Section-C

Ans.1-(A) Interconversion Reactions of Esters

esters
acids

   amides 

Reaction type:  Nucleophilic Acyl Substitution

Summary
 Esters can be converted into other esters (transesterification), the parent carboxylic acid
(hydrolysis) or amides  (see above).
o Transesterification : heat with alcohol and acid catalyst
o Hydrolysis : heat with aq. acid or base (e.g. aq. H2SO4 or aq. NaOH) (see hydrolysis of
esters for more details)
o Amide preparation :  heat with the amine, methyl  or ethyl esters are the most reactive
Hydrolysis of Esters

Reaction type:  Nucleophilic Acyl Substitution

Summary
 Carboxylic esters hydrolyze to the parent carboxylic acid and an alcohol.
 Reagents : aqueous acid (e.g. H2SO4) / heat, or aqueous NaOH / heat (known as
"saponification").
 These mechanisms are among some of the most studied in organic chemistry.
 Both are based on the formation of a tetrahedral intermediate which then dissociates.
 In both cases it is the C-O bond between the acyl group and the oxygen that is cleaved.
Related Reactions
 Fischer esterification
 Hydrolysis of Amides
Reaction under BASIC conditions:
 The mechanism shown below leads to acyl-oxygen cleavage (see step 2).
 The mechanism is supported by experiments using 18O labeled compounds and esters of chiral
alcohols.
 This reaction is known as "saponification" because it is the basis of making soap from
glycerol triesters in fats.
 The mechanism is an example of the reactive system type.
Ans.1(B) The Knoevenagel condensation (pronounced [ˈknøːvənaːɡl̩]) reaction is anorganic reaction named
after Emil Knoevenagel. It is a modification of the aldol condensation.[1][2]
A Knoevenagel condensation is a nucleophilic addition of an active hydrogen compound to a carbonyl group
followed by a dehydration reaction in which a molecule of water is eliminated (hence condensation). The product is
often an αβ-unsaturated ketone (a conjugated enone).
In this reaction the carbonyl group is an aldehyde or a ketone. The catalyst is usually a weakly basic amine. The
active hydrogen component has the form [3]
 Z–CH2-Z or Z–CHR–Z for instance diethyl malonate, Meldrum's acid, ethyl acetoacetate or malonic acid,
or cyanoacetic acid.[4]
 Z–CHR1R2 for instance nitromethane.
where Z is an electron withdrawing functional group. Z must be powerful enough to facilitate deprotonation to
the enolate ioneven with a mild base. Using a strong base in this reaction would induce self-condensation of the
aldehyde or ketone.
The Hantzsch pyridine synthesis, the Gewald reaction and the Feist–Benary furan synthesis all contain a
Knoevenagel reaction step. The reaction also led to the discovery of CS gas.
Ans.2- Azulene, which has a specific structure of ring-fused unsaturated seven-membered and five-membered
rings, is a typical non-benzenoid aromatic compound. Whereas naphthalene or other hydrocarbon compounds are
generally colorless, azulene, a structural isomer of naphthalene, is dark blue, and the name comes from the Spanish
word azul, meaning "blue". Three practical manufacturing methods have been known so far as follows:
The first method, which was developed by Ziegler and Hafner, is a reaction of ring-opened pyridinium salts or
pyrylium salts with cyclopentadienides. The second one, which was developed by Nozoe and Seto et al.is a reaction of
tropone derivatives bearing halogen, methoxy, or tosyloxy groups at the 2 position and active methylene compounds,
such as cyanoacetates and malonates, in the presence of base. The last method, which was developed by Yasunami
and Takase et al., is a reaction of oxaazulanones with enamines.
　Tropolone derivatives are also classified as non-benzenoid aromatic compounds. Hinokitiol, a typical tropolone
compound, has been known to exhibit an antibacterial effect. Also colchicine, an alkaloid compound with a tropolone
ring, shows strong antitumor effects. Thus, tropolone compounds have possibilities in the pharmaceutical field,
especially for anticancer drugs.

The vector stencils library "Aromatics" contains 23 symbols of aromatic rings for chemical drawing of molecular
structural formulas and reaction mechanism schemes in organic chemistry. 
"In organic chemistry, aromaticity is a chemical property describing the way in which a conjugated ring of
unsaturated bonds, lone pairs, or empty orbitals exhibits a stabilization stronger than would be expected by the
stabilization of conjugation alone. ... Aromaticity can also be considered a manifestation of cyclic delocalization and
of resonance. This is usually considered to be because electrons are free to cycle around circular arrangements of
atoms that are alternately single- and double-bonded to one another. These bonds may be seen as a hybrid of a
single bond and a double bond, each bond in the ring identical to every other. This commonly seen model of
aromatic rings, namely the idea that benzene was formed from a six-membered carbon ring with alternating single
and double bonds (cyclohexatriene), was developed by Kekulé (see History section below). The model for benzene
consists of two resonance forms, which corresponds to the double and single bonds superimposing to give rise to
six one-and-a-half bonds. Benzene is a more stable molecule than would be expected without accounting for charge
delocalization. ... Types of aromatic compounds. The overwhelming majority of aromatic compounds are
compounds of carbon, but they need not be hydrocarbons. 1. Neutral homocyclics. Benzene, as well as most other
annulenes (cyclodecapentaene excepted) with the formula CnHn where n is an even number, such as
cyclotetradecaheptaene. 2. Heterocyclics. In heterocyclic aromatics (heteroaromats), one or more of the atoms in
the aromatic ring is of an element other than carbon. This can lessen the ring's aromaticity, and thus (as in the case
of furan) increase its reactivity. Other examples include pyridine, pyrazine, imidazole, pyrazole, oxazole, thiophene,
and their benzannulated analogs (benzimidazole, for example). 3. Polycyclics. Polycyclic aromatic hydrocarbons are
molecules containing two or more simple aromatic rings fused together by sharing two neighboring carbon atoms
(see also simple aromatic rings). Examples are naphthalene, anthracene, and phenanthrene. 4. Substituted
aromatics. Many chemical compounds are aromatic rings with other functional groups attached. Examples include
trinitrotoluene (TNT), acetylsalicylic acid (aspirin), paracetamol, and the nucleotides of DNA. 5. Atypical aromatic
compounds. Aromaticity is found in ions as well: the cyclopropenyl cation (2e system), the cyclopentadienyl anion
(6e system), the tropylium ion (6e), and the cyclooctatetraene dianion (10e). Aromatic properties have been
attributed to non-benzenoid compounds such as tropone. Aromatic properties are tested to the limit in a class of
compounds called cyclophanes. A special case of aromaticity is found in homoaromaticity where conjugation is
interrupted by a single sp³ hybridized carbon atom. When carbon in benzene is replaced by other elements in
borabenzene, silabenzene, germanabenzene, stannabenzene, phosphorine or pyrylium salts the aromaticity is still
retained. Aromaticity also occurs in compounds that are not carbon-based at all. Inorganic 6-membered-ring
compounds analogous to benzene have been synthesized. Hexasilabenzene (Si6H6) and borazine (B3N3H6) are
structurally analogous to benzene, with the carbon atoms replaced by another element or elements. In borazine, the
boron and nitrogen atoms alternate around the ring.
Ans.4- Regioselective, Stereoselective, and Stereospecific Reactions
In Chapter 4 we saw that alkenes undergo electrophilic addition reactions, and we looked at the different
kinds of reagents that add to alkenes. We also examined the step-by-step process by which each reaction
occurs (the mechanism of the reaction), and we determined what products are formed. However, we did not
consider the stereochemistry of the reactions.
Stereochemistry is the field of chemistry that deals with the structures of molecules in three dimensions.
When we study the stereochemistry of a reaction, we are concerned with the following questions:
1. If a reaction product can exist as two or more stereoisomers, does the reaction produce a single
stereoisomer, a set of particular stereoisomers, or all possible stereoisomers?
2. If stereoisomers are possible for the reactant, do all stereoisomers react to form the same
stereoisomeric product, or does each reactant form a different stereoisomer or a different set of
stereoisomers?
Before we examine the stereochemistry of electrophilic addition reactions, we need to become familiar with
some terms used in describing the stereochemistry of a reaction. 
a regioselective reaction is one in which two constitutional isomers can be obtained as products but more of
one is obtained than of the other. In other words, a regioselective reaction selects for a particular
constitutional isomer. Recall that a reaction can be moderately regioselective, highly regioselective, or
completely regioselective depending on the relative amounts of the constitutional isomers formed in the
reaction. 

Stereoselective is a similar term, but it refers to the preferential formation of a stereoisomer rather than a
constitutional isomer. If a reaction that generates a carbon– carbon double bond or an asymmetric carbon in a
product forms one stereoisomer preferentially over another, it is a stereoselective reaction. In other words, it
selects for a particular stereoisomer. Depending on the degree of preference for a particular stereoisomer, a
reaction can be described as being moderately stereoselective, highly stereoselective, or completely
stereoselective. 
A reaction is stereospecific if the reactant can exist as stereoisomers and each stereoisomeric reactant leads
to a different stereoisomeric product or a different set of stereoisomeric products. 

In the preceding reaction, stereoisomer A forms stereoisomer B but does not form D, so the reaction is
stereoselective in addition to being stereospecific. All stereospecific reactions, therefore, are also
stereoselective. All stereoselective reactions are not stereospecific, however, because there are
stereoselective reactions in which the reactant does not have a carbon–carbon double bond or an asymmetric
carbon, so it cannot exist as stereoisomers.

SECTION-B
Ans.1- The SN2 reaction is concerted. That is, the SN2 occurs in one step, and both the nucleophile and
substrate are involved in the rate determining step. ... The SN1 reaction proceeds stepwise. The leaving group
first leaves, whereupon a carbocation forms that is attacked by the nucleophile.
Ans.2- Electrophilic aromatic substitution is an organic reaction in which an atom that is attached to an aromatic
system(usually hydrogen) is replaced by an electrophile. Some of the most important electrophilic aromatic
substitutions arearomatic nitration, aromatic halogenation, aromatic sulfonation, and acylation and
alkylating Friedel–Crafts reaction.

Ans.-3 In chemistry, a carbene is a molecule containing a neutral carbon atom with a valence of two and two
unshared valence electrons. The general formula is R-(C:)-R' or R=C:.
The term "carbene" may also refer to the specific compound H2C:, also called methylene, the parenthydride from
which all other carbene compounds are formally derived. [1][2] Carbenes are classified as either singlets or triplets,
depending upon their electronic structure. Most carbenes are very short lived, although persistent carbenes are
known. One well-studied carbene is dichlorocarbene Cl2C:, which can be generated in situ from chloroform and a
strong base.
Ans.5. Chirality /kaɪˈrælɪti/ is a geometric property of some molecules and ions. A chiral molecule/ion is non-
superposable on its mirror image. The presence of an asymmetric carbon center is one of several structural features
that induce chirality in organic and inorganic molecules.[1][2][3][4]The term chirality is derived from the Greek word for
hand, χειρ (kheir).
The mirror images of a chiral molecule/ion are called enantiomers oroptical isomers. Individual enantiomers are
often designated as either "right-" or "left-handed". Chirality is an essential consideration when discussing
the stereochemistry in organic and inorganic chemistry. The concept is of great practical importance because most
biomolecules and pharmaceuticals are chiral.
Ans.-7- Benzyne is an example of an aryne (-yne = triple bond) This is no ordinary triple bond as the second
p interaction results from a weak interaction of sp2 hybrid orbitals lying in the plane of the ring. The triple bond
is non-linear due to the constraints of the 6-membered ring. Benzyne is strained and highly reactive.