1. business and industrial
2. energy
3. oil

Chemical class
Name
Structure
Oxides in volatile oils
Cineole
Peroxides in volatile oils
Ascaridole
1
Cineole is also called:
Eucalyptol or Cajuputol
(Cajeputol)
O
O
4
Ketones in volatile o
Ascaridole
Source

Properties



Isolation
Major constituent of oils :
1. Of Eucalyptus species ‫الكافور‬
2. Oil of cajuput
Camphor – like odor
Pungent taste
Syrupy oil
Oil of Chenopodium
Acyclic or
aliphatic ketones
 Most common are:
 Acetone and diacetyl
Based on its amount in the oils :
 Terpenoid of the group
 Fractional distillation, followed by cooling the fraction.
are rare :
 Formation of additive products with :
1-Syrup phosphoric acid : regeneration by hot water
 Tagetone
(used for quantitative estimation in case of oils rich in
the constituent)
2-Halogen acids Hcl or HBr crystalline products
3-Phenols e.g. 50% resorcinol
N.B: (from practical)
-Cineole phosphoric acid is a solid mass "by compression" to exclude non-cineole
portion  put the remaining mass in cassia flask with decomposition by hot water.



Disagreeable odor & flavor
Soluble in acetic acid
Alicyclic
terpenoid
It explodes with violence
if :
ο
ketones
1. Heated to 130 -135 C (decomposition)
2. Treated with H2SO4 , HCl , HNO3 or
H3PO4

Most distillation
important group
of ketones
By repeated fractional
of the oil
under detect
 Monocyclic
e.g. :
vacuum (to prevent
explosionmonoterpenoids
due to the 2 oxygen)
 Menthone
 Carvone
 Diosphenol
 Bicyclic monoterpenoids e.g.:
 camphor
1
Determination
Uses
-We must use Syrupy phosphoric acid & with specific gravity=1.74.
Determination: (see practical notes)
*Phosphoric acid method: (Scammel’s method, modified by Baker & Smith)
This method is used for large amounts of cineole (not less than 50%).
*Colorimetric methods: are useful in cases of low cineole-containing oils "It
is used for quantitative determination"
-Cineole + Vanillin/H2SO4 Azure Blue color, this color detected by
spectrophotometry & must obey beer-lambert’s law, its conc. directly
proportional with the intensity of color & stable color
 Locally:
1. Mild anesthetic , antiseptic , analgesic and anti-inflammatory "so
used in rheumatic pain"
2. Used in skin lotions & other types of cosmetics
 Internally:
1. Stimulant
2. Expectorant in cases of chronic bronchitis.
 In room sprays
 Has a cockroach repellent activity
It liberates I2 from KI in acetic acid solution, then
iodine is back titrated with Na thiosulfate using
starch as indicator.
(used for determination )
As anthelmintic in ascariasis
Organo-nitrogen compounds [Nitrogenous compounds]
Skatole (Methyl indole)
Name
Source
-Volatile oil of the wood of Celtis reticulate, Ulmaceae.
Properties
Uses
It has a strong fecal odor, in low concentration it has a flowery smell.
Used in small amounts as a fragrance & fixative of floral perfumes.
-Human excrements ( as a degradation product of albuminous matter)
-From strychnine alkaloid by heating with soda lime (semi-synthesis)
Structure
2
Name
Source
Organo-sulphur compounds
Allylisothiocyanate


It occurs in glycosidal combination as sinigrin in the seeds of black mustard (Brassica nigra , Cruciferae)
Sinigrin (or K myronate) on hydrolysis with myrosin enzyme
allyl isothiocyanate + D-glucose + Potassium hydrogen sulfate
(KHSO4).
H2
C
H2C
‫ بس‬Allyl isothiocyanate ‫ ال‬structure ‫علينا حفظ‬
‫والباقي اسماء بس‬
Properties




Preparation
Determination

Uses


C
H
Sinigrin
C
N O.SO2.OK
S C6H12 O6
H2O
Myrosin
S
H2
C
H2C
C
H
C
+ C6H12O6
+ KHSO4
N
Allyl isothiocyanate
Glucose
Potassium
acid sulfate
Pungent irritating odor
Remember:
Acid taste
Oils present as
Heavier than water
glycosides: mehtyl
N.B: Any oil present as glycoside nearly 100% oil on hydrolysis.
salicylate- Eugenol1. Powdered black mustard seeds are defatted
ο
vanillin- allyl
2. Macerated in water for about 5 hours at a temp. of 37 – 40 C to induce enzymatic action
isothiocyanate3. Then steam distilled
benzaldehyde
4. The oily layer , heavier than water, is collected "dried" over anhydrous CaCl2, redistilled
5. The fraction boiling between 145 – 152 οC (= pure allyl isothiocyanate ) (Collected by steam distillation)
N.B: Defatted means extraction of fixed oils by organic solvents "as petroleum ether" to remove them.
By Volhard's method
1. Treatment the oil sample with an excess of standard AgNO3 in presence of ammonia
2. The precipitated Ag2S is filtered
3. The unreacted AgNO3 titrated against NH4SCN using ferric alum as indicator  White ppt. & first buff is the end point.
Locally
1. Used as rubefacient & counter irritant or vesicant in certain plasters
2. Flavoring of food products especially mustards
Internally
1. It causes severe GIT irritation
3
2. Aromatic constituents from animal origin
Animal derived fragrant constituents are usually macrocyclic compounds of high M.wt.
Used in minute amounts as fixatives in high grade perfumes.
Musks
Natural musk



‫ مش حفظ‬structures ‫ال‬
Uses
N.B:
-Muscone is 15 carbons, 14 carbons of them form macrocyclic ring & No. 15 is Ketone or lactone.
-Civetone is 17 carbons, 16 carbons of them form macrocyclic ring & No. 17 is Ketone.
Versalide is an example of synthetic musks (C 18 ketone) used in: 1-Perfuming 2-Cosmetics
3-Soaps
Name
Source
Natural source
A group of perfume fixatives having a characteristic persistent aroma
Obtained from plant , animal sources and through chemical synthesis
The odor becomes pleasant in extreme dilution
Musk and musk-like products : Secretions produced in the Musk glands of:
-The male musk deer
male musk deer & Lousiana & ‫الدكتور قالت ممكن نعرف ال‬
-Civet cat
‫بس‬certain plant organs
-Louisiana musk rat
Also obtained from certain plant organs such as : Ambrette seeds & angelica root
Macrocyclic ketons or lactons :
 At least 15 carbons in their ring structure e.g Muscone (muskone)
-Civetone : the 17-membered macrocyclic musk constituent of civet
The musk odor : is confined to a very specific ring size (15 – 17 C atoms)
The basic ring structure must contain :
1. At least 14 C
2. In addition to either C=O (carbonyl) or NH (imino) group
Properties



Constituents
Name
Introduction
Uses


Ambergris
 It is a secretion from
the intestinal tract of
the sperm whale.
‫حوت العنبر‬
 With fragrant musk –
like odor
 Grey to black waxy masses
 The chief constituent
of ambergris is
ambrein (a tricyclic
triterpenoid alcohol )
 In perfumery , as a
tincture for fixation
of delicate odors
4
Resins
 Definition:
1- “Resin” is a group of solid or semi-solid substances of complex chemical nature and variable composition. They are brittle secretions or
exudations of plant tissues, produced either normally or due to pathogenic conditions.
2- “Artificial resins”
3-“Balsams” pathogenic condition are resinous mixtures that contain cinnamic acid, benzoic acid, or both, or esters of these acids.
 Physical Properties:
 Resin preparation depend on solubility
 Resin is prepared by alcohol, then adding water ppt.
 Solubility:
 Insoluble in water.
 Soluble in alcohol.
 Chemical Properties: (Depend on chemical structure, each chemical structure has chemical properties)
›They are complex mixtures of resin acids, resin alcohols, resin esters and resenes (neutral compounds, mostly hydrocarbons).
›Their chemical properties depend on the type of functional groups present: e.g. acidic resins react with alkalis to form soaps which are not
salted out by addition of NaCl (c.f. common soaps).
5
 Localization in the plant:
› May impregnate all the element of a tissue.
› They may occur in specialized secretory structures:
 Resin cells e.g. ginger.
 Schizogeneous or schizolysegenous ducts or cavities e. g. Pinus.
 Glandular hairs e.g. cannabis.
› They may be normal physiological products the yield of which is often increased by injury e.g. Pinus.
› They are sometimes formed only after induced injury i.e. having a pathological origin e.g. benzoin and balsam Tolu.
 Resin Combinations:
› Resins occur frequently in homogeneous mixtures with either volatile oils or gums or both to form:
 Oleoresins "Resin with V.O as in ginger" (V.O are separated by steam distillation)
 Gum-resins (gums could be easily separated by extraction with water & precipitated by alcohol)
 Oleo-gum-resins. (RESINS are soluble in alcohol and precipitated by water)
Note: extracting a plant containing
oleo-resin with ether or acetone
followed by distillation to remove the oil
 Preparation:
› Prepared resins (or resin combinations), these are obtained by extraction with alcohol, ether or acetone.
›Natural resins are those collected from the plants in which they are produced through natural or artificial punctures.
6
 Principal constituents of resins:
1) Resin acids:
› These are diterpenoid oxyacids, usually combining the properties of carboxylic acids & phenols.
› They occur both in the free state and as esters.
› They are soluble in aqueous alkalis forming soap-like solutions or colloidal suspensions.
› Their metallic salts are known as resinates.
2) Resin alcohols: ›They are subclassified into resinotannols and resinols.
* Resinotannols give a tannin reaction with ferric chloride
*Resinols give NO color reaction with ferric chloride
N.B: FeCl3 is a special test to differentiate between
resinotannols & resinols.
3) Resenes
› These are complex neutral INERT oxygenated substances devoid of characteristic chemical properties.
› They do not form salts or esters.
› They are insoluble in & resist hydrolysis with alkalis.
› They resist the action of oxidizing agents and climatic conditions.
4) Glycosidal mixtures:
› These are complex mixtures yielding on hydrolysis sugars and complex resin alcohol as aglycones.
7
Classification of resins
1. According to the botanical origin
2. According to the chemical constituent: acid resin, resene resins, glycosidal resins etc….
3. According to the predominating component in the resin combination e.g resins, oleoresins, oleo-gum resins, balsams…

Official resins and resin-combinations:
 Resins: Colophony, cannabis & podophyllin
 Oleo-gum-resins: myrrh.
 Balsams "Pathological": benzoin, balsam of Peru, balsam of Tolu.
Chemical
class
Name
A- Resins
Colophony or Rosin
Cannabis" Indian Hemp or Marihuana"
Podophyllum resin
"Podophyllin"
B- Oleo-gumresins
Myrrh
Source
Colophony is the solid resin
obtained from Pinus species
especially pinus paltustris [Fam.
Pinaceae].
It consists of the dried flowering tops of the pistillate
plants (female plants) of Cannabis sativa (Fam.
Moraceae). The resin is known in Arabic as hashish.
It is a mixture of resins
obtained from the dried roots
& rhizomes of Podophyllum
peltatum (American
podophyllum) and
Podophyllum hexandrum
(Indian podophyllum). Fam.
Berberidaceae.
-Obtained from the
stem & branches of
Commiphora
molmol (Fam.
Burseraceae)
-“Myrrh” is derived
from the Arabic
name “Murr”‫مر‬
Composition
-Resin acids:, mainly abietic
acid
-Resene: represented by a
small proportion of
hydrocarbons.
-These are meroterpenoid C21 compounds collectively
known as Cannabinoids.
-The main active constituent of the resin is (-)-∆9-transtetrahydrocannabinol (∆9- THC).
-Other constituents isolated from the resin include
-Chief constituent belong to
lignans (C18 compounds
related to flavonoids being
dimmers of 2 C6-C3 units).
-Resin composed
of: diterpenoid
resin acids (α-,β- &
γ- commiphoric
acids).
Present free & in glycosidal
combination.
8
cannabinol, cannabidiolic acid, cannabichromene,
cannabigerol and ∆8-trans-tetrahydrocannabinol (∆8THC).
double bond ً‫∆ العالمة دي معناها ان ف‬9
.
position 9 ‫عند‬
The structure is for
identification :D
Test for
-Copper acetate test (for
identificat abietic acid):
ion
 Extract the powder with
petroleum ether & filter.
Shake the filtrate with twice
its volume of Cu acetate
"blue". The petroleum ether
layer turns green due to the
formation of the copper salt
of abietic acid.
-Modified Beam’s test:
 Extract the drug with methanol, evaporate the
extract to dryness & extract the residue with
petroleum ether. Filter & wash the filtrate with dilute
Na2CO3 (take acidic) followed by dilute H2SO4 (take
basic) & water.
 Decolorize with charcoal & evaporate to dryness. To
the residue, add few drops of N/10 alcoholic KOH a
purple color is produced.
› In pharmaceutical industries,
colophony is used as
ingredient in cerates plasters
& ointments.
› Commercially, used in the
manufacture of varnishes,
paint dryers, printing inks,
Pharmacological action :
›Tetrahydrocannabinols (THC) possess euphoric activity.
Uses
›Cannabinol is weakly active.
›Cannabichromene & cannabidiolic acid are sedative.
Uses :
-The main components of the
resins are: podophyllotoxin,
α-peltatin and β- peltatin.
-Their concentrations in the
resins of the two species are
different:
 Indian resin:
podophyllotoxin (40%)
)lignans C18) with little or
no peltatins.
 American resin: 20% of
podophyllotoxin, 10% β peltatin and 5% α-peltatin.
-For Indian resin :
 The alcoholic solution of
the Indian resin gives a stiff
gel when treated with alkali
due to its high content of
podophyllotoxin.
-Podophyllotoxin contains a lactone
ring, when treated with alkali alkali
salt of podophyllic acid (gelatinous)
-Lignans: have anti-tumor
activities & anti-oxidant
effect.
-Peltatins: responsible for
most of the purgative effect of
the drugs.
-V.O
-Gum
-A Bitter principle
-The residue
obtained on
evaporation of the
ethereal extract of
the resin when
treated with either
conc.HNO3
Or exposed to Br2
vapors gives a violet
color.
-Externally, myrrh
used as a
protective
-Internally acts as
stimulant &
stomachic.
-Used in
9
soapsm sealing wax, floor
coverings.
›Medicinally, Indian hemp: as a sedative & hypnotic.
›∆9-Tetrahydrocannabinol or Dronabinol has an
antiemetic effect & used orally in the treatment of the
nausea & vomiting associated with cytotoxic drugs used
in cancer chemotherapy. It acts probably by blocking the
opiate receptors in the brain & indirectly inhibiting the
-The resin has also anti-mitotic mouthwashes as
astringent &
activity.
antiseptic.
Externally: tincture applied as
paint for treatment of soft
venereal warts
Internally: resin used as
drastic but slow purgative
emetic center.
›It also stimulates the appetite & ∴ used in treatment of
anorexia associated with weight loss in patients
suffering from AIDS.
Others
 The resin is secreted into trichomes (shaggy hair) found
on the bracts (small leaves) & bracteoles that
encloses the ovary of the flowering tops of the
female plant.
 For medicinal purposes either the resin (hashish) is
used or the flowering tops of the female plants
(marihuana).
 Pure resin from hashish.
Pharmaceutical preparations:
For skin conditions as:
-Ano-genital warts (paint of
podophyllum resin 20% in alcohol
or podophyllum resin 50% in
tincture benzoin us used.
-Malignant neoplasm of skin, an
alc. Soln of podophyllum resin
containing salicylic acid.
-Carcinoma of skin: ointment of
podophyllum resin 20% & linseed
oil in lanolin.
**How to differentiate
between Indian & American
resins?!
Treatment of the alcoholic
solution of the resins with few
drops of copper acetate gives:
*Bright-green color: American
resin
-Myrrh was found as
an ingredient of the
embalming material
of the ancient
Egyptians.
11
 The male plant produces an equivalent amount of
active constituents distributed throughout the plant
not concentrated into a resin. Not used as source of
resin.
 The amount of resin decreases when the plants are
cultivated in temperate regions. Thus, Indian
cannabis contains 20% or more resin, hemp
cultivated in temperate regions produces 6% or less.
-Toxicity:
On ingestion or inhalation by smoking, Indian hemp may
cause:
• euphoria
• Delirium ) ‫(زغلله فى العين‬
• Hallucination
• Weakness
• Hyperplesia
• Drowsiness.
*Brown color/ ppt.: Indian
resin
11
Balsams
-From pathological condition & Rich of benzioc acid or cinnamic acid or both of them.
Name
Peruvian balsam, Peru balsam, or balsam of Peru
Tolu balsam, or balsam of Tolu
Pathologic product formed by injury of the tree
Physical properties
Constituents
Uses
Dark brown, viscid liquid
-Cinnamein
-Volatile oil mainly benzyl cinnamate & a lesser amount of benzyl
benzoate.
- Resin esters, peruresinotannol cinnamate & benzoate
-Free cinnamic acid.
-Vanillin.
Internally: Expectorant.
Externally: antiseptic, protectant, rubefacient, parasiticide in certain
skin diseases e.g scabies & astringent in hemorrhoids.
Plastic solid masses
- Volatile oil mainly benzyl benzoate.
-Resin esters, toluresinotannol cinnamate & a small
amount of benzoate.
-Free benzoic acid
-Free cinnamic acid.
-Vanillin.
An ingredient of Tincture Benzoin Co. )‫)صبغة جاوى‬,
expectorant, flavoring agent.
Benzoins
Name
Constituents
Sumatra Benzoin (obtained from styrax benzoin fam. Styraceae)
-Free balsamic acids: chiefly cinnamic & benzoic acids.
-Traces of vanillin.
-Esters of balsamic acids.
-Terpenoid acids
Test For
gives a faint odour of benzaldehyde on warming with KMnO4 (oxidizing agent)
Identification due to high content of cinnamic acid (c.f. Siam benzoin).
-Antiseptic, stimulant, expectorant & diuretic properties, preservative, anti-fungal.
Uses
-An ingredient of Tincture benzoin compound. (topical protectant)
Siam Benzoin
-Small amounts of free benzoic acid only .
-Traces of vanillin.
-Coniferyl benzoate
-Triterpenoid compound (siaresinol).
An ethereal solution of the resin gives a deep purplish colour on
treatment with few drops of conc.H2SO4 (c.f. Sumatra benzoin)
is confined to perfumery.
12