Heterocyclization of β,γ-unsaturated onium compounds of phosphorus and nitrogen under the action of phenylhydrazine

Full text of DOI:10.1134/S107036321009032X

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 9, pp. 1891–1893. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © M.Zh. Ovakimyan, G.A. Gasparyan, A.S. Pogosyan, M.L. Movsisyan, M.G. Indzhikyan, G.A. Panosyan, 2010, published in Zhurnal
Obshchei Khimii, 2010, Vol. 80, No. 9, pp. 1577–1579.
LETTERS
TO THE EDITOR
Heterocyclization of β,γ-Unsaturated Onium Compounds
of Phosphorus and Nitrogen Under the Action
of Phenylhydrazine
M. Zh. Ovakimyana, G. A. Gasparyana, A. S. Pogosyana,
M. L. Movsisyana, M. G. Indzhikyana, and G. A. Panosyanb
a Institute of Organic Chemistry of National Academy of Sciences of Armenia,
ul. Zakariya Kanakertsi 167, Yerevan, 375091 Armenia
e-mail: ioc_phos@mail.ru
b Center of Studies of Structure of Molecules of National Academy of Sciences of Armenia, Yerevan, Armenia
Received December 14, 2009
DOI: 10.1134/S107036321009032X
Recently we found that triphenyl and tributyl-4-
bromo-3-chlorobut-2-enylphosphonium bromides re-
acted even at room temperature with two equivalents
of phenylhydrazine to form the products of dehydra-
tion of phenylhydrazine intermediates, phenylhyd-
razones of triphenyl- and tributyl-3-chlorocrotonoyl-
phosphonium salts respectively [1].
have studied the reactions of trimethyl- and triethyl-4-
bromo-3-chlorobut-2-enylammonium bromides I, II
with two equivalents of phenylhydrazine. Unexpec-
tedly the formation of trimethyl(1-phenyl-2,5-dihydro-
pyrazol-3-yl)methylammonium bromide hydrochloride
III and triethyl(1-phenyl-2,5-dihydropyrazol-3-yl)-
methylammonium bromide IV in 66% and 75% yields
respectively and of phenylhydrazine hydrobromide
in 95% yield was observed. The formation of
compounds II and IV may be described by the
following scheme.
In extension of these studies with the purpose of
establishing the possibility of dehydration in the
analogously arranged quaternary ammonium salts we
+
+
R3NCH2CH
R3NCH2CH
CCH2NNH2
CCH2Br + 2PhNHNH2
Cl
_
_
Br
Br
Cl
Ph
R = CH3 (I), R = C2H5 (II)
+
Me3N
HCl
N
N
B_r
Ph
Cl
N
H
+
R3N
_PhNHNH2 HBr
N
B_r
III
Ph
N
H
+
Et3N
B_r
Ph
N
H
IV
1891

1892
OVAKIMYAN et al.
The heterocyclization was observed also in the
dehydrated derivatives IX, X were obtained. Reaction
pathway may be described by the following scheme
including the prototropic isomerization of salts V, VI
to the allene intermediates.
reaction of tributylphosphonium salts containing 4-
bromobyt-2-ynyl group V, VI with phenylhydrazine.
In both cases the pyrazoles VII, VIII and also their
R3PCH
Br
+
2PhNHNH2
R3PCH2 C C CH2NNH2
2 C C CH2Br
_PhNHNH2 HBr
Br
Ph
V, VI
R = Ph (V), R = Bu (VI)
R3P
Br
R3P CH
Br
N
C
CHCH2NNH2
Ph
Ph
N
H
R = Ph (VII, IX), R = Bu (VIII, X)
R3P
Br
R3P
N
+
N
N
Ph
Ph
Br
N
IX, X
VII, VIII
Alkaline hydrolysis of a mixture of compounds
VII, IX with 25% aqueous solution of alkali yielded
triphenylphosphine oxide and a mixture of 3-methyl-1-
phenyl-4,5-dihydro- and 3-methyl-1-phenylpyrazoles.
1.7 g of the salt V and 0.8 g of phenylhydrazine in
chloroform at 5–0°C 1 g of a mixture of compounds
VII and IX in 1:1 ratio was obtained.
1H NMR spectrum of compound VII (DMSO-d6/
CCl4 1:3), δ, ppm (J, Hz): 2.95 t (2H, CH2, J 10.4),
3.65 t (2H, NCH2, J 10.4), 5.35 d (2H, PCH2, J 15.2
Hz), 6.48 m (2H, 2.6-HPh), 6.67 m (1H, 4-HPh), 7.04 m
(2H, 3,5-HPh), 7.68–7.97 m (15H, PPh3). 31P NMR
spectrum (DMSO-d6/CCl4, 1:3), δp 27.1 ppm.
1H NMR spectrum of compound IX (DMSO-d6/
CCl4 1:3), δ, ppm (J, Hz): 5.40 d (2H, PCH2, J 15.2),
6.31 d.d (1H, 4-HPyr, J1 2.3, J2 1.4). 7.23 m (1H, 4-
HPh), 7.38 m (2H, 3,5-HPh), 7.53 m (2H, 2,6-HPh),
7.68–7.97 m (15H, PPh3), 8.25 d (1H, 5-HPyr, J 2.3).
31P NMR spectrum (DMSO-d6/CCl4 1:3) δP 27.6 ppm.
Trimethyl(1-phenyl-2,5-dihydropyrazol-3-yl)me-
thylammonium bromide hydrochloride (III). The
reaction of 1.4 g of the salt I and phehylhydrazine in
methanol at room temperature gave 1 g (66%) of
1
yellow powder with mp 207°C. H NMR spectrum
(DMSO-d6), δ, ppm (J, Hz): 3.25 s (9H, N+CH3), 4.30
d (2H, NCH2, J 7.2), 4.57 s (2H, N+CH2), 6.63 t (1H,
=CH, J 7.2), 7.08 m (1H, 4-H, C6H5), 7.26 m (2H, 2,6-
H, C6H5), 7.37 m (3H, 3,5-H, C6H5), 10.30 br.s (2H,
NH·HCl). Found, %: C 46.64, H 6.28. C13H21BrClN3.
Calculated, %: C 46.54; H 6.32.
Reaction of triethyl(3-chloro-4-bromobut-2-enyl)-
ammonium bromide (II) with phenylhydrazine. From
1.5 g of the salt II and 0.9 g of phenylhydrazine in
acetonitrile at room temperature 1.55 g of the viscous
mixture containing ~75–80% of compound IV accord-
Alkaline hydrolysis of a mixture of compounds
VII and IX. By the reaction of 1 g of a mixture of
compounds VII and IX with a solution of 0.16 g of
sodium hydroxide in 0.48 g of water 0.4 g of
triphenylphosphine oxide and 0.2 g of a mixture of 3-
methyl-1-phenyl-4,5-dihydro- and 3-methyl-1-phenyl-
pyrazoles in 3:2 ratio was obtained.
1H NMR spectrum of compound VII (DMSO-d6-
CCl4 1:3), δ, ppm (J, Hz): 2.05 s (3H, CH3), 2.84 t
(2H, CH2, J 10.1), 3.64 t (2H, NCH2, J 10.1), 6.67 m
(1H, 4-HPh), 6.88 m (2H, 2,6-HPh), 7.13 m (2H, 3,5-
HPh).
1
1
ing to H NMR data was obtained. H NMR spectrum
(CDCl3), δ, ppm (J, Hz): 1.33 t (6H, CH2-CH3, J 7.3),
3.40 q (4H, CH2CH3, J 7.3), 4.12 d (2H, NCH2, J 7.2),
4.46 s (2H, N+CH2), 6.43 t (1H, =CH, J 7.2), 6.84 m
(1H, 4-H, C6H5), 7.04 m (2H, 2,6-H, C6H5), 7.23 m
(2H, 3,5-H, C6H5).
Reaction of triphenyl(4-bromobut-2-ynyl)phos-
phonium bromide (V) with phenylhydrazine. From
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 9 2010

HETEROCYCLIZATION OF β,γ-UNSATURATED ONIUM COMPOUNDS
1893
1
1H NMR spectrum of compound IX (DMSO-d6/
CCl4 1:3), δ, ppm (J, Hz): 2.31 s (3H, CH3), 6.18 d
(1H, 4-HPy, J 2.4), 7.18 m (1H, 4-HPh), 7.39 m (2H,
3,5-HPh), 7.71 m (2H, 2,6 HPh), 8.04 d (1H, 5-HPyr,
J 2.4).
C4H9, JPC 47.1), 18.6 d (PCH2, JPC 47.2), 22.7 d (β-
1
2
CH2, C4H9, JPC 4.6), 23.2 (γ-CH2, C4H9), 108.9 d (4-
CPyr, 3JPC 5.1), 117.9 and 128.8 (2,3,5,6-CPh), 125.8 (4-
2
CPh), 128.5 (5-CPyr), 142.3 d (N=C, JPC 8.5), 145.5
(1CPh). 31P NMR spectrum of compound X (DMSO-d6/
CCl4 1:3) δP 38.8 ppm.
Reaction of tributyl(4-bromobut-2-ynyl)phos-
phonium bromide VI with phenylhydrazine. By the
reaction of 1 g of salt VI with 0.52 g of phenyl-
hydrazine in chloroform at –5–0oC 0.6 g of a mixture
of compounds VIII and X in 2:3 ratio was obtained.
For the attribution of signals in H and 31P NMR
1
spectra DEPT and NOESY were registered. 1,3-Loca-
tion of substituents in the pyrazole ring of compound
X was confirmed by the presence of strong NOE peak
between 5-H protons of the pyrazole ring and the
protons in o-position of the phenyl group. NOE is
observed also between the protons of NCH2 group and
the protons in o-position of the phenyl group in the
compound VIII.
1H NMR spectrum of compound VIII (DMSO-d6/
CCl4 1:3), δ, ppm (J, Hz): 0.98 t (9H, CH3, J 7.1),
1.42-1.69 m (12H, β,γ-CH2, C4H9), 2.34–2.53 m (6H,
α-CH2, C4H9), 3.11 t.d (2H, CH2, J1 10.4, J2 1.9), 3.77 t
(2H, NCH2, J 10.4), 3.91 d (2H, PCH2, J 14.8), 6.75 t.t
(1H, 4-HPh, J1 7.3, J2 1.0), 6.87 m (2H, 2,6-HPh), 7.18
m (2H, 3,5-HPh). 13C NMR spectrum of compound
VIII (DMSO-d6/CCl4 1:3), δC, ppm (J, Hz): 13.0
1H, 13C, and 31P NMR spectra were taken on a
Varian Mercury-300 spectrometer (300.077 MHz for
13
31
protons, 75.46 MHz for C, and 121.46 MHz for P)
1
1
(CH3), 18.6 d (α-CH2, G4H9, JPC 47.2), 19.9 d (PCH2,
at 303oK. H and 13C chemical shifts are presented
1JPC 47.3), 22.9 d (β-CH2, C4H9, 2JPC 4.7), 23.4 (γ-CH2,
against TMS as the internal standard. Starting salts I
and II were synthesized according to [2], and the salts
V, VI were obtained by the reaction of the corres-
ponding phosphine with the five-fold excess of 1,5-
dibromobut-2-yne without a solvent.
3
C4H9), 36.0 d (CH2, JPC 5.8), 47.7 (NCH2), 112.0 and
128.4 (2,3,5,6-CPh), 118.4 (4-CPh), 139.1 (1-CPh), 144.6
2
d (N=C, JPC 10.0). 31P NMR spectrum of compound
VIII (DMSO-d6/CCl4 1:3), δP 39.0 ppm.
1H NMR spectrum of compound X (DMSO-d6/CCl4
1:3), δ, ppm (J, Hz): 0.98 t (8H, CH3, J 7.1), 1.42–1.69
m (12H, β,γ-CH2, C4H9), 2.34-2.53 m (6H, α-CH2,
C4H9), 4.06 d (2H, PCH2, J 14.8), 6.63 d.d (1H, 4HPyr,
J1 2.4, J2 1.3), 7.27 m (1H, 4-HPh), 7.45 m (2H, 3,5-
HPh), 7.76 m (2H, 2.6-HPh), 8.37 d (1H, 5-HPyr, J 2.4).
13C NMR spectrum of compound X (DMSO-d6/CCl4
1:3), δC, ppm (J, Hz): 13.0 (CH3), 18.2 d (α-CH2,
REFERENCES
1. Ovakimyan, M.Zh., Barsegyan, S.K., Pogosyan, A.S.,
Kikoyan, N.M., Panosya,n G.A., and Indzhikyan, M.G.,
Zh. Obshch. Khim., 2004, vo.l 74, no. 12, p. 1992.
2. Babayan, A.T., Martirosyan, G.T., Gyulnazaryan, A.Kh.,
Arakelyan, E.M., Grigoryan, D.V., and Davtyan, N.M.,
Arm. Khim. Zh., 1972, vol. 25, no. 2, p. 123.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 9 2010