Hydrazides of Organic Acids in the Transformations of the Peroxide Products of Non-1-ene Ozonolysis

Article abstract of DOI:10.1134/S1070428019110113

The reaction of hydrazides of alicyclic capric and aromatic benzoic and p-hydroxybenzoic acids with the peroxide product of non-1-ene ozonolysis was studied. Capric acid hydrazide exhibits the strongest reducing properties in aprotic solvents (methylene chloride, THF) and leads to chemoselective and high-yield (~ 80%) formation of the corresponding acylhydrazone. p-Hydroxybenzoic acid hydrazide forms a similar derivative with a yield of 67% only in THF.

Full text of DOI:10.1134/S1070428019110113

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2019, Vol. 55, No. 11, pp. 1712–1715. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Zhurnal Organicheskoi Khimii, 2019, Vol. 55, No. 11, pp. 1746–1750.
Hydrazides of Organic Acids in the Transformations
of the Peroxide Products of Non-1-ene Ozonolysis
a,
a
a
a
Yu. V. Myasoedova *, L. R. Garifullina , E. R. Nurieva , and G. Yu. Ishmuratov
a
Ufa Institute of Chemistry, Ufa Research Center, Russian Academy of Sciences,
pr. Oktyabrya 71, Ufa, Republic of Bashkortostan, 450054 Russia
*
е-mail: legostaevayuv@yandex.ru
Received April 29, 2019; revised September 18, 2019; accepted September 20, 2019
Abstract—The reaction of hydrazides of alicyclic capric and aromatic benzoic and p-hydroxybenzoic acids
with the peroxide product of non-1-ene ozonolysis was studied. Capric acid hydrazide exhibits the strongest
reducing properties in aprotic solvents (methylene chloride, THF) and leads to chemoselective and high-yield
(
~ 80%) formation of the corresponding acylhydrazone. p-Hydroxybenzoic acid hydrazide forms a similar
derivative with a yield of 67% only in THF.
Keywords: ozonolysis–reduction, capric, benzoic, and p-hydroxybenzoic acid hydrazides, acylhydrazones
DOI: 10.1134/S1070428019110113
Hydrazides of carboxylic acids attract attention by
their coordination properties and the promise their
derivatives offer in technology, medicine, and
agriculture [1]. For example, hydrazides of aromatic
acids and their derivatives exhibit diverse biological
activity (anti-tuberculosis, antimycobacterial, antiviral,
antibacterial, etc.) [2], complexing properties [1, 3],
and are also used in the synthesis of biologically active
compounds [4, 5].
draw up a possible scheme of transformations of
peroxides from non-1-ene (1), as well as to suggest
reaction products. Thus, α-methoxyhydroperoxide 2
and ozonide 3 can undergo both reduction to
hemiacetal 4 or aldehyde 7 and dehydration or
cleavage with formaldehyde elimination to form ester
5 or acid 8, respectively. The condensation of carbonyl
compounds 4 and 7 with acid hydrazides, in its turn,
leads to target hydrazones 6 (Scheme 1).
One of the ways to introduce the acylhydrazone
fragment into molecules involves the condensation of
organic acid hydrazides with carbonyl compounds [2,
Thus, the reducing ability of the studied acid
hydrazides with respect to the peroxide products of
ozonolysis of non-1-ene (1) can be empirically
estimated by the yield of carboxyl derivatives 5 and 8:
the higher their yield, the weaker reducing ability of
the hydrazide.
6
–7]. In their turn, the latter can be prepared by the
ozonolysis of alkene substrates in the presence of
reducing agents, such as Me S, PPh , etc. [8].
2
3
Aiming at developing a one-pot synthesis of
acylhydrazones (without isolation of the intermediate
carbonyl compounds), we studied the ability of organic
acid hydrazides (benzoic, p-hydroxybenzoic, and
capric) to reduce the peroxide products of alkene
ozonolysis in solvents of different nature (МеОН,
CH Cl , THF). As the substrate we used non-1-ene (1).
Treatment with capric acid hydrazide 9 of the
peroxide ozonolysis product of non-1-ene (1) (0°С)
gave acylhydrazone 10 in yields from 16 to 80%,
depending on the solvent. The lowest yield of
hydrazone 10 was obtained in methanol, and the most
abundant component of the reaction mixture was
methyl octanoate (5). In aprotic solvents (CH Cl ,
2
2
2 2
THF), the main product is acylhydrazone 10, while
octanoic acid (8) forms in trace mounts (Scheme 2).
As known, the nature of the solvent has a strong
impact on the structure of the peroxide products of
ozonolysis [9]. In methanol, the preferential products
are α-methoxyhydroperoxides and in aprotic solvents
Treatment of the peroxides from alkene 1 with
benzoic acid hydrazide (11) and p-hydroxybenzoic
acid hydrazide (13) showed that the aromatic
(
CH Cl , THF), ozonides. With this in mind, we can
2 2
1
712

HYDRAZIDES OF ORGANIC ACIDS IN THE TRANSFORMATIONS OF THE PEROXIDE PRODUCTS
1713
Scheme 1.
O
OH
O
[
H]
2
NH NHCR
OOH
OMe
OMe
_MeOH
NNHCR
O
3
, MeOH, 0°C
4
5
6
O
2
_H
OMe
2
O
2 6
(CH )
O
1
2
NH NHCR
O
3
,
[H]
6
CH
2
Cl
0
2
or THF
°C
O
O
O
O
7
8
O
_CH
2
O
OH
3
hydrazides were weaker reducers compared to alicyclic
hydrazide 9. Thus, the reactions in methanol both
resulted in the exclusive formation of methyl octanoate
With hydrazide 13 in CH Cl , acylhydrazone 14
2 2
forms chemoselectively and in a good yield (67%). At
the same time, the reaction in THF occurs with a lower
selectivity and provides a lower yield of hydrazone 14
(5) in high yields (Schemes 3 and 4).
(
Scheme 4).
Target acylhydrazones 12 and 14 were obtained in
the reactions of aprotic solvents. With benzoic acid
The obtained experimental results allow us to
hydrazide (11) in methylene chloride, acylhydrazone
conclude the aliphatic capric acid hydrazide exhibits a
higher reducing ability with respect to the peroxide
products of ozonolysis compared to the aromatic
p-hydroxybenzoic and, especially, benzoic acid hydra-
1
2 forms in a mixture with a small amount (5%) of
octanoic acid (8), whereas in THF, hydrazone 12 and
acid 8 form in nearly equal amounts (Scheme 3).
Scheme 2.
N
o
1
. O3, MeOH, 0 C
NH
+
5, 35%
O
2
.
O
HN
9
10, 16%
NH2
o
1
2
. O , CH Cl , 0 C
. 9
3
2
2
1
10, 80% + 8, 3%
o
1
2
. O , THF, 0 C
. 9
3
1
0, 78% + 8, 12%
Scheme 3.
o
1
. O , MeOH, 0 C
3
5
, 73%
NH
2
.
H N
2
O
1
1
O
o
1
2
. O , CH Cl , 0 C
. 11
3
2
2
N
1
N
+ 8, 5%
H
1
2, 32%
o
1
2
. O , THF, 0 C
. 11
3
1
2, 33% + 8, 30%
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 11 2019

1
714
MYASOEDOVA et al.
Scheme 4.
1
. O , MeOH, 0°C
3
5
, 89%
OH
2
.
NH
H N
2
O
1
3
O
1
2
. O , CH Cl , 0°C
. 13
3
2
2
N
N
1
H
OH
1
4, 67%
1
2
. O , THF, 0°C
. 13
3
1
4, 37% + 8, 13%
zides, which is evidently explained by the electronic
effects in the molecules of these reagents.
CHCl , the solution was washed with saturated NaCl,
3
dried with Na SO , and evaporated.
2
4
Treatment with capric acid hydrazide (9).
EXPERIMENTAL
Ozonolysis in methanol. Column chromatography
The work was performed using the equipment of
the Khimiya Center for Collective Use, Ufa Institute of
Chemistry, Ufa Research Center, Russian Academy of
Sciences. The IR spectra were measured on a Shimadzu
Prestige-21 FTIR Spectrophotometer in thin films. The
NMR spectra were obtained on a Bruker Avance III
[
(
0
SiO , petroleum ether (PE)–tert-butyl methyl ether
2
MTBE), 20 : 1→1 : 1] of the residue (2.20 g) gave
.56 g (16%) acylhydrazone 10 and 0.43 g (35%) of
methyl octanoate (5) [11].
Ozonolysis in CH Cl . Column chromatography
2
2
1
13
(
SiO , PE– MTBE, 20 : 1→1 : 1) of the residue (2.10 g)
5
00 spectrometer at 500.13 ( Н) and 125.47 ( С) MHz
2
gave 1.88 g (80%) acylhydrazone 10 and 0.03 g (3%)
of octanoic acid (8) [12].
in CDCl , internal reference TMS. Gas chromatogra-
3
phy was performed on a Chrom-5 chromatograph
[
column length 1.2 m, packing 5% SE-30 on Chroma-
Ozonolysis in THF. Column chromatography
ton N-AW-DMCS (0.16–0.20 mm), working tempera-
ture 50–300°С], carrier gas helium. Thin-layer chro-
matography was performed on Sorbfil silica gel plates,
and column chromatography, on Lancaster silica gel
(
SiO , PE– MTBE, 20 : 1→1 : 1) of the residue (2.30 g)
2
gave 1.80 g (78%) acylhydrazone 10 and 0.14 g (12%)
of octanoic acid (8).
N-[(1E)-Octylidene]decanohydrazide (10). White
(
70–230 μm). Benzoic (Sigma Aldrich, CAS No. 65-
crystals, mp 69–70°С, R 0.3 (hexane–MTBE, 2 : 1).
8
4
9
5-0), capric (Sigma Aldrich, CAS No. 334-48-0), and
-hydroxybenzoic acids (Sigma Aldrich, CAS No. 99-
6-7), each 99% pure, were used. The elemental ana-
f
–
1
IR spectrum (KBr), ν, cm : 3200 [C(=O)NH], 1663
1
(
0
C=N), 1556 (NН). Н NMR spectrum, δ, ppm: 0.82–
9
18
5–8
.91 m (6Н, С Н , С Н ), 1.18–1.4 m (18Н, С Н ,
lyses of all products were consistent with the cal-
culated values. Ozonizer performance 40 mmol О /h.
3 3 2
1
2
14–17
4
С Н , С
Н ), 1.46–1.53 m (2Н, С Н ), 1.60–1.67
2 2
m (2Н, С Н ), 2.19–2.23 m (2Н, C H ), 2.60 t (2Н,
С Н , J 7.3 Hz), 7.18 t (1Н, С Н=N, J 5.3 Hz), 9.80 s
1Н, NH). C NMR spectrum, δ, ppm: 14.02 q (CН ),
2
3
1
1
10
2
2
General experimental procedure. Ozon–oxygen
3
2
2
mixture was bubbled through a solution of 1.0 g
(
МеОН, THF, or CH Cl at 0°С until 8 mmol of О had
been consumed. The reaction mixture was purged with
argon, after which 15.84 mmol of hydrazide 9, 11, or
1
at room temperature until peroxide had been consumed
completely (72 h, starch iodine test). The solvent was
removed by distillation, the residue was dissolved in
13
(
3
7.92 mmol) of non-1-ene (1) in 20 mL of absolute
1
2
3
4.05 q (CН ), 22.57, 22.62, 24.65, 26.27, 28.99,
3
2
2
3
9.05, 29.26, 29.33, 29.43, 31.63, 31.69, 31.84, 32.10,
2.53 all t (CH ), 147.64 d (CН=N), 176.27 (C=O).
2
+
Mass spectrum, m/z (I , %): 297 (100) [M + H] .
rel
3 [10] was added (0°С), and the mixture was stirred
Found, %: C 72.41; H 12.52; N 9.68. С Н N O. Cal-
1
8
36
2
culated, %: C 72.92; H 12.24; N 9.45.
Treatment with benzoic acid hydrazide (11).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 11 2019

HYDRAZIDES OF ORGANIC ACIDS IN THE TRANSFORMATIONS OF THE PEROXIDE PRODUCTS
1715
Ozonolysis in methanol. Column chromatography
FUNDING
(
SiO , PE–MTBE, 20 : 1→1 : 1) of the residue (1.28 g)
2
This work was financially supported by the
Fundamentals of Chemistry” Program of the Russian
Academy of Sciences, topic no. 8 “Chemo-, Regio-, and
Stereoselective Transformations of Terpenoids, Steroids, and
Lipids in the Directed Synthesis of Low-Molecular-Weight
Bioregulators” (Reg. no. AAAA-A17-117011910023-2, 2017).
gave 0.90 g (73%) of ester 5.
“
Ozonolysis in CH Cl . Column chromatography of
2
2
the residue gave 0.62 g (32%) of hydrazone 12 and
0
.06 g (5%) of octanoic acid (8).
Ozonolysis in THF. Column chromatography of
the residue gave 0.35 g (30%) of octanoic acid (8) and
CONFLICT OF INTEREST
The authors declare no conflict of interest.
REFERENCES
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.65 g (33%) of acylhydrazone 12.
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f
–
1
IR spectrum (KBr), ν, cm : 3212 (NН), 1652 (C=N).
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.20–1.40 m (6Н, С Н ), 1.52–1.65 m (4Н, С Н ,
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2
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2
С Н ), 2.25–2.31 m (2Н, С Н ), 7.30–7.45 m (3Н,
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СНarom), 7.52 t (1Н, С Н=N, J 7.3 Hz), 7.80 br.s (1Н,
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δ, ppm: 14.03 q (CН ), 22.55 t, 24.76 t, 28.89 t, 29.02 t,
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1.60 t, 34.09 t (CH ), 127.51 d (2СНarom), 129.49 d
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100) [M + H] . Found, %: C 73.41; H 9.55; N 11.23.
rel
+
С Н N O. Calculated, %: C 73.13; H 9.0; N 11.37.
1
5
22
2
Treatment with p-hydroxybenzoic acid hydrazi-
de (13).
Ozonolysis in methanol. Methyl ester 5, 1.10 g
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Ozonolysis in CH Cl . Hydrazone 14, 1.39 g
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2
67%), was obtained.
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2
7
. Nurkenov, O.A., Satpaeva, Zh.B., Schepetkin, I.A.,
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hydrazone 14.
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8
(
14). White crystals, mp 121–122°С, R 0.10 (hexane–
f
–
1
MTBE, 2 : 1). IR spectrum (KBr), ν, cm : 3165 (NН),
https://doi.org/10.1134/S107042801901007X
1
1
0
1
715 (С=О), 1662 (C=N). Н NMR spectrum, δ, ppm:
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.88 t (3Н, С Н , J 7.4 Hz), 1.10–1.40 m (6Н, С Н ),
3
2
3
7
.45–1.65 m (4Н, С Н , С Н ), 2.25–2.31 m (2Н,
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2
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2
С Н ), 6.90 br.s (1Н, NН), 6.85 d (3Н, 2СНarom, J
8
7
ppm: 14.05 q (CН ), 22.59, 24.32, 26.99, 29.10, 31.57,
3
1
ОН), 167.20 (C=O). Found, %: C 68.51; H 8.25; N 10.31.
С Н N O . Calculated, %: C 68.67; H 8.45; N 10.68.
Mass spectrum, m/z (I , %): 263 (100) [M + H] .
2
1
1
.7 Hz), 7.05 br.s (ОН), 7.52 t (1Н, С Н=N, J 5.8 Hz),
.90 d (2Н, 2СНarom, J 8.6 Hz). C NMR spectrum, δ,
1
3
3
2.16 all t (CH ), 115.36 d (2СНarom), 121.70 (Сarom),
2
31.78 d (2СНarom), 153.44 d (СН=N), 161.18 (Carom
–
15
22
2
2
+
https://doi.org/10.1134/S1070428014080016
rel
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 11 2019