Introduction to Organic Molecules and Functional Groups 3±1

C Orrggaanniicc M
Chhaapptteerr 33:: IInnttrroodduuccttiioonn ttoo O Moolleeccuulleess aanndd FFuunnccttiioonnaall G
Grroouuppss

TTyyppeess ooff iinntteerrm

moolleeccuullaarr ffoorrcceess ((33..33))

Type of force Cause Examples

van der Waals Due to the interaction of temporary dipoles All organic compounds
(VDW) • Larger surface area, stronger forces
Increasing strength

• Larger, more polarizable atoms, stronger

forces
dipole–dipole Due to the interaction of permanent dipoles (CH3)2C=O, H2O
(DD)
hydrogen bonding Due to the electrostatic interaction of a H atom H2O
(HB or H-bonding) in an O–H, N–H, or H–F bond with another N,
O, or F atom.
ion–ion Due to the interaction of two ions NaCl, LiF

PPhhyyssiiccaall pprrooppeerrttiieess

Property Observation
Boiling • For compounds of comparable molecular weight, the stronger the forces the higher
point the bp.
(3.4A) CH3CH2CH2CH2CH3 CH3CH2CH2CHO CH3CH2CH2CH2OH
VDW VDW, DD VDW, DD, HB
MW = 72 MW = 72 MW = 74
bp = 36 oC bp = 76 oC bp = 118 oC

Increasing strength of intermolecular forces

Increasing boiling point

3.1 For compounds with similar functional groups, the larger the surface area, the higher
the bp.
CH3CH2CH2CH3 CH3CH2CH2CH2CH3
bp = 0 oC bp = 36 oC

Increasing surface area

Increasing boiling point

• For compounds with similar functional groups, the more polarizable the atoms, the
higher the bp.
CH3F CH3I
bp =
78 oC bp = 42 oC

Increasing polarizability
Increasing boiling point
Chapter 3±2

Melting • For compounds of comparable molecular weight, the stronger the forces the higher
point the mp.
(3.4B)
CH3CH2CH2CH2CH3 CH3CH2CH2CHO CH3CH2CH2CH2OH
VDW VDW, DD VDW, DD, HB
MW = 72 MW = 72 MW = 74
mp =
130 oC mp =
96 oC mp =
90 oC

Increasing strength of intermolecular forces

Increasing melting point

• For compounds with similar functional groups, the more symmetrical the
compound, the higher the mp.

CH3CH2CH(CH3)2 (CH3)4C
mp =
160 oC mp =
17 oC

Increasing symmetry
Increasing melting point
Solubility Types of water-soluble compounds:
(3.4C) • Ionic compounds
• Organic compounds having
5 C’s, and an O or N atom for hydrogen bonding (for
a compound with one functional group).

Types of compounds soluble in organic solvents:

• Organic compounds regardless of size or functional group.
• Examples:
CCl4 CCl4
soluble soluble
O
CH3CH2CH2CH3 C
CH3 CH3
butane H2O H2O
insoluble acetone soluble

Key: VDW = van der Waals, DD = dipole–dipole, HB = hydrogen bonding

MW = molecular weight

R
 Reeaaccttiivviittyy ((33..88))
• Nucleophiles react with electrophiles.
• Electronegative heteroatoms create electrophilic carbon atoms, which tend to react with
nucleophiles.
• Lone pairs and  bonds are nucleophilic sites that tend to react with electrophiles.

CH3
CH3CH2 Cl OH CH3 O CH3

+
+ CH3 N CH3

electrophilic site basic and nucleophilic site

 Introduction to Organic Molecules and Functional Groups 3±3

Chapter 3: A
Annssw
weerrss ttoo PPrroobblleem
mss

3.1
H OSO3H H2SO4
CH3CH2 OH CH3CH2 OH2 + HSO4 CH3CH3 no reaction

Na+ H NaH
CH3CH2 O H CH3CH2 O Na+ + H2 CH3CH3 no reaction

3.2 Identify the functional groups based on Tables 3.1, 3.2, and 3.3.

alkene alkene
(double bond) (double bond)
HO CO2H ether O CO2CH2CH3
O

HO carboxylic acid N ester

OH H
NH2
shikimic acid amide oseltamivir
alcohols
amine
(hydroxy groups)

3.3 One possible structure for each functional group:

O O O O
C C C C
a. aldehyde = R H CH3CH2CH2 H c. carboxylic acid = R OH CH3CH2CH2 OH

O O O
O
b. ketone = C C R C CH3
C CH3 CH2CH3 d. ester = R O
R R CH3CH2 O

3.4 One possible structure for each description:

O O

a. C5H10O CH3CH2CH2CH2 C H CH3CH2CH2

C
CH3
aldehyde ketone
O H O H
ketone ketone
b. C6H10O C C C C H
CH3CH2 C CH3 CH3CH2 C C
H H H H
alkene
alkene
Chapter 3±4

3.5 Summary of forces:

• All compounds exhibit van der Waals forces (VDW).
• Polar molecules have dipole–dipole forces (DD).
• Hydrogen bonding (H-bonding) can occur only when a H is bonded to an O, N, or F.

a. c. (CH3CH2)3N e. CH3CH2CH2COOH
only nonpolar C–C • VDW forces • VDW forces
and C–H bonds • polar C–N bonds - DD • polar C–O bonds
VDW only • no H on N so and a net dipole - DD
no H-bonding • H bonded to O -
H-bonding
O
b. d. CH2 CHCl f. CH3 C C CH3

• VDW forces • VDW forces only nonpolar C–H and

• 2 polar C–O bonds • polar C–Cl bond - DD C–C bonds
and a net dipole - DD VDW only
• no H on O so
no H-bonding

3.6 One principle governs boiling point:

• Stronger intermolecular forces = higher bp.
Increasing intermolecular forces: van der Waals < dipole–dipole < hydrogen bonding

Two factors affect the strength of van der Waals forces, and thus affect bp:
• Increasing surface area = increasing bp.
Longer molecules have a larger surface area. Any branching decreases the surface area of a
molecule.
• Increasing polarizability = increasing bp.

a. (CH3)2C=CH2 or (CH3)2C=O c. CH3(CH2)4CH3 or CH3(CH2)5CH3

only VDW VDW and DD longer molecule, more surface area

polar, stronger intermolecular forces higher boiling point
higher boiling point

b. CH3CH2COOH or CH3COOCH3 d. CH2 CHCl or CH2 CHI

no H-bonding I is more polarizable.

VDW, DD, and H-bonding higher boiling point
stronger intermolecular forces
higher boiling point

3.7 Increasing intermolecular forces: van der Waals < dipole–dipole < hydrogen bonding

O O
C C CH3
CH3CH2 NH2 H N
CH3
N–H bonds allow for hydrogen bonding. no hydrogen bonding
stronger intermolecular forces weaker intermolecular forces
higher boiling point
 Introduction to Organic Molecules and Functional Groups 3±5

3.8
a. or NH2 b. or

more polar
stronger intermolecular forces more spherical
(H-bonding) packs better
higher mp higher mp

3.9 Compare the intermolecular forces to explain why sodium acetate has a higher melting point than
acetic acid.

O O
C C
CH3 OH CH3 O– Na+
acetic acid sodium acetate

a. VDW, DD, and H-bonding a. VDW, DD, ionic bonds

b. not ionic, lower melting point b. Ionic bonds are the strongest: higher melting point.

3.10 In the more ordered solid phase, molecules are much closer together than in the less ordered
liquid phase. The shape of a molecule determines how closely it can pack in the solid phase so
symmetry is important. In the liquid phase, molecules are already farther apart, so symmetry is
less important and thus it doesn't affect boiling point.

3.11 A compound is water soluble if it is ionic or if it has an O or N atom and
5 C’s.

a. CH3CH2OCH2CH3 b. CH3CH2CH2CH2CH3 c. (CH3CH2CH2CH2)3N

an O atom that nonpolar an N atom that can

can H-bond with water not water soluble H-bond to H2O, but

5 C's > 5 C's
water soluble not water soluble

3.12 Hydrophobic portions will primarily be hydrocarbon chains. Hydrophilic portions will be polar.

Circled regions are hydrophilic because they are polar.

All other regions are hydrophobic since they have only C and H.

OH
C C H O
COOH
a. b. c.
HO
O OH
arachidonic acid
norethindrone benzo[a]pyrene derivative
Chapter 3±6

3.13 Like dissolves like.

• To be soluble in water, a molecule must be ionic, or have a polar functional group capable of H-
bonding for every 5 C’s.
• Organic compounds are generally soluble in organic solvents regardless of size or functional
group.
nonpolar
long hydrocarbon chain
polar O
O

OH
a. b.
N polar
O
vitamin B3 nonpolar vitamin K1
(niacin) (phylloquinone)
soluble in water due to soluble in organic solvents
two polar functional groups two polar C–O bonds but the
and only 6 C's in the molecule compound has > 10 C's
water insoluble

3.14 A soap contains both a long hydrocarbon chain and a carboxylic acid salt.

ionic salt ionic salt

a. CH3CO2–Na+ b. CH3(CH2)14CO2–Na+ c. CH3(CH2)12COOH d. CH3(CH2)9CO2–Na+

short chain long chain no salt long chain

carboxylic acid salt This is a soap because it contains This is a soap because it contains
both a long chain and a carboxylic both a long chain and a carboxylic
acid salt. acid salt.

3.15 Detergents have a polar head consisting of oppositely charged ions, and a nonpolar tail consisting
of C–C and C–H bonds, just like soaps do. Detergents clean by having the hydrophobic ends of
molecules surround grease, while the hydrophilic portion of the molecule interacts with the
polar solvent (usually water).
a detergent

SO3 Na+

polar head
nonpolar tail ionic - hydrophilic
hydrophobic This end interacts with the water solvent
This end interacts with to maintain the micelle's solubility in water.
the grease to dissolve it.
 Introduction to Organic Molecules and Functional Groups 3±7

3.16
amide ester amide
ester
ester
ester
ether
ester ether
H O H
O ester N N O
O O
O O O
O O O O H
O O N amide
O O
O HN O O
O O O O H O O
N O
O O O N
ether amide O H
ether
ester
ester ester ester
amide amide

nonactin valinomycin

3.17 Electronegative heteroatoms like N, O, or X make a carbon atom an electrophile.

A lone pair on a heteroatom makes it basic and nucleophilic.

Bonds create nucleophilic sites and are more easily broken than  bonds.

nucleophilic nucleophilic nucleophilic

electrophilic

a. Br b. H O H c. d. N
CH3

C bonded to Br nucleophilic
electrophilic electrophilic

3.18 Electrophiles and nucleophiles react with each other.

O
a. CH3CH2 Br + OH YES c. C + OCH3 YES
CH3 Cl

electrophile nucleophile electrophile nucleophile

b. CH3 C C CH3 + Br NO d. CH3 C C CH3 + Br YES

nucleophile nucleophile nucleophile electrophile

Chapter 3±8

3.19 Identify the functional groups based on Tables 3.1, 3.2, and 3.3.
amide
aromatic rings aromatic ring
aromatic ring amide sulfide
H
O N S
a. CH2 HO CH3
c. e.
CH3CH2CO2 C O N CH3
O
CH3 C H carboxylic acid COOH
ester CH2N(CH3)2 ibuprofen penicillin G

Darvon amine carboxylic acid

amine alkene
NH2 amine
N
CO2H OH f. O
d. H
b. alkenes
alkene O O
carboxylic acid alcohol alkene
alkyne ester
pregabalin ketone
histrionicotoxin
pyrethrin I
3.20
CH3
OH CH2OH CH3 C OH
CH3 CH CH2 CH3 CH3CH2CH2CH2 OH CH3 CH CH3 CH3
alcohol alcohol alcohol alcohol

CH3
CH3CH2 O CH3CH2 CH3 O CH CH3 CH3 O CH2CH2CH3

ether ether ether

3.21 A cyclic ester is called a lactone. A cyclic amide is called a lactam.

O
a. N CH3 b. O c. d. NH
O O
amine ether ester amide
lactone lactam

3.22 Draw the constitutional isomers and identify the functional groups.

O O O O O
ketone aldehyde aldehyde
OH O
OH H O H OH H
carboxylic acid
alcohol ether
ester alcohol
O O
aldehyde
H O
alcohol OH
ester
 Introduction to Organic Molecules and Functional Groups 3±9

3.23 Use the rules from Answer 3.5.

O O

OH OCH3
a. b. c. d.
N

VDW VDW VDW VDW

dipole–dipole dipole–dipole dipole–dipole no dipole–dipole
H-bonding (O–H bond) no H-bonding (no O–H bond) no H-bonding (no N–H bond) (nonpolar C–C, C–H bonds)
no H-bonding (no O, N, F)

3.24 Increasing intermolecular forces: van der Waals < dipole–dipole < H-bonding

a. increasing intermolecular forces: c. increasing intermolecular forces:

CH3CH3 < CH3Cl < CH3NH2
(CH3)2C=C(CH3)2 < (CH3)2CHCOCH3 < (CH3)2CHCOOH

VDW VDW VDW VDW VDW

dipole–dipole dipole–dipole VDW
dipole–dipole dipole–dipole
H-bonding
H-bonding
b. increasing intermolecular forces: d. increasing intermolecular forces:
CH3Cl < CH3Br < CH3I
CH3Cl < CH3OH < NaCl

Increasing polarizability
stronger intermolecular forces
VDW VDW ionic
dipole–dipole dipole–dipole
H-bonding

3.25
O H O
hydrogen bonding between
CH3 C C CH3
two acetic acid molecules
O H O

3.26 A = VDW forces; B = H-bonding; C = ion–ion interactions; D = H-bonding; E = H-bonding;

F = VDW forces.

3.27 Use the principles from Answer 3.6.

a. CH3(CH2)4 I CH3(CH2)5 I CH3(CH2)6 I

Increasing size, increasing surface area, increasing boiling point

b. CH3CH2CH2CH3 < (CH3)3N < CH3CH2CH2NH2

VDW VDW VDW
dipole–dipole dipole–dipole
H-bonding

Increasing boiling point

Chapter 3±10

c. (CH3)3COC(CH3)3 < CH3(CH2)3O(CH2)3CH3 < CH3(CH2)7OH

VDW VDW VDW
dipole–dipole dipole–dipole dipole–dipole
smaller surface area larger surface area H-bonding
highest bp
Increasing boiling point
OH
d. < Br < OH <
VDW VDW VDW VDW
dipole–dipole dipole–dipole dipole–dipole
H-bonding H-bonding
larger surface area
Increasing boiling point

e. < <
smallest surface area largest surface area
most branching

Increasing boiling point

O OH
f. < <

VDW VDW VDW

dipole–dipole dipole–dipole
H-bonding

Increasing boiling point

3.28 In CH3CH2NHCH3, there is a N–H bond so the molecules exhibit intermolecular hydrogen
bonding, whereas in (CH3)3N the N is bonded only to C, so there is no hydrogen bonding. The
hydrogen bonding in CH3CH2NHCH3 makes it have much stronger intermolecular forces than
(CH3)3N. As intermolecular forces increase, the boiling point of a molecule of the same
molecular weight increases.

3.29 Stronger forces, higher mp.

CH3 O CH3 OH

CH(CH3)2 CH(CH3)2
menthone menthol
VDW VDW
dipole–dipole dipole–dipole
lower melting point H-bonding
stronger forces
higher melting point
 Introduction to Organic Molecules and Functional Groups 3±11

3.30 Stronger forces, higher mp. More symmetrical compounds, higher mp.

a. (CH3)3CH < (CH3)2C=O < (CH3)2CHOH CH3 Cl NH2

VDW VDW VDW c. < <
DD DD
H-bonding VDW VDW VDW
Increasing intermolecular forces DD DD
H-bonding
Increasing melting point
Increasing intermolecular forces
b. CH3F < CH3Cl < CH3I
Increasing melting point
Increasing polarizability

Increasing melting point

3.31

119 oC
118 oC
91 oC
25 oC

not symmetrical not symmetrical symmetrical most spherical
higher mp highest mp
In both compounds the CH3 group dangling This molecule can pack somewhat better This compound
from the chain makes packing in the solid since it has no CH3 group dangling packs the best
difficult, so the mp is low. from the chain, so the mp is somewhat since it is the
higher. It also has the most surface area most spherical in
and this increases VDW forces compared shape, increasing
to the first two compounds. its mp.

3.32 Boiling point is determined solely by the strength of the intermolecular forces. Since
benzene has a smaller size, it has less surface area and weaker VDW interactions and therefore a
lower boiling point than toluene. The increased melting point for benzene can be explained by
symmetry: benzene is much more symmetrical than toluene. More symmetrical molecules can
pack more tightly together, increasing their melting point. Symmetry has no effect on boiling
point.

CH3 toluene
benzene
bp = 111 oC
bp = 80 oC and
mp =
93 oC
mp = 5 oC
very symmetrical less symmetrical
closer packing in solid form lower mp
higher mp
Chapter 3±12

3.33 Increasing polarity = increasing water solubility.

Neither compound is very H2O soluble.

a. CH3CH2CH2CH3 < (CH3)3CH < CH3OCH2CH3 < CH3CH2CH2OH

VDW VDW VDW VDW
more spherical DD DD
(This nonpolar, hydrophobic H-bonding
molecule is more compact,
making it more water soluble than its
straight-chain isomer, drawn to the left.)

b. Br O OH

polar polar polar and

no H-bonding H-bonding to H2O, H-bonding
not itself More opportunities
for H-bonding with its
O atom and its H on O.

3.34 Look for two things:

• To H-bond to another molecule like itself, the molecule must contain a H bonded to O,
N, or F.
• To H-bond with water, a molecule need only contain an O, N, or F.

Each of these molecules can H-bond to another These molecules can H-bond with water. All of
molecule like itself. Both compounds have these molecules have an O or N atom.
N–H bonds. b. CH3NH2, c. CH3OCH3, d. (CH3CH2)3N,
b. CH3NH2, e. CH3CH2CH2CONH2 e. CH3CH2CH2CONH2, g. CH3SOCH3,
h. CH3CH2COOCH3

3.35 Draw the molecules in question and look at the intermolecular forces involved.

no H bonded to O
H bonded to O:
O OH
hydrogen bonding
diethyl ether 1-butanol
VDW forces VDW forces
dipole–dipole forces dipole–dipole forces
H-bonding
• Both have
5 C's and an electronegative O atom, so they can H-bond to water,
making them soluble in water.
• Only 1-butanol can H-bond to another molecule like itself, and this increases its boiling point.
 Introduction to Organic Molecules and Functional Groups 3±13

3.36 Use the solubility rule from Answer 3.13.

OH
CCl3
O
Cl C Cl
a. c. e. H2N OCH3
H N
mestranol H
DDT CH3O O
COOH
no N or O 2 polar functional groups
not water soluble but > 10 C's aspartame
not water soluble many polar bonds with N and O atoms
many opportunities for H-bonding
O OH water soluble
CH3 HO
CH3 N HO OH
N O
HO O OH
b. N d.
O N O f.
CH3 HO OH
OH
caffeine sucrose carotatoxin
many polar bonds with N and O many polar bonds with O 1 polar functional group
atoms 11 O's and 12 C's but > 10 C's
many opportunities for H-bonding many opportunities for H-bonding with H2O not water soluble
water soluble water soluble

3.37
(CH3)2CHCH(CH3)2 CH3(CH2)4CH3 CH3(CH2)5CH3 CH3(CH2)6CH3
B C D A
6 C's 6 C's 7 C's 8 C's
Branching makes less no branching highest bp
surface area, weaker VDW.
lowest bp
C, D, and A are all long chain hydrocarbons,
but the size increases from C to D to A, increasing
the VDW forces and increasing bp.

3.38 Water solubility is determined by polarity. Polar molecules are soluble in water, while nonpolar
molecules are soluble in organic solvents.

CH3 Arrows indicate polar functional groups.

a. b. CH2NH2
HO
HOCH2 OH
CH3
CH3 O CH3 CH3 CH3 CH3 N CH3
CH3
pyridoxine
vitamin E
vitamin B6
only 2 polar functional groups
many polar bonds and few nonpolar bonds
many nonpolar C–C and C–H bonds (29 C's)
soluble in H2O
soluble in organic solvents
It is also soluble in organic solvents since it
insoluble in H2O
is organic, but is probably more soluble in H2O.
Chapter 3±14

3.39 Compare the functional groups in the two components of sunscreen. Dioxybenzone will most
likely be washed off in water because it contains two hydroxy groups and is more water soluble.

O O OH O OH

CH3O C(CH3)3 OCH3

avobenzone dioxybenzone
two ketones two hydroxy groups
one ether one ketone
one ether
more water soluble

3.40 Because of the O atoms, PEG is capable of hydrogen bonding with water, which makes PEG
water soluble and suitable for a product like shampoo. PVC cannot hydrogen bond to water, so
PVC is water insoluble, even though it has many polar bonds. Since PVC is water insoluble, it
can be used to transport and hold water.

H
O
H no H-bonding
H-bond
O O
O O
Cl Cl Cl Cl
poly(ethylene glycol) poly(vinyl chloride)
PEG PVC
water soluble water insoluble

3.41 Molecules that dissolve in water are readily excreted from the body in urine whereas less polar
molecules that dissolve in organic solvents are soluble in fatty tissue and are retained for longer
periods. Compare the solubility properties of THC and ethanol to determine why drug
screenings can detect THC and not ethanol weeks after introduction to the body.
CH3

OH

CH3CH2 OH
CH3 O (CH2)4CH3
CH3 ethanol

tetrahydrocannabinol
THC
THC has relatively few polar Ethanol has 1 O atom and
bonds compared to the number only 2 C's, making it
of nonpolar bonds, making it soluble in water.
soluble in organic solvents
and therefore soluble in fatty tissue.
Due to their solubilities, THC is retained much longer in the fatty tissue of the body, being
slowly excreted over many weeks, while ethanol is excreted rapidly in urine after ingestion.
 Introduction to Organic Molecules and Functional Groups 3±15

3.42 Compare the intermolecular forces of crack and cocaine hydrochloride. Stronger intermolecular
forces increase both the boiling point and the water solubility.

CH3 ionic bond H CH3

N N
COOCH3 Cl COOCH3

O O
O C O C
H H

cocaine (crack) cocaine hydrochloride

neutral organic molecule a salt

The molecules are identical except for the ionic bond in cocaine hydrochloride. Ionic forces are
extremely strong forces, and therefore the cocaine hydrochloride salt has a much higher boiling
point and is more water soluble. Since the salt is highly water soluble, it can be injected
directly into the bloodstream where it dissolves. Crack is smoked because it can dissolve in the
organic tissues of the nasal passage and lungs.

3.43 A laundry detergent must have both a highly polar end of the molecule and a nonpolar end of the
molecule. The polar end will interact with water, while the nonpolar end surrounds the
grease/organic material.

H O H H O H
a. OCH2CH2O CH2CH2O H

polar
nonpolar interacts with water
interacts with organic material by H-bonding at all O atoms,
as well as H's bonded to O's.
H
H O H
O
H O H CH2CH2O H H H
b. N CH2CH2O H O
O H O H H

H O H
nonpolar polar
interacts with interacts with water
organic material by H-bonding
at O and H atoms
Chapter 3±16

3.44 An emulsifying agent is one that dissolves a compound in a solvent in which it is not normally
soluble. In this case the phospholipids can dissolve the oil in its nonpolar tails and bring it into
solution in the aqueous vinegar solution. Or, the nonpolar tails dissolve in the oil, and the polar
head brings the water-soluble compounds into solution. In any case, the phospholipids make a
uniform medium, mayonnaise, from two insoluble layers.

vinegar oil
aqueous organic
hydrophilic hydrophobic
These two ingredients will not mix. The emulsifying agent (egg yolk) has phospholipids that
have both hydrophobic and hydrophilic portions, making the mayonnaise uniform.

3.45
O O
OH OH H H
H
O N HCl O N
a. O O Cl–

N N
H H

O O
OH OH HH
H Cl–
O N O N
b. O O

N N
H H
five functional groups that have ionic salt
many opportunities for H-bonding more water soluble
water soluble

c. Since the hydrochloride salt is ionic and therefore more water soluble, it is more readily
transported in the bloodstream.

3.46 Use the rules from Answer 3.17.

nucleophilic nucleophilic
nucleophilic

+ + + +
a. + I  c. O e. CH3OH

electrophilic electrophilic
electrophilic
O
nucleophilic
C
b. CH2 d. f. CH3 + Cl

nucleophilic electrophilic
All the C=C's are (All lone pairs on O and
nucleophilic. Cl are nucleophilic.)
 Introduction to Organic Molecules and Functional Groups 3±17

3.47
+ Br NO + OH NO
a. d.
nucleophilic
nucleophilic
nucleophilic
nucleophilic

e. + H3O YES
b. CH2Cl + CN YES
electrophilic
nucleophilic nucleophilic
electrophilic
O
c. C
CH3 CH3 + CH3 YES
nucleophilic
electrophilic

3.48 More rigid cell membranes have phospholipids with fewer C=C’s. Each C=C introduces a bend
in the molecule, making the phospholipids pack less tightly. Phospholipids without C=C’s can
pack very tightly, making the membrane less fluid, and more rigid.

The double bonds introduce kinks in the

chain, making packing of the hydrocarbon
chains less efficient. This makes the cell
membrane formed from them more fluid.

CH2O

H C O
O
(CH3)3NCH2CH2 O P O CH2 O
O

3.49
amine a. 7 amide groups [regular (unbolded)
can H-bond hydroxy group arrows]
can H-bond
b. OH groups bonded to sp3 C's are
circled. OH groups bonded to sp2 C's
NH2 OH
HO HO
OH have a square.
O c. Despite its size, vancomycin is water
O O
soluble because it contains many polar
O Cl
groups and many N and O atoms that
O O
can H-bond to H2O.
HO OH d. The most acidic proton is labeled
Cl
O H O H
O (COOH group).
O
N
N
N
N
N
NHCH3 e. Four functional groups capable of H-
HN
H
O
H
O
H bonding are ROH, RCOOH, amides,
HO
C
H2N and amines.
O amide
most O
can H-bond
acidic OH
proton HO OH vancomycin
Chapter 3±18

3.50
O OH O
OH H H
= O =
C
CHO
H CHO C
H O
A B
The OH and CHO groups are close enough that they can The OH and the CHO are too far
intramolecularly H-bond to each other. Since the two polar apart to intramolecularly H-bond
functional groups are involved in intramolecular H- to each other, leaving more
bonding, they are less available for H-bonding to H2O. opportunity to H-bond with
This makes A less H2O soluble than B, whose two solvent.
functional groups are both available for H-bonding to the
H2O solvent.
3.51
a. melting point

HOOC H Fumaric acid has its two larger COOH groups on opposite
C C ends of the molecule, and in this way it can pack better
H COOH in a lattice than maleic acid, giving it a higher mp.
fumaric acid
b. solubility
H H
Maleic acid is more polar, giving it
C C
greater H2O solubility. The bond
HOOC
+
+COOH dipoles in fumaric acid cancel.
maleic acid

c. removal of the first proton (pKa1)

H H HOOC H
C C C C
HOOC COOH H COOH
loss of 1 proton loss of 1 proton
H H
C C HOOC H
O C C O C C
O O H COO
H
In maleic acid, intramolecular H-bonding Intramolecular H-bonding
stabilizes the conjugate base after one H is is not possible here.
removed, making maleic acid more acidic
than fumaric acid.
d. removal of the second proton (pKa2)
H H
OOC H
C C
O C C O C C
O O H COO

Now the dianion is held in close proximity The two negative charges are
in maleic acid, and this destabilizes the conjugate much farther apart. This makes the
base. Thus, removing the second H in maleic dianion from fumaric acid more
acid is harder, making it a weaker acid than stable and thus pKa2 is lower for
fumaric acid for removal of the second proton. fumaric acid than maleic acid.