EP0215799B1 - Tricyclo [5.2.1.0/2,6] decane/decene derivatives with functionalized alkylidene side chains and utilization thereof as perfuming substances - Google Patents

Abstract

New tricyclo AD5.2.1.02,6 BD decane/decene derivatives having the formula (I) wherein Rd, in the case where Rd = -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

• R^a = R^b = R^c = R^d = H
• R^a,R^b,R^c = H, CH₃(2 x H, 1 ^x CH₃),
  • _R ^d = CH₃
       OH
• X: =O,
     H
• R¹, R²: H, C₁-C₆-Alkyl
• 2,6-endo 2,6-exo 9,1'-Z 9,1'-E

worin der Rest R^d im Falle R^d = -CH₃ an C-7 oder C-8 steht, die gestrichelten Linien zwischen C-3 und C-4 sowie C-4 und C-5 entweder zwei C-C-Einfachbindungen oder eine C-C-Einfachbindung und eine C-C-Doppelbindung darstellen sowie die geschlängelten Linien stereoisomere Formen bedeuten. Die Erfindung betrifft weiterhin die Verwendung der neuen Verbindungen gemäss der allgemeinen Formel A als Riechstoffe bzw. als Bestandteile von Parfümölen für kosmetische oder technische Konsumgüter.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 = H
• R ^a , R ^b , R ^c = H, CH ₃ (2 x H, 1 ^x CH ₃ ),
  • _R ^d = CH ₃
    OH
• X: = O,
  H
• R ¹ , R ² : H, C ₁ -C ₆ alkyl
• 2,6-endo 2,6-exo 9,1'-Z 9,1'-E

where 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 are either two CC single bonds or one CC Represent a single bond and a CC double bond and the serpentine lines mean 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.

• R¹,R² = H, CH₃
  • X = -O-CH-COOR
    • (R=H, C₁-C₄-Alkyl)
      • -CHO
      • -CH=CH-CO-R'
    • (R'=C₁-C₅-Alkyl)
      • -CH₂-CH₂-CO-R'

als Riechstoffe bekannt. Die Ringverknüpfungen an C-2 und C-6 sollen dabei exofiguriert sein, und über die Stereochemie der Seitenketten-Verknüpfung an C-8 oder C-9 wird nichts ausgesagt. Der Aldehyd gemäss der Formel 2 besitzt einen frischen Geruch mit erdigen Noten, und die in der Seitenkette ungesättigten Ketone gemäss der Formel 2 riechen trocken-holzig mit Wein-Note (R=Methyl) bzw. trocken-holzig mit Iris-Note (R=Ethyl).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 an im Ring system saturated 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 218643 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 alkyl)
      • -CHO
      • -CH = CH-CO-R '
    • (R '= C ₁ -C ₅ alkyl)
      • -CH ₂ -CH ₂ -CO-R '

known as fragrances. The ring links at C-2 and C-6 are said to be exofigured, 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 according to formula 2 in the side chain smell dry-woody with a wine note (R = methyl) or dry-woody with an iris note (R = Ethyl).

Holz-Typ mit Nebennoten von Iriswurzel und Honig und können als Riechstoffe verwendet werden.Hydroformylation of the endo-dicyclopentadiene (endo-1) present at room temperature using rhodium catalysts gives the aldehyde 3 with a relative 9-exo-2,6-endo configuration (Y. Fujikura, Y. Inamoto, N. Takaishi and H. Ikeda, Synth. Commun., 6, 199-207 (1976), GB-OS 2020277 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 link 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, the corresponding aldol condensation of the 9-exo-2,6-endo-configured aldehyde 3 with aliphatic is in GB-OS 2020656 Ketones are described in which the unsaturated tricyclodecene ketones 5 in the side chain are obtained with exo arrangement of the functionalized side chain and endo ring linkage at C-2 and C-6, the broken 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.

• R^a = R^b = R^c = R^d = H
• R^a,R^b,R^c = H, CH₃(2 ^x H, 1 ^x CH₃),
  • Rd = CH₃
  • OH
• X: ^=0,
  • H
• R¹,R²: H, C_i-C₅-Alkyl

Linien eine C-C-Doppelbindung fakultativ an C-3 oder C-4 bedeuten) als bekannt. Alle die unter die Formel 6 fallenden Aldehyde oder Ketone sind dabei in der Seitenkette ebenso wie die bekannten Verbindungen 4 und 5 sowie die ungesättigten Ketone gemäss der Formel 2 in bezug auf die Carbonylgruppe a,ß-ungesättigt. Ihre Darstellung kann auf verschiedene Weise erfolgen, z. B. analog der Darstellung der Verbindungen 4 und 5 von exo-Dicyclopentadien (exo-1) ausgehend. Die entsprechenden primären oder sekundären Alkohole ergeben sich durch Reduktion der Aldehyde und Ketone gemäss der Formel 6, wobei die Lage der Doppelbindung in der Seitenkette erhalten bleibt. Die Aldehyde gemäss der allgemeinen Formel 6 riechen frisch, holzig, süss und die primären Alkohole weich, holzig-buttrig mit Sandelholzaspekten. Die entsprechenden Ketone besitzen urinartige animalische und die sekundären Alkohole weiche holzig-animalische Duftnoten.Finally, DE-OS 3303893 gives the structurally isomeric 2,6-exo-configured tricyclo [5.2.1.02 · 6] decene derivatives of the general formula 6 (in which the dashed lines

• R ^a = R ^b = R ^c = R ^d = H
• R ^a , R ^b , R ^c = H, CH ₃ (2 ^x H, 1 ^x CH ₃ ),
  • Rd = CH ₃
  • OH
• X: ^{= 0,}
  • H
• R ¹ , R ² : H, C _i -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 a, β-unsaturated. They can be displayed in different ways, e.g. B. starting from the representation of compounds 4 and 5 of 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 general formula 6 smell fresh, woody, sweet and the primary alcohols soft, woody-buttery with sandalwood aspects. The corresponding ketones have urine-like animal scents 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. Finding such odoriferous substances that meet all of these conditions has proven to be relatively complex and requires extensive investigations, especially 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 fundamentally from all known aldehydes and ketones in that they are β, Y-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 α, β-unsaturated compounds and were not predictable. In the case of the derivatives falling under 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 acid 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 the formula A - for 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 fragrances are almost always used in contact with other substances and therefore the influence of acids and oxidizing agents (e.g. atmospheric oxygen), a very important further advantage of the invention.

In addition, the derivatives A according to the invention also meet all other requirements for a fragrance. They can be produced inexpensively 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 z according to the invention is already possible. 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} expediently used, some of which are known or can be prepared analogously to the known compounds. Surprisingly, it was found that the a, β-unsaturated aldehydes or ketones in the presence of acidic catalysts (preferably adipic acid) and favored by increasing the temperature (e.g. with slow vacuum distillation in the presence of adipic acid) convert into the corresponding β, Y- rearrange 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.

Aldehyden oder Ketonen die a,ß-ungesättigten Derivate endo-9 bzw. exo-9 gebildet, die durch Dekonjugation in die erfindungsgemässen Aldehyde oder Ketone endo-10 bzw. exo-10 umgesetzt werden. Die Aldehyde oder Ketone endo-10 bzw. exo-10 können ggfs. noch zu den ebenfalls erfindungsgemässen primären oder sekundären Alkoholen endo-11 bzw. exo-11 reduziert werden.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 unsaturated and not methyl-substituted in the ring system according to formula A are prepared starting from the unsaturated tricyclodecene aldehyde 8, which in a known manner from endodicyclopentadiene (endo-1) or exodicyclopentadiene (exo-1) is formed by selective hydroformylation 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 form the α, β-unsaturated derivatives endo-9 or exo-9, which are converted into the aldehydes or ketones endo-10 or exo-10 according to the invention by deconjugation. 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.

wird, lässt sich analog dem Aldehyd 8 zu den a,ß- ungesättigten Carbonylverbindungen 12 kondensieren, aus denen durch Dekonjugation die erfindungsgemässen β,Y-ungesättigten Carbonylverbindungen entstehen, die dann ihrerseits ggfs. zu den ebenfalls erfindungsgemässen ß,y-ungesättigten Alkoholen 14 reduziert werden. Auf diese Weise können die im Ringsystem gesättigten, nicht methylsubstituierten Tricyclodecan-Derivate gemäss der Formel A hergestellt werden.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 tricyclodecane aldehyde 7 saturated in the ring system 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, Y-unsaturated carbonyl compounds according to the invention are formed by deconjugation, which in turn, if necessary, reduces them to the β, y-unsaturated alcohols 14 likewise according to the invention will. 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.

gesättigten Tricyclodecan-Aldehyd 19 umgesetzt. Daraus können durch Aldolkondensation die a,ß- ungesättigten Carbonylverbindungen 16 oder 20 hergestellt werden, aus denen sich durch Dekonjugation die erfindungsgemässen β,Y-ungesättigten Carbonylverbindungen 17 oder 21 und durch anschliessende Reduktion die ebenfalls erfindungsgemässen ß,vT-ungesättigten Alkohole 18 oder 22 ergeben.To prepare 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 in the ring system or in the methylated and in the ring system

saturated tricyclodecane aldehyde 19 implemented. From this, the a, β-unsaturated carbonyl compounds 16 or 20 can be prepared by aldol condensation, from which the β, Y-unsaturated carbonyl compounds 17 or 21 according to the invention are obtained by deconjugation and the β, vT-unsaturated alcohols 18 or 22 likewise according to the invention are subsequently obtained .

The derivatives 13, 14, 17, 18, 21 and 22 according to the invention are, as has been described for the derivatives 10 and 1.1, 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, Y-permanent double bond (9,1'-Z and 9,1 '-E), whereby it depends 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 isomers of the derivatives A according to the invention have similar and valuable smell properties, whereas the 2,6-endo / exo isomers of the same C-9 substitution differ in smell from one another, as is also the case with the known a, β-unsaturated ones 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 each case 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, y-unsaturated carbonyl compounds 10, 13, 17 and 21 (see Fig. 3-6) a band appears in the IR spectra at 1710-1730 cm- ¹ , which indicates a saturated carbonyl group, while in the a, β-unsaturated carbonyl compounds 9, 12, 16 and 20 IR bands occur at 1670 cm ^-1 . In the ¹ H-NMR spectrum of the mixture of deconjugated derivatives with R ² = methyl, the methyl group in the side chain gives a doublet at 6 = 1.05-1.08 ppm (see Fig. 1), while in the a, ß-conjugated derivatives for this a singlet appears at 6 = 1.6-1.7 ppm.

Table 1 shows some of the derivatives for the production of the derivatives according to the invention Formula A is compiled into the lower aliphatic aldehydes or ketones used in the aldol condensation, and at the same time the particular type of substitution that results in each case (ie the specifically resulting substituents R ¹ and R ² ) is indicated.

The following exemplary embodiments are intended to explain the invention without restricting it. They relate to the production of some selected derivatives according to the 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. 9.0 ^2.6 ] decen-3 (4) a) Representation of the α, β-unsaturated ketone

324 g (1.7 mol) of formaltricyclodecene exo-8 (85% strength) were added 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 ) added dropwise. After stirring at room temperature for 6 hours, the mixture was acidified 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 bicarbonate solution, concentration in vacuo and distillation gave 370 g of the a, 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

3 g of adipic acid were added to the ketone mixture obtained according to Example 1a and then distilled slowly (within 2 days) over a 1 m steel packed column. The main fraction 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-1 Oe and exo-9d).

: = 1.0088;Boiling point: bp (0.2 mbar) = 92 ° C; Density: D

: = 1.0088;

= 1.5153;Refractive index: n

= 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 (19), 149 (11), 131 (10), 117 (11), 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; Molar weight: 216.4.

Example 2: exo-11d 9- (2-methyl-3-hydroxybutylidene) -2,6-exo-tricyclo [5.2.9.02,6] decen-3 (4)

108 g (0.5 mol) of the ketone exo-10d (according to Example 1) in 200 ml of ether were added dropwise to a suspension of 7.5 g (0.2 mol) of lithium aluminum hydride in 300 ml of ether while stirring in room temperature. After stirring at 30 ° C. for 1 hour, the mixture was worked up in the usual manner. Distillation over a rotating column column gave 93.8 g of exo-11 d as a colorless oil.

= 1.0051;Boiling point: bp (0.1 mbar) = 94 ° C; Density: D

= 1.0051;

= 1.5204;Refractive index: n

= 1.5204;

¹ H-NMR spectrum: 6 = 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 (3rd '-H), 4.7-5.2, "t"(1'-H), 5.2-5.7 ppm, 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 isomer): 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-3 (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, taking up in saturated sodium chloride solution, neutralizing 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 ^-1 (a, ß-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 of 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 100-200 ° 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-1 oc were obtained as a colorless oil.

= 1.0299;Boiling point: bp (1 mbar) = 104 ° C; Density: D

= 1.0299;

= 1.5229;Refractive index: n

= 1.5229;

¹ H-NMR spectrum: 6 = 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 isomer 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-hydroxybutylidene) -2,6-exo-tricyclo- [5.2.9.0 ^2,6 ] decen-3 (4)

The preparation was carried out analogously to Example 2 by reducing the ketone exo-1 Oc.

= 1.0192;Boiling point: bp (0.4 mbar) = 106 ° C; Density: D

= 1.0192;

= 1.5246;Refractive index: n

= 1.5246;

¹ H-NMR spectrum: δ = 1.15, d, J = 7 Hz (CH ₃ -4 '), 3.4-3.9, m (CH-3'), 4.8-5.3, m (1'-H), 5.5 -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-oxo-hexylidene) -2,6-exo-tricyclo [5.2.1.0 ^2,6 ] -decen-3 (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.

'H-NMR spectrum: δ = 0.87, t, J = 7 Hz (CH ₃ -6'), 4 x 85-5 x 25, m (1'-H), 5 x 25-5 x 75 ppm ( 3-, 4-H, or 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 ] decen-3 (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-1 Od), 8.69 (53, E-endo-1 0d), 10.05 (10 , E-endo-10e), 10.24 (5, Z-endo-1 Oe).

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-endotricyclo [5.2.1.0 ^2.6 ] decen-3 (4)

Analogously to Example 2, 10.8 g (0.05 mol) of the ketone endo-1 Od according to Example 6 were reduced with 0.75 g (0.02 mol) of lithium aluminum hydride. Distillation on a rotary column gave 8.4 g of endo-11 d as a colorless oil.

Boiling point: Kp (0.5 mbar) = 102 ° C.

Infrared spectrum (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 derivatives exo-11c and exo-11d in a chypre-type perfume oil

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

200 pbw of the alcohol exo-11 c (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-10c in a perfume oil with herbaceous notes

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

This perfume oil has a fresh, spicy fragrance with distinctive lavender aspects. When 70 parts of the ketone exo-1 Oc 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

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

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

Claims (2)

1. Tricyclo[5.2.1.0^2,6]decane/decene derivatives having the general formula A

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

R^a,R^b,R^c = H, CH3(2 x H, 1 x CH3),

R^d = CH₃

OH

X: =O,
   H

R¹, R²: H, C₁-C₆-Alkyl

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

wherein
the residue R^d, in the case where R^d = -CH₃, is in position C-7 or C-8, the dotted lines between C-3 and C-4 and also C-4 and C-5 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.

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