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Carbonylation

August 25, 2023

See also: Protein carbonylation

In chemistry, carbonylation refers to reactions that introduce carbon monoxide (CO) into organic and inorganic substrates. Carbon monoxide is abundantly available and conveniently reactive, so it is widely used as a reactant in industrial chemistry. The term carbonylation also refers to oxidation of protein side chains.

Organic chemistry Edit

Several industrially useful organic chemicals are prepared by carbonylations, which can be highly selective reactions. Carbonylations produce organic carbonyls, i.e., compounds that contain the C=O functional group such as aldehydes (−CH=O), carboxylic acids (−C(=O)OH) and esters (−C(=O)O−).[1][2] Carbonylations are the basis of many types of reactions, including hydroformylation and Reppe reactions. These reactions require metal catalysts, which bind and activate the CO.[3] These processes involve transition metal acyl complexes as intermediates. Much of this theme was developed by Walter Reppe.

Hydroformylation Edit

Main article: Hydroformylation

Hydroformylation entails the addition of both carbon monoxide and hydrogen to unsaturated organic compounds, usually alkenes. The usual products are aldehydes:

 

The reaction requires metal catalysts that bind CO, forming intermediate metal carbonyls. Many of the commodity carboxylic acids, i.e. propionic, butyric, valeric, etc, as well as many of the commodity alcohols, i.e. propanol, butanol, amyl alcohol, are derived from aldehydes produced by hydroformylation. In this way, hydroformylation is a gateway from alkenes to oxygenates.

Decarbonylation Edit

Many organic carbonyls undergo decarbonylation. A common transformation involves the conversion of aldehydes to alkanes, usually catalyzed by metal complexes:[4]

 

Few catalysts are highly active or exhibit broad scope.[5]

Acetic acid and acetic anhydride Edit

Large-scale applications of carbonylation are the Monsanto acetic acid process and Cativa process, which convert methanol to acetic acid. In another major industrial process, acetic anhydride is prepared by a related carbonylation of methyl acetate.[6]

Oxidative carbonylation Edit

Dimethyl carbonate and dimethyl oxalate are produced industrially using carbon monoxide and an oxidant, in effect as a source of CO2+.[1]

 

The oxidative carbonylation of methanol is catalyzed by copper(I) salts, which form transient carbonyl complexes. For the oxidative carbonylation of alkenes, palladium complexes are used.

Hydrocarboxylation and hydroesterification Edit

In hydrocarboxylation, alkenes and alkynes are the substrates. This method is used industrially to produce propionic acid from ethylene using nickel carbonyl as the catalyst:[1]

 

In the industrial synthesis of ibuprofen, a benzylic alcohol is converted to the corresponding arylacetic acid via a Pd-catalyzed carbonylation:[1]

 

Acrylic acid was once mainly prepared by the hydrocarboxylation of acetylene.[7]

 
Synthesis of acrylic acid using "Reppe chemistry"; a metal catalyst is required.

Nowadays, however, the preferred route to acrylic acid entails the oxidation of propene, exploiting its low cost and the high reactivity of the allylic C−H bonds.

Hydroesterification is like hydrocarboxylation, but it uses alcohols in place of water.[8]

 

The process is catalyzed by Herrmann's catalyst, Pd[C6H4(CH2PBu-t)2]2. Under similar conditions, other Pd-diphosphines catalyze formation of polyketones.

Other reactions Edit

The Koch reaction is a special case of hydrocarboxylation reaction that does not rely on metal catalysts. Instead, the process is catalyzed by strong acids such as sulfuric acid or the combination of phosphoric acid and boron trifluoride. The reaction is less applicable to simple alkene. The industrial synthesis of glycolic acid is achieved in this way:[9]

 

The conversion of isobutene to pivalic acid is also illustrative:

 

Alkyl, benzyl, vinyl, aryl, and allyl halides can also be carbonylated in the presence carbon monoxide and suitable catalysts such as manganese, iron, or nickel powders.[10]

Carbonylation in inorganic chemistry Edit

Main article: metal carbonyl

Metal carbonyls, compounds with the formula M(CO)xLy (M = metal; L = other ligands) are prepared by carbonylation of transition metals. Iron and nickel powder react directly with CO to give Fe(CO)5 and Ni(CO)4, respectively. Most other metals form carbonyls less directly, such as from their oxides or halides. Metal carbonyls are widely employed as catalysts in the hydroformylation and Reppe processes discussed above.[11] Inorganic compounds that contain CO ligands can also undergo decarbonylation, often via a photochemical reaction.

References Edit

  1. ^ a b c d W. Bertleff; M. Roeper; X. Sava. "Carbonylation". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a05_217.
  2. ^ Arpe, .J.: Industrielle organische Chemie: Bedeutende vor- und Zwischenprodukte, 2007, Wiley-VCH-Verlag, ISBN 3-527-31540-3
  3. ^ Beller, Matthias; Cornils, B.; Frohning, C. D.; Kohlpaintner, C. W. (1995). "Progress in hydroformylation and carbonylation". Journal of Molecular Catalysis A: Chemical. 104: 17–85. doi:10.1016/1381-1169(95)00130-1.
  4. ^ Hartwig, J. F. Organotransition Metal Chemistry, from Bonding to Catalysis; University Science Books: New York, 2010.
  5. ^ Kreis, M.; Palmelund, A.; Bunch, L.; Madsen, R., "A General and Convenient Method for the Rhodium-Catalyzed Decarbonylation of Aldehydes", Advanced Synthesis & Catalysis 2006, 348, 2148-2154. doi:10.1002/adsc.200600228
  6. ^ Zoeller, J. R.; Agreda, V. H.; Cook, S. L.; Lafferty, N. L.; Polichnowski, S. W.; Pond, D. M. (1992). "Eastman Chemical Company Acetic Anhydride Process". Catalysis Today. 13: 73–91. doi:10.1016/0920-5861(92)80188-S.
  7. ^ Takashi Ohara, Takahisa Sato, Noboru Shimizu, Günter Prescher Helmut Schwind, Otto Weiberg, Klaus Marten, Helmut Greim (2003). "Acrylic Acid and Derivatives". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a01_161.pub2.{{cite encyclopedia}}: CS1 maint: multiple names: authors list (link)
  8. ^ El Ali, B.; Alper, H. "Hydrocarboxylation and hydroesterification reactions catalyzed by transition metal complexes" In Transition Metals for Organic Synthesis, 2nd ed.; Beller, M., Bolm, C., Eds.; Wiley-VCH:Weinheim, 2004. ISBN 978-3-527-30613-8
  9. ^ Karlheinz Miltenberger, "Hydroxycarboxylic Acids, Aliphatic" in Ullmann’s Encyclopedia of Industrial Chemistry, Wiley-VCH: Weinheim, 2003
  10. ^ Riemenschneider, Wilhelm; Bolt, Hermann (2000). Esters, Organic. p. 10. doi:10.1002/14356007.a09_565. ISBN 978-3527306732. {{cite book}}: |journal= ignored (help)
  11. ^ Elschenbroich, C. ”Organometallics” (2006) Wiley-VCH: Weinheim. ISBN 978-3-527-29390-2

August 25, 2023
carbonylation, also, protein, carbonylation, chemistry, carbonylation, refers, reactions, that, introduce, carbon, monoxide, into, organic, inorganic, substrates, carbon, monoxide, abundantly, available, conveniently, reactive, widely, used, reactant, industri. See also Protein carbonylation In chemistry carbonylation refers to reactions that introduce carbon monoxide CO into organic and inorganic substrates Carbon monoxide is abundantly available and conveniently reactive so it is widely used as a reactant in industrial chemistry The term carbonylation also refers to oxidation of protein side chains Contents 1 Organic chemistry 1 1 Hydroformylation 1 2 Decarbonylation 1 3 Acetic acid and acetic anhydride 1 4 Oxidative carbonylation 1 5 Hydrocarboxylation and hydroesterification 1 6 Other reactions 2 Carbonylation in inorganic chemistry 3 ReferencesOrganic chemistry EditSeveral industrially useful organic chemicals are prepared by carbonylations which can be highly selective reactions Carbonylations produce organic carbonyls i e compounds that contain the C O functional group such as aldehydes CH O carboxylic acids C O OH and esters C O O 1 2 Carbonylations are the basis of many types of reactions including hydroformylation and Reppe reactions These reactions require metal catalysts which bind and activate the CO 3 These processes involve transition metal acyl complexes as intermediates Much of this theme was developed by Walter Reppe Hydroformylation Edit Main article Hydroformylation Hydroformylation entails the addition of both carbon monoxide and hydrogen to unsaturated organic compounds usually alkenes The usual products are aldehydes RCH CH 2 H 2 CO RCH 2 CH 2 C H O displaystyle ce RCH CH2 H2 color red ce CO longrightarrow ce RCH2CH2 color red ce C ce H color red ce O The reaction requires metal catalysts that bind CO forming intermediate metal carbonyls Many of the commodity carboxylic acids i e propionic butyric valeric etc as well as many of the commodity alcohols i e propanol butanol amyl alcohol are derived from aldehydes produced by hydroformylation In this way hydroformylation is a gateway from alkenes to oxygenates Decarbonylation Edit Many organic carbonyls undergo decarbonylation A common transformation involves the conversion of aldehydes to alkanes usually catalyzed by metal complexes 4 R C H O RH CO displaystyle ce R color red ce C ce H color red ce O longrightarrow ce RH color red ce CO Few catalysts are highly active or exhibit broad scope 5 Acetic acid and acetic anhydride Edit Large scale applications of carbonylation are the Monsanto acetic acid process and Cativa process which convert methanol to acetic acid In another major industrial process acetic anhydride is prepared by a related carbonylation of methyl acetate 6 Oxidative carbonylation Edit Dimethyl carbonate and dimethyl oxalate are produced industrially using carbon monoxide and an oxidant in effect as a source of CO2 1 4 CH 3 OH O 2 2 CO 2 CH 3 O 2 CO 2 H 2 O displaystyle ce 4 CH3OH O2 2 color red ce CO longrightarrow ce 2 CH3O 2 color red ce CO ce 2 H2O The oxidative carbonylation of methanol is catalyzed by copper I salts which form transient carbonyl complexes For the oxidative carbonylation of alkenes palladium complexes are used Hydrocarboxylation and hydroesterification Edit In hydrocarboxylation alkenes and alkynes are the substrates This method is used industrially to produce propionic acid from ethylene using nickel carbonyl as the catalyst 1 RCH CH 2 H 2 O CO RCH 2 CH 2 CO OH displaystyle ce RCH CH2 H2O color red ce CO longrightarrow ce RCH2CH2 color red ce CO ce OH In the industrial synthesis of ibuprofen a benzylic alcohol is converted to the corresponding arylacetic acid via a Pd catalyzed carbonylation 1 ArCH CH 3 OH CO ArCH CH 3 CO OH displaystyle ce ArCH CH3 OH color red ce CO longrightarrow ce ArCH CH3 color red ce CO ce OH Acrylic acid was once mainly prepared by the hydrocarboxylation of acetylene 7 Synthesis of acrylic acid using Reppe chemistry a metal catalyst is required Nowadays however the preferred route to acrylic acid entails the oxidation of propene exploiting its low cost and the high reactivity of the allylic C H bonds Hydroesterification is like hydrocarboxylation but it uses alcohols in place of water 8 C 2 H 4 CO MeOH CH 3 CH 2 CO OMe displaystyle ce C2H4 color red ce CO ce MeOH gt CH3CH2 color red ce CO ce OMe The process is catalyzed by Herrmann s catalyst Pd C6H4 CH2PBu t 2 2 Under similar conditions other Pd diphosphines catalyze formation of polyketones Other reactions Edit The Koch reaction is a special case of hydrocarboxylation reaction that does not rely on metal catalysts Instead the process is catalyzed by strong acids such as sulfuric acid or the combination of phosphoric acid and boron trifluoride The reaction is less applicable to simple alkene The industrial synthesis of glycolic acid is achieved in this way 9 CH 2 O CO H 2 O HOCH 2 CO OH displaystyle ce CH2O color red ce CO ce H2O gt HOCH2 color red ce CO ce OH The conversion of isobutene to pivalic acid is also illustrative Me 2 C CH 2 H 2 O CO Me 3 C CO OH displaystyle ce Me2C CH2 H2O color red ce CO longrightarrow ce Me3C color red ce CO ce OH Alkyl benzyl vinyl aryl and allyl halides can also be carbonylated in the presence carbon monoxide and suitable catalysts such as manganese iron or nickel powders 10 Carbonylation in inorganic chemistry EditMain article metal carbonyl Metal carbonyls compounds with the formula M CO xLy M metal L other ligands are prepared by carbonylation of transition metals Iron and nickel powder react directly with CO to give Fe CO 5 and Ni CO 4 respectively Most other metals form carbonyls less directly such as from their oxides or halides Metal carbonyls are widely employed as catalysts in the hydroformylation and Reppe processes discussed above 11 Inorganic compounds that contain CO ligands can also undergo decarbonylation often via a photochemical reaction References Edit a b c d W Bertleff M Roeper X Sava Carbonylation Ullmann s Encyclopedia of Industrial Chemistry Weinheim Wiley VCH doi 10 1002 14356007 a05 217 Arpe J Industrielle organische Chemie Bedeutende vor und Zwischenprodukte 2007 Wiley VCH Verlag ISBN 3 527 31540 3 Beller Matthias Cornils B Frohning C D Kohlpaintner C W 1995 Progress in hydroformylation and carbonylation Journal of Molecular Catalysis A Chemical 104 17 85 doi 10 1016 1381 1169 95 00130 1 Hartwig J F Organotransition Metal Chemistry from Bonding to Catalysis University Science Books New York 2010 Kreis M Palmelund A Bunch L Madsen R A General and Convenient Method for the Rhodium Catalyzed Decarbonylation of Aldehydes Advanced Synthesis amp Catalysis 2006 348 2148 2154 doi 10 1002 adsc 200600228 Zoeller J R Agreda V H Cook S L Lafferty N L Polichnowski S W Pond D M 1992 Eastman Chemical Company Acetic Anhydride Process Catalysis Today 13 73 91 doi 10 1016 0920 5861 92 80188 S Takashi Ohara Takahisa Sato Noboru Shimizu Gunter Prescher Helmut Schwind Otto Weiberg Klaus Marten Helmut Greim 2003 Acrylic Acid and Derivatives Ullmann s Encyclopedia of Industrial Chemistry Weinheim Wiley VCH doi 10 1002 14356007 a01 161 pub2 a href Template Cite encyclopedia html title Template Cite encyclopedia cite encyclopedia a CS1 maint multiple names authors list link El Ali B Alper H Hydrocarboxylation and hydroesterification reactions catalyzed by transition metal complexes In Transition Metals for Organic Synthesis 2nd ed Beller M Bolm C Eds Wiley VCH Weinheim 2004 ISBN 978 3 527 30613 8 Karlheinz Miltenberger Hydroxycarboxylic Acids Aliphatic in Ullmann s Encyclopedia of Industrial Chemistry Wiley VCH Weinheim 2003 Riemenschneider Wilhelm Bolt Hermann 2000 Esters Organic p 10 doi 10 1002 14356007 a09 565 ISBN 978 3527306732 a href Template Cite book html title Template Cite book cite book a journal ignored help Elschenbroich C Organometallics 2006 Wiley VCH Weinheim ISBN 978 3 527 29390 2 Retrieved from https en wikipedia org w index php title Carbonylation amp oldid 1136698030, wikipedia, wiki, book, books, library,

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