2-[(3-METHOXYANILINO)METHYLENE]-5,5-DIMETHYL-1,3-CYCLOHEXANEDIONE synthesis

Yield:64869-19-8 90%

Reaction Conditions:

Heating;

Steps:

2.1 Synthesis

Enaminone derivative, 2-(((3-methoxyphenyl)amino)methylene)-5,5-dimethylcyclohexane-1,3-dione (HL), was synthesized by heating slowly with stirring a mixture of dimedone (7.1mmol, 1.0g,), 3-methoxyaniline (7.1mmol, 0.88g) and excess of triethylorthoformate (9.0mmol, 1.5ml, 0.891g/ml) until homogenization. After boiling for 3-4min, the melt was cooled and treated with n-BuOH (10ml). The solid was filtered off, washed with cold EtOH and light petroleum, as well as dried at 70°C as a result giving analytically pure target product as light yellow powder. Yield: 1.75g (90%). (0005) ¹H NMR (500MHz, CDCl₃) δ 1.07 (s, 6H, CH₃), 2.39 (s, 2H, 4-CH₂), 2.44 (s, 2H, 6-CH₂), 3.81 (s, 3H, O-CH₃), 6.75 (s, 1H, 2′-CH), 6.75-6.78 (m, 1H, 4′-CH), 6.80-6.86 (m, 1H, 6′-CH), 7.25-7.31 (m, 1H, 5′-CH), 8.56 (d, 1H, J=13.7Hz, 2-CH), 12.81 (br. d, 1H, NH). (0006) ¹³C NMR (126MHz, CDCl₃) δ 28.72 (CH₃), 31.29 (5-C), 51.50 (4-C), 51.86 (6-C), 55.69 (O-CH₃), 104.08 (2′-C), 109.05 (1-C), 110.56 (6′-C), 112.37 (4′-C), 130.96 (5′-C), 139.82 (1′-C), 150.54 (2-C), 161.14 (3′-C), 196.38 (3-C; ²J_CH=6,2 Hz, ³J_cis-CH, = 3.3Hz), 200.10 (7-C; ²J_CH = ³J_trans-CH, = 6.6Hz). ¹⁵N NMR (51MHz, HCONH₂) δ 141.2 (¹J_NH=88Hz).

References:

Smirnova;Ivanova;Eltsov;Pozdnyakov;Russkikh;Dotsenko;Lider [Polyhedron,2022,vol. 227,art. no. 116122]