Protatranes as synthetic malting biostimulants

Full text of DOI:10.1007/s11172-020-2742-6

Russian Chemical Bulletin, International Edition, Vol. 69, No. 1, pp. 179—181, January, 2020
179
Letters to the Editor
Protatranes as synthetic malting biostimulants
S. N. Adamovich and E. N. Oborina
A. E. Favorsky Irkutsk Institute of Chemistry,
Siberian Branch of the Russian Academy of Sciences,
1
ul. Favorskogo, 664033 Irkutsk, Russian Federation.
E-mail: mir@irioch.irk.ru
The tricyclic organoelement derivatives of triethanol-
(production of food, citric acid, yeast, bioethanol, etc.).7,8
One of these processes is the production of barley malt,
which serves as the basis for the production of fermented
drinks such as kvass, beer, whiskey, etc. The use of prota-
tranes in the production of malt practically is not studied.
The classic method of malting with three-day soaking and
eight-day germination of barley is the loosening of the
seed, the accumulation of amylolytic enzymes, nitrogen
substances and malt sugar (maltose). This is a long and
laborious process which does not meet today´s require-
ments. There are means for intensification of this technol-
ogy using natural activators such as vitamins, phytohor-
amine, "atranes" (silatranes, metallatranes, etc.), represent
a recognized class of compounds.1
—3
Earlier, we used
triethanolamine and biologically active arylchalcogenyl-
acetic acids to obtain a number of "protatranes",
+
–
[
HN(CH CH OH) ] •[ArYCH COO] and established
2 2 3 2
their structure.
4
—6
9
mones, and enzymes. However, from an economic point
of view, these methods are very expensive. Therefore, the
search for inexpensive synthetic malting stimulants is an
actual issue. This will reduce the preparation time, improve
the quality (extractability, amylolytic activity, amine ni-
trogen content, etc.), and raise the yield of malt, as well
as reduce the cost of the process.
Y = O, S, SO , Se
2
Their low toxicity (LD50 2000—4000 mg kg–1) and
high pharmacological activity (hemo-, immuno- and
cardiotropic, antiinflammatory, antitumor, antithrom-
botic, antioxidant, adaptogenic, hypocholesterolemic)
open up broad prospects for the design of advanced
drugs.3 In addition, protatranes in extremely low con-
We suggested that protatranes could become barley
malt growth stimulants. In this work, we used our improved
1
0
method to synthesize new protatranes and their analogs
1—6 (Scheme 1).
,4
–
10
centrations (down to 1•10
powerful biostimulants of various biological processes
mol.%) turned out to be
The essence of the method is the use in the reaction of
mono-, di-, or triethanolamine hydrochlorides and potas-
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 0179—0181, January, 2020.
066-5285/20/6901-0179 © 2020 Springer Science+Business Media, Inc.
1

180
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 1, January, 2020
Adamovich and Oborina
9
Scheme 1
known procedures. Soaking barley, growing and drying
malt was carried out in laboratory installations.
Compounds 1—6 were applied as aqueous solutions in
doses of 6•10– —6•10 g kg by spraying. A control
sample was not sprayed. Preliminary results showed that
the main technological characteristics (maltose content,
extractivity, yield) of malt obtained using all the synthe-
sized compounds 1—6 significantly exceeded the control.
However, the best performance was observed for protatrane
4, therefore, it was used in further in-depth studies (Table 1).
Table 1 presents the indicators of malt obtained from
barley treated with protatrane 4 in different doses.
5
–6
–1
M = Na, K
Compound
Ar
2
Y
S
S
R
H
Me
Et
—
—
—
n
1
1
2
3
3
3
1
2
3
4
5
6
4-O NC H
4-O NC H
6
4
4
2
6
4-ClC H
4-ClC H
SO2
SO2
SO2
S
6
4
6
4
Analysis of the data obtained (see Table 1) shows that
the best qualitative and quantitative characteristics of malt
are observed when barley is treated with protatrane 4 in a
4-MeC H
6
4
4-O NC H
2
6
4
sium or sodium salts of arylchalcogenylacetic acids ob-
tained in situ. The reaction is carried out as a one pot
procedure in refluxing solvent (methanol, ethanol) for
–6
–1
microdose of 6•10 g kg of grain. Thus, the following
parameters are noticeably reduced in comparison with the
control (not treated): the duration of germination (from
3
—4 h with subsequent filtering off the formed sodium or
7
to 5 days) and saccharification (from 16 to 13 min),
color (from 0.25 to 0.20 units), acidity (from 14.80 to
3.00 units). At the same time, the following parameters
potassium chlorides and evaporation of the solvent, the
yields of 1—6 having been up to 99.8% with the purity up
to 99.8%. The novelty of the method is that, instead of
dense, hygroscopic, difficult-to-purify, colored ethanol-
amines, we used solid, chemically stable, easily purified
by ordinary recrystallization, colorless, and convenient in
handling ethanolamine hydrochlorides and, instead of
acids, their Na or K salts generated in situ during the
synthesis of compounds 1—6. It is noteworthy that such
irreversible ion exchange reactions for ethanolamine hy-
drochlorides earlier were not described. The structures of
protatranes and their analogs were previously established
and confirmed by IR and multinuclear NMR spectroscopy,
elemental and X-ray diffraction analysis, as well as by
quantum chemical calculations.3
1
significantly increase: malt yield (from 79 to 84%), extrac-
tivity (from 74.8 to 78.8%), amylolytic activity (from 212
to 244 units), amine nitrogen content (from 320.70 to
3
83.15 mg) and maltose (from 63.02 to 69.93%). However,
treatment of barley with protatrane 4 in high concentration
–4
–1
(
6•10 g kg of grain) leads to a decrease in the amount
of amine nitrogen (309.11 mg) and maltose (59.24%).
Thus, using available reactants and simple synthetic
procedure we obtained a number of new protatranes and
their analogs 1—6, which turned to be efficient biostimu-
lants of malting. The use of protatrane 4 in a microdose
–6
–1
of 6•10 g kg of barley is the best option: it reduces the
preparation time, increases the yield, and improves the
quality of the malt.
—6,11
The effect of compounds 1—6 on the process of malt-
ing and the quality of the final product was investigated.
The object of the study was barley varieties "Linovice".
The evaluation of the finished malt and processing of the
results (three repetitions) was carried out according to the
IR spectra of suspensions 1—6 in Nujol or KBr pellets were
1
13
recorded on a Varian 3100 FTIR75 spectrophotometer, Н, С,
1
5
N NMR spectra in D O or methanol D were recorded on a
2
4
1
DPX 400 spectrometer (400.13 МHz for H, 101.62 МHz for
Table 1. The effect of protatrane 4 on malt indicators
Parameter
Indicators of finished malt at a dose of protatrane 4
–
1
/
g kg of grain
6
•10–4
6•10–6
6•10–8
0 (control)
Germination time/days
Extractivity (%)
5
5
78.8
244
5
75.0
231
7
74.8
212
72.4
202
20
–
1
Амилолитическая активность/ед•г
Amylolytic activity/units g–
1
13
16
16
Color/mL of 0.1 M I per 100 mL of water
0.25
14.4
309.11
59.24
78
0.20
13.00
383.15
69.93
84
0.22
14.20
371.94
63.17
82
0.25
14.80
320.70
63.02
79
2
Acidity/mL of 1 M NaOH per 100 g of extract
Amine nitrogen/mg 100 g–
Maltose content (% to extract)
Malt yield (%)
1

Protatranes as biostimulants of malting
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 1, January, 2020
181
13С, 40.18 МHz for 15
N). The purity of the compounds was
Tris(2-hydroxyethyl)ammonium 4-nitrophenylsulfanylacetate
(6). The yield was 97%. The purity was 99.7%. A powder with
determined by potentiometric titration (an EA-74 ionometer).
Synthesis of protatranes and their analogs 1—6 (general
procedure). A mixture of arylchalcogenylacetic acid (0.01 mol)
and NaOH or KOH (0.01 mol) in methanol or ethanol (30 mL)
was refluxed with stirring for 1 h, then mono-, di-, or triethan-
olamine hydrochloride (0.01 mol) was added. The mixture was
stirred for more 2 h, then cooled to 5 C. The precipitate of NaCl
or KCl was filtered off, the solvent was evaporated to obtain
a solid or an oily product in up to 99.8% yield.
–
1
–
1
m.p. 97 C. IR, /cm : 1666 (СОО ), 3328 (ОН). H NMR
(D O), δ: 7.72—7.35 (m, 4 Н, С Н ); 4.11 (s, 2 Н, СН СОО);
2
6
4
2
1
3
3.75 (t, 6 Н, ОСН ); 2.79 (t, 6 Н, NСН ). C NMR (D O),
2
2
2
δ: 168.17 (С=О), 133.15—112.62 (С Н ), 61.11 (СН СОО),
6
4
2
1
5
55.17 (ОСН ), 54.79 (NСН ). N NMR (CD OD), δ: –341.90
2
2
3
(rel. МеNО ). Found (%): C, 46.45; H, 6.11; N, 7.64.
2
C14H22N O S. Calculated (%): C, 46.39; H, 6.12; N, 7.73.
2
7
The purity of compounds 1—6 was 99.7—99.8%.
The authors are grateful to N. A. Derkanosov (Voronezh
State University of Engineering Technologies) for con-
ducting experiments on malting and discussion of the data.
The main results were obtained using the equipment of
the Baikal Analytical Center for Collective use of the
Siberian Branch of the Russian Academy of Sciences.
This work was financially supported by the Russian
Foundation for Basic Research and the Government of the
Irkutsk Region (Project Nos 20-43-38001 and 20-016-
00114).
2
-Hydroxyethylammonium 4-nitrophenylsulfanylacetate (1).
The yield was 98%. The purity was 99.6%. A colorless oil. IR,
–
1
–
1

7
/cm : 1654 (СОО ), 3290 (ОН). H NMR (D O), δ: 7.56—
2
.19 (m, 4 Н, С Н ); 4.21 (s, 2 Н, СН СОО); 3.74 (t, 2 Н,
6 4 2
1
3
ОСН ); 2.75 (t, 2 Н, NСН ). C NMR (D O), δ: 171.07 (С=О),
2
2
2
1
(
21.71—111.55 (С Н ), 60.44 (СН СОО), 55.09 (ОСН ), 54.55
6 4 2 2
1
5
NСН ). N NMR (CD OD), δ: –338.83 (rel. to МеNО ).
2
3
2
Found (%): C, 43.82; H, 5.11; N, 10.24. C10H14N O S.
2
5
Calculated (%): C, 43.79; H, 5.14; N 10.21.
N-(2-Hydroxyethyl)-N,N-dimethylammonium 4-nitrophenyl-
sulfanylacetate (2). The yield was 99.8%. The purity was 99.7%.
a colorless oil. IR, /cm– : 1649 (СОО ), 3310 (ОН). H NMR
1
–
1
References
(
D O), δ: 7.62—7.23 (m, 4 Н, С Н ); 4.14 (s, 2 Н, СН СОО);
2 6 4 2
.75 (t, 2 Н, ОСН ); 2.82 (t, 2 Н, NСН ); 1.64 (s, 6 Н, N(Me) ).
2 2 2
3
1. M. G. Voronkov, V. M. Dyakov, S. V. Kirpichenko,
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1
3
C NMR (D O), δ: 173.13 (С=О), 130.72—112.23 (С Н ),
2 2 2
N NMR (CD OD), δ: –339.73 (rel. to МеNО ). Found (%):
2
6
4
6
1.27 (СН СОО), 55.13 (ОСН ), 54.59 (NСН ), 14.01 (Ме).
1
5
3
2
C, 47.70; H, 6.08; N, 9.29. C12H18N O S. Calculated (%):
C, 47.67; H, 6.00; N, 9.27.
2
5
3
N,N-Bis(2-hydroxyethyl)-N-ethylammonium 4-chlorophenyl-
sulfonylacetate (3). The yield was 97%. The purity was 99.7%.
A powder with m.p. 49 C. IR, /cm : 1657 (СОО ), 1188,
4
–
1
–
1
1
4
324 (SO ), 3351 (ОН). H NMR (D O), δ: 7.65—7.43 (m,
2
2
Н, С Н ); 4.01 (s, 2 Н, СН СОО); 3.78 (t, 4 Н, ОСН ); 2.87
6
4
2
2
1
3
(
(
(
t, 4 Н, NСН ); 2.81 (t, 2 Н, NCH ); 1.33 (s, Ме). C NMR
2
2
D O), δ: 169.22 (С=О), 142.20 (С Н SО ), 133.71—113.44
2
6
4
2
1
5
С Н ), 60.41 (СН СОО), 55.21 (ОСН ), 54.76 (NСН ).
N
6
4
2
2
2
NMR (CD OD), δ: –340.01 (rel. to МеNО ). Found (%):
3
2
C, 45.75; H, 6.11; N 3.77. C14H22ClNO S. Calculated (%):
6
C, 45.71; H, 6.03; N, 3.81.
Tris(2-hydroxyethyl)ammonium 4-chlorophenylsulfonylacetate
(
4). The yield was 99.2%. The purity was 99.8%. A powder
8
. E. A. Privalova, N. P. Tiguntseva, S. N. Adamovich, R. G.
Mirskov, A. N. Mirskova, Russ.Chem. Bull., 2017, 66, 1320;
DOI:10.1007/s11172-017-1893-6.
–
1
–
with m.p. 94 C. IR, /cm : 1640 (СОО ), 1180, 1320 (SO ),
2
1
3
380 (ОН). H NMR (D O), δ: 7.76—7.51 (m, 4 Н, С Н ); 4.07
2
6
4
(
s, 2 Н, СН СОО); 3.82 (t, 6 Н, ОСН ); 2.81 (t, 6 Н, NСН ).
2 2 2
9. Narziss von L. Die, Technologie der Malzbereitung, 7th ed.,
Weinheim, Wiley-VCH Verlag GmbH and Co., 1999, 584 p.
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Mirskova, Russ. J. Gen. Chem., 2018, 88, 2227; DOI:10.1134/
S1070363218100353.
1
3
C NMR (D O), δ: 167.27 (С=О), 140.27 (С Н SО ), 135.75—
2
6
4
2
1
14.45 (С Н ), 62.45 (СН СОО), 54.91 (ОСН ), 54.63 (NСН ).
6 4 2 2 2
1
5
N NMR (CD OD), δ: –340.43 (rel. to МеNО ). Found (%):
3
2
C, 43.91; H, 5.69; Cl, 9.20; N, 3.72; S, 8.29. C14H22ClNO S.
7
Calculated (%): C, 43.80; H, 5.79; Cl, 9.23; N, 3.65; S, 8.35.
Tris(2-hydroxyethyl)ammonium 4-methylphenylsulfonylace-
tate (5). The yield was 96%. The purity was 99.7%. A powder
1
1. N. N. Chipanina, T. N. Aksamentova, S. N. Adamovich,
A. I. Albanov, A. N. Mirskova, R. G. Mirskov, M. G.
Voronkov, Comput. Theoret. Chem., 2012, 985, 36—45;
DOI:10.1016/j.comptc.2012.01.033.
–
1
–
with m.p. 91 C. IR, /cm : 1660 (СОО ), 1182, 1312 (SO ),
2
1
3
351 (ОН). H NMR (D O), δ: 7.70—7.42 (m, 4 Н, С Н ); 4.01
2
6
4
(
s, 2 Н, СН СОО); 3.76 (t, 6 Н, ОСН ); 2.76 (t, 6 Н, NСН ).
2 2 2
1
3
C NMR (D O), δ: 168.01 (С=О), 141.22 (С Н SО ), 135.05—
2
6
4
2
1
13.46 (С Н ), 62.02 (СН СОО), 55.11 (ОСН ), 54.76 (NСН ).
6 4 2 2 2
1
5
N NMR (CD OD), δ: –341.32 (rel. to МеNО ). Found (%):
Received July 23, 2019;
in revised form November 8, 2019;
accepted November 11, 2019
3
2
C, 49.62; H, 6.82; N, 3.78. C15H25NO S. Calculated (%):
7
C, 49.57; H, 6.93; N, 3.85.