Quantum Chemical Studies of the Substituent Effect on the Reaction of

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Quantum Chemical Studies of the Substituent Effect on the Reaction of Carbonyl Oxime With Amine Yunus Kaya J. Phys. Chem. A, Just Accepted Manuscript • DOI: 10.1021/acs.jpca.6b05147 • Publication Date (Web): 30 Jun 2016 Downloaded from http://pubs.acs.org on July 3, 2016

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The Journal of Physical Chemistry

Quantum Chemical Studies of the Substituent Effect on the Reaction of Carbonyl Oxime with Amine Yunus Kaya† †

Bursa Tech Univ, Fac Nat Sci Architecture & Engn, Dept Chem, TR-16190 Bursa, Turkey.

ABSTRACT: The reaction of the two different substitue carbonyl oximes (isonitrosoacetylnaphtaline, inanH and nitro-isonitrosoacetophenone, ninapH) with two different amines (1-phenylethanol amine, pea and ethanol amine, ea) were synthesized and characterized by elemental analyses, IR,

1

H and

13

C NMR

spectroscopic methods. As a result of these experimental studies, two different levels for all reactions were determined: (I) formation of imine oxime, (II) rearrangement of imine oxime or formation of amido alcohol. After a mechanism was suggested for all these reactions, the reaction mechanism of carbonyl oxime with amine was first studied by means of the B3LYP/6-311G(d,p) method. Because of the deficiency of the density functionals theory (DFT) on dispersion effects, wB97X-D/6-311G(d,p) method which includes dispersion correction was used to obtain the reaction heat and free energy barriers to explain why the formation (imine oxime) and unexpected rearrangement products (amido alcohol) occur or not. The statistical thermodynamic method was used to obtain the changes on thermodynamic properties between 100 and 500 K of the studied molecules. In kinetic viewpoint, the slowest step of the reactions is IN1-TS2-IN2 step, which determines step of reaction kinetic. In addition, the spectroscopic properties such as vibrational and NMR chemical shifts were studied for all the molecules. The Frontier Molecular Orbitals (FMOs), HOMOs and LUMOs are monitored for all the molecules.

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1. INTRODUCTION The imine oximes are oxime compounds containing the imine and the oxime groups, usually acting as bidentate ligands through the imine and oxime nitrogen atoms to form a five-membered chelate ring.1 General structure of imine oxime is shown in Fig. 1. Upon complexation, the oxime hydrogen can generally dissociate. Because of the imine oximes have potential electron donor groups, their coordination capability are high.2 Also, imine oxime derivatives have pharmacological activity3 and widely used as a metal extracting agent in analytical chemistry.4 Some of imine oxime derivatives, such as imipenem,5 panipenem6 and meropenem7 currently are used in clinical studies, due to their potent antibacterial effects. In recent years, much attention has been given to theoretical studies of oximes, as well as their complexes. Especially, density functional theory (DFT) has been frequently used in theoretical modeling for oximes, and theirs metal complexes.8–14 DFT method is more accurately calculated many molecular properties than the traditional correlated ab initio methods due to better echange-correlation functionals. It is also more favorable computational efforts.15 It has been shown from literature investigations that DFT method shows the high degree of accuracy of DFT methods in reproducing the experimental values in terms of geometry, dipole moment, vibrational frequency, NMR and UV-vis. spectroscopic studies.12,16–27 Although theoretical studies of oximes and their metal complexes intensively have been worked, quantum chemical studies of imine oximes and their metal complexes have received less interest. Furthermore, the formation mechanism and the rearrengment reactions of the imine oximes, and substituent effects of these reactions have not been studied as experimentally and theoretically in the literature. Recently, DFT studies of the reaction mechanism of two imine oximes, namely (3E)-3-aza-5-(hydroxyimino)-1,4-diphenylpent-3-en-1-ol

and

(1E,2E)-[(2-

hydroxyethyl)imino]-2-phenyl-ethanal oxime, and their novel rearrangments were performed by our group.28 In this study, two different products obtained experimentally in the literature were modelled by DFT and the dispersive effect were studied. The reaction mechanism was suggested for these two products. In current study, four different molecules (I-IV) were firstly synthesized, and then the suggested reaction mechanism were studied for these four molecules. The aim of this work is to


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to explain the reason of the formation and unexpected rearrangement of the products and how the substituent effect of the rearrangement of imine oxime. Experimentaly, the imine oxime (IIa) was obtained by the reaction of inanH and ea, while the unexpected rearrangement products (Ib, IIIb and IVb) were synthesized by the other carbonyl oxime and amine reactions. For this purpose, first, DFT/B3LYP method and 6-311G(d,p) basis set was used for optimizations, and then the wB97X-D/6311G(d,p) level of theory was selected to determine the reaction heats and free energy barriers of the formation mechanisms of the imine oximes (Ia-IVa) and amido alcohols (Ib-IVb). Further, kinetics and thermodynamics of the rate-limiting steps, that is, formation and rearregment reactions, were explored in detail. Some molecular structure parameters, vibrational frequencies and NMR chemical shifts of the title compounds (Ib, IIa, IIIb and IVb) have been calculated by B3LYP/6-311G(d,p) level of theory and compared with the experimental data. Frontier molecular orbitals (FMOs), HOMOs and LUMOs of the final molecules were monitored with the same level.

2. EXPERIMENTAL AND COMPUTATIONAL DETAILS 2.1. Materials and Methods. The elemental analyses (C, H and N) were performed using a EuroEA 3000 CHNS elemental analyser. IR spectra were recorded on a Thermo Nicolet 6700 FT-IR spectrophotometer as KBr in the frequency range 4000-400 cm–1 pellet. 1H NMR (400 MHz) and

13

C NMR (100 MHz)

spectra were recorded on a Varian Mercury plus spectrometer in DMSO-d6 and TMS was used as an internal standard. 2.1.1. Synthesis. The all compounds were prepared by our previous study,28 and details on the synthesis and characterizations which are elemental anaylsis, IR and NMR spectra are presented in Supporting Information. 2.2. Computational Methods. All calculations were conducted using density functional theory (DFT) with the Becke–Lee–Yang–Parr functional (B3LYP) method29 as implemented in the GAUSSIAN 03 program package.30 In the first step, all molecules of neutral formation mechanism of I-IV(a,b) were optimized using the B3LYP method and 6-311G(d,p) basis set. Then, the wB97X-D/6-311G(d,p) level developed by Grimme and co-workers31 were used for Gibbs free energy



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calculations. Vibrational frequencies of all molecules were performed at the same level to find local minima (all real vibrational frequencies) or transition states (one imaginary vibrational frequency). The intrinsic reaction coordinate (IRC) calculation was used to check true transition structure at the reaction path. The Integral Equation Formalism of the Polarizable Continuum Model (IEFPCM) with ethanol solvent was used for the single point SCRF calculations at wB97X-D/6-311G(d,p) level. Geometries calculated in the gas phase have been used for SCRF calculations.32–34 The harmonic vibrational frequencies were calculated at B3LYP/6-311G(d,p) level for the optimized structures, and the obtained frequencies were scaled by 0.95835 for 4000-1700 cm−1 and 0.97836 for 1700-400 cm−1 ranges, respectively. Furthermore, theoretical vibrational spectra of the I-IV were interpreted by means of PEDs using VEDA 4 program.37 1H and

13

C NMR chemical shifts (δH and δC) of HL1

and HL2 were calculated using the GIAO method38 in DMSO at the B3LYP/6311G(d,p) level and using the TMS shielding calculated as a reference. The global electrophilicity index, ω, is given by the following expression39 ω = µ2/2η, in terms of the electronic chemical potential µ and the chemical hardness η. Both quantities may be approached in terms of the one-electron energies of the frontier molecular orbitals (FMOs) HOMO and LUMO, εH and εL, as µ ≅ −(εH + εL)/2 and η ≅ (εL - εH)/2, respectively. Global softness, S is related to global hardness and is given by the inverse of 2η.39

3. RESULTS AND DISCUSSION The synthesis of all molecules are given in Scheme 1. Generally, all of the molecules were synthesized by reaction of carbonyl oxime (isonitrosoacetylnaphtaline, inanH and nitro-isonitrosoacetophenone, ninapH) with amine (1-phenylethanol amine, pea and ethanol amine, ea) afforded moderate to good yields (73–86%) of imine oxime or amido alcohol. In this study, the effect on product formation, which is imine oxime (IIVa) or amido alcohol (I-IVb) was investigated with different substituents. In this context, two different carbonyl oximes whose substituents are naphthyl and nitrophenyl and two different amines whose substituents are phenyl and hydrogen have been selected. The synthesized compounds were characterized by elemental analyses, IR, 1H and

13

C NMR spectral data. Detailed information regarding the


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characterization of the molecules are stated in Supporting Information. According to experimental results, the proposed structures for the four products (Ib, IIa, IIIb and IVb) are compatible. These results showed that as a result of the reaction between inanH and ethanol amine (ea), imine oxime (IIa) is obtained, while the amido alcohols (Ib, IIIb and IVb) are synthesized the other reactions between carbonyl oxime and amine. 3.1. Optimized structures. The optimized parameters (bond lengths and bond angles) of Ib, IIa, IIIb and IVb obtained using the B3LYP/6-311G(d,p) basis set are listed in Table S3 and the optimized structures of all molecules are shown in Fig. 2. The most important bonds of the amido alcohol compounds are CO and NH of amides, while the imine oximes are CN imine and oxime. The CO/NH bond lengths of Ib, IIIb and IVb were calculated as 1.224/1.007, 1.221/1.007 and 1.221/1.006 Å, respectively. Moreover, the CN imine and oxime bond lengths were obtained as 1.279 and 1.277 Å in the IIa. In addition, the OH bond length was calculated as ca. 0.963 Å in the all molecules. The O-C-N/C-N-C bond angles of Ib, IIIb and IVb were calculated as 121.7°/121.8°, 122.9°/122.2° and 122.6°/121.4°, respectively. In the imine oxime compound, IIa, the C-N-C and C-N-O bond angles were found as 121.2° and 111.4°, respectively. The oxime bond angle, N-O-H belonging to imine oxime was calculated as 102.8°. 3.2. Theoretical approach on reaction mechanism. In our previous study, the reactions between isonitrosoacetophenone (inapH) and two different substitue amines, pea and ea were studied experimentally.40,41 Then, 28

mechanisms were performed theoretically by our group.

these reaction

In this section, the

suggested reaction mechanism was studied as theoretically for synthesizing four different molecules (I-IV). In the all calculations, Lenovo Thinkstation D20 workstation and the GAUSSIAN 03 program package were used. First, DFT/B3LYP method was performed for all optimizations. Because of the deficiency of the DFT functionals on dispersion effects, wB97X-D/6-311G(d,p)

method which includes

dispersion

correction has been used to obtain the reaction heat and free energy barriers to explain why the formation (imine oxime) and unexpected rearrangement products (amido alcohol) occur or not.



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DFT is the most popular and widely used method in computational chemistry. It provides very precise results as easly, and feasible level of theory for number of problems supporting chemical experimental research. However, It is insufficient in describing dispersion and the energies of all molecules. Johnson et al.42 and Grimme43 developed the dispersion corrections on the energies of the DFT method. They presented the DFT-D44,45 and DFT-D3 methods31 to decrase the deficiency on dispersion interaction of the DFT. So the results calculated by wB97XD/6-311G(d,p) which includes dispersion corrections have been used for energy discussions.

In general, the reaction mechanism is in two levels:

I) Formation of imine oxime. The mechanism of the formation reaction of imine oxime involves two steps, namely: (i) formation of a carbinolamine intermediate, and (ii) dehydration of the carbinolamine to give the final imine oxime. II) Rearrangement of imine oxime or formation of amido alcohol. The rearragement mechanism of imine oxime in ethylalcohol has theoretically investigated. The mechanism is three steps which are (i) dehydration of imine oxime, (ii) water attack to imine, and (iii) removal of HCN to give the final amido alcohol. The potential energy surfaces (PES’s) of the studied molecules has been given in Fig. 3. Relative energies of the reactants, intermediates (IN), transition states (TS) and products are given in Table 1. All calculations were performed with adding an ethanol molecule for the mechanism. In the first step of the mechanism, N atom of amine attack as a nucleophile to C atom of the substrate, and the carbinolamine (hemiaminal) intermediate (IN1) forms through TS1 transition state as a result of this nucleophilic attack. The attack of the amine molecule results in an interaction of the imine C atom through the O atom. Then, the six-membered ring transition structure, TS2 is formed at that position consequently. This energy barrier (Ea) of this step is quite high, being 100.24, 92.45, 91.28 and 94.69 kJmol−1 for all molecules, I, II, III and IV, respectively. The other carbinolamine, IN2 is obtained with result of transforming TS2, whose energy barriers (Ea) are rather low at 41.23, 44.56, 37.54 and 39.87 kJmol−1, compared to TS2, for all molecules, respectively. The distance between the C and N


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atoms in the carbonyl oxime+amine is ca. 4.0 Å, while this distance was calculated at ca. 1.5 Å in the IN2 for all reactions. This change in the bond distance indicate that the single bond forms between C and N atoms. This is followed by the approach of the amine hydrogen to the hydroxyl oxygen to form TS3 with a relatively high energy barrier of ca. 80 kJmol−1 for I and II, and 53 kJmol-1 for III and IV. The ∆Gcal values of the formation of the final imine oxime are -21.23, -10.42, -11.62, -13.84 kJmol−1, for Ia, IIa, IIIa and IVa, respectively. The optimized geometries of the studied molecules has given in Figs. 4 and 5 for the reactions I and II, and in Figs S5 and S6 for the reactions III and IV. As shown in Figs. 4, 5, S5 and S6, in the rearragement mechanism of imine oxime, the hydroxyhethyl H atom interacts with the oxime O atom, and dehydration occurs from oxime group in the first step. Then, a water molecule attacks to the C atom of imine as a nucleophile, and forms the tetrahedral intermediate IN4 through transition state TS5. The activation barrier of this step was calculated 96.72, 108.45, 88.47 and 90.13 kJmol−1 for all molecules, I, II, III and IV, respectively. In the last step, the H atom of hydroxyl group transfers via TS6 transition state which is sixmembered ring. The energy barriers of this step were determined at 92.61, 91.26, 82.44 and 87.46 kJmol−1 for all molecules. The ∆Gcal values calculated for the rearragement reactions of imine oximes are 7.21, 41.23, -2.81 and 5.87 kJmol−1 for all molecules. According to these results, all formation reactions of the imine oximes are exothermic. Therefore all of the molecules are formed as possible in ethylalcohol solution. On the other hand, in the first, third and fourth reactions (I, III and IV), the Gibbs free energy exchange, ∆G of the rearrangement reactions are exothermic or low endothermic energy, which are affordable in the ethylalcohol solution. Henceforth, the amido alcohols (Ib, IIIb and IVb) are formed due to rearrangement of the imine oximes (Ia, IIIa and IVa). But, the amido alcohol (IIb) does not occur in ethylalcohol solution, since the ∆G of the rearrangement reaction is endothermic and the energy value is high, 41.23 kJ/mol. These results are confirmed experimentally during the synthesis of all molecules. 3.3. Theoretical approach on thermodynamic parameter. The statistical thermodynamic method has been used to obtain the changes on thermodynamic



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properties which were calculated from theoretically frequencies between 100 and 500 K of the studied molecules at B3LYP/6-311G(d,p) level. The changes on Gibbs free energy (∆G) at various temperatures are given in Table 1. The formations of imine oximes, I-IVa are exothermic process, while the amido alcohols, Ib, IIb and IVb are positive, so these reactions are endothermic, except IIIb, calculated at negative values. The ∆G values are predicted to be 8.88, 45.86, 1.63 and 7.75 kJmol-1 at 100 K for formations of I-IVb, respectively. These relative free energies decreased to 4.42, 33.14, -5.62 and 4.68 kJmol-1, respectively at 500 K. In the course of formations of amido alcohols, I-IVb the calculated ∆G decreases with increasing temperature. It is easier to obtain the rearrangement products, I-IVb from the thermodynamic results. 3.4. Theoretical approach on rate constant. Rate constant is a key parameter in the kinetic study. It can be calculated from statistical mechanics. Rate constant equation is obtained from transition state theory (TST) based on statistical thermodynamics. Therefore, the rate constants were calculated at various temperatures, which are 100 to 500 K by RRKM46–48 and TST48,49 theories. The results reveal that the slowest step of the reactions, which is determined the rate constant of reaction is IN1-TS2-IN2 step. Therefore, this step is the rate-determining step of all the reactions. The values of the rate constants for the I-IV have been reported in Table 2 at different temperatures (100–500 K). The all rate constants were obtained at atmospheric pressure. It is evident from Table 2 that the rate constant increases with the increase of temperature. Also, the reaction of inanH with pea is carried out slowly, while the reaction of ninapH with pea is the fastest reaction. The rate constants of the I-IV were calculated at 298 K 1.67x10-5, 3.87x10-4, 6.20x10-4 and 1.57x10-4 s-1 in atmospheric condition, respectively. The rate constants for the reactions of formation or rearragement imine oximes indicate that these reactions can be fast at 298 K. According to data results, the rate constants of the reactions of formation or rearragement imine oximes under atmospheric pressure increase with temperature, which indicates that the reaction will be faster in higher temperatures. Fig. 6 is Arrhenius curves for reactions of formation or rearragement imine oximes, where ln k versus 1000/T are plotted. From the ln k plot versus 1000/T, Arrhenius equation of the reactions I-IV can be calculated as follow:


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kI = 1.778 x 1011 e-90.764 kJ/mol/RT

(1)

kII = 1.206 x 1011 e-82.003 kJ/mol/RT

(2)

kIII = 1.997 x 1011 e-81.627 kJ/mol/RT

(3)

kIV = 9.739 x 1010 e-83.108 kJ/mol/RT

(4)

3.5. Frontier Molecular Orbitals (FMOs). Frontier molecular orbitals (FMOs) which are the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) are important for some aspects of molecules, such as chemical stability, chemical reactivity, electronegativity (χ), electrophilicity index (ω) and the hardness (η) / softness (S).

50-52

These properties and HOMO, LUMO

energies of final products are listed in Table 3. The HOMO is an electron donor, while the LUMO acts as an electron acceptor. The energy band gap (∆E) of the system shows the chemical reactivity of compounds. If the compound has a lower value of energy gap, it is more reactive or less stable. As seen in Table 3, IIIb is the smallest energy gap among all molecules. The hardness (η) and softness (S) of the molecules are related to directly energy gap, ∆E. If the molecule has a higher energy gap, it is more hardness or less softness. Thus, Ib and IIa are referred to as a hard molecule when matched with IIIb and IVb.53 The chemical potential (I) is represented by HOMO energy. It occurs from the charge distribution between two systems having different chemical potentials. In this study, electronic potentials (I) are negative for all compounds, since they act as electrophiles. On the other hand, the electron accepting ability of the systems is defined very similar to η and I from the electrophilicity index (ω). High values of the electrophilicity index increases the electron accepting abilities of the molecules. Here, the electron accepting abilities of final products are arranged in the following order: IVb > IIIb > Ib > IIa . In the HOMO of all compounds, the electron density mainly delocalized over the associated phenyl/naphthyl ring except IVb molecule, which HOMO orbital consists of amide group. The electron density is delocalized on the phenyl/naphthyl ring except IIa molecule which is delocalized over the associated imine oxime group in the LUMO orbital, as shown in Fig. 7.



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4. CONCLUSIONS In this work, first, the four different reactions were studied experimentally, and then these reaction mechanisms were performed theoretically to explain why the formation (imine oxime) and unexpected rearrangement products (amido alcohol) occur or not. The formation mechanisms of compounds imine oximes (Ia, IIa, IIIa and IVa), and their rearrangement mechanisms in the ethylalcohol solution were studied using the B3LYP/6-311G(d,p) and wB97XD/6-311G(d,p) levels of calculations with the solvent effects of ethanol using the IEFPCM continuum model. The formations of the carbinolamine intermediates (IN2) are the rate-determining steps which occurs via nucleophilic attack of the pea / ea molecules to the carbonyl C atom of inanH and ninapH. The ∆Gcal values of the formations of compounds Ia, IIa, IIIa and IVa as 21.23, -10.42, -11.62, -13.84 kJmol−1, respectively. These results confirm the imine oxime compounds. The energy barriers of rearrangement of imine oximes (formation of amido alcohols, Ib, IIb, IIIb and IVb) were calculated to be 7.21, 41.23, -2.81 and 5.87 kJmol−1 in the ethylalcohol solution, respectively. These results indicate that the IIa was not rearranged in ethylalcohol solution, while the Ib, IIIb and IVb were obtained by the results of the rearrangement of the related imine oximes.

The

spectroscopic properties such as vibrational and NMR chemical shifts were calculated for the all molecules, and compared with experimental results. IR spectral analyses show that the predicted vibrational frequencies are in good agreement with the experimental values. 1H and

13

C atoms of Ib, IIa, IIIb and IVb were marked with

NMR calculations. The thermodynamic results show that the rearrangement products, I-IVb, can be obtained easier at higher temperatures. Rate constant equation is obtained from transition state theory (TST) based on statistical thermodynamics. The kinetic results show that the reaction will be faster in higher temperatures. The FMOs orbitals played an important role for the molecules were calculated at the same basis set. The electron accepting abilities of Ib, IIa, IIIb and IVb were determined in the following order: IVb > IIIb > Ib > IIa.


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ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpca PPP. Manufacturers and purity of the chemicals used in this study. The experimental and discussion sections were presented for synthesis, IR and NMR spectra. IR spectra (Table S1, Figs S1 and S2) and NMR spectra (Table S2, Figs. S3 and S4) were given. The selected bond distances and angles were listed in Table S3. The optimized geometries of the reactants, intermediates, transition states and products for the reaction of ninapH and pea were given in Fig S5, while demonstrated for the reaction of ninapH and ea in Fig. S6.



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Abbreviations inanH

isonitrosoacetylnaphtaline

ninapH

nitro-isonitrosoacetophenone

pea

1-phenylethanol amine

ea

ethanol amine

Ia

(2-Hydroxy-2-phenyl-ethylimino)-naphthalen-2-yl-acetaldehyde oxime

Ib

Naphthalene-2-carboxylic acid (2-hydroxy-2-phenyl-ethyl)-amide

IIa

(2-Hydroxy-ethylimino)-naphthalen-2-yl-acetaldehyde oxime

IIb

Naphthalene-2-carboxylic acid (2-hydroxy-ethyl)-amide

IIIa

(2-Hydroxy-2-phenyl-ethylimino)-(4-nitro-phenyl)-acetaldehyde oxime

IIIb

N-(2-Hydroxy-2-phenyl-ethyl)-4-nitro-benzamide

IVa

(2-Hydroxy-ethylimino)-(4-nitro-phenyl)-acetaldehyde oxime

IVb

N-(2-Hydroxy-ethyl)-4-nitro-benzamide

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]; Phone: +90-224-294-1738. Notes The authors declare no competing financial interest.

ACKNOWLEDGMENTS This work is a part of a research project KUAP(F)-2015/20. We thank Uludag University for the financial support given to the projects.


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Table 1 Gibbs free energy changes (in kJmol-1) of the reactions of I - IV at the different temperatures. T (K)

100

200

298.15

400

500 24.32 (13.82)

inanH+pea (ea) – Ia → Ib (IIa → IIb) inanH+pea (ea)

17.21 (7.96)

18.64 (9.12)

21.23 (10.42)

23.05 (12.12)

TS1

82.23 (84.02)

83.82 (85.95)

85.46 (87.43)

88.11 (89.42)

90.01 (92.23

IN1

56.46(41.84)

58.88 (43.62)

61.53 (46.34)

64.09 (49.19)

68.06 (52.82) 106.08 (100.25)

TS2

92.80 (84.42)

95.90 (87.42)

100.24 (92.45)

104.41 (96.15)

IN2

31.72 (33.53)

36.14 (37.42)

41.23 (44.56)

44.56 (47.63)

48.30 (49.76)

TS3

76.96 (72.03)

80.23 (74.52)

83.12 (78.81)

86.14 (82.36)

89.51 (85.31)

Ia (IIa) + water

0

0

0

0

0

Ia (IIa)

0

0

0

0

0

73.94 (79.09)

77.52 (82.00)

80.21 (88.23)

82.96 (90.12)

86.02 (91.94)

TS4 IN3

46.96 (52.14)

50.73 (55.84)

53.42 (59.97)

56.0 (62.14)

59.42 (66.30)

TS5

90.10 (99.46)

93.45 (103.97)

96.72 (108.45)

98.46 (110.88)

101.23 (112.56)

IN4

66.12 (66.86)

69.02 (70.66)

71.86 (73.43)

74.34 (75.63)

76.69 (77.45)

TS6

85.61 (85.42)

89.88 (86.62)

92.61 (91.26)

95.11 (94.83)

97.53 (97.06)

8.88 (45.86)

8.10 (43.41)

7.21 (41.23)

5.86 (36.47)

4.42 (33.14)

Ib (IIb) + HCN

ninanH+pea (ea) – IIIa → IIIb (IVa → IVb) ninapH+pea (ea)

8.91 (9.96)

9.76 (11.85)

11.62 (13.84)

13.34 (15.93)

15.84 (18.89)

TS1

58.12 (64.84)

60.86 (68.65)

64.36 (71.35)

67.10 (74.63)

70.21 (78.43)

IN1

34.03 (41.78)

36.21 (44.96)

39.67 (48.64)

44.16 (51.74)

46.41 (54.75)

TS2

83.46 (85.42)

86.97 (90.26)

91.28 (94.69)

93.88 (97.35)

96.21 (99.97)

IN2

30.17 (33.72)

34.62 (36.45)

37.54 (39.87)

39.65 (42.77)

43.87 (46.06)

TS3

45.12 (48.01)

47.62 (50.26)

51.76 (54.42)

53.87 (57.96)

56.09 (60.06)

IIIa (IVa) + water

0

0

0

0

0

IIIa (IVa)

0

0

0

0

0

TS4

70.52 (74.61)

73.20 (77.46)

75.61 (81.43)

78.86 (85.41)

81.76 (88.63)

IN3

31.63 (37.63)

35.35 (39.61)

39.59 (42.89)

42.61 (45.94)

45.30 (47.98)

TS5

80.74 (82.64)

84.09 (85.56)

88.47 (90.13)

91.96 (94.88)

94.76 (98.36)

IN4

52.84 (57.11)

55.85 (60.31)

59.86 (64.13)

63.01 (68.41)

66.86 (70.96)

TS6

75.32 (80.79)

79.88 (84.21)

82.44 (87.46)

85.36 (90.01)

87.63 (92.88)

1.63 (7.75)

1.05 (7.82)

-2.81 (5.87)

-4.88 (5.21)

-5.62 (4.68)

IIIb (IVb) + HCN



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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Table 2 The total rate constant data (in s-1) are calculated at the B3LYP/6-311G(d,p) level. k (s-1) Temperature (K)

I

II -37

III -32

IV

100

6.97x10

1.66x10

5.27x10

4.99x10-33

200

3.97x10-13

6.12x10-11

8.03x10-11

1.11x10-11

298

1.67x10-5

3.87x10-4

6.20x10-4

1.57x10-4

400

0.19

2.31

4.58

1.61

500

86.11

350.03

925.12

374.20


-32

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Table 3 HOMO and LUMO energies, energy gap (∆E), absolute electronegativity (χ) chemical hardness (η), softness (S) and electrophilicity index (ω) of Ib, IIa, IIIb and IVb Compound

Ib

IIa

IIIb

IVb

E (HOMO, a.u.)

-0.228

-0.226

-0.260

-0.270

E (LUMO, a.u.)

-0.059

-0.057

-0.107

-0.108

4.60

4.60

4.16

4.41

χ

-3.903

-3.849

-4.991

-5.141

η

2.298

2.298

2.081

2.203

S

0.218

0.218

0.240

0.227

ω

3.314

3.223

5.985

5.999

Global Reactivity Descriptors

∆E (eV)



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure captions

Scheme 1 Synthesis reaction of the title compounds

Fig. 1 The general structure of imine oximes

Fig. 2 The optimized structures of Ib, IIa, IIIb and IVb molecules

Fig. 3 The potential energy diagrams showing the formation of compounds I, II, III and IV calculated by wB97XD/6–311G(d,p)

Fig. 4 The optimized geometries of the reactants, intermediates, transition states and products for the reaction of inanH and pea

Fig. 5 The optimized geometries of the reactants, intermediates, transition states and products for the reaction of inanH and ea

Fig. 6 Arrhenius curves for the reaction rate constants for I-IV reactions

Fig. 7 Frontier molecular orbitals (FMOs) of Ib, IIa, IIIb and IVb molecules


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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Scheme 1



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 1

R

N R''

N

R'

OH


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Figure 2



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 3


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Figure 4



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 5


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Figure 6



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 7


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Table of Contents


Quantum Chemical Studies of the Substituent Effect on the Reaction of

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