Chemistry 31-Summer 2017

Organic Chemistry I

Class Packet

Dr. Brian McNelis

Chemistry Department
Santa Clara University
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Review Material to Study for the Class Begins

Lewis Structures, Molecular Geometry, Determing the Hybridization of Any

Atom

These three topics should be familiar to you from your general chemistry classes,
and they are foundational to understanding bonding in organic molecules as well. I’ll
provide some summary information here, but consult your notes and/or textbook
from last year for supplemental information, and come see me if you struggle with
the problems.

You’ll need to know how to draw Lewis structures, see the detailed guide for
drawing Lewis structures on page 20.

Remember the octet rule. According to the octet rule, every atom is most stable
when it has eight electrons around it. For atoms in row 2 of the periodic table that
we’ll encounter frequently in this class (C, O, N), there can be fewer than eight
electrons around a given atom, but never MORE than eight. Atoms from rows 3 and
higher (e.g., S and P) have d-orbitals, which enable them to accommodate more
than eight electrons around the atom, but there are other ways we can visualize their
bonding as well that does not violate the octet rule.

Molecular Geometry

You’ll need to be able to predict the geometry around a given atom. You’ll need
to be able to estimate bond angles.

Molecular geometry can be predicted by the VSEPR (valence shell electron pair
repulsion) theory. This theory states that an atom will arrange areas of electron
density (bonds or unshared pairs) as far away from one another as possible to
maximize repulsion of the negative charges.

First, count the number of attached atoms and lone pairs. You can refer to this as
counting the areas of electron density. Any bond (single, double, or triple) is just one
area of electron density. Sometimes students want to count each bond as a region
of electron density. Counting attached atoms avoids any confusion. One nonbonding
pair or lone pair electrons is also an area of electron density.

If there are four areas of electron density (four attached atoms and/or lone pairs
such as: four single bonds, two bonds and two unshared pairs, etc.), the atom will
adopt a tetrahedral geometry. Bond angles around that atom will be approximately
109.5°.

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The convention for drawing a tetrahedral atom is to show two bonds in the plane of
the paper as straight lines, one bond “wedged” to indicate that it’s coming out of the
plane of the paper toward the viewer, and one bond “dashed” to indicate that it’s
pointing behind the plane of the paper away from the viewer.

Example: CH4, methane (tetrahedral geometry)

H
All Bond Angles
109.5 o

C
H
H
H

Unshared pairs repel more strongly than bonded electrons. This will compress bond
angles around the atom with unshared pairs to <109.5° (see the first two examples
on page 11)

If there are three areas of electron density, the atom will have a trigonal planar
geometry. Bond angles around that atom will be approximately 120°.

Example: ethylene, H2C=CH2

Each carbon has trigonal planar geometry. Either drawing shown above is
appropriate to illustrate this. On the left is the most common representation, all of the
bonds are in the plane of the paper. In the representation on the right, all of the
bonds are in the plane perpendicular to the paper, so the H’s that are on wedges are
pointing toward you, and the H’s on dashes are pointing away from you. This “edge
on” view is used when we want to show the p-orbitals overlapping to form a π-bond,
see below.

If there are two areas of electron density, the atom will have a linear geometry. Bond
angles around that atom will be 180°.

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Example: acetylene, HC≡CH

Hybridization

You’ll need to be able to assign the hybridization of any atom in a molecule.

You will need to be able to draw p-orbitals in sp2- and sp-hybridized atoms.

To start, make sure you know what σ- and π-bonds are:

Any single bond between two atoms is a σ-bond and is formed by the overlap of
hybrid orbitals.

Multiple bonds comprise a σ-bond and one or more π-bonds. A double bond has one
σ-bond and one π-bond. A triple bond has one σ-bond and two π-bonds. Π-bonds
are formed by the side-to-side overlap of p-orbitals.

Orbital hybridization theory is a way to reconcile the observed molecular geometry,

bond lengths, etc. with our model of valence electrons.

For example, if we look at CH4, methane, we see that carbon forms four equivalent
bonds to H. We can go into the lab and measure the bond length and bond angles of
methane and know that they are all equal. However, if we look at carbon’s 4 valence
electrons, they look like this: 2s22p2. How do valence electrons that are in two
different orbitals (s and p), each of which have different shapes, form four bonds that
are identical in length and bond angles? Under the hybridization theory, neither the s
or p orbital electrons of carbon alone make bonds, rather we mix the s-orbitals and
the three p-orbitals all together to make four hybridized orbitals. These hybridized
orbitals are what make the C-H bonds with the correct geometry around the central
carbon atom. Below I use a wedge and dash notation in the out-of-plane orbitals to
show the plane that orbital resides in. This is non-standard use of the wedge and
dash notation, but it works here to show perspective.

H
H
sp3 orbital

sp3
sp3
C
H H
H sp3 H
H H

methane orbital picture of methane

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In this case, we need to make four bonds, so we need four hybridized orbitals. In its
valence shell, carbon has four total orbitals: one s-orbital and three p-orbitals. We’ll
mix these four orbitals to make four new hybridized orbitals. Four orbitals go in, and
four orbitals come out of the mixing. We call these sp3-hybridized orbitals because
we mixed together the s orbital and 3 p-orbitals. Each makes a σ-bond, and all σ-
bonds are made from the overlap of hybrid orbitals. All four hybridized orbitals are
equivalent in energy and they collectively have the tetrahedral geometry. C is sp3-
hybridized.

Another example: Ethylene, H2C=CH2

Looking at one of the carbons in ethylene, it makes three σ-bonds. Because these
are the same kinds of bonds, it would make sense if they all came from orbitals with
equal energy. It also has a π-bond, which comes from a different kind of orbital. As
we did for methane, we make σ-bonds from hybridized orbitals. In the case of one
ethylene carbon, we’ll need three. So, of carbon’s four valence electron orbitals, we’ll
mix three, one s and two p orbitals. This will make three sp2-hybridized orbitals. The
fourth orbital, a p-orbital, wasn’t included in the mixing, so it stays as a p-orbital.
Both C’s in ethylene are sp2-hybridized.

The π-bond is made from electron density in p-orbitals on adjacent atoms (in this
case, the two carbons). In a π-bond, there will be electron density perpendicular to
the σ-bond. This is because p-orbitals are always perpendicular to the other p-
orbitals (here the other p-orbitals are included in the hybridized, σ-bonding orbitals).
We can show the p-orbitals that make up the π-bond in ethylene using either
drawing perspective that we showed previously. The second picture, it is easier to
see the π-bond and in the first picture we have to use the wedge and dash notation
in the orbital to show the plane that the orbital resides in.

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 H H p-orbital p-orbital

H H
p-orbital
p-orbital
H H
H H
In the rendering on the left, the lobes of the p-orbital that are coming out of the plane
of the paper are denoted with the wedge, while the lobes that are going into the
plane of the paper. Note that a wedge and dash lobe combined make one p-orbital.
In the rendering on the right, the p-orbitals have both lobes in the plane of the paper.
Also, I am only showing the p-orbitals for simplicity here, there are three sp2 orbitals
on each carbon, which make up the σ-bonds (in trigonal plane geometry) simply
shown as lines in these pictures.

Last example, Acetylene, HC≡CH

Consider one carbon in acetylene. It makes two σ-bonds and two π-bonds. As in the
previous example, we’ll make σ-bonds from hybridized orbitals. We’ll need two of
these, so they’re made by mixing an s- and a p-orbital to make two sp-hybridized
orbitals. Two p-orbitals remain unhybridized; these will make the two π-bonds. Each
carbon is sp-hybridized.

We can draw the p-orbitals that make up the π-bonds in acetylene to show the plan
of each π-bond. Each p-orbital is perpendicular both the σ-bonds and the other p-
orbital. The σ-bonds are in the plane of the paper, and are shown as lines rather
than the sp hydrid orbitals overlapping, for simiplicity. One set of p-orbitals has
electron density above and below the σ-bond in the same plane, and the other has
electron density in front of and behind the σ-bond.
represents side to side overlap
of p-orbitals in plane of the page
H H represents side to side overlap
of p-orbitals in plane orthogonal
to plane the page

Other atoms besides C can also be hybridized. For now, we’ll say that all σ-bonds
and all lone pairs around an atom are in hybridized orbitals.
The number attached atoms (or number of σ-bonds) + lone pairs around an atom =
number of hybridized orbitals. π-bonds are always made from p-orbitals.

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 Orbital Shapes and Size
s orbitals

p orbitals

d orbitals

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Orbital Picture Drawing Practice

For the following compounds, draw an orbital picture showing the s-bonds and lines and
the p-bonds as overlapping p-orbitals. Are the H’s in allene and cumulene coplanar?
Are the H’s and the nonbonding electrons on oxygen in ketene coplanar?

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Hybridization Practice Problems

1. The molecule shown below is Biotin, a necessary vitamin for cell growth.

a. Draw in all lone pairs in this molecule consistent with the bonding rules. All atoms
are uncharged.

b. Give the bond angles for angle a and b. Assume no distortions from lone pairs or
other effect.

c. Give the hybridization of carbon 1, 2 and 3. Also give the hybridization of sulfur,
either nitrogen and oxygen 1.

C1: ________ C2: ________ C3: ________

S: __________, N: __________, O1: _________

d. What is the total number of sp2 oxygen atoms? ________

e. What is the total number of sp3 carbons?__________

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2. The molecule shown below is Tetracycline, a common antibacterial drug.

a. Draw in all lone pairs in this molecule consistent with the bonding rules. All atoms
are uncharged.

b. Give the hybridization of Carbons 1, 2, 3 and Oxygen 4

C1: ________ C2: ________ C3 _________ O4 _________

c. What is the geometry at each of these atoms? (ignoring distortions)

C1: ________ C2: ________ C3 _________ O4 _________

d. What is the geometry of 6-membered ring on the left of the structure above?

e. What is the total number of sp2 oxygen atoms? ________

f. What is the total number of sp2 carbons?__________

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3. Determine the hybridization of all atoms in the following structural formulas. Add to
the structures any lone pair electrons before assigning hybridizaiton.

Just for fun, give the name of these amino acids.

4. Two possible orbital pictures for BCl3 are shown below.

A. B.

a. What hybridization for Boron is depicted in A and B?

b. Which picture is the best orbital representation of BCl3?

Why is A or B a better structure?

c. What type of orbital is the empty orbital in A and B?

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 - -
d. BCl3 reacts with Cl to form BCl4 as the product. Predict the hybridization of this
compound and draw an orbital picture.

5. Draw a complete orbital picture for formaldehyde, CH2O and label hybridized orbitals
(sp3, sp2 or sp), sigma and pi bonds and p-orbitals that overlap to form any pi bonds.

6. Two possible charged states for carbon are +1 and -1, which we call a carbocation
and a carbanion, respectively. Example structures for each of these charged species
are given below. Determine the hybridization for both structures and draw an orbital
picture. Note: you can do this problem now, even though we have not discussed
formal charge-we will cover that topic next week. Also, all the electrons are shown, the
carbon in the carbocation has only three bonds and no lone pair.

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Bonding Rules for Nonmetals: Carbon, Oxygen, Nitrogen, Halogens

How to quickly determine the number of bonds for each nonmetal, for zero charged atoms,
without using the Lewis Structure Rules by simply looking at the periodic table. Lewis structure
rules are useful but not really practical for complicated molecules. You will need to able to
predict plausible structures based on bonding rules and knowing the arrangement of atoms.
Also, it is important to be able to determine the number of lone pairs on oxygen, nitrogen, sulfur,
phosphorous and the halogens.

Recall that to form a covalent bond one electron is used from each atom that is sharing
electrons to form the bond. So to form a bond between O and H starting with 6 valence
electrons for O:

O H
H O H H O H
Bond show show
bond as bond as
line line

The octet rule for nonmetals (except for H) gives us a clear prediction of the number of bonds
each nonmetal will form to achieve an octet. Count the number of valence electrons, and the
number of covalent bonds will be the difference between the number of valence electrons and 8.
This makes sense, since carbon needs 4 electrons to achieve an octet and for each covalent
bond made, the atom gains one electron.

For example, Carbon has 4 valence electrons, so carbon will form 4 covalent bonds at zero
charge. So for CH? , the ? has to be 4, CH4

But what about C2H? ? There are three possible structure, but all the structures must have 4
bonds to carbon.
C 2H 6 C 2H 4 C 2H 2
Both carbons have No octet-only 3 bonds No octet-only 2 bonds
an octet each carbon each carbon
H H H H
H C C H C C H C C H
H H H H
Add muitple
Structure Add muitple bonds, 2 between
complete! bond carbons

H H H C C H
C C
H H Structure
complete!
Structure
complete!

Oxygen has 6 valence electrons, so two covalent bonds. But what about the other 4 valence
electrons? They are on the on the oxygen in form of 2 lone pairs. Complete the structures of
following condensed formulas, which give the approximate arrangement of atoms.

CH3CH2OH (CH3)2CHCO2H CH3CHO

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 H H H H O Add another H H O O Add another O
bond H C C H H C bond H C
H C H H C C H
C O C O C O C H C H
H H H H H H H
C and lone C and lone
H
H HH pairs H HH pairs
Not correct
Not correct

Nitrogen has 5 valence electrons, so forms three bonds and has one lone pair:

H
H N H
C C
H H
H H

-Halogens (F, Cl, Br, I) have 7 valence electrons, so form one bond with 3 lone pairs:

H H
H C
C Br
H
H

From this process, we can always remind ourselves of the bonding rules by looking at the
periodic table and this allows us to quickly construct accurate structures without using the
tedious Lewis Structure rules. What about Boron? With only 3 valence electrons, Boron can
form 3 bonds only, so can not achieve an octet. Not surprisingly, Boron’s chemical reactivity is
very different from the other nonmetals that can achieve an octet. What about charged atoms?
See the Formal Charge Rules and Standard Charge States for these same atoms.

Bonding Rules for Zero Charged Nonmetal Atoms

Atom Number of Number Number of

Valence Electrons of Bonds Lone Pairs
C 4 4 0
N 5 3 1
O 6 2 2
F, Cl, Br, I 7 1 3
P 5 3 1
S 6 2 2
H 1 1 0
B 3 3 0

What about Sulfur and the so-called expanded octet? See the Formal Charge Rules, we will
cover that topic in that section.

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Bonding Rules and Lewis Structures Practice Problems

1. Given what you know about the bonding rules for nonmetals, use the molecule
formula to complete the following structures. Also draw in any lone pair electrons to
complete the structures.

2. Complete the molecular formulas below and draw a Lewis structure for the
compound.

CF? CH?Cl2 CH3SH? CH3NH?

NH?OH CH?O

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3. Draw the Lewis structure for the following molecular and condensed formulas.

N2 H4 CH3CO2H

BF3 CH3OCH3

4. Given the molecular formulas and the templates given, complete the following Lewis
structures.

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 Skeletal Drawings in Organic Chemistry
Rules:
1. Carbon atoms are represented by the ends of lines or the junctions between lines without using
the chemical symbol, C. The lines represent the bonds between carbon atoms.
2. Hydrogen atoms attached to carbon atoms are not shown explicitly. Sufficient hydrogen atoms
are assumed to be attached to the carbons so that each carbon has four bonds. Be sure to count
the correct number of bonds - double bonds count as two bonds and triple bonds count as three
bonds.
3. All other types of atoms (e.g. O, S, N, Cl) are shown explicitly.
4. Hydrogens attached to atoms other than carbon are always shown explicitly.
5. Nonbonding electron pairs on atoms are not typically shown. Sufficient nonbonding pairs are
assumed so that each atom has a full outer shell of 8 electrons.

Note- at times carbon atoms, assumed hydrogens and nonbonding electron pairs will be shown
for emphasis.

Examples and Practice – Convert the following Lewis structures to skeletal drawings and convert
the following skeletal drawings to complete Lewis structures.

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Wedges and Dashes
As introduced in the molecular geometry discussion, to show the three-dimensional
perspective, we represent bonds as wedges or dashes. A bond that is shown as a wedge
indicates that the atom shown is coming OUT OF the plane of the paper. A bond that is
shown as a dash indicates that the attached atom is going INTO the plane of the paper.
Bonds shown as straight lines are in the plane of the paper.

Typically, we’ll represent any tetrahedral atom with two bonds that are in the plane of the
paper (straight lines), one bond coming toward you (wedge), and one bond going away from
you (dash). So, other representations may show this level of spatial detail where it needs to
be highlighted specifically.

Helpful tips and mistakes to avoid when drawing organic molecule structures and to
improve the quality/readability of your structures:

1. NEVER draw a carbon with more than four bonds.

2. If you show explicit carbons in a molecule, you must also show all H’s bonded to that
carbon. For example:

3. Try to draw the bonds as far apart as possible in the skeletal drawings.

4. There can be more than one correct way to show the same structure. For example, the
molecules below are all identical. This tends to confuse student initially. Recognizing that
two structures are identical is a skill we will work on in class when we discuss isomers
(see page ? in the class packet) and superimposability.

5. When adding wedges and dashes to a skeletal structure, like pentane, follow the process
below.
The molecule is "telling" you which way to draw in the wedges and dashes. Start with the carbons in the central part of the molecule, not the ends:
pointing up,
just like an arrow head Note, to left or right does
not matter

H H HH H H HH H H HH
H H H H
Add Add H's
Add H H Add H's H H Add HHH H HH
Wedges (or Wedges (or
pointing down dashes) on each wedges and
dashes) dashes for 4
pointing up pointing up end
and down additioal H's
and down

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Drawing Lewis Structures
1. Sum the valence electrons from all atoms.
(Use the periodic table as necessary to help you determine the number of valence electrons each atom.)
For an anion, add an electron for each negative charge. For a cation, subtract an electron for each
positive charge. Don’t worry about keeping track of which electrons come from which atoms. Only
the total number is important.

2. Write the symbols for the atoms to show which atoms are attached to which, and connect them with
a single bond (a dash, representing two electrons). Chemical formulas are often written in the order in
which the atoms are connected in the molecule or ion, as in HCN. When a central atom has a group of
other atoms bonded to it, the central atom is usually written first, as in CO32- and SF4. In other cases,
you may need more information before you can draw the Lewis structure.

3. Complete the octets of the atoms bonded to the central atom. (Remember, however, that hydrogen
can have only two electrons.)

4. Place any leftover electrons on the central atom, even if doing so results in more than an octet.

5. If there are not enough electrons to give the central atom an octet, try multiple bonds. Use one or
more of the unshared pairs of electrons on the atoms bonded of the central atom to form double or
triple bonds.

Example: CO3-2
1. Total valence electrons = 4 + 3 x 6 + 2 = 24 electrons
(H) (O) (Charge)
2. Place the atoms in order of attachment, and
3. Place a bond (using a line) between attached atoms. Each bond accounts for two electrons.

4. Fill in remaining electrons on the peripheral atoms first to achieve and octet for those atoms. Do
not put electrons on hydrogen atoms. Any leftover electrons go on the central atom.
24 – 6 bonding electrons = 18 electrons on perpheral atoms.

5. Check for octets on all atoms. If central atom does not have an octet, “move” electrons from
peripheral atoms “in” creating multiple bonds to the central atom. Do this until octet on central
atom is achieved.
Oxygens have octet, carbon has only 6 electrons. Move one pair in, gives carbon octet
See picture above.

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Bond polarity, dipoles, and dipole moments

A polar covalent bond refers to a bond in which the electrons that make up the bond are not shared
equally between the two atoms. Which atom gets more electron density is determined by the atoms’
electronegativities. Electronegativity is the tendency of an atom to attract electrons to itself in a bond.

The most common scale is the Pauling Electronegativity scale, shown below. I’ll never ask you to
memorize these numbers, but you should know the periodic trends. Electronegativity increases left
to right and bottom to top.

Dipoles are formed when opposite charges are separated. Polar bonds can form dipoles. We represent
the dipole of a bond using the conventions shown in the examples below. For the polar O-H bond in
ethanol, we can draw a hatched arrow (shown on the left). The arrow points to the more
electronegative element and is hatched by the less electronegative atom. Alternately, we can show
partial charges, δ+ and δ-, next to the corresponding atoms. The more electronegative atom in the bond
will have a partial negative charge (δ-). Organic chemists use the partial positive and negative signs
frequently when denoting polarity and we do this to understand a molecule’s reactivity.

δ+ δ-
H H O
Br δ-
O O
δ- δ+
δ+

1 2
Electronegativity of the
H Elements He
2.1 ----

3 4 5 6 7 8 9 10
Li Be B C N O F Ne
1.0 1.6 2.0 2.5 3.0 3.5 4.0 ----

11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
0.9 1.2 1.5 1.8 2.1 2.5 3.0 ----

19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
0.8 1.0 1.3 1.5 1.6 1.6 1.5 1.8 1.9 1.9 1.9 1.6 1.6 1.8 2.0 2.4 2.8 ----

37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
0.8 1.0 1.2 1.4 1.6 1.8 1.9 2.2 2.2 2.2 1.9 1.7 1.7 1.8 1.9 2.1 2.5 ----

55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
0.7 0.9 1.0 1.3 1.5 1.7 1.9 2.2 2.2 2.2 2.4 1.9 1.8 1.9 1.9 2.0 2.1 ----

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Bond Length and Strength
Bond Bond Length (Å) Bond Strength (kcal/mol)

1.54 90

1.33 146

1.20 200

1.38 116

1.78 79

1.94 66

2.14 52

1.41 86

1.06 98

Bond Length and Strength – McNelis Numbers

Bond Bond Length (Å) Bond Strength (kcal/mol)

1.5 90

1.3 150

1.2 200

1.4 120

1.8 80

1.9 70

2.1 50

1.4 90

1.1 100

Standard σ 1.5 100

Standard π 1.3 50

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Formal Charges
A charge on an atom arises when there is a bonding motif different than the typical valence for that
atom. Usually, there is one more or one less bond than is typical (C:4; N:3; O:2, H:1). The three
structures below illustrate charge states for nitrogen and oxygen.

Ozone Nitromethane Azide

The formal charge on an atom may be calculated by the following formula:

This is the method for formal charge calculation in most texts, both for General Chemistry and
Organic, and this formula is useful but it has to be memorized.

Easier Methods to Determine Formal Charge

There is an easier method that I use to determine the charge on any atom by comparing the number
of electrons around the bound atom with the number of valence electrons in the element. Count the
electrons around the atom in an intuitive manner, half of the bonding electrons (since a covalent bond
shares two electrons, we count only one electron for each covalent bond) and all the nonbonding
electrons. Compare this number of electrons to the number of electrons for the element. If these
numbers of electrons are the same, then the atom is zero charged. If the atom has one more electron
than the valence electrons in the element, the charge is -1. If the atom has two more electrons, the
charge is -2 (which is rare). If the atom has one less electron that the valence electrons in the
element, the charge is +1, two less electrons and the charge is +2. The sign of the charges here make
sense, since an atom that has more electrons will be negative charged and the atom that has less
electrons than the element will be positively charged as compared to the element. It is important to
note that If you have a charge that is -3 or +3, in this course, you are assigned the formal charge
incorrectly.

A useful approach for most beginning organic chemists is to simply recognize the common charge
states that we observe in organic compounds. Although it is possible, you will rarely see +2 or -2
charge states for nonmetal atoms. Given this, we can detail the general Lewis structures that we will
see for the nonmetal atoms with the +1 and -1 charge states.

Below are these general Lewis structures along with the zero charge states for comparison. In the
pictures of the charge states, the number of bonds is represents by a line, and this bond can arise
from a sigma bond or a pi bond. Notice that nitrogen and phosphorous have the same charge states.
The same is true for oxygen and sulfur and all the halogens (F, Cl, Br and I).

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Unusual Charge States:
There are some unusual charge states that we will see, especially for sulfur, but we will cover those
as we encounter them. We are striving to learn the most common structural features of organic
compounds, not the exceptions.

You can always rely on the rules and the charge states above to determine the charge of any atom in
a molecule, even if it is an unusual structure. Determine the formal charges all the atoms in the
following structures, all lone pair electrons are shown.

Structure Drawing and Charge Conventions

Although we teach how to determine formal charge from complete Lewis structures, with all atoms
and lone pair electrons shown, it is more common that the charge for an atom is given and the
number of electrons or assumed hydrogen atoms are not shown. This is the convention in most texts
and journal articles. For the beginning organic student, using the formal charge to determine the
number of attached atoms and lone pair electrons to complete a structure will be an important first
step in understanding the reactivity of a compound. There are problems to practice this skill in the
Class Packet

30
Formal Charge Practice:
1. For the following compounds, determine the formal charge for all the heteroatoms (O, N and S).
All nonbonding electrons are shown. For carbon atoms, assume zero charge and fill in the correct
number of assumed hydrogens. Note: there are no assumed electrons on carbon, they have to be
explicitly shown with nonbonding electrons and/or with a charge notation.

2. For the following compounds, determine the charge for all the atoms. All assumed hydrogens and
nonbonding electrons are shown.

3. For the following compounds, all charges are shown as they might typically be in texts or the
chemical literature. Add to these structures the correct number of assumed nonbonding electrons
and hydrogens consistent with the formal charges as shown. Recall from the drawing conventions,
hydrogens are always shown on heteroatoms (O, N and S) so only hydrogens on carbons are
assumed and need to be added to the structure below. As always, assume zero charge unless a
charge is shown.

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Nomenclature Rules : IUPAC System
Prefix-Parent-Suffix

A. Define the Parent Chain:

1. Pick out the longest continuous carbon chain.
2. With two chains the same length: chose the one with largest number of branches.
3. Number the carbon chain from the end nearest to the first branching on the chain.

B. Assemble the Prefix:

1. Name the substituents *(see below for special cases- F* and G*)
2. Give a location number on the parent chain for each substituent
3. For more than one of the same substituent use prefixes (di, tri, tetra, penta etc.) and the
location numbers separated by a comma. i.e. 2, 6-dimethyl

C. Suffix: Family Designation

1. For the family of Alkanes: -ane.
2. Other family suffixes will be learned in due course.
D. Writing the Name:
1. Written as a single word, hyphens separating the numbers and words. (i.e. no spaces in a
chemical name)
2. Write the substituents in alphabetical order.
a. Use the main name of the substituent for order placement.
b. Any number prefixes (di, tri, tetra) and hyphenated prefixes (sec-, tert- or t- ) are not
used for alphabetizing purposes.
c. Non hyphenated prefixes such as iso are used in alphabetizing (i.e. isopropyl and
isobutyl).

F*. Complex Substituents:

1. Begin numbering at the point of attachment to the main chain of the molecule.
2. Number the longest chain and name it as an alkyl substituent (i.e. propyl, butyl, pentyl etc.)
3. Create a prefix using the rules above for naming the substituents and giving location
numbers on the chain.
4. This name is set off in parenthesis with a location number on the main chain in front.

G. Common Names for Substituents:

1. Nonsystematic common names to know: isopropyl, tert-butyl or t-butyl isobutyl.
You might encounter but will not be expected to know: sec-butyl, isobutyl. (see below for
structures).
2. Others are less common and can be named by complex substituent rules.

32
 Names of Straight Chain Alkanes:
C1- methane C6- hexane C11- undecane
C2- ethane C7- heptane C12- dodecane
C3- propane C8- octane C13- tridecane
C4- butane C9- nonane
C5- pentane C10- decane

Most Common Alkyl Groups:

Methyl: -CH3 Ethyl: -CH2CH3 Propyl: -CH2CH2CH3
Butyl: -CH2CH2CH2CH3 Pentyl: -CH2CH2CH2CH2CH3

Common Groups Structures:

Need to know: Other common groups:

Cycloalkanes:

Naming Cycloalkanes:

A. Parent Cyclic is usually the main name

1. Unless side branch has more carbons than cyclic then named as a substituent on the chain
2. Cycloalkanes as substituents are named as alkyl group (i.e. cyclopropyl, cyclobutyl,
cyclopentyl, etc).

B. Number from point of attachment of the substituent

1. If more than one substituent, number on the ring to achieve the lowest location numbers.
2. If location numbers are the same for two numbering schemes:
a. Give number priority to the groups by alphabetical priority (i.e. number ethyl before
methyl).
b. Halogens are named exactly like alkyl groups. Use fluoro, chloro, bromo, iodo in naming
prefix with location number before name.

33
Electromagetic Spectrum - Introduction to Spectroscopy

34
35
Infrared Spectroscopy: Simplified Correlation Table, Structural Examples

36
IR Example Spectra

1. Pentane

2. Cyclohexene

37
3. Styrene

4. 1-Pentyne

38
5. 1-Hexanol

6. 2-Butanol

39
7. 3-Methyl- 2-butanone

8. Pentanal

40
9. Ethyl butanoate

10. Acetophenone

41
11. Propanoic acid

12. Acetamide

42
13. Butyl propenoate

14. 3-Nitrobenzoic acid

43
15. Acetonitrile

44
IR Spectra In-Class Problems

1.

2.

45
3.

4.

46
 5.

6.

47
IR Practice Problems
1.

2.

48
3.

4.

49
5.

6.

50
7.

8.

51
IR Problem Set - List of Compounds

Match the compounds below to the appropriate spectrum, 1-8 above.

52
 Isomers1
Different compounds having the same molecular formula are called isomers. Simply stated, for a
specific molecular formula, how many unique structures exist? When these structures have completely different
atom-atom attachments (or the atoms in the molecule are bonded together in fundamentally different ways), we
refer to such compounds as constitutional or structural isomers. Since this is the most simple form of
isomerism, we can just say "isomers" and the structural/constitutional term is implied. There are two structural
or constitutional isomers of C4H10 and three for C5H10. The structural formulas for these molecular formulas are
drawn below. These structures represent all the possible C4H10 and C5H10 compounds that can exist for these
specfic molecular formulas. Note that there are no double or triple bonds and no rings in any of these
structures. We will discuss these structural features below when we consider the Degree of Unsaturation.

Two Structural Formulas for C4H10 Isomers Three Structural Formulas for C5H12 Isomers

A simple method for drawing isomers is to begin with a three carbon chain and draw all the possible
permutations for adding the number of carbons to complete the molecular formula. For example, we can work
through drawing the different isomers for C4H10 in the following systematic manner:

We also need to develop the ability to "see" if a structure is unique or not. Although this seems very
obvious with simple structures, for more complicated structures we determine if the compounds are
superimposable. We envision picking up one of the structures and placing the molecule on top of the other and
if all the atoms match up (are superimposable), then the structures are equivalent. This is especially easy if you
make models of each molecule you are comparing with your molecular model kits. Eventually, you will not need
models as often because you will develop 3D-imaging capability so you can do the “mental gymnastics” in your
head.

When drawing isomers that correspond to a molecular formula containing noncarbon atoms (O, N, S,
Halogens etc.), we have to be careful to follow the bonding rules to draw valid structures. This is very good
practice and a good test whether you have the bonding rules firmly in your understanding of organic structures.
Try drawing the isomers for the following molecular formulas--the answers are on the following page:

C6H14 C4H9Br C 3H 8O C 3H 9N

53
C6H14 C4H9Br C 3H 8O C 3H 9N

Degree of Substitution

When discussing a compounds structure, it is often useful to distinguish different groups of carbon
atoms by their structural features. One such description is to look at how many carbon chains are attached to
any specific carbon atom. We refer to this as degree of substitution. A primary carbon (1º) is one that is bonded
to no more than one other carbon atom. A secondary carbon (2º) is bonded to two other carbon atoms, tertiary
(3º) is bonded to three other carbon atoms and quaternary (4º) carbon atoms are bonded four other carbons. It
is important to recognize that when considering the degree of substitution for any atom, we only count the
number of carbon atoms directly attached to the carbon atom being examined. The three C5H12 isomers shown
below illustrate the use of this terminology:

To practice with the C6H14 isomers, determine the number of each type substituted carbon for each compound:

o o o o o o o o o o o o o o o o o o o o
1 :__2 :__3 :__4 :__ 1 :__2 :__3 :__4 :__ 1 :__2 :__3 :__4 :__ 1 :__2 :__3 :__4 :__ 1 :__2 :__3 :__4 :__

We will use these terms often to refer to a carbon atom and its substitution. The degree of substitution
can be important to the stability of a charged carbon, like a carbocation, or the reactivity of an alkyl halide. For
o o o
example, we will refer to alkyl halides as 1 , 2 and 3 , which tells us the number of carbon-chain substituents
o o o
attached to the carbon that bears the halogen. Below are examples of 1 , 2 and 3 bromides. Note, that you
o
can not have a 4 alkyl halide, there would no place to put the halogen, or you would have too many bonds to
carbon!!

We can use this terminology to refer to other compounds as well. For example, determine the degree of
substitution of the following alcohols:

Finally, there is another term that is used when discussing the number of substituents in a more general
way. To refer to a carbon chain without specifying its structure, we use the term R-group. An R-group can be a
hydrocarbon chain with any structure, number atoms, number of branches etc. Below are some general
examples of degree of substitution for alkanes, alkyl halides and alcohols using the R-group designation for the
carbon chains attached:

54
 o o o o o o o o o o
1 2 3 4 1 2 3 1 2 3

Degree of Unsaturation- Molecular Formula Analysis

Although skeletal or Lewis structures are essential to describe a unique organic compound, it is often
useful to evaluate the structural information that may be obtained directly from a molecular formula. As we saw
from our discussion of isomers above, many structures can be drawn with the same molecular formula. By
examining the molecular formula, we can determine some of the structural features of the isomer compounds
we could draw for a given molecular formula. Two useful rules for the examination of alkane (C and H only)
molecular formulas are below:

1. The number of hydrogen atoms that can be bonded to a given number of carbon atoms is limited by the
maximum number of bonds to a carbon atom - four. For compounds of carbon and hydrogen (hydrocarbons) the
maximum number of hydrogen atoms that can be bonded to n carbons is 2n + 2 (n is an integer). Consider CH4,
n=1, therefore 2n + 2 = 4. In a chain of carbon atoms, the middle carbons will have two hydrogens each and the
two end carbons have three hydrogens each. For a six-carbon chain (n = 6) we have CH3CH2CH2CH2CH2CH3,
and the total number of hydrogen atoms using the 2n+2 formula is (2 x 6) + 2 = 14. Below are some possible
and impossible molecular formulas. Note that the molecular formula can have less than a 2n+2 number but not
more than 2n+2.

2. The number of hydrogen atoms in stable compounds of carbon and hydrogen reflects the number of double
bonds and rings in their structural formulas. Consider a hydrocarbon with a molecular structure consisting of a
simple chain of four carbon atoms, CH3CH2CH2CH3. The molecular formula is C4H10 (maximum number of
hydrogens = 2n+2, where n=4, number of H's is 10). If a molecular formula has this maximum number we refer
to that molecule as "saturated", meaning the molecule has as many hydrogens as it can "hold" (like a saturated
solution has as much solute as can dissolve). If the four carbon atoms form a ring, two hydrogens must be
“removed” from the structure to adhere to the bonding rules for carbon. Similarly, the introduction of a double
bond requires the loss of two hydrogens, and a triple bond the loss of four hydrogens. For each two hydrogens
that are "missing" from the saturated molecular formula (CnH2n+2), we refer to that as one degree of unsaturation.
Again, for each degree of unsaturation, there must be either a π-bond or a ring in the possible isomeric
structures that are drawn.
o o
C4H8: 1 of unsaturation, 1 π-bond or 1 ring C4H6: 2 of unsaturation, 2 π-bonds or 2 rings
or 1 π-bond and 1 ring

From the above discussion and examples, the molecular formula of a hydrocarbon can give some
structural information, which helps us in drawing isomers. In comparing C4H10 and C4H8, there are two
o
hydrogens missing (1 of unsaturation) so we know a π-bond or ring must be included in the structures we draw.
All the possible structures have to have either one of these structural features. As you can see for C4H6 isomers
above, the process of drawing isomers can become complicated rather quickly and it is often challenging to
draw all the possible structural permutations, especially for molecular formulas with more carbons. We will not
expect that you can draw the 20 isomers for specific molecular formula, but for small molecules, drawing
isomers is good practice and reinforces much of the structural basics we have been learning.

1. Adapted from Virtual Text in Organic Chemistry, William Reusch, Michigan State University.

55
13
C NMR Example Spectra

Which spectrum best correlates to the following compounds:

A.

B.

56
13
C NMR Problem Set:

1. Determine the numbers of peaks observed in the 13C NMR spectrum for the following
compounds.

2. You have been given a sample that contains one of the two following compounds. How
would determine which compound you have?

57
58
Conformational Analysis

Purpose: Determining the most stable shape for a compound

Simple Systems

Ethane Propane Butane

H H H H H
H H H
H H H
or H H H
H 3C CH 3 H
H H H H
H H H H H

-Ethane

Ethane H 3C CH 3

1
2 2
1

Eclipsing 1
Conformation 1

Rotate 60o Rotate 60o

1
2
2 1

1
Staggered
Confomation

59
-Propane

Propane

1
2 2
1

Eclipsing
Conformation 1 1

Rotate 60o
Rotate 60o

1 2
2 1

1
Staggered
Confomation

Steric Interaction Angle Energy (kcal/mol)

H H 0o 1.0
Eclisped

CH 3 H 0o 1.4

CH 3 CH 3 0o 2.5

H H 60o 0
Staggered

CH 3 H 60o 0

CH 3 CH 3 60o 0.9

60
-Butane

Butane

1
2 2
1

Eclipsing
Conformation 1
1

Rotate 60o Rotate 60o

1
2 2
1

Staggered 1
Confomation

Rotate 60o
Rotate 60o

1
2 2

1
Eclipsing
Conformation 1
1

Rotate 60o Rotate 60o

1 2
2 1

1
Staggered
Confomation

61
-Graph of Angle vs. Energy (kcal/mol)

1 1
5- -5
1
1

4- -4

3- -3

2- -2

1- -1

0o 60o 120 o 180 o 240o 300o 360o

Dihedral Angle (Degrees)

1 1
1

62
-Application to Cyclohexane Conformational Analysis
-Flat or Chair
H H
H H H
H H
H H
H H
H H H H
H
H H H
H H H H
H

-Drawing Chair Cyclohexanes

H H H
H H
H
H H
H H
H H H
H H
H
H H
H H
H H H H

-Simple Conformational Analyses - Ring “Flip” Conformational Change

-Methylcyclohexane

CH 3
- 1,2-Dimethylcyclohexane - Cis and Trans

CH 3

CH 3

64
65
66
67
Process for Cyclohexane Conformational Analysis

1. Draw both chair conformations. Draw good, correct chair structures with the correct relative
stereochemistry

a. Common mistake is not checking if groups are cis or trans in the chair cyclohexane drawn,
ensuring that the chair structure matches the stereochemistry of the starting compound.

b. Substituents on chairs must be rendered clearly in the axial or equatorial positions and with
equatorial substituents clearly shown as pointing equatorial up or equatorial down. Template
below and can used, label all equatorial up and equatorial down groups on each chair.

2. Analyze both structures for steric interactions.

a. Look for 1, 3 Diaxial interactions, use table in CP p. 42 for steric energies for each
substituent.

b, Look for any gauche interactions. These arise when substituents are on adjacent carbons.
Gauche, or 60o steric interactions will occur in all cases except when both groups are in the
axial position. Any substituent can be can located at the axial and equatorial positions shown
below and can yield a qauche interaction with another substituent on the adjacent carbon.

Equatorial-Axial or Equatorial-Equatorial: Gauche Interaction Axial-Axial: No Gauche

Interaction

3. Total the steric energy for both conformations and determine energy difference between the
conformations.

4. Using table or graph in CP; estimate the ratio of chair conformations. Make sure the largest
number of the ratio matches the lowest energy chair conformation.

68
69
 Steric Strain Due to 1,3-Diaxial Interactions

Strain of one H-Y 1,3-diaxial interaction

Y (kcal/mol) (kJ/mol)
-F 0.12 0.5

-Cl 0.25 1.4

-Br 0.25 1.4

-OH 0.5 2.1

-CH3 0.9 3.8

-CH2CH3 0.95 4.0

-CH(CH3)2 1.1 4.6

-C(CH3)3 2.7 11.3

-C6H5 1.5 6.3

-COOH 0.7 2.9

-CN 0.1 0.4

70
Relationship Between Stability and Isomer Percentages at
Equilibrium**

More stable Less stable Energy difference at 25˚C

isomer (%) isomer (%) (kcal/mol) (kJ/mol)

50 50 0 0
75 25 0.651 2.72
90 10 1.302 5.45
95 5 1.744 7.29
99 1 2.722 11.38
99.9 0.1 4.092 17.11

-(∆E/RT)
**The values in this table are calculated from the equation K = e , where K is the equilibrium
constant between isomers; e ≈ 2.718 (the base of natural logarithms); ∆E = energy difference between
isomers; T = absolute temperature (in kelvins); and R = 1.986 cal/mol •K (the gas constant).

71
Conformational Analysis Practice Problems:

1. For the following molecule, perform a complete conformational analysis using the data
provided in the Steric Strain Tables. Follow the following steps to complete the analysis.
(Assume no distortion of the ring due to the oxygen, and assume no steric strain due to electron
pairs on oxygen.)

a. Draw the two chair conformations possible for the compound.

b. Calculate the energy difference between the two chair conformations drawn above.

c. Estimate the ratio of most stable to least stable conformation that could be found in a sample
of this compound at 25oC.

72
2. Identify the more stable conformation in each of the following pairs and explain your
answer.

73
R and S Designation Assignment
1. Assign priorities to the four substituents by looking at the atoms attached directly to
the chiral center.
a. The higher the atomic number of the immediate substituent atom, the higher the priority.
For example:

b. If two substituents have the same immediate substituent atom,

evaluate atoms progressively further away from the chiral center until a difference is found.

For example:

c. If double or triple bonded groups are encountered as substituents, they are treated as an
equivalent set of single-bonded atoms.
For example:

Note: this rule is confusing, for our purposes with the atoms being the same, the more -bonds,
the higher the priority. In many cases, you don’t need to use this rule since many -bonded
systems contain different atoms and atomic number of the atoms (rule a) can be used.
For examples:

2. Orient the low priority group (4) pointing away from you.
By convention, you must do this step, but if the low priority group is pointing at you (these two
possibilites, low priority group pointing at you or away from you, covers 95-98% of the structures
you will see); you can make the assignment as normal, then invert the assignment (you see “R”,
but low priority group is pointing at you, so actually the assignment is S; or you see “S” but low
priority group is pointing at you, so actually the assignment is R). This avoids flipping the
molecule over and redrawing the structure when the low priority group is pointing at you. For
compounds with many chiral centers this is a big advantage.

74
For example, the two possible enantiomers for 2-pentanol are shown below (to the right and left
of the line below). For the second structure, we can take either approach to assign the
configuration for R or S enantiomer when the low priority group (-H) is pointing at us (on the
wedge):

3. Trace from priority group 1 -> 2 ->3 (ignor 4). This tracing will give either a clockwise (to the
right) or counterclockwise (to the left) direction. Assignments below confirm the two compounds
are enantiomers.

Clockwise, to the right, is R Counterclockwise, to the left, is S

As expected, for the compounds to be enantiomers, one must be R and one must be S.

Practice Problems: Assign R and S to all Chiral Centers

75
Optical Activity Measurement – Polarimeter

76
77
78
79
80
Resonance Form Rules:

1. Resonance forms differ only in the location of pi bonding electrons and non-bonding
electrons. No atoms change position.
A common error in drawing resonance structures is to disregard hydrogen atoms- Draw
in H's so you do not move any atoms in the process of drawing resonance structures.
2. Resonance forms are localized “versions” of the major contributing structures to the “actual”
structure. You can think of the actual structure as an average between the two or more resonance
structures. A resonance hybrid is a useful way of depicting a molecule with many resonance
forms.
3. Resonance forms do not have to be equivalent. The more stable resonance form will be the
larger contributor to the resonance hybrid.
4. Rules of valency must be followed - do not exceed normal valency to draw extra resonance
structures. Never more than 8 electrons around an atom, although you can have less than 8.
5. Resonance and the opportunity for resonance results in overall stabilization for the molecule -
"Resonance Stabilization". This information is extremely useful in predicting a molecules
reactivity.

Resonance Forms: Drawing and Interpreting

Resonance is a valuable tool to explain and predict a molecules behavior and the results of
chemical reactions. For example: How might one explain that for benzene and carbonate the
interatomic distances are all the same?

There are three possible resonance forms of carbonate - no one resonance form is more stable
than any others; all the oxygens share the negative charge equally, as demonstrated by the
resonance hybrid.

The benzene ring has two contributing resonance structures, which contribute equally to the
resonance hybrid. In fact, you will often see the benzene ring depicted as a resonance hybrid
using the shorthand notation of a circle in the center of the ring. (Although we will not use this
notation!)

81
Resonance Practice Problems
Draw additional resonance structures for each of the following molecules. Because most of the
molecules are drawn using skeletal structures, be particularly aware of the valence electrons and
where the implicit hydrogens are. Make sure to assign formal charges where appropriate and use
curved arrows to indicate the movement of electrons to reach the next resonance structure. As a
hint, I have indicated the number of additional resonance structures you should find in each case.

82
Draw all valid resonance structures for the following molecules. Note that in some cases there
may not be any.

83
Draw the Resonance Hybrid (using dashed bonds as partial bonds and partial charges) for the
following resonance structures.

84
85
86
87
 STABILITY RULES IN THE EVALUATION OF ORGANIC COMPOUNDS

We will evaluate whether reactions occur based on the stability of the products as compared to
reactants. In addition, we will decide on the product’s structure based on the energetics of
reaction pathways, which will require us to determine the stability of charged species (anions
and cations), often referred to as intermediates.

We have a number of tools to evaluate a compound’s stability:

1. Resonance
2. Electronegativity
3. Inductive effect
4. Hybridization
5. Bond strengths
6. Size of atoms – bond strength and anion stability
7. Steric interactions between substituents
8. pKa – ranking of acidity and conjugate base (anion) stability

The evaluation of stability using these tools is extremely valuable in organic chemistry, because
reaction results can be rationalized and as we master these skills, we can predict reaction
outcomes rather than simply memorize them. Importantly, we will use these tools all year so it
will be a good investment to learn these concepts.

Below are example compounds exhibiting the use of these tools. This document is a template
to facilitate lecture and allow for you to think about the questions presented rather than just
writing content down to be learned later. The goal is to present examples that elucidate how the
tools we have learned are applied to stability evaluations.

Stability of Uncharged Compounds

1. Alkene Stability – Cis or Trans

Which is more stable, products or reactants?

a.

or

b.

88
2. Alkene Stability – Degree of Substitution

or

Why?
Hyperconjugation: stabilizing effect due to partial “bonding” interactions (sharing of electron
density) between a filled σ-bonding orbital and an empty adjacent orbital. Increasing the
substitution of an alkene, increases the number of possible hyperconjugation interactions
between the adjacent σ-bonding orbitals and the π* molecular orbital of the alkene.

WHAT????!! We will discuss later…

3. Alkene Stability – Conjugation

Special Case:

89
4. Cis or Trans Substituents in Cyclics

5. Bond Strengths and Product vs. Reactant Stability

Recall our approximate numbers for ⌠-bonds vs. π-bonds:

~ 100 kcal/mol for σ-bonds
~ 50 kcal/mol for π-bond

As we go down a column on the periodic table, atomic size increases, bond length increases
and bond strength decreases. Halogens are a good example, H-F is a weak acid and HI is a
very strong acid. Bond strengths with carbon: C-F > C-Cl > C-Br > C-I. Note, C-Br and C-I ⌠-
bonds are not much stronger than π-bond.

This same analysis works for other periodic table column comparisons:

H2S vs. H2O which is more acidic?

The H-S bond should be a ____________ bond therefore H2S is _______ acidic.
Could check pKa of each, but you do not need pKa to answer these questions.

Do the following reactions occur as written? Why?

90
5. Bond Strengths, continued
Do the following reactions occur as written? Why?

But one has to be careful with bond strengths:

6. Acidity

We can determine if an acid-base reaction occurs, since the product acid must be more stable
and therefore have a higher pKa. This gives us information about the strength of a Y-H bond (Y
= any atom) using pKa’s. Anion analysis works here as well (just like in our acidity comparisons
where we considered the conjugate bases or anions in most cases), which is especially
effective if you do not have pKa values.

Examples: We did many of these in class, this is just a refresher

But sometimes need pKa’s for less obvious examples, especially for compounds that you have
not seen comparable pKa values.

91
Stability of Charged Compounds

1. Anions

Which is more stable and why?

Applications of resonance, inductive effects, electronegativity, size of the atom. Could use pKa
table, but you will not have a pKa table most of the time.

Recall that the Inductive effect is a shift of electron density in a molecule due to the polarization
of a bond by a nearby electronegative atom.

Which is most stable and why?

Orbital Pictures:

92
2. Carbocations

or

Orbital Picture of a Carbocation: 3o carbocation

Hyperconjugation involves partial sharing of electron density between a σ-bonding orbital and
an adjacent empty orbital. In carbocations, the empty p-orbital receives electron density from
neighboring σ-bonds by partial sharing of σ-bonding electrons. This process explains why alkyl
groups are weak electron donating groups (EDG).

Below are two orbital pictures of a 2o carbocation and the partial donation of σ -bonding
electrons via hyperconjugation. Note that any alkyl group attached to the carbocation (including
the –CH3 group on the left side of the molecule) can do this same partial donation of σ -bonding
electrons (hyperconjugation) to help stabilize the positive charge, which is why more alkyl
groups attached is more stable.

93
Which carbocation is more stable and why?

Bonus Topic:
Alkene Stabilization via Hyperconjugation

Hyperconjugation: stabilizing effect due to partial “bonding” interactions (sharing of electron

density) between a filled σ-bonding orbital and an empty adjacent orbital. Increasing the
substitution of an alkene, increases the number of possible hyperconjugation interactions
between the adjacent σ -bonding orbitals and the π * molecular orbital of the alkene.

In common language, we know that more highly substituted alkenes are more stable and we are
not really sure why. Best theoretical explanation is the partial donation of the σ-bonding
electrons to the π* antibonding orbital, when one considers the molecular orbital description of a
compound with a π-bond. Below are two pictures that might help you visualize this:

Why does donation of electron density to the π∗ antibonding orbital yield stabilization for the
alkene compound? And what is the π * antibonding orbital? We will cover molecular orbital
theory in more detail later in the course, so be happy for now that you can talk about
complicated chemistry terms you know nothing about.

94
EXAMPLE REACTIONS-MECHANISM TEMPLATES

Substitution Reaction

Stereochemistry of Substitution Reaction

95
Elimination Reaction

Predict Products Using Stability Rules

96
Addition Reaction

Predict Products Using Stability Rules

97
Reaction Coordinate for Substitution Reaction

Mechanism:

98
Reaction Coordinate for Elimination Reaction

Mechanism:

99
Reaction Coordinate for Addition Reaction

Mechanism:

100
101
102
103
104
Steric Hindrance and the SN2 Reaction

105
Elimination versus Substitution Reactions:

The basicity of the base/nucleophile and the structure of the alkyl halide are the most important
factors to consider when deciding whether a reaction proceeds by a Substitution or Elimination
mechanism. Also the structure of the base can be important when bulky bases are used to effect
an E2 elimination.

1. Primary Alkyl Halides:

a. SN2 reaction is favored, even with strong bases/nucleophiles such as CH3CH2ONa or NaOH.
They will not act as bases in the reaction but as a Nucleophile and attack the primary halide, and
do a SN2 displacement.
b. The only time you get an elimination reaction is with a bulky base such as (H3C)3CONa
(sodium t-butoxide). With added steric bulk, t-butoxide can not act as a nucleophile, therefore
only an elimination process (E2) can occur.
c. Even with a poor nucleophiles such as H2O, ROH or H2S, any substitution reaction that will
occur will proceed via an SN2 mechanism.

2. Secondary Alkyl Halides:

a. With Bases/Nucleophiles that are strongly basic, such as NaOH (pKa of H2O=15) and RONa
(pKa of alcohols=16-18) elimination will predominate. Other bases that could lead to
elimination with secondary alkyl halides : Acetylene anion( HC=CNa) NaNH2 and other
conjugate bases of acids with a pKa>15.
b. With weakly basic but good nucleophiles (NaCN, NaO2CCH3, NaN3, NH3) SN2 will
predominate (pKa range 5-12 for the above bases/nucleophiles). A polar aprotic solvent will
improve conditions for an SN2 process.
c. For the above two scenarios (a and b) one must realize that although we are predicting the
major product in these reactions, SN2 and E2 reactions are competitive processes. Both products
most likely will be observed, with one compound in a greater proportion. We would have to do
the chemistry to test accuracy and usefulness of our predictions. (i.e. Good desired product ratio
such as 80:20 vs a poor ratio such as 60:40)
d. With poor nucleophiles such as H2O or ROH, an SN1 reaction process would predominate,
with the accompanying minor product being the E1 product. Anything that might stabilize the
intermediate cation (Resonance) such as the cation being allylic (or benzylic) or the use of a
polar protic solvent would increase the likelihood of and SN1 reaction.

3. Tertiary Alkyl Halides:

a. With Bases/Nucleophiles that are strongly basic, such as NaOH and RONa elimination (E2)
will predominate. Other bases that could lead to elimination : Acetylene anion, HC=CNa,
NaNH2 and other conjugate bases of acids with a pKa>15.
b. With poor nucleophiles such as H2O or ROH, an SN1 reaction process would predominate,
with the accompanying minor product being the E1 product. The SN1 process is aided by the
use of a polar protic solvent.
c. SN1 reactions also occur with tertiary alcohols with treatment with a mineral acid (HX such
as: HCl, HBr etc.) to form tertiary alkyl halides.

106
Nature of Nucleophiles:

Strongly Basic/Nucleophilic:
General Rule: pKa>15
NaOH, RONa, NaNH2
HC=CNa

Moderately Nucleophilic, Weakly Basic:

General Rule: 5<pKa<12
NaCN, NaN3, NH3
NaO2CCH3 (Sodium Acetate)
NaSR

Non-Basic, Weakly Nucleophilic:

General Rule: pKa<5
H2O, ROH

107
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SN2 vs. E2 Reactions
The basicity of the base/nucleophile and the structure of the alkyl halide (1o, 2o or 3o) are the
most important factors to consider when deciding whether a reaction proceeds by a SN2 or E2
mechanism. See the rules for SN2 vs. E2 below.

Primary (1o) Alkyl Halides:

SN2 reaction is favored, E2 can only occur in one special case, when a bulky base/nucleophole
is used such as tBuONa or larger base/nucleophile

Secondary (2o) Alkyl Halides:

a. With Bases/Nucleophiles that are strongly basic, such as NaOH (pKa of H2O=15) and RONa
(pKa of alcohols=16-18) elimination will predominate. Bases that lead to E2 reaction with
secondary alkyl halides are the conjugate bases of acids with a pKa>15.
b. With weakly basic but good nucleophiles (such as NaCN, RCO2Na, NaN3) SN2 will
predominate (pKa range 5-15 for the above bases/nucleophiles).

3. Tertiary (3o) Alkyl Halides:

Bases/Nucleophiles that are strongly basic, such as NaOH and RONa will yield E2 reaction
outcomes. Note that under any reaction conditions, SN2 can not occur with 3o alkyl halides.

Reactivity of Nucleophiles:

Strongly Basic/Nucleophilic:
General Rule: pKa>15 Examples: NaOH, RONa, NaNH2,

Moderately Nucleophilic, Weakly Basic:

General Rule: 5<pKa<12 Examples: NaCN, NaN3, NH3, NaSR, RCO2Na or

Weakly Nucleophilic, Non-Basic:

General Rule: pKa<5 Examples: H2O, ROH

SN2 vs. E2 Table

(We will add to this table as we learn more reaction types)

109
110
Practice Problems-SN2 or E2
Give the major product of the reaction and the mechanism by which it is produced (SN2 and E2
only for this set of reactions; we will add in SN1 /E1 later). Be sure to include the stereochemical
outcome. Be sure to follow the guidelines we discussed in class for 1o, 2o and 3o alkyl halides
and the pKa ranges for 2o systems. The pKa table from the class packet on the last page of this
problem set could also be useful in deciding if the product is an SN2 or E2 product.
a.

b.

c.

d.

e.

f.

h.

i.

111
j.

k.

l.

m.

n.

o.

p.

q.

r.

112
s.

t.

u.

v.

113
Substitution vs Elimination Practice Problems:
For the following reactions give the major product of the reaction and the mechanism (SN1,
SN2, E1, E2). Be sure to include the stereochemical outcome.
a.

b.

d.

e.

f.

g.

h.

i.

114
Substitution vs Elimination Practice Problems: In Class Problems 2
For the following reactions give the major product of the reaction and the mechanism (SN1,
SN2, E1, E2). Be sure to include the stereochemical outcome.

a.

b.

d.

e.

f.

g.

115
Nomenclature Rules: Alkenes

Prefix-Parent-Suffix

A. Number the Carbon Chain:

1. Use the longest chain including the double bond.
2. Start numbering the chain closest to the first carbon of the double bond.
3. The double bond(s) takes priority over chain length. The main chain has to include the double bond.
4. If the numbering to the double bond is the same from either end of the chain, use branching to determine
numbering as before.

B. Assemble the Prefix:

1. Name the substituents, give a location number for each and list them alphabetically as before.
For special cases see D*
2. The double bond is numbered from the first double bond carbon on the chain

C. Suffix: Family Designation: ene for Alkene

1. For more than one double bond use diene, triene, tetraene etc. as the suffix part of the main name.
2. Give location numbers of the alkene or alkenes before the main name. i.e. 1-butene or 1,3-pentadiene.

D*. Common Names for Alkene Substituents:

1. Nonsystematic common names to remember: methylene, vinyl, allyl. (see below for structure).
2. Others are less common and can be named by complex substituent rules.** This is for your
information, we will not be concerned with more complex alkene substituents.
Note: Alkene complex groups would be named as a alkenyl. i.e. 1-propenyl -CH=CH-CH3

Common Groups Structure:

Naming Cycloalkenes:

A. Parent cyclic name used for the main name.

1. Make similar changes in suffix as in the straight chain alkenes.
2. Examples: cyclopentene, cyclohexadiene

B. Number from the first carbon of the double bond.

1. If more than one double bond in the ring, number on the ring to achieve the lowest location
numbers. C1 and C2 must include the double bond
2. Again double bonds have priority over other substituents.
3. Give number priority to substituents as before.

E and Z System of Nomenclature for Alkenes:

A. Assign priority to each group on the two carbons of the double bond.
1. Atoms with a higher atomic number have priority. i.e. Br > Cl > O > N > C > H
2. If the first atom provides no differentiation go to the next atom until a difference is found.
i.e. -CH2CH3 > -CH3
3. For multiple-bonded atoms consider each bond, s and p, to be a bond to an atom of that type.
i.e. C=O is considered a carbon bonded to two oxygen atoms.

B. Once priority is assigned the E and Z configuration can be determined.

1. E configuration: Higher priority groups on the opposite sides of the alkene. (trans)
2. Z configuration: Higher priority groups on the same side of the alkene. (cis)

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123
Alkene Reaction Drill Problems

124
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126
127
128
129
130
131
132
Alkyne Addition Reactions-Predict HBr Addition to Alkynes
-Addition of 1 equivalent of HBr or Addition of 2 equivalents of HBr

133
Bromine Addition (Br2) - Addition of 1 equivalent of Br2 or Addition of 2 equivalents of Br2
-Bromonium Ion Intermediate?

134
Hydration Reactions
-Overview of Hydration and Tautomerization of Enols to Carbonyl – Mechanism
-Oxymercuration and Hydroboration: Differences in Regiochemistry to form Enols

135
Hydrogenation – Addition of H2 to an Alkyne
-Alkyne vs. Alkene Stability

-Addition of H2 and Pd/C catalyst – Can not stop at 1 H2 addition

Addition of 1 equivalent of H2
-Lindlar’s Catalyst and H2 -- A catalyst that is “deactivated” to stop the reaction at the Alkene
stage. So Reaction 2 (shown above) is so slow it effectively does not occur. Reaction 1 is faster
and can occur even with the deactivated Lindlar’s Catalyst:

-Reduction using Na or Li and NH3, Mechanism of Na or Li and NH3 reduction

-Na or Li metal is a one electron donor, mechanism is a complex, stepwise process that yields
Anti addition predominantly. Not all Anti or Trans products are formed, but major product is
trans alkene

-Mechanism is complicated but interesting and explains the stereochemical outcome (you don’t
need to know this mechanism). Why does it explain the stereochemical outcome?

136
Oxidative Cleavage of Alkynes
-Ozonolysis (1. O3; 2. Zn AcOH)

Oxidation States in Organic Compounds

137
Synthesis Problems – Two Step Process
1. Prepare the carbon skeleton using alkyne anions and alkylation

Lets Consider Two Possible Targets:

-Deprotonation of Alkynes Using Butyl Lithium (BuLi) or NaNH2, either can be used
Example 1:

Mechanism of Acid-Base Reaction:

Example 2: Acetylene Anion Formation:

Mechanism:

-Carbon-Carbon Formation via SN2 reaction

Example 1 Alkylation:

Mechanism:

Example 2 Acetylene Anion Alkylation:

Mechanism:

138
2. Transform the Alkyne to the Desired Functional Group
-Functional Group Interconversion (FGI) – change or transform the triple bond to another
functional group

To make our two target compounds:

We have our compounds with the correct chain length with the triple bond in the proper location:
So now we just need to transform the triple bond to the functional group we need in the target
compound. Could take one or more reactions.

Synthesis Planning – Retrosynthetic Analysis

-Thinking Backwards in Synthetic Planning from Final Product: How do we plan a synthesis
when presented with a target compound?

Step 1: Find the two carbons that “come from” the triple bond

Step 2: Determine how to make the carbon backbone by specifically deciding on what R-Br
compound(s) will be needed to make the chain the correct length.
Compound 1: Compound 2:

139
Alkyne Addition Reactions—Drill Problems

140
141
142
143
144
145
146
147
148
149
150
151
Nomenclature Rules: Alkynes

Prefix-Parent-Suffix

A. Number the Carbon Chain:

1. Use the longest chain including the most triple bonds or other functional
groups.
2. Begin numbering at the end nearest the triple bond to give it the lowest
location number.**(If only triple bond(s) in the chain. If double bond(s) in the
chain as well see E below)
3. If the numbering to the triple bond is the same from either end of the chain,
use branching to determine numbering as before.

B. Assemble the Prefix:

1. Name the substituents, give a location number for each and list them
alphabetically as before.
2. The triple bond is numbered from the first triple bond carbon on the chain.

C. Suffix: Family Designation: yne for Alkyne

1. For more than one triple bond use diyne, triynes, tetrayne etc. as the suffix
part of the main name.
2. Give location numbers of the alkyne or alkynes before the main name. i.e. 1-
butyne or 3-pentadiyne.

D. Names for Alkyne Substituents:

1. There are no nonsystematic common names to remember.
2. Complex substituent rules can be applied to an alkyne containing
substituent. Alkyne complex groups would be named as a alkynyl group:
i.e. 2-propynyl
CH2 C CH

E. Compound with Double and Triple Bonds:

1. A compound with both double and triple bonds is called an enyne.
2. Numbering an enyne chain starts at the end nearest the first multiple bond
whether double or triple.
3. If the same distance to a double or triple bond give the lower location number
to the double bond.
4. For enynes give the location of the alkene in front of the parent name as
before, but include the alkyne location number before the –yne suffix set off by
dashes.
i.e. 1-hexen-4-yne.

152
153
Chem 31 -Reaction Review Sheet -Mercurium ion intermediate: partial mercurium
Alkene Reactions ion is best explanation for regiochemistry
1. HX Addition "δ+"
Hg+2 Hg+2
HX X δ+
H
-More substituted alcohol product
X = Cl, Br, I
-No specific stereochemistry observed in the
H product
-Carbocation intermediate:
-Carbocation stability controls regiochemistry 6. Hydration Reaction: Acid Catalyzed
OH
-More substituted halide product H2SO4
-Cation intemediate can lead to rearrangements H

2. Bromine Addition H
X2 X -Carbocation intermediate:
-Carbocation stability controls regiochemistry
X
-More substituted alcohol product
X = Cl, Br -Cation intemediate can lead to rearrangements
-Anti addition of Bromine (or Chlorine) 7. Dihydroxylation
-Bromonium (or Chloronium) intermediate:
1. OsO4 OH
Br
2. NaHSO3
OH
3. Bromohydrin Formation
OH -Syn addition of OsO4 to form osmate ester:
X2 O O
Os
H2O O O
X
-Syn (or cis) 1,2-diol products
X = Cl, Br
-Also, NBS, H2O is used
-Anti addition 8. Hydrogenation
-More substituted alcohol product H
-Bromonium intermediate: partial bromonium
ion is best explanation for regiochemistry Pd/C
H
Br δ+ Br -Syn addition of H2,
δ+ -Aromatic rings and carbonyls unreactive
4. Hydration Reaction: Hydroboration -Other catalysts possible, e.g. Pt, Rh
1. BH3, THF 9. Oxidative Cleavage
H
2. H2O2, NaOH 1. O3 O O
OH +
2. Zn, AcOH H H H
-Syn addition of borane (BH3,THF):
-Double bond is cleaved to give carbonyl
H compounds. Pneumonic:
H
Chop H Add H
B H + ? H + O H
? oxygens O
H H H
-Boron adds to the less substituted side
-Alcohol (-OH) replaces boron with retention of 10. Oxidative Cleavage of Diols
stereochemistry (with 2. NaOH, H2O2)
OH HIO4 O O
5. Hydration Reaction: Oxymercuration
OH +
1. Hg(OAc)2, H2O or H H H
OH
NaIO4 ,H+
H
2. NaBH4 -Same products as ozonolysis
154
Reactions of Alkynes:
1. BH3, THF H
1. HX Addition
2. H2O2, -OH
HX X
O
X= Cl, Br
H -Aldehyde product from terminal alkynes
1 equiv.
-Enol intermediate with less substituted -OH,
enol is unstable and never the final product,
-More substituted halogen product tautomerizes to aldehyde:
-Trans addition of HX
-Carbocation intermediate H
H O H H O H O H O
-Stereochemistry results from largest groups -H Resonance
H

trans H H H H

HX X X
4. Reduction
X= Cl, Br
2 equiv. or H H H2
excess
-Reacts with excess HX to give geminal Pd/C
dihalide (both halogens on the same carbon)
H2
2. Bromine and Chlorine Addition Lindlar
X
X2
-H2 and Pd/C catalyst reduces triple bond and
X= Cl, Br alkene p-bonds (phenyl rings are not reduced)
X
1 equiv. -H2 and Lindlar’s catalyst only reduces the triple
bond, double bonds are not reduced
-Trans addition of Br2 or Cl2 -Cis addition of H2, cis or Z alkene product
-Carbocation intermediate Li, NH3
-Stereochemistry results from largest groups
trans
-Double bonds are not reduced
X2 X X -Trans addition of H2, trans or E alkene product

X= Cl, Br
2 equiv. or X X 5. Oxidative Cleavage
excess
-Reacts with excess X2 to give tetrahalide 1. O3 O
+ CO2
3. Hydration 2. Zn, H+ OH

HgSO4, H2O O -Triple bond cleaved completely to form two

carboxylic acids
H2SO4 -Terminal alkynes yield CO2

-Ketone products only 6. Deprotonation and Alkylation

-Enol intermediate with more substituted -OH
group, enol is unstable and never the final R
BuLi R
product, tautomerizes to ketone: Br

or NaNH2
1o Halide only

H O H -H O H Resonance O H O H
H -Anion formed in first step with BuLi or NaNH2
H H H -SN2 reaction with alkyl halide in second step
-RX can only be a 1o alkyl halide

155
 - - - - -
7. Formation of Alkynes-Double E2 -GLG’s: I > RSO2O > Br > Cl ; Never F
-With methyl, 1° substrates, most
Br
NaOtBu
nucleophiles/bases can be used in SN2
Br -No SN2 with hindered Nucs/Bases
or NaNH2 -With 2° substrates, non-basic nucleophiles
must be used (conjugate acid pKa < 12):
O
-Dihalides can be treated with base to yield NaCN, NaN3, NH3, NaSR, RCO2Na or R O Na
alkynes in two successive E2 reactions
-No SN2 reaction with aryl or vinyl halides:
Br Br
7. Synthesis using Alkynes

C-C Bond Formation C-C Bond Formation

[Link] [Link]
or NaNH2 R1 or NaNH2 R1 2. E2 Reactions
HC CH C C
2. R1
HC C 2. R2 For 2°, 3° substrates:
Br R2
Br
X Base
Functional Group
Interconversion
R1
Synthetic
C C Target
X Base
R2
i.e.: All the Alkene
and Alkyne Reactions

X = Good Leaving Group (GLG)

-C-C bond formation using alkyne anion Base= Base/Nucleophile
-Functional group interconversion uses any of
the alkene and alkyne reactions to install the -E2 mechanisms are common for 2°, 3°
functional group required in the target substrates, only E2 with hindered bases and 1o
-E2 reaction occurs when SN2 reaction is slow,
due to steric hindrance
ALKYL HALIDE REACTIONS
1. SN2 Reactions -One step reaction, bond forming and bond
For methyl, 1°, 2° substrates: breaking occurs simultaneously
-Rate Law: Rate = k[Base][RX]
Nuc -E2 regiochemistry and stereochemistry in
H3C X H3C Nuc general: most highly substituted π-bond and
largest groups trans.
X Nuc Nuc - E2 regiochemistry and stereochemistry is
actually controlled by removal of the hydrogen
X Nuc
Anti to GLG. This gives ”180o approach” of the
Nuc electron pair for effective displacement of GLG
and formation of π-bond.
- - - - -
-GLG’s: I > RSO2O > Br > Cl ; Never F
X = Good Leaving Group (GLG) -With 1° substrates, E2 only with any hindered
Nuc = Nucleophile/Base base. Example: tBuONa
-With 2° substrates, may use any strong base
-SN2 mechanisms are common for 1°, 2°
(conjugate acid pKa > 12): NaOH, RONa,
substrates, never 3o
-SN2 reaction is sensitive to steric hindrance NaNH2, HC CLi
-One step reaction, bond forming and bond - With 3° substrates, almost any base will lead
breaking occurs simultaneously to E2, SN2 can not occur with 3o. Strong
-Rate Law: Rate = k[Nuc][RX] bases are good for E2; Weak bases result in
-SN2 leads to inversion of stereochemistry; 180o very slow E2 reaction.
approach of the nucleophile
156
3. SN1 Reactions Nucleophiles and Bases:
For 3° and 2o substrates:
Strongly Basic/Nucleophilic: General Rule:
OH OH pKa>12. Examples: NaOH, RONa, NaNH2,
X H2O
+ HC CLi

Moderately Nucleophilic/Basic: General Rule:

X HOR OR 5<pKa<12. Examples: NaCN, NaN3, NH3,
+ RO O

NaSR, RCO2Na or R O Na

X = Good Leaving Group (GLG)

Nuc = Weak Nuc such as H2O, HOR Weakly Nucleophilic/Basic:
General Rule: pKa<5. Examples: H2O, ROH
-Carbocation intermediate
Special Case:
-SN1 mechanism are common for 2°, 3°
Hindered nucleophiles/bases: tBuONa
substrates, never 1o. 2o is more favorable
Can only do SN2 on H3CX; E2 with 1o, 2o, 3o
when cation is resonance stabilized.
-E1 product a minor product from SN1 reactions
-Two-step (or more) reaction, C-X bond
ELIMINATION VERSUS SUBSTITUTION
breaking is rate-limiting step.
The structure/basicity of the base/nucleophile
-Rate Law: Rate = k[RX]
and the structure of the alkyl halide are the most
-Stereochemistry: cation intermediates lead to
important factors to consider when deciding
racemic mixtures
- - - - - whether a reaction proceeds by a substitution or
-GLG’s: I > RSO2O > Br > Cl ; Never F elimination mechanism.
-Weak nucleophiles/bases most common:
H2O, ROH , H2S 1. Primary Alkyl Halides:
-SN1 Special Case: 3o and 2o Alcohols with HX a. SN2 reaction is favored, even with strong
H2O is the GLG: bases/strong nucleophiles.
b. The only time you get an elimination reaction
Br Br
OH HBr
+ (E2) is with strong bases that are hindered
making them non-ucleophilic due to sterics.

OH Cl c. Even with weak nucleophiles/bases any

HCl + Cl substitution reaction will proceed via an SN2
mechanism.

4. E1 Reaction 2. Secondary Alkyl Halides:

E1 Special Case: 3o and 2o Alcohols with H2SO4 a. With strong bases, E2 elimination will
predominate.
OH H2SO4 b. With moderate nucleophiles/bases, SN2 will
predominate. A polar aprotic solvent will
improve conditions for an SN2 process.
OH H2SO4
c. Although we predict the major product in
these reactions, SN2 and E2 reactions are
competitive processes. In practice, both
products most likely will be observed, with one
-Carbocation intermediate
compound in a greater proportion. We would
-E1 mechanism are common for 2°, 3°
have to do the chemistry to test the accuracy of
alcohol substrates (never 1o) when treated with
our predictions.
H2SO4. 2o alcohol and E1 is more favorable
when cation is resonance stabilized. d. With weak nucleophiles/bases the SN1
-Two-step (or more) reaction, C-X or C-OH2+ reaction process predominates, with the
bond breaking is rate-limiting step. accompanying E1 minor product. Anything that
-E1 regiochemistry and stereochemistry follows might stabilize the intermediate cation
stability rules: most highly substituted π-bond (resonance) would increase the likelihood of an
and largest groups trans. SN1 mechanism.
157
3. Tertiary Alkyl Halides: Acid Conjugate Base

a. With strong or moderate nucleophiles/bases, Weak CH4 49 CH3 Strong

E2 elimination will predominate. Acid Base

NH3 36 NH2
b. With weak nucleophiles/bases the SN1
reaction process predominates, with the H C C H 25 H C C
accompanying E1 minor product.
R OH 16 H3C O

15.7 OH
Summary Tables: H 2O

11 R S Increasing
R SH
Nucleophilicty/
Alkyl Halide Basicity
Structure: 1o 2o 3o NH4 9.2 NH3
R R R
X X X R
Nuc/Base 9.1
Structure &
R R H C N C N
Reactivity:

H 2S 7.0 SH
Strong Base/Nuc
pKa>15
SN2 E2 E2
Examples: O
NaOH, RONa, Except: O
NaNH2 , HC CLi tBuONa,
then E2 4.8 R
R OH O
Moderate Base/Nuc
5<pKa<15 4.7
H N N N N N N
Examples:
SN2 SN2 E2
NaCN, NaN3,
NH3, NaSR H-F 3.2 F
O
RCO2Na or
R O
Na
Poor
R OH2 -2.2 R OH Nucleophiles
Weak Base/Nuc
H2O
SN1 SN1 H3O -1.7 H2O
SN2
HOR
very slow minor E1 minor E1
reaction product O
product O
** R S OH -6.5 **
R S O
O O
Alcohol alkyl sulfonic acid Mesylate (R=CH3) or Increasing
1o 2o 3o
Structure: R R Tosylate (R=PhCH3)
R Leaving Group
HO HO HO R Capabilities
Acid R R
H-Cl -7.0 Cl
Structure:
HX SN2 SN1 SN1
X = Ci, Br, I H-Br -9.0 Br

Strong -10.0 Weak

H2SO4 No Reaction* E1 E1 Acid H-I I
Base

*Reaction can be complex, yield ether products and other side products

158
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