AlkanesDISCLAIMER “The content provided herein are created and owned by various authors and licensed to Sorting Hat Technologies Private Limited (“Company”). The Company disclaims all rights and liabilities in relation to the content. The author of the content shall be solely responsible towards, without limitation, any claims, liabilities, damages or suits which may arise with respect to the same.”Alkanes Electrophile In a reaction between two organic molecules, it is difficult to specify the reagent and the substrate. Ordinarily, the one with full charge is more reactive and may be considered as the reagent. Thus, C,H,0° is the reagent in the reaction given below: R—X + CeHsO®Na® > C2HsOR +NaX Substrate Reagent Product Reagents are of Two Type The one which attacks the positive site in the molecule is called the nucleophile or nucleophilic reagent and the one which attacks the negative site in the molecule is called the electrophile or electrophilic reagent, 1, Electrophile: Electron deficient species which are attracted towards electron Electrophiles are positively charged or neutral species which have vacant orbital. ‘Types of Eloctrophile: ° (A) Cations: R+(CH,®, CH,-CH,*) H®, No, No, 80,4, H-E = 0, als, EH=NH, cle, Br? NH? and 1:0" 1A and IIA cations Na’, K Mage, Ca®* * Do not work as electrophile because they have complete octet. y + N, as 2s? 2p? HIS ss TetNy i inn 4 H we ae(®) Neutral Electron: AICL,, BF,, BCL, BH,, SiCl,, PCl,, PCL, (Vacant orbital), SnCl,, SnCl,, SbCl, All Lewis Acids are E® E® deficient species (C) Polar x-bond: Example: ot RGR o> a (O) induced Dipole interaction : Example : Br,. CL. |, ILLUSTRATIONS | Anelectrophilic reagent is: (A) Electron rich species (B) Electron deficient species (C) A Lewis acid (D) Negatively charged species Sol: ® Anucleophile (A) Electron-rich species (8) Electron deficient speci (C) a Lewis acid (D) Positively charged species Sol: 4Which of the following will act as an electrophilic reagent? (A) H,0 (B) OH- (C) NO; (D) None Sol: ¢ Which one is not an electrophile in given below? (A) AlBr, (8) BF, (©) Snel, (0) NH, Sol: 0 | Which among the following is not a Lewis acid? (A) BF, (B) Alct, (Cc) NH, (D) Hg Sol: ¢ | Which of the following is an electrophile? (A) NH, (B) ROH (C) “OR (0) Bcl, Sol: 0 2. Nucleophiles: Electron rich species which attack on electron deficient centre [except H*] attracted towards electron deficient centre. OH? + “Hcl? 5 H.0 + cl? | Points to remember © Base Allanions and lone pair containing substance are all Nucleophiles. OH® + °CH,-Cl° > HO - CH, + CP Nucleophile© Electron rich species which attack on _@ Electron rich species which accept H* electron deficient centre ions [except H®] &, = ont ce + H,0 + el? P+ a — HO-CH; + Cl? ically controlled Thermodynamically controlled that is How much fast accept H* ions form Attacking speed Attacking speed stable product. high’ low J ‘strong Nu® weak Nu? As steric hinderance 7, nucleophilicity Steric hinderance have no effect on decienses basicity as acid-base reaction take places. (Nu®* 4) ‘Types of Nucleophile: (A) All anionic species : (i) R° (CHS®, CHs-CH.") (ii) OH®, NO." (iit) F, cl, Br®, 1° ° (iv) CN®, SH®, R-0® ™) ,CHj-U-08(®) Allllone pair containing: RBH fi) Win, Rit, R-NH-R, Rolie Gil) RSH, Be, Bet, ® (iv) H-0-0-H, NH,-NH, on NH-NH, NO» NOs oMP DMPH No» 0; 0 “a ay (©) n-bond: Alkene, alkyne and phenyl Example: R-CH =CH,,R-C = CH Factors affecting Nucleophilicity: (A) Electron Density : = Electron density 1 Nucleophilicity t (OH > HG (i) NHA*> Nie, (ii) SHY > (8) Nucleophilicity in Periodic Tabl @ ima period: Etectronegativity 4 Nucleophiticity L Nucleophilicity : CH,*> NH," > OH*> Fe Basic Strength : CH,*> NH.°> OH®> F# Gi) Inagroup: © Points to remember Some species act as both electrophile nucleophile called as ambiphiles : Electrophiles as well Nucleophile Vacantcrbit Lone pair. In a group, size of species/cation/anion changes so solvent effect is applicable. We will discuss solvent effect in groups at nucleoph derivatives before SN2 reaction ity in halogenILLUSTRATIONS Sol: Sol: Which one is not a nucleophile in below? (A) NH, (8) BF, (C) -OH (0) Hso; A nucleophile must necessarily contain (A) an overall positive charge (B) an overall negative charge (C) a lone pair of electrons (0) an unpaired electron c Which of the following is an electrophile? (A) RNH, (B) H,0 (C) :CN- @) :CH, a ss 3. Reaction Intermediates : Definitions Reaction intermediates are basically related to species formed inbetween reaction. Bond Reactive, short lived, high breaking is either hetrolytic cr homolytic. energy, unstable species, those are formed in the course (A) Homolysis (Bond breaking in equal sharing of organic reactions are called basis) reaction intermediates. Low electronegative difference leads to formation of radical inter mediate result due to hemolytic bond breaking. oq Qj 8 > Ae +8 Homolytic bond cleavage Radicals(B) Hetrolysis (Unequal ution of electrons): Bond breaking in such a manner that bond electron shift permanently to one fragment charged fragment produce (positive and negative) ions. AB 3 At #:8- Heterolytic bond cleavage aie tons Bond polarity is key reason behind hetrolysis. Energy Profile Diagram - @ * Energy profile diagram is started from reactant to (Lot's understand ‘ion state form. ~ product in which transit Those diagrams which explain the conversion of reactant into product with energy is known as energy profile diagram. Ts. E Time conc. 1 x I 2 2 2 Inter Inter i > = > Time conc. —» Time conc. —» Number of transition tate = number of step = 1+ intermediate zThe rate determining step is a slow step in which maximum activation energy is required, To count activation energy cifference between reactant and highest energy transition state. Intermediate means those species which form between two Transition state. Examples of intermediate: 1. Carbecation CH,” 2. Carbanion CH,” 3. Free radical CH} 4. Carbene SO 470 470 . 0 5. Nitrene Re R-N@ O° os & sensre Oh CY Transition State : Those Species formed during a reaction which TS cannot be isolated or separated is known as transition state. HO-CH, + Cl’ 2 2 Exception: BF 5 +¢H, —— [oco “> CD #, | > CH,=CH,‘Type of transition state : (A) Exothermic Transition Stato : Transition state is close enough to energy to the reactants than to the products. Therefore, the transition state is having reactant character. (8) Endothermic Transition State : The transition state is closer enough to energy to the products than to the reactants. Therefore, Transition state is having product character. (C)_Isoenthalpic Transition State : Transition state is closer enough to both reactant and product which means both characters. ILLUSTRATION 2 Q Energy —» Time conc. —»Number of step =3 R.DS of step=Il Number of transition state = 2(8.0.F) Number of intermediate = 2 (C.E) B resembles with D resembles with C (vil) F resemble with E (vill) C resemble with B Rearrangement of Carbocations a= @ In areaction ifintermeciate carbocation will form, then it may reaaranges. Only that carbocation will rearrange which can produce more stable species + Cation formatio slow step, but rearrangement is a fast step. a- OH, a’ Um stable cation It can be done either by (i) Shifting of hydride (H-), alkyl (R-), aryl (Ph-), bond, (1, 2 shifting) i) Ring expansion (more strained ring to less strained ring) ii) Ring contraction If the carbocation formed in areacticn is unstable, by 1, 2 shift. rearranges to a more stable carbocation V2 He shift 1, 2 alkyl shift 1,2 CHE shift 1, 2 ring expansion * All are fast step * All are possible 1, 2 shift 1,2 Ph® shift 1, 2 ring contraction 10.Types of Shifting 1. 1,2 Hydride Shift G> wH e mh, shi “SS ue Me Me PC 2° (Less stable) (More stable) 2. 1,2-Maethyl shift and 1,2-phenyl shift Ph Me, ie —| seth ys shift 1 Me 3° benzylic C (More stable) * 1° Possibility Cr) Ph I eS 120% Me SMe Me—f—CH—me Me Me (less stable) * 2° Possibility (Resonance is absent) 3. Neopentyl rearrangement we He gec® : ree! n*For 1, 2 shifting cation must be more stable than before *In alkyl, only cation shift (not anion, radical) * th he oe p Leo wot chitin TC hs, Jee shifting) Count the number of shifting in the following: Concept Building Exercis Qi H vA CH Le CHS Sol: 4 ut ch a2 @ 12H shite | fast, nt CH, CH H 2aH 4aH 8aH * 2 times shift 1a:Q12 H H H 4 Sol: This is already in stable statel. - » No change should take palce. H H. -—<—— H H ° H H H H 4aH 4aH Q13 "6 nef Bnen—én cH, Resonance Stablized due to back bondingSol: Sol: Sol: “S4; SZ Z > ‘Be (Octet compete cation) Ph Ph H * Ho— CH. t 4 Pho Ph —__ y cizach, CH-ch, tats | ae a e 4 times H ~ A n~AX, TAA OASO17 Wc-o— cn, Sold yc oon GOLEM, — yc 0— . 2 . we-B een mcn, Resonance gis HC —O—CH,—CH,~CH,-CH, a e HC —O—CH,—CH,—CH,—CH, ——> H,C—OCH,—CH,—CH—CH, 1 shift t Sa-H More stable Sol. Cr O-9 Resonance (not shifting) 15.CH,CH ° Ph CH, sina ey IRE Bi Sol. group to form given carbocation?? eh f opm | Ph Zi Resonance stabilised Benzylic carbocation * Transition state 16.Su H shitt preferred Ring Expansion Carbocation out of Ring 3 membered > 4 membered > 5 membered > 6 membered —><+ 7 membered ee gre nen Possible «For ring expansion, numbering start from carbocation to carbon and end to that carbon which is having more e- donor. © If cation in the ring then ring contraction occur.Concept Building Exercis 923 4 HAC H,c—CH, ® Sol: 18.CPM (cyclopropyl methyl carbocation) : 3 member cyclopropyl carbocation highly strained due to ring angle strain. When positive charge present just outside of ring bondelectron delocalization possible due to high relief in strain and lowering energy stabilize system. 2 c electron and 3 ‘C’ involved in delocalization. 4 1 ' bp + — SS ~47% © sm Bent orbital tend to shift towards vacant orbital of cationic carbon. ILLUSTRATION O25 HO me teHo Sol. ve Me Z ee ba reat Me a } C ‘ » — “| HO Me OH Q26 u¢ 7 |e C—CH,,Sol. Hye zs ‘Though, we formed 4-membered as a result of ring expansion that carbocation outside 3 members ring is more stable. es i Q27 Be By Sol. Hi | L2H oy Less Stable cH More Stable4 I 7 7 3 Sol. 3 4 3 H 2 4 2 1 CH 5 Ta. + angle strain | ee: : 5 2 we > 4 3 6-H 2a -H (most stable) Q29 2s cH, Se 4 Le 5 cHSol. Q30 Sol. Passage Under common reaction conditions, for greater stat fj’) chy 4 ® 2 A chs : oy wae or 3 5 cH ° 4 (Ring Expansion) How many of the following carbocations have stability greater than iso- propyl cation (CH,),CH? 0. Ari, Por, aN 4 H oO 1 — h ‘ Nv. 7 onN PA AE. Z™ Ca 126 fo} 2°SP~ cut 1. 3 Resonance stabilized. . GF ORG aconance inch bendindiniilbel i BAN ALe Revonaree (28 ) stabilized ity a carbocation rearranges to another carbocation. Like, secondary carbocation will rearrange to a tertiary carbocation, It will not rearrange to a less stable primary carbocation. T generalization is not absolute, and because there is not a high energy barrier to the rearrangement of carbocations, rearrangement to a less stable cation can occur if it offers the chance to form a more stable product.Sol. Sol. In which of the following rate of cations rearrangement is maximum? 4 4 le e w C\-1-, ® ncfts, i du, cH, © ALS © . A 0 a 2 (Nits mB, I 1 cH, cH, As Rearranged carbocation is resonance stabilized by benzene ring.Q33 Sol. Sol. In the following cation, a that is most likely to migrate to the positively chargedcarbonis: = “Yt: H H (A) CH, atc- 4 (B)Hatc-4 (C) CH, atC-2 (D) H atc -2 oD As when we move H for C-2 we get back bonding stabilized carbocation. 4 CH CH, —+ HjC—C—CH, HC, ‘cH ‘The following carbocation rearranges to CH; CH, Te 1 H.C=C—C—CH-CH—CHy CHCH, chs CHy cH, CH, rt I { (A) Hxe=C—CH-CH—CH—CH, (BY HaC=E—C—CH ECs Cy Ho CH, CH i id er 8 = = 4y,C=C—C—CH—CH—-CH, (ce) C=C CCH E—CH, py CHEE 3 CH, CH3 H CH, CHy o 1,2-methyl shift results into more stable carbocation which is stable due to delocalisation and hyperconjugation. 2s.Sol. Which of the following carbocation can undergo rearrangement? @ (d) (e) (c) (d) U 0) No colour, No odour {b) C, to C,, = colourless & odourless liquid (©) Rest are colourless solids. Gi) Non polar molecules, not soluble in polar solvent like water. With- increase in size of hydrophobic part solubility decreases. MELTING AND BOILING POINTS Increases with molecular mass and decreases with No. of branches. As far as melting point is concerned the alkane having even carbons has more M.P. than odd carbons, since the intermolecular forces in a crystal depend not only upon the size of the molecules but also upon a crystal lattice. AA NALA, ven see (both methyl group (both methyl group are directed on are adversely same side) directed) M.P. [even > odd no. of atoms} (iv) Boiling point decreases with the increment of branches. (v) Physical state: Alkanes C,- C, Gaseous state C, - C,, Liquid state (except neo-pentane) Cy, & above Solid like wax (vi) Alkanes are lighter than water, so it floats over water. Concept Building Exercis > For atkanes having molecular formula C,H,,, write structures of different 7 chain isomers. Also write their IUPAC names. Sol, CHs-CH,-CH,-CH,-CH.-CH, : n-Hexane (ii), CH a GH-CHa- GHs- CHs 2-Methylpentane CH; 29.(ili) CH3-CH2-CH-C! 3-Methylpentane CH; (iv) CHsSCHaGH= Cs 2,3-Dimethylbutane CH; CH3 ine (v) CHs-C-CH2-CH; 2,2-Dimethylbutane CH; Write IUPAC names of the following compounds : @ (CH,), C CH,C(CH,), Gi) (CH), C(C,HD), Sol. (2,2, 4, 4-Tetramethylpentane ~ (ii) 3, 3-Dimethylpentane In the above structures (1-iv), Count the number of sigma (0) and pi (x) bonds. Q38 Sol, bonds : 33 x bonds : 2 g bonds : 17 x bonds : 4 6 bonds : 23 x bonds : 1 6 bonds : 41x bonds : 1 Alker 1. General Introduction Hydrocarbons that contain a carbon-carbon (C=C) double bond are called alkenes. Each double-bonded carbon(C=C) of of an alkene has three sp? orbital of another atom to form aa bond Thus, one of the carbon-carbon bonds (C-C) in a double bond is a o bond, formed by the overlap of an sp? orbital of one carbon with an sp? orbital of the other carbon.The second carbon-carbon(C-C) bond in the double bond (the x bonds) is formed from side- to-side overlap of the remaining p-orbitals on the sp? carbons. Because three points determine a plane, each sp? hybridized carbon and two of the three atoms bonded to it are in a plane. In order to achieve maximum orbital-orbital ‘overlapping, the two p-orbitals must be parallel to each other. So that, all six atoms of the double bond system are in the same plane. A molecular orbital description of a carbon-carbon double P orbitals overtap to form anbond bond It is important to remember that the x bond represents the electrons cloud that is above and below the plane defined by the two sp? hybridised carbons and the four atoms bonded to them. Because the two p-orbitals that form the = bond must be parallel to one another to attain maximum overlap, and rotation about a double bond dees not occur. If rotation about a double bond did occur. the two p-orbitals would ceases to overlap and the x bond would be destroyed. jond is broker Ea, tts ao “es ¢ c. zn “oo Gsisorer 2. Characteristics of Alkene (@) General formula :C,H,,. (b) Functional group : in alkenes is > C=C < (©) The double bond(C=C) is made up of one sigma and one pi bond. (@) The doubly bonded carbon atoms are sp* hybridized (@) Geometry of unsaturated trigonal planar. carbon is a(C=C bone length is 1.34 A. (8) C-H bond length is 110 A bond energy is 143: k cal mot" @ — C-H bond energy is 98.69 k cal mot” @_ Alkene shows chain, position, functional (ring chain), optical & geometrical isomerism. Cumulated polyene can exhibit geometrical as wellas optical isomerism. for example. Isomers of C,H,: (i) Chain isomers —> CH)-CH.- CH=CH, & HS C= CH, cH, (ii) Position isomers — CH.=CH-CH:-CH, & CH,-CH=CH-CH, {ii Functional isomers (ring chain isomerism) CHa-CH.-CH=CH, & Hao —CH 1 H,C—CH, 1-butene cyclobutane (iv) Geometrical isomers» (v) __ Optical isomerism > CH.-C-H CH)-C-H CHECH, i] & Il | CHi-C-H1 H-C-CH, H-G-cH cis-2-butene___cis-2-butene CH-CH 3. Structure, IUPAC name, and Common Name of Some Alkenes CH=CH, Ethene Ethylene CH,-CH=CH, oN Propene Propylene [> CH CH: CH=CH ANA erene 1-Butylene CH-CH=CH-CHs But-2-ene or —2-Butylene Hs ZR Mbutene L—_H.c—C=cH, 2 2-Methyl Iscbutylene or isobutene 31 Propetvene 32.4. Physical Properties @ From C,-C, they are colourless, odourless gases, from C,-C., they are colourless liquids, C., onwards alkenes are solids. Gi) Alkenes are practically insoluble in water because they cannot form hydrogen bonds with H,0 molecule. They dissolve freely in organic solvents like benzene, chloroform, CCl, petroleum ether, etc. (Like dissolves like) Gi) if branching increases, boiling point and melting point both de @w L LJ o an, MP. Gi) > (i) (Symmetry) B.P. (i) > (ii) (Polarity) () The boiling points of cis isomers are higher than trans isomers because cis-alkenes has greater polarity (Dipole moment) than trans one. Alkenes floats over water. (vil) The increase in branching in carbon chain decreases the boiling point among isomeric alkenes. 5. Chemical Properties The main reactions of alkene are electrophilic addition reaction and the mechanism is based on ionic. It was proved by Francis. ° JE, Ne 3” Fast, SL cacy — EL, “c---t7 —East, Scec: 7 NT Slow 7 SON TN Nu Alkkyne 1. General Introduction Similar to alkene, having one ‘o’ and 2'x’ bonds. Gi) Other term used for alkyne is acetylenes considering derivatives of Ethyne (acetylene), the simplest hydrocarbon Gil) Industrial significance cf acetylene (Ethyne) is welding purpose. Colorless, foul-smelling gas famous in domestic and commercial use. When acetylene flame (sooty flame) is supplied with pure oxygen, color turns to light blue and flame temperature increases dramatically. 33,(iv) Bond angle in alkyne is 1808. (v) Their general formula is CnH,,., (wi) C-C triple bond length is 1.20 A. (vii) C-H bond length is 1.08 A 2. IUPAC and Common Name of Some Acetylenes and Its De ate Structure Tm: ‘Common name a ethyne Acetylene Pent-i-yne Propylacetylene Peni-2-yne Ethyl methylacetylene oer Comer 4-Bromobut-1-yne 2-Bromoethyi acetylene 2,2,5-Trimethyl hex-3-yne tert-butyl isopropyl acetylene bP H-3 1.2-Dicyclopropyl eth-1-yne Dieyclopropyt (Numbers are not necessary, —_| acetylene but are used for clarity) = 3-(2-Propynyl-cyclopentata- |= i 34,3. Physical Proper (a) Colourltess, odourtess and tasteless hydrocarbon. (b) Polarization power in case of lower alkyne (example C,H,), lead and partial solubility in H,0. (©) With increase in size of hydrophobic part, solubility decreases dramatically. (@) Solubility in organic solvent. (e) |Melting point T]M.W. T Branching 4 (consider MP or BP increasing) Boiling point T|M.w. T Branching 4 (consider MP or BP increasing) (f) C.-C, Gaseous C.-C, Liquid. C,, & up Solid. 4, Chemical Properties The chemical behaviour of alkynes is similar to that of alkenes. Alkynes form addition products with two or four univalent atoms or groups. They are generally less reactive than alkenes towards electrophilic addition reactions even though x electron density is higher in alkynes. This is because on moving from alkene to alkyne, the C—H bond has more of s character (33% in alkenes as compared to 50% in alkynes). Therefore, the x-electrons are more firmly held by carbon nuclei in alkynes and are thus less reactive to an electrophile. 35.Concept Building Exercis Sol. Write IUPAC names of the following compound: Z OF PSO iy 7A Gil) CH, = © (CH.CH.CH) vy CHACHACHACHACH, — CHCH Hc—cHcH=! cH, —CHCH, I cH, (i) 2, 8-Dimethyl-3, 6-decadiene; , 3, 5, 7 Octatetraene; (iii) 2-n-Propylpent-1-ene; (iv) 4-Ethyl-2,6-dimethyl-dec-4-ene Write IUPAC names of all the isomers corresponding to the 5 member of alkyne series also draw structures differant isomers. What kind of isomer- ism is exhibited by different pairs of isomers? Write possible isomers of S* member of alkyne has the molecular formula CeHro. (a) HC = C~CH2-CH:-CH.-CH; Hex-1-yne (b) CHC #C-CH:- CH: CH Hex-2-yne (©) CHs-CH.~C = C-CH.-CHs Hex-3-yne (d) HC ~ C-CH-CH-CH bu 3-Methylpent-1-yne fe) HE = C-CH-CH-CH, Hh 4-Methylpent-1-yne(CH= ogee H 4-Methylpent-2-yne s-Dimetnytba-1-yne Application of Stereochemistry 1. Photo halogenation of Alkane Substrate > Alkane Reagent > Xs hvor XA Intermediate + Carbon free radical Mechanism > Free radical substitution reaction Product > Haloalkane (Mono halogenated, Di halogenated, etc.) Reaction > R-H —4& 4 R-X4H Mechaniem (i) Chain initiation Step (always endothermic) (ii) Chain Propogation Step slow step sae CH, +H-x cH, +x Step-1 CH, -X +H (Unstable Step-2 CH, +X-X CH, -X+X" (may be endothermic or exothermic) (ii) Chain Terminating Step (Always exothermic AH = negative) —— CH, - CH, (Dimer) —— CH, - xX (Desired product) —*, 37,ILLUSTRATION Q41 ~~. —> Sol. x w Gi) Characteristics of Reaction 1. Rate of photo halogenation : Rate of reaction « Stability of carbon free radical Stability of carbon free radical : 3° > 2° > 1° Rate of reaction « Bond strength of H-X Bond strength of H-X : H-F > H-Cl > H-Br > H-I Rate of Photo halogenation: F, >>> Cl, > Br, >>>> 1, 2. Direct fluorination is not possible as it is explosive, so fluorination takes place in dark. 3. lodination is reversible reaction as in this reaction strong reducing agent HI is formed which reduces alkyl iodide into alkane again. So in iodination we use strong oxidizing agent like HNO,, HIO, etc. So that reaction move in forward direction. (Follows Le-chatelier principle) RHR 1H S11 410, —» @) +310 (Follows Le-chatetier principle) Reaction move in forward direction. ILLUSTRATION 942, cH, a5 Sol. cH, —% + cH,-cl+cH,-cl, + cH-cl, + CCl, 38.CH, (excess) + Cl, —*> CH,CL Think about rote of excess CH, ? Sol, _ Excess CH, will consume all Cl, so no further chlorination. Sol. CH, + Cl, (excess) —Y> cet, Sol. CH, - CH, —S#" 5 CH,-CH,Cl+CHCL-CCL,+CH,Cl-CH,Cl+CH,-CHCl, + CH,-CCl, + CHCL-CHCL+CCI,-CCI,#CH,CI-CCI,+CH,Cl-CHCL, O46 A\, —SL2~, number of monohatogenated product Sol. aoe cl “™. ey + hs GL (Major) O47 Cli/hy Number of monohalogenated productSol. Sol. Q49 Sol. cl Ooo +t —— Number of monohalogenated product ‘Cl (f@) Total number of monochlorinated product = (6) Enantiomer pair = © — Enantiom (¢) Number of product separated by fractional distillation = (©) Number of chiral product = ( Number of structural product = cl INT Skee ~? £ —\ cl (2) R/S (@) Total number of monochlorinated product = 3 (6) Enantiomer pair = 1 (© Enantiomer = (4) Number of product separated by fractional distillation = 2 (©) Number of chiral product = 2 (f) Number of structural product = 2 40.Sol. Sol. gO Bro/hv Number of dihalogenated product Br : a Br 3 Bro br br Br ) © . ( (2) ( (1) (i) Total number of product = 5 Gi) Number of product separated by fractional distillation = 4 cH, Cyr —- @ Total number of monohalogenated product = i) Total number of structural monohalogenated product = Gii) Total number of product separated by fractional distillation = Gv) Enantiomer pair = (¥) Chiral (i) Achiral = 5=0 5 OOO cl a) (1) (4) (4) (2) (i) Total number of monohalogenated product = 12 Gi) Total number of structural monohalogenated product Total number of praduct separated by fractional distillation = 8 fiomer pair = 4 a.Oa Sol. H.C-CH-CH,-cH, — cH Mone halogenation G) Total number of monohalogenated product = Gi) Total number of structural monohalogenated product = Gi) Total number of product separated by fractional distillation = (iv) Enantiomer pair = (v) Chiral = (vi) Optical inactive = cl aun hg H oarech -CH , CICH, rd CH.-ch), i CHE SEG cH cH CH @ a + ct I HiC-GH-CH-CH.CI , HxC-CH.-CH-CH cH o 2) (i) Total number of monohalogenated product = 6 Total number of structural monchalogenated product = 4 (iii) Total number of product separated by fractional distillation = 4 (iv) Enantiomer pair = 2 ) Chiral = 4 (vi) Optical inactive = 2 cr (@) Total number of monohalogenated product Gi) Total number of structural monohalogenated product Gii) Total number of product separated by fractional distillation 42.Sol. cH cH. tic~ct cH H Clo HCL ai noe feat Boch Clk wife H.C-CH H.C-CH CH CH H.C-CH.-Cl a) a) a) a) a () Total number of monohalogenated product = § Gi) Total number of structural monohalogenated product = 5 Gi) Total number of product separated by fractional distillation = 5 How to decide Major and Minor product in Photo halogenation 1 1 1 A cl 1 35 5 er, 1 82 1600 Selectivity * Reactivity Reaction of product = Relative rate of H x Number of that H ILLUSTRATOIN O86 ch, ch, - cH, ay Sol. CH, —CH, ~CH, Bi CH, - CH CH, CH Hy Oy Fe + Fe X% ys 25% 75% w> 2°Sol. Sol. Number of monochloro products : (a) Including stereoisomers (b) Excluding stereoisomers HyC—CHp-CHy __u/h a2 (2 MECH CH, Ae, Hood —oy | Hal CH Oe o a 2<39= oxi=6 2.100 £100 3 3 52.8% 46.1% 10,6 Number of monochloroproduct = 10 Number of monochloroproduct = 6 (excluding sterecisomer) PD AAg oa we 22 ol aayeo 4 Sol. &4 Number of monochloroproduct = € = 4 (excluding stereoisomer) Ak - & SA é duh 2 & JAA. * Sol. *%1 Number of monochloroproduct = 1 Number of monochloropraduct = 1 (excluding stereoisomer) ‘oP Xe 4s.Q59 oa Sol. Sol. 2,2 Number of moncchloroproduct = 2 Number of moncchloroproduct = 2 (excluding sterecisomer) tr teh, R-2-chlorobutane 5.3 Number of Dichloroproduct = 5 Optically active product = 4 (in- cluding sterecisomer) =1 = Optically active =2 i.e. One optically active ‘One meso compound =1 = Optically active a1 = Optically active 46.Sol. 7& Number of Dichloroproduct = 7 Optically active product = 6 (including sterecisomer) * or =2 Optically active ¥ 1 1 * © =4 Optically active a cl ~~ =1 Optically inactive cl Sol, 12.10 Number of Dichloroproduct = 12 Optically active product = 10 (including stereoisomer) 4 =2 Pu kA a cl c-* =4 cl cl cl * * =3 i.e. Two optically active One meso compound de aoe, =2 Reaction of Alkane with SO,Cl,/hv: (Reed Reaction) Points to remember » R-H—224 yR-S0, -Cl Chlore Sulphonation C,H, + SO, +Cl; —“> C,H,SO,Cl + HCL orpoare suteho brieagg tenor Reaction with NBS (N-Bromo succinimide)/hv: Substrate . Alkene, Benzene (Aromatic compound) Reagent : NBS / hv Intermediate : Carbon free radical Mechanism: Free radical substitution reaction Product % Allylic and Benzylic substituted bromide Reaction: (i) CH, = CH--CH, #8 54.0 = CH-CH, | 8r @ (\-, iit Oo er 48.9 9 ° ° bow —t 4 Zz So Me [nn + Br, > i—Br C—O cm ~ a ra 8 8 8 Succinic acid Succinic anhydride Succinamide —_N- Brome Succinamide 9 oO on — Ce +6 5 0 CH, = CH-CH, +8r—24—+CH, = CH- “CH, + HBr Chain Propagation Step CH, = CH- CH, +Br-Br——>CH, =CH-CH, -Br+Br Br’ +8r ——+Br, (Chain terminating step) Note: Along with NBS some amount of HBr is also used to maintain the proper concentration of Br,. Method to Calculate Structural Product in this Reaction Step-1: First identify allylic or benzylic carbon in the given substrate. Step-2: By the removal of H-atom at this allylic or benzylic position convert into free radical. Step-3: Draw all pos benzene ring. ‘Step-4: Add bromine radical to all possible position of carbon radical formed. 3 le resonating structure for allylic or benzylic position except in 49,ILLUSTRATIONS Q Sol. CH, - CH = CH-CH, —“—-> (A) Total number of products (x) = ? (8) Total number of structural products (y) = 7 (C) Total number of products separated by fractional distillation (z)=? (0) Chiral product = 7 {E) Optically Inactive = ? CH, - CH = CH-CH, => CH, - CH = CH- CH, - Br +CH, - CH-CH= CH, I Br (2 Geometrical isomer Q) Optical isomer (a) Total number of products (x) = 4 (@) Total number of structural products (y) = 2 (©) Total number of products separated by fractional distillation (z)=3 (0) Chiral produet = 2 (€) Optically inactive = 2 Sol. (@) Total number of products (x) = ? (b) Total number of structural products (y) = ? (©) Total number of products separated by fractional distillation (z)=? SaSbed.< (2) Total number of products (x) = 9 (©) Total number of structural products (y) = 5 () Total number of products separated by fractional distillation (z)=5 50,by = (a) Total numbor of products (x) = 7 (b) Total number of structural products (y) = ? (©) Total number of products separated by fractional distillation (2)=? (@) Total number of products (x) =1 (b) Total number of structural products (y) = 1 (©) Total number of products separated by fractional cistillation (z)=1 Qs ms, (a) Total number of products (x) (b) Total number of structural products (y) = (©) Total number of products separated by fractional distillation (z)= © bat. bode (a) Total number of products (x) = 12 (b) Total number of structural products (y) = 4 (© Total number of products separated by fractional cistillation @=6 51