One-pot reaction of secondary phosphine selenides with selenium and nitrogen bases: A novel synthesis of diorganodiselenophosphinates

Article abstract of DOI:10.1055/s-0029-1216948

A three-component reaction of secondary phosphine selenides R ₂P(Se)H [R = PhCH₂CH₂, PhCH(Me)CH₂, 4-t-BuC₆H₄CH₂CH₂, (2-methyl-5-pyridyl)CH2CH2, Ph], elemental selenium

Full text of DOI:10.1055/s-0029-1216948

3332
PAPER
One-Pot Reaction of Secondary Phosphine Selenides with Selenium and
Nitrogen Bases: A Novel Synthesis of Diorganodiselenophosphinates
Synthesis of
D
ior
o
ganodiseleno
r
phosphinates s A. Trofimov,*a Alexander V. Artem’ev,a Nina K. Gusarova,a Svetlana F. Malysheva,a Sergei V. Fedorov,a
Olga N. Kazheva,b Grigorii G. Alexandrov,b Oleg A. Dyachenkob
a
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
Institute of Problems of Chemical Physics, Russian Academy of Sciences, 1 Academician N. N. Semenov Str., 142432 Chernogolovka,
Russian Federation
b
Received 15 May 2009; revised 21 May 2009
nium fragment have been reported: triethylammonium
diisopropyldiselenophosphinate, triethylammonium di-
tert-butyldiselenophosphinate, and triethylammonium
diphenyldiselenophosphinate. These compounds were
Abstract: A three-component reaction of secondary phosphine
selenides R2P(Se)H [R = PhCH2CH2, PhCH(Me)CH2, 4-t-
BuC6H4CH2CH2, (2-methyl-5-pyridyl)CH2CH2, Ph], elemental se-
lenium, and primary, secondary, and tertiary amines and diamines
proceeds under mild conditions (25–85 °C, 1–90 min) in tetrahy- prepared by multistep reactions of toxic and unavailable
drofuran–ethanol as medium to give previously unknown mono-,
monochlorophosphines (R2PCl) with triethylsilane, trieth-
di-, and triorganoammonium salts of diorganodiselenophosphinates
ylamine, and selenium in toluene, and involve long peri-
in high yields (up to 99%).
ods of boiling (Scheme 1).2
Key words: secondary phosphine selenides, elemental selenium,
amines, three-component atom-economic reactions, diselenophos-
phinates, phosphorus compounds
1. HSiEt3, Et3N, r.t., 6 h
R2PCl
[HNEt3][R2PSe2] + [HNEt3]Cl + Si2Et66
2. Se, reflux, 20 h
R = i-Pr, t-Bu, Ph
In the last few years, salts of diselenophosphinic acids,
convenient ‘single-source’ precursors (SSPs) for the prep-
aration of nanostructured semiconductors and nanomate-
rials possessing unique magneto-optical properties,1–3
have attracted ever-increasing interest amongst research-
ers. For example, europium(III) diphenyldiselenophosph-
inate [Eu(Ph2PSe2)3], generated in situ, was used for the
synthesis of europium selenide [Eu1–xSe], a starting block
for the design of novel magneto-optical nanomaterials.3e
Nanorods (2D nanoparticulars) of zinc(II) selenide
(ZnSe), exhibiting semiconductive properties were
synthesized2 from zinc(II) diisopropyldiselenophosphi-
nate [Zn(i-Pr2PSe2)2]. Moreover, diselenophosphinates
can be used as ligands for metal complexes,4 are promis-
ing extractants of heavy, rare, and transuranium ele-
ments,5 have potential biological activity as antimicrobial
and antifungal agents,6 and can also be used as building
blocks for organic and elementoorganic synthesis.7 For in-
Scheme 1 Synthesis of triethylammonium diselenophosphinates
The known procedure allows only the preparation of tri-
ethylammonium salts. In addition, the method is labori-
ous, and requires an argon atmosphere in Schlenk
equipment and especially pure anhydrous solvents. Along
with the target compounds the reaction results in the for-
mation of some byproducts.2
Herein, we report a novel general and simple approach to
the atom-economic synthesis of various diorganodisele-
nophosphinates of nitrogen bases. To reach this goal, we
have studied for the first time the three-component reac-
tion of secondary phosphine selenides with elemental se-
lenium and primary, secondary, and tertiary amines and
diamines of different natures. The starting secondary
phosphine selenides are now available, since they are eas-
ily prepared from red phosphorus, aryl(or hetaryl)ethenes,
and elemental selenium11 (Scheme 2).
stance, esters of diselenophosphinic acids [R1 P(Se)SeR2]
2
can act as efficient initiaters (RAFT agents) in pseudoliv-
ing radical polymerization.8 One might expect that disele-
nophosphinates of nitrogen bases will also possess the
features typical for ammonium compounds, including
those applied in pharmaceutics9 as well as protonic ionic
liquids (PILs).10
1. KOH/H2O
R1
R2
R2
2. R1
, KOH/DMSO
X
X
Se
H
X
P
Pn
R2
3. Se, toluene
R1
However, to the best of our knowledge, only three repre-
sentatives of diselenophosphinates containing an ammo-
1–4
R1, R2 = H, alkyl; X = CH, N
SYNTHESIS 2009, No. 19, pp 3332–3338
Advanced online publication: 21.08.2009
x
x.
x
x
.
2
0
0
9
Scheme 2 Synthesis of secondary phosphine selenides
DOI: 10.1055/s-0029-1216948; Art ID: Z10009SS
© Georg Thieme Verlag Stuttgart · New York

PAPER
Synthesis of Diorganodiselenophosphinates
3333
Table 1 Synthesis of Diorganodiselenophosphinates from Secondary Phosphine Selenides, Elemental Selenium, and Aminesa
R1
R1
R2
R2
R2
R2
R4
R5
R3
H
R4
R5
X
X
X
X
Se
–
Se
H
THF–EtOH
+
N
+
Se
+
R3
N
P
P
85 °C, 10–90 min
Se
R1
R1
1–4
5–12
13a–j
Entry Phosphine selenide R1
R2
X
Amine
5–12
R3
Et
R4
R5
Time
(min)
Salt
13
Yieldb
1–4
(%)
94
95
90
79
93
98
91
86
87
95
1
2
1
1
1
1
1
1
1
2
3
4
H
H
H
H
H
H
H
H
H
H
CH
CH
CH
CH
CH
5
6
7
8
9
Et
Et
60
50
90
60
10
10
15
60
15
15
13a
13b
13c
13d
13e
13f
13g
13h
13i
H
n-Bu
n-Bu
allyl
n-Bu
3
H
allyl
allyl
4
H
(CH2)2OH
n-Pr
Cy
(CH2)2OH
(CH2)2OH
5
H
n-Pr
H
H
H
H
Et
H
H
6
H
CH 10
CH 11
7
H
allyl
Et
H
8
t-Bu
Me
H
CH
N
5
9
Et
9
n-Pr
i-Pr
n-Pr
i-Pr
10
Me CH 12
13j
a Reagents and conditions: phosphine selenide 1–4 (1 mmol), Se (1 mmol), amine 5–12 (1.3 mmol), THF–EtOH, 85 °C.
b All yields refer to isolated products.
As our experiments have shown, secondary phosphine Previously, salt 13k was synthesized by a multistep proto-
selenides 1–4 react with elemental selenium and amines col from expensive reactants of limited availability2 (see
5–12 under mild conditions (85 °C, 10–90 min) in tet- also Scheme 1). To synthesize salts of diselenophosphinic
rahydrofuran–ethanol to afford new diorganodiseleno- acid containing functional nitrogen bases (biologically ac-
phosphinates 13a–j in high yields (79–98%) (Table 1).
tive compounds and semiproducts for fine organic synthe-
sis) directly, we carried out the reactions of secondary
phosphine selenide 1 and elemental selenium with avail-
able bicyclic amines 1,4-diazabicyclo[2.2.2]octane
(DABCO) (Scheme 4) and 1,8-diazabicyclo[5.4.0]undec-
7-ene (DBU) (Scheme 5). Bicyclic diamine 1,4-diazabi-
cyclo[2.2.2]octane reacts with one equivalent of second-
ary phosphine selenide 1 and elemental selenium at 85 °C
for 60 minutes in the solvent system tetrahydrofuran–
ethanol to give salt 13l in 84% yield (Scheme 4).
As can be seen from Table 1, secondary phosphine se-
lenides with aryl(or hetaryl)alkyl substituents as well as
primary, secondary, and tertiary amines, including unsat-
urated and functionalized tertiary amines, participate
readily in this three-component reaction.
Aromatic secondary phosphine selenides can also be used
in this reaction. For example, diphenylphosphine selenide
(14) easily (THF–EtOH, 60 °C, 50 min) reacted with the
selenium/triethylamine system to furnish triethylammoni-
um diphenyldiselenophosphinate (13k) in 88% yield
(Scheme 3).
The presence of the nonquaternized nitrogen atom in salt
13l provides additional synthetic possibilities for further
functionalization. In particular, this salt is a promising in-
termediate for the design of polycationic catalysts for the
cleavage of phosphodiether bonds in RNA.12
Se
H
Se
Se
THF–EtOH
P
HNEt3
The reaction of phosphine selenide 1 and elemental sele-
nium with bicyclic amidine 1,8-diazabicyclo[5.4.0]un-
dec-7-ene proceeds at 25 °C and is completed unusually
fast (ca. 1 min), probably due to the high affinity of 1,8-
Se
Et3N
+
P
+
60 °C, 50 min
14
13k
diazabicyclo[5.4.0]undec-7-ene
for
the
proton
Scheme 3 Synthesis of triethylammonium diphenyldiselenophos-
phinate (13k)
(Scheme 5). The reaction results in the quantitative for-
mation of diselenophosphinate 13m (99% yield) – a valu-
able high-temperature (mp 101–102 °C) proton ionic
liquid.10
Synthesis 2009, No. 19, 3332–3338 © Thieme Stuttgart · New York

3334
B. A. Trofimov et al.
PAPER
Se
–
Se
H
THF–EtOH
N
N
P
P
+
Se
+
85 °C, 60 min
Se
N
N
H
DABCO
1
13l
Scheme 4 Synthesis of diselenophosphinate 13l
Se
–
THF–EtOH
r.t., ~ 1 min
N
N
1
+
Se
+
P
+
Se
N
N
H
DBU
13m
Scheme 5 Synthesis of diselenophosphinate 13m
The mechanism of the formation of diselenophosphinates symmetric vibrations (ns) of the PSe2 group. Asymmetric
can be presented as follows (Scheme 6). In the first stage stretching vibrations (nas) of this group are observed in the
(1), the secondary phosphine selenide is deprotonated by region of 540–570 cm–1.
the nitrogen base to afford P,Se-ambident selenophos-
phinite anion A, which further reacts with elemental sele-
nium to provide the diselenophosphinate anion B (stage
2).
In addition, the structure of compound 13l was established
by X-ray crystallographic analysis. The molecular struc-
ture of salt 13l consists of an anion of the bis(2-pheneth-
yl)diselenophosphinic acid and
a
cation of
diazobicyclooctane (Figure 1). The distances Se(1)–P
[2.133(2) Å] and Se(2)–P [2.167(2) Å] are comparable to
those (2.14–2.17 Å) in similar ionic compounds with P–
Se end bonds.2
Se
Se
H
H
1
+
N
Se–
+
+
P
P
P
–
N
A
Se
–
2
A
+
Se
P
Se
B
Scheme 6
The synthesized salts 13a–m are colorless crystalline sol-
ids (except for 13d, an oil), stable in air, poorly soluble in
water (except for 13d and 13i), and with good solubility
in organic solvents (EtOH, acetone, THF, CHCl3,
DMSO). The structures of compounds 13a–m were
proved by multinuclear (1H, 13C, 31P, and 77Se) NMR and
IR spectroscopy, and the compositions were confirmed by
elemental analysis.
Figure 1 Molecular structure of compound 13l
In conclusion, a three-component reaction between sec-
ondary phosphine selenides, elemental selenium, and ni-
trogen bases, cleanly affording the corresponding salts of
diselenophosphinic acids in high yields, has been devel-
oped. The generality and preparative efficiency of the
method was demonstrated by the synthesis of a series of
previously unknown mono-, di-, and triorganoammonium
salts of disilenophosphinic acids bearing arylalkyl and
aryl substituents. The salts prepared are promising inter-
mediates to produce conducting nanomaterials and SSPs
in metalorganic vapor deposition to manufacture semi-
conducting thin films and protonic ionic liquids, precur-
sors for the design of bioactive agents, as well as building
blocks for the design of diverse phosphorus–selenium
organic compounds.
Equivalency of the selenium atoms in salts 13a–m follows
from 31P and 77Se NMR data. For example, in the 77Se
NMR spectra, a doublet (1JSeP = 550–613 Hz) is present;
in the 31P NMR spectra, a singlet with one typical satellite
1
pair is observed (1JSeP = 550–613 Hz). The JSeP value
(550–613 Hz) is intermediate between the coupling con-
stant values for P–Se and P=Se moieties (200–600 and
800–1200 Hz, respectively), thus corresponding to an or-
der of 1.5 for the phosphorus–selenium bonds. In the 1H
NMR spectra, hydrogen atoms of ammonium N+–H bonds
appear as broad singlets in the region of d = 7.93–10.38.
The IR spectra of the compounds synthesized contain a
strong band at 470–490 cm–1, corresponding to stretching
Synthesis 2009, No. 19, 3332–3338 © Thieme Stuttgart · New York

PAPER
Synthesis of Diorganodiselenophosphinates
3335
Tri-n-butylammonium Bis(2-phenethyl)diselenophosphinate
(13b)
Yield: 0.35 g (95%); colorless solid; mp 84–85 °C.
All experimental steps were carried out under an anhyd inert atmo-
sphere (argon). The solvents were purified and dried by standard
methods.13 All commercially available reagents were used as re-
ceived. The secondary phosphine selenides 1–4 were prepared from
styrenes or vinylpyridine, red phosphorus, and elemental selenium
as described in the literature.11 Diphenylphosphine selenide (14)
was prepared by oxidation of commercially available diphenylphos-
IR (KBr): 3105, 3084, 3059, 3024, 2958, 2931, 2872, 2620, 2521,
1642, 1602, 1582, 1496, 1466, 1454, 1398, 1376, 1310, 1266, 1233,
1205, 1193, 1131, 1102, 1066, 1031, 1018, 961, 945, 926, 910, 852,
832, 801, 759, 745, 707, 698, 577, 568, 504, 492, 477, 432, 399
cm–1.
1
phine (Aldrich, 2008) with elemental selenium. The H, 13C, 31P,
and 77Se NMR spectra were recorded on a Bruker DPX 400 and
Bruker AV-400 spectrometer (400.13, 100.61, 161.98, and 76.31
MHz, respectively); samples were prepared as CDCl3 or D2O solns
and spectra were referenced to HMDS (1H NMR, 13C NMR), H3PO4
(31P NMR), and Me2Se (77Se NMR). IR spectra were run on a
Bruker IFS 25 instrument. Melting points were measured on a
Kofler micro hot-stage apparatus.
3
1H NMR (400.13 MHz, CDCl3): d = 0.96 (t, JHH = 7.4 Hz, 9 H,
CH3), 1.36–1.45 (m, 6 H, CH2Me), 1.73–1.81 (m, 6 H, CH2Et),
2.51–2.58 (m, 4 H, CH2P), 3.10–3.17 (m, 10 H, CH2Ph, CH2N),
7.13–7.27 (m, 10 H, Ph), 8.74 (s, 1 H, NH).
13C NMR (100.61 MHz, CDCl3): d = 13.67 (Me), 20.04 (CH2Me),
1
25.19 (CH2Et), 30.80 (CH2Ph), 44.36 (d, JPC = 35.6 Hz, CH2P),
51.87 (CH2N), 125.71 (p-C), 127.61 (o-C), 128.32 (m-C), 142.49
(d, 3JPC = 17.5 Hz, ipso-C).
X-ray Crystallography of 13l
The X-ray diffraction study of 13l was carried out at 123 K on a
Bruker SMART APEX2 CCD diffractometer, using Mo-Ka radia-
tion. The crystal structure was solved by direct methods followed by
Fourier synthesis using SHELXS-97.14 The structure was refined
using an anisotropic full-matrix approximation for all non-hydro-
gen atoms with SHELXL-97.14 The coordinates of the hydrogen
atoms were calculated from geometrical positions.
31P NMR (161.98 MHz, CDCl3): d = 24.46 (s) (+d satellite,
1JPSe = 573.3 Hz).
77Se NMR (76.31 Hz, CDCl3): d = –45.60 (d, 1JPSe = 573.3 Hz).
Anal. Calcd for C28H46NPSe2: C, 57.43; H, 7.92; N, 2.39; P, 5.29;
Se, 26.97. Found: C, 57.44; H, 7.95; N, 2.33; P, 5.35; Se, 27.01.
Triallylammonium Bis(2-phenethyl)diselenophosphinate (13c)
Yield: 0.30 g (90%); yellowish solid; mp 90–92 °C.
Crystal data and structural refinement for 13l: C22H31N2PSe2,
M = 512.38, T = 123 K, monoclinic, P21/c, a = 18.878(2) Å,
b = 6.614(1) Å, c = 19.350(3) Å, b = 111.364(4)°, U = 2250.0(5)
Å3, Z = 4, Dcalc = 1.51 g·cm–3, m = 3.367 mm–1, (2q)max = 50.70°,
10735 reflections measured, 4034 independent reflections, 244 pa-
rameters refined, R = 0.070 for 2029 reflections with [F0 > 4s(F0)].
CCDC 725047 contains the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
IR (KBr): 3078, 3055, 3018, 2972, 2911, 2790, 2741, 2702, 2644,
2524, 1953, 1878, 1643, 1598, 1491, 1445, 1327, 1286, 1256, 1234,
1209, 1176, 1146, 1118, 1073, 1048, 1004, 992, 975, 953, 934, 906,
879, 827, 756, 712, 696, 599, 563, 512, 490, 469, 416 cm–1.
1H NMR (400.13 MHz, CDCl3): d = 2.56–2.63 (m, 4 H, CH2P),
3
3.12–3.19 (m, 4 H, PhCH2), 3.93 (d, JHH = 6.9 Hz, 6 H, CH2N),
3
3
5.52 (d, JHH = 17.1 Hz, 3 H, =CH2), 5.57 (d, JHH = 10.3 Hz, 3
H, =CH2), 6.15–6.26 (m, 3 H, =CH), 7.18–7.28 (m, 10 H, Ph), 10.31
(s, 1 H, HN).
Diselenophosphinates 13a–j; General Procedure (Table 1)
The amorphous gray selenium (0.049 g, 0.623 mmol) was added to
a soln of the secondary phosphine selenide 1–4 (0.623 mmol) in
THF (4 mL) at 85 °C under argon. The appropriate nitrogen base
(0.810 mmol) in EtOH (5 mL) was added to the stirred suspension.
The suspension was heated until full dissolution of selenium (10–90
min, see Table 1); this gave a colorless, transparent soln. The sol-
vents were removed under reduced pressure and the residue was
washed with Et2O (7 mL) and dried in vacuo (1 Torr, r.t.); this gave
the corresponding salts 13a–j.
13C NMR (100.61 MHz, CDCl3): d = 30.61 (CH2Ph), 43.83 (d,
1JPC = 34.9 Hz, CH2P), 53.93 (CH2N), 125.49 (p-C, =CH2), 125. 85
(=CH), 128.02 (o-C), 128.14 (m-C), 141.55 (d, 3JPC = 17.2 Hz, ipso-
C).
31P NMR (161.98 Hz, CDCl3): d = 24.57 (s) (+d satellite,
1JPSe = 576.1 Hz).
77Se NMR (76.31 Hz, CDCl3): d = –43.91 (d, 1JPSe = 576.1 Hz).
Anal. Calcd for C25H34NPSe2: C, 55.87; H, 6.38; N, 2.61; P, 5.76;
Se, 29.38. Found: C, 56.15; H, 6.38; N, 2.87; P, 5.60; Se, 29.45.
Triethylammonium Bis(2-phenethyl)diselenophosphinate (13a)
Yield: 0.29 g (94%); colorless solid; mp 91–92 °C.
Tris(2-hydroxyethyl)ammonium Bis(2-phenethyl)diseleno-
phosphinate (13d)
Yield: 0.27 g (79%); colorless oil.
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.
IR (film): 3289, 3061, 3025, 2999, 2930, 2893, 1955, 1880, 1813,
1661, 1602, 1582, 1495, 1453, 1398, 1321, 1261, 1207, 1155, 1094,
1067, 1029, 1007, 945, 912, 846, 752, 699, 574, 508, 480, 415, 397
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, CH2P), 3.11–3.17 (m, 4 H, PhCH2), 3.31–
3.36 (m, 6 H, CH2N), 7.17–7.27 (m, 10 H, Ph), 8.86 (s, 1 H, HN).
1H NMR (400.13 MHz, D2O): d = 2.31–2.37 (m, 4 H, CH2P), 2.81–
3
13C NMR (100.61 Hz, CDCl3): d = 8.48 (CH3), 30.86 (CH2Ph),
2.87 (m, 4 H, CH2Ph), 3.29 (t, JHH = 4.8 Hz, 6 H, CH2N), 3.85 (t,
3JHH = 4.8 Hz, 6 H, CH2O), 6.99–7.14 (m, 10 H, Ph).
1
44.22 (d, JPC = 36.4 Hz, CH2P), 45.83 (CH2N), 125.69 (p-C),
128.24 (o-C), 128.36 (m-C), 141.87 (d, 3JPC = 17.6 Hz, ipso-C).
13C NMR (100.61 MHz, D2O): d = 30.78 (CH2Ph), 43.01 (d,
1JPC = 35.5 Hz, CH2P), 55.21 (CH2N), 55.31 (CH2O), 126.03 (p-C),
128.45 (o-C), 129.23 (m-C), 141.15 (d, 3JPC = 16.0 Hz, ipso-C).
31P NMR (161.98 Hz, D2O): d = 26.37 (s) (+d satellite, 1JPSe = 566.1
Hz).
31P NMR (161.98 Hz, CDCl3): d = 24.84 (s) (+d satellite,
1JPSe = 575.0 Hz).
77Se NMR (76.31 Hz, CDCl3): d = –48.46 (d, 1JPSe = 575.0 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.
77Se NMR (76.31 Hz, D2O): d = –48.11 (d, 1JPSe = 566.1 Hz).
Synthesis 2009, No. 19, 3332–3338 © Thieme Stuttgart · New York

3336
B. A. Trofimov et al.
PAPER
Anal. Calcd for C22H34NO3PSe2: C, 48.09; H, 6.24; N, 2.55; P, 5.64;
Se, 28.74. Found: C, 48.15; H, 6.19; N, 2.81; P, 5.50; Se, 28.94.
31P NMR (161.98 Hz, CDCl3): d = 24.83 (s) (+d satellite,
1JPSe = 556.3 Hz).
77Se NMR (76.31 Hz, CDCl3): d = –58.97 (d, 1JPSe = 556.3 Hz).
Di-n-propylammonium Bis(2-phenethyl)diselenophosphinate
(13e)
Yield: 0.29 g (93%); colorless solid; mp 170–172 °C.
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.
IR (KBr): 3086, 3060, 3025, 2966, 2935, 2880, 2771, 2512, 2311,
1746, 1602, 1582, 1538, 1496, 1466, 1453, 1429, 1399, 1333, 1295,
1269, 1209, 1189, 1156, 1126, 1067, 1046, 1030, 1005, 947, 907,
836, 787, 762, 733, 697, 578, 565, 475, 386 cm–1.
Triethylammonium Bis(4-tert-butylphenethyl)diselenophos-
phinate (13h)
Yield: 0.33 g (86%); colorless solid; mp 107–109 °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, t-Bu), 1.46 (t,
3JHH = 7.4 Hz, 9 H, Me), 2.55–2.62 (m, 4 H, CH2P), 3.11–3.17 (m,
4 H, CH2C6H4), 3.36–3.42 (m, 6 H, CH2N), 7.22–7.34 (m, 8 H,
C6H4), 9.76 (s, 1 H, NH).
3
1H NMR (400.13 MHz, CDCl3): d = 1.05 (t, JHH = 7.4 Hz, 6 H,
Me), 1.89–1.99 (m, 4 H, CH2Me), 2.51–2.58 (m, 4 H, CH2P), 3.02–
3.12 (m, 8 H, CH2Ph, CH2N), 7.15–7.28 (m, 10 H, Ph), 8.82 (s, 2 H,
NH).
13C NMR: (100.61 MHz, CDCl3): d = 11.36 (Me), 19.35 (CH2Me),
1
30.81 (CH2Ph), 43.81 (d, JPC = 36.5 Hz, CH2P), 47.99 (CH2N),
3
125.94 (p-C), 128.18 (o-C), 128.43 (m-C), 141.63 (d, JPC = 17.6
Hz, ipso-C).
31P NMR (161.98 Hz, CDCl3): d = 25.42 (s) (+d satellite,
13C NMR (100.61 MHz, CDCl3): d = 8.55 (Me), 30.41 (CH2Ph),
1JPSe = 566.3 Hz).
1
31.40 (Me3C), 34.33 (CMe3), 44.29 (d, JPC = 36.3 Hz, CH2P),
77Se NMR (76.31 Hz, CDCl3): d = –59.83 (d, 1JPSe = 566.3 Hz).
45.86 (CH2N), 125.25 (C2,6 in C6H4), 128.16 (C3,5 in C6H4),
138.87 (d, 3JPC = 17.2 Hz, C1 in C6H4), 148.58 (C4-C6H4).
Anal. Calcd for C22H34NPSe2: C, 52.70; H, 6.83; N, 2.79; P, 6.18;
Se, 31.50. Found: C, 52.56; H, 7.10; N, 2.89; P, 6.23; Se, 31.30.
31P NMR (161.98 Hz, CDCl3): d = 25.23 (s) (+d satellite,
1JPSe = 571.8 Hz).
Cyclohexylammonium Bis(2-phenethyl)diselenophosphinate
(13f)
Yield: 0.30 g (98%); colorless solid; mp 177–178 °C.
77Se NMR (76.31 Hz, CDCl3): d = –48.46 (d, 1JPSe = 571.8 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.
IR (KBr): 3081, 3057, 3021, 2996, 2936, 2886, 2856, 2554, 2497,
1944, 1638, 1600, 1562, 1496, 1449, 1396, 1378, 1347, 1277, 1262,
1215, 1192, 1181, 1141, 1121, 1077, 1062, 1028, 1007, 958, 939,
909, 893, 844, 829, 802, 756, 727, 712, 695, 577, 563, 549, 507,
482, 470, 427, 406 cm–1.
Di-n-propylammonium Bis[2-(2-methyl-5-pyridyl)ethyl]disele-
nophosphinate (13i)
Yield: 0.29 g (87%); colorless solid; mp 170–171 °C.
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.
1H NMR (400.13 MHz, CDCl3): d = 1.16–1.33, 1.62–1.67, 1.79–
1.82, 2.27–2.30 (m, 10 H, CH2-cyclo), 2.51–2.58 (m, 4 H, CH2P),
3.01–3.07 (m, 4 H, CH2Ph), 3.39–3.44 (m, 1 H, CHN), 7.17–7.30
(m, 10 H, Ph), 7.93 (s, 3 H, NH).
3
1H NMR (400.13 MHz, CDCl3): d = 1.04 (t, JHH = 7.4 Hz, 6 H,
13C NMR (100.61 MHz, CDCl3): d = 24.29, 24.72, 31.21 (CH2-cy-
Me), 1.90–1.99 (m, 4 H, CH2Me), 2.48–2.54 (m, 10 H, CH2P, Me-
Py), 3.06–3.12 (m, 8 H, CH2Ph, CH2N), 7.06 (d, 2 H, Py), 7.46 (d,
2 H, Py), 8.38 (s, 2 H, Py), 8.87 (s, 2 H, NH).
clo), 31.97 (CH2Ph), 43.58 (d, 1JPC = 35.4 Hz, CH2P), 51.61 (CHN),
3
126.28 (p-C), 128.49 (o-C), 128.67 (m-C), 141.28 (d, JPC = 16.8
Hz, ipso-C).
13C NMR (100.61 MHz, CDCl3): d = 11.37 (Me), 19.44 (CH2Me),
31P NMR (161.98 Hz, CDCl3): d = 24.79 (s) (+d satellite,
1
23.94 (MePy), 27.64 (CH2Ph), 43.59 (d, JPC = 36.6 Hz, CH2P),
1JPSe = 558.2 Hz).
48.49 (CH2N), 123.11, 134.00 d, 136.54, 148.86, 155.74 (Py).
77Se NMR (76.31 Hz, CDCl3): d = –58.97 (d, 1JPSe = 558.2 Hz).
31P NMR (161.98 Hz, CDCl3): d = 24.28 (s) (+d satellite,
Anal. Calcd for C22H32NPSe2: C, 52.91; H, 6.46; N, 2.80; P, 6.20;
Se, 31.62. Found: C, 52.88; H, 6.49; N, 3.01; P, 6.12; Se, 31.74.
1JPSe = 574.0 Hz).
77Se NMR (76.31 Hz, CDCl3): d = –58.97 (d, 1JPSe = 574.0 Hz).
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; S, 29.83.
Allylammonium Bis(2-phenethyl)diselenophosphinate (13g)
Yield: 0.26 g (91%); colorless solid; mp 115–116 °C.
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.
Diisopropylammonium Bis(2-phenylpropyl)diselenophos-
phinate (13j)
Yield: 0.31 g (95%); colorless solid; mp 98–99 °C.
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.
1H NMR (400.13 MHz, CDCl3): d = 1.33, 1.38 (d, 3JHH = 7.1 Hz, 6
H, MeCHPh), 1.52 (d, 3JHH = 6.5 Hz, 12 H, Me), 2.18–2.32, 2.38–
2.50 (m, 4 H, CH2P), 3.39–3.52 (m, 4 H, CHPh, CHN), 7.08–7.25
(m, 10 H, Ph), 8.91 (s, 2 H, NH).
1H NMR (400.13 MHz, CDCl3): d = 2.48–2.55 (m, 4 H, CH2P),
3
2.97–3.04 (m, 4 H, CH2Ph), 3.82 (d, JHH = 6.2 Hz, 2 H, CH2N),
3
3
5.34 (d, JHH = 10.5 Hz, 1 H, =CH2), 5.51 (d, JHH = 17.2 Hz, 1
H, =CH2), 6.02–6.12 (m, 1 H, =CH), 7.15–7.28 (m, 10 H, Ph), 8.31
(s, 3 H, HN).
13C NMR (100.61 MHz, CDCl3): d = 31.14 (CH2Ph), 41.99
1
(CH2N), 43.43 (d, JPC = 35.0 Hz, CH2P), 122.75 (=CH2), 126.36
(p-C), 128.57 (o-C), 128.70 (m-C), 128.88 (CH = ), 141.13 (d,
3JPC = 16.7 Hz, ipso-C).
Synthesis 2009, No. 19, 3332–3338 © Thieme Stuttgart · New York

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Synthesis of Diorganodiselenophosphinates
3337
13C NMR (100.61 MHz, CDCl3): d = 20.45 (Me), 23.86, 24.30 (d,
31P NMR (161.98 Hz, CDCl3): d = 25.09 (s) (+d satellite,
1JPSe = 571.1 Hz).
77Se NMR (76.31 Hz, CDCl3): d = –69.55 (d, 1JPSe = 571.1 Hz).
2
3JCP = 7.6 Hz, MeCHPh), 37.39 (d, JCP = 25.4 Hz, CHPh), 48.59
(CHN), 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, 3JPC = 9.6 Hz, ipso-C).
Anal. Calcd for C22H31N2PSe2: C, 51.57; H, 6.10; N, 5.47; P, 6.04;
Se, 30.82. Found: C, 51.70; H, 6.12; N, 5.56; P, 6.07; Se, 31.04.
31P NMR (161.98 Hz, CDCl3): d = 24.23, 25.17 (+d satellite,
1JPSe = 566.6 Hz, 1JPSe = 563.4 Hz, respectively).
1
77Se NMR (76.31 Hz, CDCl3): d = –34.91 (d, JPSe = 563.5 Hz),
2,3,4,6,7,8,9,10-Octahydropyrimido[1,2-a]azepin-1-ium Bis(2-
phenethyl)diselenophosphinate (13m)
–10.55 (d, 1JPSe = 566.6 Hz), 10.46 (d, 1JPSe = 564.5 Hz).
The amorphous gray selenium (0.049 g, 0.623 mmol) was added to
a soln of bis(2-phenethyl)phosphine selenide (1; 0.200 g, 0.623
mmol) in THF (4 mL) at r.t. under argon. DBU (0.123 g, 0.810
mmol) in EtOH (5 mL) was added to the stirring suspension. The
suspension was stirred until complete dissolution of selenium (ca. 1
min); this gave a colorless, transparent soln. The solvents were re-
moved under reduced pressure and the residue was washed with
Et2O (5 mL) and dried in vacuo (1 Torr, r.t.); this gave the salt 13m.
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.
Triethylammonium Diphenyldiselenophosphinate (13k)
The amorphous gray selenium (0.049 g, 0.623 mmol) was added to
a soln of diphenylphosphine selenide (14; 0.165 g, 0.623 mmol) in
THF (4 mL) at 60 °C under argon. Et3N (0.082 g, 0.810 mmol) in
EtOH (5 mL) was added to the stirred suspension. The mixture was
heated until full dissolution of selenium (50 min); this gave a color-
less transparent soln. The solvents were removed under reduced
pressure and the residue was washed with Et2O (5 mL) and dried in
vacuo (1 Torr, r.t.); this gave the salt 13k.
Yield: 0.34 g (99%); colorless solid; mp 101–102 °C.
IR (KBr): 3219, 3074, 3012, 2927, 2869, 2797, 2339, 1639, 1586,
1488, 1443, 1393, 1317, 1276, 1198, 1146, 1133, 1102, 1013, 949,
925, 904, 826, 756, 694, 617, 572, 477 cm–1.
Yield: 0.24 g (88%); colorless solid; mp 97–100 °C.
1H NMR (400.13 MHz, CDCl3): d = 1.69 (m, 2 H, C9-H2), 1.77 (m,
2 H, C8-H2), 1.85 (m, 2 H, C10-H2), 2.05–2.11 (m, 2 H, C3-H2),
2.54–2.61 (m, 4 H, CH2P), 3.08–3.19 (m, 6 H, CH2Ph, C7-H2),
3.44–3.51 (m, 4 H, C2,11-H2), 3.62–3.65 (m, 2 H, C4-H2), 7.17–
7.28 (m, 10 H, Ph), 10.26 (s, 1 H, HN).
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.
3
1H NMR (400.13 MHz, CDCl3): d = 1.21 (t, JHH = 7.4 Hz, 9 H,
13C NMR (100.61 MHz, CDCl3): d = 19.19 (C10), 23.53 (C4),
26.43 (C5), 28.63 (C4) 30.68 (CH2Ph), 32.41 (C6), 44.48 (d,
1JPC = 36.6 Hz, CH2P), 44.42 (C11), 54.12 (C2), 125.34 (p-C),
127.95 (o-C), 128.14 (m-C), 141.94 (d, JPC = 17.6 Hz, ipso-C),
165.92 (C7).
Me), 3.11–3.16 (m, 6 H, CH2N), 8.11–8.16 (m, 10 H, Ph), 10.11 (s,
1 H, NH).
13C NMR (100.61 MHz, CDCl3): d = 8.53 (Me), 45.82 (CH2N),
127.34, 127.46 (o-C), 129.29, 129.32 (p-C), 131.04, 131.16 (m-C),
141.63 (d, 1JPC = 62.8 Hz, ipso-C).
3
31P NMR (161.98 Hz, CDCl3): d = 25.08 (s) (+d satellite,
1JPSe = 583.0 Hz).
31P NMR (161.98 Hz, CDCl3): d = 22.07 (s) (+d satellite,
1JPSe = 602.6 Hz).
77Se NMR (76.31 Hz, CDCl3): d = –66.86 (d, 1JPSe = 583.0 Hz).
77Se NMR (76.31 Hz, CDCl3): d = 24.43 (d, 1JPSe = 602.6 Hz).
Anal. Calcd for C25H35N2PSe2: C, 54.35; H, 6.39; N, 5.07; P, 5.61;
Se, 28.59. Found: C, 54.25; H, 6.45; N, 5.11; P, 5.50; Se, 28.43.
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.
Acknowledgment
4-Aza-1-azoniabicyclo[2.2.2]octane Bis(2-phenethyl)diseleno-
phosphinate (13l)
Financial support from the Russian Foundation for Basic Research
(Grant nos. 07-03-00562 and 08-03-00251) is gratefully acknow-
ledged.
The amorphous gray selenium (0.049 g, 0.623 mmol) was added to
a soln of bis(2-phenethyl)phosphine selenide (1; 0.200 g, 0.623
mmol) in THF (4 mL) at 85 °C under argon. DABCO (0.091 g,
0.810 mmol) in EtOH (5 mL) was added to the stirring suspension.
The suspension was heated until the complete dissolution of seleni-
um (60 min); this gave a colorless, transparent soln. The solvents
were removed under reduced pressure and the residue was washed
with Et2O (5 mL) and dried in vacuo (1 Torr, r.t.); this gave the salt
13l.
References
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348. (b) Davies, R. P.; Martinelli, M. G.; Wheatley, A. E. H.;
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Yield: 0.27 g (84%); colorless solid; mp 191–193 °C.
IR (KBr): 3059, 3025, 2882, 2743, 2578, 2541, 2500, 2459, 2125,
1948, 1811, 1636, 1600, 1496, 1452, 1427, 1417, 1390, 1378, 1350,
1316, 1299, 1264, 1242, 1207, 1195, 1178, 1156, 1125, 1066, 1051,
1030, 1007, 974, 945, 919, 910, 837, 825, 781, 769, 734, 723, 706,
698, 593, 569, 507, 485 cm–1.
1H NMR (400.13 MHz, CDCl3): d = 2.53–2.60 (m, 4 H, CH2P),
3.09–3.16 (m, 4 H, CH2Ph), 3.32 (s, 12 H, CH2N), 7.19–7.30 (m, 10
H, Ph), 10.38 (s, 1 H, HN).
13C NMR (100.61 MHz, CDCl3): d = 30.74 (CH2Ph), 43.81 (d,
1JPC = 36.5 Hz, CH2P), 44.96 (CH2N), 125.62 (p-C), 128.12 (o-C),
128.20 (m-C), 141.49 (d, 3JPC = 17.2 Hz, ipso-C).
Synthesis 2009, No. 19, 3332–3338 © Thieme Stuttgart · New York

3338
B. A. Trofimov et al.
PAPER
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Synthesis 2009, No. 19, 3332–3338 © Thieme Stuttgart · New York