DE2350388C3 - Use of tricyclic compounds as odor-giving components in perfumes - Google Patents

Description

The invention relates to the use of tricyclic compounds of the formula

(I)

which has a single bond or double bond in position 5.6 and in which the indices m, η and ρ denote the number O or 1, the symbols X taken together an oxygen atom or one of these symbols is an acyl, hydroxyl, O- Acyl, CH ₂ OH, CHjO-acyl or COO-alkyl group and the other represents a hydrogen atom, and in which

a) the symbol R represents a lower alkyl group if in and ρ are identical and equal to O and η is equal to I, or

b) the symbol R represents a lower alkylidep group if in and η are identical and equal to 1 and ρ is equal to O, or

c) one of the symbols R and R 'represents a lower alkyl group and the other ^{1 represents} hydrogen, if each of the subscripts in, η and ρ is equal to 1,

as an odor-giving component in perfumes.

In the present description, “lower alkyl groups” are to be understood as meaning straight or branched alkyl groups with 1-6 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, η-butyl, isobutyl or tert-butyl.
Of the tricyclic compounds that can be used according to the invention are 7,7-dimethyl-6-methylen-tricyclo [6.2.1.0'- ⁵ ] undecan-2-one and 7,7-dimethyl-6-methylen-tricyclo [6.2.1.0'- ⁵ ] undec-2-ylmethyl alcohol naturally occurring compounds. These two connections are by means of a very

ίο Complicated and expensive process isolated from vetiver oil [see "The Flavor Industry" 1,623 (1970) and "Perfume & Essential Oil Records" 60 307 Π 963)]. This process essentially consists in the essential oil being subjected to several fractional distillations and subjected to numerous separations by column chromatography. These two connections are trace subsurface plants that are found in essential oils in a concentration of 0.1-0.5% by weight each.

χ It has now been found that pure 7,7-dimethyl-6-methylene-tricyclo- [6 ^ .1.0'- ^s ] undecan-2-one develops a characteristic and strong odor with a peculiar fine wood-like note . It has also been found that this odor is very persistent and easily reproducible, while the odor of the natural essential oil, which is the result of the odors of the individual components of the essential oil, depending on the origin and the purity of the natural

in essential oils is not always the same.

Thanks to its special olfactory properties, the aforementioned tricyclic ketone is used in perfumery usable for a variety of purposes. Its range of use is wider than that of natural Vetiver oils. The said ketone allows to create novel, original wood smells, and exercises one reinforcing and fixative effects.

It has been found that the compounds of the formula I have interesting organoleptic properties and therefore for the manufacture of perfume compositions and for the manufacture of artificial ones essential oils are useful.

In perfumery, the tricyclic compounds of the formula I to improve or

4 "> Strengthening certain odor notes, e.g. woody-amber-like or balsamic scents. By using these connections it is possible to create novel perfume compositions that have an original, often surprising woody odor character who in certain cases have the smell of certain exotic woods, /. B. Cedar, Sandal, Olibanum or rosewood, or even reminiscent of amber, myrrh, ylang or patchouli. It was further found that the woody ones produced in this way

v> Notes are special. The use of the compounds of the formula I is particularly indicated in fine perfumery. The compounds mentioned can also be used to perfume soaps, detergents, waxes, household items and cosmetics

«Ι preparations are used.

When the compounds of the formula I are used according to the invention, interesting odor effects are achieved with amounts of about 1-5% of the total weight of a Parlüms. ] e according to the desired Gc-

odor effect or the nature of the other components of a perfume, however, there are also lower concentrations, / Ii. vo, ι 0.01% or higher con / enlra options of around 10 - 20% are possible. If the named

ten compounds are used as odor-enhancing additives in perfume bases, so the amounts up to about 80% of the total weight of the perfume base.

Several tricyclic compounds of the formula I have already been described in the chemical literature, for example:

a) 7,7-dimethyl-6-methylene-tricyclo [6J2.1.0 ^1-5] undecane-2-one:

was isolated from vetiver oil by the method described in "The Flavor Industry" I, 623 (1970).

M.p. 77-79 ° C; [α] = -117.4 ° (c = 9.5 JnCHCI ₃ ), IR (CCI ₄ ): 3100, 1740, 1645, 1465, 1410, 1385, 1255, 1220, 1170, 1150, 1010,980,900 cm- ',
KRS (CG ₄ ): 1.10 (6H, s); 4.64 and 4.81 (2 H, 2 broad s) δ ppm,
MS: M ⁺ = 204; m / e = 189, 161, 133, 108.

b) 6,7,7-trimethyl-tricyclo [6.2.1.0 ' ⁵ ] undecap.-2-one:
was produced by catalytic hydrogenation (10% palladium on carbon) of the unsaturated ketone mentioned under a).

[λ] = -137.3 ° (c = 3.4% in CHCl ₃ ),

IR (clear): 1740, 1460 cm ¹ ,

KRS (CCl ₄ : 0.82 (3 H, s); 0.88 (3 H, s); 0.84 (3 H, d, J = 5 Hz) ό ppm,

MS: M ⁺ = 206; m / e = 151, 150.41.

c) 7,7-Dimethyl-6-melhy! en-iricyclo [6.2.1.0 ^l - ⁵ ] undecan-2-ol:

was prepared by reducing the corresponding ketone (see, a)) using lithium aluminum hydride according to the method described in "The Flavor Industry" I, 623 (1970).
M.p. 57 ° C; [λ] = + 15.5 ° (c = 0.8% in CHCIι),
IR (CCl ₄ ): 3630, 3360, 3090, 1638, 1380, 1360, 1097, 1067, 890, 8bO cm ',

KRS (CCl ₄ ): 1.07 (6H, s); 3.10 (1 H. s); 4.02 (1H, t, 1 = 5.5 Hz); 4.53 (1 H. s); 4.78 (IH, s) δ ppm,
MS: M ¹ = 206: m / e = 136, 135, 119.91.

d) 6,7,7-trimethyl-tricyclo [6.2.1.0 ¹ ' ⁱ ] undecan-2-ol:
was prepared from öyj-Trimeihyl-tricyclcfJjJ.l.O '^ andcc-2-yi-methyl-kcton according to the method described in "Perfume and Essential Oii Records" 60, 307 (1969).

M.p. 135 ° C; [/ x] ', V = +40.4 "(c = 8.9% in CHCl ₁ ), IR (CCl ₄ ): 3620, 1460, 1380, 1370, 1050, 950 cm', KRS (CCI ₄ / DMSO -d ,,): 0.76 (3 H, d indefinite signal); 0.78 (3 H. s); 0.82 (3 H, s); 3.63 (1 H, d,) = 5 Hz); 3.65 (1H, s) (5 ppm,
MS: M '= 208; m / e = 190, 147, 44, 41.

c) 6,7,7-trimethyl-tricydo [6.2.1.0 ⁱ - '"'] undcc-2-ylc.stcr of acetic acid:

was obtained by oxidation of 6,7,7-trimethyl-trieyclo [6.2.1.0 ' "'] undec-2-yl-methyl-ketone using m-chloroprincnzoic acid according to the method of Baycr-Villigcr (see the references mentioned under d)).

M.p. 7b-77 C; [λ], = + 18, b "(c = 1.9 in CIICI ₁ ), IR (Cdi): 17 35.14b (>, 1 375, 1245, 1025cm ',
KRS (CCLi): 0.81 (3 11th undetermined signal); 0.82 (3 11, s); 0.85 (3 11th s); 1.93 (3 11, s); 4.8b (I II, d, I = 5 II /) <) ppm,
MS: pi / c = 140, 147, 120, I 19/4 5.

6,7,7 Trimethy] -t.-icyclo [6il.0 ¹ - ⁵ ] undec-2-ylmethyl-ketone:

was prepared by treating 6,7,7-trimethyltricyclo [6ü.0 ¹ J] undec-2-yl-carboxylic acid with methyllithium (see the literature cited under d))
[α] ;; = + 101.2 ° (c = 4.2% in CHCl ₃ ), IR (clear): 1705, 1455, 1355, l! 65cm- ', KRS (CCl ₄ ): 0.75 (3 H, s) ; 0.80 (3 H, d undetermined signal); 0.83 (3H, s); 2.05 (3H, s); 2.60-2.90 (1H, m) δ ppm,
MS: M + = 234; m / e = 163, 72, 43.

g) 7,7-Dimethyl-6-methylen-tricyclo [6.2.1.0'- ⁵ ] undecane-2-carboxylic acid methyl ester: was prepared from the corresponding acid by the method described in "Tetrahedron Letters" 1967, 2815.
[λ]? = + 54.5 ° (C = 1.8% in CHCl ₃ ), IR (clear): 3100, 1735, 1640, 1460, 1350, 1165, 890 cm- ',

KRS (CCl ₄ ): 1.05 (3H, s); 1.06 (3H, s); 2.53 (2H, m); 3.56 (3H, s); 4.60 (1H, broad s); 4.75 (1H, broad s) δ ppm,
MS: M + = 248; m / e = 183, 145, 119.41.

h) 6,7,7-trimethyl-tricyclo [6.2.1.0'- ⁵ ] undec-5-en-2-carbisiic acid methyl ester:
was prepared by treating the ester described under g) with formic acid (see the literature mentioned under d)). M.p. 46-48 ° C; [*] = + 50.5 ° (c = 2.8% in CHCIi),

IR (KBr): 1730, 1430, 1350, 1200-1150, 1038.980. 863, 725 cm ',

KBS (CCU / CDCIj): 0.99 (6H, s); 1.47 (3H, s); 2.31 (2H, t, | = 6.5 Hz); 2.70 (1H, d of d, J, = 6 Hz, J ₂ = 4.5 Hz); 3.57 (3 H, s) Ά ppm, MS: M ⁺ = 248; m / e = 248, 233, 145, 119.

i) 7,7-Dimethyl-6-methylen-trieyclo [6.2.1.0 ¹⁵ ] undec-2-yl-methyl-alcohol:

isolated from vetiver oil or by reduction of vctivensäurc with lithium aluminum hydride (see the literature mentioned under d)).

[λ] = + 35, r (c = 2% in CHCIj), IR (clear): 3350, 3100, 1635, 1465, 1380, 1362, 1025, 890 cm ',

KRS (CCl ₄ ): 1.06 (6H, s); 3.53 (2H, m); 4.57 and 4.71 (2x1 H, broad s); 4.96 (1H, s) O ppm, MS: M * = 220; m / e = 119, 91, 44, 41.

j) 6,7,7-trimethyl-tricyclo [6.2.l.0 ^l ' ⁱ ] undec-2-ylmethyl alcohol:

was prepared by catalytic hydrogenation of the corresponding unsaturated alcohol (see i)) in the presence of PtCh (see the literature mentioned under d)).
[λ]; '= +70.4 "(c = 2.2% in CHCh). IR (clear): 1735, MbO, 1355, 1195, 1180, 1160cm', KRS (CCI ₄ ): 0.78 ( J II, s); 0.78 (3 H, d, | = 5 Hz); 0.85 (3 H, s); 2, "3O (I 11, s); 3.58 (3 M ₁ s) δ ppm, MS: M '= 250; m / e = 190, 55, 41.

7,7-Dimethyl-6-melhylen-lricyclo [b.2.IO ^l - ⁱ "'] undecan-2-one (see; ι) can also be prepared as follows (temperatures in degrees Celsius):

a) Acetic acid-yj-dimethyl-e-methylentricyclofeü. O '-' jundec ^ -yl-ester

A mixture of 4.68 g (20 mmol) of 7,7-dimethyl

6-methylen-tricyclo [6.2.1.O'-sjundec ^ -yl-carboxylic acid (vetivenic acid) and a solution of 16.4 g of anhydrous sodium acetate in 45 ml of acetic acid was heated to 75 °. The reaction mixture was all at once 12.0 g lead tetraacetate added. _{CO 2} development started immediately. The reaction mixture was kept at 75 ° for 60 minutes, then cooled, diluted with 300 ml of water and finally extracted with 6 portions of 200 ml of n-pentane. After washing and drying, the combined organic extracts were concentrated. 4.61 g (92%) of crude product were obtained, which consisted of 80% of the desired acetate (as the chromatography in the gas phase on CARBOWAX 20 M / 250 "showed). This product was used for the subsequent reaction without further purification. A pure sample was obtained by colon chromatography (silica gel 0.05-0.2 mm; hexane / ethyl acetate 98: 2). The pure product had the following physical properties:

[«]?" = + 16.3 ° (c = 1.2% in CHCl ₃ ).

IR (CCU): 3085, 1730, 1633, 1240, 1030, 890 cm- '.

KRS (CCl ₄ ): 1.07 (3H, s); 1.10 (3H, s); 1.96 (3H, s); 2.70 (1H, m); 4.60 (1H, broad s); 4.78 (1H, broad s), 4.95 (1H, d, J = 5 Hz) O ppm.

MS: m / e = 188 (100), 173 (80), 145 (93), 43 (71). _{i (} ,

b) 7,7-Dimethyl-6-methylentricyclo [6.2.1.0'- ⁵ ] undecan-2-ol

A solution of 9.7 g (39 mmol) of the acetate prepared according to a) in 50 ml of anhydrous ether was added dropwise to a suspension of 1.85 g (48 mmol) of lithium aluminum hydride in 100 ml of anhydrous ether at 20 °. The reaction mixture was refluxed for 2 hours and then diluted with an equal volume of water. The organic phase was washed, dried and concentrated by customary methods. 8.4 g of crude product were obtained, 80% of which consisted of 7,7-dimethyl-6-methylen-tricyclo- [6.2.1.0'- ⁵ ] undecan-2-ol (like chromatography in the gas phase on CARBOWAX 20 M / 250 ° 4-. Showed).

1 »] ΐ = + 39.3 ° (c = 0.7% in CHCl ₃ ).

c) Oxidation of the 7,7-dimethyl-6-methylentricyclo [6.2.1.0'- ⁵ ] undecan-2-ol

5 (1

It was first O ₇ · 2 H ₂ O water produced mil in 300 ml of water to 136 ml concentrated sulfuric acid and diluting to 500 ml of a solution of chromic acid by adding a solution of 100 g (33OmMoI) Na ₂ Cr. ₂ r>

52 g of the chromic acid solution were added dropwise with vigorous stirring to a solution, cooled to 0 °, of 5.2 g of the alcohol prepared according to b) in 120 ml of ether. The reaction mixture was stirred for 15 min., Then poured into crushed ice and washed with ether. The organic phase was washed first with 10% aqueous sodium bicarbonate solution and then with saturated aqueous sodium chloride solution A narrow extract by customary methods gave t, ^r > 3.8 g of crude product, 80% of which consisted of the desired ketone: pure 7,7-dimethyl-6-methylene-tricyclo [6.2.1.0'- ⁵ ] undecane -2-one was obtained by column chromatography (silica gel 0.05 to 0.2 mm; hexane / ethyl acetate 90:10) The purified product was identical to an authentic sample of the same compound.

The 7,7-dimethyl-

6-methylen-tricyclo [6.2.1.0'- ⁵ ] undec-2-yl-carboxylic acid (vetivenic acid) can be used directly in the form available on the market (degree of purity about 90%) or purified in the manner described below before use :

A solution of 50.0 g of crude vetivenic acid in 250 ml of acetone was added to 25 g of cyclohexylalmine. Of the solid precipitate was made 3 times from a 10:! mixture crystallized from acetone and methanol and then hydrolyzed using 2η hydrochloric acid. 41.5 g were obtained (83%) pure vetivenic acid.

M.p. 76-78 °: [λ]? = + 25.9 ° (c = 1.5% in CHCl ₃ ).

IR (CCI ₄ ): 3100, 2800-2400, 1700, 1640, 1462, 1420, 1380, 1365, 1230.895 cm- '.

KRS (CCI ₄ ): 1.08 and 1.11 (6 H, 2 s); 4.66 (1 H. m); 4.82 (1H, m); 11.03 (1H, s) ö ppm.

MS: M + = 234; m / e = 219, 164, 119.

The new compounds of the formula I described below were prepared as follows:

6,7,7-trimethyl-tricyclo [6.2.1.0 ' ⁵ ] undec-5-en-2-one

350 mg of 7,7-dimethyl-6-methylen-tricyclo [6.2.1.0 '· ⁵ ] -undecan-2-one were heated for 5 days at 40 ° in the presence of 20 ml of 98% formic acid. The reaction product was obtained in the usual manner by extraction. Washing, drying and evaporation worked up. 330 mg of crude product were obtained (degree of purity 90%). The pure compound was obtained by crystallization from n-pentane.

M.p. 35-36 °; [α], = -211.7 ° (c = 1.5% in CHCl ₃ ).

IR (KBr): 1740, 1450, 1405, 1383, 1360, 1310, 1195, 1170, 1008.978 cm- '.

KRS (CCl ₄ ): 1.01 (6H, s); 1.52 (3H, s); 1.9-2.7 (4H, m) <5ppm.

MS: M ⁺ = 204; m / e = 189, 161, 133, 119.

The same procedure was used under analogous conditions (one night at 20 °) to convert the acetic acid 7,7-dimethyl-6-methylene-tricyclo [6.2.1.0 '· ⁵ ] -undec-2-yl methyl ester. One received:

6,7,7-trimethyl-tricyclo [6.2.1.0'- ⁵ ] undec-5-en-2-yl methyl ester

[α] V = + 46.5 ° (C = 1.5% in CHCl j).

IR: 1740, 1455, 1383, 1362, 1240, 1030 cm- ¹ .

KRS (CCI ₄ ): 0.96 (3H, s); 0.99 (3H, s); 1.43 (3H, s); 1.93 (3H, s); 3.84 (2H, m) δ ppm.

MS: M ⁺ = 262; m / e = 202, 187, 159, 43.

The invention is illustrated by the following working examples.

example 1

A perfume base was made by mixing the following substances:

Parts by weight

Decanal 10% *)
Undecanal 10% *)
Dodecanal 10% *)
Methyl nonylacelaldehyde 10% *
Angclica root oil 10% *)
Castorcum 10% *)

10 40 10 10 10 20th

Natural defatted civet 10% *

Galbanum oil

Jasmine absolute

Olibanum oil

Patchouli

A-phenylethyl acetate

Oi- isomethylionon

Coriander oil

Hydroxycitronellol

Cyclopentadecanolide 10% *)

Synthetic jasmine

Synthetic Bergamo »

Synthetic lemon oil

Oak moss absolute 50% *)

Oriental sandalwood oil

Synthetic neroli

Muscon 10% *)

Coumarin

Ambrette musk

Ketone musk

Diethyl phthalate

Total

Weighted part c

10 10 50 10 80 15 95 5

65 50

too

100 40 30 30 20 50 50 10 30 50

1000

*) Solution in diethyl phthalate.

5 g of 7,7-dimethyl-6-methylene-tricyclo [6.2.1.0'- ⁵ ] undecan-2-one were added to 95 g of this perfume base. In this way, a new perfume composition was obtained which had an original and very harmonious woody odor groove.

By using the corresponding saturated tricyclic ketone in the same amount instead of the unsaturated one Ketones, a perfume composition was obtained which had a distinctive, pleasant woody odor note.

Example 2

A perfume base with a Chypre odor was made by mixing the substances listed below manufactured:

Weight share a-phenylethyl acetate 30th Undecenal 10% *) 100 x-methylundecenal 10% *) 20th Coumarin 60 Vanillin 5 rNClU! | -IVI \ J3t "l! L13 55 Cyclopentadecanone 10% *) 30th oil isomethylionon 60 Oak moss absolutely 20th Labdanum absolutely 10 Synthetic galbanum 10 Synthetic castoreum 20th 2-pentyl-3-oxo-cyclopenty-acetic acid 50 methyl ester Benzyl acetate 100 Indole 10% *) 10 Hexyl cinnamaldehyde 50 Synthetic rose 50 Patchouli 20th Synthetic bergamot 200

To 90 g of this perfume base were 10 g of a 10% solution of 7,7-dimethyl-6-methylene-tricyclo [6.2.1.0 ^l5] undecane-2-one in diethylphthalate. In this way, a new perfume composition was obtained that had a very elegant and original woody scent note with a very natural fullness.

By adding the same amount of 6,7,7-trimethyl-tricyclo [6.2.1.0 ^l5] undec-5-en-2-one or 6,7,7-trimethyl-tricyclo [6.2.1.0 ^15] undecan-2- On the perfume base, a perfume composition was obtained which had a markedly woody and amber-like fragrance.

By adding the same amount of 6,7,7-trimethyl-tricycloljj ^ .l.O '-' Jundec ^ -yl-methyl-ketone or acetic acid-7.7-dimethyl-6-methylene-tricyclo [6.2.1.0'- ⁵ lundec-2-yl-methyl-ester to the perfume base an original and particularly pleasant woody and slightly balsamic fragrance was obtained, which is reminiscent of cedarwood.

Example 3

A perfume base for a eau de cologne for men was made by mixing those enumerated below Substances made:

Weight share Sage oil 20th Lavender oil 150 Synthetic bergamot 200 lemon oil 140 Sweet orange oil 40 Synthetic galbanum 10% *) 20th Muscon 10% *) 50 2-pentyl-3-oxo-cyclopentyl acetic acid 10 methyl ester 1.1-Dimethyl-6-tert-butyl-4-acetylindane 10 Oi- isomethylionon 50 Synthetic ylang 80 Synthetic jasmine 25th Synthetic geranium 50 Synthetic neroli 100 Coriander oil 5

Total
Solution in diethyl phthalate.

950

Total
*) Solution in diethyl phthalate.

900

By adding 5 g of a 10% solution of

7.7-Dimethy -6-methylene-tricyclo! [6.2.1.0 ^1-5] undecane-2-one in diethyl phthalate 95 g of perfume base of a new perfume composition was obtained that a Sehi original and elegant woody scent with a very abundance natflrlicher exhibited.

By using the same amount of 6,7,7-trimethyl-tricyclopj ^ -l.O'-Sjundec-S-en ^ -one or 6,7,7-trimethyl-tricyclo [6.2.1.0 ¹⁵ ] undecan- 2-on, a perfume composition was obtained which had a very pronounced woody and amber-like fragrance.

By adding the same amount of 6,7,7-trimethyl-tricyclo [6.2.1.0 ^I ' ⁵ ] undec-2-yl-methyl-ketone or acetic acid-7,7-dimethylene-tricyclo [6.2.l.0 ¹ ' ⁵ ] undec-2-ylmethyl ester to the perfume base, a new and particularly pleasant woody and slightly balsamic note was created that was reminiscent of cedarwood.

Claims (1)

Claim: Use of tricyclic compounds of the formula which has a single bond or double bond in the 5, 6 position and in which the indices m, η and ρ denote the number 0 or 1, the symbols X taken together an oxygen atom or one of these symbols is an acyl, hydroxyl, O- Acyl, CH ₂ OH, CH ₂ O-ACyI or COO-alkyl group and the other represents a hydrogen atom, and in which a) the symbol R represents a lower alkyl group when m and ρ are identical and equal to O and η is equal to 1, or b) the symbol R represents a lower alkylidene group when m and η are identical and equal to 1 and ρ is equal to O, or c) one of the symbols R and R 'represents a lower alkyl group and the other represents hydrogen if each of the subscripts / η, η and ρ is equal to 1, as an odor-giving component in perfumes.