Reactions product-promoted

In some reactions, the rate increases rather than decreases as conversion progresses. This is loosely called autocatalysis, although no genuine catalysis may be involved. The acceleration may stem from promotion by a product or major early intermediate, or from consumption of a reactant that functions as inhibitor. In product-promoted reactions, the kinetics order with respect to a product (or early intermediate) is positive. This causes the rate to increase to a maximum and then to decline as the effect of consumption of the reactant or reactants begins to overcompensate that of promotion by the product. In reactant-inhibited reactions, the order with respect to a reactant is negative. The rate may increase until the respective reactant is used up and, in some cases, may theoretically approach infinity. The latter behavior is, of course, physically impossible, and another mechanism or event necessarily takes over. 

In a product-promoted reaction, fast mass transfer of the accelerating product into another phase slows the rate by depressing autocatalysis. 

In product-promoted reactions in which the accelerating species exits into another phase, or in reactant-inhibited reactions in which the respective reactant enters from another phase, slow mass transfer may boosts rather than depresses the reaction rate. In reactant-inhibited reactions, slow supply of the inhibiting reactant may cause the system to become unstable There may be a sharp stability limit beyond which catastrophic selfacceleration occurs until the phase has become depleted of the reactant or reactants or some other phenomenon has come into play. 

Unusual reaction orders are found in product-promoted or reactant-inhibited ("autocatalytic") reactions, the former with positive apparent order with respect to a product, the latter with negative apparent order with respect to a reactant (see Section 8.9). An example of a product-promoted reaction is acid-catalyzed ester hydrolysis. An example of a reactant-inhibited reaction has already been encountered, namely, olefin hydroformylation, whose order with respect to CO is negative (see eqn 6.12 in Section 6.3). Such behavior is also not uncommon in heterogeneous catalysis (see Section 9.3.2) and enzyme catalysis ("substrate-inhibited" reactions in biochemistry lingo, Section 8.3). A reaction having an order with respect to a silent partner—CO in a homogeneous hydrogenation—will be examined in some detail later in this chapter (see Examples 7.3 and 7.4). 

Positive order with respect to a product (product-promoted reaction)... 

Rather than because of promotion by a product or intermediate, the rate may accelerate because a reactant that acts as inhibitor is consumed. For example, a small amount of inhibitor present initially may depress the rate of a chain reaction until used up (see Section 10.8). More interesting are reactions inhibited by one of the principal reactants (called substrate-inhibited in biochemistry parlance). An example is hydroformylation, in which CO is a reactant with negative reaction order (see Example 6.2 in Section 6.3). There is a subtle but important difference between product-promoted and reactant-inhibited reactions The rate of a product-promoted reaction builds up to a maximum and then declines as reactant depletion overpowers product promotion. In contrast, the rate of a reactant-inhibited reaction keeps escalating, possibly catastrophically, until the respective reactant is almost completely exhausted. Typically, some other mechanism then takes over. [The negative apparent reaction order of the respective reactant arises from an additive denominator term in a one-plus rate equation, but the other terms may be small or insignificant by comparison.] Possible mass-transfer implications of such behavior will be examined in Section 13.3. 

The lower temperatures and reduced degree of oxygen starvation in LPO (vs VPO) generally reduce carbon monoxide production markedly by promoting reaction 18 and suppressing reaction 21. As a consequence, acids, from further oxidation of aldehydes, are usually the main products. 

Furan and thiophene undergo addition reactions with carbenes. Thus cyclopropane derivatives are obtained from these heterocycles on copper(I) bromide-catalyzed reaction with diazomethane and light-promoted reaction with diazoacetic acid ester (Scheme 41). The copper-catalyzed reaction of pyrrole with diazoacetic acid ester, however, gives a 2-substituted product (Scheme 42). 

A catalyst is a substance that increases the rate of a reaction, other than by a medium effect, regardless of the ultimate fate of this substance. For example, in hydroxide-catalyzed ester hydrolysis the catalyst OH is consumed by reaction with the product acid some writers, therefore, call this a hydroxide-promoted reaction, because the catalyst is not regenerated, although the essential chemical event is a catalysis. 

The effectiveness of nitromethane can be attributed to its high dielectric constant, at least in part, which tends to promote reactions which involve electron-rich intermediates. It may also result from the low solubility of the indole products in nitromethane since the indoles precipitate out of the reaction mixture in many cases. ... 

The diastereofacial selectivity of Lewis acid promoted reactions of allylsilancs with chiral aldehydes has been thoroughly investigated58. Aldehydes with alkyl substituted a-stereogenic centers react with a mild preference for the formation of Cram products, this preference being enhanced by the use of boron trifluoride-diethyl ether complex as catalyst58. 

The stereoselectivity of Lewis acid promoted reactions between 2-butenylstannanes and aldehydes has been widely studied, and several very useful procedures for stereoselective synthesis have been developed. In particular syn-products are formed stereoselectively in reactions between trialkyl- and triaryl(2-butenyl)stannanes, and aldehydes induced by boron trifluoride-diethyl ether complex, irrespective of the stannane geometry66. 

While general agreement has been reached concerning the catalytic behaviour of the product metal in promoting reaction, other aspects of the rate process have been less satisfactorily characterized these include the changes which precede nucleus formation, the distribution of such sites and development of the reaction interface. 

Changes in the composition of gaseous products as reaction proceeds may make definition of the fractional decomposition, a, difficult. For example, product CO and residual carbon may be capable of reducing a metallic oxide, particularly at high a and the catalytic properties of an accumulating solid product may result in promotion of secondary gas reactions. 

The radical-promoted reaction between polyethylene and hexafluoro-acetone is shown in Equation 1. It had been demonstrated previously in the case of simple hydrocarbons (8) that the addition of a carbon radical to the carbonyl group of hexafluoroacetone can take place in two modes, to yield the product, of substitution with either a fluoro-... 

Oda et al. reported that under reflux conditions, the zinc-promoted reaction of 2,3-dichloro-l-propene with aldehydes and ketones in a two-phase system of water and toluene containing a small amount of acetic acid gave 2-chloroallylation products (Eq. 8.31).64 No conversion occurred when tin was used as the promoter. The absence of water completely shuts down the reaction. Interestingly, the action of 2,3-dichloropropene plus zinc powder in aqueous ethanol gives the dechlorination product, allene.65... 

Tsuji, J. Applications of Palladium-Catalyzed or Promoted Reactions to Natural Product Syntheses. 91, 29-74 (1980). 

For the Cu(OTf)2-promoted reaction between ethyl diazoacetate and cinnam-aldehyde dimethyl acetal, products 143-145 account for only 35% the total yield. C/C and C/H insertion products 151 and 152 are obtained additionally in 49 and 14% yield, respectively154). It was assumed that the copper compound acts through Lewis-acid catalysis here, just as it is believed to do when orthoesters are used as substrates 160). According to this, catalyst-induced formation of a methoxy-... 

The reaction mechanism in the irradiated flue gas is probably quite complex, but basically the EB excites the gas molecules and promotes reactions that convert the oxides to acids. These then react with ammonia or calcium compounds to give solid products that are removed by the filter. The initiation reaction is believed to be brought about by radical formation, such as OH,... 

---