Chemistry:Pinacolone
Pinacolone (3,3-dimethyl-2-butanone) is an important ketone in organic chemistry. It is a colorless liquid with a slight peppermint or camphor odor. The molecule is an asymmetrical ketone. The α-methyl group can participate in condensation reactions. The carbonyl group can undergo the usual reactions (hydrogenation, reductive amination, etc.). It is a Schedule 3 compound under the Chemical Weapons Convention 1993, due to being related to pinacolyl alcohol, which is used in the production of soman.[1] It is also a controlled export in Australia Group member states.[2]
Preparation
Most famously, at least in the classroom, pinacolone arises by the pinacol rearrangement, which occurs by protonation of pinacol (2,3-dimethylbutane-2,3-diol).[3]
- 580px
Industrially, pinacolone is made by the hydrolysis of 4,4,5-trimethyl-1,3-dioxane, which is the product of isoprene and formaldehyde via the Prins reaction. It also is generated by ketonization of pivalic acid and acetic acid or acetone over metal oxide catalysts. 3-Methylbutanal is a starting material for 2,3-dimethyl-2-butene, which in turn is converted to pinacolone. Pinacolone can also be produced from 2-methy-2-butanol when reacted with C5 alcohols.[4]
Isoamylene is another starting point for the synthesis of pinacolone.[5]
Uses
Pinacolone is produced in large amounts for use in fungicides, herbicides, and pesticides. Some derivatives include:
- Tebuconazole aka Elite®.
- Vibunazole[6] & Bay-i 19139 [55362-18-0].
- It is also used to prepare pinacidil, as well as naminidil.
- Stiripentol[7][8]
- Tribuzone[9]
- Pivaloylacetonitrile is used in the synthesis of Doramapimod.[10]
- Triadimefon[11] & Triadimenol[12] & Nexinhib 20.
- Bitertanol[12]
- Paclobutrazol & Diclobutrazole
- Valconazole
- Thiofanox
- Metribuzin.
See also
References
- ↑ Handbook of chemical and biological warfare agents (2nd ed.). CRC Press. 24 August 2007. ISBN 9780849314346.
- ↑ "Export Control List: Chemical Weapons Precursors". australiagroup.net. http://www.australiagroup.net/en/precursors.html.
- ↑ G. A. Hill and E. W. Flosdorf (1941). "Pinacolone". Organic Syntheses. http://www.orgsyn.org/demo.aspx?prep=CV1P0462.; Collective Volume, 1, pp. 462
- ↑ Siegel, Hardo; Eggersdorfer, Manfred (2012). "Ketones". Ullmann's Encyclopedia of Industrial Chemistry. 5. 20. doi:10.1002/14356007.a15_077. ISBN 9783527306732.
- ↑ "Scale-Up of Synthesizing 3,3-Dimethyl-2-butyl Ketone (Pinacolone) from 2-Methyl-2-butene (β-Isoamylene) and Its Kinetic Study". Industrial & Engineering Chemistry Research 62 (24): 9453–9462. 21 June 2023. doi:10.1021/acs.iecr.3c00908. https://pubs.acs.org/doi/10.1021/acs.iecr.3c00908.
- ↑ "BAY-N-7133". Drugs of the Future 9 (6): 404. 1984. doi:10.1358/dof.1984.009.06.67103. ISSN 0377-8282. http://journals.prous.com/journals/servlet/xmlxsl/pk_journals.xml_summary_pr?p_JournalId=2&p_RefId=67103&p_IsPs=N. Retrieved 27 August 2026.
- ↑ "Stiripentol". Drugs of the Future 5 (8): 413. 1980. doi:10.1358/dof.1980.005.08.70107. ISSN 0377-8282. http://journals.prous.com/journals/servlet/xmlxsl/pk_journals.xml_summary_pr?p_JournalId=2&p_RefId=70107&p_IsPs=N. Retrieved 27 August 2026.
- ↑ Astoin, J. et al, Eur. J. Med. Chem.-Chim. Ther., 1978, 13, 41.
- ↑ "Über ein neues Darstellungsverfahren von 1,2-Diphenyl-3,5-dioxypyrazolidin-, 1,3-Dimethyl- und 1,3-Diphenylbarbitursäure-Derivaten". Collection of Czechoslovak Chemical Communications 33 (8): 2681–2689. 1968. doi:10.1135/cccc19682681. http://cccc.uochb.cas.cz/33/8/2681/. Retrieved 27 August 2026.
- ↑ "Pyrazole Urea-Based Inhibitors of p38 MAP Kinase: From Lead Compound to Clinical Candidate". Journal of Medicinal Chemistry 45 (14): 2994–3008. 1 July 2002. doi:10.1021/jm020057r. https://pubs.acs.org/doi/10.1021/jm020057r. Retrieved 27 August 2026.
- ↑ "Synthesis of the fungicide [ 14 Ctriadimefon"]. Journal of Labelled Compounds and Radiopharmaceuticals 19 (1): 111–116. January 1982. doi:10.1002/jlcr.2580190113. https://analyticalsciencejournals.onlinelibrary.wiley.com/doi/10.1002/jlcr.2580190113. Retrieved 27 August 2026.
- ↑ 12.0 12.1 "Eine einfache Synthese von Keten‐O,N‐ und Keten‐O,O‐acetalen durch Tosylat‐Eliminierung". Liebigs Annalen der Chemie 1988 (3): 235–240. 14 March 1988. doi:10.1002/jlac.198819880310. https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/jlac.198819880310. Retrieved 27 August 2026.
 |  |
