Formation production, patented method

Ghlorohydrination with Nonaqueous Hypochlorous Acid. Because the presence of chloride ions has been shown to promote the formation of the dichloro by-product, it is desirable to perform the chlorohydrination in the absence of chloride ion. For this reason, methods have been reported to produce hypochlorous acid solutions free of chloride ions. A patented method (48) involves the extraction of hypochlorous acid with solvents such as methyl ethyl ketone [78-93-3J, acetonitrile, and ethyl acetate [141-78-6J. In one example hypochlorous acid was extracted from an aqueous brine with methyl ethyl ketone in a 98.9% yield based on the chlorine used. However, when propylene reacted with a 1 Af solution of hypochlorous acid in either methyl ethyl ketone or ethyl acetate, chlorohydrin yields of only 60—70% were obtained (10). 

Penny, G.S. "Method of Increasing Hydrocarbon Production from Subterranean Formations," US Patent 4,702,849(1987). 

The fermentative fixing of CO2 and water to acetic acid by a species of acetobacterium has been patented acetyl coen2yme A is the primary reduction product (62). Different species of clostridia have also been used. Pseudomonads (63) have been patented for the fermentation of certain compounds and their derivatives, eg, methyl formate. These methods have been reviewed (64). The manufacture of acetic acid from CO2 and its dewatering and refining to glacial acid has been discussed (65,66). 

Physical Chemical Characterization. Thiamine, its derivatives, and its degradation products have been fully characterized by spectroscopic methods (9,10). The ultraviolet spectmm of thiamine shows pH-dependent maxima (11). H, and nuclear magnetic resonance spectra show protonation occurs at the 1-nitrogen, and not the 4-amino position (12—14). The H spectmm in D2O shows no resonance for the thiazole 2-hydrogen, as this is acidic and readily exchanged via formation of the thiazole yUd (13) an important intermediate in the biochemical functions of thiamine. Recent work has revised the piC values for the two ionization reactions to 4.8 and 18 respectively (9,10,15). The mass spectmm of thiamine hydrochloride shows no molecular ion under standard electron impact ionization conditions, but fast atom bombardment and chemical ionization allow observation of both an intense peak for the patent cation and its major fragmentation ion, the pyrimidinylmethyl cation (16). 

Several other processes for extracting Be from beryl have been patented the most feasible involves the formation of BeCl2 by direct chlorination of beryl under reducing conditions several volatile chlorides are produced by this reaction (BeCl2, AICI3, SiCl4 and FeClj) and are separated by fractional condensation to give the product in a pure state. Other methods involve the fusion of beryl with carbon and pyrites, with calcium carbide and with silicon. 

G. S. Penny. Method of increasing hydrocarbon production from subterranean formations. Patent US 4702849,1987. 

Other similar lipase/esterase resolution processes have been developed such as the use of Bacillus that esterase to produce the substituted propanoic acids that are precursors of non-steroidal anti-inflammatory drags, snch as naproxen and ibuprofen etc., and the formation of chiral amines by Celgene. Other methods start from prochiral precursors and have the advantage that enantioselective synthesis allows the production of particular isomers in yields approaching 100%, rather than the 50% yields characteristic of resolution processes. For instance Hoechst have patented the production of enantiomers using Pseudomonas fluorescens lipase to either acylate diols or hydrolyse diacetate esters. 

Electrochemical Nitrations. A method developed in 1956 in Sweden by Ohman for prepn of nitric acid esters has been described in several patents. The method consists in anodic oxidation (using a bright platinum anode) in presence of nitric acid, or its salts (such.as Ca nitrate). The compds to be nitrated areunsaturated hydrocarbons (such as ethylene, propylene, butylene, etc), which can be dissolved in nonaqueous solvents (such as acetone). The OH concn is maintained low during the reaction by adding either coned nitric acid or glacial acetic acid. Water should be absent to prevent the formation of various by-products... 

A method of considerable industrial importance for the large-scale preparation of ethylene oxide is direct oxidation of ethylene at elevated temperatures over a suitably prepared metallic silver catalyst. Although the reaction may be written aa indicated in Eq. (09), in actual practice only about half the ethylene is converted into ethylene oxide, the remainder being oxidized further to carbon dioxide and water. In spite of this seeming disadvantage, catalytic oxidation appears at present to bo economically competitive with chlorohydrin formation aa a means for the commercial production of ethylene oxide.MM Unfortunately, other olefins, such as propylene and mo-butylene for example, apparently give only carbon dioxide and water under the usual oxidation conditions,1310 so that until now the patent hu balance ethylene oxide has been the only representative accessible by tins route. 

If polymerization catalysts, for instance for alkenc polymerization (Zicglcr-Natta-type catalysts), are prepared by precipitation methods, they can be formed by precipitation from organic solvents, as claimed in several patents [22], In these patents the precipitation of titanium-magnesium compounds in THF with hexane as precipitating agent is used for the formation of the catalyst. Many important Zicgler-Natta initiators are solids, and heterogeneous initiator systems seem to be necessary for the production of isotactic polyalkenes [23]. However, not much information on the details of catalyst preparation is available in the open literature. 

Since 1910 the method of Bart has been modified by a number of investigators, Bart, himself, being the first to improve the reaction. He found that coupling of aryldiazonium compounds with alkali arsenites is catalyzed by copper salts and by silver or copper powder. In a later patent the use of metallic catalysts, copper, nickel, or cobalt, as well as their salts is said to facilitate the removal of diazo nitrogen at low temperatures and to obviate the formation of by-products. Though many have since observed that the coupling reaction is speeded by the use of the above catalysts, no systematic study has been made to determine the effect of such catalysts on the final yield. 

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