Haloalkanes and Haloarenes POINTS TO 1, Haloalkanes or alkyl halides are the compounds which have the general formula RX, where R is an alkyl or substituted alkyl group and X is a halogen (F, Cl, Br, I). Likewise, Haloarenes or Aryl halides are the compounds containing halogens attached directly to an aromatic ring, They have the general formula ArX (where Ar is phenyl, or substituted phenyl), RX ArX Analky! halide Anaryl halide (Haloalkane) (Haloarene) R= Alkyl or substituted alkyl Ar-= Phenyl or substituted phenyl X=F,CLBr,1 X=F,CLBr,1 (Classifieatior (a) Classification based on the number of halogen atoms: These may be classified as mono, di, or polyhalogen compounds depending on whether they contain one, two or more halogen atoms in their structures. For example, 5 = ma | wn 4 S) 2) ima mS i = (ee) m ze, CH,X, tT CoHsX I CHX CH.X i cHx Monobalolkane Dinatoatkane “Tahalalhane x os goo (on je Monobaloarene Dihaloarene Dihalogen compounds may be further clussified as discussed below: © Gem-dihalides: The two halogen atoms are attached to the same carbon atom in gem-dihalides, Foreaanpl wow an weet wena hah ha Isopropylidene chloride ‘Ethylidene chloride ,3-Dichloropropane) (.1-Dichloroetiane)foe lu co =a peu) >a lu ia e) F wn eR < le) io ‘© Vic-dihalides: In these compounds, the two halogen atoms are attached to adjacent carbon atoms. For example, a cl-cH,—CH,—C1 CH,—CH—CH,—¢1 "Byles dle Propper chore (6,2 Diherohane (0,2 Dactenopopane) (®) Classification based on hybridisation of carbon atom: (@ Halogen compounds in which halogen is bonded to sp* hybridised carbon. This class includes: (@) Haloalkanes or alkyl halides: They are the halogen compounds of saturated hydrocarbon. ‘Their general formula is C,H, 4:X. They are further classified as primary haloalkane, secondary haloatkane or tertiary haloalkane according to whether the halogen atom is bonded to primary, secondary or tertiary carbon atom. H R ! xd R' ae R' ft H H Primary halalane Secondary halolkane If in R—X, R is an alicyclic, Ze., cyclic aliphatic hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, etc, they are known as halocycloalkane or cycloalkyihalide. For example, x du +H,C- H,C—CH—X ad Yu | >cu-x II Lt HC H,C—CHy HyC — CH Halocyclopropane ‘Haloeyclobutane Halocyclopentane (b) Allylic halides: In these compounds, halogen is bonded to allylic carbon, ie., to the sp? hnybridised carbon atom next to a carbon-carbon double bond. Examples are: (CH=CH—CH, x Aliythatige (3-Halopop- Lene) 3 Haleysioher Lene (¢) Benzylic halides: In these halides, the halogen atom is bonded to an sp’ hybridised carbon ‘alo next to an aromatic ring, i. to a benzylic carbon. For example, x ® x coe CO Of Benzyl halide Leitalo-,2,3,4 _Dialkybenzyt halide terahydr naptalene Benzylic halides may be primary, secondary or tertiary. (ii) Halogen compounds in which halogen is bonded to sp* or sp hybridised carbon. (@) Vinylic halides: In these halides, halogen is bonded to one of the carbon atoms of a vinylic carbon, i.e., carbon-carbon double bond which is sp” hybridised. The examples are : — or Vinyl halide 1-Halocyclohex-Iene(®) Aryl halides: In these halides, the halogen atom is directly bonded to carbon atom of aromatic, ting. These are called haloarene or aryl halides, e.g., halobenzene, CG = 2 Common and TUPAC names of some halides: ‘Table 6.1: Common and IUPAC Names of Some Halides cH ety he aes = cua —aI =F re oe S) cHy i Isopropyl hlrige 2-Chlorpropane ze) cH —CH—c1 m (CH,—CH,—CH,—CH,—C1_ ‘n-Butyl chloride 1-Chlorobutane_ rd (CHy—CH,—CH—CHts m 1 sec-Butyl chloride 2-Chlorobutane “ Es ‘CHs i iaateay eect i ceaceee etal fue] CH, —CH—CH,—cL m CH; ie a eS tert-Butyl bromide ‘2-Bromo-2-methylpropane Br cH | Cec ‘neo-Pentyl bromide 1 -Bromo-2,2-dimethylpropane CH, CH I Tsopentyl chloride 1-Chloro-3-methylbutane CH, —CH—CH,—CH,—C1 CH=CH Vinyl ehloride Chloroethene (CH,=CH—CHy—Br Allyl bromide 3-Bromoprop-l-ene CHa, Methylene chloride Dichloromethane CHC, Chloroform ‘Trichloromethane CCl, Carbon tetrachloride Tetrachloromethane Is 2-Chorotoluene cl ‘o-Chlorotoluene or 1-Choro-2-methyibenzene I—Ch Benzyl chloride Chlorophenylmethane3. Methods of Preparation of Haloalkanes (@) From alcohols: Alky! halides are best prepared from alcohols, which are easily accessible. za ROOH + HX ME. RX +HLO (X= Br, 1) R—OH +NaBr + H,SO, ——- R—Br + NaHSO, + HO 3R—OH + PX; ——~ 3R—X + H3PO3 (X=CI,Br) ROH + PCl, ——~ RCI + POC}, + HCL Rel Ps ROH SEE RX ROH + SOC, —~ RCI + SO. + HCI ‘The reactions of primary and secondary alcohols with HX require the presence of the catalyst, ZnCl. ja lu faa) = pea) 7 lu a) [e) ad Va) — 2 (2) (ey (®) From hydrocarbons By free radical halogenation: aa oye i,CH, CH,CH,, na ~ CH;CH,CH,CH,CI + CH,CH,CHCICH, ‘n= Butsne “ ‘n=Buiyl chloride ‘sec~Butyl chloride Cts CH | ve | Bie ais + Ch Chit + HCL CHs CHs iaiReee eo Peg code (c) From alkenes (@ Addition of hydrogen halides Scacc + HEX ——- Dec (k= BrD a at Po “ths, ee I od ae ak Ne R=CH-CH; + Bx See. R—CH—CHs x er, coy poi ROCHE CHe + HTP Gemimtatorov aia” CH CHa Br Gi) Addition of halogens # H Scaccl + Bry —8> Brc—CHBr H SH i e-Dibromide (@) Halide exchange (@ By Finkelstein reaction ROX + Nal PVE. RI + Nox 1, Br) (ii) By Swarts reaction RX ABHEBCOR OSG pp (CH,—Br + Agf — CH,—F + Agbr4, Physical Properties of Haloalkanes (a) Melting and boiling point: Haloalkanes have higher boiling points as compared to those of corresponding alkanes, This is due to their polar nature and strong dipole-dipole interactions between their molecules. ‘The boiling points of haloatkanes are in the order RCI < RBr (acetiaoa) e-Chlrosctopcrone ‘OCH poe oS “inornicd (sor protic) % (@) Stereoisomerism: Isomerism exhibited by two or more compounds with the same molecular and structural formulae but different spatial arrangements of atoms or groups in space is called stereoisomerism, () Plane-polarised light: The beam of light whose oscillations or vibrations are confined to one plane only is called plane-polarised light. It is obtained by passing a monochromatic light (light of single wavelength) through a Nicol prism, (c) Optically active substances: Those substances which rotate the plane of polarisation of plane- polarised light when it is passed through their solutions are called optically active substances. This phenomenon is called optical activity. (@) Optical rotation: The property of rotating the plane of polarisation either towards eft or towards right is called optical rotation. (@ Laevorotatory: Those substances which rotate the plane of polarisation of light towards the left direction are called laevorotatory. (i) Dextrorotatory: Those substances which rotate the plane of polarisation of light rowards right are called dextrorotatory. Currently, dextro and laevo rotations are represented by algebraic signs of (+) and (), respectively. (6) Specific rotation: Specific rotation is defined as the number of degrees of rotation observed when the concentration of optically active substance is |g em”® and length of polarimeter tube is 1 decimetre (dm) for D-line of sodium vapour lamp at 25°C. Observed rotation (01...) Specific rotation [ol] =| ———____SENCE ARNON (gs) _____ Length of tube (dm) * Concentration of solution (g mL“) While reporting (al, the wavelength of light used is given as subscript and the temperature (in degrees celsius) as a superscript. It is also customary to designate the solvent and concentration. ‘Thus, [a]° = - 2.25° (C; 0.50 ethanol) means that « was measured at 25°C using sodium D-line and. the sample concentration was 0.50 g/ml. in ethanol. (P Asymmetric molecule: If all the four substituents attached to carbon are different, the resulting molecule will lack symmetry. Such a molecule is called asymmetric molecule. Asymmetry of molecule is responsible for optical activity in such organic compounds. (@) Chiral: An object which is non-superimposable on its mirror image is said to be chiral. The property of being chiral is known as chirality. vu = Z = Va) =) e) v2) a < ua < wo a Aja rm fan) = ir a i jaia§ fe) F rv) eR = (e) fee 10, (h) Asymmetric earbon: The carbon atom which is attached with four different groups of atoms is called asymmettic carbon, The molecule having asymmetric carbon atom is called asymmetric. (@® Enantiomers: The stereoisomers which are non-superimposable mirror images are called enantiomers. Enantiomers rotate the plane of polarised light to the same extent but in opposite direction. @ Racemic mixture: An equimolar mixture of a pair of enantiomers is called racemic mixture, A racemic mixture is optically inactive due to external compensation. (&) Racemisation: The process of conversion of an enantiomer into racemic mixture is known as racemisation, (© Resolution of a racemie mixture: Resolution is a process of separating a racemic mixture into its ‘enantiomer constituents, i, dextto d{+) and laevo-rotatory 1(-) substances. (mm) Meso compounds: The compounds containing two or more chirality centres but possessing achiral molecular structure because of having plane of symmetry are called meso compounds. A meso ‘compound is optically inactive due to internal compensation. (n) Diastereomers: The stereoisomers which are non-superimposable and do not bear a mirror-image relationship. (0) Retention: if in an optically active molecule the relative configuration of the atoms/groups around a chiral centre remains the same before and after the reaction, the reaction is said to proceed with retention of configuration. () Inversion: If the relative configuration of stoms/groups around a stereo centre in the product is opposite to that in reactant, the reaction is said to proceed with inversion of configuration. ‘There are three outcomes for a reaction at an asymmetric carbon atom. Consider the replacement of a group X by Y in the following reaction: Day GH; Hs Ln Ke ss / _t, CH, ‘CH; 3 ¥ iB d f , A+B If (A) is the only compound obtained, the process is called retention of configuration. If (B) is the only compound obtained, the process is called inversion of configuration. ‘If 50 : 50 mixture of the above two is obtained then the process is called racemisation and the product is optically inactive, as one isomer will rotate light in the direction opposite to another. Mechanism of Nucleophilie Substitution in Alkyl Halides ‘The nucleophilic substitution reactions in alkyl halides can take place by either of two mechanisms: Syl and Sy2 Substitution nucleophilic unimolecular (Sy) It takes place in two steps and the reaction is of first order. In the first step, alkyl halide undergoes slow heterolysis to produce carbonium ion (an intermediate) and a halide ion. In the second step, nucleophile rapidly combines with the carbonium ion to complete the substitution reaction. R R Step 1: ke x se goo 4x Cabo on (ferme) Rg R Step 2: RSC + Nu + Rc he Sx! reactions of optically active halides are accompanied by racemisation. This is because the carbonium formed in the slow step being sp" hybridised is planar (achiral) therefore, the attack of nucleophile on it can‘occur from both the faces with equal ease giving a mixture containing two enantiomers in equal amounts. ‘This may be illustrated by hydrolysis of optically active 2-bromobutane, which gives (+) butan-2-o1. Hy Hy Hew Br + Br He HCH. ‘CH;CHs ()0r@)2-Bromobutane Carboni ion /WN8 4 i 40 in i en er [ON ete version i ssc, ‘CHCH,, HCH,C Substitution nucleophilic bimolecular (Sy2) It takes place in one step and the reaction is of second order. In this process the nucleophile attacks the partially positive carbon of the C—X bond of the substrate, alkyl halide, from the back side of the C—X bond and the leaving group, X", departs simultaneously. tL i i Nu + ie —_—— wx ——> Nu H x wf u/ Na “eansiton state ‘S,2 reactions of optically active halides are accompanied by inversion of configuration. This is because the attack of nucleophile occurs from a direction opposite to the one from where the halogen atom leaves. ‘The order of reactivity of alkyl halides towards Sw1 and Sy? reactions is as follows: ‘Sylreactivity increases CHAX RCHX, ee R » > ‘S,2 reactivity increases ‘An alkyl group at the a-carbon, being bigger in size than H atom, tends to block the approach of the nucleophile to carbon due to steric hindrance in $y? mechanism and makes the reaction difficult to occur. In the S41 mechanism, a carbocation is formed in the first, slow step. The mote stable the carbocation, ‘more easily is the product formed. Tertiary alkyl halides undergo Syl reaction very fast because of the high stability of tertiary carbocation. CHy < RCH, < R—CH—R’ < R-C—4 EL Primary allylic and benzylic halides show higher reactivity in Syl reactions than other primary halides This is due to stabilisation of allylic and benzylic carbocation intermediates by resonance. 2 @ cH cli, cH=cH, Resonance inalyl eboetion $-§-8-8 Resonance stabilisation in benzyl carbocation vu = a = Va) =) e) v2) a < ua < wo a az‘Thus, primary alkyl halides always react predominantly by Sy2 mechanism. Tertiary alkyl halides react predominantly by Sy mechanism. Secondary alkyl halides may react by both the mechanisms without ‘much preference. Polar solvents favour Syl and non-polar solvents favour S,2 reactions. 1, Polyhalogen Compounds: Carbon compounds containing more than one halogen atom are usually referred to as polyhalogen compounds. Many of these compounds are useful in industry and agricutture. ‘Some polyhalogen compounds are described as follows: (@) Methylene chloride (Dichloromethane): It is prepared industrially by the direct chlorination of methane, chy +2 "> CHCl, + 281 Uses: Itis an effective solvent used in pharmaceutical and food industry. (b) Chloroform (Trichloromethane): It is manufactured by chlorination of methane followed by separation by fractional disilation. (CH, + 3Ch * wage CHCh + 3HCI Properties: (@ It is a sweet smelling liquid with boiling point 61°C. (di It is stored in dark coloured bottles because it gets oxidised in the presence of sunlight to form a poisonous gas, phosgene (COCI). 2CHCl; + 0) —“~ 2COC1, + 2HCI {cis therefore stored in closed dark coloured bottles completely filled so that air is kept out. 1% ethanol is added so as to convert phosgene gas to diethyl carbonate which is non-volatile and non- toxic. [oe lu a a peu) >a lu ce e) F n eR rs le) oe COC! + 2CzHsOH —~ (C2Hs)2CO; + 2HCL Diethyl atone Uses: (@ It is widely used in industry as a solvent for fats, waxes, resins, rubber, etc i) I was once used as an anaesthetic agent in surgery and as flavouring agent in cough syrups but ‘now itis not used because it forms phosgene gas which is poisonous. (€) Triiodomethane (Iodoform): fodoform is prepared by the action of iodine and alkali on ethyl alcohol ‘or acetone, Reactions involved in the preparation of fodoform from ethyl alcohol are: 2NaOH + 1; —~ Nal + | NaOl + HO ‘Sot boise CaHsOH + Naor 8" CHCHO + 3N201 CHsCHO + Nal + H20 Bit. C1,CHO + 3NAOH Toa CLCHO + NaoH 4" CHI,1 + HCOONa Indfors Som frie ‘The complete reaction may be written as: CH,CH,OH + 41, + 6Na0H ——~ CHI, | + HCOONa + SNal + 5H,O However, when sodium carbonate is used in place of sodium hydroxide then the complete reaction, may be written as: CH;CH,0H + 4l, + 3Na,CO; —~ CHI; | + SNal + HCOONa + 3CO; + 2H;0 Reactions involved in the preparation of fodoform from acetone are: OCR HNL — Ey C22 NSO, ° °Cl,—C—CH, + 3NaOH —— CHI;} + CH;—C—ONa Il Totoform Il ° a) ‘The reaction of iodine and sodium hydroxide or iodine and sodium carbonate to give yellow precipitate ‘of iodoform is called iodoform reaction. CH,CHO + 31, + 4NaOH —- CHI, + HCOONa + 3Nal + 3H,0 On I CH;—CH—CH; + 4k; + 6NaOH ——~ CH! + CHsCOONa + SNal + SHO Fropan- 2-31 CH,COCH, + 31, + 4NaOH —= CHIy| + CHyCOONa + 3Nal + 3H,0 Prego (CHCOCH,CH, + 31; + 4NaOH — CHI, | + CHyCH,COONa + 3Nal + 3H,0. Physical properties: odoform is a yellow coloured solid having m.p. 392 K. Itis insoluble in water but dissolves readily in ‘organic solvents, Uses: It is used as an antiseptic for dressing wounds. ‘The haloform reaction is commonly used to distinguish between methy! ketones of methyl carbinols ‘from other Ketones and alcohols. (@) Carbon tetrachloride (Tetrachloromethane): It is prepared by chlorination of methane and by action of chlorine on C3, in presence of AICI, as catalyst cs, +30, M2 cc + S4Ch ine wots CH, + acl, “+ cl, + 4HCI Properties: (@ CCl, is a colourless liquid with boiting point 350 K. (ii) Ithas a sickly sweet smell Uses: It is produced in large quantities for use in the manufacture of refrigerants and propellants for zerosol cans. Its also used as feedstock in the synthesis of chlorofluorocarbons and other chemicals, ‘pharmaceutical manufacturing, and generally used as a solvent. There is some evidence that exposure to carbon tetrachloride causes liver cancer in humans. The most common effects are dizziness, light-headedness, nausea and vomiting which can cause permanent damage to nerve cells. When ‘carbon tetrachloride is released into the air, it rises to the atmosphere and depletes the ozone layer. (€) Freon: The chlorofluorocarbon compounds of methane and ethane are collectively called freons, It is manufactured from CCI, by Swarts reaction. 3CCl, + 2SbF, 3CCILF + 2SbCl; ‘ieon-12 ‘ste, Properties: (@ Dichlorodifluoromethane (CC1,F,, Freon-12) is one of the most common freons in industrial use. (ii) They are extremely stable, unreactive, non-toxic, non-corrosive and easily liquifiable gases. Uses: ‘They have also been used extensively as propellants, for aerosols and foams to spray out deodorants, cleansers, hair spray, shaving creams. Use of freon is being reduced and banned because they are responsible for ozone layer depletion. vu = a = Va) =) e) v2) a < ua < wo a azfoe lu co =a peu) >a lu ia e) F wn eR < le) io (f DDT @,p'-Dichlorodiphenyl trichloroethane): Itis a white powder insoluble in water, but soluble in oi. It is used as an insecticide. It fails in pollaon doe to to cxteme sui. Ns now iO) biodegradable. Many species of insects developed resistance 10g, Gra DDT, and it was also discovered to have high toxicity in fish. The ‘chemical stability of DDT and its fat solubility compounded the por problem. DDT is not metabotised rapidly by animals, 12. Important Name Reactions (a) Sandmeyer's Reaction: Benzene diazonium chloride is converted to chlorobenzene, bromobenzene, cyanobenzene on treatment with CuCVHC1, CuBd/HBr and CuCN/KCN, respectively. 1 Oo +m (Chlorobenzene Br ne Gu Ne cr Sa § -« () Finkelstein Reaction: Chloroalkanes or bromoalkanes are converted into corresponding iodoalkanes bby treating with sodium iodide dissolved in acetone. CH;CHSC1 + Nal —°?*"". CH,CH,I + NaCl Enylehande Btyliate Dry atone CH,CH:Br + Nal CHyCHyI + NaBr ‘yt bre ide (©) Wurtz Reaction: Alkyl halides react with metallic sodium in the presence of dry ether to form alkanes. ‘This reaction is used for the preparation of higher alkanes, For example, CH;Br + 2Na + Br—CH, —"™" CH,CH, + 2NaBr ety Bomie ‘ime oe cH, CH, CH, CH,—CH—Br + 2Na + Br—CH—CH, 22". CH, —CH—CH—CH, + 2NaBr eps mie "23-Dinady ane ‘Wurtz reaction is only useful for the preparation of alkanes containing even number of carbon atoms and not for the alkanes containing odd number of carbon atoms. (@ Wortz-Fittig Reaction: Aryl halides when treated with alkyl halide and sodium in dry ether give alkylbenzenes. Opoemes cra, + Gay «ama Opa + ava + cc, > G)-cu + ar(©) Fittig’s Reaction: In this reaction two molecules of haloarene combine with metallic sodium in the presence of dry ether to give diphenyl or biphenyl. Oper + m+ GS) BH GS) + mac Dipkenylorbipteny (P Friedel-Crafts Alkylation: Benzene and other aromatic compounds react with alkyl halides in the presence of anhydrous AICI; to form alkyl benzene. Hy © + cry. state + HCI Benzene Toluene Hy +H; ewer, CH, ae ot Tobiene oXylene yh Hy pXylene (@) Dow's Process: When chlorobenzene is treated with an aqueous solution of NaOH at 623 K, 300 atm pressure sodium phenoxide is formed which on acidification gives phenol. ql Na OH vu = a = Va) =) e) v2) a < ua < wo a az sno ENE SO) A (h) Tlunsdiecker’s Reaction: Bromoalkanes are obtained by this method by refluxing silver salts of fatty ‘acids with Br, in CCl,. R—COOAg + Br, R-Br + AgBr + CO,T CHCH:COOAg + Brs = CHsCH2Br + AgBr + COs? ‘This method can be employed to decrease the number of carbon atoms. @ Gatterman’s Reaction: The reaction of diazonium salts with *Cu’ powder in the presence of corresponding halogen acids is known as Gatterman’s reaction. Ora 8 Opasnt Njcl —See# ‘Br + Njt+ HCL ©>» Oy aeens 13. Distinctions between Pairs of Organic Compounds Containing Halogen Silver nitrate test: In this test, the halide is warmed with aqueous or alcoholic KOH. ‘The solution is then acidified with dil. HNO, followed by addition of AgNO, solution Alkyl, benzyl and ally! halides give precipitate. Aryl and vinyl halides do not give precipitate. It may be noted that the precipitate formed should be insoluble in HNO,.Qn Ans. a2 Ans. Ans, ‘Write the structures of the following compound: ( 2-Chloro-3-methylpentane (i) 1-Chloro-4-ethyleyctohexane (ii) 4-tert-Butyl-3-iodoheptane (iv) 1, 4-Dibromobut-2-ene (0) 1-Bromo-4-sec-butyl-2- methylbenzene C1 (0 Chiy— Creat “i Lo cl cH (Gi) CHC —CH-CHCHCHACH, Go) BICHCHCHCH Be I T CCH); CHs o cH, —ch OHO) CH; ‘Why is sulphuric acid not used during the reaction of alcohols with KI? H,SO, cannot be used along with KI in the conversion of an alcoho! to an alkyl iodide as it converts KI to. corresponding HI and then oxidises it to I. Write structures of different dihalogen derivatives of propane. () CICH.CHCHLCI ( CICH,CHCICH, (iid) C1,CHCH,CH, (iv) CH,CCLCH,, ag to GX Cf Nai Se chlorination yields () Asingle monochloride [CBSE (F) 2017) (@ Three isomeric monochlorides (i) Four isomeric monochlorides (d All the hydrogen atoms are equivalent and replacement of any hydrogen will give the same product. Ci I BjO—0 ch pi CH; Gif) The equivalent hydrogens are grouped as a, b and ¢. The replacement of eq give the same product. lent hydrogens will (C7H,C°H,C’H,C°H,C'H, pentane (Gii) Similarly the equivalent hydrogens are grouped as a, b, cand d. Thus, four isomeric products are possible. C*H,CHHCH, CH, | ‘2-methylbutane CHE .. Draw the structures of major monohalo product in each of the following reactions: ou CH,CH, oe 0 Cy” +s0a, — “ LS ue tare OW cin a) SCY +H Ht. a or Ms an HO (0) CHsCH,Br + Nal — oo oO +B Sion Ans. ()) Co + soc, ——> pa + SO, + HCl Cycaeaol Chersylexae Br H;—CH; HCH; w sapcsine Oat Wie ON ‘+ethylnitrobenzene 41-Bromoethy!) nitrobenzene +cH,0H - “CHCl Gi oo 20" ee ot ue He H ‘tydymatpbna 4+Chlromeiyphena Only aleohotie but not phenolic OH groups are replaced by Cl on heating with HCL CH: 1H: * Ci a gg Mark adn Cr b Methyleyetohexone |odo-L-methyleyelohexane (») CH,CH,—Br + Nal ——+ CH,CH,—I + NaBr Iodide ion is a strong nucleophile and hence it displaces bromide ion. 0 OJ +3_ i ‘e + HBr 3:Bromocyelohexene Q.6. Arrange each set of compounds in the order of increasing boiling points. (® Bromomethane, Bromoform, Chloromethane, Dibromomethane. (W 1-Chloropropane, Isopropyl chloride, 1-Chlorobutane. Ans. (j) Chloromethane < Bromomethane < Dibromomethane < Bromoform. Boiling point increases with increase in molecular mass. (i) Isopropyl chloride < 1-Chloropropane < 1-Chlorobutane. Isopropyl chloride being branched has lower b.p. than I-Chloropropane. Q.7. Which alkyl halide from the following pairs would you expect to react more rapidly by an S,2 ‘mechanism? Explain your answer. @ CHCHLCH CH rr CH,CH,CHEH, Br CH; | w CEM or nei Br CH; Git) CH CHCH,CHBr or CHC CHCH Be CH CH Ans. (i) CHJCH,CH,CH,Br Being primary halide, there won’t be any steric hindrance. Gi) CHjCH,CHCH, — Being a secondary halide, there will be less crowding around a-carbon than tertiary halide. Br (iii) CHyCHCH;CHBr The presence of methyl group closer to the halide group will increase the steric hindrance and decreases the rate. CHsQ.8. In the following pairs of halogen compounds, which compound undergoes faster Syl reaction? a a a @ @r>AK ™ AAA a ans 2-Chaloro-2-methylpropane asthe tertiary earbocationismore stable than secondary carbocation. a w AnK 2-Chloroheptane as the secondary carbocation is more stable than primary ‘carbocation, Q.9. Identify A,B, C,D,E, R and R’ in the following: (nie + Me Prete gO RoBr + Mg Pasi. © 9. CHCHCH, CH, CH, cu,—— ben, Nelater_ pl_y Me, pio, p brnsc, Ans. A= (_)—Mgir B= () CH CH CHcHy—CHMgbr D=CH—E Mgbr cH, bi, bis CH CH, R=CH,—CH— R!=CHy o CHs Q.1. Name the following halides according to TUPAC system and classify them as (primary, secondary, tertiary), vinyl or aryl halides. yl, allyl, benzyl () (CH),CHCH(C)CH, (i) CH,CH,CH(CH)CH(C,HC1 (ii) CH,CHACCH),CHI (is) (CH) CCH,CH(BrCH, (@) CH,CH(CH,)CH(Br)CH, (00) CH,C(C,H)xCHBr (vil) CHyC(CI(C,H)CHCH, (vil) CH,CH=C(C)CH,CH(CH,) (x) CH,CH—CHC(Br)(CH), () p-CICH,CH,CH(CH,), (xf) m-CICH.CHACHLC(CHS); (aid) 0-Br-C,H,CH(CH)CH;CH, Ans. (#) 2-Chloro-3-methylbutane; 2° alky! halide (i) 3-Chloro-4-methylhexane: 2° alkyl halide (Gi) L-lodo-2, 2-cimethylbutane; 1° alkyl halide (iv) 1-Bromo-3,3-dimethyl-1-phenylbutane; 2° benzylic halide () 2-Bromo-3-methylbutane; 2°alky! halide (vi) 1-Bromo-2-ethyl-2-methylbutane; 1° alkyl halide (vi) 3-Chloro-3-methylpentane; 3° alkyl halide (viii) 3-Chloro-S-methylhex-2-ene; vinylic halideQ.3. Ans. Qs (ix) 4-Bromo-4-methylpent-2-ene: allylic halide () 1-Chloro-4-(2-methylpropyl) benzene: aryl halide (ai) 1-Chloromethyl-3-(2, 2-dimethylpropyl) benzene; 1° benzylic halide (sil) 1-Bromo-2-(1-methylpropyl) benzene: aryl halide . Give the IUPAC names of the following compounds: () CH,CH(CYCH(Br)CH, (i CHE,CBrClF (ii) CICH,C=CCH,Br i») (CC1),CCL () CHCp-CIC AH) xCH(BNCH, (00) (CHy)3CCH=C(CDC HEP (8 2-Bromo-3-chlorobutane (@ 1-Bromo-L-chloro-1, 2, 2-trifuoroethane (if) 1-Bromo-4-chlorobut-2-yne (iv) 2-(Trichloromethyl)-1, 1, 1,2, 3, 3. -heptachloropropane (9) 2-Bromo-3, 3-Bis (4-chloropheny! butane (vi) 1-Chloro-1--iodophenyl)-3, 3-imethylbut-L-ene ‘Write the structures of the following organic halogen compounds: (8 2-Chloro-3-methylpentane (ii) p-Bromochlorobenzene (ii) 1-Chlore-4-ethyleyctohexane (iv) 2-2-Chlorephenyl)-1-iodooctane () 2-Bromobutane (00) 4-tert. Butyl-3-iodoheptane (vil) 1-Bromo-4-sec. butyl-2-methylbenzene (iii) 1, 4-Dibromobut-2-ene ( CH,CH,CH(CHYCHCICH, ww Br-{O)-c1 1 «i ty i) 1H, —CH-(CH,),CH, HC or o CHSFHCHACHs (i CH;CH,CH,CHCH()CH,CH; Br H3C—C—CH3 I CH; (vin oe emraeneerc OHSS cH CH HC” ‘Which one of the following has the highest dipole moment? @ CH,Cl, (i) CHC, Gi) CC, ‘The three-dimensional structures of the three compounds along with the direction of dipole moment in each of their bonds are given as follows: NZ NZ aa od Na ae aS Ci, being symmetrical has zero dipole moment. In CHCl, the resultant of two C—CI dipoles is opposed by the result of C—H and C—Cl bond. As the latter resultant is expected to be smaller than the former, HCI, has a finite dipote (1.03 D) moment In CH,Cl,, the resultant of two C—Cl dipole moments is reinforced by the resultant of two C—H dipoles, hence, CH;Cl, (1.62 D) has a dipole moment higher than that of CHCl ‘Therefore, CH,CI, has the highest dipole moment,Qs Ans. 2.6. Ans. Q7. Ans, Qs. Ans. Q.10. Ans. A hydrocarbon CH,» does not react with chlorine in dark but gives a single monochloro compound, (C,H1gC1 in bright sunlight. Identify the hydrocarbon. (O The hydrocarbon with molecular formula C;Hp can be either a cycloalkane or an alkene. (i) Since the hydrocarbon does not react with Clp in the dark, itcannot be an alkene but must be a cycloalkane. (ii) As the cycloalkane reacts with Cl, in the presence of bright sunlight, to give a single monochloro compound, CsHoCI, therefore all the ten hydrogen atoms of the cycloalkane must be equivalent. ‘Therefore, the cycloalkane is cyclopentane. ‘on cn cl Nowsoie —- CY me CY (Cyelopentane( Cato) Monschloro- cyelopentane (CsHsC1) ‘Write the isomers of the compound having formula C,l1,Br. thas the following four isomers: CHs a bo () CH;CH,CHCHBr (i) CH,—CH—CH,Br {-Bromabutane 1 -Brom-2-metyropane CH; 4302 4 aoa (in CH, CHCA, Gh Cea Br chy 2-Bromobatine 2-Bromo*2-methyropae ‘Write the equations for the preparation of 1-iodobutane from (@) butan-1-ol (if) 1-chlorobutane, and (i) but-t-ene. (i) 3CHjCH,CH,CH,OH + Pl, ——> 3CH,CH,CH,CH,I + H;PO, Butane rol ‘dota eaty w@ CHsCH:CH,CH2Cl + Ka CH,CH,CH,CHyL +Ka (di) CH,CH,CH = CH, + HBr SS CH, CH, CH, CHBr Krceone ~Faetsea easy” CHsCH2CH.CHaT ‘What are ambident nucleophiles? Explain with an example. The nucleophiles which can attack through two different sites are called ambident nucleophiles. For example, cyanide ion is a resonance hybrid of the following two structures: “Cm: +> Itcan attack through carbon to form cyanides and through N to form isocyanides or carbylamines. ‘Which compound in each of the following pairs will react faster in Sy2 reaction with OH”? ( CH;Br or CHyL (i (CHyyCCI or CHC (B Since 1” ion is a better leaving group than Br” ion, hence, CHsl reacts faster than CHBr in Sy2 reaction with OH" ion. (i) On steric grounds, 1° alkyl halides are more reactive than tert-alky1 halides in Sy2 reactions. Hence, (CHCl will react at a faster rate than (CH,),CC1 in a Sy2 reaction with OH" ion. Predict all the alkenes that would be formed by dehydrohalogenation of the following halides with sodium ethoxide in ethanol and identify the major alkene. (D 1-Bromo-1-methyleyclohexane (i 2-Chloro-2-methylbutane (it) 2, 2, 3-Trimethyl-3-bromopentane. (d In 1-bromo-I-methyleyclohexane, the B-hydrogens on either side of the Br atom are equivalent, therefore, only L-alkene is formed.Be cmosecsion Hs a — HBr ‘ Lathe i All Bohydrogens in 2-chloro-2-methylbutane ate not equivalent, hence on treatment with C.H,ONalCHOH, it gives two alkenes. B T CH; 8 8 cs CH, —SMBONseO8 CH CH,—C= CH + oH CH-CH, a - cH, 2-coor"2-methyaane 2M 2- ane ‘jor proc (if) 2, 2, 3-Trimethyl-3-bromopentane has two different sets of B-hydrogen and therefore, in principle, can give two alkenes (I and Il). But according to Saytzeff rule, more highly substituted alkene (ID, being more stable is the major product. 1 sa fds > Cy — —CH.CH, cH, Gh Ci 2-Ehyh'3,3dimethyuct-ene one ene, ino ded CH, Br 2,2, 3-Trimethyl-3-bromopentane Hs CHs crowed lad 2ud, ane CHE 3 CHy 3.4, 4:Timetypnt-ene (Saor product 2.11. How will you bring the following conversions? ( Ethanol to but-t-yne (i Ethane to bromoethene (iii) Propene to 1-nitropropane (G8) Toluene to benzyl alcohol (i) Ethanol to ethyl fluoride (0) Propene to propyne (vil) Bromomethane to propanone (vlif) But-L-ene to but-2-ene (é) 1-Chlorobutane to n-octane (4) Benzene to biphenyl Am. (@ CyCHOH 7S. CHCHOL —_ ARS". chow, = cH ‘haa TaN Batslnye @ CHy—CH, + Bry, "=. cHycH,—Br “SESE. CH, = CH, Ehane ‘once i ‘Eten eee ano Me ea Ee (ii) CH; —CH = CH, 8 CH, —CH)—CH;—Br A822: OFFO__ CH, CH, CHINO» ones a 1-Bronopopne ~ Agr 1 -Riropopane Hs HC HOH in) aR Ky co) +o, SE AEROELA 5. Tae, Bessy chide Bessy ealcou () CH,—CH = CH + Bry CH;—CH—CH; Penn | Br Br 1,2-Ditemepopne (i) CH;CH,OH —SSCSP=ES. CH|CH,Cl —J22—> CHsCH2F ‘Edad =80n-HO” “pustcilonde “HCH” ish ere (vil) CH;—Br + KCN(ale.) —~ CH;CN —S*Mseeste_ —o Keston Chiy—Com NMgBr] smo oy C= 0 cH bu, (viii) CHyCH:CH = CH, + HBr “SS 3 Bite Br Rong. CH, CH = CH-CH, se Bue (jr pote) (ix) 2CH,CH,CH,CH,CI + 2Na — P28 —_ CH, CH,CH,CH,CH,CH,CH,CH, + 2NaCl 1 -Chocbtine a) note . tp, RS. 2a, ry ther, ae © +8 ge Ops “furem> (XO) + 2N08 ewe Ironstone Biche Q.12. Explain why (D the dipole moment of chlorobenzene is lower than that of cyclohexyl chloride? (ii) alkyl halides, though polar, are immiscible with water? (it) Grignard reagents should be prepared under anhydrous conditions? ‘Ans. () Due to greater s-character, sp” hybrid carbon atom is more electronegative than sp* hybrid carbon atom. Therefore, the sp" hybrid carbon of C-Cl bond in chlorobenzene has less tendency to release electrons to Cl than an sp* hybrid carbon of cyclohexyl chloride. As a result, the magnitude of negative charge is less on Cl atom of chlorobenzene than in cyclohexyl chloride. sp hybrid carbon sp hybrid carbon e 5 C¥ Less negative charge Ci <— More negative charge CClorobenzene Cycle chloride Further, due to resonance the C—C! bond in chlorobenzene acquires partial double bond character whereas the bond in cyclohexyl chloride is a pure single bond. In other words, C—CI bond in chlorobenzene is shorter than in cyclohexyl chloride. x é Ox oN “cet bond Bocitond ——yeteyt 4S Clan acquires partial chloride bond character oubie bond character As dipole moment is a product of charge and distance. Therefore, dipole moment of chlorobenzene is less than that of cyclohexyl chloride. i) Alkyl halides, though polar, are immiscible in water because they are unable to form hydrogen bonds with water molecules.Q.13. Ans. Qu. Q.15. (Gif) Grignard reagents are very reactive. They react with moisture present in the apparatus or the starting materials to give hydrocarbons. ae R—Mgx + H-OH —~ RH + Mg(OH)X kgs reagent Hence, Grignard reagent must be prepared under anhydrous conditions. Give the uses of Freon-12, DDT, carbon tetrachloride and iodoform. Refer to Points to remember 11 ‘Write the structure of the major organic product in each of the following reactions: (0) CHyCH;CH; Cl + Nal "=". (i) (CHy)3CBr + KOH ee ht (iil) CHyCH(r) CH, CH, + aon (iv) CH3CH,Br + KCN — “estate (0) CgHsONa + C,HsCl —~ (vi) CHyCH,CH,OH + soc, —-~ (in CHJCH,CH =CH, + HBr P= (ou cucu = CCH), + Be ( CyCHCH,CI + Nat — AM CHCH,CH + NaCl 1 diecenee vase cH, shots | Dactaignaiay 7 CHs—C= CH, + KBr + 1,0 2 Mignone i) (CH,);CBr_— + KOH 2-Brom-2-mmetilpropane pai (i Cr —ea_-Ca,cH + Mion Stic CHGCH + Nie >t (iv) CH,CH,Br + KON — AS CHsCHCN + KBr () CHgO"Na” + CoH Cl SEES — CoH,—O—CaHs + NaCl Sod. phenoxie ——-Eylchende Preneoie (i) CH,CH,CH,OH + soci, —"*_. CH,CH.CH,CI + HCI + SO, Propan- 1-0 sabetnten | Chlropropane Peroxide (id) CHsCHsCH = CH: + HBr Gott ggay ~ CHsCHsCHsCHBr CH as I Matt CHC cH (viii) CH,CI CH, + HBr 2 Migr 2-000 Br 2-toma-2-metiyltane ‘Write the mechanism of the following reaction: (Hors) nBuBr + KCN —"#=™2°_- aBuCN ‘The above reaction is an Sy2 reaction. CNT ion is an ambident nucleophile so it can attack the carbon atom of C—Br bond in n-BuBr through C or N. As C—C bond is stronger than C—N bond, therefore attack occurs through C to form n-BuCN. a NCK* + CH,CH,CH,CH,Br CH;CH;CH{CH,CN + KBrQ16. Qi. Ans. Qs. Ans. Qs. Arrange the compounds of each set in order of reactivity towards $2 displacement: [CBSE Dethi 2011] (H 2-Bromo-2-methylbutane, I-Bromopentane, 2-Bromopentane. (i) 1-Bromo-3-methylbutane, 2-Bromo-2-methylbutane, 2-Bromo-3-methylbutane. (ii) 1-Bromobutane, 1-Bromo-2, 2-dimethylpropane, !-Bromo-2-methylbuta 1-Bromo-3-methylbutane, ‘The reactivity in S,2 reactions depends upon steric hindrance: more the steric hindrance, slower the reaction (d Due to steric reasons, the order of reactivity in $2 reactions follows the order: 1°> 2° > 3°, therefore, order of reactivity of the given alkyl bromides is as follows: I-Bromopentane > 2-Bromopentane > 2-Bromo-2-methylpentane, (i Due to steric reasons, the order of reactivity of alkyl halides in Sy2 reactions follows the order: 1° >2° > 3°, therefore, the order of reactivity of the given alkyl bromides is as follows: 1-Bromo-3-methylbutane > 2-Bromo-3-methylbutane > 2-Bromo-2-methylbutane. ii) As in case of 1° alkyl halides, steric hindrance increases in the order: nalkyl halides, alkyl halide with a substituent at any position other than the f-position, one substituent at the Beposition, two substituents at the f-position. Therefore, the reactivity decreases in the same order. Hence, the reactivity of the given alkyl bromides decreases in the order: | -Bromobutane> I-Bromo-3-methylbutane> 1-Bromo-2-methylbutane> I-Btomo-2, 2-dimethylpropane. Out of CeH CH CCH @ o cH #4 a c CHy-C=CHy + HBr |= —_____, CH,—C—CHs, we “Mark. adn) | 6 Br © mi oe (CH;—CH—CH,—Br + 2Na +Br—CH,—CH—CH, @ CH; cH, | | — a CH, —CH—CH,—CH,—CH—CH, + 2NaBr @ ‘Wore eatin) Q.22. What happens when (8 n-butyl chloride is treated with alcoholic KOH, (i) bromobenzene is treated with Mg in the presence of dry ether, (ii) chlorobenzene is subjected to hydrolysis, (iv) ethyl chloride is treated with aqueous KOH, (0) methyl bromide is treated with sodium in the presence of dry ether, (vi) methyl chloride is treated with KCN? a Ams. () CH,CH,CH,CH;C1 + KOH(@le) CH, CH,CH = CH, + KCI + H,0 ‘Butyl chloride eA: But-i-ene ti) © + Mg —Dastier (Oven Brobezee Aarpbreriiniinih on ii re nt a Opo+ mow =A» GC) bese Pa (iv) CH,CH,CI + KOH (ag) —""2"*. CH,CH.—OH + KCI + 1,0 es oe @) CHsBr + 2Na + BrCH; —22*™*—_- CH;CH, + 2NaBr “Methyl bromide eee Ethane sot t0.8 (vi) CH;Cl_ + KCN ——————___. CH,C=N + KCl Metiyl chloride ‘Nuceophile subsiaaion) 3 cyanide (jor produc)Multiple Choice Questions Choose and write the correct option(s) in the following questions. au ‘Which of the following is vinylic halide? Br Br (a) CH,CH=CHCH,Br (6) O © or (@) CH,CHCH=CH, be ‘The position of Br in the compound in CH,CH—=CHC(Br)(CH,), can be classified as, Z INCERT Exemplar] @ Allyl Want (© Vinyl (@) Secondary ‘Which of the following is an example of vie-dihalide? [NCERT Exemplar} (@) Dichloromethane (b) 1,2-dichloroethane (©) Bihylidene chloride (@) Allyl chioride Ethylidene chloride is afan ‘ INCERT Exemplar] ©@ vie-dinalide (©) gem-dinalide (©) allylic halide (d) vinylic halide Haloalkanes contain halogen atoms) attached to the sp" hybridised carbon atom of an alkyl group. Identify haloalkane from the following compounds. (@) 2-Bromopentane () Vinyl chloride (chloroethene) (©) 2-Chloroacetophenone (@ Chlorobenzene ‘Which is the correct TUPAC name for CHj—CH— CH,—Br? INCERT Exemplar] bt (@) 1-Bromo-2-ethylpropane (6) 1-Bromo-2-ethyl-2-methylethane (©) 1-Bromo-2-methylbutane (@ 2-Methy!-1-bromobutane Consider the following reaction: HBr (CH;—CH = CH, — 704. KoH * ‘The major end product is [CBSE 2022 (56/3/4)) (@) CHs—CH—CHt, (6) Cis —GH—CHs OH Br (© CH;—CH—CH,—OH (@) CHy—CH,—CH,—Br ‘The synthesis of alkyl fluoride is best obtained from : ICBSE 2023 (S6/1/1)) (a) Free radicals (6) Swarts reaction (c) Sandmeyer reaction (@) Finkelstein reaction Ethylene chloride and ethylidene chloride are isomers. Identify the correct statements. (Both the compounds form same product on treatment with alcoholic KOH. (ii Both the compounds form same product on treatment with aq. NaOH. (ii) Both the compounds form same product on reduction. (i) Both the compounds are optically active. INCERT Exemplar] (@ Gand diy (©) (i and Git (©) @ andi») (a) @ and Gi)10. uM 2 3 rn 1S. 16. 17. Arrange the following compounds in the increasing order of their densities. [NCERT Exemplar] a a Br o « Qo i CO cy oO 0 cl cl @ @ <6) < ti CH—CH,Br (ii) CHyCH,CH,CH,Br ii) H,JC—C—CH, a | Br @ W<) Racemisation occurs in (CBSE 2023 (56/2/1)] (@) Syl reaction (b) Sy2 reaction (c) Neither Sy nor $y2 reaction (d) Sy2 reaction as well as Sy reaction ‘The order of reactivity of following alcohols with halogen acids is + [NCERT Exemplar] cH I (A) CH;—CH;—CH;—OH = (B) CH3;CH;—CH—OH (C) CH3CH;—C—OH CH; CH; @A>B>© OO>B>A OB>A>C©Q WA>O>e) In which of the following molecules carbon atom marked with asterisk (*) is asymmetric? H D H H [NCERT Exemplar] he ke whe oh fa ,&a ScH, yn, ICS eS 8a? Boa o w tity a) © ©. Gi.) () ©. G, id (© Gi, Gid, © Outi), @) Which of the following structures is enantiomeric with the molecule (A) given below: H [NCERT Exemplar] | CH oe Nor cy) H oBr (e) HC © HS Non,Assertion-Reason Questions In the following questions, two statements are given—one labeled Assertion (A) and the other labeled Reason (R). Select the correct answer to these questions from the codes (a), (6), (c) and (d) as given below: @ ) © @ £ Both Assertion (A) and Reason (R) are correct statements, and Reason (R) is the correct explanation of the Assertion (A). Both Assertion (A) and Reason (R) are correct statements, but Reason (R) is not the correct explanation of the Assertion (A). Assertion (A) is correct, but Reason (R) is incorrect statement. Assertion (A) is incorrect, but Reason (R) is correct statement. Assertion (A) : Thionyl chloride are preferred over Phosphorus chlorides (tri and penta) forthe preparation of alkyl chlorides from alcohols. Reason (R) : Thionyl chloride give pure alky! halides. 2 Assertion (A) + Alkyl halides are insofuble in water. Reason (R) : Alkyl halides have halogen attached to sp* hybrid carbon. [CBSE Sample Paper 2022] 3. Assertion (A) : KCN reacts with methyl chloride to give methyl isocyanide. Reason (R) : CN" is an ambident nucleophile. 4. Assertion (A) + tert-Butyl bromide undergoes Wurtz reaction to give 2, 2, 3, 3-tetramethylbutane. Reason (R) + In Wurtz reaction, alkyl halides react with sodium in dry ether to give hydrocarbon containing double the number of carbon atoms present in the halide. 5. Assertion (A) : Hydrolysis of (~)-2-bromooctane proceeds with inversion of configuration Reason (R) + This reaction proceeds through the formation of a carbocation, 6. Assertion (A) : Nucleophilic substitution of iodoethane is easier than chloroethane. Reason (R) + Bond enthalpy of C-I bond is less than that of C—Ci bond. [CBSE 2023 (56/2/1)) 7. Assertion (A) : Aryl halides undergo nucleophilic substitution reactions with ease. Reason (R) : The carbon halogen bond in aryl halides has partial double bond character. [CBSE Sample Paper 2020) 8. Assertion (A) + Chlorobenzene is less reactive towards nucleophilic substitution reaction. Reason (RK) + Nitro group in chlorobenzene increases its reactivity towards nucleophilic substitution reaction, ICBSE Sample Paper 2021 (56/3/4)] 9. Assertion (A) : Nitration of chlorobenzene leads to the formation of m-nitrochlorobenzene. Reason (R) : —NO, group is a m-directing group. 10. Assertion (A) : It is difficult to replace chlorine by —OH in chlorobenzene in comparison to that in chloroethane, Reason (R) : Chilorine-carbon (C—C1) bond in chlorobenzene has a partial double bond character due to resonance. 11. Assertion (A) + In monohatoarenes, futher electrophilic substitution occurs at ortho and para positions. Reason (R) : Halogen atom is a ring deactivator. 12. Assertion (A) + Aryl iodides can be prepated by reaction of arenes with iodine in the presence of an oxidising agent Reason (R) + Oxidising agent oxidises I, into HI. Answers L@ 20 3 4@ 50 6a Td Re) 9d) 10.(@) UL. () 12)