Phenylethenyl-substituted silicones via Heck coupling reaction

Article abstract of DOI:10.1016/j.jorganchem.2009.07.001

Systematic studies of several palladium complexes (Pd(OAc)₂, [PdCl₂(cod)], [Pd₂(dba)₃], [Pd(PPh3)4], [PdCl(SnCl₃)(P{p-Tol}₃)₂], [Pd₂Cl₂(SnCl₃)

Full text of DOI:10.1016/j.jorganchem.2009.07.001

Journal of Organometallic Chemistry 694 (2009) 3386–3389
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Phenylethenyl-substituted silicones via Heck coupling reaction
a
b
c
b,
b
*
´
Anna Czech , Tomasz Ganicz , Małgorzata Noskowska , Włodzimierz A. Stanczyk , Anna Szela˛g
a GE Silicones, 771 Old Sawmill River Road, Tarrytown, New York 10591, USA
b
´
Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Łódz, Poland
c Hollister, Poleczki 47, 02-822 Warszawa, Poland
a r t i c l e i n f o
a b s t r a c t
Article history:
Systematic studies of several palladium complexes (Pd(OAc)2, [PdCl2(cod)], [Pd2(dba)3], [Pd(PPh3)4],
[PdCl(SnCl3)(P{p-Tol}3)2], [Pd2Cl2(SnCl3)2(P{p-Tol}3)2]) as potential catalytic systems for arylation of
vinylsiloxanes via Heck coupling reactions are described. Catalytic activity and selectivity were studied
for a model reaction of trimethylvinylsilane with PhBr and m-ClC6H6Br and then the most effective sys-
tems were applied for functionalisation of tetramethyltetravinylcyclotetrasiloxane and poly(dimethylsi-
loxane-co-methylvinylsiloxane), leading to the silicone fluids having high refractive index (1.5–1.6).
Ó 2009 Elsevier B.V. All rights reserved.
Received 29 April 2009
Received in revised form 16 June 2009
Accepted 1 July 2009
Available online 4 July 2009
Keywords:
Heck reaction
Palladium catalysts
High refractive fluids
Arylated polysiloxanes
1. Introduction
tained by hydrosilylation of phenyl- and diphenylacetylene with
linear poly(dimethylsiloxane-co-methylhydridosiloxane)s and
Carbon–carbon double bond formation is one of the essential
aims of organic and polymer chemistry, leading, e.g. to fine organ-
ics, pharmaceuticals, monomers and specialty materials. Palladium
catalysed coupling of aryl halides and olefins (Heck reaction), is
widely recognised as a powerful tool for synthesis of substituted
olefins, dienes and a variety of unsaturated compounds, including
processes run on industrial scale [1–5]. This is also a useful route
yielding conjugated polymer systems and nanocomposite materi-
als [6,7], applied in optoelectronics. Currently, organosilicon poly-
mers and oligomers incorporating arylethenyl moieties in the main
or side chains have received considerable attention [8]. Their po-
tential applications, as materials in personal care as gloss ingredi-
ents [8], polymers for non-linear optics and light emitting devices
tetramethylcyclotetrasiloxane (Scheme 1A) [8,14]. Recently, we
presented alternative routes involving cross-metathesis (Scheme
1B and C) and silylative coupling of vinylsilicones and styrenes,
in the presence of ruthenium and molybdenum complexes [15].
All three pathways, i.e. hydrosilylation, metathesis and silylative
coupling are limited, from technological point of view, due to a
rather elevated catalyst cost. In the case of silylative coupling,
which was earlier also described for reaction of styrene with six
and eight-membered cyclosiloxanes [16], the method requires
higher concentrations of transition metal complexes (1–
2 ꢀ 10ꢁ2 mol/per 1 mol of Vi moieties), compared to the ones ap-
plied in Heck coupling. Additionally, we have detected a rather
serious disadvantageous side process, both in silylative coupling
and metathesis. Due to the use of excess styrene as a substrate in
both methods, free radical polymerisation of styrene takes place.
Formation of polystyrene was reported, independently, by Marci-
niec et al. [16]. The extent of this undesired polyreaction and for-
mation of polystyrene can be limited or eliminated either by the
[6,9], result from the presence of
p-conjugated moieties. In the
synthesis of main chain conjugated oligo(phenylenevinylenes)s,
the Heck reaction was found to be an effective, alternate route to
cross-metathesis [10,11], where unsaturated carbon–carbon bonds
are rearranged in the presence of metal carbene complexes.
On the other hand, structurally related oligo(phenylenesilylene-
vinylene)s were made by silylative coupling [12] in the presence of
non-carbene transition metal complexes [13].
use of free radical scavengers or applying
substrate [15].
a-methylstyrene as a
Our interest, for some time now, has focused on high refractive
index (closed to human hair RI) siloxane fluids, bearing phenyleth-
enyl moieties as side chain pendants. Such materials are important
components of haircare products. For the first time, they were ob-
2. Results and discussion
The aim of the present work was to select the most effective
palladium complexes and to determine reaction conditions, which
would ensure high yields of phenylethenyl-modified linear and
cyclic siloxanes, leading to silicone fluids with high refractive
indices. The fourth pathway (Scheme 1D), via Heck type coupling
* Corresponding author. Tel.: +48 42 680 3208; fax: +48 42 684 7126.
E-mail address: was@bilbo.cbmm.lodz.pl (W.A. Stan´ czyk).
0022-328X/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.07.001

A. Czech et al. / Journal of Organometallic Chemistry 694 (2009) 3386–3389
3387
R = H
(A)
(B)
+ PhC CH, [Pt]
R = CH CH2
Me
Si
Me
+ PhCH CH2, [Ru ][Mo
]
O
Si O
CH
CH
R = CH CH2
R
(C)
+ PhCH CH2, [Ru]
R = CH CH2
+ PhBr, [Pd]
(D)
Scheme 1. Alternative routes to phenylethenyl substituted silicones: (A) hydrosi-
lylation, [Pt] = PTDD; (B) metathesis, [Ru=], [Mo=] = Grubbs and Schrock type
catalysts; (C) silylative coupling, [Ru] = e.g. [RuH(Cl)(CO)(PPh3)3]; (D) Heck reaction,
[Pd] = e.g. [PdCl2(cod)].
offers, the use of less expensive catalysts, at lower concentration
and elimination of the undesired formation of polystyrene
(metathesis, silylative coupling). Although, there are a number of
patents referring, in general, also to vinylsilicones as substrates
in the Heck reaction [17,18], one cannot find any reliable compar-
ison of the real effectiveness of various palladium complexes for
such reactants. Dependence of coupling yield on reaction condi-
tions has not been given and most of all refraction indices, impor-
tant from the point of view of application of the materials, were not
reported. In a number of patent applications, describing processes
designed for synthesis of a wide range of structures [19–24], the
reactions were carried out in solution [25–28], which does not
make the process technologically attractive.
Below, we present results from systematic studies of several
palladium complexes as catalytic systems for arylation of vinyl-
siloxanes in bulk. Apart from typical palladium complexes and
Pd(OAc)2 two novel compounds with ꢁSnCl3 ligands ([PdCl(SnCl3)-
(P{p-Tol}3)2], [Pd2Cl2(SnCl3)2(P{p-Tol}3)2]) were also applied. They
are known to facilitate reduction of Pd(II) to in situ generated cat-
alytically active Pd(0) species [29,30].
As a preliminary step, we chose to the evaluate effectiveness of
palladium catalysts, known to be effective in Heck coupling, basing
on a low molecular weight model system. It involved coupling
trimethylvinylsilane with PhBr and m-ClC6H4Br (Table 1). Evalua-
tion of conversion of vinyl groups into phenylethenyl ones was,
in this work, based on 1H NMR analysis (Fig. 1) and integration
of unreacted vinyl groups at siloxy monomeric units and the
formed phenylethenyl substituents. The range of 5.80–6.10 ppm
(3H, –MeSiViO–, unreacted) and 6.15–6.45 ppm (1H, MeSiCH =
CHPh) was taken into account as the resonances corresponding
Fig. 1. 1H NMR spectrum of reaction mixture in the Heck coupling of tetrame-
thyltetravinylcyclotetrasiloxane and bromobenzene at 27% conversion.
to the other vinylene proton at 6.95–7.15 ppm (1H, MeS-
iCH = CHPh) slightly overlap with aromatic protons. Apart from –
SnCl3 ligand bearing complexes, other catalysts used in this work
were claimed to be efficient in Heck reaction of organic substrates
[2]. Among the palladium catalysts both Pd2(dba)3 and Pd(OAc)2
led to formation of arylethenyltrimethylsilanes with high yield
(82.5% yield, entries 5 and 9) for the reaction with m-ClC6H4Br
and 72.5–78% (entries 4 and 7) with PhBr as the aryl substrate.
For (1,5-cyclooctadiene)dichloropalladium the respective yields
were 78% and 70%. It was confirmed, that the use of sterically
demanding tri-ortho-tolyl phosphine generates higher conversions,
compared to triphenyl phosphine. On the other hand the catalyst,
frequently used in Heck and Suzuki coupling reactions – tetra-
kis(triphenylphosphine)palladium(0) (entry 10) gave low
efficiencies (26% yield) in the model process. The yield of phenyl-
ethenyltrimethylsilane was even lower in the presence of –SnCl3
ligand containing palladium complexes (21% and 16.5% respec-
tively for entries 11 and 12), used as catalyst precursors. Thus,
the simple model reaction allowed for choosing the most effective
palladium catalytic systems, which were subsequently applied in
studies of Heck coupling, involving oligomeric and polymeric silox-
anes. The above preliminary evaluation have shown the following
general order of catalytic activity:
PdðOAcÞ2 ꢂ ½Pd2ðdbaÞ3ꢃ > ½PdðcodÞCl2ꢃ >> ½PdðPPhÞ4ꢃ
> ½Pd2Cl2ðSnCl3Þ2ðPfp ꢁ Tolg3Þ2ꢃ
Table 1
Heck reaction of aryl bromides with trimethylvinylsilane (molar ratio 1:1) in toluene
(50% by volume); reaction conditions: 80 °C, 24 h, PR3 (R = o-Tola, R = Phb), NEt3;
molar ratios: [Me3SiVi]:[ArBr]:[NEt3] = 1:1:1, [Pd]:[PR3]:[Me3SiVi] = 1:2:3700.
> ½PdClðSnCl3ÞðPfp ꢁ Tolg3Þ2ꢃ
The three most effective catalysts – Pd(OAc)2, [Pd2(dba)3], [Pd(cod)-
Entry
Aryl bromide
Catalyst
Yield [ 0.5%]
Cl2] were subsequently used in reaction of organosilicon
1
2
3
4
5
6
7
8
PhBr
[Pd(cod)Cl2]
[Pd(cod)Cl2]
[Pd(cod)Cl2]
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
[Pd2(dba)3]
[Pd2(dba)3]
[Pd2(dba)3]
[Pd(PPh3)4]
[Pd2Cl2(SnCl3)2(P{p-Tol}3)2]
[PdCl(SnCl3)(P{p-Tol}3)2]
70.0a
77.5a
77.0b
78.0a
82.5a
65.0b
72.5a
82.5a
64.5b
26.0a
21.0a
16.5a
Me,Vi
substrates – tetramethyltetravinylcyclotetrasiloxane (I) (D4
)
m-ClC6H4Br
m-ClC6H4Br
PhBr
m-ClC6H4Br
m-ClC6H4Br
PhBr
m-ClC6H4Br
m-ClC6H4Br
PhBr
and poly(dimethylsiloxane-co-methylvinylsiloxane), containing 65%
of ꢄMeViSiOꢄ monomeric units (Mn = 3200; Mw/Mn = 1.1) (II), and
aryl compounds. The arylhalides used in the Heck coupling reaction
included bromo- and chlorobenzene, bromotoluenes and m-bromo-
chlorobenzene. For reactions with PhBr and (I) the highest conver-
sion rate (97%) was obtained with Pd(OAc)2 as a catalyst (Table 2,
entry 12). Under the same reaction conditions, [PdCl2(cod)] and
[Pd2(dba)3] gave 93 and 95% conversion, respectively (entries 5
and 10). Once chlorobenzene was applied as a substrate (entry 6)
9
10
11
12
PhBr
PhBr

3388
A. Czech et al. / Journal of Organometallic Chemistry 694 (2009) 3386–3389
Table 2
Heck coupling of silicone vinyl bearing fluids with aryl halides.
Entry
Siloxanea
ArXb
Catalystb
[Pd]b
Temp (°C)
React. time (h)
Conversion (%)
Product RI
1
2
3
4
5
6
7
8
I
I
I
I
I
I
I
I
I
I
I
I
I
I
II
II
II
C6H5Br
C6H5Br
C6H5Br
C6H5Br
[PdCl2(cod)]c
[PdCl2(cod)]
[PdCl2(cod)]
[PdCl2(cod)]
[PdCl2(cod)]
[PdCl2(cod)]
[PdCl2(cod)]
[PdCl2(cod)]
[PdCl2(cod)]
[Pd2(dba)3]e
[Pd2(dba)3]
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
[Pd2(dba)3]
[Pd2(dba)3]
[Pd2(dba)3]
5.0 10ꢁ4
1.4 10ꢁ4
1.4 10ꢁ4
5.0 10ꢁ3
1.4 10ꢁ3
1.4 10ꢁ3
1.4 10ꢁ3
1.4 10ꢁ3
1.4 10ꢁ3
1.4 10ꢁ3
1.4 10ꢁ3
1.4 10ꢁ3
1.4 10ꢁ3
1.4 10ꢁ3
1.4 10ꢁ3
1.4 10ꢁ3
5.0 10ꢁ3
100
100
80
100
100
100
100
80
100
100
100
100
100
100
100
100
100
24
12
96
12
24
96
24
24
24
24
24
24
24
24
12
24
24
95
65
59
90
93
56
53
47
53
95
52
97
53
52
73
80
83
1.582
1.453
1.441
1.575
1.58
C6H5Br
C6H5Cld
1.442
1.59
m-MeC6H4Br
m-MeC6H4Br
p-MeC6H4Br
C6H5Br
m-MeC6H4Br
C6H5Br
m-MeC6H4Br
m-ClC6H4Br
C6H5Br
1.581
1.565
1.583
1.589
1.591
1.591
1.595
1.477
1.496
1.504
9
10
11
12
13
14
15
16
17
f
C6H5Br
C6H5Br
a
I – tetramethyltetravinylcyclotetrasiloxane (D4Me,Vi), II – poly(dimethylsiloxane-co-methylvinylsiloxane) (65% MeViSiO m.u., Mn = 3200).
[–MeViSiO–]:[ArX]:[Et3N] = 1:1:1, [Pd]:[P(o-Tol)3]:[–MeSiViO–] = 1:2:3700 = 1:2.
[PdCl2(cod)] = (1,5-cyclooctadienedichloropalladium (II).
In the presence of CuI.
[Pd2(dba)3] – tris(dibenzylideneacetone)dipalladium(0).
b
c
d
e
f
Pd(OAc) – palladium (II) acetate.
the coupling yield was low (56%) even after extended reaction time
(96 h) and in the presence of 2 mol% of CuI as a co-catalyst [31].
There is also a clear effect of reaction temperature and concen-
tration of the palladium catalyst. Lowering both, the temperature
(entries 2, 3 and 7, 8) and the catalyst concentration (entries 1, 5
and 16, 17) leads to decreases in reaction rates. In such cases, the
reaction times must be prolonged to obtain higher conversions.
Once m-MeC6H4Br, p-MeC6H4Br or m-ClC6H4Br were used, the cat-
alytic effectiveness of the three palladium catalytic systems was al-
most the same (52–53% conversion, entries 7, 11, 13). The coupling
yield did not depend on the electron-withdrawing or electron-
donating character of substituents and one could expect that steric
factor dominated for the processes involving cyclic siloxane sys-
tem. On close examination of the published results [32–34], what
seems to be a general picture and once substituted aryl halides
are used, higher coupling yields are assured by longer reaction
time. Such substituents, changing electron density, can affect the
relative strength of the C–X and Pd–C, and Pd–X bonds in a transi-
0.16
0.14
0.12
0.1
A
0.08
0.06
0.04
0.02
0
B
tion state of oxidative addition to palladium. GC/MS analysis of the
Me,Vi
siloxane products, run for the reaction between D4
and PhBr,
0
2000
4000
6000
8000
10000
revealed that the resultant silicone fluid contains mono-, di- and
tri-phenylethenyl substituted cyclosiloxane isomers (see Experi-
mental and Supplementary material). Under experimental condi-
tions, tetra-substituted cyclosiloxane isomers could not be
detected due to long retention times.
[s]
Fig. 2. A second order dependence for the Heck coupling in bulk (A) and in toluene
(B). ([Me3SiVi] = [PhBr], 100 °C).
(1.548) [36]. Thus, such materials shall have excellent ‘‘shine”
properties, once applied in hair care products. Although in the case
of substituted aryl bromides the Heck coupling proceeds slower
than for bromobenzene, as a substrate, the refraction indices reach
relatively high values (m-ClC6H4Br) as a result of higher RI of the
substituted aryl bromides themselves (e.g. RI for C6H5Br = 1.559,
RI for m-ClC6H4Br = 1.576).
One additional factor concerning the Heck process under sol-
vent-less conditions should be mentioned. The process carried
out in bulk involving equimolar amounts of PhBr and Me3SiVi with
Pd(OAc)2 as
a
catalyst, (k = 3.5 10ꢁ5 l molꢁ1sꢁ1
)
is ꢄ8 times
faster than the one run in toluene (50% by volume) (k =
4.4 10ꢁ6 l molꢁ1sꢁ1) (Fig. 2).
At the end it is important to underline the applied aspect of the
above results as the Heck coupling leads to organosilicon products,
both oligomers and polymers, that consist potential hair care addi-
tives. In the case of materials obtained from co-polysiloxane (II),
having both [–MeViSiO–] and [–Me2SiO–] monomeric units, due
to relative ‘‘dilution” of phenylethenyl moieties, the respective RI
values are rather low (1.47–1.50, entries 15–17). For the oligomeric
cyclotetrasiloxane without [–Me2SiO–] units, the RI values of the
coupling products are much higher and in general, they depend
on conversion and the structure of aryl bromide, falling in the
range of 1.58–1.59, which is even higher than human hair RI
3. Conclusions
We have developed an efficient and convenient catalytic path-
way leading to high RI siloxane fluids in the course of the Heck
coupling of aryl bromides with vinyl substituted cyclic and linear
siloxanes. Although similar processes are described in the litera-
ture, they were typically performed in solutions of organic solvents
[35], including ionic liquids [33,37] or in water-organic solvent
mixtures [27,34]. In this work we have evaluated effectiveness of

A. Czech et al. / Journal of Organometallic Chemistry 694 (2009) 3386–3389
3389
a series of palladium catalysts in a reaction involving model
organosilicon substrate – trimethylvinylsilane and aryl bromides
as: Pd(OAc)2 P [Pd2(dba)3] > [Pd(cod)Cl2] >> [Pd(PPh)4] > [Pd2Cl2-
(SnCl3)2(P{p-Tol}3)2] > [PdCl(SnCl3)(P{p-Tol}3)2]. The three most
effective catalysts have been successfully used in several Heck cou-
pling reactions under solvent-less conditions, providing an useful
method leading to high refraction index silicone fluids (from RI
of 1.430 (II) and 1.433 (I) to even 1.590). It has been also shown
that reactions carried out without solvent proceed faster than the
ones performed in solution.
(Vi)O][Si(Me)(CH@CHPh)O]3 572 (M+), 366 (M+ꢁ2 CH@CHPh),
Conditions for all other coupling reactions are given in Tables 1
and 2.
4.3. Comparative rate measurements for reactions of PhBr with
Me3SiVi in bulk and in toluene
Reactions were carried out as described above, using Me3SiVi
(1.50 g, 0.015 mol), PhBr (2.36 g, 0.015 mol), Et3N (1.53 g,
0.015 mol), PPh3 (0.012 g, 4.4 10ꢁ5 mol) and Pd(OAc)2 (0.005 g,
2.2 10ꢁ5 mol). In a solution experiment the reaction mixture was
diluted with toluene (1:1). Reaction mixtures were heated at
100 °C for 1 h (bulk experiment) or over 2 h (solution experiment).
At time intervals small samples (0.2 ml) were withdrawn, ex-
tracted with hexane, dried and analysed (1H NMR). The results
are shown in Fig. 2.
4. Experimental
4.1. General
Poly(dimethylsiloxane-co-methylvinylsiloxane) was made by
ring-opening cationic polymerisation of octamethylcycloterasilox-
Vi,Me
ane (D4) with teramethyltetravinylcyclotetra-siloxane (D4
)
Appendix A. Supplementary material
using decamethyltetrasiloxane (MD2M) as chain terminator [15].
Vi,Me
D4
(Aldrich), [Pd(dba)3], [Pd(PPh3)4], Pd(OAc)2, [PdCl2(cod)],
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.jorganchem.2009.07.001.
[PdCl2(P{o-Tol}3)2] (all from Strem) were used as supplied.
[PdCl(SnCl3)(P{p-Tol}3)2] and [Pd2Cl2(SnCl3)2(P{p-Tol}3)2] were
prepared as described in [29]. Triethylamine (Fluka) was purified
using standard method [38]. The 1H and 29Si NMR spectra were re-
corded using a Bruker MSL 200 MHz and a Bruker DRX 500 MHz
spectrometers in CDCl3 solutions. GC–MS (EI) analyses were run
on a Thermo-Quest apparatus using 30 m DB-1 column (the tem-
perature was programmed as follows: 50 °C (2 min), then a linear
increase at the rate of 10 °C/min up to isotherm of 250 °C
(10 min). All experiments were carried out in inert atmosphere
(Ar). RI measurements were performed with Carl Zeiss Refractom-
eter, equipped with Haake DC-10 Thermostat at 20 °C.
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was purged with argon for 15 min. at room temperature and then
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ladium(II) (38.5 mg, 0.14 mmol) and tri(o-tolyl)phosphine
(82 mg, 0.28 mmol) were added. The reaction mixture was stirred
at 80 °C for 96 h. After cooling to room temperature, hexane
(50 ml) was added, the mixture was washed with water, the layers
were separated and the organic one was filtered through Celite.
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line connected to mercury pump (10ꢁ3 mmHg) at room tempera-
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1H NMR: d (CDCl3): 0.10–0.25 (m, 3H, MeSiViO, unreacted);
0.25–0.50 (m, 3H, MeSiCH = CHPh); 5.80–6.10 (m, 3H, MeSiViO,
unreacted); 6.15–6.45 (d, 1H, MeSiCH = CHPh, JCH@CH = 18.9 Hz);
6.95–7.15 (m, 1H, MeSiCH = CHPh, JCH@CH = 18.9 Hz); 7.15–7.55
(m, Ph). Proportions of monomeric units based on 1H NMR: 59%
of –[MeSi(CH@CHPh)O]– and 41% of –[MeSiViO]–; 29Si NMR: d
(CDCl3, Cr(acac)3): ꢁ18.6 (MeSiViO); ꢁ17.6 (MeSi(CH@CHPh)O);
EI GC/MS (m/z): [Si(Me)(Vi)O]3[Si(Me)(CH@CHPh)O] 420 (M+),
405 (M+ꢁMe), 392 (M+ꢁCH2@CH2), 378 (M+ꢁMeꢁVi), 290
(M+ꢁCH@CHPh–Vi,), 275 (M+ꢁMeꢁViꢁCH@CHPh); [Si(Me)
(Vi)O]2[Si(Me)(CH@CHPh)O]2 496 (M+), 392 (M+ꢁCH2@CHPh),
365 (M+ꢁCH2@CH2ꢁCH@CHPh), 351 (M+ꢁMeꢁViꢁCH@CHPh),
325 (M+ꢁMeꢁ2C6H6), 288 (M+ꢁ2 CH2@CHPh), 275 (M+ꢁMeꢁ2
CH@CHPh), 251 (M+ꢁCH2@CH2ꢁViꢁSi(Me)(CH@CHPh)O); [Si(Me)-
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