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AN INTRODUCTION TO

THE CHEMISTRY
OF ALKANES
Alkanes
Introduction
• Recall that alkanes are aliphatic hydrocarbons having
C—C and C—H  bonds. They can be categorized as
acyclic or cyclic.
• Acyclic alkanes have the molecular formula CnH2n+2
(where n = an integer) and contain only linear and
branched chains of carbon atoms. They are also called
saturated hydrocarbons because they have the
maximum number of hydrogen atoms per carbon.
• Cycloalkanes contain carbons joined in one or more
rings. Because their general formula is CnH2n, they have
two fewer H atoms than an acyclic alkane with the same
number of carbons.
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• All C atoms in an alkane are surrounded by four groups, making
them sp3 hybridized and tetrahedral, and all bond angles are
109.5°.
• The 3-D representations and ball-and-stick models for these
alkanes indicate the tetrahedral geometry around each C atom.
In contrast, the Lewis structures are not meant to imply any 3-D
arrangement. Additionally, in propane and higher molecular
weight alkanes, the carbon skeleton can be drawn in a variety of
ways and still represent the same molecule.

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• The three-carbon alkane CH3CH2CH3, called propane,
has a molecular formula C3H8. Note in the 3-D drawing
that each C atom has two bonds in the plane (solid
lines), one bond in front (on a wedge) and one bond
behind the plane (on a dashed line).

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• Additionally, in propane and higher molecular weight
alkanes, the carbon skeleton can be drawn in a variety
of ways and still represent the same molecule. For
example, the three carbons of propane can be drawn in
a horizontal row or with a bend. These representations
are equivalent.
• In a Lewis structure, the bends in a carbon chain don’t
matter.

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• There are two different ways to arrange four carbons, giving
two compounds with molecular formula C4H10, named butane
and isobutane.
• Butane and isobutane are isomers—two different compounds
with the same molecular formula. Specifically, they are
constitutional or structural isomers.
• Constitutional isomers differ in the way the atoms are
connected to each other.

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• Carbon atoms in alkanes and other organic compounds are
classified by the number of other carbons directly bonded to
them.

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• Hydrogen atoms are classified as primary (1°), secondary (2°),
or tertiary (3°) depending on the type of carbon atom to which
they are bonded.

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• The maximum number of possible constitutional
isomers increases dramatically as the number of
carbon atoms in the alkane increases. For example,
there are 75 possible isomers for an alkane having 10
carbon atoms, but 366,319 possible isomers for one
having 20 carbons.
• The suffix “ane” identifies a molecule as an alkane.
• By increasing the number of carbons in an alkane by a
CH2 group, one obtains a “homologous series” of
alkanes, as shown in Table 4.1. The CH2 group is called
“methylene.”

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Cycloalkanes
Cycloalkanes have molecular formula CnH2n and contain
carbon atoms arranged in a ring. Simple cycloalkanes are
named by adding the prefix cyclo- to the name of the
acyclic alkane having the same number of carbons.

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Nomenclature
The name of every organic molecule has 3 parts:
1. The parent name indicates the number of carbons in
the longest continuous chain.
2. The suffix indicates what functional group is present.
3. The prefix tells us the identity, location, and number of
substituents attached to the carbon chain.

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• Carbon substituents bonded to a long carbon chain are
called alkyl groups.
• An alkyl group is formed by removing one H atom from
an alkane.
• To name an alkyl group, change the –ane ending of the
parent alkane to –yl. Thus, methane (CH4) becomes
methyl (CH3-) and ethane (CH3CH3) becomes ethyl
(CH3CH2-).

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Naming three- or four-carbon alkyl groups is more
complicated because the parent hydrocarbons have more
than one type of hydrogen atom. For example, propane has
both 1° and 2° H atoms, and removal of each of these H atoms
forms a different alkyl group with a different name, propyl or
isopropyl.

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1. Find the parent carbon chain and add the suffix.

Note that it does not matter if the chain is straight or it bends.

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Also note that if there are two chains of equal length, pick the
chain with more substituents. In the following example, two
different chains in the same alkane have seven C atoms. We
circle the longest continuous chain as shown in the diagram
on the left, since this results in the greater number of
substituents.

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2. Number the atoms in the carbon chain to give the first
substituent the lowest number.

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If the first substituent is the same distance from both ends,
number the chain to give the second substituent the lower
number.

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When numbering a carbon chain results in the same numbers
from either end of the chain, assign the lower number
alphabetically to the first substituent.

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3. Name and number the substituents.

• Name the substituents as alkyl groups.


• Every carbon belongs to either the longest chain or a
substituent, not both.
• Each substituent needs its own number.
• If two or more identical substituents are bonded to the
longest chain, use prefixes to indicate how many: di- for two
groups, tri- for three groups, tetra- for four groups, and so
forth.

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4. Combine substituent names and numbers + parent and suffix.

• Precede the name of the parent by the names of the substituents.


• Alphabetize the names of the substituents, ignoring all prefixes
except iso, as in isopropyl and isobutyl.
• Precede the name of each substituent by the number that indicates
its location.
• Separate numbers by commas and separate numbers from letters
by hyphens. The name of an alkane is a single word, with no
spaces after hyphens and commas.

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Cycloalkanes are named by using similar rules, but the prefix
cyclo- immediately precedes the name of the parent.

1. Find the parent cycloalkane.

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2. Name and number the substituents. No number is needed to
indicate the location of a single substituent.

For rings with more than one substituent, begin numbering at


one substituent and proceed around the ring to give the
second substituent the lowest number.

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With two different substituents, number the ring to assign the
lower number to the substituents alphabetically.

Note the special case of an alkane composed of both a ring


and a long chain. If the number of carbons in the ring is
greater than or equal to the number of carbons in the longest
chain, the compound is named as a cycloalkane. 24
Figure 4.2
Two contrasting examples—
Naming compounds containing
both a ring and a long chain
of carbon atoms

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Figure 4.3
Examples of cycloalkane
nomenclature

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Nomenclature—Common Names
Some organic compounds are identified using common
names that do not follow the IUPAC system of
nomenclature. Many of these names were given long ago
before the IUPAC system was adopted, and are still widely
used. Additionally, some names are descriptive of shape
and structure, like those below:
Figure 4.4
Common names for some
polycyclic alkanes

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Physical Properties of Alkanes

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THE CHEMISTRY OF ALKANES

CONTENTS
• Structure of alkanes
• Physical properties of alkanes
• Chemical properties of alkanes
• Breaking covalent bonds
• Chlorination via free radical substitution
• Cracking
• Revision check list
THE CHEMISTRY OF ALKANES

Before you start it would be helpful to…

• Recall the definition of a covalent bond


• Be able to balance simple equations
• Be able to write out structures for hydrocarbons
ALKANES

General members of a homologous series


general formula is CnH2n+2 - for non-cyclic alkanes
saturated hydrocarbons - all carbon-carbon bonding is single
bonds are spaced tetrahedrally about carbon atoms.

Isomerism the first example of structural isomerism occurs with C4H10

BUTANE 2-METHYLPROPANE

Structural isomers have the SAME MOLECULAR FORMULA BUT


DIFFERENT STRUCTURAL FORMULA

They possess different physical properties such as boiling point,


melting point and density
HYBRIDISATION OF ORBITALS

2p
The electronic configuration of a 2
carbon atom is 1s22s22p2 2s

1 1s
HYBRIDISATION OF ORBITALS

2p
The electronic configuration of a 2
carbon atom is 1s22s22p2 2s

1 1s

If you provide a bit of energy you 2p


2
can promote (lift) one of the s 2s
electrons into a p orbital. The
configuration is now 1s22s12p3
1 1s

The process is favourable because the of arrangement of


electrons; four unpaired and with less repulsion is more stable
HYBRIDISATION OF ORBITALS IN ALKANES

The four orbitals (an s and three p’s) combine or HYBRIDISE to give four
new orbitals. All four orbitals are equivalent.

Because one s and three p orbitals are used, it is called sp3 hybridisation

2s22p2 2s12p3 4 x sp3


THE STRUCTURE OF ALKANES

In ALKANES, the four sp3


orbitals of carbon repel each
other into a TETRAHEDRAL
arrangement with bond angles
of 109.5º.

Each sp3 orbital in


109.5º
carbon overlaps with
the 1s orbital of a
hydrogen atom to form
a C-H bond.
PHYSICAL PROPERTIES OF ALKANES

Boiling point increases as they get more carbon atoms in their formula
more atoms = greater intermolecular Van der Waals’ forces
greater intermolecular force = more energy to separate the molecules
greater energy required = higher boiling point

CH4 (-161°C) C2H6 (-88°C) C3H8 (-42°C) C4H10 (-0.5°C)

difference gets less - mass increases by a smaller percentage


straight chains molecules have greater interaction than branched

“The greater the branching, the lower the boiling point”

Melting point general increase with molecular mass


the trend is not as regular as that for boiling point.

Solubility alkanes are non-polar so are immiscible with water


they are soluble in most organic solvents.
CHEMICAL PROPERTIES OF ALKANES

Introduction - fairly unreactive; (old family name, paraffin, meant little reactivity)
- have relatively strong, almost NON-POLAR, SINGLE covalent bonds
- they have no real sites that will encourage substances to attack them

Combustion - make useful fuels - especially the lower members of the series
- react with oxygen in an exothermic reaction

complete CH4(g) + 2O2(g) ——> CO2(g) + 2H2O(l)


combustion

incomplete CH4(g) + 1½O2(g) ——> CO(g) + 2H2O(l)


combustion

the greater the number of carbon atoms, the more energy produced
BUT the greater the amount of oxygen needed for complete combustion.

Handy tip When balancing equations involving complete combustion, remember...


every carbon in the original hydrocarbon gives one carbon dioxide and
every two hydrogen atoms gives a water molecule.

Put the numbers into the equation, count up the O’s and H’s on the RHS
of the equation then balance the oxygen molecules on the LHS.
POLLUTION
Processes involving combustion give rise to a variety of pollutants...

power stations SO2 emissions produce acid rain


internal combustion engines CO, NOx and unburnt hydrocarbons

Removal
SO2 react effluent gases with a suitable compound (e.g. CaO)
CO and NOx pass exhaust gases through a catalytic converter

Catalytic converters
In the catalytic converter ... CO is converted to CO2
NOx are converted to N2
Unburnt hydrocarbons are converted to CO2 and H2O

e.g. 2NO + 2CO ———> N2 + 2CO2

• catalysts are made of finely divided rare metals Rh, Pd, Pt


• leaded petrol must not pass through the catalyst as the lead
deposits on the catalyst’s surface and “poisons” it, thus blocking
sites for reactions to take place.
BREAKING COVALENT BONDS

There are 2 ways to split the shared electron pair in an unsymmetrical covalent bond.

UNEQUAL SPLITTING
produces IONS
known as HETEROLYSIS or
HETEROLYTIC FISSION

EQUAL SPLITTING
produces RADICALS
known as HOMOLYSIS or
HOMOLYTIC FISSION

• If several bonds are present the weakest bond is usually broken first
• Energy to break bonds can come from a variety of energy sources - heat / light
• In the reaction between methane and chlorine either can be used, however...
• In the laboratory a source of UV light (or sunlight) is favoured.
FREE RADICALS

TYPICAL PROPERTIES

• reactive species (atoms or groups) which possess an unpaired electron

• their reactivity is due to them wanting to pair up the single electron

• formed by homolytic fission (homolysis) of covalent bonds

• formed during the reaction between chlorine and methane

• formed during thermal cracking

• involved in the reactions taking place in the ozone layer


CHLORINATION OF METHANE

Reagents chlorine and methane

Conditions UV light or sunlight - heat is an alternative energy source

Equation(s) CH4(g) + Cl2(g) ——> HCl(g) + CH3Cl(g) chloromethane


CH3Cl(g) + Cl2(g) ——> HCl(g) + CH2Cl2(l) dichloromethane
CH2Cl2(l) + Cl2(g) ——> HCl(g) + CHCl3(l) trichloromethane
CHCl3(l) + Cl2(g) ——> HCl(g) + CCl4(l) tetrachloromethane

Mixtures free radicals are very reactive - they are trying to pair their electron
with sufficient chlorine, every hydrogen will eventually be replaced.
CHLORINATION OF METHANE

Reagents chlorine and methane

Conditions UV light or sunlight - heat is an alternative energy source

Equation(s) CH4(g) + Cl2(g) ——> HCl(g) + CH3Cl(g) chloromethane


CH3Cl(g) + Cl2(g) ——> HCl(g) + CH2Cl2(l) dichloromethane
CH2Cl2(l) + Cl2(g) ——> HCl(g) + CHCl3(l) trichloromethane
CHCl3(l) + Cl2(g) ——> HCl(g) + CCl4(l) tetrachloromethane

Mixtures free radicals are very reactive - they are trying to pair their electron
with sufficient chlorine, every hydrogen will eventually be replaced.

Mechanism Mechanisms portray what chemists think is going on in the reaction,


whereas an equation tells you the ratio of products and reactants.

Chlorination of methane proceeds via FREE RADICAL SUBSTITUTION


because the methane is attacked by free radicals resulting in
hydrogen atoms being substituted by chlorine atoms.

The process is a chain reaction.


In the propagation step, one radical is produced for each one used
CHLORINATION OF METHANE

Initiation Cl2 ——> 2Cl• RADICALS CREATED

The single dots represent UNPAIRED ELECTRONS

During initiation, the WEAKEST BOND IS BROKEN as it requires less energy.


There are three possible bonds in a mixture of alkanes and chlorine.

412 348 242


Average bond enthalpy kJ mol-1

The Cl-Cl bond is broken in preference to the others as it is the weakest and
requires requires less energy to separate the atoms.
CHLORINATION OF METHANE

Propagation Cl• + CH4 ——> CH3• + HCl RADICALS USED and


Cl2 + CH3• ——> CH3Cl + Cl• then RE-GENERATED

Free radicals are very reactive because they want to pair up their single electron.
They do this by abstracting a hydrogen atom from methane; a methyl radical is formed
The methyl radical is also very reactive and attacks a chlorine molecule
A chlorine radical is produced and the whole process can start over again
CHLORINATION OF METHANE

Termination l• + Cl• ——> Cl2 RADICALS REMOVED


Cl• + CH3• ——> CH3Cl
CH3• + CH3• ——> C2H6

Removing the
reactive free
radicals brings an
end to the reaction.

This is not very


likely at the start of
the reaction
because of their low
concentration.
CHLORINATION OF METHANE

OVERVIEW

Initiation Cl2 ——> 2Cl• radicals created

Propagation Cl• + CH4 ——> CH3• + HCl radicals used and


Cl2 + CH3• ——> CH3Cl + Cl• then re-generated

Termination Cl• + Cl• ——> Cl2 radicals removed


Cl• + CH3• ——> CH3Cl
CH3• + CH3• ——> C2H6

Summary
Due to lack of reactivity, alkanes need a very reactive species to persuade them to react
Free radicals need to be formed by homolytic fission of covalent bonds
This is done by shining UV light on the mixture (heat could be used)
Chlorine radicals are produced because the Cl-Cl bond is the weakest
You only need one chlorine radical to start things off
With excess chlorine you get further substitution and a mixture of chlorinated products
CHLORINATION OF METHANE

RADICALS
Initiation
PRODUCED

Propagation
RADICALS USED
AND REGENERATED

Termination

RADICALS
REMOVED
CHLORINATION OF METHANE

Further
propagation If excess chlorine is present, further substitution takes place
The equations show the propagation steps for the formation of...

dichloromethane Cl• + CH3Cl ——> CH2Cl• + HCl


Cl2 + CH2Cl• ——> CH2Cl2 + Cl•

trichloromethane Cl• + CH2Cl2 ——> CHCl2• + HCl


Cl2 + CHCl2• ——> CHCl3 + Cl•

tetrachloromethane Cl• + CHCl3 ——> CCl3• + HCl


Cl2 + CCl3• ——> CCl4 + Cl•

Mixtures Because of the many possible reactions there will be a mixture of products.
Individual haloalkanes can be separated by fractional distillation.
CRACKING
Involves the breaking of C-C bonds in alkanes
Converts heavy fractions into higher value products

THERMAL proceeds via a free radical mechanism


CATALYTIC proceeds via a carbocation (carbonium ion) mechanism

THERMAL

HIGH PRESSURE ... 7000 kPa


HIGH TEMPERATURE ... 400°C to 900°C
FREE RADICAL MECHANISM
HOMOLYTIC FISSION
PRODUCES MOSTLY ALKENES ... e.g. ETHENE for making polymers and ethanol
PRODUCES HYDROGEN ... used in the Haber Process and in margarine manufacture

Bonds can be broken anywhere in the molecule by C-C bond fission or C-H bond fission
CRACKING
Involves the breaking of C-C bonds in alkanes
Converts heavy fractions into higher value products

THERMAL proceeds via a free radical mechanism


CATALYTIC proceeds via a carbocation (carbonium ion) mechanism

CATALYTIC

SLIGHT PRESSURE
HIGH TEMPERATURE ... 450°C
ZEOLITE CATALYST
CARBOCATION (IONIC) MECHANISM
HETEROLYTIC FISSION
PRODUCES BRANCHED AND CYCLIC ALKANES, AROMATIC HYDROCARBONS
USED FOR MOTOR FUELS

ZEOLITES are crystalline aluminosilicates; clay like substances


AN INTRODUCTION TO

THE CHEMISTRY
OF ALKANES
THE END

© 2003 JONATHAN HOPTON & KNOCKHARDY PUBLISHING


5. An Overview of
Organic Reactions

Based on McMurry’s Organic Chemistry, 7th edition


5.1 Kinds of Organic
Reactions
• In general, we look at what occurs and try to learn how it
happens
• Common patterns describe the changes
– Addition reactions – two molecules combine

– Elimination reactions – one molecule splits into two

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– Substitution – parts from two molecules exchange

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– Rearrangement reactions – a molecule undergoes
changes in the way its atoms are connected

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5.2 How Organic Reactions
Occur: Mechanisms
• In a clock the hands move but the mechanism behind the
face is what causes the movement
• In an organic reaction, we see the transformation that has
occurred. The mechanism describes the steps behind the
changes that we can observe
• Reactions occur in defined steps that lead from reactant to
product

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Steps in Mechanisms
• We classify the types of steps in a sequence
• A step involves either the formation or breaking of a
covalent bond
• Steps can occur in individually or in combination with
other steps
• When several steps occur at the same time they are said to
be concerted

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Types of Steps in Reaction
Mechanisms
• Bond formation or breakage can be symmetrical or
unsymetrical
• Symmetrical- homolytic
• Unsymmetrical- heterolytic

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Indicating Steps in
Mechanisms
• Curved arrows indicate breaking and
forming of bonds
• Arrowheads with a “half” head (“fish-
hook”) indicate homolytic and
homogenic steps (called ‘radical
processes’)
• Arrowheads with a complete head
indicate heterolytic and heterogenic
steps (called ‘polar processes’)

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5.3 Radical Reactions
• Not as common as polar reactions
• Radicals react to complete electron octet of valence shell
– A radical can break a bond in another molecule and
abstract a partner with an electron, giving substitution
in the original molecule
– A radical can add to an alkene to give a new radical,
causing an addition reaction

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Steps in Radical Substitution
• Three types of steps
– Initiation – homolytic formation of two reactive species with
unpaired electrons
• Example – formation of Cl atoms form Cl2 and light
– Propagation – reaction with molecule to generate radical
• Example - reaction of chlorine atom with methane to
give HCl and CH3.

– Termination – combination of two radicals to form a stable


64 product: CH3. + CH3.  CH3CH3
5.4 Polar Reactions
• Molecules can contain local unsymmetrical electron distributions due
to differences in electronegativities

• This causes a partial negative charge on an atom and a compensating


partial positive charge on an adjacent atom

• The more electronegative atom has the greater electron density


• Elements such as O, F, N, Cl more electronegative than carbon

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Polarizability
• Polarization is a change in electron distribution as a
response to change in electronic nature of the surroundings
• Polarizability is the tendency to undergo polarization
• Polar reactions occur between regions of high electron
density and regions of low electron density

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Generalized Polar Reactions
• An electrophile, an electron-poor species, combines with a
nucleophile, an electron-rich species
• An electrophile is a Lewis acid
• A nucleophile is a Lewis base
• The combination is indicate with a curved arrow from
nucleophile to electrophile

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5.5 An Example of a Polar Reaction:
Addition of HBr to Ethylene
• HBr adds to the  part of C-C double bond
• The  bond is electron-rich, allowing it to function as a
nucleophile
• H-Br is electron deficient at the H since Br is much more
electronegative, making HBr an electrophile

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Mechanism of Addition of HBr
to Ethylene
• HBr electrophile is attacked by 
electrons of ethylene
(nucleophile) to form a
carbocation intermediate and
bromide ion
• Bromide adds to the positive
center of the carbocation,
which is an electrophile, forming
a C-Br  bond
• The result is that ethylene and
HBr combine to form
bromoethane
• All polar reactions occur by
combination of an electron-rich
site of a nucleophile and an
electron-deficient site of an
71 electrophile
5.6 Using Curved Arrows in
Polar Reaction Mechanisms
• Curved arrows are a way to keep track of changes in
bonding in polar reaction
• The arrows track “electron movement”
• Electrons always move in pairs
• Charges change during the reaction
• One curved arrow corresponds to one step in a reaction
mechanism
• The arrow goes from the nucleophilic reaction site to the
electrophilic reaction site

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Rules for Using Curved
Arrows
• The nucleophilic site can be neutral or negatively charged

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• The electrophilic site can be neutral or
positively charged

• Don’t exceed the octet rule (or duet)

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