Chapter 4: Q 44P (page 234)
Write a mechanism for light-initiated reaction of cyclobutene with chlorine to give chlorocyclobutane. Label the initiation and propagation steps.
Short Answer
Mechanism for free-radical chlorination of cyclobutane
Chapter 4: Q 44P (page 234)
Write a mechanism for light-initiated reaction of cyclobutene with chlorine to give chlorocyclobutane. Label the initiation and propagation steps.
Mechanism for free-radical chlorination of cyclobutane
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Get started for freeIodination of alkanes using iodine (I2)is usually an unfavorable reaction. (See problem 4-17, for example). Tetraiodomethane (Cl4) can be used as the iodine source for iodination in the presence of a free-radical initiator such as hydrogen peroxide. Propose a mechanism (involving mildly exothermic propagation steps) for the following proposed reaction. Calculate the value of ΔHfor each of the steps in your proposed mechanism.
The following bond-dissociation energies may be helpful:
Draw a reaction-energy diagram for a two-step endothermic reaction with a rate-limiting step.
Question: Free-radical chlorination of hexane gives very poor yields of 1 clorohexyane, while cyclohexane can be converted to chlorocyclohexane in good yield.
(a)How do you account for this difference?
(b) What ratio of reactants (cyclohexane and chlorine)
For each compound, predict the major product of free-radical bromination. Remember that bromination is highly selective, and only the most stable radical will be formed.
(a) cyclohexane
(b) methylcyclopentane
(c) decalin
(d) hexane
(e)
(f)
When a small amount of iodine is added to a mixture of chlorine and methane, it prevents chlorination from occurring. Therefore, iodine is a free-radical inhibitor for this reaction. CalculateΔH0values for the possible reactions of iodine with species present in the chlorination of methane and use these values to explain why iodine inhibits the reaction. (The I-Clbond-dissociation enthalpy is 211 kJ/molor 50 kcal/mol).
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