Gattermann - Koch Reaction: Mechanism, Limitations and Examples

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Jasmine Grover

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Gattermann - Koch reaction is used for the purpose of manufacturing benzaldehyde industrially. It is one of the most significant naming reactions. Ludwig Gattermann and Julius Arnold Koch developed the Gattermann-Koch reaction. The basic purpose of the reaction is to attach a -CHO (formyl group) to any given aromatic system. The Gattermann - Koch reaction does not work with phenol and phenol ether as a substrate. Copper(I) chloride is necessary as a co-catalyst in the reaction when zinc chloride is employed as a catalyst in the Gattermann Koch reaction. In this article, we will understand the mechanism of the Gattermann Koch reaction, understand its limitations, and look at some related sample questions.

Keyterms: Benzaldehyde, Zinc Chloride, Ether, Phenol, Copper (I) chloride, Carbon Monoxide, Carbon, Proton, Electrophile, Neucleophile, Benzene


What is the Gattermann – Koch reaction?

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Benzene is reacted with carbon monoxide in an acidic solution in the presence of anhydrous aluminium chloride to yield benzaldehyde in the Gattermann – Koch reaction. Anhydrous aluminium chloride acts as a catalyst in this process. It follows the mechanism of an electrophilic substitution reaction. The Gattermann – Koch Reaction does not work with phenol and phenol ether substrates.

An example of Gattermann - Koch is as given below:

Gattermann - Koch Reaction

Gattermann - Koch Reaction

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Mechanism of Gattermann – Koch Reaction 

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The Gattermann–Koch response mechanism may be broken down into three steps:

Step 1: Forming Formyl Chloride

The production of reactive species, which can subsequently be utilized to react on the aromatic ring, is the first step in the Gattermann Koch reaction process. Carbon monoxide may receive a proton from hydrochloric acid since it is a Lewis base. As a result, a positively charged molecule with various resonance configurations emerges. One of these resonance structures has a positive charge on the carbon, which explains the hybrid's reactivity. While interacting with the aromatic ring, this species might function as an electrophile.

It is, however, more likely to be attacked nucleophilically by the chloride ion in hydrochloric acid.

Step 2: 

Mechanism of Gattermann – Koch Reaction 
Mechanism of Gattermann – Koch Reaction 

When a Lewis acid (aluminium chloride) is introduced to the species, it quickly eliminates a chloride ion. The species has now reverted to the formyl cation, which is reactive.

Step 3: At the aromatic ring, an electrophilic aromatic substitution occurs. The formyl cation receives an electron pair from the aromatic ring, which serves as a nucleophile. The loss of aromaticity is quickly restored when a proton is ejected.

Mechanism of Gattermann – Koch Reaction 
Mechanism of Gattermann – Koch Reaction 

As a result of the Gattermann – Koch reaction, the formyl group is linked to the aromatic ring. Benzaldehyde is produced when benzene is treated with carbon monoxide and hydrochloric acid in the presence of aluminium chloride, as illustrated in the above process.


Limitations of Gattermann – Koch reaction

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The Gattermann-Koch reaction is restricted to alkylbenzenes due to a lack of appropriate substrates, hence Gattermann devised a modification that allowed for the formylation of phenols, phenolic ethers, and heteroaromatic compounds such as pyrroles and indoles.

The Gattermann formulation has one major flaw: it required the use of anhydrous hydrogen cyanide (HCN). R. Adams, therefore, created HCN in-situ from zinc cyanide and hydrochloric acid to avoid handling it; this approach became known as the Adams modification, and it is now more commonly employed in organic synthesis.

Gattermann - Koch reaction with phenol substrates

Gattermann - Koch reaction with phenol substrates


Things to Remember

  • Using formyl chloride (HCOCl) as an acylating agent under Friedel-Crafts acylation conditions, L Gattermann and J.A. Koch effectively inserted an aldehyde group on toluene in 1897. 
  • Gattermann-Koch formylation was named after the addition of a formyl group to electron-rich aromatic rings using CO/HCl/Lewis acid catalysts (AlX3, FeX3, where X = Cl, Br, I) to produce aromatic aldehydes.
  • The Gattermann-Koch Reaction uses carbon monoxide and hydrochloric acid as reactants to produce an aryl aldehyde. 
  • Aluminium trichloride catalyses the process in the presence of trace quantities of cuprous chloride.
  • Because phenol and phenol ethers "could not be effectively formylated at atmospheric pressure in benzene as a solvent," the Gattermann-Koch Reaction is not applicable to them. "The insolubility of the cuprous chloride in the reaction mixture was blamed for the failure to react."
  • To make substituted benzaldehydes, the Gattermann-Koch Formylation method is utilised. The formyl cation is the important intermediate here, and once produced, it interacts like the other acyl cations in Friedel-Crafts processes.

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Sample Questions

Ques. Who was the first to discover the Gattermann Koch reaction? (1 mark)

Ans. Ludwig Gattermann (1860–1920), a German chemist, developed it in 1890.

Ques. State with an example, what is Gattermann - Koch reaction? (2 marks) 

Ans. Benzaldehyde or substituted benzaldehyde is formed when benzene or one of its derivatives is treated with hydrogen chloride and carbon monoxide in the presence of cuprous chloride or anhydrous aluminium chloride.

The Gattermann Koch response is the name for this reaction.

The Gattermann Koch response is the name for this reaction.
The Gattermann Koch response is the name for this reaction.

Ques. State the product in the Gattermann-Koch reaction. (3 marks) 

Ans. The Gattermann Koch Reaction Mechanism begins with the production of reactive species using acid as a catalyst. The reaction's ultimate goal is to attach a formyl group (-CHO group) to an aromatic system, resulting in the formation of an aromatic aldehyde as a product.

Benzaldehyde is produced when benzene is reacted with carbon monoxide in an acidic solution in the presence of anhydrous aluminium chloride. In this process, anhydrous aluminium chloride functions as a catalyst. An electrophilic substitution reaction is what occurs.

Ques. Elucidate the mechanism of Gattermann Koch Reaction. (5 marks) 

Ans. The mechanism of the Gattermann - Koch reaction is as follows:

Step 1: Carbon monoxide functions as a Lewis base, accepting a proton from hydrochloric acid to produce a positively charged molecule with various resonance configurations. One of these has a positive charge on the carbon and reacts with the aromatic ring as an electrophile. The chloride ion in hydrochloric acid, on the other hand, attacks it nucleophilically.

Carbon monoxide reacts with hydrochloric acid to create formyl chloride, which is the first step in the process.

Step 2: The formyl chloride generates an electrophile or aldehyde intermediate when it interacts with anhydrous aluminium chloride, which acts as a catalyst.

Step 3: The electrophile or aldehyde group finally interacts with the benzene ring to produce the end product, benzaldehyde. The aromatic ring acts as a nucleophile, giving the formyl cation an electron pair. The simultaneous ejection of a proton resolves the transient loss of aromaticity. Hydrochloric acid and aluminium chloride are both eliminated as a result of this reaction.

Ques. In Friedel Crafts acylation, how is a Lewis acid used? (2 marks) 

Ans. The Gattermann – Koch process is one of the most popular aromatic chemistry procedures utilized in the production of aryl ketones. When stoichiometric quantities of Lewis acid are used, a complex form at the conclusion of the reaction between the aryl ketone produced and the Lewis acid.

Ques. What is the limitation of the Gattermann – Koch reaction? (2 marks) 

Ans. Phenol and phenol ether substrates are not suitable for the Gattermann-Koch reaction. If we employ zinc chloride as a catalyst in the Gattermann – Koch reaction, we must additionally add traces of copper(I) chloride, which acts as a co-catalyst, enhancing the activity of catalysts. 

Ques. When Pyrrole undergoes the Gattermann - Koch reaction, what happens? (5 marks) 

Ans. The electron density of the ring is significant because it usually starts with a nucleophilic assault by the aromatic group. Regioselective formylation is known to occur in certain aromatic compounds, such as pyrrole. The Gattermann reaction and the Gattermann-Koch reaction may both be used to formylate benzene rings.

Other electron-rich substrates such as mesitylene, pyrrole, or fused aromatic rings might also be anticipated to react since they can be quickly deprotonated to produce phenoxides, which are good nucleophiles. Under strong circumstances, benzene will react, although deactivated rings like pyridine are difficult to formylate efficiently.

Many formylation methods would produce just the ortho result, whereas phenol would generally produce a mixture of ortho and para molecules (e.g. 2-hydroxybenzaldehyde). This can be explained through the strong attractive forces that exist between the formylating reagent and phenoxide during the reaction, such as ionic interactions with the nitrogen centers that are cationic in the Vilsmeier–Haack reaction and Duff reaction, or coordination to metals of high oxidation in the Rieche formylation (Kolbe–Schmitt reaction) and the Casiraghi formylation.

The Casiraghi formylation allows phenol to react directly with paraformaldehyde; all earlier techniques utilized disguised forms of formaldehyde, in part to prevent the production of phenol-formaldehyde resins. Because aldehydes are highly deactivating, phenols usually only react once; nevertheless, some reactions, such as the Duff reaction, might result in multiple additions.

Ques. What is used in the Gattermann Koch reaction? (2 marks) 

Ans. The Gattermann – Koch reaction is a variation of the Gattermann reaction that uses carbon monoxide (CO) instead of hydrogen cyanide. It is named after German scientists Ludwig Gattermann and Julius Arnold Koch.

Ques. What is the difference between the Koch and Gattermann reactions? (2 marks) 

Ans. A variant of the Gattermann response is the Gattermann Koch reaction. The main distinction between the Gattermann and Gattermann Koch reactions is that the former utilizes a combination of hydrogen cyanide and hydrochloric acid, whilst the latter uses carbon monoxide instead of hydrogen cyanide.

Ques. Why does the Gattermann Koch reaction not work with phenol? (2 marks) 

Ans. As phenol and phenol ethers "could not be effectively formylated at atmospheric pressure in benzene as a solvent," the Gattermann-Koch Reaction is not applicable to them. "The insolubility of the cuprous chloride in the reaction mixture was blamed for the failure to react."

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CBSE CLASS XII Related Questions

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    Conductivity of \( 2.5 \times 10^{-4} \) M methanoic acid solution is \( 5.25 \times 10^{-5} \) S cm\(^{-1}\).

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                      • 6.

                        Organic compounds containing carbonyl group as the functional group are aldehydes, ketones and carboxylic acids. The carbon-oxygen double bond is polarised due to higher electronegativity of oxygen as compared to carbon. Aldehydes are generally more reactive than ketones in nucleophilic addition reactions due to steric and electronic reasons. They react with HCN, Sodium bisulphite, Grignard reagent and a number of ammonia derivatives like Hydroxylamine, Hydrazine, Semicarbazide, etc. Aldehydes and ketones undergo various reactions due to the acidic nature of \(\alpha\)-hydrogen. Aldehydes and ketones having at least one \(\alpha\)-hydrogen atom undergo a reaction in the presence of dilute alkali as a catalyst to form \(\beta\)-hydroxy aldehydes or \(\beta\)-hydroxy ketones. On the other hand, aldehydes which do not possess an \(\alpha\)-hydrogen undergo self-oxidation and reduction in the presence of concentrated alkali.

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                          CBSE CLASS XII Previous Year Papers

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