Special Issue on Biological Engineering & Natural Science, September-October 2013

ISSN: 2347 6087 2013 | Published by The Standard International Journals (The SIJ) 12



AbstractNew substituted pyrazolopyridines and hydrazinopyridines were synthesized by reacting 4,6-
dimethyl-2-chloro-, 4,6-dimethyl-2,5-dichloro- and 4-methyl-2,6-dichlornicotinonitriles with hydrazine, alkyl
hydrazines and phenylhydrazine, and the peculiarities of the reactions were identified. 4-Methyl-6-(pyrazol-1-
yl)- chlornicotinonitriles obtained through condensation of hydrazinopyridine with acetylacetone and ethyl
acetoacetate, which exhibit similar characteristics in reactions with hydrazines. Quite representative ranks of
derivatives of 3-cyanopyrid-6- hydrazide of carboxylic acids, -semicarbazides, -hydrazones, as well as
pyrazolopyridyl-3-urea and carboxamides are synthesized on the basis of key structures. The representatives
exhibiting antidotal activity on sunflower plants and growth-stimulating effect on sunflower and sugar beet
were detected among the synthesized compounds.
KeywordsBiological Activity; Cyclization; Hydrazinopyridines; Pyrazolopyridines; Synthesis.

I. INTRODUCTION & RELATED WORKS
ETEROCYCLIC compounds are widely spread in
nature in the form of vitamins, alkaloids, pigments;
they are a part of animal and plant cells; many of
them are of primary importance for living systems and serve
as key components in biological processes. They are applied
in different crop production areas as bactericides, herbicides,
defoliants, desiccants etc.; most medicines were developed
based on heterocyclic compounds [Gilchrist, 1996].
Derivatives of pyrazolopyridines are one of the most
promising chemical classes for a search of biologically active
compounds. To obtain 3-aminopyrazolo [3,4-b]pyridines the
interaction of 2-chloronicotinonitriles with hydrazines is used
most frequently [Lynch et al., 1988; Kamal El-Dean et al.,
1991; Hahn & Muszyski, 1996]. However, there are rare
references about the interaction of 2-chloronicotinonitriles
with hydrazine and its derivatives and almost all of them
describe reactions with hydrazine hydrate. Only few
publications [Lynch et al., 1988] contain data about the
interaction with methylhydrazine while there are no
evidences about reactions with other alkyl derivatives of
hydrazine. At the same time, hydrazinonicotinonitriles and
aminopyrazolopyridines resulting from these reactions
contain highly reactive hydrazino and amino groups,
respectively, and are of interest as appropriate synthon for
fine organic synthesis. These facts show that further studies
in this field are necessary.
II. METHODS
We studied nucleophilic substitution of a chlorine atom in the
series of chloronicotinonitriles 1- in reactions with
hydrazine, alkylhydrazines and phenylhydrazine (Scheme 1)
to obtain key structures for synthesis of biologically active
compounds [Dyadyuchenko, 2013].
For this purpose, chloronicotinonitriles 1- interacted
with hydrazine hydrate, methyl-, dimethyl- ethyl-, 1,1-
dimethyl- and phenylhydrazines. The reactions were
H
*Key Researcher, Laboratory for Plant Growth Regulators, All-Russian Research Institute of Biological Plant Protection, Krasnodar,
RUSSIA. E-Mail: ludm.dyadiuchenko@yandex.ru
**Head of the Laboratory for Plant Growth Regulators, All-Russian Research Institute of Biological Plant Protection, Krasnodar, RUSSIA.
E-Mail: vladstrelkov@yandex.ru
***Senior Researcher, Laboratory for Plant Growth Regulators, All-Russian Research Institute of Biological Plant Protection, Krasnodar,
RUSSIA. E-Mail: danazarenko@yandex.ru
****Associate Professor, Department of Organic Chemistry, Kuban State Agrarian University, Krasnodar, RUSSIA.
E-Mail: dm.a.dm@rambler.ru
L.V. Dyadyuchenko
*
, V.D. Strelkov
**
, D.Y. Nazarenko
***
& I.G. Dmitrieva****
Synthesis of Substituted
Hydrazinopyridines, Pyrazolopyridins
and their Derivatives.
Screening of Bioactive Compounds
Special Issue on Biological Engineering & Natural Science, September-October 2013
ISSN: 2347 6087 2013 | Published by The Standard International Journals (The SIJ) 13
performed in the ethanol medium at the boiling point of the
reaction mass.
The nicotinonitriles 1- appeared to have ambiguous
reactions with hydrazine and its derivatives. The reaction
product structures were dependent on character and position
of substituents in the pyridine cycle.
So, nicotinonitriles 1a,b which reacted with hydrazine
hydrate and methylhydrazine yielded similar products 3-
amino-4,6-dimethyl-5-(H, chloro)-pyrazolo[3,4-b]pyridines
(2a-b) and 3-amino-1,4,6-trimethyl-5-(H, chloro)-
pyrazolo[3,4-b]pyridines
3a-b, respectively. That means that these reactions
include two consecutive stages: 1) nucleophilic substitution
of a chlorine atom in the position of pyridine 2 for hydrazino
(methylhydrazino) group; 2) intramolecular attack with a
terminal nitrogen atom of hydrazino (methylhydrazino) group
against a carbon atom that lacks electrons and is a part of a
cyano group. This attack ends in forming a pyrazole cycle. It
was impossible to isolate intermediate 2-hydrazino-, 2-
methylhydrazino derivatives.
Scheme 1
N Cl
R CN
NH
2
NH
2
NH
2
NH
2
N
N
N
NH
2
R
N Cl
CN
N N H
2
NH
2
NHEt
N Cl
CN
N N H
2
NH
2
NHEt
N
N
N
NH
2
R
NH
2
NHMe
NH
2
NMe
2
N Cl
CN
N N H
2
NH
2
NHMe
NH
2
NMe
2
R
1
.
H
2
O
.
H
2
O
R
1
1a-c
2a-b
H
4
H
3a-b
6
5

1a R=H, R
1
=CH
3
; b R=Cl, R
1
=CH
3
; c R=H, R
1
=Cl; 2, 3a R=H, b R=Cl.
Other results were produced through interaction of 4-
methyl-2,6-dichloronicotinonitrile 1 with hydrazine hydrate
and methylhydrazine. In this case, the reaction ended in the
formation of respective monohydrazino and
monomethylhydrazino derivatives, there was not any further
heterocyclization leading to the formation of a pyrazolo
cycle. It should be noted that a change of the initial reagent
ratio towards increasing excess hydrazines does not lead to
obtaining dihydrazine-substituted products.
While in the case of the above-mentioned nicotinonitriles
1a,b the substitution of a chlorine atom is possible only in
position 2 (nucleophilic groups cannot be substituted for a
chlorine atom in position 5 as it is located in the electrophilic
center of pyridine), on the contrary, in the case of 4-methyl-
2,6-dichloronicotinonitrile 1 a chlorine atom may be
substituted both in position 2 and in position 6. Neither
NMR
1
H spectroscopy nor mass spectrometry provided
reliable identification of the carbon atom that is involved in
the reaction. For this purpose, we used the two-dimensional
homonuclear (
1
-
1
) magnetic resonance method.
Structures were determined taking methylhydrazino-
substituted product 5 as an example (Scheme 1) by using
Nuclear Overhauser Effect Spectroscopy (NOESY)
[Dmitrieva et al., 2006]. This method enables the correlation
of chemical shifts of protons which are closely (2-5
angstrms) located in space, irrespective of the number of
bonds between them.
In the NOESY spectrum of compound 5 Figure 1,
correlation peaks characterizing the interaction of protons
NH
2
and
3
of the methylhydrazino group with -5 of the
pyridine cycle were recorded which shows the location of
group NMeNH
2
in position 6 of the pyridine ring:
Special Issue on Biological Engineering & Natural Science, September-October 2013
ISSN: 2347 6087 2013 | Published by The Standard International Journals (The SIJ) 14
N Cl N
CN
CH
3
N H
2
C H
3
5

Figure 1: Main interactions with proton -5 of the pyridine cycle in
the NESY spectrum of 6-(1-methylhydrazino)-4-methyl-2-
chloronicotinonitrile 5
Thus, an additive effect of substituents and steric factors
led to selective reactions of nucleophilic substitution for
pyridine ring carbon atom 6 in 4-methyl-2,6-
dichloronicotinonitrile.
It was also determined that nicotinonitriles 1a,b reacted
with ethyl hydrazine by eliminating
2

5
group and forming
pyrazolopyridines 2a-b. However, unlike the latter, in
nicotinonitril 1c the ethyl hydrazine group was easily
substituted for the chlorine atom (Compound 6).
In reactions between 1,1-dimethylhidrazine and initial
compounds 1a,b, one methyl group undergoes an elimination
reaction which results in the formation of products 3a-b. The
interaction of 1,1-dimethylhydrazine with nicotinonitrile 1c is
also accompanied by the elimination of a methyl group and,
as a result, 6-methylhydrazino derivative 5 is obtained.
Phenylhydrasine does not react with compounds 1a-c,
perhaps, because of its low nucleophilicity.
Novel bisheterocyclic systems were synthesized through
reactions of 6-hydrazino-4-methyl-2-chloronicotinonitrile 4
with acetylacetone and acetoacetic ester (Scheme 2).
Scheme 2
N Cl
CH
3
CN
N
H
N H
2
AcCH
2
COOEt
CH
2
(Ac)
2
N N
N Cl
CH
3
CN
CH
3
C H
3
NH
2
NHR
N
N
N N
N
CH
3
CH
3
C H
3
NH
2
R
N N
N Cl
CH
3
CN
OH
C H
3
N N
N Cl
CH
3
CN
C H
3 O
NH
2
NHR
N
N
N N
N
CH
3
C H
3
NH
2
R
O
NH
2
(CH
3
)
2
NH
2
(CH
3
)
2
NH
2
Et
NH
2
Et
4
7
8a,b
9
10a,b
10b
8b
10a
8a

where 8a R=H; 8b CH
3
; R
1
=CH
3
; 10a R=H; 10b CH
3
.
It was determined that condensation of hydrazine group
with acetylacetone resulting in the pyrazole cycle with high
yield takes place in a subacid medium containing a catalytic
amount of acetic acid (Compound 7). The reaction with
acetoacetic ether requires stricter conditions: increasing
heating time of the reaction mass and a stronger acid as a
catalyst, such as hydrochloric acid (Compound 9).
Further, the synthesized 6-pyrazolo- and 6-
pyrazolonicotinonitriles (compounds 7 and 9, respectively)
were subjected to reactions with hydrazine hydrate, methyl-,
dimethyl- 1,1-dimethyl-, and ethyl hydrazines. In all these
cases, the reactions ended with intramolecular cyclization
into a pyrazolic cycle. The activity of 1,1-dimethylhydrazine
caused elimination of one methyl group in compounds 7 and
9 and that led to obtaining new products 8b and 10b which
were the same as in reactions with methylhydrazine. In case
of the interaction with ethyl hydrazine, the
2

5
group
underwent elimination and products 8 and 10 were
obtained.
So, the reactions including 1,1-dimethyl- and ethyl
hydrazines demonstrated the same regularities which were
described above.
The structures of compounds 2,3a-b, 4-6, 8,10a-b were
validated using the combination of elemental analysis, IR,
NMR
1
and mass spectra Tables 1, 2.

Special Issue on Biological Engineering & Natural Science, September-October 2013
ISSN: 2347 6087 2013 | Published by The Standard International Journals (The SIJ) 15
Table 1: Physicochemical Characteristics of Compounds Synthesized
Compound mp,

Brutto Formula
Found, %
Calculated, %
Yield,
%
N
2a 239-240 C
8
H
10
N
4

59.63
59.24
6.33
6.21
34.20
34.55
76
2b 318-319 C
8
H
9
ClN
4

48.41
48.86
4.48
4.62
28.88
28.49
68
3a 116-117 C
9
H
12
N
4

61.62
61.34
6.65
6.87
31.53
31.80
85
3b 178-179 C
9
H
11
ClN
4

51.87
51.31
5.47
5.26
26.32
26.60
80
4 258-260 C
7
H
7
ClN
4

46.50
46.04
3.62
3.86
30.40
30.68
82
5 184-185 C
8
H
9
IN
4

48.46
48.86
4.43
4.61
28.38
28.49
78
6 142-143 C
9
H
11
CIN
4

51.41
51.31
5.38
5.26
26.26
26.59
68
7 162-163 C
12
H
11
CIN
4

58.61
58.42
4.26
4.49
22.50
22.71
75
8 185-186 C
12
H
14
N
6

59.14
59.49
6.04
5.82
34.77
34.69
72
8b 189-190 C
13
H
16
N
6

61.12
60.92
6.15
6.29
32.44
32.79
76
9 265-267 C
11
H
9
CIN
4

53.48
53.13
3.71
3.65
22.81
22.53
73
10a 256-257 C
11
H
12
N
6

54.68
54.41
4.73
4.95
34.59
34.41
70
10b 222-224 C
11
H
14
N
6

55.61
55.80
5.31
5.46
22.80
22.54
68
Table 2: NMR
1
, IR and mass spectra of compounds 1-10
Compound NMR
1
spectrum, , ppm (J, Hz), DMS-d
6

Mass spectrum,
+
(relative intensity, %)
IR spectrum, , cm
-1

2a
2.40 (3H, s, 4-CH
3
); 2.60 (3H, s, 6-CH
3
); 5.09 (2, brs, N
2
); 6.59
(1, s, 5- Py*); 11.72 (1, s, N-).
162 (100)
3380, 3281 (NH); 1575, 1560
(C=C, C=N).
2b
2.55 (3H, s, 4-CH
3
); 2.65 (3H, s, 6-CH
3
); 5.12 (2, brs, N
2
); 11.92
(1, s, N-).
196 (100)
3374, 3252 (NH); 1597, 1563
(C=C, C=N).
3a
2.45 (3H, s, 4-CH
3
); 2.55 (3, s, 6-CH
3
); 3.70 (3, s,
3
-N); 5.18
(2, brs, N
2
); 6.60 (1, s, 5- Py).
176 (100)
3360 (NH); 1620, 1570 (C=C,
C=N).
3b
2.58 (3H, s, 4-CH
3
); 2.65 (3H, s, 6-CH
3
); 3.70 (3, s,
3
-N); 5.31
(2, brs, N
2
).
210 (100)
3375 (NH); 1602, 1562 (C=C,
C=N).
4
2.35 (3H, s, 4-CH
3
); 4.55 (2, brs, N
2
); 6.85 (1, s, 5- Py); 8.95
(1, s, N-).
182 (100);
3385, 3276 (NH); 2225 (CN);
1596, 1563 (C=C, C=N).
5
2.65 (3H, s, 4-CH
3
); 3.25 (3, s,
3
-N ); 5.02 (2, brs, N
2
); 7.05
(1, s, 5- Py).
196 (49);
3376 (NH
2
); 2221 (CN); 1582,
1561 (C=C, C=N).
6
1.10 (3, t, J=6,8; CH
2
CH
3
); 2.65 (3H, s, 4-CH
3
); 3.81 (2H, q, J=6,8;
CH
2
CH
3
); 4.90 (2, brs, N
2
); 7.85 (1, s, 5- Py).
210 (28);
3371 (NH
2
); 2216 (CN); 1578,
1566 (C=C, C=N).
7
2.29 (3H, s, 3-CH
3
Pr**); 2.51 (3H, s, 4-CH
3
Py); 2.62 (3H, s, 5-CH
3
Pr); 5.93 (1H, s, 4-H Pr); 7.38 (1, s, 5- Py).
246(88)
2230 (CN); 1597, 1581(C=C,
C=N).
8
2.34 (3H, s, 3-CH
3
Pr); 2.62 (3H, s, 4-CH
3
Py); 2.70 (3H, s, 5-CH
3
Pr);
5.60 (2, brs, N
2
); 6.05 (1H, s, 4-H Pr); 6.88 (1, s, 5- Py); 11.09
(1, s, N-).
242(52)
3332(NH
2
);1561, 1540(C=C,
C=N).
8b
2,.32 (3H, s, 3-CH
3
Pr); 2.60 (3H, s, 4-CH
3
Py); 2.68 (3H, s, 5-CH
3
Pr);
3.97 (3H, s, N-CH
3
);

5.42 (2, brs, N
2
); 6.02 (1H, s, 4-H Pr); 6.56
(1, s, 5- Py).
256(49)
3306(NH
2
);1558, 1535(C=C,
C=N).
9
2.03 (3H, s, 3-CH
3
Pr); 2.65 (3H, s, 4-CH
3
Py); 3.32 (2H, s, 4-CH
2
Pr);
7.46 (1, s, 5- Py).
248(60)
2226 (CN); 1651(C=O),1593,
1563(C=C, C=N).
10a
2.36 (3H, s, 3-CH
3
Pr); 2.84 (3H, s, 4-CH
3
Py); 3.30 (2H, s, 4-CH
2
Pr);
5.90 (2, brs, N
2
); 6.81 (1, s, 5- Py); 11.65 (1, s, N-).
244(36)
3329(NH
2
); 1606(C=O),1550,
1523(C=C, C=N).
10b
2.36 (3H, s, 3-CH
3
Pr); 2.86 (3H, s, 4-CH
3
Py); 3.34 (2H, s, 4-CH
2
Pr);
3.88 (3H, s, N-CH
3
);6.11 (2, brs, N
2
); 6.77 (1, s, 5- Py).
256(33)
3306(NH
2
); 1622(C=O),1543,
1539(C=C, C=N).
* Py pyridine; ** Pr - pyrazole
Special Issue on Biological Engineering & Natural Science, September-October 2013
ISSN: 2347 6087 2013 | Published by The Standard International Journals (The SIJ) 16
The obtained 3-aminopyrazolopyridines 2a-b, 3a-b, 8a-b,
and 10a-b were used as basic structures for synthesis of
potential biologically active compounds. For this purpose,
they underwent acylation with isocyanates and carboxylic
acid chlorides (Scheme 3).
It was determined experimentally that the interaction
with aromatic and alicyclic isocyanates ran smoothly while
boiling them in anhydrous dioxane medium for 4-5 hours and
led to obtaining N-substituted ureas 10- with yield 61-76
%.
Scheme 3
N
N
N
NH
2
N
N
N
N N
O
N
N
N
N
O
Cl
O
N=C=O
H H
H
R
R
11a-c
R
12a-s
R
1
R
1
R
1
R
2
R
3
R
2
R
3
R
4
R
4
R
2
2,3,8,10a-b

11a R = R
1
= H, R
2
= CH
3
, R
3
= cyclohexyl; 11b R = R
1
= H, R
2
= CH
3
, R
3
= 3,4- dichlorophenyl; 11 R = R
1
= H, R
2
= CH
3
, R
3
=
3- chlorophenyl; 12 R= H, R
1
= R
2
= CH
3
, R
4
= 4- methylphenyl; 12b R= H, R
1
= R
2
= CH
3
, R
4
= 4- chlorophenyl; 12 R= H, R
1
= R
2
= CH
3
, R
4
= CH=CHC
6
H
5
; 12d R= H, R
1
= R
2
= CH
3
, R
4
= 2- methoxyphenyl; 12 R= H, R
1
= R
2
= CH
3
, R
4
= phenyl; 12f
R= H, R
1
= R
2
= CH
3
, R
4
= 2- chlorophenyl; 12g R= H, R
1
= R
2
= CH
3
, R
4
= n-butyl; 11h R= CI, R
1
= R
2
= CH
3
, R
4
= 2-
chlorophenyl; 11i R= CI, R
1
= R
2
= CH
3
, R
4
= 2- methoxyphenyl; 12j R= CI, R
1
= R
2
= CH
3
, R
4
= CH=CHC
6
H
5
; 12k R= CI, R
1
=
R
2
= CH
3
, R
4
= isobutyl; 12l R= CI, R
1
= R
2
= CH
3
, R
4
= ethyl; 12m R= R
1
= H, R
2
= CH
3
, R
4
= 4- chlorophenyl; 12n R= CI, R
1
=
R
2
= CH
3
, R
4
= 2- fluorophenyl; 12o R= CI, R
1
= R
2
= CH
3
, R
4
= 4- bromophenyl; 12p R= CI, R
1
= R
2
= CH
3
, R
4
= 3-
chlorophenyl; 12q R= CI, R
1
= R
2
= CH
3
, R
4
= 3,5-dinitrophenyl; 12r R= CI, R
1
= R
2
= CH
3
, R
4
= 4- methylphenyl; 12s R= R
1
=
H, R
2
= CH
3
, R
4
= neopentyl.
The acylation with carboxylic acids chlorides was done
under milder conditions, at room temperature, and was
completed after 2-4 hours. For this reaction, the acid chloride
solution in benzene was added in drops while mixing to the
suspension of 3-aminopyrazolo[3,4-b]pyridine 2,3,8,10-b
and equimolar amount of anhydrous benzene. The yield of
targeted N-(pyrazolo[3,4-b]-pyridyl-3)-carboxamides 11a-s
was 66-82 %.
Hydrazinopyridines 4-6 were also used for synthesis of
biologically active compounds.
It is known that hydrazinopyridines are capable to be
acidylated by anhydrides or halides of carboxylic acids
[Kobrakov et al., 2003]. Depending on the reactivity of
hydrazinopyridines, the reaction may occur at room
temperature or under heating in a solvent or without a
solvent. At the same time there is no data in the literature on
reactions of hydrazinopyridines with isocyanates.
Reactions of 6-hydrazino (alkylhydrazino)-4-methyl-2-
chlornicotinonitriles 4-6 with iso - and isothiocyanates,
carboxylic acid chlorides and aldehydes were studied
(Scheme 4).
Scheme 4
N Cl N
NH
2
R
NC
N Cl N
NC
R
N
N
X
N C
N Cl N
R
N
NC
O
H
N Cl N
R
NC
N
O
O
CI
H
H H
X
R
1
R
3
R
3
4-6
15a-i
R
2
R
2
13a-n
R
1
14a-f

13a R= CH
3
, R
1
= phenyl; 13b R = CH
3
, R
1
= 3- methylphenyl; 13 R = CH
3
, R
1
= 2- methoxyphenyl; 13d R = CH
3
, R
1
= 2-
chlorophenyl; 13 R = CH
3
, R
1
= 4- methylphenyl; 13f R = CH
3
, R
1
= 4- chlorophenyl; 13g R = CH
3
, R
1
= isobutyl; 13h R =
C
2
H
5
, R
1
= 4- methylphenyl; 13i R = C
2
H
5
, R
1
= n-butyl; 13j R = C
2
H
5
, R
1
= phenyl; 13k R, R
1
= C
2
H
5
; 13l R= H, R
1
= n-butyl;
13m R = H, R
1
= CH
2
C
6
H
5
CI
2
-2,4; 13n R = CH
3
, R
1
= t-butyl; 14 R= H, R
2
= 3,4- dichlorophenyl, X = O; 14b R = H, R
2
=
cyclohexyl, X = O; 14c R =H, R
2
= ethyl, X = S; 14d R = CH
3
, R
2
= naphthyl -1, = ;14 R = CH
3
, R
2
= ethyl, = S; 14f R =
CH
3
, R
2
= phenyl, = S; 15a R = CH
3
, R
3
= 2- nitrophenyl; 15b R = CH
3
, R
3
= 4- methylphenyl; 15 R = C
2
H
5
, R
3
= 4- phenetyl;
15d R = C
2
H
5
, R
3
= 4- diethylaminophenyl; 15 R = C
2
H
5
, R
3
= 4- methylphenyl; 15f R = C
2
H
5
, R
3
= 2- hydroxy -5-
brominephenyl; 15g R = C
2
H
5
, R
3
= 3,4- dichlorophenyl; 15h R = C
2
H
5
, R
3
= 4- nitrophenyl; 15i R = C
2
H
5
, R
3
= 4- acetamid
phenyl
Special Issue on Biological Engineering & Natural Science, September-October 2013
ISSN: 2347 6087 2013 | Published by The Standard International Journals (The SIJ) 17
6-Alkylhydrazinonicotinenitrites 5-6 show high activity
in reactions with carboxylic acid chlorides. The best results
are obtained by conducting the reaction in the temperature
range 8-12 C in anhydrous benzene in the presence of Et3N.
Output of thus obtained products 13a-n was 64-82%, and
only the compound 13k was synthesized with 54% output.
The increase of the reaction temperature to ambient leads to a
considerable decrease in the output of the target products as a
result of partial resinification of reaction mass.
Acylation of 6-hydrazinonicotinonitrile 4 with carboxylic
acid chlorides requires heating of the reaction mixture to 40-
45 C, which is due, presumably, to the absence of electron
donating alkyl groups on the nitrogen atom.
Reaction with isocyanates and isothiocyanates smoothly
proceeds at boiling of the starting components in the
anhydrous dioxane solution and leads to the formation of 4-
methyl-2-chloro-3-cyanopyridyl-6-semicarbazides and
thiosemicarbazides 14a-f with output 69-80%.
Some of the corresponding 4-methyl-2-chloro-3-
cyanopyridyl-6-hydrazones 15a-i are obtained by reacting
pyridyl-6-alkylhydrazines 5-6 with aromatic aldehydes. The
reaction is carried out at boiling equimolar amounts of the
starting components in ethanol for 2-4 hours and leads to the
formation of the desired hydrazone 15a-i with high output
(76-88%).
The structures of all compounds 11-15 were also
confirmed by data of elemental analysis, IR, NMR
1
- and
mass spectra, the characteristics of some of them are shown
in Tables 3; 4.
Table 3: Physical and-chemical characteristics of some compounds 11-15
Compound mp,

Brutto formula
Found, %
Calculated, %
Yield,
%
N
11a 308-310 C
15
H
21
N
5

62.37
62.69
7.51
7.37
24.56
24.37
76
11b 323-325 C
15
H
13
Cl
2
N
5

51.76
51.44
3.54
3.77
20.34
20.00
61
12a 236-238 C
17
H
18
N
4

69.68
69.37
6.24
6.16
19.16
19.04
70
12b 278-280 C
16
H
15
ClN
4

61.28
61.05
4.79
4.80
17.93
17.80
61
12d 158-159 C
17
H
18
N
4
O
2

66.08
65.79
5.92
5.85
18.21
18.05
69
12e 226-227 C
16
H
16
N
4

68.30
68.55
5.83
5.75
20.17
19.99
71
12f 159-160 C
16
H
15
ClN
4

61.31
61.05
4.79
4.80
17.93
17.80
82
12h 224-225 C
16
H
14
Cl
2
N
4

55.39
55.01
4.19
4.04
15.91
16.04
69
13b 162-163 C
16
H
15
ClN
4

61.37
61.05
4.71
4.80
17.59
17.80
68
13c 181-182 C
16
H
15
ClN
4

2

58.31
58.10
4.68
4.57
17.74
17.94
77
14b 232-334 C
14
H
18
ClN
5

54.48
54.63
5.96
5.89
22.53
22.76
80
15 274-275 C
15
H
12
lN
5

2

54,79
54,63
3,49
3,67
21,09
21,24
83












Special Issue on Biological Engineering & Natural Science, September-October 2013
ISSN: 2347 6087 2013 | Published by The Standard International Journals (The SIJ) 18
Table 4: NMR
1
and mass spectra of some compounds 11-15
Compound NMR
1
spectrum, , ppm (J, Hz), DMS-d
6
Mass spectrum,
+
(relative intensity, %)
11b
2.55 (3, s, 4-
3
Py); 2.65 (3, s, 6-
3
Py ); 6.86 (1H, s, 5-H
Py); 7.407.84 (3H, m, -r); 8.68 & 9.25 (1, brs,
NH(CO)NH); 11.65 (1, brs, N Pr).

+
349 (10); [-3,4-CI
2
-C
6
H
3
-N]
+
189 (11); [-3,4-
CI
2
-C
6
H
3
-N
2
]
+
188 (1); [188-N]
+
162 (100); [162-
HN
2
]
+
133 (12).
12a
2.35 (3, s
3
Ph); 2.55 (3, s, 4-
3
Py); 2.65 (3, s, 6-
3
Py
); 3.98 (3, s, N-CH
3
); 6.88 (1H, s, 5-H Py); 7.357.93 (4H, m,
-r); 10.45 (1, brs, NH).

+
294 (32); [-4-CH
3
-C
6
H
4
-CO]
+
175 (11); [4-CH
3
-
C
6
H
4
-CO]
+
119 (100); [175- C
3
,-N
2
]
+
132 (21); [4-CH
3
-
C
6
H
4
]
+
91 (16).
12b
2.45 (3, s, 4-
3
Py); 2.65 (3, s, 6-
3
Py ); 3.98 (3, s, N-
CH
3
); 6.90 (1H, s, 5-H Py); 7.638.03 (4H, m, -r); 10.68 (1,
brs, NH).

+
314 (26); [-4-C1-C
6
H
4
-CO]
+
175 (6); [4-C1-C
6
H
4
-
CO]
+
139 (100); [175- C
3
,-N
2
]
+
132 (38); [4-C1-C
6
H
4
]
+

111 (26).
12d
2.45 (3, s, 4-
3
Py); 2.58 (3, s, 6-
3
Py ); 3.90 (3, s, N-
CH
3
); 4.05 (3, s, O
3
); 6.90 (1H, s, 5-H Py); 7.097.75 (4H,
m, -r); 10.12 (1, brs, NH).

+
310 (13); [-CH
3
]
+
279 (4); [-2-C
3
-C
6
H
4
-
CO]
+
175 (4); [2-C
3
-C
6
H
4
-CO]
+
135 (100); [135-
CH
3
]
+
104 (6).
12e
2.40 (3, s, 4-
3
Py); 2.58 (3, s, 6-
3
Py ); 3.98 (3, s, N-
CH
3
); 6.89 (1H, s, 5-H Py); 7.567.05 (5H, m, -r); 10.58 (1,
brs, NH).

+
280 (22); [-C
6
H
5
]
+
175 (4); [C
6
H
5
]
+
105
(100); [C
6
H
5
]
+
77 (41).
12f
2.42 (3, s, 4-
3
Py); 2.60 (3, s, 6-
3
Py ); 3.97 (3, s, N-
CH
3
); 6.92 (1H, s, 5-H Py); 7.477.59 (4H, m, -r); 10.64 (1,
brs, NH).

+
314 (11); [-1]
+
279 (12); [-2-C1-C
6
H
4
-CO]
+

175 (5); [2-C1-C
6
H
4
-CO]
+
139 (100); [175- 2C
3
]
+
145
(88); [2-C1-C
6
H
4
]
+
111 (27).
12h
2.65 (3, s, 4-
3
Py); 2.70 (3, s, 6-
3
Py ); 4.00 (3, s, N-
CH
3
); 7.477.67 (4H, m, -r); 10.72 (1, brs, NH).

+
348 (22); [-1]
+
313 (14); [2-C1-C
6
H
4
-CO]
+
139
(100); [2-C1-C
6
H
4
]
+
111 (22).
13b
2.43 (3, s, 4-
3
Py); 3.38 (3, s, N-CH
3
); 6.75 (1H, s, 5-H Py);
7.357.84 (4H, m, -r); 11.00 (1, brs, NH).

+
314 (4); [-3-C
3
-C
6
H
4
-CO]
+
195 (5); [195- C
3
]
+

180 (4); [180-N
2
]
+
152 (6); [3-C
3
-C
6
H
4
-CO]
+
119
(100); [152-Cl]
+
117 (11); [3-C
3
-C
6
H
4
]
+
91 (6).
13c
2.47 (3, s, 4-
3
Py); 3.38 (3, s, N-CH
3
); 3.94 (3, s, O
3
);
6.75 (1H, s, 5-H Py); 7.117.67 (4H, m, -r); 10.59 (1, brs,
NH).

+
330 (3); [-2-C
3
-C
6
H
4
-CO]
+
195 (3); [195- C
3
]
+

180 (4); [180-N
2
]
+
152 (5); [2-C
3
-C
6
H
4
-CO]
+
135
(100); [152-Cl]
+
117 (10).
14b
Cyclohexane ring: 1,08 (m), 1,20 (m), 1,28 (m), 1,54 (m), 1,64 (m),
1,73 (m), 3,39 (m); 2.34 (3, s, 4-
3
Py); 6.51 (1H, s, 5-H Py);
6.35 & 8.02 & 9.35 (1, brs, NH).

+
307 (6); [-C
6
H
5
-NCO]
+
182 (100); [182-NH-NH]
+

152 (16); [152-Cl]
+
117 (15).

14c
1.01 (3H, t, J = 6.4 Gz, N-CH
2
CH
3
); 2.39 (3, s, 4-
3
Py); 3.44
(2H, k, J = 6.4 Gz, N-CH
2
CH
3
); 8.28 & 9.32 & 9.61 (1, brs, NH).

+
269 (70); [-C
2
H
5
-N
2
]
+
224 (32); [-C
2
H
5
-NS]
+

182 (100); [182-
3
]
+
167 (32); [182-NH-NH]
+
152
(24); [167-N]
+
140 (12); [152-Cl]
+
117 (22).
15
2.55 (3, s, 4-
3
Py); 3.62 (3, s, N-CH
3
); 7.50 (1H, s, 5-H Py);
7.257.74 (4H, m, -r); 8.30 (1H, c, N=CH)

+
329 (10); [M-]
+
312 (10); [312-C1]
+
277 (18); [-
2-NO
2
C
6
H
4
]
+
207 (60); [207-CN]
+
181 (100); [181-
HCN]
+
153 (31); [153-HCI]
+
117 (20).
15b
2.35 (3H, c, 4-
3
Ar), 2.55 (3, s, 4-
3
Py); 3.65 (3, s, N-
CH
3
); 7.65 (1H, s, 5-H Py); 7.007.60 (4H, m, -r); 8.07 (1H, c,
N=CH)

+
298 (10); [-4-CH
3
C
6
H
4
]
+
207 (51); [207-CN]
+
181
(100); [181-HCN]
+
153 (64); [153-HCI]
+
117 (22).
* Py pyridine; ** Pr - pyrazole
NOESY spectrum was recorded for 6-(N2-tert-
butylcarbonyl-N1-methylhydrazine)-4-methyl-2-
chloronicotinonitrile 13n. Correlation peaks of proton
interaction of 5 - carbon pyridine atoms with protons N-H
and N-Me of hydrazide fragment (strong interaction), as well
as with protons and CMe
3
(weak interaction) are present in
the spectrum ("Figure 2").
N
CH
3
Cl N
CH
3
NC
O
CH
3
CH
3
C H
3 H
N
13 n

Figure 2: The main interaction with the proton H-5 of the pyridine
ring in the NOESY spectrum 6-(N2-tert-butylcarbonyl-N1-
methylhydrazine)-4- methyl-2-chloronicotinonitrile 13n
The availability of the examined correlation peaks
additionally indicates the location of hydrazide group in the 6
carbon atom of the pyridine ring.
All the compounds synthesized were subjected to
screening for their antidote activity against hormone-type
herbicides and for their growth-stimulating activity.
Herbicide 2,4-D can be used as a convenient test for
studying antidote activity of the synthesized compounds.
Sunflower was chosen as a test crop because of its high
sensitivity to the above-named herbicide. Primary evaluation
of antidote characteristics of the compounds was made in the
laboratory. Further, the compounds which showed antidote
effect were tested under the field conditions by conducting
small-plot experiments.
In the screening process, the derivatives of
pyrazolopyridines with high antidote activity were identified
and patented. So, compounds 11, 11d, 11i 11l reduced
inhibiting activity of 2,4-D on sunflower seedlings by 29-55
% [Dmitrieva et al., 2007], while pyrazolopyridine 11q
Special Issue on Biological Engineering & Natural Science, September-October 2013
ISSN: 2347 6087 2013 | Published by The Standard International Journals (The SIJ) 19
applied under the field conditions decreased negative effect
of the herbicide by 48 %, ensuring therewith sunflower yield
increase of 9.1 metric centners per hectare [Strel-kov et al.,
2009].
Growth-stimulating properties of the synthesized
pyrazolopyridines were evaluated under the field conditions
by taking sugar beet and sunflower as test crops. Compounds
11 and 11r appeared to be most active, by increasing beet
yields by 4.5 and 3.3 t/ha, respectively when applied at the
rate of 28 g/ha, and by 5.3 and 4.5 t/ha, respectively, when
their dosage was 40 g/ha; simultaneously, sugar content in
beets increased by 0.7-2.2 % [Nazarenko et al., 2008]. In
addition, hydrazones 15a and 15h provide additional yield of
sugar beet from 5.25 to 6.40 t / ha, increasing the sugar
content 2.4-3.6% [Nazarenko et al., 2008A].
Hydrazide 13h contributes to the growth of sunflower
seedling root by 39% and the stem - by 42-44% compared to
control [Dmitrieva et al., 2009].
2.1. Experimental Part
IR spectra were recorded for samples in the form of tablets
with KBr by using FT-IR Spectrometer InfraLUM FT-02.
NMR
1
spectra were obtained for the sample solutions in
DMSO-d
6
(TMS internal standard) using a radio spectrometer
Bruker WM-500 with operating frequency 500.13 mHz. Mass
spectra produced by electron impact were registered with
mass spectrometer Finnigan MAT INCOS 50 (ionizing
radiation energy: 70 eV). Elemental analysis of synthesized
compounds for C, H, N was made using an analyzer Carlo-
Erba, Model 1106.
3-amino-4,6-dimethyl(1H)pyrazolo[3,4-b]pyridines (2a-b)
Method I. Mixture of 6.0 mmol of 2-chloronicotinonitrile
I or 1b, 24.0 mmol of hydrazine hydrate and 20 mL of
ethanol was boiled for 4-7 hours. After cooling the reaction
mass, the precipitate was filtered out, washed with alcohol,
then with water, and dried. After recrystallization, target
products 2a-b were obtained.
Products 8 and 10 were obtained in a similar way;
solvent: isopropanol; boiling time: 10-14 h.
Method II. Mixture of 6.0 mmol of 2-
chloronicotinonitrile I or 1b, 12.0 mmol of ethyl hydrazine
and 20 mL of ethanol was boiled for 4-7 hours. After cooling
the reaction mass, the precipitate was filtered out, washed
with alcohol, then with water, and dried. After
recrystallization, target products 2a-b were obtained.
3-amino-1,4,6-trimethylpyrazolo[3,4-b]pyridines (3a-b)
Method I. Suspension of 12.0 mmol of 2-
chloronicotinonitrile I or 1b, 48.0 mmol of methyl hydrazine
and 30 mL of ethanol was boiled for 1.5-3 hours. The
reaction mass was evaporated to of its volume, the rest was
diluted with 50 mL of water. The precipitate was filtered out,
washed with water and dried. After recrystallization, target
products 2a-b were obtained.
Method II. Suspension of 12.0 mmol of 2-
chloronicotinonitrile I or 1b, 48.0 mmol of 1,1-dimethyl
hydrazine and 30 mL of ethanol was boiled for 2-3 hours.
After isolation and purification as in Method 1, target
products 2a-b were obtained.
Products 8b and 10b were obtained in a similar way;
solvent: isopropanol; boiling time: 4-6 h.
6-hydrazino-4-methyl-2-chloronicotinonitrile (4)
Reaction mass containing 1.4 g (7.5 mmol) of 4-methyl-
2,6-dichloronicotinonitrile I, 1.5 g (30.0 mmol) of hydrazine
hydrate and 20 mL of ethanol was boiled for 0.5 h. The
reaction mass was cooled, the precipitate was filtered out,
washed with ethanol and water and dried. After
recrystallization using aqueous dimethylformamide, 1.1 g
(82%) of target product 4 was obtained.
Product 6 was obtained in a similar way by boiling with
ethylhydrazine.
6-(1-methylhydrazino)-4-methyl-2-chloronicotinonitrile (5)
5 g (8.02 mmol) of 4-methyl-2,6-dichloro-nicotinonitrile
I was diluted in 20 mL of ethanol and 1.48 g (32 mmol) of
methylhydrazine was added while mixing. In 1-2 min after
starting to add methylhydrazine, there was precipitation.
Then, the reaction mass was mixed at room temperature for
1.5-2 h, and the precipitate was filtered out. The solvent was
evaporated and additional quantity of the product was
obtained. The precipitates were combined, washed with water
and dried. After recrystallization with ethanol, 1.2 g (78%) of
target product 5 was obtained.
4-methyl-6-(3,5-dimethylpyrazol-1-yl)-2-chloronicotinonitrile
(7)
Mixture containing 1.5 g (8.2 mmol) of 6-hydrazino-4-
methyl-2-chloronicotinonitrile 4, 4.1 g (40 mmol)
acetylacetone, 5 drops of acetic acid and 12 mL ethanol was
boiled for 12 h. The precipitate was filtered out of the cooled
reaction mass and dried. After recrystallization with
ethylacetate, 1.6 g (75%) of target product 7 was obtained.
4-methyl-6-(3-methyl-5-hydroxypyrazol-1-yl)-2-
chloronicotinonitrile (9)
Mixture of 1.5 g (8.2 mmol) of 6-hydrazino-4-methyl-2-
chloronicotinonitrile 4, 5.0 g (40 mmol) of acetacetic ether, 5
drops of HCI and 15 mL of ethanol was boiled for 14 h. The
precipitate was filtered out of the cooled reaction mass and
dried. After recrystallization with dioxane, 1.5 g (73%) of
target product 9 was obtained.
General method for the synthesis of N-substituted
pyrazolo[3,4-b]pyridyl-3-ureas (11-c)
Mixture of 7.4 mmol of 3-aminopyrazolo[3,4-b]pyridine
2-b, 7.4 mmol of appropriate isocyanate and 40 mL of
absolute dioxane was boiled for 4-6 h. After cooling the
reaction mass, the precipitate was filtered out, washed with
dioxane and dried. After recrystallization, target products
11- were obtained.
General method for the synthesis of pyrazolo[3,4-b]pyridyl-
3-carboxamides (12-s)
Solution of 5.0 mmol of carbonic acid chloride solved in
8 mL of benzene was added in drops to suspension of 4.5
mmol of 3-amino-pyrazolo[3,4-b] pyridine 2,3-b and 4.5
mmol of triethylamine diluted in 15 mL of absolute benzene
while mixing at room temperature for 40-50 min. Mixing
continued for further 2-2.5 h; afterwards, the reaction solution
Special Issue on Biological Engineering & Natural Science, September-October 2013
ISSN: 2347 6087 2013 | Published by The Standard International Journals (The SIJ) 20
was isolated from the triethylamine hydrochloride precipitate,
evaporated to dryness. The precipitate was washed with
water, dried and, after purification, target products 12- s.
General method for the synthesis of 6 - [N2-(acyl,
arylcarbonyl)-N1-(Me, Et) hydrazino]-4-methyl-2-
chloronicotinonitriles (13a-k)
A mixture of 4.5 mmol of 6 - (1-methyl-, ethyl-
hydrazino)-4-methyl-2-chloronicotinonitrile 5 or 6, 4.5
mmol) of triethylamine and 12 ml absolute benzene is cooled
to 8-10 C and under stirring, a solution of 5.0 mmol of the
appropriate carboxylic acid chloride is added dropwise into 7
ml of benzene so that the reaction temperature is kept
constant. After 2-5 hours of stirring, the temperature is raised
to RT and maintained for 1-2 hours. The precipitate is
filtered, washed with water and dried. After purification by
recrystallization the target products 13a-k are obtained.
General method for the synthesis of 6 - [N2-(acyl,
arylcarbonyl)-N1- () hydrazino]-4-methyl-
2-chloronicotinonitriles (13 l-m)
A solution of 3.5 mmol of carboxylic acid chloride is
poured into a suspension of 3.3 mmol of 6-hydrazino-4-
methyl-2-chloronicotinonitrile 4, 3.3 mmol of triethylamine
in 10 ml of dry benzene and heated at 40-45 C for 3-4 hrs.
The precipitate is filtered from the cooled reaction mixture,
washed with water and dried. After purification the target
products 13 l-m are obtained.
General method for the synthesis of 4-methyl-2-chloro-3-
cyanopyridyl-6-semicarbazides and
thiosemicarbazides (14 -f)
A mixture of 5.1 mmol of 6 - (1-methylhydra-zino) -4-
methyl-2-chloronicotinonitrile 5, 7.6 mmol of the appropriate
isothiocyanate or isothiocyanate and 15 ml of absolute
dioxane is boiled for 5-6 hrs. The cooled reaction mixture is
twice diluted with water; the separated precipitate is filtered
off and dried. The target products 14 a-f are obtained after
purification by recrystallization.
General method for the synthesis of 4-methyl-2-chloro-3-
cyanopyridyl-6-hydrazones (15 a-i)
The mixture of 4.75 mmol of 6-
alkylhydrazinonicotinonitrile 5-6, and 4.75 mmol of the
appropriate aldehyde in 30 ml of ethanol is boiled for 2-2.5
hours. The reaction mixture is cooled, the separated
precipitate is filtered off, washed with ethanol and dried. The
target products 15a-i are obtained after purification by
recrystallization.
III. RESULTS
The systematic study of the reactions of 4,6-dimethyl-2-
chloro-, 4,6-dimethyl-2,5-dichloro- and 4-methyl-2,6-
dichloronicotinonitriles with hydrazine, methyl-, dimethyl-
and ethylhydrazines has been undertaken.
It was established that 4,6-dimethyl-2-chloro-, 4,6-
dimethyl-2,5-dichloronicotinonitriles substitute a chlorine
atom in position 2 for the hydrazine (alkyl-hydrazine) group
by reaction with hydrazine and alkylhydrazines with
subsequent heterocyclization to the pyrazole cycle, and the
reactions with ethyl-, and 1,1-dimethylhydrazine proceed
with the elimination of C
2
H
5
- and CH
3
- groups respectively.
4-Methyl-2,6-dichloronicotinonitrile reacts with
hydrazine by substitution of the chlorine atom in position 6 of
the pyridine ring.
4-methyl-6-(pyrazol-1-yl)-chloronicotinonitriles were
obtained by condensation of 6-hydrazino-4-methyl-2-
chloronicotinonitrile with acetoacetic ester and acetylacetone,
that repeat the detected patterns in the reaction with
hydrazines.
Quite the multiple rows of derivatives were synthesized
on the basis of the underlying structures, including the
identified compounds, greatly reducing the negative effects of
hormonal herbicides on sunflower plants, and providing
growth-stimulating effects on sugar beet and sunflower.
IV. CONCLUSION & FUTURE WORK
The study has provided new information in the field of
synthetic organic chemistry and substances with biological
activity have been found. Thus, this direction is promising;
the study of the interaction of initial compounds with other
nucleophilic reagents is appropriate hereinafter.
ACKNOWLEDGEMENTS
This work was supported by the International Science and
Technology Center (#3035 ISTC Project). The authors
express their gratitude to their collaborators from USDA-
ARS Natural Products Utilization Research Unit (Oxford,
MS) Stephen Duke, Scott Baerson, Franck Dayan and Agnes
Rimando for their methodological assistance and advice.
REFERENCES
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b]pyridines: Synthesis, Reactions, and Nuclear Magnetic
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Dyadyuchenko Lyudmila Vsevolodovna,
works as a leading researcher in the
Laboratory for Plant Growth Regulators of
All-Russian Research Institute of Biological
Plant Protection, Krasnodar, Russia. She
holds a PhD and is an associate professor. Her
research interests are synthesis of new
chemical compounds belonging to the
pyridine derivative, pyridine fused
heterocycles: pyrazoles, triazoles, thiophenes, pyrimidines, search
for biologically active substances having antidotal and growth
regulating activities. She has participated in 103 scientific works;
among them are 32 articles in scientific journals, 50 patents, 21
conference papers. She has personally taken part in 12 scientific
conferences.
Strelkov Vladimir Denisovich, graduated
from Krasnodar Polytechnic Institute in 1974
with a degree in chemical technology,
chemicals and plastics technology specialty.
He has been working in All-Russian Research
Institute of Biological Plant Protection since
1974. In 1988 he defended his PhD thesis.
Since 1992 he has been the Head of the
Laboratory for Plant Growth Regulators. In
2006 he defended his doctoral thesis on the topic: "Synthesis of
chlorinated pyridine derivatives and their biological activity." His
research interests are the synthesis and screening of new biologically
active compounds for integrated plant protection. Since 2010 he has
combined the research with teaching the course of organic chemistry
at the Kuban State University, being the Head of the Department of
Organic Chemistry and Technology.
Nazarenko Daria Yurievna, graduated from
Kuban State Agrarian University on specialty
"Chemistry and soil science" in 2002. Since
2002 she has been working as a researcher in
All-Russian Research Institute of Biological
Plant Protection. She is preparing to defend
her thesis on "Bio-stimulants in plant
protection" in the near future. She has 18
scientific articles, 9 RF patents, attended 13
scientific conferences. Her research interests are biological plant
protection, analytical chemistry, plant physiology, insect
pheromones, biostimulators, antidotes, pesticides based on natural
compounds. Twice she has been an intern in the U.S. at the Centre
for Natural Products Utilization Research Unit, under the leadership
of Franck Dayan researcher at USDA-ARS, University of
Mississippi.
Dmitrieva Irina Gennadievna, is an
associate professor of Organic Chemistry
Department of Kuban State Agrarian
University, Krasnodar, Russia. She holds a
PhD and is an associate professor. Her
research interests are synthesis of
nicotinonitriles, pyrazolopyridinyls,
thienopyridines, tetrazolopyridines and other
annelated heterocycles. She has 57
publications including 16 articles, 26 patents, 15 conference
materials. She has taken part in 10 domestic and international
conferences.