1,3,5-Trisubstituted hexahy drotriazines as mannich reagents. I. Preparation of secondary aminomethyl sulfide hydrochlorides

1,3,5-Trisubstituted hexahy drotriazines react with hydrogen chloride in the presence of anhydrous solvents to form useful intermediates for the introduction of the RNHCH₂- group into compounds which undergo the Mannich reaction. The effectiveness of the new aminomethyl-ating agent has been demonstrated by the preparation of secondary aminomethyl sulfide hydro-chlorides.     

Snapshots of dioxygen activation by copper: the structure of a 1:1 Cu/O(2) adduct and its use in syntheses of asymmetric Bis(mu-oxo) complexes

The X-ray structure of a 1:1 Cu/O(2) adduct revealed side-on (eta(2)) O(2) coordination. Density functional calculations corroborated the structure, indicated a significant contribution of a Cu(III)-(O(2)(2-)) resonance form, and provided insights into the key bonding interactions. Reaction of a 1:1 adduct supported by a slightly different beta-diketiminate ligand with Cu(I) reagents resulted in the formation of novel asymmetric bis(mu-oxo) complexes that were identified by EPR, UV-vis, and Raman spectroscopy, as well as by an X-ray structure in one instance.     

Synthesis of Pyranthiones

A general method for the preparations of pyranthiones is particularly useful for preparing substituted xanthiones which are unavailable by established procedures. Reaction of a xanthone with p-tosyl isocyanate or with trichloroacetyl isocyanate produces the corresponding imino derivatives, which upon treatment with n-butylamine followed by hydrogen sulfide gives the desired xanthione in good yield.     

Simultaneous analysis of methionine- and leucine-enkephalin from rat brain: quantification by liquid chromatography-electrochemistry

This study focuses on the application of liquid chromatography with electrochemical detection (LC-ED) for the analysis of methionine-enkephalin (ME) and leucine-enkephalin (LE) extracted from rat brain regions. The high applied potentials necessary for enkephalin detection required the development of an efficient sample processing protocol. Brain extracts were processed using chromatographic mode sequencing (CMS). The decrease in electroactive interfering substances by CMS improved the chromatographic resolution of ME and LE and the electrode performance. Other qualitative and analytical methods were used to evaluate the enkephalin data obtained by LC-ED for rat brain regions. This study demonstrates that LC-ED provides both the sensitivity and specificity necessary for the analysis of enkephalins from rat brain regions.     

13C NMR studies of molecular relaxation processes in polar fluids

A study of the dynamical molecular structure of a dilute polar fluid is reported, in which ¹³C spin-lattice relaxation times of decanol in deuterated cyclohexane are presented for the individual carbon atoms, and the results are discussed in the context of viscosity data of decanol in alkane systems. The two techniques provide complementary information about the mobility of the alcohol chains and the onset of multimer formation, which is also pertinent to the dynamics of electron solvation in the same systems.     

The reactions of 4-dicyanomethylene-2-phenyl-4H-1-benzopyran and some benzologs with nucleophiles

4-Dicyanomethylene-2-phenyl-4H-1-benzopyran (1) reacts with primary amines under mild conditions to give 4-imino-3-alkyl-5-alkylimino-2-phenyl-3,4-dihydro-5H-[1]benzopyrano[3,4-c]-pyridine derivatives which, in turn, are hydrolyzed with acid to 4-imino-3-alkyl-2-phenyl-3,4-dihydro-5H-[1]benzopyrano[3,4-c]pyridin-5-ones. When more vigorous conditions are employed for the reactions of 1 with primary amines, Dimroth rearrangements take place and the products are derivatives of 4-alkyl- (or aryl)amino-5-alkyl- (or aryl)imino-2-phenyl-5H-[1]benzopyrano-[3,4-c]pyridine. The latter compounds are hydrolyzed by acid to the corresponding 5-pyridone derivatives. The reaction of 1 with piperidine gives 2-phenyl-4-piperidyl-5H-[1]benzopyrano-[3,4-c]pyridin-5-one. Sodium methoxide reacts with 1 to give 3-cyano-2-methoxy-4-(2-hydroxyphenyl)-6-phenylpyridine. Two benzologs of 1 have been allowed to react with primary and secondary amines and the products are analogous to those obtained from 1 .     

Theoretical calculation of electrode potentials: Electron-withdrawing compounds

The electrode potential of 2,3-dicyanobenzoquinone in aqueous solution has been calculated relative to parabenzoquinone using a thermodynamic cycle approach that includes accurate gasphase ab initio calculations and calculation of differences in free energies of hydration using the free-energy perturbation method. The discrepancy between the calculated and experimental electrode potential is disappointingly large (99 mV) compared to previous studies using this approach. This, along with the experimental evidence, suggests that the experimental value itself is too large and that theoretical approaches may indeed be as reliable as experimental ones for determining redox properties of molecules such as 2,3-dicyanobenzoquinone. In the light of this discrepancy we have examined the variation of the results with the basis set, inclusion of electron correlation and changes in the parameters used in the molecular dynamics free-energy simulations. The results are shown to be dependent upon the torsional parameters and especially dependent upon the basis set or semiempirical method used to obtain the electrostatic potential-derived charges. The best charge set was determined using the ab initio criteria of completeness—as far as it can be applied to large molecules—and also by studying the effect of hydration on these charges. This was done by allowing the solvent to perturb the wave function prior to the electrostatic potential determination. Thus, 3-21G and 6-31G * basis sets were found to give satisfactory results. Similar results were obtained using semiempirical and ab initio geometries.     

Radius of clusters at the percolation threshold: A position space renormalization group study

Using a direct position-space renormalization-group approach we study percolation clusters in the limits , wheres is the number of occupied elements in a cluster. We do this by assigning a fugacityK per cluster element; asK approaches a critical valueK _c , the conjugate variables . All exponents along the path (K–K _c ) 0 are then related to a corresponding exponent along the paths . We calculate the exponent , which describes how the radius of ans-site cluster grows withs at the percolation threshold, in dimensionsd=2, 3. Ind=2 our numerical estimate of =0.52±0.02, obtained from extrapolation and from cell-to-cell transformation procedures, is in agreement with the best known estimates. We combine this result with previous PSRG calculations for the connectedness-length exponent , to make an indirect test of cluster-radius scaling by calculating the scaling function exponent using the relation =/. Our result for is in agreement with direct Monte-Carlo calculations of , and thus supports the cluster-radius scaling assumption. We also calculate ind=3 for both site and bond percolation, using a cell of linear sizeb=2 on the simple-cubic lattice. Although the result of such small-cell calculations are at best only approximate, they nevertheless are consistent with the most recent numerical estimates.Supported in part by grants from ARO and ONR