Synthesis and Fungicidal Activity of Substituted N-(Alkoxy)-1-(3-pyridinyl)methanonimines

Article abstract of DOI:10.1134/S1070363219110045

A number of new substituted N-(alkoxy)-1-phenyl- and N-(alkoxy)-1-cyclohexyl-1-(3-pyridinyl)-methanonymines were prepared by reacting the corresponding N-hydroxyl derivatives with benzyl chloride under phase transfer catalysis in a 10% NaOH-benzene system

Full text of DOI:10.1134/S1070363219110045

ISSN 1070-3632, Russian Journal of General Chemistry, 2019, Vol. 89, No. 11, pp. 2190–2195. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Zhurnal Obshchei Khimii, 2019, Vol. 89, No. 11, pp. 1666–1672.
Synthesis and Fungicidal Activity
of Substituted N-(Alkoxy)-1-(3-pyridinyl)methanonimines
A. V. Kuzenkova,* and V. V. Zakharychev
a D.I. Mendeleev Russian Chemical-Technological University, Moscow, 125047 Russia
*e-mail: kuzalex71@yandex.ru
Received July 15, 2019; revised July 15, 2019; accepted July 19, 2019
Abstract―A number of new substituted N-(alkoxy)-1-phenyl- and N-(alkoxy)-1-cyclohexyl-1-(3-pyridinyl)-
methanonymines were prepared by reacting the corresponding N-hydroxyl derivatives with benzyl chloride under
phase transfer catalysis in a 10% NaOH–benzene system, as well as with 1-bromohexane and bromocyclohexane
in DMF in the presence of NaH. The fungicidal activity of the obtained compounds was studied in vitro towards
phytopathogenic fungi Venturia inaequalis, Rhizoctonia solani, Fusarium oxysporum, F. moniliforme, and
Helminthosporium sativum.
Keywords: pyridine, O-alkylation, ketoximes, fungicidal activity
DOI: 10.1134/S1070363219110045
Fungicides based on triazole, imidazole and pyridine
derivatives are capable of using a heterocycle to coor-
dinate the iron atom in the C14-demethylase heme, the
CYP51 enzyme from the P450 monooxygenase group,
disrupting its work. Demethylase blocking leads to cessa-
tion of the synthesis of ergosterol, an essential component
of the cell membranes of fungi [1], and the accumulation
of its toxic precursors. Among the sterol biosynthesis
inhibitors, β-picoline 1 derivatives [2] have been the first
discovered in the mid-1960s. Demethylase inhibitors have
become the largest, most widely used and most commer-
cially successful group of fungicides. However, from the
beginning of the 1990s to the mid-2000s, new compounds
of this class did not appear. Interest in the search for new
representatives of this series resumed after the release of
pyrisoxazole 2 [3, 4], a broad-spectrum fungicide against
asco-, basidio- and deuteromycetes (Scheme 1).
We synthesized a number of new substituted N-(alk-
oxy)-1-phenyl- and N-(alkoxy)-1-cyclohexyl-1-(3-pyri-
dinyl)methanonimines 7a–7l, which are close in structure
to pyrifenox and parinol, and examined their fungicidal
properties.
To obtain the target compounds 7a–7l, oximes 9a–9d
were obtained by treating the corresponding ketone with
hydroxylamine hydrochloride and NaOH, which was add-
ed to the neutral reaction, in aqueous ethanol (Scheme 2)
[8, 9]. The neutral medium turned out to be optimal when
ketones 8a–8d were oximated. The basicity of pyridine
for the accepting of HCl was insufficient; an excess of
alkali also led to a decrease in the yield of the product.
Further, oximes 9a–9d were alkylated with benzyl chlo-
ride, 1-bromohexane or bromocyclohexane (Scheme 2).
The reactions with benzyl chloride proceeded smoothly
in a two-phase system (10% NaOH–benzene) using 5
mol% of benzyltriethylammonium chloride (TEBAC)
as a phase transfer catalyst. Despite the high alkylating
activity of benzyl chloride, in none of the experiments we
were able to achieve complete conversion of the starting
oxime. Along with the target O-(benzyloxy)imines, the
products of alkylation at the pyridine and hydroxyimine
nitrogen atoms were also obtained. In the case of benzy-
loxime 7b synthesis, isomeric nitrone was predominantly
formed. The highest conversion of the starting oxime 9b
was observed in this series.
Comparison of the structure of many compounds
with such an activity mechanism revealed the similarity
of structural elements in triadimefon 3 and pyrifenox 4
(Scheme 1) [5], in particular, the presence of a diatomic
chain separating the heterocyclic and phenyl nuclei. The
molecule of oxyconazole 5, a medical antifungal drug, is
constructed in a similar way [6]. At the same time, C14-
demethylase inhibitors of a different structure are known,
such as parinol 6 [7], in which molecule only one carbon
atom binds the ring.
2190

SYNTHESIS AND FUNGICIDAL ACTIVITY
2191
Scheme 1.
N
CH3
N
N
R
Cl
Ar
X
O
CH3
1
Cl
O
2
Cl
N
Cl
Cl
N
N
O
Cl
N
N
Cl
N
CH3
OH
Cl
O
N
O
N
CH3
H
3C
N
CH3
Cl
Cl
4
3
6
5
When using weaker alkylating agents (1-bromohexane
and bromocyclohexane), the reaction proceeded under
more severe conditions, and the use of NaH in DMF was
required for deprotonation of oximes. In the reaction with
bromocyclohexane, the conversion of the starting oximes
was significantly lower than with benzylation, and signifi-
cant amounts of olefin, the product of the elimination of
HBr from alkyl bromide, were formed. It was possible to
separate the unreacted oxime from the target compound
by repeatedly washing the reaction mixture with a 15%
KOH solution. Purification of the target reaction products
was carried out by flash chromatography on a dry column
[10] filled with silica gel.
doubled proton signal at position 4 of the pyridine ring in
1H NMR spectra, with the predominance of the E-form
(55–85%). This proton in the spectra was manifested by
a doublet signal with a characteristic constant of spin-
spin coupling (7.5–8.1 Hz). The isomeric composition
of the mixtures was established based on the ratio of
signal intensities. In the case of Z-isomers, the proton in
the position 4 of the pyridine ring was deshielded by an
approximate oxygen atom, shifting its signal to a weak
field. Similarly, in the case of (Z)-O-benzyl derivatives
7a–7d, the protons of the CH2O group were deshielded
by the electron-deficient pyridine nucleus.
The obtained compounds 7a–7l were tested for fun-
gicidal activity in vitro on a solid nutrient medium on
five phytopathogenic fungi belonging to the classes of
All the obtained oximes were mixtures of E- and Z-
isomers in different ratios, clearly distinguished by the
Scheme 2.
O
NOH
R1
N
(1) BnCl, C H , NaOH, TEBAC, ¨
6
6
R1
NH
6 13
(2) p-C H Br, NaH, DMF, 20–60°C
R1
(3) c-C H Br, NaH, DMF, 20–60°C
6
11
2OH·HCl, NaOH
EtOH, 100o
C
N
N
N
R2
O
ꢀ
9a 9d
8a 8d
ꢀ
ꢀ
7a 7l
1
1
2
R = 4-FC H (ꢀɚ, ꢁɚ), 4-ClC H (8b, 9b), 4-BrC H (8c, 9c), c-C H (8d, 9d); R = 4-FC H , R = PhCH
2
6
4
6
4
6
4
6
11
6
2
4
1
2
1
2
1
(ꢂɚ); R = 4-ClC H , R = PhCH (7b); R = 4-BrC H , R = PhCH (7c); R = c-C H , R = PhCH (7d);
6
4
2
6
4
2
6
11
2
1
2
1
2
1
2
R = 4-FC H , R = p-C H (7e); R = 4-ClC H , R = p-C H (7f); R = 4-BrC H , R = p-C H (7g);
6
4
6
13
6
4
6
13
6
4
6 13
1
2
1
2
1
2
R = c-C H , R = p-C H (7h); R = 4-FC H , R = c-C H (7i); R = 4-ClC H , R = c-C H (7j);
6
11
6
13
6
4
6
11
6
4
6 11
1
2
1
2
R = 4-BrC H , R = c-C H (7k); R = R = c-C H (7l).
6
4
6
11
6 11
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 11 2019

2192
KUZENKOV, ZAKHARYCHEV
Inhibition of in vitro radial growth of fungal mycelium by compounds 7a–7l (c = 30 mg/mL)
Inhibition of radial growth of fungal mycelium relative to the control±standard deviation, %
Compound
V. inaequalis
50±1
R. solani
56±3
45±3
51±3
54±4
43±2
12±5
29±4
63±2
60±2
43±4
38±5
43±5
54±4
F. oxysporum F. moniliforme
H. sativum
74±2
59±2
43±3
65±2
52±2
37±5
36±5
74±3
52±3
55±4
48±4
24±5
60±5
S. sclerotiorum
17±2
7a
34±2
33±2
23±1
32±2
29±1
17±1
12±1
33±1
24±1
33±2
25±1
23±1
72±5
52±3
41±4
44±4
57±3
58±2
45±5
36±4
67±2
60±2
51±3
47±3
60±3
85±7
7b
39±3
16±2
7c
30±3
10±1
7d
51±2
18±2
7e
54±2
20±2
7f
54±2
4±1
7g
43±3
11±1
7h
86±1
17±1
7i
54±3
22±1
7j
30±5
16±1
7k
34±5
16±1
7l
57±1
16±2
60±5
67±6
Triadimefon
asco-, basidio- and deuteromycetes: Venturia inaequalis
(Cooke) Winter, Rhizoctonia solani Kühn, Fusarium
oxysporum Schlecht, Fusarium moniliforme Sheldon и
Helminthosporium sativum Pammel, King et Bakke from
the collection of the All-Russian Research Institute of
Plant Protection Chemicals (Moscow). An analysis of
biological test data (see Table) shows that V. inaequalis,
R. solani, andF. moniliformeturnedouttobethemostsensi-
tive to the tested compounds, and S. sclerotiorum the least.
All the obtained compounds suppressed fungal growth;
however, in most cases, fungitoxicity inferior to triad-
imefon. N-(Benzyloxy)imines 7a–7d and N-(hexyloxy)-
imine 7h showed the greatest activity. The high activity
of compound 7h was somewhat unexpected, since it is
known [11] that the presence of a halogen atom in the
structure is important for CYP51 cytochrome oxidase
ligands. Considering that the main field of application of
C14-demethylase inhibitors is the fight against obligate
pathogens of powdery mildew (Erysiphe graminis) and
rust (Puccinia recondita) and the optional causative agent
of septoria (Septoria tritici) crops [12], it is advisable to
study the obtained compounds in planta against relevant
pathogens.
known CYP51 enzyme inhibitors pyrifenox, parinol and
oxyconazole used as agricultural and medical fungi-
cides. All the obtained compounds inhibited in vitro the
growth of fungi of different taxonomic classes, in some
cases exceeding the activity of the commercial fungicide
triadimefon, which also inhibits CYP51. The resulting
compounds can be recommended for the second stage
of screening studies in planta.
EXPERIMENTAL
1H NMR spectra were recorded on a Bruker AM300
(300 MHz) instrument from DMSO-d6 solutions.
N-Hydroxy-1-(4-fluorophenyl)-1-(3-pyridinyl)-
methanimine (9a). A solution of 0.695 g (10 mmol) of
hydroxylamine hydrochloride in 1 mLof water was added
to a solution of 1.010 g (5 mmol) of 4-fluorophenyl-(3-
pyridinyl)methanone 8a in 15 mLof ethanol. The mixture
was heated in a water bath for 1 h, then cooled to room
temperature. A solution of 0.400 g (10 mmol) of NaOH
in 1 mL of water was added. Carbon dioxide was passed
through the solution, adjusting pH ~ 7. The precipitate
was filtered off, heated with 5 mL of ethanol to a boil.
Then, 5 mL of tetrahydrofuran was added, the resulting
mixture was cooled to room temperature and filtered. The
organic extract was evaporated to dryness, and the residue
In conclusion, new substituted N-(alkoxy)-1-phenyl-
and N-(alkoxy)-1-cyclohexyl-1-(3-pyridinyl)metha-
nonimines were synthesized, similar in structure to the
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 11 2019

SYNTHESIS AND FUNGICIDAL ACTIVITY
2193
was recrystallized from ethanol. Yield 1.027 g (95.1%),
mp 154–156°С (mp 155–156°С [9]).
(1Н, 4-СНPy, J = 8.1, E-isomer), 7.73 d (1Н, 4-СНPy, J =
8.1, Z-isomer), 8.59 s (1Н, 2-СНPy), 8.65 m (1Н, 6-СНPy).
Found, %: С 62.11; Н 4.15; N 7.65. C19H15BrN2O. Cal-
culated, %: С 62.04; Н 4.12; N 7.53.
Compounds 9b–9d were prepared similarly.
N-Hydroxy-1-(4-chlorophenyl)-1-(3-pyridinyl)-
methanimine (9b). Yield 1.100 g (94.6%), mp 152–
153°С (mp 151°С [9]).
N-(Benzyloxy)-1-cyclohexyl-1-(3-pyridinyl)metha-
nimine (7d). Yield 0.429 g (62.4%, E : Z = 55 : 45),
1
reddish brown oil. Н NMR spectrum, δ, ppm (J, Hz):
N-Hydroxy-1-(4-bromophenyl)-1-(3-pyridinyl)-
methanimine (9c). Yield 0.630 g (46.1%), mp 159–
161°С (mp 159–161°С [9]).
1.06–1.81 m (11Н, с-С6Н11), 5.05 s (2Н, ОСН2, E-
isomer), 5.19 s (2Н, ОСН2, Z-isomer), 7.22–7.44 m (6Н,
5-СНPy, Ph), 7.64 d (1Н, 4-СНPy, J = 7.6, E-isomer), 7.73
d (1Н, 4-СНPy, J = 7.6, Z-isomer), 8.55 s (1Н, 2-СНPy),
8.62 d (1Н, 6-СНPy, J = 5.0). Found, %: С 77.50; Н 7.57;
N 9.40. C19H22N2O. Calculated, %: С 77.52; Н 7.53; N
9.52.
N-Hydroxy-1-cyclohexyl-1-(3-pyridinyl)methani-
mine (9d). Yield 0.911 g (89.3%), mp 174–175°С (mp
173–175°С [9]).
N-(Benzyloxy)-1-(4-fluorophenyl)-1-(3-pyridinyl)-
methanimine (7a). Asolution of 0.300 g (2.37 mmol) of
benzyl chloride and 0.230 g (0.1 mmol) of benzyltrieth-
ylammonium chloride in 4.2 mL of benzene was added
to a solution of 0.432 g (2 mmol) of oxime 9a in a 10%
aqueous solution of NaOH (3.08 g, 77 mmol) in 28 mLof
water. The biphasic system was vigorously stirred at re-
flux for 8.5 h, monitoring the reaction progress using TLC.
After the reaction completed, the mixture was cooled to
room temperature. The organic layer was separated, and
the solvent was distilled off. The residue was separated by
flash chromatography on silica gel 5/40, eluent CH2Cl2‒
ethyl acetate, 1 : 1. Yield 0.348 g (56.9%, E : Z = 75 : 25),
oil. 1Н NMR spectrum, δ, ppm (J, Hz): 5.18 s (2Н, ОСН2,
E-isomer), 5.28 s (2Н, ОСН2, Z-isomer), 7.27–7.48 m
(10Н, 5-СНPy, Ph, FC6H4), 7.66 d (1Н, 4-СНPy, J = 8.1,
E-isomer), 7.74 d (1Н, 4-СНPy, J = 8.1, Z-isomer), 8.59 s
(1Н, 2-СНPy), 8.64 m (1Н, 6-СНPy). Found, %: С 74.35;
Н 4.50; N 9.10. C19H15FN2O. Calculated, %: С 74.50;
Н 4.94; N 9.14.
N-(Hexyloxy)-1-(4-fluorophenyl)-1-(3-pyridinyl)-
methanimine (7e). To a solution of 0.432 g (2 mmol)
of oxime 9a in 7 mL of absolute DMF was added under
cooling with an ice bath 0.120 g (3 mmol) of 60% sus-
pension of NaH under argon atmosphere. The mixture
was stirred for 30 min, and then 0.34 mL (2.5 mmol)
of 1-bromohexane was added. The resulting mixture
was stirred for 24 h at room temperature, then 2.5 h at
60°С. The reaction mixture was poured into ice water
(50 mL). The aqueous phase was extracted with diethyl
ether, and the organic layer was washed 3 times with
water, 4 times with a 15% KOH solution and dried with
Na2SO4. The solvent was distilled off. An admixture of
olefin and DMF was distilled off in vacuum of 1 Torr.
The product was purified by flash chromatography on
silica gel 5/40, eluent CH2Cl2–ethyl acetate. Yield 0.546 g
1
(91%, E : Z = 57 : 43), yellow oil. Н NMR spec-
trum, δ, ppm (J, Hz): 0.80 t [3Н, СН3(СН2)5, J = 0.5],
1.20–1.35 m [6Н, СН3(СН2)3СН2СН2О], 1.35–1.50 m
(2Н, С4Н9СН2СН2О), 4.10 t (2Н, С5Н11СН2О, J = 3.0),
7.20–7.50 m (5Н, 5-СНPy, FC6H4), 7.65 d (1H, 4-CHPy,
J = 8.1, Z-isomer) 7.73 d (1H, 4-CHPy, J = 8.1, E-isomer),
8.57 s (1Н, 2-СНPy), 8.61 d (1Н, 6-СНPy, J = 5.0). Found,
%: С 71.90; Н 7.01; N 9.25. C18H21FN2O. Calculated,
%: С 71.98; Н 7.05; N 9.33.
Compounds 7b–7d were prepared similarly.
N-(Benzyloxy)-1-(4-chlorophenyl)-1-(3-pyridinyl)-
methanimine (7b). Yield 0.44 g (68.2%, E : Z = 56 : 44),
1
reddish brown oil. Н NMR spectrum, δ, ppm (J, Hz):
5.19 s (2Н, ОСН2, E-isomer), 5.30 s (2Н, ОСН2, Z-
isomer), 7.20–7.50 m (10Н, 5-СНPy, Ph, ClC6H4), 7.65
d (1Н, 4-СНPy, J = 8.1, E-isomer), 7.73 d (1Н, 4-СНPy,
J = 8.1, Z-isomer), 8.57 s (1Н, 2-СНPy), 8.65 s (1Н,
6-СНPy, J = 8.0). Found, %: С 70.67; Н 4.71; N 8.67.
C19H15ClN2O. Calculated, %: С 70.70; Н 4.60; N 8.58.
Compounds 7e–7l were prepared similarly.
N-(Hexyloxy)-1-(4-chlorophenyl)-1-(3-pyridinyl)-
methanimine (7f). Eluent – hexane–acetone. Yield
1
0.208 g (32.7%, E : Z = 71 : 29), yellow oil. Н NMR
N-(Benzyloxy)-1-(4-bromophenyl)-1-(3-pyridinyl)-
methanimine (7c). Yield 0.458 g (62.4%, E : Z = 67 : 33),
reddish brown oil. Н NMR spectrum, δ, ppm (J, Hz):
5.20 s (2Н, ОСН2, E-isomer), 5.29 s (2Н, ОСН2, Z-
isomer), 7.28–7.50 m (10Н, 5-СНPy, Ph, BrC6H4), 7.65 d
spectrum, δ, ppm (J, Hz): 0.90 t [3Н, СН3(СН2)5О, J =
1.0], 1.20–1.45 m [6Н, СН3(СН2)3СН2СН2О], 1.60–1.80
m (2Н, С4Н9СН2СН2О), 4.0 t (2Н, С5Н11СН2О, J = 3.5),
7.25–7.50 m (5Н, 5-СНPy, ClC6H4), 7.65 d (1Н, 4-СНPy,
J = 7.5, E-isomer), 7.73 d (1H, 4-CHPy, J = 7.5, Z-isomer),
1
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KUZENKOV, ZAKHARYCHEV
8.57 s (1Н, 2-СНPy) 8.65 d (1Н, 6-СНPy, J = 5.0). Found,
%: С 68.15; Н 6.76; N 8.75. C18H21ClN2O. Calculated,
%: С 68.24; Н 6.68; N 8.84.
8.0, Z-isomer), 8.57 s (1Н, 2-СНPy), 8.65 d (1Н, 6-СНPy,
J = 5.0). Found, %: С 60.09; Н 5.39; N 7.69. C18H19Br-
N2O. Calculated, %: С 60.18; Н 5.33; N 7.80.
N-(Hexyloxy)-1-(4-bromophenyl)-1-(3-pyridinyl)-
methanimine (7g). Yield 0.356 g (51.3%, E : Z =
67 : 33), yellow oil. 1Н NMR spectrum, δ, ppm (J, Hz):
0.80 t [3Н, СН3(СН2)5О, J = 1.0], 1.20–1.40 m (6Н,
С4Н9СН2СН2О), 1.70–1.90 m (2Н, С4Н9СН2СН2О),
4.20 t (2Н, С5Н11СН2О, J = 4.0), 7.25–7.50 m (5Н,
5-СНPy, BrC6H4), 7.65 d (1Н, 4-СНPy, J = 7.5, E-isomer),
7.73 d (1H, 4-CHPy, J = 7.5, Z-isomer), 8.57 s (1Н,
2-СНPy), 8.65 d (1Н, 6-СНPy, J = 5.0). Found, %: С 59.80;
Н 5.96; N 7.66. C18H21BrN2O. Calculated, %: С 59.84;
Н 5.86; N 7.75.
N-(Cyclohexyloxy)-1-cyclohexyl-1-(3-pyridinyl)-
methanimine (7l). Yield 0.102 g (17.9%, E : Z = 67 : 33),
yellow oil. 1Н NMR spectrum, δ, ppm (J, Hz): 1.02–2.05
m and 4.00–4.25 m (22Н, с-С6Н11), 7.37–7.50 m (1Н,
5-СНPy), 7.65 d (1Н, 4-СНPy, J = 7.6, E-isomer), 7.70
d (1Н, 4-СНPy, J = 7.6, Z-isomer), 8.57 s (1Н, 2-СНPy),
8.65 m (1Н, 6-СНPy). Found, %: С 75.32; Н 9.19; N 9.68.
C18H26N2O. Calculated, %: С 75.48; Н 9.15; N 9.78.
Screening of in vitro biological activity. Before the
study, mushrooms were grown on sucrose-potato agar in
Petri dishes at 25±0.5°C for 10 days. The nutrient medium
was prepared from filtered through a filter potato broth
(200 g/L chopped potatoes), sucrose (20 g/L) and agar
(10 g/L). After preparation, the medium was autoclaved
at 120°С for 20 min.
N-(Hexyloxy)-1-cyclohexyl-1-(3-pyridinyl)metha-
nimine (7h). Yield 0.450 g (78.2%, E : Z = 75 : 25), yel-
low oil. 1Н NMR spectrum, δ, ppm (J, Hz): 0.75–0.90 m
[8Н, СН3(СН2)4СН2], 1.10–1.40 m (11Н, с-С6Н11), 1.50
t [3Н, СН3(СН2)5О, J = 2.0], 3.90 t (2Н, С5Н11СН2О,
J = 3.5), 7.40 t (1Н, 5-СНPy, J = 3.0), 7.62 d (1Н, 4-СНPy,
J = 8.0, E-isomer), 7.73 d (1H, 4-CHPy, J = 8.0, Z-isomer),
8.57 s (1Н, 2-СНPy), 8.65 d (1Н, 6-СНPy, J = 5.0). Found,
%: С 74.90; Н 9.83; N 9.62. C18H28N2O. Calculated, %:
С 74.96; Н 9.78; N 9.71.
Solutions of test compounds in acetone were prepared
at a concentration of 3 mg/mL. The resulting solutions
were added to molten potato-sucrose agar at 50°C at the
rate of 1 mL per 100 mL of agar. Medium containing
30 mg/L of the test substance was obtained, which under
aseptic conditions was poured into 15 mLinto Petri dishes
with an inner diameter of 10 cm. The final concentra-
tion of acetone in all the media was 1%. As a control, a
medium containing only acetone was used. The surface
of agar chilled and hardened at room temperature was
inoculated with slices of mycelium fungi. Three colonies
of mushrooms were sown per cup; in total, six replicates
were used for each experiment. After incubation of the
fungi in a thermostat at 25±0.5°С for 72 h, the diameter
of the colonies of microorganisms was measured. The
inhibition of mycelial growth was calculated in % rela-
tive to the untreated control and its standard deviation.
As a reference substance, the commercial fungicide
triadimefon 3 [3,3-dimethyl-1-(1,2,4-triazol-1-yl)-1-(4-
chlorophenoxy)butan-2-one] containing 98% of active
substances (ZAO Shchelkovo Agrochem) was used. The
test results are presented in the table.
N-(Cyclohexyloxy)-1-(4-fluorophenyl)-1-(3-pyri-
dinyl)methanimine (7i). Yield 0.139 g (23.4%, E : Z =
60 : 40), yellow oil. 1Н NMR spectrum, δ, ppm (J, Hz):
1.15–1.60 m and 1.70–1.90 m [10Н, (СН2)5)], 4.12–4.27
m (1Н, СНО), 7.25–7.50 m (5Н, 5-СНPy, FC6H4), 7.60 d
(1Н, 4-СНPy, J = 7.6, E-isomer), 7.72 d (1Н, 4-СНPy, J =
7.6, Z-isomer), 8.58 s (1Н, 2-СНPy), 8.64 d (1Н, 6-СНPy,
J = 4.0). Found, %: С 72.34; Н 6.48; N 9.30. C18H19FN2O.
Calculated, %: С 72.46; Н 6.42; N 9.39.
N-(Cyclohexyloxy)-1-(4-chlorophenyl)-1-(3-pyr-
idinyl)methanimine (7j). Yield 0.160 g (25.4%, E : Z =
85 : 15), yellow oil. 1Н NMR spectrum, δ, ppm (J, Hz):
1.10–1.90 m [10Н, (СН2)5], 4.10–4.25 m (1Н, СНО),
7.30–7.45 m (4Н, ClC6H4), 7.50 t (1Н, 5-СНPy, J = 3.0),
7.64 d (1Н, 4-СНPy, J = 8.0, E-isomer), 7.73 d (1Н,
4-СНPy, J = 8.0, Z-isomer), 8.56 s (1Н, 2-СНPy), 8.62 d
(1Н, 6-СНPy, J = 4.0). Found, %: С 68.61; Н 6.10; N 8.79.
C18H19ClN2O. Calculated, %: С 68.67; Н 6.08; N 8.90.
CONFLICT OF INTEREST
No conflict of interest was declared by the authors.
REFERENCES
N-(Cyclohexyloxy)-1-(4-bromophenyl)-1-(3-pyr-
idinyl)methanimine (7k). Yield 0.175 g (24.4%, E : Z =
67 : 33), yellow oil. 1Н NMR spectrum, δ, ppm (J, Hz):
1.16–1.57 m and 1.73–1.94 m [10Н, (СН2)5], 4.15–4.29
m (1Н, СНО), 7.20–7.50 m (5Н, 5-СНPy, BrC6H4), 7.66 d
(1Н, 4-СНPy, J = 8.0, E-isomer), 7.74 d (1Н, 4-СНPy, J =
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