Name reactions – Online Chemistry notes https://chemicalnote.com Simple Notes for All Students. Thu, 20 Feb 2025 16:54:15 +0000 en-US hourly 1 https://wordpress.org/?v=6.9.4 https://chemicalnote.com/wp-content/uploads/2020/04/cropped-Logo-32x32.png Name reactions – Online Chemistry notes https://chemicalnote.com 32 32 Name reactions: 30 most important organic named reactions for class 12 https://chemicalnote.com/name-reactions-30-most-important-organic-named-reactions-for-class-12/?utm_source=rss&utm_medium=rss&utm_campaign=name-reactions-30-most-important-organic-named-reactions-for-class-12 https://chemicalnote.com/name-reactions-30-most-important-organic-named-reactions-for-class-12/#respond Thu, 20 Feb 2025 16:45:59 +0000 https://chemicalnote.com/?p=4165 Name reactions are chemical reactions that are recognized by a specific name. Name reactions are usually named after the person who discovered or developed it. Hundreds of well known organic reactions have been named after people who discovered it. But name reactions are not always named after their discoverers. Some reactions are named on the […]

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Name reactions are chemical reactions that are recognized by a specific name. Name reactions are usually named after the person who discovered or developed it. Hundreds of well known organic reactions have been named after people who discovered it. But name reactions are not always named after their discoverers. Some reactions are named on the basis of the key reactants used, the type of product formed, or the main transformation that happens in the reaction.

30 most important name reactions which are frequently asked in class 12 chemistry exams are listed below:


1. Dehydrohalogenation reaction (Elimination reaction)


When an alkyl halide is heated with alcoholic solution of KOH, then a molecule of hydrogen halide is eliminated from the haloalkane and alkene is formed. Therefore this reaction is also called dehydrohalogenation reaction. Eg.

Dehydrohalogenation reaction (Elimination reaction)

Elimination reaction involves the removal of halogen atom of haloalkane and a hydrogen atom from the β- carbon (i.e. adjacent carbon). Therefore, this reaction is also known as β- elimination reaction.


2. Wurtz reaction


When an alkyl halide( haloalkane) is heated with sodium metal in presence of dry ether, a symmetrical alkane containing double number of carbon atoms than in haloalkane is formed. This reaction is called Wurtz reaction.

Wurtz reaction


3. Fittig reaction


Haloarenes when treated with sodium in the presence of dry ether, diaryls are produced. This reaction is known as Fittig reaction.

Fittig reaction


4. Wurtz-Fittig reaction


Haloarenes when treated with sodium and alkyl halide in presence of dry ether gives toluene. This reaction is known as Wurtz-Fittig reaction.

Wurtz-Fittig reaction


5. Carbylamine reaction: Test reaction of primary amines


When chloroform is warmed with a primary amine in the presence of alcoholic KOH, an offensive(unpleasant) smell of carbylamines ( i.e. isocyanide) is obtained. This reaction is known as carbylamine reaction.

Carbylamine reaction: Test reaction of primary amines

Carbylamine reaction: Test reaction of primary amines


6. Sandmeyer reaction


Chlorobenzene can be prepared by treating benzene diazonium chloride with cuprous chloride dissolved in HCl. This reaction is called Sandmeyer reaction.

Sandmeyer reaction


7. Gattermann reaction


Chlorobenzene is prepared by treating benzene diazonium chloride with copper powder dissolved in HCl. This reaction is the modification of Sandmeyer’s reaction and called Gattermann reaction.

Gattermann reaction


8. Diazotization reaction


When aniline is treated with sodium nitrite (NaNO2) and dil.HCl at temperature below 50C, benzene diazonium chloride is obtained. This reaction is known as diazotization reaction.

diazotization reaction


9. Dows Process


When chlorobenzene is heated with an aqueous solution of NaOH at 3000C and 200 atm gives sodium phenoxide which on acidification gives phenol.

dows process


10. Oxo-process (Carbonylation reaction)


Alkenes react with carbon monoxide and hydrogen in the presence of cobalt carbonyl catalyst [Co(CO)4]2 at high pressure and temperature to give aldehyde, which on catalytic hydrogenation gives primary alcohol. Eg.

oxo-process


11. Fermentation


Fermentation is a biochemical process of degradation (slow decomposition/ breaking down) of large organic molecules like sugars and starches into simpler compounds by the catalytic action of enzymes.

Eg. Ethanol from sugar: Enzymes invertase and zymase are obtained from yeast. The reactions occurring during the fermentation of sugar are:

fermentation


12. Esterification reaction


Alcohols react with carboxylic acids in the presence of few drops of conc. H2SO4 to form esters. This reaction is known as esterification reaction.

esterification reaction


13. Kolbe’s reaction (Carboxylation reaction)


Sodium phenoxide when heated with CO2 at1350C under a pressure of 4-7 atm, sodium salicylate is obtained which when acidified gives salicylic acid.

Kolbe’s reaction (Carboxylation reaction)


14. Haloform reaction


Aldehydes and ketones containing CH3CO- group on reaction with excess halogen in presence of NaOH gives haloform (chloroform’ bromoform, iodoform). Eg.

haloform reaction


15. Coupling reaction


Phenol or aniline reacts with benzene diazonium chloride in slightly alkaline medium and at low temperature to form coloured compounds called azo dyes. This reaction is called coupling reaction.

coupling reaction of phenol

Coupling reaction of aniline


16. Reimer-Tiemann reaction


When phenol is refluxed with chloroform and aq. NaOH at 600C, a mixture of o-hydroxybenzaldehyde and p-hydroxybenzaldehyde is obtained. This reaction is called Reimer-Tiemann reaction.

Reimer-Tiemann reaction


17. Williamson’s ether synthesis


The reaction in which alkyl halide and sodium or potassium alkoxide are reacted to form ether is known as Williamson’s etherification reaction. Eg.

https://chemicalnote.com/wp-content/uploads/2020/08/word-image-5.png

Both symmetrical and unsymmetrical ether can be prepared from this reaction. Eg.

preparation of ether by williamsons method


18. Ozonolysis reaction


Alkene reacts with ozone to give ozonide. On warming ozonide with Zn in water, it breaks down to give two molecules of carbonyl compounds (aldehyde or ketone). This process of formation of ozonide and it’s decomposition to give carbonyl compounds is called ozonolysis.

ozonolysis reaction


19. Rosenmund reduction


Aldehydes can be prepared by reducing acid chloride solution with hydrogen in the presence of Palladium(Pd) catalyst deposited on barium sulphate and partially poisoned with sulphur or quinoline. This reaction is called Rosenmund reduction.

Rosenmund reduction


20. Clemmensen’s reduction


The reduction of aldehydes and ketones to alkane using zinc amalgam and conc. HCl is Clemmensen’s reduction. In this reaction, carbonyl group (-CO-) is reduced to -CH2– group. Eg.

Clemmensen’s reduction


21 . Wolff-Kishner reduction


In this method aldehyde and ketone is treated with hydrazine to form hydrazone which is then heated with KOH in presence of glycol to give alkane. Eg.

Wolff-Kishner reduction


22. Aldol condensation reaction


Condensation between two molecules of aldehydes or ketones having at least one α – hydrogen atom in presence of dilute alkali to form β-hydroxy aldehyde or β-hydroxy ketone is known as aldol condensation reaction. Examples:

Aldol condensation reaction

Aldol condensation reaction

Aldehydes and ketones which do not contain any α – hydrogen atom such as HCHO, (CH3)3CCHO, C6H5CHO, etc. do not undergo aldol condensation reaction.


23. Cannizzaro’s reaction


Aldehydes which do not contain α-hydrogen like HCHO, C6H5CHO,etc. undergo self oxidation and reduction on treatment with conc. alkali. In this reaction one molecule is oxidized to carboxylic acid and other molecule is reduced to alcohol. Thus, a mixture of an alcohol and a salt of carboxylic acid is formed by Cannizzaro’s reaction

Cannizzaro’s reaction


24. Perkin’s (condensation) reaction


The condensation of an aromatic aldehyde with an acid anhydride in the presence of sodium or potassium salt of the same acid to produce α,β-unsaturated acid is known as the Perkin’s condensation.

Perkin’s (condensation) reaction


25. Benzoin condensation reaction


Benzaldehyde when heated with alcoholic solution of potassium cyanide, undergoes self condensation between two molecules to form an α-hydroxy ketone known as benzoin. This reaction is called benzoin condensation reaction. Eg.

Benzoin condensation reaction


26. Hell-Volhard Zelinsky [HVZ] reaction


Carboxylic acids (except formic acid) reacts with chlorine or bromine in presence of red phosphorous to give α-chloro or α-bromo acids. The reaction does not stop at monosubstituted product but continues till all α-hydrogen atoms are replaced.

Hell-Volhard Zelinsky [HVZ] reaction


27. Claisen condensation reaction


Condensation between two molecules of esters having α-hydrogen atom in the presence of strong base like sodium ethoxide and an acid to form β-keto ester is known as Claisen condensation reaction. Eg.

Claisen condensation reaction


28. Hoffmann’s Bromamide reaction: Decarbonylation reaction


When an amide is treated with bromine in NaOH or KOH, carbonyl group is removed from made to form primary amine containing one carbon less than that of amide. This reaction is known as Hoffmann bromamide reaction or decarbonylation reaction.

Hoffmann’s Bromamide reaction: Decarbonylation reaction


29. Friedel Craft’s reaction


a. Friedel Craft’s alkylation reaction: Introduction of an alkyl group ( – R ) in the benzene ring by treating benzene with an alkyl halide in the presence of anhydrous AlCl3 is known as Friedel- Craft’s alkylation reaction.

Friedel Craft’s alkylation reaction

b. Friedel craft’s acylation reaction : Introduction of an acyl group (i.e.keto group) in the benzene ring by treating benzene with acid chloride or acid anhydride in the presence of anhydrous AlCl3 is known as Friedel- Craft’s acylation reaction.

Friedel craft’s acylation reaction


30. Hydroboration-Oxidation of alkene


In this method, alkene is treated with diborane, (BH3)2 or B2H6 followed by alkaline oxidation with H2O2 to get primary alcohol.

Hydroboration is a reduction process, which is carried out by treating with diborane, (BH3)2 to give trialkyl borane, which upon oxidation with alkaline solution of H2O2 gives primary alcohol. For example:

Hydroboration-Oxidation of alkene


Links to get mechanism of some name reactions


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Diazotization reaction: Mechanism and Uses https://chemicalnote.com/diazotization-reaction-mechanism-and-uses/?utm_source=rss&utm_medium=rss&utm_campaign=diazotization-reaction-mechanism-and-uses https://chemicalnote.com/diazotization-reaction-mechanism-and-uses/#respond Thu, 25 May 2023 15:29:53 +0000 https://chemicalnote.com/?p=3938 What is Diazotization reaction? When aniline is treated with sodium nitrite (NaNO2) and dilute hydrochloric acid (HCl) at ice cold temperature (0-50C), benzene diazonium chloride salt is obtained. This reaction is called diazotization reaction. At first nitrous acid(HNO2) is obtained by the action of NaNO2 and dil.HCl and then the nitrous acid reacts with with […]

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What is Diazotization reaction?

When aniline is treated with sodium nitrite (NaNO2) and dilute hydrochloric acid (HCl) at ice cold temperature (0-50C), benzene diazonium chloride salt is obtained. This reaction is called diazotization reaction.

At first nitrous acid(HNO2) is obtained by the action of NaNO2 and dil.HCl and then the nitrous acid reacts with with aniline to give benzene diazonium chloride.

Diazotization reaction

Mechanism of diazotization reaction


Step-I : Nitrous acid (HNO2) is obtained by the action of NaNO2 and dil. HCl in-situ.
Diazotization reaction mechanism

Step-II : Protonation of nitrous acid followed by loss of water gives nitrosonium ion.

Step-III : Nucleophilic attack of aniline on nitrosonium ion gives nitrosoaniline.

Diazotization reaction mechanism

Step-IV : Protonation of the oxygen in the nitrosoaniline, followed by elimination of water gives diazonium ion ,which gets chloride ion and forms benzenediazonium chloride.

Diazotization reaction mechanism

Uses of Diazotization reaction


Diazotization reactions have several important uses in organic chemistry. Here are some of the main applications:

1. Synthesis of azo dyes: Diazotization reactions are widely employed in the production of azo dyes. Azo dyes are an important class of organic compounds used extensively in the textile, printing, and coloring industries. By diazotizing an aromatic amine and coupling it with a suitable coupling agent, various colored azo compounds can be synthesized.

Diazotization reaction uses

2. Preparation of aryl halides: Diazotization reactions can be used to convert aromatic amines into aryl halides, such as aryl chlorides or aryl bromides. The diazonium salt can be treated with a copper halide or cuprous salt, resulting in the replacement of the diazonium group with a halogen atom.

Sandmeyer application

Gattermann reaction

Some other uses are :

3. Pharmaceutical synthesis: Diazotization reactions are utilized in the synthesis of pharmaceutical compounds. The diazonium salts obtained can be reacted with a range of nucleophiles, such as phenols, amines, and thiols, to produce pharmaceutical intermediates or active pharmaceutical ingredients (APIs).

4. Formation of heterocyclic compounds: Diazotization reactions are employed in the synthesis of various heterocyclic compounds. The diazonium salt can react with compounds containing active methylene groups, such as β-ketoesters or malonates, leading to the formation of fused or isolated heterocyclic rings.

5. Preparation of aromatic fluorides: Diazotization reactions can also be used to produce aromatic fluorides. By reacting the diazonium salt with hydrogen fluoride (HF), the diazonium group is replaced by a fluorine atom, resulting in the formation of aryl fluorides.

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Witting reaction: Examples and Mechanism https://chemicalnote.com/witting-reaction-examples-and-mechanism/?utm_source=rss&utm_medium=rss&utm_campaign=witting-reaction-examples-and-mechanism https://chemicalnote.com/witting-reaction-examples-and-mechanism/#respond Tue, 19 Jul 2022 14:58:54 +0000 https://chemicalnote.com/?p=3751 What is witting reaction? Triphenyl phosphonium alkylide (simply phosphorous ylide) is called witting reagent. When carbonyl compound (aldehyde or ketone) is treated with an ylide, olefin (alkene) is formed. This reaction is called witting reaction. Mechanism of witting reaction Question- Answer from witting reaction Q) Give the reaction and mechanism when 2-hexanone is treated with […]

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What is witting reaction?

Triphenyl phosphonium alkylide (simply phosphorous ylide) is called witting reagent. When carbonyl compound (aldehyde or ketone) is treated with an ylide, olefin (alkene) is formed. This reaction is called witting reaction.

witting reaction


Mechanism of witting reaction


witting reaction mechanism


Question- Answer from witting reaction


Q) Give the reaction and mechanism when 2-hexanone is treated with witting reagent.

When 2-hexanone is treated with witting reagent, 2-methylhex-1-ene is formed. This reaction is called witting reaction. The reaction involved and mechanism is given below.

witting reaction

Mechanism:

Mechanism of witting reaction

Q) Give two different methods for witting synthesis of 2-methyl-1-hexene.

2-methyl-1-hexene can be prepared using witting synthesis by following two methods:

Method-I :

Give two different methods for witting synthesis of 2-methyl-1-hexene.

Method-II :

Q) Write product and mechanism of the reaction:

This reaction is witting reaction. The reaction involved and mechanism is given below:

Mechanism:


References


  • Morrison, R.T. , Boyd, R.N., Organic Chemistry, Sixth edition, Prentice-Hall of India Pvt. Ltd., 2008.
  • March, j., Advanced Organic Chemistry, Fourth edition, Wiley Eastern Ltd. India, 2005.
  • https://chemicalnote.com/category/organic-chemistry/name-reactions/

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Acetoacetic ester synthesis (of ketones) https://chemicalnote.com/acetoacetic-ester-synthesis-of-ketones/?utm_source=rss&utm_medium=rss&utm_campaign=acetoacetic-ester-synthesis-of-ketones https://chemicalnote.com/acetoacetic-ester-synthesis-of-ketones/#respond Sat, 02 Jul 2022 14:34:22 +0000 https://chemicalnote.com/?p=3730 Acetoacetic ester synthesis (of ketones) Ethyl acetoacetate is called as acetoacetic ester. Acetoacetic ester is an extremely useful molecule that can be used to prepare ketones and other molecules. Synthesis of wide variety of organic compounds starting from acetoacetic ester is called acetoacetic ester synthesis. Acetoacetic ester synthesis resembles with malonic ester synthesis and involves […]

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Acetoacetic ester synthesis (of ketones)

Ethyl acetoacetate is called as acetoacetic ester.

acetoacetic ester

Acetoacetic ester is an extremely useful molecule that can be used to prepare ketones and other molecules.

Synthesis of wide variety of organic compounds starting from acetoacetic ester is called acetoacetic ester synthesis.

Acetoacetic ester synthesis resembles with malonic ester synthesis and involves the following steps:

Step I : The α-hydrogen in acetoacetic ester is acidic in nature. When acetoacetic ester is treated with strong base like sodium ethoxide, it is converted into salt known as sodioacetoacetic ester.

acetoacetic ester synthesis

Step-II : The carbanion thus produced is a nucleophile and attacks alkyl halide to form an alkylacetoacetic ester.

acetoacetic ester synthesis

If required, the alkylation can be repeated to produce dialkyl acetoacetic ester.

acetoacetic ester synthesis

Step-III : These mono and dialkyl acetoacetic esters give the corresponding acids on hydrolysis. These acids undergo decarboxylation to form ketones.

acetoacetic ester synthesis

acetoacetic ester synthesis


Examples of acetoacetic ester synthesis


Q) Outline the synthesis of 3-methyl-2-pentanone from acetoacetic ester.

Structure of 3-methyl-2-pentanone is:

Outline the synthesis of 3-methyl-2-pentanone from acetoacetic ester

3-methyl-2-pentanone can be synthesized from acetoacetic ester by following reaction mechanism:

Outline the synthesis of 3-methyl-2-pentanone from acetoacetic ester

Q) Outline the synthesis of 3-methyl-2-hexanone from acetoacetic ester.

Hint:

Outline the synthesis of 3-methyl-2-hexanone from acetoacetic ester

Two alkyl halides used:

Q) Outline the synthesis of 5-methyl-2-hexanone from ethyl acetoacetate.

Structure of 5-methyl-2-hexanone is:

Outline the synthesis of 5-methyl-2-hexanone from ethyl acetoacetate

5-methyl-2-hexanone can be synthesized from acetoacetic ester by following reaction mechanism:

Outline the synthesis of 5-methyl-2-hexanone from ethyl acetoacetate

Q) Outline the synthesis of methyl isopropyl ketone from ethyl acetoacetate.

Hint:

Outline the synthesis of methyl isopropyl ketone from ethyl acetoacetate

Alkyl halides used:

CH3-Br two times.

Q) What are A, B and C?

What are A, B and C?

Ans:

What are A, B and C?


References


  • Ghosh, S.K., Advanced General Organic Chemistry, Second Edition, New Central Book Agency Pvt. Ltd., Kolkatta, 2007.
  • Morrison, R.T. , Boyd, R.N., Organic Chemistry, Sixth edition, Prentice-Hall of India Pvt. Ltd., 2008.
  • March, j., Advanced Organic Chemistry, Fourth edition, Wiley Eastern Ltd. India, 2005.
  • https://chemicalnote.com/malonic-ester-synthesis-of-carboxylic-acids/

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Malonic ester synthesis (of carboxylic acids): https://chemicalnote.com/malonic-ester-synthesis-of-carboxylic-acids/?utm_source=rss&utm_medium=rss&utm_campaign=malonic-ester-synthesis-of-carboxylic-acids https://chemicalnote.com/malonic-ester-synthesis-of-carboxylic-acids/#respond Wed, 22 Jun 2022 16:53:29 +0000 https://chemicalnote.com/?p=3707 Malonic ester synthesis Ethyl malonate is called as malonic ester. Synthesis of wide variety of organic compounds starting from malonic ester is called malonic ester synthesis. Malonic ester synthesis involves following steps: Step I : The α-hydrogen in malonic ester are acidic. When malonic ester is treated with a strong base such as sodium ethoxide, […]

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Malonic ester synthesis

Ethyl malonate is called as malonic ester.

Malonic ester

Synthesis of wide variety of organic compounds starting from malonic ester is called malonic ester synthesis. Malonic ester synthesis involves following steps:

Step I : The α-hydrogen in malonic ester are acidic. When malonic ester is treated with a strong base such as sodium ethoxide, it is converted into salt, known as sodiomalonic ester.

Malonic ester synthesis

Step II : The carbanion present in sodiomalonic ester is a nucleophile and therefore this step involves nucleophilic attack on the alkyl halide by the carbanion to give monoalkylmalonic ester.

Malonic ester synthesis

The monoalkyl malonic ester have one acidic hydrogen, so it can be alkylate again using same or different alkyl halides to get dialkylmalonic ester.

Malonic ester synthesis

Step III : The mono- or dialkylmalonic ester thus formed can be hydrolysed to give a mono or dialkylmalonic acid. These acids undergo decarboxylation easily to form mono- or disubstituted acetic acid.

Malonic ester synthesis

Malonic ester synthesis


Examples of malonic ester synthesis


Synthesis of 2-methylpentanoc acid by malonic ester synthesis

Structure of 2-methylpentanoic acid is:

2-methylpentanoc acid

2-methylpentanoic acid can be synthesized from malonic ester by following reaction mechanism:

Synthesis of 2-methylpentanoc acid by malonic ester synthesis

Q) Outline the synthesis of pentanoic acid from malonic ester.

Structure of pentanoic acid is:

Pentanoic acid can be synthesized from malonic ester by following reaction mechanism:

synthesis of pentanoic acid from malonic ester

Q) Outline the synthesis of 4-methyl pentanoic acid from malonic ester.

Structure of 4-methyl pentanoic acid is:

4-methyl pentanoic acid can be synthesized from malonic ester by following reaction mechanism:

synthesis of 4-methyl pentanoic acid from malonic ester

Q) Outline the synthesis of 2-ethyl heptanoic acid from malonic ester.

Structure of 2-ethylheptanoic acid is:

2-ethylheptanoic acid can be synthesized from malonic ester by following reaction mechanism:

synthesis of 2-ethyl heptanoic acid from malonic ester

Q) Outline the synthesis of cyclobutane carboxylic acid from malonic ester.

Structure of cyclobutane carboxylic acid is:

Cyclobutane carboxylic acid can be synthesized from malonic ester by following reaction mechanism:

synthesis of cyclobutane carboxylic acid from malonic ester


References


  • Ghosh, S.K., Advanced General Organic Chemistry, Second Edition, New Central Book Agency Pvt. Ltd., Kolkatta, 2007.
  • Morrison, R.T. , Boyd, R.N., Organic Chemistry, Sixth edition, Prentice-Hall of India Pvt. Ltd., 2008.
  • March, j., Advanced Organic Chemistry, Fourth edition, Wiley Eastern Ltd. India, 2005.

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Claisen condensation reaction – Examples and Mechanism https://chemicalnote.com/claisen-condensation-reaction-examples-and-mechanism/?utm_source=rss&utm_medium=rss&utm_campaign=claisen-condensation-reaction-examples-and-mechanism https://chemicalnote.com/claisen-condensation-reaction-examples-and-mechanism/#respond Tue, 08 Jun 2021 15:06:36 +0000 https://chemicalnote.com/?p=3228 Claisen condensation reaction Condensation between two molecules of esters having α-hydrogen atom in the presence of strong base like sodium ethoxide and an acid to form β-keto ester is known as Claisen condensation reaction. Eg. Mechanism of Claisen condensation reaction Taking ethyl acetate (ethyl ethanoate) as an example, Claisen condensation reaction involves following steps: Step-I: […]

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Claisen condensation reaction

Condensation between two molecules of esters having α-hydrogen atom in the presence of strong base like sodium ethoxide and an acid to form β-keto ester is known as Claisen condensation reaction. Eg.

Claisen condensation reaction


Mechanism of Claisen condensation reaction


Taking ethyl acetate (ethyl ethanoate) as an example, Claisen condensation reaction involves following steps:

Step-I: In this step, ethoxide ion removes a proton from α-carbon of one molecule of ethyl acetate to form a carbocation.

  • This step is similar to aldol condensation reaction.

Mechanism of Claisen condensation reaction

Step-II: In this step, the carbanion (i.e. nucleophile) attacks the carbonyl carbon of second ester molecule to displace ethoxide ion and forms the keto ester.

Mechanism of Claisen condensation reaction

  • The claisen condensation differs from aldol condensation at this point. In the aldol condensation, nucleophilic attack leads to addition and in the claisen condensation reaction it leads to substitution.

Step-III: In this step, there is an acid base reaction between ethoxide ion and β-keto ester to give β-keto ester anion and ethanol.

Step-IV: In this step, an acid is added to the reaction mixture which gives proton to the β-keto ester anion to form the β-keto ester which is in equilibrium with its enol form.

Mechanism of Claisen condensation reaction

Note:

Keto-enol tautomerism :

Keto-enol tautomerism is a special type of isomerism in which two isomeric forms, keto and enol exist in dynamic equilibrium with each other. There is transfer of a α- hydrogen to the oxygen atom of carbonyl group and vice-versa.

Keto-enol tautomerism


References


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Cannizzaro’s reaction and Crossed Cannizzaro’s reaction – Definition, Examples and Mechanism https://chemicalnote.com/cannizzaros-reaction-and-crossed-cannizzaros-reaction-definition-examples-and-mechanism/?utm_source=rss&utm_medium=rss&utm_campaign=cannizzaros-reaction-and-crossed-cannizzaros-reaction-definition-examples-and-mechanism https://chemicalnote.com/cannizzaros-reaction-and-crossed-cannizzaros-reaction-definition-examples-and-mechanism/#comments Sun, 06 Jun 2021 13:42:00 +0000 https://chemicalnote.com/?p=3214 Cannizzaro’s reaction Aldehydes which do not contain α-hydrogen like HCHO, C6H5CHO,etc. undergo self oxidation and reduction on treatment with conc. alkali. In this reaction one molecule is oxidized to carboxylic acid and other molecule is reduced to alcohol. Thus, a mixture of an alcohol and a salt of carboxylic acid is formed by Cannizzaro’s reaction […]

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Cannizzaro’s reaction


Aldehydes which do not contain α-hydrogen like HCHO, C6H5CHO,etc. undergo self oxidation and reduction on treatment with conc. alkali. In this reaction one molecule is oxidized to carboxylic acid and other molecule is reduced to alcohol. Thus, a mixture of an alcohol and a salt of carboxylic acid is formed by Cannizzaro’s reaction

•	Ghosh, S.K., Advanced General Organic Chemistry, Second Edition, New Central Book Agency Pvt. Ltd., Kolkatta, 2007. •	Morrison, R.T. , Boyd, R.N., Organic Chemistry, Sixth edition, Prentice-Hall of India Pvt. Ltd., 2008. •	March, j., Advanced Organic Chemistry, Fourth edition, Wiley Eastern Ltd. India, 2005.


Mechanism of Cannizzaro’s reaction

Taking benzaldehyde as an example, Cannizzaro’s reaction involves following steps:

Step I : In first step, there is nucleophilic addition of the hydroxide ion on the carbonyl group to give anion.

Mechanism of Cannizzaro’s reaction

Step II : In this step, the anion transfers a hydride ion to the electron deficient carbonyl carbon of another aldehyde molecule to give carboxylic acid and alkoxide ion.

Mechanism of Cannizzaro’s reaction

Step III : In this step, there is proton exchange between the carboxylic acid and the alkoxide ion to give salt of carboxylic acid and alcohol.

Mechanism of Cannizzaro’s reaction


Crossed Cannizzaro’s reaction


When a mixture of formaldehyde and other aldehyde which has no α-hydrogen atom is treated with conc. alkali, formaldehyde is oxidized to carboxylic acid and another aldehyde is reduced to alcohol. This reaction is crossed cannizzaro’s reaction.

For example, benzyl alcohol and sodium formate is formed when a mixture of benzaldehyde and formaldehyde is treated with conc. NaOH.

Crossed Cannizzaro’s reaction


Mechanism of crossed cannizzaro’s reaction

Taking a mixture of benzaldehyde and formaldehyde as an example, crossed cannizzaro’s reaction involves following steps:

Step-I : In first step, there is nucleophilic addition of the hydroxide ion on the carbonyl group of formaldehyde to give anion.

Mechanism of crossed cannizzaro’s reaction

Step II : In this step, the anion transfers a hydride ion to the electron deficient carbonyl carbon of benzaldehyde molecule to give carboxylic acid and alkoxide ion.

Step III : In this step, there is proton exchange between the carboxylic acid and the alkoxide ion to give salt of carboxylic acid (sod. formate) and alcohol( benzyl alcohol).

Advantage of crossed- cannizzaro’s reaction:

In this reaction an aldehyde is treated with formaldehyde. Here, formaldehyde is oxidized to sodium formate and required alcohol is obtained from the reduction of the other aldehyde. Since both the aldehydes used are completely converted into the required products, there is no wastage of the valuable chemicals.

Why does methyl alcohol is not formed instead of sodium formate in crossed cannizzaro’s reaction?

The initial nucleophilic addition of hydroxide ion is faster on formaldehyde than on other aldehyde as there is no electron donating groups on formaldehyde. Hence, formic acid (sodium formate) is formed but not methyl alcohol.


References


  • Ghosh, S.K., Advanced General Organic Chemistry, Second Edition, New Central Book Agency Pvt. Ltd., Kolkatta, 2007.
  • Morrison, R.T. , Boyd, R.N., Organic Chemistry, Sixth edition, Prentice-Hall of India Pvt. Ltd., 2008.
  • March, j., Advanced Organic Chemistry, Fourth edition, Wiley Eastern Ltd. India, 2005.
  • https://www.toppr.com/ask/content/story/amp/crossed-cannizaro-reaction-6282/
  • https://chemicalnote.com/aldol-condensation-and-crossed-aldol-condensation-reaction-definition-examples-mechanism-and-uses/

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Aldol condensation and Crossed aldol condensation reaction- Definition, Examples, Mechanism and Uses. https://chemicalnote.com/aldol-condensation-and-crossed-aldol-condensation-reaction-definition-examples-mechanism-and-uses/?utm_source=rss&utm_medium=rss&utm_campaign=aldol-condensation-and-crossed-aldol-condensation-reaction-definition-examples-mechanism-and-uses https://chemicalnote.com/aldol-condensation-and-crossed-aldol-condensation-reaction-definition-examples-mechanism-and-uses/#respond Sun, 23 May 2021 13:01:54 +0000 https://chemicalnote.com/?p=3164 Aldol condensation reaction Aldol condensation reaction is one of the important reactions of carbonyl compounds (i.e. aldehydes and ketones) Condensation between two molecules of aldehydes or ketones having at least one α – hydrogen atom in presence of dilute alkali to form β-hydroxy aldehyde or β-hydroxy ketone is known as aldol condensation reaction. Examples: Aldehydes […]

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Aldol condensation reaction


Aldol condensation reaction is one of the important reactions of carbonyl compounds (i.e. aldehydes and ketones)

Condensation between two molecules of aldehydes or ketones having at least one α – hydrogen atom in presence of dilute alkali to form β-hydroxy aldehyde or β-hydroxy ketone is known as aldol condensation reaction. Examples:

Aldol condensation reaction

Aldehydes and ketones which do not contain any α – hydrogen atom such as HCHO, (CH3)3CCHO, C6H5CHO, etc. do not undergo aldol condensation reaction.


Mechanism of aldol condensation reaction


Taking acetaldehyde (ethanal) as an example, aldol condensation involves following steps:

Step-I :

In this step, hydroxide ion from alkali removes a proton from the α – carbon of one molecule of ethanal to give a carbanion (i.e. enolate ion).

Mechanism of aldol condensation reaction

Step-II :

In this step, there is nucleophilic addition of enolate ion to the carbonyl carbon of second molecule of ethanal to produce an alkoxide ion.

Mechanism of aldol condensation reaction

Step-III :

In this step, the alkoxide ion takes up a proton from water to form β-hydroxy aldehyde (aldol).

Mechanism of aldol condensation reaction


Dehydration of aldol products


The product of aldol condensation on heating with dilute acids undergo dehydration to form α, β-unsaturated aldehydes or ketones. Examples:

Dehydration of aldol products


Uses of aldol condensation in synthesis


Aldol products contain two functional groups (-OH and –CHO) and hence they can be used in a number of reactions to give various products. For example:

1. Catalytic hydrogenation of α, β-unsaturated aldehydes or ketones, obtained from dehydration of aldol products gives saturated alcohols.

Uses of aldol condensation in synthesis

2. Reduction of α, β-unsaturated aldehydes or ketones by LiAlH4 gives unsaturated alcohol.

Uses of aldol condensation in synthesis


Crossed aldol condensation reaction


  • Aldol condensation between two different carbonyl compounds is called a crossed aldol condensation.
  • Crossed aldol condensation is not useful in laboratories if both of the carbonyl compounds have α-hydrogen, because a mixture of products are formed.
  • However, it is useful when one of the carbonyl compounds does not have α-hydrogen and therefore cannot undergo self condensation. For example: benzaldehyde can be used with other aldehydes and ketones containing α-hydrogen.

Crossed aldol condensation reaction


Mechanism of crossed-aldol condensation reaction


[same as that of aldol condensation reaction]

Taking acetaldehyde (ethanal) and benzaldehyde as examples of aldehydes, crossed aldol condensation involves following steps:

Step-I :

In this step, hydroxide ion from alkali removes a proton from the α – carbon of ethanal to give a carbanion (i.e. enolate ion).

Mechanism of crossed-aldol condensation reaction

Step-II :

In this step, there is nucleophilic addition of enolate ion to the carbonyl carbon of benzaldehyde to produce an alkoxide ion.

Mechanism of crossed-aldol condensation reaction

Step-III :

In this step, the alkoxide ion takes up a proton from water to form β-hydroxy aldehyde (aldol).

Mechanism of crossed-aldol condensation reaction


References


  • Finar, I. L., Organic Chemistry, Vol. I and Vol. II, Prentice Hall, London, 1995.
  • Ghosh, S.K., Advanced General Organic Chemistry, Second Edition, New Central Book Agency Pvt. Ltd., Kolkatta, 2007.
  • Morrison, R.T. , Boyd, R.N., Organic Chemistry, Sixth edition, Prentice-Hall of India Pvt. Ltd., 2008.
  • March, j., Advanced Organic Chemistry, Fourth edition, Wiley Eastern Ltd. India, 2005.

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