This document provides an overview of 9 organic reactions: 1) Metal hydride reduction using NaBH4 and LiAlH4, 2) Clemmensen reduction, 3) Birch reduction, 4) Wolff-Kishner reaction, 5) Oppenauer oxidation, 6) Dakin reaction, 7) Beckmann rearrangement, 8) Schmidt rearrangement, and 9) Claisen-Schmidt condensation. For each reaction, it discusses the reaction mechanism, modifications, and applications in organic synthesis and drug development. The document serves as a reference for graduate students and researchers on important carbonyl reactions and their uses in pharmaceutical chemistry.
This slide discusses about fused heterocyclic compound Acridine..the structural analogue of anthracene with one carbon group is replaced with nitrogen atom.
The document discusses two important metal hydride reductions - Clemmensen reduction and metal hydride reductions using sodium borohydride and lithium aluminium hydride. Clemmensen reduction involves the reduction of carbonyl groups to hydrocarbons using zinc amalgam and hydrochloric acid. Sodium borohydride is a mild reducing agent that reduces carbonyl groups to secondary alcohols. Lithium aluminium hydride is a strong reducing agent that can reduce a wide range of functional groups such as carbonyls, carboxylic acids, nitriles, and nitro groups to the corresponding alcohols or amines. Both sodium borohydride and lithium aluminium hydride reactions proceed by
Relative Aromaticity & Reactivity of Pyrrole, Furan & ThiopheneSowmiya Perinbaraj
Pyrrole, furan, and thiophene can all be aromatic according to Hückel's rule. Thiophene exhibits the greatest aromaticity followed by pyrrole then furan. This order correlates with the electronegativity of the heteroatoms, with sulfur being the least electronegative. In terms of reactivity towards electrophilic substitution, pyrrole reacts most readily followed by furan then thiophene. Pyrrole's carbon atoms are most electron-rich due to nitrogen's mesomeric effect outweighing its inductive effect.
The Dakin reaction involves the oxidation of an ortho- or para-hydroxylated phenyl aldehyde or ketone with hydrogen peroxide in a basic solution. This results in the oxidation of the carbonyl group to a benzenediol and the formation of a carboxylate. The reaction proceeds through a nucleophilic addition, 1,2 aryl migration, hydrolysis, and phenoxide ion formation steps. The reactivity depends on factors like the electrophilicity of the carbonyl carbon and the speed of the 1,2 migration. Phenyl aldehydes react faster than ketones and ortho-hydroxy compounds faster than para-hydroxy derivatives in weak basic conditions. Electron donating groups increase reactivity while electron
This document discusses heterocyclic compounds, specifically pyrazoles. It describes pyrazoles as a 5-membered heterocyclic ring containing two nitrogen atoms at the 1st and 2nd positions. Several common synthesis routes for pyrazoles are outlined, including the Paal-Knorr synthesis using 1,3-dicarbonyl compounds and hydrazines. The document also reviews reactions that pyrazoles undergo, such as electrophilic substitution, oxidation, and reduction. Finally, some medicinal uses of pyrazoles are provided, including their use as anti-pyretic, analgesic, and anti-inflammatory drugs.
This slide discusses about fused heterocyclic compound Acridine..the structural analogue of anthracene with one carbon group is replaced with nitrogen atom.
The document discusses two important metal hydride reductions - Clemmensen reduction and metal hydride reductions using sodium borohydride and lithium aluminium hydride. Clemmensen reduction involves the reduction of carbonyl groups to hydrocarbons using zinc amalgam and hydrochloric acid. Sodium borohydride is a mild reducing agent that reduces carbonyl groups to secondary alcohols. Lithium aluminium hydride is a strong reducing agent that can reduce a wide range of functional groups such as carbonyls, carboxylic acids, nitriles, and nitro groups to the corresponding alcohols or amines. Both sodium borohydride and lithium aluminium hydride reactions proceed by
Relative Aromaticity & Reactivity of Pyrrole, Furan & ThiopheneSowmiya Perinbaraj
Pyrrole, furan, and thiophene can all be aromatic according to Hückel's rule. Thiophene exhibits the greatest aromaticity followed by pyrrole then furan. This order correlates with the electronegativity of the heteroatoms, with sulfur being the least electronegative. In terms of reactivity towards electrophilic substitution, pyrrole reacts most readily followed by furan then thiophene. Pyrrole's carbon atoms are most electron-rich due to nitrogen's mesomeric effect outweighing its inductive effect.
The Dakin reaction involves the oxidation of an ortho- or para-hydroxylated phenyl aldehyde or ketone with hydrogen peroxide in a basic solution. This results in the oxidation of the carbonyl group to a benzenediol and the formation of a carboxylate. The reaction proceeds through a nucleophilic addition, 1,2 aryl migration, hydrolysis, and phenoxide ion formation steps. The reactivity depends on factors like the electrophilicity of the carbonyl carbon and the speed of the 1,2 migration. Phenyl aldehydes react faster than ketones and ortho-hydroxy compounds faster than para-hydroxy derivatives in weak basic conditions. Electron donating groups increase reactivity while electron
This document discusses heterocyclic compounds, specifically pyrazoles. It describes pyrazoles as a 5-membered heterocyclic ring containing two nitrogen atoms at the 1st and 2nd positions. Several common synthesis routes for pyrazoles are outlined, including the Paal-Knorr synthesis using 1,3-dicarbonyl compounds and hydrazines. The document also reviews reactions that pyrazoles undergo, such as electrophilic substitution, oxidation, and reduction. Finally, some medicinal uses of pyrazoles are provided, including their use as anti-pyretic, analgesic, and anti-inflammatory drugs.
This document discusses the properties and synthesis of pyridine. Pyridine is an aromatic heterocyclic compound containing a six-membered ring with one nitrogen atom. It has a planar structure and is aromatic according to Huckel's rule. Pyridine can be synthesized through several methods including the Hantzsch synthesis and from acetylene. It undergoes electrophilic substitution at the C-3 position and nucleophilic substitution at C-2 or C-4. Pyridine is used as a base in medicines such as isoniazid and omeprazole.
This document discusses the properties and synthesis of pyrrole. Pyrrole is a colorless liquid that is weakly basic and more reactive than benzene. It undergoes electrophilic substitution reactions like halogenation and nitration. Pyrrole can be synthesized through several methods, including from furan over an alumina catalyst, from succinaldehyde and ammonia in a condensation reaction, and by passing acetylene and ammonia through a hot tube. Pyrrole has medicinal uses including in cardiac medications and as an antibacterial, antipsychotic, and anticancer agent.
Baeyer-Villiger Oxidation Reaction M Pharm Chemistry.pptxDiwakar Mishra
Baeyer-Villiger Oxidation Reaction is incuded in the syllabus of Advance Organic Chemistry of first semester of the M Pharm (Pharmaceutical chemistry).
The document provides information about geometrical isomerism including definitions, examples, and methods of determination. It defines geometrical isomerism as arising from restricted rotation around a double bond that leads to different spatial arrangements of atoms. Common types of geometrical isomers include cis-trans, E-Z, and syn-anti. Methods for determining configurations include cyclization reactions, conversion to compounds of known configuration, differences in physical properties, and use of stereoselective or stereospecific reactions.
This presentation is helpful for students and faculties
of B. Pharm Second year. It has all the named reactions that are included in PCI syllabus in Pharmaceutical Organic Chemistry-3 (Unit -5). Every named reaction the presentation has introduction, mechanism and its application.This presentation is also useful for grade 12 students
B.phram
Semester .4
Subject : Organic chemistry - III
Use as reference and also usable for examination prearation.
gtu afflitited phramacy college's student may using this ppt.
Pyridine is a basic heterocyclic organic compound with the chemical formula C5H5N. It has 5 carbon atoms and 1 nitrogen atom arranged in a six-membered aromatic ring. Pyridine can be obtained from coal tar or synthesized by passing acetylene and hydrogen cyanide over a hot tube. It undergoes electrophilic aromatic substitution preferably at the carbon-3 position due to stabilization of the intermediate carbocation. Nucleophilic substitution also occurs, preferentially at the carbon-2 position. Pyridine is used as a solvent, in organic reactions, to denature alcohol, and in preparing certain drugs that contain a pyridine ring system.
The Schmidt reaction is an organic reaction in which an azide reacts with a carbonyl derivative, usually a aldehyde, ketone, or carboxylic acid, under acidic conditions to give an amine or amide, with expulsion of nitrogen
The document discusses chiral molecules and their reactions. Chiral molecules have non-superimposable mirror images due to having four different groups attached to a carbon atom without symmetry. There are three major reactions for chiral molecules: retention, where the configuration of substrate and product remain the same; inversion, where the isomer converts to the other form through an SN2 mechanism; and racemization, where a second chiral center forms diastereomers.
This document discusses the heterocyclic compound pyrrole. It begins by defining pyrrole as an unsaturated five-membered ring containing nitrogen. Pyrrole is an important compound found naturally in substances like alkaloids, hemoglobin, and chlorophyll. The document then describes several methods for synthesizing pyrrole, including the Paal-Knorr, Hantzsch, and Knorr syntheses. It also discusses some reactions pyrrole undergoes, such as electrophilic substitution and reduction. Finally, it lists several medicinal uses of pyrrole derivatives, including the amino acid proline, the stimulant nicotine, and drugs used to treat Parkinson's disease and peptic
This slide discusses about basic indole nucleus, its chemistry, synthesis, reactions and medicinal uses of Indolyl derivatives..Indole is basically fused heterocyclic compound
Indole is an aromatic heterocyclic organic compound. It contains a benzene ring fused to a pyrrole ring. Indole occurs naturally in human feces and has an intense fecal odor. It is also found in coal tar and contributes to the scents of many flowers. Electrophilic aromatic substitution of indole occurs preferentially on the five-membered pyrrole ring. Indole can be synthesized via Fischer indole synthesis or Leimgruber synthesis. It has several pharmaceutical and medical uses including for treating cancer, fibromyalgia, and schizophrenia.
Clemmensen reduction- Heterocyclic and Organic chemistry- As per PCI syllabusAkhil Nagar
The Clemmensen reduction allows the deoxygenation of aldehydes or ketones using zinc amalgam and hydrochloric acid. This converts the carbonyl group to a methylene group, producing the corresponding hydrocarbon. It is useful for substrates that are stable to strong acid, as the acidic conditions would degrade acid-labile molecules. The mechanism involves zinc carbenoids as intermediates in the reduction, without requiring alcohol intermediates. Zinc amalgam is an alloy of zinc and mercury that dissolves zinc smoothly and evenly in the reaction mixture to facilitate the reduction.
1) Furan and thiophene are 5-membered heterocyclic compounds containing oxygen and sulfur respectively. They are prepared via various synthetic routes and undergo electrophilic substitution and addition reactions.
2) Furan and thiophene have several medicinal uses. Furan derivatives like furosemide and ranitidine are used as diuretics and antiulcer drugs. Thiophene derivatives are used as antibiotics, antihistamines, anticonvulsants and anti-inflammatory drugs.
3) The document discusses the structures, properties, synthesis and reactions of furan and thiophene. It also outlines some of their common medicinal applications.
This document summarizes information about two adrenergic drugs. Phenylephrine is used for temporary relief of stuffy nose, sinus, and ear symptoms caused by common colds, flu, allergies, or other breathing illnesses by decreasing swelling in the nose and ears. Salbutamol relaxes the smooth muscle in the lungs and opens airways to improve breathing and is used to treat asthma, chronic bronchitis, emphysema, and prevent exercise-related asthma. The document was written by Dr. P Parthiban, a professor at Vellalar College of Pharmacy.
The document provides information about quinoline, isoquinoline, and indole. It discusses their structures, properties, synthesis methods, and reactions. Quinoline and isoquinoline are both heterocyclic aromatic compounds composed of a benzene ring fused to a pyridine ring. They undergo similar electrophilic and nucleophilic substitution reactions. Common synthesis routes for quinoline include the Skraup, Doebner-Miller, and Conrad-Limpach reactions. Isoquinoline synthesis methods include the Pomeranz-Fritsch and Bischler-Napieralski reactions. Indole is a bicyclic molecule with a benzene and pyrrole ring. It does not readily
Baeyer Villiger Oxidation of Ketones, Cannizzaro Reaction, MPVADITYA ARYA
The document summarizes several organic chemistry reactions:
1) The Baeyer-Villiger oxidation reaction involves the oxidation of ketones with peroxy acids to form esters through a rearrangement reaction.
2) The Cannizzaro reaction involves the base-induced disproportionation of two aldehyde molecules to form a carboxylic acid and primary alcohol.
3) The Meerwein-Ponndorf-Verley (MPV) reduction uses aluminum isopropoxide catalyst in isopropanol to reduce aldehydes and ketones to the corresponding alcohols through a reversible reaction.
This document discusses the properties and synthesis of pyridine. Pyridine is an aromatic heterocyclic compound containing a six-membered ring with one nitrogen atom. It has a planar structure and is aromatic according to Huckel's rule. Pyridine can be synthesized through several methods including the Hantzsch synthesis and from acetylene. It undergoes electrophilic substitution at the C-3 position and nucleophilic substitution at C-2 or C-4. Pyridine is used as a base in medicines such as isoniazid and omeprazole.
This document discusses the properties and synthesis of pyrrole. Pyrrole is a colorless liquid that is weakly basic and more reactive than benzene. It undergoes electrophilic substitution reactions like halogenation and nitration. Pyrrole can be synthesized through several methods, including from furan over an alumina catalyst, from succinaldehyde and ammonia in a condensation reaction, and by passing acetylene and ammonia through a hot tube. Pyrrole has medicinal uses including in cardiac medications and as an antibacterial, antipsychotic, and anticancer agent.
Baeyer-Villiger Oxidation Reaction M Pharm Chemistry.pptxDiwakar Mishra
Baeyer-Villiger Oxidation Reaction is incuded in the syllabus of Advance Organic Chemistry of first semester of the M Pharm (Pharmaceutical chemistry).
The document provides information about geometrical isomerism including definitions, examples, and methods of determination. It defines geometrical isomerism as arising from restricted rotation around a double bond that leads to different spatial arrangements of atoms. Common types of geometrical isomers include cis-trans, E-Z, and syn-anti. Methods for determining configurations include cyclization reactions, conversion to compounds of known configuration, differences in physical properties, and use of stereoselective or stereospecific reactions.
This presentation is helpful for students and faculties
of B. Pharm Second year. It has all the named reactions that are included in PCI syllabus in Pharmaceutical Organic Chemistry-3 (Unit -5). Every named reaction the presentation has introduction, mechanism and its application.This presentation is also useful for grade 12 students
B.phram
Semester .4
Subject : Organic chemistry - III
Use as reference and also usable for examination prearation.
gtu afflitited phramacy college's student may using this ppt.
Pyridine is a basic heterocyclic organic compound with the chemical formula C5H5N. It has 5 carbon atoms and 1 nitrogen atom arranged in a six-membered aromatic ring. Pyridine can be obtained from coal tar or synthesized by passing acetylene and hydrogen cyanide over a hot tube. It undergoes electrophilic aromatic substitution preferably at the carbon-3 position due to stabilization of the intermediate carbocation. Nucleophilic substitution also occurs, preferentially at the carbon-2 position. Pyridine is used as a solvent, in organic reactions, to denature alcohol, and in preparing certain drugs that contain a pyridine ring system.
The Schmidt reaction is an organic reaction in which an azide reacts with a carbonyl derivative, usually a aldehyde, ketone, or carboxylic acid, under acidic conditions to give an amine or amide, with expulsion of nitrogen
The document discusses chiral molecules and their reactions. Chiral molecules have non-superimposable mirror images due to having four different groups attached to a carbon atom without symmetry. There are three major reactions for chiral molecules: retention, where the configuration of substrate and product remain the same; inversion, where the isomer converts to the other form through an SN2 mechanism; and racemization, where a second chiral center forms diastereomers.
This document discusses the heterocyclic compound pyrrole. It begins by defining pyrrole as an unsaturated five-membered ring containing nitrogen. Pyrrole is an important compound found naturally in substances like alkaloids, hemoglobin, and chlorophyll. The document then describes several methods for synthesizing pyrrole, including the Paal-Knorr, Hantzsch, and Knorr syntheses. It also discusses some reactions pyrrole undergoes, such as electrophilic substitution and reduction. Finally, it lists several medicinal uses of pyrrole derivatives, including the amino acid proline, the stimulant nicotine, and drugs used to treat Parkinson's disease and peptic
This slide discusses about basic indole nucleus, its chemistry, synthesis, reactions and medicinal uses of Indolyl derivatives..Indole is basically fused heterocyclic compound
Indole is an aromatic heterocyclic organic compound. It contains a benzene ring fused to a pyrrole ring. Indole occurs naturally in human feces and has an intense fecal odor. It is also found in coal tar and contributes to the scents of many flowers. Electrophilic aromatic substitution of indole occurs preferentially on the five-membered pyrrole ring. Indole can be synthesized via Fischer indole synthesis or Leimgruber synthesis. It has several pharmaceutical and medical uses including for treating cancer, fibromyalgia, and schizophrenia.
Clemmensen reduction- Heterocyclic and Organic chemistry- As per PCI syllabusAkhil Nagar
The Clemmensen reduction allows the deoxygenation of aldehydes or ketones using zinc amalgam and hydrochloric acid. This converts the carbonyl group to a methylene group, producing the corresponding hydrocarbon. It is useful for substrates that are stable to strong acid, as the acidic conditions would degrade acid-labile molecules. The mechanism involves zinc carbenoids as intermediates in the reduction, without requiring alcohol intermediates. Zinc amalgam is an alloy of zinc and mercury that dissolves zinc smoothly and evenly in the reaction mixture to facilitate the reduction.
1) Furan and thiophene are 5-membered heterocyclic compounds containing oxygen and sulfur respectively. They are prepared via various synthetic routes and undergo electrophilic substitution and addition reactions.
2) Furan and thiophene have several medicinal uses. Furan derivatives like furosemide and ranitidine are used as diuretics and antiulcer drugs. Thiophene derivatives are used as antibiotics, antihistamines, anticonvulsants and anti-inflammatory drugs.
3) The document discusses the structures, properties, synthesis and reactions of furan and thiophene. It also outlines some of their common medicinal applications.
This document summarizes information about two adrenergic drugs. Phenylephrine is used for temporary relief of stuffy nose, sinus, and ear symptoms caused by common colds, flu, allergies, or other breathing illnesses by decreasing swelling in the nose and ears. Salbutamol relaxes the smooth muscle in the lungs and opens airways to improve breathing and is used to treat asthma, chronic bronchitis, emphysema, and prevent exercise-related asthma. The document was written by Dr. P Parthiban, a professor at Vellalar College of Pharmacy.
The document provides information about quinoline, isoquinoline, and indole. It discusses their structures, properties, synthesis methods, and reactions. Quinoline and isoquinoline are both heterocyclic aromatic compounds composed of a benzene ring fused to a pyridine ring. They undergo similar electrophilic and nucleophilic substitution reactions. Common synthesis routes for quinoline include the Skraup, Doebner-Miller, and Conrad-Limpach reactions. Isoquinoline synthesis methods include the Pomeranz-Fritsch and Bischler-Napieralski reactions. Indole is a bicyclic molecule with a benzene and pyrrole ring. It does not readily
Baeyer Villiger Oxidation of Ketones, Cannizzaro Reaction, MPVADITYA ARYA
The document summarizes several organic chemistry reactions:
1) The Baeyer-Villiger oxidation reaction involves the oxidation of ketones with peroxy acids to form esters through a rearrangement reaction.
2) The Cannizzaro reaction involves the base-induced disproportionation of two aldehyde molecules to form a carboxylic acid and primary alcohol.
3) The Meerwein-Ponndorf-Verley (MPV) reduction uses aluminum isopropoxide catalyst in isopropanol to reduce aldehydes and ketones to the corresponding alcohols through a reversible reaction.
The combination of a carbonyl group and a hydroxyl on the same carbon atom is called a carboxyl group. Compounds containing the carboxyl group are called carboxylic acids. The carboxyl group is one of the most widely occurring functional groups in organic chemistry.
Aromatic Carboxylic acids: Carboxylic acids have an aryl group bound to the carboxyl group is known as aromatic carboxylic acids. The general formula of an aliphatic aromatic carboxylic acid is Ar-COOH.
Acidity of carboxylic acid:
A carboxylic acid may dissociate in water to give a proton and a carboxylate ion. Dissociation of a carboxylic acid involves breaking an O-H bond gives a carboxylate ion with the negative charge spread out equally over two oxygen atoms, compared with just one oxygen atom in an alkoxide ion. The delocalized charge makes the carboxylate ion more stable therefore; dissociation of a carboxylic acid to a carboxylate ion is less endothermic.
Preparation Methods:
1. Oxidation:
The oxidation of aldehyde with oxidizing agents such as CrO3 to forms carboxylic acids containing the same numbers of carbon atoms with a oxidizing agents like chromic acid, chromium trioxide. The silver oxide (Ag2O) in aqueous ammonia solution (Tollen’s reagent) is mild reagent give good yield at room temperature. E.g. Acetaldehyde reacts with CrO3 in aqueous acid to give acetic acid.
2. Grignard reagents (from CO2):
Carboxylic acid can be prepared by the reaction of Grignard reagent (alkyl magnesium halide) with carbon dioxide (CO2) in presence of dry ether. Grignard reagents react with carbon dioxide to forms a magnesium carboxylates which on hydrolysis by dilute HCl produces carboxylic acids.
3. Hydrolysis of nitrile:
The hydrolysis of nitrile or cyanide in presence of dilute acid to forms a carboxylic acid. In this reaction –CN group is converted to a –COOH group.
4. Hydrolysis Reactions:
All the carboxylic acid derivatives can be hydrolyzed into the carboxylic acid in the acidic or basic media; the hydrolysis reaction is fast and occurs in presence of water with no acid or base catalyst.
1. From Ester (Hydrolysis of ester): Ester can be hydrolyzed in either acidic or basic medium to yield carboxylic acid. The ester is heated with an excess of water contains strong acid or base catalyst.
Properties of Carboxylic Acids:
1. Low molecular weights carboxylic acids are colourless liquid at room temperature i.e. lower member ate liquid up to C9 and have characteristic odors whereas higher members are solid.
2. Carboxylic acids are polar organic compound. Low molecular weight carboxylic acids (first four members) are soluble in water whereas solubility in water decrease as molecular weight and chain lengthing increases.
3. Aromatic acids are insoluble in water.
4. Carboxylic acids have higher melting and boiling point due to their capacity to readily form stable hydrogen-bonded dimers.
Aldehydes and ketones contain a carbonyl group (>C=O) and can undergo numerous reactions. In aldehydes, the carbonyl is bonded to one alkyl group and one hydrogen. In ketones, it is bonded to two alkyl groups. Common reactions include reduction to alcohols using LiAlH4 or NaBH4, addition of Grignard reagents, and reactions involving the acidic alpha-hydrogens like benzoin condensation, Cannizzaro reaction, and Clemmenson reduction. Other important reactions are the Wittig reaction, Knoevenagel condensation, Wolf-Kishner reduction, and Baeyer-Villiger oxidation.
The reactions of aldehydes or ketones with ammonia, primary amines, or secondary amines in the presence of reducing agents to give primary, secondary, or tertiary amines, respectively are known as reductive aminations (of the carbonyl compounds) or reductive alkylation's (of the amines).
The document discusses the chemistry of quinazoline and its derivatives. It begins with an introduction to quinazoline, which is a heterocyclic compound formed from the fusion of benzene and pyrimidine rings. It then describes some of the common synthetic methods used to produce quinazoline derivatives, including metal-catalyzed reactions using copper or zinc, and reagent-base reactions. The document also briefly mentions some of the biological activities of quinazoline derivatives, focusing on their potential use as anticancer and antibacterial agents.
Organic chemistry: Hydrocarbons, Alkyl Halides and alcoholsIndra Yudhipratama
This document outlines topics in organic chemistry including hydrocarbons, alkyl halides, and alcohols. It discusses the reactions and properties of alkanes such as combustion and free radical reactions. Alkenes and alkynes are introduced along with elimination and addition reactions. Alkyl halides are explored with substitution reactions. Finally, the document covers alcohols and their elimination through dehydration and oxidation reactions.
Aldehydes and ketones contain a carbonyl group consisting of a carbon double-bonded to an oxygen. Chapter 17 discusses the properties, nomenclature, synthesis, and reactions of aldehydes and ketones. Key reactions include nucleophilic additions to the carbonyl carbon to form alcohols, such as hydration to form geminal diols or addition of alcohols or amines. Other reactions include oxidations of alcohols to form aldehydes or ketones, and reductions of aldehydes or ketones using reagents such as sodium borohydride or lithium aluminum hydride.
Aldehydes and ketones contain a carbonyl functional group consisting of a carbon double-bonded to an oxygen. They exhibit characteristic reactivity including nucleophilic addition reactions that form alcohols. Aldehydes and ketones undergo hydration to form geminal diols, addition of alcohols to form hemiacetals and acetals, and addition of amines to form imines through a condensation reaction. Their carbonyl group absorbs strongly in the infrared region and gives deshielded peaks in NMR spectroscopy due to polarization effects.
This document provides information about carboxylic acids and their derivatives. It begins by stating the learning outcomes, which are to provide nomenclature of carboxylic acids and derivatives, describe physical properties of carboxylic acids, and explain the synthesis and reactions of carboxylic acids and derivatives. The document then discusses the structure, naming rules, physical properties, acid strength, and synthesis methods of carboxylic acids. It also explains the nomenclature and reactions of common carboxylic acid derivatives like esters, acid halides, anhydrides, and amides.
1) Wilkinson catalyst, chlorotris(triphenylphosphine)rhodium(I), is an efficient homogeneous catalyst for hydrogenation of alkenes.
2) The mechanism of hydrogenation involves oxidative addition, ligand dissociation, alkene coordination, migratory insertion, ligand association, and reductive elimination steps.
3) The hydrogenation is selective based on sterics and substitution - less substituted and sterically hindered alkenes react first, followed by exocyclic over endocyclic and cis over trans alkenes.
Carboxylic acids contain the carboxyl group and include common derivatives like acid halides, acid anhydrides, esters, and amides. They are named using IUPAC or common systems and are acidic due to resonance stabilization of the carboxyl group. Carboxylic acids are prepared through oxidation reactions of alkenes, alcohols, aldehydes, and alkyl benzenes or by hydrolysis of nitriles and carbonation of Grignard reagents. Common reactions produce esters, acid halides, anhydrides, and amides. Ibuprofen is a carboxylic acid used as an NSAID with adverse effects including nausea, diarrhea, and headache.
Ketones are organic compounds that contain a carbonyl functional group (C=O). Ketones can be prepared through oxidation of secondary alcohols, hydration of alkynes, ozonolysis of alkenes, Friedel-Crafts acylation, and use of Grignard reagents. Ketones undergo reactions such as reduction to alcohols, nucleophilic addition, reactions with Grignard reagents, and addition of derivatives of ammonia. Some pharmaceutical drugs contain ketone groups, such as antibiotics, drugs that interfere with tumor growth, and pain medications.
This document discusses the reactivity of various carboxylic acid derivatives including alkanoyl halides, anhydrides, esters, amides, and alkanenitriles. It compares their relative reactivities and describes common reaction mechanisms. Alkanoyl halides are the most reactive and undergo nucleophilic substitution reactions. Anhydrides and esters undergo similar reactions but are less reactive. Amides have lower acidity than esters due to resonance and undergo hydrolysis or reduction. Alkanenitriles undergo hydrolysis to carboxylic acids or reactions with organometallic reagents to form ketones or aldehydes.
This document discusses the reactivity of various carboxylic acid derivatives including alkanoyl halides, anhydrides, esters, amides, and alkanenitriles. It provides the relative reactivity of these derivatives, with alkanoyl halides being the most reactive and alkanenitriles being the least reactive. The document discusses the origins of reactivity through inductive and resonance effects. It then summarizes common reactions for each derivative including hydrolysis, reactions with alcohols/amines/organometallic reagents, and reductions. Mass spectrometry is also briefly discussed.
This document summarizes various methods of chemical reduction. It discusses heterogeneous catalytic hydrogenation using platinum, palladium, nickel, and copper chromite catalysts. Alkenes are converted to alkanes, and unsaturated functional groups like carbonyls, nitriles, and aromatics can be reduced. Homogenous hydrogenation uses soluble transition metal complexes as catalysts, like rhodium and ruthenium. Rhodium complexes selectively reduce double bonds without affecting other functional groups. Reduction of alkynes, aromatics, aldehydes, ketones, nitriles, oximes and nitro compounds are also summarized. The mechanisms of catalytic and homogenous hydrogenation are provided.
1. Carboxyl derivatives such as acid chlorides, anhydrides, esters, amides, and nitriles undergo nucleophilic acyl substitution or hydrolysis reactions depending on conditions.
2. Acid chlorides undergo substitution readily due to the good leaving ability of the chloride ion. Esters hydrolyze slowly in water but more readily with acid or base via addition-elimination mechanisms.
3. Amides hydrolyze in acidic conditions through a resonance-stabilized cation intermediate or in basic conditions via a dianion intermediate to give carboxylic acids. Nitriles hydrolyze to carboxylic acids or amides.
Geometrical isomerism, also known as cis-trans isomerism, results from restricted rotation around a carbon-carbon double bond. There are two types of geometrical isomers: cis isomers have substituents on the same side of the double bond, while trans isomers have substituents on opposite sides. The E-Z system can unambiguously assign configurations using CIP priority rules to rank substituents. Geometrical isomers have the same connectivity but different spatial arrangements, making them stereoisomers.
1. Optical isomerism refers to compounds that exist in two forms that are non-superimposable mirror images and rotate plane-polarized light in opposite directions.
2. Compounds are optically active if they contain a chiral carbon - a carbon bonded to four different groups - and lack a plane of symmetry.
3. The two enantiomers of an optically active compound have equal but opposite rotations of plane-polarized light and are distinguished as (+) and (-) forms. Their mixture is optically inactive.
The document discusses heterocyclic compounds and provides information about pyrrole. It begins by defining heterocyclic compounds as ring compounds containing elements other than carbon, such as oxygen, nitrogen, and sulfur. It then discusses the nomenclature of heterocyclic compounds using prefixes and suffixes to indicate the heteroatom and ring size. Specific heterocycles are named, including pyrrole. The properties of pyrrole are described, such as its aromaticity due to satisfying Huckel's rule. Its physical and chemical properties, including its basicity, are explained. Methods for synthesizing pyrrole from acetylene, ammonium mucate, and succinimide are presented.
1. Aromatic acids contain one or more carboxyl groups directly attached to an aromatic ring. The acidity of aromatic acids is influenced by electron withdrawing and donating groups on the ring through inductive or resonance effects.
2. Electron withdrawing groups increase the acidity of benzoic acid by stabilizing the anion through resonance. Electron donating groups decrease acidity by increasing the electron density of the aromatic ring.
3. Aromatic acids undergo various reactions including salt formation, esterification, acylation, reduction, decarboxylation, and electrophilic substitution.
This document provides information about fats, oils, and their properties. It defines fats and oils as lipids that are saponifiable (containing ester groups) and made up of triglycerides consisting of glycerol bonded to three fatty acid chains. The document discusses the hydrolysis, hydrogenation, saponification, and rancidification reactions of fats and oils. It also defines analytical values used to characterize fats and oils such as saponification value, iodine value, and acid value. Sources and extraction methods of fats and oils from plants and animals are also summarized.
Cycloalkanes are cyclic hydrocarbons containing only carbon and hydrogen. They have properties similar to alkanes but are more rigid due to their cyclic structure. Cycloalkanes are important compounds that are used in various industries and as precursors to other organic compounds.
Amines are organic compounds derived from ammonia by replacing one or more hydrogen atoms with alkyl or aryl groups. They can be classified as primary, secondary, or tertiary depending on the number of alkyl/aryl groups attached to the nitrogen atom. Aromatic amines have an amine group directly attached to an aromatic ring. Amines can act as bases by accepting protons. Their basicity depends on factors like substitution, with electron-donating groups increasing basicity. Amines undergo reactions like salt formation with acids, nitrosoamine formation with nitrous acid, amide formation with acyl chlorides/anhydrides, and halogenation of aromatic amines.
Phenols are aromatic compounds containing one or more hydroxyl (OH) groups directly attached to the carbon atoms of a benzene ring. The simplest phenol is carbolic acid (C6H5OH). Phenols are more acidic than alcohols due to resonance stabilization of the phenoxide ion. The acidity of phenols increases with electron-withdrawing substituents due to delocalization of the phenoxide ion's negative charge. Phenols undergo electrophilic aromatic substitution and oxidation reactions. Common methods for phenol preparation include the hydrolysis of chlorobenzene, oxidation of cumene, and the reaction of aryl diazonium salts with water.
Hetero-cyclic compounds unit III as per PCI syllabus for second year B pharmacy students.
It covers all the details regarding Furan, Pyrrole and Thiophene ring
The ability to recreate computational results with minimal effort and actionable metrics provides a solid foundation for scientific research and software development. When people can replicate an analysis at the touch of a button using open-source software, open data, and methods to assess and compare proposals, it significantly eases verification of results, engagement with a diverse range of contributors, and progress. However, we have yet to fully achieve this; there are still many sociotechnical frictions.
Inspired by David Donoho's vision, this talk aims to revisit the three crucial pillars of frictionless reproducibility (data sharing, code sharing, and competitive challenges) with the perspective of deep software variability.
Our observation is that multiple layers — hardware, operating systems, third-party libraries, software versions, input data, compile-time options, and parameters — are subject to variability that exacerbates frictions but is also essential for achieving robust, generalizable results and fostering innovation. I will first review the literature, providing evidence of how the complex variability interactions across these layers affect qualitative and quantitative software properties, thereby complicating the reproduction and replication of scientific studies in various fields.
I will then present some software engineering and AI techniques that can support the strategic exploration of variability spaces. These include the use of abstractions and models (e.g., feature models), sampling strategies (e.g., uniform, random), cost-effective measurements (e.g., incremental build of software configurations), and dimensionality reduction methods (e.g., transfer learning, feature selection, software debloating).
I will finally argue that deep variability is both the problem and solution of frictionless reproducibility, calling the software science community to develop new methods and tools to manage variability and foster reproducibility in software systems.
Exposé invité Journées Nationales du GDR GPL 2024
Or: Beyond linear.
Abstract: Equivariant neural networks are neural networks that incorporate symmetries. The nonlinear activation functions in these networks result in interesting nonlinear equivariant maps between simple representations, and motivate the key player of this talk: piecewise linear representation theory.
Disclaimer: No one is perfect, so please mind that there might be mistakes and typos.
dtubbenhauer@gmail.com
Corrected slides: dtubbenhauer.com/talks.html
Deep Behavioral Phenotyping in Systems Neuroscience for Functional Atlasing a...Ana Luísa Pinho
Functional Magnetic Resonance Imaging (fMRI) provides means to characterize brain activations in response to behavior. However, cognitive neuroscience has been limited to group-level effects referring to the performance of specific tasks. To obtain the functional profile of elementary cognitive mechanisms, the combination of brain responses to many tasks is required. Yet, to date, both structural atlases and parcellation-based activations do not fully account for cognitive function and still present several limitations. Further, they do not adapt overall to individual characteristics. In this talk, I will give an account of deep-behavioral phenotyping strategies, namely data-driven methods in large task-fMRI datasets, to optimize functional brain-data collection and improve inference of effects-of-interest related to mental processes. Key to this approach is the employment of fast multi-functional paradigms rich on features that can be well parametrized and, consequently, facilitate the creation of psycho-physiological constructs to be modelled with imaging data. Particular emphasis will be given to music stimuli when studying high-order cognitive mechanisms, due to their ecological nature and quality to enable complex behavior compounded by discrete entities. I will also discuss how deep-behavioral phenotyping and individualized models applied to neuroimaging data can better account for the subject-specific organization of domain-general cognitive systems in the human brain. Finally, the accumulation of functional brain signatures brings the possibility to clarify relationships among tasks and create a univocal link between brain systems and mental functions through: (1) the development of ontologies proposing an organization of cognitive processes; and (2) brain-network taxonomies describing functional specialization. To this end, tools to improve commensurability in cognitive science are necessary, such as public repositories, ontology-based platforms and automated meta-analysis tools. I will thus discuss some brain-atlasing resources currently under development, and their applicability in cognitive as well as clinical neuroscience.
Comparing Evolved Extractive Text Summary Scores of Bidirectional Encoder Rep...University of Maribor
Slides from:
11th International Conference on Electrical, Electronics and Computer Engineering (IcETRAN), Niš, 3-6 June 2024
Track: Artificial Intelligence
https://www.etran.rs/2024/en/home-english/
Unlocking the mysteries of reproduction: Exploring fecundity and gonadosomati...AbdullaAlAsif1
The pygmy halfbeak Dermogenys colletei, is known for its viviparous nature, this presents an intriguing case of relatively low fecundity, raising questions about potential compensatory reproductive strategies employed by this species. Our study delves into the examination of fecundity and the Gonadosomatic Index (GSI) in the Pygmy Halfbeak, D. colletei (Meisner, 2001), an intriguing viviparous fish indigenous to Sarawak, Borneo. We hypothesize that the Pygmy halfbeak, D. colletei, may exhibit unique reproductive adaptations to offset its low fecundity, thus enhancing its survival and fitness. To address this, we conducted a comprehensive study utilizing 28 mature female specimens of D. colletei, carefully measuring fecundity and GSI to shed light on the reproductive adaptations of this species. Our findings reveal that D. colletei indeed exhibits low fecundity, with a mean of 16.76 ± 2.01, and a mean GSI of 12.83 ± 1.27, providing crucial insights into the reproductive mechanisms at play in this species. These results underscore the existence of unique reproductive strategies in D. colletei, enabling its adaptation and persistence in Borneo's diverse aquatic ecosystems, and call for further ecological research to elucidate these mechanisms. This study lends to a better understanding of viviparous fish in Borneo and contributes to the broader field of aquatic ecology, enhancing our knowledge of species adaptations to unique ecological challenges.
Nucleophilic Addition of carbonyl compounds.pptxSSR02
Nucleophilic addition is the most important reaction of carbonyls. Not just aldehydes and ketones, but also carboxylic acid derivatives in general.
Carbonyls undergo addition reactions with a large range of nucleophiles.
Comparing the relative basicity of the nucleophile and the product is extremely helpful in determining how reversible the addition reaction is. Reactions with Grignards and hydrides are irreversible. Reactions with weak bases like halides and carboxylates generally don’t happen.
Electronic effects (inductive effects, electron donation) have a large impact on reactivity.
Large groups adjacent to the carbonyl will slow the rate of reaction.
Neutral nucleophiles can also add to carbonyls, although their additions are generally slower and more reversible. Acid catalysis is sometimes employed to increase the rate of addition.
EWOCS-I: The catalog of X-ray sources in Westerlund 1 from the Extended Weste...Sérgio Sacani
Context. With a mass exceeding several 104 M⊙ and a rich and dense population of massive stars, supermassive young star clusters
represent the most massive star-forming environment that is dominated by the feedback from massive stars and gravitational interactions
among stars.
Aims. In this paper we present the Extended Westerlund 1 and 2 Open Clusters Survey (EWOCS) project, which aims to investigate
the influence of the starburst environment on the formation of stars and planets, and on the evolution of both low and high mass stars.
The primary targets of this project are Westerlund 1 and 2, the closest supermassive star clusters to the Sun.
Methods. The project is based primarily on recent observations conducted with the Chandra and JWST observatories. Specifically,
the Chandra survey of Westerlund 1 consists of 36 new ACIS-I observations, nearly co-pointed, for a total exposure time of 1 Msec.
Additionally, we included 8 archival Chandra/ACIS-S observations. This paper presents the resulting catalog of X-ray sources within
and around Westerlund 1. Sources were detected by combining various existing methods, and photon extraction and source validation
were carried out using the ACIS-Extract software.
Results. The EWOCS X-ray catalog comprises 5963 validated sources out of the 9420 initially provided to ACIS-Extract, reaching a
photon flux threshold of approximately 2 × 10−8 photons cm−2
s
−1
. The X-ray sources exhibit a highly concentrated spatial distribution,
with 1075 sources located within the central 1 arcmin. We have successfully detected X-ray emissions from 126 out of the 166 known
massive stars of the cluster, and we have collected over 71 000 photons from the magnetar CXO J164710.20-455217.
The binding of cosmological structures by massless topological defectsSérgio Sacani
Assuming spherical symmetry and weak field, it is shown that if one solves the Poisson equation or the Einstein field
equations sourced by a topological defect, i.e. a singularity of a very specific form, the result is a localized gravitational
field capable of driving flat rotation (i.e. Keplerian circular orbits at a constant speed for all radii) of test masses on a thin
spherical shell without any underlying mass. Moreover, a large-scale structure which exploits this solution by assembling
concentrically a number of such topological defects can establish a flat stellar or galactic rotation curve, and can also deflect
light in the same manner as an equipotential (isothermal) sphere. Thus, the need for dark matter or modified gravity theory is
mitigated, at least in part.
ANAMOLOUS SECONDARY GROWTH IN DICOT ROOTS.pptxRASHMI M G
Abnormal or anomalous secondary growth in plants. It defines secondary growth as an increase in plant girth due to vascular cambium or cork cambium. Anomalous secondary growth does not follow the normal pattern of a single vascular cambium producing xylem internally and phloem externally.
This presentation explores a brief idea about the structural and functional attributes of nucleotides, the structure and function of genetic materials along with the impact of UV rays and pH upon them.
Phenomics assisted breeding in crop improvementIshaGoswami9
As the population is increasing and will reach about 9 billion upto 2050. Also due to climate change, it is difficult to meet the food requirement of such a large population. Facing the challenges presented by resource shortages, climate
change, and increasing global population, crop yield and quality need to be improved in a sustainable way over the coming decades. Genetic improvement by breeding is the best way to increase crop productivity. With the rapid progression of functional
genomics, an increasing number of crop genomes have been sequenced and dozens of genes influencing key agronomic traits have been identified. However, current genome sequence information has not been adequately exploited for understanding
the complex characteristics of multiple gene, owing to a lack of crop phenotypic data. Efficient, automatic, and accurate technologies and platforms that can capture phenotypic data that can
be linked to genomics information for crop improvement at all growth stages have become as important as genotyping. Thus,
high-throughput phenotyping has become the major bottleneck restricting crop breeding. Plant phenomics has been defined as the high-throughput, accurate acquisition and analysis of multi-dimensional phenotypes
during crop growing stages at the organism level, including the cell, tissue, organ, individual plant, plot, and field levels. With the rapid development of novel sensors, imaging technology,
and analysis methods, numerous infrastructure platforms have been developed for phenotyping.
Travis Hills' Endeavors in Minnesota: Fostering Environmental and Economic Pr...Travis Hills MN
Travis Hills of Minnesota developed a method to convert waste into high-value dry fertilizer, significantly enriching soil quality. By providing farmers with a valuable resource derived from waste, Travis Hills helps enhance farm profitability while promoting environmental stewardship. Travis Hills' sustainable practices lead to cost savings and increased revenue for farmers by improving resource efficiency and reducing waste.
hematic appreciation test is a psychological assessment tool used to measure an individual's appreciation and understanding of specific themes or topics. This test helps to evaluate an individual's ability to connect different ideas and concepts within a given theme, as well as their overall comprehension and interpretation skills. The results of the test can provide valuable insights into an individual's cognitive abilities, creativity, and critical thinking skills
3. Metal hydride reduction (NaBH4 and LiAlH4)
The most common sources of the hydride Nucleophile are lithium aluminum hydride
(LiAlH4) and sodium borohydride (NaBH4).
The hydride anion is not present during this reaction; rather, these reagents serve as a
source of hydride due to the presence of a polar metal-hydrogen bond
Because aluminium is less electronegative than boron, the Al-H bond in LiAlH4 is
more polar, thereby, making LiAlH4 a stronger reducing agent.
Addition of a hydride anion (H:-) to an aldehyde or ketone gives an alkoxide anion,
which on protonation yields the corresponding alcohol .
Aldehydes produce 1°-alcohols and ketones produce 2°-alcohols.
Al
H
H H
H
Li B
H
H H
H
Na H
R.C.P.KASEGAON
4. Metal hydride reduction by LiAlH4 and NaBH4
R C
O
H
LiAlH4
R C
H
OH
H LiOH
+ + AlH3
R C
O
H
NaBH4
R C
H
OH
H NaCl
+ + BH3
HCl
2
H O
R.C.P.KASEGAON
5. Mechanism of Metal hydride reduction by LiAlH4
R C
O
H + Al
H
H
H
H
Li R C
O
H
H
Li+
+ AlH3
1. Nucleophilic attack by hydride
2.Protonation of Alkoxide ion
R C
O
H
H
Li+
+ H OH R C
OH
H
H
+ LiOH
R.C.P.KASEGAON
6. Mechanism of Metal hydride reduction by NaBH4
R C
O
H + B
H
H
H
H
Na R C
O
H
H
Na+
+ BH3
1. Nucleophilic attack by hydride
2.Protonation of Alkoxide ion
R C
O
H
H
Na+
+ H Cl R C
OH
H
H
+ NaCl
R.C.P.KASEGAON
7. Examples of Metal hydride reduction by LiAlH4&bNaBH4
O
H
LiAlH4
H3C C
H
OH
H LiOH
+ + AlH3
O
H
NaBH4
H3C C
H
H NaCl
+ + BH3
HCl
2
H O
H3C C
acetaldehyde
H3C C
acetaldehyde ethanol
ethanol
OH
H3C C
O
CH3
LiAlH4
H3C C
H
OH
LiOH + AlH3
H3C C
O
CH3
NaBH4
H3C C
H
CH3 NaCl + BH3
HCl
2
H O
Acetone
acetone
CH3
+
+
propan-2-ol
OH
propan-2-ol
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8. Application
1. Aldehydes are converted into primary alcohol(Alcohol preparation)
2. Ketones are converted into secondary alcohol (Alcohol Preparation)
3. Identification Class of alcohol
R.C.P.KASEGAON
10. INTRODUCTION
4
This reaction was first reported by Clemmensen of
Park Davis in 1913.
It is the reduction of carbonyl groups ( in
aldehyde and ketone) to methylene group.
This reaction done with zinc amalgam and hydrochloric
acid and it is generally known as Clemmensen reduction.
The Clemmensen reduction is particularly effective at reducing aryl-
alkyl ketones,such as those formed in a Friedel-Crafts acylation.
R.C.P.KASEGAON
14. APPLICATIONS
🠶 This reaction has widely used to convert a carbonyl group into a
methylene group.
🠶 Also important application in the preparation of polycyclic
aromatics and aromatics containing unbranched side
hydrocarbon chains.
🠶 To reduce aliphatic and mixed aliphatic-aromatic carbonyl
compounds
8
R.C.P.KASEGAON
16. Birch Reduction
The reduction of aromatic substrates with alkali metals, alcohol in liquid
ammonia is known as "Birch reduction
This reaction is named after a Australian chemist Sir Arthur John Birch.
The Birch reduction is an organic reaction where
aromatic rings undergo a
1,4-reduction to provide unconjugated cyclohexadienes .
The reduction is conducted by sodium or lithium metal in liquid ammonia
and in the presence of an alcohol.
R.C.P.KASEGAON
17. Birch Reduction
The mechanism begins with a Single Electron Transfer (SET) from the
metal to the aromatic ring, forming a radical anion.
The anion then picks up a proton from the alcohol which results in a neutral
radical intermediate.
Another SET, and abstraction of a proton from the alcohol results in the
final cyclohexadiene product and two equivalents of metal alkoxide salt as a
by-product.
R.C.P.KASEGAON
19. Mechanism of Birch Reduction
2Na+
e-
2e-
H
H
H
HO CH3
2 Na NH3
H H
H
H
e-
H
H
HO CH3
H
H H
-CH3O
H
-CH3O
H
O + 2Na
2 CH3 2CH3ONa
R.C.P.KASEGAON
20. Application of Birch Reduction
1) Naphthalene can be reduced to 1,4,5,8-tetrahydronaphthalene by
using Birch reduction conditions.
Na, NH3(Liq)-78°C
EtOH, Et2O
1,4,5,8-tetrahydronaphthalene
2) In the birch reduction of benzoic acid, the protonation occurs at ipso and para
positions
relative to -COOH group on the benzene ring.
COOH
Na, NH3
C2H5OH
COOH
cyclohexa-2,5-dienecarboxylic acid
benzoic acid R.C.P.KASEGAON
22. Kishner
INTRODUCTION
The Wolff– Kishner reduction was discovered independently by N.
in 1911 and L. Wolff in 1912.
TheWolff–Kishner reduction is a reaction used in organic chemistry to
convert carbonyl functionalities into methylene groups.
The Wolff-Kishner reduction is an organic reaction used to convert an
aldehyde or ketone to an alkane using hydrazine, base, and thermal
conditions
Because the Wolff–Kishner reduction requires highly basic conditions, it is
unsuitable for base-sensitive substrates.
R.C.P.KASEGAON
26. MODIFICATION
🠶 The reaction has been extensively modified.
🠶 One of the modification uses the Huang Minlon modification
using distillation to remove excess water and also used 85% hydrazine
and solvent used is ethylene glycol.
🠶 In addition, the Wolff- kishner reduction has been carried out in
DMSO instead of hydroxylic solvent by addition of hydrazones into
anhydrous DMSO containing freshly sublimed potassium tert-
butoxide at 250C.
🠶 Moreover,it has been reported that the Wolff-Kishner reduction
can occur in a very short period of time in a microwave irradiation,
affording product with high purity.
13
R.C.P.KASEGAON
27. APPLICATIONS
🠶 This reaction has very broad application in organic synthesis,
especially for the multiwalled carbon nanotubes.
🠶 In 2011, Pettus and Green reduced a tricyclic carbonyl compound
using the Huang Minlon modification of the Wolff–Kishner
reduction.Several attempts towards decarbonylation of tricyclic allylic
acetate containing ketone failed and the acetate functionality had to be
removed to allow successful Wolff–Kishner reduction. Finally, the
allylic alcohol was installed via oxyplumbation.
🠶 The Wolff–Kishner reduction has also been used on kilogram scale
for the synthesis of a functionalized imidazole substrate.
14
R.C.P.KASEGAON
29. INTRODUCTION
Named after Rupert Viktor Oppenauer.
It is a gentle method for selectively oxidizing secondary alcohols to
ketones.
The reaction is the opposite of Meerwein– Ponndorf –Verley reduction.
The alcohol is oxidized with aluminium isopropoxide in excess
acetone.
This shifts the equilibrium toward the product side.
R.C.P.KASEGAON
30. The oxidation is highly selective for secondary alcohols and does not
oxidize other sensitive functional groups such as amines and sulfides,
Though primary alcohols can be oxidized under Oppenauer conditions,
primary alcohols are seldom oxidized by this method due to the
competing aldol condensation of aldehyde products.
The Oppenauer oxidation is still used for the oxidation of acid labile
substrates.
Cont……
R.C.P.KASEGAON
33. MODIFICATION
Woodward modification
🠶 In the Woodward modification, Woodward substituted potassium
tert- butoxide for the aluminium alkoxide.
🠶 The Woodward modification of the Oppenauer oxidation is used
when certain alcohol groups do not oxidize under the standard
Oppenauer reaction conditions.
🠶 For example, Woodward used potassium tert-butoxide
and benzophenone for the oxidation of quinine to quininone, as the
traditional aluminium catalytic system failed to oxidize quinine due
to the complex formed by coordination of the Lewis- basic nitrogen
to the aluminium centre.
28
R.C.P.KASEGAON
34. Cont……
Other modifications
•Several modified aluminium alkoxide catalysts have been also reported
•For example, a highly active aluminium catalyst was reported by Maruoka and
co-workers which was utilized in the oxidation of carveol to carvone (a member
of a family of chemicals called terpenoids) in excellent yield (94%)
29
R.C.P.KASEGAON
36. APPLICATIONS
The Oppenauer oxidation is used to prepare analgesics in the
pharmaceutical industry such as morphine and codeine. For
instance, codeinone is prepared by the Oppenauer oxidation
of codeine.
R.C.P.KASEGAON
37. Cont……
The Oppenauer oxidation is also used to synthesize hormones.
Progesterone is prepared by the Oppenauer oxidation of
pregnenolone.
R.C.P.KASEGAON
39. 6. Dakin Reaction
Dakin Reaction is the replacement of the aldehyde group of ortho and para hydroxy and
ortho amino-benzaldehyde (or ketone) by a hydroxyl group on reaction with alkaline
hydrogen peroxide.
H2O2
NaOH
OH
C
O
H
OH
OH
+ H-COOH
Catechol
Salicylic acid
R.C.P.KASEGAON
40. 6. Dakin Reaction- Mechanism
NaOH +
OH Na
OH-
HO OH H2O
OH O
HO O
C H
O OH
OH O
C H
O OH
Na
-NaOH
OH
O
O
C H
H-OH
OH
OH
Catechol
+ HCOOH
salicylic acid
1 2.
3.
R.C.P.KASEGAON
41. Applications of Dakin oxidation reaction
1. Synthesis of Pyrro gallol mono methyl ether- Anesthetic agent
2. Synthesis of Hydroquinone-Treatment of acne
3. Phenol preparation
CHO
OH
H2O2
NaOH, H2O
OCH3
OH
OH
OCH3
2,3 Dihydroxy anisole
(Pyrrogallol monomethyl ether)
C OH
CH3
H2O2
2
NaOH, H O
HO OH
O
p-hydroxyacetophenone Hydroquinone
-2-hydroxy, 3-3methoxy
benzaldehyde
R.C.P.KASEGAON
42. Beckmann rearrangement
• The acid-catalysed conversion of ketoximes to amides is known as
the Beckmann rearrangement
• The Beckmann rearrangement, named after the German chemist
Ernst Otto Beckmann (1853–1923)
• This rearrangement is occurs in both cyclic and acyclic
compoun
ds
.
• Aldoximes are less reactive.
• Cyclic oximes yield lactams and acyclic oximes yield amides
2
R.C.P.KASEGAON
44. Reaction mechanism
The first step in the process is formation of an oxime from the aldehyde or
ketone,
4
4
R.C.P.KASEGAON
45. Reaction mechanism
This rearrangement take place an alkyl migration with expulsion of the
hydroxyl group to form a nitrilium ion followed by hydrolysis.
4
5
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46. Migratory aptitude
• The relative migratory aptitudes of different groups in Beckmann rearrangement
is illustrated below.
4
6
R.C.P.KASEGAON
47. Applications in drug synthesis:-
• An alternative industrial synthesis method for Paracetamol. It is involves direct
acylation of phenol with acetic anhydride catalyzed by HF, conversion of the
ketone to a ketoxime with hydroxylamine, followed by the acid-catalyzed
Beckmann Rearrangement to give the amide
7
Paracetamol
R.C.P.KASEGAON
48. 4
8
Applications in drug synthesis:-
• The Beckmann rearrangement is also used in the
synthesi
s of
1. DHEA
2. Benazepril
3. Etazepine etc.
R.C.P.KASEGAON
49. Applications in polymer synthesis:-
• Beckmann rearrangement can be rendered catalytic using cyanuric chloride and
zinc chloride as a co-catalyst. For
example, cyclododecanone can be converted to the
correspondi
ng lactam,
the monomer used in the production of Nylon 12
4
9
R.C.P.KASEGAON
50. Applications in polymer synthesis:-
• The Beckmann rearrangement is also used in the
synthesis of Nylon 6
5
0
R.C.P.KASEGAON
51. Schmidt Rearrangement
The Schmidt reaction is an organic reaction in which an azide reacts with a carbonyl derivative, usually an aldehyde, ketone, or
carboxylic acid, under acidic conditions to give an amine or amide, with expulsion of nitrogen.
The reaction is superior to the Curtius or Hofmann rearrangement because it directly converts an acid or ester to amine, without
making the acid derivatives.
The reaction is limited to acid insensitive compounds.
The reaction is effective with carboxylic acids to give amines, and with ketones to give amides.
R.C.P.KASEGAON
53. The reaction proceeds with faster rate with sterically hindered acids which forms acyl cation in presence of acids, even
without heating.
Acids that do not form acyl cation react through the protonation of the acid under heating, as shown previously.
acyl cation
Crowding around the center of the “R” group facilitates the formation of acyl cation, thus enhances the rate.
R.C.P.KASEGAON
56. (A)
(B)
(6)
Evidence for the carbocation intermediate formation
Formation of the carbocation step (6) in Schmidt reaction can be evidenced by the formation of the tetrazole (A) and
the substituted urea (B), which are often isolated from the reaction medium when excess of azide is used. These
products are obtained from the intermediate carbocation as the amide does not react with hydrogen azide in the
reaction condition.
Unsymmetrical ketone gives a mixture of two product
R.C.P.KASEGAON
57. Application of Schmidt Rearrangement
1. Preparation of Primary Amines
COOH
3
H C +NH3
H2SO4
NH2
H3C
Toludine
Tolueic acid
+ NH3
H2SO4
2. Preparation of Capro-lactams and polymerisation of caprolactam with base to form nylone
O
O
NH
Lactam
Cyclohexanone
R.C.P.KASEGAON
58. Application of Schmidt Rearrangement
3. Synthesis of Acetanilide from acetophenone- Analgesic, Antirhuematic
4. Synthesis of Benzanilide from Benzophenone- Perfume and dye
C
O
CH3
+ NH3
H2SO4
acetophenone
NH C
O
CH3
Acetanilide
C
O
+ NH3
H2SO4
NH C
O
benzophenone
Benzanilide
R.C.P.KASEGAON
59. Claisen–Schmidt Condensation Reaction
The reaction between an aldehyde or ketone having an alpha-hydrogen with an
aromatic carbonyl compound lacking an alpha hydrogen is called the Claisen–
Schmidt condensation.
In cases where the product formed still has reactive alpha hydrogen and a hydroxide
adjacent to an aromatic ring, the reaction will quickly undergo dehydration leading to the
condensation product
C
O
H
+ CH3
C
O
CH3
NaOH, Aq. EtOH
H
C CH
C
O
C
H
H
C
Dibenzal acetone
Benzaldehyde
2
R.C.P.KASEGAON
62. Application
1. A reaction employed for preparation of unsaturated aldehydes and ketones
by condensation of aromatic aldehydes with aliphatic aldehyde or ketone in presence of
sodium hydroxide. E.g. synthesis of cinnamaldehyde which is used in perfumery industry
C
O
H
+ CH3 C
O
H
H H
C C C
O
H
10% NaOH
Cinnamaldehyde
Bezaldehyde
2. Synthesis of Dibenzalacetone which is used as sun protecting agent in sun screen lotion
C
O
H
+ C H 3
C
O
C H 3
N a O H , Aq. E t O H
H
C C H
C
O
C
H
H
C
Dibenzal acetone
B enzaldehyde
2
R.C.P.KASEGAON
63. Application
3. Synthesis of Chacone
4. This reaction also used to synthesis of natural products such as ionone, Flavonone,
piperine etc
C
O
CH3
+ H C
O
C
H
C CH
10% NaOH
Chalcones
Acetophenone
O
Benzaldehyde
ethanol
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