ee. Unit 1 Nucleophilic Unit 4... Aromatic Substitution Reactions Unit 5 Elimination ReactionsUNIT | Nucleophilic Substitution At Saturated Carbon Syllabus e¢.. SN’, SN" and SN’ reactions, Mechanism and stereochemistry, regioselectivity and stercospecificity of substitution reaction. Scope at saturated carbon, allylic carbon and vinylic carbon. Factors affecting rate of SN', SN’ and SN reactions (Effect of nature of substrate, nucleophile, leaving group and solvent). Neighboring group participation (norbornyl &* norborneny! systems), Non-classical carbocations. (09L, 12”) 1.1 Introduction Substitution is the replacement of one group by another. When basic, electron rich reagent as nucleophile attacks the saturated carbon which bears a leaving group results in the substitution reaction, the reaction is called nucleophilic substitution. t called 3S RX + Nu ee Ne Xa Substrate Nucleophile Product Leaving group The compound on which substitution takes place is called substratre. The substrate is characterized by the presence of a leaving group. The leaving group is displaced, taking the electron pair with it and departs from the molecule. Nucleophilic substitution is an important class of organic reactions. For example, Alkyl halides undergo nucleophilic substitution reactions with a variety of nucleophilic reagents. CH 503 : Organic Reaction Mechanism onY suopeonang aeyseg QE ‘uonoeat sejnoo[oug HORDE Sty 29424 “FIO "2 a[doafonu Jo “aU0d se Jom se ns Jo “2uoo wodn spusdap wonoeou si Jo aie ayy re ss393ns uopeNbo ayy “yurysu0o aes = ¥ SHOU loon wornysqns Se POUo) St aH 7 [ti9g}[2—oti}x= au ba—oin] » [Hg] [oe] see “ria pasosqo st! soneas sn Jo pms nu 3 045 a0 9 | spun ENG = eee HO. + 2a—o'H 8 (Joweqpatm) }oyooT ou Jo ssseu96y 392915409 8 ss} UORDEAS NS ‘sen6ud pousouoa dors auo s1 st yowar zeyno2ouNTg [aeinaajouny 5) sejnqouun aqugdoorny wounsans. 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An ‘2 group with an unshared pair of electrons bets tothe leaving group (oF sometimes ther the mechanism operating in such cases is called as neighbouring group part [ED Posen rico quence of these intramolecular reactions is often seen in the rates of the reactions ia pentane proceeds 3 X10"times faster than the hydrolysis of I~ CH, — 1—hexanol CH, ~CH, ~OH 5m Onanc Reson Nec ISep sea rsx ‘Mechanism: sar that sulphur at chloride and enhancing leaving group and relief of times in such reactions eyelic products are formed. Ee ED Prashant Publications x rr c? HAC — CH — +x® é oO lactone 2 HC; S- CH, - CH, -OH + #30 rain from three membered ring also enfances the reactivity. Some Neighbouring group participation by C= C(n) and sigma (o) bonds: We have seen the neighbouring group participation by nucleophilic atom by using its unshared pair. Such participation can also be observed by x and « bonds. The = orbitals of double electron bond are able to carbocation. For of the saturated analogue 7-norboryl of 7-norbornenyl tosylate (1) is ind proceeds with retention of configuration. 130) H coat 1 ee ° : WA “ors ZL oncuscaatretin RbuotntGi . Bac e -OTs Inversion of confignsation The above reaction gives a strong evidence that C=C x bond can act as a neighbouring group and the intermediate formed is called nonclassical carbocation. Such anchimeric assistance is not 503: Orne Rescon Meceais EEalso called carbenium ion, For eg. 1 ; I ae @ 2 & a ont Gor bie) crbeetin Ht nln pecs elect ci Same cervus of -€ oy pecs of 6-Coab adv 6 Norbomyl cation EXERCISE @ J products in the following reactions [2 marks each, solved} CH, -CH-CH, + HBr—>? CH, ~CH-cu, iy f ans ORF aH, ou Ic 2) (Cth), C-0Ts+KoH—BO+? ‘Ans. (CH,),C-OH —cucen NAN ans, CH) -C=C~cHy, SD emcss ii) CCH; CHT [EID recon 3 » Ans, PhCH, -CH,-OH+SOCl,—>? Ans. PhCH, ~CH, Cl HH, Acetone coy-cn,-mrvc-6-OR A? cH, cH, I . CH, ~CH, -O-F CH, cH, [Rate of reaction of n-propyl bromide with CN” is high in DMF than in methanol expla |. Methanol is polar, protic solvent. In Reaction of n-propyl bromide with CN" is SN? reac this solvent the nucleophile CN© is highly solvated through hydrogen bonding. So it acts as ‘a weak nucleophile therefore rate of SN? reaction is slow in methanol But insolvent lke DME which i apolar, aprotic solvent the nucleophile CN® is not strongly ‘with aq. NaOH takes place by SN! mechanism. As in SN' mechanism carbonium ion PhCH" is formed as an intermediate this carbonium ion is more stable due to electron donating effect of phenyl ring. As Of intermediate carbonium jon increases, percentage of racemisation of the product increases. Hence hydrolysis of Ph;CH-Br with aq, NaOH leads to almost 100% racemic product. 1© sa good nucleopile as well as good lenving group. ° sa good nucleophile because it has strong electron donating ability. Ils electronegativity is also less Hence itis a good nucleophile. i155: Os Reason Mecaisn. EEhas large size and less electrone ‘weak conjugal od leaving group because lod ‘weak bond and led as nucleopig HO pec) E22 ROH + HCI (Slow reaction) #0 Rep 22 + ROH + HCL (Fast reaction KI 7 y he ae Rcl ——> RA + Ci (asa good nucleopile) #0 Rt CROW + (Las good leaving group) QUESTIONS Multiple Choice Questions 1. In SN? reaction, product is obtained with ........0f configuration. a) Retension Inversion ©) Recemisstion 4) Bothaandb 2, In SN' reaction, product is obtained with cof configuration. 4) Retension crsion )Recemisstion 4) Botha andb 3. The intermediate in SN! reaction is a) Carbor ») Carbanion ©) Carbon feraliacal 4) Carbene 14,» Which substrate generally prefer to undergo SN’ reactions ? b) Secondaiy a) Primary {. Reaction, product is obtained with ret sn’ reaction is b) Carbanion 4) Carbene 18) Carbonium i ©) alkylehloros fos Prashant Publ u 2 2B. ‘Tertiary substrates prefer to undergo nucleoph mechanise, a) SN? b) SN! 1d) both aand b Benzyl chloride undergoes nucleophilic substi rmechanisin. as by) sn? 4) None of these In SN* mechanism 4) Nucleophile attacks substrate in fast step b) Attack of nucleophile is from back side «) Leaving group departs and then nucleophile attacks, There are two steps involved Correct statement about SN! mechanism is 4) Nucleophile attacks inthe second step, ) Step-is rate determining step In SN' mechanism, rate of reaction is proportional b)Socl 4) Substrate only fs lead to more percentage of racemisation on ’) Leaving group departs in the first step. )Cs~ Cl ) CoH — CH: ~Cl CH - Rate of SN! reaction increases with 42) Increase in polarity of solvent ©) aprotic polar solvent Rate of SN? will be a) Water ) Ethanol Select the wrong statement a) As crowding at a carbon increas b) As crowding at carbon increases, rate of SN* decreases. ©) Benzylie substrates undergo SN? mechs (es undrgo SN! mechanism. ») decrease in polarity of solvent 4) nonpolar solvent solvent ©) Methanol ) DMF SN’ all [Nucleophilicity is the ability o donate electron pair to .. ‘) Hydrogen) Oxygen ©) Carbon tH 50: Onc Remton ectanism ER atom 4) Nitrogen18, Select the wrong statement is less nucleophi )CN” acts as ambi 19, Which one ofthe following is a good leaving group ? a) -OTs 4) -OR 20. Which one ofthe following is aprotic polar so ») DMSO. 4) CHO 24 isthe ambient nucleophile. a) OH byoR- en” 22. Fora good leaving grovp, a)Small, less b) large, ©) Large ess 23. _Inneidhbouring group participation reactions the produet is obtained with ) Retention ©)Racemization —d) None of these Neighbouring group participation is... a) Intermolecular) Botha and b 25, The rate law for neighbouring group mech ‘) second order) First order 4) None ofthese 8) Zero onder Answers 1b) 2 9 3 @ 9 6 4 7% bw & a a o 2 a) 1 a 9 » 1 9) 1 Ww » a 2g 2 25, by ‘Questions for 2 Marks Predict the product in the following 1 (cH), cH-oTs+ Nal ASSN, 9 [ED rote rsiestos 5. 5 cos = EE yy Ny CH Z5acrAcetone 0. Sv _CHVONAICH: F nc -cf—or, SE st ne-cec-H SR, 9 4 CH, MeBr + CH,Br —> 7 + S0Cl, —> ? Ph-CH,— ci4-ciy-Br + Nocn SE 2 cH,-cH=cH, KO 2 a 2) Leaving group 4) Basicity 6) Classical carbocations 8) Neighboring group participation ‘Questions for 3 Marks Explain the following Benzyl halides react by SN mechanism not by SN* mechanism, (CH, -CHH, - Bron treatment with NaCN gives CH, ~CH, ~CN as major product. Allyl chloride reacts by SN' mechanism not by SN? mechanism. 11509: Oc Recon ecerism E3) Stereochemistry 0 4) Ambident nucleophile 5) Effect of structure o 6) Effect of solvent on 7) Effect of leaving group on rate ofS 8) SN’ react 9) Neighbouring group participation 10. Classical and nonclassicalcarbocations Other Questions for 4 Marks 1) Compare between SN’ and SN? reaction. 2 iguish between nucleopilcty and basicity. 4 5) 9 b) Or + NaOH or aw 7) Which alkyl halide in following prs would react faster em ci, cab OR (Ch), b) CH,-CH,-Cl OR CH, =CH-Cl EID rosie rnin by SN? ‘mechanism justify your ions for 6 Marks Discuss SN? mechanism with suitable example and comment on its stereochemical aspects ss SN! mechanise with suitable example and comment on its stereochemical aspect. ¢' mechanism with Deseribe stereochemical evidences to support Si hat is SN? reaction? Discuss its mechanism with suitable example. What is effect of substrate structure and nature of solvent on the rate of SN? reaction? 6) What is SN' reaction? Discuss its mechanism. What is effect of substrate structure and nature of leaving group on of SN'reaction. Questions for 12 Marks cuss neighbouring group participation by nucleophilic atom and by C=C (n)orbitals. 4) Discuss the effect of nucleophile, leaving group and solvent on the rates of SN!, SN"reactions. 5) Discuss the scope of nucleophilic substitution at benzyl jc and vinylic carbon atoms. cit503 Ori Reton eds: EEUNIT 2 Electrophilic Addition to C=C SYP ADUS geen a sen Menon of pion C=C tod cin, of Indrogen halides, orientation of edition: Morkownikoff's and Anti stereochemistry, addition of halogens: ‘experimental evidences foro step mechanism mechanism of ation of bromine, factors offecting antstercoscectniny, effect of substiuens on rate of addltion of hxpokalous acids (HON), Hydroxslation(Mechanim of formation of cs and tans 1,2- dls), Hycroboration- Oxidation (Formation of alcoho), Hydrogenation (Formation of zonoyeis (formation of ldehyces &hetores). (091, 128) rhownikoff's addition (peroxide fe 2.1 Introduction When an unsaturated compound containing carbon carbon double bond is treated with coloured bromine water, there is decoloussation of bromine water. This is simplest example addition reaction. Unsaturated compounds containing functional groups ikeC=C, C=C, C=N, C=0,C=N fete. undergo addition of reagent completely across mukiple bond, Unsaturated comp. undergo these reactions very easily. Because, these compounds ar capable of al atoms or groups from reagents due to their tendeny of breaking of m in presence of atacking reagents “Adeition reaction is a reaction in which unsaturated compounds combine with afachiny ‘eaent 10 from asngle product containing al the atoms of reactant as well as reagent During addition reaction hybri changes from SP->SP*> spand_unsatuatl vd to less unsaturated product ot he sated product. In adit compound is convert oro x bond breaks and woo bond OM: Consider some adtion eatin. < bk See + HX ~C-C~ ae Ak L bon Nceo + HON — ‘ cca ‘N ‘Types of Addition reactions Breaking of a x bond between two atoms may be homolytic or heterolytic. Homolytic fission is found to predominate in nonpolar solvents in presence of light. It leads to free mechanism. While heterolytic fission is found to predominate in polar solvents. It ton reactions in polar solvents, rection is initiated by attack of an elecrophile om bond of reactant and the reation is completed by attack of nucleophilic part of reagent. Addition o C= C of alkenes isan example of eecropilc ation. 2) Nacleophilic addition Nucleophite adtion reaction is initiated by atack of @ nucleophile on = bond of reactant and the reaction is competed by atack of electrophilic part of reagent ‘Addition to C-O of carbonyl compounds is an example of nucleopilcaditon. ectrophilic addition to carbon carbon double bond ‘carbon carbon double bond(C=C) consists of a strong o bond and a weak x bond. The pair of electrons present in x orbitals are more difused and less firmly held by carbon atomic Hence x electrons ate readily polarized, leading to characteristic reactivity of such unsaturated compounds. Now, consider structure of simplest alkene, ethylene. Hg, Sel 1 Du + electron cloud les above and below the plane of molecule. Attack ofan clectrophile on this + electron cloud is very much favour attack of a nucleophile is unfavourable, ted by atack ofan eletropile on such x electron cloud present in all alkenes. Inelectophilic addition reactions, alkene containing = electrons are electron rich and they act 45 4 mucleophile therefore, there is attack of x electrons on the electrophilic end of the reagent, C03: orp Resin Nec ERUNIT 2 Electrophilic Addition to C=C Syllabus #@———— 4 1, Mechanism of electrophilic addition to C = C bond (AdE2Mechanismy, Itoduction, Mechanism of electro ‘addtion of Frdropen lids. orientation of Markonnitef's eddiion (perxide fei) stercochen experimental evidences fortwo step mechanism, mechanism of addi ‘afecting otstereoselectis, effect of substituents on rae of a ‘pokalous acids (HON), Hydrostation (Mechanism of formation of els and trans 1,2. dhol, Hydvoboration- Oridetion (Formation of alcohol. Hydrogenation (Formation of tiane), Ozanobss formation of acd & Ketones). (091, 1269 2.1 Introduction When an unsaturated compound containing carbon carbon double bond is treated with red colouted bromine water, there is decoloursation of bromine water. This i simplest example of addition reaction Unsaturated compounds containing functional groups like C=C, CaC, C=N, C=0,C=N, etc. undergo addition of reagent completely across multiple bond. Unsaturated compounds undergo these reactions very easily. Because, these compounds are capable of accepting additional atoms or groups from reagents due to their tendency of breaking of multiple bonds in presence of tacking reagents Addition reaction is a reaction in which unsaturated compounds combine with attacking reagent to froma single product containing all the atoms of reactant as well as reagent. During addition reaetion hybridization changes from SP—>SP*—>SP¥and unsaturated compound is converted to less unsaturated product or to the saturated product, In addition reactions ax bond breaks and two o bonds are formed. (Consider some addition reactions Saeed i ZORCL + HX 4 -E-C- 1 hk S 1 yo=0 + HON — -C-O-H éw HEED rasta PubticationsPrashant Publications »9| Fast eadad ans ‘Addition product‘Mechanism Let us consider one important ob alkene. When different dit fon and the other's secondary carbon in. oe symmetrical alkene takes place in such a way that having more number of hydrogens and nucleophile umber of hydrogens. Teatiary > Secondary > Primary (CH $03 : Organic Reaction MechanismMechanism Let as consider one important observation t mM OF HX y alkene. When different hydrogen halides alkene, reg X is involedg takes place in 0 steps, ep. there 2 of earbonium ion in attack of electrophile H” on x electrons of alker diate sep, reaction is completed by nucleophilic attack of X rests in isa slow step. n of reagent HX to alkene, thete is a choice which carbon of © = carbon gets X. But we cannot jon of attack by alkene. Therefore, we iis added to a symmettieal alkene ik] rashant Publications oe it cu, CH=CH, " Secondary carbonium ion (more stable) cH, CH CH, complex cH, -ct,- Primary carbonium ion (Less stable) se two carbonium ions formed in this reaction on the basis of Now, consider the stability of inductive effect and hyperconjugation. ‘carbonium ion is more stable than primary carbonium ion. Because, ion is stabilized by +1 effect of two methyl groups. Due to presence of six more stabilized by hyperconjugation effect also. less stabilized by +1 effect of only presence of only two «hydrogens, itis less stabilized by hyperconjugation effec. ‘Therefore, energy of mn requited for the formation of secondary carbontu that for ium ion. As a result, only secondary carbonium WF attacks only secondary secondary 1¢ ethyl group. Due t0 is less ‘carbon having less number of hydrogens. ther reagents across mcu, doen, 2-methyl propene Anti-Markovnikov"s Rule (Pers If addi Br (R-O-O-R), addi \drogen pero Benzoyl peroxide er is also known as peroxide effect. For example. if adk ‘get [-bromo propane according to ant sof HBr to propene is cared out in presence of benzoyl peroxide, We ovnikov rule, Peroxide cH,-cH=CH: > HBr SNE cH, ci, cH, Br Propene ‘bromo propane |-butene on reaction with HBr in presence of peroxide produces !-bromo butane CHy-CH.-CH=CH, + HBr -butene ~ CHh~ CH, — CH; -Br Vbrome butane fe reactions rddtion of HBr to propenc in presence of peroxide according yo dddition. Markovnikov's addi Regiosel The a is called regioselective 3 Tete i Markvnicov le so regiosel Wve addition Particult path of roo ation is preferred oF vei one of the two products is preferred over SS Tee a pe ee ‘When both parts of reagent syn addition ‘Syn addition parts of the reagent add from opposite side of the double bond, it is called ‘carbonium ion may occur from both sides. Ai alkenes, For example, cis 1, 2 dime OK cH, + HBr —>ee oe oP | eS Oi is obsered tht this reaction das not prosed by ne step pth” This on chars is refused on th basis of some experiment evens, Experimental evidences fort step Mecham 1) If addon of Br to elves cared ot in psec ofa meopieY" we ge products. One produc dibromide which is an expected ‘| expe ad, The second pe obtained by addition of Br atom and Y across C=C. oat ne yO mew cm pug, + cen : (CH, be be oa a Se ¢ reaction which is attacked 2) Addition of Br; to trans 2-butene occurs such thet two Br atoms add 7 to C=C from opposite side and anti addition reaction takes place. C for > Prashant Publications In one step pathway we ean get only syn addition product. Because ad xn opposite side is not possible in one step. Formation of anti-addition pro must be occurring in two steps. atoms fro tep is formation of cyclic ‘Addition of Br: 0 alkenes takes place in two steps. The fir bromonium ion intermediate. And in second step there is nucleop tromonium jon. In case of some alkenes, intermediate formed in the reaction may be @ carbonium ion +r mechanism of addition of bromine to cis 2-butene. ‘Step I: Formation of cyelie bromonium ion ‘There is polarization of Br; molecule as it approaches to the alkene molecule. There is action between 7 electrons of alkene and electrophilic partial positive charge. The complex then rearranges to termediate which is a 3 membered cyelic intermediate, ‘The eyelic intermedi then by attack of lone pair of adjacent Bromine on the carbonium ion. This step is a slow step. Step Il: Attack of nucleophile Br” ‘There is atack of nucleophile Br” on eyclic bromonium ion in the second step. The attack of Bri fiom the side opposite to large and bulky bromonium ion. It results into opening of 4 u Nec” cnc: 1 01, 70° Cen, S10" cH, 7° Neat A SY HOCH; HH CHy Cis2-butene reore Cyeiebromonium ion step ie cu a \/ H Gi Ue eA a | al Ng iF ta, @ (®) C1503: Opie Reston Measisn70% anti addition. Trans 2-butene adi ui (More stable) ‘Trans I-phensl propene ae For example, trans 2-b _ rey pc Rate is fast reaction [as it does not have any substituent, CH=CH, 96 1503: Omsic Retin Mest HC1> HBr> Hl b) HF A SEB + HO sand CH,=CH-Br +) Ethylidene dibromide and ethanal tye oni ad hal ree d) 1, 2—dibromoethane and ethanal zonolysis of isobutylene produces a) Propanone and ethanol «) Ethanal and propanone b) propanone and methanal 9) propionic acid and ethanoic acid Py oye eee he CBee ene? 9 2. )@ & &@ & Bw 1 » 2 Bw 1D » 1 9 BB 2 DD by) 2b), BY) 2H, BY 25D Question for 2 Marks What are addition reactions? Which compounds undergo addition reactions? [Name the two types of addition reactions. Define electrophilic addltion reactions. Why alkenes undergo electrophilic addition? Define hydrohalogenation of alkenes. Define Markovnikov's nile Whats peroxide effect? How electronegativity halogen effects the antistereoselectvity? \Whatis effect of solvent on aatistereoseectivity during addition of halogens? ‘efine hydration of alkenes. What is bydroboration-oxidation? How wil you prepare a chlorohydrin? 5 amy out conversion of ethylene to ethylene bromobyrin. Which reagents ean be used for cis and trans hydroxylation of alkenes? i150: ogni Recton Mesa, EE16) i) 18) 19) 20) 2) 23) 24) 25) 26) Define hydroxylation of alkenes, Which catalysts are used during hydrogenation of alkenes? Define ozo Write any two resonance structure of ozone. Predict the product (2 Marks each) Propene + HI —>? 2-butene + H,0 B52,» Propene + HOCL —+? Cis2-buene 304-42 LKMOOs 5 Cis 2-butene > |Ditorane _, 9 Propylene —s ya0TtH 0. Cyclopentene + Br —Sy2 Question for 3 Marks b 2 3) 4) 3) 6) 2 8) % 10) n) 12) Discuss general mechanism of electrophilic addition, Discuss mechanism of addition of HX to alkenes ‘Addition of HBr to propene gives 2-bromo propane as major product. Explain, Deseribe anti-Markovnikov's rule. Give experimental evidences fortwo step mechanism of edition of halogen to alkenes. How structure of alkene plays important role in antsercoseletvty during halogenation of alkene. Give mechani Discuss hydroxylat ‘Discuss hydroxylation of alkene by us How ozonolysis is an important re Discuss meckanism of hydrogenation ofalkenes wre of alkenes tat on ozonolysis ets fllowing carbonyl compings 7 ', Only CH; ~CO~ CH pound = CHO sm of addition of hypohalous acid to alkenes, 1 of alkene by using Os, reagent, 1g KMn0 for identification of stucture of alkenes? Give struct ‘a. CHy~ CHO and HCHO CHO - CH:-CH:~ CH seston for 4 Marks : : as Discuss. ‘AdE? mechanism swith suitable exampl 2 acs mechanism of ago of Ba ED roe 2 4 3’ 6 a 8%) % 10) ) 2) Question for 6 Marks 2 a 4 3d 9 0 (Question for 12 Marks » a » a Ba | What is effect of sub Discuss orientation of addition of 1X to alkenes, |What is hydration? Discuss mechanism of hydration of propylene. Write a note on ant Discuss Cis hydroxylation of alkenes by OsO. and KMnOx Describe mechanism of trans hydroxylation of alkenes by per acids {Write not on hydrogenation of alkenes with its mechanism. ism of ozonolysis of alkenes. Discuss stereochemistry of addition of HX to alkenes. Why alkenes undergo electrophilic addition? Discuss ic addition Define electrophilic adlt ‘general mechanism of eleetropl Deseribe addition of halogens to alkenes. Discuss mechani Cis 2-butene. ism of addition of bromine to addition of halogen to alkenes. Discuss hydroxylation of alkenes u i)050, i) peracid Give mechnism of ozonolysis reaction. How ozonolysis is helpful in structure determination of alkenes. jon of bromine and addition of ty in mechanism of a Discuss the simi hypobromous acid to an alkene. its mechanisin. Describe orientation of ad le and anti-Markovnikov’s rule to alkene. Describe the factors affecting anti- ttuents on rate of addition of halogen to alkene. schanism of eis hydroxylat Diseuss addition of HX to alkenes THX with reference to Markovnikov’s Discuss mechanism of addition of bron stereoselecivity. Discuss the effect of sul ‘What is hydroxylation of alkenes? Describe in det Aroxylation ‘ozonolysis? Describe in details mechanism of ozonolysis of alkenes. Discuss role ton of structure of alkenes. ‘of ozonolysis reaction in determi CH 503 : Organic Re ton Mechanism. QQ |UNIT 3 Nucleophilic Addition To C=O Syllabus « 3.1 Introduction ‘Addition reactions are those in which atoms or gfoups are simply added to a double or triple bond. Double bonds become saturated, and triple bonds are converted in to double bonds or ‘may become saturated by further addition, ‘Carbon forms multiple bonds with other atoms. These are of two kinds le bond with carbon atomeg. C=C, CaC (C= 0) carbon oxygen double bond differs from (C = C) carbon towards nucleophilic an ‘The polar character of >C = O bond mak reagents. Most ofthe important reactions of carbonyl group consist of clap aditons. .2. Structure and reactivity ae srr ieretivity of carbons] group depends on polity (pols sictuc) factors. a) Structure (Pol Both aldehydes an referred to as the Carbony! group- op petones contain 2 carbon oxygen double bond C0), Tig ge cred one Bo rom tn i 2 Prashant Publ i . (i) Structure of Carbonyl group ‘The earbon oxygen double bond consists ofa strong o bond and a weaker x-bond. The ectrons inthe bond of the carbonyl group are not equally shared; they are pulled more towards more electronegative oxygen. As a result the bond is polarized with the oxygen stom being slightly negative (5) and the carbon atom being slightly positive(6+). This In terns of resonance the carbonyl group is represented by the two contributing structures AandB +578 lS + SEP <> had A B c Resonance hybrid N\ 4 “eo with YE Brett carbon reacts with bases & nucleophiles leetronic and sterie factors + Nuclophitie addition The carbonyl compounds undergo nucleophilic addition reactions by the following general ‘mechanism, H503 Organic Reaction Mestanism QUelectrons ae shifted on oxygen. Nu 46-8 Ng Ceo = Se-d nweoo7u Y Step It ‘The negatively charged oxygen abstracts the proton to give the product | no-g-P Mn Bo -G-o1 Su ‘may be catalysed by acids or bases. — ® H+ + BH Weak 8 nucleophile hucleophile aa nS uP. Sy Water Strong (Weak nucleophile) rucleophite Under acidic conditions the electrophilic H” fom acid adds 1 give protonated product. Ne NN CBF WP Sepsn ON, a DS o-m ‘The protonation makes the carbonyl exon moe eecop Structures) The nucleophile then acts the protons Addition produc. 2 MASE o-u don In both acid and base catalysed mechanisms the adition products same, bond bras gy ‘strong one by removing a proton. first to electronegative ox We. (as shown in reson] yl group to form k by nucleophile. ‘carbon, more will be the rate of 9 wns orba 5» onebircs ‘As the number of electron donating substituent on the carbonyl carbon increases, electron donating inductive effect increases and the electropositive character of carbonyl carbon decreases, hence the rate of nucleophilic addition decreases. snyde carbonyl group is more electro positive (electrophilic) than ketone carbonyl fore aldehydes are more reactive than ketones. rate of nucleophilic additions increases, if the electron withdrawing substitutents are z d D-H > present on carbonyl carbon. g 3 one cn -bn > ec. cu,-C-n , while the ‘The groups which exert +R, will decrease the rate of nucleophilic addit groups with -R will inerease the rate of nucleophilic additions. Orbe OL “PO =R effect +R effect Sterie factors also play a pat in the relative reactivity of aldehydes and ketones. )prosch by the nucleophile to’ the carbonyl from back (reat) of the carbon, Increasing ate as the SP* hybridised carbon atom in the ®. Thus if more crowding is there in the state will be decreased. conor C109: Oi Rete Mean ER [EID er rataion ? Ce Bae oe‘The relative reactivity of some ketones is 9 9 In general all these factors affect the rate of reaction and influence the position equilibrium. ‘Size of nucleophile “The size of the nucleophile also affects the rate of reaction. Eg the K value for bisugty (5.0%) adition to diethyl Ketone is 4% 10" wile for aditon of CN to ethyl met Ketone is 38. “Addition reactions of carbonyl group are studied under three heads (a) simple addi (b) Addition-climinations(¢) carbon uncleophilic ations 3.3 (a) Simple addition reactions 3.3.4 Addition of Hydrogen cyanide “The addition reaction of hydrogen cyanide with carbonyl compounds gives the formation ceyanohydrins. * OH : orf | o + HN =— ~ cn H # Faas Aldehyde eyanohydrin vas almost certainly the first organic reaction for which the mechanism ICN is 2 weak nucleophile and requires base catalyst that action follows the rate equat®} CCN ads to the carbonyl carbon ina slow s# which is @ strong base and % ducenew CN aetaets ap =» Prashant Publications @ name 146 i : a HH, fo} a cn A . Tow cx uf Now Acetaldehyde ‘Analkoxide Hen te a ee Ne hestsinerae important as a new carbon-carbon bond is formed and 1 of catbonyl compounds with aleohols forms hemi-acetals. R RoR ‘ °o ‘oH == Nc Re Rr” Nou Hemi-acetl Inprsence of ai catalyst, the equim i toward ight only w dehyde, but stable hemiacetals groups, 1 be isolated from carbonyl compounds containing electron withdrawing. i BnC-CHO + C:HOH —> Conversion of hemiacetals to acetals requires acid catalyst, the mechanism is as follows. e R Ror === R Ne-0 + now == ce a \ we won WNP Aldehyde Hemiacetal H i103: Reaction skis QE+ HO Rv \o— CH, Cyclic acetal ketal Hydrolysis of acetals to carbonyl compound is possible in dilute acids, but not possible in ba stays. Synthetic use ofthe above reaction: 1 fantions as ffs protecting soup because its ast pun i) Stays on em 0 form hemi-thioaceals and thioacetals rath tore readily than with ROH. This is due to greater nucleophilic of sulphur compared wid oxygen. z CH, i Dry HCL con, lecn, + 2c sn POEL. oon cuts -cr, Addition of derivatives of Ny, suchas hydroxyl amine (NHOH), semicarbaide(HN-CO- NHI ‘compounds in to solid derivatives for their characterization, 2, 4initro phenyl hydrazine is particularly useful in this respect. Reaction with strong nucleophiles such as H;N-OH do not require catalyst but weaker ones such as PHNHNH; often require acid catalyst. ce a H H _——— © en ligrapon — onl d Hydroxyl H-N@H amine bu 4 4 — nd Bn BL ca, -c=n-on HG i a Oxime of benzaldehyde ,H -,0 i) G\H,-¢ = 0 + H,N-NH-CH, "25 C,H,-C = N-NH-C,H, H, cH, Phenyl hydrazone of acetophenone ') Addition of primary amines: Primary amines add to the carbonyl group of aldehydes or ketones to form imines. iH 9 N-cHy 2 ie nego o a NR-cH eg toy, fet] ix) ia CoH ne N-cH, i nes are general ‘aromatic eq. Ar R-CH=N~CH, ‘An imine Ione of the substituents on the carbonyl carbon atom. i stable products are formed known as Schiff bases, CH 303; Orgmic Reaction Mecham QESa cleavage between carbon 8 a Ne Scr — 8.8 Cartaiog 43.5:1 Carbanion formation by a fuse ~The RSE 26 oF ate, yaad egal ccex StL (SCH om, se} sno EID poser nse: Thus more the “$* He = c® H+ NaNUL. ¢ but polar-e ing acidty isSep cH cite AP, Bei HE h e BED erotic (CH 503 : Organic Reaction Meor “Te cakes ofertas sabi primary, secciny ad tert crbenions ar sy g S ~~ Hc-E= cu, 2 2 HC-GH, > HC-CH > 3 fe cxcfopnton wit the matiple bonds, then stabilization thal 14s 8 = ASS coopert with simple atkene sty on lt eet xtacion in eelpene sed em (oats sem ike benzene) \ | Py. , Ac [Se 7D (3.53 Aldol condensation a padensation berweca two molecules ofan aldehyde ora Ketone ving a-tydrogen siccs io “eaence of a base to form B -hydroryalichyde or B -bydrony ketone cy-bo0 -npeeo Oe cH-€- 6 -€-0 H OH H ‘Two moles of aldehyde B-bydrony aldehyde pee fac 2 EY é cH,-cHO == i, ; <—— CH=0 Sept H H - enue Ce 8 e wen HE Lo ae cH -CH-cH, cH = H ) Sep cy GH - cH,-cHo BO. cH, -cH - cH, - CHO B -béroxy butanal Ose aldehyde molecule loses its a-bfdrogen atom to form carbanion (a), this carbanion 9 2 i Step1 CH, ~€-CH, oe > z A, — vl @ Hf CHS: OrasicReaton Micon EBlO Step CH Step cI Under acidic c 4, unsaturated ier) molecu “The cannizzaro rea ‘Aldehydes. havi = CHO) is heated condensation he carbonyl groups are present within the same molecule, intramolecular aldol takes 1 is a disproportionation now hydrogen atoms (for example formaldehyde, benzaldehyde, hydroxide, undergo Jf oxidation reduction) foming approximately equimolar amounts of the OH {eduction product) ©.H,COOK (Oxidation product) sa} + 1Onidation product 2 Aldehyde HCOONa + NaOH —> 10Step I Step tt: CH, -C-0H-+ H-C- GH, Carborsic acid k alkoxide a ft, © ft, cy, -c-0%+ A proion exchang Hq cH, Benzoate ion 1 H Benaslaleoho ‘Similarly in case of formaldehyde - Lo e n-coH te H-c-H & e on 4 ony a cee gh M aa be - Kl 5° Co Hcg ge gk : prion extn, y—C-OS+ H-C-on I tf & Crossed Cannizzaro reaction CjH,CHO + H-CHO + NsOH —> C,H,OH + HCOONa In crossed cannizzaro react always better to use formaldehyde as one ofthe aldehydes tu formaldehyde carbonyl is extremely reactive and in the frst step equilibrium willie on the fide of formaldehyde tetrahedral intermediate, and the other aldehyde will remain as aldehyde. Inthe second step formaldehyde immediately undergoes hydride transfer to enother aldehyde that wil lead to the formation of alcohol in good yield. ° ° ° i] I i] 2 R-C-H+H-C-H aR -cHoH+H-C-0° ° Hu ~ I lo fo —sH-C -on+ R-C -O' ctt50:OrpnicRewien Main EY3.5.5 Perkin reaction ‘The condensation between aromatic aldchyde and sodium or potass yield 6, B unsatraty aromatic acid known as perkin reaction GUCOONS cu, -cH=CH_-COOH + CHCOOH. benzaldehyde Acetic Cinnamic acid anhydride ‘Mechanism ‘The carbanion is obtained by removal of «-H atom froma molecule of acid anhydride. & 9° HH, -CO, &i,-co, i) No kiscoona ~ vse Chee (O mths B00, i) T eo o H >= cc ci,-co~ CoH H 4 ity) mag gG ~ CON no, ™$=C-c0 HOH oo — H ~ 4 0 cHy-CO Hie~co 7 suonyobse_, Ph=Cl'=CH~COOH + 1,6 _HyOtaydrolysis_, Suphenylpropsncicacid (cinnamie acid) ERD sen rico |. perkin seston proceeds more realy when the aromatic aldehyde contains halogen stom or anit group in the nucleus. 5,546 Witig reaction ul reaction for the synthesis of alkenes. Ths involves a usually called as Witig reagent to the carbonyl group of aldehyde or of triphenyl This oo wong ten + rene HC s Bewapheone Na) pace z ; | ee tog : . Phosphiorane form ‘An ylid form is a earbanion having an adjacent hetero atom, such species can be generated by very often Ph,P- to yield a ed by abstraction of a proton by a stong base like PhLi. In genera can be shown as + PhLi + = PhyP + RR'CHX ——> phyPH—CHRR' ——> PhyP—CRR’ | PhP === CRR' For eg. When triphenyl phosphine reacts with methyl bromide in ether methyl tiphenyl Phosphonium bromide is formed, which on treatment with strong base gives an ylid, CyeisLi Se cuiyye = Ch + LiBr + Cyt, Methylene trphenyl phosphorine| cit sts: Ori Reson Mechanism QEig reaction carbonyl compound is added to ne product Mechanism one i Betaine Oxaphosphetane Ll, 3s == cH, + ° PhP—=o Mei per HC PPhy Alkene oe give oxaphosphetane intermediate which is '80°C) that decomposes to the products alk raising the temperature. is very useful and versatile method to symtbesize panicularly valuable in getting the double bor methylene groups + nein, CY + mp0 ‘Triphenyl phosphine oxide cyclohexanone 35:7 Reformatsky reaction “Thisis the method for preparing P -hyroxy ester. In this resction oganocine derivative of halo ester react with carbonyl compound to produce B-hydrony eter, ci Br—CH, -COOC,H, + Zn BrZnCH, COOC,H, ethyl bromo acetate Ethyl bromo Zinc acetate ods sen BrZaCH,COOC HA — Cals “EHC, coc, y, [ED Paste rstons Mechanism : achaloester reacts with Zn metal in presence of benzene to form organo Zine lo ester. This of «-halo ester on addition of carbonyl compound Na C08 <——= Bren CH; ——c—on, BrCH,COOEt is analogues to RMgX. The organozine compounds are less reactive than Grignard reagent and do not normally react to its own ester group. It cannot add to sterically hindered carbonyl compounds, it best proceeds with aldehydes, methyl ketones and cyclic hetones. Example: ea H,S0, Caucocts * BrcHscooR, —* cqiy— GOH) —CHACOOE 2)H0 cs | a= Gr exc008 CH; x ' ‘6 Reduction reactions using NaBH, LiAIH fideon 45 nucleophile (Reduction) dene 28 P9Ra Tou to an aloha involves ation of hydrogen (H —H)aeos the Of aso eis special entaysts and often high presue conditions, Ihe re beth St C = O group Jing compound jyde and trichloro acetaldehyde wyde v 2) ii PE a oda “Reffect sleffeet Wie aldehydes are more reactive than aromatic aldehyde, hence than benzaldehyde acetaldehyde the CH;~ group exerts +I effect of the carbonyl group. While as compared to resonance effec, therefore le of inductive effect is s ore electrophilic. ° I & ot RIS) a aR ‘more reactive than acetophenone. [a acetone the two methyl groups exert +1 in acetophenone CHy~ group exerts + effect and phenyl group exerts +R effect, c11503:crguic Recon Netin OHiii) Acetaldebyde and trichloro acctaldehyde 9 ao i ad ch, -C-8 & clef —t-H Acealdehyde cc Chon acetaldehyde “is more reactive than acetaldehyde, because the three cleces, ‘withdrawing chlorine atoms exert -I effect and due to which the positive character of carbo carbon increases, thst increases the reactivity too acetaldehyde and chloro acetaldehyde 9 , i O:N—+cH, -C-H & c+ CH,-C-1 acetaldehyde is more reactive than chlord acetaldehyde as -NO: groups is strong jestron withdrawing than chlorine, hence NO: group increases the positive character ai Ams. R RoR Yevo mn HE, Sed R R’ OR ssc R, eo Rs Yero sans aie Nef R 7 sy Thio acetal tn thiols sulphur exom is nucleophilic andi lobo nye som smug cf ‘oxygen because it is les lie. Sulphur is mere nucleoplic than OxyES ara Hence thiols react at faster rate. “The product thio seta isms tan par ta oxyge 45, Wh aqueous medium canzot be wsed for retin by LAM? ; eye aldehyde and ketone, AIH. ISW08* BAH aye {a to primary alcohols ete. “ae Tor LIAIHL reduction, aqueous medium cannot Be Wed sige it rear vig product H; which may get ignited ds tothe Hes oduced, (50: ia ly with water t LAM, + 41,0 —> Liot + Aon, + 44,4 nrefore non aqueous medium sich as dey! ether, terahyrofuran (THF) ae nomaly the Product. ) Gil CH= CH-CHO + Lill, —> A 122" 3 t jes GjHy~ CH = CH-C-H + LiAlH, —> H I © ® yom GH, -CH=CH-C-O-PAl Li #9! 4c,H,-CH=CH-CH, -OH 4 | B A ° » rcv -le, SH, , ow y a ° on i me mdiven boy St mle t ——» Ph-cH=cH-C-cH, ® 2 : ° ~CHy+CHsH _H, 4 BN ip ns, i @ WC. SCalls 4c CH, -C-CH, +C,H,SH H \Z HyNi > oN ee Hc* Scat HC ry e B (CH.503 : Organic Reaction Mechanism RC BCH > AFB CHS-CR ©) AP> RC =CH > HC=C> CH,-CR, whe ‘Acctaldehyde on réaction with dilute alkali gives, 4) a hydroxy butyradehyde ©) 7-hydroxy butyraldehyde Cinnamaldehyde can be prepared by cross- aldol condensation of 4) Benzaldehyde and acetone sive a, B- unsaturated carboxy 2) Perkin renetion ©) aldol condensation ©) 3— phenyl propenoi Aldol condensation involves intermediate ) B - hydroxy butyraldehyde 6) 8 hydroxy butyraldehyde ») Benzaldchyde and formaldehyde 4) Benzaldchyde and acet anhydride in presence of sodium ace lehyde ion condensation b)3 ~ phenyl propanoic aci 4) 2— phenyl propanoic acid 1) NaBH ena ) following undergo Cannizaaro reaction? a Formaldehyde and acetalichyde 8) Bead NU and acetaldehyde slsandenslehde ——€) Acclyacang eee lonaldehyde 2) Analdchyle molecule undergoes oxidation b) An aldehyde molecule undergoes redvetion «) Aldehyde molecules undergo disproportionation B89 4 ow ay » 2 Y Boo O18. » om b& Bd a) 20. 9 m2 fds eee 2aee 1) as for 2 marks i ues ine structure of carbonyl group, 1) Discuss t 2) What aro enamines' a 4 9 th carbonyl compounds. on, when NH,OH reacts mechanism (2 marks) i) Et,0 cH,COONs ,C0),0 SECON, 9 a 8) on dn » Cy owe =e, CHS CH, =O + HAC = P(CQH), — 2CHyCHO + KOH —> 2HCHO + Nao —> 1150: Orme Retion Mecham SB eemechani a real of meal to °C cusos:ommicrecioa Mccainin reaction, giving mechanism, Diseuss the general mechanism of addition of nucleophile to >C = O group. Deduce the selationship between the structure and reactivity towards nucleophilic addition to carbonyl group. Discuss the mechanism of Cannizzaro reaction’? reactions with respect 10 addition of hydrogen eyanide ili) Addition of water Explain carbanion formation, stabilization in details i) Reformatsky reaction with mechanism, m1 reactions to carbonyl compounds with respect to addition of CCH 503 : Organi Reaction MechUNIT 4 Aromatic Substitution Reactions Syllabus 6. —_— " Electrophilic substitution Inaroduction, arenium ion mechanism, Effect of substituent group (orientation, orthofpara directing and meta directing groups). Classification of sl tration, Sulphonaion, Halogenation, (091, 1249 ‘Aromatic compounds undergo substitution reactions in which one or more hyde atoms attached tothe aromatic ring are replaced of ubstiuedby other atoms or groups fo attacking reagents. This typeof reactions are called Aromatic Substitution Reactions. Substitution reactions are characteristic reactions of aromatic compounds, not ad reactions. Even though benzene and other aromatic compounds contin altemave double ingle bonds, they do not undergo addition rescons. Beease, afer eddtion rest aromatic compound is converted to non-aromatic compound and aromatic. character ¢| Compound is Tost. While afer substtson reaction, somatic carter ot compou maintained. The attacking reagent in aromatic substitution reactions may be an electropho: nucleophile. Therefore, onthe basis of atacking e220! ve can divide aromatic soba ing to discuss these both types of aromatic gut reactions In this chapter we are g by one. [ELD entrees of aromatic compounds are classified as electrophilic ns, attacking reagent is an elecrophite. During en carbon and hydrogen from aromatic ring breaks replaces arity of substitution reactions. these dtetoptilic substitution, the bond ada new bond between carbon and el natom or group other than hydrogen atom also. is attached to aromatic ring are replaced »matic Substitution reactions. jon reaction in which benzene is bythe electrophiles, are called Elect For example, consider a common eles reacted with Br in presence of FeBn replaced by an eletrophile Br. Benzene Bromobenzene set a dibromide, in such reactions, If'we carry out addition of Br, across a double bond of benzene, we hich is a non-aromatic compound and aromaticity of the compound ‘Therefore, benzene and other aromatic compounds do not undergo addition reactions. ar alum ion intermediate is formed, Therefore, mechanism of electrophilic subs ‘Arenium ion mechanism, clectrophile and delocalized 7 electrons of benzene to forma 9 tron, S087 The x complex then earanged to fom te. comple whish also Seium ion oF carbonium ion intermediate o Whelan ntemedite . cHs03:Onpnie Reason Metain QE