Synthesis of novel styryl-: N -isopropyl-9 H -carbazoles for designing trans -conjugated regular silicon hybrid materials

Article abstract of DOI:10.1039/c6ob01560c

An efficient synthesis and characterization of several new, conjugated styryl-carbazole compounds functionalized by monovinylsilanes in a stereocontrolled approach is presented. All N-organic derivatives were successfully examined in silylative coupling in the presence of ruthenium-hydride complexes 4 and 5. Furthermore, a novel class of vinylene-arylene linear oligomeric materials with 1,4-bis(dimethylvinylsilyl)naphthalene in the main chain was produced. Both reactions proceed very effectively, stereo- and regioselectively, allowing one to obtain E-isomer derivatives with high isolation yields.

Full text of DOI:10.1039/c6ob01560c

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Synthesis of novel styryl-N-isopropyl-9H-carbazoles
for designing trans-conjugated regular silicon hybrid
materials†
Cite this: DOI: 10.1039/c6ob01560c
Mariusz Majchrzak,*a Magdalena Grzelaka and Bogdan Marciniec*a,b
An efficient synthesis and characterization of several new, conjugated styryl-carbazole compounds func-
tionalized by monovinylsilanes in a stereocontrolled approach is presented. All N-organic derivatives were
successfully examined in silylative coupling in the presence of ruthenium-hydride complexes 4 and 5.
Furthermore, a novel class of vinylene–arylene linear oligomeric materials with 1,4-bis(dimethylvinylsilyl)
naphthalene in the main chain was produced. Both reactions proceed very effectively, stereo- and regio-
selectively, allowing one to obtain E-isomer derivatives with high isolation yields.
Received 21st July 2016,
Accepted 5th September 2016
DOI: 10.1039/c6ob01560c
www.rsc.org/obc
forms a resonance structure like poly(p-phenylene)s and it
emits blue light in the film state based on the conjugation
Introduction
Carbazole-based materials, namely small molecular and low length.12,13 The palladium-catalyzed Suzuki cross-coupling14–17
weight macromolecular ones, have become attractive com- of boronic acid with aryl, alkenyl halides or triflate has been
pounds for OLED applications, especially as hole-transporting employed recently as the most efficient alternative to the well-
layers and host compounds since they show high charge mobi- established Hiyama,18 Stille and Negishi reactions.19,20 This
lity.1,2 With their interesting optical and electronic properties catalytic process is one of the most useful instruments in the
such as photoconductivity and photorefractivity,3,4 carbazole organic synthesis of arylene-conjugated compounds. The for-
derivatives can be used in light emitting layers because they mation of a carbon–carbon bond is of vital importance in pre-
are thermally stable and display blue photo- and electrolumine- parative organic processes from molecular model chemistry to
scence based on the large band gap of the biphenyl unit and macromolecular and nanomaterials science. In combination
planarity improved by the bridging nitrogen atom.5 A lot of with the silylative coupling (SC) reaction, they are powerful
poly(carbazole)s which contain carbazolylene fragments in the tools for designing new material structures. The SC coupling
main chain have been synthesized. The position of the 3,6- or reaction of olefins with vinyl-substituted organosilicon com-
2,7-linkage inside the chain influences the properties of the pounds has been studied and developed for the last two
final material. It is of vital importance then to understand the decades as a new, stereo-controlled catalytic activation of the
structural differences resulting from the choice of the linkage carbon–hydrogen (–HCvC–H) bond of olefin and the carbon–
position in the carbazole. This position defines the possible silicon (H2CvHC–Si) bond of silane in the presence of com-
use of particular carbazole derivatives for specific purposes.6–9 plexes containing initially or generating in situ metal–hydrogen
Conjugation of 3,6-linked poly(carbazole)s is not long, because and metal–silicon bonds.21,22 The silylative coupling is a
one-electron abstraction from the nitrogen atom forms stable highly regio- and stereoselective way to functionalize molecular
cation radical species that disturb it.10,11 Compared to 3,6- and macromolecular compounds that contain one or a few
linked poly(carbazole)s, the main chain conjugation of 2,7- vinyl groups connected to the silicon atom. Certainly, this
linked poly(carbazole)s is long. This is because the main chain method is a suitable and useful tool to synthesize conjugated
compounds.23–25 We previously described the catalytic trans-
formation of vinylsilyl-carbazole derivatives via this coupling
reaction to linear – vinylene–silylene–arylene–silylene–vinylene
– species as a link between 1,4-divinylbenzenes.26,27
aFaculty of Chemistry, Department of Organometallic Chemistry, Adam Mickiewicz
University in Poznań, Umultowska 89b, 61-614 Poznan, Poland.
Herein, we focus on a productive and selective procedure
for the synthesis of a new type of styryl-carbazole via very
efficient Suzuki coupling and their functionalization to new
organosilicon π-conjugated compounds by highly controlled
silylative coupling with vinylsilanes, for example trimethyl-
vinylsilane and dimethylphenylvinylsilane.
E-mail: mariusz.majchrzak@amu.edu.pl; Tel: +48618291729
bWielkopolska Centere of Advanced Technology, Adam Mickiewicz University in
Poznan, Umultowska 89c, 61-614 Poznań, Poland. E-mail: marcinb@amu.edu.pll;
Tel: +48618291988
†Electronic supplementary information (ESI) available: General synthetic pro-
cedures and characterization for 6–11; analytical details: 1H, 13C, and 29Si NMR
spectra; MS(EI); GPC graphs of 28-P1 and 29-P2. See DOI: 10.1039/c6ob01560c
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Finally, we extend this methodology for the production of
novel E-stereo-regular vinylene–silylene(naphthalene)–silylene–
vinylene–phenylene-N-alkylcarbazole oligomeric materials by
the respective reaction of distyryl-substituted carbazole deriva-
tives with 1,4-bis(dimethylvinylsilyl)naphthalene.
Scheme 2 Synthesis of 3-styryl-N-isopropylcarbazoles.
Results and discussion
At the beginning we synthesized bromocarbazole derivatives as
a starting material for the synthesis of new olefins. We used
the fully controlled and selective bromination process using
N-bromosuccinimide (NBS) (see Scheme 1). In accordance with
the following scheme, mono- and dibrominated carbazoles 9,
10, and 11 were quite easily produced in high yields using one
and two equivalents of NBS (dissolved in DMF) in CH2Cl2 at
10–25 °C (mild conditions). Then, the N-alkylation reaction
was performed using a strong base KOH, acetone as a solvent,
isopropyl bromide and tetra-n-butylammonium bromide
(C4H9)4NBr as a phase-transfer catalyst.
Scheme 3 Synthetic pathway for the preparation of distyryl-N-iso-
propyl-carbazoles in the presence of 2.
In addition, in the synthesis of bromo-N-isopropyl-
carbazoles we used interchangeably another synthetic route
involving N-alkylation at the beginning and later bromination.
The progress of the reaction was monitored by TLC and ana-
lyzed by GCMS methods. We observed little differences in the
yields of the final products 9, 10 and 11. The solubility of
bromocarbazoles was good in common organic solvents.
Therefore, all of them were purified in cold hexane by stirring
and filtered through a glass filter. The typical Suzuki coupling
conditions were used to prepare the novel monostyryl-carba-
zoles (see Schemes 2 and 3). For all reactions, we chose well-
defined two, three coordination, 16e palladium(0) complexes
with different kinds of phosphines and one dibenzylideneace-
tone – ‘dba’ (see Fig. 1).
Fig. 1 Well-defined palladium complex structures.
at this stage because the molar ratio between the substrates
could be 1 : 1. Otherwise, the by-product 4,4′-divinylbiphenyl
would be synthesized. Therefore, we focused on the selective
synthesis of 3-(4- or 3-vinylphenyl)-N-isopropylcarbazoles, see
Scheme 2.
The reaction conditions were optimized with the use of 9
and 4-vinylphenylboronic acid or 3-vinylphenylboronic acid.
For preliminary results of the coupling reaction, a small excess
of boronic acid (1.05 eq.) was used, and the reaction was con-
ducted following the original procedure: Pd(dba)(PR3)2 (where
R = Cy or o-tolyl) as a catalyst (1 mol%), in an open system con-
ducted in a nonpolar–polar phase mixture of toluene/ethanol/
2 M base solution at the 60–85 °C temperature range to give a
mono-substituted product with quantitative conversions of
both substrates (see Table 1).
The above mentioned Pd(0) complexes, Pd(dba)(PCy3)2 (1)
and Pd(dba)(P(o-tolyl)3)2 (2) were tentatively screened in cata-
lytic tests. The appropriate reaction conditions were essential
Depending on the synthesis system, the activity of the first
one (1) in the Suzuki coupling reaction was lower than of the
second one (2). To monitor comfortably the progress of the
tested reaction, particularly the coupling of bromocarbazoles,
we decided to use both TLC and GCMS analyses. We also
identified
trace
amounts
of
side
compounds
N-isopropylcarbazoles on the basis of MS spectra. Especially
the debromination process proceeded fast at a low temperature
in the presence of 1. As a result of a series of catalytic tests, a
successful procedure that ensures high efficiency of the reac-
tion was developed. To obtain more carbazole compounds, we
applied the same conditions in the synthesis of three new
styryl-substituted carbazoles. After several attempts with a
Scheme 1 Synthetic pathways for the synthesis of mono- and
dibromo-N-isopropyl-carbazole derivatives. Reaction conditions: (i) NBS
1 or 2 eq. in DMF (highly concentrated), CH2Cl2 as a solvent; (ii) carba-
zole/Br-carbazole/Br2-carbazole, (CH3)2CHBr, KOH, (C4H9)4NBr – cata-
lyst (molar ratio 1 : 1.7 : 1.6 : 0.055) in acetone, under reflux; (%) isolated
yield.
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Table 1 Determination of the catalytic reaction conditions of the Suzuki coupling of 9 with vinylphenyl boronic acidsa
Cat. No.
Structure of Br-carb.
Structure of ViPhB(OH)2
T/t (°C)/(h)
Conversion of Br-carb.b (%)
Conversion of acidb (%)
Yieldb (%)
1
60/2
48
75
82
87
95
51
74
83
89
94
54
83
87
99
55
80
89
99
50
77
89
90
96
62
78
88
91
>99
55
85
92
>99
58
82
93
>99
48
75
82
87
95
51
74
83
89
94
54
83
60/12
60/24
85/2
85/4
60/2
60/12
60/24
85/2
85/4
60/2
2
60/12
60/24
85/2
87
99/(96)c
55
60/2
60/12
60/24
85/2
80
89
99/(91)c
a Reaction conditions: [Br-carbazole] : [ViPhB(OH)2] : [Pd] = 1 : 1.05 : 0.01; open system, argon. b Determined by GC and GCMS methods. c Isolated
yield.
slight modification (10% more toluene) of the original pro-
cedure, we found out that the coupling reaction of dibromo-N-
isopropylcarbazole (1 eq.) with vinylphenylboronic acid (2.1
eq.) in the presence of 2 – Pd(dba)(P(o-tolyl3))2 (2 mol%) in an
open system conducted in the previously discussed mixture of
solvents at high temperature afforded exclusively distyryl-N-iso-
propylcarbazoles after 2 h (Scheme 3).
We discovered that after such a short time the conversion
of substrates was complete up to 100% (15–17). Next, we
applied new olefins for the silylative coupling reaction with
vinylsilanes. At the beginning of catalytic screening we used
well-defined ruthenium-hydride(II) complexes consisting of tri-
phenyl- or tricyclohexyl phosphine with or without carbonyl
ligands which have been recently reported as good catalysts in
the silylative coupling process.28
Scheme 4 Silylative coupling 13 with vinylsilane in the presence of 3, 4
or 5.
reactivity of the vinyl group in dimethylphenylvinylsilane but
We focused on this reaction using the well-known com- more selective than the trimethyl derivative.
34
27,29
plexes, e.g.: Ru(Cl)H(PPh3)3 (3), Ru(CO)H(Cl)(PPh3)2
Ru(CO)H(Cl)(PCy3)2
(4),
In this study, we have demonstrated that a small excess
27,29
(5). We assumed that the use of the (5%) of vinylphenylsilane was enough to obtain product 20 in
ruthenium species would allow us to carry out efficiently the high yield. Moreover, complex 3 has lower reactivity than 4 and
coupling reaction of monovinyl-substituted organosilicon com- 5 under these reaction conditions. We think that the amount
pound with styryl-carbazole (13), see Scheme 4.
and type of ligands have the influence on the reactivity.
Heating up the mixture of 13 and suitably selected vinyl- Compared to complex 4, which also has a triphenyl phosphine
silanes (molar ratio 1 : 1.0–5.0) in toluene at 85–90 °C with ligand, it is precisely the lack of carbonyl that lowers the
1 mol% of 3, 4 or 5 (in relation to a molar amount of 13) led to activity of 3. The proton spectrum of 19 showed us a pretty
the evolution of ethylene and the formation of the desired sub- clean new conjugated organosilicon compound (see Fig. 2).
stituted-carbazole (see Scheme 4 and Table 2.). Due to the vola- Two characteristic signals B and C with coupling constants JHH
tility of vinyltrimethylsilane it had to be used in excess. It was = 19.5 Hz and JHH = 19.2 Hz resulted from the typical trans-
only a threefold excess that allowed us to achieve a high con- isomer part ((CH3)3Si–HBCvCHC–Ci<). The signal at 1.25 ppm
version of olefins.
(s, br) came from Apiezon® brand H grease.31 The second
On the basis of MS spectral analysis we identified further signal did not come from the structure of our compound but
by-products, i.e. two isomers E- and gem-bis(trimethylsilyl) from methylene chloride (5.30 ppm).
ethenes.27,30 A typical compound is formed by treating an
On the basis of our experiments, we decided to start with
excess of vinylsilanes, but this one is easily separated from the the coupling reaction of styrylcarbazoles and vinylsilanes. It
main product (by using a vacuum pump). We observed lower was conducted following the procedure: 5 eq. of trimethyl-
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Table 2 Catalytic screening of the silylative coupling reaction of vinyltrimethylsilane or vinyldimethylphenylsilane with 3(4-vinylphenyl)-N-
isopropylcarbazolea
Vinylsilane
structure
Molar ratio
[ViSi] : [St-carb.]
Conversion of
St-carb.b (%)
Selectivity of 19 or 20:
Cat. No.
by-productsb (%)
Yield of 19b (%)
3
1.1 : 1
3.0 : 1
5.0 : 1
1 : 1
31c 36d 48e
42c 50d 61e
49c 55d 60e
24d 36e
99 : 1
—
—
90 : 10
90 : 10
48
61
60
36
40
1 : 1.05
26d 40e
4
5
1.1 : 1
3.0 : 1
5.0 : 1
1 : 1
53c 72d 81e
74c 90d 95e
78c 90d 94e
87d 95e
90 : 10
—
—
98 : 2
97 : 3
80
95
94
95
97
1 : 1.05
89d 97e
1.1 : 1
3.0 : 1
5.0 : 1
1 : 1
79c 84d 87e
91c 98d
98 : 2
—
—
99 : 1
100 : 0
87
98
96c 99d
99 (96)f
92
92d 99e
87c 99d
1 : 1.05
99 (95)f
a Reaction conditions: [St-carb.] : [Ru] = 1 : 0.01; T = 85–90 °C; close system; argon. b Determined by GC and GCMS methods; t. c 4 h. d 12 h. e 24 h.
f Isolated yield.
Scheme 5 Synthetic pathways for functionalization of mono- and dis-
tyryl-N-isopropyl-carbazole by vinylsilanes. Reaction conditions:
toluene, 90 °C, under Ar.
Fig. 2 Example of the 1H NMR spectrum of 19 (after isolation) in CDCl3
at 25 °C.
1
HCvCH–Ci<) at the vinylene fragment shows exactly in the H
NMR spectrum that only E- or E,E-isomers are obtained under
vinylsilane or 1.05 eq. of dimethylphenylvinylsilane, catalyst selected reaction conditions. This confirms that the chosen
Ru(CO)H(Cl)(PCy3)2 – (5) (1 mol%), toluene (0.5 M solution), method distinguishes high stereoselectivity and is a clean
12 hours at 90 °C, sealed Schlenk’s system under an argon method (only ethylene is evolved as a by-product) to functiona-
atmosphere to afford exclusively four mono- and six-di- lize conjugated carbazoles. All compounds are good and very
substituted, new conjugated compounds: (E)-3-(4(or 3)-(2-(tri- soluble in common organic solvents, also non-polar hydro-
methylsilyl)vinylene)phenyl)-N-isopropyl-carbazoles (18, 19), carbons (e.g. hexane). Each product was isolated using a very
(E)-3-(4(or 3)-(2-(dimethylphenylsilyl)-vinylene)phenyl)-N-iso- simple method of a flash-fast filtration system (glass filter type
propylcarbazoles (20, 21) – first pathway and 3,6-bis(4- or 3 ((E)- G3 or G4/SiO2/Celite®). The results of the earlier studies
2(Me2Rsilyl)vinyl)phenyl)-N-isopropyl-carbazole
22–27 – second pathway with good yields 95–99% (GCMS), make it effective in the selectively controlled synthesis of new
according to Scheme 5. materials. The positive results obtained for mono- and difunc-
derivatives enabled us to optimize the conditions of a catalytic system to
The MS and 1H NMR spectral analysis of the reaction tionalization of highly π-conjugated 13–17 carbazole deriva-
mixture showed only one type of product obtained by two tives via SC with a series of vinylsilanes encouraged us to
similar ways. The coupling constant value (JHH of about extend the range of new olefins to copolycondensation with
18.5–19.5 Hz) for protons connected to carbon atoms (–Si– 1,4′-bis(dimethylvinylsilyl)naphthalene (12). A typical reaction
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based on styryl-arenes has evolved to be a major trend in their
development. Complex 2 appeared to be an effective homo-
geneous catalyst in the Suzuki coupling of vinylphenyl boronic
acid with mono- and dibromocarbazoles. A highly selective
method for the synthesis of new π-conjugated olefins is pre-
sented (13–17). We have shown that 4-(or 3)vinylphenyl-(3,6- or
2,7)-substituted carbazoles undergo efficient functionalization
via silylative coupling reaction with a series of vinylsilanes to
afford several new highly π-conjugated compounds. This reac-
tion proceeds effectively and with a very high stereo-selectivity
for all styryl-derivatives leading to the selective formation of
E-isomers 19 and 20 and E,E-isomers 22–27. An example syn-
thesis of new E-π-conjugated linear co-oligomers (28-P1, 29-P2)
is also presented. This methodology can also be extended to
the synthesis of a new class of E-regular controlled silyl-
organic-hybrid polymeric materials. Suzuki and silylative coup-
ling reactions are useful and complementary synthetic routes
leading to the design of vinyl-substituted silicon compounds.
At the moment we are concentrating on the study of opto-
electronic, electrochemical and thermal properties of the new
materials.
Scheme 6 Copolycondensation reaction of distyryl-N-isopropyl-
carbazoles (15 or 17) with 12.
system consisted of 0.25 M olefin solution in toluene, 12 and
the best complex 5, (molar ratio: [olefin] : [vinylsilane] : [cat.] =
1 : 1 : 1 × 10−2). The production system was placed in an oil
bath at 90 °C for 120 h under a slow flow of argon. The release
of ethylene was observed, see Scheme 6.
The copolycondensation progress was monitored by proton
1H NMR and we prolonged the time of the reaction until full
conversion of substrates and selective formation of expected
products (28-P1, 29-P2). Detailed analysis of the proton spec-
trum confirmed the formation of an oligomer made up of only
E-vinylene fragments in mers (coupling constants for the
protons of the –Si–HCvCH–Ci< unit, for P1 JHH = 18.6 Hz and
for P2 JHH = 18.9 Hz) in this reaction. Standard analysis using
high pressure gel permeation chromatography (GPC) allowed
the determination of the basic mass parameters. On the basis
of the data obtained it can be noticed that the SC polyconden-
sation process led to the formation of π-conjugated products
of relatively average molecular weights (Mn, Mw – for 28 (P1):
Mn = 1383–3503 g mol−1, Mw = 1535–4094 g mol−1; for 29 (P2)
Mn = 1121–7470 g mol−1, Mw = 1254–8658 g mol−1) and narrow
size distributions PDI = 1.41–1.65 (see Fig. 3–6 in the ESI†).
Additionally, GPC curves showed us the typical oligomeric
mixture composition (‘ragged’ type). The crude materials were
purified by successive precipitations from methylene chloride
into hexane. Then the last fraction was vacuum dried. These oli-
gomer materials are white or yellow solids and show good solu-
bility in common organic solvents such as CHCl3, THF, and
CH2Cl2. All styrylcarbazoles and their E- and E,E-silane deriva-
tives were isolated and characterized spectroscopically. Several
novel functionalized carbazoles were synthesized. Each of the
organic and silyl products were obtained in an excellent yield
and selectivity. Both reaction systems are characterized by
stereoselectivity and selection of appropriate conditions for
functionalization depending on the type of the used com-
pounds. The literature does not provide information on similar
systems with silylene–styrylene–carbazole–styrylene fragments.
Experimental
Instruments and measurement
Nuclear magnetic resonance (NMR) spectroscopy: 1H NMR (300,
400, 500 MHz), 13C NMR (75, 101, 125 MHz) and 29Si NMR (75,
99 MHz) spectra were recorded on a Varian XL 300 MHz
spectrometer, Varian VNMR-S 400 MHz spectrometer and
Varian 500 MHz spectrometer in CDCl3 solution. Chemical
shifts are reported in δ (ppm) with reference to the residue
solvent (1H δH = 7.26 ppm, 13C δC = 77.36 ppm for CDCl3) peak
for 1H, 13C and to TMS (29Si δH = 0.00 ppm). Analytical gas
chromatographic (GC) analyses were performed on a Varian
Star 3400CX with a DB-5 fused silica capillary column (30 m ×
0.15 mm) and TCD. The mass spectra of the substrates and pro-
ducts were obtained by GCMS analysis (Varian Saturn 2100T,
equipped with a CP-SLI 6CB capillary column (30 m × 0.25 mm)
and an ion trap detector). High-resolution mass spectroscopic
(HRMS) analyses were performed on an AMD-402 mass spectro-
meter. An elemental analysis was performed on a Vario EL
Elementar (Germany) three times. Melting points (mp) of the
organic and organosilicon carbazole derivatives were deter-
mined on a MPA120 EZ-Melt automated melting point appar-
atus from Stanford Research Systems (temperature resolution
0.1 °C; temperature sensor Pt RTD).
Gel permeation chromatography (GPC) analyses were per-
formed using an Agilent HPLC system equipped with a UV
absorbance detector and an RI detector (analysis conditions:
mobile phase – THF; flow rate 0.80 mL min−1; temperature
20 °C; injection volume −17 μL). The numerical average mole-
cular weight (Mn), average molecular weight (Mw) and poly-
Conclusions
Over the last three or four years, the concept of the synthesis dispersity index (PDI) were determined by a polystyrene
of molecular and macromolecular organosilicon compounds standard calibration curve (1.31 × 103, 3.64 × 106 Da).
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Thin-layer chromatography (TLC) was made on plates pre- 2 × 10−2. The reaction was monitored by TLC, GC and GCMS
coated with a plastic sheet with 250 μm thick silica gel analysis. For the isolation step, the final mixture was isolated
(Polygram SilG/UV254, ROTH), and column chromatography by a very quick ‘flash system’ (filter-G3/SiO2/Celite®). The
was conducted with silica gel 60 (70–230 mesh, Fluka).
excess of solvent was evaporated under vacuum. The isolated
yields were over 99%. All carbazole derivatives were yellow
solids. Proton NMR spectroscopic analysis confirmed the for-
Materials and methods
The chemicals were obtained from the following sources: mation of the expected E-products.
toluene, petroleum ether, dichloromethane (DCM), chloroform
(CHCl3), pentane, hexane, acetone and dimethylformamide
Synthetic part
(DMF) were purchased from Chempur and P.O.Ch., Gliwice;
magnesium (Mg), magnesium sulfate (MgSO4), potassium
Synthesis of an organosilicon monomer
1,4-Bis(vinyldimethylsilyl)naphthalene (12). A solution of 1,4-
hydroxide (KOH) and RuCl3·3H2O from P.O.Ch., Gliwice; carba- dibromonaphthalene (5 g, 0.01748 mol) in 10 mL of THF was
zole (95%) and 1,4-dibromonaphthalene from Alfa Aesar; added slowly dropwise to a suspension of Mg (1.02 g,
CDCl3, tetrabutylammonium bromide (TBAB), 2-bromopro- 0.04195 mol), whose surface was activated by the use of 1,2-
pane, 1,2-dibromoethane, N-bromosuccinimide (NBS), potass- dibromomethane (50 µL) at 15 °C and vinyldimethyl-
ium carbonate (K2CO3), 4-vinylphenylboronic acid (97%), chlorosilane (5.31 mL, 0.03846 mol) in 20 mL of THF (the
3-vinylphenylboronic acid (97%), 2,7-dibromocarbazole, mixture was lightly warmed at 35 °C). After the addition was
ethanol, THF, Celite® 545, 1,5-cyclooctadiene (COD), dimethyl- complete, the reaction mixture was heated at 40 °C for 4 hours
phenylvinylsilane, triphenylphosphine, tris(o-tolyl)phosphine, and then it was cooled at room temperature, 2 mL of water was
and bis(dibenzylideneacetone)palladium(0) – [Pd(dba)2] from added and the reaction mixture was filtered off. The organic
Aldrich; silica gel – 60 from Fluka, and tri(cyclohexyl)phos- solvent was removed, and the residue was distilled under
phine, trimethylvinylsilane and chloro(dimethyl)vinylsilane reduced pressure (b. p. 125–127 °C/0.6 mmHg) to obtain 12 as
from ABCR. Toluene, hexane and THF were purified by an a colorless liquid (4.39 g, yield 85%).
mBraun MB SPS 800 purification system. Then toluene,
1H NMR (300 MHz, CDCl3): δ 0.6 (s, 12H, (D)), 5.9 (d, 2H,
hexane and ethanol were stored over molecular sieves type 4 Å. (C), JHH = 16.8 Hz), 6.16 (d, 2H, (A), JHH = 18.3 Hz), 6.55 (dd,
Ethanol was distilled from calcium hydride under argon. All 2H, (B), JHH = 20.4 Hz), 7.55 (m, 2H, (G)), 7.77 (s, 2H, (E)), 8.22
liquid substrates were distilled and degassed by ‘bulb-to-bulb’ (t, 2H, (F)). 13C NMR (75 MHz, CDCl3): δ 138.9, 138.5, 136.9,
Schlenk’s system. Palladium complexes [Pd(η2-dba)(PCy3)2] 133.3, 132.9, 129.6, 125.3, −1.5. 29Si NMR (75 MHz, CDCl3):
(1),32 [Pd(η2-dba)(P(o-tolyl)3)2] (2)33 and ruthenium species δ −10.89. MS (EI) (m/z (relat. int. %)): 295.9 (53.1) (M+•), 280.9
[Ru(Cl)H(PPh3)3] (3),34 [Ru(CO)H(Cl)(PPh3)3] (4),35 and [Ru(CO) (95.1), 269.0 (23.2), 254.9 (41.7), 237.0 (45.7), 220.9 (11.4),
H(Cl)(PCy3)2] (5)36 were prepared according to a literature pro- 210.9 (62.7), 194.9 (35.7), 168.7 (22.6), 154.8 (16.3), 106.9
cedure. All the syntheses and catalytic tests were carried out (23.9), 84.9 (72.3), 58.9 (100). HRMS (m/z) calcd for C18H24Si2:
under an inert argon or air atmosphere.
295.14165, found 295.14161.
Preparation and characterization of new mono-styryl-carba-
zole derivatives (13, 14). A two-neck round bottom flask
Catalytic part
General procedure for the catalytic test 3-bromo-N-isopropyl- equipped with a condenser and magnetic stirring bar was
carbazole with vinylphenyl boronic acid. A mixture of 3-bromo- charged under argon with 3-bromo-N-isopropylcarbazole,
N-isopropyl-carbazole (0.1 g, 3.46 × 10−4 mol), 3(or 4)-vinyl- 4-vinylphenylboronic acid or 3-vinylphenylboronic acid,
phenyl boronic acid (0.054 g, 3.63 × 10−4 mol), K2CO3 (1.05 mL, toluene, ethanol, palladium(0) complex Pd(dba)(P(o-tolyl)3)2
2 M aq. base solution), ethanol (0.7 mL), toluene (2.1 mL), and (2) and potassium carbonate aqua solution. The reaction
a palladium(0) catalyst (1, 2; 1 mol%) was placed in a two-neck mixture was stirred and heated in an oil bath at 80–90 °C for
glass reactor equipped with a magnetic stirring bar and a reflux 2 hours. The molar ratio of the reactants was as follows: [Br-
condenser. The suspension was degassed and heated in an oil substrate] : [boronic acid] : [palladium complex] 1 : 1.05 : 1 ×
bath at 60–85 °C for 2–24 h. The reaction progress was moni- 10−2. The reaction progress was monitored by TLC and GCMS
tored by TLC (eluent mixture: hexane/DCM – 10 : 1, Rf = 0.4–0.6 analysis. The final products were filtered off and dried under
in relation to carbazole), GC and GCMS to complete.
vacuum. The isolated yields were from 91 to 96%. NMR
General procedure for the catalytic screening of coupling spectroscopic analysis confirmed the formation of the
vinylsilane with 3-(4-vinylphenyl)-N-isopropylcarbazole.
A
expected products.
Schlenk reactor equipped with a magnetic stirring bar was
3-(4-Vinylphenyl)-N-isopropylcarbazole (13). A two-neck round
charged under argon with 3-styryl-N-isopropyl-carbazole (1.61 bottom flask equipped with a condenser and magnetic stirring
× 10−4 mol), trimethylvinylsilane (1.1–5.0 mol%) or dimethyl- bar was charged under argon with 3-bromo-N-isopropyl-carba-
phenylvinylsilane (1.0–1.05 mol%), toluene (0.320 mL, 0.5 M – zole (0.25 g, 0.0008675 mol), 4-vinylphenylboronic acid
calculated per carbazole) and ruthenium(II) complex (3, 4 or 5; (0.135 g, 0.00091 mol), toluene (5.27 mL), ethanol (1.77 mL),
1 mol%). The solution was stirred and heated in an oil bath at palladium complex (2) (8.4 mg, 0.000008675 mol) and potas-
90 °C for 6–24 hours. The molar ratio of the reactants was as sium carbonate (2.6 mL, 2 M solution in water). The solution
follows: [olefin] : [vinylsilane] : [Ru–H] = 1 : 1.0–5.0 : 1 × 10−2 or was stirred and heated in an oil bath at 85 °C for 4 h. The
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mixture was isolated by a very quick ‘flash’ column system stirring bar was charged under argon with 3,6-dibromo-N-iso-
(glass filter G3, silica gel, Celite®) connected to a membrane propyl-carbazole (0.5 g, 0.00136 mol), 4-vinylphenylboronic
pump, and then extracted from DCM/H2O and dried over an- acid (0.42 g, 0.00286 mol), toluene (8.16 mL), ethanol (2.8 mL),
hydrous MgSO4 for 24 h and filtered. After that the excess of palladium complex 2 (26.2 mg, 0.0000272 mol) and potassium
solvent was evaporated under vacuum. The olefin was purified carbonate (4 mL, 2 M solution in water). The solution was
by repeated precipitation from the DCM/hexane system. The stirred and heated in an oil bath at 85 °C for 2.5 hours. The
final product was filtered off and dried under vacuum. The iso- isolated yield was 95% (0.53 g) as a white solid.
lated yield was 96% (0.26 g) as a yellowish solid.
1H NMR (400 MHz, CDCl3): δ 1.76 (d, 6H, (I), JHH = 7.2 Hz),
1H NMR (300 MHz, CDCl3): δ 1.74 (d, 6H, (G), JHH = 6.9 Hz), 5.03 (m, 1H, (J)), 5.27 (d, 2H, (B’), JHH = 11.6 Hz), 5.38 (d, 2H,
5.02 (m, 1H, (F)), 5.27 (d, 1H, (A), JHH = 10.8 Hz), 5.8 (d, 1H, (B), JHH = 11.2 Hz), 5.81 (d, 2H, (A′), JHH = 17.2 Hz), 5.91 (d, 2H
(B), JHH = 16.8 Hz), 6.79 (dd, 1H, (C), JHH = 17.7 Hz), 7.19 (t, (A), JHH = 17.6 Hz), 6.79 (dd, 2H, (C’), JHH = 17.2 Hz), 6.8 (dd,
1H, (L)), 7.45 (t, 1H, (H)), 7.52 (d, 2H, (D), JHH = 8.1 Hz), 7.56 2H, (C), JHH = 18 Hz), 7.54 (d, 4H, (D), JHH = 8 Hz), 7.6 (s, 2H,
(d, 1H, (I), JHH = 4.2 Hz), 7.6 (s, 1H, (J)), 7.69 (d, 2H, (E), JHH
8.4 Hz), 8.16 (d, 1H, (M), JHH = 7.8 Hz), 8.14 (d, 1H, (N), JHH
=
=
(F)), 8.19 (d, 4H, (E), JHH = 8 Hz), 8.38 (d, 2H, (G), JHH = 1.2 Hz).
13C NMR (75 MHz, CDCl3): δ 141.6, 139.6, 136.9, 136.1, 131.8,
1.5 Hz), 8.33 (d, 1H, (K), JHH = 1.2 Hz). 13C NMR (75 MHz, 127.4, 126.8, 125.9, 125.1, 124.1, 118.8, 115.8, 113.6, 110.5,
CDCl3): δ 141.6, 140.1, 139.1, 136.7, 135.8, 134.8, 132.2, 131.6, 47.2, 21.0. MS (FAB, m/z (%)) (M+, 100): 413. HRMS (m/z) calcd
127.4, 126.8, 125.7, 124.8, 124.0, 123.9, 123.5, 120.6, 118.9, for C31H27N: 413.21435, found 413.21433.
118.7, 46.9, 21.0. MS (EI) (m/z (relat. int. %)): 312.2 (24.8) (M+•),
3,6-Di(3-vinylphenyl)-N-isopropylcarbazole (16). This com-
311.3 (100), 297.8 (9.6), 296.8 (66.4), 268.8 (5.7), 267.8 (4.8). MS pound was synthesized by the same method as 15 with 3,6-
(FAB, m/z (%)) (M+, 100): 311. HRMS (m/z) calcd for C23H21N: dibromo-N-isopropyl-carbazole (0.5 g, 0.00136 mol), 3-vinyl-
311.16740, found 311.16737.
phenylboronic acid (0.42 g, 0.00286 mol), toluene (8.16 mL),
3-(3-Vinylphenyl)-N-isopropylcarbazole (14). This compound ethanol (2.8 mL), complex 2 (26.2 mg, 0.0000272 mol) and pot-
was synthesized by the same method as 13 using 3-bromo-N- assium carbonate (4 mL, 2 M solution in water). The isolated
isopropyl-carbazole (0.4 g, 0.00139 mol), 3-vinylphenylboronic yield was 91% (0.51 g) as a white solid.
acid (0.216 g, 0.00146 mol), toluene (8.4 mL), ethanol
1H NMR (400 MHz, CDCl3): δ 1.76 (d, 6H, (L), JHH = 6.8 Hz),
(2.83 mL), complex 2 (13.4 mg, 0.0000139 mol) and potassium 5.02 (m, 1H, (K)), 5.33(d, 2H, (B), JHH = 17.6Hz), 5.87 (d, 2H,
carbonate (4.16 mL, 2 M solution in water). The isolated yield (A), JHH = 18.4 Hz), 6.85 (dd, 2H, (C), JHH = 17.2 Hz), 7.4 (d, 2H,
was 91% (0.39 g) as a yellowish solid.
(D), JHH = 2.4 Hz), 7.42 (t, 2H, (F)), 7.71 (t, 2H, (G)), 7.73 (t, 2H,
1H NMR (300 MHz, CDCl3): δ 1.73 (d, 6H, (I), JHH = 6.9 Hz), (E)), 7.81 (d, 2H, (J), JHH = 1.6 Hz), 7.73 (d, 2H, (I), JHH = 2 Hz),
5.19 (m, 1H, (H)), 5.30 (d, 1H, (B), JHH = 11.7 Hz), 5.94 (d, 1H, 7.86 (s, 2H, (H)). 13C NMR (75 MHz, CDCl3): δ 142.4, 139.6,
(A), JHH = 17.7 Hz), 6.87 (dd, 1H, (C), JHH = 17.7 Hz), 7.19 (d, 138.2, 137.1, 132.2, 129.1, 126.9, 125.4, 125.2, 124.4, 124.1,
1H, (E), JHH = 0.9 Hz), 7.23 (d, 1H, (G), JHH = 0.9 Hz), 7.42 (d, 119.1, 114.2, 110.5, 47.2, 21.1. MS (EI) (m/z (relat. int. %)):
1H, (K), JHH = 1.2 Hz), 7.47 (d, 1H, (L) JHH = 1,2 Hz),7.67 (s, 1H, 414.3 (33) (M+•), 413.4 (100), 400.5 (7.7), 399.6 (33.3), 398.8
(J)), 7.69 (d, 1H, (M), JHH = 0.9 Hz), 7.8 (s, 1H, (D)), 8.24 (t, 1H, (84.7), 371.7 (9.9), 370.7 (12.9), 355.7 (5.1), 206.5 (5.5). MS
(O)), 8.27 (t, 1H, (N)), 8.49 (t, 1H, (F)). 13C NMR (75 MHz, (FAB, m/z (%)) (M+, 100): 413. HRMS (m/z) calcd for C31H27N:
CDCl3): δ 142.6, 140.1, 139.1, 138.2, 137.2, 132.0, 129.1, 128.4, 413.21435, found 413.21432.
127.0, 125.7, 125.5, 125.0, 124.4, 124.0, 123.6, 120.5, 118.9,
2,7-Di(4-vinylphenyl)-N-isopropylcarbazole (17). This com-
118.9, 114.2, 110.4, 110.2, 46.9, 21.0. MS (EI) (m/z (relat. int. pound was synthesized by the same method as 15 with 2,7-
%)): 312.3 (24.6) (M+•), 311.3 (100), 297.5 (20.2), 296.7 (84), dibromo-N-isopropylcarbazole (0.2 g, 0.000545 mol), 4-vinyl-
268.6 (5.6). MS (FAB, m/z (%)) (M+, 100): 311. HRMS (m/z) calcd phenylboronic acid (0.17 g, 0.0011445 mol), toluene (3.27 mL),
for C23H21N: 311.16740; found 311.16739.
ethanol (1.09 mL), complex (2) (10 mg, 0.0000109 mol) and
Preparation and characterization of new distyryl-carbazole potassium carbonate (1.635 mL of 2 M solution in water). The
derivatives (15–17). Distyryl-carbazole derivatives were syn- solution was stirred and heated in an oil bath at 85 °C for
thesized by the same method as monostyryl-carbazole deriva- 2 hours. The isolated yield was from 98% (0.22 g) as a white
tives (13 and 14). The molar ratio of the reactants was as solid.
follows: [Br2-carbazole] : [ViPhB(OH)2] : [Pd] 1 : 2.1 : 2 × 10−2
.
1H NMR (400MHz, CDCl3): δ 1.79 (d, 6H, (J), JHH = 6.8 Hz),
The reaction progress was monitored by TLC and GCMS ana- 5.11 (m, 1H, (I)), 5.3 (d, 2H, (B), JHH = 11.2 Hz), 5.83 (d, 2H, (A),
lysis. The mixture was isolated by a very quick flash column JHH = 17.6 Hz), 6.79 (dd, 2H, (C),), JHH = 17.6 Hz), 7.48 (d, 2H,
system (glass filter G3, silica gel, Celite®) connected to a mem- (F), JHH = 8 Hz), 7.54 (d, 4H, (D), JHH = 8.4 Hz), 7.7 (d, 4H, (E),
brane pump, and then extracted from DCM/H2O and dried JHH = 8.4 Hz), 7.71 (s, 2H, (H)), 8.15 (d, 2H (G), JHH = 8 Hz). 13
C
over anhydrous MgSO4 for 24 h. After that the excess of solvent NMR (101 MHz, CDCl3): δ 141.7, 140.5, 138.4, 136.4, 136.4,
was evaporated under vacuum. The olefin was purified by 127.6, 126.6, 122.4, 120.6, 118.4, 113.8, 108.4, 29.7, 20.9. MS
repeated precipitation from the DCM/hexane system. The final (FAB, m/z (%)) (M+, 100): 413. HRMS (m/z) calcd for C31H27N:
product was filtered off and dried under vacuum.
413.21435, found 413.21433.
3,6-Di(4-vinylphenyl)-N-isopropylcarbazole (15). A two-neck
General procedure for the synthesis of monosubstituted-
round bottom flask equipped with a condenser and magnetic organo-silicon carbazole derivatives via silylative coupling. A
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Schlenk reactor equipped with a magnetic stirring bar was Hz), 7.71 (d, 2H, (E), JHH = 8.5 Hz), 7.2–7.7 (N, M, L, K, J, H, O,
charged under argon with monostyryl-carbazole derivatives P, R, 9H), 8.17 (d, 1H, (I), JHH = 7.5), 8.33 (s, 1H, (K)). 13C NMR
(3.21 × 10−4 mol) and respectively trimethylvinylsilane or di- (126 MHz, CDCl3): δ 150.5, 145.2, 141.9, 140.1, 138.9, 136.5,
methylphenyl-vinylsilane, toluene (0.5 M solution, calculated 134.1, 131.6, 129.2, 127.9, 127.4, 127.1, 126.7, 125.7, 124.8,
per styrylcarbazole) and Ru(CO)H(Cl)(PCy3)2 (5) complex. The 124.0, 123.6, 120.6, 118.9, 118.7, 110.4, 110.2, 46.9, 21.0, −2.3.
solution was stirred and heated in an oil bath at 90 °C for 29Si NMR (99 MHz, CDCl3): δ −10.32. MS (FAB, m/z (%))
4–24 h. The molar ratio of the reactants was as follows: (M+, 100): 445. HRMS (m/z) calcd for C31H31NSi: 445.22258,
[olefin] : [vinylsilane] : [Ru–H] = 1 : 1.05 : 1 × 10−2 (in the case of found 445.22253. Mp. 129.3–129.5 °C.
dimethylphenyl-vinylsilane) or 1 : 5 : 1 × 10−2 (in the case of tri-
methylvinylsilane). The reaction was monitored by TLC and (21). Yield 97% (138 mg) as a white solid.
3-(3-((E)-2-(Phenyldimethylsilyl)vinyl)phenyl)-N-isopropylcarbazole
GCMS analysis. The mixture was isolated by a very quick ‘flash’
1H NMR (500 MHz, CDCl3): δ 0.48 (s, 6H, (A)), 1.75 (d, 6H,
column system (glass filter G3, silica gel, Celite®) connected to (H), JHH = 7 Hz), 5.03 (m, 1H, (I)), 6.71 (d, 2H, (B), JHH = 19.2
a membrane pump. It was then extracted from DCM/H2O and Hz), 7.07 (d, 2H, (C), JHH = 19.2 Hz), 7.2–7.6 (10H, N, O, P, L, G,
dried over anhydrous MgSO4 for 24 h. After that the excess of F, E, R, S, T), 7.7 (d, 1H, (K), JHH = 7 Hz), 7.71 (d, 1H, (J), JHH
=
solvent was evaporated under vacuum. The products were puri- 7 Hz), 7.79 (s, 1H, (D)), 8.33 (d, 1H, (M), JHH = 7 Hz). 13C NMR
fied by repeated precipitation from the DCM/hexane system. (126 MHz, CDCl3): δ 150.5, 145.6, 142.6, 140.1, 138.8, 138.7,
The final products were filtered off and dried under vacuum. 134.1, 133.0, 132.0, 129.2, 129.1, 127.9, 127.5, 127.3, 126.2,
The isolated yields were over 96–99%. All carbazole derivatives 125.7, 125.0, 124.7, 123.9, 123.6, 120.6, 119.8, 119.0, 118.8,
were yellow solids. NMR spectroscopic analysis confirmed the 110.9, 110.3, 77.2, 46.9, 21.0, 1.2, −2.3. 29Si NMR (99 MHz,
formation of the expected products.
Analytical data (18–21)
CDCl3): δ −10.27. MS (FAB, m/z (%)) (M+, 100): 445. HRMS
(m/z) calcd for 31H31NSi: 445.22258, found 445.22249.
C
3-(3-((E)-2(Trimethylsilyl)vinyl)phenyl)-N-isopropylcarbazole (18). Mp. 131.1–131.2 °C.
Yield 98% (120 mg) as a white solid.
General procedure for the synthesis of disubstituted-organo-
1H NMR (500 MHz, CDCl3): δ 0.2 (s, 9H, (A)), 1.75 (d, 6H, silicon carbazole derivatives via silylative coupling. A Schlenk
(H), JHH = 7 Hz), 5.02 (m, 1H, (I)), 6.6 (d, 1H, (B), JHH = 19 Hz), reactor equipped with a magnetic stirring bar was charged
6.99 (d, 1H, (C), JHH = 19.2 Hz), 7.24 (d, 1H, (G), JHH = 7 Hz), under argon with distyryl-carbazole derivatives (3.5 × 10−4 mol)
7.40–7.72 (N, O, P, J, 4H) 7.44 (t, 1H, (F)), 7.55 (d, 1H, (E), JHH
=
and
respectively
trimethylvinylsilane
or
dimethyl-
8.5 Hz), 7.78 (s, 1H, (J)), 8.18 (d, 1H, (K), JHH = 7.5 Hz), 8.34 (d, phenylvinylsilane, toluene (0.5 M solution calculated per carba-
1H, (M), JHH = 1.5 Hz). 13C NMR (126 MHz, CDCl3): δ 144.2, zole) and complex (5). The solution was stirred and heated in
142.8, 140.3, 139.4, 139.2, 132.3, 130.2, 129.3, 127.4, 125.9, an oil bath at 90 °C for 10–24 hours. The molar ratio of the reac-
125.8, 125.3, 124.8, 124.2, 123.8, 120.8, 119.2, 119.1, 110.6, tants was as follows: [olefin] : [vinylsilane] : [ruthenium] 1 : 2.1 : 2
110.5, 47.2, 21.3, −0.8. 29Si NMR (99 MHz, CDCl3): δ −6.20. MS × 10−2 (in the case dimethylphenylvinylsilane) or 1 : 10 : 2 × 10−2
(EI) (m/z (relat. int. %)): 384.5 (32.6) (M+•), 383.5 (100), 370.7 (in the case of trimethylvinylsilane). The reaction was moni-
(9.8), 369.8 (32), 369 (80.2), 73.2 (12.8), 59.1 (9.1). MS (FAB, m/z tored by TLC and GCMS analysis. The mixture was isolated by a
(%)) (M+, 100): 383. HRMS (m/z) calcd for C26H29NSi: very quick ‘flash’ column system (glass filter G3, silica gel,
383.20693, found 383.20689. Mp. 126.6–126.8 °C.
Celite®). The excess of solvent was evaporated under vacuum.
3-(4-((E)-2(Trimethylsilyl)vinyl)phenyl)-N-isopropylcarbazole (19). The products were purified by repeated precipitation from the
Yield 97% (119 mg) as a white solid.
DCM/hexane system. The final products were filtered off and
1H NMR (500 MHz, CDCl3): δ 0.19 (s, 9H, (A)), 1.74 (d, 6H, dried under vacuum. The isolated yields were 97–99%. All car-
(G), JHH = 7 Hz), 5.02 (m, 1H, (F)), 6.53 (d, 2H, (B), JHH = 19.5 bazole derivatives were yellow solids. NMR spectroscopic ana-
Hz), 6.95 (d, 2H, (C), JHH = 19.2 Hz), 7.2–7.7 (L, M, N, H, 4H), lysis confirmed the formation of the expected products.
7.53 (d, 2H, (D), JHH = 8 Hz), 7.59 (s, 1H, (J)), 7.69 (d, 2H, (E),
JHH = 6 Hz), 8.16 (d, 1H, (I), JHH = 8 Hz), 8.33 (d, 1H, (K), JHH
Analytical data (22–27)
=
3,6-Bis(4-((E)-2(trimethylsilyl)vinyl)phenyl)-N-isopropylcarbazole
1.6 Hz). 13C NMR (126 MHz, CDCl3): δ 143.4, 141.6, 140.1, (22). Yield 99% (193 mg) as a white solid.
139.1, 136.7, 131.7, 129.2, 127.4, 127.4, 126.9, 126.8, 125.7,
1H NMR (500 MHz, CDCl3): δ 0.08 (s, 18H, (A)), 1.76 (d, 6H,
124.8, 124.0, 120.6, 118.9, 118.7, 113.5, 110.4, 110.2, 46.9, 21.0, (G), JHH = 7 Hz), 5.01 (m, 1H, (F)), 6.54 (d, 2H, (B), JHH = 19.5
−1.0. 29Si NMR (99 MHz, CDCl3): δ −6.26. MS (EI) (m/z (relat. Hz), 6.95 (d, 2H, (C), JHH = 19.5 Hz), 7.55 (d, 4H, (D), JHH
=
int. %)): 384.5 (34.5) (M+•), 383.5 (100), 370.8 (9.4), 369.9 8 Hz), 7.71 (d, 4H, (E), JHH = 7 Hz), 7.72 (d, 2H, (H), JHH = 8
(26.3), 369 (49.9), 73.2 (2.8), 59.1 (3.4). MS (FAB, m/z (%)) Hz), 8.2 (d, 2H, (I), JHH = 8 Hz), 8.39 (s, 2H, (J)). 13C NMR
(M+, 100): 383. HRMS (m/z) calcd for C26H29NSi: 383.20693, (126 MHz, CDCl3): δ 143.4, 141.6, 136.1, 131.8, 129.2, 127.4,
found 383.20687. Mp. 127.0–127.2 °C.
3-(4-((E)-2-(Phenyldimethylsilyl)vinyl)phenyl)-N-isopropylcarbazole (99 MHz, CDCl3): δ −6.25. MS (FAB, m/z (%)) (M+, 100): 557.
(20). Yield 96% (137 mg) as a white solid. HRMS (m/z) calcd for C37H43NSi2: 557.29340, found 557.29332.
1H NMR (500 MHz, CDCl3): δ 0.48 (s, 6H, (A)), 1.74 (d, 6H, Mp. 136.8–136.9 °C.
126.9, 126.1, 125.1, 118.8, 110.5, 47.2, 21.1, −1.0. 29Si NMR
(G), JHH = 7 Hz), 5.02 (m, 1H, (F)), 6.64 (d, 1H, (B), JHH = 19.5
3,6-Bis(3-((E)-2(trimethylsilyl)vinyl)phenyl)-N-isopropylcarbazole
Hz), 7.02 (d, 1H, (C), JHH = 19.2 Hz), 7.56 (d, 2H, (D), JHH = 8.5 (23). Yield 98% (191 mg) as a white solid.
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1H NMR (500 MHz, CDCl3): δ 0.08 (s, 18H, (A)), 1.77 (d, 6H, calcd for C47H47NSi2: 681.32470, found 681.32469.
(H), JHH = 14 Hz), 5.03 (m, 1H, (I)), 6.61 (d, 1H, (B), JHH = 18.5 Mp. 148.2–148.4 °C.
Hz), 7.01 (d, 1H, (C), JHH = 19.0 Hz), 7.92(s,1H, (D)) 6.98–8.49
A general procedure for silylative coupling polycondensation
(E, F, G, J, K, L, 12.0 Hz). 13C NMR (126 MHz, CDCl3): δ 150.8, (SCP) (28-P1, 29-P2). A glass reactor equipped with a reflux
143.9, 142.4, 139.6, 138.9, 132.3, 129.9, 129.1, 127.1, 125.6, condenser and magnetic stirring bar was charged under argon
125.3, 124.6, 119.1, 110.5, 47.2, 21.1, −1.0. 29Si NMR (99 MHz, with distyryl-N-isopropylcarbazole (15, 17) derivatives (0.1 g,
CDCl3): δ −6.19. MS (FAB, m/z (%)) (M+, 100): 557. HRMS (m/z) 2.42 × 10−4 mol), 1,4-bis(vinyldimethylsilyl)naphthalene (12)
calcd for C37H43NSi2: 557.29340, found 557.29335. (0.072g, 2.42 × 10−4 mol), toluene (0.970 mL, 0.25 M solution
Mp. 138.3–138.4 °C.
2,7-Bis(3-((E)-2(trimethylsilyl)vinyl)phenyl)-N-isopropylcarbazole The solution was stirred and heated in an oil bath at 95 °C for
calculated per olefin) and complex 5 (1.7 mg, 2.42 × 10−6 mol).
(24). Yield 97% (189 mg) as a white solid.
120 hours. The molar ratio of the reactants was as follows:
1H NMR (300 MHz, CDCl3): δ 0.19 (s, 18H, (A)),1.79 (d, 6H, [olefin] : [vinylsilane] : [ruthenium] 1 : 1 : 1 × 10−2. The mixture
(J), JHH = 7.2 Hz), 5.11 (m, 1H, (I)), 6.55 (d, 1H, (B), JHH = 18.8 was isolated by a very quick ‘flash’ column system (glass filter
Hz), 6.95 (d, 1H, (C), JHH = 18.8 Hz), 7.48 (d, 2H, (F), JHH
=
G3, silica gel, Celite®) connected to a membrane pump. The
8 Hz), 7.55 (d, 4H, (D), JHH = 8.4 Hz), 7,7 (d, 4H, (E), JHH = 8.4 excess of solvent was evaporated under vacuum. The products
Hz), 7.71 (s, 2H, (H)), 8.15 (d, 2H (G), JHH = 8 Hz). 13C NMR were purified by repeated precipitation from the DCM/hexane
(75 MHz, CDCl3): δ 141.9, 140.7, 138.6, 137.3, 132.5, 131.1, system. The final products were filtered off and dried under
129.7, 128.9, 127.8, 126.9, 122.6, 120.7, 29.8, 22.8, 1.2. vacuum. The isolated yields were accordingly: P1 92%
29Si NMR (75 MHz, CDCl3): δ −6.21. MS (FAB, m/z (%)) (158 mg) and P2 88% (150 mg) as yellowish solids. The struc-
(M+, 100): 557. HRMS (m/z) calcd for C37H43NSi2: 557.29340, ture of the oligomeric material was confirmed by NMR spectro-
found 557.29342. Mp. 138.3–138.5 °C.
scopic methods.
3,6-Bis(4-((E)-2-(phenyldimethylsilyl)vinyl)phenyl)-N-isopropyl-
carbazole (25). Yield 98% (233 mg) as a white solid.
Poly[3,6-di(4-phenylene)-N-isopropylcarbazole-(E)-vinylene-(1,4-
1
bis(dimethylsilylene)naphthalene)-(E)-vinylene]s (28-P1). H NMR
1H NMR (500 MHz, CDCl3 (ppm)): δ 0.08 (s, 12H, (A)), 1.76 (300 MHz, CDCl3; (ppm)): δ 0.64 (s, 12H, (E)), 1.74 (d, 6H, (A)),
(d, 6H, (F), JHH = 7 Hz), 5.03 (m, 1H, (G)), 6.59 (d, 2H, (B), JHH
=
5.01 (m, 1H, (B)), 5.52–6.62 (3H, trace of a terminal vinyl
19.0 Hz), 6.64 (d, 2H, (B′), JHH = 19.0 Hz), 6.95 (d, 2H, (C’), group), 6.83 (d, 1H, JHH = 18.6 Hz, (C)), 7.11 (d, 1H, JHH = 18.6
JHH = 19 Hz), 7.01 (d, 2H, (C), JHH = 19 Hz), 7.3–7.7 (10H, K, L, Hz, (D)), 7.31–8.38 (20H, aromatic protons). 13C NMR (75 MHz,
M, I, H), 7.33 (d, 4H, (D), JHH = 7.5 Hz), 7.45 (d, 4H, (E), JHH
=
CDCl3; (ppm)): δ 141.8, 139.6, 137.0, 136.9, 136.6, 134.7, 133.6,
7.5 Hz), 8.39 (s, 2H, (J)). 13C NMR (126 MHz, CDCl3): δ 145.4, 133.4, 132.2, 131.8, 129.5, 128.6, 127.4, 127.3, 127.2, 126.6,
142.0, 139.9, 136.8, 134.3, 132.0, 129.4, 128.9, 128.6, 128.2, 126.2, 125.0, 124.1, 120.2, 118.8, 116.9, 110.9, 41.7, 21.1,
127.6, 127.4, 126.9, 125.3, 119.1, 110.8, 47.4, 21.3, −2.01. 29Si −1.01. 29Si NMR (75 MHz, CDCl3; (ppm)): δ −10.28. Elemental
NMR (99 MHz, CDCl3): δ −10.29. MS (FAB, m/z (%)) (M+, 100): analyses calcd for (C43H41NSi2)n: C 82.24, H 6.58, N 2.23;
682. HRMS (m/z) calcd for C47H47NSi2: 681.32470, found found
681.32467. Mp. 143.7–143.9 °C.
1383–3503 g mol−1, Mw = 1535–4094 g mol−1, PDI (Mw/Mn) =
3,6-Bis(3-((E)-2-(phenyldimethylsilyl)vinyl)phenyl)-N-isopropyl- 1.11–1.17, n = 2–6.
carbazole (26). Yield 97% (231 mg) as a white solid. Poly[2,7-di(4-phenylene)-N-isopropylcarbazole-(E)-vinylene-(1,4-
C
81.87,
H
6.52,
N
2.21. GPC data: Mn
=
1
1H NMR (500 MHz, CDCl3): δ 0.09 (s, 12H, (A)), 1.78 (d, 6H, bis(dimethylsilylene)naphthalene)-(E)-vinylene]s (29-P2). H NMR
(H), JHH = 8 Hz), 5.02 (m, 1H, (I)), 6.71 (d, 2H, (B), JHH = 19.5 (300 MHz, CDCl3; (ppm)): δ 0.56 (s, 6H, (E’)), 0.66 (s, 12H, (E)),
Hz), 7.07 (d, 2H, (C), JHH = 19.5 Hz), 7.27–7.8 (14H, L, G, F, E, 1.79 (d, 6H, JHH = 6.9 Hz, (A)), 5.11 (m, 1H, (B)), 5.83–6.57 (3H,
M, N, O), 7.92 (s, 2H, (D)), 8.39 (t, 2H, (K)), 8.43 (t, 2H, (J)). trace of a terminal vinyl group), 6.87 (d, 1H, JHH = 18.9 Hz, (C)),
13C NMR (126 MHz, CDCl3): δ 145.4, 145.1, 141.8, 139.6, 138.9, 7.14 (d, 1H, JHH = 18.9 Hz, (D)), 7.47–8.33 (20H, aromatic
136.6, 134.1, 131.8, 129.2, 128.7, 128.4, 128.0, 127.4, 127.2, protons). 13C NMR (75 MHz, CDCl3; (ppm)): δ 146.6, 144.9,
126.7, 125.0, 118.8, 110.5, 47.2, 21.0, −2.3. 29Si NMR (99 MHz, 142.2, 141.3, 140.6, 138.8, 138.5, 138.2, 137.1, 135.4, 133.4,
CDCl3): δ −10.30. MS (FAB, m/z (%)) (M+, 100): 682. HRMS 129.58, 127.8, 127.7, 127.2, 125.4, 124.2, 122.6, 122.2, 120.8,
(m/z) calcd for C47H47NSi2: 681.32470, found 681.32464. 118.5, 108.6, 46.9, 21.1, 1.2, −1.0 (internal), −1.5 (external).
Mp. 146.4–146.5 °C.
29Si NMR (75 MHz, CDCl3; δ(ppm)): −10.23 (internal), −10.90
2,7-Bis(3-((E)-2-(phenyldimethylsilyl)vinyl)phenyl)-N-isopropyl- (external). Elemental analyses calcd for (C43H41NSi2)n: C 82.24,
carbazole (27). Yield 97% (230 mg) as a white solid.
H 6.58, N 2.23; found C 80.97, H 6.50, N 2.19. GPC data: Mn =
1H NMR (300 MHz, CDCl3): δ 0.1 (s, 12H, (A)),1.79 (d, 6H, 1121–7470 g mol−1, Mw = 1254–8658 g mol−1, PDI (Mw/Mn) =
(J), JHH = 7.2Hz), 5.11 (m, 1H, (I)), 6.66 (d, 1H, (B), JHH = 19.4 1.03–1.16, n = 2–14.
Hz), 7,0 (d, 1H, (C), JHH = 19.4 Hz), 7.34–7.6 (18H, D, F, H, K, L,
M) 7.7 (d, 4H, (E), JHH = 8.4 Hz), 8.15 (d, 2H (G), JHH = 8 Hz).
13C NMR (75 MHz, CDCl3): δ 145.0, 142.2, 140.7, 138.8, 137.1,
134.1, 131.1, 129.2, 128.0, 127.8, 127.1, 122.6, 120.8, 118.6,
Conflict of interest
108.6, 101.1, 29.8, 21.1, −2.4. 29Si NMR (75 MHz, CDCl3):
δ −10.30. MS (FAB, m/z (%)) (M+, 100): 682. HRMS (m/z) The authors declare no competing financial interest.
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Organic & Biomolecular Chemistry
17 S. Kotha, K. Lahin and D. Kashinath, Tetrahedron, 2002, 58,
9633–9695.
Acknowledgements
We gratefully acknowledge financial support from the National 18 T. Hiyama, Handbook of Organopalladium Chemistry for
Science Centre (Poland) (Project UMO-2011/02/A/ST5/00472).
Organic Synthesis, ed. E.-I. Negishi, Wiley-Interscience,
New York, NY, USA, 2002, pp. 285–309.
19 Y. Nakao and T. Hiyama, Chem. Soc. Rev., 2011, 40, 4893–
4901.
20 H. F. Sore and W. R. J. D. Galloway, Chem. Soc. Rev., 2012,
41, 1845–1866.
21 B. Marciniec and C. Pietraszuk, Curr. Org. Chem., 2003, 7,
691–735.
22 B. Marciniec and C. Pietraszuk, Metathesis of Silicon-
Containing Olefins, in Handbook of Metathesis, ed.
R. H. Grubbs, Wiley, Weinheim, 2003, pp. 463–486.
23 B. Marciniec, Coord. Chem. Rev., 2005, 249, 2374–2390.
24 B. Marciniec, Acc. Chem. Res., 2007, 40, 943–952.
25 M. Majchrzak, M. Hybsz, S. Kostera, M. Kubicki and
B. Marciniec, Tetrahedron Lett., 2014, 55, 3055–3058.
26 M. Ludwiczak, M. Majchrzak, M. Bayda, B. Marciniak,
M. Kubicki and B. Marciniec, J. Organomet. Chem., 2014,
750, 150–161.
Notes and references
1 B. Kippelen, A. Golemme, E. Hendrickx, J. F. Wang,
S. R. Marder and N. Peyghambarian, in Field Responsive
Polymers: Electroresponsive, Photoresponsive, and Responsive
Polymers in Chemistry and Biology, ed. I. M. Khan and
J. S. Harrison, ACS Symposium Series, ACS, Washington,
DC, 1999, vol. 726, p. 204.
2 Y. Z. Wang and A. Epstein, Acc. Chem. Res., 1999, 32, 217–
224.
3 H. Sasabe, Supramol. Sci., 1996, 3, 91–101.
4 J. V. Grazulevicius, P. Strohriegl, J. Pielichowski and
K. Pielichowski, Prog. Polym. Sci., 2003, 28, 1297–1353.
5 J. F. Morin and M. Leclerc, Macromolecules, 2002, 35, 8413–
8417.
27 M. Majchrzak, Y. Itami and B. Marciniec, Adv. Synth. Catal.,
2005, 347, 1285–1294.
6 J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. Marks,
N. K. Mackay, R. H. Friend and A. B. Holmes, Nature, 1990,
347, 539–541.
7 R. H. Friend, et al., Nature, 1999, 397, 121–128.
8 A. Kraft, A. C. Grimsdale and A. B. Holmes, Angew. Chem.,
Int. Ed., 1998, 37, 402–428.
9 J.-F. Morin, M. Leclerc, D. Ades and A. Siove, Macromol.
Rapid Commun., 2005, 26, 761–778.
10 K. Faid, A. Siove, D. Ades and C. Chevrot, Synth. Met., 1993,
55, 1656–1661.
28 B. Marciniec and C. Pietraszuk, Synthesis of Silicon
Derivatives with Ruthenium Catalysts, inRuthenium
Catalysts and Fine Chemistry, ed. C. Bruneau and
P. H. Dixneuf, Springer-Verlag, Berlin, Heidelberg, 2004,
p. 197–248.
29 Y. Itami, B. Marciniec, M. Majchrzak and M. Kubicki,
Organometallics, 2003, 22, 18351842.
30 T. Mise;, Y. Takaguchi;, T. Umemiya;, S. Shimizu; and
Y. Wakatsuki, Chem. Commun., 1998, 6, 699–700.
31 G. R. Fulmer, H. E. Gottlieb, A. J. M. Miller, A. Nudelman,
N. H. Sherden, B. M. Stoltz, J. E. Bercaw and K. I. Goldberg,
Organometallics, 2010, 29, 2176–2179.
11 Z. B. Zhang, M. Fujiki, H. Z. Tang, M. Motonaga and
K. Torimitsu, Macromolecules, 2002, 35, 1988–1990.
12 N. Blouin and M. Leclerc, Acc. Chem. Res., 2008, 41, 1110–
1119.
32 M. Majchrzak, S. Kostera, M. Kubicki and I. Kownacki,
Dalton Trans., 2013, 42, 15535–15539.
13 P. L. T. Boudreault, N. Blouin and M. Leclerc, Adv. Polym.
Sci., 2008, 212, 99–124.
33 B. A. Harding, P. R. Melvin, W. Dougherty Jr., S. Kassel and
F. E. Goodson, Organometallics, 2013, 32, 3570–3573.
34 R. A. Schunn, E. R. Wonchoba and G. Wilkinson, Inorg.
Synth., 1971, 13, 131–134.
14 B. M. Trost and T. R. Verhoeven, in Comprehensive
Organometallic Chemistry, ed. G. Wilkinson, F. G. Stone and
E. W. Abel, Pergamon Press, Oxford, 1982, vol. 8, pp.
799–938.
35 J. J. Levison and S. D. Robinson, J. Chem. Soc. A, 1970,
2947.
15 R. F. Heck, Palladium Reagents in Organic Synthesis,
Academic Press, New York, 1985.
36 C. S. Yi, D. W. Lee and Y. Chen, Organometallics, 1999, 18,
2043–2045.
16 J. Hassan and M. Sevignon, Chem. Rev., 2002, 102, 1359–
1469.
Org. Biomol. Chem.
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