Perfume compositions – Perfume compositions – Oxygen containing active ingredient
Reexamination Certificate
2002-01-10
2004-04-13
Warden, Jill (Department: 1743)
Perfume compositions
Perfume compositions
Oxygen containing active ingredient
C512S026000, C512S027000, C549S263000, C549S296000, C426S534000, C426S650000
Reexamination Certificate
active
06720302
ABSTRACT:
TECHNICAL FIELD
The present invention relates to the field of perfumery and the flavourings industry. More particularly, it relates to the use of (6R)-4,5,6,7-tetrahydro-3,6-dimethyl-3H-benzo[b]furan-2-one of the formula
as a flavouring or perfuming ingredient. The lactone of the formula (I) has excellent organoleptic properties, enabling it to be used to great advantage in perfumery and the flavourings industry.
The present invention also relates to a new process for the preparation of the lactone of the formula (I).
PRIOR ART
The chemical structure of (6R)-4,5,6,7-tetrahydro-3,6-dimethyl-3H-benzo [b]furan-2-one is known. In fact, K. Schulte-Elte et al in Tetrahedron (1967), 23(6), 2583-2599 identified the compound of the formula (I) in a mixture of lactones resulting from the photooxidation of menthofuran. Furthermore, J. Hirsch et al in J. Org. Chem. (1967), 32(9), 2915-2916 also identified the lactone (I) from among other end products resulting from the hydrolysis of &agr;,&agr;′-dimethoxydihydromenthofuran. However, these authors specify that the lactone (I) oxidises very easily under the synthesis conditions described to give a hydroxylactone, 5,6,7,7a-tetrahydro-7a-hydroxy-3,6-dimethyl-4H-benzo[b]furan-2-one of the formula
Moreover, some authors such as R. Woodward et al in J. Am. Chem. Soc. (1950), 72, 399-403, who have studied the oxidation of menthofuran by employing greatly varying experimental conditions, have never identified the lactone (I), but have obtained the hydroxylactone (II) as the only oxidation product.
So, although (6R)-4,5,6,7-tetrahydro-3,6-dimethyl-3H-benzo[b]furan-2-one has been detected among other reaction products during the course of studies into the reactivity of menthofuran, no document of the prior art describes optimum synthesis enabling the lactone (I) to be obtained without it oxidising rapidly to form the hydroxylactone (II). In addition, these references give no indication or even a suggestion of the possible use of the lactone (I) as a perfuming or flavouring ingredient.
Moreover, it is important to point out that certain documents of the prior art, which have analysed the constituents of natural products such as the essential oil
Pycnanthemum floridanum
(C. Shu et al, J. Ess. Oil Res. (1994), 6(5), 529-531) or wild species of peppermint (Nakayama T.; Higashiyama T.; Sakata I.; Hashizume T., Koryo, (1970), 97, 47-56) have identified a product that they refer to as “menthofurolactone”, without specifying its structure. It seems that there is some confusion in the literature with respect to the structure associated with this name: while Chemical Abstracts uses menthofurolactone to refer to the structure (6R)-4,5,6,7-tetrahydro-3,6-dimethyl-3H-benzo[b]furan-2-one, i.e. the lactone (I), documents of the prior art use this name to designate 5,6,7,7a-tetrahydro-7a-hydroxy-3,6-dimethyl-4H-benzo[b]furan-2-one of the formula (II).
For example, Ito et al in Kitami Kogyo Tanki Daigaku, Kenkyu Hokoku (1969), 2(4), 585-587, who describe “the isolation of menthofurolactone from
Mentha arvensis
”, associate the structure (II) with the name “menthofuro-lactone” and also describe its synthesis by the oxidation of menthofuran. Without doubt, the confusion arises from the fact that, as mentioned hereinabove, both the lactone (I) and the hydroxylactone (II) are products of the oxidation of menthofuran and, according to the prior art, the lactone (I) oxidises very easily to form the hydroxylactone (II). Consequently, the documents of the prior art by C. Shu et al and K. Umemoto, which refer to menthofurolactone as a constituent of a natural product without describing its structure and which date from later than the document by Ito et al referred to hereinabove, do not make it possible to establish what the structure of the lactone detected and named “menthofurolactone” was. On the basis of the experimental conditions employed in the prior art, the compound detected in the natural products is in fact the hydroxylactone of the formula (II). However, we have discovered quite surprisingly that the lactone of the formula (I) is present in the concrete of peppermint in trace form, although this constituent is very difficult to detect. In particular, we were able to ascertain that only certain experimental conditions, with respect to the choice of GC capillary column, allow the detection of the product by gas chromatography coupled with mass spectrometry, GCMS. For example, during GCMS analysis carried out using a polar column of the type used in the documents of the prior art which disclose analyses of natural products, the lactone (I) is not detected. In contrast, the same GCMS analysis carried out over an apolar column enabled us to observe the presence of (6R)-4,5,6,7-tetrahydro-3,6-dimethyl-3H-benzo[b]furan-2-one. It is clearly apparent from this comparison that the two documents referred to hereinabove are using the name “menthofuro-lactone” to designate the hydroxylactone (II).
Therefore, although of known structure, no document of the prior art describes an optimum synthesis of the lactone (I) which would prevent its rapid oxidation into hydroxylactone (II). Moreover, it seems that this lactone has never been identified as a constituent of a natural product. Finally, there is no mention or suggestion in the prior art of the use of (6R)-4,5,6,7-tetrahydro-3,6-dimethyl-3H-benzo[b]furan-2-one as a perfuming or flavouring ingredient.
REFERENCES:
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patent: 4113891 (1978-09-01), Winter et al.
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K.H. Schulte-Elte,“Photosensitized oxygenation of Alkyl-Substituted Furans”,Tetrahedron, Vol 23, pp. 2583-2599 (1967).
J. A. Hirsch and R.H. Eastman,“The Hydrolysis of &agr;, &agr;′-Dimethoxydihydromenthofuran”,Journal of Organic Chemistry,vol. 32, No. 9, pp. 2915-2916 (1967).
Woodward et al., “The Autoxidation of Menthofuran”, Converse Memorial Lab. of Harvard Univ., pp. 399-403, (1950).
Chi-Keun Shu et al., “Chemical Composition of the Essential Oil ofPycnanthemum foridanum”, Journal of Essential Oil Research, Vo. 6, No. 5, pp. 529-531 (1994).
K. Umemoto, “Essential Oil of Wind Mints Containing Pulegone and Menthofuran as Major constituents”, Laboratory of Chemistry, Nagoya Gakuin University, Vo. 18, No. 2, pp. 79-86 (1981).
T. Nakayama, “A New Japanese Peppermint”Shubi“ Developed in Okayama”, Department of Food Science and Technology, Kyoto University, No. 97, pp. 46-56, (1970).
Masaaki Ito et al, “Isolation of Menthofurolactone fromMentha arvensisand Solvent Effect fo Oil Components on the Fromation”, Kitami Kogyp Ta anki Daigaku, Kerkyu Hokoku, Vol 2, No. 4, pp 585-587 (1969).
Bagnoud Alain
Frerot Eric
Cole Monique T.
Firmenich SA
Warden Jill
Winston & Strawn LLP
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