WO1986003737A1

WO1986003737A1 - Tricyclo ad5.2.1.02,6 bd decane/decene derivatives with functionalized alkylidene side chains and utilization thereof as perfuming substances

Info

Publication number: WO1986003737A1
Application number: PCT/DE1985/000531
Authority: WO
Inventors: Ernst-Joachim Brunke
Original assignee: Dragoco Gerberding & Co. Gmbh
Priority date: 1984-12-19
Filing date: 1985-12-16
Publication date: 1986-07-03
Also published as: EP0215799A1; JPS62501149A; DE3564564D1; JPH0471895B2; EP0215799B1

Abstract

New tricyclo [5.2.1.0<2,6>] decane/decene derivatives having the formula (I) wherein R<d>, in the case where R<d> = -CH3, is in position C7 or C8, the dotted lines between C3 and C4 and C4 and C5 represent either two single C-C bonds or a C-C double bond and a C-C single bond and the waved lines represent stereoisomer forms which may be prepared by deconjugation of the corresponding alpha , beta -unsaturated carbonyl compounds which is optionally followed by a reduction and are preferably used as perfuming substances, in particular in perfume compositions for perfuming cosmetic and technical products.

Description

Tricyclo [5.2.1.0 ^2.6 ] decane / decene derivatives with a functionalized alkylidene side chain and their use as fragrances

The invention relates to new tricyclo [5 .2. 1 .0 ^{2, 6} ] decane / decene derivatives with the general formula A

R ^a = R ^b = R ^c = R ^d = HR ^a , R ^b , R ^c = H, CH ₃ (2xH, 1xCH ₃ ), R ^d = CH ₃

R ¹ , R ² : H, C ₁ -C ₆ alkyl

2,6-endo 2,6-exo 9,1'-Z 9,1'-E

wherein the radical R ^d in the case of R ^d = -CH ₃ at C-7 or C-8, the dashed lines between C-3 and C-4 and C-4 and C-5 ent represent neither two CC single bonds or one CC single bond and one CC double bond and the serpentine lines denote stereoisomeric forms. The invention further relates to the use of the new compounds of the general formula A as fragrances or as components of perfume oils for cosmetic or technical consumer goods.

Tricyclo [5.3.1.0 ² , ⁶ ] deca-4,8-diene 1, also known as dicyclopentadiene, is an industrially important raw material for the production of chemicals, including the manufacture of fragrances with a saturated ring system, which is produced in large quantities or unsaturated tricyclo¬ [5.2.1.0 ^{2, 6} ] decane backbone (overview in: H. Aebi, E. Baumgartner, HP Fiedler and G. Ohloff, "Cosmetics, Fragrances and Food Additives", G. Thieme Verlag, Stuttgart 1978, Pp. 55-57). Among the well-known fragrances with this basic structure there are already some with functionalized side chains. DE-AS 1 218 643 describes the tricyclodecane derivatives 2 saturated in the ring system, in which the radical X is a glycidate, formyl or straight-chain 3'-oxoalkyl group,

R ¹ , R ² = H, CH ₃

X = -O-CH-COOR (R = H, C ₁ -C ₄ -AlkyI) -CHO

-CH = CH-CO-R '(R' = C ₁ -C ₅ alkyl) -CH ₂ -CH ₂ -CO-R '

known as fragrances. The ring linkages at C-2 and C-6 are said to be exo-configured, and nothing is said about the stereochemistry of the side chain linkage at C-8 or C-9. The aldehyde according to Formula 2 has a fresh smell with earthy notes, and the unsaturated ketones in the side chain according to Formula 2 smell dry woody with a wine note (R = methyl) or dry woody with an iris note (R = ethyl).

Hydroformylation of the endo-dicyclopentadiene (endo-1) present at room temperature using rhodium catalysts gives the aldehyde 3 with a relative 9-exo2,6-endo configuration (Y. Fujikura, Y. Inamoto, N. Takaishi and H. Ikeda, Synth. Commun., 6, 199 - 207 (1976) GB-OS 2 020 277 describes the aldol condensation of this aldehyde 3 with aliphatic aldehydes, which lead to the unsaturated tricyclodecene-aldehydes 4 in the side chain with the exo arrangement of the functionalized ones Side chain and endo linkage at C-2 and C-6 leads, the dashed line means an optional double bond at C-4. These aldehydes 4 have odor notes from

Wood type with secondary notes of iris root and honey and can be used as fragrances.

Furthermore, GB-OS 2 020 656 describes the corresponding aldol condensation of the 9-exo-2,6-endo-configured aldehyde 3 with aliphatic ketones, in which the tricyclodecene ketones 5 unsaturated in the side chain with exo arrangement of the functionalized side chain and endo ring linkage at C-2 and C-6 are obtained, the dashed line again signifying an optional double bond at C-4. These ketones 5, which are present as geometric isomers (double bond in the side chain), also have woody odor notes with additional odor aspects of the iris root or honey type.

Finally, DE-OS 33 03 893 gives the structurally isomeric 2,6-exo-configured tricyclo [5.2.1.0 ^{2, 6} ] decene derivatives of the general formula 6 (in which the dashed lines

R ^a = R ^b = R ^c = R ^d = HR ^a , R ^b , R ^c = H, CH ₃ (2xH.1xCH ₃ ), R ^d = CH ₃

R ¹ , R ² : H, C ₁ -C ₅ alkyl

Lines mean a CC double bond optionally at C-3 or C-4) as known. All the aldehydes or ketones falling under the formula 6 are in the side chain as well as the known compounds 4 and 5 and the unsaturated ketones according to the formula 2 with respect to the carbonyl group α, β-unsaturated. They can be displayed in different ways, e.g. B. analogous to the representation of compounds 4 and 5 starting from exo-dicyclopentadiene (exo-1). The corresponding primary or secondary alcohols are obtained by reducing the aldehydes and ketones according to formula 6, the position of the double bond in the side chain being retained. The aldehydes according to the general formula 6 smell fresh, woody, sweet and the primary alcohols soft, woody-buttery with sandalwood aspects. The correspond the ketones have urine-like animal and the secondary alcohols have soft woody-animal scents.

In general, there is a constant need for synthetic fragrances that can be produced cheaply and with consistent quality, remain stable in contact with other substances after prolonged storage, and have desired olfactory properties, i. H. have pleasant, as natural as possible scent notes of sufficient intensity and are able to influence the scent of cosmetic or technical consumer goods in an advantageous manner. Finding such odoriferous substances that meet all of these conditions has proven to be relatively complex and requires extensive investigations, particularly when interesting novel fragrance notes are sought. To make matters worse, the fact that the quality of the individual fragrance notes cannot be described quantitatively, and that neither the mechanism of the fragrance development nor the connection between the fragrance development and the chemical structure of fragrances has been sufficiently researched systematically. Even minor changes in the structure of known odoriferous substances can result in major changes in the olfactory properties in both the positive and negative directions, and sometimes such changes have practically no effect at all.

The tricyclodecane / decene derivatives according to the general formula A with a functionalized alkylidene side chain are new, and nothing has been known about their olfactory properties. The aldehydes and ketones covered by this formula A differ in principle from all known aldehydes and ketones in that they are β, ɣ-unsaturated with respect to the carbonyl group, that is to say the CC double bond in the side chain is deconjugated to the carbonyl group and no longer, as in the known compounds, is conjugated. The associated shift of the double bond in the side chain is the same for the associated primary and secondary alcohols. Surprisingly, this shift in the double bond also leads to completely different odor properties. While the known compounds are essentially to be assigned to the basic odor type "woody", the derivatives A according to the invention have a significantly different odor characteristic, namely strong floral fragrance notes with possibly soft woody side notes, e.g. T. also milk / cream notes. These notes, which are new and very desirable, do not occur with the known ct.ß-unsaturated compounds and were not predictable. In the case of the derivatives of the formula A with a methyl-substituted tricyclic ring system, an increased fixation, ie a longer adhesion of the fragrance, can also be observed.

Furthermore, the derivatives A according to the invention are notable for high stability compared to the known compounds. The known aldehydes and ketones are both sensitive to acids and sensitive to oxidation, which is probably related to the fact that the known aldehydes and ketones are to be regarded as the direct reaction product of an aldol condensation and the aldol condensation is a normally reversible reaction, i.e. is in equilibrium with an aldol cleavage. In contrast, the aldehydes and ketones according to the formula A according to the invention are not a direct reaction product of an aldol condensation and are also not subject to the aldol cleavage. The same applies to the known alcohols, which - unlike the alcohols according to the invention according to formula A - belong to the type of allyl alcohols and therefore, like all allyl alcohols, are not very stable to acids and oxidation processes. The high stability of the derivatives A according to the invention, which is apparently supported by the direct connection of the double bond to the tricyclic ring system, is due to the fact that fragrance substances are almost always used in contact with other substances and are therefore easily influenced by acids and May be exposed to oxidizing agents (e.g. atmospheric oxygen), a very important further advantage of the invention. Otherwise, the derivatives A according to the invention also meet all other requirements for a fragrance. They can be inexpensively produced with constant quality, and their fragrance notes are also very intense and are such that an addition of relatively small amounts of the derivatives A according to the invention, for. B. to perfume oils has a significantly improving effect. Overall, the derivatives A according to the invention thus represent very valuable odoriferous substances. In addition, however, they are also well suited as aroma substances or as constituents of aroma concentrates for foodstuffs and luxury foods or animal feeds.

To prepare the derivatives A according to the invention, the α, β-unsaturated aldehydes or ketones with the same substituents R ¹ and R ² and R ^a to R ^{d are} advantageously used, some of which are known or can be prepared analogously to the known compounds, Surprisingly, it was found that the α, β-unsaturated aldehydes or ketones in the presence of acidic catalysts (preferably adipic acid) and favored by an increase in temperature (e.g. in the case of slow vacuum distillation in the presence of adipic acid) convert into the corresponding β with good yield, Rearrange ɣ-unsaturated, i.e. deconjugated carbonyl compounds without significant side reactions. From these deconjugated carbonyl compounds by reduction, e.g. B. using complex hydrides such as sodium borohydride and lithium aluminum hydride, the associated deconjugated alcohols.

The ring system of the derivatives A according to the invention may be unsaturated or saturated, may have additional methyl substituents and may also be in the endo form or exo form. The tricyclodecene derivatives which are unsaturated and not methyl-substituted in the ring system according to the formula A are prepared starting from the unsaturated tricyclodecerw aldehyde 8, which in a known manner from endodicyclopentadiene (endo-1) or exodicyclopentadiene (exo-1) through selective hydroformylation arises and is used either in its endo form (endo-8) or in its exo form (exo-8). The aldehyde endo-8 and exo-8 are aldol condensed with lower aliphatic

Aldehydes or ketones formed the α, β-unsaturated derivatives endo-9 or exo-9, which are converted by deconjugation into the aldehydes or ketones endo-10 or exo-10 according to the invention. The aldehydes or ketones endo-10 or exo-10 can optionally be reduced to the primary or secondary alcohols endo-11 or exo-11, which are also according to the invention.

The hydroformylation of the dicyclopentadiene endo-1 or exo-1 can also be carried out in such a way that instead of the aldehyde 8 unsaturated in the ring system, the tricyclo saturated in the ring system decane-aldehyde 7 is formed. This saturated aldehyde 7, which is also used again in its endo form or in its exo form

can be condensed analogously to the aldehyde 8 to the α, β-unsaturated carbonyl compounds 12, from which the β, ɣ-unsaturated carbonyl compounds according to the invention are formed by deconjugation, which in turn may then be reduced to the β, ɣ-unsaturated alcohols 14 likewise according to the invention become. In this way, the non-methyl-substituted tricyclodecane derivatives which are saturated in the ring system can be prepared in accordance with the formula A.

To produce the methyl-substituted tricyclodecane or tricyclodecene derivatives according to formula A, methyl-substituted dicyclopentadiene is obtained by selective hydroformylation either in the methylated and unsaturated tricyclodecene aldehyde 15 or in the ring system in the methylated and ring system

unsaturated tricyclodecane-Aledhyd 19 implemented. From this, the α, β-unsaturated carbonyl compounds 16 or 20 can be produced by aldol condensation, from which deconju gation the ß, ɣ-unsaturated carbonyl compounds 17 or 21 according to the invention and, by subsequent reduction, also give the ß, ɣ-unsaturated alcohols 18 or 22 according to the invention.

The derivatives 13, 14, 17, 18, 21 and 22 according to the invention are, as has been described for the derivatives 10 and 11, in their endo form or in their exo form, depending on whether the ( possibly methyl-substituted) dicyclopentadiene was used in the endo form or the exo form. As a result of the deconjugation, all derivatives A according to the invention have, in addition to this predetermined 2,6-endo / exo isomerism, also a cis / trans isomerism on the β, st-permanent double bond (9,1'-Z and 9 , 1'-E), it depending on the conditions of the individual case whether during deconjugation essentially only one of the cis / trans isomers is formed or both of these isomers are obtained. The cis / trans isomerism apparently has no appreciable influence on the olfactory character of the derivatives A according to the invention, whereas the 2,6-endo / exo isomers of the same C-9 substitution have different smells, as is also the case with the known α, β-unsaturated compounds of the same C-9 substitution were observed. Otherwise, the 2,6-endo / exo isomers of the same C-9 substitution also differ in their gas-chromatic retention behavior, while their

IR spectra, ¹ H NMR spectra and mass spectra are each very similar.

The deconjugated structure of the derivatives A according to the invention is undoubtedly confirmed by the spectroscopic data. For the ß, ɣ-unsaturated carbonyl compounds 10, 13, 17 and 21 (see Fig. 3-6) a band at 1710-1730 cm ^-1 appears in the IR spectra, which indicates a saturated carbonyl group, while in the α, β-unsaturated carbonyl compounds 9, 12, 16 and 20 IR bands occur at 1670 cm ^-1 . In the

¹ H-NMR spectra of the deconjugated derivatives with R ² = methyl give the methyl group in the side chain a doublet at δ = 1.05 ppm

(see Fig. 1), while for the α, β-conjugated derivatives a singlet appears at δ = 1.6-1.7 ppm.

Table 1 lists some of the lower aliphatic aldehydes or ketones used for the preparation of the derivatives according to the formula A according to formula A in the aldol condensation, and at the same time the particular type of substitution that results in each case (ie the specific substituents R ¹ and R ^{2 that result} ) specified.

The following exemplary embodiments are intended to explain the invention without restricting it. They relate to the preparation of some selected derivatives according to formula A and their use, the letters a, b, etc. appended to the respective numbers of the compounds denoting the specific type of substitution. Example 1: exo-10d

9- (2-methyl-3-oxo-butylidene) -2,6-exo-tricyclo [5.2.1.0 ^{2, 6]} decene-4

a) Representation of the α, β-unsaturated ketone

324 g (1.7 mol) of formyltricyclodecene exo-8 were added dropwise to a solution of 440 g (6.1 mol) of methyl ethyl ketone in 566 g of methanol, 30.6 g of potassium hydroxide solution (85% strength) and 380 g of water at about 30 ° C. with stirring . After stirring for 6 hours at room temperature, the mixture was neutralized with 75 g of acetic acid and the solvent was largely distilled off. The residue was mixed with 300 ml of water and extracted with gasoline. Washing with saturated sodium hydrogen carbonate solution, concentration in vacuo and distillation gave 370 g of the α, β-unsaturated ketone mixture exo-9d and exo-9e in a ratio of about 4: 1.

Infrared spectrum (Fig. 3): 1670, 1635 cm ^-1

b) deconjugation

The ketone mixture obtained according to Example 1a was mixed with 3 g of adipic acid and then slowly (within 2 days) distilled over a 1 m steel packed column. The main fraction obtained was 176.3 g (48%) of pure ketone exo-10d as a colorless oil; Purity according to gas chromatogram: 92% (the minor fractions contained exo-10e and exo-9d).

Boiling point: bp (0.2 mbar) = 92 ° C; Density: D ²⁰ ₄ ^º _º = 1.0088; Refractive index: n ²⁰ _D ^° = 1.5153;

¹ H-NMR spectrum: Fig. 1.

Infrared spectrum (Fig. 4): 1710 (saturated ketone), 1620 cm ^-1

(Double bond, Z-disubstituted).

Mass spectrum (Fig. 2): m / z (%) = 216 (5, M ⁺ ), 173 (66), 150

(1 9), 1 49 (1 1), 1 31 (10), 1 17 (1 1), 107 (95), 105 (18), 93 (10),

91 (36), 79 (43), 78 (11), 77 (29), 67 (200), 65 (14), 43 (34).

Molecular formula: C ₁₅ H ₂₀ O; 5 Molar weight: 216.4 Example 2: exo-11d

9- (2-Methyl-3-hydroxybutylidene) -2,6-exo-tricyclo [5.2.1.0 ^{2, 6} ] decene

108 g (0.5 mol) of the ketone exo-10d (according to Example 1) in 200 ml of ether were added dropwise at room temperature to a suspension of 7.5 g (0.22 mol) of lithium aluminum hydride in 300 ml of ether with stirring. After stirring at 30 ° C. for 1 hour, the mixture was worked up in the usual manner. Distillation over a rotating band column gave 93.8 g of exo- 1 1 d as a colorless oil.

Boiling point: bp (0.1 mbar) = 94 ° C; Density: D \ z = 1.0051; Refractive index: n ²⁰ _D ^° = 1.5204;

¹ H-NMR spectrum: δ = 0.92 and 0.95, 2d, J = 7 Hz, (isomeric CH ₃ -4 '),

1.10, d, J = / Hz (2'-CH ₃ ), 3-3-3.7, m (3'-H), 4.7-5.2, "t" _R (1'-H),

5.2-5.7 p-pm, m (3-, 4-H, or 4-, 5-H).

Infrared spectrum: 3360 (OH), 1675 (trisubst. Double bond),

1620 cm ^-1 (Z-disubst. Double bond).

Mass spectrum (main peak): m / z (%) = 218 (3, M ⁺ ), 173 (22),

151 (8), 145 (3), 131 (7), 117 (5), 107 (100), 91 (42), 79 (50),

67 (84).

Molecular formula: C ₁₅ -H ₂₂ O; Molar weight: 218.4

Example 3: exo-10c

9- (3-Oxo-butylidene) -2,6-exo-tricyclo [5.2.1.0 ² ' ⁶ ] decen-4

a) Representation of the α, β-unsaturated ketone

A solution of 243 g (1.5 mol) of aldehyde exo-8, 350 g of acetone and 350 g of water was mixed with stirring with 34 g of sodium hydroxide solution (25%) and then stirred at 50 ° C. for a further hour. After distilling off the acetone under reduced pressure, take up In saturated sodium chloride solution, neutralization with acetic acid, extraction with ether and concentration, 250 g of crude ketone exo-9c were present as a light yellow oil.

Infrared spectrum (Fig. 5): 1670 and 1620 cm (α, β-unsaturated ketone);

Gas chromatogram: (50 m FFAP, temperature program 100 - 220 ° C, 6 ° C / min): t _R [min] (%) = 19.1 (10) and 19.5 (90) exo-9c (geometric isomers).

b) deconjugation

The ketone exo-9c obtained according to Example 3a was mixed with 1 g adipic acid and stirred for 1 hour at 60 ° C. under a nitrogen atmosphere. Partial deconjugation occurred.

Infrared spectrum: 1715, 1670, 1620 cm ^-1 ;

Gas chromatogram: (50 m FFAP, temperature program 100 - 220 ° C, 6 ° C / min): t _R [min] (%) = 17.1 (18) and 17.4 (36) exo-10c (geometric isomers), 19.1 (8 ) and 19-5 (34) exo-9c (geometric isomers).

Extensive deconjugation and simultaneous trans-isomerization were achieved by distillation of the crude ketone mixed with adipic acid via a 40 cm Vigreux column. 165 g of exo-10c were obtained as a colorless oil.

Boiling point: bp (1 mbar) = 104 ° C; Density: D ²⁰ ₄ ^º _º = 1.0299; Refractive index: n ²⁰ _D ^° = 1.5229;

¹ H-NMR spectrum: δ = 2 .03, 2 .05, 2s (-CO-CH ₃ , 1 '-Z- and 1' -E),

4.95-5.35, m (1'-H), 5.35-5.75 ppm, m (3-, 4-H, or 4-, 5-H).

Infrared spectrum (Fig. 6): 1715 cm ^-1 (total ketone).

Gas chromatogram: (50 m DB-WAX, 230 ° C); t _R [min] (%) = 41.0

(36.5), 41.6 (44.2).

Mass spectrum (main peak 1): m / z (%) = 202 (8, M ⁺ ), 159 (10),

144 (13), 136 (65), 137 (67), 129 (6), 117 (10), 105 (7), 93

(91), 91 (50), 77 (38), 67 (100), ..., 43 (82).

Molecular formula: C ₁₄ H ₁₈ O; Molar weight: 202.2 Example 4: exo-11c

9- (3-Hydroxy-butylidene) -2, 6-exo-tricyclo [5.2.1.0 ^{2, 6} ] decen-4

The preparation was carried out analogously to Example 2 by reducing the ketone exo-10c.

Boiling point: bp (0.4 mbar) = 106 ° C; Density: D = 1.0192 ²⁰ _{4 °} ^º; Refractive index: n ² _D ^{0 °} = 1.5246;

¹ H-NMR spectrum: δ = 1. 1 5, d, J = 7 Hz (CH ₃ , -4 '), 3 .4 - 3 .9, m (CH-3'),

4.8 - 5.3, m (1'-H), 5.3 - 5.75 ppm, m (3-, 4-H, or 4-, 5-H).

Infrared spectrum: 3350 (OH), 1680 (double bond, trisubstituted), 1615 cm ^-1 (double bond Z-disubstituted).

Mass spectrum (main peak): m / z (%) = 204 (3, M ⁺ ), 160 (8), 137

(11), 131 (6), 117 (8), 105 (6), 93 (100), 91 (35), 79 (25),

77 (25), 67 (43).

Molecular formula: C ₁₄ , H ₂₀ O; Molecular weight: 204.3

Example 5: exo-10h

9- (3-0xo-hexylidene) -2,6-exo-tricyclo [5.2.1.0 ^{2, 6} ] decen-4

The preparation was carried out analogously to Example 1, methyl propyl ketone being used as the reactant in the aldol condensation and the main fraction being isolated.

¹ H-NMR spectrum: δ = 0.87, t, J = 7 Hz (CH ₃ -6 '), 4.85 - 5.25, m (1'-H), 5.25 - 5.75 ppm (3-, 4-H, resp . 4-, 5-H).

Infrared spectrum: 1710 cm ^-1 (total ketone).

Mass spectrum (main peak): m / z (%) = 230 (4, M ⁺ ), 164 (46), 159 (21), 144 (6), 117 (8), 93 (62), 77 (26). Molecular formula: C ₁₆ H ₂₂ O; Molar weight: 230.4 Example 6: endo-10d

9- (2-methyl-3-oxo-butylidene) -2,6-endo-tricyclo [5.2.1.0 ^{2, 6]} decene-4

From 324 g of endo-8 and 440 g of methyl ethyl ketone, analogous to the two steps of Example 1, 380 g of product mixture endo-9d / endo-9e (7: 2) were first produced (infrared spectrum: 1670, 1620 cm ^-1 ), which in the second stage was mixed with 3 g of adipic acid and distilled over a 1 m steel packed column within 2 days.

Boiling point: Kp (0.3 mbar) = 95 ° C

Gas chromatogram (50 m glass capillary, WG 11, 220 ° C): t _R [min] (%)

= 8.58 (23, Z-endo-10d, 8.69 (53, E-endo-10d, 10.05 (10, E-endo-10e),

10.24 (5, Z-endo-10e).

Pure ketone E-endo-10d was obtained by distillation over a rotating band column.

Infrared spectrum (film): 1715, 1620 cm ^-1 (total ketone, cis-disubstituted double layer.

¹ H-NMR spectrum: Fig.7

Mass spectrum (Fig.8): m / z (%) = 216 (M ⁺ , 1), 173 (16), 150

(26), 117 (8), 108 (8), 107 (100), 105 (9), 91 (25), 79 (34), 77

(15), 67 (57), 43 (14).

Molecular formula: C ₁₅ H ₂₀ O; Molar weight: 216.4

Example 7: endo-11d

9- (2-Methyl-3-hydroxybutylidene) -2,6-endo-tricyclo [5.2.1.0 ^2,6 ] decen-2

Analogously to Example 2, 10.8 g (0.5 mol) of the ketone endo-10d according to Example 6 were reduced with 0.75 g (0.22 mol) of lithium aluminum hydride. Distillation on a rotating column column gave 8.4 g of endo-11d as a colorless oil. Boiling point: Kp (0.5 mbar) = 102 ° C.

Infrared structure (film): 3380 cm ^-1 (OH).

Mass spectrum (main peak): m / z (%) = 218 (M ⁺ , 11), 203 (2), 173

(26), 152 (12), 145 (5), 134 (10), 131 (11), 119 (10), 117 (9),

108 (45), 107 (100), 91 (72), 81 (55), 79 (73), 67 (85).

Molecular formula: C ₁₅ H ₂₂ O; Molar weight: 218.4

Example 8

Use of the Exo-11c and Exo-11d Derivatives in a Chypre-Type Perfume Oil The starting point was a perfume oil with the following composition (GT = parts by weight):

215 pbp tertiary butylcyclohexyl acetate

115 pbv vetiveryl acetate

100 pbw methyl ionone, gamma

90 pbw of linalyl acetate

65 GT Linalool

50 GT ß-Jonon

40 GT lime, right

40 pbw of 2-methyl-4- (2,3,3-trimethyl-cyclopent-3-enyl-1 -) - butanol-1

30 pbw 1,4-dioxa-cyclohexadecan-5,16-dione

20 GT orange oil, Brazilian

12 GT oakmoss extract

10 GT coumarin

6 pbw of undecalactone, 10% in dipropylene glycol

2 pbw of aldehyde C-12, 10% in dipropylene glycol

800 GT

200 pbw of the alcohol exo-11c (mixture A) and 200 pbw of the alcohol exo-11d (mixture B) were incorporated into this perfume oil. Both mixtures A and B each have a balanced, original fragrance complex of the chypre type, whereby in A light-flowery and in B soft-woody odor aspects are emphasized. Example 9

Use of the derivative exo-IOc in a part oil with herbaceous notes

The starting point was a perfume oil with the following composition (GT = parts by weight):

270 GT bergamot oil, Reggio

210 GT lavender oil, French

120 pbw of phenylethyl alcohol

70 GT geranium oil, bourbon

50 GT eugenol

40 GT allspice oil

30 pbw of 2-methyl-4- (2,3,3-trimethyl-cyclopent-3-enyl-1) -butanol 1

30 pbw of isobutyl salicylate

20 pbw of benzyl salicylate

20 GT coumarin

20 pbw 1,4-dioxa-cyclohexadecane-5,16-dione

20 GT musk, ketone

15 GT oakmoss extract

10 GT menthol

5 GT cinnamon oil, Ceylon

930 GT

This perfume oil has a fresh, spicy fragrance with distinctive lavender aspects. When 70 parts of the ketone exo-10c are added, a new, spicy-herb fragrance complex is created with great harmony and charisma. Example 10

Use of the derivatives endo-11d or exo-11d in a perfume oil with fruity, woody notes

120 GT Bergamot Oil Reggio

100 pbw of tertiary butyl cyclohexyl acetate

80 pbw methylnonylacetaldehyde, 10% in dipropylene glycol

80 GT lemon oil, Messina

80 pbw of benzyl acetate

60 GT French lavender oil

50 GT clove oil

50 GT neroli oil

50 GT orange oil, Brazilian

30 pbw of aldehyde C-10, 1% in dipropylene glycol

30 GT oakmoss extract, 50%

30 pbw of styrolylacetate

20 GT patchouli oil

20 pbw of 2-methyl-4- (2,2,3-trimethyl-cyclopent-3-enyl-1 -) - butanol-1

20 pbw 1,4-dioxa-cyclohexadecane-5,16-dione

20 pbw of galbanum resinoid

10 pbw of 1,4-dimethyl-8-hydroxomino-bicyclo [3.2.1] octane

850 GT

The fruity-woody character of this mixture is rounded off by adding 150 parts of the alcohol exo-11d in a very desired way, while a soft-woody tonality occurs at the same time. The alternative addition of 150 parts of the alcohol endo-11d also results in a rounding-off, whereby a soft, flowery tonality emerges at the same time.

Fig. 1: ¹ H-NMR spectrum (60 MHz, CCl ₄ ) of exo-10d

Fig. 2: Mass spectrum of exo-10d (main peak)

Fig. 3: IR spectrum (film) of the α, β-unsaturated ketone exo-9d

(+ exo-9e)

Fig. 4: IR spectrum (film) of the ß, ɣ-unsaturated ketone exo-10d

(+ exo-10) e)

Fig. 5: IR spectrum (film) of the α, β-unsaturated ketone exo-9c

Fig. 6: IR spectrum (film) of the β, ɣ-unsaturated ketone exo-10c

Fig. 7: H-NMR spectrum (60 MHz CCl ₄ ) of endo-10d

Fig. 8: Mass spectrum of endo-10d (main peak)

Claims

Patent claims

1. Tricyclo [5.2.1.0 ^2.6 ] decane / decene derivatives of the general formula A

R ^a = R ^b = R ^c = R ^d = H

R ^a , R ^b , R ^c = H, CH ₃ (2xH, 1xCH ₃ ),

R ^d = CH ₃

R ¹ , R ² : H, C ₁ -C ₆ alkyl

2,6-endo 2,6-exo 9,1'-Z 9.1'-E in which the radical R ^d in the case of R ^d = -CH _{3 is} at C-7 or C-8, the dashed lines between C-3 and C-4 and C-4 and C-5 represent either two CC single bonds or one CC double bond and one CC single bond, and the serpentine lines represent stereoisomeric forms.

2. Use of the compounds according to claim 1 as fragrances or constituents of perfume compositions for perfuming cosmetic or technical consumer goods.