C 2 Exercise-! [| ‘Bond formation is: (A) always exothermic (6) always endothermic (C) neither exothermic nor endothermic (D) sometimes exothermic and sometimes endot- hermic CH, = CH- CN 3° 021 C1~C2 bond of this molecules is formed by: (A) sp?-sp? overt (8) sp*-sp? overtap (C) sp-sp overlap (0) sp*-sp* overlap In which of the following molecules resonance takes place through out the entire system oO) coc, ©) boon, eG In which of the following molecules ~ NO, group is. not coplanar with pheny ing ? cH, CH, (A) (8) oo on 07% é JEE MAIN ] In which of the following molecels both phenyl rings are not coplanar ? cH, cH, ° (O) “ a, cH, cH, So &, cH, ( 0 (2) cH ©) CH, aH, cH, In which Of the following molecules, all atoms are i (cH, - (1) CH, = CH= OH ay cH,-cH-8 ‘Among, these, which are canonical structures ? (A) Land 1 (8) 1and ttt (©) Hang (yal (1) cH, = CH-CH= cH, (ay tx, - (ay Gh, -cH= cH- GH, ‘Among, these, which are canonical structures ? (A) Tang It (8)Tand 1 (©) Mand (O)ait cH=CH-CH,9. 10. a. 12, 13. Rank the following compounds in order of decreas- {ng acidity of the indicated hydrogen : cle —ofopee oll. (I> i> mr (e)M>1>1 (Cyt> > 0 (0)m>m>1 ° o o too toe ly won SNH SH 1 " mw ‘Among these canonical structures, the correct order of stability is (A> >IT (I> M1 (e)m>m>1 (o> 1> mI () CH, = CH-CH=CH- OCH, t (i) CH, CH= CH-CH = OCH, 2 (myeH, = GH- GH GH OCH, (ncn, «CH= GH 8H Sock, ‘Amongt thesé’canonical structures which one is least stable ? ai com (ey (oy1v (GH, = CH CH = CH- CH, is more stable than CH, ~ CH = C = CH - CH, because (A) there is resonance in I but not in I (B) there is tautomerism in I but not in IT (C) there is hyperconjugation in I but not in I (D) IThas more cononical structures than 1. For phenol which ofthe following resonating struc- ture is the most stable ? c “OH “ o (8) &d © é ¥ (0) All haveequal stability 14, (1) CH, - O- CH = CH- CH=CH, (1) ci,-0-CH-cH = CH EH, ( ci, = o4- cH = cH-EH, Among these three canonical structures (through tore ae possible) what would be ther relative Contribution inthe hybrid (to n> tt (I> > 1 The most stable resonating structure of fllowing compound i (a) m>m>1 (0) >1>11 15. (ay ON 16. ‘Among these canonical structures of pyridiine, the correct order of stability is (A) (I= V) > (I= IV) > II (8) (=I) >(1=¥) > (C) (l= V)>Ml> (=) (0) I> (I= 1v)> (=v) O- O-D 4 fk 4 0 0 a18, 19. a. ~Q-G ae (4) (IT = 1v) > (=v) >1 (8) 1> (l= V) > (l= Iv) (C)1 > (IIT = IV) > (I= v) (0) (=v) > (ll =v) >1 9-8-9 0 my amy ‘The least stable canonical structure among these ts (AT (8) 1 (cyt (0) all are equally stable Rank the following compounds in order of decreas- ing acidity. o~_—aD DE © ay am (A) MI >T>T (8)1>%> (C) M1 > 42m (0) 1>all> 0 mo oH In phenol, r-electron-density is maximum on (A) ort 1d meta positions (B) ortho and para positions (C) meta and pera positions (D) none of these Which of the following compounds has maximum, electron density in ring ? No, yy 8) O° *O cod ° Oo 22. In which of the following molecules x-electron neat c 7 Ol” oY - oS No, No, «© HN . In which of the following molecules r-electron density ining ts maximum? ‘NO, 0” “ Oo (8) or oct, @ / “OW (A) C1 and C3 (8) C2 and ca (C) C2 and C3, (D) Ci and ca In which of the following pairs, first species is more stable than second ? (A) CH,CH,O- or CH,CO™ ® a (©) cH, ncn fen, oF CH. werden ook CH,COOH —CH,COONa—CH,CONH, @ aq qa ‘Among these compounds, the correct order of resonance energy 15 (I> > UT (8) > >1 (C)>M>1 (0)0>1>m27. Rank the following free radicals in order of de- creasing stability A) GH, CHEM, (Ql) C,H, - GH - CH = CH, am) cH, ~ 6H - cH, (W)CH,CH cHCH,éH, (V1) CH, - CH, - 6—CH, IV) GH, ~ GH - CH, cH, (A)I> I> IV> I> I> (8)VI>V>IV> > M>1 (C)I> 11> M>V>V>Vl (O)1>V>Vi>V>l>m oO Oo Of OF ‘ : wll oY ‘Among these compounds, which one has maxi- sgt ee (al (c)m CO-GOrgo napthalene. Examine them and find correct state- meee lone (A) All C-C bonds are of some length 1 ts en ee (rcrczbon mioerban crc tee (D) None. (ey (ov Which of the following has longest C - © bond: ° ° oy 9 0 «) Cy (0) cH, mC) ‘Among these compounds, the correct order of C- Nbond length is (A) IV>1> >I (C)M>1>1>1V (8)M>1> > (0)M>1>1v>1 C1 ~ C2 bond is shortest in fi 2 é-cn by eon, oO oO GA-cH, b-cn © OF oCl ‘Among the following molecules, the correct order of C- C bond length is (A) CH, > GH,> GH,> GH, (8) CH, > GH, > CyHY > C\H, (C,H, is benzene) (OCH,> CH,> CH}> CH, (©) GH.> CH> CH. > CH, structutres are equivalent (A) HCOO” OL “ (c) Ne, oY @) qa) \ ; cm \ ; y 8 (AL (yu (cj (D) all of these In which of the following molecules resonance (8)CH, = CH-CH= cH, Which of these cyclopropene systems is aromaticeG e =o [Lo I am L] . 2 Which of these species is anti-aromatic ? (A) Tonty (8) Ht only (C)IM only () both Il and 111 37. Which of the following compouds is not aromatic SS wll © 4 of The most stable canonical structure of this mol- ecule is want olOent (cy ©»tes (D) All areéqually stable ‘O-D ‘The most stable canonical structure of this mol- eculeis ee aN (0) @ ( (a) as S © A 40. a. 42, 43, ‘The barrier for rotation about the indicated bonds will be maximum in which of these three com- Bounds ? (AL (eu om ; (0) samein all a oO i) ey «a cS I 4 ‘The aromatic character is maximum in which of these three compounds 2, (Ay (8) (im (0) samein alt Find out the hybridisation state of carbon atoms ‘in given compounds from left to right. CH, - CH = CH-CH = C= CH-C=C-CcH, (A) Sp” sp’ sp’ sp? sp sp” sp sp sp” (8) sp°sp* sp sp sp sp sp sp sp? () sp? sp? sp? sp? sp” sp” sp sp sp (0) sp*spspsp*spsp'spspspt ‘Total number of « and x-bonds are in naphtha- lene is (A) Sr and 180 (8) 6: and 19. (C) 5m and 190 (D) 7x and 260 . Writecorrect order of stability of following carbocations: M Ay One, «my oe ie Me amy Este avy) ~ Me te (8)M>M>1>1v (D)MI>1> Wat (A> I> > v (C)M>1>1>1v45. The abstraction of proton will be fastest, in which carbon in the following compound x @y (©: ©)p 46. Number of r-electron in (C,H,)* is wz (8)4 as (8 47. Identity the odd species out Which of the spe- les among the following is different from others ? (} A (8) | ‘> 48. Which one of the following carbonyl compound when treated with dilute acid forms the more stable carbocation ? * nota 9G Y A ; (c) (0) CH, - C- CH, op. I 9. The order of the rate of formation of carbocations: from the following iodo compound Is: rub rmdd (Ai>m>m (@)1>m> 1 (Q)m>n>1 (o)N>m>1 50, Write correct order of reactivity of following halo- ‘gen derivatives towards AgNO, g 0 Q)ne,-e-cemae-a (Mppnci,a mpnc-a 51. 52. (A)1>V>Iv> I> IL (8)V>IV>1>01> 0 (Q)v>i>v>m> I (O)I>V>M>Wv>tl ‘Which of the following heterocyclic compounds would have aromatic character ? “ OQ @) Sen AH = © CK ole ‘Arrange the following carbocations in the increas- v (A> > th (®)1> =m (C)> ut> 1 (0)MI>1>11 ‘Which of the following carbocation will be more stable? neve 4 ai © Wee, (7 meme ‘Statement-t: ye _ Cu, is more stable than MeO - cH ‘Statement-2: Me is a +1 group where as MeO is 2 -Tgroup, (A) Statement-1 Is true, statement-2 is true and statement-2 is correct explanation for statement- 1 (8) Statement-1 is true, statement-2 is true and statement-2 is NOT correct explanation for state- ment-1, (C) Statement Is false, statement-2 is true. (©) Statement! is true, statement-2 is false.cH, I = groups cH, are introduced on benzene ring then correct or- der of thelr inductive effect is 55. When - CH,, CH.—GH— ang OH, cH, a (A)CH,~ > CH,» OH, = cH cH, om, (8) H.-G = > oH GH > CH, cH, on, r (0) OH, GH > OH, > CHG - , cH, (0) CH.-¢— > cH,- > CH-cH- q t “2 2 cH, ‘The correct order of Increasing basic nature of the bases NH,, CH,NH, and (CH,),NH Is gas phase’ (A) NH, < CHAN, < Reiove sci (C)CHNH, < NH, < (CH,),NH (0) (CA),NH < NE, < CNH, 57. Consider the acidity of the carboxylic acids (2) PRCOOH (b) 0-NO,C,H,COOH (©) p-NO,C,H,COOH (€) m-NO,CH,COOH Which of the following order is correct ? (A)a>b>cod (B)b>d>c>a (C)b>d>a>c (D)b >c>d>a 58. Which of the following is the strongest base Don owes NH, © ©) CHNH, ‘CH, 59. Amongst the following the most basic compound 's (A) Aniline (8) Benzylamine (©) prritroanitine (0) Acetanilide |. The increasing order of stability of the following free radicals is (A) (CHY.E < (CH).8H < (CH) < (CH) (8) (CHY.EH < (CH).E < (CHE <(CH)EH (0) (CH )BH «toMy < (CHE < (CHI oH (D) (CH).EH < (CHE < (CHYEH< (CHE 61, The correct order of increasing acid strength of the compounds (2) CH,CO,H (b) MeOCH,CO,H (©) CF,CO,H (oNe>—con (A)d Eel, > CHEH, > (CHIE (B) Ges, > CH,EH, > (cH,) GH > (CHE (C) (CHE > (CHy,EH > CHEH,> Eas, (0) GHEH, > Eel > (CH) E > (CH) TH 64, Consider the following carbanions 0 on- bn, Gi) CH= @ Correct order of stabilityof these carboanions in decreasing order is (Ayia i> ih 3) (C)iii> i> ro) 65, The order of stability of the following carbanion is, Hen, a) 0) Co ay) Cy (a)I> > I> V (8) I> m>1>1v (C)IV>M>M>1 (0)M>IV>1>11 66. Rank thefollowing radicals in order of decreasing stability oC oO mom (ayt>1>1>1v (2) M>Wv>I>7 (C)>m>1>1V (0)Iv>M>1> I67. Arrange in decreasing pk, (2) F - CH,CH, COOH (b) OPH CH, COOH a (©) F - CH, - COOH (4) Br - CH, - CH, - COOH Correct answeris (A)b>d>arc (C)e>b>ard (B)arc>d>b (D)d>b>arc 68. Which of the following species is not aromatic ? OOOO “2 ‘Nitrogen atom of pyridine is (A) sp hybridized (8) sp? hybridized (C)sp hybridized (D) Not hybridized nl \ ‘a Oxygen atom of furan is (A) 3p hybridized (B) sp? hybridized (C) sp hybridized (0) Not hybridized 71, Ease of ionization to produce carbocation and bromide ion under the treatment of Agtwill be ‘maximum in which ofthe fllowing compounds? 0. Noms, ~ om " Se ot —s 4 cH, 2 l Van \ qu Oo ° N H 4 Which of the following choice is the correct ‘order of resonance energy of these molecules ? (A> >t () >> m1 (C)it> > 1 (ym >1> 0. 73, Which can lase a proton more readily, 9 methyl group bonded to cyclohexane or a methyl group sapaeeses wn anon (B) I> 1 (C) equal (0) None (AI>0 74, Hg ‘Among these aromatic compounds the correct order of resonance energy per ring is (i> n> mr (8) M1> U>1 (Qmt>t> 1 (O)>1>m OYAASY (uy oO Which of the following orders is correct for the resonance energy of these two compounds ? (AyL> (ay>1 (tet (D) there is nothing like z-electron energy OAAa (a) As Which of the following order is correct for the Fesonance energy of these two compounds 7 (A> (e)it> 1, (len (D) there is nothing like x+électron energy © ca, “\ch cH, a V ‘Which of the following order is correct for ‘resonance energy of these cation (A)I> (@yM>1 (Qi=0 (0) there is nother like x-election energy Contribution of second resonating structure Is ‘more than first ? (A) CH,CH = CHCH,* oF CH,CH*CH = CH, “ae ae (0) All of these ol Vay L \an @) N I 4 ‘The aromatic character is maximum in which of these three compounds ? Wr 8) ah (ay (©) Same inal[Exercise - 1 J OBJECTIVE PROBLEMS (JEE ADVANCED) H-O-CaN H-N=C=0 (Cyanic acid) (Isocyanic acid) Loss of proton from these two acids produces (A) same anion (B) different anions (C) same cation (0) different cations. Which of the following statements would be true ‘about this compound: (A) All three C - N bonds are of same length, (B) C1 - Nand C3 - N bonds are of same length but shorter than CS - N bond (C) C1 - N and C3 - N bonds are of same length but longer than C5 - N bond (0) C1 - N and C3 ~ N bonds are of different length but bot are longer than C5 —N bond. 3. Ease of ionization to produce carbocation and bro, mide ion under the treatment of Ag’ will be maxi- ‘mum in whichof the following compounds ? e “ or ® Oo och, er © II (0) Co oe 4, Ease of ionization to produce carbocation and bro- mide ion under the treatment of Ag? will be maxi- ‘mum in whichof the following compounds ? ® tb oA” " OA, oe 25d, P will be : (c) O (D) mixture of (a) and (b) / — tee (C) mixture of (A) & (8) ol (0) none of these Which one of the following statements is True: "Ox a (A) Phu adds to both compound with equal ease (B) PhLi does not add to elther of the compound (C) PhU react readily with 1 but does not add to 2 (0) PHU react readility with 2 but does not add to 1 Correct order of rate of hydrolysis or rate of re- action toward AgNO, for following compounds is im Or m™m AA (AI > > V>1 (8)1> > m>v (> 1>u>v (0) >1>1>1V10. u. 12. Damen (er (@)e “ O) co, (D)Moture of (A)8 (8) ae A, ” [Seer (C) Mixture of (A) & (8) @) pe (D) None of these ‘Arrange the'given phenols in their decreasing order of acidity: a rXO)-o eayo~{O)-on ™ os-{O)-on Select the correct answer from the given code: (A> M>1>M (B)IV>0>M>1 (Q)v>m>M>1 (0) >> M>T (1) GH,-08 Which one of the following is the most acidic? 13. Which one of the following phenols will show highest acidity? Hy 1) (8) O,f Hy 10 My o Hy! NO, Onc °. : Which of the following is weakest acid? 0 «© 14, COOH “Q Moy 15:"The correct pka order of the follwoing acids is o » a (i> > mr (@)mM>n>1 (C)\M>1>1 (O)I> mon 16. Arrange pH of the given compounds in decreasing order: (1) Phenol (2) Ethyl alcoho! (3) Formic acid (4) Benzolc aad (A)1>2>3>4 (C)3>2>4>1 ()2>1>4>3 (0)4>3>1>2 17. Arrange acidity of given compounds in decreasing order: (1) Cry-NH-CH,-CH,-O# (1) CH,-NH-~CH,-CH,-CH,-OH (III) (CHy)g- CH, - CH, - OH (aym>1> 0 (e)m>1>1 (C)l> a> mt (0)N>I>m18. Consider the following compound on “ TL ©) Oro" ‘cooH 1H OH ON. (0) NO, © crnfcoon 02 Which of the above compounds reacts with NaHCO, giving CO, ‘More than one Correct 19. Which of the following is a 2° Amine ? @ CA (nye-¢-e-c tw Nt N © oy ). Identity electron - withdrawing groups in reso- nance among the following: (2)- COOH {b) -CONHCH, (€)- coor (9) -cN © QO 21, Identify electron - donating groups in resonance ‘among the following: (e)-0-CH= CH, (2)- CONH, {b)- NO, (<)- ococh, (d)- codcH, (e)- CHO, (f)- NHCOCH, 22. In which of the following lone-pair indicated is magenta i \ ow 4 O OW ay 4 (b) 26. (e) CH, = CH- CH, (f) CH, = CH-CH = NH ._In which of the following lone-pair indicated is jot involved in resonance : (a) CH, = CH - NH- CH, (0) CH, = CH- CH= § (©) CH, = CH- -CH= CH, ch=cH-c=aN Ge) en O |. Aromatic compounds are: oC I ‘Which of the following reactions give aromatic compound ? oM “5 © *, oO) ”> my ™ In which of the following molecules resonance takes place through out the entire system. (A) CH,CH,NHCH,CH = CH, NH CHNH, 6 6 (0) CH, = CHCH,CH = CH, VO oD2. @) (e) () @) ) Oy (9) (h) © C “CO o ~~ Which of the following pairs of structures are resonance contributors ? ond (8) CH,CH = CHCHCH = CH, and nO on onkencn cn CH,CHCH = CHCH = CH, Ht Consider structural formulas A, B and C: HyCNeNS HyC=N-REHC-N-N: a) 6) © Are A, B and C constitutional isomers, or are they resonance forms? Which structures have a negatively charged ‘carbon? Which structures have a positively charged carbon? Which structures have a positively charged nitrogen? Which structures have a negatively charged nitrogen? What is the net charge on each structure? Which isa more stable structure, A or 8? Why? Which is a more stable structure, B or C? Why? 3. In each of the following pairs, determine whether the two represent resonance forms. of @ single species or depict different sub- stances. If two structures are not resonance froms, explain why. (2) RENeNs (b) sf¥-Nens Determine the hybridization around the indi- cated atom in the following anion. t O- eu, (c) on ost Using hybridization, predict how the bond legnth of the C - Ca bond in HC = C- C= CH should compare with the C - C @ bonds in CH,CH, and CH, = CH CH= CH, “ once In each of the following pairs of ions which ion is more stable: (2) () GHj-Clls and (a1) cH,=CH-Cils (©) (I) CHy-CH> and (a) cH, = CH eu; én, aa Os and (11) cr (@) @) CH,-CH-CH, and | cH, -C-CH, ® (i) CH,-N-CH, | cH,-g-cH,Draw the resonance forms to shaw the delo- Ccalization of charges in the following ions (2) ome 8a, ° Ot cne onde, oC oi of) (0) CH, - CH= CH- CH= CH- CH - cH, (n) () CH, - CH= CH CH= CH (k) CH, * CH EH- CH= CH, (m) cH, 6H = Cl Draw a second resonance structure and the hybrid for each species, and then rank the two resonance streutures and the hybrid in ‘order of increasing stability fim, (8) 20 a (A) (CH), - 4 For acetic acid (CH,CO,H): (a) Draw three reso- ‘ance structures; (b) draw a structure for the resonance hybridis (c) rank the three reso ‘nance structures and the resonance hybrid in order of increasing energy. Use resonance theory to explain why both C - ‘Obond lengths are equal in the acetate anion. 0. Z on ewval bond lengths acetate O> 37. _ Inthe following sets of resonance forms, la- 'bel the major and minor contributors and state which structures would be of equal energy. ‘Add any missing resonance forms. (ay |cH,—BH-c= 0) ct Cac Hc, Ho CCH | > CH,—cHec- ( c | ft Poe ue e, e c cee, ( a ) 10H, EH CH= O4-NO, + H.-H CHG ( e Nu, Nu, ICH, —CH,ACNHY > CH—CH,—C = SH, 3, |From each set of resonance structure that follow, designate the one that would contrib- ‘ute mast to the hybrid and explain your choice. oH, oH () cHOHE= CH GHP —> cHOHE- CH= oH, o “ bk w (©) Gi, -WicH), —> cH, = NICH, 0 “ ‘ 9 (8) c.g > ob 28 © “ (€) NH, - CEN e+ fin, = cen o “ |39. Identify more stable canonical structure in each ofthe fllowing pars ” ° An WA Nin oe -® ton, “ony () €n,-cu=cn-6— cn, =cH-cH=0 wo I-O 40, a. @) (b) © Identity less stable canonical structure in ‘each of the following pairs : () &4,-0-cH, —+cn, = 3-cH, 8 De nu fw ro — MSA A, (e) "cH, Hy Which of the following statements is (are) true about resonance. Resonance is an intramolecular process. Resonance involves delocalization of both and x electrons. Resonance involves delocalization of x electrons and lone pair only. (O} ro} 2) (9) o) 0 w () 0 (mn) 42. @) (b) @) @) () @ © ) Resonance decreases potential energy of a molecule. Resonance has no effect on the potential energy of a molecule. Resonance is the only way to increase ‘molecular stability Resonance is not the only way to increase ‘molecular stability. ‘Any resonating molecule is always more stable than any nonresonating molecule. The canonical structure explains all features of a molecule. The resonance hybrid explains all features of a molecule. Resonating structures are real and resonance hhybridis imaginary. Resonance hybrid Is real and resonating structures are imaginary. Resonance hybrid is always more stable than all canonical structures. Resonance energy will bemoreif canonical structures are equivalent than If canonical structures are non-equivalent. molecule is aromatic than’ if molecule is not aromatic. A’canonical structure will be more stable if it has more number of x bonds than if it has less number of x bonds. the octate of all atoms are complete than if octate of all atoms are not complete. Itinvolves cycic delocalization of (4n + 2) x- electrons than if it involves acyclic delocalization of (4n + 2) x - electrons. it Involves cyclic delocalization (4n) x - electrons than if it involves acyclic delocaltzationot (4n) x ~ electrons. ++ve charge is on more electronegative atom than if +ve charge is on less electronegative ators. =ve charge is on more electronegative atom ian if -ve charge Is on less electronegative atom. Which of the following pairs has higher resonance energy: (a) CH,COOH and CH,COONa (b) CH, = CH ~& and CH, = CH - OH coo” oF O MarOs45, 4. “OGD cel )wroer, sono or-08- 0, Which of the following pairs has less reso- nance energy: (2) CO,* and HCOO- ope CH, = CH- CH, ca >emtoy «e104; ‘Which of the following pairs has higher resonance energy ~CONS* olY mY (0) CH, = CH= OH and CH, = CH- CH= CH-OH ) AYT™ ond AAs 9. Which of the following pairs has less reso- nance energy : ol) mlb wh) m De a= Oe (2) CH,-CH, Br and CH,-CH (0) CH,-CH=CH @ ny (cu, =cugcn Which of the following pairs has higher resonance energy : oO) and OS (0) CH, = CH-O- CH=CH, and CH, = CH= NH - CH= cH, (©) Clly=CH-=NU end “HN In which of the following pairs, indicated bond is of greater strength : and CH) —FH-CH, Br i Nev and cHy-CH eI CH, and CH, = CHy¢CH,-CH, fsi. In which of the following pairs, indicated bond having less bond dissociation energy : © Cm on go (>) CH,-C CH and HC=CH For ane Hes “id iS Compare the C-N bond-length in the follow- ing species: Hy Wy 10) 5S ui) 5 Wy ui) Rank the following sets of intermediates in increasing order of their stability given ap- propriate reasons for your choice (3) Es PNOME HI EMCI BH “ANDO 55. Explain why each compound is aromatic, antiaromatic or nonaromatic. | 3thiazole u @ (7 pytan Pynylium ion l te) J (fy @ Hpyrone | ,2edihydropyridine NH, A Np H cytosine Ordinarily the barrier to rotation about a carbon~ carbon double bond is quite high but compound Ahave 2 rotational barrier of only about 20 K cal / mot is a diprotic acid OH ‘with both protons being more acidic than aceticacid. In the di-anionafterthe loss of both protons all of the C-C bonds are the same Jength as well as all of the C-O bonds. Provide ‘2 explanaton for these observations. 57. Match each alkene with the appropriate heat ‘of combustion: Heats of combustion (k3/mol) : 5293 ; 4658; 4650; 4638; 4632 (2) I-Heptene (>) 2,4-Dimethyi-1-pentene (ce) 2,4-Dimethyl-2-pentene (4) 4,4-Dimethyl-2-pentene (e) 2,4,4-Trimethyl-2-pentene 58. Choose the more stable alkene in each of the following pairs. Explain your reasoning, (2) I-Methyicyclohexene or 3-methyicyclohexene (0) _Isopropenylcyclopentane or allyicyclopentane wo [ or 59. Consider the given reaction: In the above reaction which one of the given ing will undergo reduction? 60. Compare heat of hydrogenation (Decreasing order) (2) heat of hydrogenation W Qo (b) () @ (e) 61. (1) Stability order and (11) heat of hydrogenation orders. «aw oo “CO(a) Oo) () @ 0 aw i) tw) the following pairs identify the one which ives higher hee ot yarogenation oO) ~O~O (6) CHy— CH= CH CH, ond CH, - CH, ~ CH = CH, iy On OA, cH, Discuss the following observations: CCI bond in vinyl chloride is stronger than in chloroethane. Carbon-carbon bond length in ethene is shorter thanin CH, = CHOCH, CH,SH is stronger acid than CH,OH CHJCH,NH, is stronger base than CH, = CHNH,, Write stability order of following intermediates: (@)CH,-CH; ——(®) CH, -CH-CH, ve © c,-co | a, (a) a (o) ey ob "OX 9X (2)CHy - Che om, > ' (0) CHs ~ CH CHs (€) cH, - Co \ Hy w) ) wi) (ait) () oo ) os) (2) on, -cw ' Hy (b) CH, = CH65. Write stability order of following intermediates: cH He Oo @ (b) » iy ™ 2 * oy Gc) CH 8 ° 0 ° “ w AN ° cHy cucu, (a) (a) Q () Q “0 mo oA CHMe0 ai) ul) ww) w) ™) iy) (wit) cue Wy ) @ CH Me, CMe, White increasing order of heat of hydrogenation : QO “A as\ (&) /\ © = ( rp o— (&) /— © = (6) rf (@) Oo (b) Co ©) CO (@) oO (o) Oo © Co (HOH per x bond) @) Co () CO © CCS (HOH per benzene ring) @ABRAWRWA OO 67. w ow) ) Give decreasing order of heat of combustion “OO =ey “O © (a @)\_/ (b) = on (oy m4 © Arrange If order of C-H bond energy ag 4 How many of sodium fs treated°with excess of ethyl alcohol. rams of H, released when 46 Use the following data to answer the questions is : a, “ COCO = COD ane stsokaime ‘Anthracene Calculate the resonance energy of anthracene inkcal/mol.mn. (A) Which compound has the greater electron density on its nitrogen atom 7 oY (8) Which coompound has the greater electron density on Its oxygen atom ? Orrin pole (P) Sox electrons 1% 75. ‘Cohwnn tt (©) Hybnd state of each stom sp" Q) Ant sromatic (8) Nonaromatc (1) Obeys Huckets Ruse for aromatically Match the column: oon Column (©) First is more stable then second (Q) Second is more stable than frst (R)_Notresonating structure of each other (8) Resonance is present in bath carbocationEXERCI JEE ADVANCED Qt Write the correct order of acidic strength of following compounds: O GH (Ha (oH-Br (oH GD @) CH, b) NH, uy Og ) (4,0 (ii) (2) CHy-CH,-O-H (b) CH, ~CH-O-H I cH, (©) CHy-¢-0-4 CH (iv) (8) F-CH,-CH,-O-H (©) NO,-CH,-CH,-O-H (©) Br-CH,-CH,-O-H (8) Ni-CH, - CH, -O-H Q.2 Write the correct order of acidic'strength of following compounds (i) (2) CH,COOH (€) CgHgOH, (b) CH,CH,OH (6) CHsSO.H Gi) (@) on (b) on. (c0n COOH “COOH cH, COOH © b4, -coon Q3 Write correct order of acidic strength of following ‘compounds: 0 Mg cen { (ec) of don (b) OGM, C-O-H @ movorngton i wy oreproncom i CH,-CHj-C-O-H, (6) (0) no, ~cH, -C-0-H i (0) fc, -C-0-H " (©) Ph-cH,-C-0-H tl (4) CH -CH; -C-O-4 Q.4 Write correct order of acidic strength of following ‘compounds: 1-H H -4 SS H SH Bn o “or “OL © a clSH 4 w oO ©) GH on «© “6 QS Write correct order of acidic strength of following ‘compounds: 0-4 "Cle *o wi (a) © No, Q.6 Write correct order of acidic strength of following ‘compounds: 9 a -0-H 0 0) (00H @ oO) “ Raw g w) @ © ) o. roMe time C-0-4 © five 0-H w) (2) @ ©, oS 10 C-o-n © mr 7 Select the strongest acid in each of the following sets : OH oH 0 @ (b) Oy NO, OH 4 © @ a NH,IH H ai) (2) (b) & 2 F 4 i) ro) Hy cH Ht Me cw) (2) (b) ‘OMe H H & (o) OMe 8 Say which pk, belong to which functional group’ incase of following amino acids : (OOH cysteine : sere 18,8.38108 NH) (i) glutamic acid : More 00H Ne 12.19, 4.25, 9.67 Q.9 Record the following sets of compounds according toincreasing pk, (= - log Ka) oH OH () C: cyclohexane carboxylic acid. (b) 1-butyne, 1-butene, butane (c) Propanoic acid, 3-bromopropanoic acid, 2- nitropropenoic 306 (0) Phenol,o-nitrophencl, o-cresol (€)_Hexylamine, aniline, methylamine Q.10 Explain which is a stronger acid. (a) CH,CH, BrCH,NO, (b) CH,-C-CH, & CH,-C-CH,CN (c) CH, - CHO. CH, - NO, Q.11 Explain which is a weaker add. 6-6 Q. 1H H. ° @ A ® o-€-cHy My ° © “ © Q.12 Which of the following would you predict to be the stronger acid ? @ on or Sito (b) CH, ~ CH, ~ CH, - OH or CH, - CH = CH - OH (©) CHy~ CH= CH~ CH, - OH oF CH, CH = CH - OH Q.13 Write increasing order of basic strength of following: © @ (®) cr" (© be" or (i) (@) cHY (b) Ny (c) OH” (a) Fr(i) (2) R-NH, (b) Ph-NH, © “7M (i) (a) NH, (b) MenH, (e) Me,NH (2) Me,N” (Gas phase) () (2) NH (b) Ment, (©) Me.NH (4)Me,N (in H,0) Q.14 Write increasing order of basic strength of following: : oo) tin, iin, (a) CO “6) wl) WU E ices) i) (a) ©) ° ones M N © JO » £0) Su, Sn, 0) (2) » 9) Nui, Su, Su, © ® DO cu; QS Write increasing order of basic strength of fallowing: () (2) CH,-CH,-Wi, (b) CHy~ CH = Ni () CH,- CaN (2) cHy-E-Hin,—(B) CHy~ CH, ~ Ni oO (4) Ne,-¢-HiH, i of N (iil) (2) (c) (iv) (2) () ) "oO ie ‘Wi-cn,-cH, ° C Me. ) @ Wn, Me Ni o7 "So win, ) By, N ov SoQ.16 Write increasing order of basic strength allowing: Wu, @ (a) © No; iH, @lO we (©) we NH, on® iin, e or ) @) ff ; iim, lO -H § > = xfer iH, () OL (w) (a) OMe Mew, Me e o™ NMe, Q.17 Select the strongest base in following compound oe O «© =e) i) (a) @lO (wi) (a) C\ OD cH, 8 = (b) g (0) O) 4 ) CL j @) % " | ml s 4" nu i CORON ? wMe¢ ? i r i Hi (©) { 7 Or ? Q.18 Arrange the following compound in decressing ‘Order of their basicity. @ (@)H,C= CHV (b)CH,CH,Na (€)CH,CH,ONa (4) HC=CNa Gi) (a) Orn (b) (Oyen NH, NH, 7 oO mw) Ors us No, 8 GW) (a) HO™ (b) NH, (H,0 Q.19 Basicity order in following compound Is ? (A)b>d>a>c (Cla>b>e>d (B)a>b>d>c (D)a>c>b>d Q.20 Consider the following bases: (1)o-nitroaniline (11) m-nitroanitine (UID p-nitroanitine ‘The decreasing order of basicity is: (A> > (8) > 1> (> mem (0)1>m>1 Q.21 Consider the basicity of the following aromatic ‘amines: (aniline (U1) p-nitroaniline (IID p-methoxyaniline (IV) p-methylaniline ‘The correct order of decreasing basicity is: (A) > IV>1> 11 (8) IM >IV> > 1 (C)1>M> > Iv (0)IV>M> > Q.22 Which one of the following is least basic in character? (0) Q.23 In each of the following pair of compounds, which 1s more basic in aqueous solution? Give an ‘explanation for your choice: (2) CH,NH, or CF,NH, NH (b) CHCONH, or HN NH, (©) n-PrNH, or CHCN (0) CyHgN(CH,), 0F2,6-dimetinf-N-N-dimethylanitine (e)_ m-nitroaniline or p-nitroaniline Q.24 From the following pair, select the stronger base: {a) p-methoxy aniline or p-cyanoaniline (b) pyridine oF pyrrole (©) CH,CN or CH,CHLNH, Q.25 Choose the member of each of the following pairs ‘of compunds that is likely to be the weaker base. (2) H,0 or #0 (b) HS, HS", S* (©) C-, SH (4) F>, OH, NH", CHS (e) HF, H,0, NH, (1) OH, SH, SeH- Q.26 Explain which compound Is the weaker base. NH, NH, ®) 6 or 9 0, (b) CH, = CH- CH = CH - CH," or CH, = CH - CH,” 0 ob bon © nol Lon “bn S"Q.27 Rank the following amines in increasing basic a ° om G- Oo (wi) (iv) NH, NH, “~~ O © A rts (a) Ot (CH,COO- a. o iy (i) (b) CH=C CHy= CH” CH,CHY oO iy aii) (©) (i) CH, = CHCH,NH, (il) CHSCH,CH,NH, (ii) CH= C-CH,NH, Q.29 Arrange the basic strength of the following ‘compounds. iH, ° 6 ® NH-CH, NH, ay ay NH, NH, se o Q, (b) ni, NH, eo” 1D LT on ) o) Q.30 Arrange the following compounds in order of increasing basicity. (3) CH,NH,, CH, NHY, CH,NH (b) CH,O-, CHAN, CH, CH5 (¢) CH,CH = CH™, CH,CH, CH, CHyC=C~ Q.31 Rank the amines in each set in order of increasing basicity. w oe” on SO oft fe Pyrimidine Imidazole nM Purine ‘Among the following which statement(s) is/are ture: (A) Both N of pyrimidine are of same basic strength (B) In imidazole protonation takes places on N-1. (C) Purine has 3 basic N. 0 w ) (0) Pyrimidine imidazole and purine all are aromatic[_ Exercise - IV ] PREVIOUS YEARS qa Qa Inthe following benzyl/alky! system R-CH = CH, or €-R (Ris alky group) increasing order of inductive eects ~ [ATEEE-2002) (A) (CH), C- > (CH, CH => CHCH,— (B) (CH,CH, ~ > (CH), CH -> (CH),C — (C) (CH), CH - > CHyCH, -> (CHy),;C— (D) (CHy)C - > CH,CH, -> (CH,),CH— cH, When = CH, CH, CH a cH, -¢- groups are introduced on benzene ring then correct order of their inductive effect is ~ [AIEEE-2002] chy (ACH, - > OH, -cH- > cH, -d oH, (oye, “d- V5 GH, “ch Sch, - CH ! (©) CH, -CH- > CH,- > CH, -c- by, ba, cH, (0) cH, > CHy~ > CHy-CH- bs, The correct order of increasing basic no. of the bases NH,, CNH, and (CH) NH is ~ [ATBEE-2003) (A) NIH, < CHNH, < (CH,),NH (B) CH,NH, < (CH,),NH < NHy (C) CHNH, < NH < (CH,),NH (0) (CH,),NH < NH, < CH,NH, et Q7 Rate of the reaction [AIEEE- 2004] a Pano 2 eh 2 ie te fata wan Z8- wa (8) NH, (©) OCH, (D) OcocH, Consider the acidity of the carboxylic acids [ATEEE-2004] (2) PRCOOH (b) 0 NO,C,H,COOH (€)p~ NO,C,H,COOH (4) m-NO,C,H,COOH ‘Which of the following order is correct ? (A)a>b>cad (B)b>d>c>a (C)b>d>a>rc -(D)b>c>dra Which of the following is the strongest base - [ATEEE-2004] ‘The decreasing order of nucleophilicity among the nucleophiles, [ATEEE-2005] (2) creo" (©) CHO" wor ome} oO s (A) (8), (€) , (0), (@) (8) (2), (b), (€) , (8) (©) (€) , (B) , (@) , (4) (D) (0), Ce), (2). (8)qs Qo 10 ar Qaz ‘The reaction nd. ae xe is fastest when X is ~ [AIEEE-2005] (A) NH, @a (C)OcoR ( D ) OCHS Amongst the following the most basic ‘compound is— [ATEEE-2005) (A) aniline (B) benzylamine (©) p-nitroanitine (D) acetanitide ‘The increasing order of stability ofthe follow= ing freeradicalsis- [ATE 2006] (A) (CgHs)36 < (CyHs)2CH < (CH), < (CHy).6H (B) (CgHs)26H< (CoHs)36 < (CHy)36_ < (CHy)26H (C) (CHy), CH B>C>0 (0)D>C>A>B (A)D>C>B>A (C)B>D>C>A ‘The correct order of increasing acid strength ofthe compounds [AIEEE 2006) (2) 04,0034 (0) MeOcH,cO,4 Me (©) CF,CO,H (Deut is (A)dcacecb ()acd Tea,> CeHgTH, > (CH,),E (8) Gch, > Ces CH, > (CHy), CH > (CHy)E (C) (CH), > (CH,),CH >CyHs CH, > Cor, (0) CyttsCH, > Cay, > (CHS), > (CH,),CH Q.16 The correct order of increasing basicity of the given conjugate bases (R = CH,)is. [AIEEE 2010) (A) RCOO- < HC -C- «> (0) RCOO- < HC #C- yoz (B)z>y>x (dy >z>x (D)x>z>y¥ Which ofthe folowng is more acide and wiry 7 a2. 13 14. 15. 16. For 1-methoxy-1,3-butadiene, which of the following resonating structure is the least stable ? [JeE-2005] (A) 48-84-ch = cH- 0-H, (8) 4@-cH= cH-cH=-cH, (© nc= cn = aH-&4-0-cH, (©) 4.c=cH-CH-cH=6-cH, Predict whether the folowing molecules are iso struc tural or not. Justify your answer. (DEE-2005) (NMe, WN(SiMe,), When benzene sulfonic acid and p-nitrophenol are treated with NaHCO., the gases released respectively are (yeE-2006) (A) SO,, NO, (8) SO,,NO (C)$0,,Co, (D) CO,,Co, (1)1, 2-ditydroxy beznené (11) 1, 3-dihydroxy benzene (Ui) 1, 4-dihydroxy benzene (IV) Hydroxy benzene ‘The increasing order of boiling points of above mentioned alcohols is [386-2006] ()I 01> I> (0)1> > > © ANG™N am AA (A> v>1>m (Ql>1> vom ‘The correct acidity onder of the Téllowing is (DEE-2009] a a ay, ay) cH, (8)1v>I>1> 1 (0) > M> > (A) > Iv>T>1 (C)IM >>> ‘The correct stability order of the following reso- ‘Nance structures is (DEE-2009) Onc =hef (UD H2-N=® (0) 4,2-K=n (M) Hé-nen (A)E> > Iv> m1 (8)1>M>>1v (C)>1 >t >1v (0) >1>1V> 1 2 Inthe following carbocation; H/CH, that is mast likely to migrate to the positively charged car- (3EE-2009] (8) H at C-4 (D)H at c-2 ‘The total number of basic group in the follow- ing form oflysineis [38-2010] oO fhe -0H-o4-on.- pK Among the following compounds, the most acidic is: (388-2011) (A) p-nitrophenol (B) p-hydroxybenzoie acid (C) o-hydroxybenzoieacid (D) p-toluicacié ‘The total number of contrubting structure showing hyperconjugation (involving C-H bonds) for the following carbocation is CH. 9 -CHCH (DEE-2011] In Allen (C,H,), the type (s) of hybridisation of the carbon atoms is (are)[JEE-2012] (A) 50 and sp? (8) sp and sp? (C) only sp? (0) sp? and sp? ‘Which of the following molecules in pure from ts (are) unstable at room temperature [986-2012] “ oO oE) ° ° «© a oC)[ Answers ] Exercise-I 1A 2c 38 4c 5.0 6c 7.8 a0 2.8 10.¢ 11.0 124 13.¢ 44.c 15.0 16.A 17.C 18.8 19.C 20.8 2.C 22.0 23.8 24.8 25.0 26.C 27.4 28.C 29.8 30.8 3. 320 33.8 34k 35.C 36.4 37.0 38.0 40.8 4A 42a 43.c 4B 45.4 46.0 47.8 48.0 aac 50.4 51.0 SA SA s4.c 38.8) Sea 57.0 58.0 59.8 60.0 61.8 62.C 6.8 64.C 65.0 66.A 688 69.8 70.8 71.0 72.0 73.8 THA 75.8 76.4 77.8 78.0 79.C Exercise-II ra 2c 3c 4A 5B 6B 70 BA oA 10.4 11.C 12.8 13.€ 14.8 15.8 16.8 17a 18. ABCD 19.B,0 20.a,b,c.d,f 21.¢f 22.bde 23.bde 24AB,0 25-AB,C 26.8,6,1 27, 8,0 2B. a= Resonance form, b= A,c=C,d=A&B,e=B&C,f=0,9=8,h=8 29, (2) is resonance form; (b) is not resonance form due to different number of /.p. and b. p. (6) Is not resoanance form due to different no. of /.p. and b.p.30, (A) sp’, (B) sp?, (C) sp?, (0) sp? 34, HC=C~- C= CH init all carbon are sp hybridized C - C a-bond is shorter than both CH,CH, & CH,=CH - CH=CH 32 (a) (b) 1, (c) H (4) ¢ 33. (2) CH 0D Qe Cnet On 0 On oO ) Gg (cH, EH —cHect—otm HoH, ()) 0, BHC CtecH, (k) H,@ - cH = CH- CH=CH, o S (mm) Me-cH= 21 a se wonerds, omni, om OL fe 2 9 37. (2), (0), Ce), cH, - L- 4- CH= C- CH, (A), CH,-CHACH- CH= Hifi, (ey, cH, - on, - Un, (2) ii, (b) i, (€) H, (4) i, Ce) (2) 1, (D)1, (€) 1, (6) M1, (ey HE (a) 1, (b) M, (€) ML, (4) TL, (e) + (8), (€D, (8), (9), G4), (1), (Om) . (D) (a), (b), (e), (a) M, (0) 1 (€) 1, (6) 1, (e) (a) H, (b) 1, (€) 1, (8) (@) (b) 1, (c) M1, (4) H, (e) tt (a) ML, (b) M, (c) H, (4) (2) L (b) H, (©) IL, (9) Le) (2) H, (bYT, (@ 1,(0) 1, (ed (2) 1, (b) Ce) Ht (4) 1 (e) 141) T > i (aiicWeicili (BQ 2e3 8 g OH > S N, =H fo JH Restablized & intra H-bonding 4E@. RS. OH (a) 4658, (b) 4638, (c) 4632, (d) 4656 (e) 5293 (2)1, (0), (C9 a (2) ()D>C>B>A(IE>C>D>B>A(b)2> 1(c)2<1(d)1<2(e)1>2 (A) iv> tii> i> 1, (I)i> > ti> iv (®) (i> w>1 ANi>u>m (2) 1, (0) 1, (e) M1, (4) 1 (2) Due to resonance H,CaecHE Ge» CCH (0) In cit,=CH=OCH,,therels single bond character due to resonance wn rcnkBcn, b>a (li)e>b>a (li)b>e>a (ivy)e>b>a ()e>b>a (vi)b>c>a (vil >b>e(vilJa>b>c (iQa>e>b (X)d>c>b>a — (x)arboc Gi)e> boa (b>c>a (l)b>c>ard — (iye>ard (acd ()e>b — (vi)a>boe (vil) >b>e (Will)a>b>e (arb (e>b>ard — (xarcod Gil)e>a>b (ili)a>d>erdon. mn. 72 4, Wb>a —(i)a>b>d>c — fiil)a>b>e>d>elvb>e>a (Warb>c (Warb>c (wil) b>a (wii) b> a WMc>b>a (iarb>c>d — (iil)a>b (wye>b>a dc>b>a (i)d>c>b>a [il)a>b>e (iv) d > D> amc ()d>arcob (i)e>b>a (iQa>b>e Werboa (Warb>e (ii)a>b>e>d arbre (iparbre (ii)d>b>e>e Werarb>d (i)d>c>ard Wb>e (iyb>e GiQe>b>a — vyemarb (> Wa WineAton Woe. A coon 8 (9 omtene: HST ngitamicaae: 125 [28 108 oe QI (a) 3<2< 1; (b) 1 <2<3;(c)3<2<1;(d)2<1<3;(e)2<3<1 Q10 (a) 2; (6) 2; (c)2 Quad (a) 2; (b) 2; (c)2 Qu2 (a) 2; (b) 2; (c)2 QI3(a>b>c>d (i)a>b>e>d (il)a>b>e (iv) ac b b> d>a Qua (acdec (ie>a>b —(il)b>e>a_—(ive>d>b>a Qs (arbre (i)d>e>b>a (il)b>e>a —(ive>b>a (vy b>a Qi6()d>e>b>a (i)c>b>a — il) b> a>e_—iv)a>b>e (vem a> G17) WD (ia (Ya QIB ()>a>d>c (il) b>a>c>d (ii)ard>c Qquse Q20 A 21 A Q22 A 23 (a) i, (b) i, (€) 1, (4) H, Ce)! 24 (2) 1, (0), (c) 25 (2) 25 (b) 4; (6) 15 (4); (€)15 (3 2G (0) 2; (b) 19(C) 2; (4)2 Q.27 (2) 3<2<1<4;(d)1<2<3<4 G28, (2)1 > 2>3; (b)1<23;()3<1<2 G29 (a) 2<1.< 3; (b) 1 <2< 3; (c)2F1 >IT" QO (a)2<1 <3; (b)1<2€3;(c)3<1<2 G31 (a) 2> 1> 3, (b)1>2>3,()1'>3>2, / QS2 A,B,c,D —___—_————_—_—_———_— Exercise-IV S——— eee ————————E———Ee LEVEL-1 eer eee LEVEL-2 ee 1.8 ze 2A “40 S.A 6. Anhydroush AICI, is more soluble in diethyl ethera? Xa 4 ygrous A, (Octet complete) od wp (ua five we ° nH, © ny co Cienega vena F wc 12 a) me, Ns, N 13, MeL eMe Sime” SsiMe, (rameat Given componds are not isostrucutral Delocalised of |.p. of nitrogen in vacant d-orbital of silicon makes compound plar 14.0 15. 16.4 17.0 18.8 19.0 20.4 21.8 320 23.2 24.c 25.6 26.8 27.8Goc [_Exercise-1 ] OBJECTIVE PROBLEMS (JEE MAIN) Sol. ‘Sol.2 Sole Sols ‘Bond Formation is- (A) Always exothermic In Bond formation heat always release. (8) Complete Resonance wo! “1 ean Here'T are bulky groups so NO, group goes out of plane So -N {snot coplanar Ann 10, group g pl 10, group coplanar with Coplanar means -allc are sp? ©) He cH, (0) CH, Here methyl groups repail to each other and any one ring goes not of plane. (2) Hc. Coplanar = carbon should have sp? hybridised.Sol7 (1) CH-CHeg (1) CH,=CH-OH = (IM) 8 -+(1) & (IIL) are canonical structures. SolB (I) CH, =CH-CH=CH, 1, II, III are canonical structures to each other. 1) ,-cHacH-GH, amy G,-cH=cH-8x, ll Soh9 (1) cH (I) CH,-C-CH,-CH,-CH,-C-CH, | ee ‘This Is at more distance so least stable. Active methylene group H: here both side resonance ® pie ttt Sol.10 I u or t ° y — - Sou ou Sou Neuve! A ovis cure Sond ()t>m>n ‘Sol.12 IV str. Is least stable cH,=cH-CH-CH-UCH, due to repulsion b/w © & I.p. sota2 Wat cHY¥GRcH-ch, <—> Gh,-cHach-CH-CH, (en, cH = C= CH= Cry Here lst. (1) Resonance oécurs But notin 4,‘$01.13 (C) (7 }] Neutral specie is most stable. ‘Sol.14 (I) CH, - O- CH = CH-CH = CH, Neutral (U0) @H,-0-CH-CH=CH-CH, 2-covalent Bond (i) o4 -Becn-cnecs-Bn, 3-covalent Bond (C)1>M1 > 290-90 a ay a (levy > (l>M >m Neutral Opposite Opposite charge at charge more distances nearest BA QO+O-O-G ! C r 1 sola7 4 4 4 H H © ay am «vy (4) ()> =v > ev Opposite opposite charge charge near have more distance sntate(°9) resecreenve ton a Sv ng nt tae . suis ARONSON a |e «ay |: e SO Oe ‘more Resonanceam) > (1) > wom sugagherve comes at ortho & pera positon so ae" density ts maximum on ortho & pera Sol.21 +of 0" is maximum so e* density maximum in ring. é NO, No, NO, (-1 effect) occur at two places So xe" density is minimum, many" + Leffect of o° is maximum so.e~Gensity maximum in ring ‘Sol.24 > ae" density is more on C, & © 2 &C, ° ° e \e $01.25 0 G “ S ° 2(-1 groups are here) So - ve ion stable. S0l.26 (1) cH,-COSH (1) cH,coONs (11) CH,CONH, ont “ Sa more delocalisation less E.N. of N © atom is more E.N. due to -ve chargeRE. order = I> I> 1 R27 CHA eH-CH, GH CH-CHECH, cHeeH-cH, §— GH-CH-CH, oO ( amt) «yy more RS. Reso, + hyper conj. (2) + I group: RS. )cH-CH-CH-CH,-CH, (my HcH.-C-EH, cH, (1) + I group (3) + I group: (A I> ll>W>V>iI>v ° 0 ° ‘Sol.28 (I) cy a cy «ay (iy) cy more resonance so max, Resonance energy 0-0-0 no QM C3 Bond has single Bond in 2 structure, }) SoC, — C, Bond is shorter than:C, — C, Bond. Gn Ga é oJ ‘Sol.30 (B) Longest C—O Bond. cy ¥ iH, NH, iH, cn fin Sol.31 (1) an amy m -, chant cHo Partial Pure single bond b/w Double Bond CoN chi More resonance more double ‘Bond. m>>I>1V wns SCL ‘Bcoz only this str 2 e c=cH, - C, Bond contain double Bond So bond length short. Sol33(B) CH, > GHe > GM, > GH, nn? Pure single Partial ‘Triple Bond Bond double HF a Hce0 sotasonly Jp have equivalent type ofS. wT VY a m qm (4n+2) xe (4x02) = 2re ‘Aromatic. (all carbon show sp? hybridization state) ww of Et a (m am) axe" ‘Anti Aromatic wasre) (J esemtvomns aft ‘ Sol.38 (C) —* = ‘Aromatic + opposite charge nearest +90) ee) erate > aromatic Both are aromaticKR 9 DK Dy ry a ay qm) Teqt. st. - os + § 8 3 8 t Tf KS unstable east Rotation energy SolAt Ans. (1), O {\ (1) equivalent (II) more E.N. Aromatic RS. less delocalisation CH,-CH=CH-CH=C=CH-CaC-CH, wa Lili ddl sp’ sp’ sp’ sp’ sp sp’ sp spsp' “ How 4. H Bond = 19 Sols |, H-Bond = 5 more Rotational Aro. energy. eo Anti Aro. ® 1 4 less E.N. ‘more delocalisationcH, 2 cZcn, Sol ay Now ome, 3aH (1) Noalpha hydrogen @ < cue, Me Ne ft n> to Beedt rule long Resonance more stablize so abstraction of proton will be fastest at x position. ‘SOLAS (C,H,)? > »aromatic Gre" } Li ‘S0l.47 (A) A ©) anu © & (©) oO ‘Aromatic ‘Aromatic ‘Aromatic ‘Aromatic ‘Sot.48 (C)cH, cH, He OH He H( "OH Ht "OH a ° ° Ht Stable carbocation a7 DL 6 : f ) Tropyiium C” o a, any, 4 4 4 (Anti (Non (Aromatic), aromatic) aromatic) (am) > (1) > 1) a oO (Il) CH=CH-cl (IIT) Et,C-Cl_ (IV) PhCH,CL (vy) PhC-cr J 4 t 1 1 CH=CH ELC Ph-cH, prt @ (yt group * @) RS. more RS. Tropylium QAro.(A)I>V>Iv> I> BS. — Ten masse aromatic Tecmieeniee’ = | | co CO +2uH Extended cross conjugation conjugation $01.53 (A) cH, OH CH, Most Stable non-bonding e Bonding wena (cH Xe, cH, ve (0) CH, Non ans. A Sol.S4(1) Me-CH, is more stable than Meo -CH, rit false becouse Me-GEH, <> Me-O=CH, ee" ber By Resonance stabilized ‘So MeO-CH, Is more stable than Me - CH, So statement (1) Is False. (2) Meisa +1 group where as Me-O's 8-I group.‘SoLSS The correct order of these groups were are attached with Benzene ring ts- * CH—g— > CGH > OH cH, cH, e 2 10 Sol.56 Basic character of Bases :~ NH, < CH,NH, < (CH,),NH due to +1 effect of City So more electron availability on (CH), NH. SoL57 (2) Ph—C—OH (b) 0—NO, C4H,COOH ‘00H 10,(—1) group (c) PHNO,CH,COOH (d) M—NO2 CH, COOH 00H ‘OOH No,-1 =D) group more distance near distance more stable acidity order b>e>d>e Sol.58 (A) Om @) Owen NH, “ (c) (0) ‘CH,—NH, ‘cH, No Resonance of lone pair of 'N’ So more Basicity nH, $0158 (A) Anitne oni, (8) Benzyl amine LP. Is localised so Most BasieNH, (©) Prnitroaniline (D) Acetanilide Ans. (8) Sol.60(0) cH-CH < CH, FcHs . O40 ce Resonance More Resonance! ry ‘Sol.61(A) CH,—COOH ——> c-P @y Q 41 (8) MeO CH, COOH —» GDeitcoe (c) CFCOOH —+ ©-C—coe” (2) n>-coon —+ Wc Acid strength order :~ d NH, (8) aniline = Oo (C) Dimethyl amine = cH,—H—CH, More electron density on 'N’ more Basicity (itis more basic than 3° amine because 3° amine is sterically hindered) (Dy Matty! Arne = co,—net, Ans - (C)Sol.63 Ans-B eye > GEER) > &4e +1 groups “1 groups +1 groups. S$0l.64 (i) cH—CH, (il) CH=CH, W) CH sp’ sp’ sp (more E.N.) (less E.N.) ‘Stability order Hi >ti>t sp sp” sp + (0) MI>IV>1>1 so ‘se’ \pe \ \ soles) cH-EH, (11) qu ay ° x -&~8 oH + less resonance more resonance order () Ml>t>1>1v1, S0h87 (4) FACHCH.COOH =} O-CH-CH,-COO 4 (b) O-eH-co cooH =) @)-CH-cH,-co8 a F-CH,-COOH H,-Cod less distance C) ‘001 302 COG less aistanct (4) Br-CH,-CH,-COOH 2 cH.-cod 1 acaity «ka gt Pa acidity order = > b>a>d Phy order=c>b>a>d won of oO \\ wD Gren tore (aromatic) one (aromatic) »\ B- Bu S0l.71(A) Sree NM oan, Ann, © “ene — Noe Ph Pra ‘Anti aromatic (Not aromatic) Sol. DL ©) Ne — a om, cH, +1 Hyperconjugation (stable)wnt ww SP +veon'N' ] ts more stable than‘. Both RS. are neutral & equivalent type R.S. So more resonance energy. order of resonance energy. III > II > 1. 0) Cyn a C- Benzylcarbanion “sO 9D OOO Fries Rule - More the Benzenold Structure, more —> Order of R.E. per Ring >I > I > III will be the Resonance energy S0h.75(1) ZAZA of ‘Non Aromatic Aromatic Reorder I> Sh76) AZ MAR Resonance No Resonance present RE. order > IT$01.77 (1) cHacH—CH, am VY Non aromatic Resonance Re.order-Il>1 aromatic ‘Sol.78 (a) CH-CH=CH—CH, << CH.—CH—-CH=CH, ¥ x cH, oH, ne e) <4 2w Sa 9 o "OO wn? a 4 Its Resonating structures are Neutral & Benzene like Resonance ‘So, maximum aromatic character.[[xercise - [OBJECTIVE PROBLEMS (JEE ADVANCED) ] sou nf dt renee eN=C=0 No, Bris Bulky So NOs arp. goes out of plane SoC, — NB C — N Bond areot same length & longer than Cs — Bond. * ‘Sol.3 (C) OCH? os ‘more'stable the Cerbocation more easy the ionization Sols op — > ‘Quasi aromatic so more ease ionisation. sas ~, =O Sol6 (8) x ~] bu Pp Base abstract the H. CH, Sol? (1) aa @ OX. |r, Base Of OF Sun a petro So phU reacts readily with 1 But does not add to 2 sas One - Beige hen . eae Or- Quasi amy Aromatic 8r wn ra ay m > 1 >» w > 1 4 4 t QA Reso, x‘Sol Sol.10 qu Qu2 Q13 Quad 2 — Ox Oo” Dy a Dew Sp (GHy-OH (1) GXO)-0# ct) D{O)-oh (.GXO)-on +M>oT “b> aT V>Ml> n> OZ SO oO) won-or-ey rmecongtebaeofcanpoind mat sable eto aroma .e. © oH Hic A 0 Keo “OL, yoy" © Oo " ©, 5 5 6 tt ; &y, ie No, Maximum acidity (C). Ans. (C) oon coon coon 00H a ® © OY (OY (ortho ettect o Q Omens @ M cH, oh - + (mnost acidic) Compound (B) Is less acidic due to (+M) effect of ~OH group because itis present on pera position.4 eq. Aromatic R.S. 1 acidity « 5 H YH i) cut | 1 r 0. o | J o . So Non aromatic ‘acidity (ka) order = 1 > I> TIT Pk, order = IIT > 11> 1 Q16 (1)Phenot (2) Ethyl alcohol (3) Formicacid (4) Benzoic acid oH COOH H-¢-0H GH,oH 1 1 1 OM scigity ~ Stability of conjugate Base ‘Stability of conjugate base = C,H,O" > C,H,0- > C,H,COO~ > HCOO- a, ay Q7 CH, - NH - CH, - CH, "0H ==» CHy= NH CH, - CH, -O- GING ae_ Ve on MS 'Ey, SWC, — cH, - 0° Cu) (cH, f cH, SCHy= OHSS’ mEH), 4, cH, - 0° Srey ot eheet Ady abet = Tk> T> 1 Q.18 Compound which are Stronger acid than H,CO, glves CO, with NaHCO, > Compound (A), (B),(C), (0) all are stronger acid ther’ H,cO,. H, H \ © “ys 2 Sobi9(4) © Ans.B,D Sol.20(2) -COOH ©) conn, ( Q (©) coc (i (i ‘These are electron-withdrawina arp, (@) -cn (con)‘Sol.21 electron - donating groups (©) -6-coce, (0) -fiHcocH, ag Sol.22(B) | 4 aromatic (SoL.P, Part in resonance) Qu © 1 |.P. is in conjugation & paticipate in resonance. 4 K © ctdakey, b-cr ‘SoL23(b) CH, CH-CH-& (4) CHy@CH-C=N in these three structure lone pair notiin,conjugation. ‘Sol.24 Aromatic compounds are “ C ee © Oo Gre" Gre" Gre" HM og ‘Sol25 (A) oO a QO (8) = 7 + — ‘Aromatic 6re" ‘Aromatic 6x" O28 Tropylium (Aromatic)$01.26 (8) Gj — os RS(1) RS Q R53) o iin, NH, ag) — R.S(5) RS(4) 6-5-8 -Gx8 a Pxgror— ai ~~ © CHpCH= CH —CH—CH=CH, and CHy €H—CH=CH— CH=CH, $01.27 (8) CHp-CH — CH = CH CH=CH, CH CH = CH CH—CH = CH, "@ - oO wPlndd, needed, heii 28 (A) (B) (cy(a) Resonance form (b) A (c) C (d) AB fe) BC (1) 0 (zero) {g) B because -ve charge on Nis more stable in compare to carbon tn) 8 because in (C) sturucture C-atom has in complete octact. $0129 (0) :W—NMEN: and :N=N= Resonance form (0) :H-NEIN: and :N-N=N: Itis not Resonance form due to different number of '.p and B.p. (©) N-NEN: and Wel: Itis not resonance form 1e to different number of #.p. and B.p. 5 oe 0.30 (A) Ch = cH GH Om, 3) Or j 2 50131 HCC —_C SCH in tal earbon are sp hybridized, oC — C.o-bond is shorter than both CH, CH, 8 CH, = CH— CH= CH ‘Sol.32 (a) (1) w cH, = cH oH, more RS, more stable ©) cH, di, and cH, = GH Sah o * do not show Reso. It showsOm FA a @ (cH, CCH, ay HW GH 5 hyper conjugation p-orbital Reso. $01.33 @ on, EL, onto, RS(1) RS (2) ° is} © nn Bd onde on Eons on RS (1) _ RS (2) ? H—C=CH-CH= cH, R.S (3) s . : O- ) co - (©) : RSQ) RS) R.S(3) R.S(4) R.S(S) S608 3G RS(1) R.S(2) RS(3) RS(4) r. O RS(5)® cy cH = cH cH ERY Get — Cee cr, — cH LENE On — CH e CH, Rs (1) 12 ° (CH, — CH — CH = CH CH= RS (3) 0) che cH = cH — cH Len” Bn, eo cle OF «GY Et OE Om, t 2 CH—CH — CH = CH— CH = CH, 1 chen LEY Sy, oo Bir cn cn cn =o Noueat cH cH- cH, Be on io 0 on OM a oxen = RS (1) RS (2) tm on ta Led: ec cne R.S. (1) R.S. (2) “OF Or RS (1) RS (2) RS (3) RS (4)Sy: © 2 Sol.34 (A) (CH) - CH "NH , <—» (CH) CH = NH as. (1) mi RS.(2) =: se. 58 (cH) C— NH, RH. ‘Stability RS. (1) < R.S. (2) (8) ‘Stability order R,So(1))< RS!(2) SoL35 CH= g4o- Ho Ch F= o-H 9 nm cH uw & asa 4 co-Me, as.03) Be a, -c=O-H Q 5, RM. Stability order RS. (3) < R.S. (2) < RS. (1)$01.36 $0.37 % ; 4 a cc > cH *oo Xo asa ns.) RS. (1) & R.S. (2) both are eqt. type R.S. so both C — 0 bond length are equal in the acetate anion. Rs.) Stability order R.S.(2)>R.S. (1) RS. (2) is more stable ‘So its major contribution in R.H. ra oO La e (&) cH, C Sc * CH CHye—> on Scr cht) as.) ] #5 ° " CH= C— CH= CH CH, nS.) stability order RS.(3)> RS. (2)> RS. (1) ot AAP on, oteor fon fe a Ng fg CH,—C—CH=C—CH, Stability order RS. (3) = RS. (2) > RS. (1) both R.S. (2) & R.S, (3) are eqt. type R.S. O #—+CH,— CH= CH— CH—NO, RS.(2) (0) cry HE cH Et — nea Stability order RS. (21> RS. (1)hi, wn, if ua Lie (e) oH, = cH, — CF Hi, @—s cH, — co, — C=, asa) ont R.S (2) and R.S. (2) are eqt type R.S. $0 ‘Stability order RS. (3) = R. (2)>RS.(1) Hy A Sol.38 (a) CH,—CH,—C=CH—CH, ¢—> CH,— as.) [1s-carbocation) ‘Stability order RS. (2)> RS. (1) RS. (2) is more stable R.S. so it have major contribution in resonance hydbrid s Lh Cote meat RS (1) RS (1) EH,— NCH), eo» CH= NICHD, () asa Rs.) (complete octet} {complete ocact} SORS (2)>R.S. (1) ° g t. te og THEW oO Lada ‘ asc) asa) {neta speoes} {Ouarged soecies) So, RLS. (1) > RS. (2) (©) NHL CN <> Aiye C= NP RS. (1) RAS. (2) [neutral] [Charged]°° (Gn OMe sol39 (a) 4 as.) as.) teats} (herged] RS. (1) >R.S. (2) , »O-6 BG RS. (1) RS. (2) [Complete octact] [incomplete octact) RS. (1) > RLS. (2) ob f Rs.(1) RS.) (Aromatic) (Ant Aromatic) RS.(1) > R.SH(2) ® © CH, CH = CHO <—» CH,= CH— CH= 0 @) RS. (1) RS. (2) [incomplete octate) [compiete octate) RAS. (2) > RS. (1) » OQ [Onas sve charge] (W has ¢ve charge) RS.(1) RS(2) R.S.(2)> RS. (1)e © S040 (a) CHO —CH, ¢—» CH= O-CH, RLS. (1) RS. (2) [incomplete octate [complete octact less stable) more stable) - (by 6a®) (620) (4x0) (400) R.S. (1) R.S. (2) [Unstable or less stable) ; i — i © HSH, WONG, asc 25.0) (0s -vechrge more sable] {Chas -ve care uta et ste) , g fin £ a , @ Woy weak, aaah asa) {Ohad-vecnarde mire sable UW has ve charge soles tale] °“O-O H, SH: asc) ns. (2) una we) (dros) ‘Sol.41 (a) True Resonance is a Intramolecular process () False Resonance involves delocalisation of s-electron not -electron (c) Tue Resonance involves delocatization of x-electron and lone pair (6) True Resonance decreses potential energy of a molecular and increases the ‘stability. (e) False Resonance decreases the P.E.Sol.42 Qa3 (f) False Resonance is not only way to increases the stability (g) True Resonance is not the only way to increase molecular stability (h) False not always. (False Canonical structure not explain all features of a molecular. G) True The resonacne hybrid explains all features of a molecule. (k) False Resonating structure are in inaginary but Resonating hybrid are Real. () True (mm) True Resonance hybrid is always more stable than all canonical structures. (2) Resonating structure which are equivalent having more resonance energy (b) The structure which are aromatic they have more energy. (2) If structure has more number. of x-bonds then the structure will be more stable. (b) If the structure which has complete octact of atom which is more stable (c) Cyclic delocalization of (4n + 2)" electron canonical structure Is more stable than acyclic delocalization of (4n+ 2) electron: (f)_A.contnical structrue which as -ve charge is on more electro negative atom is more stable in compare to =Ve charge is on less electronegative ator. (@) CH G—O-H and CH, G— Or Nat ° RS. (1) RS. (2) Tonic compound R.S (2) has higher Resonance energy because it is ionic compound. : “Or ~O RS. (1) RS. (2) eqtR.s. So it has higher Resonance energy(©) Isolated system Fussed system s0 it has higher Resonance energy wo Cm over orser onsen Aromatic Non - Aromatic o-c- and ‘-* a ‘Sol.45 (a) oO ° More Resonance Less Resonance 3 - and CH, = CH— CH, ©) “ant Non Aro aro 6 ae Gy201-01-05 ‘Antl ‘Aro ® @ > and CH, = CH—CH, wo Non -Aro sols (0) Oo and Fries Rule : - More will be the benzoid like structure more will be the Reso. energy “OO -O~ 2+ benzene 1 benzeneExtended ‘conjugation conjugation (6) CH,=CH-OH = and CH, = CH CH= CH—OH, tess Reso, more Reso, ©) Page ang Force Cross Extended Conjugation Conjugation cx LS as . $9" Carbon ao, Non-Aro of) = Ds ‘Aro. 50” Carbon Non-Ar0 a-sp* carbon “O”~ O 0, fo, Aco Non = Aro° re e ~O 1 & of here +ve charge —_here +ve charge have more have less distance distance d - aa UN Wi ot Nigless electronegative atom n compare © tom 200 atom cannot denote the easly in Reso. OC and S 948 (a) N eat. RS. (b) cH, = CH-O— CH=CH, and CH, = CH — NH — CH=CH, 0 atom is more N atom is less E.N. electronegative atorn ‘atom in compare to 0- atom to Been At ant wh on Lh ove charge on ve charge on N atom C-atom is stable is more stable in compare to C-atom “Oo wed cect, Non = Aro() CH,=CH-F and CH, = CH—Br 2p+ 2p 2+ 4p SoL49 (2) CH,—CH—Br and CH, - CH, Cl 1 t here Cl atom is more E.N, in compare to Br (0) CH, — CH= CH Br: and CHL CH—CH, Oh= CH () Resonance No Resonance CH=CH, and CH,=GH,— CH, — Clty “OE Os 1 — CH 0 ve wun Cle me ore Oak () CH,-CmCH and = HCmCH 3aH OaH © OER Aho om ne ore ern cH, Single Side Reso. Both Side Reso.te qi "and : 7 Fin, “7 Win, Both Side Reso. Single Side Reso. s0 more Single more double character character soli HH Hal) "2 “ ) ai) Oatoitlis more €.N. atom Sothis compound have double bond character. oQ g Oo 2 Sol.52 cH, 4 oA ag Aro Non Aro. Anti Aro ss 0) Grune e620 cont ie © LPS: aromatic‘Aromatic non - Aro iin, iim, ft — &, > - 4 Aromatic! — AGH, o<{ GH, OCH, Are AON GH, q q g “ J «8 4 se hon - Aro, ! Co Aro. Kt —K I R de i 3 Sol'57 HOC « number of Carbon in hydrocarbon 1 Hoc «| —————___—_____ ‘Stability of Isomeric Alkene (a) CH, — CH, — CH, — CH, — CH, — CH= CH, att(e) Oh G2 Ec by Ho Gut 8-Carbon Hy 6 . ‘Sol.58 (2) 70H oH © CS “ A aa oOo « Co ma rf o a oh * 3H, __ reve If reduction of A ring then all ring will be Aromatic‘SoL.60 (1) (a) ‘omed long Reso 9aH Of ore 2olt en Siabiy af eamerc Aen 0) ait rH (e) ‘CH, CH, OO ET of Pal? ane = 1 1 HOMa Stability ofisomeric Aikene == SO Stabiity of womeric Alkene @) oe { and my Trans-form ‘cis-form 1 HON Seabiity of isomeric AKene Hola Srapilty of isomeric AKene S0L61 (A) CO oO ‘9t has not anv 2nbond areinconjugative system conjugation “CO wy CoO here 3x bond are in ‘Aromatic wee = “QO 3r-bond are in conjugative sasa oO mnQ Qu Re aeBing Kind 1 HOH HOHa ability of isomenc AKene (C) CH,—CH=CH—CH, and j—CH, ~ CH=CH, nO otemne e" notes Sabin A isomeric Avene ok, WOT. 3aH HOHa 1 aabiiy of Teomene ‘Sol.63 (a)CH. ncn 3 (CH-CH-C aS ho Reso on -cn, (A401, t tere Get eso Theres double bond char CHsH CH.—OH ot 1 cH-8 a8 Size of O-atom is less in Compare to s-atom @ cH-cH.-iH,— Klewkda, ‘This Ip is localized This |.P. is delocalizedHy SoL64 (0)(@) cH—EH, (cH, — GH, — cH, © onf &, att 6a suit 0) @) d (e) oO 0 O 4 Ton 7A - wOX Ox é wml () won To 7aH 30H 2 ad Ww) cnet, (b) CH GH-CH, (©) CHE ba, SoH (a) O 5) oO © O teal Jon Tal wi) @) R< (ey Ox TH 7a (wil) Heae more €.Nhas-ve 2 Anion charge is more stable (vill) (@) (by © 18 Raion 2° Anion ae Reta (waa Ox< oo) Ox« © s 1 Anion 3°Anion 2PAnion©) (2) more will be the (b) angle strain less will be the stability 2 © QO Di fae In chair ‘on boat form (iy (a) HEE (0) chy=cH © cH,-&H, more E.N have the -ve charge then It will more stable then less E.N. have -ve charge 4) Hom (b) CH=CH (©) CH=CH, more E.N. have free Radical then It will less stable In compare to free Radical on less E.N. . s H, ‘Sol6S (1) (a) (b) ofp 2 tn Gi) (b) ©) (@) é -M, —+-NO, shows more 1 effect from -CNH, uy (a) oy 4M, -1 wy) (a) )@) O1ZaH0 “ oa Resonance H, (wii) (a) 5 whole Compound ‘Shows Reso. (1) whole compound Shows Reso. (1x) (a), whole compound ‘Shows Reso, 909) ype. Conjugation © O Reso H »O, . © +M Cl shows vacant ‘e-orbeal (0) G4 cons (>) single side Reso, cH, 6) ° hyper Conjugation po © | Sp'carbon (b) wnote compound do net Shows Res oQ Re. (a) charge is not distributed tis localized 2 (©) | not shows (c) charge is not distributed It is delocalized pow °C _oO eD 6A 3A tu, bu, H on a a " (xi) (@) (b) © Reso Reso nr +hyper + nyber conjugation ‘H, , ai ©) sh ah bu, a, © @ a4 Me, tai Out 01.66 (i) (a) oO (o) oO Reso ‘Not Shows Reso. yan / OOLAN © ee e (2) Fepulsion repulsion ‘© repulsion (©) repute r y 0) Aan (c) 6a @ ©wy (ay oO ) oO me) oO ) oO we) oO © oCce (HOH per benzeve ing) more Reso more Energy loss less HoH ae (4) (2) nance (willy (a) O (b) Reso. 1 HOHa isormenic sabi » CY 7-a] the energy (HOH per +-bone) (cy Mle see per s-bond then Its HOH is less because it loss the energy due to reso oases hyper conjugation hyper conjugation > ‘8-carbon (a) ANmore repulsion > woe \_/ . af ain a ‘or stability of isormeric Alkenes- me Ze © ro © ~~ 4-carbon S-carbon 1 (C-H Bond Energy Sabiityot Carbontree Redical Stability order of Carbon free Radical + d>fSb3e>a>e ‘There fore C —H Band energy + d7 _@)Detocalisation of z-Bond (S) Non - Aromatic @) ‘sp’ carbon © A (8) Non- Aromatic J (P) Hybrid state of each atom sp” ° A (Q) Anti Aromatic (R) Delocalisation of x-Bondrine (Nom Aromatic sre wy (R) Resonance (P) Non - Aromatic ” aA (R) Resonance (P) Resonace (R) Aromatic: (P) Non - Aromatic i (R) Resonance 2 8 S075 (A) CH,—G—CH, or CH, — iH — CH, atom is more E.N. atom form N -atom so O-atom can not denote the I.P easily fromiN-atom in Resonance so (Q) Second is more stable than first (R) Not Resonating structure of each other (S) Resonance Is present in both carbocation (®) cH, — 0 — CH,— CHy_oF Ch ch, (Q) Second is more stable than first (R)_Not Resonating structure of each other oe chs (SIR effect) (P) First is more stable than second (R) Not Resonating structure of each other ; : .CH,CH, .CH—CH, os OF Reso. (P) First is more stable than second (R) Not resonating structure of each other,[ EXERCISE — I JEE ADVANCED ] qr 0 0) wi) (wv) Q.20) (a) H-F (c) H- Br 4. 4 F lm Br> rr In aroun we see the size factor more the size, more stable the anion, more the acidity. d>c>b>a (acidic strength) (b) H- ch ()H-1 4 ¢. oe Ni, 20 H-F Ora od worl ay hb 4, on é In period we see the E.N. factor more the electron negativity, more stable the anion, more the acidity. EN. order > F > “OH > “NH, > CH, Acidity order = d>e>b>a @) (0) CH, CH-O-H +1@3)- cH, - 0 oe More stable ee bu, 2(+1) effect om (9 o,-¢-0-4 cH, + ‘Three + I group less stable {acidic strength) a>b>e (a) F- CH, - CH,-O-H = F-CH,-CH,-o (b) NO, - CH, -CH,-O-H 2 NO,- CH, ~ CHy- (6) Br = CH, - CH, - O-H = Br - CH, - CH;- (6) NHy~ CH, - CH, - 0-H = NH = CH, OH “lorder = -WiHy > -NO, > - F> -Br acidic strength = d>b>a>c (2) CH, - COOH _=HY, CH, =~ o (b) CH, CH, - OH _=Ht, +1€H)- CH, 0w (wy Q3 Ans. (©) CHSOH _=HY, Coy - oo om (Phenoxide ion) oS rs OC caer - > PI (More the resonating structures, more the stability) pae> 1 coon T Von Noon nd ney © gy f ‘ 4 ye Lr Lye | . 26 % * (more-1) Stability=C>b>a acidity =¢>B>a , - COOH on coon cH, - coon coon | ‘Cook " HL “ ‘ cH, -c-0 @) Coo" (by 7000 ©) |" § oo coo. oH,-¢-0 8 fa>bod @) cl-cH,-¢-0-H =H, Cl- CH, - C - O- (one -I group) ) G-GH,-C-0-H ay 0-61,-£- 0 (eta a a (© a-fbo. HE, -G-€-0 (Three -1 groups) a a (rnost stable) c>bra’ (a) CH= CH, CH= C-O-H SH, OCH, = CH= C= 07 F F be) CH, CH-CH,- 0-H aH CH, - CH CH, - C-0- ° peg 7 T q F ° F ° © gu-on-o,- Loon ay na f F In this type of case are see spNpr rule. Distancd | *Poner Number Acidic strength = a> b> fi - (i) @)NO,-cH,-C-O-H HLS NO, CH, - Cg (&) F-CH,-C-0-H aH (2) Ph-CH,-C-O-H ph cH, = C- o (8) CH, - CH= C + OH, ah, Acidie Strength: a> b> o> QA) (a) 6 ®) No, (tronge! acie) 1 1 o 6 2 2 9 (most stable ' a Conjugate base) Acidic strength = a> b>c 4 0 @ & @ a. Inductive effect by distance decreases.Acidity order a> b> c 4 «) “| -H] o - stability of Conjugate base :d>b>c> a acidity order:d>b>e>a S-H SH " 0 oon (i “o -1 asi) (2) oO cool Aon © he, ag (-M) Hydrogen Bonding ‘0. 0 Acidity order=c>a>b>¢ O-H 2g O-H ‘on ors o”™ on A no, ® @) 4b) © @ fo, H-Bonding ho, No, “M om) “T 1 Acidity order = 4 >c>a>b Ki) (2) 9 1 -0-H om "| (e) ’ ° om Due to ortho effect COOH goes out of plane b>a Somax. acidity‘COOH 00H ® @ Oo" (GY oie mre by ten cota test b> a i a H -o-4 me SMe t t ww) @) ty (e) fo 7 oO Qo x ‘ oH) Acidity order ¢ > b> a g -O-H -O-# = OH ™ @ O) © or * NO, a OFtho effect of =o =o M, 1 ‘Acidity order = ¢ > 3>b ani) cH, «© © () z4Oye ‘Strongest acid = (b) On cH yH Ww & O. () & © & (a) - "NO, . CH, Lis more ‘So maximum acidity of a. ©‘OH OH wn CS oO) = “© acidity = with drawing tendency of group. 50 (b) max. acidity. 8 (i) Cysteine: coon wd YC NH 1 deity « Ee Acidity order = coo? > -5® > - NH acidity, of “COOH (2) > -COOH (1) due to - 1 effect to -NH, ‘order of acidity : ~ CODH (2) > ~ COOH (1) > - NH, ‘order of Pk: - NH, > ~ COOH (1) > - COOH (2) on on coon % (a) O © cyclohexane carboxilic acid acidity stabity of CB coon OH On acidity = > > Pyorder=3<2<1 (b) 1 = butyne, -butenen, butane dy -8s, 8 & Oy Cy CH= Oy cH Hy GH = Cy sp 5acidity order = 1>2>3 Pk, order=1<2<3 (©) Prophanoic acid, 3+Bromo propanoic acid 2-nitro propanclc acid 3431 21 c-c-c-o# &-€-6-on c-8-b-o é & § No; 4 oD acidity 3>2>1 3<2<1 (6) Phenol, O-cresol on on chy +1 tH acidity order = 2>1>3 PLorder=2<1<3 (e) Hexytamine, aniline, Methyl amine wa ° (Ch - NH + CH - NH 2 eM e@ (a), = Cry ~ Cry — CH - Hy NH, ° (CHy ~ CH, - CH - CH) ~ CH - CH, -NH acidity « stability of conjugate Base stability order = 2>3> 1 acidity order = 2>3>1 Peazedel (2) CHy -CH, ~Br & CH -NO, (b) cry -C-cH, (CCH, CHO + 0)" Ga “CH-er 8 -c-cr cH OF NO, 8 ¢ ney 2 (1) Cyc (2) CH, -NO, 0) 4, -E-a, ne “1 "41. 12. (2)is stronger acid (2) CHy-C-CH-CN (2) 2y,-no, Woo ° (>a) (2)>@) (>) on on (@) as (2) acidity « - M effect O=C-CH; + -M So (2)(s weaked aia 9. 2 "ose- cH, ms So at tS weaker acid sH OH es es s° of cS) oF Stability of C.B. = > Acidity « stability of C. °0 So is weaker acid ° coon or ye tt N -C-OH / ° 4 1 (a) ° wae Ow :3 4, acidity # - M effect ‘$0 (2) is more acidic (b) CHy-CH,-CH,-OH or = CH,-CH= CH-O# ' 4 CH, ~ CH, - CH, - oP CH, - CH=CH of ‘Showing Resonance so more acidic ‘So (2)is stronger acid (©) CH,-CH=CH-CH,-OH = or = CH,- CH = CH- OH t CH, - CH ® CH -CH,~ o® (2) CH,- CH= CH- oP ‘Show Resonance so more acidic ‘so (2) is stronger acid ()__Basicity « Stability of enion Stability order F~ < CI” < Br” CI > Br >I (i) Stability order CH; < NHj < OH (E.N.) Basicity order CH; > NH; > OH > F Ri, pn SHH n-o Ain, 1.91 localised 4p. detocalised i ‘(more basic) (weak base) top. Dore delocalised (least base) basicity order a> b> (iv) Ingas phase basicity « (+1) effect. Basicity order NM, < Me o- NM, < Meo NH are < Mea We Me ato at bat Me 4 (v)__InH,0, 3°-amine is less basic than 1°-amine due toless solvation. Basicity order : 2°-amine > 1*-amine > 3°-amine > NH, Oo GO G15.(1) (a) CH, CH, Ni, @w) » ghd igubcatsed iin, iin, w © 1 mine Basicity c>a>b & ‘Strong-1 Shetfect 1 Basicity « Cy atect = (HMeffect Basicityb>c>a tw) (a) WA Strong-I-effect of, AIH, least basic oa © +1 effect of -CH,, most basic 3p? Least electronegative. most basic order a>b>c (2) cH, - 6 fin, ° feast basic, l.p. of nitrogen is delocalised. delocalised C2 NH" ON 1B: localised (2° amine) & Weak -1 effect iin, over Weak -I effect of Cl, less basic fin, (2) No effect of any group. Weaker than C, but stronger than a & b compound. (CH, - CoN sp most electronegative least basic. (b) CH,CH, fie, Lone pair localised@ a, -¢ fii (©) fin c Gin, ha he More basic due to Most basic, due to more elocalisation of only delocalisation of | one lip. Basicity orderd >c>b>a iy (a) l \ (b) J © ‘NH . NH, * Compound ‘a's least basic, because |.p. of Nitrogen will more take participate in resonance due to aromaticity. Compound 'b' is most basic, because its |.p. is localised. Compound 'c' is more basic than ‘b’ because its |.p. is delocalised. b>c>a. aE on, tw) |.p. of nitrogen is in conjugation with benzene as well as - C - CH,, least ° basic. Wh, |Lp. of nitrogen is in conjugation only with benzene. it is more basic than compound ‘a’. fin - cH.cH, due to extra +1 effect of -CH,CH, group, compound ‘cis most basic than a ab. orderc>b>a NH, NH, CHy, , w) L dL, boa No, No; is least basic than b, due to ortho effect of two -CH, group.16(i) wy a) (w) ) NH, f -™ O -— " +M Orderof-M -NO, > -CN Order of +M_-NH; > -OMe 1 Basicity « +M «5 Basicity order d > ¢ > b > aincreasing order. NH, Ortho effect eG, NH, ‘Compound C is most basic due to +H effect of -CH, group. But compound ais least basic due to ortho effect of =CH, group. Basicity order c> b> & NH, NA, 5 aX, By NOs Basicity order b > > c. NH, NH, 0 oO Ortho effect, less basic Ordera>b>c Mey ome Mey Me Qo o, 4 OMe Basicity order c > a>b NH, ontne ettect NO, NH, Me CMe Me Greater ortho effect, least basic. Mey Me on17.4) info) iy (w) 18.1) w 19, Q 9 sp 4 sp" & delocalisation of .p. 0 (oC) sagen ' hsp Hsp In compound '6', hybridisation of N is sp Ie. less electronegative and -I effect of Sis less. In compound b, N atom is sp? hybridised, and I.p. of nitrogen is localised. ‘Compound a is most basic because charge density on double bonded nitrogen is very high due to resonance. In compound a, the e~ charge density Is very high due to -ve charge. 1 Basiclty « EN of anion Order of E.N. CH,CH, < CH, = CH” < HC# C < CH,CH,O- o ” 0 8 Decreasing order of basicity b > a 3d > c. » Orin 5 (O)-en. i, oye path wit, beleonehing. Lp. localised, most basic o@em aw Oppm i NO; Ortho effect |up. is in conjugation with a Which is most with drawing. Decreasing order of basicity:b>a>c>d Hye Hs =o HAN - C= Hic. CH NH - C= CH NH cH cn,'a Is most basic due to high charge density. bis more basic than d and c due to ortho effect. 2e Latur tecnce!n eens cred ah -5 =n. oursarteere NH, NH, NH, s Y NO; least basic due nos NO, _y cashes i NH, NH, NH, NH, » 06) a) amy 6 NOs 44 OCH 44 Heit Order : I> IV>1> 11 h " ‘This'fone pair very much delocalised because of getting Aromaticity so do not donate lone pair $0 itis least basic. 2B.) CHM, « an ern, =f Fc - in, cH, - Rin, 7 have more tendensity to donate the pair of e-. NH (b&b) CH,CONH, em In aquous solution 2° are more basic because of solvation energy. 2>1 (2) nPrNH, or CHCN@) © @) (b) ©) chy- Ch, - cH, - fi, oH,-e-N sp''N’ ‘sp Nitrogen 12 more EN weak basic CyHgN (CH,), or 2,6-d1 methyl-N, N-dimethy! aniline, HyCA a, CH? Ges out of plane Hic cH So more basic ¥ "Cy O ortha effect So2>1 mit anilineor —_p-nitro aniline iin, fin, No, " Somore basic 1 > 2 P-methoxy aniline or P-cyano aniline Ny NH, H +m ov ‘So more basic 1 > 2 a Puridine or Pyrrale "y on lone par E> 2 Localised lone pair Hh so least basic. CHyC=N o HCH, NH, ‘ t ‘sp nitrogen so less basic sp Nitrogen 2>4) Oy @® 46 . Ho" (2) _+ve charged spcie is weak base. (b) HS, -SH, S* (1) Neutral so weak base More -ve charge more donating tendency. (ce) Cr, “SH Q)) S___ GEN. tsizesmait More sable less basic (FO NH CH CHy NH OH F te (1) F° Somore stable less basic Er H,6, fin, (1)'F more electronegative so do not donate the pair of e so less basic. ‘OH SH Sei Big size (3) -ve charge stable, So weak base. 1 Basielty «Stay fa, ia, (@y ow No, -M 50 more tendency to donate the pair of e° of NH, in the ring. So weak base (b) CH, = CH=CH = CH=CH, or CH, = CH- CH" long resonance ‘So-ve charge delocalised ‘So weak base wo bb © BB ‘Anions are more Basic than Neutral. So (2) is a weak base.27.10) (0) On cH, + o Strong Base Nin, fim, is, . CH, NO; Ww or mor =m (iy) O Lhtaiael Localised |.p. of N 3 CH,COO > GH Basicity order : OH > CH,COO > Ci o o o w CHac (ii) CHy= OH (ii) CHC Stability = (i) > (1) > (lit) Basicity = (1) < (li) < (i) oe uh CH, = CH - CH, ~ NH, sp os hs, ~ cn, cn, fi, cc ~ cn, - iH, 2 Basic strength : 3<1<2Ret cay NH NH, 29.(a) (0) O a © qu OQ Move resonance (b) «© (b) © ai. More delocalised s0 least basic wedi NH, NH, NH, 1 wo or a) iy cl Ortho eftect More -1 a Less -1 1<2<3 NH, NH, NH; a i, S 4, +1 oe 2>1>3, (2) CH,NH, (Neutral), CH, "NH, (+-ve charged), CH,NH™ (-ve charged) 2<1<3 CHO", CHNH", CHCH,- More E.N. more stable 1 <2<3 CHCA = CH, CHLCHLE , CH, C= sp’ 5 sp Stability = 3>1>2 Basicity order = 3<1<2 o Oo oo More resonance least basic 2>1>3Localised I.p. oC 1>2>3 HNN Wow NoH MN Portipate in resonance so feast besic C GB EY Ci Wen 2 ye Me LA Pyrimidine ipsione urine Ubcalsed lone pair wants fen Three basic ‘N’ of, 6xe-aroratic ploee on ol NIN, N7 nH ee aromatic So (A), (C) & (D) are aromatic.EXERCISE - IV PREVIOUS YEARS ‘Soi A More the ~CH, groups, more will be the +1 effect. (CH)),C ~ > (CH,),CH * > CH,CH, - Sol2 A aa CH, - > CH, -CH- > CH,-C- Hy Sols A ‘As the no. of e~ donating groups increase, basicity increases. INH, < CH.NH, < (CH,),NH Sola A Clis betterleaving group. SolS D e“ withdrawing group increases acidity. NO, is ortho and para directing group. Sols D Lone pair of N is not in conjugation with benzene ning. Sol? D ‘As the bulkiness increases, nucleophilicity decreases, More is the electronegativity, more will be the nucleophilicity. 8 lis better leaving group. Solo 8 Lone pair of N Is not in conjugation with benzene ring. Sol.10D More is the resonance or a-H, more will be the stability of free radical. (CH),CH < (CH,),E < (CH,),CH < HE SoLt1b Reaction with bulkier nucleophile will be slower, sou128 © withdrawing groups increase the acidity and e~ donating groups decrease the acidity. Solasc Due to less steric effect and more +1 effect. soli40 Nitro group decreases the e~ density at benzene ring. SohISB withdrawing groups stabilise and e~ donating groups destabilise the carbanions. Sol16D Correct order of increasing basic strength is, RCOO- I > 1 > Iv ‘4 molecular mass sol.16 “le Oy ‘00H cooH 4 ermeen.seneng Ht Sol.17 oH BP. inter molecular H-bonding Intra molecular H-bonding Sol.18 0g. CH,- CH= CH, State Sle &, It means o (sigma) Convert into x (pie) > @-xoverlapOH COOH oH coon ‘Sol.20 (i) oO of Co) QO (wv) O a cH, 1 1 1 1 . e:RS. eq:-R.S. ° ° coo 00 ch 4 +H Ph - COO: is more stable than PhO- MI>Iv>>1 S220 c= RAW Swen wy wed " MEW I>M> > v 22 Hk la nec ec ES, I ft & OHH Ot, HoH ett weng-¢-E-o% hh ba, tia en, Sol, 23 fit, — cH, — cH — cH — cH, — oH — C2 oo NH OR because —NH, and ~COO- both have lone pair (two basic gp in following compound).H wan e a oC" O No, on oH, 1 L 1 1 y 00° coo" ‘00° g oO Q oer M,-1 Sol.25 cH, _CH—cH, ‘This compound have 61H So It form six hyperconjugative structure. Sol. 268, Inalliene (C,H,) HO=C=C H, sp Sp sp" Sol.27 8 Its anti-aromatic compound. It dimerise at room temperature. 00 ee