The Synthesis of Various 2-Imino-2H-chromene-3-carbonitrile Derivatives †
Abstract
:1. Introduction
2. Results and Discussion
3. Experimental
3.1. General Information, Instrumentation, and Chemicals
3.2. Synthesis and Characterization of the Compounds
- 2-(4,5-diamino-1-cyano-2H-chromeno[3,4-c]pyridin-2-ylidene)malononitrile 3a and 2-(4-amino-1-cyano-5-imino-1,3,5,10b-tetrahydro-2H-chromeno[3,4-c]pyridin-2-ylidene)malononitrile 3a′
- (A) Equimolar amounts of malononitrile (0.13 g, 0.002 mol) and salicylic aldehyde (0.002 mol) were refluxed in dioxane for 6 h. The beige crystals that precipitated were filtered off, washed with hexane, and dried in desiccators. (B) 2a (0.3 g) was stirred in IPA at 60 °C for 1 h. The beige crystals that precipitated were filtered off, washed with hexane, and dried in desiccators. (C) 2a (0.3 g) was stirred in dioxane in an ultrasonic bath at room temperature for 1 h. The crystals that precipitated were filtered off, washed with hexane, and dried in desiccators.
- M.p. = 287–288 °C. Found, %; C, 62.37; H, 3.11; N, 27.46. C16H10N6O. Calculated, %: C, 63.57; H, 3.33; N, 27.80; O, 5.29. beige crystals. 1H NMR (CDCl3), δ, ppm: (3a): 4.83 (H1, d, 1H. J = 3.6 Hz), 4.91 (H10b, d, 1H. J = 3.6 Hz), 6.69 (-NH2, s, 2H), 7.08 (-NH2, s, 2H), 7.20 (H7, d, 1H. J = 8 Hz), 7.23–7.28 (H8-H10, m, 3H). (3a’): 4.58 (H1, d, 1H. J = 3.6 Hz), 5.05 (H10b, d, 1H. J = 3.6 Hz), 7.12 (H7, d, 1H. J = 8 Hz), 7.41 (H8-H9, t, 2H. J = 8 Hz), 7.46 (H10, d, 1H. J = 8 Hz), 7.51 (-NH2, s, 2H), 8.37 (=NH, s, 1H), 8.85 (=NH, s, 1H). Yield: 70% (A), 86% (B), 87% (C).
- 2-(4,5-diamino-9-bromo-1-cyano-2H-chromeno[3,4-c]pyridin-2-ylidene)malononitrile 3b and 2-(4-amino-9-bromo-1-cyano-5-imino-1,3,5,10b-tetrahydro-2H-chromeno[3,4-c]pyridin-2-ylidene)malononitrile 3b′
- (A) Equimolar amounts of malononitrile (0.13 g, 0.002 mol) and salicylic aldehyde (0.002 mol) were refluxed in IPA in the presence of Et3N (3 drops) for 6 h. The brown crystals that precipitated were filtered off, washed with hexane, and dried in desiccators. (B) 2b (0.35 g) in IPA was refluxed for 4 h. After cooling, the crystalline solid was filtered off, washed with hexane, and dried in desiccators. (C) 2b (0.3 g) was stirred in dioxane in ultrasonic bath at room temperature for 2 h. Brown crystals that precipitated were filtered off, washed with hexane, and dried in desiccators.
- M.p. = 280–282 °C. Brown crystals. Calculated, %: C, 50.41; H, 2.38; Br, 20.96; N, 22.05; O, 4.20. C16H9BrN6O. Found, %: C, 50.47; H, 2.87; N, 22.52. 1H NMR (DMSO-d6), δ, ppm: 4.8–4.9 (H1-H10b, dd, 2H. J = 4 Hz) (3b): 7.1 (=NH, s, 1H), 6.72 (-NH2, s, 2H), 7.64–7.61 (H8, d, 1H. J = 8 Hz), 7.5 (H10, s, 1H), 7.21–7.19 (H7, d, 1H. J = 8 Hz); (3b’): 3.65 (=NH, s, 1H), 6.34 (=NH, s, 1H), 6.53 (=NH, s, 1H), 6.97–6.95 (H7, d, 1H. J = 8 Hz), 7.38–7.35 (H8, d, 1H. J = 8 Hz), 7.29 (H10, s, 1H). Yield: 76% (A), 78% (B), 85% (C).
- 2-(4-amino-1-cyano-5-imino-3,5-dihydro-2H-chromeno[3,4-c]pyridin-2-ylidene)malononitrile 4a
- (A) Equimolar amounts of malononitrile (0.13 g, 0.002 mol) and salicylic aldehyde (0.002 mol) were stirred in H2O-PEG-400 solution at 40 °C for 4 h The orange-brown crystals that precipitated were filtered off, washed with hexane, and dried in air. (B) 2a (0.35 g) in IPA was refluxed for 4 h. After cooling, the crystalline solid was filtered off and dried in air.
- M.p. = 250–252 °C. Orange-brown crystals. Calculated, %: C, 64.00; H, 2.69; N, 27.99; O, 5.33. C16H8N6O. Found, %: C, 63.76.00; H, 2.99; N, 28.05. 1H NMR (DMSO-d6), δ, ppm: 3.65 (=NH, s, 1H), 6.31 (=NH, s, 2H), 6.50 (-NH2, s, 2H), 6.98 (H10, d, 1H. J = 8 Hz), 7.06 (H9, t, 1H. J = 8 Hz), 7.54 (H7, d, 1H. J = 8 Hz), 7.79 (H8, t, 1H. J = 8 Hz). 1H/13C HSQC (DMSO-d6), δ, ppm: 6.98/116.74 (H10/C10), 7.06/124.23 (H9/C9), 7.54/125.79 (H7/C7), 7.79/134.80 (H8/C8). 1H/13C HMBC (DMSO-d6), δ, ppm: 3.65/86.05 (=NH/C1), 3.65/119.48 (=NH/C10a), 3.65/151.08 (=NH/C4), 3.66/168.96 (=NH/C5), 6.52/70.54 (-NH2/C4a), 6.52/86.05, (-NH2/C1),6.31/70.54 (=NH/C4a). Yield: 84% (A), 75% (B).
- 2-(4-amino-9-bromo-1-cyano-5-imino-3,5-dihydro-2H-chromeno[3,4-c]pyridin-2-ylidene)malononitrile 4b
- (A) Equimolar amounts of malononitrile (0.13 g, 0.002 mol) and 5-bromsalicylic aldehyde (0.002 mol) were refluxed in IPA for 6 h. After cooling, the crystalline solid was filtered off and dried in air. (B) 2b (0.35 g) in IPA was refluxed for 5 h. The crystalline solid was filtered off and dried in air. (C) 2b (0.35 g) was stirred in THF at 40 °C for 5 h. The crystalline solid was filtered off and dried in air.
- M.p. = 270–272 °C. Brown crystals. Calculated, %: C, 50.68; H, 1.86; Br, 21.07; N, 22.16; O, 4.22. C16H7BrN6O. Found, C, %: 50,47; H, 2.05; N, 22.49. 1H NMR (DMSO-d6), δ, ppm: 3.66 (=NH, s, 1H), 6.20 (=NH, s, 2H), 6.50 (-NH2, s, 2H), 7.54 (H7, d, 1H. J = 8 Hz), 7.94 (H8, d, 1H. J = 8 Hz), 9.05 (H10, s, 1H. J = 8 Hz). 1H/13C HSQC (DMSO-d6), δ, ppm: 7.53/121.27 (H7/C7), 7.94/137.17 (H8/C8), 9.05/127.63 (H10/C10). 1H/13C HMBC (DMSO-d6), δ, ppm: 3.66/85.56 57 (=NH/C1). 3.66/122.76 (=NH/C10a), 3.66/131.83 (=NH/C10b), 3.66/150.42 (=NH/C4), 3.66/158.87 (=NH/C5), 6.32/70.70 (=NH/C4a), 6.50/70.70 (-NH2/C4a), 6.50/85.56 (-NH2/C1). Yield: 70% (A), 75% (B), 86% (C).
- 2-amino-6-R-4-((6-R-3-cyano-2H-chromen-2-ylidene)amino)-4H-chromene-3-carbonitriles 5b
- (A) Equimolar amounts of malononitrile (0.13 g, 0.002 mol) and 5-bromsalicylic aldehyde (0.002 mol) were heated in ethanol in an ultrasonic bath at 55 °C for 1 h. The beige crystals that precipitated were filtered off, washed with hexane, and dried in a desiccator. (B) Equimolar amounts of malononitrile (0.13 g, 0.002 mol) and 5-bromsalicylic aldehyde (0.002 mol) were heated in aqueous–ethanolic medium (1:1) in the presence of potassium carbonate (3 mol %) in an ultrasonic bath at 55 °C for 1 h. The beige crystals were filtered off, washed with hexane, and dried in a desiccator.
- M.p. = 200–201 °C. Beige crystals. Calculated, %: C, 48.22; H, 2.02; Br, 32.08; N, 11.25; O, 6.42. C20H10Br2N4O2. Found, %: C, 47.98; H, 2.07; N, 11.85. 1H NMR (DMSO-d6), δ, ppm: 5.81 (H4, s, 1H), 7.06 (H8, d, 1H. J = 8 Hz), 7.22 (-NH2, s, 2H), 7.31 (H8′, d, 1H. J = 8 Hz), 7.49 (H7, d, 1H. J = 8 Hz), 7.53 (H5, s, 1H), 7.78–7.81 (H7′, d, 1H. J = 8 Hz), 7.83 (H5′, s, 1H), 8.29 (H4′, s, 1H). 1H/13C HSQC (DMSO-d6), δ, ppm: 5.81/48.62 (H4/C4), 7.07/118.80 (H8/C8), 7.32/118.68 (H8′/C8′), 7.49/132.22 (H7/C7), 7.53/132.10 (H5/C5), 7.80/136.76 (H7′/C7′),7.83/131.80 (H5′/C5′), 8.29/145.45 (H4′/C4′). 1H/13C HMBC (DMSO-d6), δ, ppm: 5.81/54.90 (H4/C3), 5.81/120.47 (H4/-CN), 5.81/124.94 (H4/C4a), 5.81/132.06 (H4/C5), 5.81/146.44 (H4/C2′), 5.81/148.48 (H4/C8a), 5.81/162.07 (H4/C2), 7.22/54.89 (-NH2/C3), 7.53/48.65 (H5/C4), 7.83/145.53 (H5′/C4′), 7.83/152.63 (H5′/C8a’), 8.29/115.16 (H4′/-CN’), 8.29/131.75 (H4′/C5′), 8.29/146.43 (H4′/C2′), 8.29/152.62 (H4′/C8a’). Yield: 80% (A), 83% (B).
4. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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Meshcheryakova, A.A.; Konstantinova, E.A.; Melkonyan, K.A.; Khrustaleva, A.A.; Sorokin, V.V. The Synthesis of Various 2-Imino-2H-chromene-3-carbonitrile Derivatives. Chem. Proc. 2023, 14, 42. https://doi.org/10.3390/ecsoc-27-16125
Meshcheryakova AA, Konstantinova EA, Melkonyan KA, Khrustaleva AA, Sorokin VV. The Synthesis of Various 2-Imino-2H-chromene-3-carbonitrile Derivatives. Chemistry Proceedings. 2023; 14(1):42. https://doi.org/10.3390/ecsoc-27-16125
Chicago/Turabian StyleMeshcheryakova, Anna A., Ekaterina A. Konstantinova, Karina A. Melkonyan, Alexandra A. Khrustaleva, and Vitaliy V. Sorokin. 2023. "The Synthesis of Various 2-Imino-2H-chromene-3-carbonitrile Derivatives" Chemistry Proceedings 14, no. 1: 42. https://doi.org/10.3390/ecsoc-27-16125