CH680044A5 - Di:methyl-oxa-bi:cyclo-octanone derivs. - useful as perfume components, with herbaceous, spicy notes for cosmetics, shampoo, etc. - Google Patents

Abstract

The use as perfume ingredients of the lactones of formula (I), as racemate or optically active isomers is new. m,n,r and p = 0 or 1, but m is different from n, and r is different from p; R=H or 1-4C alkyl. (I) are new cpds. except for racemic 7,7-dimethyl-2-oxabicyclo (4,1,1)octam-3-one(Ia;p=1, n=zero, R=H). The optically active, (-)-(IR,6S) and (+)-(1S,6R), forms of (Ia); is specifically claimed. USE - (I) are useful in e.g. toilet waters, shampoos, cosmetics, detergents etc., and impart herbaceous, spicy notes. In particular, (Ia) has haylike, coumarin-like and vernal grass-like top notes with a camphoroceous, fencyl-like base note, giving the odour a natural character. The 4-methyl deriv. of (Ia) has a hay-like, fenugreek odour, weaker than (Ia), but with an additional nutty character.

Description

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CH 680 044 A5

Description

The present invention relates to perfumery. It relates more particularly to the use, as perfuming ingredient, of a lactone of formula in which the indices m, n, r and p represent whole numbers of value 0 or 1, m being different from n and p being different from r, and the symbol R represents a hydrogen atom or an alkyl radical, linear or branched, from C1 to C4, in the form of a racemate or one of its optically active isomers.

The lactones of formula (I) are compounds of new chemical structure, with the exception of 7,7-dimethyl-2-oxabicyclo [4.1.1] octan-3-one whose preparation has been described by D. Joulain et al., in CR Acad. Se. Paris 273. Series C - pages 561 to 564 (1971) and D. Joulain, Doctoral thesis of 3rd cycle, University of Le Mans, 1971. However, the odorous properties of this lactone went completely unnoticed. Likewise, these authors do not mention any particular stereochemistry of the molecule.

We have now discovered that the lactones of formula (I), as well as their optically active isomers, have very interesting odorous properties, which make their use, as active ingredients in perfume compositions and perfumed articles, very advantageous. Indeed, these lactones develop odorous notes of herbaceous, spicy type which lend themselves well to a use in perfuming compositions of very varied type.

In particular, 7,7-dimethyl-2-oxabicyclo [4.1.1] octan-3-one, which we quote here as a preferential one, develops a fragrant note of head of the hay, coumarine, flouve type, while its base note has a very interesting camphor, fenchylic character. This base note is powerful and rising and gives the smell of the product a natural, slightly thujonic appearance, in the direction of sagebrush and hyssop. Due to its fragrant qualities, this lactone lends itself particularly well to use in fragrance compositions of various types, notably herbaceous, leathery and Cyprus, to which it gives a hyssop, aromatic and thuonic character.

Another preferred compound according to the invention, namely 4,7,7-trimethyl-3-oxabicyclo [4.1.1] octan-2-one, has a fenugreek, hay type odor, weaker than that of lactone cited above, also with a nutty side.

As mentioned above, the lactones (I) also lend themselves well to the preparation of various perfume compositions, and in particular of perfumes and eau de toilette, and to the scent of various products such as soaps, shower or bath gels, shampoos , body deodorants, cosmetic products and detergents or fabric softeners.

The concentrations in which the lactones of the invention can be used in the cited applications vary over a wide range of values. By way of illustration, mention may be made of concentrations of 1 to 10%, or even 20% by weight, of lactone (I) relative to the weight of a given perfume composition in which it is incorporated. For this purpose, concentrations of 1 to 5% prove to be preferable. When it comes to the use of these lactones for the perfume of the aforementioned miscellaneous articles, the concentrations of lactone (I) can be much lower than the values quoted.

It is clear that the compounds of the invention can be used in these applications either alone or as a mixture with other perfuming ingredients, solvents and carriers customary in perfumery.

As compounds of new structure, the lactones of formula (I), with the exception of 7,7-dimé-thyl-2-oxabicyclo [4.1.1] octan-3-one, are also the subject of the present invention. These lactones can be present either in the form of racemic and other mixtures, or in the form of optically active isomers in the pure state, of which the compounds represented below

(I)

R

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CH 680 044 A5

O

O

0 u

(-M1R.6S)

(+ M1S.6R)

(lia)

(Hb)

are examples relating to 7,7-dimethyl-2-oxabicyclo [4.4.1] octan-3-one.

According to the invention, the lactones (I) are prepared according to an original process which comprises the oxidation, under the conditions of the Baeyer-Villiger reaction, of a ketone of formula in which the indices n and m are different and represent whole numbers of value 0 or 1, and the symbol R represents a hydrogen atom or an alkyl radical, linear or branched, from C1 to C4. It is in fact the specific configuration of the starting ketone (III) (R = H) which determines that of the final product, since the relative configuration of the two cycles is retained in the reaction. The conditions of the Baeyer-Villiger reaction, and of the treatment for elimination of the peroxides which follows, are known to the person skilled in the art and a more detailed discussion of this subject seems to us superfluous here [see for example, the patent German DD 266 095, published on 22. 03. 1989]. The specific reaction conditions are discussed, case by case, in the examples presented below. The starting ketones (III) are products available on the market or which can be prepared by known methods.

The invention will now be described in more detail with the aid of the preparation examples presented below for purely illustrative purposes (the temperatures are given in degrees centigrade and the abbreviations have the usual meaning in the art). In particular, it should be noted that a person skilled in the art is able to use the information contained in these examples to adapt them to the preparation of other isomers not exemplified, as well as racemic or other mixtures, without having this requires an inventive effort. These examples cannot therefore be interpreted restrictively of the scope of the invention.

These reflections are just as relevant with regard to the examples of application in perfumery presented below.

Example 1

Preparation of M- (1 R.6SV7.7-dimethvl-2-oxabicvclor4.1.11octan-3-one

5.00 g of (+) - (1 R, 5S) -6,6-dimethyl-bicyclo [3.1.1] heptan-2-one or (+) - nopinone in 120 ml of methylene chloride (containing 1% ethanol) were treated with 16.0 g of 3-chloroperbenzoic acid and 4.00 g of trifluoroacetic acid for 10 days. The reaction mixture was filtered and then washed with a solution capable of removing the peroxides, dried and concentrated. The residue was etherified, washed with sodium bicarbonate and then water, and dried to provide 4.53 g of crude product. The latter was chromatographed on silica gel, using a cyclohexane / ether mixture (4: 1) as eluent. 3.04 g of the desired product (37% yield) were obtained pure.

[oc] 2o ° d = - 99.7 ° (2.0% in GHCI3)

IR: 1757 cm-1 (C = 0)

CH NMR, 360 MHz, GDCI3): 0.89 (s, 3H); 1.30 (s, 3H); 2.11 (d, 1H); 2.89 (m, 2H); 4.33 (m, 1H) 6 ppm NMR (13C): 18.4 (q); 22.1 (t); 26.4 (t); 27.3 (q); 34.0 (t); 41.2 (d); 43.0 (s); 84.0 (d); 174.7 (s) 8 ppm MS: 154 (trace, M +), 111 (25), 83 (50), 69 (100), 55 (74), 41 (20).

(! ")

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Example 2

Preparation of (1 R.6 Si-7.7-dimethvl-3-oxabicvclor4.1 .noctan-2-one

A solution of 20.0 g of (+) - nopinone and 35.0 g of 3-chloroperbenzoic acid in chloroform (250 ml, filtered through an aluminum oxide column, activity 1, to remove all traces ethanol) was left to stand for 6 days in the dark. A further 10.0 g of peracid was then added and the mixture allowed to stand for an additional three weeks. After filtering the precipitate of 3-chlorobenzoic acid and removing the peroxides as described above, the mixture was concentrated, the residue diluted slightly with cyciohexane and the additional amount of chlorobenzoic acid was filtered. The residue was chromatographed on a silica gel column as in the previous example to provide 2.30 g of chlorobenzoic acid, 3.70 g of nopinone, 7.30 g of the lactone prepared in example 1 and 0.98 g of a mixture containing the latter plus the above-mentioned desired lactone (37% by weight of the desired product). The latter, or (1R, 6S) -7,7-dimethyl-3-oxabicyclo [4.1.1] octan-2-one, was purified by preparative gas chromatography on a Carbowax column.

IR: 1756 cm-1 (C = 0)

NMR (1H, 360 MHz, CDCIs): 1.04 (s, 3H); 1.39 (s, 3H); 2.31 (d, 1H); 2.94 (m, 1H); 4.32 (dxd, 1H); 4.70 (dxt, 1 H) 5 ppm

MS: 154 (0, M +), 139 (2), 111 (18), 83 (100), 82 (36), 67 (30), 55 (63).

Example 3

Preparation of 4.7.7-trimethvl-2-oxabicvclor4.1.noctan-3-one and 4.7.7- trimethvl-3-oxabicvclor4.1 .noctan-2-one

5.00 g of (1 R, 4RS, 5S) -4,6,6-trimethyl-bicy-clo [3.1.1] heptan-2-one (methylnopinone) were left to stand for 5 weeks in the dark , 4R / 4S ~ 88/12) and, 10 g of 3-chloroperbenzoic acid (85% pure) in 100 ml of methylene chloride (from which the ethanol was removed). After the usual treatment of the reaction mixture and chromatography on a silica gel column, 800 mg of starting methylnopinone, 338 mg of (1R, 4R, 6S) -4,7,7-trimethyl-2-oxabicyc were recovered. 4.1.1] octan-3-one and 2.40 g of (1R, 4R, 6S) -4,7,7-trimethyl-3-oxabicyclo [4.1.1] octan-2-one.

Analytical data:

1. (1 R.4R.6SV4.7.7-trimethvl-2-oxabicvclo [4.1 .noctan-3-one

OH NMR, 360 MHz, CDCIs): 0.84 (s, 3H); 1.28 (s, 3H); 1.31 (d, 3H); 2.17 (d, 1H); 2.97 (m, 1H); 4.33 (t, 1H) 8 ppm

MS: 168 (0, M +), 153 (1), 124 (8), 97 (25), 69 (100), 55 (28), 41 (57).

Due to the isomeric mixture of methylnopinone used as starting material, a small amount of (1 R.4S.6SV4.7.7-trimethvl-2-oxabicvclor4.1 .noctan-3-one was also obtained, including the mass spectrum was practically identical to the one presented above.

2. (1 R.4R.6SV4.7.7-trimethvl-2-oxabicvclor4.1.1loctan-2-one P. f .: 80-81 °

NMR (1H, 360 MHz, CDCIs): 1.04 (s, 3H); 1.37 (s, 3H); 1.42 (d, 3H); 2.29 (d, 1H); 2.94 (dxd, 1H); 4.97 (m, 1 H) 8 ppm

MS: 168 (0, M +), 153 (1), 140 (1), 111 (40), 83 (100), 81 (33), 55 (65).

Example 4

Preparation of (± i-7.7-dimethvl-3-oxabicvclo [4.1.1 loctan-4-one

3.00 g of 6,6-dimethyl-bicyclo [3.1.1] hepta-3-one or isonopinone and 9.00 g of 3-chloroperbenzoic acid in chloroform (100 ml, released from ethanol) were left resting in the dark for 9 days. The 3-chlorobenzoic acid which had precipitated was filtered and the peroxides were removed. After concentrating the filter and preparative gas chromatography, 3.84 g of the desired product was obtained as a crystalline racemic mixture.

Mp: around 23 °

NMR (1H, 360 MHz, CDCIs): 0.95 (s, 3H); 1.32 (s, 3H); 1.58 (d, 1H); 1.87 (m, 1H); 2.28 (m, 1H); 2.60 (dxd, 1H); 2.81 (d, 1H); 2.89 (dxd, 1H); 4.40 (m, 2H) 8 ppm NMR (13C): 19.7 (q); 25.4 (t); 28.5 (q); 36.7 (t); 37.2 (d); 38.7 (s); 43.8 (d); 71.5 (t); 174.5 (s) 8 ppm SM: 154 (0, M +), 139 (3), 113 (8), 95 (13), 94 (16), 69 (100), 68 (40), 67 (32 ), 41 (90), 39 (26).

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Example 5

Preparation of a perfume composition

A basic perfuming composition, of the lavandin type, was prepared by mixing the following ingredients:

Ingredients

Parts by weight a-Pinene

100

Linalyl acetate

350

Geranyl acetate

75

Borneol

15

Camphor

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Linaloi

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Linalyl isopeniyrate

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Eucalyptol

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Linalyl propionate

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Geraniol

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Ethylamyl ketone 10% *

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Terpineol

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Total

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* in dipropylene glycol (DIPG)

To this herbaceous base composition was added 30 parts by weight (3%) of (-) (1 R, 6S) -7,7-dimethyl-2-oxabicyclo [4.1.1] octan-3-one. A new composition was thus obtained, of which the hysterical, aromatic and thujonic character was enriched.

A similar effect was observed for concentrations of 0.5 to 4.5% by weight of the product of the above-mentioned invention, relative to the weight of the base composition. The latter can be of varied type, from the odorous point of view. Indeed, the use of the compound of the invention in compositions of the leathery or Cyprus type, within the limits of the aforementioned concentrations, has proved to be as fortunate as in the lavandin composition exemplified, the enrichment in the henchopic, fenchylic note , sagebrush having been found each time.

Example 6

Preparation of a scented soap

To a mass of shaved soap, obtained from a sodium soap base prepared from coconut oil and tallow, was added 1% by weight of (-) - 7,7-dimethyl-2 oxabicyclo [4.4.1] octan-3-one, relative to the weight of soap. The base fatty note of the latter was then covered by a hyssop, herbaceous, aromatic note, with a natural side evoking pine.

Claims (10)

Claims 1. Use as a perfuming ingredient of a lactone of formula 5 5 10 15 20 25 30 35 40 45 50 55 CH 680 044 A5 in which the indices m, n, r and p represent whole numbers of value 0 or 1, m being different from n and p being different from r, and the symbol R represents a hydrogen atom or an alkyl radical, linear or branched, from Ci to C4, in the form of a raçémate or one of its optically active isomers. 2. Use according to claim 1, characterized in that the lactone of formula (I) is 7,7-dimé-thy! -2-oxabicyclo [4.4.1] octan-3-one, in the form of a racemate or one of its optically active isomers of formula or (-H1R.6S) (lia) (+ H1S.6R) (Hb) 3. Perfuming composition containing a lactone of formula (i) as defined in claim 1, in the form of a racemate or one of its optically active isomers, as a perfuming ingredient. 4. Perfume composition according to claim 3, characterized in that the lactone of formula (I) is 7,7-dimethyl-2-oxabicyclo [4.4.1] octan-3-one, in the form of a racemate or one of its optically active isomers of formula (IIa) or (IIb). 5. Perfumed product containing a lactone of formula (I) as defined in claim 1, in the form of a racemate or one of its optically active isomers, as a perfuming ingredient. 6. Perfumed product according to claim 5, characterized in that the lactone of formula (I) is 7,7-dimethyl-2-oxabicyclo [4.4.1] octan-3-one, in the form of a racemate or one of its optically active isomers of formula (IIa) or (IIb). 7. As a perfumed product according to claim 5 or 6, a perfume or eau de toilette, a shampoo, a body care product, a cosmetic product or a detergent. 8. 7,7-dimethyl-2-oxabicyclo [4.4.1] octan-3-one in an optically active stereoisomeric form of formula 0 u (-H1R.6S) (lia) (+ H1S.6R) (IIb) 9. Lactone of formula 6 5 10. Process for the preparation of a lactone of formula (I) as defined in claim 9, in the form of a racemate or one of its optically active isomers, characterized in that it is subjected to oxidation, under the conditions of the Baeyer-Villiger reaction, a ketone of formula in which the indices n and m are different and represent whole numbers of value 0 or 1, and the symbol R represents a hydrogen atom or an alkyl radical, linear or branched, from Ci to C4, in the form of a racemate, or respectively of an appropriate optically active isomer of said ketone, and said lactone (I) is separated in racemic form, or respectively the optically active isomer of that here, of the reaction product. 3 ("D 7 10 15 20 25 30 35 40 45 50 55 60 65 CH 680 044 A5 O <?) r (I) R in which the indices m, n, r and p represent whole numbers of value 0 or 1, m being different from n and p being different from r, and the symbol R represents a hydrogen atom or an alkyl radical, linear or branched, from Ci to C4, it being understood that the symbol R cannot represent a hydrogen atom when n = 0 and p = 1, in the form of a racemate or one of its optically active isomers.