The reaction can be simplified by replacing the HCN/AlCl3 combination with zinc cyanide.[4] Although it is also highly toxic, Zn(CN)2 is a solid, making it safer to work with than gaseous HCN.[5] The Zn(CN)2 reacts with the HCl to form the key HCN reactant and Zn(Cl)2 that serves as the Lewis-acid catalyst in-situ. An example of the Zn(CN)2 method is the synthesis of mesitaldehyde from mesitylene.[6]
The Gattermann–Koch reaction, named after the German chemists Ludwig Gattermann and Julius Arnold Koch,[7] is a variant of the Gattermann reaction in which carbon monoxide (CO) is used instead of hydrogen cyanide.[8]
Unlike the Gattermann reaction, this reaction is not applicable to phenol and phenol ether substrates.[5] Although the highly unstable formyl chloride was initially postulated as an intermediate, formyl cation (i.e., protonated carbon monoxide), [HCO]+, is now thought to be react directly with the arene without the initial formation of formyl chloride.[9] Additionally, when zinc chloride is used as the Lewis acid instead of aluminum chloride for example, or when the carbon monoxide is not used at high pressure, the presence of traces of copper(I) chloride or nickel(II) chloride co-catalyst is often necessary. The transition metal co-catalyst may server as a "carrier" by first forming reacting with CO to form a carbonyl complex, which is then transformed into the active electrophile.[10]
^Smith, Michael B.; March, Jerry (2007), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (6th ed.), New York: Wiley-Interscience, p. 725, ISBN978-0-471-72091-1
^Karrer, P. (1919). "Über Oxycarbonylverbindungen I. Eine neue Synthese von" [Hydroxycarbonyl compounds. I. A new synthesis of hydroxyaldehydes]. Helvetica Chimica Acta (in German). 2 (1): 89–94. doi:10.1002/hlca.19190020109.
^Adams R.; Levine, I. (1923). "Simplification of the Gattermann Synthesis of Hydroxy Aldehydes". J. Am. Chem. Soc.45 (10): 2373–77. doi:10.1021/ja01663a020.
^ abAdams, Roger (1957). Organic Reactions, Volume 9. New York: John Wiley & Sons, Inc. pp. 38 & 53–54. doi:10.1002/0471264180.or009.02. ISBN9780471007265.
^Fuson, R. C.; Horning, E. C.; Rowland, S. P.; Ward, M. L. (1955). "Mesitaldehyde". Organic Syntheses. doi:10.15227/orgsyn.023.0057.; Collective Volume, vol. 3, p. 549
^Li, Jie Jack (2003). Name Reactions: A Collection of Detailed Reaction Mechanisms(available on Google Books) (2nd ed.). Springer. p. 157. ISBN3-540-40203-9.
^Kurti, Laszlo. (2005). Strategic Applications of Named Reactions in Organic Synthesis : Background and Detailed Mechanisms. Czako, Barbara. Burlington: Elsevier Science. ISBN978-0-08-057541-4. OCLC 850164343.
^Dilke, M. H.; Eley, D. D. (1949). "550. The Gattermann–Koch reaction. Part II. Reaction kinetics". J. Chem. Soc.: 2613–2620. doi:10.1039/JR9490002613. ISSN 0368-1769.
December 15, 2023
gattermann, reaction, conversion, benzenediazonium, chloride, haloarene, also, referred, diazonium, compound, also, known, gattermann, formylation, gattermann, salicylaldehyde, synthesis, chemical, reaction, which, aromatic, compounds, formylated, mixture, hyd. For the conversion of benzenediazonium chloride to a haloarene also referred to as the Gattermann reaction see Diazonium compound Gattermann reaction The Gattermann reaction also known as the Gattermann formylation and the Gattermann salicylaldehyde synthesis is a chemical reaction in which aromatic compounds are formylated by a mixture of hydrogen cyanide HCN and hydrogen chloride HCl in the presence of a Lewis acid catalyst such as aluminium chloride AlCl3 1 It is named for the German chemist Ludwig Gattermann 2 and is similar to the Friedel Crafts reaction Gattermann formylationNamed after Ludwig GattermannReaction type Substitution reactionIdentifiersRSC ontology ID RXNO 0000139 Modifications have shown that it is possible to use sodium cyanide or cyanogen bromide in place of hydrogen cyanide 3 The reaction can be simplified by replacing the HCN AlCl3 combination with zinc cyanide 4 Although it is also highly toxic Zn CN 2 is a solid making it safer to work with than gaseous HCN 5 The Zn CN 2 reacts with the HCl to form the key HCN reactant and Zn Cl 2 that serves as the Lewis acid catalyst in situ An example of the Zn CN 2 method is the synthesis of mesitaldehyde from mesitylene 6 Gattermann Koch reaction editGattermann Koch formylationNamed after Ludwig Gattermann Julius Arnold KochReaction type Substitution reactionThe Gattermann Koch reaction named after the German chemists Ludwig Gattermann and Julius Arnold Koch 7 is a variant of the Gattermann reaction in which carbon monoxide CO is used instead of hydrogen cyanide 8 nbsp Unlike the Gattermann reaction this reaction is not applicable to phenol and phenol ether substrates 5 Although the highly unstable formyl chloride was initially postulated as an intermediate formyl cation i e protonated carbon monoxide HCO is now thought to be react directly with the arene without the initial formation of formyl chloride 9 Additionally when zinc chloride is used as the Lewis acid instead of aluminum chloride for example or when the carbon monoxide is not used at high pressure the presence of traces of copper I chloride or nickel II chloride co catalyst is often necessary The transition metal co catalyst may server as a carrier by first forming reacting with CO to form a carbonyl complex which is then transformed into the active electrophile 10 See also editHouben Hoesch reaction Stephen aldehyde synthesisReferences edit Smith Michael B March Jerry 2007 Advanced Organic Chemistry Reactions Mechanisms and Structure 6th ed New York Wiley Interscience p 725 ISBN 978 0 471 72091 1 Gattermann L Berchelmann W 1898 Synthese aromatischer Oxyaldehyde Berichte der deutschen chemischen Gesellschaft 31 2 1765 1769 doi 10 1002 cber 18980310281 Karrer P 1919 Uber Oxycarbonylverbindungen I Eine neue Synthese von Hydroxycarbonyl compounds I A new synthesis of hydroxyaldehydes Helvetica Chimica Acta in German 2 1 89 94 doi 10 1002 hlca 19190020109 Adams R Levine I 1923 Simplification of the Gattermann Synthesis of Hydroxy Aldehydes J Am Chem Soc 45 10 2373 77 doi 10 1021 ja01663a020 a b Adams Roger 1957 Organic Reactions Volume 9 New York John Wiley amp Sons Inc pp 38 amp 53 54 doi 10 1002 0471264180 or009 02 ISBN 9780471007265 Fuson R C Horning E C Rowland S P Ward M L 1955 Mesitaldehyde Organic Syntheses doi 10 15227 orgsyn 023 0057 Collective Volume vol 3 p 549 Gattermann L Koch J A 1897 Eine Synthese aromatischer Aldehyde Chemische Berichte 30 2 1622 1624 doi 10 1002 cber 18970300288 Li Jie Jack 2003 Name Reactions A Collection of Detailed Reaction Mechanisms available on Google Books 2nd ed Springer p 157 ISBN 3 540 40203 9 Kurti Laszlo 2005 Strategic Applications of Named Reactions in Organic Synthesis Background and Detailed Mechanisms Czako Barbara Burlington Elsevier Science ISBN 978 0 08 057541 4 OCLC 850164343 Dilke M H Eley D D 1949 550 The Gattermann Koch reaction Part II Reaction kinetics J Chem Soc 2613 2620 doi 10 1039 JR9490002613 ISSN 0368 1769 Retrieved from https en wikipedia org w index php title Gattermann reaction amp oldid 1182993500 Gattermann Koch reaction, wikipedia, wiki, book, books, library,
