Académique Documents
Professionnel Documents
Culture Documents
Semester 1
Academic year: 2013/2014
Lecturers: Mr O. Otukile
/T.M.SETAMMERE/
I.NYEPETSI
1
COURSE STRUCTURE
Tests 1
Test 2
25%
End of Semester Examination
Total
100%
25%
50%
Reference:
UNIT 1
INORGANIC CHEMISTRY
WHAT IS CHEMISTRY?
Chemistry is the branch of science
that studies the composition ,
structure and properties of
matter and the changes that
matter undergo.
3
Role of Chemistry in
modern life/ health
MATTER
Definition: Anything that has mass and
occupies space.
There are three states that matter can
exist in namely:
1. SOLID
2. LIQUID
3. GAS
This is dependent on temperature, and
other physical conditions.
5
SOLIDS
Characteristics:
LIQUIDS
Characteristics:
Particles are not closely packed but are still in
contact with each other
They have no definite shape (i.e. they take the
shape of the container).
Have definite volume.
The particles are flowing or mobile.
When they are heated, they slightly expand e.g.
Hg
Incompressible
Relatively less dense
7
GASES
Characteristics:
The particles are further away from each
other and are independent.
Their particles flow easily
No definite volume(fills up the whole
container)
Takes up shape of the container.
They expand when heated.
Low density
8
Properties of matter
Physical Properties:
tells us what a substance is (i.e they can be
measured without changing the chemical
nature of the substances present) . Some
common examples of physical properties are:
volume, mass, temperature, pressure ,
solubility, color, density, melting point,
boiling point, hardness.
Chemical properties:
Changes in matter
A change in density
A change in temperature
A change in colour
Breaking into smaller pieces.
N.B: In a physical change, no new substances
are formed.
10
11
Chemical
A new substance is
formed
Tells what the
substance does
(ability to react)
Properties of a new
substance differ from
those of the initial
substance
13
Composition of Matter
ELEMENTS
Cont
Elements present in
human body
1.Nutritionally important elements
required in amount greater than 100 mg
per day are as follows;
1. Calcium
2. Magnesium
3. Potassium
4. Sodium
5. Chlorine
6.Phosphorus
17
Cont
2.Trace elements are and their
importance
1. Iodine-thyroid hormones
2. Iron-production of red blood cells,
production of
enzymes, converts blood sugar to
energy
3. Copper-synthesis of hemoglobin, bones,
oxidative enzymes,
4. Zinc-enzymes, normal growth, nucleic acid
metabolism
18
COMPOUNDS
19
Properties of Compounds
MIXTURES
Comparison between
mixtures and compounds
MIXTURE
COMPOUND
22
MOLECULE
A molecule is a composition of
elements or combination of atoms.
In most cases, molecules are
formed from a combination of non
metals e.g.
- H2O molecule
- O2 molecule
- C2H5OH alcohol
- Cl2 molecule
23
Molecule cont
Major components of molecules in
our bodies are; O2, H2, N2, S2 and
Carbon.
24
Separation techniques
1. Filtration
Filtration
27
2. Evaporation
28
Evaporation
29
Evaporation
30
3. Centrifuging
Centrifugation cont
32
Centrifugation
33
Centrifugation
34
35
Centrifugation cont
36
4. Crystallization
Crystallization
38
Crystallization
39
5. Simple Distillation
Simple distillation
41
6. Fractional Distillation
Fractional distillation
43
7. Chromatography
Usefulness of
chromatography
Paper Chromatography
Chromatogram
47
Separating funnel
Separating funnel
Separating funnel
50
Exercise
ATOM
An atom is the smallest particle of an
element.
REMEMBER: An element is made from
only one type of atom.
It has the chemical properties of the
element it comes from
In the human body we have : atoms
cells tissue
organ system
organism
52
ATOMIC STRUCTURE
Protons
Neutron
Electrons
53
Atomic structure
Atomic models
55
Properties of sub-atomic
particles
Particle
Mass
Charge
Location
Proton
+1
Nucleus
Neutron
Nucleus
Electron
1/1840
-1
Orbits/
shells
56
Electronic configuration
The arrangement of electrons in an
atom follows the equation, 2n2.
- Where n is the shell number/energy
level
1st shell takes 2*12 = 2 electrons
2nd shell takes 2*22 = 8 electrons
3rd shell takes 2*32 = 18 electrons
E.g. Na(11 electrons); 2, 8, 1
Cl(17 electrons); 2, 8, 7
58
CHEMICAL BONDING
Ionic (electrovalent)
Covalent
59
Ionic bonding
Ionic bonding
Examples;
1. Na + Cl
Na+ + Cl- (NaCl)
In the example above , the most
important step is the transfer of
the valence electron from sodium
atom to a chlorine atom. The loss
of an electron from an atom of
sodium results in the formation of
an Na+ ion whose e.c is 2,8 (a
noble gas configuration).
61
Ionic cont
At the same time the gain of an
electron by a chlorine atom result
in a Cl- ion which has the e.c
2,8,8( a noble gas configuration).
Take home exercise:
(a)Draw a cross and dot diagram for
the bond between magnesium and
oxygen atoms. Show valence
electrons only.
(b)How many electrons must62be lost
Ionic cont
2. Mg +2 Cl
Mg2+ + 2ClMgCl2
Valency cont
65
Reason
RADICALS
Physiological importance
of ions
70
Maintains:
Osmotic pressure of cells
Electric pressure of cells
Size of cells
Proper contraction of the heart
Proper transmission of nerve
impulses
it is part of the buffer system. E.g.
in form of salt .e.g KHCO3 71
72
73
75
hyponatremia
o
o
o
o
o
goiter
78
Covalent bonds
Covalent cont
80
Properties of covalent
bonds
Covalent substances
Cont
C2H5OH (Ethanol)
Metallic bond
Definition:
Metallic bond
Properties of metallic
substances
Polar-covalent bonds:
1.
Balancing equations
1.
2.
3.
Balancing equations
cont
Ca(OH)2(s) + HCl(aq)
CaCl2(s) + H2O(l)
AgNO3 (aq) + FeCl3 (aq)
AgCl(s) + Fe (NO3)3(aq)
95
Rate of reaction
Chemical stoichiometry
Chemical stoichiometry
Avogadros number
101
102
Measurement of
Concentration
Molarity (M)
No. of Moles
Molarity
Volume of solution (in l)
104
Problems
1.
2.
3.
Problems cont
4.
ZnSO4(aq) + Cu(s)
106
Molality (m)
Molality
Difference between
Molarity and Molality
110
Calculation of Molality
(Class work)
111
solution
112
Molality
113
Normality
Normality = molarity x n
(where n = the number of protons
exchanged in a reaction)
114
Normality
115
Normality
Normality
N = normality
V = volume
Percentages(%)
Percentage composition
Uu
E.g. one type of calcium supplement
tablet states that each table contains
1500mg (1.5g) calcium carbonate.
Calculate the
119
Percentage by weight
The percent by mass( also called
percent by weight or weight percent)
is the ratio of the mass of solute to
the ratio to the mass of solution,
multiplied by 100 percent:
Percent by mass of solute = mass of
solute/ mass of solute + mass of
solvent *100%
= mass of solute/mass of soln
120
*100%
Percentage by weight
E.g: a 0.892g sample of potassium
chloride is dissolved in 54.6g of
water. what is the percent by mass
of potassium chloride in this
solution?
Solution:
% by mass of KCl = 0.892g/ 0.892g
+ 54.6 g *100% = 1.61%.
121
Titration
Problem
Reversible reactions
Example of reversible
reaction
N2 + 3H2
2NH3
If we start with a mixture of N2 and H2 at
a given temp and pressure (with a
catalyst), we will soon have some NH3
formed.
As more NH3 is formed, it will begin to
decompose into N2 and H2
When the rates of formation and
decomposition are equal, a chemical
equilibrium forms (this means that the
rate of the forward reaction equals the
126
reverse reaction)
Le Chateliers Principle
OR
H2CO3
Properties of Acids
130
Properties of Acids
Strong acids are completely
ionized in solution. Example:
weak acids are only partially
ionized.
Example:
131
Properties of Acids
HO
132
Properties of Acids
Properties of Acids
(metal oxide)
(water)
(salt)
134
Properties of Acids
135
Properties of Acids
Properties of Acids
Acids reacts with carbonates and
bicarbonates to form CO2, H2O and salts.
I.e.
1. HCl + CaCO3
CaCl + H2CO3
(Acid)
(carbonate)
H2CO3
(salt)
(carbonic acid)
H2O + CO2
2. HNO3 + NaHCO3
(Acid)
H2CO3
(bicarbonate)
NaNO3 + H2CO3
(salt)
H2O + CO2
(carbonic acid)
137
Properties of Acids
138
Precautions in handling
and storing acids
BASES
Bases are substances that yield
hydroxide ions (OH-) in a water solution.
Examples,
NaOH
Na+ + OHKOH
K+ + OH It can also be defined as proton
acceptor.
OH- + H+
H2O
Strong bases are highly ionized and
have a great attraction for protons.
143
(Table 12-3 pg 198, commonly used
Properties of bases
.
.
Properties of bases
145
Uses of Bases
Uses of Bases
Milk of magnesia Mg(OH)2 used as
an antacid for the stomach
- also used as a laxative when in the form
of a suspension of Mg(OH)2 in water.
Spirits of ammonia, containing NH OH
4
and (NH4)2CO3 is used as a heart and
respiratory stimulant.
NH OH is used as a water softener for
4
washing clothes.
147
Precaution on Bases
Precaution on Bases
Salts
150
Properties of salts
Uses of Salts
152
Solubility
pH
154
pH cont
pH exercise
Calculate the pH of solution
which a concentration of 0.01M.
What would be the
concentration of solution which
has pH value of 7.45?
Calculate the pOH of 0.025M
NaOH
2,3.5x10-8,12.4
156
pH scale
157
Methods of measuring pH
2. Indicator paper
158
Buffer
159
Buffer cont
161
162
NaOH + H2CO3
The salts KHCO3 and NaHCO3 are part of the original buffer
systems and the water produced is neutral, so the pH again
is not affected.
163
K2HPO4 + H2O
more buffer
neutral compound
164
UNIT 3
OXIDATION AND REDUCTION
166
OXIDATION
1.
2.
3.
4.
Loss of electrons
Gain of oxygen
Loss of hydrogen
An increase in oxidation number
167
1. Loss of electrons
Example;
Na + Cl
Na+ClIn the above example, Na atom
loses an electron to a Cl atom as
they form an ionic bond.
Therefore Na atom was oxidized
and Cl was reduced.
168
2. Gain of oxygen
Examples;
1. Fe + O2
Fe2O3
3. Loss of hydrogen
2CH3CH2OH + O2
2H2O
(ethanol)
2CH3CHO +
(ethanal/acetaldehyde)
170
4. An increase in the
oxidation number
0
0
2
2Na + Cl
2Na Cl
171
Reduction
1.
2.
3.
4.
Gain of electrons
Loss of oxygen
Gain of hydrogen
A decrease in oxidation number
172
Examples
Consider the following examples:
0
0
+
1. 2Na + Cl2
2Na Cl
174
Cont
0
2
+2
Pb + H2
2(+1)
175
-2
2. H
+ Pb O
-2
Application of Oxidizing
and Reducing agents
1. Antiseptic effects
.
Many antiseptics have a property of
killing bacteria. For example;
Chlorine
Calcium Hypochloride(CaCOCl2)
Cont
2.
Al2(SO4)3 + 3H2
Cu(NO3)2 + 2Ag
2H2O
178
179
Oxygen
180
Physical properties of
Oxygen
Colourless
Odourless
Tasteless
Has a high density (heavier than air)
It is transparent
On cooling, oxygen become a pale blue
liquid which boils at -182.5oc, its solid at
-218.4oc.
It is sufficiently soluble in water to allow
its diffusion from the alveoli to the
bloodstream and then to tissue cells (it
supports life).
181
Cont
182
Cont
Oxygen Hazards
Nitrous Oxide
188
It supports combustion.
In its use as an aesthetics, the
concentration should not exceed 70%,
excess of it causes Hypoxia.
Less amount of N2O results in less
potent (not active) or not potent enough
for most patients, so additional drugs
such as halothane or methoxyflurane
are used to complete anesthetia.
189
Carbon monoxide, CO
Levels of carboxy-haemoglobin
above 5 % of total likely to cause;
headache, drowsiness, fatigue
(which can lead to syncope i.e.
fainting, comma, respiratory failure
and can cause death at
concentrations of about 50%.
191
Carbondioxide
Properties
- makes up to 0.03% of the
atmosphere.
- Given off when materials that
contain carbon and oxygen
combine during burning.
- byproduct of respiration.
- used by green plants during
photosynthesis
193
Uses of Carbondioxide
Water
Cont
Physiological importance
of water
Cont
Cont
Purification of water
Impurities in water
202
Inorganic or mineral
matter
203
Organic matter.
Common methods of
water purification.
Note: Water purification is important
as it makes the water to be safe for
drinking
1. BOILING
2. Distillation
206
3. Sedimentation and
Filtration
Ozone (O3)
Medical importance of
ozone
209
Nitric oxide
211
Sulphur oxide
UNIT 4
LIQUID MIXTURES
213
LIQUID MIXTURES
Solution
A solution is a homogenous
mixture of two or more substances
evenly distributed in each other.
A liquid solution consists of two
parts namely the solute and the
solvent.
215
Properties of a solution
Solute
Solvent
218
Importance of solutions
Importance of solutions
cont
Terminology used to
describe solutions
222
Terminology used to
describe solutions cont
Properties of colloids
224
Properties of suspensions
Properties of Emulsions
226
Special properties of
solution
1. Effect of solute on b.p and f.p
A nonvolatile dissolved in a
solvent results in a higher
b.p(raises the b.p of the
substance) and a lowers f.p of the
solvent. E.g. salt and water
solution has high b.p (>100 oc)
and lower f.p (<0 oc).
227
2. Surface tension
3. Viscosity
Viscosity is a measure of
resistance to flow.
Some liquids will flow readily (e.g.
water with viscosity of 1.00) and
others do not.
Blood has a viscosity more than
water to accommodate exchange
of materials.
229
4. Diffusion (passive
transport)
5. Osmosis
6. Osmotic pressure
232
7. Reverse osmosis
Isotonic solution
234
Hypotonic solution
Hypertonic solution
238
Dialysis
Hemodialysis
240
Assignment
1. Define an antidote.
2. What are the functions of an
antidote? Give an example.
3. Give two uses of carbondioxide.
4. What are the precautions to be
taken during the administration
of carbondioxide?
243
Assignment cont
5. What are the medical importance of the
following: CaCO3, Bicarbonates and
MgCO3
6. What are the causes of temporary and
permanent hardness of water?
7. Discuss the following methods of
removal of hardness: Addition of Sodium
carbonate and Zeolite method.
8.
Discuss the following methods of water
purification: Chlorination, Aeration and
Deionization.
244
Assignment cont
Question 9
What is haemodialysis?
UNIT 5
ORGANIC CHEMISTRY
246
ORGANIC CHEMISTRY
Properties of Organic
compounds
248
Hydrocarbons
Saturated hydrocarbons
Hydrocarbons
Alkanes
H
C
H
Alkenes
Alkynes
C
C
C
C
C
C
H
Aromatics/Arenes
H
H
H
C
C
C
C
C
C
H
H
Alkanes
Isomerism
2. -C-C-CCC
3.
253
Reactions of Alkanes
1. Combustion
Alkanes react with air/O to give CO and Water.
2
2
CH4 + 2O2
CO2 +2H2O + Energy
2. Substitution/halogenation
Alkanes react with halogens by substitution of hydrogen
by halogens
i.e. CH4 + Cl2
CH3Cl (Chloro-methane)
CH2Cl2 (Dichloro-methane/methylene
chloride)
CHCl3 (chloroform / trichloro methane)
CCl4 (tetrachloro-methane)
254
Physical Properties of
saturated compounds
(Alkanes)
Cont
Uses of Saturated
Hydrocarbons
METHANE (Natural gas); - used for
heating and cooking purposes in the
Labs and home.
(C C );
5
16
- mineral oil(liquid paraffin) a mixture of
liquid saturated hydrocarbons used in
hospitals for lubricating purposes.
- lubricates catheters and surgical
instruments.
. used as laxative.
. used as an ingredient in ointment
257
Cont
258
Unsaturated Hydrocarbons
Alkenes (double bond)
Alkynes (triple bond)
Cycloalkenes
Haloalkanes
Note: Haloalkanes and
Cycloalkenes are known as
Aromatics (Benzene rings with
multiple bonds).
259
Alkenes
Cont of alkenes
Alkenes with double bonds are known as
diene and those with triple bonds
triene.
Examples of diene;
1,3-butadiene CH2 CH-CH CH2
Alkynes
Alkynes are hydrocarbons that contain a
carboncarbon triple bond.
e.g. Ethyne
-C
C Names end with suffix -yne.
General formula; C H
n 2n-2
262
Naming of Alkynes
1-Butyne (ethylacetylene)
CH3CH2C CCH3
2-Pentyne (ethylmethylacetylene)
OH
CH3CH2CHC CH
(1-Pentyn-3-ol)
263
.
264
2.Hydrogenation
Hydrogenation is the addition of
hydrogen to a compound.
E.g alkene + hydrogen
alkane
3. Halogenation
266
4.Hydro-halogenation
267
5. Hydration
268
6. Oxidation
(combustion)
269
.
.
271
Uses of Alkynes
.
.
.
.
Cycloalkanes
Cycloalkanes
CH2
Examples
Cyclopropane, C3HH
CH2
6,2C
Cyclopentane, C5H10,
Cyclobutane, C4H8
Cyclohexane, C6H12
275
Cyclopropane
Uses - General anesthetic
(Remember; Nitrous oxide is the
best anesthetic)
Disadvantages
cause muscular contraction
- very reactive and explosive
(shaking causes it to explode and
therefore need to be transported in
special apparatus)
276
Haloalkanes.
277
-.
-.
-.
Halothane
Non flammable
Non irritating to the respiratory
tract
Can be given alone or combines
with nitrous oxide(N2O) to patients
during surgery of all types and with
muscle relaxants to produce
general anesthetic effect. 278
2. Ethylchloride-C2H5Cl
279
3. Freon-12
dichlorodifluoromethane
280
4. Teflon-(C2F4)n
281
5. PVC
282
6. Chloral hydrate
Naming Hydrocarbons
(nomenclature)
IUPAC
2-butene
H
H
H3C
H
H3C CH CH CH3
C
H
CH
H3C
H3C
CH
CH3
CH3
CH3
OH
Formic acid
H
Acetylene
O
C
H3C
Acetone
CH3
IUPAC
The International Union of Pure and
Applied Chemistry (IUPAC) was
established in 1900s
Frequent revisions to nomenclature
Systematic method allows an infinite
number of compounds to be named
given a few rules
288
MethEthPropBut-
Monkeys
Eat
Peeled
Bananas
Other prefixes
Pent-
Numbering carbons
Q- draw pentene
A- Wheres the bond? H3C
5
1
We number C atoms
1-pentene
4
2
2
4
1
5
CH3 2,3-
H3C
2,4,6-nonatriyne
heptadiene
CH
2
CH3
H2C
CH
1,2,4-pentatriene
CH3CH2CH2CH=C=CH2 1,2-hexadiene
H
Cyclic structures
C
C
H
C
H
H
cyclopentane
Q- Draw these (note: carbons in a double bond
should be consecutive- 1 and 2, 5 and 6, etc.):
H
H
H2C
CH2
HC
CH
H
C
C
C
H
C
C
H
CH2
H2C
CH2
C H3
CH
C H3
H3C
CH
Names are made up
of: side chains, root
2,3-dimethylpentane
CH
C H3
Root is the longest possible HC chain
Must contain multiple bonds if present
Add -yl to get name of side chain
H3C
CH3
Common side chains include:
CH
CH3- methyl
CH3CH2- ethyl
*
CH3CH2CH2- propyl (CH3)2CH-isopropyl
CH2 CH3
CH2 C
CH3
CH3
CH2 CH3
CH2 C
CH3
CH3
CH2 CH3
CH2 C
CH3
CH3
CH2 CH3
CH2 C
CH3
CH3
CH2 CH3
CH3 CH2 C
CH2 C
3
CH3
CH3
ethyl
CH2
CH2 CH3
CH3 CH2 C
CH2 C
CH3
meth
yl
CH3
meth
yl chains
Rule 5: Determine name for side
2
1-hexene
ethyl
CH2
CH2 CH3
CH3 CH2 C
CH2 C
CH3
meth
yl
CH3
meth
yl
Rule 6: attach name of branches
2
2-ethyl-4-methyl-4-methyl-1-hexene
1-hexene
ethyl
CH2
CH2 CH3
CH3 CH2 C
CH2 C
CH3
meth
yl
CH3
meth
yl
Rule 7: list alphabetically
2
2-ethyl-4-methyl-4-methyl-1-hexene
1-hexene
ethyl
CH2
CH2 CH3
CH3 CH2 C
CH2 C
CH3
meth
yl
CH3
meth
yl
Rule 8,9: group similar branches
2
2-ethyl-4-methyl-4-methyl-1-hexene
1-hexene
ethyl
CH2
CH2 CH3
CH3 CH2 C
CH2 C
CH3
meth
yl
CH3
meth
yl
Rule 8,9: group similar branches
2
2-ethyl-4,4-dimethyl-1-hexene
H3C
CH2
CH CH3
H2C
CH2
CH CH CH2 CH3
H3C
CH3
3-methylhexane
CH
CH3
4-ethyl-2,3-dimethylheptane
CH3
CH3
CH3
5-ethyl-2,4,6-trimethyloctane
CH
CH2
CH
CH3
H2C
H3C
H3C
3-ethyl-2-methylpentane
CH3
CH3
3-ethyl-1,5,5trimethylcyclohexene
CH3
More practice
Br
4-bromo-7-methyl-2-nonene
Br
2,5-dibromo-6-chloro-1,3-cycloheptadiene
Br
Cl
CH3
H3C
C
CH3
CH2 C
F
CH CH CH CH3
5-fluoro-7,7-dimethyl-2,4-octadiene
309
Functional Groups
Functional groups
All organic compounds are grouped into
classes based on characteristic features
called functional groups.
Functional groups are special group of atoms in
molecules that are responsible for their
characteristic chemical properties. Or
is an atom or a group of atoms within a
molecule that serves as a site of chemical
reactivity.
they dictate the physical, chemical and
other
Examples of functional
groups
-OH, Alcohol (hydroxyl group)
-O-, Ether
-CHO, Aldehyde
-CO-, Ketone
-COOH, Carboxylic acid
- NH , Amine
2
-CONH , Amide
2
-COO, Ester
(check last page of the text book)
312
Alcohols
Nomenclature of alcohols
Types of alcohol
Monohydric alcohols
Have only one OH group.
Examples;
CH3OH (methanol)
C2H5OH (ethanol)
316
Classes of monohydric
alcohols
317
Classes of monohydric
alcohols
(i) Primary alcohols (1o)
They have a hydroxyl group attached
to a carbon that is bonded to just one
other carbon atom.
e.g: Propyl alcohol and 2methylpropyl alcohol.
318
319
320
Exercise
Draw structures of the following
alcohols
1. 1-Bromo-3-methyl-2-butanol
2. 1-Chloro-3-pentanol
3. 1-Propylcyclopentanol
321
Dihydric alcohols
322
Trihydric alcohols
Have three hydroxyl groups attached
to three different carbon atoms.
Examples;
CH2OHCH2OHCH2OH
(glycerol/glycerin)
or (1,2,3-propanetriol)
323
Polyhydric alcohols
More than three hydroxyl groups
attached to the carbon atoms.
Examples; - Mannitol ( sorbitol) or
Hexane-1,2,3,4,5,6-hexol (used for the
treatment of malignant brain tumors)
-Xylitol
-Carbohydrates
324
Properties of alcohol
1.
2.
3.
4.
5.
1. Ethyl alcohol
(ethanol)
2. Isopropyl alcohol
3. Ethylene glycol
4.Glycerol
5. menthol
Physiological effects of
Alcohol
In most of the
countries, the
threshold limit of
blood alcohol
content for drunk
driving is 0.08%
(i.e. 80 mg /100
ml of blood)
In Hong Kong,
the threshold
is 0.05% (i.e.
50 mg / 100
ml of blood)
Although taking
alcohol (ethanol) is
socially acceptable,
driving under the
influence of alcohol
is a crime in most
parts of the world.
inin
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ivivi
r
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ddr
bbl lo odd
f
kk
oof bloloo h
n
l
n
uu
l f b at th
r
m
r
dd
00 m l loof brerea
f
0
oof
110 0 mm of f b
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n
l o
ioionngg nool l / / 11000 m l
t
i it o n a n l /
00 m
n
o
a
0
h
l
K
o
n
eefifingg K eet th anno l / /110
DD o n
thha o l
HHo mgg eet anno
m
ha
5500 mgg eet th
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6677 gg
2
Ethers
336
Ethers
Alcohol + alcohol
Examples of Ethers:
H2SO4, 140O
CH3-O-CH3
and
ether + water
CH3CH2-O-CH2CH3
(Diethyl ether/ethyl ether)
Nomenclature of ethers
Ethers can be symmetrical, where the
two alkyl groups are the same, or
unsymmetrical, where the two alkyl
groups are different.
Diethyl ether is symmetrical while
ethyl methyl ether is unsymmetrical.
Nomenclature of ethers
339
Nomenclature of ethers
Nomenclature of ethers
a).
b.
Use IUPAC and common names.
. Draw structure of :
1. 2-Methyl-2-methoxypropane 2.341
Properties of ethers
342
Has a low bp
Highly flammable
Very good solvent because it is
chemically inert (does not react with a
solute)
Due its low bp, it can be easily
extracted/removed very fast
Should not be kept in the lab for longer
times without shaking as it undergoes
oxidation
Easy to administer
Good muscular relaxant
Little effect on the pulse rate, rate of
respiration and blood pressure
Disadvantages:
Highly flammable
Irritating to the membranes of the
respiratory tract
Have the after effect of nausea
Today it is used as an inhalation
anesthetic in laboratory work.
It has been replaced by nitrous oxide
and halothane which are nonflammable.
Functional groups:
Aldehydes: R-CHO
Aldehydes cont
Ketones cont
Ketones: R-CO-R
Nomenclature of
aldehydes and ketones
Nomenclature
Nomenclature
352
Examples
Aldehydes
Ketones
Formaldehyde (Methanal)
Ethanal
butanone
Medically important
Aldehydes and Ketones
1. Formalin
2. GLUTERALDEHYDE
3. PARALDEHYDE
4. GLYCERALDEHYDE
It is a component in the
metabolism of carbohydrates.
5. ACETONE (Propanone)
Note: it is a ketone.
It is a good solvent for fats and
oils.
It is frequently used in fingernail
polish and in polish remover.
It is found in small amounts in
blood and urine.
In cases of Diabetic mellitus, it is
found in large quantities in blood
and urine.
Ketosis
It is the overall accumulation of
ketone bodies in the blood.
Ketosis may occur with diabetes
mellitus in the period of starvation,
severe liver damage or in a diet
high in fats and oils and low in
carbohydrates.
360
Ketosis cont
ESTERS
ESTERS
Esters cont
Esters nomenclature.
Esters
e.g.
1.
2.
Ethyl-amino-benzoate (benzocaine)
3.
Local anesthetic
Amines
Amines
Amines are classified as primary (1),
secondary (2), tertiary (3) or
quaternary (4) depending on how
many alkyl groups are attached to the
N atom.
Classified as primary, secondary,
tertiary
CH3
CH3
Nomenclature of amines
Nomenclature of amines
Naming Amines
IUPAC aminoalkane
CH3CH2NH2
aminoethane
(ethylamine)
Common alkylamine
CH3NH CH3
N-methylaminomethane
NH (dimethylamine)
2
NH CH3
NH2
|
CH3CHCH3
2-aminopropane
(isopropylamine)
Aniline
N-methylaniline
Reactions of Amines
Amides
Amide nomenclature
Amides are named by replacing the
-oic acid or -ic acid suffix of the
parent carboxylic acids with the
suffix -amide, or by replacing the
-carboxylic acid ending with
-carboxamide.
Alkyl groups on nitrogen atoms are
named as substituents. The name of
the substituent is preceded by N-, or N, N,followed by the name(s) of the375alkyl
Amides
Derivatives of carboxylic acids
where an amino (-NH2) group
replaces the OH group.
O
O
CH3 COH
CH3 CNH2
carboxylic acid
amide
acetic acid
acetamide
Naming Amides
Alkanamide
from acid name
O
methanamide (IUPAC)
HCNH2 formamide (common)
O
propanamide (IUPAC)
CH3CH2CNH2 propionamide(common)
CH3CNHCH3 N-methylethanamide
(IUPAC)
N-methylacetamide (common)
O
CH3CH2CN(CH3)2
N,N-dimethylpropanamide
N,N-dimethylpropionamide
Urea
Niacinamide
Reactions of Amides
Amides undergo
acid hydrolysis
base hydrolysis
carboxylic acid
salt of carboxylic
acid
ammonium salt
and an amine
or ammonia
Reactions of Amides
acid hydrolysis
CH3CNH2
NaOH
Amides
e.g.
Carboxylic Acids
Carboxyl group
combination of the carbonyl group
and the hydroxyl group
Nomenclature of organic
acids
etone>alcohol>amine>alkene>alkyne.
386
Carboxylic acids
Acids
Structure
Physical
Properties of
Carboxylic
Acids
Variations of
boiling points with
the number of
carbon atoms of
straight-chain
carboxylic acids,
alcohols,
aldehydes and
alkanes
Density
Solubility
Carboxylic acids of low molecular masses
show appreciable solubilities in water
Carboxylic acids are polar and their
molecules can form strong hydrogen
bonds with water molecules
Solubility
The first four members of carboxylic
acids are miscible with water in all
proportions
When the length of the hydrocarbon
portion increases
the solubility of the carboxylic acids
in water declines
Formation of RCOOH
e.g.
Oxidation of Alkylbenzenes
Oxidation of Alkylbenzenes
e.g.
Oxidation of Alkylbenzenes
Alkylbenzenes with alkyl groups other than
methyl group are also oxidized to benzoic
acid by hot alkaline KMnO4
Formation of salts
Formation of salts by reacting with
1. Metals
2. Carbonates
3. Hydroxides
Medicinally important
acids and their
characteristics
1. Formic Acid
Colourless
Has a sharp irritating odour
Found in sting of bees, ants and
causes characteristic pain and
swelling when it is injected into the
tissues
One of the strongest organic acids
2. Acetic acid
3.Other acids
More acids
Citric acid
NITROGEN CONTAINING
ORGANIC COMPOUNDS
Amines
Amides
Amino acids
Amines
Amines are organic compounds derived from
ammonia
Functional group; -NH2
Genformula group: R-NH
2
Some of the Amines medicinally used in the
body are as follows;
Histamines
Barbiturates
Psychedelics
Nucleic acids
Amides are basic and readily form salts
Psychoactive drugs
Tranquilizers
Opiates
Depressants
Stimulants
Hallucinogens
Psychoactive drugs
Affect the Central Nervous System
and alter the normal functioning
of the brain resulting in behavior
changes.
CNS
Brain
Types of Psychoactive
Drugs
Stimulants
Depressant
Narcotics s
Hallucinoge
Heart Rate
Raised
Respiration
Raised
Examples of Stimulants
CAFFEINE
AMPHETAMINES
METHAMPHETAMINES
COCAINE
Examples of Depressants
SEDATIVES
TRANQUILIZERS
Questions to answer:
Solutions
1. and 2. Sorry thats your assignment
3. Examples of hallucinogens are:
1.
Phencyclidine (PCP)
2.
Lysergic Acid Diethylamide (LSD)
Natural
narcotics:
Opium
Morphine
Codeine
Opiates
Semi-synthetic
narcotics:
Heroin
Hydromorphine
Synthetic
narcotics:
Methadone
Meperidine
Opium cont
HO
1
11
Morphine
12
13
16
15
14
10
9
H
8
6
7
Morphine
Codeine
(Methylmorphine)
Brief note
MeO
Codeine
Morphine
Codeine
RELIEVE PAIN
STOP
COUGHING
Barbiturates
1.
2.
3.
Phenobarbital is used as an
anticonvulsant agent in the treatment
of epilepsy
Hallucinogens
/Psychedelics
Produce visions
Used in the treatment of terminal
cancer patients because it reduces
the pain and awareness
Causes dilation of the pupils
Increases the body temperature
WHAT TYPE OF
PSYCHOACTIVE DRUGS ARE
THE FOLLOWING?
Caffeine
Alcohol
Marijuana
Sleeping Pills
Morphine
Heroine
Nicotine
Amphetamines
STIMULANT
DEPRESSANT
HALLUCINOGEN
DEPRESSANT
NARCOTIC
NARCOTIC
STIMULANT
STIMULANT
Histamines
Nucleic acids
Amino-acids
Contains a basic amino group and an acid
carbonyl group.
NH2------------------------COOH
(basic)
(acidic)
A-acids
General formula
R-CH-COOH
NH2
437
a-acids cont
Examples:
CH3COOH + NH4
CH2COOH
NH2
(Glycin)
Amino acids exhibit both acidic and basic
properties. They react with both bases and
acids (i.e. amphoteric)
Proteins are polymers of alpha amino acids
e.g. glycol
Alpha
CH2COOH
NH2
Physiological importance
of amino acids
Aromatic compounds
Heterocyclic compounds
2.
3.
4.
5.
Examples of aromatic
compounds
1.
2.
3.
4.
5.
6.
7.
Benzene
Toluene
Xylene
Benzepyrine
Phenanthrene
Naphthalene
Anthracene
1. Benzene
Benzene (C6H6) is the simplest aromatic hydrocarbon (or
arene).
Benzene has four degrees of unsaturation, making it a highly
unsaturated hydrocarbon.
Whereas unsaturated hydrocarbons such as alkenes,
alkynes and dienes readily undergo addition reactions,
benzene does not.
Properties of Benzene
Colourless
Has gasoline like odour
Insoluble in water but soluble in alcohol
and ether
Toxic when ingested, inhaled
Decreases the amount of rbc and wbc
counts
Mildly carcinogic (cancer causing).
Therefore discontinued use in labs.
(Toluene is preferred)
2. Toluene
Importance of Toluene
Good solvent
Used as a preservative for urine
specimens
Used in the manufacture of TNT
(Tri-Nitro-Toluene) which is
explosive
An ingredient in air plane glue
when sniffed can produce blurred
vision
3. Xylene
Assignment
Benzepyrine
Phenanthrene
Naphthalene
Anthracene
BIO-CHEMISTRY
Definition
Carbohydrates
Carbohydrates are a class of
compounds that are mainly found in
plants, where they make about 75% of
the plant material. These compounds
include:
i.
ii.
iii.
iv.
v.
vi.
Glucose
Fructose
Maltose
Starch
Cellulose
Sucrose
Classification of
Carbohydrates
1.
2.
3.
Monosaccharides
1.
2.
3.
4.
Monosaccharides cont
1.
2.
3.
1. Glucose
Physiological importance of
Glucose
1.
2.
Colour
Yellow
Orange
Red
Notation % glucose in
urine
++
0.1 0.5
+++
0.5 1.5
++++
>1.5
Other tests
Clini-test tablet
1.
Tollens reagent
2.
Chemical properties of
Glucose
oxidation
reduction
CH3CH2CH2CH=O
or Ar
O
C
KMnO 4 or K2Cr 2O 7
or
C
X2
OH / H2O
O
C
(ArCOOH)
COOH
O
CH 3
RCOOH
Ag(NH3)2
(Tollens reagent)
HIO 4
HCX 3 + RCOO
RCOOH + HCOOH
+ HIO 3
KMnO4
NR
Cyclohexanone
O
+
KMnO4, heat
HOOCCH2CH2CH2CH2COOH
adipic acid
OH
enol
2) Reduction:
a) To alcohols
O
C
H2, Ni
NaBH4 or LiAlH4
then H+
OH
C
H
C
H
H2, Pt
CH2OH
benzaldehyde
CH3
CH3CHCH=O
isobutyraldehyde
benzyl alcohol
LiAlH4
H+
CH3
CH3CHCH2OH
isobutyl alcohol
Reduction
b) To hydrocarbons
O
C
O
C
NH2NH2, OHWolff-Kishner
Zn(Hg), HCl
Clemmensen
CH2
CH2
ketone
ROR
aldehyde
RCOOH
ROH
alkene
RX
Alcohols are
central to organic
syntheses
RH
alkyne
HALOALKANES
GROUP 7
SATURATED
HYDROCARBONS
Uses and
characteristics
Haloalkanes
487
1. Halothane
Non flammable
Non irritating to the respiratory
tract
Can be given alone or combines
with nitrous oxide(N2O) to patients
during surgery of all types and
with muscle relaxants to produce
general anesthetic effect.
2. Ethylchloride
489
3. Freon
490
4. Teflon
491
5. PVC
492
6. Chloral hydrate
493
H + HO
CH3
CH3
OH
H+, heat
O
O
CH3 + H2O
CH3
isoamyl
acetate
O
H3C
OH+ HO
CH3
CH3
H , heat
+
H3C
CH3
O
+ H2O
CH3
CH3
OH+ HO
CH3
H+, heat
O
H3C
CH3 + H2O
CH3
For more lessons,
visit
Chemistry of Benzene
Derivatives
497
Aniline
NH2
Formation:
Sn/HCl
NO2
NH2
498
Reactivity of Aniline
Br
NH2
499
Reactivity of Aniline
Reaction is reversible
500
acetyl chloride
NH2
CH3COOH
or
acetic anhydride
H3C
NH
O
Br2
Br
Br
+
+
Br
NH2
H /OH
NH2
Br
H3C
H3C
NH
NH
O
O
501
502
Reactivity of Aniline
Me
NH2
Cl
NH2
503
H2SO4
N+
NH2
NaHSO4
NaNO2
H2SO4
HNO2
NaHSO4
+
504
Mechanism for
diazotisation
505
Diazonium ion
N
USEFUL REACTIONS
Synthesis of Phenols.
Synthesis of benzoic acid.
Utilizing o,p direction effect
and removing the amino group.
506
I. Substitution Reactions
H2O/H+
KI
OH
warm
I
N+
CuBr2
H3PO2
warm
CuCN
Br
+
H
HOOC
NC
heat
507
A. Phenol synthesis
+
CH3
OH
508
CH3
OH
CH3
509
Br
NO2
510
diazonium ion
nucleophilic ring system (has
activating group)
M
E
C
H
A
N
I
S
M
+
N N
..
NMe2
Me
+
N
N N
Me
H
base :
N N
..
N
Me
Me
512
N
N
SO 3H
513
Azo dyes
Properties:
In most of the
states in the US,
the threshold limit
of blood alcohol
content for drunk
driving is 0.08%
(i.e. 80 mg /100
ml of blood)
In Hong Kong,
the threshold
is 0.05% (i.e.
50 mg / 100
ml of blood)
Although taking
alcohol (ethanol) is
socially acceptable,
driving under the
influence of alcohol
is a crime in most
parts of the world.
Definition
Definition of
of drunk
drunk driving
driving in
in
Hong
Hong Kong
Kong
50
50mg
mgethanol
ethanol//100
100ml
mlof
ofblood
blood
67
67mg
mgethanol
ethanol//100
100ml
mlof
ofblood
blood
22 g ethanol / 100 ml of breath
Breathalyzer
Brief note
Principle of breathalyzer
Alveolar air
Wall of
air sac
Alcohol in blood
diffuses across
alveolar wall
Blood
vessels
Principle of breathalyzer
Brief note
2 Cr2O7
2-
+ 3 C2H5OH +
AgNO
3 as
+
16 catalyst
H
Porous acid
electrolyte
Pt electrode
CH3CH2OH + O2
CH3COOH + 2H+ + 2e-
2H+ + O2 + 2eH 2O
Brief note
Benzodiazepines
H
C
H
C
3
3
N
N
H
H
C
3
H
O
N
N
3C
N
N
H
N
N
3
N C
NC
l
NC
N
l
l
NC
C
l
O
F
C
l
Chlordiazepoxide
Diazepam
Midazolam
Triazolam
Brief
note
Benzodiazepine side effects & withdrawal
symptoms
While benzodiazepines have lower overdose fatality, they
produce more serious side-effects and withdrawal symptoms to
patients and drug abusers. These side-effects include lightheadedness, drowsiness, lethargy, ataxia and the impairment
of mental and physical functions.
Abrupt discontinuation of the regular dosage of
benzodiazepines may lead to very serious, sometimes
unpredictable, withdrawal symptoms. In general, withdrawal of
the drug causes the reverse of its initial effects.
Withdrawal symptoms include insomnia, anxiety (possible
panic attacks), tachycardia, hypertension, depression (possible
suicidal ideation), tremor, perspiration, loss of appetite,
dysphoria, convulsion, delusions and psychosis.
If the withdrawal is based on a short-acting benzodiazepines,
symptoms begin fairly rapidly after drug discontinuation. For
longer-acting benzodiazepines, patients may have as much as a
week of symptom-free activity after stopping medication before
withdrawal symptoms will begin.
Disassociative anesthetics
Brief note
O
H
O O
H
Disassociative anesthetics
C
lN
H
O
Ketamine
N
Phencyclidine (PCP)
C
lC
H
3
N
HO
C
lH
N
O
(S)-Ketamine
C
l
H
N
O
(R)-Ketamine
Ketamine &
PCP site
NMDA receptor
C
lH
N
O
Brief
note
antagonist
C
lC
H
3
N
HO
C
l
H
N
O
However, popularity of
ketamine has grown
tremendously in the last
decade and has become one
of the mostly abused soft(S)-Ketamine
(R)-Ketamine
drug in Hong Kong.
It was first synthesized by Dr. Calvin Stevens at the
Parke-Davis Laboratories in 1962 and was marketed as
an anesthetic agent in 1965.
It was brought in as a safer alternative to PCP and was
extensively used in the Vietnam War as a battlefield
anesthetic.
Brief note
Ketamine and the NMDA receptor antagonist
Ketamine is able to induce disassociative anesthesia as
well as strange out-of-body, out-of-the-world
hallucinations in patients and drug abusers.
These effects are mainly caused by its interaction with
the NMDA receptors widely distributed in the CNS.
NMDA receptors are
cation channels responsive
to the excitatory
neurotransmitter
glutamate (together with a
co-agonist glycine).
Activation of NMDA
receptors results in the
opening of the ion channel
and causes cations (K+,
Na+ and Ca2+) to flux into
Ketamine &
PCP site
Ketamine abuses
Brief note
Brief note
C
lC
H
3
N
HO
C
H
C
lH
3C
N
HO
O
2N
N
O
2
NO2
OH-
NH
O
CH2
NO2
C
lC
H
3
N
H
O
N
O
2
H
N
O
2
Bloodstain revealed by
the chemiluminescent
reaction between blood
and luminol
Plasma
Percentage by weight
Proteins 7%
Percentage by
volume
Water
91%
Plasma
Other solutes 2%
55%
Particulates
Number of cell mm-3
Particulate
45%
Platelets
1.5 3.0 105
Leuocytes
10 15 103
Red blood
cells
4.5 6.0 106
Brief note
Reduced dye
[O
]
Hemoglobin in blood
as a catalyst
Brief note
Oxidized
dye
Sharp colourimetric /
luminescent change
HO
OH
H2O2
CH
COOH
Phenolphthalin, colourless
COO-
O
N
H
N
H
N
H
2O
OH-
O
NNN
H
2O
Luminol
Luminol reveals bloodstain even
after thorough cleanup of visible
blood
Hemoglobin
O
NNOON
H
2O
3% H2O2 or household
bleach
O
OON
H
2O
+ N2 +
light
HO
OH
H2O2
COOH
Fluorescin, non-fluorescent
Hemoglobin
COOH
Fluorescein,
fluorescent at max 496 nm
Brief
Precipitin test for confirmation of origin
of
blood sample
note
Porcelain dish
Drying tube
Burner
6 H2 (nascent) + 6 ZnCl2
Formation of black
Asmirror
(s) +on
3 white
H2O
substrates
Formation of white
Typical US
technique for the
opening of the
chest and
abdomen during
an examination
autopsy
medical
Brief note
Brief note
Trafficking in purported dangerous drug
(1) No person shall, on his own behalf or on behalf of any other person, whether or
not such other person is in Hong Kong(a) traffic in any substance represented or held out by him to be a dangerous
drug
but which is not in fact a dangerous drug;
(b) offer to traffic in any substance represented or held out by him to be a
dangerous
drug but which is not in fact a dangerous drug; or
(c) do or offer to do an act preparatory to or for the purpose of trafficking in
any
substance represented or held out by him to be a dangerous drug but
which is
not in fact a dangerous drug.
(2) Subsection (1) shall apply whether or not the substance represented or held
out to be a dangerous drug is in Hong Kong or is to be imported into Hong Kong or
is ascertained, appropriated or in existence.
(3) Any person who contravenes any of the provisions of subsection (1) shall be
guilty of an offence and shall be liable(a) on conviction on indictment, to a fine of $500000 and to imprisonment for
7 years;
and
(b) on summary conviction, to a fine of $100000 and to imprisonment for 1
year.
(4) No prosecution for an offence under this section shall be instituted without the
consent in writing of the Secretary for Justice, but this subsection shall not prevent
the arrest, or the issue of a warrant for the arrest, of a person for any such
offence, or the remand in custody or on bail of a person charged with such an
offence.
Brief note
Brief note
Brief
note
Cultivation of and dealing in cannabis plant and opium
poppy
(1)No person shall cultivate any plant of the genus cannabis or
the opium poppy, but nothing in this subsection shall prevent
the Government Chemist, in his capacity as such, from
cultivating a plant of the genus cannabis so far as may be
necessary for the exercise of his employment.
(2) No person shall, on his own behalf or on behalf of any other
person, whether or not such other person is in Hong Kong(a) supply or procure or offer to supply or procure;
(b) in any way deal in or with or offer or purport to deal in or
with; or
(c) import into or export from Hong Kong or do an act
preparatory to or
for the purpose of such importing or
exporting, any plant of the genus
cannabis or the opium
poppy, whether or not the same is in Hong
Kong or is
ascertained or appropriated or in existence.
(3) No person shall have in his possession any plant of the
genus cannabis or the opium poppy unless the same is in
transit.
(4) Section 14 shall apply to any plant of the genus cannabis
Aldehydes and
Ketones
Nomenclature
Properties
Preparation reactions of
Aldehydes and Ketones
Characteristic reactions of
Aldehydes and Ketones
Carbanion related reactions
Spectroscopy
Preparation of Aldehydes
and Ketones
Oxidation reactions
Hydrolysis of Geminal
Dihalides
Hydration of Alkynes
Reactions with Acid
Derivatives and Nitriles
Reaction with Carboxylic
Acids
Aldehydes/Ketones via
Oxidation Reactions
Cleavage
PCC
RCH 2 OH
R 2 CHOH
PCC
C H
O
R
O
R'CH
CR 2
ozonolysis
R' C H + R
O
R'
R
C
OH
CH 2 OH
HIO 4
C
O
O
R' + H
C H
O
Hydrolysis of
Geminal
Dihalides
Formation of Aldehydes or
Ketones
R CH Cl2
R 2CCl2
H 2O
H 2O
C H + 2 HCl
O
C R + 2 HCl
O
Hydration of
Alkynes
Markovnikov Addition
Anti-Markovnikov
Addition
H 2O/H2SO 4
R C CH
R C CH 2
HgSO 4
OH
R C CH
1. 9-BBN
2. H 2O 2/OH
RCH CH
OH
R C CH 3
O
R CH 2 C H
O
Lithium tri-tert-butoxyaluminum
hydride
Rosenmund reduction
Nomenclature
IUPAC
Common
Properties
Lithium tri-t-butoxyaluminum
hydride reduction
Rosenmund reduction
C Cl
O
C Cl
O
LiAlH(O-t-bu) 3
ether
H 2 / Pd / S
BaSO 4
Rosenmund catalyst
C H
O
C H
O
O
R C OR'
or
O
R C NH 2
or
O
R C NHR'
or
O
R C NR 2 '
1. Diisobutylaluminum
hydride
2.
H3 O
O
R C H
R C Cl
O
R C O C R
O
AlCl3
benzene
AlCl3
benzene
C R + HCl
O
C R + RCOOH
O
C Cl
O
(R') 2CuLi
R CN
DIBAH or DIBAL-H
diisobutylaluminum hydride
C H
O
C N Al(i-bu)2
H
H /H2 O
RCOO Li
R
R
R
R
RLi
H 2O
O Li
OH
OH
R
R
+
O Li
-
RCOO Li + RH
RCOOH
( H 2O )
R
R
R
+
O Li
-
O Li+
OH
OH
C R
O
Ketones from
Thioacetals
Thioacetal formation from an aldehyde
precursor
Alkylation of the thioacetal intermediate
using alkyl lithium reagents
Hydrolysis of the alkylated thioacetal to
give
ketone product
R
S
C
C 4H 9Li
(
C 4H10 )
C
R
CH 2 R'
S
C
Li
(a thioacetal)
R'CH 2X
S
C
BF 3
O
S
HSCH 2CH 2 SH )
S
C
R
C
O
+ LiX
CH 2 R'
CH 2 R'
Characteristic
Characteristic Reactions
Reactions of
of
Aldehydes
Aldehydes and
and Ketones
Ketones
Reduction reactions
Alcohol formation
Alkane formation
Oxidation reactions
Nucleophilic addition reactions
Reduction Reactions of
Aldehydes and Ketones
Alcohol
formation
Hydrogenation
Hydride
reduction
Alkane
formation
Clemmensen
reduction
C H
O
H 2 / Pt
LiAlH4
C H
ether
O
CH 2OH
H 2O
H
C H conc. HCl R CH 3
Zn(Hg)
O
NH 2NH 2
R C H
R CH 3
OH / H2O
O
CH 2OH
Oxidation of
Aldehydes and
Ketones
Conversion of Aldehydes to
Carboxylic acids
Oxidation of Aromatic
Aldehydes/Ketones to Benzoic acid
derivatives
Haloform reaction of methyl
carbonyls
Periodic acid cleavage of vicinal
Aldehyde / Ketone
Oxidations
H or Ar
KMnO 4 or K2Cr 2O 7
or
X2
OH / H2O
O
C
(ArCOOH)
COOH
O
CH 3
RCOOH
(Tollens reagent)
Ag(NH3)2
HIO 4
HCX 3 + RCOO
Aldehyde/KetoneNucleophilic
AdditionReactions
R'
H
H 2O
R"MgX
+
C
O
C
O
H or OH
R'
H 2O
C
O
R'
dry HCl
R'
R''OH
R'
R
OH
OH
R'
R'
R
HCN
R'
gem diol
OH
OR"
R'
OH
CN
OR"
OR"
ketal
cyanohydrin
R
H 2N
R'
OH
hemiketal
O
R
R"
(-H 2O)
R'
Aldol Condensation
Claisen Condensation
Self vs. Crossed
Dieckmann cyclization
Reformatsky Reaction
Wittig Reaction
Carbanion
Alkylations/Acylations/Conjugat
e Addition reactions
Aldol
Aldol
Condensations
Condensations
Self
Condensation
Crossed
H
+
Condensation
OH or H
C H
RCH C
2 RCH 2
OH
C H + R' C H
O
CH C H
RCH 2
OH or H
H R
R' C CH C H
OH
ClaisenCondensations
Self vs. Crossed
Condensation
Dieckmann
R'O
RCH 2 C CH
2RCH 2 C OR'
R'OH
Condensation
O R
O
RCH 2
R'O
R'O
C OR' + R" C OR'
R'OH
O
O
(CH 2)4
O
R'O
C
O
(CH 2)5
R'O
C OR'
R'OH
O
R'O
C OR'
R'OH
O
R" C
C OR' + R'OH
O
CH C OR' + R'OH
O R
O
C
O
C
OR' + R'OH
OR' + R'OH
Reformatsky
Reformatsky Reaction
Reaction
C H + Br CH 2 C OR'
O
C R + Br CH 2 C OR'
O
1. Zn/ benzene
2. H3O
C CH 2 C OR'
OH
1. Zn/ benzene
2. H3O
R
R
C CH 2 C OR'
OH
Wittig Reaction
RCH 2X +Ph3P
+
Ph3P
R'
C
O
Phosphonium salt
formation
Ylide formation
Alkene+ formation
SN2
CH 2R X
R'
+
CHR
PPh3
+
Ph3P
CH 2R X
phosphonium salt
NaH
+
Ph3P
CHR + NaX + H 2
ylide
(R') 2C CHR
O PPh3
oxaphosphatane
R'
R'
+ R
Ph3P O
alkene
+
triphenylphosphine oxide
Carbanion
Alkylation/Acylation/Conjugate
Addition Reactions
MalonicEsterSynthesis
Formation of alkylated acetic acid
+
derivatives
Na
C2H 5O C CH 2
O
NaOC 2H 5
C OC 2 H 5
C2 H 5 OH
O
+
Na
C2H 5O C CH C OC 2 H 5
O
O
RCH 2 X
CH 2R
C2H 5 O C CH C OC 2H 5
O
O
C2H 5 O C CH C OC 2 H 5
O
O
CH 2 R
C2H 5 O C CH C OC 2 H 5
O
O
H /H2 O
CH 2 R
strong heat
HO C CH C OH
O
O
CH 2R
HO C CH C OH
O
O
RCH 2 CH 2COOH + CO 2
Acylation/Hydrolysis/Decarboxylatio
n
Na+
C2H 5O C CH 2 C OC 2H 5
O
Na+
C2H 5O C CH C OC 2 H 5
O
C2H 5O C CH C OC 2H 5
NaOC 2H 5
C2H 5OH
O
R C X
(-NaX)
+
H /H2O
C2H 5O C CH C OC 2H 5
O
C2H 5O C CH C OC 2H 5
O
O C
R
O
HO C CH C OH
O
O C
R
O
HO C CH C OH
O
O C
R
strong heat
O
O C
R
O
R C CH 3 + 2 CO 2
O
AcetoaceticEsterSynthesis
Formation
of
alkylated
acetone
derivatives
CH 3 C CH 2 C OC 2 H 5
O
O
Na +
CH 3 C CH
O
C OC 2H 5
O
CH 2R
CH 3 C CH
O
RCH 2X
(-NaX)
H /H2O
CH 3 C CH
C OH
O
CH 3 C CH
CH 2R
CH 3 C CH
O
C OC 2 H 5
O
CH 2R
CH 3 C CH
O
strong heat
(- CO 2 )
C OC 2H 5
C OC 2H 5
CH 2 R
O
NaOC 2 H 5
C2 H 5OH
Na +
C OH
O
CH 3 C CH 2 CH 2 R
O
CH 3 C CH 2 C OC 2 H 5
O
O
Na
CH 3 C CH C OC 2 H 5
O
NaOC 2 H 5
C2 H 5 OH
O
R C X
(-NaX)
Na +
CH 3 C CH C OC 2 H 5
O
CH 3
CH 3
O C
C CH C OC 2 H 5
O
O C
+
H /H2O
C CH C OC 2 H 5
O
R
CH 3
O C
C CH C OH
O
CH 3
O C
strong heat
C CH C OH
(- CO 2 )
O
O
CH 3 C CH 2 C R
O
Formation
of Alkylated Aldehydes/Ketones
H OH
R' C C H +R 2 NH
R' C C H
NHR 2
R'
(-H 2 O )
(an aminol )
( H+ )
C H
R'
NR 2
C H
NR 2
CH 2 R"
R"CH 2 X
R'
SN 2
C H
NR 2
+
CH 2 R"
R'
C H
NR 2
+
hydrolysis
C H
(an enamine)
(a disguised carbanion)
NR 2
R'
C H
NR 2
R'
CH 2 R"
R'
C H + R 2 NH
O
StorkEnamineSynthesis
Formation of Acylated
H
H OH
Aldehydes/Ketones
R' C C H +R 2 NH
R' C C H
NHR 2
+
(an aminol )
R'
H
(-H 2 O )
R'
( H+ )
C H
R'
(a disguised carbanion)
O
O
C
C H
R" C X
R'
R'
R"
C H
NR 2
+
O
hydrolysis
R"
C H
+
(an enamine)
NR 2
NR 2
O
C H
NR 2
C H
NR 2
NR 2
R'
R'
C
C
R"
C H + R 2 NH
O
Conjugate Addition to
Unsaturated
Systems
Nu +
O
Nu
Nu
C C
C C
C C
O
Nu
C C
H
Michael
Addition
Michael
CH (COOR) 2
malonic ester
COOR
C R'
CH
RCH
C C
O
CH
R'
(Michael donor)
H 2O
unsaturated ketone
R'
R'
RCH
CH
OR'
O
unsaturated ester
-diketone
RCH
R 2 CuLi
dialkyl cuprate
unsaturated aldehyde
-ketoester
CH
Michael Product
RCH
CH
enamine
CH
C N
unsaturated nitrile
RCH
CH NO 2
unsaturated nitroalkene
CH C
Michael Addition
Robinson Annulation
C O
C
C
H 3C
OR
O C
ROH
C
C
H 3C
C Michael
C product
OR ROH
O
C
C
C
C
C
O
C
C
HO
H 2O
H 2C
C
C
C
O
O C
C
C
Aldol
H 2C
C
C
C
O
C
C
OH
C C C
H
direct addition
+ Nu
C C C
Nu
H+
H O
C C C
Nu
conjugate addition
Conjugate addition
NH 3 , RNH 2 , & R 2 NH
-1
CN
R SH
R 2 CuLi
carbanions
(Michael addition)
Direct addition
LiAlH 4
RLi or ArLi
RMgX (subject to
steric considerations)
Spectroscopy of
Aldehydes and
Ketones
Mass
Spectrometry
Infrared
Spectroscopy
Pmr Spectroscopy
Cmr Spectroscopy
Structure
O
-I effect
R C O-H
Acidity
O
R C
extra
+ve
Greater polarization of
this bond
O H
Polarization of this bond is
increased, O-H bond is
weakened. (Acidic)
Acidity
O
R C .. O
..
OR C
Question
Explain the following order of acid strength
a. RCOOH > C6H5OH > R-OH
b. CCl3COOH > CHCl2COOH > CH2ClCOOH
> CH3COOH
Acid strength
RCOOH RCOO- + H+
Acid
pKa
HCOOH
3.8
CH3COOH
4.8
CH3CH2COOH 4.9
CH3CH3CH2COOH 4.8
Reduction mechanism
O
R C
H
O H
H:-
R C
H:-
H+
H
R C OH
H
H
R C OH
R C
+
O
R
Cl
O
-
O
R C
HB:
-Z-
O
R C B
-H+
O
R C BH+
pKa
HCl
-2.2
RCOOH 4~5
ROH 16~19
NH3
34
Cl
RCOOH + HCl
O
R
H2O:
H2O:
2 RCOOH
+ (CH3CO)2O
COOH
OCOCH3 + CH3COOH
(Aspirin)
Mechanism of reduction
AlH3-
O
AlH4
R C OR
LiAlH4
O
R C H
RCH2O-AlH3-
O
R C OR
H
+ RO-AlH3H3O+
H3O+
RCH2OH
ROH
Reactions of amides
1. Hydrolysis
reflux
C6H5CONH2
C6H5CN + H2O
Reactions of amides
3. Hofmann degradation
CH3CH2CONH2 + 4KOH + Br2
CH3CH2NH2 + K2CO3 + 2KBr + 2H2O
(one carbon atom less)
4. Reduction (LiAlH4)
LiAlH4 H3O+
RCONH2
RCH2NH2
Mechanism (Hofmann)
O
R C NH + Br- + H2O
OH
R C N
Br
H
R-N=C=O + H2O
Br
O
R C N-
Br
O
R-NH-C-OH
-Br-
R-N=C=O
RNH2 + CO2
Mechanism (reduction)
O
O- Li+
R C NH2
:H-
R C NH2
:HH
LiAlH4
RCH2NH2 + Li2O
Example 32-2A
Example 32-2B
Methanoic
acid
HCOOH
101
8.4
1.220
Ethanoic
acid
CH3COOH
118
16.6
1.049
Propanoic
acid
CH3CH2COOH
141
-20.8
0.992
Butanoic
acid
CH3(CH2) COOH
164
-6.5
0.964
Pentanoic
acid
CH3(CH2) COOH
186
-34.5
0.939
Hexanoic
acid
CH3(CH2)4COOH
205
-1.5
0.927
Benzoic acid
C6H5COOH
249
122
Phenylethanoic
acid
C6H5CH COOH
266
76
Methylpropanoic (CH3)2CHCOOH
acid
154
-47
Chloroethanoic
acid
CH2ClCOOH
189
63
Dichloroethanoic CHCl2COOH
acid
194
10.8
1.566
Trichloroethanoic acid
198
57.7
CCl3COOH
0.950
32.
5Reactions of
Carboxylic
Acids
[K
C
H
O
]
[
H
O
]
C
3
3
a3
Name
3.75
Ethanoic acid
4.76
CH3COOH
4.87
Butanoic acid
CH3CH2CH2COOH
4.82
Benzoic acid
C6H5COOH
4.20
Formation of Salts
1. Reaction with Reactive Metals
e.g.
e.g.
e.g.
of
Example 32-5
32.
6Reactions of
the
Derivatives of
Carboxylic
Acids
where H Nu represents H
H NH2, etc.
OH, H
OR,
e.g.
Ethanoyl chloride is readily hydrolyzed by
water to give ethanoic acid
e.g.
Ethanoyl chloride reacts with methanol to
form methyl ethanoate and HCl
Phenoxide ion
e.g.
Ethanoyl chloride reacts with ammonia to
form ethanamide
e.g.
Ethanoic anhydride is hydrolyzed by water
to form ethanoic acid
Reactions of Esters
1. Acid-catalyzed Hydrolysis
1. Acid-catalyzed Hydrolysis
e.g.
Propyl methanoate undergoes acidcatalyzed hydrolysis
form methanoic acid and propan-1-ol
2. Alkali-catalyzed Hydrolysis
When an ester is refluxed with an alkali
such as NaOH(aq)
the sodium salt of the carboxylic
acid and the corresponding alcohol
are produced
2. Alkali-catalyzed Hydrolysis
e.g.
Ethyl ethanoate undergoes hydrolysis in
sodium hydroxide solution
form sodium ethanoate and ethanol
2. Alkali-catalyzed Hydrolysis
2. Alkali-catalyzed Hydrolysis
2. Alkali-catalyzed Hydrolysis
Alkali-catalyzed hydrolysis is an
irreversible reaction
Let's Think 1
e.g.
Methyl ethanoate reacts with ammonia
form ethanamide and methanol
e.g.
Methyl ethanoate reacts with propylamine
(a 1o amine)
give N-propylethanamide (a 2o amide)
Reactions of Amides
Amides are the least reactive carboxylic
acid derivative towards nucleophilic
substitution reactions
NH2 ion (NHR or NR2 ion) is a
strong base
thus a poor leaving group
1. Hydrolysis of Amides
Acid-catalyzed Hydrolysis
Alkali-catalyzed Hydrolysis
2. Dehydration of Amides
Amides are dehydrated by
heating with phosphorus(V) oxide
(P4O10)
form nitriles
Example 32-6
The END
Back
Example 32-2A
(b)
(c)
(d)
(a)
(b)
(c)
(d)
3-Methylbutanoic acid
N-Methylethanamide
Ethyl benzoate
Benzoic anhydride
Answer
Example 32-2B
An ester is formed by reacting an alcohol with a
carboxylic acid. Draw the structural formulae of
the following esters and in each case, give the
names of the alcohol and the carboxylic acid that
form the ester.
(a) Methyl ethanoate
Answer
Example 32-2B
Back
Answer
(a)
Answer
IUPAC name
(b)
(c)
(d)
(e)
(f)
(g)
(h)
Trichloroethan
oic acid
Back
Example 32-3
(a)Propanoic acid has a boiling point of 141C
which is considerably higher than that of
butan-1-ol (117C), although they have the
same molecular mass. Explain why.
Answer
Example 32-3
(a) Each propanoic acid molecule forms two intermolecular hydrogen
bonds with other propanoic acid molecules. However, each butan1-ol molecule can form only one intermolecular hydrogen bond with
other butan-1-ol molecules. Since molecules of propanoic acid
form more extensive intermolecular hydrogen bonds than those of
butan-1-ol, the boiling point of propanoic acid is higher than that of
butan-1-ol.
Example 32-3
(b) Arrange the following compounds in
decreasing order of solubility in water:
CH3CH2CH2COOH, CH3CH2COOCH3, CH3COOH
(b) The solubility of the compounds in water decreases in
the order:
CH3COOH > CH3CH2CH2COOH > CH3CH2COOCH3
Answer
Example 32-3
(c)Propanedioic acid forms intramolecular
hydrogen bonds. Draw its structural formula,
showing clearly the formation of
intramolecular hydrogen bonds.
Answer
(c)
Back
Answer
Answer
Back
Write the chemical equations for the acidcatalyzed and alkali-catalyzed hydrolyses of
each of the following compounds:
(c) Benzoyl chloride
(c)
Answer
Back
Example 32-5
(a)Complete and balance the following chemical
equations:
(i)
(ii)
Answer
Example 32-5
(a) (i)
(ii)
Example 32-5
(b)
(i)
(ii)
(iii)
Answer
Example 32-5
(b) (i)
(ii)
(iii)
Back
Back
Let's Think 1
The characteristic reaction of the derivatives of
carboxylic acids is nucleophilic acyl substitution.
Arrange the derivatives of carboxylic acids in
decreasing order of reactivity towards nucleophilic acyl
substitution.
Acyl chlorides > acid anhydrides > esters > amides
Back
Answer
Example 32-6
Draw the structural formulae of the missing
compounds A to H:
(a)
(b)
(c)
Answer
Example 32-6
(a)
(b)
(c)
Example 32-6
Draw the structural formulae of the missing
compounds A to H:
(d)
(e)
(f)
Answer
Example 32-6
(d)
(e)
(f)
Back