A novel type of nucleophilic substitution reactions on nonactivated aromatic compounds and benzene itself with trimethylsiliconide anions.
[reaction: see text]. The reaction of fluorobenzene with Me3Si- anion (1) in HMPA at room temperature surprisingly affords o- and p-fluorotrimethylsilylbenzenes (substitution of aromatic H for TMS, 76% yield) 7a and 7b and also 14% of trimethylsilylbenzene (2). Benzene itself reacts at 50 degrees C to furnish 4 in 45% yield. Pyridine affords p-trimethylsilylpyridine quantitatively. Mechanistic studies are presented.
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INFIQC, Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Córdoba 5000, Argentina.
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D000838:Anions; D001554:Benzene / Q000737:chemistry*; D005464:Fluorobenzenes / Q000737:chemistry; D006492:Hempa / Q000737:chemistry; D008956:Models, Chemical; D009578:Nitrobenzenes / Q000737:chemistry; D012825:Silicon / Q000737:chemistry*; D013696:Temperature; D013997:Time Factors
D000838:Anions; D005464:Fluorobenzenes; D009578:Nitrobenzenes; D001554:Benzene; D006492:Hempa; D012825:Silicon