Thermodynamic properties of sublimation of the ortho and meta isomers of acetoxy and acetamido benzoic acids
Graphical abstract
Introduction
Experimental results of thermodynamic properties of sublimation of several substituted benzoic acids and of some of their parent methyl esters have been reported by our research group [1], [2], [3], [4], [5], [6], [7], [8], [9], [10], [11], [12]. In this work these studies are extended to the ortho and meta isomers of acetoxy and acetamido benzoic acids enabling the comparison of the derived results with those reported before for the respective para isomers [7]. Moreover, we wanted to verify if a correlation relating temperatures of fusion, standard molar enthalpies and standard Gibbs energy of sublimation, derived previously for para-substituted benzoic acids [7], still hold for ortho and meta isomers. Ortho-acetoxybenzoic acid, also known as acetylsalicylic acid or aspirin, is one of the most widely used nonsteroidal anti-inflammatory drugs (NSAIDs) and its therapeutic properties have been discussed in the literature. Aspirin is often used as an antipyretic, analgesic and anti-inflammatory medication [13]. Durable use and high doses of this salicylate medication raise the risk of gastrointestinal complications; nevertheless, the ingestion of small daily doses has the potential to reduce repeated vascular events [14]. Both ortho and meta isomers of acetoxybenzoic acid are ligands of two novel organoantimony(V) and two organobismuth(V) complexes that exhibited antileishmanial and antibacterial activities [15]. The ortho isomer of acetamidobenzoic acid (N-acetylanthranilic acid) is a triboluminescent material [16], [17] and presents antimicrobial activity against some plant pathogen – antifungal activity against Fusarium avenaceum, Fusarium graminearum and Fusarium culmorum, and also antibacterial activity against Staphylococcus aureus and Escherichia coli [18]. Further, this compound is an intermediate degradation product of quinaldine in Arthrobacter sp., being metabolised to anthranilic acid [19], [20]. Representations of structures of the compounds studied in this work are presented in figure 1.
Section snippets
Materials and purity control
Table 1 reports analysis and purification details of the four compounds studied in this work: ortho-acetoxybenzoic acid (C9H8O4, CASNR 50-78-2), meta-acetoxybenzoic acid (C9H8O4, CASNR 6304-89-8), ortho-acetamidobenzoic acid (C9H9NO3, CASNR 89-52-1) and meta-acetamidobenzoic acid (C9H9NO3, CASNR 587-48-4). Prior to the experimental study, the purity of the samples was analysed by gas–liquid chromatography performed using an apparatus Agilent 4890D equipped with an HP-5 column (cross-linked,
Temperature, enthalpy and entropy of fusion
Table 2 presents the values of molar enthalpy, entropy, and temperature of fusion derived from DSC analysis of the four compounds studied in this work together with the results reported in literature: For ortho-acetoxybenzoic acid (aspirin) there are several values reported in literature. The temperature of fusion determined in this study (Tfus = 407.38 K) is 2.4 K larger than the average of 103 values reported in reference [26] and is 6.6 K, 5.3 K, and 1.8 K smaller than the values reported,
Acknowledgements
Thanks are due to Fundação para a Ciência e Tecnologia (FCT), Lisbon, Portugal, and to Programa Ciência 2008 (PEst-C/QUI/UI0081/2013), for the financial support to CIQ-UP. A.R.R.P.A also thanks FCT, Operational Program and European Union for the award of the postdoctoral fellowship (SFRH/BPD/97046/2013).
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2019, Thermochimica ActaCitation Excerpt :The enthalpy of fusion is about 1.73 kJ mol–1 higher than the previous one [2] which might be caused by unsealed pans used in the previous study. It is in good agreement with other values from literature, namely 32.56 kJ mol–1 [14], 32.19 kJ mol–1 [15], 33.51 kJ mol–1 [16] and 33.85 kJ mol–1 [17]. In some other cases [18–20] published values of the melting enthalpy of ASP are substantially lower in 25–29 kJ.mol–1 range.
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2018, Journal of Pharmaceutical SciencesCitation Excerpt :The total data set combines 2036 previously validated10,11 aliphatic and aromatic hydrocarbons and polyhalogenated hydrocarbons with additional 1072 substituted benzenes which contain large variety of functional groups, including alcohol, aldehyde, ketone, carboxylic acid, carbonate, carbamate, amine, amide, nitrile as well as aceto, and nitro groups. Melting and boiling points and vapor pressure for more than 2000, 1600, and 800 compounds were gathered from the NIST database, Acree and Chickos,19 Lian and Yalkowsky,10 Admire, et al.,11 and other references.20-83 Melting points of the studied compounds range from around 90 K to 700 K, and their boiling points range between 150 K and 850 K.
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2017, Thermochimica ActaCitation Excerpt :On the other hand, sublimation enthalpies at 298.15 K together with combustion calorimetry data lead to formation enthalpies in gas phase. Sublimation enthalpies of substituted acetanilides were obtained by gas saturation method in [9] (acetanilide, 4′-hydroxyacetanilide, 4′-ethoxyacetanilide), [10] (4′-hydroxyacetanilide), [11] (2′-hydroxyacetanilide, 3′-hydroxyacetanilide), [12] (2′-, 3′- and 4′- carboxyacetanilides); Knudsen effusion method in [13] (acetanilide, 2′-methylacetanilide, 4′-methylacetanilide), [14] (acetanilide), [15] (4′-hydroxyacetanilide), [16] (4′-hydroxyacetanilide), [17] (2′- and 3′-carboxyacetanilides), [18] (4′-carboxyacetanilide) and its modifications in [19] (4′-ethoxyacetanilide); Calvet-drop sublimation calorimetry in [16] (4′-hydroxyacetanilide). Additionally, vapor pressures of liquid acetanilide derivatives and the vaporization enthalpies were studied in [20] (4′-ethoxyacetanilide, 4′-bromoacetanilide, 4′-hydroxyacetanilide) by thermogravimetric analysis; in [21] (acetanilide, 3′-ethoxyacetanilide, 4′-ethoxyacetanilide, 4′-methoxyacetanilide, 4′-methylacetanilide) by correlation gas chromatography; in [22] (4′-methoxyacetanilide, 4′-ethoxyacetanilide) by isoteniscope.
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Present address: Requimte, Departamento de Química e Bioquímica, Faculdade de Ciências da Universidade do Porto, Rua do Campo Alegre, 4169-007 Porto, Portugal.