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Katerina Cheronis

CHEM 210-1
Acids and Bases
CHAPTER 3 OUTLINE:
Saturated hydrocarbon: no double or triple bonds
Homologous series: compounds differ only by number of CH2 (members are called homologs)
General alkane molecular formula: CnH2n+2.
Common Names (Trivial Names)
Butane:

Pentane:

IUPAC names or systematic names


STEP 1: Find the longest continuous chain of carbon atoms, and use the name of this chain as the base name
of the compound. When there are two longest chains of equal length, use the chain with the greater number of
substituents as the main chain. We start the numbering from the end nearest a branch.
Substituents: groups attached to the main chain
STEP 2: Number the longest chain, beginning with the end of the chain nearest a substituent.
STEP 3: Name the substituent groups attached to the longest chain as alkyl groups. Give the location of each
alkyl group by the number of the main-chain carbon atom to which it is attached.

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STEP 4: When two or more substituents are present, list them in alphabetical order. When two or more of the
same alkyl substituent are present, use the prefixes di-, tri-, tetra-, etc. to avoid having to name the alkyl group
twice. Include a position number for each substituent, even if it means repeating a number
more than once.
Common uses of alkanes: solvents, fuels and lubricants
Polarity: Non-polar (hydrophobic)
Boiling Point Trends

Branched alkanes have a lower boiling point than unbranched Because of their smaller surface area.
Alkanes are less dense than water
The boiling points increase smoothly with increasing numbers of carbon atoms and increasing molecular
weights. Larger molecules have larger surface areas, resulting in increased intermolecular van der Waals
attractions.
Melting Point Trends

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Melting points increase with increasing molecular weight.


Even numbers of carbon atoms pack better into a solid structure, so that higher temperatures are
needed to melt them.

Combustion:

Hydrocracking: hydrogen is added to give saturated hydrocarbons; cracking without hydrogen gives mixtures
of alkanes and alkenes.
Halogenation: Alkanes can react with halogens to form alkyl halides. Heat or light is usually needed to initiate
this halogenation.
Structures and Conformations of Alkanes:
Methane
-Tetrahedral
-109.5bond angles predicted for an sp3 hybridized carbon
-Four hydrogen atoms are covalently bonded to the central carbon atom.
Ethane
- Overlapping sp3 hybrid orbitals forming a sigma bond between them.
- Methyl groups are not fixed in a single position but are relatively free to rotate about the sigma bond
connecting the two carbon atoms
Conformations: The different arrangements formed by rotations about a single bond. Pure conformers cannot
be isolated because the molecules are constantly rotating through all the possible conformations.
Newman projections: a way of drawing a molecule looking straight down the bond connecting two carbon
atoms

Sawhorse structures: picture the molecule looking down at an angle toward the carboncarbon bond.
Dihedral angle: the angle between the bonds on the front carbon atom and the bonds on the back carbon in
the Newman projection.
= 0: Eclipsed conformation
= 60: Staggered conformation
Any other intermediate conformation is called a skew conformation.
The interactions of the electrons in the bonds make the eclipsed conformation higher in energy than the

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staggered conformation (torsional strain).

Torsional Strain: This resistance to twisting (torsion).


Conformational analysis: the study of the energetics of different conformations.
Conformations of Propane

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Conformations of Butane:

Torsional energy of butane. The anti conformation is lowest in energy, and the totally eclipsed
conformation is highest in energy.

The totally eclipsed conformation is higher in energy than the other eclipsed conformations because it forces
the two end methyl groups so close together that their electron clouds experience a strong repulsion.
Steric strain: interference between two bulky groups.
Gauche conformation releases most, but not all, of this steric strain.
Conformations of higher Alkanes:
-

Preference for anti and gauche conformations


The lowest-energy conformation for any straight chain alkane is the one with all the internal carbon
carbon bonds in their anti conformations. These anti conformations give the chain a zigzag shape.

Cycloalkanes: alkanes that contain rings of carbon atoms.


-Resemble acyclic open-chain alkanes in their physical properties and in their chemistry
-Nonpolar
-Relatively inert
-Boiling and melting points that depend on their molecular weights.
-Compact, cyclic shape, so their physical properties are similar to those of the compact, branched alkanes.
Stabilities of Cycloalkanes:

If a cycloalkane requires bond angles other than 109.5, the orbitals of its carboncarbon bonds cannot achieve
optimum overlap, and the cycloalkane must have some angle strain (Bayers strain)

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Cyclobutane: total ellipse conformation leads to torsional strain
Ring Strain = Angular Strain + Torsional Strain
Ring strain depends primarily on the size of the cycloalkane.
To measure ring strain: measure the total amount of energy in the cyclic compound and subtract the amount
of energy in a similar, strain-free reference compound.
Heat of Combustion: amount of heat released when a compound is burned with
an excess of oxygen in a sealed container called a bomb calorimeter.

Cyclopropane:
- More ring strain per methylene group than any other cycloalkane (60 VS 109.5 degrees)
- The orbitals cannot point directly toward each other, and they overlap at an angle to form
weaker bent bonds.
- Max torsional strain: The three-membered ring is planar, and all the bonds are eclipsed
- More reactive when compared to other cycloalkanes

Cyclobutane:
- A planar geometry requires eclipsing of all the bonds, however, as in cyclopropane
- Folded form (bond angles of 88 degrees) to reduce torsional strain butterfly structure
- Slight increase in angle strain compensation for decrease in large torsional strain

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Cyclopentane:
- A planar structure would require all the bonds to be eclipsed
- Envelope conformation that reduces the eclipsing and lowers the torsional strain
- Shape is not fixed, but undulates by the thermal up-and- down motion of the five methylene groups.
The flap of the envelope seems to move around the ring as the molecule undulates.

Cyclohexane:
-Cyclohexane has no ring strain
-A planar, regular hexagon would have bond angles of 120 rather than 109.5, implying some angle strain.
-The structure would also have torsional strain
BUT:
- Cyclohexane achieves tetrahedral bond angles and staggered conformations by assuming a puckered
conformation.
- The most stable conformation is the chair conformation.
- The boat conformation of cyclohexane (angles of 109.5) avoids angle strain.
- The boat conformation suffers from torsional strain, however, because there is eclipsing of bonds. Two of the
hydrogens interfere (flagpole hydrogens).

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-If you assemble your molecular model in the boat conformation and twist it slightly, the flagpole hydrogens
move away from each other and the eclipsing of the bonds is reduced. (Higher energy than chair conformation)
- The highest-energy point in this process is the conformation where the footrest is planar with the sides of the
molecule. This unstable arrangement is called the half-chair conformation.

Axial and Equatorial Positions:

Bonds directed up and down, parallel to the axis of the ring are called axial bonds.
Bonds pointing out from the ring, along the equator of the ring are called equatorial bonds

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Chair-chair interconversion, sometimes called a ring-flip, lower in energy predominates.

Chair with the methyl group in an equatorial position is the most stable conformation.

In general, if both groups cannot be equatorial, the most stable conformation has the larger group equatorial
and the smaller group axial.
Degrees of Unsaturation (DoU)
For a hydrocarbon of N carbons:
Degrees of Unsaturation = (2n + 2 (#H)) / 2
e.g. If DoU = 2: 2 rings or 2 d.b or 1 ring and 1 d.b or 1 triple bond.
- Ignore Oxygen
- Treat halogens like hydrogens
- Subtract 1 H for each N
CHAPTER 4 OUTLINE:

Intermediate Carbon forms:


- Carbocation

The greater the number of R groops the less UNSTABLE (more stable) the carbocation
Rational:
- Inductive effect: The more s character the more electronegative. Electrons stolen from hydrogen

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Hyper conjugation: Stabilization through the donation of the electrons in C-H sigma bonds to the
empty p orbital of the carbonation

- Carbanion
- 8 outer shell electrons
- Act as nucleophiles
- sp3 hybridization (can be sp2 or sp)
- Carbon radicals
- Odd number of electrons
- 7 outer shell electrons
- Order of stability: 3o > 2o > 1o > methyl
-Carbene
-Have 1 lone pair
-Act as nucleophiles
Mechanism of halogenation of alkanes:
e.g. Radical chlorination of Methane

This reaction may continue; heat (^) or light (hv) is needed for each step.
This reaction is a substitution: Chlorine does not add to methane, but a chlorine atom substitutes for one of the
hydrogen atoms, which becomes part of the HCl by-product.
1. The mechanism: step-by-step description of exactly which bonds break, and which bonds form, and in what
order to give the observed products.
2. Thermodynamics: energy changes that accompany chemical and physical transformations. It allows us to
compare the stability of reactants and products and predict which compounds are favored by the equilibrium.
3. Kinetics is the study of reaction rates, determining which products are formed fastest. Kinetics also helps to
predict how the rate will change if we change the reaction conditions.
Observations:
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Polar solvents are unecessary


Gas phase is ok
Mixtures are common (little selectivity)
Reaction requires some form of energy to initiate it.
Once initiated, self sustaining

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Can be inhibited

Chain Reaction Mechanism Steps:


1. Initiation

2. Propagation

3. Termination: decreases the number of free radicals

If anything happens to consume some of the free-radical intermediates without generating new ones, the
chain reaction will slow or stop.

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Equilibrium Constants and Free Energy

If Keq is larger than 1, the reaction is favored as written from left to right. If Keq is less than 1, the reverse
reaction is favored (from right to left as written)
The equilibrium constant for chlorination is very large (10^19) reaction goes into completion
If the energy levels of the products are lower than the energy levels of the reactants, then the reaction is
energetically favored; and this equation gives a negative value of corresponding to a decrease in the energy of
the system.

The more negative G is the more the reactants are converted into products

- Reactions tend to favor products with the lowest enthalpy


- If weaker bonds are broken and stronger bonds are formed, heat is evolved and the reaction is exothermic
- If stronger bonds are broken and weaker bonds are formed, then energy is consumed in the reaction, and the
reaction is endothermic
-Reactions tend to favor products with the greatest entropy
- When we discuss chemical reactions involving the breaking and forming of bonds, we can often use the
values of the enthalpy changes under the assumption that = G
Bond-Dissociation Enthalpies (BDE): the amount of enthalpy required to break a particular bond homolytically

(each bonded atom retains one of the bonds two electrons)

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Kinetics and the Rate Equilibrium


Rate of reaction: measure of fast the products appear and the reactants disappear
Rate equation: relationship between the concentrations of the reactants and the observed reaction rate.

The activation energy is the minimum kinetic energy the molecules must have to overcome the repulsions
between their electron clouds when they collide. The exponential term corresponds to the fraction of collisions
in which the particles have the minimum energy needed to react. We can calculate for a reaction by measuring
how k varies with temperature, and substituting into the Arrhenius equation.
The frequency factor (A) accounts for the frequency of collisions and the fraction of collisions with the
proper orientation for the reaction to occur.

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Transition state is unstable and cannot be isolated, its NOT an intermediate
Many reactions proceed by mechanisms involving several steps and several intermediates
The Rate-Limiting Step: In a multistep reaction, each step has its own characteristic rate. There can be only
one overall reaction rate, however, and it is controlled by the rate-limiting step (also called the rate determining
step). In general, the highest energy step of a multistep reaction is the bottleneck, and it determines the
overall rate. Look for higher activation energy

In a free-radical chain reaction, every propagation step must occur quickly, or the free radicals will undergo
unproductive collisions and participate in termination steps.

Chlorination of Propane: Product Ratios

We can calculate how reactive each kind of hydrogen is by dividing the amount of product observed by the
number of hydrogens that can be replaced to give that product.

Free-Radical Stabilities

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The more highly substituted the carbon atom, the less energy is required to form the free radical.

Bromination of Propane

The 97:1 reactivity ratio for bromination is much larger than the 4.5:1 ratio for chlorination. We say that
bromination is more selective than chlorination because the major reaction is favored by a larger amount.
The energy differences between chlorination and bromination result from the difference in the bonddissociation enthalpies

The HBr

bond is weaker, and

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abstraction of a hydrogen atom by Br radical is endothermic. This endothermic step explains why bromination
is much slower than chlorination, but it still does not explain the enhanced selectivity observed with
bromination.
CHAPTER 5 OUTLINE:

Stereochemistry is the study of the three-dimensional structure of molecules.


Constitutional isomers (structural isomers) differ in their bonding sequence.
Stereoisomers often have remarkably different physical, chemical
Objects that have left-handed and right-handed forms are called chiral
Superimposable if they can be placed on top of each other and the three dimensional position of each atom of
one molecule coincides with the equivalent atom of the other molecule
Non superimposable mirror-image molecules are called enantiomers.

Carbon atom that is bonded to four different groups. Such a carbon atom is called an asymmetric carbon
atom or a chiral carbon atom, and is often designated by an asterisk (*)

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General rules to determine chirality
1. If a compound has no asymmetric carbon atom, it is usually achiral.
2. If a compound has just one asymmetric carbon atom, it must be chiral.
3. If a compound has more than one asymmetric carbon, it may or may not be chiral.
Internal mirror plane, sometimes symbolized by the Greek lowercase letter sigma.

Any molecule that has an internal mirror plane of symmetry cannot be chiral, even though it may contain
asymmetric carbon atoms.
When we cannot find a mirror plane of symmetry, that does not necessarily mean that the molecule must be
chiral.
R and S Nomenclature
The CahnIngoldPrelog convention is the most widely accepted system for naming the configurations of
chirality centers.
1.
2.
3.
4.

Atoms with higher atomic numbers receive higher priorities.


In case of ties, use the next atoms along the chain of each group as tiebreakers.
Treat double and triple bonds as if each were a bond to a separate atom.
Using a three-dimensional drawing or a model, put the fourth-priority group away from you and view
the molecule with the first, second, and third priority groups radiating toward you like the spokes of a
steering wheel. Draw an arrow from the first-priority group, through the second, to the third. If the
arrow points clockwise, the asymmetric carbon atom is called (R). If the arrow points
counterclockwise, the chiral carbon atom is called (S)

Mirror-image molecules have nearly identical physical properties.


Polarimetry is a common method used to distinguish between enantiomers, based on their ability to rotate the
plane of polarized light in opposite directions.
Plane polarized light is composed of waves that vibrate in only one plane.
When polarized light passes through a solution containing a chiral compound, the chiral compound causes the
plane of vibration to rotate. Rotation of the plane of polarized light is called optical activity, and substances
that rotate the plane of polarized light are said to be optically active.
Two enantiomers have identical physical properties, except for the direction they rotate the plane of polarized
light.

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** Enantiomeric compounds rotate the plane of polarized light by exactly the same amount but in opposite
directions.
**We cannot predict which direction a particular enantiomer [either (R) or (S)] will rotate the plane of
polarized light.
A polarimeter measures the rotation of polarized light.
~ Dextrorotatory (clockwise) rotations are or (d).
~ Levorotatory (counterclockwise) rotations are or (l ).
The rotation (alpha) observed in a polarimeter depends on the concentration of the sample solution and the
length of the cell, as well as the optical activity of the compound.

Rotation depends on: wavelength of light and temperature.

A solution of equal amounts of two enantiomers, so that the mixture is optically inactive, is called a racemic
mixture.
** A reaction that uses optically inactive reactants and catalysts cannot produce a product that is optically
active. Any chiral product must be formed as a racemic mixture.
Optical purity calculations:

Chirality of Conformationally Mobile Systems:

A molecule cannot be optically active if its chiral conformations are in equilibrium with their mirror images.
We consider such a molecule to be achiral.
**To determine whether a conformationally mobile molecule can be optically active, consider its most
symmetric conformation.

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Remember: NOT just in ring systems such as cyclohexane
They are in equilibrium with the totally eclipsed conformation, which is symmetric, implying that butane must
be achiral.

Some molecules are so bulky or so highly strained that they cannot easily convert from one chiral
conformation to the mirror-image conformation. They cannot achieve the most symmetric conformation
because it has too much steric strain or ring strain. Since these molecules are locked into a conformation, we
must evaluate the individual locked-in conformation to determine whether the molecule is chiral.
Allenes not planar. Consider:

Fischer Projections:

~ Rotation by 180 is allowed.


~ A 90 rotation is NOT allowed.
The final rule for drawing Fischer projections helps to ensure that we do not rotate the drawing by 90. This
rule is that the carbon chain is drawn along the vertical line of the Fischer projection, usually with the IUPAC
numbering from top to bottom. In most cases, this numbering places the most highly oxidized carbon
substituent at the top.
To test for chirality rotate 180
Naming R and S compounds from Fisher projections: When naming (R) and (S) from Fischer projections with
the hydrogen on a horizontal bond (toward you instead of away from you), just apply the normal rules backward.

All other stereoisomers are classified as diastereomers, which are defined as stereoisomers that are not mirror
images. Most diastereomers are either geometric isomers or compounds containing two or more chirality
centers.
~ Cis-trans Isomerism on Double Bonds
~Cis-trans Isomerism on Rings

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~Two or more chirality centers

compound with n asymmetric carbon atoms might have as many as has 2^n stereoisomers. This formula is
called the 2^n rule, where n is the number of chirality centers (usually asymmetric carbon atoms). The rule
suggests we should look for a maximum of 2^n stereoisomers.
Compounds that are achiral even though they have asymmetric carbon atoms are called meso compounds.
Diastereomers, on the other hand, generally have different physical properties.
When a chiral compound is synthesized from achiral reagents, however, a racemic mixture of enantiomers
results and we must find a way to separate. Separation is called resolution
CHAPTER 6 OUTLINE:

An alkyl halide simply has a halogen atom bonded sp^3 to one of the carbon atoms of an alkyl group.
- Carbon-hydrogen bond is polar because of the electronegative difference.
- Most reactions are a result of breaking the polarized bond
A vinyl halide has a halogen atom of the sp^2 hybrid bonded to one of the carbon atoms of an alkene.
An aryl halide has a halogen sp^2 atom bonded to one of the carbon atoms of an aromatic ring.
The chemistry of vinyl halides and aryl halides is different from that of alkyl halides because their bonding and
hybridization are different.
The carbon atom has a partial positive charge, making it somewhat electrophilic.
If the halogen-bearing carbon is bonded to one carbon atom, it is primary (1) and the alkyl halide is a primary
halide.

Geminal VS Vicinal

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Larger bond == weaker electronegativity


Boiling points
~ The London force is the strongest intermolecular attraction in alkyl halides larger surface areas have larger
~ London attractions, resulting in higher boiling points.
Dipoledipole attractions also affect the boiling points, but to a smaller extent.
~ Higher molecular weights result in greater boiling points
Densities:
~Alkyl fluorides and alkyl chlorides (thosewith just one chlorine atom) are less dense than water
~Alkyl chlorides with two or more chlorine atoms are denser than water, and all alkyl bromides and alkyl
iodides are denser than water.
Free Radical Halogenation:

Does not provide good selectivity or yield


Bromination can be carried out in a highly selective manner
An allylic position is a carbon atom next to a carboncarbon double bond (allylic intermediates stabilized by
resonance).
Abstraction of allylic hydrogen to form product (same mechanism as other radiacal reactions)
This second compound is said to be the product of an allylic shift.

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For efficient allylic bromination, a large concentration of bromine must be avoided because bromine can
also add to the double bond (Chapter 8). N-Bromosuccinimide (NBS) is often used as the bromine source in
free-radical brominations because it combines with the HBr side product to regenerate a constant low
concentration of bromine.
Substitution VS Elimination
The halogen atom can leave with its bonding pair of electrons to form a stable halide ion; we say that a
halide is a good leaving group.
~When another atom replaces the halide ion, the reaction is a substitution.
~When the halide ion leaves with another atom or ion and forms a new pi bond, the reaction is an elimination.

Need to recognize:
When do these reactions happen
Which one predominates
Particular reaction features
Key factors to consider:
Nature of the base/nucleophile
Nature of the Leaving L group
Nature of the solvent
Substrate/Electrophile

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SN2
The SN2 reaction provides a useful method for synthesizing alkyl iodides and fluorides, which are more
difficult to make than alkyl chlorides and bromides. Halides can be converted to other halides by halogen
exchange reactions, in which one halide displaces another.
How does the nucleophile affect a reaction:
~ Strong nucleophile reacts FASTER in an SN2 reaction.
~ A strong nucleophile is much more effective than a weak one in attacking an electrophilic carbon atom.
~ A base is always a stronger nucleophile than its conjugate acid.
~ The more polarizable the better (Iodine is better than Fluorine)
~ Nu must NOT be bulky Avoid steric hindrance
~ Protic solvents (O-H N-H) convenient for nucleophilic substitutions because reagents quite soluble. The
enhanced solvation of smaller anions in protic solvents, requiring more energy
to strip off their solvent molecules, reduces their nucleophilicity.
The polarizability increases with increasing atomic number, and the solvation energy (in protic solvents)
decreases with increasing atomic number. Therefore, nucleophilicity (in protic solvents) generally increases
down a column in the periodic table, as long as we compare similar species with similar charges.
An anion is more reactive in an aprotic solvent because it is not so strongly solvated.
Most polar, ionic reagents are insoluble in simple aprotic solvents such as alkanes.
Polar aprotic solvents have strong dipole moments to enhance solubility, yet they have no O-H or N-H
groups to form hydrogen bonds with anions. Examples of useful polar aprotic solvents are acetonitrile,
dimethylformamide, and acetone.

DONT CONFUSE:
Basicity is defined by the equilibrium constant for abstracting a proton.
Nucleophilicity is defined by the rate of attack on an electrophilic carbon atom.
In both cases, the nucleophile (or base) forms a new bond.
Leaving Group:
To fill these roles, a good leaving group should be
1. electron withdrawing, to polarize the carbon atom,
2. stable (not a strong base) once it has left, and
3. polarizable, to stabilize the transition state.
Good leaving groups should be weak bases; therefore, they are the conjugate bases of strong acids.

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Back-side attack literally turns the tetrahedron of the carbon atom inside out.

We call this result an inversion of configuration at the carbon atom.


SN1
Because this reaction takes place with the solvent acting as the nucleophile, it is called a solvolysis
Steps:
Step 1: Formation of carbocation (rate limiting) (slow)
Step 2: Nucleophilic attack on the carbocation (fast)
Final Step: Loss of proton to solvent (fast) Only when required
Comparison of energy diagrams for SN1 and SN2

Alkyl groups stabilize carbocations by donating electrons through sigma bonds (the inductive effect) and
through overlap of filled orbitals with the empty p orbital of the carbocation (hyperconjugation). Highly
substituted carbocations are therefore more stable.
Hydride Shift

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Carbocations often rearrange to form more stable carbocations. This may occur when a hydrogen atom moves
with its bonding pair of electrons. Formally, this is the movement of a hydride ion although no actual free
hydride ion is involved.
Step 1: Unimolecular ionization gives a carbocation.
Step 2: A hydride shift forms a more stable carbocation.
Step 3: Solvent (a weak nucleophile) attacks the rearranged carbocation.
Methyl Shift
An alkyl group can rearrange to make a carbocation more stable.
Step 1: Ionization occurs with a methyl shift.
Step 2: Attack by ethanol gives a protonated version of the rearranged product.
Step 3: Deprotonation gives the rearranged product.

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CHAPTER 8 OUTLINE:

Catalytic Hydrogenation
Products are more stable than the reactants