Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2002-04-17
2003-02-25
Trinh, Ba K. (Department: 1625)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C549S546000, C514S475000, C512S013000
Reexamination Certificate
active
06525207
ABSTRACT:
TECHNICAL FIELD
This invention relates to a process for producing an epoxy compound represented by the following general formula (4):
(where R
1
denotes an alkyl group with 1 to 5 carbon atoms, alkenyl group with 2 to 5 carbon atoms or alkynyl group with 2 to 5 carbon atoms, and the wavy line denotes cis form, trans form or a mixture consisting of cis form and trans form.)
This invention also relates to a fragrance-, flavor- or scent-imparting composition containing said epoxy compound, and also to drinks & foods, perfumes, cosmetics and tobaccos respectively containing said compound.
The novel fragrance-, flavor- or scent-imparting composition containing said epoxy compound and foods & drinks, perfumes, cosmetics and tobaccos respectively containing said composition are intensified in fruity, camphoric, floral, amber or woody fragrance, flavor or scent.
BACKGROUND ART
Among the compounds represented by the general formula (4), 1-vinyl-13-oxabicyclo[10.1.0]tridecane is a publicly known chemical substance, and it is a useful compound for producing 5-cyclohexadecenone. The method of using the epoxy compound is described in JP 49-47345, A Gazette.
However, the fragrant properties of these epoxy compounds have not been recognized so far. Of course, there is no report about the use of them as fragrance-, flavor- or scent-imparting compositions and foods & drinks, perfumes, cosmetics and tobaccos respectively containing said compositions.
It is only known that 1,5,9-trimethyl-13-oxabicyclo[10.1.0]trideca-4,8-diene as an epoxy compound similar to the epoxy compounds represented by the general formula (4) has a woody amber fragrance.
As a method of synthesizing the 1-vinyl-13-oxabicyclo[10.1.0]tridecane, for example, disclosed is a process comprising the steps of letting vinylmagnesium chloride act on 2-chlorocyclododecanone, to make chlorohydrin, and cyclizing using sodium hydroxide or sodium methoxide as a base, as shown in the following reaction formula (“Synthetic Perfume Chemistry and Knowledge on Commercial Products (in Japanese)”, Yukagaku, 1974, Vol. 23, No. 6, Page 371). However, it does not describe anything at all about the stereochemistry of the obtained product.
However, the process for producing said epoxy compound has the following problem: the solvent must be once recovered after production of chlorohydrin, to increase the number of production steps; the cyclization reaction using sodium hydroxide as a base requires a long time and is low in yield; and sodium methoxide is relatively expensive and the treatment of the waste liquid after completion is difficult industrially disadvantageously.
On the other hand, it is general that compounds used as perfumes are quite different in fragrance even if they are slightly different in structure. So, it is very important for obtaining novel fragrances, to synthesize various compounds for examining their fragrances. Furthermore, the materials to be mixed are required to satisfy various demands such as low prices and unique fragrances. Numerous perfume materials that have a fruity, camphoric, floral, amber or woody fragrance are known, but the fashion of fragrances keeps changing with the age. So, it is very important to find novel perfume materials.
An object of this invention is to provide a process for producing an epoxy compound with said performance industrially advantageously at low cost in a short process.
Another object of this invention is to provide a novel fruity, camphoric, floral, amber or woody fragrance-, flavor- or scent-imparting composition, and foods & drinks, perfumes, cosmetics and tobaccos respectively containing said composition.
DISCLOSURE OF THE INVENTION
The inventors studied intensively to solve the problems of the conventional methods as described above, and found that epoxy compounds can be easily produced by means of a specific process. Thus, this invention has been completed.
The first subject matter of this invention is a process for producing an epoxy compound represented by the following general formula (4)
(where R
1
denotes an alkyl group with 1 to 5 carbon atoms, alkenyl group with 2 to 5 carbon atoms or alkynyl group with 2 to 5 carbon atoms, and the wavy line denotes cis form, trans form or a mixture consisting of cis form and transform), comprising the steps of letting an &agr;-halocyclododecanone represented by the following general formula (1)
(where X
1
denotes chlorine, bromine or iodine) and an organic magnesium compound represented by the following general formula (2)
R
1
MgX
1
(2)
(where R
1
denotes an alkyl group with 1 to 5 carbon atoms, alkenyl group with 2 to 5 carbon atoms or alkynyl group with 2 to 5 carbon atoms, and X
1
denotes chlorine, bromine or iodine) react with each other for Grignard reaction, hydrolyzing to obtain a halohydrin represented by the following general formula (3)
(where R
1
denotes an alkyl group with 1 to 5 carbon atoms, alkenyl group with 2 to 5 carbon atoms or alkynyl group with 2 to 5 carbon atoms; X
1
denotes chlorine, bromine or iodine; and the wavy line denotes cis form, trans form or a mixture consisting of cis form and trans form), and letting the halohydrin and a base react with each other in the presence of an phase transfer catalyst.
The second subject matter of this invention is a process for producing a compound represented by said general formula (4), comprising the steps of letting an &agr;-halocyclododecanone represented by the following general formula (1)
(where X
1
denotes chlorine, bromine or iodine) and an organic magnesium compound represented by the following general formula (2)
R
1
MgX
1
(2)
(where R
1
denotes an alkyl group with 1 to 5 carbon atoms, alkenyl group with 2 to 5 carbon atoms or alkynyl group with 2 to 5 carbon atoms, and X
1
denotes chlorine, bromine or iodine) react with each other for Grignard reaction, and adding an aprotic polar solvent, for epoxidation.
The third subject matter of this invention is a novel fruity, camphoric, floral, amber or woody fragrance-, flavor- or scent-imparting composition containing an epoxy compound represented by said general formula (4), and foods & drinks, perfumes, cosmetics and tobaccos respectively containing said composition.
THE BEST MODES FOR CARRYING OUT THE INVENTION
At first, an epoxy compound represented by said general formula (4) can be synthesized according to either of the following two processes.
(where R
1
denotes an alkyl group with 1 to 5 carbon atoms, alkenyl group with 2 to 5 carbon atoms or alkynyl group with 2 to 5 carbon atoms, and the wavy line denotes cis form, trans form or a mixture consisting of cis form and trans form).
In the first synthesizing process, an &agr;-haloketone represented by the formula (1) and an organic magnesium compound represented by the formula (2) are made to react with each other for Graignard reaction, to produce an alkoxymagnesium halide represented by the formula (5), and a hydrogen ion donor is added for hydrolysis, to produce chlorohydrin represented by the formula (3). Then, a base is caused to act on it in the presence of an phase transfer catalyst, for epoxidation reaction, to form an epoxy compound represented by the formula (4).
In the second process, an &agr;-haloketone represented by the formula (1) and an organic magnesium compound represented by the formula (2) are made to react with each other for Grignard reaction, to produce an alkoxymagnesium halide represented by the formula (5), and an aprotic polar solvent is added for cyclization reaction, to form an epoxy compound represented by the formula (4).
In the organic magnesium compound represented by the formula (2), R
1
denotes an alkyl group with 1 to 5 carbon atoms, alkenyl group with 2 to 5 carbon atoms or alkynyl group with 2 to 5 carbon atoms. Alkyl groups with 1 to 5 carbon atoms include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, 1-methylpropyl group, 2-methylpropyl group, pentyl group, 1,2-diemthylpropyl group, 1,1-dimethylpropyl group, 2,2-dime
Higashi Motoo
Ito Nobuhiko
Konno Yuki
Takaoka Hideaki
Schnader Harrison Segal & Lewis LLP
Soda Aromatic Co., Ltd.
Trinh Ba K.
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