Organic Chemical Reactions 5.

Acid-Base Reaction or Neutralization

Symbols

o + - and
o → vs ⇄ - irreversible, reversible
o ↓ vs ↑ - gas, precipitate
o ∆ - heat

Inorganic Chemistry Renamed in Organic Chemistry

SYNTHESIS ADDITION
A + B → AB A + B → AB
DECOMPOSITION ELIMINATION
AB → A + B AB → A + B
DOUBLE DECOMPOSITION SUBSTITUTION
AB + CD → AD + CB AB + CD → AD + CB
OXIDATION REDUCTION OXIDATION-REDUCTION 6. Oxidation-Reduction Reactions - increase or decrease in
LEORA-GEROA +O/-H - -O/+H oxidation state of two participating compounds
REARRANGEMENT o OXIDATION [O]– addition of O or removal of H, or
interchange of isomers both
o REDUCTION [R] or [H]– addition of H or removal of
O, or both
Types of Reactions o A -> B (A with higher or lower oxidation state)
1. Addition – increase in the number of atoms; from
unsaturated to saturated; a pi bond is usually used up (A +
B → AB)
o two or more reactants, one product Oxidation of ethanol to ethanoic acid

2. Elimination - decrease in the number of atoms; from

saturated to unsaturated; a pi bond is usually added (AB →
A + B)
o one reactant, two or more products

3. Substitution - atoms/groups supplied by the reagent Classify the following reactions:

replaces an atom/group of the substrate; the one replaced a.) CH3Br + KOH -> CH3OH + KBr Substitution
is called the “leaving group” b.) CH3CH2Br -> H2C=CH2 + HBr Elimination
c.) H2C=CH2 + H2 ->CH3CH3 Addition
d.) Cyclopentene reacts with bromine in carbon
tetrachloride to yield 1,2-dibromocyclopentane
Addition
e.) Phenylethanoate in the presence of aluminum
4. Rearrangement/Isomerization - internal rearrangement in chloride and carbon disulfide yield ortho-
the C skeleton of the molecule caused by the migration of ethanoylphenol. Rearrangement “Reduction”
atom/group from one atom to an adjacent one that has only f.) Ethane when heated with bromine gas yields
6 electrons in the valence shell bromoethane and hydrogen bromide Substitution
o the substituents or components of a compound g.) 2-chloropropane reacts with alcoholic potassium
become rearranged to form a new product. (A → hydroxide to yield propene, water and potassium
still A, but isomeric) chloride Elimination
h.) 2-butanone reacts with zinc in the presence of
concentrated HCl to produce n-butane Reduction
i.) Toluene reacts with hot potassium permanganate to
form benzoic acid. Oxidation
Kayla Caliba, 1EPH 1
Key “Terms” electron-poor atoms (usually positive, but NOT
necessarily/can also be partially positive)
o Prefix de– means “removal”
o Suffix –ion means “process”

Name the reaction:

a.) The addition of halogen is halogenation, while the

removal of halogen is dehalogenation.
b.) The addition of hydrogen is hydrogenation while the Which of the following species is likely to behave as
removal of hydrogen is dehydrogenation. nucleophile and which as an electrophile? `
c.) The addition of HX is hydrohalogenation while the
a. NO2+ b. CN- c. CH3NH2 d. (CH3)S+
removal of HX is dehydrohalogenation.
d.) + H2O hydration (removal of water is dehydration)
e.) - The reactant(s) is (are) heated.
f.) + NO2 Nitration
is characterized by
Reaction Intermediates
The reactant at reaching the transition state turns into a
resulting from
reaction intermediate where the bond cleavage has already
occurred. In organic chemistry, most intermediates are those of
carbon because most bonds are concentrated on it. The
following are the most common carbon intermediates:

o Carbanion (C-) – a negatively charged carbon

intermediate, attracted to positive charges
o Carbocation (C+) – a positively charged carbon
intermediate, ,attracted to negative charges
o Carbon free radical (C°) – a carbon intermediate with a Curved arrows help us imagine reactions
single electron, and is highly reactive to other free
radicals

Substrate + Reagent → Intermediate Product → PRODUCT Tips for Interpreting/Using Arrows

o Substrate – the species that is acted upon by a reagent
o Reagent – the species that attack a substrate
o Cleaving – breaking of covalent bond
- Homolytic – equal
- Heterolytic – unequal
Types of reactant (polar reagents) or intermediates:
o Free radicals – possessing an unpaired electron
o Nucleophiles (Nu-) – nucleus loving or proton loving,
neutral or negatively charged, or characterized by at
least one lone pair, electron-rich (usually negative, but
NOT necessarily/can also be partially negative)
o Electrophiles (E+) – electron loving, neutral or positively
charged, or characterized by incomplete octet or has a
FG containing an atom that is positively polarized,
o The arrow always starts with the electron source (a bond or a
lone pair)
- We never START with an atom, but we always END
with an atom
- Since arrows denote movement, you must imagine the
electron source moving to the target, then
disappearing from their original spots
o Check the formal charges of the affected atoms after the
reaction! Add negative or positive charges when needed.
o If an arrow starts from a double bond to a separate atom, a new
bond is formed and the original double becomes single
o If an arrow starts from a single bond to a separate atom, a new
bond is formed and the original single bond disappears
Kayla Caliba, 1EPH 2
o If an arrow starts from a lone pair to a separate atom, a new REACTIVITY
bond will be formed
o If an arrow starts from a lone pair to a single bond, a double  Combustion - oxidation by the use of heat; exothermic
bond will be formed a. Complete – enough oxygen
o All carbons are completely oxidized to
* These are just guides and you’re not supposed to memorize them! Carbon dioxide
There is no substitute for practice and proper analysis. CxHx → CO2↑ + H2O + heat
b. Incomplete/ Partial – limited oxygen
We usually call mechanisms in combination.
o SOME carbons completely oxidized to carbon
Mechanism Reagent Complete Name dioxide
Elimination N/A Elimination o SOME are not, and only oxidized to carbon
Addition E+ Electrophilic Addition (AE) monoxide
Substitution E+ Electrophilic Substitution (SE) o SOME don’t even get any oxygen, and exist as
Substitution Nu- Nucleophilic Substitution (SN) soot
Addition Nu- Nucleophilic Addition (AN)
Substitution Radical Radical Substitution (SR) CxHx → CO2 + CO + C + H2O + heat

*Read on Petroleum, Gasoline, and Octane Number on

Hydrocarbons page 102

o Alkanes - also known as paraffins; saturated Carbon monoxide – the silent killer
- Formula: CnH2n+2 (open-chain) | CnH2n (cyclic) - 500 deaths a year
- Tetrahedral geometry - Signs of CO poisoning: nausea, vomiting,
o Alkenes - olefins; unsaturated shortness of breath, headache
- Formula: CnH2n - Leading causes of CO poisoning
- Planar geometry o Furnace, stove, fireplace, water
o Alkynes - acetylenes; unsaturated heaters, running engines
- Formula: CnH2n – 2
- Linear geometry Men are 2x more likely to be affected by CO poisoning
than women.

 Free Radicals (SR)

ALKANES
1. The synonym paraffin comes from the Latin “parum affinis”
meaning “little affinity” (owing to stability and unreactivity)
- Sigma bonds are difficult to break
o Unreactive to any nucleophile or electrophile
o Will react to heat (combustion) and free radicals
o Chemical properties: not capable of addition
reaction and redox. It undergoes substitution and
combustion.
2. Non-polar, hydrophobic, soluble in other organic
compounds
3. As the no. of carbons increase, boiling point and density If the alkane can be turned into a radical, it could react with
increase while polarity decreases another radical. Sunlight facilitates this process.
4. Branching reduces boiling point and density
The radical often replaces hydrogen atoms, and proceeds
5. Can show conformational and configurational isomerism
as a chain reaction. The mechanism is therefore radical
6. C1 – C4 are gases; C5 – C17 are liquids and C18 and more are
substitution (SR).
solids.
7. Immiscible in water o Initiation - UV cleaves both a chlorine molecule to give
chlorine free radicals.
Cl-Cl + UV ➔ 2 Cl •
o Propagation
a. One Cl• replaces a hydrogen and makes the
organic compound a radical. On the other hand,
Kayla Caliba, 1EPH 3
 the removed hydrogen and the other chlorine
radial form hydrogen chloride.
CH3•H + 2CI • → CICH3• + HCI
b. This continues until no hydrogen can be
substituted.
CH3• + CICH3→ Cl2CH2 + HCl
CH3• + Cl2CH2 → Cl3CH + HCI
CH3• + Cl3CH → CCI4+ HCI
o Termination - chlorine radicals that cannot anymore
substitute alkanes bond to each other (as if the reverse
of Initiation). The reaction stops.
2CI• → Cl-Cl

SYNTHESIS OF ALKANES
o Decarboxylation of the Salt of an Organic Acid
R–COO- Na+ + NaOH → R–H + Na2CO3
o Wurtz Synthesis (or coupling) CYCLOALKANES
2R–X + 2Na → R–R + 2NaX Or Alicyclic Compounds
o Hydrolysis of Grignard’s Reagent (Aliphatic Cyclic)
R–X + Mg → R–Mg–X
R–Mg–X + HOH → R–H + Mg(OH)X REACTIVITY OF CYCLOALKANES
USES
o Fuel - Very similar to alkanes
- Methane – biogas, fuel - Cyclopropane is the most reactive because of its bond
- Propane strain.
- Butane (LPG) *Strains are forces in an organic compound that
o Solvents tend to destabilize it because of certain restraints
- Hexane or arrangements of bonds.
o As substrates for synthesis of other organic compounds
Ring strain Twisting of angles from expected due to
RECALL ring closures
o Single bonds are rotatable giving different Torsional strain Closing of angles between parallel bonds,
conformations. drawing atoms closer
- Eclipsed, staggered and gauche Steric effect Competition for space due to bulky
- These conformations are to relieve the strains groups, pushing bonds away from
(Torsional, Steric and Angle) expected angles
o Produces conformational isomers
- Chirality – mirror images that are not Exercises: using a chemical equation, demonstrate the
superimposable; for alkanes, determined by 4 following:
different groups attached to a C 1. Combustion of cyclohexane
 This C is aka stereocenter, steroeogenic
center, chiral center, chiral carbon, chirality
center, asymmetric carbon or asymmetric
center. 2. Halogenation of cyclohexane
 Enantiomers – mirror images that are not
superimposable; ALL chiral carbons have
been inverted (all R -> S, all S -> R)
CONFORMATIONS OF CYCLOALKANES
 Diastereomers – not mirror images and not
Cyclopentane
superimposable; SOME (not all) chiral
o Less strain than cyclopropane or cyclobutane
carbons have been inverted
o Planar cyclopentane exhibits:
- Designated as R/S using CIP priorities
- Angle strain – very minimal
- Torsional strain – large

Kayla Caliba, 1EPH 4

 o Cyclopentane twists to a nonplanar (puckered) Drawing axial and equatorial positions
conformation
- C1, C2, C3 and C4 are nearly planar but C5 is
out of the plane

Chair conformation
Cyclohexane o Angle strain – none
o Adopts chair conformation o Torsional strain – none
 Angle strain – none
- All C-C-C bonds are 111.5º, close to the ideal Twist-boat conformation
109º o Angle strain – minimal
 Torsional strain - none o Torsional strain – large amount
o Neighboring C-H bonds are staggered o Steric strain – large amount

Drawing chair conformation of cyclohexane

Step 1 – draw parallel lines, slanted downward and
slightly offset from each other Axial and Equatorial Bonds in Cyclohexane
Step 2 – place topmost carbon atom above and to Chair Conformation of Cyclohexane
the right of the plane of the other four, and connect o Chemical behavior of many substituted cyclohexanes is
the bonds influenced by conformation
Step 3 – place bottommost carbon atom below and
to the left of the plane of the middle four, and
connect the bonds

Note: Bonds to the bottommost carbon atom are

parallel to the bonds to the topmost carbon.
o Cyclohexane rings are conformationally mobile.
Chair conformation of cyclohexane
o Chair conformations easily interconvert exchanging axial
There are two kinds of positions for substituents on the
and equatorial positions - called a ring-flip. Ring-flip
cyclohexane ring:
occurs by keeping the middle four carbon atoms in place
o Axial positions – 6 axial positions perpendicular to ring
while folding the two end carbons in opposite directions.
and parallel to ring axis.
o Equatorial positions – 6 equatorial positions are in
rough plane of the ring around the equator

Legend:
axial positions
equatorial positions

Kayla Caliba, 1EPH 5

 ALKENES
RECALL!
Geometric Isomers – there is double bond or when it is cyclic
o Cis and Trans – compounds whose sp2 carbons have 3. Hydration – acid catalyzed
similar substituents (ex. H, methyl, or halogen on *Hydration of alkenes produce alcohols.
either carbon).

o E/Z – no point of comparison

Hydration of asymmetric alkenes – acid catalyzed

Alkenes
o Have the same GF as cycloalkanes Hydration of propene produced a 2° alcohol because
e.g. C4H8 (cyclobutane & 2-butene) of Markovnikov’s rule.
o How can we differentiate? IR spectroscopy and Index of
Hydrogen Deficiency MECHANISMS OF ADDITION
o Use formula: IHD = [(2n + 2) – H]/2 Markovnikov’s Rule
o Or simply determine how many pairs of H When an asymmetric reagent adds to an asymmetric
atoms need to be added to the compound alkene, the electropositive part of the reagent bonds
under study to give the formula of a saturated to the C of the double bond with the greater number
acyclic alkane (2n+2). of H atoms attached to it. The negative part of the
e.g. reagent attaches to the most highly substituted C of the
1. C3H6 IHD = 1 deg or C3H8 - C3H6 = 2H which alkene.
is equivalent to 1 deg
2. C5H10Ɵ IHD = 1 or C5H12Ɵ - C5H10 Ɵ = 2 H
which is equivalent to 1 deg
0 degree = no unsaturation
1 degree = 1 double bond or 1 ring
2 degrees = 2 double bonds, 2 rings, 1 triple
bond, or 1 double bond & 1 ring

ADDITION REACTIONS OF ALKENES

1. Hydrogenation (catalytic) – H2 addition in the
presence of metal catalyst (Pd/C or PtO4 to form an
alkane.
*Hydrogenation of alkenes produce alkanes.
Anti-Markovnikov Addition
Addition of electropositive part of the reagent bonds
to the C of the double bond with least number of H
atoms attached to it. The negative part of the reagent
attaches to the least substituted C of the alkene

Hydroboration - for alcohols that cannot be

synthesized via hydration. Addition occurs so that the
B (electrophile) is added to the less-substituted C.

2. Halogenation – X2 usually dissolved in inert solvents

such as di-, tri- or tetrachloromethane

*Halogenation of alkenes produce vicinal* dihalides.

*Vicinal – X on adjacent C; Geminal – X on the same C
Kayla Caliba, 1EPH 6
 4. Hydrohalogenation of asymmetric alkene
Oxidation of alkenes

*Illustrate the hydrohalogenation of propene following Anti-

Markovnikov addition

Hydrohalogenation of conjugated alkene

Illustrate the hydrohalogenation of butane-1,3-diene

6. Epoxidation of alkenes – using peroxy acid (RCOOH)

Halohydrin formation - addition of X (Br or Cl) and –OH

across a pi bond.

7. Polymerization of alkenes – radical addition

One Br is added across the double bond to form the bromonium

ion. While HO attacks the most substituted C.
Ethene (ethylene) Polyethylene
5. Oxidation to diols –occurs in the presence of oxidizing
agents (especially KMnO4) to for diols (glycols*).

*Compounds with 2 adjacent –OH groups

*Potassium permanganate - Also referred to as Baeyer’s Test/Test
for unsaturation of HC.

Ozonolysis - Oxidation to carbonyl compounds in the

presence of O3 with Zn and acid medium.

Ozonolysis of but-1-ene produces propanal and methanal.

Kayla Caliba, 1EPH 7

 ALKYNES 4. Hydration – acid catalyzed (protic acid) with Hg+2 salt
Alkynes catalysts to form enols (alkene with OH)
o Formula: CnH2n-2
o Classification: terminal and internal o Anti-Markovnikov
o Very reactive chemically, acts as Bronsted-Lowry acid o Hydration in Anti-Markovnikov reaction will
o Ethyne (common name: acetylene) is the simplest yield a 1° alcohol.
member
o Less dense than water
o Solubility: Hydrophobic, Lipophilic (soluble in C6H6 and
CCl4)

ADDITION REACTIONS OF ALKYNES

o An equilibrium (⇄) between enol and keto (carbonyl)
1. Hydrogenation/Reduction Reactions
form, but the equilibrium is strongly shifted to keto form.
o To corresponding alkane with finely divided
Enol and carbonyl compounds are called tautomer (an
metal catalyst (Pt, Pd or Ni)
isomer). The process of converting one to the other is
called tautomerization.
- If hydrated, alkynes become –enol groups which
o To corresponding cis-alkene with Lindlar’s tautomerize to become keto groups.
catalyst (Pb+ salts & organic base) - Propen-1-ol becomes propanal

*For hydrogenation of alkynes, the Lindlar catalyst is required

to limit it to an alkene. Otherwise, Pd converts it to alkane.

SUMMARY
Metal catalyst
Alkynes + H2 Alkane
Lindlar’s
Alkyne + H2 catalyst
Cis alkene
Alkyne + Na/NH3 Trans alkene

2. Halogenation – X2 dissolved in inert solvents such as di-, tri-

or tetrachloromethane
SUMMARY
H+/Hg2+
Alkyne + H2O Aldehydes and ketones
Markovnikov addition

5.
SUMMARY
A. Oxidation with Permanganate (KMnO4)
o 1 alkyne + 1 X2 → vicinal dihaloalkene at trans position o Mild conditions – neutral aqueous solution & moderate T
(anti-addition)
o 1 alkyne + 2 X2 → tetrahaloalkane

3. Hydrohalogenation – alkynes undergo Markovnikov

addition reactions with Bronsted-Lowry acids (HCl, HBr &
What will be the oxidation product of but-1-yne using
HI)
permanganate? 2-oxobutanal
- Therefore, this produces vicinal dicarbonyl
compound
o KMnO4/Oxidative cleavage ( )
o More rigorous conditions – strong base & ↑T
SUMMARY
1 Alkyne + 2HCl → Gem dichloroalkane
Markovnikov addition

Kayla Caliba, 1EPH 8

 Question: What alkyne is produced with propynide anion and
What will be the oxidation product of but-1-yne (asymmetric/terminal) bromoethane? Pent-2-yne
using permanganate under this conditions? Salt of propanoate (3C) and
CO2 (1C)
- Therefore, if one of the products is CO2, it means it is a
terminal alkyne. What is the subtracted if 2 moles are produced?
Ethyne

B. Oxidation with ozone (O3/Oxidative cleavage) in aqueous medium *Used in synthesis of alkynes

What will be the oxidation product of but-1-yne (asymmetric/terminal)

using permanganate under this conditions? Propanoic acid (3C) and
CO2 (1C)
- The alkyne is terminal. Therefore, CO2 is evolved

Practice: What is the product of hex-2-yne using

a. KMnO4, mild b. KMnO4, rigorous c. O3

H3C-CH2-CH2-C≡C-CH3

*Remember: No CO2 can be produced because substrate is NOT a

terminal alkyne.
Answers:
a. Hexane-2,3-dione
b. Salts of butanoic (butanoate) and ethanoic acids
(ethanoate)
c. Butanoic acid and ethanoic acid.

SUMMARY
mild
Alkyne + MnO4- Diketone
base
Alkyne + MnO4- Carboxylic acid salts
heat
Alkyne + O3 Carboxylic acids

6. Acid-base reactions – the H of terminal alkynes act as

Bronsted-Lowry acids and react in the presence of strong
base.
- Not a pi-breaking reaction

*or sodium acetylide (remember HC≡CH is commonly known as

acetylene)

Question: If propyne is used, what do you think is the salt

produced? Sodium propynide

7. Alkylation of acetylides anion with RX (X= Cl, Br or I)

Kayla Caliba, 1EPH 9