10.1002/ejoc.201900411
European Journal of Organic Chemistry
FULL PAPER
General procedure for the chlorination of electron rich arenes
[8]
[9]
4CzIPN = 2,4,5,6-Tetra(9H-carbazol-9-yl)isophthalonitrile. The catalyst
is depicted in Table 2.
A 5 mL glass crimp vial was charged with 0.1 mmol of the respective
substrate, 4CzIPN (1.6 mg, 2 mol%), MeCN (0.5 mL) and 27.4 µL of a
freshly prepared mixture of aqueous HCl and HBr (0.3 mmol, 3.0 eq. and
0.01 mmol, 0.1 eq.). The vial was closed with a septum and flushed two
times with oxygen from a balloon connected to a syringe needle. The
reaction vial was placed into a custom-built cooling system (pictures
provided in the SI) at 25 °C and irradiated under stirring by two 451 nm
LEDs through the bottom side (ca. 5 mm distance to the LEDs). The
reaction progress was monitored by TLC or GC-FID and the reaction was
stopped after 0.5 - 3.5 h, when all starting material was consumed, or no
further progress was detected. To obtain an average result, two reaction
mixtures were united and the solvent was removed under reduced
pressure after the addition of silica gel. The products were purified by
automated silica gel flash column chromatography with a mixture of petrol
ether and ethyl acetate as eluent.
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Acknowledgments
This work was financially supported by the German Science
Foundation (DFG, GRK 1626, Chemical Photocatalysis).
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up to 2.3 V vs SCE) was used as catalyst for the photocatalytic
bromination. Please see reference [6].
Keywords: Chlorination • photoredox catalysis • oxidation •
ipso-substitution • chloroarene
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