LECTURE 8: ORGANIC REACTION AND REACTION
MECHANISMS
Addition Reactions - 2 reactants form 1 product (no
byprouct)
Elimination Reaction -1 reactant split into 2 products
Substitution Reaction – 2 reactants exchange parts to give 2
new products
Rearrangement Reactions – 1 reactant reorganization of
bonds and atoms to yield isomeric product
Single-barbed arrow – “fish hook” movement of 1 e-
Double barbed arrow – “full arow” movement of pair of e-
Symemetrical bon break
Homolytic cleavage – 2e- is eually shared bet. Atoms
Heterolytic cleavage – e- os moved to a more EN atom
Organic Reation Mechanism – Step by Step mechanism of
how bonds break & form
- step by step sequence of elementary reaction by w/c overall
chemical change occur
Electrophile – positively charge atom. (lewis acid)
- accepts e-
Nucleophile – negatively charged atom. (lewis base)
- donates e-
- has free pair of e- or atleast 1 pi bond
Activation energy – must be ocercome to produce product
transition state – chemical specie wherein B-breaking& B-
forming simultaneously happen
Iintermidiate – the value bet. 2 transtitional state
Endothermic – surrounding get cooler
Exothermic – surrounding get warmer
Endothermic Reaction – reaction that absorbs energy
- products have more energy than reactnants
Exothermic Reaction – reaction that releases energy
-reactants have more energy than the products
Catalyst – additive that accelerates chemical reactions
-must not be consumed in the reaction
- lowers activation energy (wrong daw –Proffessor2019)
-provides alternative path with lower activation energy
- modifies kinetics of reaction but do not affect overall
thermodynamics of a reaction
LECTURE 9: FREE RADICAL REACTIONS OF ALKANES AND
CYCLO ALKANES

Alkanes – not very reactive but undergo several types of

transformations (radical reactions)

Radical Reactions – process that invole symetrical B-breaking Abstraction of Cl atom by CH3 radical
& B-making
Radical – neutral chemical species that conatains odd number
of e-. (not + / - ) 3. Chain Termination – combine all free radical in reaction
- has a single, unpaired e- in one of its orbital
- highly reactive
- maybe addition or substitution reaction
-stabilized by hyperconjugation

C-H Hyper Conjugation – sigma e- delocalization

Radical-redical combination
Resonance – pi e- delocalization
Dissociation Energy (DH°) – refers to how easily a bond is
broken by homolytic cleavage
Enthalpy (ΔH ) – if +, reaction is endothermic.
- ↑ DH° = Harder to break bond
- if -, reaction is exothermic
- ↑ DH° ↑EN ↓Atomic Radius
MECHANISM OF FREE RADICAL REACTION
F2 38 – ↑ EN making the bond weaker (F-nag aagawan sa e-)
1. Initiation – homolytic cleavage of Halogen – Halongen Cl2 58 strongest bond
bond producing Halogen radical Br2 46
- Enthalpy is high I2 36 weakest bond

Homolytic cleavage of the Cl-Cl bond

2. Propagation

 Step 1 – avstration of hydrogen from alkane Contributing structures – stabilizes the free radicals
producing alkyl radical
-Enthalpy is still positive   

- primary has 3 contributing structure (yung # bonding

hydrogen sa CH3). Secondary have 6. Tertiary have 9.

Methyl Radical – (probably other alkyl radicals) adopt a

Abstraction of an H atom by Cl
nearly planar configuration, best described by sp2
 Step 2 – producing of more halogen radicals hybridization
- The alkyl radical will react w/ another halogen
- Enthalpy is negative
Free Radical Reactivity

I - Least reactive (activation energy is high)

Br
Cl
F - most reactive (activation energy is low)

Pyrolysis – “bond homlysis” breaking of bond w/ high

temperature

- in the absence of oxygen, radicals can form higher- or lower-

mw alkanes:

- radicals can remove hydrogen from carbon atom adjacent to

another radical center to give alkenes:

EXERCISE (FREE RADICAL HALOGENATION): DETERMINE THE

PRODUCT
LECTURE 10 A: STRUCTURE AND PROPERTIES OF
HALOALKANES
Haloalkanes – “organohalides” or “alkyl halides”
- compounds containing C, H & 1 or more Halogen atoms
- each C forms single covalent bond bet. itself and another C
- some or all of H atoms in parent alkane molecule are
replaced with halogen atoms
IUPAC nomenclature
1. Partent name - Find the longest C chain ( including the
halogen atoms that have subtituted for H atoms)
2. Prefix – determined by number and type of halogen atom.
 Locant
 Multiplier (di, tri, tetra, penta)
 Modified name of halogen (flouro-, chloro-, bromo-,
iodo-)
3. If there are more than 1 atom of same halogen in element
is present
 Each number in the locant is separated by comma
 The lowest set of number is used
 Multiplier precedes the name of halogen atom
4. If different halogent elements are present
 Lowest set of number is used
 Haloens are at equivalent positions, the locant is
based on the alphabetical order of the halo prefixes
5. If haloalkane has alkyl substituents, the halogen
substituent is treated in the same manner as alky
substituents
Physical properties of Haloalkanes
 Bond length – depends on atomic radius of halogen
 Bond strength – depends on EN of halogen atom
- ↑EN ↑Bond str
- ↑EN of halogen ↑polar C-Halogen bond
Optical Activity – ability to rotate plane polarize light
 Light – transverse wave, vibrate perpendicular
Optical isomers
1. Dextrorotatory – rotate plane polarize light to the
right (+) (d-)
- clockwise
2. Levorotatory – rotate plane polarized light to the
left (-) (l-)
- counter clockwise
Polarimeter – measures angle of rotation(α)
Steriocenter –central carbon atom
Plane of symmetry – molecule has mirror image
- molecule is definitely not optically active pag meron nito
Chirality – exist when stereocenter is asymmetric
- asymmetric in such a way that the structure and its mirror
image are not superimposable
- no plane of symetry
- molecule exhibit chirality are almost always optically active
- contains 4 different groups atach to C atom (chiral carbon)
chiral carbon
 Absolute configuration – referes to spatial arrangement of Fischer projection
the atoms of a chiral molecular entity and its stero cchemical - least priority is at top
description rotate molecule such that:
- horizontal bond is pointing towards you
 S (sinister) – counterclockwise - vertical bonds is pointiong away from you
 R (rectus) – clockwiese - molecule can only be rotated 180°

Cahn-Inglod-Prelog rules: the atom with the highest atomic

number receives that top priority number:

 1 – highest priority (↑ atomic #)

 4 – lowest priority (↓ atomic #)

Enantiomers – non-superimposable mirror images of each

other
-optical activities have same magnitude but opposite sign
(-50° s-isomer = +50° r-isomer)
-mirror image
How to determine if it is S or R
Racimic mixture – 50-50 mixture of dextrorotatory &
1. Place the least priority at the back
levorotatory
2. Number base on priority
-optically inactive
3. Determine the rotation of atoms
*Draw the new man projection to help Diastereomers – conatins 2 or more steriocenters
- stereocenter are not mirror images of one another and non-
superimposable

2 1
R –isomer

2
2
1 Meso Compounds – contains 2 or more stereocenters, but
4
3
not chiral; superimposable on its mirror image
3 1 OCH3 - same molecule
(S) - Isomer
- no enantiomers
- has plane of symmetry
2 2
CH2 OH
4
1
CH3CH2 CHO
3 3 (R) - Isomer 1

Identify enantiomer and diastereomers

LECTURE 10 B: REACTIVITY OF HALOALKANES
(SUBSTITUTION NUCLEOPHILIC REACTION)
Subsitution Nucleophilic Reactions – substitution reaction in
w/c nucleophile (Nu-) replaces a leaving group (-L)
Checking the strength of nucleophile
- stronger the base = stronger nucleophile
- if the charge is (-) = strong nucleophile
- ↓EN = more able to share e- = stronger nucleophile
Example:
OH - ↑EN = weaker nucleophile
CH3O - ↓EN = stronger nucleophile

SN1 SN2
NUCLEOPHILE Not Strong
important(usually
weak)
ALKYL SUBSTRATE Bulky 3°>2°>1° Primary
halide>1°>2°>3°
SOLVENT Polar protic Polar aprotic
LEAVING GROUP Good Good
KINETICS Determined by Substrate &
substrate only Nucleophile Polar Protic Solvent – form hydrogen bonds (alcohols)
STEREOCHEMISTRY Retention/& Invertion
(product) Invertion
REARRANGEMENTS Hydride & methyl none
shift
“BIG BARRIER” Carbocation Steric hindrance
stability
Polar Aprotic Solvent – does not form hydrogen bonds

SN1 SN2
Unimolecular Bimolecular
2 Steps: formation of 1 step only: Attack by
carbocation & attack by nucleophile
nucleophile
Attack anywhere Backside attack
Product is recimic mixture Pi e- prevents backside attack
Carbocation (C+) – Carbon atom with only 3 bonds
Product is optically inactive If theres resonance structure
(& double bonds) –sn2 less
SN1 Mechanism - ↑stability of carbocation ↑ SN1 favor
favored
↑Steric hindrance ↓SN2 ↑# of contributing structure ↑ stability of carbocation
attack
WUZZUP YO! ↑# of bulky groups ↓SN2
favor
↓ concentration of
nucleophile ↓ rate of SN2
reaction & indirectly ↑SN1
Reaction rate
F - bad leaving group
Cl
Br
I - good leaving group

↑reactivity of leaving group ↑ rate for SN1 & SN2

Strong bases = poor leaving group

 6. Is the nucleophile Weak Strong & Strong
strong/weak? weak & weak
7. IF there are 2 CH3CH2OH CH3CH2O- CH3S-
solvents/nucleophile, Li+ Na+
which is stronger?
Conclusion:
#1 proceed SN2 Mechanism
#2 proceed SN1 Mechanism
#3 proceed SN2 Mechanism

Note: To get the product, just identify the nucleophile and

Tips to know reaction will proceed to SN1 / SN2 mechanism electrophile(leaving group) and do substitution reaction.
Used the stronger nucleophile if more than 2 are present.
SN1 SN2
1. Is there a good leaving YES YES CARBOCATION REAARANGEMENT – SN1
group? (yes/no) - goal is to make a more stable carbocation
2. How many alkyl substrate 3° 1° / methyl
are present? (1°/2°/3°) 1. 1,2 Hydride shift - is a carbocation rearrangement in
3. What is the solvent used? PROTIC APROTIC which a hydrogen atom in a carbocation migrates to
(protic /aprotic?)
the carbon atom bearing the formal charge of +1
4. Is there a steric hindrance? YES NO
from an adjacent carbon
(yes/no)
5. Can resonance structure be YES NO
formed? Or are there Pi e-
delocalization? (yes/no)
6. Is the nucleophile WEAK STRONG
strong/weak?
7. IF there are 2
solvents/nucleophile, which is 2. 1,2 alkyl shift - is a carbocation rearrangement in
stronger?
which an alkyl group in a carbocation migrates to the
Examples
carbon atom bearing the formal charge of +1 from
CH3CH2OH
1. CH3CH2CH2CH2Br + KOH CH3CH2CH2CH2OH + KBr an adjacent carbon atom.

CH3CH2O- Li+
CH3CH2OH + Licl
2.
CH3S-Na+
3. CH3CH2S + NaI
CH3CH2OH
1 2 3
1. Is there a good Yes Yes yes EXERCISE: determine the product, if its is SN1 or
leaving group? (yes/no) SN2. And if there is rearrangement needed:
2. How many alkyl 1° 1° methyl
substrate are present?
(methyl/1°/2°/3°) C5H5O-
3. What is the solvent Protic Protic Protic
used? (protic /aprotic?)
4. Is there a steric No Yes No
hindrance (sa carbon)?
(yes/no) C5H5OH
5. Can resonance No Yes No
structure be formed?
Or are there Pi e-
delocalization?(yes/no)
LECTURE 11 A: STRUCTURE AND PROPERTIES OF ALKENES
AND ALKYNES

Types of Dienes

1. Conjugated – double bond is separated by 1 bond

-all C are sp2 hybridize carbon
2. Isolated – separated by intervening sp3 carbon
3. Comulated – double bond is on the same carbon
- has sp hybridize carbon