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HALOALKANES AND HALOARENES Haloalkanes are the compounds formed by the replacement of H from an alkane(R-H) with halogen (R-X).

Haloarenes are the compounds formed by the replacement of H from benzene(C6H5-H) with halogen (C6H5-X). Halo- compound produced in our body: Thyroxine(Iodine). Chlorine containing antibiotic: Chloramphenicol. Chlorine compound in Malaria: Chloroquine. Blood substitute: Fully fluorinated/perfluorinated compounds. Compound used in Anaesthasia: Halothane(CF3CHClBr) Classification : Follow book Nomenclature rules: Follow longest chain. Follow lowest locant rule for numbering. Follow alphabetical order for naming Halogen compounds are started with prefix Halo-

Solve table 10.1,e.g ,Intext questions on pg no. 284,285. Nature of CX bond: Since halogens are more electro negative than Carbon, CX bond is polar. Order of polarity: CH3Cl>CH3F>CH3Br>CH3I (Dipole moment=Charge X distance of separation=Q X D) o-DichloroBenzene>m- DichloroBenzene>p- DichloroBenzene(p-DichloroBenzene has zero ) Methods of Preparation: Follow book. Melting point and boiling point: Boiling point depends upon the inter molecular interactions where as Melting point depends upon the symmetry and ease with which the compound can fit in a lattice. Order of Boiling point: CH3I>CH3Br>CH3Cl>CH3F(More molecular mass ,more vanderwaals force) Para-isomer of dihalobenzene Cl-- --Cl, has more m.p than o-isomer Cl-as it fits into the lattice better. Solubility: Slightly soluble in water as waterwater bond is stronger than new bonds formed between water and halocompound due to water repelling Alkyl group. Chemical properties of Haloalkanes: Reactions are divided into 3 categories: 1. Nucleophilic substitution reactions. 2. Elimination reactions 3. Reactions with metals. Nucleophilic substitution reactions Second Order SN2: OHNuceophile --CCl --- OH--------C--------Cl HOC--Haloalkane Formation of COH and Hydroxide formation Breaking of CCl simult. (Inversion) Nucleophile attacks Carbon from the opposite side of CX bond

Formation of COH bond and breaking of CCl bond happens simultaneously. No inter mediate is formed. Inversion of configuration takes place. The rate of reaction depends upon the Concentration of both the reactants. Pr. Halide > sec. halide> tert. Halide(reactivity) due to steric hinderance. Bulkier groups cause more steric hinderance to the incoming nucleophile. Nucleophilic substitution reactions First Order SN1: (CH3)3Br========(CH3)3+ + Br+OH-----------(CH3)3OH Haloalkane form carbocation after removing halide ion. Nucleophile attacks on trigonal planar carbocation from either side. The rate depends on the concentration of Alkyl halide(SN1). For Ist step energy comes to break bond from salvation of halide ion. 50% d- and 50% l- isomers are obtained in mixture and mixture has 0 optical activity. This mixture is called as Racemic mixture and process is racemisation. Tert.>sec.>Pr.(reactivity) due to extra stability of tert. Carbocation. Due to greater stabilization of allyl and benzyl carbocation intermediate, they show higher reactivity in (SN1). Some basic terms in Optical behavior: 1. Plane polarized light: Ordinary light is a combination of many waves of different wavelength and travels oscillating in all the planes. When this light is passed through a Nicol prism it vibrates only in one plane. 2. Optical activity: Some compounds rotate the plane polarized light when it passes through their solution. 3. Enantiomers: The sterio isomers related to each other as non-superimposable mirror image are called enantiomers(like our hands) example: : : : : *Carbon should have all 4 different groups. 4. Steriocentre: Carbon having all 4 different groups. 5. Chiral Objects: The objects that are Non superimposable on their mirror image. Example: our hands and this property is known as Chirality. Chiral molecule: Butan2-ol 6. Achiral Objects: The objects that are superimposable on their mirror image. Example: A Ball. Achiral Molecule: Propane2-ol. 7. Racemic Mixture: A mixture of 50% d-isomer & 50% l-isomer having zero optical activity. 8. Retention: Preservation of spatial arrangement after nucleophilic substitution. Example:

9. Inversion: Change of d- form to l- form or vice-versa. Example SN2. 10. Racemisation : Formation of equal amount of d- and l- form example SN1 mechanism. Elimination Reactions: It happens when haloalkane is heated with alcoholic KOH. This elimination is also called as -elimination or -dehydrohalogenation as Hydrogen is removed from position and halogen from -position. If there is possibility for more than one alkene due to presence of more -Hydrogens, it happens according to Saytzeff rule i.e The preferred product is that alkene in which more no. of alkyl groups attached with doubly bonded C-atom. H3CCH2CH==CHCH3 Pent2-ene (81%)
OH-

H3CCH2CH2CHCH3 OH-H3CCH2CH2CH==CH2 2-Bromopropene Pent1-ene (19%)

When haloalkanes are heated with aqueous KOH , they form corresponding alcohols as Halo group is replaced by OH group. But when reacted with alcoholic KOH they undergo elimination. The reason is that alcoholic KOH forms OR- as nucleophile where as water forms OH- as nucleophile. Bulkier nucleophiles behave as sronger base and eliminate a proton rather than substitution. Tertiary haloalkane prefer elimination over substitution. Name Reactions: Lucas Test(To distinguish between the Pr.,sec. & tert. Alcohols): ROH + HX------ZnCl2-----R-X + H2O Tert. Gives immediate turbidity,sec. gives after some time and Pr. Gives on heating. Sandmeyers reaction:

Finkelstein Halogen exchange: Swartz halogen exchange: Grignard Reagent: CH3CH2Br + Mg-------dry ether------- CH3CH2MgBr Wurtz Reaction: Fittig Reaction: Wurtz Fittig reaction:

Reasons for less reactivity of Aryl halides towards nucleophilic substitution reaction: 1. Resonance effect of halogen causes a partial double bond character. 2. Sp2 Carbon of benzene is more electronegative due to more s-character and forms a shorter bond which is more difficult to break. 3. Phenyl carbocation is highly unstable so SN1 is ruled out. 4. Benzene ring is electron rich so repels the incoming nucleophile. 5. The nucleophilic substitution happens under drastic conditions of temperature 623K,300 atm pressure. 6. Presence of electron withdrawing group on ortho or para positions requires less drastic conditions. For e.g if one NO2 group is present temperature 443K, if two --NO2 groups present 368K and if all the oand p- positions are occupied by three NO2 groups just warming the reaction mixture will cause substitution reaction. ELECTROPHILIC SUBSTITUTION REACTIONS: 1. Halogenation: 2. Sulphonation 3. Nitration : 4. Friedel Craft alkylation: 5. Friedel Craft acylation:

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