11acyl Halideisrael Jude P.
11acyl Halideisrael Jude P.
11acyl Halideisrael Jude P.
Israel, Jude P.
What are Acyl Halide?
An Acyl halide (also known as an acid halide) is a
neutral compound that reacts with water to produce an acid
and a hydrogen halide. Acid halides are ordinarily derived
from oxoacids or their salts by replacement of hydroxyl groups
by halogen atoms and are often used to prepare the other
carboxylic acid derivatives.
Nomenclature
The nomenclature of acid halides starts with the name of the
corresponding carboxylic acid. The –ic acid ending is removed and
replaced with the ending -yl followed by the name of the halogen with
an –ide ending. When the acid halide is attached to a ring, a suffix name
carbonyl followed by the halogens name with –ide ending. This is true
for both common and IUPAC nomenclature. The carbonyl carbon is
given the #1 location number.
Propanoyl bromide
Benzoyl chloride 2-methyl-cyclohexanecarbonyl chloride
Physical properties of acyl halides
An acyl halide such as ethanoyl chloride is a colorless, fuming
liquid. The strong smell of ethanoyl chloride is a mixture of the smell of
vinegar (ethanoic acid) and the acrid smell of hydrogen chloride gas.
The smell and the fumes originate from the reactions between ethanoyl
chloride and water vapor in the air.
Solubility in water
Acyl halides do not dissolve in water because they react (often
violently) with it to produce carboxylic acids and hydrogen halides (e.g.
HCl). The strong reaction makes it impossible to obtain a simple
aqueous solution of an acyl halide.
Boiling points
Taking ethanoyl chloride as a typical example: ethanoyl chloride
boils at 51°C and is a polar molecule. Therefore, it has dipole-dipole
attractions between its molecules as well as van der Waals dispersion
forces. However, it does not form hydrogen bonds. Its boiling point is,
therefore, higher than an alkane of similar size (which has no permanent
dipoles) such as ethane, which boils at -88.5°C, but not as high as a
similarly sized alcohol (which forms hydrogen bonds in addition to
everything else) such as ethanol, which boils at 78.37°C.
SYNTHESIS OF ACYL CHLORIDE
Acyl halides are synthesis through a nucleophilic addition—
elimination reaction.
Since acyl chlorides are the most reactive of the acid derivatives, we
must use special reagents to prepare them. We use other acid chlorides,
such as the acid chlorides of inorganic acids: PCL5, PC3 and SOCl2
REACTIONS OF ACYL HALIDES
HYDROLYSIS OF ACID HALIDES
Acyl halides also react with water and (even more rapidly) with aqueous
base, but these reactions are usually not carried out deliberately because they
destroy the useful acyl chloride reactant by regenerating either the carboxylic
acid or its salt:
ALCOHOLYSIS
Acyl halides reacts with alcohol to produce esters. The process is
analogous with hydrolysis of acyl halides and is commonly use for the
preparation of esters on the laboratory. As with hydrolysis, alcoholysis
reactions are usually carried out in the presence of pyridine or NaOH to
react with the HCl formed.
AMINOLYSIS
Acid chlorides react rapidly with ammonia and amines to give
amides. As with the acid chloride-plus-alcohol method for preparing
esters, this reaction of acid chlorides with amines is the most commonly
used laboratory method for preparing amides. Both monosubstituted and
disubstituted amines can be used, but not trisubstituted amines (R3N).
FORMATION OF ANHYDRIDES
Nucleophilic acyl substitution reaction of an acid chloride with a
carboxylate anion gives an acid anhydride. Both symmetrical and
unsymmetrical acid anhydrides can be prepared.
SOURCES AND USES
Acyl halides are ordinarily derived from oxoacids or their salts by
replacement of hydroxyl groups by halogens atoms and are often used
to prepare other carboxylic acid derivatives.
Acyl halides are highly reactive substances use primarily in organic
syntheses. They react with water, ammonia, and alcohols to give
carboxylic acids, amides and esters respectively. In addition, acyl
halides are commonly used as a reagents for derivatization of other
analytes. The derivatization of acyl halides as analyte can be done by
using a hydrolysis followed by subsequent derivatization of the acid.
QUIZ
QUIZ
Name the ff. compounds using IUPAC naming system.
a. b. b. c.
d. e.
ANSWERS
A.2,5-dibromopentanoyl chloride
B.6-aminohexanoyl chloride
C.Cyclopentanecarbonyl chloride
D.2-ethyl-3-methylpentanoyl chloride
E.2,4-dichlorobutanoyl chloride