Eugenol Derivatives and Caryophyllene Oxide are prepared by simple , safe ad inexpensive ways. For caryophyllene oxide the reaction proceeds at room temperature without any coolant added.

1. Simple Inexpensive & Safe Method of Preparation of
Eugenol Derivatives and Caryophyllene Oxide at
Room Temperature without any coolant
Benjamin Lukas

2. Clove Oil
Clove oil is an essential oil extracted from clove plant, Syzygium Aromaticum. It is
often found sold at health food store. It is produced by steam distillation.
There are 3 types of this essential oil of clove:
Bud oil: the most expensive type derived from flower-bud of S. Aromaticum
Stem oil: derived from twigs of S. aromaticum
Leaf oil: the least expensive type derived from leaves of S. Aromaticum
Main Components of Clove oil:
• Eugenol (up to 80%)
• Caryophyllene (up to 16%)
And other Minor Components
consisting of 20 chemicals
Including:
• Isoeugenol
• Methyl eugenol
• Methyl isoeugenol
• Eugenyl acetate
• Isoeugenyl acetate and
others

3. Production of Clove Oil
Material Steam Steam generator
Essential oil
Extraction machine
Plant extract
Chiller Condensor Distillate Oil water separator Essential
oil

4. Steam Distillation Unit for Local Farmers in
Indonesia

5. Uses of Clove Oil
Clove oil is used as analgesic and others such as:
• Home remedy for relieving toothache
• Ingredience of cat spray deterence
• Flavoring agent for some medicine
• Anaesthetic for fish
• To extract eugenol and caryophyllene from which other
derivatives of eugenol and caryophyllene are synthetically
made.

6. 1st Main Components of Clove Oil:
Eugenol
• Eugenol, 4-allyl 2-methoxyphenol is the main component of clove oil, a
derivative of a phenylpropene with a methoxy group at meta position and
hydroxy at para position.
• It is a pale yellow clear liguid present in clove, nutmeg, cinnamon,
cinnamomum tamala, bay laurel , sweet basil, African basil, Holy basil, dill,
Japanese star anise, lemon balm, vanilla, celery and pimenta racemosa
• When it is freshly produced the colour is dark brown, after purification it
becomes pale yellow but readily turn brown on exposed to the air.
• It is soluble in most organic solvents, but almost insoluble in water.
• It has strong , clove-like smell and spicy with pungent taste.

7. Extraction of Eugenol
• Crude eugenol can be extracted very easily from crude clove oil by using its
polar character and the non-polarity of the rest of the components of clove
oil. The water used in this process can reused several times until it is
saturated with the side product. Local farmers in Indonesia have been taught
the method of this extraction so that it has added value on their original
product of clove oil. The purity of this crude eugenol obtained using this
method is about 95%.
• Further purification of crude eugenol can be achieved by simple distillation to
give 99% purity . When freshly prepared it is pale yellow clear liquid which
quickly turns yellowish to finally brownish when exposed to air
• Details of this simple industrial process can be obtained on request.

8. Uses of Eugenol
• Eugenol is mainly used as antiseptic, analgesic, perfumery and as flavoring agent.
• As flavoring agent, it is used in non-alcoholic beverages, candy, baked goods,
puddings, ice creams, ices, chewing gums, condiments and meats.
• Eugenol when combimed with zinc oxide has been used in dentistry for many years as
root canal sealing.
• It is also used as wood preservative.
• Eugenol and some of its derivatives can be used as valuable thermal stabilizers and
antioxidant for plastics made from starch of tapioca or corn etc (bioplastics) for
packaging film when coated with certain compounds such as chitosan or cyclodextrin.
• Eugenol is a key ingredient in Indonesian kretek cigarette

9. Uses of Eugenol

10. Derivatives of Eugenol
• Clove oil can be extracted from either leaves, stem or buds of clove tree
• The main component of clove oil is eugenol which can be extracted by simple
chemical reaction making use of its polarity character to give min 95 % purity.
Further simple vacuum distillation will give eugenol of 99% purity.
Derivatives of eugenol produced by industry:
• Isoeugenol Hydroeugenol
• Eugenol acetate Isoeugenol acetate
• Methyl eugenol Methyl isoeugenol

11. Price of Eugenol & Caryophyllene & Derivatives
Vigon International, East Stroudberg, PA, USA
No Compound Price 1kg 1 kg (5kg
purchase)
1 kg (10kg
purchase)
1 kg (50kg
purchase)
1 kg (200kg
purchase)
1 Minyak cengkeh (Clove leaf oil)
2 Eugenol $117 $52 $38 $36 $32
3 Isoeugenol $170 $80 $60 $56 $50
4 Eugenyl acetate $185 $95 $75 $71 $65
5 Isoeugenyl acetate $184 $94 $74 $70$
6 Methyl eugenol $150 $85 $72 $69 $65
7 Methyl isoeugenol $190 $100 $80 $76 $70
8 Benzyl eugenol $611 $521 $501
9 Dihydroeugenol $147 $82 $68 $66 $62
10 Caryophyllene
11 Caryophyllene oxide
12 Caryophyllene acetate $147 $82 $68 $66 $62
13 Caryophyllene formate

12. • Clove Leaf Oil is the raw material used for
synthesis of the above compounds U$12 –
U$15/Kg (Indonesian companies such as
Indesso Aroma, Djasula Wangi, Nusaroma)

13. Isoeugenol
• Isoeugenol is an isomer of eugenol
• It has a characteristic floral odor reminiscent of carnation.
• It exist as 2 isomers as cis and trans isoeugenol
• Only trans-isoeugenol is valuable, it has softer aroma than eugenol and therefore used as
carnation note in fragrance.
• As flavoring agent it is used in non-alcoholic beverages, candy, condiments, chewing
gums, ice creams and ices.
• Isoeugenol is produced commercially by isomerization process but the proses produces
min 7% tarry side product with the catalyst used losing some of its catalytic power.
• There are 2 types of catalysts used for isomerization of eugenol, both are like secret to
most industry . One of the catalysts is an expensive Ru/Rh organometallic compounds
while the other is a very cheap one.
• Because of the difference of boiling point of the isomers trans and
is only by 5C, the separation of the isomers is only possible by
fractional distillation.
Details of the process with conversion greater than 99% conversion
can be obtained on request.

14. Isomers of Isoeugenol
Trans-Isoeugenol cis-Isoeugenol

15. Fractional distillation in Lab

16. Fractional Distillation in Industry

17. Methyl Eugenol
• Methyl eugenol is a colorless or pale yellow clear liquid with a bitter taste and clove-
carnation aroma. It is an ether compound of eugenol with the bpt of 244 C but
evaporates readily at room temperature
• It darkens and slowly thickened when exposed to air
• It is presence in some herbs and spices such as lemon grass, basil, mace, tarragon,
bay leaf, nutmeg, allspice and clove. In fruits it is found in banana, grapefruit.
• It has delicate clove-carnation odor with a bitter burning taste.
• As flavoring agent, it is used in non-alcoholic beverages, candy, baked goods, jellies ,
ice creams and ices.
• It is produced using methylation process with dimethylsulfate (DMS) as methylating
agent under certain condition as DMS is very toxic compound.
• Details of industrial process can be obtained on request.

18. Uses of Methyl Eugenol
Methyl eugenol is used as:
• Flavoring agent in various food and non-beverage drinks such
as in jellies, chewing gum, baked food, candy, pudding, relishes
and ice cream.
• As fragrance in perfumery, toiletries creams and lotions, soaps
and detergents.
• As insect attractant for fruit flies etc.

19. Methyl Isoeugenol
• Methyl isoeugenol is a methyl ether compound of isoeugenol, a colorless or pale
yellow clear liquid with a bpt of 262-264 C found in some essential oils. It occurs in
both isomers cis and trans but only the trans isomer is valuable.
• It has a delicate clove-carnation odor with burning bitter taste.
• It is used in flavor and fragrance formulations
• As flavoring agent, it is used in non-alcoholic beverages, candy, baked goods,
gelatins, puddings, chewing gums and ice creams ices.
• Is is also used as anxiolytic and antidepressant
• In industry it is prepared by first converting eugenol to trans-isoeugenol and then
methylating this product to become trans- methyl isoeugenol.
• Purification then produce pure trans methyl isoeugenol.
Separation of trans from cis can be done at the end of the
process.
• Details of the process with yield greater than 95% can be
obtained on request.

20. Isomers of Methyl Isoeugenol
trans-methyl isoeugenol cis-methyl isoeugenol

21. Eugenol Acetate
• Eugenol acetate is a white solid with mpt of 26 C and bpt 281-285 C.
. It is soluble in most organic solvents and essential oils
. It has characteristic odor reminiscent of clove oil with burning
aromatic flavor
• It is used as flavor and fragrance agents
• As flavoring agent it is used in non-alcoholic beverages, candy,
ice creams, baked goods, cheing gums, condiments and meats.
• It is prepared by esterification of eugenol in the presence of a
catalyst.
Eugenol + acetylating agent catalyst Eugenol acetate + acetic acid
• Details of the process can be obtained on request.

22. Isoeugenol Acetate
• It is 2-methoxy-4-propenylphenyl acetate, a white crystal with a mild aroma
resemblance of rose-carnation with mpt of 79C and bpt of 283C.
• It is used as floral flavor and fragrance. It is also used in fixed scent fragrance
of carnation flavor combined with vanillin.
• As flavoring agent, it is used in non-alcoholic beverages, ice creams, ices,
baked goods and chewing gums.
• It is produced by refluxing isoeugenol with acetylating agent and after
exclusion of acetic acid, crystals of isoeugenol acetate is obtained. Further
purification affords pure compound.
• The above preparation produce yield less than 20%, but if a certain catalyst is
added to the reaction more than 90% yield is obtained.
• Details of process with yield greater than 90%can be obtained on request.

23. Dihyydroeugenol
• It is eugenol with the propylene group has been fully hydrogenated. It is a
liquid with an aroma of clove, sharp, spicy, sweet similar to eugenol.
• In perfume it is a great addition to jasmin, carnation or spicy flower accords.
• It is prepared by reacting eugenol with hydrogen in the present of a catalyst
at room temperature for several hours.
• Eugenol + H2 catalyst Dihydroeugenol
• Dihydroeugenol obtained is then purified by simple distillation

24. 2nd Main Components of Clove Oil:
Caryophyllene
• Caryophyllene is a sesquiterpene found in many essential oils such as oil of
clove, cinnamomum tamala, basil, rosemarry, oregano, cannabis, hop, black
caraway, true cinnamon and black pepper . Its presence in black pepper
contributes to its spicyness.
• It is usually found in a mixture with isocaryophyllene and alpha caryophyllene
• It has terpene odor between that of clove and turpentine
• It has bpt of 254 C and soluble in alcohol but insoluble in water.
• As flavoring agent, it is used in chewing gums, candy, baked goods, ice
creams, ices, non-alcoholic beverages and condiments

25. Caryophyllene Derivatives
• After eugenol is extracted from clove oil, beta caryophyllene can be
purified using fractional distillation from 20 other components. The
industrial beta caryophyllene has purity of about 85%.
• Derivatives of beta caryophyllene produced by industry:
- Caryophyllene oxide
- Caryophyllene acetate
- Caryophyllene formate
- Caryophyllene alcohol

26. Caryophyllene Oxide
Caryophyllene oxide is widely used in industry as a flavour and
fragrance compound and recently has been patented as antitumor
agent.
It is an oxygenated form of the sesquiterpene which exists as white
crystalline solid with a melting point of 62 C.
There is no known method of preparation of this compound in the
literature as the method is kept secret by the manufacturers.
It is only known that the raw material used for production of
caryophyllene oxide in industry is beta caryophyllene derived from
the clove oil.

27. Production of Caryophyllene Oxide
CLOVE LEAF/BUD/STEM
CLOVE OIL
EUGENOL CARYOPHYLLENE
CARYOPHYLLENE OXIDE

28. Preparation of Caryophyllene Oxide
In this work caryophyllene oxide was prepared by reacting caryophyllene (86% purity)with
percarboxylic acid prepared in situ using carboxylic acid and H2O2 . A catalyst is
needed for the preparation of caryophyllene oxide at room temperature without
needing any coolant. The yield is less than 90%
RCOOH + H2O2 RCOOOH + H2O

29. Preparation of Caryophyllene Oxide
Variables used in the reaction:
Stoichiometry, reaction time and the type and amount of the catalyst used. If the
conditions are not followed then the the temperature will rise up very quickly.
Details of the process can be obtained on request.
Caryophyllene + RCOOOH catalyst, RT Caryophyllene Oxide + RCOOH

30. Price of Caryophyllene Oxide
Caryophyllene oxide is very much more expensive than caryophyllene itself or
any other eugenol derivatives because of the difficulty in producing it.
Just for comparison the price at Sigma-Aldrich for 1 gram caryophyllene oxide
of 99 % purity is $70.00 compared to the price of caryophyllene which is $ 3.00
per 1 kilogram. The price of the most expensive of eugenol derivatives is only
over $501.00 per kilogram.
The cost of chemicals used for preparation of 1 kg caryophyllene oxide is less
than $1
Clove leaf oil, eugenol and caryophyllene (86% purity) can be obtained easily
from Djasula Wangi, Indesso Aroma and Nusaroma in Indonesia.

31. GCMS of Caryophyllene Oxide
Caryophyllene obtained is 99% pure as indicated by GC MS analysis.

32. References
References:
- Chemistry of Natural Compounds 23, 393, 1987
The Chemistry of caryophyllene and related compounds by
A.V.Tkachev
- CA Patent 2440534
- US Patent 4229599
- US Patent 3978089
- Journal of Natural Products, 575 999, 1992

33. Thank you………………
For consultation of this project and
others previously reported please
contact :
benjaminlukas@yahoo.com