Synthesis of 2-aryl-1,1-bis(silyl)alkenes containing alkyl(aryl)amine groups

Article abstract of DOI:10.3184/174751914X14057852950474

4-Alkyl-(aryl)aminobenzaldehydes have been generated via the nucleophilic aromatic substitution reaction of 4-fluorobenzaldehyde with appropriated amines and N-heterocycles using hexadecyltrimethylammonium bromide as catalyst and converted to 1,1-bis(silyl)-1-alkene derivatives via the Peterson olefination reaction. The reaction of (HMe₂Si)₃CLi with these aromatic aldehydes led to new 2-aryl-1,1-bis(silyl)alkenes.

Full text of DOI:10.3184/174751914X14057852950474

498 RESEARCH PAPER
VOL. 38 AUGUST, 498–501
JOURNAL OF CHEMICAL RESEARCH 2014
Synthesis of 2‑aryl‑1,1‑bis(silyl)alkenes containing alkyl(aryl)amine groups
Kazem Dindar Safa*, Sanaz Nadimi and Maryam Alyari
Organosilicon Research Laboratory, Faculty of Chemistry, University of Tabriz, 5166616471, Tabriz, Iran
4-Alkyl-(aryl)aminobenzaldehydes have been generated via the nucleophilic aromatic substitution reaction of
4-fluorobenzaldehyde with appropriated amines and N-heterocycles using hexadecyltrimethylammonium bromide as catalyst
and converted to 1,1-bis(silyl)-1-alkene derivatives via the Peterson olefination reaction. The reaction of (HMe2Si)3CLi with these
aromatic aldehydes led to new 2-aryl-1,1-bis(silyl)alkenes.
Keywords: nucleophilic aromatic substitution, hexadecyltrimethylammonium bromide, N‑heterocycles, 2‑aryl‑1,1‑bis(silyl)
alkenes, Peterson olefination reaction
1,1‑Disilylated‑1‑alkenes are useful starting materials in organic
synthesis, and their electrophilic chemistry has attracted
attention.1 2‑Aryl‑1,1‑bis(silyl)alkenes are organometallic
compounds that are widely recognised as valuable reagents in
organic chemistry for their ability to participate in large number
of synthetically useful reactions. They are also stable to many
reagents (e.g. mild acids, strong bases, hydride reducing agents)
and can therefore be carried through a number of steps in a
synthetic sequence.2
2‑Aryl‑1,1‑bis(silyl)alkenes are precursors for the preparation
of ketones and isoxazoline derivatives, as well as a variety of
important organosilicon reagents, such as acyl silanes, epoxy
silanes and silanols.3 The low cost, stability and non‑toxic
nature of many silicon‑containing functional groups has
increased their application as synthetic intermediates.4
We have recently reported the synthesis of new 2‑aryl‑1,1‑
bis(silyl)alkene derivatives via Peterson olefination reaction.5–7
In the present work, we describe the synthesis of some 2‑aryl‑
1,1‑bis(silyl)alkene derivatives containing an amine group and
N‑heterocycles.
Initially we synthesised 4‑alkyl‑(aryl)aminobenzaldehydes
via the nucleophilic aromatic substitution reaction of
4‑fluorobenzaldehyde with an appropriate amines and
N‑heterocycles, using N,N‑dimethylformamide (DMF) as
the solvent and hexadecyltrimethylammonium bromide as a
catalyst. The reaction was performed by heating at 100 °C for
24 hours. Among different para‑substituted benzaldehydes,
4‑fluorobenzaldehyde is the more than the corresponding bromo
and chloro analogues.13 The 4‑alkyl‑(aryl)aminobenzaldehydes
that were synthesised were then reacted with (Me3Si)3CLi or
(HMe2Si)3CLi to afford the title compounds in good overall
yields (Scheme 1).
Tris(trimethylsilyl)methane, (Me3Si)3CH, has been prepared
by the reaction of CHCl3 and Li with Me3SiCl in THF.
The generation of (Me3Si)3CLi was easily accomplished
via deprotonation of (Me3Si)3CH by MeLi in THF.14
Tris(dimethylsilyl)methane has been prepared from the reaction
between CHBr3, Mg and HMe2SiCl in THF. (HMe2Si)3CLi was
then metallated by treatment of (HMe2Si)3CH with LDA at
room temperature.15
Results and discussion
By using the Peterson olefination reaction, alkoxide
intermediate A forms when (Me3Si)3CLi is treated with a
compound containing a carbonyl group. An intramolecular
alkoxide attack takes place and then gives 1 (Scheme 2). Thus,
synthetically useful 2,2‑bis(trimethylsilyl)ethenyl groups can
be prepared by the reaction of (Me3Si)3CLi with variety of
4‑dialkyl(aryl)aminobenzaldehydes (Table 1).
Recently, we have embarked on a program directed towards
the development for the generation of synthetically useful
organosilicon compounds.8,9 We paid particular attention
to N‑aryl amines, specially imidazole and benzotriazoles
because of the frequent occurrence of these structural units in
biologically active inhibitors.10–12
SiMe2R'
CHO
H
C O
(R'Me2Si)3CLi
K2CO3 /DMF
SiMe2R'
R2NH
+
C16H3 (CH3)3N Br/ 100oC
F
3
R
R
'
:
R
Me
H
1
2
:
R
N
N
N
O
N
N
N
N
N
N
N
N
Scheme 1 Synthesis of some 2-aryl-1,1-bis(silyl)alkene derivatives containing amine group and N-heterocycles.
* Correspondent. E‑mail: dsafa@tabrizu.ac.ir
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JOURNAL OF CHEMICAL RESEARCH 2014 499
Me3Si
Me3Si
e
iM
S
3
SiMe3
Me3Si
H
C O
Li
O
(Me3Si)3CLi
-
Me3SiOLi
R
R
R
A
1
Scheme 2 Synthesis of some 2,2-bis(trimethylsilyl)ethenyl derivatives containing amine group and N-heterocycles.
Table 1 The results of reaction of 4-alkyl(aryl)aminobenzaldehydes with
(Me3Si)3CLi
Conclusion
The new 2‑aryl‑1,1‑bis(silyl)alkenes were obtained from the
reaction of 4‑alkyl(aryl)aminobenzaldehydes with (Me3Si)3CLi
or (HMe2Si)3CLi. These compounds are potential intermediates
for the functionalisation of N‑aryl amine which cannot be
achieved via other methods.
R
Product
Time/min
Yield/%a
Morpholine-4-yl
Piperidine-1-yl
Pyrrolidine-1-yl
Imidazole-1-yl
Benzotriazole-1-yl
Benzotriazol-2-yl
1a
1b
1c
1d
1e
1f
10
10
10
30
15
15
92
93
90
70
80
85
Experimental
All chemicals were used as purchased and 4‑alkyl(aryl)
aminobenzaldehydes was synthesised by literature methods. The
1H and 13C NMR spectra were recorded with a Bruker FT‑400 MHz
spectrometer at room temperature and CDCl3 as a solvent. The
FTIR spectra (KBr discs) were recorded on a Bruker‑Tensor 270
spectrometer. Elemental analyses (C, H and N) were performed with
a Heraeus CHN‑O‑Rapid analyser. The products were purified by
PTLC on silica gel with hexane/ethyl acetate as eluent. All compounds
were characterised by spectroscopic data and elemental analysis.
aIsolated yield.
Table 2 The results of reaction of 4-alkyl(aryl)aminobenzaldehydes with
(HMe2Si)3CLi
R
product
Time/min
Yield/%a
Morpholine-4-yl
Piperidine-1-yl
Pyrrolidine-1-yl
Imidazole-1-yl
Benzotriazole-1-yl
Benzotriazol-2-yl
2a
2b
2c
2d
2e
2f
15
15
15
90
30
30
90
88
86
70
77
73
Synthesis of new 2‑aryl‑1,1‑bis(silyl)alkenes containing amine and
heterocycles groups; general procedure
aIsolated yield.
The 4‑alkyl(aryl)aminobenzaldehyde (1 mmol) was added to
(RMe2Si)3CLi, R=H,Me (1 mmol) in THF under argon. The mixture
was reacted according to Tables 1 and 2. The reaction was quenched
with H2O, extracted with CH2Cl2 and dried over Na2SO4. The solvent
was evaporated under reduced pressure and the residue was purified
by preparative column chromatography (n‑hexane/ethylacetate) and
the corresponding products were obtained.
4‑(4‑(2,2‑Bis(trimethylsilyl)vinyl)phenyl)morpholine (1a): Yellow
oil; yield 92%, (silica gel, n‑hexane/ethyl acetate, 10:4, Rf =0.5); FTIR
(KBr, cm–1): 2847 (HC=), 1244 and 843 (Si–C), 1120 (C–N), 1055
(C–O); 1H NMR (400 MHz, CDCl3):ꢀδꢀ0.02ꢀ(s,ꢀ9H,ꢀSiMe3), 0.19 (s, 9H,
SiMe3), 3.17 (t, 4H, J=4.7 Hz, CH2–N–CH2), 3.87 (t, 4H, J=4.7 Hz,
CH2–O–CH2), 6.85 (d, 2H, J=8.5 Hz, Ar), 7.14 (d, 2H, J=8.5 Hz, Ar),
7.68 (s, 1H, HC=); 13C NMR (100 MHz, CDCl3):ꢀδꢀ–0.36,ꢀ1.13ꢀ(SiMe3),
48.13, 65.79, 113.56, 128.03, 133.11, 143.11, 149.27, 153.72; m/z (EI):
333 (100%, [M]+), 260 (37%, [M–SiMe3]+), 73 (33%, [SiMe3]+). Anal.
calcd for C18H31NOSi2: C, 64.80; H, 9.37; N, 4.20; found: C, 64.87; H,
9.42; N, 4.12%.
The reaction of (HMe2Si)3CLi and 4‑alkyl(aryl)
aminobenzaldehydes give the corresponding 2‑aryl‑
1,1‑bis(silyl)alkenes (Table 2). We postulated that when
(HMe2Si)3CLi reacts with a carbonyl group, it initially forms
the alkoxide intermediate B, then because of the presence of
the Si–H bond, an intramolecular alkoxide attack takes place
and gives 2. It seems likely that the cyclic intermediate B is
unstable and swiftly fragments to 1,1‑bis(silyl)‑1‑alkene with
the elimination of Me2SiO (Scheme 3).
All of the newly synthesised compounds were characterised
by spectroscopic techniques. The 1H NMR spectra of the
1a show the complete disappearance of aldehydic proton
resonance and the concomitant appearance of signals assigned
to HC=C at 7.68 ppm and –SiMe3 protons at 0.02 and 0.19 ppm.
Similar results were observed for 1b–f. The Si–H IR stretching
frequency for 2a was at 2110 cm–1. The H NMR spectrum
1
4‑(4‑(2,2‑Bis(dimethylsilyl)vinyl)phenyl)morpholine (2a): Yellow oil;
yield 90%, (silica gel, n‑hexane/ethyl acetate, 10:4, Rf =0.55); FTIR
(KBr, cm–1): 2842 (HC=), 2110 (Si–H), 1245 and 830 (Si–C), 1120 (C–
N), 1052 (C–O); 1H NMR (400 MHz, CDCl3):ꢀδꢀ0.25ꢀ(d,ꢀ6H,ꢀJ=3.7 Hz,
SiMe2), 0.30 (d, 6H, J=3.7 Hz, SiMe2), 3.24 (t, 4H, J=4.7 Hz, 2
CH2–N–CH2), 3.90 (t, 4H, J=4.7 Hz, 2 CH2–C–OH2), 4.29–4.32
(m, 1H, Si–H), 4.39–4.42 (m, 1H, Si–H), 6.90 (d, 2H, J=8.5 Hz, Ar),
of 2a showed two doublets at 0.25 and 0.3 ppm assigned to
the two methyl groups on each silicon atom, one singlet at
7.72ꢀppmꢀassignedꢀtoꢀaꢀprotonꢀonꢀtheꢀβ‑carbon,ꢀandꢀoneꢀseptetꢀ
in the range 1.72–1.73 ppm for the Si–H protons, resulting from
vicinal coupling. All these results clearly show the formation of
2‑aryl‑1,1‑bis(silyl)alkenes 2a–f.
H
C O
OLi
C
H
SiMe2H
SiMe2H
O
SiMe2H
SiMe2H
SiMe2H
H
H
SiMe2
C
C
C
C
-
-
Me2Si
O
LiH
(HMe2Si)3CLi
C
SiMe2H
SiMe2H
R
R
R
R
B
2
Scheme 3 Synthesis of some 2,2-bis(dimethylsilyl)ethenyl derivatives containing amine group and N-heterocycles.
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500 JOURNAL OF CHEMICAL RESEARCH 2014
7.31 (d, 2H, J=8.5 Hz, Ar), 7.72 (s, 1H, HC=); 13C NMR (100 MHz,
CDCl3):ꢀδꢀ–3.82,ꢀ–3.26ꢀ(SiMe2), 47.76, 65.79, 113.38, 128.71, 131.12,
136.15, 149.56, 154.54; m/z (EI): 306 (30%, [M+1]+), 305 (100%,
[M]+), 246 (79%, [M–SiMe2H]+), 59 (18%, [SiM2H]+). Anal. calcd for
C16H27NOSi2: C, 62.89; H, 8.91; N, 4.58; found: C, 62.87; H, 9.06; N,
4.40%.
1‑(4‑(2,2‑Bis(trimethylsilyl)vinyl)phenyl)piperidine (1b): Red oil;
yield 93%, (silica gel, n‑hexane/ethyl acetate, 15:3, Rf =0.64); FTIR
(KBr, cm–1): 2803 (HC=), 1240 and 846 (Si–C), 1127 (C–N); 1H NMR
(400 MHz, CDCl3):ꢀδꢀ0.06ꢀ(s,ꢀ9H,ꢀSiMe3), 0.22 (s, 9H, SiMe3), 1.61–1.62
(m, 2H, CH2), 1.73–1.74 (m, 4H, 2CH2), 3.2 (t, 4H, J=4.9 Hz, CH2–N–
CH2), 6.9 (d, 2H, J=8.2 Hz, Ar), 7.14 (d, 2H, J=8.2 Hz, Ar), 7.71 (s,
1H, HC=); 13C NMR (100 MHz, CDCl3):ꢀδꢀ–0.34,ꢀ1.15ꢀ(SiMe3), 23.24,
24.62, 49.44, 114.34, 114.95, 126.17, 127.96, 142.26, 154.01; m/z (EI):
332 (31%, [M+1]+), 331 (100%, [M]+),258 (18%, [M–SiMe3]+), 73
(19%, [SiMe3]+). Anal. calcd for C19H33NSi2: C, 68.81; H, 10.03; N,
4.22; found: C, 68.93; H, 10.16; N, 4.27%.
1‑(4‑(2,2‑Bis(dimethylsilyl)vinyl)phenyl)piperidine (2b): Red oil;
yield 88%, (silica gel, n‑hexane/ethyl acetate, 15:3, Rf =0.64); FTIR
(KBr, cm–1): 2801 (HC=), 2110 (Si–H), 1235 and 891 (Si–C), 1126
(C–N); 1H NMR (400 MHz, CDCl3):ꢀδꢀ0.13ꢀ(d,ꢀ6H,ꢀJ=3.7 Hz, SiMe2),
0.16 (d, 6H, J=3.7 Hz, SiMe2), 1.51–1.54 (m, 2H, CH2), 1.60–1.65 (m,
4H, 2CH2), 3.13 (t, 4H, J=5.4 Hz, CH2–N–CH2), 4.16–4.19 (m, 1H,
Si–H), 4.27–4.31 (m, 1H, Si–H), 6.80 (d, 2H, J=8.7 Hz, Ar), 7.16 (d,
2H, J=8.7 Hz, Ar), 7.57 (s, 1H, HC=); 13C NMR (100 MHz, CDCl3):
δꢀ –3.77,ꢀ –3.25ꢀ (SiMe2), 23.27, 24.63, 48.91, 113.93, 128.69, 130.0,
134.81, 150.41, 154.88; m/z (EI): 304 (27%, [M+1]+), 303 (94%,
[M]+), 244 (100%, [M–SiMe2H]+), 59 (18%, [SiM2H]+). Anal. calcd
for C17H29NSi2: C, 67.26; H, 9.63; N, 4.61; found: C, 67.31; H, 9.97; N,
4.37%.
(s, 1H, CH=), 7.90 (s, 1H, N–CH=N); 13C NMR (100 MHz, CDCl3):ꢀδꢀ
–4.01, –3.38 (SiMe2), 112.60, 119.70, 127.88, 128.83, 131.15, 137.89,
146.61, 149.92, 153.00; m/z (EI): 286 (53%, [M]+), 227 (100%, [M–
SiMe2H]+), 59 (17%, [SiM2H]+). Anal. calcd for C15H22N2Si2: C, 62.88;
H, 7.74; N, 9.78; found: C, 63.00; H, 7.54; N, 9.72%.
1‑(4‑(2,2‑Bis(trimethylsilyl)vinyl)phenyl)‑1H‑benzo[d][1,2,3]
triazole (1e): Red oil, yield 80%, (silica gel, n‑hexane/ethyl acetate,
15:3, Rf =0.38); FTIR (KBr, cm–1): 2842 (HC=), 1251and 838 (Si–
1
C), 1029 (C–N); H NMR (400 MHz, CDCl3):ꢀδꢀ0.01ꢀ(s,ꢀ9H,ꢀSiMe3),
0.23 (s, 9H, SiMe3), 7.41–7.46 (m, 3H, Ar), 7.56 (t, 1H, J=7.6 Hz, Ar),
7.73–7.78 (m, 4H), 8.15 (d, 1H, J=8.3 Hz, Ar); 13C NMR (100 MHz,
CDCl3):ꢀδꢀ–0.57,ꢀ0.99ꢀ(SiMe3), 109.32, 119.23, 120.98, 123.32, 127.16,
128.23, 131.14, 134.61, 142.13, 145.40, 147.62, 151.90; m/z (EI): 366
(64%, [M+1]+), 365 (84%, [M]+), 73 (100%, [SiMe3]+). Anal. calcd for
C20H27N3Si2: C, 65.70; H, 7.44; N, 11.49; found: C, 65.96; H, 7.53; N,
11.21%.
1‑(4‑(2,2‑Bis(dimethylsilyl)vinyl)phenyl)‑1H‑benzo[d][1,2,3]triazole
(2e): Yellow solid, yield 77%, (silica gel, n‑hexane/ethyl acetate, 15:4,
Rf =0.52, m.p. 82–84°C); FTIR (KBr, cm–1): 2847 (HC=), 2113 (Si–H),
1250 and 894 (Si–C), 1112 (C–N); 1H NMR (400 MHz, CDCl3):ꢀδꢀ0.21ꢀ
(d, 6H, J=3.5 Hz, SiMe2), 0.29 (d, 6H, J=3.5 Hz, SiMe2), 4.29–4.33
(m, 2H, Si–H), 7.43 (t, 1H, J=7.6 Hz, Ar), 7.51–7.57 (m, 3H, Ar), 7.77
(d, 3H, J=8.2 Hz, Ar), 7.81 (s, 1H, HC=), 8.14 (d, 1H, J=8.2 Hz, Ar);
13C NMR (100 MHz, CDCl3):ꢀδꢀ–4.02,ꢀ–3.38ꢀ(SiMe2), 109.39, 119.34,
121.06, 123.39, 127.24, 128.67, 131.159, 135.06, 140.00, 142.67, 145.52,
153.08; m/z (EI): 338 (76%, [M+1]+), 337 (66%, [M]+), 278 (100%, [M–
SiMe2H]+), 59 (29%, [SiM2H]+). Anal. calcd for C18H23N3Si2: C, 64.04;
H, 6.87; N, 12.45; found: C, 64.32; H, 7.08; N, 12.22%.
2‑(4‑(2,2‑Bis(trimethylsilyl)vinyl)phenyl)‑2H‑benzo[d][1,2,3]
triazoles (1f): White solid, yield 85%, (silica gel, n‑hexane/ethyl
acetate, 15:3, Rf =0.5, m.p. 102–104°C); FTIR (KBr, cm–1): 2853
(HC=), 1248 and 839 (Si–C), 1111 (C–N); 1H NMR (400 MHz, CDCl3):
δꢀ0.015ꢀ(s,ꢀ9H,ꢀSiMe3), 0.25 (s, 9H, SiMe3), 7.44 (d, 2H, J=8.2 Hz, Ar),
7.47–7.49 (m, 2H), 7.79 (s, 1H, HC=), 7.92–7.93 (dd, 2H, J=2.5 Hz,
6.3 Hz, Ar), 8.33 (d, 2H, J=8.2 Hz, Ar); 13C NMR (100 MHz, CDCl3):
δꢀ–0.56,ꢀ0.99ꢀ(SiMe3), 109.33, 119.32, 121.02, 123.41, 127.15, 128.22,
130.99, 134.72, 142.22, 145.40, 146.87, 151.90; m/z (EI): 366 (19%,
[M+1]+), 365 (24%, [M]+), 73 (100%, [SiMe3]+). Anal. calcd for
C20H27N3Si2: C, 65.70; H, 7.44; N, 11.49; found: C, 65.89; H, 7.55; N,
11.12%.
1‑(4‑(2,2‑Bis(trimethylsilyl)vinyl)phenyl)pyrrolidine
(1c):
Red
oil; yield 90%, (silica gel, n‑hexane/ethyl acetate, 15:3, Rf =0.63);
FTIR (KBr, cm–1): 2803 (HC=), 1245 and 837 (Si–C), 1126 (C–N); 1H
NMR (400 MHz, CDCl3):ꢀδꢀ0.03ꢀ(s,ꢀ9H,ꢀSiMe3), 0.19 (s, 9H, SiMe3),
1.72 (m, 4H, 2CH2), 3.18 (d, 4H, J=4.5 Hz, CH2–N–CH2), 6.88 (d, 2H,
J=8.1 Hz, Ar), 7.12 (d, 2H, J=8.1 Hz, Ar), 7.68 (s, 1H, HC=); 13C NMR
(100 MHz, CDCl3):ꢀδꢀ–0.32,ꢀ1.13ꢀ(SiMe3), 24.62, 49.26, 114.33, 124.07,
125.11, 127.93, 148.01, 154.20; m/z (EI): 317 (100%, [M]+), 244 (32%,
[M–SiMe3]+), 73 (24%, [SiMe3]+). Anal. calcd for C18H31NSi2: C, 68.07;
H, 9.84; N, 4.41; found: C, 68.15; H, 9.87; N, 4.32%.
1‑(4‑(2,2‑Bis(dimethylsilyl)vinyl)phenyl)pyrrolidine (2c): Red oil;
yield 86%, (silica gel, n‑hexane/ethyl acetate, 15:3, Rf =0.62); FTIR
(KBr, cm–1): 2808 (HC=), 2107 (Si–H), 1245 and 891 (Si–C), 1128
(C–N); 1H NMR (400 MHz, CDCl3):ꢀδꢀ0.28ꢀ(d,ꢀ6H,ꢀJ=3.7 Hz, SiMe2),
0.3 (d, 6H, J=3.7 Hz, SiMe2), 1.72–1.73 (m, 4H, 2CH2), 3.90 (t, 4H,
J=5.4 Hz, CH2–N–CH2), 4.29–4.33 (m, 1H, Si–H), 4.39–4.43 (m, 1H,
Si–H), 6.90 (d, 2H, J=8.5 Hz, Ar), 7.14 (d, 2H, J=8.5 Hz, Ar), 7.46 (s,
1H, HC=); 13C NMR (100 MHz, CDCl3):ꢀδꢀ–3.90,ꢀ–3.28ꢀ(SiMe2), 29.79,
47.75, 113.36, 129.0, 131.12, 136.15, 150.47, 154.63; m/z (EI): 289
(100%, [M]+), 230 (76%, [M–SiMe2H]+), 59 (18%, [SiM2H]+). Anal.
calcd for C16H27NSi2: C, 66.37; H, 9.40; N, 4.84; found: C, 66.40; H,
9.48; N, 4.77%.
1‑(4‑(2,2‑Bis(trimethylsilyl(vinyl)phenyl)‑1H‑imidazole (1d): Yellow
oil, yield 70%, (silica gel, n‑hexane/ethyl acetate, 10:15, Rf =0.44);
FTIR (KBr, cm–1): 2851 (HC=), 1255 and 838 (Si–C), 1115 (C–N);
1H NMR (400 MHz, CDCl3):ꢀ δꢀ –0.02ꢀ (s,ꢀ 9H,ꢀ SiMe3), 0.21 (s, 9H,
SiMe3), 7.29–7.35 (m, 6H), 7.71 (s, 1H, HC=), 8.12 (s, 1H, N–CH=N);
13C NMR (100 MHz, CDCl3);ꢀ δꢀ –0.56,ꢀ 1.01ꢀ (SiMe3), 109.39, 119.83,
128.49, 130.08, 131.13, 136.83, 146.34, 148.56, 153.88; m/z (EI): 314
(87%, [M]+), 313 (100%, [M–1]+), 73 (63%, [SiMe3]+). Anal. calcd for
C17H26N2Si2: C, 64.91; H, 8.33; N, 8.91; found: C, 65.05; H, 8.24; N,
8.84%.
2‑(4‑(2,2‑Bis(dimethylsilyl)vinyl)phenyl)‑2H‑benzo[d][1,2,3]triazole
(2f): Yellow solid, yield 73%, (silica gel, n‑hexane/ethyl acetate, 15:4,
Rf =0.74, m.p. 64–66°C); FTIR (KBr, cm–1): 2839 (HC=), 2121 (Si–H),
1253 and 891 (Si–C), 1105 (C–N); 1H NMR (400 MHz, CDCl3):ꢀδꢀ0.19ꢀ
(d, 6H, J=3.68 Hz, SiMe2), 0.29 (d, 6H, J=3.68 Hz, SiMe2), 4.27–4.33
(m, 2H, Si–H), 7.41–7.43 (dd, 2H, J=3.0 Hz, 6.6 Hz, Ar), 7.47 (d, 2H,
J=8.5 Hz, Ar), 7.80 (s, 1H, HC=), 7.92–7.94 (dd, 2H, J=3.0 Hz, 6.5 Hz,
Ar), 8.33 (d, 2H, J=8.5 Hz, Ar); 13C NMR (100 MHz, CDCl3):ꢀδꢀ–4.01,ꢀ
–3.36 (SiMe2), 109.42, 119.36, 121.08, 123.43, 127.27, 128.69, 131.16,
135.04, 139.99, 142.66, 145.52, 153.07; m/z (EI): 337 (48%, [M]+), 336
(56%, [M–1]+), 278 (100%, [M–SiMe2H]+), 59 (26%, [SiM2H]+). Anal.
calcd for C18H23N3Si2: C, 64.04; H, 6.87; N, 12.45; found: C, 64.26; H,
6.98; N, 12.29%.
Received 15 April 2014; accepted 10 July 2014
Paper 1402584 doi: 10.3184/174751914X14057852950474
Published online: 12 August 2014
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