ELECTRONIC DISPLACEMENT EFFECT BOND CLEAVAGE Organic reaction is a process in which breaking and formation of covalent bonds takes place. In organic reaction, the organic compound which is converted into a new compound by breaking and formation of covalent bonds is known as the reactant or substrate and the new compound formed is known as the product. ‘The chemical species (more reactive) which causes the change is called reagent. CH,—CH,— Br-+ “OH —> CH,— CH, — OH + Br- substrate Reagent Product or Reactant Breaking of covalent bond is known as bond cleavage. A bond can be broken by two ways : Bond Cleavage Homolytic Heterolytic Free Radicals, Cations & Anion: are formed are formed Homolytic Fission or Homolysis © Thecovalent bondis broken in such a way that each resulting species gets its own electron, This leads to the formation of odd electron species knownas free radical. + Homolyticbond fission gives free radical asthe reaction intermediate, Bp — A+ “ free radical * The factor which favours homolysis is zero or a small difference in electronegativity between Aand B. © Homolytic bond fission takes place in gaseous phase or in the presence of non polar solvents (CCI, cs). Heterolytic Bond Fission or Heterolysis, * _Tnheterolysis the covalent bond is broken in such a way that one species (i. less electronegative) loss its own electron, while the other species (ie., more electronegative) gains both the electrons. KY © Thus formation of opposite charged species takes place. In case of organic compounds, if positive ‘charged is present on the carbon then cation is tremed as carbocation, If negative charge is present on the carbon then anion is termed as carbanion ‘© The factor which favours heterolysisiis a greater difference of electronegativity between Aand B. eo B —+A+B REACTION INTERMEDIATES Reaction intermediates are generated by the breaking of covalent bond of the substance. They are short-lived species (half life > 10~* sec.) and are highly reactive. few important types of reaction- intermediates are as follows. (1) Carbocation (2) Carbanion 3) Free radicalCarbocations ‘An organic species which has a carbon atom bearing six electrons in its outermost shell and has a positive charge is called a carbocation, Characteristics of Carbocatio1 @ —_ Carbocation have a positive charge on carbon. (i) Positively charged carbocation has only 6 electrons in the outermost shell. Ithas an incomplete octet. Soit behaves like a lewis acid. Gii) Since all electrons are in paired state so carbocations are diamagnetic. (Gv) Carbocations are sp’ hybridised. () _ Carbocations are planar with a perpendicular empty p-orbital. Due to planar structure carbocation leads racemization in stereogenic conditions. (vi) Carbocations are formed in polar solvent. (vii) Itstabilize by presence of electron donating group (EDG) Carbanions ‘Anion of carbon is known as carbanion, Carbanion carries three bond pairs and one lone pair, thus making the carbon atom negatively charged thus carbanion may be represented as ° /i\ Characteristic of Carbanions ¢ It is formed by heterolytic bond fission. “There are eight electrons in the outermost orbit of carbanionic carbon hence its octet is complete. It behaves as charged nucleophile. tis diamagnetic in character because all eight electrons are paired. Hybridisation and geometry : Alkyl carbanion has three bond pairs and one lone pair. Thus hybridisation is sp? and geometry is pyramidal Q AN Note : Geometry of allyl and benzyl cabanion is almost planar and hybridisation is sp*, (Vi) Itreacts with electrophiles. (wii) IL stabilize by presence of electron withdrawing group (EWG) Carbon Free Radical @ Carbon free radicals are odd electron species in which carbon atom bears the odd electron. (i) Homolytic bond fission of a covalent single bond gives rise to free radicals. Gii) There are seven electrons in the outer most shell of carbon free radicals. Gv) Owing to the presence of an odd electron; a carbon radical is paramagnetic in nature. Due to reason free radicals are highly reactive. () Carbon free radicals are normally sp* hybridized (i) Free radicals are neutral electrophiles. (vil) It stabilize by presence of electron releasing group (ERG) ‘Seaned with anSeannerELECTRONIC DISPLACEMENT EFFECTS (EDE) Electronic Displacement effect L Permanent Effect ‘Temporary Effect + ¥ t v + ¥ v Inductive | Mesomeric Hyperconjugation Electromeric Inductomeric Effect Effect effect effect effect INDUCTIVE EFFECT (I-EFFECT) @ @ Gi) Ww) w) wi) ‘The displacement (shifting) of an electron (shared) pair along the carbon chain due to the diffrence in electronegativity of the groups present along with carbon chain is known as inductive effect. Be BH > CHC -- C + G (G: functional group) s- 8- Bt Ce Ce € HG But the effect is insignificant beyond third carbon atom. (distance dependent effect) This effect is transmitted through the chain of 6 bonds and diminishes, with increasing chain length. Inductive effect is thus A permanent effect ‘The electrons never leave their original atomic orbital. Operates through & bonds Polarisation of electrons is always in single direction. It is generally observed in saturated compounds. Its magnitude (ie., electron withdrawing or donating power) decreases with increase in distance. On the basis of electron releasing group (ERG) or eletron withdrawing group (EWG) inductive effect, can be of two types. = reffect : The group which withdraws electrons is known as —/ group and its effect is known as — reffect. = 1 power of various group & cation. ° -Nr,> -NH,> -NO, > -SOH > -CN > -CHO > -bg > -cooH > -coor > ~CONH, >-F>-Cl >-Br >] >-OH > -OR > -C = CH > -CH, > -CH = CH, >-H 1 power of groups in decreasing order with respect to the reference H +Teffeet : The group which donates or gives electron is known as + / group and effect is known as + / effect. i eg., Alkyl groups, -Q,-C-O™ are + / groups. (Generally negative charged atoms or groups)fa) ) +I power of different type groups and anions : -CH,>-NH >-O- >-COO > tertiary alkyl> secondary alkyl > primary-alkyl >-CH >-H + I power in decreasing order with reference to H-atom + power of same type of alkyl groups : + Ipower c number of C's in same type of alkyl group CHy—CH,— +1 power in (CH,~CH, -CH,- increasing For example order (CH,-CH, - CH, CH,— APPLICATIONS OF INDUCTIVE EFFECT (a) @ @) (b) © @ © Stability of reaction intermediates @ Stability of carbocation (i) Stability of free Radical (iii) Stability of carbanion Stability of carbocation 1 =I group * Stability of carbocation « Presence of electron releasing group « +I group o (CH)),C* > (CH),CH' > CH,CH," > CH," ze 2» r 2 @ @ @ CH, — CH, > Br—CH, — CH, > Cl— CH, — Cu, > F — CH, — CH, Maximum -I of F @ e 2 CH, ~CH-CH,CH, < CH, -CH, ~CH-CH, < CH, ~CH, ~CH, ~CH, -F F F Maximum -1 Minimum 1 ‘Minimum distance Maximum distance @ @ 2 Gt, Ch, Eh < GH - CH, CH, < ,—CHE 10, F OH Hy, Dy < <) i) @) b) (©) @ Gi) @) (b) © Bredt’s Rule ; Formation of carbocation, free radical and x-bond at bridge head position is not possible due to angle strain. jge head carbon Q ° “ oO eS © cy © o Not possible Stability order: d > a>c>b Ox Stability of free Radical 1 Stability of F.R. o Presence of electron releasing group ¢ #1 gr0up © —Taroap Stability of FR. decrease in the following order (CH),C'> (CH,),CH > CH,CH,"> CH," ES e r Gu, —ch,> Br— Cu, — cH, > cl— Gn, — CH, > F — CH, — CH, Maximum -I of F cu,- én, > Gri Cri > CH, FH cu, > wo. > O NO, Stability of carbanion Stability of carbanion «Presence of electron withdrawing group eI group c= <>. +1 group (CH,),C- < (CH),CH- < CH,CH; < CHE zs 2 r 2 ° e ° CH,-CH,-+NO, > CH,-CH,-+F > CH,-CH,-> OH > CH,-CH,—> NH, e 8 Ba, en en, ct>8n,—ct gu-cin> En, CH,-CH-CH,-F F F©) 5 2, cH CN * ,COOH He C=CH CY > > ° e ° cn, H, @ H, ® * Re, NR ‘NH, > > (B) Acidic Strength Strength of Carboxylic Acid : Acid strength is measured by the position of equilibrium of ionisation in water. HA = Ht + A acid anion (tA [HA] sation constant) (K, = acid ioni or, acid strength & (H*] «: K, ra (here pK, = -logK,) or Acid strength cc concentration of [H*] or Acid strength stability of acid anion Thus strength of acid is the function of stability of acid anion. -’ Stability of carbanion & Pres f electron withdrawis 4 «——— ability of earbanion s Presence of electron withdrawing group e 1 group ce <= = . acidic strength oc Presence of electron withdrawi ea —— ii ath oc Pre leetron withdrawing group «1 group ce <> The influence of the inductive effect on acidity can be summarised as follows : Acidic strength of carboxylic acid (a) &) © @ HF < HCI < HBr < HI CH, < NH, < H,0 < HF C-CH;-COOH < Cl,CH-COOH < CCI;-COOH -1t acid strength T H-COOH>CH,-COOH> CH,~CH,-COOH> CH,-CH,-CH,- COOH + 1power of alkyl groups T Acid stength |© CH,-OH > CH ,-cH,-0Hn I I a NO; I 0 () — (CH,),COH < (CH,),CHOH < CH,CH,OH < CH,OH (©) Basic Strength Basicity of Amines = Basicity is defined as the tendency to donate an electron pair for sharing. The difference in the base strength in various amines can be explained on the basis of +1 effect. ‘The groups producing + effects (alkyl groups) tends to intensify electron density over N in amines thereby producing a base strengthening effect. 1 ‘Thus, strength of base e + 1 power of group present on — NH & Kye 5 Whereas, a group producing -I effect [-Cl, -NO,] tends to decrease electron density over N - atom in amines, thereby producing a base weakening effect. ——__+______cx, =Tpower of group present on—NH, Thus, strength of base x Relative base strength of amines : Examples (a) R - NH, < R,NH < R3N (b) H,O < NH, < NH; 9:9 +24 & <) & > CH- ir -CH, ds, Order of basic strength in solvent phase () | R=CH, > R,NH > RNH, > R,N > NH; @ = CyH; > R,NH > R;N > RNH, > NH;RESONANCE Consider structures of benzene : Go T ‘According to the given structure C,-C, bond length should be smaller then Cy-C; bond length but C)-Cy and C,-C; bond length must be equal. So this bond length data is not explained by single structure so we need two structures of benzene which is following ; A aS CO 1 ott and I1are resonating structures of CH, ‘When amolecule orion can not be represented by single lewis dot structure and more than one stureture are needed to represent all properties of the molecule these structures are known as resonating structure and combined structure of all resonating structure are known as resonance hybrid and this phenomenon known as resonance. Resonating structure have the same arrangement of atomic nuclei but differ in distribution of electrons, (only x electron detocalised) Resonating structure are hypothetical and actual structure isa resonance hybrid. Resonance generally occurs when there is a conjugation of n-bonds (alternate double - single - double bond arrangement) Condition for Resonance : a) 2) @) @) 6) 6) @ Planatity-Atoms considered in molecules must be sp? orsp-hybridised not sp? hybridised. Gi) Conjugation - System in which p-orbitals are arranged parallel and continuous to each other is considered as conjugated system. ‘Negative charge electron altemate to relectron conjugation Lone pair electron altemate to electron conjugation ‘electron alternate to electron conjugation ‘electron altemnate to vacant orbital (Positive charge) conjugation ‘electron alternate to odd electron (free radical) conjugation Lone pair electron alternate to vacant orbital (Positive charge) conjugation Conjugate positions of the molecule = ‘Altemate positions of the molecule having x bond, positive charge, negative charge, odd electron or lone pair of electrons are known as conjugative positions. CH- CH, ~CH = CH - CH = CH - CH = CH, 1, 3, 5 are alternate positions having m bonds. Hence these positons are known as conjugate positions. ca, = CH - cH = CH- GH - CH, 1,'3 and 5 are conjugate positons, cH, = CH- cH = CH - CH = CH- Nu, 1 3 ? 1, 3, 5, 7 are Conjugate positionsNote : Compound having at least two conjugate positions is known as conjugated compound. TYPES OF CONJUGATIONS @ @) @ @ Negative charge electron alternate to 1 electron conjugation : If ina conjugated system x bond and © charge at alternate position so conjugation is known as negative charge electron alternate to x electron conjugation CH,=CH-@H, CH, = CH-CH=CH- Gh, 2 CH, Lone pair electron alteranate to x electron conjugation : If in a conjugated system x bond and lone pair at alternate position so conjugation is known as fp electron aternate to x electron conjugation. CH, = CH - Nu, CH, = CH- & ch, = CH- CH = CH- CH = CH- i GO 6 CS electron alternate to x electron conjugation : If x bond alternate with x bond so conjugation is known as x electron alternate to x electron conjugation cH, = CH - cH = CH, : 3 CH - CH, ~ CH= CH ~ GH = CH ~ gH = CH, Q ‘ 5 electron alternate to vacant orbital (Positive charge) conjugation : If x bond alternate with vacent orbital so conjugation is known as positive charge alternate to 7 electron conjugation. ive charge, 1 conjugation CH, = CH - CH=CH - GH,ELECTRONIC sPLACEMENT EFFECT ag~« These species has two type of conjugation x electron alternate to x electron conjugation and positive charge alterante to x electron conjugation, (8) electron alternate to odd electron (free radical) conjugation : If x bond and odd e are in altemate position. CH - cH, Oo ~~ OHO (© Lone pair electron alternate to vacant orbital (Positive charge) conjugatio: and vacant orbital are alternate position If lone pair es ° CH; -CH-NH, «> CH,~CH=NH, e CH, -CH-OH «> CH,-CH cr, SSAA a, 2 cH,- CH Rules to draw valid resonating structures 1, Electron flow occurs from high electron density to low electron density, Negative charge > Lone pair electron > n-bond electron > 8*—> positive charge 2. Position of atom cannot be change, only the n-electrons are delocalised. ° 0° 1 8 i Ee CH, -C-0 «CH, -C=0 (A) B) A & B are Resonance forms. CH, ~C-CH, > CH, = C-CH, i i ° OH Above forms are not resonating forms because position of H is changed.3. Second period elements should not violate the octet rule while drawing resonating structures H le e ~CH=CH-N'-H <> CH, -CH-CH= H H I 1 Above structures are not resonance form because in structure II, nitrogen has 10 valence electrons which violates octet rule. 4, Each Resonating structures must have the same number of unpaired and paired electrons. CH, = CH-CH, «> CH, CH=CH, I 0 1.& Iare resonating structure because both have 8 paired electrons and 1 unpaired electron 5. Net charge should be conserved in all resonating structures. ® e CH, = CH-CH = CH, «-+CH, -CH=CH-CH, Net Charge =0 Net Charge=0 Both structures have same net charge so both are resonance forms. Rules for stability of resonating structures 1. Among various resonating structure non polar resonating structure is more stable than polar resonating structure more number of covalent bonds is considered to be more contributing than others. ® e CH, = CH-CH=CH, «> CH, ~CH=CH-CH, 2. Iftwo resonance structures have same number of bonds then that structure in which octet of every atom is complete is more contributing than structure having incomplete octet. « e —CH-NH, ©>CH,-CH=NH, 3. Ifresonating structures have same number of bonds then the neutral structures more stable than charged structure and if both are charged Resonating structure then less charged resonating structure is more stable. Incase of charged resonating structures, the most stable one is that in which the positive and negative charge reside on the most electropositive and most electronegative atoms of the structure respectively. CH? —CH =O <> CH, =CH-0° (A) @) stability of B>A 5. Resonating structure in which unlike charges are closer is more contributing than that structures in which unlike charges are far away. 6— 6— O— &e =O (uy an avyHence stability of and IV will be the same and both will be more stable than I!l, The order of stability of resonating structures in decreasing order will be as follows : V>U=Iv>m 6. Resonating structure in which like charges are farer away is more contributing as compared to structure in which like charges are closer. RESONANCE ENERGY ‘The energy differecnce between most stable resonating structure and resonance hybrid is known as resonance energy. © Isthe experimental value which is calculated by heat of hydrogenation (HOH) © Higher the value of resonance energy, greater is the resonance stabilization. Resonance Energy of Benzene : a-O “The resonance energy of benzene is calculated from the heat of hydrogenation as given below: a +B C+ 29 Kea. Dm + C) +22 nats natal but experimental value for benzene is 51 Kcal. so, Resonanceenergy =Calculated value— Experimental value I eg. R.E, CH,-C-O7 CO Aromatic compound have more resonance energy than non-aromatic compound. 3. Incase of larger conjugation, more will be the Resonance energy. =87-51 = 36 Keal. Resonance energy comparison 1, Considerbetter resonance or equivalent resonating structures, molecules having equivalent resonating structures must have more resonance energy, than non-equivalent resonating structures. ° 9 y BY <2PP 4, Resonance energy will be more, when n-bond, lone pair conjugation is present than x, n-conjugation ° 9 Ay « Age ‘Seaned with anSeannerMESOMERIC EFFECT (a) (b) © @ © © (h) Thisis apermanent effect where the displacement of conjugational x electrons are influenced by the group attached to carbon chain. ‘There isa push or pull of electrons of the conjugated system of molecule. Meffect operates only in the conjugated system, Ifthe conjugation is not available, M effect does not propagate further. ‘M-effect has no correlation with the electronegativity of the connecting atom of the group Mceffect is two type; +M and —M +M effect (+R) : If the group pushes the electrons into the 7 electron system, the effect is said as +M effect and the group is called ERG (electron releasing group) or +M group, + M Effect is shown by : ~Cl, -Br, -NH,, NHR, -NR,, -NHCOCH,, -OH , -OR Condition : Electron pair must be present at first atom of group. ~Meffect (-R) : Ifthe z electrons are present system is pulled by the group then the effect is called — Meeffect and the group is called EWG group (electron withdrawing group) or-M group. ex. ccc o € pp M effect is shown by : CHO, C = 0, -COOH, —NO,, -CN, -SO,H, -SO,CI Condition : (i) Vacant orbital must be present (ii) Multiple bond with more electron negative second atom. +Melfect order 1 -CH, >-NH>-O7 2. NH>-NH) ° ° I 3. -NR,>-NHR>—NH,>—NH-E-R>-8O |. -NR,> = —NH,>~ NH-C-R >~ 2 b Sen ° 4, -07>-OR> -0-CH=CH, 5. -NH,>-OH>-F 6 -F>-Cl>-Br>- 1 -M effect order 1. - CH,>-BH, >-PH, 0 2 = Nip ON>- G-11>—G—R>~ 6 -OR>- CNH, ° oO ° °The various resonating structures of chlorobenzene, aniline and nitrobenzene are illustrated in following diagrams. Note that — Cl and ~ NH, show + M effect and - NO, show — M effect. ; a Sig cl ql — = @ © ye Hye" :NH, NH, O Cy -O-O @ @ © Note : (Thus, mesomeric effect works at only ortho & para position, itis absent on meta position, while inductive effect works at all three position 0, m, p however intensity of effect decreases as the distance increases, (i) Mesomeric effect always dominates on inductive effect except halogen (Cl, Br, I, only). APPLICATION OF MESOMERIC EFFECT Stability of reaction intermediates (Stability of carbocation © More resonance in carbocation, more stability of carbocation. © Aromatic cations are more stable than non aromatic cations. Example: Stability order : ® ® e @ — CHy~C-CH=CH, > CH, ~CH-CH = CH, > CH, ~CH = CH CH, e e 6 @) CH, =CH-CH, > CH; > CH, -CH, >CH, = CH-CH,—-CH, Maximum resonancew Om < O» < Ge ™ oo I oe e e ° (i) CyM,)sC> (Coll CH> Cy CH, > CH, = CH-CH, > (CH); C> (CH); CH> e CH, > CH, > CH, = CH>CH = (wii) OO: (ecu, > > Ct, (ii) CH, = CH- én, Cis - GH, allyl carbocation benzyl carbocation Number of resonating Number of resonating Structures = 2 Structures = 4 Hence the benzyl carbocation is more stable than the allyl carbocation. eH, Sa &, No, “oO O NO, NO, wo ap (ah Increase in Increase in Increase in ive charge by positive charge Positive charge by “Land - R effect only by -I effect =I and - R effect ty order I> II >1 @ ey ey, GH, : @ * OCH, cH, oO qa (I) Subiied by + Refer uaa Subiied by + Refit esate by tet sey decane yTelet “ower i axis ‘Sees itauen fue oianes) acto aisunc) stability order I > I > ILi) Stal ty of carbanion : More resonance in carbanion, more stal ty of carbanion Example: stability order for following, @ @ Gi) dv) o (wi) (wii) ° ° @ CH,=CH-CH,, CH,=CH. CH,-CH, 1 u mL stability order I > I > IIL ° ® e CH,-OH > CH,-CH,-OH > CH,-CH,—CH,-OH maximum(—I) Minimum (—I) of OH ° ° ° CH,-NO, CH,-CH,-NO, CH,-CH,-NO, I 0 i stability order 1 > I > IL oO. Oo. oO resonance more resonance localized @ charge 1 0 m stability order I> 1 > TI 2 ° e e e (Ces); C> (CgHs)2 CH > CH, CH, > CH, =CH-CH,>CH, =CH e ® e ° CH, > CH, -CH, >(CH,), —CH> (CH,);C °. Or Ore Oem 2anion 1° anion 3° anion 1 i mm 8 a CH, eu, or NO, No, rT I I stability order I > III > IL 8 &, CH, gh OCH, ‘OCH, ocx, 1 u mm stability order I> 1 > IL(iii) Stability of free radicals. © More resonance, more stability of free radical. Example: Stability order Urecn-cH, cen cr=cHeH-cH=cH, lersrianmce worionmce mone ftonance stability order Il > 1 > IL -oa 8 @ i i mt resonance more resonance localized stability order IT> I> IIL Gi) (CH > (CH), CH > ChHCH, > CH,=CH-CH, > (CH,),C > (CH,),CH > CH,CH,>CH, ACIDIC STRENGTH For an acid HA, = Hit A up bia] lsian) [Hal where , K, > Acidity constant, or dissociation constant of acid K, > Explain the strength of acid » Ke Acidic strength « 1/ pK, 1 from law of mass action, K, Acidic strength oc stability of conjugate base «-M effect on «le + z Acidity of Phenol v/s alcohol C,H;OH ——> C,H,6 + #1 Phenol stabilized by resonance R-oH =" 5 R-0°+ H® Alcohol no resonance thus acidic strength of phenol > alcohol more is the stability of phenoxide ion more will be the acidity of phenol Acidity of Substituted Phenols : Acidity of substitued phenols depend on the stability of the phenoxide ion because acidity is the function of conjugate base.Ht , NO, NO, — +H @ 3 oO” @ effect and. power is maximum 0, Og Ole, ap ‘Stabilised by -1 effect only Xo, No, (a) ‘Stabilised by-R and 1 clfect and -1 power is maximum stability order should be I > Ill > It ‘Thus according to stability of anions o-derivative will be more acidic than p-derivative which will be more acidic than m-derivative. But result is as follows in case of nitrophenols, p-derivative is more acidic than o-derivative which is more acidic than m-derivative. In o-derivative , there is intramolecular hydrogen bonding which decrease acidity. Thus order of acidity is as follows H Ht mH Ht > > > NO, ho, Acidity in decreasing order‘Acidity of substituted benzoic acids Ortho substituted benzoic acid is always a stronger acid than m- and p-derivative. This is known as ortho effect COOH ‘00 NO, NO; — +H ‘Thus, anion is stabilised by -R and =I effect and —I power is maximum. S-&. % =o & NO, a Anion is stabilised only by -I effect of NO, group coon 00 — + Ko, Ko, ML ° ° VA o — n—8 ™o ap Anion is stabilised by -R and —I effect of NO, groupcoon 00" — +H Vv av) Thus decreasing order of the stability of these anions is follows : 1 > IlI> I> IV We know that ortho derivative is the most acidic therefore decreasing order of acidity of these acids is as follows = COOH ‘00H 00H HH a” > > > NO, ty in decreasing order BASIC STRENGTH For an base, BOH,)= B',y+ OH, [él loti) ae oe from law of mass action, Kj where , Ky, Basicity constant, or dissociation constant of base K, > Explains the strength of base K, & Basic strength « I/ pK, PK, = ~ log K, POH = - log [OH™} 1 basic strength & 4M ox > e+ Tec Basicity of Aromatic Amines : Basicity of nitrogen contai nitrogen, In aromatic amines, lone pair of elecrons present on nitrogen is delocalised, hence electron density decrease due to resonance. Ex. CgH,NH, is less basic than CH,NH, jing compounds cc Electron density onor o in, om lone pairis participating in noresonance of lone pair lone pair is participating in resonance ee ne so maximum basic and +1 of CH, o ay am basic order I> IIT > 1 Effect of cross conjugation on basicity : Cin | cH, - ~c4iin, <—+ CH, - c=AH, 9 Due to delocalisation and - I effect of A group, amides are less basic than amines. ° Ii. CoHs - C - NH In this amide there is cross conjugation which increases basicity; thus C,H,CONH, is more basic than CH,CONH,, x bond of C = O group is in conjugation to benzene ring as well as lone pair of NH, group. AROMATICITY (a) Aromatic Character of Compounds : According to the Huckel rule, a compound will be aromatic if it fulfils the following four conditions: () Compound should be cyclic Gi) Compound should be planar or nearly planar. ii) Compound should be conjugated through outring, (iv) Compound should have (4n + 2)r conjugated or delocalised electrons where n is a whole number n=0, 1,2,3,4,5,6,.. o LF & 3 4 2 6 10 14 18 (4n+2)nelectron 0.08.0. Vag Examples: 7¥.9 () —_Antiaromatic Compounds : According to Huckel rule, compound will be antiaromatic fit fulfils the following fourconditions @ Compound should be cyclic (i) Compound should be planar. Gi) Compound should be coniueated throueh out ring and seuud incon© «) (iv) Compound should have (4n)z conjugated or delocalised electrons where nis a whole number =1,2,3,4,5,6 (n)nelectron 4.8 2 16 8 @ A: O ‘Non aromatic compounds : these compounds are niether aromatic nor antiaromatic —TV SS aly av) Example Although cyclooctatetraene has (4n)x electrons but even then itis not an antiaromatic. Geometry of this ‘compound is non planar. Thus it is non aromatic. I, IIf” & IV* compounds are not completely conjugated. Note : Due to Aromatically extrastability is achieved by aromatic molecule, than non-aromatic or antiaromatic molecule. Bond order : Bond order in conjugated compound or bond order in compounds which exhibit resonance ‘Tota number of bonds between two atoms ‘Number of resonating siruetres Bond order = For examples : Two bonds one bond [Total bonds on —_ this carbon is Bond order of carbon in benzene = 21 = 1.5 Example : Give the correct order of bond length of following mentioned compounds. (i) CH,-CH, ;NH, Gi) CH, = CH; NH, no resonance(only single bond charecters) resonance (partial double bond characters) bond length order a>bHYPER CONJUGATION Introduction According to inductive effect order of stability of cations should be CH, CH, le | @ @ @ CH,-C-CH,> CH,- CH-CH,> CH,-CH,-CH,> CH,-CH, I CH, But acutally order should be reversed which is explained on the basis of hyper conjugation. 4K n Q i Q a © a HG" CHS CHy=—*H—¢ = CH—CH,=—eH" (= CH—CH,=—*H—C = CHCH, " & & Definition :- Delocalization of conjugated (CH) sigma electrons with x-bond or positive charge or free radical is called hyperconjugation or H-effect. a @ —_hyperconjugating structures may be written involving “no bond” between the alpha carbon and hydrogen atoms so known as “no bond resonance.” i Nathan baker observed this effect so known as “Nathan baker effect” (i) tis also permanent effect Condition for hyperconjugation: @ Compound should have at least one sp?-hybrid carbon of either alkene, alkyl carbocation or alkyl free radical. ( —_ae-carbon with respect to sp® hybrid carbon should have at least one hydrogen, If both these conditions are fulfilled then hyperconjugation will take place in the molecule. TYPES OF HYPERCONJUGATION @ 6 (C~H), vacant orbital (positive charge) hyperconjugation : This type of conjugation occurs in alkyl carbocation, CH, - CH, CH; - GH - CHy cH, - é- GH; CH, no. of a H=3 no. of aH =6 no. of aH = 9o (C-H), hyperconjugation : This type of conjugation occurs in alkenes. . CH,- CH=CH, CH;-¢H-CH=CH, CH;— ¢- CH=CH, t “hn, CH; no.ofaH=3 no, ofaH=1 no. of a H= 0 (ii) 0 (C— H), odd electron hyperconjugation : This type of conjugation occurs in alkyl free radicals - cH,-¢H, — CH,- ¢- Cn, ¢ i ° " cH, Note: Carbanion never shows hyper conjugation, if there is one ~C-H sigma bond alternate with negative charge then there will be no H-effect Hyper conjugating structures due to hyperconjugation may be written involving “no bond” between the alpha carbon and hydrogen atoms. H A 4 H I ° e | 7 I e H-C-CHECH, <—+ H-C=cH-CH, —* H G=CH-CH, «—+ H- C=CH- CH, 1 | H 4 H Hg In the above hyper conjugating structures there is no covalent bond between carbon and hydrogen. From this point of view, hyperconjugation may be regarded as “ no bond resosnance ". ordere of effectiveness of hyperconjugation : ct C-H bond > a C-D bond > a C-T bond APPLICATION OF HYPERCONJUGATION (A) Stability of Alkyl Carbocations : Stability of alkyl carbocations 2 number of hyperconjugating structures «: number of a—hydrogens. Ex.) én, CH;- GH, — CH3— CH - CH; CH, - 6- CH; bu, o a a w) no,ofaH=0 noofaH=3 no.ofaH=6 no, of @H=9 stability order IV > I> >I CH, Dy 5&, Ra, Ht, Gu, @ ° CG ° O . ach, — aCH-CH, @CILCH, Hc-CcH, 1 cH, ca, Gal) = aH) (IaH) (Oar (H effect dominates over I effect) (B) Stability of Alkenes :Hyperconjugation explains the stability of certain alkenes over other alkenes: Stability of alkenes a Number of alpha hydrogens o Number of hyperconjugating structures Fx @ CH,-CH-CH, — CH,-CH,-CH-CH, CH,-Gu -CH = CH cH, o a amy stability order 1 > 1 > IIT CH, CH; CH, CH, NN aie ~ m~ i = c=CH-CH, ‘C= CH, ® OHO Non, cy cH oO am (up. stability order I> I> IT cH, cu, \ 1 i, H=CH, CH-CH, —H,C-C-CH, “O > é -O-0 (©) Stability of Alkyl free radicals : Stability of alkyl free radicals can be explained by hyperconjugation. Stability depends on the number of hyperconjugating structures. structure cH CH,-GH, CHy-CH-CH, CH;- C- CH, | cH; © @ ay w) no.of@H=0 no.ofaH=3 no. of aH=6 no. of @H=9 No of hyperconjugating Structure 0 3 6 9 other then given structure @ Stability is in increasing order WV>m> >1(D) «) (a) ) © Bond length in alkenes: More is the number of hyperconjugating structures, the more will be single bond character in carbon-carbon double bond. ‘The bond length between carbon-carbon double bond < number of hyperconjugating structures. a b © (@ cH,-CH=CH-CHyy CH,-CH= CH,» CH,=CH, Bond length order => a> b> oO. 0 + satan 2825 a> b— iad CH; H,- CH; CH-CH, cH, Electron releasing (or donating) power of (-R) in alkyl benzene : CH; ~ (or alkyl group) is +H group, ortho-para directing group and activating group for electrophilic aromatic substitution reaction because of the hyperconjugation. " : 7 7 H-c He H- ¢ He Ho S88 Sb The electron donating power of alkyl group will depends on the number of hydrogens present on a-carbon. The electron releasing power of some groups are as follows - ch Hs —cH,> cH,—cih= >. cH > cH, cy | cH TF Electron donating power in decreasing order due to the hyperconjugation Heat of hydrogenation (HOH) : R-CH=CH, + H, —> R-CH,CH, + AH heat evolved when 1 mole of any unsaturated hydrocarbon are hydrogenated is called heat of hydrogenation (AH) If alkene is more reactive towards hydrogen then it will evolve more AH. 1 1 Stability of alkene _ number of a-H So, | AH AH o number of bonds Itis exothermic process (energy release) Examples of HOH order @ CH.=CH-CH,-CH,> CH,-CH=CH-CH,(i) CH= CH-Cit,-CH, e>b>a Note : Reverse Hyperconjugation (-H effect) : The phenomenon of hyperconjugation is also observed in the system given below : x | -c-C=C where X - halogen \ In such system the effect operates in the reverse direction. Hence the hyperconjugation in such system is known as reverse hyperconjugation. ey a o a e 6 ci-G¥CHS cH, + Che-cH-CH, —+ 8 é-cn ~ 8, ++ cl- ¢- cH-EH, The meta directing influence and deactivating effect of ~CX; group for electrophilic aromatic substitution reaction can be explained by this effect.i es x-c Xx x I -c —b-b'- : ELECTROMERIC EFFECT : (E-EFFECT) © Itis temporary effect. * The organic compounds having a unsaturation (a double or triple bond) show this effect in the presence of an attacking reagent only. It is defined as the complete transfer of a shared pair of -electrons to one of the atoms joined by a multiple bond on the demand of an attacking reagent. © The effect is annulled as soon as the attacking reagent is removed from the domain of the reaction. * Its represented by E and the shifting of the electrons is shown by a curved arrow (~y). + When inductive and electromeric effect operate in opposite directions, the electomeric effect predominates. * There are two distinct types of electromeric effect. (@ Positive Electromeric Effect (+E effect) : In this effect the x-clectrons of the multiple bond are transferred to that atom to which the reagent gets attached. For example : ° de b+n—st-c< sei “reagent H (i) —_ Negative Electromeric Effect (E effect) : In this effect the n-electrons of the multiple bond are transferred to that atom to which the attacking reagent does not get attached. For example. 8 de fb+ew—3€-c< ‘cageu? cN ATTACKING REAGENTS ‘The species which attack on a substrate and form a product is called as attacking reagents. ‘Substrate - Reactant which is less reactive is generally taken in greater amount. Attacking reagents are of two types (A) Electrophile (B) Nucleophile (A) Electrophiles or electrophilic reagents (E°) (@) They are electron deficient species. (b) They havea tendency to accept electron from another molecule (©) Inareaction, an electrophile attacks the substrate atthe point of maximum electron density. (d) Neutral molecule having electron deficient centre, CCl,,CO,‘Types of Electrophile : @ Positively charged electrophiles 20.9 fr Ro: RCH, CH): Son (@—_Neutralelectrophiles (@) All Lewis acids as : BF,,AICI,,SO,, ZnCl,, BeCl,, FeCl,, SnCl, (b) Free radicals, carbenes acts as electrophiles. (©) Transition metal cations are electrophiles, e.g. Fe, Fe*, Ag*, Ca etc.] (@) Neutral molecule having electron deficient center, eg. CCl,, CO, (B) _ Nucleophlic reagents or nucleophiles : (a) They are electron rich speci (b) —_Allnucleophiles are lewis bases. (©) Theyattack the centre of minimum electron density ina molecule in a chemical reaction. so they have a tendency to donate electron pair. ‘Types of Nucleophile : () Negatively Charged nucleophiles: F, CI, Br, F, OH; CN", RCOO>, RO, R,R- C=C, NH, SH ete. (i) Neutral nucleophile containing lone pair: HG, R-OH, R-O-R, NH, R-NH, (iii) electron containing compounds CH, = CH, CH=CH (©) Ambiphiles: Ambiphiles are those which act as both electrophile and nucleophile. Example : R-CH=0, RCOR, RCOOH etc. Electrophile ‘Nucleophile 1 | Accept electron |Supplies the electron pair Electron deficient (electron loving) Electron rich [Usually positively charged species (Usually negatively charged species [Attacks the points of high clectron density [Attacks the point of low electron denisty wl al elon o 6, @ & H,CH,, CO, NO leg. F, Cl. Br, I, HOCompound CH,C=NH HI HBr +0H il CH,CH HCL CH,SH, H,SO, H CH,CH, OCH,CH, H CH,CH, OH H,O* HNO, CH,SO,H +OH I CH,CNH, ° i E,CCOH ° i] C1,CCOH pK, values Pk, 10.1 -10 2.4 -17 0.0 0.64 ose”) ly ° Ih C1,CHCOH HSO; HPO, ° IL FCH,COH ° i CICH,COH oO IL BrCH,COH ° I ICH,COH HE 0.79 10 1.0 2.0 24 27 28 29 32 32 34 34 38 39cuso-€ si CH,C=NHCH, ( 3 CH, o oO We dl CH,CCH,CH H,CO, HNL HS pK, 40 42 43 45 46 48 49 5. 52 55 59 64 68 70 on-{ pon H,PO; CH,COOH CH,CH,NO, oO oO a) CH,CCH,CCH, HC=N a eu eX pon HOCH,CH, NH, ° i] H,NCH,CO™ HCO; CH,NO, pK, 7 12 78 80 81 82 86 89 91 93 94 95 98 10.0 10.2 10.2 10.2‘Compound pK, na )-ou 103 CH,CH,SH 10.5 oo 1 10.7 CH,CCH,COEt Cin 10.7 CH,CH, NH, 107 wf 1 HPO; 12.3 CF,CH,OH 12.4 o oO iit E1OCCH,COEt 133 HC=CCH,OH 13.5 ° i H,NCNH, 87 cH, + -H,CH,OH cure :CH,O1 139 cH, XM 144 CH,OH 15.5 HO 157 16.0 16 ‘Compound ° I, CCH; CH,CH (CH,),COH ° I cH,CCH, ° I CH,COEt HC=CH CH,C=N ° I CH,CN(CH,), NH, CH,NH,, © CH,=CHCH, CH,=CH, V CH, CH,CH, 16.0 ~7 17 20 24.5 25 30 36 40 41 43 43 46 50Qi @ Gi) ii) (iv) w) iy Q3 w Draw the resonance forms to show the delocalization of charges in the following ions fl i (a) onl Sy, ro) H-C-cH=cH-&h, © Cm @ 0. ©) Ce w+ Me @ ) 2 @ () CH,~ CH= CH-CH=CH- CH -CH, () CH,-CH=CH-CH=CH- Cu, ‘Write stability order of following intermediates: f (CH, - CH (0) CH,-CH-CH, (©) CH,-C@ | CH; @ aw oy — © AY. @ A or ~ © a (a) OX (b) O«< © Q< @ KA ) © QO @ O (@) cR-CH, )ccl,-CH, © CBr,-CH, ‘Write stability order of following intermediates: cH, e 9 (CH, () CH;-CH-CH, (©) CH, te CH,i) (iii) «vy Q4 @ (ii) (ii) (iv) Ww) (b) © (a) HC =e (b) CH, =H (©) CH,- ch, Write stability order of following intermediates: . (b) CH;-CH-CH, (©) CH,-Ce | CH, 0 (@ HC=C (b) CH, =CH (© CH,-cH, “O° "do In each of the following pairs of ions which ion is more stable: 2 © (@) = (CH-CH2 and (I) CH;=CH-CH2 ° MCHC: and CH, = CH en, eu, © o or and (ll) cr @ — () CH,-CH-CH, and (1) CH,-N-CH, CH, -¢-CH, CH, -¢-CH, 6 e © | €H.—CH-NH <> CH,-CH-NHQ6 0) Gi) Gi) (iv) (vy) (i) (ii) Oo © |cu,—c-CH-C—cu, <> cH,—C-CH-C—CH, NH, NH, @ — |cn—cH.—C—wH, <> cH—cH—c=in, Rank the following sets of intermediates in increasing order of their stability. oe 0 6 O @ AA ® AA : cHy CH; cH @ (b) Gh © GH H HH Me " e | (@) Me-c® wy Pee (© Ph CHa @ oO Ph Rank the following sets of intermediates in increasing order of their stability. @ ° e (b) Ph-CH, © oO (a) Me-C-Me | Me (a) CH, =CH (b) CH, =CH-CH, (© Cy @ Oyen, @ @ 43: (a) oyGi) (iv) ) (vi) Qs Qo @) 2 “GF » 6 @ A ) Which of the following pairs has higher resonance energy : wl Je OS (b) CH, = CH-O-CH=CH, & CH, = CH-NH-CH=CH, “Oh, oA» & oC) O Oo (© CH, =CH-NH & HN=CH-NH (@) CH, = CH-F & CH, =CH-Br Hy @) or & CH,=CH-CH, Which of the following pairs has higher resonance energy : (a) CH,COOH & CH,COONa (&) CH, = CH- 6 & CH, =CH-OH Oo” WCCO oC Jeen,-cn-cu=cn-cn=cn, ‘Scanned with CamscarerQ.10 Identify less stable canonical structure in each of the following pairs : (a GH, -0-CH, +H, = 6-CH, oOO-CO 6 o 2 8 ° t tL I IH u NU © te a @ 6 web 7 Sc, uN H~ AY HOON “+O CH, CH, Q11 Identify more stable canonical structure in each of the following pairs : e @ fo o) Q - i nw “SH Me,N7 OMe MeN~ SOMe 2 L\— CS OO 0 -@ Ne en, Cl, . SOx. On © @n,-cH=cH-8<—>CH, =CH-CH=0 oT, Q.12 Rank the following sets of intermediates in increasing order of their stability. cue oO @ (b) Q Et SO cue a @ (b) © @ ° Gi) @) ~—-CH,-CH_= (6) CH,~CH,Qu3 (a) (b) ©) @ Qu4 Quis w (ii) (ii) (iv) w) (vi) Discuss the following observations: C-Cl bond in vinyl chloride is stronger than in chloroethane Carbon-carbon bond length in ethene is shorter than in CH, = CHOCH, CH,SH is stronger acid than CH,OH CH,CH,NH, is stronger base than CH, = CHNH;. In which of the following pairs, indicated bond is of greater strength : @ Oe and CH, 3 CH, () CH;-CeCH and HCgCH ‘n= cn Sei and Cs -CH, 51 (@) CH, =CHzCH=CH, and CH, =CHy_-CH2~CHs F (©) CH, =CHZCH=CH, and CH, =CH NO, cH; wo Gilly and ua, Write correct order of acidic strength of following compounds: Hy (a) CH,-CH,-O-H__(b) CH, ~CH-O-H (¢) CHy oH | CH; CH; (@) F-CH,-CH,-O-H () NO;-CH,-CH,-O-H (©) Br-CH,-CH,-O-H (@ N-CH, -CH,-O-H ()CH,COOH = (b)CH,CH,OH (©) C,H, (@) C,H,S0,H /N as uM. @/ Yoon ©” Yoon ©” boon coon CH, -COOH OH 2 @ | war ©! cooH coo CH,-COOH ° ° co Il Il Itt -O-H — (b) Cl GH-C-0-H (©) CI-C-C-O-H | a a (@)C1-CH, -(vii) Qis @ (ii) (iii) Qi7 (@) (b) (©) @ (3) Qs ° 9 I (a) CH, -CH, ~CH-C-O-H (6) CH,-CH-CH, | F F i (©) Gils “Cit, -CHs-C-0-1 F Write correct order of acidic strength of following compounds; O-H @ ) © No, a ty a @ (oy © cl Sa OH @ © @ Record the following sets of compounds according to increasing pK, (= ~ log Ka) on on . cyclohexane carboxylic acid. 1-butyne, I-butene, butane Propanoic acid, 3-bromopropanoic acid, 2-nitropropanoic acid Phenol,o-nitrophenol, o-cresol Hexylamine, aniline, methylamine Explain which is a stronger acid. (a) CH,CH, & BrCH,NO, ° ° () cH,-C-cn, & cu,-C-cr,cn (©) CH, - CHO & CH, ~ NO, ‘Seaned with anSeannerQug @ (>) «) Q20 @ (19) (iii) «wy w) wi) (vii) (viii) Which of the following would you predict to be the stronger acid ? 0, ° con Ne on 7 CH,- CH, - CH, - OH or CH, - CH = CH- OH CH,- CH=CH - CH, OH or CH, - CH= CH-OH Write decreasing order of basic strength of following: (@ F° wae (© Be @ cu? (®) NH (© on® (a) R-NH,, (b) Ph-NH,, © R-C-NH, ° (a) NH, (b) MeNH, (©) Me,NH (a) NH, (b) MeNH, (©) Me,.NH o. @ Coe ) G2 Ni N Me Nu, NH, @ CO Co) 6) © OQ NH @) wie (d) Me,N (Gas phase) (@)Me,N (in H,0)Q21 Write decreasing order of basic strength of following: @ @ CH,CH,-Nx, (b) CHY-CH=NH (©) CH,-C=N JH, (b)CH,-CH,-Nu, (© CH,-C-Nu, (@ Nu,-C-Nu, Gi) @ cH C— i NH NH Nu, Gi) @ © © Q NH-C-cH, Nu, NH-CH,-CH, ww) @ QO © O © Nu, Me- Me wo @ on So Q.22. Write decreasing order of basic strength of following: Nu, Nn, in, Nn, ao @ (b) © (d) NO, cN OMe NH, Nu, Nu, Nu, @ @ vw CL © i) @ Q x bn H HN H NH Nn, xn i) (@) ) OL © Os NOs NO; No,(iv) (i) (iit) (iv) Q.24 @ (i) Q25 @) © © 1, * @ CQ © © cr -OMi @ © © oy . Me ‘OMe Select the strongest base in following compound : O. S. @ O o) O co ce) I | | H H H NH, © Oe GO GY | H N od S ml \ oi S wl S H I I I | i by, k i ¥ ® C ) cy oy ory Arrange the following compound in decreasing order of their basicity. (a) H,C=CHNa ——(b) CH,CH,Na (©) CH,CH,ONa = (d) HC= CNa (@) HO- () NH, HO In each of the following pair of compounds, which is more basic in aqueous solution? Give an explanation for your choice: NH CH,NH, or CF,NH, (&) — CH,CONH, or HN NH, n-PENH, or CH,CN (@)— CgH,N(CH,), or 2,6-dimethyl-N-N-dimethylanitine m-nitroaniline or p-nitroanitineQ.26 From the following pair, select the stronger base: (a) p-methoxy aniline or p-cyanoaniline () pyridine or pyrrole (©) CH,CNor CH,CH,NH, Q.27 Choose the member of each of the following pairs of compunds that is likely to be the weaker base, (a) H,O or H,0® (b) H,S, HS, S* (©) Cr, SH" (@)F, OH, NHy, CH} (e) HE, H,0, NH, (f) OH, SH”, SeH” Q28 Rank the following amines “Oo oO G& OD @ w Gi) (iv) NH a oo a i) increasing basic nature. Q2 oy Gi) (iv) Q.29 Arrange the basic strength of the following compounds. (a) OH- CH,COO- cr @ ii) Gi) (b+) CHEC (CH, = CH” CH,CH; @ (ii) (ili) (ce) CH,=CHCH,NH, CH,CH,CH,NH, © CH=C-CH,NH, (i) Gi) (iii) Q.30 Arrange the basic strength of the following compounds. “© O jw i) (iii) ® oO a a 1 Gi) (iii) © oO" Do ™Q.31 Arrange the following compounds in order of increasing basicity. (a) CH,NH,, CH, NH?, CH|NH— (>) CH,O-,CH,NH-, CH, cH; (© CH,CH=CH-, CH,CH, cH, CH,C=C~ Q32 Rank the amines in each set in order of increasing basi © o™ om ore » O'S ‘> a “ey ora Q.33 Compare heat of hydrogenation (Decreasing order) on CH; i) 0 oe oo ONO Oy (iii) x & Ao He ‘CH 1 H cH. , Ns _. CH; Gu) CH= CH-CH Coy, & CH,-CH=C Ca Q34 Compare heat of hydrogenation (Decreasing order) A B c D E Q.35 Among the following pairs identify the one which gives higher heat of hydrogenation : “a0 om (© CH,-CH=CH—CH, and CH, CH, ~ CH=CH, CH on 3 @ CH and CHQi Q2 Q3 Q4 Qs Q6 Q7 TO OPAC ark neon [SINGLE CORRECT CHOICE TYPE] Which is the correct order of stability of carbanion. () F-CH,-CH, -CHE (ll) 0,N-CH, ~CH, ~CHY e n He (IID) Cl-CH, ~ CH, -CHy (IV) Me, N-CH, ~CH, ~CHy (A> M>I>IV (B)IV>I>Ul>T ()IV>M>I> Ul (D)IV>MI>T>1 Which order is correct regarding stability of intermediates. 2 e @ () CH, =CH-CHz (i) CH, =CH (iy CH=C (Al=0=m (@yI (D)1>1> 1 Select the most stable intermediate. He He HP 1H oS (A) @) © @) Hy CH,Me CHMe, CMe, CH, = CH- CH =CH— CH, is more stable than CH, - CH = C = CH - CH, because @ a) (A) there is resonance in I but not in IT (B) there is tautomerism in I but not in TT (©) there is hyperconjugation in I but not in I (D) I has more canonical structures than I, In which of the following molecules 7 — electron density in ring is minimum NOz OCH; ‘NO. ry oO ®) Oo © oy Kos LN Which of the following compound is non aromatic. 2NH, Sy ' H 1 Se H Among the following molecules, the correct order of C - C bond length is (A) GH, > CH, > C,H, > CH, (B) C,H, > C,H, > C,H, > C,H,(C,H, is benzene) (©) C,H, > C3H,> C,H, > CH, (D) C)H, > C,H, > C,H, > CH,Qs Qo Qu0 Qu Qu2 Qu3 C1 - C2 bond is shortest in ~~ ‘ea nl 2° 1 oe wey cy ory Which of the following has longest C—O bond oo 0 0 “) cr ) oO © cr @) cn, Nis Nh Nh CH,=NH cHo 1 0 I Iv Among these compounds, the correct order of C—N bond lengths is (A)IV>I>0>I (B)MI>I>M>IV (C)M>M>I>IV (D) M>I>IV>l Select the least acidic compound. ° 9 (A) No,-CH,-C-0-H ®) pcx, -C-0-# Oo IL II (C) Ph-CH, -C-O-H (D) CH;-CH, ~C-O-H Arrange the given phenols in their decreasing order of acidity: () C,H;-OH a r{O)-on (ly a{O)-on av) oxXO)-on Select the correct answer from the given code: (A)IV>IN>I>H (B)IV>I>M>1 ()IV>M>M>1 ()IV>I>m>0 Which of the following is weakest acid? coon gow coo “ O ®) oO Oo oy or" oll ‘OHQua Quis Qi6 Qu7 Qs Quy Q20 Qa Which of the following compound is having highest pH value : (A) Phenol (B) Ethyl alcohol (C) Formic acid (D) Benzoic acid Arrange acidity of given compounds in decreasing order: () CH,-NH-CH,-CH,-OH (Il) CH,-NH-CH,-CH,-CH,-OH ° (il (CH,),N-CH, ~CH, -OH (A) Il>I>T (B) MI>0>1 (C)I>n>m (D) N>1> 1 Consider the basicity of the following aromatic amines: © aniline (QD) p-nitroaniline (IM) p-methoxyaniline (IV) p-methylaniline The correct order of decreasing basicity is: (AMI>IV>1>M (B)M>IV>I>1 (C)I>I>Il>IV (D)IV>I>I>T Which one of the following is least basic in character? £\ mr O CO N (A) i B) NIMH © ¥ @) ¥ n H Select the least basic compound. 7) Oyun, ®) (O)-cmn-Nit © Orne, @) (O)-¢-ni ‘Ni g Consider the following bases: ()o-nitroaniline (II) m-nitroaniline (III) p-nitroaniline ‘The decreasing order of basicity is: (A> MST (B) > I> 1 (I> Im (D) I> > 1 Select the most basic compound. ye Ru, Sn, Nu, a) IO) @) SO © 1) @) ® NH, cr CH; Which one of the following molecules has all the effect, namely inductive, mesomeric and hyperconjugative? (A) CH,CI (B) CH,-CH=CH, © CH,—CH=CH-C-CH, (D) CH, = CH- CH=CH, 0 ‘Seaned with anSeannerQ22 Q23 Q24 Q25 Q26 Q27 Hyperconjugation is best described as: (A) Delocalisation of z electrons into a nearby empty orbital, (B) Delocalisation of 6 electrons into a nearby empty orbital. (C) The effect of alkyl groups donating a small amount of electron density inductively into a carbocation. (D) The migration of a carbon or hydrogen from one carbocation to another. Select the correct statement. (i) Delocalisation of o-electron is hyperconjugation, (ii) Delocalisation of n-electron is resonance. (iii) Partial displacement of o-electron is inductive effect. (A)i & iii (B) ii (iii (D) it i, iii Select correct order of HOH following compounds (A)I>U>M>1V (B)IV>>M>1 (]M>I>1>1V W)IV>M>M>1 Select the correct order of HOH S a a a A Ss «cl (iv) (A)I> I> I> IV (B)IV>II>1>1 (C)M>M>IV>1_ (D) > Ml>1>1V Arrange following compounds in decreasing order of electrophilic substitution. Ms H 1 CH; CH;—C—CH, — H+C—CH, S (A)i>ii>ili>iv (B) ii) (iv) V>ii>i (C)i>iv>ii>ili (D)i>ii>iv>iii [MULTIPLE CORRECT CHOICE TYPE] Resonance energy will be more if (A) canonical structures are equivalent than if canonical structures are non-equivalent. (B) molecule is aromatic than if molecule is not aromatic, (C) Dancing Resonance is responsible for stability of tricyclo propyl methyl carbocation (D) Resonance with 2p-2p overlapping than resonance with 3p-2p overlapping. ‘Scanned with CamscarerQ28 Q29 Q.30 Q31 a3 Q33 ELECTRONIC DISPLACEMENT EFFECT In which of the following pairs II compound has higher resonance energy : on ~ ws IO -O~ of! & cr (D) CH, = CH- OH & CH, = CH-CH=CH-OH MAW &AA4 In which of the following pairs II”’ compound has less resonance energy : (A) CO} & HCOO- @) [>e & CH, =CH- CH; & CH, = CH- CH=CH, of>e & CH,=CH- GH, ol “ OO ‘Which of the following groups cannot participate in resonance with other suitable group : (A)-COoH (B) -coo) (©)- Coc! (D) —NH; e Pi (© -CH, © -cH, Identify electron — donating groups in resonance among the following (A)-CONH, (B)-NO, (C)- OCOCH, (D)- COOCH, (E)- CHO (F)- NHCOCH, Identify electron — withdrawing groups in resonance among the following : (A)-COOH (B) - CONHCH, «C)-COCcl ()-CN ()-0-cH=CcH, © QO Which of the following group can participate in resonance with other suitable group : ° ‘CHaS (A)CH, =0- (B)-cH,-TH, (©-cn,-@n, © CH=CH e oy (F)- BH, (G) PPh,ELECTRONIC DISPLACEMENT EFFECT -]—$—————— OO ororornrvrvrrvvrvovorvrre' Q34 Which one of the following pairs of structures represent the phenomenon of resonance? ° o ZN) n,c=cH-O-H 4 ch,-cu=b-n (8) CH, =CH-CHCI; CH,-CH=CH-Cl ° o © (city ,cH-C-07; (chy cH-C=0 ° o (D) CHy—CHy -C-CH: ci,-cH=¢-cn, Q35 In which of the following pairs 1I™ compound has less resonance energy : wh de le, 0 & Oho, 2 C\ c\ of) & Cr, (D) N & o. Select the correct statement about product A. (A) Product is aromatic (B) Product has high dipole moment. (C) Product has less resonance energy (D) Product is soluble in polar solvent. Q37_ Which of the following compound is / are aromatic. (A) Gs (B) nhs © Q () Q.38 Which of the following statements would be false about this compound : NO» NO, Deo Be (A) All three C-N bonds are of same length, (B) CI-N and C3 —N bonds are of same length but shorter than C5 - N bond. (C) CI-N and C3 -N bonds are of same length but longer than C5 —N bond. (D) Cl—-N and C3 — N bonds are of different length but both are longer than C5 - N_bondELECTRONIC DISPLACEMENT EFFECT Q39 Which of the following statement is /are correct ? (A) Contributing structures contributes to the resonance hybrid is directly proportion of their energies. (B) Equivalent contributing structure make the resonance very important, (C) Contributing structures represent hypothetical molecules having no real existance. (D) Contributing structures are less stable than the resonance hybrid. Q40__ In which of the following pair I™ compound is weaker base. Nh “ Or Oo (B) CH,=CH-CH=CH- eu, or CH,= CH= en, oOo oo id oi (C) O--C-C-OH or HO-C-C-OH og 6 Q41_ Among the following statements which one is/are correct (A) Cyanic acid (H - 0 - C= N) and isocyanic acid (H - (B) Ka of formic acid is higher than II® Ka(Ka,) of oxalic acid. (C) Acids which are weaker than H,CO, will liberate CO, on treatment with NaHCO,. (D) In case of dicarboxylic acid Ka, (I* dissociation), is always greater then Ka, (1™ dissociation) ©) are not separable in HOELECTRONIC DISPLACEMENT EFFECT Qu Q2 Q3 Q4 Qs Q6 Q7 Qs Qs Quo SECTION-A (JEE ADVANCED Previous Year's Questions) Phenol is less acidic than [JEE 1986] (A) Acetic acid (B) p-methoxy phenol (C) p-nitrophenol (D) Ethanol The bond between carbon atom (1) and carbon atom (2) in compound (JEE 1987] involves the hybridisations as (A) sp? and sp” (B) sp* and sp (C) sp and sp? (D) sp and sp Polarisation of electrons in acrolein may be written as, (EE 1988] & - i] ES il (A) H,C=CH-C-H (8) H,C=CH-C-H * soa f «| (C) H,C=CH-C-H (©) H,C=CH-C-H The number of sigma and pi-bonds in 1-butene 3-yne are [JEE 1989] (A) 5 sigma and 5 pi (B) 7 sigma and 3 pi (C) 8 sigma and 2 pi (D) 6 sigma and 4 pi Amongst the following, the most basic compound is [JEE 1990] (A) benzylamine (B) aniline (© acetaniline (D) prnitroaniline The shape of (CH,)* is [JEE 1990] The hybridisation of carbon atoms in C-C single bond H-C =C-CH=CH, is [JEE 1991] (A) sp sp* (B) sp?—sp" (©) sp-sp* (D) sp-sp? The molecules that will have dipole moment are : UEE 1992] (B) trans 2-pentene (C)cis 3-hexene (D) 2,2,3,3-tetramethy! butane ‘What is the decreasing order of strength of the base? (EE 1992] OH” ,NH,, H-C=C” and CH,-CH,- (A) CH, CH," >NH,~>H-C=C7>OH™ (B) H-C=C” > CH,- CH, > NH,~ > OH™ (C) OH” > NH, >H-C=C~>CH,-CH,” (D) NH, >H-C=C”>OH>CH,-CH, The bond dissociation energy needed to form the benzyl radical from toluene is than the formation of the methyl radical from methane [JEE 1994]Qu Que Qu3 Qi4 Quis Qué Qu7 Qs Qs Q20 Qi Qn ELECTRONIC DISPLACEMENT EFFECT ‘The kind of delocalisation involving sigma bond orbitals is called [JE 1994] Arrange the following in the order of their increasing basicity : p-toludine, N,N-dimethyl-p-tolui- dine, p-nitroaniline, aniline. [TEE 1995] In the following compounds: UEE 1996] 1 ou Cy a (aly ws The order of rity is: (A)MI>IV>I>M (B)I>1V>M>M (C)M>I>M>IV (D)IV>M>I>1 Although phenoxide ion has more number of resonating structures than benzoate ion, benzoic acid is a stronger acid than phenol. Why? (EE 1997] Among the following compounds, the strongest acid is [JEE 1998] (A) HC = CH (B) CH, OGH, (D)CH,OH ‘The most unlikely representation of resonance structure of p-nitrophenoxide ion is:[JEE 1998] VA Vw Re VAP (A) O (B) O © O (D) Oo o oO o 5 Give reasons for the following in one or two sentences. The central carbon - carbon bond in 1,3 butadiene is shorter than that of n-butne. [JEE 1998] Explain, why o-hydroxybenzaldehyde is aliquid at room temperature while p-hydroxybenzaldchyde is a high melting solid [EE 1999] Give reasons for the following (JEE 2000) CH, = CH is more basic than HC=C~ ‘The compound in which C uses only its sp?-hybrid orbitals for bond formation is : [JEE 2000] (A) HCOOH (B) (H.N),CO (© (CH,,COH ~— (D) CH,CHO. Which of the following has the most acidic hydrogen? [JEE 2000] (A) 3-hexanone —_—_(B) 2,4-hexanedione (C) 2,5-hexaedione _(D) 2,3-hexaedione Amongst the following the strongest base is: [JEE 2000) (A) CHNH, (B) p-O,NC,H,NH, (C) m-O,NC,H,NH, (D) C,H,CH,NH,Q.23 Qu Q25 Q26 Q27 Q28 ELECTRONIC DISPLACEMENT EFFECT The correct order of basicities of the following compounds is: [JEE 2001] NII ae, CH,CH,NH, (CH,),NH CH,CNH, @ Q) (3) @ (A)2>1>3>4 (B)1>3>2>4 (C©3>1>2>4 D1 >2>3>4 Which of the following hydrocarbons has the lowest dipole moment? [JEE 2002] (A) cis-2-butene (B) 2-butyne (©) 1-butyne (D) HC =CH-C=CH Identify the correct order of boiling points of the following compounds. [EE 2002] (1) CH,CH,CH,CH,OH 2) CH,CH,CH,CHO (@) — CH,CH,CH,COOH (A) 1>2>3 (B)3>1>2 (C)1>3>2 (D)3>2>1 Which of the following acids has the smallest dissociation constant? [JEE 2002] (A) CH,CHFCOOH (B) FCH,CH,COOH (©) BrCH,CH,COOH (D) CH,CHBrCOOH ‘coon ot on’ when X is made to react with 2.eq. of NaNH, the product formed will be: [JEE 2003] “6, oll — 0? (A) S (B) Q < see on - Q © a © (i So @) . Which of the following represent the given mode of hybridisation sp”, sp”, sp, sp from left to right ? [JEE 2003] (A) HC = CH-C=N_(B) H,C=C=CH-CH, (C) HC=C-C=CH —(D) HC=C-CH=CH,,Q29 Q30 Q31 Q32 Q33 Q34 Q35 ELECTRONIC DISPLACEMENT EFFECT Maximum dipole moment will be of : (JEE 2003] (ayccl, (B) CHCI, (©) CH,Cl, (D) cH,CI s Nn; 2 y Sey worn 2009 00H Correct order of acidic strength is: (A)x>y>z (B)z>y>x (y>z>x (D)x>z>y For I-methoxy-1,3-butadiene, which of the following resonating structure is the least stable? (a) H,€-En-CH=CH-0-CH, (B) H,e-cH-cn-cH=8-cn, (©) H,c=cH-CH-CH-0-cH, (D) H,C=CH-CH-cH=6-cH, (JEE 2005] ‘When benzene sulfonic acid and p-nitrophenol are treated with NaHCO,, the gases released respectively are [JEE 2006] (A) SO,, NO, (B) SO,, NO (C)SO,, CO, (D)CO,, co, Among the following, the least stable resonance structure is [JEE 2007] oO O Do 4 Ae Va “ § (B) b 8 Se ° 8 O o fe AS ° NAN, oN © § () | 8 8 ‘The correct stability order for the following species is [JEE 2008] 2 8 Bn Ak Agk ow mM (il) (aD (iv) (A) (I) > AV) > (1) > CI) (B) (1) > (ID) > (I) > (IV) (C) dD) > () > (IV) > (I), (D) (1) > (HID > (I) > (IV) Hyperconjugation involves overlap of the following orbitals [JE 2008} (A)s-o (B)o-p ()p-p (D)x-0Q.36 Q37 Q38 Q39 Q40 Qa4l Q42 Q43 ELECTRONIC DISPLACEMENT EFFECT ‘The correct acidity order of the following is : [JEE 2008] OH on COOH fon oO Q ab (uy Q ay) a cH, (A) (ID > Iv) >) > (B) (IV) > (MD) > > (C) (I) > (I) > (> (IV) (D) () > (I) > (IV) >) ‘The correct stability order of the following resonance structrue is : (JEE 2009) e 2°. 8 (@— HC-N-N a) HC-N=N am Hé-N=n av) He-N=N (A) @ > (ID) > AV) > (ID. (B) (1) > (HID) > (I) > (IV) (C) (Il) > (1) > (Il) > (IV) (D) (ID > (1) > (IV) > (I) Among the following compounds, the most acidic is [JEE 2011] (A) p-nitrophenol (B) p-hydroxybenzoic acid (C) o-hydroxybenzoic acid () p-toluic acid ‘The total number of contributing structures showing hyperconjugation (involving C-H bonds ) for the following carbocation is (IEE 2011] H,C\@-CHL,Cll, Which of the following molecules, in pure from, is (are) unstable at room temperature ? (JEE 2012] Oo (a) O ) Ee] on} © bd ‘The compound that does NOT liberate CO, , on treatment with aqueous sodium bicarbonate solution, is : [JEE Advance 2013] (A) Benzoic acid (B) Bezenesulphonic acid (©) Salicylic acid (D) Carbolic acid (Phenol) The hyperconjugative stabilities of tert-butyl cation and 2-butene, respectively, are due to (A) o> p (empty) and 6 -> * electron delocalistaions. [EE Advance 2013] (B) 0 + 0* and o > nelectron delocalisations (C)o p (filled) and 6 — x electron delocalisations (D) p (filled) - o* and & -> x* electron delocalisations The total number of lone-pairs of electrons in melamine is [JEE Advance 2013]ELECTRONIC DISPLACEMENT EFFECT Qi Q2 Q3 Q4 Qs SECTION-B (JEE Main Previous Year's Questions) In the following benzyValkyl system R-CH=CH, or <-> (R is alkyl group) increasing order of inductive effect is — [AIEEE-2002] (A) (CH); C-> (CH) CH -> CH,CH,— (B) (CH,CH, ~> (CH), CH -> (CH,);C— (©) (CH), CH-> CH,CH, -> (CH,),C— (D) (CH,)C -> CH,CH, -> (CH,),CH— CH; i When -CH,, CH;—~CH~ & CH,-C- groups are introduced on benzene ring then correct I | CH, CH; order of their inductive effect is [AIEEE-2002] cH; CH, (A) CH,-> CH; -CH-> cH,-¢- @) cH,-¢- > CH; -CH- >CH,- GH, &, GH, cH, cH; (C) CH,-CH- > CH,-> cHy-C- @) cHy-C- > CH,—> CH, -CH- én, cH, én, én, The correct order of increasing basic no. of the bases NH, CH,NH, and (CH,),NH is — [AIEEE-2003] (ANH, < CH.NH, < (CH,),NH (B)CH,NH, < (CH,),NH < NH, (©)CH,NH, < NH, <(CH,),NH (D)(CH,) NH < NH, < CH,NH, Rate of the reaction [ATEEE-04,05] n-€ sn? —r-6 \ \ Nu is fastest when Z.is - cl (B) NH, (©) 0C,H, (D) OcOcH, Consider the acidity of the carboxylic ac [ATEEE-2004] (a) PhCOOH () 0-NO,C,H,COOH (©)p-NO,C,H,COOH (a) m-NO,C,H,COOH Which of the following order is correct ? (Aja>b>c>d (B)b>d>c>a (C)b>d>a>c (D)b>c>d>aQ6 Q7 ELECTRONIC DISPLACEMENT EFFECT Which of the following is the strongest base - [AIEEE-2004] (a) Cm, (B) C Spurn, © Cy (D) C Y-cunm, Hy The decreasing order of nucleophilicity among the nucleophiles [ATEEE-2005] °o 2 @ane-o CHO ocr @ne—<_Y$-0- é ° is (A)d>c>b>a — (B)a>b>c>d = (C)c>b>a>d = (D) b>c >a>d Q.8 Amongst the following the most basic compoun [AIEEE-2005] (A) aniline (B) benzylamine (C) p-nitroaniline (D) acetanilide Q9 The increasing order of stability of the following free radicals is — [AIEEE 2006] (A) (CoH);6 < (CgH)) 6H < (CH);6 < (CH,),CH (B) (Ces), CH< (CgHs)36 < (CH3)36 <(CH3),CH (C) (CHy))GH <(CH,)36 < (Ces) 36 < (Ce) CH (D) (CH,),CH <(CH3)36 < (CéHls).CH < (CgH)36 Q10 CH,Br+Nu--> CH; -Nu+Br ‘The decreasing order of the rate of the above reaction with nucleophiles (Nu7) A to D is [Nu™ = (A) PhO-, (B) AcO-, (C) HO-, (D) CH;07] [AIEEE 2006] (A)D>C>B>A_ (B)A>B>C>D (C)B>D>C>A_ (D)D>C>A>B Q.I1 The correct order of increasing acid strength of the compounds [ATEEE 2006] Me, (a) CH,CO,H (b) MeOCH,CO,H —(c) CF;CO,H @ Me OOH is (A)dCCly> CoHsCH, > (CH)36 e 2 8 @ (B)CCly> C,HyCH,> (CH), CH> (CH,);6 ° e e 2 (©) (CHy)3C> (CH;), CH>CgHsCH, >CCly e 8 e 2 (D) CoHsCH,>CCl3> (CH3)3C> (CH3)2CH QUS The correct order of increasing basicity of the given conjugate bases (R = CH,) is : [AIEEE 2010) e 6 ee (A) RCOOI> I> IV (B)M>I>M>IV (©IV>M>I>M (Dy M>IV>1> Q.18_ The order of stability of the following carbocatior [JEE Main 2013] a 2 2 CH,= CH -CH,; CH,- CH,- CH,; A o a ap is (A) I> M>1 (B)I> > (QM>I>1 (D)M>M>1ELECTRONIC DISPLACEMENT EFFEGT ERT Te or} (CBSE Previous Year's Questions) Ql Why is it that phenol is acidic and hexanol is neutral towards a solution of NaQH? [CBSE 2001, 2] Q2 Explain the following observations: [CBSE 2004, 5] (@_Inaqueous solution the K, order is E,NH > Et,N > EINH, Nucleophilic substitution of p-nitrochlorobenzene is easier than that of chlorobenzene. Amines are more basic than comparable alcohols, Q3 Why are primary amines higher boiling points than tertiary amines? [CBSE 2005, 1] Q4 Give reasons for the following : [CBSE 2008, 2] (@__m-aminophenol is a stronger acid than o-aminophenol. Gi) Alcohols acta as weak bases. QS Whyis an alkylamine more basic than ammonia ? [CBSE 2009, 1] Q6 Explain the following observations: ICBSE 2009, 3] (The boiling point of ethanol is higher than that of methoxymethane. Gi) Phenol is more acidic than ethanol. (iii) 0-and p-nitrophenols are more acidic than phenol. [CBSE 2011, 3] Q.7__ State reasons for the followi (i) pK, value for aniline is more than that of methylamine. (ii) Ethylamine is soluble in water whereas aniline is not soluble in water. Gi) Primary amines have higher boiling points than tertiary amines. Q8 Accounts for the following: [CBSE 2011, 3] ‘The boiling point of ethanol is higher than that of methoxy methane. Phenol is a stronger acid than an alcohol. ‘The boiling points of ethers are lower than isomeric alcohols. Q9 Arrange C,H,NH,, (C,H,),NH and C,H,NH, in increasing order of solubility in water. [CBSE 2011, 1]ELECTRONIC DISPLACEMENT EFFECT -EXERCISE-5 (Rank Booster) Single correct A 2 L * OO-1CO- ico 3 3 3 ¥ ¥ + ‘These are three canonical structures of naphthalene. Examine shem and find correct statement among the following : (A) All C=C bonds are of same length (B) Cl— C2 bond is shorter than C2 - C3 bond (C) Cl —C2 bond is longer than C2 — C3 bond (D) None of these Q2._ In which of the following molecules ~ electron density in ring is maximum : NO SP NH OCH; A) oO ®) oO © oO ©) co Q3 Write correct order of acidic strength of following compounds: OH Lo H 6-H N ‘NO, NO» NO, a So a avy) NO, NO, (AIV>II>I>1 (B)M>M>I>IV (OIV>I>I>M (D)1>1> I> IV Q4 Which one of the following is the most acidic? 7) V ®) OS © O (D) CH,=CH-CH, Q5 The correct pKa order of the follwoing acids is : 6 0 r i W0. " 2 So @. «a (au) (A)I> > 0 (B) > M>1 (Oll>I>n (D)I>M> 1ELECTRONIC DISPLACEMENT EFFECT Qe Basicity order in following compound is : 9 OA yes H.N-C- CH, > -Cy- NH ¢-CH, 4 N cu’ cu, (A)b>d>a>c (B)a>b>d>c — (C)a>b>e>d = D)a>c>b>d More than one may be correct Q7 Qs Qo Quo A canonical structure will be more stable (A) it has more number of 1 bonds than if it has less number of x bonds. (B) the octets of all atoms are complete than if octets of all atoms are not complete. (C) itinvolves cyclic delocalization of (4n + 2) x—electrons thar wolves acyclic delocalization of(4n) 1 — electrons. (D) it involves cyclic delocalization (4n) x —electrons than if it involves acyclic delocalizationof (4n + 2) n—-clectrons. (B) +ve charge is on more electronegative atom than if +ve charge is on less electronegative atoms, (F) -ve charge is on more electronegative atom than if—ve charge is on less electronegative atom, Select the correct statement(s): (A) CH,OCH, is more stable than CH,CH, (B) Me,CH is more stable than CH,CH,CH, (©) CH, =CH-€H, is more stable than CH,CH,CH, (D) CH, =CH is more stable than CH,CH, Which of the following groups can either donate as well as_ withdraw a pair of electrons in resonance depending upon situation : (A)-NO, (B)-NO (©-CH= (2)-NH, (F)-N=NH H, — (D)-CHO Which of the following groups can only withdraw a pair of electrons in resonance depending upon situation : Ph w, Loy © solo oy or . ; ©) -NMe, (*)-CoNn,ELECTRONIC DISPLACEMENT EFFECT qu Qi2 Qs qua Consider the following compound 0: Ht ‘OH w wr o on COOH ou . No, a on 2 i © cuyccoon ©) Xo, Which of the above compounds reacts with NaHCO, giving CO, un 3 MAN Pyrimidine Imidazole Purine Among the following which statement(s) is/are true: (A) Both N of pyrimidine are of same basic strength (B) In imidazole protonation takes places on N-3. (C) Parine has 3 basic N. (D) Pyrimidine imidazole and purine all are aromatic Among the following which one is having conjugated system : Choose the correct statement of | an aml (A) Stability of (I) > (>) (B) HOC of (I) > Al) >) (© Stability of (AL) > () > (D) HOH of () >) > (a)ELECTRONIC DISPLACEMENT EFFECT Subjective QUS Consider structural formulas A, B and C: HC (A) @) «© (@) Are A, Band C constitutional isomers, or are they resonance forms? (b) 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? (8 Whats the net charge on each structure? (2) Which is a more stable structure, A or B? Why? (b) Which is a more stable structure, B or C? Why? Q.16 _Ineach of the following pairs, determine whether the two represent resonance forms of a single species or depict different substances. If two structures are not resonance froms, explain why. @) (b) © Q.17__ Rank the following sets of intermediates in increasing order of their stability. @ @CHt (b) p-NO,(C,H,)" — (€) p~CH,~(C,H,)*(@) p-CI-CH,* e HY ° 2 Ga HP jw) @ 0) o oo Me ° ap gh ou @ © © 20H 9 @ (iv) (a) | -CH, -CH, () CE-CH, © CK e e w @ CK () cal,Qs Qus Q20 w (ii) (iii) ELECTRONIC DISPLACEMENT EFFECT In which of the following pairs, indicated bond having less bond dissociation energy : (@) CH, ~Cllyg Br & CHs~CH, F (©) CHy ~CH= CH » Onn Sty A Wh Consider the given reaction: cl ClI= CH, CH =O 9 1 é ran 1 & Ba In the above reaction which one of the given ring will undergo reduction? Write correct order of acidic strength M1 C0-H @) 00H 1 @ C-O-n @) of following compounds: C-O-H CH, b) 00H Br (b) 9 1 Hi Row (b) “om ‘tiMeco) Q21 @ (ii) Q2 @ (b) &) Q23 (a) (© @ Q24 @ di) (ii) (iv) W) ELECTRONIC DISPLACEMENT EFFECT pro z ‘=O E se = @ ) © oo NO, Say which pk, belong to which functional group in case of following amino acids : ‘00H cysteine : Ml “ 18,83 & 108 N glutamic acid; HOxC ‘OOH + 9.19, 4.25, 9.67 Ni, Choose the more stable alkene in each of the following pairs. Explain your reasoning. I-Methyleyclohexene or 3-methyleyclohexene Isopropenyleyclopentane or allyleyclopentane l o f Match cach alkene with the appropriate heat of combustion: Heats of combustion (ki/mol) : 5293 ; 4658; 4650; 4638; 4632 1-Heptene (6) 2,4-Dimethyl-1-pentene 2,4-Dimethyl-2-pentene (4) 4,4-Dimethyl-2-pentene 2,4,4-Trimethyl-2-pentene ‘Write increasing order of heat of hydrogenati (a) CO (b) O @/\ 0) /\ o= o a= &) / © r~ @ rh © yx (a) CO (b) oO © oO @ oO (b) CO © (Faron perx tonELECTRONIC DISPLACEMENT EFFECT EXERCISE-1 - v QI @CH,-C=CH, (b) H-C=CH-CH=cH, HS CH, cH, CH, cH, + a" © — —f Jf y— ¥ e 0 or Ope 0 C0 6 ow 0) wD Y. > ® ™ ® () CH, ~CH-CH = CH-CH=CH-CH, () CH,-CH-CH =CH-CH=CH,] Q2 (i) cob>a (ii) besa (ill) c>b>a (iv). b> ca () dc>bra (vi) acbb>c i) a>b>e ill), “a>e>b (iv), a>b>e Q4 (i) c>b>a ii) c>b>a ill), ‘b>c>a (iv), c>b>a () a>e>b QS (A), (b) 1, (6), (A) HI, (@) I, (0), (Q) Q6 (i) a>b>c (ii) a>b (il) c>a>b (iv) d>b>e>a () d>e>bearc Q7 (i) azc>b>d ii) d>b>c>a Gill) b>a>e (iv) ade>b () b>e>a (Wi), b> e>a Q8 MLO) @1L 1 Q9 MLOLOL@LE! Q.10 (a) 1, (b) I, (c) II, (4) HI, (e) 1 QU @L)L © 1 @)1,@) 1,1 Qi2 @) ae>a>d iii) a>b ‘Scanned with CamscarerQu3 Qua Qus Qi6 Quiz Qs Q20 Q2i Q2 Q23 Q24 Q2s Q27 Q.29 Q31 Q33 Q35 (2) Due to resonance HCLCHE ELECTRONIC DISPLACEMENT EFFECT —tH,-cH=cr (b) In CH,=CH-OCH,, there is single bond character due to resonance niton® ICH; + CH,-CH=0~CH, (c) Conjugate base of CH,SH ie, CHS is more stable than conjugate base of ‘CH,OH, ie CH,O- (@) In CH,=CH-NH, lone pair of N is delocalized cfig}cHNH, —> CH, CH= NH, (a) TL, (b) I, (c) 1, @) I, (e) 1, () @) a>b>e i) bbwe Gi @) a>b>c (Wi), c>b>a i) @ ~a>b>c ii) a>b>e Gi d>a>c>b (iv) e>b>a a>b>e d>b>e>a (a) 3<2c1; (b) 1<2<3; (c) 3<2«1; (A) 2<1<3; (€) 2<3<1 (a) 2; (b) 2; () 2 Qs @ — a>b>e>d Gi) a>b>erd () e>bed>a (vi) eb>e ii), d>e>b>a_ iii) () b>a (i) d>c>b>a (i) c>b>a Gi (vy) e>a>b @ od Gi) ob Gi) () b>a>d>c (ii) a>b>e (a) i, (6) ii, (©) i, @) ii, (©)i Q26 (a) 2; 6) 15) 15 @) 15.) 1503 Q.28 (a) 1>2>3; (b) 1<2<3; (¢) 3<1<2; 230 (a) 2<1<3; (b) 1<2<3; (¢) 3<1<2 Q32 ()2>1 Gi) 2<1 Gili) 1 <2 (ivy 1>2 Q34 @T1,O)1@1,@T (a) 2; (b) 2; (c) 2 a>b>e (iv) da>b (viii) b>c>a b>e>a (iv), se > b> a b>a>e (iv), a>boe a (iv) a (@i, b)i, (ii (a) 3<2<1<4; (b) 1<2<3<4 (a) 2<1<3; (b) 1<2<3; (€:)2>1>3 (a) 2> I> 3, (b) 1 >2>3, (0) 1>3>2, E>C>D>B>AQi Qe Qu Q16 Q21 Q.26 Q31 Q36 Qal Qi Q6 Qu0 Qi3 Q16 Qus Qg Q20 Q25 Q30 Q35 40 cr ABD ABD AC 2 Q7 Qi2 Qi7 Q.22 Q27 Q.32 Q37 Q2 Triangular planar less D c Qu Qua Qi7 EXERCISE-2 D Q3.A B Qs D c Qi B A Quis D B Q23 D ABCD Q28 ACDE ABCDF = Q.33_ AEFG ABD Q38 ABD EXERCISE-3 SECTION-A c Q3 D Q7_ D hyperconjugation ELECTRONIC DISPLACEMENT EFFECT Q4 Q9 Qi4 Qus Q24 Q29 Q34 Q39 Q4 Qs Qu2 Better resonance occurs in Benzoic acid Becoz of Resonance Becoz of intramolecular H-bonding is o-hydroxybenzaldehyde Acidic strength : CH = CH > CH= Basic Strength : c BC Q2t Q.26 Q31 Q.36 Q4i Hy, Reon ab CH=C1>4>3 Qa > > ow a Qs Quo Qs Q.20 Q25 Q30 Q35 ABCD Q40 Qs Qs QuUs Q24 Q.29 Q34 Q39 D ACD A A DQi Q6 Qu Q16 Qi Q2 Q3 Q4 @ i) ELECTRONIC DISPLACEMENT EFFECT SECTION-B A Q2 B Q3 A Q4 Aa Qs D D a7 D Qs B a9 D Qi0 D B Qc Qi3 D Qi B Qs B c Qi7 B Qis c EXERCISE-4 ‘The phenoxide ion undergoes resonance stabilisation and thus phenol loses H’ ion to show acidic character. C,H,OH —> C,H,07 + Ht Resonance stabilised (On the other hand the alkoxide ion shows no such resonance stabilisation, ines, a combination of electron releasing, steric and H-bonding factors determine of ammonium cations in aqueous solution. Consequently, we get the given K, @ — Inalkyla the stabi order. Gi) The presence of nitro group facilitates nucleophilic substitution of otherwise unreactive chlorobenzene by stabilising the intermediate carbanion. a OH HH e 7 = OF -O No, NO, NO, Carbanion (iii) Weaker electronegativity of N than O makes amines more basic than alcohols. Primary amines are capable of forming hydrogen bonds due to the presence polar N-H bonds Tertiary amines cannot form hydrogen bonds due to the absence of N-H bonds. SO primary amines have higher boiling points than tertiary amines. In substituted phenols, the presence of electron withdrawing group enhances the acidic strength of phenol. This effect is more pronounced when such a group is present at ortho and para positions. It is due to the effective delocalisation of negative charge in phenoxide ion. Thus m-aminophenol is a stronger acid than o-aminophenol. Alcohols acts as Bronsted bases as well. It is due to the presence of unshared electron pair on ‘oxygen, which makes them proton acceptors.Qs Q6 Q7 Qs ELECTRONIC DISPLACEMENT EFFECT Due to dispersal of the positive charge by the 4 effect of the alkyl group, alkylamines are stronger base than ammonia, ()—_ Theboiling point of ethanol is higher than that of methoxymethane due to the presence of hydrogen bonding in alcohols. (ii) Since the phenoxide ion left after the removal of a proton is stabilised by resonance where as alkoxide ion is not which is left after the removal of a proton from alcohols, Gi) In substituted phenols, the presence of electron withdrawing group enhances the acidic strength of phenol. This effect is more pronounced when such a group is present at ortho and para positions. Itis due to the effective delocalisation of negative charge in phenoxide ion. Thus m-aminophenol is a stronger acid than o-aminophenol. Primary amines (RNH,) has two hydrogen atoms on the N atom and therefore, form intermolecular hydrogen bonding. Tertiary amines (R,N) do not have hydrogen atoms on the N atom and therefore, these do not form hydrogen bonds. As a result of hydrogen bonding in primary amines, they have higher boiling points than tertiary amines of comparable molecular mass.For example boiling point of n-butylamine is 351 K while that of tert-butylamine is 319 K. (Boiling points of alcohols are much higher than those of alkenes, haloalkanes or ethers of comparable molecular masses. This is because in alcohols intermolecular hydrogen bonding exists due to which larger amount of energy is required to break these bond. R R I | 0. 0. wow oH ° 0 I I R R The isomeric alcohols the boiling points generally follow order ~ Primary alcohol > Secondary alcohol > Tertiary alcohol (ii) Phenols is more stronger acid than alcohol : The greater acidic character of phenols as compared to alcohols can be explained on the basis of resonance. Phenol is a resonance hybrid of the fallowing structures. ion ‘OH *OH o-G- Oro O o a ati) vy) ) Itis clear that three structures of Phenol (Ill, IV and V) have +ve charge on oxygen of OH group. This oxygen attracts the electron pair of O — H bond strongly towards itself and, therefore, facilitates the release of H*. Similarly, the phenoxide ion is resonance stabilised as follow: «wp (vm) (vat, ay &)Q9 Qi Q6 qu Qs Q16 Qu7 Qs Qu9 Q20 Q22 Q23 Q24 ELECTRONIC DISPLACEMENT EFFECT Thus, we observe that both phenol and phenoxide ions are stabilized by resonance. Now, if we carefully observe the resonance structures, we observe that phenoxide ion is more resonance stabilised than phenol. (ii) Ethers have low polarity and therefore, do not show any association by intermolecular hydrogen bonding on the other hand, their isomeric alcohols have strong intermolecular hydrogen bond and therefore, their boiling points are high. Stronger the base lesser the pK, value. C\H.NH, < C.H,NH CH, < C,H.NH, < (C\H,),NH EXERCIS! B Q2 B Q3 A Q4 B Qs B B Q7 ABCF Q8 ABC Q9 BCF Qi0 F ABCD Qi2 ABCD Q13 BD Qld AB a= Resonance form, b= A, ¢ = C, d= A & B, e=B&C, f= 0, g=B,h=B (a) is resonance form; (b) is not resonance form due to different number of I.p. and b. (©) is not resonance form due to different number of /.p. and b.p Wbe>a Gi) c>a>b (iv) c>a>b () a>b (a) 1, 6) 1, (©) U, @) 1, @)1, (1 A @ — b>a Gi) b>a (iv) e>a>b (@ cysteine; COOH 83 18° Gi) glutamic acid : 110,¢ COOH 425 ana 219 NH, 108 9.67 @)i,)i,©ii (a) 4658, (b) 4638, (c) 4632, (d) 4650, (c) 5293 @ boa Gi) a>b>d>e Gil) a>b>e>d>e (iv) b>e>a W) a>boe