Catalytic reactions of hydrosiloxanes with allyl chloride

Article abstract of DOI:10.1016/j.jorganchem.2005.01.033

Catalytic reactivity of Si-H bond of di-, trisiloxanes with allyl chloride in the presence of platinum catalyst has been examined. Hydrosilylation process competes with hydrogen substitution by chlorine and/or propenyl group. The effect of the reaction conditions as well as structure of siloxane on the yield and selectivity of the number of products has been discussed. Several consecutive-competitive processes have been identified. The results obtained can be helpful in the study of the catalytic hydropolysiloxanes reactions with allyl derivatives-systems of great practical importance, to produce commercial functionalized silicones.

Full text of DOI:10.1016/j.jorganchem.2005.01.033

Journal of Organometallic Chemistry 690 (2005) 4478–4487
www.elsevier.com/locate/jorganchem
Catalytic reactions of hydrosiloxanes with allyl chloride
*
Marcin Jankowiak, Hieronim Maciejewski, Jacek Gulinski
Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznan, Poland
Received 15 October 2004; received in revised form 11 January 2005; accepted 11 January 2005
Available online 11 March 2005
Abstract
Catalytic reactivity of Si–H bond of di-, trisiloxanes with allyl chloride in the presence of platinum catalyst has been examined.
Hydrosilylation process competes with hydrogen substitution by chlorine and/or propenyl group. The effect of the reaction condi-
tions as well as structure of siloxane on the yield and selectivity of the number of products has been discussed. Several consecutive-
competitive processes have been identified. The results obtained can be helpful in the study of the catalytic hydropolysiloxanes
reactions with allyl derivatives–systems of great practical importance, to produce commercial functionalized silicones.
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: Hydrosiloxanes; Platinum catalysts; Hydrosilylation; Si–H reactivity; Synthesis
1. Introduction
or modified catalysts (in particular KarstedtÕs and
other Pt complexes) not only in the synthesis of macro-
molecular compounds but also in catalytic cure of
polysiloxanes [5].
Catalytic hydrosilylation of organic substrates pos-
sessing both unsaturated carbon–carbon bond and
other organic functionalities is an effective and still
attractive way of synthesis of carbofunctional silanes,
siloxanes and oligo(poly)siloxanes [1–6]. The resulting
addition products show the reactivity originating from
the presence of organic functional groups and substitu-
ents at silicon atom(s) – e.g. „Si–H, „Si–OR, „SiX,
etc., preserving some hydrophobic properties due to
the presence of far less reactive „Si–R or „Si–O–
Si„groups [2–4]. Widely applied and recently explored
hydrosilylation of polymeric systems [2,4] and espe-
cially hydrosilylation curing of polyvinylsiloxanes by
polyhydrosiloxanes have been attracting increasing
attention due to the practical outcome and recent
development in silicon-containing polymeric systems.
The open literature and patent descriptions are gener-
ally limited in scope to systems involving well-known
Hydrosilylation of allyl derivatives seems to be of
great practical importance [1,2]. Introduction of the
XCH2CH2CH2 group at terminal or internal position
of siloxane chain via hydrosilylation of allyl derivative
(XCH2CH@CH2, X = Cl, NH2, OR, CN, CF3, etc.)
modifies both siloxane reactivity and physicochemical
properties. Allyl chloride, due to its availability and
characteristic easy conversion of chlorine atom to other
functionalities should be a good choice although the lit-
erature on its reactivity toward hydro(poly)siloxanes is
very limited [7–9] and there is a lack of thorough inves-
tigation of the above-mentioned reaction process. Pt(0),
H2PtCl6 (cyclohexanone) and Ru3(CO)12 have been
effectively applied to the hydrosilylation of allyl deriva-
tives by oligosiloxanes having Si–H bonds [7,8]. The
conversion of siloxane has been studied using a quanti-
tative IR method (based on Si–H bond frequency) and
under the optimum conditions functionalization pro-
ceeded smoothly, however, no detailed data on allyl
chloride runs are available [7].
*
Corresponding author.
E-mail address: centech@amu.edu.pl (J. Gulinski).
0022-328X/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.01.033

M. Jankowiak et al. / Journal of Organometallic Chemistry 690 (2005) 4478–4487
4479
The reaction of allyl chloride with polydimethylsilox-
2. Results and discussion
ane having hydrogen bonded to silicon at one end in the
presence of Pt catalyst (50 ꢁC, 5 h, toluene as a solvent)
yielded effectively polydimethylsiloxane chlorinated at
one end [9]. In this reaction the Si–H substitution by
chlorine dominates over the addition process. Besides,
it has been established that a significant percentage of
the allyl groups undergo isomerization under the addi-
tion reaction conditions to propenyl groups [10]. This
isomerization can be depicted by the following equation:
2.1. Reaction of pentamethyldisiloxane (I) with allyl
chloride
Siloxane (I) represents siloxanes and/or oligo-
(poly)siloxanes with one terminal Si–H bond. First at-
tempts were carried out in the presence of KarstedtÕs
catalyst Pt2{[CH2@CHSi(CH3)2]2O}3. It was found that
typically three products 1–3 were observed with only
traces of some other ones (GC):
Pt catalyst
Cl
Cl
ð1Þ
cat.
Cl
+
+
+
Si
Si
CH3CH=CH2
Si
Si
O
1
H
O
Cl
It has become accepted practice in industry, to use
stoichiometric excesses (20% mole or more) of the allyl
group to ensure complete reaction of all silanic hydro-
gen atoms.
( I )
+
+
Cl
Si
Si
Si
Si
O
O
3
2
ð2Þ
The addition product 3 is accompanied by chloro-
disiloxane 1 and propyldisiloxane 2. Other products,
found in minor quantities, could be the result of specific
catalytic rearrangements of siloxane substrate [14], lead-
ing to Si–H redistribution products, e.g.:
On the other hand, chloropropyl substituted silox-
anes (both terminal and internal ones) are very good
substrates for tertiary aminopropylsiloxane derivatives
of practical use [11,12]. Thiol and amino-terminated sil-
icones may be prepared by reacting chloropropyl substi-
tuted siloxane with ammonia, an amine or H2S to
provide a primary amine, secondary amine or thiol
ended oligomer, respectively [13].
Di- and trisiloxanes with one or two terminal Si–H
bonds can be model compounds of a-hydro, a,x-dihy-
dro or polyhydrosiloxanes with the Si–H bond at all sil-
icon atoms in the polysiloxane backbone – chemical
models for polyhydrosiloxane fluids of market
importance.
In this paper, we would like to present the results of
our study on pentamethyldisiloxane (I), 1,1,1,3,5,5,5-
heptamethyltrisiloxane (II) and 1,1,3,3-tetramethyl-
disiloxane (III) reactions with allyl chloride in the
presence of platinum complexes and to compare the
reactivity of Si–H bond in terminal and internal
position.
H
+
Si
Si
Si
Si
Si
Si
O
H
H
O
O
ð3Þ
and their consecutive reactions products. Under mild
conditions several catalytic reactions runs have been
performed to determine the effect of the substrate molar
ratio and reaction temperature on the substrate conver-
sion, yield and selectivity of the reaction products (see
Table 1).
Higher temperature and/or catalyst concentration
lead obviously to higher substrate conversion, however
for the equimolar ratio (see runs 1–4), the conversion
of siloxane is drastically higher than that of the second
Table 1
The effect of reaction conditions on the selectivity of the products of the reaction of the siloxane (I) with allyl chloride in the presence of KarstedtÕs
catalyst (0.2 ml of siloxane, vials/glass ampoules, reaction time 24 h)
½siloxaneꢀ
½AllClꢀ
½siloxaneꢀ
½catalystꢀ
No.
Siloxane conv. (%)
AllCl conv. (%)
T (ꢁC)
Products selectivity (%)
1
2
3
Others
1
2
34
97
27
77
1
105
105
104
104
105
105
104
104
105
105
104
104
45
85
45
85
45
85
45
85
45
85
45
85
55
62
59
67
46
40
32
41
59
66
64
77
10
9
31
25
28
21
41
30
24
27
26
18
25
13
4
4
1
3
100
100
27
62
68
1
11
8
2
4
1
5
5
66
2
9
4
6
60
100
100
97
2
25
38
21
11
13
9
5
7
100
67
2
6
8
2
11
4
9
44
62
10
23
0.5
0.5
0.5
0.5
10
11
12
3
100
94
35
46
2
6
4

4480
M. Jankowiak et al. / Journal of Organometallic Chemistry 690 (2005) 4478–4487
substrate. The Si–H/Si–Cl exchange process dominates
over addition and the Si–H/Si–R exchange. The double
excess of siloxane (see runs 5–8 in Table 1) influences the
ratio of addition product 3 but in all cases chlorodisilox-
ane 1 predominates and is accompanied by traces of
propenyldisiloxane (see Section 4). In the excess of allyl
chloride (2:1) its conversion is even lower (comparing to
equimolar ratio). Both addition product 3 as well chlo-
rodisiloxane derivative 1 have been isolated from reac-
tion mixture and fully characterized (see Section 4).
Identification of 2 is based on GC-MS measurements.
The results discussed above show that under the reac-
tion conditions chlorine substitutes hydrogen at the sili-
con atom. Some propene is evolved and partially
hydrosilylated toward product 2. It is known that addi-
tion of siloxane (I) to b-methallyl chloride has resulted
in 97% yield of typical adduct (H2PtCl6, reflux, 2 h) or
96% of chlorodisiloxane (Pd/C, reflux, 2 h) [15], provid-
ing evidence that both catalyst and organic substrate
nature determine the reaction mode.
the reaction conditions on the conversion of sub-
strates and products selectivity is illustrated in
Table 2.
For equimolar reagents mixture at 85 ꢁC almost 100%
conversion of substrates is observed (see run 2) with chlo-
rotrisiloxane 4 dominating over other products. In the ex-
cess of siloxane (II) conversions remain high, however,
for lower catalyst concentrations (see run 4) adduct 7 is
not formed at all. The H/Cl exchange product seems to
be the main one despite the reaction conditions applied,
especially in the higher excess of allyl chloride in the reac-
tion mixture (see runs 6–8) which may even allow an iso-
lation of 4 (see Section 4). Hydrosilylation competes with
H/Cl and H/propenyl exchange reactions, the highest
amount of product 7 has been found for run 6. All the
products have been isolated and their structures have
been confirmed by GC and spectroscopic analyses (see
Section 4). Propene can undergo hydrosilylation towards
propyl derivative 5, especially in the excess of siloxane
(II). It is known from literature that the hydrosilylation
of allyl chloride by heptamethyltrisiloxane (Pt catalyst,
120 ꢁC, 40 min) yielded 15 % of addition product as
one of several products [16]. MeCl2SiH added at the equi-
molar level effectively enhanced the yield, but not the
rate, of the hydrosilylation reaction product up to 44%.
The use of Cl3SiH enhanced both the rate (3 min reaction
time!) and adduct yield (40%). Unfortunately, there is no
data on other products selectivity. On the other hand,
hydrosilylation of b-methallyl chloride by (Me3SiO)2Si-
(Me)H in the presence of H2PtCl6 (reflux, 1 h) leads to
a mixture of adduct (34%), SiH/Cl exchange product –
chlorosiloxane (18%) and b-methylpropenyl derivative
of trisiloxane (9%) as substitution product [15]. Pt/C cat-
alyst has shown a very similar selectivity of the products,
but in the presence of Pd/C and Ru/C chlorotrisiloxane
has been the only product observed (with yield 74%
and 60%, respectively).
2.2. Reactions of 1,1,1,3,5,5,5-heptamethyltrisiloxane
(II) with allyl chloride
Trisiloxane (II) can be another model of
oligo(poly)siloxanes with isolated [HSiO(CH3)] units.
Under the conditions comparable to described previ-
ously, reaction of trisiloxane (II) with allyl chloride led
to addition product 7, accompanied by chloro 4, propyl
5 and propenyl 6 substituted trisiloxane (Eq. (4))
Cl
Si
H
cat.
Cl
+
Si
Si
+
CH3CH=CH2
+
Si
Si
Si
O
O
O
O
( II )
4
Cl
+
+
Si
Si
Si
Si
Si
Si
+
Si
Si
Si
O
O
O
O
O
O
5
6
7
2.3. Reactions of 1,1,3,3-tetramethyldisiloxane (III)
with allyl chloride
ð4Þ
The use of standard Pt catalyst allows us to
achieve high conversion of substrates, however, in
all cases the process is unselective. The effect of
Tetramethyldisiloxane can produce both mono- and
diadducts, however, it is practically impossible to
Table 2
The effect of reaction conditions on the selectivity of the products of the reaction of the siloxane (II) with allyl chloride in the presence of KarstedtÕs
catalyst (0.2 ml of siloxane, vials/glass ampoules, reaction time 24 h)
½siloxaneꢀ
½AllClꢀ
½siloxaneꢀ
½catalystꢀ
No.
Siloxane conv. (%)
AllCl conv. (%)
T (ꢁC)
Products selectivity (%)
4
5 + 6
7
Others
1
2
3
4
5
6
7
8
33
98
59
100
93
1
105
105
104
105
104
105
104
105
45
85
45
85
85
85
85
85
45
70
67
69
51
37
85
90
9
11
14
30
23
4
26
18
19
0
0
1
0
1
1
0
0
1
1
100
42
1
100
100
60
2
56
97
2
25
59
8
0.5
0.5
0.25
100
97
52
33
7
5
4

M. Jankowiak et al. / Journal of Organometallic Chemistry 690 (2005) 4478–4487
4481
achieve monoadduct with high selectivity and yield [17].
The patent literature describes the reaction of tetrame-
thyldisiloxane with allyl chloride in the presence of
Pt(0)/divinylsiloxane (80 ꢁC, 18 h) leading only toward
monoadduct with the yield up to 24% using iPr3SiO-
SO2CF3 and ethyltriacetoxysilane as catalyst promoters
[17]. The autoclave reaction in the molar excess of allyl
chloride (3:1) in the presence of 5% Pt/C (120 ꢁC, 12 h)
led only to 1-chloro-3-chloropropyl-1,1,3,3-tetrame-
thyldisiloxane (34% yield) [18]. Typically, in the presence
of KarstedtÕs catalyst, the post-reaction mixture shows
complex composition (see Fig. 1 – GC analysis) due to
the presence of nine identified products (Eq. (5)).
Mono- and diaddition products 13 and 16 are
accompanied by chloro- and alkyl derivatives of 13
14 and 15 and several chloro- and propyldisiloxanes
8–12. Monoadduct 13 could be of great interest as a
potential candidate for substrate of diorganofunctional
disiloxanes of the mixed functionality. Diorganofuc-
tional disiloxanes are interesting substrates for modifi-
cation of a multitude of organic and inorganic
polymers and oligomers, including chemical curing
processes and synthesis of block organic-inorganic
polymers [2,4]. All the products were identified; six
of them were isolated from reaction mixture and four
of them 8, 9, 11 and 16 were synthesized indepen-
dently (details in Section 4). Separation of reaction
mixture was a difficult task since low quantity of
products and very close boiling points of several of
them. Manipulation of reaction conditions and sacri-
ficing the yield led us to isolation most of the prod-
ucts, including hydrosilylation products. There was
some evidence of the presence (in minor quantity) of
mono- and di- propenyldisiloxanes in the reaction
mixtures studied. Independent syntheses of mixture
of 8 and 9 (via chlorination of siloxane (III) with
PCl5 [19]), alcoholysis of ClSiMe2Pr leading to bis-
propyldisiloxane 11 and more complex synthesis of
diadduct 16 (via dimethylchlorosilane addition to allyl
cat.
Cl
+
Si
Si
+
Si
Si
+
+
Si
Si
CH3CH=CH2
H
O
H
Cl
O
H
Cl
O
Cl
( III )
8
9
+
Si
Si
Si
Si
+
Si
Si
+
O
O
Cl
O
H
12
11
10
+
Si
Si
Cl
Si
Si
+
Cl
Cl
O
Cl
O
H
14
13
+
Si
Si
Si
Si
Cl
Cl
O
O
15
16
ð5Þ
Fig. 1. GC-spectrum of the reaction mixture: [siloxane (III)]:[allyl chloride]:[KarstedtÕs catalyst] = 1:1:5 · 10ꢁ5, 85 ꢁC.

4482
M. Jankowiak et al. / Journal of Organometallic Chemistry 690 (2005) 4478–4487
chloride and consecutive methanolysis) allowed us to
identify all the main products of the studied siloxane
– allyl chloride system. Catalytic redistribution of
the substrate (III):
The amount of chlorosiloxane 8 increased in the first
72 h of the reaction progress and then rapidly decreased.
In the very same time dichlorodisiloxane 9 appeared in
the reaction mixture. A similar situation has been ob-
served in the presence of monoadduct 13 and diadduct
16. After the first 24 h, adduct 13 and chlorodisiloxane
8 are the main products, accompanied by chlorosubsti-
tuted adduct 14 after another 24 h. H/Cl exchange for
13 yields high amount of 14 after 72 and 96 h. Monoad-
duct 13 undergoes addition leading to high amount of
product 15. The analysis of the curves presented in
Fig. 2 allows us to propose a general scheme of the reac-
tion progress. In the first step hydrosilylation and H/Cl
exchange lead to the appropriate products 13 and 8
Si
Si
Si
+
Si
Si
Si
H
O
H
H
H
H
O
O
H
ð6Þ
was not observed. The effect of reaction conditions on
the conversion of substrates and products selectivity is
illustrated by the data in Table 3.
For the equimolar ratio of substrates, higher reac-
tion temperatures for both catalyst concentrations pre-
fer higher ratios of monochloro 8 and monopropylo
10 derivatives and monoadduct 13 in reaction mixture
and lower ratios of ‘‘chlorinated’’ adduct 14 (see runs
1–4 in Table 3). In the excess of disiloxane (III) the
amounts of 10 and adduct 13 are significantly higher
(see runs 5–6 in Table 3) relative to their presence in
the equimolar reaction mixture. On the contrary, in
the excess of allyl chloride (see runs 7–9), the mono-
adduct is missing (some amounts of diadduct 16 are
detected) as well as chloro- and propylsiloxanes 8
and 10 but chlorosubstituted adduct 14 predominates.
Interestingly, high conversion of allyl chloride (up to
100%) is observed for its two-fold excess in the reac-
tion mixture but lower than 40% conversion has been
observed for a four-fold one. In the latter case signif-
icantly higher amount of dichlorodisiloxanes 9 has
been detected (see runs 9–10) however, at higher tem-
peratures the amount of 14 is diminished due to a
higher concentration of 12.
cat.
Cl
+
Si
Si
+
CH3CH=CH2
H
O
H
( III )
Si
O
Si
Cl
Si
Si
+
+
H
Cl
O
H
13
8
ð7Þ
Then product 13, beside further addition leading to
synthesis of diadduct 16, undergoes mainly H/Cl ex-
change yielding 14:
Cl
Cl
Si
Si
Cl
Si
Si
O
Cl
O
H
14
13
ð8Þ
and, to a much less extent, hydrosilylation of propene.
In the very same manner 8 is converted to 9, however
part of 8 yields 12. Under the prolonged reaction time
(96 h and more) only traces of product 8 and substrates
can be determined. Consecutive-competitive set of
hydrosilylation, H/Cl and H/propenyl exchange pro-
cesses occurs leading to number of products, presented
in Eq. (5).
To understand this complexity, some preliminary
experiments were conducted to follow the composition
of the reaction mixture in the course of the reaction pro-
gress. Fig. 2 represents relative amounts of the reaction
substrates and products in the course of the reaction for
the chosen experiment ([siloxane]:[allyl chloride]:[Kar-
stedtÕs catalyst] = 1:2:5 · 10ꢁ5, 85 ꢁC).
Table 3
The effect of reaction conditions on the selectivity of the products of the reaction of the siloxane (III) with allyl chloride in the presence of KarstedtÕs
catalyst (0.2 ml of siloxane, vials/glass ampoules, reaction time 24 h)
½siloxaneꢀ
½AllClꢀ
½siloxaneꢀ
½catalystꢀ
No.
Siloxane conv. (%)
AllCl conv. (%)
T (ꢁC)
Products selectivity (%)
8
9
10
11
12
13
14
15
16
1
2
89
94
100
100
98
1
104
104
105
105
105
105
105
104
104
104
45
85
45
85
45
85
45
45
45
85
9
5
5
5
5
0
0
14
17
12
17
30
34
0
2
6
3
0
0
0
3
3
3
5
15
23
19
19
9
17
21
17
25
31
32
0
15
2
9
14
11
11
5
5
6
5
6
2
4
9
8
5
8
1
15
11
16
21
15
0
3
95
88
1
16
2
4
100
100
100
100
100
39
1
5
68
69
2
2
6
2
3
4
9
7
98
84
0.5
0.5
0.25
0.25
18
21
31
34
23
21
24
31
37
38
31
10
10
9
8
0
0
0
9
10
100
100
0
0
0
6
11
34
0
0
0

M. Jankowiak et al. / Journal of Organometallic Chemistry 690 (2005) 4478–4487
4483
400.00
350.00
300.00
250.00
200.00
150.00
100.00
50.00
propene
allyl chloride
siloxane (III)
product 8
product 10
product 9
product 12
product 13
product 14
product 15
product 16
0.00
0.00
Time [h]
96.00
24.00
48.00
72.00
Fig. 2. Relative amounts of the reagents in the course of reaction (III) with allyl chloride in the presence of KarstedtÕs catalyst.
3. Conclusions
From such a point of view, the structure of the reac-
tion product of polyhydrosiloxane reaction with allyl-
chloride, reported in a recent US patent [8], seems to
reflect the results of our study. Addition of oligosiloxane
Me3SiO[HSiMeO]40SiMe3 to allyl chloride (KarstedtÕs
catalyst, 100–140 ꢁC, 2.5 h) produced a modified silox-
ane of formula:
It is obvious that addition of di(tri)siloxanes to allyl
chloride leads to several products and that the reaction
conditions influence the process selectivity. All the results
discussed above lead to a conclusion that the reaction of
di- and trisiloxanes with allyl chloride involves several
processes (mainly substitution and addition). The
amounts of specific products depend on the reaction tem-
perature and the ratio of substrates, due to consecutive
additionand/orsubstitutionreactionsofseveralproducts.
Fig. 3 shows generalized reaction pathways in the sys-
tems studied:
Si
O
Si
H
O
Si
Cl
O
Si
O
Si
O
Si
Moreover, both substrates and primary products,
especially that having SiH groups 8, 13, undergo hydro-
silylation processes leading to a number of final prod-
ucts 12, 14, 15.
Cl
10
10
10
10
In the series of siloxanes studied, the increasing elec-
tron-withdrawing effect of Me3SiO substitutes increases
the strength of the Si–H bond in the order
(Me3SiO)2SiMeH > Me3SiOSiMe2H, steric shielding
seems to change in the same order. Probably both factors
affect destabilization of olefin–Pt complex and hence the
formation of chlorosiloxanes dominates over addition.
Besides, there is a striking similarity between the behav-
ior of siloxane (I) and (II) in the studied processes.
There are published evidences that „SiCH2CH2-
CH2Cl group does not undergo decomposition to
„SiCl and CH2@CHCH3 [20] or hydrosilanes SiH are
not chlorinated by ClCH2CH2CH2Si„ leading to
„SiCl and CH3CH2CH2Si„ [21]. Additionally, it is
known that for all allyl compounds, in the presence of
silanes containing SiH group, propene is formed in con-
siderable quantities [22].
supported by NMR data. The product obtained in the
second step after Na2S4 treatment leads to sulfur func-
tional polyorganosiloxanes for rubber mixtures. The
typical use of excess of allyl chloride (to cover its losses
due to catalytic isomerization toward unreactive prope-
nylchloride (1)) additionally push the competitive Si–H
substitution resulting in the low yield of chloropropyl-
substituted siloxane units in both monomeric (di- and
trisiloxanes) and oligomeric (polymeric) products.
4. Experimental
4.1. Chemicals
1,1,3,3-tetramethyldisiloxane (Aldrich), 1,1,1,3,5,5,5-
heptamethyltrisiloxane (Aldrich). Pentamethyldisilox-

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M. Jankowiak et al. / Journal of Organometallic Chemistry 690 (2005) 4478–4487
Si
H
Cl
Si
Si
Si Cl
-
2, 5, 10, 11
3, 7, 13, 16
(a)
(b)
Si
H
+
-
Cl
+
catalyst
(d)
(c)
Si
Si Cl
6
1, 4, 8, 9
(a) - alkylation
(b) - hydrosilylation
(c) - chlorination
(d) - alkenylation
Si = siloxane
Fig. 3. Generalized reaction pathways of hydrosiloxanes with allyl chloride.
ane (ABCR) were distilled and kept over molecular
sieves 4A. Chlorodimethylsilane (ABCR), and chloro-
dimethylpropylsilane (ABCR) were used as purchased.
Allyl chloride (Zachem Bydgoszcz) was distilled over cal-
cium oxide and kept over molecular sieves 4A. 3-chloro-
propyldimethylchlorosilane was synthesized according
to the literature [6]. 1,3-dichloro-tetramethyldisiloxane
was purchased from Fluka. Phosphorous pentachloride
(POCH Gliwice), trimethyl orthoformate (Aldrich) and
tetrahydrofuran (POCH Gliwice) were used as pur-
chased. Toluene (POCh Gliwice) was distilled over so-
dium and kept over molecular sieves 4A. Karstedt
catalyst solution was prepared by dissolving 0.343 g of
original catalyst (ABCR, 3–3.5% Pt solution in vinyl-
terminatedpolidimethylsiloxanes) in 5.5 ml of dried and
distilled toluene. Dichloro(1,5-cyclooctadiene)palladium
(II) (Strem) was used as purchased.
of reaction progress, GC analysis was carried out
periodically.
4.2.2. General procedure for products isolation from the
di(tri)siloxanes with allyl chloride reaction mixtures
Most reactions were performed in 50 ml glass flask
equipped with a reflux condenser, thermometer and
magnetic stirrer (10 ml of siloxane, appropriate amount
of allyl chloride and catalyst). These ones which re-
quired temperatures above boiling point of the reactants
were carried out in 10 ml vials sealed with aluminum
caps and PTFE/rubber septa (2ml of siloxane, appropri-
ate amount of allyl chloride and catalyst). GC analysis
was carried out periodically. Evaporation of volatile
matters and products distillation were performed on
an Aldrich micro short-path distillation apparatus with
jacketed head. Products were collected in liquid nitrogen
cooled trap. Distillation pressures varied from ambient
to 1 mmHg.
4.2. Typical procedures of catalytic processes and
products isolation
4.2.3. Synthesis of chloropentamethyldisiloxane 1
1 ml of pentamethyldisiloxane, 1.724 ml of allyl chlo-
ride and 47 ll ml of KarstedtÕs catalyst solution in tolu-
ene were mixed. Vial was sealed and kept at 85 ꢁC for
one day, then 1 was distilled from the reaction mixture.
Chloropentamethyldisiloxane 1, b.p. 117–120 ꢁC/
760 mmHg.
1H NMR (CDCl3): d (ppm) = 0.147 (s, 9H), 0.482 (s,
6H); 13C NMR (CDCl3): d (ppm) = 1.602, 4.168; 29Si
NMR (CDCl3): d (ppm) = 4.107, 12.033; IR (neat film
on KBr, cmꢁ1): 2.960(m), 2902(w), 1259(s), 1071(s),
4.2.1. General procedure for reactions of di(tri)siloxanes
with allyl chloride in the presence of Pt catalyst
In 2 ml vials equipped with PTFE/rubber septa 200 ll
of appropriate siloxane, appropriate amount of allyl
chloride and KarstedtÕs catalyst were placed. In some
cases, due to high overpressure glass ampoules were
used instead of vials. Reactors were sealed, put into drier
thermostated at a given temperature and shaken occa-
sionally. GC analysis was carried out at the beginning
and at the reaction completion. In the case of examing

M. Jankowiak et al. / Journal of Organometallic Chemistry 690 (2005) 4478–4487
4485
876(m), 844(s), 812(s), 801(s), 755(m), 545(w), 465(w);
Spectroscopic data evidenced the presence of trace
amounts of propenylpentamethyldisiloxane,, b.p. 140–
143 ꢁC/740 mmHg: H NMR (CDCl3): d (ppm) = 0.067
(s, 15H), 1.563 (m, 2H), 4.90 (m, 2H), 5.78 (m, 1H);
1H NMR (CDCl3): d (ppm) = 0.125–0.201 (m), 0.598
(CH3CH2CH2Si – m, 2H), 1.022 (CH3CH2CH2Si – t,
3H, J = 7.142), 1.481 (CH3CH2CH2Si – m, 2H), 3.192
(CH2@CHCH2Si – t, 2H, J = 6.866), 4.996 (CH2@
CHCH2Si – m, 2H), 5.885 (CH2@CHCH2Si – m, 1H);
13C NMR (CDCl3): d (ppm) = 0.079(=), 0.316(–),
2.172(=), 2.242(–), 17.335(–), 18.391(–), 20.898(–),
27.475(=), 114.184(=), 134.171(=); 29Si NMR (CDCl3):
d (ppm) = 7.491, 8.144, 8,208; IR (neat film on KBr,
cmꢁ1): 3079(w), 2959(s), 2901(m), 2872(m), 1633(w),
1259(s), 1079(s), 932(w), 895(m), 870(s), 841(s), 806(s),
792(s), 754(s), 688(w).
1
13C NMR (CDCl3):
d
(ppm) = ꢁ0.146, 26.432,
113.179, 129.029; 29Si NMR (CDCl3): d (ppm) =
31.062, 7.233–8.416; IR (neat film on KBr, cmꢁ1):
1589–1665(w).
4.2.4. Synthesis of (3-chloropropyl)pentamethyl-
disiloxane 3
1 ml of pentamethyldisiloxane, 215 ll of allyl chloride
and 4.7 ll ml of KarstedtÕs catalyst solution in toluene
were mixed in a vial. The vial was sealed and kept at
45 ꢁC for one day, then 3 was distilled from the reaction
mixture.
4.2.7. Procedure for synthesis of siloxanes 1, 4, and 9
All reactions were carried out in 2 ml vials. 400 ll
of disiloxane or trisiloxane and appropriate amount
of allyl chloride and PdCl2(cod) catalyst were placed
in them. [SiH]:[AllCl]:[PdCl2(cod)] = 1:2:10ꢁ3. The vials
were sealed with PTFE/rubber septa and put into drier
(85 ꢁC). Reactions were monitored by GC. After quan-
titative consumption of siloxanes (usually 3 days) vol-
atiles were evaporated and residue was analyzed.
Chloro (di, tri)siloxanes 1, 4 and 9 were identified,
respectively. The analytical data were identical to
those, described previously (see Sections 4.2.3, 4.2.5
and 4.2.8).
(3-chloropropyl)Pentamethyldisiloxane 3, b.p. 96–
99 ꢁC/40 mmHg.
1H NMR (CDCl3): d (ppm) = 0.065 (s, 15H), 0.608
(m, 2H), 1.785 (m, 2H), 3.506 (t, 2H, J = 6.862); 13C
NMR (CDCl3): d (ppm) = 0.238, 1.913, 15.914, 27.080,
47.888; IR (neat film on KBr, cmꢁ1): 2957(s), 1255(s),
1067(s), 842(s), 804(s).
4.2.5. Synthesis of 3-chloro-1,1,1,3,5,5,5-
heptamethyltrisiloxane 4 and 3-(3-chloropropyl)-
1,1,1,3,5,5,5-heptamethyltrisiloxane 7
4.2.8. Synthesis of chlorotetramethyldisiloxane 8,
1,3-dichlorotetramethyldisiloxane 9, 1-chloro-3-
(3-chloropropyl)tetramethyldisiloxane 14, 1,3-
bis(3-chloropropyl)tetramethyldisiloxane 16
10 ml of 1,1,3,3-tetramethyldisiloxane, 18.4 ml of al-
lyl chloride and 1 ml of KarstedtÕs catalyst solution in
toluene were mixed and kept under reflux. After one
day 5 ml of the reaction mixture was subjected to distil-
lation – chlorotetramethyldisiloxane 8 was collected.
The remaining part was refluxed for one more day and
then distilled to other products 9, 14, 16. GC analysis
was carried out periodically.
1 ml of 1,1,1,3,5,5,5-heptamethyltrisiloxane, 602 ll of
allyl chloride and 3.3 ll ml of Karstedt catalyst solution
in toluene were mixed. Vial was sealed and kept at 85 ꢁC
for one day. Distillation led to isolation of 4 and 7.
3-Chloro-1,1,1,3,5,5,5-heptamethyltrisiloxane 4, b.p.
170–174 ꢁC/760 mmHg.
1H NMR (CDCl3): d (ppm) = 0.156 (s, 18H), 0.375 (s,
3H); 13C NMR (CDCl3): d (ppm) = 1.466, 1.662; IR
(neat film on KBr, cmꢁ1): 2960(s), 2901(w), 1268(s),
1253(s), 1074(s), 870(s), 844(s), 794(s), 758(s), 559(m).
3-(3-chloropropyl)-1,1,1,3,5,5,5-Heptamethyltrisilox-
ane 7, b.p. 92–95 ꢁC/7 mmHg.
Chlorotetramethyldisiloxane 8, b.p. 104–107 ꢁC/
751 mmHg.
1H NMR (CDCl3): d (ppm) = 0.067 (s, 3 H), 0.093 (s,
18H), 0.564 (m, 2H), 1.780 (m, 2H), 3.503 (t, 2H,
J = 6.826); 13C NMR (CDCl3): d (ppm) = 1.812, 1.849,
15.152, 26.870, 47.765; IR (neat film on KBr, cmꢁ1):
2959(s), 2902(w), 1260(s), 1081(s), 843(s), 797(s), 756(s).
1H NMR (CDCl3): d (ppm) = 0.281 (d, 6 H,
J = 2.747), 0.481 (s, 6H), 4.763 (m, 1H); 13C NMR
(CDCl3): d (ppm) = 0.537, 4.026; 29Si NMR (CDCl3):
d (ppm) = ꢁ2.082, 6.825; IR (neat film on KBr, cmꢁ1):
2961(s), 2904(m), 2128(s), 1260(s), 1072(s), 910(s),
833(s), 805(s), 769(m), 488(m), 466(m).
4.2.6. Synthesis of 3-propyl-1,1,1,3,5,5,5-
heptamethyltrisiloxane 5 and 3-propenyl-1,1,1,3,5,5,5-
heptamethyltrisiloxane 6
2 ml of 1,1,1,3,5,5,5-heptamethyltrisiloxane, 301 ll of
allyl chloride and 6.6 ll ml of Karstedt catalyst solution
in toluene were mixed in a vial. The vial was sealed and
kept at 85 ꢁC for one day. Distillation led to isolation of
5 and 6 as one mixture (b.p. 54–57 ꢁC/7 mmHg). The
mixture was analyzed. Protons in 1H NMR were
counted separately for each compound.
1,3-Dichlorotetramethyldisiloxane 9, b.p. 136–
140 ꢁC/760 mmHg.
1H NMR (CDCl3): d (ppm) = 0.507 (s, 6 H); 13C
NMR (CDCl3): d (ppm) = 3.926; 29Si NMR (CDCl3):
d
(ppm) = 8.045; IR (neat film on KBr, cmꢁ1):
2964(m), 2905(w), 1262(s), 1078(s), 830(s), 806(s),
488(m), 465(m).
1-Chloro-3-(3-chloropropyl)tetramethyldisiloxane 14,
b.p. 98–101 ꢁC/15 mmHg.

4486
M. Jankowiak et al. / Journal of Organometallic Chemistry 690 (2005) 4478–4487
1H NMR (CDCl3): d (ppm) = 0.150 (s, 6 H), 0.432 (s,
6H), 0.696 (m, 2H), 1.810 (m, 2H), 3.519 (t, 2H,
5.2. Synthesis of 1,3-bispropyltetramethyldisiloxane 11
J = 7.141); 13C NMR (CDCl3): d (ppm) = 0.064, 4.148,
In 2 ml vial equipped with PTFE/rubber septa, 400 ll
(2.55 mmol) of chlorodimethylpropylsilane and 413 is ll
(10.2 mmol) of methanol were placed. The reactor was
sealed, put into a drier (60 ꢁC) and shaken occasionally.
GC analysis was carried out periodically. After 21 h
(85% conversion of chlorodimethylpropylsilane) sub-
strates were evaporated and product was analyzed by
1H NMR.
15.511, 26.803, 47.716; 29Si NMR (CDCl3):
d
(ppm) = 5.262, 12.455; IR (neat film on KBr, cmꢁ1):
2960(m), 2904(w), 1261(s), 1073(s), 865(m), 830(s),
803(s), 552(w), 466(m).
1,3-Bis(3-chloropropyl)tetramethyldisiloxane 16, b.p.
125–129 ꢁC/6 mmHg.
Analytical data were almost identical to that obtained
in Section 5.3.
1H NMR (CDCl3): d (ppm) = 0.130 (s, 12H), 0.581
(m, 2H), 1.013 (t, 3H, J = 7.318), 1.424 (m, 2H); IR
(neat film on KBr, cmꢁ1): 2957 (s), 2929 (s), 2871 (s),
1253 (s), 1203 (m), 1055 (s), 998 (m), 896 (m), 838 (s),
795 (s), 771 (s); MS: 177(17) (M-Pr + H), 175(10),
161(8) (M–Pr–Me + H), 149(65) (M–Pr–2Me + 3H),
133(100) (M–2Pr + H), 119(23) (M–2Pr–Me + 2H),
103(4), 87(2), 73(18) (OSiMe2–H), 59(7), 45(4).
4.2.9. Synthesis of propyltetramethyldisiloxane 10 and
3-chloropropyltetramethyldisiloxane 13
6 ml of 1,1,3,3-tetramethyldisiloxane, 1.38 ml of allyl
chloride and 60 ll of KarstedtÕs catalyst solution in tol-
uene were mixed and kept in 45 ꢁC for one day. GC
analysis was carried out periodically to control substrate
conversion. Distillation of the reaction mixture led to
two main products:
5.3. Synthesis of 1,3-bis(3-chloropropyl)tetramethyl-
disiloxane 16
Propyltetramethyldisiloxane 10.
1H NMR (CDCl3): d (ppm) = 0.064 (s, 6H), 0.166 (d,
6H, J = 2.747), 0.542 (m, 2H), 0.965 (t, 3H, J = 7.141),
1.370 (m, 2H), 4.675 (m, 1H); 13C NMR (CDCl3): d
(ppm) = 0.216, 1.021, 4.030, 16.831, 18.184, 20.877;
29Si NMR (CDCl3): d (ppm) = ꢁ6.256, 10.432; IR (neat
film on KBr, cmꢁ1): 2960(s), 2930(m), 2904(m), 2872(m),
2127(s), 1258(s), 1068(s), 911(s), 837(s), 802(s), 771(s).
3-Chloropropyltetramethyldisiloxane 13, b.p. 62–
66 ꢁC/7 mmHg.
In a three-necked flask equipped with a reflux con-
denser, drying tube and magnetic stirrer, a portion of
100 ml (0.61 mol) of 3-chloropropyldimethylchlorosi-
lane was placed and 74.27 ml (1.83 mol) of methanol
was added by dropping funnel. Reaction proceeded in
66–70 ꢁC for 3 h. Volatile matter was evaporated. The
residue was distilled at reduced pressure (7 mmHg).
Product with b.p. 126–130 ꢁC/7 mmHg, 99% purity
and 57% yield was collected.
1H NMR (CDCl3): d (ppm) = 0.088 (s, 6 H), 0.166
(d, 6H, J = 2.747), 0.639 (m, 2H), 1.792 (m, 2H),
3.502 (t, 2 H, J = 7.141), 4.686 (m, 1H); 13C NMR
1H NMR (CDCl3): d (ppm) = 0.073 (s, 12 H), 0.616
(m, 4H), 1.770 (m, 4H), 3.509 (t, 4H, J = 7.141); 13C
(CDCl3):
d
(ppm) = 0.058, 0.961, 15.821, 27.078,
NMR (CDCl3): d (ppm) = 0.393, 15.980, 27.129,
47.804; 29Si NMR (CDCl3):
d
(ppm) = ꢁ5.530,
47.888; 29Si NMR (CDCl3): d (ppm) = 8.321; IR (neat
film on KBr, cmꢁ1): 3257(s), 2913(m, wide), 1258(s),
1068(s), 864(m), 838(s), 802(s).
10.012; IR (neat film on KBr, cmꢁ1): 2959(s),
2903(m), 2125(s), 1257(s), 1061(s), 910(s), 865(m),
839(s), 801(s), 768(m).
6. Procedure for the examination of reaction (5) progress
5. Procedures for alternative syntheses
The reaction was carried out according to the general
procedure described at 4.2.1. Temp. 85 ꢁC, [tetrame-
thyldisiloxane]:[allyl chloride]:[KarstedÕs catalyst] =
1:2:5 · 10ꢁ5. The reaction was monitored by GC at the
beginning, then after 2, 4, 24 h and each next day till
complete substrates conversion (4 days).
5.1. Synthesis of chlorotetramethyldisiloxane 8 and
1,3-dichlorotetramethylodisiloxane 9 [19]
In 100 ml flask equipped with a reflux condenser
(with drier), thermometer and magnetic stirrer 5 ml of
1,1,3,3-tetramethylodisiloxane, 12.9 g of PCl5 and
50 ml of CCl4 were mixed and refluxed for one day.
GC analysis was carried out periodically. Two products
were observed. According to the literature these prod-
ucts were assigned as chlorotetramethylodisiloxane 8
and 1,3-dichlorotetramethylodisiloxane 9. Retention
times (GC) were identical to those obtained for the same
products collected from the reaction mixture (see Sec-
tion 4.2.8).
7. Analytical measurements
GC analysis was performed using an SRI 8610C gas
chromatograph with TCD, Perkin Elmer elite PE-1
30 m capillary column. NMR spectroscopy (1H, 13C,
29Si) was carried out on Varian XL 300 with CDCl3 as
solvent. The infrared spectra were recorded on Bruker

M. Jankowiak et al. / Journal of Organometallic Chemistry 690 (2005) 4478–4487
4487
[5] B. Marciniec, Silicon Chem. 1 (2002) 155–175.
IFS 113v instrument. GC-MS spectroscopy was per-
formed on Varian 3300 chromatograph equipped with
J&W DB-1 30 m capillary column and Finnigan
MAT&TD 800 spectrometer.
[6] J. Gulinski, B. Marciniec, H. Maciejewski, K. Pancer, I. Dabek,
R. Fiedorow, Przemysl Chemiczny 82/ (8–9) (2003) 605.
[7] B. Marciniec, J. Gulinski, L. Kopylova, H. Maciejewski, M.
Grunwald-Wyspianska, M. Lewandowski, Appl. Organomet.
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[8] US 6,472,481 B1 (2002).
[9] US 5,071,936 (1991).
[10] US 4,160,775 (1979).
Acknowledgments
[11] J. Chojnowski, K. Rozga, W. Fortuniak, A. Kowalewska,
Makromol. Chem. Macromol. Symp. 73 (1993) 183.
[12] US 4,587,321 (1986).
We thank Prof. Bogdan Marciniec for valuable dis-
cussion that stimulated us to carry out this study. Finan-
cial support from the Polish Committee for Scientific
Research (Research Project 3 T09B 121 26) is gratefully
acknowledged.
[13] US Pat. Appl. 20020170465.
[14] M.D. Curtis, P.S. Epstein, Adv. Organomet. Chem. 19 (1981)
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[15] T.A. Barry, F.A. Davis, P.J. Chiesa, J. Org. Chem. 38 (1973)
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[16] US 4,614,812 (1986).
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