Atom-sparing synthesis of tertiary diphosphine dichalcogenides from acetylenes and secondary phosphine chalcogenides

Article abstract of DOI:10.1134/S1070363210020076

Secondary phosphine oxides and phosphine sulfides react with acetylene, methylacetylene, and phenylacetylene in the presence of strong bases (KOH-DMSO, KOH-THF) by the mechanism of double nucleophilic α,β-addition to form tertiary diphosphine dioxides and

Full text of DOI:10.1134/S1070363210020076

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 2, pp. 232–238. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © S.F. Маlysheva, N.А. Belogorlova, V.A. Kuimov, N.I. Ivanova, P.A. Volkov, I.A. Ushakov, N.K. Gusarova, B.А. Тrоfimоv, 2010,
published in Zhurnal Obshchei Khimii, 2010, Vol. 80, No. 2, pp. 206–212.
Atom-Sparing Synthesis
of Tertiary Diphosphine Dichalcogenides from Acetylenes
and Secondary Phosphine Chalcogenides
S. F. Маlysheva, N. А. Belogorlova, V. A. Kuimov, N. I. Ivanova,
P. A. Volkov, I. A. Ushakov, N. K. Gusarova, and B. А. Тrоfimоv
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: gusarova@irioch.irk.ru
Received March 18, 2009
Abstract―Secondary phosphine oxides and phosphine sulfides react with acetylene, methylacetylene, and
phenylacetylene in the presence of strong bases (KOH–DMSO, KOH–THF) by the mechanism of double
nucleophilic α,β-addition to form tertiary diphosphine dioxides and diphosphine disulfides in high yield (up to
97%).
DOI: 10.1134/S1070363210020076
Diphosphine dichalcogenides are promising poly-
dentate ligands for the design of the metal complex
catalysts [1–6], selective podands, for example, for
preparation of the phase transfer catalysts [7, 8],
antipyrenes [9, 10], intermediates for the synthesis of
fluorescent and electroluminescent sensors [11–13].
Diphosphine dioxides were also used as organo-
catalysts for reactions of allylation [14], opening of
epoxides [14], addition of organozinc compounds to
aldehydes [15], and Mukaiyama aldol reaction [8].
Among diphosphine oxides containing aromatic frag-
ments effective extragents of rare and transuranium
elements were found [16–19] whose extractive ability
is increased upon introduction of the ethylene linkage
between the phosphoryl groups as well as in the
presence of alkyl radicals in the benzene ring [20].
closest and most available aliphatic and aromatic
homologs (methyl- and phenylacetylene), the reactions
of double nucleophilic addition of secondary phos-
phine chalcogenides are described sketchily and
mainly by the example of diphenylphosphine oxide
[28–31]. Moreover, neither diphenylphosphine oxide
nor diphenylphosphine sulfide react with phenyl-
acetylene and hexyne under nucleophilic conditions
[28].
In the present paper the reactions of phos-
phorylation of acetylene, methylacetylene, and
phenylacetylene with bis(2-arylalkyl)phosphine oxides
(Ia, Ib) and -phosphine sulfides Ic, Id in the presence
of strong bases are studied in detail aiming at
elaboration of a general expedient method of synthesis
of diphosphine dichalcogenides, in particular, chiral
ones. The starting phosphine chalcogenides Iа–Id are
easily prepared from red phosphorus and styrenes by
the scheme including generation of phosphine-hydro-
gen mixture from red phosphorus and potassium
hydroxide in the system water–toluene, addition of
phosphine to styrene in the presence of a strong base
(KOH–DMSO), and oxidation of the intermediate bis-
(2-arylalkyl)phosphines by air oxygen or elemental
sulfur in toluene [32, 33] (Scheme 1).
At the same time, the methods of synthesis of
diphosphine dichalcogenides, as a rule, are laborious,
multistep, and based on toxic phosphorus halides and
organometallic reagents [21–24]. More convenient
approach to the synthesis of tertiary diphosphine
dichalcogenides is based on the direct phosphorylation
of acetylenes by secondary phosphine chalcogenides,
which proceeds as double nucleophilic addition.
However, this reaction was described mainly for
acetylenes having electron-withdrawing functions at
the triple bond [25–28]. As to acetylene itself and its
We have shown that bis(2-phenylalkyl)phosphine
oxides (Iа, Ib) and bis(2-arylethyl)phosphine sulfides
232

ATOM-SPARING SYNTHESIS OF TERTIARY DIPHOSPHINE DICHALCOGENIDES
233
Scheme 1.
R2
R2
R2
R1
R1
R1
R1
X
KOH/H2O/PhMe
60oC
R1
O2 or S8
25−50oC, 0.5 h
P
Pn
H
P
PH3/H2
KOH/DMSO
45−70oC, 1.5 h
H
R2
R2
Iа−Id
R1 = R2 = H, X = O (а); R1 = Me, R2 = H, X = O (b); R1 = R2 = H, X = S (c); R1 = H, R2 = t-Bu, X = S (d).
Scheme 2.
R2
R2
R1
R1
R1
R1
X X
KOH/DMSO
P
P
Iа−Id
CH
+ HC
R2
R2
IIа−IId
R1 = R2 = H, X = O (а); R1 = Me, R2 = H, X = O (b); R1 = R2 = H, X = S (c); R1 = H, R2 = t-Bu, X = S (d).
(Ic, Id) react with acetylene in the system KOH–
DMSO (50–70°C, 3 h) both at atmospheric pressure
and in an autoclave to form diphosphine dichalco-
genides IIа–IId, the products of double α,β-addition
(see the table, Scheme 2).
As can be seen from the table, the reaction in an
autoclave (initial pressure of acetylene 14 atm, residual
pressure 11 atm) proceeds more effectively than in a
flow system and furnishes diadducts IIа–IId in 81, 72,
97, and 68% yield, respectively (runs 1–4). With this,
Reaction of secondary phosphine oxides Iа, Ib and phosphine sulfides Ic, Id with acetylenesа
Run R2P(X)H,
Acetylene,
(initial pressure, atm)
KOH,
mmol
DMSO, Temperature, °C
Diadduct
R
X
no.
mmol
ml
(time, h)
(yield, %)b
1
2
3
4
5
6
7
8
9
Ia, 1.2
Ib, 1.2
Ic, 1.1
Id, 0.78
Ia, 2.3
Ic, 1.1
Ia, 3.9
Ic, 1.1
Ic, 0.4
PhCH2CH2
O
O
S
HC≡CH (14)
HC≡CH (14)
HC≡CH (14)
HC≡CH (14)
HC≡CH (1)
HC≡CH (1)
MeC≡CH (1)
MeC≡CH (1)
PhC≡CHc (1)
18.6
62.5
18.6
18.6
26.8
18.6
62.5
18.6
0.2
35
70
35
35
35
15
15
50 (3)
70 (3)
50 (3)
50 (3)
50 (3)
50 (3)
60 (2)
50 (2)
25 (3)
IIa (81)
IIb (72)
IIc (97)
IId (68)
IIа (57)
IIc (58)
IV (93)
V (94)
PhCH(Me)CH2
PhCH2CH2
4-t-BuC6H4CH2CH2
PhCH2CH2
S
O
S
PhCH2CH2
PhCH2CH2
O
S
PhCH2CH2
15
d
PhCH2CH2
S
VI (77)
a
All experiments were carried out in an inert atmosphere (argon); runs 1–4 were performed in an autoclave, initial pressure of acetylene
14 atm, residual pressure 11 atm; runs 5 and 6 were performed in the flow of acetylene; runs 7 and 8, in the flow of methylacetylene;
b Yield calculated to the taken phosphine chalcogenide; c run 9: in solution of phenylacetylene (0.02 g, 0.2 mmol) in THF at atmospheric
pressure; d THF (3 ml) as a solvent.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 2 2010

234
МАLYSHEVA et al.
phosphorylation of bis(2-arylethyl)phosphine chalco-
genides Iа, Ic, Id was carried out at 50°C whereas the
less reactive bis(2-phenylpropyl)phosphine oxide (Ib)
required higher temperature (70°C ). Under the
comparable conditions (KOH–DMSO, 50°C, 3 h) but
at atmospheric pressure, bis(2-phenylethyl)phosphine
chalcogenides (Iа, Ic) react with acetylene to form the
corresponding diphosphine chalcogenides IIа, IIc in
57 and 58% yield (see the table, runs 5 and 6). Even
less effective is the addition of diphosphine chalco-
genides Iа, Ic to acetylene in the system KOH–
dioxane. When the process was carried out in an
autoclave (initial pressure of acetylene 14 atm, residual
pressure 13 atm) the expected diadduct was formed
only in the case of the secondary phosphine sulfide Ic
and in a low yield (25%). The secondary phosphine
oxide Iа does not react with acetylene under these
conditions. No reaction of phosphine oxide Iа with
acetylene occurs at room temperature (KOH–DMSO,
autoclave, 3 h). The main product under these
conditions was the potassium salt of bis(2-phenylethyl)-
phosphinic acid (III), apparently, formed as a result of
oxidation of the secondary phosphine oxide Iа in the
system KOH–DMSO [34].
With methylacetylene, in the system KOH–DMSO
(atmospheric pressure, 60–70°C, 2 h) the secondary
phosphine chalcogenides Ia, Ic react practically
quantitatively to form the corresponding diphosphine
dioxide IV and diphosphine disulfide V in preparative
yields of 93 and 94% (see the table, runs 7 and 8,
Scheme 3).
Scheme 3.
X X
KOH/DMSO
Iа, Ic
C
Me
P
P
+ HC
Me
IV, V
X = O (IV); S (V).
The double addition of the secondary phosphine
sulfide Ic to phenylacetylene proceeds readily even at
room temperature in the system KOH–THF with the
formation of the diphosphine disulfide VI (see the
table, run 9, Scheme 4).
plained by a higher nucleophilicity of the conjugate
thiophosphinite anions compared to the phosphinite
anions.
We also tried to accomplish the reaction of
acetylene with bis(2-phenylethyl)phosphine selenide.
It turned out that the heating of the reagents in the
system KOH–DMSO (50°C, 3 h) leads to formation of
elemental selenium. The 31P NMR analysis of the
reaction mixture suggests the formation of a complex
mixture of organophosphorus compounds.
At the same time, we failed to perform the reaction
of the secondary phosphine oxide Ia with
phenylacetylene in the system KOH–THF neither at
room temperature nor upon heating (65°C, 3 h). Under
these conditions, the secondary phosphine oxide Ia
affords the salt III.
Therefore, 100% atom-sparing double nucleophilic
α,β-addition of secondary phosphine oxides and
phosphine sulfides to acetylene, methylacetylene, and
The fact that phosphine sulfides react with
acetylene faster than phosphine oxides can be ex-
Scheme 4.
S
S
KOH/ТHF
P
P
Ic
C
Ph
+ HC
Ph
VI
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 2 2010

ATOM-SPARING SYNTHESIS OF TERTIARY DIPHOSPHINE DICHALCOGENIDES
235
phenylacetylene is a general approach to the synthesis
of diphosphine dichalcogenides, including compounds
of the type II, IV–VI with chiral carbon atom,
promising polydentate ligands for designing metal
complex catalysts including those for asymmetric
synthesis. The presence in the obtained diphosphine
dichalcogenides of the ethylene linkage between the
phosphoryl groups opens real prospects for creation on
their basis of effective extragents for the rare and noble
metals as well as transuranium elements.
spectrum (CDCl3), δC, ppm: 20.81, 20.38, 20.51 and
21.81 m (PCH2CH2P), 24.84 m (CH3), 33.89, 34.17,
34.37 m (CHPh), 36.47, 36.97, 37.10, 37.59, 37.79 and
1
37.94 m (CH2P, JPC 48.0, 51.5, 52.4, 47.1, 41.8 and
53.0 Hz), 126.87 and 126.91 (Cp), 127.01 and 127.06
(Co), 128.85 (Cm), 146.43 m (Ci). 31P NMR spectrum
(CDCl3), δP, ppm: 45.76 : 46.08 : 46.69 : 46.99 = 1 :
3.8 : 6.6 : 1.7. Found, %: C 76.30; H 8.14; P 10.26.
C38H48О2P2. Calculated, %: C 76.23; H 8.08; P 10.35.
1,2-Bis[bis(2-phenylethyl)phosphoryl]ethane (IIа)
(see the table, run 1). By an autoclave synthesis using
the conditions as above for synthesis of compound IIb,
0.26 g (81%) of compound IIа was obtained as a white
powder with mp 209°C (hexane) from phosphine oxide
Ia (0.3 g, 1.2 mmol) and KOH (1.04 g, 18.6 mmol) in
35 ml of DMSO at 50°C after 3 h. IR spectrum (KBr),
ν, cm–1: 3106, 3085, 3060, 3026, 3000 (=CH–Ph);
2949, 2932, 2906, 2869 (CH); 1602, 1584, 1495
(C=C–Ph); 1451 [δ(CH2)]; 1212 [δ(CH–Ph)]; 1153
(P=О); 944, 834 [δ(CH–Ph)]; 781 [δ(CH2)]; 746, 700
[δ(CH–Ph)]; 499 [δ(CPC)]. 1H NMR spectrum
(CDCl3), δH, ppm: 1.84–1.86 m (4H, PCH2CH2P),
1.99–2.00 m (8H, CH2P), 2.88–2.89 m (8H, CH2Ph),
7.18–7.28 m (20H, Ph). 13C NMR spectrum (CDCl3),
EXPERIMENTAL
IR spectra were recorded on a Specord IR-75
instrument. 1H, 13C, and 31P NMR spectra were
registered on a Bruker DPX 400 spectrometer (400,
100, and 161.98 MHz, respectively) with HMDS as an
internal reference, 85% H3PО4 as an external reference
(31P NMR) in CDCl3 and CD3OD. For assignment of
1
13
the signals in the H and C NMR spectra the homo-
and heteronuclear procedures NOESY and HSQC were
used. HSQC analysis of the cross-sections in the two-
dimensional NMR spectrum allowed us to determine
the positions of the aliphatic protons signals which
represent complex superimposed multiplets due to
1
1
1
homonuclear H–1H and heteronuclear H–31P spin–
spin coupling. Nonequivalence of protons in the
CH2P=S and CH2P=O fragments is due to their
diastereotopicity. The signals in the 31P NMR spectra
were assigned by the use of the 2D homonuclear
technique HMBC 31P and HSQC 13C.
δC, ppm: 20.44 m (PCH2CH2P, JPC 57.8 Hz), 27.79
(CH2Ph), 30.12 m (PCH2CH2Ph, 1JPC 63.4 Hz), 126.74
3
(Cp), 128.17 (Co), 128.87 (Cm), 140.59 m (Ci, JPC
31
12.6 Hz). P NMR spectrum (CDCl3) δP, ppm: 47.30.
Found, %: C 75.35; H 7.48; P 11.61. C34H40О2P2.
Calculated, %: C 75.26; H 7.43; P 11.42.
Reaction of bis(2-phenylethyl)phosphine sulfide
with acetylene: synthesis of 1,2-bis[bis(2-phenyl-
ethyl)thiophosphoryl]ethane (IIc) (see the table,
run 6). Suspension of KOH (1.04 g, 18.6 mmol) in
10 ml of DMSO was saturated with acetylene and the
solution of phosphine sulfide Ic (0.26 g, 1.0 mmol) in
4 ml of DMSO was added dropwise during 1.5 h at 50°C
with acetylene bubbling. The mixture was stirred for
another 0.5 h, the supply of acetylene was stopped,
0.07 g of phosphine sulfide in 1 ml of DMSO was
added and stabilized during 1 h at 50°C. The reaction
mixture was cooled, diluted with water, extracted with
benzene. Benzene extracts were washed with water,
dried with potassium carbonate, benzene was removed,
the residue was dried in a vacuum. 0.16 g (59%) of
compound IIc was obtained as white crystals, mp 166–
168°C (hexane). IR spectrum (KBr), ν, cm–1: 3100,
3079, 3063, 3025, 3000 (=CH–Ph); 2895, 2864, 2851
(CH); 1601, 1583, 1494 (C=C–Ph), 1452, 1436, 1401
[δ(CH2)]; 1189, 1180, 1141, 952, 858 [δ(CH–Ph)]; 780
Reaction of bis(2-phenylpropyl)phosphine oxide
with acetylene: synthesis of 1,2-bis[bis(2-phenyl-
propyl)phosphoryl]ethane (IIb) (see the table, run 2).
An autoclave was charged with phosphine oxide Ib
(1.2 g, 4.2 mmol) and KOH (3.5 g, 62.5 mmol) in
70 ml of DMSO and saturated with acetylene. The
mixture was stirred for 3 h at 70°C, cooled, diluted
with water, extracted with benzene. Benzene extracts
were washed with water, dried with potassium car-
bonate, benzene was removed, the residue was dried in
a vacuum. 0.9 g (72%) of compound IIb was obtained
as white crystals, mp 158–160°C (hexane). IR
spectrum (KBr), ν, cm–1: 3100, 3060, 3040, 3026, 3000
(=CH–Ph); 2960, 2945, 2920, 2900, 2869 (CH); 1600,
1584, 1495 (C=C–Ph) 1445 [δ(CH2)]; 1412, 1375
[δ(CH3)]; 1205 [δ(CH–Ph)]; 1145 (P=O); 840, 820
[δ(CH–Ph)]; 780 [δ(CH2)]; 738, 695 [δ(CH–Ph)]; 520
1
[δ(CPC)]. H NMR spectrum (CDCl3), δH, ppm: 1.11–
1.32 m (12H, CH3), 1.50–1.69 m (12H, CH2P), 3.03–
3.17 m (4H, CHPh), 6.95–7.34 m (20H, Ph). 13C NMR
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 2 2010

236
МАLYSHEVA et al.
[δ(CH2)]; 759 (P–C), 746, 702 [δ(CH–Ph)]; 545 (P=S);
3000 (=CH–Ph); 2970, 2949, 2928, 2900, 2864 (CH);
1
503 [δ(CPC)]. H NMR spectrum (CDCl3), δH, ppm:
1601, 1583, 1495, 1452 (C=C–Ph); 744, 698 [δ(CH–Ph)];
1
1.93–1.95 m (4H, PCH2CH2P), 2.04–2.06 m (8H,
CH2P), 2.90–2.92 m (8H, CH2Ph), 7.17–7.27 m (20H,
560, 545 (P=S). H NMR spectrum (CDCl3), δH, ppm:
1.37 d.d (3H, Ме, 2JHH 7.1, 3JPH 17.6 Hz), 1.54–1.58 m
(1H, CHCH2P), 2.02–2.04 m (1H, CHP), 2.15-2.17 m
(8H, CH2P), 2.48–2.64 m (1H, CHCH2P), 2.79–2.98 m
(8H, CH2Ph), 7.19–7.28 m (20H, Ph). 13C NMR
spectrum (CDCl3), δC, ppm: 15.42 (Me), 28.66 d
13
Ph). C NMR spectrum (CDCl3), δC, ppm: 24.07 m
1
(PCH2CH2P, JPC 56.1 Hz), 28.49 (CH2Ph), 32.55 m
1
(PCH2CH2Ph, JPC 48.9 Hz) 126.71 (Cp), 128.44 (Co),
3
128.87 (Cm), 140.24 m (Ci, JPC 12.8 Hz). 31P NMR
2
1
spectrum (CDCl3), δP, ppm: 51.32. Found, %: C 70.65;
H 7.58; P 10.89, S 11.03. C34H40P2S2. Calculated, %: C
71.05; H 7.01; P 10.78; S 11.16.
(CH2Ph, JPC 2.9 Hz), 29.79 d (CHP, JPC 45.7 Hz),
1
30.03 d (CH2P, JPC 46.4 Hz), 30.40 d and 30.57 d
1
(Ме, JPC 45.7 Hz), 33.76 d and 34.68 d (CHCH2P,
1JPC 47.9 Hz), 126.31 (Cp) 127.96 (Co), 128.42 (Cm),
1,2-Bis{bis[4-(tert-butyl)-2-phenylethyl]thiophos-
phoryl}ethane (IId) (see the table, run 4). Under the
conditions of synthesis of compound IIb, 0.21 g (68%)
of compound IId was obtained as a white powder with
mp 242°C (hexane) from phosphine sulfide Id (0.3 g,
0.78 mmol) and KOH (1.04 g, 18.6 mmol) in 35 ml of
DMSO at 50°C after 3 h. IR spectrum (KBr), ν, cm–1:
3094, 3055, 3024 (=CH–C6H4); 2962, 2933, 2902,
2866 (CH); 1516 (C=C–C6H4); 1474, 1463, 1446
[δ(CH2)]; 1410, 1394, 1363, 1269 [δ(CH3)]; 811
140.11 d (Ci, JPC 12.8 Hz). 31P NMR spectrum
3
3
(CDCl3), δP, ppm: 50.43 d (PCH2, JPP 43.6 Hz) and
60.41 d (PCH, 3JPP 43.6 Hz). The signals in the 1H NMR
spectrum were assigned using the 2D homonuclear
technique H–1H COSY with decoupling from 31P.
1
Found, %: C 71.45; H 7.17; P 10.89, S 10.59.
C35H42S2P2. Calculated, %: C 71.40; H 7.19; P 10.52;
S 10.89.
1,2-Bis[bis(2-phenylethyl)phosphoryl]propane (IV)
(see the table, run 7). Under the conditions of synthesis
of compound V, 1.02 g (93%) of compound IV was
obtained as transparent colorless crystals, mp 96°C
(hexane) from phosphine oxide Iа (1.0 g, 3.9 mmol)
and KOH (3.5 g, 62.5 mmol) at 60°C after 3 h. IR
spectrum (KBr), ν, cm–1: 3103, 3083, 3060, 3024, 3000
(=CH–Ph); 2921, 2900, 2853 (CH); 1601, 1583, 1494,
1452 (C=C–Ph); 1175(P=O); 750, 698 [δ(CH–Ph)].
1H–{31P} NMR spectrum, (CDCl3), δ, ppm: 1.36 d or
1
[δ(CH–C6H4)]; 561, 552 (P=S). H NMR spectrum
(CDCl3), δH, ppm: 1.25 s (36H, CH3), 2.04–2.06 m
(12H, CH2P), 2.81–2.91 m (8H, CH2C6H4), 7.09–7.27
m (16H, C6H4). 13C NMR spectrum (CDCl3), δC, ppm:
1
23.94 m (PCH2CH2P, JPC 45.0 Hz), 28.04 (CH2C6H4),
1
31.38 с (CH3), 32.76 m (PCH2CH2C6H4, JPC 48.0 Hz),
34.44 [C(CH3)], 125.68 (Co), 127.96 (Cm), 137.15 (Ci,
3JPC 13.3 Hz), 149.63 (Cp). 31P NMR spectrum
(CDCl3), δP, ppm: 51.45. Found, %: C 74.90; H 9.01; P
7.53, S 8.17. C50H72P2S2. Calculated, %: C 75.14; H
9.08; P 7.75; S 8.02.
31
d.d in the spectrum without decoupling from P (3H,
Ме, 2JHH 7.0 Hz, 3JPH 16.6 Hz), 1.52 d.d (1H, CHCH2P,
3
Reaction of bis(2-phenylethyl)phosphine sulfide
with methylacetylene: synthesis of 1,2-bis[bis(2-
phenylethyl)thiophosphoryl]propane (V) (see the
table, run 8). Suspension of KOH (1.04 g, 18.6 mmol)
in 10 ml of DMSO was saturated with methylacetylene
and the solution of phosphine sulfide Ic (0.26 g,
1.0 mmol) in 5 ml of DMSO was added dropwise
during 0.5 h at 50°C with methylacetylene bubbling.
The mixture was stirred for another 0.5 h, then the
supply of methylacetylene was stopped, 0.07 g of
phosphine sulfide in 1 ml of DMSO was added and
stabilized during 1 h at 50°C. The reaction mixture was
cooled, diluted with water, extracted with benzene.
Benzene extracts were washed with water, dried with
potassium carbonate, benzene was removed, the residue
was dried in a vacuum. 0.33 g (94%) of transparent
colorless crystals were obtained, mp 106°C (hexane).
IR spectrum (KBr), ν, cm–1: 3103, 3083, 3062, 3024,
2JHH 15.0 Hz, JHH 11.2 Hz), 1.88 m (1H, CH2P), 2.03
m (6H, CH2P), 2.15 m (1H, CH2P), 2.27 d (1H,
3
CHCH2P, JHH cannot be determined), 2.34 d.q (1H,
CH), 2.93 m (8H, CH2Ph), 7.08-7.30 m (20H, Ph). 13C
NMR spectrum (CDCl3), δ, ppm: 15.37 (Me), 27.08 d
(CHCH2P, 1JPC 59.8 Hz), 27.51 d.d (CHP, 1JPC 63.6 Hz),
2
27.69, 27.83, 27.87 and 27.93 d (CH2Ph, JPC 3.5, 5.2,
3.8 and 6.8 Hz, respectively), 27.67, 28.16, 30.53 and
1
31.78 d (CH2P, JPC 58.1, 61.2, 62.7 and 62.2 Hz),
126.64, 126.67 (Cp), 128.18, 128.20, 128.25 and
128.28 (Co), 128.83 (Cm), 140.81 d and 140.88 d (Ci,
3JPC 11.9 Hz). 31P NMR spectrum (CDCl3), δP, ppm:
3
3
49.9 d (PCH2, JPP 44.4 Hz) and 59.9 d (PCH, JPP
1
44.4 Hz). The signals in the H NMR spectrum were
assigned using the 2D homonuclear technique H–1H
1
31
COSY with decoupling from P. Found, %: C 75.45;
H 7.17; P 10.88. C35H42О2P2. Calculated, %: C 75.54;
H 7.55; P 11.15.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 2 2010

ATOM-SPARING SYNTHESIS OF TERTIARY DIPHOSPHINE DICHALCOGENIDES
237
Reaction of bis(2-phenylethyl)phosphine sulfide
with phenylacetylene: synthesis of 1,2-bis[bis(2-
phenylethyl)thiophosphoryl]-2-phenylethane (VI)
(see the table, run 9). To the solution of phosphine
sulfide Ic (0.11 g, 0.4 mmol) and phenylacetylene
(0.02 g, 0.2 mmol) in 3 ml of THF 0.01 g (0.2 mmol)
of KOH was added, and the mixture was stirred at 25°C
for 3 h, THF was removed, the residue was dissolved
in ether, filtered, ether was removed to obtain 0.1 g
(77%) of compound VI as transparent colorless
crystals, mp 138–140°C (hexane). IR spectrum (KBr),
ν, cm–1: 3103, 3083, 3060, 3024, 3000 (=CH–Ph);
2921, 2900, 2853 (C–H); 1601, 1583, 1494, 1452
spectrum, (CD3OD) δP: 40.07. Found, %: C 61.71; H
6.03; P 9.57; K 12.49. C16H18KO2P. Calculated, %: C
61.52; H 5.81; P 9.92, K 12.52.
ACKNOWLEDGMENTS
This work was performed with the financial support
from the Russian Foundation for Basic Research
(grants nos. 07-03-00562 and 08-03-00251).
REFERENCES
1. Genge, A., R., J., Levason, W., and Reid, G., Inorg.
Chim. Acta., 1999, vol. 288, no. 2, p. 142.
2. Belletti, D., Graiff, C., Lostao, V., Pattacini, R.,
Predieri, G., and Tiripicchio, A., Inorg. Chim. Acta.,
2003, vol. 347, p. 137.
3. Allen, D.W., in Organophosphorus Chemistry, Allen, D.W.
and Tebby, J.C., Eds., London: The Royal Society of
Chemistry, 2003, vol. 33, p. 1.
4. Peveling, K., Henn, M., Löw Ch., Mehring, M.,
Schürmann, M., Costisella, B., and Jurkschat, K.,
Organometallics, 2004, vol. 23, no. 7, p. 1501.
1
(C=C–Ph); 750, 698 [δ(CH–Ph)];569 (P=S). H NMR
spectrum, (CDCl3) δH, ppm: 1. 50–1.55 m (1H,
CHCH2P), 2.05–2.07 m (1H, CHP), 2.12–2.17 m (8H,
CH2P), 2.22–2.68 (1H, CHCH2P), 2.70–3.07 m (8H,
CH2Ph), 7.12–7.64 m (25H, Ph). 13C NMR spectrum,
(CDCl3) δC, ppm: 28.55 d and 28.40, 28.70, 28.89 and
1
29.03 (CH2Ph), 31.37 d (CHP, JPC 48.1), 31.94, 32.97,
1
33.42 and 33.65 m (CH2P, JPC 48.1, 45.2, 45.9 and
1
45.2 Hz, respectively), 40.72 d (PCH2CHP, JPC
48.2 Hz), 126.48 and 126.74 (Cp), 127.95, 128.19,
128.39 and 128.65 (Co), 128.54 and 128.86 (Cm),
5. Gáti, T., Simon, A., Tóth, G., Szmigielska, A., Maj, A.M.,
Pietrusiewicz, K.M., Moeller, S., Magiera, D., and
Duddeck, H., Eur. J. Inorg. Chem., 2004, no. 10, p. 2160.
3
140.07, 140.37, 140.73 m (Ci, JPC 15.0, 12.4 and
14.7 Hz, respectively). 31P NMR spectrum, (CDCl3) δP,
ppm: 52.53 d (3JPP 49.3 Hz) and 58.26 d (3JPP 49.3 Hz).
The observed in the 2D NOESY spectrum correlations
allowed to assign the signals of the CHPhCH2
fragment. The assignment of the quarternary carbons
13C signals was performed using the 2D HMBC
technique. All the observed in the 2D NMR spectra
correlations allow to make an unequivocal assignment
of the resonance signals and to confirm the structure of
the compound. Found, %: C 73.45; H 7.10; P 9.89, S
10.59. C40H44S2P2. Calculated, %: C 73.81; H 6.81; P
9.52; S 9.85.
6. Matulova, V., Man, S., and Necas, M., Polyhedron.,
2007, vol. 26, no. 12, p. 2569.
7. Bondarenko, N.A., Doctorate (Chem.) Dissertation,
Мoscow, 1995
8. Hatano, M., Takagi, E., and Ishihara, K., Org. Lett.,
2007, vol. 9, no. 22, p. 4527.
9. Aufmuth, W., Levchik, S.V., Levchik, G.F., and Klatt, M.,
Fire and Mater., 1999, vol. 23, no. 1, p. 1.
10. Plotnikova, G.V., Malysheva, S.F., Gusarova, N.K.,
Khaliullin, A.K., Udilov, V.P., and Kuznetsov, K.L.,
Russ. J. Appl. Chem., 2008, vol. 81, no. 2, p. 304.
11. Mastryukova, T.A., Artyushin, O.I., Odinets, I.L., and
Tananaev, I.G., Ross. Khim Zh., 2005, vol. 49, no. 2,
p. 86.
12. Turanov, A.N., Karandashev, V.K., Kharitonov, A.V.,
Yarkevich, A.N., and Safronova, Z.V., Solv. Extr. and
Ion Exch., 2000, vol. 18, no. 6, p. 1109.
Potassium bis(2-phenylethyl)phosphinate (III).
Colorless powder, mp 87–89°C. IR spectrum (KBr), ν,
cm–1: 3400, 3277 (K+, H2O); 3090, 3060, 3027 (=CH–
Ph); 2957, 2933, 2904, 2860 (C–H); 2281, 2140–2420
(K+); 1584, 1601, 1495, 1453 (C=C–Ph); 1404, 1212
[δ(CH2)]; 1136 (P=O); 1117 [νas(P)]; 1033 [νs(PO2–)];
862, 833 [δ(CH2)]; 784, 737, 698 [δ(CH–Ph)]; 750
13. Stoyanov, E.S., Vorob’yova, T.P., and Smirnov, I.V.,
Russ. J. Struct. Chem., 2005, vol. 46, no. 5, p. 839.
14. Smirnov, I.V., Babain, V.A., Shadrin, A.Yu., Efremo-
va, T.I., Bondarenko, N.A., Herbst, R.S., Peter-
man, D.R., and Tood, T.A., Solv. Extr. and Ion Exch.,
2005, vol. 23, no. 1, p. 1.
15. Christou, V., Salata, O.V., Ly, T.Q., Capecchi, S.,
Bailey, N.J., Cowley, A., and Chippindale, A.M., Synth.
Met., 2000, vols. 111–112, p. 7.
1
[δ(PC)]; 572, 502, 479 [δ(P)]. H NMR spectrum,
(CD3OD) δH, ppm: 1.71–1.78 m (4H, CH2P), 2.77–
2.81 m (4H, CH2Ph), 7.09–7.17 m (10H, Ph). 13C
NMR spectrum, (CD3OD) δC, ppm: 30.30 CH2Ph,
34.00 d (CH2P, 1JPC 88.5 Hz ), 126.7 (Cp), 129.12 (Co),
3
129.37 (Cm), 144.4 d (Ci, JPC 14.3 Hz). 31P NMR
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 2 2010

238
МАLYSHEVA et al.
16. Ha-Thi, M.–H., Penhoat, M., Michelet, V., and Leray, I.,
27. Semenzin, D., Etemad-Moghadam, G., Albouy, D.,
Diallo, O., and Koenig, M., J. Org. Chem., 1997,
vol. 62, no. 8, p. 2414.
28. Khachatryan, R.A., Sayadyan, S.V., Grigoryan, N.Yu.,
and Indzhikyan, M.G., Zh. Obshch. Khim., 1988,
vol. 58, no. 11, p. 2472.
29. Khachatryan, R.A., Grigoryan, N.Yu., and Indzhi-
kyan, M.G., Zh. Obshch. Khim., 1994, vol. 64, no. 8,
p. 1260.
30. Trofimov, B.A., Sukhov, B.G., Malysheva, S.F.,
Belogorlova, N.A., Arbuzova, S.N., Tunik, S.P., and
Gusarova, N.K., Russ. J. Org. Chem., 2004, vol. 40,
no. 1, p. 129.
Org. Lett., 2007, vol. 9, no. 6, p. 1133.
17. Fukazawa, A., Hara, M., Okamoto, T., Son, E.-Ch., Xu, C.,
Tamao, K., and Yamaguchi, Sh., Org. Lett., 2008,
vol. 10, no. 5, p. 913.
18. Simonini, V., Benaglia, M., and Benincori, T., Adv.
Synth. Catal., 2008, vol. 350, no. 4, p. 561.
19. Hatano, M., Miyamoto, T., and Ishihara, K., Adv. Synth.
Catal., 2005, vol. 347, nos. 11–13, p. 1561.
20. Ishida, T. and Sasaoka, Sh., Japan Patent no. 308412,
2007, C. A., 2008, vol. 148, no. 2. 33886w.
21. Keglevich, G., in Organophosphorus Chemistry,
Allen, D.W. and Tebby, J.C., Eds., London: The Royal
Society of Chemistry, 2007, vol. 36, p. 73.
31. Rozen, A.M. and Krupnov, B.V., Russ. Chem. Rev.,
22. Shimizu, H., Hagasaki, I., Matsumura, K., Sayo, N., and
1996, vol. 65, no. 11, p. 973.
Saito, T., Acc. Chem. Res., 2007, vol. 40, no. 12, p. 1385.
32. Gusarova, N.K., Bogdanova, M.V., Ivanova, N.I.,
Chernysheva, N.A., Sukhov, B.G., Sinegovskaya, L.M.,
Kazheva, O.A., Alexandrov, G.G., D’yachenko, O.A.,
and Trofimov, B.A., Synthesis, 2005, no. 18, p. 3103.
33. Gusarova, N.K., Malysheva, S.F., Kuimov, V.A.,
Belogorlova, N.A., Mikhailenko, V.L., and Trofi-
mov, B.A., Mendeleev Comm., 2008, vol. 18, no. 5,
p. 260.
23. Japan Patent no. 6472539, 2001, Russ. Khim. Zh., 2003,
03.21–19N, 110P.
24. Antoshin, A.E., Kharitonov, A.V., and Tsvetkov, E.N.,
Zh. Obshch. Khim., 1992, vol. 62, no. 6, p. 1264.
25. Glotova, T.E., Dvorko, M.Yu., Arbuzova, S.N.,
Ushakov, I.A., Verkhoturova, S.I., Gusarova, N.K., and
Trofimov, B.A., Lett. Org. Chem., 2007, no. 4, p. 109.
26. Arbuzova, S.N., Gusarova, N.K., Bogdanova, M.V.,
Ivanova, N.I., Ushakov, I.A., Mal’kina, A.G., and
Trofimov, B.А., Mendeleev Commun., 2005, no. 5,
p. 183.
34. Tsvetkov, V.N., Bondarenko, N.A., Malakhova, I.G.,
and Kabachnik, M.I., Zh. Obshch. Khim., 1985, vol. 55,
no. 1, p. 11.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 2 2010