RASHRASANT TUKDOJI MAHARAJ NAGPUR UNIVERSITY

SEMINAR SEMESTER – I
2017 – 2018

SYNTHETIC APPLICATIONS OF CARBENES AND

NITRENES

Name of Student :- DIPALI P. GARGHATE.

Name of Supervisor :- PROF. B. N. BERAD

Name of the Department and address :-

DEPARTMENT OF CHEMISTRY
Amravati Road, Nagpur – 440033

Date of Presentation :- 05/10/2017

Time :- 2.00 Pm to 5.00 Pm
 INTRODUCTION

• When a chemical reaction takes place the reactant molecules get

converted into product molecules. However, in between these two
steps, there is formation and consumption of number of spices. They
are highly reactive and short lived. Their isolation is not possible in
most of the cases. However, their formation can be confirmed
experimentally. Intermediate species obtained during the course of
reaction are called Reactive intermediates or reaction intermediate.

• For example. Carbene and nitrene are some of the reactive

intermediates.
CARBENES

Carbenes are neutral reactive intermediates contains a bivalent carbon atom

in which the carbon atom has six electrons in the valence shell of which four are
bonded and two are unshared.

Highly reactive carbon intermediate represented by.

Carbenes are usually thought to be SP2 hybridized out of the four electrons in
valence shell of carbon atom two electrons are bonding and two are unshared. The
two bonding electrons are in two hybrid orbital's. The unpaired electrons may be
eighter present in single orbital or in two orbital's. If both the electronics are paired
in SP hybrid orbital. The total spin quantum number becomes S = 0 and so the
multiplicity becomes M = 25 + 1. Hence it is called as singlet carbene.
 If unshared electrons remains unpaired, one in SP hybrid orbital and
second in P – orbital, the total spin quantum number becomes S = 1 and so the
multiplicity becomes M = 25 + 1 hence, it is called as triplet carbene.
Generation of carbene
Carbenes are endothermic species so, for their seneration energy is
supplied in the form of heat or light.
i) Mostly these are prepared by thermal or photolytic elimination reaction.

ii) From Diazo Compunds :-

Diazocompounds easily decompose thermally and
photochemically to give carbenes.
Application of carbenes :-
Single carbenes are more reactive than the triplet species. This may be
due to the electron repulsion energy that must be overcome to pair two
electrons in an orbital. So the ground state both singlet and triplet carbenes are
highly reactive species. Their reactivity can be moderated by using copper
powder in their reaction.

Carbenes undergo a variety of reaction. The synthetics applications are

listes below :-
1) Carbenes being the electron deficient species may take part in
electrophilic aromatic substitution reaction.

For example, in Reimer – Tiemann reaction

ii) II – Insertion Reaction :-

Carbenes undergo cycloaddition with C = C bond the give

cyclopropanes. Singlet carbenes undergo cis-stereospecific insertion
with cis-alkenes giving thermodynamically less stable sun-products.
Triplet carbenes give a mixture of both syn-and anti – adducts.

Whereas the above cycloddition of singlet carbenes is a concerted

process the triplet carbenes react in step involving a diradical
intermediate.
Insertion reaction :-
Like II insertions carbenes may also take part in insertion reaction. But
the reactions are of a little synthetic importance since these takes place
indiscriminately.

ii) Carbenes react with nucleophilic to from different classes of

compound.
for example

v) Sektletal Rearrans Ements :-

Acyl carbenes undergo anionotrapic 1,2- shift to form ketenes in Wolff
rearrangement.
Nitrenes
The nitrogen analogues of carbenes are called nitrenes.
These are neutral reaction intermediates where the central
nitrogen atom is electron – deficient and has a sextet of electron.

Like carbenes, nitrones also may exist as a singlet nitrene where

the N-atom is SP hybridized. Two of the three hybrid Aos accommodate
two nonbonded electron pairs, and the third hybrid AO is engaged in a
6-bond formation. The unhybridized P – AO remains empty. The shape
of such nitrenes is planar. Nitrenes may also be formed as a triplet
diradiacal form, in which the N-atom is sp-hybridired.
 One of the two hybrid Aos accomodates a nonbonded electron
pair and the other hybrid AO is involved in a 6-bond formation. Each
unhybridized P-AO accomodates and electron of parallel spic. This
imparts a diradical nature of triplet nitrenes that are linear in shape.
 GENERATION OF NITRENES

Like carbenes these are also generated by Photolytic, thermal, or base

catalysed elimination reactions.
For example
 APPLICATION S OF NITRENES
The synthetic applications of nitrenes are listed below :-
1) Singlet nitrene undergoes a 6 insertion to give 20 amines.
for example :
6-Insertion into a C – C bond and insertion into the carbonyl group of
ketones give amider.

2) II – Insertion of nitrenes into a C = C bond gives aziridines.

3) Acyl nitrene undergo skeletal rearrangment to give alkyl

isocynates. This rearrangment is involved in curtius and Hoffmann
rearrangements.