47 Common Named Substitution Reactions

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Coupling Reactions

Castro-Stephens Coupling

Coupling of alkynyl cuprates and aryl halides.


Friedel-Crafts Acylation

Coupling of aryls and acyl halides with Lewis acid catalyst.


Friedel-Crafts Alkylation

Coupling of aryls and alkyl halides with Lewis acid catalyst.


Friedel-Crafts Arylation

Also known as: Scholl Reaction

Coupling of two substituted aryls with Lewis acid catalyst.


Gomberg Reaction

Also known as: Gomberg-Bachmann Reaction

Coupling of aryls and aryl diazonium salts in alkaline solution.


Heck Reaction

Coupling of alkyls and aryls with Pd catalyst.


Pschorr Reaction

Intramolecular coupling of aryls and aryl diazonium salts.

Note: Intramolecular variation of the Gomberg reaction.


Sonogashira Coupling

Coupling of terminal alkynes and aryl halides with Pd catalyst.


Stille Reaction

Coupling of alkyl halides and organotins with Pd catalyst.


Suzuki Reaction 

Also known as: Suzuki-Miyaura Reaction

Coupling of arylboronic acids and aryl halides.


Ullmann Reaction

Coupling of two aryl halides with Lewis acid catalyst.


Wurtz Reaction

Coupling of two alkyl halides with sodium.


Nucleophilic Aliphatic Substitution Reactions

Bunte Salt Formation

Reaction between alkyl halides and disulfur trioxides (S2O32-) forming Bunte salts.


Finkelstein Reaction

Also known as: Halogen exchange reaction

Reaction between alkyl halides and halide salts resulting in halogen exchange.


Gabriel Synthesis

Reaction between alkyl halides and phthalimide salts forming phthalimides that are hydrolysed into primary amines.

Note: RNH3+ salts are usually formed and can be converted to the amine.


Ing-Manske Procedure

A variation of the Gabriel synthesis. In the second step, the phthalimide is heated with hydrazine to form the primary amine instead.


Menshutkin Reaction

Reaction between alkyl halides and tertiary amines forming quaternary ammonium salts.

Note: Similar reactions involving primary and secondary amines exist (alkylation of amines).


Meyers Synthesis

Three-step reaction forming aldehydes from oxazines.


Mitsunobu Reaction

Reaction between alkyl halides and carboxylates forming esters.

Note: Carboxylic acids are sometimes used as well.


Stork Enamine Reaction

Also known as: Stork enamine alkylation

Reaction between carbonyls and secondary amines forming α-alkylated products.


von Braun Reaction

Also known as: Cyanamide formation

Reaction between bromonitriles and tertiary amines forming cyanamides.


Williamson Ether Synthesis

Reaction between alkyl halides and alkoxide anions forming ethers.


Electrophilic Aliphatic Substitution Reactions

Haller-Bauer Reaction

Reaction between ketones and sodium amide resulting in the ketone being cleaved.


Hell-Volhard-Zelinsky Reaction

Reaction between molecular halides and carboxylic acids resulting in α-halogenation.

Note: Usually only Cl2 or Br2 is used.


Japp-Klingemann Reaction

Reaction between carbonyls and diazonium salts forming hydrazones at the α-position.


Regitz Diazo-Transfer Reaction

Reaction between activated aliphatics and tosyl azides forming diazo compounds.

Note: Rarely do unactivated carbonyl compounds react via this method.


Nucleophilic Aromatic Substitution Reactions

Bucherer Reaction

Reaction between naphthols and ammonia forming naphthamines.


Chichibabin Reaction

Reaction between pyridines and sodium amide resulting in amination.


Goldberg Reaction

Intramolecular reaction between aryl halides and sodium amide forming amines.


Hurtley Reaction

Reaction between aryl halides and carbons with active hydrogens resulting in arylation.

Note: Catalysis is performed by copper halides.


Meerwein Arylation

Reaction between activated alkenes and aryl diazonium salts resulting in arylation.


Rosenmund von Braun Reaction

Reaction between aryl halides and CuCN forming aryl nitriles.


Sommelet-Hauser Rearrangement

Reaction between benzylic quaternary ammonium salts and sodium amide resulting in rearrangement of the ammonium salt (not the carbon it is bonded to).


Smiles Rearrangement

Intramolecular reaction of nucleophilic substituents and activated aryls.

Note: A variation is the Truce-Smiles rearrangement where the nucleophile is a carbanion.


Ullmann Condensation

Also known as: Ullmann ether synthesis

Reaction between aryl halides and activated phenols forming diaryl ethers.

Note: Not to be confused with the Ullmann reaction.


von Richter Rearrangement

Reaction between nitrobenzenes and cyanide ions resulting in cine substitution of a carboxylic acid (hydrolysis is not involved).

Note: Cine substitution is where the substituent forms adjacent to the leaving group carbon.


Ziegler Alkylation

Reaction between aryls containing heteroatoms and alkyllithiums resulting in arylation.


Electrophilic Aromatic Substitution Reactions

Balz-Schiemann Reaction

Reaction between aryl diazonium salts and fluoroborates forming fluorobenzenes.


Fischer-Hepp Rearrangement

Reaction between nitrosobenzenes and HCl resulting in rearrangement.


Fries Rearrangement

Rearrangement of phenolic esters with Lewis acid catalyst.


Gatterman Reaction

Reaction between aryls and zinc nitriles in HCl resulting in formylation.

Note: Variation of the Vilsmeier-Haack formylation.


Henkel Reaction

Rearrangement of phthalates to terphthalates with cadmium catalyst.


Hofmann-Martius Rearrangement

Reaction between secondary amines and HCl resulting in rearrangement of the R group.


Houben-Hoesch Reaction

Reaction between aryls and nitriles in HCl resulting in acylation.

Note: Variation of Friedel-Crafts acylation.


Jacobsen Rearrangement

Reaction between polyalkylbenzenes and H2SO4 resulting in sulfonation and rearrangement of alkyl groups.

Note: Usually, the polyalkylbenzene must have four or more alkyl groups.


Orton Rearrangement

Reaction between an N-chloro arylamines and HCl causes migration of the chloride.


Vilsmeier-Haack Reaction

Also known as: Vilsmeier-Haack formylation

Reaction between aryls, disubstituted formamides and POCl3 resulting in formylation.


chemshard

Just a first-year university student with a passion for organic chemistry and reactions.

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