Organic Chemistry: Structure and Function
Organic Chemistry: Structure and Function
8th Edition
ISBN: 9781319079451
Author: K. Peter C. Vollhardt, Neil E. Schore
Publisher: W. H. Freeman
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Chapter 3, Problem 26P
Interpretation Introduction

Interpretation:Diagrams drawn for the propagation steps of radical bromination of benzene should be identified as either representative of early or late transition states.

Concept introduction:Hammond postulate states that exothermic reactions are characterized by early transition states that resemble the structure of substrate more than the product. Slow or endothermic processes are characterized by late transition states that resemble the almost formed bonds as in the products.

Analogous to hydrocarbons the benzene can also undergo initiation to generate bromine radicals; propagation of radicals formed and finally termination. This sequence can be outlined as follows:

Step1: Initiation via homolytic cleavage of BrBr bond: Br2 initiates the reaction; undergoes homolysis and forms bromine radical atom. Energy for homolytic cleavage is provided by the heat or ultraviolet light.

  Organic Chemistry: Structure and Function, Chapter 3, Problem 26P , additional homework tip  1

Step2: Propagation: In first of the propagation steps bromine radical from step 1 abstracts hydrogen radical from C6H6 as follows:

  Organic Chemistry: Structure and Function, Chapter 3, Problem 26P , additional homework tip  2

In subsequent propagation step,phenyl radical abstracts Br· radical from another Br2 , and liberates bromobenzene and new bromine radical.

  Organic Chemistry: Structure and Function, Chapter 3, Problem 26P , additional homework tip  3

Step3: Termination: Bromine radicals generated in propagation steps get quenched upon combination with one another illustrated as follows:

  Organic Chemistry: Structure and Function, Chapter 3, Problem 26P , additional homework tip  4

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What best defines a transition state?
Consider the simple reaction S <--> P, with the forward rate characterized by a rate constant k1, the reverse rate constant characterized by a rate constant k2, and the equilibrium constant for the reaction given by Keq. Which of the listed effects would be brought about by an enzyme catalyzing this reaction?a) increased Keqb) increased k1c) decreased transition state free energy changed) increased k2
Which of the following is NOT true of the transition state? O a. It is unstable and dissociate into products O b. Old bonds are weakened and new bonds begin to form O c. It has a greater energy than the products O d. It cannot dissociate into products without needing any additional energy е. It has a greater energy than the reactants
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