Browsing by Author "Cabrera, Adolfo L."

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    Experimental measurement and modeling of the solubility of fluorinated compounds derived from dichlone in supercritical carbon dioxide
    (2024) Arevalo, Vicente D.; Cabrera, Adolfo L.; Zacconi, Flavia C.; Morales-Guerrero, Sebastian; del Valle, Jose M.; Taborga, Lautaro; de la Fuente, Juan C.
    Dichlone, also known as 2,3-dichloronaphthalene-1,4-dione, is a solid organic substance employed in the field of agriculture for its fungicidal properties and as a retardant for vegetable decomposition. The bioactive properties of dichlone can be enhanced by modifying its structure, specifically through the synthesis of new derivatives achieved by replacing the functional groups within its molecular structure. Two new solid dichlone derivatives were synthesized in this work, namely 2-chloro-3-((4-fluorobenzyl)amino)naphthalene-1,4-dione (dCl-2B-F) and 2-chloro-3-((4-fluorophenethyl)amino)naphthalene-1,4-dione (dCl-3 P -F) and measured their solubility in supercritical carbon dioxide at (313, 323, and 333) K and pressures between (9. to 32) MPa. The results indicated that solubility ranged between 30.5 and 47.9 mu mol of solute/mol of CO 2 for dCl-2B-F, and from 2.2 to 243.5 mu mol of solute/mol of CO 2 for dCl-3 P -F. The solubility data of dichlone and its synthesized derivatives (dCl-2B-F, dCl3 P -F, 2-chloro-3-((4-chlorobenzyl)amino)naphthalene-1,4-dione (dCl-2B-Cl), 2-chloro-3-((4-chlorophenethyl) amino)naphthalene-1,4-dione (dCl-3 P -Cl), 2-(benzylamino)-3-chloronaphthalene-1,4-dione (dCl-2B) and 2chloro-3-(phenethylamino)naphthalene-1,4-dione (dCl-3 P)) was compared using the density-based correlation of Chrastil and the Statistical Associating Fluid Theory of Variable Range Mie-potential (SAFT-VR Mie) equation of state (EoS), to better comprehend the effects of the structural differences on the solubility. As a result, for the Chrastil model, a root mean square deviation ( rmsd ) of 3% was obtained for dCl-2B-F and 16% for dCl-3 P -F, whereas for the SAFT-VR Mie equation, it averaged 24% for dCl-2B-F and 28% for dCl-3 P -F. It was found that the solubility of the homologous compounds, differing only in one methylene group, increased with solute size (-2B derivatives were less soluble in CO 2 than the -3 P ones), contrary to the expected trend, which could be attributed to the increased probability of ring -to -ring interactions as the chain length connecting the rings decreases. This demonstrates that geometric factors, along with the pressure and temperature, affect the behavior of the solubility and these should be accurately represented in the predictive models.
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    Solubility in supercritical carbon dioxide of two novel amine derivatives of 2,3-dichloronaphthalene-1,4-dione (dichlone)
    (2023) Schulz, Alex C.; Zacconi, Flavia C.; Cabrera, Adolfo L.; del Valle, Jose M.; Espinoza, Luis; de la Fuente, Juan C.
    Dichlone (2,3-dichloronaphthalene-1,4-dione) is an important antimicrobial agent for agriculture, which effectiveness could be improved by modifying its structure, while the recovery of high-purity synthesized derivatives from a reaction mixture could be accomplished by extracting them with supercritical carbon dioxide. Two new amine derivatives, 2-chloro-3-((4-chlorobenzyl)amino)naphthalene-1,4-dione (dCl-2B-Cl) and 2-chloro-3-((4-chlorophenethyl)amino)naphthalene-1,4-dione (dCl-3P-Cl), were synthesized from dichlone, and their solubility in supercritical carbon dioxide was measured afterwards at (313, 323 and 333) K and a pressure range from (8-33) MPa. Experimental solubilities spanned from (10.3 center dot 10(-6) to 22.1 center dot 10(-6)) mol center dot mol(-1) for dCl-2B-Cl, and from (32.7 center dot 10(-6) to 131 center dot 10(-6)) mol center dot mol(-1) for dCl-3P-Cl. The solubility data of the dichlone family (dichlone, dCl-2B-Cl, dCl-3P-Cl, 2-(benzylamino)-3-chloronaphthalene-1,4-dione (dCl-2B) and 2-chloro-3-(phenethylamino)naphthalene-1,4-dione (dCl-3P)) was compared using three models, i.e., the Chrastil equation, the Molecular Connectivity Indices model, and the Statistical Associating Fluid Theory of Variable Range and Mie Potential equation of state, to identify the quantitative structure-property relationship between them. Solubility had an inverse relation with solute size and polarity, but there were some exceptions that could be explained by performing a stereochemical analysis, which showed that steric effects involved in the folding of dCl-3P and dCl-3P-Cl provided them a better geometry for solvation than dCl-2B and dCl-2B-Cl, respectively, making them more soluble. This demonstrates that the solute geometry is an important factor in the solvation process, and it must be represented accurately to develop better predictive models.
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    Solubility of menadione and dichlone in supercritical carbon dioxide
    (2016) Reveco Chilla, Andrea G.; Cabrera, Adolfo L.; De La Fuente, Juan C.; Zacconi, Flavia C. M.; Valle Lladser, José Manuel del; Valenzuela Roediger, Loreto Margarita
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    Synthesis and solubility measurement in supercritical carbon dioxide of two solid derivatives of 2-methylnaphthalene-1,4-dione (menadione) : 2-(Benzylamino)-3-methylnaphthalene-1,4-dione and 3-(phenethylamino)-2-methylnaphthalene-1,4-dione
    (2016) Zacconi, Flavia C. M.; Núñez, Olga N.; Cabrera, Adolfo L.; Valenzuela Roediger, Loreto Margarita; Valle Lladser, José Manuel del; De La Fuente, Juan C.