REVIEW IN

ORGANIC CHEMISTRY
Part 1
Prepared by:
Engr. Josephine Arce Ng
ORGANIC CHEMISTRY
chemistry that deals with C
compounds
VITAL FORCE THEORY - Only living
organisms had the vital force
necessary to produce organic
compounds.
Friedrich Wohler disproved the
theory in 1828 after synthesizing
UREA from ammonium cyanate.
NH
4
CNO NH
2
CONH
2
(urea)
STRUCTURAL THEORY
Atoms of the elements in organic
compounds can form a fixed
number of bonds. The measure of
this ability is called valence. (Ex: C,
O, H, X)
Carbons ability to form bonds with
other carbon atoms to form chains
and rings is called catenation
COVALENT BONDING involves
sharing of electrons of two or more
nonmetals
bond polarity the greater the
electronegativity difference, the
greater is the bond polarity
Formal charge = group # shared
e
-
unshared e
-

bond length optimum distance
between the nuclei of two bonded
atoms
bond energy energy required to
break the bonding between a pair of
atoms
bond angle angle between two
adjacent bonds.

LEWIS STRUCTURE covalent
bonding in w/c
shared electrons are shown as pair
of dots & lone pairs are shown as
pairs of dots.
RESONANCE THEORY:
A molecule or an ion represented in
two or more Lewis structures that
differ only in the position of
electrons exhibit the property of
resonance
HYBRIDIZATION mixing of two or
more atomic orbitals to give the
same number of new orbitals called
hybrid orbitals
Hybrid orbitals of carbon:
sp
3
hybrid orbitals formed by
combination of one s and three p
atomic orbitals; tetrahedral
sp
2
hybrid orbitals formed by
combination of one s and two p
atomic orbitals; trigonal planar
sp hybrid orbitals formed by
combination of one s and one p
atomic orbitals; linear
Functional Groups






























CLASSIFICATION of ORGANIC
COMPOUNDS
I.Hydrocarbons
A.Aliphatic hydrocarbons in chains
a. Alkanes (C
n
H
2n+2
) contain single
bonds
b. Alkenes (C
n
H
2
) contain double
bonds
c. Alkynes (C
n
H
2n2
) contain triple
bonds
d. Alkadienes contain two double
bonds
B. Alicyclic hydrocarbons in a ring
system
1. Cycloalkanes alkanes in closed
chain
2. Cycloalkenes non-conjugated
alkenes in a ring system
3. Aromatic compounds
containing carbon atoms with
conjugated double bonds in a ring
system
II.Hydrocarbon Derivatives
A. Derivatives containing Oxygen
a. Alcohols (R-OH) and Phenols (Ar-
OH) hydrogen is replaced by OH
group
b.Ethers (R-OR) two hydrocarbon
group attached to oxygen

c. Epoxides cyclic ethers in which
oxygen is included in a three-
membered ring
d. Aldehydes (RCHO) and Ketones
(RCOR) hydrocarbons with one or
two alkyl groups attached to C=O
(carbonyl group)
e. Carboxylic Acids (RCOOH)
hydrocarbons with attached to
COOH (carboxyl group)
f. Esters (RCOOR) carboxylic acid
derivatives with the hydrogen
replaced by an alkyl group
g. Acid Anhydrides - carboxylic acid
derivatives with the hydrogen
replaced by RC=O
B. Derivatives containing Halogen
Alkyl/Aryl Halides hydrocarbons
with hydrogen atom replaced by
one or more halogens
C. Derivatives containing Sulfur
a. Thiols hydrocarbon derivatives
with hydrogen atom replaced with
SH
b. Disulfides hydrocarbon
derivatives with general formula R
SSR
D. Derivatives containing Nitrogen
a. Amides carboxylic acid
derivatives with
NH
2
, NHR or NHR
b. Amines organic derivatives of
NH
3






FAMILY FORMULA
Alkane C H and C - C
Alkene



Alkyne


Aromatic




Alkyl halide or
Haloalkane

R - X

Alcohol R - OH
Ether R OR
Amine R NH2

C C
C C
FAMILY FORMULA
Aldehyde



Ketones



Carboxylic
Acid



Esters



Amide



Anhydride




Nitriles

R
C
O
H
R
C
O
R'
R
C
O
OH
R
C
O
OR'
R
C
O
NH
2
R
C
O
O
C
O
R'
C N
General Reactions in
Organic Chemistry


















Electrophiles
are reagents which in their reactions
seek the extra electrons that will
give them stability
Examples: carbocation
Nucleophiles
reagents that seek a proton or some
other positive center
Examples: Carbanion , HO
-

RO
-
, H
2
O, NH
3

ACID-BASE IN ORGANIC
COMPOUNDS










ALKANES
also called paraffins
contains sp
3
hybridized carbon
bond angle of 109.5
o

obtained from fractional distillation
of petroleum
insoluble in water & soluble in C
6
H
6
,
CHCl
3
& CCl
4

boiling point increases as carbon
chain increases
boiling point decreases due to
branching
Preparation of Alkanes
1. Grignard Synthesis of Alkyl halide
Mg in dry ether, (2) H
3
O
+

RX RH
2. Hydrogenation of Alkene
H
2
in Ni/Pt/Pd


H
2
C=CH
2
H
3
CCH
3

3. Reduction of Alkyl halide
Zn (2) HBr


RX RH
4. Wurtz Synthesis (Coupling
Reaction
RX RCH
2
H

















Reactions of Alkanes
1. Halogenation
RH RX
involves initiation, propagation and
termination steps
2.Combustion
C
2
H
2n+2
+ (3n+1/2) O
2
nCO
2
+ (n+1) H
2
O
ALKENES
also called olefins
contains sp
2
hybridized carbon
bond angle 120
o

Preparation of Alkenes
Dehydration of Alcohol
H
3
O
+
, heat
CH
3
CH(CH
3
)CH(OH)CH
3
(CH
3
)
2
C=CHCH
3

Dehydrogenation of Alkyl Halide
KOH, CH
3
CH
2
OH
(CH
3
)
2
CHCH(Br)CH
3
(CH
3
)
2
C=CHCH
3

Saitsevs Rule: The alkene formed is
the one that is more alkyl
substituted.


Debromination of Dibromides
Zn


CH
3
CH(Br)CH(Br)CH
3
CH
3
CH=CHCH
3

Reactions of Alkenes
1.Hydrogenation
H
2
in Ni/Pt/Pd
(CH
3
)
2
C=CHCH
3
(CH
3
)
2
CHCH
2
CH
3

2. Halogenation
X
2
in CCl
4

(CH
3
)
2
C=CHCH
3
(CH
3
)
2
CXCHXCH
3

Halogen add via trans addition
3. Hydrohalogenation
(CH
3
)
2
C=CHCH
3
(CH
3
)
2
CXCH
2
CH
3

Markovnikovs Rule: The halogen
attaches to the carbon that has the
greater number of hydrogen
atoms.
Anti-Markovnikovs take place in the
addition of HX in the presence of
peroxides
4. Hydroxylation
KMnO
4
in basic medium


(CH
3
)
2
C=CHCH
3
(CH
3
)
2
C(OH)CH(OH)CH
3

OsO
4
in NaHSO
4

(CH
3
)
2
C=CHCH
3
(CH
3
)
2
C(OH)CH(OH)CH
3

5. Ozonolysis
O
3,
(2) Zn, H
2
O


(CH
3
)
2
C=CHCH
3
(CH
3
)
2
C=O + CH
3
CHO
6. Oxidation/Cleavage
KMnO
4
in acidic medium


(CH
3
)
2
C=CHCH
3
(CH
3
)
2
C=O + CH
3
CO
2
H


7. Acid-Catalyzed Hydration
H
+
, HOH
(CH
3
)
2
C=CHCH
3
(CH
3
)
2
C(OH)CH
2
CH
3

8. Oxymercuration-Demercuration
Hg(CH
3
COO)
2
/THF,H
2
O
NaBH
4
, HO
-

(CH
3
)
2
C=CHCH
3
(CH
3
)
2
C(OH)CH
2
CH
3

9. Hydroboration-Oxidation
THF, BH
3

H
2
O
2
, HO
-

(CH
3
)
2
C=CHCH
3
(CH
3
)
2
CHCH(OH)CH
3

Follow Anti-Markownikoffs
Addition
10. Halohydrin Formation
X
2
in H
2
O


(CH
3
)
2
C=CHCH
3
(CH
3
)
2
C(OH)CHXCH
3

H
2
O attaches to the highly
substituted carbon
Conjugated, Unsaturated System







Reactions:
1,4-Addition
- carried out at high temperature
- influenced by thermodynamic
control
- more stable product than 1,2-
addition product

SUBSTITUTIONS
C H
3
Cl
+
Na
+
OH-
H
2
O
C H
3
OH +
NaCl
ADDITION
C C
+ X X
CCl
4
C C
X X
ELIMINATION
C C
H X
KOH
C C
-HX
REARRANGEMENTS
C
CH
3
C H
3
C H
3
C
C
H
H
H
ACID CATALYST
C C
CH
3
C H
3
C H
3
CH
3
ACIDS BASES
Bronsted-Lowry
Acid
Lewis Acid Lewis Base
Bronsted-Lowry
Base
Proton
Donor
Electron Pair
Acceptor
Electron Pair
Donor
Proton
Acceptor
Small or negative
Values of pKa
and large Ka
values
Large or positive
Values of pKa
and small Ka
values
Electrophiles Nucleophiles
Strong Acids Strong Bases carbocations carbanions
Weak Conjugate Base Weak Conjugate Acid
C H
2
CH CH CH
2
Conjugated
C H
2
C C CH
2
Cumulated
C H
2
CH CH
2
CH CH CH
3
Isolated
1,2-Addition
-carried out at lower temperature
- kinetically favored product
- less stable product formed

ALKYNES
also called acetylenes
contains sp hybridized carbon
bond angle 180
o

Preparation of Alkynes
Reaction of Sodium Acetylide w/
Alkyl Halides
NaNH
2

CH
3
CCH CH
3
CC
-
Na
+
+ NH
3

Dehydrogenation of Vicinal Halides
KOH, CH
3
CH
2
OH
CH
3
CH(Br)CH(Br)CH
3
CH
3
CCCH
3

Dehalogenation of Tetrahalides
2Zn
CH3C(Br) 2C(Br)3CH3 CH3CCCH3 + 2ZnBr2
Reactions of Alkynes
1. Hydrogenation
2H
2
in Ni/Pt/Pd
CH
3
CCCH
3
CH
3
CH
2
CH
2
CH
3

H
2
in Lindlars Catalyst


CH
3
CCCH
3
CH
3
CH=CHCH
3
(cis)
H
2
in Na/Li in NH
3

CH
3
CCCH
3
CH
3
CH=CHCH
3
(trans)
2. Halogenation
2X
2


CH
3
CCCH
3
CH
3
CX
2
CX
2
CH
3

3. Hydrohalogenation
2HX
CH
3
CCH CH
3
CX
2
CH
3

Follows Markownikoffs Addition
4. Hydration
H
2
O, H
+
, HgSO4
CH3CCH CH3C(OH)=CH2 CH3COCH3
5. Oxidation
KMnO
4
, HO
-
, heat (2) H
3
O
+

CH
3
CCH CH
3
CO
2
H + CO
2

AROMATIC HYDROCARBONS
fragrant, aromatic
low hydrogen to carbon ratio
planar, cyclic and follows Huckels
Rule
Huckels Rule: 4n +2 = electrons
BENZENE
stabilized by resonance
all CH bonds are equivalent
does not decolorize KMnO
4

undergoes substitution reaction
Reactions of Benzene















Other Reactions of
Aromatic Hydrocarbons















Effect of Substituent on Reactivity
of Aromatic Compounds


















































































X
+
HX
X
2
, FeX
3
X = Cl, Br
HONO
2
H
2
SO
4
SO
3
NO
2
O H
2 +
H
2
SO
4
SO
3
RCl, AlCl
3
R can
rearrange
R
RCOCl,
AlCl
3
C
CH
3
O
+
Cl H
+ Cl H
Halogenation
Nitration
Sulfonation
Friedel Crafts Alkylation
Friedel Crafts Acylation
C
R
O
C
OH
O
KMnO
4
, OH
-
, heat
H
3
O
+
CH
2
R
KMnO
4
, OH
-
, heat
H
3
O
+
Zn(Hg), HCl
X
2
hv, heat or ROOR
CH
R
Cl
Na, NH
3
, ethanol
R
(Birch Reduction)
R
H
2
, pressure, Ni
or Pt catalyst
HOOC R
O
3
Zn, HOAc
Activating Substituents ortho/para directing
Strongly activating Moderately activating Weakly activating
-NH2 -NHC=OR -R
-NHR -0C=OR -Ar
-NR2 -CH=CR2
-OH
-OR
Standard Comparison: -H
Deactivating Substituents -
meta directing ortho/para directing
Strongly deactivating Moderately deactivating Weakly deactivating
-NO2 -C=OCl -I
-NHR2, -NR3 -COOH -Br
-NH3, -NH2R -COOR -Cl
-SO3H -C=OR -F
-CN -C=OH

ISOMERS
Constitutional
Differrent
connectivity
Stereoisomers
Enantiomers Diastereomers
Non-superposable
mirror images
Have identical physical
properties (except optical
rotation)
Stereoisomers that
are NOT mirror
images
Have different
physical
properties
Chiral
Molecules
Non-superposable
mirror images
Can Rotate the
plane polarized
light
Optically active
Resolution
Separation of
enantiomers
Racemic Mixtures
a 50/50
mixture of
enantiomer
No optical activity
There is an internal symmetry
Superposable mirror image
Achiral
Molecule
Meso Compounds
Alkene (E or Z
isomers)
SAMPLE PROBLEM
Identify the relationship between the structure by telling if they are
enantiomer, diastereomer, constitutional, or identical
A.
C
F
Br H
CH
3
and
C
Br
H F
CH
3
B.
C
F
Br H
CH
3
and
C
F
H Br
CH
3
C.
and
D.
and
Cahn-Ingold-Prelog Rules (R and S
system)
assign priorities to the atom directly
bonded to the chiral center (high
atomic number or atomic mass =
high priority) Assign number 4 as
the lowest.
Direct 4 away from you and look at
1 2 and 3. Clockwise rotation = R
(rectus) and Counterclockwise
rotation = S (sinister)
If there are multiple bonds present
consider it as multiple atoms





























ORGANIC HALIDES
alkyl halides: RX
vinylic halides: CH
2
=CHX
aryl halides: ArX
most alkyl and aryl halides have very
low solubilities in water, miscible
with each other and other non-polar
solvents
Nucleophilic Substitution Reactions

































S
N
2 (Substitution Nucleophilic
Bimolecular)
One step mechanism
Backside attack
Characterized by Walden inversion
Dependent on concentration of
substrate and nucleophile
Follow 2
nd
order kinetics
Rate = K[substrate][nucleophile]

General Mechanism:






S
N1
(Substitution Nucleophilic
Unimolecular)
Two-step mechanism with
carbocation formation
Dependent on stability of
carbocation formed
Dependent on concentration of
substrate
Follow 1
st
order kinetics
Rate = K[substrate]
Give products of retained and
inverted configuration
General Mechanism:












elimination Reactions
E2 (Elimination Bimolecular)
One step mechanism
Takes place without intermediate
Takes place in 3
o
substrates and
strong basic conditions
rate is dependent on both the
substrate and the alkoxide ion
E1 (Elimination Unimolecular)
Two-step mechanism
Dependent on stability of
carbocation formed
Dependent on concentration of
substrate

















The roots of education are bitter,
but the fruits are sweet.
Thank you.

SAMPLE PROBLEM
Identify if it is R or S.
A.
C CH
2
CH
2
I Cl
CH
2
Br
CH
2
CH
2
CH
3
B.
C CH
2
CH
2
I CH
CH
2
CH
2
SH
CH
2
Cl
C H
3
C H
3
C CH O H
CH
3
CH
2
CH
2
CH
3
CH
2
C.
CONFORMERS
Molecules that differ only by
rotation about sigma bonds
Newman Projections
Eclipsed
conformation
Staggered
conformation
H
H
H
H
H
H
H
H H
H
H H
Anti Gauche
G
G G
G
Chair Conformers
Axial Equatorial
Boat
or
twist boat
C X
Nu:
C X Nu C Nu
+
X-
transition state
C X
-X
-
slow
C
+
C
+
O
H H
fast
C O
+
H
H
O
H
H
enantiomers
C O
+ H
H
O
H
H
fast
C O
H
+
O H
3
+
racemic
mixture
C O
H
+
O H
3
+
C C
Y Z
Elimination
C C
Overall Summary of S
N
1, S
N
2, E1, E2
C H
3
X RCH
2
X RCH X
R
R
2
C X
R
Gives
S
N
2 only
Gives mainly
S
N
2 except
with hindered
strong base
and then gives
mainly E2
Gives mainly
S
N
2 with weak
bases and
mainly E2 with
strong bases
No S
N
2 reaction. In solvolysis
gives E1/S
N
1 and at lower
temperature S
N
1 is favored.
When a strong base is used,
E2 predomenates