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    Plant Steroids: Anna Drew

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    harishkumar kakrani
    This document summarizes plant steroids, including their structure, sources, and commercial uses. Plant steroids are derived from sapogenins found in plants like yams, fenugreek seeds, and sisal leaves. The most common sapogenins are tigogenin, diosgenin, and hecogenin, which have a steroid nucleus and sugars attached. Diosgenin is widely used commercially because it can be converted to progesterone and other steroids. Extraction involves hydrolysis, solvent extraction, and recrystallization. Plant steroids are important precursors for corticosteroids, contraceptive pills, and other steroid drugs.

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    Plant Steroids: Anna Drew

    Uploaded by

    harishkumar kakrani
    148 views20 pages
    This document summarizes plant steroids, including their structure, sources, and commercial uses. Plant steroids are derived from sapogenins found in plants like yams, fenugreek seeds, and sisal leaves. The most common sapogenins are tigogenin, diosgenin, and hecogenin, which have a steroid nucleus and sugars attached. Diosgenin is widely used commercially because it can be converted to progesterone and other steroids. Extraction involves hydrolysis, solvent extraction, and recrystallization. Plant steroids are important precursors for corticosteroids, contraceptive pills, and other steroid drugs.

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    Plant steroids an introduction

    Original Title

    Plant Steroids

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    © Attribution Non-Commercial (BY-NC)

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    This document summarizes plant steroids, including their structure, sources, and commercial uses. Plant steroids are derived from sapogenins found in plants like yams, fenugreek seeds, and sisal leaves. The most common sapogenins are tigogenin, diosgenin, and hecogenin, which have a steroid nucleus and sugars attached. Diosgenin is widely used commercially because it can be converted to progesterone and other steroids. Extraction involves hydrolysis, solvent extraction, and recrystallization. Plant steroids are important precursors for corticosteroids, contraceptive pills, and other steroid drugs.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    148 views20 pages

    Plant Steroids: Anna Drew

    Uploaded by

    harishkumar kakrani
    This document summarizes plant steroids, including their structure, sources, and commercial uses. Plant steroids are derived from sapogenins found in plants like yams, fenugreek seeds, and sisal leaves. The most common sapogenins are tigogenin, diosgenin, and hecogenin, which have a steroid nucleus and sugars attached. Diosgenin is widely used commercially because it can be converted to progesterone and other steroids. Extraction involves hydrolysis, solvent extraction, and recrystallization. Plant steroids are important precursors for corticosteroids, contraceptive pills, and other steroid drugs.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    of 20

    Plant steroids

    Anna Drew
    with grateful acknowledgement for inspirational teaching received at
    The School of Pharmacy, University of London
    PLANT STEROIDS
    • Used for:
    – replacement therapy (male +female)
    – athletes (glucocorticoids)
    – skin conditions (hydrocortisone)
    – antifertility pill (oestrogens + progesterones)
    – cancer (breast, testes, prostrate)
    – rheumatoid arthritis

    • Industrial demand may be met by plant sources


    or replaced by synthetic sources (expensive)
    Structure
    • Hydrocarbons
    – (3 x 6C) + (1 x 5C) = tetracyclic triterpenoid type
    – ring junctions sometimes contain 3y methyl groups

    – normally side chains are at C17 (classified by this)


    – and functional groups at C3 (-O or -OH groups)
    – also at C11 (-O, –OH gives oxygen function)
    – shape very important for biological activity
    – 3D determined by ring junction AB – CD

    Trans AB Cis AB
    isomer isomer

    • AB-CD trans junction tend to have a flat, planar


    structure
    – important for hormonal activity
    • AB-CD cis junction are bent or buckled
    – allows them to fit on heart / smooth muscle and blood
    protein receptor sites
    – poisonous steroids – some used in heart disease
    Hormones – plant sources
    • GROUP 1 sapogenins • GROUP 2 phytosterols

    • occur as glycosides • occur as ester linked to


    linked to a sugar fatty acids
    • polar, soluble in alcohol • non-polar, soluble in
    and alcohol/water hexane and petroleum
    mixtures spirits
    • occur in leaves -> roots, • occur in fruits and seeds
    rhizomes

    Occur in very large amounts in plants


    – 10-25% by weight of plant material
    Sapogenins
    • Sapogenin = steroid nucleus
    • Saponin = glycosides + sugars

    – ‘soap-like’ in nature
    – have been used to poison fish
    • accumulates in gills preventing O2 transfer
    – also frogs and toads
    • breathe through skin and hence are killed
    • not poisonous to mammals when eaten
    – not absorbed in intestine or stomach
    – may irritate bowel causing diarrhoea
    – few effects
    • if injected different
    – used in arrow poisons
    – cause haemolysis of red blood cells
    • breaks down red blood cell membrane
    • haemoglobinuria
    • some used as emulsifying agents
    • interested in the aglycone from a saponin

    • Saponins occur widely in plants


    – some economically important ones:

    Sources:
    [1] Dioscoreaceae (yam family)
    • Dioscorea genus – dicots – vines
    – sweet yam – food source, very low steroid content
    – bitter yam – Mexico, South America – high content
    [2] Liliaceae family
    • monocots – Far East, Phillipines
    – Smilax or Yucca
    • very important since these provide sapogenins for manufacture of
    corticosteroids

    [3] Amaryllidaceae
    • Agave sisalana sisal leaf, East Africa

    [4] Solanaceae
    • can be used when supply of [1] and [2] short or too expensive
    • Solanum sp. contain steroidal saponins
    – as well as tropane alkaloids, atropine, etc
    – eg tomato, potato, woody nightshade

    [5] Scrophulariaceae
    • Digitalis seeds full of steroids, rich source

    [6] Leguminosae
    • Trigonella-foeum-graecum fengreek seed
    Structure:
    – based on steroid nucleus
    • flat trans- shape
    – right shape steroid to make hormones
    – occurs in a high concentration in plants
    – spiroketal side chain easily oxidised off (leaves unstable
    progesterone)
    • spiroketal side chain at C17
    • 2 isomers at C25 due to free rotation around it
    – no other isomers occur naturally

    25 α 25 β
    iso-series neo-series

    • sugars attach at C3 to make sapogenins saponins


    – tend to have quite large molecular weight
    » eg 3-12 sugars = polysaccharide side chain
    – common sugars: xylose, galactose, rhamnose, glucose
    – combination of these sugars is usually a branched
    complex structure with high mol wt (ie not linear sugar
    chains)
    – lipid soluble steroid part + water soluble sugar part
    » can orientate at water|oil or air|water interface
    Tigogenin

    Structure courtesy of
    www.chemblink.com

    – simplest sapogenin
    – has correct configuration from which to make steroids
    – occurs with the isomer neotigogenin
    – widely distributed in plants:
    • yam, digitalis seeds, fenugreek seeds
    Diosgenin

    Structure courtesy of
    www.chemblink.com

    – can obtain prednenolone and progesterone from it


    – occurs with isomer yamogenin
    – occurs with some tigogenin in
    • fenugreek seeds and Mexican wild yam Dioscorea mexicana
    (and Japanese types)
    – hard to cultivate yams – tubers underground – may
    take years to grow large enough – mostly taken from
    wild
    Hecogenin

    Structure courtesy of
    www.chemblink.com

    – from the sisal plant, various species of yucca


    • Philipines and Far East
    – isomer is sisalgenin
    – keto function at C12 important
    – corticosteroids have C11 =O group giving activity
    – here C11 cannot be substituted; C12 =O enables
    halogenation at C11, then =O removed at C12
    Commercial extraction
    • sources crushed
    – tubers – yams; seeds – fenugreek, digitalis; leaves –
    sisal
    • fermentation
    – add excess water in fermenting vat and leave 24-48
    hour
    – saponins are covalently bonded into cellulose wall
    – own enzymes act on the polysaccharides in the cell
    wall to liberate them
    • filtration to collect plant powder
    • acid hydrolysis to split off saponins from sapogenins
    – equal HCL, MeOH, H2O
    • plant material dried in an oven
    • Soxhlet extraction with petroleum spirit
    – to distill over saponins
    – crystallise out in receiver
    – 10g/100g yam tuber – high yield – economic
    • recrystallise
    – using various solvents depending on desired
    compound
    – can be carried out on a large scale
    – cheap
    • no chromatographic process
    • materials cheap (H2O, HCl) – petroleum spirit can be
    recovered
    • recrystallisation expensive but gives a high yield
    • p’ceutical companies will buy compounds in pure
    Analysis of plant material
    • Qualitative:
    – TLC on sulphuric acid to indicate spot position
    (chloroform solvent)

    • Quantitative:
    – i) colorimetric assay – sulphuric acid produces orange
    colour with steroids
    – ii) IR spectrometry – 960cm-1
    – need a lot of plant material
    – iii) GLC micromethod – draw up assay with suitable
    standard and do many samples in one day
    – quickest
    – qualitative and quantitative
    Commerical use
    • production of steroids from diosgenin

    • before 1940 isolate from animal glands or urine


    – expensive

    • 1940 Marker (USA) discovered a process –


    essentially same process is still used

    • diosgenin extracted from Mexican yam


    • then spiroketone chain is opened up....
    • in theory process gave 100% yield
    • progesterone known to prevent ovulation – tried to
    produce ‘the pill’ (1950)
    • now have combination pills

    • 1950-1960 corticosteroids needed


    – antiinflammatory, anticancer, antirheumatoid
    • hydrocortisone and cortisone (which can be fluorinated)
    couldn’t be produced from progesterone

    [1] Fermentation
    – arose by accident when making antibiotics from Rhizopus
    – needed steroids in medium to grow
    – produced 11 keto progesterone
    – analysed fermentation to confirm pregnenolone / progesterone
    were producing 11 keto progesterone (from which
    hydrocortisone can be made)
    – biotechnology expensive
    [2] Hecogenins
    – more economical

    11 keto
    progesterone Marker
    tautomers
    11 keto
    diosgenin
    hydrocortisone
    – NB Diosgenin can be used to produce hydrocortisone but a
    fermentation stage is needed to introduce O- at C 11 keto α position of
    pregnane nucleus

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