Theoretical Study of Mechanism of 2,3-Dihydro-1,5-benzodiazepin-2-ones Hydrazinolysis

Okovytyy, Sergiy I.; Sviatenko, Liudmyla K.; Gaponov, Alexandr O.; Tarabara, I. N.; Kas’yan, L. I.; Leszczyński, Jerzy

doi:10.1021/jp807644e

Cited by 5 publications

(7 citation statements)

References 16 publications

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“…Full gas-phase geometry optimizations were performed using the density functional theory with the Beck's three-parameter nonlocal exchange functional and the gradient-corrected functional of Lee et al (B3LYP), [72][73][74] due to its successful application in a number of hydrazinolysis [75,76] and analogous substituted hydrazine systems, [9,11,12] obtaining reasonable molecular structures, vibrational frequencies, and bond energies. Basis set of double-f split valence plus polarization and diffusion quality (6-31þG(d,p)) [77] was employed in all optimization calculations.…”

Section: Computational Detailsmentioning

confidence: 99%

Mechanism for the reaction of 2‐naphthol with N‐methyl‐N‐phenyl‐hydrazine suggested by the density functional theory investigations

et al. 2011

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For the first time the computed mechanisms for the novel reaction of 2-naphthol with N-methyl-N-phenylhydrazine, leading to 1-amino-2-naphthol (Tang et al., J Am Chem Soc 2008, 130, 5840), have been investigated using the density functional theory. Four distinct possible pathways were evaluated: two amination mechanisms with the attack of NH(2) group respectively at the α-position C1 and β-position C3 atoms of 2-naphthol (pathways 1 and 2) as well as two rearrangement processes with displacement of the phenolic hydroxyl group followed by the benzidine-like rearrangement at the α-position C1 and β-position C3 atoms of 2-naphthol, respectively (pathways 3 and 4). Solvent effect has been tested based on the optimized geometries of the stationary points in solution at the B3LYP/PCM/6-31+G(d,p) level of theory with an averaged dielectric constant of binary solvent. Single-point energies of the optimized structures have been calculated using three hybrid density functionals, B3LYP, MPW3LYP, and B3PW91 with the 6-311++G(3df,2p) basis set. Our computed results clearly manifest that pathway 1 (α-amination) has the highest possibility to occur, with the Gibbs free energies being lower by 6 to 20 kcal/mol compared with the other three pathways, which leads to 1-amino-2-naphthol and N-methylaniline as products. It is in excellent agreement with the experimental observation.

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Section: Computational Detailsmentioning

confidence: 99%

Mechanism for the reaction of 2‐naphthol with N‐methyl‐N‐phenyl‐hydrazine suggested by the density functional theory investigations

et al. 2011

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“…Okovytyy and co-workers described the hyrazinolysis mechanism of 2,3-dihidro-1,5benzodiazipine-2-thiones 13 and the 2,3-dihidro-1,5-benzodiazipin-2-ones. 14 They have examined in detail the possible mechanisms of the initial step of the reactions and concluded that the benzodiazipine systems were attacked by a hydrazine molecule toward the azomethine bond. The system considered here is similar to 3-R- [1,2,4]triazino [2,3-c]quinazolin-2-ones (condensed aromatic and heterocyclic rings with azomethine bond), and we suggest that interaction with the nucleophile will proceed in a similar manner.…”

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…Despite the abundance of data based on experimental results, only a few studies − have dealt with the overall mechanism of nucleophile addition reactions. Okovytyy and co-workers described the hyrazinolysis mechanism of 2,3-dihidro-1,5-benzodiazipine-2-thiones and the 2,3-dihidro-1,5-benzodiazipin-2-ones . They have examined in detail the possible mechanisms of the initial step of the reactions and concluded that the benzodiazipine systems were attacked by a hydrazine molecule toward the azomethine bond.…”

Section: Introductionmentioning

confidence: 99%

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Hydrazinolysis of 3-R-[1,2,4]Triazino[2,3-c]quinazolin-2-ones. Synthetic and Theoretical Aspects

et al. 2014

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It has been shown that heating of 3-R-[1,2,4]triazino[2,3-c]quinazolin-2-ones with 5-fold excess of hydrazine hydrate in propanol-2 gave the corresponding 3-(2-aminophenyl)-6-R-1,2,4-triazin-5-ones with high yields. The mechanism of the reaction has been proposed based on the results of theoretical investigation at B3LYP and MP2 levels of theory. According to calculations, an attack of the hydrazine molecule on the C6═N7 double bond leads to ring-opening with N5-C6 bond cleavage. The process continues by addition of the second nucleophile molecule and elimination of the formazan fragment through a series of transformations that yield the target product.

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“…The recyclization of heterocyclic compounds in reactions with hydrazine and its derivatives has been extensively studied experimentally and has been shown to be very important in organic synthesis. − Despite numerous predictions of the possible mechanisms of the recyclization processes, theoretical verification for the proposed mechanisms by quantum mechanical calculations has not been yet accomplished. In a recent paper, we reported the theoretical investigation on hydrazinolysis of 4-methyl-2,3-dihydro-1,5-benzodiazepin-2-one leading to 3-methylpyrazolone-5. To broaden our analysis of the 1,5-benzodiazepines, in this study, we investigated the mechanism of the recyclization reaction which takes place during interaction of 2,3-dihydro-1,5-benzodiazepine-2-thiones with hydrazine (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

Comprehensive DFT and MP2 Level Investigations of Reaction of 2,3-Dihydro-1,5-benzodiazepine-2-thiones with Hydrazine

et al. 2009

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Density functional theory approach was used for the 4-phenyl-2,3-dihydro-1,5-benzodiazepine-2-thione compound to determine the mechanism of hydrazinolysis of 4-substituted 2,3-dihydro-1,5-benzodiazepine-2-thiones. Single-point calculations at the MP2/6-311+G(d,p)//B3LYP/6-311+G(d,p) level were performed for the more accurate energy prediction. The solvent effect was taken into account by carrying out single-point calculations using the PCM methodology. The obtained results show that in the investigating mechanism the first step consists of the hydrazine molecule addition to the thiocarbonyl bond of the 4-phenyl-2,3-dihydro-1,5-benzodiazepine-2-thione following removal of H(2)S. Further addition of another hydrazine molecule to the azomethyne bond and cyclization with pyrazole ring formation occur, and then the diazepine ring-opening and the removal of hydrazine molecule proceed. Finally, imine-enamine tautomerization leads to 5-N-(2-aminophenyl-1-amino)-3-phenylpyrazole as a main product that is in agreement with the experimental observation. The cyclization step is a rate-determining step of this reaction.

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Theoretical Study of Mechanism of 2,3-Dihydro-1,5-benzodiazepin-2-ones Hydrazinolysis

Cited by 5 publications

References 16 publications

Mechanism for the reaction of 2‐naphthol with N‐methyl‐N‐phenyl‐hydrazine suggested by the density functional theory investigations

Mechanism for the reaction of 2‐naphthol with N‐methyl‐N‐phenyl‐hydrazine suggested by the density functional theory investigations

Hydrazinolysis of 3-R-[1,2,4]Triazino[2,3-c]quinazolin-2-ones. Synthetic and Theoretical Aspects

Comprehensive DFT and MP2 Level Investigations of Reaction of 2,3-Dihydro-1,5-benzodiazepine-2-thiones with Hydrazine

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