Analysis of FTIR spectra of CH2 79Br35Cl; the ν3 and ν9 fundamentals

The infrared spectrum of isotopically pure CH₂ ⁷⁹BrCl has been recorded at a resolution of 0.0025?cm^?1 and 0.0023?cm^?1 (FWHM) in the range 600–1600?cm^?1 with a Bruker IFS 120 HR Fourier transform spectrometer in Wuppertal. Here we report the full rotational analysis of the ν₃ and ν₉ fundamentals of the most abundant species CH₂ ⁷⁹Br³⁵Cl . Improved ground state constants, up to quartic terms, have been obtained from ground state combination differences (GSCD) involving transitions of the fundamentals ν₃, ν₄, ν₅ and ν₉. Both ν₃ and ν₉ transitions were fitted to a Watson-type Hamiltonian in the S-reduction, yielding accurate molecular constants for the ν₃ and ν₉ excited states. Small local perturbations were observed in both bands. Prominent features in the spectra were assigned to the ν₃ and ν₉ fundamentals of the CH₂ ⁷⁹Br³⁷Cl isotopic species and the hot-bands ν₃+ν₆???ν₆ and ν₉+ν₆???ν₆ of CH₂ ⁷⁹Br³⁵Cl.     

Synthese et N-Acylation Regiospecifique de 1,2,5-Thiadiazolidines 1,1-Dioxydes Chirales

The regiospecific synthesis of chiral N-acyl cyclosulfamides (sulfa-analogues of cyclic ureas) was carried out starting from chlorosulfonyl isocyanate (CSI), 1-substituted N-benzyl-2-chloroethylamine hydrochloride and acyl chloride. Chiral N-acyl-thiadiazolidines 1,1-dioxides have been prepared in high yield starting from the corresponding cyclosulfamides acyl chloride, triethylamine and a catalytic amount of 4-(N,N-dimethylamino)pyridine. L'accès régiospécifique aux cyclosulfamides chiraux N-acylés (analogues sulfonés d'urèes cycliques) a été développé à partir de l'isocyanate de chlorosulfonyle, de N-benzyl-2-chloroéthylamine chirale substituée en position 1 et de chlorure d'acide. Les N-acyl thiadiazolidines 1,1-dioxydes chirales ont été préparées avec des rendements élevés à partir du cyclosulfamide correspondant par traitement avec un chlorure d'acide en présence de triéthylamine et une quantité catalytique de 4-(N,N-dimethylamino)pyridine.     

Two versatile routes towards Cerpegin and analogues: applications of a one pot reaction to new analogues of Cerpegin

Simple and efficient routes to the natural alkaloid Cerpegin and new analogues are described herein. In a first approach, we extend the scope of a one pot three steps reaction, which permits the synthesis of new analogues of Cerpegin, substituted in different ways. In a second line of approach, we present an unprecedented synthesis of Cerpegin and analogues where methylfuranones are condensed with dimethylformamide diethylacetal (DMFDEA) to yield enaminolactone esters, which react easily with various primary amines affording Cerpegin and new analogues. We applied this second approach to the synthesis of new bis-Cerpegins and N-amino-Cerpegins. Most of the syntheses are performed under environmental friendly conditions.     

Heterogeneous bimetallic Au–Co nanoparticles as new efficient catalysts for the three-component coupling reactions of amines,alkynes and CH2Cl2

Research on Chemical Intermediates - Propargylamines are key intermediates for the synthesis of many biologically active molecules. A new synthesis of propargylamines via a three component-coupling...     

Electronic structure and UV–Vis spectra simulation of square planar Bis(1-(4-methylphenylazo)-2-naphtol)-Transition metal complexes [M(L)2]x (M = Ni,Pd, Pt,Cu, Ag,and x = − 1, 0, + 1): DFT and TD-DFT study

Structural Chemistry - DFT/B3LYP calculations with full geometry optimizations have been carried out on 1-phenylazo-2-naphthol and their metal complexes of formula M(MePhNap)2 (M?=?Ni,...     

Palladium-catalyzed direct arylation using free NH2 substituted thiophene derivatives with inhibition of amination type reaction

The palladium-catalyzed direct arylation at C2 or C5 of free NH₂ substituted thiophene derivatives was found to proceed in moderate to high yields using a variety of aryl halides. The choice of potassium acetate as the base was found to be crucial to inhibit the amination reaction and to promote the direct arylation.     

A new coordination complex based on a polynitrile ligand: bis(4‐amino‐3,5‐di‐2‐pyridyl‐4H‐1,2,4‐triazole)diaquairon(II) bis(1,1,3,3‐tetracyano‐2‐methylsulfanylpropenide)

The new high‐spin iron(II) complex, [Fe(C₁₂H₁₀N₆)₂(H₂O)₂](C₈H₃N₄S)₂ or [Fe(abpt)₂(H₂O)₂](tcnsme)₂ [where abpt is 4‐amino‐3,5‐di‐2‐pyridyl‐4H‐1,2,4‐triazole and tcnsme is the 1,1,3,3‐tetracyano‐2‐methylthiopropenide anion], consists of discrete [Fe(abpt)₂(H₂O)₂]²⁺ dications, where the Fe^II ion is coordinated by two N,N′‐bidentate chelating abpt ligands in the equatorial plane and two water molecules in trans positions, generating a distorted octahedral [FeN₄O₂] environment. The cationic unit is neutralized by two polynitrile tcnsme anions, in which the C—N, C—C and C—S bond lengths indicate extensive electronic delocalization. In the crystal structure, the dications and anions are linked through O—H...N and N—H...N hydrogen bonds involving the water H atoms and those of the NH₂ groups and the N atoms of the CN groups, leading to the formation of a three‐dimensional network.     

Nanoscale heterogeneity in alkyl-methylimidazolium bromide ionic liquids

High-energy x-ray diffraction measurements and atomistic molecular dynamics (AMD) numerical simulations have been carried out on 1-alkyl-3-methylimidazolium bromide ionic liquids, C(n)mimBr, with n = 2, 4, and 6. Excellent agreement between experiment and simulation is obtained, including the region of the low-Q peak that has proved problematic in previous work in the literature. In the partial structure analysis of the AMD results, a distinct peak develops at the leading edge of the ring-ring pair distribution function and shifts to lower r with increasing alkyl chain length, indicating that the preferential parallel and antiparallel alignment of neighboring cation rings plays a larger role with increasing chain length. The ring-ring, anion-anion, and ring-anion partial structure factors are dominated by strong charge-ordering peaks around 1.1 A?(-1), corresponding to a distance between neighboring polar entities of D(2) = 5.7 A?. In contrast, the tail-tail S(Q) is dominated by the low-Q peak that rises and moves to lower Q with increasing chain length; the length scale of this structural heterogeneity D(1) increases from about 10 A? in C(2)mimBr to 14.3 A? in C(4)mimBr and 18.8 A? in C(6)mimBr. Both the length scale of the structural heterogeneity and its anomalous temperature dependence in the C(n)mimBr liquids studied here show considerable similarity to results in the literature for C(n)mimPF(6) liquids, indicating a remarkable insensitivity to the form and size of the anion. Our results are consistent with the concept of nanoscale heterogeneity with small, crystal-like moieties.     

Electronic and magnetic properties of Fe<Subscript>2</Subscript>SiC

The electronic structure and magnetic properties of Fe₂SiC compound have been studiedusing the framework of an all-electron full-potential linearized augmented-plane wave(FP-LAPW) method within the local density (LSDA) and + U corrected(LSDA + U)approximations. An antiferromagnetic spin ordering of Fe atoms is shown to be the groundstate for this compound. From the electronic band structures and density of states (DOS),Fe₂SiC has ametallic character and from the analysis of the site and momentum projected densities, itis deduced that the bonding is achieved through hybridization of Fe-3d with C-2p states andFe-3d withSi-3pstates. It is also pointed out that the Fe-C bonding is more covalent than Fe-Si. In theFM phase, the spin polarized calculations indicate that the total magnetic moment ofFe₂SiC increasesfrom 0.41 to 4.33μ _B when the Hubbard U parameter for iron isconsidered.