arrow. Report your answer in ppm to the tenths' place.

Principles of Instrumental Analysis
7th Edition
ISBN:9781305577213
Author:Douglas A. Skoog, F. James Holler, Stanley R. Crouch
Publisher:Douglas A. Skoog, F. James Holler, Stanley R. Crouch
Chapter16: An Introduction To Infrared Spectrometry
Section: Chapter Questions
Problem 16.9QAP
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Using tables 22.3, 22.4, and 22.5, predict the shift for the protons attached to the atom indicated by the
arrow. Report your answer in ppm to the tenths' place.
Transcribed Image Text:Using tables 22.3, 22.4, and 22.5, predict the shift for the protons attached to the atom indicated by the arrow. Report your answer in ppm to the tenths' place.
TABLE 22.4
Group
-CH₂
-CH(CH₂)₂
-CH₂CI
-CH=CH₂
-CH=CHAr
-CH=CHCO,H
-CH-CH(C-O)Ar
Group
-Ar
-(C-O)H
-(C=O)R
-(C=O)Ar
-(C-O)CH-CHAr
-(C=O)OCH,
-(C-O)OCH,CH,
agnetic Resonance Spectroscopy
-(C=O)OH
-(C=O)CI
IC ĐỊNH,
Additive parameters for predicting NMR
chemical shifts of aromatic protons in CDCI,
Base value
7.36 ppm²
-CEN
-F
-a
-Br
-OH
-OR
-OAr
ortho
-0.18
-0.14
0.02
0.04
0.14
0.19
0.28
ortho
0.23
0.53
0.60
0.45
0.67
0.68
0.69
0.77
0.76
0.46
0.29
-0.32
-0.02
0.13
-0.53
-0.45
-0.36
-0.27
-0.14
-0.71
-0.68
0.14
0.87
meta
-0.11
-0.08
-0.01
-0.04
-0.02
0.04
0.06
meta
0.07
0.18
0.10
0.12
0.14
0.08
0.06
0.11
0.16
0.09
0.12
-0.05
-0.07
-0.13
-0.14
-0.07
-0.04
0.02
para
-0.21
-0.20
-0.04
-0.12
-0.11
0.07
-0.22
-0.15
-0.07
0.20
0.05
0.05
(Continued)
para
-0.02
0.28
0.20
0.23
0.21
0.19
0.17
0.25
0.33
0.17
0.25
-0.25
-0.13
-0.08
-0.43
-0.41
-0.28
-0.13
-0.09
-0.62
-0.73
-O(C=O)R
-O(C=O)Ar
-NH,
-N(CH₂)₂
-NH(C=O)R
-NO₂
a. Base value is the measured chemical shift of benzene in CDCI, (1% solution).
371
-0.27
0.35
Group (Y)
-R
-C-C
-C-C-Arb
-C=C(C=O)OR
-C=C-R
-CC-Ar
-Ar
-(C=O)OH
-(C=O)OR
-(C=O)H
-(C=O)R
-(C=O)Ar
IC ĐỊNH,
-(C=O)CI
-CIN
-Br
-CI
-OH
-OR
22.3 Additive parameters for predicting NMR chemical shifts of alkyl
protons in CDCI,
-OAr
-O(C=O)R
-O(C=O)Ar
-NH₂
-NH(C=O)R
NHẠC GIA
Group
-R
-CH=CH₂
-CH₂OH
-CH₂X (X-F, CI, Br)
-(C=O)OH
-(C=O)OR
-(C=O)H
-(C=O)R
-(C=O)Ar
-Ar
-Br
-CI
-OR
-OAr
-O(C=O)R
—NH, NHR, TNR,
-NH(C=O)R
Alpha (a) substituent
Methyl
Methylene
Methine
0.0
0.8
0.9
1.0
0.9
1.2
1.4
1.1
1.1
1.1
1.2
1.7
1.0
1.8
1.1
2.1
2.2
2.3
INNNN
2.1
2.8
2.8
3.1
1.5
2.1
2.3
Base values
trans
Base value
gem
0.45
1.26
0.64
0.70
0.97
0.80
1.02
1.10
1.82
1.38
1.07
1.08
1.22
1.21
2.11
0.80
2.08
0.9 ppm
1.2 ppm
1.5 ppm
Beta (3) substituent
0.0
0.2
0.1
gem
0.3
0.3
0.4
0.4
0.3
0.3
0.4
0.3
0.3
0.3
0.4
0.4
0.7
0.5
0.3
0.3
0.5
a. There may be differences of 0.1-0.5 ppm in the chemical shift values calculated from this table and those
measured from individual spectra.
b. Ar= aromatic group.
TABLE 22.5
Additive Parameters for Predicting NMR
Chemical Shifts of Vinyl Protons in CDCI,
0.5
0.5
0.2
0.3
0.4
5.28 ppm
cis
-0.22
0.08
-0.01
-0.11
1.41
1.18
0.95
1.12
1.13
Gamma (y) substituent
0.36
0.45
0.18
-1.07
-0.60
-0.35
-1.26
-0.57
H-
trans
-0.28
-0.01
-0.02
-0.04
0.71
0.55
1.17
0.87
0.63
-0.07
0.55
0.13
-1.21
-1.00
-0.64
1.21
-0.72
0.0
0.1
0.0
0.1
0.1
a. There may be small differences in the chemical-shift values calculated from this
table and those measured from individual spectra.
0.2
0.1
0.1
0.1
0.1
0.0
0.1
0.1
ddddddddddddd
0.1
0.2
0.2
0.2
0.1
0.1
0.3
0.1
0.2
0.1
0.1
0.1
Transcribed Image Text:TABLE 22.4 Group -CH₂ -CH(CH₂)₂ -CH₂CI -CH=CH₂ -CH=CHAr -CH=CHCO,H -CH-CH(C-O)Ar Group -Ar -(C-O)H -(C=O)R -(C=O)Ar -(C-O)CH-CHAr -(C=O)OCH, -(C-O)OCH,CH, agnetic Resonance Spectroscopy -(C=O)OH -(C=O)CI IC ĐỊNH, Additive parameters for predicting NMR chemical shifts of aromatic protons in CDCI, Base value 7.36 ppm² -CEN -F -a -Br -OH -OR -OAr ortho -0.18 -0.14 0.02 0.04 0.14 0.19 0.28 ortho 0.23 0.53 0.60 0.45 0.67 0.68 0.69 0.77 0.76 0.46 0.29 -0.32 -0.02 0.13 -0.53 -0.45 -0.36 -0.27 -0.14 -0.71 -0.68 0.14 0.87 meta -0.11 -0.08 -0.01 -0.04 -0.02 0.04 0.06 meta 0.07 0.18 0.10 0.12 0.14 0.08 0.06 0.11 0.16 0.09 0.12 -0.05 -0.07 -0.13 -0.14 -0.07 -0.04 0.02 para -0.21 -0.20 -0.04 -0.12 -0.11 0.07 -0.22 -0.15 -0.07 0.20 0.05 0.05 (Continued) para -0.02 0.28 0.20 0.23 0.21 0.19 0.17 0.25 0.33 0.17 0.25 -0.25 -0.13 -0.08 -0.43 -0.41 -0.28 -0.13 -0.09 -0.62 -0.73 -O(C=O)R -O(C=O)Ar -NH, -N(CH₂)₂ -NH(C=O)R -NO₂ a. Base value is the measured chemical shift of benzene in CDCI, (1% solution). 371 -0.27 0.35 Group (Y) -R -C-C -C-C-Arb -C=C(C=O)OR -C=C-R -CC-Ar -Ar -(C=O)OH -(C=O)OR -(C=O)H -(C=O)R -(C=O)Ar IC ĐỊNH, -(C=O)CI -CIN -Br -CI -OH -OR 22.3 Additive parameters for predicting NMR chemical shifts of alkyl protons in CDCI, -OAr -O(C=O)R -O(C=O)Ar -NH₂ -NH(C=O)R NHẠC GIA Group -R -CH=CH₂ -CH₂OH -CH₂X (X-F, CI, Br) -(C=O)OH -(C=O)OR -(C=O)H -(C=O)R -(C=O)Ar -Ar -Br -CI -OR -OAr -O(C=O)R —NH, NHR, TNR, -NH(C=O)R Alpha (a) substituent Methyl Methylene Methine 0.0 0.8 0.9 1.0 0.9 1.2 1.4 1.1 1.1 1.1 1.2 1.7 1.0 1.8 1.1 2.1 2.2 2.3 INNNN 2.1 2.8 2.8 3.1 1.5 2.1 2.3 Base values trans Base value gem 0.45 1.26 0.64 0.70 0.97 0.80 1.02 1.10 1.82 1.38 1.07 1.08 1.22 1.21 2.11 0.80 2.08 0.9 ppm 1.2 ppm 1.5 ppm Beta (3) substituent 0.0 0.2 0.1 gem 0.3 0.3 0.4 0.4 0.3 0.3 0.4 0.3 0.3 0.3 0.4 0.4 0.7 0.5 0.3 0.3 0.5 a. There may be differences of 0.1-0.5 ppm in the chemical shift values calculated from this table and those measured from individual spectra. b. Ar= aromatic group. TABLE 22.5 Additive Parameters for Predicting NMR Chemical Shifts of Vinyl Protons in CDCI, 0.5 0.5 0.2 0.3 0.4 5.28 ppm cis -0.22 0.08 -0.01 -0.11 1.41 1.18 0.95 1.12 1.13 Gamma (y) substituent 0.36 0.45 0.18 -1.07 -0.60 -0.35 -1.26 -0.57 H- trans -0.28 -0.01 -0.02 -0.04 0.71 0.55 1.17 0.87 0.63 -0.07 0.55 0.13 -1.21 -1.00 -0.64 1.21 -0.72 0.0 0.1 0.0 0.1 0.1 a. There may be small differences in the chemical-shift values calculated from this table and those measured from individual spectra. 0.2 0.1 0.1 0.1 0.1 0.0 0.1 0.1 ddddddddddddd 0.1 0.2 0.2 0.2 0.1 0.1 0.3 0.1 0.2 0.1 0.1 0.1
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