THE REACTION OF HALOGENO-SUBSTITUTED N,N-DIMETHYLANALINES AND POLYCYCLIC AROMATIC-HYDROCARBONS WITH CERTAIN ARYLACETONITRILES OR ALPHA-CYANO-O-TOLUNITRILE UNDER ARYNE-FORMING CONDITIONS

The scope of the tandem addition-rearrangement aryne reaction has been extended to include 2-bromo-4-methyl-N,N-dimethylaniline (1) and 6-br omo-5-methoxyindan (4). These haloarenes react with arylacetonitriles 2 under lithium diisopropylamide mediated aryne-forming conditions to give primarily ylmethyl-3-methyl-6-N,N-dimethylaminobenzonitriles 3 an d 4-arylmethyl-6-methoxyindan-5-carbonitriles 5, respectively. 9-Bromo phenanthrene (14), and 4-bromopyrene (16) react with alpha-cyano-o-tol unitrile (8) to give mainly rearranged products, nobenzyl)-3-methyl-6- N,N-dimethylaminobenzonitrile (9), 10-(2'-cyanobenzyl)phenanthrene-9-c arbonitrile (15), and 5-(2'-cyanobenzyl)pyrene-4-carbonitrile (17). Ho wever, compound 8 reacts with 3-chloro-N,N-dimethylaniline (10), 4-bro mopyrene (16) and 6-bromo-5-[(4-tolylsulfonyl)-oxy]indan (6) to give 4 + 2 cycloaddition products amino-1-N,N-dimethylaminoanthracene-9-carb onitrile (11), -dihydro-1H-cyclopent(a)anthracene-11-carbonitrile (12) , and 3-dihydro-1H-cyclopent(b)anthracene-5-carbonitrile (13), respect ively. The reaction of indan 6 with arylacetonitriles 2 and butyllithi um affords no arynic products, but rather yields alpha-(4-tolylsulfony l)arylacetonitriles 7. These results are discussed in terms of electro nic effects.