GENERAL ORGANIC CHEMISTRY 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 preduct. The chemical species (more reactive) which causes the change is called reagent. CH,— CH, — Br +“OH —+ CH,— CH, — OH + Br ‘substrate Product Reagent or Reactant Breaking of covalent bond is known as bond cleavage. A bond can be broken by two ways : Bond Cleavage Homolytic Hetrotytic Free Radical Cation & Anion. Homelytie Fission or Homolysis “The covalent bond is broken in such a waly that eich resulting species gets its own electron. This leads to the formation of odd electron specics known as free radical. Homolytic bond fission gives free radical as the reaction intermediate Ap hea fice radical “The factor which favours homolysis is 2ero ora small difference in electroncgativity between A and B. Homolytic bond fission takes place in gascous phase or in the presence of non polar solvents (CCI,, cs,). Heterolytic Bond Fission or Heterolysis, . Inheterolysis, the covalent bond is broken in such a way that one species (ic, less electronegative) loss its own cleetron, while the other species (.c., more electronegative) gains both the electrons. Mp 8-8 ‘Thus formation of opposite charged species takes place. In case of organic compounds, if positive ‘charged is present on the carbon then cation is termed as carbocation. If negative charge is present on the carbon then anion is termedas carbanion. ‘The factor which favours heterolysis is a greater difference of clectroncgativity between A and B. REACTION INTERMEDIATES Reaction intermediates are generated by the breaking of covalent bond of the substance. They are short -lived species (half life 2 10°* sec.) and are highly reactive. few important types of reaction- intermediates are as follows. (1) Carbocation 2) Carbanion @) Free radicalCarbocations Characteristics of Carbocatiot @ @ ‘An organic species which has a carbon atom bearing six electrons in its outermost shell and has a positive charge is called a carbocation. Carbocation have a positive charge on carbon. Positively changed carbocation has only 6 electrons inthe outermost shell. Ithas an incomplete octet. So it behaves like a lewis acid. (Since all electrons are in paired state so carbocations are diamagnetic. (@) —_Carbocations are sp* hybridised. (8) Carbocations are planar with a perpendicular empty p-orbital. Due to planar structure carbocation leads racemization in stereogenic conditions. (v3) Carbocations are formed in polar solvent. (sil) It stabilize 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 @ AN Characteristic of Carbanions : @ __ Itis formed by heterolytic bond fission. @_—_Thereare eight electrons in the outermost orbit of carbanionic carbon hence its octet is complete. Gi) It behaves as charged nucleophile, (@) Iti 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 pryamidal. 7X Note : Geometry of allyl and benzyl cabanion is almost planar and hybridisation is sp? (vi) Itreacts with clectrophiles. (sii) It 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. (@_—_ Homolytic bond fission of a covalent single bond gives rise to free radicals. (ii) There are seven electrons in the outer most shell of carbon free radicals. (@) Owing to the presence of an odd electron; a carbon radical is paramagnetic in nature. Due to this @) wo Gi) reason free radicals are highly reactive. Carbon free radicals are normally sp? hybridized Free radicals are neutral electrophiles. It stabilize by presence of electron releasing group (ERG)ELECTRONIC DISPLACEMENT EFFECTS (EDE) Electronic Displacement effect L Permanent Effect Temporary Effect + + £ T tT + T Inductive Mesomeric Hyperconjugation Electromeric Inductomeric Effect Effect effect effect effect INDUCTIVE EFFECT (I-EFFECT) 0 @ a) ™ w) wi) ‘The displacement (shifling) 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. a + C-+C—+- C —+ GG: functional group) 8- 8- & Cm Ce C OG But the effect is insignificant beyond third carbon atom. (distance dependent effect) ‘This effect is transmitted through the chain Of ¢ bonds and diminishes, with increasing chain length. Inductive effect is'thus A permanent effect ‘The elcetrons never leave their original atomic orbital. Operates through « bonds Polarisation of electrons is always in single direction. Itis generally observed in saturated compounds. Its magnitude (i... electron withdrawing or donating power) decreases with increase in distance. On the basis of electron realising group (ERG) or elctron withdrawing group (EWG) inductive effect, can be of two types. = 1 effect : The group which withdraws electrons is known 2s ~ / group and its effect is known as - effect. — 1 power of various group & cation. ° 1 —NNFy> -NH,> -NO, > -SOjH > ~CN > -CHO > -C-R > -COOH > -COOR > -CONH, >-F>-Cl >-Br >I >-OH > -OR > -C = CH > ~CjHy > -CH = CH, >-H — 1 power of groups in decreasing order with respect to the reference H + Leffect : The group which donates or gives clectron is known as + / group and effect is known as + reffect. a@) ©) + J power of different type groups and anions : -TH,>-NH >-O- >-COO- > tertiary alky!> secondary alkyl > primary-alky! >-CH, >-H + rpower in decreasing order with reference to H-atom + 1 power of same type of alkyl groups : + Ipower = number of C’s in same type of alkyl group CH, —CH, - + 1 power in CH,-CH, -CH,- increasing For example order (CH, -CH, - CH,-CH,- APPLICATIONS OF INDUCTIVE EFFECT @ &) © Stability of reaction intermediates @ Subility of carbocation (@) Stability of free Radical (iii) Stability of carbanion ‘Stability of carbocation Stability of carbocation Presence of electron releasing group & +1 group <=] an - (CH,),C*> (CH,),CH" > CH,CH," > CH,” x x + 2 & @ CH, — CH, > Br — CH, — CHy> ClCH, — CH, > F —CH, Maximum of F ° ° CH,-CH-CH.CH, ~ Cu, -CHl,-CH-CH, < CH, -CH, -CH,-CH, -F F F Maximum -1 Minimum -1 ‘Minimum distance Maximum distance —F @ e @ rH, CH, - CH, CH, ~CH, -CH-CH, (Distance wins over power) x0, ) or Brcen-prt (Number wins over power) No, © onan Bi a >c>b » OKxCy Stability of free Radical t Stability of F.R. « Presence of electron releasing group « +1 group % TT eroup - Stability of F.R. decrease in the following order (8) (CH,),C*>(CH,),CH"> CH,CH,"> CH,” x r r ) ¢H,—CH,> Br—CH, —CH, > Cl—~CH, —CH, > F ~CH, —CH, Maximum -I of F ©@ ) ©) @ © @® Stability of carbanion Stability of carbanion « Presence of electron withdrowing group « —1 group < 7 (CH,),C < (CH,),CH’ < CH,CH; < CH, x r r CH,-CH,-+NO, > CH,-CH,-+F > CH,-CH,> OH > CH,-CH,-> NH, e, e 1 FH -CH, CH, > CH, CH, -CH-CH,> CH, - CH, Cir CH - F F be bem, be "> o> Acidic Strength Strength of Carboxylic Acid : Acid sirengthiis measured by the position of equilibrium of ionisation in water. HA = Htet A" acid anion _ UWA) = acid ionisath or THAT (K, = acid ionisation constant) . 1 or, acid strength = (H"] = Ky =~ (here pK, = -logK,) or Acid strength « concentration of [H*] or Acid strength «c stability of acid anion Thus strength of acid is the function of stability of acid anion. +s Stability of carbanion = Presence of electron withdrowing group « ~1 group = Sewn “. acidic strength Presence of electron withdrowing group « -1 group +1 group The influence of the inductive effect on acidity can be summarised as follows :Acidic strength of carboxylic acid @) (o) ©) @ ) HF < HCI < HBr < HI CH, < NH, < H,0 < HF CI-CH,-COOH =< CI,CH-COOH < CCI,-COOH -It acid strength T H-COOH > CH,-COOH > CH,-CH,-COOH > CH,-CH,-CH;-COOH + Ipower of alkyl groups T Acid strength $ CH,-OH > CH,-CH,-on 1 1 a NO; 1 iy (CH,)\COH < (CH,),CHOH < CH,CH,OH < CH,OH Basic Strength Basicity of Amines : Basicity is defined as the tendency to donate an clectron pair for sharing. The difference in the base strength in various amines can be explained on the basis of +1.- effect. ‘The groups producing +1 effects (alkyl groups) tends to intensify electron density over N in amines thereby producing a base strengthening effect. ‘Thus, strength of base « + 1 power of group present on - NH, « Ky « - Whereas, a gfoup producing -I effect [-Cl, -NO,] tends to decrease electron density over N - atom in amines, thereby producing a base weakening effect. 1 Thus, strength of base [CF group present on = NH, * Ke Relative base strength of amines : Examples (a) R - NH; < R,NH < RN (b) H,O < NH, < NH, > @ o O- ‘Ny ‘N H H | 1 H > cu,-N-cn, © " Order of basic strength in solvent phaseMCQ Q7 Quo Homolytic fission of organic yields- (A) Nuclophile (B)Carbanion (C) Free radical (D) Carbocation The number of elerons preset inthe valence sll of atom of CHC ion bearing +ve charge: 8 (B)7 6 Inductive effect refers to - (A)q electron displacement along a carbon chain (B) complete transfer of one of the shared pair of clectrons to one of the atoms joined by a double bond (C) complete transfer of electron with the help of conjugation (D) none of the above Most acidic hydrogen is present in- (A) Ethyne (B)Ethene (C)Benzene (D) Ethane “The least acidic among the following acids is- (A) Trichloroacetic acid (B) Dichloroatetic acid (C) Monochloroacetic acid (D)Acetic acid, ‘Among the following which one is most basic- (A) NH, (B) CHINH,, (C)CH,CH,NH, — (D) c#,-NH, ' a Which one is the characteristic feature of a free radical : (A) presence of positive charge (B) presence of unpaired electron (C) presence of even number of electrons (D) associated with high stability Benzoylperoxide, when heated to about 80°C gives a- (A) Free radical (B)Carbanion (C) Carbocation (D) None of these Which one isa 1° carbocation of the following: (A) CH, ex, (B)CHH—CH, (C(CHYCH —(DY(CH),E @ CH, is less stable than e e e e (A) CH,-CH, — (B) CH;-CH-CH,(C) CH,-NO, —_(D) CH, -CH-CHsQi Qu3 Qua Q16 Quy Quy Q20 ° Decreasing order of effect ofthe triad [ o,, Bit, a ° ° (A) -NH, >-NO, >-CN (B) -NH, >-CN>-NO, ° ° (©) -CN>-NO, >NHy (D) -NO, >-CN>NH, Maximum ~1 effect is exerted by the group- (A) Colts (B)-OCH, ©-c (D) -NO, Choose the strong base from each of the following pair (1) 70C,H,, “OH QQ) HC = CCHS G3) BF 4) CH, NHy~ o @ 8 @ (A) “OCH, = CH, Br cH,” ®) Ol, cH, r NH «© On, HCec Br CH; ©) oO, cH, r NH) Basic nature of H,O*, 11,0. and OH is inorder - (A) H,O° >a ‘According to the given structure C~C, bond length should be smaller then C,-C bond length but C,-C; 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 1 1 oO I Land i are resonating structures of C,H, ‘When a molecule orion can not be represented by Single lewis dot structure and more than one sturcture are needed to represent all properties of the molectile these structures are known as resonating structure and combined structure ofall resonating structure ae known as resonance hybrid and this phenomenon isknowtias fesonance. fing Structure have the same arrangement of atomic nuclei but differ in distribution of electrons, (only x electron delocalised) Resonating structure are hypothetical and actual structure is a resonance hybrid. Resonance generally occurs when there is a conjugation of x-bonds (altcmnate double - single - double bond arrangement) ‘Condition for Resonance : w Q @) @ ) 6) @ Planarity - Atoms considered in molecules must be sp? or sp-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 alternate to x electron conjugation Lone pair electron alternate to x electron conjugation x electron alternate to x electron conjugation ‘electron alternate to vacant orbital (Positive charge) conjugation x clectron altemate to odd electron (free radical) conjugation Lone pair electron altemnatc to vacant orbital (Positive charge) conjugation Conjugate positions of the molecule : ‘Alternate positions of the molecule having x bond, positive charge, negative charge, odd electron cor lone pair of electrons are known as conjugative positions.1, 3, 5 are alternate positions having x bonds. Hence these positons are known as conjugate positions. 1, = CH CH = CH- eu - cH, 1.3 and 5 are conjugate positons. ch, = CH - GH = CH - CH = CH - Wn, 13s, 7 are Conjugate positions Note : Compound having at least two conjugate positions is known as conjugated compound. TYPES OF CONJUGATIONS a) @) ® Negative charge electron alternate to x electron conjugation : If in a conjugated system bond and © charge at alternate position so conjugation is known as negative charge electron alternate to x electron conjugation CH, = CH - GH, CH, = CH - CH= CH- CH, & Q A x 6 Lone pair electron alteranateto x clectron conjugation : If in a conjugated system x bond and lone pair at alternate position so conjugation is known as ¢p electron aternate to x electron conjugation. Serge CH, = CH-& 1, = CH - CH = CH - CH = CH é 3 electron alternate to x electron conjugation : If x bond altemate with x bond so conjugation is known as x electron alternate to x electron conjugation cu, = CH CH = CH; ~ CH ~ CH= CH - CH = CH ~ CH = CH; : 3 3® vacant orbital (Positive charge) conjugation : If x bond altemate with ‘vacent orbital so conjugation is known as positive charge alternate to x electron conjugation. cH, = CH - Gx, , > Ithas positive charge, x conjugation. CH, = CH - CH = CH - GH, ‘These species has two type of conjugation x electron alternate to m electron conjugation and positive charge alterante to x electron conjugation. ()__x electron alternate to odd electron (free radical) conjugation : If x bond and odd e~ are in alternate position. CH, = CH - CH, CH, = CH - CH = CH - CH, Sb A ww AaXoeO (6) Lone pair electrom alternate to vacant orbital (Positive charge) conjugation : If lone pair and vacant orbital are altemate position es ° CH,-CH-NH, «CH,-CH=NH, eo ° CH, -CH-OH «CH, -CH=OH 8. @ ob my cH, &i-8-cn, Aan, i Rules to draw valid resonating structures 1. Electron flow occurs from high clectron density to low electron density. Negative charge -> Lone pair electron > x-bond electron —> 5° —> positive charge 2 Position of atom cannot be change, only the x-clectrons are delocalised. o' ie i & C-0 <+CH,-C=0 |A & B are Resonance forms. CH, -C-CH, «++ CH, =C-CH, ° ou 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 H CH, -CH=CH-N*-H .<9>-CH, -CH-CH=N-H 4 H 1 u Above structures are not resonance form because in structure II, nitrogen has 10 valence electrons which violates octet rule. 4. Each Resonating strictures must have the same number of unpaired and paired electrons. CH, = CH-CH, <> CH,-CH=CH, I i 1 & Il are resonating structure because both have & paired electrons and'l_ unpaired electron 5. Net charge should be conserved in all resonating structures. ° e CH, =CH-CH =CH, «+CH;-CH=CH-CH; ‘NetCharge=0 Net Charge=0 Both structures have same net charge so both are resonance forms. Rules for stability of resofiating structures 1. Amofig 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. CH, =CH-CH=CH, —+CH,-CH=CH-CH, 2. _Iftworesonance structures have same number of bonds then that structure in which octet ofevery atom is complete is more contributing than structure having incomplete octet e CH, -CH-NH, <> CH,-CH=NH, 3, resonating structures have same number of bonds then the neutral structure is more stable than chargod structure and ifboth are charged Resonating structure then less charged resonating structure is more stable. 4. Incase of charged resonating structures, the most stable one is that in which the positive and negative charge reside on the mes eectropostive and most electronegative atoms ofthe structure respectively. CH -CH=0 <—+CH, =CH-0° (A) (B) stability of B>A. Oy6— & §& 3-5 a mw am ™ sigan tesa nat attention Tertrt uate resonating structures in decreasing order will be as follows : =V>ialV>I1 6. Resonating structure in which like changes 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. © Itsthe experimental value which is calculated by heat of hydrogenation (HOH) © Higher the value of resonance energy, greateris the resonance stabilization. Resonance Energy of Benzene : O-O ‘The resonance energy of benzene is calculated from the heat of hydrogenation as given below : OC» — Oran De eC) 29 zee rea rect ae) but experimental value for benzene is 51 Keal.so, Resonance energy = Calculated value— Experimental value =87-SI = 36 Keal. Resonance energy comparison 1. Consider better resonance or equivalent resonating structures, motecules having equivalent resonating, structures must have more resonance energy, than non-equivalent resonating structures. ° o ll eg. RE. CH,-C-O7 OC Aromatic Jhave morc resonance | ‘than non-aromaticIncase of larger conjugation, more will be the Resonance energy. O#4Y <4\4~4 Resonance energy will be more, when n-bond, lone pair conjugation is present than x, x-conjugation BS Ayn =n Q7 Which molecule does not show resonance (ayCO (B) CO, (©) CO? (0) No,- Polarization of electrons in acrolein may be written as - (A) SH, = CH-CH=6 (B) CH, = CH- Gu=0 (Cc) GH, = CH -CH=0 (D) GH, = CH-CH= 6 In pyridine ; OQ Number of conjugated electrons are - (A)6 (B)s (C) zero (Ds In which compound delocalization is not possible - (A) 2-butene (B) 1y34butadiene y “(C) 1, 3, S-hexatriene (D) Benzene Consider the following compound : SH; = SH CH=CH, carbon-carbon bond length between C and C; will be - (A) 154A (B)13A (CLA (D) Less than 1.54 and greater than 1.33 A Which compound has higher resonance energy in the following pairs H AY S AZ nO oe 0 ay (C) CH,=CH-F CH,=CH-Br wo ry Which is less stable canonical structure in the following pairsQ8 Which marked atom's lone pair participate in resonance phenomenon Oy Q.9 Which molecules is not showing resonance oo ® OQ © oO ©) OQ Q.10 Which molecules is showing x-clectron altemate to x-clectron conjugation @ e . oO (B) CH, =CH-CH, (C) CH,=CH-CH; (D) CH,=CH-CH, Q.11 Correct order for resonance energy in the following molecules A a & o ay ay (@) M>1> Hn @il=1-0 CO Mm0 Quiz tate Rowing cen ee which is most stable structure SO-9-9 wt (By «um (WIV Q.13 In the following canonical structures which is least stable structure C-O-0~9 wt @u (cm mw Iv Q.14 Which is incorrect canonical structure O-O-O-O i) avy yl ®u om IVQ.16 In which molecule resonance phenomenon operates- @NH, HH; ay Oo @) 6 © isd ©) Y ih ANSWERS: QA Q2A Q3A Q4A QS D_ Q6(A)I, (B)I, (C)T QT(AQS(B) Q9A QIOA QUA QIZA QC QI4B QISC QI6D MESOMERIC EFFECT ) This is a permanent effect where the displacement of conjugational x electrons are influenced by the ‘group attached to carbon chain. ‘There is a push or pull of x electrons of the conjugated system of molecule. M effect operates only in the conjugated system. If the conjugation is not available, M effect does not propagate further. ‘M-effect has no correlation with the electronegativity of the connecting atont ofthe group M-cffect is two type: +M and -M_ +M effect (+R) : If the group pushes the electrons into the m electron system, the effect is said as +M effect and the group is called ERG (electron releasing group) or +M group. & “ AeA _ ce + M Effects shown by : -Cly—Br, -NH,, -NHR, -NR,, -NHCOCH,, -OH , -OR Conditiom’: Electron pair must be present at first atom of group. —Meffect (-R): Ifthe x electrons are present system is pulled by the group then the effect is called — Meffectand the group is called EWG group (clectron withdrawing group) or -M group. eg CLOCLAG « € PF =M effect is shown by : CHO, C = 0, -COOH, -NO;, -CN, -SO,H, -SO,CI Condition : (i) Vacant orbital must be present ) Multiple bond with more electron negative second atom. +M-effect— order 1 -éi,>-WH>-07 2 -NH>-NH4. -07>-OR>-O-CH=CH, 5. -NH,>-OH>-F 6. -F>-CL>-Br>-1 -M-effect order e 1. -CH,>-BH,>-PH, ~o 2 -NE >-€N>- E-11>~ © -R>~F -OR>~ C-Nily ‘° 4 Wl ‘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. = te te 1@ g 8 OG Boe @) (>) © (d) {c), ee Wet H\ gH & wD “Y 3 OG O68 Qe ep fa 4° b-- Ob~ BSS Note : @ Thus, mesomeric effect works at only ortho & para position, it is absent on meta position, while inductive effect works at all three position 0, m, p however intensity of effect decreases as the distance increases. @ ~~ Mesomeric effect always dominates on inductive effect except halogen (CL, Br, I, only). APPLICATION OF MESOMERIC EFFECT Stability of reaction intermediates @ Stability of carbocationExample: Stability order : 2 2 ° () CHy~C-CH=CH, >CH, ~CH-CH =CH, >CH,-CH =CH, CH, ° ° e @@ — CH,=CH-CH,> CH, + CH,-CH, >CH, =CH-CH,--CH, @ O-m, <@¥in, < Oe @ Oe < O- < on “ oe om “oe , ° e ° (CH) C> (C\H,), CH> C,H, CH, > CH, = CH-CH}> (CH), €>(CH,), CH> ee ® e CH, -CH, >CH, >CH, =CH>CH = C. v@ O > Ora -Opn (ii) CH, = CH SCH, Cis - CH, allyl carbocation benzyl carbocation ‘Number of resonating ‘Number of resonating ‘Structures = 2 ‘Structures = 4 Hence the benzyl carbocation is more stable than the ally! carbocation. fa, 4, a) Oo” 'NO; NO, o an ay Increase in Increase in Increase in positive charge by positive charge Positive charge by -land - R effect only by -I effect -1 and - R effect stability order I> 11> 1&, Sa, &, “om OC OCH, H, oO ay din ‘Stabilised by + R effect eeuhenedty Stabilised by + R effect destabilized by -L effect vacrae destabilised by -I effect -L power is maximum -1 power is minimum mass = stability order III > 1> IL (i) Stability of carbanion : More resonance in carbanion, more stability of carbanion Example: stability order for following @ @™ 1 wi) e e e CH, =CH-CH,. CH, =CH. CH,-CH, I " m stability order 1 > I > IIT e ® CH,-on > CH,-CH,-OH > CH,-CH,-CH,-OH maximum(—1) Minimum (-1)of OH e e ° CH,-NO, CH,-CH,-NO, _CH,—CH, NO; 1 " m stability order 1 > 11 fesonamce more resonance —_ localized @ charge 1 un m stability order II > 1> Ill e e e e ° (CHs)sC> (C,H); CH > C,H, CH, > CH, =CH-CH,>CH; =CH e e e e CH, > CH, -CH, >(CH,); -CH > (CH),C Orr Qt Om 2° anion 1 aniona Ba, Oo" Cnn un WW tay order > I> (ii) Stability of free radicals. © More resonance, more stability of free radical. Example: Stability order weg ought crneripen stability order II] > 1 > II -0 Oo. Q 1 un a Oo NM & stability order I> 1 > III (i) (CH) C > (CHCA > (CyHCH, > CH, =CH-CH, > (CH,),C >(CHy;CH > CHyCH,>CH, ACIDIC STRENGTH For an acid HA, <2 Hiay+ ATay bial fain) HA, where , K, —> Acidity constant, or dissociation constant of acid K, + Explain the strength of acid pK,=-logK, . K,« Acidic strength « 1/ pK, pH = — bog [H"] from law of mass action, K, = Acidic strength « stability of conjugate base «x -M effect et ate t +1 Acidity of Phenol v/s alcoholR-on—"" 5R-0°+ H® Alcohol no resonance thus acidic strength of phenol > alcohol more isthe 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. w ‘Stabilised by-R and 1 effect and -1‘Thus according to stability of anions o-derivative will be more acidic than p-derivative which will bbe 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 : OOOO ‘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 oe & G2 Ye 0 5, Tra eA tnd“ fect and — | power is maximums. Ou One “ & ay Anion is stabilised only by I effect of NO, group 6-6.a ° oe ace, a8 NS NSO 0) Anion is stabilised by -R and -I effect of NO, group 66. “,=0 (lv) ‘Thus decreasing order of the stability of these anions is follows: 1 > [II> Il >1V ‘We know that ortho derivative is the most acidic therefore decreasing order of acidity of these acids is as follows : SSS Acidity in decreasing order BASIC STRENGTH For an base, BOH,= B+ OH, bey]oring) [Bon] where, K, > Basicity constant, or dissociation constant of base K, —> Explains the strength of base K, « Basic strength « 1/ pK, PK, =~ log K, from law of mass action, Ky =basic suength 1M x <7 +1 Basicity of Aromatic Amines : Basicity of nitrogen containing compounds = Electron density on nitrogen. In aromatic amines, lone pair of elecrons present on nitrogen is delocalised, hence clectron density. decrease due to resonance. Ex. C,HNH, is less basic than CH,NH, a* aon ao cH, lone pair is participating in no resonance of lone pair lone pair is participating in resonance resonance so maximum basic and +1 of CH, o ay ay basic order I > Ill > 1 Effect of cross conjugation on basicity : CH, - 9 Due to delocalisation and — I effect of +A group, amides are less basic than amines. CoHs b- iin, In this amide there is cross conjugation which increases basicity; thus C,HyCONH, 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 (2) Aromatic Character of Compounds : According to the Huckel rale,a compound will be aromatic if it fulfils the following four conditions : (@ Compound should be cyclic (ii) Compound should be planar or nearly planar. ii) Compound should be conjugated through out ring, (iv) Compound should have (4n + 2)x conjugated or delocalised electrons where n isa whole number n=0, 1,2,3,4,5,6, 0 1 3, 4, (4n+ 2)nelectron 2 6 4 18 Examples:& yV.O Antiaromatic Compounds : According to Huckel rule, compound will be antiaromatic ifit fulfils the following four conditions ; @ Compound should be cyclic (i) Compound should be planar, (ii) Compound should be conjugated through out ring and (iv) Compound should have (4n)zt conjugated or delocalised electrons where n is a whole number n=1,2,3,4,5.6 m= A See (4njxelectron = = 4 BIZ anes cme (A. ‘Non aromatic compounds: these compounds are niether aromatic nor antiaromatic oO ap «dp aly) Although cyclooctatetraene has (4n)r electrons but even then itis not an antiaromatic. Geometry of this ‘compound is non planar. Thus it is non aromatic. II~, III & IV* compounds are not completely ‘conjugated. ‘Nate : Duc 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 Bond order = Taal munber of bunds berween two stm ‘Number of resonating aractarcs For examples : ‘Two bonds ‘one bond (eee _ this carbon is is 244 Bond order of carbon in benzene = = = 1.5 Example : Give the correct order of bond length of following mentioned compounds. () CH, -CH, NH,MCQ Qu Q7 Which of the following carboxylic acids is most acidic in character - (A) o-methyl benaoic acid (B) m-methyl benzoic acid (C) p-methyl benzoic acid (D) Benzoie acid ‘Which one of the following is most acidic- (A)pritrophenol _(B)phenol (C)maitrophenol_(D)o-nitropheno! Consider the follownig carbocations - (a) CH,-CH, () CH=CH (©) CH=CH -CH, (@) Coy - CH, Stability of these carbocations in decreasing order is - (A)d>c>a>b (B)d>c>b>a (Chc>d>b>a (D)c>d>a>b Increasing order of acid strength among p - methoxy phenol, p-methyl phenol and p-nitrophenol is- (A)p- nitrophenol, p-methoxyphenol, p-methylphenol (B)p- methylphenol, p- methoxyphenol, p-nitrophenol (©)p-nirophenol,p-methyiphenol, p- methoxyphcnol (D)p- methoxyphenol, p- methylphenol, p-nitrophenol. ‘The groups which when present in para position tend to decrease the acidity of phenol are- (A)-NO, (B)-CN (C)-0cH, ()-F Which freé radical is the most stable - (A) CH- CH, (B)CH,=CH-CH, (C) CHy-CH-CH, (D) CHy- C- CH | chy Which carbocation is the most stable - &, &, Sy, &u, (ay oO «By 9 © 9 (0) 9 cH, OH a NO, ‘ANSWERS QIA Q2A Q3A Q4D Q5C Q6A O78. HYPER CONJUGATIONcH, CH, | @ l @ @ @ CH,-C-CH.> CH, - CH-Cit,> CH, - CH, - CH, > CH, - CH, CH, But acutally order should be reversed which is explained on the basis of hyper conjugation. i nohcn 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 @ 0 (C-H), vacant orbital (positive charge) hyperconjugation : This type of conjugation ‘occurs in alkyl carbocation. cH - CH, éx, - dn - GH, gh - G- Gey CH, no, of a H=3 no, of aH = 6 no, of aH = 9 G0 (C—W),x hyperconjugation : This type of conjugation occurs in alkenes. CH CH- CH=CH, CH,-GH-CH=CH, — CH,- d_ cH= cH, bn, no. ofaH=3 no.ofaH=1 no, of aH = 0 (iil) 0 (CH), 0d electron hyperconjugation : This type of conjugation occurs in alkyl free ni aScH,-CH, CH, ¢- CH, . ? I cH, Note: Carbanion never shows hyper conjugation, if there is one ~C-H sigma bond altemate 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. a 4 z . | * H-¢-culbn, + H-cacH-&, + A C=cH-cH, — H- becH- cH, 1 4 4 f He 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 : & C-H bond > a C-D bond > a C-T bond APPLICATION OF HYPERCONJUGATION {A) Stability of Alkyl Carbocations : Stability of alkyl carbocations a number of hyperconjugating structures o number of a-hydrogens/ Ex.() Cn, CH, ~ 6H;") CH, - én - cH, - CH; 2 “ba M a amy tv) no. of a H=0 no. of aH =3 no. of aH = 6 no. ofa H=9 29 55.6.8 H, = a CH-CH, Geen, HC-C-CH, Nl on, cu, @ @GaH) @oH) (IaH) (aH)(B) Stability of Alkenes :Hyperconjugation explains the stability of certain alkenes over other alkenes: Stability of alkenes cc Number of alpha hydrogens « Number of hyperconjugating structures Ex@) CH,-CH-CH, — CHy-CH,-CH-CH, CHy-¢u-CH= CH, om, @ a al stability order 1 > I> II CH ee CH CH ® oye" on, cu eter, owen o a any lity order 1 > 11 > II a cH, H, cH, HO een, °O-O-O -O (©) Stability of Alkyl free radicals : Stability ‘of alkyl free radicals can be explained by hyperconjugation. Stability depends on the number of hyperconjugating structures. ‘structure cn, CHy-cn, CHy-CH-CH, CHy- C- CH, | cH, © a mm) aw) no. ofa H=0 no. ofa H=3 no. of aH =6 no. of aH=9 Noofhyperconjugating Structure 0 3 6 9 other then given structure © Stability isin inereasing order. = IV > IM > > 1 (D) 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. j b © Ex. (i) CH,-CH=CH- CH, CH,-CH=CH, CH,=CH, Bond length order => a> b>«© fa) () © (i ‘O Bond length onder => a> b> _ O 1,-Cl, 2. I 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. 4 " 4 neon H-c H* ned ne Ht es 4 ‘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 - cn, e ~CH,> CHy— CH= > Sor > CHine cuy 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 | mole of any unsaturated hydrocarbon are hydrogenated is called heat of hydrogenation (AIH) If alkene is more reactive towards hydrogen then it will evolve more AH. 1 x 1 stability of alkene number of a-H AH & number of x bonds It is exothermic process (energy release) Examples of HOH order @ c,-cH-cH,-cH,>cH,-cn-cH- (@ OH-c1-cH cn e>b>a Note : Reverse Hyperconjugation (-H effect) : ‘The phenomenon of hyperconjugation is also observed in the system given! below : -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. cy ° 9 anteater, — cre -cH-tn, —» & b-cn- &4,—c1-b. cH-en, & a ¢ The meta directing influence and deactivating effect of -CX, group for electrophilic aromatic substitution reaction can be explained by this effect. x x x x I | x-cLy xc 8 xg LP oxed xt -¢ ELECTROMERIC EFFECT : (€-EFFECT) © Itistemporary effect. . The organic compounds having a unsaturation (a double or triple bond) show this effect in the‘The effect is annulled as soon as the attacking reagent is removed from the domain of the reaction. Itis represented by E and the shifling of the electrons is shown by a curved arrow (~~). 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 n-clectrons of the multiple bond are transferred to that atom to which the reagent gets attached. For example : 2 see —pb-c<¢ (attacking 1 Teagent) H Negative Electromeric Effect (-E effect): In this effect the x-electrons ofthe multiple bond are transferred to that atom to which the attacking reagent does not get attached. For example. dc fE+en —3e -< ‘Seo cN ATTACKING REAGENTS ‘The specics which attack on a substrate and form a productis called as attacking reagents. ‘Substrate - Reactant which is less reactive is generally taken in greater amount. @ ‘Attacking reagents are of two types (A) Bkectrophile: (B) Nucleophile Electrophiles or electrophilic reagents (E°): (2) They are electron deficient species. (b) They have a tendency to accept electron from another molecule (c) In areaction, an electrophile attacks the substrate at the point of maximum electron density. ‘Types of Electrophile : 0 1) Positively charged electrophiles Br Ro» RCH, Ean). So Neutral electrophiles (a) All Lewis acids as : BF, AICI,,SO,,ZnCl,, BeCl,, FeCl, Sal, (b) Free radicals, carbenes acts as electrophiles. (c) Transition metal cations are electrophiles, e.g. Fe”, Fe’, Ag’B) (a) ‘Nucleophlic reagents or nucleophiles : They are electron rich species so they have a tendency to donate electron pair. (©) Allnucteophiles are lewis bases. (©) Theyattack the centre of minimum electron density ina molecule in a chemical reaction. ‘Types of Nucleophile : @ Negatively Charged nucleophiles: F, Ct, Br, I, OH", CN, RCO, RO", R',R-C aC, NH, SH" ete. (i) Neutral nucleophile containing lone pair: ‘S.No. Electrophille HO, R-OH,R Ry Ry R- RH, electron containing compounds CH,-CH,, CH=CH Ambiphiles : “Ambiphiles are those which act as both electrophile and nucleophile. Example : R-CH=6,RCOR, RCOOH etc. Nucleophile ' [Accept electron [Supplies the electron pair 2 [Eteztron deficient (electron loving) Electron rich 3 [Ussally Positively charged species [Usually negatively charged species 4 [Awacks the points of high clectron density [Attacks thc point of low clcctron denisty Br, of ° a fe HCH, CO, NO es. F. —__—_l MC Qu Find out the correct statcment(s) about given compound neych, CH CH CH ~ oO ae ' M ay «my avy) w) (A) Order of Heat of Hydrogenation & Heat of combustion is same (B) Order of Heat of Hydrogenation & Heat of combustion is different (C) Order of rotation barrier energy for marked bond is 1> I> V>1V> IIL