연습문제 Solution

CHAPTER 1—STRUCTURE AND BONDING
1-1
(a) Nitrogen has atomic number 7, so all nitrogen atoms have 7 protons. The mass number is the total
number of neutrons and protons; therefore, 13N has 6 neutrons, 14N has 7 neutrons, 15N has 8 neutrons, 16N
has 9 neutrons, and 17N has 10 neutrons.
(b) Na 1s22s22p63s1 P 1s22s22p63s23p 13p 13p 1 x y z
Mg 1s22s22p63s2 S 1s22s22p63s23px23py13pz1
Al 1s22s22p63s23px1 Cl 1s22s22p63s23px23py23pz1
Si 1s22s22p63s23px13py1 Ar 1s22s22p63s23px23py23pz2
1-2 Lines between atom symbols represent covalent bonds between those atoms. Nonbonding electrons are
indicated with dots. H H H
(a) H N H (b) H O H (c) H O H (d) H C C C H
H H H H H
H H H H H H H H H
(e) H C N C H (f) H C C O C C H (g) H C C C Cl
H H H H H H H H H H
H
(i) H B H (j) F B F
H O H
H F
(h) H C C C H The compounds in (i) and (j) are unusual in that boron
does not have an octet of electrons—normal for boron
H H H because it has only three valence electrons.
1-3
(a) N N (b) H C N (c) H O N O (d) O C O
H O
(e) H C C N H (f) H C O H (g) H C C Cl (h) H N N H

H H H H H H
(i) H C C C H (j) H C C C H (k) H C C C H
H H H H H H
1-4 There are no unshared electron pairs in parts (i), (j), and (k).
(a) N N (b) H C N (c) H O N O (d) O C O
H O
(e) H C C N H (f) H C O H (g) H C C Cl (h) H N N H
H H H H
1
Copyright © 2017 Pearson Education, Ltd.
1-5 The symbols "δ+" and "δ–" indicate bond polarity by showing partial charge. (In the arrow
symbolism, the arrow should point to the partial negative charge.)
δ+ δ− δ+ δ− δ− δ+ δ+ δ− δ+ δ−
(a) C Br (b) C l (c) C Si (d) B Cl (e) B F
δ+ δ− δ+ δ− δ+ δ− δ+ δ−
(f) N F (g) N Br (h) Si Br (i) Si Cl (j) Si F
no assignment - same electronegativity
1-6 Non-zero formal charges are shown beside the atoms, circled for clarity. H H
H
H H C
H H
(a) H C O H (b) H N H Cl (c) H C N C H Cl
H H
H H H C
In (b) and (c), the chlorine is present as chloride H H
ion. There is no covalent bond between chloride H
and other atoms in the formula.
H H
(d) Na O C H (e) H C H (f) H C H (g) Na H B H

H H H H
H H
H H
(h) Na H B C N (i) H C O C H (j) H O N H
H H
H H
F B F
H
H H F As shown in (d), (g), (h), and (k),
C alkali metals like sodium and
H
potassium form only ionic bonds,
(k) K O C C H (l) H C O H never covalent bonds.
H
C H
H
H
H
1-7 Resonance forms in which all atoms have full octets are the most significant contributors. In resonance
forms, ALL ATOMS KEEP THEIR POSITIONS—ONLY ELECTRONS ARE SHOWN IN DIFFERENT
POSITIONS. (In this Solutions Manual, braces {} are commonly used to denote resonance forms.)
One more helpful hint when drawing resonance forms of structures with charges: move electrons toward
(+) charges and away from (–) charges. Arrows show how to alter one structure to make it into the next
one. In Chapter 1, arrows in resonance forms are the same as the green arrows in the text.
O O O Move electrons away

(a) from (–) charge.
O C O O C O O C O
H C C C H H C C C H
(b) Move electrons toward (+) charge.
H H H H H H
2
1-7 continued
(c) H C C C H H C C C H Move electrons away from (–) charge.

H H H H H H
O O O
Move electrons away
(d)
O N O O N O O N O from (–) charge.
Look how similar part (d) is to part (a) above. They are "isoelectronic", meaning the same number of electrons.
(e) O N O O N O Move electrons away from (–) charge.
O O O
(f) H C C C C H H C C C C H H C C C C H
H H H H H H H H H
Move electrons away from (–) charge.
(g) There are three resonance forms shown here; the structure given in the problem ("original") is
shown twice because the electrons can be delocalized in two different directions; each of the other
structures is derived from the original.
H H H H
H C H H C H H C H H C H
H O H O H O H O
H C C H C C H C C H C C
H O H O H O H O
H C H H C H H C H H C H
original H H original H H
Move electrons toward (+) charge. Move electrons toward (+) charge.
(h) In similar fashion to part (g), the three other resonance forms are derived from the first. In this solution,
however, for simplicity, only the first structure has the arrow showing how the first structure can be made
into the second. It should be apparent to you to see how to make the first structure into the third and fourth.
Alternatively, you can transform the second into the third directly by using two arrows.
It is very important to keep in mind that these arrows are simply helpful devices to make one picture into
another. They do not mean that electrons are moving! There is one real chemical species that is an average
of all the individual resonance forms which are just pictures.
H H H H
O O O O
H B H H B H H B H H B H
O O O O O O O O
3
1-8 Major resonance contributors would have the lowest energy. The most important factors are: maximize
full octets; maximize number of bonds; put negative charge on electronegative atoms; minimize charge
separation— see the Problem-Solving Hint above Solved Problem 1-2. Part (a) has been solved in the text.
(b) H C C N H C C N The second structure has negative charge

on the more electronegative atom.
H H
minor major
H H
(c) The first structure has full
H C O C H H C O C H
octets and one more bond.
H H H H
major minor
All atoms have octets;
same number of bonds;
(d) H C N O H C N O H C N O third structure has both
(–) charges on the more
H O H O H O electronegative oxygen
minor minor major atoms instead of carbon.
H H H
O O O The latter two
structures have
(e) H C H H C H H C H equivalent energy and
C O C O C O are major because they
H H H have full octets and
H H H more bonds.
minor major major
The first structure has the negative

(f) H C C N H H C C N H charge on the more electronegative
nitrogen atom.
H H H H
major minor
(g) There are three resonance forms shown here; the structure given in the problem ("original") is
shown twice in order to demonstrate how each of the other structures is derived from the original.
O O O O
H C C C H H C C C H
original H H The latter two structures have

minor major equivalent energy and are major
because the negative charge is on the
more electronegative oxygen atom
O O O O rather than on the less electronegative
carbon atom.
H C C C H H C C C H
original H H
minor major
4
1-8 continued
(h) There are three resonance forms shown here; the structure given in the problem ("original") is shown
twice in order to demonstrate how each of the other structures is derived from the original.
All three resonance forms have full octets and the same number of bonds. The second structure is the
most significant contributor because the negative charge is on the oxygen (most electronegative); the third
structure with negative charge on nitrogen is next; the least significant contributor is the first structure
("original") with negative charge on the least electronegative carbon atom.
O O
H C C C N H C C C N Move electrons away from (–) charge.
original H minor H major
O O
H C C C N H C C C N
original H minor H major
1-9
(a) There are four resonance forms shown here; the structure given in the problem ("original") is shown
twice in order to demonstrate how each of the other structures is derived from the original.
O H O H
Move electrons
H3C O C C C N H H3C O C C C N H
toward (+) charge.
original H H H H H H
major—full octets
O H O H
H3C O C C C N H H3C O C C C N H
original
H H H H H H
O H
H3C O C C C N H
H H H
major—full octets
Although the O and N have (+) charges in these major resonance forms, their full octets are
more important than charge in determining the significance of their contribution to the resonance
hybrid.
5
1-9 continued
(b) There are five resonance forms shown here; one of the structures is duplicated to show how the other
resonance forms are derived from it. Resonance forms with all atoms having their full octets are the most
significant contributors. In this case, the ones with full octets also have more bonds.
H this structure H
O repeated below O
H N C C C O CH3 H N C C C O CH3
Move electrons
H H H major—full octets H H H toward (+) charge.
H H
O O
H H H major—full octets H H H
H H
O O
H H H H H H major—full octets
this structure
repeated from above
(c) There are four resonance forms shown here; one of the structures is duplicated to show how the other
resonance forms are derived from it. Resonance forms with all atoms having their full octets are the most
significant contributors. In this case, the ones with full octets also have more bonds.
H N H this structure H N H
repeated below
Move electrons
H C C C O H H C C C O H toward (+) charge.
H H H H
major—
full octets
H N H
H C C C O H
H H major—full octets
H N H H N H
H C C C O H H C C C O H
H H H H
this structure
repeated from above 6
1-9 continued
(d) The lone pair of electrons on C cannot be delocalized to the C=C or the triple bond.
O O Move electrons
H3C C C C C C N H3C C C C C C N away from (–)
charge.
H H H H H H
major—negative charge on the
more electronegative atom
(e) There are four resonance forms shown here; the original structure is duplicated to show how the other
resonance forms are derived from it.
O this structure O Move electrons
repeated below away from (–)
H3C C C C C C N H3C C C C C C N charge.
H H H H H H
major—negative charge on
the more electronegative atom
O O
H3C C C C C C N H3C C C C C C N
H H H H H H
this structure
repeated from above
H3C C C C C C N
H H H
the more electronegative atom
(f) The lone pair of electrons on C cannot be delocalized to the C=C.
H N H N
Move electrons away
H C C C C H H C C C C H from (–) charge.
H H H H H H
7
1-10 Resonance structures depict the distribution of electrons around the molecule. The significant
resonance contributors suggest the areas of highest and lowest electron density.
O O O
(a) H C C N O H C C N O H C C N O
H H H H H H
lower electron density O higher electron density Although the N has a (+) charge in all
resonance forms, it still has an octet and is
H C C N O not as electron-deficient as the CH2 in the
form where the CH2 bears a (+) charge.
H H
(b) H C C C N H C C C N H C C C N
H H H H minor H H minor
lower electron density higher electron density
H C C C N
H H
O O O
(c) H C N H H C N H H C N H
H H H
minor
higher electron density
O
H C N H
H lower electron density
O O O
(d)
H C O CH3 H C O CH3 H C O CH3
minor higher electron density

O
H C O CH3
lower electron density
8
1-10 continued
O O O
(e) H C C C N H H C C C N H H C C C N H
H H H H H H H H H
minor minor
higher lower electron density

O
electron
density H C C C N H O
H H H H C C C N H
H H H
(f) H3C O C C C N H3C O C C C N
H H H H minor
H3C O C C C N H3C O C C C N
H H H H minor

H3C O C C C N
H H
1-11 Your Lewis structures may appear different from how these are drawn. As long as the atoms are
connected in the same order and by the same type of bond, they are equivalent structures. For now, the
exact placement of the atoms on the page is not significant. A Lewis structure is "complete" with
unshared electron pairs shown.
H H H H H H H H H H H O
(a) H C C C C C C H (b) H C C C Cl (c) H C C C C N
H H H H C H H C H H H
H H H H
H H
Always be alert for the implied double or triple bond. Remember that the normal valence of C is four bonds,
nitrogen has three bonds, oxygen has two bonds, and hydrogen has one bond. The only exceptions to these
valence rules are structures with formal charges. (We will see other unusual exceptions in later chapters.)
9
1-11 continued H
H H
H O H C O H H O O
(d) C C C H (e) H C C C C C (f) H C C C O H

H H H C H H H
H H
H
H
H H O H H H O H
(g) H C C C C C H (h) H C C C H
H H H H H C H
H H
H
1-12 Complete Lewis structures display all atoms, bonds, and unshared electron pairs.
H H
(a) H (b) H H (c) H H
H H H
H H C C H
C C H C C
H H C
H C C H
H C H C C
C C
H C C H H N H
H H H
N H C C H
H H
C6H13N H O H C8H16O C4H5N
H
O
(d) H H (e) H H (f) H H
H H H C C H C
C C O
H C C H H C C
H O H
C C
C5H10O H C C C7H10O H C C C6H8O
H C H C H C H
H H
H H H H
H
H O H
(g) H C C C H (h) H O H H H
C C
H H C C C C C H
C C C8H8O C5H10O
H C H H H H H
1-13 Line-angle structures, sometimes called "stick" figures, usually omit unshared electron pairs.
O O
(a) (b) Cl (c) C4H5NO (d) C3H4O
C7H16 C4H9Cl C H
N
C is usually not shown but this H on C is usually not shown
clarifies what ends this triple bond. but this is an exception; it
10 clarifies what ends this chain.
1-13 continued
O O O O
(e) (f) (g)
OH
C7H12O C5H10O
O C3H4O3
better not as good
placement
OH
OH
(h) not as good
C4H10O
1-14 If the percent values do not sum to 100%, the remainder must be oxygen. Assume 100 g of sample;
percents then translate directly to grams of each element.
There are usually MANY possible structures for a molecular formula. Yours may be different from
the examples shown here and they could still be correct.
40.0 g C some possible structures:
(a) = 3.33 moles C ÷ 3.33 moles = 1 C H O H
12.0 g/mole
6.67 g H HO C C C OH
1.01 g/mole = 6.60 moles H ÷ 3.33 moles = 1.98 ≈ 2 H
H H
53.33 g O
OH
16.0 g/mole = 3.33 moles O ÷ 3.33 moles = 1 O
empirical formula = CH2O empirical weight = 30.02
molecular weight = 90, three times the empirical weight HO OH

Other structures
three times the empirical formula = molecular formula = C3H6O3 are possible.
(b) 32.0 g C some possible structures:

= 2.67 moles C ÷ 1.34 moles = 1.99 ≈ 2 C
12.0 g/mole H H
6.67 g H
1.01 g/mole = 6.60 moles H ÷ 1.34 moles = 4.93 ≈ 5 H H C C NO2
18.7 g N H H
14.0 g/mole = 1.34 moles N ÷ 1.34 moles = 1 N
42.6 g O H O H
16.0 g/mole = 2.66 moles O ÷ 1.34 moles = 1.99 ≈ 2 O
N C O C H
empirical formula = C2H5NO2 empirical weight = 75.05 H H
molecular weight = 75, same as the empirical weight MANY other structures
are possible.
empirical formula = molecular formula = C2H5NO2
11
1-14 continued
(c) 25.6 g C some possible structures:
= 2.13 moles C ÷ 1.07 moles = 1.99 ≈ 2 C
12.0 g/mole O
4.32 g H
1.01 g/mole = 4.28 moles H ÷ 1.07 moles = 4 H H C Cl
C N
37.9 g Cl H
35.45 g/mole = 1.07 moles Cl ÷ 1.07 moles = 1 Cl H
H H
15.0 g N
14.0 g/mole = 1.07 moles N ÷ 1.07 moles = 1 N Cl C O
N C H
17.2 g O H
16.0 g/mole = 1.07 moles O ÷ 1.07 moles = 1 O H H O N
H C C Cl
empirical formula = C2H4ClNO empirical weight = 93.49
H H
molecular weight = 93, same as the empirical weight MANY other structures
are possible.
empirical formula = molecular formula = C2H4ClNO
(d) 38.4 g C some possible structures:

= 3.20 moles C ÷ 1.60 moles = 2 C
12.0 g/mole H H
4.80 g H H C C C C H
1.01 g/mole = 4.75 moles H ÷ 1.60 moles = 2.97 ≈ 3 H
H Cl Cl H
56.8 g Cl
35.45 g/mole = 1.60 moles Cl ÷ 1.60 moles = 1 Cl Cl Cl
H C C H
empirical formula = C2H3Cl empirical weight = 62.45
H C C H
molecular weight = 125, twice the empirical weight
H H
twice the empirical formula = molecular formula = C4H6Cl2
MANY other structures
are possible.
1-15 The fundamental principle of organic chemistry is that a molecule's chemical and physical properties
depend on the molecule's structure: the structure-function or structure-reactivity correlation. It is essential
that you understand the three-dimensional nature of organic molecules, and there is no better device to assist
you than a molecular model set. You are strongly encouraged to use models regularly when reading the text
and working the problems.
(a) Requires use of models.
(b)
The wedge bonds represent bonds coming out of the plane of the paper
toward you.
The dashed bonds represent bonds going behind the plane of the paper.
12
1-16 (a) The hybridization of oxygen is sp3 since it has (b) The electrostatic potential map for
two sigma bonds and two pairs of nonbonding electrons. water shows that the hydrogens have
The reason that the bond angle of 104.5° is less than the low electron potential (blue), and the
perfect tetrahedral angle of 109.5° is that the lone pairs in area of the unshared electron pairs in sp3
the two sp3 orbitals are repelling each other more orbitals has high electron potential (red).
strongly than the electron pairs in the sigma bonds,
high electron potential (red)
thereby compressing the bond angle.
repulsion O
O
H H H
H compression low electron potential (blue)
1-17 Each double-bonded atom is sp2 hybridized with bond angles about 120°; geometry around sp2 atoms
is trigonal planar. In (a), all four carbons and the two hydrogens on the sp2 carbons are all in one plane.
Each carbon on the end is sp3 hybridized with tetrahedral geometry and bond angles about 109°. In (b), the
two carbons, the nitrogen, and the two hydrogens on the sp2 carbon and nitrogen are all in one plane. The
CH3 carbon is sp3 hybridized with tetrahedral geometry and bond angles about 109°.
(a) sp2 (b) sp2

H H H H
C C 120°H C N
H 120° C H
C C 120°
109.5° 109.5°
H H H H H H
sp3 sp3
1-18 The hybridization of the nitrogen and the triple-bonded carbon are sp, giving linear geometry
(C—C—N are linear) and a bond angle around the triple-bonded carbon of 180°. The CH3 carbon is
sp3 hybridized, tetrahedral, with bond angles about 109°.
sp
H
H
109.5° C C N
H 180°
sp3
1-19
O C O
(a) linear, bond angle 180°
sp2 sp sp2
(b) All atoms are sp3; tetrahedral geometry and bond angles of 109° around each atom.
H H not a bond—shows lone not a bond—shows lone pair
pair coming out of paper going behind paper
H C O C H
H O H
H H C C
H H H H
13
1-19 continued
(c) All atoms are sp3; tetrahedral geometry and bond angles of 109° around each atom.
H H H
H H
H C O C H C
H H not a bond—shows
C H O lone pair going behind paper
H H C
H C H
H H
H H
(d) trigonal planar around the carbonyl carbon (C=O), bond angles 120°; tetrahedral around the single-
bonded oxygen and the CH3, bond angles 109°
O
sp2
H O sp3 All atoms are in one
sp3 C H
H plane except for the two
H C C O H C O H atoms on the sp3 C.
H sp2 H H
3
(e) tetrahedral around the sp carbon; the other two carbons both sp, linear, bond angle 180°
sp H
H
sp3 C C C H all three carbon atoms in a line
H C C C H
H H
H
(f) trigonal planar around the sp2 carbon and nitrogen, bond angles 120°; tetrahedral geometry and 109°
bond angles around the sp3 carbons
H
sp2 H
H 3
H
H C H sp
H C C N C H
sp3 C N
H
H H sp2
H C
H
(g) linear, 180° bond angle, around the C C O
H
central carbon; trigonal planar, 120° H
bond angles, around the sp2 carbon
sp2 H sp sp2
1-20 Carbon-2 is sp hybridized. If the p orbitals making the pi bond between C-1 and C-2 are in the plane
of the paper (putting the hydrogens in front of and behind the paper), then the other p orbital on C-2 must
be perpendicular to the plane of the paper, making the pi bond between C-2 and C-3 perpendicular to the
paper. This necessarily places the hydrogens on C-3 in the plane of the paper. (Models will surely help.)
H
H 1 2 3
C C C 1 2
C C C
H 3 model of
H
sp perpendicular π bonds
14
1-21 For clarity, electrons in sigma bonds are not shown. Part (a) has been solved in the text.
(b) Carbon and oxygen are both sp2 hybridized.
H 120° H H H
120° C O C O
H (top view) H
One pair of electrons on oxygen is

H H H H always in an sp2 orbital. The other
C O C O pair of electrons is shown in a p
H H
orbital in the first resonance form, and
sp2 sp2 in a pi bond in the second resonance
empty p form.
p orbital (side view)
(c) Oxygen and both carbons are sp2 hybridized.

H 120° H
120° C O C O
H C H C
(top view)
120° H H
sp2 sp2
H H
C O C O
sp2 sp2
H C H C
p p p p
H H
(side view)
p p
15
1-21 continued
(d) All atoms are sp2 hybridized except the C labeled as sp3 (and H which is NEVER hybridized); all bond
angles around the sp3 carbon are 109°.
H O H O H O
120° 120°
C N C N C N
H H H
C 120° O C O C O
H H H
(top view)
sp3 H H H
p p
sp2 sp2
O O
sp2 sp2
H H
H C N H C N
sp2 sp2
C C
p p O p p O p
H H
H H
sp2 sp2 sp2
(side view) p p
O
sp2
H
H C N
sp2
C
p p O
H
H
sp2
(e) The nitrogen and the carbon bonded to it are sp hybridized; the left carbon is sp2. p
H 180° H
120° C C N C C N
H H
H H
C C N C C N
H sp H sp
p p
16
1-21 continued
(f) The boron and the oxygens bonded to it are sp2 hybridized.
H O H H O H H O H H O H
B O B O B O B O
H O H O H O H O
p p
sp2 sp2
empty p
H O H O
π
p
H H
B O B O
p p
sp2 sp2
H O H O
sp2 sp2
p
sp2 π
sp2
H O π p H O p
H H
B O p B O
2 sp2 sp2
H O sp H O
sp2
(g)
O O
O O O O
All oxygens are sp2 with bond angle 120°.
This electron pair is in an sp2

π orbital behind the central oxygen. π
sp2 sp2 sp2 sp2

O O
O O O O
sp2 sp2 sp2

sp2
p p
17
1-22 Very commonly in organic chemistry, we have to determine whether two structures are the same or
different, and if they are different, what structural features are different. In order for two structures to be
the same, all bonding connections have to be identical, and in the case of double bonds, the groups must
be on the same side of the double bond in both structures. (A good exercise to do with your study group
is to draw two structures and ask if they are the same; or draw one structure and ask how to draw a
different compound.)
(a) Different compounds; H and CH3 on one carbon of the double bond, and CH3 and CH2CH3 on the
other carbon—same in both structures. Drawing a plane through the p orbitals shows the H and CH3 are
on the same side of the double bond in the first structure, and the H and the CH2CH3 are on the same side
in the second structure, so they are DIFFERENT compounds.
H3C CH2CH3 H3C CH3
C C C C These are DIFFERENT.
H CH3 H CH2CH3
compare compare
(b) Same compound; in the structure on the right, the right carbon has been rotated, but the bonding is
identical between the two structures.
(c) Different compounds; H and Br on one carbon, F and Cl on the other carbon in both structures; H and
Cl on the same side of the plane through the C=C in the first structure, and H and F on the same side of
the plane through the C=C in the second structure, so they are DIFFERENT compounds.
(d) Same compound: in the structure on the right, the right carbon has been rotated 120°.
1-23 (b) CH3 CH3
N N
(a) H H H NOT INTER-
C CONVERTIBLE C
H C C N C H CH3 H CH3 H
sp3 H H sp3 two CH3 on opposite two CH3 on the same

sp2 sides of the C=N side of the C=N
(c) The CH3 on the N is on the same CH3

N
side as another CH3 no matter how it is
drawn—only one possible structure. C
CH3 CH3
1-24 F F H F
(b) no cis-trans isomerism two identical groups on one
(a) C C and C C (c) no cis-trans isomerism carbon of the double bond
H H F H (d) no cis-trans isomerism
cis trans
CH3 H
(f)
(e) CH3 H C C and C C
C C and C C H CH3
H H H CH3
cis trans These structures show cis-trans isomerism
(also known as geometric isomerism),
1-25 Models will be helpful here. although "cis" and "trans" are not defined
(a) Constitutional isomers—the carbon skeleton is different. for this particular case. A different,
(b) Cis-trans isomers—the first is trans, the second is cis. unambiguous system for naming
(c) Constitutional isomers—the bromines are on different geometric isomers will be described in
carbons in the first structure, on the same carbon in the Chapter 7.
second structure. 18
1-25 continued
(d) same compound—just flipped over
(e) same compound—just rotated
(f) same compound—just rotated
(g) not isomers—different molecular formulas
(h) Constitutional isomers—the double bond has changed position.
(i) same compound—just reversed
(j) Constitutional isomers—the CH3 groups are in different relative positions.
(k) Constitutional isomers—the double bond is in a different position relative to the CH3 and an H has moved.
1-26
(a)
(b)
(c) The first resonance form of CO2 has no equivalent form in O3. Oxygen, a second row element, does not
have d orbitals, so it must adhere strictly to the octet rule.
1-27 (a) Sodium (b) Neon (c) Boron (d) Magnesium

1-28
valence e− 1 2 3 4 5 6 7 8
H He (2e− )
Li Be B C N O F Ne
P S Cl
Br
I
1-29
(a) Ionic only (b) Covalent (H—O– ) and ionic (K+ −OH)
(c) Covalent (H—C, C—C and C—Li), but the C—Li bond is strongly polarized
(d) Covalent only (e) Covalent (H—C and C—O− ) and ionic (K+ −OCH3)
(f) Covalent (H—C, C—C, and C=O and C—O− ) and ionic (CH3CO2− Na+ ) (g) Covalent only
1-30
(b)
(a)
NF5 violates the octet rule; nitrogen can have no more than eight electrons (or four atoms) around it.
Phosphorus, a third-row element, can have more than eight electrons because phosphorus can use d
orbitals in bonding, so PF5 is a stable, isolable compound.
19
1-31 Your Lewis structures may look different from these. As long as the atoms are connected in the
same order and by the same type of bond, they are equivalent structures. For now, the exact placement
of the atoms on the page is not significant. H H H
(a) H N N H (b) H N N H (c) H C N C H Cl
H H H H H
H H O H O H
(d) H C C N (e) H C C H (f) H C S C H

H H H H
O H H O H
(g) H O S O H (h) H C N C O (i) H C O S O C H
O H H O H
H
H H
H C
H
H N H
H C C N O
(j) H C C C H (k) H
C
H H H H
H
1-32
H O H O H O H O
(a) H C C C C C C O H (b) N C C C C C H
H H H H H H
H O H O O H
(c) H C C C C C O H (d) H C C C C C O C H
H H H H H H C H H
H H
H
1-33 (Structures from problem 1-32 are redrawn in line-angle format.) In each set below, the second
structure is a more correct line formula. Since chemists are human (surprise!), they will take shortcuts
where possible; the first structure in each pair uses a common abbreviation, either COOH or CHO. Make
sure you understand that COOH does not stand for C—O—O—H. Likewise for CHO.
(a) COOH (b) N C CHO
O O
OR
OH H
OR N C
O O O O
20
1-33 continued
(c) COOH (d) COOCH3
OR OH OR
OH O
OH O O
1-34
In some cases, you are asked for the maximum number of structures possible for a molecular formula
containing a small number of atoms. In other cases, however, there may be many more structures possible,
and your structures can be correct even if they are not the ones shown here.
H H H H H H H
These are the only two possibilities,
(a) H C C C C H and H C C C H but your structures may appear
different—making models will help
H H H H H C H you visualize these structures.
H H
H
H H H H
(b) H C C O H and H C O C H These are the only two possibilities.
H H H H
H H H H H H
These are the only two possibilities,
(c) H C C N and H C N C H but your structures may appear
different—making models will help
H H H H H you visualize these structures.
H H H H H H H H H
(d) H O C C N H C O C N H C C O N
H H H H H H H H H
Think of all the ways an oxygen could be added to the structures in (c). There are many more!
(e) There are several other possibilities as well. Your answer may be correct even if your structures do
not appear here. Check with others in your study group.
H H H H H H H H H
O C C C O O C C O C H O C C C H
H H H H H H H H H H H O H
H
H O O
These are the only three
(f) H C C H H C C O H H C C H structures with this molecular
formula.
H H H H H
21
1-35 H H H H H H H H H
(a) only three O C C C H H C C O C H H C C C H
possible
structures H H H H H H H H O H
HOCH2CH2CH3 CH3CH2OCH3 H
CH3CH(OH)CH3
(b) This is most (maybe all) of the possible structures. H
H H O H O H H O H
H C C C H H C C C H H C C C O H H C C C H
H H H H H H H H H
CH3CH2CHO CH3COCH3 H2C CHCH2OH H2C C(OH)CH3
H H H O H
H C C O C H H O C C C H H C O C H
H H H H H H H H
H C C H C C
H2C CHOCH3 HOCH CHCH3 H H H H
H2C O OH
O
H O H2C CH2 CH
C C H
C H2C CH H2C CH2
H H H CH3
H
1-36 General rule: molecular formulas of stable hydrocarbons must have an even number of hydrogens.
The formula CH2 does not have enough atoms to bond with the four orbitals of carbon.
one carbon: H H
H
two carbons: H C C H H C C H H C C H
H C H
C2H2 C2H4 H H C2H6 H H
H CH4
H H H H H
three carbons: H C C C H H C C C H H C C C H
C3H4 H C3H6 H H H C3H8 H H H
22
1-37
(a) (b) (c) (d)
(e) (f) (g) (h)
1-38
(a) C6H6O (b) C4H5N (c) C4H8O2 (d) C6H8O2 (e) C7H10
(f) C4H4O (g) CH3NO2 (h) C6H10O
1-39 The symbols "δ+" and "δ–" indicate bond polarity by showing partial charge. Electronegativity
differences greater than or equal to 0.5 are considered large.
δ+ δ− δ− δ+ δ− δ+ δ+ δ− δ+ δ−
(a) C Cl (b) C H (c) C Li (d) C N (e) C O
large small large small large
δ− δ+ δ− δ+ δ− δ+ δ− δ+ δ+ δ−
(f) C B (g) C Mg (h) N H (i) O H (j) C Br
large large large large small
1-40 Non-zero formal charges are shown by the atoms.

H H H H
H H
(a) H C N O (b) C (c) N N N (d) H C O C H
H
H H C N O Formal charges sum to –1. H C H
No formal charges. H
C H H
H
H H H H H
H H C
H H
Formal charges sum to 0. Br
(e) H C N C (f) H C N C H
H C H
H
Formal charges sum to 0. H H H The formal charges in this
ionic compound sum to 0.
23
1-41 Resonance forms must have atoms in identical positions. If any atom moves position, it is a
different structure. It is particularly helpful in this problem to draw in all of the H atoms and bonds.
(a) Different compounds—a hydrogen atom has changed position.
(b) Resonance forms—only the position of electrons is different.
(c) Different compounds—a hydrogen atom has changed position.
(d) Different compounds—a hydrogen atom has changed position.
(e) Resonance forms—only the position of electrons is different.
(f) Resonance forms—only the position of electrons is different.
(g) Resonance forms—only the position of electrons is different.
(h) Different compounds—a hydrogen atom has changed position.
(i) Different compounds—a hydrogen atom has changed position.
(j) Resonance forms—only the position of electrons is different.
(k) Resonance forms—only the position of electrons is different.
(l) Resonance forms—only the position of electrons is different.
1-42 When drawing resonance forms with charges on ring atoms, it helps to keep track of the charge by
writing the C or N or O with the charge. (In Chapter 1, arrows will be shown when drawing resonance
forms, equivalent to the green arrows in the text. This important skill should become automatic by
Chapter 2 when the arrows will not be shown.)
(a) H O H O
H C C C H H C C C H
H H H H
(b) O O O
H C C C C H H C C C C H H C C C C H
H H H H H H H H H
(c) CH
For reasons to be
CH2 CH2 HC CH2 discussed in a later
major chapter, the
structure with all
double bonds in the
CH2 CH2 ring is the major
contributor.
major CH
H
C
(d)
All resonance forms are of
CH HC equal energy.
24
1-42 continued
(e) CH *major—negative
charge on the more
O O HC O electronegative
major* atom
O O
major* CH
CH
(f) HC N H N H N H
major—all atoms have octets

CH
(g)
HC
O O O
major—all atoms have octets
H
C
(h) H C O O O

(i) H C C C C C CH3 H C C C C C CH3 All resonance

forms are of
H H H H H H H H H H equal energy.
H C C C C C CH3
H H H H H
(j) No resonance forms—the charge must be on an atom next to a double or triple bond, or next to a non-
bonded pair of electrons, in order for resonance to delocalize the charge.
(k) H C C C O C C H H C C C O C C H
H H H H H H H H H H
H C C C O C C H
H H H H H
Note that the double bond on the right
major—all atoms have octets does not contribute its electrons to the
resonance forms.
25
1-43
(a) CH3 C C N CH3 C C N
H H
minor major (negative charge
on electronegative atom)
O O O
(b) CH3 C C C CH3 CH3 C C C CH3 CH3 C C C CH3

H H H H H H
minor minor major—full octets,
no charge separation
(c) O O O O O O
CH3 C C C CH3 CH3 C C C CH3 CH3 C C C CH3
H H H
minor major major
negative charge on electronegative atoms—equal energy
(d)
CH3 C C C N O CH3 C C C N O CH3 C C C N O
H H H O H H H O H H H O
minor minor major—negative charge on
electronegative atoms
NOTE: The two structures below are resonance forms, varying from the first two structures in part (d) by
the different positions of the double bonds in the NO2 . Usually, chemists omit drawing the second form of
the NO2 group although we all understand that its presence is implied. It is a good idea to draw all of the
resonance forms until they become second nature. The importance of understanding resonance forms
cannot be overemphasized.
CH3 C C C N O CH3 C C C N O
H H H O H H H O
NH2 NH2 NH2

(e) CH3CH2 C NH2 CH3CH2 C NH2 CH3CH2 C NH2
minor major—full octets major—full octets
equal energy
26
1-44 In Chapter 1, arrows will be shown when drawing resonance forms. This important skill should become
automatic by Chapter 2 when the arrows will not be shown.
(a) O CH2 O CH2 O CH2 O CH2

HC
CH
major—all atoms have
octets
(b) O O O
CH
CH2 CH2 CH2

CH2 CH2 CH2 CH2

(c) HN HN HN HN
CH HC
major—all atoms have
octets
H H
(d) C C
AND
HC CH
O O O O O
original major—all original
atoms have octets
(e) This remarkable anion has five equivalent resonance forms, distributing the negative charge equally
on all five carbons. (Braces omitted to save space.)
H H H H H H H H H H
C C C C C C C C C C
C C C C C C C C C C
H H H H H H H H H H
C C C C C
H H H H H
(f) H major—negative charge

C
on more electronegative atom
N CH N N
27
1-45
1-45
(a)
CH3 C CH3 CH3 C O CH3 CH3 C O CH3
H H H
more stable—resonance stabilized
no resonance stabilization
H
(b)
CH3 N CH3 CH3 N CH3 CH3 C CH3 no resonance
stabilization
CH3 C CH3 CH3 C CH3 CH3 C CH3
H
(c)
no resonance
CH2 C C CH3 CH2 C C CH3 CH2 C C CH2 stabilization
H H H H H H
(d) H C CH3 H C C N H C C N
H H H
no resonance stabilization more stable—resonance stabilized
(e) CH2 CH2 CH2

C C C
H
C C C no resonance stabilization
H H C H
H
(f)
H
O O O C O O
HC
HC
C
H
some resonance stabilization, but negative more stable—more resonance stabilization, and
charge is never on an electronegative atom negative charge is on an electronegative atom
(a) higher electron density
O O O
C C C lower electron density

H3C H H3C H H3C H
28
1-46 continued
O O O
(b) H3C C N H H3C C N H H3C C N H
H H H
minor
O
H3C C N H
(c) higher electron density

NH NH NH
C C C lower electron density

H3C H H3C H H3C H
O O O
(d)
H3C C O CH3 H3C C O CH3 H3C C O CH3
minor higher electron density

O
H3C C O CH3
O O O
(e) H3C O C N H H3C O C N H H3C O C N H
H minor H H
H3C O C N H
H
O
H3C O C N H

29
1-46 continued
(f) higher
NH NH NH NH
C HC C C electron
density
O O O O
NH
(g) O
C N C N C N C N
H H C H H
N N N N
H H H H

C N

H
N
(h)
O O O O
C HC
O O O O

lower O
electron
density O
(i)
H O H O H O H O
N N C N N
HC

H O
N
lower
electron
density
30
1-46 continued
(j) O O O
H
C C C C
H H H
H3C H3C H3C

O O O
O O
C C
H H
H3C H3C C
O O
lower
O
electron higher electron density
density O C
H
C
H H3C C CH
O
H3C
O
1-47 (c) some possible structures—MANY

other structures are possible:
(a) 100% − 62.0% C − 10.4% H = 27.6% oxygen
H H
62.0 g C H C H
= 5.17 moles C ÷ 1.73 moles = 2.99 ≈ 3 C
12.0 g/mole H C C O H
10.4 g H H C C O H
1.01 g/mole = 10.3 moles H ÷ 1.73 moles = 5.95 ≈ 6 H H C H
H H
27.6 g O
16.0 g/mole = 1.73 moles O ÷ 1.73 moles = 1 O H H H H H O
(b) empirical formula = C3H6O H C C C C C C O H

empirical weight = 58
H H H H H
molecular weight = 117, about double the empirical weight
H H H H H O
double the empirical formula = molecular formula =
H O C C C C C C H
C6H12O2 H H H H H
H H H H O H
H C C C C C O C H
H H H H H
31
1-48 From the amounts of CO2 and H2O generated, the milligrams of C and H in the original sample can be
determined, thus giving by difference the amount of oxygen in the 5.00-mg sample. From these values, the
empirical formula and empirical weight can be calculated.
(a) how much carbon in 14.54 mg CO2
1 mmole CO2 1 mmole C 12.01 mg C
14.54 mg CO2 x x x = 3.968 mg C
44.01 mg CO2 1 mmole CO2 1 mmole C
how much hydrogen in 3.97 mg H2O
1 mmole H2O 2 mmoles H 1.008 mg H
3.97 mg H2O x x x = 0.444 mg H
18.016 mg H2O 1 mmole H2O 1 mmole H
how much oxygen in 5.00 mg estradiol
5.00 mg estradiol – 3.968 mg C – 0.444 mg H = 0.59 mg O
calculate empirical formula

3.968 mg C
= 0.3304 mmoles C ÷ 0.037 mmoles = 8.93 ≈ 9 C
12.01 mg/mmole
0.444 mg H
= 0.440 mmoles H ÷ 0.037 mmoles = 11.9 ≈ 12 H
1.008 mg/mmole
0.59 mg O
= 0.037 mmoles O ÷ 0.037 mmoles = 1 O
16.00 mg/mmole
empirical formula = C9H12O empirical weight = 136
(b) molecular weight = 272, exactly twice the empirical weight
twice the empirical formula = molecular formula = C18H24O2
1-49 Imagine that you had four tennis balls: two yellow, one blue and one green. If you are asked to
arrange them on a flat surface, how many different ways could you do it? There are two possible "square"
arrangements (diamonds are the same, just oriented differently): one has the two yellow spheres touching
and the two spheres (blue and green) touching, while the other arrangement has the two yellow diagonal to
each other, and the two (blue and green) diagonal. If this represented CH2ClBr, with carbon at the center,
there should be two isomers of CH2ClBr in square planar geometry—and yet only one CH2ClBr has ever
been isolated. The geometry must be something different from square planar, and the only other way of
arranging the five atoms in CH2ClBr, while satisfying carbon's valence of 4, is tetrahedral. In tetrahedral
geometry, the relationship of each sphere (tennis ball) to the other three is equivalent, no matter how the
spheres are arranged.
1-50 H H
(a) C (b) Cyclopropene must have 60° bond angles compared with the usual sp3
bond angle of 109.5° and sp2 bond angle of 120° in an acyclic molecule.
C C
H H
(c) Like a bent spring, bonds that deviate from their normal angles or positions are highly strained.
Cyclopropene is reactive because breaking the ring relieves the strain.
32
1-51
H
(a) (b) (c) H C C N

O O C sp
H H
H
H H
3
sp , ≈ 109° sp3,no bond angle because
oxygen is bonded to only one atom C=C has sp2 carbons, ≈120° angles;
C N has sp C and N, 180° angle
H
H behind the plane π
H H
C of the paper H
(d) (e) (f) sp3 sp2
H N H N C
H H sp2
C C sp3 C sp2O
C H H H
H H O sp2
H H sp3
H H
both sp3, all ≈ 109° H
all sp3, all ≈ 109° sp3
angles around sp3 atoms ≈ 109°
angles around sp2 carbon ≈ 120°
in front of the behind the plane
(g) (h) plane of the of the paper (i)
H paper
N
O
sp2
H C
O H C
C H
sp3 H H H
H C
H H
both sp2, all ≈ 120°
H
angles around sp3
atom ≈ 109°
2
angles around sp atoms ≈ 120° both sp3, all ≈ 109°
1-52 For clarity in these pictures, bonds between hydrogen and an sp3 atom are not labeled; these bonds are
s-sp3 overlap. sp2-sp3 109°
2
sp -sp2 120° H
(b) + p-p H H (c)
(a) N H C N C H
H H C O
< 109° H all angles ≈120° H H

all bonds to H are sp2-s
120° sp2-s sp2-sp2 120°
+ p-p
3 2
109° H sp -sp
H sp-sp + 120°
two p-p
(d) H C C C sp2-s (e) O
s-sp
sp2-sp2 + p-p
H H C C C H
H H
sp2-sp2
sp2-s 180°
+ p-p
sp-sp2 sp2-s
33
1-52 continued
109° 180°
H
120° sp2-sp2
(f) H N C C N (g) O + p-p
H
H H
sp-sp + H C C O H
sp3-sp3 sp3-sp two p-p
109° H 109°
sp3-sp2 sp2-sp3
H H Resonance forms show that

(h) sp3-sp3 sp3-sp2 (i) sp2-sp3 sp3-sp2the O is sp2. All atoms are
sp2-sp2
H O + p-p sp2-s H sp2 except the top C which
O is sp3. Angles ≈120°
C C O
H 109° 120° around sp2, ≈109° around
sp2-sp2 sp2-sp2 sp2-sp2
C C the sp3 C.
H H
2 H H
sp2-sp2 + p-p sp -s sp2-sp2
sp3-sp2 sp2-s + p-p sp2-s
sp2-s ≈120° around C=C
1-53 The second and third resonance forms of urea are minor but still significant. They show that the
nitrogen-carbon bonds have some double bond character, requiring that the nitrogens be sp2 hybridized
with bond angles approaching 120°.
O sp2 O O sp2
H N C N H H N C N H H N C N H
H H H H H H
1-54
(a) The major resonance contributor shows a carbon-carbon double bond, suggesting that both carbons are
sp2 hybridized with trigonal planar geometry. The CH3 carbon is sp3 hybridized with tetrahedral geometry.
H O H O sp2
H C C C H H C C C H
sp3
H H H H
minor major
(b) The major resonance contributor shows a carbon-nitrogen double bond, suggesting that all three
carbons and the nitrogen are sp2 hybridized with trigonal planar geometry.
H N C C C H H N C C C H H N C C C H
H H H H H H H H H H H H
minor minor major
34
1-54 continued
(c) The nitrogen and the carbon bonded to it are sp hybridized; the other carbon is sp2. This ion has
linear geometry. See the solution to 1-21(e) in this manual for an orbital picture.
H H
C C N C C N
H minor H major
(d) The carbon of the CH2 is sp3 hybridized. The other carbons and the nitrogen are all sp2.
H H H
H C H H C H H C H
C C C C C C
N C N C N C
C H C H C H
H H H H H H
minor minor major—negative charge on
(e) The two carbons of CH2 are sp3 hybridized. The other carbons and the nitrogen are all sp2.
H H H
H C H H C H H C H
C C C C C C
H C N H C N H C N
C H C H C H
H H H
H H H H H H
minor minor major—all atoms have octets
(f) All of the non-hydrogen atoms in this molecule are sp2 hybridized.
H H H H
C O C O C O C O
C N C N C N C N
H H H H H H H H
C C C C
H H H H
minor major—all atoms minor major—all atoms
have octets have octets
35
1-54 continued
(g) The carbon of the CH2 is sp3 hybridized. The other carbons and the nitrogen and oxygen are all sp2.
H O H O H O
C C C C C C
C N C N C N
H H H H H H
C C C
H H H H H H
major—all atoms have minor middle—all
octets; no charges atoms have octets
H O
C C This is another correct, minor resonance form;
it is not needed to determine hybridization of
H the atoms.
C N
H
C
H H
(h) The carbon of the CH2 is sp3 hybridized. The other carbons and the nitrogen and oxygen are all sp2.
H O H O H O H O
C C C C C C C C
C C H C C H C C H C C H
H H H H
N N N N
H H H H
H H H H
major—all atoms have minor minor middle—all
octets; no charges atoms have octets
(i) Only the C and O of the C=O are sp2 hybridized. All other non-hydrogen atoms are sp3 hybridized.
H O H O The minor resonance form is not necessary in this

H C C H C C case to determine the hybridization of the atoms.
C C H C C H
H H
N N
H H H H
H H
major—all atoms have minor
octets; no charges
1-55 In (c), (d), (e) and (f), the unshadowed p orbitals are vertical and parallel; the shadowed p orbitals are
perpendicular to the paper and horizontal.
(a) (b) H (c) H H N

H3C
C O C N C C C
H3C H
C C
H H
36
1-55 continued
H
(d) (e) H3C
H
CH3 C C C C C C
O
H
CH3
H
(f) H C C O
C N
H3C
1-56
(a) (b) The coplanar atoms in the structures to the left and
* *
H H below are marked with asterisks.
C* *C * cis
* CH2CH3
H3C
(c) (d) H H *
H C * CH3
* *
H CH2CH3 H C * C
C* *C * trans
* H H C * C
H3C *
H C * H
H H
There are still six
coplanar atoms. H H
H H
1-57 Collinear atoms are marked with asterisks. C C C C H
H * * * * C
H H
37
1-58
Recall that cis and trans isomers are determined by comparing two identical groups on the two carbons
of the double bond, and determining their relative position: same side of the double bond = cis;
opposite side = trans. Drawing in H atoms is a big help!
(a)
(b) no cis-trans isomerism around a triple bond

(c) no cis-trans isomerism; a 3-member cycloalkene is unable to adopt a trans isomer due to angle strain
(d) The trans isomer of cyclopropene fail to exist because of the necessity of stretched bonds and
deformed bond angles.
(e)
(f)
1-59
(a) Not isomers (different molecular formula).
(b) Constitutional isomers: The position of the chlorine atom has changed.
(c) cis-trans isomers: The first is trans, the second is cis.
(d) cis-trans isomers: The first is cis, the second is trans.
(e) Constitutional isomers: The position of the carbon double bond has changed.
(f) Same compound: Rotation of the first structure gives the second.
(g) Constitutional isomers: The carbon skeletons are different.
(h) Constitutional isomers: The position of the double bond relative to the ketone has changed.
1-60 O O O
C S S
CH3 CH3 CH3 CH3 CH3 CH3
a misleading picture
sp2—planar sp3—tetrahedral
The key to this problem is understanding that sulfur has a lone pair of electrons. The second resonance
form shows four pairs of electrons around the sulfur atom, an electronic configuration requiring sp3
hybridization. Sulfur in DMSO cannot be sp2 like carbon in acetone, so we would expect sulfur's geometry
to be pyramidal (the four electron pairs around sulfur require tetrahedral geometry, but the three atoms
around sulfur define its shape as pyramidal). The first resonance form is a misleading picture because it
suggests a p-p pi bond in DMSO that does not exist. Sulfur might use a d orbital for some pi bonding but it
is definitely not a p-p pi bond.
38
CHAPTER 2—ACIDS AND BASES; FUNCTIONAL GROUPS
2-1
(a) 2.4 D = 4.8 x δ x 1.23 Å
δ = 0.41, or 41% of a positive charge on carbon and 41% of a negative charge on oxygen
(b) O O
C C
R R R R
A B
Resonance form A must be the major contributor. If B were the major contributor, the value of the charge
separation would be between 0.5 and 1.0, meaning >50% of a positive charge on C and >50% of a negative
charge on O. Even though B is "minor", it is quite significant, explaining in part the high polarity of the
C=O.
2-2
Both NH3 and NF3 have a pair of nonbonding electrons on the nitrogen. In NH3, the direction of
polarization of the N—H bonds is toward the nitrogen; thus, all three bond polarities and the lone pair
polarity reinforce each other. In NF3, on the other hand, the direction of polarization of the N—F bonds is
away from the nitrogen; the three bond polarities cancel the lone pair polarity, so the net result is a very
small molecular dipole moment.
• • • •
polarities reinforce; polarities oppose;
large dipole moment small dipole moment
(1.50) N N (0.20)
H H F F
H F
2-3 Some magnitudes of dipole moments are difficult to predict; however, the direction of the dipole
should be straightforward, in most cases. Actual values of molecular dipole moments are given in
parentheses. (Each halogen atom has three nonbonded electron pairs, not shown below.) The C—H is
usually considered nonpolar. (Parts (a) and (b) are solved in the text.)
H
Cl H
(c) H (d) C F large dipole (1.81)
H C large dipole (1.54)
H
Cl
net
net
(e) F (f)
F
C net dipole = 0 O large dipole (1.70)
F
F
H CH3 net
(g) (h) (i)

O H
H C N N
C
net C
H CH3 net
large dipole (2.95) H H
large dipole (2.72) net
large dipole
39
2-3 continued
(j) (k)
H H
small dipole (0.67) C C
N Cl H net
H3C CH3 net
CH3 large dipole (1.45)
(l) F (m)
Cl Be Cl
B F net dipole = 0
F In (l) and (m), the symmetry of the

molecule allows the individual
net dipole = 0 bond dipoles to cancel.
2-4 With chlorines on the same side of the double bond, the bond dipole moments reinforce each other,
resulting in a large net dipole. With chlorines on opposite sides of the double bond, the bond dipole
moments exactly cancel each other, resulting in a zero net dipole.
Cl Cl H Cl
net
large net dipole C C C C net dipole = 0
(2.40)
H H Cl H
2-5 Hydrogen bonds are shown as wavy bonds.

(a) + δ− δ+ (b)
δ H
CH3CH2 O δ− N δ+
δ+ δ+
−
O δ δ+ CH3CH2CH2 H
H
CH2CH3 H δ+
−
δ+ Nδ δ+
H CH2CH2CH3
H δ+
(c) (d)
O O
δ− H δ− H δ+
O
δ+
H H δ−
δ+ δ+ δ+ δ+ H H
O δ+ δ−
δ− CH3 H3C δ− δ+
H3C N
δ+ δ+ H3C δ+ N CH3
+ δ+
δ CH3 H3C
δ+ CH3
40
2-6
(a) (CH3)2CHCH2CH2CH(CH3)2 has less branching and boils at a higher temperature than (CH3)3CC(CH3)3 .
(b) CH3(CH2)5CH2OH can form hydrogen bonds and will boil at a much higher temperature than
CH3(CH2)6CH3, which cannot form hydrogen bonds.
(c) CH3CH2CH2CH2OH can form hydrogen bonds and boils at a higher temperature than CH3CH2OCH2CH3.
(d) HOCH2(CH2)4CH2OH can form hydrogen bonds at both ends and has no branching; it will boil at a much
higher temperature than (CH3)3CCH(OH)CH3 .
(e) (CH3CH2CH2)2NH has an N—H bond and can form hydrogen bonds; it will boil at a higher temperature
than (CH3CH2)3N, which cannot form hydrogen bonds.
(f) The second compound shown (B) has the higher boiling point for two reasons: B has a higher molecular
weight than A; and B, a primary amine with two N—H bonds, has more opportunity for forming hydrogen
bonds than A, a secondary amine with only one N—H bond.
H
A N H B N
H
2-7
(a) CH3CH2OCH2CH3 can form hydrogen bonds with water and is more soluble than CH3CH2CH2CH2CH3,
which cannot form hydrogen bonds with water.
(b) CH3CH2CH2OH is more soluble in water because it has one fewer carbon than CH3CH2OCH2CH3 .
(c) CH3CH2NHCH3 is more water soluble because it can form hydrogen bonds with water; CH3CH2CH2CH3
cannot form hydrogen bonds.
(d) CH3CH2OH is more soluble in water. The polar O—H group forms hydrogen bonds with water,
overcoming the resistance of the nonpolar CH3CH2 group toward entering the water. In
CH3CH2CH2CH2OH, however, the hydrogen bonding from only one OH group cannot carry a four-carbon
chain into the water; this substance is only slightly soluble in water.
(e) Both compounds form hydrogen bonds with water at the double-bonded oxygen, but only the smaller
molecule (CH3COCH3) dissolves. The cyclic compound has too many nonpolar CH2 groups to dissolve.
2-8
1 mole HBr
(a) 5.00 g HBr x = 0.0618 moles HBr
80.9 g HBr
0.0618 moles HBr 0.0618 moles H3O + (100% dissociated)
0.0618 moles H3O + 1000 mL 0.618 moles H3O +
x =
100. mL 1L 1 L solution
pH = − log10 [ H3O+ ] = − log10 (0.618) = 0.209
(b) 1.50 g NaOH x 1 mole NaOH = 0.0375 moles NaOH

40.0 g NaOH
0.0375 moles NaOH 0.0375 moles −OH (100% dissociated)
0.0375 moles −OH 1000 mL 0.75 moles −OH
x = = 0.75 M
50. mL 1L 1 L solution
1 x 10−14 1 x 10−14
[ H3O+ ] = = = 1.33 x 10−14
[ −OH ] 0.75 (The number of decimal places
pH = − log10 [ H3 O+ ] = − log10 (1.33 x 10−14 ) = 13.88 in a pH value is the number of
significant figures.)
41
2-9
(a) By definition, an acid is any species that can donate a proton. Ammonia has a proton bonded to
nitrogen, so ammonia can be an acid (although a very weak one). A base is a proton acceptor; that is, it
must have a pair of electrons to share with a proton. In theory, any atom with an unshared electron pair can
be a base. The nitrogen in ammonia has an unshared electron pair so ammonia is basic. In water, ammonia
is too weak an acid to give up its proton; instead, it acts as a base and pulls a proton from water to a small
extent.
(b) water as an acid: H2O + NH3 –OH + NH +
4
water as a base: H2O + HCl H3O+ + Cl–

(c) Hydronium acting as an acid in water solution will have this chemical equation:
H3O+ + H2O H3O+ + H2O [H3O+] [A–] [H3O+] [H2O]
Ka = = = [H2O]
HA A– [HA] [H3O+]
1000 g H2O 1 mole H2O
[H2O] = x = 55.55 M = Ka pKa = –log(55.55) = –1.74
1 L H2O 18.0 g H2O
(d) methanol as an acid: CH3OH + NH3 CH3O– + NH4+
methanol as a base: CH3OH + H2SO4 CH3OH2+ + HSO4–
2-10 Values are from Table 2-2, or, as noted, from Appendix 4 in the text.
(a) HCOOH + −CN HCOO− + HCN FAVORS Part (a) is already
stronger stronger weaker weaker PRODUCTS solved in the text.
acid base base acid
pKa 3.76 pKa 9.22
(b) CH3COO− + CH3OH CH3COOH + CH3O− FAVORS

weaker weaker stronger stronger REACTANTS
base acid acid base
pKa 15.5 pKa 4.74
(Appendix 4)
(c) (CH3)2CHOH + NaNH2 (CH3)2CHO− Na+ + NH3 FAVORS

stronger stronger weaker weaker PRODUCTS
acid base base acid
pKa ≈15.9 pKa 36
(estimated from Table 2-2)
(d) Na+ −OCH3 + HCN HOCH3 + Na+ –CN FAVORS

base acid acid base
pKa 9.22 pKa 15.5
(Appendix 4)
(e) HCl + CH3CH2OH CH3CH2OH2+ + Cl− FAVORS

acid base acid base
pKa –7 pKa –2.4
(Appendix 4)
42
2-10 continued
(f) H3O+ + CH3O− H2O + CH3OH FAVORS
acid base base acid
pKa –1.7 pKa 15.5 (Appendix 4)
H
(g) N H + OH N + O FAVORS
H PRODUCTS
stronger stronger weaker weaker
base acid acid base
pKa 10.0 pKa 11.3
(Appendix 4) (Appendix 4)
H
(h) N H + COOH N + COO FAVORS
H PRODUCTS
base acid acid base
pKa ≈ 4.7 pKa 11.3
similar to CH3COOH
(i) SH + CH3CH2O CH3CH2OH + S FAVORS

PRODUCTS
acid base acid base
pKa 7.8 pKa 15.9
(j) C C + CH3CH3OH C CH + CH3CH2O FAVORS

PRODUCTS
base acid acid base
pKa 15.9 pKa ≈ 25
similar to HC CH
2-11 O O
(a) H3C C OH + B H B + H3C C O
strongest acid pKa 4.74
CH3CH2OH + B H B + CH3CH2O
pKa 15.9
CH3NH2 + B H B + CH3NH
weakest acid pKa 40
43
2-11 continued
(b)
CH3NH2 + H A A + CH3NH3
strongest base pKa 10.7 weakest conjugate acid
CH3CH2OH + H A A + CH3CH2OH2
pKa –2.4
O OH
H3C C OH + H A A + H3C C OH strongest conjugate acid

weakest base pKa –6.1
2-12
First, review the structures and properties of the solvents in question.
CH3CH2CH2CH2CH3 CH3CH2OCH2CH3 CH3CH2OH H2O NH3
pentane diethyl ether ethanol water ammonia
•Pentane is a hydrocarbon, neither acidic nor basic. Any acid-base reaction can occur in hydrocarbons
without interacting with the solvent.
•Diethyl ether is not acidic, so reactions with strong bases are compatible, but it is weakly basic, so reactions
with very strong acids (stronger than pKa –3.6) will be leveled by the solvent.
•Ethanol is both acidic (pKa 15.9) and basic (pKa of the conjugate acid –2.4), so only acids and bases within
this range are possible without interaction with the solvent.
•Water is both acidic (pKa 15.7) and basic (pKa of the conjugate acid –1.7), so only acids and bases within
this range are possible without interaction with the solvent.
•Ammonia is both acidic (pKa 36, very weak) and basic (pKa of the conjugate acid 9.2), so only acids and
bases within this range are possible without interaction with the solvent.
This question is asking, "Are the ultimate products compatible with the solvents?" The reactants may be
leveled by the solvent, but as long as the products can exist within the pKa limits of the solvent, the solvent is
an acceptable choice.
CH3CH2CH2CH2CH3 CH3CH2OCH2CH3 CH3CH2OH H2O NH3
Reaction pentane diethyl ether ethanol water ammonia
(a) very strong base OK OK NO NO OK
HC CLi is a strong base from an acid of pKa 25. It is not compatible with alcohols and water.
(b) strong base OK OK NO NO OK

(CH3)3COLi is a strong base from an acid of pKa 18. It is not compatible with alcohols and water.
(c) very strong acid OK NO NO NO NO
The protonated ring compound has pKa –3.8. It is compatible only with pentane.
(d) strong base OK OK NO NO OK
also a reactant
(CH3)3CONa is a strong base from an acid of pKa 18. It is not compatible with alcohols and water.
(e) very strong acid OK NO NO NO NO
The protonated oxygen compound has pKa –7.3. It is compatible only with pentane.
(e) strong acid OK OK OK OK NO
The protonated oxygen compound has pKa 0.0. It is compatible with the four solvents except ammonia.
44
2-13
favors
(a) CH3CH2 O H + CH3 N H CH3CH2 O + CH3 N H
PRODUCTS
stronger acid stronger base conjugate base
H
weaker base conjugate acid
more stable anion—
negative charge on the weaker acid
(b) F3CCOONa + Br3CCOOH F3CCOOH + Br3CCOONa favors
weaker base weaker acid conjugate acid conjugate base REACTANTS
more stable anion—F is stronger acid stronger base
more electronegative than Br
H
(c) CH3 O H + H2SO4 CH3 O H + HSO4– favors
PRODUCTS
stronger base stronger acid conjugate acid conjugate base
pKa –5 weaker acid weaker base
pKa –2.5
(d) Na O H + H S H H O H + Na S H favors
PRODUCTS
stronger base stronger acid conjugate acid conjugate base
weaker acid weaker base
H larger anion—size matters!
(e) CH3 N H + CH3 O CH3 N H + CH3 O H favors

PRODUCTS
H stronger base H conjugate acid
stronger acid conjugate base weaker acid
pKa 10.7 weaker base pKa 15.5
(f) BrCH2CH2OH + F3CCH2O– BrCH2CH2O– + F3CCH2OH favors

weaker acid weaker base conjugate base conjugate acid REACTANTS
more stable anion—F is stronger base stronger acid
more electronegative
than Br, especially 3 F
(g) NaOCH2CH3 + Cl2CHCH2OH HOCH2CH3 + Cl2CHCH2ONa favors
stronger base stronger acid conjugate acid conjugate base PRODUCTS
weaker acid weaker base
more stable anion—
2 Cl stabilize anion
(h) H2Se + NaNH2 NaHSe + NH3 favors
stronger acid stronger base conjugate base conjugate acid PRODUCTS
pKa 7.0 weaker base weaker acid
more stable anion— pKa 36
Se much larger than N
(i) CH3CHFCOOH + FCH2CH2COO– CH3CHFCOO– + FCH2CH2COOH favors
stronger acid stronger base conjugate base conjugate acid PRODUCTS
weaker base weaker acid
more stable anion—F is
closer to COO–
(j) CF3CH2O– + FCH2CH2OH CF3CH2OH + FCH2CH2O– favors
weaker base weaker acid conjugate acid conjugate base REACTANTS
more stable anion—3 F stronger acid stronger base
stabilizes anion better than
1F 45
2-14
Three principles guide the effect of electron-withdrawing substituents on acid strength. Acidity is increased by:
1. increasing strength of electron-withdrawing substituents; for single atoms, this means more electronegative;
2. increasing number of electron-withdrawing substituents;
3. closer proximity of the electron-withdrawing substituents to the acidic group.
"Electron-Withdrawing Group" is abbreviated "EWG".
strongest acid weakest acid

two, strong EWG one, strong EWG one, moderate EWG one, moderate EWG
next to acid group next to acid group next to acid group farther from acid group
2-15 H3C H3C

stronger
(a) conjugate acid C O + H2O H3O+ + C O sp2
H H H weaker base
pKa –8.0
(b) H3C H H3C H
pKa –2.4
H C O + H2O H3O+ + H C O sp3
weaker
conjugate acid H H H stronger base
An atom with sp2 hybridization is less basic than the same atom with sp3 hybridization. Therefore,
the conjugate acid of the sp2 atom must be a stronger acid than the atom when sp3 hybridized.
2-16 NHCH3 NCH3
C N
strongest base, sp3 sp2 weakest base, sp
H A H A H A
H H
NHCH3 NCH3
C N H
weakest conjugate acid sp2 strongest conjugate acid

pKa 10.7 for pKa 5.5 for pKa –10.1 for really
H NHCH3 strong!
H3CC NH
H N CH3 C
H3C CH3
CH3 46
2-17
When comparing basic atoms, sp3 atoms are stronger bases than sp2, which are stronger than sp.
Conjugate acids have the opposite order: H on sp is stronger than H on sp2, which is stronger than H on sp3.
(a) (b) OH O
C C
weaker base, sp stronger base, sp2

stronger base, sp3 weaker base, sp2
H A H A
H H A H A
OH2 OH
C C H
stronger conjugate acid weaker conjugate acid

weaker conjugate acid stronger conjugate acid
(c) (d) These structures are not the same comparison as

NH N in the other problems. They differ by a more
important feature than hybridization: an anion at
an sp3 carbon is always going to be a stronger
base than a neutral nitrogen.
stronger base, sp3 weaker base, sp2 H
H A H A
C N
NH2 NH stronger base, weaker base, neutral

anion and sp3 N and sp
H A
H A
weaker conjugate acid stronger conjugate acid H H
C N H
weaker conjugate acid stronger conjugate acid

2-18
Recall that for any conjugate acid-base pair, pKa + pKb = 14. Applying this to the structures in question:
HCN H+ + CN
hydrocyanic acid, cyanide ion, pKb = 4.78;
pKa = 9.22; weaker acid stronger conjugate base
HF H+ + F
hydrofluoric acid, fluoride ion, pKb = 10.83;
pKa = 3.17; stronger acid weaker conjugate base
47
2-19
The resonance forms of acetamide show that the oxygen, not the nitrogen, is the likely site of protonation
because the oxygen has a higher electron density than nitrogen.
H H
O O O O
+ H3O+
C C C C
H3C NH2 H3C NH2 H3C NH2 H3C NH2
pKb = 14 Protonation on oxygen also maintains resonance

stabilization, unlike protonation on nitrogen
which interrupts resonance stabilization.
pKa = 14 – pKb = 14 – 14 = 0
2-20
Protonation could occur at either oxygen.
O O O
protonation on OH No resonance
C C C stabilization with
H3C OH H3C OH H3C OH
protonation at OH.
pKb = 20 H H
protonation insignificant
on =O contributor
H H H Protonation at this oxygen makes a

O O O
positive ion that is stabilized by
C C C resonance; both major resonance
H3C OH H3C OH H3C OH contributors are equivalent, especially
major minor major stabilizing. Moreover, all three atoms
in the pi system share in the
pKa = 14 – pKb = 14 – 20 = –6 delocalization of the positive charge.
2-21 The strength of an acid is determined by the stability of its conjugate base.
This problem analyzes resonance stabilization of conjugate bases, which in this problem are anions except
for part (g). The conjugate base that has more resonance forms that are significant contributors will be
more stable, and therefore its conjugate acid is the stronger acid.
Part (a) was solved in the textbook.
(b) The anion of the first structure has three significant resonance contributors, two of which are equivalent
(particularly stable) and with negatve charge on the more electronegative atoms; high stabilization of the
anion makes the first structure the stronger acid.
H
O O O C O O O
major minor major

See the next page for the resonance forms of the other conjugate base.
48
2-21(b) continued
The anion obtained by removing the H+ from
O O O O the OH in the second structure gives only two
resonance forms, and only one has negative
charge on oxygen—not as stable as the first
C structure.
major minor H
However, there is another choice of which H+ to remove. Removing an H from the CH2 between the two
oxygens also gives a resonance-stabilized anion:
H H remove H H H
O C OH O C OH O C OH O C OH
C
H
minor major minor
Arguably, the CH is a better proton to remove than the OH because of greater resonance stabilization, but
either of the anions from the second structure is less stable than the anion from the first structure. The first
structure is still the stonger acid.
(c) The most acidic H+ from the first structure is the OH. F O no resonance forms;
The anion from removing this H+ is not stabilized by F is too far away to
resonance, and the F is too far away to have any significant stabilize anion
inductive effect.
The anion from the second structure has F F

two resonance forms, the second of which
is even more stable because of the O C O
electronegativity of F. Therefore, the
second structure is the stronger acid.
major better than minor because

of F electronegativity
(d) Removing an H+ from NH2 gives a highly stabilized anion:
O O O
C NH C NH C NH
second most significant least significant most significant
There are two choices for which H+ to remove from the second O
structure. If we want a direct comparison with the resonance-
stabilized anion directly above, we should look at removing an H+
from the N, giving this conjugate base with no resonance C NH
stabilization.
See the next page for the resonance forms of the other conjugate base.
49
2-21(d) continued
O O O O
C NH2 C NH2 C NH2 C NH2

C C C C
H
H remove H H H
minor minor major
Although removing the CH2 proton gives a more stable conjugate base than removing the NH2 proton,
neither is better than the anion from the first structure. The first structure is the stronger acid.
(e) Remove the proton from the OH in each case. The first structure gives a resonance-stabilized
conjugate base, but only one of the resonance forms has the negative charge on an electronegative atom.
H
O C N O C C N O C N
C
H
major minor minor
From the second structure:
H
O O C O O
C C
C C C C
major N minor N minor N MAJOR N
Woo hoo! With the proper placement of the CN group, the negative charge can be delocalized onto the N
as well as the O, making this the more stable conjugate base. The second structure is the stronger acid.
(f) Remove the proton from the OH in each case. The first structure gives a resonance-stabilized conjugate
base in which the negative charge is delocalized onto both oxygen atoms—hard to beat.
O O O O
H
C C
O major O minor O minor O major
See the next page for the structure of the other conjugate base.
50
2-21(f) continued O
The conjugate base of the second structure shows that
there is no resonance stabilization of the anion.
Therefore, the first structure is the stronger acid.
(g) The conjugate bases of these structures are not anions, yet the same principle applies: the stability of the
conjugate base determines the strength of the acid.
O O O
After one of the NH protons is
C
removed from the first structure, the
conjugate base is a structure that has
no charge and the NH2 is not HC
stabilized by resonance. NH2 NH2 NH2
major minor minor
After one of the NH protons is removed from the second structure, however, the conjugate base is highly
stabilized by resonance.
O O O O
C
NH2 NH2 NH2 NH2
major minor minor major—all atoms have octets
Because it has the more stable conjugate base, the second structure is the stronger acid.
(h)
After the OH proton is removed, the first
structure is stabilized by resonance only to a
small degree.
O C O
major H
minor—negative on less
electronegative atom
After one of the OH protons is removed from the second structure, however, the conjugate base is highly
stabilized by resonance.
H H
C C
O C O O O O
major H minor minor minor major

Because it has the more stable conjugate base, the second structure is the stronger acid.
51
2-21 continued
(i) In both of these structures, removal of the OH proton results in a highly stabilized anion.
O O O O
H H H C H
O C O O O
major H minor minor major

AHA! The second
O O structure does not have
this "extra" resonance
H form.
H H C
O O
major minor
Resonance forms of the anion of the second structure show that the negative charge is never delocalized
on the C=O group.
H O H O H O H O H O
H H
C C
O C O O O O
major H minor minor minor major

The first structure has the extra resonance form where the negative charge is delocalized onto the C=O,
resulting in greater stability. The first structure is the stronger acid.
Note to the student: Resonance is your friend. Many, if not most, of the effects of structure on
stability and reactivity are based on resonance, and understanding how to draw resonance forms, and
when to apply the concept of resonance, is a critical tool in your success in solving problems.
2-22
The more stable the anion, the less basic it will be. This is the corollary of: a stronger acid has a weaker
conjugate base, because a stronger acid has a more stable conjugate base.
(b) The first structure has its negative charge delocalized by resonance.
H
O O O C O O O
major minor major

52
2-22(b) continued
The negative charge in the second structure is
O O O O only slightly stabilized by one minor resonance
contributor.
C
major minor H
Because the first structure is more stable because of greater resonance delocalization of the negative charge,
the second structure will be the stronger base. Note that this is the same as problem 2-21(b), just from
the other side of the equation.
(c) The first structure has N N N
the negative charge O O O O O O
delocalized onto two
oxygens and a nitrogen:
The second structure has

the negative charge O O O O
delocalized onto one
oxygen and a carbon: NH C NH
major
H minor
Because the first structure is more stable because of greater resonance delocalization of the negative charge,
the second structure will be the stronger base.
(d) Even though there is resonance between the NO2
C=C and the NO2 group, the first structure has
the negative charge on oxygen that is not
delocalized by resonance.
O O O
The second structure has
the negative charge N N N
delocalized onto two O C O O
oxygens:
O O O
major minor major
Because the second structure is more stable because of greater resonance delocalization of the negative
charge, the first structure will be the stronger base.
(e) As shown on the next page, the negative charge in both structures is highly delocalized by resonance,
but only the second structure has the negative charge on the oxygen and the nitrogen. Because the second
structure is more stable, the first structure will be the stronger base.
53
2-22(e) continued
First structure:
H H
C C
NC O NC C O NC O NC O NC O
minor
Second structure:
N N N N N
C C H C C C
C C
O C O O O O
minor
N
C
This is the extra
resonance form that
makes this structure more O
stable. major
The first structure will be the stronger base.

2-23 Solutions for (a) and (b) are presented in the Solved Problem in the text. Here, the newly formed
bonds are shown in bold. H
Curved arrows that show
(c) H B H + CH3 O CH3 electron movement are
H B H
shown here and in the text
H Lewis base—
Lewis acid—electrophile nucleophile
CH 3 O CH 3 in red. Arrows within
resonance forms that show
imaginary movement are in
(d) O O green in the text, and in
black here.
CH3 C H + O H CH3 C H
Lewis base— The problem asks for the imaginary
Lewis acid—electrophile nucleophile O H movement of electrons in the resonance
forms.
(e) Brønsted-Lowry—proton transfer
H O H O H O
H C C H + O H H C C H H C C H + H O H
base—
H nucleophile
acid—electrophile
CH3
(f) CH3 N H + CH3 Cl CH3 N H + Cl

H Lewis acid—
electrophile H
Lewis base—
nucleophile 54
2-23 continued
F F
H
(g) CH3 C CH2 + B F CH3 C C B F
H H2
Lewis base— F F
nucleophile Lewis acid—
electrophile same
F CH3 F
H H2 H H2
(h) CH3 C CH2 + CH3 C C B F H3C C CH2 C C B F
H H
Lewis base— F F
nucleophile Lewis acid—
electrophile
O O
(i)
Cl Cl
O The problem asks for the imaginary movement of
OH H electrons in the resonance forms.
OCH3 OCH3 OCH3

(j) C C
O O
O N O N N
O O
2-24 H H
H C H H H H H H H H H H
(a) H C C H (b) H C C C C C H (c) H C C C C C C H
H C C H alkane H H H H H H H H H
H C C H alkene alkyne
H C H H H
H H (Usually, we use the term "alkane"
only when no other groups are present.)
H H H H H H H
(d) H C C C C (e) H C C C C H (f) H C C C H
C C
H C C H C C H C C
H C C H H C H
H H
HH H
H H cycloalkane and alkene
cycloalkyne and (a "cycloalkene" would aromatic hydrocarbon
cycloalkene have the C=C in the ring) and alkyne
continued on page 57 55
WHAT IS THE FUNCTIONAL GROUP?
DOES THE STRUCTURE HAVE ANY PI BONDS?
NO YES
DOES THE STRUCTURE HAVE O OR N? DOES THE STRUCTURE HAVE O OR N?
NO YES NO YES
ALKANE— DOES THE ALKENE DOES THE

no functional group STRUCTURE HAVE O? STRUCTURE HAVE O?
OR C C
NO YES NO YES
ALKYL HALIDE
OR
AMINE ALCOHOL ALDEHYDE
56
ALKYNE NITRILE
C X O
C C C N
C N C OH
C
X = F, Cl, Br, I OR H
BENZENE CARBOXYLIC ACID KETONE
OR (AROMATIC)
O O

ETHER C H C
O C C
C O C
this chart! Use it as an aid as you are becoming familiar with the functional groups.
AMIDE ESTER ACID CHLORIDE

This chart depicts only the most O O O
common functional groups.
There are many more! C C C C
N O Cl
called acid derivatives
groups are present in a molecular structure. This page is called a "concept map" that prompts you with a
Note to the student: One of the most fundamental skills in organic chemistry is to identify what functional
series of questions about a structure, leading to the determination of the functional group. Do not memorize
2-24 continued
H H H H H H
HH H H H
H C C C C H (h) H H (i) H C C
(g) H C C C C H
C C C C H
C H C C
H C C H H C C C
C H
H
C C H H H C C H
H H H H
H H H H H
cycloalkene and alkene cycloalkane and alkane aromatic hydrocarbon
and cycloalkene
2-25 H
H H O H H O H H O H H
(a) H C C C H (b) H C C C C H (c) H C C C C H
alkene and aldehyde H H H H H H H
alcohol ketone
H H H H H H
(d) (e) H C H O (f) H O H ether and
H C C O C C H H C C C O H H C C alkene
H H H C C H H C C
ether and alkene H C H H C H
H H H H
carboxylic acid
H O H
H H H H C O H
C H H
(g) H C O (h) H C (i) C
C C C C C C H
H H H H
C C C C C C
H H H H H H
H H H H H H
alkene and ketone aldehyde alcohol
2-26
H H O H H H H H H H O H
(a) H C C C N C H (b) H C C N C C H (c) H C C C O C H
H H H H H H H H H H C H
amide amine HH H ester
H H H O H H H H H H H
(d) H C C C C Cl (e) H C C O C C H (f) H C C C C N
H alkene and H H H H H H H
acid chloride ether nitrile
HH H O O H H H
(g) H C H H O (h) H C (i) H C H H C
(j)
C O C C H C N C H
H C C C C C O H H H
C C C O H C C HH
H C H H H H H C H
HH H H H H H H
carboxylic acid cycloalkene and cyclic ketone
cyclic ester and ether cyclic amine
57
2-26 continued
O O
H H H O H
(k) H C (l) H C (m) H C
H C N C H cyclic H C N C C H H C O cyclic ester
H C C H H amide H C C H H H C C H
H C H H C H H C H
H H H H H amide H H
H C H H H
O O H
(n) H N H (o) H C
H C C C H C C C C H
H
H C C H cyclic amine C C H
H C H and aldehyde H H
H H H cycloalkene
and ketone
2-27 When the identity of a functional group depends on several atoms, all of those atoms should be
circled. For example, an ether is an oxygen between two carbons, so the oxygen and both carbons should
be circled. A ketone is a carbonyl group between two other carbons, so all those atoms should be circled.
O
(a) CH2 CHCH2COOCH3 (b) CH3 O CH3
aldehyde
ester (c) CH3 C H
alkene ether
O
C OCH3 amine O
O (e) CH3 N CH3 (f) R C O H
(d) CH3 C NH2 H carboxylic acid
R is the symbol that organic chemists use to
amide represent alkyl groups. Sometimes, when the
identity of the group does not matter, aryl groups or
others can also be included in the R abbreviation.
aromatic
(g) CH2OH (h) C N (i)
O ketone
alcohol nitrile
alkene
(j) aromatic
ketone (k) ether
(also includes two alcohol (In later chapters, you will CH3
adjacent carbons) learn that the OH group on a CH3
CH2OH benzene ring is a special CH3 O
alcohol functional group called a C16H33
O "phenol". For now, it fits the
HO broad definition of an alcohol.)
OH HO
ketone
alcohol
alcohol CH3
O
alkene
58 This group is represented by C16H33 in the problem.
2-28
The triple bond between C and N is highly polarized: H3C C N H3C C N
A B
3.6 D = 4.8 x δ x 1.16 Å
δ = 0.65, or 65% of a positive charge on carbon and 65% of a negative charge on nitrogen
Resonance form B must be the major contributor. If A were the major contributor, the value of the charge
separation would be between 0.0 and 0.5, meaning <50% of a positive charge on C and <50% of a negative
charge on N.
2-29 Some magnitudes of dipole moments are difficult to predict; however, the direction of the dipole should
be straightforward in most cases. Actual values of molecular dipole moments are given in parentheses. (The
C—H bond is usually considered nonpolar.)
H2
(a) (b) C H
CH3 CH 3 H 3 C O
N N
or net
C C
H CH3 H CH3 large dipole moment (2.6)
net net
large dipole moment large dipole moment
(e)
Br N N
Br
(c) C (d) C C
Br O
C C
Br
C C C
net dipole moment = 0 net N N
CH3 CH3
Electron pairs on
bromines are not shown. large dipole moment (2.89)
net dipole moment = 0

(f) H (g) (h)
CH2 Cl
N
CH2 C
CH2 CH2 O
net
CH2 C net
CH2 CH2 C net
CH2 H
CH2 CH3 NH2
moderate dipole moment moderate dipole moment large dipole moment (3.76)
Electron pairs on
chlorine are not shown.
2-30 CO2 is linear; its bond dipoles cancel, so it has no net dipole. O3 is bent, so its bond dipoles do not
cancel.
59
2-31
2-31
(a) Can hydrogen bond with itself and with water. (b) Can hydrogen bond only with water.
(c) Can hydrogen bond with itself and with water. (d) Can hydrogen bond only with water.
(e) Cannot hydrogen bond: no N or O. (f) Cannot hydrogen bond: no N or O.
(g) Can hydrogen bond only with water. (h) Can hydrogen bond with itself and with water.
(i) Can hydrogen bond only with water. (j) Can hydrogen bond only with water.
(k) Can hydrogen bond only with water. (l) Can hydrogen bond with itself and with water.
Water solubility depends on the number of carbons and the number of hydrogen-bonding groups in a
molecule, and to a lesser extent, on the shape of the molecule and its ability to form hydrogen bonds. A
structure with one hydrogen-bonding group can carry in three carbons for sure, called "miscible", meaning
completely soluble; four carbons will be partially soluble—these are borderline cases and are the most
difficult to predict; five or more carbons will be only slightly soluble, which is sometimes called "insoluble".
•completely soluble, miscible: (c) 3C; (g) 3C; (h) 3C; (i) 3C; (l) 2C;
•moderately soluble, possibly miscible: (a), (j), (k)—each has one H-bonding group and 4C;
•slightly soluble, "insoluble": (b) 6C; (d) 6C; (e) and (f) have no H-bonding group.
2-32
As summarized in the solution to problem 2-31, water solubility depends on the number of carbons and the
number of hydrogen-bonding groups in a molecule. A structure with one hydrogen-bonding group can
carry in three carbons for sure, called "miscible", meaning completely soluble; four carbons will be
partially soluble; five or more carbons will be only slightly soluble, which is sometimes called "insoluble".
(a) The first structure with 5 carbons and no hydrogen-bonding group is completely insoluble in water.
The second structure has 4 carbons and 1 oxygen; it is miscible with water because oxygen's electron pairs
can form hydrogen bonds with water.
(b) The first structure with 5 carbons and 1 oxygen is partially soluble in water (tetrahydropyran, 8 g/100
mL water). The second structure has 4 carbons and 2 oxygens; it is miscible with water.
(c) The first structure with 4 carbons and 1 oxygen is miscible with water. The second structure with 5
carbons and 1 oxygen is only partially soluble in water (2-methyltetrahydrofuran, 14 g/100 mL).
(d) The first structure with 5 carbons and no hydrogen-bonding group is completely insoluble in water.
The second structure has 6 carbons and 1 oxygen; it is partially soluble in water.
(e) The first structure with 5 carbons and 1 oxygen is slightly soluble in water. The second structure has 5
carbons and two bromines—which do not form hydrogen bonds—and is completely insoluble in water.
(f) The first structure with 5 carbons and 1 oxygen is partially soluble in water (tetrahydropyran, 8 g/100
mL water). The second structure has 4 carbons and 1 oxygen; it is miscible with water because the electron
pairs on oxygen are exposed and can readily form hydrogen bonds with water.
2-33 The boiling point of ethanol is much higher because these molecules can form hydrogen bond with
each other, thus requiring more energy to separate one molecule from another. Dimethyl ether molecules
cannot form hydrogen bond with each other, so it is relatively easy to separate them.
60
2-34
N CH3 N H O OH
N-methylpyrrolidine piperidine tetrahydropyran cyclopentanol

b.p. 81 °C b.p. 106 °C b.p. 88 °C b.p. 141 °C
(a) Piperidine has an N—H bond, so it can hydrogen bond with other molecules of itself.
N-Methylpyrrolidine has no N—H, so it cannot hydrogen bond and will require less energy (lower boiling
point) to separate one molecule from another.
(b) Two effects need to be explained: 1) Why does cyclopentanol have a higher boiling point than
tetrahydropyran? and 2) Why do the oxygen compounds have a greater difference in boiling points than the
analogous nitrogen compounds?
The answer to the first question is the same as in (a): cyclopentanol can hydrogen bond with its
neighbors while tetrahydropyran cannot.
The answer to the second question lies in the text, Table 2-1, that shows the bond dipole moments for
C—O and H—O are much greater than C—N and H—N; bonds to oxygen are more polarized, with greater
charge separation than bonds to nitrogen.
How is this reflected in the data? The boiling points of tetrahydropyran (88 °C) and
N-methylpyrrolidine (81 °C) are close; tetrahydropyran molecules would have a slightly stronger dipole-
dipole attraction, and tetrahydropyran is a little less "branched" than N-methylpyrrolidine, so it is reasonable
that tetrahydropyran boils at a slightly higher temperature. The large difference comes when comparing the
boiling points of cyclopentanol (141 °C) and piperidine (106 °C). The greater polarity of O—H versus N—H
is reflected in a more negative oxygen (more electronegative than nitrogen) and a more positive hydrogen,
resulting in a much stronger intermolecular attraction. The conclusion is that hydrogen bonding due to O—H
is much stronger than that due to N—H.
(c) Resonance plays a large role in the properties of amides.
O CH3 O CH3 O CH3 O CH3

H C N H C N H3C C N H3C C N
CH3 CH3 H H
N,N-dimethylformamide, b.p. 150 °C N-methylacetamide, b.p. 206 °C
The first structure has no hydrogen bonding because it has no O—H or N—H bond, but it is a highly polar
structure and has a large dipole moment, so its dipole-dipole intermolecular force is very high. The second
structure has hydrogen bonding because of the N—H bond in addition to the strong dipole-dipole interaction,
reflected in its higher boiling point. Both amides boil higher than the four at the beginning of the problem
because of the dipole-dipole interactions that are accentuated by the resonance forms.
2-35 Higher-boiling compounds are the ones described.
(a) CH3CH2CH(OH)CH3 can form hydrogen bonds with other molecules of itself.
(b) CH3CH2CH2CH2CH2CH3 has a higher molecular weight than CH3CH2CH2CH2CH3.
(c) CH3CH2CH2CH2CH2CH3 has less branching than (CH3)2CHCH2CH2CH3.
(d) (CH3)2CHCH2CH2CH2Cl has a higher molecular weight AND a dipole-dipole interaction compared with
(CH3)2CHCH2CH2CH3.
(e) (f) O
NH
has two sites for hydrogen bonding, not
can form hydrogen bonds
NH just one, and a very strong dipole
with other molecule of itself because of resonance.
(actual bp 81°C; the other
structure has bp 72°C).
61
2-36 The strength of the acid depends on the stability of the conjugate base. The two primary factors
governing the strength of organic acids are resonance and inductive effects; of these two, resonance is
usually the stronger and more important effect.
Any organic structure with an —SO3H in it is a very strong acid because the anion has three significant
resonance contributors. An organic structure with —COOH is moderately strong since the conjugate base
has two significant resonance contributors. A structure with a simple —OH does not have any resonance
stabilization of the conjugate base, so it is the weakest acid. Within each group, inductive effects from an
electronegative atom like Cl will have a small effect.
CH3CH2CH2OH > CH3CH2CH2COOH > ClCH2CH2CH2COOH > CH3CH2CHClCOOH > CH3CH2CH2SO3H
(b) (c) (e) (d) (a)
weakest acid Cl further from COOH Cl closer to COOH strongest acid
2-37 These pKa values from the text, Table 2-2 and Appendix 4, provide the answers. The lower the
pKa, the stronger the acid.
least acidic most acidic
CH4 < NH3 < H2O < HCN < HCOOH < HF < H2SO4
50 36 15.7 9.22 3.76 3.17 –5
2-38 Conjugate bases of the weakest acids will be the strongest bases. The pKa values of the conjugate
acids are listed here. (The relative order of some bases was determined from the pKa values in Appendix 4
of the textbook.)
least basic most basic
HSO4− < H2O < CH3COO− < NH3 < CH3O− ~ NaOH < −NH
2
from –5 from –1.7 from 4.74 from 9.4 from 15.5 from 15.7 from 36
2-39
(a) pKa = − log10 Ka = − log10 (5.2 x 10−5 ) = 4.3 for phenylacetic acid
for propionic acid, pKa 4.87: Ka = 10−4.87 = 1.35 x 10−5
(b) Phenylacetic acid is 3.9 times stronger than propionic acid.
5.2 x 10−5
= 3.9
1.35 x 10−5
(c)
CH2COO– + CH3CH2COOH CH2COOH + CH3CH2COO–
weaker acid stronger acid
Equilibrium favors the weaker acid and base. In this reaction, reactants are favored.
62
#3
2-40
(a) #1 NH #2
CH3 N C NH2
H+ to #1 H H+ to #2
H+ to #3
H NH NH
NH2
CH3 N C NH2 CH3 N C NH3
CH3 N C NH2
H H
no other significant H no other significant
resonance forms resonance forms
NH2 NH2 NH2

CH3 N C NH2 CH3 N C NH2 CH3 N C NH2
H H H
(b) Protonation at nitrogen #3 gives four resonance forms that delocalize the positive charge over all three
nitrogens and a carbon—a very stable condition. Nitrogen #3 will be protonated preferentially, which we
interpret as being more basic.
2-41 The critical principle: the strength of an acid is determined by the stability of its conjugate base.
(a) conjugate bases
W O X O Y O Z O
C C C OH C
CH2 NH N O
O O O O
C C C OH C
CH2 NH N O
(b) X is a stronger acid than W because the more electronegative N in X can support the negative charge better
than carbon, so the anion of X is more stable than the anion of W.
(c) Y is a stronger acid than X because the negative charge in Y is stabilized by the inductive effect from the
electronegative oxygen substituent, the OH.
(d) Z is a stronger acid than Y because of two effects: O is more electronegative than N and can support the
negative charge of the anion better, plus the anion of Z has two EQUIVALENT resonance forms, which is
particularly stable.
63
2-42
(a) H2SO4 + CH3COO– HSO4– + CH3COOH
(b) CH3COOH + (CH3)3N CH3COO– + (CH3)3N H

O O
(c) C O H + –OH C O– + H2O
O O
(d) HO C OH + 2 –OH –O C O– + 2 H2O
(e) H2O + NH3 HO– + +NH

4
(f) (CH3)3N H + –OH (CH3)3N + H2O
(g) HCOOH + CH3O– HCOO– + CH3OH
(h) NH3CH2COOH + 2 –OH NH2CH2COO– + 2 H2O
2-43 Values are from Appendix 4 in the text. The side of the equation with the weaker acid and base is
favored.
OH O
(a) + + FAVORS
REACTANTS
N O2N N O2N
weaker weaker stronger
base acid H base
pKa 7.1 stronger
acid
pKa 5.2
COOH COO
(b) + + FAVORS
PRODUCTS
N O2N N O2N
stronger stronger weaker
base acid H base
pKa 3.4 weaker
acid
pKa 5.2
64
2-43 continued
(c) + NaNH2 + NH3 FAVORS

N N PRODUCTS
weaker
stronger Na+ acid
H base
pKa 36
stronger weaker
acid base
pKa 17
Na+
O O
(d) H3C C NH2 + NaOCH2CH3 H3C C NH + HOCH2CH3 FAVORS

REACTANTS
weaker weaker stronger stronger but not by much
acid base base acid
pKa 16 pKa 15.9
The reaction in part (d) merits comment. Only 0.1 pKa units separates the two acids in this equation.
When pKa values are measured in solvents other than water (any pKa value higher than 15.7), the
experimental error increases. Without specifying that these two pKa values were measured in the
same solvent, it is difficult to give the difference of 0.1 pKa units much credence. Conclusion: the
two sides of the equation are fairly equally matched, and the products and reactants would probably
be close to 50:50. In one solvent, reactants may be favored, and in a different solvent, products
favored.
O OH
(e) H3C C NH2 + HCl (aq) H3C C NH2 + Cl FAVORS

PRODUCTS
base acid: in water, acid base
leveled to H3O+ pKa 0.0
pKa –1.7
Recall from problem 2-19 that the site of protonation of the reactant is the O, not the N.
Na+
O O O O
(f) C C + NaOH (aq) C C + H2O FAVORS
H3C C OEt H3C C OEt PRODUCTS
H2 stronger H weaker
base acid
stronger weaker pKa 15.7
acid base
pKa 10.7 Et = ethyl, CH2CH3
The most acidic proton in the reactant is the CH between the two C=O because of resonance
stabilization of the resultant anion by both C=O. See the solutions to problems 1-8(g) or 1-43(c) for
similar examples.
65
2-44 Note that this question is asking for the strength of the aqueous solution (pH), not just the strength of the
acid.
H2SO4 > HI = HBr > HCOOH > CH3COOH > HCN > NH4Cl
lowest pH, pKa = 3.76 pKa = 4.74 pKa = 9.22 highest pH,
equivalent—
strongest acid weakest acid
both leveled
to H3O +
Explanation: For acids weaker than water, the pH of the aqueous solution will follow the sequence of
the pKa values: the higher the pKa, the less they ionize in water. For acids stronger than water, they
will be leveled to hydronium ion, H3O+, so 1 molar solutions of HI and HBr would be completely
ionized, giving [H+] = 1M. The exception is H2SO4 because it is a diprotic acid: the first proton is
100% ionized, but the second proton (HSO4–) has pKa 2.0, higher than water but still a strong acid, so
some portion of it will also be ionized in excess of the first proton, making this aqueous solution the
strongest acid = lowest pH, with [H+] > 1M.
2-45 (a) conjugate bases
O O O O
C C C O F3C C
H3C O F3C O H3C O C O
H2
The negative charge cannot

be delocalized by resonance
O O in either of these two O
structures.
C C F3C C
H3C O F3C O C O
H2
CH3CH2 O
(b) O O O O
F3C
C
O
> F3C
C
C
O
>HC C
O H
> C
C
O
O > CH3CH2 O
3 3
H2
most stable— delocalization of weak least stable—no
delocalization of delocalization of negative charge by delocalization of delocalization of
negative charge by negative charge by resonance only negative charge negative charge
both resonance and resonance and a by induction only
induction weaker inductive
(electronegative F) effect as F atoms
are farther away
(c) The strongest acid will have the most stable conjugate base. The actual pKa values (some from text
Appendix 4) are listed beneath each acid.
O O O O
F3C
C
OH
>
F3C
C
C
OH H3C
> C
OH H3C
C >
O
OH >
CH3CH2OH
H2 weakest acid
strongest acid pKa 15.9
pKa 0.2 pKa 3.07 pKa 4.74 pKa 8.2
66
2-46
(a) conjugate acids H O H
The oxygen is more basic
N C than the nitrogen in this
structure. See the solution to
H CH3 Problem 2-19.
H H
CH3CH2 N H H O H H OH CH3CH2 O H H NH2
H N C minor
H CH3
H O H
N C
H CH3
(b) order of decreasing stability (pKa values from Appendix 4 in the text)
H H
H O H
H NH2 > H OH > CH3CH2 N H > N C >
CH3CH2 O H
most stable— neutral H H CH3 least stable—positive
neutral molecule molecule
with less polar positive charge on less positive charge on more charge on more
pKa 15.7 electronegative atom electronegative atom electronegative atom
NH bonds, lower
electronegativity pKa 10.7 but resonance stabilized pKa –2.4
pKa 0.0
pKa 36
(c) The weakest conjugate acid will form the strongest conjugate base.
H O
NH2 > OH > CH3CH2 N H > N C > CH3CH2 O H
strongest base H H CH3 weakest base
67
2-47
(a) conjugate bases
O O O O
O
C C S H3C S O
H3C O H3C NH H3C O F S O
O
O
O O O O
O
C C S H3C S O
H3C O H3C NH H3C O F S O
O
O
O
O
H3C S O
F S O
O
O
(b) O O O O O
F S O > H3C S O > H3C
S
O
> H3C
C
O
>HC 3
C
NH
O O
delocalization of delocalization of least stable—
most stable— delocalization of negative charge by negative charge by delocalization of
delocalization of negative charge by two resonance forms two equivalent negative charge by
negative charge by three resonance and induction (S resonance forms two resonance
three resonance forms and more electronegative forms, although
forms and induction (S more than C) non-equivalent
induction (F and S electronegative
more electro- than C)
negative than C)
(c) The strongest acid will have the most stable conjugate base. The pKa values are listed beneath each acid.
O O O O O
F S OH > H3C S OH > H3C
S
OH
> H3C
C
OH
> H3C
C
NH2
O O weakest acid
pKa 2.3 pKa 4.74
strongest acid pKa –1.2 pKa 16
pKa < –5
68
2-48
Of all the substituent groups in organic molecules, the nitro group, NO2, is the best electron-withdrawing
group. Not only does it have three electronegative atoms that can stabilize negative charge by induction,
but it also has very strong resonance stabilization. Adding just one nitro group to methane increase the
acidity by 40 pKa units!
O O
CH3
H2C N H2C N
no stabilization;
one of the strongest O O
bases known
one nitro group—strong stabilization
O O O
N O N O N O
H C H C H C
N O N O N O
O O O
two nitro groups—very strong stabilization
O O O O
O N O O N O O N O O N O
N C N C N C N C
O N O O N O O N O O N O
O O O O
three nitro groups—maximum stabilization—essentially zero negative charge on central C
Each subsequent substitution of H by NO2 increases the amount of the delocalization of the electron pair
on C, stabilizing the anion.
2-49
(a) CH3OH + CH3CH2Li CH3O–Li+ + CH3CH3
(b) The conjugate acid of CH3CH2Li is CH3CH3. Text Appendix 4 gives the pKa of CH3CH3 as 50, one
of the weakest acids known. The conjugate base of one of the weakest acids known must be one of the
strongest bases known.
2-50 The newly formed bond is shown in bold.
(a) CH3 O + CH3 Cl CH3 O CH3 + Cl
nucleophile electrophile
Lewis base Lewis acid
69
2-50 continued
(b) CH3 O CH3 + H O H CH3 O CH3 + H O H
H3C nucleophile CH3

electrophile Lewis base
Lewis acid
(c)
O H O
H C H + N H H C H
H H N H
electrophile
Lewis acid nucleophile
Lewis base H
H
(d) CH3 NH2 CH3CH2 Cl CH3 N CH2CH3 + Cl

nucleophile electrophile H
Lewis base Lewis acid
H
O O O O
(e) CH3 C CH2 H O S OH CH3 C CH3 O S OH

nucleophile
Lewis base O O
electrophile plus resonance forms
Lewis acid
CH3 Cl
(f) (CH3)3C Cl + AlCl3 H3C C + Cl Al Cl

Lewis base CH3 Cl
Lewis acid
This may also be written in two steps: association of the Cl with Al, and a second step where
the C—Cl bond breaks.
O O
(g) CH3 C CH2 + O H CH3 C CH2 + H O H

electrophile H nucleophile
Lewis acid Lewis base
F
(h) F B F CH2 CH2 F B CH2 CH2
F nucleophile F
electrophile Lewis base
Lewis acid
(i) BF3 CH2 CH2 + CH2 CH2 BF3 CH2 CH2 CH2 CH2
electrophile nucleophile
Lewis acid Lewis base
70
2-51 In each product, the new bond is shown in bold.
H
(a) CH3 N CH3 + H Cl CH3 N CH3 + Cl
Lewis H Lewis H
base— acid—
CH3
(b) CH3 N CH3 + H3C Cl CH3 N CH3 + Cl
Lewis Lewis
base— H acid— H
H
O O
(c) CH3 C H + H Cl CH3 C H + Cl
Lewis Lewis
base— acid—
O O
(d) CH3 C H + O CH3 CH3 C H
Notice in parts (d) and (e) that the
Lewis Lewis O identical reactants can generate two
acid— base—
CH3 separate products.
H O O
H
(e) H C C H + O CH3 C C H + H O CH3
Lewis Lewis H
acid— H base—
In each case, look for the atom that is the most positive because of induction or resonance, or is the most
electron deficient (like boron with an empty orbital).
(a) O O Resonance forms show that the C in a C=O group always
C has some (+) charge; this carbon is an electrophile.
Nucleophiles will be attracted to it as shown here and in
parts (e) and (f).
The Na+ is a spectator ion

O O
C and plays no active role in
+ O CH2CH3 these reactions. It is not
O CH2CH3 shown here to avoid clutter.
Lewis
base—
nucleophile
71
2-52 continued
H H
(b) H N H + O CH2CH3 H N + H O CH2CH3
H H
Br H
(c) H3C C H + O CH2CH3 H3C C O CH2CH3 + Br
H H
H H
(d) H B + O CH2CH3 H B O CH2CH3
H H
(e) As shown in 2-51(d) and (e), there can be more than one reaction pathway. NaOCH2CH3 is a strong base
and can quickly remove a proton from acetic acid, CH3COOH. In addition, the reaction can occur at the C=O
(see 2-52(a)) of acetic acid, although more slowly than proton removal which is one of the fastest reactions
known.
O O
1) C H + O CH2CH3 H O CH2CH3 + C
H3C O H3C O
(draw the other resonance form)
O O
2) C H + O CH2CH3 C H
H3C O H3C O
O CH2CH3
(f) As shown in 2-51(d) and (e), and 2-52(e) above, there can be more than one reaction pathway. Draw
important resonance forms to reveal where the sites of (+) and (–) charge are.
H H H
H C O H C O H C O
C C C
site 1
H H H site 2
H H
H C O + O CH2CH3 H C O
1)
C C
O CH2CH3
H H
H
H H C O This is the most significant
2) resonance contributor.
H C O + O CH2CH3 C
Draw the other one.
C H O CH2CH3
72
H Copyright © 2017 Pearson Education, Ltd.
In each case, look for an unshared electron pair, or an electron pair in a double or triple bond, to make a
molecule nucleophilic. An arrow showing electron movement must always begin at an unshared
electron pair or a bond. F
O F O B F
(a) + B F
F F
F F
F B
(b) F
+ B
F F C
H
F F
B
O F O F CH3 F CH3 F
(c) + B (d) N + B H3C N B F

F F H3C CH3 F F
CH3 F
H F H F
(e) H3C O + B H3C O B F

C F F C
H2 H2 F
F F
(f) S + B H3C S B F
H3C CH3 F F
CH3 F
2-54 (a) Ascorbic acid has four OH groups that could act as acids. The ionization of each shows that one
gives a more stable conjugate base.
OH
OH 2 1
O localized negative charge—
O no resonance forms
O
O
O HO OH
OH
1 HO OH
2 O
3 4
ascorbic acid O localized negative charge—

O no resonance forms
OH
HO OH
continued on next page 73
2-54(a) continued
OH 2 OH OH
O 3 O O
O O O
OH OH OH C
1 HO OH O OH O OH
3 4
three resonance forms, two OH

with negative charge on
4
oxygen O
O
OH
O OH
OH OH
O O
O O
OH OH C two resonance forms, one with
HO O HO O negative charge on oxygen
(b) The ionization of the OH labeled "3" produces a conjugate base with three resonance forms, two of which
have negative charge on oxygen. This OH is the most acidic group in ascorbic acid.
(c) The conjugate base of acetic acid, the acetate ion, CH3COO– , has two resonance forms (see the solution
to problem 2-47), each of which has a C=O and a negatively charged oxygen, similar to two of the resonance
forms of the ascorbate ion. The acidity of these two very different molecules is similar because the
stabilization of the conjugate base is so similar. The strength of an acid is determined by the stability of its
conjugate base.
Note to the student: Organic chemistry professors will ask you to "explain" questions, that is, to explain a
certain trend in organic structures or behavior of an organic reaction. The professor is trying to determine
two things: 1) Does the student understand the principle underlying the behavior? 2) Does the student
understand how the principle applies in this particular example?
To answer an "explain" question, somewhere in your answer should be a statement of the principle,
like: "The strength of an acid is determined by the stability of its conjugate base." From there, show
through a series of logical steps how the principle applies, like drawing resonance forms to show which
acid has the most stable conjugate base through resonance or induction. Answering these questions is
like crossing a creek on stepping stones. Each phrase or sentence is a step to the next stone. When strung
together, the steps bridge the gap between the principle and the observation.
2-55 The examples here are representative. Your examples may be different and still be correct. What is
important in this problem is to have the same functional group.
(a) alkane: hydrocarbon (b) alkene: contains a (c) alkyne: contains a
with all single bonds; can be carbon-carbon double bond carbon-carbon triple bond
acyclic (no ring) or cyclic
H H H H H
H C C C H H C C C H H C C C H
H H H H H H H
74
2-55 continued
(d) alcohol: contains an (e) ether: contains an (f) ketone: contains a carbonyl
OH group on a carbon oxygen between two carbons group between two carbons
H H H H H O H
H C C O H H C O C H H C C C H
H H H H H H
(g) aldehyde: contains (h) aromatic hydrocarbon: (i) carboxylic acid: contains a
a carbonyl group with a a cyclic hydrocarbon with carbonyl group with an OH
hydrogen on one side alternating double and single group on one side
H H O bonds H O
H C C C H H C C O H
H H H
(j) ester: contains a carbonyl (k) amine: contains a nitrogen (l) amide: contains a carbonyl
group with an O—C on one side bonded to one, two, or three group with a nitrogen on one side
carbons
H O H H H or R group H O H or R group
H C C O C H H C N H or R group H C C N H or R group
H H H H
(m) nitrile: contains the carbon-nitrogen triple bond: H3C C N
O O O aldehyde
2-56 ether
(a) (b) (c)
C OH C
H
O ether
carboxylic acid
alkene
alkene
O
(d) (e) O (f) O (g) CH2OCH3
ketone ether
O NH aromatic
alkene
aromatic amide (cyclic) C N
ester (cyclic)
nitrile
(h) NH2 O (i) H
HN C COOH carboxylic acid
CH3 CH C OCH3 amine 2
H2C OH alcohol
amine ester
2-57
(a) penicillin G
O amide thioether ("Thio" means sulfur replaces oxygen. This
group is listed on the inside front cover of the text.)
CH2 C NH
S
aromatic N
O carboxylic acid
amide COOH
(cyclic) 75
2-57 continued
(b) dopamine
alcohol aromatic (In later chapters, you will learn that the
HO
OH group on a benzene ring is a special
NH2 functional group called a "phenol". For
alcohol amine
now, it fits the broad definition of an
HO CH2 CH2 alcohol.)
(c) capsaicin
aromatic amide
ether O
alkene
H3CO
N
H
HO (In later chapters, you will learn that the

alcohol OH group on a benzene ring is a special
functional group called a "phenol". For
now, it fits the broad definition of an
alcohol.)
(d) thyroxine
aryl iodide—
I (four of these) I aromatic amine "Aryl" iodides are attached
to aromatic rings.
NH2
alcohol
HO O CH C COOH
ether H carboxylic acid
I aromatic I
(e) testosterone OH alcohol
ketone
O
alkene
76
CHAPTER 3—STRUCTURE AND STEREOCHEMISTRY OF ALKANES
3-1 (a) CnH2n+2 where n = 27 gives C27H56 (b) CnH2n+2 where n = 42 gives C42H86
Note to the student: The IUPAC system of nomenclature has a well-defined set of rules determining how
structures are named. You will find a summary of these rules as Appendix 5 in the textbook.
3-2 Use hyphens to separate letters from numbers. Structures might not display their longest chains left to
right—you have to search for them. In the name, write substituents in alphabetical order, even though that
might be different from the numerical order of position numbers.
(a) 3-methylpentane (Always find the longest chain; it may not be written in a straight line.)
(b) 2-bromo-3-methylpentane (Always find the longest chain.)
(c) 5-ethyl-2-methyl-4-propylheptane ("When there are two longest chains of equal length, use the chain
with the greater number of substituents.")
(d) 4-isopropyl-2-methyldecane ("Number from the end closest to the first substituent." —also for (c))
3-3 This Solutions Manual will present line–angle formulas, or simply "line formulas", where a question
asks for an answer including a structure. If you use condensed structural formulas instead, be sure that you
are able to "translate" one structure type into the other.
2 4 6 8 2 6 8
(a) 2 6
(b) 1 3 5 (c) (d) 3 5
7 9 1 4
3 7
4
1 5 2 4 6
1 3 5 7
3-4 Separate numbers from numbers with commas. Separate numbers from letters with hyphens.
(a) 2-methylbutane (b) 2,2-dimethylpropane (c) 3-ethyl-2-methylhexane
(d) 2,4-dimethylhexane (e) 3-ethyl-2,2,4,5-tetramethylhexane (f) 4-tert-butyl-3-methylheptane
3-5 In some cases of an ambiguous or incorrect name, more than one possible structure might be implied.
That is often the problem with a wrong name: it does not describe a unique structure.
(a) incorrect: 3-ethyl-4-methylpentane (b) incorrect: 2-ethyl-3-methylpentane
The chain is numbered in the wrong The longest chain was not identified.
direction. The methyl should be on the
second carbon, not the fourth. 1 2
methyl 4 5
4 1 3 5 4 6
1 3 5 2 3
2
ethyl INCORRECT CORRECT

correct: 3-ethyl-2-methylpentane correct: 3,4-dimethylhexane
(c) incorrect: 3-dimethylhexane (d) incorrect: 4-isobutylheptane

Two substituents require two position This is a more subtle error. If two chains of
numbers, even if they are both 3; that is equal length are possible, select the one that
the example shown below. It is also maximizes the number of substituents.
possible that a different position methyl
number was omitted, like "3,4-". 2
4 1
1 3 5 propyl 3
2 6
1 3 5 7 5 7
2 4 6 4 6
correct: 3,3-dimethylhexane INCORRECT CORRECT

one substituent two substituents
correct: 2-methyl-4-propylheptane
77
3-5 continued (f) incorrect: 2,3-diethyl-5-isopropylheptane
(e) incorrect: 2-bromo-3-ethylbutane The longest chain is 8 carbons: octane.
The longest chain was not identified. Numbering from the lower right corner as shown
below puts the first substituent on carbon-2, and
4 5 also maximizes the number of substituents.
1 1 8
2 4 2 7
3 3 4 6 4
1 3 5 5 3
Br Br 2 6
7
2
INCORRECT CORRECT 1
correct: 2-bromo-3-methylpentane
INCORRECT CORRECT
correct: 3,5-diethyl-2,6-dimethyloctane
3-6 (Hints: systematize your approach to these problems. For the isomers of a six-carbon formula, for
example, start with the isomer containing all six carbons in a straight chain, then the isomers containing a
five-carbon chain, then a four-carbon chain, etc. Carefully check your answers to AVOID DUPLICATE
STRUCTURES.)
(a)
hexane
(or n-hexane) 2-methylpentane 3-methylpentane 2,2-dimethylbutane 2,3-dimethylbutane
(b)
heptane
(or n-heptane) 2-methylhexane 3-methylhexane 2,2-dimethylpentane
3,3-dimethylpentane 2,3-dimethylpentane 2,4-dimethylpentane 3-ethylpentane 2,2,3-trimethylbutane

3-7 For this problem, the carbon numbers in the substituents are indicated in italics. The bold bond shows
the point of attachment.
(a) CH3 (b) CH3 (c) CH3
CHCH3 CH2CHCH3 CHCH2CH3
1 2 1 2 3 1 2 3
2°
1-methylethyl 2-methylpropyl
common name = isopropyl common name = isobutyl 1-methylpropyl
common name = sec-butyl,
abbreviation for secondary-butyl
CH3 (e) CH3

(d)
1 2
C CH3 CH2CH2CHCH3
1 2 3 4
CH3 3-methylbutyl
3°
common name = isopentyl or isoamyl
1,1-dimethylethyl
common name = tert-butyl or t-butyl,
abbreviation for tertiary-butyl
78
3-8
(a) (b) (c)
3-9 Once the number of carbons is determined, CnH2n+2 gives the formula.
(a) octane = 8C; plus 1,1-dimethylethyl = 4C 12 C, C12H26
(b) nonane = 9C; plus trimethyl = 3C; plus propyl = 3C 15 C, C15H32
3-10
(a) (lowest b.p.) hexane < octane < decane (highest b.p.) —molecular weight
(b) (CH3)3C—C(CH3)3 < CH3CH2C(CH3)2CH2CH2CH3 < octane —branching differences

(lowest b.p.) (highest b.p.)
some branching no branching

actual b.p. 112 °C actual b.p. 126 °C
most branching
actual b.p. 107 °C
3-11 Part (a) was answered in the text.
(b) front carbon back carbon Newman projection
For nomenclature practice,
H H
can you name these?
Cl H Cl H
Br CH3 Br CH3
2-bromo-3-chloropentane
CH2CH3 CH2CH3
(c) front carbon back carbon Newman projection

CH2CH3 CH2CH3
H CH3 H CH3
H Br H Br
3-bromo-4-methylhexane
CH2CH3 CH2CH3
An excellent exercise for your study group is for one person to create a Newman projection,
and for the other people in the group to translate that Newman into a line formula, and name it.
79
3-12
potential energy 15.0 kJ/mole

(3.6 kcal/mole)
dihedral
0° 60° 120° angle θ
HCH3 CH3 HCH3
H H
HH H CH3 HH H
CH3 H CH3
H
eclipsed staggered eclipsed
1 x 4.2 kJ/mole + 2 x 5.4 kJ/mole = 15.0 kJ/mole (3.6 kcal/mole)
H H H CH3
3-13
Relative energies on the graph on the next page were calculated using these values from the text: 3.8 kJ/mole
(0.9 kcal/mole) for a CH3–CH3 gauche (staggered) interaction; 4.2 kJ/mole (1.0 kcal/mole) for a H–H
eclipsed interaction; 5.4 kJ/mole (1.3 kcal/mole) for a H–CH3 eclipsed interaction; 12.5 kJ/mole (3.0
kcal/mole) for a CH3–CH3 eclipsed interaction. These values in kJ/mole are noted on each structure and are
summed to give the energy value on the graph. Slight variations between values here and in the text are due
to rounding.
potential energy
22.1 kJ 16.2 kJ 7.6 kJ

All energy values
5.3 kcal 3.9 kcal 1.8 kcal are per mole.
3.8 kJ; 0.9 kcal
dihedral
0° 60° 120° 180° 240° 300° 360° angle θ
H3C 12.5 H 5.4 H3C 12.5 H3C 12.5

CH3 CH3 CH3 CH3
4.2 H 5.4 H 5.4 H 4.2 H

H HCH 3 H3C HCH 3 H3C HH H HCH 3
eclipsed 5.4 eclipsed 5.4 eclipsed4.2 eclipsed 5.4
CH3 3.8 3.8 CH3 3.8 CH3 3.8 (Note that the lowest
H CH3 H3C H H3C CH3 energy conformers at
60° and 180° have at
H H H H H H least one CH3—CH3
interaction = 3.8 kJ
CH3 CH3 H (0.9 kcal) higher than
staggered staggered staggered ethane.)
80
3-14 H H H H H H Wedge bonds are coming toward the
H reader above the plane of the paper.
H Dashed bonds are going away from the
H H H CH3 H H reader behind the plane of the paper.
All bonds are staggered.
3-15 Note that in rings, parts (a) and (b), two substituents on one carbon indicate where to begin numbering.
(a) 3-sec-butyl-1,1-dimethylcyclopentane
(b) 3-cyclopropyl-1,1-dimethylcyclohexane
(c) 4-cyclobutylnonane (The chain is longer than the ring.)
3-16 (a) C10H20 (b) C10H20 (c) C8H14 (d) C10H20
(e) C10H22 (f) C16H32
3-17 It helps to visualize cis-trans isomerism by putting in the H atoms on the carbons with substituents.
(a) no cis-trans isomerism possible The terms cis and trans designate relative
CH3 position. For cis, both substituents have to
H
(b) 3 be on the same side; it does not matter if
3
and H 2 both are up or both down. For trans, one
H 2 H
CH3 must be up and the other down; it does not
1
cis 1 trans matter which is which.
CH CH
CH2CH3 2 3
(c) CH3 CH2CH3 H CH2CH3 (d) 1 CH3 1 H

3 1 and 3 1 H 2 and H 2
H H CH3 H
H CH3
cis trans cis trans
3-18 In (a) and (b), numbering of the ring is determined by the first group alphabetically being assigned to
ring carbon 1.
(a) cis-1-methyl-3-propylcyclobutane ("M" comes before "p"—practice that alphabet!)
(b) trans-1-tert-butyl-3-ethylcyclohexane (Tert, sec, and n are ignored in assigning alphabetical priority.)
(c) trans-1,2-dimethylcyclopropane (Either carbon with a CH3 could be carbon-1; the same name results.)
3-19 Combustion of the cis isomer gives off more energy, so cis-1,2-dimethylcyclopropane must start at a
higher energy than the trans isomer. The Newman projection of the cis isomer shows the two methyls are
eclipsed with each other; in the trans isomer, the methyls are still eclipsed, but with hydrogens, not each
other—a lower energy interaction.
more strain =
CH3 higher energy H
CH3 CH3
cis trans
HH H CH3
81
3-20 trans-1,2-Dimethylcyclobutane is more stable than cis because the two methyls can be farther apart
when trans, as shown in the Newman projections.
more strain =
CH3 higher energy H
CH3 CH3
cis trans
HH H CH3
In the 1,3-dimethylcyclobutanes, however, the cis allows the methyls to be farther from other atoms and
therefore more stable than the trans.
CH3 CH3 H CH3

cis trans
H H CH3 H
3-21
axial only
equatorial only
showing both axial
and equatorial
3-22 The abbreviation for a methyl group, CH3, is "Me". Ethyl is "Et", propyl is "Pr", and butyl is "Bu".
Me Me H H
(a) Me H (b) H Me
H H Me Me
H H Me Me
H Me Me H
Me Me H H
all methyls axial all methyls equatorial
(all H equatorial) (all H axial)
Note that axial groups alternate
up and down around the ring.
3-23 Carbons 4 and 6 are the back carbons.
anti
4 H H 6
5
H CH2 H
3 1
H CH2 CH3
H 2 H
82
3-24 The isopropyl group can rotate so that its hydrogen is near the axial hydrogens on carbons 3 and 5,
similar to a methyl group's hydrogen, and therefore similar to a methyl group in energy. The tert-butyl
group, however, must point a methyl group toward the hydrogens on carbons 3 and 5, giving severe diaxial
interactions, causing the energy of this conformer to jump dramatically.
CH3 H
CH3
H H CH3 H CH3
H H
H H
isopropylcyclohexane tert-butylcyclohexane
H CH3
3-25 The most stable conformers have larger substituents equatorial. (c) CH3
H CH3 H CH3
(a) (b) CH3 H
H CH3 CH3
H H
H3C H
H3C H3C
The cis-1,4 isomer must have one group
axial and the other equatorial. The tert-
butyl group is larger and will take the
equatorial position.
3-26 The key to determining cis and trans around a cyclohexane ring is to see whether a substituent group
is "up" or "down" relative to the H at the same carbon. Two "up" groups or two "down" groups will be cis;
one "up" and one "down" will be trans. This works independent of the conformation the molecule is in!
(a) cis-1,3-dimethylcyclohexane (d) cis-1,3-dimethylcyclohexane
(b) cis-1,4-dimethylcyclohexane (e) cis-1,3-dimethylcyclohexane
(c) trans-1,2-dimethylcyclohexane (f) trans-1,4-dimethylcyclohexane
3-27 CH3 CH3

(a) cis
H H
H3C CH3
EQUAL ENERGY
H H
equatorial, axial axial, equatorial
CH3 H
(b) trans
H H3C
H CH3
CH3 H
axial, axial equatorial, equatorial
higher energy lower energy
(c) The trans isomer is more stable because BOTH substituents can be in the preferred equatorial positions.
83
3-28
Positions cis trans
1,2 (e,a) or (a,e) (e,e) or (a,a)
1,3 (e,e) or (a,a) (e,a) or (a,e)
1,4 (e,a) or (a,e) (e,e) or (a,a)
3-29 The more stable conformer places the larger group equatorial.
CH2CH3
(a) CH3
H more stable—
CH3 CH2CH3 larger group equatorial
H
H H
CH2CH3 H
(b) H
H CH2CH3 more stable—
CH2 both groups equatorial
CH2CH3 H3C H
H3C
(c) more stable— CH2CH3 H3C CH
larger group equatorial H H
(CH3)2CH CH2CH3
H H
CH2CH3 H
(d)
H CH3 more stable—
H CH2CH3 both groups equatorial
CH3 H
3-30 H H
H
(a) C(CH3)3 (b) C(CH3)3
CH3
CH2CH3
H
(c) Bulky substituents like tert-butyl adopt equatorial rather than axial positions, even if that means altering
the conformation of the ring. The twist boat conformation allows both bulky substituents to be "equatorial".
H CH3
C CH2CH3
CH3
(CH3)3C
H
84
3-31 The nomenclature of bicyclic alkanes is summarized in Appendix 5 in the textbook.
(a) bicyclo[3.1.0]hexane (b) bicyclo[3.3.1]nonane (c) bicyclo[2.2.2]octane (d) bicyclo[3.1.1]heptane
3-32 Using models is essential for this problem.

H H
1 H 2 rotate
1 picture
H 2
2 1 H
H
from text Figure 3-27
3-33
(a) Here are eighteen isomers of C8H18. An easy way to compare is to name yours and see if the names
match. Note how these isomers were generated systematically: 8C chain (only one), all the possible 7C
chains with one methyl, all the 6C chains with two methyls or 1 ethyl, etc.
8-carbon chain
octane
7-carbon chain
2-methylheptane 3-methylheptane 4-methylheptane

6-carbon chain
2,2-dimethylhexane 2,3-dimethylhexane 2,4-dimethylhexane 2,5-dimethylhexane
3,3-dimethylhexane 3,4-dimethylhexane 3-ethylhexane

5-carbon chain
2,2,3-trimethylpentane 2,2,4-trimethylpentane 2,3,3-trimethylpentane 2,3,4-trimethylpentane
3-ethyl-2-methylpentane 3-ethyl-3-methylpentane
4-carbon chain
2,2,3,3-tetramethylbutane 85
3-33 continued
(b)
constitutional isomers
ethylcyclopentane 1,1-dimethylcyclopentane
("1" is not necessary
if the ring has only cis-1,2-dimethylcyclopentane cis-1,3-dimethylcyclopentane
one substituent) geometric geometric
isomers isomers
trans-1,2-dimethylcyclopentane trans-1,3-dimethylcyclopentane
3-34
(a) The third structure is 2-methylpropane (isobutane). The other four structures are all butane (n-butane).
Remember that a compound's identity is determined by how the atoms are connected, not by the position of
the atoms when a structure is drawn on a page.
(b) The first and fourth structures are both cis-but-2-ene. The second and fifth structures are both but-1-ene.
The third structure is trans-but-2-ene. The last structure is 2-methylpropene.
(c) The first two structures are both cis-1,2-dimethylcyclopentane. The next two structures are both trans-
1,2-dimethylcyclopentane. The last structure, cis-1,3-dimethylcyclopentane, is different from all the others.
(d) Analysis of the structures shows that

some double bonds begin at carbon-2 and
some at carbon-3 of the longest chain.
The three structures labeled A are the
A A B same, with the double bond trans; B is a
geometric isomer (cis) of A. C and D are
constitutional isomers of the others.
A C D
CH3 H3C H
(e) Naming the structures
shows that three of the H H CH3
structures are trans-1,4- H
H3C H
dimethylcyclohexane, two are H CH3
the cis isomer, and one is cis- CH3
1,3-dimethylcyclohexane. cis-1,4-dimethyl trans-1,4-dimethyl cis-1,4-dimethyl
Although a structure may be
shown in two different H H CH3
H H CH3
conformations, it still
represents only one compound. H3C
CH3 CH3 H
H3C H
cis-1,3-dimethyl trans-1,4-dimethyl trans-1,4-dimethyl
86
3-34 continued
(f) An important and useful skill is the ability to translate Newman projections into other structural formulas
and vice versa. The way to do this is to start with the two carbons that represent the front and back carbons in
the middle of the Newman projections, then attach the three groups emanating from each one.
CH3 H CH3 H H
H CH3 H3C CH3 H CH3 H3C CH(CH3)2 H3C CH2CH3
H CH3 H3C CH3 H3C CH3 H H H H

CH3 H H H CH3
CH3 CH3 CH3 CH3 CH3 CH3 H CH(CH3)2 H CH2CH3

H C C H H C C H H3C C C H H C C H H C C CH3
CH3 CH3 CH3 CH3 CH3 H H CH3 H CH3
2,3-dimethylbutane 2,3-dimethylbutane 2,2-dimethylbutane 2,3-dimethylbutane 2,2-dimethylbutane
What may not be clear in the Newman projections is revealed in the structural formulas and especially in the
names. There are only two compounds represented here: the first, second, and fourth are the same; the third
and fifth are the same.
(g) Names have been incorporated into the other solutions.
3-35
(a) Start with a 5-carbon ring and work to smaller rings:
cyclopentane methylcyclobutane ethylcyclopropane 1,1-dimethylcyclopropane

has two
geometric isomers
1,2-dimethylcyclopropane cis-1,2-dimethylcyclopropane trans-1,2-dimethylcyclopropane

(b) Start with a 6-carbon ring and work to smaller rings:
cyclohexane methylcyclo- ethylcyclo- 1,1-dimethyl- propylcyclo- isopropyl- 1-ethyl-1-methyl- 1,1,3-trimethyl-

pentane butane cyclobutane propane cyclopropane cyclopropane cyclopropane
(c) Each of these four structures has two geometric isomers.
1,2-dimethyl- cis- trans- 1-ethyl-2-methyl- cis- trans-

cyclobutane cyclopropane
1,3-dimethyl- cis- trans-

1,2,3-trimethylcyclopropane all cis cis,trans
cyclobutane
87 These stereochemical names are
Copyright © 2017 Pearson Education, Ltd. descriptive, not IUPAC.
3-36 Line–angle formulas are shown.
(a) (b) (c)

CH2CH3
or
(d) (e) (f)
CH2CH3
(g) (h) (i)

H H
Cl
(j) (k) (l) Br H
3-37 There are often many possible answers to this type of problem, although some can have unique
solutions. The ones shown here are examples of correct answers. Your answers may be different AND
correct. Check your answers in your study group.
(a) 4-Isopropylheptane is the only possible answer. Why not 1- or 2- or 3- ? Draw

these structures in your study group, and name them.
(Any combination is
(b) correct except using
position numbers 1 or 2
or 9 or 10. Why won't
these work?)
4,5-diethyldecane 3,5-diethyldecane
CH2CH3 CH2CH3 CH2CH3
(c)
CH2CH3 CH3CH2
CH2CH3
cis-1,2-diethylcyclohexane cis-1,3-diethylcyclohexane cis-1,4-diethylcyclohexane
NOT 1,5—same as 1,3; NOT 1,6—same as 1,2
(d) "Halo" is the abbreviation for any of the four halogens (F, Cl, Br, I), and "X" is the symbol used in organic
structures. If unspecified, any of the four elements will satisfy the "halo" group. However, on a 5-membered
ring, the substitution can be only two possibilities: 1,2- or 1,3- .
"X" stands for any of the
X X four halogen elements.
1 1
trans-1,2-dihalocyclopentane X trans-1,3-dihalocyclopentane
2
3
X
88
3-37 continued
(e) 1 1
2 4 5 2 4 5 Other ring sizes are
3 3 possible, although they must
have 6 or more carbons to
be longer than the 5 carbons
of the substituent chain.
(2,3-dimethylpentyl)cycloheptane (2,3-dimethylpentyl)cyclooctane
(f) Any combination where the number

of carbons in the bridges sums to 7
will work. (Two carbons are the
bridgehead carbons.)
bicyclo[4.3.0]nonane
bicyclo[3.2.2]nonane bicyclo[3.3.1]nonane
3-38 Cl CH3 Cl CH2CH2CH3 Cl CH2CH2CH2CH2CH3

Cl CH2CH3 Cl CH2CH2CH2CH3 Cl CH2CH2CH2CH2CH2CH3
3-39
(a) 3-ethyl-2,2,6-trimethylheptane (b) 3-ethyl-2,6,7-trimethyloctane
(c) 3,7-diethyl-2,2,8-trimethyldecane (d) 1,1-diethyl-2-methylcyclobutane
(e) bicyclo[4.1.0]heptane (f) cis-1-ethyl-3-propylcyclopentane
(g) (1,1-diethylpropyl)cyclohexane (h) cis-1-ethyl-4-isopropylcyclodecane
3-40 The ethyl group, —CH2CH3 , is abbreviated Et. The back carbon is kept constant while the front
carbon is rotated clockwise. The problem asks for relative energies, not calculations; the ethyl group is
slightly larger than a methyl group, causing a higher energy than methyl in eclipsed conformations.
Interestingly, all of the minima and all of the maxima are at different energies; this arises because the
three groups on the back carbon (H, CH3, CH2CH3) are all different.
potential energy
H CH3
H3C 2
3
H H Et =
ethyl
dihedral
0° 60° 120° 180° 240° 300° 360° angle θ
H H H3C H H CH3 H H
H CH3 H CH3 H CH3 H CH3
highest highest
Et CH Et H Et H Et CH
energy— 3 3 energy—
CH3 eclipsed eclipsed eclipsed eclipsed CH3
eclipsing eclipsing
H CH3 H
CH2CH3 CH2CH3
H CH3 H CH3 H CH3
The pictures H3C H H H H CH3

of eclipsed
forms have Et Et Et
exaggerated staggered staggered staggered lowest energy—
bond angles. CH3 farthest
89
Copyright © 2017 Pearson Education, Ltd. from CH2CH3
3-41 1
4 6
3 5
(a) 2 (b)
3 2
5
4 6 1
correct name: 3-methylhexane correct name: 3-ethyl-2-methylhexane
(longer chain) (more branching with this numbering)
(c) (d)
2 1
5 3
6 4
Cl correct name: 2,2-dimethylbutane (Include
correct name: 2-chloro-3-methylhexane a position number for each substituent,
(Begin numbering at end closest to substituent.) regardless of redundancies.)
(e) (f) CH2CH3
CH2CH3
correct name: sec-butylcyclohexane or correct name: 1,2-diethylcyclopentane

(1-methylpropyl)cyclohexane (Position numbers are the lowest possible.)
(The longer chain or ring is the base name.) cis- or trans- is not specified.
3-42
(a) Nonane has a higher boiling point than 3-methylheptane because nonane has a higher molecular weight
and it is a linear structure as opposed to the lighter, branched 3-methylheptane.
(b) Octane has a higher boiling point than 2,3,4-trimethylpentane because linear molecules boil higher than
branched molecules of the same molecular weight (increased van der Waals interaction).
(c) Nonane boils higher than 2,3,5-trimethylhexane for the same reason as in (a).
3-43 The point of attachment is shown by the bold bond at the left of each structure.
CH2CH2CH2CH2CH3 CHCH2CH2CH3 CH2CHCH2CH3

1° 2° CH 1°
pentyl 3 1-methylbutyl CH3 2-methylbutyl
(old: amyl)
CH3
CH2CH2CHCH3 CHCH2CH3 C CH2CH3
2° 3°
1° CH2CH3 1-ethylpropyl CH3 1,1-dimethylpropyl
CH3 3-methylbutyl (tert-pentyl;
(isopentyl; old: tert-amyl)
old: isoamyl)
CH3
CH3
CHCHCH3 CH2 C CH3
2° CH3 1,2-dimethylpropyl 1° CH3 2,2-dimethylpropyl
(neo-pentyl)
90
3-44 In each case, put the largest groups on adjacent carbons in anti positions to make the most stable
conformations. 4 5
(a) 3-methylpentane CH2CH3 Newman projections were
introduced in text section 3-7.
H H They are used extensively to
2 show the three-dimensional
3 arrangement of atoms in a
2 molecule.
H CH3
C-2 is the front carbon with H, H, and CH3
C-3 is the back carbon with H, CH3, and CH2CH3 Carbon-3 is behind carbon-2.
1 CH3
5 6
CH2CH3
(b) 3,3-dimethylhexane
H3C CH3
4 Carbon-4 is behind carbon-3.
3 3
H H
C-3 is the front carbon with CH3, CH3, and CH2CH3
C-4 is the back carbon with H, H, and CH2CH3 CH2CH3
2 1
3-45 axial
axial H
(a) H
CH3 equatorial H H equatorial
equatorial CH3 CH3
CH3
axial axial
equatorial
(b) more stable less stable
(lower energy) (higher energy)
(c) From Section 3-14 of the text, each gauche interaction raises the energy 3.8 kJ/mole (0.9 kcal/mole),
and each axial methyl has two gauche interactions, so the energy is:
2 methyls x 2 interactions per methyl x 3.8 kJ/mole per interaction = 15.2 kJ/mole (3.6 kcal/mole)
(d) The steric strain from the 1,3-diaxial interaction of the methyls must be the difference between the
total energy and the energy due to gauche interactions: 23 kJ/mole – 15.2 kJ/mole = 7.8 kJ/mole
(5.4 kcal/mole – 3.6 kcal/mole = 1.8 kcal/mole)
3-46 The more stable conformer places the larger group equatorial. ax
ax ax CH CH
CH(CH3)2 CH(CH3)2 H
(a) 2 3 (b) eq
H H
CH2CH3 H CH(CH3)2
CH(CH3)2 Et
eq H eq eq H
H H CH2CH3 Et = ethyl
ax
more stable— more stable—
larger group equatorial both groups equatorial
ax ax
(c) ax CH2CH3 eq eq (d) CH2CH3
CH3 H eq
H CH3 CH2CH3 H H CH2CH3
H H ax CH3 H
H CH
more stable— eq 3 more stable—
both groups equatorial larger group equatorial
91
3-46 continued ax ax ax
CH2CH3 CH3 CH2CH3 H
(e) (f)
H H eq H CH3 eq
CH3 CH2CH3 H eq CH2CH3
eq
H H CH3 H
more stable— ax more stable—
larger group equatorial both groups equatorial
3-47 (Using models is essential to this problem.)

In both cis- and trans-decalin, the cyclohexane rings can be in chair conformations. The relative energies
will depend on the number of axial substituents.
trans cis
(one axial substituents) (two axial substituent)
MORE STABLE
3-48 Solutions are given in the boxes. The front and back carbons from the Newman projection are
denoted by a dark dot.
4 5
(a) H (b) CH2CH3
H H H CH3 3
1 2 4
2 4 2 1 5
H H 1 3 H CH3
CH2CH3 butane 1 CH3
3 4 2,3-dimethylpentane
5 6
(c) Br (d) CH2CH3
2
H CH3 Br 1 3 H Cl
4 2 3 4 6
1 3
1 5
H H H CH3
CH2CH3 1-bromo-2-methylbutane Cl
CH(CH3)2
3 4 2 1 3-chloro-2,4-dimethylhexane
2 1 Cl
5
(e) C(CH3)3 (f) CH3
1 2 3 5
Br H H CH3 2 3 4
4 6
1 5
3 3
Cl CH3 Br H H
CH2CH3 4-bromo-3-chloro- CH(CH3)2 2,3-dimethylpentane
5 6 2,2,3-trimethylhexane 2 1
This is the same structure as part (b),
sighted down a different bond.
92
3-48 continued
(g) F F Br (h) H Br
1 F Br
H CBr3 F 2
Cl
3 2 1 3 2 1
3
F Br 4
F F H Br
F Cl
H 1,1,1-tribromo-3,3,3- CH2CH3 1-bromo-2-chloro-2-
3 4
trifluoropropane fluorobutane
Br comes before F in the alphabet
2 1
Br Br
(i) CH(CH3)2 (j) Br
Cl
Br H 2 H CH3
3 1 3 5 2 3 2 1
4 6 4 F
Br H Cl F
Br
CH2CH3 CH2CH3 1-bromo-1-chloro-1-
5 6 3,4-dibromo-2- 3 4
fluoro-2-methylbutane
methylhexane
3-49
3-50 Usually, the anti conformation is more stable than the gauche because the two larger groups are farther
away in the anti conformer. There must be something special about the gauche conformer, some attractive
force that overcomes the normal repulsion between groups in the gauche conformation. What could it be?
OH OH
H H H OH
H H H H
OH H
anti gauche
Hydrogen bonding! Moving the two OH groups closer together permits the H of one to come close to the
O of the other, as can be seen in the picture below. Such intramolecular (within one molecule) hydrogen
bonding cannot take place in the anti conformation where the two OH groups are too far apart.
H
O
H O
H intramolecular hydrogen bonding, a strong attractive force
H H
H
gauche 93
3-51 chair form of
Cyclohexanehexol with all
substituents equatorial
(without ring H atoms shown)
3-52
Begin this problem by labeling the important parts of the structure given in the problem.
"headrest" of chair
axial up Cl H
5 Begin numbering at the carbon with the chloro substituent
H H
because chloro comes before ethyl in the alphabet.
1 3
H 2 CH2CH3 equatorial down
H H
partial name: 3-ethyl-1-chlorocyclohexane,
but what geometric isomer?
"footrest" of chair
(a) (b)
5
H H 6 4
H
5 Cl Cl 1 3
H
H 3
14 CH2CH3 H 2 CH2CH3
H
6
H
2
H H
(c) trans-1-chloro-3-ethylcyclohexane
H H
Note to the student: Creating practice problems for your study group is very helpful in learning new
material, and in some areas, it is not difficult. For example, to create nomenclature problems, draw a
cyclopentane, add three substituents, and name it. Then erase one of the ring bonds and name that
acyclic structure. Go around the ring, erasing one bond at a time, and you have generated five new
nomenclature problems for your group to practice naming!
94
CHAPTER 7—STRUCTURE AND SYNTHESIS OF ALKENES; ELIMINATION
7-1 The number of elements of unsaturation in a hydrocarbon formula is given by:
2(#C) + 2 – (#H)
2
(a) Solve this equation for #H. Three double bonds
#H = 10
plus one ring makes 4 elements of unsaturation.
C8H10 has 4 elements of unsaturation.
(b) C5H10 ⇒ 2(5) + 2 – (10)

= 1 element of unsaturation
2
(c) Many examples are possible. Yours may not match these structures, but all possible answers must have
either one double bond or one ring, that is, one element of unsaturation.
2(3) + 2 – (4)
7-2 C3H4 ⇒ = 2 elements of unsaturation
2
Of the three structures, one has 1 triple bond, one has 2 double bonds, one has 1 ring plus 1
double bond.
7-3 Hundreds of examples of C4H6NOCl are possible. Yours may not match these, although all must
contain two elements of unsaturation. H Cl O
O Cl C N Cl N O
Cl NH2 N C C Cl
N
OH
OH H
7-4 Many examples (sometimes thousands) of these formulas are possible. Yours may not match these,
but correct answers must have the same number of elements of unsaturation. Check your answers in your
study group.
(a) C4H4Cl2 ⇒ C4H6 = hydrocarbon equivalent Cl Cl
Cl
C4H10 = saturated formula
a 4H deficiency = Cl
2 elements of unsaturation Cl
Cl
O OH
(b) C4H8O ⇒ C4H8 = hydrocarbon equivalent
C4H10 = saturated formula
O
a 2H deficiency =
1 element of unsaturation O O
(c) C6H8O2 ⇒ C6H8 = hydrocarbon equivalent O
O
C6H14 = saturated formula H C C C C OCH CH O
3 2 3
a 6H deficiency = 158
3 elements of unsaturation Copyright © 2017 Pearson Education, Ltd.
7-4 continued
O O
O N N C O O
(d) C5H5NO2 —using the formula: C C NH2
2(5) + 2 + (1) – (5) O
= 4
2
C N
Br N C CH2 Cl
(e) C6H3NClBr —using the formula:
Br NH
2(6) + 2 + (1) – (3 + 2)
= 5
2 Cl HC C C C C CH Br Cl
Note to the student: The IUPAC system of nomenclature is undergoing many changes, most notably
in the placement of position numbers. The new system places the position number close to the
functional group designation, which is what this Solutions Manual will attempt to follow; however,
you should be able to use and recognize names in either the old or the new style. Ask your instructor
which system to use.
7-5 The E/Z system is unambiguous and is generally preferred for designating stereochemistry around a
double bond. However, cis and trans are still used for geometric isomers from substituents on a ring.
(a) 4-methylpent-1-ene (b) 2-ethylhex-1-ene (Number the longest chain containing the double bond.)
(c) penta-1,4-diene (d) penta-1,2,4-triene
(e) 2,5-dimethylcyclopenta-1,3-diene (f) 3-methylene-4-vinylcyclohex-1-ene ("1" is optional)
(g) 3-phenylprop-1-ene ("1" is optional)
For comparison, these are the old IUPAC names for problem 7-5. The old names will not be used in this
Solutions Manual.
(a) 4-methyl-1-pentene (b) 2-ethyl-1-hexene
(c) 1,4-pentadiene (d) 1,2,4-pentatriene
(e) 2,5-dimethyl-1,3-cyclopentadiene (f) 3-methylene-4-vinyl-1-cyclohexene ("1" is optional)
(g) 3-phenyl-1-propene ("1" is optional)
Note to the student: How to tell whether a double bond has geometric isomers? Look at the four
groups bonded to the two carbons of the double bond: w, x, y, and z.
w y If w ≠ x AND y ≠ z, it will have geometric isomers.

C C If w = y (or x = z), it is the cis isomer.
x z If w = z (or x = y), it is the trans isomer.
7-6 Parts (b) and (e) do not show cis,trans isomerism.

(a)
(Z)-hex-3-ene (E)-hex-3-ene
(cis-hex-3-ene) (trans-hex-3-ene)
(c)
(2Z,4Z)-hexa-2,4-diene (2Z,4E)-hexa-2,4-diene (2E,4E)-hexa-2,4-diene

cis,cis-hexa-2,4-diene cis,trans-hexa-2,4-diene trans,trans-hexa-2,4-diene
159
7-6 continued
(d) "Cis" and "trans" are not clear for this example;
"E" and "Z" are unambiguous.
(Z)-3-methylpent-2-ene (E)-3-methylpent-2-ene
1 H 1 Br In this example, cis and trans refer

(f) H H
2 4 2 4
to the relative positions of the Br
atoms, not the double bond. All
3 Br 3 H double bonds in rings of 7 or fewer
Br Br atoms must be cis.
cis-3,4-dibromocyclopent-1-ene trans-3,4-dibromocyclopent-1-ene
(Both Br atoms could also be (Both Br atoms could also
up, the enantiomer.) be inverted, the enantiomer.)
4
3 2
7-7 2
6
3 4 5
(a) 5 (b) (c) 3
2 1 1
1
4 5
trans-3-ethylhexa-1,4-diene 1-methylcyclopentene
cis-3,4-dimethylpent-2-ene (Whether cis or trans is not
(The only positions to attach two specified in the problem; the vinyl
methyl groups to make the double group is part of the main chain.
bond cis are at C-3 and C-4.) This could also be named as the E
isomer. The cis (Z) isomer is
equally good.)
4
Cl 5 2
Br
3 1 4
(d) (e) 3 (f) 5
2 1 2 3
1 4 Br
5-chlorocyclohexa-1,3-diene
(Positions of double bonds need 1,4-dimethylcyclohexene (E)-2,5-dibromo-3-ethylpent-2-ene
to be specified.) (The cis designation does not apply—
four different groups on the double
7-8 bond.)
Cl Cl Br
(a)
Br
(E)-3-bromo-2-chloropent-2-ene (Z)-3-bromo-2-chloropent-2-ene
(b)
(2E,4E)-3-ethylhexa-2,4-diene (2Z,4E)- (2E,4Z)- (2Z,4Z)-
H
(c)
H
Br (E)-3-bromo-2-methylhex-3-ene
(Z)-3-bromo-2-methylhex-3-ene Br
160
7-8 continued
(d) (e)
(Z)-penta-1,3-diene (E)-penta-1,3-diene
no geometric isomer
(f)
Cl Cl Cl Cl
(2Z,5E)-3,7-dichloroocta-2,5-diene (2E,5E)-3,7-dichloroocta-2,5-diene
Cl Cl
Cl Cl
(2Z,5Z)-3,7-dichloroocta-2,5-diene (2E,5Z)-3,7-dichloroocta-2,5-diene
(g) no geometric isomers (An E double bond would be too highly strained.)
(h)
(Z)-cyclodecene (E)-cyclodecene
(i)
(1E,5E)-cyclodeca-1,5-diene (1Z,5E)-cyclodeca-1,5-diene (1Z,5Z)-cyclodeca-1,5-diene
7-9 NOT stereogenic: two H on end C preclude geometric isomers.

(a) Stereogenic: unequal groups on each side.
C C C C C C C C
* * * * *Each of the four stereocenters is marked with *.
trans,trans-octa-1,3,5-triene
trans,cis-octa-1,3,5-triene
cis,cis-octa-1,3,5-triene
cis,trans-octa-1,3,5-triene
161
7-9 continued
(b) C C C C C C C C Whereas octa-2,4,6-triene has three stereogenic double bonds,
because of symmetry, the middle one has two equal and
indistinguishable ends, reducing the total number of
stereoisomers very much like a meso form with chiral
stereocenters.
isomers with trans in the middle isomers with cis in the middle
trans,trans,trans-octa-2,4,6-triene cis,cis,cis-octa-2,4,6-triene
trans,trans,cis-octa-2,4,6-triene cis,cis,trans-octa-2,4,6-triene
(same as cis,trans,trans- if numbered (same as trans,cis,cis- if numbered
in the reverse direction) in the reverse direction)
cis,trans,cis-octa-2,4,6-triene trans,cis,trans-octa-2,4,6-triene
7-10
The rate-limiting step in oxidation is abstraction of an atom A by atmospheric O2 to form A–OO• and a
carbon free radical. The energies of bond breaking and bond forming in this step determine whether it
will be successful, that is, whether the oxidation will occur.
It is important to note that atmospheric oxygen exists in a diradical form (•O–O•), so there is no
energy required to disrupt any bond in O2.
polyethylene
H
C + O2 C + H—OO• ∆H = –(192) + (400) =

+208 kJ/mole—endothermic—
H H 192 kJ/mole requires high temperature
400 kJ/mole
Teflon
F
C + O2 C + F—OO• ∆H = –(63) + (460) =

+397 kJ/mole—almost twice
F F 63 kJ/mole as endothermic—requires
460 kJ/mole very high temperature
Because the C-F bond is particularly strong, and the O-F bond is particularly weak, the energy required
for O2 to abstract an F atom is huge, almost twice as large as the energy required for O2 to abstract an H
from polyethylene. Both require high temperature to get over the energy barrier, but Teflon will
decompose at a much higher temperature because the rate-limiting step has a higher energy barrier.
162
7-11
(a) The dibromo compound should boil at a higher temperature because of its much larger molecular weight.
(b) The cis should boil at a higher temperature than the trans as the trans has a zero dipole moment and
therefore no dipole-dipole interactions.
(c) 1,2-Dichlorocyclohexene should boil at a higher temperature because of its much larger molecular weight
and larger dipole moment than cyclohexene.
7-12 From Table 7-2, approximate heats of hydrogenation can be determined for similarly substituted
alkenes. The energy difference is approximately 6 kJ/mole (1.4 kcal/mole), the more substituted alkene
being more stable.
gem-disubstituted tetrasubstituted
116.3 kJ/mole 110.4 kJ/mole
(27.8 kcal/mole) (26.4 kcal/mole)
7-13 Use the values in Table 7-2. Alternatively, the relative values in Figure 7-8 could be used to reach the
same conclusions. Minor discrepancies between kcal and kJ are due to rounding.
(a) 2 x (cis-disubstituted − trans-disubstituted) =

2 x (118.5 − 114.6) = 7.8 kJ/mole more stable for trans, trans trans,trans cis,cis
(2 x (28.3 − 27.4) = 1.8 kcal/mole) more stable
(b) monosubstituted − gem-disubstituted = 126.3 − 118.2 = 8.1 kJ/mole

(30.2 − 28.3 = 1.9 kcal/mole)
2-methylbut-1-ene is more stable
disubst. monosubst.
more stable
(c) gem-disubstituted − trisubstituted = 118.2 − 111.6 = 6.6 kJ/mole

(28.3 − 26.7 = 1.6 kcal/mole)
2-methylbut-2-ene is more stable
trisubst. disubst.
more stable
(d) cis-disubstituted − trisubstituted = 117.7 − 111.6 = 6.1 kJ/mole

(28.1 − 26.7 = 1.4 kcal/mole)
2-methylpent-2-ene is more stable
trisubst. cis-disubst.
more stable
7-14
CH3
(a) Slightly strained but stable (b) Could not exist as the ring size must be 8
with C=C in a 5-membered atoms or greater to include trans double
CH3 ring. bond—see answer to part (e).
(c) CH3
The trans refers to the two methyls since this compound can exist, rather than the
trans referring to the alkene, a molecule that could not exist because the ring
CH3 would have too much strain. A ring must have 8 or more atoms before a trans
double bond can exist in the ring.
163
7-14 continued
(d) CH3
stable—trans in 10-membered ring

CH3
(e) Unstable at room temperature—it cannot have trans alkene in 7-membered ring (possibly isolable at
very low temperature—this type of experiment is one of the challenges chemists attack with gusto).
(f) Stable—the alkene is not at a bridgehead.
(g) Unstable—violates Bredt's Rule (alkene at bridgehead in 6-membered ring).
(h) Stable—alkene is at bridgehead in 8-membered ring.
(i) Unstable—violates Bredt's Rule (alkene at bridgehead in 7-membered ring).
7-15
(a)
aromatic and not aromatic, not aromatic, aromatic but

conjugated; fully conjugated partially conjugated; not conjugated
MOST STABLE LEAST STABLE
O O O
(b)
only 2 pi bonds conjugated all 3 pi bonds conjugated; all 3 pi bonds isolated;

MOST STABLE LEAST STABLE
(c)
all 3 pi bonds isolated; all 3 pi bonds conjugated aromatic; only 2 pi bonds

LEAST STABLE MOST STABLE conjugated
7-16
If the CH3OH acts as a nucleophile, the product will be a substitution; the overall mechanism will be SN1.
H CH3 H CH3
H
C O O O O
H CH3 H CH3
H HH H
H H H
+ CH3OH2
7-17 H3C
(a)
Br Br– O H O CH3
C
H3C O H H3C O H + CH3OH2
The SN1 mechanism begins with ionization to form a carbocation, attack of a nucleophile, and in
the case of ROH nucleophiles, removal of a proton by a base to form a neutral product.
164
7-17 continued
(b) In the E1 reaction, the solvent (methanol, in this case) serves two functions: it aids the ionization
process by solvating both the leaving group (bromide) and the carbocation; and second, it serves as a base
to remove the proton from a carbon adjacent to the carbocation in order to form the carbon–carbon double
bond. The SN1 mechanism adds a third function to the solvent: the first step is the same as in E1,
ionization to form the carbocation; the second step has the solvent acting as a nucleophile—this step is
different from E1; third, the solvent acts like a base and removes a proton, although from an oxygen (SN1)
and not a carbon (E1). Solvents are versatile!
7-18 H H H H
H
C H CH2 H H
O CH3 O CH3
C C C C
H H
E1 C E1 C
H H
H2C H
C
C H
C
SN1
O CH3
O CH3 S N1
H
H
H H H H
CH3 CH3 H H
C C
C O CH3 C OCH3 C CH3 C CH3
O O
O CH3
H OCH3
H
H
H
165
7-19 This solution does not show CH3
complete mechanisms. Rather, it Br
shows the general sequence of all H3C 2-bromo-3-methylbutane
four pathways leading to five CH3
different products. H
Ethanol is the solvent shown here H
in the substitution products; it is
often used in solvolysis reactions. ionization
CH3 CH3
hydride shift H
unrearranged H3C H3C C rearranged
2° carbocation C CH3 CH3 3° carbocation
H
H H
E1 E1
S N1 S N1
CH3CH2 CH3 CH3 CH3 CH3

O H H
H3C H2C H3C H3C
CH3 CH3 CH3 CH2
H H O
H H H CH2CH3 H
Five unique products CH3 CH3

shown in the boxes.
One alkene can be H3C H3C
produced from either the CH3 same CH3
2° or the 3° carbocation. compound
H H
two possible E1 products two possible
E1 products
7-20 Substitution products are shown first, then elimination products.

Ph
(b) Ph
OCH2CH3
(a) +
+ Ph = phenyl
OCH3
OH
OH
(c) CH3 CH3 CH3 CH2
+ CH3 +
SN1 product without SN1 product with major E1 product with or

rearrangement rearrangement without rearrangement minor
166
without rearrangement with rearrangement
7-21
CH3 OCH2CH3
CH3 C CH CH3 CH3 C CH CH3
CH3 OCH2CH3 CH3 CH3
7-22
Br
CH CH2 Rearrangement by ring expansion is
H rearrangement theoretically possible but very
C unlikely because the ring size is
CH3OH hydride shift
already at the optimum six-
∆ membered.
ionization
unrearranged rearranged
SN1 reactions: CH3 CH3
O O
CH H
H 1
O O
H CH3 H CH3
CH3 CH3
O O
C O H O 2
H CH3 H CH3
E1 reactions: H
H
C H2C
CH CH H CH CH
H
O O
H CH3 3 H CH3 4
and
H SAME
C H CH
H
C O 3 C H O C 5
H CH3 H CH3 CH
and
5 is the major elimination product: trisubstituted and endocyclic (in the ring), the more stable position.
3 is trisubstituted but is exocyclic, a less stable position.
167
7-23
NaOCH2CH3
OCH2CH3
E2—minor E2—major SN2—probably
product—less product—more very small
Br substituted alkene substituted alkene amount because
(monosubstituted) (trisubstituted) of steric hindrance
7-24 Br OCH3
NaOCH3
(a)
minor alkene— major alkene— SN2 product—some
monosubstituted disubstituted will be formed on a
NaOCH3 (cis + trans) 2° carbon
Br
(b)
No SN2 product will be
formed; SN2 cannot
major alkene— minor alkene— occur at a 3° carbon.
trisubstituted disubstituted
(cis + trans)
Br OH
NaOH
(c)
minor alkene— major alkene— SN2 product—very

monosubstituted trisubstituted small amount because
2° carbon is hindered
7-25 H3C Br
3°
(a) NaOH Strong base (hydroxide) will give second
+ order reactions; a 3° alkyl halide precludes
acetone SN2, so E2 is the only option.
major minor
E2 E2
H3C Br
3° E2 is only option; hindered base gives less
(b) (CH3CH2)3N
+ substituted double bond as major isomer.
minor major
E2 E2
Cl OCH3
(c) 2° NaOCH3
+ Major product is difficult to predict
CH3OH for unhindered 2° halides and strong,
unhindered bases/nucleophiles; both
Cl SN2 E2 SN2 and E2.
(d) 2° NaOC(CH3)3 NaOC(CH3)3 is a bulky base and a poor
nucleophile, minimizing SN2.
(CH3)3COH
E2 168
7-26 Base:
Ph
H H
S Ph
Br H H3C H
= C C C C
S Ph
H3C H H3C Ph
Ph Br cis
Ph
7-27 CF3 H HBr CF3

CH3 H
(a) H
H Br rotate
H and Br
CH3CH2 180°
H CH3 CH3CH2 CF3 CH3 Br
CH2CH3 HO–
HO–
H OH CH3CH2 CF3
C C
CH3 H
E2 elimination
CH3CH2
CH3 HCF3
Since hydroxide is a strong base, the reaction
SN2 product will be second order: on a 2° alkyl bromide,
both substitution and elimination will occur.
(b) Ph hindered base
H H Ph Ph
(CH3CH2)3N
C C
Ph Note that these products are
Br H geometric isomers. If a reaction
Br Br
only alkene isomer starts with stereoisomers and
meso E2 produces stereoisomers, that is
Ph hindered base the definition of a stereospecific
(c) H H Ph reaction.
(CH3CH2)3N Br
C C
Br H
Ph Br Ph
one enantiomer only alkene isomer
of the d,l pair E2
H Cl HO H
(d) SN2 is the only mechanism possible because
NaOH no H can get coplanar with Cl; an elimination
acetone product would violate Bredt's Rule.
1
2 Cl (CH3)3CO
(e) H
3 D
H H
H
Models show that the H on C-3 cannot be anti-coplanar with the Cl on C-2. Thus, this E2 elimination must
occur with a syn-coplanar orientation: the D must be removed as the Cl leaves.
169
7-27 continued π bond
(f) CH3 rotate H
H CF3 back H CF3 O
carbon CH3CH2 CH3
H CF3
hindered base:
H CH2CH3 CH3CH2 CH3 E2 only
Br Br
H and Br must be 180°. H CH2CH3 only E2
product
F3C CH3
7-28 As shown in Solved Problem 7-5, the H and the Br must have trans-diaxial orientation for the E2
reaction to occur. In part (a), the cis isomer has the methyl in the equatorial position, the NaOCH3 can
remove a hydrogen from either C-2 or C-6, giving a mixture of alkenes where the most highly
substituted isomer is the major product (Zaitsev). In part (b), the trans isomer has the methyl in the axial
position at C-2, so no elimination can occur at C-2. The only possible elimination orientation is toward
C-6. Br CH3 CH3
H3C
1 NaOCH3
(a)
Zaitsev orientation
6 CH3OH
H
Either H H major minor
can be removed.
(b) Br CH3
H
1
NaOCH3
Only alkene formed; stereochemistry of E2
6 CH3OH precludes other isomer from forming.
H3C
Only this H H
can be removed.
CH3 no hydrogens trans diaxial to the Br

7-29 E2 elimination requires that the H and the
leaving group be anti-coplanar; in a chair cyclohexane, CH3
this requires that the two groups be trans diaxial. H
However, when the bromine atom is in an axial
position, there are no hydrogens in axial positions on H
adjacent carbons, so no elimination can occur. H
Br axial
170
7-30 H
H H H
(a) H
Br H
H KOH
H Br axial + H
H H
Br
Br equatorial H
H H
Showing the chair form of the decalins makes the answer clear. The top isomer locks the H and the Br that
eliminate into a trans-diaxial conformation—optimum for E2 elimination. The bottom isomer has Br
equatorial where it is exceedingly slow to eliminate.
(b) Br
KOH
In this cis isomer, the Br is in the optimum axial position

Br for elimination while the large isopropyl group is in the
Br must be axial to eliminate by E2, energetically preferred equatorial position; this will be
forcing the large isopropyl group axial, a the reactive conformer.
very unstable conformer; this trans isomer
will be exceedingly slow to react as the
preferred conformer will be diequatorial.
7-31 Models are a big help for this problem. CH3

(a) Br
CH3 CH3
NaOCH3 H
H
=
H H
H CH CH3 H CH3
3
the only H the only elimination

trans diaxial product
H H H
(b) Br
NaOCH3
= H
H H
H H D
H D D H
(from elimination of H and Br)
+
both trans diaxial—
gives two products H H
=
H H
H H H
H
(from elimination of D and Br)
171
7-32
The base NaOEt is strong and not hindered, so this
(a) + reaction will follow the E2 mechanism. The product
ratio will follow Zaitsev's Rule: trisubstituted double
MAJOR MINOR bond is major, and monosubstituted double bond is minor.
(b) This E1 reaction is complicated because the carbocation intermediate in two possible ways, and each
carbocation can give two possible alkene products.
unrearranged carbocation rearranged carbocation 1 rearranged carbocation 2
H H H
H
C C C
C
SAME +
+ +
Five different alkene products are possible in this E1 reaction. The ratio of products is difficult to
predict because it depends on the rate of rearrangement and the relative amounts of the two different
rearrangements. The safest prediction is that the most stable alkene is most likely the major product: of
these five alkenes, the trisubstituted double bond in the six-membered ring is the most stable (the one in
the box), so it is likely to be the major product.
Br δ
–
Follow-up question to Solved Problem 7-6(a):
In the E2 transition state, the C—H bond
and the C—Br bond are stretched as the CH3
O—H bond is being formed. H
H H trans diaxial to Br
δ– O
CH3
Follow-up question to Solved Problem 7-6(b):

CH3 rearrangement
CH3 CH3
CH3OH by hydride shift C All of the products
H shown below are derived
∆ C C from one of these two
I ionization H H carbocations.
I H
172
Follow-up question to Solved Problem 7-6(b), continued
SN1 on unrearranged carbocation
CH3 CH3 CH3
CH3 CH3
C O O O O
H H CH3 H CH3
H H H
E1 on unrearranged carbocation
CH3
CH3 CH3 CH3
H
O H CH3
C H CH3 C O
H H H H
major H H minor
H
SN1 on rearranged carbocation CH3 CH3

CH3 CH3
CH3
C C O C O
O H O
H CH3 H CH3
E1 on rearranged carbocation H H
H
CH3 CH3 C C
C C H C H
C O O
H H CH3 H H CH3
H major minor
7-33
(a) Ethoxide is a strong base/nucleophile—second-order conditions. The 1° bromide favors substitution
over elimination, so SN2 will predominate over E2.
O
substitution—major elimination—minor
(b) Methoxide is a strong base/nucleophile—second-order conditions. The 2° chloride will undergo SN2 by
backside attack as well as E2 to make a mixture of alkenes.
OCH3
elimination— elimination—
substitution minor alkene major alkene
(cis + trans)
(c) Ethoxide is a strong base/nucleophile—second-order conditions. The 3° chloride is hindered and cannot
undergo SN2 by backside attack. E2 is the only route possible.
CH3 C CHCH3 CH2 C CH2CH3
major minor
CH3 CH3
173
7-33 continued
(d) Heating in ethanol are conditions for solvolysis, an SN1 reaction. Heat also promotes elimination.
OCH2CH3
CH3 C CH2CH3 CH3 C CHCH3 Substitution and

elimination are possible.
CH3 SN1 CH3 E1
major elimination product
(e) Hydroxide is a strong base/nucleophile—second-order conditions. The 1° iodide is more likely to
undergo SN2 than E2, but both products will be observed.
CH3 CHCH2OH CH3 C CH2
CH3 CH3
substitution—major elimination—minor
(f) Silver nitrate in ethanol/water are ionizing conditions for 1° alkyl halides that will lead to
rearrangement followed by substitution on the 3° carbocation. (No heat, so E1 is unlikely.)
OCH2CH3 from ethanol as OH from water as
nucleophile nucleophile
CH3 C CH3 CH3 C CH3
CH3 CH3
(g) Ethoxide in ethanol on a 3° halide will lead to E2 elimination; there will be no substitution.
CH3 CH2
major alkene minor alkene

(h) Heating a 3° halide in methanol is quintessential first-order conditions, either E1 or SN1 (solvolysis).
CH3 CH2
CH3 OCH3
substitution elimination (E1): (trace)

(SN1)
Solved Problem 7-7(b): removal of protons from carbocation intermediates:

H H H
H2
C H C H C C
C C C C CH3 C CH3
H H H H H
H H C
H
H2O H2O H2O H2O
H H H
H2
C H C H C C
C C C C CH3 C CH3
H
H H C
H
SAME
174
7-34 In these mechanisms, the base removing the final proton is shown as water. Other alcohols are
just as likely to serve as the base.
(a) H
OH O H H H
H OSO3H ∆ C H2O
H as base
H H
H H
(b) OH O H
H OSO3H ∆ C
H H
H2O
as base H2O as base
cis + trans minor isomer

major isomer
H
(c) 2° H
OH O H H rearrange— H
H OSO3H ∆ C hydride shift
C
CH3 CH3 H CH3
CH3 3°
from unrearranged 2° carbocation H from rearranged 3° carbocation

H
H
H H H H2O
H2O
H H as base CH3
H
C as base greatest amount
CH3
C
H CH2
H2O H
CH3
H H
as base H
H2O
as base
CH2
CH3
least amount
greatest amount
175
7-34 continued
H OSO3H ∆
(d) C
C
OH O H
H
H
When proposing mechanisms, always look for what bonds are broken and what H2O
new bonds must be formed. In this problem, the new ring must come from the as base
pi electrons forming a new sigma bond at a 3° carbon, which must have been a
carbocation.
7-35 H—A is the generic symbol for an acid.

(a) Only one elimination product is possible.
H H
OH O H H
C H C H
H A ∆ H2O
C C
–H2O H
H H
benzylic—
resonance-stabilized
(b) Three elimination products are possible: two from an unrearranged carbocation, and two from a
rearranged carbocation, one product of which is the same to both pathways.
CH3 CH3 CH3
H H3C H
H
C C
OH H A O ∆ H
C C
H –H O H
2
from unrearranged carbocation
H2O CH3
H3C H H3C H
C C C
H H H
C AND C + C
C C
H H2O
H H
from rearranged carbocation SAME
H
H H H H
C H2O CH3 C
H H
C C C
H +
C AND C C
H H
H2O
176
7-35 continued
(c) Three elimination products are possible: the intermediate carbocation is allylic, with positive charge
shared by two different carbons. An H can be removed from any of three carbons adjacent to positively-
charged carbons.
H A ∆
H C C C
H3C OH H3C O –H2O H H
H
Although the two resonance forms do not represent real structures, each can be treated separately to
determine the alkenes that could be produced. Resonance braces omitted for space reasons.
H
H
C C
H H2O
C C
H H
H H
H2O H
C C C
H H
+
H C C H C C H C C
C H C H C H
H H
H H2O H H
7-36
(a) ∆G° = ∆H° − T∆S°
= + 116,000 J/mol − 298 °K (117 J/°K•mol) = + 116,000 J/mol – 34,866 J/mol
= + 81,134 J/mol = + 81.1 kJ/mol (+19.3 kcal/mole)
∆G° is positive, the reaction is disfavored at 25°C.
(b) ∆G1000 = + 116,000 J/mol − 1273 °K (117 J/°K•mol) = + 116,000 J/mol – 148,941 J/mol
= − 32,941 J/mol = − 32.9 kJ/mol (– 8.0 kcal/mole)
∆G is negative, the reaction is favored at 1000°C.
7-37
(a) Basic and nucleophilic mechanism: Ba(OH)2 is a strong base.
(b) Acidic and electrophilic mechanism: the catalyst is H+.
(c) Free radical chain reaction: the catalyst is a peroxide that initiates free radical reactions.
(d) Acidic and electrophilic mechanism: the catalyst BF3 is a strong Lewis acid.
177
7-38 H H H H H H H
(a) H OSO3H
CH3 C C C OH CH3 C C C OH OSO3H
H H H H H H
∆
H H H H H hydride H H H
shift
CH3 C C CH3 CH3 C C C H CH3 C C C + H2O
E+Z H2O
H H H H H
but-2-ene
major product This 1° carbocation would be
H2O very unstable.
H H H
CH3 C C C H but-1-ene
minor product
H
(b) Br H
S N2
+ NaBr
H Na+ OCH3
O CH3
as a nucleophile
Br
E2 H
H + NaBr + CH3OH
Na+ O CH3
H as a base H
H
"B"
(c)
H OSO3H ∆ H H
H2O +
C
OH O H "A"
Pi electrons
H form sigma
bond at carbo- H2O "A"
cation.
"B"
H
H
H2O
C
new bond
178
7-39
H H H
(a) H H
OH H OPO3H2 OH ∆ C
H
H2O H
H
+ H2O
H
(b) CH2 OH CH2 OH CH2
H OSO3H ∆ This 1° carbocation would be

− H2O very unstable.
Two possible rearrangements

1. Hydride shift H
CH2 H C H CH2 CH3
H C H
H2O
H
2. Alkyl shift—ring expansion
CH2 H H
H
H C C H
C H2O
H
(c) carbocation formation
HO H O H H
H OSO3H ∆ C
+ H2O
H H
continued on next page
179
7-39 (c) continued
without rearrangement
H H
H H
C H H2O H
H
H H
H H
H
C H H2O H
H H
H H
E+Z
with hydride shift

H H H
H
C H H2O
C
H H H
H H H
H2O H H
H
(d)
∆
H OSO3H C
H E1 product from
H OH H O H H unrearranged
H carbocation
+ H2O
rearrangement by alkyl shift
3°
C
C
2° H
E1 on rearranged carbocation
H H2O
H3O
C
H2O
H H H
180
7-40 (a) (b) (c) (d)
Cl
Cl alternate name: cyclopentadiene
(e) (f) (g) Br (h) (i)
7-41 (a) neither—two hydrogen on one carbon (b) Z (c) E (d) Z

7-42 Parts (a) and (d) have no geometric isomers.
(b) (c)
trans-pent-2-ene cis-pent-2-ene trans-hex-3-ene cis-hex-3-ene

(E)-pent-2-ene (Z)-pent-2-ene (E)-hex-3-ene (Z)-hex-3-ene
Br
(e) trans-1,2-dibromopropene Br cis-1,2-dibromopropene
(E)-1,2-dibromopropene (Z)-1,2-dibromopropene
Br
Br
(f) Cis and trans do not apply to the C=C at C-1, only the one at C-3. The E/Z system is unambiguous.
Br Cl Br Cl
trans trans Z Z
Cl Z E Br E E Cl Z Br E
cis cis
7-43 These names follow the modern IUPAC system of placement of position numbers.
(a) 2-ethylhex-1-ene (Number the longest chain containing the double bond.)
(b) 3-ethylhex-2-ene
(c) (3E,5E)-2,6-dimethylnona-1,3,5-triene
(d) (Z)-4-ethylhept-3-ene
(e) 1-cyclopentylcyclohexa-1,3-diene
(f) (3Z,5Z)-6-bromo-3-(chloromethyl)nona-1,3,5-triene
7-44
F
(a)
F F
F F
(Z)-1-fluoro- (E)-1-fluoro- 2-fluoro- 3-fluoro- fluorocyclopropane
prop-1-ene prop-1-ene prop-1-ene prop-1-ene
181
7-44 continued
(b) C4H7Br has one element of unsaturation, but no rings are permitted in the problem, so all the isomers
must have one double bond. Only four isomers are possible with four carbons and one double bond, so
the 12 answers must have these four skeletons with a Br substituted in all possible positions.
trans cis
enantiomers
Br Br H Br
Br
H Br
Br
Br
Br Br
Br
Br
Br
(c) Cholesterol, C27H46O, has five elements of unsaturation. If only one of those is a pi bond, the other
four must be rings. (The structure of cholesterol can be found in text section 25-6.)
7-45 (a) Neither cis nor trans is defined for the double bond beginning at C-2 because none of the four
groups are the same.
(b) All are 3-methylhepta-2,4-diene.The E/Z nomenclature is unambiguous and is preferred for all four
of these isomers.
7-46
H Cl F F F CH3
(a) Cl Cl (b)
Cl H CH3 F
H H H H
dipole moment = 0 dipole moment = 0
F F F F larger dipole moment

(c) (no bromines opposing the
Br Br H H dipole of the fluorines)
7-47
more stable than by 4 kJ/mole
more stable than by 16 kJ/mole
Steric crowding by the tert-butyl group is responsible for the energy difference. In cis-but-2-ene, the two
methyl groups have only slight interaction. However, in the 4,4-dimethylpent-2-enes, the larger size of the
tert-butyl group crowds the methyl group in the cis isomer, increasing its strain and therefore its energy.
182
7-48
endocyclic exocyclic endocyclic exocyclic

trisubstituted disubstituted trisubstituted trisubstituted
9 kJ/mole 5 kJ/mole
A standard principle of science is to compare experiments that differ by only one variable. Changing more
than one variable clouds the interpretation, possibly to the point of invalidating the experiment.
The first set of structures compares endo and exocyclic double bonds, but the degree of substitution on the
alkene is also different, so this comparison is not valid—we are not isolating simply the exo or endocyclic
effect. The second pair is a much better measure of endo versus exocyclic stability because both alkenes are
trisubstituted, so the degree of substitution plays no part in the energy values. Thus, 5 kJ/mole is a better
value.
7-49
The carbocation produced in this E1 elimination is
(a) + + 3° and will not rearrange. The product ratio follows
the Zaitsev rule.
major minor trace amount
(b) The carbocation produced in this E1

+ + elimination is 2° and can either eliminate to
give the first two alkenes, or can rearrange by
trace—from from either from rearranged a hydride shift to a 3° carbocation which
unrearranged unrearranged 3° carbocation would produce the last two products. The
2° carbocation 2° carbocation amounts of the last two products are not
or rearranged predictable as they are both trisubstituted, but
3° carbocation the first product will certainly be the least.
The carbocation produced in this E1
elimination is 2° and can either eliminate to
(c) + + give the first alkene, or can rearrange by a
methyl shift to a 3° carbocation which would
produce the last two products. The middle
trace—from major minor product is major as it is tetrasubstituted
unrearranged versus disubstituted for the last structure and
2° carbocation from rearranged from rearranged
3° carbocation 3° carbocation monosubstituted for the first structure.
7-50
(a) (b) + +
only product minor
major
CH3 CH3
(c) + (d) (e) Br NaOH
+
major minor The E2 mechanism requires anti-

coplanar orientation of H and Br.
183
7-51 The bromides are shown here. Chlorides or iodides would also work.
(a) Br (b) Br (c) (d) (e)

or
Br Br Br
Br
7-52
CH3 CH3
(a) (b) (c) (d)
disubstituted
trisubstituted
7-53 CH3 CH3
(a) (b) (c)
major minor
major minor minor
7-54
(a)
(b)
(c)
(d)
7-55
(a) + (b) +
major minor
major minor
CH3 Only product from E2—anti-
coplanar is possible only
(c) + (d) from carbon without CH3 by
removing H and Cl.
major minor D
184
7-55 continued
ax
(e) (CH3)3C Cl (CH3)3C
1 KOH
3 4 ∆
Cl (CH3)3C Cl
eq
Cl Cl
The conformation must be considered because the leaving
group must be in an axial position. The tert-butyl group is so (CH3)3C
large that it must be equatorial, locking the conformation into
the chair shown. As a result, only the Cl at position 4 is axial,
so that is the one that must leave, not the one at position 3.
Two isomers are possible but it is difficult to say which would
be formed in greater amount. Cl
(f) H H
H Br
Only one of the two Br atoms is in KOH
the required axial position for E2
elimination. There are axial H Br ∆
atoms at the two adjacent carbons, Br Br
H H H
so two alkene products can be
formed. Predicting major and minor
would be difficult.
7-56 S N2
Br2 Br Br KOH Br NaOEt OEt
(a) (b) (c)
hν ∆ cold to
avoid E2
all positions from (a) from (a)
equivalent or KO-t-Bu
or SN1: EtOH, ∆
Br Br
S N2
Br NaOH OH
NBS KOH
(d) (e) (f)
hν ∆ cold to
avoid E2
from (b) or low conc. from (d) or KO-t-Bu from (a)
or SN1: H2O, ∆
of Br2 , hν
7-57
OH H2SO4
(a)
heat
Br NaOC(CH3)3 Other bases could also be used. The hindered bases would
(b)
heat minimize the amount of substitution that would occur.
(c) Br2 , hν Br NaOC(CH3)3

heat
185
7-58 "Ph" is the abbreviation for the phenyl substituent.
Br OCH2CH3 solvolysis conditions—SN1
If the reaction mixture got too
Br2 CH3CH2OH warm, some E1 elimination might
Ph hν Ph ∆ Ph occur.
(NBS can also be used for
benzylic bromination) Using a hindered base like tert-
Benzylic bromination is very butoxide will give exclusively the
NaOC(CH3)3
selective; dibromination might E2 product, with no competing SN2
∆ Ph
occur if an excess of Br2 is used. as KOH or NaOCH3 might give.
7-59 H H H
– H2O H H
OH H OSO3H OH ∆ C H2O
H
H
H2O H
OSO3H E1 works well because only one carbocation and

only one alkene are possible. Substitution is not a
H problem here. The only nucleophiles are water,
C H which would simply form starting material by a
+ HSO4− reverse of the dehydration, and bisulfate anion.
H Bisulfate anion is an extremely weak base and poor
nucleophile; if it did attack the carbocation, the
H unstable product would quickly re-ionize, with no
net change, back to the carbocation.
7-60 δ–
(a) H O CH3 H O CH3 HOCH3
Br
δ– Br
Br
Methoxide is a strong base and nucleophile so the reaction is second order. The Br is on a 3° carbon so SN2
is not possible, only E2. The transition state shows bond-forming and bond-breaking with dashed bonds.
transition state
The reaction-energy diagram for a one-step activation
mechanism like E2 has one peak. energy
energy
reactants products
reaction coordinate
186
7-60 continued
(b) H H O CH3
H O CH3 Br
HOCH3 H H
C
∆
Br slow
3° carbocation
intermediate intermediate carbocation
The reaction-energy diagram for a two-step

mechanism like E1 has two peaks, with the
energy
first step as the slow step with higher
activation energy.
reaction coordinate
7-61
(a) HOCH3
∆ C O CH3 O CH3
– Br–
Br 3° carbocation; H O H
no rearrangement H3C H
H O CH3
S N1
C H C O
E1 H3C
C C
E1
C C
C O CH3 C
H H H H
187
7-61 continued
This 1° carbocation would be very unstable.
H
(b) H OSO3H ∆ CH2
OH O H + H2O
H
alkyl shift
hydride ring expansion
shift
H2 H
C
C C H
H H2O
H2O H
H H2O
H
This alkene could be produced from the unrearranged
carbocation, but the 1° carbocation has such a short lifetime
that it is more reasonable to propose the pathway through the H
rearranged 3° carbocation.
(c) EtOH
H OEt
∆ H OEt
C
H H OEt H OEt
Br H
H
H H OEt
Et H
H OEt O OEt
H H OEt
7-62
(a) The first step in this first-order solvolysis is ionization, followed by rearrangement.
H
H H
hydride C
Br CH2 CH3OH H CH2 shift CH2
Br – C
H ∆
allylic!
continued on next page

188
7-62(a) continued H H
E1
H C H
CH2 CH2
CH3OH CH3OH2
H
S N1 H3C
H OCH3
H O H
C CH3OH CH3OH
CH2 CH2 CH2
CH3OH2
H3C H
H H
O OCH3
CH2 CH3OH CH2 CH3OH CH2
CH3OH2
(b) The first step in this first-order solvolysis is ionization, followed by rearrangement.
CH3OH
∆ CH3OH CH3OH
C
H Br H H O H H OCH3
Br –
H3C SN1 product from
unrearranged
rearrangement by alkyl shift carbocation
C E1 on rearranged carbocation
C
H CH3OH2
C CH3OH
H H H
SN1 on rearranged carbocation
CH3OH2
C CH3OH CH3OH
O OCH3
H3C H
189
7-63 All five products (boxed) come from rearranged carbocations. Rearrangement, which may occur
simultaneously with ionization, can occur by hydride shift to the 3° methylcyclopentyl cation, or by ring
expansion to the cyclohexyl cation.
This 1° carbocation would be very unstable.
H CH2 Br H CH2
Br – +
hydride shift
H
H CH2 CH2 CH3 CH2
C H H
HOCH3
H
H
CH3 CH3 O CH3 CH3 OCH3
C
HOCH3 HOCH3
alkyl shift (ring expansion)
H CH2 H H
H
C H
HOCH3
H
H
H
H O CH3 H OCH3
C HOCH3 HOCH3
190
7-64 H H H
H
(a) H Br − H2O C
Br
SN1 OH OH Br
H
H H H
H Br Br
SN2 OH OH Br + H2O
H
(b)
H OSO3H ∆ C
C H2O
OH O H H
H
7-65 The symmetry of this molecule is crucial.
(a) Ph H Ph
Regardless of which adjacent H is removed by tert-butoxide, the
CH3 C C C CH3 product will be 2,4-diphenylpent-2-ene.
H Br H
(b) Here are a Newman projection, a three-dimensional representation, and a Fischer projection of the
required diastereomer. On both carbons 2 and 4, the H has to be anti-coplanar with the bromine while
leaving the other groups to give the same product. Not coincidentally, the correct diastereomer is a meso
structure.
π bond
Ph H Br H CH3
Ph
H 2
H3C H3C H H H Ph H
2 H3C Ph 3
Ph 2 Ph Br 3
H
H3C Ph
H3C CH3 Ph H
Br
H and Br are anti-coplanar CH3
7-66 H Ph Ph Ph
CHCH3
NaOEt CH 3 Ph
H + +
CH3 Ph CH CH
Br 2 3
Ph Ph Ph
2S,3R B A = E,Z mixture
H CHCH3
H Ph Ph Ph
NaOEt CH 3 CH 2 CH 3
+ +
CH3 Ph Ph
Ph Br Ph Ph
2S,3S C A = E,Z mixture
E2 dehydrohalogenation requires anti-coplanar arrangement of H and Br, so specific cis-trans isomers (B or
C) are generated depending on the stereochemistry of the starting material. Removing a hydrogen from C-4
(achiral) will give about the same mixture of E and Z (A) from either diastereomer.
191
7-67 Begin with a structure of (S)-2-bromo-2-fluorobutane. Since there is no H on C-2, the lowest
priority group must be the CH3 . The Br has highest priority, then F, then CH2CH3, and CH3 is fourth.
Sodium methoxide is a strong base and nucleophile, so the reaction must be second order, E2 or SN2.
(a) π bond
Br Br
H CH3 NaOCH3 H CH3 H3C H NaOCH3 H C H
3
H3C F H3C F
H3C F H3C F
H H
rotate back carbon 120° π bond
In regular structural formulas, the reaction would give three products including the stereoisomers shown
above.
H3C H H3C CH3 H2C H
NaOCH3
Br F F CH3 F H F CH3
(S) trans cis minor product from E2
(b) 4 3 4 3
NaOCH3
2 In these structures, the numbers 1 to 4 indicate the group's
1 2 S N2 1
Br F F OCH3 priority in the Cahn-Ingold-Prelog system.
(S) (S)
A cursory analysis of the designation of configuration would suggest to the uncritical mind that this
reaction proceeded with retention of configuration—but that would be wrong! You know by now
that a careful analysis is required. In the Cahn-Ingold-Prelog system, the F in the starting material
was priority group 2, but in the product, because Br has left, F is now the first priority group. So
even though the designation of configuration suggests retention of configuration, the molecule has
actually undergone inversion as would be expected with an SN2 reaction. (See the solution to
problem 6-21 for a similar example.)
192
7-68 substitution CH3 CH3
H Br Br H
+
Br H H Br
CH3 CH3 Regardless of which bromine is substituted

2S,3S 2R,3R on each molecule, the same mixture of
racemic mixture products results.
Each of the substitution products has one

KOH chiral center inverted from the starting
material. The mechanism that accounts for
inversion is SN2. If an SN1 process were
CH3 CH3 occurring, the product mixture would also
contain 2R,3R and 2S,3S diastereomers.
HO H H OH Their absence argues against an SN1
+ process occurring here.
Br H H Br
CH3 CH3
2R,3S 2S,3R
racemic mixture
elimination
H Br Br CH3
Br H HO
Br H CH3
rotate
C C
H CH3 Br
CH3 CH3 CH3 H trans
H and Br
anti-coplanar
The other enantiomer gives the same product (you should prove this to yourself).
The absence of cis product is evidence that only the E2 elimination is occurring in one step through an
anti-coplanar transition state with no chance of rotation. If E1 had been occurring, rotation around the
carbocation intermediate would have been possible, leading to both the cis and trans products.
7-69 "Ph" = phenyl
(a) Ph Ph Ph
NaOCH3
+
E2
major minor
Br Z,E mixture
193
7-69 continued
(b) H and Br must be anti-coplanar in the transition state.
H
H δ−
CH3 H OCH3
Ph H H CH3
CH3 Br H CH3 CH3
2R,3R H
Ph CH3
NaOCH3 Ph CH3 Ph CH3
Br
Ph H −
C C Br δ
CH3 CH3 transition state
methyls cis
(c) H
CH3 H Ph CH3
CH3 H
Ph CH3 C C
Ph CH3 CH3 H
Br 2S,3R methyls trans
(d) The 2S,3S is the mirror image of 2R,3R; it would give the mirror image of the alkene that 2R,3R
produced (with two methyl groups cis). The alkene product is planar, not chiral, so its mirror image is the
same: the 2S,3S and the 2R,3R give the same alkene.
7-70
A pi bond is formed from two parallel p orbitals. Rotating around a double bond breaks the pi bond by
forcing the p orbitals to be perpendicular. If anything can stabilize the transition state, the rotational energy
barrier will be lower.
H H rotate right sp2 H
carbon by 90°
H
Each radical is on a 2° carbon, not particularly
C C C C stable. Two radicals on adjacent carbons are
H3C CH3 particularly unstable.
CH3
H3C
H H rotate right sp2 H

carbon by 90°
H
Each radical is on a benzylic carbon; each is
C C C C stabilized by resonance. Review the
Ph Ph solution to 4-45(b) or 6-51 for benzylic
resonance forms.
194
7-70 continued
H3CO
H O O O
sp2
rotate right H H
C C carbon by 90° OCH3 OCH3
N O C C C C
OCH3 OCH3
H3CO N N
O O
An unequal distribution of electrons between the

two sp2 carbons gives resonance forms
O
maximizing the number of pi bonds, all atoms
H
with full octets, and negative charge on the more
OCH3
electronegative atoms! This large degree of C C
stabilization explains the lowest rotational OCH3
energy barrier: this transition state is the easiest N
to form. O
7-71 In E2, the two groups to be eliminated must be coplanar. In conformationally mobile systems like
acyclic molecules, or in cyclohexanes, anti-coplanar is the preferred orientation where the H and leaving
group are 180° apart. In rigid systems like norbornanes, however, SYN-coplanar (angle 0°) is the only
possible orientation and E2 will occur, although at a slower rate than anti-coplanar.
The structure having the H and the Br syn-coplanar is the trans, which undergoes the E2 elimination.
(It is possible that the other H and Br eliminate from the trans isomer; the results from this reaction
cannot distinguish between these two possibilities.)
195
7-72 It is interesting to note that even though three-membered rings are more strained than four-membered
rings, three-membered rings are far more common in nature than four-membered rings. Rearrangement
from a four-membered ring to something else, especially a larger ring, will happen quickly.
H
OH O H
H+ – H2O This 1° carbocation
CH2 would be very unstable.
∆
without rearrangement
H This alkene could be produced from the unrearranged

carbocation, but the 1° carbocation has such a short
H2O lifetime that it is more reasonable to propose the
CH2 CH2 minor pathway through the rearranged 3° carbocation.
with rearrangement—hydride shift

H H
H2O
CH2 C CH2 CH2 minor
3° carbocation, but
still in a strained
4-membered ring
H
H H
H2O
C CH3 CH3 minor
with rearrangement—alkyl shift—ring expansion

H
CH2 C H H MAJOR
H2O
C H2C C H
H2
H H
2° carbocation on
5-membered ring—
HOORAY!
196
7-73
H
CH2OH CH2 OH CH2 1° carbocation—terrible!—will
H+ ∆ rearrange; can't do hydride shift, must
do alkyl shift = ring expansion.
− H2O
This is an unstable carbocation even

though it is 3°; bridgehead carbons
H C H cannot be sp2 (planar—try to make
H2O a model), so this carbocation does a
H
hydride shift to a 2°, more stable
carbocation.
Abstraction of adjacent
H gives bridgehead
alkene—violates hydride shift
Bredt's Rule.
H This 2° carbocation loses an

H adjacent H to form an alkene; can't
H C form at bridgehead (Bredt's Rule)—
H H only one other choice.
H2O H
H
7-74 CH3 CH3 CH3 CH3 CH3 CH3

− H2O
CH3 C C CH3 CH3 C C CH3 CH3 C C CH3
H OSO3H ∆
HO OH HO OH2 HO
methyl shift
CH3 CH3 CH3
CH3 C C CH3 CH3 C C CH3 CH3 C C CH3

H2O
O CH3 O CH3 OH CH3
H
The driving force for this rearrangement is the great stability of the resonance-stabilized, protonated
carbonyl group.
197
7-75 Br
(a) E2— H2C CH CH3 H2C CH CH3 + H2O + Br –

one step
H
OH
Br OH
SN2— CH3 CH CH3 CH3 CH CH3 + Br –
one step
OH
(b) In the E2 reaction, a C—H bond is broken. When D is substituted for H, a C—D bond is broken,
slowing the reaction. In the SN2 reaction, no C—H (C—D) bond is broken, so the rate is unchanged.
(c) These are first-order reactions. The slow, rate-determining step is the first step in each mechanism.
Br H
slow fast
E1 H2C CH CH3 H2O H2C CH CH3 H2C CH CH3
H H H
SN1 Br O OH
slow H2O H2O
H3C CH CH3 H3C CH CH3 H3C CH CH3 H3C CH CH3
fast fast
+ Br –
The only mechanism of these two involving C—H bond cleavage is the E1, but the C—H cleavage does NOT
occur in the slow, rate-determining step. Kinetic isotope effects are observed only when C—H (C—D) bond
cleavage occurs in the rate-determining step. Thus, we would expect to observe no change in rate for the
deuterium-substituted molecules in the E1 or SN1 mechanisms. (In fact, this technique of measuring isotope
effects is one of the most useful tools chemists have for determining what mechanism a reaction follows.)
7-76 Both products are formed through E2 reactions. The difference is whether a D or an H is removed
by the base. As explained in Problem 7-75, C—D cleavage can be up to 7 times slower than C—H
cleavage, so the product from C—H cleavage should be formed about 7 times as fast. This rate preference
is reflected in the 7 : 1 product mixture. ("Ph" is the abbreviation for a benzene ring.)
D H H H H H D H
H − D, Br H − H, Br
C C C C C C C C
H Ph
Ph Br Ph H D Br Ph H
requires C—D bond cleavage; requires C—H bond cleavage;
slow; minor product 7 times faster; major product
198
HOW TO PREDICT SN vs. E MECHANISMS
Is the base/nucleophile strong or weak?
(like HO– or RO–) STRONG WEAK (like H2O or ROH)
Second order: SN2, E2 First order: SN1, E1
Type of carbon with leaving group Type of carbon with leaving group
1°, CH3
1°, CH3, esp. 2° 3° or 2°, 3°,
benzylic and hindered allylic, no appreciable
allylic benzylic reaction, very slow
E2
SN2 > E2
(SN2
easy for nucleophile
199
extremely
to attack electrophilic SN1 and E1
slow)
colleagues, Dr. Hima Joshi, who has permitted its use here.
carbon; higher temperature

higher temperature SN2 and E2
higher temperature and hindered base
and hindered base favor elimination
and hindered base

favor elimination
favor elimination
Note: a methyl halide
cannot undergo elimination.
I know whether a reaction will follow an SN1, SN2, E1, or E2 mechanism? The answer is not always
Here are some generalizations that can provide guidelines about how to make reasonable predictions.
Most instructors have their own version of this "concept map"; this one was modified from one of my
Note to the student: The most common question from students studying Chapter 7 material is: How do
simple even for experienced chemists, and mixtures of substitution and elimination products are typical.
Students: use this space for notes or to solve problems.
200
CHAPTER 9—ALKYNES
9-1 Each pi bond = 1 element of unsaturation; each ring = 1 e.u.
(a) cicutoxin: 3 double bonds + 2 triple bond + 0 ring = 7 unsaturations
capillin: 4 double bonds + 2 triple bond + 1 rings = 9 unsaturations
panaxytriol: 1 double bonds + 2 triple bonds + 0 rings = 5 unsaturations
(b) Many other structures are possible in each case; the number of unsaturations must be consistent.
(1) C5H8 2 (2) C8H10 4 (3) C9H12 4
9-2 New IUPAC names are given. The asterisk (*) denotes acetylenic hydrogens of terminal alkynes.
CH3CH2CH2 C C H
* CH3CH2 C C CH3 (CH3)2CH C C H
*
(a)
pent-1-yne pent-2-yne 3-methylbut-1-yne
(b) Do these isomer problems systematically: draw the 6-carbon chains first, then the 5-carbon chains, etc.
*
HC C C C
*
HC C
H3C C C H3C C C
hex-1-yne hex-2-yne hex-3-yne
3-methylpent-1-yne 4-methylpent-2-
*
HC C * yne
HC C
4-methylpent-1-yne 3,3-dimethylbut-1-yne
9-3 Acetylene would likely decompose into its elements. The decomposition reaction below is
exothermic (∆H° = − 234 kJ/mole) as well as having an increase in entropy. Thermodynamically, at
1500°C, an increase in entropy will have a large effect on ∆G (remember ∆G = ∆H − T∆S). Kinetically,
almost any activation energy barrier will be overcome at 1500°C.
1500 °C
HC CH 2 C + H2
9-4 Adding sodium amide to the mixture will produce the sodium salt of hex-1-yne, leaving hex-1-ene
untouched. Distillation will remove the hex-1-ene, leaving the non-volatile acetylide salt behind.
CH2 CHCH2CH2CH2CH3 NaNH2 CH2 CHCH2CH2CH2CH3
H C C CH2CH2CH2CH3 Na+ C C CH2CH2CH2CH3 non-volatile salt

9-5 The key to this problem is to understand that a proton donor will react only with the conjugate base of
a weaker acid.
(a) H C C H + NaNH2 H C C Na+ + NH3
(b) H C C H + CH3Li H C C Li+ + CH4

(c) no reaction: NaOCH3 is not a strong enough base
(d) no reaction: NaOH is not a strong enough base
(e) H C C Na+ + CH3OH H C C H + NaOCH3 (opposite of (c))
(f) H C C Na+ + H2O H C C H + NaOH (opposite of (d))
(g) no reaction : H C C Na+ is not a strong enough base

(h) no reaction: NaNH2 is not a strong enough base
(i) CH3OH + NaNH2 NaOCH3 + NH3
236
9-6 NaNH2 CH3CH2Br
H C C H H C C Na+ H C C CH2CH3
NaNH2
CH3(CH2)5Br
CH3(CH2)5 C C CH2CH3 Na+ C C CH2CH3
9-7 To be a feasible synthesis, the desired product must have the sp carbons from acetylene bonded to CH2
groups that came from 1° halides in the precursor.
1) NaNH2
(a) H C C H H C C CH2CH2CH2CH3
2) CH3CH2CH2CH2Br
1) NaNH2 1) NaNH2
(b) H C C H H C C CH2CH2CH3 CH3 C C CH2CH2CH3
2) CH3CH2CH2Br 2) CH3I
1) NaNH2 1) NaNH2
(c) H C C H H C C CH2CH3 CH3CH2 C C CH2CH3
2) CH3CH2Br 2) CH3CH2Br
(d) The desired product cannot be synthesized by an SN2 reaction—would require attack of a strong base
on a 2° alkyl halide.
Br 2°
CH3 C C Na+ + CHCH2CH3 CH3 C C CHCH2CH3
strong nucleophile; CH3 CH3
must be second order
low yields; not practical
1) NaNH2 1) NaNH2
(e) H C C H CH3 C C H CH3 C C CH2CHCH3
2) CH3I 2) BrCH2CHCH3
CH3
CH3
1) NaNH2
(f) H C C H H C C CH2
2) Br(CH2)8Br
Br
NaNH2
H2C C C CH2 Na+ C C CH2
Br
Intramolecular cyclization of large rings must be carried out in dilute solution so the last SN2 displacement
will be intramolecular (within one molecule) and not intermolecular (between two molecules).
9-8 1) NaNH2 H3O+
(a) H C C H H C C CH2OH
2) H2C O
OH
1) NaNH2 1) NaNH2
(b) H C C H CH3 C C H CH3 C C CHCH2CH2CH3
2) CH3I 2) HCCH2CH2CH3
O 3) H3O+
237
9-8 continued
OH
1) NaNH2 H3O+
(c) H C C H H3C C C C H
2) Ph CH3
Ph
O
OH
1) NaNH2 1) NaNH2 H3O+
(d) H C C H CH3 C C H CH3 C C CCH2CH3
2) CH3I 2)
CH3
O
9-9 In a synthesis problem, draw the target to see what new bonds need to be made during the synthesis.
OH new C—C bond
1) NaNH2 H3O+
H C C CH2CH3 H3C C C C CH2CH3 2-phenylhex-3-yn-2-ol
2) Ph CH3 1 2 3 4 5 6
Ph
O
9-10 The mechanism is likely to be two sequential E2 reactions. KOH usually makes internal alkynes.
H Br Br
OH OH
C C CH3 C C CH3 C C CH3
∆ ∆
H Br H 1-phenylprop-1-yne
9-11 The mechanism is likely to be two sequential E2 reactions. Where possible, NaNH2 makes terminal
alkynes because the terminal proton is removed by NaNH2 giving a stable acetylide ion as the initial product.
(This is called a thermodynamic sink, or a potential energy well, that is, a valley on the energy diagram.)
Br H Br
H2 NH2 H2 NH2 H2
C C CH C C CH C C C H
∆ ∆
Br H H
H2N
H2 H2O H2
C C CH C C C
3-phenylprop-1-yne This acetylide ion remains in the reaction

mixture until a proton source is added.
9-12
CH3CH2 CH2CH2CH2CH3
H2
(a) CH3CH2 C C CH2CH2CH2CH3 C C
Lindlar's catalyst
H H
H3C H
Na
(b) H3C C C CH2CH3 C C
NH3
H CH2CH3
238
9-12 continued
(c) Br
Br2 H NaNH2 C C
CCl4 Br 150°
cis H Na
NH3
One of the useful "tricks" of organic chemistry is the ability to trans
convert one stereoisomer into another. Having a pair of
reactions like the two reductions shown in parts (a) and (b) that
give opposite stereochemistry is very useful, because a common
intermediate (the alkyne) can be transformed into either
stereoisomer.
CH3CH2 CH2CH3
1) NaNH2 H2
(d) CH3CH2 C C H CH3CH2 C C CH2CH3 C C
2) CH3CH2Br Lindlar's
catalyst H H
HO
9-13 OH CH3CH2CH2 C Ph
1) NaNH2 H2
CH3CH2CH2 C C H CH3CH2CH2 C C CH C C H
2) O Lindlar's
Ph catalyst H H
Ph H (Z)-1-phenylhex-2-en-1-ol
3) H3O +
9-14 The goal is to add only one equivalent of bromine, always avoiding an excess of bromine, because
two molecules of bromine could add to the triple bond if bromine were in excess. If the alkyne is added to
the bromine, the first drops of alkyne will encounter a large excess of bromine. Instead, adding bromine to
the alkyne will always ensure an excess of alkyne and should give a good yield of dibromo product.
9-15 H H
H Br
CH3CH2CH2 C C H CH3CH2CH2 C C H CH3CH2CH2 C C H
2° better than Br Br
1° carbocation
H Br
Br H Br H H
CH3CH2CH2 C C H CH3CH2CH2 C C H CH3CH2CH2 C C H
Br H Br H Br H
2° carbocation and
resonance-stabilized
239
9-16 Br
(a) C CH + 2 HBr C CH3
Br Electrophilic addition to terminal
alkynes follows Markovnikov
Cl orientation.
(b) C CH + 2 HCl C CH3
Cl
Br
(c) + 2 HBr Br
Cl Cl
1 1
3 2 1 2 2
(d) C C CH3 + 2 HCl 3 + 3
Cl Cl
Electrophilic addition to unsymmetric internal alkynes will give mixtures of isomers.
9-17
hν
initiation: RO OR 2 RO •
RO • + H—Br RO—H + Br •
propagation:
Br • + H C C CH2CH2CH3 H C C CH2CH2CH3
Br
H C C CH2CHCH3 + H Br H C C CH2CH2CH3 + Br •
Br Br H
The 2° radical is more stable than 1°. The anti-Markovnikov orientation occurs because the bromine radical
attacks first to make the most stable radical, in contrast to electrophilic addition where the H+ bonds first
(see the solution to 9-15).
9-18
1 eq. Cl2
(a) H C C (CH2)3CH3 H C C (CH2)3CH3 E + Z
Cl Cl
HBr
(b) H C C (CH2)3CH3 H C C (CH2)3CH3 E + Z
ROOR
Br H
HBr
(c) H C C (CH2)3CH3 H C C (CH2)3CH3
H Br
Br Br
2 Br2
(d) H C C (CH2)3CH3 H C C (CH2)3CH3
CCl4
Br Br
240
9-18 continued
H2 HBr
(e) H C C (CH2)3CH3 H C C (CH2)3CH3 CH3 CH (CH2)3CH3
Lindlar's
catalyst H H Br
(or Na, NH3)
H Br
2 HBr
(f) H C C (CH2)3CH3 H C C (CH2)3CH3
H Br The role of the mercury catalyst is not

9-19 Dilute H2SO4 (aq) is shown shown in this mechanism. As a Lewis
here as H3O+. CH3 C C CH2CH3
acid, it may act like the proton in the first
step, helping to form vinyl cations; the
mercury is replaced when acid is added.
See further explanation on the next page.
+OH
3
H3O+
CH3 C C CH2CH3 both 2° vinyl CH3 C C CH2CH3
carbocations
H H
H2O H2O
CH3 C C CH2CH3 CH3 C C CH2CH3
H O H H O H
H H
H2O H2O
H OH HO H
H3O+ H3O+
H H H H
CH3 C C Et CH3 C C Et CH3 C C Et CH3 C C Et
H O H H O H H O H H O H
H2O H2O
H H
H O O H
pentan-3-one pentan-2-one
continued on next page 241
9-19 continued
The role of the mercury catalyst is not shown in this mechanism. As a Lewis acid, it may act like the
proton in the first step, helping to form vinyl cations; the mercury is replaced when acid is added.
H2O – H+ H3O+
CH3 C C CH2CH3 CH3 C C CH2CH3 CH3 C C CH2CH3
H2O
removes
Hg H+ Hg OH H OH
9-20
(a) But-2-yne is symmetric. Either orientation produces the same product.
CH3 CH3 CH3 CH3 O
Sia2BH H2O2 HO–
CH3 C C CH3 C C C C CH3CH2 C CH3
HO–
H BSia2 H OH
(b) Pent-2-yne is not symmetric. Different orientations of attack will lead to different products on any
unsymmetrical internal alkyne.
CH3 C C CH2CH3
Sia2BH Sia2BH
CH3 CH2CH3 CH3 CH2CH3

C C C C
H BSia2 Sia2B H
H2O2 , HO– H2O2 , HO–
CH3 CH2CH3 CH3 CH2CH3

C C C C
H OH HO H
HO– HO–
O O
CH3CH2 C CH2CH3 CH3 C CH2CH2CH3

9-21
O O
(a) (1) (2) H (b) (1) +
O
O (2) same mixture as in (b) (1)
O
(c) (1) (d) (1)
O
(2) same as in (c) (1) (2) same as in (d) (1)
242
9-22
H3C H CH3 H H CH3
(a) C C + BH3 H C C BH2 + C C
H3C CH3 CH3 CH3 H3C CH3
CH3 H H H CH3
H C C B C C H
CH3 CH3 CH3 CH3
disiamylborane, Sia2BH
(b) There is too much steric hindrance in Sia2BH for the third B—H to add across another alkene. The
reagent can add to alkynes because alkynes are linear and attack is not hindered by bulky substituents.
9-23 O O O
(a) (1) HO C C (CH2)3CH3 (2) CO2 + HO C (CH2)3CH3

Oxidation of a terminal alkyne with Oxidation of a terminal alkyne with warm,
neutral KMnO4 produces the ketone basic KMnO4 cleaves the carbon-carbon
and carboxylic acid without cleaving bond, producing the carboxylic acid after
the carbon-carbon bond. acid work-up, and carbon dioxide.
O O O O
(b) (1) CH3 C C CH2CH2CH3 (2) CH3 C OH + HO C CH2CH2CH3

O O O
(c) (1) CH3CH2 C C CH2CH3 (2) CH3CH2 C OH (2 equivalents)

O O O O
(d) (1) CH3CH C C CH2CH3 (2) CH3CH C OH + HO C CH2CH3
CH3 CH3
O
O
(e) (1) (2) OH
HO
O O
9-24
Work backwards on ozonolysis problems like this: ozonolysis of trip bonds produces RCOOH, so reconnect
the fragments at the COOH groups, creating a C≡C.
C C CH2CH3
(a) CH3 C C (CH2)4 C C CH3 (b)
C C
243
9-25 When proposing syntheses, begin by analyzing the target molecule, looking for smaller pieces that
can be combined to make the desired compound. This is especially true for targets that have more carbons
than the starting materials; immediately, you will know that a carbon-carbon bond forming reaction will be
necessary.
People who succeed at synthesis know the reactions—there is no shortcut. Practice the reactions for
each functional group until they become automatic. Use the graphical reaction summaries ("starburst
diagrams"), or customize your own—these are very effective learning tools.
(a) analysis of target from

acetylene
3° acetylenic alcohols made from alkylation

C C of acetylide
from acetylide plus ketones
OH
Put on less reactive
forward direction: Br group first.
H C C H + NaNH2 H C C Na+ H C C
NaNH2
H3O+
C C Na+ C C
OH
O
(b) H H Analysis of target: cyclopropanes are made by carbene insertion into alkenes.
To get cis substitution around cyclopropane, stereochemistry of the alkene
precursor must be cis. Cis alkenes come from catalytic hydrogenation of an
H3C CH2CH3 alkyne using Lindlar's catalyst.
NaNH2 CH3I NaNH2 CH3CH2Br
H C C H H3C C C H H3C C C CH2CH3
H2 Lindlar's
catalyst
H H H H
CH2I2
H3C CH2CH3 Zn, CuCl H3C CH2CH3
Analysis of target: epoxides are made by direct epoxidation of

(c) H CH2CH2CH3 alkenes. To get trans substitution around the epoxide,
stereochemistry of the alkene precursor must be trans. Trans
CH3CH2 O H alkenes come from sodium/ammonia reduction of an alkyne.
NaNH2 CH3CH2Br NaNH2 CH3CH2CH2Br
H C C H CH3CH2 C C H
H CH2CH2CH3 mCPBA H CH2CH2CH3 Na

CH3CH2 C C CH2CH2CH3
NH3
CH3CH2 O H CH3CH2 H
244
9-25 continued
(d) meso-hexane-3,4-diol Analysis of target: diols are prepared from the C=C by two
CH2CH3 methods: cold, dilute KMnO4 (or OsO4), a syn addition; or
H H with a peroxy acid that makes the epoxide, followed by
HO OH
H OH hydrolysis, an anti addition of the two OH groups. Recall
from the solution to 8-35 that in order to produce a meso
H OH CH3CH2 CH2CH3 structure, a syn addition requires a cis alkene, and an anti
addition requires a trans alkene.
CH2CH3
Both syntheses begin with the preparation of hex-3-yne:
NaNH2 CH3CH2Br NaNH2 CH3CH2Br
H C C H CH3CH2 C CH CH3CH2 C C CH2CH3
Route A: via an epoxide on a trans alkene

Na H CH2CH3 mCPBA H CH2CH3
CH3CH2 C C CH2CH3 meso product
NH3 H3 O+
CH3CH2 H CH3CH2 O H
Route B: via syn hydroxylation on a cis alkene
H2 H H cold, dilute KMnO4
CH3CH2 C C CH2CH3 meso product
Lindlar's or OsO4 , H2O2
catalyst CH3CH2 CH2CH3
9-26
(a) CH3 C C (CH2)4CH3 (b) CH3CH2 C C CH2CH2CH(CH3)2 (c) C C H
(d) C C H (e) CH3CH2 C C CHCH2CH2CH3

CH3
Br
C C
(f) (g) (h) C C
Br
Br Br
CH3
H
(i) H C C CH2 C C CH2CH3 (j) H C C CH CH2 (k) H C C
C CH2
H
9-27
(a) benzylacetylene (b) diethylacetylene (c) tert-butylmethylacetylene (d) ethylisopropylacetylene
9-28 (a) 3-hexyne (b) 4-ethyl-2-octyne (c) 3-bromo-1-pentyne

(d) 4,4-dimethyl-2-heptyne (e) 4-methylhept-2-yn-4-ol (f) 1-cyclohexylpent-3-yne
9-29
(a) Br2 (b) 1) NaNH2 , ∆
Br Br 2) H O
2
Br from (a) Br
245
9-29 continued
(c) 2 HBr (d) KOH
200 °C
from (b) Br Br from (c) Br Br
O
(e) H2O (f) 1) Sia2BH
H
H2SO4 2) H2O2
from (b) HgSO4 O from (b) HO–
(g) 1) O3, –78 °C (h) 1) O3, –78 °C

OH H
2) H2O 2) Me2S
from (b) O O
OR KMnO4, NaOH
(i) NaNH2 H
+
H3O+ new bond
from (b) C O
Na+ from (h) OH
10 8 7 6
5
2 1
11 9
4 3
undec-6-yn-5-ol
9-30
(a) H2 (b) H2
Lindlar's Pt or Pd or
catalyst Ni catalyst
(c) Br (d) O
Br2 H2O, H2SO4
anti HgSO4
addition
Br
from (a) two Br trans OR 1) Sia2BH, 2) H2O2, HO–
Br
(e) (f)
2 HBr NBS, hν allylic
Br bromination
OR Br2, hν
from (a)
Br
O O
(g) (h) H 1) O , –78 °C
KMnO4 3
H
H2O 2) Me2S H
O H
neutral O
from (a)
(i) O
1) KMnO4, NaOH 1) O3, –78 °C HO
OR OH
2) H3O+ 2) H3O+
O
246
9-31 O OH
H3O+
CH3CH2 C C CH CH3CH2 C C CH ethchlorvynol
NaNH2
HC HC
CHCl HC CH CHCl
9-32
9-33 Cl Cl
(a) CH2 CCH2CH3 (b) H3C C CH2CH3 (c) CH3CH2CH2CH3
Cl
H Br Br Br
(d) CH2 CHCH2CH3 (e) C C (f) H C C CH2CH3
Br CH2CH3 Br Br
O O O
(g) HO C C CH2CH3 (h) CO2 + HO C CH2CH3 (i) H2C CHCH2CH3
O O
(j) Na+ C C CH2CH3 (k) H3C C CH2CH3 (l) H C CH2CH2CH3
9-34
Br
NaNH2 H2O
(a) H3C C CH2CH3 H C C CH2CH3
150°
Br
Br
KOH
(b) H3C C CH2CH3 H3C C C CH3
200°
Br
NaNH2
(c) CH3CH2 C C H CH3CH2 C C Na+
CH3CH2CH2CH2Br
CH3CH2 C C CH2CH2CH2CH3
247
9-34 continued
H3C H Br Br
Br2 KOH
(d) C C CH3C CCH2CH2CH3 H3C C C CH2CH2CH3
CCl4 200°
H CH2CH2CH3 H H
Br 1) NaNH2
(e) H3C C CH2CH2CH2CH3 150° H C C CH2CH2CH2CH3
Br 2) H2O
H2
(f) C C
Lindlar's cis
catalyst
Na
(g) C C
NH3 trans
OH O
H2O
(h) HC C CH2CH2CH2CH3 CH2 CCH2CH2CH2CH3 H3C CCH2CH2CH2CH3
H2SO4 unstable enol
HgSO4
OH O
1) Sia2BH
(i) HC C CH2CH2CH2CH3 CH CHCH2CH2CH2CH3 H CCH2CH2CH2CH2CH3
2) H2O2,
unstable enol
HO–
H3C H Br Br
Br2 KOH
(j) C C H3C C CCH2CH2CH3 H3C C C CH2CH2CH3
CCl4 200° major
H CH2CH2CH3 H H
H2 Lindlar's
catalyst
H3C CH2CH2CH3
C C
H H
9-35
1. NaNH2 H2/ Lindlar catalyst
1. NaNH2
(a) H C C H H 3C C C H
H 3C C C CH2CH2CH2CH2CH3
2. CH3Br 2. Pentyl Bromide
cis-2-octene
H 3C CH2CH2CH2CH2CH3
248
9-35 continued
1. NaNH2 1. NaNH2 Na/NH3 (liq)
(b) H C C H 2. CH3CH2Br H3CH2C H 2. CH CH CH Br H3CH2C CH2CH2CH3
3 2 2
CH2CH2CH3
H3CH2C
trans-3-heptene
(c)
(d) The diol with the two OH groups on the same side in the Fischer projection is the equivalent of a meso
structure, although this one is not meso because the top and bottom groups are different. Still, it gives a clue
as to its synthesis. The "meso" diol can be formed by either a syn addition to a cis double bond, or by an anti
addition to a trans double bond. We saw the same thing in the solution to 9-25 (d).
9-36 CH3
(a) CH3CH2 C C CH2CH3 (b) CH3CH2 C C H + CH2 C elimination
on 3° halide
OH CH3
(c) CH3CH2 C C CH2OH (d) CH3CH2 C C
(after H2O workup) (after H2O workup)
OH
(e) CH3CH2 C C CHCH2CH2CH3 (f) CH3CH2 C C H + Na+ O
(after H2O workup)
OH
(g) CH3CH2 C C C CH2CH3
(after H2O workup) CH3
9-37
NaNH2 CH3CH2CH2CH2Br
(a) HC C H HC C Na+ HC C CH2CH2CH2CH3
249
9-37 continued
NaNH2 CH3CH2CH2Br
(b) HC C H HC C Na+ HC C CH2CH2CH3
NaNH2
H3C C C CH2CH2CH3
CH3I
H3C CH2CH2CH3
H2
(c) H3C C C CH2CH2CH3 C C
Lindlar's
synthesized in part (b) catalyst H H
H3C H
Na
(d) H3C C C CH2CH2CH3 C C
NH3
synthesized in part (b) H CH2CH2CH3
2 equiv. Br
HBr
(e) HC C CH2CH2CH2CH3 HC CH2CH2CH2CH2CH3 anti-Markovnikov
HOOH orientation
synthesized in part (a) Br
Br
2 HBr
(f) HC C CH2CH2CH2CH3 H3C C CH2CH2CH2CH3 Markovnikov
orientation
synthesized in part (a) Br
O
1) Sia2BH
(g) H C C CH2CH2CH3 H CCH2CH2CH2CH3
from (b) 2) H2O2, HO–
O
H2O
(h) H C C CH2CH2CH3 H3C CCH2CH2CH3
H2SO4
from (b)
HgSO4
NaNH2 CH3CH2Br NaNH2
(i) HC C H HC C Na+ HC C CH2CH3
CH3CH2Br
CH3CH2 CH2CH3 CH3CH2 CH2CH3
Br2 H2
C C CH3CH2 C C CH2CH3
Lindlar's
H H
H
Br H Br catalyst
Alkene must be cis to Review the stereochemistry in the

produce the (±) product solution to Problem 8-35 of this
from anti addition. Solutions Manual.
250
9-37 continued
NaNH2 CH3I 1) NaNH2
(j) HC C H HC C Na+ HC C CH3 H3C C C CH3
2) CH3I
Lindlar's
H2
Alternatively, trans-but-2-ene could be catalyst
dihydroxylated with anti stereochemistry H C CH3
using aqueous peracetic acid. 3 H3C CH3
OsO4
C C
Review the stereochemistry in the H2O2
H H
solution to Problem 8-35 of this H
OH HO H
Solutions Manual.
meso Alkene must be cis to produce the
meso product from syn addition.
NaNH2 CH3CH2Br
(k) HC C H HC C Na+ HC C CH2CH3
OH NaNH2
H3O+
H3C C C C CH2CH3
O
CH3
9-38 5 H2
Compound X CH2CH2CH2CH3
Pt
The fact that five equivalents of hydrogen are

1) O3, –78 °C consumed says that X must have five pi bonds in the
2) Me2S, H2O above carbon skeleton.
O O O O O O O O
H C CH2CH2 C C H + H C C H + H C C OH + H C OH
from C C
6 carbonyls 3 alkenes 2 carboxylic acids 1 alkyne
Whether the alkene is cis or trans cannot

CH CH C CH be determined from these results.
Compound X
9-39 Compound Z O O O O
ozonolysis ⇒ CH3(CH2)4 C H CH3 C CH2 C OH HO C H
from alkene from alkyne

Compound Z: Whether the alkene is E or
CH3(CH2)4CH C CH2 C C H
Z cannot be determined
CH3 from this information.
251
9-40 This synthesis begins the same as the solution to problem 9-35:
NaNH2 NaNH2
HC CH HC C CH2Br PhCH2 C CH PhCH2 C C
benzyl
bromide
The anion will add across the carbonyl group of the aldehyde:
O OH
H H3O+
PhCH2 C C H
acid-catalyzed H2SO4, ∆
dehydration
H
O
mCPBA
H
9-41 O
1) Sia2BH
(a) CH3CH2 C C H CH3CH2CH2 C H
2) H2O2, HO–
(b) O Et
reaction 1 H O Et
R C C H + O Et R C C
H
H O Et H O Et H O Et
H3O+
R C C R C C C C
reaction 2 R
H H H H H
H2O H
H O Et H O Et H O Et
H3O+
R C C H R C C H R C C H
H O H H2O H OH H OH
H − HOEt
H H H
R C C H R C C H R C C H
H2O
H O H O H H O H
252
9-41 continued
(c) alkyne
RO–
R C CH R C CH The closer that electrons are to the nucleus, the more stable.
An s orbital is closer to a nucleus than a p orbital is, as p
OR orbitals are elongated away from the nucleus. An sp2
sp2 carbanion carbanion is more stable than an sp3 carbanion because the
alkene sp2 carbanion has 33% s character and the electron pair is
RO– closer to the positive nucleus than in an sp3 carbanion which
R C CH2 R C CH2 is only 25% s character. The sp2 carbanion is easier to form
because of its relative stability.
H H OR
sp3 carbanion
9-42 Diols are made by two reactions from Chapter 8: either syn-dihydroxylation with OsO4 or cold
KMnO4, or anti-dihydroxylation via an epoxide using a peroxyacid and water. As this problem says to use
inorganic reagents, the solution shown here will use OsO4 rather than a peroxyacid which is organic.
Recall the stereochemical requirements of syn addition as outlined in this Solutions Manual, Problem 8-35:
cis-alkene + syn addition → meso trans-alkene + syn addition → racemic (±)
cis-alkene + anti addition → racemic (±) trans-alkene + anti addition → meso
Part (a) asks for the synthesis of the meso isomer, so syn addition will have to occur on the cis-alkene. Part
(b) will require syn addition to the trans-alkene to give the (±) product.
(a)
Br
NaNH2 NaNH2
HC C H HC C Na+ HC C
Br
OsO4 H2
H2O2 Lindlar's C C
C C
HO
H H OH catalyst
H H
Alkene must be cis to produce the meso
product from syn addition, so reduction is done
with Lindlar's catalyst to produce the cis
alkene.
(b) Br
NaNH2 NaNH2
HC C H HC C Na+ HC C
Br
OsO4 Na
H
H2O2 NH3 C C
C C
H
OH H OH
H
Alkene must be trans to produce the
(±) product from syn addition, so
reduction is done with Na/NH3.
253
9-43 Each unknown has the molecular formula C8H12 with 3 elements of unsaturation.
(a)
Addition of H2 to the triple bond gives cyclooctane. Cleavage of the triple bond with
ozone will produce an 8-carbon chain with a carboxylic acid at each end, as shown in the
W solution to 9-30(i).
(b)
Addition of H2 to the double bonds gives cyclooctane. Cleavage of the double bonds
with ozone will produce two 4-carbon chains with an aldehyde at each end.
X
(c)
Addition of H2 to the double bonds gives cyclooctane. Cleavage of the double bonds
with ozone will produce one 3-carbon chain and one 5-carbon chain with an aldehyde at
Y each end.
(d)
H2 bicyclo[4.2.0]octane
catalyst
Z
O
O3 –78 °C
Addition of H2 to the double bond gives bicyclo[4.2.0]octane.
H Cleavage of the double bond with ozone opens the larger ring but
Me2S H retains the cyclobutane with 1-carbon and 3-carbon chains with an
aldehyde at each end.
O
254

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CHAPTER 1—STRUCTURE AND BONDING

(e) H C C N H (f) H C O H (g) H C C Cl (h) H N N H

(i) H C C C H (j) H C C C H (k) H C C C H

(a) N N (b) H C N (c) H O N O (d) O C O

(e) H C C N H (f) H C O H (g) H C C Cl (h) H N N H

(d) Na O C H (e) H C H (f) H C H (g) Na H B H

O O O Move electrons away

(c) H C C C H H C C C H Move electrons away from (–) charge.

(e) O N O O N O Move electrons away from (–) charge.

(b) H C C N H C C N The second structure has negative charge

The first structure has the negative

original H H The latter two structures have

H C C C N H C C C N Move electrons away from (–) charge.

original H minor H major

(f) The lone pair of electrons on C cannot be delocalized to the C=C.

H lower electron density

minor higher electron density

lower electron density

higher lower electron density

(f) H3C O C C C N H3C O C C C N

lower electron density

(a) H C C C C C C H (b) H C C C Cl (c) H C C C C N

(d) C C C H (e) H C C C C C (f) H C C C O H

molecular weight = 90, three times the empirical weight HO OH

(b) 32.0 g C some possible structures:

(d) 38.4 g C some possible structures:

(a) sp2 (b) sp2

(b) Carbon and oxygen are both sp2 hybridized.

One pair of electrons on oxygen is

(c) Oxygen and both carbons are sp2 hybridized.

All oxygens are sp2 with bond angle 120°.

This electron pair is in an sp2

sp2 sp2 sp2 sp2

sp2 sp2 sp2

sp3 H H sp3 two CH3 on opposite two CH3 on the same

(c) The CH3 on the N is on the same CH3

1-27 (a) Sodium (b) Neon (c) Boron (d) Magnesium

(d) H C C N (e) H C C H (f) H C S C H

(g) H O S O H (h) H C N C O (i) H C O S O C H

(a) COOH (b) N C CHO

C3H4 H C3H6 H H H C3H8 H H H

(e) (f) (g) (h)

(f) C4H4O (g) CH3NO2 (h) C6H10O

1-40 Non-zero formal charges are shown by the atoms.

major—all atoms have octets

major—negative charge on the

(i) H C C C C C CH3 H C C C C C CH3 All resonance

(a) CH3 C C N CH3 C C N

(b) CH3 C C C CH3 CH3 C C C CH3 CH3 C C C CH3

CH3 C C C CH3 CH3 C C C CH3 CH3 C C C CH3

negative charge on electronegative atoms—equal energy

NH2 NH2 NH2

(a) O CH2 O CH2 O CH2 O CH2

CH2 CH2 CH2

CH2 CH2 CH2 CH2

(f) H major—negative charge

(e) CH2 CH2 CH2

C C C lower electron density

H lower electron density

(c) higher electron density