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Article

Facile Access to 2-Selenoxo-1,2,3,4-tetrahydro-4-quinazolinone Scaffolds and Corresponding Diselenides via Cyclization between Methyl Anthranilate and Isoselenocyanates: Synthesis and Structural Features

by
Vladimir K. Osmanov
1,
Evgeniy V. Chipinsky
1,
Victor N. Khrustalev
2,3,
Alexander S. Novikov
2,4,
Rizvan Kamiloglu Askerov
5,
Alexander O. Chizhov
3,
Galina N. Borisova
1,
Alexander V. Borisov
1,
Maria M. Grishina
2,
Margarita N. Kurasova
2,
Anatoly A. Kirichuk
2,
Alexander S. Peregudov
6,
Andreii S. Kritchenkov
2 and
Alexander G. Tskhovrebov
2,7,*
1
Department of Chemistry, R.E. Alekseev Nizhny Novgorod State Technical University, Minin St., 24, 603155 Nizhny Novgorod, Russia
2
Research Institute of Chemistry, Peoples’ Friendship University of Russia, Miklukho-Maklaya St., 6, 117198 Moscow, Russia
3
N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prosp., 47, 119334 Moscow, Russia
4
Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab., 7/9, 199034 Saint Petersburg, Russia
5
Department of Organic Chemistry, Baku State University, Z. Xalilov, 23, Baku 1148, Azerbaijan
6
Institute of Organoelement Compounds of the Russian Academy of Sciences, Vavilov St., 28, 119991 Moscow, Russia
7
N.N. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, Ul. Kosygina, 4, 119991 Moscow, Russia
*
Author to whom correspondence should be addressed.
Molecules 2022, 27(18), 5799; https://doi.org/10.3390/molecules27185799
Submission received: 16 August 2022 / Revised: 1 September 2022 / Accepted: 2 September 2022 / Published: 7 September 2022
(This article belongs to the Special Issue Covalent and Noncovalent Interactions in Crystal Chemistry)
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Versions Notes

Abstract

:
A practical method for the synthesis of 2-selenoxo-1,2,3,4-tetrahydro-4-quinazolinone was reported. The latter compounds were found to undergo facile oxidation with H2O2 into corresponding diselenides. Novel organoselenium derivatives were characterized by the 1H, 77Se, and 13C NMR spectroscopies, high-resolution electrospray ionization mass spectrometry, IR, elemental analyses (C, H, N), and X-ray diffraction analysis for several of them. Novel heterocycles exhibited multiple remarkable chalcogen bonding (ChB) interactions in the solid state, which were studied theoretically.

1. Introduction

Quinazolinones are an important class of heterocycles, which are widespread in natural alkaloids and synthetic biologically active compounds [1]. Quinazolinone derivatives are known to exhibit hypotensive, anticonvulsant, anti-inflammatory, antibacterial, antimalarial, fungicidal effects, and antiproliferative activity [2,3,4,5,6,7,8,9]. Interestingly, the introduction of the S or Se atoms in 2- or 4-positions of the quinazolinone core results in the enhancement of the anticancer activity [5,6,10,11,12,13,14,15].
There are several approaches to the synthesis of heterocyclic thiones and selones described in the literature. The first one includes halogen to sulfur or selenium substitution employing hydrosulphide or hydroselenide or thio- or selenourea [16,17,18,19]. The Se atom can also be conveniently introduced via substitution of the SMe moiety on treatment with NaSeH [20]. Another widely spread approach to the synthesis of sulfur-containing derivatives of quinazolinones involves the reaction between o-aminonitriles or o-aminocarboxylates and isothiocyanates or thiourea. However, this approach has been studied little for the preparation of derivatives of quinazolin-2(1H)-selones, which is probably due to the lower stability and synthetic availability of isoselenocyanates [21,22]. It should be noted that interest in chacogen-containing derivatives of quinazolinones arises due to their potential applications in supramolecular chemistry. Halogen and chalcogen bonding (ChB) is an area of increasing interest, and these weak interactions are often employed for various applications [23,24,25,26,27,28,29,30,31,32,33].
Following our interest in chalcogen heterocycles [34,35,35,36,37] and noncovalent interactions [38,39,40,41,42,43,44,45,46,47], here we reported a convenient synthesis of 2-selenoxo-1,2,3,4-tetrahydro-4-quinazolinones via cyclization reaction between methyl anthranilate and isoselenocyanates. Moreover, we demonstrated that 2-selenoxo-1,2,3,4-tetrahydro-4-quinazolinones undergo facile oxidation under mild conditions to give corresponding diselenides.

2. Results and Discussion

The addition of isoselenocyanates 2a–g to a solution of methyl anthranilate 1 in ethanol under reflux allowed the preparation of corresponding 2-selenoxo-1,2,3,4-tetrahydro-4-quinazolinones 3a–g in high yields (Scheme 1).
The structures of all new compounds were confirmed by the 1H, 77Se, and 13C NMR spectroscopies; high-resolution electrospray ionization mass spectrometry (HRESI–MS); IR; the elemental analyses (C, H, N); and X-ray diffraction analysis for 3b, 3f, and 3g (Figure 1). Compounds 3b, 3f, and 3g could be recrystallized to furnish monocrystals, suitable for analysis by single crystal X-ray crystallography. The structural investigations confirmed the formation of 2-selenoxo-1,2,3,4-tetrahydro-4-quinazolinones. The plausible mechanism for the formation of 3a–g is depicted in Scheme S1 and is similar to what was observed in the S analogs [15].
Structural investigations revealed that the 2-selenoxo-1,2,3,4-tetrahydro-4-quinazolinone fragment in 3b, 3f, and 3g is virtually planar, and the C=Se distances are within the typical range for the corresponding single bond values. Interestingly, compound 3f exhibited unsymmetrical supramolecular dimers via type II Se···Se ChB (Figure 1), while 3b and 3f were not engaged in ChB, arguably due to the prevalence of other weak interactions in the solid state. Theoretical calculations on the type II Se···Se ChB for compound 3f are given here further.
When we attempted to recrystallize 3c from ethanol, its aerobic oxidation coupled with the diselenide formation took place. Similar oxidations were observed earlier in the literature [22,48,49]. We were able to achieve synthetically viable oxidation for 3a–g to furnish 4a–g in good yields employing hydrogen peroxide as an oxidant (Scheme 2).
Compounds 4a–g are poorly soluble in common organic solvents; however, we managed to obtain single crystals of 4b and 4c, suitable for X-Ray analysis (Figure 2).
Both compounds 4b and 4c exhibited a pair of intramolecular Se···N ChB (Figure 2). Cambridge Structural Database search revealed that it contained only four other published structures (5 [49], 6 [50], 7 [51,52], and 8 [52]), which featured such a remarkable pair of intramolecular X···N (X = S, Se, Te) ChB (Figure 3).
Compound 5 is a dibenzimidazole diselenide, as are 4b and 4c, which features two intramolecular Se···N ChB. For 6, the situation is slightly more complicated: each Se atom is involved in two intramolecular Se···N ChB, and overall, the molecule features four Se···N ChB (Figure 3). Compounds 7 [51,52] and 8 [52], which were reported earlier, also featured intramolecular ChB, analogously to 4b and 4c.
In order to theoretically study chalcogen bonds Se···Se, Se···N, and Te···N observed in the X-ray structures 3f, 4b, 4c, 5, 6, 7, and 8, the DFT calculations followed by the topological analysis of the electron density distribution within the QTAIM approach [53] were carried out for model supramolecular associates (see Computational details and Table S1 in Supplementary Materials). The results of the QTAIM analysis are summarized in Table 1. The contour line diagrams of the Laplacian of electron density distribution ∇2⍴(r), bond paths, and selected zero-flux surfaces; visualization of electron localization function (ELF); and reduced density gradient (RDG) analyses for contacts Se···Se, Se···N, and Te···N in the X-ray structures 3f, 4b, 4c, 5, 6, 7, and 8 are shown in Figure 4, Figure 5, Figure 6, Figure 7, Figure 8, Figure 9 and Figure 10; the visualization of these noncovalent interactions in 3D using NCI analysis technique [54] is shown in Figure 11.
The QTAIM analysis of model supramolecular associates demonstrates the presence of bond critical points (3, –1) for contacts Se···Se, Se···N, and Te···N in the X-ray structures 3f, 4b, 4c, 5, 6, 7, and 8 (Table 1 and Figure 4, Figure 5, Figure 6, Figure 7, Figure 8, Figure 9 and Figure 10). The low magnitude of the electron density, positive values of the Laplacian of electron density, and very close to zero energy density in bond critical points (3, –1) for chalcogen bonds Se···Se (3f) and Se···N (4b, 4c, 5, 6, and 7) or Te···N (8) in studied model supramolecular associates, as well as their estimated strength, are typical for noncovalent interactions involving chalcogen atoms [34,35,35,36,37,57,58,59,60,61,62], in contrast with these descriptors (viz. relatively large magnitude of the electron density, negative Laplacian of electron density, and large negative energy density) for covalent bonds Se–Se and Te–Te in 4b, 4c, 5, 6, 7, and 8. The sign of λ2 can be utilized to distinguish bonding (attractive, λ2 < 0) interactions from nonbonding ones (repulsive, λ2 > 0) [54,63], which allows us to conclude that chalcogen bonds contact Se···Se, Se···N, and Te···N in the X-ray structures 3f, 4b, 4c, 5, 6, 7, and 8 are attractive in nature and purely noncovalent (in all cases, except Se···N interactions (2.479 Å) in 6, which has some covalent contribution), because the balance between the Lagrangian kinetic energy G(r) and potential energy density V(r) at the appropriate bond critical points (3, –1) for these contacts is –G(r)/V(r) > 1 [64].

3. Materials and Methods

Methyl anthranilate (Acros Organics, Belgium) was used in this work without additional purification. The isoselenocyanates 2 a–g used in this work were obtained by the literature method [65]. Isoselenocyanates 2b, c, g were purified by recrystallization from hexane at −20 °C. Ethanol was dried by distillation over CaO and CaH2.
All melting points were determined with a “Stuart SMP3” melting point apparatus. Infrared spectra were recorded on the “Shimadzu IR Prestige-21” (Kyoto, Japan) instrument in KBr disk (4000–400 cm−1). High-resolution mass spectra (HR-MS) were measured on a “Bruker micrOTOF II” (Karlsruhe, Germany) instrument using electrospray ionization (ESI). The measurements were performed in a positive ion mode (interface capillary voltage −4500 V); mass range from m/z 50 to m/z 30 0 0 Da; internal calibration was performed with Electrospray Calibrant Solution («Agilent Tuning Mix», «Agilent»). The most intensive peak in the isotopic pattern was reported. A syringe injection was used for solutions in acetonitrile (flow rate 5 McL/min). Nitrogen was applied as a dry gas; interface temperature was set at 180 °C.
1H, COSY, 13C-NMR, DEPT, HSQC, and HMBC spectra compounds 3a–f were measured on an “Agilent DD2 400” spectrometer (400 MHz for 1H and 100.60 MHz for 13C, Santa Clara, CA, USA) using DMSO-d6 as the NMR solvents. Chemical shifts were indicated in parts per million (ppm) relative to tetramethylsilane as an internal standard. The 77Se-NMR spectra compound 3a-f were measured on an “Agilent DD2 400” spectrometer at 76.30 MHz using diphenylselenide as a standard. The 19F-NMR spectra compound 3e were measured on an “Agilent DD2 400” spectrometer at 376.30 MHz using trichlorofluoro-methane as a standard. The 1H, COSY, 13C, JMODECHO, HSQC, and HMBC compounds 3g were measured on a “Bruker AvanceTM 600” (Karlsruhe, Germany) spectrometer (600 MHz for 1H and 150.925 MHz for 13C) using DMSO-d6 as the NMR solvents. The 1H, COSY, 13C, JMODECHO, HSQC, and HMBC compounds 4a–g were measured on a “Bruker AvanceTM 500” spectrometer (500 MHz for 1H and 125.72 MHz for 13C) using DMSO- d6 as the NMR solvents. The 77Se-NMR spectra compounds, 3g and 4a–g, were measured on a “Bruker AvanceTM 400” spectrometer at 76.35 MHz and referenced to diphenylselenide, using DMSO- d6 as the NMR solvents. The 19F-NMR spectra compounds, 3g, 4e, and 4g, were measured on a “Bruker AvanceTM 300” spectrometer at 282.38 MHz and referenced to trichlorofluoromethane, using DMSO-d6 as NMR solvent.

3.1. Synthetic Part

Synthesis of compounds 3a–g (general method). To a solution (0.01 mol) of methyl anthranilate, 1 in 100 mL of absolute ethanol (0.01 mol) of the corresponding isoselenocyanate 2 a–g in 20 mL of absolute ethanol was added, boiled for 6 h, then cooled to 0 °C. Precipitates precipitated from the solution were separated by filtration, washed with ethanol (2 × 25 mL), and dried at 40 °C.
Molecules 27 05799 i001
3-phenyl-2-selenoxo-2,3-dihydroquinazolin4(1H)-one. Light yellow solid (47%), mp 235 °C. Anal. Calcd. for C14H10N2OSe: C 55.82; H 3.35; N 9.30. Found: C 55.72; H 3.30; N 9.38. ESI+-MS, m/z: calcd for [C14H10N2OSe + H]+ 303.0031, found 303.0036 [C14H10N2OSe + H]+. IR (KBr, selected bands, sm−1): 3244, 1664, 1621, 1528, 1488, 1266, 1189, 759, 691. 1H NMR (400 MHz, DMSO-d6), δ (ppm): 13.46 (bs, 1H, NH), 7.93 (dd, J = 8.0, J = 1.0, 1H, H-5), 7.77 (t, 1H, H-7), 7.51 (d, J = 8.0 Hz, 1H, H-8), 7.46 (m, 2H, Ph), 7,39 (m, 2H, Ph and H-6), 7.24 (m, 2H, Ph). 13C NMR (100.60 MHz, DMSO-d6), δ (ppm): 176.4 (C=Se), 159.3 (C=O), 141.2 (C, Ph), 140.4 (C-8a), 136.2 (C-7), 129.5 (2CH, Ph), 129.3 (2CH, Ph), 128.7 (CH, Ph), 127.9 (C-5), 125.4 (C-6), 117.2 (C-4a), 117.2 (C-4a), 116.5 (C-8). 77Se NMR (76.30 MHz, DMSO-d6), δ (ppm): 462.0 (s).
Molecules 27 05799 i002
3-(2-methylphenyl)-2-selenoxo-2,3-dihydro-quinazolin- 4(1H)-one. Light brown solid (54%), mp 210 °C. Anal. Calcd. for C15H12N2OSe: 57.15; H 3.84; N 8.89. Found: C 57.35; H 3.72; N 8.78. ESI+-MS, m/z: calcd for [C15H12N2OSe + H]+ 317.0188, found 317.0184 [C15H12N2OSe + H]+. IR (KBr, selected bands, sm−1): 3241, 1702, 1619, 1520, 1410, 1262, 1189, 753. 1H NMR (400 MHz, DMSO-d6), δ (ppm): 13.59 (bs, 1H, NH), 7.95 (d, J = 7.5, 1H, H-5), 7.80 (m, 1H, H-7), 7.55 (d, J = 8.0, 1H, H-8), 7.41 (t, 1H, H-6), 7,26-7,33 (m, 3H, Ar), 7.20 (d, J = 10.0, 1H, Ar), 2.03 (s, 3H, CH3). 13C NMR (100.60 MHz, DMSO-d6), δ (ppm): 175.7 (C=Se), 158.7 (C=O), 140.5 (C-8a), 140.0 (C-1′), 136.4 (C-7), 135.5 (C-5′), 130.9 (C-3′), 129.4 (C-6′); 129.0 (C-4′), 128.0 (C-5), 127.2 (C-2′), 125.6 (C-6), 116.9 (C-4a), 116.6 (C-8), 17.55 (CH3). 77Se NMR (76.30 MHz, DMSO-d6), δ (ppm): 442.5 (s).
Molecules 27 05799 i003
3-(2-methoxyphenyl)-2-selenoxo-2,3-dihydroquinazolin- 4(1H)-one. Yellow solid (56%), mp 250 °C. Anal. Calcd. for C15H12N2O2Se: C 54.39; H 3.65; N 8.46. Found: C 54.24; H 3.60; N 8.35. ESI+-MS, m/z: calcd for [C15H12N2O2Se + H]+ 333.0137, found 333.0137 [C15H12N2O2Se + H]+. IR (KBr, selected bands, sm−1): 2946, 1711, 1621, 1533, 1420, 1265, 1190, 1020, 752. 1H NMR (400 MHz, DMSO-d6), δ (ppm): 13.53 (bs, 1H, NH), 7.93 (d, J = 8.0, 1H, H-5), 7.80 (m, 1H, H-7), 7.54 (d, J = 8.5, 1H, H-8), 7.40 (m, 2H, H-4′ and H-6), 7.23 (dd, J = 8.0, J = 1.5, 1H, H-6′), 7.14 (d, J = 8.0, 1H, H-3′), 7.02 (t, 1H, H-5′), 3.70 (s, 3H, OCH3). 13C NMR (100.60 MHz, DMSO-d6), δ (ppm): 176.6 (C=Se), 158.7 (C=O), 154.7 (C-2′-O), 140.4 (C-8a), 136.4 (C-7), 130.6 (C-6′), 130.4 (C-4′), 129.4 (C-1′), 128.0 (C-5), 125.5 (C-6), 121.0 (C-5′), 116.7 (C-4a), 116.5 (C-8), 112.8 (C-3′), 56.18 (OCH3). 77Se NMR (76.30 MHz, DMSO-d6), δ (ppm): 441.6 (s).
Molecules 27 05799 i004
3-(3-methoxyphenyl)-2-selenoxo-2,3-dihydro-quinazolin- 4(1H)-one. Light beige solid (29%), mp 222 °C. Anal. Calcd. for C15H12N2O2Se: C 54.39; H 3.65; N 8.46. Found: C 54.31; H 3.61; N 8.40. ESI+-MS, m/z: calcd for [C15H12N2O2Se + H]+ 333.0128, found 333.0137 [C15H12N2O2Se + H]+. IR (KBr, selected bands, sm−1): 2943, 1665, 1525, 1377, 1262, 759. 1H NMR (400 MHz, DMSO-d6), δ (ppm): 13.49 (bs, 1H, NH), 7.93 (dd, J = 8.0, J = 1.6, 1H, H-5), 7.78 (m, 1H, H-7), 7.53 (d, J = 8.4, 1H, H-8), 7.39 (m, 1H, H-6), 7.36 (t, 1H, H-5′), 6.97 (dd, J = 8.4, J = 2.5, 1H, H-6′), 6.90 (t, 1H, H-2′), 6.85 (d, J = 8.0,1H, H-4′), 3.74 (s, 3H, OCH3). 13C NMR (100.60 MHz, DMSO-d6), δ (ppm): 176.3 (C=Se), 160.1 (C3′-O), 159.2 (C=O), 142.2 (C-1′), 140.4 (C-8a), 136.1 (C-7), 129.9 (C-5′), 127.9 (C-5), 125.4 (C-6), 121.7 (C-4′), 117.2 (C-4a), 116.5 (C-8), 115.5 (C-2′), 114.2 (C-6′), 55.7 (OCH3). 77Se NMR (76.30 MHz, DMSO-d6), δ (ppm): 457.8 (s).
Molecules 27 05799 i005
3-(2-fluorophenyl)-2-selenoxo-2,3-dihydroquina-zolin-4(1H)-one. Light green solid (38%), mp 212 °C. Anal. Calcd. for C14H9FN2OSe: C 52.68; H 2.84; N 8.78. Found: C 52.62; H 2.87; N 8.67. ESI+-MS, m/z: calcd for [C14H9FN2OSe + H]+ 320.9937, found 320.9941 [C14H9FN2OSe + H]+. IR (KBr, selected bands, sm−1): 3209, 1697, 1670, 1621, 1527, 1263, 1182. 1H NMR (400 MHz, DMSO-d6), δ (ppm): 13.71 (bs, 1H, NH), 7.96 (dd, J = 8.0, J = 1.2, 1H, H-5), 7.82 (m, 1H, H-7), 7.55 (d, J = 8.0, 1H, H-8), 7.28–7.52 (m, 5H, H-6, 4H Ar). 13C NMR (100.60 MHz, DMSO-d6), δ (ppm): 176.1 (C=Se), 158.7 (C=O), 157.6 (d, 1J (13C-19F) = 310.5, C-2′-F,), 140.4 (C-8a), 136.6 (C-7), 131.8 (C-5′), 131.3 (d, 3J(13C-19F) = 10.0, C-4′), 128.3 (d., 2J(13C-19F, C-1′) = 16.5), 128.0 (C-5), 125.80 (C-6), 125.3 (d, 3J(13C-19F) = 4.5, C-6′), 116.7 (C-8), 116.5 (C-4a), 116.4 (d, 2J(13C-19F) = 24.3, C-3′). 19F NMR (376.30 MHz, DMSO-d6), δ (ppm): −122.96 (m, 1F). 77Se NMR (76.30 MHz, DMSO-d6), δ (ppm): 447.0 (d, J = 2.5).
Molecules 27 05799 i006
3-(2-chlorophenyl)-2-selenoxo-2,3-dihydroquinazolin-4(1H)-one. Beige solid (58%), mp 225 °C. Anal. Calcd. for C14H9ClN2OSe: C 50.10; H 2.70; N 8.35. Found: C 50.16; H 2.67; N 8.27. ESI+-MS, m/z: calcd for [C14H9ClN2OSe + H]+ 336.9639, found 336.9640 [C14H9ClN2OSe + H]+. IR (KBr, selected bands, sm−1): 3210, 1706, 1676, 1619, 1526, 1486, 1410, 1262, 1189, 758. 1H NMR (400 Mm, Hz, DMSO-d6), δ (ppm): 13.69 (bs, 1H, NH), 7.97 (d, J = 8.0, 1H, H-5), 7.82 (m, 1H, H-7), 7.60 (m, 1H, Ar), 7.55 (d, J = 8.0, 1H, H-8), 7.50 (m, 1H, Ar), 7.46 (m, 2H, Ar), 7.42 (t, 1H, H-6). 13C NMR (100.60 MHz, DMSO-d6), δ (ppm): 175.7 (C=Se), 158.6 (C=O), 140.4 (C-8a), 138.2 (C Ar), 136.6 (C-7), 131.93 (C, Ar), 131.86 (CH, Ar), 130.8 (CH, Ar), 130.1 (CH, Ar), 128.5 (CH, Ar), 128.0 (C-5), 125.7 (C-6), 116.7 (C-8), 116.6 (C-4a). 77Se NMR (76.30 MHz, DMSO-d6), δ (ppm): 450.0 (s).
Molecules 27 05799 i007
3-[2-chloro-5-(trifluoromethyl)phenyl]-2-selenoxo-2,3-dihydroquinazolin-4(1H)-one. Beige solid (57%), mp 201 °C. Anal. Calcd. for C15H8ClF3N2OSe: C 44.63%, H 2.00%, N 6.94%. Found: C 44.52; H 2.06; N 6.87. ESI+-MS, m/z: calcd. for [C15H8ClF3N2OSe + H]+ 404.9513, found 404.9502 [C15H8ClF3N2OSe + H]+. IR (KBr, selected bands, sm−1): 3164, 3113, 3019, 2958, 1718, 1701, 1621, 1534, 1328, 1190, 1175, 1132, 756. 1H NMR (600 MHz, DMSO-d6), δ (ppm): 13.86 (bs, 1H, NH), 8.10 (d, J = 1.9, 1H, H-6′), 8.00 (dd, J = 7.9, J = 0.9, 1H, H-5), 7.84–7.90 (m, 3H, H-7, H-3′, H-4′), 7.58 (d, 1H, H-8), 7.46 (t, 1H, H-6). 13C NMR (150.925 MHz, DMSO-d6), δ (ppm): 175.4 (C=Se), 158.6 (C=O), 140.5 (C-8a), 139.2 (C-2′), 136.81 (C-1′), 136.79(C-7), 131.4 (C-3′), 129.4 (k, 3J(13C,19F) = 3.2, C-6′), 129.2 (k, 2J(13C,19F) = 32.8, C-5′), 127.8 (k, 1J(13C-19F) = 272.6, CF3); 128.1 (C-5), 127.6 (d, 3J(13C,19F) = 2.3, C-4′), 125.9 (C-6), 116.8 (C-8), 116.7 (C-4a). 19F NMR (282.38 MHz, DMSO-d6), δ (ppm): −61.02 (s, 3F, CF3). 77Se NMR (76.35 MHz, DMSO-d6), δ (ppm): 451.0 (s).
Synthesis of compounds 4a–g. To a solution (10 mmol) of the corresponding selon 3a–g in 100 mL of absolute ethanol, 1.7 mL of 30% hydrogen peroxide was added (15 mmol) and refluxed for 1 h, then cooled to 20 °C. The solid precipitated from the solution was separated by filtration, washed with ethanol (2 × 50 mL), and dried at 40 °C.
Molecules 27 05799 i008
2,2′-diselane-1,2-diylbis(3-phenylquinazolin-4(3H)-one). Light brown solid (68%), mp 290 °C. Anal. Calcd. for C28H18N4O2Se2: C 56.01%, H 3.02%, N 9.33%. Found: C 56.09; H 3.06; N 9.37. ESI+-MS, m/z: calcd for [C28H18N4O2Se2+ H]+ 602.9838, found 602.9827 [C28H18N4O2Se2+ H]+. IR (KBr, selected bands, sm−1): 1685, 1544, 1468, 1261, 1201, 952, 770, 696. 1H NMR (500 MHz, DMSO-d6), δ (ppm): 8.05 (d, J = 8.0, 1H, H-5), 7.82 (t, 1H, H-7), 7.66 (m, 5H, Ph), 7.47 (t, 1H, H-6), 7.40 (d, J = 8.0, 1H, H-8).
Molecules 27 05799 i009
2,2′-diselane-1,2-diylbis [3-(2-methylphenyl)-quinazolin-4(3H)-one]. Orange solid (79%), mp 230 °C. Anal. Calcd. for C30H22N4O2Se2: C 57.33%, H 3.53%, N 8.91%. Found: C 57.22; H 3.56; N 8.79. ESI+-MS, m/z: calcd for [C30H22N4O2Se2+ H]+ 631.0152, found 631.0132 [C30H22N4O2Se2+ H]+. IR (KBr, selected bands, sm−1): 1684, 1610, 1575, 1538, 1467, 1254, 1199, 763, 695. 1H NMR (500 MHz, DMSO-d6), δ (ppm): 8.10 (d, 1H, H-5), 7.83 (m, 1H, H-7), 7.42–7.65 (m, 6H, H-6, H-8, 4H Ar), 2.24, 2.34 (s, 3H, CH3). 13C NMR (125.72 MHz, DMSO-d6), δ (ppm): 160.30, 160.25 (C=O), 151.00, 151.62 (C-Se), 148.4 (C-8a), 137.4 137.5 (C-2′), 135.8, 135.9 (C-1′), 135.76, 135.73, (C-7), 131.9 (C-3′), 132.0 (CH Ar), 130.2 (CH Ar), 128.2 (CH Ar), 127.5 (C-6), 127.3 (C-5), 126.4, 126.6 (C-8), 120.1 (C-4a), 17.6, 17.7 (CH3). 77Se NMR (76.35 MHz, DMSO-d6), δ (ppm): 522.3, 513.9 (s, 2Se).
Molecules 27 05799 i010
2,2′-diselane-1,2-diylbis [3-(2-methoxyphenyl)-quinazolin-4(3H)-one]. Orange solid (91%), mp 277 °C. Anal. Calcd. for C30H22N4O4Se2: C 54.56%, H 3.36%, N 8.48%. Found: 54.48; H 3.43; N 8.43. ESI+-MS, m/z: calcd for [C30H22N4O4Se2+H]+ 663.0050, found 663.0043 [C30H22N4O4Se2+H]+. IR (KBr, selected bands, sm−1): 1680, 1541, 1498, 1465, 1263, 1021, 764, 695, 640. 1H NMR (500 MHz, DMSO-d6), δ (ppm): 8.07 (dd, J = 12.5, J = 2.5, 1H, H-5), 7.81 (m, 1H, H-7), 7.70 (m, 1H, H-4′), 7.61 (m, 1H, H-6′), 7.51 (t, 1H, H-6), 7.41 (d, 1H, H-8), 7.38 (d, 1H, H-3′), 7.23 (t, 1H, H-5′), 3.84, 3.85 (3H, c, OCH3).
Molecules 27 05799 i011
2,2′-diselane-1,2-diylbis [3-(3-methoxyphenyl)-quinazolin-4(3H)-one]. Orange solid (83%), mp 271 °C. Anal. Calcd. for C30H22N4O4Se2: C 54.56%, H 3.36%, N 8.48%. Found: C 54.44; H 3.32; N 8.39. ESI+-MS, m/z: calcd for [C30H22N4O4Se2+H]+ 663.0050, found 663.0043 [C30H22N4O4Se2+H]+. IR (KBr, selected bands, sm−1): 3067, 1695, 1603, 1539, 1464, 1268, 1236, 1199, 1032, 905, 839, 768, 690. 1H NMR (500 MHz, DMSO-d6), δ (ppm): 8.08 (d, 1H, H-5), 7.80 (t, 1H, H-7), 7.60 (t, 1H, H-5′), 7.50 (t, 1H, H-6); 7.44 (d, 1H, H-8); 7.20–7.33 (m, 3H, 3H Ar), 3.85 (s, 3H, OCH3). 13C NMR (125.72 MHz, DMSO-d6), δ (ppm): 160.61 (C=O), 160.55 (C-O), 153.3 (C-Se), 147.9 (C-8a), 138.4 (C-1′), 135.56 (C-7), 131.2 (C-5′), 127.2 (C-5, C-6), 126.5 (C-8), 121.7 (C-6′), 120.5 (C-4a), 117.1 (C-4′), 115.4 (C-2′), 56.1 (OCH3). 77Se NMR (76.35 MHz, DMSO-d6), δ (ppm): 534.7 (s, 2Se).
Molecules 27 05799 i012
2,2′-diselane-1,2-diylbis [3-(2-fluorophenyl)-quinazolin-4(3H)-one]. Orange—red solid (66%), mp 250 °C. Anal. Calcd. for C28H16F2N4O2Se2: C 52.85%, H 2.53%, N 8.80%. Found: C 52.79; H 2.46; N 8.69. ESI+-MS, m/z: calcd for [C28H16F2N4O2Se2+H]+ 638.9650, found 638.9636 [C28H16F2N4O2Se2+H]+. IR (KBr, selected bands, sm−1): 1700, 1680, 1544, 1498, 1464, 1258, 1199, 1114, 951, 879, 771, 691, 638. 1H NMR (500 MHz, DMSO-d6), δ (ppm): 8.10 (d, J = 5.0, 1H, H-5), 7.70-7.82 (m, 2H, H-7, 1H Ar), 7.89 (m, 1H, 1H Ar), 7.65 (t, 1H, 1H Ar), 7.50–7.57 (m, 2H, H-6, 1H Ar), 7.48 (d, J = 8.0, 1H, H-8). 13C NMR (125.72 MHz, DMSO-d6), δ (ppm): 160.2 (C=O), 158.1 (d, 1J(13C-19F) = 252.5, C-2′-F,); 151.2 (C-Se), 147.8 (C-8a), 136.0 (C-7), 132.0 (C-5′), 134.36 (d, 3J(13C-19F) = 7.6, C-6′), 127.7 (C-6), 127.3 (C-5), 126.6 (C-8), 126.4 (d, 2J(13C-19F) = 3.8, C-3′), 124.3 (d, 2J(13C-19F) = 12.5, C-1′), 119.8 (C-4a), 117.6 (d, 3J(13C-19F) = 18.8, C-4′). 19F NMR (282.38 MHz, DMSO-d6), δ (ppm): -120.27 (s, 1F). 77Se NMR (76.35 MHz, DMSO-d6), δ (ppm): 535.6–533.8 (m, 2Se).
Molecules 27 05799 i013
2,2′-diselane-1,2-diylbis [3-(2-chlorophenyl)-quinazolin-4(3H)-one]. Cherry-red solid (87%), mp 255 °C. ESI+-MS, m/z: calcd for [C28H16Cl2N4O2Se2+H]+ 670.9051, found 670.9042 [C28H16Cl2N4O2Se2+H]+. IR (KBr, selected bands, sm−1): 3076, 1683, 1542, 1466, 1335, 1262, 1246, 1198, 947, 979, 765, 695, 637. 1H NMR (500 MHz, DMSO-d6), δ (ppm): 8.10 (dd, J = 10.0, J = 1.5, 1H, H-5), 7.80–7.95 (m, 2H, H-7, H Ar), 7.77 (m, 1H, H Ar), 7.70 (m, 1H, H Ar), 7.53 (m, 1H, H-6), 7.49 (m,1H, H-6). 13C NMR (125.72 MHz, DMSO-d6), δ (ppm): 160.0 (C=O), 150.9 (C-Se), 147.9 (C-8a), 136.0 (C-7), 134.2 (C, Ar), 133.6 (CH, Ar), 132.3 (CH, Ar), 131.2 (CH, Ar), 129.5 (CH, Ar), 127.6 (C-6), 127.3 (C-5), 126.7 (C-8), 120.0 (C-4a). 77Se NMR (76.35 MHz, DMSO-d6), δ (ppm): 532.5, 529.6, 528.5 (s, 2Se).
Molecules 27 05799 i014
2,2′-diselane-1,2-diylbis [3-[2-chloro-5-(trifluoromethyl)phenyl]quinazolin-4(3H)-one]. Orange solid (59%), mp 210 °C. Anal. Calcd. for C30H14Cl2F6N4O2Se2: C 44.74%, H 1.75%, N 6.96%. Found: C 44.66; H 1.66; N 6.87. ESI+-MS, m/z: calcd for [C30H14Cl2F6N4O2Se2+H]+ 806.8799, found 806.8784 [C30H14Cl2F6N4O2Se2+ H]+. IR (KBr, selected bands, sm−1): 1715, 1704, 1609, 1544, 1467, 1338, 1130, 1074, 959, 886, 847, 770, 694, 614. 1H NMR (500 MHz, DMSO-d6), δ (ppm): 8.53 (2 bs, 1H, H-6′), 8.16 (bs, 2H, H-3′, H-4′), 8.12 (dd, J = 8.0, J = 1.2, 1H, H-5); 7.87 (m, 1H, H-7); 7.48–7.58 (m, 2H, H-6, H-8). 13C NMR (125.72 MHz, DMSO-d6), δ (ppm): 160.1 (C=O), 149.8, 149.5 (C-Se), 147.8 (C-8a), 138.2 (C-1′), 136.1 (C-7), 135.2 (C-2′), 132.5 (C-3′), 130.37 (C-6′), 130.02 (k, 2J(13C,19F) = 33.2, C-5′), 129.8 (C-4′), 127.8 (C-5), 127.3 (C-6), 126.8 (C-8), 125.6 (к, 1J(13C-19F) = 271.3, CF3), 120.0 (C-4a). 19F NMR (282.38 MHz, DMSO-d6), δ (ppm): −61.09 (s, 3F, CF3). 77Se NMR (76.35 MHz, DMSO-d6), δ (ppm): 536.8, 533.5 (s, 2Se).

3.2. Computational Details

The DFT calculations based on the experimental X-ray geometries of 3f, 4b, 4c, 5, 6, 7, and 8 were carried out using the dispersion-corrected hybrid functional ωB97XD [66] with the help of Gaussian-09 [67] program package. The 6-311++G** basis sets were used for all atoms, except Te (for which quasi-relativistic MWB46 pseudopotentials [68], which described 46 core electrons, and the appropriate contracted basis sets were utilized). The topological analysis of the electron density distribution with the help of the quantum theory of atoms-in-molecules (QTAIM) method, electron localization function (ELF), reduced density gradient (RDG), and noncovalent interactions (NCI) analyses was performed by using the Multiwfn program (version 3.7) [69]. The VMD program [70] was used for the visualization of noncovalent interactions (NCI analysis). The Cartesian atomic coordinates for model supramolecular associates are presented in Table S1, Supplementary Materials.

4. Conclusions

In summary, we reported a convenient synthesis of series novel 2-selenoxo-1,2,3,4-tetrahydro-4-quinazolinone via a reaction between methyl anthranilate and isoselenocyanates. These compounds were found to undergo facile oxidation to furnish corresponding diselenides in high yields. The structures and purity of all compounds were unambiguously established using the 1H, 77Se, and 13C NMR spectroscopies; high-resolution electrospray ionization mass spectrometry; IR; elemental analyses; and X-ray diffraction analysis for several of them. X-Ray single crystal analysis was performed for 3f, 4b, 4c, 5, 6, 7, and 8, which revealed that selone 3f featured the formation of unsymmetrical supramolecular dimers via type II Se···Se ChB, while 3b and 3f did not exhibit ChB interactions, arguably due to dominance of other weak interactions in the crystal. For compounds 4b and 4c, a pair of intramolecular Se···N ChB were found in the solid state. Such intramolecular ChB interactions are scarce—CCDC contained only four structures featuring such contacts. The existence of all the above-mentioned ChB was additionally confirmed by DFT calculations followed by the topological analysis of the electron density distribution.

Supplementary Materials

The following supporting information can be downloaded at: https://mdpi.longhoe.net/article/10.3390/molecules27185799/s1, Figure S1: Crystal packing of 3b demonstrating the H-bonded chains of the crystallographically independent molecules A. Figure S2: Crystal packing of 3f demonstrating the ribbons towards the crystallographic c axis. Within the ribbons, the molecules are bound to each other by the strong N─H···O hydrogen bonds and weak nonvalent Se···Se interactions (Se1···Se2 [1−x, 2−y, 1−z] 3.7173(4) Å). Figure S3: The two projections of crystal packing of 3g demonstrating the two-tier layer parallel to (010). Within the layer, the molecules are bound to each other by the N─H···Se hydrogen bonds as well as the nonvalent Se···O (Se2···O2 [1−x, −0.5+y, 1.5−z] 3.3702(16) Å) and Cl···F (Cl2···F1 [1−x, −0.5+y, 1.5−z] 3.0607(17) Å) interactions. Scheme S1. Plausible mechanism for the formation of 3a–g. Table S1: Cartesian atomic coordinates for model supramolecular associates. Crystal structure determinations, Table S2: Crystal data and structure refinement for all compounds studied. References [71,72,73,74] are cited in Supplementary Materials.

Author Contributions

Conceptualization, A.V.B. and A.G.T.; methodology, A.V.B., V.K.O. and A.S.K.; investigation, A.S.N., E.V.C., V.K.O., V.N.K., R.K.A., A.O.C., G.N.B., M.M.G., M.N.K., A.A.K. and A.S.P.; writing—original draft preparation, A.S.N., V.K.O. and A.G.T.; writing—review and editing, A.S.N., V.K.O. and A.G.T.; supervision, A.V.B. All authors have read and agreed to the published version of the manuscript.

Funding

This work was performed under the support of the Russian Science Foundation (award no. 22-73-10007). X-Ray analysis was performed under the support of the RUDN University Strategic Academic Leadership Program. NMR analysis was carried out using the equipment of the Center for molecular composition studies of INEOS RAS.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Conflicts of Interest

The authors declare no conflict of interest.

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Molecules 27 05799 sch001 550
Scheme 1. Synthesis of 3a–g.
Scheme 1. Synthesis of 3a–g.
Molecules 27 05799 sch001
Molecules 27 05799 g001 550
Figure 1. Ball-and-stick representations of 3b, 3f, and 3g. Se···Se ChB for 3f is depicted as a dashed line. Grey and light grey spheres represent carbon and hydrogen atoms, respectively.
Figure 1. Ball-and-stick representations of 3b, 3f, and 3g. Se···Se ChB for 3f is depicted as a dashed line. Grey and light grey spheres represent carbon and hydrogen atoms, respectively.
Molecules 27 05799 g001
Molecules 27 05799 sch002 550
Scheme 2. Synthesis of 4a–g.
Scheme 2. Synthesis of 4a–g.
Molecules 27 05799 sch002
Molecules 27 05799 g002 550
Figure 2. Ball-and-stick representations of 4b and 4c demonstrating intramolecular Se···N ChB, depicted as dashed lines. Grey and light grey spheres represent carbon and hydrogen atoms, respectively.
Figure 2. Ball-and-stick representations of 4b and 4c demonstrating intramolecular Se···N ChB, depicted as dashed lines. Grey and light grey spheres represent carbon and hydrogen atoms, respectively.
Molecules 27 05799 g002
Molecules 27 05799 g003 550
Figure 3. Ball-and-stick representations of 5–8 demonstrating intramolecular Se···N ChB, depicted as dashed lines. Grey and light grey spheres represent carbon and hydrogen atoms, respectively.
Figure 3. Ball-and-stick representations of 5–8 demonstrating intramolecular Se···N ChB, depicted as dashed lines. Grey and light grey spheres represent carbon and hydrogen atoms, respectively.
Molecules 27 05799 g003
Molecules 27 05799 g004 550
Figure 4. Contour line diagram of the Laplacian of electron density distribution ∇2⍴(r), bond paths, and selected zero-flux surfaces (top), visualization of electron localization function (ELF, center), and reduced density gradient (RDG, bottom) analyses for contact Se···Se (chalcogen bond) in the X-ray structure 3f. Bond critical points (3, –1) are shown in blue, nuclear critical points (3, –3)—pale brown, ring critical points (3, +1)—orange, bond paths are shown as pale brown lines, length units—Å, and the color scale for the ELF and RDG maps is presented in a.u.
Figure 4. Contour line diagram of the Laplacian of electron density distribution ∇2⍴(r), bond paths, and selected zero-flux surfaces (top), visualization of electron localization function (ELF, center), and reduced density gradient (RDG, bottom) analyses for contact Se···Se (chalcogen bond) in the X-ray structure 3f. Bond critical points (3, –1) are shown in blue, nuclear critical points (3, –3)—pale brown, ring critical points (3, +1)—orange, bond paths are shown as pale brown lines, length units—Å, and the color scale for the ELF and RDG maps is presented in a.u.
Molecules 27 05799 g004
Molecules 27 05799 g005 550
Figure 5. Contour line diagram of the Laplacian of electron density distribution ∇2⍴(r), bond paths, and selected zero-flux surfaces (left), visualization of electron localization function (ELF, center), and reduced density gradient (RDG, right) analyses for contacts Se–Se and Se···N in the X-ray structure 4b. Bond critical points (3, –1) are shown in blue, nuclear critical points (3, –3)—pale brown, ring critical points (3, +1)—orange, bond paths are shown as pale brown lines, length units—Å, and the color scale for the ELF and RDG maps is presented in a.u.
Figure 5. Contour line diagram of the Laplacian of electron density distribution ∇2⍴(r), bond paths, and selected zero-flux surfaces (left), visualization of electron localization function (ELF, center), and reduced density gradient (RDG, right) analyses for contacts Se–Se and Se···N in the X-ray structure 4b. Bond critical points (3, –1) are shown in blue, nuclear critical points (3, –3)—pale brown, ring critical points (3, +1)—orange, bond paths are shown as pale brown lines, length units—Å, and the color scale for the ELF and RDG maps is presented in a.u.
Molecules 27 05799 g005
Molecules 27 05799 g006 550
Figure 6. Contour line diagram of the Laplacian of electron density distribution ∇2⍴(r), bond paths, and selected zero-flux surfaces (left), visualization of electron localization function (ELF, center), and reduced density gradient (RDG, right) analyses for contacts Se–Se and Se···N in the X-ray structure 4c. Bond critical points (3, –1) are shown in blue, nuclear critical points (3, –3)—pale brown, ring critical points (3, +1)—orange, bond paths are shown as pale brown lines, length units—Å, and the color scale for the ELF and RDG maps is presented in a.u.
Figure 6. Contour line diagram of the Laplacian of electron density distribution ∇2⍴(r), bond paths, and selected zero-flux surfaces (left), visualization of electron localization function (ELF, center), and reduced density gradient (RDG, right) analyses for contacts Se–Se and Se···N in the X-ray structure 4c. Bond critical points (3, –1) are shown in blue, nuclear critical points (3, –3)—pale brown, ring critical points (3, +1)—orange, bond paths are shown as pale brown lines, length units—Å, and the color scale for the ELF and RDG maps is presented in a.u.
Molecules 27 05799 g006
Molecules 27 05799 g007 550
Figure 7. Contour line diagram of the Laplacian of electron density distribution ∇2⍴(r), bond paths, and selected zero-flux surfaces (left), visualization of electron localization function (ELF, center), and reduced density gradient (RDG, right) analyses for contacts Se–Se and Se···N in the X-ray structure 5. Bond critical points (3, –1) are shown in blue, nuclear critical points (3, –3)—pale brown, ring critical points (3, +1)—orange, bond paths are shown as pale brown lines, length units—Å, and the color scale for the ELF and RDG maps is presented in a.u.
Figure 7. Contour line diagram of the Laplacian of electron density distribution ∇2⍴(r), bond paths, and selected zero-flux surfaces (left), visualization of electron localization function (ELF, center), and reduced density gradient (RDG, right) analyses for contacts Se–Se and Se···N in the X-ray structure 5. Bond critical points (3, –1) are shown in blue, nuclear critical points (3, –3)—pale brown, ring critical points (3, +1)—orange, bond paths are shown as pale brown lines, length units—Å, and the color scale for the ELF and RDG maps is presented in a.u.
Molecules 27 05799 g007
Molecules 27 05799 g008 550
Figure 8. Contour line diagram of the Laplacian of electron density distribution ∇2⍴(r), bond paths, and selected zero-flux surfaces (left), visualization of electron localization function (ELF, center), and reduced density gradient (RDG, right) analyses for contacts Se–Se and Se···N in the X-ray structure 6. Bond critical points (3, –1) are shown in blue, nuclear critical points (3, –3)—pale brown, ring critical points (3, +1)—orange, bond paths are shown as pale brown lines, length units—Å, and the color scale for the ELF and RDG maps is presented in a.u.
Figure 8. Contour line diagram of the Laplacian of electron density distribution ∇2⍴(r), bond paths, and selected zero-flux surfaces (left), visualization of electron localization function (ELF, center), and reduced density gradient (RDG, right) analyses for contacts Se–Se and Se···N in the X-ray structure 6. Bond critical points (3, –1) are shown in blue, nuclear critical points (3, –3)—pale brown, ring critical points (3, +1)—orange, bond paths are shown as pale brown lines, length units—Å, and the color scale for the ELF and RDG maps is presented in a.u.
Molecules 27 05799 g008
Molecules 27 05799 g009 550
Figure 9. Contour line diagram of the Laplacian of electron density distribution ∇2⍴(r), bond paths, and selected zero-flux surfaces (left), visualization of electron localization function (ELF, center), and reduced density gradient (RDG, right) analyses for contacts Se–Se and Se···N in the X-ray structure 7. Bond critical points (3, –1) are shown in blue, nuclear critical points (3, –3)—pale brown, ring critical points (3, +1)—orange, bond paths are shown as pale brown lines, length units—Å, and the color scale for the ELF and RDG maps is presented in a.u.
Figure 9. Contour line diagram of the Laplacian of electron density distribution ∇2⍴(r), bond paths, and selected zero-flux surfaces (left), visualization of electron localization function (ELF, center), and reduced density gradient (RDG, right) analyses for contacts Se–Se and Se···N in the X-ray structure 7. Bond critical points (3, –1) are shown in blue, nuclear critical points (3, –3)—pale brown, ring critical points (3, +1)—orange, bond paths are shown as pale brown lines, length units—Å, and the color scale for the ELF and RDG maps is presented in a.u.
Molecules 27 05799 g009
Molecules 27 05799 g010 550
Figure 10. Contour line diagram of the Laplacian of electron density distribution ∇2⍴(r), bond paths, and selected zero-flux surfaces (left), visualization of electron localization function (ELF, center) and reduced density gradient (RDG, right) analyses for contacts Te–Te and Te···N in the X-ray structure 8. Bond critical points (3, –1) are shown in blue, nuclear critical points (3, –3)—pale brown, ring critical points (3, +1)—orange, bond paths are shown as pale brown lines, length units—Å, and the color scale for the ELF and RDG maps is presented in a.u.
Figure 10. Contour line diagram of the Laplacian of electron density distribution ∇2⍴(r), bond paths, and selected zero-flux surfaces (left), visualization of electron localization function (ELF, center) and reduced density gradient (RDG, right) analyses for contacts Te–Te and Te···N in the X-ray structure 8. Bond critical points (3, –1) are shown in blue, nuclear critical points (3, –3)—pale brown, ring critical points (3, +1)—orange, bond paths are shown as pale brown lines, length units—Å, and the color scale for the ELF and RDG maps is presented in a.u.
Molecules 27 05799 g010
Molecules 27 05799 g011 550
Figure 11. Visualization of noncovalent interactions Se···Se, Se···N, and Te···N in 3D using NCI analysis technique in model supramolecular associates 3f, 6, 7, and 8.
Figure 11. Visualization of noncovalent interactions Se···Se, Se···N, and Te···N in 3D using NCI analysis technique in model supramolecular associates 3f, 6, 7, and 8.
Molecules 27 05799 g011
Table
Table 1. Values of the density of all electrons—⍴(r), Laplacian of electron density—∇2⍴(r) and appropriate λ2 eigenvalues, energy density—Hb, potential energy density—V(r), and Lagrangian kinetic energy—G(r) (a.u.) at the bond critical points (3, −1), corresponding to contacts Se···Se, Se···N, and Te···N in the X-ray structures 3f, 4b, 4c, 5, 6, 7, and 8, and approximately estimated strength for these interactions Eint (kcal/mol) [55].
Table 1. Values of the density of all electrons—⍴(r), Laplacian of electron density—∇2⍴(r) and appropriate λ2 eigenvalues, energy density—Hb, potential energy density—V(r), and Lagrangian kinetic energy—G(r) (a.u.) at the bond critical points (3, −1), corresponding to contacts Se···Se, Se···N, and Te···N in the X-ray structures 3f, 4b, 4c, 5, 6, 7, and 8, and approximately estimated strength for these interactions Eint (kcal/mol) [55].
Contact *⍴(r)∇2⍴(r)λ2HbV(r)G(r)Eint ≈ −V(r)/2
3f
Se···Se 3.717 Å0.0070.020−0.0070.001−0.0030.0040.9
4b
Se–Se 2.360 Å0.102−0.052−0.102−0.043−0.0740.03123.2
Se···N 2.899 Å0.0170.061−0.0170.002−0.0120.0143.8
4c
Se–Se 2.357 Å0.102−0.052−0.102−0.044−0.0750.03123.5
Se···N 2.870 Å0.0180.063−0.0180.001−0.0130.0144.1
5
Se–Se 2.359 Å0.102−0.054−0.102−0.044−0.0740.03023.2
Se···N 2.792 Å0.0210.070−0.0210.001−0.0150.0164.7
6
Se–Se 2.433 Å0.095−0.048−0.095−0.039−0.0660.02720.7
Se···N 2.733 Å0.0240.080−0.0240.001−0.0180.0195.6
Se···N 2.479 Å0.0420.115−0.042−0.003−0.0350.03211.0
7
Se–Se 2.343 Å0.104−0.052−0.104−0.045−0.0770.03224.2
Se···N 2.925 Å0.0170.059−0.0170.002−0.0110.0133.5
8
Te–Te 2.723 Å0.0720.138−0.072−0.018−0.0310.0139.7
Te···N 3.082 Å0.0160.056−0.0160.001−0.0100.0113.1
* The Bondi’s (shortest) Van der Waals radii for Te, Se, and N atoms are 2.00, 1.90, and 1.55 Å, respectively [56].
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Osmanov, V.K.; Chipinsky, E.V.; Khrustalev, V.N.; Novikov, A.S.; Askerov, R.K.; Chizhov, A.O.; Borisova, G.N.; Borisov, A.V.; Grishina, M.M.; Kurasova, M.N.; et al. Facile Access to 2-Selenoxo-1,2,3,4-tetrahydro-4-quinazolinone Scaffolds and Corresponding Diselenides via Cyclization between Methyl Anthranilate and Isoselenocyanates: Synthesis and Structural Features. Molecules 2022, 27, 5799. https://doi.org/10.3390/molecules27185799

AMA Style

Osmanov VK, Chipinsky EV, Khrustalev VN, Novikov AS, Askerov RK, Chizhov AO, Borisova GN, Borisov AV, Grishina MM, Kurasova MN, et al. Facile Access to 2-Selenoxo-1,2,3,4-tetrahydro-4-quinazolinone Scaffolds and Corresponding Diselenides via Cyclization between Methyl Anthranilate and Isoselenocyanates: Synthesis and Structural Features. Molecules. 2022; 27(18):5799. https://doi.org/10.3390/molecules27185799

Chicago/Turabian Style

Osmanov, Vladimir K., Evgeniy V. Chipinsky, Victor N. Khrustalev, Alexander S. Novikov, Rizvan Kamiloglu Askerov, Alexander O. Chizhov, Galina N. Borisova, Alexander V. Borisov, Maria M. Grishina, Margarita N. Kurasova, and et al. 2022. "Facile Access to 2-Selenoxo-1,2,3,4-tetrahydro-4-quinazolinone Scaffolds and Corresponding Diselenides via Cyclization between Methyl Anthranilate and Isoselenocyanates: Synthesis and Structural Features" Molecules 27, no. 18: 5799. https://doi.org/10.3390/molecules27185799

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