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ORGANIC CHEMISTRRY

Organic chemistry deals with the study of Carbon, Carbon compounds and its derivatives.

Chemical Formulas in Organic Chemistry

1. Empirical formulashows the type of atoms and their molecular ratio in a molecule.
Ex. Methane: contains Carbon and Hydrogen atoms in a ratio of 1:4; Ethane
contains Carbon and Hydrogen in a ratio of 1:3
2. Molecular formula - tells the actual number of atoms in a molecule not simply the ratio.
Ex. Ethane CH 3 CH3
` 3. Structural formula shows the structure of a molecule.

Ethane H H
H- C - C - H
H H

Evaluation: Show the empirical, molecular and structural formulas of the following:
1.Propane, 2. Ethene, 3. Butane, 4. Pentane, 5. Hexene,
6. Octane, 7. Heptane, 8. Nonane, 9. Decane, 10. Butyne

Acids and Bases

1. Acid (according to Bronsted-Lowry concept) an acid is a substance that can donate a
positively
charged Hydrogen ion or proton (H//+ ) . Ex. HCl and HNO3

2. Base a substance that can accept H+ Ex. OH- and NH3

Strong and Weak Acids and Bases

Strong acid undergoes complete ionization in water. Strong base contains OH, OCH3
Ex. HCl, HNO3 and H2 SO4

Weak acid partially ionized in water. Weak base - NH3 and CH 3 NH3
Ex. Carbonic acid : and Carboxylic acid

Hydrocarbons

Hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons

from which one hydrogen atom has been removed are functional groups, called hydrocarbyls.
Aromatic hydrocarbons (arenes), alkanes,alkenes, cycloalkanes and alkyne-based compounds
are different types of hydrocarbons.
The majority of hydrocarbons found on Earth naturally occur in crude oil, where decomposed
organic matter provides an abundance of carbon and hydrogen which, when bonded, can catenate to form
seemingly limitless chains.

Types of Hydrocarbons

The classifications for hydrocarbons, defined by IUPAC (International Union of Pure and Applied
Chemistry) nomenclature of organic chemistry are as follows:
1. Saturated hydrocarbons (alkanes) are the simplest of the hydrocarbon species. They are
composed
entirely of single bonds and are saturated with hydrogen. The general formula for saturated hydrocarbons
is CnH2n+2 (assuming non-cyclic structures). Saturated hydrocarbons are the basis of petroleum fuels and
are found as either linear or branched species. Substitution reaction is their characteristics property (like
chlorination reaction to form chloroform). Hydrocarbons with the same molecular formula but
different structural formulae are called structural isomers..
2. Unsaturated hydrocarbons have one or more double or triple bonds between carbon atoms.
Those with
double bond are called alkenes. Those with one double bond have the formula CnH2n (assuming non-
cyclic structures). Those containing triple bonds are called alkynes, with general formula CnH2n2]
3. Cycloalkanes are hydrocarbons containing one or more carbon rings to which hydrogen atoms
are attached.
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The general formula for a saturated hydrocarbon containing one ring is CnH2n.
4. Aromatic hydrocarbons, also known as arenes, are hydrocarbons that have at least one aromatic
ring.

Hydrocarbons can be gases (e.g. methane and propane), liquids (e.g. hexane and benzene), waxes or
low melting solids (e.g. paraffin wax and naphthalene)
or polymers (e.g.polyethylene, polypropylene and polystyrene).

General properties
Because of differences in molecular structure, the empirical formula remains different between
hydrocarbons; in linear, or "straight-run" alkanes, alkenes and alkynes, the amount of bonded hydrogen
lessens in alkenes and alkynes due to the "self-bonding" or catenation of carbon preventing entire
saturation of the hydrocarbon by the formation of double or triple bonds.
This inherent ability of hydrocarbons to bond to themselves is known as catenation, and allows
hydrocarbons to form more complex molecules, such as cyclohexane, and in rarer cases, arenes such
as benzene. This ability comes from the fact that the bond character between carbon atoms is entirely non-
polar, in that the distribution of electrons between the two elements is somewhat even due to the same
electronegativity values of the elements (~0.30), and does not result in the formation of an electrophile.
Generally, with catenation comes the loss of the total amount of bonded hydrocarbons and an
increase in the amount of energy required for bond cleavage due to strain exerted upon the molecule;in
molecules such as cyclohexane, this is referred to as ring strain, and occurs due to the "destabilized"
spatial electron configuration of the atom.
In simple chemistry, as per valence bond theory, the carbon atom must follow the "4-hydrogen
rule", which states that the maximum number of atoms available to bond with carbon is equal to the
number of electrons that are attracted into the outer shell of carbon. In terms of shells, carbon consists of
an incomplete outer shell, which comprises 4 electrons, and thus has 4 electrons available for covalent
or dative bonding.
Hydrocarbons are hydrophobic like lipids.
Some hydrocarbons also are abundant in the solar system. Lakes of liquid methane and ethane
have been found on Titan, Saturn's largest moon, confirmed by the Cassini-Huygens
Mission.[11] Hydrocarbons are also abundant in nebulae forming polycyclic aromatic hydrocarbon (PAH)
compounds.
Simple hydrocarbons and their variations
Number of Alkane
Alkene (double Alkyne (triple
carbon (single Cycloalkane Alkadiene
bond) bond)
atoms bond)
1 Methane - - - -
2 Ethane Ethene (ethylene) Ethyne (acetylene)
Propene (propylene Propyne
3 Propane Cyclopropane Propadiene (allene)
) (methylacetylene)
4 Butane Butene (butylene) Butyne Cyclobutane Butadiene
Pentadiene
5 Pentane Pentene Pentyne Cyclopentane
(piperylene)
6 Hexane Hexene Hexyne Cyclohexane Hexadiene
7 Heptane Heptene Heptyne Cycloheptane Heptadiene
8 Octane Octene Octyne Cyclooctane Octadiene
9 Nonane Nonene Nonyne Cyclononane Nonadiene
10 Decane Decene Decyne Cyclodecane Decadiene

Usage

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Oil refineries are one way hydrocarbons are processed for use. Crude oil is processed in several
stages to form desired hydrocarbons, used as fuel and in other products.
Hydrocarbons are a primary energy source for current civilizations. The predominant use of
hydrocarbons is as a combustible fuel source. In their solid form, hydrocarbons take the form of asphalt
(bitumen).
Mixtures of volatile hydrocarbons are now used in preference to the chlorofluorocarbons as
a propellant for aerosol sprays, due to chlorofluorocarbons' impact on the ozone layer.
Methane (CH4) and ethane (C2H6) are gaseous at ambient temperatures and cannot be readily
liquefied by pressure alone. Propane (C3H8) is however easily liquefied, and exists in 'propane bottles'
mostly as a liquid. Butane (C4H10) is so easily liquefied that it provides a safe, volatile fuel for small
pocket lighters. Pentane (C5H12) is a clear liquid at room temperature, commonly used in chemistry and
industry as a powerful nearly odorless solvent of waxes and high molecular weight organic compounds,
including greases. Hexane (C6H14) is also a widely used non-polar, non-aromatic solvent, as well as a
significant fraction of common gasoline. The C6 through C10 alkanes, alkenes and isomeric cycloalkanes
are the top components of gasoline, naphtha, jet fuel and specialized industrial solvent mixtures. With the
progressive addition of carbon units, the simple non-ring structured hydrocarbons have higher viscosities,
lubricating indices, boiling points, solidification temperatures, and deeper color

Poisoning
Hydrocarbon poisoning such as that of benzene and petroleum usually occurs accidentally by
inhalation or ingestion of these cytotoxic chemical compounds. Intravenous or subcutaneous injection of
petroleum compounds with intent of suicide or abuse is an extraordinary event that can result in local
damage or systemic toxicity such as tissue necrosis, abscess formation, respiratory system failure and
partial damage to the kidneys, the brain and the nervous system.

Reactions

There are three main types of reactions:

1. Substitution reaction, 2. Addition reaction 3. Combustion

Substitution reactions

Substitution reactions only occur in saturated hydrocarbons (single carboncarbon bonds). In this
reaction, an alkane reacts with a chlorine molecule. One of the chlorine atoms displace an hydrogen atom.

This forms hydrochloric acid as well as the hydrocarbon with one chlorine atom.
CH4 + Cl2 CH3Cl + HCl
CH3Cl + Cl2 CH2Cl2 + HCl . . . all the way to CCl4 (carbon tetrachloride)
C2H6 + Cl2 C2H5Cl + HCl
C2H4Cl2 + Cl2 C2H4Cl3 + HCl . . . all the way to C2Cl6 (hexachloroethane)

Addition reactions

Addition reactions involve alkenes and alkynes. In this reaction a halogen molecule breaks the
double or triple bond in the hydrocarbon and forms a bond.

Combustion
Hydrocarbons are currently the main source of the world's electric energy and heat sources (such
as home heating) because of the energy produced when burnt.
Common properties of hydrocarbons are the facts that they produce steam, carbon dioxide and
heat during combustion and that oxygen is required for combustion to take place. The simplest
hydrocarbon, methane, burns as follows:
CH4 + 2 O2 2 H2O + CO2 + energy
In inadequate supply of air, carbon monoxide gas
and water vapour are formed:
2 CH4 + 3 O2 2 CO + 4 H2O
Another example of this reaction is propane:
C3H8 + 5 O2 4 H2O + 3 CO2 + energy
CnH2n+2 + 3n + 1/2 O2 (n + 1) H2O
+ n CO2 + energy
Burning of hydrocarbons is an example of
an exothermic chemical reaction.
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Hydrocarbons can also be burned with elemental fluorine, resulting in carbon

tetrafluoride and hydrogen fluoride products.
Petroleum
Natural oil spring in Kora, Slovakia. Extracted hydrocarbons in a liquid form are referred to
as petroleum (literally "rock oil") or mineral oil, whereas hydrocarbons in a gaseous form are referred to
as natural gas. Petroleum and natural gas are found in the Earth's subsurface with the tools of petroleum
geology and are a significant source of fuel and raw materials for the production of organic chemicals.
The extraction of liquid hydrocarbon fuel from sedimentary basins is integral to modern energy
development. Hydrocarbons are mined from oil sands and oil shale, and potentially extracted from
sedimentary methane hydrates. These reserves require distillation and upgrading to produce synthetic
crude and petroleum.
Economically important hydrocarbons include fossil fuels such as coal, petroleum and natural gas,
and its derivatives such asplastics, paraffin, waxes, solvents and oils. Hydrocarbons along
with NOx and sunlight contribute to the formation oftropospheric ozone and greenhouse gases.

Safety
Many hydrocarbons are highly flammable, therefore, care should be taken to prevent injury.
Benzene and many aromatic compounds are possible carcinogens, and proper safety equipment must be
worn to prevent these harmful compounds from entering the body. If hydrocarbons undergo combustion
in tight areas, toxic carbon monoxide can form. Hydrocarbons should be kept away from fluorine
compounds due to the high probability of forming toxic hydrofluoric acid.

NOMENCLATURE
Naming Organic Compounds

The increasingly large number of organic compounds identified with each passing day, together
with the fact that many of these compounds are isomers of other compounds, requires that a systematic
nomenclature system be developed. Just as each distinct compound has a unique molecular structure
which can be designated by a structural formula, each compound must be given a characteristic and
unique name.

As organic chemistry grew and developed, many compounds were given trivial names, which are
now commonly used and recognized. Some examples are:
Name Methane Butane Acetone Toluene Acetylene Ethyl Alcohol

Formula CH4 C4H10 CH3COCH3 CH3C6H5 C2H2 C2H5OH

Such common names often have their origin in the history of the science and the natural sources
of specific compounds, but the relationship of these names to each other is arbitrary, and no rational or
systematic principles underly their assignments.

The IUPAC Systematic Approach to Nomenclature

A rational nomenclature system should do at least two things. First, it should indicate how the
carbon atoms of a given compound are bonded together in a characteristic lattice of chains and rings.
Second, it should identify and locate any functional groups present in the compound. Since hydrogen is
such a common component of organic compounds, its amount and locations can be assumed from the
tetravalency of carbon, and need not be specified in most cases.
The IUPAC nomenclature system is a set of logical rules devised and used by organic chemists to
circumvent problems caused by arbitrary nomenclature.. An IUPAC name, one should be able to write a
structural formula. In general, an IUPAC name will have three essential features:
A root or base indicating a major chain or ring of carbon atoms found in the molecular
structure.
A suffix or other element(s) designating functional groups that may be present in the
compound.
Names of substituent groups, other than hydrogen, that complete
the molecular structure.

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Alkanes
Alkanes
Hydrocarbons having no double or triple bond functional groups are classified
as alkanes or cycloalkanes, depending on whether the carbon atoms of the molecule are arranged only in
chains or also in rings. The alkanes and cycloalkanes are also members of a larger class of compounds
referred to as aliphatic. Simply put, aliphatic compounds are compounds that do not incorporate
any aromatic rings in their molecular structure. A common "ane" suffix identifies these compounds as
alkanes.
Examples of Simple Unbranched Alkanes
Molecular Structural Molecular Structural
Name Isomers Name Isomers
Formula Formula Formula Formula
methane CH4 CH4 1 Hexane C6H14 CH3(CH2)4CH3 5

ethane C2H6 CH3CH3 1 Heptanes C7H16 CH3(CH2)5CH3 9

propane C3H8 CH3CH2CH3 1 Octane C8H18 CH3(CH2)6CH3 18
butane C4H10 CH3CH2CH2CH3 2 Nonane C9H20 CH3(CH2)7CH3 35
pentane C5H12 CH3(CH2)3CH3 3 Decane C10H22 CH3(CH2)8CH3 75
Halogen substituents are easily accommodated, using the names: fluoro (F-), chloro (Cl-),
bromo (Br-) and iodo (I-). For example, (CH3)2CHCH2CH2Br would be named 1-bromo-3-methylbutane.
If the halogen is bonded to a simple alkyl group an alternative "alkyl halide" name may be used. Thus,
C2H5Cl may be named chloroethane (no locator number is needed for a two carbon chain) or ethyl
chloride. Halogenated alkyl substituents such as bromomethyl, BrCH2, and trichloromethyl, CCl3, may
be listed and are alphabetized according to their full names.
Cycloalkanes
Cycloalkanes
Cycloalkanes have one or more rings of carbon atoms. The simplest examples of this class consist of
a single, unsubstituted carbon ring, and these form a homologous series similar to the unbranched alkanes.
The IUPAC names of the first five members of this series are given in the following table. The last
(yellow shaded) column gives the general formula for a cycloalkane of any size. If a simple unbranched
alkane is converted to a cycloalkane two hydrogen atoms, one from each end of the chain, must be lost.
Hence the general formula for a cycloalkane composed of n carbons is CnH2n. Although a cycloalkane
has two fewer hydrogens than the equivalent alkane, each carbon is bonded to four other atoms so such
compounds are still considered to be saturated with hydrogen.
Examples of Simple Cycloalkanes

Name Cyclopropane Cyclobutane Cyclopentane Cyclohexane Cycloheptane Cycloalkane

Molecular
C3H6 C4H8 C5H10 C6H12 C7H14 CnH2n
Formula

Structural
(CH2)n
Formula

Alkenes & Alkynes

Alkenes and Alkynes
Alkenes and alkynes are hydrocarbons which respectively have carbon-carbon double
bond and carbon-carbon triple bond functional groups. The molecular formulas of
these unsaturated hydrocarbons reflect the multiple bonding of the functional groups:
Alkane RCH2CH2R CnH2n+2 This is the maximum H/C ratio for a given number of carbon atoms.

Alkene RCH=CHR CnH2n Each double bond reduces the number of hydrogen atoms by 2.

Alkyne RCCR CnH2n-2 Each triple bond reduces the number of hydrogen atoms by 4.
As noted earlier in the Analysis of Molecular Formulas section, the molecular formula of a
hydrocarbon provides information about the possible structural types it may represent. For example,

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consider compounds having the formula C5H8. The formula of the five-carbon alkane pentane is C5H12 so
the difference in hydrogen content is 4. This difference suggests such compounds may have a triple bond,
two double bonds, a ring plus a double bond, or two rings. Some examples are shown here, and there are
at least fourteen others!

Benzene Derivatives
Benzene Derivatives
The nomenclature of substituted benzene ring compounds is less systematic than that of the
alkanes, alkenes and alkynes. A few mono-substituted compounds are named by using a group name as a
prefix to "benzene", as shown by the combined names listed below. A majority of these compounds,
however, are referred to by singular names that are unique. There is no simple alternative to memorization
in mastering these names.
Two commonly encountered substituent groups that incorporate a benzene ring are phenyl, abbreviated
Ph-, and benzyl, abbreviated Bn-. These are shown here with examples of their use. Be careful not to
confuse a phenyl (pronounced fenyl) group with the compound phenol (pronounced feenol). A general
and useful generic notation that complements the use of R- for an alkyl group is Ar- for an aryl group
(any aromatic ring).

When more than one substituent is present on a benzene ring, the relative locations of the
substituents must be designated by numbering the ring carbons or by some other notation. In the case of
disubstituted benzenes, the prefixes ortho, meta & para are commonly used to indicate a 1,2- or 1,3- or
1,4- relationship respectively. In the following examples, the first row of compounds show this usage in
red. Some disubstitutedtoluenes have singular names (e.g. xylene, cresol & toluidine) and their isomers
are normally designated by the ortho, meta or para prefix. A few disubstituted benzenes have singular
names given to specific isomers (e.g. salicylic acid & resorcinol). Finally, if there are three or more
substituent groups, the ring is numbered in such a way as to assign the substituents the lowest possible
numbers, as illustrated by the last row of examples. The substituents are listed alphabetically in the final
name. If the substitution is symmetrical (third example from the left) the numbering corresponds to the
alphabetical order.

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REACTIONS
Organic reactions are chemical reactions involving organic compounds. The basic organic
chemistry reaction types are addition reactions, elimination reactions, substitution reactions, pericyclic
reactions, rearrangement reactions, photochemical reactions and redox reactions. In organic synthesis,
organic reactions are used in the construction of new organic molecules. The production of many man-
made chemicals such as drugs, plastics, food additives, fabrics depend on organic reactions.

The oldest organic reactions are combustion of organic fuels and saponification of fats to make
soap. Modernorganic chemistry starts with the Whler synthesis in 1828. In the history of the Nobel Prize
in Chemistry awards have been given for the invention of specific organic reactions such as the Grignard
reaction in 1912, the Diels-Alder reaction in 1950, the Wittig reaction in 1979 and olefin metathesis in
2005.

Classifications
Organic chemistry has a strong tradition of naming a specific reaction to its inventor or inventors
and a long list of so-called named reactions exists, conservatively estimated at 1000. A very old named
reaction is the Claisen rearrangement (1912) and a recent named reaction is the Bingel reaction (1993).
When the named reaction is difficult to pronounce or very long as in the Corey-House-Posner-Whitesides
reaction it helps to use the abbreviation as in the CBS reduction. The number of reactions hinting at the
actual process taking place is much smaller, for example the ene reaction or aldol reaction.
Another approach to organic reactions is by type of organic reagent, many of them inorganic,
required in a specific transformation. The major types are oxidizing agents such asosmium
tetroxide, reducing agents such as Lithium aluminium hydride, bases such as lithium
diisopropylamide and acids such as sulfuric acid.

Organic reactions by functional groups

Organic reactions can be categorized based on the type of functional group involved in the
reaction as a reactant and the functional group that is formed as a result of this reaction. For example in
the Fries rearrangement the reactant is an ester and the reaction product an alcohol.
An overview of functional groups with their preparation and reactivity is presented below:

Functional group Preparation Reactions

Acid anhydride preparation reactions
Acyl halides preparation reactions
Acyloins preparation reactions
Alcohols preparation reactions
Aldehydes preparation reactions
Alkanes preparation reactions
Alkenes preparation reactions
Alkyl halides preparation reactions
Alkyl nitrites preparation reactions
Alkynes preparation reactions
Amides preparation reactions
Amine oxide preparation reactions
Amines preparation reactions
Carboxylic acids preparation reactions
Other organic reaction classification
In heterocyclic chemistry, organic reactions are classified by the type of heterocycle formed with
respect to ring-size and type of heteroatom. See for instance the chemistry ofindoles. Reactions are also
categorized by the change in the carbon framework. Examples are ring expansion and ring
contraction, homologation reactions, polymerization reactions, insertion reactions, ring-opening
reactions and ring-closing reactions.
Organic reactions can also be classified by the type of bond to carbon with respect to the element
involved. More reactions are found in organosilicon chemistry, organosulfur
chemistry, organophosphorus chemistry and organofluorine chemistry. With the introduction of carbon-
metal bonds the field crosses over to organometallic chemistry.

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CH He
CLi CBe CB CC CN CO CF Ne
CN CM CA CC CA
CSi CP CS
a g l l r
CS CM CC CZ CG CG CS CB CK
CK CCa CTi CV CCr CFe CCo CNi CAs
c n u n a e e r r
CR CZ CN CM CR CA CC CS CT CX
CSr CY CTc CRh CPd CIn CSb CI
b r b o u g d n e e
CC CH CT CO CA CH CP CP CA
CBa CW CRe CIr CPt CTl CBi Rn
s f a s u g b o t
Uu Uu
Fr CRa Rf Db CSg Bh Hs Mt Ds Rg Cn Uut Fl Uup Lv
s o

CL CC CN CP CS CG CT CD CH CE CT CY CL
CPr CEu
a e d m m d b y o r m b u
CT CP CN CA CC CB CC CE
Ac CU CPu Fm Md No Lr
h a p m m k f s

Carboxylic acid Derivatives

Carboxylic derivatives are described as compounds that can be converted to carboxylic acids via
simple acidic or basic hydrolysis.

The most important acid derivatives are esters, amides and nitriles, although acid halides and
anhydrides are also derivatives (really activated forms of a carboxylic acid).

Esters of Carboxylic Acids

These are derivatives of carboxylic acids where the hydroxyl group is replaced by an alkoxy group.

Amides of Carboxylic Acids

An amide is a composite of a carboxylic acid and an amine (or ammonia).
Heating the salt formed when an amine and carboxylic acid react together, drives off the water
produced, and an amide is formed.

Nomenclature of Amides
To name a primary amide, identify the acid part and remove the -oic acid suffix and add -amide
E.g.

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Nitriles of Carboxylic Acids

Nitriles contain the cyano group, and although they lack the carbonyl group that the other
carboxylic acid derivatives have, they are still classified as carboxylic acid derivatives since they
are hydrolyzed to carboxylic acids, and also can be produced by dehydration of primary amides.
E.g.

Both the carbon and nitrogen atoms of a nitrile are sp hybridized, and the bond angle is 180.

The structure of a nitrile is similar to an alkyne, except the nitrogen has a lone pair of electrons
instead of a bond to hydrogen.

Since the lone pair on N is contained in an sp orbital, they are tightly held, and are therefore not
very basic.
Normal nitriles have pKb ~ 24.

Anhydrides of Carboxylic Acids

The word anhydride literally means without water, and an acid anhydride is the combination of two
molecules of carboxylic acid with the elimination of one molecule of water.

Anhydrides are also considered as activated forms of carboxylic acids, although anhydrides are
not as reactive as acid halides.
limited quantity) then this is an undesirable way of making an activated carboxylic acid, and the
acid chloride route would be more desirable.
Acid > ester > amide > nitrile > aldehyde > ketone > alcohol > amine > alkene > alkyne > alkane > ethers
> halides

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Reactivity of Acid Derivatives

The carboxylic acid derivatives vary greatly in their reactivities with nucleophiles.

For example acid chlorides hydrolyze in moist air, whereas amides hydrolyze slowly even in boiling
alkaline water.

E.g. an alcohol will attack an acid chloride, but not a carboxylic acid.

However we saw that by using a strong acid, an alcohol can react with a carboxylic acid (Fischer
esterification, Ch 20) to give an ester.

Hydrolysis of Nitriles

Nitriles are hydrolyzed to primary amides, and then on to carboxylic acids.

Mild conditions only take this hydrolysis to the amide stage.

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Acid chlorides react quickly with nucleophiles such as water.

They are the most reactive acid derivatives, and are easily converted into any other of the acid derivatives.
E.g.

Acid chlorides can be converted into primary alcohols, tertiary alcohols, aldehydes and ketones through
the choice of appropriate organometallic reagent (Ch 10, 18 and 21).

Acid chlorides are also used in Friedal Crafts acylations (Ch17).

Acid Anhydrides
Anhydrides are also activated derivatives of carboxylic acids.
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They are produced most commonly by the reaction of an acid chloride and a carboxylic acid (or
carboxylate).

Some cyclic anhydrides can be made by simply heating the diacid.

Anhydrides undergo many of the same reactions as acid chlorides. E.g.

Esters

Esters are generally sweet smelling compounds, and are widely used as flavorings and perfumes. They are
most commonly made via Fischer esterifications using a carboxylic acid and an alcohol.

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Of course they can be also be made from acid chlorides, anhydrides and other esters (trnsesterification).
Methyl esters are conveniently made using diazomethane.

Esters are less reactive than acid halides and anhydrides, and acidic or basic conditions are required for
hydrolysis, although an amine can displace the alkoxide group to generate an amide (downhill reaction).

E.g.

Lactones (cyclic esters) are made from the Fischer esterification where the hydroxyl and carboxylic acid
functionalities are in the same molecule.

E.g.

Amides

These are the least reactive acid derivatives, and are easily formed from any of the other derivatives.

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Since amides are so stable (unreactive), they are not easily converted to the other derivatives via
nucleophilic acyl substitution.

Their most important synthetic use is their reduction to amines.

Since nitriles can be hydrolyzed to primary amides, primary amides can be dehydrated to nitriles. Most
commonly phosphorous pentoxide (P2O5), or phosphorous oxychloride (POCl3) are used.

(The Hofmann rearrangement can be useful to produce amines from primary amides with one less
carbon).

Lactams (cyclic amides) are often formed by heating (or dehydrating) amino acids.

E.g.

Nitriles

Despite not containing an acyl group, nitriles are still considered carboxylic acid derivatives since on
hydrolysis they form carboxylic acids.

These are most commonly made via the conversion of a carboxylic acid to a primary amide, followed by
dehydration.

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Alkyl nitriles can be prepared by the action of cyanide ion on alkyl halides.

Aryl nitriles are easily made via Diazonium salt formation and Sandmeyer chemistry (CuCN).

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