Organic intermediates

Chemical Manufacturing. Chemical manufacturing accounts for over 50% of all U.S. caustic soda demand. It is used primarily for pH control, neutralization, off-gas scmbbing, and as a catalyst. About 50% of the total demand in this category, or approximately 25% of overall U.S. consumption, is used in the manufacture of organic intermediates, polymers, and end products. The majority of caustic soda required here is for the production of propylene oxide, polycarbonate resin, epoxies, synthetic fibers, and surface-active agents (6). 

Cycloaliphatic amines are comprised of a cyclic hydrocarbon stmctural component and an amine functional group external to that ring. Included in an extended cycloaUphatic amine definition ate aminomethyl cycloaUphatics. Although some cycloaUphatic amine and diamine products have direct end use apphcations, their major function is as low cost organic intermediates sold as moderate volume specification products. 

Cycloahphatic amine production economics are dominated by raw material charges and process equipment capital costs. Acetone (isophorone), adiponitnle, aniline, and MDA are all large-volume specification organic intermediates bordering on commodity chemicals. They are each cost-effective precursors. 

Monofunctional, cyclohexylamine is used as a polyamide polymerization chain terminator to control polymer molecular weight. 3,3,5-Trimethylcyclohexylamines ate usehil fuel additives, corrosion inhibitors, and biocides (50). Dicyclohexylamine has direct uses as a solvent for cephalosporin antibiotic production, as a corrosion inhibitor, and as a fuel oil additive, in addition to serving as an organic intermediate. Cycloahphatic tertiary amines are used as urethane catalysts (72). Dimethylcyclohexylarnine (DMCHA) is marketed by Air Products as POLYCAT 8 for pour-in-place rigid insulating foam. Methyldicyclohexylamine is POLYCAT 12 used for flexible slabstock and molded foam. DM CHA is also sold as a fuel oil additive, which acts as an antioxidant. StericaHy hindered secondary cycloahphatic amines, specifically dicyclohexylamine, effectively catalyze polycarbonate polymerization (73). 

Stabilization of Unstable Intermediates. Transition metals can stabilize normally unstable or transient organic intermediates. Cyclobutadiene has never been isolated as a free molecule, but it has been isolated and fully characterized as an iron tricarbonyl complex (138) ... 

Other Chlorobenzenes. The market for the higher chlorobenzenes (higher than di) is small in comparison to the combined mono- and dichlorobenzenes. Trichlorobenzenes are used in some pesticides, as a dye carrier, in dielectric fluids, as an organic intermediate and a chemical manufacturing solvent, in lubricants, and as a heat-transfer medium. These are small and decreasing markets. 

In spite of all these problems and difficulties, tubular reactors are the most important equipment for organic intermediate production in the petrochemicals industry. 

Other uses of HCI are legion and range from the purification of fine silica for the ceramics industry, and the refining of oils, fats and waxes, to the manufacture of chloroprene mbbers, PVC plastics, industrial solvents and organic intermediates, the production of viscose rayon yam and staple fibre, and the wet processing of textiles (where hydrochloric acid is used as a sour to neutralize residual alkali and remove metallic and other impurities). 

Fluid catalytic cracking rapidly overtook its competitors as both a source of fuel and of critical organic intermediates. Prior to 1942, the Houdry Process controlled 90 percent of the catalytic fuel market. But only three years later, in 1945, fluid cracking led all other catalytic cracking processes in market share (40 percent). At this time Thermofor technology stood at 31 percent, and Houdry at less chan 30 percent. 

The formation of isomeric aldehydes is caused by cobalt organic intermediates, which are formed by the reaction of the olefin with the cobalt carbonyl catalyst. These cobalt organic compounds isomerize rapidly into a mixture of isomer position cobalt organic compounds. The primary cobalt organic compound, carrying a terminal fixed metal atom, is thermodynamically more stable than the isomeric internal secondary cobalt organic compounds. Due to the less steric hindrance of the terminal isomers their further reaction in the catalytic cycle is favored. Therefore in the hydroformylation of an olefin the unbranched aldehyde is the main reaction product, independent of the position of the double bond in the olefinic educt ( contrathermodynamic olefin isomerization) [49]. 

The role of organic intermediates in electrode reactions was recently reviewed in some detail (Fleischmann and Fletcher, 1969 and 1971). 

Matrix Raman spectroscopy allows detection of some additional vibrations which are inactive in IR spectra (e.g. symmetrical vibrations vi in AB3 molecules having 3 symmetry) or which tie in the far infrared region. In practice, matrix-isolated organic intermediates have not been studied by Raman spectroscopy the main objects of these investigations are inorganic molecules (AICI3, PbS, Gep2, SiO, etc.) which are evaporated from solids in effusion cells. 

The results described in this review show that matrix stabilization of reactive organic intermediates at extremely low temperatures and their subsequent spectroscopic detection are convenient ways of structural investigation of these species. IR spectroscopy is the most useful technique for the identification of matrix-isolated molecules. Nevertheless, the complete study of the spectral properties and the structure of intermediates frozen in inert matrices is achieved when the IR spectroscopy is combined with UV and esr spectroscopic methods. At present theoretical calculations render considerable assistance for the explanation of the experimental spectra. Thus, along with the development of the experimental technique, matrix studies are becoming more and more complex. This fact allows one to expect further progress in the matrix spectroscopy of many more organic intermediates. 

Sun Y, JJ Pignatello (1993) Organic intermediates in the degradation of 2,4-dichlorophenoxyacetic acid by Fe YHjOj and Fe YHjOj/UV. J Agric Food Chem 41 1139-1142. 

Experimental limitations initially limited the types of molecular systems that could be studied by TRIR spectroscopy. The main obstacles were the lack of readily tunable intense IR sources and sensitive fast IR detectors. Early TRIR work focused on gas phase studies because long pathlengths and/or multipass cells could be used without interference from solvent IR bands. Pimentel and co-workers first developed a rapid scan dispersive IR spectrometer (using a carbon arc broadband IR source) with time and spectral resolution on the order of 10 ps and 1 cm , respectively, and reported the gas phase IR spectra of a number of fundamental organic intermediates (e.g., CH3, CD3, and Cp2). Subsequent gas phase approaches with improved time and spectral resolution took advantage of pulsed IR sources. 

The following representative examples of TRIR studies are not meant to be an exhaustive treatment of the various organic reactive intermediates that have been investigated by TRIR methods, but rather to demonstrate the unique insight that such studies can provide. The direct observation of organic intermediates in solution at room temperature by IR spectroscopy can reveal fundamental information related both to bonding and structure of reactive intermediates as well to mechanisms of product formation. 

Beloshapkin, S.A., Matyshak, V.A., Paukshtis, E.A. et al. (1999) IR studies of the transformations of nitrogen-containing organic intermediates during selective reduction of nitrogen oxides by hydrocarbons, React. Kinet. Catal. Lett., 66, 297. 

Shirley, D. A., Preparation of Organic Intermediates, 3, New York, Wiley, 1951... 

In summary, the combination of experimental results and theoretical advances described in this work suggests that chalcogen dications, which have been considered for a long time as hypothetical or ephemeral intermediates can be used in a variety of chemical transformations. Unusual structures of these compounds impart them with reactivities that are remarkably different from other organic intermediates. Harnessing this reactivity should lead to interesting practical applications and we foresee rapid development of this field in the future. 

The experimental observations were interpreted by assuming that the redox cycle starts with the formation of a complex between the catalyst and the substrate. This species undergoes intramolecular two-electron transfer and produces vanadium(II) and the quinone form of adrenaline. The organic intermediate rearranges into leucoadrenochrome which is oxidized to the final product also in a two-electron redox step. The +2 oxidation state of vanadium is stabilized by complex formation with the substrate. Subsequent reactions include the autoxidation of the V(II) complex to the product as well as the formation of aVOV4+ intermediate which is reoxidized to V02+ by dioxygen. These reactions also produce H2O2. The model also takes into account the rapidly established equilibria between different vanadium-substrate complexes which react with 02 at different rates. The concentration and pH dependencies of the reaction rate provided evidence for the formation of a V(C-RH)3 complex in which the formal oxidation state of vanadium is +4. 

European Committee of Surfactants and their Organic Intermediates (CESIO) (2001) CESIO News 5 http //www.cefic.be/files/Publications/cesio 5.pdf... 

Acetophenones can be obtained by various routes such as by reacting acetic anhydride with the substituted benzene (Shirley-PREPARATION OF ORGANIC INTERMEDIATES, 1951, pg. 190) and may then be isomerized, if necessary, with aluminum chlonde (JCS 232(1944)). 

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