European Journal of Organic Chemistry
10.1002/ejoc.201901868
FULL PAPER
1
In a well dried Schlenk flask, a solution of potassium tert-butoxide (16.7g,
2
H NMR (300 MHz, [D ]tetrachloroethane): 5.00 (s, 2H), 7.45 – 7.51 (m,
0
.149 mol, 5 equiv.) in anhydrous DMF (100 mL) was cooled to 0°C. To
this solution was added dropwise a solution of the tetrachloride 10a/b
10.4 g, 29.7 mmol) in anhydrous DMF (20 mL). After the complete
4H), 7.80 – 7.85 (m, 4H), 7.95 (s, 4H).
(
addition, the reaction mixture was warmed to room temperature and
finally heated at 50°C overnight under argon. The reaction mixture was
diluted with water and extracted with EtOAc. The combined organic
Acknowledgments
portions were dried over anhydrous MgSO
in vacuum and the residue was chromatographed on silica gel (gradient
from hexane/dichloromethane 6:1 to 2:1) to get the desired product 1
4
. The solvents were removed
The authors thank Yannick Coppel (LCC-Toulouse) for recording
CP-MAS spectra, David Neumeyer (CEMES) for recording TGA
spectra. A. J. acknowledges funding from the Foundation
EXPERIENTIA and from ERDF/ESF "UOCHB MSCA Mobility"
1
(
3.7g, 61 %) as a white crystalline compound. H NMR is in agreement
[
25]
with the published data.
(
No. CZ.02.2.69/0.0/0.0/17_050/0008490). This research has
1
been funded by the EraNET Cofund Initiatives QuantERA under
the European Union's Horizon 2020 research and innovation
programme grant agreement ORQUID and by the ANR-MOST
project MQwires.
3
H NMR (300 MHz, CDCl ): 3.27 (s, 6H), 3.47 (s, 2H), 5.01 (s, 4H), 5.30
(s, 4H).
13
3
C NMR (75 MHz, CDCl ): 50.90, 58.52, 103.47, 110.85, 146.65.
+
CI MS: 205 ([M+H] ).
Keywords: tetraene • cycloaddition • ozonolysis • protecting
group • carboxylation
17 2
HR CI MS: calcd for C13H O 205.1229; found 205.1230
1
5,15-dimethoxy-6,13-dihydro-6,13-methanopentacene (11)
[
[
1]
2]
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A well dried Schlenk flask was charged with tetraene 1 (500 mg, 2.45
mmol, 1 equiv.) and dry CsF (1.49 g, 9.79 mmol, 4 equiv.) under argon
and then anhydrous acetonitrile was added (50 mL). The reaction mixture
7
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cooled
to
0°C
and
then
2-(trimethylsilyl)phenyl
[
5]
[6]
7]
trifluoromethanesulfonate (1.3 mL, 5.39 mmol, 2.2 equiv.) was added
dropwise. The mixture was stirred at room temperature overnight. After
evaporation of the solvent, the residue was filtered over short plug of
silica gel and flushed with hexane/THF 20:1. Rotoevaporation of the
organic solvents gave the crude product which was well dried under
vacuum and then dissolved in anhydrous toluene (40 mL) under argon.
This solution was cooled to 0°C and DDQ (1.11 g, 4.9 mmol, 2 equiv.)
was added in one portion. The reaction mixture was warmed to room
temperature and stirred for 3 h. After filtration to remove reduce DDQ,
evaporation of solvents gave a residue which was chromatographed on
silica gel (hexane/dichloromethane 2:3) to get the product 11 (751 mg,
7
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H NMR (300 MHz, CDCl
m, 8H).
3
): 3.22 (s, 6H), 7.35 – 7.41 (m, 4H), 4.69 – 7.75
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[
[
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1
3
C NMR (75 MHz, CDCl
3
): 51.54, 55.32, 120.88, 125.49, 125.99, 128.17,
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1
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+
DCI MS: 353 ([M + H] ).
HR DCI MS: calcd for C25
21 2
H O 353.1536; found 353.1529.
[
[
6
,13-dihydro-6,13-methanopentacen-15-one (12)
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In a well-dried Schlenk flask, 11 was dissolved (140 mg, 0.4 mmol) in
anhydrous dichloromethane (15 mL) under argon. Then trimethylsilyl
iodide (68 μL, 0.48 mmol, 1.2 equiv) was added dropwise and reaction
mixture was stirred overnight at room temperature. The reaction mixture
was then heated at 40°C for 1 h, then cooled to room temperature and
rotoevaporated. Sonication of the residue in a mixture of solvents
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(
hexane/diethyl ether 4:1) yielded pure product 12 (106 mg, 87 %) as a
[
1
[33]
white powder. H NMR is in agreement with published data.
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