CC2 –ORGANIC CHEMISTRY

PREPARED BY:
ERCED ESTA URBANO
File from
desktop
Aromaticity and Hückel's Rule (4n+2 rule):
In order to be aromatic,

1. Is there a closed loop of adjacent p orbitals (FULLY CONJUGATED)

2. Is it planar
3. Does it follow 4n + 2 = pi electrons , where n is a whole integer

When 

counting

pi

electrons,

only
 the 

count
 ones 
 contribute 

that
 to 

aromaticity
 Aromatic or not

1.Aromatic - only 1 of S's lone pairs counts as π electrons, so there are 6 π

electrons, n=1

2. Not aromatic - not fully conjugated, top C is sp3 hybridized

3. Not aromatic - top C is sp2 hybridized, but there are 4 π electrons, n=1/2

4. Aromatic - N is using its 1 p orbital for the electrons in the double bond, so its
lone pair of electrons are not π electrons, there are 6 π electrons, n=1

5. Aromatic - there are 6 π electrons, n=1

Aromatic or not
6. Not aromatic - all atoms are sp2 hybridized, but only 1 of S's lone pairs
counts as π electrons, so there 8 π electrons, n=1.5

7. Not aromatic - there are 4 π electrons, n=1/2

8. Aromatic - only 1 of N's lone pairs counts as π electrons, so there are 6 π

electrons, n=1

9. Not aromatic - not fully conjugated, top C is sp3 hybridized

10. Aromatic - O is using its 1 p orbital for the elections in the double bond,
so its lone pair of electrons are not π electrons, there are 6 π electrons, n=1
 Organic reactions….
• are often not written as balanced equations
• more interested in the organic product
• side products are often ignored,
• catalysts and solution notation may be left out
• Lewis drawings of molecules are often used
instead of molecular formulas.

7/29/2019 www.themegallery.com
 ORGANIC
REACTIONS

NET RESULT MECHANISM

 ADDITION

ELIMINATION
TYPE OF ORGANIC
REACTIONS
(net result)
SUBSTITUTION

REARRANGEMENT
 Type of reactions
two reactants add together to form single new
product.
single reactant undergoes a reorganization of
bonds and atoms to yield a single isomeric
product
two reactants exchange parts to give two new
products
single reactant splits into two products often
with a formation of a small molecule such as
H2O or HCl
7/29/2019 www.themegallery.com
 HOW A REACTION OCCURS?
Functional group POLAR RADICAL
transformation REACTION REACTIONS

SYMMETRICAL
Oxidation UNSYMMETRICAL
HOMOLYTIC
Reduction HETEROLYTIC BREAKING
BREAKING

HETEROGENIC HOMOGENIC
FORMATION FORMATION

NUCLEOPHILE
FREE RADICALS
ELECTROPHILE
RADICAL / POLAR REACTIONS
Polar Reactions vs Radical Reactions
Energy Diagrams and Transition States

A reaction energy diagram

– depicts graphically the energy changes that occur
during a reaction
– follows the reaction course from reactant through
transition state to product
The transition state ‡
– is an activated complex occurring at the
highest-energy point in a reaction step
– is unstable and cannot be isolated
 Reaction Intermediates

A reaction intermediate or intermediate

– is a species formed during a multistep reaction

– is neither the reactant nor the final product

– lies at an energy minimum between steps on the reaction curve

– is more stable than either of the two transition states that neighbor
it

– is formed briefly during the course of a reaction

– cannot be isolated
Complete Reaction Energy Diagram for Addition of
HBr to Ethylene

• Two separate steps,

each with its own
transition state

• Energy minimum
between the steps
belongs to the
carbocation reaction
intermediate.
Common conversions
 Synthesis:

alkyl alkanes
halide

ALKENES

alcohol dihalide

7/29/2019 www.themegallery.com
 Synthesis:

ESTER RCOOH

ALCOHOL

RCHO RCOR

7/29/2019 www.themegallery.com
 Zaitsev's rule
(or Saytzeff's rule, Saytzev's rule)
• empirical rule for predicting the favored alkene product(s)
in elimination reactions
• small, unhindered base – such as sodium hydroxide, sodium
methoxide, or sodium ethoxide – is used for an E2 elimination
 Hoffman
• Due to steric interactions, a bulky base – such
as potassium t-butoxide, triethylamine
Markovnikov's rule (Markovnikov addition):

• addition reaction of a protic acid HX (hydrogen chloride,

hydrogen bromide, or hydrogen iodide) to an alkene or alkyne,
the hydrogen atom of HX becomes bonded to the carbon atom
that had the greatest number of hydrogen atoms in the
starting alkene or alkyne
 Anti Markovnikov rule
• indicates that hydrogen atoms are attached to the carbon
atom with the least hydrogen substituents
Complete the process:

?
? dihalide
?

?
2-butanone
?
 water
alkene V

? Oxidizing
agent U
V
Propylvalerate

U
 Alkyl Halides and Nucleophilic Substitution
Summary for predicting SN1, SN2, E1 & E2:

Halide Conditions Mechanism

1o strong nucleophile SN2

strong bulky base E2

2o strong base & nucleophile SN2 & E2

strong bulky base E2
weak base and nucleophile SN1 & E1

3o weak base and nucleophile SN1 & E1

strong base E2

Higher temp. favors elimination over substitution.

35
 protic vs aprotic
• protic solvents are capable of hydrogen bonding
because they contain at least one hydrogen atom
connected directly to an electronegative atom .
– solvate cations and anions effectively.
– (water, ethanol, methanol, ammonia, acetic acid)
• aprotic solvents contain no hydrogen atoms
connected directly to an electronegative atom
– not capable of hydrogen bonding
– acetone, dimethyl sulfoxide, DMF (N,N-
dimethylformamide), acetonitrile, HMF
(hydroxymethylfurfural)
All statement are CORRECT about
nucleophilic substitution EXCEPT:
A. SN1 occurs via a carbocation intermediate thus will
require a secondary or tertiary alkyl halide.
B. SN2 occurs via a carbocation intermediate thus will
require a secondary or tertiary alkyl halide.
C. SN2 reactions require a good nucleophile because it is
involved in the rate determining step.
D. SN1 reactions does not require a strong base since it is
not involved in the rate determining step.
 SAMPLE QUESTIONS
Classify the following reaction.

A) substitution
B) addition
C) elimination
D) rearrangement
The methyl chloride undergoes substitution to
form
a) CHCl
b) CH2Cl
c) CHCl2
d) CH2Cl2

Explanation: Chloromethane undergoes

further substitution to form hydrogen chloride
and dichloromethane (CH2Cl2).
 When chlorine gas reacts with
methane, the product formed is

a) CHCl
b) CH2Cl
c) CH3Cl
d) CH4Cl
 SAMPLE QUESTIONS

Which of the following is not a nucleophile?

A) H2O
B) CH3NH2
C) C2H5SH
D) C6H12 (cyclohexane)
 SAMPLE QUESTIONS
In order for a reagent to behave as a
nucleophile it must have ...
A) an overall positive charge.
B) an overall negative charge.
C) a non-bonding electron pair.
D) a nitrogen or sulfur atom.
 SAMPLE QUESTIONS

Which of the following is not an electrophile?

A) C2H5OC2H5
B) BF3
C) [CH3]3C(+)
D) HOCl
 SAMPLE QUESTIONS

Which of the following series contain a free

radical, a nucleophile and an electrophile?
A) Br· BF3 NH3
B) NH3 NO2+ Br2
C) H2O Cl· NH3
D) Cl2 CH4 NH3
 SAMPLE QUESTIONS

Which of the following series contain a free

radical, a nucleophile and an electrophile?
A) Br· BF3 NH3
B) NH3 NO2+ Br2
C) H2O Cl· NH3
D) Cl2 CH4 NH3
Identify the one which does not come under the
organic addition reaction
a) Hydration
b) Dehydration
c) Halogenation
d) Hydrohalogenation

Alcohol on refluxing with Cr2O7 gives:

a) Ester
b) Aldehyde
c) Sugar
d) Carboxylic acid
Alkene under high temperature and high-
pressure forms
a) Alcohol
b) Polyalkyne
c) Polyalkane
d) Polyalkene

Alkenes undergoes polymerization reaction

under high temperature and pressure to form
poly alkanes -(C-C)-n.
• Identify the one which on reaction with
carboxylic acid at high temperature gives Ester
a) Ketone
b) Alcohol
c) Aldehyde
d) Sugars
Primary alcohols undergo what reaction to form
alkenes?
a) Elimination
b) Oxidation
c) Reduction
d) Hydrolysis
Carbonyl compounds especially ketones
undergo reduction to form
a) Primary alcohols
b) Secondary alcohols
c) Alkanes
d) Alkenes

Explanation: Ketones in the presence of NaBH4

undergoes reduction to form secondary
alcohols.
 Which of the following is not true about
nucleophile?
a) donates an electron pair to an electrophile to
form a chemical bond
b) all molecules or ions with a free pair of
electrons or at least one pi bond can act as
nucleophiles
c) nucleophile are Lewis acids by definition
d) a nucleophile becomes attracted to a full or
partial positive charge

Because nucleophiles donate electron pair , Lewis bases

Which types of isomers are formed in
rearrangement reactions?
a) structural isomers
b) Geometrical isomers
c) Optical isomer
d) Conformational isomers

.
Which of the following cannot
react as a nucleophile?
a) CH3NH2
b) (CH3)2NH
c) (CH3)3N
d) (CH3)4N+
Answer: d
Nucleophile donates electron to the electrophiles and there is no lone pair
present on nitrogen (CH3)4N+, so donation of electron is not possible.
The action of nitrous acid on ethyl amine gives
which of the following?
a) Ethane
b) Ammonia
c) Ethyl acohol
d) Nitroethane

Answer: c
The action of nitrous acid on ethyl amine gives
ethyl alcohol, along with nitrogen and water.
CH3CH2NH2 + HNO2 → CH3CH2OH + N2 + H2O
The major alkyne, acetylene compound is
produced by which among the following
application on natural gas

a) Hydrogenation
b) Partial oxidation
c) Cracking
d) Hydrohalogenation
Hydrolysis of ester leads to the formation of
which of the following products in basic
medium?
a) Ether and alcohol
b) Alcohol and sodium carboxylate
c) Aldehyde and alcohol
d) Sodium carboxylate

• Under basic conditions, hydroxide acts as a

nucleophile, while an alkoxide is the leaving
group.
• Which is the mildest reducing agent which
reduces only carbonyl group in presence of
nitro, carboxyl, double bond and ester groups?
a) LiAIH4
b) Na-NH3
c) NaBH4
d) H2-Ni

NaBH4 is mild reducing agent for this conversion. It is very effective for the
reduction of aldehydes and ketones to alcohols. By itself, it will generally not
reduce esters, carboxylic acids, or amides (although it will reduce acyl chlorides
to alcohols).
Ethyl amine undergoes oxidation in the presence
of KMnO4 to form which compound?
a) An acid
b) An alcohol
c) An aldehyde
d) A nitrogen oxide
What will be the product for the given reactant
and reagents?

LiAlH4 will reduce double bond into single bond and aldehyde
group into alcohol.
Substances that will not readily
react with oxidizing agents?
A.ketones
B.tertiary alcohol
C.carboxylic acids
D.all of the choices.
7/29/2019 www.themegallery.com
For an ortho & para attack

A. the groups already attached to the benzene

ring should be , ortho & para directors
B. the entering group should be an ortho & para
directors
C. the entering group should be a meta directors
D. A & B
Sulfonation of nitrobenzene will produce
A. o-nitrobenzaldehyde
B. p-nitrobenzenesulfuric acid
C. m- nitrobenzenesulfuric acid
D. mixture of A & C
Formation of 2,4,6 trinitrotoluene is done by___

A. nitration of benzene followed by alkylation

B. alkylation of benzene followed by nitration
C. nitration of toluene followed by alkylation
D. None of the choices
To obtain p-nitrobenzoic acid

A. nitration of toluene should be done first

before oxidation
B. oxidation of toluene first before nitration
C. A or B
D. neither A nor B
 . GIVE THE MOLECULAR FORMULA OR STRUCTURE
OF COMPOUND (A to Z)
(1) CH2=CH2 + A  B (9) N + OXIDIZING AGENTS 
(2) CH2=CH2 + C  D O ( NAIL POLISH REMOVER)
(3) D + Br2  E (10) N ( DEHYDRATION)  P
(4) D + O2  A + F (11)1,2 DIBROMO ETHANE +
(5) B + OXIDIZING AGENT  Zn  Q
G + OXIDIZING AGENT  (12) R + HCl  2
H ( VINEGAR) CHLOROPROPANE
(6) I ( ANT BITES) + B  J (13) R + Br2  S ( DIHALIDE)
(7) K + A  L (CYCLIC (14) T (30 RX) + NaOH(alc)  V +
ALCOHOL WITH 6 C) A  X + W  no reaction
(8) K + C  M ( ALKANE) (15)U (USED IN WELDING TORCH) +
2HBr  Z