Structural equilibrium (S=0) ⇄ (S=1)and inversion of the configuration of the seven-membered saturated metal-containing ring in four-coordinate pyrazolealdiminate metal chelates of nickel(II) based on tetradentate ligands

¹H and¹³C NMR, x-ray structural analysis, and magnetic moment measurements have shown that in 5-thio(seleno)pyrazolealdiminate complexes of nickel(II) based on tetradentate ligands containing the fragment, with n=2, flattening of the chelate unit takes place in solution and in the solid state. A similar structure in which the diamine metal-containing ring has the twist-chair conformation is observed for the crystals of the complexes with n=4. For the complexes with n=4 in solution at a temperature below –50°C, rapid (on the NMR time scale) interconversion of the flattened (P) (S=0) and pseudotetrahedral (T) (S=1) structures is observed, not accompanied by inversion of the tetrahedral configuration of the metal atom. At temperatures above –50°C, in addition to the low-barrier reactions (T) (P), conversion of the seven-membered saturated metal-containing ring and inversion of the tetrahedral configuration of the Ni atom with activation barriers of 48–51 kJ/mole are observed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 327–335, February, 1990.     

Simultaneous determination of p-hydroxylated and dihydrodiol metabolites of phenytoin in urine by high-performance liquid chromatography

Accurate urinary measurements of the two major metabolites of phenytoin, 5-(p-hydroxyphenyl)-5-phenylhydantoin (p-HPPH) and 5-(3,4-dihydroxy-cyclohexa-1,5-dienyl)-5-phenylhydantoin (dihydrodiol, DHD), are necessary for pharmacokinetic and drug-interaction studies of this commonly used antiepileptic drug. We describe a simple, rapid, acid hydrolysis, with liquid-liquid extraction and simultaneous isocratic reversed-phase high-performance liquid chromatography of p-HPPH and 5-(m-hydroxyphenyl)-5-phenylhydantoin (m-HPPH) (hydrolytic end product of DHD). p-HPPH and m-HPPH were quantitated against their separate respective internal standards of alphenal and tolylbarb. The mobile phase consisted of water-dioxane-tetrahydrofuran (80:15:5, v/v/v) at 2 ml/min and at 50 degrees C, with detection at 225 nm. Baseline separation was achieved by use of a 16 cm x 3.9 mm Nova-Pak C18 column and total analysis time of 12 min. p-HPPH and m-HPPH concentrations ranged from 10 to 200 and from 2 to 30 micrograms/ml, respectively, with between-day coefficients of variations of 3.3-4.5% and 2.2-5.1% for controls. All standard curves were linear with r values greater than 0.993. The DHD concentration was determined by multiplying m-HPPH concentrations by 2.3.     

Water in carbon nanotubes: adsorption isotherms and thermodynamic properties from molecular simulation

Grand canonical Monte Carlo simulations are performed to study the adsorption of water in single-walled (6:6), (8:8), (10:10), (12:12), and (20:20) carbon nanotubes in the 248-548 K temperature range. At room temperature the resulting adsorption isotherms in (10:10) and wider single-walled carbon nanotubes (SWCNs) are characterized by negligible water uptake at low pressures, sudden and complete pore filling once a threshold pressure is reached, and wide adsorption/desorption hysteresis loops. The width of the hysteresis loops decreases as pore diameter narrows and it becomes negligible for water adsorption in (8:8) and (6:6) SWCNs. Results for the isosteric heat of adsorption, density profiles along the pore axis and across the pore radii, order parameter across the pore radii, and x-ray diffraction patterns are presented. Layered structures are observed when the internal diameter of the nanotubes is commensurate to the establishment of a hydrogen-bonded network. The structure of water in (8:8) and (10:10) SWCNs is ordered when the temperature is 298 and 248 K, respectively. By simulating adsorption isotherms at various temperatures, the hysteresis critical temperature, e.g., the lowest temperature at which no hysteresis can be detected, is determined for water adsorbed in (20:20), (12:12), and (10:10) SWCNs. The hysteresis critical temperature is lower than the vapor-liquid critical temperature for bulk Simple Point Charge-Extended (SPCE) water model.     

The kinetics of radical polymerization—XXVII. Investigation of the radical reactivity of 3,3′- and 4,4′-disubstituted azobenzenes in the polymerization of vinylacetate

A study was made on the inhibition by some 3,3′- and 4,4′-disubstituted azobenzenes of the polymerization of vinylacetate initiated by azoisobutyronitrile at 50°. The inhibitory effects of these substances can be attributed to their ability to engage in radical addition giving a less reactive hydrazyl type radical. The mechanism of the inhibition has been established by ESR and kinetic (stoichiometric) measurements. The value of k₅/k₂ (characteristic of the reactivity of an inhibitor) was determined for 9 substituents. The radical reactivity of the aromatic azo group was decreased by electron donor substituents and increased by electron acceptors. The substituent effect can be well interpreted by the Hammett equation; the value of the reaction constant was ? = +0.53.     

Laurenanes: fenestranes with a twist

Four isomeric alcohols derived from the diterpene lauren-1-ene (1) have been examined by NMR methods (nuclear Overhauser enhancements, coupling constants, and variable-temperature studies) and by molecular mechanics using the MM3 force field to investigate a conformational twisting of the [5.5.5.7]fenestrane ring system. Results have been correlated with a concurrent study of remote functionalization reactions induced by iodobenzene diacetate/iodine under ultrasonic irradiation. Three of the laurenan-2-ols, 6, 7, and 8, lead to the same tetrahydrofuran derivative, 2beta,14beta-epoxylaurenane (9), and evidence for beta-cleavage of the alkoxy radical intermediate is obtained through the isolation of a ring-cleavage product 11 with a rearranged carbon skeleton. The products from the remaining alcohol 3 demonstrate solution dynamics involving the conformational twisting of the laurenane skeleton.     

Novel polymer-bound chiral selenium electrophiles

[reaction: see text]. Polymer-bound chiral electrophilic selenium reagents have been developed and applied to stereoselective selenenylation reactions of various alkenes. Different cleavage protocols allow further functionalization of the addition products leading to improvements in selenium-based solid-phase chemistry.     

An improved procedure for the preparation of 2-amino-8-alkylpyrido-[2,3-d]pyrimidin-4(3H)-ones (8-alkyl-N5-deazapterins)

We report an improved procedure for the preparation of 8-alkyl-N5-deazapterins which allows clean preparation of all ring-methyl substituted compounds, including 5- and 7-methyl substituted compounds. The procedure was also successfully applied to the preparation of N5-deazapterins with improved yield over previous reports. The uv/visible and pKa data confirm the predicted increased basicity of 8-alkyl-N5-deazapterins compared with the N5-deazapterin parents, and indicate that N5-deazapterins protonate on N8 and 8-alkyl-N5-deazapterins protonate on N3.     

Homolytic dissociation of the carbon-element σ bonds by Grignard reagents

The reaction of 2-ethyl-3-tetrahydrofuryl thiocyanate (I) and triphenylacetonitrile (VIII) with methylmagnesium iodide in ether was studied using GC/MS, PMR and¹³C NMR spectroscopy. The reaction of (I) with CH₃MgI gives the product of the homolysis of the C-S bond, namely, bis(2-ethyl-3-tetrahydrofuryl) disulfide (II), in 81% yield. This reaction is assumed to be general in nature since triphenylacetonitrile (VIII) is also homolytically cleaved by the action of CH₃MgI to give triphenylmethane.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2886–2888, December, 1991.     

Crystal and molecular structure of hexacarbomethoxycyclopropane

A. N. Nesmeyanov Institute of Heteroorganic Compounds, Academy of Sciences of the USSR. N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 30, No. 3, pp. 171–173, May–June, 1989.