availability in a parte ot, Pending in carbon compounds (Sec. 2.16) tells us that electron- Rakerniines the seekiViy oF or at a particular atom in a molecule is a dominant factor which n Teacti compound. Electron-availability depends upon five factors. These Inductive effect 11. Electromeric effect 1}, Resonance, mesomeric effect or ty. Hyperconjugative effect \. Steric effect ne wien ¢ factors may operate in a molecule, in opposition or in support of each ee hae e the dine tivity and physical properties of a molecule, it is, therefore, es- bly ‘terming direction and magnitude of these five effects qualitatively and to study Conjugative effect and its M.O. equivalent Lala dipole induced in a bond by another directly along a chain of atoms within a oe effects may also operate through space by solvent molecules or ions and are often The inductive effect is a permanent effect in the ground state of a molecule and is supposed to operate through single bonds. So the inductive effect is called bonds. The C;—Li bond in the chain C, —C3— C;— C;—Li is a permanent dipole because of the greater electronegativity of C than that of Li. This dipole induces a permanent dipole in C:—C, bond and C2 becomes slightly negatively charged, the magnitude of which is smaller than that on C,, and may be represented by the symbol 65—, where 66— < —. In this way the induction of negative charge may transmit down the chain ; but the effect decreases with the ‘increasing distance from the starting dipole. Thus the example cited above may be represented as follows: dds ceqass>) Wassily Cp Cy Op CL where the arrows indicate the electron displacements in the bonds and 6— > 65— > 665— > 5565— Tn fact inductive effect is important up to second atom (here C3) and dies down beyond the fourth atom. Let us take another example to understand the inductive effect. In the chain Cs —C3— C2 — C:—F,, F is the negative pole and C, is the positive pole 5 the electronegativity of F is greater than that of C. Therefore, induction of positive charge will Sccur in the carbon chain as shown below : w+ see Cp+—-Cx>—0z>-C 1 F where 6+ > 65+ > 656+ > 6656+ 149ed General Organic Oh Most of the atoms or groups of atoms like F, Cl, Br, — OH, ete., draw electrons .. themselves, i., away from the carbon chain; these are known & electror : ns and are known as @lect0n 1) i ‘The relative strength and direction of inductive effects of different atoms and groups of, are given below (Ingold’s scale): Decreasing order of +I effect: COO™, RsC, RoCH, RCH2, CHg, D, H. Increasing order of —I effect: H, R,C=CH, Ar, RC=C, OH, SR, SH, OR, COOR, OAr, I, Br, Cl, F, COOH, CN, No, o @ Ng, NR3. Scale of measuring inductive effect Ingold proposed a scale for measurement of relative inductive effects of atoms and group, ., atoms in which H atom is taken as reference in the molecule RsC— H. Tet the H atom be replaced by a group, Gy ile, RgC— G is formed. Now, if electron densi in the RgC part of R,C—G is less than that in RsC—H, G is said to be electron- withdrawing group and its electron- withdrawing effect is termed as —Teffect. On the other hand, if the elect. density in the RaC part of R5C—G is greater than that in RsC—H, the G is said to hx electron-releasing effect and this is denoted by +1. Robinson's terminology is exactly the opposite to that of Ingold. Ingold’s terminology is use! mostly; we shall follow this too. (a) Dipole moment: Inductive effect is intimately associated with dipole moments of molecules, Generally, dipole moment increases with the increase in inductive effect provided effect due to more than one group do not act in opposition to each other. Thus the dipole mon of ci+2-butene (1) is greater than that of ‘:01i-2-butene (2) because in the latter compount! ~ effects of —CHg groups are cancelled as they act in opposition to each other. Hs CH OH; meena Peele? oN Keo 1 2 (b) Chicmical reactivity: Inductive effect has a dominant role on the reactivity of @ “.'” pound. Thus 1i:°\0-dinitrobenzene (3) when heated with fuming HNOs and fuming HoSO« ‘-trinitrobenzene (4) and the reaction takes five days to complete; but toluene (5) is very ©!" nitrated with conc. HoSO, and conc. HNOs to produce ort! and jyari-nitrotoluenes (6 a" ‘The —I effect of —NOz groups in \c\-dinitrobenzene makes the molecule much less ret" than the toluene containing a methyl group which has +I effect. For this reason nitration °' medinitrobenzene requires drastic condition but that on toluene does not. Not only that,actors Influencing Electron-avail deactivating effect of nitro groups invites the incomin, activating effect of methyl group directs the in ig nitro group to the meta position; but the ing nit i itions jn toluene. coming nitro group into ortho and para pos NO, Ree fuming HNO; Se fuming H)SO, 3 ae NOg ‘NOp 4 a OH CHs NO, cone. HNOs ——., conc. HaSO4 a NO» 5 6 7 (c) In comparing basicity of bases: According to Lewis, a base is a chemical entity which is capable of donating electron. Organic species containing N or O atom with donatable lone-pair of dlectrons may be considered as organic bases. If any electro n-releasing group is attached to such an N atom or O atom in a base, it will increase the electron density on the atom and hence the basicity of the base will increase. Thus, owing to the +I effect of —CHs group, methylamine is more basic than ammonia. Similarly, for the same reason methoxide ion is more basic than hydroxide ion. Basicity of CH3 -— NH > basicity of NHs Basicity of CH3 -— O > basicity of O—H On the other hand, any electron-withdrawing group attached to N or O atom in an organic base decreases the electron density on the atom and thereby decreases its basicity. Thus, triflu- oromethylamine (8) has a very low basicity with respect to methylamine; this is because of the —I effect of the three fluorine atoms. BK FCN is less basic than CHsNHy i 8 (d) In comparing acidity of organic acids: The ability of donating proton of a chemical entity may be called acidity of the entity and the entity is said to be an acid. If we compare the acidity of formic acid, acetic acid and chloroacetic acid, we shall see that the acidity of chloroacetic acid is the highest of the three and that of acetic acid is the lowest amongst them. This is because of the fact that any electron-releasing group attached to the carboxyl C atom decreases its ability to donate proton. Methyl group in acetic acid is an electron-releasing group, it lowers the acidity f acetic acid than that of formic acid. But electron-withdrawing effect of Cl atom, increases this lity of chloroacetic acid largely. For this reason the acidity of CICH,COOH > HCOOH > CHsCOOH.Advanced General Organi. ¢, 15! (e) Stability of carbenium ion: See Problem 4.20. Problema 4/1. Which one ofthe following will nave te Bienes dipole moment an, 1 Cl : ou—{ a4 a y he / a b ( i Solution: Tn compound a, the +1 eisote/O: ==aOns Broure Bro OPerernE in Opposition, tach Other nd hence their effects ebeleancsledimSumanelene coc 7 Op" ound ci her aoe of the two C atoms tre caneIRMERM EMCEE ap CE and —I effect of the Cl are acting in the same direction and hence compound’ © fas the j dipole moment amongst the three compounds. why ~o "The electron distribution in a o bond may change by the pa of ‘a charged and thus partial polarisation occurs; this temporary effect, ® polarisability effect, is inductomeric effect. be The temporary or time-variable effect involving the complete transfer of a shared pair electrons to one of the atoms joined by a multiple bond, double or triple, at the requirement « attacking reagent is known as electromeric effect. As soon as the attacking reagent is remove: the transferred 7 electron pair again form the bond and the molecule reverts to its grow state electronic condition. For this reason, the electromeric effect may be called polar of multiple bond. There is, of course, permanent polarisation of the sigma bond in the mu) bond, but this inductive effect is negligible with respect to the electromeric effect. ‘To understand this time-variable effect let us now consider a proton (H®) which comes «ls to a carbon-carbon double bond. To provide electron to the proton, 7 bond will break wn! electron-pair will be transferred completely to one of the C atoms as shown below: >c=c< == 6—6< The electromeric effect has no specific direction. Its direction is always that: which favours * reaction. However, if one of the atoms joined to the multiple bond is more electronegativ« the other, the transfer of electron-pair usually occurs on the more electronegative atom: ¢ electromeric effect on >C=O bond is as follows: io) Hel >C=0 —= >6—9 ‘This is because of the greater electronegativity of O than that of C. Inductive effect does also play an important role in determini ee is ; the di f the el tromeric effect. If a group with +I or —I effect is attached to a etal, bonded C cn of the system >C=C<, the direction of the electromeric effect is the the induct effect. Thus in propene (9) the transfer of electron-pair will cent an the Bre © tens (10), 1 cHj—caLb, As cHy— Sn 9 10pctors Influencing Electroy 7 ait (11), the ~1 effect of ——OH reverses the electromeric effect as the wMguctive effect. 1°T° €00 the direction of the electromeric effect is the same as that of ty. 153 @ ana H® CH=CH. CH, —— OH === CH,—CH—CH,OH 1 12 lect i 7 i ‘The el os effect being temporary, it is not reflected in the physical properties of the ‘The electromeric effect is denoted of x electron-pair is away from or to by the symbol B, It is said to be —E or +E as the transfer wards the carbon chain respectively. The ee ioe effect, i.e., the close approach of a reagent to a multiple bond enhances the Besa ty of . e fai eect and explains its addition reaction product. Thus the addition smmonia to acetaldehyde (13) may be cited. Th ter electi tivity of O atom and = Bee eractiy] cron ie greater electronegativity f oup in acetaldehyde help transfer the x electrons on O atom at the requirement of the ammonia molecule which coordinates with the double-bonded C atom. i H NE. | cHy—c=£d = CH3—C—0 —+ CH;—C—6 —~ CH;—CHOH NHy as NH 13 14 15 16 Problem 4.2. Predict the direction of the electromeric effect in the compound COOH.CH=CHOH (I effects are to be considered only). Solution: Both the —OH and —COOH group have —I effect. So, each of them will try to draw the x electrons to its side. As the —I effect of —COOH group is greater than that of the OH group, the transfer of 7 electrons will take place towards —COOH group. 8 Berge da) co on eee eee eee Problem 4.3. Distinguish between inductive effect and electromeric effect. Solution: Contd.Advanced General Organic ¢, 1 a hems, ru Tho B effect has no specific direc, electronegativity of bonded atom, effects of the attached groups may; mine the direction of the electromeric yf. In fact, its direction is that which fg..." iiapsey 2 the reaction. Hon; th. quivalent of In the discussion of the second assumption of the V.B. theory we have come to know somethin, about the resonance of covalent bonds involving o electrons. There we have found that joni, resonating structures are unimportant but resonance involving 7 electrons are very useful in th, prediction of molecular geometry, bond parameters and chemical reactivity of chemical entiti, i.e,, ions or molecules, However, we may recall that the resonance is a hypothetical state of a chemical entity i, which its electronic structure can be hypothetically represented by two or more Lewis dash-do structures, each differing in the distribution of electrons; the properties of the entity will not ty expected from any of the structures but they will be those to be expected from a combination called a resonance hybrid of them, each of the structures of the hybrid being known as resonating or canonical structure. All the units of the entity are alike and the actual structure of the entit neither does shift from one canonical form to other, nor does it consist of a mixture of them. ‘Th entity has a single structure of its own which cannot be written down by the conventional Lewis method. So we take the help of other possible, though non-existent, structures which could b: represented by the Lewis method. Generally, the resonance hybrid is projected on the plane of th paper by writing down all the resonating structures and placing a double-headed arrow betw: each pair. Resonating structures, in turn, are to be written down following certain conditions which are given below. : The following conditions are to be followed for writing resonating structures: (a) All the canonical structures must be written according to the Lewis : nding Li bonds, lone-pair of electrons and formal charges where required, (See Section 2 7) (b) The positions of the atomic nuclei of the chemical entity must remain unchanged in all the » in an ethylene molecule, each of the two C atoms have two showing H,C=CH +x H;3C— GH I Iactors Influencing Electron-avai (c) hae eee ane structures, only the x bonds can be converted to * bonds and to and vice versa. Thus, th ‘i i agai 1us, the resonance hybrid of ethylene may be written as (though ny Breit x 8 HoO—CH»-—H,0— 6,6 — CH, I ur Iv @ id ee ‘unpaired electrons in each of the structures must be the same. Thus, © ® resonating form in the resonance hybrid of ethylene as it contains two unpaired electrons which no other structure possesses, CH=" @ z. =. M @ a= CHa+—+CHa— CH, GHy— CHy—x—4C Hyp — CH I 1 Iv v (e) The several resonating structures must be of comparable energies: 1 gies; thus, for ethylene, structure IIT and TV have such a high energy in comparison to I that these should not be accepted as resonating structures. This means that structures III and IV do not explain the properties of ethylene but structure I explains. (f) All atoms involved in the resonance must lie on the same plane or nearly on the same plane; any change in structure which prevents planarity will diminish resonance simply because maximal overlap of p orbitals cannot be possible then to form the bond orbital. Thus, in allene the two =CH> units are lying in two mutually perpendicular planes and hence no interaction between the two 7 bonds can take place in allene (VI). Him, (any Ex ia i VI Following the conditions said above one may write down a resonance hybrid of an entity. But it is of importance to tick out those canonical structures which contribute significantly in the hybrid. The contribution of each form is proportional to its stability; the most stable structure contributes the most and the least stable structure contributes the least. Here are some empirical tules which are helpful in deciding the relative stability and contribution of structures. 1, Resonating structures with more covalent bonds are normally more contributing than those with a fewer number of covalent bonds since more the number of covalent bonds, the less SS the energy of the species and more is the stability. Thus, the structure VII of CO2 has major Sontribution in its resonance hybrid and the structures VIII and IX have minor contributions. @ te = — C= 0: — :0=C— 0: vi Ix 2. If the different resonating structures have the same number of covalent bonds, then un- structures have major contribution in the resonance hybrid. Thus, structure VII has ‘much greater contribution than structures X and XI of COz in its resonance hybrid.~ 5, Structures with isolated unlike charges have less contribution than thse in Which they 4. close to each other. Thus, structures X and XI of COz have less conti! ms than structys VIII and IX in its resonance hybrid; contribution to this by structure VII being the most (4, ae rule I), Structures X and XI have good contribution as per octet rule. 4, Structures with like formal charges crowded together have very ae, and hence these are less contributing than those in which like charges remain separated. Structure XII ha. no contribution to the resonance hybrid of CO2 molecule. x Xie . 5. Any structure in which a second row element of the periodic table (Li to Ne) has more than eight electrons in its outermost shell contributes nothing. Structure Xie of COz possesses aC atom with ten electrons and hence this structure contributes nothing to its resonance hybrid 6. Structures with a negative formal charge on the most electronegative atom and a positive formal charge on the least electronegative atom have significant contribution; structures with opposite charge distributions are less contributing. Thus, structures VIII and IX of CO) are more contributing than structures XIII and XIV. 7. Equivalent resonating structures are more important than non-equivalent resonating struc- tures, because in the former case the equivalent structures have the same amount of energy but in the latter case non-equivalent structures do not. Thus, resonance in the carbonate ion is more important than that in the carbonic acid. In the structures XV, XVI and XVII of CO;~ ict we see that each of them possesses two negative formal charges over two O atoms, which ar single-bonded to C atom, and one O atom is double-bonded to C atom. Hence these structures are equivalent structures. On the other hand structure XVIII, XIX and XX of carbonic acid arc non-equivalent. ,pctors Influencing Electron-availabitity Sr Note F Apatow equivalent resonating structures, the resonance hybrid of CO;~ may be represented ro 0. Sq]? ~tI80.. = c 0-2/3 I oO 0-2/3 The ator, of the C—O bonds in CO4 is neither double nor single but an intermediate vamvof the three O aterernseative charges may be shown by distributing the charge equally on cach of ia - eae em will have 2/3 unit of negative charge. 8, Iso leat resonating st » structures having the same number of covalent bonds are more ais, a than h ‘esonating structures which contain different numbers of covalent bonds. Thus, Tuctures in the resonance hybrid of benzene are very important, id thus each of th Tuctures, ie, leterovalent 1 Tesonating sti lar hexagonal structure in which all the C—C bonds are of the same length; structures XXIV, XXV and XXVI have central bonds; its length is 0.23 nm, i.e., almost twice the length of a C—c bond (0.139 nm). It is too long for significant bonding. Therefore, these three structures have minor Contributions to the resonance hybrid of benzene, ee” O-0-0-6-9 | XXII XxIV XXV XXVI 10. Structures with electron deficient atom, i.e., possessing less than eight electrons in its outermost shell, have high energy, i.c., low stability and hence they contribute lese than thee, Stuctures in which octet rule is not violated. Thus, structure XXVI contributes more thes structure XXVIII (the terminal N has 6 electrons, icc., it is in the sextet state) in the resonance hybrid of diazomethane. XXVII XXVHOI 11. Resonating structures are more important in a conjugated system (structures possessing titemate single and multiple bonds) than those in an isolated system, For example, the resonance in CH= CH— CH— CH,(A) is more important than that in CH»—CH—CH,— CH= GHa(B). The greater number of significant structures in a resonance hybrid means the greater Ice of the resonance in comparison to another hybrid Possessing a fewer number of res- hating structures. The resonance hybrid of compound A contains a greater number of resonating fures than the hybrid of compound B as shown below:a ————emenmmns Advanced General Organic Chen, x @ @ y ‘A. CH= CH— CH=CH, > Gil; — CH = CH — Clg CH — CH=CH Gy, fone is ise wos cH, =cH—CH—GH, > CH, —CH— CH=CH CH — CH Cis ¢, etc. ea B. CHy=CH— CH) — CH=CH, > CH,— CH CH — CH= CH ee, CH)=CH—CH,— CH—CH, — a, Note ‘Thus, we see that in A electrons are distributed over whole of the molecule embracing ali (© atoms and do not remain localised; this phenomenon is called delocalisation of electrons diminishes the reactivity of x electrons and lowers the energy of the system, i.e., brings sta to the system, In an isolated system delocalisation also occurs between two adjacent ato only, but such a wide range of delocalisation of electrons involving large number of atoms «: take place as in a conjugated system. So we can conclude that the more the delocalisat clectrons or positive charge, the more is the stability of the entity and the lower is its en ‘The delocalisation of electrons in butadiene may be shown as in Fig. 4.1. | The delocalisation of electrons in benzene makes the molecule stable. Each ofthe six €aton= is ep? hybridised and each of them possesses one p, orbital with an unpaired electron. Three ‘AO. are utilised to fortn ons O—H ¢ bond and two O—-C¢ bonds, In this way six C at form a planar hexagonal ring structure and six H atoms also lie on thi stitute the o skeleton of benzene unit. ao ‘Therefore six p, orbitals of six C atoms are now parallel to each other. By si é of two pz orbitals of two adjacent C atoms a m bond is formed. In this en 2 formed in five different ways in a molecule of benzene. ‘The whole picture may be obtained ft Figure 4.2.Mi 4.2. Delocaistion or electrons in Benzene The delocalisation of electrons does not only take place in alternate single and multiple eeeereing C stoms, but it may also occur ins conjugated system involving C and other atoms, €.g., i CHs— C— CH=CH, — cH;—G CH—CH, XXIXa XXIXb s = @ CHy)=CH—Gi > GH, —cH= Gk XXXa XXXb 2 e CH)=CH— CH; “— CH,—cH =CH, XXXiIa XXXIb There are also examples in which 7 orbital and p orbital (vacant or filled) overlap and the also examp! Cbsslsation of charge occurs. ‘Thus, in the structure XXXa, the filled p orbital of Cl atom is Wed in the process of delocalisation with the electrons of C= Bont j 8 Sinilaly in the structure XXXIa, the vacant p orbital of © atom in Hy part overlaps the tit of C=C bond, Thus, delocalisation of charge or electrons are of several types and a few of them are: } Delocalisation by x-1 orbital overlap 2 Delocatisation by 7p orbital overlap 4. Delocalisation by o-m orbital overlap‘Ts A IVariceI General Organic Chem 4. Delocalisation by o-p orbital overlap 5. Delocalisation by dx-p orbital overlap cl ae (OF) O ‘Types 1 and 2 have already been discussed. Types 3 and 4 are to be discussed later on Problem 4.4. Tick out the minor contributing structure, with proper reasoning, in each o¢ the following pairs of structures: ® = x ® (a) R—C=N: > R—C=N (b) CHp =N—N: <> CH =N= c D Solution: (a) Structure B; as more electronegative element N has positive charge and electronegative carbon has negative charge. (b) Structure C; because it has a fewer number of covalent bonds and electron deficient » atom which is in the sextet state. (c) Structure F; since oxygen-bonded C atom is pentacovalent, i.e., possesses 10 electrons i its outermost shell. (d) Structure H; here it contains a fewer number of covalent bonds as well as like chary¢ (-ve) on adjacent atoms. (e) None of the two structures is less contributing than the other as they are equivalent structures. Problem 4.5. Write down at least one resonating structure for each of the following str tures: @ yy Hee A. CHy—G B. NH,—C—NH, ©. CH,=CH— CH, 6—HGo 9 A nee aks, pgs 2 5 ao NO—n id 20: mh ion, —6— i — Niy=C— iy i C. CH,>=CH— GH, > GH,—CH=CH) Problem 4.6. Represent the resonance hybrids of the following structures: Oo Oy ~ Xs @) Base N=6: (c) CHy=CH—CH=CHy Solution: (a) =” —1—o— 6 H @ Beet Il 0 (© [C=CH—cH=cH, —> éH,—cH=cH— Gry « + Gi,— GH— CH=CH, @ 3. us e CH)— CH—CH=CH, <—> GH, — CH CH=CH The resonance hybrid of an entity is a more stable structure than any one of the resonating structures contributing to it. ‘The resonance energy is a measure of the extra stability of the Tsonance hybrid. It is defined as the difference in energy between the actual structure of the ‘atity and the most stable structure of the hypothetical structures. The resonance energy of @ may be calculated by either of the following methods : 1. Resonance = Observed heat of — Calculated heat of formation of the stablest ‘nergy formation resonating structure of the hybrid (4.1) 7% Chem.-11 ail162 eens Advanced General Orgy, 2. Resonance = Observed heat of — Calculated heat of combustion of the Stables, energy combustion resonating structure of the hybrid 3. Resonance = Observed heat of — Calculated heat of hydrogenation of th ., energy hydrogenation _ form of the hybrid. Note [Heat of formation: It is defined as the amount of heat given out when one mole of : stance is produced from its constituent elements. ‘Thus, heat of formation of, 394.9 kJ/mole; this means that when one mole of CO2 is produced from amount of heat is released. Heat of combustion: It is the amount of heat evolved when one mole of the subs, completely burnt down in oxygen. Thus, heat of combustion of benzene is $30.5 keJ/inoi Heat of hydrogenation: Tt is the amount of heat evolved when one mole of an unsa compound is hydrogenated. Thus, heat of hydrogenation of ethylene is 137.4 kJ/mole So resonance energy is a relative term. For example, the observed heat of hydrogenay benzene is 208.5 kJ mol? and that of the Kekule’ structure (as calculated from the hydrogenation of cyclohexene; see p. 158 Problem 4.8) is 359.1 kJ mol~!; hence energy of benzene is (208.5 — 359.1) or 150.6 kJ mol™". ‘The vertical resonance energy of a molecule is defined as the difference in interna between the actual molecule and a hypothetical molecule which has the same bond len. angles as those of the actual molecule. In calculating the heat of hydrogenation of the Kekule’ structure of benzene we have » calculated the heat of hydrogenation of cyclohexatriene which contains three C— C sing (bond length : 0.154 nm) and three C—C double bonds (bond length 0.133 nm) alr but actual benzene molecule contains six C—C bonds, each having 0.1397 nm bo So we shall have to convert the Kekule’ structure of benzene molecule to another hy structure in which all the C—C bonds are of 0.1397 nm in length; in doing so eac! single bond length is to be compressed to 0.1397 nm from 0.154 nm and each C— ( bond length is to be expanded to 0.1397 nm from 0.133 nm—this requires an extra « 113.0 kJ mol~? (calculated from the knowledge of force constants of C—C single a bonds by Coulson). 0.133 nm Bt Sac (Cou nm Cyclohexatriene Hypot ni ‘ thetical molecule hav: Kekule’ benzene the same bond lengths as = of the actual benzene molecule i 1 ‘Therefore, the vertical resonance energy of benzene is Ww mol~! where the reference molecule is II instead of I, (208.5 ~ (359.1 + 113.0)] or 264 So, the vertical resonance energy is also a relative from the resonance energy of the entity. energy. However, this is always ‘iff’Influencing Electron-ai To mnt De coplene 2 fesOnance to occur is that the involved atoms in resonating ite ot full, the involved eee Planar for maximum resonance energy. If ths cond on Stion of electrons or posse os camnot be parallel to each other and as a consequence nce is inhibited or reduced bes charge cannot occur. ‘There are many examples in which if planarity and the phenom, ecause the involved atoms and orbitals are sterically forced out mumethyt-2,4,6-trinitroanil ‘enon is called steric inhibition of resonance. For example, in DR eISPAE thes/cloasty. iat -_—NMez group is out of the plane of the ring owing to the ene oof the ——NMe ce bulky groups and consequently the lone pair of electrons on the Na “2 Broup cannot get delocalised through p-r conjugation. NO, as / »NOp ie z Me Bo A 6 No, Me Za ia i NOp The steric inhibition of resonance has profound effects on: (a) physical properties, (b) acidity and basicity, (c) the reactivity of organic compounds. These are discussed below in brief : (a) Physical properties and steric inhibition of resonance: (i) Bond length and bond strength: Owing to the involvement of resonance, a single bond assumes a partial double bond character while a double assumes a partial single bond character. Ifsteric effect inhibits resonance, the shortening or lengthening of such a bond does not occur. Since the shortening of a bond increases its strength and the lengthening of a bond decreases the same, steric inhibition of resonance changes the strength and length of a particular bond. Thus, in the examples given below C—N bond a is shorter than the C—N bond b and hence the former is stronger than the latter. »Me PNOg ee ee Ne al oO ae Me No x b Re ike XXXII XXXII In the compound XXXII owing to the steric congestion involving two methyl and one nitro groups, the © atoms of the nitro group and the vacant p A.O. of its N atom are sterically forced Sut of the plane of the ring. Thus, the —R effect of the nitro group cannot play its role and the C—N bond, b, fails to assume a partial double bond character. On the other hand, the vacant 7. AO. ofthe jrnitro group and its O atoms are on their usual plane because ofthe absence of Steric congestion. ane Me oO ? a 8 Bae bee > NOz Ne PONO7 Se Ng “Me ~O i “~~Me Me 0Advanced General Organic (,, i ase of the —R effec, the former is t So, the C—N bond, a, has a partial double bond characiat bee nitro group. Therefore, the bond a is shorter than the bond b, i-¢-, the latter. Similarly, in the compound XXXII the bond b t owing to steric inhibition of resonance; whereas the bond a in # bond character because of resonance. stron ner th, does not have a partial double bond cha, his compound has a partial 5 POs N02 oe” att aa ~ wor! eNO C2 ms! 0 no, DYNO» aN ’ ‘Therefore, the bond a is shorter and stronger than the bond b in compound XXXII (ii) Dipole moment: Steric inhibition of resonance in an aromatic compound lower : dipole moment since the distance between the two poles of such a compound is shorter than ¢} in a similar compound without steric inhibition of resonance. For example, the a momen of N,N-dimethylaniline is 1.61D whereas that of 0,0’, N,N-tetramethylaniline is only 0.94 D. Me Ape hy o/ 3 Mh — HX Tae. Me Me , _yMe 4 a /Me AiR oo EH BS Note he Meee (iii) Melting point and boiling point: Compounds involving steric inhibition of reson have lesser number of ionic resonating structures than compounds without steric inhibitior resonance; as a consequence compounds of the latter category are more ionic than those of tiv former category. We know that with increasing ionic character m.p. and b.p. increase. There! mp. and b.p.s of sterically hindered compounds are less than those of the sterically unin compounds. For example, the m.p. of 2,4,6-trichloroaniline is 785°C where as that of 2.1. trichloro-N-methylaniline is only 32°C and 2,4,6-trichloro-N,N-dimethylaniline is a liquid unde! ordinary conditions. (b) Acidity and basicity: Since steric hindrance redu itive charge or electrons through resonance, steric inhibiti on the acidity and basicity of compounds. ices OF prevents delocalisation of pos ion of resonance has appreciable eff’- Feotors Influencing Electron-availability - o Mt ORE OB —EtOH = = ae J t EtOH “ 0 0 0 oO 0 as H H iC 0 Cyclohexane-1,3-dione is much more : acidic than bicyclo [2.2.2}-octane-2,6-dione simply be- cause the enolate ion of the former gets s i stability through resonance while that of the latter does not; the filled p orbital of the enolate ion of the latter compound being out of plane of the C=0 groups, it cannot overlap with the x electrons of the carbonyl groups assuming planar trigonal geometry. (c) Reacti 165 ity: Owing to steric inhibition of resonance, electronic charge density decreases at a particular C atom of an aromatic compound, i.e., its nucleophilicity decreases. Therefore reactivity of the compound as a nucleophile decreases. For this reason N,N, 0,0/-tetramethylaniline does not couple with benzenediazonium ion (see problem 17.23). Problem 4.7. The observed heat of combustion of 1,3-butadiene is 1250 kcal/mole. Theo- retical heat of combustion values in kcal/mole for C—H bond: —99.5; C—C: -81.0 and C=C; -146.1. Find out the resonance energy of the compound. Solution: 1,3-Butadiene is CH=CH CH= CHp. It has six C—H o bonds. The heat of combustion of six C—H bonds = 99.5 x 6 or 597.3 kcal mol~!. For 1 C—C ¢ bond the heat of combustion is 81.0 kcal mol~* and that for 2 C=C part is 146.1 x 2 or, 292.2 kcal mol}. The sum of the heat of combustion values is 970.5 kcal mol~!, Resonance energy = (1250 — 970.5) or, 279.5 keal mol-}. Problem 4.8. Heat of hydrogenation of cyclohexene to cyclohexane is —28.6 keal/mole. The observed heat of hydrogenation of benzene to cyclohexane is —49.8 kcal/mole. Find out the Tesonance energy of benzene. Solution: Cyclohexene contains one C=C bond but benzene contains three C— C bonds. +, Calculated heat of hydrogenation of benzene is 3 x —28.6 = —85.8 kcal/mole. Hence resonance energy of benzene = [-49.8 — (-85.8)] kcal/mole (See Eqn. 4.3) = 36 kcal/mole The discussion on resonance involving 7 electrons tells us that it decreases the electron pene 4 one position and increases the same elsewhere in a chemical entity; this redistribution of clectrons takes place with permanent polarisation in the ground state of the entity. The effectAdvanced Cuno’ ibution of electrons with permanent polarisation in the grey = a learn and chiefly in conjugated systems via = orbitals ix falas resonance effect. MESOMERIC EFFECT includes both electromeric and resonance effect, Ney), tromeric effect, mesomeric effect may be represented by the symbol M or R. Whey 1)..." displacement is away from the group concerned, the mesomerie effect is said to 1 when the effect take place towards the group it is called ~M or —R effect The mesomeric effect being a permanent effect, the physical and chemical proper may be explained with the help of this effect. Problem 4.9. Distinguish between (a) inductive effect and mesomeric effect tromeric effect and mesomeric effect. Solution: (a) eral Orga eral Organic Chop INA stay Cony "gat M Mesomeric (M or R) effect 1. This is a permanent polarisation effect. 1. This is also a permanent polarisation , 2. This involves 7 electrons. 2. This involves ¢ electrons. 3. This occurs in the unsaturated and 3. This occurs essentially in a saturated especially in the conjugated systems. 4. This effect is transmitted over a wide 4. It is transmitted through a short dis: range, provided conjugation is present. saturated chain, (b) Electromeric effect (E) Mesomeric effect (M or 1. Temporary polarisability effect. 1. Permanent polarisation effect 2. This involves x electrons. 2. This also involves 7 electrons. 3. This occurs involving two atoms only at 3. This may occur over a wide rane. | the requirement of an attacking reagent. conjugation is there. 4. Being a temporary effect, it has nothing to 4. It can explain both the physical and do with the physical properties of an entity. properties of entities. Constitutional isomers existing in rapid equilibrium are kn ad th librium reaction is called tautomerism. For example, scalaldatyde (XXIV) ands E, (XXXIV) are tautomers that exist in solution. We detect the presence of both the como Cll —C—=0 == Cit—=CH— on H XXXIV XXXIV solution by chemical tests. ‘Therefore, tautomers have real existence and they are isola On the other hand, resonating structures are essentially hypothetical sti 7 and stent may draw some main points of differences between the two as stated in BE poce. t ne her, state of chemical enti * 1, Itisa sso : Resonating structures are hypothetical and 2. "Tnttcteers have existence and they are non-isolab) = isolable. oe OF the atc or at entity the 3. "The postions of the atomic nuclei are not x Temain the same in tautomers. 4, Only redistribution of electron is involved. s 4. Redistribution of . 5 Actual structure of the entity is one and the 5. Dabtocnend Las Aunt ad same though different resonating structures are written. Sertines TuPrium between resonating 6. There is a rapid equilibrium between tautomers. [fepResontince lowers the energy of the entity,” 7. ‘As’ tautomers aré diferent cotipounds; | the question of lowering of energy does ' not arise. Problem 4-10. Tick out the pair of compounds as tautomers or resonating structures: 9 OH 8 a. and its air and —. H ° OH Il a 8 e ay ou and CH3.C.CHs d. CH»=CH—CH» and CHyp— CH=CH OH Solution: (a) Tautomers; as there are changes in positions of two H atoms. (b) Resonating forms; because the positions of the atomic nuclei remain the same and only electron redistribution has occurred. (c) Tautomers. (d) Resonating forms. A. Resonance is used to explain the stability of an entity (i) A resonance hybrid possessing a greater number of resonating structures is more stable than the resonance hybrid consisting of a fewer number of such structures. (ii) Blectron redistribution over a wider range brings greater stability to a system than that over a shorter range. (iii) ‘The stability of the resonance hybrid increases with the increasing number of significant structures in it. Problem 4.11. Which one is more stable— (a) Acetic acid or acetate ion in the aqueous solution? (b) Benzene or cyclohexene?Advanced General Org, ie 20: 2 — CHj;—C=0—H 1 2 Here structure 2 has minor contribution because the latter structure ‘on the electronegative O atom. ‘The resonance hybrid of acetate ion is: Possesses a posit Here the two structures are equivalent and, therefore, they have equal contribution y hybrid. So resonance is more important in acetate ion than in acetic acid. Therefore, in th solution acetate ion is more stable than acetic acid. (b) The resonance hybrid of cyclohexene is: 1 \e — om le 1 E F G Charged structures being much less contributing than uncharged structures, F and b minor contribution to the hybrid and hence resonance does not bring stability to cyclohe: ‘The resonance hybrid of benzene [KXI—XXVI] shows that (@) there are isovalent struct (it) delocalization occurs over a wide range and (Iii) the number of resonating structures ax more than those in the hybrid of cyclohexene, Hence benzene is more stable than the B, Resonance can be used to explain bond length values: (i) If resonance occurs between single and doub! le bonds then the single bond length d but double bond length increases, (ii) If double and triple bonds are involved in resonance, and increases the triple bond length, Problem 4.12, O—N bond length in NH: can you explain this shortening of bond length? Solution: Structure of NHzCONH may be represented by the resonance hybrid as Wt! below: ‘i this decreases the double bond lens CONE is 0.137 nm instead of 0.147 nm. Horfactors Influencing Blectron-aVAilab lity TS 16) Thus, we see that each of the two C—N bonds j is single in two structures ; ‘onds in the compound is single in and double in one structure. So, it should be shorter than earborcnitrogen single bond but longer than caron-nitrogen double bond, ‘Therefore, the given value of the bond length, 0.137 nm, is expected: C. Resonance can be s sed to explain the dipole moment of an entity: The dipole moment (j1) Sr is directly proportional to the distance between the two poles (r). ‘This means as the distance between the two poles increases, the dipole moment increases. If resonance happens to occur over a wide range, the high dipole moment will be the result; on the ibe Haat, Tesonance over a short distance gives rise to a low dipole moment Problem 4.13. The dipole r moments of nitromethane and nitrobenzene are 3.60D and 3.95D respectively—explain, Solution: The resonance hybrid of nitromethane is: 6 oe ef _ 9 Ch—N No. » ‘The resonance hybrid of nitrobenzene is: CHy— Thus, the distance between positive and negative charges in nitrobenzene is greater than that in nitromethane. Hence, the dipole moment of nitrobenzene should be greater than that of nitromethane. D. Resonance can be used to explain the symmetry of an entity: If all the resonating structures are equivalent in the resonance hybrid of an entity, the entity will be symmetrical. Problem 4.14. Explain the symmetrical nature of carbonate ion. Solution: The carbonate ion may be represented by a resonance hybrid Possessing three equivalent resonating structures as written below. For this reason carbonate ion is a symmetrical entity. O38 of acids and bases Tespectively: E. Resonance can be used to explain the relative acidity and basicity (i) Acidity: If the conjugate base of an acid is more stable than the acid itself, then the base strength, i.e., basicity of the conjugate base is lower than the acid strength of the acid. This means, the weaker is the conjugate base, the stronger is the acid. ae CH, H H He H 9 10 id, 12 Thus, in free radicals and in carbenium ions with adjacent C—H ¢ bonds, the resonating structures display no more odd electron or charge separation that do the main structures (here 5 and 9 respectively) and all of the structures possess the same number of covalent bonds. Hence this type of hyperconjugation is termed as isovalent hyperconjugation. The effect of hyperconjugation is that of electron release from the C atom adjacent to the Tbonded C atom or electron-deficient, C atom (ie., a © atom with odd election or positive charge). ‘When it happens to occur in the ground state of a molecule, some of the physical and chemical properties of the molecule can be explained with its help. On the other hand, when hyperconjugation takes place in the excited state of the entity, it can then only be helpful in explaining chemical reactivity of the entity. It is here worth-mentioning that the hyperconjugative effect was first noted by Baker and Nathan in connection with the anomalous indwctive electron *elease by p-substituted allyl groups in benzyl bromide; this effect came to be called Baker- Nathan effect. However, hyperconjugative effect can be utilised to explain the chemical reactivity and stability of entities. These are discussed in the problems given below: Problem 4.17. In ethane the C—C bond length is 1.54 A but in propene C—C bond length is 1.50 A—explain. Solution: Owing to the hyperconjugative effect in propene, C—C single bond has some double bond character as seen from the following resonating structures:Va —=(H==CH, +——> H--C=C-—CH, «——> H HOE ‘Therefore, the C— C bond length should be a bit longer than C=C bond and shorter O-— C single bond, But charged structures with a fewer number of covalent bonds are less contributing to 1) resonance hybrid than the uncharged structure. Por this reason the shortening of bond length j not so much as expected, Hence it is very near to 1.54 A. | Problem 4.18, Propene is more stable than ethene—explain. Solution: Hyperconjugative effect plays its role in bringing stability to propene; this is | in ethene, For this reason ethene is less stable than propene; in fact, heat of hydrogenation of ethene is greater than that of propene by 2.7 kcal/mole. However, the sp*-sp” bond characte, | | also explains the stability and the shorter bond length of HsC— CH bond. Problem 4.19. Alkyl groups attached to benzene ring have electron-releasing effect in th order: Me—— > MeCH,— > MexCH— > MesC— ‘This is quite opposite to that expected from inductive electron release. Explain this anomaly Solution: Hyperconjugative effect alone can explain this anomaly. When an alkyl group is attached to a benzene ring, the O—TH o bond of the C atom, whic is directly joined to the benzene ring, overlaps with the 7 orbitals of the ring. For each C— | bond three charged resonating structures are found, As a methyl group has three C—H ¢ bonds we get nine charged resonating structures and two isovalent uncharged resonating structu! | the resonance hybrid. | H H H H H H—O—H yeC—H HeC—H Hec—y H—C—H ere e O- ee ~~ In an ethyl group there are two such C—H o bonds. We should have eight resonating st™ tures only for ethyl benzene, six of them are charged structures and the rest two are unch! structures, In the resonance hybrid of isopropylbenzene, we find only five resonating struct" two uncharged and three charged structures. This is because of the presence of only one C—!! «a bond @ to the benzene ring.Factors Influencing Electron-availabilit “ tert-Butylbenzene do bond on the C atom bor Me eS Not have an ny to-bond resonating structure as there is no O—-H nded to the ber nzene ring, Me Me Me Me H—C—H “ sy hus, . ‘ i ee ee th the hyperconjugative effect increnses negative charge density, ie., electron eel or pene ring. Therefore » Xt is expected that the greater the number of negatively = ing structures in a hybrid, the greater will be the electron density in the benzene recut decreasing order of the number of charged resonating structures of the elkylbenvense discussed above is : Methylbenzene : 9, ethylbenzene Hence, the electron-releasing effe: + 6, isopropylbenzene : 3, tert-butylbenzene : 0. cts of the said alkyl groups are in the order of: methyl > ethyl > isopropyl > tert-butyl. Problem 4.20. The order of stability of @ ® e ; @ my (CHs)sC > (CH;),CH > GucH, SCH, b: (CHs)36 > (CH)),CH «> OOROH, > CHy Explain the stability order in both the cases, Solution: (a) Two effects are to be considered for explaining the given order: (i) Hyperconjugative effect We know that the more the number of contributing structures of comparable energy in a resonance hybrid, the greater is its stability. In tert-butyl cation, there are nine a-C—H sigma bonds and henee its resonance hybrid consists of ten resonating forms, nine of which are uncharged structures; we shall have six similar resonating forms in isopropyl cation, three such in ethyl cation and none in methyl cation, Therefore, the order of stability of the carbenium ions is as given in the question. (ii) Inductive effect This can also be explained by +I effect of the methyl groups, Thus, due to the +I effect of the three methyl groups attached to the positively charged carbon atom of tert-butyl cation, its charge is neutralised to a greater extent than that of isopropyl cation which possesses only two methyl groups for such an effect; this charge neutralisation effect is still less in the case of ethyl cation as it contains only one methyl group and it is least in methyl cation because it does not. have any electron-releasing group attached to the positively charged C atom. — This is represented pictorially in Pig, 4.9. (b) The given stability order can be explained by hyperconjugative effect.cs ral Organic cy, 176 Advanced Gi 176 mamemmemneemmemmeneccemmmvcnenmencscmemnenes /\(1Viir0¢ ( (CHg)3G has nine resonating forms without odd electron in its reson, (CHg)2CH has six such structures, CH3C Hz possesses only three structures without or, and methyl radical has none, Therefore, the order of contributing structures in thy hybrid of the above radicals is: (CHg)3C > (CHs)2CH > CHsCH3 > CHy Hence the stability order of the said radicals is the same as given in the question The factor which considers the sheer bulk or volume of atoms and groups involved active part of a chemical species and their spatial arrangement in connection with its » acidity, basicity, the rate and stereochemistry (Ch. 9) of its reaction as well as th reaction product may be called the steric factor. It plays an important role in u reaction mechanism (Ch. 11). The volume of atoms or groups on the reacting part of ar species has varied types of effect on the stability and reactivity of the species and th may be called steric effects. Four types of steric effects may be considered here: (i) St (Gi) Steric acceleration, (iii) Steric retardation, (iv) Electron-availability. If the constituent atoms and groups of a chemical species require more space available for them, owing to their bulky nature, then mechanical interference amongst tli and atoms takes place and the species is said to be under steric strain. Consequently, < of normal bond angle occurs, which in its turn, brings instability to it. Owing to the great » of the tert-butyl group and small available space for it, 1,2,3-tri-tert-butylbenzene is under st and very difficult to prepare. However, the strain will be discussed in the Isomerism (Chapter 9) in detail. Note Even small groups may cause steric strain owing to the overlap of their van der WW radii known as van der Waals strain. This strain develops repulsion between two such bonded atoms or groups which is called sterle repulsion. For example, anti-conformatc 2,3-dibromobutane is the most stable conformation since amongst other factors least amour steric repulsion is found in this conformation in comparison to that in fully eclipsed a conformations. Sometimes not the bulk of the groups and atoms but their very spatial arrangement i species create distortion of bond angles and hence develop steric strain in it which is know Internal strain or -strain. This is found in small rings. Thus, cyclopropane has planar trier ring structure having C——C— C bond angle 60°, though all the Cs are in sp?-hybridised and therefore expected bond angles are 109°28’, Hence cyclopropane ring has [-strain and makes the compound highly unstable and very reactive. ‘Transition states too (Ch. 11) sometimes possess I-strain, Strained chemical species try to avoid the steric strain and thus react readily to produc: strained species. When a steric strain speeds up a reaction, it is said to be steric acceleration ©Factors Influencing Plectron-9vaila>ility LLL. as let yada array ts assisted the reaction to occur, itis called steric assistance. Tertiary alist se i boats of vier stops form tertiary catbenium fons readily when they are hydrolysed: 1 weir tendency to get ri atl 11). Steric strain, therefore, has assisted me ‘© get rid of the B-strain (Back-strain, Chapter 11) rt ert-alkyl halides to form carbenium fon readily. Thus, it is an example of steric assistance as well as dat acceleration. A sheer phy part of the substi is called steric ret val blockage owing to the greater bulk of the groups and atoms on the reactive ate hinders some reactions to occur o slows down the rate and the phenomenon a tardation or steric inhibition ot steric hindrance. a Nese ieee be the inductive and resonance effects of the substituted groups of 2, 6- substitu nzoic acid, it is very difficult to esterify. This is because of the steric hindrance owing to the crowding of bulky COOH group and two ortho substituents which physically block ROH to attack © atom of the —COOH group. It is needless to mention that the steric assistance for one reaction may be the steric hindrance for another reaction. When chloral (CCl;CHO) is hydrolysed with dil. alkali, gives chloroform via the intermediate written below within crochets: slow st cL Bie 9° Ou 7 a pi asco —C—k cl—c--o—H | > Cc + HCL > CHI; + HCOO a” Lah ou COS y Intermediate The presence of two bulky groups, CClz and OH, on the carbonyl C atom has assisted to break the C—C o bond between CCls and CH(OH)O~ groups. Thus, the steric effect is the cause for the formation of CHCl, which may be cited as an example of steric assistance; while the same effect, has hindered the stability of the intermediate species and therefore it is an example of steric hindrance too for the formation of the intermediate ion. Sometimes steric hindrance increases the electron availability on a particular atom or group in a chemical entity. In N, N-dimethyl-o-toluidine, three methyl groups are very closely spaced. ‘This creates steric strain in the molecule. To avoid steric strain—N(Me) group with its lone-pair CH CH 4 o/ CBs Cpr RS 3 of electrons rotates about the C—N bond axis. And as a consequence the filled p orbital of the 'N atom is no longer parallel to the six p orbitals of the sp* carbon atoms constituting the benzene nucleus, ‘Thus, delocalisation of the filled p orbital of the N atom cannot occur. This incre the electron-availability on the N atom; whereas in aniline those electrons are less available. 4 there is no steric strain, the electron-pair on N atom in aniline completely delocalises. Thus, electron-availability on N atom in aniline is low. Org, Chom.-12 ?5 Advanced General Oran Problem 4.21. Dipole moment of: a. HC O is 2.27 D but CH3CHO is 2.72 D. b. CHsCH,CH,CHO is 2.72 D but CHs— CH= CH— CHO is 3.67 D. ©. Ph—NH is 1.53 D, Pl—NOp is 3.95 D but p-NHy—CoHi—NOv is 6,19 1 d. CHj—CH— Cl is 1.44 D but CH=C— Cl is 0.44 D; explain the values, Solution : See Sec. 4.8.4 and 4.8.5. a H eked iN a es: | H—o~ 4} pot Pe fo ZN 1a HOH HH HOH Hyperconjugative effect increases the dipole moment of CHsCHO. H @ | H is b. H oo ‘CH: am i Ly H—C=CH— CH: { 0 ete, H H H Hyperconjugative and conjugative effects are responsible for the high dipole moment of tonaldehyde. Resonance interaction between —-NOz and ——NHp groups in the same direc e responsible for the high dipole moment of p-nitroaniline which is not equal to the sum of and 3.95 or 5.48 D as shown below: R e NH NH) Ne Ne \, La Nn oe % d. In CH2=CH—Cl and in H— ‘C— Cl p — x conjugation involving lone p electrons on Cl changes the direction of dipole moment as expected from the —I effect of Cl Contributing ionic structure decreases the dipole moments of the compounds. x @ [CH <—} CH)—CH=Cl'] = CH) CHCl overall direction #=144D overall direction #=044DFactors Influencing Electron-ayailab jit) SS |) Problem 4.22. Com trans-2-butenc Solution: is-2-butene and trans-2-butene have high hyperconjugative stability. ‘The eit ver orodee eke Stain. So stability order is trins-2-butene > cit-2-butene > 1-butene. They wil ce bas Same alkane, n-butane, on hydrogenation. The most stable alkene has least nto anal tha ratte; heat change on hydrogenation will be the lowest in the case of '7s 2butene and the highest in the case of 1-butene as shown by the graph given below: L-butene pare the heat of hydrogenation values of 1-butene, cis-2-butene and cis-2-butene trans-2-butene+—_ 1) of sepa ‘AH cis-2-butene E n-butane ‘The modern definition of aromaticity is the ability to sustain induced ring current by a flat or nearly flat cyclic system with (4n+-2) delocalised m electrons, jpaced gnc fel where n is zero or any whole number. inside the ring Benzene is the ideal molecule possessing aromaticity. It has Ning eument a planar hexagonal ring structure with (4x1+2) or 6 electrons. There are six p orbitals one on each sp? C atom. All the 6p orbitals being parallel to each other and perpendicular to the plane of the molecule, they form a delocalised electron cloud below and above the plane (See Sec. 4.4.8). When a magnetic field is applied perpendicular to the plane of the benzene molecule, the circulation of delocalised x elec- trons takes place in one direction and thereby a ring current, which induces’a counteraction magnetic field inside the ring, is Filed nt produced (Fig. 4.10). Thus, benzene has the ability to sustain ee indused|cing Gurren’. ig ADs Fined rg eurrent benzene Systems possessing aromaticity have some special physical and chemical properties which are also collectively known as aromatic character. 1, Chemical stability in excess of analogous acyclic unsaturated system, e.g. (a) Although aromatic compounds have unsaturated ring, electrophilic substitution rather than addition reaction with polar reagents like HNO3, H2SOq, Bro occur and the unsaturated ring does not get ruptured. (b) Resistance to oxidation by aqueous KMnO4, HNO3 and all except group VI oxidising agents (V20s, etc.)- Unusual thermal stability: (a) Low heat of hydrogenation, (b) Low heat of combustion,> | mes Alvaro General Oryayi, 3. Physical measurement: (a) Diamagnetic susceptibility, (b) Unique proton magnetic resonance spectra 7.85 4 in ppm. The amount of aromati above. There are three theories regarding the cause of aromaticity: y of a system is thus measured by considering the propa, (i) Valence Bond theory: This theory tells us that resonance stabilisation of structure is the cause of its aromaticity. The greater the resonance energy of snc greater is its aromaticity. Thus benzene is aromatic because it is a stable resonance: hy canonical structures with 150.8 kJ/mole resonance energy. Plana (ii) Molecular Orbital theory: According to this theory high delocalisation ener cause of aromaticity of planar cyclic systems. Six p orbitals, one from each sp? C atom, remain perpendicular to the plane of the hex, fa " benzene ring and parallel to each other. All the six p A.O.s overlap to form six delocs,. M.O.s—three bonding and three antibonding. The three bonding M.O.8 accommodate all the electrons as shown in Fig. 4.3, ‘The three bonding M.0.s have ten lobes (m — 2; 2 — 4; and m3 — 4). Th their combination is an annular electron cloud, ie,, negative charge sheet belo plane of the benzene ring, Therefore 1 electrons of benzene are highly delocalised and it possesses high deloca energy which is the cause of its aromaticity. (iii) The Hiickel (4n+2) Rule: On the basis of M.O, theory Hiickel stated that the presence of (4n+ 2) delocalised 7 electrons in a flat or nearly flat cyclic system is the cause of aroma and is known as Hiickel rule. Here n may be 0, 1, 2, 3, etc., whole number. According to (4n + 2) delocalised m electrons of a cyclic system develop high delocalisation energ resonance energy in it. A species to be aromatic should therefore satisfy the following criteria: 1. The species must be planar. 2. Tb must have a cyclic structure. 3, It must contain (4n +2) delocalised 1 electrons; where n = 0,1, 2,3, etc. Putting 0, 1, 2, 3, etc., for n in (4n +2), we get 2, 6, 10, 14, etc, and these mo called Hiickel numbers. Thus a compound to be aromatic it must have a cyclic planar sir containing Hiickel number of delocalised 7 electrons in a closed shell. Thus the rule to monocyclic, fused ring, heterocyclic, and cyclic ionic systems. From simple LCAO-MO theory we get a direct and simple explanation for the Hiickel (n rule, If we closely look at the energy level diagrams (ignoring ¢ electrons) for the even-m monocyclic conjugated polymethines of (—C—H),, type (where n = an even number, C:!! CoH, CsHs, etc.), we shall see that there is a symmetrical distribution of a strongly bond non-degenerated A level, a corresponding strongly antibonding non-degenerated B level and “ of degenerated E levels between them; each of the degenerated E levels has either two bo? or two non-bonding or two antibonding M.O.s as shown in the next page : applicCyclobutadiene . Benzene Git Gores) Gath Gite Cyclooctatetra Gy, Gites) pla Fig. 4.11, MLO. energy diagram for Cy, Cll and planar Cy Now, an aromatic system req uration having all electrons pair: red, each of the occupied degenerated E levels should contain 4 electrons, two 7 electrons in each of thi 1e degenerated orbitals of the level. Hence the general con- figuration of such a system may be written as (A)? (WEx)4({Ea)*--- (PE,)4 since it is necessary to fill up the lowest non-degenerated A level and then to fill up completely the first ‘n’ pairs of degenerated levels above it. Thus for benzene, A level will contain 2 electrons and E, level will contain 4 electrons. Similarly, a system having filled second Ep level will have 2 electrons in A level, 4 electrons in Ey level and 4 electrons in E2 level, so there will be 2 x 4 electrons in two degenerated E levels. For a system having filled Bs level, therefore, will have the configuration (WA)? (VE1)*(YE2)4(WEs)4, i.e., no. of m electrons will be 2-+3 x 4 = 14. So a system having E, level filled, will have 2 +n x 4 or (4n-+2)m electrons. Therefore 4 the number of the filled degenerated levels. w (say) luires to hold all 7 electrons paired up. To attain a close config- is a number which indicates Benzene has 6 7 electrons. The number follows (4n+2) rule; here n = 1. These are in a closed shell and all the constituent atoms of benzene are in one plane. Hence benzene is aromatic. Application of the Hiickel rule to decide whether a species is aromatic or not, is given in the problem written below: Problem 4.23. Are the following compounds aromatic? (a) Naphthalene, (b) Furan, (c) Pyrrole, (d) Pyridine, (¢) 1,3-Cyclopentadiene, (f) 1,3- Cyclopentadieny] anion, (g) Cyclooctatetraene, (h) Cyclopropenyl cation, (i) Cycloheptatrienyl cation. Solution: (a) Naphthalene, C1oHs, is a resonance hybrid of the following canonical structures with 255.4 kJ/mole of resonance energy. Owing to resonance stabilisation, naphthalene is aromatic.152 OOOO, Advanced General Organ: ‘Ten C atoms of naphthalene lie at the corners of two fused hexagons. All the ¢, hybridised and each of them bears one-electron p orbital which is perpendicular to the," plane of naphthalene on which C and H atoms lie, Thus ten parallel p orbitals overlay , P her to forin (4x 2+2) or 10 delocalised m electrons. Because of the presence of Hiici (i0) of delocalised 7 electrons in the flat eyclic system of naphthalene, it Is aromatic, to the Hiickel theory of aromaticity. nique From the experimental standpoint, it has high chemical and thermal stab spectrum and it has the ability to sustain induced ring current. Hence it is aromatic (b) The structure of furan is : pAo. EH pao ‘The O atom and each of the four C atoms are in sp” hybridised state forming a flat pen! structure. One of the two lone-pairs of electrons of the O atom is in sp? orbital and the oth p orbital, Four p orbitals of four C atoms, each containing one electron, and filled p orbita atom are parallel to each other and perpendicular to the plane of furan. ‘Therefore furan has 4p electrons from four C atoms and 2p electrons from the O atom it has 6 delocalised 7 electrons which is a Hiickel number. Hence it is an aromatic comp according to the Hiickel theory of aromaticity. It has also resonance stabilisation as shown b Because of the resonance stabilisation furan is aromatic. (©) electron Zao Negative charge sheet AO. t t eG elow and above the plane ines fae ee sad. 6 delocalised Flat local 1 electron ‘electrons ee Hiickel no. of delocalised 7 electrons in pyrrole being present in a planar eyclic struct" is aromaticFactors Influencing Electro, a Flos Infuencing Electron eae memmmmemesmmammmmacmmamasnsan 3 pAO. Witte / electron r 0 cos o { 0) ine / PAO. 6 delocalised 1 electron electrons Since there are 6 (a Hiickel no, ) delocalised 1 electrons in planar hexagonal structure of oP pyridine, it is aromatic, sp2_P (e) sp? sp Puckered structure Since there is no delocalisation of Hiickel 1 no. of 1 electrons, cyclopentadiene is not an aromatic compound. PBR o©f/ \ —H PDP P-orbital electrons 0 tee Yep bybridised — Planar structure 6 delocalised zr electrons 4 C atom It has planar cyclic structure with 6 delocalised x electrons. Hence Hiickel rule tells us that cyclopentadieny] anion is aromatic. (g) , = Cyclooctatetraene has 8 p electrons. It has a puckered ring structure and proper overlap of p electrons is not possible. Hence it is not an aromatic compound. (viv Cyclopropenyl cation has (4x 0+ 2) or 2 7 electrons, where n= 0. Hence it is aromatic. 2 —sp?C H @ Flat structure le on each of 6 delocalised z electrons 6 pA.0.s of 6 C atoms So there are 6 delocalised 7 electrons. Hence it is aromatic.Lo p-aromalis Fic compounds may be elossified as aromatic, 1 of the melectron energy change as stated below Ifa conjugated eyelic compound has lower electron energy than ils open chaln anainy,, compound is said to be an aromatic compound, When 1,3,5-hexatriene iy converted y, by the hypothetical abstraction of two H atoms, the electron energy diminishes in and hence benzene is classified as aromatic, I contains higher m-electron energy than 1) «, other hand, if a conjugated cyclic compound contains higher melectron energy than iv» ,, counterpart, the compound is called anti-aromatic; in fact, planar rons are called anti-aromatic. 1,3-Butadiene, a 4m electron 1,3-cyclobutadiene which is acyclic planar 47 electron system; the former on hypothetical, cyclic conjugated wyitc ter, i6 analoy CH 4 a CH 5 | UM iaetar (6 OH ye na S ye , IT to the latter by the abstraction of 2 H atoms gives a less stable and a more energetic sys r-electron energy increases through the conversion. Hence eyclobutadiene ie an anti-aror compound. If in the case of hypothetical conversion of an acyclic conjugated system iniv conjugated system, the 7-electron energy remains unchanged, the cyclic system is said to b aromatic. Hypothetical conversion of 1,3,5,7-octatetraene gives rise to 1,3,5,7-cyclooctatx This is a non-planar cyclic system and contains the same amount of m-electron encsy: acyclic counterpart. Hence cyclooctatetraene is a non-aromatic compound. ‘Annule’ means ring and ‘ene’ indicates C=C. Monocyclic hydrocarbons havin single and double bonds in their structures are called annulenes. Cyclobutadiene is a (4) « since it contains 47 electrons. Similarly, benzene and cyclooctatetraene are [6] and (8 respectively. [10] and [14] annulenes are drawn below and their nature is stated. 2 3 6 4 5 (10) annulene [10] annulene It has 1,6-(H/H) interaction Non-planar and non-aromatic [14] annulene and hence it is not planar. It is, therefore, non-aromatic. Planar and aromFactors Influencing Electro availability 185 In fact : ¥ Rina ees which is extra stable by virtue of being cyclic is nowadays classified aro uch kind. If in a cyclic 7 system one or more points are matics are of si atom but the system is still capable of significant overlap of p orbitals insulated by a saturated Ge He tasdlating zap or gaps, thy eyten Waid to be matics ar The known homoaroi @ © cyclic non-planar ions. Two examples are given below: oe 18.1.0] hexyl cation, It is a two-electron system involving 3 atoms. ii 8 ay oy bOI ag_.|-@ Bicyclo[5.1.0] octadienyl cation The geometry of these two ions thus brings extra stability to the is such that it permits significant ovarlap of p orbitals and system. When a lone pair of electrons on an atom constitutin, its aromatic character, Therefore, the compow ig an aromatic ring is utilised to preserve the lone pair of es is not readily available for donation to other species. ind will be a very weak base. For this reason pyrrole is a very weak base, the lone pair of electrons on the N atom of the pyrrole ring is a part of the six delocalised + electrons. If the N atom donates the same, it will no longer be aromatic; it will be unstable then and at the cost of instability, it does not want to show its base character. The dipole moment of a molecule is a direct consequence of its electronic configuration. The perturbation of the electronic configuration by the factors influencing electron-availability within a molecule is directly reflected in the magnitude and direction of the dipole moment. In this section we shall discuss the following effects in connection with the molecular dipole moments (i) Induction effect (ii) State of hybridisation of atoms and their electronegativity (iii) Polarisation of non-bonding electrons (iv) Hyperconjugative effect (v) Resonance effect (vi) Aromaticity.ro Advanced General Organie cy This effect is a universal one, no matter whether the compound is aaturated oF yy aromatic ot aliphatic and homocyclie or heterocyclic. However, when « polar group i molecule, it influences the dipole moment of the molecule; its induction effect. develo... bond moments on the bonds joined to the group directly or on some classes of compounds. directly. Let ws consice A. Molecular moments of halomethanes: If we consider the primary dipole moments of and C— Cl bonds, we shall find that the dipole moment of CHCl, will be 1.87 D. The cijeujy, are shown below: ee We know that jicc1, is 0.00 D. Therefore we can say fic magnitude and opposite in direction. Again ic Higa = 1.56 D. So naga = 1.87 D. Actually pone, is 112 D or something like « result is explained by a change in the magnitudes of the primary dipoles of O—H and ¢— under the influence of the permanently polar C— Cl bonds. The accumulation of polay (—¢ bonds in the molecule develops induced dipole moments on each of the C—Cl bonds in y carbon is the negative pole and Cl is the positive pole which in their turn considerably 1, the effective moments of C—CI bonds and at the same time relatively small induced «ie moment develops in the C—H bond with the polarity H+C~; as a result of the group moment of CCl is much less than ic— cr and naturally picrtciy is much less tha The explanation given for the jicric1, also holds good for other di and tri holomenthancs a and Lect, must be ¢« n= 0.31 D and pe—c1 = 01.56 H le@D at Gar ) cl 6- and 6+ are charges for primary dipoles; 6 and 6; are charges for induced dipoles own the presence of two other C—Cl bonds, Each C—Cl bond has its own primary dipole aul induced dipole though not shown in the figure. The effective C—Cl bond dipole = ( bond distance in Ax (5 ~ 6) in es. b. Dipole moments in homologou jes: It has already been stated that the presence o! p» groups induces small dipole moments in C—H bonds. As the induction effect falls rapid the increasing distance, induced moments of C—H bonds drop substantially with the dista! of these bonds from the polar group. Thus, in ethyl chloride induced C—H bond monet! methylene group is 0.09 D, while that in the methyl group is 0.02 D. Hence effective C-—H! bo! moment changes as the distance between the polar group and the C—H bond increases. [0 ls" after Cs atom C—H bond does not experience any induced moment. The dipole moment of compounds of a homologous series also depends on branching 0!" chain. The molecular moment of isopropyl derivative is greater than that of n-propy! desi"! and sec- and tert-butyl derivatives have higher dipole moments than n-butyl derivative. !* can be explained by the fact that in a branched compound the terminal C-—C and ( bonds are closer to the polar group than those in the compounds having unbranched ‘As a consequence the induced bond moments are greater in the former case than in the 10!” case. Besides this, polarisability of bonds changes with branching and that has an effect 0” molecular moment however small it may be.©: Dipole moments tn aromatic groups on o-positions show dipole m- and p-substituted isomers do moments and thereby effective For example, o-dichlorobenzene has the e setles ancl induction etfect; Aromatic compounds having polar moments which differ from calculated values; whereas those of not differ. It has been argued that polar o-groups induce dipole bond moments change. ie a *xperimental j1 = 2.27 D but the calculated y (without Berner el tsmment) Peso OY yin Cnn cede Maem aca tegen Ea calculated value becomes 2.30 D. SCREEN Rita tronegativities on dipole moments Though bond moments are principally responsible for the molecular dipole moments yet there are other factor e also. The first major factor is the asymmetry of charge in the bonding electrons that arises owing to the differences in electrone, gativities of the bonded atoms. Electronegativities of bonded atoms depend on the state of hybridisation, So the bond moments vary appreciabl atoms. The more the s character of the ativity of the atom and the table illustrates the fact, ly with the change of state of hybridisation of the bonded hybridised state of an atom, the greater is the electron: higher is the magnitude of the charge on the poles. The following ‘Table 4.1 State of hybridisation of bonded atoms and bond moments Molecule Hybridisation of carbons inD Bond length in pm. be a CHy sp? H—C 031 1094 (4c) +— H.C=CH—H sp? H—C 063 108.7 (HC) +— Ea H—C 105 1058 (H—c) + CHs—CH=CH, Cap —C gy? C—C 068 150.0 (c—c) + CH)>=CH—c: C sp’—C sp C—C 115 | 143.0 (C—o) + CH;—C=CH C sp°\—C sp - C=C 148 1460 (c—o) As the bond moments have different values owin; the molecular moment also changes. ig to the change in the state of hybridisation, Another major factor for the molecular dipole moments is the polarisation of the non-bonding electrons. For example in NHs, the resultant of HN bond dipoles and the dipole from the n ¢s on the nitrogen atom act in the same direction and as a consequence ammonia molecule has a high dipole moment, 1.47; on the other hand, in NF the resultant of N—F bond dipoles is pposed to the dipole of the n es on the N atom and naturally molecular dipole moment of NF is small, 0.23D.For the state of hybridisation as well as for the n electrons the direction of dipole mon, furan is opposite to that of pyrrole in which the lone pair of electrons are involved for preser, the aromatic character of the molecule. IGS — GS Gs « u f u IS 4 GS oe C—I and C—S bond moments are larger than expected from electronegativity valus (0 12.5 eV, S : 2.8 eV, and I : 2.5 eV). The presence of n electrons on I and $ atoms and the: polarisation are the causes for the high moments of C—I and C—S bonds. However, ti total moment of a molecule having the lone pair of electrons can be calculated by the forms Hiotal = Hlone pair +3086: Ubonds Where 0 is the angle between directions of the bond mons and the lone pair moments. Hyperconjugative effect develops charge separated structures which are responsible for tit large dipole moments of the molecules having hyperconjugative effect. For example, 110% 2.27 D and picscHacuo = 2.73 D, whereas ics — on—=cx—cuo is 3.67 D. Dipole mom of formaldehyde is due to the resonance effect and the effect of polarisation of n electrons; whe in other cases hyperconjugation has played a good role along with the effects which are acte! formaldehyde. ala, y Fy We 6 | g i I u—o Lh — pane 5 <> ete. 1 < “ Hae 2.27DH Owing to the R effect, the mo: id ali : loments of groups have arly substituted ‘ ich wae pounds (See Table 2.7). We may recall pit, in CHy—NHp and in Ph—Nk,, which are 1.46 D and 1.53 D Tespectively, The difference is called the resonance moment. However, hybrid of several resonating structures, the to the resonance hybrid. For example vinyl dipole moment than ethyl chloride (4 = 2.05 D); in the former case Reffect esponsible for the dipole moment values. kL ae x ® (Chh}=cCH— a: CH» —CH=Ch] = CH — if a molecule is a resonance HCl — overall direction In ethynyl chloride, the direction of the dipole moment is as well as high electron: reverse owing to the resonance effect \egativity of sp hybridised carbons. overall direction u=044D in compounds where resonance interact R effect plays a very vital role i ‘tion or through resonance takes place as in the case of p-nitroaniline (4: 6.10 D) PhNH) has: dipole moment 1.53 D whereas PhNO2 has 3.95 D. Since the group mon ments of NHz and —NQp act in the same direction, one may expect that the dipole moment of p-nitroaniline will be the sum of the two moments but itis greater than the sum of the moments, Resonance interaction involving NHy~ and ~ N02 groups is held responsible for the increase in the dipole moment. ‘The difference between the actual moment and the calculated moment i called the resonance interaction moment (6.10 D — 5.58 D = 0.62 D). NED Nip @ ne ait) >, PENI Owing to the steric inhibition of resonance dipole moments of compounds are found to be less than what it could have been if there were no steric inhibition of resonance.