An efficient and general synthesis of se-esters of diselenophosphinic acids via reaction of alkali metal diselenophosphinates with organic halides

Article abstract of DOI:10.1055/s-0030-1258471

Alkali metal diselenophosphinates RSe (R = aryl, arylalkyl, hetarylalkyl; M = Na, K, or Cs) readily react with organic halides RHal (R = alkyl, allyl, propargyl, benzyl; Hal = Cl, Br, or I) under mild conditions (EtOH, 50-55 C, 30 min) to afford the corre

Full text of DOI:10.1055/s-0030-1258471

PAPER
1309
An Efficient and General Synthesis of Se-Esters of Diselenophosphinic Acids
via Reaction of Alkali Metal Diselenophosphinates with Organic Halides
S
ynthesis of Se-E
s
l
ters of
e
D
iselenoph
x
osphinic Ac
i
a
ds nder V. Artem’ev, Nataliya A. Chernysheva, Nina K. Gusarova, Svetlana F. Malysheva, Svetlana V. Yas’ko,
Alexander I. Albanov, Boris A. Trofimov*
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk,
Russian Federation
Fax +7(3952)419346 ; E-mail: boris_trofimov@irioch.irk.ru
Received 24 January 2011; revised 10 February 2011
tion of methyl iodide with sodium tert-butylphenyldisele-
Abstract: Alkali metal diselenophosphinates R1 PSe2M (R1 = aryl,
2
nophosphinate,7a generated in situ from tert-butyl-
arylalkyl, hetarylalkyl; M = Na, K, or Cs) readily react with organic
halides R2Hal (R2 = alkyl, allyl, propargyl, benzyl; Hal = Cl, Br, or
I) under mild conditions (EtOH, 50–55 °C, 30 min) to afford the
phenylselenophosphinic chloride and sodium selenide,
which proceeds in acetonitrile to give the methyl ester.
corresponding Se-esters of diselenophosphinic acids R1 P(Se)SeR2
2
in high yields (77–95%).
Ph
Ph
Se
Cl
Ph
Ph
Se, toluene
120 °C, 3 h
P
Cl
P
Key words: diselenophosphinates, organic halides, esters, alkyla-
tion
Se, THF
RMgCl
RSeMgCl
0 °C, 30 min
The last few years have seen considerable expansion in re-
search on the chemistry of diselenophosphinates due to
their applications as ‘single-source’ precursors of remark-
able magneto-optical and semiconducting nanomateri-
als,1,2 ligands for metal complexes,3 promising binary
extractants of heavy metals,4 and prospective pharmaceu-
tical compounds.
Ph
P
Ph
Se
Cl
Ph
Ph
Se
THF
+
RSeMgCl
P
r.t., 1 h
SeR
51–91%
Scheme 1 Multistep synthesis of Se-esters of diphenyldiseleno-
phosphinic acid
In particular, Se-alkyl(aryl) diselenophosphinates
R1 P(Se)SeR2 (R1, R2 = alkyl, aryl) have gained special
2
R
R
R
R
Se
Se
attention as efficient iniferters5 (RAFT-agents) for pseu-
do-living radical polymerization and they are highly
promising candidates for a new generation of pesticides.6
At the same time, the conventional syntheses of these
Se-esters are multistep, tedious, and involve utilizing
moisture- and air-sensitive chlorodiphenylphosphine and
Grignard reagents5,7 (Scheme 1).
EtOH
P
H
+
2 Se
+
MOH
P
M
r.t., 5 min
71–96%
R = aryl, arylalkyl, hetarylalkyl
M = Li, Na, K, Rb, Cs
Scheme 2 General and efficient synthesis of alkali metal diseleno-
phosphinates from secondary phosphines, elemental selenium, and al-
kali metal hydroxides
Therefore, the development of a direct, efficient, and or-
ganometallic-free method for the preparation of Se-esters
of diselenophosphinic acids is highly desirable. Obvious-
ly, one such approach is the reaction of organic halides
with alkali metal diselenophosphinates. The latter are now
accessible since they can be easily prepared from readily
available8 secondary phosphines9 (or secondary phos-
phine selenides10), elemental selenium, and alkali metal
hydroxides under environmentally friendly conditions
(Scheme 2).
Our experiments have shown that the reaction of alkali
metal diselenophosphinates 1–5 with diverse organic ha-
lides occurs under mild conditions (50–55 °C, 30 min) in
ethanol to afford the corresponding Se-esters 6a–n in high
yields (77–95%) (Table 1).
As seen from Table 1, the reaction has a general character.
Various sodium, potassium, and cesium diselenophosphi-
nates, with aryl, arylalkyl, and hetarylalkyl substituents,
and organic chlorides, bromides, and iodides, including
unsaturated examples, participate readily in the studied re-
action.
In this paper, we report a convenient synthesis of Se-esters
of diselenophosphinic acids based on the reaction of alkali
metal diselenophosphinates with organic halides. To our
knowledge, there is no previously published data on such
a reaction in the literature. The only exception is the reac-
Interestingly, reaction of sodium bis[2-(2-pyridyl)eth-
yl]diselenophosphinate (5) with ethyl iodide (Table 1, en-
try 14) proceeds with high degree of selectivity. No
byproducts, in particular, the expected N-ethylpyridinium
iodides, in this alkylation process were found.
SYNTHESIS 2011, No. 8, pp 1309–1313
x
x
.
x
x
.2
0
1
1
Advanced online publication: 10.03.2011
DOI: 10.1055/s-0030-1258471; Art ID: Z14211SS
© Georg Thieme Verlag Stuttgart · New York

1310
A. V. Artem’ev et al.
PAPER
Table 1 Synthesis of Se-Esters of Diselenophosphinic Acids by the Reaction of Diselenophosphinates with Organic Halidesa
R1
R1
Se
Se
R1
R1
Se
EtOH
+
R2 Hal
P
P
M
Se R2
50–55 °C, 30 min
1–5
6a–n
Entry
1
[R1 PSe2]–M+
R1
Ph
Ph
Ph
Ph
Ph
Ph
M
Cs
K
R2-Hal
Product
6a
Yieldb (%)
2
1
MeI
95
91
87
89
92
94
95
84
90
87
90
77
91
2
2
2
2
2
1
3
3
4
4
4
4
3
EtI
6b
6c
3
K
Me(CH2)4Br
Me(CH2)5Br
H2C=CHCH2Br
HC≡CCH2Br
MeI
4
K
6d
6e
5
K
6
Cs
Na
Na
K
6f
7
(CH2)2Ph
(CH2)2Ph
(CH2)2Ph
(CH2)2Ph
(CH2)2Ph
(CH2)2Ph
(CH2)2Ph
6g
8
EtI
6h
6i
9
Me(CH2)4Br
Me(CH2)5Br
BnCl
10
11c
12
13
K
6j
K
6k
6l
K
H2C=CHCH2Br
HC≡CCH2Br
Na
6m
14
5
Na
EtI
6n
79
N
a Reaction conditions: 1–5 (0.50 mmol), R2-Hal (0.51 mmol), EtOH, 50–55 °C, 30 min.
b All yields refer to isolated products.
c Reaction was carried out at 70–75 °C for 90 min.
The synthesized esters are colorless or yellow viscous oils mild conditions (EtOH, 50–55 °C, 30 min) affording the
(except for 6a,c,d,n, the solids), soluble in most organic target Se-esters in high yields. The latter are now available
solvents (acetone, MeCN, EtOH, CHCl3, benzene), insol- due to the developed methodology; they represent highly
uble in water. Their structure unambiguously follows potent inifertes (RAFT-agents) for pseudo-living radical
from multinuclear (31P, 77Se, 1H, 13C) NMR spectra. Thus, polymerization, prospective pesticides, promising build-
in the 31P NMR spectra, a singlet at d = 40.53–52.0 with a ing blocks for organic synthesis, and ligands for the de-
two typical satellite pairs5 was observed. The coupling sign of coordination structures.
constants between the phosphorus and selenium atoms of
Se-esters 6a–n were 1JP-Se = 334–369 Hz and
All steps of the experiment were carried out under a dry inert atmo-
sphere (argon). Brand EtOH (96%) was used in the reaction as a
1JP=Se = 743–791 Hz, which belonged to typical values for
coupling constants for P–Se single and P=Se double
bonds.11 In the 77Se NMR spectra, the doublet signals of
the selenium atom in the P=Se double bond were observed
in the range of d = –254 to –167, whereas the signals of
the selenium atom of the P–Se single bond were observed
in the region d = 130–329. The IR spectrum of the com-
pounds prepared shows strong absorptions at 450–600
cm–1, which can be assigned to the stretching vibrations of
the P=Se double bonds. Elemental analysis of all the com-
pounds isolated support their structures.
solvent without additional purification. Alkali metal diselenophos-
phinates 1–5 were prepared according to the published method.9
Organic halides were distilled prior to use. The 1H, 13C, 31P, and 77Se
NMR spectra were recorded on a Bruker DPX 400 and Bruker AV-
400 spectrometers (400.13, 101.61, 161.98, and 76.31 MHz, respec-
tively) and referenced to H3PO4 (31P NMR) and Me2Se (77Se NMR).
FTIR spectra were run on a Bruker Vertex 70 instrument. Melting
points were measured on a Kofler micro hot stage apparatus and are
uncorrected.
Synthesis of Se-Esters of Diselenophosphinic Acids 6a–n; Gen-
eral Procedure
To a soln of the alkali metal diselenophosphinate 1–5 (0.50 mmol)
in EtOH (6 mL) was added at r.t. the corresponding organic halide
(0.51 mmol). The mixture was stirred at 50–55 °C for 30 min. The
solvent and excess organic halide were removed under reduced
In conclusion, a general and efficient protocol of the reac-
tion between various alkali metal diselenophosphinates
and organic halides to give Se-esters of diselenophosphin-
ic acids has been elaborated. The reaction proceeds under
Synthesis 2011, No. 8, 1309–1313 © Thieme Stuttgart · New York

PAPER
Synthesis of Se-Esters of Diselenophosphinic Acids
1311
pressure, and Et2O (10 mL) was added to the residue. The precipi-
tated white powder (alkali metal halide) was filtered, and Et2O was
evaporated from the filtrate. The residue obtained was dried in
vacuo (1.3 mbar/40–45 °C) to afford the corresponding Se-esters of
diselenophosphinic acids 6a–n.
77Se NMR (76.31 MHz, CDCl3): d = –175 (d, 1JP=Se = 766 Hz), 287
(d, 1JP-Se = 369 Hz).
Anal. Calcd for C17H21PSe2: C, 49.29; H, 5.11; P, 7.48; Se, 38.12.
Found: C, 49.32; H, 5.08; P, 7.27; Se, 38.22.
Se-Hexyl Diphenyldiselenophosphinate (6d)
Light-yellow powder; yield: 89%; mp 42–45 °C.
Se-Methyl Diphenyldiselenophosphinate (6a)
White powder; yield: 95%; mp 56–57 °C.
FTIR (KBr): 3064, 3046, 2956, 2925, 2870, 2854, 1584, 1570,
1476, 1465, 1434, 1410, 1376, 1333, 1308, 1286, 1250, 1190, 1181,
1156, 1115, 1087, 1069, 1025, 996, 846, 755, 746, 705, 690, 641,
618, 549, 513, 477, 426 cm–1.
FTIR (KBr): 3068, 3049, 3016, 2999, 2920, 1968, 1914, 1638,
1581, 1570, 1473, 1454, 1434, 1333, 1308, 1289, 1266, 1196, 1178,
1160, 1132, 1116, 1088, 1069, 1025, 997, 926, 907, 855, 753, 743,
720, 708, 694, 689, 619, 557, 542, 512, 476 cm–1.
3
1H NMR (400.13 MHz, CDCl3): d = 0.83 (t, JHH = 7.2 Hz, 3 H,
2
1H NMR (400.13 MHz, C6D6): d = 2.03 (d, JSeH = 12.8 Hz, 3 H,
Me), 1.20 (m, 4 H, CH2CH2Me), 1.31 (m, 2 H, CH2Pr), 1.62 (m,
3JHH = 7.2 Hz, 2 H, CH2Bu), 3.00 (dt, 3JPH = 12.7 Hz, 3JHH = 7.2 Hz,
2 H, SeCH2), 7.45 (m, 6 H, m-HPh, p-HPh), 7.93 (dm, 3JPH = 14.6 Hz,
4 H, o-HPh).
Me), 8.03–8.12 (m, 10 H, Ph).
13C NMR (101.61 Hz, C6D6): d = 9.6 (Me), 128.5 (d, 2JPC = 13.2 Hz,
o-CPh), 131.5 (d, 4JPC = 2.5 Hz, p-CPh), 132.0 (d, 3JPC = 11.4 Hz, m-
CPh), 134.3 (d, 1JPC = 66.8 Hz, i-CPh).
13C NMR (101.61 MHz, CDCl3): d = 13.8 (Me), 22.3 (CH2Me),
31P NMR (161.98 Hz, C6D6): d = 42.55 (s + dd satellites: JP-Se
=
29.3 (CH2Pr), 30.0 (d, 2JPC = 3.9 Hz, CH2Se), 31.0 (CH2Et), 31.8 (d,
1
3
351 Hz, 1JP=Se = 788 Hz).
3JPC = 2.0 Hz, CH2Bu), 128.3 (d, JPC = 13.0 Hz, o-CPh), 131.5 (d,
2
4JPC = 3.1 Hz, p-CPh), 131.7 (d, JPC = 11.4 Hz, m-CPh), 133.8 (d,
77Se NMR (76.31 Hz, C6D6): d = –188 (d, 1JP=Se = 788 Hz), 216 (d,
1JP-Se = 351 Hz).
1JPC = 68.6 Hz, i-CPh).
31P NMR (161.98 MHz, CDCl3): d = 40.85 (s + dd satellites: 1JP-Se
=
Anal. Calcd for C13H13PSe2: C, 43.60; H, 3.66; P, 8.65; Se, 44.09.
Found: C, 43.49; H, 3.56; P, 8.49; Se, 44.16.
367 Hz, 1JP=Se = 765 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –175 (d, 1JP=Se = 765 Hz), 292
(d, 1JP-Se = 367 Hz).
Se-Ethyl Diphenyldiselenophosphinate (6b)
Light-yellow oil; yield: 91%.
Anal. Calcd for C18H23PSe2: C, 50.48; H, 5.41; P, 7.23; Se, 36.87.
Found: C, 50.62; H, 5.68; P, 7.01; Se, 36.69.
FTIR (film): 3073, 3053, 3006, 2955, 2926, 2869, 2855, 1587,
1573, 1481, 1464, 1436, 1402, 1378, 1333, 1309, 1266, 1243, 1188,
1167, 1130, 1100, 1070, 1027, 998, 924, 883, 847, 747, 720, 708,
691, 643, 548, 531 cm–1.
Se-Prop-2-enyl Diphenyldiselenophosphinate (6e)
Yellow oil; yield: 92%.
3
1H NMR (400.13 MHz, CDCl3): d = 1.36 (t, JHH = 7.5 Hz, 3 H,
FTIR (film): 3073, 3053, 3006, 2976, 2916, 1632, 1585, 1573,
1478, 1436, 1395, 1332, 1308, 1194, 1183, 1159, 1131, 1092, 1069,
1027, 997, 987, 920, 832, 745, 689, 618, 554, 505, 475 cm–1.
Me), 3.00 (dq, 3JPH = 13.1 Hz, 3JHH = 7.5 Hz, 2 H, SeCH2Me), 7.44
(m, 6 H, m-HPh, p-HPh), 7.93 (dm, 3JPH = 14.8 Hz, 4 H, o-HPh).
3
3
13C NMR (101.61 MHz, CDCl3): d = 15.8 (d, JPC = 4.4 Hz, Me),
1H NMR (400.13 MHz, CDCl3): d = 3.67 (dddd, JPH = 12.2 Hz,
25.7 (d, 2JPC = 2.2 Hz, SeCH2Me), 128.5 (d, 2JPC = 12.8 Hz, o-CPh),
131.7 (d, JPC = 3.3 Hz, p-CPh), 131.8 (d, JPC = 11.4 Hz, m-CPh),
3JHH = 7.6 Hz, 4JHH = 7.6 Hz, 4JHH = 0.8 Hz, 2 H, CH2Se), 4.95 (dd,
3Jcis = 10.0 Hz, 1 Hcis, =CH2), 5.17 (dddd, Jtrans = 16.8 Hz,
4
3
3
133.9 (d, 1JPC = 67.9 Hz, i-CPh).
2JHH = 1.3 Hz, 1 Htrans, =CH2), 5.81 (ddt, 1 H, =CH), 7.40–7.50 (m,
6 H, m-HPh, p-HPh), 7.90, 7.93 (dm, 3JPH = 14.7 Hz, 4 H, o-HPh).
31P NMR (161.98 MHz, CDCl3): d = 40.53 (s + dd satellites: 1JP-Se
367 Hz, 1JP=Se = 766 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –177 (d, 1JP=Se = 766 Hz), 321
=
13C NMR (101.61 MHz, CDCl3): d = 34.0 (d, JPC = 2.2 Hz,
2
3
CH2Se), 118.5 (=CH2), 128.6 (d, JPC = 13.2 Hz, o-CPh), 131.8 (d,
4JPC = 3.3 Hz, p-CPh), 132.0 (d, JPC = 11.7 Hz, m-CPh), 133.5 (d,
2
(d, 1JP-Se = 367 Hz).
3JPC = 4.8 Hz, =CH), 133.7 (d, 1JPC = 67.5 Hz, i-CPh).
Anal. Calcd for C14H15PSe2: C, 45.18; H, 4.06; P, 8.32; Se, 42.43.
Found: C, 45.38; H, 4.06; P, 8.12; Se, 42.44.
31P NMR (161.98 MHz, CDCl3): d = 40.93 (s + dd satellites: 1JP-Se
=
362 Hz, 1JP=Se = 769 Hz).
Se-Pentyl Diphenyldiselenophosphinate (6c)
Light-yellow powder; yield: 87%; mp 40–42 °C.
77Se NMR (76.31 MHz, CDCl3): d = –167 (d, 1JP=Se = 769 Hz), 329
(d, 1JP-Se = 362 Hz).
FTIR (KBr): 3066, 3047, 2955, 2926, 2868, 2855, 1584, 1570,
1475, 1464, 1435, 1412, 1376, 1333, 1309, 1289, 1266, 1243, 1193,
1182, 1158, 1087, 1069, 1025, 996, 848, 759, 747, 706, 691, 646,
630, 618, 549, 513, 479, 426 cm–1.
Anal. Calcd for C15H15PSe2: C, 46.90; H, 3.94; P, 8.06; Se, 41.11.
Found: C, 47.02; H, 3.99; P, 7.93; Se, 41.15.
Se-Prop-2-ynyl Diphenyldiselenophosphinate (6f)
Yellow oil; yield: 94%.
3
1H NMR (400.13 MHz, CDCl3): d = 0.81 (t, JHH = 7.2 Hz, 3 H,
Me), 1.23 (m, 2 H, CH2Me), 1.30 (m, 2 H, CH2Et), 1.63 (m,
3JHH = 7.5 Hz, 2 H, CH2Pr), 2.99 (dt, 3JPH = 12.8 Hz, 3JHH = 7.5 Hz,
2 H, SeCH2), 7.40–7.49 (m, 6 H, m-HPh, p-HPh), 7.92 (dm,
3JPH = 14.7 Hz, 4 H, o-HPh).
FTIR (film): 3360, 3303, 3072, 3053, 2934, 2884, 1658, 1614,
1586, 1573, 1554, 1479, 1454, 1436, 1409, 1331, 1308, 1277, 1261,
1231, 1193, 1187, 1159, 1128, 1096, 1069, 1042, 1028, 998, 972,
923, 845, 812, 799, 746, 690, 582, 553, 502, 475 cm–1.
3
13C NMR (101.61 MHz, CDCl3): d = 14.0 (Me), 22.2 (CH2CMe),
1H NMR (400.13 MHz, C6D6): d = 1.16 (dd, JHH = 2.7 Hz, 1 H,
3
30.0 (d, JPC = 3.7 Hz, CH2Pr), 32.02 (CH2Et), 32.04 (SeCH2),
HC≡), 2.88 (dd, 3JHH = 2.7 Hz, 2JSeH = 12.0 Hz, 2 H, CH2C≡), 7.29–
3
4
128.6 (d, JPC = 13.3 Hz, o-CPh), 131.8 (d, JPC = 3.0 Hz, p-CPh),
7.35 (m, 10 H, Ph).
132.0 (d, 2JPC = 11.4 Hz, m-CPh), 134.2 (d, 1JPC = 67.8 Hz, i-CPh).
13C NMR (101.61 Hz, C6D6): d = 17.3 (CH2), 73.3 (HC≡), 79.8
31P NMR (161.98 MHz, CDCl3): d = 40.82 (s + dd satellites: 1JP-Se
369 Hz, 1JP=Se = 766 Hz).
=
(≡CCH2), 128.6 (d, 2JPC = 13.2 Hz, o-CPh), 131.8 (d, 4JPC = 2.7 Hz,
Synthesis 2011, No. 8, 1309–1313 © Thieme Stuttgart · New York

1312
A. V. Artem’ev et al.
PAPER
p-CPh), 132.2 (d, 3JPC = 11.4 Hz, m-CPh), 134.00 (d, 1JPC = 68.2 Hz,
i-CPh).
13C NMR (101.61 MHz, CDCl3): d = 13.9 (Me), 22.2 (CH2Me),
30.2 (d, 2JPC = 2.9 Hz, CH2Ph), 31.0 (d, 2JPC = 2.7 Hz, CH2Se), 31.9
(d, JPC = 2.4 Hz, CH2Pr), 32.0 (CH2Et), 39.4 (d, JPC = 36.6 Hz,
CH2P), 126.5 (p-CPh), 128.3 (o-CPh), 128.7 (m-CPh), 140.2 (d,
3JPC = 17.0 Hz, i-CPh).
3
1
1
31P NMR (161.98 Hz, C6D6): d = 43.31 (s + dd satellites: JP-Se
=
344 Hz, 1JP=Se = 791 Hz).
77Se NMR (76.31 Hz, C6D6): d = –174 (d, 1JP=Se = 791 Hz), 210 (d,
1JP-Se = 344 Hz).
31P NMR (161.98 MHz, CDCl3): d = 48.72 (s + dd satellites: 1JP-Se
=
355 Hz, 1JP=Se = 746 Hz).
Anal. Calcd for C15H13PSe2: C, 47.14; H, 3.43; P, 8.10; Se, 41.32.
Found: C, 47.04; H, 3.39; P, 7.96; Se, 41.25.
77Se NMR (76.31 MHz, CDCl3): d = –248 (d, 1JP=Se = 746 Hz), 214
(d, 3JP-Se = 355 Hz).
Se-Methyl Bis(2-phenylethyl)diselenophosphinate (6g)
Colorless oil; yield: 95%.
Anal. Calcd for C21H29PSe2: C, 53.63; H, 6.21; P, 6.59; Se, 33.58.
Found: C, 53.75; H, 6.34; P, 6.38; Se, 33.49.
FTIR (film): 3084, 3061, 3026, 3001, 2921, 2860, 2809, 2631,
2604, 1949, 1874, 1807, 1776, 1744, 1656, 1648, 1602, 1583, 1545,
1496, 1453, 1416, 1396, 1323, 1271, 1210, 1197, 1180, 1156, 1131,
1073, 1029, 1006, 946, 911, 851, 837, 747, 698, 636, 621, 576, 507,
472 cm–1.
Se-Hexyl Bis(2-phenylethyl)diselenophosphinate (6j)
Light-yellow oil; yield: 87%.
FTIR (film): 3085, 3062, 3026, 2955, 2926, 2855, 1602, 1584,
1496, 1454, 1397, 1378, 1251, 1234, 1210, 1195, 1156, 1131, 1071,
1030, 1005, 945, 908, 837, 746, 698, 577, 556, 507, 473 cm–1.
2
1H NMR (400.13 MHz, C6D6): d = 0.90 (d, JSeH = 12.2 Hz, 3 H,
Me), 1.06–1.22 (m, 4 H, CH2P), 1.74–1.99 (m, 4 H, CH2Ph), 5.89–
6.09 (m, 10 H, Ph).
1H NMR (400.13 MHz, CDCl3): d = 0.95 (m, 3 H, Me), 1.36 (m, 4
H, CH2CH2Me), 1.48 (m, 2 H, CH2Pr), 1.82 (m, 2 H, CH2Bu), 2.61
2
3
(m, 4 H, CH2P), 3.04 (dt, JSeH = 12.3 Hz, JHH = 7.2 Hz, 2 H,
CH2Se), 2.94–3.16 (m, 4 H, CH2Ph), 7.17 (m, 4 H, o-HPh), 7.23 (m,
2 H, p-HPh), 7.33 (m, 4 H, m-HPh, Ph).
13C NMR (101.61 Hz, C6D6): d = 9.8 (Me), 30.3 (CH2Ph), 39.2 (d,
1JPC = 36.8 Hz, CH2P), 126.5 (p-CPh), 128.58 (o-CPh), 128.74 (m-
CPh), 140.55 (d, 3JPC = 16.8 Hz, i-CPh).
13C NMR (101.61 MHz, CDCl3): d = 14.0 (Me), 22.5 (CH2Me),
1
31P NMR (161.98 Hz, C6D6): d = 49.85 (s + dd satellites: JP-Se
=
29.5 (CH2Pr), 30.1 (d, 2JPC = 2.9 Hz, CH2Ph), 31.22 (CH2Bu), 31.23
340 Hz, 1JP=Se = 768 Hz).
3
1
(CH2Et), 31.9 (d, JPC = 2.2 Hz, CH2Se), 39.4 (d, JPC = 36.7 Hz,
CH2P), 126.5 (p-CPh), 128.3 (o-CPh), 128.6 (m-CPh), 140.1 (d,
3JPC = 16.9 Hz, i-CPh).
77Se NMR (76.31 Hz, C6D6): d = –254 (d, 1JP=Se = 768 Hz), 132 (d,
1JP-Se = 340 Hz).
31P NMR (161.98 MHz, CDCl3): d = 48.68 (s + dd satellites: 1JP-Se
=
Anal. Calcd for C17H21PSe2: C, 49.29; H, 5.11; P, 7.48; Se, 38.12.
Found: C, 49.15; H, 5.18; P, 7.31; Se, 38.25.
356 Hz, 1JP=Se = 747 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –248 (d, 1JP=Se = 747 Hz), 213
(d, 1JP-Se = 356 Hz).
Se-Ethyl Bis(2-phenylethyl)diselenophosphinate (6h)
Light-yellow oil; yield: 84%.
Anal. Calcd for C22H31PSe2: C, 54.55; H, 6.45; P, 6.39; Se, 32.60.
Found: C, 54.68; H, 6.61; P, 6.22; Se, 32.44.
FTIR (film): 3084, 3061, 3026, 3001, 2957, 2920, 2863, 1603,
1584, 1496, 1453, 1396, 1373, 1323, 1266, 1233, 1211, 1180, 1156,
1131, 1071, 1030, 1005, 960, 945, 909, 837, 747, 698, 577, 555,
507, 472 cm–1.
Se-Benzyl Bis(2-phenylethyl)diselenophosphinate (6k)
Light-yellow oil; yield: 90%.
3
1H NMR (400.13 MHz, CDCl3): d = 1.52 (t, JHH = 7.5 Hz, 3 H,
FTIR (film): 3084, 3061, 3026, 2924, 2862, 1602, 1583, 1495,
1453, 1396, 1266, 1216, 1180, 1131, 1069, 1030, 1005, 945, 911,
832, 750, 696, 603, 577, 551, 506, 471 cm–1.
1H NMR (400.13 MHz, CDCl3): d = 2.52 (m, 4 H, CH2P), 2.96 (m,
4 H, CH2Ph), 4.26 (d, 3JPH = 12.3 Hz, 2 H, CH2Se), 7.15 (m, 4 H, o-
HPh), 7.20 (m, 2 H, p-HPh), 7.30 (m, 4 H, m-HPh), 7.20–7.35 (m, 3 H,
m-HBn, p-HBn), 7.47 (m, 2 H, o-HBn).
Me), 2.57 (m, 4 H, CH2P), 3.01 (dq, 3JPH = 13.1 Hz, 3JHH = 7.5 Hz,
2 H, CH2Se), 2.95–3.08 (m, 4 H, CH2Ph), 7.21 (m, 4 H, o-HPh), 7.22
(m, 2 H, p-HPh), 7.30 (m, 4 H, m-HPh).
3
13C NMR (101.61 MHz, CDCl3): d = 16.9 (d, JPC = 3.3 Hz, Me),
25.8 (d, 2JPC = 2.6 Hz, CH2Se), 30.1 (d, 2JPC = 2.9 Hz, CH2Ph), 39.4
(d, 1JPC = 37.1 Hz, CH2P), 126.5 (p-CPh), 128.3 (o-CPh), 128.6 (m-
CPh), 140.1 (d, 3JPC = 16.9 Hz, i-CPh).
2
13C NMR (101.61 MHz, CDCl3): d = 30.1 (d, JPC = 2.9 Hz,
31P NMR (161.98 MHz, CDCl3): d = 48.46 (s + dd satellites: 1JP-Se
=
2
1
CH2Ph), 34.6 (d, JPC = 2.4 Hz, CH2Se), 38.9 (d, JPC = 36.1 Hz,
CH2P), 126.4 (p-CPh), 127.4 (p-CBn), 128.2 (o-CPh), 128.6 (o-CBn,
m-CBn, o-CPh, m-CPh), 129.4 (m-CBn), 138.4 (d, 3JPC = 3.1 Hz, i-CBn),
140.0 (d, 3JPC = 16.9 Hz, i-CPh).
354 Hz, 1JP=Se = 747 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –251 (d, 1JP=Se = 747 Hz), 241
(d, 3JP-Se = 354 Hz).
31P NMR (161.98 MHz, CDCl3): d = 49.21 (s + dd satellites: 1JP-Se
=
Anal. Calcd for C18H23PSe2: C, 50.48; H, 5.41; P, 7.23; Se, 36.87.
Found: C, 50.61; H, 5.47; P, 7.10; Se, 36.82.
353 Hz, 1JP=Se = 748 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –230 (d, 1JP=Se = 748 Hz), 304
(d, 1JP-Se = 353 Hz).
Se-Pentyl Bis(2-phenylethyl)diselenophosphinate (6i)
Light-yellow oil; yield: 90%.
Anal. Calcd for C23H25PSe2: C, 56.34; H, 5.14; P, 6.32; Se, 32.21.
Found: C, 56.40; H, 5.19; P, 6.17; Se, 32.27.
FTIR (film): 3085, 3062, 3026, 2955, 2927, 2869, 2858, 1603,
1584, 1496, 1454, 1397, 1379, 1267, 1243, 1198, 1180, 1157, 1131,
1071, 1030, 1006, 945, 908, 837, 747, 698, 577, 556, 507, 473 cm–1.
Se-Prop-2-enyl Bis(2-phenylethyl)diselenophosphinate (6l)
Orange oil; yield: 77%.
3
1H NMR (400.13 MHz, CDCl3): d = 0.91 (t, JHH = 7.1 Hz, 3 H,
3
Me), 1.38 (m, 4 H, CH2CH2Me), 1.78 (m, JHH = 7.1 Hz, 2 H,
FTIR (film): 3084, 3062, 3026, 2975, 2919, 2862, 1632, 1603,
1584, 1496, 1454, 1425, 1396, 1267, 1210, 1196, 1156, 1131, 1071,
1030, sh 1004, 988, 945, 921, 855, 835, 747, 697, 577, 556, 506,
471 cm–1.
3
3
CH2Pr), 2.56 (m, 4 H, CH2P), 3.00 (dt, JPH = 12.8 Hz, JHH = 7.1
Hz, 2 H, CH2Se), 2.89–3.12 (m, 4 H, CH2Ph), 7.21 (m, 6 H, o-HPh,
p-HPh), 7.30 (m, 4 H, m-HPh).
Synthesis 2011, No. 8, 1309–1313 © Thieme Stuttgart · New York

PAPER
Synthesis of Se-Esters of Diselenophosphinic Acids
1313
1H NMR (400.13 MHz, CDCl3): d = 2.57 (m, 4 H, CH2P), 3.00 (m,
4 H, CH2Ph), 3.67 (dd, 3JHH = 7.6 Hz, 3JPH = 12.6 Hz, 2 H, CH2Se),
5.11 (d, Jcis = 9.8 Hz, 1 Hcis, =CH2), 5.34 (d, Jtrans = 16.9 Hz, 1
Htrans, =CH2), 5.81 (ddt, 1 H, =CH), 7.20 (m, 4 H, o-HPh), 7.22 (m,
2 H, p-HPh), 7.30 (m, 4 H, m-HPh).
Acknowledgment
3
3
This work has been carried out under financial support of leading
scientific schools (Grant NSh-3230.2010.3) and young Russian
Scientists (grant MK-629-2010.3) by the President of the Russian
Federation.
2
13C NMR (101.61 MHz, CDCl3): d = 30.2 (d, JPC = 2.9 Hz,
2
1
CH2Ph), 33.8 (d, JPC = 2.2 Hz, CH2Se), 39.2 (d, JPC = 36.3 Hz,
CH2P), 118.5 (=CH2), 126.6 (p-CPh), 128.4 (o-CPh), 128.8 (m-CPh),
134.7 (d, 3JPC = 2.8 Hz, =CH), 140.2 (d, 3JPC = 16.9 Hz, i-CPh).
References
(1) For reviews, see: (a) Fan, D.; Afzaal, M.; Mallik, M. A.;
Nguyen, C. Q.; O’Brien, P.; Thomas, P. J. Coord. Chem.
Rev. 2007, 251, 1878. (b) Malik, M. A.; Afzaal, M.;
O’Brien, P. Chem. Rev. 2010, 110, 4417.
31P NMR (161.98 MHz, CDCl3): d = 49.61 (s + dd satellites: 1JP-Se
=
353 Hz, 1JP=Se = 743 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –237 (d, 1JP=Se = 743 Hz), 252
(d, 1JP-Se = 353 Hz).
(2) For examples of heavy-metal diselenophosphinates applies
as single-source precursors of nanomaterials, see:
(a) Nguyen, C. Q.; Afzaal, M.; Malik, M. A.; Helliwell, M.;
Raftery, J.; O’Brien, P. J. Organomet. Chem. 2007, 692,
2669. (b) Panneerselvam, A.; Nguyen, C. Q.; Waters, J.;
Malik, M. A.; O’Brien, P.; Raftery, J.; Helliwell, M. Dalton
Trans. 2008, 4499. (c) Hasegawa, Y.; Adachi, T.; Tanaka,
A.; Afzaal, M.; O’Brien, P.; Doi, T.; Hinatsu, Y.; Fujita, K.;
Tanaka, K.; Kawai, T. J. Am. Chem. Soc. 2008, 130, 5710.
(d) Maneeprakorn, W.; Nguyen, C. Q.; Malik, M. A.;
O’Brien, P.; Raftery, J. Dalton Trans. 2009, 2103.
(e) Panneerselvam, A.; Nguyen, C. Q.; Malik, M. A.;
O’Brien, P.; Raftery, J. J. Mater. Chem. 2009, 19, 419.
(f) Tanaka, A.; Adachi, T.; Hasegawa, Y.; Kawai, T. J.
Alloys Compd. 2009, 488, 538. (g) Kawai, T.; Hasegawa,
Y.; Adachi, T. US 20,090,015,919, 2009.
(h) Maneeprakorn, W.; Malik, M. A.; O’Brien, P. J. Mater.
Chem. 2010, 20, 2329.
(3) Lobana, T. S.; Wang, J.-C.; Liu, C. W. Coord. Chem. Rev.
2007, 251, 91.
(4) Egorova, N. S.; Belova, V. V.; Voshkin, A. A.; Zhilov, V. I.;
Kholkin, A. I. Russ. J. Inorg. Chem. (Engl. Transl.) 2005,
50, 1902.
(5) (a) Moon, J.; Nam, H.; Kim, S.; Ryu, J.; Han, C.; Lee, C.;
Lee, S. Tetrahedron Lett. 2008, 49, 5137. (b) Song, E.; Jo,
Y.; Bae, G.; Oh, I.-K.; Jung, H. M.; Lee, S. Bull. Korean
Chem. Soc. 2009, 30, 2129.
Anal. Calcd for C19H23PSe2: C, 51.83; H, 5.27; P, 7.04; Se, 35.87.
Found: C, 51.95; H, 5.42; P, 6.96; Se, 35.62.
Se-Prop-2-ynyl Bis(2-phenylethyl)diselenophosphinate (6m)
Yellow viscous oil; yield: 91%.
FTIR (film): 3085, 3062,, 3026, 3002, 2928, 2892, 2863, 2783,
2603, 2385, 2337, 2208, 2114, 1949, 1877, 1807, 1748, 1602, 1583,
1496, 1453, 1437, 1395, 1319, 1289, 1266, 1210, 1191, 1156, 1131,
1071, 1030, 1005, 945, 909, 852, 837, 810, 747, 735, 698, 648, 576,
556, 506, 482, 470, 398 cm–1.
1H NMR (400.13 MHz, C6D6): d = 1.80–1.84 (m, 1 H, ≡CH), 2.05–
2.23 (m, 4 H, CH2P), 2.72–2.95 (m, 4 H, CH2Ph), 3.32–3.35 (m, 2
H, CH2), 6.86–7.07 (m, 10 H, Ph).
13C NMR (101.61 Hz, C6D6): d = 16.4 (CH2), 30.0 (CH2Ph), 38.5
1
(d, JPC = 36.4 Hz, CH2P), 72.7 (HC≡), 80.8 (≡CCH2), 126.3 (p-
CPh), 128.3 (o-CPh), 128.5 (m-CPh), 140.1 (d, 3JPC = 16.6 Hz, i-CPh).
1
31P NMR (161.98 Hz, C6D6): d = 52.50 (s + dd satellites: JP-Se
=
334 Hz, 1JP=Se = 770 Hz).
77Se NMR (76.31 Hz, C6D6): d = –250 (d, 1JP=Se = 770 Hz), 130 (d,
1JP-Se = 334 Hz).
Anal. Calcd for C19H21PSe2: C, 52.07; H, 4.83; P, 7.07; Se, 36.03.
Found: C, 52.11; H, 4.86; P, 7.01; Se, 36.10.
Se-Ethyl Bis[2-(2-pyridyl)ethyl]diselenophosphinate (6n)
Light-yellow powder; yield: 79%; mp 31–34 °C.
(6) Matolcsy, G.; Nadasy, M.; Andriska, V. Pesticide
Chemistry; Elsevier: Budapest, 1988.
(7) (a) Kimura, T.; Murai, T. J. Org. Chem. 2005, 70, 952.
(b) Kimura, T.; Murai, T.; Mizuhata, N. Heteroat. Chem.
2005, 16, 185. (c) Murai, T.; Kimura, T. Curr. Org. Chem.
2006, 10, 1963.
FTIR (KBr): 3080, 3063, 3043, 3003, 2956, 2921, 2860, 1592,
1567, 1474, 1434, 1405, 1372, 1317, 1289, 1272, 1231, 1201, 1148,
1131, 1083, 1049, 1034, 993, 958, 942, 883, 838, 829, 771, 749,
731, 705, 628, 595, 590, 553, 510, 494, 475, 437, 418 cm–1.
(8) For reviews about the availability of secondary phosphines
from red phosphorus, see: (a) Trofimov, B. A.; Arbuzova, S.
N.; Gusarova, N. K. Russ. Chem. Rev. (Engl. Transl.) 1999,
68, 215. (b) Trofimov, B. A.; Gusarova, N. K. Mendeleev
Commun. 2009, 19, 295.
(9) For examples of synthesis of alkali metal diselenophos-
phinates from secondary phosphines, see: Artem’ev, A. V.;
Malysheva, S. F.; Gusarova, N. K.; Trofimov, B. A.
Synthesis 2010, 2463.
(10) For examples of synthesis of alkali metal diselenophos-
phinates from secondary phosphine selenides, see:
Trofimov, B. A.; Artem’ev, A. V.; Malysheva, S. F.;
Gusarova, N. K. J. Organomet. Chem. 2009, 694, 4116.
(11) (a) Duddeck, H. Prog. Nucl. Magn. Reson. Spectrosc. 1995,
27, 1. (b) Duddeck, H. In Encyclopedia of Nuclear
Magnetic Resonance, Vol. 7; Grant, D. M.; Harris, R. K.,
Eds.; Wiley: New York, 1996, 4623.
3
1H NMR (400.13 MHz, CDCl3): d = 1.46 (t, JHH = 7.6 Hz, 3 H,
Me), 2.78 (m, 4 H, CH2P), 2.94 (dq, 3JPH = 12.9 Hz, 2 H, CH2Me),
3.20 (m, 4 H, CH2Py), 7.10 (dd, 3JH5-H4 = 7.6 Hz, 3JH5-H6 = 5.6 Hz, 2
H, H5Py), 7.18 (d, 3JH3-H4 = 7.7 Hz, 2 H, H3Py), 7.57 (ddd, 3JH4-H5
=
3
4
7.7 Hz, JH4-H3 = 7.7 Hz, JH4-H6 = 1.8 Hz, 2 H, H4Py), 8.46 (br d,
3JH6-H5 = 5.6 Hz, 2 H, H6Py).
3
13C NMR (101.61 MHz, CDCl3): d = 16.8 (d, JPC = 3.3 Hz, Me),
25.7 (d, 2JPC = 2.6 Hz, CH2Se), 32.3 (d, 2JPC = 2.0 Hz, CH2Py), 36.8
(d, 1JPC = 39.4 Hz, CH2P), 121.6 (C5Py), 123.2 (C3Py), 136.6 (C4Py),
149.4 (C6Py), 159.6 (d, 3JPC = 17.2 Hz, C2Py).
31P NMR (161.98 MHz, CDCl3): d = 49.40 (s + dd satellites: 1JP-Se
=
359 Hz, 1JP=Se = 745 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –253 (d, 1JP=Se = 745 Hz), 245
(d, 1JP-Se = 359 Hz).
Anal. Calcd for C16H21N2PSe2: C, 44.67; H, 4.92; N, 6.51; P, 7.20;
Se, 36.70. Found: C, 44.75; H, 4.99; N, 6.33; P, 7.07; Se, 36.61.
Synthesis 2011, No. 8, 1309–1313 © Thieme Stuttgart · New York