Aripiprazole salts. I. Aripiprazole nitrate

The crystal structure of aripiprazole nitrate (systematic name: 4‐(2,3‐dichlorophenyl)‐1‐{4‐[(2‐oxo‐1,2,3,4‐tetrahydroquinolin‐7‐yl)oxy]butyl}piperazin‐1‐ium nitrate), C₂₃H₂₈Cl₂N₃O₂⁺·NO₃⁻ or AripH⁺·NO₃⁻, is presented and the molecule compared with the aripiprazole molecules reported so far in the literature. Bond distances and angles appear very similar, except for a slight lengthening of the C—NH distances involving the protonated N atom, and the main differences are to be found in the molecular spatial arrangement (revealed by the sequence of torsion angles) and the intermolecular interactions (resulting from structural elements specific to this structure, viz. the nitrate counter‐ions on one hand and the extra protons on the other hand as hydrogen‐bond acceptors and donors, respectively). The result is the formation of [100] strips, laterally linked by weak π–π and C—Cl...π interactions, leading to a family of undulating sheets parallel to (010).     

Structures of deoxypeganine salts

The structures of deoxypeganine (DOP) hydrochloride and oxalate were solved by x-ray structure analysis. An infinite chain along the crystallographic c axis was formed in the crystal structure of DOP oxalate. A molecular framework consisting of Cl anions and DOP cation protonated at N1 was found in the structure of unhydrated DOP hydrochloride. The molecular packing of the “host” (DOP cation) was pseudoisostructural in the studied ion-molecular crystals but differed from other known DOP salts. The “guest” molecules (acid anions) in the studied and known DOP salts formed different intermolecular contacts. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 280–283, May–June, 2006.     

The preparation and characterization of guanylurea nitrate and perchlorate salts

Guanylurea nitrate (GUN) and guanylurea perchlorate (GUP) were prepared from cyanoguanidine (CG) and concentrated nitric or perchloric acid, respectively. Both compounds were fully characterized by analytical and spectroscopic methods. Crystals of GUP were grown from water, and its crystal structure was determined by single‐crystal X‐ray diffraction. GUP crystallizes in the monoclinic space group P2₁/c with four molecules in the unit cell; different unit cell parameters are a = 8.0115(2) Å, b = 9.7328(2) Å c = 9.5770(2) Å and β = 105.89(1)°. The heats of combustion of both compounds were determined using oxygen bomb calori‐metry. Finally, the EXPLO5 computer code was used to determine the detonation velocity (D = 5734 m s⁻¹) and pressure (P = 10.6 GPa) of GUN as well as those of formulations with ammonium nitrate and dinitramide. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:301–306, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20419     

Separation of AM(III) by extraction from nitrate solutions using some quaternary benzylammonium salts

Benzyldimethyldodecylammonium nitrate and benzyltrioctylammonium nitrate were used for the extraction of Am(III) from aqueous nitrate solutions. The dependence of the extraction performance for Am(III) on the concentration of nitric acid, the kind and concentration of salting-out agents in the aqueous phase, and the kind of solvent was investigated. Americium is extracted by the above quarternary salts as a R₄NAm(NO₃)₄ associate. The extraction of Am(III) is compared with the extraction of lanthanides. The high differences in the distribution coefficients for lanthanides and americium can be utilized for the separation of lanthanides and americium.     

Precipitation of surfactant salts III. Metal perfluoroalkanecarboxylates

Precipitation of perfluorocarboxylic acids (n-C₃H₇OOH, n-C₇H₁₅COOH, and n-C₉F₁₉COOH) in aqueous solutions of different metal nitrates (K⁺, Ag⁺, Ca²⁺, Ba²⁺, Zn²⁺, Al³⁺, La³⁺) was studied by solubility and calorimetric measurements. The free energy of precipitation per single surfactant chain was found to depend on the chain length but not on the charge of the reacting cation. It was shown that the precipitation of perfluorocarboxylates of multivalent cations was governed by positive entropy change and a low enthalpic contribution, whereas the soaps of monovalent cations exhibited the opposite behavior. The entropy of precipitation was not affected by the chain length of the surfactants in the presence of monovalent cations, but it increased for cations of higher charge.Supported by the NSF Grant CHE-8619509.This paper is dedicated to Professor Armin Weiss on the occasion of his 60th birthday. One of the authors (E. M.) particularly appreciates many years of cooperation with Professor Weiss in editing Colloid and Polymer Science, as well as in many other scientific interactions.     

Basic hydrolysis of glyceryl nitrate esters. III. Trinitroglycerin

Kinetics of the basic hydrolysis of glyceryl trinitrate (TNG) were investigated in CO₂-free aqueous calcium hydroxide solutions. The hydrolysis reactions were carried out in a temperature controlled reactor vessel with provision for continuous N₂ sparging of the reaction mixture. TNG hydrolyzed via second-order reaction at 25°C, 18°C, and 10°C. The activation energy of the hydrolysis reaction of TNG was calculated from the kinetic data and found to be equal to 27.53 kcal/mol. The major products of the hydrolysis of TNG in solution of calcium hydroxide were calcium nitrate and calcium nitrite, accounting for approximately 50% of the degradation products. The minor identified products such as calcium oxalate and nitrate esters amounted to approximatey 6% of the products. The remaining 30% of the isolated products was a mixture of calcium formate, a nitrate ester, and unidentified volatiles, polymerlike substances, and other organic residue.     

The thermal decomposition of cerium(III) nitrate

The thermal decomposition of anhydrous Ce(NO₃)₃ has been studied. The thermal decomposition reaction is described by the second order kinetic equation, [1/(1–)]–1=kt. The apparent activation energy was determined asE _a=104 kJ mol^–1 while the enthalpy of the reaction was estimated asH _r=111.1 kJ mol^–1. The decomposition reaction differs from that observed for Nd(NO₃)₃.

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Zusammenfassung Die thermische Zersetzung von wasserfreiem Ce(NO₃)₃ wurde untersucht. Die thermische Zersetzung wird durch die Geschwindigkeitsgleichung zweiter Ordnung[1/(1–)]–1=kt, beschrieben. Für die scheinbare Aktivierungsenergie wurde ein Wert von 104 kJ mol^–1 und für die Enthalpie der Reaktion ein Wert von 111,1 kJ mol^–1 ermittelt. Die Zersetzungsreaktion unterscheidet sich von der für Nd(NO₃)₃.

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. : [1/(1–)]– 1=kt. a, 104 · ^–1, H _r, 111.1 · ^–1. .

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The authors wish to thank the Council for Scientific and Industrial Research and the University of Pretoria for financial assistance.     

Benzothiazolium derivatives. III. Nucleophilic substitution reactions of benzothiazolium salts

The reactions of 2,3-dihydrothiazolo[2,3-b]benzothiazolium bromide 1 (A^? ?Br^?) with certain nucleophilic reagents have been performed for the purpose of ascertaining the reaction pathways and identifying the group that is displaced from the central carbon atom of the dithiocarbamate system. The nature of complex salt-like intermediates formed initially from 1 (A^? ?Br^?) has been studied and confirmed. For comparison, a number of nucleophilic substitution reactions of 2-methylthio-3-methylbenzothiazolium iodide 17 and 2-dimethylamino-3-methylbenzothiazolium perchlorate 18 have been examined.     

The interpretation of X-ray diffraction by aqueous solutions of aluminum(III) nitrate and chromium(III) nitrate

Aqueous solutions of the nitrates of aluminum (0.5 M) and chromium (0.5 M) are investigated with X-ray diffraction at t = 25° C. The experimental intensity is interpreted in terms of an electron product-function which is a sum of various pair contributions. The contribution containing the information about cationic hydration has been evaluated by combining the results of separate experiments. The method is in several aspects quite different from what is usual. Still the results obtained are in general agreement with the data reported elsewhere. That is, sixfold coordination at 1.90 Å and 1.98 Å and a second shell containing about 12 water molecules appearing at 4.10–4.15 Å and 4.20–4.25 Å for Al³⁺ and Cr³⁺ respectively.     

Hexamethyldilead: III. Reaction with metal salts and organomercurials

Hexamethyldilead reacts with various metal salts very rapidly in comparison with the rate of mixing of the reactants so that the product composition depends upon the order of addition and the competition between rapid reactions rather than any fundamental differences in mechanism.