Volatile Oils 1

8/18/2019 Volatile Oils 1

1/72

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


2/72

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


3/72

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'

;


4/72


5/72

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


6/72

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


7/72

Classi,cation o% plantconstituents may be according

to:: harmacological acti+ity [analgesics, laxatives, cardiotonicsetc……..]

/ /iosynthetic origin, solubilityproperties & ey %unctional groups

C Chemistry & common physicalproperties


8/72

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


9/72

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

>


10/72

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.


11/72

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


12/72

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)


13/72

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


14/72

5ree & Combined 5orms o% FolatileOils

They may be present 7

4 5ree → aromatic characteristic odor- or

6 Combined with7

3ugars → glycosides


15/72

@ocation in the plant

4 2odi,ed parenchyma or oil cells7

(@auraceae & Jingiberaceae)

6


16/72

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


17/72

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


18/72

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


19/72

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)


20/72

?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)


21/72

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'


22/72

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 %


23/72

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)


24/72

?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


25/72


26/72

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


27/72

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


28/72


: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


29/72

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



30/72


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


31/72

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)


32/72


33/72

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


34/72

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


35/72

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


36/72


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


37/72


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


38/72


: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


39/72


/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


40/72


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


41/72

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


42/72

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

http://images.search.yahoo.com/search/images/view?back=http%3A%2F%2Fimages.search.yahoo.com%2Fsearch%2Fimages%3Fp%3DJasmin%2Bflower%26y%3DSearch%26ei%3DUTF-8%26js%3D1%26ni%3D20%26fr%3Dyfp-t-331-s%26b%3D41&w=400&h=500&imgurl=static.flickr.com%2F2122%2F1905230772_2d78871131_m.jpg&rurl=http%3A%2F%2Fwww.flickr.com%2Fphotos%2F11882345%40N04%2F1905230772%2F&size=84.1kB&name=1905230772_2d78871131.jpg&p=Jasmin+flower&type=jpeg&no=43&tt=482&oid=f56080e7ca4a1532&fusr=Ma+Migliano&tit=Jasmin&hurl=http%3A%2F%2Fwww.flickr.com%2Fphotos%2F11882345%40N04%2F&ei=UTF-8&src=phttp://images.search.yahoo.com/search/images/view?back=http%3A%2F%2Fimages.search.yahoo.com%2Fsearch%2Fimages%3Fp%3DNarcissus%2Bflower%26y%3DSearch%26ei%3DUTF-8%26js%3D1%26ni%3D20%26fr%3Dyfp-t-331-s%26b%3D21&w=500&h=375&imgurl=static.flickr.com%2F178%2F449502985_34a29cf764_m.jpg&rurl=http%3A%2F%2Fwww.flickr.com%2Fphotos%2Fnewage%2F449502985%2F&size=84.2kB&name=449502985_34a29cf764.jpg&p=Narcissus+flower&type=jpeg&no=30&tt=11,726&oid=6b3b3e38b2da5e0e&fusr=potopoto53age&tit=multi+color%27s+Narcissus+%28RICOH+GR-DIGITAL%29&hurl=http%3A%2F%2Fwww.flickr.com%2Fphotos%2Fnewage%2F&ei=UTF-8&src=phttp://images.search.yahoo.com/search/images/view?back=http%3A%2F%2Fimages.search.yahoo.com%2Fsearch%2Fimages%3F_adv_prop%3Dimage%26fr%3Dyfp-t-331-s%26va%3Dviolet%2Bflower%26sz%3Dall&w=1024&h=768&imgurl=cordially.narod.ru%2Falbum%2Fplant%2Fimages%2Fviolet-flower.jpg&rurl=http%3A%2F%2Fcordially.narod.ru%2Falbum%2Fphoto-en.html&size=71.3kB&name=violet-flower.jpg&p=violet+flower&type=jpeg&no=1&tt=48,185&oid=2395ca9f34090102&ei=ISO-8859-1http://images.search.yahoo.com/search/images/view?back=http%3A%2F%2Fimages.search.yahoo.com%2Fsearch%2Fimages%3Fei%3DUTF-8%26p%3Dtuberose%2520flower%26sado%3D1%26fr2%3Dtab-web%26fr%3Dyfp-t-331-s&w=500&h=375&imgurl=static.flickr.com%2F208%2F503117212_5ccbf22bd3_m.jpg&rurl=http%3A%2F%2Fwww.flickr.com%2Fphotos%2Fgabisa_motonia%2F503117212%2F&size=109.9kB&name=503117212_5ccbf22bd3.jpg&p=tuberose+flower&type=jpeg&no=1&tt=543&oid=f2cae1da4083ca06&fusr=%2AGabisa+Motonia&tit=SEDAP+MALAM+%2C+A+species+of+Tuberose&hurl=http%3A%2F%2Fwww.flickr.com%2Fphotos%2Fgabisa_motonia%2F&ei=UTF-8&src=phttp://images.search.yahoo.com/search/images/view?back=http%3A%2F%2Fimages.search.yahoo.com%2Fsearch%2Fimages%3Fei%3DUTF-8%26p%3Dtuberose%2520flower%26sado%3D1%26fr2%3Dtab-web%26fr%3Dyfp-t-331-s&w=500&h=375&imgurl=static.flickr.com%2F26%2F47560433_1d302be097_m.jpg&rurl=http%3A%2F%2Fwww.flickr.com%2Fphotos%2Fbuttersweet%2F47560433%2F&size=84.5kB&name=47560433_1d302be097.jpg&p=tuberose+flower&type=jpeg&no=8&tt=543&oid=0cfb92a77efdb148&fusr=Buttersweet&tit=white+tuberose&hurl=http%3A%2F%2Fwww.flickr.com%2Fphotos%2Fbuttersweet%2F&ei=UTF-8&src=phttp://upload.wikimedia.org/wikipedia/commons/e/ec/Daffodills_%28Narcissus%29_-_25.jpg


43/72

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


44/72

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


45/72

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


46/72

http://images.search.yahoo.com/search/images/view?back=http%3A%2F%2Fimages.search.yahoo.com%2Fsearch%2Fimages%3Fp%3Dpictures%2Bof%2Bjasmine%2Bflowers%26_adv_prop%3Dimage%26sz%3Dall%26ei%3DUTF-8%26ni%3D20%26qp_p%3Djasmine%2Bflowers%26imgsz%3Dall%26fr%3Dyfp-t-331-s%26b%3D121&w=500&h=375&imgurl=static.flickr.com%2F2187%2F1614399079_2a0d4722c3_m.jpg&rurl=http%3A%2F%2Fwww.flickr.com%2Fphotos%2Fgreenhousematt%2F1614399079%2F&size=121.2kB&name=1614399079_2a0d4722c3.jpg&p=pictures+of+jasmine+flowers&type=jpeg&no=127&tt=11,296&oid=7901c2e3ace90f8e&fusr=greenhousematt&tit=pink+jasmine&hurl=http%3A%2F%2Fwww.flickr.com%2Fphotos%2Fgreenhousematt%2F&ei=UTF-8&src=p


47/72

?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

http://images.search.yahoo.com/search/images/view?back=http%3A%2F%2Fimages.search.yahoo.com%2Fsearch%2Fimages%3Fp%3Dpictures%2Bof%2Bjasmine%2Bflowers%26_adv_prop%3Dimage%26sz%3Dall%26ei%3DUTF-8%26ni%3D20%26qp_p%3Djasmine%2Bflowers%26imgsz%3Dall%26fr%3Dyfp-t-331-s%26b%3D121&w=500&h=375&imgurl=static.flickr.com%2F2187%2F1614399079_2a0d4722c3_m.jpg&rurl=http%3A%2F%2Fwww.flickr.com%2Fphotos%2Fgreenhousematt%2F1614399079%2F&size=121.2kB&name=1614399079_2a0d4722c3.jpg&p=pictures+of+jasmine+flowers&type=jpeg&no=127&tt=11,296&oid=7901c2e3ace90f8e&fusr=greenhousematt&tit=pink+jasmine&hurl=http%3A%2F%2Fwww.flickr.com%2Fphotos%2Fgreenhousematt%2F&ei=UTF-8&src=phttp://images.search.yahoo.com/search/images/view?back=http%3A%2F%2Fimages.search.yahoo.com%2Fsearch%2Fimages%3Fp%3Dpictures%2Bof%2Bjasmine%2Bflowers%26rs%3D1%26_adv_prop%3Dimage%26sz%3Dall%26ei%3DUTF-8%26ni%3D20%26fr%3Dyfp-t-331-s%26vf%3D&w=500&h=475&imgurl=static.flickr.com%2F1400%2F1144409367_944ddf2148_m.jpg&rurl=http%3A%2F%2Fwww.flickr.com%2Fphotos%2Fpapaalphaecho%2F1144409367%2F&size=113.5kB&name=1144409367_944ddf2148.jpg&p=pictures+of+jasmine+flowers&type=jpeg&no=13&tt=11,296&oid=b38ca06d03fe7a48&fusr=pennyeast&tit=Jasmine+%28Jasminium+polyanthum%29&hurl=http%3A%2F%2Fwww.flickr.com%2Fphotos%2Fpapaalphaecho%2F&ei=UTF-8&src=phttp://images.search.yahoo.com/search/images/view?back=http%3A%2F%2Fimages.search.yahoo.com%2Fsearch%2Fimages%3Fp%3Dpictures%2Bof%2Bjasmine%2Bflowers%26rs%3D1%26_adv_prop%3Dimage%26sz%3Dall%26ei%3DUTF-8%26ni%3D20%26fr%3Dyfp-t-331-s%26vf%3D&w=500&h=375&imgurl=static.flickr.com%2F17%2F21703713_e946b2d43e_m.jpg&rurl=http%3A%2F%2Fwww.flickr.com%2Fphotos%2Fkpjas%2F21703713%2F&size=55.8kB&name=21703713_e946b2d43e.jpg&p=pictures+of+jasmine+flowers&type=jpeg&no=6&tt=11,296&oid=546cdf390dad212e&fusr=Kpjas&tit=Jasmine_flowers_190605_kpjas&hurl=http%3A%2F%2Fwww.flickr.com%2Fphotos%2Fkpjas%2F&ei=UTF-8&src=phttp://images.search.yahoo.com/search/images/view?back=http%3A%2F%2Fimages.search.yahoo.com%2Fsearch%2Fimages%3F_adv_prop%3Dimage%26va%3Djasmine%2Bflowers%26sz%3Dall%26ei%3DUTF-8%26ni%3D20%26fr%3Dyfp-t-331-s%26b%3D101&w=500&h=333&imgurl=static.flickr.com%2F180%2F436499882_a106d59a75_m.jpg&rurl=http%3A%2F%2Fwww.flickr.com%2Fphotos%2Fkarinaspics%2F436499882%2F&size=71.4kB&name=436499882_a106d59a75.jpg&p=jasmine+flowers&type=jpeg&no=111&tt=11,296&oid=c39bec8dd0d78e72&fusr=karina%27s+pics&tit=jasmine&hurl=http%3A%2F%2Fwww.flickr.com%2Fphotos%2Fkarinaspics%2F&ei=UTF-8&src=p


48/72

“?n8eurage rocess

Cold ?n8eurage

Got ?n8eurage


49/72

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


50/72

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


51/72

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


52/72

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


53/72

aglycones

lant nameNonE+olatile


54/72

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%


55/72

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


56/72

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


57/72

ycnometer

olarimeter

:bbere%ractometer

Chemistry o% +olatile oils


58/72

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


59/72

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


60/72

“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


61/72

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


62/72

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


63/72

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%


64/72

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


65/72


♣ 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)



66/72

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


67/72

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


68/72

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


69/72

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



70/72


♣


71/72

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


72/72

+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

Volatile Oils 1

Documents

Transcript of Volatile Oils 1