Organic Chemistry Mechanistic Patterns Canadian 1st Edition Ogilvie Solutions Manual 1

Organic Chemistry Mechanistic Patterns
Canadian 1st Edition Ogilvie Solutions

Manual
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Chapter 5
Organic Reaction Mechanisms:
Using Curved Arrows to Analyze Reaction Mechanisms
CHECKPOINT PROBLEMS
Practice Problem 5.1
a)
b) Note: the carbamate functional group is not included in Table 2.1.
Ketones (circled with lone pairs added) Amines (circled with lone pairs added)
O O
N NH N NH
H 2N O O
H 2N
O O
O O
H2N O H2N O
Alkenes Other groups (labelled and

(circled) circled with lone pairs
added)
O O
N NH
N NH
H 2N O
H 2N O
O
O O ether
O carbamate
(see H2N O
H2N O note)
5-2
Copyright © 2018 Nelson Education Limited Copyright © 2018 Nelson Education Limited
5-2
c) Esters (circled and lone pairs added) Alcohols (circled and lone pairs added)
O O
O O OH O O OH
O NH O O NH O
O H O O O
H
OH OH O O O
OH OH O
O O O
O
Phenyls (circled) Other groups (labelled and circled with

lone pairs added)
O amide
alkene ketone
O O OH
O
O O OH
O N O
O O O NH O
H
OH OH O O
O H O
O OH OH O O
O
O O ether
Integrate the Skill 5.2

There are many possible answers to the question. One is shown below.
5-3
5-3
a) Here, both of the bonding electrons go to nitrogen. The bond was formally one electron from
N and one from C. Since both are now on N, the nitrogen has gained an electron and the
carbon has lost an electron, leading to the final charge location on C.
b) The hydroxide ion contributes both electrons in forming the new C–O bond and so has
formally lost a valence electron. The carbon still has four valence electrons and so remains
neutral. The carbonyl oxygen gained a valence electron, as it is no longer sharing the bond
electron with carbon, and is negatively charged.
c) The new bond introduces charges on the boron and oxygen atoms, as indicated.
d) A new C–H bond forms from the CH3⊝ lone pair electrons and the broken C–H bond
electrons end up on the alkyne carbon.
5-4
5-4
e) The Cl⊝ removes an H to make HCl. The C–H bond electrons make a new π bond.
f) A new C–H bond forms by formal addition of H⊝ to the C=O carbon.

a) The product is incorrect. A benzene ring and HBr would form, as in part (e) of Practice
Problem 5.3.
b) The mechanism was missing the arrow for movement of the C=N double bond electrons to
the N atom.
c) The lone pair electrons on O make the bond to H. The arrow was pointing in the wrong
direction. As well, adding lone pair electrons on the O is recommended when one is just
getting started working with mechanisms.
5-5
5-5
Practice Problems 5.5
a)
b)
c)
d)
5-6
5-6
e)
a)
b)
5-7
5-7
a) Intermolecular reaction
b) Intramolecular reaction
c) Intramolecular reaction
d) Intermolecular reaction

a) This reaction is intramolecular. Two chirality centres are created in the product.
5-8
5-8
b) This is an intermolecular reaction. Two chirality centres are produced in the product.
c) This is an intramolecular reaction. There are five chirality centres formed in the product.

a) This molecule has a lone pair beside a carbocation, leading to the resonance forms indicated
below.
b) No resonance is possible because the charge is isolated from the double bond by a saturated
CH2 group.
c) No resonance is possible because the charge is isolated from the double bond by a saturated
CH2 group.
5-9
5-9
d) No resonance is possible because the lone pair is isolated from the double bond by a
saturated carbon atom.
e) The charge is adjacent to two π systems, resulting in the following possible resonance forms.
f) The electrons adjacent to the charge lead to the following resonance forms.

a) The oxygen lone pairs can enter into resonance with the ring π–electron system.
The result of this resonance is to give some negative character to the ortho and para
positions in the ring. These will be attracted to positive charges. As well, the lone pairs on
the oxygen atom will be attracted to positive charges.
b) The molecule has possible resonance due to the lone pair being next to a π bond, leading to
the following resonance forms.
The form on the right has a formal negative charge on the oxygen, making it most attractive
to positive charges.
5-10
5-10
c) The oxygen lone pair next to a double bond can enter into resonance, as shown.
This results in a formal negative charge on the carbon indicated, which would be attracted to
positive charges. The lone pairs will be attracted to positive charges as well.

a) The major difference in these forms is the location of the negative charge. It will be more
stable on the most electronegative atom, which is N in this case.
b) The presence and separation of charges is the major factor distinguishing these forms.
O O O
least favourable: intermediate: most favourable:

charges charges adjacent no charges
further apart
c) The least favourable form has the negative charge on the least electronegative atom, C. The
other two structures have similar π systems, and so the charge on O would be equal in quality.
5-11
5-11
d) Because the bonding in each is the same, the two resonance forms on the right are of equal
importance in describing the bonding in the molecule. All atoms in these two resonance
forms have filled valence orbitals. The resonance structure on the left, with an empty
valence orbital on the carbon atom, will be of less importance than the other two.
e) The first two resonance forms each have a carbon atom with an empty valence orbital; so the
third resonance form, with each atom having all orbitals filled, will be the most important
contributor to the bonding. The carbon atom having the positive charge in the first resonance
form is positioned further from the electronegative O atom. This will be a more important
contributor to the bonding than the middle resonance form in which the carbon atom bearing
the positive charge is adjacent to the O atom.
intermediate: positive charge

further from electronegative O
O Br O Br O Br
least important: positive charge most important: all

closer to electronegative O atoms full octets

The ring electrons react with the bromine molecule, producing a positively charged intermediate
and a bromide ion.
5-12
5-12
The two main determinants of the relative contribution of each resonance form are whether the
atoms have filled or empty valence orbitals and the location of the positive charge in the
intermediate.

a) There are three apparent groupings, shown below.
Lone pair adjacent to p bond p-bonded heteroatom

beside C–C p bond
O N
O
N
D B
A F
Lone pair adjacent to 2 p bonds
NH
H
O
C E G
5-13
5-13
b) Lone pair adjacent to p bond
N N
H H
O O
p-bonded heteroatom beside C–C p bond
O H O H O H
N N N
H H H H H H
Lone pair adjacent to 2 p bonds
H H H
N N N CH2
O O O CH2
H H
5-14
5-14
Integrate the Skill
5.14
a) The basic form is a double bond beside a heteroatom with lone pairs.
b) These each have a double-bonded hetereoatom with an adjacent C–C double bond.
5-15
5-15
PROBLEMS
5.15
Answers to (a) through (h) are labelled in the diagram below.
5.16
a) e)
b) f)
c) g)
d) h)
5-16
5-16
5.17
5.18
a)
b)
c)
d)
5-17
5-17
5.19
a)
b)
c)
d)
e)
5.20
a) Intermolecular d) Intermolecular
b) Intermolecular e) Intramolecular
c) Intramolecular
5-18
5-18
5.21
a)
b)
c)
d)
e)
f)
g)
h)
5-19
5-19
5.22
a)
b)
c)
d)
e)
f)
g)
h)
i)
5-20
5-20
5.23
a)
b)
c)
d)
5.24
a)
b)
c)
d)
e)
5-21
5-21
5.25
The diagram below shows the missing curved arrows, lone pairs, and formal charges for the
reactions. As well, the steps have been classified as intra- or intermolecular.
STEP 1: Intermolecular
OH + H Cl OH2 + Cl
STEP 2: Intramolecular
OH2 + Cl H + H2 O + Cl
STEP 3: Intramolecular
H + H2 O + H2O + Cl
+ Cl H
STEP 4: Intermolecular
+ H2O + Cl + H3O + Cl
5.26
a)
b)
5-22
5-22
c)
d)
5.27
a) The H–Cl bond electrons need to move to the Cl atom to produce a chloride ion. This has
been fixed below.
b) The added sidechain should have a charge, since it has contributed both electrons in the new
bond. This is fixed in the diagram below.
c) The C–H bond electrons form a new C–C bond and a new H–Cl bond is formed with a lone
pair of electrons from the chlorine atom. The correct reaction is shown below.
d) The reaction arrow is drawn backward. The electron flow is from the double bond to the
incoming H . This is corrected below.
5-23
5-23
e) The new bond is formed between the carbonyl carbon and the incoming hydroxide ion, not
with the carbonyl oxygen atom. Corrected below.
f) The flow of electrons was reversed. The arrows are correctly redrawn below.
5.28
a)
b)
c)
d)
5-24
5-24
5.29
a) Two structures expected
b) Five structures expected
c) Four structures expected
d) Seven structures expected
e) Four structures expected
5-25
5-25
5.30
a)
b)
c)
d)
e)
f)
g)
5-26
5-26
5.31
a) Resonance forms having atoms with all valence orbitals filled will contribute more to the
resonance hybrid than those in which atoms have an empty orbital.
b) The resonance form with the negative formal charge on the electronegative nitrogen atom is
a greater contributor than the one with the negative charge on carbon.
c) The most important resonance form has no charges. The second most important has all
orbitals filled with the negative charge on O. The third has all orbitals filled with the
negative charge on C. The least important resonance form has an empty orbital on the
C atom.
5-27
5-27
d) The most important resonance form has no charges. The second most important has all
orbitals filled. Both the third most important and the least important have an empty orbital
on a C atom. The least important has the positive formal charge on the carbon atom adjacent
to the negative formal charge.
e) All structures are identical and therefore equally ranked.
f) There are three resonance forms that are equally the most important contributors. They are
equal because they differ only in the position of the C=N π bond. They are the most
important because all valence orbitals are filled. The remaining resonance form is least
important because it has an empty orbital on the C atom.
5-28
5-28
g) The most important resonance forms have the least number of formal charges. The positive
formal charge in the ring of the second most important resonance form has greater
separation from the positive formal charge on the –NO2 nitrogen atom than in the two
equivalent least important resonance forms.
O O O O O O O O O O
N N N N N
H H
H
Rank: 1 1 3 2 3
5.32
a) Structure B has electrons moving from oxygen to carbon, leaving a positive charge on O and
a negative on C next to each other. This is highly unlikely.
O O
insignificant.
N N
A B
O O O
N N N
A C D
b) Structure D is not important because it contains several formal charges.
5-29
5-29
c) Structures D and E are unimportant due to their large number of formal charges.
d) Resonance forms C and D are unlikely contributors. Structure C has a nitrogen with an
empty orbital and structure D has several formal charges, including negative charges on
adjacent atoms.
e) C and D are not important contributors because they imply charge separation between two
atoms of the same electronegativity.
5-30
5-30
5.33
a)
The circled structure would be more stable, as it is capable of delocalizing the positive
charge via resonance.
b)
The circled structure is more stable, as it has available resonance forms. The charge on the
other is isolated from the double bond by a saturated CH2 group.
c)
The circled structure would be more stable, since the negative charge is delocalized by
resonance.
5-31
5-31
d)
The negative charge in the circled structure is extensively delocalized, making it the most
stable ion.
5.34
a) The arrows were backward and incomplete. The negative charge is moved and displaces a π
bond in each shift. The correct arrows are shown below.
b) The student missed one important resonance form and did not recognize that the resonance
form labelled as the most significant is, in fact, the least significant because its C atom has
an empty valence orbital. All valence orbitals are filled in the other three (equivalent)
resonance forms.
5-32
5-32
c) The resonance forms drawn by the student would be unimportant. The important resonance
forms would place a negative charge on O and positive charge on C.
d) The third resonance form is impossible as the end carbon already has four bonds and cannot
accept any more electrons. There are only two resonance forms.
e) There was a missing arrow shift in the first structure.
f) The mechanistic arrows were all improperly drawn. The correct ones are shown below.
5-33
5-33
5.35
There are three different groupings based on similar resonance patterns.
Group 1
Group 2
5-34
5-34
Group 3
5.36
a) An electron donor would react at the empty orbital of carbon seen in its second resonance
form.
b) An electron donor would react at the empty orbital of carbon seen in its second resonance
form.
5-35
5-35
c) An electron donor would react at the empty orbital of carbon seen in its second resonance
form.
d) The resonance forms for this molecule show that there are three possible reaction sites, all of
which are carbon atoms with an empty orbital. Since they are all secondary carbons, they are
all approximately equally likely to react with an electron pair donor.
e) The second resonance form has a carbon atom with an empty orbital. This could react with
an incoming nucleophile.
f) There are three distinct sites of reaction with nucleophiles. All are carbon atoms with an
empty orbital.
5-36
5-36
5.37
a)
b)
c)
d)
e)
f)
5-37
5-37
5.38
Nucleophilic sites would react with electron-poor species. Electrophilic sites would react with
electron-rich species.
a)
b)
c)
d)
e) All the heteroatoms with lone pairs are nucleophilic.
5-38
5-38
f)
g)
MCAT Style Problems

5.39
There are 10 lone pairs, or 20 nonbonding electrons. The correct answer is (d).
5.40
Answer: (d).
a) Error: The charge is on the N, not the carbon.
b) Error: The ring formed should be six-membered not five-membered.
c) Error: One of the arrows has a head on each end.
5.41
The answer is (b). There are three resonance structures, shown below.
5-39
5-39
5.42
The answer is (c). The resonance forms for aniline are shown below.
Challenge Problem
5.43
a) The resonance form D is not possible. The p orbitals are constrained by the rigid ring
structure and cannot align to overlap and form a π bond with the adjacent C atom.
O
D
p orbitals are perpendicular;

no overlap possible
b) Similar to part (a). The lone pair on the N atom sits in an sp2 hybridized orbital that lies
perpendicular to the p orbitals of the ring, so overlap with them to establish π bonding is not
possible. The lone p orbital on N that can form π bonds with the ring carbon atoms is already
doing so.
sp2 lone pair perpendicular

to p orbitals of the ring
5-40
5-40

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Organic Chemistry Mechanistic Patterns

Canadian 1st Edition Ogilvie Solutions

Practice Problem 5.1

Alkenes Other groups (labelled and

Phenyls (circled) Other groups (labelled and circled with

Integrate the Skill 5.2

f) A new C–H bond forms by formal addition of H⊝ to the C=O carbon.

Integrate the Skill 5.4

Integrate the Skill 5.6

Integrate the Skill 5.8

Practice Problem 5.9

Integrate the Skill 5.10

Practice Problem 5.11

least favourable: intermediate: most favourable:

intermediate: positive charge

least important: positive charge most important: all

Integrate the Skill 5.12

Practice Problem 5.13

Lone pair adjacent to p bond p-bonded heteroatom

Lone pair adjacent to 2 p bonds

p-bonded heteroatom beside C–C p bond

Lone pair adjacent to 2 p bonds

a) Two structures expected

b) Five structures expected

c) Four structures expected

d) Seven structures expected

e) Four structures expected

e) All structures are identical and therefore equally ranked.

b) Structure D is not important because it contains several formal charges.

e) There was a missing arrow shift in the first structure.

e) All the heteroatoms with lone pairs are nucleophilic.

MCAT Style Problems

p orbitals are perpendicular;

sp2 lone pair perpendicular

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