Organic Chemistry Mechanistic Patterns Canadian 1St Edition Ogilvie Solutions Manual Full Chapter PDF

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
Another random document with
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General description and date of
structure.
The front room on the first floor has a well designed plaster
ceiling (Plate 79), the wall frieze being enriched with griffins, of a
slightly different type to those in No. 11. The chimneypiece is of white
marble with a central decorative panel.
The rear room on the same floor has also an ornamental
plaster ceiling of very simple design, and the white marble
chimneypiece is inlaid with Siena marble.
Condition of repair.
The premises are in good repair.
Biographical notes.
According to the ratebooks the first occupant of the house was Thos.
Hibbart, who resided there during 1780 and 1781. He was followed by Jas.
Bailey from 1782 to 1793, and from the latter year, Sir Alexander Monro was
in occupation.
In the Council’s collection are the
following:—
[734]Ornamental plaster ceiling in front room on first floor
(photograph).
Marble chimneypiece in front room on first floor (photograph).
Ornamental plaster ceiling in rear room on first floor (photograph).
LXXVI.—No. 15, BEDFORD SQUARE.
Ground landlord and lessee.
Ground landlord, His Grace the Duke of Bedford, K.G.;
lessees, the Associated Board of the Royal Academy of Music and the
Royal College of Music for Local Examinations in Music.
structure.
The front doorway (Plate 80), with its decorative leadwork
fanlight, is a typical example of the majority in the square.
The first floor front room has an ornamental plaster ceiling,
somewhat similar to others already noticed. There is an interesting
plaster cornice in the rear room of the same floor, and a carved
marble chimney piece on the second floor.
Biographical notes.
The occupants of this house, according to the ratebooks, were as
follows:—
1780–81. —— Pole.
1784–90. John Cologan.
1790–94. Jno. Stephenson.
1794–95. Mrs. Stephenson.
1795–98. Robt. Tubbs.
1798– Jas. Williams.
In the Council’s collection are:—
[735]Entrance
doorway (photograph).
Ornamental plaster ceiling in front room on first floor (photograph).
Marble chimneypiece in front room on second floor (photograph).
LXXVII.—No. 18, BEDFORD SQUARE.
Ground landlord and lessee.
Ground landlord, His Grace the Duke of Bedford, K.G.; lessee,
Herbert Sefton-Jones, Esq.
structure.
This house forms the eastern half of the central feature on the
north side of the square. Its interior has been considerably altered,
but the original carved white marble chimneypiece shown on Plate
81 still remains.
The motif of the central panel is similar to that at No. 11, but is
not quite so gracefully expressed. The shelf appears to be a modern
substitute, and out of harmony with the requirements of the design.
Biographical notes.
The earliest occupier of this house was, according to the ratebooks,
the Rev. Frederick Hamilton, who resided there from 1784 to 1786. In the
latter year he was succeeded by Thos. Hankey, who remained at the house
until after the close of the century.
In the Council’s collection is:—
[736]Marble chimneypiece in front room on ground floor
(photograph).
LXXVIII.—No. 23, BEDFORD SQUARE.
Ground landlord.
His Grace the Duke of Bedford, K.G.
structure.
This house was not in existence on 20th November, 1777,[737]
and the first mention of it in the parish ratebooks occurs in 1781. Few
of the decorations in the house are original, the two principal
exceptions being the plaster ceiling of the front room on the first
floor, and a fine doorcase and pair of doors (Plate 82), connecting
that room with the one in the rear.

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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

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