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The Curtin–Hammett principle is a principle in chemical kinetics proposed by David Yarrow Curtin and Louis Plack Hammett.It states that, for a reaction that has a pair of reactive intermediates or reactants that interconvert rapidly (as is usually the case for conformational isomers), each going irreversibly to a different product, the product ratio will depend both on the difference in ...
relating the equilibrium constant, , for a given equilibrium reaction with substituent R and the reference constant when R is a hydrogen atom to the substituent constant σ which depends only on the specific substituent R and the reaction rate constant ρ which depends only on the type of reaction but not on the substituent used.
However, all reactions can be represented as a series of elementary reactions and, if the mechanism is known in detail, the rate equation for each individual step is given by the expression so that the overall rate equation can be derived from the individual steps. When this is done the equilibrium constant is obtained correctly from the rate ...
For example, when 2-iodobutane is treated with alcoholic potassium hydroxide (KOH), but-2-ene is the major product and but-1-ene is the minor product. [1] More generally, Zaytsev's rule predicts that in an elimination reaction the most substituted product will be the most stable, and therefore the most favored.
Under kinetic reaction control, one or both forward reactions leading to the possible products is significantly faster than the equilibration between the products. After reaction time t, the product ratio is the ratio of rate constants k and thus a function of the difference in activation energies E a or ΔG ‡:
In mathematics, a paraproduct is a non-commutative bilinear operator acting on functions that in some sense is like the product of the two functions it acts on. According to Svante Janson and Jaak Peetre, in an article from 1988, [1] "the name 'paraproduct' denotes an idea rather than a unique definition; several versions exist and can be used for the same purposes."
The major product of the addition reaction will be the one formed from the more stable intermediate. Therefore, the major product of the addition of HX (where X is some atom more electronegative than H) to an alkene has the hydrogen atom in the less substituted position and X in the more substituted position.
The methyl group in toluene is small and will lead the ortho product being the major product. On the other hand, the t-butyl group is very bulky (there are 3 methyl groups attached to a single carbon) and will lead the para product as the major one. Even with toluene, the product is not 2:1 but having a slightly less ortho product.