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Chapter 1
1
Bonding in
Organic Compounds
CHAPTER SUMMARY
Organic chemistry is the study of compounds of carbon. This is a separate
branch of chemistry because of the large numbers of organic compounds and
their occurrences and applications.
Chapter 1
Chapter 1
Chapter 1
A single bond has one bonding pair of electrons; there are two bonding
pairs (four electrons) in a double bond and three bonding pairs in a triple
bond. The number of bonds formed by elements commonly found in organic
compounds is: C - 4; N - 3; O, S - 2; H - 1; F, Cl, Br, I - 1. A carbon can
have four single bonds, two double bonds, a double and two single bonds, or
a triple and a single bond; all total four bonds. These bonds can be
represented by electron dot or line bond formulas.
C. Drawing Electron Dot Formulas
In drawing electron dot formulas, one must use every atom in the
molecular formula and satisfy the valence (the number of bonds formed)
for each. A good procedure involves bonding together atoms with valences
greater than one with single bonds, inserting double and triple bonds until all
valences can be satisfied with the available monovalent atoms, and finally
attaching the monovalent atoms.
D. The Structural Nature of Compounds
Ionic compounds are composed of positive and negative ions in a ratio
that will provide an electrically neutral compound. The atoms of a covalent
compound are attached to one another to form molecules. Dissolution of an
ionic compound in water produces solvated ions whereas covalent
compounds have solvated molecules.
E. Polyatomic Ions and Formal Charge
Polyatomic ions are charged species in which several atoms are
connected by covalent bonds. The magnitude and location of the ion's
charge is called the formal charge. The formal charge on an atom is equal
to the group number of the atom on the periodic table minus the non-bonding
electrons and half of the bonding electrons.
F. Polar Covalent Bonds
A polar covalent bond is composed of atoms with similar but not equal
electronegativities. The more electronegative atom is partially negative and
the other is partially positive.
1.5 An Orbital Approach to Covalent Bonding
A. Sigma and Pi Covalent Bonds
Chapter 1
A covalent bond is formed by the overlap of two atomic orbitals each with
one electron. There are two types: sigma and pi. A sigma bond involves
the overlap of two atomic orbitals head-to-head in one position (such as two
s-orbitals, an s and a p-orbital, or two p-orbitals). A pi-bond involves the
overlap of parallel p-orbitals at both lobes.
B. Electron Configuration of Carbon
Bonding in carbon involves the promotion of a 2s electron to an empty 2p
orbital thus creating four unpaired electrons, one in the 2s and one in each of
the three 2p orbitals. This allows carbon to be tetravalent.
C. Shapes of Organic Molecules
The shapes of organic molecules are predicted using the following
principle: atoms and non-bonding electron pairs attached to a common
central atom are arranged as far apart in space as possible. If there are four
surrounding groups, the shape is tetrahedral; with three, the groups protrude
to the corners of a triangle (trigonal); and with two, the region is linear.
D. Carbon with Four Bonded Atoms
A carbon with four bonded atoms is sp 3-hybridized, tetrahedral, and
has approximately 109o bond angles. The four atomic orbitals on carbon
(an s and three p's) combine, through a process called hybridization, to
form new orbitals with different geometric orientations. The four new sp3orbitals are raindrop shaped and are oriented to the corners of a tetrahedron.
All bonds to the carbon are sigma bonds.
E. Carbon Bonded to Three Atoms
A carbon with three bonded atoms is sp2-hybridized, trigonal, and
has approximately 120o bond angles. There are three new sp2-hybrid
orbitals directed to the corners of a triangle; these form sigma bonds with
other atoms. The remaining p-orbital overlaps with a parallel p-orbital of an
adjacent, sigma bonded atom to form a pi-bond and complete the double
bond.
F. Carbon Bonded to Two Atoms
A carbon with two bonded atoms is sp-hybridized, linear, and has
180o bond angles. There are two new sp hybrid orbitals that are directed
opposite to one another on a straight line; these form sigma bonds. The two
remaining p-orbitals overlap with p-orbitals on a similarly hybridized atom to
5
Chapter 1
form two pi-bonds and complete the triple bond. Alternatively, the two porbitals can overlap with counterparts on two adjacently bonded sp2hybridized atoms forming two double bonds.
G. Bonding in Organic Compounds A Summary
A carbon with four bonded groups is tetrahedral, sp3-hybridized, and has
109.5O bond angles. A carbon with three is trigonal, sp2-hybridized, and has
120O bond angles. A carbon with two bonded groups is linear, sp-hybridized,
and has 180O bond angles.
A single bond is a sigma bond; a double bond is composed of one sigma
bond and one pi-bond; a triple bond is one sigma and two pi-bonds.
Triple bonds are stronger than double bonds and double bonds are
stronger than single bonds. The opposite order describes relative bond
lengths.
1.6 Bonding to Oxygen and Nitrogen
An oxygen with two bonded atoms and two non-bonding electron pairs is
and has two sigma bonds (single bonds). With only one bonded
atom, the oxygen is sp2-hybridized and is involved in one sigma and one pi bond,
a double bond. A nitrogen with three bonded atoms and one non-bonding
electron pair is sp3-hybridized and has three sigma bonds (single bonds). With
two bonded atoms the nitrogen is sp2-hybridized and involved in two single
bonds (sigma) and a double bond (sigma and a pi). A nitrogen with only one
bonded atom is sp-hybridized, has one single bond (sigma) and one triple bond
(one sigma and two pi-bonds).
sp3-hybridized
Chapter 1
SOLUTIONS TO PROBLEMS
mass number
12C
12
13C
13
35Cl
35
17
17
17
18
37Cl
37
17
17
17
20
(c) F 9, 19.0
16, 32.1
Al 13, 27.0
1s2
1s2
1s2
1s2
2s22p6
2s22p6
2s22p6
2s22p6
3s1
3s23p1
3s23p3
3s23p5
Mg
Si
S
Ar
1s2
1s2
1s2
1s2
2s22p6
2s22p6
2s22p6
2s22p6
3s2
3s23p2
3s23p4
3s23p6
Ca
Ga
Ge
As
Se
Br
Kr
4s1
4s2
4s24p1
4s24p2
4s24p3
4s24p4
4s24p5
4s24p6
Rb
Sr
In
Sn
Sb
Te
Xe
5s1
5s2
5s25p1
5s25p2
5s25p3
5s25p4
5s25p5
5s25p6
Chapter 1
(b) Al, 3
(c) C, 4
(d) N, 5
(e) S, 6
(f) Br, 7
Rn 6s26p6
: .F:
Li
(LiF)
1s22s22p6
O:
Mg
2-
: O:
(MgO)
1s22s22p63s2
: :
2+
Mg:
(b)
1s2
1s22s22p5
1s22s1
Li .
(a)
1s22s22p4
1s22s22p6
1s22s22p6
(b) Mg(OH)2
(c) (NH4)2SO4
(d) Li2CO3
(e) CaO
(f) CaCO3
(g) NaNO2
(h) KClO3
(b) 4
(c) 4
(d) 3
(e) 2
(f) 2
(g) 1
(h) 1
(a)
.. ..
Cl ..
.. . .. .
.
.
H C . Cl .
.. ..
.. Cl ..
..
(b)
H ..
H
. . ...
. C. . O.
(c)
..
..
.. O ....C ....O ..
(d) H .. C .. ..
.. C.. ..
.
.Cl. .
Chapter 1
C
.. .. _
H : C : O:
.. ..
.. ..H +
H : C: N : H
.. ..
H H
+
(b) C
Br
(c)
(d)
(e)
+
(f) C
C
sp3-hybridized,
H
C
C
H
C
H
H
C
H
Chapter 1
(b)
H
C
H
N
sp
sp3
sp2
H
O
H
sp
sp2
sp3
Chapter 1
(g) He
(h) Xe
(i) As
Ca
Ca2+
(b) Na2O
Na+
Na
2-
+
Na
Na+
F
Cl C F
Cl
(a)
(e) H
(b) H
(f)
(d)
Cl
Cl
(g) S
C Cl
Cl C
(h)
Cl C Cl
Cl
(k)
(l)
Cl
O
O
(c) H
(j)
(i)
Cl
S H
H
H
(m) N
(n) H N
(o)
Cl Cl
11
Chapter 1
Cl
(p) Cl Al Cl
(q)
O N
H.
.
C
H ....
H
c) ..
H .H. H
.
.. C.. ..C.. .Br.
H . .C
. .. .. ..
..
H H H
.. .
H .. ..
C. H H
.. C .. .C. .. H
.. ..
H
H H
H .H. ..
b) ..
.
. . .
H . .C
. ...C. .O. . H
.H. . .. . .H. .
.
H . ..
C ..O
. . ..C . H
H H
..
.
. . . .
.. .Cl. .. ..C .. .C. .. ..
.. .. .. .Cl. . H . ..C..C. . ..Cl .
d)
.. .. ..
. . .
H ...C
. ....C.. .C. . H
H ..Br
.. H
e) H H
.. . .. . .. .
H .. ..
C ..C
. . ..N . H
H
..H . .. . ..
.
.
H . .C
. ...N . .C. . H
H H H
H H H
. .
.H. ...Cl ...
H H
f) H H
H
..
.
.
..
.
.
.
.
H ...C
. . C .. C. H
H
. C..H
.
H.. . ... ..H
..C . C..
H.
..
.. .
e)
H ..O
.. . ..H
..
.
H .. N .. C.. ..
.. N . H
...
O.
c) H ..
..
.
.. C. .. ..O.. H
H .. .C
. ..
H
f)
.H. . .. . . . . .. .
.
H . C . N . . C . . O.
..
H
h) ..
H .H. H
.. . .H. . ...
.
.
.
.
H . .C
. . C. . C. ..C. ..S. H
H
H
.. .
g) .O
. ... ..
H .H.
..
.
.
.
H . C ...
O. .C. .. ..
C.. H
H H
.. .
O
i) H
H ...
. . ..
.
.
..
.. C .. ..O.. H
H .. ..
C...C
.
.
H ..O.
..
..
H
12
H .H.
d) ..
.
.
H . C ....C.. C.. .. .. N.
j)
H H
.H. . ..
.. ..
.
H . C. .C... .C... .S... H
..
H H H
Chapter 1
(a)
Br
O
O
(b)
C C C C
H C
H H
C C
C H
H H
H C
C C C
H
C H
O
O
b) CH3
f) CH 3
c) -.. CH 3
+
N
.
N.
.H. +
..O CH3
d) CH3
..
.
g) CH 3O
...
h)
Br
13
Chapter 1
Carbonate
ion
Bicarbonate
ion
C
O
H
1.28 Polar Covalent Bonds: Section 1.4F
Most bonds in organic compounds are considered polar except carbonhydrogen and carbon-carbon bonds.
H
O +
C C
+ O H +
N
H - H +
+
+ - H
H S C
H
14
Chapter 1
sigma bond
pi bond
single bond
triple bond
double bond
H
H
(a)
(b)
C
H
(c)
H
C
H
H
C
H
15
Chapter 1
H
(d)
H
C
H
sp2
trigonal
O
120 bond angles
sp3
tetrahedral
109O bond angles
sp
linear
O
180 bond angles
Problem 1.33: Single bonds are sigma bonds; double bonds are one sigma and
one pi bond. Triple bonds are one sigma and two pi bonds.
16
Chapter 1
N
H
(b)
C
H
(c)
H
(d)
H
H
(e)
H
H
C
H
17
Chapter 1
s2 p1 p1 p1
hybridizes to
in NH3
Surrounding boron are three space occupying groups, the three fluorines.
Boron does not have an octet of electrons. Therefore it assumes a trigonal
shape and is sp2 hybridized.
B
s1 p1 p1 p0
hybridizes to
Chapter 1
nitrogen is in Group V and has five outers shell electrons, there is a non-bonding
electron pair remaining following formation of three bonds. This pair of electrons
is available for sharing with electron-deficient species unlike the bonding pairs of
CH4. Boron is in Group III of the periodic table. Since it has only three outer
shell electrons it forms three bonds. However, it does not achieve a stable octet.
Consequently, it is attracted to species that have electron pairs available for
bonding (such as the N in NH3) because, in reacting, it can achieve a stable
octet.
H:
H
..
H: B
..H
H :C
H
..
H: N:
H
..
H
..
..H
Formaldehyde
Hydrogen Cyanide
19
Chapter 1
20
The Alkanes
Chapter 2
2
THE ALKANES:
STRUCTURE AND NOMENCLATURE
OF SIMPLE HYDROCARBONS
CHAPTER SUMMARY
Organic compounds are classified according to common structural
features that impart similar chemical and physical properties to the compounds
within each group or family.
2.1 Hydrocarbons: An Introduction
Hydrocarbons are composed only of carbon and hydrogen and fall into two
major classes - saturated and unsaturated. Saturated hydrocarbons or the
alkanes are entirely constructed of single bonds and have the general formula
CnH2n+2. Unsaturated hydrocarbons include the alkenes (CnH2n) in which
there is at least one carbon-carbon double bond; the alkynes (CnH2n-2) where
there is at least one carbon-carbon triple bond; and aromatic hydrocarbons
which appear to have double bonds but actually have a special structure that is
discussed in Chapter 6.
2.2 Molecular and Structural Formulas - Isomerism
Compounds are described by molecular formulas and structural
formulas. Molecular formulas describe the kinds of atoms and numbers of
21
Chapter 2
The Alkanes
The Alkanes
Chapter 2
Chapter 2
The Alkanes
The Alkanes
Chapter 2
25
Chapter 2
The Alkanes
them to fit more easily in a crystal lattice and thus they generally have higher
melting points.
C. Solubility and Density
Hydrocarbons are non-polar and insoluble in water and, because they
are less dense, they float on the surface of water.
CONNECTIONS 2.1:
Petroleum
SOLUTIONS TO PROBLEMS
2.1
2.2
H
H
H
H
Skeletal Isomers
H
H
H
H
H
H
26
The Alkanes
Chapter 2
Now draw five carbon chains and place one two-carbon chain or two one-carbon
chains on it. If the two-carbon side chain is placed on either the first or second
carbon, it merely extends the longest chain. However, placing it on the third
carbon gives us another isomer.
CH2CH 3
CH3CH 2 CHCH2CH3
Now attach two one-carbon chains to the carbon skeleton.
CH 3
CH 3 CCH 2CH 2CH 3
CH 3
CH 3
CH 3
CH 3
CH 3
CH 3
Finally, draw a four carbon chain with three one carbon side chains.
CH3 CH3
CH3C
CHCH3
CH3
2.5 Skeletal Isomers of Cycloalkanes: Five cyclic compounds of C5H10.
Start with a five-membered ring. Then use a four-membered ring with a onecarbon side chain. Finally, draw a three-membered ring with either one twocarbon side chain or two one-carbon side chains.
CH2CH 3 CH3
CH3
CH3
CH3
CH3
27
Chapter 2
The Alkanes
(b) C8H12
(c) C15H29Br
Br
Br
CH2
CH2
Br
Five isomers of C3H6BrCl
Br
CH 3CH 2CHBr CH3CH
Cl
Cl
CH2
CH2
Br
Cl
Cl
Br
Br
CH 3CCH 3
28
Cl
The Alkanes
Chapter 2
CH3
CH 2CHCH 3
CH3
CH2CH 3
CH3
CHCH 3
CH3
1-isobutyl-3-isopropylcyclopentane
CH2CH 3
5,6-diethyl-2,2,4,8-tetramethylnonane
1-chloropentane
Cl
Cl
2-chloropentane
CH 3
CH 2CHCH 2CH 3
Cl
1-chloro-2-methylbutane
3-chloropentane
CH 3
CH 3CCH 2CH 3
Cl
2-chloro-2-methylbutane
29
Chapter 2
The Alkanes
CH 3
CH 3
CH 3CHCH 2CH 2
CH 3CHCHCH 3
Cl
Cl
2-chloro-3-methylbutane
CH 3
H3C C CH 2Cl
CH 3
1-chloro-3-methylbutane
1-chloro-2,2-dimethylpropane
CH 3
H
H
Eclipsed
Staggered
H
H
H
H H
Least Stable
Most Stable
2.14 Conformational Isomers of Butane
CH3
H3C
H
H
H
H 3C
H
CH3
H H
CH3
CH3
H
H
H 3C H
Least Stable
CH3
Most Stable
CH3
b)
c)
Br
H
30
CH3
H Br
The Alkanes
Chapter 2
e)
Br
d)
H
H
Br
Br
Br
H
2.16 Equilibrium between Chair Forms
(a) The equatorial position is more spacious and the isomer more stable.
more
stable
ax Br
H
eq
eq
Br
H
ax
(b) The equatorial positions are more spacious and preferred in the equilibrium.
ax CH(CH 3)2
H eq
H eq
ax CH 3
more
stable
ax
H
CH 3
eq
H
ax
CH(CH 3)2
eq
31
Chapter 2
The Alkanes
(c) The equilibrium favors the isomer in which the larger isopropyl group
is in the more spacious equatorial position.
ax CH(CH 3)2
H
eq
H3C
more
stable
ax
H
eq
eq
CH 3
eq
CH(CH 3)2
H ax
2.17
H ax
Br
Br
CH 3
Br
Br
H
CH 3
cis
trans
1-bromo-2-methylcyclopentane
cis
CH 3
trans
1-bromo-3-methylcyclopentane
32
The Alkanes
Chapter 2
CH 2CH 3
CH 3
CH 3
CH 3CH 2CHCH 2CH 2CH 3 CH 3CCH 2CH 2CH 2CH 3 CH 3CH 2CCH 2CH 2CH 3
CH 3
3-ethylhexane
CH 3CH
2,2-dimethylhexane
CH 3
CH 3 CH 3
CH 3
3,3-dimethylhexane
CH 3
CH 3
CH 3
2,3-dimethylhexane
2,4-dimethylhexane
2,5-dimethylhexane
CH 3
CH 3 CH 3
CH 3CH 2CH
CH 3
CH 3 CH 2
CH 2CH 3
CH 2
CH 3
3,4-dimethylhexane 3-ethyl-2-methylpentane 3-ethyl-3-methylpentane
CH 3 CH 3
CH 3C
CH 3 CH 3
CHCH 2CH 3
CH 3
CH 3CCH 2CHCH 3
CH 3
CH 3CH
CH 3
C
CH 2CH 3
CH 3
CH 3
H3C
H3CCH
CH 3 CH 3
CH
CHCH 3
CH 3CH 3
H3C
CH 3
CH 3CH 3
2,3,4-trimethypentane
2,2,3,3-tetramethylbutane
33
Chapter 2
The Alkanes
(b) three isomers of C9H20 with eight carbons in the longest chain: write the
longest chain straight across. Don't put anything on the chain that would make it
longer.
CH 3
CH 3
CH 3CHCH 2CH 2CH 2CH 2CH 2CH 3
2-methyloctane
3-methyloctane
CH 3
CH 3CH 2CH 2CHCH 2CH 2CH 2CH 3
4-methyloctane
CH 3
CH3CCH 2CH2CH2CH2CH3
CH 3
CH 3
2,2-dimethylheptane
CH 3CH 3
3,3-dimethylheptane
CH 3
2,3-dimethylheptane
CH 3
CH 3
CH 3
CH 3
CH 3
4,4-dimethylheptane
CH 3
CH 3
2,4-dimethylheptane
CH 3CH 3
2,5-dimethylheptane
CH 3
CH 3
CH 3CHCH 2CH 2CH2CHCH 3 CH 3CH 2CHCHCH 2CH 2CH 3 CH 3CH 2CHCH 2CHCH 2CH 3
2,6-dimethylheptane
3,4-dimethylheptane
3,5-dimethylheptane
(d) Eight isomers of C9H20 with five carbons in longest chain: Draw a fivecarbon chain across the paper in a straight line. Arrange the remaining four
34
The Alkanes
Chapter 2
carbons in as many ways as possible without making the chain longer. The ways
to consider arranging the remaining four carbons are: a) one four-carbon chain;
b) a three- and a one-carbon chain, c) 2 two-carbon chains; d) 1 two- and 2
one-carbon chains; and e) 4 one-carbon chains. Variations a) and b) are not
usable as there is no way to place a four- or three-carbon unit on a five-carbon
chain without extending the longest chain.
CH3CH 2
CH3
CH3
CH3
CH2
CH2 CH3
CH2
CH2CH 3
CH3CH 2CH
CH2
CCH3
CH 3CHCHCHCH 3
CH3
CH3 CH3
CH3
3,3-diethylpentane 2,2-dimethyl-3-ethylpentane 2,4-dimethyl-3-ethylpentane
CH3
CH3 CH3
CH2
CH3CH
CH3C
CCH2CH3
CH3
CH3C
CCH2CH3
CH3 CH3
CH3 CH3
2,3-dimethyl-3-ethylpentane
CH2
CH3
CCH3
CH3
2,2,3,3-tetramethylpentane 2,2,4,4-tetramethylpentane
CH3
CH
CHCH3
CH3
CH3CH
CHCH 3
CH3
CH3
2,2,3,4-tetramethylpentane
CH3 CH3
2,3,3,4-tetramethylpentane
(e) four isomers of C10H22 with nine carbons in the longest chain:
CH3
CH 3CHCH 2CH 2CH 2CH 2CH 2CH 2CH 3
2-methylnonane
CH3
CH3CH 2CHCH 2CH 2CH 2CH 2CH 2CH 3
3-methylnonane
35
Chapter 2
The Alkanes
CH3
CH3
4-methylnonane
5-methylnonane
(f) two isomers of C10H22 with only two alkyl groups on a six carbon chain:
CH2CH 3
CH2CH 3
CH
3CH 2CHCHCH 2CH 3
CH2CH 3
CH2CH 3
3,4-diethylhexane
3,3-diethylhexane
(g) six isomers of C10H22 with five carbons in the longest chain:
CH3
CH 3CH
CH3 CH2CH 3
CH2CH 3
CH 3C
CCH 2CH 3
CH3 CH2CH 3
CCH 2CH 3
CH 3C
CH3 CH3
CH2CH 3
3,3-diethyl-2-methylpentane
CH3
CHCHCH 3
CH3
3-ethyl-2,2,3-trimethylpentane
3-ethyl-2,2,4-trimethylpentane
CH 2CH 3
CH 3CH C
CH 3 CH 3 CH 3
CHCH 3 CH 3C
CH 3 CH 3 CH 3
CHCH 3
CH 3 CH 3CH 3
CH 3C
CH 3 CH 3
3-ethyl-2,3,4-trimethylpentane
CH 3
CH 3
2,2,3,4,4-pentamethylpentane
2,2,3,3,4-pentamethylpentane
36
CH-CCH 3
The Alkanes
Chapter 2
(h) the isomer of C13H28 with the shortest longest chain possible
CH3 CH 3 CH3
CH 2
CH 3C
CCH 3
3,3-diethyl-2,2,4,4-tetramethylpentane
CH
CH3 CH 2 CH3
3
(i) five cyclic compounds of C5H10
CH3
CH2CH 3
CH3
CH3
CH3
CH3
CH2CH 3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH2CH 2CH3
CH3
CH
CH3
CH2CH 3
CH3
CH2CH 3
CH3
CH3
CH3
CH3
CH3
37
Chapter 2
The Alkanes
CH 3
CH 3
CH 3
Names in Order: ethylcyclohexane; 1,1-dimethylcyclohexane
1,2-dimethylcyclohexane; 1,3-dimethylcyclohexane;
1,4-dimethylcyclohexane
(l) 12 isomers of C9H18 that have a six-membered ring
CH 3
CH 2CH 2CH 3
CHCH 3
H3C
CH 3
CH 2CH 3
CH 2CH 3
CH 3
CH 3
H3C
CH 3
CH 3
H3C
CH 3
CH 3
CH 2CH 3
CH 2CH 3
Names in Order: 1-ethyl-3-methylcyclohexane;
1-ethyl-4-methylcyclohexane; 1,1,2-trimethylcyclohexane;
1,1,3-trimethylcyclohexane
38
The Alkanes
Chapter 2
CH 3
H3C
CH 3
CH 3
CH 3
CH 3
CH 3
CH 3
H3C
CH 3
CH 3
CH 3
b)
CH3
1
CH3
CH3
CH3
5 isomers
Cl
d)
1
CH3
3 isomers
c)
CH3
1 isomer
5 isomers
2.22 Skeletal and Positional Isomerism: Sections 2.3 and 2.5
a) three isomers of C2H3Br2F
Br H
Br Br
H Br
H
Br
1,1-dibromo-1-fluoroethane
Br H
1,1-dibromo-2-fluoroethane
1,2-dibromo-1-fluoroethane
39
Chapter 2
The Alkanes
CH 3CH
CH 3CCH 3
Br
Br
Br
CH 2
CH 2CH 2CH 2
Br
Br
Br
Br
CH 3CH 2CHCH 3
CH 3CH 2CHCH 2
CH 3CHCH 2CH 2
Br
F Br
Br
Br
CH2
Br
Br
CHCH3
F
CH3
CH3
CH 3CHCHBr
CH3
CH3
CH2
Br
CH3C
Br
CH3
CH2
CH2
CH2
Br
40
Br
CH 3CH 2CCH 3
Br Br
CH 3CH 2CHCH 2
Br
2,2-dibromobutane
1,2-dibromobutane
The Alkanes
Chapter 2
Br
Br
Br
Br
Br Br
CH 3CHCH 2CH 2
CH 3CHCHCH 3
1,3-dibromobutane
1,4-dibromobutane
2,3-dibromobutane
(e) nine isomers of C5H10Br2 with four carbons in the longest chain
For simplicity let us just show the required carbon skeleton and move the two
bromines around systematically. First, place two bromines on the same carbon.
C
C
Br
Br
Br
C
Br
Br
Br
1,1-dibromo-3-methylbutane
1,1-dibromo-2-methylbutane
2,2-dibromo-3-methylbutane
Now put a bromine on carbon-1 and vary the position of the other bromine.
C
C
Br
Br
C
C
Br
Br
Br
1,2-dibromo-2-methylbutane
Br
1,4-dibromo-2-methylbutane
1,3-dibromo-2-methylbutane
Finally, draw isomers in which the bromines are on the middle two carbons and
the two carbons on the other end.
Br
C
C
Br
1,3-dibromo-2-ethylpropane
Br
Br
Br
Br
1,2-dibromo-3-methylbutane
2,3-dibromo-2-methylbutane
41
Chapter 2
The Alkanes
(f) five isomers of C6H13Cl with four carbons in the longest chain.
Again let us draw the carbon skeletons, there are two, and vary the position of
the chlorine.
C
C
Cl
C
C
1-chloro-2,2-dimethylbutane
Cl
C
Cl
1-chloro-3,3-dimethylbutane
3-chloro-2,2-dimethylbutane
Cl
1-chloro-2,3-dimethylbutane
Cl
2-chloro-2,3-dimethylbutane
The Alkanes
Chapter 2
Section 2.6
CH3 CH3
Cl
(c)
CH3
CH3 CH2CH 3 CH
3
(d) CH 3CCH 2CHCH
CH3
Cl
Cl
Cl
Cl
Cl
CHCH2CH3
CH2CH 2CH3
(a)
H
C OH
View
front to back
H
OH
H
H
OH
H
H
H
43
Chapter 2
The Alkanes
HOCH 2
(b)
CH 2OH
HO
View
HO
H
OH
HO
OH
H
H
HH
(c)
H
OH
H
CH3
C OH
View
front to back
H H
front to back
OH
H
H
H
HO
H
H
H
OH
H
OH
H
H
OH
OH
H
H
CH3H
CH3
44
The Alkanes
(b)
Chapter 2
ax
H ax
H ax
CH3
CH3
CH3
CH3
eq
eq
eq
eq
H ax
CH3
eq
H ax
CH3
eq
H ax
(c)
CH3 ax
H
eq
eq
CH3 ax
CH3 ax
ax
CH3
eq
eq
H
eq
eq
CH3 ax
H
ax
(d)
CH3
CH3 ax
H eq
CH3 eq
H ax
45
Chapter 2
The Alkanes
(e) most stable chair form of 1-butyl-3-methylcyclohexane with one group axial
and one equatorial
H ax
CH2CH 2CH2CH3
ax
CH3
eq
eq
Br
Br
H
Br
Br
diaxial
less stable
(c)
diequatorial
more stable
one Br axial
one Br equatorial
1-ethyl-3-methylcyclohexane
CH3
CH3CH 2
H
CH3
less stable
both groups axial
CH2CH 3
46
Br
Br
more stable
both groups equatorial
The Alkanes
Chapter 2
ax
CH2CH 3 ax
H eq
eq
H eq
CH3
less stablelarger group
in crowded axial
position
(d)
CH3
ax
CH2CH 3
eq
H ax
1-ethyl-4-methylcyclohexane
CH2CH 3
H
ring flip
H
CH3
CH3
H
CH2CH 3
CH2CH 3
H
ring flip
CH3
CH3
CH2CH 3
(e) 1,3,5-tribromocyclohexane
Br
more stableonly one Br
Br
in crowded
axial position;
other two in
spacious equatorial
H H
ring
H
Br
flip
Br Br
Br
47
Chapter 2
The Alkanes
another that they cannot be bridged by a single carbon. The two single bonds
are not long enough nor can they be conveniently directed in the necessary
geometry.
CH3
O
CH2
CH 2
CH3
CH2
H
CH3
CH3
CH3
CH3
CH3
CH3
Camphor
O
H
Boat Form
CH3 O
Chair Form
CH 3
H
CH 3
CH 3
H3C
identical structures
H
CH 3
H
H
CH 3
H
H3C
CH 3
CH3
CH3
cis
trans
H
48
CH3
The Alkanes
(b)
Chapter 2
1-bromo-3-chlorocyclobutane
Br
Cl
Br
H
trans
cis
H
Cl
cis
1,2-dimethylcyclohexane
CH3
CH3
CH3
trans
CH3
H
(b)
1,3-dimethylcyclohexane
CH3
CH3
cis
CH3
trans
CH3
H
(c)
1,4-dimethylcyclohexane
H
CH3
CH3
CH3
trans
cis
CH3
1,2-dibromo-3-chlorocyclopropane
Br
Cl
Br
Br
H
Br
Cl
H
Cl
H
Br
H
H
Br
49
Chapter 2
(b)
The Alkanes
1,2,3-tribromocyclopropane
Br
Br
Br
Br
H
Br
H
H
Br
H
(c)
1,2,4-tribromocyclopentane
Br
Br
Br
Br
Br
Br
Br
H
H
(d)
Br
H
H
Br
2-chloro-1,4-dibromocyclopentane
Br
Br
Cl
H
Br
Cl
H
Br
Br
Br
Cl
H
Br
H
Br
H
Cl
50
u ax
eq
ax u u
ax u
eq d
d ax
d eq
u eq
d d ax
eq
eq u
d ax
cis
u/u or d/d
trans u/d or d/u
The Alkanes
(a)
Chapter 2
cis 1,2-dimethylcyclohexane
CH 3 ax,u
(b)
CH 3
ax,u
CH 3
eq,u
CH 3
eq,u
cis 1-bromo-3-chlorocyclohexane
Br ax,u
ax,u
Cl
Cl
eq/u
H
less stable
H
more stable
H
(c)
Br
eq/u
trans 1,4-diethylcyclohexane
ax,u CH 2CH 3
H
eq/d
more stable
CH 2CH 3 ax,d
(d)
eq,u
CH 2CH 3
eq/u
cis 1-ethyl-4-methylcyclohexane
CH3 ax,u
CH2CH 3 ax,u
CH3
CH 3CH 2
less stable
(e)
less stable
CH2CH 3
more stable
H
trans 1-ethyl-3-methylcyclohexane
eq,u
51
Chapter 2
less
stable
The Alkanes
ax,u
CH2CH 3
more
stable
H
H
H
CH3
CH3
ax,d
eq,d
CH2CH 3
eq,u
Now put lines on each atom corresponding to the number of monovalent atoms
will be necessary to satisfy the valence. Note below you need eight monovalent
elements.
There are two bromines in the molecule so you still need six hydrogens to
provide a total of eight monovalent atoms.
2.38 Physical Properties: Section 2.9
(a) Boiling points increase with molecular weight within a homologous series.
Both examples are alkanes; ethane has the greater molecular weight.
(b) These two compounds are isomers and have the same molecular weight.
The unbranched isomer has greater surface area and thus there are more
opportunities for intermolecular attraction. The greater the attractions between
52
The Alkanes
Chapter 2
molecules, the more energy necessary to break these attractions and the higher
is the boiling point. The branched isomer has less surface area and less
intermolecular interactions as a result.
(c) CBr4 has the higher molecular weight and thus the higher boiling point.
(d) Cyclohexane is more symmetrical and compact and consequently forms a
more stable crystal lattice. Such a lattice requires more energy to disrupt and
cyclohexane has a higher melting point.
(e) Melting points generally increase with molecular weight (all other factors
being equal) since it requires more energy (higher temperatures) to give the
heavier molecules enough motion to break out of a stationary crystal lattice.
2.39 Combustion: Connection 2
(a)
CH4
2O
CO2
2H 2O
(b)
C3H8
5O
3CO 2
4H2O
(c)
2C8H18
+ 25O2
16CO 2
18H 2O
Connection 2
Gas - any hydrocarbon with 1-4 carbons; for example CH4, the main
53
Chapter 2
The Alkanes
any
hydrocarbon
with
11-18
carbons;
for
example
54
The Alkanes
Chapter 2
1
2
3 isomers
1
1
4 isomers
1 isomer
3. Make a model of ethane, C2H6. Rotate the two carbons relative to each other
around the carbon-carbon bond.
Make the staggered and eclipsed
conformations.
staggered
eclipsed
55
Chapter 2
The Alkanes
4. Using your models from exercise 3, remove one hydrogen and replace it with
a bromine. Find the one staggered and one eclipsed conformation. Now
replace a second hydrogen, on the other carbon, with a bromine. Find the
two staggered and two eclipsed conformations.
The Br symbol is put into one of the hydrogens on one carbon to show where you
should place a bromine and what two conformations you will see.
Br
Br
In the following models, there are two bromines, one on each carbon. In the first
structure they are totally eclipsed. To get the other three models, the rear carbon
is rotated to give staggered, eclipsed, and finally another staggered.
Br
Br
Br Br
Br
Br
Br
Br
5. Make a model of the chair form of cyclohexane. Notice that each carboncarbon bond is in a staggered conformation. Identify the axial and equatorial
hydrogens.
6. Using the model from exercise 5, remove one axial hydrogen and place a
methyl (CH 3) group in its place. Replace the hydrogen and put the methyl group
in the place of an equatorial hydrogen.
56
The Alkanes
Chapter 2
Cyclohexane
With 1,3-dimethylcyclohexane
With 1,4-dimethylcyclohexane
57
Chapter 3
3
Alkenes and Alkynes:
Structure and Nomenclature
CHAPTER SUMMARY
58
Chapter 3
alkynes. The carbon chain is numbered to give the lowest possible number
to the multiple bond nearest the end of the longest chain; when there is a
choice, double bonds take precedence.
B. Procedure for Naming Alkenes and Alkynes
(1) Name the longest continuous chain of carbons first making sure to
select the chain so that it contains the double and triple bonds. (2) Use the
suffix -ene for double bonds and -yne for triple bonds. (3) Number the chain
giving preference to double or triple bonds (double over triple if necessary).
(4) Name all other groups connected to the longest chain with prefixes.
C. Naming Compounds with Both Double and Triple Bonds
The suffix will have both -enes and -ynes. Lowest numbers are given to
multiple bonds with double bonds taking priority over triple when necessary.
D. Common Nomenclature
Simple alkenes are named by following the name of the corresponding alkyl
group with ene, as in ethylene and propylene. Alkynes can be named as
derivatives of the simplest alkyne, acetylene. Vinyl is the prefix designation
for a two carbon alkene and allyl for a three carbon alkene.
CONNECTIONS 3.1 Oral Contraceptives
3.3 Skeletal, Positional, and Functional Isomerism in Alkenes and Alkynes
Alkenes and alkynes exhibit skeletal isomerism in which the carbon chain is
varied and positional isomerism where the position of the multiple bond is
different. Functional isomers differ in the class of compounds to which they
belong. For example, functional isomers of an alkyne could be a diene,
cycloalkene, or bicyclic alkane.
3.4 Functional Isomerism in Organic Chemistry
Common functional groups in organic chemistry include: alkanes, alkenes,
alkynes, aromatic hydrocarbons, carboxylic acids, aldehydes, ketones,
alcohols, ethers, amines.
59
Chapter 3
60
Chapter 3
SOLUTIONS TO PROBLEMS
3.1 General Molecular Formulas
Alkanes: CnH2n+2; Cycloalkanes: CnH2n; Alkenes: CnH2n;
Alkynes: CnH2n-2 Cycloalkenes: CnH2n-2; Dienes: CnH2n-2;
Cycloalkynes: CnH2n-4
3.2 Nomenclature of Alkenes and Alkynes
(a) 1-heptene; (b) 2-heptyne; (c) 3-methylcyclohexene; (d) 2,4-heptadiyne
3.3 Nomenclature of Compounds with Both Double and Triple Bonds
(a) 2-hexen-4-yne; (b) 6-ethyl-4-octen-1-yne
3.4 Skeletal, Positional, and Functional Isomerism
CH3CH 2CH 2CH2CH2CH
CH2
1-heptene
CHCH3
positional isomer
CH3
CH3CHCH2CH2CH
CH2
skeletal isomer
functional isomer
(cycloalkane)
CH
CCH3
positional isomer
61
Chapter 3
CH3
CH3CHCH2CH2C
H2C
CH
CHCH2CH
CHCH2CH3
skeletal isomer
CH
CH 2
Propyne
CH 2
Propadiene
Cyclopropene
CH 3CH 2C
CH
1-Pentyne
CCH 3
2-Pentyne
CH 3CHC
CH
3-Methyl-1-butyne
CH 2
CH 3CH 2CH
CHCH 3
1-Pentene2-Pentene
CH 3
CH 3
CH 3CHCH CH 2
CH 3C CHCH 3
3-Methyl-1-butene2-Methyl-2-butene2-Methyl-1-butene
62
CH 3
CH 3CH 2C
CH 2
Chapter 3
CH 3
CH 3
CH 3 O
CH 3C
CH 3CHCH 2 COH
COH
CH 3
(b) two alcohols and one ether with the formula C3H8O
CH 3CH 2CH 2OH
CH3CHCH 3
CH3OCH 2CH 3
OH
(c) four amines with the formula C3H9N
CH 3
CH 3CH 2CH 2NH 2
CH3CHNH 2
CH 3
CH3NHCH 2CH 3
CH3NCH 3
(d) three straight chain aldehydes and ketones with the formula
O
CH 3CH 2CH 2CH 2CH 2CH CH 3CH 2CH 2CH 2CCH 3 CH 3CH 2CH 2CCH 2CH 3
3.10 Functional Groups
O
CH 3CH
CH 2
alkene
CH 3C
CH
alkyne
CH 3CH 2COH
carboxylic acid
O
CH 3CH 2CH
aldehyde
63
Chapter 3
O
CH 3CCH 3
ketone
alcohol
CH3OCH 2CH 3
amine
ether
CH3
CH3
C
cis:
CH3
trans:
H
C
CH3
(b) For geometric isomerism, each carbon in the double bond must have two
different attached groups. In 2-butene, each carbon has a hydrogen and methyl.
In 1-butene, the first carbon has two identical groups, hydrogens, and thus cistrans isomers do not exist.
3.13 Geometric Isomerism
(a) 1-bromopropene has two different groups on each carbon involved in the
double bond and exhibits geometric isomerism.
Br
cis
CH 3
C
trans
CH 3
C
Br
C
H
CH 3
C
64
CH 2Br
C
C
Br
C
H
Chapter 3
(b) 1-pentene has two hydrogens on one of the double bond carbons but 2pentene has two different groups on each of these carbons.
CH 3CH 2CH 2
CH 3CH 2
C
H
CH 3
C
1-pentene
CH 3
H
C
H
CH 3CH 2
cis 2-pentene
trans 2-pentene
(c) In 2-methyl-2-pentene, there are two methyl groups on one of the double
bond carbons and geometric isomerism is not possible. In 3-methyl-2-pentene,
each carbon of the double bond has two different bonded groups. Notice that the
cis and trans designations are made on the basis of the longest chain of carbon
and whether it crosses the double bond in a cis or trans fashion.
CH 3CH 2
CH 3CH 2
CH 3
C
H3C
CH 3
2-methyl-2-pentene
H3C
CH 3
CH 3
C
C
H
C
H
CH 3CH 2
cis 3- methyl-2-pentene
trans 2-methyl-2-pentene
CH 3CH 2
C
cis
CH 3CH 2CH 2
C
H
C
H
CH 3CH 2
cis
CH 2CH 3
C
trans
H3C
(b)
H3C
CH 2CH 3
CH 3CH 2CH 2
Br
trans
C
H
H
C
Br
H3C
Br
C
Br
(b)
CH 3
C
CH 3
C
H
65
Chapter 3
H
C
Br
H
C
Br
(c) 4
(d) 5
66
CHCH 2CH 3
3-hexene
Chapter 3
CH 3
CH 3
CH 3CH 2CH 2C CH 2
2-methyl-1-pentene
CH 3
CH 3CH 2CHCH
CH 2
3-methyl-1-pentene
CH 3
CH 3CHCH 2CH CH 2
4-methyl-1-pentene
CH 3
CH 3
CH 3CH 2C CHCH 3
CH 3CHCH
2-methyl-2-pentene
3-methyl-2-pentene
4-methyl-2-pentene
CH 2CH 3
CH 3CH 3
CH 3CH 2CH
CH 3CH 2C
CCH 3
CH 3CH-C
CH 2
2-ethyl-1-butene
CHCH 3
CH 3
CH 2
CH 3CCH
CH 2
CH 3
3,3-dimethyl-1-butene
2,3-dimethyl-1-butene
CH 3CH 3
CH 3C CCH 3
2,3-dimethyl-2-butene
CH3
CH3
CH3
CH3
CH3
CH3
CH2CH 2CH3
CH
CH3
CH3
CH3
CH2CH 3 CH2CH 3
CH3
CH3
CH3
CH3
CH3
67
Chapter 3
CH 3
CH 3
CH 3CH 2CHC
CH
CH 3CHCH 2C
3-methyl-1-pentyne
CH 3
CH
CH 3CHC
4-methyl-1-pentyne
CCH 3
4-methyl-2-pentyne
CH 3
CH 3C
CH
3,3-dimethyl-1-butyne
CH 3
3.21 Nomenclature of Alkenes, Alkynes, and Cycloalkanes
Section 3.2; Please see names in problem 3.20 solutions.
3.22 Nomenclature of Alkenes: Section 3.2
(a) 1-heptene; (b) 3,4-dimethyl-3-heptene; (c) 4,4-dimethyl-2-pentene;
(d) 4-ethyl-1-cyclopentene; (e) 2-cyclopropyl-5-propyl-3-octene;
(f) 3,5-diethyl-8-methyl-3-nonene; (g) 2,4-octadiene;
(h) 1,3,5,7-cyclooctatetraene; (i) 4,5-dibromo-2-methyl-2,4,6-nonatriene.
Let us illustrate the procedure with the last example:
(i)
1. Nine carbons in the longest chain: non
2. Three triple bonds: nonatriene
3. Number the chain left to right; complete suffix: 2,4,6-nonatriene
4. Name all other groups with prefixes. The complete name is:
4,5-dibromo-2-methyl-2,4,6-nonatriene
3.23 Nomenclature of Alkynes: Section 3.2
(a) 1-butyne; (b) 2,2-dibromo-7-methyl-3-octyne;
(d) 3-ethyl-3-methyl-1-pentyne; (e) cyclooctyne;
(f) 9-methyl-2,4,6-decatriyne
68
(c) 4-methyl-2-pentyne;
Chapter 3
CHC
CH 3
CHCH 2CH
CCH 3
3,7-dimethyl-1,3,6-octatriene
CH2
CH CH
CH C
Cl
CH 2
C CH
CH 2
tetrafluoroethene 2-chloro-1,3-butadiene
C CH
CHCH3
1,3,11-tridecatrien-5,7,9-triyne
CH3 CH3
CH2
CH 3CCH 2CHCH 3
CCl2
1,1-dichloroethene
CH3
2,2,4-trimethylpentane
CHCH2CH3
CHCH3
CHCH2CH2CH3
69
Chapter 3
(b)
CH3
CH3
CH3
CH 3CHCHCH 3
OH
CH3
CH 3CCH 2CH 3
OH
CH 2CHCH 2CH 3
OH
(c)
CH 3CH 2CCH 2CH 2CH 2CH 3 CH 3CH 2CH 2CCH 2CH 2CH 3
(d)
CH3
CH3
CH
CH 3CCH 2CH 2C
CH3
CH3
CH3
CH3
CH 3CCH 2C
CH 3CC
CCH2CH3
CCH3
CCH2CH2CH 3
CH3
CH3
(e)
CH2NH 2
CH3
CH3
NH2
CH3
NH2
NH2
(f)
CH3
CH3
CH3
CH3
CH 3CHCH 2CCH 3
Br
70
CH3
CH3
CH 3CHCHCHCH 3
Br
Chapter 3
CH 3O
CH 3CCH 2CH 2CH 3 CH 3CH 2CH 2CH 2CH CH 3CH 2CCH 2CH 3 CH 3CH-CCH 3
ketone
functional-aldehyde
positional
skeletal
(b)
CH 3
CH 3CH 2CH 2OCH 3
ether
positional
skeletal
(c)
CH 3
CH 3CH=CHCH 3
CH 3CH 2CH=CH 2
alkene
functional-cycloalkane
CH3C=CH 2
positional
skeletal
(d)
CH 3
CH 3 O
CH 3CHCH 2CH
aldehyde
O CH 3
positional
skeletal
(e)
O
HO
alcohol
CH 3
CH 3(CH 2)5CH
functional-aldehyde
HO
CH 3CH 2
OH
CH 3
positional
skeletal
71
Chapter 3
(f)
O
CH 3
CH 3
functional: aldehyde/ether
CH 3O
CH 3(CH 2)4COH
positional
skeletal
(g)
CH 3CH 2CH 2C
CH
CH 2=CHCH=CHCH 3
alkyne
CH 3C
CH 3CHC
CCH 2CH 3
positional
CCH 3
skeletal
alcohol-aldehyde
O
d) CH 3OCH 2CH 2CH
alcohol-ketone
O
e) CH 3OCH2CCH 3
ether-aldehyde
f) HOCH2CH
ether-ketone
CHCH2OH
alkene-dialcohol
O
g) CH3OCH
CHOCH3
i)
h)
OH j)
HO
OH
alkene-diether
72
alcohol-ether
dialcohol
diether
Chapter 3
O
CH
CH 3CHCH 2CCH 3
O
CH 3
CH 3CHCH 2CCH 3
O
O
(c) aldehydes or ketones with the formula C5H10O
O
O
CH 3CH 2CH 2CH 2CH
CH 3 O
CH 3CH
CH 3
CCH 3
CH 3CHCH 2CH
CH 3 O
CH 3
HC
CHCH 2CH 3
CH 3C
CH
CH 3
(d) carboxylic acids with the formula C6H12O2
O
O
CH 3CH 2CH 2CH 2CH 2COH
CH3
O
O
CH 3CHCH 2CH 2COH
CH 3CH 2CHCOH
CH 3
CH 2CH 3
O
CH 3 O
CH 3CCH 2COH
CH 3
CH 3CH
CH3
CH 3 O
CH 3CH 2C
COH
CH 3
CHCOH
CH 3 CH 3
73
Chapter 3
CH 3CH 2CHCH 3
CH 3
CH 3CHCH 2OH
CH 3CCH 3
OH
OH
CH 3OCH 2CH 2CH 3
CH 3OCHCH 3
CH 3
(f) alcohols or ethers with the formula C5H12O
CH 3CH 2CH 2CH 2CH 2OH
OH
CH 3
CH 3
CH 3
CH 3
OH
CH 2CHCH 2CH 3
OH
CH3
CH3
CH 3CCH 2OH
CH 3OCHCH 2CH 3
CH3
CH 3
CH 3
CH 3
CH 3
(g) amines with the formula C4H11N
CH3
CH 3CH 2CH 2CH 2NH 2
CH3
NH2
74
CH3
Chapter 3
CH2
alkene-alcohol
ketone
aldehyde
CHCH2CH2CH2OH
OH
CH2
CHCH2CH2OCH3
alkene-ether
alcohol
ether
Identify the two groups on each carbon and attach them to the above template.
This is one geometric isomer. Interchange the two groups on one of the carbons
to obtain the other isomer.
(a)
H
C
Br
Br
H
C
c) CH3CH 2
H
C
CH3CH
CH3
CH3CH
CH2CH 3
C
CH2CH 3
Cl
CH3
H
C
CH2CH 2CH2OH
Cl
H
C
CH3CH 2
Br
Br
CH3
H
d)
H
C
Cl
Cl
(b)
C
CH2CH 2CH2OH
CH3
75
Chapter 3
CH 3
CH 3
C
CH 2CH 3
C
CH 2CH 3
trans or E
CH 3
cis or Z
H3C
H
C
(b)
H3C
Br
(c) CH CH
3
2
Cl
(d)
CH 2CH 3
H3C
Cl
C
C
CH 2Br
E 2-octene
The alkyl groups are the
higher priority on each
ring and they are on
opposite sides.
E 3,6-dibromo-2-hexene:
On the left carbon of the double bond,
the methyl (C) is the higher priority group.
The right carbon has a C and Br directly
attached. The Br is of higher priority. The
two higher priority groups are opposite.
Z 3-chloro-3-hexene:
On the left carbon, the chlorine is of higher
priority than the carbon of the ethyl and on
the right, the carbon of the ethyl is higher
priority than the hydrogen. The two high
priority groups are put on the same side.
Z 1-bromo-2-chloro-2-butene:
On the left carbon of the double bond, the methyl
group is of higher priority (C>H). Don't be fooled
on the right; a Cl not a Br is directly attached. The
Cl is of higher priority than CH2Br.
The Cl and CH3 are placed on the same side for Z.
76
Chapter 3
(a) This molecule is capable of exhibiting four geometric isomers since each
double bond shows geometric isomerism and the molecule is not symmetrical.
H
H
C
H
Cl
Br
H
C
Br
C
C
Cl
cis-cis
cis-trans
Br
H
C
Br
Cl
C
H
C
C
Cl
H
trans-trans
trans-cis
(b) This molecule has two double bonds, both capable of geometric isomerism.
However, each double bond has the same attached groups and the molecule is
symmetrical. As a result the cis/trans and trans/cis isomers are the same and
the total number of geometric isomers is only three.
H
H
C
CH3
C
H
cis-cis
CH3
CH3
C
H
C
H
H
C
C
CH3
CH3
C
H
C
H
trans-cis or cis-trans
H
H
C
C
H
C
CH3
trans-trans
(c) This compound has three double bonds capable of geometric isomerism and
it is not symmetrical; there are eight possible isomers. All double bonds can be
cis, all trans, two cis and one trans in three different ways, and one cis and two
trans in three different ways.
cis cis cis
cis cis trans
cis trans trans
trans trans trans
cis trans cis
trans cis trans
trans cis cis
trans trans cis
77
Chapter 3
CH3
C
CH3
H
C
CH2CH 3
H
C
H
cis-cis-cis
CH2CH 3
trans-trans-trans
H
C
H
C
CH 3
C
H
(b)
H
C
C
CH 3
CH 3CH 2
cis-trans-cis
2,4,6-octatriene
CH 2CH 3
C
C
H
cis-cis
3,5-octadiene
more
stable
78
H3C
CH 3
C
C
H
H3C
less
stable
CH 3 H3C
C
H3C
C
C
CH 3
CH 3
C
H
Chapter 3
CC
CH 2
CH
C
CH 2
CHCH
CHCH
CHCH
CH 2
CH 2
CH 2
C
CH
CH 2
(b) C 6H8: This formula has three units of unsaturation than can be expressed as
one triple and one double bonds, three double bonds, one triple bond and one
ring, two double bonds and a ring, one double bond and two rings, or three rings.
CH2
CH
C CH2CH 3
CH2
CH CH
CH2
C
CH2
CH
CH2
CH2
CH
C
CH
CH2
CH
CH2
CH
79
Chapter 3
80
Chapter 3
CH3
C
CH2
CH3
C
H
C
CH3
CH3
CH3
CH3C
CH2
BrCH2CH
CH2 CH3C
CH2
H
Br
Br CH3
CH3
Br
Br
CH3C
b) CH 3CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 3
CCH3
O
c) CH 3CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2COH
CH3 CH3
O
d) HC
CCCH
CH 2
e) HC
CH
C
C
CH 3
C
H
CH
H
C
f)
HC
CH 3
CH 3
CH 3
C
H
81
Chapter 3
OH
h) HC
g)
CH
CHCH 3
i) CH3OCH 2OCH 3
CH3
CH3
j) CH3
CH2CH 3
CH3
k)
OH
CH3
:
OH
CH 2
CH 2
C
CH 2
CH 2
CH 2
CH 2
CH 2
CH 2
C
H
cis
trans
CH 2
CH 2
H
C
CH 2
CH 2
C
H
C
H
cis
cis
82
Chapter 3
83
Chapter 3
3. Make a model of ethyne. Now replace the hydrogens with methyl groups to
get 2-butyne. Compare to 2-butene which exhibits cis-trans isomerism. Why
does 2-butene show geometric isomerism but not 2-butyne?
84
4
C
C
.
C
: -
An Introduction to
Organic Reactions
CHAPTER SUMMARY
In the previous three chapters we have progressed from atoms and electrons to
bonds and molecules to sophisticated structural representations and
nomenclature of organic molecules. Chapter 4 uses this knowledge of organic
structure to introduce organic chemical reactions.
4.1 General Principles of Organic Reactions
A. Types of Reactions: The Reaction Equation
A reaction equation describes what happens in a chemical reaction by
displaying the reactants and products. It describes what bonds break in the
reactants and what new bonds form in the products. There are three main
types of organic reactions. In substitution reactions, an atom or group of
atoms is replaced by another species. Elimination reactions involve the
removal of a pair of atoms or groups from two adjacent atoms to form a
85
Chapter 4
Chapter 4
87
Chapter 4
Chapter 4
Use of Curved Arrows: Curved arrows are used to describe the movement of
electrons in a reaction mechanism. The arrow starts with the electron(s) to be
moved and ends at the atom or bond where they move. Full arrows are used to
denote the movement of electron pairs and fish hook arrows are used to show
the movement of single electrons.
89
Chapter 4
or
+ 2AB
+ 2AB
or
CH2
HBr
CH3CH
CH2
Br
CH2
HBr
CH3CHCH3
CH3CH
H
CH3CH
Br
Br2
Br
CH
+ 2Br2
CH3C
Br
90
Br
CH
Br
HBr
Chapter 4
(c) addition;
(f) substitution
Br
Br
Br
Br
homolytic cleavage
Br Br
free radicals
carbanions
CH3CH 2CH 2
CH3CH 2CH 2
CH3CH 2CH 2
CH3CHCH3
CH3CHCH3
CH3CHCH3
4.7
(a)
(b)
(c)
(d)
(e)
(f)
91
Chapter 4
(a)
Cl
-
CH2C
+ +
H +
(b)
O
-
+
H
CH3
+
N
-
(c)
+ +
CH2CH 2
O
-
+
CH3C
+
H
H+
CH3CH 2NH 2 +
(b)
H+
Cl
CH3CH 2NH 2
Cl
Cl
Cl
O
O
H
O H
O
(c)
CH3CCH3
(d) CH3C
H+
Cl
H+
Cl
CH3CCH3
Cl
CH3C
N H
Cl
92
Chapter 4
polar
bond
+
H
..
O
..
multiple
bond
+
CH2CH
..
:O
polar
bond
Lewis
base
CH 3CCH 2CH 2
+
++
CH2
Br
+ H
CH 3CH 2CH 2
+
polar
bond
Lewis
base
N
..
-
Lewis
base
Br2
+
light
Cl2
light
CH3Br
HBr
CH3CH 2Cl
HCl
93
+
H
Chapter 4
CH3
light
CH3CHCH2CH3
CH3
CH2CHCH2CH3
Cl2
CH3CCH2CH3
Cl
monochlorination conditions
Cl
CH3
CH3
CH3CHCHCH3
CH3CHCH2CH2
Cl
Cl
light
Initiation
Br2
Propagation
CH3CH3 + Br
Propagation
CH3CH2 + Br2
2 Br
CH3CH2
HBr
CH3CH2Br + Br
(a) CH3CH2CH2OH
CH3CH
CH2
aqueous
(b) CH3CH2CH2CH2Br
KOH
H2O
CH3CH 2CH
alcohol
CH2
+ KBr + H2O
(c) CH3CH2CHCH3
KOH
aqueous
CH3CH 2CH
CH2
+
CH3CH
CHCH3
alcohol
Br
+ KBr + H2O
4.17 Preparation of Alkynes
(a)
94
HC
CH
+ 2NaCl + 2 NH3
Chapter 4
CH3CH 2C
CH
+ 2 NaBr +
2 NH3
Br
CH
CH 3C
H2C
CH 2
+ 2NaBr + 2NH3
Br
4.18 Orientation of Elimination: See Example 4.2
In (a), two alkenes are possible. Concentrate on the carbon with the OH. If the
H on the carbon to the right eliminates, the product is monosubstituted; if the H
on the carbon to the left is eliminated the major product, trisubstituted, is formed.
In (b) a disubstituted alkene is formed if a hydrogen from the carbon to the left of
the carbon-chlorine bond is eliminated.
The product shown, which is
tetrasubstituted, is formed if the H on the carbon to the right is eliminated.
a)
b)
CH3
CH3C
CHCH3
CH3 CH3
CH3C
CCH3
CH 3
CH 3
H2SO 4
CH 3CCH 2CH 3
CH2=CCH 2CH 3
OH
+
CH3C=CHCH 3
predominant product
trisubstituted
Reaction Mechanism
CH 3
CH 3CCH 2CH 3
:OH
..
Step 1:
protonation
CH 3
CH 3
..
CH 3CCH 2CH 3
:OH
..
H
-H2O:
CH 2=CCH 2CH 3
CH 3
CH 3CCH 2CH 3
+
Step 2:
loss of H 2O;
carbocation
formation
-H
Step 3:
loss of
hydrogen
ion to form
alkene
CH 3
CH 3C=CHCH 3
predominant
product
95
Chapter 4
Na +
_
C
N
CH3CH 2
+
C + +C
CH3CH 2CH2CH
C
N CH3 O H
+
-
S -
Br
Br
Al
Br
b)
CH3
.N.
acid
..
..O
c) CH3
CH3
base
base
a) CH3CH 2
b)
Cl
Cl
Al
Cl
c)
H + H+
.. ..O
CH3CH 2
Cl
N.
+ HCl
CH 3
H
d)
CH 3
CH 3
N.
CH 3
96
+
H
Cl
H
CH 3
.H.
..O
Al
-. .. +
.O
Cl H
H
+
.
N . H Cl
H
F
+
+ B
F
CH 3
CH 3 F
N
..
CH 3 F
B
acid
..
..O
d)
Chapter 4
.. O:
polar
bond
Lewis
base
H
CH3C(CH2)5
C
C
+
+ ..
H
C O
.. H +
multiple
bond
O
..:
-
Lewis
base
polar
bond
CH 3
CH 3C. A
CH 3
CH 3C+
carbocation
.A
free radical
CH 3
CH 3C . A
CH 3C.
CH 3
CH 3
CH 3
CH 3
CH 3
CH 3
CH 3
.
CH 3C .
CH 3C
A+
carbanion
CH 3
97
Chapter 4
A+
A.
_
A:
..
..
..
A :C
C
+
carbocation
A :C
C.
free radical
A :C
C
..
_
carbanion
CH3
CH3
CH3
CH3
CH3
Cl
Cl
Cl
Cl
b)
CH3
CH3
CH3
CH3
CH3
CH3
Cl
CH3
Cl
CH3
CH 3CHCH 2CHCCH 3
CH 3CHCHCH 2CCH 3
CH3
Cl
CH3
CH3
Cl CH3
4.28 Halogenation of Alkanes: Section 4.4C
CH3
a) C5H 12
CH3
C
CH3
98
CH3
b) C8H 18
CH3
CH3 CH3
CH3C
CCH3
CH3 CH3
CH3
Chapter 4
light
Br3CCBr 3 + 6 HBr
.. Br light
Br . + CH4
CH 3. + Br2
Initiation
Br
Propagation
2Br.
CH 3. + HBr
CH 3Br + Br.
CH 3CH 2 .+ CH4
Propagation
CH 3. + Cl2
Cl . + CH4
CH 3Cl + Cl .
CH 3 .+ HCl
CH 3CH 2Cl + Cl .
Propagation
Cl . + CH4
CH 3. + Cl2
CH 3. + HCl
CH 3Cl + Cl .
99
Chapter 4
H+
CH 3CH 2CHCH 2CH 3
.. OH
..
.. O
..
..
- H2O..
+ H
1. Protonation
2. Loss of water to
form carbocation
3. Loss of proton to
form alkene
CH 3CH 2CH
CHCH 3
H
CH 3CH 2CHCHCH 3
+
- H+
from
adjacent
carbon
CH2
b) CH3CH 2CH
CH3
d) CH3C
CH3
CCH3
CHCH3
c) CH3CH
CH3
e)
(f) CH2=CH-CH=CH 2
CH3
4.34 Elimination Reactions to Produce Alkynes: Section 4.5A-B
CH3
a) CH3C
b) CH3CC
CH
CH
CH3
4.35 Preparation of Alkenes and Alkynes: Section 4.5A-B
CH3
CH3
a) CH 3CHCH 2CH 2
Reagent
CH3CHCH
CH2
100
X = OH
Reagent = H2SO4
X = Cl, Br, I
Reagent = KOH
CCH3
Chapter 4
The previous equation is the preferred method for preparing the desired product
since having X on the next carbon would give the most substituted product
predominantly.
CH3
b) CH 3CHCHCH 2CH 3
Reagent
CH3
CH3
X
X = OH
Reagent = H2SO4
X = Cl, Br, I
Reagent = KOH
X
c) CH 3CH 2CH 2CH + 2NaNH 2
CH 3CH 2C
CH + 2 NaX + 2 NH3
X
X = Cl, Br, I
The other two possible dihalide starting materials are less desirable as they can
give a diene product or 2-butyne as well as the desired 1-butyne.
NaNH2
CH 3CH 2CH
X
CH 2
CH 3CH 2C
CH + CH 3CH
CH 2
X
CH 3CH 2CCH 3
NaNH2
CH 3CH 2C
CH + CH 3C
CCH 3 + CH 3CH
CH 2
X
4.36 Preparation of Alkenes and Alkynes: Section 4.5A-B
101
Chapter 4
(b) 1,1-dichloropropane can only form propyne upon dehydrohalogenation. 2,2dichloropropane could possibly eliminate in two different directions to give a
diene.
H Cl H
H Cl
CH 3C-CH
CH3C
HC-C-CH
CH
H 2C=C=CH 2
H Cl H
H Cl
(c) Either compound can produce the desired product. The first one can
produce two alkenes whereas the second forms only one, the target compound.
(CH 3)2CCH 2CH 2CH 3
H2SO 4
(CH 3)2C
CHCH 2CH 2
H2O
OH
4.37 Carbocations: Section 4.1D
A carbocation has three bonded groups and is trigonal,
sp2 hybridized, and has 120 o bond angles. The empty
orbital is the unhybridized p-orbital.
..
C
CH 3
+
Al
Cl
102
Cl
Cl
O
CH 3
Cl
CH 3
Al
Cl
CH 3
Chapter 4
Al: The aluminum in the AlCl3 has three bonded groups and is thus trigonal, sp2hybridized and has 120O bond angles. However, in the product the aluminum
has four bonded groups and is tetrahedral, sp3-hybridized, and has 109O bond
angles.
O: In the reactants, the oxygen has two bonded groups and two non-bonding
pairs. In the product, it has three bonded groups and one non-bonding electron
pair. In both cases it has four space-occupying groups and thus is tetrahedral,
sp3-hybridized, and has 109O bond angles.
4.40 Reaction Mechanisms: Section 4.5C
CH 3CHCH 3
H+
CH 3CHCH 3
OH
- H2O
Br
CH 3CHCH 3
OH
CH 3CHCH 3
Br
H
1. Protonation
2. Loss of water to
form carbocation
3. Bromide neutralizes
the carbocation
Chapter 4
1-bromobutane gives the first product 1-butene as it is the only one possible
from simple elimination. 2-bromobutane, you can see, can give the first
product and the next two, the cis and trans forms of 2-butene. 2-butene is the
more stable product and predominates over 1-butene.
104
5
H2C
CH2
Br2
Br
H2C
Br
CH2
Br
HC
Br
Br
2 Br2
CH
HC
CH
Br
Reactions of
Alkenes and Alkynes
CHAPTER SUMMARY
105
Chapter 5
106
Chapter 5
usually regioselective and the rule for predicting the predominant product
is known as Markovnikov's rule.
5.2 Addition Reactions of Alkynes
A. General Reaction Equation for Addition to Alkynes
Alkynes add hydrogen, hydrogen halides, and halogens (chlorine
and bromine). They can add one mole of reagent to produce a double
bond or two moles to form a single bond.
B. Mechanism of Catalytic Hydrogenation
of Alkenes and Alkynes
Hydrogenation of alkenes and alkynes is accomplished in the
presence of a metal catalyst which attracts both the hydrogen and
hydrocarbon to its surface. As a result of the reactants being adsorbed
onto the same surface, the reaction occurs with cis addition.
C. Electrophilic Addition Mechanism for Alkynes
The mechanism of electrophilic addition to alkynes is the same as
with alkenes. Orientation of addition of unsymmetrical reagents to
unsymmetrical alkynes is determined by the stability of the intermediate
carbocation.
D. Addition of Water to Alkynes
Alkynes add water to form aldehydes and ketones.
5.3 Addition Polymers
A polymer is a giant molecule composed of a repeating structural unit
called a monomer. Addition polymers result from the addition of alkene
molecules to one another. The polymerization occurs by cationic, freeradical, and anionic reaction mechanisms. Examples of addition polymers
include polyethylene, polystyrene, PVC, and Teflon.
107
Chapter 5
108
Chapter 5
Chapter 5
B. Ozonolysis
Ozonolysis cleaves the carbon-carbon double bond of an alkene to
form aldehydes and ketones.
5.8 Acidity of Terminal Alkynes
Terminal alkynes have weakly acidic hydrogens that can be abstracted by
strong bases such as sodium amide.
CONNECTIONS 5.4 The Treatment of Atherosclerosis
SOLUTIONS TO PROBLEMS
5.1 Addition and Elimination Reactions
(a) H2C
Br
H2C
CH 2 + KOH
H2C
H2C
CH 2 + HBr
OH
CH 2
H2SO 4
CH 2
CH 2 + H 2O
H2C
H2C
OH
110
Addition
CH 2
Elimination
+ H 2O
H
H2SO 4
H2C
Elimination
+ KBr + H 2O
Br
(b) H2C
CH 2
CH 2
H
Addition
Chapter 5
CHCH3 + H2
b) CH3CH
CHCH3 + Cl2
Pt
CHCH3
Cl
Cl
c) CH3CH
d) CH3CH
CHCH3 + HBr
CH3CH
CHCH3 + H2O
H2SO 4
CHCH3
Br
H
CH3CH
HO
CHCH3
H
(a)
HCl
Cl
CH 2 + HBr
H
CH 3CH 2CH
Br
CH 2
or
H
CH 2
CH 3CH 2CH
H
Br
CH 3CH 2CH
CH 2
Br -
CH 3CH 2CH
Br
H
CH 3CH 2CH
CH 2
H
CH 2
CH 3CH 2CH
H
CH 2
Br -
CH 3CH 2CH
CH 2
Br
111
Chapter 5
CH 3CH
CH 2
CH 3CH
Cl2
CH 2
Cl
(b)
H3C
Br2
Br
CH 3
Cl
CH 3
H3C
Br
(a) CH 3CH
CH 2
Cl
CH 3CH
CH 2
Cl
CH 3CH
Cl
Cl
(b)
CH 2
Cl
Br
H3C
CH 3
CH 3CH
CHCH 3 + H2O
H2SO 4
CH 3CH
OH
(b) CH 3CH
CHCH 3
H+
CH 3CH
CHCH 3
CHCH 3
H
H2O
H
CH 3CH
OH
H
112
CHCH 3
H
- H+
CH 3CH
OH
CHCH 3
H
Chapter 5
5.8 Carbocations
Arranged most to least stable:
CH 3
CH 3
CH 3CCH 3 > CH 3CHCH 2CH 3 > CH 3CHCH 2 and CH3CH 2CH 2CH 2
3O
2O
1O
1O
most stable
5.9 Orientation of Addition
(a)
CH3
H+
CH3CH 2C
+
Cl
CH3CH 2C
CH3
CH3CH 2C
CH2
CH3
Cl H
predominant
product
more stable
3 carbocation
CH2
CH3
CH3CH 2C
H+
CH2
+
CH2
Cl
CH3
CH3CH 2C
H
CH2
Cl
less stable
1 carbocation
(b)
H+
CH3 H2O
- H+
CH3
OH
CH3
predominant
product
more stable
3 carbocation
CH3
H2O
- H+
CH3
H
OH
less stable
2 carbocation
113
Chapter 5
CCH3 +
1Br2
CH3C
CCH3
Br Br
Br
(b) CH3C
CCH3
2Br2
Br
CH3C
CCH3
Br Br
(c) CH3C
CCH3 +
1Cl2
CH3C
CCH3
Cl Cl
H
(d) CH3C
CCH3
Ni
2H2
CH3C
CCH3
CH3CH 2
CH3
C
Pt
+
H3C
114
CH 3
cis
addition
CCH3
2H 2
Pt
H2
H3C
CH 3
Chapter 5
CH
2HBr
CH3CH 2CH2C
H
CH
Br
Reaction Mechanism
.. _
:Br
.. :
H+
CH3CH 2CH2C
CH3CH2CH2C
CH
HBr adds to
triple bond
and then to
Br
the resulting
double bond.
CH3CH2CH2C
In each case
the more stable
Br
carbocation is formed.
H
.. _
:Br
.. :
CH3CH2CH2C
CH
CH
Br H
CH3CH 2CH2C
CH
H+
CH
Br H
CH 3C
CH +
H2O
H2SO 4
CH 3C
HgSO 4
CH 2
CH 3CCH 3
OH
enol
ketone
CH2
.. CH
H .. CH2
CH3
H .. CH2
CH
CH3
CH2
CH+
CH2
.. CH
CH3
CH+ etc. etc.
CH3
.. A -
CH3
H
CH2
CH
CH3
115
Chapter 5
ROOR
Cl
RO.
CH 2
.. C
RO..CH 2
Cl
RO.. CH2
Cl
CH 2
Cl
Cl
Cl
C. CH2
C.
Cl
Cl
Cl
.. C
Cl
Cl
etc. etc.
RO
CH2
OR
Cl
(a)
CH
CH 2
Br
H
1,2 addition
CH 2 CH
CH
CH 2
+ 1HBr
CH 2 CH
CH
CH 2
H
Br
1,4 addition
(b)
Br
+ Br2
Br
Br
+
Br
1,2 addition
116
1,4 addition
Chapter 5
Reaction Mechanism
STEP 1: Electrophile, H+
is attracted to pi-cloud and uses
two pi-electrons to bond. More
stable allylic carbocation results.
CH 2 CH
CH 2 CH
CH 2
H+
CH
+
CH 2
CH 2 CH
+
CH 2
H
Br-
CH
CH 2
Br
CH 2 CH
CH
Br
1,2 addition
(b)
CH
Resonance Forms
CH 2 CH
CH
CH 2
H
1,4 addition
Reaction Mechanism
Br+
Br
Br
Resonance Forms
Br-
Br
+
Br
Br
Br
1,2 addition
1,4 addition
117
Chapter 5
CH 3CH
CHCH 2
CH 3CH
CH
CH 3CHCH
CH 2
+
CH 3CH
(b)
CH 3CH
CHCH 2
CH 3CH
CH
CH
CH 3CHCH
CH 2
CH 2
CH 2
CH 3CH
(c)
CH 2
CH 3CH
CHCH 2
CH 3CH
CH
CH
CH 3CHCH
CH 2
CH 2
CH 2
CH 3CH
CH
CH 2
(d)
CH 3
CH 3
CH 3
5.20 Terpenes
(a) monocyclic monoterpene
118
CH 3
Chapter 5
CH 3CH
KMnO 4
CH 2
CH 3CH
H2O
OH
KMnO 4
(b)
CH 2
OH
H CH
3
H2O
HO
CH 3
OH
5.22 Ozonolysis
Each double bond is cleaved; the carbons become carbon-oxygen double
bonds.
CH3
(a) CH3C=CHCH2CH 3
O3
H2O
O
+
CH 3CCH3
CH 3CH 2CH
Zn
CH 3
CH 3
O3
H2O
O CH 3
O
+
HCH
HC
Zn
O
O
+
HCCH 2CH
c)
O3
H2O
Zn
CH 3CCH 3
5.23 Ozonolysis
Whereever you see a carbon-oxygen double bond, there was originally a
carbon-carbon double bond. Since there are only two carbon-oxygen double
bonds, they must have been involved in the carbon-carbon double bond.
CH 3 CH=CHCH2 CH 3
5.24 Acidity of Terminal Alkynes
CH3CH 2C CH + NaNH 2
CH3CH 2C
CNa + NH3
119
Chapter 5
CH 3
CH 2
(b)
CH 3
CH 3
(e)
CH 3C
Cl
Cl
Br
Br
CH 3CH 2CCH 3
(g) CH 2
(c)
CH 2CH 3
CH 3
CH
CH
CH 2
Cl
Cl
Cl
OH
CH 2CH 3
(h)
OH
CH
Cl
b) CH3CH 2C
CCH3
c) CH3CH 2CH2CH2CH
CH2
Br Br
Cl
Br
(e)
CH 3CH 2CH 2C
CH 2
Br
Br
Br
(a) CH 3CH
CH 2
CH 3CH
CH 2
CH 3CH
Br
The carbocation in this case is actually a bromonium ion.
CH 3
(b)
CH 3C
CHCH 3
H+
CH 3
CH 3C
CHCH 3
H
120
Cl
CH 2
Br
Br
CH 3
CH 3C
CHCH 3
Cl H
CH 3
(c)
Chapter 5
+ CH 3
Br
CH 3
Br
CH 3
(d)
CH 3C
CH 2
CH 3
H+
CH 3C
CH 3
H2O
CH 2
CH 3C
CH 2
+ OH
-H
CH 3
CH 3C
CH 2
OH H
CH 3C
CCH 3
H+
Cl
CH 3C
CCH 3
CH 3C
H
Cl
CH 3C
Cl
CCH 3
Cl
Cl
+
CH 3C
CCH 3
H
CCH 3
Cl
H
H+
CH3CHC
CCH3
(b)
+
CH3
CH3
1H2
1H2
Pd
CH3
CH3CH
C
H
Pd
H
CH3
CH3
H
121
Chapter 5
OH OH
KMnO 4/H2O
H3C
H3C
(a) CH3CH 2C
H2SO 4
H2O HgSO
4
CH 3CH 2CCH3
O
(b) CH3C
CCH3
H2SO 4
H2O HgSO
4
CH 3CH 2CCH3
CH 2
CH
CH 2
H+
CH 3
CH 3
H2C
CH
H2C
CH 2
CH
CH 2
resonance forms
H2 O
- H+
CH 3
H2C
H
CH
OH
1,2 addition
122
CH 3
CH 2
H2C
CH
H
1,4 addition
CH 2
OH
Chapter 5
Cl +
(b)
Cl
Cl
+
resonance forms
The electrophile
attacks one of the
double bonds to
form an allylic
carbocation that
is described by
two resonance
forms. Neutralization forms two
products.
Cl
Cl
Cl
Cl
+
Cl
1,2 addition
1,4 addition
(a) CH3CH
CH CH
. 2
Resonance hybrid
CH3CH CH
(c)
CH 2
..
_
CH
..
O:
..
CH 2
H
CH3
CH2
CH 2
H
CH3
CH3CH
.. _
:O:
..
O:
(b)
CH2
C
H
CH3
CH3
+
+
(d)
O
123
Chapter 5
-. ..
. .O.
.. .
O.
C
... ..O.
. ..O
.. ..O
.O..
2-
O
O
-. ..
.. .O. ..-
.. ..O..C
...
..O. -
CH2
CF2
b)
CH2
CH
Br
KMnO4
CH 3CHCH2
OHOH
(b)
KMnO4
OHOH
5.38 Ozonolysis: Section 5.7B
Each place there is a carbon-carbon double bond it cleaves and each carbon
becomes a carbon-oxygen double bond.
124
a) CH 3CCH3
O
c) CH3C
HCCH2CH2C
CCH2CHCH2CH
Chapter 5
CH3
C
2 HCH
CH
O
O
CH3
b)
CH3
HCH
CH2CH
O
CCH3
O
CH 3CH 2C
(b)
CCH 2CH 3
CH 3 CH 3
CCH 3
CH 3
CH 3
(c)
CH 3C
CH 3
(d)
CH 3
CH 3
NH3
CHCH3
CH3
OH
OH
CH3
d) D = CH3CHCH
c) C = CH 3CHCH2CHCH3
CH2
e) E =
F=
125
Chapter 5
H = CH3CH
CH2
X = Cl, Br, I
X
g) I = CH 3CH
CHCH 3
K =CH 3CH
CHCH 3
J = CH 3CH 2CHCH 3
Br
..
:OH
CH3
CH3
CH2
CH3
+ :..
OH
CH3
..+
-H
OH
CH3
:O :
CH3CH 2C CCH3
1H2
Pt
CH3CH 2
CH3
C C
H
CH3
(b)
1H2
Pt
CH3
CH3CH 2CH
H
CH3
C C
2HBr
126
CH3
Chapter 5
Cl
2HCl
2Cl2
CH 3CH 2CCH2CH 3
Cl
Cl Cl
CH3CH 2C CCH3
Cl Cl
C8H10
4H2
C8H18
hydrogenation product
127
Chapter 5
resonance forms
products
CH 3CH=CH-CH=CH-CHCH2CH 3
CH 3CH=CH-CH=CH-CHCH2CH 3
Br
CH 3CH=CH-CH-CH=CHCH2CH 3
Br CH 3CH=CH-CH-CH=CHCH2CH 3
Br
CH 3CH-CH=CH-CH=CHCH2CH 3
CH 3CH-CH=CH-CH=CHCH2CH 3
Br
+ Br 2
2Br2
128
Chapter 5
HBr
HBr
major
product
3. Make a model of 2-butyne and the product of cis addition of hydrogen.
H2
Pt
129
Chapter 5
Br2
130
6
Aromatic
Compounds
CHAPTER SUMMARY
6.1 Introduction to Aromatic Compounds
Aromatic compounds are compounds that are similar to benzene in
structure and chemical behavior. Benzene, C6 H6 , is a cyclic compound
commonly written as a hexagon with alternating double and single bonds.
131
Chapter 6
Aromatic Compounds
Aromatic Compounds
Chapter 6
Gasoline
Chapter 6
Aromatic Compounds
Aromatic Compounds
Chapter 6
the negative character of the ring and are deactivating groups. The
directing and activating or deactivating effects of substituents must be
taken into account in devising synthesis schemes.
6.5 Oxidation of Alkylbenzenes
Alkyl side chains on benzene can be oxidized to carboxylic acids using
potassium permanganate.
CONNECTIONS 6.3
Herbicides
SOLUTIONS TO PROBLEMS
135
Chapter 6
Aromatic Compounds
Br
a)
Br
Br
b)
Br
,
Br
C 1 0 H 7 Br
C 1 4 H 9 Br
Br
Br
c)
C 1 4 H 9 Br
,
Br
Br ,
Br
136
Aromatic Compounds
Chapter 6
+
CH3
O
CH3
CH3
Cl
a)
CH3
Br
b)
CH3
CH3
CCH3
d)
CH3
e)
CH2CH 3
c)
CH3
CH3
NO2
CH3
CH3
SO3H
(f)
CH3
CH3
Cl 2
FeCl3
H
Cl+
Two-Step
Substitution
Cl+
Cl
+
FeCl4-
Cl
-
FeCl 4
+ HCl + FeCl 3
Br2
FeBr3
H
Two-Step
Substitution
Br+
Br+
Br
+
FeBr4-
Br
FeBr4-
+ HBr + FeBr3
137
Chapter 6
Generation
of the
Electrophile
Aromatic Compounds
O
O
CH 3CCl + AlCl 3
O
Two-step
Substitution
CH 3C+
+ AlCl 4-
CH 3C
O
CCH 3
+
AlCl 4
CCH 3
+ HCl + AlCl3
(b) Alkylation
Generation
of the
Electrophile
Two-step
Substitution
CH 3CH 2+
CH 2CH 3
CH 2CH 3
+
AlCl
4
+ HCl + AlCl3
CH3
CH3
NO2+
Two-step
Substitution
HSO 4
+
CH3
NO2
+ H2SO 4
NO2
CH3
CH3
CH3
SO 3H+
Two-step
Substitution
CH3
-
HSO 4
+
CH3
138
CH3
HSO4- + H2O
CH3
SO3H
+ H2SO 4
SO3H
CH3
Aromatic Compounds
Chapter 6
NO2
a)
Br
CH2CH 3
SO3H
CCH3
b)
c)
Cl
NO2
CO2H
d)
Br
CN
NO2
OCH3
H2SO 4
SO3H
Cl 2
FeCl 3
CH3
b)
CH 3Cl
AlCl 3
Cl
CH3
HNO3
H2SO 4
+ ortho isomer
NO2
CO2H
KMnO4
139
Chapter 6
Aromatic Compounds
140
Aromatic Compounds
(c) 9-methylanthracene;
Chapter 6
(d) 9-ethylphenanthrene
CH 3
a)
NO 2
(b)
(c)
O 2N
CH 3
Cl
OH
(d)
NO 2
O
CH 3 OH
CH 3C
(e)
CH 3
CH 3
CH
CH 3
CCH 3
(g)
(f)
CH 3
CH 3
OH
CH 3
Cl
Cl
O 2N
NO 2
(i)
(h)
Cl
Cl
Cl
NO 2
Chapter 6
Aromatic Compounds
(f) 1,2; 1,3; 1,4; 1,5; 1,6; 1,7; 1,8; 1,9; 1,10; 2,3; 2,4; 2,5; 2,6; 2,7;
2,9;
2,10;
3,4;
3,5;
3,6;
3,9;
3,10;
4,5;
4,9;
4,10;
and
9,10 dinitrophenanthrenes
Br
Br
Br
ortho
+6 C
HNO3
H2SO 4
Br
+
NO2
Br
meta
-7 C
Br
Br
HNO3
H2SO 4
Br
NO2
NO2
Br
Br
Br
NO2
Br
para
87 C
Br
HNO3
H2SO 4
Br
two possible
isomers
Br O2N
three
possible
isomers
Br
NO2
only one possible isomer
Br
CH3
b)
a)
CH3
CH2CH 3
CH3
142
Aromatic Compounds
Chapter 6
O
a)
Br
CH3
b)
C(CH2)8CH3
c)
CCH2CH3
Br
SO3H
+
CH3
CH3
SO3H
d)
NO2
+
e)
Br
Br
h)
g)
NO 2
O2N
SO3H
SO3H
Br
CH 2CH 3
CH 3C
CH 3
Br
Cl
j)
Cl
f)
i) CH 3C
Br
Br
CH3
NO2
SO 3H
SO3H
CO2H
CH 2CH 3
CH 3
Br
Br
Br
NO 2
SO 3H
O 2N
k)
Cl
CO 2H
a)
NO2
b)
Br
Br
NO2
c)
Cl
Br
Cl
NO2
Br
d)
SO3H
CH3
Br
e)
OCH3
Br
OCH3
+
Br
143
Chapter 6
Aromatic Compounds
E-A
CH 3
ortho
attack
CH 3
E+
catalyst/reagent
CH 3
E
-H+
E+
CH 3
CH 3
Two-step
Substitution
-H+
+
para
attack
The mechanism is the same for all cases, only the electrophile differs.
Following are the equations for generation of the electrophiles.
a) E+ = Cl+
Cl 2 + FeCl3
O
Cl + + FeCl4-
b) E+ = CH3CH 2C+
c) E+ = CH3CHCH3
+
CH 3CHCH3 + AlCl3
CH 3CHCH3 + AlCl4+
d)
E =
NO2+
+
e) E+ = SO3H
Cl
HNO3 + H2SO 4
NO2+ + HSO4- + H2O
+
2 H2SO 4
SO 3H + HSO4 + H2O
144
Aromatic Compounds
Chapter 6
O
Generation
of the
Electrophile
..
..
CH 3C-Cl :
..
: Cl
.. : ..
Al: Cl
.. .. :
:Cl
.. :
CH3
Two-step
Substitution
CH 3C +
CH3
ortho
attack
..
_
.. : ..
.. : Cl
: Cl
.. : Al
.. :
..: Cl
:Cl
.. :
CH3
C CH 3
- H+
O
C CH 3
CH 3C +
CH3
para
attack
CH3
- H+
+
H
CH 3C
CH 3C
In this reaction, the catalyst is regenerated when hydrogen ion reacts with
the aluminum tetrachloride anion.
AlCl4+
H+
AlCl 3
+
HCl
6.33 Reactions of Aromatic Compounds: Section 6.4
To predict each product, first determine what group will be introduced on the
benzene ring. If one or more groups are already on the ring, determine where
they direct (o,p or m) and bond the incoming group accordingly.
SO3H
a) A =
SO3H
CH2CH 3
B=
b) C =
D=
CH2CH 3
NO2
+
CH2CH 3
Cl
NO2
c) E =
CCH3
CCH3
CCH3
F=
G=
SO3H
Br
SO3H
145
Chapter 6
Aromatic Compounds
SO3H
d) H =
SO3H
SO3H
I=
J=
NO2
Cl
NO2
CO2H
a)
CH3
b)
c) A =
B=
CO2H
CO2H
CO2H
C=
Br
Br2
FeBr3
Br
Cl 2
FeCl 3
Cl
146
Aromatic Compounds
Chapter 6
CH 3CHCH3
b)
+ CH 3CHCH3
AlCl 3
CH 3CHCH3
H2SO 4
Cl
SO3H
SO3H
c)
SO3H
Br2
FeBr3
H2SO 4
NO2
d)
NO2
Cl 2
FeCl 3
HNO3
H2SO 4
Cl
e)
Br
Cl 2
FeCl 3
Cl
Cl
HNO3
H2SO 4
NO2
CH2CH 3
f)
HNO3
H2SO 4
CH 3CH 2Cl
AlCl 3
KMnO4
CH 3Cl
AlCl 3
HNO3
H2SO 4
CH3
h)
Br2
FeBr3
NO2
CO2H
CH3
g)
CH 3Cl
AlCl 3
CH2CH 3
Br
CH2CH 3
CH3
HNO3
H2SO 4
NO2
CO2H
NO2
CO2H
KMnO4
NO2
NO2
Cl 2
FeCl 3
Cl
Cl 2
FeCl 3
Cl
147
Chapter 6
Aromatic Compounds
CH 3
b)
O 2N
+ 3HNO3
CH 3
NO 2
H2SO 4
NO 2
OH
OH
Cl
Cl
c)
FeCl 3
+ 5 Cl2
Cl
Cl
Cl
CH3
d)
+ CH 3CH(CH2)9CH 3
AlCl 3
CH 3(CH 2)9CH
CH3
CH3
CH 3(CH 2)9CH
e)
CH3
H2SO 4
Cl
SO3Na
NaOH CH (CH ) CH
3
2 9
KMnO4
CO2H
SO3H
NaOH
CO2Na
E+
C
+
C
E
Electrophilic
Aromatic
Substitution
148
E
E+
H
+
+ HA
Aromatic Compounds
Chapter 6
Br+ + FeBr4-
Br2 + FeBr3
CH3
Br
-H+
CH3
Two-step
Substitution
CH3
Br
H
+ Br+
CH3
CH3
-H+
+
Br
Br
Br2
Propagation
light
2 Br .
CH 3 + Br .
CH 2. + HBr
CH 2. + Br2
CH 2Br + Br .
CH(CH 3)2
+
-H+
CH(CH 3)2
The difference in the three procedures described is in the way the electrophile
is generated.
149
Chapter 6
Aromatic Compounds
CH 3CHCH 3 + AlCl 4
CH 3CHCH 3+ AlCl3
Cl
CH 3CHCH 3
H2SO 4
CH 3CHCH 3
OH 2
OH
CH 3CH
CH 3CHCH 3+ H O
2
CH 2
H2SO 4
CH 3CHCH 3
a)
b)
NO 2
CH 2
OCH 3
150
Aromatic Compounds
Chapter 6
CH 3CCH 2CHCH 3
CH 2CH 3
CH 2
CH 3
Research
Octane
Number
100
101
91
107
151
Chapter 6
Aromatic Compounds
2. How many different places on a benzene ring can you replace one
hydrogen with a bromine?
3. How many places on a benzene ring can you substitute two bromines for
two hydrogens?
152
7
CO 2H
H
CO 2H
OH
HO
CH 3
CH 3
Stereochemistry
CHAPTER SUMMARY
7.1 Introduction
Isomers are compounds with identical molecular formulas but different
structural formulas. Structural or constitutional isomers differ in the
bonding arrangement of atoms; different atoms are attached to one another in
the isomers. There are three types of structural isomers. Skeletal isomers
differ in their carbon skeletons or chains. In positional isomers, the
difference is in the position of a non-carbon group or multiple bond.
Functional isomers belong to different groups or classes of organic
153
CHAPTER 7
Stereochemistry
154
Stereochemistry
CHAPTER 7
155
CHAPTER 7
Stereochemistry
Stereochemistry
CHAPTER 7
priority is directed away from the observer. The remaining three groups
are in a plane and are visualized from highest to lowest priority. If in
visualizing from the highest priority group to next highest, the eye moves
clockwise, the configuration is R; if the eye moves counterclockwise,
the configuration is S .
B. Determining Group Priorities
Priority depends on the atomic number of atoms directly attached to the
chiral carbon atom. If two or more directly attached atoms are identical,
one proceeds along the groups until differences are found. In double and
triple bonds the groups are considered to be duplicated or triplicated.
C. Determining R and S Configurations
To determine R and S configurations it is necessary to orient the
lowest priority group away from the observer. Using a Fischer projection
for each chiral carbon with the lowest priority group going away from the
observer is a convenient way to do this. To get the lowest priority group
where you want it, you can use the rotation method or the interchange
method (remember interchanges have to be made in pairs to retain the
original configuration).
We have already seen in Chapter 3, Section 3.5B, the configuration of
geometric isomers can be expressed using the E,Z system. If the two
high priority groups are on the same side of the double bond, E is
assigned; if they are on opposite sides, the configuration is Z.
7.7 Resolution of Enantiomers
Since enantiomers have identical physical properties they cannot be
separated by physical means. They can be separated by resolution through
diastereomers. In this method, enantiomers are converted to diastereomers
by reaction with a pure optically active compound. Diastereomers have
different physical properties and can be separated. After separation, the
diastereomers are converted back to the original enantiomers.
157
CHAPTER 7
Stereochemistry
SOLUTIONS TO PROBLEMS
7.1 Chiral Objects
The answers to this question can vary in a few items depending on the type of
item being considered or depending on ones concept of the item. Most are
fairly straightforward, however.
Chiral Objects: a, c, d, f, h, j, k, m, n, o, r, s
7.2 Structural Isomers
Structural Isomers
functional
CH 3
OH
skeletal
positional
158
Stereochemistry
CHAPTER 7
7.3 Isomerism
CH 3
(a) skeletal
CH 3CH 2CH 2CH 2CH 2CH 2OH , CH3CHCH 2CH 2CH 2OH
(b) positional CH 3CH 2CH 2CH 2CH 2CH 2OH, CH3CH 2CH 2CH 2CHCH 3
OH
(c) functional CH 3CH 2CH 2CH 2CH 2CH 2OH, CH3CH 2CH 2CH 2CH 2OCH 3
(d) geometric
H
OH
CH 3
CH 3
OH
(e) conformational
CH 3
OH
H
OH
H3C
CH 2CH 2CH 3
CH 2CH 2CH 3
(a)
CH 3
Cl
CH
(b) 3 H3C
(c) C
H
H
C
H3C
(d) C
CH 2CH 3 H
(e)
CH 3
CHCH 3
C
H
159
CHAPTER 7
Stereochemistry
CH3
CH3CHCHCH2CH 3
CH3
CO 2H
CO 2H
(b)
CH 2NH 2
CH 2NH 2
H3C
NH 2 H2N
CH 2
OH HO
CH 3
CH 2
HO
OH
(c)
CH 3
C
CH 2
OH
OH
CH 3
NH 2 H2N
CH 2
160
Stereochemistry
CHAPTER 7
CO2H
CO2H
CO2H
NH 2
H2N
H2N
OH
HO
OH
CH 3
CH 3
CH 3
A
Enantiomers: AB, CD
CO2H
H
NH 2
HO
CH 3
D
Br
Br
Br
Br
Cl
Cl
Cl
Cl
CH 3
A
CH 3
CH 3
CH 3
Enantiomers: AB, CD
Diastereomers: AC, AD, BC, BD
(b) This molecule can be drawn so that the top and bottom halves are
identically constituted thus allowing for 180 o rotation to test for
superimposability. There is one pair of enantiomers and one meso structure. B
when rotated 180o is superimposable on A, its mirror image. Thus A is a meso
structure. C and D are not superimposable and are enantiomers.
CH 3
CH 3
CH 3
CH 3
Br
Br
Br
Br
Br
Br
Br
Br
CH 3
A
Meso structure: A
CH 3
B
Enantiomers: CD
CH 3
C
CH 3
D
Diastereomers: AC and AD
161
CHAPTER 7
Stereochemistry
Br
Br
Br
Br
Br
Br
Br
A=B; A is a meso
C and D are enantiomers
Diastereomers: AC, AD
(b) There is no symmetry in this molecule and thus rotations to find
superimposable mirror images will be fruitless.
Br
Cl
Cl
Br
Cl
Cl
Br
Br
Enantiomers: AB, CD
162
Stereochemistry
CHAPTER 7
S
2
(b) Group priorities: N higher than the Cs; C with 2Hs and Br higher than C
with 2Hs and C higher than C with the Hs.
2
Interchange
4
1
1 and 4
2 and 3
(c) Group priorities: All Cs, look at what is on the Cs. #1 is a C with three Cs
because of triple bond; #2 is C with two Cs and a H. We have to look at the
second C on the next two because in each case the first C has a C and 2Hs.
#3 has 2Hs and I and #4 has 3 oxygens; the I is of higher atomic number.
Interchange
1
2 and 4
1 and 3
(d) Group priorities: #1 is O. The next three are all Cs. #2 has O on C. #3 has
C and 2H and #4 has 3H. No need to interchange as #4 is back.
163
CHAPTER 7
Stereochemistry
CH 3
C
H
4
2
CH 2CH 2Br BrCH 2CH 2
S
CH 3 1
C
CH 2Cl
H
4
CH 3
CH 3
CH 3
CH 3
CH 3
OH
OH
(b)
H3C
KMnO 4
OH
OH
CH 3
CH 3
OH
OH
164
Stereochemistry
(c)
CHAPTER 7
CH 3
CH 3
CH 3
H2/Ni
H
CH 3
H
H
H3C
CH 3
H
H
(d)
CH 3
CH 3
CH 3
Br2
H
Br
Br
H
Br
H
H
Br
(e)
CH 3
CH 3
CH 3
Br2
H
Br
Br
CH 3
CH 3
Br
CH 3
H
Br
165
CHAPTER 7
Stereochemistry
H3C
CH 3
CH 3
CH 3
CH 3
CH 3
Br
Br
CH 3
CH 3
Br
Br
CH 3
CH 3
CH 3
(b) O
(a)
C HCH 2OH
(c) NaO2CCH 2CH 2
OH
CH
CH 3
HO
OH
CH
NH 2
CH 3
(8)
(4)
CH 3
(d)
(2)
CH 3
(e)
CH 2CHCH 3
NH 2
HO
166
CO 2H
(256)
(2)
Stereochemistry
CHAPTER 7
CO 2H
CH 3
(f)
CH
C
CH 3
(g)
CH
C H NHCCH 2
CH 3
N
(2)
(8)
(h)
CH 2
C H C H C H CH 2
OH
OH
OH
OH
OH
(8)
H3C
O
(b) CH3CH 2CH 2CHCH
H3C
CH
CH
H
CH 3
CH 2CH 2CH 3
CH 2CH
CH 3CH 2CHCH2CH
H3C
CH 2CH 3
CH 3
CH 2CH 2CH 3
CH 3
CH 2CH 3
CH 2CH 3
CH 3
CCH 3
CCH 3
CH 2CH
H
CH 3
CH 2CH 3
167
CHAPTER 7
Stereochemistry
O
CH 3CH-CHCH
H3C
CH
CH
CH 3CH 3
CH 3 Br
CH3CH-CHCH 3
CH 3
CH 2CH 2CH 3
CH 3
Br
Br
CH 2CH 2CH 3
CH 3
H
CH(CH3)2
7.19 Enantiomers
Please see problem 7.18.
7.20 Enantiomers and Diastereomers: Section 7.4
CH 3
CH 3
H
Br
CH 3
Br
H3C
CH 3
CH 2CH 3
Diastereomer
Enantiomers
7.21 Enantiomers: Section 7.2A-B
a)
OH
OH
CH 3CH 2
168
C
H
CH 3
CH 3C
CH 3
CH 2CH 3
CH 3
CH 2Br
Br
CH(CH3)2
CH 2CH 3
Br
CH 2CH 3
b)
CH 3
CH(CH3)2
CH(CH3)2
Br
BrCH 2
CCH3
Stereochemistry
c)
CHAPTER 7
Cl
CH 2 CH
Cl
CH 3
CH 3
CH
CH 2
CH 3
CH 3
CH 3
CH 3
OH
HO
HO
OH
Br
Br
Br
Br
CH 3
CH 3
CH 3
CH 3
Enantiomers: AB, CD
b)
CH 3
CH 3
CH 3
CH 3
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
CH 3
CH 3
B
repeat of A
Enantiomers: CD
Meso: A
CH 3
C
CH 3
D
Diastereomers: AC, AD
169
CHAPTER 7
Stereochemistry
c)
CH 3
CH 3
CH 3
CH 3
OH
HO
HO
OH
HO
OH
CH 2CH 3
CH 2CH 3
CH 2CH 3
A
Enantiomers: AB, CD
d)
CH 3
H
Cl
CH 2
H
Cl
CH 3
Cl
CH 2CH 3
D
CH 3
H
Cl
Cl
CH 3
Meso: A
Cl
CH 2
CH 3
B
repeat of A
Enantiomers: CD
HO
CH 2
CH 3
OH
CH 3
CH 2
Cl
CH 3
Cl
Diastereomers: AC, AD
(a)
Br
Br
Br
Br
Br
Br
Br
Br
170
Stereochemistry
CHAPTER 7
(b)
Cl
Br Br
Cl
Cl
Br Br
Cl
Cl Cl
Cl
Cl
Cl Cl
Cl
CH 3
CH 3
CH 3
CH 3
Br
Br
Br
Br
Br
Br
Br
Br
Cl
Cl
Cl
Cl
CH 3
CH 3
CH 3
CH 3
CH 3
CH 3
CH 3
CH 3
Br
Br
Br
Br
Br
Br
Br
Br
Cl
Cl
Cl
Cl
CH 3
E
CH 3
F
CH 3
CH 3
CHAPTER 7
b)
Stereochemistry
CH 3
CH 3
CH 3
CH 3
Br
Br
Br
Br
Cl
Cl
Cl
Cl
Br
Br
Br
Br
CH 3
CH 3
CH 3
CH 3
B
repeat of A
CH 3
CH 3
CH 3
CH 3
Br
Br
Br
Br
Cl
Cl
Cl
Cl
Br
Br
Br
Br
CH 3
E
CH 3
F
repeat of E
CH 3
CH 3
G
H
same as C and D (G = D, H = C)
Stereochemistry
CHAPTER 7
(b) Group priorities: O highest, H lowest of directly attached atoms. Carbon with
C and 2H higher than carbon with 3H.
3
2
R
1
(c) Group priorities: Directly attached atoms all carbon. #1 is C with 2C,1H
attached; all the others have one C and 2H. Looking at next carbons, #2 has a
Cl; the other two have C and 2H. Looking at next carbons, #3 has a Br.
2
Interchange
4
3
3 and 4
1 and 2
173
CHAPTER 7
Stereochemistry
2
Interchange
1 and 4
2 and 3
(e) Group priorities: H is #4; all other directly attached are carbon. Looking at
the carbons, the highest atomic number attached group is Br and this is #1. The
one with Cl is #2, and the one with three carbons is #3.
S
3
(f) Group priorities: Oxygen is first, the other directly attached atoms are
carbons. The carbon with 3H is #4. The other two differ at the second carbon.
(g) Group priorities: N is the highest atomic number directly attached atom; H is
the lowest. The C with the C and 2H is #2.
174
Stereochemistry
CHAPTER 7
3
Interchange
4
R
3
1 and 4
2 and 3
4
(h) Group priorities: Of directly attached atoms, Cl has highest atomic number
followed by O, followed by C, followed by H.
1
Interchange
4
R
1
2 and 4
1 and 3
4
Br > H
and
CH=CHBr > H
CHAPTER 7
Stereochemistry
configuration, but keep the hydrogens back. Note that in each case the other
chiral carbon happens to be the second priority group. Since the low priority
groups are behind the plane we can read the configuration directly.
2S, 3R 2-bromo-3-chloropentane
Interchange
CH 3
H C
Br
H C Cl
3 and 4
Interchange
CH 2CH 3
3 and 4
3
Interchange
3
1 and 3
Interchange
1 and 3
CH 2CH 2CH 3
(a)
CH 3
CH 2CH 3
C
Cl
(b)
S
CH 2CH 3
CH 3
H
(c)
BrCH 2
176
H
(d)
CH 2CH 3
C
CH 3
CH 2CH 3
CH 3CH
CH 3
C
H
CH 3
Stereochemistry
CHAPTER 7
1st
interchange
HO
OH
H
H
H
CO2H
2nd
interchange
OH
OH
CH 3CH 2
CO2H 2
CH 3CH 2
H2
CH 3
CH 3
H
CH 3
Ni
CH 3
CH 2
CH 3
CH 3
CH 3
The second compound already has a chiral carbon atom. When the new one is
generated, a pair of diastereomers is formed in unequal amounts. An
examination of the diastereomers compared to the enantiomers can explain the
production of enantiomers in equal amounts and diastereomers in unequal
amounts. In one diastereomer, the newly generated methyl is on the same side
of the ring as the existing methyl, a less stable cis arrangement.. The two larger
groups are on opposite sides in the other, a more stable trans arrangement. The
products are of unequal stability and it is understandable they are formed in
177
CHAPTER 7
Stereochemistry
unequal amounts. The enantiomers are of equal stability and formed in equal
amounts. Identical paths of reaction in the first reaction and different ones in the
second also support the difference in product ratio.
CH 3
CH 3
CH 3
H2
CH 3
Ni
H
CH 2
CH 3
(b)
CH 2CH 3
CH
CH 3
CH 3
CH 2CH 3
OH
HO
CH 3
CH 2CH 3
(c)
CO 2H
(d)
CO 2H
CH 3
CH 3
Cl
Cl
Br
Br
Cl
Cl
Br
Br
Br
Br
CH 3
CH 3
CH 3
(e)
CH 3
CH 3
CH 3
Br
Br
Br
Br
Br
Br
Br
Br
CH 3
CH 3
178
Stereochemistry
CHAPTER 7
(a) Enantiomers
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
CH
CH 2OH
HO
OH
OH
OH
CH2OH
HO
H2
cat.
H
H
CH 2OH
CH
HO
OH
OH
OH
OH
OH
HO
CH 2OH
CH2OH
HO
H2
OH
cat.
OH
HO
CH 2OH
179
CHAPTER 7
Stereochemistry
This is
2-bromo-3-chlorobutane
CH 3
CH 3
Cl
CH 3
C-3
Br
CH 3
C-2
H
Now look up the C2-C 3
bond of the eclipsed
Fischer projection and
translated it to a
Newman projection.
Br Cl
CH 3
CH 3
C 2 in front
C 3 behind
HH
(b)
Cl
Cl
H3C
7.37 Stereoisomers:
CH 3 H
S, cis
Br
CH 3
S, trans
Br
C
H
180
C
H
H CH 3
CH 3
CH 3
CH 3
Br
H
C
R, cis
CH 3
CH 3
C
H
R, trans
Br
Stereochemistry
CHAPTER 7
2R, 3R
2S, 3S
2S, 3R
2R, 3S
CH 3
CH 3CH 2
Si
CH 2CH 2CH 3
Cl
H
a)
Cl
CH 2
C
CH 2
Cl
C
CH 2
CH 2
Cl
CH 2
C
CH 2
H
C
CH 2
Cl
The middle carbon is common to both rings. Since it is tetrahedral, one ring will
be in the plane of the paper and other perpendicular (in and out of the paper).
The H and Cl on the ring in and out of the paper are above and below the ring
and thus in the plane of the paper. Those on the other ring are in front of and
behind the paper plane. One cannot superimpose both rings and the Cls (or
Hs) simultaneously.
181
CHAPTER 7
Stereochemistry
Cl
H
b)
Cl
Cl
H
C
Cl
Since the middle carbon is involved in both double bonds, it has two p-orbitals
which are perpendicular (90) to each other. Thus the two pi-bonds are in
perpendicular planes. Consequently, the Hs and Cls on each end are in
perpendicular planes. No amount of rotating or turning the molecules will allow
the simultaneous superimposition of both chlorines.
182
Organic
Halogen Compounds
CHAPTER SUMMARY
8.1 Introduction
Although organic halogen compounds are rarely found in nature, they do
have a variety of commercial applications including use as insecticides,
herbicides, dry-cleaning agents and degreasers, aerosol propellants and
refrigerants, and important polymers.
8.2 Structure, Nomenclature, and Physical Properties
A. Structure and Properties
Alkyl halides are organic halogen compounds in which one or
more hydrogens of a hydrocarbon have been replaced with a halogen.
These compounds can be classified as primary, secondary, or tertiary
depending on whether there are one, two, or three carbons respectively
connected to the carbon bearing the halogen.
183
Chapter 8
attached to a benzene ring. If the halogen is directly attached to a carboncarbon double bond, it is termed vinyl, and if it is attached to a carbon
directly attached to the double bond it is allylic.
Alkyl halides are generally water insoluble and have a greater
density than water. Their boiling points increase with molecular
weight; alkyl iodides have higher boiling points than the corresponding
alkyl bromides which boil at higher temperatures than the chlorides
B. IUPAC Nomenclature
IUPAC nomenclature involves using the prefixes fluoro, chloro,
bromo, and iodo to designate halogen in a molecule.
C. Common Nomenclature
A salt-type nomenclature is frequently used with alkyl halides in
which the alkyl groups name precedes the name of the halide.
In
Drug Design
A. General Reaction
A characteristic reaction of alkyl halides is nucleophilic
substitution. In this reaction, a nucleophile (Lewis base) replaces a
halide ion, the leaving group . Chloride, bromide, and iodide are
184
Chapter 8
185
Chapter 8
Chapter 8
187
Chapter 8
SOLUTIONS TO PROBLEMS
8.1 Nomenclature
(a) 2-chloropentane;
(b) 1,4-dibromo-2-butene;
(c) p-difluorobenzene;
(d) 1,1,1-trichloro-2,2-difluoroethane
8.2 Nomenclature
(a) CBr4 ; b) CH 2 Br2 ; (c) CHI3 ;
CH 2Cl ;
e) O2N
(d) CH 2 =CHBr;
f) CH 3CHCH3
I
g) CH3N(CH3)2 ;
h) CH3CN ;
i) CH 3C
CCH3
NaCN
+
NaOH
NaSCH3
NaBr
CH3SCH 3
NaCl
NaI
(c)
OCH3
CH 3CHCH2CH 3
N(CH3)2
S N 2 Mechanism
CH 3
CH 3
HO
Br
HO
Br
H H
HO
Transition state
Br
C
H
188
CH 3
H
Chapter 8
(b) 4x
(c) 6x
H
CH 3CH 2CH 2
CH3S
Cl
Pure enantiomer;
optically active.
C
H
CH 3
Cl
CH3S
Cl
H
CH2CH 2CH 3
CH2CH 2CH 3
Transition state
showing nucleophile
attacking from opposite
side of leaving bromide
Pure enantiomer;
optically active;
inverted mirror image
configuration
(a)
S
H3C
CH(CH 3)2
C
R
+
NaOH
HO
H
S
(b)
Br
CH 3
CH 2CH 3
C
CH(CH 3)2
R CH 2CH 3
+
NaOCH 3
CH 3
OCH 3
CH 3
CH 3
CH 3CCH2CH 3
Cl
CH 3CH 2OH
CH 3CCH2CH 3
HCl
OCH2CH 3
189
Chapter 8
8.13 S N 1 Mechanism
CH 3
CH 3
CH 3CCH 2CH 3
CH 3CH 2OH
CH 3CCH 2CH 3
+
Cl
CH 3
CH 3
- H+
CH 3CCH 2CH 3
CH 3CCH 2CH 3
OCH 2CH 3
H +
OCH 2CH 3
(d) 3x
CH 3CH 2CH 2
C
H3C
CH 3CH 2
Cl
-H
C+
Cl
H3C CH 2CH 3
Pure enantiomer;
optically active.
Nucleophile attacks
planar carbocation
equally from either side
O
H
CH 3CH 2CH 2
CH 3CH 2O
CH 2CH 3
CH 3CH 2CH 2
+
CH 3
CH 2CH 3
H3C
CH 3CH 2
OCH 2CH 3
190
Chapter 8
(b) S N2 Mechanism
CH 2CH 2CH 3
CH 3CH 2CH 2
CH 3CH 2O
CH 3CH 2O
H
CH 3CH 2
CH 3CH 2CH 2
Cl
Cl
C
CH 3
CH 2CH 3
transition state
Pure enantiomer;
optically active.
Pure enantiomer;
inversion of configuration
(a)
R
H3C
CH(CH 3)2
C
R
+
H2O
H3C
CH 2CH 3
R
(b)
Br
HO C
OH
CH 2CH 3
CH 2CH 3
C
CH(CH 3)2
R
+
CH3OH
CH 3
CH 2CH 3
CH 2CH 3
CH 3O
CH(CH 3)2
CH 2CH 3
OCH 3
CH3CHCHCH3
Br
1o halide
SN2
Br
2o halide
SN2
SN1
CH3
CH3CCH2CH3
Br
CH3
CH2CHCH2CH3
Br
3o halide
1o halide
SN1
SN2
191
Chapter 8
CH 3CHCH 3
Br
CH 3C
E1
H
C H
H
CH 3CHCH 3
+
CH 3C
OH
-H +
H
CH + H 2O + Br
H
CH 3CH
CH 2
192
Chapter 8
CH 3
CH 3CH 2
Br
E2
H
CH 3CH 2
CH 3CH 2
anti
elimination
CH 3
C
H
3S, 4R
cis
(b) Interchanging two groups on the other carbon gives the mirror image
configuration.
H3C
CH 2CH 3
Br
H
CH 3CH 2
H3C
E2
C
H
3S, 4S
CH 3CH 2
anti
elimination
CH 2CH 3
CH 2CH 3
CH 2CH 3
trans
H3C
E2
anti
elimination
H
C
CH 2CH 3
CH 2CH 3
3R, 4S
cis
193
Chapter 8
Br
CH 3
anti
elimination
H
CH 2CH 3
CH 3
C
CH 2CH 3
C
CH 2CH 3
CH 3CH 2
Br H
syn
elimination
CH 2CH 3
C
CH 3CH 2 H
C
CH 3
CH 3CH 2
CH CH 3
CH 32
CH 3
CH 3CHOCH 2CH 3
NaBr
Cl
e)
C
Cl
Br
Cl
Cl
C
CH 2
d) CCl 4
Cl
Cl
Cl
C
Cl
c) CH 2
f) CF2Cl 2
Cl
194
Chapter 8
b)
c) CH3CH 2SH
CH 2CN
OH
d) CH 3CH 2CH 2NCH 3
CH 3
g)
CH 2CH 2C
e) CH 3
f) CH 3
CH 3CHOCH 2CH 3
CH 3CHCH 2SCH 3
CCH 3
h) CH3NH 2
CH 3
CH 3
CH 2NCH 3
OCH 3
8.34 Williamson Synthesis of Ethers: Sections 8.4A and 8.6
T he halogen can be Cl, Br, or I.
(a) CH3CH 2CH 2ONa + CH3CH 2Cl
(b) CH 3
CH 3CHONa
+ CH 3CH 2Cl
a) HC
CH
NaNH2
HC
CNa
CH 3CH 2Br
HC
CCH 2CH 3
195
Chapter 8
b) HC
CH
CH 3C
c) HC
CH
NaNH2
HC
CNa
CH 3CH 2Cl
CCH 2CH 3
HC
CCH 2CH 3
NaNH2
CH 3I
NaC
CCH 2CH 3
CH 2Br
HC
CNa
HC
CCH 2
S N2
Rate Expression
Rate = k(RX)
Rate = k(RX)(Nu)
Reaction Intermediate
Carbocation (two
steps)
Racemization:
inversion and
retention.
3 O > 2O > 1O
1 O > 2O > 3O
Effect of Increasing
Nucleophile
Concentration
Reaction rate is
increased
Effect of Increasing
Alkyl Halide
Concentration
Reaction rate is
increased
Reaction rate is
increased
Stereochemistry
196
Inversion of
configuration
Chapter 8
Increases rate of
reaction and
likelihood of S N1
Effect of Non-Polar
Solvent
Favors S N1 as
crowding decreased
in carbocation
Disfavors S N2 as
transition state is
more crowded
(pentavalent)
Strength of the
Nucleophile
Disfavors S N1
Favors S N2
S N2
CH 3
_
HO
HO
Br
Br
HO
Br
CH 3
Br
C+
Br
H
Transition state
showing nucleophile
attacking from opposite
side of leaving bromide
Pure enantiomer;
optically active.
S N1 CH 3
CH 3
Pure enantiomer:
optically active;
mirror image
configuration
CH 3
-H
HO
CH 3
+
C
H
OH
H
Pure enantiomer;
optically active.
O
H
H
Nucleophile attacks
planar carbocation
equally from either side
CH 3C
CHCH 2CH 3
197
Chapter 8
CH 3
Br
CH 3
OH
CH 3CCHCH 2CH 3
+
Br
CH 3C
CHCH 2CH 3
E2
OH
CH 3
CH 3
CH 3C
H
CHCH2CH 3
CH 3
Br
Br
CH 3C
CHCH 2CH 3
CH 3 + CH 3SH
CH 2CH 2CH 3
CH 3
C
H
198
SCH 3 + CH 3S
CH 2CH 3
b) CH 3
Cl + NaNH 2
C
H
C
H
CH 2CH 3
H2N
CH 2CH 2CH 3
CH 3
CH 3
Chapter 8
CH(CH 3)2
c) CH 3
CH(CH 3)2
+ NaOCH 2CH 3
CH 3CH 2O
(CH 2)3CH 3
d) Cl
CH 3
(CH 2)3CH 3
CH 2CH 3 + H 2O
HO
CH 3
(CH 2)3CH 3
CH 2CH 3 + CH 3CH 2
CH 3
OH
CH 3
(a)
H3CO
(b)
CH2CH(CH3)2
CH3
CN
CH 3
CH 3
C
E1
CH 3
CH 3
C
CH 3
C
CH 3
Chapter 8
Cl
3S
Cl
CH3
CH3
H3C
CH3
Cl
2R
CH3
H CH3
Cl
CH 3
anti
elimination
H3C
CH 3
C
CH 3
H
Cl H
syn
elimination
H3C
C
H3C
C
CH 3
CH 3
H3C
H3C
C
H3C
H
200
CH 3
C
Chapter 8
Cl
anti
elimination
H3C
H3C
C
CH 3
2R, 3R
CH 3
Cl
anti
elimination
2S, 3S
CH 3
H3C
C
H3C
CH 3
H
Cl
CH 3
H
Cl
CH 3
H
H
CH 3
CH 3
H
H
E 2 reactions proceed by
anti elimination. The only
anti possibility is shown
and it does not give the
most stable product (Saytzeff).
E 1 reactions proceed
by syn or anti elimination. The syn shown
gives the most stable
alkene (Saytzeff).
201
Chapter 8
NaOCH 2CH 3
S N2
CH 3 Br
CH 3 H
OCH 2CH 3
S N1
CH 3 H
CH 3 OCH 2CH 3
CH 3CH 2OH
H
OCH 2CH 3
8.48 E 2 Elimination
(a) The chair shown has two possibilities for anti elimination.
substituted Saytzeff Rule product predominates as it is more stable.
The more
Br
H
CH 3
CH 3
CH 3
H
predominant
product
(b) The chair shown here has only one possibility for anti elimination and that
product forms exclusively despite the fact that it is not the most substituted.
You may notice that both groups are axial. Actually the diequatorial conformer
is more stable and preferred but E2 elimination occurs only on the small amount
that exist at any one time in the diaxial conformation.
Br
H
H
H
H
202
CH 3
CH 3
Chapter 8
C H3C H C H2Cl
These are both primary halides and because they do not form stable
carbocations and because they are relatively unhindered sterically, they react
by S N2.
C H3
C H3C C H3
Cl
C H3C H C H2C H3
Cl
CH 3CCH 2CH 3
least
Br
most
203
Chapter 8
204
9
OH
CH3OCH3
CH3CH2OH
205
Chapter 9
Chapter 9
B. Polyhydric Alcohols
Ethylene glycol is antifreeze and glycerol is a humectant.
Glycerol can be converted into the explosive nitroglycerin.
C. Diethyl Ether
Diethyl ether is an important solvent and was once widely used as
a general anesthetic.
D. Phenols
Phenol and many of its derivatives are used in over-the-counter
medications as disinfectants and local anesthetics. They are also used as
antioxidants, preservatives and photographic developers.
CONNECTIONS 9.2 Neurotransmitters - The Heart of the Matter
9.4 Preparations of Alcohols and Ethers
A. Hydration of Alkenes
B. Nucleophilic Substitution
C. Reduction of Aldehydes and Ketones
9.5 Reaction Sites in Alcohols, Phenols, and Ethers
The reaction sites in alcohols, phenols, and ethers are the polar bonds
(carbon-oxygen and oxygen-hydrogen) and the lone pairs of electrons on
the oxygen. The unshared electron-pairs on alcohols and ethers make these
compounds Lewis bases. Oxoniums ions, in which the oxygen has three
bonds and is positive, result from the protonation of alcohols and ethers. Most
reactions of alcohols involve the O-H bond, C-O bond, or both.
9.6 Reactions Involving the O-H Bond of Alcohols and Phenols
A. Relative Acidities of Alcohols and Phenols
207
Chapter 9
The polar O-H bond of alcohols makes them weak acids. By the
Bronsted-Lowry definition, acids are hydrogen ion donors and bases
are hydrogen ion acceptors in chemical reactions. Strong acids are
100% ionized in water and weak acids are only partially ionized. Weak
acids establish an equilibrium in water between their ionized and unionized forms. This equilibrium and the strength of an acid is described by
the acidity constant, K a . Ka is defined as the concentrations of the
ionized forms of the acids (H3O+ and A -) divided by the un-ionized form
(HA). The stronger the acid, the greater will be the value of the acidity
constant. Acid strengths are also expressed by pK a , which is defined as
the negative logarithm of Ka. Numerically smaller pK a's signify stronger
acids and larger pKa's, weaker acids. Approximate pKa's include 50 for
alkanes, 25 for terminal alkynes, 16 for alcohols, 10 for phenols, 5 for
carboxylic acids, and -2 or so for strong inorganic acids.
The ion or molecule formed by the loss of a proton from an acid is the
conjugate base. Strong acids form weak conjugate bases and weak
acids form strong conjugate bases.
Phenols are one million to one billion times more acidic than alcohols
and this is the characteristic property that distinguishes them. Phenols will
react with the base sodium hydroxide but alcohols will not. The acidity of
phenols is explained by resonance stabilization of the phenoxide
ion; the negative charge is dispersed throughout the benzene ring as
opposed to being concentrated on the oxygen as it is in the alkoxide ion.
Electron-withdrawing groups on the benzene ring increase the
acidity of phenols.
B. Reactions of Alcohols with Sodium Metal:
Reaction of the O-H Bond
Although alcohols will not react with sodium hydroxide as do phenols,
they will react with sodium metal to form alkoxide ions and hydrogen gas.
C. Formation of Esters: Reaction of the O-H Bond
Alcohols will also react with organic and inorganic acids to form
esters.
CONNECTIONS 9.3 Insecticides and Nerve Gases
208
Chapter 9
Chapter 9
Chapter 9
SOLUTIONS TO PROBLEMS
9.1 Primary, Secondary, and Tertiary Alcohols
CH 3
(a-b)
CH 3CH 2CH 2CH 2OH
1O
1-butanol
CH 3CH 2CHCH 3
2O
2-butanol
CH 3CHCH 2OH
OH
1O
CH 3
CH 3CCH 3
3O
OH
2-methyl-1-propanol 2-methyl-2-propanol
211
Chapter 9
O
H
CH 2 CH 2
CH 2 CH 2
H
HO
212
O
H
O
CH 2CH 2
H
O
H
Chapter 9
..O
..
+
CH
CH2
+
H
non-bonding electrons
Lewis base site
multiple
bond
CH 2
..
CHOH
..
CH 2
H
.. +
CHOH
..
HCl
acid
H+
CH 3OH
conjugate
acid
Cl-
conjugate
base
Chapter 9
NaO
+ NaOH
+ H2O
+ HCl
OH
Cl
HBr
(c) CH3CH(CH2)2CH 3
HCl
CH3CH(CH2)2CH 3
OH
H2O
+
H2O
Cl
CH3
CH 3CHCH2CH 2
CH 3CHCHCH 3
OH
0
1 Alcohol one
hour with heat
214
CH3
CH 3CCH 2CH 3
OH
OH
o
2 Alcohol
3 Alcohol
5-15 minutes
instantaneous
CH3
CH 2CHCH2CH 3
OH
0
1 Alcohol one
hour with heat
Chapter 9
S N 2 Mechanism:
H+
..
OH
..
..
: Cl
..
H
+ ..
C OH
..
C
H
H
CH3CH 2
..H
OH
..
..
: Cl
..
CH2CH 3
H
C
H
CH2CH 3
Transition state
showing bromide displacing
water molecule from the opposite
side to form final product.
(b)
CH3
C
H
H+
S N 1 Mechanism:
A Two-Step Process
CH3
C
H
..
OH
..
CH3
..H + - H2O
OH
..
C+
Br
Br
CH 3CH 2OH
CH3
CH3
Br
Pure enantiomer;
optically active
alcohol is
protonated to
optically active
oxonium ion.
Br
PBr3
CH3CH 2Cl
SO 2
CH3CH 2Br
P(OH)3
HCl
215
Chapter 9
can be converted to
CH3
+
HBr
CH3CBr
CH3
CH3OH
CH3
CH 3
CH 3COCH 3
CH 3
+
2HBr
CH3CBr
CH 3
+ CH3Br + H2O
CH 3
..
CH 3COCH
.. 3
S N1 Mechanism:
A two-step process
CH 3
CH 3
..
CH 3COCH
.. 3
H+
CH 3
oxonium ion
216
..
-CH 3..
OH
CH 3
..
: Br
..:
CH 3
..
CH 3C +
CH 3CBr
..:
CH 3
CH 3
carbocation
H
C
Chapter 9
S N 2 Mechanism:
H+
..
OH
..
H
H
H
+H
..
C OH
..
..
: Br
..
C
H
..H
OH
..
..
: Br
..
C
H
H
Primary alcohol protonated
to form primary oxonium ion.
Oxonium ion is attacked by
bromide.
Transition state
showing bromide displacing
water molecule from the opposite
side to form the final product.
+ HI
O
+ HI
H2O
CH 3CHCH 3
OH
OH
-H
- H2O
CH 3CH-CH 2
CH 3CH
CH 2
217
Chapter 9
S N1
H+
Br
- H2O
CH 3CHCH 3
CH 3CHCH 3
OH
OH
CH 3CHCH 3
CH 3CHCH 3
Br
S N1
H+
CH 3CHCH 3
Br
- CH3OH
CH 3CHCH 3
CH 3CHCH 3
OCH 3
CH 3CHCH 3
Br
OCH 3
H
H2SO 4
CH3CH
CH2
H2O
OH
CH3
(b) CH3CCH2CH 3
H2SO 4
CH3
CH3C
CHCH3
H2O
OH
CH3
(c) CH3CHCHCH2CH 3
OH
218
CH3
H2SO 4
CH3CH
CCH2CH3
H2O
Chapter 9
CH 3CH 2CHCH 3
CH 3
CH3CHCH 2OH
CH 3CCH 3
OH
OH
CrO3
CH 3
CH 3CH 2CH 2CO 2H
CH3CH 2CCH 3
CH3CHCO 2H
No Reaction
O
9.29 Oxidation of Alcohols
OH
and CrO 3
(a)
CH2OH
CH2OH
(b)
and CrO 3
(c)
and PCC
OH Br
(c)
CH 3CH -CHCH3
OH OH
OH OCH2CH3
1-pentanol
CH3
3-methyl-1-butanol 2
CH 3CH 2CHCH2CH 3
2o
2-pentanol
CH3
CH 3CHCH2CH 2OH
o
OH
CH 3CHCHCH3
o
3-pentanol
CH3
CH 3CCH2CH 3
OH
3-methyl-2-butanol 3 o
OH
2-methyl-2-butanol
219
Chapter 9
CH3
CH3
HOCH 2CHCH2CH 3
CH 3CCH2OH
CH3
2-methyl-1-butanol
2,2-dimethyl-1-propanol
(d-e) Ethers
CH3
CH 3OCH2CH 2CH 2CH 3
1-methoxybutane
CH 3OCHCH2CH 3
2-methoxybutane
CH 3OCH2CHCH3
1-methoxy-2methylpropane
CH3
CH3
CH 3OCCH 3
CH3
CH3
2-methoxy-2-methylpropane 1-ethoxypropane
CH 3CH 2OCHCH3
2-ethoxypropane
220
Chapter 9
b) CH 3CCH2OH
OCH3
c) CH 3CH 2OCHCH3
CH3
OH
d)
CH3
e) CH2
CHCH2OH
f)
OCH
CH2
a)
SH
OH
OH
OH
OH
e)
CH2CH 3
f)
OCH3
CH 3CHCH3
g) CH 3CH 2CHCH2OH
OCH3
Chapter 9
O
N
H
N
OH
HO
CH 2OH
HO
Sucrose has 12 carbons; there are OH groups on eight of them. This allows for
tremendous hydrogen bonding with water and thus high water solubility.
9.43 Water Solubility: Section 9.2
(a) hexanol < pentanol < ethanol: increasing ratio of OH to hydrocarbon
as boiling points increase.
(b) pentane < heptanol < propanol: pentane has no OH and cannot
hydrogen bond to water; propanol has a higher ratio of OH to hydrocarbon than
heptanol, is more like water and more water soluble.
(c) hexane < hexanol < 1,2-ethanediol: hexane has no OH and no
hydrogen bonding; hexanol can hydrogen bond with water but has only one
OH for all six carbons and has only slight water solubility; ethanediol has an
OH on each carbon and is infinitely soluble in water.
222
Chapter 9
(d) pentane < ethoxyethane < butanol: these compounds have similar
molecular weights but the first two have no OH and thus no hydrogen bonding;
the second is polar and has some slight water solubility and butanol has an OH
and thus can hydrogen bond with water.
9.44 Acidity: Section 9.6A
(a) No: the conjugate acid and base are stronger than the original acid and
base
(b) Yes: the original acid and base are stronger than the conjugate forms
(c) Yes; (d) Yes; (e) Yes; (f) No; (g) Yes; (h) No
9.45 Acid Base Neutralization: Section 9.6A
Acid
Base
CH3CO2Na
(c)
H2SO 4
2 NaOH
(d)
CH3OH
(e) CH3CO2H
(g)
OH
Conjugate Base
CH3CH 2SO 3Na
Conjugate Acid
+
CH3CO2H
Na2SO 4
2 H2O
CH3Na
CH3ONa
CH4
CH3ONa
CH3CO2Na
CH3OH
CH3ONa
ONa
CH3OH
10 -5
5
(IV) H3C
OH
10 -11
11
Chapter 9
(c) II < IV < I < III: The methyl group decreases acidity and thus IV is more
acidic than II. The nitro group increases acidity and III has more of them than
does I.
9.48 Acidity of Phenols: Section 9.6A.2
(a)
CH 3
OH
+ NaOH
CH 3
ONa
NO 2
NO 2
(b)
+ H2O
OH
NaOH
ONa
H2O
II
III
CH3
CH 3CHCH2CH 3
CH 3CCH3
OH
OH
CH3
a)
Na
CH 3CCH3
ONa
CH3
b)
H2SO 4
CH3CH 2CH
CH2
CH3CH
CHCH3
CH3C
CH2
CH3
c)
HCl/ZnCl 2
CH 3CHCH2CH 3
Cl
d)
CrO3/H+
CH 3CCH2CH 3
O
e)
HNO3
CH 3CHCH2CH 3
ONO2
224
CH 3CCH3
Cl
No Reaction
CH3
CH 3CCH3
ONO2
Chapter 9
Br
Cl
CH 3
(b) CH 3CCHCH 3
O
(c) CH3(CH 2)10CH
O
9.52 Reactions of Ethers: Section 9.7C
CH 3
(a) CH3Br + BrCH2CHCH 3
CH 3
(c) CH3CHI + CH3CH 2I
225
Chapter 9
H
+ ..
C OH
..
H
CH3CH 2
226
S N 2 Mechanism:
H+
..
OH
..
..
: Br
..
C
H
..H
OH
..
CH2CH 3
..
: Br
..
H
C
Transition state
showing bromide displacing
water molecule from the opposite
side to form final product.
H
CH2CH 3
..
OH
..
Chapter 9
H+
S N1 Mechanism:
A Two-Step Process
CH 3
..H + - H 2O
OH
..
C+
H
CH 3
Br
Br
H
CH 3
CH 3
Br
CH 3
Br
H
H3C
(identical structures)
(c)
H
S N 2 Mechanism:
.. H+
OCH
.. 3
C
H
CH3CH 2CH2
H
+ ..
C OCH
.. 3
..
: Cl
..
C
H
H
CH3CH 2CH2
..H
OCH
.. 3
CH2CH 2CH3
..
: Cl
..
H
CH2CH 2CH3
FOLLOWED BY
H
H
S N 2 Mechanism:
H+
..
OH
..
H
H
H
H
+ ..
C OH
..
..
: Cl
..
C
H
..H
OH
..
..
: Cl
..
H
C
H
227
Chapter 9
(d) CH 3
C
H
CH 3CH 2
CH 3
C
H
CH 3CH 2
..
H+
S N1 Mechanism:
OCH
.. 3
A Two-Step Process
CH 3
H
+
CH
OH
3
..
OCH
C+
.. 3
H
Cl
Cl
C Cl
H
CH 3CH 2
H
CH 2CH 3
CH 2CH 3
Cl
CH 3
CH 3
(enantiomers)
FOLLOWED BY
H
H
S N 2 Mechanism:
H+
..
OH
..
H
H
H
H
+ ..
C OH
..
228
..
: Cl
..
C
H
..H
OH
..
..
: Cl
..
H
C
H
Chapter 9
(a)
CH 3
..
OH
..
C
CH 3CH 2
CH 3CH 2CH 2
CH 3
C
CH 3CH 2
CH 3CH 2CH 2
C
H
CH 3CH 2
CH 3
C
H
CH 3CH 2
S N1 Mechanism:
A Two-Step Process
..H + - H 2O
OH
..
CH 3
Cl
C+
..
OCH 3
..
Cl
+
C
CH 2CH 3 CH 3CH 2
CH 2CH 2CH 3 CH 3CH 2CH 2
Cl
Cl
H+
S N1 Mechanism:
A Two-Step Process
CH 3
H
+
CH
O
H
3
..
OCH 3
C+
Br
..
Pure enantiomer;
optically active
alcohol is
protonated to
optically active
oxonium ion.
CH 3
CH 3
Pure enantiomer;
optically active
alcohol is
protonated to
optically active
oxonium ion.
(b) CH 3
H+
CH 2CH 3
Br -
CH 3
Br
CH 3
+
C
H
H
CH 2CH 3 CH 3CH 2
Br
229
Chapter 9
- H2O
H CH3
H CH3
C C CH3 CH3
C C CH3
H OH
H OH
H+
Step 1: Oxygen
(Lewis base)
protonated by H +
(Lewis acid).
H CH3
CH3
- H+
C C CH3
+
H
CH3
CH3
C C
CH3
Step 3: Carbocation
neutralized by elimination
of hydrogen ion. C=C
results.
Step 2: Oxonium
ion loses water
molecule to form
carbocation.
H+
Step 1: Oxygen
(Lewis base)
protonated by H +
(Lewis acid).
H+
OH
- H2O
Step 2: Oxonium
ion loses water
molecule to form
carbocation.
- H+
Step 3: Carbocation
neutralized by elimination
of hydrogen ion. C=C
results.
OH + NaOH
CH3CH 2
ONa + H2O
(b) Treatment of each of these alcohols with the Lucas reagent will produce a
turbid mixture as the alkyl halide is formed. However the reaction proceeds at
different rates depending on the structure of the alcohol.
230
Chapter 9
CH3
ZnCl
2
+ HCl
CH 3CCH2CH 3 + H2O
OH
CH3
Instantaneous
reaction at
room temperature
Cl
CH3
Instantaneous
2 CH 3CHCHCH3 + HCl
CH 3CHCHCH3 + H2O reaction only
if heated
OH
Cl
CH3
CH3
Slow reaction
ZnCl 2
1 CH 3CHCH2CH 2OH + HCl
CH 3CHCH2Cl + H2O even if heated
ZnCl 2
(c) The secondary alcohol is subject to oxidation but the tertiary alcohol is not.
The positive reaction is observable as the yellow-orange oxidation reagent
becomes green as the reaction proceeds.
CH 3
CrO3
CrO3
CH 3CHCH 2CH 3
CH3CCH 2CH 3
CH3CCH 3
No Reaction
O
OH
OH
CH2
NH3
HOCH2
CH2 N
3
CH 3
(b)
H3C C
CCH 2CH 3 +
H2O
H2SO 4
H2O
H2SO 4
Chapter 9
CH 3CH 2ONa
CH3CH 2Br
+ NaBr
CH3
OH
and H 2SO 4
PBr3
CH 3ONa
232
CH 3OH
Na
Chapter 9
2. Make molecular models of the isomers of C3H6O, two alcohols and one ether.
How many non-bonding electron pairs reside on the oxygen? What is the
hybridization and geometric orientation of the carbons and the oxygen?
Each oxygen has two non-bonding electron pairs. The carbons and oxygens all
have four bonding and non-bonding electron pairs total and are sp3 hybridized
with a tetrahedral geometry.
3. Make a model of one of the seven isomers of C4H10O and then convert it into
the other alcohols (four total) and ethers (three total). Draw each structure.
Identify skeletal, positional, and functional isomers. Determine if the alcohols
are primary, secondary, or tertiary.
The four structures below are alcohols. The first two are positional isomers of
one another and the second two are also positional isomers of one another.
The first two are skeletal isomers of the second two. The first and last alcohol
are primary, the second is secondary, and the third in tertiary.
233
Chapter 9
The following three compounds are all ethers and they are functional isomers of
the previous four alcohols. The first two ethers are positional isomers of each
other and the third is a skeletal isomer of the other two.
234
10
N
..
..
Amines
CHAPTER SUMMARY
235
Chapter 10
Amines
10.1
Nasal
Decongestants,
Diet
Pills,
and
Amines
Chapter 10
Because of their basicity, amines react readily with strong mineral acids to
form ammonium salts.
B. Expressing Relative Basicities of Amines: The Basicity
Constant
Relative basicities are expressed using the basicity constant, K b ,
which is defined as the concentrations of the ionized amine products in
water (ammonium salt and hydroxide) divided by the concentration of the
un-ionized amine. Larger Kb 's mean greater basicity. pK b is the negative
logarithm of K b ; the smaller the pKb the stronger the base.
C. Relationship of Structure and Basicity in Amines
1.
Electron-releasing groups increase the availability of
nitrogen's lone pair and, as a result, also increase the basicity of amines;
alkyl amines are more basic than ammonia.
2. Electron-withdrawing groups decrease the availability of the
non-bonding electron pair and decrease basicity; amides are much
less basic than ammonia.
3. In aromatic amines, the non-bonding electron pair on nitrogen
overlaps with the benzene pi-cloud by resonance; this decreases the
availability of the lone pair and stabilizes the compound. As a result,
aromatic amines are considerably less basic than aliphatic
amines. Electron-donating groups on an aromatic amine increase
availability of the non-bonding pair whereas electron-withdrawing groups
decrease availability; as a result electron-donating groups on an
aromatic ring increase basicity and electron-withdrawing
groups decrease basicity. The effect of these groups is greatest at
the ortho and para positions.
D. Expressing Basicity with Acidity Constants
Basicity can also be expressed with acidity constants. With amines,
Ka defines the equilibrium in the direction of the ammonium salt ionizing to
the free amine and hydronium ion in water. Since this is the opposite of
the definition of Kb , small Ka's and large pKa's mean strong basicity.
237
Chapter 10
Amines
10.5
Amines as Nucleophiles: Alkylation by Nucleophilic
Substitution
Alkylation involves treating ammonia or an amine with an alkyl halide.
The amine, as a Lewis base with a non-bonding electron pair, is a good
nucleophile and displaces the halide ion from the alkyl halide; the reaction is
nucleophilic substitution with a neutral nucleophile. S N2 reactions are
common. Since alkylation tends to continue until four groups are bonded to the
nitrogen, it has limited synthetic utility.
CONNECTIONS 10.3 Acetylcholine and Neuromuscular Blockade
10.6 Preparations of Amines by Reduction Reactions
A. Reduction of Aromatic Nitro Compounds
Amines can be synthesized by reduction of nitro compounds with
hydrogen and platinum catalyst or with a tin and hydrochloric acid
solution. Aromatic nitro compounds can be made by treating benzene or a
benzene derivative with nitric and sulfuric acids.
B. Reduction of Nitriles
Nitriles can be reduced using hydrogen gas and nickel catalyst to
produce amines.
C. Reduction of Amides
Lithium aluminum hydride is used to reduce amides. In both cases
amines are the reduction products.
CONNECTIONS 10.4 Sulfa Drugs
10.7 Aromatic Diazonium Salts
A. Preparation
Upon treatment with sodium nitrite and hydrochloric acid at 0o C,
primary aromatic amines can be converted to aromatic diazonium
salts, an unstable species that is very useful in organic synthesis. Since a
nitro group can be reduced to a primary amine, it is a synthetic precursor
to a diazonium salt.
238
Amines
Chapter 10
B. Replacement Reactions
Diazonium salts are quite useful in organic synthesis as the diazonium
group can be easily replaced by fluorine, chlorine, bromine, iodine,
cyanide, hydroxy, and hydrogen. In these diazonium replacement
reactions, nitrogen gas is evolved.
C. Coupling Reactions
In coupling reactions of diazonium salts, nitrogen is retained and
actually bonds to an activated aromatic ring in an electrophilic
aromatic substitution reaction. This reaction is used to make azo
dyes.
CONNECTIONS 10.5 Dyes and Dyeing
10.8 Heterocyclic Amines
Heterocycles are cyclic compounds in which one or more of the ring
atoms are not carbon.
A. Structure and Basicity of Heterocyclic Amines
Heterocyclic amines have nitrogen as one of the ring atoms.
Although they are basic, their basicity can vary widely depending on
structure and availability of nitrogen's non-bonding electron pair. Aromatic
heterocyclic amines in which the nitrogen's non-bonding electron pair is
part of the aromatic pi-cloud, the aromatic sextet, are much less basic than
those in which it is not. If the nitrogen is involved in a double bond , its
lone pair is not in the pi cloud or part of the sextet.
B. Naturally Occurring Heterocyclic Amines: Alkaloids
Alkaloids are defined as plant-produced nitrogenous bases that have
a physiological effect on humans. They are often classified according to
the heterocyclic amine present in the structure. These include the
following ring systems: pyrrolidine, pyrrole, piperidine, pyridine, quinoline,
isoquinoline, indole, and purine.
239
Chapter 10
Amines
SOLUTIONS TO PROBLEMS
10.1 Primary, Secondary, and Tertiary Amines
CH3
CH 3CH 2CH 2CH 2NH 2
1o
CH3
NH2
1o
1o
NH2
2 o CH3
2o
CH3 3 o
240
Amines
Chapter 10
and can hydrogen bond; ii has a higher boiling point because it has two N-H
bonds. i has an O-H bond and since this is much more polar than the N-H
bonds, it hydrogen bonds more extensively and has the highest boiling point.
10.6 Basicity of
.. Amines
(a) CH3CH 2CH 2NH 2
..
..
(b) CH3NHCH3
(c) (CH3CH 2)3N
HBr
+
+
HNO3
HCl
H2SO 4
(NH4)2SO 4
3 NH 3
H3PO4
(NH4)3PO4
241
Chapter 10
Amines
(d) ii < iii < iv < v < i The amines with lowest basicity have an electronwithdrawing group (the carbon-oxygen double bond). The greater the distance
of this group from the amine, the less effective. v has neither electron-releasing
or electron-withdrawing groups, and i has an electron-releasing group which
increases basicity.
10.11 Basicity of Amines
Arrangements are least basic to most basic.
(a) i < ii < iii i and ii are both aromatic amines and are much less basic than
iii which is an alkyl amine. Although ii is aromatic and not very basic, it does
have a methyl group, an electron-releasing group, that increases basicity
relative to the primary aromatic amine.
(b) i < ii < iii The nitro group is electron-withdrawing and decreases basicity.
It more effectively decreases basicity at ortho and para positions because of
resonance; thus ii is more basic than i, because the nitro is meta in ii and cannot
decrease basicity as effectively. iii has an electron-releasing group that
increases basicity.
(c) ii < i < iii ii has two withdrawing groups, i has one; electron-withdrawing
groups decrease basicity. iii has an electron-releasing group that increases
basicity.
(d) ii < iii < i ii has an electron-withdrawing group attached directly to the
nitrogen where it is most effective in decreasing lone pair availability and thus
decreasing basicity. iii has an electron-withdrawing group but it is on the
benzene ring, not right on the nitrogen. i has neither electron-releasing or
withdrawing groups.
10.12 Expression of Basicity with Acidity Constants
Least to most basic for amines.
(a) 9.9 x 10-10 < 8.3 X 10-10 < 2.3 x 10-11
(b) 5.25 < 9.81 < 10.74
10.13 Expression of Acidity with Acidity Constants
Least to most acidic for acids.
(b) 10.74 < 9.81 < 5.25
(a) 2.3 x 10-11 < 8.3 X 10-10 < 9.9 x 10-10
242
Amines
Chapter 10
+
(a) (CH 3)3NCH 2
Br
(c) CH 3CH 2
+
(b) CH 3CH 2N(CH 3)3 I -
CH 2CH 3
N+
Cl -
CH3
NO2
NO2
(b)
Cl
CH3
CH3
Br
Br2
FeBr3
HNO3
H2SO 4
(b)
NO2
NO2
1.Sn
Cl
NO2 HCl
2.NaOH
CH3
1.Sn
Br
HCl
2.NaOH
NH2
2 H2
Ni
NH2
1. LiAlH 4
2. H2O
H3C
NH 2
NaNO 2
HCl
O OC
H3C
N2 + Cl -
243
Chapter 10
Amines
HNO 3
(b) H C
3
H3C
Fe
NO 2
HCl
H2SO 4
H3C
NH 2
NaNO 2
N2 + Cl -
H3C
HCl
O OC
10.20 Diazonium Salt Replacement Reactions
NH2
Cl
(a)
N2+ Cl
NaNO 2
HCl
0oC
Cl
(b)
Cl
products of replacement
reactions
Cl
Br
(c)
Cl
I
(d)
Cl
CN
(e)
Cl
OH
(f)
Cl
(g)
Cl
Cl
NH2
b) CH3
c)
NO2
NO2
NaNO 2
- H2O
N2+ Cl
OH
HCl
0C
- HBF4
NaNO 2
NH2
CH3
N2+ Cl
CH3
HCl
0C
NaNO 2
Sn
NH2
N2+ Cl CuCN
HCl
HCl
0C
NO2
NH2
N2+ Cl
Cl 2
FeCl 3
d)
Cl
NaNO 2
HCl
Cl 0C
Sn
HCl
F
CN
Cl
CuCl
Cl
Cl
NH2
NaNO 2
HCl
0C
O2N
O2N
244
NH2
+ N N Cl
N N
NH2
Amines
Chapter 10
245
Chapter 10
Amines
(a)
(f)
Cl
NH 2
Cl
Cl
CH 3
(d) CH3CH 2NCH(CH 3)2
(e)
(h)
N(CH 3)2
H3C
N
CH 2CH 3
CH 2CH 2CH 3
246
Amines
Chapter 10
H2O
CH3NH 3+
OH -
(h) CH3NH 3+ +
H2O
CH3NH 2
H3O+
(g) CH3NH 2
247
Chapter 10
Amines
(f) Chlorine is an electron-withdrawing group. As such it makes the nonbonding electron pair on nitrogen less available. As a result, aniline is more
basic.
(g) Nitro groups are electron-withdrawing groups; they decrease electron
availability and basicity. There are two nitro groups on 2,4-dinitroaniline so it is
less basic than p-nitroaniline where there is only one.
(h) Chlorine withdraws electrons and decreases basicity; 2-chloropropanamine
is less basic than propanamine for this reason.
(i) Both of these compounds have a chlorine which is an electron-withdrawing
group and decreases basicity. In 3-chloropropanamine the chlorine is further
away from the amine group than in 2-chloropropanamine and, because of this,
it has a diminished effect. Thus 3-chloropropanamine is more basic.
10.35 Acidity and Basicity of Phenol and Aniline: Sections 9.6A.2,
and 10.4C.3
Phenols are more acidic than alcohols because one of the non-bonding
electron pairs on oxygen is drawn into the benzene ring by resonance. This
stabilizes the phenoxide ion that is formed upon ionization and thus the acidity
of phenol is enhanced by the phenomenon. This same withdrawal of electrons
by the benzene ring stabilizes aniline and decreases the availability of the nonbonding electron pair on nitrogen. Both effects decrease the basicity of aniline
relative to alkyl amines.
The withdrawal of electrons into the benzene ring makes both aniline
and phenol more electron-rich. In electrophilic aromatic substitution, the ring is
attacked by a positive electrophile; the more negative the ring, the more readily
it reacts with an electrophile.
Please see the textbook references for the resonance structures and
hybrids described.
10.36 Alkylation of Amines: Section 10.5
(a) CH3(CH 2)4CH 2NH 2
3 CH3Br
Na2CO 3
(c)
248
CH 3I
Na2CO 3
+CH 3
CH3CH 2CH 2N(CH 2CH 3)2 Cl-
CH 3
+
N(CH 2CH 3)2
I-
Amines
(d) (CH3)3N
Chapter 10
CH3CH 2
(b)
NH2
NH2
Br
1. Sn/HCl
NO2
Br
2. NaOH
NO2
HNO3
NO2
Br2
FeBr3
H2SO 4
CH3
(c)
NH2
CH 3Cl
AlCl 3
1. Sn/HCl
HNO3
Br 2. NaOH
CH3
1. Sn/HCl
H2SO 4
2. NaOH
NH2
Br
CH3
NH2
NO2
10.39 Reduction of Nitriles: Sections 8.4 and 10.6
CH 3(CH 2)4CH 2Br
NaCN
2 H2
Ni
O
CH3CH 2CH 2CH 2NHCCH 2CH 3
1. LiAlH4
2. H2O
1. LiAlH 4
2. H2O
249
Chapter 10
Amines
2 NaCN
5 H2
Ni
10.42 Reactions of Amines: Sections 10.5A and 10.6
I
II
III
CH3
Reagent
a) HCl
CH 3CH 2NHCH3
CH 3NCH3
+
CH 3CH 2CH 2NH 3Cl
H+
CH 3CH 2NHCH3 Cl
CH3
+ CH 3NCH3 Cl
H
CH3
+
+
22+
b) H2SO 4 (CH 3CH 2CH 2NH 3)2SO 4 (CH 3CH 2NHCH3)2SO 4 CH 3NH
H
excess
c) CH 3Br
CH3
CH3
CH3
CH3
+ CH 3NCH3 Br
CH3
CH3
+ CH 3CH 2NCH3 Br
CH3
2-
2 SO 4
N2+ Cl
NH2
CH3
Cl
a)
b)
CH3
h) CH3
250
Br
NaNO 2
HCl
OC
CN
c)
CH3
d)
OH
OH
i) CH3
e)
CH3
CH3
CH3
g)
f)
CH3
CH3
CH3
N(CH3)2
Amines
Chapter 10
NH 2
CH 3
CH 3
b)
Br
NaNO 2
HCl
OC
NO2
I
KI
Br
Br
N2+ Cl
NH2
Fe
HCl
c)
NaNO 2
HCl
OC
NO2
NO2
Cl 2
FeCl 3
NO2
NH2
NO2
(f)
NaNO 2
HCl
OC
Cl
Cl
N2+ Cl
H2O
Br
OH
Br
Br
Cl
HNO 3
Cl 2
H2SO 4
FeCl 3
Sn
HCl
NO 2
NO 2
Br
Br
Cl NaNO
2
Cl
NaNO 2
HCl
Br OC
Br
Br
N2+ Cl
HBF4
NH2
Sn
HCl
Br
Br
Br
CuBr
Sn
HCl
Cl
Br2
FeBr3
e)
CH 3
N2+ Cl
NH2
d)
Br
CuBr
NaNO 2
HCl
OC
a)
Cl
Cl
H2O
HCl
NH 2
N2 Cl
OH
251
Chapter 10
Amines
Sn
HCl
HNO 3
H2SO 4
(g)
NaNO 2
HCl
OC
Br
Br
Br2
FeBr3
(h)
N2+ Cl
NH 2
NO 2
HNO 3
H2SO 4
(i)
N2+ Cl
Cl
N2+ Cl
NaNO 2
HCl
OC
HBF 4
Cl
10.45 Diazonium Salts-Coupling Reactions: Section 10.7C
OH
OH
OH
NaNO 2
a)
N N + Cl
N N
NH2 HCl
OC
NH2
b)
NO2
N
NaNO 2
HCl
OC
N+ Cl
NH 2
Sn
HCl
Cl
Cl 2
FeCl 3
KI
NH 2
NO 2
Br
Br
NaNO 2
HCl
Sn
HCl
NO 2
NO 2
CuCN
Br
HNO 3
H2SO 4
CN
OH
Cl
OH
OH
N
NO2
NO2
252
Amines
Chapter 10
253
Chapter 10
Amines
2. Make models of the four isomers of C3H9N. What is the hybridization of each
carbon and the nitrogen? How many non-bonding electron pairs are on the
nitrogen? Identify primary, secondary and tertiary amines.
254
11
CHAPTER SUMMARY
11.1 Structure of Aldehydes and Ketones
Aldehydes and ketones both have a carbonyl group (carbonoxygen double bond); aldehydes have at least one carbon bonded to the
carbonyl group, whereas in ketones the carbonyl is bonded to two carbons.
255
Chapter 11
Chapter 11
257
Chapter 11
Chapter 11
devising a Grignard synthesis, one must realize that one alkyl group of the
target alcohol comes from the Grignard reagent and the other hydrogens
or alkyl groups come from the chosen aldehyde or ketone.
G. Alcohol Addition - Acetal Formation
Aldehydes and ketones react with alcohols by acid-initiated
nucleophilic addition to form hemiacetals which are usually
unstable. Reaction with a second mole of alcohol produces a acetal.
Carbohydrates usually exist in hemiacetal or acetal forms.
H. Addition of Amines
Primary amines react with aldehydes and ketones to form imines by
nucleophilic addition. Many of the products are crystalline derivatives
which have been used to characterize the original carbonyl compounds.
11.6 Reactions Involving Alpha Hydrogens
A. Acidity of Alpha Hydrogens
Alpha hydrogens are hydrogens on carbons directly attached to a
carbonyl group. They are weakly acidic and can be abstracted by base
to form a carbanion. The carbanion is called an enolate ion and is
resonance stabilized. Neutralization of the enolate ion results in an enol,
a compound in which an alcohol group is directly bonded to a carbon
involved in a carbon-carbon double bond. The enol is in equilibrium with
the original aldehyde or ketone in an equilibrium referred to as keto-enol
tautomerism. The equilibrium usually favors the keto form.
B. The Aldol Condensation
The aldol condensation involves the reaction of two molecules of an
aldehyde or ketone that has alpha hydrogens. Abstraction of an alpha
hydrogen by base produces a carbanion which attacks the carbonyl
carbon of the other molecule by base-initiated nucleophilic addition;
an alcohol group is formed. Often the alcohol dehydrates to form the final
product, an unsaturated aldehyde or ketone. In a crossed aldol
condensation, a carbonyl compound with alpha hydrogens reacts with
one without alpha hydrogens.
259
Chapter 11
SOLUTIONS TO PROBLEMS
11.1 Nomenclature of Aldehydes and Ketones
(a) 4,4-dimethylpentanal (b) 2-octanone; (c) cyclohexanone;
(d) 4-bromo-2-pentanone
11.2 Nomenclature of Multifunctional Aldehydes and Ketones
(a) 1,3,5-cyclohexantrione; (b) 5-hydroxyhexanal; (c) 7-bromo--3-hydroxy-7methyl-5-oxooctanal; (d) 6-amino-4-hydroxy-2-heptanone
11.3 Nomenclature of Unsaturated Aldehydes and Ketones
(a) 3-butynal; (b) 3-cyclopenten-1-one; (c) 7-hydroxy-2-methyl-4-oxo-5-octenal
11.4 Common Nomenclature of Aldehydes and Ketones
O
a) CH 3CHCH
CH3
b) CH 3CHCH
c) CH 3CCH2CH 2CH 3
d) CH 3C
Cl
Ag(NH 3)2OH
Tollens
O
CH 3CCH 3
Ag(NH 3)2OH
No reaction
HO
+ H2O
260
OH
Chapter 11
Acid-initiated
Nucleophilic
Addition
HO
H
-O
OH
HO
H2O
OH
H +
OH
HO
OH
-H +
H2O
Base-initiated
Nucleophilic
Addition
HO
OH
+ OH
CH 3CCH2CH 3
CN
OH
CH + HCN
CH
CN
.. .O.
....
.O.
:
CN:
CH
b) CH 3
CH 3CH
....OH
HCN
CN
CH 3CH + CN
CN
Ni
Ni
Tertiary alcohols cannot be prepared in this way because a C=O cant have
three alkyl groups attached to the carbon. There is no possible aldehyde or
ketone precursor.
261
Chapter 11
....
O
....
O ..
H
H
(b) 4 CH 3CH
CH 3CH
H
4
H2O
.
...OH
CH 3CH
H
H
11.11 Grignard Preparation of Alcohols
a) CH3Cl + Mg ether
CH 3MgCl
O
b) CH 3MgCl + HCH
O
CH 3MgCl + CH 3CH 2CH
O
CH 3MgCl + CH 3CCH3
H2O
H+
H2O
H+
CH 3CH 2OH
OH
H2O
H+
CH 3CH 2CHCH3
OH
CH 3CCH3
CH3
....
O
- +
HCH + CH 3MgCl
+
...O...-MgCl
CH 3CH
H
H2O
..
..OH
CH 3CH + MgClOH
H
262
(b)
Chapter 11
CH 2CH 3
CH 3
CH 3
CH 3CHCH 2CCH 3
OH
O
CH 3
CH 3
CH 3
CH 3CH 2CH 2CCH 2CH 3
OH
O
CH 3CH 2CH 2CCH 2CH 3 and CH3MgBr
O
CH 3CH 2CH 2CCH 3 and CH3CH 2MgBr
O
CH 3CCH 2CH 3 and CH3CH 2CH 2MgBr
See next
problem
for a more
detailed
look at the
syntheses
of this
alcohol.
263
Chapter 11
CH 3CH 2Cl
Mg
CH 3CCH2CH 2CH 3
CH 3CH 2MgCl
OH
CH 3CCH2CH 2CH 3
CH2CH 3
Method 2
CH 3I
Mg
CH 3MgI
OH
CH 3CH 2CCH2CH 2CH 3
CH3
Method 3
Mg
OMgCl
H2O
CH 3CCH2CH 2CH 3
H+
CH2CH 3
O
OMgI
H2O
CH 3CH 2CCH2CH 2CH 3
H+
CH3
O
OH
H2O
H+
CH 3CH 2CCH3
CH2CH 2CH3
264
OCH2CH3
CH
OCH2CH3
CH 3CH 2CCH3
OMgBr
CH 3CH 2CCH3
CH2CH 2CH3
Chapter 11
H+
OCH2CH3
CH
OH
CH
+
H+
CH 3CH 2OH
OCH2CH3
H+
H+
OH
CH
-H2O
+
CH
OCH2CH3
OH
CH
CH 3CH 2OH
OCH2CH3
OCH2CH3
-H+
OCH2CH3
CH
acetal
OH
CH
OCH2CH3
OCH2CH3
hemiacetal
CH2
CH2
CH2
CH2
HO
OH
+
-H+
H
O
H
O
H+
HO
CH2
O CH2
H+
H2O
H
O
CH2
CH2
CH + H2NNH
NO2
NO2
NO2 + H2O
CH NNH
NO2
265
Chapter 11
NOH
CHOH
O
CH 3CH
(b) CH3CHCH
OOH
H
CH 3CH 2CH 2CHCHCH 2CH 3
CH
CH
Dehydration Product
O
Cl
HCC C
CH CH H
3
Cl
266
Chapter 11
O
OH -
CH 3CH 2CHCH
..
HCCH C
Cl
OH
HCCH C
CH 3CH 2 H
Cl
CH 3CH 2 H
O
c) CH 3CCH2CH 2CH 2CH
O
d) CH 2CH 2CCH2CHCH2CH
OH
e)
OH
267
Chapter 11
CH 2CH 3
g) CH 2CH 2C C
f) Br3CCCH 2CCBr 3
Br
OH
CCH
CCC
O
h)
i) CH3CH 2CCH2
CH
CH3
b) CH 3CCH3
c) HCH
O
f)
Cl
11.31 Preparations of Aldehydes and Ketones: Section 11.3
O
O
O
b) CH 3CCH3 + CH 3CH
a) CH 3CCH2CH 3
O
c)
O
d) CH 3CH 2CCH2CH 3
CCH2CH2CH 3
CH3 CH3
(b) CH3CH 2C
O3
CCH2CH3
Zn
H2O
2 CH3CCH2CH 3
O
(c)
CH3CH 2CH2C
CH
+ H2O
OH
Na 2Cr2O7
(d)
CH3
268
H2SO 4
HgSO4
O
CH3
Chapter 11
O
(e)
PCC
CH 3(CH 2)8CH
Reagent
CCH3
O
a) Tollens' Reagent
Ag(NH 3)2OH
b) HCN
CONH4 + Ag
No reaction
OH
OH
C CN
C CN
CH 3
CH 2OH
c) H2/Ni
CHCH 3
OH
d) NaBH 4,
then H2O
e) CH3MgCl,
then H2O
f)
CHCH 3
OH
CH 3
CHCH 3
C CH 3
OH
OH
CH
OH
OH
MgBr,
then H2O
g)
CH 2OH
NHNH2
h) H2NOH
i) CH3OH/H +
CH
NNH
CH 3
NNH
CH 3
CH
NOH
NOH
OH
CH 3
OH
C OCH 3
C CH 3
OCH 3
269
Chapter 11
j) 2 CH3OH/H +
k) D2O, NaOD
OCH 3
OCH 3
C OCH 3
C CH 3
OCH 3
O
CCD 3
No Reaction
Mg
H2O
H+
b) CH 3Br
Mg
CH 3CH 2CH
CH 3MgBr
CH 3CHCH 23CH 3
OMgBr
H2O
H+
CH 3CHCH 23CH 3
OH
Second Method
CH 3CH 2Br + Mg
CH 3CHCH 23CH 3
OMgBr
270
CH 3CH 2MgBr
H2O
H+
CH 3CHCH 23CH 3
OH
CH 3CH
Chapter 11
c) Method 1
CH 3CH 2CH 2Cl + Mg
OH
H2O
CCH2CH3
H+
CH2CH 2CH3
O
CCH2CH3
OMgCl
CCH2CH3
CH2CH 2CH3
Method 2
CH 3CH 2I + Mg
OH
CCH2CH2CH 3
CH2CH 3
CH 3CH 2MgI
CCH2CH2CH 3
OMgI
H2O
CCH2CH2CH 3
H+
CH2CH 3
Method 3
Br + Mg
OH
CH 3CH 2CCH2CH2CH 3
MgBr
OMgBr
H2O
CH 3CH 2CCH2CH2CH 3
H+
b)
OH
OH
CH 2C CH 3
c) CH 3CCH 2CH 3
CH 3
271
Chapter 11
OH H O
CH2CH 2CH3
O
CH3CH 2CH2CH2C C
C CH
CH2CH 2CH3
H+
CH
(-H2O)
H CH2CH 2CH3
H O
OH H O
OH
CHCH
(CH3)2CHCH2
CH(CH3)2
C CH
CH(CH3)2
O
CCH
(CH3)2CHCH2C
H
(c)
H O
CH 2C
OH
H+
(-H2O)
CH(CH3)2
OH H O
CHC
CH 3
CH 3
H+
(-H2O)
C CHC
CH 3
CH2C
OH
C
H
O
C
H
272
OH H O
CHC
CHC
H+
(-H2O)
Chapter 11
b)
c)
CH
CH 3CH 2CH
.. _
: O:
..
O:
(a)
CH3CH 2CH2CH
_
..
O:
.. _
: O:
(CH3)2CHCH
..
_
CH
.. _
: O:
..
:O
(c)
CH
C=CH2
CCH
.. 2
OH
(c)
C=CH2
H
OCH3
CH 3CCH3 + H2O
OCH3
273
Chapter 11
O
c)
+ CH2
OH
CH2
H+
CH2
CH2
+ H2O
OH
CH3
Mg
CH 3MgBr
Mg
OH
CH 3CH 2CH 2CHCH3
H2O
H+
O
CH 3CH
H2O
H+
OH
CH 3CH 2CH 2CHCH3
Reductions
O
OH
Ni
274
b)
OH
c) CH 3CH
OH
CH 2
NCH3
CH
Chapter 11
....
O
....
O
.. ..
O ..
4 CH 3CH 2CH
..
OH
..
H2NOH
CH 3CH 2C+
+
d) CH 3CH 2CH H
CH3CH 2C
H
..
H2O..
NOH
+
-H +
CH3CH 2C NOH
O
e) CH 3CH 2CH
OH
O
CH 3CH 2CH
CH 3..
CHCH
CN
....OH H
+
CH3CH 2C .. NOH
H+
.. OH
H
OH
CH 3CH 2CH
H2O
H+
...O.
CH 3CH 2CCH3
...O. ..-Na +
H+
CH 3CH 2..
CH
H2O
CN..
+ . Na .CN ..
b) CH 3CH 2CH
OH
....
O
CH 3CH 2CH
..O....- O
CH 3CH 2C.. CHCH
H CH 3
OH
O
dehydration CH CH CH
3
2
CCH
CH 3
275
Chapter 11
...O.
f) CH 3CH 2CH
..
..OH
CH 3CH 2C
..
CH 3..
OH
..+
CH 3CH 2C OCH 3
..
-H2O..
+
CH 3CH 2C
..
CH 3..
OH
..
OCH
.. 3
.
...OH
H
CH 3CH 2C
..
.OCH
. 3
+ .. OCH 3
CH 3CH 2C
+ H
OH
..
-H +
OCH
.. 3
.
...OCH
..3
CH 3CH 2C OCH
.. 3
b)
OH
CH + CH3CN base
CHCH2CN
O
c)
CO2CH3
CH + CH 2
-H2O
OH CO2CH3
base
CO2CH3
CH CH
CH
CH
-H2O
CHNO2
CHCN
CO2CH3
CH
CO2CH3
CO2CH3
CH 3
O
O
OH
dehydration
CH 3CCH 2CCH 3
CHCCH 3
O
CH 3C
CH 3
276
CH 3
H2O
Chapter 11
O
b) CH 3CH 2CH
OH
O-
CH
CH 3..
CH 2CH
CH
CCH
CHCH
CH3
OH
O
dehydration
H2O
CHCHCH
CH3
CH3
OH
HO
H
CH2OH
H
O
H
OH
HO
H
O
CH2OH
HO
H HO
277
Chapter 11
1. Make models of the aldehyde and ketone with the formula C3H6O.
2. Make models of the three isomers of C4H8O. Identify aldehydes and ketones.
How many non-bonding electron pairs are on the oxygen of each model? What
are the hybridizations of the carbons and the oxygen?
278
12
O
R C
C R
O H
H O
CARBOXYLIC ACIDS
CHAPTER SUMMARY
279
Chapter 12
Carboxylic Acids
Carboxylic acids are almost always named using a suffix. The suffix
oic acid is attached to the name for the longest continuous carbon chain.
If the acid group is attached to a ring the suffix carboxylic acid is used.
B. Polyfunctional Carboxylic Acids
Of the functional groups, carboxylic acids are the highest priority and
named with a suffix; the other functional groups - aldehydes, ketones,
alcohols and amines are named with prefixes if in a molecule where a
carboxylic acid has received the suffix designation.
C. General Procedure for Naming Organic Compounds
A general procedure for naming organic compounds is given in this
chapter since this is the last major functional group covered. The
procedure for naming organic compounds is:
(1) Name the longest continuous carbon chain.
(2) Name carbon-carbon double and triple bonds with suffixes en and yn
respectively; if all carbon-carbon bonds are single, use an.
(3) Name the highest priority functional group with a suffix (acid >
aldehyde > ketone > alcohol > amine) and the others with prefixes.
(4) Number the carbon chain giving preference to the functional group
named by a suffix, then multiple bonds (carbon-carbon double bonds take
priority over triple bonds when making a choice is necessary), then groups
named with prefixes.
(5) Name all other groups with prefixes and number them.
D. Common Names of Carboxylic Acids
Carboxylic acids are also named with common names that often
describe a familiar source or property of the compound.
12.3 Physical Properties of Carboxylic Acids
The boiling points of carboxylic acids are high relative to other classes of
compounds due to hydrogen bonding; carboxylic acid molecules can
hydrogen bond in two places and as a result often exist as dimers. Lower
molecular weight carboxylic acids are water soluble.
12.4 Acidity of Carboxylic Acids
280
Carboxylic Acids
Chapter 12
Chapter 12
Carboxylic Acids
SOLUTIONS TO PROBLEMS
12.1 IUPAC Nomenclature
(a) heptanoic acid;
(b) 4,4,4-tribromobutanoic acid;
(c) 1,5-pentandioic
acid; (d) cyclohexanecarboxylic acid (e) m-methylbenzoic acid;
(f) 3-chlorocyclobutanecarboxylic acid
CO2H
282
NaOH
+
Ca(OH)2
CO2Na
(CH 3CH 2CO2)2Ca
H2O
+
2H2O
Carboxylic Acids
Chapter 12
+ NaOH
CH3CH=CH-CH=CHCO 2K + H2O
most
acidic
However, smaller
283
Chapter 12
Carboxylic Acids
The most acidic, iii, has two acid groups; each acts as an electron-withdrawing
group on the other and increases acidity. ii has neither electron-withdrawing or
electron-releasing groups, and i has one electron-releasing group which
decreases acidity.
(d) meta < para < ortho
Each has one electron-withdrawing group. Because of resonance, the ortho
and para chloros increase acidity more than meta. In addition, the ortho is
closer and thus this is the most acidic.
12.11 Nomenclature of Carboxylic Acid Salts
(a) Sodium ethanoate; (b) calcium propanoate; (c) potassium 2-butenoate
(d) ammonium p-bromobenzoate
12.12 Preparations of Carboxylic Acids
(a)
CH2CH 2CH3
CO2H
(b)
CH3
KMnO4
H3C
CH3
CO2H
KMnO4
HO2C
CO2H
284
Carboxylic Acids
CH3
HNO3
Chapter 12
CH3
Br2
FeBr3
H2SO 4
NO2
CH3
Br
KMnO4
NO2
CO2H
Br
NO2
H2O
H+
OH
CH 3(CH 2)3CCO2H
CH3
H2O
H+
285
Chapter 12
Carboxylic Acids
CO 2H
286
CH2OH
KMnO4
COH
Carboxylic Acids
Chapter 12
O
c)
d)
Br
H2O
N
H+
Mg
COH
MgBr
CO 2
H O
COMgBr 2+
H
COH
H2O
H+
NaCN
CO2
CH 3(CH 2)4CHCH3
CO2MgCl
OH
OH
O
NaCN
H2O
CH 3(CH 2)3CHCO 2H
CH 3(CH 2)3CHCN
(d) CH 3(CH 2)3CH
+
H
H+
CH 3CH 2CH 2CH 2CH 2CH 2CO2H
(e) CH3CH 2CH 2CH 2CH 2CH 2CH 2OH CrO3
+
H
12.27 Physical Properties: Section 12.3
O
H O
O
O
O
CCH 3
HCOCH < HOCH CH < CH COH CH 3C
3
O H O
The lowest boiling compound has no O-H bonds and cannot hydrogen bond. In
the compound with the highest boiling point, the O-H bond is polarized by the
C=O making the hydrogen bonding even stronger. Also in ethanoic acid, two
molecules can orient so that hydrogen bonding can occur in two positions.
12.28 Physical Properties: Section 12.3
The dramatic difference in boiling points between chloroethane and ethanoic
acid is a result of the ability of ethanoic acid to hydrogen bond. Bromoethane
has a higher boiling point than chloroethane because bromoethane has a
higher molecular weight. However, this increase in molecular weight doesn't
287
Chapter 12
Carboxylic Acids
Most Acidic
c) 2 < 4 < 1 < 3
f) 3 < 1 < 4 < 2
(a) The electronegativity of the halogens is F>Cl>Br; the acidity is in the same
direction because electron-withdrawing groups increase acidity. The #4
compound doesnt have an electron-withdrawing group and is least acidic.
(b) The carbon oxygen double bond is an electron-withdrawing group and will
increase acidity. The closer to the acid group, the more effective and acidity is
in this direction.
(c) Each compound has two bromines; these are electron-withdrawing groups
and will increase acidity. The proximity of the bromines to the acid group is the
determining factor. In the least acidic they are on carbons 3 and 4; in the next,
carbons 2 and 4; in the next, carbons 2 and 3; and in the most acidic, both are
on carbon 2.
(d) Chlorine is electron-withdrawing and will increase acidity. On a benzene
ring the effect will be greatest with the chlorine is ortho or para to the acid group.
In the least acidic, there is only one chlorine and it is meta; the compound with
just one chlorine, but para, is next. The other two compounds have two
chlorines. In each one is para and the other is either meta or ortho; the ortho is
more efffective and this is the most acidic.
(e) These are dicarboxylic acids. Acid groups are electron-withdrawing so
each can increase the acidity of the other. The determining factor here is how
close they are to one another.
(f) These are four different classes of organic compounds. Alkanes are not
acidic. Alcohols are very slightly acidic but no so much as phenols in which the
anion formed from ionization is resonance stabilized. Carboxylic acids are the
most acidic because of the electron-withdrawing carbon-oxygen double bond
and the resonance stabilization of the anion.
288
Carboxylic Acids
Chapter 12
c) ( O2C(CH2)3CO2 )2Ca 2+
+
d) CH 3CO-2NH 4
2. There are two carboxylic acids with the formula of C4H8O2. Make molecular
models of each.
289
13
O
O
RCCl
O O
RCOCR
RCOH
RCNH 2
RCOR
DERIVATIVES OF
CARBOXYLIC ACIDS
CHAPTER SUMMARY
290
Chapter 13
anhydrides are very reactive and are used in synthetic organic chemistry;
the others are found abundantly in nature.
The reactivity of carboxylic acids and their derivatives is a result of
polar bonds, non-bonding electron pairs and the carbonoxygen double bond. The C=O can attract both nucleophiles and
electrophiles.
B. Nomenclature of Carboxylic Acid Derivatives
Carboxylic acids are named by adding the suffix oic acid to the
base name. Acid chlorides are name by changing the ic acid of the
parent carboxylic acid to yl chloride. The suffix acid is changed to
anhydride to name acid anhydrides. Esters are named like acid
salts by changing ic acid to ate and preceding the name by the name of
the alkyl group. To name amides, the oic acid is changed to amide.
CONNECTIONS 13.1 Aspirin and Other Analgesics
13.2 Nucleophilic Acyl Substitution Reactions
A. The Reaction
A characteristic reaction of carboxylic acid derivatives is
nucleophilic acyl substitution. In this reaction a negative or neutral
nucleophile replaces a leaving group to form a substitution product. The
leaving groups and nucleophiles are the groups that define the
various acid derivatives; as a result, the reaction usually involves the
conversion of one acid derivative into another. The order of reactivity
of acid derivatives is: acid chloride > anhydride > acid or ester >
amide. In general, reaction of any of these derivatives with water
produces acids; with alcohols, esters result; and with amines, amides are
formed.
B. The Reaction Mechanism
Nucleophilic acyl substitution can be initiated by a negative or
neutral nucleophile attacking the partially positive carbonyl carbon.
In this two-step mechanism, a tetrahedral intermediate is formed;
loss of the leaving group produces the new acid derivative. Alternatively,
291
Chapter 13
292
Chapter 13
293
Chapter 13
Chapter 13
SOLUTIONS TO PROBLEMS
CH3
CH3CHCO 2H
HCO2CHCH3
O
HCN(CH3)2
O
(CH3)2CHCCl
O O
CH3CH 2COCCH2CH 3
O O
CH3COCCH2CH3
(c) p-nitrobenzoyl chloride
295
Chapter 13
O
CCl
+ SO 2 + HCl
+ HCl (NaCl in c)
O O
c) CH 3COCCH3
O
f) CH 3CN(CH2CH 3)2
..
..
H2O:
:O
..
:O :
- HCl
CH 3C Cl
+
: OH
.. 2
CH 3C Cl
CH3CH 2CONa
O
O
CH 3CONa
296
CH 3CH 2CCl
..
:O
..
..
CH 3C OH
tetrahedral
intermediate
O O
CH3COCCH 2CH 3
HCl
HCl
O O
CH3COCCH 2CH 3
Chapter 13
O
CH 3CNH2
tetrahedral
+ NH3 intermediate
O
O
(a) CH CH CCl (b) CH CH COCH (c) CH CH CNH (d) CH CH CNHCH
3
2
3
2
3
3
2
2
3
2
3
CO2H
(CH3)2NH
O
C
H+
OH
CH 3OH
OCH3
H2O
The Mechanism
H+
O
C
OH
CH 3OH
OH
C
+
OH
OH
C OH
OCH 3 tetrahedral
intermediate
H+
297
Chapter 13
OH
OH
- H2O
H+
C OH
OCH 3
C+
OCH 3
OCH 3
+ CH3CH 2OH
O
b) CH 3COCH 3
- H+
c) CH 3CNH2
d) CH 3CN(CH2CH 3)2
OCH3
H2O
OH
CH 3OH
O
C
OCH 3
OH
- H+
C+
OCH 3
OH
H+
C OH
tetrahedral
OCH 3 intermediate
OH
CH 3OH
C OH
OCH 3
H+
OH
-H2O
C OH
+
H+
OH
OH
OCH 3
O
C
O
OH
OCH 3 tetrahedral
intermediate
O
C
298
+ CH3OH
OH
+ CH3O
Chapter 13
COH
CH 3CNH2 + H2O
CH 3COH + NH4+
OH
13.19 Preparations of Amides
O
CH 3
CH 3CH 2CCl + HNCH 3
O
O CH 3
O CH 3
HNCH 3
O CH 3
CH 3
CH 3CH 2COCH 3
+ HCl
CH 3CH 2C-NCH 3
CH 3
CH 3CO + NH3
CH 3CH 2C-NCH 3
HNCH 3
+ CH3OH
13.20 Polyamides
O
H2N
NH2
ClC
O
CCl
13.21 Polyesters
CH2O
OCH2
299
Chapter 13
O O
CH 2COCCH 2
CH 2COH
(c)
CH2N(CH2CH 3)2
MgBr
CH 3COCH 3
CH 3COCH 3
tetrahedral
intermediate
CH 3C
CH 3Cketone
OH
final
product
CH 3O
H2O/H
CH 3C
MgBr
tetrahedral
intermediate
COEt
CH2
COEt
NaOEt
CH 3(CH 2)3Br
CH(CH2)3CH3
COEt
COEt
H2O
OH
H+
COH
O
CO2 + CH 3(CH 2)3CH 2COH
heat
CH(CH2)3CH3
COH
O
CH 3CH 2CCHCOCH2CH 3
CH3
13.27 Nomenclature of Carboxylic Acids: Section 12.2
(a) butanoic acid; (b) 7-methyloctanoic acid; (c) 2-pentenoic acid;
300
Chapter 13
(d) 4-oxopentanoic acid; (e) 2-aminoethanoic acid; (f) 6-hydroxy-2,4heptadienoic acid; (g) m-bromobenzoic acid; (h) cyclopentanecarboxylic
acid; (i) 1,6-hexandioic acid
13.28 Nomenclature of Acid Chlorides: Section 13.1B.1
(a) butanoyl chloride; (b) 2-butenoyl chloride; (c) 3-oxopentanoyl chloride;
(d) p-chlorobenzoyl chloride
13.29 Nomenclature of Acid Anhydrides: Section 13.1B.2
(a) butanoic anhydride; (b) propanoic anhydride;
(c) butanoic propanoic anhydride
13.30 Nomenclature of Esters: Section 13.1B.3
(a) methyl pentanoate; (b) ethyl butanoate; (c) propyl propanoate;
(d) butyl ethanoate; (e) pentyl methanoate; (f) isopropyl propanoate;
(g) methyl p-nitrobenzoate; (h) butyl 2,4-hexadienoate
13.31 Nomenclature of Amides: Section 13.1B.4
(a) pentanamide; (b) N-methylbutanamide; (c) N-ethylpropanamide;
(d) N,N-dimethylpropanamide; (e) N-ethyl-N-methylethanamide;
(f) N,N-diethyl-o-methylbenzamide; (g) 4-hyroxy-N-propyl-2-pentenamide
13.32 Nomenclature of Carboxylic Acid Derivatives: Section 13.1
O
(a) CH3CH 2CH 2CO2H
(b) H2N
CO2H
(c) H2N
COCH2CH 3
O
(e) CH3CH=CH-CH=CHCO2K
(d) CH3CH 2CH 2COCH 2CH 2CH 2CH 2CH 3
O
O
O
(f)
(g) HCN(CH3)2
(h)
CN(CH2CH3)2
CNH2
OH
CH3
O O
O O
O
(i) CH3(CH 2)2COC(CH2)4CH 3
CCl
Cl
13.33 Reactions of Acid Derivatives: Section 13.3-13.7
O
O
(a) CH 3CH 2CCl
H2O
CH 3CH 2COH
HCl
301
Chapter 13
(b) CH CH COCCH CH + H O
3
2
2
3
2
O
(c) CH 3CH 2COCH 3
O
(d)
CH 3CH 2CNH2
O
+
H2O
CH 3CH 2COH
O
CH 3OH
H2O
CH 3CH 2COH
NH 3
COCCH 2CH 3
O
(d)
(c)
COH
(b)
CNH 2
(e)
COCH 3
CNHCH 3
(f)
CNCH 2CH 3
CH 3
O
(c) CH 3CH 2CNH 2
O
(d) CH 3CH 2C N
302
Chapter 13
O
CH3NHCH3
(g) O 2N
CO 2H
+ CH3OH
303
Chapter 13
H2O
OH
elimination
of water here
OH
O
C
Heat
OH
CH3
H2O
Cl
CH 3C
:O
Cl
- HCl
CH 3C
: :
: :
CH 3C
CH 3OH
: O: _
:O
OCH 3
: OCH 3
H+
CH 3C-O-CCH 3
CH 3CH 2OH
:O
: O :O
:O: :O
- CH3CO 2H
CH 3COCH 2CH 3
CH 3C-O-CCH 3
CH 3CH 2OH
:O
304
: :
: :
: :
+ NH 3
CH 3C-NH 2
Chapter 13
OH
CH3O : -
: :
: :
: :
: :
:O
: OH
:O
+
: :
: :
O: -
CH 3OH
CH 3CH 2C
+
OH
H+
-H2O
CH 3CH 2 C OH
OCH2CH3
OH
CH 3CH 2OH
OH
CH 3CH 2 C
OH
OCH2CH3
H+
OH
OH
- H+
CH 3CH 2 C +
OCH2CH3
OCH2CH3
:O
: :
: :
CH 3CH 2 C
C-O:
(e)
H3C
CH2N(CH3)2
305
Chapter 13
:O
: O:
H: -
: :
CH 3C-OCH 3
: :
CH 3C-OCH 3
H: -
:O:
:O
H2O
CH 3CH H+
H
CH 3CH
: OH
CH 3CH
H
(b) As with the previous mechanism, this one involves nucleophilic acyl
substitution and nucleophilic addition.
:O
: O: MgBr
:O
CH 3MgBr
- CH3O CH 3C-OCH 3
CH 3C-OCH 3
CH 3CCH3
: :
CH3
:
: OH
H2O
H+
CH 3CCH3
: O:
MgBr
CH 3MgBr
CH 3CCH3
CH3
CH3
Br
O
(b)
CH2CH 2COCH3 +
H2O
H+
OH
CH2CH 2CCH2CH2CH2CH 3
CH2CH 2CH2CH3
Chapter 13
OH
+
CO2H
H2O
CH3CO2H
acetic acid
COH
H2O
OH O
Hydrolysis
occurs
here; Salol is
an ester.
OH
CONa
NaOH
Phenol
the basic
environment of
the small intestine
converts salicylic acid
to the salt, sodium salicylate.
b) nylon 4-6
O
O
H
H
N(CH2)4N C(CH2)4C
CH3
c) polycarbonates
C
CH3
n
O
O C
n
307
Chapter 13
CH 3CH 2CH
CO2H
CO2Et
b) CH2
CO2H
NaOEt
CH 3CH 2Cl
CO2Et
CH 3CH 2CH
CO2Et
CH 3Br
NaOEt
CO2Et
CO2Et
CH 3CH 2CCH3
CO2Et
H2O
OH
CO2H
CH3
heat
CH 3CH 2CCH 3
CH 3CH 2CHCO 2H+ CO2
CO2H
H2O
+ H2O
O
CH 3COCH 2(CH 2)6CH 3
+ H2O
H+
O
CH 3CH 2CH 2CO(CH 2)4CH 3 + H2O
308
Chapter 13
CH 3O
CH 3COCH 3
O
O-
O
CH 3COCH 3
CH 3C OCH3
._CH
. 2COCH 3
- OCH
3
CH2COCH 3
CH 3CCH2COCH 3
13.57 Claisen Condensation: Section 13.10B
O
a) 2 CH 3COCH 3
NaOCH 3
O
b) 2 CH 3CH 2COCH 3
CH 3CCH2COCH 3 + CH3OH
NaOCH 3
c)
O
NaOCH 3
COCH 3 + CH 3COCH 3
CCH2COCH3 + CH3OH
13.58 Proteins
Proline
Phenylalanine
O
CH2
CHC OH
CH2
NH
Glycine
O
H
H NCH 2COH
O
H
H NCHC OH
CH2
CH2
CH2
CHCNHCHCNHCH2COH
CH2
NH
CH2
CH2
309
Chapter 13
OH
CO2H
+ NaOH
a)
CO2Na
+ H2O
O O
b) CH 3CH 2O
NH2 + CH 3COCCH3
CH 3CO2H + CH 3CH 2O
O
NHCCH3
O O
NH2 + CH 3COCCH3
c) HO
O
d) H2N
OH
OH
OH
OH
COH
+ NH3 heat
CO 2H
OH
g)
310
+ H2O
CO 2H
OCCH 3
+ CH 3CO 2H
O
O
H
HN
CH3CH 2
C
HN
H
COCH2CH 3+ H2O
H2N
CNH2
+ CH 3COCCH 3
CH3CH 2
COEt
h)
C
COEt
O O
H+
COCH3
+ H2O
COH
H+
+ CH3OH
e)
f)
NHCCH3 + CH3CO2H
HO
C NH
C
C O
C NH
O
Chapter 13
+
COH + CH3O H H
18
In the starting materials, the methanol has the labeled oxygen. Since the ester
oxygen has the labeled oxygen in the ester product, the oxygen of the ester
must have come from the alcohol.
311
Chapter 13
4. Make models of the two acid chlorides with the formula C4H7OCl..
312
14
HO
HO
CH2OH
O
OH
O
HO
CH2OH
O
OH O
HO
cellulose
Carbohydrates
CH2OH
O
OH O CH2OH
HO
O
OH OH
amylose
CHAPTER SUMMARY
14.1 Chemical Nature of Carbohydrates Polyhydroxy Aldehydes and Ketones
Carbohydrates are a class of organic biopolymers which consist of
polyhydroxy aldehydes and ketones, their derivatives and polymers. Other
terms for carbohydrates include sugars and saccharides. A single monomer
unit is called a monosaccharide; several units are referred to as an
oligosaccharide; larger polymers are called polysaccharides.
The
simplest carbohydrates are glyceraldehyde and dihydroxyacetone.
14.2 Nomenclature of Carbohydrates
The nomenclature of carbohydrates usually includes the suffix -ose.
Monosaccharides may also be identified according to the nature of the carbonyl
functional group (aldose or ketose), the number of carbons in the molecule
(tri-, tetr-, pent- ose) or a combination of these two. Monosaccharides also
have common names such as ribose, glucose, galactose, and fructose
(four of the most common monosaccharides found in nature).
14.3 Structures of Monosaccharides
A. D,L - Aldoses: Open Chain Structures
Monosaccharides have one or more chiral carbon centers and can
thereby form enantiomers and diastereomers.
Most common
monosaccharides are in the D-family. This means that, using Dglyceraldehyde as a starting point, other chiral carbons can be inserted
between the carbonyl group and the D- carbon, producing families of
313
Chapter 14
Carbohydrates
314
Carbohydrates
Chapter 14
315
Chapter 14
Carbohydrates
OH
H
H
OH
CH2OH
CHOH
H C OH
H C
HO C
HO C
H C
OH
H
H
OH
CH2OH
CHO
HO C H
H C
HO C
HO C
H C
OH
H
H
OH
CH2OH
Carbohydrates
Chapter 14
OH
HO
CH
H- C-OH
HO- C-H
HO-C-H
HO-C-H
CH2
CH2
CH2
CH2
H-C-O
H-C-O
HO-C-H
H-C-O
CH2OH
CH2OH
CH2OH
CH2OH
The epimers are A & B; the anomers are B & D ; the diasteromers are A & B,
A & D , B & D . Compound C could be an enantiomer to the open-chain form of
A. In its current form, however, it doesn't have the same number of chiral
carbon centers as do the other compounds.
D-mannose + O
H
C
OH
H
D-mannose C
H
HO
D-mannose C
HO C
HO C
HO C
HO C
HO C
HO C
H C
OH
H C O H
+
CH2OH
H C
OH
H C
OH
H C
H C
CH2OH
CH2OH
317
Chapter 14
Carbohydrates
+ O
C
D-glucose
H
H C OH
HO C
OH
H
D-glucose
H C
OH
H C O H
+
CH2OH
H C
OH
HO C
H C
H
HO
D-glucose C
OH
HO C
H C
OH
H C
OH
H C
H C
CH2OH
CH2OH
Five-membered rings
H
H + O
OH
H
HO
HO
C
C
C
O OH
HOCH
HOCH
HCOH
HCOH
+
HC O H
CH2OH
D-arabinose
HOCH
OH
OH
HCOH
OH
OH
O
HO
HC O
HC O
CH2OH
D-arabinose
CH2OH
OH
D-arabinose
H + O
C
HCOH
HOCH
HC O H
+
CH2OH
D-xylose
318
OH
HO
HO
C
O
OH
OH
HCOH
HCOH
OH
HOCH
HOCH
HC
CH2OH
D-xylose
HC
CH2OH
D-xylose
HO
OH
O
OH
OH
Carbohydrates
Chapter 14
Six-membered rings
OH
HO
HCOH
HCOH
HCOH
H2C
HCOH
HCOH
HCOH
HCOH
OH
CH2
OH
HCOH
OH
OH
HCOH
CH2
CH2
HO
OH
CH2OH
D-galactose
OH
OH
(Cyclic
and
Open-chain
OH
HO
CH2OH
O
OH
OH
HCOH
HOCH
HC
HO
OH
CH2OH
HOCH
HCOH
OH
CH2OH
OH
OH
OH
HCOH
HOCH
OH
HOCH
HCOH
HOCH
OH
HCOH
HOCH
HCOH
OH
HOCH
HC=O
OH
OH
HCOH
D-xylose
OH
D-arabinose
D-arabinose
CH2OH
OH
HCOH
CH2
OH
O
O H
HC=O
OH
OH
HCOH
D-arabinose
OH
OH
OH
CH2OH
OH
HO
O
CH2OH
Haworth OH
Fischer
ConformationalHO
projection Formulas
Structures
OH
319
Chapter 14
Carbohydrates
HCOH
OH
O
HO
HO
HOCH
HCOH
OH
CH2OH
CH2OH
OH
HO
CH2OH
HCOH
CH2OH
unwind
c)
Open-chain
HC O
OH
HOCH
HO
and
d)
CH2OH
O
OH
CH2OH
HOCH
OH
HOCH
OH
C OH
CH2OH
CHOH
HO
C O
C OH
C OH
HO
C H
C H
C OH
C OH
C OH
C OH
C OH
CH2OH
D-fructose
320
CH2OH
enol
HCOH
HOCH
CH2OH
CH2OH
HCOH
HCOH
HO
CH2OH
C H
CH2OH
D-glucose
HC O
HO
C H
HO
C H
C OH
H
D-mannose
C OH
CH2OH
Carbohydrates
Chapter 14
14.12
14.4B
CH2OH
H C
HO C
H C
iduronic acid
oxidized on C-6
xylonic acid
oxidized on C-1
CH2OH
OH
HO C
HO C
OH
H C
OH
CH2OH
CH2OH
D-xylitol
D-arabitol
Section
CH2OH
1 4
OH
OH
OH
OH
OH
1
OH
O
OH
OH
OH
- H2O
CH2OH
CH2OH
OH
OH OH
OH
CH2OH
OH
OH
1,4
maltose
CH2OH
O
OH
CH2OH
O
OH
CH2OH
O
OH
O
OH
OH
- H 2O
OH
OH
OH
OH
OH
OH
1,4
Cellobiose
321
Chapter 14
Carbohydrates
OH
OH
O
HO
HO
OH
HO
OH
O
O
maltose
HO
OH
O
O
O
HO
OH
OH
OH
HO
OH
OH
cellobiose
(a)
5
O
HO
OH
1,5
(b)
HO
OOH
OH
1'
OH
HO
(d)
HO
1'
OH
HO 2
3
O
HO
OH OH
OH
1,4
O
OH
HO O
4
O 1
O
HO
OH
(c)
OH
OH OH
HO
6
1,3
OOH
OH
HO
OH OH
2,6
OH
a)
CH2OH
HO
O
HO
HO
HO
CH2OH
O
OH
OH
1,3
b)
O CH2OH
HO
HO
OH
CH2OH
O
OH
HO
322
-1,2
Carbohydrates
Chapter 14
f)
g)
h)
i)
glucose with opposite configurations for the -OH group attached to the
new chiral center, the former carbonyl group.
Fischer projections are structures drawn vertically with the most oxidized
carbon appearing at the top. They are not related spatially to real
structures. Haworth formulas are cyclic carbohydrate structures in the
form of cyclopentane and cyclohexane-type rings.
Amylose is the linear form of starch in which all of the glucose units are
linked -1,4 while amylopectin is branched, its main chain of glucose
units linked through an -1,4 glycosidic bond with -1,6 bondedbranches about every 25 monomer units.
Glycogen is a polymer of glucose with a main chain having -1,4
glycosidic bonds and -1,6 branches every 8-10 units. Cellulose is
polyglucose linked -1,4.
Type 1 diabetes involves the absence or near absence of insulin to
regulate body glucose concentrations. Type 2 diabetes is a more
complicated condition in which insulin is usually present but not
functioning properly.
323
Chapter 14
j)
k)
Carbohydrates
d)
e)
f)
g)
b) -D-idose
c) -D-talose
CH2OH
CH2OH
O OH
OH
OH
OH
O
OH
CH2OH
OH
324
OH
OH
OH
OH
d) -D-lyxose
O OH
OH
OH
OH
O
OH
OH
Carbohydrates
Chapter 14
2-deoxyribose
open-chain form
HC OH
CH2OH
O
OH
2-deoxyribose
Haworth form
HC OH
OH
CH2OH
14.21 Reactions: Section 14.4
CH2OH
O
CH2OH
O
OH
OH
OH
OH
OH
2-deoxyribose
ribose
HC O
(b)
HC OH
OHOH
OH
OH
HC OH
OH
CH2
OH OH
HO
CH2OH
(c) OH
HO
HC O
OH
O
CH2
OH
HO CH
HO CH
CH2OH
C O
HO CH
HC OH
HC OH
CH2OH
(d)
HO
HO
HC O
OH
OH
HC OH
HC OH
HC OH
HC OH
CH2OH
CH2OH
325
Chapter 14
Carbohydrates
OH
HO C
HO C
H C
HO C
HO C
H C
OH
H C
CH2OH
H C
OH
OH
HO C
HO C
H
H
H
H
H C
OH
OH
CH2OH
CH2OH
a/b are identical because you can rotate b in the plane of the page and it
will superimpose on a . a is also obviously meso and is therefore not optically
active. c/d are enantiomers. a is a diastereomer of c and d.
14.24 Reactions: Section 14.4
In the presence of acid, which also assumes an aqueous solution, the
and forms of D-glucose will rapidly come into equilibrium with the openchain aldehyde. Both the and anomers can react with methanol to form
the methyl acetal.
14.25 Structure: Section 14.5
ketoheptose
OH
(a)
OH
(b)
O
OH
HO
HO
aldopentose
OH
OH
OH
HO
HO
OH
OH
O
aldohexose
aldopentose
- 1,4
OH
OH
- 1,5
OH
OH
ketohexose
(c)
HO
O
aldopentose
OH
HO
- 2,6
OH
aldohexose
326
HO
OH
HO
ketopentose
OH
O
- 1,2
HO
OH OH
(d)
HO
Carbohydrates
Chapter 14
(a)
OH
(b)
OH
OH
OH
OHO
HO
OH
HO
HO
OH
OH
- 1,4
OH
OH
- 1,5
OH
OH
(c)
HO
OH
HO
HO
O
- 1,2
HO
O
OH
- 2,6
OH OH
(d)
HO
OH
HO
OH
OH
O
OH OH
OH
O
OH
OH
O
OH
O
OH
OH
O
OH
OH
O OH
OH
OH
327
Chapter 14
b)
Carbohydrates
HO
c)
O
OH
O
HO
O
OH
OH
O
HO
OH
O
O
HO
OH
OH
OH
O
HO
O
HO
O
OH
OH
d)
O
OH
O
OH
O
HO
OH
OH
O
HO
OH
OH
2,6
OH
2,4
O
HO
OH
14.28 Reactions: Sections 14.4 and 14.5
OH
OH
OH
O OH
OH
O
(a)
OH
OH
+ CH3OH
OH
OCH3
OH
(b)
OH
OH
O
OH
OH
+
OH
OH
O OH
OH HO
OH
OH
OH
OH
OH
O
OH
CO2H
(c)
OH
O
OH
OH
+
OH
OH
OH
HO
HO
OH
Cu2+
OH
CH2OH
328
+ Cu2O
O OH
OH HO
Carbohydrates
Chapter 14
(d)
OH
O
OH
O
HO
OH
OH
OH
OH
OH
OH
OH
OH
OH
O
HO
OH
OH
OH
OH
OH
329
H3C
H3C
H3C
CH3
CH3
15
Lipids
HO
Views of
Cholesterol
CHAPTER SUMMARY
15.1 The Nature of Lipids
Lipids can best be defined as biomolecules which are soluble to a
great extent in nonpolar solvents. In contrast to carbohydrates, proteins
and nucleic acids, lipids do not have polymeric forms. By virtue of their
hydrophobic nature they aggregate into large complexes, held together to a
significant degree by nonpolar interactions.
The structures of lipids are quite varied: triacylglycerols (fats and oils),
waxes, phospholipids, sphingolipids, steroids, eicosanoids, fat soluble vitamins,
and pigments. Some lipids are simple in structure while others are more
complex. Among these molecules are those which are esters in nature and
therefore saponifiable in aqueous base. Others are nonsaponifiable.
Many are completely nonpolar while others are amphipathic, that is, they
have a polar/nonpolar nature.
15.2 Waxes - Simple Esters of Long-Chain Alcohols and Acids
Waxes are functionally the simplest of the lipids and are probably the
most nonpolar.
15.3 Fats and Oils - Triesters of Glycerol
Fats and oils are triesters of glycerol and long-chain fatty
acids. The fatty acids are usually 10-24 carbons in length; they can be
Chapter 12
Lipids
331
Chapter 15
Lipids
332
Chapter 12
Lipids
D. Steroids
A fused multiple-ring system is the structural framework for steroids.
Cholesterol is the nonpolar, nonsaponifiable progenitor of the
metabolic and gonadal hormones such as cortisol, testosterone and
estrogen as well as the bile acids used for the intestinal absorption of fats
and oils. Many toxins fit into this lipid subclass.
CONNECTIONS 15.2 RU-486
E. Eicosanoids
Eicosanoids in the form of prostaglandins, prostacyclins,
thromboxanes, and leukotrienes are short-lived metabolites of fatty acids
which affect a variety of tissues in the body.
F. Vitamins
Vitamins A, D, E, and K are called the fat-soluble vitamins and must
be part of the diet for health and vigor.
G. Pigments
Many pigments found in algae, bacteria and plants, such as chlorophyll,
are lipid in nature. These molecules help to convert light energy to
metabolic energy by systems of conjugated bonds.
SOLUTIONS TO PROBLEMS
15.1 Structure and Reactions: Sections 15.2, 15.3
O
CH3(CH 2)14CO(CH 2)29CH 3
O
CH3(CH 2)24CO(CH 2)25CH 3
H2O
H2O
333
Chapter 15
Lipids
CH2O
C(CH2)14CH3
CH
CH2O
C(CH2)16CH3
C(CH2)7CH=CH(CH2)7CH3
O
C(CH2)7CH=CHCH2CH=CHCH2CH=CHCH2CH 3
Reduction with H2
CH2O
HO CH
CH2O
334
O
C(CH2)7CH2CH2(CH 2)7CH 3
O
C(CH2)7CH2CH2CH 2CH 2CH2CH2CH2CH 2CH2CH3
Chapter 12
Lipids
Rancidification O
CH2O
HO CH
CH2O
C(CH2)7COOH HOOC(CH2)7CH3
O
HOOCCH2COOH
C(CH2)7COOH
HOOCCH2COOH
HOOCCH2CH 3
Saponification
CH2OH
OC(CH2)7CH=CH(CH2)7CH3
Na
HO CH
CH2OH
OC(CH2)7CH=CHCH2CH=CHCH2CH=CHCH2CH3
Na
CH2OH
H3C
(a)
(b)
HO
OH
O
OH
HO
H3C
(c)
COOC
H3+N
HO
polar groups
nonpolar groups
CH2
H
335
Chapter 15
Lipids
O CH2OPOCH2CHCOO
NH3
R1COCH O
+
CH2OCR2
HOCH2CHCOONH3
+
serine
HOCH
CH2OH
glycerol
+ 4 H2O
HOPOH
R1COH HOCR2
fatty acids
15.12 Structures of Fats and Oils: Section 15.3
O
a.
b.
O CH2OC(CH 2)10CH 3
OH
phosphoric
acid
O CH2OC(CH 2)12CH 3
myristic
CH3(CH 2)10COCH O
CH3(CH 2)14COCH O
CH2OC(CH 2)10CH 3
palmitic
CH2OC(CH 2)16CH 3
stearic
c.
O
O CH2OC(CH 2)12CH 3
CH3(CH 2)12COCH
myristic
or
O CH2OC(CH 2)12CH 3
oleic
myristic
CH3(CH 2)7CH=CH(CH2)7COCH O
myristic
CH2OC(CH 2)7CH=CH(CH2)7CH3
oleic
336
CH2OC(CH 2)12CH 3
myristic
Chapter 12
d.
Lipids
For example, an
isolated triglyceride
molecule might have
three oleic acids while
palmitic another could have
three linoleics.
CH2OC(CH 2)7CH=CHCH2CH=CH(CH2)4CH3
linoleic
e.
b. hydrogenation
O
c. I2/CCl4
O
CH2OC(CH 2)16CH 3
O
CH2OC(CH 2)7CH-CH(CH2)7CH3
O
I I
CHOC(CH2)16CH 3
O
CHOC(CH2)7(CH-CHCH2)3CH 3
O
CH2OC(CH 2)14CH 3
CH2OC(CH 2)14CH 3
Chapter 15
b)
Lipids
b)
c)
be effective as a soap.
CH 3 CH 2 CO2 -Na + does not have a long nonpolar carbon chain and
d)
e)
f)
g)
338
Chapter 12
Lipids
CH3 OH
alcohol; polar
H is a hydrogen bond donor;
O is a hydrogen bond acceptor
CH3
aromatic ring;
nonpolar
CH3 OH
b.
unsaturation; nonpolar
ketone;
polar-hydrogen bond acceptor
HO
c.
ketone; polar
aldehyde; polar hydrogen bond acceptor
hydrogen bond
acceptor
O O
HO
CH CCH2OH
phenol; polar
H is a hydrogen bond donor;
O is a hydrogen bond acceptor
CH3
O
ketone;
polar-hydrogen bond acceptor
339
Chapter 15
Lipids
d.
alcohol
OH H3C
CH3
CNHCH2CO2H
carboxyl; polar
carbonyl O is a hydrogen bond
acceptor as is carboxyl O; H of
carboxyl is a hydrogen bond
donor
amide; polar
carbonyl O is a hydrogen bond acceptor;
amide N is a hydrogen bond acceptor;
amide H is a hydrogen bond donor
CH3
OH
HO
alcohol; polar
H is a hydrogen bond
donor; O is a hydrogen
bond acceptor
alcohol
schematic of a
bile acid
H2O
H2O
nonpolar
aggregation
nonpolar
fats & oils
nonpolar
ring system
polar
interactions
polar groups
chiral centers
H 3C
CH3
340
CH3
H2
H2
OH
CH3
CH3
Proteins
Chapter 16
16
Proteins
CHAPTER SUMMARY
Proteins are polymers of amino acids. With 20 different
fundamental amino acids as building blocks, an extraordinarily large variety
of proteins can be biosynthesized under the direction of the genetic code.
16.1 Structure of Amino Acids
A. Fundamental Structure - An Amine and An Acid
As the term amino acid describes, each monomer has an amine group
and a carboxylic acid group attached to a prochiral carbon. In
addition side chains can also be present. These range from a simple
hydrogen to long carbon chains with functional groups.
B. Ionization of Amino Acids
The amine and carboxyl groups exhibit typical acid-base behavior
which is pH-dependent. At low pH both groups are protonated:
the
amine group has a plus (+) charge and the carboxyl is neutral (0). As the
pH rises the carboxyl loses its proton becoming negatively charged (-).
At higher pH values the amine (+) deprotonates to produce a neutral
amine (0). The result of this sequential deprotonation is a series of
charged forms ranging from + to 0 to -. If the side chains are capable of
acid-base reactions, the number of possible charged forms
depends upon the number and types of amino acids present,
the pH, and the pK a of each ionizable group. This is true of
proteins as well as amino acids. The pH at which the molecule has a net
341
Chapter 16
Proteins
342
Proteins
Chapter 16
343
Chapter 16
Proteins
Proteins
Chapter 16
345
Chapter 16
Proteins
SOLUTIONS TO PROBLEMS
16.1 Amino Acid Structure: Ionization Section 16.1B
Arginine, lysine, and histidine have (+1) to (0) ionization transitions, while
aspartic acid, glutamic acid, cysteine, and tyrosine have (0) to (-1) transitions.
16.2 Ionized Forms of Amino Acids: Section 16.1
Lysine
8.9
2.2
+
H3NCHCOH
346
pKa values
are boxed.
O
+
H3NCHCO
H2NCHCO
H2NCHCO
(CH2)4
(CH2)4
(CH2)4
(CH2)4
NH3+
10.3
NH3+
NH3+
NH2
+2
+1
Net Charge
0
-1
Proteins
Chapter 16
Glutamic
Acid
O
+
H3NCHCOH
9.7
2.2
+
H3NCHCO
O
+
H3NCHCO
(CH2)2
(CH2)2
(CH2)2
COOH
4.3
COOH
COO
H2NCHCO
(CH2)2
COO
Net Charge
+1
-1
-2
Alanine
O
2.4
+
H3NCHCOH
9.9 CH
3
+
H3NCHCO
O
H2NCHCO
CH3
CH3
Net Charge
+1
Tyrosine
O
2.2
+
H3NCHCOH
9.1
+1
pKa values
are boxed.
O
+
H3NCHCO
O
H2NCHCO
CH2
CH2
OH
-1
10.1
OH
0
Net Charge
O
-
H2NCHCO
CH2
CH2
OH
O-
-1
-2
347
Chapter 16
Proteins
Aspartic
Acid
H2NCHCO
9.6
Serine
CH2
pH
COO
pKa1
9.2
CH2
COO
H3NCHCO
CH2OH
Equivalents of base
added
COOH
H3NCHCOH
CH2
COOH
pKa3
Arginine
H2NCHCO
pKa2
11.8
(CH 2) 3
C=NH
O
pH
H2NCHCO
9.1
pKa1
C=NH2
NH2
C=NH2
(CH 2) 3
NH2
NH2
H3NCHCOH
348
(CH 2) 3
C=NH2
(CH 2) 3
H3NCHCO
2.2
NH2
H3NCHCOH
CH2
Equivalents of base
added
CH2OH
H3NCHCO
2.2
H2NCHCO
H3NCHCO
3.65 pKa1
1.9
pKa2
pKa2
CH2OH
Equivalents of base
added
Proteins
Chapter 16
movement
glutamic acid
-COOH
net -1
2.2
0 -1
-1
towards
-NH 2
9.7
+1 0
+1
(+) pole
4.3
0 -1
-1
arginine
-COOH
net +1
2.2
0 -1
-1
towards
-NH 2
9.1
+1 0
+1
(-) pole
11.8
+1 0
+1
threonine
-COOH
net 0
2.2
0 -1
-1
no
-NH 2
9.1
+1 0
+1
movement
tyrosine
-COOH
net 0
2.2
0 -1
-1
no
-NH 2
9.1
+1 0
+1
movement
10.1
0 -1
histidine
-COOH
net 0
1.8
0 -1
-1
no
-NH 2
9.0
+1 0
+1
movement
6.0
+1 0
_
+
H3NCHCO
O
_
+
H3NCHCO
CH2
CH2
+
HN
NH
+2
NH
+1
pI =
6.0 + 9.0
H2NCHCO
CH2
NH
0
NH
-1
= 7.5
2
349
Chapter 16
Proteins
isoleucine
O
+
2.3
H3NCHCOH
9.8
CH-CH3
O
_
+
H3NCHCO
O
_
+
H3NCHCO
CH-CH3
CH-CH3
CH2CH 3 0
CH2CH 3
-1
CH2CH 3 +1
pI =
2.3 + 9.8
= 6.05
2
cysteine
O
+
1.7
H3NCHCOH
10.8
CH2
SH
8.3
O
_
+
H3NCHCO
O
_
+
H3NCHCO
CH2
CH2
CH2
SH
S_
S_
+1
pI =
-1
1.7 + 8.3
H2NCHCO
-2
= 5.0
2
16.6 Ionization ofAmino Acids: Section 16.1
glutamine
9.7
2.2
+
H3NCHCOH
+
H3NCHCO
(CH2)2
(CH2)2
CONH2
Net Charge
+1
CONH2
O
H2NCHCO
(CH2)2
CONH2
-1
0
2.2 +9.7
pI =
= 5.95
The pI for Gln is higher than that for Glu due to the loss
of ionizability of the side chain carboxyl group.
350
Proteins
Chapter 16
glutamic acid
O
2.2
+
H3NCHCOH
9.7
+
H3NCHCO
(CH2)2
COOH
4.3
Net Charge
+1
O
+
H3NCHCO
(CH2)2
(CH2)2
COOH
COO
H2NCHCO
(CH2)2
COO
-2
-1
2.2 +4.3
pI =
= 3.25
L-alanine
is S.
3
CH3
C
H2N
1
3
CH3
4
H
COOH
2
C
HOOC
2
D-alanine
is R.
4
H
NH2
1
Charge
at low
pH
+
NH3 Ala~Lys~Asp~Tyr~Asp~His~CySH~Leu~Phe~Gln
+
pKa 9.9
Charge
at +
pH 8.2
+
10.3
+
10.1
6.0
3.65
3.65
8.3
_
_
0
0 0
COOH
0
2.2
_
Chapter 16
Proteins
+1
2.0
Charge at
pH 7.4
-1
H3N
proline
H
The net charge
at pH 7.4 will be +1.
6.0
histidine
asparagine
NH2
11.8
+1
arginine
352
Proteins
Chapter 16
Ala, Ser, and Gly could work in a beta sheet structure because of their
small or nonexistent side chains which could allow the stacking of beta chains.
Pro with its ring structure would not fit into either of the conventional
secondary structures but rather would be a place where one secondary
structure could transition into another. Gly, with its ability for free rotation, could
also be found at bends and breaks in regular secondary structure.
Lys has a charged, nitrogen-containing side chain under most pH
conditions. It could exist in an alpha helix if there weren't any other positively
charged groups in the area. Also at pHs above the pKa of the R group, Lys
would be "happy" in a helix.
16.15 Hierarchy of Protein Structure: Section 16.3C
H
NH
CHCH2
O C
NH
CCH2CH 2CH
NH
CHCH2
O C
O C
NH
CCH2CH 2CH
O
O C
NHCHC
NHCHC
CH2
NHCHC
CH2
O
+
H
Ser
Ser
(CH2)2
Gln
C
O
+H N
H
+
O
H
O
NHCHC
(CH2)2
C Gln
O
+H N
H
+
353
Chapter 16
Proteins
NH
C
H
PTH-Tyr
NH
CH2CH2SCH3
C
CH2
Met
PTH-Gly
OH
16.20 Determination of Protein Structure: Section 16.5B
The theoretical yield for a five-step N-terminal sequential degradation would be
Step 1:
85%
Step 2:
(0.85) * 85% = 72.25%
Step 3:
(0.85) * 72.25% = 61.4%
Step 4:
(0.85) * 61.4% = 52.2 %
Step 5:
(0.85) * 52.2% = 44.4%
16.21 Determination of Protein Structure: Section 16.5B
Chymotrypsin digestion of the polypeptide in Example 16.4 would have
produced the fragments: Gly ~ His ~ Lys ~ Gly ~ Phe and free Ile.
Trypsin digestion followed by chymotrypsin would produce the following three
fragments: Gly ~ His ~ Lys, Gly ~ Phe and free Ile.
16.22 The Organic Synthesis of Polypeptides: Section 16.6
For the hypothetical amino acids - A, B, C, and D - 4! or 24 possible
combinations exist.
ABCD
ADBC
BCDA
BACD
ABDC
ADCB
BCAD
BADC
ACDB
BDAC
ACBD
BDCA
354
Proteins
Chapter 16
CDAB
CDBA
CABD
CADB
CBDA
CBAD
DABC
DACB
DBCA
DBAC
DCAB
DCBA
e)
f)
g)
proline
serine, threonine,
asparagine, glutamine,
histidine, tryptophan, tyrosine
threonine, isoleucine
HN
modified
Pro
H
CHCH2OH
CH
CH
HN
CH
Gly
O
C
HN
CH2
ODD
BOND
CH
N
CH H
OH
O
Asn
CH
HN
CH2CONH2
C
NH
Ile
H 2C
CH
HO
hydroxy
Trp
CH
HN
CySH
C
O
CH2
CH3
CH
CH2CH3
O
NH
Gly
355
Chapter 16
Proteins
10.3
b.
= 5.7
+
9.9
10.3
+
Lys
pI=10.3
1.7
Thr ~ Phe ~ Thr ~ Ser ~ Cy-COOH
S
6
Glu
Val
change of +2
C
6
Glu
Lys
change of +4
Chesapeake
92
Arg
Leu
change of -2
Hasharon
47
Asp
His
change of +2
Koln
98
Val
Met
no change
356
Proteins
Chapter 16
pole
+
pole
HbA
HbS
change of +2
NH
PTH-Leu
NH
PTH-Met
CH2
C
H
CH2CH2SCH3
CH(CH3)2
NH
PTH-His
+
H3NCHCOOH
CH2OH
C
H
Ser
CH2
N
NH
357
Chapter 16
Proteins
Leu~Arg
Ala~Leu~Phe
Leu~Arg
Ala~Leu~Phe
Tyr~Ile~Phe~Lys
must be between the other two
carboxypeptidase
peptide
Phe>Leu>Ala
C-terminus is Ala~Leu~Phe
dansyl
chloride
DNS-Leu
N-terminus
trypsin
trypsin
Leu~Arg~Tyr~Ile~Phe~Lys~Ala~Leu~Phe
chymotrypsin
dansyl
chloride
358
carboxypeptidase
Proteins
Chapter 16
from peptide C
Lys~Arg~(Ala, Gly)Phe
DNS-Ala
Sequence is Ala~(Gly, Phe)
Lys~Arg~Ala~Gly~Phe~Leu~Lys~Ala
Ala2
Arg1
Gly1
Leu 1
Lys2
Phe1
aminopeptidase
carboxypeptidase
chymotrypsin
trypsin
N-terminus is Lys
C-terminus is Ala
peptide A
peptide B
sequence is
unknown at this point
Lys is probably at
N-terminus; Arg may
precede it.
But Ala is at
C-terminus.
trypsin
The key factor is to keep an open mind while
piecing the fragments together.
peptide C + free amino acids
359
recombinant DNA
NH2
N
O O
genetic code
O
N
HOPOPOPO
17
viruses
_O _O _ O
AIDS
Nucleic Acids
CHAPTER SUMMARY
17.1 The Chemical Structure of Nucleic Acids
Nucleic acids are the biopolymers which constitute our genes.
The monomer unit is called a nucleotide. A nucleotide is composed of a
heterocyclic base, either a purine or pyrimidine, a ribose or
deoxyribose sugar unit, and a phosphate group.
The two types of nucleic acids are DNA (deoxyribonucleic acid) and
RNA (ribonucleic acid). These differ in their chemical makeup in the sugar
group: deoxyribose in DNA and ribose in RNA; and in the heterocyclic bases:
DNA has adenine(A), guanine(G), thymine(T), and cytosine(C)
while RNA has uracil(U) in place of thymine. The primary structures of
DNA and RNA polymers have phosphodiester bridges between (deoxy)ribose
units to form a sugar-phosphate backbone. The bases are covalently bound
from the hemiacetal group of the sugar to a ring nitrogen. Nucleic acid
polymers are usually written from the 5 end (of the sugar unit) to the 3 end, left
to right. Often the backbone is represented simply as a horizontal line with the
bases protruding. The acidity of the polyprotic phosphate imparts a negative
charge and hydrophilicity to the sugar-phosphate backbone at physiological
pH.
The polymerization of just a few nucleotides produces an
oligonucleotide while many comprise a polynucleotide and a very large
number, a nucleic acid.
360
Nucleic Acids
Chapter 17
361
Chapter 17
Nucleic Acids
362
Nucleic Acids
Chapter 17
predisposition to disease,
evolutionary progress.
CONNECTIONS 17.2
AIDS
congenital
malformations
or
syndromes,
or
17.7 Viruses
Viruses are species consisting of nucleic acids, usually ssRNA,
encased in a protein coat and require a host organism for their replication.
Once a virus invades a host cell, it uses its own reverse transcriptase
enzyme to encode its genome into the host DNA thereby ensuring its survival.
AIDS, acquired immune deficiency syndrome, is produced by a
retrovirus that attacks the immune system.
17.8 Oncogenes
Oncogenes are those genes which are believed responsible for
uncontrolled, cancerous cell growth. Cancer can be due to the production of
growth factors or the inhibition of growth suppressors.
17.9 Recombinant DNA and Biotechnology
Manipulation of the genetic code through recombinant DNA allows
molecular biologists to modify and transfer genes both for the study of disease
and the production of new cellular characteristics.
CONNECTIONS 17.3 DNA Fingerprinting
SOLUTIONS TO PROBLEMS
17.1 Structure: Section 17.1, Chapters 15, 16, 17
Carbohydrates
Functional laldehydes
Groups
lketones
lalcohols
Macro
Structure
lpolymers
of
saccharides
Lipids
lalkyl
Proteins
Nucleic Acids
groups
and rings
lcarboxylic and
phosphoric
acids and
esters
lamines
lcarbohydrate
lcarboxylic
lheterocyclic
acids
lamides
bases
lphosphate
esters
lno
lpolymers
polymers
laggregates
of lpolymers of
amino acids nucleotides
(base, sugar,
phosphate)
363
Chapter 17
Nucleic Acids
5'
or
dS
dS
dS
dS
OH 3'
NH2
U
HO
O
OH
O P O
O-
N
NH2
C
O
N
O
OH
A
O P O
O
OO
OH
O P O
O-
N
N
O
N
N
G
O
O
OH
O P OO-
364
NH
N
NH2
Nucleic Acids
Chapter 17
NH2
CMP
HN
O
O
-O P O P O
OO-
N
O
O
-O P O
O-
OH OH
17.5 Structure: Section 17.2
O
OH
OH
HO-P-O-P-O O
5'
3'
antisense strand
3'
5'
codon
anticodon
peptide
5'
365
Chapter 17
Nucleic Acids
anticodon
3'
peptide
b)
5'
modified codon
anticodon
3'
5'
peptide
H2N
NH
O
-O P O
O-
N
O
O
OH
O
OH
O
NH
N
O
OH
366
OH
O
O P OO-
OH OH
O
-O P O
O-
N
H2N
OH OH
O
N
N
OO P OO
Nucleic Acids
Chapter 17
3'
3'
C A T T G C A G C G A A
5'
5'
G U A A C G U C G C U U
3'
tRNA (anticodon)
peptide
Val
Thr
Ser Leu
moles
moles
moles
12
moles
deoxyribose
12
moles
phosphate
10 nucleotides
o
34 A
helix turn
10 nucleotides
helix turn
10-10 meters
o
A
Number of moles
Ribose
Phosphate
ATP
adenine
FAD
flavin
adenine
1
1
nicotinamide 1
adenine
1
flavin
NADH
FMN
367
Chapter 17
Nucleic Acids
368
18
Spectroscopy
CHAPTER SUMMARY
18.1 Spectroscopy
Spectroscopy involves instrumental methods for determining the
structure of organic compounds by measuring and interpreting their interaction
with electromagnetic radiation.
Radiation can cause a measurable
transformation or pertubation in molecules such as molecular rotation, bond
vibration, promotion of electrons to higher energy levels, or even permanent
disruption of the molecule.
Energy is described in wavelengths or frequency. The wavelength is
the distance between two maxima in an energy wave. Frequency is the
number of waves per unit distance or cycles per second. The energy of a
electromagnetic radiation is directly proportional to frequency (the greater the
frequency, the greater the energy), and inversely proportional to wavelength
(the shorter the wavelength, the greater the energy).
Spectroscopy is possible because molecules absorb exactly the
wavelength of energy necessary for a particular permutation and the absorption
of these wavelengths is often characteristic of a particular structural feature. It is
not possible either to accumulate radiation of lower energies to attain the total
needed for a molecular transition or to extract it from higher energy radiation; it
must be the exact wavelength or frequency corresponding to the energy of the
transition. A spectrometer is an instrument that measures the absorption of
energy by a chemical compound.
369
Chapter 18
Spectroscopy
H NMR
370
Spectroscopy
Chapter 18
to
B. Integration
The area under an NMR peak can be determined by integration.
Comparison of the integration (areas) of the signals on an NMR
spectrum gives the ratio of hydrogen types in a molecule; if the molecular
formula is known, the actual number of each type of hydrogen can be
determined.
C. Splitting
Splitting is caused by the influence of the magnetic fields
generated by hydrogens on adjacent carbons on the total magnetic field
felt by a proton. The number of peaks into which a signal is split is one
more that the total number of hydrogens on directly adjacent carbons.
D. Summary of Proton NMR
To interpret the proton NMR of a compound, the following procedure
is useful. First, using integration write a possible fragment for each peak
in the spectrum; for example if the area of a peak is 3, write down CH3 as
an initial idea. Arrange additional atoms in reasonable and simple units.
Using the chemical shift and splitting, start putting the pieces of the
puzzle together until a complete compound has been constructed that is
consistent with chemical shift, integration, and splitting.
18.5 Carbon-13 NMR
Carbon-13 NMR requires sophisticated instrumentation since 13 C is
only 1.1% of naturally occurring carbon. 13 C NMR is useful in the following
ways. (1) The number of peaks in a spectrum is the number of non-equivalent
carbons in the molecule. (2) The chemical shift provides information about the
structural environment of each carbon. The range in 13 C NMR is more than 200
delta units. (3) The number of peaks into which a signal is split is one more
than the number of hydrogens bonded to that carbon.
CONNECTIONS 14.1: MRI: Magnetic Resonance Imaging
371
Chapter 18
Spectroscopy
Spectroscopy
Chapter 18
(b) CH3CH2CH
a
b
c
(c) CH3CCH3
a
a
(d) CH3CCH2CH3
a
b c
373
Chapter 18
Spectroscopy
O
(b) BrCH2CH2CCHCl2
a
1
2 Br
= 3
b next to C=O,
= 2-2.5
1
2.5 Cl
2.5 Cl
= 6
O
c
CHCOH d
(c)
a
OH b
a: These are aromatic hydrogens and generally come in the = 7-8 range.
b: Alcohol hydrogens are variable and cannot be accurately predicted.
c: If this hydrogen were next to nothing it would be an alkane and come around
= 1. But it is next to three groups that shift it in addition to the normal = 1.
The benzene shifts it another 1.4, the C=O shifts it another 1, and the oxygen
shifts it another 2.4-3.4, lets say 2.9. So the approximate chemical shift will be
1+1.4+1+2.9 or = 6.3.
d: Carboxylic acid hydrogens come in the = 9-12 region.
18.5 Proton NMR: Integration
(1) First add up the integration values: 149+58+91=298
(2) There are 10 hydrogens causing this total integration. Divide 298 by 10;
each hydrogen is worth 29.8 integration units.
(3) Since a hydrogen is worth 29.8 integration units, if we divide 29.8 into the
integration units for each signal, we will obtain the number of hydrogens in each
signal.
= 7: 149 units divided by 29.8units/H gives us 5 hydrogens.
= 2.3: 58 units divided by 29.8 units/H rounds off to 2 hydrogens.
= 1.1: 91 units divided by 29.8 units/H gives us the nearest whole number, 3
hydrogens.
18.6 Proton NMR: Splitting
The number of peaks into which a signal is split is one more than the total
number of hydrogens on directly adjacent carbons.
374
Spectroscopy
Chapter 18
(a) CH3CH2OH
(b)
triplet quartet
triplet triplet
OH
(d)
triplet pentet
18.7 Proton NMR
O
a) CH3CCH 3
O
COCH3
CH3
c) CH 3OCHCH3
a
b c
a b
d) CH3CH 2
CH3
(c)
CHCH2OH
sextet
doublet
OH
(e) CH3CHCH3
CHCH2CH3
b)
CH2CH2OH
doublet
triplet
doublet septet
doublet
CH2CH 3
375
Chapter 18
Spectroscopy
CH 3
c
e
CH 3
d CH a
3
CH 3
CH 3 b
d
CH 3
e
f
c
e
i
h
a CH 3 b
c b
CH 3
CH 3 a
6 types of carbons
6 NMR signals
9 types of carbons
9 NMR signals
3 types of carbons
3 NMR signals
CH 3 c
CH 3
d
CH 3 b
d
c CH 3
a
e
e
CH 3
d
f
CH 3
g
CH 3 a
bCH 3 a
CH 3
CH 3
5 types of carbons
5 signals
135,134,127,21,16
CH 3 b
CH 3
7 types of carbons
3 types of carbons
7 signals
3 signals
136,134,132,128,21,20,15 134,131,19
The methyl groups carbons are the signals in the range of 15-21; the chemical
shifts around 127-136 are aromatic carbons.
18.10 Carbon-13 NMR
CH 3
In hexamethylbenzene, the six methyl carbons are
CH 3
CH 3
equivalent and the six benzene carbons are equivalent. As a result, there are only two carbon-13
CH 3
CH 3
NMR signals in the spectrum.
CH 3
18.11 Carbon-13 NMR with Splitting
C 3H8O isomers
OH
CH 3CH 2CH 2OH
a
3 signals
a: quartet
b: triplet
c: triplet
376
CH3CHCH 3
b a
2 signals
a: quartet
b: doublet
CH3CH 2OCH 3
3 signals
a: quartet
b: triplet
c: quartet
Spectroscopy
Chapter 18
Chapter 18
Spectroscopy
85
O
57
CH 3
C
77
CH 2CH 3
378
Spectroscopy
Chapter 18
69
CH 3CH 2CH=CHCH 2CH 3
69
18.14
a)
O
b)
CCH3
c) CH3C
CH
d) CH 3CH 2COH
e) CH3CH 2CH 2NH 2
CH3NHCH2CH 3
(CH 3)3N
f) CH3CH 2C
O
g)
CH
379
Chapter 18
Spectroscopy
there is the characteristic O-H stretch around 3400-3650 cmin the alcohol but absent in the ether.
h) CH3CH 2OH
i) CH3NO2
O
j)
both have carbonyl and benzene signals but the acid has
a broad O-H stretch between 2500 and 3300 cm-1
COH
k) CH3CH 2NHCH3
(a) CH4
(b) CH3OCH 3
= 3.3-5 singlet
O
= 7-8 singlet
= 2.7-3.8
(c) CH3CCH 3
= 2-2.5 singlet
(d)
(h)
a
(i)CH 3
a
(e) CH3Br
CH 3 a: = 7-8 singlet, 5H
b: = 2.3-2.9 singlet, 3H
b
CH 3 a: = 2.3-2.9 singlet, 6H
b: = 7-8 singlet, 4H
a
O
(j)
a
a: 7-8 singlet, 5H
CH 2OCCH 3 b: 5.5 singlet, 2H
c: 2.3 singlet, 3H
b
c
380
Spectroscopy
Chapter 18
a: = 2.7-3.8 triplet, 4H
b: = 1-1.6 pentet, 2H
a: = 7-8 singlet, 5H
b: = 3.4 singlet, 2H
c: = 4.5 singlet, 2H
CH 2CCH 2Cl
a
c
c d
CH 2CH 3
(p)
CH 2NCH 2CH 3
a
b c
(r)
CHCH 3
Br
a: = 4.5-6 singlet, 2H
b: = 3.3-5 quartet, 4H
c: = 0.9-1.6 triplet, 6H
a: = 7-8 singlet, 5H
b: = 4.5 quartet, 1H
c: = 1.3 doublet, 3H
(b)
(c)
b
O CH 3
CH 3COCCH 3 b
a
CH 3
b
CH 3CH 2OH
a b c
O
a b a
CH 3CHCH 3
Br
a: = 2.1, singlet, 3H
b: = 1.4, singlet, 9H
a: = 1.1, triplet, 3H
b: = 4.4, quartet, 2H
c: = 3.6, singlet, 1H
a: = 2.1, singlet, 3H
b: = 2.4,quartet, 2H
c: = 1.1, triplet, 3H
a: = 1.7, doublet, 6H
b: = 3.4, heptet, 1H
381
Chapter 18
Spectroscopy
O
(f)
a: = 2.0, singlet, 3H
b: = 11.4, singlet, 1H
CH 3COH
a
b
Cl
(g)
ClCH 2CHCl
a b
(h)
CH 3
a
a
a: = 7.2, singlet, 5H
b: = 2.3, singlet, 3H
b
b
i)
a: = 3.9, doublet, 2H
b: = 5.8, triplet, 1H
a
a: = 7.3, singlet, 10H
b: = 6.1, singlet, 1H
CH
Cl
b O c
CHCCH 3
j)
a
a
(k)
O
a b
CH 3CHCOH
c
Cl
a: = 1.8, doublet, 3H
b: = 4.5, quartet, 1H
c: = 11.2, singlet, 1H
O
(l)
CH 3CH 2OCCHCl 2
a b
c
O
382
a: = 1.4, triplet, 3H
b: = 4.3, quartet, 2H
c: = 6.9, singlet, 1H
a: = 1.3, triplet, 6H
b: = 4.2, quartet, 4H
c: = 3.4, singlet, 2H
Spectroscopy
n)
Chapter 18
a: = 7.2, singlet, 5H
b: = 2.7, quartet, 2H
c: = 1.3, triplet, 3H
CH2CH 3
b c
CH 3 a
CH 3 a
CH 3CH 2CHCH 3
a
CH 3CHCH 2Cl
b c
Cl
four signals
four signals
three signals
a
CH 3CCH 3 a
b
Cl
two signals
(c) Dibromobenzenes
Each isomer has a different number of different types of carbons and thus can
easily be identified by C-13 NMR.
Br
b
c
Br
b
c
ortho: 134,128,125
3 types of C's, 3 signals
Br
d
c
Br
a
a Br
meta: 134,131,130,123
4 types of C's, 4 signals
b
a
Br
para: 133,121
2 types of C's, 2 signals
383
Chapter 18
Spectroscopy
CH 3
c
CH3CHCH 2OH
CH 3
CH3CCH 3a
b
OH
2 types of C
2 signals
CH3CH 2CHCH 3
OH
4 types of C
4 signals
4 types of C
4 signals
a
a
3 types of C
3 signals
a
a
CH3 c
CH3CHOCH3
4 types of C
4 signals
3 types of C
3 signals
2 types of C
2 signals
CH3CH 2OCH2CH 3
CH 3
b c
CH3CHCH 2CH 3
CH 3
a
CH3CCH 3a
CH 3
a
3 types of carbons
3 signals
4 types of carbons
4 signals
2 types of carbons
2 signals
d e
cb
O
5 types of carbons
5 signals
O
3 types of carbons
3 signals: 212,35,8
CH 3
b c d
CH3CHCCH 3
O
4 types of carbons
4 signals
CH 3
CH 3 CH 3
C
b a
CH 3
CH 3 CH 3
a
384
Spectroscopy
Chapter 18
CH 3CH 2OH
a
There is only one kind of carbon and thus only one signal.
Since the carbons have three attached hydrogens the one
signal appears as a quartet
CH 3OCH3
a
(b) C 4H8O
O
b
CH3CH 2CCH 3
a
4 signals
a: quartet b: triplet
c: triplet d: doublet
4 signals
a: quartet b: triplet
c: singlet d: quartet
(c) C 4H10
a
CH3CHCH
c
a CH 3
3 signals
a: quartet b: doublet
c: doublet
a
c d
a
a
CH 3
CH3CHCH 3
b
2 signals
a: quartet
2 signals
a: quartet
b: triplet
b: doublet
aCH
CH 3
CH3CHCH 2CH 3
b
4 signals
a: quartet b: doublet
c: triplet d: quartet
CH3CCH 3a
CH 3 a
2 signals
a: quartet
b: singlet
385
Chapter 18
Spectroscopy
a: = 161; doublet
O CH3
c
b: = 81; singlet
HCOCCH3
a
c: = 28; quartet
CH3
c
115
165
55
CH3O
190
CH
131
115
133
No. of
M + 1
carbons = 0.011 x M
8.8
= 0.011 x 100
= 8
No. of
b) C 2 H 5 Cl carbons
M + 1
2.2
= 0.011 x M = 0.011 x 100 = 2
The M + 2 peak is 33% of M indicating one chlorine.
M = 2 C's (24) + 1 Cl (35) + 5 H (5) = 64
No. of
c) C 3 H 5 BrO carbons
M + 1
1.3
= 0.011 x M = 0.011 x 40 = 3
The M + 2 peak is almost equal to the M indicating the presence of one
bromine (or three chlorines).
M = 3 C's (36) + 1 Br (79) + 1 O (16) + 5 H (5) = 136
d) C H 4 S
No. of
carbons
M + 1
1.1
= 0.011 x M = 0.011 x 100 = 1
The M + 2 peak is 4.5% of M indicating one sulfur.
M = 1 C (12) + 1 S (32) + 4 H (4) = 48
No. of
e) C 2 H 2 Cl 2 carbons
386
M + 1
= 0.011 x M
1.8
= 0.011 x 80
= 2
Spectroscopy
Chapter 18
M + 2
54
=
= 0.675
M
80
The M + 2 peak is 0.675 of M peak indicating the presence of two
chlorines.
M = 2 C's (24) + 2 Cl's (70) + 2 H (2) = 96
No. of
f) C 6 H 4 Br 2 carbons
M + 1
= 0.011 x M
3.3
= 0.011 x 50
= 6
M + 2
99
=
= 1.98
M
50
The M + 2 peak is twice M indicating the presence of two
bromines.
M = 6 C's (72) + 2 Br's (158) + 4 H (4) = 234
g) C 3 H 9 N
No. of
carbons
M + 1
2.5
= 0.011 x M = 0.011 x 75 = 3
The M peak is odd indicating the presence of an odd number of
nitrogens.
M = 3 C's (36) + 1 N (14) + 9 H (9) = 59
No. of
h) C 7 H 5 OCl carbons
M + 1
= 0.011 x M
2.3
= 0.011 x 30
= 7
M + 2
10
=
= 0.33
M
30
The M + 2 is one third of M indicating one chlorine.
M = 7 C's (84) + 1 Cl (35) + 1 O (16) + 5 H (5) = 140
No. of
i) C 2 H 4 S 2 carbons
M + 1
= 0.011 x M
1.5
= 0.011 x 70
= 2
M + 2
6.3
=
M
70 x 100% = 9%
M + 2 is 9% of M indicating two sulfurs (4.5% of M for each).
M = 2 C's (24) + 2 S's (64) + 4 H (4) = 92
387
Chapter 18
Spectroscopy
O
CH 3CH 2CH 2CH 2CH 2C+
O
CH 3CH 2CH 2CH 2CH 2CCH2CH 3
c) R1
CH3
CH 3CH 2CCH2CH3
+ CCH2CH3
+
CH 3CH 2CCH2CH3
(133) and
d) R1CHR2
OH
(147)
Spectroscopy
Chapter 18
87 - 58 = 29 indicating other R is CH3CH 2-
R1COR2
R1C+
COR2
CH 3(CH 2)5C+
85
113
O
b) CH3CH 2+
29
c) CH3(CH 2)5+
CH 3CH 2C+
57
O
CH 3(CH 2)5C+
85
e)
113
+
77
O
CH 3(CH 2)3+
57
CH 3(CH 2)3C+
85
O
+COH
45
O
d) CH3+
15
CH 3C+
43
O
+COCH 2CH 3
73
CH2+
91
389
Chapter 18
f)
Spectroscopy
+
CCH2CH3
CH2CH 2CH3
161
77
CH3
g) +CHCH
CHCH2CH2CH2CH 3
111
CH3
C+
CH2CH 2CH3
147
CH3
CCH2CH3
+
133
+
CH3CH 2CHCH CHCH2CH2CH2CH 3
125
CH3
CH3CH 2CHCH
97
CH3 CH3
h) +CH2C
CCH3
83
390
CHCH2+
CH3
i) +CH2NCH2CH 3 ,
72
CH3
CH 3CH 2CH 2NCH2+
86