Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
  • C11B9/00—Essential oils; Perfumes
  • C11B9/0061—Essential oils; Perfumes compounds containing a six-membered aromatic ring not condensed with another ring

Definitions

• the invention relates to new tricyclo [5 .2. 1 .0 2, 6 ] decane / decene derivatives with the general formula A
• R 1 , R 2 H, C 1 -C 6 alkyl
• 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).
• 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
• fragrances 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.
• 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
• 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.
• 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.
• 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 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 ⁇ , ⁇ -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.
• 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 ⁇ , ⁇ -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.
• 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.
• an increased fixation ie a longer adhesion of the fragrance, can also be observed.
• 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.
• 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 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.
• the derivatives A according to the invention thus represent very valuable odoriferous substances.
• they are also well suited as aroma substances or as constituents of aroma concentrates for foodstuffs and luxury foods or animal feeds.
• the ⁇ , ⁇ -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.
• acidic catalysts preferably adipic acid
• 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 ⁇ with good yield Rearrange ⁇ -unsaturated, i.e. deconjugated carbonyl compounds without significant side reactions.
• 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 ⁇ , ⁇ -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.
• 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
• the ⁇ , ⁇ -unsaturated carbonyl compounds 16 or 20 can be produced by aldol condensation, from which deconju gation the ß, ⁇ -unsaturated carbonyl compounds 17 or 21 according to the invention and, by subsequent reduction, also give the ß, ⁇ -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.
• 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 ⁇ , 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 ⁇ , ⁇ -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
• 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 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).
• 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.
• 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. 3 IR spectrum (film) of the ⁇ , ⁇ -unsaturated ketone exo-9d
• Fig. 4 IR spectrum (film) of the ß, ⁇ -unsaturated ketone exo-10d
• Fig. 5 IR spectrum (film) of the ⁇ , ⁇ -unsaturated ketone exo-9c
• Fig. 6 IR spectrum (film) of the ⁇ , ⁇ -unsaturated ketone exo-10c

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Fats And Perfumes (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Cosmetics (AREA)

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Citations (5)

• 1985
  • 1985-12-16 WO PCT/DE1985/000531 patent/WO1986003737A1/de not_active Ceased
  • 1985-12-16 EP EP86900063A patent/EP0215799B1/de not_active Expired
  • 1985-12-16 DE DE8686900063T patent/DE3564564D1/de not_active Expired
  • 1985-12-16 JP JP61500440A patent/JPS62501149A/ja active Granted

Patent Citations (5)

Non-Patent Citations (1)

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