Synthesis of new imines and amines containing organosilicon groups

Article abstract of DOI:10.1016/j.jorganchem.2010.09.074

The Peterson olefination reaction of terephthalaldehyde with tris(trimethylsilyl)methyl lithium, (Me₃Si)₃CLi, in THF at 0 °C gives 4-[2,2-bis(trimethylsilyl)ethenyl]benzaldehyde (1) and 4,4-bis[2,2-bis(trimethylsilyl)ethenyl]benzene

Full text of DOI:10.1016/j.jorganchem.2010.09.074

Journal of Organometallic Chemistry 696 (2011) 802e806
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Synthesis of new imines and amines containing organosilicon groups
*
Kazem D. Safa , J. Vahid Mardipour, 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:
The Peterson olefination reaction of terephthalaldehyde with tris(trimethylsilyl)methyl lithium,
(Me3Si)3CLi, in THF at 0 ꢀC gives 4-[2,2-bis(trimethylsilyl)ethenyl]benzaldehyde (1) and 4,4-bis[2,2-bis
(trimethylsilyl)ethenyl]benzene (2). The new aldehyde (1) reacts with variety of amines in ethanol to
afford the corresponding imines (3) containing vinylbis(trimethylsilyl) group. The newly synthesized
imines (3) can be completely converted into amines containing vinylbis(trimethylsilyl) group with an
excess amount of NaBH4 . In the case of N-[4-(2,2-bis(trimethylsilyl)ethenyl)benzyl]-2,6-dimethylaniline
LiAlH4 was used as a reducing agent in THF.
Received 23 August 2010
Received in revised form
26 September 2010
Accepted 30 September 2010
Available online 12 October 2010
Keywords:
Vinylbis(silanes)
Organosilicon
Imine
Ó 2010 Elsevier B.V. All rights reserved.
Amine
1. Introduction
constitute important precursors to compounds that are of such
interest in pharmaceutical and agricultural industries [7,8].
Vinylsilanes are useful reagents in organic synthesis because the
C (sp2)-Si bonds undergo numerous transformation [1]. Vinylbis
(silanes), which show a number of similar properties, have received
significant attention as potential synthons in organic and organo-
silicon synthesis [2]. The potential of the vinylbis(silanes) as
precursors for the preparation of ketones and isoxazoline deriva-
tives, as well as a variety of important organosilicon reagents, such
as acylsilanes, epoxy silanes, silanols, has stimulated their deve-
lopment. In contrast to vinyl silanes however, vinylbis(silanes) are
relatively unexplored [3]. We have recently reported [4] new
derivatives of vinylbis(silanes) via Peterson-type olefination reac-
tion. However, no vinylbis(silanes) containing imine and amine
group have hitherto been reported.
Imine, also known as azomethine, is formed by the reversible
condensation between amine and carbonyl group. This reaction
was discovered by the German chemist Hugo Schiff in 1864 and
since then imines are also called as Schiff base [5]. An imine is
a chemical compound containing carbonenitrogen double bond
with a general structure R1R2C]NR3 used as a key intermediate for
the synthesis of nitrogen hetrocycles [6]. From the fundamental
point of view, reduction of imines to the corresponding amines
represent one of the most widely used and valuable functional
group transformations in synthetic organic chemistry, since amines
In the present work, we describe the synthesis of some vinylbis
(silane) derivatives containing imine and amine groups. The newly
synthesized vinylbis(silanes) containing imine and amine group
might be used for the preparation of hetrocycles and other organic
compounds containing organosilicon group, which cannot be
achieved via other methods.
2. Results and discussion
Tris(trimethylsilyl)methane, (Me3Si)3CH, has been conveniently
prepared by the reaction of CHCl3 and Li with Me3SiCl in THF. The
generation of (Me3Si)3CLi was easily accomplished via deprotona-
tion of (Me3Si)3CH by MeLi in THF [9,10].
The precursor 4-[2,2-bis(trimethylsilyl)ethenyl]benzaldehyde
(1) was prepared from the reaction of terephthalaldehyde with
[(trimethylsilyl)methyl]lithium, (Me3Si)3CLi, (Scheme 1).
In order to optimize the conditions for the formation of 1, we
decided to investigate the reaction of (Me3Si)3CLi (1 equiv.) with
various amounts of terephthalaldehyde at different temperatures
(Table 1). When 5 equivalent of terephthalaldehyde was used at
0
ꢀC, 1 was the major product.
The newly synthesized 4-[2,2-bis(trimethylsilyl)ethenyl]benz-
aldehyde (1) was treated with an excess of various aromatic
amines, the formation of the corresponding imines took place quite
smoothly (Scheme 2). The reaction was performed in alcohol
(methanol or ethanol) and was monitored via FTIR, actually, the
infrared spectra of imines showed the expected absorptions in the
* Corresponding author. Tel.: þ98 411 3393124; fax: þ98 411 3340191.
E-mail address: dsafa@tabrizu.ac.ir (K.D. Safa).
0022-328X/$ e see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.09.074

K.D. Safa et al. / Journal of Organometallic Chemistry 696 (2011) 802e806
803
Me3Si
SiMe3
Me3Si
O
O
O
THF
+
C
H
C
H
C
H
+ (Me3Si)3CLi
Me3Si
SiMe3
Me3Si
H
H
H
(2)
(1)
excess
Scheme 1. The preparation of 4-[2,2-bis(trimethylsilyl)ethenyl]benzaldehyde via Peterson protocol.
Table 1
Summary of experimental conditions and yields obtained in the reaction of terephthalaldehyde with (Me3Si)3CLi.
Entry
Terephthalaldehyde
(equiv.)
(Me3Si)3CLi
(equiv.)
Temperature
Condition
1a (%)
2a (%)
1
2
3
4
5
5
5
5
1
1
1
1
r.t
(Me3Si)3CLi was added dropwise over terephthalaldehyde
and the reaction mixture was mixed for 15 h.
(Me3Si)3CLi was added quickly over terephthalaldehyde
and the reaction mixture was mixed for 15 h.
(Me3Si)3CLi was added quickly over terephthalaldehyde
and the reaction mixture was mixed for 15 h.
(Me3Si)3CLi was added quickly over terephthalaldehyde
and the reaction mixture was mixed for 30 min.
43
33
56
65
45
55
33
25
reflux
r.t
0
ꢀC
a
Isolated yields.
Me3Si
Me3Si
O
Me3Si
EtOH
H
H
H
ArNH2
+
C
C
N
C
Ar
H
Me3Si
(3)
(1)
Scheme 2. The synthesis of imines containing vinylbis(trimethylsilyl) group.
range of 1550e1690 cmꢁ1usually attributed to C]N stretching. In
addition, the 1H NMR spectrum of the raw product of the imines
showed a complete disappearance of eCHO at 9.99 ppm.
All the new synthesized imines (Table 2) were identified by GC-
Mass method. In order to separate pure imines containing vinylbis
(trimethylsilyl) group from the reaction mixture, preparative TLC
was used. But in the presence of silica gel, the newly synthesized
imines were converted to the precursor 1.
The newly synthesized imines containing vinylbis(trime-
thylsilyl) group were obtained from the reaction of 1 with variety of
amines. These imines might be used as intermediate for the
synthesis of attractive molecules containing organosilicon group.
The reaction of imines containing organosilicon groups with NaBH4
gives the corresponding secondary amines containing organo-
silicon groups, which cannot be achieved via other methods.
So, we decided to apply direct reductive amination of imines
which are attractive methods for the preparation of amine deriv-
atives in organic synthesis [6].
4. Experimental
4.1. Solvent and reagents
Sodium borohydride, as a kind of common reducing agent, has
been used widely in organic synthesis and there are several reports
in the literature for reducing the imines by sodium borohydride
[11e13].
Reactions involving organolithium reagents were carried out
under dry argon. Solvents were dried by standard methods.
Substrates for preparation of (Me3Si)3CLi, viz., Me3SiCl, Li, CHCl3
and terephthaldehyde, and also all amines used in synthesis of
imines, NaBH4 and LiAlH4 were purchased from Merck and Fluka
and used without further purification.
We initially studied the reductive amination of the newly
synthesized aldehyde (1) with aniline in ethanol, which afforded
the corresponding imine (Scheme 3) that was then reduced with
NaBH4 to give the corresponding amine in 65%, isolated yield.
With the first successful result in hand, reduction of other
imines with NaBH4 was carried out under similar reduction
conditions. The obtained results are presented in Table 3.
As shown in Table 3, high yield in the reduction of the imines
was achieved in the presence of halogen (flourine) functional
groups. In the case of 2,6-dimethylaniline, reaction was not
completed in the presence of NaBH4, so LiAlH4 was used as the
reducing agent in THF.
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
the solvent. The Mass spectra were obtained with a GC-Mass Agi-
lent, quadrupole model 5973 N instrument, operating at 70 eV. The
FTIR spectra were recorded on a Bruker-Tensor 270 spectrometer.
Elemental analysis were carried out with an elemental Vario EL III
instrument.
3. Conclusion
4.3. Preparation of tris(trimethylsilyl)methyllithium, (Me3Si)3CLi, in
THF
We demonstrated the convenient one-pot preparation of 4-[2,2-
bis(trimethylsilyl)ethenyl]benzaldehyde (1) via Peterson protocol.
When 5-fold the mol ratio of terephthaldehyde was used at 0 ꢀC, 1
was the major product.
The reagent was prepared as described by Grobel and co-
workers [10].

804
K.D. Safa et al. / Journal of Organometallic Chemistry 696 (2011) 802e806
Table 2
4.4. Preparation of 4-[2,2-bis(trimethylsilyl)ethenyl]benzaldehyde
Reaction of 4-[2,2-bis(trimethylsilyl)ethenyl]benzaldehyde with various amines.
Tris(trimethylsilyl)methyllithium (22.4 mmol) was poured
quickly onto terephthaldehyde 18.7 g (139.4 mmol) in THF at 0 ꢀC
under argon and was mixed for 30 min, then the reaction mixture
was poured into 200 ml of water and extracted into ether
(3 ꢂ 100 ml). The organic layer was dried (Na2SO4) and the solvent
was evaporated and the residue was purified by preparative
column chromatography (n-hexane/ethyl acetate, 10:1, Rf ¼ 0.7) to
give highly viscose yellow oil (65%). FTIR (KBr, cmꢁ1): 840, 1251
(SieCH3), 1558, 1603 (Ph), 1703 (C]O); 1H NMR (400 MHz, CDCl3,
Entry
Amine
Condition
Time (h)
Yielda (%)
1
Reflux
44
91
ppm):
J ¼ 7.9 Hz, Ar), 7.7 (s, 1H, HC ¼ ), 7.8e7.82 (d, 2H, J ¼ 8.7 Hz, Ar), 9.99
(s,1H, HC]O); 13C NMR (100 MHz, CDCl3, ppm):
127.4, 128.3, 133.9, 148.2, 148.6, 151.9, 190.9; m/z (EI): 276 (45%,
[M]þ), 261 (100%, [M ꢁ Me]þ), 73 (73%, [SiMe3]þ); Anal. Calcd for
C15H24OSi2 (276.14): C, 65.15; H, 8.75. Found: C, 65.00; H, 8.61%.
d
ꢁ0.05 (s, 9H, SiMe3), 0.2 (s, 9H, SiMe3), 7.32e7.34 (d, 2H,
2
Reflux
85
70
d
ꢁ0.6, 0.9 (SiMe3),
4.5. General procedure for the synthesis of new imines and amines
containing vinylbis(trimethylsilyl) groups
3
4
5
Reflux
1
30
2
99
98
98
To a 50-ml round-bottom flask were added 0.72 mmol of 4-[2.2-
bis(trimethylsilyl)ethenyl]benzaldehyde, 0.86 mmol of amine and
5 ml of ethanol. The mixture was performed according to Table 2.
The reaction progress was monitored by FTIR spectroscopy, GC-
Mass and TLC. After all the aldehyde precursor was consumed,
2.17 mmol of NaBH4 was added and the mixture was stirred (Table
3) at room temperature. Then the reaction mixture poured into
water (50 ml) and extracted into ether (3 ꢂ 15 ml). The organic
layer was dried (Na2SO4) and the solvent was evaporated and the
residue was purified by preparative TLC (n-hexane/ethyl acetate;
10:1) to give the corresponding amines.
r.t
r.t
4.5.1. N-[4-(2,2,-bis(trimethylsilyl)ethenyl)benzyl]aniline
A white solid (silica gel, n-hexane/ethyl acetate, 10:1, Rf ¼ 0.43),
m.p. 70e72 ꢀC; FTIR (KBr, cmꢁ1): 837.9, 1257.9, (SieCH3), 1559.8,
1603.4 (Ph), 3423.1 (NeH); 1H NMR (400 MHz, CDCl3, ppm):
6
7
r.t
12
98
d
ꢁ0.04 (s, 9H, SiMe3), 0.18 (s, 9H, SiMe3), 4.02 (bs, 1H, NeH), 4.3 (s,
2H, CH2), 6.62e6.64 (d, 2H, J ¼ 7.6 Hz, Ar), 6.69e6.73 (t, 1H,
J ¼ 7.3 Hz, Ar), 7.14e7.19 (m, 4H, Ar), 7.28e7.3(d, 2H, J ¼ 8.0 Hz, Ar),
7.7(s, 1H, HC]); 13C NMR (100 MHz, CDCl3, ppm):
d
ꢁ0.48, 1.0
(SiMe3), 47.13 (CH2), 111.8, 116.5, 125.1, 127.1, 128.2, 137.1, 140.7,
145.4, 147.1, 153.5; m/z (EI): 352 (100%, [M]þ), 73 (38%, [SiMe3]þ);
Anal. Calcd for C21H31NSi2 (353.2): C, 71.32; H, 8.84; N, 3.96. Found:
C, 71.51; H, 8.80; N, 3.75%.
r.t
16
86
71
82
4.5.2. N-[4-(2,2-bis(trimethylsilyl)ethenyl)]benzylpyridin-2-amine
A yellow solid (silica gel, n-hexane/ethyl acetate, 10:1, Rf ¼ 0.3),
m.p. 75e77 ꢀC; FTIR (KBr, cmꢁ1): 836.8, 1248.8 (SieCH3), 1522.8,
1602.8 (Ph), 3420.8 (NeH); 1H NMR (400 MHz, CDCl3, ppm):
8
Reflux
d
ꢁ0.05 (s, 9H, SiMe3), 0.18 (s, 9H, SiMe3), 4.4 (s, 2H, CH2), 4.84 (bs,
1H, NeH), 6.35e6.37 (d, 1H, J ¼ 8.4 Hz, Ar), 6.57e6.6 (m, 1H, Ar),
7.13e7.15 (d, 2H, J ¼ 7.8 Hz, Ar), 7.27e7.29 (d, 2H, J ¼ 7.9 Hz, Ar),
7.37e7.42 (m, 1H, Ar), 7.71 (s, 1H, HC]), 8.0e8.1 (m, 1H, Ar); 13C
a
Yields obtained by GC-Mass.
NMR (100 MHz, CDCl3, ppm):
d
ꢁ0.5, 0.99 (SiMe3), 45.1 (CH2), 105.6,
Me3Si
Me3Si
Me3Si
H
NaBH4
H
H
C
H2
C
H
C
N
Ar
C
N
Ar
Me3Si
(4)
(3)
Scheme 3. The synthesis of secondary amine containing vinylbis(trimethylsilyl) group.

K.D. Safa et al. / Journal of Organometallic Chemistry 696 (2011) 802e806
805
Table 3
Reducing various imines containing vinylbis(trimethylsilyl) group to the corresponding secondary amine by NaBH4 at room temperature.
Entry
Substrate
Product
Time (h)
15
Yielda (%)
1
65
60
75
2
3
15
24
4
12
80
5
6
18
10
95
78
7
18
48
67
60
8b
a
Isolated yields.
LiAlH4 was used as reducing agent in THF.
b
112.1, 125.7, 127.1, 136.4, 136.8, 140.8, 145.5, 147.2, 153.4, 157.6; m/z
(EI): 354 (100%, [M]þ), 73 (37%, [SiMe3]þ); Anal. for C20H30N2Si2
(354.19): C, 67.74; H, 8.53; N, 7.9. Found: C, 67.70; H, 8.31; N, 7.75%.
(Ph), 3444.7 (NeH); 1H NMR (400 MHz, CDCl3, ppm):
d
0.01 (s, 9H,
SiMe3), 0.2(s, 9H, SiMe3), 4.52 (s, 2H, CH2), 4.73 (bs, 1H, NeH),
6.61e6.63 (d, 2H, J ¼ 7.4 Hz, Ar), 7.21e7.23 (d, 2H, J ¼ 7.9 Hz, Ar),
7.27e7.29 (d, 1H, J ¼ 8.0 Hz, Ar), 7.32e7.36 (t, 1H, J ¼ 7.4 Hz, Ar),
7.39e7.41 (d, 2H, J ¼ 7.9 Hz, Ar), 7.44e7.51 (m, 2H, Ar), 7.79 (s, 1H,
HC]), 7.82e7.86 (t, 1H, J ¼ 7.7 Hz, Ar); 13C NMR (100 MHz, CDCl3,
4.5.3. 4-[4-(2,2-bis(trimethylsilyl)ethenyl)benzylamino]phenol
A yellow solid (silica gel, n-hexane/ethyl acetate, 10:1, Rf ¼ 0.43),
m.p. 105e107 ꢀC; FTIR (KBr, cmꢁ1): 835.9, 1251.0 (SieCH3), 1514.5,
1609.5 (Ph), 3297.9 (OeH), 3434.9 (NeH); 1H NMR (400, MHz,
ppm):
d
ꢁ0.46, 1.03 (SiMe3), 47 (CH2), 103.8, 116.5, 118.8, 122.3,
123.7, 124.7, 125.5, 125.9, 127.2, 127.6, 133.2, 136.8, 140.9, 142.1,
145.5, 1534; m/z (EI): 403.4 (100%, [M]þ), 73 (22%, [SiMe3]þ); Anal.
Calcd for C25H33NSi2 (403.22): C, 74.38; H, 8.24; N, 3.47. Found: C,
74.40; H, 8.5; N, 3.65%.
CDCl3):
d
ꢁ0.05 (s, 9H, SiMe3), 0.18 (s, 9H, SiMe3), 3.8 (bs, 1H, NeH),
4.27 (s, 2H, CH2), 5.3 (bs, 1H, OH), 6.53e6.56 (d, 2H, J ¼ 8.7 Hz, Ar),
6.68e6.7 (d, 2H, J ¼ 8.7 Hz, Ar), 7.13e7.15 (d, 2H, J ¼ 8 Hz, Ar),
7.27e7.29 (d, 2H, J ¼ 7.9 Hz, Ar), 7.72 (s, 1H, HC]); 13C NMR
(100 MHz CDCl3, ppm):
d
ꢁ0.47, 1.0 (SiMe3), 48.1 (CH2), 113.3, 115.1,
4.5.5. N-[4-(2,2-bis(trimethylsilyl)ethenyl)benzyl]-4-chloroaniline
A yellow viscose oil (silica gel, n-hexane/ethyl acetate, 10:1,
Rf ¼ 0.56); FTIR(KBr, cmꢁ1): 838.8, 1249.9 (SieCH3), 1501.9, 1601.7
125.8, 127.1, 138, 140.7, 141.4, 146, 145, 153.5; m/z (EI): 369 (100%,
[M]þ), 91 (39%, [PhCH2]þ), 73 (35%, [SiMe3]þ); Anal. Calcd For
C21H31NOSi2 (369.19): C, 68.23; H, 8.45; N, 3.79. Found: C, 68.49; H,
8.22; N, 3.81%.
(Ph), 3418.2 (NeH); 1H NMR (400 MHz, CDCl3, ppm):
d
ꢁ0.04 (s, 9H,
SiMe3), 0.2 (s, 9H, SiMe3), 4.06 (bs, 1H, NeH), 4.3 (s, 2H, CH2),
6.53e6.55 (d, 2H, J ¼ 8.7 Hz, Ar), 7.09e7.1 (d, 2H, J ¼ 7.9 Hz, Ar),
7.15e7.17(d, 2H, J ¼ 8.01 Hz, Ar), 7.26e7.28 (d, 2H, J ¼ 7.9 Hz, Ar) 7.73
4.5.4. N-[4-(2,2-bis(trimethylsilyl)ethenyl)benzyl]naphtalen-1-
amine
(s, 1H, CH]); 13C NMR (100 MHz, CDCl3, ppm):
d
ꢁ0.48, 1.0 (SiMe3),
A yellow viscose oil (silica gel, n-hexane/ethyl acetate, 10:1,
47.1 (CH2), 112.9, 121.1, 125.7, 127.2, 128.0, 136.6, 140.9, 145.6, 145.7,
Rf ¼ 0.7); FTIR (KBr, cmꢁ1): 837.9, 1248.8 (SieCH3), 1525.6, 1580.9
153.3; m/z (EI): 389.2 (44%, [M þ 2]þ), 388.2 (34%, [M þ 1]þ), 387.2

806
K.D. Safa et al. / Journal of Organometallic Chemistry 696 (2011) 802e806
(100%, [M]þ), 73 (45%, [SiMe3]þ); Anal. Calcd for C21H30ClNSi2
(387.16): C, 64.99; H, 7.79; N, 3.61. Found: C, 64.97; H, 7.81; N, 3.60%.
SiMe3), 0.25 (s, 9H, SiMe3), 2.3 (s, 6H, Me), 3.2 (bs, 1H, NeH), 4.1 (s,
2H, CH2), 6.87e6.91 (t, 1H, J ¼ 7.45 Hz, Ar), 7.04e7.06 (d, 2H,
J ¼ 7.4 Hz, Ar), 7.19e7.21 (d, 2H, J ¼ 7.8 Hz, Ar), 7.3e7.32 (d, 2H,
J ¼ 8 Hz, Ar), 7.79 (s, 1H, HC]); 13C NMR (100 MHz, CDCl3, ppm):
4.5.6. N-[4-(2,2-bis(trimethylsilyl)ethenyl)benzyl]-2-bromoaniline
A colorless viscose oil (silica gel, n-hexane/ethyl acetate, 10:1,
Rf ¼ 0.64); FTIR (KBr, cmꢁ1): 838.6, 1248.3 (SieCH3), 1506.1, 1597.2
d
ꢁ0.45, 0.94 (SiMe3), 17.5 (CH3), 51.65 (CH2), 121.0, 126.3, 127.0,
127.8, 128.6, 138.2, 140.7, 144.8, 145.4, 153.5; m/z (EI): 381.2 (100%,
[M]þ), 91 (72%, [PhCH2]þ), 73 (57%, [SiMe3]þ); Anal. Calcd for
C23H35NSi2 (381.23): C, 72.37; H, 9.24; N, 3.67. Found: C, 72.18; H,
9.14; N, 3.72%.
(Ph), 3422.4 (NeH); 1H NMR (400 MHz, CDCl3, ppm):
d 0.005 (s, 9H,
SiMe3), 0.24 (s, 9H, SiMe3), 4.4 (s, 2H, CH2), 4.8 (bs,1H, NeH), 6.5e6.6
(m, 2H, Ar), 7.11e7.16 (m, 1H, Ar), 7.19e7.21 (d, 2H, J ¼ 7.9 Hz, Ar),
7.31e7.33 (d, 2H, J ¼ 8.0 Hz, Ar), 7.46e7.48 (q, 2H, Ar), 7.78 (s, 1H,
HC]); 13C NMR (100 MHz, CDCl3, ppm):
d
ꢁ0.4, 1.0 (SiMe3), 46.8
References
(CH2), 108.6, 110.7, 116.9, 125.5, 127.2, 127.4, 131.3, 136.4, 140.8, 143.7,
145.6, 153.4; m/z (EI): 433.1 (100%, [M þ 1]þ), 431.1 (93%, [M ꢁ 1]þ), 73
(52%, [SiMe3]þ); Anal. Calcd for C21H30BrNSi2 (431.11): C, 58.31; H,
6.99; N, 3.24. Found: C, 58.30; H, 7.1; N, 3.50%.
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A yellow viscose oil (silica gel, n-hexane/ethyl acetate, 10:1,
Rf ¼ 0.59); FTIR (KBr, cm1-): 839.8, 1250.2 (SieCH3), 1512.8, 1611.4
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(Ph), 3427.6 (NeH); 1H NMR (400 MHz, CDCl3, ppm):
d
ꢁ0.01 (s, 9H,
SiMe3), 0.2 (s, 9H, SiMe3), 3.9 (bs, 1H, NeH), 4.3 (s, 2H, CH2),
6.55e6.58 (q, 2H, Ar), 6.87e6.91 (t, 2H, J ¼ 8.6 Hz, Ar), 7.17e7.19 (d,
2H, J ¼ 7.9 Hz, Ar), 7.29e7.31 (d, 2H, J ¼ 8.0 Hz, Ar), 7.79 (s, 1H,
(b) K.D. Safa, M. Namvari, A. Hassanpour, Sh. Tofangdarzade, J. Organomet.
Chem. 694 (2009) 2448e2453;
HC]); 13C NMR (100 MHz, CDCl3, ppm):
d
ꢁ0.47, 1.0 (SiMe3), 47.7
(c) K.D. Safa, Y. Mosaei Oskoei, J. Organomet. Chem. 695 (2010) 26e31.
[5] C.D. Meyer, C.S. Joiner, J.F. Stoddart, Chem. Soc. Rev. 36 (2007) 1705e1723.
[6] S.F. Martin, Pure Appl. Chem. 81 (2009) 195e204.
[7] R.O. Hutchins, M.K. Hutchins, Comprehensive Organic Synthesis, vol. 8, Per-
gamon Press, Oxford, 1991, pp. 25.
(CH2), 112.7, 114.7, 125.7, 127.2, 136.9, 140.8, 143.4, 145.6, 153.7, 156;
m/z (EI): 372.2 (32%, [M þ 1]þ), 371.2 (100%, [M]þ), 73 (31%,
[SiMe3]þ); Anal. Calcd for C21H30FNSi2 (371.19): C, 67.87; H, 8.14; N,
3.77. Found: C, 67.98; H, 8.30; N, 3.56%.
[8] I. Shibata, T.M. Kawakami, D. Tanizawa, T. Suwa, E. Sugiyama, H. Matsuda,
A. Baba, J. Org. Chem. 63 (1998) 383.
[9] K.D. Safa, M. Babazadeh, Eur. Polym. J. 40 (2004) 1659.
[10] B.T. Gröbel, D. Seebach, Chem. Ber. 110 (1977) 825.
[11] R. Bolton, T.N. Danks, J.M. Paul, Tetrahedron Lett. 35 (1994) 3411.
[12] B.T. Cho, S.K. Kang, Synlett (2004) 1484.
4.5.8. N-[4-(2,2-bis(trimetylsilyl)ethenyl)benzyl]-2,6-dimetylaniline
A yellow viscose oil (silica gel, n-hexane/ethyl acetate, 10:1,
Rf ¼ 0.58); FTIR (KBr, cmꢁ1): 839.5, 1250.8 (SieCH3), 1552.6, 1596.9
(Ph), 3381.7 (NeH); 1H NMR (400 MHz, CDCl3, ppm):
d
0.03 (s, 9H,
[13] B.T. Cho, S.K. Kang, Tetrahedron 61 (2005) 5734.