Functionalisation of the upper rim of calix[4]arene via alcoholysis and hydrosilylation reactions

Article abstract of DOI:10.1016/j.jorganchem.2009.11.029

Metalation of 5,17-dibromo-25,26,27,28-tetra propoxy calix[4]arene (1) with n-BuLi in THF at -78 °C gave organolithium reagent, which reacted with Me₂HSiCl to give 5,17-bis(dimethylsilyl)-25,26,27,28-tetra propoxy calix[4]arene (2). The Si-H gr

Full text of DOI:10.1016/j.jorganchem.2009.11.029

Journal of Organometallic Chemistry 695 (2010) 505–511
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Functionalisation of the upper rim of calix[4]arene via alcoholysis
and hydrosilylation reactions
*
Kazem D. Safa , Yones Mosaei Oskoei
Organosilicon Research Laboratory, Faculty of Chemistry, University of Tabriz, 5166616471 Tabriz, Iran
a r t i c l e i n f o
a b s t r a c t
Article history:
Metalation of 5,17-dibromo-25,26,27,28-tetra propoxy calix[4]arene (1) with n-BuLi in THF at ꢀ78 °C
gave organolithium reagent, which reacted with Me2HSiCl to give 5,17-bis(dimethylsilyl)-25,26,27,28-
tetra propoxy calix[4]arene (2). The Si–H groups of calixarene 2 were treated with methanol, ethanol,
propanol, butanol, pentanol, hexanol, 2-propanol and 2-methyl propanol in the presence of Karstedt
catalyst (platinum(0)-1,3-divinyl-1,1,3,3-tetramethyl disiloxane complex, solution in xylene) to give
the corresponding 5,17-bis(alkoxydimethylsilyl)-25,26,27,28-tetra propoxy calix[4]arene (3). Moreover,
calixarene 2 was easily functionalized with a variety of alkenes using Karstedt catalyst to give the
corresponding organosilylated calix[4]arene (4).
Received 28 September 2009
Received in revised form 16 November 2009
Accepted 18 November 2009
Available online 23 November 2009
Keywords:
Calixarene
Organosilicon
Alcoholysis
Hydrosilylation
Ó 2009 Elsevier B.V. All rights reserved.
1. Introduction
oxygen atoms at the lower rim and anions through the silicon
atoms on the upper rim [8].
Calixarenes, the cyclic products of the condensation of mole-
cules such as para-substituted phenol and formaldehyde, represent
a class of receptors which are readily available in varying ring sizes
[1]. Organosilylated calixarenes are of potential interest for
molecular recognition of anions [2] because silicon can expand
its coordination shell to become pentacordinate or hexacordinate,
especially when bonded to electronegative atoms [3], but few such
calixarenes have hitherto been reported [4–10].
The dehydrocoupling reaction between hydrosilane and alcohol
is a typical well-known method for the preparation of Si–O bonds
using transition metal catalyst [11]. Since calixarenes containing
alkoxysilane introduce a new field in the calixarene chemistry, it
multiplied our great interest in the preparation of calix[4]arene
molecules containing two alkoxydimethylsilyl groups appended
to the upper rim of the cone conformation.
The hydrosilylation of alkenes is an important industrial pro-
cess, but is also extremely valuable in laboratory scale synthesis
as well. The hydrosilylation reaction also provide an easy method
for introducing different functionality on the upper rim of
calix[4]arenes. Many metal complexes are known to be catalysts
for the reaction [12]. Si–C bonds are often prepared by platinum-
catalyzed hydrosilylation reactions in which, the anti-Markovnikov
addition of a Si–H bond across a C@C double bond is usually ob-
served [13]. The silylated calix[4]arenes were designed to function
as ditopic receptor molecules that will bind cations through the
In this work, we report the use of the dehydrocoupling and
hydrosilylation reactions as new methods for functionalization of
the upper rim of calix[4]arenes, which cannot be achieved via
other methods.
2. Results and discussion
The precursor 5,17-dibromo-25,26,27,28-tetra propoxy ca-
lix[4]arene (1) was obtained in 75% yield according to Scheme 1
[14]. The starting point for the synthesis of calixarenes containing
organosilicon derivatives on the upper rim was the preparation of
5,17-bis(dimethylsilyl)-25,26,27,28-tetra propoxy calix[4]arene
(2), which was obtained in 72% yield (Scheme 2). The organolith-
ium reagent of calixarene was prepared from dibromo calixarene
1 by halogen–lithium exchange using an excess of n-BuLi in
THF at ꢀ78 °C for 15 min. Quenching with Me2HSiCl gave 5,17-
bis(dimethylsilyl)-25,26,27,28-tetra propoxy calix[4]arene 2.
Calixarene 2 having hydrosilane (Si–H) substituents are poten-
tially useful for the preparation of new derivatives of calixarene
containing organosilicon groups. The addition of the hydrosilane
to alcohol is an attractive route to silylethers because the only
side-product is hydrogen gas.
R4ꢀxSiH þ xR0OH catalyst R4ꢀxSiðOR0 Þ þ xH2
ƒƒ!
x
x
The alcoholysis requires a catalyst because alcohols are not gener-
ally sufficiently nucleophilic to attack hydrosilanes [15,16]. Since
we were interested in extending of the applied methodology in
* Corresponding author. Tel.: +98 411 3393124; fax: +98 411 3340191.
E-mail address: dsafa@tabrizu.ac.ir (K.D. Safa).
0022-328X/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.11.029

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K.D. Safa, Y.M. Oskoei / Journal of Organometallic Chemistry 695 (2010) 505–511
AlCl3/PhOH
NaH/DMF/PrBr
Toluene,1h, rt
OH
OH
HO
OH
OPr
PrO
OPr
OPr
OH
OH
HO
OH
NBS
Butanone
Br
Br
Br
Br
Br
Br
1) 2equiv. n-BuLi/THF
2)MeOH
OPr
OPr
PrO
OPr
OPr
OPr
PrO
OPr
(1)
Scheme 1. Preparation of calixarene 1.
H
Si
H
Si
Br
Br
CH3
H3C
PrO
CH3
OPr
H3C
Li
Li
2 eq n-BuLi/THF
Me2HSiCl(excess)
-78 0
-78 0
C
C
OPr
OPr
PrO
OPr
OPr
OPr
OPr
OPr
PrO
OPr
(1)
(2)
Scheme 2. Preparation of calixarene 2.
R
O
Si
R
O
Si
H
Si
H
Si
CH3
H3C
PrO
CH3
OPr
H3C
CH3
H3C
CH3
OPr
H3C
ROH / Karstedt catalyst
THF
OPr
OPr
OPr
OPr
PrO
(2)
(3)
Scheme 3. Preparation of calixarene 3.
the grafting of calixarene containing Si–H group 2 to various alco-
hols, it was decided to study the dehydrocoupling reaction between
compound 2 and some alcohols under different conditions (Scheme
3).
to homogenous black-colored solution, indicating the generation
of colloidal Pt° particles. These reactions occurred in air. In con-
trast, most reported alcoholysis reactions prompted by transition
metal catalysts have been carried out under inert atmospheres
such as argon or nitrogen. Reaction of calixarene 2 with primary
alcohols gave higher yields than analogous reactions with second-
ary alcohols, probably because of the increase in steric hindrance
(Table 1).
Monofunctional alcohols (methanol, ethanol, propanol and
butanol) were treated with 2 in the presence of H2PtCl6ꢁ6H2O as
the catalyst in air under reflux condition. The related 5,17-bis(alk-
oxydimethylsilyl)-25,26,27,28-tetra propoxy calix[4]arenes were
produced, but the reaction time was long (t > 24 h) under reflux
condition. In order to optimize the alcoholysis of calixarene 2,
the Karested catalyst (platinum(0)-1,3-divinyl-1,1,3,3-tetramethyl
disiloxane complex, solution in xylene) was decided to be used
which is more active than Speier catalyst (H2PtCl6ꢁ6H2O). Calixa-
rene 2 was insoluble in alcohols, therefore high reaction tempera-
ture was applied. For this reason, calixarene 2 was disolved in 5 ml
of dry THF and the corresponding alcohol was added to the reac-
The reaction progress was monitored by FTIR spectroscopy on
the basis of absorption measurements at the Si–H stretching bond
frequency (2114 cmꢀ1). For instance, the FTIR spectrum of the ob-
tained calixarene 3a does not show a sharp peak at 2114 cmꢀ1
,
indicating the absence of Si–H bond, and concomitant appearance
of Si–O peak at 1085 cmꢀ1 (Fig. 1). In addition the 1H NMR spec-
trum of calixarene 3a shows the complete disappearance of Si–H
at 4.43 ppm and concomitant appearance of signals assigned to
OCH3 at 3.44 ppm (Fig. 2). Similar results were observed for other
alcohols.
tion mixture. Then Karstedt catalyst was added (20 ll, [Pt]/[Si–
H] = 3.1 ꢂ 10ꢀ6). The colorless reaction mixture gradually turned

K.D. Safa, Y.M. Oskoei / Journal of Organometallic Chemistry 695 (2010) 505–511
507
Table 1
freshly distilled dry THF and catalyzed by the addition of Karstedt
catalyst. Typically 5 mol equivalents of alkene were added per Si–H
group. Hydrosilylation of alkenes with 2 proceeded very fast in the
presence of Karstedt catalyst in THF at room temperature. After a
short initial period (about 5 min) an exothermic reaction took
place. The reaction mixture turned black due to the formation of
colloidal platinum. FTIR spectrum recorded after 15 min, proved
the complete disappearance of Si–H bond. It is worth noting that
the Speier catalyst was less active than the Karstedt catalyst at
room temperature. The best result was obtained using Karstedt
Yields of alcoholysis of various hydroxyl compounds with calixarene 2 in the presence
of the Karstedt catalyst.
Compound
Hydroxy compound
Yields (%)
3a
3b
3c
3d
3e
3f
CH3OH
CH3CH2OH
77
75
75
70
67
65
62
60
CH3CH2CH2OH
CH3CH2CH2CH2OH
CH3CH2CH2CH2CH2OH
CH3CH2CH2CH2CH2CH2OH
(CH3)2CHOH
3g
3h
catalyst (25
l
l, [Pt]/[Si–H] = 3.9 ꢂ 10ꢀ6) in dry THF at room tem-
(CH3)2CHCH2OH
perature. Hydrosilylation of styrene derivatives (styrene, p-chloro
methyl styrene,
a-methyl styrene) and allyl glycidyl ether were
successful with Karstedt catalyst. However, with acrylate deriva-
tives (glycidyl methacrylate, butylacrylate), allylbromide and 1,1-
dichloroethene, the hydrosilylation reactions were unsuccessful
and we were not able to identify the products (Table 2).
The 1H NMR spectrum of the calixarene 4d (Fig. 3) shows the
complete disappearance of the Si–H resonance at 4.43 ppm and
the concomitant disappearance of the allyl group in allyl glycidyl
ether at 5.5 and 6.6 ppm. In addition, the peaks at d = 0.7, 1.7 and
3.5 ppm are the resonance peaks of the silyl propyl group, while
those at d = 2.6, 2.8 and 3.1 ppm represent the resonance peaks
of the epoxide group. These results clearly indicate that the hydro-
silylation reaction of 4d was successful.
3. Conclusion
In conclusion, this paper reports that a series of new calixarenes
substituted with organosilicon groups on the upper rim were ob-
tained in good yields from the catalytic reaction of calixarene 2
with several alcohols. It was found that using the Speier catalyst,
alcoholysis rate was low under reflux condition, but in the pres-
ence of the Karstedt catalyst, alcoholysis took place during 1–2 h
in high yields at room temperature. It should be mentioned that
the primary alcohols gave higher yields than the secondary alco-
hols, which might be the result of the increase in the steric hin-
Fig. 1. Comparing the FTIR spectra of the compound 2 and 3a.
We also investigated the synthesis of calixarenes substituted
with organosilicon groups on the upper rim. Thus calixarene 2 con-
taining Si–H groups were easily functionalized with a variety of al-
kenes using Karstedt catalyst to give the corresponding product (4)
(Scheme 4). All of the hydosilylation reactions were carried out in
drance. Hydrosilylation of calixarene
2 with functionalized
alkenes such as styrene, methylstyrene, p-chloromethyl styrene
and allyl glycidyl ether in the presence of Karstedt catalyst, insert
Fig. 2. The 1H NMR spectrum of the calixarene 3a.

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K.D. Safa, Y.M. Oskoei / Journal of Organometallic Chemistry 695 (2010) 505–511
R
R
H
Si
X
H
Si
X
H3C
CH3
H3C
PrO
CH3
OPr
H3C
R
CH3
H3C
PrO
CH3
OPr
Si
Si
X
THF / Karstedt catalyst
OPr
OPr
OPr
OPr
(2)
(4)
Scheme 4. Preparation of calixarene 4.
Table 2
a solvent. The FTIR spectra were recorded on a Bruker–Tensor 270
spectrometer. Elemental analyses were carried out with a Heareus
CHN-ORAPID instrument.
Hydrosilylation of various alkenes with calixarene 2 in the presence of the Karstedt
catalyst.
Compound
Yield (%)
R
X
4.3. Preparation of the 5,17-dibromo-25,26,27,28-tetra propoxy
R
X
calix[4]arene (1)
4a
4b
4c
H
80
65
72
This was synthesized according to the literature [14].
H
CH2Cl
4.4. Preparation of the 5,17-bis(dimethylsilyl)-25,26,27,28-tetra
propoxy calix[4]arene (2)
CH3
4d
4e
H
85
O
To the stirred solution of 5.3 mmol calixarene 1 in 200 ml dry
THF at ꢀ78 °C was added 9.3 ml (1.51 M, 14 mmol) n-BuLi/hexane.
The yellow solution was stirred at ꢀ78 °C for 15 min, quenched
with Me2HSiCl (10 ml) and stirred for another 30 min. The reaction
mixture was poured into ice cold 2 M hydrochloric acid (200 ml)
and extracted with CHCl3 (2 ꢂ 100 ml). The organic phase was
washed with 100 ml water and dried with Na2SO4, and the solvent
was removed in vacuum to yield a solid. The raw product was
recrystallized from MeOH gave 2 in 72% yield as a white crystals:
m.p. 180–181 °C; FTIR (KBr,cmꢀ1): 3062(HC@), 2114 (Si–H),
CH2-O-CH2
a
CH3
O
O
O-CH2
a
4f
H
O
O
a
a
4g
4h
H
Cl
CH2Br
Cl
1585, 1457 (Ph), 1248, 890 (Si–CH3); 1H NMR (400 MHz, CDCl3,
a
The Si–H peak disappeared in the 1H NMR and the FTIR spectra but the prod-
ucts have not been identified.
3
ppm):
d
0.3 (d, 12H, JHH = 3.5 Hz, 2 ꢂ SiMe2), 0.88 (t, 6H,
J = 7.4 Hz, 2ꢂCH3CH2CH2O), 1.09 (t, 6H, J = 7.4 Hz, 2ꢂCH3CH2CH2O),
1.85–1.97 (m, 8H, 4 ꢂ CH3CH2CH2O), 3.1 (d, 4H, J = 13.4 Hz,
4 ꢂ ArCHAr), 3.69 (t, 4H, J = 7 Hz, 2 ꢂ CH3CH2CH2O), 4.01 (t, 4H,
J = 8.1 Hz, 2 ꢂ CH3CH2CH2O), 4.4 (d, 4H, J = 13.5 Hz, 4 ꢂ ArCHAr),
4.42–4.46 (m, overlapped with doublet, 2H, 2 ꢂ Si–H), 6.0 (d, 4H,
J = 7.6 Hz, aromatic), 6.2 (t, 2H, J = 7.6 Hz, aromatic), 7.21 (s, 4H,
aromatic); 13C NMR (100 MHz, CDCl3, ppm): d ꢀ3.4 (SiMe), 9.8,
10.8, 23.0, 23.4, 31.0, 76.4, 76.6, 122.0, 127.3, 129.4, 133.3, 134.8,
136.4, 155.2, 159.1 ppm; Anal. Calc. for C44H60O4Si2: C, 74.5%; H,
8.5. Found: C, 74.3; H, 8.4%.
new functional groups to calixarene moieties which cannot be
achieved via other methods. On the other hand, the insertion of
acrylates to the upper rim of calixarene with this method was
unsuccessful. These compounds may be used as ditopic receptor
molecules that will bind cations through the oxygen atom at the
lower rim and anions through the silicon atom on the upper rim.
4. Experimental
4.1. Solvents and reagents
4.5. General procedure for the synthesis of 5,17-
bis(alkoxydimethylsilyl)-25,26,27,28-tetra propoxy calix[4]arene
Reactions involving organolithium reagents were carried out
under dry argon. Solvents were dried by standard methods. Sub-
strates for preparation of calixarene 2, viz, p-tert-butyl phenol,
formaldehyde 35–40%, NaH, DMF, 1-bromopropane, NBS, 2-buta-
none, Me2HSiCl and all alcohols used in alcoholysis, also all alkenes
used in hydrosilylation reactions were purchased from Merck and
Fluka and NBS, Me2HSiCl, all alcohols and alkenes purified by stan-
dard methods. Karstedt catalyst was purchased from Aldrich.
A 50 ml round-bottom two-neck flask with magnetic stirring
was charged with 0.20 g (0.28 mmol) calixarene 2, 1 ml ROH, and
5 ml dry THF as a solvent. Then 20 ll of Karstedt catalyst ([Pt]/
[Si–H] = 3.1 ꢂ 10ꢀ6) was added. To follow the reaction progress,
several samples were taken at different times and were analyzed
by FTIR spectroscopy. The reaction mixture was stirred at room
temperature until the complete disappearance of Si–H bond in FTIR
spectroscopy. The alcohols and THF were evaporated under re-
duced pressure and the residue purified by column chromatogra-
phy (n-hexane-ethylacetate, 10:1) to give the corresponding
products.
4.2. Spectra
The 1H NMR and 13C NMR spectra were recorded with a Bruker
FT-400 MHz spectrometer at room temperature and with CDCl3 as

K.D. Safa, Y.M. Oskoei / Journal of Organometallic Chemistry 695 (2010) 505–511
509
Fig. 3. The 1H NMR spectrum of the calixarene 4d.
4.5.1. 5,17-Bis(methoxydimethylsilyl)-25,26,27,28-tetra propoxy
4.5.3. 5,17-Bis(propoxydimethylsilyl)-25,26,27,28-tetra propoxy
calix[4]arene (3a)
calix[4]arene (3c)
Yield 77%; m.p. 127–129 °C; FTIR (KBr, cmꢀ1): 3061 (HC@),
1581, 1454 (Ph), 1249 (Si–CH3), 1084 (Si–O); 1H NMR (400 MHz,
CDCl3, ppm): d 0.39 (s, 12H, 2 ꢂ SiMe2), 0.85 (t, 6H, J = 7.5 Hz,
2 ꢂ CH3CH2CH2O), 1.07 (t, 6H, J = 7.4 Hz, 2 ꢂ CH3CH2CH2O), 1.82–
1.95 (m, 8H, 4 ꢂ CH3CH2CH2O), 3.1 (d, 4H, J = 13.4 Hz, 4 ꢂ ArCHAr),
3.44 (s, 6H, 2 ꢂ CH3O), 3.6 (t, 4H, J = 6.7 Hz, 2 ꢂ CH3CH2CH2O), 4.00
(t, 4H, J = 8.1 Hz, 2 ꢂ CH3CH2CH2O), 4.4 (d, 4H, J = 13.3 Hz,
4 ꢂ ArCHAr), 6.0 (d, 4H, J = 7.5 Hz, aromatic), 6.1 (t, 2H, J = 7.3 Hz,
aromatic), 7.26 (s, 4H, aromatic); 13C NMR (100 MHz, CDCl3,
ppm): d ꢀ3.0 (SiMe), 8.9, 9.9, 22.1, 22.6, 30.1, 49.7, 75.5, 75.8,
121.2, 126.4, 128.6, 132.3, 133.5, 135.6, 154.2, 158.7 ppm; Anal.
Calc. for C46H64O6Si2: C, 71.8; H, 8.4. Found: C, 71.5; H, 8.5.
Yield 75%; m.p. 106–108 °C; FTIR (KBr, cmꢀ1): 3060 (HC@),
1584, 1457 (Ph), 1251 (Si–CH3), 1085 (Si–O);1H NMR (400 MHz,
CDCl3, ppm):
d
0.43 (s, 12H, 2 ꢂ SiMe2), 0.83–0.94 (m, 12,
2 ꢂ CH3CH2CH2O overlapped with 2 ꢂ CH3CH2CH2OSi), 1.10 (t,
6H, J = 7.2 Hz, 2 ꢂ CH3CH2CH2O), 1.56–1.58 (m, 4H, 2 ꢂ CH3-
CH2CH2O), 1.84–1.95 (m, 8H, 4 ꢂ CH3CH2CH2O), 3.1 (d, 4H,
J = 13.3 Hz, 4 ꢂ ArCHAr), 3.59 (t, 4H, J = 7 Hz, 2 ꢂ CH3CH2CH2O),
3.68 (t, 4H, J = 8 Hz, 2 ꢂ CH3CH2CH2O), 4.04 (t, 4H, J = 8.5 Hz,
2 ꢂ CH3CH2CH2O), 4.4 (d, 4H, J = 13.2 Hz, 4 ꢂ ArCHAr), 6.0 (d, 4H,
J = 7.8 Hz, aromatic), 6.1 (t, 2H, J = 7.5 Hz, aromatic), 7.31 (s, 4H,
aromatic); 13C NMR (100 MHz, CDCl3, ppm): d ꢀ2.8 (SiMe), 9.7,
10.2, 10.9, 22.7, 23.2, 23.7, 30.3, 68.1, 76.5, 76.7, 121.6, 127.2,
128.7, 132.5, 134.1, 135.1, 154.5, 158.4 ppm; Anal. Calc. for
C50H72O6Si2: C, 72.8; H, 8.8. Found: C, 72.5; H, 8.6%.
4.5.2. 5,17-Bis(ethoxydimethylsilyl)-25,26,27,28-tetra propoxy
calix[4]arene (3b)
4.5.4. 5,17-Bis(butoxydimethylsilyl)-25,26,27,28-tetra propoxy
calix[4]arene (3d)
Yield 75%; m.p. 115–117 °C; FTIR (KBr, cmꢀ1): 3059 (HC@),
1584, 1456 (Ph), 1251 (Si–CH3), 1109 (Si–O); 1H NMR (400 MHz,
CDCl3, ppm): d 0.31 (s, 12H, 2 ꢂ SiMe2), 0.86 (t, 6H, J = 7.5 Hz,
2 ꢂ CH3CH2CH2O), 0.9 (t, 6H, J = 8 Hz, 2 ꢂ CH3CH2O), 1.1 (t, 6H,
J = 7.3 Hz, 2 ꢂ CH3CH2CH2O), 1.82–1.94 (m, 8H, 4 ꢂ CH3CH2CH2O),
3.1 (d, 4H, J = 13.5 Hz, 4 ꢂ ArCHAr), 3.45 (t, 4H, J = 8 Hz,
2 ꢂ CH3CH2O), 3.65 (t, 4H, J = 6.7 Hz, 2 ꢂ CH3CH2CH2O), 4.00 (t,
4H, J = 8 Hz, 2 ꢂ CH3CH2CH2O), 4.4 (d, 4H, J = 13.5 Hz, 4 ꢂ ArCHAr),
6.0 (d, 4H, J = 7.5 Hz, aromatic), 6.1 (t, 2H, J = 7 Hz, aromatic), 7.33
(s, 4H, aromatic); 13C NMR (100 MHz, CDCl3, ppm): d ꢀ2.8 (SiMe),
9.0, 10.0, 22.1, 22.6, 22.7, 30.1, 57.12, 75.4, 75.7, 121.0, 126.2,
128.4, 132.0, 133.4, 135.2, 154.0, 158.4 ppm; Anal. Calc. for
C48H68O6Si2: C, 72.3; H, 8.6. Found: C, 72.1; H, 8.4%.
Yield 70%; m.p. 90–92 °C; FTIR (KBr, cmꢀ1): 3065 (HC@), 1583,
1457 (Ph), 1252 (Si–CH3), 1087 (Si–O); 1H NMR (400 MHz, CDCl3,
ppm):
d
0.41 (s, 12H, 2 ꢂ SiMe2), 0.86 (t, 6H, J = 7.5 Hz,
2 ꢂ CH3CH2CH2O), 0.89 (t, 6H, J = 7.3 Hz, 2 ꢂ CH3CH2CH2CH2O),
1.10 (t, 6H, J = 7.4 Hz, 2 ꢂ CH3CH2CH2O), 1.31–1.38 (m, 4H,
2 ꢂ CH3CH2CH2CH2O), 1.50–1.57 (m, 4H, 2 ꢂ CH3CH2CH2CH2O),
1.84–1.96 (m, 8H, 4 ꢂ CH3CH2CH2O), 3.1 (d, 4H, J = 13.4 Hz,
4 ꢂ ArCHAr), 3.63–3.68 (m, 8H, 2 ꢂ CH3CH2CH2O overlapped with
2 ꢂ CH3CH2CH2CH2O), 4.03 (t, 4H, J = 8 Hz, 2 ꢂ CH3CH2CH2O), 4.4
(d, 4H, J = 13.3 Hz, 4 ꢂ ArCHAr), 6.0 (d, 4H, J = 7.5 Hz, aromatic),
6.14 (t, 2H, J = 7.4 Hz, aromatic), 7.30 (s, 4H, aromatic); 13C NMR
(100 MHz, CDCl3, ppm): d ꢀ2.6 (SiMe), 8.7, 9.8, 12.8, 18.0, 21.9,

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K.D. Safa, Y.M. Oskoei / Journal of Organometallic Chemistry 695 (2010) 505–511
22.5, 30.0, 33.8, 61.8, 75.6, 75.8, 120.9, 126.2, 128.0, 132.1, 133.4,
135.1, 154.0, 158.6 ppm; Anal. Calc. for C52H76O6Si2: C, 73.2; H,
8.9. Found: C, 72.9; H, 8.7%.
4H, J = 13.2 Hz, 4 ꢂ ArCHAr), 6.04 (d, 4H, J = 7.5 Hz, aromatic),
6.11 (t, 2H, J = 7 Hz, aromatic), 7.3 (s, 4H, aromatic); 13C NMR
(100 MHz, CDCl3, ppm): d ꢀ1.5 (SiMe), 8.7, 9.9, 18.2, 21.9, 22.5,
29.7, 30.1, 67.1, 76.4, 76.6, 120.5, 126.3, 128.0, 131.3, 131.5,
136.2, 153.9, 158.3 ppm; Anal. Calc. for C52H76O6Si2: C, 73.2; H,
8.9. Found: C, 72.8; H, 8.7%.
4.5.5. 5,17-Bis(pentoxydimethylsilyl)-25,26,27,28-tetra propoxy
calix[4]arene (3e)
Yield 67%; m.p. 89–91 °C; FTIR (KBr, cmꢀ1): 3062 (HC@), 1584,
1457 (Ph), 1250 (Si–CH3), 1090 (Si–O); 1H NMR (400 MHz, CDCl3,
4.6. General procedure for the hydrosilylation of 5,17-
bis(dimethylsilyl)-25,26,27,28-tetra propoxy calix[4]arene (2) with
various alkenes
ppm):
d
0.41 (s, 12H, 2 ꢂ SiMe2), 0.87–0.94 (m, 12H,
2 ꢂ CH3CH2CH2O overlapped with 2 ꢂ CH3(CH2)3CH2O), 1.10 (t,
6H, J = 7.3 Hz, 2 ꢂ CH3CH2CH2O), 1.27–1.33 (m, 8H, 2 ꢂ CH3(CH2)2-
CH2CH2O), 1.53–1.57 (m, 4H, 2 ꢂ CH3(CH2)2CH2CH2O), 1.87–1.96
(m, 8H, 4 ꢂ CH3CH2CH2O), 3.1 (d, 4H, J = 13.4 Hz, 4 ꢂ ArCHAr),
3.64 (t, 4H, J = 6.8 Hz, 2 ꢂ CH3(CH2)2CH2CH2O), 3.66 (t, 4H,
J = 7 Hz, 2 ꢂ CH3CH2CH2O), 4.03 (t, 4H, J = 8 Hz, 2 ꢂ CH3CH2CH2O),
4.4 (d, 4H, J = 13.4 Hz, 4 ꢂ ArCHAr), 5.99 (d, 4H, J = 7.5 Hz, aro-
matic), 6.11 (t, 2H, J = 7.5 Hz, aromatic), 7.30 (s, 4H, aromatic);
13C NMR (100 MHz, CDCl3, ppm): d ꢀ2.6 (SiMe), 8.7, 9.8, 13.0,
21.4, 22.0, 22.5, 27.0, 30.0, 31.4, 62.0, 75.6, 75.8, 120.9, 126.2,
127.7, 132.8, 133.6, 135.5, 154.0, 158.6 ppm; Anal. Calc. for
C54H80O6Si2: C, 73.6; H, 9.1. Found: C, 73.4; H, 8.7%.
In 50 ml round-bottom two-neck flask with a magnetic stirring
under argon 2.8 mmol of alkene was dissolved in 5 ml of freshly
distilled dry THF. To this solution was added 25 ll ([Pt]/[Si–
H] = 3.9 ꢂ 10ꢀ6) of Karstedt catalyst, 0.28 mmol of calixarene 2 in
5 ml dry THF was added via syringe and the reaction was stirred
at room temperature until all of the starting material was con-
sumed (10–15 min). After a short initial period, the reaction mix-
ture turned black due to the formation of colloidal platinum.
Several samples were taken at different times and were analyzed
by FTIR spectroscopy. After the reaction was complete, activated
carbon was added to the solution to help remove the colloidal plat-
inum and the solution was filtered and concentrated under re-
duced pressure to provide viscous oil. The products were
recrystallized (CH2Cl2–MeOH, 10:90) to yield the analytical pure
samples.
4.5.6. 5,17-Bis(hexoxydimethylsilyl)-25,26,27,28-tetra propoxy
calix[4]arene (3f)
Yield 65%; m.p. 85–87 °C; FTIR (KBr, cmꢀ1): 3066 (HC@), 1586,
1460 (Ph), 1253 (Si–CH3), 1110 (Si–O); 1H NMR (400 MHz, CDCl3,
ppm): d 0.41 (s, 12H, 2 ꢂ SiMe2), 0.85–0.91 (m, 12H, 2 ꢂ CH3CH2-
CH2O overlapped with 2 ꢂ CH3(CH2)4CH2O), 1.10 (t, 6H, J = 7 Hz,
2 ꢂ CH3CH2CH2O), 1.27–1.35 (m, 12H, 2 ꢂ CH3(CH2)3CH2CH2O),
1.54–1.57 (m, 4H, 2 ꢂ CH3(CH2)3CH2CH2O), 1.86–1.94 (m, 8H,
4 ꢂ CH3CH2CH2O), 3.1 (d, 4H, J = 13.4 Hz, 4 ꢂ ArCHAr), 3.62 (t, 4H,
J = 7 Hz, 2 ꢂ CH3(CH2)3CH2CH2O), 3.68 (t, 4H, J = 6.8 Hz, 2 ꢂ CH3-
CH2CH2O), 4.04 (t, 4H, J = 8 Hz, 2 ꢂ CH3CH2CH2O), 4.4 (d, 4H,
J = 13.4 Hz, 4 ꢂ ArCHAr), 6.0 (d, 4H, J = 7.5 Hz, aromatic), 6.1 (t,
2H, J = 7.6 Hz, aromatic), 7.30 (s, 4H, aromatic); 13C NMR
(100 MHz, CDCl3, ppm): d ꢀ2.6 (SiMe), 8.7, 9.8, 13.0, 21.6, 22.0,
22.5, 24.5, 28.6, 30.0, 31.6, 62.2, 75.4, 75.6, 120.9, 126.2, 127.7,
132.4, 133.4, 135.5, 154.0, 158.6 ppm; Anal. Calc. for C56H84O6Si2:
C, 73.9; H, 9.3. Found: C, 73.5; H, 8.9%.
4.6.1. 5,17-Bis(2-phenyl ethyl dimethylsilyl)-25,26,27,28-tetra
propoxy calix[4]arene (4a)
Yield 80%; m.p. 106–108 °C; FTIR (KBr, cmꢀ1): 3060 (HC@),
1584, 1455 (Ph), 1248 (Si–CH3); 1H NMR (400 MHz, CDCl3, ppm):
d 0.35 (s, 12H, 2 ꢂ SiMe2), 0.89 (t, 6H, J = 7.5 Hz, 2 ꢂ CH3CH2CH2O),
1.14 (t, 6H, J = 6.8 Hz, 2 ꢂ CH3CH2CH2O), 1.18 (t, 4H, J = 5 Hz,
2 ꢂ CH2CH2Si), 1.84–1.99 (m, 8H, 4 ꢂ CH3CH2CH2O), 2.67 (m, 4H,
2 ꢂ PhCH2CH2), 3.1 (d, 4H, J = 13.5 Hz, 4 ꢂ ArCHAr), 3.68 (t, 4H,
J = 6.6 Hz, 2 ꢂ CH3CH2CH2O), 4.05 (t, 4H, J = 8.1 Hz, 2 ꢂ CH3CH2-
CH2O), 4.4 (d, 4H, J = 13.5 Hz, 4 ꢂ ArCHAr), 6.0 (d, 4H, J = 7.5 Hz,
aromatic), 6.1 (t, 2H, J = 7.2 Hz, aromatic), 7.16–7.27 (m, 14H, aro-
matic); 13C NMR (100 MHz, CDCl3, ppm): d ꢀ2.8 (SiMe), 9.7, 10.8,
18.5, 23.0, 23.5, 30.2, 31.0, 76.3, 76.5, 122.0, 125.4, 127.1, 127.7,
128.2, 131.1, 133.1, 134.4, 136.5, 146.5, 155.1, 158.
4.5.7. 5,17-Bis(1-methyl ethoxydimethylsilyl)-25,26,27,28- tetra
propoxy calix[4]arene (3g)
Yield 62%; m.p. 79–81 °C; FTIR (KBr, cmꢀ1): 3068 (HC@), 1582,
4.6.2. 5,17-Bis(2-(p-chloromethyl phenyl) ethyl dimethylsilyl)-
25,26,27,28-tetra propoxy calix[4]arene (4b)
1457 (Ph), 1250 (Si–CH3), 1112 (Si–O); 1H NMR (400 MHz, CDCl3,
ppm):
d
0.45 (s, 12H, 2 ꢂ SiMe2), 0.91 (t, 6H, J = 7.2 Hz,
Yield 65%; m.p. 108–110 °C; FTIR (KBr, cmꢀ1): 3065 (HC@),
1585, 1456 (Ph), 1252 (Si–CH3), 1H NMR (400 MHz, CDCl3, ppm):
d 0.36 (s, 12H, 2 ꢂ SiMe2), 0.90 (t, 6H, J = 7.5 Hz, 2 ꢂ CH3CH2CH2O),
1.02 (t, 4H, J = 5 Hz, 2 ꢂ CH2CH2Si), 1.12 (t, 6H, J = 7.5 Hz,
2 ꢂ CH3CH2CH2O) 1.85–1.98 (m, 8H, 4 ꢂ CH3CH2CH2O), 2.69 (m,
4H, 2 ꢂ PhCH2CH2), 3.1 (d, 4H, J = 13.5 Hz, 4 ꢂ ArCHAr), 3.69 (t,
4H, J = 7 Hz, 2 ꢂ CH3CH2CH2O), 4.06 (t, 4H, J = 8 Hz, 2 ꢂ CH3CH2-
CH2O), 4.4 (d, 4H, J = 13.2 Hz, 4 ꢂ ArCHAr), 4.58 (s, 4H,
2 ꢂ ClCH2Ph), 6.0 (d, 4H, J = 7.8 Hz, aromatic), 6.1 (t, 2H,
J = 7.2 Hz, aromatic), 7.19–7.32 (m, 12H, aromatic); 13C NMR
(100 MHz, CDCl3, ppm): d ꢀ2.7 (SiMe), 9.7, 10.3, 18.5, 23.0, 23.5,
30.0, 31.0, 46.2, 76.3, 76.5, 121.9, 122.0, 127.9, 128.5,128.8,
131.0, 133.1, 134.4, 136.5, 145.8, 155.1, 159.1 ppm.
2 ꢂ CH3CH2CH2O), 1.09 (t, 6H, J = 7 Hz, 2 ꢂ CH3CH2CH2O), 1.18 (d,
12H, J = 6.3 Hz, 2 ꢂ (CH3)2CHO), 1.85–1.95 (m, 8H, 4 ꢂ CH3CH2-
CH2O), 3.1 (d, 4H, J = 13.5 Hz, 4 ꢂ ArCHAr), 3.68 (t, 4H, J = 6.6 Hz,
2 ꢂ CH3CH2CH2O), 4.03–4.10 (m, 6H, 2 ꢂ CH3CH2CH2O overlapped
with 2 ꢂ (CH3)2CHO), 4.4 (d, 4H, J = 13.2 Hz, 4 ꢂ ArCHAr), 6.06 (d,
4H, J = 7.5 Hz, aromatic), 6.15 (t, 2H, J = 7.6 Hz, aromatic), 7.30 (s,
4H, aromatic); 13C NMR (100 MHz, CDCl3, ppm): d ꢀ1.2 (SiMe),
9.7, 10.9, 23.0, 23.5, 25.6, 29.6, 65.11, 76.3, 76.5, 121.9, 127.2,
130.8, 133.1, 134.5, 136.5, 155.0, 159.5, ppm; Anal. Calc. for
C50H72O6Si2: C, 72.8; H, 8.8. Found: C, 72.5; H, 8.6%.
4.5.8. 5,17-Bis(2-methyl propoxydimethylsilyl)-25,26,27,28-tetra
propoxy calix[4]arene (3h)
Yield 60%; m.p. 82–84 °C; FTIR (KBr, cmꢀ1): 3059 (HC@), 1585,
1459 (Ph), 1252 (Si–CH3), 1087 (Si–O); 1H NMR (400 MHz, CDCl3,
ppm): d 0.42 (s, 12H, 2 ꢂ SiMe2), 0.85–0.94 (m, 18H, 2 ꢂ CH3CH2-
CH2O overlapped with 2 ꢂ (CH3)2CHCH2O), 1.12 (t, 6H, J = 8 Hz,
2 ꢂ CH3CH2CH2O), 1.7–1.8 (m, 10H, 4 ꢂ CH3CH2CH2O overlapped
with 2 ꢂ (CH3)2CHCH2O), 3.1 (d, 4H, J = 13.5 Hz, 4 ꢂ ArCHAr), 3.4
(d, 4H, J = 7 Hz, 2 ꢂ (CH3)2CHCH2O), 3.68 (t, 4H, J = 8 Hz,
2 ꢂ CH3CH2CH2O), 4.06 (t, 4H, J = 8 Hz, 2 ꢂ CH3CH2CH2O), 4.4 (d,
4.6.3. 5,17-Bis(2-methyl-2-phenyl ethyl dimethylsilyl)-25,26,27,28-
tetra propoxy calix[4]arene (4c)
Yield 72%; m.p. 67–69 °C; FTIR (KBr, cmꢀ1): 3058 (HC@), 1586,
1458 (Ph), 1255 (Si–CH3); 1H NMR (400 MHz, CDCl3, ppm): d 0.3 (s,
12H, 2 ꢂ SiMe2), 0.88–0.94 (m, 12H, 2 ꢂ CH3CH2CH2O over lapped
with 2 ꢂ CH2CH(CH3)Ph), 1.02 (t, 4H, J = 5 Hz, 2 ꢂ CH2CH2Si), 1.12
(t, 6H, J = 7.5 Hz, 2 ꢂ CH3CH2CH2O) 1.86–1.98 (m, 8H, 4 ꢂ CH3CH2-
CH2O), 3.1 (d, 4H, J = 13.5 Hz, 4 ꢂ ArCHAr), 3.6 (t, 4H, J = 6.7 Hz,

K.D. Safa, Y.M. Oskoei / Journal of Organometallic Chemistry 695 (2010) 505–511
511
2 ꢂ CH3CH2CH2O), 4.02 (t, 4H, J = 8 Hz, 2 ꢂ CH3CH2CH2O), 4.2(m,
References
2H, 2 ꢂ CH2CH(CH3)Ph), 4.4 (d, 4H, J = 13.5 Hz, 4 ꢂ ArCHAr), 6.0
(d, 4H, J = 7.8 Hz, aromatic), 6.1 (t, 2H, J = 7.2 Hz, aromatic), 7.10–
7.27 (m, 14H, aromatic); 13C NMR (100 MHz, CDCl3, ppm): d ꢀ2.7
(SiMe), 9.5, 10.1, 14.0, 22.6, 22.9, 30.2, 31.9, 76.3, 76.5, 121.7,
121.8, 127.7, 128.0, 128.5, 130.8, 132.4, 134.2, 136.3, 145.7,
155.1, 158.1 ppm.
[1] (a) C.D. Gutsche, Acc. Chem. Res. 16 (1983) 161;
(b) C.D. Gutsche, Top. Curr. Chem. 123 (1984) 1;
[c] C.D. Gutsche, ‘‘Calixarenes”, in: J.F. Stoddart (Ed.), Monographs in
Supramolecular Chemistry, RSC, Cambridge, 1989.;
(d) Z. Asfari, J. Vicens, Janssen Chim. Acta 10 (1992) 3–10;
(e) M. Takeshita, S. Shinkai, Bull. Chem. Soc. Jpn. 68 (1995) 1088–1097.
[2] (a) P.D. Beer, P.A. Gale, Angew. Chem., Int. Ed. 40 (2001) 486–516;
S.E. Matthews, P.D. Beer (Eds.), Calixarenes 2001, Kluwer Academic Publishers,
Dordrecht, 2001. pp. 421–439.
[3] (a) C. Chuit, R.J.P. Corriu, C. Reye, J.C. Young, Chem. Rev. 93 (1993) 1371–1448;
[b] C. Chuit, R.J.P. Corriu, C. Reye, in: K. Akiba (Ed.), Chemistry of Hypervalant
Compounds, Wiley-VCH, New York, 1999, pp. 81–146.;
[c] M. Kira, L.C. Zhang, in: K. Akiba (Ed.), Chemistry of Hypervalent
Compounds, Wiley-VCH, New York, 1999, pp. 147–169.
[4] F. Billo, R.M. Musau, A. Whiting, ARKIVOC, Part (x) (2006) 199–210.
[5] H. Ihm, K. Paek, Bull. Korean Chem. Soc. 16 (1995) 71–73.
[6] P.F. Hudrlik, A.M. Hudrlik, L. Zhang, W.D. Arasho, J. Cho, J. Org. Chem. 72 (2007)
7858–7862.
[7] P.F. Hudrlik, W.D. Arasho, A.M. Hudrlik, J. Org. Chem. 72 (2007) 8107–8110.
[8] M.T. Blanda, J. Frels, J. Lewicki, Supramol. Chem. 9 (1998) 255–261.
[9] K.D. Safa, Y. Mosaei Oskoei, J. Organomet. Chem. 695 (2010) 26–31.
[10] P.F. Hudrlik, A.M. Hudrlik, W.D. Arasho, R.J. Butcher, Synthesis 18 (2008) 2968.
[11] M.A. Brook, Silicon in Organic, Organometallic and Polymer Chemistry, Wiley-
Interscience Publication, 2003. pp. 175–184.
[12] J.L. Speier, J.A. Webster, G.H. Barnes, The addition of silicon hydrides to olefinic
double bonds. Part ii. The use of group viii metal catalysts, J. Am. Chem. Soc. 79
(1957) 974.
4.6.4. 5,17-Bis(3-(2,3-epoxypropoxy)propyl dimethylsilyl)-
25,26,27,28-tetra propoxy calix[4]arene (4d)
Yield 85%; m.p. 76–78 °C; FTIR (KBr, cmꢀ1): 3060 (HC@), 1585,
1457 (Ph), 1251 (Si–CH3), 1109 (C–O–C); 1H NMR (400 MHz, CDCl3,
ppm):
d
0.33 (s, 12H, 2 ꢂ SiMe2), 0.79 (t, 4H, J = 7.8 Hz,
2 ꢂ CH2CH2CH2Si), 0.88 (t, 6H, J = 7.2 Hz, 2 ꢂ CH3CH2CH2O), 1.11
(t, 6H, J = 7.2 Hz, 2 ꢂ CH3CH2CH2O), 1.6 (m, 4H, 2 ꢂ CH2CH2CH2Si),
1.84–1.97(m, 8H, 4 ꢂ CH3CH2CH2O), 2.6(q, 2H, J = 2.7 Hz, 2 ꢂ CH2–
CH(O)CH–H), 2.8 (t, 2H, J = 4 Hz, 2 ꢂ CH2–CH(O)CH–H), 3.1 (m, 6H,
4 ꢂ ArCHAr over lapped with 2 ꢂ CH2–CH(O)CH–H), 3.37–3.53(m,
8H, 2 ꢂ CH2CH2CH2OCH2–CH(O)CH–H overlapped with 2 ꢂ CH2-
CH2CH2OCH2–CH(O)CH–H), 3.6 (t, 4H, J = 7 Hz, 2 ꢂ CH3CH2CH2O),
4.03 (t, 4H, J = 8 Hz, 2 ꢂ CH3CH2CH2O), 4.4 (d, 4H, J = 13.5 Hz,
4 ꢂ ArCHAr), 6.0 (d, 4H, J = 6.6 Hz, aromatic), 6.1 (t, 2H, J=7 Hz, aro-
matic), 7.27 (s, 4H, aromatic); 13C NMR (100 MHz, CDCl3, ppm): d
ꢀ2.6 (SiMe), 9.7, 10.8, 12.1, 23.0, 23.5, 24.2, 31.0, 44.3, 50.9, 71.4,
74.4, 76.3, 76.5, 122.0, 127.2, 131.3, 133.2, 134.4, 136.4, 155.1,
159.0 ppm.
[13] B. Marciniec, Silicon Chem. 1 (2002) 155–175.
[14] M. Larsen, M. Jorgensen, J. Org. Chem. 61 (1996) 6651.
[15] A. Purkayshtha, J.B. Baruah, J. Mol. Catal. A: Chem. (2003) 47–55.
[16] J. Dwyer, H.S. Hilal, R.V. Parish, J. Organomet. Chem. 228 (1982) 191–201.