Organic Chemistry 2

Engr. Quennie Marie L.
Bañares, RChT
Definition, Structure,
C
Properties, Nomenclature,
Syntheses and Reactions of: O
AROMATIC COMPOUNDS N
ALCOHOLS AND ETHERS T
ALDEHYDES AND KETONES
E
CARBOXYLIC ACID AND ITS
DERIVATIVES N
AMINES T
S
Compounds that contains
a benzene ring and
behaves chemically like
benzene.
- The simplest aromatic hydrocarbon (or arene)
DEFINITION
- Discovery:
In 1825, Michael Faraday (English chemist) discovered Structure
benzene by isolating it from a compressed illuminating gas
Properties
that had been made by pyrolyzing whale oil and called it
“bicarburet of hydrogen”. Nomenclature
In 1834, Eilhardt Mitscherlich (German chemist)
Synthesis
synthesized benzene by heating benzoic acid with calcium
oxide. He also showed that benzene has a molecular Reactions
formula of C6H6 using vapor density measurements.
Aromaticity
- Presented by using a hexagon with a
Definition
circle in the middle to depict the six
pi electrons STRUCTURE
- has only as many hydrogen atoms as
Properties
it has carbon atoms
Nomenclature
- Last half of 19th century: August Kekulé proposed the
Synthesis
possible structure of benzene called Kekulé Structures
which in description, the bond between any two carbon Reactions
atoms is sometimes a single bond and sometimes a
Aromaticity
double bond
- Contains six-membered ring and three additional degrees
Definition
of unsaturation
- Planar STRUCTURE
- All C-C bond lengths are equal (as opposed to Kekulé
Properties
Structures)
RESONANCE Nomenclature
- Consist of two equivalent Lewis structures Synthesis

- The two structures are NOT in equilibrium with each
Reactions
other, instead, it is a resonance hybrid of the two Lewis
structures Aromaticity
- Explains why all C-C bond lengths are the

same: 1.39 Å (intermediate between C-C single
bond (1.53 Å) and C-C double bond (1.34 Å))
HYBRIDIZATION AND ORBITALS Definition
- sp2 hybridized and trigonal planar with all bond angles
STRUCTURE
120°
Properties
Nomenclature
Synthesis
Reactions
- The six adjacent p orbitals overlap, delocalizing the six Aromaticity

electrons over the six atoms making the benzene a
conjugated molecule
THEN NOW Definition
Low H to C ratio Six-carbon unit (Kekulé) Structure
PROPERTIES
“fragrant” Retains this six-carbon
unit through most Nomenclature
chemical transformations Synthesis
and degradations
Reactions
Stabilized by Aromaticity
delocalization of pi
electrons
Important IR and NMR absorptions of aromatic compounds:
Definition
Structure
PROPERTIES
Nomenclature
Synthesis
Reactions
Aromaticity
Source: Organic Chemistry by Smith, J.G.

13C NMR SPECTROSCOPY Definition
- Used to determine the substitution patterns in Structure
disubstituted benzenes, for example:
PROPERTIES
Nomenclature
Synthesis
Reactions
Aromaticity
INFRARED SPECTRA OF SUBSTITUTED BENZENES Definition
Structure
TYPE IR ABSORPTIONS (cm-1)
PROPERTIES
Monosubstituted Nomenclature
Synthesis
Ortho-substituted
Reactions
Meta-substituted Aromaticity
Para-substituted
UV SPECTRA Definition
- Near 205 nm (moderate intensity) Structure
- Range of 250-275 nm (less intense)
- Conjugation outside the benzene ring leads to PROPERTIES
absorptions at other wavelengths
Nomenclature
MASS SPECTRA Synthesis
- Major ion: m/z 91 (C6H5CH2+) Reactions
- Another ion: m/z 77 (C6H5+)
Aromaticity
Do not:
Definition
- Decolorize bromine through addition
- Decolorize the aqueous potassium permanganate Structure
through oxidation
PROPERTIES
- Add hydrogen rapidly even in the presence of metal
catalysts Nomenclature
- Add water in the presence of strong acids
Synthesis
However, Reactions
- It does add H in the presence of finely divided nickel at
Aromaticity
high temperature and pressure
- It does react with bromine in the presence of Lewis acid
catalysts such as ferric bromide, not by addition but by
substitution
BENZENE SUBSTITUTION Definition
- Only one monobromobenzene is formed since: Structure
1. Only one of the six carbons in the benzene is reactive.
2. All six hydrogen atoms in benzene are equivalent, and PROPERTIES
replacing any one of them with a substituent results in
Nomenclature
the same product.
Synthesis
Reactions
Aromaticity
RESONANCE ENERGY Definition
- difference between the amount of heat actually released Structure
and that calculated on the basis of the Kekulé structure
PROPERTIES
Using the concept of resonance energies, hydrogenation of
Nomenclature
cyclohexene to cyclohexane gives:
Synthesis
Reactions
Aromaticity
We would now expect that hydrogenation of 1,3-

cyclohexadiene would liberate roughly twice as much heat.
But,
Definition
Structure
PROPERTIES
The difference accounts for the stability of compounds Nomenclature
containing conjugated double bonds.
Synthesis
Extending this way of thinking, if benzene is simply 1,3,5-
cyclohexatriene, we would predict benzene to liberate Reactions
approximately 360 kJ/mol, but,
Aromaticity
Definition
Structure
PROPERTIES
Therefore, the low heat of hydrogenation of benzene Nomenclature
means that benzene is especially stable, even more so than Synthesis
the conjugated compounds. Reactions
Aromaticity
MONOSUBSTITUTED Definition
- Two ways of naming: Structure
1. Benzene is the parent name and the substituent is
simply indicated by a prefix. Carbon substituents are Properties
named as alkyl groups. NOMENCLATURE
Synthesis
Reactions
Aromaticity
MONOSUBSTITUTED Definition
2. For other simple and common compounds, the Structure
substituent and the benzene ring taken together may
form a commonly accepted parent name. Properties
NOMENCLATURE
Synthesis
Reactions
Aromaticity
DISUBSTITUTED Definition
1. Relative positions of the two substituents are indicated Structure
by the prefixes ortho-, meta-, and para- (abbreviated o-,
m-, and p-) or by the use of numbers (ring is numbered Properties
that gives the lowest number for the substituents). NOMENCLATURE
Synthesis
Reactions
Aromaticity
DISUBSTITUTED Definition
2. If the two groups are different, alphabetize the names of Structure
the substituents preceding the word benzene. If one of
the substituents is part of a common root, name the Properties
molecule as a derivative of that monosubstituted NOMENCLATURE
benzene.
Synthesis
Reactions
Aromaticity
Some Common Names of Disubstituted Benzenes Definition
Structure
Properties
NOMENCLATURE
Synthesis
Reactions
Aromaticity
POLYSUBSTITUTED Definition
- Indicated by the use of numbers: Structure
1. Number the ring in a way that gives the lowest possible
numbers for the substituents. Properties
NOMENCLATURE
2. If different substituents are present, alphabetize the
substituent names. Synthesis
Reactions
3. When the substituents are a part of a common root,
name the molecule as a derivative of that Aromaticity
monosubstituted benzene and the substituent that
comprises the common root is assumed to be at
position 1.
POLYSUBSTITUTED Definition
For example: Structure
Properties
NOMENCLATURE
Synthesis
Reactions
Aromaticity
AROMATIC RINGS AS SUBSTITUENT Definition
BENZYL Structure
PHENYL GROUP ARYL GROUP
GROUP
Properties
Definition NOMENCLATURE
Synthesis
Abbreviation -, -, 𝜑- -, - -
Reactions
Aromaticity
Structure and
Example
AROMATIC RINGS AS SUBSTITUENT Definition
Rules in considering aromatic rings as substituent: Structure
1. A hydrocarbon composed of one saturated chain and a
benzene ring is usually named as a derivative of the Properties
larger structural unit. NOMENCLATURE
Synthesis
Reactions
2. If the chain is unsaturated, the compound is named as a
derivative of that chain, regardless of ring size. Aromaticity
- obtained from catalytic dehydrogenation of cyclohexane
Definition
and from coal tars
Structure
PLASTIC RESIN NYLON RUBBER
Properties
Nomenclature
SYNTHESIS
Some Uses of Benzene Reactions
Aromaticity
BENZENE DYES DRUGS

DETERGENTS
ELECTROPHILIC AROMATIC SUBSTITUTION Definition
General reaction: Structure
Properties
Nomenclature
Five reactions through electrophilic aromatic substitution:
1. Halogenation Synthesis
2. Nitration
REACTIONS
3. Sulfonation
4. Friedel-Crafts Alkylation Aromaticity
5. Friedel-Crafts Acylation
*Since di naman tinatanong sa board exam kung pano nangyari ang mga bagay bagay, and kadalasan
product lang naman tinatanong, di ko na sinabay yung mechanisms, but if you want to know the mechanisms of the
reactions, you can check Organic Chemistry books
1. Halogenation Structure
Properties
Nomenclature
Synthesis
REACTIONS
Aromaticity
Lewis Acids typically used: AlCl3, FeCl3, FeBr3
Purpose of LA: To make the halogen a stronger
electrophile
2. Nitration Structure
Properties
Nomenclature
Synthesis
REACTIONS
Concentrated sulfuric acid: increases rate of reaction by
increasing the concentration of the electrophile Aromaticity
3. Sulfonation
Structure
Properties
Nomenclature
Synthesis
REACTIONS
Benzene reacts with fuming sulfuric acid (contains added
sulfur trioxide). If reacted with concentrated sulfuric acid, Aromaticity
reaction is slow.
To desulfonate (remove sulfonic acid group): use dilute

sulfuric acid and let mixture pass through steam
4. Friedel-Crafts Alkylation Structure
- discovered by Charles Friedel, a French chemist,
and his American collaborator, James M. Crafts in 1877 Properties
Nomenclature
Synthesis
REACTIONS
These reaction are NOT restricted to the use of alkyl halides
and aluminum chloride, other pairs of reagents that from Aromaticity
carbocations may be used as well, for example, use of an
alkene and an acid and the mixture of an alcohol and an
acid.
X represents halides (F, Cl, Br, I) and R represents alkyl groups
5. Friedel-Crafts Acylation Structure
- often carried out by treating the aromatic
compound with an acyl halide (often an acyl chloride) Properties
Nomenclature
Acyl group: Examples:
Synthesis
REACTIONS
Aromaticity
Reaction:
R represents alkyl groups

Limitations Friedel-Crafts Reactions: Structure
1. Rearrangements can occur. Properties

2. Usually give poor yields when powerful electron- Nomenclature
withdrawing groups (-NH2, -NHR, or -NR2 group) are
present. Synthesis
3. Aryl and vinylic halides do not react.
REACTIONS
4. Polyalkylations often occur.
Aromaticity
SYNTHETIC APPLICATIONS OF F-C ACYLATIONS Definition
1. The Clemmensen Reduction (acidic conditions) Structure
- general method for reducing a ketone to a
methylene group Properties
- consists of refluxing the ketone with hydrochloric Nomenclature
acid containing amalgamated zinc
Synthesis
REACTIONS
Aromaticity

SYNTHETIC APPLICATIONS OF F-C ACYLATIONS Definition
2. The Wolff-Kishner Reduction (basic conditions) Structure
- also a method for reducing a ketone to a methylene
group by heating the ketone with hydrazine and base Properties
Nomenclature
Synthesis
REACTIONS
Aromaticity
EFFECTS OF SUBSTITUENTS Definition
A substituent group already present on a benzene Structure
ring can affect both the reactivity of the ring and the
orientation that the incoming group takes on the ring. Properties
Nomenclature
Activating group - a substituent that can make the ring
more reactive Synthesis
REACTIONS
Deactivating group - a substituent that can make the ring
less reactive Aromaticity
1. Effect on reactivity Structure
In theory, Inductive effect: Properties
Nomenclature
Synthesis
REACTIONS
Aromaticity
2. Effect on orientation Structure
Two general classes:
1. Ortho-para directors - predominantly direct the Properties
incoming group to a position ortho or para to itself Nomenclature
Synthesis
REACTIONS
Aromaticity
2. Meta directors - predominantly direct the incoming Structure
group to a position meta to itself
Properties
Nomenclature
Synthesis
REACTIONS
Aromaticity
Summary of Examples of the Two Classes are on the next

page.
Definition
Structure
Properties
Nomenclature
Synthesis
REACTIONS
Aromaticity
Source: Organic Chemistry by T.W.G Solomons, C.B. Frhyle, and S.A. Snyder
SUBSTITUTED BENZENES Definition
Arenes - hydrocarbons that consist of both aliphatic Structure
and aromatic groups
Properties
Side chain - the aliphatic portion of these compounds Nomenclature
Examples: Synthesis
REACTIONS
Aromaticity
MONOSUBSTITUTED BENZENES Definition
For example, halogenation of toluene.
Properties
Effect of substituent: reacts faster and methyl group (CH3) Nomenclature
is an ortho-para director.
Synthesis
REACTIONS
Aromaticity
Another example, halogenation of nitrobenzene.
Properties
Effect of substituent: reacts slower and nitro group (NO2) is Nomenclature
a meta director.
Synthesis
REACTIONS
Aromaticity
2. Halogenation of Activated Benzenes Structure
Activated benzenes – benzene rings activated by strong Properties

electron-donating groups (-OH, -NH2, -OR, -NHR, -NR2) Nomenclature
These benzenes undergo: Synthesis

a. Polyhalogenation – when treated with X 2 and FeX3
REACTIONS
- gives trihalide derivatives
Aromaticity
b. Monosubstitution – without catalyst
- forms a mixture of ortho and
para products
X represents halides (F, Cl, Br, I)
Examples Properties
a. Polyhalogenation Nomenclature
Synthesis
REACTIONS
Aromaticity
Examples Properties
b. Monosubstitution Nomenclature
Synthesis
REACTIONS
Aromaticity
3. Oxidation of the Benzene ring Structure
- done by ozonolysis, followed by treatment with
hydrogen peroxide Properties
Nomenclature
Synthesis
REACTIONS
Aromaticity

DISUBSTITUTED BENZENES Definition
Undergoes electrophilic aromatic substitution. Structure
Three Guidelines:
1. When the directing effects of two groups reinforce, the Properties
new substituent is located on the position directed by Nomenclature
both groups.
Synthesis
REACTIONS
Aromaticity
Three Guidelines: Structure
2. If the directing effects of two groups oppose each other,
the more powerful activator “wins out”. Properties
Nomenclature
Synthesis
REACTIONS
Aromaticity
Three Guidelines: Structure
3. No substitution occurs between two meta substituents
because of crowding. Properties
Nomenclature
Synthesis
REACTIONS
Aromaticity
REACTIONS OF THE SIDE CHAIN Definition
1. Benzylic Halogenation of the Side Chain Structure
For example, benzylic chlorination of toluene which
takes place in the gas phase at 400–600 °C or in the Properties
presence of UV light. Nomenclature
Synthesis
REACTIONS
Aromaticity
Multiple substitutions occur with an excess of

chlorine.
1. Benzylic Halogenation of the Side Chain Structure
Another example, benzylic bromination.
Properties
Nomenclature
Synthesis
REACTIONS
Aromaticity
*NBS is N-bromosuccinimide, often used because it provides a

stoichiometric amount of bromine in low concentration.
To avoid confusion in which position the halide will
Definition
replace an H atom, check the conditions of the reaction.
Structure
Ionic condition - with the use of X2 and FeX3, results in
Properties
the replacement of H by X on the aromatic ring to form
ortho and para isomers (keep in mind that activated Nomenclature
benzene rings are an exception)
Synthesis
Radical condition - with the use of X2 and light or heat, REACTIONS

results in the replacement of H by X at the benzylic
Aromaticity
carbon of the alkyl group
X represents halides (F, Cl, Br, I)

Example of Halogenation in Ionic and Radical Condition:
Definition
Structure
Properties
Nomenclature
Synthesis
REACTIONS
Aromaticity
2. Oxidation of Alkyl Benzenes Structure
- an important characteristic of side-chain oxidations
is that oxidation takes place initially at the benzylic carbon Properties
Nomenclature
Synthesis
REACTIONS
Aromaticity
2. Oxidation of Alkyl Benzenes Structure
- for substrates with more than one alkyl group, it is
converted to dicarboxylic acids Properties
Nomenclature
Synthesis
REACTIONS
Aromaticity
3. Reduction of Nitro Groups Structure
Properties
Nomenclature
Synthesis
REACTIONS
Aromaticity
MULTISTEP SYNTHESIS Definition
Basically, a series of reactions. For example: Structure
Properties
Nomenclature
Synthesis
REACTIONS
Aromaticity
REDUCTION OF AROMATIC COMPOUNDS Definition
1. Catalytic Hydrogenation Structure
- takes place under pressure with a metal catalyst
such as nickel Properties
Nomenclature
Synthesis
REACTIONS
Aromaticity
REDUCTION OF AROMATIC COMPOUNDS Definition
2. Birch Reduction Structure
- developed by A.J. Birch, an Australian chemist
Properties
Nomenclature
Synthesis
REACTIONS
With substituent: synthesis of 2-cyclohexenone
Aromaticity
FOUR STRUCTURAL CRITERIA Definition
1. A molecule must be cyclic. Structure
- each p orbital must overlap with p orbitals on two
adjacent atoms Properties
Nomenclature
Synthesis
Reactions
AROMATICITY
2. A molecule must be planar. Structure
- all adjacent p orbitals must be aligned so that the pi
electron density can be delocalized Properties
Nomenclature
For example,
Synthesis
Reactions
AROMATICITY
3. A molecule must be completely conjugated. Structure
- must have a p orbital in every atom
Properties
Nomenclature
Synthesis
Reactions
AROMATICITY
4. A molecule must satisfy Hückel’s Rule. Structure
- must contain a particular number of pi electrons
Properties
Hückel’s Rule – established by Erich Hückel in 1931 Nomenclature
- an aromatic compound must contain
4𝑛 + 2 𝜋 electrons where n should be an integer (0, 1, 2, and Synthesis
so forth) Reactions
For example, Benzene, an aromatic compound: AROMATICITY
4𝑛 + 2 = 6 𝜋 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠
∴ 𝑛 = 1 (𝑎𝑛 𝑖𝑛𝑡𝑒𝑔𝑒𝑟)
Structure
Properties
Nomenclature
Synthesis
Reactions
AROMATICITY

CLASSIFICATION OF COMPOUNDS (considering aromaticity)
Definition
1. Aromatic - cyclic, planar, completely conjugated Structure
with 4n + 2 pi electrons
Properties
2. Antiaromatic - cyclic, planar, completely conjugated Nomenclature
with 4n pi electrons
Synthesis
3. Not aromatic - or nonaromatic Reactions
- a compound that lacks one or more of
the four requirements to be aromatic or AROMATICITY
antiaromatic
STABILITY COMPARISON Definition
- compared to an acyclic compound with the same Structure
number of pi electrons
Properties
1. Aromatic - more stable Nomenclature
2. Antiaromatic - less stable
3. Not aromatic - same stability Synthesis
Reactions
AROMATICITY
PO L Y M E R S
1. BTX Mixture - composed of benzene and toluene
(aromatic compounds) together with p-xylene
- useful starting materials for synthetic
polymers
MOTHBALLS
2. Naphthalene - simplest polycyclic aromatic
hydrocarbons (PAHs)*; active ingredient in mothballs
3. Benzo(a)pyrene - formed by the incomplete

combustion of organic materials; found in cigarette
EXHAUST
smokes, automobile exhaust and fumes from charcoal
grills
*definition on page 75 CIGARETTE

PO L Y M E R S
MOTHBALLS
Synthetic PAHs
EXHAUST
Benzo(a)pyrene
Helicene Twistoflex
CIGARETTE
ZOLOFT
VALIUM
VIRACEPT
Source: Organic
Chemistry by J.G.
Smith CLARITIN
ALMONDS
WINTERGREEN
CINNAMON
Source: Organic Chemistry by T.W.G Solomons, C.B. Frhyle, and S.A. Snyder VANILLA
ANNULENES
- hydrocarbons containing a single ring with
alternating double and single bonds
TO NAME:
1. Indicate the number of atoms in the ring in brackets.
2. Add the word annulene.
Examples of an annulene:
Annulenes and their Aromaticity
EXAMPLES
Aromatic
[16]annulene, [24]annulene, [12]annulene

Antiaromatic
Nonaromatic
POLYCYCLIC AROMATIC HYDROCARBONS (PAHs)
- compounds containing two or more benzene rings
that share carbon-carbon bonds
- as the number of fused benzene rings increases, the
number of resonance structures increases
Examples:
AROMATIC HETEROCYCLES
- heterocycles containing oxygen, nitrogen, or sulfur
can also be aromatic
Heterocycles - rings that contain at least one

heteroatom
Examples:
1. Pyridine
2. Pyrrole
3. Histamine
4. Furan
5. Thiophene
1. Pyridine
- heterocycle containing a six-membered ring with
three pi bonds and one nitrogen atom
- cyclic, planar, completely conjugated and has 6 pi
electrons (from the double bonds) satisfying the Hückel’s
rule
- the nitrogen atom is sp2 hybridized
Aromatic and
weakly basic
2. Pyrrole
- heterocycle containing a five-membered ring with
two pi bonds and one nitrogen atom
electrons (four from the pi bonds and two from the lone
pair) satisfying the Hückel’s rule
- the nitrogen atom is sp2 hybridized
Aromatic and
not basic
3. Histamine
- biologically active amine formed in many tissues
- five-membered ring with two pi bonds and two N
atoms, one of which is similar to pyridine and one is similar
to pyrrole
electrons
Aromatic
4. Furan and Thiophene
- both resembles a pyrrole but instead of nitrogen, it
contains oxygen (furan) and sulfur (thiophene) atoms
Both Aromatic
CHARGED AROMATIC COMPOUNDS
- both positively and negatively charged can be
aromatic
1. Cyclopentadienyl Anion
- cyclic and planar anion with two double bonds and
a non-bonded electron pair (resembles pyrrole)
- completely conjugated and has 6 pi electrons
- negatively charged carbon is sp2 hybridized
Aromatic
CHARGED AROMATIC COMPOUNDS
2. Tropylium Cation
- planar carbocation with three double bonds and a
positive charge contained in seven-membered ring
- completely conjugated since the positively charged
carbon is sp2 hybridized
- has 6 pi electrons from the pi bonds satisfying the
Hückel’s rule
Aromatic
1985 - established the structure and existence of
fullerenes by H. W. Kroto, R. E. Smalley and R. F. Curl and
had found both C60 and C70 ; on 1996, they shared a Nobel
Prize in Chemistry
1990 - W. Krätschmer, D. Huffman and co-workers

described the first practical synthesis of C60, a molecule
shaped like a soccer ball and called buckminsterfullerene
Fullerenes - cage-like molecules with the geometry of a

truncated icosahedron or geodesic dome, named after the
architect Buckminster Fuller; composed of a network of
pentagons and hexagons
- completely conjugated since each carbon is sp2
hybridized and forms sigma bonds to three other carbon
atoms
C60 - have 12 pentagons and 20 hexagons

C70 - have 12 pentagons and 25 hexagons
Not Aromatic
(since not planar)
Organic derivatives of
water (H2O). Compounds
that contain carbon-
oxygen sigma bonds.
- Compounds that contain a hydroxyl group (-OH) bonded
DEFINITION
to an sp3 hybridized carbon atom
Structure
CLASSIFICATIONS
1. Primary Alcohol (1°) Properties
2. Secondary Alcohol (2°) Nomenclature

3. Tertiary Alcohol (3°)
Synthesis
- classification is based on the number of carbon Reactions

atoms bonded to the carbon with the hydroxyl group
HYDROXYL GROUP ON AN SP2 HYBRIDIZED C ATOM DEFINITION
1. Enols
- Compounds that have an –OH group on a carbon of Structure
a C-C double bond Properties
Nomenclature
Synthesis
2. Phenols
- Compounds that have a hydroxyl group attached Reactions
directly to a benzene ring

The alcohol carbon atom may also be a saturated
DEFINITION
carbon atom adjacent to an alkenyl or alkynyl group, or the
carbon atom may be a saturated carbon atom that is Structure
attached to a benzene ring:
Properties
Nomenclature
Synthesis
Reactions
- Compounds that have two alkyl groups bonded to an
DEFINITION
oxygen atom
Structure
CLASSIFICATIONS
1. Symmetrical - if the two alkyl groups are the Properties
same Nomenclature
2. Unsymmetrical - if the two alkyl groups are the
different Synthesis
Reactions
EPOXIDES DEFINITION
- are ethers having the oxygen atom in a three-
Structure
membered ring
- also called oxiranes Properties
Nomenclature
Synthesis
Reactions
- Contains an oxygen atom surrounded by two atoms and
Definition
two nonbonded electron pairs
- Oxygen atom is tetrahedral and sp3 hybridized STRUCTURE
- Bent shape (like H2O)
Properties
- Bond angle around oxygen atom is similar to a tetrahedral
bond angle of 109.5° (approximately) Nomenclature
- However epoxides have angle strain, with a C-O-C bond
Synthesis
angle of 60° (therefore more reactive than ethers)
Reactions
Alcohol Ether Epoxide

HYDROGEN BONDING Definition
- alcohols, ethers and epoxides exhibit dipole-dipole Structure
interactions because of their bent structure
- alcohols are capable of intermolecular hydrogen bonding PROPERTIES
because of the hydrogen bonded to the oxygen atom
Nomenclature
making them more polar than ethers and epoxides
- Steric factors affect the extent of hydrogen bonding Synthesis
Reactions
BOILING POINT Definition
- Ethers have boiling points that are roughly comparable Structure
with those of hydrocarbons of the same molecular
weight (MW) PROPERTIES
- Alcohols have much higher boiling points than
Nomenclature
comparable ethers or hydrocarbons
Synthesis
SOLUBILITY IN WATER
Reactions
- Ethers have solubilities in water that are similar to those
of alcohols of the same molecular weight
- solubility of alcohols decreases as the hydrocarbon
portion increases because they become more “alkane-
like” rather than “water-like”
Definition
Structure
PROPERTIES
Nomenclature
Synthesis
Reactions

SUBSTITUTIVE NOMENCLATURE Definition
Four Features: Structure
1. Locants
2. Prefixes Properties
3. Parent Compound NOMENCLATURE
4. Suffixes
Synthesis
In general, numbering of the chain always begins at Reactions
the end nearer the group named as a suffix.
Also, the locant for the suffix may be placed before
(such as the example above) or after the parent name, both
are acceptable. Hence, the compound above can be named
as 4-methylhexan-1-ol.
STEPS (IUPAC) Definition
1. Select the longest continuous carbon chain to which the Structure
hydroxyl group is attached. Change the –e ending of the
parent alkane to the suffix –ol. Properties
2. Number the carbon chain to give the carbon bearing the NOMENCLATURE
hydroxyl group the lower number, then apply all other
rules of nomenclature. Synthesis
Reactions
STEPS (COMMON NAME) Definition
1. Name all the carbon atoms of the molecule as a single Structure
alkyl group.
2. Add the word alcohol, separating the words with a Properties
space. These alcohols are called alkyl alcohols. NOMENCLATURE
Synthesis
Reactions
HYDROXYL GROUP BONDED TO A RING Definition
1. The ring is numbered beginning with the hydroxyl Structure
group.
2. The ring is numbered in either clockwise or Properties
counterclockwise fashion to give the next substituent NOMENCLATURE
the lower number.
Synthesis
Reactions
GLYCOLS OR DIOLS Definition
Glycols (Common) or Diols (IUPAC) - compounds with two Structure
hydroxyl groups
Properties
To name, the suffix –diol is added to the name of the NOMENCLATURE
parent alkane, and numbers are used in the prefix to
indicate the location of the two OH groups. Synthesis
Reactions
IUPAC
COMMON NAME
NOTE: Definition
The hydroxyl group has precedence over double Structure
bonds and triple bonds in deciding which functional group
to name as the suffix. Properties
NOMENCLATURE
For example:
Synthesis
Reactions
STEPS (COMMON) Definition
- used for simple ethers Structure
1. Name both alkyl groups bonded to the oxygen.
2. Arrange the names of the alkyl groups alphabetically Properties
and add the word ether. NOMENCLATURE
For example, Synthesis
Reactions
For symmetrical ethers, name the alkyl group and add the Structure
prefix di-.
Prefixes such as sec-, tert-, iso-, etc. are not included in the Properties
alphabetization. NOMENCLATURE
Synthesis
Reactions
- used for more complex ethers and for compounds Structure
with more than one ether linkage
1. Name the simpler alkyl group + O atom as an alkoxy Properties
substituent (alkoxy group: RO-) by changing the –yl NOMENCLATURE
ending of the alkyl group to –oxy.
2. Name the remaining alkyl group as an alkane (usually Synthesis
the longer chain), with the alkoxy group as a substituent Reactions
of this chain.
CYCLIC ETHERS (EPOXIDES) Definition
- can be named in several ways: Structure
1. By replacement nomenclature Properties

- relate the cyclic ether to the corresponding NOMENCLATURE
hydrocarbon ring system and use the prefix oxa- to indicate
that an oxygen atom replaces a CH2 group Synthesis
Reactions
2. As an epoxyalkane Properties
- name the alkane chain or ring to which the oxygen NOMENCLATURE
is attached and use the prefix epoxy- to name the epoxide
as a substituent (use two numbers to indicate the location Synthesis
of the atoms to which the O is bonded) Reactions
3. As derivatives of oxirane Properties

- a cyclic three-membered ether is named oxirane NOMENCLATURE
and a four-membered ether is called oxetane
- with substituents, the oxirane ring is numbered to Synthesis
put the O atom in position 1 and the next substituent at Reactions
position 2 (for monosubstituted, no number is used)
4. As alkene oxides Properties

- mentally replace the epoxide oxygen by a double NOMENCLATURE
bond, name the alkene, and then add the word oxide
- common names for cyclic ethers (in parentheses) Synthesis
Reactions
ACID-CATALYZED HYDRATION OF ALKENES Definition
- Takes place with Markovnikov regioselectivity Structure
- A reversible reaction
- One complication is occurrence of rearrangements Properties
(hydride or alkanide shift) to a more stable carbocation Nomenclature
thus resulting to a mixture of isomeric alcohol products
SYNTHESIS
Reactions
Alkene Water Alcohol

OXYMERCURATION-DEMERCURATION Definition
- Markovnikov addition of H and OH Structure
- generally takes place without the complication of
rearrangements Properties
- Supplements acid-catalyzed hydration Nomenclature
SYNTHESIS
Reactions
Ac represents acetate ion

HYDROBORATION-OXIDATION Definition
- Results in Anti-Markovnikov and syn hydration of an Structure
alkene
Properties
For example: Nomenclature
SYNTHESIS
Reactions
REDUCTION OF CARBONYL COMPOUNDS Definition
- Carbonyl compounds: has sp2 hybridized carbon atom, Structure
trigonal planar in structure and has bond angles of 120°
Properties
Nomenclature
SYNTHESIS
Reactions
- Reduction: usually corresponds to increasing its

hydrogen content or to decreasing its oxygen content
1. Using Lithium Aluminum Hydride (LiAlH4 or LAH) Structure
- reduces carboxylic acids and esters to primary
alcohols Properties
Specific examples: Nomenclature
SYNTHESIS
Reactions
Et2O is anhydrous diethyl ether which is used as solvent

2. Using Sodium Borohydride (NaBH4) Structure
- reduces aldehydes and ketones
- can be used safely and effectively in water as well Properties
as alcohol solvents Nomenclature
Specific examples:
SYNTHESIS
Reactions
Summary: Structure
Sodium borohydride is a less powerful reducing
agent than lithium aluminum hydride. Properties
Nomenclature
SYNTHESIS
Reactions
USING GRIGNARD REAGENT* (RMgX) AND Definition
ORGANOLITHIUM COMPOUNDS (RLi)
Structure
- Organolithium compounds: are often prepared by the
Properties
reduction of organic halides with lithium metal usually
carried out in ether solvents (diethyl ether and Nomenclature
tetrahydrofuran)
- Preparation of organolithium compounds: SYNTHESIS
Reactions
*Grignard Reagent is discussed previously on the first PPT (Synthesis of Alkanes)

USING GRIGNARD REAGENT (RMgX) AND Definition
Structure
1. Reaction with Epoxides
Properties
- the RMgX or RLi react as nucleophiles
Nomenclature
SYNTHESIS
Reactions
Structure
2. Reaction with Carbonyl Compounds
Properties
- the RMgX or RLi react as nucleophiles and attack
the unsaturated carbon Nomenclature
CARBONYL COMPOUND PRODUCT SYNTHESIS

Formaldehyde (Methanal) Primary Alcohol
Reactions
Aldehyde Secondary Alcohol
Ketone Tertiary Alcohol

Ester Tertiary Alcohol
Structure
Properties
- Specific examples:
Nomenclature
SYNTHESIS
Reactions
Structure
Properties
Nomenclature
SYNTHESIS
Reactions
Structure
Properties
Nomenclature
SYNTHESIS
Reactions
Structure
Properties
Nomenclature
SYNTHESIS
Reactions
DEHYDRATION OF ALCOHOLS (SYMMETRICAL ETHERS)
Definition
- Two alcohol molecules can form an ether by loss of water Structure
through an acid-catalyzed substitution reaction
Properties
Nomenclature
- Take note that this takes place at lower temperature than SYNTHESIS
dehydration to an alkene:
Reactions
DEHYDRATION OF ALCOHOLS Definition
Complications of the Reaction: Structure
1. Attempts to synthesize ethers by intermolecular
dehydration of secondary alcohols are usually Properties
unsuccessful because alkenes form too easily. Nomenclature
2. Attempts to make ethers with tertiary alkyl groups lead SYNTHESIS

predominantly to alkenes.
Reactions
3. Intermolecular dehydration is not useful for the

preparation of unsymmetrical ethers from primary
alcohols because the reaction leads to a mixture of
products.
WILLIAMSON ETHER SYNTHESIS (UNSYMMETRICAL ETHERS)
Definition
- nucleophilic substitution reaction Structure
- consists of an SN2 reaction of a sodium alkoxide with an
alkyl halide, alkyl sulfonate, or alkyl sulfate Properties
Nomenclature
For example:
SYNTHESIS
Reactions
ALKOXYMERCURATION-DEMERCURATION Definition
- reaction of an alkene with an alcohol in the presence of a Structure
mercury salt such as mercuric acetate or trifluoroacetate
leads to an alkoxymercury intermediate, which on Properties
reaction with sodium borohydride yields an ether Nomenclature
SYNTHESIS
Reactions
Solvomercuration-demercuration - When the alcohol

reactant is also the solvent
EPOXIDATION Definition
- Reaction of an alkene with an organic peroxy acid Structure
(RCO3H—sometimes called simply a peracid)
- meta-Chloroperoxybenzoic acid (mCPBA) is one peroxy Properties
acid reagent commonly used for epoxidation Nomenclature
SYNTHESIS
Reactions
By-product
(often not written)
CONVERSION TO ALKYL HALIDES Definition
1. Reaction with Hydrogen Halides Structure
- substitution reaction
- acid-catalyzed reaction Properties
Nomenclature
Synthesis
Order of Reactivity of Alcohols:
REACTIONS
3° > 2° > 1° > methyl
Order of Reactivity of Hydrogen Halides:

HI > HBr > HCl (HF is generally unreactive)
2. Reaction with Phosphorus Tribromide (PBr3) Structure
- primary and secondary alcohols react with PBr3 to
yield to alkyl bromides Properties
- usually occurs without rearrangements Nomenclature
Synthesis
REACTIONS
3. Reaction with Thionyl Chloride (SOCl2) Structure
- converts primary and secondary alcohols to alkyl
chlorides Properties
- Pyridine (C5H5N) is often included to promote the Nomenclature
reaction
Synthesis
REACTIONS
1° or 2°
OXIDATION TO CARBONYL COMPOUNDS Definition
- Oxidation: Increasing the oxygen content of an organic Structure
molecule or decreasing its hydrogen content
Properties
ALCOHOL OXIDIZED TO
Primary Aldehyde and Carboxylic acid Nomenclature
Synthesis
Secondary Ketone REACTIONS

Tertiary Cannot be oxidized
1. Swern Oxidation Structure
- reaction is conducted in the absence of water, thus
primary alcohols form aldehydes and not carboxylic acids Properties
Nomenclature
Synthesis
REACTIONS
DMSO is dimethyl sulfoxide

2. Chromic Acid (H2CrO4) Oxidation Structure
- Chromic acid is an example of Chromium (IV)
reagent and is a carcinogen and an environmental hazard Properties
- a well-known source of chromic acid is the Jones Nomenclature
reagent
Synthesis
REACTIONS
Cyclooctanone
2. Chromic Acid (H2CrO4) Oxidation Structure
- Primary alcohols are oxidized to carboxylic acids
while secondary alcohols are oxidized to ketones Properties
- additional info: the color change of chromic acid Nomenclature
solutions are basis for the original breathalyzer alcohol test
Synthesis
REACTIONS
3. Using Pyridinium Chlorochromate (PCC) Structure
- PCC is a Chromium (IV) salt and is soluble in
dichloromethane, thus it can be used under conditions that Properties
exclude water, allowing for the oxidization of primary Nomenclature
alcohols to aldehydes because the aldehyde hydrate is not
present under anhydrous conditions Synthesis
- the structure of PCC:
REACTIONS
3. Using Pyridinium Chlorochromate (PCC) Structure
- specific examples:
Properties
Nomenclature
Synthesis
REACTIONS
4. Using Potassium Permanganate (KMnO4) Structure
- Primary alcohols and aldehydes can be oxidized by
potassium permanganate (KMnO4) to the corresponding Properties
carboxylic acids Nomenclature
- reaction is usually carried out in basic aqueous
solution Synthesis
REACTIONS
ACID CLEAVAGE Definition
- Reaction with very strong acids (HI, HBr, H2SO4) to cause Structure
the carbon-oxygen bond to break
Properties
Nomenclature
Synthesis
REACTIONS
ACID-CATALYZED HYDROLYSIS Definition
- Acid-catalyzed ring opening of an unsymmetrical Structure
epoxide occurs primarily by attack of the nucleophile at
the more substituted carbon atom Properties
- Produces an alcohol Nomenclature
Synthesis
REACTIONS
BASE-CATALYZED HYDROLYSIS Definition
- Base-catalyzed ring opening of an unsymmetrical Structure
epoxide occurs primarily by attack of the nucleophile at
the less substituted carbon atom Properties
- Produces an alcohol Nomenclature
Synthesis
REACTIONS
ANIONIC POLYMERIZATION Definition
- Treating ethylene oxide with sodium methoxide (in the Structure
presence of a small amount of methanol) can result in the
formation of a polyether (commercially known as Properties
carbowaxes) Nomenclature
Synthesis
REACTIONS
ALCOHOL THYME
PEPPERMINT
ETHER
VANILLA
Source: Organic Chemistry by T.W.G Solomons, C.B. Frhyle, and S.A. Snyder FENNEL
METHANOL
- Also called wood alcohol because it can be obtained by
heating wood at high temperatures in the absence of air
(destructive distillation)
- Nowadays, most methanol is prepared by the catalytic METHANOL
hydrogenation of carbon monoxide
- Highly toxic because of the oxidation products formed
when it is metabolized in the liver
- Methanol poisoning can occur by ingestion, inhalation of
vapors or prolonged exposure to skin
- Ingestion can cause blindness (mild, approx. 15 mL), even
death (large, approx. 100 mL)
WOOD
ETHANOL
- Also called grain alcohol
- Formed by fermentation of sugars and is carried out by
adding yeast to a mixture of sugars and water
- Alcohol of all alcoholic beverages ETHANOL
- Fermentation alone produces only up to 12-15% because
enzymes of the yeast are deactivated at higher
concentrations, therefore distillation is done to produce
higher alcohol content (proof: twice the %alcohol by
volume) GRAPES
- Important industrial chemical produced by the acid-
catalyzed hydration of ethene
WINE
ETHANOL
- Is hypnotic (sleep producer) by depressing the central
nervous system and the activity in the upper brain
- Increases the production of stomach acid
- Dilates blood vessels ETHANOL
- Used as a gasoline additive because it readily combusts
with the release of energy
GASOLINE
ADDITIVE
2-PROPANOL
- Major component of rubbing alcohol
- When rubbed in skin it evaporates readily producing a
pleasant cooling sensation
- Used to clean skin before minor surgery and sterilize
medical instruments due to its weak antibacterial
properties
ETHYLENE GLYCOL
- Ethylene glycol (HOCH2CH2OH) is a major component of
antifreeze
- Has low molecular weight, a high boiling point, and is ETHYLENE
miscible with water GLYCOL
- Sweet tasting but toxic
- Propylene glycol (1,2-propanediol) is an alternative
because of its low toxicity
ANTIFREEZE
DIETHYL ETHER
- CH3CH2OCH2CH3
- is a very low boiling, highly flammable liquid
- general anesthetic revolutionized in the nineteenth
century but is highly flammable and causes nausea in
many patients therefore is replaced by halothane
(CF3CHBrCl)
PERIPLANONE B
- Sex pheromone of the female American cockroach
EPOTHILONE B
- Active against many taxol-resistant tumors and are
readily produced by the fermentation of soil bacteria
- Novel anticancer drug
Organic compounds that
contain a carbonyl group.
- Compounds that have a carbonyl group bonded to a
DEFINITION
carbon atom on one side and a hydrogen atom on the
other side Structure
- As for the case of formaldehyde, it has hydrogen atoms
Properties
on both sides
Nomenclature
Synthesis
Reactions
- Compounds that have a carbonyl group bonded to
DEFINITION
carbon atoms on both sides
- Has two alkyl or aryl groups bonded to the carbonyl Structure
group
Properties
Nomenclature
Synthesis
Reactions
- The carbonyl group is sp2 hybridized and is trigonal
Definition
planar, making it relatively uncrowded
- The electronegative oxygen atom polarizes the carbonyl STRUCTURE
group, making the carbonyl carbon electrophilic
Properties
Nomenclature
Synthesis
Reactions
DIPOLE-DIPOLE INTERACTIONS Definition
- This interaction is caused by the polar carbonyl group Structure
- They do not have O-H bond, therefore two molecules of
RCHO or RCOR are incapable of intermolecular hydrogen PROPERTIES
bonding making them less polar than alcohols and
Nomenclature
carboxylic acids
Synthesis
Reactions
- Have higher boiling points than hydrocarbons of the Structure
same molecular weight because of the polar carbonyl
group PROPERTIES
- Have lower boiling points than corresponding alcohols
Nomenclature
because of their incapability to form hydrogen bond
Synthesis
SOLUBILITY IN WATER
Reactions
- Low-molecular-weight aldehydes and ketones show
appreciable solubilities in water because of the ability of
the carbonyl oxygen atom to form strong hydrogen
bonds with water
- Acetone and acetaldehyde are soluble in water in all
proportions
Definition
Structure
PROPERTIES
Nomenclature
Synthesis
Reactions

- Aldehydes and ketones react with nucleophiles
Definition
- The relative reactivity of the carbonyl group is
determined by the number of R groups bonded to it Structure
- As the number of R groups around the carbonyl carbon
PROPERTIES
increases, the reactivity decreases
Nomenclature
Synthesis
Reactions
IR SPECTRA Definition
- Carbonyl group (C=O): strong peak at approx. 1700 cm-1 Structure
- C-H bond: one or two peaks at approx. 2700-2830 cm-1
PROPERTIES
1H AND 13C NMR SPECTRA
Nomenclature
- C-H bond: absorbs downfield at 9-10 ppm
- Protons on the alpha carbon: absorb at 2-2.5 ppm Synthesis
- 13C NMR: 190-215 ppm region Reactions
UV SPECTRA
- Carbonyl groups: between 270 and 300 nm
- C=O conjugated with double bonds: 300-350 nm
1. If the CHO is bonded to a chain of carbons, find the Structure
longest chain containing the CHO group, and change the
–e ending of the parent alkane to the suffix –al. If the Properties
CHO group is bonded to a ring, name the ring and add NOMENCLATURE
the suffix –carbaldehyde.
2. Number the chain or ring to put the CHO group at Synthesis
position 1, but omit this number from the name. Apply Reactions
the other usual rules of nomenclature.
1. A common name for aldehyde is formed by taking the Structure
common parent name and adding the suffix –aldehyde.
Common parent names are listed in the table next slide. Properties
NOMENCLATURE
Synthesis
Reactions
2. Greek letters are used to
designate the location of
substituents in common names.
The carbon adjacent to the CHO
group is the 𝜶 carbon, and so forth.
COMMON PARENT NAMES Definition
IUPAC COMMON NO. OF C ATOMS
Metha- *Form- 1 Structure
Etha- *Acet- 2 Properties
Propan- Propion- 3
Buta- *Butyr- 4 NOMENCLATURE
Penta- *Valer- 5 Synthesis
Hexa- *Capro- 6
Hepta- Enantho- 7 Reactions
Octa- Capryl- 8
Nona- Pevargon- 9
Deca- Capri- 10
Octadeca- *Stear- 18
*Formica: ant; Acetum: vinegar; Butyrum: butter; Valerian: perennial herb; Caper: goat; Stear: tallow
Definition
Some specific examples using IUPAC and Common names: Structure
Properties
NOMENCLATURE
Synthesis
Reactions
1. Find the longest chain containing the carbonyl group, Structure
and change the –e ending of the parent alkane to the
suffix –one. Properties
2. Number the carbon chain to give the carbonyl carbon NOMENCLATURE
the lower number. Apply all the other usual rules of
nomenclature. With cyclic ketones, numbering always Synthesis
begin at the carbonyl carbon. Reactions
3. Some ketones have common names that are retained in Structure
the IUPAC system. (Common names in parentheses)
Properties
NOMENCLATURE
Synthesis
Reactions
1. Most common names are formed by naming both alkyl Structure
groups on the carbonyl carbon, arranging them
alphabetically, and adding the word ketone. (Common Properties
names in parentheses) NOMENCLATURE
Synthesis
Reactions
ACYL GROUPS (RCO-) AS SUBSTITUENTS Definition
1. Take either the IUPAC or common parent name and add Structure
the suffix –yl or –oyl.
Some common acyl groups: Properties
NOMENCLATURE
or methanoyl or ethanoyl
Examples: Synthesis
Reactions
WITH DOUBLE BONDS Definition
1. Aldehydes with double bonds are named as enals, while Structure
ketones with double bonds are named enones.
2. The chain is numbered to give the carbonyl carbon the Properties
lower number. NOMENCLATURE
Synthesis
Reactions
OXIDATION OF PRIMARY ALCOHOLS Definition
1. Swern Oxidation Structure
2. Oxidation with Pyridinium Chlorochromate (PCC)
- See Reaction of Alcohols Properties
Nomenclature
Specific examples:
SYNTHESIS
Reactions
OXIDATION OF ALKENES Definition
1. Cleavage using Ozone: Ozonolysis Structure
- See Organic Chemistry 1 PPT, under Reaction of
Alkenes, Oxidation of Alkenes, (3) Ozonolysis Properties
Nomenclature
Specific examples:
SYNTHESIS
Reactions
REDUCTION OF ACYL CHLORIDES, ESTERS AND Definition
NITRILES
Structure
- The reagents used are derivatives of LAH which are less
Properties
reactive since they are much more sterically hindered,
lithium tri-tert-butoxy-aluminum hydride and Nomenclature
diisobutylaluminum hydride (DIBAL-H):
SYNTHESIS
Reactions
NITRILES
Structure
- General reactions:
Properties
Nomenclature
SYNTHESIS
Reactions
NITRILES
Structure
Properties
1. Aldehydes from Acyl Chlorides: Nomenclature
SYNTHESIS
Reactions
Acyl Chloride Aldehyde

NITRILES
Structure
Properties
2. Aldehydes from Esters: Nomenclature
SYNTHESIS
Reactions
Ester Aldehyde
NITRILES
Structure
Properties
3. Aldehydes from Nitriles: Nomenclature
SYNTHESIS
Reactions
Nitrile Aldehyde
HYDROBORATION-OXIDATION Definition
- Is the hydration of an alkyne Structure
- See Organic Chemistry 1 PPT, under Reaction of Alkynes,
Hydroboration-Oxidation Properties
Nomenclature
SYNTHESIS
Reactions
HYDROLYSIS OF ACETALS Definition
- Happens when the acetal* is placed in water and Structure
catalytic amount of acid is added
Properties
Nomenclature
SYNTHESIS
Reactions
*acetals are further discussed in Reaction of Aldehydes and Ketones, under Addition of Alcohols
OZONOLYSIS OF ALKENES Definition
- See Organic Chemistry 1 PPT, under Reaction of Alkenes, Structure
Oxidation of Alkenes, (3) Ozonolysis
Properties
Nomenclature
SYNTHESIS
Reactions
FRIEDEL-CRAFTS ACYLATION Definition
- See Reaction of Benzenes, under Electrophilic Aromatic Structure
Substitution, (5) Friedel-Crafts Acylation
Properties
Nomenclature
SYNTHESIS
Reactions
- Alternatively:
OXIDATION FROM SECONDARY ALCOHOLS Definition
- See Reactions of Alcohols, under Oxidation to Carbonyl Structure
Compounds (all the methods there produce ketones)
Properties
Swern Oxidation: Nomenclature
SYNTHESIS
Reactions
KETONES FROM NITRILES Definition
- Treating the nitrile with either a Grignard reagent (RMgX) Structure
or an organolithium reagent (RLi) followed by hydrolysis
yields a ketone Properties
Nomenclature
SYNTHESIS
Reactions
KETONES FROM NITRILES Definition
- Specific examples: Structure
Properties
Nomenclature
SYNTHESIS
Reactions
HYDRATION OF AN ALKYNE Definition
- See Organic Chemistry 1 PPT, under Reactions of Structure
Alkynes, Hydration
Properties
General Reaction: Nomenclature
SYNTHESIS
Reactions
NUCLEOPHILIC ADDITION Definition
- Most characteristic reaction of aldehydes and ketones Structure
- Reaction to the carbon-oxygen double bond
Properties
Nomenclature
Synthesis
REACTIONS
Occurs in Two General Ways:

1. When the reagent is a strong nucleophile.
2. When an acid catalyst is present and the nucleophile is
weak.
Relative Reactivity: Structure
In general, aldehydes are more reactive in
nucleophilic additions than are ketones. Properties
Nomenclature
Two Factors (both favors aldehydes):
1. Steric Factors Synthesis
- the aldehyde is less crowded and the product is
REACTIONS
more stable
2. Electronic Factors
- aldehydes have only one electron-releasing group
to partially neutralize, and thereby stabilize while
ketones have two
1. Addition of Alcohols Structure
- Aldehydes and ketones react with alcohols to form
hemiacetals and acetals by an equilibrium reaction Properties
Nomenclature
Hemiacetal – compound that contains an –OH and –OR
group attached to the same carbon atom Synthesis
REACTIONS
Acetal – compound that has two –OR groups attached to
the same carbon atom
- General Reaction:
Properties
Nomenclature
Synthesis
R’’ may be H (aldehyde) or an alkyl group (ketone)
REACTIONS
- cyclic acetals are formed when treated with excess
1,2-diol:
- thioacetals are formed when aldehydes and ketones
react with thiols Properties
Nomenclature
Synthesis
REACTIONS
2. Addition of Ammonia and Derivatives Structure
- the table below summarizes the products of these
kind of reactions Properties
REAGENT PRODUCT Nomenclature

Primary Amine Imine
Synthesis
Secondary Amine Enamine
Hydroxylamine Oxime REACTIONS
Hydrazine Hydrazone then alkane
Phenylhydrazine Phenylhydrazone
2,4-dinitrophenylhydrazine 2,4-dinitrophenylhydrazone
a. Addition of Primary and Secondary Amines Properties

- Imines have a carbon–nitrogen double bond Nomenclature
- generally takes place fastest between pH 4 and 5
and is slow at very low or very high pH Synthesis
REACTIONS
b. Addition of Secondary Amines Properties

- Enamines have an amino group joined to a carbon– Nomenclature
carbon double bond (alkeneamines)
Synthesis
REACTIONS
c. Addition of Hydroxylamines Properties

- Compounds such as hydroxylamine (NH2OH), Nomenclature
hydrazine (NH2NH2), and substituted hydrazines such as
phenylhydrazine (C6H5NHNH2) and 2,4- Synthesis
dinitrophenylhydrazine form C=N derivatives of aldehydes
REACTIONS
and ketones
d. Addition of Phenylhydrazine and 2,4- Properties

dinitrophenylhydrazine Nomenclature
- same mechanism as imine formation
Synthesis
REACTIONS
e. Wolff-Kishner Reduction (Addition of Hydrazine) Properties

- See Reactions of Benzenes, Synthetic Applications Nomenclature
of F-C Acylation, (2) Wolff-Kishner Reduction
Synthesis
REACTIONS
3. Addition of Hydrogen Cyanide (HCN) Structure
- Hydrogen cyanide adds to the carbonyl groups of
aldehydes and most ketones (highly hindered ketones do Properties
not undergo this reaction) to form compounds called Nomenclature
cyanohydrins
Synthesis
REACTIONS
4. Addition of Ylides: The Wittig Reaction Structure
- Aldehydes and ketones react with phosphorus
ylides (phosphoranes) to yield alkenes and Properties
triphenylphosphine oxide (by-product) Nomenclature
- no ambiguity exists as to the location of the double
bond in the product Synthesis
REACTIONS
5. Addition of Grignard Reagents or Organolithium Structure
Compounds
- See Synthesis of Alcohols, under Using Grignard Properties
Reagents or Organolithium Compounds, (2) Reaction with Nomenclature
Carbonyl Compounds
Synthesis
REACTIONS
6. Reduction of Aldehydes and Ketones Structure
- See Synthesis of Alcohols, under Reduction of
Carbonyl Compounds, (2) Using Sodium Borohydride Properties
- both LAH and Sodium Borohydride can be used to Nomenclature
reduce aldehydes and ketones
Synthesis
Specific examples:
REACTIONS
7. Oxidation of Aldehydes Structure
- Aldehydes are much more easily oxidized than
ketones Properties
- Aldehydes are readily oxidized by strong oxidizing Nomenclature
agents such as potassium permanganate, and they are also
oxidized by such mild oxidizing agents as silver oxide Synthesis
REACTIONS
8. Baeyer-Villiger Oxidation Structure
- a useful method for conversion of aldehydes or
ketones to esters by the insertion of an oxygen atom from a Properties
peroxycarboxylic acid (RCO3H) Nomenclature
For example: Synthesis
REACTIONS
TOLLEN’S TEST
- Also known as the silver mirror test
- Test for aldehydes using silver nitrate with aqueous
ammonia (Tollen’s reagent) to form silver mirror metal
deposits inside the test tube T O L L E N ‘S
- Tollens’ reagent gives a negative result with all ketones
except a-hydroxy ketones
BENEDICT’S TEST
- Test for aldehydes
- A metal ion is reduced and we know that a positive test
has taken place when we see the product come out of
the solution, for aldehydes, a red precipitate (Cu2O)
BENEDICT’S
FORMALDEHYDE
- Starting material for the synthesis of many plastics and
resins
- Also sold as a 37% aqueous solution known as formalin,
which is used as disinfectant, antiseptic and preservative
for biological specimens
- Product of incomplete combustion of coal and other
fossil fuels, partly responsible for the irritation caused by
smoggy air
FORMALIN
ACETONE
- An industrial solvent and starting material in the
synthesis of some organic polymers
- Produced in vivo during breakdown of fatty acids
- Individuals with diabetes often have unusually high levels ACETONE
of acetone in their bloodstreams which is detected in the
breath of diabetic patients when their disease is poorly
controlled
- Used as nail polish remover
NAIL POLISH
REMOVING
LEMONGRASS
CINNAMON
ALMONDS
Source: Organic Chemistry by J.G. Smith BLEU CHEESE

MEADOWSWEET
LEMONS
SAFROLE
Source: Organic Chemistry by T.W.G Solomons, C.B. Frhyle, and S.A. Snyder SPEARMINT
Organic compounds that
contain the functional
group –COOH or carboxyl
group.
- Are organic compounds containing a carboxyl group,
DEFINITION
abbreviated as –CO2H or –COOH
- The word carboxyl is derived from carbonyl (C=O) and Structure
hydroxyl (-OH)
Properties
Nomenclature
Synthesis
Reactions
- Carboxylic acid derivatives: obtained by replacing the
hydroxyl group, –OH, by chlorine, carboxylate, alkoxy, and
amino group
DEFINITION
Structure
Properties
Nomenclature
Synthesis
Reactions
Source: Organic Chemistry by T.W.G Solomons, C.B. Frhyle, and S.A. Snyder
- The carbon atom of the carboxyl group is sp2 hybridized
Definition
and is trigonal planar
- The bond angles are approximately 120° STRUCTURE
- The C=O is shorter than its C-O
Properties
- C-O and O-H bonds are polar
Nomenclature
Synthesis
Reactions
- This interaction is caused by the polar carbonyl and Structure
hydroxyl groups
- They also exhibit intermolecular hydrogen bonding PROPERTIES
because of the hydrogen bonded to an electronegative
Nomenclature
oxygen atom (OH bond)
- Often exist as dimers Synthesis
- The most polar of the organic compounds we tackled so
Reactions
far
Definition
Structure
PROPERTIES
Nomenclature
Synthesis
Reactions

- CA are strong acids so they react readily with aqueous
Definition
solutions of sodium hydroxide and sodium bicarbonate
to form soluble sodium salts Structure
PROPERTIES
Factors affecting Acidity:
1. CA having electron-withdrawing groups are more acidic Nomenclature
than unsubstituted acids.
Synthesis
2. The larger the number of electronegative substituents,
the stronger the acid. Reactions
3. The more electronegative the substituent, the stronger
Definition
the acid.
Structure
PROPERTIES
Nomenclature
4. The closer the electron-withdrawing group to the COOH,
Synthesis
the stronger the acid.
Reactions
- Hydroxyl group (OH): broad peak in the 2500–3100 cm-1 Structure
- N-H bond of amides: between 3140 and 3500 cm-1
- Carboxyl group (C=O): occurs at different frequencies for PROPERTIES
acids, esters, and amides, and its precise location is often
Nomenclature
helpful in structure determination; but typical location of
C=O bond is at approx. 1710 cm-1 (See Solomons, Figure Synthesis
17.2, page 779 for exact frequencies)
Reactions
1H NMR SPECTRA Definition
- Acidic protons of CA: highly deshielded and absorb Structure
downfield between 10-12 ppm
- Protons on the alpha carbon: absorb at 2-2.5 ppm PROPERTIES
13C NMR SPECTRA Nomenclature
- Carbonyl carbon: downfield between 160-180 ppm Synthesis
- Nitrile carbon: absorbs in the 115-120 ppm region Reactions

- Lower than those of acids and alcohols of comparable Structure
molecular weight
- Are about the same as those of comparable aldehydes PROPERTIES
and ketones
Nomenclature
ODOR Synthesis
- Pleasant odor, some resembling those of fruits Reactions

BOILING POINT OF ACYL CHLORIDES AND Definition
ACID ANHYDRIDES
Structure
- In the same range as esters of comparable molecular
weight PROPERTIES
Nomenclature
BOILING POINT OF AMIDES
Synthesis
- Amides with nitrogen atoms bearing one or two
hydrogen atoms have high melting points and boiling Reactions
points
- N,N-disubstituted amides have lower melting points and
boiling points
1. If the COOH is bonded to a chain of carbons, find the Structure
longest chain containing the COOH group and change
the –e ending of the parent alkane to the suffix –oic acid. Properties
If bonded to a ring, name the ring then add the words NOMENCLATURE
carboxylic acid.
2. Number the chain or ring to put the COOH group at Synthesis
position 1, but omit this number from the name. apply all Reactions
other rules of nomenclature.
1. A common name is formed by using a common parent Structure
name followed by the suffix –ic acid. The table for this
common parent names are listed previously, under Properties
Nomenclature of Aldehydes. NOMENCLATURE
2. Greek letters are used to designate the location of
substituents in common names. The last carbon in chain Synthesis
is sometimes called the omega carbon. Reactions
CARBOXYLATE SALTS Definition
1. Named as –ates, in both common and IUPAC names. Structure
Replace the –oic acid with the suffix –oate.
2. The name of the cation precedes that of the carboxylate Properties
anion. NOMENCLATURE
Synthesis
Reactions
or sodium ethanoate
DICARBOXYLIC ACIDS Definition
1. These are compounds containing two carboxyl groups. Structure
Named as alkanedioic acids in the IUPAC system. Add to
the parent alkane the suffix –dioic acid. The IUPAC Properties
names of the examples below are those in parentheses. NOMENCLATURE
2. For common names, the tables on next slides list some
of the commonly used. Synthesis
Reactions
NO. OF CARBON ATOMS COMMON NAME
Structure
2 Oxalic acid
3 Malonic acid Properties
4 Succinic acid
NOMENCLATURE
5 Glutaric acid
6 Adipic acid Synthesis
7 Piralic acid
Reactions
8 Subaric acid
9 Azelaic acid
10 Sebacic acid
OH MY! SUCH GOOD APPLE PIE SWEET AS SUGAR

POSITION OF CARBON ATOMS COMMON NAME Structure

In chain, with double bond
Properties
-cis Maleic acid
-trans Fumaric acid NOMENCLATURE
In benzene rings
Synthesis
-ortho Phthalic acid
-meta Isophthalic acid Reactions
-para Terephthalic acid
1. The alkyl substituent is named first, followed by the
Definition
carboxylic acid, replacing the –oic acid with –oate.
Structure
Properties
NOMENCLATURE
Synthesis
Reactions
1. Named by dropping the word acid from the name of the
Definition
carboxylic acid then adding the word anhydride.
Structure
Properties
NOMENCLATURE
Synthesis
Reactions
1. Named by dropping –oic acid from the name of the acid
Definition
and then adding –oyl chloride.
Structure
Properties
NOMENCLATURE
Synthesis
Reactions
1. Amides that have no substituent on nitrogen are named
Definition
by dropping –oic acid from the common name of the
acid and then adding –amide. Structure
Properties
General Formula NOMENCLATURE
Synthesis
Reactions
Specific example
2. Alkyl groups on the nitrogen atom of amides are named
Definition
as substituents, and the named substituent is prefaced
by N- or N,N-. Structure
Properties
General
NOMENCLATURE
Formula
Synthesis
Reactions
Specific
example
1. Named by adding the suffix –nitrile to the name of the
Definition
corresponding hydrocarbon. The carbon of the carbon
with the triple bond is assigned at position 1. The Structure
common names are inside the parentheses.
Properties
NOMENCLATURE
Synthesis
Reactions
OXIDATION OF ALKENES Definition
- See Organic Chemistry 1 PPT, under Reactions of Structure
Alkenes, Oxidation of Alkenes, (2) Oxidative Cleavage
using KMnO4 and (3) Cleavage using Oxone: Ozonolysis Properties
Nomenclature
Potassium
SYNTHESIS
permanganate
Reactions
Ozonolysis
OXIDATION OF ALDEHYDES AND 1° ALCOHOLS Definition
- For aldehydes, See Reactions of Aldehydes and Ketones, Structure
under Nucleophilic Addition, (7) Oxidation of Aldehydes
Properties
Nomenclature
SYNTHESIS
- For primary alcohols, See Reactions of Alcohols, under
Oxidation to Carbonyl Compounds, (4) Using Potassium Reactions
Permanganate (KMnO4)
OXIDATION OF ALDEHYDES AND 1° ALCOHOLS Definition
- For both aldehydes and primary alcohols, See Reactions Structure
of Alcohols, Oxidation to Carbonyl Compounds, (2)
Chromic Acid (H2CrO4) Oxidation Properties
Nomenclature
SYNTHESIS
Reactions
BENZYLIC OXIDATION OF ALKYLBENZENES Definition
- Primary and secondary alkyl groups (but not 3° groups) Structure
directly attached to a benzene ring are oxidized by
KMnO4 to a -CO2H group Properties
- See Reactions of Benzene, under Reactions of the Side Nomenclature
Chain, (2) Oxidation of Alkyl Benzenes
SYNTHESIS
Reactions
OXIDATION OF BENZENE RING Definition
- The benzene ring of an alkylbenzene can be converted to Structure
a carboxyl group by ozonolysis, followed by treatment
with hydrogen peroxide Properties
- See Reactions of Benzene, under Monosubstituted Nomenclature
Benzenes, (3) Oxidation of the Benzene Ring
SYNTHESIS
Reactions
OXIDATION OF METHYL KETONES Definition
- Also called the haloform reaction (chloroform, Structure
bromoform, iodoform)
- Acyl substitution reaction occurs forming a carboxylate Properties
salt and the haloform, hydration (reaction with water) of Nomenclature
the carboxylate salt leads to carboxylic acids
SYNTHESIS
Reactions
Carboxylate
salt
HYDROLYSIS OF CYANOHYDRIN AND NITRILES Definition
- Cyanohydrins can be hydrolyzed to 𝛼 – hydroxy acids Structure
Properties
Nomenclature
- Limited to the use of primary alkyl halides
Specific examples: SYNTHESIS
Reactions
CARBONATION OF GRIGNARD REAGENTS Definition
- Grignard reagents react with carbon dioxide to yield Structure
magnesium carboxylates, then acidification produces
carboxylic acids Properties
Nomenclature
SYNTHESIS
Reactions
NEUTRALIZATION Definition
- Reaction with bases (acid-base reaction) Structure
Properties
Nomenclature
Synthesis
REACTIONS
REDUCTION
SYNTHESIS OF CARBOXYLIC ACID DERIVATIVES Definition
Mnemonics for Reactions with Carboxylic Acids Structure
- gamit na gamit ko to sa ChE and ChT Boards HAHA
Properties
AlES CANA WACAR MAMA Nomenclature
Synthesis
CA plus Alcohol CA plus Water REACTIONS

yields Ester yields CA plus
Carboxylic Amine
acid yields Amide
CA plus CA
yields Anhydride
1. Synthesis of Acyl Chlorides Structure
- acyl chlorides are the most reactive of the acid
derivatives Properties
- involve nucleophilic addition–elimination by a Nomenclature
chloride ion on a highly reactive intermediate: a protonated
acyl chlorosulfite, a protonated acyl chlorophosphite, or a Synthesis
protonated acyl chlorophosphite
REACTIONS
- the general reactions are on the next slide
1. Synthesis of Acyl Chlorides Structure
Properties
Nomenclature
Synthesis
REACTIONS
2. Synthesis of Acid Anhydrides Structure
- Carboxylic acids react with acyl chlorides in the
presence of pyridine to give carboxylic acid anhydrides Properties
Nomenclature
Synthesis
REACTIONS
- Sodium salts of carboxylic acids also react with acyl
chlorides to give anhydrides
2. Synthesis of Acid Anhydrides Structure
- Cyclic anhydrides can sometimes be prepared
simply by heating the appropriate dicarboxylic acid Properties
(appropriate only to five- or six-membered ring) Nomenclature
Synthesis
REACTIONS
3. Synthesis of Ester: Esterification Structure
- Carboxylic acids react with alcohols to form esters
through a condensation reaction known as esterification Properties
Nomenclature
Synthesis
REACTIONS
- acid-catalyzed esterifications are called Fischer

esterifications
3. Synthesis of Ester: Esterification Structure
- some specific examples of Fischer esterifications
Properties
Nomenclature
Synthesis
REACTIONS
4. Synthesis of Amides Structure
- Carboxylic acids react with aqueous ammonia to
form ammonium salts, this salt is then converted to an Properties
amide through dehydration Nomenclature
Synthesis
REACTIONS
Amide
DECARBOXYLATION Definition
- Reaction whereby a carboxylic acid loses carbon dioxide Structure
(CO2)
- Exothermic reaction and very slow Properties
Nomenclature
Synthesis
REACTIONS
- Example, decarboxylation of 𝛽- keto acids:
CONVERSION TO LESS REACTIVE CA DERIVATIVES Definition
1. Conversion to Structure
Acid
Anhydrides Properties
2. Conversion to Nomenclature
Ester
3. Conversion to Synthesis
Amide
REACTIONS
(Reaction with
1° and 2°
amines and
ammonia)
HYDROLYSIS Definition
- Reaction with water and (even more rapidly) with Structure
aqueous base
- Forms carboxylic acid or its salt Properties
Nomenclature
Synthesis
REACTIONS
CONVERSION TO KETONES Definition
- An example of Friedel-Crafts Acylation, See Reactions of Structure
Benzenes, under Electrophilic Aromatic Substitution, (5)
Friedel-Crafts Acylation Properties
Nomenclature
Synthesis
REACTIONS
CONVERSION TO ALDEHYDES Definition
- An example of Reduction, See Synthesis of Aldehydes, Structure
under Reduction of Acyl Chlorides, Esters, and Nitriles,
(1) Aldehydes from Acyl Chlorides Properties
Nomenclature
Synthesis
REACTIONS
CONVERSION TO LESS REACTIVE CA DERIVATIVES Definition
1. Conversion to Ester Structure
2. Conversion to Amide (Reaction with 1° and 2° amines)
Properties
Nomenclature
Synthesis
REACTIONS
- Forms carboxylic acid or its salt Structure
Properties
Nomenclature
Synthesis
REACTIONS
CONVERSION TO ARYL KETONES Definition
- An example of Friedel-Crafts Acylation Structure
Properties
Nomenclature
Synthesis
REACTIONS
CONVERSION TO AMIDES Definition
- Esters undergo nucleophilic addition–elimination at their Structure
acyl carbon atoms when they are treated with ammonia
(called ammonolysis) or with primary and secondary Properties
amines Nomenclature
Synthesis
REACTIONS
ACID-CATALYZED HYDROLYSIS Definition
- Reverse of acid-catalyzed esterification Structure
- Forms carboxylic acid and alcohol
Properties
Nomenclature
Synthesis
REACTIONS
BASE-PROMOTED HYDROLYSIS: SAPONIFICATION Definition
- Saponification comes from the Latin word “sapo” Structure
meaning soap
- Refluxing an ester with aqueous sodium hydroxide Properties
produces an alcohol and the sodium salt of the acid Nomenclature
Synthesis
REACTIONS
TRANSESTERIFICATION Definition
- Conversion to other esters Structure
Properties
Nomenclature
Synthesis
REACTION WITH GRIGNARD REAGENTS
REACTIONS
(2) Aldehydes from Esters Properties
Nomenclature
Synthesis
REACTIONS
- Amides undergo hydrolysis when they are heated with Structure
aqueous acid or aqueous base
Properties
Nomenclature
Synthesis
REACTIONS
- Hydrolysis of amides by enzymes is central to the

digestion of proteins
SYNTHESIS OF NITRILES: DEHYDRATION Definition
- Amides react with P4O10 (a compound that is often called Structure
phosphorus pentoxide and written P2O5) or with boiling
acetic anhydride to form nitriles Properties
Nomenclature
Synthesis
REACTIONS
- Nitriles are related to carboxylic acids because complete Structure
hydrolysis of a nitrile produces a carboxylic acid or a
carboxylate anion Properties
Nomenclature
Synthesis
REACTIONS
(2) Aldehydes from Nitriles Properties
Nomenclature
Synthesis
REACTION WITH GRIGNARD OR ORGANOLITHIUM REACTIONS
- Conversion to ketones
FORMIC ACID
- Has an acrid odor and a biting taste
- Responsible for the sting of some type of ants
- From Latin word “formica” meaning ant
ANTS
ACETIC ACID
- The sour-tasting component of vinegar
- Comes from the Latin word “acetum” meaning vinegar
- An industrial starting material for polymers used in paints
and adhesives
- Pure acetic acid is called glacial acetic acid, because it
freezes below room temperature (MP is 17°C) forming
white crystals that resembles ice in a glacier
VINEGAR
BUTANOIC ACID
- Oxidation product that contributes to the disagreeable
smell of body odor
- Derived from the Latin word “butyrum” meaning butter
- Gives the rancid butter its peculiar odor and taste BUTTER
CAPROIC ACID
- Common name for hexanoic acid
- Foul odor associated with dirty socks and locker rooms
- From the Latin word “caper” meaning goat
- Contributes to the unpleasant odor of Gingkgo seeds
GINGKGO
OXALIC ACID
- Occurs naturally in spinach and rhubarb
- Although toxic, you need to eat about nine pounds of
spinach at one time to ingest a fatal dose
SPINACH
LACTIC ACID
- Gives sour milk its distinctive taste
- Formed during the metabolism of glucose to carbon
dioxide and water
- During exercise, lactic acid forms resulting in the aching
feeling of tired muscles
MILK
Organic derivatives of
ammonia with alkyl or aryl
substituents.
- Are organic nitrogen compounds, formed by replacing
DEFINITION
one or more hydrogen atoms of ammonia with alkyl
groups Structure
Properties
Nomenclature
CLASSIFICATIONS Synthesis
1. Primary Amine (1°)
Reactions
2. Secondary Amine (2°)
3. Tertiary Amine (3°)
- classification is based on the number of organic

groups that are attached to the nitrogen atom
- The N atom is sp3 hybridized with the unshared electron
Definition
pair occupying one orbital and is trigonal pyramidal in
shape STRUCTURE
- Bond angles are approximately 108.7°
Properties
- The C-N and N-H bonds are all polar, with the N atom
electron rich and C and H atoms electron poor Nomenclature
Synthesis
Reactions
- This interaction is caused by the polar C-N and N-H Structure
bonds
- Primary and secondary amines are capable of PROPERTIES
intermolecular hydrogen bonding because of the N-H
Nomenclature
bonds
- Tertiary amines cannot form hydrogen bonds to each Synthesis
other, but they can form hydrogen bonds to molecules of
Reactions
water or other hydroxylic solvents
- Moderately polar substances
Definition
Structure
PROPERTIES
Nomenclature
Synthesis
Reactions

- Primary amines: two NH absorptions at 3300-3500 cm-1 Structure
- Secondary amines: one NH absorption at 3300-3500 cm-1
PROPERTIES
1H AND 13C NMR SPECTRA Nomenclature
- NH signal: between 0.5 to 5.0 ppm Synthesis
- Protons on carbon bonded to amine nitrogen: 2.3-3.0 Reactions

ppm
- 13C NMR, carbon bonded to N: 30-50 ppm
PRIMARY AMINES Definition
1. For IUPAC system: Find the longest continuous chain Structure
bonded to the amine nitrogen and change the –e ending
of the parent alkane to the suffix –amine. Then apply the Properties
usual rules of nomenclature. (Names written in blue) NOMENCLATURE
2. For common name: named as alkylamines.
Synthesis
Reactions
SECONDARY AND TERTIARY AMINES Definition
Most secondary and tertiary amines are named in the Structure
same general way.
1. For common name: Designate the organic groups Properties
individually if they are different or use the prefixes di- or NOMENCLATURE
tri- if they are the same.
2. For IUPAC system for amines with more than one kind of Synthesis
alkyl group: Designate the longest alkyl chain bonded to Reactions
the N as the parent amine and the other groups as alkyl
substituents. Use N to designate substituents. (Names
written in blue)
SECONDARY AND TERTIARY AMINES Definition
Examples: Structure
Properties
NOMENCLATURE
Synthesis
Reactions
NH2 AS SUBSTITUENT Definition
1. The –NH2 group is called the amino group. This system is Structure
often used for naming amines containing an –OH group
or a -CO2H group. Properties
NOMENCLATURE
Synthesis
Reactions
ARYL AMINES Definition
1. Named as derivatives of aniline. Structure
Properties
NOMENCLATURE
Synthesis
Reactions
HETEROCYCLIC AMINES Definition
1. For common names: may tawag sa kanila na default. Structure
2. For IUPAC system: The prefixes aza-, diaza-, and triaza-
are used to indicate that nitrogen atoms have replaced Properties
carbon atoms in the corresponding hydrocarbon. The NOMENCLATURE
nitrogen atom is designated at position 1.
Synthesis
The examples are on the next slide. The IUPAC names are Reactions
written in blue.
HETEROCYCLIC AMINES
Definition
Structure
Properties
NOMENCLATURE
Synthesis
Reactions
NUCLEOPHILIC SUBSTITUTION REACTIONS Definition
1. Alkylation of Ammonia Structure
- Subsequent treatment of the resulting aminium
salts with a base gives primary amines Properties
- multiple alkylations occur, but can be minimized by Nomenclature
using large excess of ammonia
SYNTHESIS
Reactions
2. Alkylation of Azide Ion and Reduction Structure
- first is conversion of the alkyl halide to an alkyl
azide (R-N3) by a nucleophilic substitution reaction, then Properties
reduction of the azide to a primary amine with lithium Nomenclature
aluminum hydride (LAH)
SYNTHESIS
Reactions
3. Gabriel Synthesis Structure
- avoids the complications of multiple alkylations that
occur when alkyl halides are treated with ammonia Properties
Nomenclature
SYNTHESIS
Reactions
Continuation
of reaction
4. Alkylation of Tertiary Amines Structure
- here, multiple alkylations is not a problem
Properties
Nomenclature
SYNTHESIS
Reactions
REDUCTION OF NITRO COMPOUNDS Definition
- involves nitration of the ring and subsequent reduction of Structure
the nitro group to an amino group
Properties
Nomenclature
SYNTHESIS
Reactions
REDUCTIVE AMINATION Definition
- Aldehydes and ketones can be converted to amines Structure
through catalytic or chemical reduction in the presence
of ammonia or an amine Properties
Nomenclature
SYNTHESIS
Reactions
REDUCTION OF NITRILES, OXIMES AND AMIDES Definition
- Reduction of a nitrile or an oxime yields a primary amine Structure
while reduction of an amide can yield a primary,
secondary, or tertiary amine Properties
Nomenclature
SYNTHESIS
Reactions
HOFMANN AND CURTIUS REARRANGEMENTS Definition
Structure
Properties
Nomenclature
SYNTHESIS
Reactions
ACID-BASE REACTIONS Definition
Structure
Properties
Nomenclature
ALKYLATION AND ACYLATION
Synthesis
REACTIONS
REPLACEMENT REACTIONS Definition
- Diazotization of 1° arylamines and replacement of, or Structure
coupling with, the diazonium group
Properties
Nomenclature
Synthesis
REACTIONS
CONVERSION TO SULFONAMIDES Definition
- Primary and secondary amines react with sulfonyl Structure
chlorides to form sulfonamides
Properties
Nomenclature
Synthesis
REACTIONS
CONVERSION TO AMIDES Definition
- See Reactions of Acyl Chlorides, under Conversion to Structure
Less Reactive CA Derivatives, (3) Conversion to Amides
Properties
Nomenclature
Synthesis
REACTIONS
HOFFMAN AND COPE ELIMINATIONS Definition
Structure
Properties
Nomenclature
Synthesis
REACTIONS
TRIMETHYLAMINE
- Formed when enzymes break down certain fish proteins
- Has the characteristic odor of rotting fish
PUTRESCINE AND CADAVERINE ROTTING FISH
- Are poisonous diamines with putrid odors

- Present in rotting fish and decaying meat, also partly
responsible for odors of semen, urine and bad breath
ROTTING MEAT
HISTAMINE
- Simple triamine responsible for a wide variety of
physiological effects
- Is a vasodilator, it dilates capillaries, so it is released at
the site of an injury or infection to increase blood flow
- Responsible for the symptoms of allergies, including
runny nose and watery eyes
- In stomach: stimulates secretion of acid
ANTIHISTAMINE
- Bind to he same active site of the enzyme that binds
histamine in the cell but invoke a different response:
a. Brompheniramine – inhibits vasodilation, used to
treat symptoms of common colds and allergies
b. Cimetidine – blocks the secretion of hydrochloric acid
in the stomach, used to treat patients with ulcers
DERIVATIVES OF 2-PHENYLETHYLAMINE
- Synthesized in cells to maintain healthy mental function
- Examples:
DERIVATIVES OF 2-PHENYLETHYLAMINE
- Another example is the dopamine, it is a
neurotransmitter which affects brain processes that
control movement and emotions
- Proper dopamine levels are necessary to maintain an
individual’s mental and physical health
- If dopamine level drops, it may result to Parkinson’s
disease (loss of motor control)
ALKALOIDS
- Derived from plant sources
1. Atropine
- from nightshade plant NIGHTSHADE
- can increase heart rate, relax smooth muscles,
interferes with nerve impulses transmitted by
acetylcholine
- poisonous at higher dosage
2. Quinine
- isolated from the bark of the Cinchona tree
- effective antimalarial drug that reduces fever
CINCHONA TREE
ALKALOIDS
3. Nicotine
- an addictive and highly toxic compound isolated
from tobacco plant
- in small doses: stimulant; in large doses: can cause TOBACCO
depression, nausea and death
- commercially used as insecticide
4. Coniine
- poisonous alkaloid from the seeds, leaves and roots
of hemlock
- ingestion can cause weakness, paralysis and death
- Socrates was executed by being forced to drink a
potion prepared from hemlock (339 BC)
HEMLOCK
Olaño, S.S.B., et. al. (2012).
Reviewer
Engineering
for Chemical
Licensure
S
Examination, 3rd ed. Manila.
Manila Review Institute, Inc.
O
Smith, J.G. (2008). Organic U
R
Chemistry, 2nd ed. New York.
The McGraw-Hill Companies,
Inc.
Solomons, T.W.G., Fryhle, C.B., &

C
Snyder, S.A. (2014). Organic
Chemistry, 11th ed. United
E
States of America. John
Wiley & Sons, Inc. S

Organic Chemistry 2

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Organic Chemistry 2

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Engr. Quennie Marie L.

- Consist of two equivalent Lewis structures Synthesis

- Explains why all C-C bond lengths are the

- The six adjacent p orbitals overlap, delocalizing the six Aromaticity

Low H to C ratio Six-carbon unit (Kekulé) Structure

Source: Organic Chemistry by Smith, J.G.

We would now expect that hydrogenation of 1,3-

the conjugated compounds. Reactions

Some Uses of Benzene Reactions

BENZENE DYES DRUGS

To desulfonate (remove sulfonic acid group): use dilute

R represents alkyl groups

1. Rearrangements can occur. Properties

R represents alkyl groups

In theory, Inductive effect: Properties

Summary of Examples of the Two Classes are on the next

Activated benzenes – benzene rings activated by strong Properties

These benzenes undergo: Synthesis

R represents alkyl groups

Multiple substitutions occur with an excess of

*NBS is N-bromosuccinimide, often used because it provides a

Radical condition - with the use of X2 and light or heat, REACTIONS

X represents halides (F, Cl, Br, I)

For example, Benzene, an aromatic compound: AROMATICITY

Source: Organic Chemistry by Smith, J.G.

3. Benzo(a)pyrene - formed by the incomplete

*definition on page 75 CIGARETTE

[16]annulene, [24]annulene, [12]annulene

Heterocycles - rings that contain at least one

1990 - W. Krätschmer, D. Huffman and co-workers

Fullerenes - cage-like molecules with the geometry of a

C60 - have 12 pentagons and 20 hexagons

2. Secondary Alcohol (2°) Nomenclature

- classification is based on the number of carbon Reactions

a C-C double bond Properties

directly to a benzene ring

Alcohol Ether Epoxide

Source: Organic Chemistry by Smith, J.G.

For example, Synthesis

1. By replacement nomenclature Properties

3. As derivatives of oxirane Properties

4. As alkene oxides Properties

Alkene Water Alcohol

Ac represents acetate ion

- Reduction: usually corresponds to increasing its

Et2O is anhydrous diethyl ether which is used as solvent

*Grignard Reagent is discussed previously on the first PPT (Synthesis of Alkanes)

CARBONYL COMPOUND PRODUCT SYNTHESIS

Ketone Tertiary Alcohol

2. Attempts to make ethers with tertiary alkyl groups lead SYNTHESIS

3. Intermolecular dehydration is not useful for the

Solvomercuration-demercuration - When the alcohol

Order of Reactivity of Hydrogen Halides:

Secondary Ketone REACTIONS

DMSO is dimethyl sulfoxide

Source: Organic Chemistry by Smith, J.G.

- 13C NMR: 190-215 ppm region Reactions

1. Aldehydes from Acyl Chlorides: Nomenclature

Acyl Chloride Aldehyde

2. Aldehydes from Esters: Nomenclature

3. Aldehydes from Nitriles: Nomenclature

Occurs in Two General Ways:

REAGENT PRODUCT Nomenclature

a. Addition of Primary and Secondary Amines Properties