Tetrahydropyridine

Last updated
Tetrahydropyridine
Tetrahydropyridines.svg
Three isomers of tetrahydropyridine
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
EC Number
  • 1,2,3,6:211-766-2
KEGG
PubChem CID
UNII
UN number 2410
  • 2,3,4,5:InChI=1S/C5H9N/c1-2-4-6-5-3-1/h4H,1-3,5H2
    Key: DWKUKQRKVCMOLP-UHFFFAOYSA-N
  • 1,2,3,4:InChI=1S/C5H9N/c1-2-4-6-5-3-1/h2,4,6H,1,3,5H2
    Key: VSWICNJIUPRZIK-UHFFFAOYSA-N
  • 1,2,3,6:InChI=1S/C5H9N/c1-2-4-6-5-3-1/h1-2,6H,3-5H2
    Key: FTAHXMZRJCZXDL-UHFFFAOYSA-N
  • 2,3,4,5:C1CCN=CC1
  • 1,2,3,4:C1CC=CNC1
  • 1,2,3,6:C1CNCC=C1
Properties
C5H9N
Molar mass 83.134 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Tetrahydropyridines (or piperideines) are heterocycles with the formula C5H9N. Three isomers exist, which differ by the location of the double bond. None of the parent species occur widely, so they are mainly of theoretical interest. Although the parent tetrahydropyridines are rare, many substituted tetrahydropyridines are known.

Contents

Preparation and occurrence

1-Methyl-4-phenyl-1,2,3,6-tetrahydropyridine causes permanent symptoms of Parkinson's disease. MPTP.svg
1-Methyl-4-phenyl-1,2,3,6-tetrahydropyridine causes permanent symptoms of Parkinson's disease.
(-)-Mitragynine is a naturally occurring tetrahydropyridine. (-)-Mitragynine Structural Formula V1.svg
(–)-Mitragynine is a naturally occurring tetrahydropyridine.

2,3,4,5-tetrahydropyridine, a colorless liquid, is commercially available. It is an imine and readily trimerizes, forming the hexahydro-1,3,5-triazine and fused hexahydro-1,3-diazine derivatives α-, β-, and iso- tripiperideine  [ wd ]. [1] [2]

6-acetyl-2,3,4,5-tetrahydropyridine contributes to the flavor of baked goods such as bread. [3]

N-Alkyl derivatives

While true tetrahydropyridine are rare, N-alkyl derivatives are more common. Partial reduction of pyridinium salts gives N-alkyltetrahydropyridines. Treatment of N-methylpyridinium salts with borohydride reagents gives 1-methyl-1,2,3,6-tetrahydropyridine. [4] [5]

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A modified Ireland-Claisen rearrangement leads to tetrahydropyridines via a silyl ketene acetal intermediate. [6]

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Ring-closing olefin metathesis has also been used to establish the tetrahydropyridine ring system. [7]

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References

  1. ↑ Claxton, George P.; Allen, Lloyd; Grisar, J. Martin (1977). "2,3,4,5-Tetrahydropyridine Trimer". Organic Syntheses. 56: 118. doi:10.15227/orgsyn.056.0118.
  2. ↑ Smolin, Edwin M.; Rapoport, Lorence, eds. (1959). s-Triazines and Derivatives. The Chemistry of Heterocyclic Compounds. Vol. 13. New York: John Wiley & Sons. p. 446. ISBN   978-0-470-18812-5.{{cite book}}: ISBN / Date incompatibility (help)
  3. ↑ De Kimpe, Norbert; Stevens, Christian (1993). "A convenient synthesis of 6-acetyl-1,2,3,4-tetrahydropyridine, the principle bread flavor component". Journal of Organic Chemistry. 58 (10): 2904–2906. doi:10.1021/jo00062a042.
  4. ↑ Balasubramanian, Marudai (2013). "Formation of Completely or Partially Reduced Pyridines and Quinolines". Pyridines: From lab to production. pp. 413–458. doi:10.1016/B978-0-12-385235-9.00005-9. ISBN   9780123852359.
  5. ↑ Thyagarajan, G.; May, E. L. (1971). "Improved synthesis of 2-benzyl-1,2,5,6-tetrahydropyridines, precursors of analgetic 6,7-benzomorphans". J. Heterocycl. Chem. 8 (3): 465. doi:10.1002/jhet.5570080317.
  6. ↑ Angle, S. R.; Henry, R. M. (1998). "Studies toward the Synthesis of (+)-Palustrine: The First Asymmetric Synthesis of (−)-Methyl Palustramate". J. Org. Chem. 63 (21): 7490–7497. doi:10.1021/jo980749g. PMID   11672402.
  7. ↑ Deiters, A.; Martin, S. F. (2004). "Synthesis of oxygen- and nitrogen-containing heterocycles by ring-closing metathesis". Chem. Rev. 104 (5): 2199–238. doi:10.1021/cr0200872. PMID   15137789.
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