4. Alcaloides - UTM · Alcaloides 1 . 2 Two hundred years of scientific research as not yet fully explained the connections between alkaloids and life, nor has it explained why these

4.1 Ocurrencia

4.2 Función de los alcaloides en plantas

4.3 Clasificación

4.4 Nomenclatura

4.5 Aplicaciones

4.6 Aislamiento

4.7 Pruebas cualitativas

4.8 Métodos generales de elucidación estructural

Maestría en Ciencias: Productos Naturales y

Alimentos

Química de Productos Naturales

4. Alcaloides

1

2

Two hundred years of scientific research as not yet fully explained the

connections between alkaloids and life, nor has it explained why these

diverse chemicals are produced and degraded by organisms, or why they

have such a very large spectrum of biological activities. Alkaloids are the

products of the life process, and their diversity is similar to the diversity

of life on Earth. Therefore, they can be said to encapsulate the very

secrets of life.

Tadeusz Aniszewski

24 June 2006

cocaine

ornithine

(-)-hyoscine(scopolamine)

3

lobelanine

Lys

N-methylpelletierine

4

salsolinol

mescaline

nicotinic acid nicotine

Tyr

5

harmine

physostigmine (eserine)

tryptophan

6

peganine (vasicine)

anthranilic acid

7

Alkaloids derived from ornithine

Medicinal Natural Products. Paul M. Dewick, 2002 John Wiley & Sons, Ltd. England. 8

Medicinal Natural Products. Paul M Dewick, 2002 John Wiley & Sons, Ltd. England. 9

En las aminotransferasas, el piridoxal fosfato forma

bases de Schiff intermediarias

10

11

12

13

Mecanismo de transaminación

14

15


17

(-)-hygrine

putrescine

Erythroxylon coca

cocaine

Alkaloids derived from ornithine

18

cuscohygrine

putrescine

Extracted from plants of the family Solanaceae

Atropa belladonna Datura inoxia Datura stramonium

19

tropine

(-)-hyoscyamine

L-Phe

20




Pyrrolizidine alkaloids

Bioactive compounds in foods. Edited by J. G. Hamide Z. Şenyuva. John Wiley & Sons Ltd. 2007, UK.

1

2

8

6

7

5 43

Pyrrolizidine alkaloids are found mainly in

the families Compositae (Asteraceae),

Boraginacea, and Leguminosae, but also

in Apocyanacae, Ranunculacae, and

Scrophulariacae.

The genera Senecio, Eupatorium,

Symphytum, Cynoglossum, Heliotropium,

and Crotalaria contain the species most

frequently associated with human illness.

24

Bioactive compounds in foods. Edited by J. G. Hamide Z. Şenyuva. John Wiley & Sons Ltd. 2007, UK. 25



Symphytum officinale

28

Alkaloids derived from lysine


Medicinal Natural Products. Paul M Dewick, 2002 John Wiley & Sons, Ltd. England.

lobeline

lobelanine

L-Lys

N-methylpelletierine

30


piperine

32

Medicinal Natural Products. Paul M Dewick, 2002. John Wiley & Sons, Ltd. England. 33

Quinolizidine Alkaloids

(-)-lupinine

34

Lupinus luteus


Indolizidine Alkaloids

36


swainsonine castanospermine

Swainsona canescens

(Leguminosae/Fabaceae)

Castanospermum australe, moreton Bay

chestnut (Leguminosae/Fabaceae)

37

swainsonine castanospermine

Polyhydroxyindolizidines such as swainsonine and castanospermine have demonstrated activity

against the AIDS virus HIV, by their ability to inhibit glycosidase enzymes involved in glycoprotein

biosynthesis. The glycoprotein coating is essential for the proliferation of the AIDS virus. This has

stimulated considerable research on related structures and their mode of action. The ester 6-O-

butanoylcastanospermine is currently in clinical trials as an anti-AIDS agent.

6-O-butanoylcastanospermine

38

39

Alkaloids derived from nicotinic acid

Pyridine Alkaloids

Nicotiana tabacum

(Solanaceae), an annual herb

indigenous to tropical America,

but cultivated widely for smoking.

Tobacco leaves may contain from

0.6–9% of (-)-nicotine.

40

41

Nicotiana tabacum

42

Pyridine Alkaloids


43 Medicinal Natural Products. Paul M Dewick, 2002 John Wiley & Sons, Ltd. England.




47

salsolinol

mescaline

Tyr

Lophophora williamsii (Cactaceae)

Corydalis spp. (Papaveraceae)


Alkaloids derived from tyrosine

Phenylethylamines and simple tetrahydroisoquinoline alkaloids



50

morphine(R)-reticuline

Tyr

Papaver somniferum (Papaveraceae)


51

Alkaloids derived from tryptophan

Simple Indole Alkaloids

These two compounds are responsible for the hallucinogenic properties of so-called

magic mushrooms, which include species of Psilocybe∗, Panaeolus, etc.

Psilocybe Panaeolus

psilocybin psilocin

52

54

55

Barley

Hordeum vulgare

gramine

56

Pyrroloindole Alkaloids

Physostigma venenosum

(Leguminosae/Fabaceae)


57

Flustra foliacea

(flustramines)

58

Ergot Alkaloids


59

Cinchona (Rubiaceae)

Quinoline Alkaloids


60

Alkaloids derived from Histidine

Imidazole alkaloids


61

The Dragendorff Reagent

Two stock solutions are prepared: 0.6 g bismuth subnitrate in 2 mL concentrated

HCl (37% w/v) and 10 mL distilled water, and 6 g potassium iodide in 10 mL

distilled water. These stock solutions are mixed together with 7 mL HCl (37% w/v)

and 15 mL distilled water and diluted to 400 mL with distilled water. Dragendorff

reagent gives orange-brown spots on a yellow background.

4.7 Pruebas cualitativas

62

Mayer’s reagent. K2HgI4

(potassiomercuric iodide solution)

Wagner’s reagent (iodine dissolved in potassium iodide)

Hager’s reagent (saturated solution of picric acid in water)

Chloropatinic acid (H2PtCl6)

Frohde’s reagent (molybdic acid)

63

Introduction to Mass Spectrometry

64

Una uma es igual a 1.66054 x 10-24 g

65

66

Basics

Mass spectrometry is based on slightly different principles to the other spectroscopic

methods.

67

Triple cuadrupolo

(QqQ)

Rubinson, K. A.; Rubinson, J. F. 2001. Análisis instrumental. Pearson Editorial, S. A. 1ra. edición. Madrid, España.

Kotretsou, S. I.; Koutsodimou, A. Food Reviews International. 2006, 21, 3, 125-164. 68

69

The Mass Spectrum

Masses are graphed or tabulated according to

their relative abundance.

70

71

de Andrade, J. P.; Pigni, N. B.; Torras-Claveria L.; Berkov, S; Codina, C.; Viladomata, F.; Bastida. J. Bioactive alkaloid extracts from

Narcissus broussonetii: Mass spectral studies. Journal of Pharmaceutical and Biomedical Analysis. 2012, 70, 13–25.

72

de Andrade, J. P.; Pigni, N. B-; Torras-Claveria L.; Berkov, S; Codina, C.; Viladomata, F.; Bastida. J. Bioactive alkaloid extracts from

Narcissus broussonetii: Mass spectral studies. Journal of Pharmaceutical and Biomedical Analysis. 2012, 70, 13– 25.

73



Tentative fragmentation of obliquine (21).

74



ESI-MS/MS of the [M+H]+ ions of obliquine (21).

75



Tentative fragmentation of plicamine (22).

76



ESI-MS/MS of the [M+H]+ ions of plicamine (22).

77

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4. Alcaloides - UTM · Alcaloides 1 . 2 Two hundred years of scientific research as not yet fully explained the connections between alkaloids and life, nor has it explained why these