Acid Halides

Acid halide, neutral compound that reacts with water to produce an acid and a hydrogen halide.
Acid halides are ordinarily derived from acids or their salts by replacement of hydroxyl groups
by halogen atoms. The most important organic acid halides are the chlorides derived from
carboxylic acids and from sulfonic acids. The carboxylic acid chlorides, called acyl halides, are
generally more reactive than the sulfonic acid chlorides, called sulfonyl chlorides.

The 3 Preparation of acyl halide

Aliphatic acyl halides

Common laboratory methods for the synthesis of acyl halides entail the reaction of carboxylic
acids with reagents such as thionyl chloride[4] or phosphorus trichloride[5] for acyl chlorides,
phosphorus pentabromide for acyl bromides, and cyanuric fluoride for acyl fluorides.

Aromatic acyl halides

Aromatic acyl halides can be prepared in similar reactions with similar reagents;[6] however,
some specialty reactions are also available to produce these compounds. For example,
chloroformylation, a specific type of Friedel-Crafts acylation which uses formaldehyde as a
reagent[citation needed], or by the direct chlorination of benzaldehyde derivatives.[7]

Acyl fluorides
Acyl chlorides react with HF to give acyl fluorides.[8] Aromatic (as well as aliphatic) acyl
fluorides are conveniently prepared directly from carboxylic acids, using stable, inexpensive
commodity chemicals: PPh3, NBS and Et3N-3HF in a bench-top protocol.[9]

Reactions
Acid halides are rather reactive compounds often synthesized to be used as intermediates in the
synthesis of other organic compounds. For example, an acyl halide can react with:
water, to form a carboxylic acid. This hydrolysis is the most heavily exploited reaction for acyl
halides as it occurs in the industrial synthesis of acetic acid.

An alcohol to form an ester

an amine to form an amide

Acid anhydride

An acid anhydride is a chemical compound which is non- metal oxide which is obtained by
removal of a water molecule from an acid. The word ‘’anhydride’’ means without water. It reacts
with water and form an acidic solution [1].
Nomenclature

The name of organic acid anhydride is derived from carboxylic acid, undergo dehydration to
form a compound. In symmetrical acid anhydride carboxylic acid the only constituent used to
form the compound so the prefix is carboxylic and suffix anhydride is used. In asymmetrical acid
anhydride, two different carboxylic acids are used like the dehydration of benzoic acid and
propanoic acid, so the prefix is benzoic propanoic and anhydride is a suffix. Ethanoic acid forms
ethanoic anhydride, propanoic forms propanoic anhydride, etc. [2].

Preparation

It was first prepared by French chemist Charles Frederic Gerhardt in 1852 through heating
potassium acetate with benzoyl chloride.

Acetic anhydride is prepared by carbonylation of methyl acetate [3].

CH3CO2CH3 + CO → (CH3CO)2O

It is also prepared by another process that was developed by Wacker Chemie in 1922. In this
method acetic anhydride is prepared by reaction of ketene (ethenone) with acetic acid at 45-550C
and pressure is about 0.05-0.2 bar.

H2C=C=O + CH3COOH → (CH3CO)2O

Acid chloride is effective precursor for the preparation of organic acid anhydride [6].
 CH3C(O)Cl + HCO2Na → HCO2COCH3 + NaCl

Physical properties

Acetic anhydride or ethanoic anhydride is simplest insoluble anhydride of carboxylic acid. It is

flexible molecule with a nonplanar structure.

Appearance
Acetic anhydride is a colorless liquid but have vinegar like smell. Its smell is due to its reaction
with water vapor in the air which produce ethanoic again.

Solubility
It may not dissolve in water but it reacts to prepare ethanoic acid again.

Electrophilic character
Its internal asymmetry contribute a lot because it makes one side of compound more reactive
than the other one, that’s why it has electrophilic character as carboxylate is the leaving group.

Boiling point
Ethanoic anhydride boiling point is 1400C because it is big polar molecule. It has both types of
forces like van der Waals dispersion force and dipole- dipole force of attraction. But it does not
has hydrogen bonds that’s why it boiling point is less than other carboxylic acid like pentanoic
acid (1860C).

Chemical properties

Combustion

Acetic anhydride has strong irritating odor and combustible in nature.

Acetylation of alcohol and amines

In this reaction acetic anhydride is consider as a source of CH3CO. Alcohol and amines are
acetylated quickly. The reaction of acetic anhydride with ethanol produced ethyl acetate.

(CH3CO)2O + CH3CH2OH → CH3CO2CH2CH3 + CH3COOH

Pyridine is added as a catalyst, for specialized conditions Lewis acidic scandium salts are used as
catalyst.

Aromatic rings

These are acetylated by acetic anhydride, in which acid catalyst are used to speed up the reaction,
conversion of benzene to acetophenone and ferrocene to acetylferrocene.

(CH3CO)2O + C6H6 → CH3COC6H5 + CH3CO2H

 (C5H5)2Fe + (CH3CO)2O → (C2H5)Fe(C5H4COCH3) + CH3CO2H

Preparation of other acid anhydride

Upon treatment with acetic anhydride dicarboxylic acids are converted into anhydrides. Acid
anhydride also used in the preparation of anhydrides like reaction with nitric acid make acetyl
nitrate.

Precursor to germinal diacetates

Acetic anhydride react with aldehyde in the presence of acidic catalyst to produce germinal
diacetate. On industrial scale vinyl acetate are used for the preparation of ethylidene diacetate.

CH3CHO + (CH3CO)2O → (CH3CO2)2CHCH3

Hydrolysis

It dissolves in water about 2.6% by weight. Mostly acid anhydrides hydrolyses to give carboxylic
acids. In acetic anhydride it formed acetic acid.

(CH3CO)2O + H2O → 2 CH3CO2H

Chemical reaction with water, ethanol and phenol

The similarity present between them is having –OH group, in water it is attached with hydrogen
atom, in ethanol it is present with alkyl group and in phenol it is present with a benzene ring.

Acid Anhydride 1
Reaction with water

Acid anhydride react with water and produced two molecules of ethanoic acid. This reaction is
carried out very slowly at room temperature.

(CH3CO)2O + H2O → 2CH3COOH

Reaction with alcohol

Alcohol react with ethanoic anhydride it produced an ester and ethanoic acid.

(CH3CO)2O + ROH → CH3COOR + CH3COOH

An ester ethanoic acid

Reaction with ethanol produced ester ethyl ethanote. This reaction required heating at a moderate
temperature.
 (CH3CO)2O + CH3CH2OH → CH3COOCH2CH3 + CH3COOH

Ethyl ethanoate

Reaction with phenol

In the reaction of phenol and acid anhydride produced an ester called phenyl ethanote [4].

(CH3CO)2O +C6H5OH → CH3COOC6H5 + CH3COOH

Acid Anhydride 2
Comparing acid anhydride with acyl chloride

Acid Anhydride 3
During the reactions of ethanoic anhydride, the red part behave just like chlorine atom of acyl
chloride, it is always intact and replace just like chlorine atom.

Acid Anhydride 4
The reaction is carried out slowly, and the difference is that ethanoic acid is produced instead of
HCl.

Reaction with Ammonia

Amides contain –CONH2 group, during the reaction of ethanoic anhydride and ammonia, the
amide is produced which is called as ethanamide.

Acid Anhydride 5
(CH3CO)2O +NH3 → CH3CONH2 + CH3COOH

Ethanamide

With excess it produced to give ammonium ethanote.

CH3COOH + NH3 → CH3COO– +NH4

Ammonium ethanoate

Overall reaction is

(CH3CO)2O + 2NH3 → CH3CONH2 + CH3COO– +NH4

The reaction is acyl chloride is

CH3COCl + 2NH3 → CH3CONH2 + NH4+Cl–

Carboxylic Ester Definition

Esters are the derivatives of carboxylic acids in which the hydrogen of carboxylic acid (-COOH)
has been replaced by an alkyl group (-R) like methyl, ethyl or a benzene ring like phenyl. The
ester functional group may be represented as -COOR.

Ester 1

Esters are found in flowers and fruits which owe their fragrance for these compounds. Esters are
very important class of acid derivatives because of their uses in many synthetic products such as
perfumes, pesticides, solvents etc.

Nomenclature

The name of an ester has two part. First the name of the alkyl group R’ which is directly attached
with one of the oxygen in RCOOR’. Second part is the name of parent acid with the ending ‘-ic
acid’ changed to ‘-ate’ for ester. For example methyl methanoate, methyl ethanoate and ethyl
methanoate are the names of following three esters.

Ester 2

Preparation

The preparation of ester is known as esterification. Esterification is an equilibrium reaction to

form ester mainly from alcohols and carboxylic acids. Esters can also be made from the reactions
between acyl chlorides (acid chlorides) and alcohols, and from acid anhydrides and alcohols.

Ester 3

Here carboxylic acid and alcohol reacts to form an ester. Thus this is an esterification reaction.
Esterification can occur in three different ways

From carboxylic acid and alcohol

From acid chloride and alcohol
From acid anhydride and alcohol
1. From carboxylic acid and alcohol

Esters are mainly produced from carboxylic acid and alcohols by heating in presence of acid
catalyst. Usually concentrated sulfuric acid is used as a catalyst. This is also know as Fischer
esterification reaction. For example ethanoic acid and propanol reacts to form propyl-ethanoate
and water.

Ester 4
2. From acid chloride and alcohol

Esters can also be made from acid chloride and alcohol at room temperature. After a vigorous
(even violent) reation ester is formed with steamy acidic fume of hydrogen chloride. For
example, benzoyl chloride and alcohol reacts to form ester.

Ester 5

3. From acid anhydride and alcohol

The reaction between acid anhydride and alcohol is comparatively slower than with acid chloride
and usually need to warm the mixture to get more esters. For example, 2,6-diiodophenol reacts
with acid anhydride to form ester.

Ester 6

Physical properties

Boiling point

Small esters have boiling points, similar to those of aldehydes and ketones with the same number
of carbon atoms. Esters are polar molecule like aldehydes and ketones. But they don’t form
hydrogen bonds. Thus the boiling point of esters are lower than the acid with same number of
carbon atoms.

Molecule Type Boiling point (oC)

CH3COOCH2CH3 Ester 77.1
CH3CH2CH2COOH Carboxylic acid 164
Solubility

The small esters are fairly soluble in water but the solubility falls with increasing carbon chain
length. Although esters can not attach themselves with intermolecular hydrogen bond, but they
can make hydrogen bond with water molecules.The lone pair of oxygen in ester molecule can
make hydrogen bond with the partially positive hydrogen atom in water molecule.

As increasing the carbon chain length, the hydrocarbon part of the ester molecule get in the way
to form hydrogen bond between ester and water. Thus the solubility decreases.

Name of the ester Formula Solubility (g per 100 g of water)

Ethyl methanoate HCOOCH2CH3 10.5
Ethyl ethanoate CH3COOCH2CH3 8.7
Ethyl propanoate CH3CH2COOCH2CH3 1.7
Characterization
Esters are generally characterized by gas chromatography, because of their volatility. In the IR
spectrum, esters show a characteristic intense sharp band in the range between 1730–1750 cm−1
for νC=O.

Chemical properties

The carbonyl carbon in ester acts as a weak electrophile and is attacked by strong nucleophile
like amines, alkoxides, hydride sources etc. Thus ester gives nucleophilic substitution reaction
like acid halides and anhydrides.

Hydrolysis of ester

Upon hydrolysis by heating with water in presence of acid (H2SO4 or HCl) as a catalyst ester
gives parent carboxylic acid and alcohol. The reaction is reversible.

Ester 7

The hydrolysis of ester can also be achieved by heating with reflux in presence of aqueous
solution of strong base like sodium hydroxide.

Ester 8

Definition of Amides

Amides (RCONH2) are functional group where carbonyl group attached to a amine group. In
simple amides nitrogen attached with two hydrogen atoms. And in complex amides nitrogen
attached with one or two aliphatic or aromatic group replacing the hydrogen atom.

The carbon-nitrogen bond in amide is known as amide linkage. This bond is also present in
protein molecules where it is known as peptide linkage.

Structure of amide

The nitrogen, carbon and oxygen atoms in amide group, are sp2 hybridized. Thus the electrons of
three p orbitals on three atoms oxygen, carbon and nitrogen are are on the same plane and
delocalized. The resonance structures of amide is as follows:
Nomenclature

As amides are the derivatives of acid, by changing the end -oic acid to -amide we can name the
corresponding amides. Normally the name starts with the name of long chain aliphatic. As for
example, the name of the first compound is ethanamide. When aliphatic or aromatic group is
attached to the nitrogen atom, the name of these groups are placed at first, like in the second one,
the name is N,N-dimethylmethanamide.

Properties of amides

Melting point

Although the melting point of methanamide is liquid but the other higher carbon chain amides
are solid at room temperature. This is because of the presence of intermolecular hydrogen bond
between the partially positive hydrogen atoms attached with nitrogen of one molecule and
partially negative charged oxygen atom in another molecule. Each molecule has two partially
positive hydrogens, makes it more possible sites to have hydrogen bonding. To break these
hydrogen bonds more energy is needed and thus the melting point increases.

Solubility

Low amides are soluble in water because they can have hydrogen bond with water molecules.
Amides both act as a hydrogen bond donor and acceptor. The nitrogen and oxygen atom act as
acceptor and the hydrogens attached with nitrogen atom act as donor. As the aliphatic carbon
chain increases the solubility decreases because of the long chain get in the way of hydrogen
bond.
Basicity

Unlike amines, amides show no measurable basicity because of the presence of more
electronegative atom near to it. The lone pair of electron on the nitrogen atom is pulled and
delocalized through the oxygen, carbon and nitrogen atoms. As a result there are no available
electrons on nitrogen to show the basicity of the compound.

Synthesis of amides

Amides are usually formed from the reaction between an amine and a carboxylic acid. This is an
condensation reaction and water molecule is removed during the reaction.

This reaction is occurred in

few steps:

Step 1: A nucleophilic nitrogen attacks the carbonyl carbon center of carboxylic acid and oxygen
atom pulls the electron pair from the pi-bond simultaneously. Thus a zwiterrion is formed (a
positive ion on nitrogen atom and a negative ion on oxygen atom).

Step 2: The electron pair on oxygen reform the pi-bond and kicks the hydroxyl group (OH–) out
from the zwiterrion.

Step 3: The negatively charged hydrogen takes one of the hydrogen (H+) attached to nitrogen
atom to get rid of the charge from this stage. And thus the amide is formed.

Reaction of Amides

Amide breaks down to its corresponding amine and carboxylic acid. Amides are comparatively
unreactive because of delocalization of electrons. However an electronegative atom can attack on
the carbonyl carbon and break the pi-bond. The tetrahedral intermediate eventually breaks to
form amine and carboxylic acid under acidic condition.

Definition of Cyclic Amide

A lactam is a cyclic amide. The term is a portmanteau of the words lactone + amide.
A cyclic amide, or any compound containing it, formed by the intramolecular condensation of an
amino carboxylic acid.
(Elements & Compounds) chem any of a group of inner amides, derived from amino acids,
having the characteristic group -CONH-
[C20: from lact(one) + am(ide)]
any of a group of cyclic amides characterized by the NHCO group.

R-5.7.8.1 Monoacyl derivatives of ammonia (primary amides) are named by replacing the
suffixes "-oic acid", "-ic acid", or "-carboxylic acid" of the name of the acid corresponding to the
acyl group by "-amide" or "-carboxamide". The substituent prefix corresponding to is
"carbamoyl-"
Examples to R-5.7.8.

Substituted primary amides with general structures such as , . and the corresponding
sulfonamides, are named by citing the substituents R' and R" as prefixes (but see below for N-
phenyl derivatives).

Examples to R-5.7.8.1
N-Phenyl derivatives of primary amides are called "anilides" and may be named using the suffix
"-anilide" in place of the suffix "-amide". Locants for substituents in the N-phenyl ring are
primed.
Examples to R-5.7.8.1

Alternatively, an N-acyl group may be named as a N-substituent of an amine. This method is

used mainly for N-derivatives of nitrogenous heterocycles.

Example to R-5.7.8.1

When a group having preference for citation as a principal characteristic group is present, the
group of an N-substituted amide may be treated as a substituent of the compound HR'. The
group may be expressed as a substituent by changing the "-amide" or "-carboxamide" suffix of
the amide name to "amido-" or "carboxamido-", respectively, or alternatively, by the appropriate
"acylamino-" preix.
Examples to R-5.7.8.1
R-5.7.8.2 Symmetrical diacyl and triacyl derivatives of ammonia, i.e., and respectively, are
named as di- and triacyl derivatives of the parent hydride azane, or as di- and triacylamines.

Examples to R-5.7.8.2

The trivial names diacetamide and triacetamide for the compounds and , respectively, and
dibenzamide and tribenzamide for and , respectively, have been used but are not included in
these recommendations for use in naming carbon-substituted derivatives.
Unsymmetrical di- and triacyl derivatives of ammonia, such as , , and , may be named (a) on the
basis of the parent hydride azane; (b) as a diacylamine, a diacylalkyl- (or aryl, etc.) amine, or a
triacylamine; or (c) as alkyl (or aryl, etc.) or acyl derivatives of a primary amide (see R-5.7.8.1),
diacetamide, or dibenzamide.

Examples to R-5.7.8.2
Definition of Imides

In organic chemistry, an imide is a functional group consisting of two acyl groups bound to
nitrogen.[1] The compounds are structurally related to acid anhydrides, although imides are more
resistant toward hydrolysis. In terms of commercial applications, imides are best known as
components of high-strength polymers, called polyimides.

General linear Imide functional group

Nomenclature

Most imides are cyclic compounds derived from dicarboxylic acids, and their names reflect the
parent acid[2]. Examples are succinimide, derived from succinic acid, and phthalimide, derived
from phthalic acid. For imides derived from amines (as opposed to ammonia), the N-substituent
is indicated by a prefix. For example, N-ethylsuccinimide is derived from succinic acid and
ethylamine. Isoimides are isomeric with normal imides and have the formula RC(O)OC(NR′)R″.
They are often intermediates that convert to the more symmetrical imides. Organic compounds
called carbodiimides have the formula RN=C=NR. They are unrelated to imides.

Preparation

Most common imides are prepared by heating dicarboxylic acids or their anhydrides and
ammonia or primary amines. The result is a condensation reaction:[5]

(RCO)2O + R′NH2 → (RCO)2NR′ + H2O

These reactions proceed via the intermediacy of amides. The intramolecular reaction of a
carboxylic acid with an amide is far faster than the intermolecular reaction, which is rarely
observed.

They may also be produced via the oxidation of amides, particularly when starting from lactams.
[6]
R(CO)NHCH2R' + 2 [O] → R(CO)N(CO)R' + H2O
Certain imides can also be prepared in the isoimide-to-imide Mumm rearrangement.

Reactions

For imides derived from ammonia, the N–H center is weakly acidic. Thus, alkali metal salts of
imides can be prepared by conventional bases such as potassium hydroxide. The conjugate base
of phthalimide is potassium phthalimide. These anion can be alkylated to give N-alkylimides,
which in turn can be degraded to release the primary amine. Strong nucleophiles, such as
potassium hydroxide or hydrazine are used in the release step.

Treatment of imides with halogens and base gives the N-halo derivatives. Examples that are
useful in organic synthesis are N-chlorosuccinimide and N-bromosuccinimide, which
respectively serve as sources of "Cl+" and "Br+" in organic synthesis.

Imides are compounds containing the structural grouping and may be considered as nitrogen
analogues of anhydrides or as diacyl derivatives of ammonia. Acyclic imides are named
according to R-5.7.8.2. Cyclic imides are named by replacing the suffixes "-dioic acid", "-ic
acid", or "-dicarboxylic acid" of the corresponding dibasic acid by "-imide" or "-dicarboximide".
They can also be named as heterocycles.
Examples to R-5.7.8.3

Definition of Nitriles

Nitriles are the organic compounds in the organic chemistry which are also called as Cyano
Compounds. These class of organic compounds the functional group called cyano group
represented as (−C ≡ N), and it is attached to the carbon atom.

The structure of Nitrile, the functional group is highlighted blue

Properties
The chemical and physical properties of nitriles

1. Nitriles are somewhat like colorless solids and liquids having unique odors
2. They have boiling points measuring between 82-118 °C.
3. Nitriles exhibit strong dipole-dipole movements and also the van der Waals forces of
dispersion between the molecules.
4. They also show high polar and electronegativity.
5. These are said to be highly soluble in water, and the solubility decreases as the length of
chain increases.

Reactions
Nitrile undergoes various process of reactions

Hydrolysis- The hydrolysis of nitriles in the presence of an acid or a base produces carboxamides
and carboxylic acids in an efficient way.
Reduction- Nitriles are reduced to primary and tertiary amines by treating them with lithium
aluminium hydride. The reduction process occurs in the presence of some catalysts.

Alkylation- The Alkylation of nitrile compounds leads to the formation of nitrile anions.
The other reactions are nucleophilic addition reactions, Friedel–Crafts acylation, etc.

Uses

Nitriles finds its uses in various medical and industrial application

Nitriles are used in the manufacture of nitrile gloves, seals, and hoses as they exhibit resistance
to chemicals.
They are used as an antidiabetic drug which is used in the treatment of breast cancers.
The compound of nitrile called as pericyazine is used in treating opiate dependence as
antipsychotic.
This compound is found in many plant and animal sources.
They are utilized in the applications of oil resistant substances and also for low-temperature uses
They are also employed in automotive systems, hydraulic hoses and also in aircraft systems.

Nitriles Compounds with the general structure are called "nitriles" or "cyanides" generically and
may be named substitutively in a manner closely related to that for acids and other related
compounds. Acyclic mono- and dinitriles in which may be considered to have replaced the
group(s) of an acid named by an "-oic acid" or "-dioic acid" suffix are named by adding the
suffix "-nitrile" or "-dinitrile" to the name of the hydrocarbon from which the acid name was
derived.
Examples to R-5.7.9.1
Nitriles in which may be considered to have replaced of an acid with a retained trivial name
(see R-9.1, Table 28(a)) are named by changing the "-ic acid", or "-oic acid" ending of the name
of the acid to "-onitrile".
Examples to R-5.7.9.1

Nitriles in which may be considered to have replaced the group(s) of an acid named by a "-
carboxylic acid" suffix are named by replacing that suffix with "carbonitrile".
Examples to R-5.7.9.1

Functional class names for nitriles of the general structure are formed by citing the prefix name
for the group R followed by the class name "cyanide" as a separate word. Compounds with a
general structure such as and may be named similarly.
Examples to R-5.7.9.1

When a group is present that has priority for citation as the principal characteristic group or when
all groups cannot be expressed as the principal characteristic group, groups are described by the
prefix "cyano-".
Examples to R-5.7.9.1
Nitrile oxides. Compounds with the general structure have the generic name "nitrile oxides". In
specific cases, the class name "oxide" is added as a separate word after a nitrile name, but not a
cyanide name.
Example to R-5.7.9.3