Carbocation

by

[I Manoja Devi] [Msc org Chem] [101309503051]

TABLE OF CONTENTS

CARBCATION:

 Structure

 Stability

 Generation of Carbocation’s

 Reaction’s of Carbocation’s

 Application’s

 Non-Classical Carbocation’s

 Detection of Carbocation’s

17

STRUCTURE: 17 . which means that it is closely associated with a negative ion called a counter ion or gegenion. Carbon free radical. cannot be isolated to study during the course of reaction because of their less stability and high reactivity. They are unstable. Carbanion. Ylides & Enamines REACTANTS Stable PRODUCTS REACTIVE INTERMEDIATES Carbocation’s are intermediate’s in several kinds of reactions. Carbine. Nitrene.CARBOCATION Carbocation’s are the intermediate’s formed during heterolytic cleavage of covalent bond in alkyl halides.Unstable. Ionpairs more likely in nonpolar solvents. the carbocation may be free (in polar solvents) or it may exist as an ionpair. RX R+ + X- Majority of organic reactions proceeds via the formation of short lived species which are highly reactive are known as “Reactive Intermediates”. In solution. Ex: Carbocation.They are short lived species formed during the course of reaction. Benzyne . The more stable one have been prepared in solution & in some cases even as solid salts.

instead of the usual four. and those that are stabilized by resonance (either through lone pair electrons on adjacent atoms or through conjugated pi bonding electrons).Carbocations are species bearing a formal "+" charge on carbon. secondary (2°). primary (1°). or no attached alkyl groups. one attached group. perpendicular to the plane containing the substituents (see diagrams shown to the right). planar (sp2) configuration is more stable than the pyramidal (sp3) by ~84 KJ (20 K. There are basically two types of carbocation’s: those that are not stabilized by resonance effects. respectively. or methyl carbocation’s.. These would be referred to as tertiary (3°). Carbocation’s are "hypovalent" species. These four possibilities have been shown below. this incomplete octet around carbon makes carbocation’s very unstable and very reactive. in as much as they have only three shared pairs of electrons around carbon.cal) mol-1. Of course. According to Quantum Mechanical Calculation’s. Simple Alkyl Carbocation’s: There are four possible degrees of alkyl substitution on a carbocation: three attached alkyl groups. two attached groups. with an empty p orbital on carbon. They have sp2 hybridization and trigonal planar geometry. Structure Name (type) Relative stability tert-butyl cation (a 3° carbocation) most stable isopropyl cation (a 2° carbocation) next-to-most stable ethyl cation (a 1° carbocation) next-to-least stable methyl cation least stable  An essential requirement for such stabilization is that the carbocation should be planar due to effective delocalization. 17 .

due to inability to assume the planar configuration preventing formation of the carbocation. R3B with which they are isoelectronic. secondary (II). they thus parallel the trialkyl boron's..M. and primary (I) alkyl carbocations  The sequence is resulting from increasing substitution of the cationic carbon atom leading to increasing delocalization of the positive charge by Inductive. As planarity is departed leads to instability of the carbocation & consequent difficulty in its formation increase very rapidly. 17 . Mesomeric & solvation effect’s. STABILITY: Order of stability of examples of tertiary (III). Hyperconjugation. This has been seen in extreme inertness of 1-bromo tryptycene to SN1 attack. stability of Me3C+ is borne out by the fact that it may often be formed under vigorous conditions. All electron donating groups containing lonepair of electron’s are ‘+I’ groups & all electron withdrawing groups are ‘–I’ groups. Br Ph C Ph Ph SN1 No Reaction  The expected planar structure of even simple cation’s has been confined by analysis of N. by the isomerisation of other first formed carbocation’s & also by the observation that it remained unchanged after heating at 1700 in SbF5 / FSo3H for 4 weeks.R & I. CH3F + SbF5 CH3+SbF6- 1) INDUCTIVE EFFECT: Displacement of sigma electrons towards the more electronegative atom is called “Inductive Effect”.R spectra of species such as Me3C+SbF6.

9 Hyperconjugative Structure’s.C+ R R groups (+I groups) donate the electrons towards carbocation & increase in the stability of carbocation takes place. 3 Hyperconjugative Structure’s. Greater the –CH3 groups attached to carbocation. Ex : Stability Order: C+ OCH3 > C+ CN 2) HYPERCONJUGATION EFFECT: This is also called as “No bond resonance effect”. Therefore +I groups increase the stability of carbocation. greater will be the stability. 17 . Therefore –I groups decrease the stability of carbocation. 6 Hyperconjugative Structure’s.stability of carbocation decrease. C+ W W groups (-I groups) withdraw the electrons from carbocation so.

higher will be the stability.3) RESONANCE / MESOMERIC EFFECT: Higher the resonance in the structure . The Resonance Stabilization of the Allylic Carbocation The Resonance Stabilization of the Benzyl Carbocation: 17 .

 Ph H H Ph C+ > Ph C+ > Ph C+ Ph Ph H  Over All Order Of Stability: Tropylium C+ > TriPhenyl Methyl C+ > C6H5–CH2+ > CH2=CH–CH2+ >  The Cyclo Propyl rings present on the carbocation also stabilized. As in the Benzyl C+ . if H’s are replaced by the Phenyl rings the stability still increases. 17 .

Delocalization of positive charge is increased to maximum extent.In this carbocation. 17 . Thus the action of SbF5 in liquid So2 on P-MeOC6H4CH2CH2Cl(1) results in formation of (2) rather than the expected cation (3). It should not react with solvent to give some other product. Therefore stability is increased. The carbocation should be inert to the solvent. Stabilization can also occur again by delocalization through the operation of a Neibouring Group Effect resulting in the formation of a “Bridged Carbocation”. Order: H C+ > H C+ > H C+ > H C+ H H 4) SOLVATION EFFECT: Solvation Effect increases the stability of carbocation.the P-Orbitals of CH2+ are parallel to P-Orbitals of Cyclo Propyl carbon atom’s. Phenyl ring acting as Neighbouring Group.

CH2 CH2 + H+ + CH2 CH3 Alkyl Carbocation 17 . solvlysis is found to occur ~106 times more rapidly under comparable conditions & matter’s can be so arranged as to make possible the isolation of a bridged intermediate . alkenes are protonated and give carbocation’s. albeit not now a carbocation. GENERATION OF CARBOCATION: 1) From Alkene’s: In presence of acidic media. The NG Effect is even more pronounced with ‘-OH’ rather than an ‘-OMe’ substituted in P-Position .OMe : OMe SbF5/SO2 OMe SbF5Cl-700 CH2 CH2+ (3) H2C (1) CH2 Cl H2C (2) CH2 Such species with a bridging phenyl group are known as “Phenonium Ions”.

R N+ N R+ + N2 4) From Alkyl Halides: 17 . R OH + H+ R OH2+ -H2O R+ O CH3 C OH + H+ O CH3 C + O OH H -H2O Acyl Carbocation CH3 C+ 3) From Diazonium Ion’s: The alkyl Diazonium Ion’s are unstable & decompose at room temperature to give carbocation’s.+ H+ + 2) From Alcohol’s: Alcohols on treatment with concentrated acids get protonated and the protonated alcohols lose a molecule of water to form carbocations.

In place of alkyl halides. which decomposes to give alkyl carbocation’s. alkyl tosylates & alkyl mesylates can also be used. 17 . undergo reaction’s (as soon as they are formed) to give stable product’s. O R C Cl Anhydrous AlCl 3 O RCO+---Cl-AlCl3 R C+ Acyl Carbocation + AlCl4+ REACTIONS OF CARBOCATION’S: The carbocation’s being very reactive & unstable.Br. 5) From Acyl Halides: The acyl halides on treatment with anhydrous Alcl3 gives a complex. in general carbocation’s undrgo following types’s of a) Elimination of a proton.Cl) R+ + X- The process is accelerated by the presence of powerful Ion-Solvation medium or metal ion’s such as Ag+ Ions.The Alkyl Halides on ionization give carbocation’s. AlCl3 R X Or Ag+ (X=I.

followed by decomposition of the formed diazonium salt ) may eliminate a hydrogen ion to form an alkene (propane). Thus. d) Molecular rearrangement’s  Elimination of a proton: A carbocation may lose a proton to form an alkene. 1-propyl carbocation may rearrange to more stable secondary carbocation. 1-propyl carbocation (which can be generated from 1-amino propane by diazotization. c) Addition to unsaturated compound’s. which may lose a proton to give propene.b) Reaction with Nucleophile. NaNo2/HCl CH3CH2CH2NH2 1-Amino propane 0-50C CH3CH2CH2 N+ N Propyl diazonium cation -N2 H+ CH3 CH CH2 Propene H Primary carbocation CH3 CH CH2+ Rearrangement 17 . Alternatively.

Similarly.+ CH3 CH CH3 Secondary carbocation(More Stable) -H+ CH3 CH CH2 Propene  Reaction with Nucleophiles: A carbocation may combine with a nucleophile to form a new bond. secondary propyl carbocation reacts with Cl. CH3 CH2 CH2+ Propyl carbocation + Br- CH3 CH2 CH2Br Propyl bromide + CH3 CH CH Secondary carbotion + Cl- CH3 CH CH3 Cl Isopropyl chloride 17 .ion to form isopropyl chloride.forms n-proply bromide. For ex: proply carbocation on reaction with Br.

which eliminates a proton to give tertiary butyl alcohol. CH3 CH3 + CH3 CH3 C+ + O H CH3 C O H CH3 C OH CH3 H H3C H CH3 t-butyl alcohol Tertiary butyl water Carbocation (Neutral nucleophile) H + + -H CH3 CH2+ + NH3 Ethyl Carbocation CH3 CH2 N H H CH3 CH2 NH2 Ethyl amine  Addition to unsaturated compounds: 17 . Tertiary butyl carbocation .The reaction of a carbocation with a neutral nucleophile such as water gives a protonated alcohol. for ex. reacts with water(neutral nucleophile) to give protonated tertiary butyl alcohol.

A primary carbocation on rearrangement gives a more stable carbocation (20 C+ or 30 C+) Rearrangement CH3CH2CH2+ 10 carbocation 1.A carbocation may react with an alkene to produce another carbocation. i. + CH2 CH2 + CH3 CH3 CH2 CH2+ Propyl carbocation CH3 CH3 + CH3 CH3 CH3 C CH2 + C CH3 CH3 C CH2 C CH3 + CH3 2-Methyl propene CH3  Molecular rearrangements: A carbocation undergoes molecular rearrangement to produce a more stable carbocation.2 Hydride shift + CH3 CH CH3 20 carbocation 17 .

For ex: HO CH2NH2 HO CH2N2+ HO CH2+ NaNO2/HCl 0-50 1-Amino methyl Cyclohexanol -N2 17 .3 Dimethyl-2-butyl carbocation(30 C+)  In some cases molecular rearrangements involving carbocation’s may lead to ring expansion.3 Dimethyl 2-butyl Carbocation(20 C+) 2. A secondary carbocation on rearrangement gives a tertiary carbocation.ii. CH3 Rearrangement CH3 C CH CH3 + CH3 1.2 alkyl shift H3C CH3 CH3 C C CH3 + H 3.

H H3C Y R H CH3 H3C Z+R H R H CH3 CH3 H3C H H R H H H3C Z H3C Z 17 . Thus. the configuration of the carbon atom from which migration takes place (migration origin). Due to this there is no chance for change in its configuration i.+ O -H+ OH Cyclo Heptanone  STEREOCHEMISTRY OF REARRANGEMENT: In rearrangements involving carbocation’s . there is retention of configuration in a chiral migration group ® . the migration of group proceeds through the formation of a bridged intermediate. Further evidences show that the configuration at both the chiral centers (migration terminus & migration origin) is inverted which is a typical of a molecular rearrangement’s. the migrating group gets associated with the migration terminus before it has completely broken its connection with the migration origin. the configuration of the carbon atom to which migration takes place (migration terminus) & the configuration of the migrating group (if it is a chiral). there are three centre’s of steriochemical interest.e. It was observed that in intramolecular rearrangement.

 APPLICATIONS: Generation of carbocation’s in a large number of synthetic sequences is very well established. Friedal-Craft Reaction is useful for introducing . Some common examples of acylation are: COCH3 + AlCl3 CH3COCl HO OH AlCl3 + CH3COCl HO OH COCH3 The yield of the acyl products is good (70-80%). Thus .COCH3 group in an aromatic moiety (acylation) & also for introducing alkyl group (alkylation). Some examples of alkylation are given below. + AlCl3 X-R R 17 .

WAGNER-MEERWEIN REARRANGEMENT: The rearrangement which takes place by involving the change in the carbon skeleton of the reactant via the formation of carbocation intermediate is known as Wagner Meerwein Rearrangement. The formation of carbocations is sometimes accompanied by a structural rearrangement. in somewhat greater yield than 3-chloro-2. Such rearrangements take place by a shift of a neighbouring alkyl group or hydrogen. for example. Pincol-Pinacolone Rearrangement & Wagner Meerwein Rearrangement. The addition of HCl to 3. leads to an unexpected product. 17 . 2-chloro-2. Beckmann Rearrangement.3dimethyl-1-butene. and are favoured when the rearranged carbocation is more stable than the initial cation.2-shift of a methyl group. This surprising result may be explained by a carbocation rearrangement of the initially formed 2ºcarbocation to a 3º-carbocation by a 1. the expected Markovnikov product.2-dimethylbutane.AlCl3 + (CH3)2CHCl CH(CH3)2 There are some other useful reactions involving carbocations For ex: Baeyer Villeger Oxidation.3-dimethylbutane.

2-diol to a carbonyl compound in organic chemistry. The name of the reaction comes from the rearrangement of pinacol to pinacolone.PINACOL-PINACOLONE REARRANGEMENT: The pinacol rearrangement or pinacol-pinacolone rearrangement is a method for converting a 1. 17 . This rearrangement takes place under acidic conditions.

3-butanediol (1) in H2SO4 was studied.The reaction of 2. BECKMANN REARRANGEMENT: The rearrangement of Oximes in presence of acid catalyst PCl5/PCl3 to form n-substituted amine is Beckmann Rearrangament 17 .3-di-(3-pyridyl)-2.

BAEYER VILLEGER OXIDATION: The Baeyer-Villiger oxidation is an organic reaction in which a ketone is oxidized to an ester by treatment with peroxy acids or hydrogen peroxide.[1][2] Key features of the BaeyerVilliger oxidation are its stereospecificity and predictable regiochemistry.[3] 17 .

bonding) ex. Further optically active exo-brosylate gives completely racemic exo-acetate.. 17 . It is well known that acetolysis of both exo-2-norbornyl brosylate and endo-2-norbornyl brosylate produce exclusively exo-2-norbornyl acetate. The exo isomer is more reactive than the endo isomer.the norbornyl carbocation. These carbcation’s are cyclic. bridged ions and possess a 3 center bond in which 3 atoms share two electrons (3 center. 2e.Mechanism:  NON CLASSICAL CARBOCATION: Carbocation’s which are more than tri-coordinate are called Non-classical carbocation’s.

c6 is penta coordinate and serves as a bridging atom in the cation.Both acetolysis proceed via formation of a carbocation.c-6 and the mid point of c-1. The non-classical ion is stabilized relative to a secondary ion by c-c sigma bond delocalization. Some other examples of non-classical carbocations are given below: 17 . This intermediate is achiral & has a plane of symmetry passing through c-4.(neighbouring single bond participation) & led to the formation of non-classical carbocation as an intermediate.c-2 bond.c-5. Ionization of exo-brosylate is assisted by the c1-c6 bonding electrons..

cannot be isolated. In NMR spectroscopy. CH3 SbF5 CH3 C F Liq So3 CH3 Singlet 3-4ppm CH3 H3C C+ + SbF6 – CH3 singlet 4-5ppm H3C CH3 SbF5 H3C CH3 17 . After reaction with SbF5 tertiary carbocation also gives a singlet but there is an increase in the chemical shift.+ +  DETECTION OF CARBOCATION: Majority of carbocation are unstable. The increase in the chemical shift of carbocation than reactants indicates the formation of intermediate. and studied. Therefore they can be detected by NMR &IR spectroscopy. NMR spectroscopy: Tertiary butyl fluoride on reaction with SbF5 produces tertiary carbocation. tertiary butyl fluoride gives a singlet at 3-4ppm.

But when SbF5 is added.CH3 C C CH3 Liq So3 Br Br CH3 C C CH3 Br+ singlet (increase in chemical shift than reactant) Singlet 3-4ppm IR SPECTROSCOPY: In the below reaction. 17 . peaks corresponding to the Sp3C-H stretching and C-F stretching is observed in reactant. CH3 SbF5 CH3 C F Liq So3 CH3 CH3 H3C C+ + SbF6 – CH3 The gas-phase IR spectra of the diamantyl and triamantyl carbocations are presented. peak corresponding to C-F stretching is disappeared indicating that some intermediate is formed may be carbocation. when IR spectroscopy is observed.

BIBLIOGRAPHY First reference. Advanced Organic Chemistry (4th Edition) – Jerry March.Ahulwalia & Rakesh Kumar Parashar. Mechanism in Organic Chemistry (6th Edition) – Petersykes. Additional references.K. Organic Reaction Mechanisms (3rd Edition) – V. Internet 17 .