Meta - And para -Functionalized Thermally Crosslinkable OLED-Materials through Selective Transition-Metal-Catalyzed Cross-Coupling Reactions

Article abstract of DOI:10.1055/s-0036-1590824

Herein, a synthetic approach using selective transition-metal-catalyzed cross-coupling reactions to thermally crosslinkable OLED materials based on vinyl-functionalized arylamines is reported. In a modular approach, 9,9-dialkyl-2,7-diiodo-9 H -fluorene underwent a selective Ullmann cross-coupling reaction with bromo-substituted-diphenylamines to give 9,9-dialkyl-2,7-bis(bromo-substituted-diphenylamino)-9 H -fluorenes that underwent end-functionalization by the Suzuki-Miyaura reaction using potassium vinyltrifluoroborate to give the corresponding 9,9-dialkyl-2,7-bis(vinyl-substituted-diphenylamino)-9 H -fluorenes. Novel meta -functionalized materials were synthesized, which are difficult to prepare by traditional synthetic pathways. The thermal behavior of the compounds was investigated by DSC measurements, indicating a lower thermal sensitivity of the meta -substituted materials than their para -functionalized analogues.

Full text of DOI:10.1055/s-0036-1590824

SYNTHESIS
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© Georg Thieme Verlag Stuttgart · New York
2017, 49, A–K
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en
M. Hempe et al.
Paper
Synthesis
meta- and para-Functionalized Thermally Crosslinkable OLED-
Materials through Selective Transition-Metal-Catalyzed Cross-
Coupling Reactions
Matthias Hempe
Lutz Schnellbächer
Tobias Wiesner
Michael Reggelin*
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Clemens-Schöpf-Institut für Organische Chemie und
Biochemie, Technische Universität Darmstadt, Alarich-
Weiss-Straße 4, 64287 Darmstadt, Germany
re@chemie.tu-darmstadt.de
Received: 03.04.2017
Accepted after revision: 06.06.2017
Published online: 26.07.2017
ized either by the formation of benzylic ethers with corre-
sponding styrene segments14,15 or by de novo synthesis
which most commonly involves Vilsmeier formylation, fol-
lowed by a Wittig reaction (Scheme 1).16–18 Unfortunately,
this strategy has several drawbacks: (1) the reaction se-
quence suffers from poor atom economy, (2) only para-sub-
stituted derivatives are accessible, and (3) the insufficient
regioselectivity of the Vilsmeier reaction, especially when
functionalizing more complex molecules. Therefore, this
synthetic approach often comprises the additional necessi-
ty of blocking reactive molecular positions, thus limiting
the scope of the functionalization method.
In this work we demonstrate a strategy to overcome the
aforementioned limitations. Retrosynthetically, the attach-
ment of the thermolabile vinyl moieties could be achieved
by key Suzuki–Miyaura reactions using potassium vinyltri-
fluoroborate, introduced by Genêt and Molander et al.19,20 In
this way the corresponding halogenated precursor mole-
cules, obtained following a selective modular synthetic ap-
proach, undergo a transition-metal-catalyzed cross-cou-
pling reaction. Thereby, even meta-functionalized materials
are obtainable, which are not accessible by electrophilic ar-
omatic substitution reactions. In addition to this, modula-
tion of the thermal properties of the materials was achieved
by varying the length of the attached alkyl chains. The ther-
mal behavior, as well as the crosslinkability of the deriva-
tives synthesized, was investigated by differential scanning
calorimetry (DSC).
DOI: 10.1055/s-0036-1590824; Art ID: ss-2017-z0223-op
Abstract Herein, a synthetic approach using selective transition-metal-
catalyzed cross-coupling reactions to thermally crosslinkable OLED
materials based on vinyl-functionalized arylamines is reported. In a
modular approach, 9,9-dialkyl-2,7-diiodo-9H-fluorene underwent a se-
lective Ullmann cross-coupling reaction with bromo-substituted-diphe-
nylamines to give 9,9-dialkyl-2,7-bis(bromo-substituted-diphenylami-
no)-9H-fluorenes that underwent end-functionalization by the Suzuki–
Miyaura reaction using potassium vinyltrifluoroborate to give the corre-
sponding 9,9-dialkyl-2,7-bis(vinyl-substituted-diphenylamino)-9H-fluo-
renes. Novel meta-functionalized materials were synthesized, which are
difficult to prepare by traditional synthetic pathways. The thermal be-
havior of the compounds was investigated by DSC measurements, indi-
cating a lower thermal sensitivity of the meta-substituted materials
than their para-functionalized analogues.
Key words cross-link, vinylation, OLED materials, Suzuki–Miyaura,
solution-processing, DSC
One key challenge for the production of high-efficiency
organic light-emitting diodes (OLEDs) by low-cost solution
based processes is the fabrication of well-defined multilay-
er architectures. During successive deposition of layers, the
preceding layers can be affected by dissolution, swelling, or
intermixing of the functional organic materials, resulting in
undefined interfaces and significantly reduced device effi-
ciencies. One effective strategy to avoid this problem is the
use of crosslinkable materials, rendering deposited layers
insoluble before further processing.
In this context, reactive moieties, such as trifluorovinyl
ethers,1 benzocyclobutanes,2 cinnamates,3 acrylates,4
azides,5–7 or oxetanes,8–10 have been applied in the field of
organic electronics. Furthermore, organic materials have
been functionalized with styrene groups for thermal, self-
initiated crosslinking of thin films.11–13 The attachment of
styrene groups to the molecular backbone has been real-
Synthesis of the materials was accomplished by cou-
pling of a central fluorene segment and lateral diphenyl-
amine components. The central fluorene core was synthe-
sized in a two-step reaction sequence, starting with selec-
tive iodination21 of 9H-fluorene (1) using iodine and
periodic acid (Scheme 2). Thereafter, geminal dialkylation
reactions22 yield the fluorene components 3a–d with di-
verse alkyl chain length.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–K

B
M. Hempe et al.
Paper
Synthesis
O
O
Common synthetic approach:
H
H
Wittig
reaction
Vilsmeier
reaction
N-arylation
N
N
N
N
Ar
Ar
N
N
Ar
X
Ar
X
X
X
Y
Y
(Y = Me, H)
selective
N-arylation
Suzuki–Miyaura reaction
N
N
Ar
Alkyl
Alkyl
In this work:
Ar =
(X = Br)
Scheme 1 Synthetic approach
Alkyl
Alkyl
I2, H5IO6
R-X, KOtBu
I
I
I
I
AcOH–H2O–H2SO4
(100:20:3)
THF, rt
80 °C, 51%
(86%)
(88%)
(90%)
(90%)
3a : Alkyl = methyl
2
1
3b : Alkyl = butyl
3c : Alkyl = hexyl
3d : Alkyl = octyl
Scheme 2 Synthesis of alkylated 2,7-diiodofluorenes 3a–d
The synthesis of the halogenated secondary arylamines
was achieved by Buchwald–Hartwig cross-coupling reac-
tions of anilines with 1-bromo-4- or -3-iodobenzenes 5a,b,
selecting iodine over bromine (Scheme 3). Using the bis-
dentate ligand DPE-Phos,23,24 diphenylamine components
7a, 7c, and 7d, respectively, were obtained in good yields
(71–85%). The synthesis of the bis(4-bromophenyl)amine
(7b) was achieved more conveniently by dibromination of
diphenylamine (6) using NBS as reported by Ishow et al.25
Pd(OAc)2, DPE-Phos
NaOtBu
NH2
NH2
para-components
meta-components
5a
Br
I
to 7c
PhMe (abs.), 110 °C
17 h, 84%
Br
Pd(OAc)2
DPE-Phos
NaOtBu
to 7a
4a
4a
Br
NH
NH
Br
5b
I
to 7b
PhMe (abs.)
110 °C
X
NH2
X
NBS
NH
DMF, 24 h
77%
7a : X = H
7b : X = Br
7c : X = H (85%)
7d : X = Br (71%)
to 7d
Br
6
4b
Scheme 3 Synthesis of brominated diphenylamine components by selective Buchwald–Hartwig cross-coupling
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–K

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M. Hempe et al.
Paper
Synthesis
X2
X1
X1
X1
X2
X2
Alkyl
Alkyl
Alkyl
Alkyl
CuI, KOH
1,10-phenanthroline
NH
X3
I
I
N
N
PhMe (abs.), 100 °C
X4
X3
X3
X4
X4
3
7
8
Scheme 4 Synthesis of brominated precursor molecules 8 by selective Ullmann coupling
Table 1 Results of Synthesis of Compounds 8
Entry Fluorene (alkyl) Amine X1 X2 X3
Table 2 Results of Synthesis of Compounds 10
X4
Product Yield (%)
Entry Fluorene R1
R2
R3
R4
Product
Yield
(%)
1
2
3
4
5
6
7
3a (Me)
3a (Me)
3b (Bu)
7a
7b
7b
7b
7b
7c
7d
Br
Br
Br
Br
Br
H
H
H
H
8a
8b
8c
8d
8e
8f
90
75
69
52
74
64
76
1
2
3
4
5
6
7
8a
8b
8c
8d
8e
8f
vinyl
vinyl
vinyl
vinyl
vinyl
H
H
H
H
2V-Methyl (10a)
34
H
Br
Br
Br
Br
H
H
H
H
H
H
Br
H
vinyl
vinyl
vinyl
vinyl
H
H
H
H
H
H
4V-Methyl (10b)
4V-Butyl (10c)
4V-Hexyl (10d)
4V-Octyl (10e)
41
18
–
H
H
3c (hexyl)
3d (octyl)
3a (Me)
3a (Me)
H
H
H
H
–
Br
Br
vinyl
vinyl
m2V-Methyl (10f) 68
H
H
8g
8g
H
H
vinyl m4V-Methyl (10g) 60
Following the modular approach, the synthesis of the
The thermal behavior and crosslinkability of the vi-
halogenated precursor molecules 8 was accomplished by
the twofold Ullmann cross-coupling reaction of the diiodo-
fluorenes 3a–d with the diphenylamines 7a–d, thereby se-
lecting iodine over the bromine-substituent of the electron-
rich diphenylamine components (Scheme 4, Table 1). The
compounds were obtained in acceptable to excellent yields.
The vinylation of the halogenated precursor molecules 8
was achieved by Suzuki–Miyaura cross-coupling reactions
using potassium vinyltrifluoroborate (9) (Scheme 5, Table
2).20 The crosslinkable compounds 10a–c,f,g were isolated
in moderate to good yields, provided care is taken due to
the thermal instability of compounds 10 and their mina-
cious polymerization under work-up conditions.
nylated derivatives 10 was investigated by DSC measure-
ments (Figure 1). The thermograms of the first heating cy-
cles show endothermic signals, which were assigned to the
melting of the non-crosslinked molecules. It can be seen
that the number of vinyl groups per molecule has only a
minor impact on the melting temperature. In comparison to
the para-substituted derivatives, the meta-functionalized
analogues m2V-Methyl 10f and m4V-Methyl 10g tend to
melt at lower temperatures. By substituting the fluorene
segment with longer alkyl chains, the melting temperature
of the functional materials can be lowered even further, e.g.
10c.
At higher temperatures the thermograms of all deriva-
tives 10 feature a broad and intense exothermic signal in
their first heating cycles, which is caused by the progressing
thermal crosslinking reaction. The absence of any exother-
mic behavior at those temperatures in the course of subse-
This tendency is even more pronounced in case of the
derivatives bearing longer alkyl chains and therefore, the
compounds 4V-Hexyl 10d and 4V-Octyl 10e could not be
isolated.
R1
R1
X1
X1
Pd(OAc)2, Ph3P
Cs2CO3
R2
R2
X2
X2
Alkyl
Alkyl
Alkyl
Alkyl
BF3K
9
N
N
N
N
THF–H2O (9:1)
90 °C
R3
R3
X3
X3
R4
R4
X4
X4
10
8
Scheme 5 Functionalization of precursor molecules 8 by Suzuki–Miyaura cross-coupling
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–K

D
M. Hempe et al.
Paper
Synthesis
als were obtained for the first time. In addition to this, the
described cross-coupling chemistry does not suffer from re-
gioselectivity restrictions associated with the electrophilic
aromatic substitution reactions of earlier preparations.
The thermal behavior and crosslinkability of the report-
ed derivatives was investigated by DSC measurements. The
synthetic strategy described in this paper should be easily
transferable to more complex functional molecules and
presents an attractive alternative to the traditional synthet-
ic approach towards this kind of crosslinkable materials.
Solvents and reagents: THF and toluene were distilled from Na/ben-
zophenone under an argon atmosphere. Reagents were obtained from
commercial sources and were used without further purification.
Moisture and/or air sensitive experiments were conducted using
flame-dried glassware under argon atmosphere. NMR: 1H NMR spec-
tra were recorded on Bruker ARX 300 and DRX 500 spectrometers op-
erating at 300 and 500 MHz, respectively at 300 K and 13C NMR spec-
tra were recorded on the same instruments at 75 and 125 MHz, both
were referenced against the residual solvent signal as reported in the
literature.29 Assigned peaks are indicated by numbering used in the
corresponding figure. Flash chromatography was carried out on silica
gel 60 (15–40 μm) by Merck KGaA at a pressure of 2–3 bar. Mass spec-
tra: EI-MS and EI-HRMS were recorded on a double focusing mass
spectrometer MAT 95. Elemental analysis were performed by the ser-
vice of Technische Universität Darmstadt on a Vario El by Elementar.
Differential scanning calorimetry (DSC) was performed on a DSC1 by
Mettler-Toledo.
Figure 1 DSC measurements of thermally crosslinkable derivatives 10
(N2 atmosphere, 10 K/min, black line: first heating cycle, blue line: sec-
ond heating cycle). The traces have been shifted vertically for clarity.
2,7-Diiodo-9H-fluorene (2)
7
1
6
quent heating cycles indicates complete crosslinking in the
first place. The meta-substituted derivatives are generally
less sensitive towards thermal crosslinking than the para-
substituted compounds. This results in higher onset- and
peak-maxima temperatures of the corresponding signals. A
possible explanation of this behavior can be found in the
mechanism of the self-initiated radical polymerization of
styrene derivatives, involving an initial dimerization step
via Diels–Alder reaction, followed by a subsequent radical
transfer step.26–28 The resulting benzylic radical initiates the
chain growth reaction. Because of the distinct steric and
electronic situations of the vinyl groups in the case of the
meta- and para-functionalization, different reactivities of
the derivatives in both initiation steps are plausible as ex-
perimentally observed in the DSC thermograms.
2
I
I
5
3
4
Figure 2
In a modification of the literature procedure,21 fluorene (1, 50.00 g,
300.81 mmol) was suspended in a mixture of glacial AcOH (800 mL),
H2O (165 mL), and concd H2SO4 (25 mL). The suspension was initially
heated to 95 °C and then cooled to 80 °C. At this temperature, H5IO6
(25.00 g, 109.68 mmol, 0.36 equiv) and I2 (50.50 g, 198.97 mmol, 0.66
equiv) were added and the resulting mixture was vigorously stirred
for 4 h. Then the mixture was cooled to r.t. The resulting precipitate
was filtered and washed with aq sat. NaHCO3 solution and water. The
solid was dried and then recrystallized (n-hexane) to give the product
(Figure 2) as colorless needles; yield: 64.49 g (154.29 mmol, 51%).
Analytical data match data reported in the literature.21
In conclusion, we have demonstrated a synthetic ap-
proach to thermally crosslinkable model compounds based
on selective transition-metal-catalyzed cross-coupling re-
actions. The strategy features the end-functionalization of
halogenated precursor molecules 8 by Suzuki–Miyaura re-
action with potassium vinyltrifluoroborate (9), introducing
the thermolabile, crosslinkable vinyl moiety in the very last
step of the synthesis. Thus, novel meta-substituted materi-
1H NMR (CDCl3, 300 MHz, 300 K): δ = 3.831 (s, 2 H, 7-H), 7.491 (d, 2 H,
4-H), 7.706 (d, 2 H, 3-H), 7.879 (s, 2 H, 1-H); 3J3,4 = 8.1 Hz.
9,9-Dialkyl-2,7-diiodo-9H-fluorenes 3; General Procedure
In a modification of the literature procedure,30 in a flame-dried flask,
2,7-diiodo-9H-fluorene (2) was dissolved in abs THF (2 mL/mmol)
and the resulting solution was cooled to 0 °C. The solution was slowly
mixed with KOtBu (2.70 equiv) and the mixture was stirred at r.t. for 2
h. The mixture was cooled to 0 °C, mixed with the haloalkane (3.00
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–K

E
M. Hempe et al.
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Synthesis
equiv) and the mixture was stirred at r.t. for 24 h. The mixture was
filtered through silica gel and the solvent was removed in vacuo. The
resulting solid was purified by recrystallization.
9,9-Dihexyl-2,7-diiodo-9H-fluorene (3c)
12
10
8
9
13
11
1
6
2,7-Diiodo-9,9-dimethyl-9H-fluorene (3a)
7
2
I
I
5
3
8
4
1
6
7
2
I
I
Figure 5
5
3
4
According to the general procedure using 2 (30.00 g, 71.77 mmol),
KOtBu (21.74 g, 193.77 mmol, 2.70 equiv), and 1-bromohexane
(30.22 mL, 215.31 mmol, 3.00 equiv) gave a solid that was purified by
column chromatography (silica gel, cyclohexane/n-hexane, 1:1) and
recrystallized (EtOH) to give the product (Figure 5) as colorless crys-
tals; yield: 37.68 g (64.27 mmol, 90%); mp 60 °C.
1H NMR (CDCl3, 500 MHz, 300 K): δ = 0.599 (m, 4 H, 9-H), 0.790 (t, 6
H, 13-H), 1.000–1.093 (m, 8 H, 10-H, 11-H), 1.124 (m, 4 H, 12-H),
1.897 (m, 4 H, 8-H), 7.405 (d, 2 H, 4-H), 7.645 (s, 2 H, 1-H), 7.654 (d, 2
H, 3-H).
13C NMR (CDCl3, 125 MHz, 300 K): δ = 14.13 (13-C), 22.69 (12-C),
23.78 (9-C), 29.69 (10-C or 11-C), 31.56 (10-C or 11-C), 40.23 (8-C),
55.68 (7-C), 93.24 (2-C), 121.63 (4-C), 132.20 (1-C), 136.17 (3-C),
139.61 (5-C), 152.65 (6-C).
Figure 3
According to the general procedure using 2, (50.00 g, 119.60 mmol),
KOtBu (36.24 g, 322.96 mmol, 2.70 equiv), and MeI (22.44 mL, 358.00
mmol, 3.00 equiv) gave a solid that was purified by recrystallization
(toluene) to give the product (Figure 3) as colorless crystals; yield:
45.67 g (102.38 mmol, 86%); mp 203 °C.
Analytical data matched data reported in the literature.31
1H NMR (CDCl3, 300 MHz, 300 K): δ = 1.451 (s, 6 H, 8-H), 7.443 (d, 2 H,
4-H), 7.664 (d, 2 H, 3-H), 7.744 (s, 2 H, 1-H); 4J1,3 = 1.53 Hz, 3J3,4 = 7.94
Hz.
MS (EI): m/z (%) = 446 (100, [M]+]), 431 (45, [M – CH3]+), 319 (10, [M –
I]+), 304 (20, [M – I – CH3]+), 192 (5, [M – I2]+).
MS (EI): m/z (%) = 586 (100, [M]+]), 501 (25, [M – C6H13]+), 417 (30, [M
Anal. Calcd for C15H12I2: C, 40.39; H, 2.71. Found: C, 40.40; H, 2.81.
– 2 (C6H13)]+), 374 (35, [M – C6H13 – I]+).
HRMS (EI): m/z [M] calcd for C25H32I2: 586.0592; found: 586.0634.
9,9-Dibutyl-2,7-diiodo-9H-fluorene (3b)
Anal. Calcd for C25H32I2: C, 51.21; H, 5.50. Found: C, 51.25; H, 5.49.
11
8
10
2,7-Diiodo-9,9-dioctyl-9H-fluorene (3d)
9
1
6
7
2
I
I
14
12
10
5
15
8
3
9
13
4
11
1
6
7
2
Figure 4
I
I
5
3
4
According to the general procedure using 2 (30.00 g, 71.77 mmol),
KOtBu (21.74 g, 193.77 mmol, 2.70 equiv), and BuI (24.50 mL, 215.30
mmol, 3.00 equiv) gave a solid that was purified by column chroma-
tography (silica gel, cyclohexane/n-hexane, 1:1) and recrystallized
(EtOH/EtOAc) to give the product (Figure 4) as colorless crystals;
yield: 33.44 g (63.07 mmol, 88%); mp 137 °C.
1H NMR (CDCl3, 500 MHz, 300 K): δ = 0.578 (m, 4 H, 9-H), 0.697 (t, 6
H, 11-H), 1.092 (m, 4 H, 10-H), 1.907 (m, 4 H, 8-H), 7.409 (d, 2 H, 4-H),
7.649 (s, 2 H, 1-H), 7.659 (d, 2 H, 3-H); 3J3,4 = 7.00 Hz.
Figure 6
According to the general procedure using 2 (30.00 g, 71.77 mmol),
KOtBu (21.74 g, 193.77 mmol, 2.70 equiv), and 1-bromooctane (37.46
mL, 215.31 mmol, 3.00 equiv) gave a solid that was purified by col-
umn chromatography (silica gel, cyclohexane/n-hexane, 1:1) and re-
crystallized (EtOH) to give the product (Figure 6) as colorless crystals;
yield: 41.47 g (64.54 mmol, 90%); mp 58 °C.
1H NMR (CDCl3, 500 MHz, 300 K): δ = 0.596 (m, 4 H, 9-H), 0.841 (t, 6
H, 15-H), 1.014–1.188 (m, 16 H, 10-H, 11-H, 12-H, 13-H), 1.223 (m, 4
H, 14-H), 1.896 (m, 4 H, 8-H), 7.404 (d, 2 H, 4-H), 7.646 (s, 2 H, 1-H),
7.655 (d, 2 H, 3-H).
13C NMR (CDCl3, 125 MHz, 300 K): δ = 14.22 (15-C), 22.75 (14-C),
23.76 (9-C), 29.25 (CH2), 29.30 (CH2), 31.90 (CH2), 40.20 (8-C), 55.69
(7-C), 93.25 (2-C), 121.62 (4-C), 132.20 (1-C), 136.17 (3-C), 139.91 (5-
C), 152.66 (6-C).
13C NMR (CDCl3, 125 MHz, 300 K): δ = 13.89 (11-C), 23.08 (10-C),
25.98 (9-C), 40.08 (8-C), 55.60 (7-C), 93.27 (2-C), 121.64 (4-C), 132.19
(1-C), 136.19 (3-C), 139.91 (5-C), 152.65 (6-C).
MS (EI): m/z (%) = 530 (100, [M]+]), 473 (40, [M – C4H9]+), 417 (30, [M
– 2 (C4H9)]+), 346 (50, [M – C4H9 – I]+).
HRMS (EI): m/z [M] calcd for C21H24I2: 529.9966; found: 529.9927.
Anal. Calcd for C21H24I2: C, 47.57; H, 4.56. Found: C, 47.56; H, 4.56.
MS (EI): m/z (%) = 642 (100, [M]+]), 529 (20, [M – C8H17]+), 417 (25, [M
– 2 (C8H17)]+), 402 (35, [M – C8H17 – I]+).
HRMS (EI): m/z [M] calcd for C29H40I2: 642.1218; found: 642.1184.
Anal. Calcd for C29H40I2: C, 54.22; H, 6.28. Found: C, 54.17; H, 6.26.
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M. Hempe et al.
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Synthesis
4-Bromo-N-phenylaniline (7a)
MS (EI): m/z (%) = 327 (100, [M]+]), 247 (10, [M – Br]+), 167 (50, [M – 2
Br2]+).
3
Br
4
Anal. Calcd for C12H9Br2N: C, 44.07; H, 2.77; N, 4.28. Found: C, 44.10;
H, 2.82; N, 4.32.
2
1
NH
1'
3-Bromo-N-phenylaniline (7c)
2'
3'
4'
Br
NH
Figure 7
According to the literature procedure,32 in a flame-dried Schlenk-flask
1-bromo-4-iodobenzene (5a, 14.50 g, 51.25 mmol), aniline (4a, 4.68
mL, 51.25 mmol, 1.00 equiv), DPE-Phos (1.66 g, 3.08 mmol, 0.06
equiv), and Pd(OAc)2 (0.469 g, 2.05 mmol, 0.04 equiv) were suspend-
ed in abs toluene (25 mL) and the mixture was stirred for 20 min at
r.t. Then NaOtBu (5.23 g, 56.38 mmol, 1.10 equiv) was added and the
dark red suspension was stirred at 110 °C for 17 h. After cooling to r.t.,
the mixture was filtered through a pad of silica gel and the solvent
was removed in vacuo. The residue was purified by column chroma-
tography (silica gel, petroleum ether/Et2O, 8:1 + 3 vol% Me2NEt), to
give the product (Figure 7) as a colorless solid; yield: 10.67 g (43.00
mmol, 84%); mp 87 °C.
Figure 9
In a flame-dried flask and under argon atmosphere, a mixture of ani-
line (4a, 1.83 mL, 20 mmol), 1-bromo-3-iodoaniline (5b, 2.56 mL, 20
mmol, 1.00 equiv), Pd(OAc)2 (22.6 mg, 0.10 mmol, 0.005 equiv), and
DPE-Phos (81.2 mg, 0.15 mmol, 0.0075 equiv) was dissolved in abs
toluene (20 mL) and the mixture was stirred for 1 h at r.t. Then NaOt-
Bu (2.69 g, 28 mmol, 1.40 equiv) was added and the mixture was
heated to 110 °C for 2 h. After cooling to r.t., the mixture was filtered
through a pad of silica gel and the solvent was removed in vacuo. The
residue was purified by kugelrohr distillation under reduced pressure
to give the product (Figure 9) as a yellow oil; yield: 4.19 g (16.9 mmol,
85%).
Analytical data match data reported in the literature.32
1H NMR (CDCl3, 300 MHz, 300 K): δ = 5.690 (br, N–H), 6.928 (t, 1 H),
6.958 (t, 1 H), 6.966–7.014 (m, 1 H), 7.037–7.092 (m, 2 H), 7.255–
7.331 (m, 2 H), 7.338 (m, 1 H), 7.367 (m, 1 H).
Analytical data match data reported in the literature.33
Anal. Calcd for C12H10BrN: C, 58.09; H, 4.06; N, 5.65. Found: C, 58.16;
H, 4.09; N, 5.64.
MS (EI): m/z (%) = 249 (97, [MBr(81)]+]), 247 (100, [MBr(79)]+), 167 (100,
[M – Br]+).
HRMS (EI): m/z [M] calcd for C12H10BrN: 246.9997; found: 247.0004.
Bis(3-bromophenyl)amine (7d)
Anal. Calcd for C12H10BrN: C, 58.09; H, 4.06; N, 5.65. Found: C, 58.09;
H, 4.00; N, 5.61.
5
4
6
Bis(4-bromophenyl)amine (7b)
3
1
Br
NH
2
3
Br
4
2
Br
1
NH
Br
Figure 10
In a flame-dried flask and under argon atmosphere, a mixture of 3-
bromoaniline (9.80 mL, 15.50 g, 90 mmol), 1-bromo-3-iodoaniline
(11.5 mL, 25.50 g, 90 mmol, 1.00 equiv), Pd(OAc)2 (507 mg,
2.26 mmol, 0.025 equiv), and DPE-Phos (1.82 g, 3.38 mmol, 0.038
equiv) was dissolved in abs toluene (90 mL) and the mixture was
stirred for 1 h at r.t. Then NaOtBu (12.10 g, 126 mmol, 1.40 equiv) was
added and the mixture was heated to 110 °C for 2 h. After cooling to
r.t., the mixture was filtered through a pad of silica gel and the solvent
was removed in vacuo. The residue was purified by kugelrohr distilla-
tion under reduced pressure to give the product (Figure 10) as a color-
less oil; yield: 20.80 g (63.5 mmol, 71%).
Figure 8
According to a literature procedure,25 Ph2NH (6, 60.00 g, 354.56
mmol) was dissolved in DMF (200 mL) and cooled to 0 °C. Under vig-
orous stirring, a solution NBS (126.88 g, 712. mmol, 2.01 equiv) in
DMF (400 mL) was added dropwise and the mixture was stirred at r.t.
for 48 h. Then, the mixture was poured into H2O (1.5 L) and the result-
ing precipitate was filtered. The solid was recrystallized (EtOH/H2O)
to give the product (Figure 8) as colorless crystals; yield: 89.77 g
(274.5 mmol, 77%); mp 107.5 °C.
1H NMR (CDCl3, 500 MHz, 303 K): δ = 5.690 (br, N–H), 6.978 (ddd, 2 H,
4-H), 7.089 (ddd, 2 H, 6-H), 7.136 (‘t’, 2 H, 5-H), 7.199 (‘t’, 2 H, 2-H);
4J2,4 = 1.7 Hz, 4J2,6 = 2.1 Hz, 3J4,5 = 7.9 Hz, 4J4,6 = 1.2 Hz, 3J5,6 = 7.9 Hz.
Analytical data match data reported in the literature.25
13C NMR (CDCl3, 125 MHz, 303 K): δ = 116.62 (4-C), 120.89 (2-C),
1H NMR (CDCl3, 500 MHz, 300 K): δ = 5.624 (br, N–H), 6.915 (d, 4 H, 2-
123.18 (3-C), 124.58 (6-C), 130.72 (5-C), 143.78 (1-C).
H), 7.362 (d, 4 H, 3-H).
3J2,3 = 8.70 Hz.
Anal. Calcd for C12H9Br2N: C, 44.07; H, 2.77; N, 4.28; Br, 48.87. Found:
C, 44.10; H, 2.92; N, 4.19.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–K

G
M. Hempe et al.
Paper
Synthesis
Synthesis of Halogen-Substituted N2,N2,N7,N7-Tetraaryl-9H-fluo-
rene-2,7-diamines 8; General Procedure
equiv), and KOH (5.106 g, 91 mmol, 7.97 equiv) gave a solid that was
purified by column chromatography (silica gel, cyclohexane/petro-
leum ether/Et2O, 1000:998:2) to give the product (Figure 12) as a col-
orless solid; yield: 7.205 g (8.534 mmol, 75%); mp 144.0–146.0 °C.
1H NMR (CDCl3, 500 MHz, 300 K): δ = 1.360 (s, 6 H, 8-H), 6.983 (d, 8 H,
10-H), 7.008 (d, 2 H, 3-H), 7.115 (s, 2 H, 1-H), 7.358 (d, 8 H, 11-H),
7.519 (d, 2 H, 4-H); 4J1,3 = 1.6 Hz, 3J3,4 = 8.1 Hz, 3J10,11 = 8.6 Hz.
13C NMR (CDCl3, 125 MHz, 300 K): δ = 27.12 (8-C), 47.09 (7-C), 115.52
(12-C), 119.14 (1-C), 120.60 (4-C), 123.56 (3-C), 125.44 (10-C), 132.49
(11-C), 135.74 (5-C), 146.05 (2-C), 146.81 (9-C), 155.48 (6-C).
In a flame-dried flask and under an argon atmosphere, a mixture of
alkyl-substituted 2,7-diiodo-9H-fluorene 3, brominated diphenyl-
amine 7 (2.00 equiv), CuI (21 mol%), and 1,10-phenanthroline
(40 mol%) was suspended in abs toluene (2 mL/mmol). Then, finely
ground KOH (8.00 equiv) was added and the resulting mixture was
heated to 100 °C until the reaction was complete. After cooling to r.t.,
the mixture was filtered through a pad of silica gel and the solvent
was removed in vacuo. The remaining solid was purified by column
chromatography (silica gel) or by recrystallization.
MS (EI): m/z (%) = 844 (100, [M]+), 765 (10, C39H28Br3N2).
N2,N7-Bis(4-bromophenyl)-9,9-dimethyl-N2,N7-diphenyl-9H-fluo-
HRMS (EI): m/z [M] calcd for C39H28Br4N2: 839.8985; found: 839.8944.
rene-2,7-diamine (8a)
N2,N2,N7,N7-Tetrakis(4-bromophenyl)-9,9-dibutyl-9H-fluorene-
2,7-diamine (8c)
12
11
10
8
15
Br
Br
1
6
14
9
7
11
2
N
N
13
13
12
10
5
3
9
1
14
4
8
6
16
7
2
3
N
N
15
Br
Br
5
Figure 11
4
Br
Br
According to the general procedure using 3a (800 mg, 1.79 mmol), 7a
(890 mg, 3.59 mmol, 2.00 equiv), CuI (73.6 mg, 0.38 mmol, 0.21
equiv), 1,10-phenanthroline (129.3 mg, 0.72 mmol, 0.40 equiv), and
KOH (805 mg, 14.35 mmol, 8.00 equiv) gave the product (Figure 11)
as a yellow glass; yield: 1.103 g (1.61 mmol, 90%); mp 215.5 °C.
1H NMR (CDCl3, 500 MHz, 300 K): δ = 1.352 (s, 6 H, 8-H), 6.988 (d, 8 H,
14-H), 7.042 (t, 2 H, 12-H), 7.115 (d, 2 H, 3-H), 7.133 (s, 2 H, 1-H),
7.271 (t, 4 H, 11-H), 7.343 (d, 4 H, 14-H), 7.503 (d, 2 H, 4-H); 3J3,4 = 7.9
Hz, 3J14,15 = 8.6 Hz.
13C NMR (CDCl3, 125 MHz, 300 K): δ = 27.13 (8-C), 46.99 (7-C), 114.80
(16-C), 119.06 (1-C), 120.37 (4-C), 123.26 (3-C), 123.86 (12-C), 124.38
(10-C), 125.18 (14-C), 129.45 (11-C), 132.28 (15-C), 134.52 (5-C),
146.44 (2-C), 147.31 (13-C), 147.64 (9-C), 155.35 (6-C).
Figure 13
According to the general procedure using 3b (14.00 g, 26.40 mmol),
7b (17.23 g, 52.81 mmol, 2.00 equiv), CuI (1.08 g, 5.54 mmol, 0.21
equiv), 1,10-phenanthroline (1.903 g, 10.56 mmol, 0.40 equiv), and
KOH (11.85 g, 211.23 mmol, 8.00 equiv) with purification by recrys-
tallization (CH2Cl2/petroleum ether) gave the product (Figure 13) as
yellow crystals; yield: 16.89 g (18.19 mmol, 69%); mp 213.5 °C.
1H NMR (CDCl3, 500 MHz, 300 K): δ = 0.642 (m, 4 H, 13-H), 0.719 (t, 6
H, 15-H), 1.028–1.119 (m, 4 H, 14-H), 1.778 (m, 4 H, 12-H), 6.895–
7.006 (br, 10 H, 9-H, 3-H), 7.022 (br, 2 H, 1-H), 7.346 (d, 8 H, 10-H),
7.498 (br, 2 H, 4-H).
13C NMR (CDCl3, 125 MHz, 300 K): δ = 14.13 (15-C), 23.07 (14-C),
26.32 (13-C), 19.80 (12-C), 55.24 (7-C), 115.46 (11-C), 119.63 (1-C),
120.34 (4-C), 123.97 (3-C), 125.31 (9-C), 132.44 (10-C), 136.87 (5-C),
145.86 (2-C), 146.76 (8-C), 152.60 (6-C).
MS (EI): m/z (%) = 688 (49, [MBr(81)]+]), 686 (100, [MBr(79)]+), 671 (10, [M
– CH3]+), 606 (10, [M – Br]+), 591 (5, [M – Br – CH3]+).
HRMS (EI): m/z [M] calcd for C39H30Br2N2: 684.0776; found: 684.0804.
MS (EI): m/z (%) = 928 (100, [M]+]), 828 (20, [M – 2 (C4H9)]+).
Anal. Calcd for C39H30Br2N2: C, 68.23; H, 4.40; N, 4.08. Found: C, 67.44;
H, 4.28; N, 4.27.
Anal. Calcd for C45H40Br4N2: C, 58.21; H, 4.34; N, 3.02. Found: C, 58.32;
H, 4.34; N, 3.07.
N2,N2,N7,N7-Tetrakis(4-bromophenyl)-9,9-dimethyl-9H-fluorene-
2,7-diamine (8b)
N2,N2,N7,N7-Tetrakis(4-bromophenyl)-9,9-dihexyl-9H-fluorene-
2,7-diamine (8d)
Br
Br
According to the general procedure using 3c (10.00 g, 17.06 mmol),
7b (17.28 g, 52.84 mmol, 3.10 equiv), CuI (1.08 g, 5.54 mmol, 0.21
equiv), 1,10-phenanthroline (1.93 g, 10.71 mmol, 0.40 equiv), and
KOH (7.66 g, 136.44 mmol, 8.00 equiv) with purification by recrystal-
lization (CH2Cl2/petroleum ether) gave the product (Figure 14) as fine
crystals; yield: 8.67 g (8.80 mmol, 52%); mp 208 °C.
12
11
10
8
1
6
9
7
2
N
N
5
3
4
1H NMR (CDCl3, 500 MHz, 300 K): δ = 0.659 (m, 4 H, 13-H), 0.838 (t, 6
H, 17-H), 1.011–1.112 (m, 8 H, 14-H, 15-H), 1.161 (m, 4 H, 16-H),
1.773 (m, 4 H, 12-H), 6.965 (d, 8 H, 9-H), 6.984 (d, 2 H, 3-H), 7.021 (s,
2 H, 1-H), 7.341 (d, 8 H, 10-H), 7.503 (d, 2 H, 4-H); 3J9,10 = 8.5 Hz.
Br
Br
Figure 12
According to the general procedure using 3a (5.097 mg, 11.426
mmol), 7b (7.313 g, 22.363 mmol, 1.96 equiv), CuI (431 mg, 2.264
mmol, 0.20 equiv), 1,10-phenanthroline (836 mg, 4.636 mmol, 0.41
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–K

H
M. Hempe et al.
Paper
Synthesis
N2,N7-Bis(3-bromophenyl)-9,9-dimethyl-N2,N7-diphenyl-9H-fluo-
17
rene-2,7-diamine (8f)
16
15
Br
Br
14
18
17
11
13
10
8
16
12
1
9
1
6
15
8
6
7
7
2
3
N
N
2
N
N
10
5
11
9
5
Br
Br
3
4
4
14
12
13
Br
Br
Figure 14
Figure 16
According to the general procedure using 3a (11.90 g, 26.60 mmol),
7c (15.30 g, 61.80 mmol, 2.30 equiv), CuI (435 mg, 2.28 mmol, 0.086
equiv), 1,10-phenanthroline (413 mg, 2.29 mmol, 0.086 equiv), and
KOH (14.30 g, 216 mmol, 8.10 equiv) with purification by column
chromatography (silica gel, petroleum ether/Et2O) and recrystalliza-
tion (cyclohexane/n-hexane) gave the product (Figure 16) as colorless
crystals; yield: 11.60 g (16.90 mmol, 64%); mp 206–207 °C.
1H NMR (CDCl3, 500 MHz, 303 K): δ = 1.361 (s, 6 H, 8-H), 6.970–7.040
(m, 2 H, 3-H), 7.040–7.100 (m, 6 H, 1-H, 13-H, 18-H), 7.131 (d, 4 H,
16-H), 7.287 (‘t’, 4 H, 17-H), 7.537 (d, 2 H, 4-H), 6.97–7.04, 7.21–7.25,
7.14–7.17 (m, 6 H, 10-H, 12-H, 14-H); 3J3,4 = 8.0 Hz, 3J16,17 = 7.6 Hz.
13C NMR (CDCl3, 125 MHz, 303 K): δ = 26.95 (8-C), 46.89 (7-C), 119.30
(C-H), 120.34 (4-C), 121.40 (3-C), 122.80 (11-C), 123.42 (18-C),
124.06 (C-H), 124.56 (16-C), 124.83 (1- C), 125.62 (C-H), 129.41 (17-
C), 130.31 (13-C), 134.59 (5-C), 146.13 (2-C), 147.29 (15-C), 149.52
(9-C), 155.26 (6-C).
13C NMR (CDCl3, 125 MHz, 300 K): δ = 14.23 (17-C), 22.67 (16-C),
24.01 (13-C), 29.69 (15-C), 31.72 (14-C), 40.16 (12-C), 55.33 (7-C),
115.37 (11-C), 119.72 (1-C), 120.33 (4-C), 124.01 (3-C), 125.23 (9-C),
132.45 (10-C), 136.87 (5-C), 145.87 (2-C), 146.82 (8-C), 152.58 (6-C).
HRMS (EI): m/z [M] calcd for
C
49H4879Br4N2: 980.0546; found:
980.0555.
Anal. Calcd for C49H48Br4N2: C, 59.78; H, 4.91; N, 2.85. Found: C, 59.76;
H, 4.89; N, 2.72.
N2,N2,N7,N7-Tetrakis(4-bromophenyl)-9,9-dioctyl-9H-fluorene-
2,7-diamine (8e)
19
18
17
16
15
MS (EI): m/z (%) = 686 (100, [C39H30N2Br2]+), 607 (2, [C39H30N2Br]+).
Br
Br
HRMS (EI): m/z [M] calcd for C39H30N2Br2: 684.0776; found: 684.0788.
14
11
13
10
12
N2,N2,N7,N7-Tetrakis(3-bromophenyl)-9,9-dimethyl-9H-fluorene-
2,7-diamine (8g)
9
1
6
8
7
2
N
N
5
3
4
Br
Br
8
Br
Br
1
6
7
Figure 15
2
N
N
10
11
9
5
Br
Br
3
4
14
According to the general procedure using 3d (17.00 g, 26.46 mmol),
7b (17.31 g, 52.92 mmol, 2.00 equiv), CuI (1.08 g, 5.56 mmol, 0.21
equiv), 1,10-phenanthroline (1.93 g, 10.71 mmol, 0.40 equiv), and
KOH (11.87 g, 211.69 mmol, 8.00 equiv) with purification by recrys-
tallization (EtOAc) gave the product (Figure 15) as fine, colorless crys-
tals; yield: 20.49 g (19.69 mmol, 74%); mp 185.5 °C.
12
13
Figure 17
According to the general procedure using 3a (18.70 g, 41.80 mmol),
7d (31.40 g, 69.20 mmol, 2.30 equiv), CuI (804 mg, 4.22 mmol, 0.10
equiv), 1,10-phenanthroline (767 mg, 4.26 mmol, 0.010 equiv), and
KOH (21.50 g, 216 mmol, 7.80 equiv) with purification by column
chromatography (silica gel, cyclohexane/petroleum ether/Et2O) and
recrystallization (cyclohexane/n-hexane) gave the product (Figure
17) as colorless crystals; yield: 26.70 g (31.60 mmol, 76%); mp 239 °C
1H NMR (CDCl3, 500 MHz, 300 K): δ = 0.658 (m, 4 H, 13-H), 0.874 (t, 6
H, 19-H), 0.991–1.236 (m, 16 H, 14-H, 15-H, 16-H, 17-H), 1.269 (m,
4 H, 18-H), 1.772 (m, 4 H, 12-H), 6.964 (d, 8 H, 9-H), 6.983 (d, 2 H, 3-
H), 7.023 (s, 2 H, 1-H), 7.346 (d, 8 H, 10-H), 7.504 (d, 2 H, 4-H); 3J9,10
=
8.7 Hz.
13C NMR (CDCl3, 125 MHz, 300 K): δ = 14.30 (19-C), 22.80 (18-C),
24.10 (13-C), 29.41 (15-C or 16-C), 29.52 (15-C or 16-C), 30.09 (14-C),
31.96 (17-C), 40.17 (12-C), 55.35 (7-C), 115.37 (11-C), 119.69 (1-C),
120.36 (4-C), 123.97 (3-C), 125.23 (9-C), 132.44 (10-C), 136.88 (5-C),
145.86 (2-C), 146.81 (8-C), 152.57 (6-C).
1H NMR (CDCl3, 500 MHz, 303 K): δ = 1.376 (s, 6 H, 8-H), 6.970–7.060
(m, 2 H, 3-H), 7.090–7.180 (m, 6 H, 1-H, 13-H), 7.21–7.25 (m, 4 H, 10-
H), 7.562 (d, 2 H, 4-H), 6.970–7.060, 7.090–7.180 (m, 8 H, 12-H, 14-
H); 3J3,4 = 8.1 Hz.
13C NMR (CDCl3, 125 MHz, 303 K): δ = 26.91 (8-C), 46.99 (7-C), 119.58
(C-H), 120.65 (4-C), 122.18 (C-H), 122.95 (11-C), 124.37 (C-H), 125.90
(C-H), 126.46 (10-C), 128.77 (C-H), 130.55 (C-H), 135.04 (5-C), 145.68
(2-C), 148.83 (9-C), 155.48 (6-C).
HRMS (EI): m/z [M] calcd for
C53H56Br4N2: 1036.1172; found:
1036.1172.
Anal. Calcd for C53H56Br4N2: C, 61.17; H, 5.42; N, 2.69. Found: C, 61.18;
H, 5.49; N, 2.62.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–K

I
M. Hempe et al.
Paper
Synthesis
MS (EI): m/z (%) = 844 (100, [C39H28N2Br4]+), 764 (5, [C39H28N2Br3]+),
9,9-Dimethyl-N2,N2,N7,N7-tetrakis(4-vinylphenyl)-9H-fluorene-
2,7-diamine (4V-Methyl) (10b)
747 (4, [C38H25N2Br3]+).
HRMS (EI): m/z [M] calcd for C39H28N2Br4: 839.8985; found: 839.8992.
End-Functionalization by Suzuki–Miyaura Cross-Coupling; Gener-
al Procedure
8
1
6
7
In modification of the literature procedure,20 in a flame-dried flask
and under an argon atmosphere, a mixture of the halogenated precur-
sor molecule 8, potassium vinyltrifluoroborate (1.75 equiv,/halide),
Cs2CO3 (1.75 equiv/halide), Pd(OAc)2 (0.03 equiv/halide), and Ph3P
(0.09 equiv/halide) was suspended in a degassed mixture of THF (3.6
mL/mmol) and H2O (0.4 mL/mmol). Under vigorous stirring, the sus-
pension was heated to 90 °C until the reaction was complete. The
mixture was cooled to r.t., and then it was filtered through a pad of
silica gel and the solvent was removed in vacuo. The residue was puri-
fied by column chromatography (silica gel).
2
N
N
9
5
3
H14B
4
10
14
H14A
12
11
13
Figure 19
According to the general procedure, a mixture of 8b (2.02 g, 2.39
mmol), potassium vinyltrifluoroborate (2.57 g, 19.00 mmol, 7.95
equiv), Cs2CO3 (6.27 g, 19.22 mmol, 8.04 equiv), Pd(OAc)2 (60 mg, 0.27
mmol, 0.11 equiv), and Ph3P (198 mg, 0.75 mmol, 0.32 equiv) was
suspended in a degassed mixture of THF (45 mL) and H2O (5 mL). Pu-
rification by column chromatography (cyclohexane/petroleum
ether/Et2O, 1000:998:2) gave the product (Figure 19) as a yellow sol-
id; yield: 617 mg (0.98 mmol, 41%).
9,9-Dimethyl-N2,N7-diphenyl-N2,N7-bis(4-vinylphenyl)-9H-fluo-
rene-2,7-diamine (2V-Methyl) (10a)
12
1H NMR (CDCl3, 500 MHz, 300 K): δ = 1.364 (s, 6 H, 8-H), 5.183 (d, 4 H,
14A-H), 5.669 (d, 4 H, 14B-H), 6.689 (dd, 4 H, 13-H), 7.037 (d, 2 H, 3-
H), 7.087 (d, 8 H, 10-H), 7.176 (s, 2 H, 1-H), 7.317 (d, 8 H, 11-H), 7.513
11
10
8
1
6
9
7
2
N
N
4
3
3
3
13
5
(d, 2 H, 4-H); J1,3 = 1.8 Hz, J3,4 = 8.2 Hz, J10,11 = 8.2 Hz, J13,14A = 10.8
3
H18B
4
14
Hz, 3J13,14B = 17.4 Hz, 2J14A,14B = 0.6 Hz.
16
17
18
H18A
15
13C NMR (CDCl3, 125 MHz, 300 K): δ = 27.12 (8-C), 47.01 (7-C), 112.34
(14-C), 119.18 (1-C), 123.84 (10, 3-C), 127.22 (11-C), 132.17 (12-C),
134.46 (5-C), 136.36 (13-C), 146.35 (2-C), 147.51 (9-C), 155.27 (6-C).
Figure 18
MS (EI): m/z (%) = 632 (100, [M]+), 605 (20, C45H37N2).
According to the general procedure, a mixture of 8a (6.00 g, 8.74
mmol), potassium vinyltrifluoroborate (4.10 g, 30.59 mmol, 3.50
equiv), Cs2CO3 (9.97 g, 30.59 mmol, 3.50 equiv), Pd(OAc)2 (118 mg,
0.52 mmol, 0.06 equiv), and Ph3P (413 mg, 1.57 mmol, 0.18 equiv)
were suspended in a degassed mixture of THF (31.5 mL) and H2O
(3.50 mL). Purification by column chromatography gave the product
(Figure 18) as a yellow glass; yield: 1.70 g (2.93 mmol, 34%).
HRMS (EI): m/z [M] calcd for C47H40N2: 632.3192; found: 632.3207.
9,9-Dibutyl-N2,N2,N7,N7-tetrakis(4-vinylphenyl)-9H-fluorene-2,7-
diamine (4V-Butyl) (10c)
H13A
17
16
13
H13B
12
1H NMR (CDCl3, 500 MHz, 300 K): δ = 1.255 (s, 6 H, 8-H), 5.066 (d, 2 H,
18A-H), 5.552 (d, 2 H, 18B-H), 6.581 (dd, 2 H, 17-H), 6.923 (d, 2 H, 3-
H), 6.935 (t, 2 H, 12-H), 6.973 (d, 4 H, 14-H), 7.042 (d, 4 H, 10-H),
7.069 (s, 2 H, 1-H), 7.163 (t, 4 H, 11-H), 7.206 (d, 4 H, 15-H), 7.403 (d,
2 H, 4-H); 3J3,4 = 8.0 Hz, 3J14,15 = 8.5 Hz, 3J17,18A = 10.9 Hz, 3J17,18B = 17.6
Hz, 2J18A,18B = 0.6 Hz.
11
9
15
14
10
1
6
8
7
2
3
N
N
5
4
13C NMR (CDCl3, 125 MHz, 300 K): δ = 27.15 (8-C), 46.99 (7-C), 112.19
(18-C), 119.1 (1-C), 120.23 (4-C), 122.94 (12-C), 123.57 (14-C), 123.86
(3-C), 124.36 (10-C), 127.21 (15-C), 129.38 (11-C), 131.90 (16-C),
134.36 (5-C), 136.43 (17-C), 146.59 (2-C), 147.83 (13-C), 147.94 (9-C),
155.25 (6-C).
Figure 20
According to the general procedure, a mixture of 8c (8.00 g, 8.62
mmol), potassium vinyltrifluoroborate (8.08 g, 60.32 mmol, 7.00
equiv), Cs2CO3 (19.65 g, 60.32 mmol, 7.00 equiv), Pd(OAc)2 (193 mg,
0.86 mmol, 0.10 equiv), and Ph3P (678 mg, 2.59 mmol, 0.30 equiv)
was suspended in a degassed mixture of THF (38.8 mL) and H2O (4.31
mL). Purification by column chromatography gave the product (Figure
20) as a yellow solid; yield: 1.10 g (1.53 mmol, 18%).
MS (EI): m/z (%) = 580 (100, [M]+]), 554 (15, [M – (C2H3)]+), 371 (5, [M
– N(C6H5)(C8H7) – (CH3)]+).
HRMS (EI): m/z [M] calcd for C43H36N2: 580.2879; found: 580.2832.
Anal. Calcd for C43H36N2: C, 88.93; H, 6.25; N, 4.82. Found: C, 88.49; H,
6.30; N, 4.58.
1H NMR (CDCl3, 500 MHz, 300 K): δ = 0.651 (m, 4 H, 15-H), 0.743 (t, 6
H, 17-H), 1.048–1.137 (m, 4 H, 16-H), 1.784 (m, 4 H, 14-H), 5.178 (d, 4
H, 13A-H), 5.660 (d, 4 H, 13B-H), 6.686 (dd, 4 H, 12-H), 7.029 (d, 2 H,
4-H), 7.081 (d, 8 H, 9-H), 7.094 (s, 2 H, 1-H), 7.305 (d, 8 H, 10-H),
7.501 (d, 2 H, 3-H); 3J3,4 = 8.2 Hz, 3J9,10 = 8.6 Hz, 3J12,13A = 10.8 Hz, 3J12,13B
= 17.54 Hz, 2J13A,13B = 0.9 Hz.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–K

J
M. Hempe et al.
Paper
Synthesis
13C NMR (CDCl3, 125 MHz, 300 K): δ = 14.09 (17-C), 23.10 (16-C),
24.01 (13-C), 26.31 (15-C), 30.50 (14-C), 39.87 (12-C), 55.17 (7-C),
112.31 (13-C), 119.78 (1-C), 120.03 (3-C), 123.67 (9-C), 123.98 (4-C),
127.19 (10-C), 132.11 (11-C), 136.39 (12-C), 136.65 (5-C), 146.19 (2-
C), 147.52 (8-C), 152.31 (6-C).
was suspended in a degassed mixture of THF (48 mL) and H2O (5.3
mL). Purification by column chromatography gave the product (Figure
22) as an off-white solid; yield: 4.05 g (6.40 mmol, 60%).
1H NMR (CDCl3, 500 MHz, 303 K): δ = 1.360 (s, 6 H, 8-H), 5.193 (d, 4 H,
16A-H), 5.645 (d, 4 H, 16B-H), 6.624 (dd, 4 H, 15-H), 6.97–7.30 (m, 20
MS (EI): m/z (%) = 716 (60, [M]+]), 690 (10, [M – C2H3]+), 220 (30,
H, 3-H, 4-H, 10-H, 12-H, 13-H, 14-H), 7.518 (br, 2 H, 1-H); J15,16B
=
3
[N(C8H7)2]+).
17.1 Hz, 3J15,16A = 10.7 Hz.
13C NMR (CDCl3, 125 MHz, 303 K): δ = 26.96 (8-C), 46.82 (7-C), 114.03
(16-C), 120.08 (1- C), 134.13 (5-C), 136.37 (15-C), 138.75 (11-C),
146.51 (2-C), 148.11 (9-C), 155.05 (6-C), 118.83, 120.47, 121.81,
123.57, and 129.33 (3-C, 4-C, 10-C, 12-C, 13-C, 14-C).
9,9-Dimethyl-N2,N7-diphenyl-N2,N7-bis(3-vinylphenyl)-9H-fluo-
rene-2,7-diamine (m2V-Methyl) (10f)
18
17
MS (EI): m/z (%) = 632 (100, [C47H40N2]+), 617 (5, [C26H37N2]+), 605 (3,
[C45H38N2]+), 397 (3, [C30H23N]+), 28 (14, [C2H4]+).
8
16
20BH
1
15
6
HRMS (EI): m/z [M] calcd for C47H40N2: 632.3192; found: 632.3219.
7
H20A
20
2
N
N
10
Anal. Calcd for C47H40N2: C, 89.20; H, 6.37; N, 4.43. Found: C, 88.92; H,
6.50; N, 4.09.
9
5
19
3
11
12
4
14
13
Figure 21
Acknowledgment
According to the general procedure, a mixture of 8f (6.00 g, 8.74
mmol), potassium vinyltrifluoroborate (4.11 g, 30.60 mmol, 3.50
equiv), Cs2CO3 (9.97 g, 30.60 mmol, 3.50 equiv), Pd(OAc)2 (118 mg,
0.52 mmol, 0.06 equiv), and Ph3P (413 mg, 1.57 mmol, 0.18 equiv)
was suspended in a degassed mixture of THF (31.5 mL) and H2O (3.5
mL). Purification by column chromatography gave the product (Figure
21) as an off-white solid; yield: 3.48 g (5.99 mmol, 68%).
The authors would like to thank Christian Rüttiger (Rehahn group,
TU-Darmstadt) for conducting the DSC measurements. We gratefully
acknowledge financial support from Merck KGaA, Darmstadt.
Supporting Information
Supporting information for this article is available online at
1H NMR (CDCl3, 500 MHz, 303 K): δ = 1.352 (s, 6 H, 8-H), 5.188 (dd, 2
H, 20A-H), 5.636 (dd, 2 H, 20B-H), 6.618 (dd, 2 H, 19-H), 6.98–7.29
(m, 22 H, 1-H, 3-H, 16-H, 17-H, 18-H, 10-H, 12-H, 13-H, 14-H), 7.503
https://doi.org/10.1055/s-0036-1590824.
S
u
p
p
ortiInfogrmoaitn
S
u
p
p
o
nrtogI
f
rmoaitn
(d, 2 H, 4-H); 3J3,4 = 7.9 Hz, 3J19,20B = 17.5 Hz, 3J19,20A = 10.9 Hz, 2J20A,20B
=
References
0.6 Hz.
13C NMR (CDCl3, 125 MHz, 303 K): δ = 26.98 (8-C), 46.81 (7-C), 113.98
(20-C), 120.04 (4- C), 134.10 (5-C), 136.69 (19-C), 138.71 (11-C),
146.58 (2-C), 155.04 (6-C), 118.85, 120.34, 121.69, 122.60, 123.38,
123.58, 124.02, 129.20, and 129.29 (1-C, 3-C, 10-C, 12-C, 13-C, 14-C,
16-C, 17 C, 18-C), 147.92 and 148.30 (9-C, 15-C).
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