Synthesis of functionalized 2-alkylidenetetrahydrofurans by cyclization of 1,3-bis(trimethylsilyloxy)-1,3-butadienes with epoxides

The Lewis acid mediated cyclization of epoxides with 1,3-bis(trimethylsilyloxy)-1,3-butadienes, electroneutral equivalents of 1,3-dicarbonyl dianions, results in the formation of 2-alkylidenetetrahydrofurans with a great variety of substitution patterns and functional groups. This includes the synthesis of 2,3'-bifuranylidenes and 7-oxabicyclo[4.3.0]nonanes. The cyclization of dienes with functionalized epoxides containing base-labile groups proceeds with good chemoselectivity. In all reactions, good regio- and E diastereoselectivities are observed. Based on the stereoselectivities observed for reactions of 1,2-disubstituted epoxides, a working hypothesis for the mechanism of the reaction is suggested.     

Untersuchungen an Alkylmetallalkoxiden der Elemente Aluminium,Gallium und Indium. III. Eigenschaften und Schwingungsspektren von Dialkylgallium- und Indiumalkoxiden

Studies on Alkyl Metal Alkoxides of Aluminium, Gallium, and Indium. III. Properties and Vibrational Spectra of Dialkylgallium- and Indium Alkoxides The preparation and the properties of dialkyl metal alkoxides R₂MOR′ (with R = CH₃, CD₃, C₂H₅; R′ = CH₃, CD₃ and M = Ga, In) are described. The vibrational data (IR and Raman) of the trimeric methyl derivatives point to puckered six-membered M₃O₃-ring systems.     

Phenazine, 3. Mitt.: N-(o-Aminophenyl)-benzo[a]phenazin-5-amin, das vermeintliche “Dihydronaphthodiphenazin”Kehrmanns, und seine Derivate

The dihydronaphthodiphenazine ofKehrmann, which is according toBadger andPettit reported to be 14-o-aminophenyl-13,14-dihydro-5,8,13,14-tetraaza-6,7-benzopentaphene, is N-(o-aminophenyl)-benzo[a]phenazin-5-amine. This was proved by chemical and spectroscopic investigations. The structures of the derivatives prepared byBadger andPettit are also corrected and the acetylation processes are cleared up.     

Enediynes in 11-membered rings. Synthesis, structure, and reactivity of highly strained but unusually stable macrocycles.

The synthesis of two new aromatic cyclic enediynes 1a and 1b using a double Wittig condensation, followed by bromination and di-dehydrobromination, is reported. The structures were determined using X-ray crystallography. The observed C(1)-C(6) distances of the enediyne moiety in the oxygen- and sulfur-containing eleven-membered rings are quite short with 3.44 and 3.50 A, respectively, indicating the highly strained nature of these compounds. Isodesmic calculations at the B3LYP/6-31G level of theory indicate a strain energy of 8.2 and 5.8 kcal/mol, respectively. Despite the highly strained ring system, the compounds were found to be stable under thermal, photochemical, and electron-transfer conditions. Using BLYP/6-311+G/BLYP/6-31G calculations, the origin of this unusual stability was traced to the high energy of the 1,4 benzyne diradicals formed via Bergman cyclization. For the radical cation, both the C(1)-C(6) and the C(1)-C(5) cyclization mode previously reported for acyclic analogues of 1 were found to be energetically prohibitive.     

Negatively charged hyperbranched polyether-based polyelectrolytes

The preparation of carboxylated hyperbranched polyglycerols of narrow polydispersity was achieved by modification (78–90%) of the hydroxyl end groups via Michael addition of acrylonitrile, followed by hydrolysis. High conversion could only be achieved for low molecular weight starting materials (520 and 1,030 g mol⁻¹). The solution properties of the resulting materials were investigated by dynamic light scattering (DLS), showing the formation of large aggregates with size depending on the pH value. After deposition on a negatively charged mica surface, the structures observed by atomic force microscope (AFM) show the coexistence of aggregates and single macromolecules. Most interesting, in the case of the lower molecular weight sample (PG 520 g mol⁻¹), extended and ordered terrace structures were formed, which are unprecedented for hyperbranched polymers and are of interest for surface modification in general.     

The effect of the ammonium paratungstate source on the tungsten crystallite size

In an investigation into the effects of CaCl₂ on the sulfation of limestones in a laboratory furnace simulating fluidized-bed coal combustion conditions, small additions of CaCl₂ (<1 mole%) to the limestone prior to calcination were found to increase the extent of sulfation by changing the limestone pore structure. These changes were effected by trace amounts of liquid in the system in a synthetic SO₂/O₂ flue gas at 850°C. At much higher concentrations of CaCl₂, large amounts of a liquid phase are produced, containing a substantial quantity of dissolved CaO and leading to greatly enhanced sulfation when exposed to SO₂/O₂. The use of CaCl₂ additive in fluidized-bed combustion would reduce the quantity of limestones required to meet air pollution standards for SO₂ and also reduce the quantity of solid waste generated.     

Vesicle adsorption and lipid bilayer formation on glass studied by atomic force microscopy

The adsorption of phosphatidylcholine (PC) vesicles (30, 50, and 100 nm nominal diameters) and of dye-labeled PC vesicles (labeled with 6% Texas Red fluorophore (TR) and encapsulated carboxy fluorescein (CF)) to glass surfaces was studied by contact mode atomic force microscopy in aqueous buffer. These studies were performed in part to unravel details of the previously observed isolated rupture of dye-labeled PC vesicles on glass (Johnson, J. M.; Ha, T.; Chu, S.; Boxer, S. G. Biophys. J. 2002, 83, 3371-3379), specifically to differentiate partial rupture, that is, pore formation and leakage of entrapped dye, from full rupture to form bilayer disks. In addition, the adhesion potential of PC vesicles on glass was calculated based upon the adhesion-driven flattening of adsorbed vesicles and a newly developed theoretical model. The vesicles were found to flatten considerably upon adsorption to glass (width-to-height ratio of approximately 5), which leads to an estimate for the adhesion potential and for the critical rupture radius of 1.5 x 10(-4) J/m2 and 250 nm, respectively. Independent of vesicle size and loading with dye molecules, the adsorption of intact vesicles was observed at all concentrations below a threshold concentration, above which the formation of smooth lipid bilayers occurred. In conjunction with previous work (Johnson, J. M.; Ha, T.; Chu, S.; Boxer, S. G. Biophys. J. 2002, 83, 3371-3379), these data show that 6% TR 20 mM CF vesicles adsorb to the surface intact but undergo partial rupture in which they exchange content with the external buffer.     

Coligand role in the NHC nickel catalyzed C–F bond activation: investigations on the insertion of bis(NHC) nickel into the C–F bond of hexafluorobenzene

The reaction of [Ni(Mes₂Im)₂] (1) (Mes₂Im = 1,3-dimesityl-imidazolin-2-ylidene) with polyfluorinated arenes as well as mechanistic investigations concerning the insertion of 1 and [Ni(ⁱPr₂Im)₂] (1ipr) (ⁱPr₂Im = 1,3-diisopropyl-imidazolin-2-ylidene) into the C–F bond of C₆F₆ is reported. The reaction of 1 with different fluoroaromatics leads to formation of the nickel fluoroaryl fluoride complexes trans-[Ni(Mes₂Im)₂(F)(Ar^F)] (Ar^F = 4-CF₃-C₆F₄2, C₆F₅3, 2,3,5,6-C₆F₄N 4, 2,3,5,6-C₆F₄H 5, 2,3,5-C₆F₃H₂6, 3,5-C₆F₂H₃7) in fair to good yields with the exception of the formation of the pentafluorophenyl complex 3 (less than 20%). Radical species and other diamagnetic side products were detected for the reaction of 1 with C₆F₆, in line with a radical pathway for the C–F bond activation step using 1. The difluoride complex trans-[Ni(Mes₂Im)₂(F)₂] (9), the bis(aryl) complex trans-[Ni(Mes₂Im)₂(C₆F₅)₂] (15), the structurally characterized nickel(i) complex trans-[Ni^I(Mes₂Im)₂(C₆F₅)] (11) and the metal radical trans-[Ni^I(Mes₂Im)₂(F)] (12) were identified. Complex 11, and related [Ni^I(Mes₂Im)₂(2,3,5,6-C₆F₄H)] (13) and [Ni^I(Mes₂Im)₂(2,3,5-C₆F₃H₂)] (14), were synthesized independently by reaction of trans-[Ni(Mes₂Im)₂(F)(Ar^F)] with PhSiH₃. Simple electron transfer from 1 to C₆F₆ was excluded, as the redox potentials of the reaction partners do not match and [Ni(Mes₂Im)₂]⁺, which was prepared independently, was not detected. DFT calculations were performed on the insertion of [Ni(ⁱPr₂Im)₂] (1ipr) and [Ni(Mes₂Im)₂] (1) into the C–F bond of C₆F₆. For 1ipr, concerted and NHC-assisted pathways were identified as having the lowest kinetic barriers, whereas for 1, a radical mechanism with fluoride abstraction and an NHC-assisted pathway are both associated with almost the same kinetic barrier.

A combined experimental and theoretical study on the mechanism of the C–F bond activation of C₆F₆ with [Ni(NHC)₂] is provided.     

Quecksilber(II)‐chlorid‐ und ‐iodid‐Komplexe von Dithia‐ und Tetrathiakronenethern

Mercury(II) Chloride and Iodide Complexes of Dithia‐ and Tetrathiacrown Ethers The complexes [(HgCl₂)₂((ch)₂30S₄O₆)] ( 1 ), [HgCl₂(mn21S₂O₅)] ( 2 ), [HgCl₂(ch18S₂O₄)] ( 3 ) and [HgI(meb12S₂O₂)]₂[Hg₂I₆] ( 4 ) have been synthesized, characterized and their crystal structures were determined. In [(HgCl₂)₂((ch)₂30S₄O₆)] two HgCl₂ units are discretely bonded within the ligand cavity of the 30‐membered dichinoxaline‐tetrathia‐30‐crown‐10 ((ch)₂30S₄O₆) forming a binuclear complex. HgCl₂ forms 1 : 1 “in‐cavity” complexes with the 21‐membered maleonitrile‐dithia‐21‐crown‐7 (mn21S₂O₅) ligand and the 18‐membered chinoxaline‐dithia‐18‐crown‐6 (ch18S₂O₄) ligand, respectively. The 12‐membered 4‐methyl‐benzo‐dithia‐12‐crown‐4 (meb12S₂O₂) ligand gave with two equivalents HgI₂ the compound [HgI(meb12S₂O₂)]₂[Hg₂I₆]. In the cation [HgI(meb12S₂O₂)]⁺ meb12S₂O₂ forms with the cation HgI⁺ a half‐sandwich complex.     

Electron-transfer reduction of selected alcohols with alkalide K, K(15-crown-5)2 via organometallic intermediates

The course of the reaction of alkalide K⁻, K⁺(15-crown-5)₂1 with selected alcohols depends on the kind of alcohol and the mode of substrate delivery. In the case of methanol, potassium methoxide formed initially undergoes destruction at the excess of 1. It results in potassium oxide and methylpotassium. The latter opens the crown ether ring giving potassium tetraethylene glycoxide vinyl ether and methane. A similar course of the process is observed for propanol. Potassium glycidoxide is the main product formed in the reaction of 1 with glycidol. Its oxirane ring is opened at the excess of 1. Organopotassium alkoxides, i.e., potassium potassiomethoxide and dipotassium potassiopropane-1,2-dioxide are intermediate products of this reaction. They react then with the crown ether. Potassium methoxide, potassium enolate of acetaldehyde, dipotassium propane-1,2-dioxide and potassium tetraethylene glycoxide vinyl ether are the final products of this process.