Unusual course of reaction of buta-1,3-diene-1,4- diylbis(triphenylphosphonium chloride) with phenylhydrazine

Full text of DOI:10.1134/S1070363211020344

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 2, pp. 444–446. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © M.Zh. Ovakimyan, M.L. Movsisyan, G.A. Gasparyan, M.G. Indzhikyan, 2011, published in Zhurnal Obshchei Khimii, 2011, Vol. 81,
No. 2, pp. 346–348.
LETTERS
TO THE EDITOR
Unusual Course of Reaction of Buta-1,3-diene-
1,4-diylbis(triphenylphosphonium Chloride)
with Phenylhydrazine
M. Zh. Ovakimyan, M. L. Movsisyan, G. A. Gasparyan, and M. G. Indzhikyan
Institute of Organic Chemistry, National Academy of Sciences of Armenia,
ul. Z. Kanakertsy 167a, Yerevan, 375091 Armenia
e-mail: ioc_phos@mail.ru
Received July 20, 2010
DOI: 10.1134/S1070363211020344
Previously we have found that triphenyl- and tri-
butyl-2-phenylhydrazinoethylphosphonium salts when
heated in ethanol or DMF are dehydrated to form
phenylhydrazones of the corresponding phosphonium
acetic aldehydes in high yields [1]. The same reaction
occurred in the case of triphenyl- and tributyl-
phosphonium salts with 4-N-phenylhydrazino-3-chloro-
but-2-enyl group [2].
of phenylhydrazine in chloroform formed 2-phenyl-
hydrazonobutane-1,4-diylbis(triphosphonium chloride)
II in 85% yield. Yield of compound II decreased to
51% when the starting reagents were used in the
equimolar ratio. The reaction was accompanied in both
cases with the formation of phenylhydrazine hydro-
chloride in high amounts. The latter was established to
form by the reaction of phenylhydrazine with
chloroform. As expected, the reaction of salt I with
equimolr amount of phenylhydrazine in acetonitrile
affords compound II almost in the quantitative yield.
Probably the formation of salt II occurs through initial
addition of phenylhydrazine at one of multiple bonds
of salt I to give intermediate III followed by hydro-
genation of the multiple bond involving the transfer of
a hydride ion by the cyclic mechanism:
Based on the results of these studies we suggested
that this reaction had a cyclic nature including the shift
of a lone electron pair to the onium phosphorus atom
and the hydride ion expulsion from the neighboring
sp3-carbon atom [3].
We found that buta-1,3-diene-1,4-diylbis-
(triphenylphosphonium chloride) I at reflux with 2 mol
H
+
PPh3
+
+
+
PhNHNH2
Cl−
Ph3P
PPh3
+
PPh3
+
Cl−
Cl−
Cl−
Ph3P
Ph3P
Cl−
Cl−
N
H
NNHPh
PhNH
II
III
I
Compound II was found to form also from 2-
butene-1,4-diylbis(triphenylphosphonium chloride) IV
via the reaction with threefold excess of phenyl-
hydrazine in chloroform, but its yield was 7% only. At
the same time among the reaction products were also
triphenyl(4-phenylhydrazonobut-2-enyl)phosphonium
chloride V (46%), triphenylphosphine oxide (34%),
and N-phenyltriphenylphosphine imine hydrochloride
VI (19%), identified by the Н NMR and elemental
analysis data, and phenylhydrazine hydrochloride.
1
3 PhNHNH2
+
+
NNHPh
PPh3
+
+
+ II + Ph3P=NHNHPh + Ph3PO
Cl−
Ph3P
Ph3P
Cl−
VI
Cl−
IV
V
444

UNUSUAL COURSE OF REACTION OF BUTA-1,3-DIENE-...
445
The formation of phenylhydrazone derivatives II
and V can be represented as follows:
NMR spectrum (DMSO-d6), δP, ppm (J, Hz): 28.12,
30.64. Found, %: C 73.06; H 5.59; Cl 9.44; N 3.71; P
8.02. С46Н42Cl2N2P2. Calculated, %: C 73.11; H 5.56;
Cl 9.40; N 3.71; P 8.21.
IV + 3 PhNHNH2
1,3-H shift
1,4-splitting
−Ph3P
Reaction of salt IV with phenylhydrazine. A
mixture of 0.7443 g of IV and 0.35 g of phenyl-
hydrazine in 15 ml of chloroform was heated for 10 h
at 55–57°С. The reaction mixture was treated with
water and extracted with chloroform. After chloroform
removal the residue was subjected to fractional
recrystallization (acetone, isopropanol). Compounds V
(0.23 g, mp 162–164°С), II (0.058 g, mp 215–220°С),
VI (0.085 g, mp 240–245°С), triphenylphosphine
oxide (0.1025 g, mp 154°С) and phenylhydrazine
hydrochloride (0.37 g) were otained. Compound V.
1Н NMR spectrum (DMSO-d6), δ, ppm (J, Hz.): 4.55
+
+
PPh3
+
Ph3P
Ph3P
Cl−
Cl−
Cl−
PhNHNH2
PhNHNH2
+
NHNHPh
+
PPh3
+
Ph3P
Ph3P
Cl−
Cl−
Cl−
NHNHPh
−H2
−H2
2
3
d.d (2Н, Р+CH2, JРН 16.2, J 7.5), 5.49 d. t. d (1Н,
3
3
3
CH2СН, J 15.4, J 7.5, JРН 6.6), 6.39 d.d.d (1Н,
CH2СН=СН, 3J 15.4, 3J 9.1, 4JРН 5.2), 6.65 m (1Н, 4-H
Ph), 6.94 m (2H, 2,6-H Ph), 7.05 m (2H, 3,5-H Ph),
V
II
Triphenylphosphine was not detected in the
reaction product. We found that triphenylphosphine
reacts with phenylhydrazine to afford compound VI. It
is possible that the triphenylphosphine oxide is a
product of partial hydrolysis of VI.
3
7.54 d (1Н, N=СН, J 9.1), 7.60–7.84 m (15Н, Ph3Р+)
10.34 br. s (1H, NH). 13С NMR spectrum (DMSO-d6),
δC, ppm (J, Hz.): 23.7 d (СН2, 1JРС 49.4), 112.0 (2,6-С,
2
NHPh), 115.2 d CH2СН, JРС 11.5), 117.5 d (1-С,
Р+Ph3, 1JРС 85.3), 118.6 d (4-С, NHPh), 128.2 (3,5-С,
NHPh), 129.7 d (2,6-С, Ph 3Р+, 2JРС 12.5), 133.3 d (3,5-
С, Ph3Р+, 3JРС 9.7), 134.6 d (4-С, Ph3Р+, 4JРС 2.8), 135.8
d (1С, N=СН, 4JРС 5.2), 137.7 d (=СНСНN, 3JРС 13.8),
144.3 (1-С, NHPh). 31Р NMR spectrum (DMSO-d6),
δP, ppm (J, Hz): 25.7. Found, %: C 73.64; H 5.67; Cl
7.73; N 6.15; P 6.81. С28Н26ClN2Р. Calculated, %: C
73.60; H 5.69; Cl 7.77; N 6.13; P 6.79. Compound
The Н, 13С and 31Р NMR spectra were registered
1
on a Varian Mercury-300 spectrometer operating at
300.077 (1H), 75.46 (13С) and 121.47 MHz (31Р),
respectively, at 303 K, internal reference TMS. The
starting salts I and IV were obtained by procedures [4, 5].
2-Phenylhydrazonobutane-1,4-diylbis(triphenyl-
phosphonium chloride) (II). A mixture of 2 g of salt I
and 0.67 g of phenylhydrazine in chloroform was
stirred at 60°С, then treated with water and chloroform
to obtain 0.5 g of phenylhydrazine hydrochloride and
1
VI. Н NMR spectrum (DMSO-d6), δ, ppm (J, Hz.):
6.69 t. t (1Н, 4-H NHPh, J 3.1), 6.83 m (2H, 2,6-H
NHPh), 7.03 m (2H, 3,5-H NHPh), 7.63–7.70 m (6Н,
2,6-Н Ph3Р+), 7.79-7.92 m (9Н, 3,5-Н, 4-Н Ph3Р+),
8.46 s (1H, NHPh), 10.51 d (1Н, =NН, JРС 31.3). 31Р
NMR spectrum (DMSO-d6), δP, ppm (J, Hz): 43.1.
Found, %: C 71.02; H 5.35; Cl 8.52; N 6.80; P 7.53.
С24Н22ClN2Р. Calculated, %: C 71.19; H 5.44; Cl 8.78;
N 6.92; P 7.66.
1
2 g of II. Yield 85%, mp 215–220°С. Н NMR
spectrum (DMSO-d6), δ, ppm (J, Hz.): 2.85 m (2Н,
СCH2CH2), 4.52 m (2Н, СCH2CH2), 5.60 d (2Н,
Р+CH2С, J 14.2), 6.19 m (2Н, 2,6-H Ph), 6.58 m (1H,
4-H Ph), 6.84 m (2H, 3,5-H Ph), 7.64-8.04 m (30H,
Р+Ph3), 9.45 br.s (1Н, NH). 13С NMR spectrum
(DMSO-d6), δC, ppm (J, Hz): 17.9 d (Р+СН2СН2,
J 50.7), 23.2 d (Р+СН2СН2, J 8.9), 29.7 d (Р+СН2С=,
J 55.9), 112.5 (2,6-С, NНPh), 118.0 d (1-С, Р+Ph3,
J 85.9), 118.5 (4-C, NHPh), 120.2 d (1-С, Р+Ph3,
J 88.6), 127.7 (3,5-С, NНPh), 129.2 d (2,6-C, Р+Ph3,
J 12.7), 129.8 d (2,6-C, Ph3Р+, J 12.6), 133.5 d (4-C,
Р+Ph3, J 2.8), 133.6 d (3,5-C, Р+Ph3, J10.3), 134.0 d
(3,5-C, Р+Ph3, J 10.4), 134.3 d (4-C, Р+Ph3, J 2.8),
137.2 d.d (N=C, J1 17.8, J2 8.8), 145.1 (NPh). 31Р
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