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TRANSCRIPT
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48
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FTIR, FT−RAMAN, CONFORMATIONAL STUDIES,
THE MOLECULAR GEOMETRY AND VIBRATIONAL
FREQUENCIES OF 5−BROMO−O−ANISALDEHYDE
AND 3−FLUORO−P−ANISALDEHYDE
4.1. INTRODUCTION
Anisole is one of the simplest aromatic compound to which ether group
is linked. But it is different with aromatic compounds like furan where the
oxygen is a part of the ring. Anisole, C6H5OCH3 (methyl phenyl ether), is a
clear liquid that is soluble in ether and alcohol insoluble in water boiling point
155°C. Anisole and its derivatives are used as solvents and in perfumery.
Anisole can be obtained from anise seed. Anisic acid, p-methoxybenzoic acid,
is a part of cresol class antiseptic compounds. It is also used as an insect
repellent and ovicide. Anisole, anisic acid, and their derivatives are also widely
used in chemical reaction as intermediates to obtain target materials such as
dyes, pharmaceuticals, perfumes, photoinitiators and agrochemicals.
p-Anisaldehyde, an aromatic aldehyde with mothoxy gruop, is a clear liquid
may discolor to yellow on storage (limited shelf life for 6 months) melting at
-1°C, boiling at 249.5°C insoluble in water, soluble in alcohol and ether. It is
used in the synthesis of other organic compounds including pharmaceuticals
(especially antihistamines), agrochemicals, dyes and plastic additives. It is an
important intermediate for the processing of perfumes and flavouring
compounds.
49
Benzaldehyde (also called Benzenecarbonal) is the simplest
representative of the aromatic aldehydes. It is a colorless liquid aldehyde with a
characteristic almond odor. It boils at 180°C, is soluble in ethanol, but is
insoluble in water. Benzaldehyde is formed by partial oxidation of benzyl
alcohol and readily oxidized to benzoic acid and is converted to addition
products by hydrocyanic acid or sodium bisulfite. It is also prepared by
oxidation of toluene or benzyl chloride or by treating benzal chloride with an
alkali, e.g., sodium hydroxide. It is used chiefly in the synthesis of other
organic compounds, ranging from pharmaceuticals to plastic additives and
benzaldehyde is an important intermediate for the processing of perfume and
flavouring compounds and in the preparation of certain aniline dyes. It is the
first step in the synthesis for fragrances. It undergoes simultaneous oxidation
and reduction with alcoholic potassium hydroxide, giving potassium benzoate
and benzyl alcohol. It is converted to benzoin with alcoholic potassium
cyanide, with anhydrous sodium acetate and acetic anhydride, giving cinnamic
acid. Compounds which do not have alpha-hydrogen atoms cannot form an
enolate ion and do not undergo electrophilic alpha-substitution and aldol
condensation. Aromatic aldehydes such as benzaldehyde and formaldehyde
may undergo disproportionation in concentrated alkali (Cannizaro's reaction)
one molecule of the aldehyde is reduced to the corresponding alcohol and
another molecule is simultaneously oxidized to the salt of a carboxylic acid.
The speed of the reaction depends on the substituents in the aromatic ring.
50
Two different types of aldehydes (aromatic and aliphatic) can undergo crossing
reaction to form fomaldehyde and aromatic alcohols.
The assignment of bands in the vibrational spectra of aromatic and
another conjugated systems are an essential step in application of vibrational
spectroscopy for solving various structural chemical problems. Assignments
for complex systems can be proposed on the basis of frequency agreement
between the computed harmonics and the observed fundamentals. Density
functional theory (DFT) is becoming increasingly popular among
experimentalists and theoreticians in the present chemical literature [88,89].
Numerous reports have been made citing the success of DFT compared with
the conventional ab initio methods in computing molecular and chemical
properties such as geometries, harmonics frequencies, and energies [57,90-92].
DFT is superior to the conventional methods such as Hartree-Fock (HF) and
second-order Moller-Plesset perturbation theory (MP2), for the calculation of
polyatomic vibrational frequencies with empirical scaling factors approaching
unity [57,58]. The cost effectiveness of DFT over conventional methods is an
additional feature.
In this study, the conformational behaviour and vibrational analysis of
5-bromo-o-anisaldehyde (BOA) and 3-fluoro-p-anisaldehyde (FPA) have been
carried out by the application of the Becke3-Lee-Yang-Parr (B3LYP)/6-31+G(d,p)
basis sets-based on scaled quantum mechanical (SQM) method [62]. The
energies have been carried out for the various possible conformers of the title
51
compounds and the optimized geometrical parameters also obtained by the
DFT calculations. Based on these calculations, the calculated frequencies
were obtained. The observed and the calculated frequencies agree well.
4.2. EXPERIMENTAL PROCEDURES
BOA and FPA were purchased from Lancaster Chemical Company, UK
and used without further purification. Fourier transform infrared spectra for the
title compounds were recorded in the region 4000 - 400 cm-1
using BRUKER
IFS 66V FTIR spectrometer equipped with an MCT detector, a KBr beam
splitter and globar source at a resolution of ±1 cm-1
. The FT-Raman spectra
were recorded on the same instrument with FRA 106 Raman accessories in the
region 3500 - 100 cm-1
. The 1064 nm Nd:YAG laser was used as excitation
source, and the laser power was set to 200 mW.
4.3. COMPUTATIONAL METHODS
The molecular geometry optimizations and vibrational frequency
calculations were performed with the GAUSSIAN 03W software package [75]
with B3LYP-DFT functional and the standard 6-31+G(d,p) basis set [59,60].
The normal grid (50,194) was used for numerical integration. The Cartesian
representation of the theoretical force constants has been computed at the fully
optimized geometry by assuming Cs point group symmetry. Scaling of the
force fields was performed by the scaled quantum mechanical (SQM)
procedure with selective scaling in the local symmetry coordinate
52
representation [55] using transferable scale factors available in the literature
[62]. The transformations of the force field and the subsequent normal
coordinate analysis including the least square refinement of the scaling factors
calculation of the total energy distribution (TED), and the prediction of IR and
Raman intensities were done on a PC with the MOLVIB program (Version
V7.0 - G77) written by Tom Sundius [68,69]. For the plots of simulated IR and
Raman spectra, pure Lorentzian band shapes were used with a bandwidth
(FWHM) of 10 cm-1
.
The vibrational modes were assigned by means of visual inspection
using the GAUSSVIEW program [93]. The symmetry of the molecule was
also helpful in making vibrational assignments. The symmetries of the
vibrational modes were determined by using standard procedure [62,52] of
decomposing the traces of the symmetry operations into the irreducible
represents. The symmetry analysis for the vibrational modes of BOA and FPA
were presented in some detail in order to better describe the basis for the
assignments.
The Raman activities (Si) calculated with the GAUSSIAN-03 program
and adjusted during the scaling procedure with MOLVIB were converted to
relative Raman intensities (Ii) using the following relationship derived from the
basic theory of Raman scattering [94-96].
Ii = 4
o i i
ii
f(� - � ) S
hc�� 1- exp -
kT
� � � �� � �� �
... (4.1)
53
where νo is the exciting frequency (in cm-1
), νi is the vibrational wavenumber
of the ith
normal mode, h, c and k are fundamental constants, and f is a suitably
chosen common normalization factor for all peak intensities.
4.4. RESULTS AND DISCUSSION
4.4.1. Geometrical parameters
The molecular structures and stable conformers of BOA and FPA were
belong to Cs symmetry and were shown in Figs. 4.1 and 4.2, respectively. In
order to find the most optimized geometry, the energy calculations were carried
out for various possible conformers. The global minimum energy calculations
of the title compounds were found using 6-31+G(d,p) (for four different
possible conformers. The total energies obtained for these conformers were
listed in Table 4.1. The stable conformers Fig. 4.1(c) of BOA and Fig. 4.2(c)
of FPA have produced the global energy minimum. The most optimized
geometrical parameters for BOA and FPA were also calculated and they were
listed in Table 4.2 and 4.3, respectively.
4.4.2. Vibrational band assignments
Both the molecules BOA and FPA having 18 atoms give rise to 48
normal modes of vibrations and they were distributed among the symmetry
species as Γvib = 33A' + 15A". The A' and A" represents the in-plane and
out-of-plane vibrations, respectively. All vibrations are active both in the
infrared absorption and Raman scattering.
(a) (b)
(d) (c)
Fig.4.1: Molecular structure and various conformers of 5-bromo-o-anisaldehyde
(a) (b)
(d) (c)
Fig.4.2: Molecular structure and variable conformers of 3-fluoro-p-anisaldehyde
54
Detailed description of vibrational modes can be given by means of
normal coordinate analysis. For this purpose, the full sets of (61 for both BOA
and FPA) standard internal coordinates (containing 13 redundancies for both
the title compounds) were defined as given in Tables 4.4 and 4.5, respectively.
From these, a non-redundant set of local symmetry coordinates were
constructed by suitable linear combinations of internal coordinates following
the recommendations of Fogarasi and Pulay [97] and they were presented in
Tables 4.6 and 4.7. The theoretically calculated DFT force fields were
transformed to this later set of vibrational coordinates and used in all
subsequent calculations.
The observed, calculated frequencies, calculated IR and Raman
intensities and normal mode descriptions (characterized by TED) for the
conformers (Figs.4.1 (c) and 4.2(c)) of the title compounds were presented in
Tables 4.8 and 4.9, respectively. The observed FT-IR and FT-Raman spectra
of the title compounds were presented in Figs. 4.3 - 4.6, which helps to
understand the observed spectral features.
Root mean square error of the frequencies (unscaled) observed for BOA
and FPA were found 84.45 and 82.11 cm-1
, respectively. In order to reproduce
the observed frequencies, refinement of scaling factors were applied and
optimized via least square refinement algorithm which resulted a weighted
RMS deviation 4.8 cm-1
for BOA and 4.3 cm-1
for FPA, respectively, between
the experimental and scaled quantum frequencies for 6-31+G(d,p) basis set.
Fig
. 4.3
: F
T-I
R S
pec
tru
m o
f 5-
bro
mo-
o-an
isal
deh
yde
40
0
Fig
. 4.4
: F
T-R
aman
Sp
ectr
um
of
5-b
rom
o-o-
anis
ald
ehyd
e
Fig
. 4.5
: F
T-I
R S
pec
tru
m o
f 2-
flu
ro-p
-an
isal
deh
yde
Fig
. 4.6
: F
T-R
aman
Sp
ectr
um
of
2-fl
uro
-p-a
nis
ald
ehyd
e
55
The vibrational frequencies of the various functional groups present in the title
compounds were discussed below:
C–H Vibrations
The aromatic structure shows the presence of C–H stretching vibrations
in the region 3100–3000 cm–1
which is the characteristic region for the ready
identification of the C–H stretching vibrations. In this region, the bands are not
affected appreciably by the nature of the substitutents. Hence, in the present
investigation, the FT-IR and FT-Raman bands are observed at 3103, 3073,
3015 cm–1
and 3051, 3022, 3000 cm–1
, respectively in BOA and FPA have
been designated to C–H stretching vibrations. The B3LYP level at 6-31+G(d,p)
after scaling down give the frequency values at 3106, 3082, 3009 cm–1
and
3060, 3026, 3003 cm–1
. In general the aromatic C–H vibrations calculated
theoretically are in good agreement with the experimentally reported values
[10,98] for trisubstituted benzene.
The in-plane aromatic C–H deformation vibrations occur in the region
1450–990 cm–1
. The bands are sharp but are weak to medium intensity. The
C–H in-plane bending vibrations computed at 1491, 1466, 1453 cm-1
and 1395,
1389, 1345 cm-1
for BOA and FPA by B3LYP method shows good agreement
with experimental value. The medium and very strong intensity bands at 1497,
1480, 1461 cm–1
and 1396, 1285 cm–1
in FT-IR spectra are due to in-plane C–H
deformations for BOA and FPA, respectively. The same vibrations appear in
56
the Raman spectra at 1460 cm–1
with medium intensity for BOA and 1348 cm–1
in FT-Raman for FPA.
C–H out-of-plane bending vibrations are strongly coupled vibrations and
occur in the region 900–667 cm–1
[99]. Theoretically computed frequencies at
1145, 1106, 1018 cm-1
and 1020, 949, 885 cm–1
for BOA and FAP by
B3LYP/6-31+G(d,p) method are assigned to C–H out-of-plane bending
vibrations coincides with experimental value. In this current work, the peaks at
1142, 1100, 1020 cm–1
in IR, and 1095 cm–1
in FT-Raman while the peaks at
1021, 949, 884 cm–1
in IR counterpart confirms the C–H out-of-plane bending
vibration for BOA and FPA, which agrees with the above said literature values
[82,99].
C–C Vibrations
The bands 1430–1650 cm–1
were assigned to C–C stretching modes [1].
Socrates [48] mentioned that the presence of conjugate substituents such as
C=C causes a heavy doublet formation around the region 1625–1575 cm–1
. The
six ring carbon atoms undergo coupled vibrations, called skeletal vibrations
and give a maximum of four bands with region 1660–1220 cm–1
[100]. As
predicted in the earlier references, in this title compounds also there are
prominent peaks at 1634, 1593, 1575, 1395, 1267, 1244, 1179 cm–1
for BOA
and 1610, 1588, 1586, 1186, 1121 cm–1
for FPA due to strong C–C stretching
vibrations. The C–C in-plane bending results 705 cm–1
and 750 cm–1
harmonic
57
frequencies calculated by B3LYP/6-31+G(d,p) method for the title molecules
show good agreement with experimental results.
Aldehyde group vibrations
The C–H stretching vibrations of the aldehyde group [101] usually
appear in the region 2806–2871 cm–1
. Hence, in the present work, the C–H
stretching vibrations computed by B3LYP/6-31+G(d,p) method at 2886 cm–1
for BOA and 2835 cm–1
for FPA show very good agreement with recorded
value. The weak band observed in the FT-IR spectra 2878 and 2830 cm–1
for
BOA and FPA, respectively are due to C–H stretching vibration of the
aldehyde group. The in-plane C–H deformation mode of aldehyde group is
observed at 1480 and 1388 cm–1
with weak intensity both in the FT-IR spectra
for the title molecules. The carbonyl (C=O) stretching vibrations in the
substituted benzaldehydes is reported near 1700 cm–1
[48]. The very strong
band centered at 168 cm–1
in FT-IR and 1681 cm–1
in FT-Raman for BOA and
1693 cm–1
in FT-IR spectrum for FPA are attributed to C=O stretching
vibrations of the aldehyde group. Singh et al., [102] have assigned the C=O
in-plane bending vibrations for isomers of methoxy benzaldehydes in the
region 585–820 cm–1
. Hence, in the present investigation, the strong bands
observed at 824 cm–1
and 836 cm–1
for BOA and FPA, respectively, could be
assigned to C=O in-plane bending vibrations. Hanken et al., [103] have
assigned the band at 173 cm–1
in the Raman spectrum of chlorobenzalddehyde
as aldehyde out-of-plane bending vibration. In BOA and FPA, respectively the
58
very weak band centered at 188 cm–1
and 230 cm–1
in Raman spectra could be
due to C=O out-of-plane bending vibrations of aldehyde groups. A weak to
medium intensity band due to the aldehyde group CHO deformation vibration
[104] is found in the region 975–780 cm–1
. In consonance with this, the
medium and weak intensity band at 803 cm–1
and 813 cm–1
could be assigned
to CHO out-of-plane deformation for MHB and HMB, respectively.
CH3 group vibrations
In the region of 3102-2843 cm-1
, three bands have been observed at
2967, 2941 and 2843 cm-1
for BOA, have been assigned to two CH3
asymmetrical (CH3 ips) and symmetrical (CH3 ss) in-plane stretching modes,
asymmetric (CH3 ops) out-of-plane stretch modes of methyl group and three
CH stretching vibrations. In FPA, there were 6 bands have been observed
between the region 3251-2811 cm-1
were assigned to the CH3 asymmetric and
symmetric in-plane stretches, CH3 asymmetric out-of-plane stretches, CH2
asymmetric and symmetric stretches and CH stretches based on the calculated
frequencies and Raman activities. The bands due to the scissoring, rocking,
wagging and twisting modes of methylene group and rocking and wagging
modes of methyl groups of the title compounds have also been assigned and
listed in Tables 4.8 and 4.9.
C–Br vibrations
Strong characteristic absorption due to the C–Br stretching vibration is
observed [48] with the position of the band being influenced by neighboring
59
atoms or groups, the smaller the halide atom, the greater the influence of the
neighbour. Bands of weak to medium intensity are also observed for the C–Br
stretching vibrations. According to these early reports [104,105], the C–Br
stretching vibration gives generally strong band in the region 650–485 cm–1
. In
the present compound, a strong band is observed at 623 cm–1
in FT-IR
spectrum and 627 cm-1
in FT-Raman spectrum are assigned to C–Br stretching
vibrations for BOA. The calculated C–Br stretching bands are found at
625 cm–1
and this assignment is slightly above the literature value.
The theoretically computed value at 364 cm–1
is assigned to C–Br
in-plane by B3LYP/6-31+G(d,p) method. The C−Br in-plane bending bands
are observed at 362 cm–1
in FT-Raman spectrum. The C–Br out-of-plane
bending bands are observed at 201 cm–1
in FT-Raman spectrum and is assigned
to C–Br out-of-plane bending of BOA. This shows that the other vibrations can
hold back the C–Br vibrations due to its weak force constant [106]. The
influence of other substitution on C–Br stretching and deformation band is
significant in this compound.
C–F vibration
Aromatic fluorine compounds give stretching bands in the region
1270-1100 cm-1
[106]. The very strong band at 1226 cm-1
in FPA is assigned
to C-F stretching vibration. The predicted band corresponding to C-F
stretching mode is 1228 cm-1
. C-F in-plane bending vibrations are expected in
the range 420-254 cm-1
[10,106]. In FPA, a weak band at 504 cm-1
and
60
computed value 505 cm-1
is assigned to C-F in-plane-bending vibration. C-F
out-of-plane bending vibrations were observed in the range 520-101 cm-1
[106,107]. The observed FT-Raman band at 176 cm-1
is assigned to C-F
out-of-plane vibration.
4.5. CONCLUSION
In this study, the SQM force field method based on DFT calculations at
the B3LYP/6-31+G(d,p) level have been carried out to analyse the vibrational
assignments of BOA and FPA. Refinement of the scaling factors applied in
this study achieved a weighted RMS deviation of 4.8 cm-1
for BOA and for
FPA, 4.3 cm-1
for the 6-31+G(d,p) basis set, respectively, between the
experimental and SQM frequencies. The close agreement established between
the experimental and scaled frequencies obtained using the basis set
(6-31+G(d,p)) calculation are proved to be more reliable. This accuracy is
desirable for resolving disputes in vibrational assignments and provides
valuable insight for understanding the observed spectral features.
61
Table 4.1
Total energies of different conformations of 5-bromo-o-anisaldehyde and 3-fluoro-p-anisaldehyde, calculated at the DFT (B3LYP)/6-31+G(d,p) level of theory
Total energies (in Hartrees)
Conformer
BOA FPA
a -3031.232151 -559.345051
b -3031.080163 -559.347346
c -3031.236802* -559.320102*
d -3031.157013 -559.35236
*global minimum energy
62
Tab
le 4
.2
Op
tim
ized
geo
met
rica
l p
aram
eter
s of
5-b
rom
o-o-
anis
ald
ehyd
e ob
tain
ed b
y B
3LY
P/6
-31+
G(d
,p)
den
sity
fu
nct
ion
al
calc
ula
tion
s
Par
amet
ers
Bon
d l
engt
h (
Å)
Par
amet
ers
Bon
d a
ngl
e(°)
P
aram
eter
s D
ihed
ral
angl
e(°)
C1
-C2
1
.39
97
C
2-C
1-C
6
11
9.9
C
6-C
1-C
2-C
3
−0
.00
03
C1
-C6
1
.38
91
C
2-C
1-C
7
12
1.1
C
6-C
1-C
2-O
10
1
80
.0
C1
-C7
1
.48
68
C
6-C
1-C
7
11
8.8
C
7-C
1-C
2-C
3
0.0
C2
-C3
1
.39
07
C
1-C
2-C
3
11
9.4
C
7-C
1-C
2-O
10
−
18
0.0
C2
-O1
0
1.3
41
7
C1
-C2
-O1
0
11
6.7
C
2-C
1-C
6-C
5
0.0
C3
-C4
1
.38
53
C
3-C
2-O
10
1
23
.7
C2
-C1
-C6
-H1
8
0.0
C3
-H1
5
1.0
71
9
C2
-C3
-C4
1
19
.9
C7
-C1
-C6
-C5
−
17
9.9
C4
-C5
1
.38
30
C
2-C
3-H
15
1
21
.1
C7
-C1
-C6
-H1
8
18
0.0
C4
-H1
6
1.0
74
0
C4
-C3
-H1
5
11
8.8
C
2-C
1-C
7-O
8
0.0
C5
-C6
1
.89
19
C
3-C
4-C
5
12
0.4
C
2-C
1-C
7-H
9
−0
.00
08
C5
-Br1
7
1.3
78
7
C3
-C4
-H1
6
11
9.3
C
6-C
1-C
7-O
8
−0
.00
08
C6
-H1
8
1.0
73
0
C5
-C4
-H1
6
12
0.1
C
6-C
1-C
7-H
9
−1
80
.00
09
C7
-O8
1
.93
70
C
4-C
5-C
6
12
0.0
C
1-C
2-C
3-C
4
0.0
00
1
C7
-H9
1
.08
76
C
4-C
5-B
r17
11
9.8
C
1-C
2-C
3-H
15
1
80
.00
07
O1
0-C
11
1
.40
59
C
6-C
5-B
r17
1
20
.1
O1
0-C
2-C
2-C
4
17
9.9
C1
1-H
11
1
.08
44
C
1-C
6-C
5
12
0.2
O
10
-C2
-C3
-H1
5
−0
.00
09
63
C1
1-H
12
1
.07
92
C
1-C
6-H
18
1
18
.4
C1
-C2
-O1
0-C
11
1
80
.0
C1
1-H
13
1
.08
44
C
5-C
6-H
18
1
21
.3
C1
-C2
-O1
0-C
11
0
.00
33
C1
-C8
-O8
1
23
.0
C2
-C3
-C4
-C5
0
.00
02
C1
-C7
-H9
1
16
.1
C2
-C3
-C4
-H1
6
18
0.0
O8
-C7
-H9
1
20
.8
H1
5-C
3-C
4-C
5
−1
80
.0
C2
-O1
0-C
11
1
20
.5
C3
-C4
-C5
-C6
−
0.0
00
2
O1
0-C
11-H
12
1
11
.0
C3
-C4
-C5
-Br1
7
−1
80
.0
O1
0-C
11-H
13
1
05
.8
H1
6-C
4-C
5-C
6
−1
80
.0
O1
0-C
11-H
14
1
11
.0
H1
6-C
4-C
5-B
r17
−
0.0
00
1
H1
2-C
11-H
13
1
09
.3
C4
-C5
-C6
-C1
0
.0
H1
2-C
11-H
14
1
09
.9
C4
-C5
-C6
-H1
8
18
0.0
H1
3-C
11-H
14
1
09
.3
Br1
7-C
5-C
6-H
18
1
80
.
Br1
7-C
5-C
6-C
1
0.0
00
1
C2
-O1
0-H
11
-H1
2
61
.4
C2
-O1
0-H
11
-H1
3
−1
79
.9
C2
-O1
0-H
11
-H1
4
−6
1.2
Fo
r n
um
ber
ing o
f at
om
ref
er F
ig.
4.2
.
64
Tab
le 4
.3
Op
tim
ized
ge
omet
rica
l p
aram
eter
s of
3-
flu
oro-
p-a
nis
ald
ehyd
e ob
tain
ed
by
B3L
YP
/6-3
1+G
(d,p
) d
ensi
ty f
un
ctio
nal
ca
lcu
lati
ons
Par
amet
ers
Bon
d l
engt
h (
Å)
Par
amet
ers
Bon
d a
ngl
e(°)
P
aram
eter
s D
ihed
ral
angl
e(°)
C1
-C2
1
.40
69
C2
-C1
-C6
1
19
.3
C6
-C1
-C2
-C3
0
.00
11
C1
-C6
1
.40
14
C2
-C1
-C7
1
19
.5
C6
-C1
-C2
-H1
0
17
9.9
C1
-C7
1
.47
55
C6
-C1
-C7
1
21
.1
C7
-C1
-C2
-C3
−
17
9.9
C2
-C3
1
.37
92
C1
-C2
-C3
1
19
.5
C7
-C1
-C2
-H1
0
−0
.00
1
C2
-H1
0
1.0
86
3
C1
-C2
-H1
0
12
1.3
C
2-C
1-C
6-C
5
−0
.00
12
C3
-C4
1
.40
85
C3
-C2
-H1
0
11
9.1
C
2-C
1-C
6-H
18
−
18
0.0
C3
-F1
1
1.3
53
2
C2
-C3
-C4
1
21
.9
C7
-C1
-C6
-C5
−
18
0.0
C4
-C5
1
.40
55
C2
-C3
-F1
1
11
9.7
C
7-C
1-C
6-H
18
−
0.0
02
3
C4
-O1
26
1
.35
15
C4
-C3
-F1
1
11
8.2
C
2-C
1-C
7-O
8
−1
79
.9
C5
-C6
1
.39
29
C3
-C4
-C5
1
18
.0
C2
-C1
-C7
-H9
0
.0
C5
-H1
7
1.0
83
3
C3
-C4
-O1
2
11
6.3
C
6-C
1-C
7-O
8
0.0
C6
-H1
8
1.0
85
1
C5
-C4
-O1
2
12
5.6
C
6-C
1-C
7-H
9
−1
79
.9
C7
-O8
1
.21
98
C4
-C5
-C6
1
20
.3
C1
-C2
-C3
-C4
0
.0
C7
-H9
1
.11
14
C4
-C5
-H1
71
20
.0
C1
-C2
-C3
-F1
1
−1
80
.0
O1
2-C
13
1
.42
74
C6
-C5
-H1
7
11
9.5
H
10
-C2
-C2
-C4
1
80
.0
C1
3-H
14
1
.08
98
C1
-C6
-C5
1
20
.7
H1
0-C
2-C
3-F
11
0
.0
65
C1
3-H
15
1
.09
61
C1
-C6
-H1
8
11
8.7
C
2-C
3-C
4-C
5
−0
.00
18
C1
3-H
16
1
.09
61
C5
-C6
-H1
8
12
0.3
C
2-C
3-C
4-O
12
−
17
9.9
C1
-C8
-O8
1
24
.8
F1
1-C
3-C
4-C
5
17
9.9
C1
-C7
-H9
1
14
.7
F1
1-C
3-C
4-O
12
0
.0
O8
-C7
-H9
1
20
.3
C3
-C4
-C5
-C6
0
.0
C4
-O1
2-C
13
11
8.6
C
3-C
4-C
5-H
17
1
80
.0
O1
2-C
13
-H1
4
10
5.4
O
12
-C4
-C5
-C6
−
18
0.0
O1
2-C
13
-H1
5
11
1.1
O
12
-C4
-C5
-H1
7
−0
.00
05
O1
2-C
13
-H1
6
11
1.1
C
3-C
4-O
12
-C1
3
18
0.0
H1
4-C
13
-H1
5
10
9.5
C
5-C
4-O
12
-C1
3
0.0
71
H1
4-C
13
-H1
6
10
9.5
C
4-C
5-C
6-C
1
−0
.00
02
H1
5-C
13
-H1
6
10
9.8
C
4-C
5-C
6-H
18
−
17
9.9
H1
7-C
5-C
6-C
1
−1
80
.0
H1
7-C
5-C
6-H
18
−
0.0
01
4
C4
-O1
2-C
13
-H1
4
−1
80
.0
C4
-O1
2-C
13
-H1
5
−1
61
.3
C4
-O1
2-C
13
-H1
6
−6
1.2
Fo
r n
um
beri
ng
of
ato
m r
efer
Fig
. 4
.3.
66
Table 4.4
Definition of internal coordinates of 5-bromo-o-anisaldehyde
No. (i) Symbol Type Definition
Stretching
1-3 ri C-H C3-H15, C4-H16, C6-H18
4 Ri C-C C1 – C7
5 ri C-H C7 – H94
6-7 pi C-O C2-O10, C11-O10
8 Pi C-Br C5 – Br17
9 pi C=O C7 – O8
10-12 ri C-H C11 - H12, C11 - H13, C11 - H14
13-18 qi C-C C1 - C2, C2 - C3, C3 - C4, C4 - C5,
C5 - C6, C6 - C1
Bending
19-24 βi bCH C1 - C6-H18, C5-C6-H18, C5-C4-H16,
C3-C4-H16, C4-C3-H15, C2-C3-H15
25-26 αi bCC C2-C1-C7, C6-C1-C7
27-28 σi bCO C1-C2-O10, C3-C2-O10
29-30 ρi BCBr C4-C5-Br17, C6-C5-Br17
31 αi bCC C1-C7-H9
32 αi bCC C1-C7-O8
33 δi bOH O8-C7-H9
34-36 φi bOC O10-C11-H12, O10-C11-H13,
O10-C11-H14
37-39 πi H-C-H H12-C11-H13, H12-C11-H14,
H13-C11-H14
40-45 γi C-C-C C1-C2-C3, C2-C3-C4, C3-C4-C5,
C4-C5-C6, C5-C6-C1, C6-C1-C2
67
Out-of-plane bending
46-48 ωi C-H H15-C3-C2-C4, H16-C4-C3-C5,
H18-C5-C1-C5
49 ϕi C-C C7-C1-C2-C6
50 i C-O O10-C2-C1-C3
51 ψi C-Br Br17-C5-C4-C6
52 θi O-H O8-C7-C1-C6 (C2)
53 ωi C-H H9-C7-C1-C6(C2)
54 τi t CO C2-O10-C11-(H12, H13, H14)
55 τi t CO H9-C7-O8-C1
56-61 τi t Ring C1-C2-C3-C4, C2-C3-C4-C5,
C3-C4-C5-C6, C4-C5-C6-C1,
C5-C6-C1-C2, C6-C1-C2-C3
For numbering of atoms refer Fig.4.2
68
Table 4.5
Definition of internal coordinates of 3-fluoro-p-anisaldehyde
No. (i) Symbol Type Definition
Stretching
1-3 ri C-H C2-H10, C5-H17, C6-H18
4 Ri C-C C1-C7
5 ri C-H C7-H94
6-7 pi C-O C4-O12, C13-O12
8 Pi C-Br C3-F11
9 pi C=O C7-O8
10-12 ri C-H C13-H14, C13-H15, C13-H16
13-18 qi C-C C1-C2, C2-C3, C3-C4, C4-C5, C5-C6,
C6-C1
In-plane Bending
19-24 βi bCH C1-C6-H10, C3-C2-H10, C1-C6-H18,
C5-C6-H18, C6-C5-H17, C4-C5-H17
25-26 αi bCC C2-C1-C7, C6-C1-C7
27-28 σi bCO C3-C4-O12, C5-C4-O12
29-30 ρi bCBr C2-C3-F11, C4-C3-F11
31 αi bCC C1-C7-H9
32 αi bCC C1-C7-O8
33 δi bOH O8-C7-H9
34-36 φi bOC O12-C13-H14, O12-C13-H15,
O12-C13-H16
37-39 πi H-C-H H14-C13-H15, H14-C13-H15,
H15-C13-H16
40-45 γi C-C-C C1-C2-C3, C2-C3-C4, C3-C4-C5,
C4-C5-C6, C5-C6-C1, C6-C1-C2
69
Out-of-plane bending
46-48 ωi C-H H10-C2-C4-C3, H17-C5-C4-C6,
H18-C6-C1-C5
49 ϕi C-C C7-C1-C2-C6
50 i C-O O12-C4-C3-C5
51 ψi C-F F11-C3-C2-C4
52 θi O-H O8-C7-C1-C6 (C2)
53 ωi C-H H9-C7-C1-C6(C2)
54 τi t CO H9-C7-O8-C1
55 τi t CO C4-O12-C13-(H14, H15, H16)
56-61 τi t Ring C1-C2-C3-C4, C2-C3-C4-C5,
C3-C4-C5-C6, C4-C5-C6-C1, C5-C6-C1-C2,
C6-C1-C2-C3
For numbering of atoms refer Fig.4.3
70
Table 4.6
Definition of local symmetry coordinates of 5-bromo-o-anisaldehyde
No. (i) Symbol Definition
1-3 CH r1, r2, r3
4 CC R4
5 CH r5
6,7 CO p6, p7
8 CBr P8
9 CO p9
10 CH3 ss (r10+r11+r13) / 3
11 CH3 ips (2r10 -r11 -r13) / 6
12 CH3 ops (r11 -r12) / 2
13-18 CO q13, q14, q15, q16, q17, q18
19-21 bCH (β19 -β20) / 2 , (β21 -β22) / 2 , (β23 -β24) / 2
22 bCC (α25 - α26) / 2
23 bCO (σ27 - σ28) / 2
24 bCBr (ρ29 - ρ30) / 2
25 bCC α31
26 bCC α32
27 bOH δ33
71
28 CH3 sb (-φ34 – φ35 – φ36+ π37+ π38+ π39)/ 6
29 CH3 ipb (- π37 - π38 - 2π39)/ 6
30 CH3 opb (π38 - π39) / 2
31 CH3 ipr (2φ34 – φ35 – φ36) / 6
32 CH3 opr (φ35 – φ36) / 2
33 Rtrigd (γ40 -γ41+γ42 -γ43 + γ44 - γ45) / 6
34 Rsymd (-γ40 -γ41+2γ42 -γ43 - γ44 + 2γ45) / 12
35 Rasymd (γ40 -γ4 + γ43 - γ44) / 2
36-38 ωCH ω46, ω47, ω48
39 ωCC ϕ49
40 ωCO φ50
41 ωCBr ψ51
42 ωOH ω52
43 ωCH ω63
44 ωCO τ54
45 τCOH τ54
46 tRtrig (τ56+τ57+τ58+τ59+τ60+τ61) / 6
47 tRsym (τ56+τ57+τ59+τ60) / 2
48 tRasy (-τ56 +2τ57-τ58-τ59+2τ60-τ61)/ 12
72
Table 4.7
Definition of local symmetry coordinates of 3-fluoro-p-anisaldehyde
No. (i) Symbol Definition
1-3 CH r1, r2, r3
4 CC R4
5 CH r5
6,7 CO p6, p7
8 CBr P8
9 CO p9
10 CH3 ss (r10+r11+r13) / 3
11 CH3 ips (2r10 -r11 -r13) / 6
12 CH3 ops (r11 -r12) / 2
13-18 CO q13, q14, q15, q16, q17, q18
19-21 bCH (β19 -β20) / 2 , (β21 -β22) / 2 , (β23 -β24) / 2
22 bCC (α25 - α26) / 2
23 bCO (σ27 - σ28) / 2
24 bCF (ρ29 - ρ30) / 2
25 bCC α31
26 bCC α32
27 bOH δ33
73
28 CH3 sb (-φ34 – φ35 – φ36+ π37+ π38+ π39)/ 6
29 CH3 ipb (- π37 - π38 -2π39)/ 6
30 CH3 opb (π38 - π39) / 2
31 CH3 ipr (2φ34 – φ35 – φ36) / 6
32 CH3 opr φ35 – φ36) / 2
33 R trigd (γ40 -γ41+γ42 -γ43 + γ44 - γ45) / 6
34 R symd (-γ40 -γ41+2γ42 -γ43 - γ44 + 2γ45) / 12
35 R asymd (γ40 -γ4 + γ43 - γ44) / 2
36-38 ωCH ω46, ω47, ω48
39 ωCC ϕ49
40 ωCO φ50
41 ωCF ψ51
42 ωOH ω52
43 ωCH ω63
44 ωCO τ54
45 τCOH τ54
46 t R trig (τ56+τ57+τ58+τ59+τ60+τ61) / 6
47 t R symd (τ56+τ57+τ59+τ60) / 2
48 t R asymd (-τ56 +2τ57-τ58-τ59+2τ60-τ61)/ 12
74
Tab
le 4
.8
Th
e ob
serv
ed F
TIR
, F
T R
aman
an
d c
alcu
late
d (
Un
scal
ed a
nd
Sca
led
) fr
equ
enci
es (
cm-1
), I
R i
nte
nsi
ty (
kM
mol
-1),
R
aman
ac
tivi
ty
(Å
amu
-1),
R
edu
ced
m
asse
s (a
mu
) an
d
forc
e co
nst
ant
(md
yne
Å-1
) an
d
pro
bab
le
assi
gnm
ents
(c
har
acte
rize
d b
y T
ED
) of
5-b
rom
o-o-
anis
ald
ehyd
e u
sin
g B
3LY
P/6
-31+
G(d
,p)
Cal
cula
ted
fr
equ
enci
es (
cm-1
) F
un
dam
enta
ls (
cm-1
) S
ymm
etry
sp
ecie
s C
s
FT
-IR
R
aman
U
nsc
aled
S
cale
d
Red
uce
d
mas
s F
orce
co
nst
ants
In
frar
ed
inte
nsi
ty
Ram
an
acti
vity
T
ED
(%
) am
ong
typ
es o
f in
tern
al c
oord
inat
es
A′
31
03
ms
31
00
ms
34
03
3
10
6
1.0
94
5
7.4
00
8
.24
14
1.1
3
νC
H(9
9)
A′
30
73
ms
30
74
w
34
02
3
08
2
1.0
93
5
7.4
54
8
1.3
2
5.0
3
νC
H(9
9)
A′
30
15
ms
30
15
w
33
79
3
00
9
1.0
91
5
7.3
43
8
1.4
3
48
.22
ν
CH
(99
)
A″
29
67
ms
- 3
31
9
29
75
1
.10
28
7
.15
81
2
8.0
8
11
8.3
0
CH
3 a
s(8
5)
A′
29
41
ms
- 3
26
5
29
55
1
.10
78
6
.95
72
3
9.1
1
45
.32
C
H3as
(86
)
A′
28
78
w
28
81
w
32
36
2
88
6
1.0
89
2
6.7
21
7
54
.05
10
2.4
6
νC
H(9
7)
A′
28
43
w
28
48
w
31
94
2
84
9
1.0
33
6
6.2
12
5
54
.21
13
2.2
7
CH
3ss
(88
)
A′
16
80
vs
16
81
vs
19
67
1
68
5
9.8
14
2
22
.36
57
3
78
.79
93
.39
νC
O(9
3)
A′
16
34
w
- 1
79
3
16
41
5
.87
45
1
1.1
22
1
87
.96
74
.42
ν
CC
(84
), δ
CH
(12
)
A′
15
93
w
15
96
ms
17
64
1
59
0
7.0
90
6
12
.99
75
2
4.7
5
20
.07
ν
CC
(75
),δC
H(1
5),
δC
O(1
0)
A′
15
75
vs
15
72
ms
16
56
1
57
8
2.2
45
6
3.6
28
5
18
5.5
5
10
.05
ν
CC
(75
),δC
H(2
0)
A″
15
61
w
- 1
63
5
15
66
1
.06
92
1
.68
47
5
0.0
8
8.0
5
CH
3 o
pb
(8
4)
75
A′
15
33
w
- 1
62
9
15
30
1
.04
63
1
.63
67
8
.06
14
.79
C
H3 i
pb
(8
5)
A′
15
19
w
- 1
61
2
15
25
1
.24
57
1
.90
72
3
1.5
2
2.7
2
CH
3 s
b (
84
)
A′
14
97
vs
- 1
55
8
14
91
2
.27
68
3
.25
83
1
6.4
1
3.1
2
δC
H (
72
), ν
CC
(1
5)
A′
14
80
vs
- 1
54
1
14
80
1
.60
56
2
.24
68
1
29
.52
2.8
2
δC
H (
74
), ν
CC
(1
2)
A′
14
61
ms
14
60
ms
14
24
1
46
6
2.1
22
7
2.5
38
7
26
8.1
8
10
.98
δC
H (
74
), ν
CC
(1
4)
A′
14
55
ms
14
50
w
13
93
1
45
3
1.9
48
8
2.2
28
1
11
7.5
8
16
.81
δC
H (
74
), ν
CC
(1
0)
A′
14
41
w
- 1
33
2
14
40
1
.68
99
1
.76
64
7
.91
6.6
4
CH
3 i
pr(
76
),δC
H(2
0)
A′
13
95
vs
13
96
ms
13
07
1
39
4
1.6
77
2
1.6
88
2
19
.43
2.0
7
νC
C(7
1),
δC
H(1
5)
A″
12
98
vs
13
00
w
12
81
1
29
9
1.2
66
1
1.2
24
2
3.3
4
2.0
8
CH
3 o
pr(
79)
A′
12
67
vs
12
65
s 1
24
0
12
63
2
.26
76
2
.05
36
8
4.7
2
4.0
1
νC
C(7
1),
δC
H(1
6)
A′
12
44
w
- 1
23
4
12
46
6
.91
53
6
.20
50
5
7.4
3
40
.69
ν
CC
(70
), δ
CO
(16
)
A′
11
79
vs
11
80
vs
11
94
1
18
0
2.1
11
7
1.7
73
6
5.0
4
2.8
9
νC
C(7
5),
δC
H(1
2)
A″
11
42
ms
- 1
16
3
11
45
1
.89
49
1
.51
21
0
.00
3.5
7
γCH
(37
), γ
CC
(19
)
A′
11
26
w
11
25
w
11
56
1
12
8
6.2
88
5
4.9
54
0
55
.97
6.1
1
νC
O(4
2),
νC
C(1
8),
δC
H(1
5)
A″
11
00
w
10
95
w
11
09
1
10
6
1.4
50
1
1.0
52
4
0.1
0
0.1
6
γCH
(37
), γ
CC
(25
)
A″
10
20
vs
- 1
08
2
10
18
1
.50
28
1
.03
64
1
0.5
1
0.6
1
γCH
(40
), γ
CC
(32
)
A′
89
1m
s -
96
1
89
0
5.7
38
1
3.1
27
3
25
.73
3.0
1
δC
O(5
5),
δR
ing(3
2),
νC
Br(
12
)
A″
88
2vs
88
5w
9
38
8
84
1
.61
85
0
.83
81
4
1.6
9
0.3
8
γCH
(29
), γ
CC
(19
)
A′
82
4w
-
85
9
82
3
5.2
93
3
2.3
01
9
8.1
1
23
.06
δC
O(4
5),
νC
C(2
1),
δC
H(1
5)
76
A′
80
3w
7
99
s 8
29
8
04
3
.04
49
1
.23
18
4
.03
1.4
2
γCO
(3
5),
γC
H (
21)
A′
70
6m
s 7
06
w
72
0
70
5
2.8
09
2
0.8
59
4
12
.64
0.1
4
δC
C (
55
), δ
CO
(2
9)
A′
64
6s
65
1m
s 7
02
6
47
5
.85
49
1
.70
30
2
1.1
1
3.1
4
δR
ing(4
9),
δC
O(3
1)
A′
62
3s
62
7s
68
0
62
5
6.1
70
8
1.6
80
7
31
.18
3.1
4
νC
Br(
61),
δC
C(2
2),
δC
O(1
0)
A′
53
9w
-
56
5
54
0
5.9
48
2
1.1
22
2
33
.98
2.1
8
γCO
(55
), γ
CH
(19),
γR
ing(1
2)
A′
52
2s
52
5vw
5
23
5
23
3
.03
81
0
.49
09
6
.20
0.0
9
δR
ing(2
9),
δC
O(1
3)
A″
- 4
25
w
43
2
42
5
6.0
29
7
0.6
61
9
1.0
6
4.7
9
γRin
g(3
2),
γC
O(1
2)
A″
- 4
10
s 4
19
4
13
4
.41
33
0
.45
82
0
.18
1.3
2
γRin
g(3
1),
γC
O(1
8)
A′
- 3
62
w
35
1
36
4
5.1
86
5
0.3
77
6
4.8
5
1.3
1
δC
Br(
25
), δ
CO
(16
)
A′
- 3
18
w
29
5
32
0
9.7
94
0
0.5
05
1
2.3
3
8.0
6
δR
ing(2
9),
δC
O(1
8)
A″
- 2
58
s 2
65
2
56
1
.11
44
0
.04
64
0
.98
0.1
5
tCH
3 (
76
)
A″
- 2
01
ms
20
9
20
0
2.8
87
9
0.0
74
4
5.4
5
2.0
6
γCB
r(2
8),
γC
C(1
8)
A″
- 1
88
s 2
01
1
89
4
.30
98
0
.10
31
0
.14
0.8
6
γCO
(33
), γ
CC
(15
)
A″
- -
15
5
15
4
11
.67
13
0
.16
58
3
.39
1.4
2
γCO
(39
), γ
Rin
g(2
0)
A″
- -
14
4
14
6
4.3
95
0
0.0
54
3
14
.88
0.3
2
γCO
(28
), γ
Rin
g(1
5)
A″
- -
11
0
10
8
4.1
38
2
0.0
29
5
4.0
6
0.7
9
γCO
(27
), γ
Rin
g(1
5)
A″
- -
71
7
0
3.3
91
2
0.0
10
1
1.1
9
0.4
1
γCO
(28
), γ
Rin
g(1
3)
Ab
bre
via
tion
s:
t, t
ors
ion;
R1 t
rig
d,
Rin
g 1
tri
gonal
def
orm
ati
on;
R2 t
rig
d,
Rin
g 2
tri
gonal
def
orm
ati
on;
asy
m,
asy
mm
etri
c; s
, sy
mm
etri
c; �
, ben
din
g o
ut-
of-
pla
ne;
asy
md,a
sym
met
ric
def
orm
ati
on;
sym
d,
sym
met
ric
def
orm
ati
on;
b,
ben
din
g i
n-p
lane;
s,
stro
ng
; w
, w
eak;
m,
med
ium
; vs
, ve
ry w
eak;
ms,
med
ium
stro
ng,
Harm
onic
Fre
quen
cies
in c
m-1
. T
he
abso
lute
IR
inte
nsi
ty i
n K
m m
ol-1
. R
am
an s
catt
erin
g a
ctiv
ity
in A
4 a
mu
-1.
Dep
ola
riza
tion r
ati
ons
for
pla
ne
and u
np
ola
rise
d i
n a
mu.
Red
uce
d m
ass
es i
n A
MU
Forc
e co
nst
ants
in m
Dyn
e A
.
77
Tab
le 4
.9
Th
e ob
serv
ed F
TIR
, F
T R
aman
an
d c
alcu
late
d (
Un
scal
ed a
nd
Sca
led
) fr
equ
enci
es (
cm-1
), I
R i
nte
nsi
ty (
kM
mol
-1),
R
aman
ac
tivi
ty
(Å
amu
-1),
R
edu
ced
m
asse
s (a
mu
) an
d
forc
e co
nst
ant
(md
yne
Å-1
) an
d
pro
bab
le
assi
gnm
ents
(c
har
acte
rize
d b
y T
ED
) of
3-f
luor
o-p
-an
isal
deh
yde
usi
ng
B3L
YP
/6-3
1+G
(d,p
)
Cal
cula
ted
fr
equ
enci
es (
cm-1
) F
un
dam
enta
ls (
cm-1
) S
ymm
etry
sp
ecie
s C
s
FT
-IR
R
aman
U
nsc
aled
S
cale
d
Red
uce
d
mas
s F
orce
co
nst
ants
In
frar
ed
inte
nsi
ty
Ram
an
acti
vity
T
ED
(%
) am
ong
typ
es o
f in
tern
al c
oord
inat
es
A′
30
51
w
- 3
22
8
30
60
1
.09
31
6
.71
00
5
.68
1
12
.08
ν
CH
(98
)
A′
30
22
w
- 3
21
2
30
26
1
.08
88
6
.61
91
0
.23
3
9.1
7
νC
H(9
7)
A′
30
00
w
- 3
20
0
30
03
1
.09
13
6
.58
44
1
.70
8
8.8
ν
CH
(97
)
A″
29
41
ms
- 3
16
5
29
40
1
.10
10
6
.49
87
1
4.1
7
13
3.6
1
CH
3 a
s(8
2)
A′
28
47
w
- 3
09
9
28
44
1
.10
71
6
.26
45
2
9.7
9
56
.95
C
H3as
(82
)
A′
28
30
w
- 3
02
9
28
35
1
.03
37
5
.59
01
5
1.5
8
15
4.4
3
νC
H(9
5)
A′
28
11
ms
- 2
91
4
28
16
1
.08
36
5
.42
36
1
24
.22
16
9.6
2
CH
3ss
(85
)
A′
16
93
vs
15
95
vs
17
69
1
69
0
9.8
69
8
18
.19
33
3
04
.39
17
9.9
4
νC
O(9
0)
A′
16
10
vs
16
11
vs
16
52
1
61
5
6.4
76
8
10
.42
.14
2
15
.55
27
0.2
6
νC
C(7
8),
δC
H(1
2)
A′
15
88
s 1
58
8s
16
19
1
58
3
7.8
00
8
12
.05
13
5
8.8
1
5.4
5
νC
C(7
7),
δCH
(15),
δC
O(1
2)
A′
15
86
vs
- 1
55
5
15
19
3
.19
47
4
.55
52
1
32
.65
5.5
2
νC
C(7
5),
δC
H(2
2)
A″
14
62
w
- 1
50
6
14
61
1
.05
72
1
.41
36
4
1.7
5
8.7
6
CH
3 i
pb
(8
5)
78
A′
- 1
45
2m
s 1
50
1
14
52
1
.04
56
1
.38
74
9
.79
1
5.1
7
CH
3 o
pb
(8
6)
A′
14
43
s -
14
84
1
44
8
1.2
93
4
1.6
78
5
17
.52
4.4
2
CH
3 s
b (
84
)
A′
13
96
ms
- 1
46
8
13
95
2
.51
28
3
.18
52
1
1.7
6
1.4
3
δC
H(7
0),
νC
C (
19
)
A′
13
88
w
- 1
41
7
13
89
1
.57
31
1
.86
05
2
.77
9
.07
δC
H(7
5),
νC
C (
18
)
A′
- 1
34
8m
s 1
36
4
13
45
6
.21
28
6
.81
48
8
5.7
4
25
.02
δC
H(7
4),
νC
C (
14
)
A′
12
85
vs
12
89
ms
13
22
1
28
6
4.2
92
5
4.4
19
0
43
4.5
7
39
.02
δC
H(7
3),
νC
C (
12
)
A′
12
59
w
12
60
ms
13
03
1
25
7
1.7
70
8
1.7
72
5
30
.69
9.5
6
CH
3ip
r(7
7),
δC
H(1
8)
A′
12
26
ms
12
30
ms
12
47
1
22
8
2.8
18
2
2.5
82
0
30
.82
29
.10
ν
CF
(88
), δ
CH
(10
)
A″
11
86
w
- 1
20
8
11
85
1
.36
81
1
.17
67
2
.84
5
.94
ν
CC
(73
), δ
CH
(17
)
A′
11
53
w
- 1
17
9
11
53
1
.47
22
1
.20
62
8
.21
1
.68
C
H3 o
pr(
78
), ν
CC
(10
)
A′
11
21
vs
11
21
ms
11
72
1
12
4
1.2
68
8
1.0
27
1
0.9
7
1.8
7
νC
C(7
1),
δC
H(1
6)
A′
11
09
s -
11
32
1
10
5
1.7
52
6
1.3
24
3
13
7.5
9
12
.32
ν
CC
(68
), δ
CO
(14
)
A″
10
21
s 1
02
0w
1
05
2
10
20
7
.86
89
5
.14
01
4
3.9
6
1.7
8
νC
C(7
5),
δC
H(1
3)
A′
97
1w
-
10
23
9
74
1
.76
81
1
.09
13
1
.52
2
.45
γC
H(3
7),
γC
C(1
4)
A″
94
9m
s -
96
8
94
9
1.3
20
1
0.7
28
2
0.0
9
0.1
6
νC
O(4
0),
νC
C(1
8),
δC
H(1
1)
A″
89
4m
s -
96
3
89
7
3.6
27
0
1.9
83
2
20
.26
6.6
5
γCH
(39
), γ
CC
(25
)
A′
88
4m
s -
89
3
88
5
1.3
62
7
0.6
40
2
22
.51
0.1
6
γCH
(44
), γ
CC
(28
)
A″
83
6m
s -
82
8
83
8
1.4
44
6
0.5
84
0
35
.73
0.1
4
δC
O(5
4),
δR
ing(3
5),
A′
81
3m
s -
79
0
81
0
6.0
79
1
2.2
36
1
54
.72
13
.57
γC
H(2
9),
γC
C(1
9)
79
A′
78
3m
s 7
85
ms
77
3
78
5
4.6
44
0
1.6
35
2
11
.41
15
.56
δC
O(4
5),
νC
C(2
1),
δC
H(1
5)
A′
74
5m
s -
71
4
75
0
4.4
64
1
1.3
42
9
0.1
3
0.1
2
γCO
(3
7),
γC
H (
20)
A′
63
7m
s 6
38
ms
63
8
63
9
6.6
33
7
1.5
92
7
18
.74
1.0
3
δC
C (
55
), δ
CO
(2
9)
A′
58
6m
s -
59
2
59
0
5.7
41
1
.18
59
1
0.8
9
3.7
9
δR
ing(4
7),
δC
O(3
0)
A′
- 5
71
w
58
6
57
3
4.0
02
1
0.8
10
1
5.7
8
0.4
3
γCO
(52
),γC
H(2
0),
γRin
g(1
2)
A′
50
4w
-
49
0
50
5
7.1
17
9
1.0
09
0
9.3
9
5.6
7
δC
Br(
55
),ν
CC
(20
),δC
H(1
4)
A″
48
6w
-
46
7
48
9
3.1
91
9
0.4
10
7
0.9
0
0.4
4
δR
ing(3
0),
δC
O(1
2)
A″
41
0w
-
38
0
41
2
10
.04
94
0
.85
59
0
.46
7
.51
γR
ing(3
6),
γC
O(1
5)
A′
- 3
69
w
34
9
37
0
4.3
05
4
0.3
10
1
2.8
1
1.5
8
γRin
g(3
0),
γC
O(1
3)
A′
- 3
21
w
33
9
32
2
4.7
47
6
0.3
22
1
0.1
8
4.2
4
δR
ing(3
2),
δC
O(1
2)
A″
- 2
55
w
26
0
25
6
3.1
10
1
0.1
24
4
4.2
3
0.3
1
tCH
3 (
74
)
A″
- 2
36
w
23
6
23
6
1.1
60
3
0.0
38
1
0.2
4
0.4
5
γCO
(31
), γ
CC
(17
)
A″
- 2
30
w
23
3
23
1
5.6
46
5
0.1
81
3
3.6
6
0.3
4
γCO
(36
), γ
Rin
g(2
2)
A″
- 1
76
w
16
7
17
5
5.5
55
9
0.0
92
0
8.5
5
1.2
3
γCF
(33
), γ
Rin
g(2
0)
A″
- 1
16
w
15
9
16
3
3.5
41
6
0.0
53
0
0.5
8
2.3
9
γCO
(27
), γ
Rin
g(1
6)
A″
- 1
06
w
11
3
10
5
4.5
26
0
0.0
34
5
14
.52
1.4
3
γCO
(23
), γ
Rin
g(1
7)
A″
- -
79
5
9
4.2
17
0
0.0
15
6
0.0
0
0.3
9
γCO
(25
), γ
Rin
g(1
9)
Ab
bre
via
tion
s:
t, t
ors
ion;
R1 t
rig
d,
Rin
g 1
tri
gonal
def
orm
ati
on;
R2 t
rig
d,
Rin
g 2
tri
gonal
def
orm
ati
on;
asy
m,
asy
mm
etri
c; s
, sy
mm
etri
c; �
, ben
din
g o
ut-
of-
pla
ne;
asy
md,a
sym
met
ric
def
orm
ati
on;
sym
d,
sym
met
ric
def
orm
ati
on;
b,
ben
din
g i
n-p
lane;
s,
stro
ng
; w
, w
eak;
m,
med
ium
; vs
, ve
ry w
eak;
ms,
med
ium
stro
ng,
Harm
onic
Fre
quen
cies
in c
m-1
. T
he
abso
lute
IR
inte
nsi
ty i
n K
m m
ol-1
. R
am
an s
catt
erin
g a
ctiv
ity
in A
4 a
mu
-1.
Dep
ola
riza
tion r
ati
ons
for
pla
ne
and u
np
ola
rise
d i
n a
mu.
Red
uce
d m
ass
es i
n A
MU
Forc
e co
nst
ants
in m
Dyn
e A
.