Diels-Alder reaction of myrcene with carbonyl containing dienophiles supported on silica gel under microwave irradiation

Article abstract of DOI:10.1080/10426500490459777

Diels-Alder reactions of myrcene (7-methyl-3-methene-1,6-octadiene) with carbonyl containing dienophiles supported on silica gel under microwave irradiation have been studied.

Full text of DOI:10.1080/10426500490459777

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Phosphorus, Sulfur, and Silicon and the Related
Elements
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DIELS-ALDER REACTION OF MYRCENE WITH CARBONYL
CONTAINING DIENOPHILES SUPPORTED ON SILICA GEL
UNDER MICROWAVE IRRADIATION
a
Hossein Abdi Oskooie
a
Azzahra University, Tehran, Iran
Published online: 16 Aug 2010.
To cite this article: Hossein Abdi Oskooie (2004) DIELS-ALDER REACTION OF MYRCENE WITH CARBONYL CONTAINING
DIENOPHILES SUPPORTED ON SILICA GEL UNDER MICROWAVE IRRADIATION, Phosphorus, Sulfur, and Silicon and the Related
Elements, 179:6, 1165-1167, DOI: 10.1080/10426500490459777
To link to this article: http://dx.doi.org/10.1080/10426500490459777
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Phosphorus, Sulfur, and Silicon, 179:1165–1167, 2004
Copyright ꢀC Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500490459777
DIELS-ALDER REACTION OF MYRCENE WITH
CARBONYL CONTAINING DIENOPHILES
SUPPORTED ON SILICA GEL UNDER MICROWAVE
IRRADIATION
Hossein Abdi Oskooie
Azzahra University, Tehran, Iran
(
Received September 23, 2003; accepted October 14, 2003)
Diels-Alder reactions of myrcene (7-methyl-3-methene-1,6-octadiene)
with carbonyl containing dienophiles supported on silica gel under mi-
crowave irradiation have been studied.
Keywords: Cycloaddition reaction; Diels-Alder reaction; microwave;
mycerene; regioselectivity
The Diels-Alder reaction is a concerted (4π + 2π) cycloaddition reac-
tion of a conjugated diene on a dienophile. This reaction is one of the
most useful C C bond forming reactions and provides several path-
ways toward the simultaneous construction of substituted cyclohex-
enes with a high degree of regioselectivity, diastereoselectivity, and
enantioselectivity.1
Reagents and substrates impregnated on mineral solid supports have
popularity in organic synthesis because of their selectivity and ease of
2
manipulation. Recently, there has been growing interest in the appli-
3
cation of microwave irradiation in chemical reactions. Microwave as-
sisted reactions under dry conditions are especially appealing as they
provide an opportunity to work with open vessels thus avoiding the risk
of high pressure and with a possibility of upscaling the reaction on the
preparative scale.4
Several examples of solid supported Diels-Alder reactions mostly
on polymeric support including classical intermolecular, inverse elec-
tron demand, hetero and intramolecular Diels-Alder reaction have
The author is thankful to the Research Council of Azzahra University for partial
financial assistance.
Address correspondence to Hossein Abdi Oskooie, Department of Chemistry, School
of Sciences, Azzahra University, Vanak, Tehran, Iran.
1
165

1
166
H. A. Oskooie
been reported and can be found in an excellent review article by
Yli-Kauhaluoma.5
Myrcene (7-methyl-3-methene-1,6-octadiene) prepared by craking β-
pinene which was obtained from turpentine oil, and can react with
different dienophile giving rise to a variety of fragrant compounds or
6
their intermediate. The reaction of myrcene with carbonyl containing
dienophiles can give para/meta regioselectivity. For example, reaction
of myrcene with acrolein or methyl acrylate can give para/meta isomers
6
(
Scheme 1).
SCHEME 1
In this article I report that the reaction of myrcene with acrolein and
with methyl acrylate supported on silica gel under microwave irradia-
tion give a high para/meta regioselectivity and the reaction rates are
also enhanced dramatically.
The result of the reaction between myrcene with acrolein and
myrcene with methyl acrylate at different temperature without any
7
catalyst recently has been reported. In the thermal reaction, the yield
8
of the “para” adduct is greater than that of the “meta” adduc. The se-
lectivity of the cycloadduct is decreased with increasing the reaction
temperature. Therefore we can not obtain the “para” adduct in high
yield by increasing the temperature.
7
D. Yin et al. have reported a regioselective Diels-Alder reaction of
myrcene with carbonyl containing dienophiles catalyzed by Lewis acids.
We obtained almost the same regioselectivity by using silica gel as solid
support and microwave irradiation. The regioselectivity of p/m for 1a/2a
was 10:5 and for 1b/2b was 4:9. In the thermal reaction the p/m regios-
7
electivity has been reported to be 2.6 and 2 respectively.
In conclusion, silica gel can be used as an excellent support for regios-
elective Diels-Alder reactions of myrcene under microwave irradiation.
These conditions have the advantages of offering a practical and en-
vironmentally benign protocol that decrease the time, gives a cleaner
reaction and leads to easier work up.

Diels-Adler Reaction of Myrcene
1167
EXPERIMENTAL SECTION
The products are known and their physical data were identified by
7
comparison with those reported in the literature.
Reaction of Myrcene with Acrolein and Methyl Acrylate
(
General Procedure)
Myrcene (200 mg, 1.47 mmol) was put onto silica gel (0.5 g) which
was moistened with water (2 drops) in a small beaker. The appropri-
ate dienophile (1.47 mmol) was added to the beaker and mixed with
the supported myrcene thoroughly. The beaker was placed in a mi-
crowave oven for 10 min. The progress of the reaction was monitored by
TLC. To the product mixture CHCI3 (10 mL) was added. The mixture
was filtered and the solvent was evaporated. The crude residue was
passed through a small coloumn packed with silica gel using petroleum
ether/chloroform (5:5, v:v) as eluent to obtain the Diels-Alder product.
Conversion of myrcene in the reaction with acrolein was 85% and its
regioselectivity was 10:5. The Conversion of myrcene for the reaction
with methyl acrylate was 98.5 and its p/m regioselectivity was 4:9.
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