Entrainment reactions

This is of great preparative importance as the Grig-nard reagent of 3-bromosubstituted thiophenes and the dibromothio-phenes can be obtained only by the entrainment method and with inferior The mechanism of the entrainment reaction... 

The anion of nitromethane is particularly reactive in S l reactions. Various kinds of tertiary nitro groups are replaced by a nitromethyl group on treatment with the anion of nitromethane (Section 7.1).49 2-Iodoadamantane reacts with the anion of nitromethane in the presence of acetone enolate (entrainment reaction) under irradiation of a 400-W UV lamp to give 2-ni-tromethyladamantane in 68% yield, (see Eq. 5.32).50a 1-Iodoadamantane also reacts with the anion of nitromethane in a similar way.50b... 

The atomic proportions of magnesium are not related to the mole quantity of hexachlorobenzene in this or any other entrainment reaction. The excess magnesium (1.1 g. atoms in this case) is used to react with ethylene bromide and leave 0.5 g. atom of dean-surfaced magnesium. Ordinarily 1 mole of entrainment reagent is used per mole of inert halide, but for this preparation 2 moles of entrainment reagent per mole of halide gives a better yield. 

For nucleophiles which are unable to initiate the reaction but are quite reactive in the propagation steps, the addition of minute amounts of another nucleophile capable of initiating the reaction increases the generation of intermediates. This allows the less-reactive initiation-nucleophile to start its own propagation. This entrainment reaction allows an extension of the SRN1 mechanism to nucleophiles that are poor donors, supporting the chain nature of the reaction [9]. 

On the other hand, no reaction was observed under irradiation with nitronate ion (31) alone. It is known that in S l reactions a more reactive nucleophile can induce the reaction of a less reactive one (entrainment reaction)5,8,13,14. Thus nitronate ion gave the substitution product 32 in the presence of acetophenone 27b (58%) or acetone 27a (87%) enolate ions (equation 43). 

Thus the increased reactivity of this compound vs the parent l-chloro-3,3-dimethyl-bicyclo[2.2.2]octane can be explained through an intramolecular entrainment reaction. 

The enolate anions of 2-acetylthiophene and 2-acetylfuran have been arylated under photochemical conditions in the presence of t-BuOK and good electron donors such as acetone enolate (entrainment reaction) to give the corresponding benzyl 2-thienyl and 2-furanyl ketones respectively. Use of FeBr2 as initiator in a dark reaction gives good yields of the substitution products without the need for added nucleophiles, and it is suggested that these arylation processes occur by an SrnI mechanism. 

Such a mathematical model must fulfill the following requirements (1) It must include all hydrodynamic transport phenomena and all physicochemical aggregation, sedimentation, and entrainment reactions that have been found significant, yet it should not attempt impractical completeness (such as including the still unknown factor of consolidation of sedimented material). (2) It should require input data—including global parameters that reflect less known reaction steps— that are readily... 

Coke (deposited on the catalyst) which is burned in the regenerator producing energy (electricity, steam) and the necessary heat for the reaction. Produced gases are cleansed when necessary of SOj and NO as well as particles of entrained catalyst. 

The reaction rate is increased by using an entraining agent such as hexane, benzene, toluene, or cyclohexane, depending on the reactant alcohol, to remove the water formed. The concentration of water in the reaction medium can be measured, either by means of the Kad-Eischer reagent, or automatically by specific conductance and used as a control of the rate. The specific electrical conductance of acetic acid containing small amounts of water is given in Table 6. 

The unit has virtually the same flow sheet (see Fig. 2) as that of methanol carbonylation to acetic acid (qv). Any water present in the methyl acetate feed is destroyed by recycle anhydride. Water impairs the catalyst. Carbonylation occurs in a sparged reactor, fitted with baffles to diminish entrainment of the catalyst-rich Hquid. Carbon monoxide is introduced at about 15—18 MPa from centrifugal, multistage compressors. Gaseous dimethyl ether from the reactor is recycled with the CO and occasional injections of methyl iodide and methyl acetate may be introduced. Near the end of the life of a catalyst charge, additional rhodium chloride, with or without a ligand, can be put into the system to increase anhydride production based on net noble metal introduced. The reaction is exothermic, thus no heat need be added and surplus heat can be recovered as low pressure steam. 

Direct, acid catalyzed esterification of acryhc acid is the main route for the manufacture of higher alkyl esters. The most important higher alkyl acrylate is 2-ethyIhexyi acrylate prepared from the available 0x0 alcohol 2-ethyl-1-hexanol (see Alcohols, higher aliphatic). The most common catalysts are sulfuric or toluenesulfonic acid and sulfonic acid functional cation-exchange resins. Solvents are used as entraining agents for the removal of water of reaction. The product is washed with base to remove unreacted acryhc acid and catalyst and then purified by distillation. The esters are obtained in 80—90% yield and in exceUent purity. 

Anhydrous Acetic Acid. In the manufacture of acetic acid by direct oxidation of a petroleum-based feedstock, solvent extraction has been used to separate acetic acid [64-19-7] from the aqueous reaction Hquor containing significant quantities of formic and propionic acids. Isoamyl acetate [123-92-2] is used as solvent to extract nearly all the acetic acid, and some water, from the aqueous feed (236). The extract is then dehydrated by azeotropic distillation using isoamyl acetate as water entrainer (see DISTILLATION, AZEOTROPIC AND EXTRACTIVE). It is claimed that the extraction step in this process affords substantial savings in plant capital investment and operating cost (see Acetic acid and derivatives). A detailed description of various extraction processes is available (237). 

Thermochemical Liquefaction. Most of the research done since 1970 on the direct thermochemical Hquefaction of biomass has been concentrated on the use of various pyrolytic techniques for the production of Hquid fuels and fuel components (96,112,125,166,167). Some of the techniques investigated are entrained-flow pyrolysis, vacuum pyrolysis, rapid and flash pyrolysis, ultrafast pyrolysis in vortex reactors, fluid-bed pyrolysis, low temperature pyrolysis at long reaction times, and updraft fixed-bed pyrolysis. Other research has been done to develop low cost, upgrading methods to convert the complex mixtures formed on pyrolysis of biomass to high quaHty transportation fuels, and to study Hquefaction at high pressures via solvolysis, steam—water treatment, catalytic hydrotreatment, and noncatalytic and catalytic treatment in aqueous systems. 

Substituted Amides. Monosubstituted and disubstituted amides can be synthesized with or without solvents from fatty acids and aLkylamines. Fatty acids, their esters, and acid halides can be converted to substituted amides by reaction with primary or secondary aLkylamines, arylamines, polyamines, or hydroxyaLkylamines (30). Di- -butylamine reacts with oleic acid (2 1 mole ratio) at 200—230°C and 1380 kPa (200 psi) to produce di-A/-butyloleamide. Entrained water with excess -butylamine is separated for recycling later (31). 

Sasol Fischer-Tropsch Process. 1-Propanol is one of the products from Sasol s Fischer-Tropsch process (7). Coal (qv) is gasified ia Lurgi reactors to produce synthesis gas (H2/CO). After separation from gas Hquids and purification, the synthesis gas is fed iato the Sasol Synthol plant where it is entrained with a powdered iron-based catalyst within the fluid-bed reactors. The exothermic Fischer-Tropsch reaction produces a mixture of hydrocarbons (qv) and oxygenates. The condensation products from the process consist of hydrocarbon Hquids and an aqueous stream that contains a mixture of ketones (qv) and alcohols. The ketones and alcohols are recovered and most of the alcohols are used for the blending of high octane gasoline. Some of the alcohol streams are further purified by distillation to yield pure 1-propanol and ethanol ia a multiunit plant, which has a total capacity of 25,000-30,000 t/yr (see Coal conversion processes, gasification). 

An excess of crotonaldehyde or aUphatic, ahcyhc, and aromatic hydrocarbons and their derivatives is used as a solvent to produce compounds of molecular weights of 1000—5000 (25—28). After removal of unreacted components and solvent, the adduct referred to as polyester is decomposed in acidic media or by pyrolysis (29—36). Proper operation of acidic decomposition can give high yields of pure /n j ,/n7 j -2,4-hexadienoic acid, whereas the pyrolysis gives a mixture of isomers that must be converted to the pure trans,trans form. The thermal decomposition is carried out in the presence of alkaU or amine catalysts. A simultaneous codistillation of the sorbic acid as it forms and the component used as the solvent can simplify the process scheme. The catalyst remains in the reaction batch. Suitable solvents and entraining agents include most inert Hquids that bod at 200—300°C, eg, aUphatic hydrocarbons. When the polyester is spHt thermally at 170—180°C and the sorbic acid is distilled direcdy with the solvent, production and purification can be combined in a single step. The solvent can be reused after removal of the sorbic acid (34). The isomeric mixture can be converted to the thermodynamically more stable trans,trans form in the presence of iodine, alkaU, or sulfuric or hydrochloric acid (37,38). 

After the SO converter has stabilized, the 6—7% SO gas stream can be further diluted with dry air, I, to provide the SO reaction gas at a prescribed concentration, ca 4 vol % for LAB sulfonation and ca 2.5% for alcohol ethoxylate sulfation. The molten sulfur is accurately measured and controlled by mass flow meters. The organic feedstock is also accurately controlled by mass flow meters and a variable speed-driven gear pump. The high velocity SO reaction gas and organic feedstock are introduced into the top of the sulfonation reactor,, in cocurrent downward flow where the reaction product and gas are separated in a cyclone separator, K, then pumped to a cooler, L, and circulated back into a quench cooling reservoir at the base of the reactor, unique to Chemithon concentric reactor systems. The gas stream from the cyclone separator, M, is sent to an electrostatic precipitator (ESP), N, which removes entrained acidic organics, and then sent to the packed tower, H, where SO2 and any SO traces are adsorbed in a dilute NaOH solution and finally vented, O. Even a 99% conversion of SO2 to SO contributes ca 500 ppm SO2 to the effluent gas. 

Passing a stream of nitrogen at 95—100°C through a reaction mixture of ethyl ether and 30 wt % oleum prepared at 15°C results in the entrainment of diethyl sulfate. Continuous operation provides a >50% yield (96). The most economical process for the manufacture of diethyl sulfate starts with ethylene and 96 wt % sulfuric acid heated at 60°C. The resulting mixture of 43 wt % diethyl sulfate, 45 wt % ethyl hydrogen sulfate, and 12 wt % sulfuric acid is heated with anhydrous sodium sulfate under vacuum, and diethyl sulfate is obtained in 86% yield the commercial product is >99% pure (97). 

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