INTRODUCTION TO GENERAL CHEMISTRY 1B

ASSIGNMENT
ONLINE SUBMISSION DEADLINE SUNDAY 11/09/2022 @ 11:59 PM

/3 1. For each pair of compounds, predict which compound has the higher boiling point.
Support your prediction with a valid scientific argument.
(a) isopropyl bromide and n-butyl bromide
n-butyl bromide Br 1
n-butyl bromine is expected to have higher boiling point because of its huge surface area
(b) isopropyl chloride and tert-butyl bromide

tert-butyl bromide Br 1
tert-butyl bromide has a higher molecular weight and a larger halogen, and despite its
greater branching, boils at higher temperature than isopropyl chloride
(c) 1-bromobutane and 1-chlorobutane
1-bromobutane Br 1
1-Bromotutane has a higher molecular weight and a larger halogen, and boils at higher
temperature than 1-chlorobutane.

/4 2. For each pair, predict the stronger nucleophile in the reaction (using an alcohol as the
solvent). Explain your prediction.
(a) (CH3CH2)3N or (CH3CH2)2NH
(CH3CH2)2NH is better nucleophile because it is less hindered. 1
(b) I- or Cl-
I- is a better nucleophile because of its large size hence, more polarizable than Cl 1
(c) (CH3)2O or (CH3)2S
(CH3)2S is better nucleophile because S is larger than O hence, more polarizable than N 1
 (d) (CH3)2CHO- or CH3CH2CH2O-
CH3CH2CH2O- is a better nucleophile because it is less branched hence, less steric
hindrance. 1

/1 3. Rank the following compounds in decreasing order of their reactivity toward the SN2
reaction with sodium ethoxide (Na+-OCH2CH3) in ethanol
(a) methyl chloride
(b) tert-butyl iodide
(c) neopentyl bromide
(d) isopropyl bromide
Methyl chloride > isopropyl bromide > neopentyl bromide > tert-butyl iodate
a > d > c > b 1

/11 4. When the following compound is heated in methanol, several different products are
formed as shown below. Propose the mechanisms to account for each of the four
products.

H Br heat H Br
C C CH2

1
H H
1
CH3OH

The carbocation can be rearranged following the SN1 or E1 mechanisms to form different
product

CH2 CH2
HOCH3
H CH3OH2 + Br-
1
 H
CH3 H3C OCH3 H3C OCH3
CH2 Br-
1,2-hydride shift HOCH3
HBr
H
1 1 1

1
CH2 1,2-Alkyl shift
1
1
OCH3 Br- OCH3
HOCH3
H
1
H 1
HOCH3

/12 5. Solvolysis of bromomethylcyclopentane in methanol gives a complex product mixture

of the following five compounds. Propose mechanisms to account for these products.
CH2Br CH2 CH3 H3C OCH3 OCH3
CH3OH

heat

H Br H Br
C CH3OH C CH2
H H
Heat
1 1

CH2 CH2
HOCH3
H CH3OH2 + Br-
1
H 1
CH2 CH3 H3C OCH3 H3C OCH3
1,2-hydride shift HOCH3 Br-
H
1 1
 CH3 CH3
HOCH3
H
1

CH2 1,2-Alkyl shift

1 1
1
HOCH3 OCH3 OCH3
Br-
H
1
H 1HOCH3

/6 6. Under certain conditions, when (R)-2-bromobutane is heated with water, the SN1
substitution proceeds twice as fast as the SN2. Calculate the e.e. and the specific rotation
expected for the product. The specific rotation of (R)-butan-2-ol is -13.5o. Assume that
SN1 the gives equal gives equal amounts of the two enantiomers.
CH3 CH3
H2O, 
SN2 inversion
H3CH2C
H
1 H3CH2C
OH
1
Br H
H2O,
 CH3 CH3
SN1
recemization

H H3CH2C
OH 1
1
H3CH2C
OH H
If SN1, which gives racemization, occurs exactly twice as SN2, which gives inversion,
then the racemic mixture (50%R:50%S) is 66.7% of the mixture and the rest, 33.3%, the
 enantiomeric mixture, the R and S cancel each other algebraically as well as in optical

1
rotation)
The optical rotation of pure (s)-butan-1-ol is + 13.5o. The optical rotation of this mixture
is: 33.3% x 13.5o = 4.5o 1

/6 7. Under second-order conditions (strong base nucleophile), SN2 and E2 reactions may
occur simultaneously and compete with each other. Show what products might be
expected from the reaction of 2-bromo-3-methylbutane (a moderately hindered 2° alkyl
halide) with sodium ethoxide.

1
Br Na+-OCH2CH3
1
H3CH2CO
1 1 SN2
1
E21 E22
E22 is the major product because is the most sustituted 1

/3 8. Show how you would convert (in one or two steps) 1-phenylpropane to the three
products shown below. In each case, explain what unwanted reactions might produce
undesirable impurities in the product.
(a) Propenyl-benzene
(b) (1-Methoxy-propyl)-benzene
(c) (1-Bromo-propyl)-benzene
Br OCH3
Br2 CH3OH

hv
N
aO hv (b) 1
C(
CH
(c) 
1 3 )
3

(a) 1
/9 9. (a) Under certain conditions, the reaction of 0.5 M 1-bromobutane with 1.0 M sodium
methoxide forms 1-methoxybutane at a rate of 0.05 mol/L per second. What would be the
rate if 0.1 M 1-bromobutane and 2.0 M NaOCH3 were used?
(b) Consider the reaction of 1-bromobutane with a large excess of ammonia (NH3). Draw
the reactants, the transition state, and the products. Note that the initial product is the salt
of an amine (RNH+ Br-) which is deprotonated by the excess ammonia to give the amine.
(c) Show another SN2 reaction using a different combination of an alkoxide and an alkyl
bromide that also produces 1-methoxybutane.
(a) Rate = K [CH4H9Br][NaOCH3]

= (0.1 L mol-1 sec-1) (0.1 mol L-1) (2.0 mol L-1)

= 0.02 moleL-1. Sec-1 2

H
(b)   H
NH3 Br H N C Br N 1
1 H H HH
H
1
NH3
H
1 N
H
Br
ONa O
(c)
alkoxide alkylbromine Ether
1 1 1
Students can give their own structures

/1 10. Rank the following carbocations in decreasing order of their stability.

CH3 CH2 CH2 CH3 CH3
 CH3 CH2 CH3 CH3 CH2

> > > > 1

/2 11. Because the SN1 reaction goes through a flat carbocation, we might expect an
optically active starting material to give a completely racemized product. In most cases,
however, SN1 reactions actually give more of the inversion product. In general, as the
stability of the carbocation increases, the excess inversion product decreases. Extremely
stable carbocations give completely racemic products. Explain these observations.
Two related factors could explain this observation:
1. As the carbocation stability increases, the leaving group will be less tightly held by the
carbocation for stabilization., the more stable carbocations are more ‘’free’’ in solution,
meaning more exposed. 1
2. More the carbocation will have longer lifetimes, allowing the leaving group to drift off
in the solvent, leading to more possibility for the incoming nucleophile to attack from
the side that the leaving group just left. 1
The less stable carbocations hold tightly to their leaving groups, preventing nucleophiles
from attacking this side. Backside attack with inversions the preferred stereochemical
route in this case

/3 12. Design an alkyl halide that will give only 2,4-diphenylpent-2-ene upon treatment with
potassium tert-butoxide (a bulky base that promotes E2 elimination).

1
(CH3)3OK

Br 1 1
/3 13. For each molecular formula below, draw all the possible cyclic constitutional isomers
of alcohols. Give the IUPAC name for each of them.
(a) C3H4O

OH and OH
O O
CH2 2
(b) C3H6O

1
O
OH

/4 14. Predict which member of each pair will be more acidic. Explain your answers.
(a) methanol or tert-butyl alcohol
Methanol is more acidic than tert-butyl alcohol. The greater the substitution, the lower the

1
acidity.
(b) 2-chloropropan-1-ol or 3-chloropropan-1-ol
2-Chloropropan-1-ol is more acidic because the electron-withdrawing chlorine atom is
closer to the OH group than in 3-chloropropan-1-ol. 1
(c) 2-chloroethanol or 2,2-dichloroethanol
2,2-dichloroethanol is more acidic because two electron-withdrawing chlorine atoms
increase acidity more than just the one chlorine in 2-chloroethanol. 1
(d) 2,2-dichloropropan-1-ol or 2,2-difluoropropan-1-ol
2,2-difluoropropan-1-ol is more acidic because fluorine is more electronegative than
chlorine; the stronger the electron-withdrawing, the more acidic the alcohol. 1

/3 15. Show how you would synthesize the following alcohol from compounds containing no
more than five carbon atoms.

OH
 This is a tertiary alcohol; any one of the three alkyl groups might be added in the form of
a Grignard reagent. We can propose three combinations of Grignard reagents with
ketones:
O OH
+
H3O CH2CH3
MgBr + H3C
1 1
CH3
1 CH3

/6 16. Show how you would use Grignard syntheses to prepare the following alcohols from
the indicated starting materials and any other necessary reagents.
(a) cyclopentylphenylmethanol from benzaldehyde

O MgI HO
H3O+

1 1
1
O
(b) OH from
O
O CH3
H3O+
OCH2CH3 2 CH3MgI OH
1 1 1 CH3

/6 17. Show how you would synthesize the following compound from any starting material
containing no more than six carbon atoms.

Two synthetic routes are possible to prepare this unsaturated hydrocarbon.

Route 1
 O
OH
Br Mg1 MgBr 1 H2SO4

1 Ether
1 1 heat1
H3O+
Route 2

BrMg
Br OH H2SO4
1
Mg
H3O+
1
heat
1 ether
1 O
1
1

/6 18. Compound A (C7H11Br) is treated with magnesium in ether to give B (C7H11MgBr)

which reacts violently with D2O to give 1-methylcyclohexene with a deuterium atom on
the methyl group (C). Reaction of B with acetone followed by hydrolysis gives D
(C10H18O). Heating D with concentrated H2SO4 gives E (C10H16), which decolorizes two
equivalents of Br2 to give F (C10H16Br4). E undergoes hydrogenation with excess of H2
and a Pt catalyst to give isobutylcyclohexane. Determine the structures of compounds A
through F by showing clearly all the reactions involved.

BrMg D
Br
Mg D2O

Ether
O 1+
B
C 1 excess
of H2
A
1 H3O Pt
Br
Br
OH Br
H2SO4 Br
2 Br2

1
heat
1 1
D E F
/5 19. Many hunting dogs enjoy standing nose-to-nose with a skunk while barking furiously,
oblivious to the skunk spray directed toward them. One moderately effective way of
lessening the amount of odor is to wash the dog in a bath containing dilute hydrogen
peroxide, sodium bicarbonate, and some mild dish detergent. Use chemical reactions to
describe how this mixture helps to remove the skunk spray from the dog. The two major
components of skunk oil are 3-methylbutane-1-thiol and but-2-ene-1-thiol. (This
question need personal research).

The most important component in the deskunking mixiture is hydrogen peroxide. Thiols
are oxidized to structures having one, two, or three oxygens on the sulfur; all of these
functional groups are acidic, less volatile so they don’t reach the nose, and less stinky.
The sodium bicarbonate is basic enough to ionize these acids, making them water soluble
where the soap can wash them away.

H2O2 H2O2
Route 1 O
SH S
O
H 1 1
S H
1 1 O
H2O2

O
1
O
S H
1 O
H2O2 H2O2
Route 2 O O
1 1
SH S H
1
S H
1 O
H2O2

O
S
O
H 1
O

/6 20. Some alcohols undergo rearrangement or other unwanted side reactions when they
dehydrate in acid. Alcohols may be dehydrated under mildly basic conditions using
 phosphorus oxychloride (POCl3) in pyridine. The alcohol reacts with phosphorus
oxychloride much like it reacts with tosyl chloride, displacing a chloride ion from
phosphorus to give an alkyl dichlorophosphate ester. The dichlorophosphate group is an
outstanding leaving group. Pyridine reacts as a base with the dichlorophosphate ester to
give an E2 elimination. Propose a reasonable mechanism for the dehydration of 2-
methylcyclohexanol by POCl3 in pyridine.

1 1
1 O H O
N
O
H
N
P O P Cl O P Cl
O Cl Cl
1
H Cl Cl Cl
H
1 N

H
O N
O P Cl
Cl 1

/8 21. Develop syntheses for the following compounds. As starting materials, you may use
cyclopentanol, alcohols containing no more than four carbon atoms, and any common
reagents and solvents.
OCH3
CH3

O OMgBr
1 Mg MgBr 1
1
Br O
PBr3 CH3I
OH ether 1 1
1 1 1
0.5 H3O
+
or
OH
O 0.5
CH3OH

H2SO4