1,3-Cyclohexanedione edit
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| Names | |
|---|---|
| IUPAC name
1,3-Cyclohexanedione
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| Other names
Dihydroresorcinol
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| Identifiers | |
3D model (JSmol)
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PubChem CID
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| UNII | |
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| Properties | |
| C6H8O2 | |
| Molar mass | 112.127 |
| Appearance | beige |
| Density | 1.0861 |
| Melting point | 101 - 105 °C (214 - 221 °F) |
| Boiling point | no data availible |
| H2O, EtOH, MeOH, ace, chl; sl eth, bz | |
| Hazards | |
| Occupational safety and health (OHS/OSH): | |
Main hazards
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May be harmful if swallowed or inhaled. Skin and Eye irritant |
| Flash point | Not flammable or combustible. |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Properties edit
1,3 Cyclohexanedione's chemical properties produce a molecular environment that is very useful in organic reactions. The molecule has importance as an intermediate in chemical reactions because of its electron deficient alpha carbon between two carbonyl functional groups and has been used to form 2-substituted aducts in a laboratory environment. The chemical has also been cited as intermediates during the synthesis of spirocyclopentanols, oxathioles, and triquinanes.[1] The molecule exists mainly in its enol form in the solid state. The inter molecular electrostatic interactions creates an ordered anti configuration due to hydrogen bonding interactions. The interactions between the heterotopic oxygen atoms are strong, describing short O-O hydrogen bonding and result in the solid state at room temperature (25 degrees Celsius). A domino effect is created from the polarization of the molecule from a single hydrogen bond and results in multiple sites for hydrogen bonding. Because of the geometry of the two carbonyls, the molecule is able to form constructive overlap between the molecules oxygen lone pairs (n) and the sigma* orbitals of the hydrogen atoms on an adjacent molecule (Frontier molecular orbital theory). The solid crystalline structure produces more than seven molecular units per linear chain of molecules and this structure has created applications to the understanding of the stability of globular proteins. [2] Stereoselective reactions can be induced to create unique stereocenters on products. 1,3 Cyclohexanedione has been cited by Maiti and Menéndz in their effort on the preparation of the amphibian alkaloid pumiliotoxin C. Reactions that involve the creation of new stereocenters can benefit from the symmetric nature of 1,3 cyclohexanedione. With nucleophilic addition to only one of the carbonyls, the remaining carbonyl pi system and oxygen can create electrostatic interactions as well as steric interactions that effect the remainder of the reaction scheme. The production of alkalois pumilio toxin C takes advantage of the stereoselectivity produced by addition to a single carbonyl. The initial reaction produces a less hindered face(sterically) and results in the production of four stereocenters. [3]
Occurrences edit
Industrial applications can range from organic reaction synthesis and catalysis. Changing the molecular structure can create a domino effect to increase the efficiency of other molecular reactions. During the synthesis of tetrahydrobenzofuran-4-ones, an alkylated 1, 3 cyclohexanedione molecule is able to transform of the core TBF. The synthesis of the TBF core is derived from using 1,3 cyclohexanedione and electrophiles. Specifically, the Feist-Benary reaction enables the synthesis of TBF's by 1,2 addition of 1,3 cyclohexanedione to haloketones or epoxyaldehydes. The TFB core is used in active research of derivatives which are present in pharmaceuticals, natural products, and pharmaceuticals. [4] Stereoselective reactions can be induced for the 1,3 cyclohexanedione to benefit the outcome of a reaction scheme. Stereoselectivity is important for reactions mechanisms when there is the possibly of two products that are not homomers. 1,3 cyclohexanedione's properties have been cited by Maiti and Menéndez in the production of an amphibian alkaloid pumiliotoxin C. Diastereoselective synthesis was produced from the application of 1,3 cyclohexanedione because of a less hindered face which allowed for greater re activity on one side of a substrate than another. This result was produced by using 1,3 cyclohexanedione as a reactant molecule. [5]
History edit
Pennsylvania state university has a historical connection through the production of progeesterone. The applications of this molecule include birth control agent or correcting diseases such as sterility or irregular menstruation. Professor of Chemistry Russell E. Marker synthesized progesterone, a hormone originally prepared form cholesterol and animal products, from the Mexican plant Cabeza de Negro. This reduced the cost of the the hormone by $76 per gram. The dione structure of 1,3 cyclohexanedione made the molecule an ideal candidate for Michael addition because of the formation of a stabilized enolate. The Michael reaction was produced through the use of 2-methyl-1,3-cyclohexanedione, a derivative of 1,3 cyclohexanedione. The reacting molecule of a ketone and the dione (1,3- cyclohexanedione) with water and hydrooquinone L-proline produce this crucial molecule for the production of the hormone progesterone. [6]
Production edit
Production of the molecule through chemical companies is common. Because of the simple but powerful structure of 1,3 cyclohexanedione, it can be used as a substrate in the progression of complicated mechanism pathways. This employs chemical companies to create a very pure version of the molecule to sell (i.g Sigma Alrich 97% purity) .[7] This molecule has also been cited in an article by Vodolazenko M.A., Gorobets N.Y., Yermolayev S.A. et.al. describing the increasing popularity of creating a reaction environment with multiple substrates in so called "one-pot reactions" (1106). 1,3 cycloheaxnediones were effective with the synthesis of poyfunctionalized fused dienolates with DMFDMA and active methylene nitriles. The reactions are made possible by the lack of defined functional groups on 1,3 cyclohexanedione combined with specific reaction conditions. Applying these reaction types has become a modern strategy for the diversifying small drug molecules. [8] Reaction conditions such as the one cited above, makes 1,3 cyclohexanedione a major component and creates demand for the production of the chemical.
Reactions edit
Dicarbonyl compounds including 1,3 cyclohexanedione have been cited in the production of furan molecules catalyzed by palladium. These reactions produce good yields because of the electron withdrawing nature of the dicarbonlys in conjunction with another electron-donating reactant. The furans are useful intermediates for bio active and natural compounds. [9]
References edit
- ^ "1,3-Cyclohexanedione". Sigma Aldrich. Retrieved 12 November 2012.
- ^ Hudson, Bruce (30). "The Crystalline Enol of 1,3-Cyclohexanedione and Its Complex with Benzene: Vibrational". Journal of Physical Chemisry (108): 7356–7363. doi:10.1021/jp048613b.
{{cite journal}}: Check date values in:|date=and|year=/|date=mismatch (help); Unknown parameter|coauthors=ignored (|author=suggested) (help); Unknown parameter|month=ignored (help) - ^ Maiti, S (18). "Brief, efficient and highly diastereoselective synthesis of pumiliotoxin". Chem. Commun. 47. doi:10.1039/c1cc11246e.
{{cite journal}}: Check date values in:|date=and|year=/|date=mismatch (help); Unknown parameter|coauthors=ignored (|author=suggested) (help); Unknown parameter|month=ignored (help) - ^ Devi, R.B. (8). "Domino alkylation/oxa-Michael of 1,3-cyclohexanediones: Steering the C/O chemoselectivity to reach tetrahydrobenzofuranes". Organic and Biomolecular Chemistry. 9. doi:10.1039/c1ob05923h.
{{cite journal}}: Check date values in:|date=and|year=/|date=mismatch (help); Unknown parameter|coauthors=ignored (|author=suggested) (help); Unknown parameter|month=ignored (help) - ^ Maiti, S (18). "Brief, efficient and highly diastereoselective synthesis of pumiliotoxin". Chem. Commun. 47. doi:10.1039/c1cc11246e.
{{cite journal}}: Check date values in:|date=and|year=/|date=mismatch (help); Unknown parameter|coauthors=ignored (|author=suggested) (help); Unknown parameter|month=ignored (help) - ^ Afnew, H.D. "Synthesis of the Wieland-Miescher Ketone:".
{{cite journal}}: Cite journal requires|journal=(help); Unknown parameter|coauthors=ignored (|author=suggested) (help) - ^ "1,3-Cyclohexanedione". Sigma Aldrich. Retrieved 12 November 2012.
- ^ Vodolazhenko, M.A. (14). "Application of stable fused dienolates for diversity oriented synthesis of 2,5-dioxo-5,6,7,8-tetrahydro-2H-chromene-3-carboxamides". RSC Advances. 2. doi:10.1039/c1ra00723h.
{{cite journal}}: Check date values in:|date=and|year=/|date=mismatch (help); Unknown parameter|coauthors=ignored (|author=suggested) (help); Unknown parameter|month=ignored (help) - ^ Cao, H. (5). "Pd-Catalyzed cyclization reaction: a convenient domino process for synthesis". Org. Biomol. Chem. 9: 7313–7317. doi:10.1039/c1ob06105d.
{{cite journal}}: Check date values in:|date=and|year=/|date=mismatch (help); Unknown parameter|coauthors=ignored (|author=suggested) (help); Unknown parameter|month=ignored (help)