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DOI: 10.1055/s-2007-986657
1-Methylimidazole-Catalyzed Regioselective Synthesis of Highly Substituted Benzenes
Publikationsverlauf
Publikationsdatum:
12. September 2007 (online)
Abstract
A novel 1-methylimidazole-catalyzed synthesis of 4-amino-3,5-dicyano-6-arylphthalates is described. A one-pot, three-component reaction between arylidenemalononitriles, dialkyl acetylenedicarboxylates, and malononitrile gave highly substituted benzenes in good to excellent yields.
Key words
multicomponent reactions - regioselective synthesis - ring closure - 4-amino-3,5-dicyano-6-arylphthalates - 1-methylimidazole - catalysis
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References and Notes
Preparation of Dimethyl 4-Amino-3,5-dicyano-6-phenylphthalate (3a) - General Procedure
To a solution of benzylidenemalononitrile (0.308 g, 2 mmol) and 1-methylimidazole (0.033 g, 0.4 mmol) in anhydrous CH2Cl2 (4 mL) was added dropwise a solution of dimethyl acetylenedicarboxylate (0.284 g, 2 mmol) in anhydrous CH2Cl2 (2 mL) at -10 °C over 5 min, and was stirred at 25 °C for 25 min. Then, a solution of malononitrile (0.132 g, 2 mmol) in anhydrous CH2Cl2 (1 mL) was added to the reaction mixture and was stirred at 25 °C for 2 h (progress of the reaction followed by TLC monitoring). Afterwards, the solvent was removed and the residue was purified with column chromatography [n-hexane-EtOAc (4:1) as eluent]. The product 3a was obtained as colorless crystals; yield 0.64 g (95%). IR (KBr): 3435, 3340 and 3245 (NH), 2190 (CN), 1732 (C=O) cm-1. 1H NMR (500.1 MHz, CDCl3): δ = 3.50 and 3.99 (2 × s, 6 H, 2 × OCH3), 5.61 (br s, 2 H, NH2), 7.29-7.32 (m, 2 H, 2 × CH), 7.46-7.49 (m, 3 H, 3 × CH). 13C NMR (125.8 MHz, CDCl3): δ = 53.20 and 54.26 (2 × OCH3), 95.89 and 101.15 (2 × CN), 114.28, 114.67, and 124.40 (3 × C), 128.64, 129.24, and 130.41 (3 × CH), 135.95, 139.24, 150.65, and 152.80 (4 × C), 164.89 and 166.26 (2 × C=O). MS: m/z (%) = 335 (40) [M+], 304(84), 272 (20), 245 (12), 217 (35), 189 (42), 163 (32), 77 (40), 59 (100), 57 (36), 39 (36). Anal. Calcd (%) for C18H13N3O4 (335.32): C, 64.48; H, 3.91; N, 12.53. Found: C, 64.4; H, 4.0; N, 12.4.
Compound 3c: colorless crystals; yield 0.62 g (85%). IR (KBr): 3430, 3340, and 3245 (NH), 2190 (CN), 1732 (C=O) cm-1. 1H NMR (300.1 MHz, CDCl3): δ = 3.55, 3.86, and 3.99 (3 × s, 9 H, 3 × OCH3), 5.58 (br s, 2 H, NH2), 6.99 (d, J = 8.8 Hz, 2 H, 2 × CH), 7.26 (d, J = 8.8 Hz, 2 H, 2 × CH). 13C NMR (75.5 MHz, CDCl3): δ = 52.70, 53.65, and 55.31 (3 × OCH3), 94.84 and 100.98 (2 × CN), 113.81 (C), 114.15 (CH), 114.37, 124.05, and 127.33 (3 × C), 129.62 (CH), 138.20, 149.81, and 152.23 (3 × C), 160.76 (C-O), 164.30 and 165.96 (2 × C=O). MS: m/z (%) = 365 (61) [M+], 334 (39), 302 (32), 274 (19), 246 (21), 204 (52), 177 (21), 101 (86), 86 (99), 58 (100). Anal. Calcd (%) for C19H15N3O5 (365.35): C, 62.46; H, 4.14; N, 11.50. Found: C, 62.4; H, 4.3; N, 11.4.
Compound 3h: colorless crystals; yield 0.75 g (95%). IR (KBr): 3450, 3350, and 3200 (NH), 2190 (CN), 1722 (C=O) cm-1. 1H NMR (300.1 MHz, CDCl3): δ = 0.96 and 1.40 (2 × t, J = 7.1 Hz, 6 H, 2 × OCH2CH
3), 3.98 and 4.45 (2 × q, J = 7.1 Hz, 4 H, 2 × OCH
2CH3), 5.71 (br s, 2 H, NH2), 7.25 (d, J = 8.5 Hz, 2 H, 2 × CH), 7.45 (d, J = 8.5 Hz, 2 H, 2 × CH). 13C NMR (75.5 MHz, CDCl3): δ = 13.39 and 13.72 (2 OCH2
CH3), 61.98 and 63.37 (2 × OCH2CH3), 95.46 and 99.97 (2 × CN), 113.54, 113.96, and 123.35 (3 × C), 128.87 and 129.53 (2 × CH), 133.92, 136.00, 139.37, 148.72, and 152.29 (5 × C), 163.84 and 164.94 (2 × C=O). MS: m/z (%) = 399 (16) [M+ + 2], 397 (36) [M+], 352 (18), 324 (98), 252 (42), 217 (39), 189 (52), 163 (10), 97 (12), 83 (19), 69 (41), 57 (58), 43 (100). Anal. Calcd (%) for C20H16ClN3O4 (397.82): C, 60.38; H, 4.05; N, 10.56. Found: C, 60.4; H, 4.2; N, 10.4.
Selected X-ray Crystallographic Data for Compound 3a
C18H13N3O4, M = 335.31, triclinic, space group P1, final R indices [I > 2σ(I)], R1 = 0.0396, wR2 = 0.1208, R indices (all data) R1 = 0.0512, wR2 = 0.1248, a = 7.8994(6) Å, b = 9.8692(7) Å, c = 11.7832(10) Å, α = 108.772(7)°, β = 96.067(7)°, γ = 102.822(7)°, V = 832.32(11)Å3, T = 290(2) K, Z = 2, reflections collected/unique: 12943/3994 (R
int = 0.0421), number of observations [>2σ(I)] 3015, parameters: 255. CCDC 638396 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.