Uma nova síntese de alfa-bromo-acetofenonas e sua aplicação na obtenção de 2-benzoil-benzofuranas

alpha-Bromoacetophenones are important in organic synthesis. They have been widely used as precursors of several natural products. Several methods of bromination aiming at their synthesis have been described, however they furnish a mixture of starting material 10, mono 8 and dibromide 11 products. We developed a novel, simple and efficient synthesis of these compounds with applications in the synthesis of benzoylbenzofurans 9, compounds with important pharmacological properties, such as the ability of dilating the coronary artery and analgesic action. Such compounds have also been used as key intermediates to obtain quinone systems.

Exchange reactions of organic halides and organo-silicon compounds with boron tribromide and boron triiodide

Reactions of the boron halides with organic halides and organo-silicon compounds have been investigated. The results show exchange of halogens between the BX3 (X = Br# 1) and the organic halidef exchange of the halogen of the C-X bond being proved. The rates of halogen exchange vary. Reaction of the heavier halides with organo-silicon compounds indicated that the silicon-carbon bonds ruptured in the absence of electronegative atom attached to the silicon. The presence of an electronegative atom (halogen or oxygen) attached to the silicon causes the bond between the silicon and the electronegative atom to be preferentially broken. Products of exchange reactions of the boron halides and the organic halides or the organo-silicon compounds were studied by use of 1H NMR and GC/MS. From these results some possible mechanisms for the exchange reactions are postulated, but further work is indicated to prove the real courses of the reactions

Molecular and ionic sublimation of erbium tribromide

The molecular and ionic composition of vapor over erbium tribromide sublimed from the Knudsen effusion cell and the open surface of a single crystal was studied by high-temperature mass spectrometry. The partial pressures of ErBr3 and Er2Br6 molecules in saturated vapor and the ratio between their sublimation coefficients under free vaporization conditions were determined. The enthalpies and activation energies of sublimation of ErBr3 crystals in the form of monomers and dimers were calculated. The emission of and Er2 was recorded in studies of ionic sublimation in both modes. The enthalpies of formation of gas molecules and ions were determined.

X-Ray Diffraction Study of Boron Produced by Pyrolysis of Boron Tribromide

The goal of this research was to determine the composition of boron deposits produced by pyrolysis of boron tribromide, and to use the results to (a) determine the experimental conditions (reaction temperature, etc.) necessary to produce alpha-rhombohedral boron and (b) guide the development/refinement of the pyrolysis experiments such that large, high purity crystals of alpha-rhombohedral boron can be produced with consistency. Developing a method for producing large, high purity alpha-rhombohedral boron crystals is of interest because such crystals could potentially be used to achieve an alpha-rhombohedral boron based neutron detector design (a solid-state detector) that could serve as an alternative to existing neutron detector technologies. The supply of neutron detectors in the United States has been hampered for a number of years due to the current shortage of helium-3 (a gas used in many existing neutron detector technologies); the development of alternative neutron detector technology such as an alpha-rhombohedral boron based detector would help provide a more sustainable supply of neutron detectors in this country. In addition, the prospect/concept of an alpha-rhombohedral boron based neutron detector is attractive because it offers the possibility of achieving a design that is smaller, longer life, less power consuming, and potentially more sensitive than existing neutron detectors. The main difficulty associated with creating an alpha-rhombohedral boron based neutron detector is that producing large, high purity crystals of alpha-rhombohedral boron is extremely challenging. Past researchers have successfully made alpha-rhombohedral boron via a number of methods, but no one has developed a method for consistently producing large, high purity crystals. Alpha-rhombohedral boron is difficult to make because it is only stable at temperatures below around 1100-1200 °C, its formation is very sensitive to impurities, and the conditions necessary for its formation are not fully understood or agreed upon in the literature. In this research, the method of pyrolysis of boron tribromide (hydrogen reduction of boron tribromide) was used to deposit boron on a tantalum filament. The goal was to refine this method, or potentially use it in combination with a second method (amorphous boron crystallization), to the point where it is possible to grow large, high purity alpha-rhombohedral boron crystals with consistency. A pyrolysis apparatus was designed and built, and a number of trials were run to determine the conditions (reaction temperature, etc.) necessary for alpha-rhombohedral boron production. This work was focused on the x-ray diffraction analysis of the boron deposits; x-ray diffraction was performed on a number of samples to determine the types of boron (and other compounds) formed in each trial and to guide the choices of test conditions for subsequent trials. It was found that at low reaction temperatures (in the range of around 830-950 °C), amorphous boron was the primary form of boron produced. Reaction temperatures in the range of around 950-1000 °C yielded various combinations of crystalline boron and amorphous boron. In the first trial performed at a temperature of 950 °C, a mix of amorphous boron and alpha-rhombohedral boron was formed. Using a scanning electron microscope, it was possible to see small alpha-rhombohedral boron crystals (on the order of ~1 micron in size) embedded in the surface of the deposit. In subsequent trials carried out at reaction temperatures in the range of 950 °C – 1000 °C, it was found that various combinations of alpha-rhombohedral boron, beta-rhombohedral boron, and amorphous boron were produced; the results tended to be unpredictable (alpha-rhombohedral boron was not produced in every trial), and the factors leading to success/failure were difficult to pinpoint. These results illustrate how sensitive of a process producing alpha-rhombohedral boron can be, and indicate that further improvements to the test apparatus and test conditions (for example, higher purity/cleanliness) may be necessary to optimize the boron deposition. Although alpha-rhombohedral boron crystals of large size were not achieved, this research was successful in (a) developing a pyrolysis apparatus and test procedure that can serve as a platform for future testing, (b) determining reaction temperatures at which alpha-rhombohedral boron can form, and (c) developing a consistent process for analyzing the boron deposits and determining their composition. Further experimentation is necessary to achieve a pyrolysis apparatus and test procedure that can yield large alpha-rhombohedral boron crystals with consistency.

Preparation of Boron by Pyrolytic Decomposition of Boron Tribromide

The national shortage of helium-3 has made it critical to develop an alternative to helium-3 neutron detectors. Boron-10, if it could be produced in macroscopic alpha-rhombohedral crystalline form, would be a viable alternative to helium-3. This work has determined the critical parameters needed for the preparation of alpha-rhombohedral boron by the pyrolytic decomposition of boron tribromide on tantalum wire. The primary parameters that must be met are wire temperature and feedstock purity. The minimum purity level for boron tribromide was determined to be 99.999% and it has been found that alpha-rhombohedral boron cannot be produced using 99.99% boron tribromide. The decomposition temperature was experimentally tested between 830°C and 1000°C. Alpha-rhombohedral boron was found at temperatures between 950°C and 1000°C using 99.999% pure boron tribromide.

A Novel Short-Step Synthesis of New Xanthenedione Derivatives from the Cyclization of 3-Cinnamoyl-2-styrylchromones

Novel (E)-3-aryl-4-benzylidene-8-hydroxy-3,4-dihydro-1 H-xanthene-1,9(2H)-diones are prepared by the cyclization of (E,E)-3-cinnamoyl-5-hydroxy-2-styrylchromones efficiently catalyzed with boron tribromide. The (E,E)-3-cinnamoyl-5-hydroxy-2-styrylchromones are obtained from the Baker–Venkataraman rearrangement of (E,E)-2-acetyl-1,3-phenylene bis(3-phenylacrylate), which is greatly improved under microwave irradiation.

Chemical synthesis of glycosylated oligoribonucleotides for siRNA development

In this study, an efficient methodology for the preparation of carbohydrate-RNA conjugates was established, which involved the use of 3,4~diethoxy-3-cyclobutene-l,2- dione (diethyl squarate) as the linking reagent. First, a glycan moiety containing an amino group reacted with diethyl squarate to form an activated glycan, which further reacted with an amino modified oligoribonucleotide to form a glycoconjugate under slightly basic conditions. The effect of glycosylation on the stability of RNA molecules was evaluated on two glycoconjugates, monomannosyl UlO-mer and dimannosyl UlO-mer. In the synthesis of aromatic fluorescent ribosides, perbenzylated ribofuranosyl pyrene and phenanthrene were synthesized from perbenzylated ribolactone. Deprotection of benzyl-protected ribofuranosyl phenanthrene and pyrene by boron tribromide gave ribofuranosyl phenanthrene and ribopyranosyl pyrene, respectively. UV/vis and fluorescent properties of the ribosides were characterized.

[Bmim]Br-3 as a new reagent for regioselective mono-bromination of activated aromatics under solvent-free conditions

Reaction of activated aromatics containing phenols, naphthol, methoxynaphthalenes, anisole etc. with 1-butyl-3-methylimidazolium tribromide ([Bmim]Br-3) under solvent-free conditions, selectively gave the corresponding monobromination products with excellent yields.

[bmim]Br3 as a new reagent for regioselective monobromination of arylamines under solvent-free conditions

Reaction of arylamines with 1-butyl-3-methylimidazolium tribromide ([bmim]Br3) under solvent-free conditions, gave selectively the corresponding monobromination products with excellent, yields.

Structural studies in tellurium chemistry

The primary theme of this research was the characterisation of new and novel organo-tellurium complexes, using the technique of single crystal X-ray analysis to establish more firmly the various coordination modes of tellurium. In each study the unit cell dimensions and intensity data were collected using an Enraf-Nonius CAD-4, four circle diffractometer. The raw data collected in turn was transferred to the Birmingham University Honeywell Multics System and processed using the appropriate computer packages for the determination of crystal structures. The molecular and crystal structures of: bis[2-(2-pyridyl)phenyl]tritelluride, bis[2-(N-hydroxy)iminophenyl] ditelluride, 2-(2-pyridyl)phenyltellurium(IV) tribromide, (2-N,N-dimethylbenzylamine-C,N')tellurium(IV)tribromide, 2-dichloro(butyl)tellurobenzaldehyde, 2-dichlorobutotelluro-N-dimethylbenzyl ammonium chloride, dimethyldithiocarbamato[2-(2-pyridyl)phenyl]tellurium(II), dimethyldithiocarbamato[2-(2-quinolinyl)phenyl]tellurium(II) and para-ethoxypheny[2-(2-pyridyl)phenyl]telluride are described. In each structure, the Lewis acidity of tellurium appears to be satisfied by autocomplex formation, through short-range intramolecular secondary bonds between tellurium and an electron denoting species, (generally nitrogen in these structures) with long range weak inter molecular contacts forming in the majority of the tellurium(IV) structures. The order of Lewis acidity in each structure can be considered to be reflected by the length of the short range intramolecular secondary bond, identified, that is, when tellurium has a low Lewis acidity this interaction is long. Interestingly, no primary bonds are found trans to a Te-C covalent bond in any of the above structures, highlighting the strong trans effect of aromatic and aryl groups in tellurium complexes.

Mechanistic studies of organotellurium chemistry

The oxidation of bis(p-ethoxyphenyl) ditelluride by hydrogen peroxide has been studied kinetically. The reaction monitored was an oxidation from tellurium(I) to tellurium(II). The reaction stoichiometry ratio was found to depend upon the initial reagent concentrations. The presence of dioxygen was found to retard the rate and attributed to a dioxygen-ditelluride adduct. The rate varies in the following order of different atmospheres N2> Air> > O2. The final product obtained from the oxidation has been characterised by IR, NMR and ESR spectroscopy. A mechanism for the oxidation has been suggested. The reduction of p-EtOPhTeCl3 by the hydrazinium ion has been studied kinetically. The stoichiometric measurements show that four moles p-EtOPhTeCl3 are equivalent to three moles hydrazinium ion. The kinetics were studied under pseudo first order conditions. No ammonia was detected as a nitrogen containing product. The reduction proceeds via a two-electron process which indicates that it is inner-sphere in nature. A mechanism for the reduction is suggested. The solvolysis of p-EtOPhTeCl3 by methanol in benzene/methanol media has been studied. The study shows that the solvolysis is a reversible, acid catalysed reaction. Replacement of the chlorides on tellurium by methanol is agreed to be associative and replacement of the first chloride is rate determining. The rate of solvolysis varies in the order trichloride > tribromide > triiodide. A mechanism for the solvolysis is suggested. The synthesis of some tellurium heterocyclics is reported. The synthesis and characterisation of telluranthrene is reported. The attempted synthesis of telluraxanthene was unsuccessful.