems 429
2808.72
2801.00
2048.35
2042.10
2035.85
2032.54
2026.66
2020.41
1797.96
1796.49
1795.02
1790.24
1788.77
1786.93
1782.52
1781.05
1779.21
1774.43
1772.96
1771.49
e d c
9.36 9.34 9.32 6.84 6.82 6.80 6.78 6.76 6.74 6.72 6.00 5.98 5.96 5.94 5.92 5.90 5.88
(ppm) (ppm) (ppm)

678.37
676.90
671.02
669.55
663.30
657.41
655.94
650.06
648.22
295.25
287.89
280.54
b a
2.26 2.24 2.22 2.20 2.18 2.16 2.14 1.00 0.98 0.96 0.94 0.92
(ppm) (ppm)
*6. In which of the following two compounds are you likely to see allylic (4J) coupling?
Problems 437
*15. The proton NMR spectral information shown in this problem is for a compound with formula
C10H12O3. A broad peak appearing at 12.5 ppm is not shown in the proton NMR reproduced
here. The normal carbon-13 spectral results, including DEPT-135 and DEPT-90 results, are
tabulated:

40 Negative No peak
63 Negative No peak
125 No peak No peak
158 No peak No peak
179 No peak No peak
Draw the structure of this compound.
quartet
doublets triplet
10 9 8 7 6 5 4 3 2 1 0
19. The spectrum shown in this problem is of 1-methoxy-1-buten-3-yne. Expansions are shown for
each proton. Determine the coupling constants for each of the protons and draw tree diagrams
for each. The interesting part of this problem is the presence of significant long-range coupling
constants. There are 3J, 4J, and 5J couplings in this compound. Be sure to include all of them in
your tree diagram (graphical analysis).
3H
(b)
CH3
O
H
(a) C C
C H (d)
C
H
(c)
1H 1H 1H
6.8 6.6 6.4 6.2 6.0 5.8 5.6 5.4 5.2 5.0 4.8 4.6 4.4 4.2 4.0 3.8 3.6 3.4 3.2 3.0 2.8 2.6
(ppm)
1923.24
1922.76
1917.24
1916.76
1384.50
1381.50
1378.50
1375.50
931.77
931.25
928.77
928.25
6.42 6.40 6.38 4.62 4.60 4.58 3.12 3.10 3.08
(ppm) (ppm) (ppm)
*25.The proton NMR spectral information shown in this problem is for a compound with formula
C9H8F4O. Expansions are shown for all of the protons. The aromatic ring is disubstituted. In the
region from 7.10 to 6.95 ppm, there are two doublets (1H each). One of the doublets is partially
overlapped with a singlet (1H). The interesting part of the spectrum is the one proton pattern
found in the region from 6.05 to 5.68 ppm. Draw the structure of the compound and draw a tree
diagram for the proton at 5.85 ppm. (see Section 7.12 for proton-to-fluorine coupling constants).
10 9 8 7 6 5 4 3 2 1 0
2177.65
2176.48
2170.09
2169.00
2162.75
2161.52
2121.99
2114.07
2106.00
2098.66
1814.34
1811.44
1808.53
1761.23
1758.32
1755.41
1708.04
1705.13
1702.30
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 5.6
(ppm)
Problems 455
35. The heliannuols are a family of natural products isolated from the sunflower, Helianthus
annuus, with unusual sesquiterpenoid structures. Heliannuol G was originally assigned the
structure shown [Journal of Natural Products, 62 (1999): 1636–9]. When a compound with
that structure was later synthesized, however, the NMR spectra of the synthetic compound did
not match the data from the natural material. Using the following NMR data for the natural
product, propose a different reasonable structure for heliannuol G. Note that the OH proton is
not visible in the NMR spectrum.
OH
originally proposed HO
(incorrect) structure of
heliannuol G
O
Natural heliannuol G: 1H NMR (400 MHz, CDCl3): δ (ppm): 6.59 (s, 1H), 6.56 (s, 1H), 5.98 (d,
1H, J = 15.5 Hz), 5.79 (dd, 1H, J = 15.5, 8.4 Hz), 5.09 (dd, 1H, J = 8.4, 7.4 Hz), 3.43 (dq, 1H,
J = 7.2, 7.2 Hz), 2.19 (s, 3H), 1.34 (s, 6H), 1.10 (d, 1H, J = 7.2 Hz).
492 Nuclear Magnetic Resonance Spectroscopy • Part Four
*3. Determine the structure of the aromatic compound with formula C6H5BrO. The peak at about
5.6 ppm is exchangeable and shifts readily when the sample is diluted. The expansions that are
provided show 4J couplings of about 1.6 Hz.
7.8 7.6 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)
2236.67
2235.06
2228.58
2227.05
2168.00
2166.47
2160.68
2159.91
2159.15
2158.31
2152.59
2150.99
7.46 7.44 7.42 7.22 7.20 7.18 7.16
(ppm) (ppm)
2044.48
2042.88
2037.16
2036.47
2035.55
2034.87
2029.15
2027.54
2108.95
2107.42
2100.79
2099.26
7.04 7.02 7.00 6.98 6.82 6.80 6.78 6.76
(ppm) (ppm)
Problems 493
*5. The spectrum and expansions provided in this problem are for one of the compounds shown
below. The broad peak at 5.25 ppm is exchangeable and solvent dependent. Using calculations
of the approximate chemical shifts and the appearance and position of the peaks (singlet and
doublets), determine the correct structure. The chemical shifts may be calculated from the in-
formation provided in Appendix 6. The calculated values will be only approximate but should
allow you to determine the correct structure.
CH3 OH OH
OH CH3
CH3
CH3 CH3 CH3
2094.31
2086.59
1991.36
1978.13
1970.04
7.00 6.95 6.90 6.85 6.80 6.75 6.70 6.65 6.60 6.55 6.50
(ppm)
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 1.0 0.5 0.0
(ppm)
*6. The proton NMR spectrum for a compound with formula C5H10O is shown. Determine the
structure of this compound. The peak at 2.1 ppm is solvent dependent. Expansions are pro-
vided for some of the protons. Comment on the fine structure on the peak at 4.78 ppm. The
normal carbon-13, DEPT-135, and DEPT-90 spectra data are tabulated.

41 Negative No peak
60 Negative No peak
112 Negative No peak
142 No peak No peak
0
1456.40
1435.32
1434.38
1433.33
1432.44
1119.97
1113.52
1107.13
693.25
686.91
680.46
4.88 4.84 4.80 4.76 3.76 3.72 3.68 2.32 2.28 2.24
(ppm) (ppm)
18. The proton NMR spectrum shown in this problem is for a common insect repellent,
N,N-diethyl-m-toluamide, determined at 360 K. This problem also shows a stacked plot
of this compound determined in the temperature range of 290 to 360 K (27–87°C). Explain
why the spectrum changes from two pairs of broadened peaks near 1.2 and 3.4 ppm at low
temperature to a triplet and quartet at the higher temperatures.
6H
3H
4H 4H
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 1.0 0.5 0.0
(ppm)
360K
350
340
330
310
290
3.8 3.6 3.4 3.2 3.0 2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0 0.8
(ppm)
Problems 549
PROBLEMS
*1. Using the following set of DEPT-135, COSY, and HETCOR spectra, provide a complete
assignment of all protons and carbons for C4H9Cl.
200 180 160 140 120 100 80 60 40 20 0

PPM
550 Nuclear Magnetic Resonance Spectroscopy • Part Five: Advanced NMR Techniques
Problems 551
0.0
1.0
2.0
3.0
4.0
PPM
60 50 40 30 20 10
PPM
*2. Assign each of the peaks in the following DEPT spectrum of C6H14O. The infrared spectrum
shows a strong and broad peak at about 3350 cm⫺1. (Note: There is more than one possible
answer.)
220 200 180 160 140 120 100 80 60 40 20 0
(ppm)
Problems 553
*3. The upper spectrum is a HETCOR (HSQC) spectrum for citronellol in the range of 0.8 to
5.5 ppm. The lower spectrum is an expansion of the same compound in the region between 0.8
and 2.2 ppm. Use the structural formula on p. 531, as well as the stacked full-edited DEPT
spectrum in Figure 9.12 and the gCOSY spectra shown in Figures 9.15a and 9.15b, to provide
a complete assignment of all carbon and hydrogen atoms in the molecule, especially the
diastereotopic protons at 25, 37, and 40 ppm. Complete assignments have been provided in the
Answers to Selected Problems.
Problems 555
*4. Geraniol has the structure
10
CH3
3 1
4
2 OH
5
6
7
CH3 CH3
8 and 9
Use the stacked full-edited DEPT spectrum shown on this page, the gCOSY spectrum shown
on the next page, and finally the HETCOR (HSQC) spectrum shown on the third page.
Carbons 3 and 7 do not show on the DEPT spectrum because the spectrum only shows proto-
nated carbon atoms. The assignments you determined in Problem 3 may help you here.
Complete assignments have been provided in the Answers to Selected Problems.
CH3 carbons
CH2 carbons
CH carbons
All protonated carbons
Problems 557
*5. The following set of spectra includes an expansion of the aromatic region of the 1H NMR
spectrum of methyl salicylate as well as a HETCOR spectrum. Provide a complete
assignment of all aromatic protons and unsubstituted ring carbons in methyl salicylate. (Hint:
Consider the resonance effects of the substituents to determine relative chemical shifts of the
aromatic hydrogens. Also try calculating the expected chemical shifts using the data provided
in Appendix 6.)
METHYL SALICYLATE EXPANSION

2256.49
2086.93
2086.61
2078.50
2336.21
2334.89
2334.52
2328.28
2326.99
2326.48
2320.64
2226.37
2225.78
2224.63
2224.06
2209.00
2208.46
2122.58
2078.17
2053.30
2052.24
2046.08
2045.33
2045.04
2044.31
2036.44
2919.50
2216.37
2176.65
2038.15
2210.77
2219.12
2210.16
2051.55
2167.22
2037.03
2217.99
2217.41
HERTZ
7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8
PPM
Problems 559
0.0
2.0
4.0
6.0
8.0
10.0
PPM
130 120 110 100 90 80 70 60 50
PPM

有機光譜Ch5~9習題

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Problems 277

CH3 CH3 CH3 CH3 CH3 CH3

1.01 ppm 0.85 ppm 0.72 ppm

*8. Make a three-dimensional drawing illustrating the magnetic anisotropy in 15,16-dihydro-15,

1000 800 600 400 200 0 CPS

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0 PPM

1000 800 600 400 200 0 CPS

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0 PPM

4.0 3.5 3.0 2.5 2.0 1.5

2.00 1.95 1.90 1.85

1.97 1.92 1.04 2.89 5.85

4.0 3.5 3.0 2.5 2.0 1.5 1.0

1.98 8.60 2.97

4.0 3.5 3.0 2.5 2.0 1.5 1.0

1.33 1.30 1.31 1.35 1.87 1.94

4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5

1.10 2.15 3.04 2.94

4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5

2.14 2.06 2.06 2.98

4.0 3.5 3.0 2.5 2.0 1.5 1.0

2.04 2.02 2.06

200 150 100 50 0

Carbon spectrum C4H9Br

Proton spectrum C4H9Br

Carbon spectrum C4H9Br

Proton spectrum C4H9Br

0.89 1.78 2.52 2.59

Carbon spectrum C4H9Br

1.80 1.83 1.87 2.64

2.1 2.0 1.9

1.82 0.93 5.37

200 150 100 50 0

1.96 2.00 2.91

3.0 2.5 2.0 1.5 1.0 0.5 0.0

200 150 100 50 0

Proton spectrum C7H14O

2.9 2.8 2.7

3.0 2.5 2.0 1.5 1.0 0.5 0.0

Carbon spectrum C7H14O

200 150 100 50 0

Proton spectrum C7H14O

1.95 2.98 8.91

3.0 2.5 2.0 1.5 1.0 0.5 0.0

Normal Carbon DEPT-135 DEPT-90

29 ppm Positive No peak

1.91 2.01 3.13 2.15 3.01

Normal Carbon DEPT-135 DEPT-90

22.2 ppm Positive No peak

Proton spectrum C5H10O

2.11 2.13 1.97 1.22 2.99

5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5

Normal Carbon DEPT-135 DEPT-90

118.0 ppm Positive Positive

1.96 0.99 2.13

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0

(ppm) (ppm) (ppm)

1.72 1.68 0.92 0.88 0.84

(ppm) (ppm) (ppm)

Normal Carbon DEPT-135 DEPT-90

15 ppm Positive No peak

Draw the structure of this compound.

6.42 6.40 6.38 4.62 4.60 4.58 3.12 3.10 3.08

(ppm) (ppm) (ppm)

7.46 7.44 7.42 7.22 7.20 7.18 7.16