Catalysis of the beta-elimination of HF from isomeric 2-fluoroethylpyridines and 1-methyl-2-fluoroethylpyridinium salts. Proton-activating factors and methyl-activating factors as a mechanistic test to distinguish between concerted E2 and E1cb irreversible mechanisms

Second-order rate constants, k(OH)(N), M(-)(1) s(-)(1), for the beta-elimination reactions of HF with 2-(2-fluoroethyl)pyridine (2), 3-(2-fluoroethyl)pyridine (3), and 4-(2-fluoroethyl)pyridine (4) in OH(-)/H(2)O, at 50 degrees C and mu = 1 M KCl, are = 0.646 x 10(-)(4) M(-)(1) s(-)(1), = 2.97 x 10(-)(6) M(-)(1) s(-)(1), and = 5.28 x 10(-)(4) M(-)(1) s(-)(1), respectively. When compared with the second-order rate constants for the same processes with the nitrogen-methylated substrates 1-methyl-2-(2-fluoroethyl)pyridinium iodide (5), 1-methyl-3-(2-fluoroethyl)pyridinium iodide (6), and 1-methyl-4-(2-fluoroethyl)pyridinium iodide (7), the methyl-activating factor (MethylAF) can be calculated from the ratio k(OH)(NCH)3/, and a value of 8.7 x 10(5) is obtained with substrates 5/2, a value of 1.6 x 10(3) with 6/3, and a value of 2.1 x 10(4) with 7/4. The high values of MethylAF are in agreement with an irreversible E1cb mechanism (A(N)D(E) + D(N)) for substrates 5 and 7 and with the high stability of the intermediate carbanion related to its enamine-type structure. In acetohydroxamate/acetohydroxamic acid buffers (pH 8.45-9.42) and acetate/acetic acid buffers (pH 4.13-5.13), the beta-elimination reactions of HF, with substrates 2 and 4, occur at NH(+), the substrates protonated at the nitrogen atom of the pyridine ring, even when the [NH(+)] is much lower than the [N], the unprotonated substrate, due to the high proton-activating factor (PAF) value observed: 3.6 x 10(5) for 2 and 6.5 x 10(4) for 4 with acetohydroxamate base. These high PAF values are indicative of an irreversible E1cb mechanism rather than a concerted E2 (A(N)D(E)D(N)) mechanism. Finally, the rate constant for carbanion formation from NH(+) with 2 is k(B)(NH)+ = 0.35 M(-)(1) s(-)(1), which is lower than when chlorine is the leaving group ( = 1.05 M(-)(1) s(-)(1); Alunni, S.; Busti, A. J. Chem. Soc., Perkin Trans. 2 2001, 778). This is direct experimental evidence that some lengthening of the carbon-leaving group bond can occur in the intermediate carbanion. This is a point of interest for interpreting a heavy-atom isotope effect.     

Macromolecule Loading into Spherical,Elliptical, Star‐Like and Cubic Calcium Carbonate Carriers

We fabricated calcium carbonate particles with spherical, elliptical, star‐like and cubical morphologies by varying relative salt concentrations and adding ethylene glycol as a solvent to slow down the rate of particle formation. The loading capacity of particles of different isotropic (spherical and cubical) and anisotropic (elliptical and star‐like) geometries is investigated, and the surface area of such carriers is analysed. Potential applications of such drug delivery carriers are highlighted.     

Study of ruthenium(II) complexes with anticancer drugs as ligands. Design of metal-based phototherapeutic agents

The reaction of trans-[RuCl(2)(PPh(3))(3)] (Ph = C(6)H(5)) with 2-thio-1,3-pyrimidine (HTPYM) and 6-thiopurines (TPs) produced mainly crystalline solids that consist of cis,cis,trans-[Ru(PPh(3))(2)(N,S-TPYM)(2)] (1) and cis,cis,trans-[Ru(PPh(3))(2)(N(7),S-TPs)(2)]X(2) (X = Cl(-), CF(3)SO(3)(-)). In the case of TPs, other coordination isomers have never been isolated and reported. Instead, the mother liquor obtained after filtration of 1 produced red single crystals of trans,cis,cis-[Ru(PPh(3))(2)(N,S-TPYM)(2)].2H(3)O(+).2Cl(-) (2.2H(3)O(+).2Cl(-)). Selected ruthenium(II)-thiobase complexes were studied for their structural, reactivity, spectroscopic, redox, and cytotoxic properties. Single crystals of 1 contain thiopyrimidinato anions chelated to the metal center via N and S. The Ru[bond]N bonds are significantly elongated for 1 [2.122(2) and 2.167(2) A] with respect to 2 [2.063(3) A] because of the trans influence from PPh(3). The coordination pseudo-octahedron for 2 is significantly elongated at the apical sites (PPh(3) ligands). Solutions of cis,cis,trans isomers in air are stable for weeks, whereas those of 2 turn green within 24 h, in agreement with the respective redox potentials. cis,cis,trans- and trans,cis,cis-[Ru(PH(3))(2)(N,S-TPYM)(2)], as optimized through the DFT methods at the Becke3LYP level are in good agreement with experimental geometrical parameters (1 and 2), with cis,cis,trans being more stable than trans,cis,cis by 3.88 kcal. The trend is confirmed by molecular modeling based on semiempirical (ZINDO/1) and molecular mechanics (MM) methods. Cytotoxic activity measurements for cis,cis,trans-[Ru(PPh(3))(N-THZ)(N(7),S -H(2)TP)(2)]Cl(2) (4) (THZ = thiazole, H(2)TP = 6-thiopurine) and cis,cis,trans-[Ru(PPh(3))(2)(N(7),S-HTPR)2]Cl(2) (5) (HTPR = 6-thiopurine riboside) against ovarian cancer cells A2780/S gave IC(50) values of 17 +/- 1 and 29 +/- 9 microM, respectively. Furthermore, the spectral analysis of HTPYM, TPs, and their Ru(II) complexes in solution shows that intense absorptions occur in the UVA/vis region of light, whereas standard nucleobases absorb in the UVB region.     

A boundary-integral equation method for free surface viscous flows

Summary A boundary integral equation method is proposed for the solution of viscous recirculating flows with free surfaces. In particular the method is applied to thermocapillary convection and to drop formation, both in micro-gravity conditions, the latter to test its capability to handle real unsteady problems.The presence of non linear terms in Navier-Stokes equations leads to a volume integral, which has to be approximated by a linearization procedure.Several numerical results for thermocapillary flows, both with fixed and moving free surface, are discussed in comparison with previously obtained finite difference solutions. Some preliminary results, and in particular the time evolution of the free surface shape, are also presented for the drop formation problem. Only plane two dimensional fields are considered for both problems.

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Sommario Si propone un metodo basato sulla soluzione di equazioni integrali di contorno per flussi viscosi con superficie libera. Tale metodo è applicato allo studio della convezione termocapillare ed al processo di formazione di una goccia, entrambi in condizioni di microgravità. La presenza dei termini non lineari nell'equazione di Navier-Stokes comporta un integrale di volume che viene approssimato mediante un processo di linearizzazione.Risultati numerici per flussi termocapillari con superficie libera sia fissa che mobile sono confrontati con altri ottenuti in precedenza con un metodo alle differenze finite. Si presentano inoltre alcuni risultati preliminari sul problema della formazione della goccia ed in particolare l'evoluzione nel tempo della configurazione geometrica della superficie libera. Nei due casi si analizzano solo campi bidimensionali.

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Presented at the VII National Conference AIDAA, Naples, September 1983.

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In leave of absence from Tianjin University, China.     

Bleaching cellulosic fibers via pre-sorption of N-[4-(triethylammoniomethyl)-benzoyl]-butyrolactam chloride

The sorption of a novel cationic bleach activator, N-[4-(Triethylammoniomethyl)benzoyl]-butyrolactam Chloride (TBBC), was measured on regenerated bamboo fiber. At 25 °C near neutral pH, the sorption rate of TBBC onto the fiber was initially rapid and equilibrium was reached within 20 min. Adsorption equilibria experiments followed a Freundlich isotherm. At the sorption equilibrium, bleaching was initiated by addition of sodium perborate to liberate hydrogen peroxide, which reacted with TBBC to generate a peracid that is a more kinetically active oxidant than peroxide. A sorption–activation model was developed that supports the enhanced bleaching of cellulosic fibers using cationic bleach activators under neutral to alkaline conditions.     

Solvent- and temperature-dependent functionalisation of enantioenriched aziridines

A highly stereo‐ and regioselective functionalisation of chiral non‐racemic aziridines is reported. By starting from a parent enantioenriched aziridine and finely tuning the reaction conditions, it is possible to address the regio‐ and stereoselectivity of the lithiation/electrophile trapping sequence, thereby allowing the preparation of highly enantioenriched functionalised aziridines. From chiral N‐alkyl trans‐2,3‐diphenylaziridines (S,S)‐ 1 a , b , two differently configured chiral aziridinyllithiums could be generated (trans‐ 1 a , b‐Li in toluene and cis‐ 1 a , b‐Li in THF), thus disclosing a solvent‐dependent reactivity that is useful for the synthesis of chiral tri‐substituted aziridines with different stereochemistry. In contrast, chiral aziridine (S,S)‐ 1 c showed a temperature‐dependent reactivity to give chiral ortho‐lithiated aziridine 1 c‐ ortho ‐Li at ?78 °C and α‐lithiated aziridine 1 c‐α‐Li at 0 °C. Both lithiated intermediates react with electrophiles to give enantioenriched ortho‐ and α‐functionalised aziridines. The reaction of all the lithiated aziridines with carbonyl compounds furnished useful chiral hydroxyalkylated derivatives, the stereochemistry of which was ascertained by X‐ray and NMR spectroscopic analysis. The usefulness of chiral non‐racemic functionalised aziridines has been demonstrated by reductive ring‐opening reactions furnishing chiral amines that bear quaternary stereogenic centres and chiral 1,2‐, 1,3‐ and 1,5‐aminoalcohols. It is remarkable that the solvent‐dependent reactivity observed with (S,S)‐ 1 a , b permits the preparation of both the enantiomers of amines ( 11 and ent‐ 11 ) and 1,2‐aminoalcohols ( 13 and ent‐ 13 ) starting from the same parent aziridine. Interestingly, for the first time, a configurationally stable chiral α‐lithiated aziridine ( 1 c‐α‐Li ) has been generated at 0 °C. In addition, ortho‐hydroxyalkylated aziridines have been easily converted into chiral aminoalkyl phthalans, which are useful building blocks in medicinal chemistry.     

Synthesis of allylic alcohols from oxazolinyloxiranes

Lithium diisopropylamide (LDA) (or s-BuLi/TMEDA) in diethyl ether promotes smooth ring opening of oxazolinyl alkyl oxiranes to give oxazolinyl allylic alcohols, which are masked Baylis-Hillman adducts, in good to excellent yields. An E2-E1cb-like syn-beta-elimination is proposed to explain the easy base-promoted isomerization of the studied oxiranes.     

Vector green's function method for unsteady Navier-Stokes equations

Summary The Green's function method is reformulated in general terms to treat vector unsteady and nonlinear equations. The particular expressions of the adjoint linear operator, the Green's formula and the integral representation of the solution are derived for unsteady Navier Stokes equations. The appropriate fundamental solutions for incompressible and for certain compressible flows have been obtained in closed form. Both the positive features and the possible limits of the method are briefly outlined.

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Sommario Si riformula in termini generali il metodo della funzione di Green per estenderlo al caso di equazioni vettoriali e non lineari. In particolare si ricavano le espressioni della formula di Green e della rappresentazione integrale della soluzione per le equazioni di Navier Stokes non stazionarie. Si ottengono le soluzioni fondamentali in forma chiusa sia per il caso di fluidi comprimibili che incomprimibili. Si discutono infine brevemente i lati positivi ed i possibili limiti della metodologia illustrata.