Che106 Technical Communicatin

Chemical Engineering Departmant

Engineering Faculty
Ege University
Bornova/İzmir

ALKALOIDS

Prepared by Alper Baran SÖZMEN

Table of Contents

1. Summary

2. Introduction

3. History, Naming and Definition

4. Classification

a. True alkaloids

b. Protoalkaloids

c. Polyamine alkaloids

d. Peptide (cyclopeptide) alkaloids

e. Pseudalkaloids

5. Properties

6. Distribution in Nature

7. Extraction

8. Bio-synthesis

9. Applications

a. In Medicine

b. In Agriculture

10. References
Introduction
Summary
History, Naming and Definition
The definition of the term alkaloid is not a simple one, and is in many cases
a source of academic controversy. Difficulties with the definition of such a
group of secondary and natural molecules as alkaloids stem from similarities
of alkaloids with other secondary compounds. Attempts to define the term
“alkaloid” originated at the time of the discovery of these compounds. Friedrich
Sertürner, an apothecary’s assistant from Westphalia, first isolated morphine,
one of the most important alkaloids in the applied sense. This was in
1805, and proved a significant step forward in chemistry and pharmacology.
Using the method developed by Friedrich Sertürner, the pharmacists Pierre
Joseph Pelletier and Joseph Benaimé Caventou isolated, from 1817 to 1821, a
remarkable range of other alkaloids, such as febrifuge, quinine, caffeine and
veratrine. The term “alkaloid” was first mentioned in 1819 by W. Meißner, an
apothecary from Halle. [1]
The name "alkaloids" (German: Alkaloide) was introduced in 1819 by the German
chemist Carl F.W. Meißner ,[and is derived from late Latin root Latin:alkali (which, in
turn, comes from the Arabic al qualja - "ashes of plants") and the suffix Greek: ειδοσ -
"like". However, the term came into wide use only after the publication of a review
article by O. Jacobsen in the chemical dictionary of Albert Ladenburg in the 1880s.
Carl F.W. Meißner observed that these compounds appeared “like alkali”, and so
named them alkaloids.
There is no unique method of naming alkaloids. Many individual names are formed
by adding the suffix "-ine" to the species or generic alkaloids. For
example, atropine is isolated from the plant Atropa belladonna, strychnine is obtained
from the seed of Strychnine tree. If several alkaloids are extracted from one plant
then their names often contain suffixes "-idine", "-anine", "-aline", "-inine", etc. There
are also at least 86 alkaloids containing the root "vin" (extracted from
the Vinca plant). [2]
Chemistry has provided a definition of alkaloids in purely chemical terms. Chemists
stress that alkaloids are any group of complex heterocyclic nitrogen
compounds, which have strong physiological activity, are often toxic, and retain
their own basic chemical properties. It is also stated that there are a few exceptions
to this definition29. In another chemical definition, it is stated only that
alkaloids are nitrogen-containing compounds derived from plants and animals30.
Later, chemists stressed that alkaloids were biogenic, nitrogen-containing and
mostly N-heterocyclic compounds. In this definition it is also stated that amino
acids, peptides, nucleosides, amino sugars and antibiotics are not considered as
to be alkaloids. Inspite of differences between the research fields of biology,
medicine and chemistry, and the fact that there remain some differences of
accentuation in
alkaloid definitions, such definitions are very similar, indeed almost identical.
Scientists are recognizing the vital importance of these products for biology,
medicine and chemistry. What has been learnt about alkaloids from the last 200
years of studies? It is fascinating that alkaloids are just a product of nature, and a
very small unit of global nature both in the material sense and in processes as they
occur. [3]
Classification

Compared with most other classes of natural compounds, alkaloids are characterized
by a great structural diversity and there is no uniform classification of
alkaloids. Historically, first classification methods combined alkaloids by the common
natural source, e.g., a certain type of plants. This classification was justified by the
lack of knowledge about the chemical structure of alkaloids and is now considered
obsolete. [4]
More recent classifications are based on similarity of the carbon skeleton or
biogenetic precursor. However, they require compromises in borderline cases; for
example, nicotine contains a pyridine fragment from nicotinamide and pyrrolidine part
from ornithine and therefore can be assigned to both classes. [5]
Alkaloids can be classified in the terms of their (1) biological and ecological
activity; (2) chemical structures and (3) biosynthetic pathway. From the point of
view of biological activity, it is possible to divide alkaloids into (1) neutral or
weakly basic molecules (e.g., lactams such as ricinine, certain N-oxides such as
indicine), (2) animal-derived alkaloids (e.g., anuran, mammalian and arthropod
alkaloids), (3) marine alkaloids, (4) moss alkaloids, (5) fungal and bacterial
alkaloids and (6) non-natural alkaloids (structurally modified or analogues).
Nowadays, the group of compounds mentioned as non-natural alkaloids
is growing especially rapidly as a result of bio-organic and stereochemistry
research. Pharmacological research and the drug industry rapidly advance and
promote the most promising new molecules for possible production applications.
This is necessary since the sources of infections (micro-organisms) are
constantly changing their species and infection ability, becoming resistant to
medicines and antibiotics.

Alkaloids are generally classified by their common molecular precursors,

based on the biological pathway used to construct the molecule. From a structural
point of view, alkaloids are divided according to their shapes and origins. There
are three main types of alkaloids: (1) true alkaloids, (2) protoalkaloids and
(3) pseudoalkaloids. True alkaloids and protoalkaloids are derived from amino
acids, whereas pseudoalkaloids are not derived from these compounds.[6]

Alkaloids are often divided into the following major groups:

PİCTURE HERE
a. True alkaloids

True alkaloids derive from amino acid and they share a heterocyclic ring with
nitrogen. These alkaloids are highly reactive substances with biological activity
even in low doses. All true alkaloids have a bitter taste and appear as a
white solid, with the exception of nicotine which has a brown liquid. True
alkaloids form water-soluble salts. Moreover, most of them are well-defined
crystalline substances which unite with acids to form salts. True alkaloids may
occur in plants (1) in the free state, (2) as salts and (3) as N-oxides. These
alkaloids occur in a limited number of species and families, and are those
compounds in which decarboxylated amino acids are condensed with a nonnitrogenous
structural moiety. The primary precursors of true alkaloids are such
amino acids as l-ornithine, l-lysine, l-phenylalanine/l-tyrosine, l-tryptophan
and l-histidine23_32. Examples of true alkaloids include such biologically active
alkaloids as cocaine, quinine, dopamine, morphine and usambarensine.[7]

PİCTURE HERE

b. Protoalkaloids

Protoalkaloids are compounds, in which the N atom derived from an amino acid
is not a part of the heterocyclic31. Such kinds of alkaloid include compounds
derived from l-tyrosine and l-tryptophan. Protoalkaloids are those with a closed ring, being
perfect but structurally simple alkaloids. They form
a minority of all alkaloids. Hordenine, mescaline and yohimbine are
good examples of these kinds of alkaloid. Chini et al.33 have found new alkaloids,
stachydrine and 4-hydroxystachydrine, derived from Boscia angustifolia, a plant
belonging to the Capparidacea family. These alkaloids have a pyrroline nucleus
and are basic alkaloids in the genus Boscia. The species from this genus have
been used in folk medicine in East and South Africa. Boscia angustifolia is
used for the treatment of mental illness, and occasionally to combat pain and
neuralgia.[8]

PİCTURE HERE
c.Polyamine alkaloids

Polyamines either in their free basic form or conjugated to other molecules such as fatty
acids, cinnamic acids or other biomolecules occur in nature and show a large variety of
biological activities. The structures of these compounds can be linear, mono- or polycyclic.
They occur in humans, animals, plants and microorganisms, i.e. in the whole biosphere.
In 1996 we reported the first isolation of a compound containing both polyamines,
spermidine and spermine, connected by a C16 diamido bridge. This alkaloid was called
tenuilobine) because of its natural source the plant Oncinotis tenuiloba Stapf (Apocynaceae).
[9]

PİCTURE HERE

d. Peptide (Cyclopeptide) alkaloids

Cyclopeptide alkaloids are defined as basic compounds embodying an ansa structure, in

which a 10 or 12 membered peptide type bridge spans 1.3 or 1.4 positions of a benzene ring.
They are widely distrubuted among plants of the Rhamnaceae family, but their occurence
has also been confirmed in representatives of Asteraceae, Cellastraceae, Euphorbiaceae,
Menispermac eae, Pandaceae, Rubiaceae, Sterculiaceae and Urticaeae.[10]

PİCTURE HERE

e.Pseudoalkaloids

Pseudoalkaloids are compounds, the basic carbon skeletons of which are not
derived from amino acids31. In reality, pseudoalkaloids are connected with amino acid
pathways. They are derived from the precursors or postcursors (derivatives
the indegradation process) of amino acids. They can also result from the amination
and transamination reactions32 of the different pathways connected with
precursors or postcursors of amino acids. These alkaloids can also be derived from non-
aminoacid precursors. The N atom is inserted into the molecule at a relatively late stage, for
example, in the case of steroidal or terpenoid skeletons. Certainly, the N atom can also be
donated by an amino acid source across a transamination reaction, if there is a
suitable aldehyde or ketone. Pseudoalkaloids can be acetate and phenylalaninederived
or terpenoid, as well as steroidal alkaloids. Examples of pseudoalkaloids
include such compounds as coniine, capsaicin, ephedrine, solanidine, caffeine,
theobromine and pinidine. [11]
PİCTURE HERE

Properties