Aaron Wood chem.

2050 study guide Exam 2

Benzene Chemistry Br
With cyclohexene, if you add Br2 you will get two Br’s Br
attached at the double bond.

Benzene will only accept 1 Br and requires a Lewis Acid Br

as a catalyst and will also get H-Br biproduct.

Lewis Acid: An electron pair acceptor, Feribromide, i.e.

FeBr3, Aluminumbromide, AlBr3.

Benzene is flat! Cyclohexane is in boat form.

Benzene is thus a perfect hexagon.

Electrons in Benzene π bonds are 1.39 Angstrom

(10-10 m), σ bonds are usually 1.54 and π are usually
1.34, Benzene is stable, despite electrons bouncing all
around.

All the carbons have sp2 orbitals (double bonds) despite

only 3 double bonds at a time.

Benzene functional groups and nomenclature CH3

Common name: Toluene (methyl group)
IUPAC: MethylBenzene

Common name: Aniline (nitrile group) NH2

IUPAC: Amenobenzene

Common name: Styrene (vinyl group)

IUPAC: Vinylbenzene
Vinyl is an Alkene, C=C, connected to a benzene.

OH
Common name: Phenol (hydroxy group, or alcohol)
IUPAC: Hydroxybenzene
Br

Any group attached will be named according to the

atomic name.

Bromobenzene Propylbenzene
Aaron Wood chem. 2050 study guide Exam 2

Benzene Nomenclature continued

Disubstituted (two or more functional groups)

Use the common name as the root: 4-chlorophenol

The number can be replaced by a word,

Ortho -- 2nd position
Meta -- 3rd position
Para -- 4th position
OH
CH3 OH

Br
NO2
Cl

3 – nitrotoluene 2 – bromophenol 4 - Chlorophenol

Metanitrotoluene Orthobromophenol Parachlorophenol

If the benzene is attached to a longer chain (nonane), the chain gets the base and the benzene is called
a PHENYL, not phenol (with an alcohol group) unless it does have an OH attached.
Br

5 – Phenylnonane 5 – (4 – bromophenyl) nonane

It is energetically favorable to have 3 pi bonds in a cycle. Lined P orbitals (especially 6 of them in benzene)

Electrophilic Aromatic Substitution (EAS)

Electrophiles (electron lovers) E+ are created when reacted with a lewis acid (it steals an electron).

+ - +
Br – Br + AlBr3 Br – Br AlBr3 Br + AlBr4 The Bromide is now an E

After an E+ is formed, the Benzene will react with the E+ to form a functional group.
Chlorination:
Aaron Wood chem. 2050 study guide Exam 2

FeCl3 or AlCl3 H Cl H+ Cl
+ Cl – Cl σ YThis will never happen if Y is electronegative!
complex X
Lewis acid +

The lewis acid creates a Cl+ as the E+. Chlorobenzene

Nitrogenation:

H 2SO4 H NO 2 H+ NO 2
+ HNO 3 σ complex
Sulfuric acid +
Lewis acid

The lewis acid steals an Oxygen and Hydrogen, creating NO 2+ as the E+. Nitrobenzene
SOHO 2

Sulphination works in the same manner and creates

Meta and OP directors

Disubstituting benzene molecules and determining where the functional groups will attach.

Ortho-Para selective
These are functional groups with a group that can double bond to the benzene if the + charge in resonance can be put
on the original group.
Bromination of Phenol:

OH

+ Br-Br The bromine will attach to Ortho, Meta, or Para depending on what director it is. In
this case the plus charge needs to be on the Oxygen to form a double bond with it.

OH OH OH OH OH OH

Para Meta H H H
Br Br Br
H Br H Br H Br

OH OH OH You will only get ortho and para groups out of the
H H H reaction. Absolutely no meta. Thus this reaction is
Ortho Br Br Br OP selective.

Meta directors
Aaron Wood chem. 2050 study guide Exam 2

These are groups on benzene rings that have this formula:

A plus charge will never end up on the connection to x

if y is electronegative
(oxygen or fluorine)

O O O O O O
OCH 3 OCH 3 OCH3 OCH 3 OCH3 OCH 3
H H H
Para Ortho Br Br Br

H Br H BR H Br

O O O
OCH 3 OCH 3 OCH 3 This molecule is meta selective.
Meta You will only get meta out of this
H H H reaction!
Br Br Br

Benzene reaction speeds

OH CH 3 Cl NO 2

1000* 24.5 1 0.037 0.0000001~

Phenol Toluene Benzene chlorobenzene Nitrobenzene
-7
*(1000 time faster than benzene) ~(10 time the speed of benzene)

σ height of the hills determines the reaction speed. The lower the hills, the faster the
reaction. The higher the hills, the slower the reaction. (more energy must be put in
to react. σ complex is the energy that needs to be put in to form a sigma bond hop
over of the hydrogen in the intermediate step of the EAS.

H E+ E

H+

Chapter 5
Aaron Wood chem. 2050 study guide Exam 2

Chirality: The condition of non-superimposable mirror image.

i.e. Hands are chiral.

They are mirror images of each other.

But if you put them on top of each other (superimpose) they don’t match up. Thus these are chiral.

If a carbon has 4 different groups attached, the carbon is called a chiral center, the molecule is called an enatiomer.

Achiral: any molecule that is super imposable but not a mirror image. Simply change any of the two groups of a chiral
carbon to get Achiral.

Chiral Achiral
Mirror images But cannot superimpose Not mirror image But can superimpose

CIP rules
Aaron Wood chem. 2050 study guide Exam 2

R & S rules (chirality)

#1. Rank the substituents by atomic number. (highest number = 1, lowest atomic number = 4)
#2. If there is a tie, look for the first point of difference. C-C-C is higher than C-C.
#3. Hold the #4 atom pointing away from you. And count from 1-2-3.
If clockwise, R configuration.
If counterclockwise, S configuration.

4 1
H
H Iodine Iodine = 1 H Since the rotation
Ethane = 2 is clockwise from
C Methane = 3 1-2-3, This is
Hydrogen = 4 R configuration.

C C (R) – 2 – Iodobutane
3 2

R and S configurations are enatiomers of each other.

Enantiomers have the same chemical properties in achiral environments. Different in biological systems.
CO2H 4
R and S Fisher projections Same as 1 S - config
H2N H
Horizontal lines are coming out at me! 2 3
Vertical lines are going into the page! CH3
The model can be rotated 180˚ but NOT 90˚. 90˚ will make the enatiomer.
It will turn and S into an R or vice versa

E and Z isomerization (cis and trans for alkenes)

This is another way of expressing cis and trans for alkenes. E is trans, Z is cis. You number from 1 to 2 on each side. You
give the halide group the 1 and the carbon groups a 2.

2 CH3 Br 1 2 CH3 CH3 2

C C C C

1 F CH3 2 1 F Br 1

E – isomerization Z – isomerization
(E) 2 – Bromo – 3 – Fluoro – 2 – Butene (Z) 2 – Bromo – 3 – Fluoro – 2 – Butene

Molecules with two or more stereocenters

Enantiomers: Stereoisomers that are non-superimposable mirror images.
Aaron Wood chem. 2050 study guide Exam 2

Diastereomers: stereoisomers that are not enantiomers. Diastereomerism occurs when two or more stereoisomers of a
compound have different configurations at one or more (but not all) of the related stereocenters and are not mirror
images of each other, they can or cannot be superimposable.

Diastereomers.
They only differ at one stereocenter, and are not mirror images.

Diastereomers have different physical & chemical properties!

Enantiomers have the same physical and chemical properties in Achiral environments!

How many stereoisomers are possible?

N is the number of stereocenters.

2N = the # of stereoisomers.
Thus is a molecule has 2 stereocenters, there are at max 4 configurations. Unless they are Meso compounds.

Meso compounds are molecules that are mirror images AND and superimposable. This happens if there is a line of
symmetry between the stereocenters.
R CH3 CH 3 R

H Br Br H

H Br Br H line of symmetry

S CH3 CH 3 S

They can mirror and if flipped, they can superimpose. These compounds are Identical.
The # of possible configurations decreases by one if they are mesocompounds.
2 stereocenters. 22 – 1 identical configuration = 3 possible configurations.

Stereochemistry in Reactions
When an atom wants to connect to a stereocenter (an Alkene), it will choose a side to go to one side of the double bond.

If it doesn’t matter which side, it will make a 1 : 1

If it does prefer one side of the molecule, most of the
mixture (racemic mixture) of being on one side and on
products will be in that configuration.
the other. Racemic mixture (A mixture of 1 : 1 R & S
configurations of a molecule)

Stereochemistry in Reactions (continued)

Take these reactions for example;
Aaron Wood chem. 2050 study guide Exam 2

The Cl doesn’t care which side it joins, so it will The Cl does care which side it goes to in this molecule.
form a 1 : 1 mixture. (doesn’t matter how much to us in this class which side)

+ HCl H CH 3 + HCl

H
+ 50% 80%
C CH 3 . Cl .
-
C CH 3 Cl 20%
50%
H + CH 3 H

Separating enantiomers
If you react a 1 : 1 mixture of R & S (racemic) with an S solvent. You will get R connected to the S solvent and S
connected to the S solvent. You can then break these bonds to get S solvent, R, and S individually.

1 : 1 R/S mixture + S* R S* + S S* 2 S* + R + S
React separate
S* is solvent

Chapter 6 Organic Halides

Primary carbocation 1 carbon attached to the carbon in question.
Secondary carbocation 2 carbons attached to the carbon in question.
Tertiary carbocation 3 carbons attached to the carbon in question.

4 Mechanisms of Halide reactions

Nucleophilic substitution
(nucleus lover, electron giver, A benzene ring is a nucleotide in the first step of a reaction.)

Elimination

2 types of substitution
Aaron Wood chem. 2050 study guide Exam 2

S N2
Requires a good nucleophile. Negatives are better nucleophiles than neutral but it cannot be an O - or N- negative unless
it can resonate through the rest of the molecule.

Down the column and from right to left (bottom and far left are best) are better nucleophiles.

Requires a WEAK base to form, if it has oxygen it must be OCH 2CH3 to form SN2.
Any Nu that has Sulphur is a weak base.
A 3˚ carbon with an Oxygen nucleophile (OCH 3CH3CH3) will not do SN2, The methyl’s will get in the way of elimination.

All bonding happens in one step, no cation formed. 1˚ and 2˚ work for these reactions. 3˚ do NOT work.
The nucleophile (negative or neutral charge) will come from the back and push out the halide.

The configuration of the bond will be reversed when this happens, turning S into R or R into S.
3˚ do not work with SN2 because the starting molecule’s other carbon groups repel the nucleophile.

S N1
A Carbocation is formed (intermediate step)! Requires a strong base! NaOH, NaOCH3, NaOCCH 3CH3CH3, NaNH2.
Will work with 3˚ and 2˚, but NOT 1˚.

2 types of elimination
E2
no intermediate step is formed.

E1
An intermediate step is needed.
 Aaron Wood chem. 2050 study guide Exam 2

If a weak base, Sulpher, or Oxygen

with resonance or attached to a 3˚
carbon. The reaction will be SN2 and
will push out the halide and join
where it left, inverting the orbitals. R
If Primary, Is the to S or S to R. 1 step process!
solvent a strong or
weak base? If a strong base, Nitrogen, or oxygen
without resoance and not attached
to 3˚ carbon. The reaction will be E2
and will eliminate the halide and will
form a double bond where the
elimination occured. 1 step process!

If a weak base or Nu, The reaction

will favor SN2.

Is the reactant a If secondary, Is the If a strong nucleophile,

primary, secondary, or solvent a strong or the reaction will favor
tertiary carbon? weak base? Is it a weak nucleophile? SN2 over SN1.
nucleophiles get stronger as
you go down a column and
to the right. Most of the If it is a weak
time it will prefer E2.
nucleophile, the
reaction will favor SN1
If a weak base, nothing will
happen. The weak base (-S-H) over SN2.
will be repulsed and will do
anything to the halide. But will
If tertiary, Is the favor E1 at high temps.
solvent a strong base
If a strong base, Nitrogen, or oxygen
or weak base? without resonance and not attached to a 3˚
carbon. The reaction will be SN1, it will
form a carbocation with a plus charge
where the halide left as an intermediate
step. the nucleophile will then join the
carbocation to form a product. 2 step
process!

Weak base:
Aaron Wood chem. 2050 study guide Exam 2

OCH2CH3 . SN2 (1˚)

SCH3. SN2 (1˚)
CN, cyanide, SN2 (1˚)

Strong Base:
OH. E2 (1˚) or SN1 (3˚)
OCH3. E2 (1˚) or E1 (3˚)
O-CCH3(CH3)CH3 O-3˚ carbon (carbons get in the way of substitution). E2

Reaction speeds
If the leaving group is larger, the speed will be higher.
Down a column and to the right of a row. = faster