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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:
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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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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).
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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:
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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.
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:
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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Can be inhibited
2. Propagation
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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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
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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.
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
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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:
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.
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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.
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:
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:
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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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.
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