Named reactions of organic chemistry- an overview

Table of Contents

This article on organic reactions is a special one in our organic chemistry series. It will guide you through how chemical transformations unlock diversity at the molecular level.

You will find it one of the most comprehensive sources on named reactions in organic chemistry available on the web.

Moreover, we have also included a cheat sheet for you at the end of this article so that you can have a road map to learn organic chemistry in the most fun way possible.

Thus, without any further ado, let’s start reading!  

List of organic chemistry reactions

Reactions of alkanes

  • Halogenation reaction of alkanes

Substrate: Saturated hydrocarbons/alkanes (CH4, C2H6, C3H8, etc.)

Reagent: Halogen X2 (F2, Cl2, Br2, I2)

Conditions: UV-light, 25°C temperature or Heating at (250-400) °C

Mechanism: Free radical substitution

Order of reactivity:

The reactivity of halogens follows the order: F2 >> Cl2 > Br2 > I2

Product: Halogenoalkane or alkyl halide (R-X)

  • Nitration of alkanes

Substrate: Saturated hydrocarbons/alkanes (CH4, C2H6, C3H8, etc.)

Reagent: Nitric acid (HNO3)

Conditions: Excess of 60% HNO3 at 400° C temperature

Product:  Nitroalkane (R-NO2)

  • Sulfonation of alkanes

Substrate: Saturated hydrocarbons/alkanes (CH4, C2H6, C3H8, etc.)

Reagent & Conditions: H2SO4 + SO3 or fuming sulfuric acid (H2S2O7)

Product:  Alkane sulfonic acid (R-SO3H)

  • Combustion reaction of alkanes

Substrate: Saturated hydrocarbons/alkanes (CH4, C2H6, C3H8, etc.)

Reagent & Conditions: Ignition at very high temperatures in the presence of air or oxygen 

Products:  Carbon dioxide (CO2) + water (H2O)

  • Oxidation reaction of alkanes

Substrate: Alkanes containing tertiary hydrogen (R2-CH-R)  

Reagent: Oxidizing agent (KMnO4)

Mechanism: Addition of oxygen

Products:  Tertiary alcohol

  • Hydroforming or catalytic reforming of alkanes

Substrate: Long-chain alkanes (such as n-hexane) 

Reagent & Conditions: Heating at 450-550 °C under pressure in the presence of chromic oxide supported on Al2O3.

Mechanism: Hydrogenation, cyclization followed by isomerization 

Product:  Aromatic compound (such as benzene from n-hexane)

  • Pyrolysis or cracking of alkanes

Substrate: Long-chain alkanes

Condition:  Heating at high temperatures (500°C)

Mechanism: Thermal decomposition

Products:  A mixture of short-chain alkanes and alkenes 

  • Isomerization of alkanes

Substrate: Alkane

Reagents: HCl

Conditions: AlCl3 at 300°C temperature 

Products:  Isomer of the parent molecule 

  • Oxidation of methane

Substrate: Methane (CH4)

Reagents & Conditions: Copper tube, 200°C temperature, 100 atm pressure

Product:  Formaldehyde (HCHO)  

Reactions of alkenes

  • Hydrogenation of alkenes

Substrate: Unsaturated hydrocarbon/alkenes (C2H4, C3H6, C4H8)   

Reagent: Hydrogen (H2) gas

Conditions: Pt, Pd or Ir catalyst in finely divided form or Raney Nickel

Mechanism: Electrophilic addition reaction 

Product:  Saturated hydrocarbons (alkanes)

  • Addition of hydrogen halides to alkenes

Substrate: Unsaturated hydrocarbon/alkenes (C2H4, C3H6, C4H8)   

Reagent: Hydrogen halide (HX)

Conditions: Passing dry gaseous HX directly through the alkene sample  

Mechanism: Electrophilic addition reaction (involving a carbocation intermediate)  

Product:  Alkyl halide (R-X)

Order of reactivity:

The reactivity of hydrogen halide follows the order: HI > HBr > HCl > HF

  • Hydration of alkenes

Substrate: Unsaturated hydrocarbon/alkenes (C2H4, C3H6, C4H8)   

Reagent: Water (H2O) 

Conditions: Acidic conditions  

Mechanism: Electrophilic addition reaction

Product:  Alcohol (R-OH)

  • Addition of halogens

Substrate: Unsaturated hydrocarbon/alkenes (C2H4, C3H6, C4H8)   

Reagent: Halogen (Cl2, Br2, etc)  

Conditions: Inert solvent (such as CCl4) at room temperature   

Mechanism: Electrophilic addition reaction (a cyclic halonium ion is formed as an intermediate)

Product:  Halogenoalkane (vic-dichlorides or vic-dibromides) 

  • Epoxidation reaction

Substrate: Unsaturated hydrocarbon/alkenes (C2H4, C3H6, C4H8)   

Reagent: Peracetic acid

Mechanism: Electrophilic addition

Product:  Cyclic ether

  • Hydroxylation reaction

Substrate: Unsaturated hydrocarbon/alkenes (C2H4, C3H6, C4H8)   

Reagents: Osmium tetrachloride (OsO4) and H2O

Mechanism: Oxidation (addition of OsO4 followed by hydrolysis with water)

Product:  Syn-diol 

  • Ozonolysis

Substrate: Cyclic alkenes (such as cyclohexene)    

Reagents: Ozone (O3) gas and hydrogen peroxide (H2O2)

Mechanism: Oxidation  

Product:  Dioic acid (an Ozonide)

  • Polymerization reaction of alkenes 

Substrate: A large number of alkene monomers     

Mechanism: Chain addition of monomers

Product:  Polymer 

  • Addition of carbenes (Simmon Smith reaction) 

Substrate: Unsaturated hydrocarbon/alkenes (C2H4, C3H6, C4H8)   

Reagent & Conditions: Simmon Smith reaction mixture (I2CH3 and Zn/Cu couple in anhydrous ether)

Mechanism: Electrophilic addition via a carbene (CR2) intermediate

Product: Cycloalkane   

  • Isomerization of alkenes

Substrate:  Unsaturated hydrocarbon/alkenes (C2H4, C3H6, C4H8)   

Reagent & Conditions: Very high temperature (500-700°C) or low temperature in the presence of an AlCl3 catalyst

Product: Isomer of the parent molecule

Reactions of alkyl halides

  • Reduction reaction

Substrate:  Alkyl halides (R-Cl, R-Br, R-I)

Reagent & Conditions: Reducing agents (LiAlH4 or NaBH4) in ether

Mechanism: Hydride transfer 

Product: Alkane (R-H)

  • Catalytic hydrogenolysis of alkyl halides

Substrate: Alkyl halides (R-Cl, R-Br, R-I)

Reagent & Conditions: Grignard reagent (R-Mg-X) prepared in ether 

Mechanism: Hydrolysis  

Product: Alkane (R-H)

  • Dehydrohalogenation of alkyl halides

Substrate:  Alkyl halides (R-Cl, R-Br, R-I)

Reagents: Sodium ethoxide (CH3CH2ONa+) prepared in ethanol (CH3CH2OH)

Condition: High temperature (300-400°C)

Mechanism: Elimination  

Product: Alkene (R-C=C-R)

  • Dehalogenation of vic-dihalides

Substrate:  Vic-dihalide (Cl-R-R-Cl, Br-R-R-Br)

Reagent & Conditions: Zinc dust in an anhydrous solvent (CH3OH or CH3COOH)

Mechanism: Elimination  

Product: Alkene (R-C=C-R)

Reactions of alcohols 

  • Dehydration of alcohols

Substrate:  Alcohol (primary, secondary or tertiary) 

Reagent: Sulfuric acid (H2SO4)

Conditions:

  • Conc. H2SO4, 180° C temperature for primary alcohols
  • 60-80 % H2SO4, 100°C for secondary alcohols
  • 20 % H2SO4, 85 °C for tertiary alcohols

Mechanism: Elimination

Product:  Alkene (R-C=C-R)

  • Reaction of alcohols with metals

Substrate:  Alcohol (R-OH)

Reagent: Sodium (Na) metal

Products: Sodium alkoxide (R-ONa+) and hydrogen (H2)

Order of reactivity: The reactivity of alcohols decreases in the order: primary > secondary > tertiary.

  • Esterification reaction of alcohols with carboxylic acids

Substrate:  Alcohol (R-OH)

Reagent: Carboxylic acid (R-COOH)

Conditions: Acidic (conc. H2SO4) + heat 

Mechanism: Condensation reaction 

Products: Sodium alkoxide (R-ONa+) and water (H2O)

  • Oxidation of primary alcohols

Substrate:  Primary alcohol (R-CH2-OH) 

Reagent & Conditions: Acidified oxidizing agent (K2Cr2O7/H+) + heat

Mechanism: Addition of oxygen  

Products: Aldehyde (R-CHO) under controlled conditions followed by carboxylic acid (R-COOH) after complete oxidation.

  •  Oxidation of secondary alcohols

Substrate:  Secondary alcohol (R-CH(OH)-R) 

Reagent & Conditions: Acidified oxidizing agent (K2Cr2O7/H+) + heat

Mechanism: Removal of hydrogen   

Product: Ketone (R-CO-R) 

Reactions of aldehydes and ketones

  • Reduction reaction of aldehydes 

Substrate:  Aldehyde (R-CHO)  

Reagent: Reducing agents (such as LiAlH4)

Mechanism: Nucleophilic addition

Product:  Primary alcohol (R-CH2-OH)

  • Reduction reaction of ketones

Substrate:  Ketone (R-CO-R)  

Reagent: Reducing agents (such as LiAlH4)

Mechanism: Nucleophilic addition

Product:  Secondary alcohol (R-CH(OH)-R)

Important named reactions in organic chemistry

An organic reaction is usually named on the name of the scientist who introduced it. Given below are some popular named reactions in organic chemistry. These are mentioned in alphabetical order.  

  • Aldol condensation

Substrate:  2 equivalents of carbonyl compounds (aldehydes or ketones having one or more alpha hydrogens) such as acetaldehyde.  

Reagent & Conditions: NaOH + H2O + Heat

Mechanism: Nucleophilic addition, an enolate is formed as an intermediate

Product:  Aldol (possessing both aldehyde (CHO) and alcohol (OH) functional groups)

  • Azo coupling

Substrate: Diazonium salt (Ar-N≡N-X) + aromatic compound (Ar-H) such as phenol or aniline  

Reagent & Conditions: Mildly alkaline solution  

Mechanism: Electrophilic aromatic substitution

Product:  Azo dye  

  • Beckmann rearrangement

Substrate:  Cyclohexanone + hydroxylamine

Reagent & Conditions: Acidic conditions +heat   

Mechanism: Rearrangement reaction that proceeds via oxime formation   

Product:  Cyclic amide (such as Caprolactam)

  • Cannizzaro’s reaction

Substrate:  2 equivalents of aldehydes containing no alpha hydrogen, such as formaldehyde

Reagent & Conditions: 50% aq. or alcoholic NaOH at room temperature

Mechanism: Self-oxidation followed by reduction of the aldehyde

Products:  Alcohol + Metal oxide  

  • Claisen-Schmidt condensation

Substrate:  Phenolic allyl ether

Conditions: Heat  

Mechanism: Molecular rearrangement via [3,3]-sigmatropic shift

Product:  2-allyl phenol   

The Claisen-Schmidt condensation is also known as crossed aldol condensation.

  • Clemmensen reduction

Substrate:  Carbonyl compound (Aldehyde or Ketone)  

Reagent & Conditions:  Zinc amalgam in hydrochloric acid

Mechanism: Removal of oxygen and addition of hydrogen, zinc organyl formed as an intermediate

Product:  Alkane

  • Diels-Alder reaction

Substrate:  Diene + Dienophile (alpha, beta-unsaturated carbonyl compound)   

Reagent & Conditions:  Benzene + 20°C temperature  

Mechanism: Cycloaddition  

Product:  Adduct (six-membered ring)

  • Frankland reaction

Substrate:  Iodomethane (CH3I)

Reagent & Conditions: Zinc (Zn) metal and ether  

Product:  Ethane (CH3-CH3)

  • Friedel craft reaction 

The Friedal craft catalyst is a Lewis acid (AlCl3) used for the following two types of coupling reactions:

1. Friedel craft alkylation

Substrate:  Benzene     

Reagent: Alkyl halide (R-X)

Conditions: AlCl3 catalyst, reflux anhydrous conditions    

Mechanism: Electrophilic aromatic substitution

Product:  Alkyl benzene  

2. Friedel craft acylation

Substrate:  Benzene     

Reagent: Acyl halide (R-(C=O)-X)

Conditions: AlCl3 catalyst  

Mechanism: Electrophilic aromatic substitution

Product:  Alkyl phenyl ketone    

  • Gattermann reaction

Substrate:  Benzene    

Reagents: A mixture of hydrogen cyanide (HCN) and hydrochloric acid (HCl)  

Conditions: AlCl3 catalyst 

Mechanism: Electrophilic aromatic substitution

Product:  Benzaldehyde    

  • Hofmann rearrangement

Substrate:  Amide (R-CONH2 or Ar-CONH2)  

Reagent & Conditions: Br2 + NaOH

Mechanism: Rearrangement reaction via an isocyanate intermediate

Product:  Amine (R-NH2 or Ar-NH2)   

  • Meerwein-Ponndorf-Verley (MPV) reduction

Substrate:  Aldehyde or Ketone

Reagent & Conditions: Alcohol (such as isopropanol) and aluminum alkoxide (Al(OPri)3)

Mechanism: Pericyclic (hydride transfer)

Product:  Primary alcohol (for aldehyde)/ Secondary alcohol (for ketone) 

  • Oppenauer oxidation

Oppenauer oxidation is the reverse of MPV reduction.

Substrate:  Alcohol 

Reagent & Conditions: Aluminium alkoxide (Al(OPri)3)

Mechanism: Pericyclic  

Product:  Carbonyl compound (aldehyde or ketone) 

  • Pinacol-pinacolone rearrangement

Substrate:  Dihydric alcohol, i.e., Pinacol (2,3-dimethylbutan-2,3-diol)   

Reagent & Conditions: Conc. H2SO4 + Heat

Mechanism: Rearrangement  

Product:  Pinacolone (3,3-dimethylbutan-2-one)

  •  Sandmeyer’s reaction

Substrate:  Benzene diazonium salt (ArN2+X)  

Reagent & Conditions: Cu-X + HCl or CuCN + KCN at room temperature

Mechanism: Replacement of the diazonium group by another group 

Product:  Ar-X’ or Ar-CN

  • Walden inversion

Walden inversion refers to any chemical reaction that yields a product whose stereochemical configuration is opposite to that of the reactant molecule.

For example;

Substrate: levorotatory-2-bromooctane   

Reagent & Conditions: Alkaline (NaOH) 

Mechanism: Nucleophilic substitution (SN2)

Product: dextrorotatory-2-Octanol

  • Williamson ether synthesis

Substrate: Phenol (Ar-OH)    

Reagent: Alkyl halide (R-X)

Conditions: Aqueous NaOH + heat under reflux for 3 hrs.

Mechanism: Nucleophilic substitution (SN2)

Product: Ether (Ar-O-R)

  • Witting reaction

Substrate: Aldehyde or Ketone     

Reagents: Alkyl halide (R-X) + Triphenylphosphine (PPh3)

Conditions:  NaOH in an inert solvent such as xylene 

Mechanism: Nucleophilic addition via a ylide intermediate

Product: Alkene   

  • Wurtz-Fitting reaction

Substrate:  Iodomethane (CH3I)

Reagent & Conditions: Sodium (Na) metal and ether  

Product:  Ethane (CH3-CH3)

  • Wohler synthesis

The Wohler synthesis is often cited as the foundation stone for organic chemistry.

Reagent & Conditions: A mixture of sodium cyanate (NaCNO) and ammonium chloride (NH4Cl) is heated and then cooled to produce ammonium cyanate 

Mechanism: Proton transfer to ammonium cyanate followed by tautomerism

Product:  Urea (H2N-C(=O)-NH2)

  • Wolff-Kisnher reduction

Substrate:  Aromatic ketone (Ar-C(=O)-R)

Reagent:  Reducing agent, i.e., hydrazine (NH2NH2)

Conditions:  Strong base (conc. KOH) prepared in ethylene glycol (HO-(CH2)2-OH) + heat

Mechanism: Reduction via a semicarbazone intermediate

Products:  Aromatic hydrocarbon (Ar-H) + Nitrogen (N2)

For a detailed study of the above-mentioned reaction mechanisms, you may consult our article: 6 main types of reactions in organic chemistry.

Meanwhile, the cheat sheet provided below shows the important reactions of benzene, the parent member of the aromatic family.

All the reaction mechanisms given in this article are drawn by the writer herself (Ammara W.)

Also, check out this other wonderful source on organic reactions and mechanisms.

You may also want to learn some tips and tricks on studying organic chemistry.

Last but not least, we would like you to test your knowledge on organic reactions via this very helpful exercise.  

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