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Calorimetric and Computational Study of Indanones

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Calorimetric and Computational Study of Indanones BATCH: jp11a20 USER: emm29 DIV: @xyv04/data1/CLS_pj/GRP_jx/JOB_i43/DIV_jp074718d DATE: September 20, 2007 1 Calorimetric and Computational Study of Indanones 2 M. Agostinha R. Matos,† Margarida S. Miranda,† Manuel J. S. Monte,† | 3 Luı´s M. N. B. F. Santos,† Victor M. F. Morais,†,‡ James S. Chickos, | 4 Patamaporn Umnahanant, and Joel F. Liebman*,§ 5 Centro de InVestigac¸a˜oemQuı´mica, Departamento de Quı´mica, Faculdade de Cieˆncias, UniVersidade do 6 Porto, Rua do Campo Alegre, 687, P-4169-007 Porto, Portugal, Instituto de Cieˆncias Biome´dicas Abel Salazar, 7 ICBAS, UniVersidade do Porto, P-4099-003 Porto, Portugal, Department of Chemistry, UniVersity of 8 MissourisSt. Louis, St. Louis, Missouri 63121, and Department of Chemistry and Biochemistry, UniVersity of 9 Maryland, Baltimore County, Baltimore, Maryland 21250 10 ReceiVed: June 18, 2007; In Final Form: August 21, 2007 11 Condensed phase standard (p° ) 0.1 MPa) molar enthalpies of formation for 1-indanone, 2-indanone, and 12 1,3-indandione were derived from the standard molar enthalpies of combustion, in oxygen, at T ) 298.15 K, 13 measured by static bomb combustion calorimetry. The standard molar enthalpies of sublimation for 1-indanone 14 and 2-indanone, at T ) 298.15 K, were measured both by correlation-gas chromatography and by Calvet 15 microcalorimetry leading to a mean value for each compound. For 1,3-indandione, the standard molar enthalpy 16 of sublimation was derived from the vapor pressure dependence on temperature. The following enthalpies of - 17 formation in gas phase, at T ) 298.15 K, were then derived: 1-indanone, -64.0 ( 3.8 kJ mol 1; 2-indanone, - - 18 -56.6 ( 4.8 kJ mol 1; 1,3-indandione, -165.0 ( 2.6 kJ mol 1. The vaporization and fusion enthalpies of 19 the indanones studied are also reported. In addition, theoretical calculations using the density functional theory 20 with the B3LYP and MPW1B95 energy functionals and the 6-311G** and cc-pVTZ basis sets have been 21 performed for these molecules and the corresponding one-ring species to obtain the most stable geometries 22 and to access their energetic stabilities. 23 Introduction SCHEME 1: Structures of the Compounds Studied 24 Although indole and its derivatives are well-known to have 25 considerable biomedical activity ranging from the amino acid 26 tryptophan and the plant auxin, indole-3-acetic acid, to the 27 psychopharmacologically active melatonin and serotonin, per- 28 haps generally less appreciated, the related carbocycles indene, 29 indan, and their derivatives such as substituted 1-indanones (2,3- 30 dihydro-1H-inden-1-one) also have a wide range of biomedical 31 applications.1 The study of the acidity of 2-indanone provided 32 seminal information as to the effects of phenyl groups on the 33 acidification of ketones,2 and thereby led to insights into the 34 physical bioorganic chemistry of unsaturated ketones, in par- 35 ticular steroids such as testosterone.3 Indoles and indans also 36 appear on both sides of the legal fulcrum: the illicit drug LSD studied as they are not available in pure and/or anhydrous form. 47 37 is an indole derivative. 1,2,3-Indantrione enjoys considerable This is in contradistinction to 2,3-indoledione, also known as 48 38 criminological importance: its covalent hydrate is better known isatin, and investigated by us earlier, calorimetrically.5 As in 49 39 as ninhydrin, an important reagent for fingerprint detection at this last study, our current results were obtained from measure- 50 40 crime scenes.4 Despite these enunciated applications, there has ments of combustion energies using a static bomb calorimeter. 51 41 been little work reported regarding the structure and energetics The enthalpies of sublimation were measured by Calvet micro- 52 42 of carbonyl-containing indene compounds. calorimetry and by correlation-gas chromatography (1- and 53 43 In the present work we report the standard molar enthalpies 2-indanone) or derived from the vapor pressure dependence on 54 44 of formation of three indanones, 1-indanone, 2-indanone, and temperature (1,3-indandione). Density functional theory calcula- 55 45 1,3-indandione in the gaseous phase (Scheme 1). The remaining tions were also performed for these two-ring molecules and for 56 46 indanones, 1,2-indandione and 1,2,3-indantrione, were not the related one-ring cyclopentanone and 2- and 3-cyclopenten- 57 one. There is good agreement between experimentally and 58 * Corresponding author. E-mail [email protected]. Phone: -1-410- theoretically calculated enthalpies of isodesmic reactions. 59 455-2549. Fax: -1-410-455-2608. † Centro de Investigac¸a˜o em Quı´mica, Departamento de Quı´mica, Faculdade de Cieˆncias, Universidade do Porto. Experimental Section 60 ‡ ICBAS, Universidade do Porto. | University of MissourisSt. Louis. The compounds studied were obtained commercially from 61 § University of Maryland. Aldrich Chemical Co with the assigned mass fraction purities 62 10.1021/jp074718d CCC: $37.00 © xxxx American Chemical Society Published on Web 00/00/0000 PAGE EST: 7 BATCH: jp11a20 USER: emm29 DIV: @xyv04/data1/CLS_pj/GRP_jx/JOB_i43/DIV_jp074718d DATE: September 20, 2007 B J. Phys. Chem. A Matos er al. 63 of: 1-indanone [83-33-0] 99.90%, 2-indanone [615-13-4] The mass of compound, m(compound), used in each experi- 127 64 98.20%, and 1,3-indandione [606-23-5] 99.5% determined by ment was determined from the total mass of carbon dioxide, 128 65 gas-liquid chromatography. The compounds were further m(CO2,total), produced after allowance for that formed from 129 66 purified by repeated sublimation before the calorimetric mea- the cotton thread fuse, Melinex and n-hexadecane. 130 67 surements. The final purity of 1- and 2-indanone was assessed An estimated pressure coefficient of specific energy: (∂u/ 131 6 -1 -1 68 by DSC analysis using the fractional fusion technique. The DSC ∂p)T )-0.2Jg MPa at T ) 298.15 K, a typical value for 132 69 experiments were performed with a Setaram DSC 141 calo- most organic compounds, was assumed.14 For each compound, 133 70 rimeter. The samples were hermetically sealed in stainless steel the corrections to the standard state to calculate the standard 134 -2 -1 71 crucibles and the heating rate was 1.67 × 10 Ks . No phase massic energy of combustion, ∆cu°, were made by the procedure 135 72 transitions were observed between T ) 298.15 K and the fusion given by Hubbard et al.15 136 73 temperature. The power scale of the calorimeter was calibrated 74 with high purity indium (mass fraction >0.99999) and its Calvet Microcalorimetry Experiments 137 75 temperature scale was calibrated by measuring the melting The standard molar enthalpies of sublimation were measured 138 76 temperature of the following three high purity reference materi- using the “vacuum sublimation” drop microcalorimetric method,16 139 77 als:7 naphthalene, benzoic acid, and indium. a method shown to be in good agreement with other sublimation 140 78 The composition of the crystalline samples was also assessed methods, e.g., ref 16. Samples of about 3-5mgofthe 141 79 through the carbon dioxide recovery ratio. The average ratios crystalline compounds contained in thin glass capillary tubes 142 80 of the mass of carbon dioxide recovered to that calculated from sealed at one end, were dropped from room temperature into 143 81 the mass of sample, together with the standard deviation of the the hot reaction vessel in the Calvet high-temperature micro- 144 82 mean, were 1-indanone, 100.00 ( 0.03, 2-indanone, 100.04 ( calorimeter (SETARAM HT 1000D) held at a convenient 145 83 0.03, and 1,3-indandione, 100.00 ( 0.02. The specific densities - temperature, T, and then removed from the hot zone by vacuum 146 84 of the samples were taken from ref 8 as F)1.103 g cm 3 - sublimation. An empty capillary tube was dropped in the 147 85 (1-indanone), F)1.0712 g cm 3 (2-indanone), and F)1.37 - reference calorimetric cell, simultaneously. For these measure- 148 86 gcm 3 (1,3-indandione). ments, the microcalorimeter was calibrated in situ using the 149 87 Combustion Calorimetry Measurements reported standard molar enthalpy of sublimation of naphthalene 150 - 72.600 ( 0.600 kJ mol 1.17 Accuracy tests were performed with 151 88 The energies of combustion of the compounds were measured benzoic acid. 152 89 using a static bomb calorimeter. Because the apparatus and the g,T The observed enthalpies of sublimation, ∆ H°, were 153 90 technique have been described;9,10 only a brief description will cr,298.15K m corrected to T ) 298.15 K using the equation 154 91 be given here. The energy equivalent of the calorimeter was 92 determined from the combustion of benzoic acid BDH Ther- T ∆T H°(g) ) ∫ C° (g)dT (1) 93 mochemical Standard, batch 69376/01, certified at Manchester 298.15 K m 298.15 K p,m 94 University, having a massic energy of combustion of ∆cu ) - 95 -26435.1 ( 3.5Jg 1, under certificate conditions. Calibration where T is the temperature of the hot reaction vessel and 155 ° 96 experiments were carried out in oxygen at the pressure 3.04 Cp,m(g) is the molar heat capacity of the gaseous compound. 156 97 MPa in the presence of 1.00 cm3 of water added to the bomb. The heat capacity and its temperature dependence for 1-in- 157 98 One set of seven calibration experiments was performed, leading danone, 2-indanone, and 1,3-indandione, respectively, 158 99 to the value of the energy equivalent of the calorimeter: cal ) ( -1 ° -1 -1 )- 2 + - 100 16005.0 2.0JK , where the uncertainty quoted is the Cp,m(g)/(J mol K ) 0.000326(T/K) 0.682(T/K) 101 standard deviation of the mean.
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