studying this Unit, you will be to haloalkanes and haloarenes to the IUPAC system of jomenclature from their given aa Halogenated compounds persist in the en e invol Tesisi reakdown by soil ba Pparaion a ae red 8 tance to breakdown by soil b aloarenes and understand arious reactions that they The replacement of hydrogen atom(s) in an aliphatic undergo; or aromatic hydrocarbon by halogen atom(s) results correlate the structures of in the formation of alkyl halide (haloalkane) and aryl haloalkanes and haloarenes with halide (haloarene), respectively. Haloalkanes contaii various types of reactions; halogen atom(s) attached to the sp” hybridised carbo use stereochemistry as a tool for atom of an alkyl group whereas haloarenes contai understanding the reaction jralogen atom(s) attached to sp? hybridised carbon : atom(s) of an aryl group. Many halogen containin, Scale cae °F organic compounds occur in nature and some ofjus highlight the environmental effects {eS are clinically useful, These classes of compounds ft polyhlogen eouspounds. find wide applications in industry as well as in day- ; : to-day Iife. They are used | ment due to th Gqytenpons ‘and as starting materials for | the synthesis of wide range of organic compound: . Chlorine containing antibiotic, produced by microorganisms eae ie a “teatmen op fe Our body produces iodine containing hormone, thyroxine, the deficiency of which causes a disease called gotedimstitetie_halogen_ compounds, e is used for the treatment is used as. an anaesthetic In this Unit, you will study the important methods of preparation, physical and chemical properties and uses of organohalogen compounds.SE 7 Gestation Haloatkanes and haloarenes may be classified a8 follows: a 4h or pbyalogen (eng, Cont Chemistry 2905 These may be classified as mono, ae ‘compounds ‘on whether they contain ont, two or mora atoms in their structures. For example, CH, Fax GHX by, fe CH CH,x Monohaloalkane Dihaloalkane Trihaloalkane . x x x ‘oe Oo ; Monohaloarene Dihaloarene Trihaloarene Monohalocompounds may further be classified according to hybridisation of the carbon atom to which the halogen is bonded, discussed below. tal Moan tncludes Alkyl halides or haloatkanes (R—X) In alkyl halides, the halogen atom is bonded to an alkyl group (R ‘They form a homologous series represented by C,H,,,.X. They are farther classified as primary, secondary or tertiary according to the nature of carbon to which halogen is attached. Ifhalogen is attached tp @ primary carbon atom in an alkyl halide, the alkyl halide is called primary alkyl halide or 1° alky! halide, Similarly, if halogen is attached to secondary or tertiary carbon atom, the alkyl halide is called Secondary alkyl halide (2*) and tertiary (3°) alkyi halide, respectively. Hw R R R-0-X R'-0-X "-0-X f r Pak H H R” Primary (1°) Secondary (2°) Tertiary (3°) } Allylic halides ‘These are the compounds in which the halogen atom is bonded to an sp*-hybridised carbon atom adjacent to carbon-carbon double bond (C=C) ie. to an allylic carbon. X Allylic carbon = kK x Allylic carbon Benzylic halides ‘These are the compounds in which the halogen atom is bonded to an sp’-hybridised carbon atom attached to an aromatic ring,R xX om ox ay CH,, R"=H(2") R" = CH, (3°) Compounds This class includes: Containing se Vinylic halides sp0—K Bond TUPAC name: Common name: . TUPAC name: TUPAC name: ‘These are the compounds in which the halogen atom {s bonded to a sp*-hybridised carbon atom of a carbon-carbon double bond (C=O. = x x Or Aryl halides These are the compounds in which the halogen atom is directly bonded to the sp*-hybridised carbon atom of an aromatic ring. oO Yo 10.2 Nomenclature Havinglearnt the classification rage compounds, let us now learn 7s how these are named. The common names of alkyl halides are derived by naming the alkyl group followed by'the name of halide. In the IUPAC system nomenclature, alkyl halides are named as halosubstituted logen derivatives, the prefixes o-, m-, p-are used in common system but in IUPAC system, as you have learnt in Class XI, Unit 12, the numerals 1,2; 1,3 and 1,4 are used. CH, C-CH-CH, s CHC HA I H,CH,CH, Br r Ho-bH-CH.CI n-Propyl bromide Isopropyl chloride (USBbItyT/Chloride 1-Bromopropane 2-Chloropropane 1-Chloro-2-methylpropane ir : ir 7 Oo Br : Br Br Br Bromobenzene m-Dibromobenzene Bromobenzene 1,3-Dibromobenzene » 1,3,5-Tribromobenzene CH, .C—CH-CH. H,C-C-CHr Cl Heng i ba, Br 1-Chloro-2,2-dimethylpropane -_-2-Bromopropane ‘The dihaloalkanes having the same type of halogen atoms are named as alkylidene or alkylene dihalides, The dihalo-compounds havgng both the halogen atoms are further classified as geminal halides or gem-dihalides when both the halogen atoms are present on the same carbon atom of the (QQdgllaloalkanes and Haloarenesjes when halogen atoms are ies w chain and vieinal halides gt vic =ammon name system, Bemi-dthay on adjacent carbon atoms. Tn Co! dv! es are named ag named as_alkylidene halides ane named as dinaloalkanes, Aihalides, in IUPAC system, on H-CH, HC-" aa Ethylene@ehloride “Common name: Buiylene San {vie-dihalide) (gem 1, 2-Dichloroethane TUPAC name: 1, 1-Dichloroethane tioned in Tab on examples of halocompounds are men "e0, Names of some Halides e 10.1: Common and IUPAC ean 2-Chlorobutane 1-Bromo-2,2-dimethylpropang| 2-Bromo-2-methylpropane CHSCH,CH{(CI)CH, | sec-Butyl. chloride (CHJ,CCH,Br (CHJsCBr CH= CHCL CH, = CHCH,Br neo-Pentyl bromide tert-Butyl bromide Vinyl chloride Chloroethene Allyl bromide 3-Bromopropene 1-Chloro-2-methylbenzene or 2-Chlorotoluene ©-Chlorotoluene Chlorophenylmethane Benzyl chloride Dichloromethane ‘Trichloromethane ‘Tribromomethane Carbon tetrachloride| Tetrachloromethane n-Propyl fluoride | 1-Fluoropropane le 10.1 Solution Draw the structures of all the eighit\striiéturallisomers that have the molecular formula @jJHyjBr. Name each isomer according to IUPAC system and classify them as primary, secondary or tertiary bromide. CH,CH,CH,CH,CHig; — 1-Bromopentane (1°) CH,CH,CH,CH(g;JCH, 2-Bromopentane(2°) CH,CH,CH(piJCH:CH, 3-Bromopentane (2°) (CHy,CHCH,CHip; —_1-Bromo-3-methylbutane (1°)(CH),CHCHiiCH, 2-Bromo-3-methylbutane(2’) «(€Hy,CBrCH,CH, 2-Bromo-2-methylbutane (3°) (CH,CH,CH(CH,)CH,Br = 1-Bromo- /-methylbutane(1") (CH,)sCCH, Br 1-Bromo-2,2-dimethylpropane (1°) TUPAC names of the following: a H_ pts MG __ fa in = H br A iv, oe HC HC. ve Cy H CH =H H CH oh H H. H 4-Bromopent-2-ene (i) 3-Bromo-2-methylbut-l-ene Solution ) 4-Bromo-3-methylpent-2-ene (tv) 1:Brorno-2-methylbut-2-ene ’) 1-Bromobut-2-ene.__ (vi) 3-Bromo-2-methylpropene > Tntext y iy ose following compounds: ‘hloro-3-inethylpentane Goutae tert. Butyl-3-iodoheptane Vp remota 1. -Bromo-4-sec. butyl-2-methylbenzene, Halogen atoms are more electronegative than carbon, therefore, carbon-halogen bond of alkyl halide is polarised; the carbon atom bears a partial positive charge whereas the halogen, atom bears a partial negative charge. \S+_§- fs ‘As we go down the group in the periodic table, the size of halogen atom increases. Fluorine atom is the smallest and iodine atom is the largest. Consequently the carbon-halogent bond length also increases from C—F to C—I. Some typical bond lengths, bond enthalpies and dipole moments are given in Table 10.2. Alky! halides which are accessible. 293,Haloalkanes and Haloarenesi ee SN on? SEB a1 e4- _ 4 vengths, Bond or Halogen (C—X) BO Table 10.2: ceed pipole Momen 10.4 Methods of ced by halogen on reaction ‘The hydroxyl group of an alcohol 1s repla My Preparation constr Feiegen acids phosp! halides « of Haloalkanes Thlanyl chloride is p cause 0 10.4.1 From Alcohols YJ Ron + Ho] > RI + HO Y/ROH + NaBr +HSOQ—> RBr + NaHSO, + H,0 /SR-OH + PX, ———> SRX* HPO, X=Cl, Br) v ROH + Pcl, —— RCI + POCI, + HCI a ROH RX V Ron + —— R&I + 80, + HCI ‘The preparation of alkyl chloride is carried out either by passing dry hydrogen chloride gas through a solution of alcohol or by heating a mixture of alcohol and concentrated aqueous halogen acid. "The above methods are not applicable for the preparation of aryi mnd int phenols has a partial doubk ge the carbon-oxygen bond in. Bap bond. difficult to break being stronger than a single ond (Unit 11, Class XN” ——4 ‘From alkanes by free radical halogenation Free radical chlorination or bromination of alkanes gives a complex mixture of isomeric mono- and polyhaloalkanes, which is difficult to 10.4.2 From _____ chemistrySeparate as pure compounds. Consequently, thélyieldiof any single (GompounaS ecm 13, Class XI), CHsCHaCH,CHy SLAW Wit, cH cHCH CHC! + CHyCH;CHCICHs aire alkenes Addition of hydrogen halides: An alkene 18 converted to corresponding allyl halide by reaction with hydrogen chloride, hydrogen bromide or hydrogen iodide. No” 7 C= 00 + HK — No 7 AN HX Propene yields two products, however only one pred : predominates as Per Markovnikov's rule. (Unit 13, Class XI) CH,CH = CH,+ H4—> CH,CH,CH, + CH,CHICH, A minor major Addition of halogens: In the I addition of bromine in CCl, to an of bromine constitutes an important method for the detection of double bo: its in the synthesis often, ich ae abut 19, Class XD, CCl, > + B,—,. BrCH,-CH,Br vic-Dibromide Identify all the possible monochlsro structural isomers expected to be formed on free radical monochlorination of (CH,), CHCH,CH,, Inthe given molecule, there are four different types of hydrogen atoms. Solution Replacement of these hydrogen atoms will glve the following (CH,,CHCH,CH,C1 (CH,,CHCHICICH, (CH), C(C)CH,CH, CH,CHICH,CI}CH,CH, 10.4.3 Halogen Alkyl iodides are often d by the reaction of alkyl chlorides/ Exchange —_ bromides with Nain dry acetone, This reaction is known as\Rinkelstein reaction, —— RX + Nal——>RI + NX X=Cl, Br ‘ NaCl or NaBr thus formed is precipitated in dry acetone. It facilitates the forward reaction according to Le Chatelier's Principle. = The synthesis of alkyl fluorides is best accomplished by heating an alkyl chloride/bromide in the presence of a metallic fluoride such as :295Haloalkanes and Haloarenes10.5 . Breparation of Af From hydrocarbons by elec eee Chemistry 296, - When a primary aromatic amine, reaction is term pyc-F * ABBE trophic substitution easily prepared by elect, ‘promine res} ‘The H,C-Br+ AF Aryl chlorides and bromides can be substitution of arenes with © lorine presence of Lewis acid catalysts I req HIO, to oxidise the HI formed during iodine! are not prepared by this method due to nigh reactivity of fluoring From amines by Sandmeyer's reaction dissolved or suspended in aqueous mineral acid, is treated with sodium nitrite, a diazoni xing the solution of fres} salt is formed (Unit 13, Class XII). Mi Prepared dlazonium salt ‘vith cuprous chloride or cupro romide results in the replacement of the diazonium - grouy] by -Cl or -Br. ve o™ NaNO, + HX NX ae 273-278 KWrite the products of the following reactions: a Ho yHpr— CH,-CH,-CH-CH, + HCl HH we 4+ HBr Beroside, H H ® ay CCH - an) oe Her HH Why is sulphuric acid not used during the reaction of alcohols with KI? Write structures of different dihalogen derivatives of propane. {104 Among the isomeric alkanes of molecular formula Hyp Hdentify the one that on photochemical chlorination yields a ‘a single monochloride. .e isomeric monochlorides. vata isomeric monochlorides. 6 Draw the structures of major monohalo products in each of the following reactions: CH,CH, OH A Of + a ee CHOH cH, ut Cw + HL By 5 % Ht oH at wr CH,CH,Br + Nal —> er CO) Br, rir 10.6 Dhysical Alkyl halides . Howevel P s Properties lany volatile halogen compounds have sweet smel Ko" Haloalkanes and Haloarenes___Chemistry 206 Melting and boiling points le, methyl_bromide, ethyl chloride and son, chiorofluoromethanes are gases at room temperature. Higher member, are liquids or solids. As we have already learnt, molecules of o; halogen compounds are generally polar. Due to greater polarity as as higher molecular mass as compared to the parent hydrocarbon, intermolecular forces of attraction (dipole-dipole and van der Waaj,) are stronger in the halogen derivatives. That is why the boiling poin;, of chlorides, bromides and iodides are considerably higher than thog. of the hydrocarbons of comparable molecular mass. The attractions get stronger as the molecules get bigger in size have more electrons. The pattern of variation of boiling points of diffe halides is depicted in Fig. 10.1. For the si ame alkyl group, the balling points of alkyl halides decrease in the orde: is because with the increase in size and mass of halogen atom, magnitude of van der Waal forces increases. BP(K) 400 300 200 100 ° CHX CH,CH,X CH,CH,CH,X Taffox Comparison of bolling points of some alkyl halides The boiling points of isomeric haloalkan es decreas in branching (Unit 12, Class XI). For example. “pebrome:® methylpropane has the lowest boiling point among the three ‘sone CHs CHCH,CH,CH,Br CHgCH2GHCHs Hgc-b-CHy . Br bp 375 364 246@ en atoms and atomic mass of the halogen atoms (Table 10.3). Table 10.3: Density of Some Haloalkanes Cn Density (g/mL) Compound Pena) Solubility The haloakanes areWaR Sal SHUBNeEUaLer In order to aslve haloalkane in water, energy is required to overcome the attractions between the haloalkane molecules and break the hydrogen bonds between water molecules. Less energy is released when new attractions are set up between the haloalkane and the water molecules as these are not as strong as the original hydrogen bonds in water. Asa result, the: ste ofhaloalkanes in water is low. because the new intermolecular attractions between anc 7 solvent molecules have much the same strength as the ones being broken in the separate haloalkane and solvent molecules. ry : fe each set of compounds in order of increasing bolling points. AT brent Bromoform, Chloromethane, Dibromomethane. , _91-Chioropropane, Isopropyl chloride, 1-Chlorobutane. 10.7 Chemical Teepe Sn ht bast ee Reactions ‘Nycleophilic substitution React ition reactions ee eee Reaction with metals. Haloalkanes leophilic substitution reactions You have leamt in Class XI that nucleophiles are electron rich species. ‘Therefore, they attack at that part of the substrate molecule which Is electron deficient. The-reaction in which a nucleophile replaces 12QQ¢Haloalkanes and Haloarenescalled m1 already existing nucleophile in & molecule ce called nucleo already fon reaction. Haloalkanes af SY 0 with these eters In this type of reaction, @ nucleophile a re substrate) having @ charge ae ad to halogen. A substitution reaction takes lace ee nlogen atom, Called leaving group departs as halide lon’ TT eg nucl tut carton ta ialtiated by a nucleophile, 1 15 cleophin. ‘substitution reaction. \5 x x \ Nat SOX pone + ee halides in which logen is ‘bonded to sp? hybridised m. The products formed by the reaction of haloalkanes with some common nucleophiles are given in Table 10.4. Table 10.4: Nucleophilic Substitution of Alkyl Halides (RX) R-X+Nu" > R-Nu+X Reagent Perea eer Cer ) eae es NaOH (KOH) HO NaOR’ wnt ct goes rare nr cent hybrid of two contributing structures and tects SOUP Is 8 and therefore can act as @ nucleophile in two different ways [° ys [CaN :C=N9J, Le, Le., linking through Chemistloalkanes react with KCN to form alkyl cyanides as main product le ACN forms isocyanides as the chief product. Explain. N is predominantly ionic and provides cyanide ions in solution. Solution Ithough both carbon and nitrogen atoms are in a position to donate lectron pairs, the attack takes place mainly through carbon atom and not through nitrogen atom since C—C bond is more stable than C—N |. However s covalent in nature and nitrogen is free lonate electron pair forming isocyanide as the main product. carbon atom resulting in alkyl cyanides and through nitrogen atom leading to isocyanides, Similarly nitrite ion also represents an ambident nucleophile with two different points of linkage [O—N =O]. The linkage qorouen oxygen results in alkyl nitrites while through nitrogen atom, it leads to —— Mechanism: This reaction has been found to proceed by two different m ‘which are described below: Substitution nucleophilic bimolecular (S,2) ‘The reaction between CH,Cl and hy ide ion to yield methanol and chloride ion follows ssn are ket e., the rate depends upon the concentration of both the reactants. eee oft +P L8] mo, ‘You have already learnt in Section 12.3.2 of Class XI, the solid wedge represents thé bond’ coming out of the paper, dashed line going down the paper and a straight line representing bond in the plane of the paper. The above reaction can be represented diagrammatically as shown in o poh ove o 6. 0.2: Red ball represents the incoming hydroxide ion and green ball represents the outgoing halide ion 7, It depicts a bimolecular nucleophilic substitution (S,2) reaction; the incoming nucleophile interacts with alkyl halide causing the carbon-halide bond to break’ and a new bond is formed between _ carbon and attacking nucleophile. Here it is C-O bond formed between C and -OH. These two processes take place’ simultaneously:in a (@omHaloalkanes and Haloarenes__tion Spacial arrangement of functional | See the structures (a) Hughes worked under Ingold and earned a carbon bearing the leavin D.Se. degree from the eeup. University of London. " icteophile and thee can the bond etween the incoming pen atom, aaa ea, atom starts forming, the aaeuarrens carbon-hydrogen } sroup weakens, eee eee from the attacking nucleoppy,* : attached Putte attacking and leaving nucleophiles a eee carbon. As the attacking nucleophile aj : bonds still keep on moving in the same aos Eee ne attacteng nucleophile attaches to carbon and leaving group the carbo As a result AER ARTE the configuration (See box P carbon atom under attack inverts in much the sa way a8 an umbrella is turned inside out when cauglit in a strong wind, Process is called as inversion of configuration. In the transi state, the carbon atom is simultaneously bonded to inco; nucleophile and the outgoing"leaving group. Such structures ar, unstable and cannot be isolated. Thus, groups around carbon is called its configuration, and (B) given below carefully. Mirror Since this reaction requires the @pproach of the nucleophile to tht the pre: on orga the carbon alan have a armatc oie suatuen® ‘simple alkyl halides, methyl halides react most rapidly in 8,2 re .ctions because there are only three small hydrogen atoms. Tertiary halide’ are the least reactive because bully 7 Sroups hinder the approaching|r =r Nu: oy wa ® ® ‘o ; “wy - 2 Steric effects in Sy2 reaction. ‘The relative rate of Sy2 reaction is given in parenthesis AS Substitution nucleophitic unimolecular (Sq1) Sil reactions are general carried out inplanspatesluen's (ike water, alcohol, acetic acid, etc.). The reaction between butyl bromide and hydroxide ion yields tert-butyl alcohol and follows the first order kinetics; Le., the rate of reaction depends upon the concentration of only one reactant, which is tert-butyl bromide. (CH),CBr + OH ————> (CH),COH + Br 2-Bromo-2-methylpropane 2-Methylpropan-2-ol It occurs in two steps. In step I, the polarised C—Br bond undergoes slow cleavage to produce a carbocation and a bromide ion. The carbocation thus formed is then attacked by nucleophile in step II to complete the substitution reaction. cH, step I 9 (CH), ——— + BF HC cH, cH, : 4 on, ee (CH),COH HC CHa - )803)Haloalkanes and Haloarenesny Step lis the slowest and reversible. It involves the C-Br eae Sree frerey ts obtained through solvation of halide ton with the prot amvaepende see Sh the rate of reaction depends upon the slowest step. the rate of Fea ees only ont foncentration of alkyl halide and not on the concentration of bye alkyl halide Bret, the stability of carbocation, greater will be Its ease of formation from o alee and taste Will be the rate of reaction. In case of alkyl halides, 3° alkyl halides ee a . ler of rene tlon very fast because of the high stability of 3° carbocations. We can sum up ” TeACtivity of alkyl halides towards Sy1 and S,2 reactions as follows: For S,2 reaction, ‘Tertiary halide; Secondary halide; Primary halide; CH.X For S,1 reaction For the same reasons, allylic and benzylic halides show high reactivity towards the Syl reaction. The carbocation thus formed gets stabilised through resonance (Unit 12, Class XI) as shown below: noBeaf —— we-P-cHy 2 CH, 2. CH CH CH, — — — bd e Fe ‘or a given alkyl _ the reactivity of the halide, R-X, follows the same order in both the mechani sda RESO] In the following pairs of S,2 reaction faster? Opycneiana()-t; A ana Ng (-cinet itis primary halide and therefore undergoes S, Solution reaction faster. 7 halogen compounds, which would undergo ~N As iodine is a better leaving group because of its large size, it will be released at a faster rate in the presence of incoming nucleophile. Predict the order of reactivity of the following compounds in S,1 and S,2 pedctions: four isomeric bromobutanes: preneHere, ,CHIC,H,)Br. C,H CHICH Br, C,H,CICH,)(C,H BrSolution ( CHCH,CH,CH,Br < (CH), CHCH,Br < CH,CH,CH(BNCH, <(CH),CBr (S,) CHsCH,CH,CH,Br > (CH,),CHCH,Br > CH,CH,CHIBr)CH> (CHj),CBr (S,2) Of the two primary bromides, the carbocation intermediate derived from (CHy,CHCH,Br is more stable than derived from CH,CH,CH,CH,Br because of greater electron donating inductive effect of (CH,),CH- group. Therefore, (CH),CHCH,Br ts more reactive than CH,CH,CH,CH,Br in Sy1 reactions. CH,CH,CH(Br)CH, is a secondary bromide and (CH,)sCBr is a tertiary! bromide. Hence the above order is followed in.Sy1. The reactivity in S,2 Teactions follows the reverse order as the steric hinderance around the electrophilic carbon increases in that order. (i) CJHsC(CH,)(C.H,)Br > C,H,CH(C,H,JBr > C.H,CH(CH,JBr > CoHsCH,Br (Sy1) C,H,C(CH,)(C,H,)Br < C,H,CH(C,H,Br-< C,H,CH(CH)Br < C,H,CH,Br (S,2) Of the two secondary bromides, the carbocation intermediate obtained from CHHCHIC HY ig more stable than obtained from C,H,CH(CH,)Br because it is stabilised'by two phenyl groups due to resonance. Therefore, the former bromide is more reactive than the latter in S,1 reactions. A phenyl group is bulkier than a methyl group. Therefore, C,H,CH(C,HJBr is less reactive than C,H,CH(CH,)Br in §,2 reactions. } Stereochemical aspects of nucleophilic substitution reactions In order to understand the stereochemical aspects of substitution reactions, we need to learn some basic stereochemical principles and notations (optical activity, chirality, retention, inversion, racegaisation, etc.). Optical activity: Plane of plane polarised light produced by passing ordinary light through Nicol prism is rotated when it is passed through the solutions of certain compounds. Such ‘compounds are called optically active compounds. Th aris it is rotated is meastired by an ‘the compound rotates the plane ie right, i.e., clockwise direction, it for right rotating) or the d-form and is indicated by placing a positive (+) sign before the degree of rotation. If the light is rotated towards left (anticlockwise direction), the compound is said to ‘the Lform and a negative (-) sign is placed:before the degree of rotation. Such.(+) and (-) isomers of a compound are called optical isomers and the phenomenon is termed as optical ot Molecular as: and enantiomers: ,The observation that crystals of certain compounds exis e form of mirror images laid the foundation of modern stereochemistry. He demonstrated that aqueous solutions of both types of crystals showed optical rotation, equal in magnitude (for solution of equal concentration) but opposite in direction. He believed that this difference in optical activity was associated with the three dimensional arrangements of atoms in the molecules (configurations) of s@QhHaloalkanes and Haloarenes. J. Van't Hoff ana of crystals, Dutch sclentist, Selontet. ©. Le Bel in the same year (1874), indepenge®s i ement of four groups (valerety argued that the spatial arrangement oO one (lena und a central carbon attached to that, carbon are ene cenn ties ior image nae molecule is not superimpose: such a carbon ts called asymmetric carbon or storeoceae ‘The resulting molecule would lack symmetry and is referreg as asymmetric molecule, The asymmetry of the molecule gig with non superimposabily of mirror images is responsibjer€ the optical activity in such gi . a: The as) are also ol many day to pet aas “Mojects: ephere a cube, acone, ae al dential? their mirror images and can be superimpoeg? However, many objects are non their mirror images, For example, your left and; hand looker but you put your et hand hand by moving them in the same Tig do nreamann aes ‘objects which a superimposable on the image (tke a pay of hands) are said to be ‘and this property is known as chirality. lecules are opticaly ‘active, while the objects, which are, ‘The above test of molecular chirality can be applied to organic molecules by constructing models and its mirror images or by ‘three dimensional structures and attempting to ‘Superimpose them in our minds. There are other aids, however, that can assist us in recognising # Some common examples of chiral and Chiral molecules. One such aid is the precenee - : a asingle ‘carbon atom. Let us consider two simple moleciiles-propan: bu (Fig. 10.6) and their mirror images. ig. ‘and butan-2-ol PIG 10.8: B is miror image of A: Bis rotated by 180" and Cl obtained; C ts supertmposable on A, u ana __——_chematry salts© and its mirror image le {0.8 Identify chiral and achiral molecules in each of the following pair of compounds. (Wedge and Dash representations according to Class XI, ear" ‘H ‘Mirror image of | Rotated mirror image butan-2-ol E F 180° Bb 08: Ets mirror image of D; Ets rotated by 180° to get F and F is non superimposable on its mirror tmage D. Butan-2-ol has four different groups attached to the tetrahedral carbon and as expected is chiral. Some common examples of chiral = molecules = such _—as 2-chlorobutane, 2, 3-dihyroxypropanal, (OHC-CHOH-CH,OH), bromochloro-iodomethane (BrCICHI), 2-bromopropanoic acid (H,C-CHBr-COOH), etc. The _stéreoisomers related to each _other_as_non- superimposable mirror images are calle B in Fig. 10.5, and D and enantiomers, Enantiomers namely, melt int, i ive index, etc. They only differ with respect to the rotation of plane polarised light. If one of the in A mixture containing two enantiomers in equal proportions will have zero optical rotation, as the rotation due to one isomer will be cancelled by the rotation due to the other isomer. Such a mixture is known or_racemic modification. A racemic mixture is represent prefixing J before the name, for example (#) butan-2-ol. The process of conversion of enantiomer into a racemic mixture is own a8 race: ion. Fig. 12.1). H H ‘Hyg aC HsCin 0 4 OH Bw pr oo He Xe wr w (i) (i) CH,CHCH,CH, CH,CH,CH,CH,Br | Br (i) 1@Q%Haloalkanes and HaloarenesCH,CHCH,CH, — Solution, tif Retention: Retention of configuration is the preservation ofthe spay arrangement of bonds to an asymmetric centre during a chemye:t Teaction or transformation. a —= In general, if during a reaction, no bond to the stereocent the product will have the same general configuration of aroun, around the stereocentre as that of reactant. Such a reaction js gait to proceed with retention of the configuration. Consider as a, example, the reaction that takes place when (-)-2-methylbutan-) is heated with concentrated hydrochloric acid. (+2-Methyibutan-4-o1 (#}1-Chloro-2-methylbutane It is important to note that configuration at a symmetric centre in the reactant and product is same but the sign of optical rotation ha : Seen ae mens optical rotation) optical rotation). Inversion, retention and racemisation: There are three outcomes for a reaction at an asymmetric carbon atom, when a bond linked to an asymmetric carbon atom is broken. Consider the replacement of a group X by Y in the following reacti cH, on fare oh ’ tH x7 cH, —*, y7 Nou, B A Y A+B 7 | If (A) Is the only compound obtained, the process is called retentio. fi of configuration. Note that configuration has been ina. If (B) is the only compound obtained, the process is wwersiot I of configuration. Configuration has been inverted in B.If 50:50 mixture of A and B is obtained then the process is called racemisation and the product is optically inactive, as one isomer will rotate the plane polarised light in the direction opposite to another. Now let us have a fresh look at 5,1 and §,2 mechanisms by taking examples of optically active alkyl halides. In case of optically active alkyl halides, the product formed as a result of Sy2 mechanism has the inverted configuration as compared to the reactant. This is because the nucleophile attaches itself on the side opposite to the one where the halogen atom is present. When (J-2-bromooctane is allowed to react with sodium hydroxide, (#)-octan-2-ol is formed with the -OH group occupying the position opposite to what bromide had occupied. rw ton —ono-{i ne 7 OH —> HOH + Br eee Cats Thu: reactions of optically active halides are accompanied by In case of optically active alkyl halides, Sa reactions are accompanied by acest. Can you think of the reason why it happens? Actually the carbocation formed in the slow step being sP hybridised is planar (achiral). The attack of the nucleophile may be accomplished from either side of the plane of carbocation resulting in a mixture of products, one having the same configuration (the -OH cH, H,C: ° sel afscucn, * BF H,CH,C CH, HO, ” ‘y_CHs HC. Hof HO 8 on, POH CH,CH, — H ‘CH,CH, H CCH, (+)-Butan-2-ol “OH (Butan-2-01 attaching on the same position as halide ion) and the other having [Location of a and |. opposite configuration (the -OH attaching on the side opposite to halide B carbon in a ion). This may be illustrated by hydrolysis of optically active 2-pfomobutane, which results in the formation of (#)-butan-2-ol. Carbon on which \#@- Elimination reactions halogen atom is) When a haloalkane with B-hydrogen atom is heated with|/AIGOHGLG} directly attached is solution of potassium hydroxide, there is elimination of hydrogen called a-carbon and atom from B-carbon and a halogen atom from the a-carbon atom. the carbon atom vadjacent to this carbon is called B-carbon. tt of ex —— oa + BOH +X BzBase; X=Leaving group 309, Haloalkanes and Haloarenes4 as a product. Since B-hy As a result, an alkene 1s on it is often 2056 atom is involved in elimins one If there is possibility of formation of more, ee ee alkene ey the availabilty of more than one Prhydrogen atoms, Usually one alga is formed as the major. product. These at at tem ns observed by Russtan chemist. ‘Aes Zailo Reptialeo p cet who in 1875 formulated a rule whic! su = marised, ‘ = Be er oatcsenation reactions, the preferre roc ct te alkene which has the greater number of alkyl groups attached wt doubly bonded carbon atoms.” Thus, 2-bromopentane giv, Ppent-2-ene as the major product. Br x OH H.C-CH,-CH=cH-cH,<28_ H,C-CH-CH-CH-CH, > H,C-CH-CH,-CHi=cy, Pent-2-ene (81%) 2-Bromopentane. ©, ries Ged Elimination versus _ substitution A chemical reaction is the result of competition; it is a race that is won by the fastest Tunner. A collection of molecules tend to do, by and large, what is easiest for them. An alkyl halide with B-hydrogen atoms when reacted with a base or a nucleophile has two Competing routes: substitution (S,1 and S,2) and elimination. Which route will be taken up depends upon the nature of alkyl halide, strength and size of base/nucleophile and reaction conditions. Thus, a bulkier nucleophile will prefer to act as a base and abstracts @ proton rather than approach a tetravalent carbon atom (steric reasons) and vice versa. ‘Similarly, a primary alkyl halide will prefer a S,2 reaction, a secondary halide- S,2 or elimination depending upon the ‘strength of base/nucleophile and a tertiary halide- S,1 or elimination depending upon the stability of carbocation or the more substituted alkene. ‘Substitution. Reaction with metals metal organic chlorides, bromides and iodides r rtalt s to give compounds containing carbon-ment Pivis: Sut! compounds are known as organo-metailic compounds. At important class of organo-metallic compounds discovered ate Grignard in 1900 ts alkyl magnesium halide, RMgx, referred # Grignard Reagents, These reagents are obtained eee haloalkanes with magnesium metal ae ane CHLCH.by + Mg (@Sietner Secuees Grignard reagent Chemistry 310,chemist - he Victor Grignard had a strange start in academic Wfe for a Wook a maths degree, When he eventually switched to chemist tt was ta the mathematical province of physteal chemistry but fo orgeree chemistry. While attempting to find an ef catalyst for the process of methylation, he noted been used Jor this purpose and wondered whether ether combination might be ciieessful Grignard reagents were first reported in 1900 and, Grig used this work for his doctoral thests in 1901. In 1910 Grignard obt Grignard reagents are highly reactive and react with any source of proton to give hydrocarbons. Even water, alcohols, amines are sufficiently acidic to convert them to corresponding hydrocarbons. RMgx + H,O ———> RH + Mg(OH)X It is therefore necessary to avoid even traces of moisture from a Grignard reagent. is why reaction. ether. On the other hand, this could be considered as one of the met 1g halides to hy ons. Alkyl ser react i STE give hydrocarbons containing double the numt present in the halide. This reaction is known as Wurtz reaction (Unit 13, Class X1). 2RX + 2Na ———> RR+2NaX PResctlons of Aycleopii substitution Aryl halides are extremely less reactive towards nucleophilic cubst{tution reactions due to the following reasons: ‘Resonance effect : In haloarenes, the electron pairs on halogen atom are in conjugation with 1-electrons of the ring and the following resonating structures are possible. —§—B—3 ‘C—CI bond acquires a partial double bond character due to resonance. As a result, the Bort cleavage in Raloarene is difficult than haloalkane and therefore, they are less reactive towards nucleophilic substitution reaction. Haloalkanes and HaloarenesChemistry 3425 Difference in hybridisation haloalkane, the carbon al hybridised while in case of haloarene, to halogen ts sp?-hybridised. a _ . oo (ee bybra carbon) b (> (SP hybrid carbon ee ‘The sp? hybridised carbon with a greater S-character ts mo, electronegative and can hold the electron pair of C—x bon, more tightly than sp’-hybridised carbon in haloalkane wig, 1 wate Thus, C—€l length in haloalkane 4 of carbon atom in C—) ; (om attached to halogen 4," 4 the carbon atom atta,'?* Hach while in haloarene is . Since it 1s difficuit j ‘a shorter bond than a longer bond, therefore, hak are less reactive than haloalkanes towards nucleophyjj J , substitution reaction. AG Instability of phenyl cation: In case of haloarenes, the phen cation formed as a result of self-ionisation will not be stabilise by resonance and therefore, S,1 mechanism is ruled out, Because of the possible repulsion, it is less likely for the electrn rich nucleophile to approach electron rich arenes. Replacement by hydroxyl group Chlorobenzeneéan be converted into phenol by heating in aqueous sodium hydroxide solution at a temperature of 623K and a pressur of 300 atmospheres. 6. 6 ‘The presence of an electron withdrawing group (-NO,) at ortho- and para-positions increases the reactivity of haloarenes, HH No,tei OH ON. NO, ON NO, warm HO No, NO, ‘The effect is pronounced when (-NO,) group is introduced at ortho- and para- positions. However. ism of the reaction is as depicte OH on sa Gas ala sa 8 ofS of) o88 — ob8 leon? 8 @ g eon? ° NO o Slow step, ee 0 4 @)) 0H : oi 2 ei on? on 5 ©) Bo ms grt +0 Gl_OH lO Gn you think why does NO, group show its effect only at ortho- and para- positions aid not at meta- position? ‘As shown, the presence of nitro group at ortho- and para-positions withdraws the electron density from the benzene ring and thus facilitates the attack of the nucleophile | on haloarene. The carbanion thus formed is stabilised through resonance. The negative | | | | charge appeared at ortho- and para- positions with respect to the halogen substituent 1s | stabilised by -NO, group while in case of meta-nitrobenzene, none of the resonating | structures bear the negative charge on carbon atom bearing the -NO, group. Therefore, ‘of nitro group at meta- position does not stabilise the negative charge and the no effect 5 reactivity is observed by the presence of -NO, group at meta-position. (gm Haloalkanes and Haloarenes __AC Btectrophitic substitution reactions Haloarenes undergo the usual electrophilic reactions of the p, ring such as halogenation, nitration, sulphonation and Friede}-¢2% dactons. Halogen atom besides being slightly deactivating 4, oh directing; therefore, further substitution occurs at ortho- rab Positions with respect to the halogen atom. The o, p-directing influe of halogen atom can be easily understood if we consider the *esonaty structures of halobenzene as shown: X g £ 2 y cs o a I Il mm Iv Due to resonance, the electron density increases more at ortho. Pare-Positions than at meta-positions. Further, the halogen a, because of its -1 effect has some tendency to withdraw electrons the benzene ring. As a result, the ring gets somewhat deactivated compared to benzene and hence the el stitution reaction, in haloarenes occur slowly and ® Ferrer ea a cl (eo + ci, Ambyd Pech, + 124 1 4 Dicorobenzene ae} 8 Nitration e ct HNO, NO, “cone. 1,50,” + No, 1-Chloro-2-nitrobenzene (Minor) ya Sulphonation er ci ch o== co e ; fonic acid 2-Chlorobenzenesulfonic acid (Minor)Sif Priedel-crans reaction ch el el CH, Oo +cH,0) Anny alc or + CO CH, 1-Chloro-2-methylbenzene ls (Minor) oe ne ch O FS wold Anhyd. AIC, clo I ‘CH, 2-Chloroacetophenone CH, = “ai Although chlorine is an electron withdrawing group, yet it is ortho-, Para- directing in electrophilic aromatic substitution reactions. Why? Solution Chlorine withdraws electrons through inductive effect and releases slettians through resonance. Through inductive effect, chlorine stabilises the intermediate carbocation formed during the electrophilic substitution. cl + Oh (sy — es Inductive effect destabilises the intermediate carbocation Cl: rl HH (attack at ortho-position) +? — ; : Ch (attack at para-position) +p —— Ce EOH Resonance effect stabilises the intermediate carbocation Through resonance, halogen tends to stabilise the carbocation nounced at ortho- tends to oppose the inductive effect Bel at ortho aed cae positions and hence makes the deactivation less for pare Pitack, Reactivity is thus controlled t :cleaved A Reaction with metals fu aon an alkylaren ema ae a halide and aryl halide era Heeig ene Whey, treated with sodium in dry ether and Is calle tio R Dry ether NaX Oo + Na +RX ——~ Co . Fittig reaction hen treated with sodj analogous compounds wi tum thy ether in nich two aryl groupe aze Joined together. 1t 1 cag Fittig reaction. ; on ona DUS +2NaX Diphenyl .7 Which alkyl halide from the following pairs would you expect to react more rapidly by an S,2 mechanism? Explain your answer. Vv -_ cH, 80 CH,CH,CH,CH.BY or crtcriHon,W cncngricn, or HC-¢—Br ee : oa, (Gi cH,cHcH,cH.BF or CH,cH,CHCH,E 196 In the following pairs of halogen compounds, which compound undergoes faster Sv Identify A, B, C, D, E, R and -R’ in the following: (br + a yether, , HO, Bp Rr + Mg —dvether, ¢ _DO, CH.CHCH, CH, CH, D Na/ether pi x ME, 110.7 Polyhalogen Compounds containing more than one halogen atom are usuall 10.7.1 Dichloro- methane (Methytene chloride) chloride’ 1uman central nervous levels of methylene chloride in air can lead to slighily impaired h and vision. levels of methylene chloride in air cause d | - nausea, tingling and numbness in the fingers and toes. In humans, direct skin contact with methylene chloride eee a mild redness of the skin. Direct contact with the eyes can 10.7.2 Trichloro- Chemically, chloroform is employed as a methane —_iodine and other substances. Th (Chloroform) the production of the It was once used as a sthetic in surgery but has bee toxie, fer anaesthetics, such as ether. As might be ‘ted from its use a5 an anaesthetic, inhaling chloroform vapour ‘nervous system. Breathing sboat 0 po chlorofo: i parts of air (900 parts per million) for a short time can cause dizziness, fatigue, and headache, Chronic chloroform exposure may cause damage to eta )) and to the kidneys, ‘and some people develop sores when the skin is immersed in owly oxidised ‘by air in the presence of | for fats, alkaloids, loroform today is in 10.7.3 Triiodo- methane (lodoform) to its objectionable smell, it has been replaced by other formulations containing todme. 10.7.4 Tetrachio- It is produced in large quantities for use in the manufacture of romethane ‘refrigerants and propellants for aerosol cans. It is also used as (Carbon feedstock in the synthesis of chlorofluorocarbons and other chemicals, tetrachloride) pharmaceutical manufacturing, and general solvent use. Until the mid 1960s, it was also widely used as a’ cleaning fluid, both in industry, as a degreasing agent, and in the home, as a spot remover and as fire extinguisher. There is some evidence that exposure to carbon tetrachloride rin humans. The most common effects are dizziness eadedness, nausea and vomiting, which can cause pernianent damage to nerve cells. In severe cases, these effects can lead rapidly to s yusness or death. Exposure to CCl, can make .e chemical may irritate @ eyes on contact. When carbon tetrachloride is released into the air, it rises to the atmosphere and depletes the ozone layer. Depletion of the (aiHaloalkanes“ahd Haloarenes___: re to ultra ozone layer is believed to increase humar | aengiter teewlet ny, leading to increased skin cancer, 8 oa. TS, ant Possible disruption of the immune sy°" 10.7.5 Freons The jown. ; thane by Swarts Tem These are usually progys® for aerosol propellants, refrigeration ca a oe oat Ses, 1974, total freon production in the worl \(@RAWAlly. Most freon, even that used in refrigeration, eventually changed into its way into the atmosphere where it diffuses unt it stratosphere. In stratosphere, freon is able to initiate radical reactions that can upset the natural ozone balance (Unit'14, Class yy 10.7.6 p,p’-Dichlo- DDT, HF (CH),CBr + KOH —£thanol eat yx CH,CHIBNICH,CH, + NaoH —Wwater_, VW Ercnsr + Kon 24 éthanol , PTEHONA + 04,01 (CH,CH,CH,OH + soc, + aT on,cH,cH = cH, + npr Peroxide wf CH,CH = C(CH), + HBr YAS Write the mechanism of the following reaction: nBuBr + KCN «_EtOH-H,O nBuCN haw Arrange the compounds of each set in order of reactivity towards S,2 lacement: 0) () J-Bromo-2-mpthylbutane, 1-Bromopentane, 2-Bromopentane, 2 1-Bromo-3-methylbutane, 2-Brotio-2-methylbutane, 2-Bromo-3-methylbutane (tit) 1-Bromobutane, 1-Bromo-2,2-dimethylpropane, 1-Bromo-2 1-Bromo-3-methylbutane. 2647 out of GH,CH,Cl and C,H,cHeIC KOH. Oe ee How the following conversions can be carried out? Propene to propan-1-ol ‘thanol to but-1-yne 1-Bromopropane to 2-bromopropane -methylbutane, which ts more easily hydrolysed by aqueous chemistry sie‘oluene to benzyl alcohol Benzene to 4-bromonitrobenzene Benzyl alcohol to 2-phenylethanole acid . ‘anol to propanenitrile iline to chlorobenzene }-*Chlorobutane (0 3, 4-dimethylhexane ZMethyl-1-propene to 2-chloro-2-methylpropane ans chloride to propanoic acid . fut-l-ene to n-butyllodide Spa cia to 1-propanol ‘propyl alcohol to fodoform | Chlorobenzene to p-nitrophenol Ep Bromnropane to 1-bromopropane Chloroethane to butane Gey Benzene to diphenyl Butyl bromide to isobutyl bromide Aniline to phenylisocyanidé aleoholic KOH, alkenes are major products. Explain. 10.21 Primary alkyl halide C\H,Br (a) reacted with alcoholic KOH to give compound (b). Compound (b) is reacted with HBr to give (e) which is an. isomer of (a). When (2) ts reacted with sodium metal it gives compound (4), C,H, which is different from the compound formed when n-butyl bromide is reacted with sodium, Give the structural formula of (a) and write the equations for all the reactions, 10.22 What happens when n-butyl chloride is treated with alcoholic KOH, bromobenzene is treated with Mg in the presence of dry ether, chlorobenzene is subjected to hydrolysis, JA cthyl chloride is treated with aqueous KOH, thyl bromide is treated with sodium in the presence of dry ether, “yrmethyt chloride is treated with KCN? Answers to Some Intext Questions C) 10-1 (i) CH,CH,CHICH,CHCICH, w) Ol (61) CH,CH,CH,CH CH(JCH,CH, (iv) BrCH,CH = CHCH,Br 1 HyC—C-CH, ” on co 4 oc ‘CH, bi Ho 10.2 (i) H,SO, cannot be used along with KI in the conversion of an alcohol to oe alkyl iodide as it converts KI to corresponding acid, HI which is then oxidised by it to 1,. 10.3 (i) CICH,CH,CH,CI (i) CICH,CHCICH, (ii!) Cl,CHCH,CH, (1v) CH,CCI cH, Szeh Haloalkanes and Haloarenes