Phytochemistry

Phytochemistry is in the strict sense of the word the study of phytochemicals. These are chemicals derived from plants. In a narrower sense the terms are often used to describe the large number of secondary metabolic compounds found in plants. Many of these are known to provide protection against insect attacks and plant diseases. They also exhibit a number of protective functions for .human consumers Techniques commonly used in the field of phytochemistry are extraction, isolation and structural elucidation (MS,1D and 2D NMR) of natural products, as well as various chromatography techniques (MPLC, HPLC, LC.(MS

Constituent elements
The list of simple elements of which plants are primarily constructedcarbon, oxygen, hydrogen, calcium, phosphorus, etc.is not different from similar lists for animals, fungi, or even bacteria. The fundamental atomic components of plants are the same as for all life; only the details of the way

.in which they are assembled differs The following tables list element nutrients essential .to plants. Uses within plants are generalized
Macronutrients. (Necessary in large (quantities Element Nitrogen Oxygen Carbon Hydrogen Potassium Calcium Magnesiu m Phosphor us Sulfur
+ +

Form of uptake NO3 NH4 O2 H2O CO2 H2O

+

Notes .Nucleic acids, proteins, hormones, etc Various organic compounds Various organic compounds Various organic compounds

K .Cofactor in protein synthesis, water balance, etc Membrane synthesis and stabilization Element essential for chlorophyll Nucleic acids, phospholipids, ATP Constituent of proteins and coenzymes

Ca2

Mg2

H2PO4

SO42

Micronutrients. (Necessary in small (quantities Element Chlorine Boron Mangane se Zinc Copper Form of uptake
-

Notes Aids in root growth Affects reproduction Activity of some enzymes

Cl

H BO3
+

Mn2

Zn2 Involved in the synthesis of enzymes and chlorophyll Cu Enzymes for lignin synthesis

Molybde num Nickel

MoO42
+

Nitrogen fixation, reduction of nitrates Enzymatic cofactor in the metabolism of nitrogen compounds Eastern medicine

Ni2

Phytochemistry is widely used in the field of Chinese medicine

.especially in the field of herbal medicine Phytochemical technique mainly applies to the quality control of Chinese medicine or herbal medicine of various chemical components, such as saponins, alkaloids, volatile oils, flavonoids and anthraquinones. In the development of rapid and reproducible analytical techniques, the combination of HPLC with different detectors, such as diode array detector (DAD), refractive index detector (RID), evaporative light scattering detector (ELSD) and mass spectrometric .detector (MSD), has been widely developed In most cases, biologically active compounds in Chinese medicine or herbal medicine have not been determined. Therefore, it is important to use the phytochemical methods to screen and analyze bioactive components, not only for the quality control of crude drugs, but also for the elucidation of their therapeutic mechanisms. Modern pharmacological studies indicate that binding to receptors or ion channels on cell

membranes is the first step of some drug actions. A new method in phytochemistry called biochromatography has been developed. This method combines human red cell membrane extraction and high performance liquid chromatography to screen potential active components in .Chinese medicine

INTRODUCTION
Alkaloids are a chemically heterogenous group of natural substance and compose more than 6000 basicNitrogen containing organic compounds which occur in about 15% of all vascular terresterial plants and in more than 150 different plant families. The alkaloids exhibit diversity of structure and also show an extraordinary spectrum of pharmacological activities. Because of these characters, they are important for chemical, physiological studies, taxonomical studies and biogenetic studies.Introduction Two main source of medicine are, one is synthetic and another is naturally occurring. Synthetic drugs show rapid onset of action but having more side effects in comparison to naturally occurring drugs. The modern trend are back to choose natural medicine against synthetic medicine. Natural source of drugs are plants, animals, or minerals. About 8000 plants are listed in medicinal uses. In this 1800 in Ayurveda, 1100 in Shiddha, ,750 in Unani in Tibetan and 4700 plants are used as traditionally ethno 300 .medicinally The world over the total trade of medicinal plants about 8800lakh .dollar, of which contribution of India in world trade less then 1% Out of this majority of plants are yet to be study photochemical,

estimated of such pants to the extent of 5000 to 6000. Phytochemistry is branch of Chemistry, which deals with the study of chemistry of plants. Where the term phytochemistry is comes out from phyta chemistry (phyta plant).Pharmaphytochemistry The word + pharmaphytochemistry is derived from pharmakon drugs phyta plants i.e. chemistry of medicinal substance inside the plants.Alkaloids Chemistry: Sertuerner in 1806 laid the foundation of Alkaloids Chemistry. It is the branch of Pharma Phyto Chemistry, which deals with the study of Alkaloids. He reported isolation .of Morphine from opium What is Alkaloids: Alkaloids means Alkali likes. The Pharmacist W.Meissner proposed the term Alkaloids in 1819. Acc. to him "Alkaloids alkali = base, oid=like sub) are basic nitrogenous compd. of plant) origin which have complex molecular structure & many pharmacological ".activity Acc to Landenberg "Alkaloids are defined as natural plant compounds that have a basic character and contain at least one nitrogen atom in a heterocyclic ring and having biological activities."Acc to characteristic features Alkaloids are basic nitrogenous plant origin, mostly optically active & possessing nitrogen hetero cycles as there .structural units with physiological action

Contents

HISTORY 1 DEFINITION 2 PROPERTIES 3

PHYSICAL PROPERTIES 7.1 CHEMICAL PROPERTIES 7.2

CHEMICAL TESTS FOR ALKALOIDS 4

BY DRAGENDROFF REAGENT 7.1 BY MAYERS REAGENT 7.2 BY WAGNER REAGENT 7.2 BY HAGER REAGENT 7.2 BY TANNIC ACID 7.2 BY PICROLONIC ACID 7.2

ISOLATION AND EXTRACTION OF ALKALOIDS 5 CLASSIFICTION OF ALKALOIDS 6

Pharmacological classification 7.1 Taxonomic classification 7.2 Biosynthetic classification 7.2 Chemical classification 7.2

ROLE OF ALKALOIDS IN PLANTS 7

HISTORY
The term alkaloids or Pflanzenlkalien was coined by Meissner, a German pharmacist, in 1819. the mankind has been using alkaloids for various purposes like poison, medicine, poultices, teas, etc The French chemist, Derosne in 1803, isolated narcotine. In the same year, morphine from opium was isolated by Serturner, a pharmacist of Padeborn near hannover in 1803. Pelletier and Caventon from the Faculty of pharmacy of Paris isolated emetine in 1817 and colchicines in 1819. this was followed by isolation of series of alkaloids from vegetable drug, like strychnine (1817); brucine, piperine andcaffine ( 1819), quinine, colchicines and cinchonine (1820); co niine (1826), papaverine(1821) and thebaine (1835). By

1884, about 25 alkaloids were reported to be isolated from cinchona bark alone. But in 1870, a landmark in domain of alkaloid was achieved by determining thestructure of coniine, which also become first synthesized alkaloid in 1889. From the beginning of 19th century till to date, it has proved to be a perpetual work of discover new alkaloids from the plant and animal. In the present century, the proper structure were assigned to various alkaloids with the help ofchromatographic and another sophisticated physical method of analysis. As per a Russian review in 1973, the number of known alkaloids had reached upto 4959, amongst which, the structure of 3293 alkaloids were elucidate. At present, the number of .alkaloids discovered has exceeded 6000

DEFINTION
In the view of their chemical and physiological diversity, there is no comprehensive definition of alkaloids. The term is derived from the word alkali-like and hence, they resemble some of the characters of naturally occurring complex amines. The term alkaloids also cover proto

alkaloids and pseudoalksloids. In view of all such variations, the only definition that bring all such :compounds under one title is as follows These are the organic product of natural and synthetic origin which are basic in nature and contain one or more than one nitrogen compound normally in heterocyclic in nature, and posses specific physiological action on human and animal body, when use in small quantities The true alkaloids are toxic in nature and contain one or more heterocyclic nitrogen compound which is derived from amines and always basic in nature. True alkaloids are normally present in plants as salts of organic acids. The proto-alkaloids or amino-alkaloids in which nitrogen is not .present in heterocyclic ring Some times they are considered as biological amines. They are basic in nature and prepared in plants from amino acids. Some of the examples of these alkaloids are mescaline, N-dimethyl tryptamine, colchine and ephedrine. The term pseudoalkaloid includes mainly steroidal terpenoides alkaloids and purine. They are not derived from amino acids. They do not show many of typical characters of alkaloids, but give the standard qualitative test for alkaloids. The example of .pseudoalkaloids are conessine and caffine

OCCURRENCE OF ALKALOIDS

Alkaloids are chemically nitrogenous heterocyclic basic compound occur in nature, about15% of vascular plant & widely distributed in - ..higher plant e.g Apocynace, papaveraceae, papilanaceae, rananeulaceae, .solenaceae They are present in the form of salts of organic acid, like acetic ,acid oxalic acid, malic, lactic, tartaric, tannic, aconitic acid, few are .with sugar e.g :Solanum, veratrum groups. Acc. to parts of plants Leaves: Nicotine .Bark: Cinchonine, Quinine .Seeds: Strychnine, Nibidine Roots: Rawelfinine, Glycyrrhizin, Punarnavine I & II

NOMENCLATURE
There was no systematic nomenclature. But there are some methods for .nomenclature are mention below

:According to their source

There are named according to the family in which they are .found e.g. papavarine, punarnavin, ephedrin :According to their Physiological response There are named according to their physiological response e.g.. Morphine means God of dreams, emetine means to .vomit :According to there discover There are named according to there discover e.g.. pelletierine group has been named its discoverer, P.J. .Pelletier :Prefixes There are named by some prefixes are fix in nomenclature of alkaloids, e.g. epi, iso, neo, pseudo, nor- CH3 group not attach to Nitrogen 4

PROPERTIES
PHYSICAL PROPERTIES With few exemptions, all the alkaloids are colourless, crystalline solids with a sharp melting points or decomposition range. Some alkaloids are amorphous gum, while other coniine, spartine, nicotine etc. are liquid and volatile in naruer. Some alkaloids are coloured in nature,

eg. Betanidin is red, berberine is yellow and salts are .copper-red in colour In general, the free bases of alkaloids are soluble in organic non-polar, immiscible solvents. The salts of more alkaloids are soluble in water. In contrast, free bases are insoluble in water and their salts are also sparingly soluble in organic solvents. The alkaloids containing quaternary bases are only water soluble. Some of the pseudoalkalods and protoalkaloids shows higher solubility in water. For examples, colchicines is soluble in alkaline water, acid and water and caffeine (free base) is freely soluble in water. Quinine hydrochloride is highly soluble in water i.e. 1 part of quinine hydrochloride is soluble in less than 1 part of water, while only 1 part of quinine sulphate in 1000 parts .of water The solubility of alkaloids and salts is useful in pharmaceutical industry for the extraction and formulation of final pharmaceutical properties

CHEMICAL PROPERTIES Most of the alkaloids are basic in reaction, due to availability of lone pair of electron on the nitrogen ring. The basic character of the alkaloidal compound is enhanced if the adjust function groups are electron releasing. The alkaloid turns to be natural or acidic when the adjust functional groups are electron withdrawing like amide group which reduces availability of lone pair of electrons. But alkaloids exhibits basic characters are very much sensitive to decomposition and cause a problem during their storage. Their salt formation with inorganic .acid prevents many a time their decomposition The alkaloids may contain one or more number of nitrogen

and it may exist in the form as primary(R-NH2), eg. Mescaline, secondary amine (R2-NH),eg.ephedrine; tertiary amine(R3-N),eg. Atropine; and quaternary amine (R4N+X),eg. Tubocuarine chloride. In the last type, their properties vary from other alkaloids, owing to quaternary .nature of nitrogen In the natural for, the alkaloids exist either in free form , as amine or as salt with acid or alkaloids N-oxides

CHEMICAL TESTS FOR ALKALOIDS

The qualitative chemical tests used for detection of alkaloids are depend on the character of alkaloids to give precipitate as salts of organic acids or with compound of heavy metals like Hg, Au, .Pt, etc Test by Dragendorff reagent(Potassium-bismuth-iodide - : (solution Alkaloids give reddish-brown precipitate with this .reagent test by Mayer reagent (Potassium-mercuric-iodide - :(solution Alkaloids gives cream colour precipitate with this .reagent

test by Wagner reagent (iodine-potassium-iodide - :(solution Alkaloids give Brown colour precipitate with this .reagent - :(test by Hager reagent (Saturated solution of picric acid alkaloids give yellow colour precipitate with this .reagent - :Test by Tannic acid Alkaloids gives buff colour precipitate with this acid - :Test by Picrolonic acid Alkaloids give yellow colour precipitate with this acid

CLASSIFICTION OF ALKALOIDS
The other methods proposed for classification of alkalids are as - :follows

:Pharmacological Classification.1
Depending on the physiological response, the alkaloids are classified under various pharmacological categories, like central nervous system stimulants or depressants, symphatomimentics, analgesic, purgative, etc. this method dose not take into account chemical nature of crude drugs with in the same drugs, the individual alkaloid may exhibit different action e.g. morphine is narcotic analgesic, while codenine is mainly antiussive. In cinchona, quinine is antimalarial, while .quinidine is cardiac depressant

- :Taxonomic classification.2 this method classifies the vast number of alkaloids based on their distribution in various plants families, like solanaceous or papillionaceous alkaloids. Preferably, they are grouped as per the name of genus in which they occur, e.g. ephedra, cinchona, etc. from this classification the .chemotaxonomic classification has been further derived

:Biosynthetic Classification.3
This method gives significance to the precious from which the alkaloids are biosynthesized in the plant. Hence, the varity of alkaloids with different taxonomic distribution and physiological activities can be brought under same group if they are derived from same procedure. E.g. all indole alkaloids from tryptophan

are grouped together. The alkaloidal drugs are catagorised on the fact whether are derived from amino acid procedure as .ornithine, lysine, tyrosine, phenylalanine, tryptophen, etc

- :Chemical classification.4
This is a most accepted way of classification of alkaloids. The main criterion for chemical classification is the type of fundamental(normally heterocyclic) ring structure present in alkaloids. The alkaloidal drugs are broadly categorized into two .divisions true alkaloids(heterocyclic alkaloids) are divided into twelve group according to the nature of their heterocyclic ring

b) protoalkaloids or biological amine and) .pseudoalkaloids

other modes of classification TAXONOMIC BASED ON THEIR FAMILY ,e.g. solanaceous papilionaceous without reference their chemical type of alkaloids present & another according to genus. e.g.. ephedra, cinchona etc. Pharmacological based: Their :pharmacological activity or response. For example Analgesic alkaloids .1 Cardio active alkaloids etc. Do not have chemical .2 .similarity in their group Economic species in Solanaceae

A brief account of the many useful species in the genus Solanum can be found on the Solanaceae Source pages .maintained by the Natural History Museum in London Other useful background information can be found on the Wikipedia pages for other Solanaceous species of economic importance such as Tomato, Capsicum, Eggplant, Potato, Physalis and Nicotiana for which of course there are huge .literature and web resources Mrs Grieves Modern Herbal supplies a considerable amount of information on many Solanaceous species and while some of it .is dated it can still be of considerable historical interest While there are numerous garden sites which deal with Solanaceae species used in horticulture the plant and garden .wiki encyclopedia Gardenology might be worth checking

BIO SYNTHETIC BASED According to this alkaloids are usually classified by their common molecular precursors, based on themetabolic pathway used to construct the molecule. When not much was known about the biosynthesis of alkaloids, they were grouped under the names of known compounds, even some nonnitrogenous ones (since those molecules' structures appear in the finished product; the opium alkaloids are sometimes called "phenanthrenes", for example), or by the plants or animals they were isolated from. When more is learned about a certain alkaloid, the grouping is changed to reflect the new knowledge, usually taking the name of a biologically-important amine that .stands out in the synthesis process
Pyridine group:piperine,coniine,trigonelline,arecaidine,guv .acine,pilocarpine,cytisine,nicotine,sparteine,pelletierine

Pyrrolidine group: hygrine,cuscohygrine,nicotine

Tropane group: atropine, cocaine, ecgonine, scopolamine, catuabine Quinoline group: quinine, quinidine, dihydroquinine, dih ydroquinidine, strychnine,brucine, veratrine,cevadine Isoquinoline group: The opium alkaloids (morphine, codeine, thebaine, Isopapa-dimethoxyaniline,papaverine, narcotine, sanguinarine, narceine, hy drastine, berberine), emetine, berbamine,oxyacanthine Phenethylamine group: mescaline, ephedrine, dopamine, amphetamine :Indole group Tryptamines: DMT, N-methyltryptamine, psilocybin, serotonin Ergolines: the ergot alkaloids .(ergine, ergotamine, lysergic acid, LSD etc Beta-carbolines: harmine, harmaline, yohimbine, reserpine Rauwolfia alkaloids: Reserpine :Purine group Xanthines: caffeine, theobromine, theophylline

:Terpenoid group Aconite alkaloids: aconitine Steroids: solanine, samandaris (quaternary ammonium compounds): muscarine, choline, neurine

Vinca alkaloids: vinblastine, vincristine. They are antineoplastic and binds free tubulin dimers thereby disrupting balance between microtuble polymerization and delpolymerization resulting in arrest of cells in .metaphase Miscellaneous: capsaicin, cynarin, phytolaccine, phytolaccotoxin

Chemical classification: This classification is universally adopted & depends on the fundamental ring structure. According to these two main .groups Non-heterocyclic Alkaloids: In this group of alkaloid not has .1 any one Heterocyclic ring in their structure. e.g.- Hordinine (Hordeum ,(vulgare .Ephedrine(Ephedra gerardiana) Genateceae Heterocyclic Alkaloids: According to heterocyclic ring the .2 alkaloids are - :sub divide in following

PYRROLE This type of alkaloids contains pyroll or pyrrolidine ring : in their structure e.g.. Hygrines Coca sp. For detailed information click here

PYRROLIZIDINE Alkaloids containing Pyrrolizidine Heterocyclic ring in their structure e.g.. - seneciphylline Senecio sp. For detailed information click here

PYRIDINE & PIPERIDINE Alkaloids containing Pyridine Heterocyclic ring in their structure e.g. Nicotine, Lobaline, Piperidine, Ricinine. For detailed information click here&click here

&

(PIPERIDINE(TROPANE

Alkaloid containing tropone ring. e.g..-Hyoscyomine, Atropine Hyoscine- Solanceae Cocain- Coca sp. Tropane Quinoline Iso Quinoline Nor Lupinane Iodole For detailed information click here ortropane

QUINOLINE Those Alkaloids containing quinolin ring in their structure e.g..- Quinine, Quinidine. (Cinchona bark) Cinchonine, Cinchonidine & cusparin -(cusparia bark) For detailed information click here

ISO QUINOLINE Alkaloids containing iso quinoline ring in thier chemical structure e.g. Papavarine, Narceine Emetine & cephaline. (Cephalis sp Rubiaceae). For detailed information

(REDUSED ISO QUINOLINE(APORPHINE The alkaloid contain reduced isoquinoline ring in their structure e.g. Baldine, (Peumus Baldus) (Manioniaceae) For detailed information

NOR LUPINANE Alkaloids present in leguminoceae plants e.g. .spartine, lupanine INDOLE ALKALOIDS Alkaloids containing indole ring. e.g. Yohimbine, Aspidospermine (Apocynaceae) Vinblasine, vincristine (catheranthus roseus). For detailed information click here

ISOLATION AND EXTRACTION OF ALKALOIDS

The extraction of alkaloids is based upon their basic character and solubility pattern. The normal procedures followed are to treat moistened drug with alkali so as to set free the base as it exists in salt form and then to separate free base with organic solvent. This is known as Stas Otto process. Through the method of extraction vary, gernally following procedure is applied for small scale extraction of alkaloids. First the plant is defatted with patrollium ether, eapatially in case of seed and leaf forms of drugs. Before applying this treatment the alkaloid should be tested for its solubility in patrolleum ether. Otherwise the drug should be pretreated with acid to be convert alkaloid into the salts. This happens in case of extraction of regotamine .from ergot In the second stage the drugs may be extacted with polar solvents like water, ehanol, methnol aqueous alcohol mixture or with acidified aqueous solution. By this treatment alkaloidal salts are transferred to polar solvent. It also helps in remving pigments sugar and other organic constituents in the following stage. The alcohol solution is evaporated to a thick syrup and is subjected to partition between aqueous acid solution and an organic solvent. After continous extraction with organic solvent for some time the aqueous phase is made alkaline with ether sodium carbonate or ammonia. The basic aqueous solution is then extracted with convenient organic solvent

followed by drying off alkaloid containing solution normally with sodium sulphate, filtered and evaporated to .yield alkaloid residue The other method ment for extraction for alkaloids employs the treatment of drug with ammonia so as to covert the alkaloidal salt into their free bases such librated alkaloids in free base form are conveniently extracted with organic solvents like ether, benzene, chloroform, etc. the method is not useful for isolating alkaloids with .quaternary nitrogen The further purification of crude extract of alkaloids is done by following ways which may however, vary for .indivisual for alkaloids

Purification or isolation of alkaloids from a plant is always difficult process because an alkaloids bearing plant generally contains a complex mixture of several alkaloids with glycoside organic acid also .complicate the process .Following steps are involved in isolation process :Detection of presence of Alkaloids First of all confirm the presence of alkaloids in raw material or crud drugs by various reagents called Alkaloids .reagents e.g

a,Mayer (Cream Co lour) Test .b.Marquis (Conc. HCHO) Test

c.Erdmann (Conc. HNO3) Test d.Hager's (Yellow Colour) Test e.Frohdes (Molybdic acid) Test

- :Extraction
The plants is dried, then finally powdered and extracted with boiling methanol. The solvent is distilled off and the residue treated with inorganic acids, when the bases (alkaloids) are extracted as their soluble salts. The aqueous layer containing the salt of alkaloids and soluble plant impurities is made basic with NaOH. The insoluble alkaloids are set free precipitate out. The solid man (ppt.) so obtained is then extracted with ether when .alkaloid pass into solution and impurity left behind

- :Flow Chart of extraction

:Separation of Alkaloids

After detection of next step is separation of a relatively small percentage of alkaloids from large amount of crude drugs. E.g.- Opium contains 10% Morphine, Chincona contains 5-8 % Quinine, .Belladona- 0.2% of Hyoscyamine The required alkaloid is separated from the mixture from fractional, crystallization, chromatography and .ion exchange method Physical-Property

They are colorless, crystalline solid. Exception - .(Berberin (Yellow), Nicotine Coniine (liquid They are insoluble in water (exception liquid alkaloids soluble in water), soluble in organic (solvent ( CHCl3, Ethyl alcohol ether .Taste: They are bitter in taste Optically active, Most of levo ratatory but few are -Dextro rotatory e.g. Coniine, some inactive.e.g.- papaverine

General Methods for Structure

Determination of Alkaloids
Molecular formula of majority of Alkaloids is complex so very little achievement in their elucidation of structure. During 19th Century. Now general procedures for elucidation of structure of .alkaloids are adopted

:Molecular formula molecular weight A pure specimen of alkaloids its empirical formula and molecular weight by elemental or combustion analysis. No. Of double bond is determined by double bond .equivalent method - :Number of Double bond Number of Rings present in an alkaloids can be determine by following formula- Ca Hb Nc Od Then number of double bond present in Ring= a-b/2 + C/2 + 1 :Functional group Analysis - :Functional Nature of Oxygen .1 - :Oxygen presents in alkaloids as OH (Phenolic/ Alcoholic), - OCH3 Methoxy, OCOCH3 (Acetoxy), - OCOC6H5 (Benzoxyl), -COOH (Carboxylic),- COOK (carboxylate),>C=O (Carbonyl),=C-O-O (Lactones Ring).It can be .determined by infra red or organic analysis method

- :Hydroxyl group .2 Formation of Acetate on treatment with Acetic anhydride /Acetyl chloride or benzoate on treatment .with Benzyl chloride

Soluble in NaOH Re precipitated by CO2 Giving coloration with FeCl3

- :Carboxylic group .3 Soluble in aqueous solution sodium carbonate or ammonia on treat with alcohol form ester.Number of -COOH group can be determined by volumetrically

by titration against a standard. Ba(OH)2 solution by .using phenolphthalein as an indicator - :Oxo-group .4 On treatment with Hydroxylamine. Semicanbezide, phenylhydrazide ,oxime ,semicarbazone phenyl Hydrazine

The distinction between aldehyde and ketone is done by oxidation or reduction, also by NMR, IR, and UV .techniques - :Methoxyle group .4 BY Zeisel determination method. When methoxy group present in a alkaloids treated with HI at 126 0 C perform methyl iodide which can treated further with silver nitrites to perform silver iodide precipitate. Which estimated gravimetrically e.g.. .Papavarine

- :Methylenedioxy group .5

On heated with concentrated with HCL or H2SO4 to form formaldehyde and further formation of dime .done derivative, which estimated gravimetrically

:b) Ester Amide lacton & Lactum group These groups are identified by the estimation of .product

c) Nature of Nitrogen Majority of nitrogen presence in alkaloids are secondary and tertiary: If tertiary when treated with .H2 O2 (50%) form

If alkaloids react with one molecule of methyl-iodide .to form N-methyl derivative, it means secondary e.g

DIRECT CRYSTALLISATION FROM.1 - :SOLVENT it is a very simple method of isolation and may not be useful in case of complex mixture - :STEAM DISTILLATION .2 This method is espateially employed for volatile liquid alcohols like coniine, sparteine, and nicotine, but other wise this process is not suitable for alcohols .with high molecular weights

- :CHROMATOGRAPHY TECHNIQUES .3 This method has provided to be ideal for separation of a vast number of plant alkaloids. The different technique of chromatography (thin layer, column, gas, liquid, ion exchange chromatography, HPTLC, etc.) are used for separation of indivisual alkaloids .from complex mixture - :GRADIENT pH TECHNIQUES .4 Tthough alkaloids are basic in nature, there are variations in the extent in the basicity of various alkaloids of the same plant. Depending on this character, the crude alkaloidal mixture is dissolved in 2% tartaric acid solution and extracted with benzene so that the first fraction contains natural and/or very weakly basic alkaloids. pH of the aqueous solution is increased gradually by 0.5 increment upto pH 9, and extraction is carried out at each pH level with organic solvent, by this way alkaloids with different basicity are extracted. Strongly basic alkaloids are extracted .at the end

ROLE OF ALKALOIDS IN PLANTS

The alkaloids are poisonous in nature, but when used in small quantities, exert useful physiological effects on animals and human beings and hence they have secured significant place in medicine. There exact role in nature and function in the plants, if any, are still a topic ambiguity. Only one aspect is clearly understood that they are synthesized by particular, stereospecific, many a time complicated, and energy consuming pathways and further they are metabolized to other alkaloidal or non-alkaloidal substances. Some of the predicted roles of alkaloids in the - :plants are discussed below

They are the reserve substance with an ability to .supply nitrogen They might be the defensive mechanism for plant growing in dry regions to protect from grazing .animals, herbivores and insects It is also possible that they are end product of detoxification mechanism in plants, and by this way check formation substance which may prove to be .harmful to the plants They might have a possible role as growth regulatory factors in plants The are present normally in conjugation with plants acids, like meconic acid, cinchotannic acid etc. there foe alkaloids could be acting as carriers with in plants .for transportation of such acids

.ANIMAL BASED ALKALOIDS The vast majority of the alkaloids are plant-derived, although in recent times more and more alkaloids are found in animals. Samandarine (20 mg applied on the skin of an adult human is lethal !), samandarone and cycloneosamandarine were isolated from the skin glands of the European fire salamander (Salamandra maculosa); all exhibit the .usual properties of alkaloids

Batrachotoxinin A, a steroidal alkaloid from the Colombian arrow-poison frog Phyllobates aurotaenia), bufotenine (a tryptamine-type) alkaloid from the common European toad), deoxy-nuphradine and castoramine from the (Canadian beaver (Castor fiber and muscopyridine from the scent gland of the musk deer ((Moschus moschiferus are other animal based alkaloids. Especially toad poisons, ,and the mystic around it

would require a separate study, as a lot can be learned from them, also taking benefit .from what nature has to offer SAMANDARIINE

Gallery

Dautora stramonium var.tatula, flower

D. stramonium var.tatula

(D. stramonium var.tatula, flower (front

(D. stramonium var.tatula, flower (side

D. stramonium leaves

D. stramonium var.tatula, fruit

D. stramonium seed

References
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McNaught and A. Wilkinson. Blackwell Scientific Publications, Oxford

R. H. F. Manske. The Alkaloids. Chemistry and Physiology. Volume VIII. - New.3 York: Academic Press, 1965, p. 673 Robert Alan Lewis. Lewis' dictionary of toxicology. CRC Press, 1998, p. 51 ISBN 1-56670- ^.4 223-2
a b c d

Chemical Encyclopedia: alkaloids ^.5

Rhoades, David F (1979). "Evolution of Plant Chemical Defense against Herbivores". In ^.6 Rosenthal, Gerald A., and Janzen, Daniel H. Herbivores: Their Interaction with Secondary .Plant Metabolites. New York: Academic Press. p. 41. ISBN 0-12-597180-X
a b c

Robert A. Meyers Encyclopedia of Physical Science and Technology, Eighteen-Volume ^.7 Set, Third Edition. - AlkaloidsISBN 0-12-227411-3

Leland J. Cseke Natural Products from Plants Second Edition. - CRC, 2006, p. 30 ISBN 0- ^.8 8493-2976-0 A. William Johnson Invitation to Organic Chemistry, Jones and Bartlett, 1999, p. 433 ISBN ^.9 0-7637-0432-6 Raj K Bansal A Text Book of Organic Chemistry. 4th Edition, New Age International, 2004, ^.10 p. 644 ISBN 81-224-1459-1
a b c d

Aniszewski, p. 110 ^.11

Biographical information about German pharmacist Carl Friedrich Wilhelm Meiner (1792- ^.12 1853) is available in the German .(Wikipedia: http://de.wikipedia.org/wiki/Carl_Friedrich_Wilhelm_Mei%C3%9Fner (in German Hesse, pp. 13
a b

^.13

Hesse, p. 5 ^.14

The suffix "ine" is a Greek feminine patronymic suffix and means "daughter of"; hence, for ^.15 example, "atropine" means "daughter of Atropa (belladonna)". See:https://webspace.yale.edu/chem125/125/history99/5Valence/Nomenclature/alkanena . mes.html Hesse, p. 7
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