Atom-economic synthesis of tertiary 2-alkoxyethylphosphine sulfides

Article abstract of DOI:10.1070/MC2004v014n05ABEH001922

Secondary phosphine sulfides react chemo- and regiospecifically with alkyl vinyl ethers under radical conditions in the anti-Markovnikov mode giving corresponding tertiary phosphine sulfides in high yield.

Full text of DOI:10.1070/MC2004v014n05ABEH001922

,
2004, 14(5), 216–217
Atom-economic synthesis of tertiary 2-alkoxyethylphosphine sulfides
Nina K. Gusarova, Nina I. Ivanova, Maria V. Bogdanova, Svetlana F. Malysheva, Nataliya A. Belogorlova,
Boris G. Sukhov and Boris A. Trofimov*
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 664033 Irkutsk,
Russian Federation. Fax: +7 3952 41 9346; e-mail: tba@irioch.irk.ru
DOI: 10.1070/MC2004v014n05ABEH001922
Secondary phosphine sulfides react chemo- and regiospecifically with alkyl vinyl ethers under radical conditions in the anti-
Markovnikov mode giving corresponding tertiary phosphine sulfides in high yield.
Reactions of PH acids with alkenes represent one of the most
convenient approaches to C–P bond formation and continue
to attract attention as an efficient method for the synthesis of
phosphines and their derivatives, including asymmetrical and
functional ones. Addition of phosphines to double carbon–
This work was supported by the Ministry of Industry,
Science and Technologies of the Russian Federation (grant no.
NSH-2241.2003.3).
1
carbon bonds (including those of vinyl ethers) can proceed
†
General procedure for the preparation of compounds 3a–c (method A).
1
,2
1
under radical conditions or under the action of acidic or
A mixture of secondary phosphine sulfide 2 (0.41 g, 1.5 mmol), ether
a (0.11 g, 1.5 mmol) and AIBN (5 mg) in 5 ml of THF was stirred at
3
4
basic catalysts or metal complexes. At the same time, data
concerning the hydrothiophosphorylation of alkenes are scarce.
Thus, diorganylphosphine sulfides were reported to react with
alkenes and triethoxyvinylsilane in the presence of azaiso-
butyronitrile (AIBN) giving anti-Markovnikov adducts. There
was also a brief communication describing the base-catalysed
addition of secondary phosphine sulfides to acrylonitrile. How-
ever, no experimental details were given and reaction products
1
6
0–65 °C for 5 h under argon in a glass vial sealed with a rubber septum
and equipped with a small Teflon stirring bar. The solvent was then
removed under reduced pressure. The crude product was purified by
column chromatography (Al O , eluent: chloroform–acetone, 5:1; column
5
6
2
3
height, 90 mm; diameter, 12 mm) to give 0.51 g (98%) of 3a as a honey-
like product.
Phosphine sulfides 3b,c (honey-like products) were prepared in the
same way in 92 and 97% yields, respectively.
7
were neither isolated nor characterised.
1
H, C and 31PNMR spectra were recorded on a Bruker DPX 400
13
In this work, to obtain new information on the addition of
PH acids to alkenes and to extend the synthetic potential of this
reaction, we studied the hydrothiophosphorylation of alkyl
vinyl ethers 1a–c with secondary phosphine sulfide 2. The
reaction was found to proceed in the presence of AIBN under
mild conditions (60–65 °C, 5 h, THF) with chemo- and regio-
specific formation of bis(2-phenethyl)(2-alkoxyethyl)phosphine
sulfides 3a–c in 92–98% yield (method A).†
(
400.13, 101.61 and 161.98 MHz, respectively) spectrometer. IR spectra
were measured on a Bruker IFS-25 spectrometer in a microlayer.
1
Bis(2-phenethyl)(2-ethoxyethyl)phosphine sulfide 3a. H NMR (CDCl )
3
3
d: 7.32–7.25 (m, 10H, Ph), 3.85 and 3.80 (2dd, 2H, CH OEt, J
=
2
HH
3
3
=
J
6.4 Hz), 3.53 (q, 2H, CH Me, J 7.1 Hz), 3.07–2.96 (m, 4H,
PH 2 HH
CH Ph), 2.33–2.15 (m, 6H, CH P), 1.22 (t, 3H, Me). 13C NMR (CDCl )
2
2
3
3
d: 140.88 (d, Cipso, J 14.7 Hz), 128.78 (C ), 128.36 (C ), 126.56 (C ),
PC
m
o
p
2
66.71 (CH Me), 64.50 (d, CH OEt, JPC 3.9 Hz), 33.71 (d, 2CH P,
2
2
2
1
1
2
JPC 48.0 Hz), 32.13 (d, CH P, J 49.3 Hz), 28.71 (d, CH Ph, JPC
.0 Hz), 17.03 (Me). PNMR (CDCl ) d: 47.4 (s). IR (n/cm ): 600
2
PC
2
3
1
–1
3
3
Ph
Ph
(
P=S). Found (%): C, 69.31; H, 7.89; P, 8.89; S, 9.30. Calc. for
H
S
R
C H OPS (%): C, 69.33; H, 7.85; P, 8.94; S, 9.26.
2
0
27
P
P
SH
1
O
Bis(2-phenethyl)(2-butoxyethyl)phosphine sulfide 3b. H NMR (CDCl )
3
=
3
d: 7.29–7.21 (m, 10H, Ph), 3.80 and 3.76 (2dd, 2H, CH OBu, J
=
2
HH
Ph
Ph
R
3
3
JPH 5.9 Hz), 3.43 (dd, 2H, CH Pr, J 6.6 Hz), 2.99–2.93 (m, 4H,
2 HH
1
a–c
2
CH Ph), 2.28–2.11 (m, 6H, CH P), 1.52 (m, 2H, CH Et), 1.33 (m, 2H,
2
2
2
3
13
CH Me), 0.89 (t, 3H, Me, J 7.4 Hz). C NMR (CDCl ) d: 140.41
Ph
Ph
2
HH
3
3
(d, Cipso, J 14.2 Hz), 128.36 (C ), 127.94 (C ), 126.15 (C ), 70.86
PC
m
o
p
AIBN, 60–65 °C
THF
2
1
O
(
CH Pr), 64.36 (CH OBu, J 3.9 Hz), 33.27 (d, 2CH P, J 48.0 Hz),
2 2 PC 2 PC
P
a R = Et
b R = Bu
c R = Bui
31.46 (CH Et), 31.45 (d, CH P, 1J 49.7 Hz), 28.70 (CH Ph, 2J
S
2 2 PC 2 PC
9
2–98%
3
1
2.7 Hz), 19.13 (CH Me), 13.56 (Me). PNMR (CDCl ) d: 47.9 (s). IR
(n/cm ): 601 (P =S). Found (%): C, 70.51; H, 8.31; P, 8.25; S, 8.53.
2
3
–1
3a–c
Calc. for C H OPS (%): C, 70.55; H, 8.34; P, 8.27; S, 8.56.
2
2
31
Scheme 1
1
Bis(2-phenethyl)(2-isobutoxyethyl)phosphine sulfide 3c. H NMR
i
(
CDCl ) d: 7.28–7.19 (m, 10H, Ph), 3.78 and 3.73 (2dd, 2H, CH OBu ,
3
3
2
The structure of phosphine sulfides 3a–c was confirmed
3
i 3
JHH = J 6.1 Hz), 3.18 (d, 2H, CH Pr , J 6.6 Hz), 2.98–2.91 (m,
1
13
31
PH
2
HH
using NMR ( H, C, P) and IR spectroscopy, as well as by an
4
H, CH Ph), 2.29–2.12 (m, 6H, CH P), 1.82 (m, 1H, CH), 0.86 (d, 6H,
2
2
independent synthesis of compound 3b according to Scheme 2
3
13
3
Me, J 6.7 Hz). C NMR (CDCl ) d: 140.60 (d, C , J 14.4 Hz),
HH
3
ipso
PC
(
method B).‡
i
1
28.63 (C ), 128.21 (C ), 126.32 (C ), 78.31 (OCH Pr ), 64.45
m o p
2
i
2
1
(
CH OBu , J 3.5 Hz), 33.52 (d, 2CH P, J 48.6 Hz), 31.75 (CH P,
J
2 PC 2 PC 2
49.8 Hz), 28.58 (d, CH Ph, J 2.6 Hz), 28.37 (CH), 19.39 (Me).
PC 2 PC
Ph
Ph
1
2
i, AIBN, 65 °C, 5 h
3
1
–1
ii, S , PhMe, 50 °C, 3 h
PNMR (CDCl ) d: 48.2 (s). IR (n/cm ): 601 (P=S). Found (%): C,
8
3
1b
P
H
3b
9
8%
70.54; H, 8.32; P, 8.23; S, 8.54. Calc. for C 22H31OPS (%): C, 70.55; H,
8
.34;P, 8.27;S, 8.56.
Synthesis of compound 3b (method B).
‡
Scheme 2
A mixture of bis(2-phenethyl)phosphine (0.31 g, 1.3 mmol) and ether
b (0.13 g, 1.3 mmol) was heated at 65 °C in the presence of AIBN
1
(
Thus, the chemo- and regioselective addition of P,S-ambident
4 mg) in a sealed ampoule for 5 h to give bis(2-phenethyl)(2-butoxy-
secondary phosphine sulfides to alkyl vinyl ethers contributes
to understanding the reactivity of these compounds and offers
a facile straightforward atom-economic route to products 3, which
1
31
ethyl)phosphine, whose H and PNMR spectra corresponded to pub-
lished data.
1
(a)
Toluene (4 ml) and elemental sulfur (0.06 g, 1.8 mmol)
were successively added to the product obtained. The reaction mixture
was heated at 50 °C for 3 h; then, the solvent was removed under reduced
pressure. The residue was dissolved in diethyl ether, and unreacted
sulfur was filtered off. Removal of the ether gave 0.47 g (98%) of 3b as a
honey-like product.
8
9
are potent special solvents, cocatalysts, ‘hemilabile’ ligands
for example, triphenylphosphine sulfide is a more effective
ligand for palladium-catalysed bisalkoxycarbonylation of olefines
(
1
0
11
than triphenylphosphine ), and complex-forming agents.
2
16 Mendeleev Commun. 2004

,
2004, 14(5), 216–217
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Received: 5th April 2004; Com. 04/2248
Mendeleev Commun. 2004 217