Cannizaro reaction it is an organic name reaction.
Size: 878.9 KB
Language: en
Added: Feb 07, 2012
Slides: 71 pages
Slide Content
Cannizzaro
reaction
Introduction
Synthesis
Application
Variants
Recent literature
Stanislao Cannizaro was an Italian
Chemist.
1826-1910
Cannizzaro reaction
The first to clearify the difference
between Molecular and Atomic weights
In 1858 Cannizzaro published his "Sketch
of a Course in Chemical Philosophy"
in the journal Il Nuovo Cimento , in which
he undertook to resolve many of
chemistry's outstanding issues, basing his
arguments on the work of Avogadro
Stanislao Cannizaro
Only works with aldehydes that are
non-enolisable, i.e. does not have any
α-protons.
In case of aldehydes that do have α-
hydrogens, the aldol condensation
reaction takes place preferentially.
Applicability
Aldehyde containing NO Alpha hydrogen
undergo a Auto self-oxidation-reduction,
Disproportion, BasicHydrolysis,
Nucleophilic addition reaction when
treated with conc. aqueous
base(NaoH/KoH) & it gives Acid and alcohol
Definition
Synthesis
Chemical
reagent
s
Starting reagent
Aldehyde containing NO
Alpha hydrogen
Base
(NaoH/KoH)
Synthesis
One molecule of aldehyde is
reduced to the corresponding
alcohol, while a second one is
oxidized to the carboxylic acid.
The applicability of Cannizzaro reaction in
organic synthesis is limited as the yield is
not more than 50% for either acid or alcohol
formed.
The α,α,α-Trihalo aldehyde undergo haloform
reaction in strongly alkaline medium. E.g.
Choral will give chloroform in presence of an
alkali.
Explanation
Explanation
Involves the bas-induced disproportionation of an
aldehyde lacking a hydrogen atom in the alpha
position.
The overall order of the reaction is usually 3 or 4.
The Cannizzaro reaction takes place very slowly
when electron-donating groups are present. But the
reaction occurs at faster rates when electron
withdrawing groups are present.
Mechanism
In case Dianion form
In Aromatic aldehyde
Argument ….
hydrogen is transferred from the second
aldehyde molecule is from the solvent.
* When the reaction is carried out with D
2
O
as solvent, the resulting alcohol does not
show carbon bonded deuterium. It indicates
the hydrogen is transferred from the
second aldehyde molecule, and not from the
solvent.
In case of aldehydes that do have α-hydrogens, the aldol
condensation reaction takes place preferentially.
The Biological Analogue of
the Cannizzaro Reaction
1) Formaldehyde is disproportionate
to Formic acid and Methyl alcohol
in strong alkali.
ILLUSTRATIONS
Formic acid
It is used for decalcifier, reducer in dyeing for
wool fast colures.
Grain preservation.
As a cleaning agent in cleaning products,such as
limescale remover and toilet bowl cleaner.
Alkylating agent for Alcohols, carboxylating
agent for tertiary compounds.
Rubber industry
Formic acid is a source for a formyl group for
example in the formylation of methylaniline to
N-methylformanilide in toluene
Methyl alcohol
Methanol is used on a limited basis to fuel
internal combustion engines.
Methanol is also used as a solvent, and as an
antifreeze in pipelines and windshield washer
fluid.
About 80 per cent of methanol is used for the
manufacture of formaldehyde to produce urea
and melamine formaldehyde adhesive resins.
ILLUSTRATIONS
2) Benzaldehyde can be converted to
benzoic acid and benzyl alcohol.
Benzoic Acid uses
Food preservative
Against yeasts and bacteria n a long list of foods such as
coffee extract, cooked pickled meat and pork; jam,
jelly and marmalade; fruit juice, beverages and
sherbet and syrups, sauces and tomato paste
chemistry
Benzoic acid is the most commonly used chemical
standard to determine the heat of capacity of a bomb
calorimeter
Medicinal
Benzoic acid is a constituent of Whitfield's ointment
which is used for the treatment of fungal skin
diseases such as tinea, ringworm, and athlete's foot
Benzyl alcohol uses
Chemistry
Benzyl alcohol is used as a general solvent for
inks, paints, and epoxy resin coatings.
it is also a precursor to a variety of esters, used in
the soap, perfume, and flavor industries.
Food preservative
Against yeasts and bacteria
3) Furfural gives Furoic acid and
Furfuryl alcohol in presence of
strong alkali.
ILLUSTRATIONS
Applications
Furoic acid
Starting material in numerous furoatester.its
derivative use in flavoring agent and ofcource
preservative
Furfuryl alcohol
Uses in the production of foundry resins,
adhesive, welting agent.
as a flavoring agent.
In a cosmetics & fragrance.
4) When a mixture of Formaldehyde
and a non Enolizable aldehyde is
treated with a strong base, the later is
preferentially reduced to alcohol while
formaldehyde is oxidized to formic acid.
This variant is known as crossed
Cannizzaro reaction.
ILLUSTRATIONS
Crossed Cannizzaro
reaction.
Benzyl alcohol and Formic acid are
obtained when a mixture of
Benzaldehyde and Formaldehyde is
treated with alkali.
5) α-keto aldehyde can be converted
to α-hydroxy carboxylic acids by
an Intermolecular Cannizzaro
reaction
.
ILLUSTRATIONS
Intramolecular cannizzaro
reaction
Phenylglyoxal undergoes
intramolecular cannizzaro reaction by
giving Mandelic acid (α-
hydroxyphenylacetic acid or 2-Hydroxy-2-
phenylethanoic acid)
Mandelic acid
Mandelic acid
Cosmetics industry because it helps in reducing
wrinkles, sign of aging, initial acne
In medical industry uses as a anti bacterial, it is
also an alternative to glycolic acid in skin care
products.
The drugs cyclandelate and homatropine are
esters of mandelic acid.
6) Phthalaldehyde can undergo
intramolecular Cannizzaro reaction by giving
(o-hydroxymethyl) benzoic acid.
Intramolecular
cannizzaro
reactio n
Intramolecular Cannizaro
Reaction
Mechanism
Step 1
Step 2
Step 3
The
combination
of crossed-
Cannizaro
reaction and
aldol
condensation
Industrial
importance
The combination of aldol condensation and
crossed-Cannizaro reaction generates polyols
from formaldehyde and other aldehyde.
Used in industry to prepare polyols.
An important use of the reaction is the
preparation of Pentaerythrit from acetaldehyde
Polyols are very useful and find many applications
in industry.
• In this process, advantage is being taken of the
fact that all α-hydrogen atoms of the aldehyde
react with formaldehyde in an aldol
condensation. In a subsequent crossed-Cannizaro
reaction, the aldehyde group is then reduced to
alcohol with excess formaldehyde .
Idea .
……
Step1:Neopentylglycol
synthesis
Neopentylglycol (2,2-dimethyl-1,.3-propanediol)
is synthesized from isobutyraldehyde
(isobutanal) and formaldehyde.
The α-hydrogen atom is removed by base followed by
Aldol condensation with formaldehyde.
Step2:Neopentylglycol
synthesis
•The reaction is carried out with an
excess of formaldehyde
•. The crossed-Cannizaro reaction yields
Neopentylglycol
Applications
•Neopentylglycol is used in polyesters
(for resins used in airplane or boat
manufacturing), varnish coatings,
synthetic lubricants, and plasticizers.
The neopentyl structure provides
excellent resistance to light, heat and
hydrolysis.
Synthesis of
pentaerythrit &
trimethylolpropane
•The polyols pentaerythrit (2,2-
bis(hydroxymethyl)-1,3-propanediol) and
trimethylolpropane (2-ethyl-2-
hydroxymethyl-1,3-propanediol) are
prepared in similar fashion.
•
Applications
pentaerythrit is produced in
largest quantities.
Its main use is as raw material in
the varnish industry.
Its tetranitrate is an explosive.
Some esters of pentaerythrit with
higher fatty acids are being used
as oil additives, plasticizers and
emulsifiers.
Applications
Because of its low-cost synthesis,
trimethylolpropane has been used in
many applications as a glycerin
substitute, for example in alkyd
resins.
Similar to other polyols, it is
being used for the preparation of
polyesters and polyurethanes
A solvent-free reaction has been
reported involving mixing 2-
chlorobenzaldehyde with potassium
hydroxide in a mortar & pestle.
Solvent free
Cannizzaro
For preparative purposes, the
Cannizaro reaction as such is rather
unimportant, because one equivalent
of aldehyde generates only half an
equivalent each of acid and alcohol.
But…….
Recent Literature
But……….
At the present time, various oxidizing and
reducing agents can be used to carry out
such conversions (with higher yields), so the
Cannizzaro Reaction has limited synthetic
utility except for the conversion of α-keto
aldehydes.
Tishchenko
reaction
A variant of the Cannizzaro reaction, known
as the Tischenko reaction is a
disproportionate reaction of an Aldehyde
lacking a hydrogen atom in the alpha
position in the presence of an Alcoxide.
Catalyst are aluminium alkoxides or sodium
alkoxides. In this reaction the alcohol and
acid products combine to form an ester.
Tishchenko
reaction
Para Benzaldehyde
Mechanism of the
Reaction
• One molecule of aluminum alkoxide act
as a Lewis base to Coordinate with one
molecule of the aldehyde,and to facilate the
addition of the second equivalent of
aldehyde generating Hemiacetal
intermediate
Mechanism
This species undergoes an
intramolecular 1,3-hydride shift that
results in the production of the
aluminium-coordinated ester
CONTINUED
Lithium Bromide as a
Flexible, Mild, and
Recyclable Reagent for
Solvent-Free Cannizzaro,
Tishchenko, and Meerwein-
Ponndorf-Verley Reactions
Recent Literature
Recent Literature
►Lithium Bromide as a Flexible, Lithium Bromide as a Flexible,
Mild, and Recyclable Reagent Mild, and Recyclable Reagent
for Solvent-Free Cannizzaro, for Solvent-Free Cannizzaro,
Tishchenko, and Meerwein-Tishchenko, and Meerwein-
Ponndorf-Verley ReactionsPonndorf-Verley Reactions
Recent Literature
A convenient disproportionation or
reduction of aldehydes is promoted by
lithium bromide and triethylamine in a
solvent-free environment at room
temperature.
Recent Literature
Recent Literature
•Products of Cannizzaro or Tishchenko
reactions can be isolated using different
workup methods. In the presence of a
hydrogen donor alcohol, a Meerwein-
Ponndorf-Verley reaction takes place.
Meerwein-Ponndorf-
Verley reaction
Meerwein-Ponndorf-Verley
reaction
•Ytterbium Triflate-Promoted
Tandem One-Pot Oxidation-
Cannizzaro Reaction of Aryl
Methyl Ketones
One-Pot Oxidation-Cannizzaro
Reaction of Aryl Methyl Ketones
Recent literature
•Ytterbium triflate is an effective
catalyst for the synthesis of
either isopropyl esters or free α-
hydroxy-arylacetic acids
(mandelic acid derivatives) from
substituted aromatic glyoxals and
aryl methyl ketenes, respectively.
One-Pot Oxidation-Cannizzaro
Reaction of Aryl Methyl Ketones
One-Pot Oxidation-Cannizzaro
Reaction of Aryl Methyl Ketones
. The environmentally friendly
synthesis of mandelic acid derivatives
provides products in excellent yield
without any further purification after
the
usual workup.
One-Pot Oxidation-Cannizzaro
Reaction of Aryl Methyl Ketones
REFRENCE
THAT MAY
HELP YOU
Refrence
Massimo Curini,* Francesco Epifano,
Salvatore Genovese, M. Carla Marcotullio
and Ornelio Rosati
*Dipartimento di Chimica e Tecnologia del
Farmaco, Sezione di Chimica Organica, Via del
Liceo, 06123 Perugia, Italy, Email: curmax
unipg.it
M. Curini, F. Epifano, S. Genovese, M. C.
Marcotullio, O. Rosati, Org. Lett., 2005, 7,
1331-1333.
•^ Cannizzaro, S. (1853). "Ueber den der Benzoësäure entsprechenden Alkohol".
Liebigs Annalen 88: 129–130.
•^ List, K.; Limpricht, H. (1854). "Ueber das sogenannte Benzoëoxyd und einige
andere gepaarte Verbindungen". Liebigs Annalen 90 (2): 190–210
•.
•^ Geissman, T. A. Org. React. 1944, 2, 94. (Review)
•^ A Facile Solvent-Free Cannizzaro Reaction Phonchaiya, Sonthi; ; Panijpan, Bhinyo
Rajviroongit, Shuleewan; Wright, Tony; Blanchfield, Joanne T. J. Chem. Educ. 2009,
Refrence
Refrence
Mohammad M. Mojtahedi, Elahe Akbarzadeh,
Roholah Sharifi and M. Saeed Abaee*
*Organic Chemistry Department, Chemistry &
Chemical Engineering Research Center of Iran,
P.O. Box 14335-186, Tehran, Iran,
Email: abaeeccerci.ac.ir
M. M. Mojtahedi, E. Akbarzadeh, R. Sharifi, M. S.
Abaee,
Reference
•ADICHEMISTRY: ONLINE CHEMISTRY RESOURCE
(ORGANIC, INORGANIC, PHYSICAL & ANALYTICAL FOR CSIR UGC
NET, GATE, SAT, IIT-JEE, AIEEE, JAM, AP CHEMISTRY)
;Wikipedia
•.Cobb, Cathy, and Goldwhite, Harold (1995). Creations of Fire:
Chemistry's Lively History from Alchemy to the Atomic Age. New York:
Plenum.
•DeMilt, Clara (1965). "The Congress at Karlsruhe." In Selected
Readings in the History of Chemistry , ed. Aaron J. Ihde and William F.
Kieffer. Easton, PA: Division of Chemical Education of the American
Chemical Society.
•Ihde, Aaron (1964). The Development of Modern Chemistry. New York:
Harper & Row.
•Partington, J. R. (1989). A Short History of Chemistry. New York:
Dover Publications.
•