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Efficient Utilization of Supercritical Carbon Dioxide as Both Reactant and Reaction Medium for Synthetic Applications

  • Sodeh SadjadiEmail author
Reference work entry

Abstract

Carbon dioxide is an attractive C1 building block in organic synthesis. However, due to the inert nature of CO2, its activation and incorporation into organic substrates still remain a significant synthetic challenge. Accordingly, special methodologies (catalysts and/or reaction media) have been developed for CO2 activation.

Supercritical CO2 is considered to offer advantages as a reaction medium and a substrate because of its unique physicochemical properties, such as high gaseous miscibility, efficient mass transfer due to enhanced diffusivity, easily tunable properties with variation of pressure or temperature, and disappearance of the gas–liquid phase boundary peculiar to the supercritical state. In addition, CO2, which is nontoxic and has an easily accessible critical point, can replace hazardous organic solvents. Moreover, by utilizing supercritical CO2 we can simplify the separation process.

This chapter first provides an introduction to the supercritical fluids. Some of the applications of supercritical CO2 both as a reactant and as a green reaction medium in synthesis of heterocyclic compounds such as cyclic carbonates, oxazolidinones, quinazolines, etc. are exemplified and discussed in the next sections.

References

  1. 1.
    Chen W, Zhong L-x, Peng X-w, Sun R-c, Lu F-c (2015) Chemical fixation of carbon dioxide using a green and efficient catalytic system based on sugarcane bagasse. An agricultural waste. ACS Sustain Chem Eng 3:147–152CrossRefGoogle Scholar
  2. 2.
    Ballivet-Tkatchenko D, Chambrey S, Keiski R, Ligabue R, Plasseraud L et al (2006) Direct synthesis of dimethyl carbonate with supercritical carbon dioxide: characterization of a key organotin oxide intermediate. Catal Today 115:80–87CrossRefGoogle Scholar
  3. 3.
    Tamura M, Honda M, Nakagawa Y, Tomishige K (2014) Direct conversion of CO2 with diols, aminoalcohols and diamines to cyclic carbonates, cyclic carbamates and cyclic ureas using heterogeneous catalysts. J Chem Technol Biotechnol 89:19–33CrossRefGoogle Scholar
  4. 4.
    Mizuno T, Iwai T, Ishino Y (2004) The simple solvent-free synthesis of 1H-quinazoline-2,4-diones using supercritical carbon dioxide and catalytic amount of base. Tetrahedron Lett 45:7073–7075CrossRefGoogle Scholar
  5. 5.
    Sadjadi S (2016) Supercritical fluids in nanoreactor technology. In: Sadjadi S (ed) Organic nanoreactors: from molecular to supramolecular organic compounds. Academic, Chennai, pp 373–420CrossRefGoogle Scholar
  6. 6.
    Kawanami H, Ikushima Y (2002) Regioselectivity and selective enhancement of carbon dioxide fixation of 2-substituted aziridines to 2-oxazolidinones under supercritical conditions. Tetrahedron Lett 43:3841–3844CrossRefGoogle Scholar
  7. 7.
  8. 8.
    Weibel GL, Ober CK (2003) An overview of supercritical CO2 applications in microelectronics processing. Microelectron Eng 65:145–152CrossRefGoogle Scholar
  9. 9.
    Knez Z, Markočič E, Leitgeb M, Primožič M, Knez Hrnčič M et al (2014) Industrial applications of supercritical fluids: a review. Energy 77:235–243CrossRefGoogle Scholar
  10. 10.
    Beckman EJ (2004) Supercritical and near-critical CO2 in green chemical synthesis and processing. J Supercrit Fluids 28:121–191CrossRefGoogle Scholar
  11. 11.
    Miners SA, Rance GA, Khlobystov AN (2016) Chemical reactions confined within carbon nanotubes. ChemSocRev 45:4727–4746Google Scholar
  12. 12.
    Zhang X, Heinonen S, Levanen E (2014) Applications of supercritical carbon dioxide in materials processing and synthesis. RSC Adv 4:61137–61152CrossRefGoogle Scholar
  13. 13.
    Oakes RS, Clifford AA, Rayner CM (2001) The use of supercritical fluids in synthetic organic chemistry. J Chem Soc Perkin Trans 1:917–941CrossRefGoogle Scholar
  14. 14.
    Munshi P, Ghosh A, Beckman EJ, Patel Y, George J et al (2010) Tuning catalyst solubility in CO2 by changing molar volume. Green Chem Lett Rev 3:319–328CrossRefGoogle Scholar
  15. 15.
  16. 16.
    Peach J, Eastoe J (2014) Supercritical carbon dioxide: a solvent like no other. Beilstein J Org Chem 10:1878–1895CrossRefGoogle Scholar
  17. 17.
    Sako T, Fukai T, Sahashi R (2002) Cycloaddition of oxirane group with carbon dioxide in the supercritical homogeneous state. Ind Eng Chem Res 41:5353–5358CrossRefGoogle Scholar
  18. 18.
    Sun J, Fujita S-I, Zhao F, Arai M (2005) A highly efficient catalyst system of ZnBr2/n-Bu4NI for the synthesis of styrene carbonate from styrene oxide and supercritical carbon dioxide. Appl Catal A Gen 287:221–226CrossRefGoogle Scholar
  19. 19.
    Yasuda H, He L-N, Sakakura T (2002) Cyclic carbonate synthesis from supercritical carbon dioxide and epoxide over lanthanide oxychloride. J Catal 209:547–550CrossRefGoogle Scholar
  20. 20.
    Kawanami H, Ikushima Y (2000) Chemical fixation of carbon dioxide to styrene carbonate under supercritical conditions with DMF in the absence of any additional catalysts. Chem Commun 2089–2090Google Scholar
  21. 21.
    Lu X-B, Xiu J-H, He R, Jin K, Luo L-M et al (2004) Chemical fixation of CO2 to ethylene carbonate under supercritical conditions: continuous and selective. Appl Catal A Gen 275:73–78CrossRefGoogle Scholar
  22. 22.
    He L-N, Yasuda H, Sakakura T (2003) New procedure for recycling homogeneous catalyst: propylene carbonate synthesis under supercritical CO2 conditions. Green Chem 5:92–94CrossRefGoogle Scholar
  23. 23.
    Aprile C, Giacalone F, Agrigento P, Liotta LF, Martens JA et al (2011) Multilayered supported ionic liquids as catalysts for chemical fixation of carbon dioxide: a high-throughput study in supercritical conditions. Chem Sus Chem 4:1830–1837CrossRefGoogle Scholar
  24. 24.
    Jiang J-L, Gao F, Hua R, Qiu X (2005) Re(CO)5Br-catalyzed coupling of epoxides with CO2 affording cyclic carbonates under solvent-free conditions. J Org Chem 70:381–383CrossRefGoogle Scholar
  25. 25.
    ChaoRong Q, HuanFeng J (2010) Histidine-catalyzed synthesis of cyclic carbonates in supercritical carbon dioxide. Sci China Chem 53:1566–1570CrossRefGoogle Scholar
  26. 26.
    Yasuda H, He L-N, Takahashi T, Sakakura T (2006) Non-halogen catalysts for propylene carbonate synthesis from CO2 under supercritical conditions. Appl Catal A Gen 298:177–180CrossRefGoogle Scholar
  27. 27.
    Wang J-Q, Yue X-D, Cai F, He L-N (2007) Solventless synthesis of cyclic carbonates from carbon dioxide and epoxides catalyzed by silica-supported ionic liquids under supercritical conditions. Catal Commun 8:167–172CrossRefGoogle Scholar
  28. 28.
    Du Y, Cai F, Kong D-L, He L-N (2005) Organic solvent-free process for the synthesis of propylene carbonate from supercritical carbon dioxide and propylene oxide catalyzed by insoluble ion exchange resins. Green Chem 7:518–523CrossRefGoogle Scholar
  29. 29.
    Kawanami H, Sasaki A, Matsui K, Ikushima Y (2003) A rapid and effective synthesis of propylene carbonate using a supercritical CO2-ionic liquid system. Chem Commun 896–897Google Scholar
  30. 30.
    Du Y, Wang J-Q, Chen J-Y, Cai F, Tian J-S et al (2006) A poly(ethylene glycol)-supported quaternary ammonium salt for highly efficient and environmentally friendly chemical fixation of CO2 with epoxides under supercritical conditions. Tetrahedron Lett 47:1271–1275CrossRefGoogle Scholar
  31. 31.
    Jutz F, Grunwaldt J-D, Baiker A (2008) Mn(III)(salen)-catalyzed synthesis of cyclic organic carbonates from propylene and styrene oxide in “supercritical” CO2. J Mol Catal A Chem 279:94–103CrossRefGoogle Scholar
  32. 32.
    Qiu J, Zhao Y, Li Z, Wang H, Fan M et al (2016) Efficient ionic-liquid-promoted chemical fixation of CO2 into a-alkylidene cyclic carbonates. Chem Sus Chem 9:1–9CrossRefGoogle Scholar
  33. 33.
    Kayaki Y, Yamamoto M, Ikariya T (2007) Stereoselective formation of α-alkylidene cyclic carbonates via carboxylative cyclization of propargyl alcohols in supercritical carbon dioxide. J Org Chem 72:647–649CrossRefGoogle Scholar
  34. 34.
    Ca’ ND, Gabriele B, Ruffolo G, Veltri L, Zanetta T et al (2011) Effective guanidine-catalyzed synthesis of carbonate and carbamate derivatives from propargyl alcohols in supercritical carbon dioxide. Adv Synth Catal 353:133–146CrossRefGoogle Scholar
  35. 35.
    Jiang H-F, Wang A-Z, Liu H-L, Qi C-R (2008) Reusable polymer-supported amine-copper catalyst for the formation of α-alkylidene cyclic carbonates in supercritical carbon dioxide. Eur J Org Chem 2008(13):2309–2312CrossRefGoogle Scholar
  36. 36.
    Du Y, Kong D-L, Wang H-Y, Cai F, Tian J-S et al (2005) Sn-catalyzed synthesis of propylene carbonate from propylene glycol and CO2 under supercritical conditions. J Mol Catal A Chem 241:233–237CrossRefGoogle Scholar
  37. 37.
    Aresta M, Dibenedetto A, Dileo C, Tommasi I, Amodio E (2003) The first synthesis of a cyclic carbonate from a ketal in SC-CO2. J Supercrit Fluids 25:177–182CrossRefGoogle Scholar
  38. 38.
    Miura T, Fujioka S, Takemura N, Iwasaki H, Ozeki M et al (2014) Sythesis of 6-substituted 3-(alkoxycarbonyl)-5-aryl-α-pyrones. Synthesis 46:496–502Google Scholar
  39. 39.
    Lee JS (2015) Recent advances in the synthesis of 2-pyrones. Mar Drugs 13:1581–1620CrossRefGoogle Scholar
  40. 40.
    Reetz MT, Konen W, Strack T (1993) Supercritical carbon dioxide as a reaction medium and reaction partner. Chimia 47:493–493Google Scholar
  41. 41.
    Inoue Y, ltoh Y, Kazama H, Hashimoto H (1980) Reaction of dialkyl-substituted alkynes with carbon dioxide catalyzed by nickel(0) complexes. Incorporation of carbon dioxide in alkyne dimers and novel cyclotrimerization of the alkynes. Bull Chem Soc Jpn 53:3329–3333CrossRefGoogle Scholar
  42. 42.
    Shestakov AS, Sidorenko OE, Bushmarinov IS, Shikhaliev KS, Antipin MY (2009) 3-aryl(alkyl)quinazoline-2,4(1H,3H)-diones and their alkyl derivatives. Russ J Org Chem 45:1691–1696CrossRefGoogle Scholar
  43. 43.
    Gao J, He L-N, Miao C-X, Chanfreau S (2010) Chemical fixation of CO2: efficient synthesis of quinazoline-2,4(1H, 3H)-diones catalyzed by guanidines under solvent-free conditions. Tetrahedron 66:4063–4067CrossRefGoogle Scholar
  44. 44.
    Nale DB, Saigaonkar SD, Bhanage BM (2014) An efficient synthesis of quinazoline-2,4(1H,3H)-Dione from CO2 and 2-aminobenzonitrile using [Hmim]OH/SiO2 as a base functionalized supported ionic liquid phase catalyst. J CO2 Util 8: 67–73Google Scholar
  45. 45.
  46. 46.
  47. 47.
    Seki T, Kokubo Y, Ichikawa S, Suzuki T, Kayaki Y et al (2009) Mesoporous silica-catalysed continuous chemical fixation of CO2 with N,N′-dimethylethylenediamine in supercritical CO2: the efficient synthesis of 1,3-dimethyl-2-imidazolidinone. Chem Commun 21(3):349–351CrossRefGoogle Scholar
  48. 48.
    Xiao L-f, Xu L-w, Xia C-g (2007) A method for the synthesis of 2-oxazolidinones and 2-imidazolidinones from five-membered cyclic carbonates and b-aminoalcohols or 1,2-diamines. Green Chem 9:369–372CrossRefGoogle Scholar
  49. 49.
    Soldi L, Massera C, Costa M, N. Della Ca’ (2014) A novel one-pot synthesis of oxazolidinones through direct introduction of CO2 into allylamine derivatives. Tetrahedron Lett 55: 1379–1383CrossRefGoogle Scholar
  50. 50.
    Du Y, Wu Y, Liu A-H, He L-N (2008) Quaternary ammonium bromide functionalized polyethylene glycol: a highly efficient and recyclable catalyst for selective synthesis of 5-aryl-2-oxazolidinones from carbon dioxide and aziridines under solvent-free conditions. J Org Chem 73:4709–4712CrossRefGoogle Scholar
  51. 51.
    Lu X-B (2016) CO2-mediated formation of chiral fine chemicals. In: Lu X-B (ed) Carbon dioxide and organometallics (topics in organometallic chemistry), vol 53. Springer, ChamCrossRefGoogle Scholar
  52. 52.
    Kathalikkattil AC, Tharun J, Roshan R, Soek H-G, Park D-W (2012) Efficient route for oxazolidinone synthesis using heterogeneous biopolymer catalysts from unactivated alkyl aziridine and CO2 under mild conditions. Appl Catal A 447–448:107–114CrossRefGoogle Scholar
  53. 53.
    Liu X-F, Wang M-Y, He L-N (2017) Heterogeneous catalysis for oxazolidinone synthesis from aziridines and CO2. Curr Org Chem 21:698–707CrossRefGoogle Scholar
  54. 54.
    Dou X-Y, He L-N, Yang Z-Z (2012) Proline-catalyzed synthesis of 5-aryl-2-oxazolidinones from carbon dioxide and aziridines under solvent-free conditions. Synth Commun 42:62–74CrossRefGoogle Scholar
  55. 55.
    Dou X-Y, He L-N, Yang Z-Z, Wang J-L (2010) Catalyst-free process for the synthesis of 5-aryl-2-oxazolidinones via cycloaddition reaction of aziridines and carbon dioxide. Synlett 14:2159–2163Google Scholar
  56. 56.
    Jiang H-F, Ye I-W, Qi C-R, Huang L-B (2010) Naturally occurring a-amino acid: a simple and inexpensive catalyst for the selective synthesis of 5-aryl-2-oxazolidinones from CO2 and aziridines under solvent-free conditions. Tetrahedron Lett 51:928–932CrossRefGoogle Scholar
  57. 57.
    AnHua L, LiangNian H, ShiYong P, ZhongDa P, JingLun W et al (2010) Environmentally benign chemical fixation of CO2 catalyzed by the functionalized ion-exchange resins. Sci China Chem 53:1578–1585CrossRefGoogle Scholar
  58. 58.
    Xu JX, Zhao JW, Jia ZB (2011) Efficient catalyst-free chemical fixation of carbon dioxide into 2-oxazolidinones under supercritical condition. Chin Chem Lett 22:1063–1066CrossRefGoogle Scholar
  59. 59.
    Jiang H-F, Zhao J-W (2009) Silver-catalyzed activation of internal propargylic alcohols in supercritical carbon dioxide: efficient and eco-friendly synthesis of 4-alkylidene-1,3-oxazolidin-2-ones. Tetrahedron Lett 50:60–62CrossRefGoogle Scholar
  60. 60.
    Jiang H-F, Zhao J, Wang A (2008) An efficient and eco-friendly process for the conversion of carbon dioxide into oxazolones and oxazolidinones under supercritical conditions. Synthesis 5:763–769CrossRefGoogle Scholar
  61. 61.
    Maggi R, Bertolotti C, Orlandini E, Oro C, Sartori G et al (2007) Synthesis of oxazolidinones in supercritical CO2 under heterogeneous catalysis. Tetrahedron Lett 48:2131–2134CrossRefGoogle Scholar
  62. 62.
    Kayaki Y, Yamamoto M, Suzuki T, Ikariya T (2006) Carboxylative cyclization of propargylamines with supercritical carbon dioxide. Green Chem 8:1019–1021CrossRefGoogle Scholar
  63. 63.
    Patil YP, Tambade PJ, Jagtap SR, Bhanage B (2008) Synthesis of 2-oxazolidinones/2-imidazolidinones from CO2, different epoxides and amino alcohols/alkylene diamines using BrPh3+P-PEG600-P+Ph3Br as homogenous recyclable catalyst. J Mol Catal A Chem 289:14–21CrossRefGoogle Scholar
  64. 64.
    Fujita S-i, Kanamaru H, Senboku H, Arai M (2006) Preparation of cyclic urethanes from amino alcohols and carbon dioxide using ionic liquid catalysts with alkali metal promoters. Int J Mol Sci 7:438–450CrossRefGoogle Scholar
  65. 65.
    Pulla S, Felton CM, Gartia Y, Ramidi P, Ghosh A (2013) Synthesis of 2-oxazolidinones by direct condensation of 2-aminoalcohols with carbon dioxide using chlorostannoxanes. Sustainable Chem Eng 1:309–312CrossRefGoogle Scholar
  66. 66.
    Kawanami H, Ikushima Y (2002) Synthesis of 2-oxazolidinone from b-aminoalcohol using supercritical carbon dioxide. J Jpn Petrol Inst 45:321–324CrossRefGoogle Scholar
  67. 67.
    Zhao J, Jiang H (2012) Copper (I) catalyzed synthesis of 1,3-oxazolidin-2-ones from alkynes, amines, and carbon dioxide under solvent-free conditions. Tetrahedron Lett 53:6999–7002CrossRefGoogle Scholar

Copyright information

© Springer Nature Switzerland AG 2019

Authors and Affiliations

  1. 1.Nuclear Science and Technology Research InstituteEnd of North Karegar Ave.TehranIran

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