Journal of the Brazilian Chemical Society
Print version ISSN 0103-5053On-line version ISSN 1678-4790
Computational Study of Electronic Effects from β-Substituents on the Tautomerism of Naphthazarin Derivatives
aInstituto de Química, Universidade Federal vì Rio Grande do Sul, Avenida Bento lớn Gonçalves, 9500, 91501-970 Porto Alegre-RS, Brazil
bTANAC S/A, Rua Torbjorn Weibull, 199, 95780-000 Montenegro-RS, Brazil
cCurso de Química, Universidade Luteramãng cầu bởi Brasil, Farroupilha, 8001, 92452-900 Canoas-RS, Brazil
dDepartamento de Engenharia de Processos, Fundação de Ciência e Tecnologia, Washington Luiz, 675, 90010-460 Porto lớn Alegre-RS, Brazil
In this work, semi-empirical AM1 và DFT B3LYP/6-31G** calculations were applied in the study of the interconversion aao ước tautomers of several naphthazarin & 5-amino-8-hydroxy-1,4-naphthoquinone β-substituted derivatives bearing electron-donor or electron-withdrawing groups. Using a semi-empirical method, detailed potential energy landscapes for proton transfers were built, from which four tautomers và four transition states of interconversions were identified for each compound. These structures were recalculated without restraints and, using the Boltzmann distribution, the populations for each of the four tautomers and their respective sầu molar fractions were calculated. The calculations showed that the tautomeric equilibrium is shifted lớn the tautomer where the ring with the substituent has a quinonic nature & is more pronounced when the β-substituent is an electron donor group. For derivatives of 5-amino-8-hydroxy-1,4-naphthoquinone, an equilibrium between an aromatic and a 1,5-naphthoquinonic non-aromatic enamine was observed, being the former the most stable.
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Keywords: tautomerism; B3LYP; AM1; molecular modeling; electronic effect
Naphthoquinones belong khổng lồ a large class of natural and synthetic compounds. These compounds are frequently found in plants and on a smaller scale in inferior animals, exhibiting a broad scope of applications, such as drugs & dyes.1-9 5,8-Dihydroxy-1,4-naphthoquinone (1), naphthazarin, và its derivatives are particularly important due lớn their biological và pharmacological activities10-15 và versatility as intermediates in the synthesis of more diversified chemical structures.9,16-24 One of their features is the presence of tautomerism.12,25
The tautomeric equilibrium changes their reactivity & spectroscopic properties.16,18,đôi mươi Therefore, a systematic investigation of dihydroxy-1,4-naphthoquinones tautomerism can contribute to lớn the understanding of their chemical reactivity, pharmacological activity, & spectroscopic characteristics. Despite being a quite simple concept, tautomerism is a phenomenon that still arises interest & has been the ayên ổn of several recent studies due lớn its great importance to lớn organic & medicinal chemistry, biochemistry, pharmacology and molecular biology.26 In many cases, the biological activity of a molecule or its reaction mechanism with biological receptors is strongly dependent on the tautomerism. However, experimental studies involving tautomerism are very difficult due to lớn the fast reaction rate of these processes.
Naphthazarin (1) và its derivatives are able of hydroren transfer from the hydroxyl khổng lồ the syn periplanar carbonyl groups. For each derivative sầu, four tautomers can be drawn (Scheme 1).27
Scheme 1 Four possible tautomeric structures of naphthazarin và its derivatives. The derivatives studied in the present work constitute three groups: (i) 1-7; (ii) 8-13 and (iii) 14-19.
Glazunov and Berdyshev28 studied the effect from mono khổng lồ tetrachloro substitution on naphthazarin using DFT B3LYP/6-31G**. Their results showed that the strength of the intramolecular H-bond increases when the chlorine β-substitution is near lớn hydroxyl groups, but decreases in the proximity of carbonyl groups. A similar study was performed by Zahedi-Tabrizi and Farahati29 using DFT/B3LYP/6-311++G(d,p) in order khổng lồ investigate the effect of methyl substituents on the intramolecular H-bond strength. According to the authors, the strength of this bond is increased with the substitution at different positions of the naphthazarin.
Moore & Scheurer,25 in a pioneer study published in 1966, studied the tautomerism in naphthazarin (1) và β-substituted derivatives by 1H nuclear magnetic resonance (NMR) (CDCl3). Naphtazarin showed identical 1a và 1b tautomers (Scheme 1), therefore, all β-hydroren absorbs in the same frequency, leading to signals at chemical shifts considered intermediate between the quinoidal & aromatic ones, which can be attributed lớn a fast equilibrium. These authors also observed the influence of electronic effects from the β-substituents: for electron donor (R=OH, OMe, OAc, Et), equilibrium is shifted to lớn the 2-substituted tautomer. For electron withdrawing substituents (Ac), equilibrium is shifted khổng lồ the 6-substituted one. In 1976, Kobayashi et al.30 reported (for the first time) the 13C NMR spectrum of naphthazarin (1). The presence of only three signals denoting the symmetry of the two six-member condensed rings can be explained again by the quiông xã tautomers conversion.
Carreño et al.31 analyzed, using 13C NMR (CDCl3), β-substituted thioderivatives of 1 (R=STol, SOTol, SO2Tol) &, similarly to lớn Moore & Scheurer,25 they found a relationship between the substituent electronic effect & the tautomer stability. Glazunov et al.32-36 investigated the tautomerism of 2 (R=OH) and other polyhydroxynaphthazarines by infrared (IR) spectroscopy in solution (CHCl3, CCl4, CDCl3 and CH2Cl2). Once more, 2a was the only observed structure.
In 1982, de La Vega et al.37 reported the first computational study of tautomerism in naphthazarin (1) and methyl derivatives by ab initio calculations applying a minimum basis set. The authors concluded that 1a and 1b are global energetic minima while 1c & 1d are saddle points 104.6 kJ mol-1 higher in energy. Such observations suggested that this tautomerism is not concerted, with the hydrogene transfers occurring in two consecutive steps. Mariam et al.38,39 studied 5-amine-8-hydroxy-1,4-naphthoquinone (20) tautomerism by semi-empirical, ab initio, & mật độ trùng lặp từ khóa functional theory (DFT) calculations. Tautomer 20a was found the most stable one.27,38 NMR studies in CDCl3 reported by Fariña et al.40 support this result. Mariam and Musin27 studied the naphthazarin (1) tautomerism by B3LYP/6-31G**. Differently from de La Vega et al.,37 these authors found 1c & 1d as local minima, instead of saddle points. In this case, a 15.1 kJ mol-1 barrier was estimated.
Liang và Yi41 studied the alkannin tautomerism (Scheme 1, X=Y=O, & R=CH(OH)CH2CH=C(CH3)2) at the same cấp độ of theory. Once more, 2-substituted tautomer (a) is the most stable, but the energy difference from the 6-substituted one (b) is only 5.5 kJ mol-1. A 24.2 kJ mol-1 interconversion barrier was found. Mel"man et al.,42 in 2009, synthesized 8a by ammonolysis of 2a. 1H NMR spectrum in dimethyl sulfoxide (DMSO-d6), however, matches the 8b tautomer. Authors, indeed, found 8b khổng lồ be 23.0 kJ mol-1 more stable than 8a by B3LYP/6-31G* calculation. Jacquemin et al.43 reported a CAM-B3LYP/6-31G** study of naphthazarin tautomerism in order lớn investigate its electronic structure. They concluded that 1,5-naphthoquinone structure (c and d) have a transition state with activation energy higher than 41.8 kJ mol-1.
In the present study, the tautomerism of naphthazarin (1) và several β-substituted derivatives or analogues was investigated by AM1 semi-empirical Hamiltonian & DFT B3LYP/6-31G** calculations. Detailed potential energy landscapes for proton transfer (prototropy) were built using semi-empirical methods, the most stable geometries và transition states were refined with the higher màn chơi calculations and Boltzmann distribution was used lớn estimate the relative sầu populations of possible equilibrium structures. The prototropic mechanism và transition states were also evaluated.
The naphthoquinones studied in this work are shown in Scheme 1. AM144 semi-empirical & mật độ trùng lặp từ khóa functional B3LYP45-47 with 6-31G** basis mix calculations were carried out using Spartan" 08 (1.2.0).48 The tautomers (a), 2-substituted structures were used as the starting structures for semi-empirical calculations. Bond distances d1 (Y-H) & d2 (O-H) were hold fixed in each calculation và varied from 1 khổng lồ 2 Å with 0.1 Å increments. Heats of formation (ΔHF) were calculated for all optimized geometries. Heats of formations (ΔHF) were plotted in function of d1 and d2. The estimated potential energy surfaces allowed lớn locate four equilibrium geometries (a-d) và four transition state estimates. For each naphthoquinone derivative, the eight structures were optimized without any constraint by semi-empirical calculations và then used as đầu vào for the ab initio calculations.
In addition, vibrational frequencies were calculated, for transition states as well as for the minima. The frequency calculations established the nature of the stationary points by confirming that the stable minima have sầu all positive vibrational frequencies và the transition states have only one imaginary frequency relative sầu to lớn the path connecting between two minima.
The global maxima found by AM1 calculations were also optimized by DFT with length restriction of the bonds d1 và d2. The values found were compared with the four local minima and the four transition states to evaluate whether the energy value remains higher as observed by AM1 calculations. The eight structures optimized by DFT (four minima & four transition states) were plotted in an 8th degree polynomial fit graphic.
The zero-point energy (ZPE) corrected electronic energies
Results và Discussion
Naphthoquinones 1-19 can be divided into lớn three groups: (i) naphthazarin (1) và its 2-substituted derivatives (2-7); (ii) 2-substituted derivatives of 5-amino-8-hydroxy-1,4-naphthoquinone (8-13); (iii) 2-substituted derivatives of 8-amino-5-hydroxy-1,4-naphthoquinone (14-19). Besides keto-enamine tautomerism, enol-imine equilibrium is also observed on groups (ii) and (iii). In each group, the effect of electron donor (OH, OMe, OAC) & electron withdrawing (Ac, công nhân, NO2) groups were evaluated.
As result of semi-empirical calculations, potential energy surfaces were constructed, using d1 và d2 as reaction coordinates. In Figures 1, 2 and 3 are shown the potential energy surface for naphthazarin (1, Figure 1), 5-amino-6,8-dihydroxy-1,4-naphtoquinone (8, Figure 2) & 8-amino,2,5-dihydroxy-1,4-naphtoquinone (14, Figure 3), one example of each group. All other systems have sầu potential energy surfaces with very similar qualitative sầu features, as shown in the Supplementary Information section.
Figure 1 Tautomerism (prototropy) of 5,8-dihydroxy-1,4-naphtoquinone (naphthazarin, 1): heats of formation (ΔHF, AM1 Hamiltonian) versus bonds distances Y-H (d1) & O-H (d2).
Figure 2 Tautomerism (prototropy) of 5-amino-6,8-dihydroxy-1,4-naphtoquinone (8): heats of formation (ΔHF, AM1 Hamiltonian) versus bonds distances Y-H (d1) and O-H (d2).
Figure 3 Tautomerism (prototropy) of 8-amino-2,5-dihydroxy-1,4-naphtoquinone (14): heats of formation (ΔHF, AM1 Hamiltonian) versus bonds distances Y-H (d1) và O-H (d2).
For each system, four local minima are found at the vertices of the diagrams, which correspond khổng lồ the four tautomers (1a-d). In the case of naphthazarin, tautomers 1a và 1b, as well as 1c và 1d, are identical to each other. A global maximum is observed for d1 and d2 equal to lớn 1.3 Å. For each system, four transition state estimates are found along the edges. This indicates that the mechanism is not concerted và the transfer of the second hydrogene only takes place after the first one is already finished, otherwise a low potential energy path with simultaneous changes of d1 and d2 would be found. Two alternative sầu pathways are possible in which either 1c or 1d are intermediates. For all pathways the saddle points assumed as the transition states are always early ones. These results are in agreement khổng lồ those reported by Mariam và Musin.27
For each system, the four tautomers (a, b, c và d) và the four estimates of transition states (ac, ad, cb & db) were reoptimized with the same semi-empirical method, without distance restrictions. After that, they were calculated using DFT with functional B3LYP và basis set 6-31G**. The frequencies were calculated for transition states and for the minima. The frequency calculations established the nature of the stationary points by confirming that the stable minima have sầu all positive vibrational frequencies & the transition states have sầu only one imaginary frequency relative lớn the path connecting between two minima. Visual inspections (by animation) of the normal mode with imaginary frequency (not shown) confirm that this mode is related lớn the path connecting in two minima. The estimate of the global maximum found by AM1 calculations (d1 and d2 equal khổng lồ 1.3 Å) were optimized by DFT. The energy values found were compared with the four local minima & the four transition states confirming that the maximum global energy remains higher as observed by AM1 calculations.
The relative heats of formation obtained by DFT, considering the most stable tautomer form as zero, are shown in Table 1 for the groups (i), (ii) & (iii) defined above. Based on these data, interconversion energy protệp tin diagrams were built and are shown in Figures 4, 5 & 6. The tautomers had their molar fraction estimated at 300 K by the Boltzmann distribution law. These results are presented in Table 2.
Table 1 Relative sầu total energies (ΔET / kJ mol-1): equilibrium geometries and transition states on the tautomerism of naphthazarin and its derivatives B3LYP/6-31G**
Figure 4 Total energy (ET) variation in tautomerism of β-substituted 5,8-dihydroxy-1,4-naphthoquinones (B3LYP/6-31G**), group (i).
Figure 5 Total energy (ET) variation in tautomerism of β-substituted 5-amino-8-hydroxy-1,4-naphthoquinones (B3LYP/6-31G**), group (ii).
Figure 6 Total energy (ET) variation in tautomerism of β-substituted 8-amino-5-hydroxy-1,4-naphthoquinones (B3LYP/6-31G**) group (iii).
Table 2 Naphthazarin and its derivatives tautomers molar fraction (xi) obtained from total energies (B3LYP/6-31G**) màn chơi of theory with ZPE correction
Naphthazarin has two possible equilibrium tautomers, 1,4- và 1,5-naphthoquinone structures, 1a (identical to 1b) and 1c (identical lớn 1d), respectively. However, the first one has molar fraction equal khổng lồ 1. As it occurs for naphthazarin, for all the other compounds, 1,5-dicarbonylic structures (c or d tautomers) are negligible. For the naphthoquinones from group (i), (see Tables 1 and 2 and Figure 4) the exclusive tautomer is the 2-substituted one if the substituent is electron donor (2a-4a). Otherwise, in the case of electron-withdrawing groups, both tautomers (a and b) are present in equilibrium (5a-7a và 5b-7b), but the b tautomers were favored. Indeed, the electron-donor substituent stabilizes the carbonyl group. In the second case, the 6-substituted tautomer molar fraction increases because the electron withdrawing group is stabilized by the phenolic OH. Results are in agreement with experimental & theoretical studies previously reported.25,32,36
Conversion between tautomers a & b occurs, as mentioned, through 2- or 6-substituted 1,5-naphthoquinones, c or d, respectively, never in a concerted fashion. The favored pathway depends on transition states energies, not intermediate relative sầu stability. However, the pathway mechanism involves two steps và, hence, two energy barriers. The highest one determines the reaction rate, while the lowest one can be neglected for the purpose of mechanism study. In the present discussion about the kinetics, we are assuming that the interconversion is dominated only by the thermally activated hopping over the barrier. However, it is known that, at least for low temperatures, a significant contribution of incoherent tunneling may play a significant role in the proton transfer dynamics in naphthazarin49,50 yielding lower effective activation barriers.51 An estimate of the tunneling effect for our systems, however, is out of the scope of the present work và therefore our kinetic Mã Sản Phẩm focus the high temperature regime. The same considerations apply also khổng lồ the discussion about the tautomerism kinetics of molecules in groups (ii) and (iii). For group (i) naphthoquinones, the path through intermediate c is preferential, independently of electronic effects from the β-substituent. According to the energy profiles (Figure 4), the proton transfer rate with electron-donor substituents is expected to be controlled by the step cb. For electron-withdrawing groups, the barrier height is smaller, so the proton transfer is expected khổng lồ be faster for these compounds.
Naphthoquinones from group (ii) (see Tables 1 & 2 and Figure 5), on the other h&, exhibit also imine (a); amine (b) equilibria, besides keto-enol tautomerism. In these cases, imine tautomer (8a-13a) is always disfavored, as showed by Mariam et al.38,39 and Fariña et al.40 In the interconversion between tautomers a and b, the transition state da has the highest barrier và therefore is a limiting step to the proton transfer mechanism. Electron-donor substituents decrease the barrier height. According to Tables 1 và 2, 1,5-naphthoquinonic tautomers (d) in group (ii) are always more stable than the corresponding 1,4-naphthoquinonic tautomers (a). The same behavior was also observed by Marian và Chantranupong39 using BLYP/6-31G** for the 5-amino-8-hydroxy-1,4-naphthoquinone. According lớn these authors, the tautomeric equilibrium is shifted towards the enamines, with preference for the aromatic ones. Besides that, it is noteworthy that tautomer c is not stable for compounds 11 & 13, as shown in Figure 7. This behavior is due lớn the fact that the electron-withdrawing substituents stabilize the aromatic system. Moreover, the imine, when making a hydroren bond with the substituent, has its basiđô thị enhanced, favoring the proton transfer. This behavior was not observed for the compound 12 (-CN) which, despite being electron-withdrawing, does not make hydroren bonds with the imine.
Figure 7 Tautomeric equilibrium for 5-amino-8-hydroxy-6-nitro-1,4-naphthoquinone (13).
In this case, the transition state a-c was not found for the compounds 11 and 13 & a double proton transfer could occur. However, the preferred path would be a-d-b (see Figure 5).
Analogously, in group (iii) (see Tables 1 và 2 and Figure 6), tautomers 14a-19a are the most stable, showing molar fractions very nearly lớn 1, in equilibrium with c tautomers when electron-withdrawing substituents are present. Similar lớn group (ii) compounds, the enamine tautomers are also preferred. This behavior was already observed by Marian và Chantranupong39 using BLYP/6-31G** for the 5-amino-8-hydroxy-1,4-naphthoquinone. The intramolecular 1,5-proton shift, depends, however, on the structure itself và its substituents. In contrast khổng lồ the group (ii) compounds, in the interconversion between tautomers a và b, the transition state cb is the limiting step in the proton transfer mechanism.
The electronic effects of different substituents on tautomeric equilibrium of naphthazarin & 19 derivatives were studied by semi-empirical AM1 & DFT B3LYP/6-31G** calculations. Starting from detailed potential energy landscapes calculated using AM1, it was possible to identify, for each compound, four equilibrium tautomers và four transition states. Moreover, it can be concluded that the proton transfer does not occur in concerted fashion. Based on these structures, a structural refinement, followed by a DFT calculation using B3LYP/6-31G** & a molar fraction calculation of tautomers was carried out. For 2-substituted 5,8-dihydroxy-1,4-naphtoquinones, group (i), there was a clear shift towards the tautomer with substituent in the quinone ring (a) for the electron-donor substituents & towards the tautomer with substituent in the aromatic ring (b) for electron-withdrawing groups. For group (ii), the tautomeric equilibrium shifted almost entirely to tautomer b, with a small presence of tautomer d when the substituent is electron donor. For group (iii), the tautomeric equilibrium is shifted towards tautomer a, with a small presence of tautomer c, when the substituent is electron-withdrawing. Through the proposed methodology it can be predicted the tautomeric equilibrium of naphthazarin và derivatives, providing useful information to lớn elaboration of synthetic routes and interactions in biological systems.
Supplementary data are available không lấy phí of charge at http://jbcs.sbq.org.br as PDF tệp tin.
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