Jasmonic acid compounds and process for the preparation thereof

Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters

Reexamination Certificate

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Reexamination Certificate

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06187946

ABSTRACT:

TECHNICAL FIELD
This invention relates to novel jasmonic acid compounds and a process for preparing the same.
BACKGROUND ART
The jasmonic acid compounds which have been known prior to the filing of the present application are limited to the alkyl esters and amides of jasmonic acid and dihydrojasmonic acid, and it has been desired to develop other jasmonic acid compounds.
Accordingly, an object of the present invention is to provide novel jasmonic acid compounds and a process for preparing the same.
DISCLOSURE OF THE INVENTION
According to the present invention, there is provided a jasmonic acid compound of the following general formula (1)
wherein R is a group selected from the group consisting of an alkenyl group of 3 to 6 carbon atoms, an alkynyl group of 3 to 6 carbon atoms, and a hydroxyalkyl group of 2 or 3 carbon atoms, and X is CH
2
—CH
2
or CH═CH.
According to the present invention, there is also provided process for preparing a jasmonic acid compound of the following general formula (1)
wherein R is a group selected from the group consisting of an alkenyl group of 3 to 6 carbon atoms, an alkynyl group of 3 to 6 carbon atoms, and a hydroxyalkyl group of 2 or 3 carbon atoms, and X is CH
2
—CH
2
or CH═CH, which comprises effecting an ester exchange reaction by allowing an alcohol of the following general formula (3)
R—OH  (3)
wherein R is a group selected from the group consisting of an alkenyl group of 3 to 6 carbon atoms, an alkynyl group of 3 to 6 carbon atoms, and a hydroxyalkyl group of 2 or 3 carbon atoms, to act on a jasmonic acid methyl ester of the following general formula (2)
wherein X is CH
2
—CH
2
or CH═CH.
In the above-described ester exchange reaction of a jasmonic acid methyl ester with an alcohol, the alcohol is usually used in an amount of 1 to 6 moles, preferably 3 to 4 moles, per mole of the jasmonic acid methyl ester.
As to the catalyst for the ester exchange reaction, any catalyst that are commonly used for ester exchange reactions may be used without limitation Usable catalysts include, for example, basic catalysts such as hydroxides and alkoxides of alkali metals and alkaline earth metals; protic acids such as sulfuric acid and p-toluenesulfonic acid; acidic ion-exchange resins; and metallic catalysts such as titanium alkoxides, aluminum alkoxides, tin compounds and lead compounds. These catalysts may be used alone or in admixture of two or more. These catalysts are usually used in an amount of about 0.05 to 20% by weight based on the weight of the alcohol.
It is not strictly necessary to use a solvent in the ester exchange reaction. Where a solvent is used, no particular limitation is placed on the type of the solvent, provided that it does not hinder the reaction. Among others, hydrocarbon solvents are preferred. Examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene; and aliphatic hydrocarbons such as hexane and cyclohexane. These solvents may be used alone or in admixture of two or more. These solvents are usually used in an amount of 0 to 1,000% by weight, preferably 0 to 500% by weight and more preferably 0 to 300% by weight, based on the combined weight of the jasmonic acid methyl ester and the alcohol.
The reaction temperature for the ester exchange may usually range from room temperature to 300° C., and the pressure therefor may be either atmospheric pressure or reduced pressure.
Although the reaction is preferably carried out in an inert atmosphere, the present invention is not limited thereto. In order to promote the reaction, the methanol formed during the reaction is preferably removed by distillation. Where methanol forms an azeotrope with the solvent used, it is favorable for the promotion of the reaction to distill off the methanol from the system as an azeotrope with the solvent. Employing the above-described conditions, the reaction may usually be completed in a period of time ranging from about 30 minutes to about 20 hours. After completion of the reaction, the reaction mixture is cooled and the catalyst is removed by a suitable means such as neutralization with an aqueous alkaline solution (e.g., a solution of sodium hydroxide, sodium hydrogen carbonate or sodium carbonate), filtration, washing or acid hydrolysis. Then, the reaction mixture from which the catalyst has been removed is washed with water and optionally with a saturated aqueous solution of sodium chloride or the like. After the aqueous layer is separated, the organic layer is dried over magnesium sulfate, sodium sulfate, molecular sieve or the like, and then distilled to remove any residual solvent and any residual starting compounds. Thus, the desired jasmonic acid ester compound can be obtained. Each of the aforesaid operations may be suitably omitted, and the order of these operations may be suitably changed as required. The ester thus obtained may further be purified by distillation under reduced pressure or atmospheric pressure, chromatography or the like.
Examples of the aforesaid alcohol include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, 2-methylbutyl alcohol, allyl alcohol, cis-2-penten-1-ol, trans-2-hexen-1-ol, 3-buten-1-ol, 4-methyl-3-penten-1-ol, cis-3-hexen-1-ol, propargyl alcohol, 2-pentyn-1-ol, 3-butyn-1-ol, 3-hexyn-1-ol, ethylene glycol and propylene glycol.
Industrial Applicability
The jasmonic acid compounds of the present invention have the ability to induce the germination of parasitic plants (in particular, parasitic weeds). There is a tendency for parasitic plants to be germinated only by some components emanating from host plants. However, prior to the planting of host plants, the germination of parasitic plants can be induced by the application of a compound in accordance with the present invention. Thus, the germinated parasitic plants are made to wither before attaching themselves to hosts (i.e., the so-called suicidal germination can be induced). Accordingly, the compounds of the present invention are useful as germination inducing agents for parasitic plants.
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention is further illustrated by the following examples. However, these examples are not to be construed to limit the scope of the invention. The resulting compounds were identified by proton NMR spectroscopy, IR spectroscopy and mass spectrometry.


REFERENCES:
patent: 5776860 (1998-07-01), Kamuro et al.
patent: 241 821 A3 (1987-08-01), None
patent: 2-11512 (1990-01-01), None
Meyers et al, “Dihydro-1,3-oxazines. XVI. A General Synthesis of 2-Alkylcyclopentenones and a Method for Adding CH2CO2Me to Electrophilic Olefins. Application to the Synthesis of Methyl Jasmonate” in J.Org.Chem. 1973, 38, 175-176.

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