Thermodynamic behavior of mixed benzodiazepines by a new liquid chromatographic method

Summary Using a rapid chemometric methodology to determine the separation factor, , at different temperatures, Gibbs Helmholtz parameters ( (H), (S), (G)) of two adjacent benodiazepines on a chromatogram were obtained from ln versus T^–1 plots. A temperature dependent reversal of the elution order was studied and the mobile phase composition and column temperature were optimized to obtain the best separation. A flow rate of 0.80 ml min^–1 with 52.6% methanol in the methanol-water mixture and a column temperature of 48°C gave the most efficient separation of ten benzodiazepines.     

Study on the Melting Process of Nitrocellulose by Thermal Analysis Method

The melting process of NC is studied by using modulated differential scanning calorimetry (MDSC) technique, the microscope carrier method for measuring the melting point and the simultaneous device of the solid reaction cell in situ/RSFT-IR. The results show that the endothermic process in the MDSC curve is reversible. It is caused by the phase change from solid to liquid of the mixture of initial NC, decomposition partly into condensed phase products. The values of the melting point, melting enthalpy (H_m), melting entropy (S_m), the enthalpy of decomposition (H_dec) and the heat-temperature quotient (S_dec) obtained by the MDSC curve of NC at a heating rate of 10 K min^–1 are 476.84 K, 205.6 J g^–1, 0.4312 J g^–1 K^–1, –2475.0 J g^–1 and –5.242 Jg^–1K^–1, respectively. The MDSC results of NC with different nitrogen contents show that with increasing the nitrogen content in NC, the absolute values of H_m, S_m, H_dec and S_dec increase.This revised version was published online in November 2005 with corrections to the Cover Date.     

Reaction of methylmagnesium iodide with steroid keto oxides

Summary The reaction of the 3-acetate of the 20-ketal of 16,17-oxido-⁵-pregnenol-3-one-20 with methylmagnesium iodide and subsequent hydrolysis of the reaction product yielded 16-methyl-⁵-pregnenediol-3 –17-one –20. 18-Nor-17-methyl-17-iso-^5.11-pregnadienediol-3,16-one-20 was formed as a by-product.     

The position of plutonium/III/ in the lanthanide series in respect to thermodynamic functions of complex formation with nitrates and thiocyanates

The position of Pu/III/ within lanthanides in respect to G⁰, H⁰ and S⁰ of complex formation with nitrate and thiocyanate ligands was determined by the extraction method. It was found that in respect to G⁰, Pu/III/ is a light pseudolanthanide for nitrate ligands and a heavy pseudolanthanide for thiocyanate ligands. A comparison of the positions of Pu/III/ and Am/III/ in respect to G⁰, H⁰ and S⁰ shows that the radius of plutonium is greater than that of americium in the An/NO₃/ ₅ ^2– complex and smaller in the An/NCS/₃/TBP/_n complex. The increase in the radii between plutonium and americium in the thiocyanate complex points out to a contribution from 5f orbitals to bonding.     

Oxidation of [Co(en)2(SOCH2CO2)]+ by S2O82− and by IO4− in binary aqueous solvent mixtures at pressures up to 1.25 kbar

Second order rate constants and activation parameters H, S, and V have been measured for the oxidation of [Co(en)2(SOCH2CO2)]+ by S2O82– and by IO4– in highly aqueous H2O – t-BuOH mixtures. The changes in solvation on going from the initial to the transition state are discussed on the basis of the transfer functions Gto, Hto and Sto. Whereas Gt changes smoothly as the proportion of t-BuOH increases, the plots of Ht and TSt exhibit mirror behaviour and pass through extrema located around x2(t- BuOH)=0.038. Information on the role of solvation is complemented by the determination of activation volumes. These are discussed in terms of intrinsic and solvational contributions. It is proposed that changes in hydrophobic hydration are of principal importance in determining the response of H, S, and V to changes in solvent composition in H2O – t-BuOH mixtures.     

Isomeric composition of pyrazolines obtained from unsaturated carbonyl compounds and hydrazine

The ²-pyrazolines synthesized under the usual conditions from unsaturated aldehydes and hydrazine contain from 2 to 3% of the ¹-isomers and considerable amounts of the isomeric 3-alkyl-²-pyrazolines, which are formed as a consequence of migration of the double bond. Mixtures of the stereoisomeric ²-pyrazolines are formed from ,-dialkyl-substituted acroleins. Migration of the double bond does not occur in the condensation of unsaturated ketones with hydrazine, and ²-pyrazolines that are free from admixtures of the structural isomers are obtained.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1225–1229, September, 1971.     

A calorimetric investigation into copper–arginine and copper–alanine solid state interactions

Complexes of formula CuCl₂ · 2arg and CuCl₂ · 4ala (arg = arginine; ala = alanine) were prepared at room temperature by a solid state route. The metal–amino acid solid state interactions were studied by i.r. spectroscopy and solution calorimetry. For both complexes, participation of the carboxylate group as well as nitrogen in coordination are inferred, based on the i.r. data. For the copper–arginine compound, the calculated thermochemical parameters are: _rH_m = –114.9 ± 1.42 and _fH_m = –1608.3 ± 11.6 kJ mol^–1. For copper–alanine compound, a complete set of thermochemical parameters were calculated: _rH_m = –18.0 ± 0.9; _fH_m = –2490.4 ± 4.3; _DH_m = 597.2 ± 17.7; _MH_m = 771.9 ± 18.7; _gH_m = 627.1 ± 22.3 and D (Cu–L) = 156.8 ± 5.7 kJ mol^–1. Based on _rH_m and dissolution enthalpy values, a stronger intermolecular solid state interaction can be inferred for the arginine complex, than for the alanine one complex, probably due to the formation of intermolecular hydrogen bonds in the former.     

Kinetics and mechanism of the interaction of azide with [(H2O)(tap)2RuORu(tap)2-(H2O)]2+ ion at physiological pH

The title reaction has been studied spectrophotometrically in aqueous medium as a function of [substrate complex], [ligand], pH and temperature at constant ionic strength. At the physiological pH (7.4) the interaction with azide shows two distinct consecutive steps, i.e., it shows a non-linear dependence on the concentration of N₃ ^–; both processes are [ligand]-dependent. The rate constant for the processes are: k ₁10^–3 s^–1 and k ₂10^–5 s^–1. The activation parameters calculated from Eyring plots are: H ₁ = 14.8 ± 1 kJ mol^–1, S ₁ = –240 ± 3 J K^–1 mol^–1, H ₂ = 44.0 ± 1.5 kJ mol^–1 and S ₂ = –190 ± 4 J K^–1 mol^–1. Based on the kinetic and activation parameters an associative interchange mechanism is proposed for the interaction process. From the temperature dependence of the outersphere association equilibrium constant, the thermodynamic parameters calculated are: H ₁ ⁰ = 4.4 ± 0.9 kJ mol^–1, S ₁ ⁰ = 64 ± 3 J K^–1 mol^–1 and H ₂ ⁰ = 14.2 ± 2.9 kJ mol^–1, S ₂ ⁰ = 90 ± 9 J K^–1 mol^–1, which gives a negative G ⁰ value at all temperatures studied, supporting the spontaneous formation of an outersphere association complex.     

Thermodynamic quantities for the interaction of Cl− with Mg2+, Ca2+ and H+ in aqueous solution from 250 to 325°C

The aqueous reactions, Mg²⁺+Cl^–=MgCl⁺, Ca²⁺+Cl^–=CaCl⁺, and H⁺ +Cl^–=HCl(aq), were studied as a function of ionic strength at 250, 275, 300, and 325°C using a flow calorimetric technique. The logK, H, S and C_p values were determined from the fits of the calculated and experimental heast. The data were reduced assuming a known functionality of the activity coefficient. Hence, the logK, H, S and C_p values determined in this study are dependent on the activity coefficient model used. These thermodynamic values were compared with literature results. The logK values for the formation of MgCl⁺ agree reasonably well with those reported in the literature. The logK values for CaCl⁺ formation agree reasonably well with those reported in the literature at 300 and 325°C. At lower temperatures, the agreement is poorer. The logK values for the formation of HCl(aq) are generally lower than those reported in the literature. The logK, H, S and C_p values for all three ion association reactions are positive and increase with temperature over the temperature range studied. These values are the first determined calorimetrically for the formation of MgCl⁺ and CaCl⁺ in the temperature range 275–325°C.Presented at the Second International Symposium on Chemistry in High Temperature Water, Provo, UT, August 1991.     

Research on 1-aza two-ring systems

Reduction of 5-[2-(methoxycarbonyl)ethyl]-1,3-dihydropyrrolizines with lithium aluminum hydride gave 5-(-hydroxypropyl)-1,2-dihydropyrrolizines (in 70–90% yields), which have intramolecular -hydrogen bonds in dilute solutions. The parameters of the -hydrogen bonds were determined in the IR spectra, and their enthalpies were found. The data obtained (_OH 95–99 cm^–1, –H 3.05 kJ·mole^–1) show that among compounds with an aliphatic hydroxyl group and a system of electrons, 5-(-hydroxypropyl)-1,2-dihydropyrrolizines have some of the strongest intramolecular -hydrogen bonds.See [1] for communication XVI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 359–363, March, 1978.     

Reduction of some D-homosteroids with an aromatic a ring by alkali metals under the conditions of the birch reaction. I

Summary In the Birch reduction of steroid compounds with a phenylbutadiene grouping, i.e., the ketal of 3-methoxy-^{1, 3, 5(10), 8, 14}-D-homoestrapentaen-17a-one (III), the corresponding ketone (IIIa), and 3-methoxy-^{1, 3, 5(10), 8, 14}-D-homoestrapentaen-17a-ol (VI), 1, 4 addition of the hydrogen takes place first, and is followed by reduction of the aromatic nucleus. In this way, 3-methoxy-^{1, 3, 5(10), 8(14)}-D-homoestratetraenone (XII), ^{4, 8(14)}-19-nor-D-homoandrostadienedione (VIII), and ^{4, 8(14)}-19-nor-D-homoandrostadien-17a-ol-3-one (IX) have been obtained.Khimiya prirodnykh soedinenii, Vol. 1, No. 1, pp. 7–15, 1965     

Complexation,solubilities and thermodynamic functions for cerium(III) fluoride-water system

The solubility, solubility product and the thermodynamic functions for the CeF₃–H₂O system have been measured using the radiometric, conductometric and potentiometric techniques. The radiometric values for the solubility and solubility product, the lowest and more acceptable for reasons cited in previous papers, are 3.14·10^–5 M and 2.17·10^–17 respectively. The enthalpy change measured by the conductometric method is almost twice as that obtained by potentiometric method due to abnormal conductances registered at higher temperatures. The average values for H^o and G^o and S^o at 298 K are 53.0±17.4, 91.7±4.0 and –129.7±58.2 KJ·mol^–1 respectively. The positive values for H^o and G^o and the negative value for S^o are indicative of the low solubility of this salt in water. The stability constants for the mono- and difluoride complexes of Ce(III) have been determined potentiometrically using unsaturated solution mixtures of Ce(III) and F^–. These values for CeF⁺ and CeF ₂ ⁺ are 997±98 and (1.03±0.44)·10⁵, respectively. Studies on pH dependence of the solubility shows that the solubility reaches a minimum value at a pH of about 3.2.     

The Influence of Dimerization of Water-Soluble Metalloporphyrins as Photosensitizers on the Efficiency of Generation of Singlet Oxygen

Quantum yields () for the generation of singlet oxygen sensitized by Pd(II) complexes of water-soluble porphyrins: meso-tetrakis(4-N-methylpyridyl)porphine [PdTMPyP]⁴⁺ ( = 0.9), meso-tetrakis(4-N,N,N-trimethylaminophenyl)porphine [PdTTMAPP]⁴⁺ ( = 0.8), meso-tetrakis(4-carboxyphenyl)porphine [PdTCPP]^4– ( = 0.7), and meso-tetrakis(4-sulfonatophenyl)porphine [PdTSPP]^4– ( = 0.5) were determined using a chemical method. It was found that the dimerization and aggregation of metalloporphyrins greatly influence the value. The quantum yields evaluated for the formation of singlet oxygen sensitized by metalloporphyrin monomeric and dimeric forms are _{, M} 0.9 and _{, D} 0.2, respectively, and do not depend on the porphyrin nature.     

Far infrared spectra (500–50 cm−1) of the 2,2′-bipyridine complexes of palladium and platinum halides

Summary The far-i.r. spectra of the title complexes have been examined. Band assignments are based on the shifts induced by ligand deuteration and halide substitution. Deuteration of bipyridine causes large shifts ( >10 cm^–1) in internal ligand modes, intermediate shifts between 2 and 9 cm^–1) in metal-nitrogen stretching and bending modes and small to zero shifts in metal-halide stretching and bending vibrations. Generally, the requirements for square planarC _2v synanetry [two (M–N) and two (M–X) bands] are observed. Previous ambiguities in the assignment of the (M–N) bands have been resolved by the isotopic labelling technique employed in this study.     

Enthalpies of solution of thymine and uracil in water and dimethylsulfoxide

Enthalpies of solution of thymine and uracil in water and in dimethylsulfoxide (DMSO) were measured calorimetrically in the temperature range 25–40°C. H _s ^o at 25°C for thymine and uracil in water were found to be 23.1±0.5 and 29.5±0.3 kJ-mol^–1, respectively. In DMSO, H _s ^o were 7.9±0.1 and 10.2±0.1 kJ-mol^–1, respectively. In aqueous solution C _p ^o for the two nucleic acid bases were relatively large and positive with C _p ^o of thymine being larger. Both transfer quantities H _t ^o and C _p,t ^o for the proceses H₂ODMSO for the two nucleic acid bases were negative. It is proposed that, the differences in the values obtained for the two bases is due principally to increased order in the water adjacent to the methyl group in thymine.     

Dissociation constants of the ampholyte glycine in 50 mass % methanol-water from 5 to 55°C,with related thermodynamic quantities

The two thermodynamic dissociation constants of glycine at 11 temperatures from 5 to 55°C in 50 mass % methanol-water mixed solvent have been determined from precise emf measurements with hydrogen-silver bromide electrodes in cells without liquid junction. The first acidic dissociation constant (K ₁)for the process HG⁺H⁺+G^± is expressed as a function ofT(^oK) by the equation pK ₁ = 2043.5/T – 9.6504 + 0.019308T. At 25°C, pK ₁is 2.961 in the mixed solvent, as compared with 2.350 in water, with H°=1497 cal-mole^–1, G°=4038 cal-mole^–1, S°=–8.52 cal-°K^–1-mole^–1, and C _p ^o =–53 cal-°K^–1-mole^–1. The second acidic dissociation constant (K ₂)for the process G^±H⁺+G^– over the temperature range studied is given by the equation pK ₂ = 3627.1/T – 7.2371 + 0.015587T. At 25°C, pK ₂is 9.578 in MeOH–H₂O as compared with 9.780 in water, whereas H° is 10,257 cal-mole^–1, G° is 13,063 cal-mole^–1, S° is –9.41 cal-°K^–1-mole^–1, and C _p ^o is –43 cal-°K^–1-mole^–1. The protonated glycine becomes weaker in 50 mass % methanol-water, whereas the second dissociation process becomes stronger despite the lower dielectric constant of the mixed solvent (=56.3 at 25°C).     

Determination of enthalpy of ionization of water from 250 to 350° C

The enthalpy changes at zero ionic strength (H°) for the ionization of water (H₂O=H⁺+OH^–) were determined by flow calorimetry from the heats of mixing of aqueous NaOH and HCl solutions in the temperature range 250 to 350°C. Pitzer ion-interaction models developed by other workers were used to calculate enthalpies of dilution of aqueous NaOH, HCl, and NaCl solutions for the extrapolation of H values from the conditions of the experiment to infinite dilution. Equations are derived for thermodynamic quantities (log K, H°, S°, C _p ^° and V°) for the ionization of water using the H° values determined in this study from 250 to 350°C and literature log K and H° values from 0 to 225°C. Smoothed values of log K, H°, S°, C _p ^° , and V° are presented at rounded temperatures from 0 to 350°C and at the saturation pressure of water for each temperature. The equations in the present study provide a better representation of experimental thermodynamic data from 0 to 350°C than the Marshall-Franck equation.     

Spectrochemistry of solutions,part 23. Changes of enthalpy and entropy in the formation of contact ion pairs: A vibrational spectroscopic appraisal using thiocyanate and azide solutions

Summary The vibrational spectra of solutions have been analyzed to assess both qualitatively and quantitatively the changes in enthalpy and entropy for ion pair formation in solutions of LiNCS, Mg(NCS)₂, and LiN₃ in liquid ammonia, dimethylformamide, dimethylsulphoxide and acetonitrile. Contrary to predictions both the H _ass and S _ass terms are all positive in the cases examined, indicating that the driving force in the ion association process derives from solvent-solute restructuring, and not the energy of the interaction between the cation and anion. This characteristic of contact ion pair formation is likely to be found to be applicable over a wide range of solvents. The following specific values of the thermodynamic parameters at 298 K have been obtained: LiNCS/DMF, G=–1.3 (1) kJ mol^–1, H _ass =+1.8 (5) kJ mol^–, S _ass =+10 (2) J mol^–1 K^–1; LiNCS/DMSO, G=+0.9 (2) kJ mol^–1, H _ass =+0.3 (3) kJ mol^–1; Mg(NCS)₂/DMF, G _ass =–4.0 (3) kJ mol^–1, H _ass =+15 (4) kJ mol^–1, S=+64 (17) kJ mol^–1; LiN₃/DMSO, G _ass =–2.5 (3) kJ mol^–1, H _ass =+4.9 (9) kJ mol^–1, S _ass =+25 (10) J K^–1 mol^–1.Submitted to celebrate the 70th Birthday of Professor Viktor Gutmann, and in recognition of his considerable contributions towards the better understanding of Chemistry in the Solution Phase     

Preparation of the simplest Δ1-pyrazolines by isomerization of Δ2-pyrazolines

²-Pyrazolines that do not have substituants in the 1- and 3-positions are not capable of isomerization to 3-substituted pyrazolines and can be converted to ¹-pyrazolines by slow distillation in the presence of bases. This method, which is completely analogous to the synthesis of azo compounds from alkylhydrazones, gives good results when applied to 4-alkyl- and 5,5-dialkyl-²-pyrazolines and makes it possible to obtain the corresponding ¹-pyrazolines in yields of 40–70%. 4-Ethyl-, 5-methyl-5-ethyl-, and 5,5-diethyl-¹-pyrazolines are described for the first time.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 956–957, July, 1971.     

Kinetics of formation,dissociation and equilibrium constants of pentacyanoaquoruthenate(II) with heterocycles

The kinetics of formation and dissociation reactions of [Ru(CN)₅L]^3– with a series of heterocyclic ligands were studied in aqueous media. In this presence of an excess of heterocycle, the observed second order rate constants were calculated from the k_obs versus [ligand] plot at =0.100m NaClO₄. Activation parameters for the formation reactions (H=28±7kJmol^–1 and S=140±35JK^–1mol^–1) are comparable for all systems, indicating a common mechanism. The kinetics of exchange of coordinated heterocycles for 1,3,5-triazine yielded a rate saturation typical of a limiting dissociative mechanism. Activation parameters of the limiting first order specific rate of dissociation reactions were H=85±7kJmol^–1 and S=18±4JK^–1mol^–1. Equilibrium constants were calculated from the second order rates of formation and pseudo-first order rates of dissociation reaction.