1,6-Dioxaspiro(4.4)nonane-2,7-dione

Spirodilacton Struktur.svg 1,6-Dioxaspiro[4.4]nonane-2,7-dione 3505-67-7 69487 222-499-6 77041 1S/C7H8O4/c8-5-1-3-7(10-5)4-2-6(9)11-7/h1-4H2 VTQYOGUFKHVWOO-UHFFFAOYSA-N C1CC2(CCC(=O)O2)OC1=O C7H8O4 156.14 g·mol−1 1,6-Dioxaspiro[4.4]nonane-2,7-dione or spirodilactone is a spiro compound derived from the dicarboxylic acid 4,4-dihydroxypimelic acid, formed through double internal esterification into a symmetrical lactone. The short name spirodilactone is also occasionally used for the anellation Spiro[2-benzofuran-3,5'-oxolane]-1,2'-dione. The exceptionally straightforward synthesis of 1,6-dioxaspiro[4.4]nonane-2,7-dione from the platform chemical succinic acid offers promising prospects for future applications of this compound. The dilactone already serves as a starting material for heterocyclic pyrrolizidine, for the polyol 3-hydroxymethyl-1,3,6-hexanetriol, for esters of γ-ketopimelic acid, and as a dicarboxylic acid derivative for functional polymers such as polyethers and polyamides. Occurrence and representation 1,6-Dioxaspiro[4.4]nonane-2,7-dione (here referred to as the dilactone of acetone diacetic acid or hydrochelidonic acid) was first obtained in 1889 by Jacob Volhard through heating succinic acid or succinic anhydride, with the elimination of carbon dioxide,J. Volhard 1889 10.1002/jlac.18892530119 1 206–239 Liebigs Ann. Chem. Ueber Acetondiessigsäure oder Hydrochelidonsäure 253 and was further characterized in 1892.J. Volhard 1892 10.1002/jlac.18922670103 1 48–106 Liebigs Ann. Chem. Ueber Hydrochelidonsäure und Acetondiessigsäure. Zweite Abhandlung 267 400px|center|Synthesis of spirodilactone Although the succinic acid or its anhydride used in the reaction "largely converts into a neutral, beautifully crystallizing substance", a significant residue consists of dark, oily, and resinous decomposition products. The pure spirodilactone can only be obtained from these residues through vacuum distillation and repeated recrystallization. More recent publications indicate that adding small (catalytic) amounts of solid potassium hydroxide to succinic anhydride improves the reaction.R.J. Pariza F. Kuo P.L. Fuchs 1983 10.1080/00397918308065996 3 243–254 Synth. Commun. An improved procedure for the synthesis of 4-oxopimelate-derived materials 13 By reducing the reaction timeDE 2136886 Verfahren zur Herstellung von Pyrrolizidinen 1973-02-01 1971-07-23 W. Mesch, D. Voges, S. Winderl BASF AG and implementing continuous operation,DE 753472 Verfahren zur Herstellung von γ-Ketopimelinsäuredilacton 1941-10-19 F. Ebel, F. Pyzik, G. Pöhler I.G. Farbenindustrie AG yields exceeding 80% can be achieved. A "Safety Note"M.S. Hoekstra 1984 10.1080/00397918408057679 14 1379–1380 Synth. Commun. Safety Note 14 warns that performing the reaction unattended (heating to 185 °C for several hours in a mantle heater) may result in explosive decomposition of the reaction mixture. Properties 1,6-Dioxaspiro[4.4]nonane-2,7-dione, in its pure form, crystallizes as large, colorless, transparent prismatic crystals that are soluble in many organic solvents. For purification, recrystallization from 95% ethanol is suitable. In aqueous media, hydrolysis to 4-oxoheptanedioic acid occurs. 400px|center|Hydrolysis of spirodilactone During ring opening, two geminal hydroxy groups are formed at the carbon atom in the 4-position, which, in accordance with the Erlenmeyer rule, are converted into a carbonyl group with the elimination of water. Applications Reduction of spirodilactone with lithium aluminum hydride (LiAlH4) yields the tetrahydric alcohol 3-hydroxymethyl-1,3,6-hexanetriol in high yield (89%).M. Päri M. Lüll A. Paju T. Pekh M. Lopp 2006 129 Icos 2006 Synthesis of 3-hydroxymethyl-1,3,6-hexanetriol from chiral spirodilactone https://www.etis.ee/Portal/Publications/Display/b1cfe383-b628-4b20-93c9-aab6a113e668?lang=ENG 400px|center|Reduction of spirodilactone with LiAlH4 As a dilactone, 1,6-dioxaspiro[4.4]nonane-2,7-dione can undergo transesterification with alcohols via ring opening to form diesters of 4-oxoheptanedioic acid. Using 2-ethylhexanol as the alcohol component produces excellent plasticizers for plastics such as polyvinyl chloride (PVC) (compound (A)), while reaction with methyl glycol yields a highly effective water-soluble paint stripper (compound (B)).US 2665303 Esters of gamma-ketopimelic acid 1954-5-1 1949-7-28 H.R. Gamrath Monsanto Chemical Co. 350px|center|Diester of spirodilactone From 1,6-dioxaspiro[4.4]nonane-2,7-dione, pyrrolizidine—the parent compound of hepatotoxic pyrrolizidine alkaloids—can be synthesized readily on an industrial scale. The potential of 1,6-dioxaspiro[4.4]nonane-2,7-dione as a dicarboxylic acid equivalent for polymers with both thermosetUS 4939251 Novel spirolactones 1990-7-3 1988-9-16 P.C. Wang Shell Oil Co. and thermoplasticUS 5034504 Spirolactam polyamide polymer 1991-7-23 1990-5-14 P.C. Wang Shell Oil Co. properties was studied extensively around 1990. Spirodilactams, obtained by reacting spirodilactone with primary functional amines, are highly rigid and temperature-resistant molecular building blocks for high-performance polymers.P.-C. Wang W.J. Asbell H.H. Chuah W.P. Gergen 1994 10.1002/pen.760340105 1 6–11 Polym. Engin. Sci. Polyspirolactam: A new family of high temperature polymers 34 1994PESci..34....6W 500px|center|Polymer building blocks from spirodilactams Reaction with p-phenylenediamine (I) produces the spirodilactam-dianiline (SDA), while reaction with aminophenols yields the spirodilactam-diphenol (SDD). The diphenol derivative (SDD) in particular was used as a precursor for thermoplastics based on epoxy resin or maleimide and was identified as a potential substitute for bisphenol A (BPA). The resulting polymers exhibit glass transition temperatures (Tg) approximately 80 °C higher than those of BPA-based reference materials. Fluorine-substituted aromatic compounds have been employed to synthesize thermoplastic aromatic polyethers and polyether ketones that display very high glass transition temperatures (>240 °C), low water absorption, low dielectric constants, and thermal stability exceeding 500 °C.H. Zhou E. Bucio S.R. Venumbaka J.W. Fitch P. Cassidy 2006 10.1016/j.polymer.2006.07.040 6927–6930 Polymer New spirolactam polymer 47 20 The ready availability of cost-effective succinic acidE. Mancini etal 2022 10.1016/j.cherd.2022.01.040 401–414 Chem. Eng. Res. Des. Economic and environmental analysis of bio-succinic acid production: From established processes to a new continuous fermentation approach with in-situ electrolytic extraction 179 2022CERD..179..401M 11382/572876 free derived from renewable raw materials,R. Dickson E. Mancini N. Garg J.M. Woodley K.V. Gernaey M. Pinelo J. Liu S.S. Mansouri 2021 10.1039/D0EE03545A 6 3542–3558 Energy Environ. Sci. Sustainable bio-succinic acid production: superstructure optimization, techno-economic, and lifecycle assessment 14 2021EnEnS..14.3542D together with the compound's promising potential as a building block for small molecules and polymers, could stimulate renewed research interest in 1,6-dioxaspiro[4.4]nonane-2,7-dione. References Category:Gamma-lactones Category:Spiroketals