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2N group into a very strong acceptor, which would deactivate the aromatic ring toward electrophilic substitutions. However, there is always some free amine in equilibrium with an ammonium cation.
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The synthesis of (±)-2e was very recently reported by Lützen and co-workers, Ref. 9. We thank Prof. A. Lützen and Dr. U. Kiehne for the helpful discussion concerning the variation of conditions in this reaction.
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69
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44349115614
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note
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3COOH in one portion without cooling resulted in an exothermic reaction that produced a tarry, dark material and only traces of the desired Tröger's base analogue.
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70
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44349146702
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note
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Di- or tetramethyl derivatives (±)-3c-f should be more reactive toward electrophilic substitution than (±)-1b. In a preliminary experiment, we confirmed a much higher reactivity of (±)-3c compared to (±)-1b in the electrophilic bromination. This study is currently in progress and will be published in due course.
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