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Synthesis 1996; 1996(1): 59-63
DOI: 10.1055/s-1996-4178
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The Reaction of Halogeno-Substituted N,N-Dimethylanalines and Polycyclic Aromatic Hydrocarbons with Certain Arylacetonitriles or α-Cyano-o-tolunitrile Under Aryne-Forming Conditions

Wei Han, Yingchun Lu, He Zhao, Mahesh Dutt, Edward R. Biehl*
  • *Department of Chemistry, Southern Methodist University, Dallas, Texas 75275, USA, Fax +1(214)7684089
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Publication Date:
31 December 2000 (online)

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The scope of the tandem addition-rearrangement aryne reaction has been extended to include 2-bromo-4-methyl-N,N-dimethylaniline (1) and 6-bromo-5-methoxyindan (4). These haloarenes react with arylacetonitriles 2 under lithium diisopropylamide mediated aryne-forming conditions to give primarily 2-arylmethyl-3-methyl-6-N,N-dimethylaminobenzonitriles 3 and 4-arylmethyl-6-methoxyindan-5-carbonitriles 5, respectively. 9-Bromophenanthrene (14), and 4-bromopyrene (16) react with α-cyano-o-tolunitrile (8) to give mainly rearranged products 2-(2’-cyanobenzyl)-3-methyl-6-N,N-dimethylaminobenzonitrile (9), 10-(2’-cyanobenzyl)phenanthrene-9-carbonitrile (15), and 5-(2’-cyanobenzyl)pyrene-4-carbonitrile (17). However, compound 8 reacts with 3-chloro-N,N-dimethylaniline (10), 4-bromopyrene (16) and 6-bromo-5-[(4-tolylsulfonyl)-oxy]indan (6) to give 4+2 cycloaddition products 10-amino-1-N,N-dimethylaminoanthracene-9-carbonitrile (11), 6-amino-5-methoxy-2,3-dihydro-1H-cyclopent(a)anthracene-11-carbonitrile (12), and 10-amino-2,3-dihydro-1H-cyclopent(b)-anthracene-5-carbonitrile (13), respectively. The reaction of indan 6 with arylacetonitriles 2 and butyllithium affords no arynic products, but rather yields α-(4-tolylsulfonyl)arylacetonitriles 7. These results are discussed in terms of electronic effects.

aryne - tandem addition-rearrangement - cycloaddition - nucleophilic addition