Reaction of secondary phosphine chalcogenides with diallylamine

Article abstract of DOI:10.1134/S1070363214090175

Diphenyl- or bis(2-phenylethyl)phosphine sulfides and -phosphine selenides react with diallylamine under radical initiation (UV or AIBN) to afford the corresponding diadducts and tetrahydropyrrolylmethyl phosphine chalcogenides. The yield and the ratio of

Full text of DOI:10.1134/S1070363214090175

ISSN 1070-3632, Russian Journal of General Chemistry, 2014, Vol. 84, No. 9, pp. 1742–1747. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © S.I. Verkhoturova, T.I. Kazantseva, S.N. Arbuzova, A.I. Albanov, N.K. Gusarova, B.A. Trofimov, 2014, published in Zhurnal
Obshchei Khimii, 2014, Vol. 84, No. 9, pp. 1502–1508.
Reaction of Secondary Phosphine Chalcogenides
with Diallylamine
S. I. Verkhoturova, T. I. Kazantseva, S. N. Arbuzova,
A. I. Albanov, N. K. Gusarova, and B. A. Trofimov
A.E. Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: boris_trofimov@irioch.irk.ru
Received April 21, 2014
Abstract—Diphenyl- or bis(2-phenylethyl)phosphine sulfides and -phosphine selenides react with diallylamine
under radical initiation (UV or AIBN) to afford the corresponding diadducts and tetrahydropyrrolylmethyl
phosphine chalcogenides. The yield and the ratio of the products depend on the structure of the starting
secondary phosphine chalcogenides.
Keywords: secondary phosphine chalcogenides, diallylamine, radical initiation, cyclization
DOI: 10.1134/S1070363214090175
Addition of secondary phosphines and phosphine
chalcogenides to polyalkenes is a convenient atom-
economic approach to the synthesis of polyphosphines
and polyphosphine chalcogenides including their
functional derivatives. Reactions of this type have been
successfully realized under radical conditions by the
example of divinyl [1], diallyl [2, 3], trivinyl [4],
tetravinyl [5] ethers, divinyl chalcogenides [6–9], as
well as tris(4-vinylbenzyl)phosphine oxide [10]. As a
result, promising polydentate ligands for metal
complexes, including metallacrown ethers [1, 11–13]
have been synthesized.
In the present work we have studied for the first
time the radical addition of secondary phosphine sulfides
and phosphine selenides to diallylamine in order to
develop a general convenient atom-economic method
of the synthesis of functional tertiary phosphine chalco-
genides containing an amino group.
Diphenylphosphine sulfide (I) turned out to react
with diallylamine (in the ratio 2 : 1) in benzene or
dioxane at UV irradiation (200W Hg arc Lamp) or in
the presence of AIBN (5 wt %, 60–65оС) in 2–2.5 h to
give diadduct II as the main product (the isolated yield
52%). For the equimolar ratio of the reagents, com-
pound II is also the main product (Scheme 2).
At the same time, there are no data in the literature
on the reaction of diallylamine with secondary phos-
phine chalcogenides, although substituted diallyl-
amines react with diphenylphosphine oxide (AIBN-
initiation) [2] and diphenylphosphine sulfide (micro-
wave activation) [3] to give cyclic adducts, phosphorus-
containing pyrrolidines (Scheme 1).
Scheme 2.
Ph
Ph
S
N
H
P
+
H
I
Scheme 1.
Ph
Ph
P
Me
Ph
P
Ph
Ph
Ph
AIBN (60−65oC)
Ph
Ph
X
H
S
S
N
H
P
N
R
+
X
or UV
N
R
P
R = PhC(O), X = O [2]; R = t-BuOC(O), X = S [3].
II
1742

REACTION OF SECONDARY PHOSPHINE CHALCOGENIDES
1743
Scheme 3.
Ph
Ph
Ph
Ph
Me
S
UV
P
+
P
N
H
dioxane
H
S
N
H
V
IV
Scheme 4.
R
N
H
P
R
R
R
R
R
S
AIBN (60−65oC)
S
P
S
N
H
P
or UV
H
I, V
A
Ph
Ph
Ph
Ph
S
P
Ph
P
P
Ph
Ph
Ph
Ph
H
S
S
S
A1
P
S
+
N
H
N
H
Ph
P
II
Ph
Ph
Me
A2
P
S
N
H
IV
R = Ph (A1), Ph(CH2)2 (A2).
Besides, under these conditions, the formation of a
small amount of side cyclic product, (4-methyltetra-
hydro-1H-pyrrol-3-yl)methyl(diphenyl)phosphine sul-
radical addition (UV or AIBN-initiation, 60–65°С) of
bis(2-phenylethyl)phosphine sulfide (V) to diallyl-
amine in benzene or dioxane. Under optimal con-
ditions (UV irradiation, dioxane, 7.5 h, the ratio of the
reagents 1 : 1) compound (IV) was isolated in
preparative yield of 45% (Scheme 3).
1
fide (III) was detected by H, 31P NMR and chro-
matomass spectrometry:
Ph
Me
The difference in chemoselectivity of the studied
reaction of diallylamine phosphorylation with phos-
phine sulfides I, V and the formation of tertiary
phosphine sulfides II–IV can be rationalized as
follows (Scheme 4). The P-centered radical generated
from secondary phosphine sulfides adds to the double
bond of the diallylamine molecule to form the C-
centered radical (A), which can further react in two
ways. In the case of diphenylphosphine sulfide I
Ph
P
S
N
H
III
At the same time, a similar heterocycle, (4-
methyltetrahydro-1H-pyrrol-3-yl)methyl(diphenethyl)-
phosphine sulfide (IV), is the major product of the
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 9 2014

1744
VERKHOTUROVA et al.
Scheme 5.
Ph
Ph
Se
H
Ph
Ph
Me
UV
P
+
P
N
H
dioxane
Se
N
H
VI
Scheme 6.
Ph
Ph
Se
H
H
Ph
Ph
Se
+
−
P
+
P
+ Se
H
N
N
H
Se
VIII
Scheme 7.
N
Ph
Ph
Se
H
H
Ph
Ph
Ph
Ph
Ph
Se
H
Se
H
+
−
P
P
P
H +
P
2
N
SeH
Ph
Se
VII
IX
VIII
radical (А1) readily abstracts hydrogen atom from the
second molecule of phosphine sulfide to give a new P-
centered radical. The latter is added to the double bond
of the monoadduct to give diadduct II. As distinct of
that, radical (А2) does not react with bis(2-phenylethyl)-
phosphine sulfide (V) (where the P–H bond is,
apparently, more strong as compared to that in the
molecule of diphenylphosphine sulfide), but rather is
added intramolecularly to the second double bond to
form the cyclic product IV.
At the same time, the main products of the reaction
of diphenylphosphine selenide with diallylamine under
UV irradiation are diphenylphosphine VII and
diallylammonium diphenylselenophosphinate VIII,
whereas the expected acyclic and cyclic adducts are formed
in small amounts. We failed to isolate compounds VII,
VIII from the complex reaction mixture, but they were
identified by 31P NMR spectroscopy comparing with
authentic samples. To this end, diselenophosphinate
VIII was specially first synthesized by us from di-
phenylphosphine selenide, diallylamine, and elemental
selenium by the known reaction [14] (Scheme 6).
The reaction of secondary phosphine selenides with
diallylamine under the conditions of radical initiation
proceeds in a less selective manner. Thus, bis(2-phe-
nylethyl)phosphine selenide reacts with diallylamine in
the presence of AIBN (60–65°С, benzene) or under
UV irradiation to form a mixture of organophos-
phorous compounds among which the main one (~60%
according to the 31P NMR spectra) is (4-methyl-
tetrahydro-1H-pyrrol-3-yl)methyl(diphenethyl)phos-
phine selenide (VI) (Scheme 5). Under optimal
conditions (UV irradiation, dioxane, 4 h, the ratio of
the reagents 1 : 1) phosphine selenide VI was isolated
in preparative yield of 32%.
The formation of compounds VII, VIII can be
represented by Scheme 7 including the stage of
reversible disproportionation of the secondary phos-
phine selenide to the corresponding secondary phos-
phine VII and diselenophosphinic acid IX. The latter
reacts with diallylamine to give diselenophosphinate
VIII thus shifting the equilibrium to the right.
A similar reaction of secondary phosphine selenides
with amines at room temperature without initiator was
described earlier [15].
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REACTION OF SECONDARY PHOSPHINE CHALCOGENIDES
1745
Scheme 8.
Ph
Ph
Ph
Se
H
Se
AIBN
P
+
P
H
VII + VIII +
N
60−65oC
Ph
N
All
All
X
In the case of chemical initiation (AIBN, 60–65°С,
dioxane), diphenylphosphine selenide reacts with
diallylamine to afford, along with compounds VII,
VIII, also the amide of N,N-diallyl(diphenyl)seleno-
phosphinic acid (X) (Scheme 8).
It turned out that this reaction takes place in the
absence of initiator (60–65°С, dioxane). Under these
conditions, amide X was isolated with the yield of
24%. The latter is formed, apparently, due to thermal
decomposition of diselenophosphinate VIII according
to Scheme 9 as suggested earlier [16].
Note that secondary phosphine oxides practically
do not react with diallylamine under the developed
conditions (UV initiation or in the presence of AIBN).
This fact is in contradiction with the aforementioned
literature data [2], but it is in accordance with the
commonly accepted notions of a relatively low
reactivity of secondary phosphine oxides in the reac-
tions of radical addition to the double bond [3, 17–19].
It is important that the starting bis(2-phenylethyl)-
phosphine sulfide and selenide are now available and
can be readily prepared from elemental phosphorus,
styrene, and elemental chalcogenides [20, 21].
Therefore, new fundamental data on the reactions
of secondary phosphine chalcogenides with diallyl-
amine were obtained. The course of the reaction
depends both on the reaction conditions and on the
structure of organic radical and the nature of the
chalcogene in the molecule of the starting phosphine
chalcogenide. Diorganylphosphine sulfides and bis(2-
phenylethyl)phosphine selenide react with diallylamine
under the conditions of radical initiation (AIBN, UV
irradiation) via the diaddition route and/or mono-
cycloaddition to afford the corresponding diadducts
and tetrahydropyrrolylmethylphosphine chalcogenides.
An original reaction of diphenylphosphine selenide
with diallylamine was found leading to the mixture of
organophosphorous compounds, the main products
being diphenylphosphine, diallylammonium diphenyl-
diselenophosphinate, and amide of N,N-diallyl(di-
phenyl)seleno-phosphinic acid. Secondary phosphine
oxides practically do not react with diallylamine under
the studied conditions.
EXPERIMENTAL
1Н, 13C, 31Р, and 77Se spectra were registered on a
Bruker DPX 400 spectrometer (400.13, 100.62,
161.98, and 76.31 MHz, respectively) in CDCl3,
internal reference HMDS (1Н, 13C), Me2Se (77Se),
external reference 85% H3PO4 (31P). The signals in the
1Н, 13C NMR spectra were assigned using 2D homo-
and heteronuclear NMR techniques: COSY, HSQC.
Mass spectra of electron impact (70 eV) were obtained
on
a
GCMS-QP5050A SHIMADZU instrument
(quadruple mass analyzer, the range of detected masses
34–450 Da, capillary column, SPB–5 phase).
N,N-Bis[3-(diphenylphosphorothioyl)propyl]
amine (II). The solution of diphenylphosphine sulfide
I (0.093 g, 0.43 mmol) and diallylamine (0.021 g,
0.215 mmol) in 1.2 mL of benzene was placed in a
quartz ampule flushed with argon and irradiated with
UV light for 2.5 h. Benzene was removed under a
reduced pressure, the residue was dried in a vacuum.
The 31P NMR spectrum of the obtained oily product
contains signals at 47.3, 42.6, 41.51 ppm belonging to
N,N-bis[3-(diphenylphosphorothioyl)propyl]amine II,
cis- and trans-isomers of (4-methyltetrahydro-1H-
pyrrol-3-yl)methyl(diphenyl)phosphine sulfide (III),
and non-identified signals at 57.3 and 60.7 ppm (the
1
ratio of signals 25 : 8 : 2 : 1 : 1, respectively). The H
NMR spectrum, along with the signals characteristic of
diadduct (II), shows the signals belonging to the cis-
and trans-isomers of adduct III: 0.96 d (Me, 3JHН 7.0 Hz),
0.99 d (Me, 3JHН 6.7 Hz) in the ratio 4 : 1, respectively.
In the mass spectrum two peaks of molecular ions with
m/z 315 are present. The obtained oily product was
dissolved in dioxane (2 mL) and passed through Al2O3
Scheme 9.
60−65oC
X
VIII
− H2Se
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 9 2014

1746
VERKHOTUROVA et al.
layer (6 mm) (eluent dioxane). Dioxane was removed
under a reduced pressure, the residue was dried in a
vacuum. Yield 0.06 g (52%), oily light-yellow
3.7 Hz), 49.85 d (С2, 3JCP 15.6 Hz), 52.70 (С5), 126.51
(Cp), 128.24, 128.34, 128.37, 128.67 (Co, Cm), 140.56
3
d, 142.16 d (Сipso, JCP 13.9 and 16.9 Hz respectively).
31P NMR spectrum, δР, ppm: 49.4 (cis-isomer), 48.3
(trans-isomer). Found, %: C 70.88; Н 7.98; N 3.59; Р
8.12; S 8.45. С22Н30NPS. Calculated, %: s 71.12; Н
8.14; N 3.77; P 8.34; S 8.63.
1
compound. H NMR spectrum, δH, ppm: 1.73 m (4Н,
СН2СН2СН2), 2.49 m (4H, СН2Р), 2.59 t (4Н, СН2N,
3JHH 6.7 Hz), 7.42 m (12H, m-Ph, p-Ph), 7.81 m (8H,
3
о-Ph, JHP 13.0 Hz). 13С NMR spectrum, δC, ppm:
1
22.25 (СН2СН2СН2), 29.99 d (СН2Р, JСP 57.1 Hz),
(4-Methyltetrahydro-1H-pyrrol-3-yl)methyl(di-
phenethyl)phosphine selenide (VI). The solution of
bis(2-phenylethyl)phosphine selenide (V) (0.049 g,
0.15 mmol) and diallylamine (0.014 g, 0.15 mmol) in
1 mL of dioxane was placed in a quartz ampule,
flushed with argon and irradiated with UV light for
4 h. Dioxane was removed under reduced pressure, the
residue was dissolved in chloroform (2 mL) and passed
through Al2O3 layer (5 mm) (eluent chloroform,
20 mL). Chloroform was removed under a reduced
pressure, the residue was washed with diethyl ether
(3 × 2 mL), dried in a vacuum. Yield 0.02 g (32%,
purity 95 %), (cis- and trans-isomers in the ratio of
3
3
49.21 d (СН2N, JСP 16.8 Hz), 128.43 d (Сm, JСP
12.8 Hz), 130.85 d (Со, JСP 10.3 Hz), 131.25 (Сp),
2
132.53 d (Сipso, JСP 80.2 Hz). 31P NMR spectrum, δР,
1
ppm: 43.7. Found, %: s 67.38; Н 6.40; N 2.47; Р
11.28; S 11.77. С30Н33NР2S2. Calculated, %: C 67.52;
Н 6.23; N 2.62; Р 11.61; S 12.02.
(4-Methyltetrahydro-1H-pyrrol-3-yl)methyl(di-
phenethyl)phosphine sulfide (IV). The solution of bis-
(2-phenylethyl)phosphine sulfide (V) (0.114 g,
0.42 mmol) and diallylamine (0.041 g, 0.42 mmol) in
1 mL of dioxane was placed in a quartz ampule,
flushed with argon and irradiated with UV light for
7.5 h. Dioxane was removed under a reduced pressure,
the residue was dissolved in benzene (2 mL) and
passed through Al2O3 layer (5 mm) (eluent benzene,
then chloroform). From the chloroform solution the
solvent was removed under a reduced pressure, the
residue was dried in a vacuum. Yield 0.07 g (45%)
(cis- and trans-isomers in the ratio of 5 : 1), oily light-
1
4 : 1, oily light-yellow compound. H NMR spectrum,
3
δH, ppm (cis-isomer): 0.94 d (3Н, Ме, JHН 7.1 Hz),
1.93 m (2Н, PCH2Pyr), 2.24 m (4Н, PCH2), 2.44 m
5
(1Н, СН4), 2.32 m, 2.96 m (2Н, СН2 ), 2.51 m, 3.04 m
2
3
(2Н, СН2 ), 2.59 m, 3.04 m (1Н, СН2 ), 2.96 m (4Н,
CH2Ph), 7.20 m, 7.25 m (10Н, Ph). 1H NMR spectrum,
3
δ, ppm (trans-isomer): 1.02 d (3Н, Ме, JHН 6.6 Hz),
1
the rest of signals of the trans-isomer are masked by
the signals of the major cis-isomer. 13C NMR spectrum,
δ, ppm (cis-isomer): 13.41 (Me), 29.39 d (PhCH2, 2JCP
yellow compound. H NMR spectrum, δH, ppm (cis-
isomer): 0.80 d (3Н, Ме, 3JHН 7.1 Hz), 1.65 d.d.d, 1.82
2
2
3
d.d.d (2Н, PCH2Pyr, JHН' 15.0 Hz, JНP = JHН
=
1
3
2
3.0 Hz), 33.21 d, 33.28 d (PhCH2CH2, JCP 41.8 and
10.0 Hz, JH'Н 4.0 Hz, JH'P 12.3 Hz), 2.04 m (4Н,
PCH2), 2.21 m (1Н, СН4), 2.41 m (1Н, СН3), 2.59 d.d,
41.4 Hz respectively), 35.92 d (С3, 2JCP 9.9 Hz), 37.06
d (С4, JCP 2.2 Hz), 40.28 d (РCH2Pyr, JCP 57.8 Hz),
3
1
5
2
3
3.11 d.d (2Н, СН2 , JHН' 11.0 Hz, JH5Н4 4.4 Hz,
48.26 d (С2, JCP 4.3 Hz), 50.37 (С5), 126.74 (Cp),
3
2
2
3JH5' 4' 6.6 Hz), 2.71 d.d, 3.27 d.d (2Н, СН2 , JHН'
Н
128.30, 128.40, 128.50, 128.81 (Co Cm), 141.57 d,
141.74 d (Сipso, 3JCP 17.3 and 16.1 Hz ,respectively). 31P
NMR spectrum, δР, ppm: 37.7 (+ satellites, 1JPSe 706.5 Hz)
(cis-isomer), 36.3 (trans-isomer). 77Se NMR spectrum,
δSe, ppm (cis-isomer): –75.0 d (1JSeP 706.5 Hz).
3
3
10.7 Hz, JH2Н3 7.2 Hz, JH2' 3 8.8 Hz), 2.83 m (4Н,
Н
CH2Ph), 4.01 br.s (1Н, NH), 7.10 m, 7.19 m (10Н, Ph).
1H NMR spectrum, δH, ppm (trans-isomer): 0.94 d
(3Н, Ме, 3JHН 6.5 Hz), 1.65–1.82 m (1Н, СН4), the rest
of signals of the trans-isomer are masked by the
signals of the major cis-isomer. 13C NMR spectrum, δ,
ppm (cis-isomer): 14.11 (Me), 28.62 (PhCH2), 32.74 d
(РCH2Pyr, 1JCP 48.4 Hz), 33.39 d, 33.67 d (PhCH2CH2,
Diallylammonium diphenyldiselenophosphinate
(VIII). To the solution of diphenylphosphine selenide
(0.117 g, 0.44 mmol) and diallylamine (0.064 g,
0.66 mmol) in 3 mL of dioxane amorphous selenium
was added (0.035 g, 0.44 mmol). The mixture was
stirred at 60–65°С for 3.5 h, filtered, dioxane removed
under a reduced pressure, the residue was washed with
diethyl ether (3 × 2 mL), dried in a vacuum. Yield
0.13 g (67 %), powder of light pink color, mp. 89–92°С.
2
1JCP 48.0 and 48.3 Hz respectively), 36.46 d (С3, JCP
3
3
10.3 Hz), 37.13 d (С4, JCP 3.2 Hz), 50.77 d (С2, JCP
4.4 Hz), 52.83 (С5), 126.58 (Cp), 128.21, 128.25,
128.28, 128.71 (Co, Cm), 140.41 d, 140.43 d (Сipso, 3JCP
13.3 and 13.5 Hz respectively). 13C NMR spectrum, δ,
2
ppm (trans-isomer): 16.46 (Me), 28.54 d (PhCH2, JCP
1
3
1H NMR spectrum, δH, ppm: 3.58 d (4Н, СН2N, JHH
2.7 Hz), 33.35 d (РCH2Pyr, JCP 48.1 Hz), 33.70 d,
1
3
34.24 d (PhCH2CH2, JCP 49.7 and 47.7 Hz respec-
6.9 Hz), 5.28 br.d (2Нtrans, =CH2, JНН 17.1 Hz), 5.29
tively), 41.43 d (С3, JCP 12.5 Hz), 41.63 d (С4, JCP
2
3
3
br.d (2Нcis, =CH2, JНН 10.2 Hz), 5.81 d.d.t (2Н, =СН,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 9 2014

REACTION OF SECONDARY PHOSPHINE CHALCOGENIDES
1747
3
3
3JНН 10.2 Hz, JНН 17.1 Hz, JНН 6.9 Hz), 7.23 m (6H,
m-Ph, p-Ph), 8.10 m (4H, o-Ph). 13С NMR spectrum,
δC, ppm: 48.25 (СН2N), 123.95 (=CH2), 128.29 d (Сm,
Tetrahedron Lett., 2003. vol. 44, p. 479.
3. Jessop, C.M., Parsons, A.F., Routledge, A., and Irvine, D.J.,
Eur. J. Org. Chem., 2006, no. 6, p. 1547.
3JСР 12.1 Hz), 129.03 (=СН), 130.49 d (Сp, JСР 1.7
4
4. Oparina, L.A., Gusarova, N.K., Vysotskaya, O.V.,
Artem’ev, A.V., Kolyvanov, N.A., and Trofimov, B.A.,
Synthesis, 2014, no. 46, p. 653.
5. Trofimov, B.A., Malysheva, S.F., Belogorlova, N.A.,
Kuimov, V.A., Albanov, A.I., and Gusarova, N.K., Eur.
J. Org. Chem., 2009, p. 3427.
6. Trofimov, B.A., Gusarova, N.K., Malysheva, S.F.,
Sukhov, B.G., Belogorlova, N.A., Kuimov, V.A., and
Al’pert, M.L., Sulfur Lett., 2003, vol. 26, no. 2, p. 63.
7. Gusarova, N.K., Volkov, P.A., Ivanova, N.I., Cher-
nysheva, N.A., Yas’ko, S.V., Albanov, A.I., and Tro-
fimov, B.A., Russ. J. Gen. Chem., 2010, vol. 80, no. 8,
p. 1602.
8. Gusarova, N.K., Chernysheva, N.A., Yas’ko, S.V.,
Klyba, L.V., and Trofimov, B.A., Russ. J. Gen. Chem.,
2011, vol. 81, no. 12, p. 2506.
Hz), 131.88 d (Со, JСР 12.1 Hz), 140.76 d (Сipso, JСР
78.0 Hz). 31P NMR spectrum, δР, ppm: 22.7
(+ satellites, 1JPSe 586 Hz). Found, %: s 48.72; Н 4.98;
N 3.06; Р 6.76; Se 35.52. С18Н22NРSe2. Calculated, %:
C 48.99; Н 5.03; N 3.17; Р 7.02; Se 35.79.
2
1
Amide of N,N-diallyl(diphenyl)selenophosphinic
acid (X). The solution of diphenylphosphine selenide
(0.093 g, 0.35 mmol) and diallylamine (0.034 g,
0.35 mmol) in 2 mL of dioxane was flushed with argon
and stirred at 60–65°С for 3 h. The 31P NMR spectrum
of the reaction mixture contains the signals at –40.0
(1JPH 210 Hz), 22.4 (satellites, JPSe 586 Hz) and
1
1
69.4 ppm (satellites: JPSe 754.8 Hz) from diphenyl-
9. Gusarova, N.K., Chernysheva, N.A., Klyba, L.V.,
Shagun, V.A., Yas’ko, S.V., Smirnov, V.I., and Tro-
fimov, B.A., J. Organomet. Chem., 2013, vols. 745–
746, p. 126.
phosphine VII, diselenophosphinate VIII, and amide
X, and a non-identified signal at 53.0 ppm (the ratio of
signals 1 : 2 : 2 : 1 respectively). Dioxane was removed
under a reduced pressure, the residue was dissolved in
benzene, the solution was passed through Al2O3 layer
(1 cm) (eluent benzene). Benzene was removed under
a reduced pressure, the residue was dried in a vacuum.
10. Gusarova, N.K., Kuimov, V.A., Malysheva, S.F.,
Belogorlova, N.A., Albanov, A.I., and Trofimov, B.A.,
Tetrahedron, 2012, vol. 68, p. 9218.
11. Smith, D.C., Lake, C.H., and Gray, G.M., Dalton
Trans., 2003, p. 2950.
1
Yield 0.03 g (24%), light-yellow waxy product. H
NMR spectrum, δH, ppm: 3.55 d.d (4Н, СН2N, 3JHН 6.5 Hz,
12. Owens, S.B., Smith, D.C., Lake, C.H., and Gray, G.M.,
Eur. J. Inorg. Chem., 2008, p. 4710.
3JHР 11.7 Hz), 5.06 d.d.t (2Нtrans, =CH2, JНН 17.0 Hz,
3
2JНН 1.3 Hz, 4JНН 1.2 Hz), 5.12 br.d (2Hcis, =CH2, 3JНН
=
13. Owens, S.B. and Gray, G.M., Organometallics, 2008,
vol. 27, p. 4282.
10.2 Hz), 5.83 d.d.t (2Н, =CH, 3JНН 17.0 Hz, 3JНН 10.2 Hz,
3JHH 6.5 Hz), 7.43 m (6H, m-Ph, p-Ph), 8.00 m (4Н, o-
Ph). 13С NMR spectrum, δC, ppm: 49.74 (СН2N),
14. Trofimov, B.A., Artem’ev, A.V., Gusarova, N.K., Maly-
sheva, S.F., Fedorov, S.V., Kazheva, O.N., Alexan-
drov, G.G., and Dyachenko, O.A., Synthesis, 2009,
no. 19, p. 3332.
118.58 (=CH2), 128.41 d (Сm, JСР 13.4 Hz), 131.82 d
3
(=СН, JСР 2.6 Hz), 132.52 d (Со, JСР 11.2 Hz),
3
2
15. Trofimov, B.A., Artem’ev, A.V., Malysheva, S.F., and
Gusarova, N.K., Dokl. Chem., 2009, vol. 428, no. 1,
p. 225.
16. Gusarova, N.K., Verkhoturova, S.I., Kazantseva, T.I.,
Arbuzova, S.N., Albanov, A.I., and Trofimov, B.A.,
Mendeleev Commun., 2013, vol. 23, no. 5, p. 253.
17. Trofimov, B.A., Gusarova, N.K., Chernysheva, N.A.,
Yas’ko, S.V., Kazantseva, T.I., and Ushakov, I.A.,
Synthesis, 2008, no. 17, p. 2743.
18. Gusarova, N.K., Kuimov, V.A., Malysheva, S.F.,
Belogorlova, N.A, Albanov, A.I., and Trofimov, B.A.,
Tetrahedron, 2012, vol. 68, p. 9218.
19. Gusarova, N.K., Verkhoturova, S.I., Kazantseva, T.I.,
Arbuzova, S.N., Albanov, A.I., Tatarinova, А.А., and
Trofimov, B.A., Russ. J. Gen. Chem., 2013, vol. 83,
no. 10, p. 1895.
132.86 d (Сipso, JСР 114.7 Hz), 133.97 d (Сp, JСР 6.0
Hz). 31P NMR spectrum, δР, ppm: 69.3 (+ satellites,
1JPSe 754.8 Hz). 77Se NMR spectrum, δSe, ppm: –267.5
d (1JSeP 754.8 Hz). Found, %: s 59.86; Н 5.42; N 3.67;
Р 8.43; Se 21.78. С18Н20NРSe. Calculated, %: C 60.00;
Н 5.60; N 3.89; Р 8.60; Se 21.92.
1
4
ACKNOWLEDGMENTS
This work was performed with the financial support
from the Grant of the President of the Russian
Federation for the State support of leading scientific
schools No. NSh-156.2014.3.
REFERENCES
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2. Jessop, C.M., Parsons, A.F., Routledge, A., and Irvine, D.J.,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 9 2014