Synthesis and Odor of Chiral Partial Structures of Khusimone. Part 1

Khusimone (1), one of the main odor-donating compounds of vetiver oil is subject of the following study on structure/odor relationship. The omittance of the ethano bridge of the tricyclic khusimone leads to a bicyclic system. The stereoselective approach to this degraded structure is described, and the olfactory properties are studied. The key step of the synthesis of the hydrindane nucleus is based on a highly diastereoselective conjugate addition to a chiral oxo-cyclopentene-2-carboxylate.     

Oligosaccharide analogues of polysaccharides. Part 14:. Carbocyclic cyclodextrin analogues. Synthesis of all trimeric and tetrameric isomers by homo- and heterocoupling of 1,4-cis-diethynylated 1,5-anhydroglucitols

Hetero- or homocoupling of protected 1,4-cis-diethynylated 1,5-anhydroglucitols leads to two isomeric cyclotrimers and to four isomeric cyclotetramers. The C₃-symmetric cyciotrimer 31 , the C₄-symmetric cyclotetramer 35 , and the D₂-symmetric cyclotetramer 6 have been prepared before. We have now synthesized the C₁-symmetric cyciotrimer 13 , and the C₁- and the C₂-symmetric cyclotetramers 22 and 27 , respectively. The cyclotrimer 13 was prepared by intramolecular, oxidative homocoupling and, alternatively, by a one-pot trimerization/cyclization of the monomer 36 (Schemes 1 and 5, resp.). Oxidative homocoupling was used for the cyclization of the tetramers 19 and 25 , leading to 22 and 27. The tetramer 19 was made by sequential Cadiot-Chod-kiewicz coupling (Scheme 2)and the tetramer 25 by a combination of a Cadiot-Chodkiewicz reaction and an intermolecular, oxidalive homocoupling (Scheme 3). The acetates 34 and 38 , corresponding to 35 and 27 , respectively, were also made by a one-pot dimerization/cyclization of the dimer 37 (Scheme 5). Intramolecular oxidative heterocoupling is also feasible and results in an alternative, more convenient synthesis of the acetylated cyclotrimer 30 and the acetylated cyclotetramer 34 (corresponding to 31 and 35 , resp.; Scheme 4). The solid-state conformation of the C₄-symmetric cyclotetramer 34 corresponds well to the one predicted by force-field calculations. We compared the water-solubilities of the cyclotrimers 13 and 31 and the tetramers 6, 22, 27 , and 35 , their calculated conformations (MM3*), and the D -adenosine binding properties of the cyclotetramers 6, 27 , and 35 .     

Synthesis of Spiropyrimidodiazepines and Spirodiazepinopurines by Tandem Nitroso‐ene/Diels–Alder Reactions

New spirocyclic heterocycles 8, 16, 19/20, 25, 27 , and 30 derived from pyrimido[4,5‐b][1,4]diazepin]‐8′(9′H)‐one were synthesised by a tandem nitroso‐ene/Diels–Alder reaction of 4‐(alkenoylamino)‐5‐nitrosopyrimides. The crystal structure of 16 was established by X‐ray analysis. It is characterised by four pairs of intermolecular H‐bonds linking every two molecules in the unit cell. Sequential imine reduction and intramolecular condensation of the C(4′)‐(acylamino)‐pyrimido[4,5‐b][1,4]diazepines 27 and 30 led to the [1,4]diazepino[1,2,3‐gh]purines 28 / 29 and 31 , respectively.     

DFT computational study of the mechanism of allyl halides carbonylation catalyzed by nickel tetracarbonyl

A theoretical investigation at the DFT(B3LYP) level on the carbonylation reaction of allyl bromide catalyzed by nickel tetra-carbonyl Ni(CO)(4) is discussed. The computational results show the following: (i) Three main steps characterize the catalytic cycle: (a) an oxidative addition step, (b) a carbonylation step, and (c) a reductive elimination step where the acyl product is obtained and the catalyst is regenerated. (ii) Both Ni(CO)(3) and Ni(CO)(4) complexes can behave as "active" catalytic species. (iii) The oxidative addition leads to the formation of either eta(3) or eta(1)-allyl nickel complexes, which are involved in a fast equilibrium. (iv) The carbonylation occurs much more easily on the eta(1) than on the eta(3) intermediates.     

Role of montmorillonite in flame retardancy of ethylene-vinyl acetate copolymer

The effects of non-treated (MMT), organophilic (OMM), and olefin/silicone polymer intercalated (IMM) montmorillonites on the thermal stability of ethylene-vinyl acetate copolymer (EVA) and on the flammability of magnesium hydroxide filled EVA were studied. The influence of various treatments on the delamination of montmorillonites in EVA was detected by rheological measurements and by Raman microscopy. The latter was a unique method for rapid detection of the dispersion also in highly filled EVA. Enhancement of thermo-oxidative stability of EVA and flame-retarded EVA could be observed by thermal analysis in the presence of variously treated montmorillonites. The flame-retardant efficiency of magnesium hydroxide was improved by simultaneous application of MMT and IMM. The increased performance of magnesium hydroxide was explained by the rheological effect of the IMM, catalytic effect of MMT and chemical interactions of montmorillonites with the metal hydroxide.     

Banana-shaped molecules peculiarly oriented in a magnetic field: (2)H NMR spectroscopy and quantum mechanical calculations.

The orientational properties of the banana-shaped liquid crystal 4-chloro-1,3-phenylenebis{4-[4'-(10-undecenyloxy)]benzoyloxy} benzoate (ClPbis11BB) are reported in the nematic phase under the effect of an external magnetic field. A new hypothesis, which states that the central ring of the aromatic core is oriented perpendicularly to the external magnetic field, is proposed. In support of this hypothesis, a series of studies based on (2)H NMR spectroscopy, both in the bulk and in solution, are discussed. (2)H NMR measurements on three selectively deuterium-labelled isotopomers are presented, together with DFT results from B3LYP/cc-pvDz calculations performed on the aromatic core. The rather flat shape of the investigated intramolecular energy surface allows for several different conformations to be populated, the computed magnetic susceptibilities of which are consistent with the proposed hypothesis of peculiar orientation of banana-shaped molecules. Moreover, the orientation of the magnetic susceptibility tensor is shown to be strongly dependent on the internal conformation of the banana-shaped molecules.     

On the power of the zeros of Bessel functions

For ν≥0 let c_νk be the k-th positive zero of the cylinder functionC _v(t)=J _v(t)cosα-Y _v(t)sinα, 0≤α>π whereJ _ν(t) andY _ν(t) denote the Bessel functions of the first and the second kind, respectively. We prove thatC _v,k ^1+H(x) is convex as a function of ν, ifc _νk≥x>0 and ν≥0, whereH(x) is specified in Theorem 1.1.     

Existence and uniqueness for nonlinear boundary value problems in kinetic theory

A boundary value problem for the stationary nonlinear Boltzmann equation in a slab has been examined in a weightedL space. It has been proved that the problem possesses a unique solution for boundary data small enough. The proof is based on the implicit function theorem. It has also been shown that for the linearized problem the Fredholm alternative applies.