The application of aryl substituted derivatives of xylose as environmentally friendly multipurpose pesticides

Article abstract of DOI:10.1134/S1070363216130120

A series of aryl substituted derivatives of xylose have been synthesized. Biological tests have revealed high fungicidal activity of the resulting compounds against various phythopathogenic fungi. Additional biological studies have demonstrated high plant growth regulatory activity of the compounds synthesized.

Full text of DOI:10.1134/S1070363216130120

ISSN 1070-3632, Russian Journal of General Chemistry, 2016, Vol. 86, No. 13, pp. 3002–3007. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © V.V. Belakhov, A.V. Garabadzhiu, 2016, published in Ekologicheskaya Khimiya, 2016, Vol. 25, No. 3, pp. 125–131.
The Application of Aryl Substituted Derivatives of Xylose
as Environmentally Friendly Multipurpose Pesticides
V. V. Belakhova* and A. V. Garabadzhiub
a Schulich Faculty of Chemistry, Technion – Israel Institute of Technology, Haifa, Israel
*e-mail: chvalery@techunix.technion.ac.il
b St. Petersburg State Institute of Technology (Technical University), Moskovskii pr. 26, St. Petersburg, 190013 Russia
Received October 15, 2015
Abstract—A series of aryl substituted derivatives of xylose have been synthesized. Biological tests have
revealed high fungicidal activity of the resulting compounds against various phythopathogenic fungi. Addi-
tional biological studies have demonstrated high plant growth regulatory activity of the compounds synthesized.
Keywords: xylose, aryl substituted derivatives, fungicidal activity, plant growth regulatory activity
DOI: 10.1134/S1070363216130120
INTRODUCTION
The aim of this study was to obtain aryl substituted
derivatives of xylose and examine their fungicidal and
growth regulatory activities.
Pesticides are most commonly used for crop
protection against diseases caused by phytopathogenic
fungi and bacteria and for insect destruction and also
are extensively applied as plant growth regulators
[1–3]. They belong to different classes of chemical
compounds, with the chemistry and technology of
chemical plant protection products being a constantly
developing field [4–5]. Over 2500 patents suggesting
pesticidal application for compounds obtained by both
inorganic and organic chemistry methods are published
globally every year, and over 200000 chemicals are
tested annually for different pesticidal activity profiles
[6–8]. However, crop protection chemicals include
negligible number of carbohydrates, in particular
functionally substituted monosaccharides [6, 9–14]. In
this context, our intention was to prepare practically
significant monosaccharides that would produce a dual
effect of a fungicide with respect to plant pathogens
and of a plant growth regulator. The plant growth
regulator activity is ensured by the ability of agricul-
tural plants to take carbohydrates as a source of carbon
nutrition for increasing their green mass. As a result,
such potential pesticides will not only afford a
multipurpose positive effect but also will be almost
completely spent without formation of byproducts that
need to be disposed of, thereby promoting environ-
mental safety.
EXPERIMENTAL
Chemical part. We used chemicals available from
Sigma-Aldrich (US) or Fluka (Switzerland) without
further purification. Organic solvents were purified
before use by the techniques from [15].
1
The H and 13C NMR spectra were obtained on a
Bruker Avance III (FRG) instrument (600 MHz
frequency) from 10–15% solutions in D2O or in MeOH-
d4, with TMS as internal standard. MALDI-TOF mass
spectra were measured on a MALDI Micromass (US)
spectrometer with α-cyano-4-hydroxycinnamic acid
matrix. The IR spectra were recorded on a Bruker
vector 22 (FRG) from samples pressed into KBr
pellets. To monitor the progress of the reaction and
identity of the compounds obtained we used thin-layer
chromatography on Silica Gel 60 F254 (0.25 mm,
Merck, FRG) plates in different solvent systems: ethyl
acetate–hexane, 1: 1; ethyl acetate–hexane, 3 : 2; and
methanol–chloroform, 1 : 9. Substances were detected
in the chromatograms using a special developing
solution containing 120 g of ammonium molybdate
(NH4)6Mo7O24·4H2O and 5 g of cerium(IV) ammonium
nitrate (NH4)2Ce(NO3)6 in 10% sulfuric acid H2SO4.
3002

THE APPLICATION OF ARYL SUBSTITUTED DERIVATIVES OF XYLOSE
3003
Silica Gel 60 (63–200 mm, Merck, FRG) was used as
sorbent. The melting point (decomposition tempera-
ture) was determined on an Electrothermal IA9300
(UK) instrument.
the suspensions the plants were inoculated with an
aqueous suspension of the fungus containing
50 thousand conidia per milliliter of water. The
suspension was prepared by growing the Phytophtora
infestans culture for 5–7 days on potato tuber pieces,
from which the conidia were washed off with water.
Prior to the inoculation the conidial suspension was
kept at 10°C for 20–60 min for swarmer production;
the presence of swarmers was checked microsco-
pically. After inoculation the test plants were placed
into a moist chamber and exposed for one day at 16–
20°C. Then the plants were kept in a glasshouse until
the appearance of disease manifestations, typically on
day 6–8 after inoculation. As references (standards)
served Zineb (zinc N,N'-ethylene-bis-dithiocarbamate)
[6, 9] or Polycarbacin (zinc ethylene-bis-dithiocar-
bamate-ethylene thiuram disulfide complex) [6, 9].
The damage was assessed by the presence of charac-
teristic spots on the leave surface.
Biological part. Determination of the fungicidal
activity against test cultures. The substances syn-
thesized were tested on the Fusarium moniliforme and
Rhizoctonia solani (root rot and wilting pathogens of
plants) and Venturia inaequalis (apple scab pathogen)
phytopathogenic fungi using a potato-agar medium
into which the dissolved compound at a 0.3% concen-
tration was injected. After 17–20 h the agar plate was
inoculated with mycelium of the phytopathogenic
fungi. Fungal colonies were counted on day 3 by
measuring the diameter of the fungal colony and
calculating the percentage inhibition of fungal growth
by the formula:
FCDC FCDT
× 100 %,
PIFG =
FCDC
Study of the activity against bean gray rot. Bean
plants were grown until the appearance of 6–8 leaves
which were sprayed with a suspension of the test
compound. The reference (standard) was Difenoco-
nazole {(cis,trans-3-chloro-4-[4-methyl-2-(1H)-1,2,4-
triazol-1-yl-methyl)-1,3-dioxolan-2-yl]phenyl-4-chloro-
phenyl ether, cis : trans isomer ratio, 45 : 55} [9], and
the test compound was used at a 0.1% concentration.
After drying of the suspension, the treated (for the
control, untreated) leaves of the plants were inoculated
with a Botrytis fabae spore suspension prepared 2 h
before the treatment using a 1% glucose solution
(containing at least 200 thousand spores per milliliter
of solution). Then the test plants were transferred into
a moist chamber and kept therein for 72–96 h at 22–
23°C and relative humidity of 90%. The damage was
assessed on day 4 day after inoculation.
where PIFG is the percentage inhibition of fungal
growth compared to the control, FCDC, fungal colony
diameter on the control plate, and FCDT, and fungal
colony diameter on the test plate.
The fungicidal activity was tested under glasshouse
conditions using green plants: cucumbers, tomatoes,
and beans.
Determination of the fungicidal activity against
plant diseases caused by various phytopathogens. Study
of the activity against cucumber powdery mildew.
Cucumber plants in the true leaves stage were sprayed
with an aqueous suspension of the test compounds at a
0.05% concentration of active material. The control
plant was sprayed with water. After drying of the
suspension the plants were artificially inoculated with
an aqueous suspension of the Erysiphe cichorociarum
fungus, containing 200 thousand conidia per solution
milliliter. The suspension was prepared by washing off
the Erysiphe cichorociarum conidia from the powdery
mildew-infected leaves. The inoculated plants were
kept in a glasshouse at 22–30°C. Karathane [2-(1-methyl-
heptyl)-4,6-dinitrophenyl crotonate] [6, 9] served as
standard fungicide. The tests were run in triplicate or
in quadruplicate. The plant disease development of the
cucumbers was assessed on day 10–15.
Determination of acute toxicity of aryl sub-
stituted xylose derivatives (4a–4o). Acute toxicity
(LD50) of aryl substituted derivatives of xylose 4a–4o
was studied in mongrel white male mice weighing 18–
20 g, which were maintained on a standard diet under
natural lighting conditions at room temperature. The
experimental animals were divided into groups with
10 animals in each group; the observations lasted for
5 days. The tested compounds were suspended in 0.5%
aqueous carboxymethyl cellulose solution and injected
intraperitoneally. The test results were used for
calculating LD50 for 4a–4o by the Kerber method
[16, 17]. The pharmacological experiments were carried
out in full compliance with the European Convention
Study of the activity against tomato phyto-
phtorosis. Tomato plants having several leaves were
treated with aqueous suspensions containing the tested
compounds at a 0.1% concentration. After drying of
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BELAKHOV, GARABADZHIU
Scheme 1. Synthesis of aryl substituted derivatives of β-D-xylopyranoside.
O
O
b
a
O
AcO
AcO
AcO
AcO
OAc
OAc
HO
HO
OH
OH
AcO
Br
D-(+)-xylose
1
2
R2
R5
R2
R5
R3
R4
R3
R4
R1
R1
d
c
O
O
AcO
AcO
HO
HO
O
O
OAc
OH
3a−3o
4a−4o
Reaction conditions: (a) (CH3CO)2O, C5H5N, DMAP, 0–20° C, (b) HBr (33% CH3COOH), CH2Cl2, 0°C; (c) corresponding
substituted phenol, 2,6-lutidine, Ag2CO3, acetonitrile, 20°C; and (d) NaOCH3, CH3OH, 0°C.
R1 = R2 = R3 = R4 = R5 = H (3a, 4a); R1 = R2 = R3 = R5 = H, R4 = NO2 (3b, 4b); R1 = R2 = R4 = R5 = H, R3 = NO2 (3c, 4c); R1 =
R2 = R5 = H, R3 = R4 = NO2 (3d, 4d); R1 = R5 = NO2, R2 = R3 = R4 = H (3e, 4e); R1 = R2 = R4 = R5 = H, R3 = Br (3f, 4f); R1 =
R2 = R4 = R5 = H, R3 = F (3g, 4g); R1 = R2 = R4 = R5 = H, R3 = Cl (3h, 4h); R1 = R2 = R4 = R5 = H, R3 = OCH3 (3i, 4i); R1 = R2 =
R4 = R5 = H, R3 = OCH2CH3 (3j, 4j); R1 = R2 = R5 = H, R3 = R4 = CH3 (3k, 4k); R1 = R2 = R4 = R5 = H, R3 = N(CH3)2 (3l, 4l);
R1 = R3 = R5 = Cl, R2 = R4 = H (3m, 4m); R1 = R2 = R4 = R5 = H, R3 = Si(CH3)3 (3n, 4n); R1 = R2 = R4 = R5 = H, R3 = Si
(CH2CH3)3 (3o, 4o).
for the Protection of Vertebrate Animals Used for
Experimental and Other Scientific Purposes (ETS no.
23, Strasbourg, 18.03.1986) [18].
degradable in soil, and environmentally friendly
compounds [4, 5, 25–28].
In view of the above-said, we synthesized here a
series of aryl substituted derivatives of xylose,
containing different functional groups in the aromatic
moiety, including halogens and nitro(dinitro), alkyl,
methoxy, and silyl groups (see Scheme 1).
RESULTS AND DISCUSSION
Previously, we have synthesized mono- and dis-
accharides of different classes, containing functional
groups S–Hg–R (where R is alkyl or phenyl
substituent) at the anomeric carbon atom and studied
their fungicidal and herbicidal activities [19].
Biological tests revealed pronounced fungicidal and
herbicidal activities in these derivatives, which were
even superior in biological activity to the known
effective fungicides Delsene [2-(methoxycarbonyl-
amino)benzimidazole], Vectra (bromoconazol), and
Rubigan [(±)2,4-dichloro-α-(pyrimidin-5-yl)benzhydryl
alcohol)], which are commonly used for controlling
phytopathogenic fungi. However, the presence of the
mercury atoms in the molecules of the saccharides
tested greatly limits their practical use as pesticides.
Mercury is known to be concentrated in living
organisms and to be able of transforming into highly
toxic and carcinogenic methylmercury derivatives,
resistant to degradation [20–24]. Hence, despite a high
pesticidal value, mercury compounds currently find
negligible application in most countries. The
development of new pesticides is focused today on the
preparation of high-performance, low-toxic, easily
The first stage consisted of acetylation of D-(+)-
xylose with acetic acid anhydride in pyridine,
catalyzed by 4-dimethylaminopyridine (DMAP). The
resulting xylose tetraacetate 1 was treated with hyd-
rogen bromide (in 33% acetic acid) in anhydrous
dichloromethane [29]. The bromination reaction
yielded bromo 2,3,4-tri-O-acetyl-α-D-xylopyranoside
2 which, because of instability, was introduced without
purification in the condensation reactions with various
substituted phenols in anhydrous acetonitrile in the
presence of 2,6-lutidine (2,6-dimethylpyridine) and
silver carbonate (Ag2CO3) as described in [30–32],
which yielded fully protected xylose derivatives, aryl
substituted
2,3,4-tri-O-acetyl-β-D-xylopyranosides
(3a–3o). These compounds were treated with sodium
methoxide in anhydrous methanol to remove the
acetate groups. The resulting deacetylated derivatives
were subjected to chromatographic purification with
the use of silica gel to give target aryl substituted
xylose derivatives 4a–4o. The 1H and 13C NMR
spectral parameters and physicochemical charac-
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THE APPLICATION OF ARYL SUBSTITUTED DERIVATIVES OF XYLOSE
3005
Fungicidal activity of the aryl substituted derivatives of xylose
Plant disease development suppression, %
Fungal mycelium growth inhibition, %
cucumber
powdery mildew phytophtorosis
tomato
bean gray
rot
Fusarium
moniliforme
Rhizoctonia
solani
Venturia
inaequalis
Compound
4a
4b
4c
4d
4e
4f
27
39
36
75
70
54
50
61
30
32
29
35
91
34
30
19
31
27
64
59
47
41
52
21
20
25
29
82
23
21
11
23
29
53
50
42
39
45
17
15
19
23
76
19
15
12
54
51
62
71
46
40
56
32
36
32
30
89
24
29
10
46
43
57
60
37
45
49
24
29
22
18
100
19
15
7
63
60
82
75
54
39
55
21
33
19
28
100
15
11
4g
4h
4i
4j
4k
4l
4m
4n
4o
teristics of 4a–4o were fully consistent with the
moderate (4b, 4c, and 4g–4l) to low (4a, 4n, and 4o)
published data [30–35].
fungicidal effect.
Aryl substituted derivatives of β-D-xylopyranoside
4a–4o were tested as wheat seed protectants against a
complex of mold pathogens. It was shown that, in
fungicidal activity, 4d, 4e, and 4m were slightly
inferior to the reference Granosan [N-(ethylmercury)-p-
toluenesulfonanilide] and equal to another reference,
Dazomet (tetrahydro-3,5-dimethyl-2H-1,3,5-thiadiazine-
2-thione) [6, 9]. Pharmacological studies of aryl
substituted β-D-xylopyranoside derivatives 4a–4o
revealed the acute toxicity (LD50) of 770–920 mg/kg
(white mice, intraperitoneal injection), which is
30 times lower than that of Granosan (26–30 mg/kg)
[9], and 1.5–2.0 times lower than that of Dazomet
(450 mg/kg) [9]. However, the use of 4a–4o under the
test conditions was found to reduce seed germination.
The remaining derivatives showed moderate (4b, 4c,
and 4f–4l) or low (4a, 4n, and 4o) fungicidal activities.
The biological tests showed that the resulting aryl
substituted xylose derivatives 4d, 4e, and 4m
containing two nitro groups (4d, 4e) and three chlorine
atoms (4m) in the phenyl ring showed high activity
against phytopathogenic fungi that cause diseases in
agricultural plants (see table). Derivatives 4f, 4g, and
4h containing halogens bromine, fluorine, and
chlorine, respectively, in the para position of the
phenyl ring exhibited moderate fungicidal activity
against phytopathogenic fungi. The fungicidal activity
of the remaining derivatives, 4a–4c, 4i–4l, 4n, and 4o
was not high, with plant disease development sup-
pressed by no greater than 40% (see table). Derivative
4m exhibited very high activity against the test
cultures of phytopathogenic fungi. For example, its use
resulted in 100% suppression of the mycelial growth
of Rhizoctonia solani (the causal agent of root rot and
wilting of plants) and Venturia inaequalis (apple scab
pathogen), as seen from the table. The fungicidal
activity of 4d and 4e was also high, ranging from 60 to
82%. The remaining derivatives exhibited from
Along with different types of biological activity
(fungicidal, antibacterial, insecticidal, etc.), agricul-
turally applied pesticides displayed a growth regu-
latory activity in some cases [36–39]. Additional
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BELAKHOV, GARABADZHIU
boleznei (Protection of Plants against Diseases),
Moscow: KolosS, 2004.
biological tests of derivatives 4a–4o revealed a growth
regulatory activity on the cells cultures of higher
plants. The application of these compounds was shown
to increase the growth rate of cabbage cell culture and
the specific respiration rate by 7–10%, in which
parameter they are not inferior to the known plant
growth regulators such as Ethephon (2-chloroethyl-
phosphonic acid) [6], NIA-10656 (propylphosphonic
acid) [6, 9] and Alar (N-dimethylaminosuccinamic acid)
[9].
8. Soldatenkov, A.T., Kolyadina, N.M., and Le Tuan, A.,
Pestitsidy i regulyatory rosta rastenii: prikladnaya
organicheskaya khimiya (Pesticides and Plant Growth
Regulators: Applied Organic Chemistry), Moscow:
BINOM, 2013.
9. Mel’nikov, N.N., Novozhilov, K.V., and Belan, S.R.,
Pestitsidy i regulyatory rosta rastenii (Pesticides and
Plant Growth Regulators), Moscow: Khimiya, 1995.
10. Pesticides in the Modern World – Pesticides Use and
Management, Stoytcheva, M., Ed., Rijeka (Croatia):
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CONCLUSIONS
11. Popova, L.M., Kurzin, A.V., and Evdokimov, A.N.,
Pestitsidy (Pesticides), St. Petersburg: Prospekt Nauki,
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and Howe-Grant, M., Eds., New York: Wiley, 1996,
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(1) Aryl substituted derivatives of xylose have been
synthesized with a low toxicity and a high fungicidal
activity against a range of phytopathogenic fungi that
cause both diseases of agricultural plants and mold
development on seeds.
13. Geldmacher-v.Mallinckrodt, M. and Machbert, G., in
Analytical Toxicology for Clinical, Forensic, and
Pharmaceutical Chemists, Brandenberger, H. and
Maes, R.A.A., Eds., Berlin: Walter de Gruyter, 1997,
pp. 215–263.
(2) The resulting aryl substituted derivatives of
xylose are also suitable as plant growth regulators,
which allows them to be considered as environ-
mentally acceptable pesticides for potential multi-
purpose use.
14. Rose, R.L., in Toxicology, Marquardt, H., Ed., San
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ACKNOWLEDGMENTS
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Laboratory Chemicals, Oxford: Butterworth-Heine-
mann, 2012.
The authors are grateful to Dr. D. Metrine,
(Institute of Antibiotics and Medical Enzymes, Saint-
Petersburg, Russia) for carrying out the biological
tests.
16. Ashmarin, I.P. and Vorob’ev, A.A., Statisticheskie
metody
v
mikrobiologicheskikh issledovaniyakh
(Statistical Methods in Microbiological Studies),
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