Efficient general synthesis of alkylammonium diselenophosphinates via multicomponent one-pot reaction of secondary phosphines with elemental selenium and amines

Article abstract of DOI:10.1055/s-0030-1258232

The multicomponent reaction between secondary phosphines, elemental selenium, and primary, secondary, or tertiary amines is accomplished efficiently in ethanol (60C, 0.5 h) to give the corresponding mono-, di-, or trialkylammonium diselenophosphinates in

Full text of DOI:10.1055/s-0030-1258232

3724
PAPER
Efficient General Synthesis of Alkylammonium Diselenophosphinates via
Multicomponent One-Pot Reaction of Secondary Phosphines with Elemental
Selenium and Amines
S
ynthesis of
A
lkyl
l
a
mmon
e
ium
D
isele
x
nophosphina
a
tes nder V. Artem’ev, Nina K. Gusarova, Svetlana F. Malysheva, Peter B. Kraikivskii, Nataliya A. Belogorlova,
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 5 July 2010; revised 13 July 2010
sess features typical for ammonium compounds, includ-
Abstract: The multicomponent reaction between secondary phos-
ing those applied in pharmaceutics as well as protonic
phines, elemental selenium, and primary, secondary, or tertiary
ionic liquids.14
amines is accomplished efficiently in ethanol (60 °C, 0.5 h) to give
the corresponding mono-, di-, or trialkylammonium diselenophos-
phinates in high yield (up to 97%).
At the same time, the conventional synthesis of alkylam-
monium diselenophosphinates is multistep and laborious
Key words: secondary phosphines, elemental selenium, amines,
three-component reaction, diselenophosphinates
and requires aggressive and poisonous phosphorus ha-
lides and flammable unstable organometallic reactants.10
Triethylammonium diselenophosphinates were prepared
by the multistep reaction of toxic and unavailable
monochlorophosphines R2PCl with triethylsilane, triethyl-
amine, and selenium in toluene by reflux for period of ca.
20 hours.10 Furthermore, the reaction resulted in some
byproducts together with the target compounds
(Scheme 1).
In recent years, the chemistry of diselenophosphinates has
received special attention due to their potential and prac-
tical applications as SSPs (single-source precursors) of
magneto-optical and semiconducting nanomaterials,1
ligands for metal complexes,2 building blocks for organic
and elemento-organic synthesis,3 promising extractants of
heavy elements,4 and prospective pharmaceutical com-
pounds.5 For example, heavy metal diselenophosphinates
are now employed as efficient SSPs for the preparation of
metal phosphide or selenide nanoparticles possessing
many unique properties.6 Nickel and cobalt dialkyldisele-
HSiEt3, Et3N, r.t., 6 h
– [Et3NH]Cl
Se, Et3N
R2PCl
R2PSiEt3
[R2PSe2][HNEt3]
toluene,
refluxed, 20 h
– Si2Et6
R = i-Pr, t-Bu, Ph
Scheme 1 Preparation of triethylammonium diselenophosphinates
nophosphinates are used for the synthesis of phosphide or from R2PCl, triethylsilane, triethylamine and selenium10
selenide nanoparticles with good electrical, semiconduc-
tive, and magnetic properties.7 Silver diselenophosphinate
Recently, a facile synthesis of alkylammonium diseleno-
is employed as an SSP to obtain silver selenide nano-
phosphinates from secondary phosphine selenides,
films.8 Europium diselenophosphinates are actively ap-
R2P(Se)H, elemental selenium, and amines was report-
ed.15 Secondary phosphine selenides were obtained by the
oxidation of secondary phosphines R2PH by elemental se-
lenium. The data on the possible variation in the second-
ary phosphines in this reaction are limited in the short
communication which covers only the reaction of bis(2-
phenylethyl)phosphine with selenium and diethylamine
or diisopropylamine.16 Therefore, the scope and synthetic
importance of this synthesis have not been examined. In
particular, it is unclear what amines and secondary phos-
phines can be employed in this synthesis.
plied to design europium selenide nanocrystals showing
remarkable magneto-optical properties.9 Nanorods of zinc
selenide exhibiting semiconductive properties have been
synthesized from zinc diselenophosphinate.10 In 2010, P.
O’Brien et. al. developed the efficient synthesis of CoSe2,
CoP, or Co2P nanoparticles from cobalt diselenophosphi-
nates, [Co(Se2PR2)2].11
The convenient syntheses of the aforementioned heavy
metal diselenophosphinates are based on the reaction of
alkylammonium diselenophosphinates with heavy metal
halides.7–11 In addition, alkylammonium diselenophosph-
inates are key intermediates in the synthesis of Se-esters
of diselenophosphinic acids.3 The latter represent efficient
iniferters12 and prospective pesticides.13 One might expect
that alkylammonium diselenophosphinates will also pos-
Thus, the aim of this work is to evaluate the true generality
of this promising reaction. We have systematically stud-
ied the reaction of various secondary phosphines with el-
emental selenium and primary, secondary, or tertiary
amines.
The experiments have shown that the three-component re-
action between secondary phosphines 1–8, elemental se-
lenium, and amines proceeds under mild conditions (60
SYNTHESIS 2010, No. 21, pp 3724–3730
Advanced online publication: 25.08.2010
DOI: 10.1055/s-0030-1258232; Art ID: Z17010SS
x
x.
x
x
.
2
0
1
0
© Georg Thieme Verlag Stuttgart · New York

PAPER
Synthesis of Alkylammonium Diselenophosphinates
3725
Table 1 One-Pot Synthesis of Alkylammonium Diselenophosphinates from Secondary Phosphines, Elemental Selenium, and Amines
R1
R1
R1
Se
Se
EtOH
+ 2 Se + NR2nH3–n
H
NR2nH3–n
P
H
P
60 °C, 0.5 h
R1
1–8
9a–n
Entry
Phosphine
R1
Amine, NR2 H3–n
Product
9a
Yielda (%)
n
1
2
3
4
5
6
7
1
1
2
2
2
2
3
Ph
Ph
Et3N
92
97
88
91
94
85
87
allylNH2
Et3N
9b
(CH2)2Ph
(CH2)2Ph
(CH2)2Ph
(CH2)2Ph
9c
Et2NH
i-Pr2NH
allylNH2
i-Pr2NH
9d
9e
9f
CH2CH(Me)Ph
9g
8
4
Et3N
9h
85
t-Bu
9
10
11
12
5
6
7
7
Pr2NH
Et3N
9i
94
91
89
94
N
9j
9k
9l
N
Et3N
N
N
allylNH2
13
14
8
8
Et3N
9m
9n
87
96
O
O
allylNH2
a All yields refer to isolated products.
°C, 0.5 h) in ethanol to afford diselenophosphinates 9a–n The general character of the reaction is additionally sup-
in 85–97% yields (Table 1).
ported by the fact that chiral and functional amines can
also be employed in this reaction. For example, secondary
phosphine 2 easily reacts with elemental selenium and op-
tically active (R)-1-aminobutan-2-ol (EtOH, 60 °C, 0.5 h)
to furnish diselenophosphinate 9o in 86% yield
(Scheme 2).
As seen from Table 1, the reaction was found to be of gen-
eral character. Various secondary phosphines with aryl,
arylalkyl, and hetarylalkyl substituents as well as primary,
secondary, and tertiary amines including an unsaturated
one participate readily in this three-component reaction.
The choice of initial secondary phosphines 2–8 is not ar-
bitrary since these phosphines are now easily prepared
Se
EtOH
H2N
2 + 2 Se +
P
H3N
60 °C, 0.5 h
OH
Se
OH
9o
Scheme 2 Synthesis of optically active diselenophosphinate 9o
Synthesis 2010, No. 21, 3724–3730 © Thieme Stuttgart · New York

3726
A. V. Artem’ev et al.
PAPER
from red phosphorus and vinylarenes or vinylhetarenes
(e.g., styrenes,17 vinylpyridines,18 2-vinylfuran17) in one
step.
The synthesized salts are crystalline colorless compounds
that are soluble in most organic solvents (acetone, MeCN,
CHCl3, DMSO, EtOH, MeOH), but they are insoluble in
water. Their structure unambiguously follows from X-ray
analysis data and 31P, 77Se, 1H, and 13C NMR spectra.
X-ray diffraction studies of diselenophosphinates 9d,e
have shown that the molecular structure of these salts is
formed by the anion of the bis(2-phenylethyl)diseleno-
phosphinic acid and cation of diethylammonium or diiso-
propylammonium, respectively (Figure 1 and Figure 2).
The geometry of the anion in compounds 9d,e is charac-
terized by high symmetry relative to the phosphorus atom.
The coordination geometry around phosphorus is a dis-
torted tetrahedral with the bond angles ranging between
102.4 and 114.46°. The P–Se bond lengths of 2.130–2.158
Å are intermediate between those expected for P–Se sin-
gle (2.26 Å)19 and P=Se (2.09 Å)20 bonds and it is indica-
tive of delocalization of the negative charge across the
PSe2 unit and a P–Se bond order of 1.5. This delocaliza-
tion can also be observed in solution using 31P NMR spec-
Figure 2 Thermal ellipsoid plot (50% probability) of the structure
of 9e
ary phosphine selenide B. The latter is deprotonated by
the amine to afford selenophosphinite anion C (stage 2),
which further reacts with a second equivalent of elemental
selenium to provide the diselenophosphinate anion D
(stage 3).
1
troscopy from the JPSe coupling constant (556–621 Hz),
which is midway between the expected values for P–Se
(200–600 Hz) and P=Se (800–1200 Hz) bonds.21 In the
77Se NMR spectra, the doublet with 1JSeP = 556–621 Hz at
d = 24–(–76) confirms also the chemical equivalency of
both selenium atoms of the PSe2 fragment. The IR spec-
trum of the compounds synthesized shows strong absorp-
tions at 530–560 and 460–470 cm–1 which can be assigned
to the asymmetric (nas) and symmetric (ns) stretching vi-
brations of the PSe2 groups. The elemental analysis of all
the compounds isolated corresponds to their structures.
Se
Se
Se
H
Se
NRnH3–n
(2)
Se
(1)
Se
(3)
••
P
H
P
P
P
Se
P
A
B
C
D
Scheme 3 Probable mechanism of alkylammonium diselenophos-
phinates formation
To summarize, a general and efficient operationally con-
venient protocol of the multicomponent reaction between
various secondary phosphines, elemental selenium, and
aliphatic amines to give mono-, di-, or trialkylammonium
diselenophosphinates ensembles has been elaborated. The
reaction proceeds under mild conditions (EtOH, 60 °C,
0.5 h) affording the target diselenophosphinates in high
yields. The diselenophosphinates that have now become
available due to the methodology developed herein repre-
sent highly potent precursors for the preparation of mag-
neto-optical and semiconducting nanomaterials,1 ligands
for design of coordination structures,2 and promising
building blocks for elemento-organic synthesis.3
All steps of the experiment were carried out under a dry inert atmo-
sphere (argon). Brand EtOH was used in the reaction as a solvent
without additional purification. Ph2PH (1) was employed as com-
mercial product (Aldrich). Secondary phosphines 2–8 were pre-
pared from styrene,17a a-methylstyrene,17a 4-tert-butylstyrene,17b 2-
vinylpyridine,18 4-vinylpyridine,18 2-methyl-5-vinylpyridine,18 or
2-vinylfuran17a and red phosphorus as described in the literature.
The 1H, 13C, 31P, and 77Se NMR spectra were recorded on a Bruker
Figure 1 Thermal ellipsoid plot (50% probability) of the structure
of 9d
The tentative mechanism of the formation of diseleno-
phosphinates can be rationalized as follows (Scheme 3).
In the first stage (1), the secondary phosphine A reacts DPX 400 and Bruker AV-400 spectrometer (400.13, 100.61, 161.98
and 76.31 MHz, respectively) and referenced to H3PO4 (31P NMR)
with one equivalent of elemental selenium to give second-
and Me2Se (77Se NMR). IR spectra were run on a Bruker IFS 25 in-
Synthesis 2010, No. 21, 3724–3730 © Thieme Stuttgart · New York

PAPER
Synthesis of Alkylammonium Diselenophosphinates
3727
strument. Melting points were measured on a Kofler micro hot stage
apparatus.
Allylammonium Diphenyldiselenophosphinate (9b)
White powder; yield: 0.39 g (97%); mp 110–112 °C (EtOH–hex-
ane).
X-ray Crystallography of 9d,e
IR (KBr): 3453, 3046, 2980, 2885, 2667, 2585, 1576, 1477, 1433,
1422, 1356, 1331, 1300, 1178, 1156, 1126, 1087, 1066, 1025, 997,
981, 941, 924, 876, 853, 746, 704, 688, 637, 618, 541, 514, 467
cm–1.
X-ray diffractions studies were carried out with an Xcalibur Oxford
Diffraction diffractometer. The crystal structure was solved by di-
rect methods followed with Fourier synthesis using SHELXS-97.22
All non-hydrogen atoms were refined using anisotropic full-matrix
approximation using SHELXL-97.22 The coordinates of the hydro-
gen atoms were calculated from geometrical positions.23
3
1H NMR (400.13 MHz, CDCl3): d = 3.23 (d, JHH = 5.9 Hz, 2 H,
3
3
NCH2), 5.03 (d, JHH = 10.3 Hz, 1 H, =CH2), 5.09 (d, JHH = 17.1
Hz, 1 H, =CH2), 5.51–5.60 (m, 1 H, CH=), 7.24–7.30, 8.04–8.09 (m,
10 H, Ph), 7.67 (br s, 1 H, NH).
Crystal data and structural refinement for 9d: C20H30NPSe2,
M = 473.34, T = 302 K, orthorhombic, P212121, a = 9.7085(3) Å,
b = 12.7313 Å, c = 18.8589(7) Å, a = b = g = 90°, V = 2330.99(13)
Å3, Z = 4, Dcalc = 1.349 g·cm–3, m = 3.243 mm–1, (2q)max = 26.37°,
reflections measured 8939, reflections independent 4760, 224 pa-
rameters refined, final R indices [I > 2s(I)] R1 = 0.0281,
wR2 = 0.0496. Selected bond lengths (Å): C1–P: 1.804(3), C9–P:
1.820(3), P–Se1: 2.1432(9), P–Se2: 2.1478(8), N–H: 0.91(4),
0.99(4). Selected bond angles (°): Se1–P–C9: 109.84(10), Se1–P–
C1: 108.83(10), Se2–P–C9: 110.37(10), Se2–P–C1: 109.80(10),
Se1–P–Se2: 116.12(3), C1–P–C9: 100.77(13).
13C NMR (100.61 MHz, CDCl3): d = 41.43 (NCH2CH=), 121.67
2
(CH=CH2), 127.67 (d, JCP = 12.4 Hz, o-C), 128.45 (CH=CH2),
4
3
129.80 (d, JCP = 2.2 Hz, p-C), 131.00 (d, JCP = 11.7 Hz, m-C),
140.21 (d, 1JCP = 62.5 Hz, ipso-C).
31P NMR (161.98 MHz, CDCl3): d = 22.20 (s + d satellites:
1JPSe = 584 Hz).
77Se NMR (76.31 MHz, CDCl3): d = 10 (d, 1JPSe = 584 Hz).
Anal. Calcd for C15H18NPSe2: C, 44.90; H, 4.52; N, 3.49; P, 7.72;
Se, 39.36. Found: C, 44.81; H, 4.58; N, 3.40; P, 7.51; Se, 39.41.
Crystal data and structural refinement for 9e: C22H34NPSe2,
M = 501.39, T = 302 K, monoclinic, P21/c, a = 12.668(3) Å,
b = 6.4258(8) Å, c = 30.342(8) Å, a = 90°, b = 91.16(3)°, g = 90°,
V = 2469.4(9) Å3, Z = 4, Dcalc = 1.349 g·cm–3, m = 3.065 mm–1,
(2q)max = 26.37°, reflections measured 9304, reflections indepen-
dent 4983, 245 parameters refined, final R indices [I > 2s(I)]
R1 = 0.0629, wR2 = 0.1275. Selected bond lengths (Å): C1–P:
1.822(5), C9–P: 1.812(5), P–Se1: 2.1303(14), P–Se2: 2.1582(15),
N–H: 0.83(6), 1.06(6). Selected bond angles (°): Se1–P–C9:
110.46(19), Se1–P–C1: 110.65(18), Se2–P–C9: 109.0(2), Se2–P–
C1: 109.14(19), Se1–P–Se2: 114.46(6), C1–P–C9: 102.4(2).
Triethylammonium Bis(2-phenylethyl)diselenophosphinate
(9c)
White powder; yield: 0.44 g (88%); mp 91–92 °C (EtOH).
IR (KBr): 3061, 3028, 2977, 2928, 2754, 2651, 2485, 1601, 1494,
1467, 1454, 1397, 1360, 1308, 1209, 1190, 1176, 1156, 1136, 1122,
1058, 1033, 1009, 951, 935, 919, 833, 807, 790, 770, 759, 733, 707,
620, 575, 495, 479 cm–1.
3
1H NMR (400.13 MHz, CDCl3): d = 1.42 (t, JHH = 7.0 Hz, 9 H,
CH3), 2.54–2.61 (m, 4 H, PCH2), 3.11–3.17 (m, 4 H, CH2Ph), 3.31–
3.36 (m, 6 H, NCH2), 7.17–7.27 (m, 10 H, Ph), 8.86 (br s, 1 H, NH).
Alkylammonium Diselenophosphinates 9a–o; General Proce-
dure
13C NMR (100.61 MHz, CDCl3): d = 8.48 (CH3), 30.86 (CH2Ph),
1
44.22 (d, JCP = 36.4 Hz, PCH2), 45.83 (NCH2), 125.69 (p-C),
Amorphous gray selenium (0.158 g, 2.00 mmol) was added to a
mixture of secondary phosphine 1–8 (1.00 mmol) and the aliphatic
amine (1.10 mmol) in EtOH (10 mL) at r.t. under argon. The sus-
pension was stirred at 60 °C until full dissolution of selenium (~0.5
h) to give a colorless, transparent soln. The solvents were removed
under reduced pressure, the residue was washed with Et2O (2 × 10
mL), and dried in vacuo (45 °C/1.33 mbar) to afford the salt 9a–o.
128.24 (o-C), 128.36 (m-C), 141.87 (d, 3JCP = 17.6 Hz, ipso-C).
31P NMR (161.98 MHz, CDCl3): d = 24.84 (s + d satellites:
1JPSe = 575 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –49 (d, 1JPSe = 575 Hz).
Anal. Calcd for C22H34NPSe2: C, 52.70; H, 6.83; N, 2.79; P, 6.18;
Se, 31.50. Found: C, 52.73; H, 6.52; N, 2.70; P, 6.03; Se, 31.41.
Triethylammonium Diphenyldiselenophosphinate (9a)
White powder; yield: 0.41 g (92%); mp 97–100 °C (EtOH).
Diethylammonium Bis(2-phenylethyl)diselenophosphinate (9d)
White powder; yield: 0.43 g (91%); mp 192–194 °C (EtOH).
IR (KBr): 3063, 3042, 2970, 2937, 2783, 2744, 2653, 2477, 1468,
1454, 1436, 1387, 1356, 1307, 1283, 1173, 1159, 1106, 1085, 1052,
1028, 1011, 997, 896, 837, 804, 769, 756, 697, 622, 547, 522, 476,
442, 418 cm–1.
IR (KBr): 3445, 3058, 3024, 2968, 2837, 2785, 2715, 1601, 1531,
1496, 1452, 1431, 1397, 1385, 1372, 1332, 1266, 1195, 1160, 1137,
1123, 1063, 1047, 1019, 949, 933, 905, 870, 850, 820, 749, 737,
720, 696, 576, 491, 478 cm–1.
3
1H NMR (400.13 MHz, CDCl3): d = 1.21 (t, JHH = 7.4 Hz, 9 H,
3
1H NMR (400.13 MHz, CDCl3): d = 1.54 (t, JHH = 7.3 Hz, 6 H,
CH3), 3.11–3.16 (m, 6 H, NCH2), 8.11–8.16 (m, 10 H, Ph), 10.11 (br
s, 1 H, NH).
CH3), 2.55–2.61 (m, 4 H, PCH2), 3.08–3.15 (m, 4 H, CH2Ph), 3.19–
3.24 (m, 4 H, NCH2), 7.19–7.31 (m, 10 H, Ph), 8.58 (br s, 2 H, NH).
13C NMR (100.61 MHz, CDCl3): d = 8.53 (NCH2CH3), 45.82
13C NMR (100.61 MHz, CDCl3): d = 11.52 (CH3), 30.96 (CH2Ph),
(NCH2CH3), 127.40 (d, 2JCP = 12.1 Hz, o-C), 129.30 (d, 4JCP = 3.0
1
3
1
41.18 (CH2CH3), 43.96 (d, JCP = 36.7 Hz, PCH2), 126.08 (p-C),
Hz, p-C), 131.10 (d, JCP = 12.0 Hz, m-C), 141.63 (d, JCP = 62.8
Hz, ipso-C).
128.55 (o,m-C), 141.72 (d, 3JCP = 17.1 Hz, ipso-C).
31P NMR (161.98 MHz, CDCl3): d = 25.42 (s + d satellites:
31P NMR (161.98 MHz, CDCl3): d = 22.07 (s + d satellites:
1JPSe = 562 Hz).
1JPSe = 603 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –67 (d, 1JPSe = 562 Hz).
77Se NMR (76.31 MHz, CDCl3): d = 24 (d, 1JPSe = 603 Hz).
Anal. Calcd for C20H30NPSe2: C, 50.75; H, 6.39; N, 2.96; P, 6.54;
Se, 33.36. Found: C, 52.73; H, 6.52; N, 2.70; P, 6.43; Se, 33.41.
Anal. Calcd for C18H26NPSe2: C, 48.55; H, 5.89; N, 3.15; P, 6.96;
Se, 35.46. Found: C, 48.50; H, 5.88; N, 3.23; P, 7.06; Se, 35.41.
Synthesis 2010, No. 21, 3724–3730 © Thieme Stuttgart · New York

3728
A. V. Artem’ev et al.
PAPER
Diisopropylammonium Bis(2-phenylethyl)diselenophosphinate
(9e)
77Se NMR(76.31 MHz, CDCl3): d = –35 (d, 1JPSe = 563 Hz), –11 (d,
1JPSe = 567 Hz), 10 (d, 1JPSe = 565 Hz).
White powder; yield: 0.47 g (94%); mp 190–192 °C (EtOH).
Anal. Calcd for C24H38NPSe2: C, 54.44; H, 7.23; N, 2.65; P, 5.85;
Se, 29.83. Found: C, 54.37; H, 7.42; N, 2.64; P, 5.60; Se, 29.80.
IR (KBr): 3454, 3058, 3021, 2822, 2755, 2707, 1601, 1582, 1524,
1496, 1462, 1392, 1377, 1332, 1269, 1189, 1183, 1144, 1124, 1099,
1086, 1030, 1007, 971, 942, 911, 823, 761, 750, 734, 697, 490, 475
cm–1.
Triethylammonium Bis[2-(4-tert-butylphenyl)ethyl]diseleno-
phosphinate (9h)
White powder; yield: 0.52 g (85%); mp 107–109 °C (EtOH).
3
1H NMR (400.13 MHz, CDCl3): d = 1.55 (d, JHH = 6.5 Hz, 12 H,
CH3), 2.51–2.58 (m, 4 H, PCH2), 3.06–3.13 (m, 4 H, CH2Ph), 3.43–
3.50 (m, 2 H, NCH), 7.16–7.27 (m, 10 H, Ph), 8.63 (br s, 2 H, NH).
13C NMR (100.61 MHz, CDCl3): d = 20.13 (CH3), 30.42 (CH2Ph),
43.71 (d, 1JCP = 37.1 Hz, CH2P), 48.31 [CH(CH3)2], 125.59 (p-C),
128.11 (o-C), 128.18 (m-C), 141.52 (d, 3JCP = 17.3 Hz, ipso-C).
IR (KBr): 3090, 3053, 3018, 2959, 2902, 2866, 2778, 2704, 2664,
2607, 2474, 1638, 1516, 1508, 1463, 1437, 1412, 1390, 1363, 1314,
1293, 1267, 1200, 1184, 1161, 1137, 1108, 1067, 1016, 935, 876,
851, 835, 817, 771, 753, 737, 710, 682, 661, 559, 516, 498, 467, 456
cm–1.
1H NMR (400.13 MHz, CDCl3): d = 1.34 [s, 18 H, C(CH3)3], 1.46
(t, 3JHH = 7.4 Hz, 9 H, CH2CH3), 2.55–2.62 (m, 4 H, PCH2), 3.11–
3.17 (m, 4 H, CH2C6H4), 3.36–3.42 (m, 6 H, NCH2), 7.22–7.34 (m,
8 H, C6H4), 9.76 (br s, 1 H, NH).
31P NMR (161.98 MHz, CDCl3): d = 25.02 (s + d satellites:
1JPSe = 569 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –63 (d, 1JPSe = 569 Hz).
13C NMR (100.61 MHz, CDCl3): d = 8.55 (CH2CH3), 30.41
(CH2C6H4), 31.40 [C(CH3)3], 34.33 [C(CH3)3], 44.29 (d, 1JCP = 36.3
Hz, PCH2), 45.86 (NCH2), 125.25 (C2Ar, C6Ar), 128.16 (C3Ar, C5Ar),
138.87 (d, 3JCP = 17.2 Hz, C1Ar), 148.58 (C4Ar).
Anal. Calcd for C22H34NPSe2: C, 52.70; H, 6.83; N, 2.79; P, 6.18;
Se, 31.50. Found: C, 52.73; H, 6.52; N, 2.70; P, 6.03; Se, 31.41.
Allylammonium Bis(2-phenylethyl)diselenophosphinate (9f)
White powder; yield: 0.39 g (85%); mp 115–116 °C (EtOH).
31P NMR (161.98 MHz, CDCl3): d = 25.23 (s + d satellites:
1JPSe = 572 Hz).
IR (KBr): 3021, 2924, 2861, 2776, 2586, 2345, 1948, 1806, 1648,
1599, 1582, 1495, 1474, 1451, 1441, 1424, 1402, 1330, 1313, 1284,
1261, 1212, 1196, 1154, 1135, 1119, 1076, 1028, 1008, 987, 959,
939, 929, 906, 893, 869, 845, 833, 758, 733, 725, 709, 694, 668,
638, 579, 563, 543, 503, 473, 413 cm–1.
77Se NMR (76.31 MHz, CDCl3): d = –48 (d, 1JPSe = 572 Hz).
Anal. Calcd for C30H50NPSe2: C, 58.72; H, 8.21; N, 2.28; P, 5.05;
Se, 25.74. Found: C, 58.70; H, 8.18; N, 2.39; P, 5.10; Se, 25.68.
1H NMR (400.13 MHz, CDCl3): d = 2.48–2.55 (m, 4 H, PCH2),
Dipropylammonium Bis[2-(6-methyl-3-pyridyl)ethyl]diseleno-
phosphinate (9i)
White powder; yield: 0.50 g (94%); mp 170–171 °C (EtOH).
3
2.97–3.04 (m, 4 H, CH2Ph), 3.82 (d, JHH = 6.2 Hz, 2 H, NCH2),
5.34 (d, 3JHH = 10.5 Hz, 1 H, =CH2), 5.51 (d, 3JHH = 17.2 Hz, 1 H,
=CH2), 6.02–6.12 (m, 1 H, CH=), 7.15–7.28 (m, 10 H, Ph), 8.31 (br
s, 3 H, NH).
IR (KBr): 3030, 3002, 2969, 2920, 2881, 2768, 2506, 2487, 1657,
1600, 1568, 1535, 1490, 1466, 1450, 1396, 1320, 1302, 1246, 1200,
1189, 1143, 1118, 1094, 1066, 1029, 1007, 949, 855, 829, 788, 761,
743, 728, 720, 645, 537, 476, 422, 406, 383 cm–1.
13C NMR (100.61 MHz, CDCl3): d = 31.14 (CH2Ph), 41.99
1
(NCH2CH=), 43.43 (d, JCP = 35.0 Hz, PCH2), 122.75 (CH=CH2),
126.36 (p-C), 126.16 (CH=CH2), 128.57 (o-C), 128.70 (m-C),
141.13 (d, 3JCP = 16.7 Hz, ipso-C).
1H NMR (400.13 MHz, CDCl3): d = 1.04 (t, JHH = 7.4 Hz, 6 H,
3
CH3), 1.90–1.99 (m, 4 H, CH2CH3), 2.48–2.54 (m, 10 H, PCH2,
CH3), 3.06–3.12 (m, 8 H, CH2Py, NCH2), 7.06 (d, 2 H, Py), 7.46 (d,
2 H, Py), 8.38 (s, 2 H, Py), 8.87 (br s, 2 H, NH).
31P NMR (161.98 MHz, CDCl3): d = 24.83 (s + d satellites:
1JPSe = 556 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –59 (d, 1JPSe = 556 Hz).
13C NMR (100.61 MHz, CDCl3): d = 11.37 (CH3), 19.44 (CH2CH3),
23.94 (CH3), 27.64 (CH2Py), 43.59 (d, 1JCP = 36.6 Hz, PCH2), 48.49
Anal. Calcd for C19H26NPSe2: C, 49.90; H, 5.73; N, 3.06; P, 6.77;
Se, 34.53. Found: C, 49.91; H, 5.70; N, 2.91; P, 6.60; Se, 34.41.
3
(NCH2), 123.11 (C5Py), 134.00 (d, JCP = 16.2 Hz, C1Py), 136.54
(C6Py), 148.86 (C2Py), 155.74 (C4Py).
Diisopropylammonium Bis(2-phenylpropyl)diselenophosphi-
nate (9g)
White powder; yield: 0.46 g (87%); mp 98–99 °C (EtOH).
31P NMR (161.98 MHz, CDCl3): d = 24.28 (s + d satellites:
1JPSe = 574 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –59 (d, 1JPSe = 574 Hz).
IR (KBr): 3059, 3024, 2976, 2821, 2715, 2535, 2395, 2345, 1941,
1868, 1799, 1743, 1601, 1582, 1573, 1531, 1491, 1463, 1450, 1393,
1377, 1337, 1316, 1299, 1235, 1195, 1181, 1171, 1144, 1100, 1087,
1071, 1043, 1030, 999, 973, 943, 906, 875, 819, 796, 772, 762, 729,
699, 587, 573, 527, 491, 454, 402, 376 cm–1.
Anal. Calcd for C22H36N3PSe2: C, 49.72; H, 6.83; N, 7.91; P, 5.83;
Se, 29.72. Found: C, 49.60; H, 7.08; N, 7.89; P, 6.02; Se, 29.83.
TriethylammoniumBis[2-(4-pyridyl)ethyl]diselenophosphinate
(9j)
1H NMR (400.13 MHz, CDCl3): d = 1.33, 1.38 [d, 3JHH = 7.1 Hz, 6
H, CH(CH3)Ph], 1.52 [d, 3JHH = 6.5 Hz, 12 H, NCH(CH3)2], 2.18–
2.32, 2.38–2.50 (m, 4 H, PCH2), 3.39–3.52 (m, 4 H, CHPh, NCH),
7.08–7.25 (m, 10 H, Ph), 8.91 (br s, 2 H, NH).
White powder; yield: 0.46 g (91%); mp >200 °C dec.
IR (KBr): 3490, 3068, 3043, 2979, 2953, 2894, 2849, 2162, 2068,
1976, 1615, 1556, 1506, 1413, 1393, 1316, 1276, 1248, 1230, 1207,
1169, 1139, 1085, 1065, 1014, 956, 938, 923, 888, 810, 763, 737,
702, 658, 526, 489 cm–1.
1H NMR (400.13 MHz, DMSO-d6): d = 1.17 (t, 3JHH = 7.3 Hz, 9 H,
CH3), 2.30–2.36 (m, 4 H, CH2P), 3.03–3.13 (m, 10 H, CH2Py,
NCH2), 7.35, 8.47 (d, 8 H, Py).
13C NMR (100.61 MHz, CDCl3): d = 20.45 [NCH(CH3)2], 23.86,
3
2
24.30 [d, JCP = 7.6 Hz, CH(CH3)Ph], 37.39 (d, JCP = 25.4 Hz,
CHPh), 48.59 (NCH), 50.78 (d, 1JCP = 34.8 Hz, CH2P), 125.97 (p-
C), 127.41 (o-C), 128.37 (m-C), 148.04, 148.08 (d, JCP = 9.6 Hz,
3
ipso-C).
31P NMR (161.98 MHz, CDCl3): d = 24.23 and 25.17 (s + d satel-
31P NMR (161.98 MHz, DMSO-d6): d = 23.35 (s + d satellites:
lites: 1JPSe = 567 Hz and 1JPSe = 563 Hz, respectively).
1JPSe = 621 Hz).
Synthesis 2010, No. 21, 3724–3730 © Thieme Stuttgart · New York

PAPER
Synthesis of Alkylammonium Diselenophosphinates
3729
Anal. Calcd for C20H32N3PSe2: C, 47.72; H, 6.41; N, 8.35; P, 6.15;
Se, 31.37. Found: C, 47.60; H, 6.32; N, 8.45; P, 6.02; Se, 31.51.
3.30–3.36 (m, 6 H, NCH2), 6.01, 6.25, 7.27 (m, 6 H, Fur), 9.61 (br
s, 1 H, NH).
13C NMR (100.61 MHz, CDCl3): d = 8.49 (CH3), 23.73 (CH2Fur),
TriethylammoniumBis[2-(2-pyridyl)ethyl]diselenophosphinate
(9k)
White powder; yield: 0.45 g (89%); mp >200 °C dec.
1
40.47 (d, JCP = 38.2 Hz, PCH2), 45.92 (NCH2), 104.84 (C3Fur),
110.04 (C4Fur), 140.82 (C5Fur), 155.25 (d, 3JCP = 20.2 Hz, C2Fur).
31P NMR (161.98 MHz, CDCl3): d = 23.06 (s + d satellites:
IR (KBr): 3425, 3062, 3005, 2976, 2905, 2862, 2774, 2662, 2474,
1627, 1593, 1567, 1551, 1473, 1435, 1400, 1388, 1340, 1321, 1300,
1266, 1224, 1198, 1179, 1156, 1130, 1094, 1069, 1051, 1012, 992,
944, 930, 895, 843, 817, 770, 760, 732, 713, 640, 628, 618, 595,
584, 513, 501, 484, 403 cm–1.
1JPSe = 580 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –55 (d, 1JPSe = 580 Hz).
Anal. Calcd for C18H30NO2PSe2: C, 44.92; H, 6.28; N, 2.91; P, 6.44;
Se, 32.81. Found: C, 44.78; H, 6.10; N, 2.89; P, 6.22; Se, 32.71.
1H NMR (400.13 MHz, DMSO-d6): d = 1.18 (t, 3JHH = 7.3 Hz, 9 H,
CH3), 2.37–2.44 (m, 4 H, PCH2), 3.09–3.18 (m, 10 H, CH2Py,
NCH2), 7.18–7.35 (m, 4 H, H3Ph, H5Py), 7.68–7.72 (m, 2 H, H4Py),
8.46–8.47 (m, 2 H, H6Py), 8.87 (br s, 1 H, NH).
Allylammonium Bis[2-(2-furyl)ethyl]diselenophosphinate (9n)
White powder; yield: 0.42 g (96%); mp 152–154 °C (EtOH–hex-
ane).
13C NMR (100.61 MHz, DMSO-d6): d = 9.67 (CH3), 33.97
IR (KBr): 3457, 2968, 2930, 2856, 2780, 1994, 1586, 1505, 1474,
1443, 1424, 1402, 1383, 1330, 1285, 1232, 1213, 1167, 1072, 1038,
1007, 986, 939, 912, 883, 869, 790, 771, 730, 677, 641, 597, 545,
497, 479, 438 cm–1.
1
(CH2Py), 43.85 (d, JCP = 37.9 Hz, PCH2), 46.80 (NCH2), 122.21
(C5Py), 123.75 (C3Py), 137.84 (C4Py), 149.51 (C6Py), 162.50 (d,
3JCP = 17.4 Hz, C2Py).
1H NMR (400.13 MHz, CDCl3): d = 2.47–2.54 (m, 4 H, PCH2),
31P NMR (161.98 MHz, DMSO-d6): d = 24.57 (s + d satellites:
3
1JPSe = 612 Hz).
2.99–3.05 (m, 4 H, CH2Fur), 3.83 (d, JHH = 5.7 Hz, 2 H, NCH2),
5.40 (d, 3JHH = 10.2 Hz, 1 H, =CH2), 5.54 (d, 3JHH = 17.2 Hz, 1 H,
=CH2), 6.02–6.13 (m, 3 H, CH=, Fur), 6.24, 7.26 (m, 4 H, Fur), 8.15
(br s, 1 H, NH).
77Se NMR (76.31 MHz, DMSO-d6): d = –70 (d, 1JPSe = 612 Hz).
Anal. Calcd for C20H32N3PSe2: C, 47.72; H, 6.41; N, 8.35; P, 6.15;
Se, 31.37. Found: C, 47.64; H, 6.33; N, 8.31; P, 6.02; Se, 31.45.
13C NMR (100.61 MHz, CDCl3): d = 23.74 (CH2Fur), 39.42 (d,
1JCP = 36.8 Hz, PCH2), 41.79 (NCH2CH=), 105.32 (C3Fur), 110.18
(C4Fur), 122.50 (CH=CH2), 128.67 (CH=CH2), 141.05 (C5Fur),
154.15 (d, 3JCP = 19.01 Hz, C2Fur).
Allylammonium Bis[2-(2-pyridyl)ethyl]diselenophosphinate
(9l)
White powder; yield: 0.43 g (94%); mp >200 °C dec.
31P NMR (161.98 MHz, CDCl3): d = 25.01 (s + d satellites:
IR (KBr): 3450, 2951, 2853, 2794, 2698, 2071, 1647, 1627, 1591,
1566, 1473, 1433, 1404, 1328, 1310, 1292, 1265, 1229, 1192, 1150,
1123, 1080, 1051, 1002, 989, 940, 925, 897, 883, 842, 781, 763,
742, 719, 699, 634, 589, 555, 512, 484 cm–1.
1JPSe = 561 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –58 (d, 1JPSe = 561 Hz).
Anal. Calcd for C15H22NO2PSe2: C, 41.20; H, 5.07; N, 3.20; P, 7.08;
Se, 36.12. Found: C, 41.34; H, 5.14; N, 3.10; P, 7.19; Se, 36.17.
1H NMR (400.13 MHz, DMSO-d6): d = 2.37–2.43 (m, 4 H, PCH2),
3
3.11–3.17 (m, 4 H, CH2Py), 3.49 (d, JHH = 5.8 Hz, 2 H, NCH2),
5.30 (d, 3JHH = 10.7 Hz, 1 H, =CH2), 5.37 (d, 3JHH = 17.4 Hz, 1 H,
=CH2), 5.82–5.92 (m, 1 H, CH=), 7.15–7.26 (m, 4 H, H3Py, H5Py),
7.65–7.69 (m, 2 H, H4Py), 7.90 (s, 3 H, NH), 8.44–8.45 (m, 2 H,
H6Py).
(R)-2-Hydroxybutylammonium Bis(2-phenylethyl)diseleno-
phosphinate (9o)
White powder; yield: 0.42 g (86%); mp >150 °C dec.
[a]D23 –6.88 (c 0.025, EtOH).
13C NMR (100.61 MHz, DMSO-d6): d = 33.48 (CH2Py), 41.37
IR (KBr): 3412, 3266, 3102, 3082, 3060, 3024, 2974, 2960, 2931,
2895, 2843, 2767, 2729, 2657, 2606, 2517, 2024, 2004, 1972, 1949,
1892, 1613, 1601, 1580, 1494, 1481, 1467, 1453, 1433, 1412, 1390,
1368, 1345, 1329, 1297, 1274, 1262, 1237, 1202, 1178, 1157, 1125,
1082, 1069, 1042, 1031, 1015, 988, 945, 927, 910, 860, 822, 771,
759, 750, 740, 718, 699, 660, 622, 570, 557, 515, 496, 481, 448, 423
cm–1.
1
(NCH2CH=), 43.18 (d, JCP = 37.9 Hz, PCH2), 120.28 (CH=CH2),
121.49 (C5Py), 123.01 (C3Py), 131.16 (CH=CH2), 136.89 (C4Py),
149.19 (C6Py), 162.02 (d, 3JCP = 17.8 Hz, C2Py).
31P NMR (161.98 MHz, DMSO-d6): d = 24.70 (s + d satellites:
1JPSe = 610 Hz).
77Se NMR (76.31 MHz, DMSO-d6): d = –76 (d, 1JPSe = 610 Hz).
3
1H NMR (400.13 MHz, CDCl3): d = 1.00 (t, JHH = 7.5 Hz, 3 H,
Anal. Calcd for C17H24N3PSe2: C, 44.46; H, 5.27; N, 9.15; P, 6.74;
Se, 34.38. Found: C, 44.60; H, 5.20; N, 9.23; P, 6.52; Se, 34.21.
CH3), 1.67–1.80 (m, 2 H, CH2CH3), 2.49–2.56 (m, 4 H, PCH2),
2.99–3.05 (m, 4 H, CH2Ph), 3.32–3.38 (m, 1 H, CHOH), 3.72–3.77
(m, 1 H, NCH2), 3.91–3.94 (m, 1 H, NCH2), 6.27 (br s, 4 H, NH,
OH), 7.14–7.26 (m, 10 H, Ph).
Triethylammonium Bis[2-(2-furyl)ethyl]diselenophosphinate
(9m)
White powder; yield: 0.42 g (87%); mp 171–173 °C (EtOH–hex-
ane).
13C NMR (100.61 MHz, CDCl3): d = 10.36 (CH3), 23.66 (CH2CH3),
1
31.02 (CH2Ph), 43.45 (d, JCP = 35.1 Hz, PCH2), 55.42 (NCH2),
61.47 (CHOH), 126.15 (p-C), 128.40 (o-C), 128.55 (m-C), 141.15
IR (KBr): 3444, 3140, 3099, 2977, 2931, 2850, 2763, 2740, 2704,
2636, 2472, 1653, 1589, 1507, 1487, 1469, 1437, 1415, 1395, 1359,
1333, 1288, 1272, 1232, 1213, 1167, 1142, 1086, 1071, 1029, 1001,
967, 937, 926, 910, 884, 873, 834, 811, 794, 748, 727, 676, 598,
511, 424, 404 cm–1.
(d, 3JCP = 16.6 Hz, ipso-C).
31P NMR (161.98 MHz, CDCl3): d = 25.82 (s + d satellites:
1JPSe = 560 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –51 (d, 1JPSe = 560 Hz).
3
1H NMR (400.13 MHz, CDCl3): d = 1.41 (t, JHH = 7.3 Hz, 9 H,
Anal. Calcd for C20H30NOPSe2: C, 49.09; H, 6.18; N, 2.86; P, 6.33;
Se, 32.27. Found: C, 49.30; H, 6.08; N, 2.89; P, 6.12; Se, 32.04.
CH3), 2.52–2.59 (m, 4 H, PCH2), 3.10–3.17 (m, 4 H, CH2Fur),
Synthesis 2010, No. 21, 3724–3730 © Thieme Stuttgart · New York

3730
A. V. Artem’ev et al.
PAPER
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Raftery, J.; O’Brien, P. J. Organomet. Chem. 2007, 692,
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Chem. 2010, 20, 2329.
(12) (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
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Acknowledgment
This work was supported by the President of the Russian Federation
(Programme for the support of leading scientific schools, grant
NSH 3230-2010.3) and the Russian Foundation for Basic Research
(grant no. 08-03-00251).
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Synthesis 2010, No. 21, 3724–3730 © Thieme Stuttgart · New York