Isoeugenol or Methyl eugenol can be converted easily by refluxing eugenol or methyl eugenol with an inexpensive catalyst (0.1%) much cheaper than the usual catalyst employed at industry (Ru or Rh compounds)

1. VALUABLE PERFUMERY MATERIAL: SIMPLE PROCESS OF
PREPARATION OF METHYL ISOEUGENOL USING CHEAP
CATALYST RATHER THAN EXPENSIVE Ru(acac)3
benjaminlukas@yahoo.com

2. Clove Essential Oil
Main Components
• Eugenol
• Caryophyllene
Minor Components
20 chemicals incl
• Isoeugenol
• Methyl eugenol
• Methyl isoeugenol

3. Price of Eugenol & Caryophyllene & Derivatives
Vigon International, East Stroudberg, PA, USA
No Compound Price
1kg
5kg 10kg 50kg 200kg
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

4. Price:
• 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)
Catalysts reported in literature used for Preparation of
Isoeugenol/Methyl Isoeugenol:
• Ru 3(CO)12 U$168.99/g
• Ru (acac)3 U$121.98/g
• RhCl3 U$357.03 /g

5. Structure:
• Eugenol
• Methyl Eugenol
• Isoeugenol
• Methyl Isoeugenol

6. Eugenol
OH
OCH3
CH2CH=CH2

7. Methyl Eugenol
OCH3
OCH3
CH2CH=CH2

8. Isoeugenol
OH
OCH3
CH=CHCH2

9. Methyl Isoeugenol
OCH3
OCH3
CH=CHCH2

10. Existing Methods for Preparation of Isoeugenol
/Methyl Isoeugenol from Eugenol/Methyl
Eugenol
1. Base catalyzed isomerisation.(1,2)
KOH + Eugenol/methyl eugenol is reacted at high T&P to
produce isoeugenol/methyl isoeugenol plus tarry side
products.
Disadvantage : -KOH ~ 2 x weight of eugenols
-The mixture is viscous
- Tarry side products 7%

11. 2.Transition metal compounds catalyzed
process.(3,4)
US Patent 4,138,411 : Ru compound used as catalyst
0,01%-0,1% weight of
eugenol/methyl eugenol
Disadvantage : Price Ru compound U$168.99/g
Tarry side product min 7%

12. .
GB patent 1,489,451 : RhCl3 as catalyst 0.01%-0,1%
weight of eugenol/methyl-
eugenol
Disadvantage : Price RhCl3 = U$357.03 /g
7% Tarry side products
Multi national Companies that produce these aromatic
chemicals are : Firmenich SA
International Flavor & Fragrance
Givaudan
Rhone-Poulenck SA

13. 3. Metal hydrotalcite isomerisation (5,7)
The conversion to isoeugenol/methyl isoeugenol is not
industrially feasible at 70%
4. Base catalyzed isomerisation using microwave
heating(6)
The conversion is about 98% with shorter reaction time but
the amount of base used is very high, 2.2 x weight of
eugenols.Therefore combined with expensive equipment,this
method is non-feasible for industry.

14. Scope of the work :
The work relates to a cheap method to produce methyl isoeugenol using a
different catalyst which cost less than 1 % of the method that is being used by
the industry with the new method produces no any waste tarry side product.
Catalyst:
• Ru 3(CO)12 U$168.99/g
• Ru (acac)3 U$121.98/g
• RhCl3 U$357.03/g
• New Catalyst U$4.10/kg
Procedure:
100 g methyl eugenol and 0.1 g new catalyst are placed in a 2 liter spherical
flask equipped with a thermometer, stirrer system and a reflux condenser with
the contents are then heated to reflux for 5 hours. The reaction mixture is
then distilled and analysed using gas liquid chromatography.

15. THE NEW CATALYST VS THE PRESENTLY USED METHOD IN
INDUSTRY
no New
catalyst
Ru(acac)3
catalyst
TIME
(hours)
TEMP
( ° C )
%Unreacted
Eugenol
Tarry
product
( % )
Information
1 - 0.01% 7 160 0.8 7 The expensive catalyst
lose some of its catalytic
power after the reaction
as it is embedded in the
tarry side product and
therefore some must be
added for new reaction
2 1% - 5 144 - 145 0.6 0 After the distillation of
the product, the catalyst
can be re
used.
Purity as checked using
GC consists of trans
product of 97.9% and cis
product of 1.76%

19. References
1. A.J. Hubert and H. Reimlinger, Synthesis 97, 1969
2. G. V. Salmoria, E. C. Dall’Oglio and Z.Zucco, Synth. Commun., 27, 4335, 1997
3. L. Givaudan, GB Patent 1 489 451
4. P. Gandilhon, US Patent 4 138 411
5. D. Kishore and S. Kannan, Appl. Catalysis A, 270, 2004
6. L. N. Thach and C. R. Strauss, J. Chem., 38, 76, 2000
7. G.M. Jinesh, C.A. Antonyraj and S.Kannan, Catalysis Today, 141, 176,2009