Abstract
C14H13NO5, monoclinic, P21 (no. 4), a = 4.6967(7) Å, b = 10.7175(16) Å, c = 12.945(2) Å, β = 94.827(8)°, V = 649.30(17) Å3, Z = 2, R gt (F) = 0.0577, wR ref (F2) = 0.1302, T = 223(2) K.
The molecular structure is shown in the figure. Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.
Data collection and handling.
| Crystal: | Colourless plate |
| Size: | 0.14 × 0.12 × 0.05 mm |
| Wavelength: | Mo Kα radiation (0.71073 Å) |
| μ: | 0.11 mm−1 |
| Diffractometer, scan mode: | PHOTON 100 CMOS, φ and ω |
| θmax, completeness: | 28.4°, >99% |
| N(hkl)measured, N(hkl)unique, Rint: | 26,931, 3254, 0.137 |
| Criterion for Iobs, N(hkl)gt: | Iobs > 2 σ(Iobs), 1835 |
| N(param)refined: | 182 |
| Programs: | Bruker [1], SHELX [2, 3], Olex2 [4] |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).
| Atom | x | y | z | Uiso*/Ueq |
|---|---|---|---|---|
| C1 | 0.1748 (6) | 0.0642 (3) | 0.4571 (2) | 0.0320 (7) |
| O1 | 0.2163 (4) | 0.1571 (2) | 0.51261 (16) | 0.0406 (5) |
| C2 | −0.0446 (7) | 0.0647 (3) | 0.3685 (2) | 0.0344 (7) |
| C3 | −0.2081 (6) | 0.1703 (3) | 0.3418 (2) | 0.0401 (8) |
| H3 | −0.1774 | 0.2444 | 0.3801 | 0.048* |
| C4 | −0.4142 (7) | 0.1666 (4) | 0.2598 (3) | 0.0491 (9) |
| H4 | −0.5247 | 0.2379 | 0.2426 | 0.059* |
| C5 | −0.4597 (8) | 0.0588 (4) | 0.2025 (3) | 0.0532 (10) |
| H5 | −0.6013 | 0.0576 | 0.1466 | 0.064* |
| C6 | −0.3004 (8) | −0.0470 (4) | 0.2259 (3) | 0.0487 (9) |
| H6 | −0.3307 | −0.1204 | 0.1867 | 0.058* |
| C7 | −0.0941 (6) | −0.0423 (3) | 0.3090 (2) | 0.0375 (8) |
| O2 | 0.0594 (5) | −0.1498 (2) | 0.32907 (18) | 0.0441 (6) |
| C8 | 0.2634 (7) | −0.1500 (3) | 0.4085 (3) | 0.0417 (8) |
| H8 | 0.3667 | −0.2243 | 0.4213 | 0.050* |
| C9 | 0.3316 (6) | −0.0519 (3) | 0.4714 (2) | 0.0326 (7) |
| C10 | 0.5677 (7) | −0.0726 (3) | 0.5499 (3) | 0.0368 (8) |
| H10 | 0.6522 | −0.1522 | 0.5534 | 0.044* |
| N1 | 0.6678 (6) | 0.0101 (3) | 0.6143 (2) | 0.0397 (7) |
| O3 | 0.9037 (5) | −0.0459 (2) | 0.67441 (19) | 0.0482 (6) |
| C11 | 1.0344 (7) | 0.0452 (3) | 0.7422 (2) | 0.0410 (8) |
| H11A | 1.0473 | 0.1242 | 0.7047 | 0.049* |
| H11B | 1.2291 | 0.0185 | 0.7651 | 0.049* |
| C12 | 0.8707 (8) | 0.0653 (4) | 0.8346 (3) | 0.0517 (9) |
| O4 | 0.6764 (6) | 0.0028 (3) | 0.8604 (2) | 0.0822 (10) |
| O5 | 0.9754 (7) | 0.1624 (3) | 0.88836 (19) | 0.0763 (9) |
| C13 | 0.8423 (15) | 0.1892 (6) | 0.9839 (4) | 0.129 (3) |
| H13A | 0.6413 | 0.1638 | 0.9753 | 0.155* |
| H13B | 0.9369 | 0.1397 | 1.0404 | 0.155* |
| C14 | 0.8570 (19) | 0.3090 (6) | 1.0096 (5) | 0.158 (3) |
| H14A | 1.0552 | 0.3325 | 1.0258 | 0.237* |
| H14B | 0.7513 | 0.3231 | 1.0698 | 0.237* |
| H14C | 0.7752 | 0.3591 | 0.9521 | 0.237* |
Source of material
The starting material 4-oxo-4H-chromene-3-carbaldehyde (522 mg, 3 mmol), purchased from Aldrich, was dissolved in 40 mL of methanol to give a clear solution. Two equivalents of hydroxyl amine (6 mmol, 420 mg) and sodium acetate (6 mmol, 490 mg) in 15 mL of water were added to the above solution, and reaction mixture was stirred at 70 °C for 5 h. The reaction mixture was cooled down to room temperature to furnish precipitation of the corresponding oxime compound. The solid was filtered and washed with cold methanol. The oxime compound (2 mmol, 380 mg) and K2CO3 (3 mmol, 415 mg) were dissolved in 30 mL of DMF to give a clear solution. To the solution, was added ethylbromoacetate (3 mmol, 0.4 mL) and the reaction mixture was stirred at 50 °C. After the completion of the reaction (checked by TLC), the reaction mixture was cooled down to room temperature and poured into 100 mL of ice-water to form a precipitate. Crystals of the title compound were obtained by recrystallization from an ethanol solution.
Experimental details
Data collections and reduction were carried out using the Bruker software APEX2 and SAINT including SADABS [1]. Hydrogen atoms were placed in their geometrically idealized positions and constrained to ride on their parent atoms.
Comment
Oxime esters are one of the most important moiety in a large number of bioactive compounds with a wide range of activities [5, 6]. In addition they have been known as photoinitiators in the field of photochemistry [7, 8]. Chromenon is an indispensable structure in flavonoids which have demonstrated diverse biological activities in medicinal chemistry [9], [10], [11], [12]. Isoflavonoids have substituent at three-position of the chromenone structure and they have shown structural difference from other flavonoids which have substituent at two-position. Because of the critical structural differences, isoflavones exhibit physiological functions that are different to those of other flavonoids [13]. Recent research has shown that isoflavones have broad biological activities including an influence on osteoporosis [14], cardiovascular diseases [15], and it has been shown that an inhibition of thyroid peroxidase is possible [16]. In an extension of our previous studies on isoflavones [17], [18], [19], chromenone was combined with an oxime ester to obtain isoflavone analogs.
In the title compound (see the Figure), the chromenone ring (C1–C9/O2) is almost planar, with a maximum deviation of 0.023 Å at C1 (r.m.s. deviation = 0.010 Å). The chromenone ring and the C10=N1 double bond of the oxime unit lie in the same plane [N1–C10–C9–C1 = −1.3(5)]. The C10=N1 imine double bond adopts an E-configuration, which was defined by a dihedral angle of −177.6(3)° for C9–C10–N1–O3. In the oxime unit, the ethylacetate group attached to the oxygen forms an anti-conformation with the imine C10=N1 double bond as it moves away from the hydrogen attached to the imine carbon [C11–O3–N1–C10 = 176.0(3)°]. In the crystal, the carbonyl oxygen (O1) forms weak and branched C(10)–H(10)⃛O(1) and C(8)–H(8)⃛O(1) hydrogen bonds to form a six-membered ring, which propagates along the b-axis by a C(11)–H(11A)⃛O(2) hydrogen bond. The chain is further stabilized by additional C(11)–H(11B)⃛O(4) interactions.
Funding source: Basic Science Research Program
Award Identifier / Grant number: NRF-2019R1F1A1058747
-
Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
-
Research funding: Basic Science Research Program (award No. NRF-2019R1F1A1058747).
-
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.
References
1. Bruker. SAINT, APEX2 and SADABS; Bruker AXS Inc.: Madison, WI, USA, 2012.Search in Google Scholar
2. Sheldrick, G. M. SHELXTL – integrated space-group and crystal-structure determination. Acta Crystallogr. 2015, A71, 3–8; https://doi.org/10.1107/s2053273314026370.Search in Google Scholar
3. Sheldrick, G. M. Crystal structure refinement with SHELXL. Acta Crystallogr. 2015, C71, 3–8; https://doi.org/10.1107/s2053229614024218.Search in Google Scholar
4. Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K., Puschmann, H. OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Crystallogr. 2009, 42, 339–341; https://doi.org/10.1107/s0021889808042726.Search in Google Scholar
5. Vessally, E., Saeidian, H., Hosseinian, A., Edjlali, L., Bekhradnia, A. A. Review on synthetic applications of oxime esters. Curr. Org. Chem. 2017, 21, 249–271.10.2174/1385272820666161018150925Search in Google Scholar
6. Wang, X., Zhong, X., Zhu, X., Wang, H., Li, Q., Zhang, J., Ruan, X., Xue, W. Synthesis and antibacterial activity of oxime ester derivatives containing 1,2,4-triazole or 1,3,4-oxadiazole moiety. Chem. Pap. 2017, 71, 1953–1960; https://doi.org/10.1007/s11696-017-0189-5.Search in Google Scholar
7. Fast, D. E., Lauer, A., Menzel, J. P., Kelterer, A. M., Gescheidt, G., Barner-Kowollik, C. Wavelength-dependent photochemistry of oxime ester photoinitiators. Macromolecules 2017, 50, 1815–1823; https://doi.org/10.1021/acs.macromol.7b00089.Search in Google Scholar
8. Qiu, W., Zhu, J., Dietliker, K., Li, Z. Polymerizable oxime esters: an efficient photoinitiator with low migration ability for 3D printing to fabricate luminescent devices. ChemPhotoChem 2020, 4, 5296–5303; https://doi.org/10.1002/cptc.202000146.Search in Google Scholar
9. Medzhitov, R Inflammation 2010: new adventures of an old flame. Cell 2010, 140, 771–776; https://doi.org/10.1016/j.cell.2010.03.006.Search in Google Scholar
10. Cushnie, T. P. T., Lamb, A. J. Antimicrobial activity of flavonoids. Int. J. Antimicrob. Agents 2005, 26, 343–356; https://doi.org/10.1016/j.ijantimicag.2005.09.002.Search in Google Scholar
11. Lebeau, J., Furman, C., Bernier, J. L., Duriez, P., Teissier, E., Cotelle, N. Antioxidant properties of di-tert-butylhydroxylated flavonoids. Free Radical Biol. Med. 2000, 29, 900–912; https://doi.org/10.1016/s0891-5849(00)00390-7.Search in Google Scholar
12. Shukla, S., Gupta, S. Apigenin: a promising molecule for cancer prevention. Pharm. Res. 2010, 27, 962–978; https://doi.org/10.1007/s11095-010-0089-7.Search in Google Scholar
13. Tikkanen, M. J., Adlercreutz, H. Dietary soy-derived isoflavone phytoestrogens: could they have a role in coronary heart disease prevention? Biochem. Pharmacol. 2000, 60, 1–5; https://doi.org/10.1016/s0006-2952(99)00409-8.Search in Google Scholar
14. Ye, Y.-B., Tang, X.-Y., Verbruggen, M. A., Su, Y.-X. Soy isoflavones attenuate bone loss in early postmenopausal Chinese women: a single-blind randomized, placebo-controlled trial. Eur. J. Nutr. 2006, 45, 327–334; https://doi.org/10.1007/s00394-006-0602-2.Search in Google Scholar PubMed
15. Zhan, S., Ho, S. C. Meta-analysis of the effects of soy protein containing isoflavones on the lipid profile. Am. J. Clin. Nutr. 2005, 81, 397–408; https://doi.org/10.1093/ajcn.81.2.397.Search in Google Scholar PubMed
16. Chang, H. C., Doerge, D. R. Dietary genistein inactivates rat thyroid peroxidase in vivo without an apparent hypothyroid effect. Toxicol. Appl. Pharmacol. 2000, 168, 244–252; https://doi.org/10.1006/taap.2000.9019.Search in Google Scholar PubMed
17. Shin, S. Y., Lee, Y. H., Lim, Y., Lee, H. J., Lee, J. H., Yoo, M., Ahn, S., Koh, D. Single crystal X-ray structure for the disordered two independent molecules of novel isoflavone: synthesis, hirshfeld surface analysis, inhibition and docking studies on IKKβ of 3-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-6,7-dimethoxy-4H- chromen-4-one. Crystals 2020, 10, 911; https://doi.org/10.3390/cryst10100911.Search in Google Scholar
18. Jeong, M., Jung, E., Lee, Y. H., Seo, J. K., Ahn, S., Koh, D., Lim, Y., Shin, S. Y. A novel synthetic compound (E)-5-((4-oxo-4H-chromen-3-yl)methyleneamino)-1-phenyl- 1H-pyrazole-4-carbonitrile inhibits TNFα-induced MMP9 expression via EGR-1 downregulation in MDA-MB-231 human breast cancer cells. Int. J. Mol. Sci. 2020, 21, 5080; https://doi.org/10.3390/ijms21145080.Search in Google Scholar PubMed PubMed Central
19. Ahn, S., Sung, J., Lee, J. H., Yoo, M., Lim, Y., Shin, S. Y., Koh, D. Synthesis, single crystal X-ray structure, Hirshfeld surface analysis, DFT computations, docking studies on aurora kinases and an anticancer property of 3-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-6-methoxy-4H-chromen-4- one. Crystals 2020, 10, 413; https://doi.org/10.3390/cryst10050413.Search in Google Scholar
© 2021 Miri Yoo and Dongsoo Koh, published by De Gruyter, Berlin/Boston
This work is licensed under the Creative Commons Attribution 4.0 International License.
