Superbase-assisted addition of phosphine to 1-methoxy-4-vinylbenzene: Toward a rare family of organic phosphines

Article abstract of DOI:10.1080/00397911.2010.542864

Phosphine reacts with 1-methoxy-4-vinylbenzene in the superbase suspension KOH-dimethylsulfoxide (70-100 °C, atmospheric pressure) to form regiospecifically anti- Markovnikov adducts, bis[2-(4-methoxyphenyl)ethyl] phosphine (1) and tris[2-(4-methoxyphenyl

Full text of DOI:10.1080/00397911.2010.542864

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Superbase-Assisted Addition of
Phosphine to 1-Methoxy-4-vinylbenzene:
Toward a Rare Family of Organic
Phosphines
S. F. Malysheva a , N. K. Gusarova a , A. V. Artem'ev a , N. A.
Belogorlova a , V. I. Smirnov a , V. A. Shagun a , V. A. Kuimov a & B.
A. Trofimov a
a A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the
Russian Academy of Sciences, Irkutsk, Russian Federation
Accepted author version posted online: 17 Nov 2011.Version of
record first published: 03 Feb 2012.
To cite this article: S. F. Malysheva , N. K. Gusarova , A. V. Artem'ev , N. A. Belogorlova , V. I.
Smirnov , V. A. Shagun , V. A. Kuimov & B. A. Trofimov (2012): Superbase-Assisted Addition of
Phosphine to 1-Methoxy-4-vinylbenzene: Toward a Rare Family of Organic Phosphines, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry,
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Synthetic Communications1, 42: 1685–1694, 2012
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397911.2010.542864
SUPERBASE-ASSISTED ADDITION OF PHOSPHINE TO
1-METHOXY-4-VINYLBENZENE: TOWARD A RARE
FAMILY OF ORGANIC PHOSPHINES
S. F. Malysheva, N. K. Gusarova, A. V. Artem’ev,
N. A. Belogorlova, V. I. Smirnov, V. A. Shagun, V. A. Kuimov,
and B. A. Trofimov
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the
Russian Academy of Sciences, Irkutsk, Russian Federation
GRAPHICAL ABSTRACT
Abstract Phosphine reacts with 1-methoxy-4-vinylbenzene in the superbase suspension
KOH-dimethylsulfoxide (70–100 ꢀC, atmospheric pressure) to form regiospecifically anti-
Markovnikov adducts, bis[2-(4-methoxyphenyl)ethyl]phosphine (1) and tris[2-
(4-methoxyphenyl)ethyl]phosphine (2), representatives of rare arylalkylphosphines. The
conditions for the selective preparation of phosphines 1 or 2 in 67% and 80% yields, respect-
ively, have been elaborated. The phosphines have been oxidized with aqueous solution of
H2O2, elemental sulfur, or selenium to afford the corresponding phosphine chalcogenides
in good yields (95–99%).
Keywords 1-Methoxy-4-vinylbenzene; nucleophilic addition; phosphine; phosphine chal-
cogenides; secondary and tertiary phosphines
INTRODUCTION
Organic phosphines and phosphine chalcogenides are intensively employed as
effective ligands[1] and preligands[2] for metal-complex catalysts, extractants of
noble, rare-earth, and transuranic elements,[3] special solvents for the preparation
of conductive nanomaterials,[4] flame retardants,[5] and building blocks for the design
of diverse organophosphorus compounds.[6] Among such compounds, the phos-
phines and phosphine chalcogenides bearing electron-rich and sterically hindered
alkoxyaryl substituents attract particular interest.[1e] They are used as ligands for
Received October 28, 2010.
Address correspondence to B. A. Trofimov, A. E. Favorsky Irkutsk Institute of Chemistry,
Siberian Branch of the Russian Academy of Sciences, 664033 Irkutsk, Russian Federation. E-mail:
mal@irioch.irk.ru
1685

1686
S. F. MALYSHEVA ET AL.
Scheme 1.
the design of new catalytic systems for cross-coupling reactions,[7] the C-H bond acti-
vation reactions,[8] hydrogenation of esters,[9] addition of arylboronic acids to alde-
hydes,[10] cyanosilylation and cyanocarbonation of carbonyl compounds,[11] and
aminocarbonylation of alkyl iodides.[12]
Meanwhile, the syntheses of these ligands (e.g., tris(4-methoxyphenyl)pho-
sphine) are multistep and laborious,[13] requiring the hazardous phosphorus trichlo-
ride and organomagnesium reagents.[13,14] An alternative safer and atom-economical
approach to the preparations of phosphines with alkoxyaryl moieties might be the
addition of phosphine to alkoxyvinylarenes. However, the radical addition of phos-
phine to styrenes gave mixtures of all possible adducts and needs high pressure
(28 atm).[15] The electrophilic addition to alkenes is not typical for phosphine, which
is actually a base,[16] and in a few known cases requires extra-stoichiometric amounts
of acids.[17] In contrast, the nucleophilic addition of phosphine to the multiple bonds
now attracts growing interest because of the discovery of simple and safe versions of
these reactions using superbase suspensions and controlled generation of
phosphine–hydrogen mixture by the red phosphorus = KOH = H2O = toluene
three-phase system.[18]
At the same time, the nucleophilic addition of phosphine to para- (or ortho)alk-
oxyvinylbenzenes is not favored on both kinetic and thermodynamic grounds.
In the case of 1-methoxy-4-vinylbenzene, the intermediate carbon anion will be
destabilized by the electron-donating effect of 4-methoxygroup (Scheme 1).
Indeed, our quantum chemical calculations [B3LYP=6-311 þ G(d,p) account-
ing for the solvent effect (IPCM, E ¼ 45)] showed that the lowest unoccupied molecu-
lar orbital (LUMO) of 1-methoxy-4-vinylbenzene is a little higher (by 0.13 eV) than
that of unsubstituted styrene.
Therefore, the nucleophilic addition of phosphine to 1-alkoxy-4-vinylarenes
appears to be of lower probability. Nevertheless, the LUMO energy difference is
not ultimately high enough to completely prohibit the nucleophilic addition in the
case of 1-methoxy-4-vinylbenzene.
Despite the lower probability of this reaction, we have found that 1-methoxy-4-
vinylbenzene proved to be a sufficiently reactive electrophile relative to the phos-
phide anion.
RESULTS AND DISCUSSION
The experiments have showed that phosphine reacts with 1-methoxy-4-vinyl-
benzene under the action of the superbase catalytic system KOH–dimethylsulfoxide

PHOSPHENE ADDITION TO 1-METHOXY-4-VINYLBENZENE
1687
Scheme 2.
(DMSO) in the presence of small amounts of water at 70–100 ꢀC (argon blanket) to
form regiospecifically anti-Markovnikov adducts, bis[2-(4-methoxyphenyl)ethyl]-
phosphine (1) and tris[2-(4-methoxyphenyl)ethyl]phosphine (2). In the reaction, the
protons of water play the role of the intermediate carbanion interceptor thus pre-
venting the anionic polymerization of 1-methoxy-4-vinylbenzene. Indeed, in the
absence of water, the yield of the target products drops and the amounts of oligo-
mers increase. At greater concentrations of water, the reaction slows down because
of the lower basicity of the medium and hence decreased ionization of phosphine.
Controlled generation of phosphine together with hydrogen[19] was rendered in a
separate reactor by the addition of an aqueous solution of KOH to suspension of
red phosphorus in toluene.[18d] (Scheme 2).
Phosphines 1 or 2 have been selectively prepared under the following con-
ditions. Slow addition (1.5 h) of 1-methoxy-4-vinylbenzene to a suspension of
KOH-DMSO (in the presence of a small amount of H2O) heated to 70 ꢀC with sim-
ultaneous vigorous passing of a phosphine stream through the suspension gave sec-
ondary phosphine 1 in 67% yield. When the reaction is performed at at 100 ꢀC in
KOH-DMSO with additional introduction of 1-methoxy-4-vinylbenzene to the reac-
tion mixture after completion of phosphine feeding (the total time of the reaction is
1 h 40 min), phosphine 2 is formed in 80% yield.
In the absence of KOH, no reaction occurs. It proves the nucleophilic mech-
anism of the addition, which is assumed to be via the phosphide anions generated
Scheme 3.

1688
S. F. MALYSHEVA ET AL.
Scheme 4.
Scheme 5.
from phosphine in the superbase system KOH-DMSO (Scheme 3). The product
of monoaddition of phosphine to 1-methoxy-4-vinylbenzene, primary 2-(4-
methoxyphenyl)ethylphosphine, has been identified in the reaction mixture by
31P NMR.
Secondary phosphine 1 reacts easily with aqueous solution of H2O2 (acetone,
rt, 1 h), elemental sulfur, and selenium in toluene (rt, 30 min) to afford the corre-
sponding secondary phosphine oxide 3a, phosphine sulfide 3b, and phosphine selen-
ide 3c in 95–98% yields (Scheme 4).
Under analogous conditions, tertiary phosphine 2 furnishes the corresponding
tertiary phosphine oxide 4a, phosphine sulfide 4b, and phosphine selenide 4c in good
yields (98–99%) (Scheme 5).
CONCLUSIONS
In summary, in the example of 1-methoxy-4-vinylbenzene and phosphine, the
nucleophilic addition of PH acids to the weakly electrophilic double bond of alkoxy-
vinylarenes has been accomplished for the first time. The reaction proceeds in the
KOH-DMSO system and represents a convenient approach to the synthesis of novel
secondary and tertiary phosphine and phosphine chalcogenides with electron-rich and
sterically hindered methoxyphenyl substituents, possible ligands for the design of the
special metal complex catalysts and building blocks for organic synthesis. For
example, bis[2-(4-methoxyphenyl)ethyl]phosphine 1 and its selenide 3c were success-
fully used for the preparation of diselenophosphinates via three-component reactions
of secondary phosphines or phosphine selenides, elemental selenium, and bases (alkali
metal hydroxides, ammonia, amines),[20] as well as for the synthesis of bis(diorganose-
lenophosphoryl)selenides from secondary phosphines and elemental selenium.[21]

PHOSPHENE ADDITION TO 1-METHOXY-4-VINYLBENZENE
1689
EXPERIMENTAL
All manipulations were carried out in an argon atmosphere. Infrared (IR) spec-
tra were measured with a Bruker IFS 25 instrument in KBr (cmꢁ1). The 1H, 13C, 31
P
and 77Se NMR spectra were measured on a Bruker DPX 400 spectrometer (400.13,
100.61, 161.98 and 76.31 MHz, respectively) in CDCl3 solutions and referenced to
internal hexamethyldisilazane (HMDS) (1H), CDCl3 (13C), external 85%
H3PO4 (31P), and Me2Se (77Se NMR) standards. 4-Metoxystyrene was synthesized
according to the literature.[22]
Synthesis of Bis[2-(4-methoxyphenyl)ethyl]phosphine (1)
A suspension of KOH.0.5H2O (10.00 g, 153.60 mmol), DMSO (40 mL), H2O
(1.5 mL), and hydroquinone (0.03 g) was blown through with argon and saturated
with phosphine. To this suspension, a solution of 1-methoꢀxy-4-vinylbenzene
(7.00 g, 52.17 mmol) in DMSO (5 mL) was added dropwise at 70 C for 1.5 h under
stirring and continuous bubbling of the phosphine. The reaction mixture was
additionally heated (70 ꢀC) for 0.5 h in the flow of phosphine, and then the phosphine
feeding was stopped. In the 31P NMR spectrum, the following signals are observed: -
1
137.76 (t, JPH 227.5 Hz) for 2-[(4-methoxyphenyl)ethyl]phosphine and ꢁ71.08 (d,
1JPH 200.5 Hz) for phosphine 1 in a ratio of 1 : 10. The mixture was blown through
with argon, cooled, diluted with water (100 mL), and extracted with toluene
(50 mL ꢂ 2). The toluene extract was washed with water (40 mL ꢂ 2), dried over
K2CO3, toluene was distilled, and the residue was fractionized in vacuo to give
5.28 g (67%) of secondary phosphine 1, colorless transparent oil, bp 221 ꢀC (1 Torr).
IR (film, n, cmꢁ1): 3100, 3060, 3002, 2925, 2838, 2266, 1610, 1582, 1513, 1463, 1443,
1350, 1245, 1177, 1107, 1033, 821, 721, 549, 514. 1H NMR (400.13 MHz, CDCl3), dH
1.66–1.76 (m, 2H, CH2P), 1.82–1.91 (m, 2H, CH2P), 2.63–2.71 (m, 4H, CH2Ar), 3.08
(d, 1H,1JPH 200.3 Hz, PH), 3.70 (s, 6H, MeO), 6.77 and 7.03 (m, 8H, Ar). 13C NMR
2
1
(100.62 MHz, CDCl3), dC 22.71 (d, JPC 11.2 Hz, CH2Ar), 33.86 (d, JPC 10.3 Hz,
CH2P), 55.36 (MeO), 114.01 (C-2 in Ar), 129.27 (C-3 in Ar), 134.68 (d, JPC
3
8.4 Hz, C-1 in Ar), 158.13 (C-4 in Ar). 31P NMR (161.98 MHz, CDCl3), dP ꢁ71.08
1
(d, JPH 200.5 Hz). Anal. calc. for C18H23O2P (302.35): C, 71.50; H, 7.67; P,
10.24%. Found: C, 71.47; H, 7.43; P, 9.91%.
Synthesis of Tris[2-(4-methoxyphenyl)ethyl]phosphine (2)
A suspension of KOH.0.5H2O (20.00 g, 307.19 mmol), DMSO (50 mL), H2O
(1.5 mL), and hydroquinone (0.03 g) was blown through with argon and saturated
with phosphine. To this suspension, a solution of 1-methoxy-4-vinylbenzene
(3.40 g, 25.34 mmol) in DMSO (5 mL) was added dropwise for 40 min at 70 ꢀC under
stirring and continuous bubbling of the phosphine. The phosphine feeding was
stopped, the mixture was blown through with argon, and a solution of 1-methoxy-4-
vinylbenzene (1.60 g, 11.92 mmol) in DMSO (5 mL) was added. The reaction mixture
was heated (100 ꢀC) and stirred for 1 h, then cooled, diluted with water (100 mL), and
extracted with toluene (70 mL ꢂ 2). The toluene extract was washed with water
(50 mL ꢂ 2) and dried over K2CO3, and the toluene was removed. The residue was

1690
S. F. MALYSHEVA ET AL.
dissolved in hexane (20 mL), and the unsolved part was filtered off. The solvent was
removed, and the residue was dried in vacuo to give 4.34 g (80%) of phosphine 2, yel-
lowish oil. IR (film, n, cmꢁ1): 3007, 2930, 2834, 1610, 1512, 1460, 1440, 1301, 1244,
1178, 1034, 849, 816, 717, 704, 544, 523. 1H NMR (400.13 MHz, CDCl3), dH
1.68–1.71 (m, 6H, CH2P), 2.63–2.69 (m, 6H, CH2Ar), 3.74 (s, 9H, MeO), 6.80 and
2
7.07 (m, 12H, Ar). 13C NMR (100.62 MHz, CDCl3), dC 29.22 (d, JPC 13.9 Hz,
1
CH2Ar), 31.36 (d, JPC 13.9 Hz, CH2P), 55.22 (MeO), 113.85 (C-2 in Ar), 129.02
3
(C-3 in Ar), 134.97 (d, JPC 10.3 Hz, C-1 in Ar), 157.87 (C-4 in Ar). 31P NMR
(161.98 MHz, CDCl3), dP ꢁ28.13. Anal. calc. for C27H33O3P (436.52): C, 74.29; H,
7.62; P, 7.10%. Found: C, 73.98; H, 7.69; P, 6.91%.
Synthesis of Phosphine Oxides 3a and 4a (General Procedure)
To a solution of phosphine 1 or 2 (3.31 mmol) in acetone (20 mL), 35% aque-
ous solution H2O2 (0.32 mL, ꢃ3.31 mmol) was added. The mixture was stirred at
room temperature for 1 h, solvent was distilled in vacuo, the residue was dissolved
in chloroform (2 mL) and reprecipitated to hexane (10 mL), and the product formed
was dried in vacuo.
Bis[2-(4-methoxyphenyl)ethyl]phosphine Oxide (3a). Colorless powder,
yield 94%, 0.99 g, mp 84–86 ꢀC (hexane). IR (KBr, n, cmꢁ1): 3005, 2958, 2905,
2839, 2299, 1611, 1514, 1453, 1303, 1249, 1178, 1161, 1136, 1115, 1032, 851, 720,
5171H NMR (400.13 MHz, CDCl3), dH 1.95–2.02 (m, 2H, CH2P), 2.11–2.17 (m,
1
2H, CH2P), 2.86-2.96 (m, 4H, CH2Ar), 3.80 (s, 6H, MeO), 6.87 (d, 1H, JPH
452.6 Hz, PH), 6.84 and 7.12 (m, 8H, Ar). 13C NMR (100.62 MHz, CDCl3), dC
26.82 (CH2Ar), 30.24 (d, JPC 64.6 Hz, CH2P), 55.12 (MeO), 113.99 (C-2 in Ar),
1
3
129.00 (C-3 in Ar), 131.88 (d, JPC 13.0 Hz, C-1 in Ar), 158.20 (C-4 in Ar). 31P
1
NMR (161.98 MHz, CDCl3), dP 33.11 (d, JPH 453.0 Hz). Anal. calc. for
C18H23O3P (318.35): C, 67.91; H, 7.28; P, 9.73%. Found: C, 67.87; H, 7.13; P, 9.93%.
Tris[2-(4-methoxyphenyl)ethyl]phosphine Oxide (4a). Colorless powder,
yield 98%, 1.02 g, mp 129-131 ꢀC (hexane). IR (KBr, n, cmꢁ1): 3015, 2954, 2932,
2835, 1610, 1512, 1461, 1440, 1301, 1243, 1180, 1161, 1033, 851, 817, 788, 751. H
1
NMR (400.13 MHz, CDCl3), dH 1.92–2.00 (m, 6H, CH2P), 2.79–2.86 (m, 6H,
CH2Ar), 3.76 (m, 9H, MeO), 6.81 and 7.06 (m, 12H, Ar)13C NMR (100.62 MHz,
1
CDCl3), dC 26.91 (CH2Ar), 30.40 (d, JPC 61.5 Hz, CH2P), 55.28 (MeO), 114.10
(C-2 in Ar), 129.04 (C-3 in Ar), 132.75 (d, JPC 12.4 Hz, C-1 in Ar), 158.56 (C-4 in
3
Ar)31P NMR (161.98 MHz, CDCl3), dP 47.01. Anal. Calc. for C27H33O4P (452.52):
C, 71.66; H, 7.35; P, 6.84%. Found: C, 71.57; H, 7.33; P, 6.70%.
Synthesis of Phosphine Sulfides 3b, 4b, and Phosphine Selenides 3c,
4c (General Procedure)
A mixture of phosphine 1 or 2 (6.61 mmol), elemental sulfur or selenium
(6.61 mmol), and toluene (30 mL) was stirred at room temperature for 1 h under
an argon atmosphere. Then toluene was distilled, the residue was washed with
hexane (10 mL), and the product obtained was dried in vacuo to give the target
compounds.

PHOSPHENE ADDITION TO 1-METHOXY-4-VINYLBENZENE
1691
Bis[2-(4-methoxyphenyl)ethyl]phosphine sulfide (3b). Colorless powder,
yield 97%, 2.15 g, mp 110–112 ꢀC (toluene). IR (KBr, NMR (100.62 MHz, CDCl3),
1
dC 27.78 (CH2Ar), 33.09 (d, JPC 29.5 Hz, n, cmꢁ1): 3100, 3010, 2921, 2938, 2906,
2839, 2299, 1610, 1514, 1457, 1445, 1301, 1245, 1177, 1143, 1028, 995, 836, 815,
731, 597, 532, 5221H NMR (400.13 MHz, CDCl3), dH 2.06–2.20 (m, 4H, CH2P),
2.87–3.02 (m, 4H, CH2Ar), 3.80 (s, 6H, MeO), 6.45 (d, 1H, JPH 440.5 Hz, PH),
1
6.84 and 7.00 (m, 8H, Ar)13C NMR (100.62 MHz, CDCl3), dC 28.05 (CH2Ar),
32.12 (d, JPC 50.7 Hz, CH2P), 55.33 (MeO), 114.19 (C-2 in Ar), 129.39 (C-3 in
1
3
Ar), 131.83 (d, JPC 12.4 Hz, C-1 in Ar), 158.43 (C-4 in Ar)31P NMR
1
(161.98 MHz, CDCl3), dP 20.64 (d, JPH 440.5 Hz). Anal. calc. for C18H23O2PS
(334.41): C, 64.65; H, 6.93; P, 9.26, S, 9.59%. Found: C, 64.67; H, 6.90; P, 9.11; S,
9.34%.
Bis[2-(4-methoxyphenyl)ethyl]phosphine selenide (3c). Colorless pow-
der, yield 98%, 2.47 g, mp 114–115 ꢀC (ethanol). IR (KBr, n, cmꢁ1): 3100, 3010,
2967, 2841, 2343, 1610, 1514, 1457, 1445, 1319, 1245, 1178, 1142, 1102, 1028,
1002, 997, 852, 835, 814, 788, 764, 738, 723, 546, 521, 462, 4331H NMR
(400.13 MHz, CDCl3), dH 2.17–2.29 (m, 4H, CH2P), 2.32–2.40 (m, 2H, CH2P),
1
2.87–3.06 (m, 2H, CH2Ar), 3.80 (s, 6H, MeO), 5.97 (d, 1H, JPH 442.1 Hz, PH),
6.84 and 7.14 (m, 8H, Ar). 13C NMR (100.62 MHz, CDCl3), dC 28.86 (CH2Ar),
31.00 (d, JPC 43.5 Hz, CH2P), 55.34 (MeO), 114.21 (C-2 in Ar), 129.43 (C-3 in
1
3
Ar), 131.57 (d, JPC 12.0 Hz, C-1 in Ar), 158.47 (C-4 in Ar). 31P NMR
1
(161.98 MHz, CDCl3), dP 1.88 (d, JPH 442.1 Hz).77Se NMR (76.31 MHz, CDCl3),
1
dSe ꢁ414.83 (d, JPSe 707.1 Hz). Anal. Calc. for C18H23O2PSe (381.31): C, 56.70;
H, 6.08; P, 8.12, Se, 20.71%. Found: C, 56.60; H, 8.19; P, 8.01; Se, 20.49%.
Tris[2-(4-methoxyphenyl)ethyl]phosphine sulfide (4b). Colorless pow-
der, yield 98%, 1.58 g, mp 115–117 ꢀC (hexane). IR (KBr, n, cmꢁ1): 3032, 3007,
2953, 2933, 2835, 1609, 1514, 1467, 1445, 1301, 1273, 1247, 1174, 1138, 1032, 947,
1
789, 743, 588, 548, 522. H NMR (400.13 MHz, CDCl3), dH 2.03–2.10 (m, 6H,
CH2P), 2.82–2.90 (m, 6H, CH2Ar), 3.77 (s, 9H, MeO), 6.81 and 7.06 (m, 12H,
Ar). 13C CH2P), 55.34 (MeO), 114.14 (C-2 in Ar), 129.28 (C-3 in Ar), 132.62 (d,
3JPC 13.9 Hz, C-1 in Ar), 158.34 (C-4 in Ar). 31P NMR (161.98 MHz, CDCl3), dP
48.28. Anal. calc. for C27H33O3PS (468.59): C, 69.21; H, 7.10; P, 6.61; S, 6.84%.
Found: C, 69.27; H, 7.05; P, 6.49; S, 6.71%.
Tris[2-(4-methoxyphenyl)ethyl]phosphine selenide (4c). Colorless pow-
der, yield 99%, 1.75 g, mp 123–125 ꢀC (hexane). IR (KBr, n, cmꢁ1): 3031, 2952,
2932, 2834, 1610, 1514, 1465, 1444, 1301, 1246, 1172, 1138, 1127, 1032, 947, 810,
1
781, 741, 677, 550, 520, 466. H NMR (400.13 MHz, CDCl3), dH 2.12–2.19 (m,
6H, CH2P), 2.81–2.87 (m, 6H, CH2Ar), 3.76 (s, 9H, MeO), 6.80 and 7.06 (m,
1
12H, Ar). 13C NMR (100.62 MHz, CDCl3), dC 28.52 (CH2Ar), 32.64 (d, JPC
40.3 Hz, CH2P), 55.33 (MeO), 114.14 (C-2 in Ar), 129.31 (C-3 in Ar), 132.35 (d,
3JPC 13.2 Hz, C-1 in Ar), 158.37 (C-4 in Ar). 31P NMR (161.98 MHz, CDCl3), dP
1
37.05.77Se NMR (76.31 MHz, CDCl3), dSe ꢁ387.27 (d, JPSe 691.3 Hz). Anal. calc.
for C27H33O3PSe (515.48): C, 62.91; H, 6.45; P, 6.01; Se, 15.32%. Found: C,
62.93; H, 6.59; P, 5.88; Se, 15.45%.

1692
S. F. MALYSHEVA ET AL.
ACKNOWLEDGMENTS
This work was supported by the president of the Russian Federation (Program
for the support of Young Russian Scientists and Leading Scientific Schools, Grants
MK-629-2010.3 and NSH 3230-2010.3) and the Russian Foundation for Basic
Research (Grant No. 08-03-00251).
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