GENERAL ORGANIC CHEMISTRY & SOMERISM in general, organic reactions can be re substrate + Reagent ——> Intermed The mechanism of organic re (i) Electronte effect (i). Fission of covalent bonds (iii) Nature of attacking reagents Presented as, Hale — Produ tions can be ¢: any be explained on the basis of three factors, ELECTRONIC EFFECTS Inductive Effect ‘The polarity produced in the molecule di lue to elect two gpes of inductive effects Teer oof rete iference among the bonded atoms. There are +L fleet : Groups (electron releasing) fa (CH:)sC- > (CHsCH-> CHCH-> CHy-> 4 J effect : Groups (electron withdrawing) N(CH), > NO; >CN > F>Cl> Br>1> 0H SOCH, > CH, Mesomeric Effect The polarity produced in the molecule due to interaction between two x bonds or a x jone pair of ae Is or a x bond and lone pair of =0 Electromeric Effect Under the influence of attacking reagent, there is a transfer of shared pair of electrons to one of atoms joined by multiple bonds. It is a temporary effect. : \ / \s / r\ fN Hyperconjugation Effect The effect of transfer of clectrons from occupied orbital or double bond to an unoccupied orbital 4 ] uw TASS NS OSa. FISSION OF BONDS (BREAKING) (1) Homolytic fission: Generation of free radicals, (it) Heterolytic fission: Generation of earbocations and carbanions REACTION INTERMEDIATES stability factors | Order of |< eae Intermediate Shape siabiliy Hyperconju- Inductive Stey Resonance gation effect hindrance Se ty : Ppewey acArcn, WS 2° > 3° ml) Carbanion “i pe ‘ Teffect 6 ° HA A. wy Singlet sp? : "ScD Carbene Triplet sp - : iQ, ORGANIC REACTIONS Substitution Reactions (i) Free radical substitution: CH, +CL >CH,CI+HCI (ii) Nucleophilic substitution: (a) Sy mechanism (intermediate-carbocation) (CH), CBr + Nu —9(CH,),CNu + Br (b) Sx2 mechanism (no transition state formation) CH, -Cl+ Nu —>CH, -Nu+Cl sss EEA Ke SSO SSIS(c) Sy mechanism Gntermediate carbocation) 1,0. Br + OH (ag) —¢ 1,0 (iu) Electrophilic substitution: CH ECL oe HCH NCH ate addition Reactions (1) Electrophilic addition reaction; Intermediate carbocation . cr Cyc cn, hy a lic (1) Nucleophilic addition reaction: Intermediate highly stable Br anion cw eff a) (iu), Free radical addition reaction: CHCH= CH" SCHCHCH pe Elimination Reactions (i) a-elimination ; Intermediate carbene CHC ZS CCh, (ii) B-elimination : (a) El mechanism (intermedhate-carbocation) 1 4x (c)_ El-c mechanism (intermediate-carbanion) " om, °. cn, om Hoch ASAT SRT 5 STRY & ISOMER!- fn YI Se7 (SOL on Rearrangement Rei (i) HF shifting: 1, 2- (ji) Alkyl group shifting® (iii) Bond shifting: Beckmann rearran| actions ide cei sift inalky! al ge thy shi in iO} jgement - formula show different structural IsOMERISM me molecula ssomerism isa property by virtue of which compounds having formula and properties. Types OF ISOMERISM Structural Isomerism (i) Chain: cH, CH,CH,CH,CH, and CH,CH cH, (i) Position: HC: \_ oa, mf ne I (iii) Funetional: (a) CHyCH:OH and CHsOCHs (b) Alkene and cycloalkane (CoH:s) (c) Aldehyde, ketone and cyclic ether (CrHax0) (€) Carboxylic acid, ester and hydroxyaldehyde (CaH2202) (iv) Tautomerism: H os (—c—=0 == eae | 7 (keto-enol tautomerism) (v) Metamerism: (CHsCH,0CH:CHb and CHsOCH2CH:CHs Stereoisomerism (i) Geometrical: HOO cooH HOOC H and H H H COOH Co trans ee TASS Ae() Optical: CH, HC a PROPERTIES OF CIs AND TRANS Forms (1) Physical properties: (2) Dipole moment, cis > trans (b) Melting point, trans > gig (11) Optical activity: plane of plane pol COOH Plane of symmetry (optically mative) Total isomers: Optical isomers having ‘n’ number of chiral centre fany molecule is not s lanize d light. Such symmetry line of symmetry pl No, of d and | forms (a) CH | " 4 | Hy Contre of symmetry (optically inactive) lane of symmetry, etc No. of Mesoforms (m) ‘uperimposable on its mirror image, its bulk sample rotates the Molecules do not have any symmetry element like point of Total no. of optical isomers (a + m) When molecule has no Pe in oe symmetry If'nt yn» 0 When molecule has symmetry eeeee a 2 Ifa" is odd ame gun Representation of stereoisomers: For example, 1, 2-dibromobutane Fischer projection Sawhorse projection Newman projection CHy We meet, i BH He a! / HBr 4 cH, Bae Dand L configuration I CHOH CH,OH L R and S configuration: The priorities are to be decided using Chann ~ Ingold and Prelog sequence rules 2 cHO CHO a Au H-t—on HOH oo | Hj} 0H © CH,OH 7 COOH 2R.38) MP-CHEMISTRY-GENERAL ORGANIC CHEMISTRY & ISOMERISIGES ILLUSTRATIVE PROBLEMS after removal of the proton is stabilized by Sol. The proton is removed easily because the anion formed resonance with three -NO, groups as shown HP HW r r Ko ° lo ol S So oN Ne NO, No, 9 | CHO (a) (® Accis stereoisomer j (il) A pair of enantiomers Gil) Meso form BAPE tke a iaasititt Sol. (i) (aii) (b)(c) (iii) (d) (iv) (©), (e) (v) (b), (c) CESSSok (a) e NN ly Be < Heer, < HC Bcc a 3 (b) 2-hexene < 3-hexene < I-hexene HC. o -\ CH, : He en, © eT I \subjective Question if prob. 1. Give proper explanations (i Compound th of the following: 8 grea Ph, Sreater dipole moment than compound II 9 ) A Ph 1 Ph “p, Gi) Which : — has the greater electron denciSty on its nitrogen atom ? Yo N N—-H H (iii) Species lis more stuble than 1 De pe Sol. (i) Greater charge separation is] assign ita higher dipole moment, i) Y iy e/ a N A i in | NH No such resonance is possible, Hence ¢° density is more over on N atom, Objective Questions Prob. 1. The type of isomerism due to different types of allyl group on either side of functional groups in the molecule of compounds CHsCH;OCH2CHs and CHsOCsH) is referred as (A) metamerism (B) chain isomerism (©) functional isomerism (D) position isomerism Sol. It is definition of metamerism, Hence, (A) is the correct answer, Prob. 2. Number of isomers possible for CyHy are (a4 (B)3 (C)2 (D)5 CURES TSSe MOON oe daa a charge of eatncaton, heer incense IY Cll OUP shows +1 elfen, o it wil depere the charge an Nf, -OF group, Wer NO: group shows - Mit effet due to wiven the positive charge on the carbocation increases. stability decreases, he stability Hence, (B) is the correct answer o of i of oO snd oi b. 6. Prol Pr Hy . a : H ‘Which of the following statement is ‘rue for the above two compounds? (A) Above pais ae resonance contributors B) They are structural isomers (©) They ate group isomers (D) They are tautomers. Sol. (B, D) Prob. 7. For, H H H (A) cis form is more stable d (B) cis form is less stable du (C) trans form is more stab} (D) trans form is less stable ue to H-bonding ie to steric hindrance ic due to lesser crowding in the absence of H-bonding So. (B,C) Prob. 8. Which has asymmetric carbon atoms? A) ol er 7 ve H: H HOH HH Oar ©) wt a it » CH: oe Br OH Sol. (C,D) Prob. 9. Which of the following has an asymmetric carbon atom er 8) 4 omy A) ye i { Br CHS i Hs CH, 0 CHs (Cc) ie ae x & be ‘Che So. B,C) MP-CHEMISTRY-GENERAL ORGANIC CHEMISTRY & ISOMERI:12120 COMPREHENSION Read the following paragraph and answer the questions given below: Organic molecules show chemical reaction on account of hemolytic bond fission or heterolytic bond fission in addition to inductive effect, electromeric effect, resonance and hyperconjugation. The usual reactions shown by organic molecules are substitution (Sy1 and Sx2) addition (syn and anti) and elimination (FE, and E2) reactions alongwith rearrangement reactions. In addition to these, various oxidation and reduction reactions are also Biven. The species which attacks a +ve centre is called nucleophile and the species capable of attacking ~ye centres are called electrophile 1 Sol, Sol. Sol. The most stable carbocation among the following is * (A) CHs (B) CgHsCHCH, CHy © CH, -C(CH,), ©) ¢,H,CH, © During nitration of an organic compound, HNO; acts as (A) acid (B) base (C) neutral (D) salt B) Which of the following is neither a nucleophile or electrophile? (A) NO; (B) cr (C) CN" (D) (CH3).N* @) eS CNAAE AS eee OEEREASONING TYPE QUESTIONS uch ection CONLAINS reasoning e if whicl ONLY ‘DNE is comer as NINE '9PE questions, Each question has 4 choices (A), (B), (C) and (D), out 0 STATE MENT-: Heat of neutralization of CHsCOOH Vs NaOH is numerically less than $7.1 KJ €4 STATEMENT-2 wa Some heat is us. caidas STATEMENT — 1 ig True, epaynotize weak acetic acid STATE 1 explanation for STATEMENT. | "ue, STATEMENT-2 is True; STATEMENT -2 is correct expl (B) STATEMENT TATEMENT-2 iy True, STATEMENT -2 is NOT a correct MENT-1 Vis True, STATEMENT:2 is False "is False, STATEMENT-2 1s True Sol (A) > STATEMENT-1: There 's evidence for existence of N-methyl acetamide in two structural forms 1 and II as shown below: 7 mG Hy Hi, and STATEMENT-2: Rotation about C-N bond is restricted due to resonance. (A) STATEMENT ~ 1 is True, STATEMENT-2 i True, STATEMENT -2 is correct explanation for STATEMENT-1 (B) STATEMENT ~ 1 is True, STATEMENT:2 is True; STATEMENT -2 is NOT a corect explanation for STATEMENT-1 (©) STATEMENT ~ 1 is True, STATEMENT-? is False (D) STATEMENT ~ 1 is False, STATEMENT-2 is True Sok (A) 3 STATEME CH, adds to >C = O group irreversibly but CN" ion adds reversibly and STATEMEN CH; ion is much stronger nucleophile than CN° ion. (A) STATEMENT ~ 1 is True, STATEMENT-? is True; STATEMENT-1 (B) STATEMENT ~ | is True, STATEMENT-2 is True: STATEMENT -2 is NOT a correct explanation for STATEMENT-1 (C) STATEMENT ~ 1 is True, STATEMENT-2 is False (D) STATEMENT ~ 1 is False, STATEMENT-2 is True STATEMENT -2 is correct explanation for Sol (A) TASS ATs NR IO TSSol. Sol. Sol. Sol. CS STATEMENT-1: Grignard’s reagent and dialkyleadmium both react with acid chlorides to form tex alcohols. and STATEMENT-2: Grignard reagents are less reactive than dialkylcadmium, (A) STATEMENT - 1 is True, STATEMENT-2 is True; STATEMENT -2 is correct explanation for STATEMENT-1 ; (B) STATEMENT — 1 is Truc, STATEMENT-2 is True; STATEMENT -2 is NOT a correc explanation for STATEMENT-1 (C) STATEMENT ~ 1 is True, STATEMENT-2 is False (D) STATEMENT ~ 1 is False, STATEMENT-2 is True @) STATEMENT-1; Allyl carbocation is more stable than vinyl carbocation. and STATEMENT-2: Vinyl carbocation is destabilized by resonance. (A) STATEMENT - | is True, STATEMENT-2 is True; STATEMENT -2 is correct explanation for STATEMENT-1 (B) STATEMENT ~ | is True, STATEMENT-2 is True; STATEMENT -2 is NOT a correct explanation for STATEMENT-1 (C) STATEMENT — | is True, STATEMENT-2 is False (D) STATEMENT ~ 1 is False, STATEMENT-2 is True © STATEMENT-1: Phenol gives Friedal craft alkylation reaction faster than benzene, and STATEMENT-2: -OH group is activating group for electrophilic aromatic substitution reaction when present on benzene. (A) STATEMENT ~ 1 is True, STATEMENT-2 is True; STATEMENT -2 is correct explanation for STATEMENT-1 (B) STATEMENT ~ 1 is True, STATEMENT-2 is True; STATEMENT -2 is NOT a correct explanation for STATEMENT-1 (C) STATEMENT ~ | is True, STATEMENT-? is False (D) STATEMENT - | is False, STATEMENT-? is True “| STATEMENT-1: Acidic strength boron halide is as BF; < BCh < BBr; < Bly and STATEMENT-2: Fluorine is more electronegative & creates greater electron deficiency on boron. (A) STATEMENT - 1 is True, STATEMENT-2 is True; STATEMENT STATEMENT-1 (B) STATEMENT - 1 is True, STATEMENT-2 is True, STATEMENT -2 is NOT a correct explanation for STATEMENT-1 (C) STATEMENT - | is True, STATEMENT-2 is False (D) STATEMENT - 1 is False, STATEMENT-2 is True -2 is correct explanation for © eS ea EOECle Sol. Sol. 7 NH, STATEMENT-1; \ y / 'S less basic than and NH, STATEMENT-2; Lone pair of \s delocalized (A) STATEMENT ~ 1 is True, STATEMENT-? is True; STATEMENT -2 is correct explanation for STATEMENT-1 (B) STATEMENT ~ 1 is True, STATEMENT-2 is True; STATEMENT -2 is NOT a correct explanation for STATEMENT-1 (C) STATEMENT ~ | is True, STATEMENT-2 is False (D) STATEMENT ~ 1 is False, STATEMENT-2 is True © STATEMENT-1: Carboxylic acid can not be converted to amide directly by heating with NHs and STATEMENT-2: NH; reacts with acid to give carboxylate ion which is inactive for nucleophilic attack. (A) STATEMENT ~ 1 is True, STATEMENT-2 is True; STATEMENT -2 is correct explanation for STATEMENT-1 (B) STATEMENT ~ 1 is True, STATEMENT-2 is True; STATEMENT -2 is NOT a correct explanation for STATEMENT-1 (C) STATEMENT - 1 is True, STATEMENT-2 is False (D) STATEMENT - 1 is False, STATEMENT-2 is True ) CUES ae SO aan. CESS MATRIX — MATCH TYPE QUESTIONS 1. Match the following “(p) Chiral molecule l@ | j __ Achiral molecule | (| Optically active (3) Optically inactive (t)_| Plane of symmetry Eerste Sol A—(p,r) B (p, 8) C (Qs) D> (Qs) Ais chiral, and optically active. B is chiral but optically inactive due to pyramidal inversion Cis achiral because of plane of symmetry. D has a plane of symmetry. | a) th an ie order of carbocationstabilit oO | i nee | CH;—C—CH, CH;—N==CH—-CH, CH;—C—CH, io |B 1> I> | w () (i |__| decreasing order of Pus | OH OH OH jaa | | | © (@ must a Br F | | ) 0) (i) ite} Increasing order of Pha [H,0, OoF> O5Cl, | (D)} (I) (tl) (itty () >>) Decreasing order of (O—O) bond length Sol. (A) > q; (B) > Fr; (C) > q3 (D) > p OSA NCL Oetable. | Antiaromaticity | due to the presen 4, haractetistic of a eyelie molecule witha x elecivon sytem that his Ae ae + Dx lee ot 4M electrons in it. Unlike aromatic iv lesas ed a ecene UR ily (Gn * 2) electrons and are highly sable antiaromatic compounds are highly stable and bil reactive. To avoid the insubils fore : 1 : ae hange shape, becoming, no fore breakin some of th 10m electrons, : : io) | la | L eae a ce : Non-planar | | au | | Gil) | 2 equivatont Rs (iv) S equivatent RS Aromatic Huckel number of re 3 For the given species in column I, the only correct combination is [A] () Gi) (S) {B] () Gi) (P) [C1 OW {D] Gt) (i) (R) 4 For aromaticity, the only incorrect combination is TA] (ID (iv) (P) [B] (IM) (iii) (P) [C] (LV) Gi) (S) [D} () Gi) (R) 5. Which of the following options is the only correct combination ? (A) © Gi) P) (B] dD Gyr) {C] (i Gi) (RY {D] (IV) Gi) (8) Sol, 3 c 4 c 5. B CURES SNS© semctural ay well as stereo isomers possible for a compound with the @) —CHe Sactuiy of which compounds for the above reaction will be mininnum, See '¢ following, calculate the —ve value of reson: nergy of the cyclopentadienyl cation, in AH = =14.58 kal / mol AH = ~72.91 keai / mol Sol 43.78 On hydrogenation of the allyl cation liberates 14,58 K.cal'mol. So two should liberate -29.16 Xsal mol. Hydrogenstion actualy gains -72.91 kcal/mol making the eation higher in energy by 43.75 Kcal mol. The resonance energy is negative : 43,75 kcal/mol Prob. 2. Pure natural lysergic acid has [ap Optical purity of the mixture is Sol. 0.. » = *40°. A certain (dl) mixture of lysergic acid has [ao = +10° [oh _1 tical < eee [oes 40° Prob. 3 The equilibrium constant for the ring-lip of fuorocy clohexane is 1.2 at 25°C Calculate the percentage of the axial conformer at that temperature. Sol 454 fed) % axial =], 199 fax} (eq.]+[ax] =— «100 x100= 45.45 il MP -CHEMISTRY-GENERAL ORGANIC CHEMISTRY & ISOMERISM13 ELECTROPHILIC A ROMAT SUBSTITUTION AROMATIC SUBSTITUTION REACTION The replacement of an atom or gr ou oe the important substitution Tatoos : = aromatic ring is known as aromatic substitution reaction. Some of and Friedel~Crafls reaction, ‘Ogenation, nitration, sulphonation, chloromethylation, formylation General mechanism: Step 1: E-2—S™" ype oy. ay BH EH EH _ OC a. O O — EH E . Step 3: +f +H Halogenation FE —>x (cI’,Br',1') Nitration E' NO} Sulphonation $034 SO,H eso, M804 ‘SO3H No reaction HRTF yin? Chloromethylation feat Cl Teen Se ESS)tion is known as Gattermann-Koch aldehyde synthesis. (This is not valid for phenols ¢ Phenolic ethers), ius yde syn Phenols ang 10 0) CO Wc, Oo 0 This reaction is known as Gattermann aldchyde reaction, Friedel—crafts Alkylation Alkylation is possible with alkene, methanol and dialkyl sulphate, Cs Omlom Note: In general alkylation can be carried out using alcohols/alkene in presence of protic/Lewis acids, Friedel-Crafts Reactions HyC_CH, [Dueto rearrangement of carbocation} 9 +Hoh +H WeCo_ ONE I i “CH 0 [Note: 1. _Nitrobenzene does not undergoes Friedel-Crafts reaction due to deactivating nature of NOs group. 2. In aniline due to acid base reaction between NH) group and AICI; a bond forms causing loss of Jone pair on -NH; thereby removing the +M effect and highly incre —_—_——_——— CRS GAS NSaoe DIRECTIVE INFLUENCE OF Suastrryenrs = group already present in edits incoming group. This i eee Product exerts a great influence on the position to be taken by 4s directive influenc pifet of substituents on electrophilic arom pide director eS aay ian een : Meta directors “NH, -NHR, -NR, -OH, -0 Moderately deactivating -C=N, -SOsH, ~COOH, ~ COOR, - CHO, ~COR Ortho and p; Moderately activating “NHCOCHs, -NHCOR, -OCH,, -OR Strongly deactivating NO;, -NR}, ~CF,, - CCl, ‘Weakly activating -CHy, ~CaHs, -R, -CoHls Weakly deactivating +f, -Cl,-Br-T Effect of Activating Group This may take place due to #1 and +M by considering the following structures, ~Tand—M (with +M > -1) preferably. The +M effect can be understood Effect of Deactivating Group Could be due to ~ I only, - I, - M, +1 and -M (with ~ M>+1), The ~ M effect can be understood by considering the following resonating structures for nitrobenzene. ° 9 ® 0 O oO 2 NO xe One PF One O-8- 0-8 UAC SSOENEILLUSTRATIVE PROBLEMS Sol. Both reaction have same rate because C - H or C - D bond breaking will not participate in rate determining step. Sol. The product of acylation co-ordinates with is a carbonyl compound which can bind the Lewis acid catalyst. For this reason, Friedel-Crafts acylation requires an excess of the catalyst. The product of alkylation can act as Lewis base catalyst. So, all the catalyst is always available for alkylation. Sol. The initially formed primary carbocation rearranges by methyl migration to form a more stable tertiary carbocation which acts as a electrophile and attack the benzene to give the major product. CH, CH, H.C +AICh—> Hc—}—CH, + AICI, cH, Cl cH, CH, methyl shift H.C: ‘CH, cH, / HC IGMP-CHEMISTRY-ELECTROPHILIC AROMATIC SUBSTITUTIOMinor NH» a Major ®) om i = RR + cl SIZES!oa Sol, OES] (a) Since the final product is an aldehyde, one precursor could be the 1,1-dichloride: these compounds are readily hydrolysed to carbonyl compounds. cl a CHO Cc cl cl " There is also an alternative route. Cee eo Ph Ph 7 Ph. a 7 © 2X gor OX Ph Ph Ph The use of two molecules of a 1,1-dichloride and copper suggests the formation of an alkene. This is an extension of the Wurtz reaction. cr o Os Ot. Br The given reagents clearly indicates that a Grignard reagent is involved. However, aryl chlorides do not form Grignard reagents in ether; THF is necessarily a solvent. On the other hand, ary! bromides (and iodides) readily react in ether solution. The use of aqueous ammonium chloride is a safety precaution to prevent the possibility of dehydration of the alcohol (which might occur if acid is used). CH, cH, CH, « CO CC + CH, ‘CH, cH, ‘The use of iron indicates nuclear substitution. Me is o/p directing, and there is always the Possibility of a steric effect at the o-position. So, we can suggest that 4-Br product will predominate. Experimental work would have to be done to find out what are the actual results. From the literature, it appears that the 4-Br compound is formed exclusively. t-butyl like - -N(CH,), group. So, the CN group should give the greater ortho/para ratio. The actual data is mentioned in the table below: The -CN group, being a linear two-atom group, is much less sterically demanding than the [ Group %Meta_| %Ortho | % Para | Ortho/ para ratio | -N(CH,), 87 2 i 0.18 -CN 81 17 2 ef 8.5Also -QH has -1 effect. But in alkaline medium, Phenol is converted to phenoxide ion which has both -M and =I effect. Hence, ring is more activated and hence electrophilic substitution occurs more readily. TESS Sees LOon | 7 ( A s-C00H COs went Oxidation of D with atkaline KMaQ, and woic acid. Treatment of (B) with SeO,/H,O gives E (CxH(O,) h d with alkali followed by acidification. Identify A, B, C, D and E with OH H Broo f oO Br A o ©) ( wy) o \ c44,0 CHO CH,OBr A) (B) «) : } nn Tee CHOH-COOH CHOH-COONa | | ee oy =I O WC) w Sram QV Wy 4 CHO, (D) H H oO CHOH-COH | a! Eee Ss sa ORY SA Le]SOLVED PROBLEMS subjective Questions prob. Hea) In the mechanism for electro does nucleophilic attack occu the nitrogen atom bonded to 1 by) Propose a mechanism for the ch c, why as the electrophile, Why hile substitution using dhazonium ton as the eleetphn I on the terminal nitrogen atom of the diazoniunt ion Fa he benzene ring? following HCH Hac lected to ©) A student had prepared three ethyl ~ substituted benzaldchydes X, Y and Z, but had neg! ed label them. The premed student at the next bench said that they could be identified by ere the 4 sample of each and determining how many bromo ~ substituted product were formed, Is premed student's advice sound? I~ © \ Sok a) lama )) YS Because the nitrogen bonded to benzene can not become pentavalent due to lack of d ~ orbitals b) gRCUgH— CH=CH, oH cHge—CH—cr, Hs Oy © | emmy steabooion © cucu ——cncny fl Oy TSS SS eT OEYHo eno 0) ; OL ( | Sills ally Yes the premed student was right. 3 different types of substituted cthyl benzaldehyde on bromination will give 3 different number of products Prob. 2. How can you carry out the following conversion? o Sol, ek Objective Questions Objective Questio Prob. 1. In aniline, the NH, group (A) activates the benzene ri (B) deactivates the benzen (C) activates the benzene (D) activates the benzene ing via both inductive and resonance effects ring via both inductive and resonance effects ing via resonance effect and deactivates it via, inductive effect Ting via inductive effect and deactivates it via resonance effect, ‘Sol. Due to lone pair on N atom, it activates the ring. On the other hand, electronegativity of N is more than C so it deactivates the benzene ring via inductive effect, Hence, (C) is the correct answer. Prob. 2. Which of the following structures correspond to the product expected, when excess of CoH reacts with CHCl; in the presence of, anhydrous AICh;? oval, (B) QO 3 Yo ® tJ Sol (D) IGMP-CHEMISTRY-ELECTROPHILIC AROMATIC SUBSTITUTIOIrab, 3. The most basic compound a (A) benzylamine : (©) acetanilide (B) aniline . (D) p-nitroanitine Sol Except benzylamine, all show lege SSS tendency to donate electron pair due to resonance. Hence, (A) is the correct answer, Prob 4. Nirobenzene can be prepared from benzene by using a mixture of cone. HNO, and conc. H»SOs In the nitrating mixture HNO) acts as a (A) base ‘ (B) acid (C) reducing agent (D) catalyst Sok HNOs accepts a proton from 1,50, H Wig H,SO, + HNO, == Hso, + —=0 N: be Hence, (A) is the correct answer, Prob. $. Which of the following is characteristic of a carbocation? (i) Itcan rearrange to a more stable carbocation, (ii) It can eliminate a hydride ion to form an alkene, (iii) It can add to an alkene to form a new carbocation, (iv) It can abstract a hydride ion from an alkane. A @ (B) (ii) © wy (D) (ii) Sol (A,B, C,D) Prob. 6. Which will lead to Se reactions at meta position? (A) Gs ®) ict), (goo i) : NHCOCH, Sol (A,B) MP-CHEMISTRY-ELECTROPHILIC AROMATIC SUBSTITUTION= Ca Reaction | oe In number of cases of Friedel-Crafts alkylation, the final product - a Generally with stronger Lewis acid product is rearranged due ee rca weak Lewis acid no such effect is observed. Temperature is also favour rearrange product Read the above passage carefully and answer the questions given below it 1 What is electrophile in given reaction? (A) x (By R (C) (Lewis acid x)” (D) None o' Sol, (B) ‘ SS I + Me,CCH,Cl*_ Product Product is Me Me Me Me | Me——/ ae A) B) a) as { ] SAH Me Me vo—|_Me Me: Me Me (D) © ms e “AN U J A NF Sol (A) eee eee OSES)Po Ce MATRIX-MATCH TYPE QUESTION [ 1 Match the mee ia Column-1 with Columt 7 COOH (A) econ | (P) | 6, pedirecting compound | | (q) | Activated compound | |() | Noreaction @) | (8)_| Deactivated compound () | Meta directing So. A 76 0.B>49,C>(0,q,D> 6H) 2. Match the following: | (A) | Friedel-Crafts acylation | (p) | Electrophile substitution | (B) | Reimer-Tiemann Reaction (q) | Cumene t lo CoH, —SCHeSUAC (®) | Nitronium ion HC—CH, | | 0 ae (5) | Dichlorocarbene 9 | Rearrangement of Carbocation So. (Ap), B>p,), Copa, 0>p,0, eS STOOion given in the thr Answer 3, 4 and § by appropriately matching the information given in Ce columns oF thes, nswer 3, 4 and 5 by ly table. tle (P) | Solvent dependeny (i) | Temporary effect a ‘an | Hyperconjugation Permanent effect (Q) | Solvent independen yper iad erin | 2. | Seete : | (D__ | Inductive effect [amy | Mesomerie effect (ii) | Involves @ electrons | (R) | Occurs in benzene [avy | Elecwomeric effect (iv) | Involves n-electrons. | (S) Occurs in toluene 3 Which of the following combination is correct ? : Alay) iQ) BB) (I) (iii) (RY {C] (I) (iii) (S) 1} Gi (Q 4 Which of the following combination is incorrect ? : 1A] () Gii)(Q)——[B} aN Gi) (Q) [c] MQ) (D} (MW) (iy ¢g) 5 Which of the following combination is correct ? TA] AY) (i) (Q) [B] 0) R) {C] () )(Q) {D) (11) Gi) (gy Sol. 3 D 4 c 5. D SINGLE INTEGER TYPE QUESTION Se 1 Nitration of given compound will takes place at which one of the carbons indicated by member NO, 4 1 3 x COOH Sol (3) ETS Neal ONT SUBSTITUTIONano NUMERICAL VALUE ANSWER TYPE Probl. Sol. Prob.2. Sol. Prob.3. Sol. Prob.4. Sol. Prob.5. Sol. Prob.6. Sol, NH) a } ats c ae Total number of mononitro derivatives is x, Calculate * 15 : Nit, (yma aor produ ot oc x the final product the number of carbon atom is x and the number of lone pairs is y. Calculate 5 OH © no? Major product. Calculate Mmber of O atoms in product number of H atoms in product 2.33 OH on Br Br CO) +x. Br x Calculate 25 12 12 3.4 bastion The number which will be attacked most rapidly by -NO} is x. Calculate : 1.33 Hl Og A 0 Ne ‘number of carbon in given compound Sulphonation is most favourable at carbon number x. Calculate x 43 Tees Ss SOOT]NO, Prob.7. HINO HHESO4_ x. ‘NO, ‘The number of oxygen atom Compound X is 5 (par = Trinitrobenzene). MM reactany ay Calculate P= 4+ Sol. Prob.8, Lb SLAG, Q (major product) The position at which Cl attaches is x in the product. The number of Hydrogen atoms in eactant Calculate * y So, 65 ‘on Prob.9. ‘oO ee 4 mmorevelaile less vole 3 The position at which NO ataches in product B is x. The number of m bonds in product isy Calcutate* 7 Sol 1.25 ma. Q) + Ca (2 mole) The number of carbon-carbon bonds in product P is x and number of x bonds if'y. Calculate y Sol 6.67 Tees EST)HYDROCARBONS | 4 or Cyclic yen chai or be or a Closed chain |__ Aliphatic 7 a Sara are enney v Alicyclic Aromatic: | ea (ALKANES The general formula of alkane: C,H. Methods of Preparation (i) Reduetion: (a) Hyrum a (Py RCT H (b) 2 oni ‘ { Hy HH Gi) Wurtz reaction: 2R -X—SPase SRR (iii) Corey-House synthesis: R-X—SOH 4R-R (iv) Reduetion: (a) R-OH—=4M2 5R-H (b) 9 Ren, () Clemmensen reduction: oO RR(vi) Wolff-Kishner reduction: ° LL _Nitp-Niig/ak: KOH! RCH - Ry R Ry (vii) Decarboxytation: ° Jk MONO’ YR-H R™ “oH (viii) Kolbe’s electroly’ ° tL __Pileeoode/_y RR 7 oH Bastoftieaed Chemical Properties (i) Reaction by X:: R-H—“.4R —X (usually a mixture) (i) Combustior C,Hyy4) —E 2» CO, + (n+ HO (iii) Pyrolysis or cracking: Alkane 2-207 wih vston nb", }1, + Smaller Alkene + Alkenes (iv) Isomerization: HC (v) Aromatization ALKENES ‘The general formula of alkene: C,H2n Methods of Preparation (i) Addition reaction: (a) Syn addition: H H — —Hp/intarscast FX (b) Trans or anti addition: H Naini. Ny ’ ( H (ii) B—elimination : R-CH, -CH, ~X—*#84 RCH CH, (iii) Dehydration: R-CH, -CH, -OH eH “>R-CH=CH, WSUS AecS (iv) Dehalogenation: R-CH(X)-CH(X)-R—C0H0 5c CHR (Nal in acetone) (v) Hofmann elimination: : on 6, ts 2 i —5CH, -cH, -cH= Eicon. Ch; CH, (Major) + CH -CH = CH-CH, (Minor) Chemical Properties (i) Hydrogenation: (ii) Anti addition: (ii) Halohydrin formation (anti addition): Br OH (iv) Markonikov’s addition: _t J an —, (v) Anti Markonikoy’s addition: CH, ~CH = CH, —#te™# CH, -CH, -CH, -Br (vi) Syn-hydroxylation: CH, = CH, —S##°_ CH, (OH) -CH, (OH) (vii) Hydration reaction: (HoH (viii) Anti Markonikov’s (Ba rT R-CH =CH, —S Gi? RCH, ~ CH; ~ OH (ix) Markonikov’s without rearrangement: ()HelOAe) /HON/THF (i) NaBH /NOH OH H &) | | (0s + C=C HOF oe CRAEp. (xi) Epoxidation: _£aHs6op00 (sii) Alkylation: Cet ttanion 4. Hk ALKYNES The general formula of alkyne: C,H» 2 Methods of Preparation (i) Dehydrohalogenation: x x pt ek oe R-C=#C-R (ii) Kolbe hydrocarbon synthesis: R cook _, Bem sR-C#C-R R cdot Gil) C= C-He NINN 4 CCR (iv) Dehalogenation or coupling: 2R-CX, #4 R-C=C-R Chemical Properties () Hydrogenation: NaN y CH, CH, ~ (ii) Halogenation: 22/CCU_, CX, ~CX, ~ (iii) Reaction with HX: 22, -CH, -CX, - (iv) -C=C- + H,O B84. 5 CH = C(OH)- <—> CH, ~ C- ° (v) Markonikov’s addition: g R-C=C-H—™* 4R-C-CH,X (vi) Oxidation: te R-CaC- RO no ars R—C-C-R (vii) Isomerization: CH, -C =C-CH, —“*" 4CH, - CH, -C =CH (viii) Oxidative ozonolysis: CH, -C=C——!2_+ CH,COOH + HCOOH # —_—_— TEEA Ee eens~ACOSM acd 239 ee Noni, —CEC~ CH; H ae NaNH(). ie : H—C—pr rst Ut | eee at to? i CH; (D) Erythro form ‘Sol. Corey's house synthesis. This Method can be used for the preparation of unsymmetrical Alkanes. 1 0, FOonEPerce ey Mm Sol (i) (A) reacts with sodium in liquid ammonia and thus it is terminal alkyne i.e. CH (1) CHC ® CH C,H,C = CNa’ H.C = C-CH, -CH, -CH, (ii) C,HLC = CH #84 €,H,CO- CH, (iv) CHC = C-CH, «CH, CH, ah, CH, - CH, CH, - COOH + C,H,COOH Since (D) and (E) are isomers, thus the structure of (E) is Ho COOH He cH, Thus (A) 1s ca uitg wn | xMnovOH (cold) Syn addition cu cu, HO GH / Aten Ho: H it H — (By anti addition) i Ht ‘OH H Hy is con Gu, © GH, rs _HCOM Lindlar anti-addition a HyC—C=C—CH, Lind a = Beis iomers (By syn addition) p coed CH; CH; » 5 cH,—ch thc, te KOH “HBr Irchcn, CHs—CH-C= Cc, a ‘Tetra alkyl substituted oe, CHy—CH=C—CH—cH, gy rill! substituted if CHs—CH—C—cH ony © Dialky! substituted" The order of decreasing yield is A>BSC. According to Saytzeff rule, more substituted alkene is more stable. Sol. (a) Four fractions can be generated mF ee yr wet ne Ya act oh Ge « 2) Mair oa Br ® ont oytatto—\ 4 raaHs Sol (a) Lye ae yb Dee Do i) y: « yy cen, Mt uy, wf exer si aH ng Bae cn De >: c a \ c u CCM), ND CUCM) Wh 5 wsaavney % Anydroearbon (A) of molecular weight 54 reaets with excess of Bry in CCl, to § (B) whose molecular weight is 493% more than that of (A). However, on Dine Brae ate: (A) forms oy whose molecular weight is only 7. ise ats ‘yields diiketone (FE). (E) on oxation sives propanoie ac (A) to (E) with reasons, wv Sol. Compound (A) i : (B) Molecular weight 54 = Molecular weight 7 | \ (493% more than A) o caus (¢y ENE SON Molecular weight 7.4% of (A) Diketone (E) o Propanoic acid To 100 gm of (A), add Br, and the new weight is 593 gm ©. To S4 gm of (A), add Br, and the new weight is one = 320.2 gm Weight _ 320.2 Molecular weight 160 +. No. of moles of Br; =2 moles (As two moles of Br; were added, compound has two bonds hence general formula should be n=4 molecular formula = CyHy (A) reacts with CHsCHsBr in presence of NaNHs—> Compound (A) should be terminal alkyne, i.e, I-butyne —————— IANS eeBr CH CHC ach —% cH,cH, d CuBr, w . pas \, Be Gunpmg—> CH ~ CH, ~ CH ~CHy o CHy~Clh-Cac_oH, ” Lo lo 2CH,CH;,COOH i ——e TET| SOLVED PROBLEMS Subjective Question zB - - Prob. 1 Suggest a mechanism forthe dehyration of cryCHOHCH, 7 Proceed through gg intermediate, Assign a catalytic rate (0 the aid and keep in mind that the O in ROW ig g set is 7 0 in HO. "Se i jy) So, CH CHC tH cy on +OH; CH)—cH—CH, _f_, CHy cacy + 120 +0OH; ca Gn_cre usos 8+ CH CH= CH + H:80, )- 5 4 H,SO, act as an acid i in first step and base in third step. Since it is regenerated back jt isag catalyst ting ay Objective Questions _ Prob. 1. 1,2-dibromopropane on treatment with X moles of NaNH; followed by treatment with - nl Wl bron, de gave a pentyne, the value of X is (A) one (B) two (C) three (D) four Sol. HG Hy Br rr XQ wef IS a \ Ss One BE cH, Thus, X is three. Hence, (C) is the correct answer. Prob. 2. Ozonolysis of 2,3~dimethylbut-1-ene followed by reduction with zinc and water gives (A) methanoic acid and 3-methyl-2-butanone _(B) methanal and 3-methyl-2-butan ~butanone (©) methanal and 2-methyl-3-butanone (D) methanoic acid and 2-methy!-7-butay Sob. cH, =f CH, He ) 0 i i ct, samo? CHAO + CH; HC HC 2,3-dimethylbut-1-ene Hence, (B) is the correct answer. IGMP-CHEMISTRY-HYDROCARBONS|prob. 3. Dehydration of 1-butanol give tutene as a majo ch of the f termediate the compound 2-butene cabin en NO et, by which ofthe allowing i + (A) CH, * He h my et HC CH. 2 ‘ + CH, 3 © We NG hb > + Ke CHy Sol. He NN ‘on + cu, We NP ° Hence, (C) is the correct answer, Prob. 4. Propyne, when treated wit hn (A) Propan-I-ot " Ball followed by HROVOH gives (C) Propen-1-ol ® a ana Sol. (D) Prob. 8. But-2-ene reacts with diazomethane to (A) Hex-24 sive o 1, dedimethy iclopr (B) Hex-3-ene oe oeropane (D) 1, 2-dimethyl cyclopropane Sol. (Cc) Prob. 6. Hydrocarbons are obtained by (A) potassium acetate (B) potassium fumarate (C) potassium succinate (D) potassium formate electrolysis of Sol (A,B,C) Prob, 7. Which alkenes give CH:CHO on reductive ozonolysis (A) Hex-2-ene (©) Propene Sol. (A, B, C, D) REASONING TYPE QUESTIONS (B) But-2-ene (D) 1, 2-butadiene This section contains reasoning type questions. Each question has 4 choices (A), (B), (C) and (D), out of which ONLY ONE is correct. STATEMENT-1: Alkene is more reactive than alkyne for electrophilic a and STATEMENT-2: Alkyl carbocation is more stable than vinyl carbocation, (A) Statement-I is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1. (B) Statement-I is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1 (C) Statement-I is True, Statement -2 is False. (D) Statement-1 is False, Statement-2 is True. Sol (B) TSUNSol. Sol. Sol. Sol. jan the corresponding alkane, int of alkyne is more th STATEMENT-1: Melting poi rode like structure) and hence, compact sry and STATEMENT-2: Alkyne has symmetrical ( : : (A) Statement-| is True, Statement-2 is Trucs Statement-2 is a correct explanation for Statement| + is True; Statement-2 is NOT 8 correct explanation op (B) Statement-1 is True, Statement-. Statement-! (C) Statement-| is True, Statement -2is False (D) Statement-| is False, Statement-2 is True (A) STATEMENT-1: 2-Methyl-I-Butene is more reactive than I-butene for electrophitic « reaction. ity and STATEMENT-2: 2-Methyl- -butene has more a-hydrogens than I-butene. (A) Statement-1 is True, Statement-2 is ‘True; Statement-2 is a correct explanation for Statement-1 (B) Statemente1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1. (C) Statement-1 is True, Statement -2 (D) Statement-I is False, Statement-2 is True. is False. (A) STATEMENT-1: Alkynes give two type of reduction: total and partial and : converts non-terminal alkyne into cis alkene. STATEMENT-2: H,/Pd—BaSO; (A) Statement-1 is True, Statement-2 is True; ‘Statement-2 is a correct explanation for Statement-1 (B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1. (C) Statement-I is True, Statement -2 is False. (D) Statement-1 is False, Statement-2 is True. (@) STATEMENT-1: cis-2-butene gives (dl) mixture with bromine, and STATEMENT-2: Bromine gives anti addition reaction with alkene. (A) Statement-I is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1 (B) Statement-I is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1 (C) Statement-1 is True, Statement -2 is False. (D) Statement-1 is False, Statement-2 is True. (a) ee Wee Sen eeeCs COMPREHENSION Read the paragraph Carefully and answer the Tlloning gu ions: Alkenes can be oxidized in presence of different reagents t presence of silver at high temperature ive ee eageats to gi ‘Alkenes on reductive ozonolysi ‘yclic ethers, whicl Pay Hh also can be synthesized by using pet a acidic KMnO,, it also produces cma compounds in presence of zinc and peroxide. On reaction ‘ ; of, eee trey eae nee ele 1, Cyclohexene is allowed Wve different products. Alkenes on oxidation in (ay caallcada to gs with ozone and subsequently with H3O, and water. The product formed is Sol. (D) (B) malonic acid (C) succinic acid (D) adipic acid 2. Ethene on reaction with me 7 subsequent hydrolysis gives 2" CHCl: forms a compound (A), which on reaction with CHs-Mgl and Ves a compound (B). (A) and (B) are, respectively Wao (A) OH Te eee Oy, ® V7 as ° 2 OH HAC. CH; (©) \ / OH o = Hew N (D) 4yC—cHo and Sol. (C) On 7 a. 3 eee (CoH), on ozonolysis produces propanone, methanal and 2-oxopropanal HC. chy cu, “ ie Ne Hy None of the | ®) — 2 2 cH, CH, ay, Sol. (©) 4 ee ae on exidation with a hot acidified solution of KMnO, forms 2-butanone and . carbon is, cu. (A) (CH,),C = C(CH,CH,), w aa , cu, pe oye oh cy © 0) ee i ay Sol. (D) 5. A hydrocarbon (CeH) absorbs two moles of hydrogen in the presence of a platinum catalyst. The eduction product is inert to bromine and KMnO, solution. The hydrocarbon on ozonolysis produces malonic acid only. The structure of hydrocarbon is Bye, ae (A) CH, = CH-CH = CH-CH=CH, TERENASEr roo ® Cr eo @ ne (4 2) additi — Sci ci=oH, Sa @ | 4¥2) addition reaction tare i, o Ch (s)_| Birch reduction | CHOR | ) Sol. Cae G anC ae Cee OCH. ° (A) Nein aN O20 te +CH,OH ® 8 a wer - =o “of L- L-@rQ, 2. Match the following: CRT GTA ele“CH-Ch ey, NC CHh-Ch=cy, HA P- Nucleophitie addition CH.—CH=¢y, NBS cn, he Free radical addition | 1 | | | | «) [ex-con athe * Peroxide cnScu {eSOvHon So, AGB), C5, Answer 3, 4 and 5 by appro table. DQ Priately matching the information given in the three columns of the following | |) | Zine metal Anti-addition ln (gms | ec RO | | ¢y—Ch, CF,;—C—0-0H OH wm fe ti) OY Q) | Br Br ied | yt-on | | ee CH, | rer Hl oe Oo (ut) Ce —c4 Br (CCl, R) | CH=CH, | f Scr, 2 (R) | CH=CH, Senos pe looee : Br Vy = : oe tiv) | NBs ) | oa,-ch=cu—H-cHy, | Which of the following combination is correct ? (AL Gi) [B] a Gi) (R) Which of the following combination is incorrect ? [A]. 1) (i) (R) {B] (Hh Gi) (P) Which of the following combination is correct ? [A] (IV) Gi) (RY [B] (I (i) (R) [C] all) Gi) (Q) [C] (LY) (ii) (Q) [C] WH) Q [D} (IV) (i) (S) [D} AV) (iv) R) [D] (ID (iti) (P) IGMP-CHEMISTRY-HYDSINGLE INTEGER ANSWER TYPE : C-Hho by oxidative ozonolysis form 9 i on What is the degree of unsaturation. Sok (ay >. (Two rings & ane double bond) UL : Number of products in the following reaction: cos [ + NBS—+ a So ay Br. Br ~ SS SS om +Nps—> [ : ]: ] Ae — 5 How many types of alkyl halides can be produced from monochlorination of A? chy l s Sol (5)NUMERICAL VALUE ANSWER Type Cl=CH—cy, > Pliajon, the final produc p In the final ‘ne Let x = number of carbons and y = degree of unsaturation + number of -OH 8 xis y rou then the value of Sol. 4.50 Pe Chon CHy—Ch,-cH, x29 yel+}=2 4 Prob. 2. © CH ABO. (major) Ratio of degree of unsatura Sol 1.20 Mion in reactant produet is Onno — © DOU =6 £-120 5 Prob. 3. Aes J Ee Ratio of = bonds in product/ reactants is Prob. 4. wor} cH0 Zn-HipiCl_, p oO Calculate the ratio of number of carbon atoms in final product by moles of reducing agent utilised for complete reaction ? Sol. 1.50 0 woe} 80 ee 0 c-atom = 6 moles used = 4 coldalk Prob. 5. kano,” Calculate the ratio of number of hydroxyl groups in the product by number of °C’ atoms ? Sol 0.4 HO, O— LD HO =04 TESap. CH, éx=cH-CH, | CH;—CH=CH, CH)=CH, 0 : wm uD (vy Ratio of the most stable compound to most unstable compound out of the following is ? Sok 0.25 Most stable -> (1) Most unstable — (IV) Prob. J gos 77028 Prob.7, HOOC—(CH;), —CooH—M2H P Sta) Ratio of number of carboxylic group in product by reactant is: Sok 08 COOK —(CH,), — COOH —> COOH — (CH3); — © Prob. 8, a —HEL, Major product Ratio of bromine by hydrogen atom in product is Sol. 0.076 cS ial | = 0.076 a a a Prob. 9. NO, cH, @ a cm Ratio of least reactive by most reactive compound towards HCL is Sol. 0.33 4 =033 3 Prob.10. CH,;—CHs=CH, a, Facet Ratio of position of Br in product by total number of carbon is ? Sol 0.33 CHy CH=CH, —— CHy—~CH,—CH,Br 3 2 1 = = 033 3 ————— HEMISTRY-HYDROCARBONS}