Abstract
Heating activated halobenzenes with 1,1,3,3-tetramethylguanidine affords mixtures of dimethylaminobenzenes and 2-aryl-1,1,3,3-tetramethylguanidines.
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Typical experimental procedure: A solution of 2-chloro-5-nitrobenzotrifluoride (4.5 mmol) in TMG (10 cm3) was stirred at RT for 30 minutes, and then gradually heated to 100°C, and maintained at this temperature until TLC indicated that no aromatic halide remained. The mixture was cooled to room temperature, and then poured into water (200 cm3), and then partially neutralised with HCl (2M aq.). The resulting solution was extracted with EtOAc (4 × 30 cm3). The combined extracts were washed with water (2 × 50 cm3), dried, and evaporated to afford the crude product. Elution from silica with 40% EtOAc in hexane gave two fractions. Fraction 1; 2-dimethylamino-5-nitrobenzotrifluoride (18%) as a bright orange solid, m.p. 44-45°C [lit m.p. 44.5–45°C23], and Fraction 2; 2-(4-nitro-2-trifluoromethylphenyl)-1,1,3,3-tetramethylguanidine (58%) as bright yellow cubes from hexane, and EtOAc, m.p. 94–95°C, δH 2.80 (12H, s, 2(NMe2)), 6.36 (1H, d, J 9.0, 6-H), 8.13 (1H, dd, J 9.0, 2.7, 5-H), 8.44 (1H, d, J 2.7, 3-H), (Found: MH+, 305.1227; C, 47.3; H, 5.0; N, 18.2. C12H15F3N4O2 requires MH+, 305.1225(3); C, 47.4; H, 5.0; N, 18.4%).
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