Apparicine

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Apparicine
Names
IUPAC name
(13S,14E)-14-Ethylidene-12-methylene-1,10-diazatetracyclo[11.2.2.03,11.04,9]heptadeca-3(11),4,6,8-tetraene
Identifiers
3D model (JSmol)
3DMet
ChEBI
ChEMBL
ChemSpider
KEGG
  • InChI=1S/C18H20N2/c1-3-13-10-20-9-8-14(13)12(2)18-16(11-20)15-6-4-5-7-17(15)19-18/h3-7,14,19H,2,8-11H2,1H3/b13-3-/t14-/m1/s1
    Key: LCVACABZTLIWCE-CRAFIKPXSA-N
  • C\C=C1\C[N@]2CC[C@@H]1C(=C)c1[nH]c3ccccc3c1C2
Properties
C18H20N2
Molar mass 264.372 g·mol−1
Density 0.945875
log P 3.404
Acidity (pKa) 8.37
1.665
0.552121
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Apparicine is a monoterpenoid indole alkaloid.[1] It is named after Apparicio Duarte, a Brazilian botanist who studied the Aspidosperma species from which apparicine was first isolated.[2][3] It was the first member of the vallesamine group of alkaloids to be isolated and have its structure established,[3] which was first published in 1965.[4] It has also been known by the synonyms gomezine, pericalline, and tabernoschizine.[5]

Biochemistry

The biosynthesis of apparicine and uleine have a similar pathway.

The alkaloid has been isolated from seven species of Aspidosperma.[6] It is the principal alkaloid found in the callus of Tabernaemontana elegans, and has also been identified in other Tabernaemontana species, including T. africana, T. divaricata, T. orientalis, and T. pachysiphon.[7][8] In studies of T. pachysiphon, it was found that alkaloid content including that of apparicine was greatest in young leaves and leaves receiving greater shade, and varied with leaf age, plant age, and provenance.[9]

Research on Aspidosperma pyricollum has led to the discovery that apparicine is biosynthesised from tryptophan by "loss of C-2 and retention of C-3".[10] The biosynthesis of apparicine requires alteration of the usual tryptamine side chain with loss of C-1.[1]

Structure determination

Its structure was established through the methods of chemical decomposition, and the nascent field of nuclear magnetic resonance (NMR) decoupling using the 1H isotope of hydrogen.[11] Ultraviolet–visible spectroscopy showed that apparicine has a similar UV absorption to uleine,[12] and their chromophores were found to be identical.[11]

NMR decoupling experiments revealed that apparicine lacks an N-methyl signal and has one methylenic carbon atom between the nitrogen atom and the indole rings, allowing researchers to distinguish it from uleine.[12] This was a notable early use of NMR decoupling to determine a chemical structure.[12] Its carbon skeleton was found to be related but different from that of uleine, and the structures of vallesamine and O-acetyl-vallesamine to be related to apparicine.[13]

Dehydrogenation of apparicine followed by oxidation with permanganate allowed location of the two piperidine ring carbon substituents.[14]

Applications

Apparicine may have several potential applications. In cell cultures, it has shown cytotoxicity against the experimental lymphocytic leukemia P388 cell line.[15] It exhibits strong activity against poliovirus type 3 (PV3),[15] and has moderate to strong activity against some human pathogens.[16] It is also active at opioid receptors[15] and has micromolar affinity for adenosine receptors.[17] Apparicine has local analgesic properties.[16]

Notes

  1. ^ a b Saxton 1983, p. 13.
  2. ^ Schmelzer & Gurib-Fakim 2008, p. 594.
  3. ^ a b Saxton 1983, p. 286.
  4. ^ Joule et al. 1965, p. 4773.
  5. ^ Helmuth, Manske & Holmes 1968, p. 273.
  6. ^ Monteiro 1966, p. 39.
  7. ^ Kurz 2012, p. 139.
  8. ^ Schmelzer & Gurib-Fakim 2008, p. 593.
  9. ^ Schmelzer & Gurib-Fakim 2008, p. 596.
  10. ^ Cain 1970, p. 324.
  11. ^ a b Phillipson & Zenk 1980, p. 230.
  12. ^ a b c Saxton 1983, p. 287.
  13. ^ Biemann et al. 2012, p. 40.
  14. ^ Saxton 1983, p. 288.
  15. ^ a b c Schmelzer & Gurib-Fakim 2008, p. 592.
  16. ^ a b Schmelzer & Gurib-Fakim 2008, p. 590.
  17. ^ Ingkaninan et al. 1999, p. 1441.

References

  • Biemann, K.; Erdtman, H.; Fraenkel-Conrat, H.; Hoffmann-Ostenhof, O.; Kindl, H.; Norin, T.; Tschesche, R.; Turner, A.B.; Warren, F.L. (2012). Progress in the Chemistry of Organic Natural Products. Fortschritte der Chemie organischer Naturstoffe Progress in the Chemistry of Organic Natural Products. Vol. 24. Springer Science & Business Media. ISBN 978-3-7091-8143-0. {{cite book}}: Invalid |ref=harv (help)
  • Cain, Cornelius K., ed. (1970). Annual Reports in Medicinal Chemistry, 1969. Annual Reports in Medicinal Chemistry. Vol. 5. Academic Press. ISBN 0-08-058349-0. {{cite book}}: Invalid |ref=harv (help)
  • Helmuth, Richard; Manske, Fred; Holmes, Henry Lavergne, eds. (1968). The Alkaloids: Chemistry and Physiology. Vol. 11. Academic Press. {{cite encyclopedia}}: Invalid |ref=harv (help); Missing or empty |title= (help)
  • Ingkaninan, K.; Ijzerman, A.P.; Taesotikul, T.; Verpoorte, R. (1999). "Isolation of Opioid-active Compounds from Tabernaemontana pachysiphon leaves". Journal of Pharmacy and Pharmacology. 51 (12). Blackwell Publishing: 1441–1446. doi:10.1211/0022357991777092. ISSN 2042-7158. PMID 10678501. {{cite journal}}: Invalid |ref=harv (help)
  • Joule, J. A.; Monteiro, H.; Durham, L.J.; Gilbert, B.; Djerassi, Carl (1965). "Alkaloid studies. Part XLVIII. The structure of apparicine, a novel aspidosperma alkaloid". Journal of the Chemical Society. Chemical Society: 4773–4780. doi:10.1039/JR9650004773. {{cite journal}}: Invalid |ref=harv (help)
  • Kurz, Wolfgang G.W. (2012). "Secondary Metabolites in Cell Cultures of Tabernaemontana Species". Primary and Secondary Metabolism of Plant Cell Cultures II. Primary and Secondary Metabolism of Plant Cell Cultures II. Springer-Verlag. p. 138. doi:10.1007/978-3-642-74551-5_16. ISBN 978-3-642-74551-5. {{cite encyclopedia}}: Invalid |ref=harv (help)
  • Monteiro, Hugo Jorge (1966). Studies on some indole alkaloids: the structure of vallesiachotamine. apparicine, an indole alkaloid of novel structure. the structure and chemistry of nervobscurine. tubulosine and its chemical correlation with deoxytubulosine, Parts 1–4. {{cite book}}: Invalid |ref=harv (help)
  • Phillipson, John David; Zenk, M.H., eds. (1980). Indole and Biogenetically Related Alkaloids. Annual proceedings of the Phytochemical Society of Europe. Vol. 17. Phytochemical Society of Europe. Academic Press. ISBN 0-12-554450-2. ISSN 0309-9393. {{cite book}}: Invalid |ref=harv (help)
  • Saxton, J. Edwin, ed. (1983). "Indoles: Part Four: The Monoterpenoid Indole Alkaloids". The Chemistry of Heterocyclic Compound. Vol. 25. John Wiley & Sons. ISBN 0-470-18844-8. {{cite encyclopedia}}: Invalid |ref=harv (help)
  • Schmelzer, G.H.; Gurib-Fakim, A., eds. (2008). Medicinal Plants. Vol. 1. PROTA Foundation, Backhuys Publishers. ISBN 9789057822049. ISSN 1877-430X. {{cite book}}: Invalid |ref=harv (help)

External links

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