Chem 229 – Organic Chemistry for Engineers - 2020-2021 Fall

December 2020

Problem Set 6

1. Give the product (or products) that you would expect to be formed in each of the
following reactions. In each case give the mechanism (SN1, SN2, E1 or E2) by which the
product is formed and predict the relative amount of each (Major, minor etc.)

2. Starting with an appropriate alkyl halide and using any other needed reagents, outline
synthesis of each of the following.

a. Butyl sec-butyl ether

b. (S)-2-Pentanol
c. (CH3)3CCH=CH2
d. cis-4-Isopropylcyclohexanol
e. CH3CO2CH2C6H5 (C6H5 = phenyl)
Chem 229 – Organic Chemistry for Engineers - 2020-2021 Fall

3.

4.

PROBLEMS

EtO
– Cl
Br
(a) EtOH, 50 C
(f) t-Bu
MeOH, 25 °C
Br t -BuOK
(b) t -BuOH, 50 C MeO
(g) 3-Chloropentane MeOH, 50 °C
–
(c) MeO
(h) 3-Chloropentane
CH3CO2
MeOH, 50 C CH3CO2H, 50 C
Br
HO
(i) (R)-2-bromobutane
(d) t -BuOK 25 °C
t -BuOH, 50 C
Br 25 C
(j) (S)-3-Bromo-3-methylhexane
MeOH
Cl
I
I (k) (S)-2-Bromooctane
(e) t-Bu
acetone, 50 °C
MeOH, 50 C

5. 6.30 Write conformational str uctures for the substitution pr oducts of the following deuterium-labeled compounds:

Cl Cl
H
H I H I
(a) D MeOH
(c) MeOH
D
H

Cl Cl
H I CH3
(b) D MeOH
(d) H MeOH, H2O

H D

6.31 Although ethyl bromide and isobutyl bromide are both primary halides, ethyl bromide undergoes SN 2 reactions more tha
10 times faster than isobutyl br omide does. When each compound is treated with a strong base/nucleophile ( EtO ), isobutyl bro
gives a greater yield of elimination pr oducts than substitution pr oducts, whereas with ethyl bromide this behavior is reversed. W
accounts for these results?
6.32 Consider the reaction of I with CH3CH2Cl.
(a) Would you expect the reaction to be SN 1 or SN 2?The rate constant for the r eaction at 60 C is 5 10 5 L mol 1
s 1.
(b) What is the reaction rate if [ I ] 0.1 mol L 1 and [ CH3CH2Cl] 0.1 mol L 1?
(c) If [ I ] 0.1 mol L 1 and [ CH3CH2Cl] 0.2 mol L 1?
(d) If [ I ] 0.2 mol L 1 and [ CH3CH2Cl] 0.1 mol L 1?
(e) If [ I ] 0.2 mol L 1 and [ CH3CH2Cl] 0.2 mol L 1?

6.33 Which reagent in each pair listed here would be the more reactive nucleophile in a polar aprotic solvent?
(a) CH3NH or CH3NH2 (d) (C6H5)3N or (C6H5)3P (g) H2S or HS
(b) CH3O or CH3CO2 ( OAc) (e) H2O or H3O (h) CH3CO2 ( OAc) or HO
(c) CH3SH or CH3OH (f) NH3 or NH4

6.34 Write mechanisms that account for the pr oducts of the following reactions:
Br HO Br HO
(a) HO H O (b) H N