Transformations of peroxide ozonolysis products of terminal olefins treated with tosylhydrazide

Full text of DOI:10.1134/S1070428016110294

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2016, Vol. 52, No. 11, pp. 1708–1710. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © Yu.V. Legostaeva, L.R. Garifullina, I.S. Nazarov, A.A. Kravchenko, L.V. Kravchenko, G.Yu. Ishmuratov, 2016, published in Zhurnal
Organicheskoi Khimii, 2016, Vol. 52, No. 11, pp. 1712–1714.
SHORT
COMMUNICATIONS
Transformations of Peroxide Ozonolysis Products
of Terminal Olefins Treated with Tosylhydrazide
Yu. V. Legostaeva, L. R. Garifullina, I. S. Nazarov, A. A. Kravchenko,
L. V. Kravchenko, and G. Yu. Ishmuratov*
Ufa Institute of Chemistry, Russian Academy of Sciences, pr. Oktyabrya 71, Ufa, 450054 Russia
*е-mail: insect@anrb.ru
Received June 7, 2016
DOI: 10.1134/S1070428016110294
Hydrazine derivatives (semicarbazide, 2,4-
dinitrophenylhydrazine, and also hydrochlorides of
phenylhydrazine, semicarbazide, thiosemicarbazide)
[1, 2] and hydroxylamine hydrochloride [1, 3] in
solvents of diverse nature efficiently reduce the
peroxide ozonolysis products of versatile substituted
alkenes into carbonyl compounds and their О- or N-
derivatives.
Transformation of peroxide ozonolysis products of alkenes 1–3 treated with tosylhydrazide in protic solvents at 0°С
Run no.
Unsaturated compound
Solvent
MeOH
Reaction product (yield, %)
H
N
1
2
N
Ts
1
1
4 (76)
i-PrOH
4 (70)
O
4 (42) +
3
1
AcOH–CH2Cl2
OH
5 (19)
O
O
N
Ts
4
5
MeOH
HO
HO
N
H
2
2
6 (68)
6 (82)
i-PrOH
O
OH
HO
O
6
7
2
AcOH–CH2Cl2
MeOH
O
7 (80)
O
N
Ts
MeO
N
H
MeO
3
3
8 (70)
8 (74)
8
9
i-PrOH
3
AcOH–CH2Cl2
8 (86)
1708

TRANSFORMATIONS OF PEROXIDE OZONOLYSIS PRODUCTS
1709
OOH
OR'
R
N
Ts
O3, R'OH, 0oC
NH2NHTs
NH2NHTs
O
N
H
R
R
_
H2O
R
H
1_3
9
10
11
_
H2O
O
AcOH
R
R
O
H2O
_
AcOH
OAc
OH
12
13
R = C7H15 (1), C8H16COOH (2), C8H16COOMe (3); R' = Me, i-Pr, Ac.
The ability of p-toluenesulfonic acid hydrazide to
reduce efficiently peroxide ozonolysis products of termi-
nal olefins in protic solvents underlies the one-pot ozo-
nolysis synthesis of nor-analogs of tosylhydrazones.
The results of the conversion of synthesized at 0°С pe-
roxide ozonolysis products of terminal alkenes (1-no-
nene 1, 10-undecenoic acid 2, its methyl ester 3) in protic
solvents (MeOH, i-PrOH, AcOH‒CH2Cl2) under the treat-
ment with tosylhydrazide are compiled in the table.
dissolved in 150 mL of CHCl3, washed with brine (4 ×
35 mL), dried with Na2SO4, and evaporated.
4-Methyl-N'-octilidenebenzene-1-sulfonohydra-
zide (4). а. After chromatographing on SiO2 (eluent
petroleum ether–tert-butyl methyl ether, 10 : 1→1 : 1,
МеОН) of 2.60 g of the reaction mixture obtained by
ozonolysis of 1-nonene 1 in methanol, yield 2.25 g
(76%). Rf 0.60 (eluent petroleum ether–tert-butyl
methyl ether, 1 : 2). IR spectrum, ν, cm–1: 3215 (NH).
1Н NMR spectrum, δ, ppm: 1.00‒1.80 m (13Н, 5СН2,
СН3, С3Н2‒С8Н3), 2.40 s (3Н, СН3), 2.75‒2.95 m (2Н,
С2Н2), 7.10 m (CН=N), 7.45 d (2Нarom), 7.70 d
(2Нarom), 7.95 br.s (NH). 13С NMR spectrum, δ, ppm:
13.75 q (C8H3), 21.06 q (CH3), 22.26 t (C7H2), 25.35 t
(C3H2), 28.57 t (C4H2), 28.74 t (C5H2), 29.31 t (C6H2),
33.75 t (C2H2), 128.51 d (2СaromН), 129.41 d
(2СaromН), 136.11 s (С‒S), 144.62 s (Carom‒CH3),
165.28 d (C1Н=N). Found, %: C 60.67; H 8.30; N
9.51; S 10.71. C15H24N2O2S. Calculated, %: C 60.78;
H 8.16; N 9.45; S 10.82.
The analysis of obtained experimental data makes it
possible to conclude that we have developed a one-pot
ozonolysis method of conversion of terminal alkenes
in methanol and 2-propanol into the corresponding nor
-analogous tosylhydrazones by using tosylhydrazi-de
in the reduction stage of the intermediate peroxides. In
the system AcOH‒CH2Cl2 along with tosylhydrazo-nes
the corresponding carboxylic acids formed as an admi-
xture (run no. 5) or as a single reaction product (run no. 6)
due apparently to the nature of the unsaturated compound.
The formation of tosylhydrazones 11 originates from
the condensation of tosylhydrazide with aldehydes 10,
products of hydride reduction of primary formed hydro-
peroxides 9. In the solvent system AcOH–CH2Cl2 appa-
rently alongside the reduction of peroxides 9 their dehydra-
tion occurs affording mixed anhydrides 12, which are hyd-
rolyzed giving the corresponding carboxylic acids 13.
b. After chromatographing on SiO2 (eluent petroleum
ether–tert-butyl methyl ether, 10 : 1→1 : 1, МеОН) of
2.40 g of the reaction mixture obtained by ozonolysis
of 1-nonene 1 in 2-propanol, yield 2.01 g (70%).
c. After chromatographing on SiO2 (eluent petroleum
ether–tert-butyl methyl ether, 10 : 1→1 : 1, МеОН) of
1.7 g of the reaction mixture obtained by ozonolysis of
1-nonene 1 in a mixture AcOH‒CH2Cl2, yield 1.26 g
(42%) of hydrazone 4 and 0.27 g (19%) acid 5.
Ozonolysis of alkenes (1–3). General procedure.
Through a solution of 10.0 mmol of alkene 1–3 in
25 mL of anhydrous alcohol (MeOH or i-PrOH) or in a
mixture of 25 mL of CH2Cl2 and 5.7 mL of АсОН at
0°С was bubbled the ozone-oxygen mixture till
10 mmol of ozone was consumed. The reaction
mixture was flushed with argon. At 0°С 6.51 g
(35.0 mmol) of ТsNHNH2 was added, the reaction
mixture was stirred at room temperature till disap-
pearance of preoxides (monitoring by the starch iodide
test), the solvent was distilled off, the residue was
Octanoic acid (5). Rf 0.25 (hexane–tert-butyl
1
methyl ether, 2 : 1). IR, 13С and Н NMR spectra are
identical to previously described [4, 5].
10-[(2-Methylbenzene-1-sulfonyl)hydrazinyli-
dene]decanoic acid (6). а. After chromatographing on
SiO2 (eluent petroleum ether–tert-butyl methyl ether,
10 : 1→1 : 1, МеОН) of 2.75 g of the reaction mixture
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 11 2016

LEGOSTAEVA et al.
1710
obtained by ozonolysis of 10-undecenoic acid 2 in
methanol, yield 2.40 g (68%). Rf 0.25 (eluent petro-
leum ether–tert-butyl methyl ether, 1 : 2). IR spectrum,
1 : 1) of 3.10 g of the reaction mixture obtained by
ozonolysis of compound 3 in 2-propanol yield 2.71 g
(74%).
1
ν, cm–1: 3250 (NH, СООН), 1709 (С=О). Н NMR
c. After chromatographing on SiO2 (eluent
petroleum ether–tert-butyl methyl ether, 10 : 1→1 : 1,
МеОН) of 3.60 g of the reaction mixture obtained by
ozonolysis of compound 3 in the mixture AcOH‒
CH2Cl2 yield 3.20 g (86%).
spectrum, δ, ppm: 1.10‒1.40 m (12Н, 6СН2), 1.45–
1.60 m (2Н, СН2СН=N), 2.15‒2.40 m (2Н, СН2СО2),
2.40 s (3Н, СН3), 7.10 m (CН=N), 7.20 d (2Нarom),
7.70 d (2Нarom), 9.70–10.25 br.s (NH, ОН). 13С NMR
spectrum, δ, ppm: 21.28 q (CH3), 23.63, 24.64, 24.90,
28.92, 28.97, 29.14 t (6СН2), 33.98 t (CH2CН=N),
34.62 t (CH2CO2), 128.62 d (2СaromН), 129.54 d
(2СaromН), 136.39 d (CН=N), 142.07 s (С‒S), 143.91 s
(Carom‒CH3), 179.11 s (СО2Н). Found, %: C 57.45; H
7.44; N 8.02; S 9.01. C17H26N2O4S. Calculated, %: C
57.60; H 7.39; N 7.90; S 9.05.
The study was performed using the equipment of
the Center of joint busage “Chemistry” of the Ufa
Institue of Chemistry of the Russian Academy of
Sciences. IR spectra were recorded on a spectro-
photometer IR Prestige-21 (Fourier Transform
Spectrophotometer – Shimadzu) from thin films. NMR
spectra were registered on a spectrometer Bruker АМ-
300 [operating frequencies 300 (1Н), 75.47 (13С) MHz]
in CDCl3, internal reference TMS. GLC was per-
formed on a chromatograph Chrom-5 [column 1.2 m
long, stationary phase SE-30 (5%) on the carrier
Chromaton N-AW-DMCS (0.16–0.20 mm), ramp 50–
300°С], carrier gas helium. TLC monitoring was
carried out on SiO2 Sorbfil (Russia). For column
chromatography SiO2 (70–230) Lancaster (England)
was used. The elemental analysis data of all studied
compounds were in agreement with the calculated
values. Ozonator output was 40 mmol О3/h.
b. After chromatographing on SiO2 (eluent
petroleum ether–tert-butyl methyl ether, 10 : 1→1 : 1,
МеОН) 3.22 g of the reaction mixture obtained by
ozonolysis of 10-undecenoic acid 2 in 2-propanol,
yield 2.87 g (82%).
1,10-Decandioic acid (7). After chromatographing
on SiO2 (eluent petroleum ether–tert-butyl methyl ether,
10 : 1→1 : 1, МеОН) of 1.88 g of the reaction mixture
obtained by ozonolysis of 10-undecenoic acid 2 in a
mixture AcOH‒CH2Cl2, yield 1.62 g (80%). Rf 0.35
(hexane–tert-butyl methyl ether, 1 : 1), mp 130–132°С.
1
IR spectrum, ν, cm–1: 3180, 1703 (CO2Н). Н and 13С
The study was carried out under the financial
support of Bashkortostan Republic Government for
young scientists and young scientific teams (grant
no. 48 of 18.02.2016).
NMR spectra are identical to previously described [6].
Methyl 10-[(2-methylbenzene-1-sulfonyl)hydra-
zinylidene]decanoate (8). а. After chromatographing
on а SiO2 (eluent petroleum ether–tert-butyl methyl ether,
10 : 1→1 : 1, МеОН) of 6.30 g of the reaction mixture
obtained by ozonolysis of methyl 10-undecenoate 3 in
methanol, yield 2.57 g (70%). Rf 0.41 (eluent petroleum
ether–tert-butyl methyl ether, 1 : 2). IR spectrum, ν,
cm–1: 3226 (NH), 1738 (С=О), 1174‒1234 (С‒О‒С). 1Н
NMR spectrum, δ, ppm: 1.10‒1.40 m (12Н, 6СН2), 1.45‒
1.60 m (2Н, СН2СН=N), 2.18‒2.30 m (2Н, СН2СО2),
2.35 s (3Н, СН3), 3.50 s (3Н, СООСН3), 7.05 m (CН=N),
7.25 d (2Нarom), 7.65 d (2Нarom), 9.05 br.s (NH). 13С NMR
spectrum, δ, ppm: 21.17 q (CH3), 25.33, 28.69, 28.74,
28.92, 29.07, 29.23 t (6СН2), 33.66 t (CH2CН=N), 33.77 t
(CH2CO2), 51.21 q (CH3O), 128.62 d (2СaromН),
129.28 d (2СaromН), 136.17 d (CН=N), 141.86 s (С‒S),
144.47 s (Carom‒CH3), 174.15 s (СО2Me). Found, %: C
58.55; H 7.71; N 7.76; S 8.62. C18H28N2O4S.
Calculated, %: C 58.67; H 7.66; N 7.60; S 8.70.
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