An efficient method to synthesize chlorosilanes from hydrosilanes

Article abstract of DOI:10.1016/j.jorganchem.2014.06.029

An efficient, highly selective and productive synthesis of chlorosilanes from hydrosilanes is reported. Ceramic spheres were added to chlorination reaction systems and found to greatly increase the efficiency and yields of the reactions. PhSiH₂Cl, PhSiHCl₂, PhSiCl₃, Ph ₂SiHCl, Ph₂SiCl₂, PhMeSiHCl and PhMeSiCl ₂ were synthesized from the corresponding hydrosilanes in only a few hours with yields that typically exceeded 90%. This is the first time PhSiCl₃, Ph₂SiHCl, Ph₂SiCl₂ and PhMeSiCl₂ have been synthesized by this method. The factors that affect the rate of the chlorination reaction were studied. In addition the rate constant, reaction order and apparent activation energy of the chlorination reaction were also determined by kinetics study. The reaction was found to have an induction period.

Full text of DOI:10.1016/j.jorganchem.2014.06.029

Journal of Organometallic Chemistry 769 (2014) 29e33
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
An efficient method to synthesize chlorosilanes from hydrosilanes
*
Wenchao Wang, Yongxia Tan, Zemin Xie, Zhijie Zhang
Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 21 March 2014
Received in revised form
An efficient, highly selective and productive synthesis of chlorosilanes from hydrosilanes is reported.
Ceramic spheres were added to chlorination reaction systems and found to greatly increase the ef-
ficiency and yields of the reactions. PhSiH
PhMeSiCl were synthesized from the corresponding hydrosilanes in only a few hours with yields
that typically exceeded 90%. This is the first time PhSiCl , Ph SiHCl, Ph SiCl and PhMeSiCl have
2 2 3 2 2 2
Cl, PhSiHCl , PhSiCl , Ph SiHCl, Ph SiCl , PhMeSiHCl and
23 June 2014
2
Accepted 30 June 2014
Available online 8 July 2014
3
2
2
2
2
been synthesized by this method. The factors that affect the rate of the chlorination reaction were
studied. In addition the rate constant, reaction order and apparent activation energy of the chlori-
nation reaction were also determined by kinetics study. The reaction was found to have an induction
period.
Keywords:
Synthesis of chlorosilanes
Efficiently
High yields
© 2014 Elsevier B.V. All rights reserved.
Kinetics
Introduction
2
bonds. They used CuCl as the chlorinating agent and diethyl
ether or tetrahydrofuran as the solvent in the presence of a
catalytic amount of CuI to produce a chlorosilanes containing
both SieH and SieCl bonds as a single product. However, this
method still has some problems, such as a long reaction time, a
relatively low yield and it uses too much solvent. This is because
the by-product of the chlorination reaction is CuCl, which has
poor solubility in diethyl ether and tetrahydrofuran. Therefore
Chlorosilanes are organosilicon compounds which can be used
for a variety of functional group transformations and they are useful
starting materials in synthetic organosilicon chemistry. Reactions
involving nucleophilic attack by nucleophilic reagents such as
water, alcohols, organic acids, metallic oxides and organometallic
reagents have been used in the synthesis of numerous substituted
products [1e4]. Chlorosilanes which contain both SieCl and SieH
bonds are useful as blocking agents and can be used to synthesize
other chlorosilanes, hydro-silicone oil and silane coupling agents
the CuCl can easily deposit onto the CuCl
2
which prevents
further reaction with the hydrosilanes. Even if the amount of
solvent, reaction time and stirring intensity are increased, there
[5e9].
2
is still some CuCl that cannot participate in the reaction, which
One of the common routes to synthesize chlorosilanes uses
results in the low yield.
silicanes. To date, several methods have been used to prepare
chlorosilanes from hydrosilanes and various chlorinating agents
have been used to transform SieH bonds to SieCl bonds such as
In the method developed by Kunai et al. [18], 2 M equiv of
CuCl were needed to convert each SieH bond to SieCl in the
2
presence of a catalytic amount of CuI in diethyl ether or tetrahy-
drofuran at room temperature. This system needs a large amount
of solvent, requires a long reaction time and gives a relatively low
yield. In order to solve these drawbacks, we report an improved
method to synthesize chlorosilanes. Ceramic spheres were added
to the reaction system and the reaction conditions were opti-
mized. With this method, nearly 100% of the SieH bonds were
transformed into SieCl bonds in less than 4 h, and the dosage of
solvent was four times less than that for the method developed by
Kunai et al. [18]. The main parameters that affect the rate of the
chlorination reaction were also investigated and the reaction rate
constant, reaction order and the apparent activation energy were
also determined.
2
Cl [10], acyl chloride [11,12], alkyl halide [13,14], phosphorous
pentachloride [15], trichloroisocyanuric acid [16], transition-
metal complex [17e23] and organosilicon radicals [24e26].
However, all these methods have one or more of the following
drawbacks: low yield, difficulty in handling the reagents, long
reaction time, and tedious workup procedures. In addition, few
of the methods can produce chlorosilanes which contain both
SieH and SieCl bonds. Kunai et al. [18] developed a method to
partially chlorinate silicanes and to control the number of SieCl
*
Corresponding author.
E-mail addresses: zhangzj@iccas.ac.cn, wangwenchao@iccas.ac.cn (Z. Zhang).
http://dx.doi.org/10.1016/j.jorganchem.2014.06.029
022-328X/© 2014 Elsevier B.V. All rights reserved.
0

30
W. Wang et al. / Journal of Organometallic Chemistry 769 (2014) 29e33
Results and discussion
Table 2
Comparison with Kunai's method [18].
Synthesis of chlorosilane
Chlorosilanes Solvent
Solvent Reaction
time
Kunai) (h)
Reaction Yield
time (h) (Kunai)
Yield
(0.1 mol) (Kunai) (mL) (mL)
(
Ceramic spheres were added to the reaction system in order to
increase the friction between the reagents. With this method, not
only were the reaction times reduced to less than 4 h, but the yields
of the target materials were close to 100% as determined by Si
NMR of the crude reaction mixture, and the yield of target materials
were all exceeding 90%, as is shown in Table 1. In addition,
compared to the original method the amount of solvent was also
reduced by at least four times, as is shown in Table 2. The general
reaction is shown in Scheme 1. We speculate that the ceramic
spheres effectively and continuously remove the CuCl deposits
Ph
PhMeSiHCl
PhSiH Cl
PhSiHCl
2
SiHCl
300
300
200
250
40
40
40
60
24
36
72
94
2
2
2
3
79.8% 92.6%
77%
70%
66%
91.5%
91.7%
90.8%
2
9
2
2
phosphorous pentachloride [15]. However, phenyltrichlorosilane
was synthesized in 92.9% yield in 4 h using our method. The
number of phenyl groups has little effect on the reaction time and
yield in this method.
Attempts were also made to synthesize 1-chloro-1,1,3,3-
tetramethyldisiloxane and 1,3-dichloro-1,1,3,3-tetramethyldisilo
xane from 1,1,3,3-tetramethyldisiloxane by this method. However,
the target materials were not obtained. Instead dimethyl-
chlorosilane was obtained as the main product. This is mainly
because the SieO bonds were broken by the HCl which was
generated during the chlorination process; so dimethylchlorosilane
was generated.
from the surface of the CuCl
forms a fresh surface on the CuCl
2
during the reaction. This continually
, so it can fully react with the
2
hydrosilanes. It is assumed that the addition of ceramic spheres
would also be beneficial for other similar solideliquid reaction
systems.
Chloro- and dichlorodiphenylsilane were readily and selectively
synthesized from diphenylsilane by this method. Both compounds
were synthesized in less than 4 h at room temperature with yields
of nearly 100% and with the exception of trace amounts of siloxanes
due to the hydrolysis of the product no other products were
detected. These hydrolysis products were also observed by Kunai
Factors that affect the reaction rate
et al. [18]. and are the result of trace water crystals in the CuCl
yields of diphenylchlorosilane and diphenyldichlorosilane were
2.6% and 94.1% respectively after purification. The loss of the
products probably primarily comes from the distillation process
and the hydrolysis of the chlorosilanes. Since the original paper did
not synthesize diphenylchlorosilane, we synthesized it using
Kunai's method and achieved a yield of only 79.8% in 24 h.
The data in the gray shaded areas are for our reaction conditions
and the data in the white shaded areas are for the reaction condi-
tions of Kunai et al.
2
. The
2
The synthesis of Ph SiHCl was used as an example to determine
9
which parameters affect the rate of chlorination. The factors that
were studied include the amount of CuI, the amount of ceramic
spheres, the amount of solvent, and the stirring speed. The results
are shown in Fig. 1aed. Each group of experiments was carried out
by varying only a single variable and the dosages of materials were
appropriate for 0.025 mol of Ph
2 2
SiH . All of these experiments were
sampled after 30 min of reaction and the conversions of the sam-
2
9
ples were determined by Si-NMR.
Methylphenylsilane reacted with 2 equiv of CuCl
same conditions to give methyphenylchlorosilane in 91.5% yield
after purification and it reacted with 4 equiv of CuCl to give
methyphenyldichlorosilane in 94.2% yield. The reactions were
monitored by 29Si NMR and after a few hours of reaction, the SieH
bonds were quantitatively transformed into SieCl bonds. Kunai
et al. [18] reported a yield of only 77% for methyphenylchlorosilane
in 36 h.
2
under the
As is shown in Fig. 1a, increasing the rotation rate substantially
increases the conversion of diphenylsilane, and the conversion is
almost linear with speed. This is mainly because an increase in the
rotation rate can more effectively remove the CuCl that has become
2
2
coated on the surface of CuCl . Similarly, the addition of ceramic
spheres also significantly affects the reaction rate, and again the
conversion is linear with the amount of ceramic spheres (Fig. 1b).
Apparently, adding more ceramic spheres has a similar effect to
increasing rotation rate i.e. more spheres results in better friction.
Thus increasing the rotation speed or the amount of ceramic
spheres within practical limits are simple and useful methods to
accelerate the reaction rate. Fig. 1c shows the effect of the amount
of solvent on the reaction rate. As the amount of solvent was
reduced, the reaction rate increased. This is mainly because the
amount of friction in the reaction system is much larger when there
2
Phenylsilane also reacted with 2 equiv of CuCl under similar
conditions to give phenylchlorosilane in 91.7% yield after purifica-
tion. Kunai et al. [18] only achieved a yield of 70% after 72 h. Phe-
nylsilane reacted with 4 equiv of CuCl
in 90.8% yield whereas Kunai et al. [18]. only achieved 66% after
4 h. It has been reported that when more silicane hydrogen atoms
2
to give phenyldichlorosilane
9
are replaced by chlorine atoms, the remaining hydrogen atoms
have lower reactivities and in fact phenyltrichlorosilane cannot be
synthesized from phenylsilane with chlorinating agents like
2
is less solvent. Thus the CuCl on the surface of the CuCl is more
efficiently removed and the reaction rate increases. It is easy to see
which factors will increase the amount of friction in the system and
thus accelerate the reaction rate. However, again it has to be noted
that the amount of ceramic spheres or solvent can only be changed
within practical limits. Fig. 1d shows the effect of the amount of CuI
on the reaction rate. Typically, as the amount of CuI increased, the
Table 1
Synthesis of chlorosilanes.
Hydrosilane
mol)
CuCl
(mol)
2
/CuI Solvent Ceramic
Reaction Yield (%)
(
(mL) spheres (g) time (h)
PhSiH
PhSiH
PhSiH
3
3
3
(0.1)
(0.1)
(0.1)
0.2/0.0040 40
0.4/0.0068 60
0.6/0.0096 80
0.2/0.0048 40
0.4/0.0076 60
80
120
160
80
120
80
2
3
4
2
4
2
3
PhSiH
PhSiHCl
PhSiCl (92.9)
SiHCl (92.6)
SiCl (94.1)
2
Cl (91.7)
2
(90.8)
3
Ph
Ph
2
SiH
SiH
2
(0.1)
(0.1)
Ph
Ph
2
2
2
2
2
PhMeSiH
PhMeSiH
2
2
(0.1) 0.2/0.0041 40
(0.1) 0.4/0.0069 60
PhMeSiHCl (91.5)
PhMeSiCl (94.2)
120
2
Scheme 1. General hydrosilane chlorination reaction.

W. Wang et al. / Journal of Organometallic Chemistry 769 (2014) 29e33
31
Fig. 1. Effects of rotation speed (a), the amount of ceramic spheres (b), solvent (c) and CuI (d) on the reaction rate.
conversion of diphenylsilane also increased. However, at higher
catalyst amounts the increase with catalyst amount was not as
great and the conversion maximum leveled off at high catalyst
loadings.
formed a complex, so the reaction rate is relatively low. Based on
this supposition, the experimental method was improved by add-
ing the Ph
2
SiH
2
only after the other materials were stirred for
and CuCl have had time to fully
30 min. This ensures that the CuCl
2
form a complex. The results are shown in Fig. 3.
As shown in Fig. 3, the induction period is completely gone and
the reaction rate is accelerated. A linear fit of the data gave slopes
Kinetics study of the chlorination reaction
À3 À1
ꢀ
(
rate constants) for the lines of 2.18 Â 10
s
at 25 C and
À3 À1
ꢀ
In order to investigate the kinetics of the chlorination reaction,
4.07 Â 10
s
at 35 C. The apparent activation energy was
À1
the synthesis of Ph
2
SiHCl was studied. Ph
2
SiHCl were synthesized
calculated to be 47.69 kJ mol based on the Arrhenius equation
(Scheme 2). This low value for the activation energy means that it is
very easy to initiate this reaction. We believed that the chlorination
developed by Kunai et al. [18]. is in fact fast and smooth during the
initial stage of the reaction, however, as the reaction proceeds, too
ꢀ
ꢀ
at 25 C and 35 C respectively and sampled at set intervals. The
results of 29Si-NMR of these samples are dealt as first-order reac-
tion, as is shown in Fig. 2. The nearly linear results indicate that the
chlorination reaction is indeed a first-order reaction with an in-
duction period of about 30 min. This is probably because during the
much solid CuCl is produced which then covers the CuCl . This
2
initial stage of the reaction, the CuCl
2
and CuCl have not fully
causes the reaction rate to gradually decrease since some of the
2
CuCl cannot participate in the reaction and a relatively low yield
results. So the addition of ceramic spheres is an easy way to
maintain a rapid reaction rate and produce a high yield.
Conclusion
An efficient synthetic methodology has been developed for the
conversion of hydrosilanes to chlorosilanes using CuCl as the
2
chlorination agent in the presence of ceramic spheres. The con-
versions are efficient, highly selective and the isolated product
yields exceeded 90%. Since there were no other side reactions, the
workup after the reaction was quite simple and the pure products
can be obtained through distillation or simple fractional distilla-
tion. Increasing the amount of CuI or ceramic spheres, accelerating
the rotation rate, or reducing the amount of solvent, all accelerate
the rate of chlorination. The chlorination reaction has an induction
period and the reaction is a first-order reaction. The reaction rate
À3 À1
ꢀ
À3 À1
À1
ꢀ
constants are 2.18 Â 10
s
at 25 C and 4.07 Â 10
s
at 35 C,
and the apparent activation energy is 47.69 kJ mol based on the
Arrhenius equation.
Fig. 2. Kinetics study of the chlorination reaction.

32
W. Wang et al. / Journal of Organometallic Chemistry 769 (2014) 29e33
ꢀ
C (2100pa): 1H NMR:
4
6
d
6.00 [s, 1H, SiH], 7.47e7.77 [m, 5H,
128.63, 131.04, 132.34, 133.35 [m, 6C,
À2.43 [s, 1Si, PhSiHCl ].
13
Si(C
Si(C
6
H
H
5
)]. C NMR: d
2
9
6
5
)]. Si NMR:
d
2
Synthesis of phenyltrichlorosilane
A mixture of 10.82 g (0.1 mol) of PhSiH
3
, 80.7 g (0.6 mol) of
anhydrous CuCl , 1.84 g (0.0096 mol) of anhydrous CuI, 160 g of
2
ceramic spheres and 80 mL of diethyl ether was stirred by a me-
chanical stirrer at 400 rpm at room temperature for 4 h. The
resulting mixture was filtered to remove the copper salts and
ceramic spheres. The solution was concentrated, and the residue
was distilled under reduced pressure to give PhSiCl
3
d
(19.7 g, 92.9%)
7.50e7.84 [m,
ꢀ
1
as a colorless liquid. Bp. 63 C (1100pa): H NMR:
1
3
5
Si(C
H, Si(C
6
H
5
)]. C NMR:
d
128.76, 131.62, 132.91, 133.27 [m, 6C,
2
9
6
H
5
)]. Si NMR:
d
À1.87 [s, 1Si, PhSiCl ].
3
Synthesis of diphenylchlorosilane
Fig. 3. Kinetics study of the improved chlorination reaction.
2 2
A mixture of 18.44 g (0.1 mol) of Ph SiH , 26.9 g (0.2 mol) of
anhydrous CuCl , 0.92 g (0.0048 mol) of anhydrous CuI, 80 g of
2
ceramic spheres and 40 mL of diethyl ether was stirred with a
mechanical stirrer at 400 rpm at room temperature for 2 h. The
mixture was filtered, and the filtrate was concentrated. The residue
Scheme 2. Arrhenius equation.
was distilled under reduced pressure to give Ph
2
SiHCl (20.24 g,
ꢀ
1
9
1
2.6%) as a colorless liquid. Bp. 117 C (210pa): H NMR: 5.82 [s,
d
13
H, SiH], 7.47e7.76 [m, 10H, Si(C
H
6 5
)]. C NMR:
d
128.36, 131.10,
À5.94 [s, 1Si,
2
9
Experimental
131.85, 134.52 [m, 12C, Si(C
H
6 5
)].
Si NMR:
d
2
Ph SiHCl].
General
Synthesis of diphenyldichlorosilane
All experiments were carried out under the exclusion of mois-
ture in an inert nitrogen atmosphere and solvents were dried and
A mixture of 18.44 g (0.1 mol) of Ph
2 2
SiH , 53.8 g (0.4 mol) of
distilled prior to use. The CuCl
2
, CuI and silanes were purchased
anhydrous CuCl , 1.44 g (0.0076 mol) of anhydrous CuI, 120 g of
2
from J&K and used as received. The NMR spectra were recorded on
ceramic spheres and 60 mL of diethyl ether was stirred with a
mechanical stirrer at 400 rpm at room temperature for 4 h. The
mixture was filtered, and the filtrate was concentrated. The residue
1
13
29
Bruker AVANCE 400 ( H, C 400 MHz) and DMX 300 ( Si
3
d
00 MHz) spectrometers. All chemical shifts are reported as
values (ppm) relative to residual chloroform ( 7.26), the central
77.16) or tetramethylsilane ( Si 0.0). All of the H,
C and Si NMR spectra for PhSiH Cl, PhSiHCl , PhSiCl , Ph SiHCl,
Ph SiCl , PhMeSiHCl and PhMeSiCl are given in the Supplementary
d
H
was distilled under reduced pressure to give Ph
2
SiCl
2
(23.8 g, 94.1%)
7.49e7.83 [m,
1
ꢀ
1
peak of CDCl
3
(d
C
d
as a colorless liquid. Bp. 150 C (210pa): H NMR:
d
13
29
13
2
2
3
2
1
6 5
0H, Si(C H )]. C NMR: d
128.47, 131.87, 131.91, 134.11 [m, 12C,
5.41 [s, 1Si, Ph SiCl ].
2
9
2
2
2
Si(C
H
5
)]. Si NMR:
d
6
2
2
material.
Synthesis of methylphenylchlorosilane
A mixture of 12.22 g (0.1 mol) of PhMeSiH
Synthesis of phenylchlorosilane
2
, 26.9 g (0.2 mol) of
A mixture of 10.82 g (0.1 mol) of PhSiH
3
, 26.9 g (0.2 mol) of
anhydrous CuCl , 0.78 g (0.0041 mol) of anhydrous CuI, 80 g of
2
anhydrous CuCl , 0.76 g (0.004 mol) of anhydrous CuI, 80 g of
2
ceramic spheres and 40 mL of diethyl ether was stirred with a
ceramic spheres and 40 mL of diethyl ether was stirred with a
mechanical stirrer at 400 rpm at room temperature for 2 h. The
resulting mixture was filtered to remove the copper salts and
ceramic spheres, and the solid was washed three times with diethyl
ether. The solution was then fractionally distilled under reduced
mechanical stirrer at 400 rpm at room temperature for 2 h. The
mixture was filtered, and the filtrate was concentrated. The residue
was distilled under reduced pressure to give PhMeSiHCl (14.34 g,
ꢀ
1
91.5%) as a colorless liquid. Bp. 52 C (990pa): H NMR:
d 0.80, 0.81
[d, 3H, Si(CH )], 5.36, 5.37 [d, 1H, SiH], 7.41e7.70 [m, 5H, Si(C H )].
3
6 5
13
pressure to give PhSiH
2
Cl (13.1 g, 91.7%) as a colorless liquid. Bp.
C (990 pa): H NMR: 5.30 [s, 2H, SiH], 7.47e7.74 [m, 5H,
128.42, 130.01, 131.33, 134.40 [m, 6C,
À18.26 [s, 1Si, PhSiH Cl].
3
C NMR: d 0.10 [s, 1C, Si(CH )], 128.32, 130.91, 133.67 [t, 12C,
Si(C H )]. Si NMR: d 3.5 [s, 1Si, PhMeSiHCl].
6 5
ꢀ
1
29
3
Si(C
Si(C
9
d
1
3
6
H
H
5
)]. C NMR: d
29
6
5
)]. Si NMR:
d
2
Synthesis of methylphenyldichlorosilane
Synthesis of phenyldichlorosilane
2
A mixture of 12.22 g (0.1 mol) of PhMeSiH , 53.8 g (0.4 mol) of
2
anhydrous CuCl , 1.32 g (0.0069 mol) of anhydrous CuI, 120 g of
A mixture of 10.82 g (0.1 mol) of PhSiH
3
, 53.8 g (0.4 mol) of
ceramic spheres and 60 mL of diethyl ether was stirred with a
mechanical stirrer at 400 rpm at room temperature for 3 h. The
mixture was filtered, and the filtrate was concentrated. The residue
anhydrous CuCl , 1.3 g (0.0068 mol) of anhydrous CuI, 120 g of
2
ceramic spheres and 60 mL of diethyl ether was stirred with a
mechanical stirrer at 400 rpm at room temperature for 3 h. The
mixture was filtered, and fractionally distilled under reduced
was distilled under reduced pressure to give PhMeSiCl
2
(18.0 g,
1.06 [s, 1H,
3 6 5
Si(CH )], 7.46e7.77 [m, 5H, Si(C H )]. C NMR: d 5.50 [s, 1C,
ꢀ
1
94.2%) as a colorless liquid. Bp. 69 C (980pa): H NMR:
d
13
pressure to give PhSiHCl
2
(16.1 g, 90.8%) as a colorless liquid. Bp.

W. Wang et al. / Journal of Organometallic Chemistry 769 (2014) 29e33
33
)]. 29Si NMR:
mechanical stirrer at 400 rpm at 25 or 35 C. Each experiment was
sampled every 10 min and the conversion ratios were determined
by Si-NMR.
ꢀ
Si(CH
3
)], 128.48, 131.75, 133.10, 133.37 [m, 6C, Si(C
].
6
H
5
d
17.88 [s, 1Si, PhMeSiCl
2
2
9
Effect of rotation rate on the reaction rate
Kinetics of the improved chlorination reaction
2 2
A mixture of 4.61 g (0.025 mol) of Ph SiH , 6.73 g (0.05 mol) of
anhydrous CuCl , 0.23 g (0.0012 mol) of anhydrous CuI, 20 g of
2
A mixture of 33.65 g (0.25 mol) of anhydrous CuCl , 1.14 g
2
ceramic spheres and 20 mL of diethyl ether was stirred with a
mechanical stirrer at 200, 300, 400, 500, or 600 rpm at room
temperature. Each experiment was sampled at 30 min and the
(0.006 mol) of anhydrous CuI, 100 g of ceramic spheres and 100 mL
of diethyl ether was stirred with a mechanical stirrer at 400 rpm at
ꢀ
25 or 35 C for 30 min. Then 23.05 g (0.125 mol) of Ph SiH was
2
2
2
9
conversions were determined by Si-NMR.
added and the reaction was continued under the same conditions.
Each experiment was sampled every 5 min. In addition, extra
samples were taken at 3, 8 and 13 min in order to monitor the initial
stage of the reaction. The conversion ratios were determined by
Effect of the amount of ceramic spheres on the reaction rate
2
9
A mixture of 4.61 g (0.025 mol) of Ph
2
SiH
2
, 6.73 g (0.05 mol) of
Si-NMR.
anhydrous CuCl , 0.23 g (0.0012 mol) of anhydrous CuI, a variable
2
amount of ceramic spheres and 20 mL of diethyl ether was stirred
with a mechanical stirrer at 400 rpm at room temperature. The
amount of ceramic spheres was 10, 15, 20, 25, or 30 g. Each
experiment was sampled at 30 min and the conversions were
determined by 29Si-NMR.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jorganchem.2014.06.029.
References
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experiment was sampled at 30 min and the conversions were
[7] U. S. P. 2770634.
[8] U. S. P. 5189393 (118e234666).
determined by 29Si-NMR.
[
9] Pol P. 162752 (122e133411).
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[11] J.W. Jenkins, H.W. Post, J. Org. Chem. 15 (1950) 556e559.
[
Effect of the amount of CuI on the reaction rate
[
[
12] S. Risto, Z. Wojciech, L. Reko, Organometallics 31 (2012) 3199e3206.
13] F.C. Whitmore, E.W. Pietrusza, L.H. Sommer, J. Am. Chem. Soc. 69 (1947)
2 2
A mixture of 4.61 g (0.025 mol) of Ph SiH , 6.73 g (0.05 mol) of
2
108e2110.
[14] J. Ohshita, R. Taketsugu, Y. Nakahara, A. Kunai, J. Organomet. Chem. 689
2004) 3258e3264.
anhydrous CuCl , a variable amount of anhydrous CuI, 20 g of
2
(
ceramic spheres and 20 mL of diethyl ether was stirred with a
mechanical stirrer at 400 rpm at room temperature. The amount of
CuI was 0.11 g (0.0006 mol), 0.23 g (0.0012 mol), 0.34 g
[
[
15] S. Mawaziny, J. Chem. Soc. A (1970) 1641e1642.
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478e2482.
18] A. Kunai, T. Kawakami, E. Toyoda, M. Ishikawa, Organometallics 11 (1992)
708e2711.
2
(
(
(
0.0018 mol), 0.45 g (0.0024 mol), 0.57 g (0.003 mol), 0.68 g
0.0036 mol), 0.79 g (0.0042 mol), 0.91 g (0.0048 mol), 1.02 g
0.0054 mol), or 1.13 g (0.006 mol). Each experiment was sampled
[
2
[19] M. Ishikawa, E. Toyoda, M. Ishii, A. Kunai, Y. Yamamoto, M. Yamamoto, Or-
2
9
at 30 min and the conversions were determined by Si-NMR.
ganometallics 13 (1994) 808e812.
[
[
[
[
20] A. Herbert, G. Lewis, J. Org. Chem. 26 (1961) 2006e2008.
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Kinetics of the chlorination reaction
23] R.F. Cunico, E.M. Dexheimer, Synth. React. Inorg. Metal-Org. Chem. 4 (1974)
2
3e26.
A mixture of 23.05 g (0.125 mol) of Ph
anhydrous CuCl , 1.14 g (0.006 mol) of anhydrous CuI, 100 g of
ceramic spheres and 100 mL of diethyl ether was stirred with a
2 2
SiH , 33.65 g (0.25 mol) of
[
[
24] C. Jay, G. Henry, H. George, J. Am. Chem. Soc. 79 (1957) 4754e4759.
25] H. Sakurai, M. Murakami, M. Kumada, J. Am. Chem. Soc. 91 (1969) 519e520.
[26] I.N. Jung, W.P. Weber, J. Org. Chem. 41 (1976) 946e948.
2