Preparative isolation of (+)-beta-eudesmol fromAmyris balsamifera

Summary Optically pure (+)-beta-eudesmol is a possible starting material for the synthesis of several termite defense compounds. A two step procedure for the isolation of gram quantities of (+)-beta-eudesmol from commercially availableAmyris balsamifera oil (syn. West Indian sandalwood oil), containing 8% beta-eudesmol, was developed. Step one consisted of an efficient vacuum distillation of the total oil. Step two was a medium pressure LC separation with an AgNO₃ impregnated silica gel stationary phase. Several other separation procedures failed due to the presence of many closely related sesquiterpene alcohols (75% of the oil).     

Friedel-Craft acylation of ar-himachalene: synthesis of acyl-ar-himachalene and a new acyl-hydroperoxide

Friedel-Craft acylation at 100 °C of 2,5,9,9-tetramethyl-6,7,8,9-tetrahydro-5H-benzocycloheptene [ar-himachalene], a sesquiterpenic hydrocarbon obtained by catalytic dehydrogenation of α-, β- and γ-himachalenes, produces a mixture of two compounds: (3,5,5,9-tetramethyl-6,7,8,9-tetrahydro-5H-benzocyclohepten-2-yl)-ethanone (2, in 69% yield), with a conserved reactant backbone, and 3, with a different skeleton, in 21% yield. The crystal structure of 3 reveals it to be 1-(8-ethyl-8-hydroperoxy-3,5,5-trimethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-ethanone. In this compound O-H…O bonds form dimers. These hydrogen-bonds, in conjunction with weaker C-H…O interactions, form a more extended supramolecular arrangement in the crystal.     

Ni(0)-CMC-Na - nickel colloids in sodium carboxymethyl-cellulose: catalytic evaluation in hydrogenation reactions

A recyclable catalyst, Ni(0)-CMC-Na, composed of nickel colloids dispersed in a water soluble bioorganic polymer, sodium carboxymethylcellulose (CMC-Na), was synthesized by a simple procedure from readily available reagents. The catalyst thus obtained is stable and highly active in alkene hydrogenations.     

Novel palladium nanoparticles supported on mesoporous natural phosphate: Catalytic ability for the preparation of aromatic hydrocarbons from natural terpenes

Various ratios of palladium nanoparticles supported on mesoporous natural phosphate (Pd@NP) were prepared using the wetness impregnation method. The prepared catalysts were characterized by IR, XRD, CV, SEM, EDX, XRF, TEM and BET analysis. The reduction and preparation of the palladium nanoparticles afford a crystallite size of 10.88 nm. The performance of the synthesized catalyst was investigated in the solvent-free dehydroaromatization of α-, β- and γ-himachalene mixture from Cedrus atlantica oil as a model substrate. In order to achieve an efficient and selective catalysis, the catalytic dehydroaromatization of various terpenes such as limonene, limonaketone, carvone, carveol and perillyl alcohol was studied. The Pd@NP catalyst performed a high catalytic activity, selectivity and recyclability in the terpenes dehydroaromatization reaction.     

A ruthenium(II) complex with p‐cymene and (S)‐2‐(anilinomethyl)pyrrolidine

The title compound, [(S)‐2‐(anilino­methyl)­pyrrolidine‐N,N′]‐chloro(η⁶‐para‐cymene)­ruthenium(II) chloride, [RuCl‐(C₁₀H₁₄)(C₁₁H₁₆N₂)]Cl, has been synthesized by the reaction of [RuCl₂(p‐cymene)]₂ (p‐cymene is para‐iso­propyl­toluene) with (S)‐2‐(anilinomethyl)­pyrrolidine in triethyl­amine/2‐propanol. The Ru atom is in a pseudo‐tetrahedral environment coordinated by a chloride ligand, the aromatic hydro­carbon is linked in a η⁶ manner and the amine is linked via its two N atoms. The chloride anion is involved in hydrogen bonding with the di­amine moieties through N—H?Cl interactions, with N?Cl distances of 3.273 (4) and 3.352 (4) Å.     

Molecular orbital investigation of the protonated H2X2AlNHn(CH3)3-n+ (X = F, Cl, and Br; n = 0-3) complexes

Structures of protonated alane-Lewis base donor-acceptor complexes H2X2AlNHn(CH3)(3-n)+ (X = F, Cl, and Br; n = 0-3) as well as their neutral parents were investigated. All the monocations H2X2AlNHn(CH3)(3-n)+ are Al-H protonated involving hypercoordinated alane with a three-center two-electron bond and adopt the C(s) symmetry arrangement. The energetic results show that the protonated alane-Lewis complexes are more stable than the neutral ones. They also show that this stability decreases on descending in the corresponding periodic table column from fluorine to bromine atoms. The calculated protonation energies of HX2AlNHn(CH3)(3-n) to form H2X2AlNHn(CH3)(3-n)+ were found to be highly exothermic. The possible dissociation of the cations H2X2AlNHn(CH3)(3-n)+ into X2AlNHn(CH3)(3-n)+ and molecular H2 is calculated to be endothermic.     

Characterization of the glycosidic linkage of underivatized disaccharides by interaction with Pb(2+) ions

Electrospray ionization in combination with tandem mass spectrometry and lead cationization is used to characterize the linkage position of underivatized disaccharides. Lead(II) ions react mainly with disaccharides by proton abstraction to generate [Pb(disaccharide)(m)-H](+) ions (m = 1-2). At low cone voltages, an intense series of doubly charged ions of general formula [Pb(disaccharide)(n)](2+) are also observed. Our study shows that MS/MS experiments have to be performed to differentiate Pb(2+)-coordinated disaccharides. Upon collision, [Pb(disaccharide)-H](+) species mainly dissociate according to glycosidic bond cleavage and cross-ring cleavages, leading to the elimination of C(n)H(2n)O(n) neutrals (n = 2-4). The various fragmentation processes allow the position of the glycosidic bond to be unambiguously located. Distinction between glc-glc and glc-fru disaccharides also appears straightforward. Furthermore, for homodimers of D-glucose our data demonstrate that the anomericity of the glycosidic bond can be characterized for the 1 --> n linkages (n = 2, 4, 6). Consequently, Pb(2+) cationization combined with tandem mass spectrometry appears particularly useful to identify underivatized disaccharides.     

Density functional theory study of the hydrogen bond interaction between lactones, lactams, and methanol

The structure and relative stability of methanol complexes with various cyclic ketones, lactones, lactams, and N-methyl lactams from three- to seven-membered rings have been investigated using the density functional theory method. The geometries, harmonic frequencies, and energies were calculated at the B3LYP/6-311+G(d,p) level. Three stable structures, cis-a, cis-b, and trans, with respect to the ring oxygen (nitrogen) atom, were found to be local minima of the potential energy surface. For lactones and N-methyl lactams, the most stable structure is trans; it is stabilized, as in cyclic ketones, through the conventional hydrogen bond (HB) interaction between the basic carbonyl oxygen and the acidic methanolic hydrogen and an unconventional HB interaction between the methanolic oxygen and the CH hydrogen, in the alpha position of the carbonyl group. For unsubstituted lactams, the cis-a structure, stabilized through a HB interaction between the NH group and the methanol oxygen in addition to the conventional HB interaction, is the most stable. The topological properties of the electron density ratify the existence of conventional (N,O-H. . .O) and unconventional (C-H. . .O) hydrogen bonding. A good correlation was found between the HB distances and the electron density at the HB critical point. The unsubstituted lactams yield more stable complexes with methanol than N-methyl lactams, lactones, and cyclic ketones. In the most stable complexes, both components behave simultaneously as a HB donor and as a HB acceptor.     

Catalytic oxidation of α-pinene by transition metal using t-butyl hydroperoxide and hydrogen peroxide

The allylic oxidation of α-pinene 1 was investigated using various catalytic systems. By a proper choice of the latter, the reaction can be directed toward the selective synthesis of verbenol 2 or verbenone 3. High yield into verbenone was achieved under mild conditions with copper salts as catalysts and t-butyl hydroperoxide (TBHP) as oxidant. On the other hand, when Pd(acac)₂ was used with hydrogen peroxide, verbenol was obtained as the main product.