1. Haloalkanes Introduction: (a) (b) Haloalkanes have the general formula RX, where R is an alkyl or substituted alkyl group.

(X is any halogen atom [F, Cl, Br, I] ) In haloarenes, the halogen is attached directly to a benzene ring.

Nomenclature and classification: (a) (b) The name is based on the original alkane skeleton with a prefix indicating halogens and their position. Haloalkanes are classified according to what is attached to the functional group, as follows:

Synthesis of haloalkanes: (a) (b) (c) Halogenation of alkanes with Br2 or Cl2 is free radical substitution reaction. Addition of HX to alkenes is electrophilic addition reaction. Reaction of alcohols with HX or PX3 or SOCl2.

Physical properties of haloalkanes: (a) Chloromethane, bromoethane and chloroethane are gases at room temperature and pressure. (b) The other simple haloalkanes are mostly liquids. (c) The boiling points of the isomers of a haloalkane increase in the order: tertiary < secondary < primary. (d) Haloalkanes are insoluble in water. Haloalkane molecules are only weakly polar and do not form hydrogen bonds with water molecules.

Chemical reactions of haloalkanes: Haloalkanes undergo mainly nucleophilic substitution reactions but elimination reactions may occur depending on the conditions of reaction. 2. Nucleophilic substitution reactions 1. Halogen are more electronegative than carbon. A dipole is induced in the C-X bond and it becomes polar. The carbon atom becomes electron deficient and is thus open to attack by nucleophiles. 2. During the reaction, the nucleophile uses its lone pair of electrons to form a new covalent bond while the halogen is displaced. The mechanism is known as nucleophilic substitution. Examples of nucleophiles are : OH- , CN- , H2O They are attracted to the slightly positive carbon. 3. Reactivity of the haloalkane depends on the strength of the C-X bond , the atomic radius of halogen atom , the type of nucleophilic substitution mechanism( SN1 or SN2) and the class of haloalkane. Nucleophilic substitution reactions of haloalkanes 1. Reaction with aqueous alkali (hydrolysis) Reagent: aqueous sodium hydroxide Conditions: heat under reflux in aqueous solution Nucleophile: hydroxide ion Product: alcohol Equation: RX + OH- ROH + XExample: C2H5Br + NaOH C2H5OH +

NaBr

(a) During hydrolysis the nucleophile involved is actually the H20 molecule, but the reaction is very slow. The OH- ions in the alkaline solution is a stronger nucleophile. (b) Hydrolysis with water can also be carried out in the presence of Ag+ ions as catalyst by using ethanolic silver nitrate solution or boiling with solid silver oxide.

2.

Reaction with potassium cyanide Reagent: ethanolic potassium cyanide, KCN Conditions: heat under reflux in alcoholic solution Nucleophile: cyanide ion Product: nitrile Equation: RX + KCN RCN + KX Example: CH3CH2CH2Br + KCN CH3CH2CH2CN + KBr butanenitrile (a) The reaction with cyanide ions is a useful way of lengthening the carbon chain. It is fairly easy to change the CN group at the end of the new chain into other groups. (b) For example, CH3CH2CH2Cl (3C) can converted into CH3CH2CH2CH2NH2 and CH3CH2CH2COOH (4C)

3. Reaction with ammonia Reagent: alcoholic concentrated ammonia Conditions: heat in alcoholic solution under pressire in a sealed tube Nucleophile: ammonia Product: Amine Equation: RX + NH3 RNH2 + HX Example: CH3CH2Br + 2NH3 CH3CH2NH2 + NH4Br Ethanamine (a) A series of amines will be formed depending on the amount of ammonia and haloalkane present. (b) If ammonia is in excess, a primary amine will be produced. (c) If haloalkane is in excess: the amine produced is also a nucleophile can attack another molecule of haloalkane to produce a 20 amine. This in turn is a nucleophile and can react further producing a 30 amine and finally an ionic quarternary ammonium salt.

Mechanism of nucleophilic substitution reaction in haloalkanes 1. The nucleophilic substitution reactions of haloalkanes can follow one of two reaction paths, that is SN1(unimolecular) and SN2( bimolecular). 2. SN1 nucleophilic substitution reaction (a) This is a two step mechanism that involves the formation of a carbocation/ carbonium ion followed by an attack by a nucleophile which uses its lone pair of electrons to form a covalent bond with the carbon atom.

(b) Step 1 (slow) is the rate determining step and involves only the haloalkane (unimolecular), hence the reaction is first order. Rate=k[(CH3)3CBr] (c) Since the mechanism involves the formation of an intermediate carbacation, this mechanism is most likely with tertiary haloalkanes as a tertiary carbacation would be the most stable.

3. SN2 nucleophilic substitution (a) SN2 (bimolecular) is a one step collision mechanism. In this mechanism, the process goes through a transition state or activated complex (highly unstable) before the final products are formed. Example: the C-Br bond is polarized. The lone pair on the nucleophile will be strongly attracted to the + carbon atom, beginning to make a coordinate bond. At the same time, the electrons in the C-Br bond will be pushing closer towards the bromine, making it increasingly negative, this continues until the nucleophile has been firmly bonded to the carbon and the bromine expelled as Br- as shown below:

(b) There is only one step in the reaction, so it is the rate-determining step. (c) It involves both the haloalkane and the nucleophile, hence the reaction is a second order reaction. Rate= k[CH3CH2Br][:Nu] (d) Tertiary haloalkanes usually do not undergo SN2 nucleophilic substitution due to steric hindrance by the many big alkyl groups as the nucleophile approaches the + carbon atom from side away from the halogen atom.

Elimination reaction of haloalkanes (a) Elimination reaction of haloalkane with sodium hydroxide Reagent: concentrated solution of sodium hydroxide in ethanol (ethanolic alcoholic NaOH Conditions: heat under reflux in alcoholic solution Product: Alkene Example:

(b) In the elimination reaction, the OH- ion is acting as a base. In some elimination reactions, a mixture of isomers may be produced. For example, the elimination of HCl from 2-chlorobutane produces both 1-butene and 2-butene.

Reaction with alcoholic silver nitrate solution (a) Alcoholic silver nitrate solution can be used to identify as well as compare reactivities of haloalkanes. (b) The reaction involves a solution os silver nitrate in ethanol which is mixed with the haloalkane and warmed. (c) The reaction is represented by RX + AgNO3 + H2O ROH + AgX + HNO3

To identify the type of halogen present in the haloalkane (a) The haloalkanes are mixed separately with the ethanolic silver nitrate and warmed. (b) White precipitate, soluble in ammonia solution chloroalkane Cream coloured precipitate, soluble in concentrated ammonia solution bromoalkane Pale yellow precipitate, insoluble in ammonia solution iodoalkane

To compare the reactivities of chloro-, bromo- , and iodo- alkanes (a) alkyl group of the haloalkane, amount of compound and reagent, and temperature must be kept constant. The time for the first appearance of precipitate is noted. Time taken for R-I < R-Br < R-Cl Order of reactivity: R-I > R-Br > R-Cl It is because bond strength of C-I < C-Br < C-Cl as bong length of C-I > C-Br > C-Cl due to atomic radius of I > Br > Cl. To compare the reactivity of primary, secondary, and tertiary haloalkanes (a) The halogen atom is kept constant as well as the amount of reagent and temperature. The time taken for precipitate to first appear is noted. (b) Time taken : tertiary < secondary < primary Order of reactivity: 30 haloalkane > 20 haloalkane > 10 haloalkane

Organometallic compounds 1. One important use of haloalkane is to convert them into reactive compounds called organometallic compounds that can be used to increase the number of carbon atoms in organic synthesis. 2. Organometallic compounds are compounds where a metal atom is covalently bonded to a carbon atom in an organic group. 3. Organometallic compounds of lithium and magnesium are important organic reagents. Organomagnesium compounds (RMgX) are commonly called Grignard reagents. Lithium compounds (RLi) are called organolithium compounds. 4. Organometallic compounds are normally named as substituted metals, e.g. alkyl metal or alkyl metal halide. Examples: CH3Li= methyl lithium, CH3MgBr= methyl magnesium bromide. Preparations of organometallic compounds

1. Organometallic compounds are prepared by reacting a haloalkane with the respective metals in the presence of a dry inert solvent, ether. Since lithium is more electropositive than magnesium, it is more reactive and lower temp are required for its preparation. Equations:

Example:

Reactions of organomagnesium and organolithium compounds 1. Reaction with water a. Conditions: In the presence of dilute acid, the organometallic reagent in ether reacts with water to form an alkane. Hydrolysis occurs. b. Equation: RMgX + H2O c. Examples: C2H5MgBr + H2O C3H7Li + H2O 2. Reaction with CO2 a. Conditions: Dry carbon dioxide is bubbled through a solution of the Grignard reagent in dry ether, followed by heating with dilute acid. RH + Mg(OH)X

C2H6 + Mg(OH)Br C3H8 + LiOH

b. Equation: RMgX + CO2 + H2O c. Example:

RCOOH + Mg(OH)X

3. Reaction with aldehydes and ketones The carbonyl compound is first reacted with the organometallic compound in dry ether, followed by hydrolysis with a dilute acid such as hydrochloric acid.

(a) with methanal (simplest aldehyde)

(b) with other aldehydes

(c) with a ketone

Commercial uses of organometallic compounds 1. Production of silicones

a. Grignard reagent or alkyllithium is used to first convert silicon halides into alkyl chlorosilanes: i. SiCl4 + RMgCl ii. RSiCl3 + RMgCl RSiCl3 + MgCl2 R2SiCl2 + MgCl2

b. The alkyl chlorosilane is then hydrolysed: R2SiCl2 + 2NaOH R2Si(OH) 2 + 2NaCl c. R2Si(OH) 2 is then polymerized to silicone. 2. Organotin compounds a. Organotin compounds are used as pesticides, fungicides, and heat stabilizers for PVC plastics. b. They are produced by reacting tin(IV) chloride with Grignard reagent. RMgCl + SnCl4 RSnCl3 + MgCl2

3. Tetraethyllead(IV) is used as an anti-knock in petrol a. It can be produced from reaction between ethyllithium and lead(II) chloride 2PbCl2 + 4C2H5Li (C2H5) 4Pb + Pb + 4LiCl

b. It can also be prepared by reacting chloroethane with a Na/Pb alloy 4C2H5Cl + 4Na/Pb (C2H5) 4Pb + 4NaCl

Chlorofluorocarbons (CFCs) CFCs are haloalkanes containing carbon, chlorine and fluorine They are used as fluids in refrigerators and air conditioners because they are gases at room temp which can easily be liquefied by compression, and also because they are not inflammable, stable, inert, and non-toxic They are also used as foaming agents for production of polystyrene foam plastics as well as in the fire extinguishers and as propellants in spray cans for paint, insecticide, etc.

Effects of CFCs on the environment CFCs destroy the ozone in the stratosphere. Ozone is important as it absorbs or filters out short wavelength UV adiation that can cause sunburn, skin cancer, and eye disorders. Ozone is normally formed: (a)(i) in the atmosphere through a photochemical reaction:

(ii) in factory when oxygen gas passes through a high voltage electric field:

(b) In the stratosphere, ozone is produced from oxygen through the action of UV light. Since oxygen is steadily produced by plants during photosynthesis, an ozone layer is slowly built up until equilibrium is established, where the rate of formation of ozone is equal to the rate of its decomposition.

Excessive CFCs destroy ozone in the following way: CFC is chemically inert and insoluble in water. Hence they are not destroyed nor dissolved in rainwater. They remain in the environment for a long time and diffuse up to the stratosphere. In the stratosphere, the CFC are decomposed in the presence of UV to produce chlorine radicals (which will initiate the reactions that destroy ozone).

The free chlorine radical then reacts with the ozone molecule:

The above chain reaction destroy a large portion of the ozone layer, creating a hole and letting UV rays to reach the surface of the earth.

To protect the ozone layer, the use of CFCs should be reduced and replaced with compounds that are degradable. CFCs cab be replaced by HCFCs (hydrochlorofluorocarbons), compounds containing at least one H atom. The C-H bond makes these compounds more reactive in the atmosphere so they are destroyed more quickly and are less able to diffuse into the stratosphere. Hydrofluorocarbons (HFCs) can also replaced CFCs. Since they do not contain any chlorine atoms, Cl radicals that destroy the ozone layer will not be formed.

Other uses of haloalkanes o o o o In the manufacture of insecticides like DDT which can damage the CNS. As solvents e.g. CHCl3 and CCl4 As anesthetic e.g. 2-bromo-2-chloro-1,1,1-trifluoroethane In the manufacture of monomers like chloroethene to make polymers like poly(chloroethene)