Unequivocal structural assignments of three cardanol derivatives: An experimental and theoretical approach

Article abstract of DOI:10.1016/j.molstruc.2018.07.112

Cardanol was obtained by vacuum distillation of ‘‘cashew nut shell liquid’’ (CNSL). Cardanol is a by-product of cashew production and a building block for chemical synthesis; cardanol and its derivatives can be used for different types of applications. Three of these compounds are the subject of the present NMR study and theoretical comparison. ¹H and ¹³C NMR signals were assigned using 1D and 2D NMR experiments. The DFT/B3LYP method using the cc-pVTZ basis set was employed for the calculations of the ¹H and ¹³C NMR chemical shifts (δ). The obtained data were used as an auxiliary tool for unequivocal assignment of all ¹H and ¹3C NMR signals. For these compounds, the adopted theoretical model was sufficient to obtain a good description of the chemical shifts.

Full text of DOI:10.1016/j.molstruc.2018.07.112

Accepted Manuscript
Unequivocal Structural Assignments of Three Cardanol Derivatives: An
Experimental and Theoretical Approach
Layla R. Barbosa, Daiane S. Souza, Luiz H.K. Queiroz, Alvaro C. Neto, Denis P.
de Lima, Adilson Beatriz, Wanderson Romão, Eustaquio V.R. de Castro, Valdemar Lacerda
PII:
S0022-2860(18)30937-2
10.1016/j.molstruc.2018.07.112
MOLSTR 25517
DOI:
Reference:
To appear in:
Journal of Molecular Structure
Received Date:
Accepted Date:
22 April 2018
30 July 2018
Please cite this article as: Layla R. Barbosa, Daiane S. Souza, Luiz H.K. Queiroz, Alvaro C. Neto,
Denis P. de Lima, Adilson Beatriz, Wanderson Romão, Eustaquio V.R. de Castro, Valdemar
Lacerda, Unequivocal Structural Assignments of Three Cardanol Derivatives: An Experimental and
Theoretical Approach, Journal of Molecular Structure (2018), doi: 10.1016/j.molstruc.2018.07.112
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Cardanol is a by-product of cashew production and a building block for chemical
synthesis; cardanol and its derivatives can be used for different types of applications.
Three of these compounds are the subject of the present NMR study and theoretical
comparison.
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Unequivocal Structural Assignments of Three Cardanol
Derivatives: An Experimental and Theoretical Approach
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Layla R. Barbosa , Daiane S. Souza , Luiz H. K. Queiroz Jr. , Alvaro C. Neto , Denis P.
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de Lima , Adilson Beatriz , Wanderson Romão , Eustaquio V. R. de Castro ,
Valdemar Lacerda Jr. 1*
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Departamento de Química, Centro de Ciências Exatas, Universidade Federal do
Espírito Santo, Av. Fernando Ferrari 514, 29.075-910 – Vitória – ES, Brasil. *e-mail:
vljuniorqui@gmail.com
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Instituto de Química, Centro de Ciências Exatas e Tecnologia, Universidade Federal
do Mato Grosso do Sul, Av. Senador Filinto Müller 1555, 79.074-460, Campo Grande -
MS, Brasil.
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Instituto de Química, Universidade Federal de Goiás, Goiânia, PO Box 131, Brazil
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Instituto Federal do Espírito Santo, 29106-010 Vila Velha, ES, Brazil
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ABSTRACT: Cardanol was obtained by vacuum distillation of ‘‘cashew nut shell
liquid’’ (CNSL). Cardanol is a by-product of cashew production and a building block
for chemical synthesis; cardanol and its derivatives can be used for different types of
applications. Three of these compounds are the subject of the present NMR study and
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theoretical comparison. H and C NMR signals were assigned using 1D and 2D NMR
experiments. The DFT/B3LYP method using the cc-pVTZ basis set was employed for
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the calculations of the H and C NMR chemical shifts (δ). The obtained data were
used as an auxiliary tool for unequivocal assignment of all ¹H and ¹³C NMR signals. For
these compounds, the adopted theoretical model was sufficient to obtain a good
description of the chemical shifts.
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Keywords: NMR, H NMR, 13C NMR, HMBC, HSQC, Cardanol, CNSL, NMR
calculations.
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INTRODUCTION
For several decades, ab initio NMR chemical shift calculations have been used
to interpret experimental spectroscopic data and therefore to assign the structures, the
stereostructures, and the conformations of complex molecules.[1]
In fact, the combination of NMR and computational chemistry techniques has
emerged as a powerful tool for the determination of the connectivity, conformation and
stereochemistry of particularly challenging systems.[2]
Currently, theoretical methods (especially DFT) permit highly reliable
calculations of shielding tensors and spin-spin coupling constants.[3-6]
Cardanol is an industrial oil obtained by vacuum distillation of ‘‘cashew nut
shell liquid’’ (CNSL), consisting of an alkyl phenolic oil contained in the spongy
mesocarp of the cashew nut shell obtained from the cashew tree Anacardium
occidentale L., and it is a low-cost by-product of the cashew industry that is also a
powerful phenolic pollutant.[7-10]
CNSL is well-known for its abundant in phenolic lipid microcomponents such as
anacardic acid (a), cardol (b), cardanol (c), and 2-methylcardol (d) (Figure 1).[7-14]
Figure 1
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When the nut is heated in industry (denoted as technical CNSL), the amount of
cardanol present in the CNSL is increased because anacardic acid is converted to
cardanol during this process through decarboxylation. Thus, low-quantity cardanol in
natural CNSL is the major component of technical CNSL.[12-15]
Cardanol can be considered as a building block for chemical synthesis, and it
adds value to the CNSL.[12] Much research has been devoted to the use of cardanol,
suggesting different types of applications for it and its derivatives. Cardanol
frameworks are involved in the construction of phenolic resins, bio-based polymers,
epoxy curing resins, reactive diluents and fluorescent compounds. Moreover, its
derivatives exhibit many biological activities such as fungicidal, bactericidal,
molluscicidal, larvicidal, anti-inflammatory, and antioxidant activities as well as activity
towards serious disorders such as cancer and obesity.[9, 13-29]
Considering the search for renewable and biodegradable sources and the high
fraction of cardanol obtained from industrial processes, research for new applications of
this compound has become highly important.

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We present here a complete NMR assignment for three cardanol derivatives (1, 2
and 3, Figure 2). These studies were performed using 1D and 2D NMR techniques, and
the obtained NMR spectra were compared to the theoretical predictions of the chemical
shifts using DFT calculations.
Figure 2
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EXPERIMENTAL
Materials
The procedure for preparation of the compounds is well-described in the
literature, and the relevant reactions are presented in Figures 3 and 4.[9,10]
Figure 3
Figure 4
NMR measurements
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The H, C{ H}, DEPT, gCOSY, gHSQC and gHMBC NMR spectra of these
compounds were obtained using a Varian 400 MHz spectrometer equipped with a 5-mm
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direct probe ATB BroadBand H/ F/X with a field z-gradient. Tetramethylsilane was
used as an internal reference and CDCl as a solvent. Chemical shifts are given on the δ
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scale. The spectra were opened and edited in the ACDLabs program.
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Using the H NMR spectra with the values of chemical shift (δ) in ppm, the
coupling constants (J) in Hz and the number of hydrogen atoms were obtained. The
multiplicities of the signals are abbreviated as follows: s = singlet; d = doublet; dd =
double doublet; t = triplet; q = quintet; m = multiplet.
Theoretical calculations
The structures of the compounds in question were drawn in PCMODEL 7.5[30]
software followed by conformational search.
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The structures of the lower energy optimised conformations were designed in the
program GaussView 4.1.2.[31] Then, optimisations of these conformations were carried
out with GAUSSIAN 03[32] using DFT at the MP2/cc-pVDZ level of theory. This set of

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conformations was used for the chemical shift calculations. The final reported result is a
weighted average of the conformations considering the population.
All calculations of the NMR shielding tensors were performed using the optimised
structures at the B3LYP level of theory and with the basis set functions cc-pVTZ[33,34]
as input using the GIAO[35,36] methods. The calculated NMR shielding tensors were
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converted into chemical shifts (δ) by considering the isotropic values of the TMS H
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and C shielding tensors, calculated at the same levels of theory. The effect of the
solvent was also included in the shielding tensor calculations using the PCM model.
Chloroform (dielectric constant) was used as a solvent.
RESULTS AND DISCUSSION
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All compounds were analysed based on H, C{ H}, DEPT-135, gCOSY,
gHSQC and gHMBC NMR results. The numbering of carbon atoms in the compounds
does not follow any standard or official guidelines. The purpose of this numbering is to
facilitate the identification of the carbon and hydrogen atoms in the discussion of the
spectra and theoretical data.
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The unequivocal assignments of H and C NMR signals of compounds 1 - 3
are listed in Tables 1 – 3.
Table 1
Table 2
Table 3
The above assignments were performed by analysing the 1D and 2D NMR
spectra to extract the chemical shifts and coupling constants. For compound 1, the H ,
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for example, appears in the aromatic region (at 7.14 ppm) and is assigned as a triplet
from the coupling with hydrogen atoms H and H .
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From C and DEPT-135 spectra, it is known that the C and C carbon signals
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respectively. The signals from these carbons were differentiated with the HMBC
spectrum. Coupling of C16 with H15 occurs (which is two bonds from hydrogen 15, as
already known). The same does not occur with C , which is four bonds away.
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By expanding a small region of the HMBC spectrum (Figure 4), it is possible to
identify C for compound 2. Among C , C and C , the last does not couple with H
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(five bonds away). Additionally, from the examination of this figure, it is possible to
identify the hydrogens 24 since they couple with C (it is not possible to observe this
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coupling for the hydrogens 22). These signals are in the region characteristic of the
hydrogens deprotected by the inductive effect of electronegative atoms and refer to the
region of the molecule derived from epichlorohydrin.
Figure 7
For compound 3, the signals at 4.3-3.6 ppm refer to the hydrogens deshielding
by the inductive effect of the electronegative atoms. Here, the hydrogens from the
methylene group H are slightly overlapping. Hydrogens 24 appear in 3.79 and 3.73 as
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two double doublets (Figure 8) because they are diastereotopic hydrogens, with J=11.2
Hz (from the geminal coupling) and J=5.7 Hz from the coupling with H '.
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Figure 8
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These experimental data were compared to the theoretical data obtained by the
calculations.
The shielding tensor calculations were performed both with and without the
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inclusion of the solvent effect. The comparisons of the experimental values of C and
1H NMR chemical shifts of compounds 1 – 3 and the theoretical values are presented in
Tables 4 – 6. A statistical study aiming to correlate the theoretical and experimental data
was carried out. We calculated the standard deviation (SD) and mean deviation (MD)
from the differences between theoretical and experimental values, with these values also
shown in Tables 4-6. The linear correlation factor (R) values presented in Tables 4 – 6
were obtained from the graphs for the correlations of the theoretical and experimental

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values (Figure 9, 11 and 13 for compounds 1, 2 and 3, respectively). Figures 10, 11 and
14 (for compounds 1, 2 and 3, respectively) present the graphs showing the difference
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(Δδ) between the theoretical and experimental values for H and C NMR chemical
shifts with and without the solvent effect.
Table 4
Table 5
Table 6

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By analysing the standard deviation (SD), mean deviation (MD) and linear
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correlation coefficient (R), it was possible to unequivocally assign the C and H NMR
signals for the studied compounds. We note that a good correlation is observed between
the theoretical and experimental data (R> 0.99176).
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For compound 1, it was observed that the best results for C were obtained
when the solvent effect was not taken into account (SD=3.6, MD=6.2, R=0.99876
without the solvent and SD=3.8, MD=6.6, R=0.99872 with the solvent). This small
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difference is visible in Figure 10. For the H NMR data, slightly better results were
obtained when the solvent effect was considered (SD=0.16, MD=0.25 with the solvent
and SD=0.21, MD=0.24 without the solvent).
In compound 2, the  13C calculations with the solvent effect are the most
advantageous because these calculations presented slightly better values of mean
deviation and linear correlation factor (MD = 2.3 and R = 0.99614) than the calculations
including the solvent effect (MD = 2.4 and R = 0.99613). This subtle advantage can be
seen in Figure 12. For hydrogen, the results were again better for the calculations
without the solvent effect, except for H and H hydrogens, where the results with the
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inclusion of the solvent effect were substantially better.
Table 6 and Figures 13 and 14 show that the experimental and calculated C
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and H NMR results of compound 3 are very similar, with no significant advantage for
either method.
For compound 1, no erroneous assignments were found for the chemical shifts,
indicating that the B3LYP / cc-pVTZ model obtained good calculation results.
The NMR chemical shift values depend on the electron densities around the
nuclei, and thus can be influenced by the chemical environment. Chemical shift
variations in solution provide important structural information on solute-solvent
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interactions. In this way, differences in chemical shifts observed in calculations with
and without the solvent effect are due in these atoms that experience greater changes in

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the chemical environment caused by the interactions with the solvent and, consequently,
changes in their chemical shifts.
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CONCLUSION
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In the present study, three compounds (1, 2 and 3) obtained from cardanol
extracted from CNSL were analysed by NMR spectroscopy. The H and 13C NMR
signals were assigned by the means of 1D and 2D NMR experiments.
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The experimental chemical shift data were correlated with the theoretical results.
The B3LYP/cc-pVTZ model was used to calculate all properties (with and without the
solvent). From the correlation between the theoretical and experimental data, it was
concluded that the model used in this study was effective for the calculation of the
shielding tensors for the studied compounds and could be used to assign the NMR
signals of these compounds. Overall, better results were obtained for the calculations
without the solvent effect.
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ACKNOWLEDGEMENTS
The authors thank the Conselho Nacional de Desenvolvimento Científico e Tecnológico
(CNPq), Coordenadoria de Aperfeiçoamento de Pessoal do Nível Superior (CAPES),
Fundação de Amparo à Pesquisa do Espírito Santo (FAPES) for the financial support
and fellowship. NCQP (Núcleo de Competências em Química do Petróleo) for their
financial and technical support.
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Figure 1. Chemical structures of CNSL's main components.
Figure 2. Cardanol derivatives studied in the present work.
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Figure 3. Synthesis of compound 1 from cardanol.
Figure 4. Reaction of saturated cardanol with epichlorohydrin.
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Figure 5. Expansion of the H NMR spectrum (H ) of compound 1.
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Figure 6 Expansion of the 2D NMR spectrum ( H, C-HMBC) of compound 1.
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Figure 7. Expansion of the 2D NMR spectrum ( H, C-HMBC) of compound 2.
1
Figure 8. Expansion of the H NMR spectrum (H e H ) of compound 3.
2
4a
24b
1
3
9
0
1
2
Figure 9. Correlation plots for compound 1 of (a) C NMR chemical shifts with the
1
3
1
1
1
1
solvent effect, (b) C NMR chemical shifts without the solvent effect, (c) H NMR
chemical shifts with the solvent effect and (d) H NMR chemical shifts without the
1
solvent effect.
1
3
1
1
1
3
4
Figure 10. Comparison of the Δδ values for the C and H NMR data of compound 1
with and without the solvent effect
1
3
1
1
1
1
5
6
7
8
Figure 11. Correlation plots for compound 2 of (a) C NMR chemical shifts with the
1
3
1
solvent effect, (b) C NMR chemical shifts without the solvent effect, (c) H NMR
1
chemical shifts with the solvent effect and (d) H NMR chemical shifts without the
solvent effect.
1
3
1
1
2
9
0
Figure 12. Comparison of the Δδ values for the C and H NMR data of compound 2
with and without the solvent effect.
1
3
2
2
2
2
1
2
3
4
Figure 13. Correlation plots for compound 3 of (a) C NMR chemical shifts with the
1
3
1
solvent effect, (b) C NMR chemical shifts without the solvent effect, (c) H NMR
1
chemical shifts with the solvent effect and (d) H NMR chemical shifts without the
solvent effect.
1
3
1
2
2
5
6
Figure 14. Comparison of the Δδ values for the C and H NMR data of compound 3
with and without the solvent effect.
1
13
2
2
2
3
3
3
7
8
9
0
1
2
Table 1. H and C NMR chemical shifts, (ppm), multiplicities and coupling constants
1
1
1
1
13
1
J( H, H) (Hz), H– H and C– H correlations in gCOSY and gHMBC spectra for
compound 1.
1
13
Table 2. H and C NMR chemical shifts, (ppm), multiplicities and coupling constants
1
1
1
1
13
1
J( H, H) (Hz), H– H and C– H correlations in gCOSY and gHMBC spectra for
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Table 3. H and C NMR chemical shifts, (ppm), multiplicities and coupling constants
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1
1
1
13
1
J( H, H) (Hz), H– H and C– H correlations in gCOSY and gHMBC spectra for
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3
1
Table 4. Calculated and experimental C and H NMR (ppm) chemical shifts, δ, with
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3
1
Table 5. Calculated and experimental C and H NMR (ppm) chemical shifts, δ, with
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3
1
Table 6. Calculated and experimental C and H NMR (ppm) chemical shifts, δ, with
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Highlights



Chemical shift calculations using the DFT/B3LYP method.
Complete NMR assignment for three cardanol derivatives.
Experimental and theoretical approach.

1
Table 1
Coupling
Constants (Hz)
1
3
1
C
δ ( C)
δ ( H)
Multiplicities
gCOSY
gHMBC
1
14.1
31.9 -29.4
31.3
0.89 (3H)
1.22 - 1.36(24H)
1.60 (2H)
2.56 (2H)
-
6.7
-
t
m
q
t
H2
-
-
2
-13
-
H15
1
4
5
6
7
8
9
0
1
7.6
7.6
-
H ; H
13
1
5
1
1
1
1
1
2
2
35.8
H14
-
H , H , H
21
13
17
145.0
115.3
155.4
112.5
129.4
121.0
-
H , H
14
20
21
6.69 – 6.61 (1H)
-
-
m
-
H , H
-
15
-
-
H20
6.69 – 6.61 (1H)
7.14 (1H)
6.73 (1H)
-
m
t
H20
H , H
17
21
7.6
7.6
H ; H
21
-
1
9
d
H20
H , H , H
15 17 19
2