Supporting information for: Water-Tuned Tautomer-Selective Tandem Synthesis of the 5,6-Dihydropyrimidin-4(3 H )-ones, Driven under the Umbrella of Sustainable Chemistry

The selective synthesis of 5,6-dihydropyrimidin-4(3H)-one scaffold (precursor of dihydrouracil) was a very difficult synthetic challenge that, so far, has not been achieved. For the first time, in this paper, green, selective and high-yields approach to 40 novel 5,6-dihydropyrimidin-4(3H)-ones (DHPMs) by one-pot reaction of aldehydes, Meldrum's acid and isothioureas under solvent-free conditions, in the presence of water, since an additive is presented. In the majority of cases, introduced methodology gave an unprecedented tautomer-selective fashion toward targeted compounds with excellent tautomeric purity (>99.9%), which reached 100% in few cases. The molecular structure of the five compounds has been determined by X-ray crystallography. In each one of them, very short length for the corresponding N2-C1 bond was noticed, making them especially interesting from a structural standpoint. This experimental fact can imply a highly localized electron π density in this part of each heterocyclic ring. The obtained experimental results, which are determined from NMR and ESI-MS study, indicate that this Biginelli-type reaction smoothly proceeds in a one-pot mode, pointing to the three-step tandem process, proceeding via the Knoevenagel, aza-Michael, and retro-Diels-Alder reactions. The presented strategy also had the following advantages: reduction amount of waste, excellent values of green chemistry metrics (cEF, EcoScale and GCIS), and it is the first eco-friendly strategy toward the DHPMs scaffold. © Copyright 2018 American Chemical Society.Supplementary data for the article: [https://dx.doi.org/10.1021/acssuschemeng.8b03127]Related to: [http://vinar.vin.bg.ac.rs/handle/123456789/7886

Dehydrozingerone analogues: Reaction of O-alkyl derivatives of vanillin and methyl cyclopropyl ketone

O-Alkyl vanillines and methyl cyclopropyl ketone reacts under Claisen- Schmidt conditions yielding corresponding enone derivatives, dehydrozingerone analogues with cyclopropane ring fragment, (E)-1-cyclopropyl-3-(4-alkoxy-3- methoxyphenyl)prop-2-en-1-ones. All new compounds were well characterized by IR, 1H and 13C NMR spectroscopy and physical data

4-[(4-Methylphenyl)sulfanyl]butan-2-one

In the title compound, C(11)H(14)OS, all non-H atoms are essentially coplanar, with a mean deviation of 0.023 Å. In the crystal, centrosymmetrically related mol­ecules are weakly connected into dimers by pairs of C—H⋯O inter­actions. The dimers are further linked along the a axis by weak C—H⋯π and C—H⋯S inter­actions

4-Ethoxy-3-methoxybenzaldehyde

In the title compound, C10H12O3, all non-H atoms are approximately coplanar, with an r.m.s. deviation of 0.046 Å. In the crystal, very weak C-H⋯O interactions link the molecules into sheets parallel to (101)

4-[(4-Methylphenyl)sulfanyl]butan-2-one

In the title compound, C11H14OS, all non-H atoms are essentially coplanar, with a mean deviation of 0.023 Å. In the crystal, centrosymmetrically related molecules are weakly connected into dimers by pairs of C - H⋯O interactions. The dimers are further linked along the a axis by weak C - H⋯π and C - H⋯S interactions

Synthesis, structural properties and DNA protective activity of ferrocenyl N-acyl pyrazolines

Two series of new ferrocenyl pyrazolines have been synthesized by the reac-tion of ferrocenyl chalcones and their analogues with hydrazine hydrate in thepresence of corresponding carboxylic acid. Single-crystal X-ray crystallographicdata were used for detailed analysis of the interesting versatility of four com-pounds in the formation of intermolecular interactions. The analysis revealedan excellent structural flexibility of the present ferrocenyl pyrazoline moleculesfor the non-covalent interactions, with a particular contribution of the ferro-cene units. In addition, for comparison with crystallographic findings, weinvestigated the protective effect of all compounds on DNA against hydroxyland peroxyl radicals induced by Fe2+,H2O2, and 2,20-azobis(2-amidinopro-pane) dihydrochloride (AAPH). The results indicated that all compoundsshowed rather similar DNA protective activity, which was comparable withquercetin as a well-known protective compound. This similarity in antigeno-toxic action could be explained by the established excellent structural flexibil-ity of ferrocenyl pyrazolines for the formation of different intermolecularinteractions as important structural property for molecular recognition

Structural and spectroscopic investigation of 1-acetyl-2-(4-ethoxy-3-methoxyphenyl) cyclopropane and its NLO activity

To identify promising compounds and to develop a potent non-linear optical material, the molecule 1-acetyl-2-(4-ethoxy-3-methoxyphenyl) cyclopropane (AEMC) was selected. FTIR and FT-Raman spectroscopy techniques were employed to predict the functional groups and vibrational modes of AEMC. Gaussian 09 W software was utilised to analyse the parameters of the optimised title compound. Reactive sites were forecasted using MEP plots. To clarify the chemical significance of the molecule, ELF and LOL are utilised. Furthermore, the presence of interactions within the molecule is confirmed by RDG analysis. The strong and weak hydrogen bonds between the non-bonding atoms of AEMC are studied with the aid of AIM analysis. Additionally, the material's capacity to produce non-linear effects (NLO) was ascertained by examining the linear polarizability and first order hyper polarizability values

Density functional theory calculations, vibrational spectral analysis and topological analysis of 1-acethyl-2(4-isopropoxy-3-methoxyphenyl) cyclopropane with docking studies

A systematic spectroscopic investigationof 1-acethyl-2(4-isopropoxy-3-methoxyphenyl) cyclopropanewasperformed by utilizing Density functional theory approaches at B3LYP level usingGaussian 09 W software package. The FT-IR and FT-Raman techniques were utilized to assign the spectral properties of the title compound. On the basis of Natural Bond Orbital (NBO) analysis,the transfer of second order perturbation energies and ElectronDensity (ED) from filled lone pairs of Lewis base to unfilled Lewis acid sites wereanalysed. The chemical stability,distribution of energy and energetic behaviour of the compound were calculated from the Highest Occupied and Lowest Unoccupied Molecular Orbital (HOMO-LUMO) Analysis. The nucleophilic and electrophilic locales of the moleculewas perceived by the Molecular electrostatic potential (MEP). NCI investigation gives data around the inter and intra non covalent interlinkages. By using the Multiwavefunction software the topological analysis of ELF and LOL were performed. The chemical reactivity sites were determined by means of the fukui function. The assignments of vibrational spectra were computed using thevibration energy distribution analysis (VEDA). Drug similarityfactors were intended to understand the biological aspects. Vadar software was used to generate the Ramachandran plot. The bioactivity of the title compound was confirmed fromthe molecular docking studies