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functional groups
A functional group is an atom or group of atoms in a molecule that gives the molecule its characteristic chemical properties i.e. they are the action group or reactive site in a chemical reaction and the remaining hydrocarbon part remains inert. Each functional group shows its characteristic chemical reactions. Functional group helps in nomenclature of organic compounds. Functional group serves to classify organic compounds into different classes or families i.e. compounds with same functional group belong to same class.
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Ajnish Rule: During any organic reaction if an intermediate is formed in the rate determining step then stability of intermediate will decide the formation of major product. Greater is the stability of intermediate, major is the corresponding product and the stability of intermediate is generally decided by Resonance, Hyperconjugation & Inductive effect.
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Inductive effect
When bond is formed between two atoms of different electronegativity then bond pair electron density is shifted towards more electronegative atom and due to shifting of electron cloud dipole is created between the two atoms. Due to this dipole in bond, electron density in the chain is also shifted and progressively moves into the chain. This permanent effect of polarization in the chain due to a dipole is called as inductive effect. Inductive effect is represented as I effect. I effect is a permanent effect i.e. it will always be present when carbon is attached to a more electronegative or less electronegative atom. This effect is distance dependent and its strength is generally negligible after 3 carbon atom in the chain. I effect is additive in nature i.e. when two groups of similar nature are present in molecule then their effects are added and if two groups of dissimilar nature are present in molecule then their effects are subtracted. One point should always be kept in mind that I effect always operate along bond. Never think of inductive effect in bonds because in bond some other effects are operative. www.OrganicChemistry.co.in
Inductive effect
The C H sigma bond is taken as a reference for I effect. Shifting of electron density or polarity in C H sigma bond is considered to be negligible and I effect of H is taken to be zero. I effect is weak effect since the bond electrons are strongly held. A crossed arrow ( ) is often used to indicate the direction of movement of electron. By convention the electrons are displaced in the direction of the arrow. The tail of the arrow (which looks like a plus sign) is electron poor + & the head of arrow is electron rich (-). It is also important to remember that I effect creates only polarity in the sigma bond and not the ionization in the bond. Inductive effect is also called as transmission effect. In case of organometallic compounds for example lithium alkyl (R-Li) & Grignard reagent (R-MgX) carbon is bonded to the less electronegative metal atom. Due to this electronegativity difference between metal & Carbon, metals are electron donating in nature leading to creation of partial negative charge over carbon www.OrganicChemistry.co.in
Inductive effect
It is also important to remember that inductive effect is atoms ability to polarize the bond i.e. shifting of electrons in a sigma bond in response to the electronegativity of nearby atoms. Types of I effect. On the basic of direction of electron flow along sigma bond which either make carbon electron deficient or electron rich in nature. So on the basis of it, inductive effect is of two types. I effect: The atom or group which withdraws electron density (EWG group) from the carbon making carbon electron deficient are called as I groups and effect is called as I effect. I groups create partial positive charge over the carbon & partial negative charge over more electronegative atom. Various groups with decreasing order of I strength follows: -NR3+ > -SR2+ > -NH3+ > -NO2 > -SO3H > -CN > -CHO > -COOH > -F > -Cl > -Br > -I > -OR > -OH > CCH > -NH2 > -C6H5 > -CH=CH2 > -H www.OrganicChemistry.co.in
Inductive effect
+ I effect:
The atom or group which release, repel or donate electron density (EDG group) to the carbon making carbon electron rich are called as + I groups and effect is called as + I effect. + I groups create partial negative charge over the carbon & partial positive charge over less electronegative atom.
Capsule:
If there is any electronegativity difference between two atoms along a sigma bond inductive effect is always operative. In organic chemistry always look for the carbon whether substituent attach to it donate electron to it or withdraws electron from it. Electron donating group of any form is + group for carbon & electron withdrawing group of any form is group for carbon. www.OrganicChemistry.co.in
Resonance
There are so many organic molecules (neutral molecules, ions, free radicals) where all the observed properties i.e. physical & chemical properties cant be satisfactorily explained with the help of a single structural formula i.e. Lewis structure or valence bond structure. In order to satisfactorily explain all the properties of such molecules we represent the molecule by two or more structures just by shifting of p orbital electrons or delocalization of electrons without changing relative positions of the atomic nuclei. These structures are known as resonating structure, canonical structure, contributing structure or resonance unperturbed structures and phenomenon is called as resonance. The resonating structures are only the hypothetical structures and the real structure lies in between them. The resonating structures contribute to the real structure which is called as Resonance hybrid. The resonance hybrid is more stable than any of the resonating structures. Compound showing resonance is not a mixture of some molecules having the structures shown by one canonical form and some having structures shown by another but the compound showing resonance have the same structure all the time www.OrganicChemistry.co.in
Capsules:
1. A=B C+/ / / /=/ 2. A / B 3. A B C+/ / / /
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Mesomeric effect
It is simply the resonance occuring in a molecule when any atom or group of atoms is in conjugation with organic molecule. In general there is no difference between resonance and mesomeric effect. Heinsenberg (1926) called it as resonance and Ingold (1933) called it as mesomeric effect. A very minute difference is there between resonance and mesomeric effect i.e. when a molecule which do not have any polarity, such as CH2=CH-CH=CH2 ,is considered then pi electrons may move in either direction (i.e. from left to right or from right to left), in such case resonance is operating in the molecule but when the same compound is attached with CHO group i.e. CH2=CH-CH=CH-CH=O then electrons will always moves from left to right, in such case due to CHO group carbon aquires positive charge and oxygen aquires negative charge. Therefore in such case resonance is called as mesomeric effect.
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Hyperconjugation
Inductive effect of alkyl group follows following order (CH3)3C- > (CH3)2CH- > CH3CH2- > CH3- when they are attached to saturated carbon. But when they are attach to unsaturated carbon i.e. C=C or aromatic system then order is reversed. This abnormal behavior of electron release can be explained by a new concept other than resonance and inductive effect which is called as Hyperconjugation. Here electron releasing effect can be explained by assuming that orbital of C-H bond overlap with the adjacent orbital. This displacement of electron pairs of C-H bond cause a partial positive charge on the H atom without the actual proton release. ability of sigma bonded electrons of an alpha C-H bond to undergo conjugation with the adjacent pi electron is called as hyperconjugation. Concept of hyperconjugation is generally applied to carbocation , free radical & C=C double bonded system such as alkene and aromatic compounds. www.OrganicChemistry.co.in
Hyperconjugation
In case of carbocations & free radicals, the carbon atom having positive charge or unpaired electron respectively is carbon. Therefore in that case only the electrons in the CH bond that are to the positively charged carbon or free radical show hyperconjugation & can stabilize them. In case of alkenes the carbon adjacent to double bonded carbon is carbon. Here the electrons in the CH bond that are to the double bonded carbon atom stabilize it by hyperconjugation. Hyperconjugation is also permanent effect similar to Resonance & Inductive effect. It is distance independent similar to resonance. Hyperconjugation also increases the stability of molecule. Greater is the number of hyperconjugation greater is the stability because it is also a stabilizinh phenomenon similar to resonance.
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Hyperconjugation
As no bond structures are obtained similar to resonance so hyperconjugation is also called as no bond resonance. One point should always kept in mind that the stability of carcanion is not decided by hyperconjugation in general case. For that we use the concept of M effect or I effect. To calculate the number of hyperconjugation or no bond resonance always count the hydrogen present over the carbon adjacent to the carbon having + charge, free radical or double C=C bond. If proton is released from the system completely then such effect is called resonance & if proton is present in the vicinity with no bonding with any atom then same effect is called as hyperconjugation. One most important point must always kept in mind that concept of hyperconjugation is only applied to carbocation, free radical and alkenes. So never think the concept of hyperconjugation in C=O, C=N, C=S, CN etc. www.OrganicChemistry.co.in