Nucleophilic additon of phosphine to 1-(tert-butyl)-4-vinylbenzene: a short-cut to bulky secondary and tertiary phosphines and their chalcogenides

Article abstract of DOI:10.1016/j.mencom.2008.09.011

Phosphine readily adds to 1-(tert-butyl)-4-vinylbenzene in the KOH-DMSO system (70-120 °C, 3 h, atmospheric pressure) to form bis[4-(tert-butyl)phenethyl]phosphine and tris[4-(tert-butyl)phenethyl]phosphine, which are further oxidized to corresponding phosphine oxides, sulfides and selenides.

Full text of DOI:10.1016/j.mencom.2008.09.011

Mendeleev
Communications
Mendeleev Commun., 2008, 18, 260–261
Nucleophilic additon of phosphine to
1-(tert-butyl)-4-vinylbenzene: a short-cut to bulky
secondary and tertiary phosphines and their chalcogenides
Nina K. Gusarova, Svetlana F. Malysheva, Vladimir A. Kuimov,
Nataliya A. Belogorlova, Valentina L. Mikhailenko 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: gusarova@irioch.irk.ru
DOI: 10.1016/j.mencom.2008.09.011
Phosphine readily adds to 1-(tert-butyl)-4-vinylbenzene in the KOH–DMSO system (70–120 °C, 3 h, atmospheric pressure) to
form bis[4-(tert-butyl)phenethyl]phosphine and tris[4-(tert-butyl)phenethyl]phosphine, which are further oxidized to corresponding
phosphine oxides, sulfides and selenides.
Organic phosphines and phosphine chalcogenides are widely
KOH/DMSO (H2O)
used as ligands for metal-complex catalysts.1 Among such
ligands, bulky phosphines and phosphine chalcogenides are of
special importance. They are employed as building blocks to
design new catalytic systems for activation of cross-coupling
But
PH3
+
Ar
1
But
reactions,2
(a)–(c)
amination,
2(d),(e)
cyanation,
2(f)
silylation,
2(g),(h)
2(i)
2(j)
hydroboration of vinylarenes, arylation of ketones, reactions
But
2
(k)
2(l)
2(m)
of cyclization,
dimerization, trimerization,
and poly-
merization2
(n),(o)
of unsaturated compounds, etc.
As a rule, the bulky phosphines and phosphine chalcogenides
are synthesized from hazardous phosphorus halides and organo-
metallic reagents. An alternative and convenient approach to
the C–P bond formation is the reactions of PH addends with
PH
+
P
But
3
4
But
Scheme 1
But
alkenes. The simplest available PH addend is phosphine (PH ).
2
3
3
However, this alternative is not systematically elaborated, though
a few addition reactions of phosphine to multiple C–C bonds
have been published.3
(d),5
Conditions for selective preparation of phosphines 2 or 3
have been elaborated. Secondary phosphine 2 has been syn-
thesized in 87% yield by slow addition of styrene 1 to a
suspension of KOH–DMSO (~2 wt% H O from total weight of
the reaction mixture styrene–KOH–DMSO) heated to 70 °C with
simultaneous vigorous passing of a phosphine stream through
This paper reports a facile atom-economic one-pot method
for the synthesis of secondary and tertiary phosphines and
phosphine chalcogenides bearing bulky sterically hindered
tert-butylphenyl substituents. Here, the method is exemplified
by the nucleophilic addition of phosphine to 1-(tert-butyl)-
2
‡
4
-vinylbenzene in the KOH–DMSO system. The investigation
the suspension. Exhausting and selective 4-tert-butylphenylation
of the reaction is also of basic importance both for organo-
phosphorus and alkene chemistry. Indeed, the addition of PH
nucleophiles to arylalkenes is unusual and, to our knowledge, is
described only for styrene, α-methyl- and α-phenylstyrene.3
Under specially forced superbasic conditions (the sodium naph-
thalenide–TMEDA–THF system), a CH acid (2-methylpropanoic)
seems to be the only nucleophile capable of adding to styrene.7
As far as the electron donating substituents in the benzene
ring should slow down the nucleophilic addition to the double
bond of vinylbenzene, a possibility of the reaction of phosphine
with 1-(tert-butyl)-4-vinylbenzene is far from to be obvious.
of phosphine occurs at 70–120 °C in the KOH–DMSO system
in the presence of H O (1.5 wt%) under additional introduction
2
of styrene 1 (~ one third from the total weight) to the reaction
(d),6
†
Preparation of phosphine. Red phosphorus (15.5 g, 500 mmol) and
toluene (50 ml) were placed in a 500-ml conical three-necked flask fitted
with a gas inlet, combined with a pressure-equalizing dropping funnel, a
magnetic stirrer, a reflux condenser, and a combination of outlet. An aqueous
solution of 50 wt% KOH (50 g, 893 mmol) was added in the dropping
funnel. The flask was connected, via a washing bottle [containing a mixture
of aqueous KOH (50%) and DMSO] with a 200-ml four-necked flask
containing KOH–DMSO–H O. This second flask was equipped with an
2
†
efficient mechanical stirrer, a combination of gas-inlet tube and a dropping
funnel containing a mixture of the styrene 1 and DMSO, and a combina-
tion of gas-outlet and thermometer. The outlet of the flask was connected
We have found that phosphine reacts with 1-(tert-butyl)-
4
-vinylbenzene 1 in a KOH–DMSO suspension in the presence
of a small quantity of H O at 70–120 °C for 3 h to give
2
with another washing bottle containing an aqueous solution of CuSO (for
4
bis[4-(tert-butyl)phenethyl]phosphine 2 and tris[4-(tert-butyl)-
phenethyl]phosphine 3 (Scheme 1).
In the absence of KOH no reaction occurs. This fact confirms
a nucleophilic mechanism of addition, which is presumed to be
through the phosphide anions, formed from phosphine under
the action of the superbase KOH–DMSO system.
trapping unreacted phosphine and converting it into cupric phosphide).
The contents of the first flask were refluxed to ~60–70 °C, those of the
second flask, to 70 °C.
The rate of this addition was adjusted so that PH was evolved at a rate
3
of 45–50 bubbles per min. 10 min after the evolution of PH began, the
3
addition of the styrene–DMSO mixture was started.
©
2008 Mendeleev Communications. All rights reserved.
– 260 –

Mendeleev Commun., 2008, 18, 260–261
But
sponding secondary 4a,b and tertiary 5a–c phosphine chalco-
genides in high yields (Scheme 2).¶
Thus, the reaction of phosphine with styrene 1 is a convenient
approach to the synthesis of secondary and tertiary phosphine
and phosphine chalcogenides with bulky sterically hindered
tert-butylphenyl moieties, possible ligands for the design of the
special metal complex catalysts, as well as intermediates and
coordinating solvents for the preparation of conductive nano-
materials.8
X
H
i or ii
2
P
But
1
4
4
a X = O
b X = Se
But
This work was supported by the Russian Foundation for
Basic Research (grant no. 07-03-00562a).
X
i or ii
3
P
Online Supplementary Materials
But
But
Supplementary data associated with this article can be found
in the online version at doi:10.1016/j.mencom.2008.09.011.
5
5
5
a X = O
b X = S
c X = Se
References
Scheme 2 Reagents and conditions: i, aqueous H O2 (36%), acetone,
1 (a) M. K. Whittlesey, in Organometallic Chemistry, ed. M. Green, The Royal
Society of Chemistry, London, 2000, vol. 28, p. 367; (b) N. T. S. Phan,
M. Van Der Sluys and Ch. W. Jones, Adv. Synth. Catal., 2006, 348, 609;
2
5
0 °C, 2 h; ii, S or Se, toluene, Ar, 60 °C, 2 h.
8
mixture after completion of phosphine feeding. These condi-
(c) J. J. M. de Pater, B.-J. Deelman, C. J. Elsevier and G. van Koten, Adv.
§
tions allow phosphine 3 to be prepared in 69% yield.
Synth. Catal., 2006, 348, 1447; (d) S. E. Gibson and M. Rudd, Adv. Synth.
Catal., 2007, 349, 781.
Note that, under radical conditions (60–65 °C, AIBN, dioxane),
phosphine adds to styrene 1 non-selectively to form a mixture
of corresponding primary, secondary and tertiary phosphines in
low yields.
2
(a) J.-C. Hierso, A. Fihri, R. Amardeil, Ph. Meunier, H. Doucet and
M. Santelli, Tetrahedron, 2005, 61, 9759; (b) M. Moreno-Manas, R. Pleixats
and A. Serra-Muns, Synlett, 2006, 3001; (c) Ya-H. Gan, J.-Ch. Lee and
F.-E. Hong, Polyhedron, 2006, 25, 3555; (d) J.-Ch. Lee, M.-G. Wang and
F.-E. Hong, Eur. J. Inorg. Chem., 2005, 5011; (e) L. L. Hill, L. R. Moore,
R. Huang, R. Craciun, A. J. Vincent, D. A. Dixon, J. Chou, Ch. J. Woltermann
and K. H. Shaughnessy, J. Org. Chem., 2006, 71, 5117; (f) T. Schareina,
A. Zapf, W. Mägerlein, N. Müller and M. Beller, Tetrahedron Lett., 2007,
Phosphines 2, 3 react smoothly with an aqueous solution of
H O , elemental sulfur and selenium in toluene to give corre-
2
2
‡
Preparation of bis[4-(tert-butyl)phenethyl]phosphine 2. A solution of
styrene 1 (8.3 g, 51.8 mmol) in DMSO (5 ml) was added dropwise for
h to a suspension of KOH (10 g, 178.6 mmol), DMSO (40 ml) and
water (1.5 ml), blown through argon and saturated with phosphine, at
0 °C under stirring and continuous bubbling of phosphine. The reaction
4
8, 1087; (g) Y. Yamanoi, J. Org. Chem., 2005, 70, 9607; (h) Y. Yamanoi,
T. Taira, J.-I. Sato, I. Nakamula and H. Nishihara, Org. Lett., 2007, 9, 4543;
i) D. I. McIsaac, S. J. Geier, Ch. M. Vogels, A. Decken and S. A. Westcott,
2
(
Inorg. Chim. Acta., 2006, 359, 2771; (j) H. R. Chobanian, P. Liu,
M. D. Chioda, Y. Guo and L. S. Lin, Tetrahedron Lett., 2007, 48, 1213;
7
mixture was additionally heated (70 °C) for 1 h in the flow of phosphine,
and then the phosphine feeding was stopped. The mixture was blown
through argon, cooled, diluted with water and extracted with benzene. The
benzene extract was washed with water, dried over K CO , benzene was
(
k) A. Ochida, H. Ito and M. Sawamura, J. Am. Chem. Soc., 2006, 128,
1
2
6486; (l) S. Ogoshi, M. Ueta, M. Oka and H. Kurosawa, Chem. Commun.,
004, 2732; (m) K. Blann, A. Bollmann, J. T. Dixon, F. M. Hess, E. Killian,
2
3
H. Maumela, D. H. Morgan, A. Neveling, S. Otto and M. J. Overett, Chem.
Commun., 2005, 620; (n) W. Liu, J. M. Malinoski and M. Brookhart,
Organometallics, 2002, 21, 2836; (o) M. Jimenez-Tenorio, M. C. Puerta,
I. Salcedo, P. Valerga, S. I. Costa, L. C. Silva and P. T. Gomes, Organo-
metallics, 2004, 23, 3139.
distilled, and the residue was fractionated in a vacuum to recover 2.1 g
of styrene 1 (75% conversion). The residue was washed with hexane
(
10 ml) and dried in a vacuum to furnish 6 g (87%, calculated with
conversion 1) of phosphine 2.
The H, C, P and 77Se NMR spectra were recorded on a Bruker DPX 400
1
13 31
3 (a) M. O. Shulyupin, M. A. Kazankova and I. P. Beletskaya, Org. Lett., 2002,
4, 761; (b) M. Tanaka, in Topics in Current Chemistry, ed. J.-P. Majoral,
Springer, Berlin, Heidelberg, 2003, vol. 229, p. 26; (c) R. Engel and
spectrometer (400.13, 100.61, 161.98 and 76.31 MHz, respectively).
1
For 2: colourless powder, mp 138–139 °C (hexane). H NMR (C D )
6
6
nd
d: 1.35 (s, 18H, Me), 1.71–1.79 and 1.83–1.91 (m, 4H, CH P), 2.74–2.81
J. I. Cohen, Synthesis of Carbon–Phosphorus Bonds, 2 edn., CRC Press,
2
1
3
(
m, 4H, CH Ar), 3.27 (dq, 1H, J 195.3 Hz, J 7 Hz), 7.15–7.17 and
London, 2004; (d) F. Alonso, I. P. Beletskaya and M. Yus, Chem. Rev.,
2004, 104, 3079; (e) S. N. Arbuzova, N. K. Gusarova and B. A. Trofimov,
Arkivoc, 2006, v, 12; (f) D. Enders, A. Saint-Dizier, M.-I. Lannou and
A. Lenzen, Eur. J. Org. Chem., 2006, 29.
4 B. A. Trofimov, L. Brandsma, S. N. Arbuzova, S. F. Malysheva and
N. K. Gusarova, Tetrahedron Lett., 1994, 35, 7647.
5 N. K. Gusarova, N. I. Ivanova, M. V. Bogdanova, L. M. Sinegovskaya,
A. V. Gusarov and B. A. Trofimov, Phosphorus Sulfur Silicon Relat.
Elem., 2005, 180, 1749.
2
PH
HH
1
3
1
7
3
1
.36–7.38 (m, 8H, Ar). C NMR (C D ) d: 22.31 (d, CH P, J 11.9 Hz),
6 6 2 PC
1
1.08 (Me), 33.90 (CMe), 34.03 (d, CH Ar, J 10.7 Hz), 125.07 (Co-Ar),
27.80 (Cm-Ar), 139.35 (d, C , J 8.0 Hz), 148.32 (Cp-Ar). 31P NMR
CDCl ) d: –68.67 (d, J 195.9 Hz). Found (%): C, 81.47; H, 10.03;
2
PC
3
i-Ar
PC
1
(
3 PH
P, 8.81. Calc. for C H P (%): C, 81.31; H, 9.95; P, 8.74.
2
4
35
§
Preparation of tris[4-(tert-butyl)phenethyl]phosphine 3. A solution of
styrene 1 (5.5 g, 34.3 mmol) in DMSO (6.5 ml) was added dropwise for
h 40 min to a suspension of KOH (20 g, 357.1 mmol), DMSO (60 ml)
1
6
(a) D. Semenzin, G. Etemad-Moghadam, D. Albouy, O. Diallo and M. Koenig,
and water (1.5 ml), blown through argon and saturated with phosphine,
at 70 °C under stirring and continuous bubbling of the phosphine. The
phosphine feeding was stopped, the mixture was blown through argon,
and a solution of styrene 1 (2.8 g, 17.5 mmol) was added. The reaction
mixture was heated (120 °C) and stirred for 1 h, then cooled, diluted
with water, and extracted with toluene. The toluene extract was washed
with water, dried over K CO , the toluene was removed, the residue was
J. Org. Chem., 1997, 62, 2414; (b) T. Bunlaksananusorn and P. Knochel,
Tetrahedron Lett., 2002, 43, 5817.
7
8
T. Fujita, S. Watanabe, K. Suga and H. Nakayama, Synthesis, 1979, 310.
(a) The Chemistry of Nanomaterials, eds. C. N. R. Rao, A. Müller and
A. K. Cheetham, Wiley-VCH, New York, 2004, vol. 2; (b) A. Sashchiuk,
L. Amirav, M. Bashouti, M. Krueger, U. Sivan and E. Lifshitz, Nano Lett.,
2004, 4, 159; (c) S. P. Gubin, N. A. Kataeva and G. B. Khomutov, Izv.
Akad. Nauk, Ser. Khim., 2005, 811 (Russ. Chem. Bull., Int. Ed., 2005, 54,
827); (d) J. E. Halpert, V. J. Porter, J. P. Zimmer and M. G. Bawendi, J.
Am. Chem. Soc., 2006, 128, 12590; (e) A. H. Latham, M. J. Wilson,
P. Schiffer and M. E. Williams, J. Am. Chem. Soc., 2006, 128, 12632.
2
3
washed with hexane (10 ml) and dried in a vacuum to afford 6.1 g (69%)
1
of phosphine 3, colourless powder, mp 114–116 °C (hexane). H NMR
(
C D ) d: 1.37 (s, 27H, Me), 1.75–1.79 (m, 6H, CH P), 2.08–2.86 (m,
6
6
2
3
1
6
2
3
1
H, CH Ar), 7.20–7.26 and 7.39–7.40 (m, 12H, Ar). C NMR (C D ) d:
2
6
6
1
2
9.55 (d, CH P, J 14.5 Hz), 31.40 (Me), 32.14 (d, CH Ar, J 14.5 Hz),
4.25 (CMe), 127.64 (Co-Ar), 127.87 (Cm-Ar), 140.24 (d, Ci-Ar, J 9.5 Hz),
48.63 (Cp-Ar). P NMR (CDCl ) d: –26.57. Found (%): C, 83.96; H, 9.83;
2
PC
2
PC
Received: 4th April 2008; Com. 08/3114
3
PC
3
1
¶
For characteristics of compounds 4a,b and 5a–c, see Online Supple-
3
P, 5.81. Calc. for C H P (%): C, 84.00; H, 9.99; P, 6.02.
mentary Materials.
3
6
51
–
261 –