CHAPTER 7BASIC PRINCIPLES OF ORGANIC CHEMISTRY Q1. Which compounds are the simplest organic compounds?

Hydrocarbons are the simplest organic compounds. They are consisting of elements like C and H. Different organic compounds can be synthesized from hydrocarbons by displacing H atom of hydrocarbon by different functional groups. Thus hydrocarbons and their derivatives constitute organic chemistry. Q2. Explain tetra-covalence of carbon. The electronic configuration of carbon is as follows:

1s

2s2

2px 2py 2pz

Thus in ground state of carbon, there are Therefore, in order to attain stable electronic configuration like inert gases, carbon atom should lose or gain four electrons. 4+ 4 But in order to do so, very large amount of energy is required and it fails to form C or C ion. [ Note to form cation 4+ atom has to absorbs the energy as a result C ion has very large energy so it cannot form while to form anion atom has 4to release the energy so in order to form C carbon atom has to release very large amount of energy therefore it is not possible to form anion.] It is found that carbon atom forms four equivalent covalent bonds with other elements by sharing its four unpaired valence electrons. Thus carbon atom exhibits tetra-covalence. The tetra-covalence of carbon can be explained as follows. In excited state of carbon, one of the electrons from electron-pair of the 2s-orbital is excited into the vacant 2pz orbital. Thus in the excited state, carbon atom has four unpaired electrons in its valence shell. If these four unpaired electrons are used to form covalent bonds, the four covalent bonds formed would not be equivalent as these four unpaired electrons belong to different kinds of orbitals, i.e. s and p-orbitals. However, it is an experimentally established fact that all four covalent bonds formed by carbon are chemically identical or equivalent. [ this fact was prove when by x-ray spectroscopy structure of methane was studied it was observed that in methane molecule all C-H bond are of the same size and each bond is directed towards the angle of tetrahedral and 0 H-C-H bond angle is 109 28. This equivalence of four covalent bonds can be explained on the basis of a new concept of hybridization. Q3. What is called hybridization? The mixing of the atomic orbitals of the same atom with slightly different energies resulting in the formation of same number of new orbitals of equal energy and identical shape is called hybridization. The new orbitals so formed are called hybrid orbitals. 3 Q4. Explain sp hybridization and shapes of methane and ethane molecules. 2 1 1 1 1 The excited state E.C. of carbon is: 6C: 1s 2s 2pX 2py 2pz

1s

2s

1 1 2p x 2p y 2p z 1

Excited state In this state, one 2s and three 2p-orbitals of carbon are mixed and form four new orbitals having same shape and same 3 energy called sp -hybrid orbitals. 3 3 3 3 6C: 1s sp sp sp sp 1 1 1 1 1s2 2s 2px 2py 2pz Hybrid state These hybrid orbitals are arranged towards the four corners of a tetrahedron at an angle of 10928' between any two adjacent of them. 3 Now these four half-filled sp -hybrid orbitals of carbon atom overlap with four half filled 1s-orbitals of four hydrogen atoms. Thus combining atoms will share their valence electrons to form covalent bond. The electrons which are shared to form a covalent bond have opposite spins. Thus all four C-H bonds formed in methane are equivalent. 0 The C-H bond angle in methane is 109 28. The shape of methane molecule is tetrahedral. 3 The four C-H bonds in methane formed by sp -1s overlap are called bond. Sigma bond: A covalent bond formed by end to end overlap of orbitals along inter nuclear axis is called bond. OR A covalent bond formed by greater extent overlapping of atomic orbitals of combining atoms is called bond.

In ethane molecule (CH3-CH3), both the carbon atoms are in sp3-hybridization. 3 An overlap between two half-filled sp hybrid orbitals of both carbon forms a C-C, bond. 3 While remaining three sp -hybrid orbitals of each carbon overlapped with half-filled 1s-orbitals of six hydrogen atoms containing electron of opposite spin to forms total six equivalent C-H -bonds.

sp3
1090 28

sp

1090 28

Dashed line indicates tetrahedral shape

sp3
sp 3
1090 28

sp

sp 3

sp

1090 28

sp 3

Q5. Explain sp hybridization and shape of ethene molecule. The excited state E.C. of carbon is,: 1s 2s 2pX 2py 2pz
2 1 1 1 1

1s2

2s

2px1 2py 2pz1

Excited state In this state, one 2s and two 2p-orbitals of carbon are mixed and form three new orbitals having same shape and same 2 energy called sp -hybrid orbitals.

1s2

2s

1 1 2px 2py 2pz

Hybrid state 0 These hybrid orbitals are arranged towards the three corners of a triangle at an angle of 120 between any two adjacent of them. Here, 2pz-orbital of carbon atom does not take part in hybridization and it is arranged perpendicular to the triangular plane of hybrid orbitals.
bond
2pz
sp
sp
2

2pz
2

120

120

bond

sp2 1200

bond

C
2

bond bond

C
H

In ethene molecule (CH2 = CH2), both the carbon atoms are in sp -hybridization. 2 An overlap between two half-filled sp hybrid orbitals of both carbon forms a C-C, -bond. 2 While remaining two sp hybridized orbitals of each carbon overlapped with half-filled 1s-orbital of four hydrogen atoms containing electrons of opposite spin to form total four equivalent C-H -bonds. Thus combining atoms share their valence electrons to form covalent bond. The electrons which are shared to form a covalent bond have opposite spins.

The unhybridized 2pz-orbitals of both the carbons each of them containing one unpaired electron overlap with each other and form a bond. Ethene molecule is planar in shape Pi-bond: A covalent bond formed by side-ways overlap of orbitals perpendicular to the inter nuclear axis is called nbond. OR A covalent bond formed by unhybridized orbitals is called n-bond.
1 1 2px 2py 2pz 1

Q6. Explain sp-hybridization and shape of ethyne molecule.

1s

2s

The excited state E.C. of carbon is: In this state, one 2s and one 2p-orbitals of carbon are mixed and form two new orbitals having same shape and same energy called sp-hybrid orbitals.

1s2

2s

1 1 1 2px 2py 2pz

Hybrid state These hybrid orbitals are arranged linearly at an angle of 180 between them. Here, 2py and 2pz orbitals of carbon atom do not take part in hybridization and they are oriented perpendicular to each other as well as perpendicular to the axis of hybrid orbitals. In ethyne molecule (CH CH), both the carbon-atoms are in sp-hybridization. An overlap between two half-filled sp hybrid orbitals of both carbon forms a C-C, bond. While overlap of remaining sp-hybrid orbitals of each carbon with half-filled 1s-orbitals of two hydrogen atoms ; containing electron of opposite spin forms total two equivalent C-H bonds. Thus combining atoms hare their valence electrons to form covalent bond. The electrons which are shared to form a covalent bond have opposite spins.
2py
180
0

90

2py
180
0

90

2pz

2pz

sp

sp

sp

sp

2pz

2py

2pz

2py

The unhybridized 2py and 2pz-orbitals of both the carbons each of them containing one unpaired electron overlap with each other and form two bonds. Ethyne molecule is linear in shape.
bond 2py 2py bond
sp

sp

2pz

2pz

H
1s and 3p Nil Four - 109.5 Tetrahedral 25 or 1/4

bond

bond
bond

bond

bond

H
sp

Type of hybridisation Number of orbitals used Number of unused p-orbitals Bond Bond angle Geometry % s-character

sp3

1s and 2p One Three - One - 120 Trigonal planar 33.33 or 1/3

sp2

1s and 1p Two Two - Two - 180 Linear 50 or 1/2

Determination of hybridisation at different carbon atoms : It can be done by two methods, (i) First method : In this method hybridisation can be know by the number of bonds present on that particular atom.

Number of bond/s Type of hybridisation Examples :

1
3

2
2

sp

sp

sp

(ii) CH 2 C CH 2
sp 2 sp sp 2

(iii)

CH 3 CH CH CH 2 C N sp sp sp 2 sp 2 sp 3 sp 3

(iv) HC C CH CH 2 In diamond carbon is sp hybridised and in graphite carbon is sp 2 hybridised.

(ii) Second method : (Electron pair method) ep = bp + lp; where ep = electron pair present in hybrid orbitals , bp = bond pair present in hybrid orbitals Number of bp = Number of atoms attached to the central atom of the species
Central atom First atom H C=C Second atom H bp = 3 H Third atom H

Number of lps can be determined as follows, (a) If carbon has - bonds or positive charge or odd electron, than lp on carbon will be zero. (b) If carbon has negative charge, then lp will be equal to one. (c)for calculation of ep pi bond pairs are not considered. Number of electron pairs (ep) tells us the type of hybridisation as follows, ep 2 3 4 5 6 Type of sp sp2 sp3 sp3d sp3d2

Example :
(i) CH 2 CH
bp 2 lp 0 ep 2, sp

hybridisation

(ii) CH 2 CH
bp 2 lp 1 ep 3, sp 2

(iii)

CH 2 C CH 3 | CH 3 bp 3 lp 0 ep 3, sp 2

(iv) CH C

bp 1 lp 1 ep 2, sp

(v)

CH 3 CH CH 3 bp 3 lp 1 ep 4 , sp 3

(3) Applications of hybridisation (i) Size of the hybrid orbitals : Since s - orbitals are closer to the nucleus than p - orbitals, it is reasonable to expect that greater the s character of an orbital the smaller it is . Thus the decreasing order of the size of the three hybrid orbitals is opposite to that of the sp 3 sp 2 sp decreasing order of s orbital character in the three hybrid orbitals. (ii) Electronegativity of different orbitals (a) Electronegativity of s-orbital is maximum. (b) Electronegativity of hybrid orbital % s-character in hybrid orbitals
Orbital sp sp 2 sp 3 % s - character 50 33 . 33 25 s-character in decreasing order and electroneg ativity in decreasing order

Thus sp-hybrid carbon is always electronegative in character and sp 3 - hybrid carbon is electropositive in character. sp 2 hybrid carbon can behave as electropositive (in carbocation) as well as electronegative (in carbanion) in character.
CH 3 CH 2

CH 2 CH

sp 2

sp
Electronegative carbon having positive charge

Electropositive carbon

(c) Electronegativities of different hybrid and unhybrid orbitals in decreasing order is as follows

s sp sp 2 sp 3 p % s - character and electroneg ativity in decreasing order.

(iii) Bond length variation in hydrocarbons % of s orbital character

What is called homologous series? Give its characteristics. A series of organic compounds in which each consecutive member differs by specific CH2- unit is called homologous CHARACTERISTICS: 1. Every compound of the series contains same elements. 2. Every member of the series can be shown by a common general formula. 3. Any two consecutive members of series differ by CH 2 unit. 4. The difference in molecular weight of any two consecutive members of the series is 14 a.m.u. 5. Every member of the series has same prefix or suffix. 6. The chemical properties of every member of the series are same if they contain the same functional group. 7. The molecular weight of the member of the series increases as the number of carbon increases. Therefore, a regular difference is observed in their physical properties like boiling points and melting points. Q10. What are called isomers and what is called isomerism? Compounds possessing same molecular formulae but different structural formulae are called isomers of each other. The phenomenon of existence of compounds having same M.F but different S.F. is called isomerism. Isomerism is broadly classified into two main types: 1. Structural isomerism and 2.Stereo isomerism. Q 11. Write note: Structural isomerism. Compounds having the same molecular formulae but differing in connectivity of atoms are called structural isomers and this phenomenon is called structural isomerism. 1. Chain isomerism: Compounds having same molecular formulae but differe!lt carbon skeleton are called chain isomers and the phenomenon of existence of such compounds is called chain isomerism. e.g.
CH3 CH2 CH2 CH3
CH3 CH CH3 CH3

iso- butane Number of structural isomers Molecular Number of isomers Molecular Number of isomers formula formula Alkanes Monohalides C4 H10 C3 H 7 X Two Two C5 H 12 C4 H 9 X Three Four C6 H 14 C 5 H 11 X Five Eight C7 H 16 Nine Dihalides C8 H18 C2 H 4 X 2 Eighteen Two C9 H 20 C3 H 6 X 2 Thirty five Four C10 H 22 C4 H 8 X 2 Seventy five Nine C 5 H 10 X 2 Alkenes and cycloalkanes Twenty one C3 H 6 2 (One alkene + one Aromatic compounds cycloalkane) C4 H 8 C 8 H 10 6(Four alkene + 2 - cycloalkane) Four
C 5 H 10

n- butane

C3 H 4 C4 H 6 C2 H 6O

9 (Five alkenes + 4 cycloalkanes) Alkynes Two Six Alcohols and ethers 2 (One alcohol and one ether)

C 9 H 12 C7 H 8 O C3 H 6O C4 H 8 O C 5 H 10 O

Nine Five Aldehydes and ketones 2(One aldehyde and one ketone) 3(2 aldehydes and one ketone) 7 (4 aldehydes and 3 ketone)

C3 H 8 O C 4 H 10 O

3 (Two alcohols and one ether)

Aliphatic amines 2 (One 1-amine and one 2-amine) 4 (2- 1-amines, 1-2-amine and one 3amine) 8 (4-1-amines, 3-2-amines and one 3-amines)

7 (Four alcohols and three ethers) C 5 H 12 O 14 (Eight alcohols and six ethers) Monocarboxylic acids and esters Two (One acid and one ester) Three (One acid and two esters) Six (Two acids and four esters) Thirteen (Four acids and nine esters)

C2 H 4 O2 C3 H 6O2 C4 H 8 O2 C 5 H 10 O 2

2. Position isomerism: Compounds having same molecular formulae, (same C skeleton) but differing in position of functional group are called position isomers and the phenomenon of existence of such compounds is called position isomer eg:
CH3 CH2 CH2 OH
CH3 CH CH3

OH 1-propano l 2-propanol

3.Functional group isomerism: Compounds having same molecular formulae (C- skeleton) but differing in functional group are called functional group isomers and the phenomenon of existence of such compounds is called functional group isomerism. eg: CH3COCH3 (propanone ) and CH3CH2CHO (propanal), acetic acid and methyl methanoate Examples : (i) Alcohols and ethers (Cn H2n+2O) C2 H 6O CH 3 CH 2 OH H 3C O CH 3 C3 H 8O CH 3 CH 2 CH 2 OH C2 H 5 O CH 3 ;
Ethyl alcohol Dimethylether

n propyl alcohol

Ethyl methylether

C4 H 10O : CH 3 CH 2 CH 2 CH 2 OH C2 H 5 O C2 H 5 ;
n Butyl alcohol Diethyl ether

(ii) Aldehydes, ketones and unsaturated alcohols etc. (C n H2nO)

O C3 H 6O : CH 3 CH 2 CHO CH 3 C CH 3 ;
Propionaldehyde Acetone ||

CH 2 CH CH 3 O
1,2 Epoxy propane

CH 2 CH CH 2 OH
Allyl alcohol

(iii) Acids, esters and hydroxy carbonyl compounds etc. (Cn H2nO2) C2 H 4O2 : CH 3COOH HCOOCH 3 ; C3 H 6O2 : CH 3 CH 2 COOH
Acetic acid Methyl formate Propionic acid

CH 3COOCH 3 ;
Methyl acetate

CH 3 C HCHO
2 Hydroxy propanal

; 1 Hydroxy propan - 2 - one (iv) Alkynes and alkadienes (Cn H2n-2)

OH

O CH 3 C CH 2 OH
CH 3 C C CH 3
2 Butyne

||

C4 H 6 : CH 3 CH 2 C CH H 2C CH CH CH 2 ;;
1,3 Butadiene

H 2 C C CH CH 3
1, 2 Butadiene

(v) Nitro alkanes and alkyl nitrites ( NO2 and O N O )

Ethyl nitrite Nitro ethane C2H5NO2 : ; (vi) Amines (Primary, secondary and tertiary)

H CH 3 CH 2 N C H 3 CH 3 CH 2 CH 2 NH 2
Propan - 1 - amine

C3H9N :

N M ethyl ethanam ine

CH 3 CH 3 CH 2 N CH 3

CH 3 C H CH 3
Propan - 2- amine

N , N D i m ethyl m ethanam ine

NH 2 O

(viii) Oximes and amides

Acetaldoxi me Acetamide C2H5NO : ; (iv) Metamerism: Compounds having the same molecular formula but different number of carbon atoms or different alkyl groups on either side of the functional group (i.e., -0-, -S- and -NH-) are called metamers and the phenomenon is called metamerism. It may be noted here that metamerism occurs among the members of the same homologous series. For example, CH3

CH3

CH2CH2CH3

CH3

CH CH3

CH3CH2

CH2CH3

1-methoxy propane

2-methoxy propane

ethoxy ethane

CH3 CH2CH2CH3 CH3 S methyl propyl thioether CH3 S CH CH3CH2 S CH2CH3 CH3 isopropyl methyl thioether

di ethyl thioether

CH3 CH3 NH CH2CH2CH3 CH3 NH CH CH3CH2 NH CH2CH3 methyl propyl amine

CH3 isopropyl methyl amine

di ethyl amine

pentan-2-one and pentan-3-one are also considered as position isomers. Concept of metamerism can also be extended to esters in which no. of C atoms on the both end of the group may be same or different. Tautomerism arises due to migration of a proton from one polyvalent atom to the other within the same molecule. The two isomers thus obtained which exist in dynamic equilibrium with each other are called tautomers and the phenomenon is called tautomerism or desmotropism or allelotropism or kryptomerism or prototropy or dynamic isomerism. Some important types of tautomerism are: (a) Keto-enol tautomerism (b) Nitro-acinitro tautomerism. (a) Keto-enol tautomerism. There are several types of tautomerism but keto-enol tautomerism is the most important. In this type of tautomerism, one form (tautomer) contains the keto group (C= 0) while the other form contains the enolic ( - C = C - OH) group. Some important examples are:

O pentan-2-one

O pentan-3-one

In case of monocarbonyl compounds the proportion of enol form is negligible because the C-O pi bond is more stronger (364kJ/mol) than C-C pi bond (254 kJ /mol). Factors affecting the relative amounts of keto and enol forms in keto-enol tautomerism. The following three factors affect the position of equilibrium in keto-enol tautomerism. (i) Stability of the enol form. As stated above in simple aldehydes and ketones (i.e. acetaldehyde, acetone etc.) the amount of enolic form is negligibly small. However, if the enolic form is stabilized by intramolecular hydrogen-bonding (chelation), such as in 1, 3-dicarbonyl compounds, the amount of enolic form is much greater than in acetaldehyde or acetone. For example, in acetoacetic ester, the amount of enolic form is 7%.

Similarly, acetylacetone (i.e. a 1, 3-diketone) also exhibits keto-enol tautomerism but the amount enolic form here is much higher (76%) than even in acetoacetic ester. This is due to the reason that keto group is a much better electron- withdrawing group than the ester group

If the enolic form besides H-bonding is also stabilized by conjugation (i.e., enolic double bond is in conjugation with a multiple bond or a benzene ring), the enol content further increases. For example,

(ii) Steric hindrance. Another factor which determines the enol content is the steric factor. To illustrate this, let us consider the enol content of acetylacetone and -methyl acetyl acetone.

Although both the enols are stabilized by H-bonding, the enol form of -methylacetylacetone is destablilized to some extent by the steric repulsion due to the presence of the -methyl group. As a result, -methylacetylacetone has lower enol content (435 - 445%) as compared to that of acetylacetone (91-93%). (iii) Effect of polarity of solvent. Polar protic solvents such as water, methanol, acetic acid etc. Which form H -bonds with the carbonyl group of the-keto-form decrease the enol-content. On the other hand, aprotic solvents such as hexane, benzene etc. (or even the absence of solvent) increase the enol content. For example, enol form of acetylacetone is 76% in ethanol but is 92% in hexane. Essential conditions. For an aldehyde or a ketone to exhibit keto-enol tautomerism, it is essential that it must have at least one -hydrogen atom. Thus, acetophenone, butan-2-one and propionaldehyde all contain -hydrogen atoms and hence show keto-enol tautomerism.

In contrast, benzaldehyde, t-butyl phenyl ketone, benzophenone etc. do not show keto-enol tautomerism because they do not contain -hydrogen atoms.

H.W. Group the following compounds into chain position or functional group isomers: 2-amino propane, methyl ethanoate, propanoinc acid, 1-amino propane, dimethyl ether. Q12. Explain the fission of a covalent bond. The fission of a covalent bond can take place in following two ways. 1. Homolytic fission. and 2. Heterolytic fission. 1. Homolytic fission: In homolytic fission, a covalent bond breaks such that one of the electrons of bond pair goes with each of the bonded U.V. atoms. eg: Cl:Cl Cl. + Cl. As a result a species formed contains unpaired electron which is known as free radical. Free radicals are very reactive. 2. Heterolytic fission: In heterolytic fission, a covalent bond breaks such that the bond pair of electron remains with one of the previously joined atoms usually which is more electronegative As a result a species formed is either a carbocation or a carbanion. Carbocations and carbanions are very reactive. Q13. Explain the following terms: 1. Carbocation: A group of atoms containing carbon, in which a carbon atom possesses sextet of electrons and a positive charge, is called a carbocation or carbonium ion. + eg: CH3:Cl CH3 + :C Carbocation is produced as a result of heterolytic fission of a covalent bond. Carbocation is very reactive and has very short life. The shape of a carbocation is trigonal planar. 2 The positively charged carbon atom of a carbocation is in sp hybrid state. Carbocations are classified as 1, 2 and 3. + + + + The stability order of carbocations is: (CH3)3C > (CH3)2CH > CH3CH2 >CH3 i.e. 3>2>1
stability of carbocation 1 EWG EDG

2. Carbanion: A group of atoms containing carbon, in which a carbon atom possess octet of electrons and a negative charge is called a carbanion. + eg: CH3CHO H + :CH2CHO Carbanion is produced as a result of heterolytic fission of a covalent bond. Carbanion is very reactive and has very short life. The shape of a carbanion is tetrahedral; 3 The negatively charged carbon atom of a carbanion is in sp hybrid state. Carbanions are classified as 1, 2 and 3. The stability order of carbanion is (CH3)3C: < (CH3)2CH: < CH3CH2: <CH3: i.e. 3<2<1
stability of carbanion 1 EDG EWG

3. Nucleophile: The negatively charged electron pair donor species obtained as a result of heterolytic fission of covalent bond is called nucleophile. Nucleophiles are Lewis bases. eg: :OH, :NH2 :X etc. 4. Electrophile: The positively charged electron pair seeking species obtained as a result of heterolytic fission of a covalent bond is called electrophile. Electrophiles are Lewis acids. + + + + + eg: N02 , Cl , CH3 , SO3H , COCH3 etc.

Q14. Explain electronic displacement in covalent bond. The displacement of electrons in covalent bond of organic molecule can take place either in the ground state under the influence of functional group present in molecule or in the presence of proper attacking reagent. Under the influence of functional group present in molecule, a permanent displacement of electron is caused. Inductive effect and resonance effect are the examples of this type of electron displacement. Whereas, when a reagent is attacking a molecule, a temporary displacement of electrons takes place. Electromeric effect is this type of displacement. 1. Inductive effect: When a carbon atom is covalently bonded with a more electronegative atom, the bond becomes polar and this polarization effect is spread along the chain of carbon atoms within a molecule. The permanent displacement of the shared electron pair in a carbon chain towards the more electronegative group is known as inductive effect. Such polarization of bond caused by polarization of adjacent bond is called inductive effect. This effect is shown by a sign -->--. + + + 1 2 3

Cl where < < CH2 CH2 eg: CH3 + + + The inductive effect of C Cl bond decreases gradually as we move away from C-1 < <
+ + +

N H 3 NO2 CN SO3 H CHO CO COOH COCl COOR CONH 2 F Cl Br I OH OR NH 2 C6 H 5 H

I power of groups in decreasing order with respect to the reference H

ter .alkyl sec.alkyl pri.alkyl CH 3 H

3 2 2 2 3 2 2 3 2 + I power in decreasing order in same type of alkyl groups (3) Applications of Inductive effect (i) Magnitude of positive and negative charges: Magnitude of +ve charge on cations and magnitude of ve charge on anions can be compared by + I or I groups present in it.

1 Ipower of the group I power of the group 1 Magnitude of ve charge Ipower of the group I power of the group

Magnitude of ve charge

(ii)Stability of carbonium ion :+I effect tends to decrease the (+ve) charge and I effect tends to increases the +ve
3 3 3 2 3 2 3 charge on carbocation. (iii) Stability of carbanion : Stability of carbanion increases with increasing I effect.

(CH ) C (CH ) CH CH CH CH

3 3 2 3 2 3 3 Additional point for inductive effect: Inductive effect or simply I-effect is of two types : (i)-I-effect and (ii) + I-effect. - I-effect. If a group is more electronegative than hydrogen, then the group withdraws electrons from the C-chain towards itself (as compared with hydrogen). It is then said to have -I-effect. + I-effect. If a group attached to the carbon is less electronegative than hydrogen, it donates electrons to the C- chain. It is then said to have + I-effect. Characteristics of inductive effect. Inductive effect causes bond polarization and exhibits the following prominent characteristics: There is virtually no displacement of electrons in a C- H bond. It is because the electro-negativities of both the atoms are very nearly the same (C = 2.5, H = 2.1). Hence, the C-H bond is nearly covalent. Inductive effect always takes place between a carbon atom and an electronegative atom or group sharing only a pair of electrons. In other words, inductive effect involves only a single bond. Inductive effect is permanent and irreversible. The electron-displacement progressively decreases along a C-chain as the distance from the C atom directly attached to + + + the substituent increases, i.e., < < and so on. It is almost negligible after two carbon atoms from the carbon atom directly attached to the more electronegative element. The displaced electrons do not leave their orbital. Only the orbital is deformed a bit and this causes polarization. Different groups cause polarity to different extent.

CH CH CH (CH ) CH (CH ) C

The important applications are listed below:

1. It explains the polarity of covalent bond in organic compounds. 2. It explains the relative stabilities of reactive intermediates like carbonium ions, carbanions;etc. 3. It explains the relative strengths of acids and bases. 2. Resonance or mesomeric effect: The polarity produced in a molecule as a result of interaction between two - bonds or bond and a loan pair of electrons present on adjacent atom is called resonance effect. This effect is transmitted through chain. This effect is depicted by a symbol .

eg:

In case of compounds having conjugated -systems (having alternate. sigma and pi-bonds) electrons can flow from one part of the system to the other due to resonance. This flow of electrons from one part of a conjugated system to the other, caused by phenomenon of resonance is called resonance effect or mesomeric effect. This is of two types: (i) + R or + M effect and (ii) - R or - M effect. + M effect: If a group donates electrons to the conjugated : -system through resonance then it is said to have + R or + M effect. For example, Cl atom and OH group have + R or +M effect because they donate electrons to the conjugated systems as shown on in next page. Some other examples of the atoms or groups which cause + R or + M effect is: F, Br, I, NH 2'SH and OR. - M effect: Groups which withdraw electrons towards themselves through resonance are said to have - R or - M effect, such as Some other examples of the groups having"- R or - M effect are : NR3 - COOH,CN ,CHO,COR and SO3H. Relative Contribution of resonance Structures. (for JEE NEET) Structures which are indistinguishable are of equal energy and hence contribute equally towards the resonance hybrid. For example Thus, the various resonance structures of a molecule should not differ much in energy. (ii) Structures with greater number of covalent bonds contribute more towards the resonance hybrid. For example Since formation of a bond is accompanied by release of energy, therefore, structure (I) with two -bonds is more stable than structure (I and III) which'contain one -bond each. Hence structure (I) makes greater contribution towards the resonance hybrid than-structures (II andIII). (ii) structures which involve separation of positive and negative charges are of higher energy and hence contribute little towards the resonance hybrid.

For example, structure (V) which involves the separation of charges contributes less than the structure (IV) towards resonance hybrid of carboxylic acids. when atoms of different electro negativities are involved, the structure with a negative charge on the- more electronegative atom and positive charge on the less electro negative atom is of lower energy and hence contribute more towards the resonace hybrid than the alternate structure in which the charges are reversed. For example structure (vIII) with the positive charge on the more electronegative atom oxygen contributes less towards the resonance hybrid of a ketone as compared to the alternate structure (VII) with the charges are reversed.

(v) Structures which help to delocalize the positive charge make significant contribution towards the resonance hybrid, regardless of the fact whether the positive charge is on the less or more electronegative atom . for example structure, (X) makes a significant contribution towards the resonance hybrid since it helps to 'disperse the positive charge. However the overall contribution of structure (X) is much less than that of structure (Ix) towards the resonance hybrid.

3. Electromeric effect: A complete transfer of to one of the atoms joined by multiple bond on demand of attacking reagent is called electromeric effect. In case of compounds having a double or triple bond, the pair of -electrons gets completely transferred to the more electronegative element under the influence of attacking reagent is called electromeric effect. This effect is seen only in presence of attacking reagent. This effect disappears as soon as the attacking reagent is removed from the reaction. Thus it is a temporary effect. Electromeric effect is indicated with the help of a curved arrow in the direction of the atom which acquires the pair o f -electrons. For example, when CN- attacks the carbon of the carbonyl-group, electron pair of the -bond gets completely transferred to oxygen atom as shown below.

-+ CN

OCN

The electron displacement can take place in any direction provided the molecule is non polar. If the molecule already contains a polar bond, the displacement of .7t-electrons takes place in one direction only. Electromeric effect is of two types: (i) + E effect and (ii) - E effect. (i)+ E effect. The presence of an electron releasing group like the methyl group (- CH3) in the molecule displaces the electrons away from it and the electromeric effect is called + E effect. (ii) - E effect. The presence of an. electron the attracting group or atom like chlorine displaces the pi-electrons towards Itself and the electromeric effect is known as - E effect as shown below:
H 3C

CH
+ E effect

CH2

Cl

Electromeric effect is a temporary effect and comes into play in the presence of an attacking reagent and ceases as soon as the attacking reagent is withdrawn. Inductive effect Electromeric effect It involves the permanent distortion of an electron pair of It involves only a temporary displacement of a pair of of a molecule. -electrons. Presence of an attacking reagent is not essential. Presence of an attacking reagent is essential. Presence of a multiple bond is not essential but polarity of bond is essential. The displaced electron pair does not leave its molecular orbital. There is only a distortion in shape of the molecular There is a partial charge separation. No ions are formed. Presence of a multiple bond is essential. The electron pair which gets transferred completely leaves its molecular orbital and takes up a new position orbital. There is complete charge separation. Ions are formed.

- E effect

CH

CH2

4. Hyper Conjugation: Delocalization of -electrons of C-H bond of alkyl group directly attached to an atom unsaturated system or to an atom with vacant p- orbital is termed as hyperconjugation. eg: hyperconjugation in propene (CH3-CH=CH2). It is also known as anchimeric effect or Baker Nathan effect or no bond resonance.
conjugation

bond

bond

H C C H C H

Above structures are called hyper conjugative structures. Since there is no bond between the carbon and hydrogen atoms in these structures, hyper conjugation is also called no bond resonance. It may be noted that although a free proton has been shown in the structures it is still bound quite firmly to the electron cloud and thus it is not free to move.

It is clear that hyper conjugation occurs through the -hydrogen atoms. If substance do not have -hydrogen atom then it will not show the hyper conjugation. It can also explain stability of alkene. 2,3 di-methyl but-2-ene < 2-methyl but-2-ene < but-2-ene < 2, methyl propene < propene < ethene

H H C H H H

H CH CH2 H C H H H
+

CH

CH2

C H
+

CH

CH2

C H

CH

CH2

Therefore; more the number of - hydrogen atoms, greater is the number of hyper conjugative structures and hence greater is the inductive effect. Since the number of -hydrogens is three (maximum) in case of methyl group, two in case of ethyl group, one in case of isopropyl group and none in case of tertiary butyl group, the order of hyper conjugation effect is in the order: CH3 - > CH3CH2 - > (CH3)2CH - > (CH3)3C. Q15. Explain briefly main types of organic reactions. Organic reactions can be classified into four main types. 1. Substitution reaction: An organic reaction in which an atom or a group of atoms present in a moleule is displaced by another atom or group of atoms is called substitution reaction. eg: CH4 + methane Cl2

U.V.

CH3Cl + chloromethane

HCl

CH3CH2I + KOH CH3CH2OH + KI ethyl iodide ethanol 2. Addition reaction: Addition of a reagent molecule across a multiple bond by breaking of -bond is called addition reaction. eg: CH2=CH2 + Cl2 Cl-CH2-CH2-Cl ethene 1,2-dichlor ethane 3. Elimination reaction: An organic reaction in which two atoms or a small molecule is removed from organic compound is called elimination reaction. eg:

CH3CH2OH

AI2O3 dehydration

CH2=CH2 + H2O

4. Rearrangement reaction: A reaction involving migration group, from one atom to another atom within the same molecule is called rearrangement reaction.

CH3-CH-CH3

CH3-CH2-CH2-CH3

AICl3

CH3 iso butane

H | CH 3 C | H (1)

H CH 3 | | CH 3 C CH 3 C | | CH 3 CH 3 (2) (3)

Coniditions for resonance. Some important conditions for resonance are given below (i)The various resonating structure should differ only in the postion of the electrons and not in the position oi atoms or nucl ei.

(ii) All the resonating structures should have' the same number of unpaired electrons. In case of atoms of the second period in the periodic table, such resonating structures which violate octet rule should not be considered. For example, structure (II) can not be considered as resonance structure of (I) since it violates the octet rule because nitrogen in this structure has 10 electrons which is wrong. The reason being that nitrogen cannot have more than 8 electrons since it does not have d-orbitals

CH2

CH I

NH3

CH2

CH II

NH3