Preparation, Full Characterization and Theoretical Studies for New Herniarin derivatives

- Novel Herniarin compounds were prepared and identified by UV– VIS, FTIR, NMR spectra. Theoretical Studies and molecular structure with optimized geometry were done by utilizing Density functional theory for the prepared compounds


Introduction
Azo-dyes are the most essential and adaptable class of synthetic organic and natural compounds, with a gigantic mixture of utilizations [1]. These can be acquired effectively and cheaply utilizing a variety of diazo and coupling compound. They have high coloring and great fastness properties and wide applications in territories, for example, coloring of material strands, plastics, cowhide, paper and bio-restorative studies [2]. Coumarins assume a vital part in natural science. While coumarin is a colorless compound, some of its derivatives shading and extreme fluorescence [3]. The preparation of coumarin dyes have pulled in the consideration of scientific experts for a long time, as countless items contain this heterocyclic core. These colors are likewise abused in concoction, biochemical, physical and pharmaceutical applications. The coumarin is not fluorescent, but rather the presentation of an electron-pulling back gathering, for example, a diazotized fragrant amine or an acetyl gathering makes it very fluorescent. The coumarins are for the most part exceptionally helpful mixes for concoction change because of the simplicity of blend [4]. Azocoumarin colors were combined in two-stage system, arrangement of diazonium salt, then coupling response with coumarin [5].

I. Computational Studies 1. Mulliken Charges and Stabilities
The hypothetical studies [8][9][10] for new herniarin uncovered that the nuclear charges have been influenced by the ring's vicinity substituent. Molecular geometries of the all molecules were fully optimized by DFT (density functional theory) B3LYP method [11] utilizing 3-21G basis set [12] by ChemBioOffice 2010 software used for all geometry optimizations is appeared in Figure 1, where the ascertained nuclear charge for the novel herniarin is likewise shown, Table 1 [13]. The form plots of the boondocks orbitals for the ground condition of new herniarins were appeared in Figure 2, including HOMO and LUMO [14]. It could be shown from Figure 2 that the HOMO orbitals are situated on the substituted particle while LUMO orbitals look like those got for the un-substituted atom and along these lines; the substitution has an impact on the electron gift capacity, yet just a little effect on electron acknowledgment capacity [15].

Experimental Section I. General
The chemicals that utilized in our preparation were supplied from Fluka and Sigma-Aldrich, and the purity was done by thin-layer-chromatography and the spot was appeared in 365 nm UV light. Infrared-spectrum was recorded utilizing SHIMADZU FT-IR 8400S spectrophotometer, at the Chemistry Department, Al-Mustansyriyah University. NMR spectrum with the DMSO-d6 as a solvent was done on Bruker-DMX 500spectrophotometer-300MHz-spectrometer at department of chemistry, Al-Bayt University, Jordan. Melting point was recorded on Gallenkamp-M.F.-B00.010-F.

II. Synthesis of 7-hydroxy-4-methylcoumarin
A mixture of the resorcinol (30 mmol), ethyl acetoacetate (30 mmol) and sulfuric acid was heated at 100-120 °C for 3 hrs. Poured the mixture (that cooled to room temperature), into 50 g of crushed-ice. Formed crystals were filtered off and suspend in water for washing than dried. Recrystallized from the ethanol to give 7-hydroxy-4-methylcoumarin.

Conclusions
In this study, the new herniarin derivative had been prepared and the structures were elucidated utilizing different techniques. These compounds were theoretically studied using utilizing and the charges of atoms in addition to stereo-chemistry were calculated and found not-planar.