2-Furonitrile

2-Furonitrile
Names
IUPAC name
furan-2-carbonitrile
Other names
2-Cyanofuran; 2-Furancarbonitrile; 2-Furyl cyanide
Identifiers
617-90-3 YesY
ChemSpider 62458 YesY
Jmol interactive 3D Image
PubChem 69245
Properties
C5H3NO
Molar mass 93.09 g·mol−1
Appearance colorless to light yellow
Density 1.0650 @20 °C
Boiling point 147 °C (297 °F; 420 K)
Hazards
Flash point 35 °C; 95 °F; 308 K
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

2-Furonitrile is a colorless to light yellow liquid furan derivative having a boiling point of 147 °C at atmospheric pressure[1] and with a density somewhat higher than that of water (1.0650 g/ml at 20 °C).[2]

Synthesis

2-Furonitrile was synthesized in 1913 by Emil Fischer from 2-furoyl chloride and hydrogen cyanide in pyridine-ether solution.[3]2-Furonitrile has been prepared in high yield and conversion from the vapor phase reaction of furfural and ammonia over bismuth molybdate catalyst. The reactants are fed in separate streams, in the presence of air and steam over the catalyst bed at 440-480 °C[4]

Additionally, furfural has been converted to 2-furonitrile by a number of reagents, including hydrazoic acid-perchloric acid, hypervalent iodine (III) and n-bromosuccinimide.[5][6] Thus, 2-furonitrile has been prepared in good yield by treating furfural with a mixture of hydrazoic acid (HN3) and perchloric acid in the presence of magnesium perchlorate in the benzene solution at 35 °C.[7][8] Similarly, a hypervalent iodine (III) reagent was used, as oxidant, together with ammonium acetate, as the nitrogen source, to provide 2-furonitrile in aqueous acetonitrile at 80 °C in 90% yield.[9] Selective conversion of furfural to 2-furonitrile was achieved under mild conditions in aqueous ammonium hydroxide solution employing n-bromosuccinimide (NBS) at ice bath temperatures.[10]

2-Furonitrile has also been prepared from other furan derivatives, including furfural aldoxime and furoic acid amide. Thus, a laboratory-scale synthesis of 2-furonitrile has been described employing the dehydration of 2-furoic acid amide or oxime via flash vacuum pyrolysis over molecular sieves in the gas phase.[11] Additionally, the dehydration of furfural aldoxime to 2-furonitrile has been accomplished in high yield employing thionyl chloride-benzotriazole[12] or triphenylphosphine-iodine reagents.[13]

Applications

2-Furonitrile has been suggested as a useful extractive distillation solvent and as a sweetening agent. It has about thirty times the sweetening power of sucrose.[14] 2-Furonitrile is also useful as an intermediate in pharmaceutical and fine chemical synthesis.

Thus, 2-furonitrile was used in the synthesis of adenosine A2a receptor antagonists (including drugs for the treatment of Parkinson's disease),[15] antiviral agents[16] and cardiotonic agents[17]

References

  1. ↑ Patrice Capdevielle; Lavigne, Andre; Maumy, Michel (1989). "Simple and efficient copper-catalyzed one-pot conversion of aldehydes into nitriles". Synthesis 6: 451–452. doi:10.1055/s-1989-27285.
  2. ↑ P. A. Pavlov; Kul'nevich, V. G. (1986). "Synthesis of 5-substituted furannitriles and their reaction with hydrazine". Khimiya Geterotsiklicheskikh Soedinenii 2: 181–186.
  3. ↑ Emil Fischer; Brauns, Fritz (1913). "Furoylformic and Furylglycolic Acids". Berichte der Deutschen Chemischen Gesellschaft 46: 892–6. doi:10.1002/cber.191304601117.
  4. ↑ Thomas J. Jennings, "Process for preparing furonitrile", US Patent 3,260,731 (1966)
  5. ↑ P. A. Pavlov; Kul'nevich, V. G. (1986). "Synthesis of 5-substituted furannitriles and their reaction with hydrazine". Khimiya Geterotsiklicheskikh Soedinenii 2: 181–186.
  6. ↑ Chenjie Zhu; Sun, Chengguo; Wei, Yunyang (2010). "Direct oxidative conversion of alcohols, aldehydes and amines into nitriles using hypervalent iodine(III) reagent". Synthesis 24: 4235–4241. doi:10.1055/s-0030-1258281.
  7. ↑ P. A. Pavlov; Kul'nevich, V. G. (1986). "Synthesis of 5-substituted furannitriles and their reaction with hydrazine". Khimiya Geterotsiklicheskikh Soedinenii 2: 181–186.
  8. ↑ B. Bandgar; Makone, S. (2006). "Organic reactions in water. Transformation of aldehydes to nitriles using NBS under mild conditions". Synthetic Communications 36 (10): 1347–1352. doi:10.1080/00397910500522009.
  9. ↑ Chenjie Zhu; Sun, Chengguo; Wei, Yunyang (2010). "Direct oxidative conversion of alcohols, aldehydes and amines into nitriles using hypervalent iodine(III) reagent". Synthesis 24: 4235–4241. doi:10.1055/s-0030-1258281.
  10. ↑ B. Bandgar; Makone, S. (2006). "Organic reactions in water. Transformation of aldehydes to nitriles using NBS under mild conditions". Synthetic Communications 36 (10): 1347–1352. doi:10.1080/00397910500522009.
  11. ↑ Jacqueline A. Campbell; McDougald, Graham; McNab, Hamish (2007). "Laboratory-scale synthesis of nitriles by catalyzed dehydration of amides and oximes under flash vacuum pyrolysis (FVP) conditions". Synthesis 20: 3179–3184. doi:10.1055/s-2007-990782.
  12. ↑ Sachin S. Chaudhari; Akamanchi, Krishnacharya G. (1999). "Thionyl chloride-benzotriazole: an efficient system for transformation of aldoximes to nitriles". Synthetic Communications 29 (10): 1741–1745. doi:10.1080/00397919908086161.
  13. ↑ A. Narsaiah; Sreenu, D.; Nagaiah, K. (2006). "Triphenylphosphine-iodine. An efficient reagent system for the synthesis of nitriles from aldoximes". Synthetic Communications 36 (2): 137–140. doi:10.1080/00397910500333225.
  14. ↑ Thomas J. Jennings, "Process for preparing furonitrile", US Patent 3,260,731 (1966)
  15. ↑ J. Kent Barbay, et al., "Preparation of methylene amines of thieno[2,3-d]pyrimidine and their use as adenosine A2a receptor antagonists", PCT Int. Appl. (2010), WO 2010045006 A1 20100422 (2010)
  16. ↑ Michele M Cudahy, et al., "Preparation of 4-oxo-4,7-dihydrofuro[2,3-b]pyridine-5-carboxamide antiviral agents", PCT Int. Appl. (2003), WO 2003059911 A2 20030724 (2003)
  17. ↑ Chau Ting. Huang, et al., "Preparation of N-hydroxy-5-phenyl-2-furancarboximidamides as cardiotonic agents", Eur. Pat. Appl., EP 321431 A1 19890621 (1989).
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