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Hydroxamic acid

February 15, 2024

In organic chemistry, hydroxamic acids are a class of organic compounds bearing the functional group R−C(=O)−N(OH)−R', with R and R' as organic residues. They are amides (R−C(=O)−NH−R') wherein the nitrogen center has a hydroxyl (−OH) substituent. They are often used as metal chelators.[1]

The general structure of a hydroxamic acid

Synthesis and reactions edit

Hydroxamic acids are usually prepared from either esters or acid chlorides by a reaction with hydroxylamine salts. For the synthesis of benzohydroxamic acid, the overall equation is:[2]

C6H5CO2Me + NH2OH → C6H5C(O)NHOH + MeOH

Hydroxamic acids can also be synthesized from aldehydes and N-sulfonylhydroxylamine via the Angeli-Rimini reaction.[3]

A well-known reaction of hydroxamic acid esters is the Lossen rearrangement.[4]

Coordination chemistry and biochemistry edit

The conjugate base of hydroxamic acids forms is called a hydroxamate. Deprotonation occurs at the NOH group. The resulting conjugate base presents the metal with an anionic, conjugated O,O chelating ligand. Many hydroxamic acids and many iron hydroxamates have been isolated from natural sources.[6]

They function as ligands, usually for iron.[7] Nature has evolved families of hydroxamic acids to function as iron-binding compounds (siderophores) in bacteria. They extract iron(III) from otherwise insoluble sources (rust, minerals, etc.). The resulting complexes are transported into the cell, where the iron is extracted and utilized metabolically.[8]

Ligands derived from hydroxamic acid and thiohydroxamic acid also form strong complexes with lead(II).[9]

Other uses and occurrences edit

Hydroxamic acids are used extensively in flotation of rare earth minerals during the concentration and extraction of ores to be subjected to further processing.[10][11]

Some hydroxamic acids (e.g. vorinostat, belinostat, panobinostat, and trichostatin A) are HDAC inhibitors with anti-cancer properties. Fosmidomycin is a natural hydroxamic acid inhibitor of 1-deoxy-D-xylulose-5-phosphate reductoisomerase (DXP reductoisomerase). Hydroxamic acids have also been investigated for reprocessing of irradiated fuel.[citation needed]

References edit

  1. ^ Munson, James W. (1992). "Hydroxamic acids". In S. Patai (ed.). Acid Derivatives (1992), Volume 2. PATAI'S Chemistry of Functional Groups. pp. 849–873. doi:10.1002/9780470772508.ch15. ISBN 9780470772508.
  2. ^ C. R. Hauser; W. B. Renfrow Jr (1939). "Benzohydroxamic Acid". Org. Synth. 19: 15. doi:10.15227/orgsyn.019.0015.
  3. ^ Li, Jie Jack (2003). Name Reactions: A Collection of Detailed Reaction Mechanisms (2nd ed.). Berlin, Heidelberg, New York: Springer. p. 9. ISBN 978-3-662-05338-6.
  4. ^ Wang, Zerong (2010). Comprehensive organic name reactions and reagents. John Wiley & Sons, Inc. pp. 1772–1776. ISBN 9780471704508.
  5. ^ Hossain, M. B.; Eng-Wilmot, D. L.; Loghry, R. A.; an der Helm, D. (1980). "Circular Dichroism, Crystal Structure, and Absolute Configuration of the Siderophore Ferric N,N',N"-Triacetylfusarinine, FeC39H57N6O15". Journal of the American Chemical Society. 102 (18): 5766–5773. doi:10.1021/ja00538a012.
  6. ^ Abraham Shanzer, Clifford E. Felder, Yaniv Barda (2008). "Natural and Biomimetic Hydroxamic Acid based Siderophores". In Zvi Rappoport, Joel F. Liebman (ed.). The Chemistry of Hydroxylamines, Oximes and Hydroxamic Acids. PATAI'S Chemistry of Functional Groups. pp. 751–815. doi:10.1002/9780470741962.ch16. ISBN 9780470512616.{{cite book}}: CS1 maint: multiple names: authors list (link)
  7. ^ Agrawal, Y K (1979). "Hydroxamic Acids and Their Metal Complexes". Russian Chemical Reviews. 48 (10): 948–963. Bibcode:1979RuCRv..48..948A. doi:10.1070/RC1979v048n10ABEH002422. S2CID 250857281.
  8. ^ Miller, Marvin J. (November 1989). "Syntheses and Therapeutic Potential of Hydroxamic Acid Based Siderophores and Analogues". Chemical Reviews. 89 (7): 1563–1579. doi:10.1021/cr00097a011.
  9. ^ Farkas, Etelka; Buglyó, Péter (2017). "Chapter 8. Lead(II) Complexes of Amino Acids, Peptides, and Other Related Ligands of Biological Interest". In Astrid, S.; Helmut, S.; Sigel, R. K. O. (eds.). Lead: Its Effects on Environment and Health. Metal Ions in Life Sciences. Vol. 17. de Gruyter. pp. 201–240. doi:10.1515/9783110434330-008. ISBN 9783110434330. PMID 28731301.
  10. ^ Marion, Christopher; Jordens, Adam; Li, Ronghao; Rudolph, Martin; Waters, Kristian E. (August 2017). "An evaluation of hydroxamate collectors for malachite flotation". Separation and Purification Technology. 183: 258–269. doi:10.1016/j.seppur.2017.02.056.
  11. ^ Jordens, Adam; Cheng, Ying Ping; Waters, Kristian E. (February 2013). "A review of the beneficiation of rare earth element bearing minerals". Minerals Engineering. 41: 97–114. Bibcode:2013MiEng..41...97J. doi:10.1016/j.mineng.2012.10.017.

Further reading edit

  • Fouché, K. F.; H. J. le Roux; F. Phillips (June 1970). "Complex formation of Zr(IV) and Hf(IV) with hydroxamic acids in acidic solutions". Journal of Inorganic and Nuclear Chemistry. 32 (6): 1949–1962. doi:10.1016/0022-1902(70)80604-2. ISSN 0022-1902. Archived from the original on 2013-01-04. Retrieved 2009-04-24.
  • Barocas, A.; F. Baroncelli; G. B. Biondi; G. Grossi (December 1966). "The complexing power of hydroxamic acids and its effect on behaviour of organic extractants in the reprocessing of irradiated fuels--II : The complexes between benzohydroxamic acid and thorium, uranium (IV) and plutonium (IV)". Journal of Inorganic and Nuclear Chemistry. 28 (12): 2961–2967. doi:10.1016/0022-1902(66)80023-4. ISSN 0022-1902. Archived from the original on 2013-01-04. Retrieved 2009-04-24.
  • Baroncelli, F.; G. Grossi (May 1965). "The complexing power of hydroxamic acids and its effect on the behaviour of organic extractants in the reprocessing of irradiated fuels--I the complexes between benzohydroxamic acid and zirconium, iron (III) and uranium (VI)". Journal of Inorganic and Nuclear Chemistry. 27 (5): 1085–1092. doi:10.1016/0022-1902(65)80420-1. ISSN 0022-1902. Archived from the original on 2013-01-04. Retrieved 2009-04-24.
  • Al-Jarrah, R. H.; A. R. Al-Karaghouli; S. A. Al-Assaf; N. H. Shamon (1981). "Solvent extraction of uranium and some other metal ions with 2-N-butyl-2-ethyl octanohydroxamic acid". Journal of Inorganic and Nuclear Chemistry. 43 (11): 2971–2973. doi:10.1016/0022-1902(81)80652-5. ISSN 0022-1902. Archived from the original on 2013-01-04. Retrieved 2009-04-24.
  • Gopalan, Aravamudan S.; Vincent J. Huber; Orhan Zincircioglu; Paul H. Smith (1992). "Novel tetrahydroxamate chelators for actinide complexation: synthesis and binding studies". Journal of the Chemical Society, Chemical Communications (17): 1266–1268. doi:10.1039/C39920001266.
  • Koshti, Nirmal; Vincent Huber; Paul Smith; Aravamudan S. Gopalan (1994-02-28). "Design and synthesis of actinide specific chelators: Synthesis of new cyclam tetrahydroxamate (CYTROX) and cyclam tetraacetonylacetone (CYTAC) chelators". Tetrahedron. 50 (9): 2657–2664. doi:10.1016/S0040-4020(01)86981-7. ISSN 0040-4020.

February 15, 2024
hydroxamic, acid, organic, chemistry, hydroxamic, acids, class, organic, compounds, bearing, functional, group, with, organic, residues, they, amides, wherein, nitrogen, center, hydroxyl, substituent, they, often, used, metal, chelators, general, structure, hy. In organic chemistry hydroxamic acids are a class of organic compounds bearing the functional group R C O N OH R with R and R as organic residues They are amides R C O NH R wherein the nitrogen center has a hydroxyl OH substituent They are often used as metal chelators 1 The general structure of a hydroxamic acid Contents 1 Synthesis and reactions 2 Coordination chemistry and biochemistry 3 Other uses and occurrences 4 References 5 Further readingSynthesis and reactions editHydroxamic acids are usually prepared from either esters or acid chlorides by a reaction with hydroxylamine salts For the synthesis of benzohydroxamic acid the overall equation is 2 C6H5CO2Me NH2OH C6H5C O NHOH MeOHHydroxamic acids can also be synthesized from aldehydes and N sulfonylhydroxylamine via the Angeli Rimini reaction 3 A well known reaction of hydroxamic acid esters is the Lossen rearrangement 4 Coordination chemistry and biochemistry editSample gallery nbsp Ferrichrome nbsp Deferoxamine nbsp Rhodotorulic acid nbsp Fe III complex of triacetylfusarinine 5 The conjugate base of hydroxamic acids forms is called a hydroxamate Deprotonation occurs at the NOH group The resulting conjugate base presents the metal with an anionic conjugated O O chelating ligand Many hydroxamic acids and many iron hydroxamates have been isolated from natural sources 6 They function as ligands usually for iron 7 Nature has evolved families of hydroxamic acids to function as iron binding compounds siderophores in bacteria They extract iron III from otherwise insoluble sources rust minerals etc The resulting complexes are transported into the cell where the iron is extracted and utilized metabolically 8 Ligands derived from hydroxamic acid and thiohydroxamic acid also form strong complexes with lead II 9 Other uses and occurrences editHydroxamic acids are used extensively in flotation of rare earth minerals during the concentration and extraction of ores to be subjected to further processing 10 11 Some hydroxamic acids e g vorinostat belinostat panobinostat and trichostatin A are HDAC inhibitors with anti cancer properties Fosmidomycin is a natural hydroxamic acid inhibitor of 1 deoxy D xylulose 5 phosphate reductoisomerase DXP reductoisomerase Hydroxamic acids have also been investigated for reprocessing of irradiated fuel citation needed References edit Munson James W 1992 Hydroxamic acids In S Patai ed Acid Derivatives 1992 Volume 2 PATAI S Chemistry of Functional Groups pp 849 873 doi 10 1002 9780470772508 ch15 ISBN 9780470772508 C R Hauser W B Renfrow Jr 1939 Benzohydroxamic Acid Org Synth 19 15 doi 10 15227 orgsyn 019 0015 Li Jie Jack 2003 Name Reactions A Collection of Detailed Reaction Mechanisms 2nd ed Berlin Heidelberg New York Springer p 9 ISBN 978 3 662 05338 6 Wang Zerong 2010 Comprehensive organic name reactions and reagents John Wiley amp Sons Inc pp 1772 1776 ISBN 9780471704508 Hossain M B Eng Wilmot D L Loghry R A an der Helm D 1980 Circular Dichroism Crystal Structure and Absolute Configuration of the Siderophore Ferric N N N Triacetylfusarinine FeC39H57N6O15 Journal of the American Chemical Society 102 18 5766 5773 doi 10 1021 ja00538a012 Abraham Shanzer Clifford E Felder Yaniv Barda 2008 Natural and Biomimetic Hydroxamic Acid based Siderophores In Zvi Rappoport Joel F Liebman ed The Chemistry of Hydroxylamines Oximes and Hydroxamic Acids PATAI S Chemistry of Functional Groups pp 751 815 doi 10 1002 9780470741962 ch16 ISBN 9780470512616 a href Template Cite book html title Template Cite book cite book a CS1 maint multiple names authors list link Agrawal Y K 1979 Hydroxamic Acids and Their Metal Complexes Russian Chemical Reviews 48 10 948 963 Bibcode 1979RuCRv 48 948A doi 10 1070 RC1979v048n10ABEH002422 S2CID 250857281 Miller Marvin J November 1989 Syntheses and Therapeutic Potential of Hydroxamic Acid Based Siderophores and Analogues Chemical Reviews 89 7 1563 1579 doi 10 1021 cr00097a011 Farkas Etelka Buglyo Peter 2017 Chapter 8 Lead II Complexes of Amino Acids Peptides and Other Related Ligands of Biological Interest In Astrid S Helmut S Sigel R K O eds Lead Its Effects on Environment and Health Metal Ions in Life Sciences Vol 17 de Gruyter pp 201 240 doi 10 1515 9783110434330 008 ISBN 9783110434330 PMID 28731301 Marion Christopher Jordens Adam Li Ronghao Rudolph Martin Waters Kristian E August 2017 An evaluation of hydroxamate collectors for malachite flotation Separation and Purification Technology 183 258 269 doi 10 1016 j seppur 2017 02 056 Jordens Adam Cheng Ying Ping Waters Kristian E February 2013 A review of the beneficiation of rare earth element bearing minerals Minerals Engineering 41 97 114 Bibcode 2013MiEng 41 97J doi 10 1016 j mineng 2012 10 017 Further reading editFouche K F H J le Roux F Phillips June 1970 Complex formation of Zr IV and Hf IV with hydroxamic acids in acidic solutions Journal of Inorganic and Nuclear Chemistry 32 6 1949 1962 doi 10 1016 0022 1902 70 80604 2 ISSN 0022 1902 Archived from the original on 2013 01 04 Retrieved 2009 04 24 Barocas A F Baroncelli G B Biondi G Grossi December 1966 The complexing power of hydroxamic acids and its effect on behaviour of organic extractants in the reprocessing of irradiated fuels II The complexes between benzohydroxamic acid and thorium uranium IV and plutonium IV Journal of Inorganic and Nuclear Chemistry 28 12 2961 2967 doi 10 1016 0022 1902 66 80023 4 ISSN 0022 1902 Archived from the original on 2013 01 04 Retrieved 2009 04 24 Baroncelli F G Grossi May 1965 The complexing power of hydroxamic acids and its effect on the behaviour of organic extractants in the reprocessing of irradiated fuels I the complexes between benzohydroxamic acid and zirconium iron III and uranium VI Journal of Inorganic and Nuclear Chemistry 27 5 1085 1092 doi 10 1016 0022 1902 65 80420 1 ISSN 0022 1902 Archived from the original on 2013 01 04 Retrieved 2009 04 24 Al Jarrah R H A R Al Karaghouli S A Al Assaf N H Shamon 1981 Solvent extraction of uranium and some other metal ions with 2 N butyl 2 ethyl octanohydroxamic acid Journal of Inorganic and Nuclear Chemistry 43 11 2971 2973 doi 10 1016 0022 1902 81 80652 5 ISSN 0022 1902 Archived from the original on 2013 01 04 Retrieved 2009 04 24 Gopalan Aravamudan S Vincent J Huber Orhan Zincircioglu Paul H Smith 1992 Novel tetrahydroxamate chelators for actinide complexation synthesis and binding studies Journal of the Chemical Society Chemical Communications 17 1266 1268 doi 10 1039 C39920001266 Koshti Nirmal Vincent Huber Paul Smith Aravamudan S Gopalan 1994 02 28 Design and synthesis of actinide specific chelators Synthesis of new cyclam tetrahydroxamate CYTROX and cyclam tetraacetonylacetone CYTAC chelators Tetrahedron 50 9 2657 2664 doi 10 1016 S0040 4020 01 86981 7 ISSN 0040 4020 Retrieved from https en wikipedia org w index php title Hydroxamic acid amp oldid 1156488529, wikipedia, wiki, book, books, library,

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