Apparicine

Last updated
Apparicine
Apparicine.svg
Names
IUPAC name
(19E)-2,7,16,17,19,20-Hexadehydro-3,7-seco-6-norcuran
Systematic IUPAC name
(2R,4E,5S)-4-Ethylidene-6-methylidene-1,3,4,5,6,7-hexahydro-2,5-ethanoazocino[4,3-b]indole
Identifiers
3D model (JSmol)
3DMet
ChEBI
ChEMBL
ChemSpider
KEGG
PubChem CID
  • 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 tricyclic 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 indole 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]

Contents

Biochemistry

The biosynthesis of apparicine and uleine have a similar pathway. Formacion de uleina y aparicina.png
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] It inhibited xanthine oxidase as potently as allopurinol (IC50 = 0.65 μM). [18]

See also

Notes

  1. 1 2 Herbert 1983, p. 13.
  2. ↑ Elia 2008, p. 594.
  3. 1 2 Joule 1983, p. 286.
  4. ↑ Joule et al. 1965, p. 4773.
  5. ↑ Gilbert 1968, p. 273.
  6. ↑ Monteiro 1966, p. 39.
  7. ↑ Verpoorte et al. 1989, p. 139.
  8. ↑ Elia 2008, p. 593.
  9. ↑ Elia 2008, p. 596.
  10. ↑ Shamma 1970, p. 324.
  11. 1 2 Joule et al. 1980, p. 230.
  12. 1 2 3 Joule 1983, p. 287.
  13. ↑ Biemann 1966, p. 40.
  14. ↑ Joule 1983, p. 288.
  15. 1 2 3 Schmelzer 2008, p. 592.
  16. 1 2 Mairura & Schmelzer 2008, p. 590.
  17. ↑ Ingkaninan et al. 1999, p. 1441.
  18. ↑ Shi BB, Chen J, Bao MF, Zeng Y, Cai XH (October 2019). "Alkaloids isolated from Tabernaemontana bufalina display xanthine oxidase inhibitory activity". Phytochemistry . 166: 112060. doi:10.1016/j.phytochem.2019.112060. PMID   31302343. S2CID   196613130.

Related Research Articles

<i>Acokanthera</i> Genus of plants

Acokanthera is a genus of flowering plants in the family Apocynaceae. It comprises 5 species and is generally restricted to Africa, although Acokanthera schimperi also occurs in Yemen. Its sap contains the deadly cardiotoxic glycoside ouabain. The sap is among the most commonly used in arrow poisons, including those used for poaching elephant.

<span class="mw-page-title-main">Indole alkaloid</span> Class of alkaloids

Indole alkaloids are a class of alkaloids containing a structural moiety of indole; many indole alkaloids also include isoprene groups and are thus called terpene indole or secologanin tryptamine alkaloids. Containing more than 4100 known different compounds, it is one of the largest classes of alkaloids. Many of them possess significant physiological activity and some of them are used in medicine. The amino acid tryptophan is the biochemical precursor of indole alkaloids.

<span class="mw-page-title-main">Plant Resources of Tropical Africa</span> International programme improving access to information about useful plants in Africa

Plant Resources of Tropical Africa, known by its acronym PROTA, is a retired NGO and interdisciplinary documentation programme active between 2000 and 2013. PROTA produced a large database and various publications about Africa's useful plants.

Pierreodendron kerstingii is a species of tree in the family Simaroubaceae. It is endemic to West Africa and found in Ivory Coast, Ghana, Togo, and Benin. It is sometimes considered synonym of Pierreodendron africanum, which would then be a widespread species distributed south to Angola and east to the Democratic Republic of the Congo.

<i>Tabernaemontana corymbosa</i> Species of plant

Tabernaemontana corymbosa is a species of plant in the family Apocynaceae. It is native to Brunei, China, Indonesia, Laos, Malaysia, Myanmar, Singapore, Thailand, and Vietnam. Glossy green leaves and faintly sweet scented flower. Flowers continuously all year. Frost tolerant. Grows to about 2 metres. Likes full sun to part shade. A number of cultivars are available.

<i>Adenium boehmianum</i> Species of plant

Adenium boehmianum, the Bushman poison, is a poisonous succulent endemic to the mostly dry regions of northern Namibia and southern Angola. The San people boil the root sap and latex to prepare arrow poison, which is sufficient for hunting large mammals, as it contains strong cardiotoxic effects. The leaves, borne only for three months a year, are arranged spirally and are clustered near the branch tips. A plant will flower for only a few weeks in winter. The oblong fruit releases many seeds through a longitudinal slit, which due to their lateral tufts, can be dispersed by wind.

<i>Acalypha ciliata</i> Species of flowering plant

Acalypha ciliata is a species in the botanical family Euphorbiaceae. It occurs widely in Africa where it is eaten as a vegetable, or fed to animals. In West Africa and East Africa it is used as a medicinal plant.

<i>Acalypha fruticosa</i> Species of flowering plant

Acalypha fruticosa is a species of flowering plant in the botanical family Euphorbiaceae. It occurs widely in East and southern Africa where it is eaten as a vegetable. It is also an important browse plant for sheep. In East Africa and southern Africa it is used as a medicinal plant. In northern Kenya arrow shafts and beehive lids are made from the stem. From the dried leaves a tea is made in Ethiopia.

Acalypha integrifolia is a species of flowering plant in the botanical family Euphorbiaceae. It is locally used as a medicinal plant. Leaf decoctions are drunk to treat intestinal worms.

Acalypha ornata is a species in the botanical family Euphorbiaceae. In Africa it is widely used as a medicinal plant. The stems are used as fibres for weaving baskets. The leaves are eaten as a vegetable; the plants are also fed to domestic animals. Acalypha ornata is sometimes planted as an ornamental plant.

Acalypha psilostachya is a species in the botanical family Euphorbiaceae. In East Africa it is used as a medicinal plant.

<i>Acalypha villicaulis</i> Species of flowering plant

Acalypha villicaulis is a species in the botanical family Euphorbiaceae. In tropical Africa it is widely used as a medicinal plant.

<i>Hymenocardia acida</i> Species of tree

Hymenocardia acida is a plant of the family Phyllanthaceae native to tropical Africa. It is a small tree that grows to 10 m tall. Occurs in the Guinea and Sudanian savannah zones and deciduous woodland, from Senegal eastwards to Ethiopia and southwards reaching Zimbabwe.

<i>Tabernaemontana elegans</i> African tree species

Tabernaemontana elegans, the toad tree, is a shrub or small tree in the family Apocynaceae. It is native to eastern Africa.

<span class="mw-page-title-main">Stemmadenine</span> Chemical compound

Stemmadenine is a terpene indole alkaloid. Stemmadenine is believed to be formed from preakuammicine by a carbon-carbon bond cleavage. Cleavage of a second carbon-carbon bond is thought to form dehydrosecodine. The enzymes forming stemmadenine and using it as a substrate remain unknown to date. It is thought to be intermediate compound in many different biosynthetic pathways such as in Aspidosperma species. Many alkaloids are proposed to be produced through intermediate stemmadenine. Some of them are:

<i>Phyllanthus maderaspatensis</i> Species of flowering plant

Phyllanthus maderaspatensis is a perennial herbaceous species of plant in the family Phyllanthaceae, widespread in tropical and subtropical areas of the old world.

<span class="mw-page-title-main">Tabernaemontanine</span> Chemical compound

Tabernaemontanine is a naturally occurring monoterpene indole alkaloid found in several species in the genus Tabernaemontana including Tabernaemontana divaricata.

<span class="mw-page-title-main">Vobasine</span> Chemical compound

Vobasine is a naturally occurring monoterpene indole alkaloid found in several species in the genus Tabernaemontana including Tabernaemontana divaricata.

<span class="mw-page-title-main">Vinervine</span> Vinca alkaloid

Vinervine is a monoterpene indole alkaloid of the Vinca sub-group. It is a derivative of akuammicine, with one additional hydroxy (OH) group in the indole portion, hence it is also known as 12-hydroxyakuammicine.

<span class="mw-page-title-main">Conopharyngine</span> Chemical compound

Conopharyngine is the major alkaloid present in the leaves and stem-bark of Tabernaemontana pachysiphon and Conopharyngia durissima. It is closely related voacangine and coronaridine. Conopharyngine pseudoindoxyl, a derivative of it, is also found in the same plant Tabernaemontana pachysiphon.

References

This page is based on this Wikipedia article
Text is available under the CC BY-SA 4.0 license; additional terms may apply.
Images, videos and audio are available under their respective licenses.