Post on 15-Jul-2015
Presented By
Mr. Kiran R. Dhangar
( M. Pharm ) IST SEM
Dept. of Pharmaceutical Chemistry
RCPIPER, Shirpur 425405
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1.Introduction
2.Definition
3.General Reaction
4.Reaction Mechanism
5.Stereochemistry
6.Applications
7.References2
The Beckmann rearrangement, named after the German
chemist Ernst Otto Beckmann (1853–1923).
The acid catalyzed rearrangement involving the conversion
of ketoximes into amide is known as the Beckmann
rearrangement.
A variety of acidic reagents such as H3PO2, H2SO4, P2O5,
SOCl2 and PCl5 have been found to catalyze this
rearrangement.3
The Beckmann rearrangement is an acid catalyzed
transformation of a ketoxime, the oxime of a ketone to an amide,
Acid converts the oxime hydroxy to a good leaving group and
promotes arrangement of an adjacent aryl or alkyl group.
Retention of configuration.
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Victor Grignard
Grignard Reagents
• Discovered by Victor Grignard in 1900
– Key factors are etheral solvent and water-free conditions
• Awarded Nobel Prize in 1912
Grignard, Victor , 1871–1935, French chemist. He shared the 1912 Nobel Prize in Chemistry for his work in organic synthesis based on his discovery (1900) of the Grignard Reagent. He taught at the Univ. of Nancy (1909–19) and at the Univ. of Lyons (from 1919 until the end of his career).
The First Organometallic Reagents…
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Organometallic compound:A compound that contains a carbon-metal
bond.
Organometallic Reagents
The Key Concepts:
Make a carbon negatively charged/polarized so it
is nucleophilic.
Reaction with electrophilic carbons can make
carbon-carbon bonds.
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Grignard Reaction:
The addition of Grignard reagent to aldehydes
and ketones is known as the Grignard reaction.
RX Mg RMgX
A Grignard Reagent
+Anhydrous
ether
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Grignard reaction is a key step in the industrial
production of Tamoxifen:
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1. Jerry March, Advanced Organic Chemistry, Reaction, Mechanism andstructure, fourth edition, Wiley publishing house, page no.1095-1096
2. Stanley H. Pine, Organic Chemistry , fifth edition, page no.987
3. G.R. Chatwal, Reaction Mechanism and reagents in Organic Chemistry,fifth edition 2012, Himalaya Publishing house, page no.16.28-16.32
4. O. P. Agarawal, Organic Chemistry Reaction and Reagents, 48th Edition,GOEL publishing house 2012, page no.539-540
5. Solomon And Fryhle , Organic Chemistry, 18th edition, Wiley publishinghouse,2004, page no.552-562
6. Joshua Howrth , Core Organic Chemistry, first edition , Wiley publication,Singapore 1998, page no. 149
Beckmann rearrangement
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7. Ernest L. Eliel, Stereochemistry of Carbon Compounds,first edition, Tata
McGraw Hill Edition,2010, page no.120,323-324.
8. Chandrasekhar, S.; Gopalaiah, K. Beckmann reaction of oximes catalyzed by
chloral: Mild and neutral procedures. Tetrahedron Lett. 2003, 44, 755–756.
9. Douglass F. Taber , Patrick J. Straney, The Synthesis of Laurolactam from
Cyclododecanone via a Beckmann Rearrangement, Journal of Chemical
Education 2006, 2-13.
Grignard Rearrangement
1. Jerry March, Advanced Organic Chemistry, Reaction, Mechanism andstructure, Wiley publishing house, fourth edition, page no.920-929
2. Robert Thornton Morrison, Robert Neilson Boyd and Saibal kantiBhattacharyajee, Organic Chemistry, Pearson publication, Seventh edition,page no.143-145.
3. G.R. Chatwal, Reaction Mechanism and reagents in Organic Chemistry,Himalaya Publishing house, fifth edition 2012 , page no.9.9-9.11
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4. O. P. Agarawal, Organic Chemistry Reaction and Reagents, 48th Edition, GOELpublishing house 2012, page no.953-954
5. Joshua Howrth , Core Organic Chemistry, first edition , Wiley publication,Singapore 1998, page no. 13, 92, 95, 105, 111, 138, 153, 514.
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