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INTRODUCTION
Crude drugs (herbs) & galenical products orphytomedicinals are widely used in complementary medicine !about "#$ o%
the total drug maret'
harmacognosy * nowledge o% drugsgi+es a scienti,c description o% natural
materials used in medicine (herbs- animalproducts & inorganic materials)
hytochemistry studies the chemistry-distribution- isolation- identi,cation-
.uantitati+e determination- biosynthesis-metabolism & biological acti+ity o% plant
constituents
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Role o% natural products inmodern medicine
Use%ul drugs which cannot be commerciallyproduced by synthesis eg opium- ergot &cinchona alaloids- digitalis glycosides & mostantibiotics
/asic compounds- which could be modi,ed to bemore e0ecti+e or less to1ic eg morphinemolecule
2odels %or production o% synthetic analogues with
similar physiological acti+ities- eg procaine
3tarting materials %or production o% potent drugseg hydrocortisone & steroidal hormones %romstigmasterol & saponins
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Di0erent %orms o% plantproducts
4 5resh plant materials !especially in per%ume industry'6 Dried plant materials7 !8a+oring agents- spices &
drugs where dosage is not critical'
9 :cellular products 7 materials deri+ed directly %romplants !gums- resins- & ,1ed & +olatile oils'
;
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Nomenclature o% plantconstituents
Root names are deri+ed %rom74 Name o% the disco+erer eg elletierine
alaloid a%ter elletier
6 Common name o% the plant eg +incaalaloids- (+incristine & +inblastine)- ergotalaloids (ergometrine & ergotamine)
9 @atin name o% the plant eg +isnagin %rom Ammi visnaga & digito1in %rom Digitalis lanata
; /iological action eg emetine alaloid whichproduces emesis
3ystematic nomenclature is diAcult due tocomple1ity o% structure Naming is based on tri+ial nomenclature
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Classi,cation o% plantconstituents
lant constituents occur as7
♣
3ingle chemicals eg glycosides &alaloids BB
♣2i1tures o% compounds eg gums-,1ed oils- %ats- wa1es- +olatileoils- resins & resin combinations
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Classi,cation o% plantconstituents may be according
to:: harmacological acti+ity [analgesics, laxatives, cardiotonicsetc……..]
/ /iosynthetic origin, solubilityproperties & ey %unctional groups
C Chemistry & common physicalproperties
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4 henolics7 eg 8a+onoids & their glycosides-phenyl propanoids- anthocyanins- 1anthones-
tannins & .uinones
6 Terpenoids7 eg carotenoids- steroids & the
maor constituents o% +olatile oils 9 Organic acids & lipids7 eg simple organicacids (citric- o1alic & ascorbic)- %atty acids (inthe %orm o% esters in ,1ed oils- %ats & wa1es)
; Nitrogenous compounds7 eg alaloids &
cyanogenic glycosides" aterEsoluble carbohydrates & their
deri+ati+es7 eg monosaccharides-oligosaccharides & waterEsoluble glycosides
> 2acromolecules7 eg proteins &
polysaccharides
/:ccording to biosynthetic origin,solubility properties & ey %unctional
groups7
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C:ccording to chemistry & commonphysical properties
This classi,cation will be adopted %or
con+enience- the maor groups are7
4Folatile oils- Resins & Resin
combinations
6Carbohydrates
9/itter rinciples
;Tannins
":laloids
>
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FO@:TI@?- ?TG?R?:@ or ?33?NTI:@OI@3
Folatile or ethereal7 as they easily
e+aporate on e1posure to air at roomtemperature (+olatile- %rom the @atin"volare" ie to 8y & ethereal * etherElie in their +olatility)
?ssential7 as they mostly represent
the essences or principal acti+eprinciples o% the plants in which they
occur
They di0er entirely %rom ,1ed oilsH inboth chemical & physical properties.
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roperty Folatile oil 5i1ed oil
Folatili=ation atordinarytemperature
Folatile NonE+olatile
3olubility 3oluble inorganic sol+ents(ether- CGCl
9) &
alcohol
@imitedsolubility inorganicsol+ents- almost
insoluble inalcohol
3tain on ,lterpaper
Transient ermanent &greasy
Composition Comple1mi1tures o%hydrocarbons &o1ygenatedcompounds
Triglycerides o%%atty acids egpalmitic- stearic-
oleic……..
Response tolong e1posure toair & light
(o1idation)
Resini,cation Rancidity
2aor Di0erences between +olatile & ,1edoils
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Gistorical
In ancient ?gypt7 embalming process(antibacterial properties o% essential oils &
resins)
In the Roman culture7 aromatic essences inmassage & baths
Incenses7 !in temples- churches & mos.ues'consist o% resins rich in +olatile oils
In %ol medicine7 inhalation o% aromatics astran.uili=ers (eg incenses in case o%
irritability) or stimulants (eg onions in caseo% %ainting)
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Distribution & Occurrence
:nimal sources:
2us - musElie
products (ci+et-castoreum) &
ambergris
3ecretionsproduced %orattraction or
protection
/otanical sources:
2ainly in higherplants
?specially ininaceae- @auraceae-Rutaceae- 2yrtaceae-
@abiateae-Jingiberaceae-Umbelli%ereae- &Compositeae
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5ree & Combined 5orms o% FolatileOils
They may be present 7
4 5ree → aromatic characteristic odor- or
6 Combined with7
3ugars → glycosides
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@ocation in the plant
4 2odi,ed parenchyma or oil cells7
(@auraceae & Jingiberaceae)
6
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Distribution in plant organs
F O may accumulate in alltypes o% plant organs7
♣ 5lowers eg rose
♣ @ea+es eg eucalyptus &peppermint
♣ /ars eg cinnamon
♣ oods eg sandalwood
♣ Roots eg +eti+er♣ Rhi=omes eg ginger
♣ 5ruits eg umbelli%erous & citrus
♣ 3eeds eg cardamon
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Variation in composition of v. oils fromdierent organs of the same plant
4 Cinnamon tree7→ bar oil rich in cinnamaldehyde→
lea% oil rich in eugenol→
root oil rich in camphor
6 /itter orange tree7 → /itter orange oil7 %rom the %resh pericarp
o% the %ruit (rind or =est)-
→ Neroli oil7 %rom the 8owers→
etit grain oil7 %rom the lea+es- twigs &unripe %ruits
These oils are di0erent in composition &
aroma
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hysiological role o% FO in theplant
4 aste products o% metabolism
(deto1i%ying agents)
6 ?nergy producers in case o% de,ciency
%rom CO6 assimilation9 GK donors in certain metabolic reactions
; rotectants against predators7 eg
insect repellents & anti%ungals (ie %or
de%ense)
" ollinators7 attracting insects during
crossEpollination (due to their nice
odors)
C h i l
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Common hysicalCharacters
4 Colorless- pleasant smelling li.uids-+olatile at room temperature
6 3team distillable9 Gigh re%racti+e inde1
; 2ostly optically acti+e" Density L water (ie lighter than
water) e1cept %or %ew ones> Immiscible with water- but suAciently
soluble to impart a %ragrance to water
→ aromatic waters !hydrosols'M 3oluble in alcohol & common organic
sol+ents Daren in color i% e1posed to air &
light (resini,cation)
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?1ceptions
4 Oils o% cinnamon- clo+e & wintergreen are hea+ier than water
6 Oils o% anise & rose solidi%y ustbelow room temperature (4" &
4oC- respecti+ely)
9 Oils containing a=ulenes are colored (eg oil o% chamomile is blue)
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Chemical Composition
♣ F O are comple1 mi1tures o% hydrocarbons
& o1ygenated compounds !alcohols- phenols-ethers- aldehydes- etones- o1ides-
pero1ides & esters' :ll o% these contribute to
the odor & physiological acti+ity o% the oil
♣ 5ew oils consist o% one main component eg 4 Oil o% mustard (9$ allylisothiocyanate)
6 Oil o% clo+e ("$ eugenol)
♣ 2ost F O constituents belong to 6 main
groups7
4 Terpenoids !deri+ed %rom acetate' &
6 henylpropanoids !aromatic compounds-
deri+ed %rom phenylpropane'
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Fariation in hysicoEChemicalCharacteristics
2ost important in8uencing %actors are7
♣The en+ironmental conditions underwhich the plant is grown
♣ The method used %or preparation o%the oil
2 di i l & C i l U %
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2edicinal & Commercial Uses o%FO.
4 Therapeutic & medicinal uses7 local stimulants-carminati+es- diuretics- mild antiseptics- local
irritants- anthelmintics- parasiticides B
6 3pices & condiments7 in %ood seasoning (to impart
aroma & 8a+or) or as preser+ati+es
9 5la+oring agents7 in %ood (eg be+erages- soups-
baery products- con%ectionery) & pharmaceutical
industries
; :romatic agents7 in all types o% per%ume industries
(cosmetics- soaps- deodori=ers- household cleaners-
polishes & insecticides)
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?1tractionDistillation
ater Distillation
Water & SteamDistillation
Direct Steam
Distillation
?1tractionwithFolatile
3ol+ents
?1tractionwithNonEFolatile
3ol+ents
Enflerage !ethod
"nematic !ethod
!aceration !ethod
3ponge 2ethod
?cuellea pi.uer2ethod
?1pression o%Rasping rocess
2achine rocesses
3teamDistillation
2ethods o% reparation o% Folatile Oils
?n=ymatic
Gydrolysis
3cari%ication&?1pression
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3election o% the suitable method isdone according to 7
4 The condition o% the plant material (moisturecontent- degree o% comminution)
6 The locali=ation o% the oil in the plant(super,cial or deep)
9 The amount o% the oil
; The nature o% the oil constituents
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Distillation methods
rinciple
♣ 2ost +olatile oil constituents boil between 4"#E9##PC In order to reduce decomposition- +olatile
oils are distilled in the presence o% water.
♣ The mi1ture will boil below 4##PC !DaltonQs lawo% partial pressure 7 Hhen 6 immiscible li.uids
are heated together- they will boil at atemperature below the boiling point o% either
one'
♣ The oil is carried o+er with steam in the %orm o%+apor
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Distillation methods
:pplication7 preparation o% thermostableoils- present in large amounts & not rich in
esters (eg oils o% turpentine- peppermint-
cardamon- anise- eucalyptus)
Types o% distillation7
4aterEdistillation
63team distillation aterEandEsteam distillation
DirectEsteam distillation
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Distillation7 Terminology
♣ Gydrodi0usion * process by which water or
steam penetrates the plant tissues to tae o+er
the oil
♣:romatic water * Gydrosols * distilled a.ueous
layer saturated with oil eg rose- orange 8ower
& peppermint waters
♣ Cohobation * return o% aromatic water to the
distillation chamber- in water distillation- in
order to reco+er the dissol+ed oil
Distillation methods
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Distillation methods
G6O
Distillation
3team Distillation
G6O & 3team Direct 3team
lant material Dried & %resh(petals)- notinured by boilingwith G6O
Dried & %resh-inured by directboiling with G
6O
5resh ( iecontaining moisture)
Commercialpreparations
Oils o% turpentine &rose
Oils o% clo+e-cinnamon &citronella
Oil o% peppermint
2ode o%charging
lant materialdipped in G
6O
EG6O present but not
in contact with theplant
E3team is generatedin the still &
penetrates the drugEDried material is
moistened be%orecharging
EG6O is absent
E3team is introduced bypipes & %orced through
the plant materialplaced on per%orated
trays
3teampressure
≈ atmospheric Can be modi,ed
Temperature ≈ 4##PC Can be modi,ed
Rate & yield Relati+ely low /etter The best
:d+antages E@east e1pensi+e Gydrolysis is 2ethod suitable %or oils
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Distillation apparatusConsists o% 9 parts7
4 The distillationchamber made o%
stainless steel %ree%rom any 5eKKK ions toa+oid degradation o%
the oil constituents → darer oils
6 The condensing system
9 The recei+er eg5lorentine recei+ers
which allow separationo% the oily layer %romwater in the distillate
(oils lighter or hea+ierthan water)
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5lorentineRecei+ers
uri,cation(Recti,cation) o%
distilled oils
/ad smelling or dar
colored oils are puri,ed
by74 Redistillation or dry
distillation under
reduced pressure
6 Dehydration by
passing o+er
anhydrous sodium
sulphate
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Remars
4 Distillation should be done ust a%ter comminution ! iereduction in si=e- crushing- powdering) → pre+ent loss by
e+aporation or deterioration o% the oil6 Coarse comminution → increase Gydrodi0usion → oils with
better yield & .uality
9 Gigh temperature & water → distilled oils di0ering incomposition %rom natural oils !arti%acts'
; InsuAcient distillation time (shorter) → %ractionation o% theoil
" Gydrolytic products (eg lower alcohols & acids) are waterEsoluble & remain in the distillation chamber
> 3team +olatile impurities eg amines & %ur%ural (degradation
product o% carbohydrates) contaminate the ,nal productM 3ensiti+e constituents could be a0ected by boiling water eg
♣ ?sters → hydroly=ed
♣ Tertiary alcohols → dehydrated → hydrocarbons
♣ Unsaturated hydrocarbons → polymeri=ed
3 i, ti & ? i
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3cari,cation & ?1pression2ethods
rinciple
2echanical procedures carried at roomtemperature & based on puncturing &
s.uee=ing o% the plant material toliberate the oil- which is collected
:pplicationsreparation o% heat sensiti+e oils- presentin large amounts in outer peels o% %ruits eg Citrus %ruits (Rutaceae) as orange-
lemon & bergamot
http://rds.yahoo.com/_ylt=A0geu5uyqrZHDyoBNA5XNyoA;_ylu=X3oDMTB0ZXRnYzZrBHNlYwNzYwRjb2xvA2FjMgR2dGlkA0gwNjZfMTI2/SIG=1eam2q3l4/EXP=1203239986/**http%3A//images.search.yahoo.com/images/view%3Fback=http%253A%252F%252Fsearch.yahoo.com%252Fsearch%253Fei%253DUTF-8%2526p%253Dpictures%252Bof%252Bcitrus%252Bfruits%26w=319%26h=216%26imgurl=www.kadagan.bz.tc%252Fimages%252Fcitrus.jpg%26size=32.8%26name=citrus.jpg%26rcurl=http%253A%252F%252Fwww.kadagan.bz.tc%252Fcustom2.html%26rurl=http%253A%252F%252Fwww.kadagan.bz.tc%252Fcustom2.html%26p=citrus%2Bfruits%26type=jpeg%26no=2%26tt=12%252C546http://rds.yahoo.com/_ylt=A0geu5uyqrZHDyoBNQ5XNyoA;_ylu=X3oDMTB0ZXRnYzZrBHNlYwNzYwRjb2xvA2FjMgR2dGlkA0gwNjZfMTI2/SIG=1gkt8b6q0/EXP=1203239986/**http%3A//images.search.yahoo.com/images/view%3Fback=http%253A%252F%252Fsearch.yahoo.com%252Fsearch%253Fei%253DUTF-8%2526p%253Dpictures%252Bof%252Bcitrus%252Bfruits%26w=500%26h=375%26imgurl=static.flickr.com%252F24%252F35413583_f2506f0655.jpg%26size=54.5%26name=35413583_f2506f0655.jpg%26rcurl=http%253A%252F%252Fwww.flickr.com%252Fphotos%252Fschattenbaum%252F35413583%252F%26rurl=http%253A%252F%252Fwww.flickr.com%252Fphotos%252Fschattenbaum%252F35413583%252F%26p=citrus%2Bfruits%26type=jpeg%26no=3%26tt=12%252C546
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3cari,cation & ?1pression2ethods
The peel o% Citrus %ruits consists o% 6 distinct layers74 Outer colored =one (wa1es K pigments K oil glands)
6 Inner white =one (pectin K cellulose)
http://en.wikipedia.org/wiki/Image:NIH_citrus.jpg
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3cari,cation & ?1pression2ethods
The process in+ol+es 9 steps7
4 3.uee=ing o% the peel under astream o% water → emulsion
(+olatile oil K water K pectin Kcellulose K pigments K traces o%wa1es)
6 Centri%ugation (to remo+e water Kpectin K cellulose)
9 3trong cooling (to remo+e wa1es)
3 i, ti & ? i
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3cari,cation & ?1pression2ethods
:E 3ponge 2ethod
/ased on s.uee=ing the remo+ed peels eg orange
4 5ruits washed- cut into hal+es & 8eshy parts
remo+ed6 eels soaed in water- turned inside out then
pressed between a con+e1 proection & a sponge
9 3ponge (saturated with oil emulsion) periodicallys.uee=ed in a +essel
The tissue o% the sponge ser+es %or7
4 Collection o% the oil
6 5iltration o% the product %rom any particles o% the
inner white =one o% the peel
3 i, ti & ? i
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3cari,cation & ?1pression2ethods
/E ?cuelleESEpi.uer method
/ased on puncturing (scari%ying) the sur%ace o% whole%ruits (lemon)- the oil e1udes %rom the outer =one o%the peels in the %orm o% emulsion
The instrument is %unnelEshaped-%ormed o% a shallow bowl with atubular proection at the centerThe bowl bears numerous pins
which scari%y the oil glands torelease the oil
The tubular part ser+es as7
4 Gandle to rotate the instrument
6 Recei+er to collect the oil
3cari,cation & ?1pression
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3cari,cation & ?1pression2ethods
CE ?1pression o% rasping process /ased on remo+al o% the outer layer o% the
peel with a grater- collecting the rasping in special bags then strong pressing
The oil emulsion is collected in large+essels
DE 2achine processes /ased on the same principles as the abo+e
9 traditional methods :- / & C but carriedout by machines
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3ol+ent e1traction methods
rinciple
/ased on e1traction o% the +olatile oil%rom the plant material with a suitablesol+ent
:ccording to the nature o% the sol+ent used- three types are distinguished7
4Folatile sol+ent e1traction6NonE+olatile sol+ent e1traction
93upercritical 8uid e1traction
3ol+ent e1traction methods
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3ol+ent e1traction methodsE:pplication
reparation o% delicate8ower oils eg asmine-
+iolet- tuberose &
narcissus which are7
4resent in +ery small amounts- not easily
obtained by distillation
or e1pression
6Oils %ormed o%
thermolabile
constituents (ie
easily decomposed by
l il l i
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Folatile sol+entEe1traction
reparation o% 8oral concretes4 3ol+ents used7 petroleum ether & nEhe1ane
6 ?1traction (Hpercolation or Hmaceration at roomtemperature- Hcontinuous hot e1traction in a 3o1hletapparatus at constant temperature)
9 3ol+ent remo+al (distillation under reduced pressure)
3o1hletapparatus
ercolator
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Folatile sol+entEe1traction
5loral absolute * consists mostly o% the o1ygenated constituents o% the oil
♣2ore e1pensi+e & puri,ed than the
corresponding concrete
♣reparation7 repeated e1traction with
absolute alcohol
♣ Impurities7 remo+ed by strong cooling &
,ltration
5loral concrete * 5ragrant constituents K
5ats K a1es K :lbuminous matter K 5atsoluble pigments eg 8oral concrete o%
asmine is semiEsolid & yellowishEorange in
color
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NonE+olatile sol+ent e1traction
3ol+ents7 @ipids o% high degree o% purity eg ♣ 5ats (lard 7 tallow in a mi1ture 674) ♣ 5i1ed (oli+e oil)
Techni.ues7 ♣ ?n8eurage (hot & cold)♣ neumatic method♣ 2aceration (in ,1ed oils)
:pplication7 reparation o% natural 8oweroils producing the ,nest per%umes
rinciple7 based on the liposolubility o%+olatile oils
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?n%leuragerocess
5lower etals
:dd %at mi1ture
!@ard &tallow(6 7 4)'
4) ?n%leurageroduct(%loral pomade)!5atsaturated withoil'
:ddabsolutealcohol Triplee1traction Cooling (remo+e most o% %at)
6) Triple e1tract!alc solutiono% +ol oil Kpigments Ktraces o% %ats'
?+aporation o% alcoholor %ractional distillation
Dilution withG#O KNaCl
9):bsolute o% ?n%leurage!3emiEsolid- alcoholE%reeproduct'
;)Folatileoil
Vasmine8owers
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“?n8eurage rocess
Cold ?n8eurage
Got ?n8eurage
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3uper critical 8uid e1traction
rinciple7 based on using li.ue,ed gases eg CO6
under speci,c temperatures & pressures ase1tracting sol+ents Under these conditionsthese gases are li.uids but maintain thepenetrating properties o% gases & allow moreeAcient e1traction The oils obtained are o%closest composition to the natural oils
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rocess :pplications :d+antages Disad+antages
Distillation 5or dried & %resh
material- rich in
+olatile oils with
thermostable
constituents
Cheapest
method
(apparatus-
sol+ent & source
o% heat)
Gigh
temperature
& presence o%
water may a0ect
the constituents
3cari,catio
n &
?1pression
5or preparation o%
oils present in large
amounts in outer
peels o% %ruits &
rich in heatE
sensiti+e
constituents
ECarried at room
temperature
EWields oils with
more natural
odors
?1pensi+e due to
need o% high
number o%
worers
?1traction 3uitable %or
%resh material with
heatEsensiti+e oils
present in small
amounts
ECarried at room
or low
temperature
EWields oils with
?1pensi+e due to
use o% sol+ent &
or high number
o% worers
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2ethods based on en=ymatichydrolysis o% glycosides
The +olatile aglycones are nownas the
essential oils o% the plants eg
4 2ethyl salycilate $ oil o%wintergreen
6 :llyl isothiocyanate $ +olatile oilo% blac mustard
9 /en=aldehyde * +olatile oil o%bitter almond
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2ethods based on en=ymatichydrolysis o% glycosides7 rinciple
4 lant material K en=ymatic hydrolysis → +olatile aglycones in the hydrolysate
6 Gydrolysate K distillation or e1traction with organic sol+ent → +olatile aglycone
5i1ed oil i% present in large amount in the plantmaterial
should be remo+ed by e1pression be%orehydrolysis
?1amples o% glycosides with +olatile
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aglycones
lant nameNonE+olatile
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reparation & puri,cation o% +olatile oilo% bitter almond
4 3eeds crushed & ,1ed oil remo+ed by e1pression
6 Cae macerated in water %or %ew hours- at ;#PC in a closed +essel
:mygdalin → hydrolysis (:mygdalase K ?mulsin) → /en=aldelhyde K 6 glucose K GCN
9 3team distillation → ben=aldehyde K GCN (%ree state or asben=aldehyde cyanohydrin)
uri,cation o% bitter almond oil or Remo+al or ,1ation o% GCN
/y trans%ormation to the nonE+olatile Ca65e(CN) > 7 Impure
distilled oil K Ca (OG)6 K5e3O;K redistillation
Detection o% residual GCN in the puri,ed oil
russian blue test7 Oil K NaOG (ts) & shae- i% any traces o%GCN → NaCN K 5e3O; (traces o% 5eKKK ions) K GCl & warm → 5e; 5e (CN)>'9 (%erric %erro cyanide)- bluish blac in color
2 HCN + Ca (OH) 2 Ca (CN)2 + 2H2O
Volatile Non-volatile
3 Ca (CN) 2 + FeSO4 Ca2 Fe (CN)6 + CaSO4
Non-volatile
Determination o%
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Determination o%percentage o% +olatileoil in plant material
2iscibility with alcohol
4 2ost +olatile oils are
miscible with absolute
alcohol
6 Oils highly miscible with
alcohol o% lowconcentrations are
usually rich in
o1ygenated constituents
9 Decreased miscibility
with alcohol o% low
concentrations →
adulteration with nonE
polar sol+ents egetroleum ether
$ +w * Fol o% oil Y 4## t o%
drug
h i l ? i ti h l i l ti % th il
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hysical ?1amination7 helps in e+aluation o% the oilsample & detection o% adulterants
Odor
Detection o% any abnormal odor (by
smelling 4 or 6 drops o% the oilapplied on a ,lter paper)
→
adulteration or deterioration duringstorage
eg orange oil ac.uires a caraway odor onbad storage due to auto1idation o%limonene to car+one & car+eol
3olubility
4 Oils are soluble in nonEpolar sol+entsas ben=ene- carbon disul,de & lightpetroleum
6 :ny turbidity→
moisture
3peci,c gra+ity
:pparatus7 pycnometer (speci,c gra+ity
bottle)
3p gr gi+es an indication on composition
4 Oils with sp gr L #- rich inhydrocarbons & aliphatic compounds
6 Oils with sp gr Z 4#- rich inaromatic & 3 compounds
9 Oils with # Z sp gr L 4#- containdi0erent types o% constituents
Optical rotation !:pparatus7 olarimeter '
4 Determination helps in detection o%
adulteration & identi,cation o% the+ariety o% the sample eg
♣ 5rench oil o% turpentine is le+orotatory !l (E)' as it contains lEpinene in high concentration
♣ :merican oil o% turpentine is de1troratory !d (K)' as its maorconstituent is dEpinene
6
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ycnometer
olarimeter
:bbere%ractometer
Chemistry o% +olatile oils
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Chemistry o% +olatile oilsconstituents
Types o% constituents detected in +olatile oils7 F O are comple1 mi1tures %ormed o%7
4 Terpenoids (mainly monoE & ses.uiterpenoids)
6 henyl propanoids (C>EC9- aromatic)
9 :liphatic compounds (acyclic- straight chaincompounds which may be terpenoids)
; 2iscellaneous compounds eg organoEnitrogen
& organoEsul%ur compounds
♣ ?ach group includes nonEo1ygenated
(hydrocarbons) & o1ygenated compounds
♣ O1ygenated constituents are generally
responsible %or the characteristic odor o% the oil
Remo+al o% terpenoid
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Remo+al o% terpenoidhydrocarbons
♣ Oils rich in terpenoid hydrocarbons deteriorate rapidlyon storage due to o1idation & polymeri=ation → bad
smelling (with turpentineElie odor) & resini,ed
products
♣ Remo+al o% most terpenoid hydrocarbons →
terpenelessEoils by any o% the %ollowing methods7
4 5ractional distillation under reduced pressure7
hydrocarbons ha+e lower bp than o1ygenated
compounds- they distill ,rst & are reected
6 Column chromatography on silica gel7 hydrocarbons
are eluted with nEhe1ane then o1ygenated
compounds with absolute alcohol
9 3electi+e e1traction o1ygenated components with
dilute alcohol %ollowed by distillation
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“Terpeneless oils”
Oils %rom which most
terpenehydrocarbons are remo+ed
4 2ore e1pensi+e than
natural oils
6 Richer in o1ygenatedcompounds
9 2ore soluble in lowE
strength alcohols
; Used in smaller amountsto gi+e the same strength
o% odor
" 2ore stable being less
liable to deterioration
4 3tearoptene * solid%raction separating on
cooling a +o (pre+iously
nown as camphors)-
consists o% 4 or more solid
(mainly o1ygenated )compounds
6 Oleoptene * remaining
li.uid %raction- mainly
%ormed o% hydrocarbons
HFolatile oil isolates
♣:n isolate is a
single chemicalsubstance isolated
%rom the oilHOleoptene &3tearoptene
Isolation o% +olatile oil
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Isolation o% +olatile oilconstituents
♣ hysical methods (cooling- %ractionaldistillation- %ractional crystalli=ation &
preparati+e gas chromatography)
♣ Chemical methods depend on7
4 3olubility di0erences in acids or alalis
6 Deri+ati=ation (due to presence o%
%unctional groups)
9 :dduct %ormation (speci,c %or certain
compounds)
Chemical methods %or isolation o% FOtit t
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constituents
3olubility in alalis7 4Compounds containing ECOOG group (strongly acidic) K mild alali
(Na6CO9) → water soluble Na salts (decomposed by acids)
6henolic compounds (mild acids) K a.ueous NaOG or OG (strongalalis) → water soluble Na or phenates (decomposed by acids)→ phenol
Deri+ati=ation74:lcohols → esteri,cation → phenyl urethans or acid phthalates
6Carbonyl compounds → deri+ati+es eg crystalline bisul,tes-semicarba=ones- phenyl hydra=ones & o1imes
5ormation o% crystalline additi+e products4
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Terpenoids (Terpenes)♣ They constitute the largest nown group o%
secondary metabolites
♣ The term Hterpenes should better be used to
indicate the unsaturated hydrocarbons
♣ :ll yield isoprene as ,nal product o% destructi+e
distillation (* pyrolysis)
♣ Isoprene- a " carbonEatom unit- is the building unit
o% all terpenoids
C
CH2
C
H2C
CH3
Isoprene, 2-meth! ":3 #$ta%&ene,
",3
&sopentene
"
23
4
h
t '##re&ate% str$t$re
h*hea%, t*ta&!
Isoprene rule %or %ormation o%
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pterpenoids
♣ Theoretical biogenetic rule which states that7 H?achgroup o% terpenes originates %rom the headEtoEtail
condensation o% a +ariable number o% isoprene units
Isoprene
Isoprene
Isoprene
:cyclic ses.uiterpene
Isoprene:cyclic
monoterpene
2onocyclicmonoterpene
/icyclic2onoterpene
Isoprene
2onocyclic ses.uiterpene
Coupling o% isoprene units to yield monoE &
Terpenoids in ?ssential Oils
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Terpenoids in ?ssential Oils
♣ Thousands are identi,ed in essential oils
♣ 2ainly monoE or ses.uiterpenoids (+olatile & o%low molecular weight)
♣ :cyclic (ie aliphatic) or :licyclic (ie with nonEaromatic ringEstructures)
♣ Gydrocarbons or o1ygenated (alcohols- aldehydes-etones- esters- ethers- o1ides or pero1ides)
♣ O%ten optically acti+e occurring as dE- lE & dlisomers
2onoterpenoids (C 4#)
4 2ost abundant class o% essential oil constituents6 Consist o% 6 molecules o% isoprene
9 Gydrocarbons ha+e the empirical %ormula C4#G4>; :cyclic or alicyclic (mainly monoE & bicyclic)
Terpenoids in ?ssential Oils
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Terpenoids in ?ssential Oils3es.uiterpenoids (C4")
4 resent in the high boiling point %ractions o% the oils (6"#E
6#oC)
6 2ostly +iscous li.uids or may be crystalline
9 Consist o% 9 molecules o% isoprene
; Gydrocarbons ha+e the empirical %ormula C4"G6;
" :cyclic- monocyclic or polycyclic
> Occur in more than 4## di0erent seletons with ring si=e
ranging %rom ;- M- - 4# & 44 C atoms
:=ulenes (C4"G4)
4 Usually discussed under ses.uiterpenoids because they ha+ethe same number o% C atoms & distill in the same boiling
range
6 /ut- they possess aromatic properties due to high
conugation & are highly colored (generally blue- green or
+iolet) eg Chama=ulene in oil o% chamomile
Nomenclature o% terpenoids
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Nomenclature o% terpenoids♣ Chemical names are deri+ed %rom the corresponding saturated
hydrocarbon seleton
4 The acyclic monoterpenoids are 6- >Edimethyl octane(myrcane) deri+ati+es
6 2ost monocyclic monoterpenoids are paraEmenthane rarely
metaEmenthane deri+ati+es
9 /icyclic monoterpenoids are thuane- carane- pinane-
camphane or %enchane deri+ati+es
; :cyclic ses.uiterpenoids are trimethyldodecane
deri+ati+es
" 2onoE & polycyclic ses.uiterpenoids are bisabolane-
humulane- elemane- germacrane cadinane- santalane-
cedrane deri+ati+es etcB
> The number & position o% the double bonds are indicated
eg a double bond between C4 & C6 by 4 [ while a double
bond between C4 & C> by 4(>)
♣ Tri+ial names are better adopted %or %acility
3aturated hydrocarbon seletons
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3aturated hydrocarbon seletonso% monoE & ses.uiterpenoids
2yrcane pE2enthane mE2enthane
Thuane Carane inane
/ornane (Camphane) 5enchane isoECamphane
2ONOT?R?NOID3
3?3\UIT?R?NOID3
Trimethyldodecane /isabolane ?lemane
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Isomerism o% 2onoterpenoids
♣ 3tructural isomerism dueto shi%t in the double
bonds- eg
♣ 3tructural isomerism due
to shi%t in the position o%
a substituent group egpEmenthadiene & mE
menthadiene
deri+ati+es
rene O&mene &moneneα
erp&nene
&monene S!estrene
Isomerism o% 2onoterpenoids
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Isomerism o% 2onoterpenoids
♣
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henyl propanoids (C>EC9) or:romatic constituents
♣ @ess common than terpenoids♣Contain a C> phenyl ring to which is attached
a C9 propane side chain
♣2any are phenols (eg eugenol)- phenol
ethers (eg- anethole- sa%role- apiole) or
aldehydes (eg- cinnamaldehyde)
♣ The propane side chain may be %ormed o% 6 C
(C>EC6) or 4 C (C>EC4) eg +anillin- methylsalicylate & methyl anthranilate
♣Certain aromatic C4# compounds eg pE
cymene- thymol & car+acrol can be
described under monoterpenoids
+olatile oils
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+olatile oils
OG
OG
OCG9 OG
OCG9
OCG9
G9CO
OG
CGO
OCG9 CGO
OCG9 CG6OG
OG
O
O
O
O
O
pECymene Thymol Car+acrol
:nethole ?ugenol 3a%%role :piole