Base catalyzed cyclization of N-aryl and N-alkyl-O-propargyl carbamates to 4-alkylidene-2-oxazolidinones

The base catalyzed cyclization of N-aryl and N-alkyl-O-propargyl carbamates is studied in detail. The effect of various bases and solvents on the efficacy of this cyclization reaction is analyzed and a new base-solvent system (LiOH in DMF) for effective cyclization of these carbamates is reported. A number of differentially substituted O-propargyl carbamates were cyclized to the corresponding 2-oxazolidinones under these conditions. The reaction conditions reported here are mild and no side reactions were observed in any of the substrates studied. A propargyl carbonate group was unaffected during the course of the cyclization of the O-propargyl carbamate group. The propargyl carbamates were prepared from the corresponding alkyl or aryl amines and the corresponding propargyl chloroformate, resulting in oxazolidinones diversely substituted at the nitrogen atom. N-Aryl-O-propargyl carbamates cyclized readily to the corresponding oxazolidinones with LiOH in DMF, whereas N-alkyl-O-propargyl carbamates reacted slowly under the same conditions. O-Propargyl carbamates substituted at the 1-position tend to cyclize faster whereas those substituted at 3-position cyclize considerably slower than the unsubstituted carbamates.     

19F and 1H NMR spectra of halocarbons

19F NMR chemical shifts and coupling constants are reported for 215 compounds. For 77 of these compounds, 1H NMR spectral data are also given. Long-range couplings, including 8J(F,F) and 5J(F,H), are reported. The complexity of halocarbon spectra owing to the presence of rotational isomers, asymmetric centers, long-range couplings, and chlorine isotope effects are illustrated, and the methods used for analyzing such complex spectra are briefly discussed.     

Equilibrium theory of two-dimensional simple liquids

Using the Wigner-Kirkwood expansion and bare Lennard-Jones (LJ) (12-6) potential, an effectiveLJ potential is derived, which includes the quantum effects through the expressions of the effective diameter∂(T, λ) and well-depth (T, λ). We use theWCA perturbation theory to calculate the free energy and pressure for theLJ and effectiveLJ potentials. Simple analytic expressions are given for the reference system and the first order correction calculated. The results are quite good at high density. The quantum effects on the free energy and pressure are also discussed.     

Intramolecular proton transfer induced by divalent alkali earth metal cation in the gas state

Interactions between divalent alkali earth metal (DAEM) ions M (M?Be, Mg, Ca, Sr, Ba) and the second stable glycine conformer in the gas phase, which can transfer into the ground‐state glycine‐M²⁺ (except the glycine–Be²⁺) among each corresponding isomers when these divalent metal ions are bound, are studied at the hybrid three‐parameter B3LYP level with three different basis sets. Proton transfers from the hydroxyl to the amino nitrogen of the glycine without energy barriers have been first observed in the gas phase in these glycine–M²⁺ systems. The interaction between the glycine and these DAEM ions except beryllium and magnesium ion only create an amino hydrogen pointing to the original hydroxyl due to their weaker interaction relative to those divalent transition metal (DTM) ion‐bound glycine derivatives, being obviously different from that between the glycine and DTM ions, in which two amino hydrogens point to the original hydroxyl oxygen when these metal‐chelated glycine derivatives are produced. The interaction energy between the glycine and divalent magnesium would be the boundary of one or two amino hydrogens pointing to the hydrogyl oxygen, i.e., the ?170.3 kcal/mol of binding energy is a critical point. Similar intramolecular proton transfer has also been predicted for those DTM ion‐chelated glycine systems; however, that in the gas state has not been observed in the monovalent metal ion‐coordinated glycine systems. The binding energy between some monovalent TM ion and the glycine is similar to that of the glycine–Ba²⁺, which has the lowest binding strength among these DAEM–ion chelated glycine complexes. The difference among them only lies in the larger electrostatic and polarized effects in the latter, which favor the stability of the zwitterionic glycine form in the gas phase. According to these observations, we predict that the zwitterionic glycine would exist in the field of two positive charges in the gas phase. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 94: 205–214, 2003     

Synthesis of novel poly(ethylene glycol) supported benzazepines: the crucial role of PEG on the selectivity of an intramolecular Heck reaction

Poly(ethylene glycol) (PEG 3400) was used as a soluble polymeric support for the synthesis of a series of novel benzazepines. The key step for the preparation of these heterocycles was a phosphine-free palladium-catalyzed Heck reaction. Palladium nanoparticles formed during the course of the reaction were characterized. The presence of PEG 3400 influenced the outcome of the reaction in terms of selectivity.     

Alkynylcyclohexadienyl tricarbonyliron complexes: A new directing effect for organoiron-mediated synthesis

The first example of an alkyne-substituted tricarbonyl(η⁵-cyclohexadienyl)iron(1+) complex has been prepared and the ω directing effect of the phenylethynyl substituent has been demonstrated in nucleophile addition reactions. Addition of NC⁻ also occurs at the a position to form an unusual η¹, η³-structure.     

Synthesis,molecular structures,and thermal decomposition of heterometallic (π-cyclooctadiene)platinum-bis(tricarbonyliron-μ3-chalcogenides)[Fe—Fe], (π-C8H12)Pt(μ3-X)2Fe2(CO)6, where X = S,Se, or Te

Transmetallation of the Fe₃(₃-X)₂(CO)₉ clusters (X = S, Se, or Te) under the action of (-C₈H₁₂)PtCl₂ afforded new heterometallic clusters (-C₈H₁₂)Pt(₃-X)₂Fe₂(CO)₆ (2—4, respectively), which were characterized by X-ray diffraction analysis. The (-C₈H₁₂)Pt fragment in these clusters is bound to two ₃-bridging chalcogen atoms X. The iron atoms are linked to each other. The coordination environment about the Pt atom is planar-square; the Pt...Fe distance is larger than 3.2 . In the synthesis of cluster 4, a new Pt complex was also obtained for which the structure (CO)₂Pt(-Te)₂Pt(CO)₂ (5) was proposed. According to the results of differential scanning calorimetry, thermal decomposition of complex 5 gave rise only to PtTe, whereas complexes 1—4 gave products with the empirical formula Fe₂PtX₂C₂O₂. The influence of the steric effects on the geometry of the clusters is discussed.     

SHAPE MEMORY EFFECT OF PU IONOMERS WITH IONIC GROUPS ON HARD-SEGMENTS

SMPU （shape memory polyurethane） non-ionomers and ionomers, synthesized with poly（c-caprolactone） （PCL）, 4, 4＇-diphenylmethane diisocyanate （MDI）, 1,4-butanediol （BDO）, dimethylolpropionic acid （DMPA） were measured with cyclic tensile test and strain recovery test. The relations between the structure and shape memory effect of these two series were studied with respect to the ionic group content and the effect of neutralization. The resulting data indicate that, with the introduction of asymmetrical extender, the stress at 100% elongation is decreased for PU non-ionomer and ionomer series, especially lowered sharply for non-ionomer series; the fixation ratio of ionomer series is not affected obviously by the ionic group content; the total recovery ratio of ionomer series is decreased greatly. After sufficient relaxation time for samples stretched beforehand, the switching temperature is raised slightly, whereas the recovery ratio measured with strain recovery test method is lowered with increased DMPA content. The characterization with FT-IR, DSC, DMA elucidated that, the ordered hard domain of the two series is disrupted with the introduction of DMPA which causes more hard segments to dissolve in soft phase; ionic groups on hard segment enhance the cohesion between hard segments especially at high ionic group content and significantly facilitate the phase separation compared with the corresponding non-ionomer at moderate ionic group content.     

Thin-layer adsorption chromatography with mixed mobile phases. 4. Extension of Ościk's equation to heterogeneous adsorbents

In this paper the equation for thin-layer adsorption chromatography with multicomponent mobile phases, proposed by O?cik in 1965 is extended to energetically heterogeneous solid surfaces. Other forms of this equation, more convenient in practical applications, are presented. Model calculations are made for TLC with binary mobile phases according to the modified form of O?cik's equation. Finally, this equation is compared with that of Snyder.     

Novel application of quantum chemical investigation in terms of substituent parameters: Statistical comparison of dual and single substituent parameter treatments

The correlation analysis of Mulliken charge (Q_M) calculated by using density functional theory (B3LYP/STO-3G) calculations of 1-(4-azido-5-hydroxymethyl-tetrahydro-selenophen-2-ylmethyl)-5-substituted-1H-pyrimidine-2,4-dione, were done by using mono substituent parameter (Hammett’s model), and dual substituent parameter (Taft’s, Reynolds’, and Swain’s models). The dual substituent parameter correlations of the Q_M data gave no significant improvement over single parameter correlations, the best correlation observed with the Taft’s Model as compared with the Swain’s and Reynolds’ Models, respectively. The correlation analysis of Mulliken charge can be used successfully to demonstrate the existence or absence of the interaction between the oxygen of the carbonyl group and selenium atom.