Course of the reaction

Because mole numbers are additive, it follows that the product A. A V will be an additive quantity provided that a for each species remains constant during the course of the reaction. This last condition implies, essentially, that the effective dipole moments and hence the orientation of each species remain constant, which is most likely to be the case at constant film pressure. Then... 

A saturated alkyl group does not exhibit functionality. It is not a d -synthon, because the functional groups, e.g. halide or metal ions, are lost in the course of the reaction. It functions as an alkyl synthon. Alkenyl anions (R. West, 1961) on the other hand, constitute d -synthons, because the C = C group remains in the product and may be subject to further synthetic operations. 

Lithiated indoles can be alkylated with primary or allylic halides and they react with aldehydes and ketones by addition to give hydroxyalkyl derivatives. Table 10.1 gives some examples of such reactions. Entry 13 is an example of a reaction with ethylene oxide which introduces a 2-(2-hydroxyethyl) substituent. Entries 14 and 15 illustrate cases of addition to aromatic ketones in which dehydration occurs during the course of the reaction. It is likely that this process occurs through intramolecular transfer of the phenylsulfonyl group. 

Only small quantities of iron(III) bromide are required It is a catalyst for the brommation and as Figure 12 6 indicates is regenerated m the course of the reaction We 11 see later m this chapter that some aromatic substrates are much more reactive than benzene and react rapidly with bromine even m the absence of a catalyst... 

The essential information implied by the chemical equation is the stoichiometry at the macroscopic level, ie, if a moles of M react, then b moles of B do also p moles of P are formed, etc. No inference should be made about behavior at the microscopic or atomic level, ie, there is no implication thatp molecules of P appear simultaneously. There may or may not be intermediates that appear and disappear in the course of the reaction. 

The rate law draws attention to the role of component concentrations. AH other influences are lumped into coefficients called reaction rate constants. The are not supposed to change as concentrations change during the course of the reaction. Although are referred to as rate constants, they change with temperature, solvent, and other reaction conditions, even if the form of the rate law remains the same. 

The zwitterion (6) can react with protic solvents to produce a variety of products. Reaction with water yields a transient hydroperoxy alcohol (10) that can dehydrate to a carboxyUc acid or spHt out H2O2 to form a carbonyl compound (aldehyde or ketone, R2CO). In alcohoHc media, the product is an isolable hydroperoxy ether (11) that can be hydrolyzed or reduced (with (CH O) or (CH2)2S) to a carbonyl compound. Reductive amination of (11) over Raney nickel produces amides and amines (64). Reaction of the zwitterion with a carboxyUc acid to form a hydroperoxy ester (12) is commercially important because it can be oxidized to other acids, RCOOH and R COOH. Reaction of zwitterion with HCN produces a-hydroxy nitriles that can be hydrolyzed to a-hydroxy carboxyUc acids. Carboxylates are obtained with H2O2/OH (65). The zwitterion can be reduced during the course of the reaction by tetracyanoethylene to produce its epoxide (66). 

The by-product ammonia is vented from the reactor during the course of the reaction. Unconverted aniline is distilled off at the end of the reaction and the diphenylamine is washed with aqueous hydrochloric acid to remove trace amounts of aniline. The product is then washed with water and purified in a refining stiU. 

Dialkyldimethyl and alkyltrknethyl quaternaries can be prepared direcdy from secondary and primary amines as shown ia equations 7 and 8, respectively. This process, known as exhaustive alkylation, is usually not the method of choice on a commercial scale. This technique requires the continuous addition of basic material over the course of the reaction to prevent the formation of amine salts (223,224). Furthermore, products such as inorganic salt and water must be removed from the quaternary. The salt represents a significant disposal problem. 

The characteristics of WC, especially grain size, are determined by purity, particle shape and grain size of the starting material, and the conditions employed for reduction and carburization. The course of the reaction WO3 — W — WC is dependent on temperature, gas flow rates, water-vapor concentration in the gas, and the depth of the powder bed. All these factors affect the coarsening of the grain. 

The acid chlorides are generally more reactive than the corresponding acid anhydrides. In fact, the alcoholysis of acid chlorides is probably the best laboratory method for preparing esters. Frequentiy, basic materials are added during the course of the reaction to neutralize by-product hydrochloric acid. When the basic material is aqueous caustic, the procedure is referred to as the Schotten-Baumann procedure (73). Esterification of tertiary alcohols by acid chlorides is described in Reference 74. Esters of tertiary alcohols can also be formed through an intermediate /-butyl thioate group (75) ... 

It would be anticipated that 1,2-benzisoxazoles undergo electrophilic substitution in the homocyclic ring, and this has been borne out by experiment. The absence or presence of substituents in the 3-position has no influence on the course of the reaction. In qualitative terms it would also be expected that substitution would occur in the 5- or 7-position (see Section 4.16.2.1.1) but most electrophilic substitutions take place at the 5-position. 

The course of the reaction is dependent on the configuration of the oxime. The (Z)-oxime gave 1,2-benzisoxazoles as the primary product while the (E)-oxime generally produced a Beckmann rearrangement product with or without subsequent cyclization to a benzisoxazole (Scheme 167) (67AHC(8)277). Bunnett conducted a kinetic study on the reaction shown in Scheme 167 and determined that cyclization to intermediate (551) was the rate determining step (61JA3805). 

A variety of 1-azirines are available (40-90%) from the thermally induced extrusion (>100 °C) of triphenylphosphine oxide from oxazaphospholines (388) (or their acyclic betaine equivalents), which are accessible through 1,3-dipolar cycloaddition of nitrile oxides (389) to alkylidenephosphoranes (390) (66AG(E)1039). Frequently, the isomeric ketenimines (391) are isolated as by-products. The presence of electron withdrawing functionality in either or both of the addition components can influence the course of the reaction. For example, addition of benzonitrile oxide to the phosphorane ester (390 = C02Et) at... 

The reactions are carried out under first-order conditions, i.e., the stoichiometric concentration of the antioxidant, a-tocopherol, is in large excess over that of 16-ArN, such that the concentration of a-tocopherol does not change significantly throughout the time course of the reaction. The emulsion employed was prepared by mixing the non-ionic emulsifier Brij 30, octane and HCl (3 mM, pH = 2.5). The resulting emulsion is opaque, thus values were obtained electrochemically by employing Linear Sweep Voltammetry (LSV). 

Semi-Batch Reactor In a semi-batch reactor, some reactants are added to the reactor at the start of the batch, while others are fed intermittently or continuously during the course of the reaction. 

If a Soxhlet extractor having a smaller capacity is employed, the cup will have to be recharged during the course of the reaction. 

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