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Alkanes-

Saturated hydrocarbons—have no double bonds

CnH2n+2

Methane, ethane, propane, butane---heating/cooking

pentane, hexane—longer tend to exist as liquids –fuels

Even further in length---oils, waxes, and tars

A PRIMARY carbon---bonded to only ONE CARBON

A SECONDARY carbon---to TWO

A TERTIARY carbon—to THREE

A QUATERNARY carbon—to FOUR


Physical properties of alkanes

Melting point--- As molecular weight increases so do the melting point. Little funky.
The more symmetrical a molecule, the higher the melting point.

Boiling point--- As molecular weight increases so do the boiling point . Weakened


intermolecular attractive forces (van der Waals) –result in a decreased boiling point.

Density—As molecular weight increases so do the density.

The heavier the molecule—harder for the molecule to break away from others enter
high –energy gas phase

Branched

Slightly lower boiling points

Reduces the surface area of the molecule available for interactions

Molecules cannot stack up as close to each other as they would prefer.

Physical properties of alkanes can be determined by these general


trends:

↑ Chain length: ↑ boiling point, ↑ melting point,↑ density.

↑ Branching: ↓ boiling point, ↓ density.

Combustion

Combustion is incomplete result carbon monoxide

Free Radical Halogenation

Alkane reactions

 Halogenation -hydrogen atoms replaced with halogen via free-radical


substitution
Three Steps

1. Initiation

Free Radical Halogenation (Overall):

R + X2→ RX

2. Propagation

Radical produces another radical that can continue the reaction. Free radical reacts
with an alkane, removes hydrogen to form HX and creates alkyl radical. Alkyl radical
reacts with X2 to form alkyl halide generating radical.
We can always identify a propagation step because it is the only step that both
begins and ends with a radical .

3. Termination

Above will continue until two free radicals combine with one another to from stable
molecule
Carbocations and FREE RADICALS are electron-deficient because have fewer than
the eight electrons needed to complete

The stability of the carbocations in terms of energetics

Remember the trends of stability of both of these species:

3° > 2° > 1° > methyl.

When we talk about secondary carbocations being more stable than primary ones, what exactly do we m
talking about energetic stability - secondary carbocations are lower down an energy "ladder"
than primary ones.
This means that it is going to take more energy to make a primary carbocation than a secondary one.
If there is a choice between making a secondary ion or a primary one, it will be much easier to make
the secondary one.
Similarly, if there is a choice between making a tertiary ion or a secondary one, it will be easier to
make the tertiary one.
This has important implications in the reactions of unsymmetrical alkenes. If you are interested
in these, follow the link below to the electrophilic addition reactions menu.
This is a good general rule to get down now: The more stable the
intermediate is, the more likely the reaction is to occur.

tertiary radical is the most likely to be formed in a free radical bromination


reaction (see Figure 4.3).

Pyrolysis

Molecule broken down by heat

Cracking

Reduce molecular weight of oils

In alkanes C-C bonds cleaved


When a reaction involves UV light, you will almost always see a free
radical. When a reaction involves heat, you should consider the possibility
of free radicals and elimination reactions (discussed in Chapter 5).

549 × 216
549 × 216
Substitution Reactions of Alkyl Halides

Nucleophiles (“nucleus lovers”)---electron rich species attracted to positively


charged / Basicity ---both imply compound wants to donate electrons. Solvent
may stabilize the species and alter trend. Aprotic—trend intact

Electrophile (“electron lovers”)—positively charged, positively polarized

First thing

Identify the nucleophile and the electrophile

Nucleophiles

Nucleophilicity depends on many factors, including charge, basisity,


solvent, polarizability, and the nature of the substituents .

Electron rich species

Basicity-- it is important that the nucleophile be a good base, meaning it


has electrons it wants to share
Nucleophile containing a negatively charged reactive atom is better
than a nucleophile containing a reactive atom that is neutral.

The O of -OH is a better nucleophile than the O of H2O, and results in a


faster reaction rate

NH2 is a better nucleophile than the N of NH3, and results in a faster reaction rate.

When comparing two nucleophiles, say both have oxygen –nucleophilicity correlated
to basicity.

The stronger the base, more likely it is to attract a positively charged proton.
bases are species that accept a proton. (browsted lowry)
Base example:NH3 (aq) + H2O   NH4+(aq) + OH­(aq)

K = 1.8x10­5

In this example, NH3 is a base and H2O is acting as an acid

Nucleophilic strength decreases in this order:

Better
When Moving Across a Row, Nucleophilicity Follows Basicity
To say that nucleophilicity follows basicity across a row means that, as basicity
increases from right to left on the periodic table, nucleophilicity also increases. As
basisity decreases from left to right on the periodic table, nucleophilicity also
decreases.

do not assign this same


When it comes to nucleophilicity,

rule when making comparisons between


the halogens located in a column. In this case of
moving up and down a column, nucleophilicity does not always follow basicity. It
depends on the type of solvent you are using.

Size and Polarizability

Attacking atoms differ DOESN’T correlate with basicity

Protic Solvent

Solvent with protons like water or alcohols

Large atoms tend to be better nucleophiles can shed the solvating protons
surrounding them and are more polarizable.

Fluorine in a protic solvent

Hence, nucleophilic strength decreases in this order:

Radius 133 114 100 72

Better
When it comes to nucleophilicity, size matters in protic solvents (those
capable of hydrogen bonding or donating protons). The smaller atoms can
easily be surrounded by the solvent, which decreases its ability to act as a
nucleophile, and a larger atom thus becomes more nucleophilic in
comparison.

Solvents and Nucleophilicity


In general chemistry, we classified solvents as being either polar or nonpolar. Polar
solvents can be further subdivided into protic and and aprotic solvents.

Protic Solvents
A protic solvent is a solvent that has a hydrogen atom bound to an oxygen or nitrogen. A
few examples of protic solvents include H2O, ROH, RNH2, and R2NH, where water is an
example of an inorganic protic solvent, and alcohols and amides are examples of organic
solvents. The diagram below shows a few examples of protic solvents we will see.

Nucleophilic strength decreases in this order:

Better
Since oxygen and nitrogen are highly electronegative atoms, the O-H and N-H bonds
that are present in protic solvents result in a hydrogen that is positively polarized.
When protic solvents are used in nucleophilic substitution reactions, the positively
polarized hydrogen of the solvent molecule can interact with the negatively charged
nucleophile.

In solution, molecules or ions that are surrounded by these solvent molecules are
said to be solvated. Solvation is the process of attraction and association of solvent
molecules with ions of a solute. The solute, in this case, is a negatively charged
nucleophile.

The following diagram depicts the interaction that can occur between a protic solvent
and a negatively charged nucleophile. The interactions are called hydrogen bonds. A
hydrogen bond results from a from a dipole-dipole force between an electronegative
atom, such as a halogen, and a hydrogen atom bonded to nitrogen, oxygen or
fluorine.

In the case below, we are using an alcohol (ROH) as an example of a protic solvent,
but be aware that this interaction can occur with other solvents containing a
positively polarized hydrogen atom, such as a molecule of water, or amides of the
form RNH2 and R2NH.
Why is this important?
Solvation weakens the nucleophile; that is, solvation decreases nucleophilicity.

This is because the solvent forms a "shell" around the nucleophile, impeding the
nucleophile's ability to attack an electrophilic carbon. Furthermore, because the
charge on smaller anions is more concentrated, small anions are more tightly
solvated than large anions.
The picture below illustrates this concept. Notice how the smaller fluoride anion is
represented as being more heavily solvated than the larger iodide anion. This means
that the fluoride anion will be a weaker nucleophile than the iodide anion. In fact, it
is important to note that fluoride will not function as a nucleophile at all in protic
solvents. It is so small that solvation creates a situation whereby fluoride's lone pair
of electrons are no longer accessible, meaning it is unable to participate in a
nucleophilic substitution reaction.
The effect of protic solvents on nucleophilicity, we learned that solvation
weakens the nucleophile, having the greatest effect on smaller anions. In
when using protic solvents,
effect,

nucleophilicity does not follow


basicity when moving up and down a column. In fact, it's the
exact opposite.

When basicity decreases , nucleophilicity increases.


When basicity increases, nucleophilicity decreases.

In the section Nucleophilic Substitution, we assigned a relationship to leaving groups


containing C, N, O, and F, showing that the strength of the leaving group follows
electronegativity. This is based on the fact that the best leaving groups are those that
are weak bases that do not want to share their electrons.

Thebest nucleophiles however, are good bases that


want to share their electrons with the electrophilic
carbon. The relationship shown below, therefore, is the exact opposite of that
shown for the strength of a leaving group.
Aprotic Solvents

Lack a positively polarized hydrogen

Polar Aprotic Solvents


tetrahydrofuran /-CH2-CH2-O- 66 0.886
7.5 1.75 D
(THF) CH2-CH2-\ °C g/mL
ethyl acetate CH3-C(=O)-O- 77 0.894
6.0 1.78 D
(EtOAc) CH2-CH3 °C g/mL
56 0.786
acetone CH3-C(=O)-CH3 21 2.88 D
°C g/mL
dimethylformamide H- 153 0.944
38 3.82 D
(DMF) C(=O)N(CH3)2 °C g/ml
82 0.786
acetonitrile (MeCN) CH3-C≡N 37 3.92 D
°C g/ml
dimethyl sulfoxide 189 1.092
CH3-S(=O)-CH3 47 3.96 D
(DMSO) °C g/ml

The nucleophiles don't have proton coats surrounding them; they are not
solvated. In this situation, nucleophilic strength is related to basicity. For
example, in the aprotic solvent dimethylsulfoxide, the order of nucleophilic
strength is the same as base strength:

Aprotic solvents, like protic, are polar but, because they lack a positively polarized
hydrogen, do not form hydrogen bonds with the anionic nucleophile. The result, with
respect to solvation, is a relatively weak interaction between the aprotic solvent and the
nucleophile

By using an aprotic solvent we can raise the reactivity of the nucleophile. Consider the
reaction between bromoethane and potassium iodide, the reaction occurs 500 times faster
in acetone than in methanol

A second consequence of weak interaction---under some conditions, there can be an


inversion of the reactivity order. An inversion would result in nucleophilicity following
basicity up and down a column. IN protic, iodine was the strongest nucleophile. NOW, in
aprotic, the fluorine anion is the strongest nucleophile.

Leaving groups

The ease with which nucleophilic substitiution takes place depends on how good a
leaving group is .

The best leaving groups are those that are weak bases, stable
anions or neutral species.

Good leaving groups (weak bases) are the conjugate bases of strong acids.

Opposite of base strength

Weak bases make good leaving groups because they are able to spread out electron
density, making the species more stable

SN1 Reactions

Unimolecular nucleophilic substitution reaction.