Reaction of divinyl selenide with secondary phosphine chalcogenides

Article abstract of DOI:10.1134/S1070363210080104

Under the conditions of free-radical initiation (AIBN, UV irradiation), divinyl selenide regioselectively reacts with secondary phosphine sulfides and phosphine selenides to afford, depending on the ratio of the reagents, mono- or diadducts mainly of the

Full text of DOI:10.1134/S1070363210080104

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 8, pp. 1602–1608. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © N.K. Gusarova, P.А. Volkov, N.I. Ivanova, N.А. Chernysheva, S.V. Yas'ko, A.I. Albanov, B.А. Trofimov , 2010, published in Zhurnal
Obshchei Khimii, 2010, Vol. 80, No. 8, pp. 1292–1297.
Reaction of Divinyl Selenide
with Secondary Phosphine Chalcogenides
N. K. Gusarova, P. А. Volkov, N. I. Ivanova, N. А. Chernysheva,
S. V. Yas'ko, A. I. Albanov, and B. А. Trofimov
Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: gusarova@irioch.irk.ru
Received January 12, 2010
Abstract—Under the conditions of free-radical initiation (AIBN, UV irradiation), divinyl selenide
regioselectively reacts with secondary phosphine sulfides and phosphine selenides to afford, depending on the
ratio of the reagents, mono- or diadducts mainly of the anti-Markownikoff structure. The conditions which
allow obtaining the diadducts in up to 97% yield are found. By the example of 2-{[2-(diphenethyl-
phosphoroselenoyl)ethyl]selanyl}ethyl(diphenethyl)phosphine selenide the diadducts were shown to react with
aqueous hydrogen peroxide at 53–56оС to give vinyl(diphenethyl)phosphine oxide in 76% yield.
DOI: 10.1134/S1070363210080104
Divinyl selenide is readily available from acetylene
and elemental selenium [1–3] and is a promising
precursor for the organic and organoelemental
synthesis. At the same time, its synthetic potential is
far from being fully realized. Divinyl selenide was
reported to react with thiols under the conditions of
free-radical initiation to form anti-Markownikoff
adducts [4]. Its reaction with selenium dichloride or
dibromide leads to new functional five-membered
selenium-containing heterocycles, 2,6-dichloro(bromo)-
1,4-diselenanes [5]. Thermal heterocyclization of di-
vinyl selenide in the gas phase results in selenophene
[6].
reaction could lead to new Se,P-containing com-
pounds, which are promising polydentate ligands [7–
10] and precursors for the design of biologically active
compounds [11, 12].
With this aim, in the present work we have ex-
amined the reaction of divinyl selenide with available
secondary phosphine chalcogenides [13–15].
It turned out that in the presence of free-radical
initiator (AIBN, 60–75оС) divinyl selenide region-
selectively reacted with two equivalents of secondary
phosphine sulfides (Iа, Ib) or phosphine selenides (Ic,
Id) to form the corresponding diadducts of the anti-
Markownikoff structure (IIа–IId), as a rule, in a high
yield (88–97%).
There are no data in the literature on the reaction of
divinyl selenide with PH-addends, although such a
X
AIBN, 60_75oC
Se
(1)
R2P
X
PR2
Se
+ 2R2P
H
X
Ia_Id
IIa_IId
R = Ph, X = S (a); R = Ph(CH2)2, X = S (b); R = Ph(CH2)2, X = Se (c); R = 2-Py(CH2)2, X = Se (d).
The reaction was monitored by 31P NMR spectro-
scopy by the disappearance of the signals of the initial
secondary phosphine chalcogenides Ia–Id at 2–22 ppm
and appearance of the signals of the formed tertiary
phosphine chalcogenides IIa–IId at 38–49 ppm.
The reaction of diphenylphosphine sulfide Iа with
divinyl selenide proceeds practically quantitatively
under mild conditions (60–65оС, 5 h, AIBN, THF) in
95% yield of diadduct IIа. Diadducts IIb, IIc were
also prepared in high yield (97 and 88%) by heating
1602

REACTION OF DIVINYL SELENIDE
1603
(75оС, 15–16 h, AIBN, dioxane) of bis(2-phenethyl)-
phosphine sulfide Ib or bis(2-phenethyl)phosphine
selenide Ic with divinyl selenide. Under the same
conditions bis[2-(2-pyridyl)ethyl]phosphine selenide
Id is completely converted after 50 h; note that, along
with diadduct IId, monoadduct IIId and another two
unidentified organophosphorus compounds are present
in the reaction mixture (the content of the di- to
monoadduct, from the 31P NMR spectrum, is 54 and
27%). Diadduct IIc was isolated in 27% preparative
yield. The lower reactivity of secondary bis
(pyridylethyl)phosphine chalcogenides as compared to
that of their phenylethyl analogs in the free-radical
processes was reported earlier by the example of the
addition of these PH-addends to 2-[(vinyloxy)methyl]
tetrahydrofuran [16] or aromatic acetylenes [17]. The
free-radical addition of thiols to vinylpyridine is also
known to proceed less actively than to styrene [18].
The use of equimolar amounts of the secondary
phosphine chalcogenides Ia, Ic, Id and divinyl
selenide allows to shift the reaction towards
predominant formation of the corresponding
monoadducts IIIа, IIIc, IIId, although the percentage
of diadducts IIа, IIc, IId in the mixture remains high
(from the 31P NMR, up to 39%). The reaction was
performed either by the UV irradiation (40оС) or in the
presence of AIBN (75оС).
X
UV or AIBN
PR2
Se
+
R2P
+ IIa, IIc, IId
Se
(2)
X
H
Ia, Ic, Id
IIIa, IIIc, IIId
R = Ph, X = S (a); R = Ph(CH2)2, X = Se (c); R = 2-Py(CH2)2, X = Se (d).
The best results were obtained by the 1 h UV
irradiation of the reaction of diphenylphosphine sulfide
Iа with divinyl selenide in dioxane. Under these
conditions, diphenyl[2-(vinylselanyl)ethyl]phosphine
sulfide IIIa and diadduct IIа are formed in the ratio of
83 : 17. The isolated yield of the monoadduct IIIa was
69%.
spectra of the reaction mixtures obtained with those of
individual diadducts IIc, IId.
By the example of bis(2-phenethyl)phosphine oxide
it was shown that secondary phosphine oxides, unlike
the secondary phosphine sulfides or -selenides, do not
add to divinyl selenide under the conditions of reaction
(1) (AIBN, 75оС, 16 h, dioxane). This is consistent
with the known data on low reactivity of secondary
phosphine oxides in free-radical processes [19–21].
However, 2-{[2-(diphenethylphosphoryl)ethyl]selanyl}-
ethyl(diphenethyl)phosphine oxide (IV) was prepared
in 84% yield under mild conditions (room temperature,
15 min) by oxidation of diphosphine selenide IIc with
two equivalents of hydrogen peroxide in aqueous
acetone.
When secondary phosphine selenides Ic, Id are
used in reaction (2) either under the UV irradiation or
in the presence of AIBN, mixtures of the mono- and
diadducts are formed, in which the percentage of the
latter products increases to 39%. We failed to isolate
individual monoadducts IIIc, IIId in these ex-
periments but their formation was unequivocally
1
proved by comparing the H, 13C, 31P, 77Se NMR
O
O
H2O2/H2O/Me2C=O
IIс
P
P
(3)
23oC, 15 min
Se
IV
Unexpectedly, treatment of diphosphine selenide
IIc with substantial (~10–12-fold) molar excess of
hydrogen peroxide in aqueous acetone upon heating to
53–56оС for 4.5 h gave vinyl(diphenethyl)phosphine
oxide (V) in 76% yield.
1Н and 31Р NMR spectra of compound V are
identical to those described in the literature [22].
Apparently, the reaction proceeds via the initial
oxidation of phosphine selenide IIc to phosphine oxide
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 8 2010

1604
GUSAROVA et al.
precipitation of elemental selenium. Further heating of
phosphine oxide IV in the system Н2О2–Н2О,
apparently leads to the corresponding unstable
selenoxide VI, which suffers fragmentation typical for
dialkylselenoxides [23] with the formation of two
molecules of vinyl phosphine oxide V. Formally, this
should result in the formation of hypothetical
selenaoxoselane (H2Se=O), which, probably, is
oxidized to inorganic selenium acids by the excess of
hydrogen peroxide (up to selenic acid).
O
H2O2/H2O/Me2C=O
53_56oC, 4.5 h
(4)
2
IIс
P
V
IV (the latter was identified in the reaction mixture by
the 31Р NMR in the initial stage of the reaction) with
O
O
H2O2/H2O
_Se
H2O2/H2O
53_56oC
H2O2/H2O
_[H2SeO4]
IIc
(5)
IV
2V
P
P
Se
O
VI
The synthesized diadducts II are expedient
precursors for synthesis of the corresponding
diphosphines, which are promising polydentate
“chemolabile” ligands for the design of metal complex
catalysts. Thus, diphosphine sulfide IIb upon reflux
with sodium metal in toluene is practically
quantitatively reduced to bis[2-(diphenethylphosphino)
ethyl]selenide (VII).
(6)
Na/toluene
IIb
P
P
_Na2S
Se
VII
Therefore, based on the reaction of free-radical
addition of secondary phosphine sulfides and
phosphine selenides to divinyl selenide an expedient,
effective, atom-economic method is elaborated for the
synthesis of the earlier unknown functional tertiary
diphosphine sulfides and diphosphine selenides with
diethylselenide functional group, which are reactive
building blocks, for example, for the synthesis of the
corresponding functional diphosphines, diphosphine
oxides or vinyl diorganyl phosphine oxides.
161.98, 76.31 MHz, respectively) in CDCl3, chemical
shifts are given with respect to HMDS (1Н, 13С),
H3PO4 (31P), Me2Se (77Se). IR spectra were recorded
on a Bruker IFS 25 spectrometer in thin layer or in
KBr pellets. Electron impact mass spectra were
recorded on
a
GCMS-QP5050A SHIMADZU
instrument at 70 eV. All experiments were run in argon
atmosphere and monitored by 31P NMR spectroscopy.
Synthesis of diadducts IIa–IIc (general proce-
dure). The mixture of phosphine chalcogenide Ia–Ic
(1.0 mmol), divinyl selenide (0.5 mmol) and AIBN
(2 wt %) in 3 ml of the solvent (THF for phosphine
sulfide Iа, dioxane for phosphine chalcogenides Ib, Ic)
were blown with argon, hermetically sealed and stirred
EXPERIMENTAL
1Н, 13C, 31Р, 77Se NMR spectra were registered on a
Bruker DPX 400 spectrometer (400.13, 101.62,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 8 2010

REACTION OF DIVINYL SELENIDE
1605
1
on a magnetic stirrer at heating (for phosphine sulfide
Iа at 60–65оС, for phosphine chalcogenides Ib, Ic at
75оС). The time of the reaction for phosphine sulfides
Ia, Ib was 5 and 15 h, respectively, for phosphine
selenide Ic, 16 h. After the reaction completed the
solvent was removed under reduced pressure, the
residue was washed with ether (0.3 ml×3), ether was
decanted, the residue was dried at 1 mm Hg to afford
diadducts IIa–IIc.
32.21 d (CH2P, JPC 40.3 Hz), 126.34 (Cp), 127.98,
128.42 (Co,m), 139.78 d (Ci, JPC 13.6 Hz). 31Р NMR
3
spectrum, δP, ppm: 38.58. 77Se NMR spectrum, δSe,
1
ppm: –386.72 d (P=Se, JP–Se 702.5 Hz), 251.77
(CH2Se). IR (KBr, cm–1): 3084, 3061, 3026, 3001 ν
(=CH of the phenyl ring); 2924, 2854 ν(CH); 1602,
1583, 1496 ν(C=C of the phenyl ring); 1454, 1404
δ(CH2); sh 1269, 1254, 1214, 1178, 1120, 1082, 1029,
1006, 949, 910, 888, 873 δ(CH of the phenyl ring); br.
s 753 ν(P–C); 698 δ(CH of the phenyl ring); sh 572,
575 ν(P=Sе). Found, %: C 56.01; H 5.69; P 7.84; Se
30.46. С36H44P2Se3. Calculated, %: C 55.75; H 5.72; P
7.99; Se 30.54.
2-{[2-(Diphenylphosphorothioyl)ethyl]selanyl}-
ethyl(diphenyl)phosphine sulfide (IIа). Yield 0.27 g
(95%), white powder, mp 146–148oC. 1Н NMR
spectrum, δH, ppm: 2.78 m (8H, PCH2CH2Se), 7.67 m
(20H, Ph). 13С NMR spectrum, δC, ppm: 14.62 d
(CH2Se, 2JPC 3.0 Hz), 33.91 d (CH2P, 1JPC 49.8 Hz),
Synthesis of 2-[(2-{bis[2-(2-pyridinyl)ethyl]phos-
phoroselenoyl}ethyl)selanyl]ethyl{bis-[2-(2-pyridi-
nyl)ethyl]}phosphine selenide (IId). A mixture of
phosphine selenide Id (0.84 mmol, 0.272 g), divinyl
selenide (0.42 mmol, 0.056 g), and AIBN (0.0066 g,
2 wt %) in 4 ml of dioxane was blown with argon,
hermetically sealed and stirred on a magnetic stirrer at
75оС for 50 h. After that time the reaction mixture
contained, according to the 31P NMR spectrum,
monoadduct IIId [40.24 ppm (27%)], diadduct IId
[40.37 ppm (54%)], and two unidentified compounds
[40.04 ppm (5.6%) and 82.18 ppm (13.4%)]. The
reaction mixture was allowed to stay overnight at room
temperature; white precipitate was formed, from which
the solution was separated by decantation. The solution
was evaporated at 1 mm Hg, the residue was washed
with cold hexane (0.2 ml×3) and ether (0.3 ml×8), the
solvent was removed by decantation, the residue was
dried at 1 mm Hg to afford diadduct IId as a viscous
oil. Yield 0.088 g (27%). 1Н NMR spectrum, δH, ppm:
2.14 m (4H, PCH2), 2.75 m (4H, CH2Se), 2.46 m (8H,
CH2P), 3.08 m (8H, PyCH2), 7.08 m (4H, H5–Py), 7.17
m (4H, H3–Py), 7.54 m (4H, H4–Py), 8.45 br. d (4H,
H6–Py). 13С NMR spectrum, δC1, ppm: 16.10 d (CH2Se,
2JPC 3.2 Hz), 26.6 d (PyCH2, JPC 34.7 Hz), 34.50 d
3
128.90 d (Со, 2JPC 12.2 Hz), 131.20 d (Сm , JPC 10.3
Hz), 131.70 d (Ср, 4JPC 3.0 Hz). 31Р NMR spectrum, δP,
ppm: 42.50. IR (KBr, cm–1): 3052 ν(=CH); 2926, 2892
ν(CH); 1478 ν(C=C, phenyl ring); 1464, 1430 δ(CH2);
1317, 1268, 1172, 1103, 1011, 920, 874, sh 778 δ(CH,
phenyl ring); 751 ν(P–C); 737, 719, 699 δ(CH, phenyl
ring); sh 620, 607 ν(P=S). Found, %: C 59.49; H 5.05;
P 10.96; S 10.61; Se 13.89. С28H28P2S2Se. Calculated,
%: C 59.05; H 4.96; P 10.88; S 11.26; Se 13.86.
2-{[2-(Diphenethylphosphorothioyl)ethyl]selanyl}-
ethyl(diphenethyl)phosphine sulfide (IIb). Yield
0.30 g (88%), viscous oil. 1Н NMR spectrum, δH, ppm:
2.20 m (12H, CH2PCH2), 2.82 m (4H, CH2Se), 2.94 m
(8H, PhCH2), 7.23 m (20H, Рh). 13С NMR spectrum,
δC, ppm: 15.22 d (CH2Se, 2JPC 3.7 Hz), 28.55 (PhCH2),
1
1
32.10 d (PCH2, JPC 44.0 Hz), 32.95 d (CH2P, JPC
47.7 Hz), 126.62 (Cp), 128.24, 128.73 (Co,m), 140.32 d
(Ci, 3JPC 13.6 Hz). 31Р NMR spectrum, δP, ppm: 49.44.
77Se NMR spectrum, δSe, ppm: 249.38 (CH2Se). IR
(KBr, cm–1): 3084, 3061, 3026, 3001 ν(=CH of the
phenyl ring); 2925, 2854 ν(CH); 1602, 1583, 1496
ν(C=C of the phenyl ring); 1453, 1405 δ(CH2); 1254,
1214, 1179, 1121, 1081, 1047, 1029, 1006, 949, 910,
sh 888, 873, sh 832, sh 808 δ(CH of the phenyl ring);
br.s 750 ν(P–C); 698 δ(CH of the phenyl ring); sh 612,
596 ν(P=S). Found, %: C 63.46; H 6.59; P 8.96; S
9.48; Se 11.51. С36H44P2S2Se. Calculated, %: C 63.42;
H 6.50; P 9.09; S 9.41; Se 11.58.
(CH2P, JPC 60.3 Hz), 31.43 (PyCH2), 121.82 (C5–Py),
1
123.28 (C3–Py), 138.17 (C4–Py), 147.60 (C6–Py),
160.07 d (C2–Py, JPC 14.8 Hz). 31Р NMR spectrum,
3
δP, ppm: 39.50. 77Se NMR spectrum, δSe, ppm: -390.64
d (P=Se, 1JP-Se 700.4 Hz), 253.2 (CH2Se). Found, %: C
49.63; H 5.36; N 7.23; P 7.63; Se 30.15.
С32H40N4P2Se3. Calculated, %: C 49.31; H 5.17; N
7.19; P 7.95; Se 30.39.
2-{[2-(Diphenethylphosphoroselenoyl)ethyl]
selanyl}-ethyl(diphenethyl)phosphine selenide.
1
(IIc). Yield 0.376 g (97%), viscous oil. Н NMR
spectrum, δH, ppm: 2.32 m (12H, CH2PCH2), 2.85 m
(8H, PhCH2), 2.97 m (4H, CH2Se), 7.27 m (20H, Рh).
Synthesis of monoadducts IIIa, IIIc, IIId.
а. Diphenyl[2-(vinylselanyl)ethyl]phosphine sulfide (IIIa).
A mixture of diphenylphosphine sulfide (0.824 mmol,
0.18 g) and divinyl selenide (0.824 mmol, 0.11 g) in
2
13С NMR spectrum, δC, ppm: 15.70 d (CH2Se, JPC
2.8 Hz), 29.00 (PhCH2), 31.32 d (PCH2, 1JPC 36.3 Hz),
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1606
GUSAROVA et al.
7 ml of dioxane was placed in a quartz ampule blown
with argon, irradiated with UV light for 1 h, and
analyzed by 31Р NMR spectroscopy. Two signals are
present in the spectrum: 42.03 and 41.91 ppm in the
ratio of 83 : 17, assigned, respectively, to the mono-
and diadducts IIIа and IIа. The solvent was removed
under reduced pressure, the residue was dried in a
vacuum and dissolved in cold ether. Upon staying, a
white powder of diadduct IIa precipitated from the
solution, (0.06 g, 13%). The ether solution was
decanted, concentrated under reduced pressure and
filtered through thin (5 mm) layer of Al2O3. The
solvent was evaporated, the residue was dried at 1 mm
Hg to obtain 0.20 g (69%) of monoadduct IIIa as a
16.9 Hz), 6.60 d. d (1Н, СН=), 7.28 m (20H, Рh). 13С
2
NMR spectrum, δC, ppm: 16.94 d (CH2Se, JPC 3.2
1
Hz), 29.0 (PhCH2), 31.09 d (PCH2, JPC 37.6 Hz),
1
32.16 d (CH2P, JPC 40.3 Hz), 118.24 (CH2=), 125.13
(CH=), 125.99 (Cp), 127.73, 128.25 (Co,m), 140.61,
3
140.46 d (Ci, JPC 12.4 Hz). 31Р NMR spectrum, δP,
ppm: 38.09. 77Se NMR, δSe, ppm: –387.44 d (P=Se,
1JP-Se 703.2 Hz), 311.15 (SeCH=CH2).
Bis[2-(2-pyridinyl)ethyl]2-(vinylselanyl)ethyl-
1
phoaphine selenide (IIId). Н NMR spectrum, δH,
ppm: 2.24 m (4H, PCH2), 2.45 m (4H, CH2Р), 2.85 d.t
3
3
(2H, CH2Se, JНН 8.4 Hz, JPН 8.3 Hz), 3.10 m (4Н,
3
3
PyCH2), 5.44, 5.66 d (1H, CH2=, Jcis 9.8 Hz, Jtrans
17.2 Hz), 6.55 d. d (1Н, СН=), 7.08 m (2H, H5–Py),
7.17 m (2H, H3–Py), 7.55 m (2H, H4–Py), 8.45 br. d
1
dark-yellow oil. Н NMR spectrum, δH, ppm: 2.88 m
3
(4Н, PCH2CH2Se), 5.42 d (1H, =CH2, JHH 16.7 Hz),
3
(2H, H6–Py, JНН 3.3 Hz). 13С NMR spectrum, δC,
3
5.71 d (1H, =CH2, JHH 9.6 Hz), 6.62 d. d (1Н, CH=),
2
ppm: 17.28 d (CH2Se, JPC 3.2 Hz), 29.84 d (CH2P,
7.52 (6Н, Ph), 7.87 (4Н, Ph). 13С NMR spectrum, δC,
1JPC 42.0 Hz), 31.96 d (PCH2, JPC 38.0 Hz), 31.47
1
2
ppm: 16.28 d (CH2Se, JPC 2.0 Hz), 33.99 d (CH2P,
(PyCH2), 118.69 (CH2=), 125.42 (CH=), 121.84 (C5–
Py), 123.30 (C3–Py), 136.77 (C4–Py), 149.34 (C6–Py),
1JPC 49.3 Hz), 118.13 (=CH2), 125.42 (CH=), 128.9 d
(Со, 2JPC 12.1 Hz), 131.1 d (Сm, 3JPC 10.4 Hz), 131.8 d
(Ср, 4JPC 2.0 Hz), 132.2 d (Сi,1JPC 74.5 Hz). 31Р NMR
spectrum, δP, ppm: 41.90. Mass spectrum, m/z (I, % for
80Se): 352 [М]+• (6), 325 [М – C2H3]+ (14), 293 [M –
C2H3–S]+ (4), 245 [M – C2H3Se]+ (7), 218 [Ph2PHS]+•
(8), 217 [Ph2PS]+ (7), 185 [Ph2P]+ (7), 183 [C12H8P]+
(11), 140 [PhPS]+• (4), 139 [C6H4PS]+ (8), 107 [C2H3Se]
+ (7), 91 [C7H7]+ (1), 77 [C6H5]+ (3), 63 [P=S]+• (2).
159.44 d (C2–Py, JPC 13.6 Hz). 31Р NMR spectrum,
3
77
δP, ppm: 39.40. ЯМР Se, δ, ppm: –392.87 d (P=Se,
1JPSe 702.0 Hz); 312.53 (SeСН=CH2).
2-{[2-(Diphenethylphosphoryl)ethyl]selanyl}-
ethyl(diphenethyl)phosphine oxide (IV). To the
solution of 0.25 g (0.32 mmol) phosphine selenide IIc
in 3 ml of acetone 0.062 g (0.64 mmol) of 35%
hydrogen peroxide was added and stirred for 15 min.
The precipitated elemental selenium was filtered off,
washed successively with water (1 ml×3), acetone
(0.5 ml×2). The filtrate and waste waters were
combined, extracted with chloroform (5 ml×3), dried
over K2СО3. The solvent was removed under reduced
pressure to obtain 0.184 g (88.5%) of the crude
product, which was washed with ether (0.3 ml×5),
ether was decanted, the residue was dried at 1 mm Hg
to afford 2-{[2-(diphenethylphosphoryl)ethyl]selanyl}-
ethyl(diphenethyl)phosphine oxide (IV). Yield 0.175 g
(84%), white powder, mp 124–126оС. 1Н NMR
spectrum, δH, ppm: 2.07 m (12H, CH2PCH2), 2.82 m
(4H, CH2Se), 2.92 m (8H, PhCH2), 7.24 m (20H, Рh).
b. Reaction of divinyl selenide with phosphine
selenides Ic, Id, 1 : 1 molar ratio of the reagents
(general procedure). A mixture of phosphine selenide
Ic, Id (0.5 mmol), divinyl selenide (0.5 mmol), and
AIBN (2 % mass) in 3 ml of dioxane was blown with
argon, hermetically sealed, and stirred at 75оС for 15 h
for phosphine selenide Ic and 50 h for phosphine
selenide Id. The solvent was removed under reduced
pressure, the residue was washed with small portions
of hexane (0.3 ml×3), the solvent was decanted, the
residue was dried in a vacuum to afford the mixture of
the mono- and diadducts IIIc and IIc in the ratio of
61 : 39, IIId and IId in the ratio of 62 : 38 (according
1
to 31P NMR spectrum). The H, 13C, 31P, 77Se NMR
1
13С NMR spectrum, δC, ppm: 14.58 d (CH2Se, JPC
spectral characteristics for monoadducts IIIc, IIId
were obtained by comparative analysis of the spectra
of mixtures of the mono- and diadducts with similar
spectra of individual diadducts IIc, IId.
2.1 Hz), 27.66 (PhCH2), 29.62 (PhCH2), 29.76 d
1
1
(PCH2, JPC 57.9 Hz), 30.19 d (CH2P, JPC 61.8 Hz),
3
126.64 (Cp), 128.07, 128.79 (Co,m), 140.51 d (Ci, JPC
12.9 Hz). 31Р NMR spectrum, δP, ppm: 46.08. IR (KBr,
cm–1): 3085, 3060, 3026, 3001 ν(=CH of the phenyl
ring); 2928, 2904, 2866 ν(CH); 1602, 1583, 1496
ν(C=C of the phenyl ring); 1453, 1414 δ(CH2); 1267,
sh 1254, 1215 δ(CH of the phenyl ring); 1162 ν(P=O);
Diphenethyl[2-(vinylselanyl)ethyl]phosphine
1
selenide (IIIc). Н NMR spectrum, δH, ppm: 2.32 m
(12H, CH2PCH2), 2.85 m (8H, PhCH2), 2.97 m (4H,
3
3
CH2Se), 5.53, 5.77 d (1H, CH2=, Jcis 9.7 Hz, Jtrans
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REACTION OF DIVINYL SELENIDE
1607
1083, 1069, 1029, 1010, 941, 906, 831 δ(CH of the
phenyl ring); br.s 775, 749 ν(P–C); 698 δ(CH of the
phenyl ring). Found, %: C 66.62; H 6.79; P 9.33; Se
12.28. С36H44О2P2Se. Calculated, %: C 66.56; H 6.83;
P 9.54; Se 12.15.
(12Н, PhCH2, CH2Se), 6.89 m (10Н, Ph). 31P NMR
spectrum, δР, ppm: –22.6.
ACKNOWLEDGMENTS
This work was supported by the Russian Founda-
tion for Basic Research (grant no. 07-03-00562).
Vinyl(diphenethyl)phosphine oxide (V). To the
solution of 0.247 g (0.318 mmol) of 2-{[2-(di-
phenethylphosphoroselenoyl)ethyl]selanyl}ethyl(di-
phenethyl)phosphine selenide (IIc) in 3.5 ml of
acetone 0.368 g (3.82 mmol) of 35% hydrogen
peroxide was added at room temperature. The mixture
self-heated to 43оС and after 3–4 min the precipitation
of elemental selenium started. The reaction mixture
was stirred with a magnetic stirrer at 53–56оС for 4.5 h
and analyzed by 31Р NMR spectroscopy for the
disappearance of the signal of the starting phosphine
selenide IIc and appearance of the signal corres-
ponding to vinyl(diphenethyl)phosphine oxide (V)
(identified in the reaction mixture with the authentic
sample) [22]. Besides, the signal corresponding to the
intermediate phosphine oxide IV was observed in the
spectra. After the reaction completed, the precipitate
was filtered off, washed successively with water,
(1 ml×3), acetone (0.5 ml×2) and dried in a vacuum to
obtain 0.05 g of elemental selenium. The filtrate and
waste waters were combined, aqueous K2CO3 was
added to pH = 8, extracted with chloroform (7 ml×5),
and dried over calcined K2CO3. Chloroform was
removed under reduced pressure, the residue was dried
at 1 mm Hg to give 0.148 g (82.0%) of the crude
product, which was filtered through thin (5 mm) layer
of Al2O3, solvent was removed, the residue was dried
in a vacuum to obtain vinyl(diphenethyl)-phosphine
oxide (V). Yield 0.137 g (76.0%), colorless crystals,
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