Synthesis and phytotoxic activity of 1,2,3-triazole derivatives

Article abstract of DOI:10.5935/0103-5053.20130121

Thirteen triazole derivatives bearing halogenated benzyl substituents were synthesized using the Cu-catalyzed azide-alkyne cycloaddition (CuAAC),a leading example of the click chemistry approach,as the key step. The biological activity of the compounds was evaluated,and it was found that these compounds interfere with the germination and radicle growth (shoots and roots) of two dicotyledonous species,Lactuca sativa and Cucumis sativus,and one monocotyledonous species,Allium cepa. The compounds showed predominantly inhibitory activity related to the evaluated species mainly at the concentration of 10^-4 mol L^-1. Some of them presented inhibitory activity comparable to 2,4-D (2,4-dichlorophenoxyacetic acid),used as positive control.

Full text of DOI:10.5935/0103-5053.20130121

http://dx.doi.org/10.5935/0103-5053.20130121
J. Braz. Chem. Soc., Vol. 24, No. 6, 953-961, 2013.
Printed in Brazil - ©2013 Sociedade Brasileira de Química
0
103 - 5053 $6.00+0.00
Article
A
Synthesis and Phytotoxic Activity of 1,2,3-Triazole Derivatives
,
a
,a
b
Thiago F. Borgati,* Rosemeire B. Alves,* Róbson R. Teixeira,
b
b
b
Rossimiriam P. de Freitas, Thays G. Perdigão, Silma F. da Silva,
Aline Aparecida dos Santos and Alberto de Jesús O. Bastidas
b
c
a
Departamento de Química, Universidade Federal de Minas Gerais,
Av. Antônio Carlos, 6627, 31270-9001 Belo Horizonte-MG, Brazil
b
Departamento de Química, Universidade Federal de Viçosa,
Av. P. H. Rolfs, s/n, 36570-000 Viçosa-MG, Brazil
c
Laboratório de Química Ecológica, Departamento de Química, Facultad de Ciencias,
Universidad de Los Andes, Núcleo Universitario Pedro Rincón Gutiérrez,
La Hechicera, Mérida 5101-A, Venezuela
Uma série de treze derivados triazólicos contendo grupos benzila-halogenados foi sintetizada
utilizando-se como etapa chave a cicloadição azida-alcino catalisada por Cu(I) (CuAAC),
transformação comumente descrita como reação click. A atividade biológica destes compostos foi
avaliada, e verificou-se que estes compostos interferem na germinação e no crescimento radicular
(
(
brotos e raízes) das espécies Allium cepa (cebola), modelo de monocotiledônea, e Cucumis sativus
pepino) e Lactuca sativa (alface), modelos de dicotiledôneas. Os compostos apresentaram
atividade predominantemente inibitória com relação às espécies avaliadas principalmente na
-
4
-1
concentração de 10 mol L , sendo que alguns deles foram tão ativos quanto o 2,4-D (ácido
2
,4-diclorofenoxiacético), o controle positivo.
Thirteen triazole derivatives bearing halogenated benzyl substituents were synthesized using
the Cu-catalyzed azide-alkyne cycloaddition (CuAAC), a leading example of the click chemistry
approach, as the key step. The biological activity of the compounds was evaluated, and it was
found that these compounds interfere with the germination and radicle growth (shoots and roots)
of two dicotyledonous species, Lactuca sativa and Cucumis sativus, and one monocotyledonous
species, Allium cepa. The compounds showed predominantly inhibitory activity related to the
-4
-1
evaluated species mainly at the concentration of 10 mol L . Some of them presented inhibitory
activity comparable to 2,4-D (2,4-dichlorophenoxyacetic acid), used as positive control.
Keywords: herbicides, 1,2,3-triazoles, click chemistry, phytotoxicity
Introduction
weeds are capable of greatly reducing both crop quality and
yield, and therefore, weed control is highly desirable.
5
,6
Weeds can be defined in several ways, for example,
as plants that grow where humans do not wish them to
be. Vegetable species that grow in the wrong place, in the
wrong quantity or at the wrong time can also be considered
weeds. Another definition of a weed is a species whose
utility has not been identified. More often than not,
weeds interfere with human activities such as agriculture.
Weeds compete with crops for nutrients, water and physical
space, and may harbor insect and disease pests. Thus,
Although there are several ways to weed, the use of
chemicals (known as herbicides or weed killers) is currently
the most cost efficient and reliable weed control method
1-3
utilized by farmers. Currently, there are several active
compounds available to control weeds, but it is still necessary
to identify new herbicides to overcome weed resistance
1
-4
7-10
problems resulting from pressure of selection. In addition,
due to the public’s concerns about the environment, modern
herbicides should have a favorable combination of properties,
such as a high level of herbicidal activity, a low application
rate, crop tolerance and low toxicity to mammals.
*e-mail: thfborgati@gmail.com, rosebrondi@yahoo.com.br

9
54
Synthesis and Phytotoxic Activity of 1,2,3-Triazole Derivatives
J. Braz. Chem. Soc.
In the search and development for new herbicides as well
CHF O- or CF O- are very active; therefore, the synthesis
2
3
as other agrochemicals and pharmaceuticals, heterocyclic
compounds play an important role. The heterocyclic core
is frequently part of the pharmacophore responsible for
of compounds containing these fragments is a primary goal
of modern agrochemistry.
19
Because of the importance of heterocycles and halogens
in the development of new agrochemicals and as well as our
1
1,12
the observed biological activity.
The heterocyclic
20-23
portion of a compound can have beneficial effects in
terms of its physicochemical properties, conferring
lipophilicity and solubility values in the optimal range
for uptake and bioavailability. Moreover, heterocycles are
ideal bioisosteres of other homocyclic rings, heterocyclic
rings and several different functional groups. In many cases,
this bioisosterism can result in compounds with improved
interest in the chemistry of triazoles and in the preparation
of bioactive compounds that can be used as new active
24-27
ingredients to control weeds, our group synthesized novel
1,2,3-triazoles bearing halogenated benzyl moieties, and
then, evaluated their phytotoxic activities.
Experimental
1
2-14
biological efficacy.
Nitrogen-containing heterocycles
are representatives of this class of organic compounds
that stand out due to their abundance in nature and great
significance in biochemistry. These structural subunits
exist in many natural compounds such as vitamins,
hormones, antibiotics and alkaloids, in addition to being
found in pharmaceuticals, herbicides, dyes and many
Materials and methods
All of the solvents used were purified by distillation.
Commercially available benzyl alcohol, 4-fluorobenzyl
alcohol, 4-chlorobenzyl alcohol, 4-bromobenzyl alcohol,
4-iodobenzyl alcohol, 3,4-difluorobenzyl alcohol,
4-(trifluoromethyl)benzyl alcohol, 4-(trifluoromethoxy)
benzyl alcohol, 5-bromo-2-chlorobenzyl alcohol,
2,4,6-trichlorobenzyl alcohol, pent-4-yn-1-ol,
prop-2-yn-1-ol, triethylamine, methanesulfonyl chloride,
sodium ascorbate, sodium azide and copper(II) sulfate were
purchased fromAldrich (USA) and utilized without further
1
4
other compounds. Triazoles are one of the most studied
classes of nitrogen heterocycles. Triazole derivatives have
a wide range of applications and are used as explosives,
drugs and agrochemicals. The 1,2,4-triazole core has been
found to be an integral part of therapeutically interesting
compounds that display significant antibacterial, central
nervous system (CNS) stimulative, sedative, antifungal and
1
13
purification. The H and C nuclear magnetic resonance
(NMR) spectra were recorded on a BrukerAvance DPX 200
14
antitumor activities. It is also worth to mention that all
15
triazole derivatives are synthetic.
spectrometer at 200 MHz using CDCl as the solvent and
3
Another class of organic compounds widely employed
as pesticides is the halogen-containing heterocycles.
These compounds are generally more polar than their
homocyclic analogs and possess lower n-octanol-water
partition coefficients. Consequently, halogen-containing
heterocycles are often more environmentally mobile. In
addition to their use as pesticides, halogen-containing
heterocycles have also been used as pharmaceuticals,
dyes and explosives.
TMS (tetramethylsilane) as the internal standard, unless
otherwise stated. The NMR data are presented as follows:
chemical shift, d in ppm, multiplicity, number of protons,
proton assignments and J in Hz. Multiplicities are indicated
by the following abbreviations: s (singlet), d (doublet), dd
(double doublet), t (triplet), m (multiplet), qn (quintet) and
brs (broad signal). Mass spectra were recorded on a
Shimadzu GC MS-QP5050A instrument using direct
insertion along with the electrospray ionization method and
a quadrupole analyzer. Infrared spectra were recorded
on a Spectra One Perkin-Elmer spectrophotometer,
fitted with a Paragon ATR accessory. Melting points
were determined using an MQAPF-301 melting point
apparatus (Microquimica, Brazil) and are uncorrected.
The progress of the reactions was monitored by thin layer
chromatography (TLC). Column chromatography was
performed over silica gel (60-230 mesh).
The past 30 years have witnessed a period of significant
expansion in the research and development of halogenated
16-18
compounds to be used as agrochemicals.
The primary
advantages of using these compounds are their economic
viability and high efficacy. This high efficacy makes these
compounds environmentally safe and user friendly because
they are used at very low concentrations. Interestingly, there
has been an increase in the number of commercial products
containing mixed-halogen compounds. The extrapolation
of the current trend indicates that an increase in the number
of fluorine-substituted agrochemicals throughout the
twenty-first century is to be expected. QSAR (quantitative
structure-activity relationship) studies have shown that
fluorinated benzyl moieties with fragments such as
Synthesis
4-Fluorobenzyl methanesulfonate (2b)
To a 50 mL round bottom flask, 4-fluorobenzyl
alcohol (126 mg, 1 mmol), dichloromethane (5 mL) and

Vol. 24, No. 6, 2013
Borgati et al.
955
triethylamine (280 mL, 2.0 mmol) were added, and
the mixture was cooled to -50 °C. Subsequently,
methanesulfonyl chloride (120 mL, 1.4 mmol) was added
to the flask, and the mixture was stirred vigorously. The
reaction was complete after 30 min. After completion, the
organic layer was washed with 1% aqueous HCl (15 mL)
under reduced pressure to afford compound 3b in a 91%
yield (106 mg).
Azides 3a, 3c-3j (Figure 1) and 7 (Figure 2) were
synthesized in yields ranging from 72 to 99% using a
procedure similar to that described for compound 3b.
The spectroscopic data of the azides are available in the
SI section.
followed by saturated aqueous NaHCO (5 mL), dried over
3
Na SO , and concentrated under reduced pressure. This
2
4
procedure afforded compound 2b in a 95% yield (193 mg,
3-[1’-(4’’-Fluorobenzyl)-1’,2’,3’-triazol-4’-yl]propan-1-ol (4b)
A total of 93 mg (0.62 mmol) of the azide derivative 3b
was added to a 10 mL round bottom flask containing 1 mL
of dichloromethane, 1 mL of water, 30.7 mg (0.12 mmol,
20 mol%) of CuSO .5H O, 48.8 mg (0.24 mmol, 40 mol%)
0.95 mmol).
Sulfonates 2a, 2c-2j (Figure 1) and 6 (Figure 2) were
synthesized in yields ranging from 77 to 100% using a
procedure similar to that described for compound 2b. The
spectroscopic data for these compounds are available in
the Supplementary Information (SI) section.
4
2
of sodium ascorbate and 55 mL of pent-4-yn-1-ol. The
resulting reaction mixture was vigorously stirred at room
temperature for 24 h. Subsequently, the mixture was
extracted with 15 mL of CH Cl , and the resulting material
1
-(Azidomethyl)-4-fluorobenzene (3b)
2
2
Mesylated compound 2b (157 mg, 0.77 mmol) was
obtained after solvent removal was purified by silica gel
column chromatography. The product was eluted with
100 mL of dichloromethane, 100 mL of dichloromethane/
ethyl acetate (1:1 v/v), 100 mL of ethyl acetate and
100 mL of ethyl acetate/methanol (9:1 v/v). The procedure
described afforded compound 4b with a 71% yield (103 mg,
0.44 mmol).
added to a 50 mL round bottom flask containing 5 mL of
DMSO (dimethyl sulfoxide) and 200 mg (3.1 mmol) of
sodium azide. The reaction mixture was stirred at room
temperature for 15 h. After this period of time, 15 mL of
dichloromethane were added to the flask. The resulting
organic layer was washed with 15 mL of saturated
aqueous NaCl solution. After separation, the organic
layer was dried over Na SO , filtered and concentrated
Compounds 4a, 4c-4j (yield ranging from 44 to 90%),
5a (87% yield), 5b (49% yield) and 8 (87% yield) were
2
4
Mesylate
Compound
Azide
1,2,3-Triazole
Yield / %
100
95
Compound
Yield / %
85
Compound
Yield / %
79
1
2
3
4
5
R = R = R = R = R = H
2a
2b
2c
2d
2e
2f
3a
3b
3c
3d
3e
3f
4a
4b
4c
4d
4e
4f
1
2
4
5
3
R = R = R = R = H, R = F
91
71
1
2
4
5
3
R = R = R = R = H, R = Cl
91
93
73
1
2
4
5
3
R = R = R = R = H, R = Br
99
96
55
1
2
4
5
3
R = R = R = R = H, R = I
90
85
90
1
2
4
5
3
R = R = R = R = H, R = OCF
100
77
99
44
3
1
2
4
5
3
R = R = R = R = H, R = CF
2g
2h
2i
3g
3h
3i
81
4g
4h
4i
80
3
1
4
5
2
3
R = R = R = H, R = R = Br
93
72
74
1
2
3
5
4
R = Cl, R = R = R = H, R = Br
98
92
64
1
3
5
2
4
R = R = R = Cl, R = R = H
2j
99
3j
92
4j
67
Figure 1. Preparation of compounds 4a-4j. Reagents and conditions: (i) MsCl, Et N, CH Cl , -50 ºC, 30 min; (ii) NaN , DMSO, r.t., 15 h; and
3
2
2
3
(
iii) pent-4-yn-1-ol, NaAsc (40 mol%), CuSO .5H O (20 mol%), CH Cl /H O (50% v/v), r.t., 24 h.
4 2 2 2 2

9
56
Synthesis and Phytotoxic Activity of 1,2,3-Triazole Derivatives
J. Braz. Chem. Soc.
Figure 2. Preparation of compounds 5a, 5b and 8. Reagents and conditions: (i) MsCl, Et N, CH Cl , -50 ºC, 30 min; (ii) NaN , DMSO, r.t., 15 h; and
3
2
2
3
(
iii) pent-4-yn-1-ol, NaAsc (40 mol%), CuSO .5H O (20 mol%), CH Cl /H O (50% v/v), r.t., 24 h. Yields are given in parentheses.
4 2 2 2 2
prepared from the corresponding azides using a procedure
similar to that described for compound 4b. The compounds
were purified by column chromatography using a typical
eluotropic sequence (dichloromethane, ethyl acetate and
methanol), and the yields are presented in Figures 1 and 2.
The structures of the triazoles are supported by the
spectroscopic and spectrometric data available in the SI
section.
dish. Three replicates were used for each target species.
After the addition of the seeds and the aqueous solutions
(10 mL), the Petri dishes were sealed with parafilm to
create closed-system models. The seeds were incubated
at 25 °C in a controlled environment growth chamber in
the absence of light. The bioassays lasted 5 days for the
dicot model species and 7 days for the monocot model
species (onion). After the growth period, the plants were
frozen at -10 °C for 24 h to prevent growth during the
measurement process. This process facilitated the handling
of the plants and allowed the more accurate measurement
of radicle elongation. The shoot and root lengths of each
radicle were measured manually to the nearest millimeter,
using a ruler. The germination rate was obtained by the
direct counting of the number of seeds that germinated,
but not necessarily developed. Seeds were considered to
have germinated if a radicle protruded at least 1 mm. All
treatments were replicated three times in a completely
randomized design. The percent inhibition or stimulation
of radicle growth (root and shoot) was calculated in relation
to the radicle growth of the negative control using the
following equation:
Biological assays
The evaluation of the phytotoxic activities of compounds
4
a-4j, 5a, 5b and 8 was performed using an adaptation of
28
the methodology described by Macías et al. The bioassays
used Petri dishes (90 mm diameter) with one sheet of
Whatman No. 1 filter paper as a substrate. The target species
were Allium cepa (onion) as the model monocotyledonous
plant and Lactuca sativa (lettuce) and Cucumis sativus
(
cucumber) as the dicotyledonous species. The plants
were germinated and grown in aqueous solutions. The
compounds to be assayed were dissolved in DMSO at
different concentrations, and these solutions were diluted
with distilled water, so that, the desired test concentrations
-
4
-6
-8
-1
(
10 , 10 and 10 mol L ) were obtained. This procedure
(
1)
facilitated the dissolution of the assayed compounds.
Twenty five commercial seeds of each target species were
placed in each Petri dish. The appropriate treatment, or
the negative control (aqueous solution containing DMSO
but no test compound), was added (10 mL) to each Petri
where S corresponds to the average value of germination
or the radicle (root and shoot) length and C corresponds to
the average growth of the negative control. When using this

Vol. 24, No. 6, 2013
Borgati et al.
957
equation, stimulatory effects correspond to values above
the graphic base line, and inhibitory effects correspond to
values below this line (Figures 3-6). Errors were estimated
using the derivative method. L. sativa, C. sativus and A. cepa
seeds (TOPSEED brand) were purchased fromAgristar do
Brasil, Petropólis city, Rio de Janeiro State, Brazil. The
commercial herbicide 2,4-D (2,4-dichlorophenoxyacetic
acid) was used as positive control.
Figure 4. Effects of compounds 4a-4j, 5a, 5b, 8 and 2,4-D on the shoot and
root lengths of L. sativa, relative to the negative control.
Figure 3. Effects of compounds 4a-4j, 5a, 5b, 8 and 2,4-D on the
germination of L. sativa, A. cepa, and C. sativus, relative to the negative
control.
Figure 5. Effects of compounds 4a-4j, 5a, 5b, 8 and 2,4-D on the shoot and
root lengths of A. cepa, relative to the negative control

9
58
Synthesis and Phytotoxic Activity of 1,2,3-Triazole Derivatives
J. Braz. Chem. Soc.
Results and Discussion
Synthesis of triazole derivatives
The compounds 4a-4j were prepared in three steps as
outlined in Figure 1.
Commercially available benzylic alcohols were
initially converted into their corresponding mesylates 2a-
2
j by the straightforward reaction with methanesulfonyl
3
0
chloride. Nucleophilic substitution reactions between
sodium azide and the mesylates yielded azides 3a-3j.
Cu-catalyzed azide-alkyne cycloaddition (CuAAC),
3
1
3
2
a leading example of the click chemistry approach,
between compounds 3a-3j and pent-4-yn-1-ol afforded
the chemicals 4a-4j in yields ranging from 44 to 90%
(
Figure 1). The click reaction is a very reliable method
to prepare 1,2,3-triazoles. The conditions of the click
reactions used to prepare 4a-4j were similar to those
3
3
reported by Iehl et al., who have shown that the reaction
time should be approximately 2 h. However, in the present
study, the product formation was not observed within less
than 20 h. The best results were observed for a period of
2
4 h at room temperature. It is necessary caution when
Figure 6. Effects of compounds 4a-4j, 5a, 5b, 8 and 2,4-D on the shoot and
root lengths of C. sativus, relative to negative the control.
manipulating any kind of azide, organic and inorganic,
due to the risk of explosion caused by mechanic shock,
electrical spark as well as heating.
3
4,35
Cluster analysis
A second set of compounds, 5a, 5b and 8, was prepared
as depicted in Figure 2.
®
The cluster analysis was performed using Statistica
software (version 5.0), and the clusters were generated
on the basis of the activity parameters for the three
concentrations. Data were statistically analyzed using
Welch’s test, with significance set at 0.01 and 0.05. Results
are expressed as percentage differences to control. Zero
represents control, positive values represent stimulation
of the studied parameter, and negative values represent
inhibition. Once the germination and growth data were
acquired, cluster analysis was used to group compounds
with similar phytotoxicity behaviors and associate them
with their molecular structure. Complete linkage was used
as an amalgamation rule and the distance measurement
was based on squared euclidean distances, given by the
equation below:
Chemicals 5a and 5b were obtained, respectively,
from azides 3a and 3d and were synthesized to evaluate
the influence of shortening the triazole side chain on the
compound biological activity (compound 5a compared
with 4a and compound 5b compared with 4d). The aim of
the preparation of triazole 8 was to evaluate the impact of
the presence of two triazole rings on the phytotoxic activity
(vide infra).
Evaluation of the phytotoxic activity of triazoles
The strategies employed for the discovery of new
chemicals to control weeds (and other agrochemicals)
are similar to those used for the discovery of bioactive
compounds in the pharmaceutical industry and involve the
assessment of the activity of extracts and pure compounds
2
d(x,y) = ∑ (x - y )
(2)
i
i
3
6
in a given biological system. Preliminary laboratory
bioassays need to be fast, economical and relevant to
the system in question, in addition to being useful to
establish the potential activity of a pure compound
or an extract. Bioassays should also be followed by
studies in greenhouses and fields to determine whether
the initial observations are reproducible on a larger
where d(x,y) is the squared euclidean distance
i-dimensional), i represents the number of variables, and
x and y the observed values. Regression analyses
(
were performed using the Microsoft Excel 2010
®
(
(
Microsoft Corporation, USA) and Graph Pad Prism
version 4).
2
9

Vol. 24, No. 6, 2013
Borgati et al.
959
3
7,38
scale.
The most widely used bioassay to evaluate
trifluoromethylphenyl group, was almost inactive. Only
the phytotoxicity of a synthesized compound is one that
monitors the germination and growth of plants (root and
shoot) of given species such as Lactuca sativa (lettuce),
Raphanus sativus L. (radish), Lepidium sativum (cress),
Cucumis sativus (cucumber) and Allium cepa (onion),
among other species, primarily due to their high
sensitivity and fast germination rates. Weeds, which would
be the ideal candidates for this initial assessment to identify
potential herbicides, are used for testing only after activity
is observed against the species mentioned above. This is
compound 4f was as phytotoxic as the positive control,
-4
-6
-1
2,4-D at the concentration of 10 and 10 mol L .
The effects of the triazole derivatives on A. cepa are
outlined in Figure 5. The growth of the shoots and roots of
this monocotyledonous species was strongly inhibited by
-4
-1
compounds 4b-4f and 8 at 10 mol L , with compound 8
being the most potent (-89%). With the exception of
compounds 4a, 5a and 5b, all of the synthesized compounds
presented superior phytotoxic effects in the development of
the onion root and shoot than the positive control, 2,4-D.
This is not a surprisingly result since this commercial
agrochemical is used as a selective herbicide controlling
dicot species and preserving monocot ones.
31,39
because weeds generally have low germination rates.
The effects of 1,2,3-triazoles 4a-4j, 5a, 5b and 8 on
the germination and radicle growth (shoot and root) of
the species Lactuca sativa (lettuce), Cucumis sativus
The effects of compounds 4a-4j, 5a, 5b and 8 on
C. sativus were also evaluated (Figure 6). In this experiment,
the most phytotoxic compound was the triazole 4b, which
caused almost 90% inhibition of the shoot development and
84% inhibition of the root development at a concentration
(
cucumber) and Allium cepa (onion) were evaluated at three
-4
-6
-8
-1
different concentrations (10 , 10 and 10 mol L ) and the
results are shown in Figures 3-6.
With respect to germination (Figure 3), the most
pronounced effects were observed on L. sativa.
Compounds 4b-4f, 4j, 5b and 8 significantly inhibited the
-6
-1
of 10 mol L . None of the synthesized compound was as
phytotoxic as the positive control on the cucumber root and
shoot development.
-4
-1
germination relative to the negative control.At 10 mol L ,
triazoles 4d, 4e, 4f, 4j and 8 exhibited inhibitory activities
greater than 90%. Regarding A. cepa, compound 4f was
the most efficient in inhibiting germination (ca. -80% at
28,29
According to Macías et al.,
the compounds tested
in standard bioassays tend to have inhibitory effect only at
the highest concentrations; at lower concentrations, their
inhibitory effect usually decreases and may sometimes
reach a stimulatory effect. This growth stimulation at lower
concentrations was observed for compounds 4d, 4e, 4h, 4j,
5a and 8, on the lettuce (Figure 4); for compounds 4b, 4c,
4i, 5a and 5b, on the onion (Figure 5); and 4g, 4h, 5a and
5b, against cucumber (Figure 6).
-4
-6
-1
1
0 and 10 mol L ). Some compounds were more effective
inhibiting the germination than the positive control (2,4-D),
especially on lettuce and onion.
For C. sativus, fluorinated 4f strongly inhibited the
germination at the highest concentration (-85%). The
germination of C. sativus was also strongly inhibited by
-6
-8
-1
-4
-1
4
b at 10 and 10 mol L , and 8 at 10 mol L (Figure 3).
The effects of compounds 4a-4j, 5a, 5b and 8 on the
Cluster analysis
radicle growth (shoot and root) of the evaluated species
are presented in Figures 4-6. As general trend, the triazole
derivatives had inhibitory effects on the tested species.
In addition, the halogenated compounds had, in general,
superior effects relative to those of their non-halogenated
counterparts (compounds 4a and 5a), demonstrating the
beneficial effects of the presence of halogen atoms on the
biological activity of the evaluated compounds.
To obtain a better understanding of the relationship
between biological activity and the structural features of
the evaluated compounds, cluster analysis was performed
on the basis of biological activity values (root and shoot
growth) for all of the concentrations tested (Figure 7).
Based on activity, the assayed compounds can
be divided into three groups (G1, G2 and G3). The
composition of each group was as follows: G1 is
composed of chemicals with low activity, 4a, 5a and 4g;
G2 contains compounds 4h, 4i, and 5b; and G3 contains
compounds 4b-4f, 4j and 8.
The compounds belonging to G1 do not possess
a halogen directly attached to the benzyl ring. The
compounds in G2 contain triazoles with two halogen
atoms attached to the aromatic ring and one triazole with
a shorter aliphatic side chain (5b). With the exception of
4f, the compounds in G3 are derivatives containing one
The growth of the shoots and roots of L. sativa was
strongly inhibited (higher than 60%) by the majority of
-4
-1
the test compounds at a concentration of 10 mol L , as
shown in Figure 4. Exceptions to this generalization were
the derivatives 4a, 4g and 5a, which can be considered
inactive against this species. Interestingly, although the
derivative 4f, which contains a trifluoromethoxyphenyl
group, inhibited the radicle growth of L. sativa by
1
00% at the highest concentration and retained this
-6
-1
effect at 10 mol L , the derivative 4g, which contains a

9
60
Synthesis and Phytotoxic Activity of 1,2,3-Triazole Derivatives
J. Braz. Chem. Soc.
The most significant results were observed for the
fluorinated derivatives (4b and 4f), and the chlorinated
derivatives (4c and 4j), and at some concentrations, these
compounds inhibited lettuce germination by up to 100%.
These compounds also inhibited the growth of shoots and
roots by approximately 60% for all target species at a
-4
-1
concentration of 10 mol L .
Considering these results, these compounds seem
worthy of further investigation and could be exploited for
the design of new ones endowed with herbicidal activity.
Synthetic efforts are under way in our laboratories to
prepare and biologically evaluate new derivatives. The
results will be submitted soon.
Figure 7. Cluster analysis of compounds 4a-4j, 5a, 5b and 8 according
to their biological profiles.
halogen attached to position 4”, or to position 4””, in case
of 8 (see Figures 1 and 2 for numbering), with compound
Supplementary Information
4
b, which has a fluorine substituent, being the most potent
among all of the synthesized triazoles. Compound 8, which
has a bromine attached to position 4’’’’, was found to be
one of the most active compounds. This result points to the
fact that the presence of a second triazole ring possibly has
a favorable impact in terms of biological activity. Further
studies will be carried out to prove such hypothesis.
A list of all spectroscopic data is available free of charge
at http://jbcs.sbq.org.br as a PDF file.
Acknowledgments
We are grateful to CNPq (Conselho Nacional de
Desenvolvimento Científico e Tecnológico), FAPEMIG
(Fundação de Amparo à Pesquisa do Estado de Minas
Gerais) and PRPq (Pró-Reitoria de Pesquisa da
Universidade Federal de Minas Gerais) for their financial
support.
Conclusions
In summary, thirteen 1,2,3-triazoles were synthesized,
purified and fully characterized. The conditions employed
were satisfactory, and thus, the formation of side
products was not observed. The phytotoxicity of these
compounds was investigated against two dicotyledonous
species, Lactuca sativa and Cucumis sativus, and one
monocotyledonous species, Allium cepa. The products
exhibited predominantly inhibitory activity on the target
species, and they were more selective for the dicotyledonous
species, in particular for lettuce. Some of them were more
phytotoxic than the positive control (2,4-D), especially
on lettuce and onion. The comparison of the activities of
products 4b-4j with the activities of compound 4a, which
was synthesized to evaluate the influence of the absence
of a halogen substituent on phytotoxic activity, revealed
that the halogenated products were much more active.
The same relationship was observed when comparing the
phytotoxicity of derivatives 5a and 5b. These products were
synthesized to evaluate the influence of shortening the chain
length on phytotoxic activity. Again, it was confirmed that
the presence of a halogen substituent on product 5b was
necessary for appreciable phytotoxic activity. It was also
noted an appreciable similarity between the phytotoxic
activities of compounds 4b and 5b, and thus, confirming
that the length of the triazole side chain does not have an
important effect on phytotoxic activity.
References
1. Cremlyn, R. J.; Agrochemicals: Preparation and Mode of
nd
Action, 2 ed.; John Wiley & Sons: New York, USA, 1991.
st
2. Cobb, A.; Herbicides and Plant Physiology, 1 ed.; Chapman
& Hall: New York, USA, 1992.
th
3. Ware, G. W.; The Pesticide Book, 5 ed.; Thomson Publications:
Fresno, USA, 2000.
4. Stetter, J.; Lieb, F.; Angew. Chem., Int. Ed. 2000, 39, 1724.
th
5. Tomlin, C. D. S.; The Pesticide Manual, 14 ed.; BCPC:Alton,
USA, 2006.
6. Böger P.; Wakabayashi, K.; Hirai, K.; Herbicide Classes in
Development. Mode of Action, Targets, Genetic Engineering,
st
Chemistry, 1 ed.; Springer-Verlag: Berlin, Germany, 2002.
7. Gressel, J.; Pest Manag. Sci. 2009, 65, 1164.
8. Vencil, W.; Grey, T.; Culpepper, S.; Herbicides and Environment,
st
1 ed.; Kortekamp, A., ed.; In Tech: Rijeka, Croatia, 2001.
9. Shaner, D. L.; Lindenmeyer, R. B.; Ostlie, M. H.; Pest. Manag.
Sci. 2012, 68, 3.
10. http://www.weedscience.org accessed in July 2012.
11. Lednicer, D.; Mitscher, L. A.; The Organic Chemistry of Drug
st
Synthesis, vol. 2, 1 ed.; Wiley-Interscience/John Wiley: New
York, USA, 1980.

Vol. 24, No. 6, 2013
Borgati et al.
961
1
2. Lamberth, C.; Dinges, J.; Bioactive Heterocyclic Compound
25. Teixeira, R. R.; Barbosa, L. C. A.; Forlani, G.; Piló-Veloso, D.;
Carneiro, J. W. de M.; J. Agric. Food Chem. 2008, 56, 2321.
26. Barbosa, L. C. A.; Nogueira, L. B.; Maltha, C. R. A.; Teixeira,
R. R.; Silva, A. A.; Molecules 2009, 14, 160.
st
Classes: Agrochemicals, 1 ed.; Wiley-VCHVerlag: NewYork,
USA, 2012.
1
1
1
3. Dua, R.; Shrivastava, S.; Sonwane, S. K.; Srivastava, S. K.;
Advan. Biol. Res. 2011, 5, 120.
27. Barbosa, L. C. A.; Demuner, A. J.; Maltha, C. R. A.; Teixeira,
R. R.; Souza, K. A. P.; Bicalho, K. V.; Z. Naturforsch., B:
J. Chem. Sci. 2009, 64, 245.
4. Pholshettiwar, V.; Varma, R. S.; Pure Appl. Chem. 2008, 80,
7
77.
5. Melo, J. O. F.; Donnici, C. L.;Augusti, R.; Ferreira,V. F.; Souza,
28. Macías, F.A.; Castellano, D.; Molinillo, J. M. G.; J. Agric. Food
Chem. 2000, 48, 2512.
M. C. B.V.; Ferreira, M. L. G.; Cunha,A. C.; Quim. Nova 2006,
2
9, 569.
29. Macías, F.A.; Fernández,A.;Varela, R. M.; Molinillo, J. M. G.;
Torres, A.; Alves, P. L. C. A.; J. Nat. Prod. 2006, 69, 795.
30. Creary, X.; Underiner, T. L.; J. Org. Chem. 1985, 50, 2165.
31. Hosoya, T.; Inoue, A.; Hiramatsu, T.; Aoyama, H.; Suzuki, M.;
Bioorg. Med. Chem. 2009, 17, 2490.
1
1
1
1
2
6. Ramanand, K.; Nagarajan, A.; Suflita, J. M.; Appl. Environ.
Microbiol. 1993, 59, 2251.
7. Ding, W. H.; Liu C. H.; Yeh, S. P.; J. Chromatogr. Sci. 2000,
8
96, 111.
8. Guibiao, Y.; Wei, Z.; Xin, C.; Canping, P.; Shuren, J.; Chin. J.
Anal. Chem. 2006, 34, 1207.
32. Sharpless, K. B.; Finn, M. G.; Kolb, H. C.; Angew. Chem.,
Int. Ed. 2001, 40, 2004.
9. Tixier,C.;Sancelme,M.;Bonnemoy,F.;Cuer,A.;Veschambre,H.;
Environ. Toxicol. Chem. 2001, 20, 1381.
33. Iehl, J.; Freitas, R. P.; Nierengarten, J. F.; Tetrahedron Lett.
2008, 49, 4063.
0. Wei, H.; Haifang, L.; Lin, J. M.; J. Chromatogr. Sci. 2009, 1216,
34. Bräse, S.; Barnet, K.; Organic Azides Synthesis and
st
9
134.
Applications, 1 ed.; John Wiley & Sons: West Sussex, UK,
1
2
9. Jeschke, P.; Pest Manag. Sci. 2010, 66, 10.
2010.
0. Santos, L. J.; Gonçalves, A. S. P.; Krambrock, K.; Pinheiro,
M.V. B.; Eberlin, M. N.;Vaz, B. G.; Freitas, R. P.;Alves, R. B.;
J. Photochem. Photobiol., A 2011, 217, 184.
35. Bräse, S.; Gil, C.; Knepper, K.; Zimmermann,V.; Angew. Chem.,
Int. Ed. 2005, 44, 5188.
36. Short, P. L.; Chem. Eng. News 2005, 83, 19.
37. Duke, S. O.; Dayan, F. E.; Romagni, J. G.; Rimando, A. M.;
Eur. Weed Res. 2000, 40, 99.
2
2
2
2
1. Rocha, G. P.; Santos, L. J.; Luduvico, I.; Alves, R. B.; Freitas,
R. P.; Tetrahedron Lett. 2010, 51, 1022.
2. Couri, M. R. C.; Luduvico, I.; Santos, L. J.; Alves, R. B.;
Auxiliadora, M.; Gil, R. P. F.; Carbohydr. Res. 2007, 342, 1096.
3. Santos, L. J.; Couri, M. R. C.; Luduvico, I.;Alves, R. B.; Prado,
M. A. F.; Gil, R. P. F.; Synth. Commun. 2007, 37, 3059.
4. Barbosa, L. C. A.; Rocha, M. E.; Teixeira, R. R.; Maltha,
C. R. A.; Forlani, G.; J. Agric. Food Chem. 2007, 55, 8562.
38. Vyvyan, J. R.; Tetrahedron 2002, 58, 1631.
39. Mizuno, C. S.; Rimando, A. M.; Duke, S. O.; J. Agric. Food
Chem. 2010, 58, 4353.
Submitted: January 14, 2013
Published online: May 21, 2013

J. Braz. Chem. Soc., Vol. 24, No. 6, S1-S63, 2013.
Printed in Brazil - ©2013 Sociedade Brasileira de Química
0
103 - 5053 $6.00+0.00
Supplementary Information
SI
Synthesis and Phytotoxic Activity of 1,2,3-Triazole Derivatives
,
a
,a
b
Thiago F. Borgati,* Rosemeire B. Alves,* Róbson R. Teixeira,
b
b
b
Rossimiriam P. de Freitas, Thays G. Perdigão, Silma F. da Silva,
Aline Aparecida dos Santos and Alberto de Jesús O. Bastidas
b
c
a
Departamento de Química, Universidade Federal de Minas Gerais,
Av. Antônio Carlos, 6627, 31270-9001 Belo Horizonte-MG, Brazil
b
Departamento de Química, Universidade Federal de Viçosa,
Av. P. H. Rolfs, s/n, 36570-000 Viçosa-MG, Brazil
c
Laboratório de Química Ecológica, Departamento de Química, Facultad de Ciencias,
Universidad de Los Andes, Núcleo Universitario Pedro Rincón Gutiérrez,
La Hechicera, Mérida 5101-A, Venezuela
Benzyl methanesulfonate (2a)
benzylic), 7.28 (d, 2H, J 8.4 Hz, H2/H6), 7.51 (d, 2H,
-1
13
Colorless liquid; yield 100%; IR (ATR) ν/cm 3064,
J 8.4 Hz, H3/H5); C NMR (50 MHz, CDCl ) d 38.2
3
3
9
031, 2866, 1496, 1454, 1357, 1172, 1071, 1025, 967,
(-CH ), 70.6 (benzylic), 123.5 (C4), 130.4 (C2/C6), 132.0
(C3/C5), 132.6 (C1).
3
1
34, 912, 734; H NMR (200 MHz, CDCl ) d 2.85 (s, 3H,
3
-
CH ), 5.17 (s, 2H, benzylic), 7.03-7.38 (m, 5H, H2/H3/
3
1
3
H4/H5/H6); C NMR (50 MHz, CDCl ) d 37.6 (-CH ),
4-Iodobenzyl methanesulfonate (2e)
3
3
o
-1
7
1.5 (benzylic), 128.5 (C4), 128.6 (C2/C6), 129.00 (C3/
Yellow solid; m.p. 181 C; yield 90%; IR (ATR) ν/cm
C5), 133.3 (C1).
3039, 3018, 2941, 1485, 1402, 1333, 1167, 1057, 1009,
1
9
94, 950, 801, 753; H NMR (200 MHz, CDCl ) d 2.94 (s,
3
4
-Fluorobenzyl methanesulfonate (2b)
Colorless liquid; yield 95%; IR (ATR) ν/cm 3017,
3H, -CH ), 5.14 (s, 2H, benzylic), 7.13 (d, 2H, J 8.0 Hz,
H2/H6), 7.70 (d, 2H, J 8.0 Hz, H3/H5); C NMR (50 MHz,
3
-
1
13
2
931, 2855, 1508, 1156, 1061, 1043, 1010, 824, 779;
CDCl ) d 38.2 (-CH ), 70.6 (benzylic), 95.4 (C4), 130.5
(C2/C6), 133.1 (C1), 137.2 (C3/C5).
3
3
1
H NMR (200 MHz, CDCl ) d 2.88 (s, 3H, -CH ), 5.11 (s,
3
3
2
H, benzylic), 6.05-7.03 (m, 2H, H3/H5), 7.28-7.36 (m, 2H,
1
3
H2/H6); C NMR (50 MHz, CDCl ) d 37.6 (-CH ), 70.8
4-(Trifluoromethoxy)benzyl methanesulfonate (2f)
3
3
-1
(
benzylic), 115.6 (d, J 21.7 Hz, C3/C5), 129.4 (d, J 2.9 Hz,
Colorless liquid; yield 100%; IR (ATR) ν/cm 2863,
C1), 130.8 (d, J 8.5 Hz, C2/C6), 162.9 (d, J 246.4 Hz, C4).
1509, 1361, 1151, 1251, 1196, 1213, 1107, 1018, 961, 920,
1
8
13, 711; H NMR (200 MHz, CDCl ) d 2.94 (s, 3H, -CH ),
3
3
4
-Chlorobenzyl methanesulfonate (2c)
5.19 (s, 2H, benzylic), 7.20 (d, 2H, J 8.0 Hz, H3/H5), 7.42
(d, 2H, J 8.0 Hz, H2/H6); C NMR (50 MHz, CDCl3)
o
-1
13
Yellow solid; m.p. 124 C; yield 91%; IR (ATR) ν/cm
1
1
488, 1340, 1087, 1009, 805, 782; H NMR (200 MHz,
d 37.9 (-CH ), 70.4 (benzylic), 120.4 (q, J 256 Hz, -CF ),
3
3
CDCl ) d 2.94 (s, 3H, -CH ), 5.17 (s, 2H, benzylic), 7.33
121.2 (C3/C5), 130.4 (C2/C6), 132.4 (C1), 149.7 (C4).
3
3
13
(
m, 4H, H2/H3/H5/H6); C NMR (50 MHz, CDCl ) d 37.9
3
(
-CH ), 70.6 (benzylic), 128.9 (C3/C5), 130.0 (C2/C6),
32.0 (C1), 135.0 (C4).
4-(Trifluoromethyl)benzyl methanesulfonate (2g)
3
-
1
1
4
2
Colorless liquid; yield 77%; IR (ATR) ν/cm 3039,
018, 2941, 1333, 1109, 1020, 922, 801, 753; H NMR
1
3
-Bromobenzyl methanesulfonate (2d)
White solid; m.p. 153 C; yield 99%; IR (ATR) ν/cm
838, 1485, 1342, 1122, 1067, 1033, 960, 793; H NMR
(200 MHz, CDCl ) d 2.97 (s, 3H, -CH ), 5.23 (s, 2H,
3
3
o
-1
benzylic), 7.47 (d, 2H, J 8.2 Hz, H2/H6), 7.57 (d, 2H,
1
13
J 8.2 Hz, H3/H5); C NMR (50 MHz, CDCl ) d 37.4
3
(
200 MHz, CDCl ) d 2.95 (s, 3H, -CH ), 5.17 (s, 2H,
(-CH ), 70.2 (benzylic), 123.9 (q, J 270 Hz, -CF ),
3
3
3
3
1
25.2 (C3/C5), 128.7 (C2/C6), 131.3 (q, J 17 Hz, C4),
*e-mail: thfborgati@gmail.com, rosebrondi@yahoo.com.br
137.8 (C1).

S2
Synthesis and Phytotoxic Activity of 1,2,3-Triazole Derivatives
J. Braz. Chem. Soc.
3
,4-(Difluoro)benzyl methanesulfonate (2h)
Yellow liquid; yield 93%; IR (ATR) ν/cm 3029,
d4.30 (s, 2H, benzylic), 7.09-7.30 (m, 4H, H2/H3/H5/H6);
-
1
13
C NMR (50 MHz, CDCl ) d 53.9 (benzylic), 115.6 (d,
3
2
9
943, 1520, 1438, 1350, 1170, 1213, 1118, 1055, 952,
J 21.5 Hz, C3/C5), 130.0 (d, J 8.2 Hz, C2/C6), 131.4 (d,
J 2.5 Hz, C1), 162.6 (d, J 245.0 Hz, C4).
1
26, 812, 779, 735; H NMR (200 MHz, CDCl ) d 2.95
3
(
s, 3H, -CH ), 5.10 (s, 2H, benzylic), 7.07-7.23 (m, 2H,
3
1
3
H2/H5/H6); C NMR (50 MHz, CDCl ) d 37.6 (-CH ),
1-(Azidomethyl)-4-chlorobenzene (3c)
3
3
-1
7
0.0 (benzylic), 117.1-118.0 (m, C2/C5), 124.9-125.1 (m,
Yellow liquid; yield 93%; IR (ATR) ν/cm 2930, 2877,
1
C6), 130.7-130.9 (m, C1), 150.0 (dd, J 15 Hz, 250 Hz, C4),
2092, 1491, 1090, 838, 796; H NMR (200 MHz, CDCl )
3
1
50.4 (dd, J 15 Hz, 250 Hz, C3).
d 4.30 (s, 2H, benzylic), 7.24 (d, 2H, J 7.5 Hz, H2/H6),
13
7
.36 (d, 2H, J 7.5 Hz, H3/H5); C NMR (50 MHz, CDCl )
3
5
-Bromo-2-chlorobenzyl methanesulfonate (2i)
d 53.9 (benzylic), 128.9 (C3/C5), 129.4 (C2/C6), 134.0
(C1), 134.1 (C4).
o
Yellow solid; m.p. 207 C; yield 98%; IR (ATR)
-
1
ν/cm 2849, 1447, 1398, 1346, 1169, 1043, 972, 806,
1
7
5
1
61; H NMR (200 MHz, CDCl ) d 3.03 (s, 3H, -CH ),
1-(Azidomethyl)-4-bromobenzene (3d)
Yellow liquid; yield 96%; IR (ATR) ν/cm 3046, 2929,
2875, 2091, 1592, 1488, 1070, 1011, 834, 791; H NMR
3
3
-1
.18 (s, 2H, benzylic), 7.17 (d, 1H, J 8.0 Hz, H3), 7.34 (d,
1
3
1
H, J 8.0 Hz, H4), 7.53 (s, 1H, H6); C NMR (50 MHz,
CDCl ) d 37.5 (-CH ), 67.5 (benzylic), 120.4 (C5), 130.9
(200 MHz, CDCl ) d 4.30 (s, 2H, benzylic), 7.18 (d, 2H,
3
3
3
13
(
C4), 132.2 (C2), 132.6 (C3), 133.1 (C6), 133.3 (C1).
J 8.4 Hz, H2/H6), 7.51 (d, 2H, J 8.4 Hz, H3/H5); C NMR
50 MHz, CDCl ) d 53.9 (benzylic), 122.2 (C4), 129.7 (C2/
(
3
2
,4,6-Trichlorobenzyl methanesulfonate (2j)
C6), 131.9 (C3/C5), 134.4 (C1).
o
-1
Yellow solid; m.p. 242 C; yield 99%; IR (ATR) ν/cm
1
1
484, 1447, 1346, 1305, 1044, 858; H NMR (200 MHz,
1-(Azidomethyl)-4-iodobenzene (3e)
-
1
-1
CDCl ) d 3.03 (s, 3H, -CH ), 5.32 (s, 2H, benzylic), 7.26
Yellow liquid; yield 85%; IR (ATR) ν/cm ν/cm
3
3
13
(
s, 2H, H3/H5); C NMR (50 MHz, CDCl ) d37.3 (-CH ),
3026, 2931, 2912, 2857, 2120, 1585, 1481, 1058, 1007,
830, 796; H NMR (200 MHz, CDCl ) d 4.29 (s, 2H,
3
3
1
6
5.3 (benzylic), 127.3 (C1), 128.5 (C3/C5), 136.5 (C4),
3
1
37.5 (C2/C6).
benzylic), 7.06 (d, 2H, J 8.2 Hz, H2/H6), 7.71 (d, 2H,
1
3
J 8.2 Hz, H3/H5); C NMR (50 MHz, CDCl ) d 54.2
3
3
-[1’-(4’’-Bromobenzyl)-1’,2’,3’-triazol-4’-yl]propyl methane-
(benzylic), 94.1 (C4), 130.0 (C2/C6), 135.1 (C1), 137.9
(C3/C5).
sulfonate (6)
o
-1
White solid; 231 C; yield 94%; IR (ATR) ν/cm
1
3
123, 2942, 1489, 1409, 1336, 1069, 1041, 773; H NMR
1-(Azidomethyl)-4-(trifluoromethoxy)benzene (3f)
-1
(200 MHz, CDCl ) d 1.89 (t, 2H, J 5.8 Hz, H3), 2.95 (s, 3H,
Yellow liquid; yield 99%; IR (ATR) ν/cm 2098, 1509,
3
-
CH ), 3.65 (qn, 2H, J 5.8 Hz, H2), 4.14 (t, 2H, J 5.8 Hz,
1251, 1195, 1213, 1153, 1107, 1018, 1107, 1019, 847,
3
1
H1), 5.35 (s, 2H, benzylic), 7.04 (d, 2H, J 7.8 Hz, H2’’/
777; H NMR (200 MHz, CDCl ) d4.36 (s, 2H, benzylic),
3
H6’’), 7.35 (d, 2H, J 7.8 Hz, H3’’/H5’’), 7.39 (s, 1H, H5’);
7.25 (d, 2H, J 8.4 Hz, H3/H5), 7.36 (d, 2H, J 8.4 Hz, H2/
1
3
13
C NMR (50 MHz, CDCl ) d 21.9 (C3), 28.3 (C2), 37.0
H6); C NMR (50 MHz, CDCl ) d54.0 (benzylic), 120.7
3
3
(
(
-CH ), 53.1 (benzylic), 69.1 (C1), 121.6 (C5’), 122.4
C4’’), 129.6 (C2’’/C6’’), 131.9 (C3’’/C5’’), 133.8 (C1’’),
(q, J 256 Hz, -CF ), 121.4 (C3/C5), 129.7 (C2/C6), 134.4
(C1), 149.2 (C4).
3
3
1
1
2
46.2 (C4’).
1
-(Azidomethyl)-4-(trifluoromethyl)benzene (3g)
Colorless liquid; yield 81%; IR (ATR) ν/cm 2091,
-
1
-(Azidomethyl)benzene (3a)
Colorless liquid; yield 85%; IR (ATR) ν/cm 2925,
872, 2092, 1588, 1484, 1059, 1006, 786; H NMR
-
1
1
1488, 1245, 1196, 1070, 1011, 1107, 834, 791; H NMR
(200 MHz, CDCl ) d 4.37 (s, 2H, benzylic), 7.40 (d, 2H,
J 8.0 Hz, H2/H6), 7.61 (d, 2H, J 8.0 Hz, H3/H5); C NMR
(50 MHz, CDCl ) d 53.8 (benzylic), 124.1 (q, J 270 Hz,
1
3
13
(
(
200 MHz, CDCl ) d 4.26 (s, 2H, benzylic), 7.09-7.26
m, 5H, H2/H3/H4/H5/H6); C NMR (50 MHz, CDCl )
3
13
3
3
d 54.8 (benzylic), 128.4 (C4), 128.3 (C3/C5), 128.9 (C2/
-CF ), 125.5 (C3/C5), 128.1 (C2/C6), 130.2 (q, J 32 Hz,
3
C6), 135.5 (C1).
C4), 139.6 (C1).
1
-(Azidomethyl)-4-fluorobenzene (3b)
1-(Azidomethyl)-3,4-(difluoro)benzene (3h)
Yellow liquid; yield 72%; IR (ATR) ν/cm 2095,
1517, 1435, 1251, 1195, 1286, 1210, 1116, 779; H NMR
-
1
-1
Colorless liquid; yield 91%; IR (ATR) ν/cm 2931,
1
1
2880, 2093, 1601, 1508, 1221; H NMR (200 MHz, CDCl )
3

Vol. 24, No. 6, 2013
Borgati et al.
S3
1
3
(
(
(
1
1
1
200 MHz, CDCl ) d 4.31 (s, 2H, benzylic), 7.00-7.23
7.42 (s, 1H, H5’); C NMR (50 MHz, CDCl ) d21.7 (C3),
3
3
13
m, 2H, H2/H5/H6); C NMR (50 MHz, CDCl ) d 53.6
31.9 (C2), 52.9 (benzylic), 60.9 (C1), 115.6 (d, JC-F 22 Hz,
C3’’/C5’’), 121.0 (C5’), 127.6 (d, JC-F 8 Hz, C2’’/C6’’),
130.7 (d, JC-F 3 Hz, C1’’), 147.9 (C4’), 162.4 (d, JC-F 246 Hz,
C4’’); HRMS (ESI) m/z 236.1165 ([M + H], C H FN O),
3
benzylic), 116.9-117.8 (m, C2/C5), 124.2-124.3 (m, C6),
32.6-132.8 (m, C1), 149.7 (m, C4), 152.5 (m, C3).
12
15
3
-(Azidomethyl)-5-bromo-2-chlorobenzene (3i)
258.0982 ([M + Na], C H FN ONa).
12 14 3
-1
Yellow liquid; yield 92%; IR (ATR) ν/cm 2097, 1459,
1
391, 1043, 811; H NMR (200 MHz, CDCl ) d5.18 (s, 2H,
3-[1’-(4’’-Chlorobenzyl)-1’,2’,3’-triazol-4’-yl]propan-1-ol (4c)
White solid; 230-235 C; yield 73%; IR (ATR) ν/cm
3297, 3115, 3063, 2938, 2866, 1492, 1434, 1033, 907,
3
o
-1
benzylic), 7.21 (d, 1H, J 8.2 Hz, H3), 7.36 (d, 1H, J 8.2 Hz,
H4), 7.53 (s, 1H, H6); C NMR (50 MHz, CDCl ) d51.6
13
3
1
(benzylic), 120.7 (C5), 130.9 (C4), 131.2 (C2), 132.3 (C3),
761; H NMR (200 MHz, CDCl ) d 1.72 (qn, 2H, J 6.4 Hz,
3
1
1
2
32.9 (C6), 135.4 (C1).
H2), 2.61 (t, 2H, J 6.4 Hz, H3), 3.48 (t, 2H, J 6.4 Hz, H1),
4
.35 (brs, 1H, -OH), 5.27 (s, 2H, benzylic), 7.02 (d, 2H,
-(Azidomethyl)-2,4,6-(trichloro)benzene (3j)
Yellow solid; m.p. 215 C; yield 92%; IR (ATR) ν/cm
094, 1579, 1548, 1071, 853; H NMR (200 MHz, CDCl )
J 8.3 Hz, H2’’/H6’’), 7.11 (d, 2H, J 8.3 Hz, H3’’/H5’’),
o
-1
13
7.31 (s, 1H, H5’); C NMR (50 MHz, CDCl ) d 21.9 (C3),
3
1
31.9 (C2), 53.2 (benzylic), 61.1 (C1), 121.2 (C5’), 128.7
(C3’’/C5’’), 129.1 (C2’’/C6’’), 133.3 (C1’’), 134.0 (C4’’),
147.8 (C4’); HRMS (ESI) m/z 252.0875 ([M + H],
C H ClN O), 274.0700 ([M + Na], C H ClN ONa).
3
1
3
d 4.60 (s, 2H, benzylic), 7.34 (s, 2H, H3/H5); C NMR
(
(
50 MHz, CDCl ) d 51.6 (benzylic), 128.4 (C1), 130.3
C3/C5), 135.3 (C4), 136.8 (C2/C6).
3
12
15
3
12 14
3
1
-(Azido)-3-[1’-(4’’-bromobenzyl)-1’,2’,3’-triazol-4’-yl]propyl
3-[1’-(4’’-Bromobenzyl)-1’,2’,3’-triazol-4’-yl]propan-1-ol (4d)
o
-1
(
7)
White solid; 237-240 C; yield 55%; IR (ATR) ν/cm
o
-1
White solid; m.p. 242 C; yield 98%; IR (ATR) ν/cm
3278, 3133, 2942, 1489, 1430, 1046, 1011, 795, 764;
1
3
193, 3114, 2921, 2857, 2096, 1483, 1398, 1056, 1006, 797;
H NMR (200 MHz, CDCl ) d 1.88 (qn, 2H, J 6.8 Hz,
3
1
H NMR (200 MHz, CDCl ) d1.80 (qn, 2H, J 5.6 Hz, H2),
H2), 2.77 (t, 2H, J 6.8 Hz, H3), 3.64 (t, 2H, J 6.8 Hz,
H1), 4.48 (brs, 1H, -OH), 5.42 (s, 2H, benzylic), 7.11 (d,
2H, J 8.3 Hz, H2’’/H6’’), 7.35 (s, 1H, H5’), 7.45 (d, 2H,
3
2.69 (t, 2H, J 5.6 Hz, H3), 3.23 (t, 2H, J 5.8 Hz, H1), 5.36
(
(
(
s, 2H, benzylic), 7.04 (d, 2H, J 7.8 Hz, H2’’/H6’’), 7.35
d, 2H, J 7.8 Hz, H3’’/H5’’), 7.20 (s, 1H, H5’); C NMR
50 MHz, CDCl ) d 22.7 (C3), 28.5 (C2), 50.7 (benzylic),
13
13
J 8.3 Hz, H3’’/H5’’); C NMR (50 MHz, CDCl ) d 21.9
3
(C3), 31.9 (C2), 53.2 (benzylic), 61.1 (C1), 121.2 (C5’),
122.6 (C4’’), 129.6 (C2’’/C6’’), 132.1 (C3’’/C5’’), 133.9
(C1’’), 148.2 (C4’); HRMS (ESI) m/z 296.0389 ([M + H],
C H BrN O), 318.0218 ([M + Na], C H BrN ONa.
3
53.4 (C1), 121.1 (C5’), 122.8 (C4’’), 129.7 (C2’’/C6’’), 132.3
(C3’’/C5’’), 134.0 (C1’’), 147.3 (C4’).
12
15
3
12 14
3
3
-(1’-Benzyl-1’,2’,3’-triazol-4’-yl)propan-1-ol (4a)
o
White solid; m.p. 215-220 C; yield 79%; IR (ATR)
3-[1’-(4’’-Iodobenzyl)-1’,2’,3’-triazol-4’-yl]propan-1-ol (4e)
-
1
1
o
ν/cm 3293, 2972, 2880, 1379, 1087, 1045; H NMR
200 MHz, CDCl ) d 1.85 (brs, 2H, H2), 2.74 (brs, 2H,
White solid; m.p. 238-241 C; yield 90%; IR (ATR)
-1
(
ν/cm 3253, 3113, 3062, 2944, 2925, 1548, 1484, 1051,
3
1
H3), 3.62 (brs, 2H, H1), 5.42 (s, 2H, benzylic), 7.18-7.25
1008, 758; H NMR (200 MHz, CDCl ) d 1.87 (brs, 2H,
3
13
(brs, 4H, H2’’/H3’’/H5’’/H6’’), 7.29 (s, 1H, H5’); C NMR
H2), 2.76 (brs, 2H, H3), 3.63 (brs, 2H, H1), 4.34 (brs,
1H, -OH), 5.40 (s, 2H, benzylic), 6.97 (d, 2H, J 7.9 Hz,
H2’’/H6’’), 7.37 (s, 1H, H5’), 7.62 (d, 2H, J 7.9 Hz,
(
50 MHz, CDCl ) d22.0 (C3), 32.0 (C2), 54.0 (benzylic),
3
6
1
1.3 (C1), 121.2 (C5’), 128.0 (C2’’/C6’’), 128.6 (C4’’),
29.1 (C3’’/C5’’), 134.8 (C1’’), 148.4 (C4’); HRMS (ESI)
13
H3’’/H5’’); CNMR(50MHz,CDCl )d21.8(C3),31.8(C2),
3
m/z 218.1258 ([M + H], C H N O), 240.1080 ([M + Na],
53.1 (benzylic), 60.9 (C1), 94.6 (C4’’), 121.2 (C5’), 129.6
(C2’’/C6’’), 134.4 (C1’’), 137.8 (C3’’/C5’’), 148.0 (C4’);
HRMS(ESI)m/z 344.0239([M+H], C H IN O), 366.0070
12
16
3
C H N ONa).
1
2
15
3
12
15
3
3
-[1’-(4’’-Fluorobenzyl)-1’,2’,3’-triazol-4’-yl]propan-1-ol (4b)
([M + Na], C H IN ONa).
12 14 3
o
White solid; m.p. 216-217 C; yield 71%; IR (ATR)
-1
ν/cm 3274, 3112, 3062, 2943, 2873, 1549, 1419, 1091,
3-[1’-(4’’-Trifluoromethoxybenzyl)-1’,2’,3’-triazol-4’-yl]
1
1
052, 821, 786; H NMR (200 MHz, CDCl ) d 1.89 (qn,
propan-1-ol (4f)
3
o
2
H, J 6 Hz, H2), 2.77 (t, 2H, J 6 Hz, H3), 3.65 (t, 2H,
White solid; m.p. 215-220 C; yield 44%; IR (ATR)
-1
J 6 Hz, H1), 4.64 (brs, 1H, -OH), 5.45 (s, 2H, benzylic),
.95-7.04 (m, 2H, H3’’/H5’’), 7.21-7.28 (m, 2H, H2’’/H6’’),
ν/cm 3292, 3119, 3072, 2946, 2931, 1511, 1232, 1199,
1
6
1214, 1162, 1046, 1021, 842, 777; H NMR (200 MHz,

S4
Synthesis and Phytotoxic Activity of 1,2,3-Triazole Derivatives
J. Braz. Chem. Soc.
CDCl ) d1.90 (brs, 2H, H2), 2.80 (brs, 2H, H3), 3.66 (brs,
(C3’’), 132.0 (C2’’), 132.9 (C6’’), 134.5 (C1’’), 148.1 (C4’);
3
2
7
H, H1), 3.98 (brs, 1H, -OH), 5.49 (s, 2H, benzylic),
.19 (d, 2H, J 8.0 Hz, H3’’/H5’’), 7.30 (d, 2H, J 8.0 Hz,
HRMS (ESI) m/z 331.9966 ([M + H], C H BrClN O),
12
14
3
353.9776 ([M + Na], C H BrClN ONa).
12
13
3
1
3
H2’’/H6’’), 7.39 (brs, 1H, H5’); C NMR (50 MHz,
CDCl ) d 22.00 (C3), 32.04 (C2), 53.08 (benzylic), 61.3
3-[1’-(2’’,4’’,6’’-Trichlorobenzyl)-1’,2’,3’-triazol-4’-yl]propan-
3
(
1
1
3
C1), 120.4 (q, JC-F 256.0 Hz, -OCF ), 121.3 (C3’’/C5’’),
1-ol (4j)
3
o
21.3 (C4’ or C4’’), 129.5 (C2’’/C6’’), 133.7 (C5’),
49.1 (C1’’), 149.1 (C4’ or C4’’); HRMS (ESI) m/z
02.1084 ([M + H], C H F N O ), 324.0911 ([M + Na],
Yellow solid; m.p. 242-246 C; yield 67%; IR (ATR)
-1
1
ν/cm 3341, 3131, 2949, 1581, 1549, 1071, 869; H NMR
(200 MHz, CDCl ) d 1.89 (brs, 2H, H2), 2.78 (brs, 2H,
13
15
3
3
2
3
C H F N O Na).
H3), 3.17 (brs, 1H, -OH), 3.67 (brs, 2H, H1), 5.76 (s, 2H,
benzylic), 7.20-7.40 (m, 2H, H3’’/H5’’/H5’); C NMR
1
3
14
3
3
2
1
3
3-[1’-(4’’-Trifluoromethylbenzyl)-1’,2’,3’-triazol-4’-yl]propan-
(50 MHz, CDCl ) d 22.1 (C3), 32.1 (C2), 48.5 (benzylic),
3
1
-ol (4g)
61.7 (C1), 121.1 (C5’), 128.8 (C3’’/C5’’), 128.8 (C1’’),
136.3 (C4’’), 137.4 (C2’’/C6’’), 147.7 (C4’); HRMS (ESI)
m/z 320.0102 ([M + H], C H Cl N O), 341.9944 ([M + Na],
o
White solid; m.p. 216-220 C; yield 80%; IR (ATR)
-
1
ν/cm 3342, 2946, 1219, 1163, 1066, 1018, 822, 779;
12
13
3
3
1
H NMR (200 MHz, CDCl ) d1.87 (qn, 2H, J 6.4 Hz, H2),
C H Cl N ONa).
12 13 3 3
3
2
.78 (t, 2H, J 6.4 Hz, H3), 3.15 (brs, 1H, -OH), 3.64 (t, 2H,
J 6.4 Hz, H1), 5.53 (s, 2H, benzylic), 7.31 (brs, 1H, H5’),
.32 (d, 2H, J 7.9 Hz, H2’’/H6’’), 7.58 (d, 2H, J 7.9 Hz,
(1’-Benzyl-1’,2’,3’-triazol-4’-yl)methanol (5a)
o
7
White solid; m.p. 215-220 C; yield 87%; IR (ATR)
1
3
-1
1
H3’’/H5’’); C NMR (50 MHz, CDCl ) d 22.0 (C3), 32.1
ν/cm 3253, 3116, 3064, 1489, 1038, 1011; H NMR
3
(
C2), 53.5 (benzylic), 61.5 (C1), 121.4 (C5’), 123.7 (q,
(200 MHz, CDCl ) d4.11 (brs, 1H, -OH), 4.67 (s, 2H, H1),
3
JC-F 247.0 Hz, -CF ), 126.1 (C3’’/C5’’), 130.9 (q, J 31 Hz,
C4’’), 128.4 (C2’’/C6’’), 138.9 (C1’’), 148.5 (C4’); HRMS
5.43 (s, 2H, benzylic), 7.30 (brs, 5H, H2’’/H3’’/H4’’/H5’’/
3
13
H6’’), 7.43 (s, 1H, H5’); C NMR (50 MHz, CDCl ) d54.3
3
(
(
ESI) m/z 286.1124 ([M + H], C H F N O), 308.0982
(benzylic), 56.1 (C1), 122.0 (C5’), 128.2 (C2’’/C6’’), 128.9
(C4’’), 129.2 (C3’’/C5’’), 134.6 (C1’’), 148.4 (C4’); HRMS
1
3
15
3
3
[M + Na], C H F N ONa).
1
3
14
3
3
(
ESI) m/z 190.0939 ([M + H], C H N O), 212.0767
10 12 3
3-[1’-(3’’,4’’-Difluorobenzyl)-1’,2’,3’-triazol-4’-yl]propan-1-ol
([M + Na], C H N ONa).
10
11
3
(
4h)
o
Yellow solid; m.p. 215-219 C; yield 74%; IR (ATR)
[1’-(4’’-Bromobenzyl)-1’,2’,3’-triazol-4’-yl]methanol (5b)
-
1
o
ν/cm 3358, 2936, 1519, 1286, 1214, 1114, 1054, 781;
White solid; m.p. 222-224 C; yield 49%; IR (ATR)
1
-1
1
H NMR (200 MHz, CDCl ) d 1.88 (qn, 2H, J 7.0 Hz,
ν/cm 3253, 3116, 3064, 1489, 1038, 1011; H NMR
3
H2), 2.77 (t, 2H, J 7.0 Hz, H3), 3.67 (t, 2H, J 7.0 Hz,
(200 MHz, CDCl ) d 4.26 (brs, 1H, -OH), 4.65 (s, 2H,
3
H1), 5.40 (s, 2H, benzylic), 6.95-7.11 (m, 2H, H2’’/H5’’/
H6’’), 7.49 (s, 1H, H5’); C NMR (50 MHz, CDCl3)
d21.7 (C3), 31.85 (C2), 52.9 (benzylic), 60.9 (C1), 117.0
H1), 5.43 (s, 2H, benzylic), 7.11 (d, 2H, J 8.4 Hz, H2’’/
1
3
H6’’), 7.42 (d, 2H, J 8.4 Hz, H3’’/H5’’), 7.63 (s, 1H, H5’);
13
C NMR (50 MHz, CDCl ) d 53.1 (benzylic), 55.3 (C1),
3
(
(
(
d, JC-F 17 Hz, C2’’), 117.9 (d, JC-F 17 Hz, C5’’), 120.8
C4’), 124.0 (dd, JC-F 4 Hz, 7 Hz, C6’’), 123.1 (C5’), 131.7
t, JC-F 5 Hz, C1’’), 150.0 (dd, JC-F 250 Hz, 15 Hz, C4’’),
122.2 (C5’), 122.5 (C4’’), 129.5 (C2’’/C6’’), 131.9 (C3’’/
C5’’), 133.5 (C1’’), 148.2 (C4’); HRMS (ESI) m/z 268.1549
([M + H], C H BrN O).
10
10
3
1
50.5 (dd, JC-F 250 Hz, 14 Hz, C3’’); HRMS (ESI) m/z
2
54.1066 ([M + H], C H F N O), 276.0902 ([M + Na],
3-(1’-{3’’-[1’’’-(4’’’’-Bromobenzyl)-1’’’,2’’’,3’’’-triazol-4’’’-yl]
1
2
14
2
3
C H F N ONa).
propyl}-1’,2’,3’-triazol-4’-yl)propan-1-ol (8)
1
2
13
2
3
o
White solid; m.p. 240-245 C; yield 87%; IR (ATR)
-1
3
-[1’-(5’’-Bromo-2’’-chlorobenzyl)-1’,2’,3’-triazol-4’-yl]
ν/cm 3329, 3138, 3115, 2949, 2873, 1489, 1431, 1048,
1
propan-1-ol (4i)
1006, 796; H NMR (200 MHz, CDCl ) d 1.87 (qn, 2H,
3
o
White solid; m.p. 237-239 C; yield 64%; IR (ATR)
J 6.8 Hz, H2), 2.15 (qn, 2H, J 6.8 Hz, H2’’), 2.58 (t, 2H,
J 6.8 Hz, H3’’), 2.70 (t, 2H, J 6.8 Hz, H3), 3.58 (t, 2H,
J 6.8 Hz, H1), 4.12 (brs, 1H, -OH), 4.27 (t, 2H, J 6.8 Hz,
H1’’), 5.36 (s, 2H, benzylic), 7.05 (d, 2H, J 7.6 Hz, H2’’’’/
H6’’’’), 7.33 (d, 2H, J 7.6 Hz, H3’’’’/H5’’’’), 7.38 (brs, 2H,
-
1
1
ν/cm 3363, 3124, 2950, 1472, 1045, 807; H NMR
200 MHz, CDCl ) d 1.81 (brs, 2H, H2), 2.71 (brs, 2H,
(
3
H3), 3.57 (brs, 2H, H1), 4.08 (brs, 1H, -OH), 5.43 (s, 2H,
benzylic), 7.10-7.35 (m, 2H, H3’’/H4’’/H6’’), 7.39 (s, 1H,
1
3
13
H5’); C NMR (50 MHz, CDCl ) d 21.9 (C3), 31.9 (C2),
H5’/H5’’’); C NMR (50 MHz, CDCl ) d 21.9 (C3), 22.2
3
3
50.6 (benzylic), 61.1 (C1), 120.9 (C5’’), 131.1 (C4’’), 132.6
(C3’’), 29.5 (C2’’), 32.0 (C2), 49.0 (C1’’), 53.2 (benzylic),

Vol. 24, No. 6, 2013
Borgati et al.
S5
61.1 (C1), 121.5 (C5’/C5’’’), 122.6 (C4’’’’), 129.61 (C2’’’’/
147.5 (C4’’’); HRMS (ESI) m/z 405.1080 ([M + H],
C6’’’’), 132.1 (C3’’’’/C5’’’’), 133.8 (C1’’’’), 146.5 (C4’),
C H BrN O), 427.0853 ([M + Na], C H BrN ONa).
17
22
6
17 22
6
Figure S1. IR (ATR) spectrum of benzyl methanesulfonate (2a).
1
Figure S2. H NMR spectrum (200 MHz, CDCl ) of benzyl methanesulfonate (2a).
3

S6
Synthesis and Phytotoxic Activity of 1,2,3-Triazole Derivatives
J. Braz. Chem. Soc.
13
Figure S3. C NMR and DEPT-135 spectrum (50 MHz, CDCl ) of benzyl methanesulfonate (2a).
3
Figure S4. IR (ATR) spectrum of 1-(azidomethyl)benzene (3a).

Vol. 24, No. 6, 2013
Borgati et al.
S7
1
Figure S5. H NMR spectrum (200 MHz, CDCl ) of 1-(azidomethyl)benzene (3a).
3
13
Figure S6. C NMR and DEPT-135 spectrum (50 MHz, CDCl ) of 1-(azidomethyl)benzene (3a).
3

S8
Synthesis and Phytotoxic Activity of 1,2,3-Triazole Derivatives
J. Braz. Chem. Soc.
Figure S7. HRMS spectrum of 3-(1’-benzyl-1’,2’,3’-triazol-4’-yl)propan-1-ol (4a).
Figure S8. IR (ATR) spectrum of 3-(1’-benzyl-1’,2’,3’-triazol-4’-yl)propan-1-ol (4a).

Vol. 24, No. 6, 2013
Borgati et al.
S9
1
Figure S9. H NMR spectrum (200 MHz, CDCl ) of 3-(1’-benzyl-1’,2’,3’-triazol-4’-yl)propan-1-ol (4a).
3
13
Figure S10. C NMR and DEPT-135 spectrum (50 MHz, CDCl ) of 3-(1’-benzyl-1’,2’,3’-triazol-4’-yl)propan-1-ol (4a).
3

S10
Synthesis and Phytotoxic Activity of 1,2,3-Triazole Derivatives
J. Braz. Chem. Soc.
Figure S11. IR (ATR) spectrum of 4-fluorobenzyl methanesulfonate (2b).
1
Figure S12. H NMR spectrum (200 MHz, CDCl ) of 4-fluorobenzyl methanesulfonate (2b).
3

Vol. 24, No. 6, 2013
Borgati et al.
S11
13
Figure S13. C NMR and DEPT-135 spectrum (50 MHz, CDCl ) of 4-fluorobenzyl methanesulfonate (2b).
3
Figure S14. IR (ATR) spectrum of 1-(azidomethyl)-4-fluorobenzene (3b).

S12
Synthesis and Phytotoxic Activity of 1,2,3-Triazole Derivatives
J. Braz. Chem. Soc.
1
Figure S15. H NMR spectrum (200 MHz, CDCl ) of 1-(azidomethyl)-4-fluorobenzene (3b).
3
13
Figure S16. C NMR and DEPT-135 spectrum (50 MHz, CDCl ) of 1-(azidomethyl)-4-fluorobenzene (3b).
3

Vol. 24, No. 6, 2013
Borgati et al.
S13
Figure S17. HRMS spectrum of 3-[1’-(4’’-fluorobenzyl)-1’,2’,3’-triazol-4’-yl]propan-1-ol (4b).
Figure S18. IR (ATR) spectrum of 3-[1’-(4’’-fluorobenzyl)-1’,2’,3’-triazol-4’-yl]propan-1-ol (4b).

S14
Synthesis and Phytotoxic Activity of 1,2,3-Triazole Derivatives
J. Braz. Chem. Soc.
1
Figure S19. H NMR spectrum (200 MHz, CDCl ) of 3-[1’-(4’’-fluorobenzyl)-1’,2’,3’-triazol-4’-yl]propan-1-ol (4b).
3
13
Figure S20. C NMR and DEPT-135 spectrum (50 MHz, CDCl ) of 3-[1’-(4’’-fluorobenzyl)-1’,2’,3’-triazol-4’-yl]propan-1-ol (4b).
3

Vol. 24, No. 6, 2013
Borgati et al.
S15
Figure S21. IR (ATR) spectrum of 4-chlorobenzyl methanesulfonate (2c).
1
Figure S22. H NMR spectrum (200 MHz, CDCl ) of 4-chlorobenzyl methanesulfonate (2c).
3

S16
Synthesis and Phytotoxic Activity of 1,2,3-Triazole Derivatives
J. Braz. Chem. Soc.
13
Figure S23. C NMR and DEPT-135 spectrum (50 MHz, CDCl ) of 4-chlorobenzyl methanesulfonate (2c).
3
Figure S24. IR (ATR) spectrum of 1-(azidomethyl)-4-chlorobenzene (3c).

Vol. 24, No. 6, 2013
Borgati et al.
S17
1
Figure S25. H NMR spectrum (200 MHz, CDCl ) of 1-(azidomethyl)-4-chlorobenzene (3c).
3
13
Figure S26. C NMR and DEPT-135 spectrum (50 MHz, CDCl ) of 1-(azidomethyl)-4-chlorobenzene (3c).
3

S18
Synthesis and Phytotoxic Activity of 1,2,3-Triazole Derivatives
J. Braz. Chem. Soc.
Figure S27. HRMS spectrum of 3-[1’-(4’’-chlorobenzyl)-1’,2’,3’-triazol-4’-yl]propan-1-ol (4c).
Figure S28. IR (ATR) spectrum of 3-[1’-(4’’-chlorobenzyl)-1’,2’,3’-triazol-4’-yl]propan-1-ol (4c).

Vol. 24, No. 6, 2013
Borgati et al.
S19
1
Figure S29. H NMR spectrum (200 MHz, CDCl ) of 3-[1’-(4’’-chlorobenzyl)-1’,2’,3’-triazol-4’-yl]propan-1-ol (4c).
3
13
Figure S30. C NMR and DEPT-135 spectrum (50 MHz, CDCl ) of 3-[1’-(4’’-chlorobenzyl)-1’,2’,3’-triazol-4’-yl]propan-1-ol (4c).
3

S20
Synthesis and Phytotoxic Activity of 1,2,3-Triazole Derivatives
J. Braz. Chem. Soc.
Figure S31. IR (ATR) spectrum of 4-bromobenzyl methanesulfonate (2d).
1
Figure S32. H NMR spectrum (200 MHz, CDCl ) of 4-bromobenzyl methanesulfonate (2d).
3

Vol. 24, No. 6, 2013
Borgati et al.
S21
13
Figure S33. C NMR and DEPT-135 spectrum (50 MHz, CDCl ) of 4-bromobenzyl methanesulfonate (2d).
3
Figure S34. IR (ATR) spectrum of 1-(azidomethyl)-4-bromobenzene (3d).