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Haloalkanes and Haloarenes: Classification and Applications

• After studying this unit, you will be able to name haloalkanes and haloarenes according to the IUPAC system of
nomenclature. They are resistant to breakdown by soil bacteria.

• Haloalkanes, containing halogen atoms attached to the sp3 hybridized carbon atom of an alkyl group, are formed
by the replacement of hydrogen atoms in aliphatic hydrocarbons by halogen atoms. Haloarenes, on the other hand,
have halogen atoms attached to sp2 hybridized carbon atom(s) of an aryl group.

• Halogenated compounds have various reactions and find applications in industry and everyday life. They are used
as solvents and starting materials for organic compound synthesis.

• Chloramphenicol, an antibiotic produced by microorganisms, is used for the treatment of typhoid fever. Thyroxine,
an iodine-containing hormone, regulates various bodily functions. Synthetic halogen compounds like chloroquine
and halothane are used in medicine.

• Haloalkanes and haloarenes may be classified based on the number of halogen atoms in their structure, as well
as the hybridization of the carbon atom to which the halogen is bonded.

• Alkyl halides or haloalkanes have the halogen atom bonded to an alkyl group and are further classified as primary,
secondary, or tertiary based on the carbon atom they are attached to.

• Allylic halides have the halogen atom bonded to an sp3-hybridized carbon atom adjacent to a carbon-carbon
double bond.

• Benzylic halides have the halogen atom bonded to an sp3-hybridized carbon atom attached to an aromatic ring.

• Vinylic halides have the halogen atom bonded to an sp2-hybridized carbon atom of a carbon-carbon double bond.

• Aryl halides are compounds in which the halogen atom is directly bonded to the sp2-hybridised carbon
atom of an aromatic ring.

• The common names of alkyl halides are derived by naming the alkyl group followed by the name of halide.

• In the IUPAC system of nomenclature, alkyl halides are named as halosubstituted hydrocarbons.

• For mono halogen substituted derivatives of benzene, common and IUPAC names are the same.

• For dihalogen derivatives, the prefixes o-, m-, p- are used in the common system, but in the IUPAC system, the
numerals 1,2; 1,3 and 1,4 are used.

• The dihaloalkanes are named as alkylidene or alkylene dihalides.

• Geminal halides or gem-dihalides have both halogen atoms on the same carbon atom, while vicinal halides or
vic-dihalides have halogen atoms on adjacent carbon atoms.

• In the common name system, gem-dihalides are named as alkylidene halides, and vic-dihalides are named as
alkylenedihalides.

• In the IUPAC system, gem-dihalides are named as dihaloalkanes.

• Halocompounds can be named using common or IUPAC names.

• Eight structural isomers with the molecular formula C6H11Br can be named and classified as primary, secondary,
or tertiary bromide.

• The carbon-halogen bond in alkyl halides is polarized, with the carbon atom bearing a partial positive charge and
the halogen atom bearing a partial negative charge.

• The size of the halogen atom increases as we go down the periodic table, resulting in an increase in
carbon-halogen bond length.

• Alkyl halides can be prepared from alcohols.

Preparation of Alkyl Halides and Haloalkanes

• The hydroxyl group of an alcohol can be replaced by a halogen using concentrated halogen acids, phosphorus
halides, or thionyl chloride.

• Thionyl chloride is preferred due to the formation of alkyl halide along with escapable gases SO and HCl, resulting
in the production of pure alkyl halides.

• Primary and secondary alcohols require a catalyst, ZnCl, when reacting with HCl, while tertiary alcohols can react
with concentrated HCl at room temperature.

• Alkyl bromides can be prepared through constant boiling with HBr (48%).

• Alkyl chlorides can be synthesized by passing dry hydrogen chloride gas through an alcohol solution or by heating
a mixture of alcohol and concentrated aqueous halogen acid.

• Aryl halides cannot be prepared using these methods due to the difficulty in breaking the carbon-oxygen bond in
phenols.

• Alkanes can be converted into mono- and polyhaloalkanes through free radical chlorination or bromination,
resulting in a complex mixture that is difficult to separate.

• Alkenes can be converted to alkyl halides through addition reactions with hydrogen halides or halogens.

• The reaction of alkyl chlorides or bromides with NaI in dry acetone, known as the Finkelstein reaction, yields alkyl
iodides and NaCl or NaBr.

• Alkyl fluorides can be synthesized by heating alkyl chloride or bromide with a metallic fluoride.

Preparation of Aryl Halides and Sandmeyer's Reaction

• Aryl chlorides and bromides can be easily prepared by electrophilic substitution of arenes with chlorine and
bromine, using iron or iron(III) chloride as a Lewis acid catalyst. Ortho and para isomers can be separated easily
due to their large difference in melting points. Fluoro compounds cannot be prepared using this method due to the
high reactivity of fluorine.

• Sandmeyer's reaction involves the formation of a diazonium salt by treating a primary aromatic amine with sodium
nitrite in cold aqueous mineral acid. The diazonium group can then be replaced by -Cl or -Br using cuprous chloride
or cuprous bromide. Replacement with iodine can be done by shaking the diazonium salt with potassium iodide.

• Sulphuric acid is not used during the reaction of alcohols with KI.

• Different dihalogen derivatives of propane can be formed by replacing hydrogen atoms with halogens.

• The boiling points of alkyl halides increase with the increase in size and mass of halogen atom, and decrease with
branching.

• Bromo, iodo, and polychloro derivatives of hydrocarbons are heavier than water.

Density and Reactions of Haloalkanes

• The density of haloalkanes increases with the number of carbon atoms, halogen atoms, and atomic mass of the
halogen atoms (Table 6.3).

• Haloalkanes have low solubility in water due to the weak intermolecular attractions between haloalkanes and
water molecules.

• Haloalkanes tend to dissolve in organic solvents as the intermolecular attractions between haloalkanes and
solvent molecules are similar in strength.

• Haloalkanes undergo nucleophilic substitution reactions, where a nucleophile replaces an existing nucleophile in
the molecule.

• Nucleophilic substitution reactions occur when a nucleophile reacts with a haloalkane, resulting in the departure of
a halide ion.

• The products formed by the reaction of haloalkanes with common nucleophiles are listed in Table 6.4.

• Haloalkanes can react with KCN to form alkyl cyanides as the main product, while AgCN forms isocyanides as the
chief product.

Nucleophilic Substitution Reactions and Configuration Inversion

• AgCN is primarily covalent and can donate an electron pair as an isocyanide product.

• Nitrogen can lead to alkyl cyanides or isocyanides in reactions with AgCN.

• The nitrite ion can link through oxygen to form alkyl nitrites or through nitrogen to form nitroalkanes.

• Substitution nucleophilic bimolecular (S 2) reactions proceed based on second order kinetics and the
concentration of reactants.

• In S 2 reactions, the incoming nucleophile interacts with the alkyl halide, breaking the carbon-halide bond and
forming a new bond between carbon and the attacking nucleophile.

• This process causes the configuration of the carbon atom under attack to invert, and bulky substituents near the
carbon atom inhibit the reaction.

• Methyl halides react most rapidly in S 2 reactions due to the absence of bulky hydrogen atoms.

Reactivity of Halides in Substitution Reactions

• Tertiary halides are the least reactive due to hindrance from bulky groups, following the order: Primary halide >
Secondary halide > Tertiary halide.

• Substitution nucleophilic unimolecular (S1) reactions occur in polar protic solvents, such as water, alcohol, and
acetic acid.

• The reaction between tert-butyl bromide and hydroxide ion follows the first order kinetics and occurs in two steps.
Step I involves slow cleavage of the C—Br bond, forming a carbocation and a bromide ion. In step II, the
carbocation is attacked by the nucleophile to complete the substitution reaction.

• Reactivity in S1 and S2 reactions of alkyl halides follows the order: 3° > 2° > 1°.

• Allylic and benzylic halides show high reactivity in S1 reactions due to carbocation stabilization through
resonance.

• The reactivity order of halides in both S1 and S2 reactions is: R–I>R–Br>R–Cl>R–F.

• Primary halides undergo S2 reaction faster due to the larger size and better leaving ability of iodine.

• The order of reactivity in S1 and S2 reactions for the isomeric bromobutanes is: CH3CH2CH2CH2Br <
CH3CH2CH(CH3)Br < CH3CH(CH3)CH2Br < CH3C(CH3)(CH3)Br.

Reactivity and Stereochemical Aspects of Substitution Reactions

• CHCH Br is more stable than derived from CH CH CH CH Br due to greater electron donating inductive effect of
(CH ) CH-group. (Text 1)

• (CH ) CHCH Br is more reactive than CH CH CH CH Br in S 1 reactions. (Text 1)

• NCH CH CH(Br)CH is a secondary bromide and (CH ) CBr is a tertiary bromide. (Text 1)

• Reactivity in S 2N reactions follows the reverse order of steric hinderance. (Text 1)

• C H C(CH ) (C H ) Br > C H CH(C H ) Br > C H CH(CH ) Br > C H CH Br in S 1 reactions. (Text 1)

• C H C(CH ) (C H ) Br < C H CH(C H ) Br < C H CH(CH ) Br < C H CH Br in S 2 reactions. (Text 1)

• Carbocation intermediate obtained from C H CH(C H ) Br is more stable than obtained from C H CH(CH )Br,
leading to greater reactivity in S 1 reactions. (Text 2)

• Phenyl group is bulkier than a methyl group, causing decreased reactivity of C H CH(C H ) Br in S 2 reactions.
(Text 2)

• Optical activity is the rotation of plane polarised light by certain compounds. (Text 3)

• Dextrorotatory compounds rotate light to the right, indicated by a positive (+) sign. Laevo-rotatory compounds
rotate light to the left, indicated by a negative (-) sign. (Text 3)

• Optical isomers are (+) and (-) isomers of a compound. (Text 3)

• Molecular asymmetry and chirality are associated with the three-dimensional arrangements of atoms in
compounds. (Text 3)

• Louis Pasteur's observation of mirror image crystals led to the understanding of enantiomers and optical rotation.
(Text 3)

Chirality and Optical Activity in Organic Molecules

• In 1874, Dutch scientist J. Van’t Hoff and French scientist C. Le Bel independently argued that the spatial
arrangement of groups around a central carbon is tetrahedral and if all the substituents attached to that carbon are
different, the resulting molecule is asymmetric.

• The asymmetry of the molecule, along with non-superimposability of mirror images, is responsible for the optical
activity in organic compounds.

• Objects that are non-superimposable on their mirror image are called chiral, while those that can be
superimposed are called achiral.

• A single asymmetric carbon atom can assist in recognizing chiral molecules.

• Propan-2-ol is an achiral molecule, while butan-2-ol is chiral due to its four different groups attached to the
tetrahedral carbon.

• Enantiomers are stereoisomers that are non-superimposable mirror images of each other. They possess identical
physical properties but differ in the rotation of plane polarized light.

Optical Rotation, Racemic Mixtures, and Configuration Changes in Chemical Reactions

• A mixture containing equal proportions of two enantiomers will have zero optical rotation, as the rotation of one
isomer cancels out the rotation of the other.

• Racemic mixtures, also known as racemic modifications, are represented by prefixing dlor (–) before the name of
the compound.

• The process of converting an enantiomer into a racemic mixture is called racemisation.

• Retention of configuration refers to the preservation of the spatial arrangement of bonds to an asymmetric center
during a chemical reaction.

• Inversion of configuration occurs when a bond directly linked to an asymmetric carbon atom is broken, resulting in
the inverted configuration of the product.
• Racemisation happens when a 50:50 mixture of two compounds with opposite configurations is obtained, making
the product optically inactive.

• S2 reactions of optically active alkyl halides lead to inversion of configuration.

• S1 reactions of optically active alkyl halides are accompanied by racemisation due to the planar nature of the
carbocation formed in the slow step.

• Attack of the nucleophile can occur from either side of the plane of the carbocation, resulting in a mixture of
products with the same or opposite configuration of the attaching group.

Alkyl Halides and Organo-Metallic Compounds

• Hydrolysis of optically active molecule 2-bromobutane results in the formation of (–)-butan-2-ol.

• When a haloalkane with a b-hydrogen atom is heated with alcoholic solution of potassium hydroxide, there is
elimination of hydrogen atom from the b-carbon and a halogen atom from the a-carbon atom.

• An alkene is formed as a product through b-elimination.

• In dehydrohalogenation reactions, the preferred product is the alkene with the greater number of alkyl groups
attached to the doubly bonded carbon atoms.

• Alkyl halides can undergo substitution (S1 and S2) or elimination reactions depending on their nature, the strength
and size of the base/nucleophile, and reaction conditions.

• Organic chlorides, bromides, and iodides react with certain metals to form organo-metallic compounds.

• Alkyl magnesium halide, RMgX, referred to as Grignard Reagents, are obtained by the reaction of haloalkanes
with magnesium metal in dry ether.

• Victor Grignard discovered organo-metallic compounds and received the Nobel prize for Chemistry in 1912.

Reactivity of Grignard reagents and haloarenes

• Grignard reagents have a polar carbon-magnesium bond and react with sources of proton to form hydrocarbons.

• Dry ether is used in Grignard reactions to avoid moisture.

• Wurtz reaction involves the reaction of alkyl halides with sodium in dry ether to produce hydrocarbons.

• Haloarenes are less reactive in nucleophilic substitution reactions due to resonance effects and differences in
hybridization.

• The electron withdrawing group (-NO2) increases reactivity at ortho- and para-positions in haloarenes, but not at
the meta-position.

• The nitro group stabilizes the carbanion formed in the reaction of haloarenes with nucleophiles.
Haloalkanes and Haloarenes: Electrophilic Substitution Reactions and Polyhalogen Compounds

• The presence of a nitro group at the meta-position has no effect on the reactivity of haloarenes.

• Haloarenes undergo electrophilic substitution reactions such as halogenation, nitration, sulphonation, and
Friedel-Crafts reactions.

• The halogen atom in haloarenes is slightly deactivating but ortho- and para-directing, causing further substitution
at those positions.

• Electrophilic substitution reactions in haloarenes occur slower and require more drastic conditions compared to
benzene due to the deactivation of the benzene ring.

• Chlorine is ortho-, para-directing in electrophilic aromatic substitution reactions due to the stronger inductive effect
and opposing resonance effect.

• The Wurtz-Fittig reaction involves the reaction of alkyl and aryl halides with sodium in dry ether to form
alkylarenes and compounds with two aryl groups.

• Polyhalogen compounds, such as dichloromethane and chloroform, have various uses in industry and can have
harmful effects on humans.

Chloroform, Iodoform, Carbon Tetrachloride, Freons, and DDT: The Uses and Dangers of Chlorinated
Organic Compounds

• Chloroform: - Major use is in the production of the refrigerant R-22 - Once used as a general anesthetic but
replaced by safer alternatives - Inhaling chloroform vapors can cause dizziness, fatigue, and headache - Chronic
exposure can damage the liver and kidneys - Skin immersion in chloroform can cause sores - Chloroform oxidizes
to produce a highly poisonous gas called phosgene - Stored in closed dark-colored bottles to prevent oxidation

• Iodoform: - Was used as an antiseptic but has been replaced due to objectionable smell - Antiseptic properties
come from liberation of free iodine, not iodoform itself

• Carbon Tetrachloride: - Produced for refrigerants, propellants, cleaning fluids, and solvent use - Exposure can
cause dizziness, nausea, and potential nerve cell damage - Severe cases can lead to coma or death - Irritates the
eyes - Can deplete the ozone layer, leading to increased health risks

• Freons: - Chlorofluorocarbon compounds used in aerosol propellants, refrigeration, and air conditioning - Stable,
non-toxic, non-corrosive gases - Freon 12 (CCl F ) is widely used and manufactured fromtetrachloromethane -
Freon production can negatively impact the ozone layer

• DDT: - First chlorinated organic insecticide - Discovered in 1939 as an effective insecticide - Developed by Paul
Muller of Geigy Pharmaceuticals

The Effects of DDT and Classification of Halides

• Paul Muller awarded Nobel Prize in Medicine and Physiology in 1948 for discovering DDT

• DDT's use increased after World War II due to its effectiveness against malaria-carrying mosquitoes and
typhus-carrying lice
• Problems with DDT appeared in the late 1940s, including resistance in insects and high toxicity towards fish

• DDT builds up in animal fatty tissues, leading to a ban in the United States in 1973

• Alkyl/Aryl halides can be classified as mono, di, or polyhalogen compounds based on the number of halogen
atoms

• Preparation methods for alkyl/aryl halides include halogenation, addition of halogen acids, and substitution
reactions

• Boiling points of organohalogen compounds are higher than hydrocarbons due to dipole-dipole and van der Waals
forces

• Alkyl halides exhibit nucleophilic substitution, elimination, and can form organometallic compounds

• Chirality affects reaction mechanisms in S1 and S2 reactions of alkyl halides

• Certain halides like DDT contribute to environmental hazards and ozone layer depletion.

Organic Chemistry - IUPAC Names, Organic Structures, Dipole Moments, Reactions, and Conversions

• Note: The given texts include questions and instructions related to organic chemistry, requiring the use of
knowledge in IUPAC naming, organic structures, dipole moments, reactions, and conversions. The texts provide
compounds and ask for their IUPAC names as well as the structures of various organic halogen compounds. The
texts also inquire about the highest dipole moment compound, a hydrocarbon's reaction with chlorine, isomers of a
certain compound, equations for preparation, ambident nucleophiles, S2 reactions with -OH, and
dehydrohalogenation reactions. Additionally, the texts pose questions about conversions between different organic
compounds.

Reactions of Haloalkanes and Haloarenes

• Isopropyl alcohol converted to iodoform.

• Chlorobenzene converted to p-nitrophenol.

• 2-Bromopropane converted to 1-bromopropane.

• Chloroethane converted to butane.

• Benzene converted to diphenyl.

• tert-Butyl bromide converted to isobutyl bromide.

• Aniline converted to phenylisocyanide.

• Alkyl chlorides treated with aqueous KOH form alcohols, while in the presence of alcoholic KOH, alkenes are
major products.

• Primary alkyl halide reacted with alcoholic KOH to form compound (b), which is then reacted with HBr to give (c)
as an isomer of (a).

• n-butyl chloride treated with alcoholic KOH.

• Bromobenzene treated with Mg in dry ether.

• Chlorobenzene subjected to hydrolysis.

• Ethyl chloride treated with aqueous KOH.

• Methyl bromide treated with sodium in dry ether.

• Methyl chloride treated with KCN.

• H2SO4 cannot be used with KI in the conversion of alcohol to alkyl iodide as it converts KI to HI, which is then
oxidized to I2.

• Structural formula for compound (a) and reactions.

• All hydrogen atoms in a molecule are equivalent, leading to the formation of four isomeric products.

• Examples of haloalkanes and their boiling points.

• Reactivity of halides based on steric hindrance and the presence of a methyl group.

• Tertiary halides react faster due to the stability of tert-carbocation.