Atom-economic, metal- and halogen-free synthesis of podands: α,ω-diphosphines and their chalcogenides separated by alkane diol spacers

Article abstract of DOI:10.1055/s-0032-1316764

Secondary phosphines and phosphine chalcogenides add to the divinyl ether of α,ω-alkane diols regio- and chemoselectively under free-radical conditions (UV irradiation or AIBN, 2:1 reactants molar ratio) to give anti-Markovnikov diadducts in good to excel

Full text of DOI:10.1055/s-0032-1316764

2938▌
PAPER
paper
Atom-Economic, Metal- and Halogen-Free Synthesis of Podands:
α,ω-Diphosphines and Their Chalcogenides Separated by Alkane Diol Spacers
Synthesis of Podands
Ludmila A. Oparina, Nina K. Gusarova, Oksana V. Vysotskaya, Nikita A. Kolyvanov, Alexander V. Artem’ev,
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: 05.06.2012; Accepted after revision: 08.07.2012
double bonds of divinyl ethers of α,ω-diols. Such reac-
Abstract: Secondary phosphines and phosphine chalcogenides add
tions have green chemistry advantages12 because they are
to the divinyl ether of α,ω-alkane diols regio- and chemoselectively
potentially 100% atom-economic and therefore do not
under free-radical conditions (UV irradiation or AIBN, 2:1 reac-
produce waste. The choice of starting compounds was
motivated by their high reactivity and availability. Divinyl
ethers of diols are readily assessable through direct vinyl-
ation of diols with acetylene in superbasic catalytic sys-
tems such as KOH/dimethyl sulfoxide (DMSO)13 and,
recently, secondary phosphines have also become readily
accessible due to the development of a direct reaction of
red phosphorus with diverse vinylarenes or vinyl-
hetarenes (e.g., styrenes, vinylpyridines, 2-vinylfuran) in
one preparative step.14
tants molar ratio) to give anti-Markovnikov diadducts in good to ex-
cellent yields (65–98%).
Key words: addition, alkenes, ethers, phosphorylation, radical re-
actions
α,ω-Diphosphines such as DIPAMP, DuPhos, PRO-
PHOS, XANTPHOS, BIPHEP, BINAP, BPE, and Dppe,
as well as their chalcogenides, are widely used as ligands
for organometallic catalysts,1–3 precursors for anticancer
drugs,4 fluorescent sensors for heavy metals,5 precursors
of nanomaterials with novel electronic, magnetic and op-
tical properties,6 and reagents for the extraction of radio-
nuclides and rare-earth elements.7
Ph
O
O
P
P
Ph
BuLi, Et2O
Br(CH2CH2O)3CH2CH2Br
–78 °C, 1.5 h
Ph2PH
Ph2PLi
O
–78 °C, 1.5 h
Over the last decades, attention of researchers has focused
on polydentate ligands with P- and ether O-donor at-
oms.2d,8–10 The use of α,ω-diphosphines bearing alkane
diol moieties as ligands is of interest for several reasons.
The chelation of these ligands with transition metals
forms cyclic polyethers with the metal center incorporated
into the ring (metallacrown ethers).10 The hard O-donor
atoms can also coordinate to alkali metal cations, thus al-
lowing these complexes to function as phase-transfer cat-
alysts.10a,d,e,n,11 It was also reported that the hemilabile
character of ether-phosphines facilitates the formation of
diamine(ether–phosphine)ruthenium(II) complexes.9
Ph
Ph
28%
Scheme 1 Synthesis of α,ω-diphosphine bearing alkane diol moi-
eties
It should be noted that the course of the free-radical reac-
tion of secondary phosphines and their chalcogenides
with divinyl ethers of α,ω-diols is far from obvious. In-
deed, the reaction of divinyl ether of ethylene glycol with
dimethyl phosphite in the presence of a radical initiator
(AIBN, 67–70 °C, 3 h) did not give the expected diadduct,
but instead afforded the cyclic product dimethyl(3-meth-
yl-1,4-dioxan-2-yl)phosphonate, in 50% yield, together
with macrocyclic and smaller phosphorus-containing
telomeres (Scheme 2).15
Conventional syntheses of α,ω-diphosphines with alkane
diol spacers are laborious, require low-temperature condi-
tions, and involve utilizing moisture- and air-sensitive or-
ganometallic compounds (see typical example in Scheme
1).10a Furthermore, these methods are not atom-economic
because they are accompanied by the formation of diverse
waste material.
MeO
O
The goal of this work was to develop a convenient metal-
and halogen-free route to α,ω-diphosphines and their
chalcogenides separated by alkane diol spacers. For this
purpose we chose the free-radical addition of secondary
phosphines and secondary phosphine chalcogenides to the
OMe
OMe
OMe
O
H
AIBN
O
P
+
P
telomeres
+
O
67–70 °C
O
excess
O
50%
Scheme 2 Free-radical reaction between divinyl ether of ethylene
glycol and dimethyl phosphite
SYNTHESIS 2012, 44, 2938–2946
Advanced online publication: 08.08.2012
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0
3
9
-
7
8
8
1
1
4
3
7
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2
1
0
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DOI: 10.1055/s-0032-1316764; Art ID: SS-2012-Z0498-OP
© Georg Thieme Verlag Stuttgart · New York

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Synthesis of Podands
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Later,16 under similar conditions (AIBN, 60 °C, THF), the 1,4-dioxane) or without solvent, to give the corresponding
addition of diethyl thiophosphite to diallyl ether was also anti-Markovnikov diadducts 3a–c (Table 1) and 4a–c (Ta-
shown to proceed through a cyclization reaction to deliver ble 2) in 65–85% yield. Reaction time was 10–12 hours
functional tetrahydrofuran, O,O-diethyl (4-methyltetra- under UV irradiation and 20–50 hours when AIBN was
hydro-3-furanyl)methylthiophosphonate, in approximate- employed. Notably, the reaction proceeded regio- and
ly 92% yield (Scheme 3).
chemoselectively; no trace of the Markovnikov, cycliza-
tion, or telomerization products were detected in the reac-
tion mixtures (1H and 31P NMR spectroscopic analysis).
S
EtO
P
S
H
OEt
OEt
AIBN, 60 °C
THF
Free-radical addition of secondary phosphine chalcogen-
ides to divinyl ethers of α,ω-diols turned out to proceed
faster and more effectively than those of secondary phos-
phines.
P
+
OEt
O
O
92%
Scheme 3 Free-radical addition of diethyl thiophosphite to diallyl
ether
Secondary phosphine sulfides 5a, 5b, and selenide 5c re-
act with divinyl ethers of 1,2-diols 2a and 2c under UV ir-
radiation (1.5–2 h) or in the presence of AIBN (65 °C, 3
h) in organic solvent (1,4-dioxane, benzene, or acetoni-
trile) to afford chemo- and regioselectively anti-
Markovnikov diadducts 6a–d in almost quantitative yield
(Table 3).
Here, we report that secondary phosphines 1a–c react
with divinyl ethers of ethylene glycol 2a and diethylene
glycol 2b under mild conditions (UV irradiation or AIBN,
65 °C, 2:1 molar ratio) either in organic solvents (MeCN,
Table 1 Exhaustive Free-Radical Addition of Secondary Phosphines to Divinyl Ether 2a
R
R
R
P
P
O
O
O
O
R
R
AIBN or UV
P
H
2
+
1a–c
R
2a
3a–c
Entry
1
R
Initiatora
Solvent
Time (h)
3
Yield (%)b
1
2
3
4
5
1a
1b
1b
1c
1c
Ph
AIBN
AIBN
UV
none
50
20
10
12
50
3a
3b
3b
3c
3c
73
78
69
67
75
Ph(CH2)2
Ph(CH2)2
2-Fur(CH2)2
2-Fur(CH2)2
MeCN
MeCN
1,4-dioxane
none
UV
AIBN
a Standard reaction conditions: molar ratio 1/2 = 2:1, argon. UV irradiation (200 W Hg arc lamp); AIBN (2 wt% of reactant mass), 65 °C.
b Isolated yield.
Table 2 Exhaustive Free-Radical Addition of Secondary Phosphines to Divinyl Ether 2b
O
R
O
R
P
P
R
R
AIBN or UV
O
2
P
H
+
O
R
O
1a,b,d
R
O
4a–c
2b
Entry
1
R
Initiator
Solvent
Time (h)
4
Yield (%)a
1
2
3
1a
1b
1d
Ph
AIBN
UV
none
48
12
24
4a
4b
4c
84
85
65
Ph(CH2)2
1,4-dioxane
1,4-dioxane
4-Cl-C6H4(CH2)2
AIBN
a Isolated yield.
© Georg Thieme Verlag Stuttgart · New York
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L. A. Oparina et al.
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Table 3 Exhaustive Free-Radical Addition of Secondary Phosphine Chalcogenides 5a–c to Divinyl Ethers of 1,2-Diols 2a and 2c
R1
X
R1
R1
P
R1
X
R1
R1
X
H
O
AIBN or UV
P
O
P
2
+
R2
R2
2a,c
O
5a–c
O
6a–d
Entry
Phosphine chalcogenide
2
R2
Initiator
Solvent
Time (h)
6
Yield (%)a
1
2
3
4
5
5a
5b
5b
5b
5c
Ph2P(S)H
2a
2a
2a
2c
2a
H
AIBN
UV
1,4-dioxane
MeCN
3
6a
6b
6b
6c
6d
95
93
95
96
92
(PhCH2CH2)2P(S)H
(PhCH2CH2)2P(S)H
(PhCH2CH2)2P(S)H
(PhCH2CH2)2P(Se)H
H
1.5
1.5
1.5
2
H
UV
benzene
Me
H
UV
MeCN
UV
1,4-dioxane
a Isolated yield.
Under the conditions given in Table 3, secondary phos-
phine chalcogenides 5a–c also add easily to divinyl ethers
of diethylene glycol 2b (Scheme 4) and triethylene glycol
2d (Scheme 5) to form the corresponding podands termi-
nated by phosphine chalcogenides functions 7a, 7b, 8a,
and 8b in near quantitative yields (90–98%).
O
O
X
UV
(PhCH2CH2)2P
+
2
H
O
5a,c
O
2d
O
O
Ph
R
O
O
P
O
O
P
P
R
X
X
S
S
Ph
Ph
R
R
S
H
UV or AIBN
+
O
O
2
P
R
R
Ph
O
5a,b
O
P
8a,b
2b
7a,b
8a: X = S (1.5 h, benzene, yield 98%)
8b: X = Se (2 h, 1,4-dioxane, yield 90%)
7a: R = Ph (AIBN, 3 h, 1,4-dioxane, yield 94%)
7b: R = (CH2)2Ph (UV, 1.5 h, benzene, yield 98%)
Scheme 5 Synthesis of podands from secondary phosphine chalco-
genides 5a, 5c and divinyl ether triethylene glycol 2d
Scheme 4 Free-radical reaction of secondary phosphine chalcogen-
ides 5a and 5b with divinyl ether of diethylene glycol 2b
Ph
The generality of the reaction was additionally supported
by the fact that divinyl ethers of diverse α,ω-alkylene gly-
cols 2e–h react with secondary chalcogenides 5b and 5c
under UV irradiation to effectively produce anti-
Markovnikov diadducts 9a–f (Table 4).
P
Ph
O
O
O
O2 (air)
r.t., 3 h
3b
O
P
Ph
Note that secondary phosphine oxides did not react with
divinyl ether 2 under the above free-radical conditions.
UV irradiation (10 h, 1,4-dioxane) of a mixture of bis(2-
phenethyl)phosphine oxide and divinyl ether 2a gave only
traces of the expected diadduct 10, with the starting mate-
rials being recovered almost quantitatively. This is consis-
tent with published data on the low reactivity of secondary
phosphine oxides in radically induced addition reac-
tions.17 However, diphosphine oxide 10 was easily pre-
pared in 98% yield by the oxidation (air, 3 h) of the
corresponding diphosphine 3b (Scheme 6).
Ph
10, 98%
Scheme 6 Oxidation of diphosphine 3b
The synthesized α,ω-diphosphines separated by alkane
diol spacers can be used as building blocks for organic
synthesis and as ligands for the design of prospective
metallocomplexes. For example, diphosphine 4a easily
reacts (room temperature, 1 h) with iodomethane to afford
diphosphonium salt 11 in 97% yield (Scheme 7).
Synthesis 2012, 44, 2938–2946
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Synthesis of Podands
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Table 4 Synthesis of Podands 9a–f from Secondary Phosphine Chalcogenides 5b, 5c and Divinyl Ether α,ω-Diols 2e–h
O
P
O
n
Ph
Ph
R
R
X
H
UV
2
P
+
P
X
X
O
O
Ph
n
Ph
2e–h
5b,c
Ph
Ph
9a–f
Entry
5
X
2
R
n
Solvent
Product
Yield (%)a
1
2
3
4
5
6
5b
5b
5b
5b
5c
5c
S
2e
2f
H
1
1
2
4
2
4
benzene
MeCN
9a
9b
9c
9d
9e
9f
96
97
97
98
93
90
S
Me
H
S
2g
2h
2g
2h
benzene
MeCN
S
H
Se
Se
H
benzene
H
1,4-dioxane
a Isolated yield.
tal sulfur and selenium.18 1H, 13C, and 31P NMR spectra were record-
ed with a Bruker DPX 400 or Bruker AV-400 spectrometer (400.13,
100.62 and 161.98 MHz, respectively) at 23 °C in CDCl3 solutions.
Chemical shifts are reported in δ (ppm) relative to CDCl3 (1H, 13C)
as internal standard or H3PO4 (31P) as external standard. Infrared
(FTIR) spectra were taken with a Bruker Vertex 70 spectrometer.
Microanalyses were performed with a Flash EA 1112 Series ele-
mental analyzer. Melting points were recorded with a ‘Stuart melt-
ing point apparatus’ and are uncorrected.
O
O
O
CH2Cl2
r.t., 1 h
4a
+
MeI
excess
+
+
I
Ph
P
I
P
Ph
Ph Me
Me Ph
11, 97%
Scheme 7 Quaternization of diphosphine 4a with MeI
Preparation of Diphosphines 3, 4 and Diphosphine Chalcogen-
ides 6–9; General Procedures
Method A: A solution of PH-addend 1, 5 (0.8 mmol) and divinyl
ether 2 (0.4 mmol) in solvent (0.5 mL) was irradiated (200 W Hg
arc lamp) in a quartz ampoule (the reaction time is given in Tables
1–4).
Preliminary data on the interaction of α,ω-diphosphine 4a
with PdCl2 were obtained. The reaction of ligand 4a with
PdCl2 (1:1 molar ratio) was carried out at room tempera-
ture in dichloromethane under high-dilution conditions.
The 31P NMR spectrum of the reaction mixture contained
three singlets at δ = 12.6, 15.0 and 26.0 ppm in a 1:1.1:1.5
ratio, respectively, the conversion of the starting α,ω-di-
phosphine 4a being 100%. Further investigations on this
reaction are under way and the results will be published in
due course.
Method B: A solution of PH-addend 1, 5 (0.8 mmol) and divinyl
ether 2 (0.4 mmol) in solvent (0.5 mL) or without solvent in the
presence of AIBN (2 wt% of the total mass of reactants) was stirred
at 65 °C in a sealed ampoule (the reaction time is given in Tables 1–
3).
The reaction was monitored by 31P NMR spectroscopy following
the disappearance of the signal (δ, ppm) of the starting PH-addends
(the –70 to –39 ppm region for phosphines 1; the 2 to 21 ppm inter-
val for phosphine chalcogenides 5) and appearance of a new reso-
nance in the –32 to –21 and 37 to 49 ppm regions, corresponding to
diphosphines 3, 4 or diphosphine chalcogenides 6–9. The reaction
mixture was dissolved in diethyl ether (3 mL), and passed through
of a layer of Al2O3 (activity level II, 0.5 cm), the latter was addition-
ally washed with a mixture of hexane–Et2O (1:1, 3 mL). The sol-
vents were removed in vacuo to give the diphosphines 3, 4 or
diphosphine chalcogenides 6–9.
In summary, the atom-economic, metal- and halogen-free
synthesis of α,ω-diphosphines and their chalcogenides
bearing alkylene glycol moieties, has been developed by
exhaustive chemo- and regioselective free-radical addi-
tion of secondary phosphines and phosphine chalcogen-
ides to divinyl ethers of α,ω-diols. This approach provides
a facile short-cut to prospective podand ligands for the de-
sign of multi-purpose metal complexes, special solvents,
and reactive building blocks for organic synthesis.
2-[2-(Diphenylphosphino)ethoxy]ethyl 2-(Diphenylphosphi-
no)ethyl Ether (3a)
Yield: 142 mg (73%) (method B); colorless oil.
IR (KBr): 740 (P–C) cm–1.
All reactions were carried out under an inert atmosphere (argon).
All solvents were dried and/or purified according to standard proce-
dures. Divinyl ethers of α,ω-alkylene diols 2a–h were synthesized
according to a published method.13 Secondary phosphines 1b and 1c
were prepared from styrene or 2-vinylfuran and red phosphorus, as
described in the literature.14 Secondary phosphines chalcogenides
5b and 5c were prepared by oxidation of phosphine 1b with elemen-
3
1H NMR (400 MHz, CDCl3): δ = 2.42 (t, JH–H = 7.8 Hz, 4 H,
3
3
PCH2), 3.52 (s, 4 H, OCH2), 3.64 (dt, JP–H = 15.2 Hz, JH–H = 7.2
Hz, 4 H, PCH2CH2O), 7.33–7.44 (m, 20 H, Ph).
13C NMR (100 MHz, CDCl3): δ = 28.7 (d, 1JP–C = 12.8 Hz, PCH2),
2
68.8 (d, JP–C = 25.5 Hz, PCH2CH2O), 70.1 (CH2O), 128.3 (p-C in
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2012, 44, 2938–2946

2942
L. A. Oparina et al.
PAPER
Ph), 128.4 (d, 3JP–C = 15.1 Hz, o-C in Ph), 132.5 (d, 2JP–C = 18.1 Hz,
m-C in Ph), 138.2 (d, 3JP–C = 12.3 Hz, ipso-C in Ph).
31P NMR (161 MHz, CDCl3): δ = –21.5.
13C NMR (100 MHz, CDCl3): δ = 27.8 (d, 2JP–C = 14.6 Hz, PhСH2),
1
1
29.4 (d, JP–C = 13.6 Hz, PCH2CH2O), 32.4 (d, JP–C = 17.6 Hz,
2
CH2P), 69.2 (d, JP–C = 20.3 Hz, PCH2CH2O), 70.2, 70.7 (OCH2),
126.0 (p-C in Ph), 128.2 (o-C in Ph), 128.5 (m-C in Ph), 142.9 (d,
3JP–C = 10.7 Hz, ipso-C in Ph).
Anal. Сalcd for C30H32O2P2: С, 74.06; Н, 6.63; Р, 12.73. Found: С,
74.37; Н, 6.77; Р, 12.89.
31P NMR (162 MHz, CDCl3): δ = –31.3.
2-[2-(Diphenethylphosphino)ethoxy]ethyl 2-(Diphenethyl-
phosphino)ethyl Ether (3b)
Yield: 165 mg (69%) (method A), 187 mg (78%) (method B); col-
orless oil.
Anal. Сalcd for C40H52O3P2: С, 74.74; Н, 8.15; Р, 9.64. Found: С,
74.52; Н, 8.26; Р, 9.32.
2-(2-{2-[Bis(4-chlorophenethyl)phosphino]ethoxy}ethoxy)ethyl
2-[Bis(4-chlorophenethyl)phosphino]ethyl Ether (4c)
Yield: 203 mg (65%) (method B); colorless oil.
IR (KBr): 757 (P–C), 614 (C–Cl) cm–1.
1H NMR (400 MHz, CDCl3): δ = 1.96–2.09 (m, 12 H, PCH2), 2.76–
2.95 (m, 8 H, CH2C6H4), 3.46–3.79 (m, 12 H, OCH2), 7.03–7.11
(m, 8 H, H-2,6 in C6H4), 7.17–7.23 (m, 8 H, H-3,5 in C6H4).
IR (KBr): 753 (P–C) cm–1.
1H NMR (400 MHz, CDCl3): δ = 1.76–1.82 (m, 12 H, PCH2), 2.73–
3
2.76 (m, 8 H, PhCH2), 3.48 (s, 4 H, OCH2), 3.62 (dt, JP–H
=
3
15.2 Hz, JH–H = 7.6 Hz, 4 H, PCH2CH2O), 7.20–7.29 (m, 20 H,
Ph).
13C NMR (100 MHz, CDCl3): δ = 27.3 (d, 2JP–C = 14.4 Hz, PhСH2),
1
1
29.1 (d, JP–C = 13.6 Hz, PCH2CH2O), 32.1 (d, JP–C = 14.4 Hz,
13C NMR (100 MHz, CDCl3): δ = 27.1 (CH2C6H4), 29.4 (d, 1JP–C
=
CH2P), 68.8 (d, 2JP–C = 21.6 Hz, PCH2CH2O), 69.9 (CH2O), 125.75
14.2 Hz, PCH2CH2O), 30.5 (d, JP–C = 15.3 Hz, PCH2), 68.6 (d,
2JP–C = 19.9 Hz, PCH2CH2O), 70.4, 70.5 (CH2O), 128.8 and 128.9
(C-2,6 in C6H4), 129.5, 129.5 (C-3,5 in C6H4), 130.4 (C-4 in C6H4),
138.5 (d, 3JP–C = 12.6 Hz, C-1 in C6H4).
1
(p-C in Ph), 127.9 (o-C in Ph), 128.2 (m-C in Ph), 142.6 (d, 3JP–C
10.8 Hz, ipso-C in Ph).
=
31P NMR (162 MHz, CDCl3): δ = –31.8.
31P NMR (162 MHz, CDCl3): δ = –31.1.
Anal. Сalcd for C38H48O2P2: С, 76.23; Н, 8.08; Р, 10.35. Found: C,
76.09; Н, 8.15; Р, 10.63.
Anal. Сalcd for C40H48Cl4O3P2: С, 61.55; Н, 6.20; Cl, 18.17; Р,
7.94. Found: C, 61.64; Н, 6.12; Cl, 18.32; Р, 6.43.
2-(2-Bis[2-(2-furyl)ethyl]phosphinoethoxy)ethyl 2-Bis[2-(2-fu-
ryl)ethyl]phosphinoethyl Ether (3c)
Yield: 150 mg (67%) (method A), 168 mg (75%) (method B); col-
orless oil.
2-{2-[2-(Diphenylphosphorothioyl)ethoxy]ethoxy}ethyl(diphe-
nyl)phosphine Sulfide (6a)
Yield: 209 mg (95%) (method B); colorless oil.
IR (KBr): 731 (P–C) cm–1.
IR (KBr): 752 (P–C), 603 (P=S) cm–1.
1H NMR (400 MHz, CDCl3): δ = 1.74–1.81 (m, 12 H, PCH2), 2.78
1H NMR (400 MHz, CDCl3): δ = 2.77 (m, 4 H, PCH2), 3.32 (s, 4 H,
OCH2), 3.76 (m, 4 H, PCH2CH2O), 7.41–7.46 (m, 12 H, Ph), 7.78–
7.83 (m, 8 H, Ph).
(dt, 3JP–H = 16.0, 3JH–H = 8.0 Hz, 8 H, CH2Fur), 3.58 (s, 4 H, OCH2),
3
3
3.63 (dt, JP–H = 15.4, JH–H = 7.5 Hz, 4 H, PCH2CH2O), 6.01 (s,
4 H, H-3 in Fur), 6.28 (s, 4 H, H-4 in Fur), 7.30 (s, 4 H, H-5 in Fur).
13C NMR (100 MHz, CDCl3): δ = 32.9 (d, 1JP–C = 56.4 Hz, PCH2),
13C NMR (100 MHz, CDCl3): δ = 20.2 (CH2Fur,), 24.5 and 25.3 (d,
65.1, 69.8 (OCH2), 128.2 (d, 3JP–C = 12.3 Hz, m-C in Ph), 130.6 (d,
2
4
1JP–C = 12.7 and 14.7 Hz, PCH2), 68.7 (d, JP–C = 20.0 Hz,
2JP–C = 10.7 Hz, o-C in Ph), 131.2 (d, JP–C = 2.3 Hz, p-C in Ph),
PCH2CH2O), 70.0 (CH2O), 104.7 (C-3 in Fur), 110.0 (C-4 in Fur),
132.7 (d, 1JP–C = 81.3 Hz, ipso-C in Ph).
31P NMR (162 MHz, CDCl3): δ = 38.7.
140.8 (C-5 in Fur), 155.8 (d, 3JP–C = 12.1 Hz, C-2 in Fur).
31P NMR (162 MHz, CDCl3): δ = –31.3.
Anal. Сalcd for C30H32O2P2S2: С, 65.44; Н, 5.86; Р, 11.25; S, 11.65.
Found: С, 65.52; Н, 5.80; Р, 11.35; S, 11.59.
Anal. Сalcd for C30H40O6P2: С, 64.51; Н, 7.22; Р, 11.09. Found: С,
64.59; Н, 7.51; Р, 11.32.
2-{2-[2-(Diphenethylphosphorothioyl)ethoxy]ethoxy}ethyl(di-
phenethyl)phosphine Sulfide (6b)
Yield: 252 mg (95%) (method A); white powder; mp 78–79 °C.
IR (KBr): 752 (P–C), 600 (P=S) cm–1.
2-{2-[2-(Diphenylphosphino)ethoxy]ethoxy}ethyl 2-(Diphenyl-
phosphino)ethyl Ether (4a)
Yield: 178 mg (84%) (method B); colorless oil.
IR (KBr): 740 (P–C) cm–1.
2
3
1H NMR (400 MHz, CDCl3): δ = 2.04 (dt, JP–H = 10.4, JH–H
=
3
1H NMR (400 MHz, CDCl3): δ = 2.34 (t, JH–H = 7.8 Hz, 4 H,
6.2 Hz, 4 H, PCH2CH2O), 2.12–2.19 (m, 8 H, PCH2), 2.92 (q,
PCH2), 3.46–3.56 (m, 12 H, OCH2), 7.25–7.37 (m, 20 H, Ph).
3JH–H = 3JP–H = 8.6 Hz, 8 H, PhCH2), 3.57 (s, 4 H, OCH2), 3.80 (dt,
3
3JP–H = 17.7 Hz, JH–H = 6.2 Hz, 4 H, PCH2CH2O), 7.19–7.29 (m,
1
13C NMR (100 MHz, CDCl3): δ = 28.8 (d, JP–C = 13.0 Hz,
20 H, Ph).
2
PCH2CH2O), 68.8 (d, JP–C = 26.1 Hz, PCH2CH2O), 70.1, 70.6
2
1
(CH2O), 128.4 (p-C in Ph), 128.5 (d, JP–C = 13.4 Hz, o-C in Ph),
13C NMR (100 MHz, CDCl3): δ = 28.5 (СH2Ph), 31.6 (d, JP–C
=
2
3
1
132.6 (d, JP–C = 18.8 Hz, m-C in Ph), 138.4 (d, JP–C = 12.7 Hz,
49.9 Hz, PCH2CH2O), 33.3 (d, JP–C = 48.3 Hz, CH2P), 64.9, 70.2
(OCH2), 126.4 (p-C in Ph), 128.2 (o-C in Ph), 128.6 (m-C in Ph),
140.8 (d, 3JP–C = 14.8 Hz, ipso-C in Ph).
ipso-C in Ph).
31P NMR (162 MHz, CDCl3): δ = –21.6.
31P NMR (162 MHz, CDCl3): δ = 48.5.
Anal. Сalcd for C32H36O3P2: С, 72.44; Н, 6.84; Р, 11.68. Found: C,
72.60; Н, 6.98; Р, 11.32.
Anal. Сalcd for C38H48O2P2S2: С, 68.85; Н, 7.30; Р, 9.35; S, 9.67.
Found: C, 69.09; Н, 7.15; Р, 9.63; S, 9.47.
2-{2-[2-(Diphenethylphosphino)ethoxy]ethoxy}ethyl 2-(Di-
phenethylphosphino)ethyl Ether (4b)
Yield: 219 mg (85%) (method A); colorless oil.
IR (KBr): 752 (P–C) cm–1.
1H NMR (400 MHz, CDCl3): δ = 1.81–1.88 (m, 12 H, PCH2), 2.76–
2.82 (m, 8 H, PhCH2), 3.62–3.70 (m, 12 H, CH2O), 7.22–7.36 (m,
20 H, Ph).
2-{2-[2-(Diphenethylphosphorothioyl)ethoxy]-1-methyl-
ethoxy}ethyl(diphenethyl)phosphine Sulfide (6c)
Yield: 260 mg (96%) (method A); colorless oil.
IR (KBr): 752 (P–C), 600 (P=S) cm–1.
1H NMR (400 MHz, CDCl3): δ = 1.13 (d, 3JH–H = 6.2 Hz, 3 H, CH3),
2.03–2.07 (m, 4 H, PCH2), 2.16–2.23 (m, 8 H, PCH2), 2.94 (dt,
Synthesis 2012, 44, 2938–2946
© Georg Thieme Verlag Stuttgart · New York

PAPER
Synthesis of Podands
2943
3JP–H = 8.9 Hz, 3JH–H = 7.3 Hz, 8 H, PhCH2), 3.42 (d, 3JH–H = 4.8 Hz,
2 H, OCH2), 3.61 (q, JH–H = 6.2 Hz, 1 H, OCH2CHO), 3.74–3.80
(m, 4 H, PCH2CH2O), 7.19–7.23 (m, 20 H, Ph).
Diphenethyl(15-phenethyl-17-phenyl-15-thioxo-3,6,9,12-tetra-
oxa-15λ5-phosphaheptadecyl)phosphine Sulfide (8a)
3
Yield: 294 mg (98%) (method A); white powder; mp 58–59 °C.
IR (KBr): 753 (P–C), 598 (P=S) cm–1.
13C NMR (100 MHz, CDCl3): δ = 16.6 (CH3), 28.2 (СH2Ph), 31.0
1
1
1H NMR (400 MHz, CDCl3): δ = 2.11–2.24 (m, 12 H, PCH2), 2.95
and 31.2 (d, JP–C = 49.5 Hz and JP–C = 49.9 Hz, PCH2CH2O,
1
3
3
PCH2CHO), 33.4 (d, JP–C = 48.3 Hz, PCH2), 62.6, 64.8, 74.4
(dt, JP–H = 9.9 Hz, JH–H = 6.2 Hz, 8 H, PhCH2), 3.47 (br s, 4 H,
3
(CH2O, CHO), 126.1 (p-C in Ph), 127.8 (o-C in Ph), 128.3 (m-C in
Ph), 140.4 and 140.3 (d, 3JP–C = 14.0 Hz and 3JP–C = 13.8 Hz, ipso-
C in Ph).
31P NMR (162 MHz, CDCl3): δ = 48.1, 48.4.
CH2O), 3.54–3.57 (m, 8 H, CH2O), 3.83 (dt, JP–H = 18.1 Hz,
3JH–H = 6.2 Hz, 4 H, PCH2CH2O), 7.18–7.30 (m, 20 H, Ph).
1
13C NMR (100 MHz, CDCl3): δ = 28.6 (PhСH2), 31.9 (d, JP–C
=
1
49.5 Hz, PCH2CH2O), 33.8 (d, JP–C = 48.3 Hz, PCH2), 65.1, 70.4
and 70.5 (OCH2), 126.5 (p-C in Ph), 128.3 (o-C in Ph), 128.7 (m-C
in Ph), 140.8 (d, 3JP–C = 14.4 Hz, ipso-C in Ph).
Anal. Сalcd for C39H50O2P2S2: С, 69.20; Н, 7.45; Р, 9.15; S, 9.47.
Found: C, 69.40; Н, 7.72; Р, 9.29; S, 9.08.
31P NMR (162 MHz, CDCl3): δ = 48.4.
2-{2-[2-(Diphenethylphosphoroselenoyl)ethoxy]ethoxy}ethyl-
(diphenethyl)phosphine Selenide (6d)
Yield: 278 mg (92%) (method A); colorless oil.
Anal. Сalcd for C42H56O4P2S2: С, 67.17; Н, 7.52; Р, 8.25; S, 8.54.
Found: C, 67.40; Н, 7.72; Р, 8.29; S, 8.08.
IR (KBr): 751 (P–C), 460 (P=Se) cm–1.
1H NMR (400 MHz, CDCl3): δ = 2.12 (dt, 2JP–H = 10.8 Hz, 3JH–H
Diphenethyl(15-phenethyl-17-phenyl-15-selenoxo-3,6,9,12-
tetraoxa-15λ5-phosphaheptadecyl)phosphine Selenide (8b)
Yield: 304 mg (90%) (method A); colorless oil.
IR (KBr): 751 (P–C), 460 (P=Se) cm–1.
=
6.0 Hz, 4 H, PCH2CH2O), 2.24–2.33 (m, 8 H, PCH2), 2.92 (q,
3JH–H = 3JP–H = 9.4 Hz, 8 H, PhCH2), 3.58 (s, 4 H, OCH2), 3.83 (dt,
3
3JP–H = 18.9 Hz, JH–H = 6.0 Hz, 4 H, PCH2CH2O), 7.18–7.31 (m,
1H NMR (400 MHz, CDCl3): δ = 2.22–2.38 (m, 12 H, PCH2), 2.93–
20 H, Ph).
2.99 (m, 8 H, PhCH2), 3.49 (s, 4 H, CH2O), 3.55–3.60 (m, 8 H,
13C NMR (100 MHz, CDCl3): δ = 29.2 (PhСH2), 31.2 (d, JP–C
=
1
3
3
CH2O), 3.85 (dt, JP–H = 18.8 Hz, JH–H = 6.2 Hz, H, PCH2CH2O),
1
43.5 Hz, PCH2CH2O), 33.4 (d, JP–C = 41.3 Hz, PCH2), 65.8, 70.3
(OCH2), 126.6 (p-C in Ph), 128.3 (o-C in Ph), 128.8 (m-C in Ph),
140.7 (d, 3JP–C = 14.8 Hz, ipso-C in Ph).
7.20–7.32 (m, 20 H, Ph).
1
13C NMR (100 MHz, CDCl3): δ = 29.4 (PhСH2), 31.5 (d, JP–C
=
1
43.1 Hz, PCH2CH2O), 33.4 (d, JP–C = 41.6 Hz, PCH2), 67.1, 70.4
(OCH2), 126.6 (p-C in Ph), 128.4 (o-C in Ph), 128.7 (m-C in Ph),
140.7 (d, 3JP–C = 14.7 Hz, ipso-C in Ph).
31P NMR (162 MHz, CDCl3): δ = 37.5 (s, 1JP–Se = 698 Hz).
Anal. Сalcd for C38H48O2P2Se2: С, 60.32; Н, 6.39; Р, 8.19; Se,
20.87. Found: C, 60.49; Н, 6.15; Р, 8.23; Se, 20.62.
31P NMR (162 MHz, CDCl3): δ = 37.4 (s, 1JP–Se = 698 Hz).
12,12-Diphenyl-12-thioxo-3,6,9-trioxa-12λ5-phosphadodec-
yl(diphenyl)phosphine Sulfide (7a)
Anal. Сalcd for C42H56O4P2Se2: С, 67.17; Н, 7.52; Р, 8.25; Se, 8.54.
Found: C, 67.40; Н, 7.72; Р, 8.29; Se, 8.08.
Yield: 224 mg (94%) (method B); colorless oil.
2-{3-[2-(Diphenethylphosphorothioyl)ethoxy]propoxy}ethyl
(Diphenethyl)phosphine Sulfide (9a)
Yield: 260 mg (96%) (method A); colorless oil.
IR (KBr): 753 (P–C), 599 (P=S) cm–1.
IR (KBr): 752 (P–C), 600 (P=S) cm–1.
1H NMR (400 MHz, CDCl3): δ = 2.76–2.81 (m, 4 H, PCH2), 3.36–
3.49 (m, 8 H, CH2O), 3.76–3.82 (m, 4 H, PCH2CH2O), 7.41–7.45
(m, 12 H, Ph), 7.78–7.81 (m, 8 H, Ph).
3
1H NMR (400 MHz, CDCl3): δ = 1.77 (quin, JH–H = 6.2 Hz, 2 H,
1
13C NMR (100 MHz, CDCl3): δ = 28.2 (PhСH2), 31.4 (d, JP–C
=
CH2), 2.07 (dt, 2JP–H = 10.7 Hz, 3JH–H = 6.1 Hz, 4 H, PCH2CH2O),
2.14–2.21 (m, 8 H, PCH2), 2.94 (dt, 3JH–H = 7.4 Hz, 3JP–H = 9.2 Hz,
1
49.5 Hz, PCH2CH2O), 33.4 (d, JP–C = 48.3 Hz, PCH2), 64.7, 69.9
3
2
8 H, PhCH2), 3.45 (t, 3JH–H = 6.1 Hz, 4 H, CH2O), 3.72 (dt, 3JP–H
17.7 Hz, JH–H = 6.2 Hz, 4 H, PCH2CH2O), 7.17–7.30 (m, 20 H,
=
(OCH2), 128.3 (d, JP–C = 12.3 Hz, m-C in Ph), 130.7 (d, JP–C
=
1
3
10.4 Hz, o-C in Ph), 131.1 (p-C in Ph), 132.7 (d, JP–C = 80.9 Hz,
ipso-C in Ph).
31P NMR (162 MHz, CDCl3): δ = 38.7.
Ph).
13C NMR (100 MHz, CDCl3): δ = 28.6 (PhСH2), 29.9 (CH2), 31.5
1
1
(d, JP–C = 49.9 Hz, PCH2CH2O), 33.6 (d, JP–C = 48.3 Hz, PCH2),
64.8, 68.1 (OCH2), 126.5 (p-C in Ph), 128.2 (o-C in Ph), 128.7 (m-
C in Ph), 140.8 (d, 3JP–C = 14.8 Hz, ipso-C in Ph).
Anal. Сalcd for C32H36O3P2S2: С, 64.63; Н, 6.10; Р, 10.42; S, 10.78.
Found: С, 64.69; Н, 6.26; Р, 10.58; S, 10.89.
Diphenethyl(12-phenethyl-14-phenyl-12-thioxo-3,6,9-trioxa-
12λ5-phosphatetradecyl)phosphine Sulfide (7b)
Yield: 277 mg (98%) (method A); colorless oil.
IR (KBr): 752 (P–C), 600 (P=S) cm–1.
31P NMR (162 MHz, CDCl3): δ = 48.3.
Anal. Сalcd for C39H50O2P2S2: С, 69.20; Н, 7.45; Р, 9.15; S, 9.47.
Found: C, 69.40; Н, 7.72; Р, 9.69; S, 9.08.
1H NMR (400 MHz, CDCl3): δ = 2.10–2.24 (m, 12 H, PCH2), 2.96
2-{3-[2-(Diphenethylphosphorothioyl)ethoxy]butoxy}ethyl
(Diphenethyl)phosphine Sulfide (9b)
3
3
(dt, JP–H = 9.4 Hz, JH–H = 7.1 Hz, 8 H, PhCH2), 3.53 (br s, 8 H,
CH2O), 3.81 (dt, 3JP–H = 17.8 Hz, 3JH–H = 6.1 Hz, 4 H, PCH2CH2O),
Yield: 268 mg (97%) (method A); colorless oil.
IR (KBr): 752 (P–C), 598 (P=S) cm–1.
1H NMR (400 MHz, CDCl3): δ = 1.10 (d, 3JH–H = 6.2 Hz, 3 H, CH3),
7.19–7.32 (m, 20 H, Ph).
1
13C NMR (100 MHz, CDCl3): δ = 28.2 (PhСH2), 31.4 (d, JP–C
=
1
49.5 Hz, PCH2CH2O), 33.4 (d, JP–C = 48.3 Hz, PCH2), 64.7, 69.9
(OCH2), 126.1 (p-C in Ph), 127.8 (o-C in Ph), 128.3 (m-C in Ph),
140.5 (d, 3JP–C = 14.4 Hz, ipso-C in Ph).
1.58–1.74 (m, 2 H, CH2), 2.03–2.22 (m, 12 H, PCH2), 2.94 (dt,
3
3JH–H = JP–H = 8.6 Hz, 8 H, PhCH2), 3.42–3.84 (m, 7 H, CH2O,
CHO), 7.17–7.28 (m, 20 H, Ph).
31P NMR (162 MHz, CDCl3): δ = 48.3.
13C NMR (100 MHz, CDCl3): δ = 19.8 (CH3), 28.7 (PhСH2), 31.6
and 31.7 (d, 1JP–C = 49.9 and 1JP–C = 50.3 Hz, PCH2CH2O), 33.9 (d,
1JP–C = 47.5 Hz, PCH2), 36.8 (CH2CHO), 62.5, 64.8, 67.8 (CH2O),
73.1 (CHO), 126.5 (p-C in Ph), 128.3 (o-C in Ph), 128.7 (m-C in
Ph), 140.8 and 140.9 (d, 3JP–C = 14.0 Hz, ipso-C in Ph).
Anal. Сalcd for C40H52O2P2S2: С, 67.96; Н, 7.41; Р, 8.76; S, 9.07.
Found: C, 68.18; Н, 7.42; Р, 9.07; S, 8.49.
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2012, 44, 2938–2946

2944
L. A. Oparina et al.
PAPER
3
3
31P NMR (162 MHz, CDCl3): δ = 48.3, 48.4.
Hz, JH–H = 7.8 Hz, 8 H, PhCH2), 3.39 (t, JH–H = 6.5 Hz, 4 H,
CH2O), 3.77 (dt, 3JP–H = 19.3 Hz, 3JH–H = 6.1 Hz, 4 H, PCH2CH2O),
7.18–7.28 (m, 20 H, Ph).
Anal. Сalcd for C40H52O2P2S2: С, 69.53; Н, 7.59; Р, 8.97; S, 9.28.
Found: C, 69.09; Н, 7.54; Р, 8.83; S, 9.49.
13C NMR (100 MHz, CDCl3): δ = 26.0 (СH2Ph), 29.4, 29.6 (СH2),
32.5 (d, JP–C = 43.5 Hz, PCH2CH2O), 33.4 (d, JP–C = 41.3 Hz,
PCH2), 64.4, 71.3 (OCH2), 126.5 (p-C in Ph), 128.3 (o-C in Ph),
128.7 (m-C in Ph), 140.5 (d, 3JP–C = 14.7 Hz, ipso-C in Ph).
1
1
2-{4-[2-(Diphenethylphosphorothioyl)ethoxy]butoxy}ethyl
(Diphenethyl)phosphine Sulfide (9c)
Yield: 268 mg (97%) (method A); white powder; mp 58–59 °C.
IR (KBr): 752 (P–C), 599 (P=S) cm–1.
31P NMR (162 MHz, CDCl3): δ = 37.1 (s, 1JP–Se = 694 Hz).
1H NMR (400 MHz, CDCl3): δ = 1.55 (m, 4 H, CH2), 2.06–2.12 (m,
4 H, PCH2CH2O), 2.14–2.22 (m, 8 H, PCH2), 2.94 (dt, 3JP–H = 9.2,
3JH–H = 7.9 Hz, 8 H, PhCH2), 3.38 (br s, 4 H, CH2O), 3.74 (dt,
Anal. Сalcd for C42H56O2P2Se2: С, 62.07; Н, 6.94; Р, 7.62; Se,
19.43. Found: C, 62.29; Н, 6.89; Р, 7.13; Se, 19.75.
3
3JP–H = 18.2 Hz, JH–H = 6.2 Hz, 4 H, PCH2CH2O), 7.17–7.30 (m,
2-{2-[2-(Diphenethylphosphoryl)ethoxy]ethoxy}ethyl
(Diphenethyl)phosphine Oxide (10)
20 H, Ph).
A solution of diphosphine 3b (174 mg, 0.29 mmol) in 1,4-dioxane
(5 mL) was stirred in air at r.t. for 3 h. The solvent was then evapo-
rated in vacuo, and the residue was reprecipitated from chloroform
to hexane and dried in vacuo to give diphosphine oxide 10.
13C NMR (100 MHz, CDCl3): δ = 26.4 (PhCH2), 28.6 (СH2), 31.9
(d, JP–C = 49.9 Hz, PCH2CH2O), 33.9 (d, JP–C = 48.3 Hz, PCH2),
64.7, 70.9 (OCH2), 126.5 (p-C in Ph), 128.2 (o-C in Ph), 128.7 (m-
C in Ph), 140.7 (d, 3JP–C = 14.4 Hz, ipso-C in Ph).
1
1
Yield: 179 mg (98%); colorless waxy solid.
IR (KBr): 1155 (P=O), 752 (P–C) cm–1.
1H NMR (400 MHz, CDCl3): δ = 1.99–2.19 (m, 12 H, PCH2), 2.91–
3.00 (m, 8 H, PhCH2), 3.61 (s, 4 H, OCH2), 3.74–3.91 (m, 4 H,
PCH2CH2O), 7.21–7.33 (m, 20 H, Ph).
31P NMR (162 MHz, CDCl3): δ = 48.3.
Anal. Сalcd for C40H52O2P2S2: С, 69.53; Н, 7.59; Р, 8.97; S, 9.28.
Found: C, 69.40; Н, 7.72; Р, 8.29; S, 9.06.
2-(6-[2-(Diphenethylphosphorothioyl)ethoxy]hexyloxy)ethyl
(Diphenethyl)phosphine Sulfide (9d)
Yield: 282 mg (98%) (method A); white powder; mp 81–83 °C.
IR (KBr): 753 (P–C), 600 (P=S) cm–1.
13C NMR (100 MHz, CDCl3): δ = 27.5 (PhСH2), 28.8 (d, JP–C
=
=
1
59.8 Hz, PCH2CH2O), 30.7 and 30.8 (d, 1JP–C = 63.3 Hz and 1JP–C
62.9 Hz, PCH2), 68.5, 69.9 (CH2O), 126.2 (p-C in Ph), 128.11 (o-C
1H NMR (400 MHz, CDCl3): δ = 1.27 (m, 4 H, CH2), 1.48 (m, 4 H,
in Ph), 128.8 (m-C in Ph), 142.4 (d, 3JP–C = 13.4 Hz, ipso-C in Ph).
CH2), 2.09–2.24 (m, 12 H, PCH2), 2.95 (dt, 3JP–H = 9.0 Hz, 3JH–H
=
31P NMR (161 MHz, CDCl3): δ = 46.5.
7.1 Hz, 8 H, PhCH2), 3.47 (t, 3JH–H = 6.4 Hz, 4 H, CH2O), 3.77 (dt,
3
3JP–H = 18.3 Hz, JH–H = 6.0 Hz, 4 H, PCH2CH2O), 7.17–7.28 (m,
Anal. Сalcd for C38H48O4P2: С, 72.36; Н, 7.67; Р, 9.82. Found: С,
72.58; Н, 7.36; Р, 9.64.
20 H, Ph).
13C NMR (100 MHz, CDCl3): δ = 26.1 (CH2), 28.4 (CH2), 29.6
Synthesis of Salt 11 (Scheme 7)
1
1
(СH2Ph), 32.0 (d, JP–C = 49.9 Hz, PCH2CH2O), 33.9 (d, JP–C
=
A solution of phosphine 4a (133 mg, 0.25 mmol) and MeI (0.3 mL)
in CH2Cl2 (2 mL) was stirred at 23–25°С for 1 h. The solvent and
excess MeI was removed in vacuo, and the residue was precipitated
from CHCl3 (1 mL) in hexane (7 mL) to give phosphonium diiodide
11.
48.3 Hz, CH2P), 64.7, 71.3 (OCH2), 126.5 (p-C in Ph), 128.3 (o-C
in Ph), 128.7 (m-C in Ph), 140.8 (d, 3JP–C = 14.8 Hz, ipso-C in Ph).
31P NMR (162 MHz, CDCl3): δ = 48.4.
Anal. Сalcd for C42H56O2P2S2: С, 70.16; Н, 7.85; Р, 8.62; S, 8.92.
Found: C, 70.29; Н, 7.19; Р, 9.13; S, 9.75.
Yield: 198 mg (97%); colorless waxy solid.
IR (KBr): 642 (P–C), 918 (P–Me) cm–1.
1Н NMR (400 MHz, CDCl3): δ = 2.74 (d, JP–H = 13.9 Hz, 6 H,
2-{4-[2-(Diphenethylphosphoroselenoyl)ethoxy]butoxy}ethyl
(Diphenethyl)phosphine Selenide (9e)
Yield: 292 mg (93%) (method A); colorless oil.
IR (KBr): 751 (P–C), 460 (P=Se) cm–1.
2
CH3), 3.28 (m, 4 H, PCH2), 3.35 (m, 4 H, OCH2), 3.52 (quin,
3JH–H = 6.0 Hz, 4 H, OCH2), 3.80 (dt, JP–H = 21.1 Hz, JH–H
=
3
3
5.7 Hz, 4 H, PCH2CH2O), 7.54 (dt, 4JP–Н = 10.6 Hz, 3JH–Н = 7.5 Hz,
8 Н, m-H in Ph), 7.64 (t, 3JH–Н = 7.5 Hz, 4 Н, p-H, Ph), 7.87 (dd,
3JP–Н = 13.0 Hz, 3JH–Н = 7.5 Hz, 8 Н, o-H in Ph).
1H NMR (400 MHz, CDCl3): δ = 1.55–1.63 (m, 4 H, CH2), 2.16–
2.23 (m, 4 H, PCH2), 2.25–2.34 (m, 8 H, PCH2), 2.95 (dt, 3JP–H = 9.2
Hz, 3JH–H = 8.0 Hz, 8 H, PhCH2), 3.39 (br s, 4 H, CH2O), 3.78 (dt,
13C NMR (100 MHz, CDCl3): δ = 9.9 (d, JP–C = 54.8 Hz, CH3),
1
3
3JP–H = 19.0 Hz, JH–H = 7.0 Hz, 4 H, PCH2CH2O), 7.18–7.29 (m,
1
2
25.0 (d, JP–C = 53.4 Hz, PCH2), 64.2 (d, JP–C = 7.0 Hz,
20 H, Ph).
1
PCH2CH2O), 70.0, 70.4 (OCH2), 119.7 (d, JP–C = 85.8 Hz, ipso-C
13C NMR (100 MHz, CDCl3): δ = 26.3 (PhCH2), 29.3 (СH2), 31.3
2
3
in Ph), 130.0 (d, JP–C = 12.6 Hz, o-C in Ph), 132.6 (d, JP–C
=
1
1
(d, JP–C = 43.5 Hz, PCH2CH2O), 33.3 (d, JP–C = 41.3 Hz, PCH2),
65.3, 70.9 (OCH2), 126.5 (p-C in Ph), 128.2 (o-C in Ph), 128.6 (m-
C in Ph), 140.4 (d, 3JP–C = 14.8 Hz, ipso-C in Ph).
9.0 Hz, m-C in Ph), 132.7 (p-C in Ph).
31P NMR (162 MHz, CDCl3): δ = 24.4.
Anal. Сalcd for C34H42I2O3P2: C, 50.14; H, 5.20; I, 31.16; P, 7.61.
Found: C, 50.32; H, 5.28; I, 30.98; P, 7.59.
31P NMR (162 MHz, CDCl3): δ = 37.1 (s, 1JP–Se = 696 Hz).
Anal. Сalcd for C40H52O2P2Se2: С, 61.22; Н, 6.68; Р, 7.89; Se,
20.12. Found: С, 61.47; Н, 6.52; Р, 7.94; Se, 20.17.
Acknowledgment
2-(6-[2-(Diphenethylphosphoroselenoyl)ethoxy]hexyloxy) Eth-
yl(diphenethyl)phosphine Selenide (9f)
Yield: 293 mg (90%) (method A); white powder; mp 88 °C.
IR (KBr): 748 (P–C), 462 (P=Se) cm–1.
This work was supported by a research grant from the Russian
Foundation of Basic Research (11–03–00286a) and the President of
the Russian Federation (program for the support of leading scienti-
fic schools, grant NSh-1550.2012.3).
1H NMR (400 MHz, CDCl3): δ = 1.26–1.34 (m, 4 H, CH2), 1.45–
1.56 (m, 4 H, CH2), 2.19–2.36 (m, 12 H, PCH2), 2.96 (dt, 3JP–H = 9.4
Synthesis 2012, 44, 2938–2946
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Synthesis of Podands
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