1

Generation, Stability and Chemical Reactions of Carbocation,

Carbanions, Carbenes, Nitrenes and Benzynes

[1]. Carbocation

Definition: “A carbocation is an organic ion or a molecule with a positively-charged carbon

atom.” OR “A carbocation is an organic cation containing an excess positive charge on one or
more carbon atoms.” Carbocation is in a state of sp2 hybridization.

Examples of Carbocation: The simplest examples are methenium ion (CH3+), methanium ion
(CH5+) and ethanium ion (C2H7+).

Di positive carbocation: Some carbocations may have two or more positive charges, on the
same carbon atom or on different atoms. Example: Ethylene dication C2H42+.

Reactive Nature of Carbocation:

 The charged carbon atom in a carbocation has only six electrons in its outer valence
shell instead of eight valence electrons. Carbon atoms with eight valence electrons have
the maximum stability (octet rule).
 Therefore, carbocations are often reactive, seeking to fill the octet of valence electrons
as well as to regain a neutral charge.
 Carbocations are reactive intermediates in many organic reactions e.g. Wagner–
Meerwein rearrangement, SN1 reaction, E1 reaction etc.

Carbocation Classification:

Carbocations are characterized as primary, secondary or tertiary depending upon the number of
bonds that the carbon atom with the positive charge has with other carbon atoms.
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[1]. Primary Carbocation: In a primary (1°) carbocation, the carbon which carries the positive
charge is only attached to one other alkyl group.

General Formula and Some Examples of Primary Carbocation:

[2]. Secondary Carbocation: In a secondary (2°) carbocation, the carbon atom bearing the
positive charge is attached to two other alkyl groups, which may be the same or different. A
secondary carbocation has the general formula shown in the box. R and R' represent alkyl groups
which may be the same or different.

General Formula and of Examples Secondary Carbocation:

[3]. Tertiary Carbocation: In a tertiary (3°) carbocation, the positive carbon atom is attached to
three alkyl groups R, R' and R", which may be same or different.

General Formula and Examples of Secondary Carbocation:

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[4]. Allylic Carbocation: If the carbon bearing the positive charge is present immediately
adjacent to a carbon-carbon double bond, the carbocation is termed an allylic carbocation.
The simplest case is called the allyl carbocation with every R group = H.

[5]. Vinyl Carbocation: If the carbon bearing the positive charge is part of an alkene, the
carbocation is termed a vinylic carbocation. The simplest case is called the vinyl carbocation.

[6]. Benzylic Carbocation: If the carbon bearing the positive charge is located immediately
adjacent to a benzene ring, it is called benzylic carbocation. Simplest E.g.: benzyl carbocation.

[7]. Aryl Carbocation: If the carbon bearing the positive charge is part of a benzene ring, the
carbocation is termed an aryl carbocation. The simplest case is called the phenyl carbocation.
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Classification of Carbocations Based on the Valency of the Charged Carbon:

Until the early 1970s, all carbocations were called carbonium ions. In present-day chemistry,
a carbocation is any ion with a positively charged carbon atom, classified in two main
categories according to the valency of the charged carbon i.e.,

[1]. Carbenium Ion: A carbenium ion is a positive ion with the structure RR′R″C+, that is, a
chemical species with one trivalent carbon that bears a +1 electric charge. E.g. H3C+.

[2]. Carbonium Ion (Non-Classical carbocation): Carbonium ion is any cation that has a
pentavalent carbon atom. The name carbonium may also be used for the simplest member of the
class, properly called methanium ion where the carbon atom is bonded with 5 hydrogen atoms.

Generation/Methods of Preparation of Carbocations:

[1]. Protonation of Unsaturated Organic Compounds: The protonation of unsaturated organic

compounds is one of the general methods for the generation of carbocations. Strong Bronsted
acids (proton or hydrogen ion donor) in which a hydrogen atom is attached directly to an atom
having high electronegativity (O, Cl, F etc.) are usually employed for this purpose.

Example:
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[2]. Ionization of a Bond between Carbon and a Leaving Group: When a bond between a
carbon atom and a leaving group ionizes, the leaving group accepts the pair of electrons that used
to be shared in the covalent bond. This may leave the carbon atom with an open octet, resulting
in a carbocation. Example - 1: From an Alkyl Halide:

Example – 2: From an Amine: Primary amines react with nitrous acid i.e., HNO2 (prepared
freshly from reaction of HCl and NaNO2) to form diazonium salts. The diazonium salts are
unstable and decompose into carbocations and nitrogen.

Example – 3 and 4: From an Alcohol: Protonation of an alcohol to give an oxonium ion

(oxygen cation with three bonds) which ionizes to the corresponding carbocation.
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Carbocation Stability:

 Carbocations have incomplete octet i.e., only six electrons are present in their valence
shell making them electron deficient species and therefore very reactive and unstable.
 Thus, carbocations behave as unstable electrophiles and will react very quickly with
nucleophiles to fill their empty p orbital forming new bonds.

Factors Stabilizing Carbocations: These include:

1. Neighboring carbon atoms (inductive effect and hyperconjugation if contain C-H bonds).
2. Neighboring carbon-carbon multiple bonds (resonance effect).
3. Neighboring atoms with lone pairs (resonance effect).

[1]. Carbocations are stabilized by neighboring carbon atoms (Due to Inductive Effect):

 Because carbocations are electron deficient, attaching electron donating groups (such as
alkyl groups) to the carbocation will help stabilize the carbocation.
 Conversely, a carbocation will be destabilized by electron withdrawing group like NO2.
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 The stability of carbocations increases as we go from primary to secondary to tertiary

carbons because alkyl groups are weakly electron donating due to hyperconjugation
and inductive effects.

Explanation: By increasing the number of C-H sigma bonds adjacent to the carbocation by
increasing the number of alkyl groups attached to the carbocation carbon, carbocation stability is
enhanced due to increased hyperconjugative interactions through donation of the electrons in C-
H sigma bonds to the empty p orbital of the carbocation.

Carbonyl groups are electron-withdrawing by inductive effects, due to the polarity of the
C=O double bond. Carbocation A below is more stable than carbocation B, even though A is a
primary carbocation and B is secondary. In species B the positive charge is closer to the carbonyl
group, thus the destabilizing electron-withdrawing effect is stronger than it is in species A.

[2]. Carbocations are stabilized by neighboring carbon-carbon multiple bonds (Due to

Resonance Effect): Carbocations where the C+ is adjacent to another carbon atom that has a
double or triple bond have extra stability because of the overlap of the empty p orbital of the
carbocation with the p orbitals of the π bond (pi bond). This overlap of the orbitals allows the
charge to be shared between multiple atoms and therefore stabilizes the carbocation. Resonance
effects can stabilize carbocations even more strongly than inductive effects.
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Example: Consider the simple case of a benzylic carbocation:

Three additional resonance structures can be drawn for this carbocation in which the positive
charge is located on one of three aromatic carbons. The positive charge is not isolated on the
benzylic carbon, rather it is delocalized around the aromatic structure. This delocalization of
charge results in significant stabilization.

Example: Allylic Carbocation: An allylic cation has two resonance contributors. The positive
charge is not localized on a single carbon, but is shared by two carbons.

Allylic and benzylic cations have delocalized electrons, so they are more stable than similarly
substituted carbocations with localized electrons.
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[3]. Carbocations are stabilized by adjacent lone pairs: Adjacent atoms with lone pairs act as
electron donors to the electron-poor carbocation. This results in forming a double bond (π
bond) and the charge is delocalized to the atom donating the electron pair (π donation - pi
donation).

 Nitrogen and oxygen atoms are the most powerful π bond donors (pi bond donors).
However, even halogen atoms stabilize carbocations through donation of a lone pair.

Figure: Stabilization of the carbocation by lone pair donation. The O atom donates an electron
pair to the C+ atom and a double bond is formed. The positive charge is delocalized to the
oxygen atom providing extra stability.
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Similarly, a N atom – or even a halogen atom - may donate an electron pair to the C+ atom and
disperse the + charge stabilizing the carbocation.

Figure: Stabilization of the carbocation by lone pair donation. The N atom donates an electron
pair to the C+ atom and a double bond is formed. The positive charge is delocalized to the
nitrogen atom providing extra stability.
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For Your Concept

Resonance is More Powerful than Inductive Effect: Because heteroatoms such as oxygen and
nitrogen are more electronegative than carbon, they seem to be electron withdrawing groups (by
negative inductive effect) that destabilize carbocations. In fact, if the oxygen or nitrogen atom is
in the correct position, the overall effect is carbocation stabilization. This is due to the fact that
although these heteroatoms are electron withdrawing groups by induction, they are electron
donating groups by resonance, and it is this resonance effect which is more powerful.

Resonance is More Powerful than Hyperconjugation: When considering the importance of

hyperconjugation versus resonance as the more important stabilizing feature, resonance
usually wins out. For example, a primary carbocation with resonance is more stable
than a secondary carbocation without resonance. A secondary carbocation with resonance
is usually more stable than a tertiary carbocation without resonance.

Chemical Reactions of Carbocations:

The chief pathways by which carbocations react to give stable products are as follows:

[1]. Combination with Nucleophile (a Lewis acid–base reaction): The carbocation is

electrophilic because it has a positive charge. It is neutralized when an electron pair is accepted
from a nucleophile (species that donates a pair of electrons) and a new covalent bond is formed.

Carbocations are very reactive, even weak nucleophiles e.g. water can be captured with ease.
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[2]. Proton Loss (or much less often, another positive ion) from the adjacent atom to form a
π bond: Accepting an electron pair from an adjacent bond to a hydrogen atom neutralizes the
positive charge or fills the open octet and forms a new π bond.

The hydrogen atom must be removed by a base, but because carbocations are generally very
reactive species and very strongly driven to dispose of the positive charge. Even a weak base
such as water or iodide ion can accomplish this deprotonation.

Note: When carbocation deprotonation can lead to more than one product, the more stable
product is major.

[3]. Rearrangement: An alkyl or aryl group or a hydrogen atom (sometimes another group)
migrates with its electron pair to the positive center, leaving another positive charge behind.

Rearrangements tend to form a more stable carbocation. For example: Rearrangement will
occur if a secondary carbocation can be formed from a primary carbocation because a secondary
carbocation is more stable than the primary carbocation. There can be two types of
rearrangements. Shift of an alkyl group is called a 1,2-alkyl shift.
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 Shift of a hydrogen atom is called a 1,2-hydride shift. Hydride ion = H.

[4.] Addition: A carbocation may add to a double bond, generating a positive charge at a new
position. The new carbocation normally reacts further in an effort to stabilize itself.

[2]. Carbanions

Definition: “Carbanions are anions of carbon, generated by the removal of one of the groups
attached to a carbon without removing the bonding electrons.” OR “An organic ion with a pair
of electrons and a negative charge on the central carbon atom is called a carbanion (carb, from
carbon + anion for negative charge).”

These are named after the parent alkyl group and adding the word carbanion. These are also
termed as primary, secondary & tertiary etc. depending upon the nature of carbon-atom bearing
negative charge.
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Structure of Carbanion:

Examples:

Characteristics of Carbanions:

 Its carbon-atom contains negative charge. It is formed by heterolytic bond fission.

 Although they are highly reactive intermediates, the valence shell of negatively charged
carbon-atom contains 8-electrons in the outermost shell. Thus its octet is complete & it
contains a lone pair of electron.
 The negatively charged carbon is in a state of sp3 hybridization.
 The hybrid orbitals are directed towards the corners of a tetrahedron. Three of the
hybrid orbitals are involved in the formation of single covalent bonds with other
atoms while the fourth hybrid orbital contains a lone pair of electron. Thus it has a
pyramidal structure similar to NH3 molecule.

Note: Geometry of allyl and benzyl cabanion is almost planar and hybridization is sp2.

 Carbanion behaves as charged nucleophile. It is readily attacked by electrophillic

reagents.
 It is diamagnetic in character because all eight electrons are paired. (Diamagnetic
means they are repelled by a magnetic field; an applied magnetic field creates an induced
magnetic field in them in the opposite direction, causing a repulsive force).
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Formation/Methods of Preparation of Carbanions:

Carbanions are formally derived from neutral organic molecules by removal of positively
charged atoms or groups of atoms, and they are important chiefly as chemical intermediates i.e.,
as substances used in the preparation of other substances.

[1]. Heterolytic Fission: When a covalent bond, in which carbon is attached to a lesser electro
negative atom, breaks up by heterolytic fission, the carbon-atom acquires a negative charge due
to an extra electron. And the group attached to a carbon leaves without its electron pair:

Example: The simplest carbanion, the methide ion (CH3-), is derived from methane (CH4) by a
loss of a proton (hydrogen ion, H+) as shown in the following chemical equation:

Leaving Group here is most often a proton. This is a simple acid–base reaction, and a base is
required to remove the proton. However, other leaving groups are also known e.g.:

[2]. Addition of a Nucleophile to Compounds containing Double Bonds: When a negative ion
(a nucleophile) attacks on organic compound specifically adding to a carbon–carbon double or
triple bond. It forms a covalent bond with the unsaturated system. The negative charge on X is
transferred to one of the carbon in the multiple bond.
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[3]. Preparation of Phosphorus Ylide: A very important nucleophilic carbon species constitute
the phosphorus ylide. The preparation of ylide is a two stage process, each state of which
belongs to a familiar reaction type: nucleophilic attack on an alkyl halide, and abstraction of a
proton by a base.

The phosphorus ylide have hybrid structure, and it is the negative charge on carbon i.e., the
carbanion character of ylide which is responsible for their characteristic reactions.

[4]. Organic Alkali Metal Compound Preparation: Any preparation of organic alkali metal
compounds is a source of carbanions. The reaction of organic compounds containing atoms of
chlorine, bromine, or iodine with alkali metals is one of the most often used methods for it.
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Chemical Reactions of Carbanions:

[1]. Combination with a Positive Species: The most common reaction of carbanions is their
action as Lewis bases i.e., combination with a positive species, usually a proton.

OR

[2]. As a Nucleophile in Substitution Reactions: A type of reaction that makes carbanions

valuable synthetic intermediates is their ability to function as nucleophiles in displacement
reactions. Methylsodium, for example, reacts with methyl bromide to give ethane, as follows:

[3]. Add to Double Bonds: Carbanions can add to double bonds (usually C=O double bonds),
for example, methyllithium adds to acetone to give lithium tert-butoxide, as shown:
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[4]. Rearrangment Reactions: In rare cases, the carbanions may undergo cationotropic 1, 2-
shift to give rearranged products, for example;

[5]. Oxidation: The carbanions may be oxidized to free radicals. For example:

Stability of Carbanions:

All the factors which decrease the negative charge density on carbanion increase its stability. The
stability of carbanion may be affected by following factors:

[1]. Orbitals:

s orbitals are closer to the nucleus than p orbitals are. So electrons that are in s orbitals will be
closer to the nucleus than electrons in p orbitals and therefore of lower energy. So nucleus will
easily attract the electrons. For this reason, electrons that are in sp orbitals are lower energy than
sp2 orbitals, which in turn are lower in energy than sp3, since sp2 orbitals have greater s character
(i.e. 33% ) than sp3 orbitals (having 25% s character). This makes the anions more stable.
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[2]. Inductive Effect:

Stability of alkyl carbanions can be explained by inductive effect. Greater the number of positive
groups [+ I effect] e.g., electron donating alkyl groups attached to the carbon atom bearing
negative charge, lesser is the stability. Because there inductive effect increase negative charge
density on the carbon. Thus the order of stability of carbanions is:

 Carbanion being rich in electrons is very unstable, so electron withdrawing group such
as Cl, CN, NO2 group makes the carbanion more stable.

[3]. Effect of resonance: A carbanion is stabilized by resonance if a double bond is located α to

the anionic carbon. Due to delocalization, negative charge diffuse over whole molecule and thus
stability increases. This explains the stability of the allylic and benzylic carbanions.
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Aromatic carbanions are most stable carbanions because unshared electron pair of carbanion
itself take part in delocalization.

Cyclopentadienyl anion being aromatic possess much greater stability than simplecyclopentyl
anion.

[4]. Stabilization by Sulphur and Phosphorous: Attachment of carbanionic carbon to a

sulphur and phosphorus atom causes an increase in carbanion stability. The cause of stability is
due to the delocalization of negative charge of carbanion into vaccant d-orbital of
phosphorus and sulphur.

Examples of Reactions which involve carbanion as reaction intermediate:

(i) Condensation reactions of carbonyl compounds, i.e., aldol condensation, Perkin

reaction etc.
(ii) Wittig reaction.

[3]. Carbenes
Carbene: “Carbene is defined as a molecule containing a neutral carbon atom with two unshared
valence electrons.” OR

“A carbene is a highly reactive species containing a carbon atom with six valence electrons,
practically all having lifetimes considerably less than one second.”
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General Formula of Carbene: A carbene has the following general structural formula:

Note: R and R’ could be any ligand. Examples:

 H2C: (also called methylene) is the simplest carbene and the parent species from which
all other carbene compounds are formally derived, although derivatives are more often
named by the carbene nomenclature.
 Thus CCl2 is generally known as dichlorocarbene, although it can also be called
dichloromethylene. Most carbenes are very short lived.

Classification of Carbenes:

Carbenes are classified as singlets or triplets, depending upon their electronic structure. A
carbene could exist in two spin states i.e., singlet carbene and triplet carbene.

[1]. In a singlet carbene, the two nonbonded valence electrons in the electron-deficient carbon
are in the same orbital with one spin-up and one spin-down [+1/2 and –1/2], i.e., they are a lone
pair. The C-atom in singlet carbene is sp2 – hybridized in which the paired electrons occupy an
sp2 orbital. Singlet carbenes occur more often stable in aqueous media.

Total electron spin angular momentum, S = 0

Degeneracy = 2S+1 = (2*0) + 1 = 0 + 1 = 1 = singlet
[2]. In a triplet carbene, the two nonbonded valence electrons in the electron-deficient carbon
are in adjacent, degenerate (equal energy) orbitals with same spin, +1/2 and +1/2. Since a triplet
carbene has two unpaired electrons, it is, by definition, a radical.
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Total electron spin angular momentum, S = 1

Degeneracy = 2S+1 = (2*1) + 1 = 2+1 = 3 = triplet

Triplet carbenes are generally stable in the gaseous state. Triplet carbenes may be either linear
(in most cases) as sp hybridized or bent as sp2 hybridized.

Generation of Carbenes: Carbenes can be generated by following methods:

[1]. From aliphatic diazo compounds: Carbenes are generated from diazoalkanes via
photolytic, thermal or transition metal-catalyzed routes. Typical catalysts are rhodium & copper.
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[2]. From ketenes: Ketenes can be decomposed thermally or photolytically to generate carbenes.

[3]. From epoxides: Photolytic decomposition of epoxides produce carbene.

[4]. From diazirines: Decomposition of diazarines generates carbenes.

[5]. From Tetrazoles: Thermal decomposition of tetrazoles generates carbenes.

[6]. From Alkyl Halide: This method is used for generation of chlorocarbenes.
Dichlorocarbene i.e. Cl2C: can be generated in situ from chloroform and a strong base. A strong
base removes an acidic proton adjacent to an electron withdrawing group to give a carbanion.
Loss of a leaving group from the carbanion creates a carbene.
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[7]. From ylides: Thermal decomposition of ylides generates carbenes.

Note: A ylide or ylid is a neutral dipolar molecule containing a formally negatively charged
atom (usually a carbanion) directly attached to a heteroatom with a formal positive charge
(usually nitrogen, phosphorus or sulfur), and in which both atoms have full octets of electrons.

Chemical Reactions of Carbenes:

[1]. Cycloadditions: Carbenes add on an alkene double bond giving a cyclopropane derivative.

When the reaction is perfomed in liquid medium, singlet carbene is formed, which adds on
in stereospecific way i.e., cis-alkene gives cis-cyclopropane and trans-alkene gives trans-
cyclopropane.
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In gaseous medium, the attacking species is triplet carbene, which does not add
stereospecifically.

[2]. Rearrangements: Alkyl carbenes can undergo rearrangement involving migration of an

alkyl group or hydrogen.
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[3]. Insertion Reaction: Carbenes can be inserted into other molecules as:

Stability of Carbenes:

[1]. Carbenes are electron-deficient and so electrophilic in nature. Carbenes have only six
electrons, not eight. Therefore carbenes with strongly electron-donating atoms for example
nitrogen atoms are particularly stable.

Important Note: Rather than being electron deficient, these carbenes are nucleophiles because
of the strong electron donation by the nitrogens. In fact, the classic isolatable carbenes all have
resonance electron-donating substituents on the carbene carbon.

[2]. Bulky substituents kinetically stabilize all types of carbenes. Increasing the steric bulk of
the carbene substituents broadens the bond angle (as in triplet state).

[3]. Resonance: Carbene in which carbene carbon is attached to two atoms, each bearing a lone
pair of electrons, are more stable due to resonance.

Stable Singlet Carbene in Nature:

• Thiamine (Vitamin B1). It is found in yeast (Saccharomyces cerevisiae). Its active form
is obtained by pyrophosphorylation of alcoholic group and deprotonation.
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[4]. Nitrenes

Definition: “A nitrene is a molecular fragment that has a formally neutral nitrogen atom
bearing four nonbonded valence electrons.” OR “These are neutral reaction intermediates
where the central nitrogen atom is electron-deficient and has a sextet of electrons (six electrons
in outer most shell).”

General Structural Formula and Examples of Nitrenes:

Characteristic Features of Nitrenes:

1. A nitrene (R–N:) is the nitrogen analogue of a carbene and most of what we have said
about carbenes also applies to them. Nitrenes are more stable than carbenes.
2. Nitrenes are too reactive for isolation under ordinary conditions but alkyl nitrenes have
been isolated by trapping at 4K and aryl nitrenes (more stable) can be trapped at 77 K.
3. The nitrogen atom has only 5 valence electrons and is therefore considered an
electrophile.
4. It is sp2 hybridized and planar in shape. In the simplest case, the linear N–H molecule
(imidogen) has its nitrogen atom sp hybridized, with two of its four non-bonded electrons
as a lone pair in an sp orbital and the other two occupying a degenerate pair of p orbitals.
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5. A nitrene is a reactive intermediate and is involved in many chemical reactions.

6. Similar to carbene, singlet and triplet states are possible for nitrenes.
7. The simplest nitrene is HN: which is also known as imidogen, azene or imene.

Generation of nitrenes:

Nitrenes are formed as reactive intermediates during a reaction by following common ways:

[1]. From azides: This is most common method for the generation of nitrenes. Azides yield
nitrenes by thermolysis or photolysis, with expulsion of nitrogen gas.

[2]. From Sulfinylamines: Pyrolysis of sulfinylamines generates nitrenes.

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[3]. From isocyanates with expulsion of carbon monoxide. This method is analogous to the
formation of carbenes from ketenes.

[4]. From N-bromo amide: When bromo amides are treated with base, acyl nitrene formed.

[5]. From Hydrazoic Acid: Hydrazoic acid also called as hydrogen azide is photolytically
cleaved into nitrogen and a nitrene.

Reactions of Nitrenes:

[1]. Insertion Reactions: Nitrenes, particularly acyl nitrenes and sulfonyl nitrenes (R-SO2N) can
be inserted into C-H bonds.
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Sigma insertion: Nitrenes react with alkanes and undergo sigma insertion to give amines.

Pi- insertion: Pi insertion of nitrene into C=C bond gives aziridines

[2]. Dimerization: The dimerization of phenyl nitrenes give azobenzene.

[3]. Rearrangement Reactions: Acyl nitrenes undergo a rearrangement reaction to give an alkyl
isocyanate.
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[4]. Addition to Alkenes: Nitrenes add on to alkenes to form corresponding alkeneimine, a

cyclic product.

Stability of Nitrenes:

Nitrenes are more stable than carbenes.

Reason No. 1: This greater thermodynamic stability of nitrenes relative to carbenes is attributed
to the large amount of 2s character in the orbital that is occupied by the lone pair of electrons in
nitrenes. It is so because nitrogen is more electronegative than carbon atom, therefore it holds
its electrons closer to the nucleus which decreases energy and increases stability.

Reason No. 2: More generally, the greater thermodynamic stability of nitrenes manifests itself in
the finding that the N−H bond dissociation energies (BDEs) of aminyl radicals are
approximately 20 kcal/mol lower than the C−H BDEs of analogous alkyl radicals.

Hint: More easily the bond breaks more stable is the generated reaction intermediate.
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[5]. Benzynes
Definition: “Benzynes (or aryn'es) are highly reactive species derived from an aromatic ring by
removal of two substituents.” The most common arynes are ortho but meta- and para-arynes are
also known. OR “It is an unsaturated cyclic hydrocarbon (with formula
C6H4) derived from and structurally similar to benzene but having one of the double bonds of
benzene replaced by a triple bond.” OR “The dehydrogenated form of benzene
with two hydrogen atoms removed to form a triple bond is commonly called as benzyne.”

General Structure:

Characteristic Features of Benzynes (Arynes):

1. This is a six membered ring containing one C-C triple bond and this triple bond gives
high reactivity to the species. The resonating structures are same as that of benzene.
2. It is non-isolatable very reactive species with the hexagonal planar ring structure
with 6 pi delocalizing and 2 additional pi electrons.
3. Benzyne is also aromatic because the triple bond is formed by sideways overlap of
sp²-sp² hybrid orbitals unlike the usual p-p overlap. This happens because these sp²
orbitals are perpendicular to the p orbitals in which the conjugated electrons of
benzene lie. So these electrons cannot jump to the p orbitals and participate in
conjugation. Note: There should be 4n+2 π electrons in 'conjugation' for a molecule to be
aromatic, the molecule should be planar as well.
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4. The term benzyne is most closely associated with ortho-benzyne (1,2-

didehydrobenzene), however meta-benzyne (1,3-didehydrobenzene) and para-benzyne
(1,4-didehydrobenzene) intermediates are also present.

Note: o-Benzyne, in which the ortho hydrogens are removed, is most important from
synthetic point of view, since it is a strong electorophile and a potent dienophile in the Diels-
Alder reaction.

Generation of benzynes:

Due to extreme reactivity of arynes they must be generated in situ.

[1]. From Aryl Halides:

Aryl halide can be treated with strong base (like sodium amide) to remove an aromatic proton
and generate benzyne via elimination.

[2]. Zwitterion Intermediate Approach:

This reaction is most commonly used with an anthranilic acid precursor. Reaction with
NaNO2 and a strong acid, such as HCl yields the diazonium salt i.e., a zwitterionic benzene-2-
carboxylate. Subsequent addition of base like NaOH deprotonates the carboxylic acid which
upon heating forms benzyne.
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[3]. From Grignard Reagents:

Under relatively mild conditions benzyne can be generated using a Grignard intermediate.
Addition of Mg metal to a dihalogen substituted benzene converts the most reactive halogen
to a Grignard intermediate, followed by expulsion of the second halogen as well via E2
elimination. This reaction is driven by production of X'MgX salts, where X'=halogen (X is
typically Br).

[4]. By N-amination of 1-H-benzotriazole: N-amination of 1-H-benzotriazole with

hydroxylamine-O-sulfonic acid generates an intermediate which can be oxidised to benzyne in
almost quantitative yield with lead (IV) acetate.

Note: Generation of biphenylene by dimerisation follows quickly.

[5]. From Diels-Alder Reaction: A hexadehydro Diels-Alder reaction (HDDA) involves

cycloaddition of 1,3-diyne and alkyne. HDDA generates benzyne, which can then be trapped,
leading to diverse benzenoid products.
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Reactions of Benzynes:

[1]. Reaction with Nucleophilic Reagents:

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[2]. Reaction with Liquid Ammonia: Benzyne reacts with ammonia to form aniline as follows:

[3]. Formation of Biphenylene: If two moles of benzyne reacts with each other they form
Biphenylene.

[4]. Rearrangement Reaction of Benzyne: Conversion of m-Bromoanisole to m-anisidine is an

example.
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[5]. Reaction with Anthracene and Furan: Benzyne is too unstable to be isolated but can be
trapped by Diels-Alder reaction with anthracene or furan.

Stability of Benzyne:

Benzyne is an unstable intermediate, which has a structure similar to benzene with an additional
pi bond. The third pi bond is formed by the overlap of sp2 hybridized orbitals outside the ring.
Since the molecule is strained it is highly unstable and highly reactive species.

………………………………………………………………………………………………………

For Your Concept

Reaction Intermediates: “If a reaction occurs in more than one step, it must involve species that
are neither the reactant nor the final product. These are called reaction intermediates or simply
“intermediates”. Reactive intermediates are usually short lived and are very seldom isolated.
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The alkali metals are a group (column) in the periodic table consisting of the chemical elements
lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), and francium (Fr).

Hybridization of Carbocation: The orbitals of carbocations are generally sp2 hybridized

meaning that the p-orbital at the cationic center is empty and that the three full orbitals are
arranged in a trigonal planar geometry about the carbon nucleus. The remaining empty p orbital
will readily accept a pair of electrons from another atom.

Hybridization of Carbanion: Hybridisation of carbanion is sp3 with a lone pair of electrons.

Geometry is tetrahedron like structure but shape of the carbanion is pyramidal with a lone pair of
electrons on carbon towards upward direction.

Note: The carbanions which are stabilized by resonance are planar. Example: Allylic and
benzylic cabanions are said to have sp2 hybridization because the lone pairs present on their
carbon is involve in delocalization. However delocalization is effective if it has more planar
arrangement (which provides maximum overlap).

Hybridization of Hydrocarbon Free Radical: Therefore, it would be reasonable to expect that

a typical hydrocarbon radical, where the orbital holds 1 electron would be somewhere in between
these two extremes and be slightly pyramidal.

Transition Metals: A transition metal as "an element whose atom has a partially filled d sub-
shell, or which can give rise to cations with an incomplete d sub-shell".

Many scientists describe a "transition metal" as any element in the d-block of the periodic table,
which includes groups 3 to 12 on the periodic table. In actual practice, the f-block lanthanide and
actinide series are also considered transition metals and are called "inner transition metals".
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Pyrolysis: Pyrolysis is the thermal decomposition of materials at elevated temperatures in an

inert atmosphere.

Phosphorylation: A biochemical process that involves the addition of phosphate group

(catalyzed by enzymes) to an organic compound. Examples include the addition of phosphate to
glucose to produce glucose monophosphate and the addition of phosphate to adenosine
diphosphate (ADP) to form adenosine triphosphate (ATP).

Pyrophosphoric Acid: Also known as diphosphoric acid, is the inorganic compound with the
formula H4P2O7.

Pyrophosphate: Pyrophosphates are phosphorus oxyanions that contain two phosphorus atoms
in a P-O-P linkage.

Rearrangements can be roughly classified on the basis of the nature of the migrating group/atom.
Nucleophilic or Anionotropic: migrating group migrates with its electron pair. Electrophilic or
cationotropic: migrating group migrates without its electron pair.

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