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Stanislao Chemist.
Stanislao Cannizaro
Cannizaro was an Italian
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
Only works with aldehydes that are non-enolisable, i.e. does not have any -protons. In case of aldehydes that do have hydrogens, the aldol condensation reaction takes place preferentially.
Applicability
Definition
undergo a Auto self-oxidation-reduction, Disproportion, BasicHydrolysis, Nucleophilic addition reaction when treated with conc. aqueous base(NaoH/KoH) & it gives Acid and alcohol
Synthesis
Chemical reagents
Starting reagent
(NaoH/KoH)
Base
One molecule of aldehyde is reduced to the corresponding alcohol, while a second one is oxidized to the carboxylic acid.
Synthesis
The applicability of Cannizzaro reaction in organic synthesis is limited as the yield is not more than 50% for either acid or alcohol formed.
Explanation
The ,,-Trihalo aldehyde undergo haloform reaction in strongly alkaline medium. E.g. Choral will give chloroform in presence of an alkali.
Mechanism
In Aromatic aldehyde
Argument .
hydrogen is transferred from the second aldehyde molecule is from the solvent.
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 -hydrogens, the aldol condensation reaction takes place preferentially.
ILLUSTRATIONS
Formic acid
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
ILLUSTRATIONS
3) Furfural gives Furoic acid and Furfuryl alcohol in presence of strong alkali.
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.
ILLUSTRATIONS
Cannizzaro reaction.
Benzyl alcohol and Formic acid are obtained when a mixture of Benzaldehyde and Formaldehyde is treated with alkali.
ILLUSTRATIONS
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.
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.
Idea.
In this process, advantage is being taken of the fact that all -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 .
Step1:Neopentylglycol synthesis
Neopentylglycol (2,2-dimethyl-1,.3-propanediol) is synthesized from isobutyraldehyde (isobutanal) and formaldehyde.
The -hydrogen atom is removed by base followed by
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.
The polyols pentaerythrit (2,2bis(hydroxymethyl)-1,3-propanediol) and trimethylolpropane (2-ethyl-2-hydroxymethyl1,3-propanediol) are prepared in similar fashion.
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.
Because of its low-cost synthesis, trimethylolpropane has been used in many applications as a glycerin substitute, for example in alkyd resins.
Applications
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.
Recent Literature
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.
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
CONTINUED
This species undergoes an intramolecular 1,3-hydride shift that results in the production of the aluminium-coordinated ester
Lithium Bromide as a Flexible, Mild, and Recyclable Reagent for Solvent-Free Cannizzaro, Tishchenko, and MeerweinPonndorf-Verley Reactions
Recent Literature
Recent Literature
Lithium
Bromide as a Flexible, Mild, and Recyclable Reagent for SolventFree Cannizzaro, Tishchenko, and Meerwein-Ponndorf-Verley Reactions
Recent Literature
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
Meerwein-Ponndorf-Verley reaction
Products of Cannizzaro or Tishchenko reactions can be isolated using different workup methods. In the presence of a hydrogen donor alcohol, a MeerweinPonndorf-Verley reaction takes place.
Meerwein-Ponndorf-Verley reaction
Recent literature
Ytterbium triflate is an effective catalyst for the synthesis of either isopropyl esters or free -hydroxy-arylacetic acids (mandelic acid derivatives) from substituted aromatic glyoxals and aryl methyl ketenes, respectively.
. The environmentally friendly synthesis of mandelic acid derivatives provides products in excellent yield without any further purification after the usual workup.
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.
Refrence
^ Cannizzaro, S. (1853). "Ueber den der Benzosure entsprechenden Alkohol". Liebigs Annalen 88: 129130. ^ List, K.; Limpricht, H. (1854). "Ueber das sogenannte Benzooxyd und einige andere gepaarte Verbindungen". Liebigs Annalen 90 (2): 190210 . ^ 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
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,
ADICHEMISTRY: ONLINE CHEMISTRY RESOURCE (ORGANIC, INORGANIC, PHYSICAL & ANALYTICAL FOR CSIR UGC NET, GATE, SAT, IIT-JEE, AIEEE, JAM, AP CHEMISTRY) ;Wikipedia
Reference
.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.
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