Synthesis of sedamine by tethered cyclofunctionalisation

The piperidine alkaloid, (+)-sedamine has been synthesised starting from (S)-1-phenyl-3-butenol using a stereoselective, intramolecular palladium-catalysed cyclocarbonylation reaction of a substituted hydroxylamine.     

Dissociation constant of acetic acid in N-methylpropionamide from 5 to 55°C and related thermodynamic quantities

The dissociation constant of acetic acid in N-methylpropionamide (NMP) has been determined at 11 temperatures from 5 to 55°C by measurement of the electromotive force of cells without liquid junction containing hydrogen gas electrodes and silver-silver chloride electrodes. The pK at 25°C was found to be 7.995 (molal scale) as compared with 4.756 in water; thus, acetic acid is much weaker in NMP than in water despite the higher dielectric constant of the nonaqueous solvent (176 as compared with 78.3 at 25°C). The standard changes of enthalpy and entropy for the dissociation of acetic acid were calculated from the temperature coefficient of pK, and thermodynamic functions for the transfer dissociation process were obtained. The weakness of acetic acid in NMP is discussed in terms of electrostatic effects and solute-solvent interactions.     

Coarse grained models for flexible liquid crystals: parameterization of the bond fluctuation model

We extend the bond fluctuation model, originally devised to investigate polymer systems, to contain anisotropic interactions suitable for the simulation of large flexible molecules such as liquid crystalline polymers and dendrimers. This extended model coarse grains the interaction between the flexible chains at a similar level of detail to the mesogenic units. Suitable interaction parameters are obtained by performing trial simulations on a low molar mass liquid crystalline system. The phase diagram of this system is determined as a function of the molecular stiffness. The nematic to isotropic transition temperature is found to increase with increasing stiffness.     

A threefold superstructure of the anti‐epileptic drug phenytoin sodium as a mixed methanol solvate hydrate

Phenytoin sodium, a salt of 5,5‐diphenylimidazolidine‐2,4‐dione, or phenytoin, is commercially available in various dosage forms for its anti‐epileptic properties to treat and prevent seizures. The title compound, poly[aquatris(μ₃‐4,4‐diphenyl‐2,5‐dioxoimidazolidin‐1‐ido)trimethanoltrisodium(I)], [Na₃(C₁₅H₁₁N₂O₂)₃(CH₄O)₃(H₂O)_1.08]_n, a methanol solvate and hydrate of phenytoin sodium, forms a modulated crystal structure that consists of a supercell made up of three close‐to‐identical repeat units. Each of the basic fragments consists of one phenytoin anion, a sodium cation, and either a methanol, or a methanol and a water molecule coordinated to the sodium ion, yielding a formula unit of Na(C₁₅H₁₁N₂O₂)(CH₃OH)_x(H₂O)_y for each of the three segments (x, y = 0 or 1; x + y = 1 or 2). Modulation along the b axis is introduced due to the presence or absence of water or methanol molecules at sodium and by the alternating torsion angles of one of the two phenytoin phenyl rings. Individual segments within the asymmetric unit are linked by covalent Na—O and Na—N bonds, with each sodium ion coordinated to one anionic amide N atom and three keto O atoms. The Na—N and one of the Na—O bonds connect (C₁₅H₁₁N₂O₂)·Na units along the modulation direction, creating an infinite [(C₁₅H₁₁N₂O₂)·Na] chain that is further stabilized by intramolecular N—H…O hydrogen bonding parallel to [010]. The second Na—O bond connects this chain with a symmetry‐equivalent copy of itself created by a screw‐axis operation, yielding double strands of [(C₁₅H₁₁N₂O₂)·Na] chains. Two of these double strands, propagating in opposite directions, constitute the content of the unit cell. Neighboring double strands are connected with each other to form layers perpendicular to the a axis, tethered together via O—H…O hydrogen bonds involving the water and methanol molecules. In addition to modulation, each of the repeat units also exhibits disorder of the modulated segments. Phenyl rings of each repeat unit are rotationally disordered, and sodium‐coordinated methanol and water molecules are also positionally disordered and/or partially occupied. The solvated structure reported here, while not matching the patterns reported for any of the known forms of phenytoin sodium, does provide a first insight into the complications and complexities involved in resolving the structure of anhydrous phenytoin sodium.     

The solvent effect of methanol on the dissociation of Bis·H+ from 10 to 40°C

The solvent effect on the acidic dissociation of the protonated base tris(hydroxymethyl)aminomethane (Tris) has been studied in aqueous mixtures of several organic constituents with qualitatively similar results. The dissociation constant of protonated 2-amino-2-methyl-1,3-propanediol (Bis), the analog of Tris with two hydroxy groups, has now been determined in 50 mass % methanol by emf measurements of cells without liquid junction in the temperature range 10 to 40°C. The conventional treatment of the data indicated abnormally low values for the activity coefficient of BisHCl, but an alternate method of calculation with allowance for ion pairing provided no advantage. The pK_a in the range from T=283.15 to 313.15 K is given by $$pK_a = 3755.63/T - 24.5127 + 3.56855 In T$$ with a standard deviation of 0.0006 at the seven temperatures. Thermodynamic quantities for the dissociation process and corresponding quantities for the transfer from water to 50 mass % methanol were derived. The implications of the results in terms of selective solute-solvent stabilization are discussed.     

Activity coefficient of hydrochloric acid in the system HCl−KCl−H2O at 25°C and lonic strengths from 0.1 to 3 moles-kg−1

The activity coefficient of hydrochloric acid has been determined in HCl–KCl–H₂O mixtures at 25°C and for seven values of the ionic strength between 0.1 and 3.0 mole-kg^–1, using the cellPt;H ₂(g, 1atm)\HCl(m _A ),KCl _B AgCl;Ag The results are compared with those of previous studies of the same system and are interpreted in terms of ionic interactions specific to the mixture by use of Pitzer's treatment of mixed electrolyte solutions.     

The correspondence between the molecular orbital and differential ionization energies methods

The correspondence between Self-Consistent Hückel MO methods and Differential Ionization Energies methods is discussed in terms of the approximations used for the diagonal matrix elements. The two methods are shown to be equivalent if electronic correlation is neglected. Ground-state properties of the hydrogen halides are calculated by these simple methods and shown to be in good overall agreement with experimental data.

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Zusammenfassung Die Übereinstimmung zwischen selbstkonsistenten Hückel MO-Methoden und Methoden der Differentiellen Ionisierungsenergien wird in Termen solcher Näherungen diskutiert, die für die diagonalen Matrixelemente benutzt werden. Es wird gezeigt, daß die beiden Methoden äquivalent sind, wenn die Elektronenkorrelation vernachlässigt wird. Grundzustandseigenschaften der hydrogen halides werden mit diesen einfachen Methoden ausgerechnet und zeigen sich in überall guter Übereinstimmung mit experimentellen Daten.

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Résumé La correspondance entre les méthodes SCF Hückel et d'énergie d'ionisation différentielle est discutée en fonction des approximations utilisées pour les éléments de matrice diagonaux. Les deux méthodes sont équivalentes si la corrélation électronique est négligée. Les propriétés de l'état fondamental des acides halogènés sont calculées par ces méthodes simples et l'on constate un accord raisonnable avec les données expérimentales.

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Work supported by the Research Corporation and the National Science Foundation (Grant GY 2657/67).