Catalytic carbonylation for the synthesis of chemical intermediates

Chemistry related to three catalytic carbonylation reactions is discussed. Synthesis of diphenylurea from nitrobenzene, aniline, and CO gives isolated yields above 98% at 100–120 °C and 15–60 bar of CO in the presence of a palladium (II) complex, PPh₃ and NEt₄Cl. Experimental evidence was provided to prove a new reaction stoichiometry and involvement of a carbamoyl intermediate. In carbonylation of HCHO over ion exchange resin catalysts, reaction temperature, time, pressure, and solvent were important variables to obtain high yields of methyl glycolate. Carbonylation of isobutylphenylethanol at 120°C and 40 bar of CO in the presence of PdCl₂−PPh₃−HCl gives 98% yield of α-(4-isobutylphenyl) propionic acid (ibuprofen). Each catalyst component had a definite role that is indispensable for an efficient overall reaction.     

Kinetics of thermal depolymerization of trimethylsiloxy end-blocked polydimethylsiloxane and polydimethylsiloxane-N-phenylsilazane copolymer

The thermal degradation of Me₃SiO end-blocked polydimethylsiloxane (eb-PDMS) and polydimethylsiloxane-N-phenylsilazane (eb-PDMS–NPhSz) copolymer was studied. For both polymers relative degree of polymerization (DP /DP ₀) as a function of conversion (1 – W/W₀) data were obtained. For eb-PDMS the results were consistent with a mechanism involving a rate determining random siloxane bond cleavage initiation step followed by a rapid and complete depropagation of the active fragments evolving volatile cyclic oligomers. Rate constants (k) for initiation were obtained at four temperatures from plots of DP ^?1 vs. time. An Arrhenius activation energy of approximately 80 kcal/mol was determined and is consistent with a SiOSi scission transition state. The degradation of eb-PDMS–NPhSz appears to follow the same depolymerization process evolving cyclic oligomers. Although DP /DP ₀ vs. C data suggest a random cleavage–complete depolymerization mechanism, an Arrhenius plot suggests a more complex degradation mechanism. The role of impurities as degradation catalysts is discussed.     

Asymmetric cationic coordination environments in new oxide materials: synthesis and characterization of Pb(4)Te(6)M(10)O(41) (M = Nb(5+) or Ta(5+))

Two new isostructural tellurites, Pb(4)Te(6)M(10)O(41) (M = Nb(5+) or Ta(5+)), have been synthesized by standard solid-state techniques using PbO, Nb(2)O(5) (or Ta(2)O(5)), and TeO(2) as reagents. The structures of Pb(4)Te(6)Nb(10)O(41) and Pb(4)Te(6)Ta(10)O(41) were determined by single-crystal and powder X-ray diffraction. The materials exhibit a three-dimensional framework consisting of layers of corner-shared NbO(6) octahedra connected by TeO(3) and PbO(6) polyhedra. The Nb(5+), Te(4+), and Pb(2+) cations are in asymmetric coordination environments attributable to second-order Jahn-Teller effects. The Nb(5+) cations undergo an intraoctahedral distortion either toward a face or a corner, whereas the Te(4+) and Pb(2+) cations are in distorted environments attributable to their lone pair. In addition, the TeO(3) polyhedra strongly influence the direction of the Nb(5+) intraoctahedral distortion. Infrared and Raman spectroscopy, thermogravimetric analysis, and dielectric measurements are also presented. Crystal data: Pb(4)Te(6)Nb(10)O(41), monoclinic, space group C2/m (No. 12), with a = 23.412(3) A, b = 20.114(3) A, c = 7.5008(10) A, beta = 99.630(4) degrees, V = 3482.4(8) A(3), and Z = 4; Pb(4)Te(6)Ta(10)O(41), monoclinic, space group C2/m (No. 12), with a = 23.340(8) A, b = 20.068(5) A, c = 7.472(2) A, beta = 99.27(3) degrees, V = 3453.8(2) A(3), and Z = 4.     

Fluorescence-based nitric oxide detection by ruthenium porphyrin fluorophore complexes

The ruthenium(II) porphyrin fluorophore complexes [Ru(TPP)(CO)(Ds-R)] (TPP = tetraphenylporphinato dianion; Ds = dansyl; R = imidazole (im), 1, or thiomorpholine (tm), 2) were synthesized and investigated for their ability to detect nitric oxide (NO) based on fluorescence. The X-ray crystal structures of 1 and 2 were determined. The Ds-im or Ds-tm ligand coordinates to an axial site of the ruthenium(II) center through a nitrogen or sulfur atom, respectively. Both exhibit quenched fluorescence when excited at 368 or 345 nm. Displacement of the metal-coordinated fluorophore by NO restores fluorescence within minutes. These observations demonstrate fluorescence-based NO detection using ruthenium porphyrin fluorophore conjugates.     

Solid state synthesis of copper(I) thiotungstate cluster compounds at low heating temperatures. Crystal structures of [(n-Bu)4N]3-[WS4Cu3Cl3Br] and [Et4N]4[WS4Cu4I6]

Summary Reaction of [NH₄]₂[WS₄] with CuX (X = Cl or I) and R₄NX (R = Et or n-Bu) in the solid state gave two new bimetallic compounds with W:Cu compositions from 1:3 to 1:4. Compound (1), [(n-Bu)₄N]₃[WS₄Cu₃Cl₃Br], crystallizes in the hexagonal space group R3c with a = 17.051(5), c = 38.372(5) Å, V = 9661.8 ų, Z = 6. The cluster anion of (1) comprises a cubane-like cluster core [WS₃Cu₃Br] of C₃ symmetry with a Cl atom attached to each of the three Cu atoms and one terminal sulphido ligand attached to the W atom. Compound (2), [Et₄N]₄[WS₄Cu₄I₆], crystallizes in the monoclinic space group C2/m with a = 29.702(6), b = 12.7887(5), c = 15.327(3)Å, = 99.69(2), V = 5738.1 ų, Z = 4. In the cluster anion of (2), four edges of the WS₄ core are coordinated by four Cu atoms, giving a WS₄Cu₄ aggregate of approximate C_2V symmetry.     

Oligoindole-based foldamers with a helical conformation induced by chloride

As a new type of foldamers, oligoindoles containing 4, 6, and 8 indole rings were synthesized, and their folding properties were characterized by a combination of 1H NMR techniques and UV/visible titration experiments. When chloride was added, the NH signals of the oligoindoles were downfield shifted as a result of hydrogen-bond formation, and the aromatic signals were upfield shifted by stacking between two indoles. Moreover, the ROESY experiment provided definitive NOE evidence for the helical stacking in the presence of chloride. Finally, the UV/visible titration experiments demonstrated that the oligoindoles formed 1:1 complexes with chloride, and the association constants greatly increased with increasing the number of the indole NHs. These observations are all consistent with the fact that oligoindoles adopt a helical conformation when complexed with chloride by hydrogen-bonding interactions.     

Density functional study of lithium-aromatic sandwich compounds and their crystals

Using density functional theory, we have theoretically studied the formation of neutral lithium-aromatic complexes R-nLi and R-nLi-R, where R is benzene, naphthalene, or pyrene. We first find that the maximum number of lithium atoms n in the complexes increases with the size of R. In addition, pyrene favors the sandwich compound R-4Li-R over R-4Li more than three times that of the corresponding tendency for benzene, strongly suggesting the possible existence of oligomer (R-4Li)x. We have also investigated energetics and band structures of infinite one-dimensional crystals of R-nLi, finding them metallic. Detailed analysis of the electronic structure shows that all these observations are related to the strong electrostatic interaction among the species, which is originated from the charge transfer from Li atoms to the aromatic rings. In addition, it is shown that the pyrene crystal is mechanically stable with respect to deformation. This also suggests the possibility of its existence, which, in turn, holds potential application in lithium storage in respect to its large Li/C ratio.     

An efficient synthesis of novel carbocyclic nucleosides with use of ring-closing metathesis from D-lactose

This paper describes an efficient synthetic route for various types of novel carbocyclic nucleosides. The required stereochemistry of the targeted nucleosides was successfully obtained with use of Grubbs cyclization and Trost allylic alkylation from the carbohydrate chiral template "D-lactose".     

Photoreactions of benzosilacyclobutenes with carbonyl compounds. SH2 reaction on SiC bond by triplet carbonyl compounds

Photoreaction of 2,3-benzo-1,1-diphenyl(or dimethyl)-1-sila-2-cyclobutene with an aldehyde or ketone results in 1:1 cycloadduct of [4+2] type, the formation of which is accountd for in terms of S_H2 process, i.e., attack of a triplet carbonyl compound on the silicon of the benzosilacyclobutene.     

XPS analysis of the effect of Pt addition to Pd catalysts for complete benzene oxidation

Pt-Pd bimetallic catalysts were prepared in order to develop and investigate catalysts having excellent activity and stability for benzene destruction. The effect of Pt addition to Pd catalysts is studied by XPS analysis. This revised version was published online in August 2006 with corrections to the Cover Date.