Академический Документы
Профессиональный Документы
Культура Документы
Chapter 5
TUTORIAL
1
TUTORIAL: LFER
1. Relate the substituent constant values of table:Hammett constants, to
the electron donating or -withdrawing character of each substituent. How
does this compare with qualitative predictions of substituent effects on
acidity? Why might you expect σm and σp values for the same substituent
to be different
TUTORIAL: LFER
2. Match the ρ values with the appropriate reactions. Explain your reasoning.
Reaction constants: +2.45, +0.75, -2.39, -7.29.
Reactions:
a) nitration of substituted benzenes
b) ionization of substituted benzenthiols
c) ionization of substituted benzenephosphonic acids
d) reaction of substituted N,N-dimethylanilines with methyl iodide
TUTORIAL: LFER
3. Determine the value of ρ for the reaction shown from the data given:
TUTORIAL: LFER
4. The basicity of a series of substituted benzyldimethylamines has been
measured. Determine whether these basicity data are correlated by the
Hammet equation. What is the value of ρ ? What interpretation do you put
on its sign?
TUTORIAL: LFER
5. Under strongly alkaline conditions (methoxide ion) HCl is eliminated from
2-chloro-2-methyl-1-phenylpropane to give 2-methyl-1-phenylprop-1-ene.
From the following results for the effect of substituents in the phenyl ring on
the rate of the reaction, determine the Hammett value for this reaction
TUTORIAL: LFER
6. The following partial rate factors(kf) were obtained for the bromination of
monosubstituated benzenes hy hypobromous acid in 50 % aqueous dioxan
containing perchloric acid.
Show that the values of kf fit a Hammet equation using σ+ values and
determine the value of ρ. Predict the kf value for p-fluorobenzene.
Do these results allow you to distinguish between H2+OBr and Br + as the
brominated spieces?
TUTORIAL: LFER
7. The mechanism of semicarbazone formation from benzaldehyde involves
condensation, followed by elimination of water:
Calculate the Hammett ρ value at both pH's and explain the difference in
terms of a change in the rate determining step.
TUTORIAL: LFER
8. The reaction between ethyl chloroformate and aniline is a two-step
process, involving addition followed by elimination
The following kinetic data were obtained for the effect of substituents in the
aniline on the rate of reaction:
What may be deduced about the rate determining step in this reaction from
the plot of log kobs against σ-.
Suggest an experimental check on the proposed mechanism.
TUTORIAL: LFER
9. In the presence of a base (potassiun t-butoxide in t-butanol) 2-phenyl-
ethylbenzene sulphonate undergoes elimination to give styrene and the
mechanism of the reaction is E2.