Radical addition of secondary phosphine sulfides and selenides to vinyl selenides

Article abstract of DOI:10.1055/s-2008-1067212

The first examples of a facile hydrochalcogenophosphorylation of alkyl vinyl selenides are reported. The regiospecific addition of secondary phosphine sulfides and phosphine selenides to vinyl selenides proceeds under radical initiation (AIBN, 65-70°C, 1 h or UV-irradiation, 1 h) to afford the anti-Markovnikov adducts in 87-95% yield. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2008-1067212

PAPER
2743
Radical Addition of Secondary Phosphine Sulfides and Selenides to Vinyl
Selenides
R
adical
A
ddition
o
i
f
Secondary
P
hosph
a
ine Sulfides and
K
Selenides to Vinyl
.
Selenides Gusarova, Nataliya A. Chernysheva, Svetlana V. Yas’ko, Tatyana I. Kazantseva, Igor A. Ushakov,
Boris A. Trofimov*
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Street, 664033 Irkutsk,
Russian Federation
Fax +7(3952)419346; E-mail: gusarova@irioch.irk.ru
Received 28 April 2008; revised 19 May 2008
Secondary phosphine oxides showed less reactivity in this
Abstract: The first examples of a facile hydrochalcogenophospho-
reaction. Thus, heating (65–70 °C, 20 h, dioxane) diphe-
nylphosphine oxide with vinyl selenide 5 in the presence
rylation of alkyl vinyl selenides are reported. The regiospecific ad-
dition of secondary phosphine sulfides and phosphine selenides to
vinyl selenides proceeds under radical initiation (AIBN, 65–70 °C,
of AIBN gave 2-(hexylselanyl)ethyl(diphenyl)phosphine
1 h or UV-irradiation, 1 h) to afford the anti-Markovnikov adducts oxide (8) in ~40% yield (31P NMR). Another product of
in 87–95% yield.
the reaction, diphenylphosphinic acid (~60% yield;
dp = 28.94 ppm), is likely to result from the oxidation of
Key words: alkyl vinyl selenides, secondary phosphine sulfides,
secondary phosphine selenides, radical addition, functional tertiary
phosphine chalcogenides
diphenylphosphine oxide by air.
At the same time, the phosphine oxide 8 was prepared in
high isolated yield by the oxidation of alkylselanylphos-
phine selenide 7g with aqueous hydrogen peroxide (r.t.,
10 min, acetone) as shown in Scheme 1.
Tertiary phosphine chalcogenides are important ligands in
the design of new metal-complex catalysts1 (in some cat-
alytic processes they show even better results than the cor-
responding tertiary phosphines1a), building blocks in the
synthesis of biologically active compounds (for example,
anti-arthritic gold complexes2) and intermediates for
semi-conducting nanomaterials.3 In recent years there has
been increasing interest in functional phosphine chalco-
genides as polydentate ‘hemilabile’ ligands4 such as
R2P(X)CH2CH2SR¢ (X = O, S), which has been used, for
example, in myocardial imaging.4c,d The substitution of an
alkyl sulfide fragment for an alkyl selenide group in these
compounds expands the scope of practical applications of
tertiary phosphine chalcogenides. Meanwhile, to the best
of our knowledge, such functional tertiary phosphine sul-
fides and phosphine selenides with alkyl selenide moieties
have not been reported in the literature.
Se
O
Ph
Ph
Ph
Ph
H2O2, H2O–acetone
– Se
P
P
SeC6H13
SeC6H13
7g
8 (82%)
Scheme 1
In summary, work described here on the addition of sec-
ondary phosphine chalcogenides to vinyl selenides con-
tributes to the understanding of the reactivity of these
compounds, provides a facile synthesis of new tertiary
phosphine chalcogenides with alkyl selenide substituents
and extends the synthetic potential of reactions of PH-ad-
dends with alkenes. Such reactions represent one of the
most convenient approaches to C–P bond formation and
continues to attract attention as a straightforward, atom-
economic (‘green’) route for the synthesis of tertiary
phosphine chalcogenides, including functional ones.5,7
The goal of the present work was to study the reaction of
available secondary phosphine chalcogenides5 with alkyl
vinyl selenides, which were easily prepared from elemen-
tal selenium, acetylene and alkyl halides,6 in order to de-
velop a general, expedient and atom-economic method for
the synthesis of functional tertiary phosphine chalco-
genides containing alkyl selenide fragments.
The 1H, 13C, 31P and 77Se NMR spectra were recorded on a Bruker
DPX 400 spectrometer (400.13, 100.69, 161.98 and 76.31 MHz, re-
spectively) in CDCl3 solutions and referenced to internal HMDS
(1H NMR), external 85% H3PO4 (31P NMR) and internal Me2Se
(77Se NMR). IR spectra were run on a Bruker IFS 25 spectrometer
in microlayer (the abbreviation ‘sh’ refers to shoulder).
We have found that secondary phosphine sulfides 1, 2 and
selenides 3, 4 add regiospecifically to alkyl vinyl se-
lenides 5, 6 under mild conditions (AIBN, 65–70 °C or
UV-irradiation, dioxane, 1 h) to give tertiary alkylsela-
nylphosphine chalcogenides 7a–h in 87–95% yield
(Table 1).
Alkylselanylphosphine Chalcogenides 7a–h; Typical Procedure
(Table 1)
A solution of phosphine chalcogenide 1–4 (0.5 mmol) and vinyl se-
lenide 5, 6 (0.575 mmol) in dioxane (3 mL) in the presence of AIBN
(2% by mass) was stirred under an argon atmosphere at 65–70 °C
for 1 h. The reaction was monitored using 31P NMR spectra, which
showed the disappearance of peaks of the initial secondary phos-
phine chalcogenide 1–4 at d = 2.65–22.85 ppm and the appearance
of new peaks at d = 33.92–48.96 ppm corresponding to tertiary
alkylselanylphosphine chalcogenides 7a–h. The solvent was then
SYNTHESIS 2008, No. 17, pp 2743–2746
x
x.
x
x
.
2
0
0
8
Advanced online publication: 06.08.2008
DOI: 10.1055/s-2008-1067212; Art ID: Z09708SS
© Georg Thieme Verlag Stuttgart · New York

2744
N. K. Gusarova et al.
PAPER
Table 1 Synthesis of Tertiary Alkylselanylphosphine Chalcogenides 7a–ha
R1
R1
R1
R1
X
X
AIBN or UV
dioxane
SeR2
5,6
P
+
P
SeR2
H
7a–h
1–4
Entry
Secondary phosphine chalcogenide
R1
Vinyl selenide
Product
Yield (%)b
X
R2
1
2
3
4
5
6
7
8
9c
1
2
3
4
1
2
3
4
1
Ph
S
5
5
5
5
6
6
6
6
6
n-C5H11
n-C5H11
n-C5H11
n-C5H11
n-C6H13
n-C6H13
n-C6H13
n-C6H13
n-C6H13
7a
7b
7c
7d
7e
7f
95
90
92
93
94
87
89
89
95
Ph(CH2)2
Ph
S
Se
Se
S
Ph(CH2)2
Ph
Ph(CH2)2
Ph
S
Se
Se
S
7g
7h
7e
Ph(CH2)2
Ph
a Reaction conditions: AIBN, 1 h (entries 1–8) or UV-irradiation, 1 h (entry 9).
b Isolated yield after purification (see experimental section).
c A solution of 1 (0.1 mmol) and 5 (0.115 mmol) in dioxane (3 mL) was irradiated under an argon atmosphere (quartz ampoule, 200W Hg arc
lamp).
removed under reduced pressure and the residue was dissolved in
Et2O (3 mL). The solution was passed through a thin layer of Al2O3
and the solvent was evaporated in vacuo to give alkylselanylphos-
phine chalcogenides 7a–h of analytical purity.
893, 857, sh 771 (d CH of phenyl rings), 752 (n P–C), 698 (d CH of
phenyl rings), sh 612, 598 (n P=S) cm–1.
1H NMR (400 MHz, CDCl3): d = 0.90 (m, 3 H, CH3), 1.34 (m, 4 H,
CH2CH2CH3), 1.65 (m, 2 H, CH2C3H7), 2.26 (m, 6 H, CH2P), 2.57
(m, 2 H, CH2C4H9), 2.73 (m, 2 H, PCH2CH2Se), 2.93 (m, 4 H,
PhCH2), 7.20 (m, 4 H, o-H, Ph), 7.23 (m, 2 H, p-H, Ph), 7.31 (m,
4 H, m-H, Ph).
2-(Pentylselanyl)ethyl(diphenyl)phosphine Sulfide (7a)
Yield: 95%; yellow oil.
IR (film): 3074, 3053 (n CH of phenyl rings), 2955, 2926, 2867,
2855 (n CH), 1586, 1574, 1480 (n C=C of phenyl rings), 1464,
1436, (d CH2), 1379 (d CH3), 1334, 1309, 1260, 1243, 1168, 1104,
1070, 1027, 1016, 998, 884, sh 770 (d CH of phenyl rings), 751 (n
P–C), 741, 724, 711, 692 (d CH of phenyl rings), sh 620, 609 (n
P=S) cm–1.
1H NMR (400 MHz, CDCl3): d = 0.85 (m, 3 H, CH3), 1.28 (m, 4 H,
CH2CH2CH3), 1.58 (m, 2 H, CH2C3H7), 2.54 (m, 2 H, CH2C4H9),
2.74 (m, 4 H, SeCH2CH2P), 7.47 (m, 6 H, Ph), 7.81 (m, 4 H, Ph).
13C NMR (100 MHz, CDCl3): d = 13.9 (CH3), 15.4 (d, 2JP–C = 3.3
Hz, PCH2CH2Se), 22.1 (CH2CH3), 24.6 (CH2C4H9), 29.3 (d, 2JP–C
2.2 Hz, CH2Ph), 30.0 (CH2C3H7), 31.9 (CH2C2H5), 32.2 (d, 1JP–C
=
=
36.1 Hz, PCH2CH2Se), 32.4 (d, 1JP–C = 40.9 Hz, CH2CH2Ph), 126.6
(p-C, Ph), 128.2 (o-C, Ph), 128.7 (m-C, Ph), 140.1 (d, 3JP–C = 13.6
Hz, i-C, Ph).
31P NMR (162 MHz, CDCl3): d = 37.93.
77Se NMR (76 MHz, CDCl3): d = 208.5 (d, 3JP–Se = 8.6 Hz).
13C NMR (100 MHz, CDCl3): d = 13.9 (CH3), 14.6 (d, 2JP–C = 3.3
Hz, PCH2CH2Se), 22.1 (CH2CH3), 24.4 (CH2C4H9), 29.9
(CH2C3H7), 31.9 (CH2C2H5), 34.4 (d, 1JP–C = 49.0 Hz, CH2P), 128.6
Anal. Calcd for C23H33PSSe: C, 61.18; H, 7.37; P, 6.86; S, 7.10; Se,
17.49. Found: C, 60.94; H, 7.15; P, 7.02; S, 7.24; Se, 17.65.
2
3
2-(Pentylselanyl)ethyl(diphenyl)phosphine Selenide (7c)
Yield: 92%; yellow oil.
(d, JP–C = 11.8 Hz, o-C, Ph), 130.9 (d, JP–C = 10.0 Hz, m-C, Ph),
4
1
131.5 (d, JP–C = 3.0 Hz, p-C, Ph), 132.2 (d, JP–C = 78.9 Hz, i-C,
Ph).
IR (film): 3073, 3053, 3006 (n CH of phenyl rings), 2955, 2926,
2869, 2855 (n CH), 1587, 1573, 1481 (n C=C of phenyl rings),
1464, 1436, 1402 (d CH2), 1378 (d CH3), 1333, 1309, 1266, 1243,
1188, 1167, 1130, 1100, 1070, 1027, 998, 924, 883, 847, 747, 720,
708, 691 (d CH of phenyl rings), 643, sh 548, 531 (n P=Se) cm–1.
1H NMR (400 MHz, CDCl3): d = 0.87 (m, 3 H, CH3), 1.31 (m, 4 H,
CH2CH2CH3), 1.59 (m, 2 H, CH2C3H7), 2.56 (m, 2 H, CH2C4H9),
2.72 (m, 2 H, SeCH2CH2P), 2.88 (m, 2 H, CH2P), 7.46 (m, 6 H, Ph),
7.82 (m, 4 H, Ph).
31P NMR (162 MHz, CDCl3): d = 42.43.
77Se NMR (76 MHz, CDCl3): d = 206.4 (d, 3JP–Se = 13.2 Hz).
Anal. Calcd for C19H25PSSe: C, 57.71; H, 6.37; P, 7.83; S, 8.11; Se,
19.97. Found: C, 57.93; H, 6.13; P, 7.82; S, 8.36; Se, 19.76.
2-(Pentylselanyl)ethyl(diphenethyl)phosphine Sulfide (7b)
Yield: 90%; yellow oil.
IR (film): 3084, 3061, 3026, 3000 (n CH of phenyl rings), 2955,
2925, 2867, 2856 (n CH), 1602, 1584, 1496 (n C=C of phenyl
rings), 1453, 1406 (d CH2), 1379 (d CH3), 1332, 1295, 1268, 1244,
1211, 1199, 1174, 1135, 1103, 1092, 1072, 1029, 1008, 948, 908,
13C NMR (101 MHz, CDCl3): d = 13.9 (CH3), 15.3 (d, 2JP–C = 2.2
Hz, PCH2CH2Se), 22.1 (CH2CH3), 24.4 (CH2C4H9), 30.0
(CH2C3H7), 31.9 (CH2C2H5), 34.2 (d, 1JP–C = 42.0 Hz, CH2P), 128.6
2
1
(d, JP–C = 12.2 Hz, o-C, Ph), 130.9 (d, JP–C = 71.1 Hz, i-C, Ph),
Synthesis 2008, No. 17, 2743–2746 © Thieme Stuttgart · New York

PAPER
Radical Addition of Secondary Phosphine Sulfides and Selenides to Vinyl Selenides
2745
131.4 (d, 3JP–C = 10.3 Hz, m-C, Ph), 131.6 (d, 4JP–C = 3.0 Hz, p-C,
1254, 1214, 1175, 1121, 1082, 1048, 1030, 1011, 949, 909, 888,
Ph).
874, sh 781, 767 (d CH of phenyl rings), 752 (n P–C), 699 (d CH of
phenyl rings), sh 612, 598 (n P=S) cm–1.
31P NMR (162 MHz, CDCl3): d = 33.92.
1H NMR (400 MHz, CDCl3): d = 0.90 (m, 3 H, CH3), 1.33 (m, 4 H,
CH2CH2CH3), 1.39 (m, 2 H, CH2C3H7), 1.67 (m, 2 H, CH2C4H9),
2.17 (m, 6 H, CH2P), 2.61 (m, 2 H, CH2C5H11), 2.76 (m, 2 H,
PCH2CH2Se), 2.95 (m, 4 H, PhCH2), 7.21 (m, 4 H, o-H, Ph), 7.24
(m, 2 H, p-H, Ph), 7.32 (m, 4 H, m-H, Ph).
77Se NMR (76 MHz, CDCl3): d = –346.6 (d, JP–Se = 728.5 Hz),
1
206.6 (d, 3JP–Se = 10.0 Hz).
Anal. Calcd for C19H25PSe2: C, 51.60; H, 5.70; P, 7.00; Se, 35.70.
Found: C, 51.32; H, 5.99; P, 6.76; Se, 35.93.
13C NMR (101 MHz, CDCl3): d = 14.1 (CH3), 14.8 (d, 2JP–C = 4.5
Hz, PCH2CH2Se), 22.6 (CH2CH3), 24.80 (CH2C5H11), 28.7 (d,
2JP–C = 2.5 Hz, CH2Ph), 29.6 (CH2C3H7), 30.5 (CH2C4H9), 31.4
2-(Pentylselanyl)ethyl(diphenethyl)phosphine Selenide (7d)
Yield: 93%; yellow oil.
(CH2C2H5), 32.8 (d, 1JP–C = 43.3 Hz, PCH2CH2Se), 33.0 (d, 1JP–C
=
IR (film): 3084, 3061, 3026, 3001 (n CH of phenyl rings), 2955,
2925, 2867, 2856 (n CH), 1603, 1584, 1496 (n C=C of phenyl
rings), 1453, 1406 (d CH2), 1378 (d CH3), 1332, 1295, 1268, 1244,
1214, 1200, 1173, 1135, 1105, 1071, 1030, 1007, 948, 909, 859,
844, 806, 752 (n P–C), 699 (d CH of phenyl rings), sh 573, 555 (n
P=Se) cm–1.
47.3 Hz, CH2CH2Ph), 126.7 (p-C, Ph), 128.3 (o-C, Ph), 128.8 (m-C,
Ph), 140.5 (d, 3JP–C = 13.6 Hz, i-C, Ph).
31P NMR (162 MHz, CDCl3): d = 48.96.
77Se NMR (76 MHz, CDCl3): d = 208.1 (d, 3JP–Se = 10.0 Hz).
1H NMR (400 MHz, CDCl3): d = 0.89 (m, 3 H, CH3), 1.34 (m, 4 H,
CH2CH2CH3), 1.66 (m, 2 H, CH2C3H7), 2.26 (m, 6 H, CH2P), 2.58
(m, 2 H, CH2C4H9), 2.74 (m, 2 H, PCH2CH2Se), 2.94 (m, 4 H,
PhCH2), 7.19 (m, 4 H, o-H, Ph), 7.23 (m, 2 H, p-H, Ph), 7.30 (m,
4 H, m-H, Ph).
Anal. Calcd for C24H35PSSe: C, 61.92; H, 7.58; P, 6.65; S, 6.89; Se,
16.96. Found: C, 61.83; H, 7.65; P, 6.80; S, 7.03; Se, 16.69.
2-(Hexylselanyl)ethyl(diphenyl)phosphine Selenide (7g)
Yield: 89%; dark-yellow oil.
13C NMR (101 MHz, CDCl3): d = 14.0 (CH3), 15.5 (d, 2JP–C = 4.8
IR (film): 3074, 3053, 3006 (n CH of phenyl rings), 2955, 2925,
2867, 2854 (n CH), 1614, 1588, 1573, 1481 (n C=C of phenyl
rings), 1465, 1436, 1404 (d CH2), 1378 (d CH3), 1334, 1309, 1278,
1251, 1234, 1188, 1168, 1131, 1100, 1070, 1027, 998, 961, 929,
885, 847, 741, 728, 707, 691 (d CH of phenyl rings), 641, sh 548,
531 (n P=Se) cm–1.
Hz, PCH2CH2Se), 22.2 (CH2CH3), 24.6 (CH2C4H9), 29.3 (d, 2JP–C
3.0 Hz, CH2Ph), 30.1 (CH2C3H7), 32.0 (CH2C2H5), 32.2 (d, 1JP–C
=
=
36.1 Hz, PCH2CH2Se), 32.4 (d, 1JP–C = 40.2 Hz, CH2CH2Ph), 126.6
3
(p-C, Ph), 128.2 (o-C, Ph), 128.7 (m-C, Ph), 140.2 (d, JP–C = 13.6
Hz, i-C, Ph).
31P NMR (162 MHz, CDCl3): d = 38.13.
1H NMR (400 MHz, CDCl3): d = 0.90 (m, 3 H, CH3), 1.33 (m, 6 H,
CH2CH2CH2CH3), 1.63 (m, 2 H, CH2C4H9), 2.60 (m, 2 H,
CH2C5H11), 2.76 (m, 2 H, SeCH2CH2P), 2.92 (m, 2 H, CH2P), 7.50
(m, 6 H, Ph), 7.85 (m, 4 H, Ph).
77Se NMR (76 MHz, CDCl3): d = –387.6 (d, JP–Se = 704.3 Hz),
1
208.5 (d, 3JP–Se = 9.5 Hz).
Anal. Calcd for C23H33PSe2: C, 55.43; H, 6.67; P, 6.21; Se, 31.69.
Found: C, 55.65; H, 6.77; P, 6.16; Se, 31.42.
13C NMR (101 MHz, CDCl3): d = 14.1 (CH3), 15.5 (d, 2JP–C = 2.2
Hz, PCH2CH2Se), 22.6 (CH2CH3), 24.6 (CH2C5H11), 29.6
(CH2C3H7), 30.4 (CH2C4H9), 31.3 (CH2C2H5), 34.4 (d, 1JP–C = 42.0
2-(Hexylselanyl)ethyl(diphenyl)phosphine Sulfide (7e)
Yield: 94%; yellow oil.
2
3
Hz, CH2P), 128.8 (d, JP–C = 12.2 Hz, o-C, Ph), 131.6 (d, JP–C
=
4
10.3 Hz, m-C, Ph), 131.8 (d, JP–C = 3.0 Hz, p-C, Ph), 132.2 (i-C,
IR (film): 3074, 3054, 3021, 3005 (n CH of phenyl rings), 2955,
2926, 2867, 2854 (n CH), 1606, 1586, 1574, 1480 (n C=C of phenyl
rings), 1465, 1436, 1404 (d CH2), 1378 (d CH3), 1332, 1309, 1279,
1254, 1234, 1187, 1168, 1104, 1070, 1027, 1013, 998, 886, 849, sh
771 (d CH of phenyl rings), 750 (n P–C), 741, 723, 711, 692 (d CH
of phenyl rings), 642, sh 620, 609 (n P=S) cm–1.
1H NMR (400 MHz, CDCl3): d = 0.88 (m, 3 H, CH3), 1.33 (m, 6 H,
CH2CH2CH2CH3), 1.61 (m, 2 H, CH2C4H9), 2.58 (m, 2 H,
CH2C5H11), 2.78 (m, 4 H, SeCH2CH2P), 7.50 (m, 6 H, Ph), 7.84 (m,
4 H, Ph).
Ph).
31P NMR (162 MHz, CDCl3): d = 33.92.
77Se NMR (76 MHz, CDCl3): d = –352.1 (d, JP–Se = 728.0 Hz),
1
200.2 (d, 3JP–Se = 10.2 Hz).
Anal. Calcd for C20H27PSe2: C, 52.64; H, 5.96; P, 6.79; Se, 34.61.
Found: C, 52.37; H, 6.07; P, 6.74; Se, 34.82.
2-(Hexylselanyl)ethyl(diphenethyl)phosphine Selenide (7h)
Yield: 89%; light-yellow oil.
13C NMR (101 MHz, CDCl3): d = 14.0 (CH3), 14.6 (d, 2JP–C = 3.0
Hz, PCH2CH2Se), 22.4 (CH2CH3), 24.4 (CH2C5H11), 29.4
(CH2C3H7), 30.2 (CH2C4H9), 31.2 (CH2C2H5), 34.4 (d, 1JP–C = 49.0
IR (film): 3085, 3061, 3026, 3001 (n CH of phenyl rings), 2954,
2925, 2854, (n CH), 1603, 1583, 1496 (n C=C of phenyl rings),
1454, 1405 (d CH2), 1378 (d CH3), 1271, 1253, 1232, 1213, 1192,
1175, 1133, 1072, 1030, 1007, 948, 903, 873, 844, 751 (n P–C), 699
(d CH of phenyl rings), sh 573, 556 (n P=Se) cm–1.
1H NMR (400 MHz, CDCl3): d = 0.91 (m, 3 H, CH3), 1.32 (m, 4 H,
CH2CH2CH3), 1.39 (m, 2 H, CH2C3H7), 1.68 (m, 2 H, CH2C4H9),
2.29 (m, 6 H, CH2P), 2.61 (m, 2 H, CH2C5H11), 2.76 (m, 2 H,
PCH2CH2Se), 2.97 (m, 4 H, PhCH2), 7.23 (m, 4 H, o-H, Ph), 7.26
(m, 2 H, p-H, Ph), 7.34 (m, 4 H, m-H, Ph).
2
3
Hz, CH2P), 128.6 (d, JP–C = 12.2 Hz, o-C, Ph), 130.9 (d, JP–C
=
4
10.3 Hz, m-C, Ph), 131.5 (d, JP–C = 3.0 Hz, p-C, Ph), 132.2 (d,
1JP–C = 79.2 Hz, i-C, Ph).
31P NMR (162 MHz, CDCl3): d = 42.49.
77Se NMR (76 MHz, CDCl3): d = 206.4 (d, 3JP–Se = 13.0 Hz).
Anal. Calcd for C20H27PSSe: C, 58.67; H, 6.65; P, 7.57; S, 7.83; Se,
19.29. Found: C, 58.78; H, 6.54; P, 7.65; S, 8.02; Se, 19.01.
13C NMR (101 MHz, CDCl3): d = 14.1 (CH3), 15.5 (d, 2JP–C = 4.1
Hz, PCH2CH2Se), 22.5 (CH2CH3), 24.7 (CH2C5H11), 29.3 (d,
2JP–C = 2.2 Hz, CH2Ph), 29.5 (CH2C3H7), 30.4 (CH2C4H9), 31.3
2-(Hexylselanyl)ethyl(diphenethyl)phosphine Sulfide (7f)
Yield: 87%; yellow oil.
(CH2C2H5), 32.2 (d, 1JP–C = 36.5 Hz, PCH2CH2Se), 32.4 (d, 1JP–C
=
IR (film): 3085, 3062, 3026, 3001 (n CH of phenyl rings), 2955,
2926, 2867, 2853 (n CH), 1603, 1583, 1496 (n C=C of phenyl
rings), 1465, 1454, 1410 (d CH2), 1378 (d CH3), 1366, 1286, 1268,
40.9 Hz, CH2CH2Ph), 126.6 (p-C, Ph), 128.3 (o-C, Ph), 128.7 (m-C,
Ph), 140.1 (d, 3JP–C = 13.6 Hz, i-C, Ph).
31P NMR (162 MHz, CDCl3): d = 37.88.
Synthesis 2008, No. 17, 2743–2746 © Thieme Stuttgart · New York

2746
N. K. Gusarova et al.
PAPER
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Chem. Int. Ed. 2004, 43, 6382. (f) Imamoto, T.; Oohara, N.;
Takahashi, H. Synthesis 2004, 1353. (g)Subasi,E.; Senturk,
O. S.; Ugur, F. Z. Naturforsch., B 2004, 59, 836.
77Se NMR (76 MHz, CDCl3): d = –346.7 (d, JP–Se = 723.9 Hz),
1
206.2 (d, 3JP–Se = 9.0 Hz).
Anal. Calcd for C24H35PSe2: C, 56.25; H, 6.88; P, 6.04; Se, 30.82.
Found: C, 56.32; H, 6.90; P, 5.77; Se, 31.01.
2-(Hexylselanyl)ethyl(diphenyl)phosphine Oxide (8)
(2) Hussain, M. S.; Isab, A. A. J. Chem. Crystallogr. 2000, 30,
731.
To a solution of hexylselanylphosphine selenide (7g; 0.44 mmol) in
acetone (3 mL), aq H2O2 (35%, 0.44 mmol) was added dropwise.
The reaction mixture was stirred at 20–22 °C for 10 min. Selenium
precipitate (0.03 g, red powder) was filtered off and the filtrate was
diluted with H2O (~3 mL) and extracted with CHCl3 (3 × 5 mL).
The extract was dried (Ca2CO3) and the solvent was removed under
reduced pressure to give the product, which was dried in vacuo.
(3) (a) Sashchiuk, A.; Amirav, L.; Bashouti, M.; Krueger, M.;
Sivan, U.; Lifshitz, E. Nano Lett. 2004, 4, 159. (b) Gubin,
S. P.; Kataeva, N. A.; Khomutov, G. B. Izv. Akad. Nauk, Ser.
Khim. 2005, 811. (c) Snee, P. T.; Somers, R. C.; Nair, G.;
Zimmer, J. P.; Bawendi, M. G.; Nocera, D. G. J. Am. Chem.
Soc. 2006, 128, 13320. (d) Liu, H.; Owen, J. S.; Alivisatos,
A. P. J. Am. Chem. Soc. 2007, 129, 305.
Yield: 0.14 g (82%); yellow oil.
(4) (a) Hingst, M.; Tepper, M.; Stelzer, O. Eur. J. Inorg. Chem.
1998, 73. (b) Herd, O.; Hebter, A.; Hingst, M.; Machnitzki,
R.; Tepper, M.; Stelzer, O. Catal. Today 1998, 42, 413.
(c) Slone, C. S.; Weinberger, D. A.; Mirkin, C. A. Prog.
Inorg. Chem. 1999, 48, 233. (d) Liek, C.; Machnitzki, R.;
Nickel, T.; Schenk, S.; Tepper, M.; Stelzer, O. Z.
Naturforsch., B 1999, 54, 1532. (e) Brauer, D. J.;
Kottsieper, K. W.; Nickel, T.; Sheldrick, W. S. Eur. J. Inorg.
Chem. 2001, 1251.
IR (film): 3073, 3054, 3006 (n CH of phenyl rings), 2954, 2925,
2867, 2853 (n CH), 1590, 1575, 1482 (n C=C of phenyl rings),
1459, 1437, 1418 (d CH2), 1378 (d CH3), 1333, 1309, 1262, 1232,
1190 (n P=O), 1172, 1120, 1102, 1070, 1027, 998, 883, 854, sh 769
(d CH of phenyl rings), 743 (n P–C), 722, 695 (d CH of phenyl
rings), 640, 550, 528 cm–1.
1H NMR (400 MHz, CDCl3): d = 0.87 (m, 3 H, CH3), 1.31 (m, 6 H,
CH2CH2CH2CH3), 1.60 (m, 2 H, CH2C4H9), 2.57 (m, 2 H,
CH2C5H11), 2.64 (m, 2 H, SeCH2CH2P), 2.74 (m, 2 H, CH2P), 7.53
(m, 6 H, Ph), 7.74 (m, 4 H, Ph).
(5) Arbuzova, S. N.; Gusarova, N. K.; Trofimov, B. A.
ARKIVOC 2006, (v), 12.
2
13C NMR (101 MHz, CDCl3): d = 13.9 (d, JP–C = 4.4 Hz,
(6) (a) Gusarova, N. K.; Potapov, V. A.; Amosova, S. V.;
Trofimov, B. A. Zh. Org. Khim. 1983, 19, 2477; Chem.
Abstr. 1984, 101, 6574r. (b) Trofimov, B. A. Sulfur Rep.
1992, 207.
PCH2CH2Se), 14.0 (CH3), 22.5 (CH2CH3), 24.5 (CH2C5H11), 29.5
(CH2C3H7), 30.3 (CH2C4H9), 31.2 (CH2C2H5), 31.9 (d, 1JP–C = 64.9
Hz, CH2P), 128.7 (d, 2JP–C = 11.8 Hz, o-C, Ph), 130.7 (d, 3JP–C = 9.6
Hz, m-C, Ph), 131.9 (d, 4JP–C = 3.0 Hz, p-C, Ph), 132.5 (i-C, Ph).
(7) (a) Bunlaksananusorn, T.; Knochel, P. Tetrahedron Lett.
2002, 43, 5817. (b) Jessop, C. M.; Parsons, A. F.; Routledge,
A.; Irvine, D. Tetrahedron Lett. 2003, 44, 479. (c) Rey, P.;
Taillades, J.; Rossi, J. C.; Gros, G. Tetrahedron Lett. 2003,
44, 6169. (d) Gusarova, N. K.; Ivanova, N. I.; Bogdanova,
M. V.; Malysheva, S. F.; Belogorlova, N. A.; Sukhov, B. G.;
Trofimov, B. A. Mendeleev Commun. 2004, 216.
(e) Bunlaksananusorn, T.; Knochel, P. J. Org. Chem. 2004,
69, 4595. (f) Gusarova, N. K.; Bogdanova, M. V.; Ivanova,
N. I.; Chernysheva, N. A.; Sukhov, B. G.; Sinegovskaya, L.
M.; Kazheva, O. N.; Alexandrov, G. G.; Dyachenko, O. A.;
Trofimov, B. A. Synthesis 2005, 3103. (g) Leca, D.;
Fensterbank, L.; Lacôte, E.; Malacria, M. Chem. Soc. Rev.
2005, 34, 858. (h) Parsons, A. F.; Sharpe, D. J.; Taylor, P.
Synlett 2005, 1. (i) Hirai, T.; Han, L. B. Org. Lett. 2007, 9,
53. (j) Gusarova, N. K.; Malysheva, S. F.; Belogorlova, N.
A.; Sukhov, B. G.; Trofimov, B. A. Synthesis 2007, 2849.
31P NMR (162 MHz, CDCl3): d = 31.46.
77Se NMR (76 MHz, CDCl3): d = 205.9 (d, 3JP–Se = 11.0 Hz).
Anal. Calcd for C20H27OPSe: C, 61.07; H, 6.92; P, 7.87; Se, 20.07.
Found: C, 60.95; H, 6.86; P, 7.66; Se, 20.22.
Acknowledgment
Financial support from the Russian Foundation for Basic Research
(grant no. 07-03-00562) is gratefully acknowledged.
References
(1) (a) Faller, J. W.; Wilt, J. C.; Parr, J. Org. Lett. 2004, 6, 1301.
(b) Skvortsov, N. K.; Spivak, V. N.; Pashnova, L. V.;
Bel’skii, V. K. Russ. J. Gen. Chem. 1997, 67, 487.
(c) Kalinin, A. B.; Trofimov, A. E.; Skvortsov, N. K. Russ.
Synthesis 2008, No. 17, 2743–2746 © Thieme Stuttgart · New York