You are on page 1of 34

1

CHAPTERS 1-3 STUDY GUIDE


Aliphaticstraight/branched chain organic compounds
Cyclicorganic compounds in ring form
Heterocycliccyclic compounds with an atom other than carbon in the ring
Alkanesorganic molecules with all single bonds, general formula Cn H2n+2
Alkenesorganic molecules with a double bonds, general formula Cn H2n
Alkynesorganic molecules with a triple bonds, general formula Cn H2n-2
Hydrocarbonsorganic molecules with hydrogen and carbon only
Isomers
Constitutional Isomers
Ionic/Covalent
Electronegativity
Resonance
Lewis Acid/base
Aromatics
Olefin
Saturated/Unsaturated
Functional Group
Polarity
Dipole Moment
Substitution/Addition/Elimination/Rearrangement
Heterolysis/Homolysis
Carbocations
Carbanions
Solubility
Hybridization
Inductive Effect
Solvation
Protic/Aprotic Solvents
Sterics
Leveling effect
Alkoxide ion

HISTORY/CHAPTER 1
History of lifeair-sea-soup-nucleics(sugar, pyrimidines, purines)-DNA-cells- life-humans
Organic chemicals around for yearsEgyptians(alizarin, indigo), Phoenicians(royal purple)
Todayceramics, plastics, synthetics, fibers, paints, food, drink, fuel.
Vitalismvital force; all organic compounds must be made from other organic compounds
Wohler and the synthesis of urea

NH 4 CNO

NH 2 CONH 2

Lavoisier, Leibig, Berzelius, Dumas, Cannizaro, Kekule, Couper, Butlerovqual/quant/ef/mf/structure


Organic vs synthetic
Organic vs. Inorganicflammable, mp, bp, solubility, bonding, complexity, reactivity
Organicsdrugs, medicine, plastics, polymers, ceramics, superconductors, fabrics, cloths, synthetics,
foods, drinks, cleansers, detergents, plants/animals/humans.
Polyester/nylonscheap clothing, easy to makeallergic reactions, waste
Adhesives/sealantsmakes building cheaper easierwaste, fumes
Polymers, plasticsconvenie nce, cost, multiple usesnon biodegradable
Herbicides, pesticides, insecticideshelps prevent illness, increases productivityenvironmental
BHA, BHT, MSGflavor enhancer, preservativeallergies
Saccharinsugar substitutecancer causing
Antibiotics, Sulfa, Steroidssaves millions of livesside effects, can be abused
CFCscheap, nonflammable, saved lives and moneyharmful to the ozone layer

STRUCTURE OF ORGANIC COMPOUNDS


Organic compounds contain covalent bonds. You need to know Lewis Structures, Formal Charge and
Resonance theories to draw correct structures(see handout).
Carbonalways 4 bonds
Nitrogenalways 3 bonds
Oxygenalways 2 bonds
Hydrogen, halogensalways 1 bond
Carbon-carbon connections can be single, double or triple bonds.

Isomersconnectivity/structure
EF vs MF vs Structural Formula
Vant Hoff/Le Bel 4 bond arrangement is a tetrahedral
Lewis/Kosselionic vs covalent bonding, octet rule
Linus Paulingelectronegativity
Linus Pauling won 2 nobel prizes. One for chemistry and a pe ace prize. His chemistry prize was
for his groundbreaking work on the bonding of chemicals(esp. orbital overlap, sigma, pi bonds)
Who else won 2?
Lewis Structure
Exceptions to the octet Ruleall molecules can violate by having less than 8, 3rd period can violate by
having more than 8, d-orbitals
Formal Charge = valence e bonds nonbonding e
Carbon with 3 bonds is positivecarbocation
Carbon with 3 bonds and lone pair is negativecarbanion
Nitrogen with 4 bonds is positive, with 2 bonds(and 2 lone pairs) is negative
Oxygen with 3 bonds is positive, with 1 bond(and 3 lone pairs) is negative
RESONANCE
Curved arrow notation
Electrons move from (-) to (+)
Can only move electrons(lone pairs or double/triple bonds)
Can not break or violate octet rules unless allowed by d-orbitals
Use correct reaction arrows to indicate resonance
Know Rules pages 16-18

Rules for Resonance Structures


1. Only move electrons(lone pairs or double bonds).
2. Electrons can move only from element to bond or vice versa.
3. Move electrons from electron dense(negative) to electron poor(positive) region.
4. When moving a pair of electrons if a violation of the octet occurs by having
more than 8 electrons on a period 1 or 2 element, that is an illegal resonance
structure.
5. When a pair of electrons moves into a bond and creates a violation of the octet
rule, other electrons must be moved away to stabilize the structure.
6. All elements can violate the octet rule by having less than 8 electrons.
7. Benzene structures have resonances by rotating the 3 double bonds inside.
8. Resonances with all closed shells and no charges are the best.
9. Charge separation lowers the stability.
10. Negative charges on less electronegative atoms and positive charges on more
electronegative atoms destabilize the resonance structure.
11. Open octets are the most destabilizing factor.
Rules for Orbital Diagrams.
1. Replace each double bonded(sp2) element with a pi-orbital.
2. Replace each triple bonded element with 2 pi-orbitals at 90 degrees to each other.
3. Connect double and triple bonded elements with 2 lines(one from top lobe and one
from bottom lobe).
4. Leave all single bonds as is.

CH3

CH3

Rank = 2
CH3

O
CH3

Rank = 2
O

CH3

CH3

Rank = 1

CH3

CH3
O

Rank = 2

MOLECULAR/ATOMIC ORBIT THEORY


MO theory is helpful for understanding the physics behind bonding of organic molecules and some of
their reactivity.
Dont get bogged down in theory though. You can know everything you need to know about organic
chemistry without understanding orbital theory.
Quantum mechanicsSchrodingerwave mechanics, wave equations, wave functions
The graph of the solutions for Schrodingers wave functions(squared) lead to a region of space where
electrons have the highest probability of being found in relation to the nucleus(zero, zero, zero). This
plot gives us the orbital shapes for s, p, d, f. Remember orbital represent a 3-d graph of space where it is
likely to find electrons. There is NOT a physical shell around the electrons.
Recall, the Aufbau principle along with Hunds Rule and Paulis Principle allow us to create a very
simple easily understood model of the electron density around the nucleus.
As two atoms approach each other, atomic orbitals of each combine to form molecular orbitals.
# of atomic orbitals = # of molecular orbitals.
Bonding molecular orbits are always lower than atomic orbitals(in Energy). They represent a positive
interference, when the two atomic orbitals enter together in phase and reinforce each other, representing a
large probability that electrons will be found in that region of space between the two nuclei. Electrons
found here increase or stabilize the newly formed covalent bond.
Nonbonding molecular orbitals are always higher than atomic orbitals(in Energy). They represent a
negative interference, when the two atomic orbitals enter together out of phase and cancel each other,
representing a small probability that electrons will be found in that region of space between the two
nuclei. Electrons found here destabilize the bond strength of the new covalent bond.
HOMOhighest occupied molecular orbital
LUMOlowest unoccupied molecular orbital
Hybridization of orbitalsIn organic chemistry orbitals are often hybridized.
For ex, singly bonded carbons exhibit sp3 hybridization. The 2s and the three 2p orbitals mix to form 4
new(s + p + p + p) sp3 orbitals that exhibit characteristics of both. These ne w orbitals are 25% s and 75%
p in character. Tetrahedral geometry. Angles = 109.5 o

Double-bonded carbons exhibit sp2 hybridization. The 2s and two of the three 2p orbitals mix to form 3
new(s + p + p) sp2 orbitals that exhibit characteristics of both. These new orbitals are 33% s and 67% p
in character. This leaves one p orbital unhybridized. This unhybridized p orbital make the double
bond. Trigonal planar geometry. Angles = 120 o
Triple-bonded carbons exhibit sp hybridization. The 2s and one of the three 2p orbitals mix to form 2
new(s + p) sp orbitals that exhibit characteristics of both. These new orbitals are 50% s and 50% p in
character. This leaves two p orbital unhybridized. These unhybridized p orbitals
make the triple bond. Linear geometry. Angles = 180o
s-orbitals(and sp, sp2 and sp3 ) make single sigma bonds. p-orbitals make double/triple pi bonds.
A double bond consists of a sigma and a pi bond. A triple bond consists of a sigma and 2 pi bonds.
The more s in a bond the shorter the bond. I.E. the shortest bonds are sp, the longest are sp3 .
Or in other words, triple bonds are shortest, single bonds are the longest and double bonds are in between
in size.
sp3 orbitals make sigma(single) bonds. They are the longest and have a tetrahedral geometry.
sp2 orbitals make sigma(single) bonds. They are middle in length and have a trigonal planar geometry.
sp orbitals make sigma(single) bonds. They are the shortest and have a linear geometry.
p orbitals make pi(double/triple) bonds. The double bonds are trigonal planar, the triple are linear.
Single bonds can rotate.
Double bonds can not rotate. Double bonds can exist as cis/trans isomers.
Cis isomers have the groups on same side of double bond. Trans have them on opposite sides.
Know summary 36-38.
VSEPRtetrahedral geometry includes trigonal pyramidal(ammonia) and angular(water)
Structural Formulasdash, condensed, bond line

Molecular Orbital Theory

H
C

MF

Condensed

Dash

O
Br

H
H

H
H

CH3CH2CH2CH3

C4H10

2
1

4
3

Bond Line

10

CH3

CH 3

CH

(CH3)2CHCHBrCH(CH3)CHCH 2

H3 C

CH

CH 2

CH

C
H

Br

CH3

CH3

CH
H 3C

CH2

CH
CH

C
H

Br
H2
C

CH3CH 2CH(OH)CHCHCH2CCH
H3 C

H2
C

H
C
CH

C
H

CH
C

OH

H2
C
H3 C

H2
C

H
C
CH

C
H

CH

OH
CH 3

H 3C
Br

OH

C
H3 C

H2
C

H
C

CH

C
H
CH 3

H
C
C

C
H

Br

O
H

(CH3)2CHC(CH3) 2CHCHCH 2CBrCHCH2OH

11

O
H2C

C
H

C
H2

OH

O
H2C

C
H

C
H2

OH

O
H2C

C
H

CH2H2C

OH

O
H2C

sp

C
H

CH2H2C

H
C

Br

C
C

HC

CH
C
H2

CH
C

CH
C
H

OH

HC

sp 2

sp

sp 3
sp

Br

12

EXTRA PRACTICE:
Draw at least 2 resonance structures for each and indicate the best resonance structures of
the ones you drew.
O

N
O

13

CH3

H2
C
H 3C

C
H2

CH H
C

H2
C
CH3

CH3

H
C
C
H2

H2C

H 3C

H2
C

O
C
H2

CH3

CH3

CH3

CH3

CH

CH

C
H

C
H2

H2
C

C
H 3C

CH3
CH3

14

O
O

15

16

CHAPTER 2
methane
ethane
propane
butane
pentane
hexane
heptane
octane
nonane
decane

CH

17

cyclopropane

cyclobutane

cyclopentane

cyclohexane

cycloheptane

cyclooctane

BenzeneKnow the Kekule Structure

According to first 2 pictures there should be alternating double and single bonds. But in reality all 6
bonds are of the same length(1.39A). This can be explained by resonance and Molecular Orbital Theory.

What is meant by delocalization? The electrons are dispersed between multiple bonds.
In benzene the electrons are delocalized through the 6 pi orbitals of the 6 carbons in the ring structure.
These electrons are able to move freely from carbon to carbon.
Know polarity/electronegativity. Be able to identify polar bonds and indicate dipole moments and/or
partial charges. Polar covalent bonds/dipole moments are responsible for all reactions/mechanism

18

P o l a r b o n d s , n e t d ip o le

P o la r b o n d s , n o n e t d ip o le
O

C
C l

H 2O

NH

C l

CH

C 5H

C l

C l

12

C
H

C l

Br

C l

C 8H

C l
C

Br

C l

H
C

C l

C l

FUNCTIONAL GROUPS
Alkyl functional groupsmethyl, ethyl, propyl, butylisopropyl

ISOBUTYL

allyl

sec-Butyl

ISOPROPYL

vinyl
2

1
4

neopent
yl
1

1
2

METHYL

C l

C
C l

N o p o la r b o n d s o r
d ip o le

ETHYL
PROPYL

tert-Butyl or
t-butyl
4

BUTYL

18

19

Phenyl
C6H5

Ph-

Benzyl
H2C

H2C

C6H5CH2-

Bn-

Alcohol/halidesF, Cl, Br, I, OH


Need to know difference between 1o , 2o and 3o alkyl halide or alcohols.

30

2o
Br

Cl

HO

OH

3o

EthersCOC
O
O

Cl
o

2o

20

AminesNR3 , if R= 3 Hs, it is ammonia; if R = 2Hs, it is a primary amine; if R = 1 H, it is a secondary


amine; if R = 0 Hs, it is a tertiary amine.

NH4+

Ammonium ion

NH3

Ammonia

2o

NH2 1o

NHCH2CH3

3o
(H3C) 2N

3o

N(CH2CH2CH2CH3) 2
NHCH3

2o

CarbonylC double bonded to an Oxygen


Aldehydecarbonyl with H attached directly to carbon
Ketonecarbonyl with two alkyl groups attached to carbon
Carboxylic acidcarbonyl with OH attached to carbon
Estercarbonyl with alkoxy group(OR) attached to carbon
Amidecarbonyl with amine attached to carbon
Nitrilecarbon triple bonded to nitrogen
Iminenitrogen double bonded to carbon

21

K eto n e

ald eh y d e
H
NH

im ine
acid
OH
O

este r
C

O CH 3

n i t ril e
CN

este r

O
O

am i d e

2 o am id e

N H2

N HC H 3

1 o am i d e

3 am i d e

NH 2

N ( C H 3 )2

PHYSICAL PROPERTIES
Melting/Boiling points
Melting/boiling points are determined by intermolecular forces. Ion- ion, dipole-dipole forces, hydrogen
bonding
In general, the larger the MW the larger the melting and boiling points. The more the branching the
lower the mp/bp. Increasing the branching decreases the Van der Waal Forces which decreases mp/bp.
Increasing MW increases Van der Waal Forces which increases mp/fp.
In general, the higher the polarity the larger the melting point.
Hydrogen bonding increases the melting point.
Symmetry increases the melting point.
1-4 Carbonsgas; 5-17 Carbonsliquids;18 and abovesolids
Solubility
Hydrophilic/hydrophobic/lipophilicity

22

In the following pictures, identify the indicated functional groups.


A

NHCH3

OH

1
N

NH

OH

Br
OH

NH2

NH
CH

C
B

3
H

Cl

NH2

N(CH 2CH3 )2

J
In the above drawings identify as primary, secondary and tertiary the indicated groups(alcohols,
halogens,
amines and amides).
1

23

CHAPTER 3
Know differences between substitutions/addition/elimination and rearrangement reactions.
Substitutions1 functional group replaces another
Additiondouble or triple bond replaced by functional group
Eliminationfunctional group replaced by double or triple bond
Rearrangementinternal structure of molecule rearranges
Homolysis/Heterolysismost reactions go through heterolysis. Homolysis is used in radical forming
reactions. In general, the more polarized the bond the easier it will be for the bond to undergo
heterolysis.
ACID/BASE
Bronsted-Lowry vs. Lewis definitions
Conjugate acid/conjugate base
In organic chemistry both forms of acid/base chemistry is important.
Bronsted-Lowrymany different situations in the upcoming chapters will involve
protonation/deprotonation reactions.
Lewisalso we will see acid/base reactions that involve electron pairs and open orbitals.
One of the main types of Lewis Acids we will see is group three halides. Boron trifluoride, aluminum
trichloridethese have open p orbital which acts as electron pair acceptor.
F
B
F

NH3
F

Carbocations(carbons with positive charge and open p orbital) are also good Lewis Acids.
Carbanions(carbons with negative charge) are good Lewis Bases.
Electrophile/Nucleophile
pKa, pKb

24

The larger the pKa the stronger the base will be that is generated from that substance.
The lower the pKa means the substance is a stronger acid.
Low pKa strong acid, high pKa weak acid.
Increasing base strength is due to the instability of the conjugate base of an acid.
The more stable the conjugate base is of an acid, the stronger it will be as an acid.
The less stable the conjugate base is of an acid, the weaker it will be as an acid.
A stable base is a weak base. An unstable base is a strong base.
Insoluble acids can be made soluble in water by adding a stronger base to it.
In general, acidity increases as you go down a column; i.e., HI is strongest of halogen acids.
In general, basicity increases as you go up a column.
In general, acidity increases left to right across periodic table and basicity decreases left to right.
The more s character of a bond the more stable the conjugate base will be; therefore, it will be a weaker
base.
Therefore, alkynes have most s-character and are the best acids and the weakest conjugate base.
Alkanes have the least s-character and are the worst acids and the strongest conjugate bases.
The more stable a base is the weaker it is(and conversely it is a stronger acid).
Stability to a base is increased by the inductive effect and by resonance delocalization of negative charge.
Electron withdrawing groups close to the negative charge will pull the negative charge towards them
through the bonds. Inducing the negative charge to move.
The more(or any) resonance hybrids that can be drawn the more stable the base.
The easier it is to ionize(deprotonate) an acid the stronger that acid will be and the weaker its conjugate
base will be.
The more stable the conjugate base the stronger the acid.

25

Solvent effects
Acids are much stronger in solvent than in gas phase.
Solutions can also help stabilize the conjugate base anion.
Protic solvents are hydrogen bondable and very good at stabilizing conjugate base.
Aprotic solvents can not hydrogen bond and do not stabilize the conjugate base.
Neutral organic bases
Alcohols can protonate to form alklyoxonium ions. Ethers can also do this.
Carbonyls can also protonate(or esp. act as Lewis Base).
Nitrogen compounds can do this as well.
Double/Triple bonds have the ability to protonate. They have large pi electron density in double bond
that acts as Lewis base.
Leveling effectIn water there can not be a stronger base than OH- or a stronger acid than H3 O+
If you need a stronger base you must use a non-water solvent. Sodium amide is often used in liquid
ammonia. Hexane and ether bases are often used also.
MECHANISM NOTATION
Curved arrows are us ed to show the movement of electrons.
Arrows are always drawn from nucleophile(electron pair, negative charge) to the electrophile(positive
charge, carbocation, lewis acid).
H

Br

B r-

Br

26

Label the acid, base, conjugate acid and conjugate base in the reaction below. Does the
reaction go forwards, backwards or is it at equilibrium? Why?
OH

OH

NH 3

NH 3

N H4

NH 2

FO R W A R D S

O R B A C K W A R D S O R E Q U IL IB R IU M

W HY?

H3PO4(aq)

H3O+ (aq)

H2O(aq)

H2PO4-2(aq)

Circle the better base from the two below and explain why it is better.
C
F

OR

E xplain

H
O

E xplain

OR

F 3C

H2
C

C
H

H
C
2

OR
OH

H3C

H2
C

C
H2

F2
C

OH

OH
OH

OR

E x p la in :

C H3
E x p la in :

OCH

27

In each pair below, circle the compound that is a stronger acid and explain why it is a stronger acid.

F3C

H2
C

C
H2

H2
C

OR
OH

H3C

H2
C

C
H2

F2
C

OH

OH
OH

OR

Explain:

Due to the inductive effect, this molecule


is a much stronger acid. The anion is
stabilized by the electron withdrawing effect
of the two fluorines adjacent to the negative
charge.
-

CH3

OCH3

Explain:

This one is stronger due to resonance


stabilization. The CH3 can not contribute
to the resonance hybrid like the carbonyl can

Negative charge can be delocalized to the


oxygen of the carbony. The other molecule
can not accomplish this.

OCH3

OCH3

28

Using the pKa chart predict and draw the product of this Bronsted acid/base reaction. For
each hydrogen indicated by an arrow, list the pKa of that hydrogen.
1
OH

1 equ ivalent

Br

OH
H2
C

Br

+
CH 3

4
NH 2

N H3

If you use excess NH3, list the hydrogens(using 1, 2, 3, 4, 5) that will deprotonate.
If you use excess CH3CH2O- list the hydrogens(using 1, 2, 3, 4, 5) that will deprotonate.

10.0
1
OH

OH

O 4.2

1 equivalent

Br

OH
H2
C

Br
NH2

4
O 9.2 O

Br

9.4

+ NH4+
OH2
C

NH3

CH3

5
19

Br
NH2

CH3
O

3
36

If you use excess NH3, list the hydrogens(using 1, 2, 3, 4, 5) that will deprotonate.
2 and 4
If you use excess CH3CH2O- list the hydrogens(using 1, 2, 3, 4, 5) that will deprotonate.
1, 2 and 4

29

Part I:
Connectivity WorksheetPage 12bottom of page B, D, G, I, J
Worksheet
Page 4Draw 3-D orbital pictures for methyl cyanate and methyl isocyanate
Page 5Draw a resonance form for this cation that has all closed shell atoms
Page 7 (page 26) b(i)
Page 8 (page 27) A (a,c)
Page 11 (page 30) a, b
Part II:
For the molecule below, list all the functional groups. On the atoms identified with an
arrow, indicate if the functional groups are primary, secondary or tertiary (1o, 2o, 3o).

30

Fill in the Cs and Hs for the following:

OH

OH

Br

Cl

31

32

PAGE 5

H
H

H
C

C
C

N
H

C
N
H

33

34

CH3
H2C

CH3
H
C

CH
H3C

H2
C

CH

CH

C
H

CH

H2C

CH3

CH3
CH3
CH3

H
C
H2C

CH
C

CH3

H2
C

OH

CH3

H2C

CH2

CH3

OH

CH3
Br

CH3

CH
H3C

CH
CH

CH

Cl

CH
H3C

H
C

CH
C
H

CH2
CH3

CH3

You might also like