US20130090390A1

US20130090390A1 - Fragrances with note of lily of the valley

Info

Publication number: US20130090390A1
Application number: US13/645,871
Authority: US
Inventors: Emilie Singer; Bernd Holscher
Original assignee: Symrise AG
Current assignee: Symrise AG
Priority date: 2011-10-07
Filing date: 2012-10-05
Publication date: 2013-04-11
Also published as: CN103030538B; EP2578671B1; US20240084216A1; EP2578671A1; CN103030538A

Abstract

A compound of formula (I) is described

and use thereof as fragrance, especially as lily-of-the-valley fragrance and/or as an agent for increasing the substantivity and/or the retention of a fragrance preparation and/or as a fixative.

Description

The present invention primarily relates to novel compounds selected from the group consisting of the compound of formula (1a)
and of the compound of formula (Ib)
and mixtures comprising the compound of formula (Ia) as defined above and the compound of formula (Ib) as defined above or consisting of the compound of formula (Ia) and the compound of formula (Ib) as defined above. In addition, the invention relates to the use of a compound of formula (I)
as fragrance, especially as lily-of-the-valley fragrance, and fragrance preparations and perfumed products comprising a (preferably sensorially effective) amount of the compound of formula (I) as defined above and methods of producing a compound of formula (I) as defined above.
Compounds with floral odor are an indispensable component in the perfume industry and in the production of cosmetics, body care products and washing and cleaning products. An especially valuable class of these floral fragrances are compounds with an odor note of lily of the valley.
Some representatives of this class of fragrances have a structure comprising a 4-alkyl-phenylpropanal as skeleton structure, for example 3-(4-tert-butylphenyl)-2-methylpropanal (formula (A); Lilial®, manufacturer: Givaudan S. A.), 3-(4-tert-butylphenyl)propanal (formula (B); Bourgeonal®, manufacturer: Quest), 3-(4-isopropylphenyl)-2-methylpropanal (formula (C), Cyclamal®, manufacturer: Givaudan S.A.) and 3-(3-isopropylphenyl)-butanal (formula (D), Florhydral®, manufacturer: Givaudan S.A.).
3-(4-tert-Butylphenyl)-2-methylpropanal (A), a synthetic fragrance, was for a long time one of the most important industrially used fragrances for floral fragrance compositions, especially with an odor note of lily of the valley, and was used in large quantities in the cosmetics and soaps industry. Then, however, results of animal tests showed that 3-(4-tert-butylphenyl)-2-methylpropanal could be reprotoxic. In addition, it was found that this compound is possibly an allergen and might cause contact dermatitis in sensitive persons. As the compounds 3-(4-tert-butylphenyl)propanal (B), 3-(4-isopropylphenyl)-2-methylpropanal (C) and 3-(3-isopropylphenyl)-2-methylpropanal (D) are very similar structurally to the compound 3-(4-tert-butylphenyl)-2-methylpropanal (A), it is entirely possible that these compounds are similarly toxic.
However, the occurrence of an odor with a note of lily of the valley is not linked to the skeleton structure described above.
Thus, patent document US 6,376,458 discloses compounds represented by the following general formula (E), which in contrast to the compounds described above of formulas (A) to (D) have a saturated or unsaturated cyclohexyl group instead of a phenyl group:
In formula (E), the endocyclic dashed line denotes a single bond or a double bond, and the group R is a methyl group or a hydrogen atom.
The compound 3-(4-tert-butyl-1-cyclohexen-1-yl)-2-methylpropanal specifically disclosed in patent document U.S. Pat. No. 6,376,458 has an odor comprising the odor notes lily of the valley, almost white flowers and freesias. The compound 3-(4-tert-butyl-1-cyclohexen-1-yl)propanal preferred according to US 6,376,458 shows an odor of the aldehyde-like, floral lily of the valley-like, fatty type with a side note of Lilial®/Bourgeonal®, but this fragrance is more floral and the note of white flowers is more pronounced than with Lilian®.
The odor notes of the compounds of formula (F) disclosed in U.S. Pat. No. 7,834,219 have a strong floral note and a note of lily of the valley. The compounds differ from compounds (A) to (D) in that they comprise a cyclohexyl group instead of a phenyl group. In formula (F), the group R denotes an ethyl, isopropyl, or sec-butyl group.
However, none of these compounds (B) to (F) known from the prior art is able to reproduce the odor impression of the natural lily of the valley blossom in its entire complexity.
Conversely, compounds are also known which, despite structural similarity to the compounds described above, do not have an odor note of lily of the valley, for example the compound pinoacetaldehyde of formula (G), described in patent document U.S. Pat. No. 3,716,498:
The odor of this molecule is described as persistent, very fresh, pungent, floral, woody and ozone-like.
The compound 3-(4-isopropyl-1-cyclohexen-1-yl)-2-methylpropanal (formula (H) also does not show any odor note of lily of the valley, despite structural similarity to compounds (A) to (F). Rather, the odor profile of this compound is aldehyde-like, sweet, watery and floral (cyclamen tendency).
Despite the large number of fragrances already available, in the perfume industry there is still a general demand for new fragrances, which in addition to their primary, namely olfactory, properties, also possess positive secondary properties, for example greater stability in particular conditions of use, greater substantivity and/or diffusivity or better adherence, or which, through synergy effects with other fragrances, lead to better sensory profiles.
Fragrances that are characterized by the aforementioned positive secondary properties allow for increased efficiency in the production of fragrance preparations and perfumed products. For example, by using fragrances with a better sensory profile, higher substantivity and/or better adherence, the number and the amounts of fragrances used in corresponding formulations can be optimized and/or minimized, which leads to a saving of sustainable resources in the production of perfumed products.
Therefore there is in the perfume industry a demand in particular for further fragrances with improved sensory profiles and/or secondary properties.
The primary problem to be solved by the present invention was to provide a fragrance with a floral, especially lily-of-the-valley odor note, whose olfactory properties are comparable to 3-(4-tert-butylphenyl)-2-methylpropanal (Lilial®), i.e. the fragrance should impart an odor impression that largely corresponds to the complexity of the natural odor of lily of the valley blossom. Furthermore, this fragrance should preferably be superior with respect to the sum of its secondary properties or at least some of its secondary properties to the lily of the valley fragrances known from the prior art.
A fragrance is, in the context of the present text, any substance that is suitable for being used for bringing about an olfactory impression, i.e. for imparting an olfactory impression, or for altering (modifying or intensifying) the olfactory perception of another substance. Moreover, in order to be used for perfumery purposes, said substance should preferably have no undesirable side-effects, e.g. effects that are injurious to health or to the environment, or have no adverse effects on the proper use of a product that contains this fragrance.
The aforementioned problem is solved according to the invention by the use of a compound of formula (I)

- as fragrance, especially as lily-of-the-valley fragrance and/or
- as an agent for increasing the substantivity and/or the retention of a fragrance preparation;
  and/or
- as fixative.

In the above formula (I) and all further formulas in this text, wavy lines denote a bond which (depending on the enantiomer in question) extends out of the plane of the drawing or behind the plane of the drawing.
Further aspects of the invention can be seen from the following description, the practical examples, the figure and the appended patent claims.

The figure shows:

FIG. 1 Assessment of the substantivity of the compound of formula (Ia) and of the compound of formula (Ib) compared to Lilial® (A) as a function of time

It was found, surprisingly, that a compound of formula (I) imparts an odor impression that comes very close to the complexity of the natural odor of lily of the valley blossom. That is, the odor impression imparted by the compound of formula (I) is characterized by outstanding naturalness and complexity, especially with respect to the odor note of lily of the valley. Such a complex odor impression, largely corresponding to the natural odor of lily of the valley blossom, has not previously been achieved with the fragrances with an odor note of lily of the valley known from the prior art.
The search for suitable substances with an odor note of lily of the valley, which led to the present invention, was hampered by the following circumstances:

- the mechanisms of odor perception are not adequately known;
- the relationships between special odor perception on the one hand and the chemical structure of the associated fragrance on the other hand have not been investigated sufficiently;
- even slight changes in the structural makeup of a known fragrance often bring about large changes in the sensory properties and impair compatibility for the human body.

The success of a search for suitable fragrances is therefore highly dependent on the intuition of the person conducting the search.
The fact that the odor profile of the compound of formula (I) to be used according to the invention is very similar to the odor profile of 3-(4-tert-butylphenyl)-2-methylpropanal was not to be expected, as the compound of formula (I) is structurally different in many respects from 3-(4-tert-butylphenyl)-2-methylpropanal (above formula (A)); the phenyl group in formula (A) is replaced in formula (I) with a cyclohexenyl group, the tert-butyl group in formula (A) is replaced with an isopropyl group, and the aldehyde side chain does not have a methyl group on the second carbon atom in formula (I), in contrast to formula (A).
The compound of formula (I) to be used according to the invention is characterized by high building-up capacity (Intrinsic adhesion on a substrate) and high substantivity (capacity for being absorbed from a, generally aqueous, phase onto a substrate or also to remain on a substrate after a washing or rinsing process). This effect is observed in particular on substrates such as the skin, the hair and textile fibers (e.g. wool, cotton, linen, synthetic fibers).
Another important technological requirement imposed on fragrances and fragrance preparations, especially for surfactant-containing products, is their substantivity with respect to the substrate or retention on the substrate, especially on the hair or on textile fibers. The terms “substantivity” and “retention” are for example explained in detail in EP 1 201 738 A1, cf. sections [0004]-[0005]. Fragrances are generally required to have high substantivity and/or retention.
In accordance with the foregoing, another aspect of the invention relates in particular to the use of the compound of formula (I) to be used according to the invention as an agent for increasing the substantivity and/or retention of a fragrance preparation (especially with respect to or on hair or textile fibers), preferably a fragrance preparation with an odor note of lily of the valley, preferably a fragrance preparation according to the invention as described below.
In addition to its high building-up capacity, the compound of formula (I) to be used according to the invention is characterized by its fixing properties, i.e. it is a fixative. As a fixative, the compound of formula (I) according to the invention increases the adherence of other fragrances, either by lowering their vapor pressure or by olfactory intensification (e.g. lowering of the threshold value). The invention therefore also relates—as mentioned above—to the use of the compound of formula (I) as a fixative.
The compound of formula (I) has indeed already been mentioned in the prior art, but its suitability as a fragrance, especially its particular suitability for imparting an odor note of lily of the valley, had not been recognized.
The publication Comptes Rendus des Séances de I'Académie des Sciences, Série C: Sciences Chimiques 1967, 264, 1083-1086 reports on investigations of the radical addition of ethanol or ethanal on β-pinene. The compound p-menthen-1-yl-7-ethanal is obtained as a minor constituent (less than 5%) of the crude product from radical addition of ethanal on β-pinene by means of benzoyl peroxide. A negative rotation value (−54.2°) is given for this compound.
The publication Zhurnal Organicheskoi Khimii 1974, 10, 1153-1157 reports on investigations of the radical addition of aliphatic aldehydes of the formula R—CH₂—CHO (R═H, methyl or ethyl) on β-pinene with Mn(III) acetate as initiator, optionally in the presence of catalytic amounts of copper(II) acetate. It was found that, depending on the reaction conditions (polarity of the solvent and amount of catalyst used), the reaction leads to an aldehyde of structure
and a ketone of structure
and/or to a dienaldehyde of the following structure
and an aldehyde ether of the following structure
wherein R in each case is selected from the group consisting of hydrogen, methyl and ethyl.
The last two aforementioned compounds are assessed as novel and characterized in detail in the publication Zhurnal Organicheskoi Khimii 1974, 10, 1153-1157. Exclusively for these compounds, it is stated in the aforementioned publication that they may be interesting as perfumes. This applied in particular in the case of the dienaldehyde with R=ethyl, as this compound is a structural analog of cyclamen aldehyde.
In the publication Bulletin de la Société Chimique de France 1973, 4, 1368-1372, a compound with the formula R—CH₂—CHO, in which
is mentioned as a product of the oxidation reaction of (p-menthen-1-yl-7)ethane-1,2-diol, which was itself produced from β-pinene and ethanol by a radical reaction. Detailed information on the physical and chemical properties of compound (I) is not disclosed.
The prior art described above does not contain any information on the olfactory properties of the compound of formula (I).
No distinction is made, in the aforementioned documents from the prior art, between the two enantiomers (compound of formula (Ia) as defined above and compound of formula (Ib) as defined above). Therefore it is not disclosed whether and in what proportions the compound disclosed in each case in the prior art contains the compound of formula (Ia) as defined above and/or the compound of formula (Ib) as defined above. The relative proportion of the two different enantiomers is determined by the enantiomeric composition of the respective educt β-pinene, since in the radical addition of an aldehyde on β-pinene, the stereochemistry remains unchanged. β-Pinene exists in two enantiomeric forms: (+β-pinene and (+)-β-pinene. In the aforementioned documents from the prior art it is only disclosed that β-pinene is used as educt. It is therefore not disclosed in what proportions the β-pinene used as educt contains the two enantiomers (−)-β-pinene or (+)-β-pinene.
Therefore the present invention also relates to a compound selected from the group consisting of the compound of formula (Ia)
and the compound of formula (Ib)
and a mixture comprising (i) the compound of formula (Ia) as defined above and (ii) the compound of formula (Ib) as defined above or consisting of the compound of formula (Ia) as defined above and the compound of formula (Ib) as defined above.
In the present text, compound of formula (Ia) or formula (Ib) means in each case the corresponding special enantiomer (as defined above), whereas the term “compound of formula (I)” comprises both the individual compounds selected from the group consisting of the compound of formula (Ia) and the compound of formula (Ib) and all mixtures (enantiomeric mixtures) consisting of these two compounds (in any mixture ratio). That is, statements relating to the “compound of formula (I)” always apply to the compound of formula (Ia) and the compound of formula (Ib) as well as to mixtures consisting of the compound of formula (Ia) and the compound of formula (Ib) in any mixture ratio.
In a mixture according to the invention consisting of the compound of formula (Ia) as defined above and the compound of formula (Ib) the mass ratio of the compound of formula (Ia) to the compound of formula (Ib) is preferably selected in such a way that the amount of rotation of the mixture is not −54.2°. Preferably, in said mixture the mass ratio of the compound of formula (Ia) to the compound of formula (Ib) is selected so as to give an amount of rotation greater than −54.2°, more preferably greater than −54°, even more preferably greater than −50°.
Mixtures that comprise the compounds of formula (Ia) as defined above and (ii) the compound of formula (Ib) as defined above or consist of these two compounds, are according to the invention mixtures preferably with

- a mass ratio of the compound of formula (Ia) to the compound of formula (Ib) in the range from 0.01 to 99.99, preferably in the range from 0.1 to 99.9, preferably in the range from 0.5 to 99.5, preferably in the range from 1.0 to 99.0, preferably in the range from 1.5 to 98.5, preferably in the range from 2.0 to 98.0
  and/or
- a total proportion of compounds of formulas (Ia) and (Ib) greater than 0.01 wt %, preferably greater than 1 wt %, preferably greater than 10 wt %, more preferably greater than 50 wt %, especially preferably greater than 90 wt %, relative to the total weight of the mixture comprising compound (Ia) and/or (Ib)

The odor profile of the compound of formula (Ia) as defined above is described as follows: odor note of lily of the valley, floral, sweet, watery, powdery and ozone-like, natural, caring, complex and radiant. In particular the complex odor impression, largely corresponding to the natural odor of lily of the valley blossom, is noteworthy. With respect to olfactory properties, the compound of formula (Ia) is therefore similar to 3-(4-tert-butylphenyl)-2-methylpropanal (formula (A)).
The odor profile of the compound of formula (Ib) as defined above is described as follows: odor note of lily of the valley, fruity, green, watery and aldehyde-like.
The compound of formula (Ia) is, owing to its odor profile, especially suitable for imparting, modifying or intensifying an odor note of lily of the valley and optionally one, several or all odor notes selected from the group consisting of floral, sweet, watery, powdery and ozone-like and/or one, several or all impressions selected from the group consisting of natural, caring, complex and radiant.
Furthermore, it was found that the compound of formula (Ia), in conjunction with one or more further fragrances, is able to produce or to intensify further odor notes that are desirable for perfumery purposes, especially the odor notes creamy (cf. examples 10 and 14), cosmetic (see example 10), rounded aldehyde-like (see example 12), green (see example 13) and watery-fruity (see example 15).
The compound of formula (Ib) is, owing to its odor profile, especially suitable for imparting, modifying or intensifying an odor note of lily of the valley and optionally one, several or all odor notes selected from the group consisting of fruity, green, watery and aldehyde-like.
Therefore the compound of formula (Ia) as defined above according to the invention is preferably used for imparting, modifying or intensifying an odor note of lily of the valley and optionally one, several or all odor notes selected from the group consisting of floral, sweet, watery, powdery and ozone-like and/or one, several or all impressions selected from the group consisting of natural, caring, complex and radiant.
Alternatively or additionally the compound of formula (Ib) as defined above is preferably used according to the invention for imparting, modifying or intensifying an odor note of lily of the valley and optionally one, several or all odor notes selected from the group consisting of fruity, green, watery and aldehyde-like.
Another aspect of the present invention relates to fragrance preparations, especially perfume oils, wherein according to the invention, owing to the odor profiles described above of the compound of formula (Ia) and of the compound of formula (Ib), in particular fragrance preparations or perfume oils with an odor note of lily of the valley are of interest.
A fragrance preparation is, in the context of the present text, a mixture of various substances, which is produced by a prescribed method from the corresponding substances according to a recipe or a formulation. Said preparations are produced and used specifically for the purpose of imparting, modifying or intensifying a desired odor impression, usually perceived as pleasant or positive in some other way. Preparations such as are used in preparative organic chemistry, especially the preparations known from the prior art described above for radical addition on β-pinene, therefore are not fragrance preparations in the sense of the present invention. Respective mixtures described in the publications Zhurnal Organicheskoi Khimii 1974, 10, 1153-1157, Comptes Rendus des Séances de I'Académie des Sciences, Series C: Sciences
Chimiques 1967, 264, 1083-1086 or Bulletin de la Société Chimique de France 1973, 4, 1368-1372, which comprise the compound of formula (I), are not an object of the present invention and in particular are not fragrance preparations according to the invention.
The following mixtures or combinations are therefore preferably also not fragrance preparations according to the invention:

- a mixture containing the compound of formula (I) as defined above, dimethylsulfoxide and optionally (p-menthen-1-yl-7)-2-ethanol tosylate as described in Comptes Rendus des Séances de I'Académie des Sciences, Series C: Sciences Chimiques 1967, 264, 1083-1086,
- a mixture containing the compound of formula (I) as defined above, the compound of formula (IV) described in Comptes Rendus des Séances de I'Académie des Sciences, Series C: Sciences Chimiques 1967, 264, 1083-1086 (as defined there) and optionally β-pinene and optionally ethanal and optionally di-tert-butyl peroxide,
- a mixture containing the compound of formula (I) as defined above, the compound of formula (4b) described in Bulletin de la Société Chimique de France 1973, 4, 1368-1372 (as defined there) and/or the compound of formula (1b) described in Bulletin de la Société Chimique de France 1973, 4, 1368-1372 (as defined there) and optionally β-pinene and optionally ethanol and optionally di-tert-butyl peroxide and/or benzoyl peroxide,
- a mixture containing the compound of formula (I) as defined above and heptane, acetic acid, copper(II) acetate, manganese(III) acetate and/or manganese(II) acetate, the compound of formula (Ia) described in Zhurnal Organicheskoi Khimii 1974, 10, 1153-1157 (as defined there) and/or the compound of formula (IIa) described in Zhurnal Organicheskoi Khimii 1974, 10, 1153-1157 (as defined there) and/or the compound of formula (IIIa) described in Zhurnal Organicheskoi Khimii 1974, 10, 1153-1157 (as defined there) and optionally β-pinene and optionally ethanal.

A fragrance preparation according to the invention is preferably not a mixture containing

- the compound of formula (I) as defined above and heptane, acetic acid, manganese(III) acetate and/or manganese(II) acetate, the compound of formula (Ia) described in Zhurnal Organicheskoi Khimii 1974, 10, 1153-1157 (as defined there) and/or the compound of formula (IIa) described in Zhurnal Organicheskoi Khimii 1974, 10, 1153-1157 (as defined there) and/or the compound of formula (IIIa) described in Zhurnal Organicheskoi Khimii 1974, 10, 1153-1157 (as defined there), and optionally β-pinene and optionally ethanal.
  or
- the compound of formula (I) as defined above and heptane, acetic acid, copper(II) acetate, manganese(III) acetate and/or manganese(II) acetate, and optionally β-pinene and optionally ethanal.
  or
- the compound of formula (I) as defined above, optionally β-pinene and optionally ethanal and optionally di-tert-butyl peroxide
  or
- the compound of formula (I) as defined above, the compound of formula (1b) described in Bulletin de la Société Chimique de France 1973, 4, 1368-1372 (as defined there) and optionally β-pinene and optionally ethanol and optionally di-tert-butyl peroxide and/or benzoyl peroxide.

Even more preferably, a fragrance preparation according to the invention is not a mixture containing

- the compound of formula (I) as defined above and heptane, acetic acid, manganese(III) acetate and/or manganese(II) acetate and optionally β-pinene and optionally ethanal
  or
- the compound of formula (I) as defined above, the compound of formula (1b) described in Bulletin de la Société Chimique de France 1973, 4, 1368-1372 (as defined there) and optionally di-tert-butyl peroxide and/or benzoyl peroxide.

Quite especially preferably, the fragrance preparation according to the invention is not a mixture containing the compound of formula (I) as defined above and one or more substances selected from the group consisting of heptane, acetic acid, β-pinene, ethanal, manganese salts, copper salts, compound of formula (Ia) from the publication Zhurnal Organicheskoi Khimii 1974, 10, 1153-1157 (as defined there), compound of formula (IIa) from the publication Zhurnal Organicheskoi Khimii 1974, 10, 1153-1157 (as defined there), compound of formula (IIIa) from the publication Zhurnal Organicheskoi Khimii 1974, 10, 1153-1157 (as defined there), dimethylsulfoxide, (p-menthen-1-yl-7)-2-ethanol tosylate, di-tert-butyl peroxide, benzoyl peroxide, the compound (4b) described in Bulletin de la Société Chimique de France 1973, 4, 1368-1372 (as defined there) and the compound (1 b) described in Bulletin de la Société Chimique de France 1973, 4, 1368-1372 (as defined there). Even more preferably, the fragrance preparation according to the invention is not a mixture containing the compound of formula (I) as defined above and one or more peroxides.
A fragrance preparation according to the invention, especially in the form of a perfume oil, preferably with an odor note of lily of the valley, consists of or comprises

- compound of formula (I) as defined above,
  and
- one, 2, 3, 4, 5, 6, 7, 8, 9, 10 or more further fragrances, which are not a compound of formula (I).

In particular, by combining the compounds of formula (I) as defined above, preferably in one of the embodiments stated as being preferable, with one or more further fragrances (preferably with one, several or all odor notes selected from the group consisting of floral, sweet, watery, ozone-like, woody, ambery, musky, fruity, animal), interesting new fragrance preparations can be produced. In this way, mixtures with particularly interesting, natural, new and original notes can be created. Fragrances that are, in the sense of the above definition, suitable as further fragrances for use in a fragrance preparation according to the invention, are given for example in S. Arctander, Perfume and Flavor Materials, Vol. I and II, Montclair, N.J. 1969, self-published, or K. Bauer et al., Common Fragrance and Flavor Materials, 4th Edition, Wiley-VCH, Weinheim 2001.
In detail, the following may be mentioned: extracts of natural raw materials such as essential oils, concretes, absolutes, resins, resinoids, balsams, tinctures, for example:
amber tincture; amyris oil; angelica seed oil; angelica root oil; anise oil; valerian oil; basil oil; tree moss absolute; bay oil; mugwort oil; gum benzoin; bergamot oil; beeswax absolute; birch tar oil; bitter almond oil; savory oil; buchu leaf oil; cabreuva oil; cade oil; calmus oil; camphor oil; cananga oil; cardamom oil; cascarilla oil; cassia oil; cassie absolute; castoreum absolute; cedar leaf oil; cedar wood oil; cistus oil; citronella oil; lemon oil; copaiba balsam; copaiba balsam oil; coriander oil; costus root oil; cumin oil; cypress oil; davana oil; dill oil; dill seed oil; eau de brouts absolute; oak moss absolute; elemi oil; tarragon oil; Eucalyptus citriodora oil; eucalyptus oil; fennel oil; spruce-needle oil; galbanum oil; galbanum resin; geranium oil; grapefruit oil; guaiac wood oil; gurjun balsam; gurjun balsam oil; helichrysum absolute; helichrysum oil; ginger oil; iris root absolute; iris root oil; jasmine absolute; calmus oil; blue chamomile oil; Roman chamomile oil; carrot seed oil; cascarilla oil; pine needle oil; spearmint oil; caraway oil; labdanum oil; labdanum absolute; labdanum resin; lavandin absolute; lavandin oil; lavender absolute; lavender oil; lemongrass oil; lovage oil; distilled lime oil; pressed lime oil; linaloe oil; Litsea cubeba oil; bay leaf oil; mace oil; marjoram oil; mandarin oil; massoy bark oil; mimosa absolute; musk seed oil; musk tincture; clary oil; nutmeg oil; myrrh absolute; myrrh oil; myrtle oil; clove leaf oil; clove blossom oil; neroli oil; olibanum absolute; olibanum oil; opopanax oil; orange blossom absolute; orange oil; origanum oil; palmarosa oil; patchouli oil; perilla oil; Peru balsam oil; parsley leaf oil; parsley seed oil; petitgrain oil; peppermint oil; pepper oil; pimento oil; pine oil; poley oil; rose absolute; rosewood oil; rose oil; rosemary oil; Dalmatian sage oil; Spanish sage oil; sandalwood oil; celery seed oil; spike lavender oil; star anise oil; styrax oil; tagetes oil; fir-needle oil; tea tree oil; turpentine oil; thyme oil; tolu balsam; tonka absolute; tuberose absolute; vanilla extract; violet leaf absolute; verbena oil; vetiver oil; juniper berry oil; wine lees oil; wormwood oil; wintergreen oil; ylang-ylang oil; hyssop oil; civet absolute; cinnamon leaf oil; cinnamon bark oil and fractions thereof, or ingredients isolated therefrom;
individual fragrances from the hydrocarbons group, for example 3-carene; α-pinene; β-pinene; α-terpinene; γ-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; farnesene; limonene; longifolene; myrcene; ocimene; valencene; (E,Z)-1,3,5-undecatriene; styrene; diphenylmethane;
of aliphatic alcohols, for example hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2-methyl-2-heptanol; 2-methyl-2-octanol; (E)-2-hexenol; 1-octen-3-ol; mixture of 3,4,5,6,6-pentamethyl-3/4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan-2-ol; (E,Z)-2,6-nonadienol; 3,7-dimethyl-7-methoxyoctan-2-ol; 9-decenol; 10-undecenol; 4-methyl-3-decen-5-ol;
of aliphatic aldehydes and acetals thereof, for example hexanal; heptanal; octanal; nonanal; decanal; undecanal; dodecanal; 2-methyloctanal; 2-methylnonanal; (E)-2-hexenal; (Z)-4-heptenal; 2,6-dimethyl-5-heptenal; 10-undecenal; (E)-4-decenal; 2-dodecenal; 2,6,1 0-trimethyl-9-undecenal; 2,6,1 0-trimethyl-5,9-undecadienal; heptanaldiethylacetal; 1,1-dimethoxy-2,2,5-trimethyl-4-hexene; citron ellyloxyacetaldehyde; 1-(1-methoxy-propoxy)-(E/Z)-3-hexene;
of aliphatic ketones and oximes thereof, for example 2-heptanone; 2-octanone; 3-octanone; 2-nonanone; 5-methyl-3-heptanone; 5-methyl-3-heptanone-oxime; 2,4,4,7-tetramethyl-6-octen-3-one; 6-methyl-5-hepten-2-one;
of aliphatic sulfur-containing compounds, for example 3-methylthiohexanol; 3-methylthiohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexyl acetate; 1-menthene-8-thiol;
of aliphatic nitriles, for example 2-nonenoic acid nitrile; 2-undecenoic acid nitrile; 2-tridecenoic acid nitrile; 3,12-tridecadienoic acid nitrile; 3,7-dimethyl-2,6-octadienoic acid nitrile; 3,7-dimethyl-6-octenoic acid nitrile;
of esters of aliphatic carboxylic acids, for example (E)- and (Z)-3-hexenyl formate; ethyl acetoacetate; isoamyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate; (E)-2-hexenyl acetate; (E)- and (Z)-3-hexenyl acetate; octyl acetate; 3-octyl acetate; 1-octen-3-yl acetate; ethyl butyrate; butyl butyrate; isoamyl butyrate; hexyl butyrate; (E)- and (Z)-3-hexenyl-isobutyrate; hexyl crotonate; ethyl isovalerate; ethyl-2-methylpentanoate; ethyl hexanoate; allyl hexanoate; ethyl heptanoate; allyl heptanoate; ethyl octanoate; ethyl-(E,Z)-2,4-decadienoate; methyl-2-octinate; methyl-2-noninate; allyl-2-isoamyloxyacetate; methyl-3,7-dimethyl-2,6-octadienoate; 4-methyl-2-pentylcrotonate;
of acyclic terpene alcohols, for example geraniol; nerol; lavandulol; nerolidol; farnesol; tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl-7-octen-2-ol; 2,6-dimethyloctan-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadien-2-ol; 2,6-dimethyl-3,5-octadien-2-ol; 3,7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl-1,5,7-octatrien-3-ol 2,6-dimethyl-2,5,7-octatrien-1-ol; and formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoates thereof;
of acyclic terpene aldehydes and ketones, for example citronellal; 7-methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9-undecenal; geranylacetone; and the dimethyl and diethyl acetals of geranial, neral,
of cyclic terpene alcohols, for example menthol; isopulegol; alpha-terpineol; terpinenol-4; menthan-8-ol; menthan-1-ol; menthan-7-ol; borneol; isoborneol; linalool oxide; nopol; cedrol; ambrinol; vetiverol; guaiol; and formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoates thereof;
of cyclic terpene aldehydes and ketones, for example menthone; isomenthone; 8-mercaptomenthan-3-one; carvone; camphor; fenchone; alpha-ionone; beta-ionone; alpha-n-methylionone; beta-n-methylionone; alpha-isomethylionone; beta-isomethylionone; alpha-irone; beta-damascenone; 1-(2,4,4-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one; 1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-methano-naphthalen-8(5H)-one; 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal; nootkatone; dihydronootkatone; 4,6,8-megastigmatrien-3-one; alpha-sinensal; beta-sinensal; acetylated cedar wood oil (methyl cedryl ketone);
of cyclic alcohols, for example 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3-isocamphylcyclohexanol; 2,6,9-trimethyl-Z2,Z5, E9-cyclododecatrien-1-ol; 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol;
of cycloaliphatic alcohols, for example alpha,3,3-trimethylcyclohexylmethanol; 1-(4-isopropylcyclohexyl)ethanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)butanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-pentan-2-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 1-(2,2,6-trimethylcyclohexyl)pentan-3-ol; 1-(2,2,6-trimethylcyclohexyl)hexan-3-ol;
of cyclic and cycloaliphatic ethers, for example cineol; cedryl methyl ether; cyclododecylmethyl ether; 1,1-dimethoxycyclododecane; (ethoxymethoxy)cyclo-dodecane; alpha-cedrene-epoxide; 3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan; 3a-ethyl-6,6,9a-trimethyldodecahydronaphtho[2,1 b]furan; 1 ,5,9-trimethyl-1 3-oxabicyclo[1 0.1.0]trideca-4,8-diene; rose oxide; 2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-1,3-dioxane;
of cyclic and macrocyclic ketones, for example 4-tert-butylcyclohexanone; 2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentyl-cyclopentanone; 2-hydroxy-3-methyl-2-cyclopenten-1-one; 3-methyl-cis-2-penten-1-yl-2-cyclopenten-1-one; 3-methyl-2-pentyl-2-cyclopenten-1-one; 3-methyl-4-cyclopentadecenone; 3-methyl-5-cyclopentadecenone; 3-methylcyclopentadecanone; 4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone; 4-tert-pentylcyclohexanone; 5-cyclohexadecen-1-one; 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone; 8-cyclohexadecen-1-one; 9-cycloheptadecen-1-one; cyclopentadecanone; cyclohexadecanone;
of cycloaliphatic aldehydes, for example 2-methyl-4-(2,2,6-trimethyl-cyclohexen-1-yl)-2-butenal; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarbaldehyde; 4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarbaldehyde;
of cycloaliphatic ketones, for example 1-(3,3-dimethylcyclohexyl)-4-penten-1-one; 2,2-dimethyl-1-(2,4-dimethyl-3-cyclohexen-1-yl)-1-propanone; 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one; 2,3,8,8-tetramethyl-1 ,2,3,4,5,6,7,8-octahydro-2-naphthalenylmethyl ketone; methyl-2,6,10-trimethyl-2,5,9-cyclododecatrienyl ketone; tert-butyl-(2,4-dimethyl-3-cyclohexen-1-yl) ketone;
of esters of cyclic alcohols, for example 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert-pentylcyclohexyl acetate; 4-tert-pentyl-cyclohexyl acetate; 3,3,5-trimethylcyclohexyl acetate; decahydro-2-naphthyl acetate; 2-cyclopentylcyclopentyl crotonate; 3-pentyltetrahydro-2H-pyran-4-yl acetate; decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexa-hydro-5, or 6-indenyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5, or 6-indenyl-propionate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5, or 6-indenylisobutyrate; 4,7-methanooctahydro-5, or 6-indenyl acetate;
of esters of cycloaliphatic alcohols, for example 1-cyclohexylethyl crotonate;
of esters of cycloaliphatic carboxylic acids, for example allyl-3-cyclohexyl propionate; allylcyclohexyloxyacetate; cis- and trans-methyldihydrojasmonate; cis- and trans-methyljasmonate; methyl-2-hexyl-3-oxocyclopentane carboxylate; ethyl-2-ethyl-6,6-dimethyl-2-cyclohexene-carboxylate; ethyl-2,3,6,6-tetramethyl-2-cyclohexene-carboxylate; ethyl-2-methyl-1,3-dioxolan-2-acetate;
of araliphatic alcohols, for example benzyl alcohol; 1-phenylethyl alcohol; 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3-(3-methylphenyl)propanol; 1,1-dimethyl-2-phenylethyl alcohol; 1,1-dimethyl-3-phenylpropanol; 1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenulpentanol; 3-methyl-5-phenylpentanol; 3-phenyl-2-propen-1-ol; 4-methoxybenzyl alcohol; 1-(4-isopropylphenyl)ethanol;
of esters of araliphatic alcohols and aliphatic carboxylic acids, for example benzyl acetate; benzyl propionate; benzyl isobutyrate; benzyl isovalerate; 2-phenylethyl acetate; 2-phenylethyl propionate; 2-phenylethyl isobutyrate; 2-phenylethyl isovalerate; 1-phenylethyl acetate; alpha-trichloromethylbenzyl acetate; alpha,alpha-dimethylphenylethyl acetate; alpha,alpha-dimethylphenylethyl butyrate; cinnamyl acetate; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate;
of araliphatic ethers, for example 2-phenylethyl methyl ether; 2-phenylethyl isoamyl ether; 2-phenylethyl-1-ethoxyethyl ether; phenyl acetaldehyde dimethylacetal; phenylacetaldehyde diethylacetal; hydratropa aldehyde dimethylacetal; phenylacetaldehyde glycerol acetal; 2,4,6-trimethyl-4-phenyl-1,3-dioxane; 4,4a,5,9b-tetra-hydroindeno[1,2-d]-m-dioxin; 4,4a,5,9b-tetrahydro-2,4-dimethylindeno[1,2-d]-m-dioxin;
of aromatic and araliphatic aldehydes, for example benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; hydratropa aldehyde; 4-methylbenzaldehyde; 4-methylphenylacetaldehyde; 3-(4-ethylphenyl)-2,2-dimethylpropanal; 2-methyl-3-(4-isopropylphenyl)propanal; 2-methyl-3-(4-isobutylphenyl)propanal; 3-(4-tert-butyl-phenyl)propanal; cinnamaldehyde; alpha-butyl cinnamaldehyde; alpha-hexyl cinnamaldehyde; 3-methyl-5-phenylpentanal; 4-methoxybenzaldehyde; 4-hydroxy-3-methoxybenzaldehyde; 4-hydroxy-3-ethoxybenzaldehyde; 3,4-methylene dioxybenzaldehyde; 3,4-dimethoxybenzaldehyde; 2-methyl-3-(4-methoxyphenyl)propanal; 2-methyl-3-(4-methylene dioxyphenyl)propanal;
of aromatic and araliphatic ketones, for example acetophenone; 4-methylacetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone; 4-(4-hydroxyphenyl)-2-butanone; 1-(2-naphthalenyl)ethanone; 2-benzofuranylethanone; (3-methyl-2-benzofuranyl)ethanone; benzophenone; 1,1,2,3,3,6-hexamethyl-5-indanylmethyl ketone; 6-tert-butyl-1 ,1-di-methyl-4-indanylmethyl ketone; 1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl)-1H-5-indenyl]ethanone; 5′,6′,7′,8′-tetrahydro-3′,5′,5′,6′,8′,8′-hexamethyl-2-acetonaphthone;
of aromatic and araliphatic carboxylic acids and esters thereof, for example benzoic acid; phenylacetic acid; methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methylphenyl acetate; ethylphenyl acetate; geranylphenyl acetate; phenylethyl-phenyl acetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenylethyl cinnamate; cinnamyl cinnamate; allylphenoxyacetate; methyl salicylate; hexyl salicylate; cyclohexyl salicylate; cis-3-hexenyl salicylate; benzyl salicylate; phenylethyl salicylate; methyl-2,4-dihydroxy-3,6-dimethyl benzoate; ethyl-3-phenylglycidate; ethyl-3-methyl-3-phenylglycidate;
of nitrogen-containing aromatic compounds, for example 2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone; cinnamic acid nitrile; 3-methyl-5-phenyl-2-pentenoic acid nitrile; 3-methyl-5-phenylpentanoic acid nitrile; methylanthranilate; methy-N-methylanthranilate; Schiff's bases of methylanthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3-(4-tert-butyl-phenyl)propanal or 2,4-dimethyl-3-cyclohexenecarbaldehyde; 6-isopropylquinoline; 6-isobutylquinoline; 6-sec-butylquinoline; 2-(3-phenylpropyl)pyridine; indole; skatole; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine;
of phenols, phenyl ethers and phenyl esters, for example estragole; anethole; eugenyl methyl ether; isoeugenol; isoeugenyl methyl ether; thymol; carvacrol; diphenyl ether; beta-naphthylmethyl ether; beta-naphthylethyl ether; beta-naphthylisobutyl ether; 1,4-dimethoxybenzene; eugenyl acetate; 2-methoxy-4-methylphenol; 2-ethoxy-5-(1-propenyl)phenol; p-cresylphenyl acetate;
of heterocyclic compounds, for example 2,5-dimethyl-4-hydroxy-2H-furan-3-one; 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one; 3-hydroxy-2-methyl-4H-pyran-4-one; 2-ethyl-3-hydroxy-4H-pyran-4-one;
of lactones, for example 1,4-octanolide; 3-methyl-1,4-octanolide; 1,4-nonanolide; 1,4-decanolide; 8-decen-1,4-olide; 1,4-undecanolide; 1,4-dodecanolide; 1,5-decanolide; 1,5-dodecanolide; 4-methyl-1,4-decanolide; 1,15-pentadecanolide; 1,16-hexadecanolide; 9-hexadecen-1,16-olide; 10-oxa-1,16-hexadecanolide; 11-oxa-1,16-hexadecanolide; 12-oxa-1,16-hexadecanolide; ethylene-1,12-dodecanedioate; ethylene-1,13-tridecandioate; 2,3-dihydrocoumarin; octahydrocoumarin.
In a fragrance preparation according to the invention, especially in the form of a perfume oil, the amount of the compound of formula (Ia) as defined above and/or of the compound of formula (Ib) as defined above is preferably in the range from 0.0001 to 40 wt %, preferably in the range from 0.001 to 25 wt %, in each case relative to the total weight of the fragrance preparation.
With respect to the preferred mass ratio of the compound of formula (Ia) to the compound of formula (Ib), the same applies as for mixtures according to the invention comprising or consisting of the compounds of formula (Ia) and formula (Ib) (see above).
In addition to the aforementioned fragrances, a fragrance preparation according to the invention optionally contains further constituents, which are not themselves fragrances in the sense of the above definition, for example solvents, solubilizers, emulsifiers, stabilizers, radical traps.
In a preferred embodiment, a fragrance preparation according to the invention, especially in the form of a perfume oil, comprises one, 2, 3 or more further fragrances with an odor note of lily of the valley and optionally one, several or all odor notes selected from the group consisting of floral, sweet, watery, ozone-like, woody, ambery, musky, fruity, animal. Corresponding fragrances are known by a person skilled in the art.
A fragrance preparation according to the invention is especially preferred in which

- (i) the amount of the compound of formula (Ia) is sufficient to endow the fragrance preparation with an odor note of lily of the valley and optionally one, several or all odor notes selected from the group consisting of floral, sweet, watery, powdery and ozone-like,
  and/or
- (ii) one, several or all further fragrances of the fragrance preparation impart an odor note of lily of the valley and optionally one, several or all odor notes selected from the group consisting of floral, sweet, watery, powdery and ozone-like, wherein the amount of the compound of formula (Ia) is sufficient, in comparison with a comparative fragrance preparation of otherwise identical composition without the compound of formula (Ia), to modify and/or to intensify the odor note of lily of the valley and optionally one, several or all the odor notes floral, sweet, watery, powdery and ozone-like,
  and/or
- (iii) the amount of the compound of formula (Ia) is sufficient to endow the fragrance preparation with one, several or all impressions selected from the group consisting of natural, caring, complex and radiant
  and/or
- (iv) the amount of the compound of formula (Ia) is sufficient to modify and/or to intensify one, several or all impressions selected from the group consisting of natural, caring, complex and radiant in comparison with a comparative fragrance preparation of otherwise identical composition without the compound of formula (Ia)
  and/or
- (v) the amount of the compound of formula (Ib) is sufficient to endow the fragrance preparation with an odor note of lily of the valley and optionally one, several or all odor notes selected from the group consisting of fruity, green, watery and aldehyde-like,
  and/or
- (vi) one, several or all further fragrances of the fragrance preparation impart an odor note of lily of the valley and optionally one, several or all odor notes selected from the group consisting of fruity, green, watery and aldehyde-like and the amount of the compound of formula (Ib) is sufficient, in comparison with a comparative fragrance preparation of otherwise identical composition without the compound of formula (Ib), to modify and/or to intensify the odor note of lily of the valley and optionally one, several or all the odor notes selected from the group consisting of fruity, green, watery and aldehyde-like.

Fragrance preparations according to the invention are for example obtainable by a method comprising the step of mixing

- compound of formula (I) as defined above
  and
- one, 2, 3, 4, 5, 6, 7, 8, 9, 10 or more further fragrances, which are not a compound of formula (I),
- and optionally further constituents, which are not fragrances.

The compound of formula (I) to be used as fragrance according to the invention, mixtures according to the invention as defined above and fragrance preparations according to the invention as defined above are used in particular for producing perfumed products (perfumed articles).
Accordingly, another aspect of the present invention relates to a perfumed product. A perfumed product according to the invention comprises the compound of formula (I) as defined above, preferably in a sensorially effective amount.
The compound of formula (I) is preferably a constituent of a mixture or fragrance preparation according to the invention. Therefore, in a preferred embodiment, a perfumed product comprises a mixture or fragrance preparation according to the invention, and a carrier or a substrate, wherein the carrier or the substrate is in direct contact with said mixture or fragrance preparation. The substrate is for example a solid substrate or the carrier is for example a solid carrier.
Preferred perfumed products according to the invention are detergents and cleaning products, hygiene or care products, especially products from the area of body and hair care, cosmetics and household products.
With respect to preferred embodiments, the statements made above apply correspondingly.
In this context, a perfumed product according to the invention is especially preferred in which the amount of the compound of formula (Ia) as defined above and/or of the compound of formula (Ib) as defined above is in the range from 0.0001 to 5 wt %, preferably in the range from 0.001 to 2.5 wt %, in each case relative to the total weight of the product.
With respect to the preferred mass ratio of the compound of formula (Ia) to the compound of formula (Ib), the same applies as for mixtures according to the invention comprising or consisting of the compounds of formula (Ia) and formula (Ib).
Preferred perfumed products according to the invention are selected from the group consisting of:
perfume extracts, eaux de parfum, eaux de toilette, shaving lotions, eaux de Cologne, pre-shave products, splash-Colognes, perfumed tissue wipes, perfumes for acid, alkaline and neutral cleansing agents, detergents, washing tablets, disinfectants, and air fresheners, aerosol sprays, waxes and polishes, and body care products, bath oils, cosmetic emulsions, for example skin creams and lotions, sunscreen creams and lotions, after-sun creams and lotions, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, after-shave creams and lotions, tanning creams and lotions, hair care products, for example hair sprays, hair gels, fixing hair lotions, hair rinses, hair dyes, hair shaping agents and hair straightening agents, hair lotions, hair creams and lotions, deodorants and antiperspirants, products for decorative cosmetics, e.g. eyelid shadow, nail varnishes, makeup, lipsticks, mascara, as well as candles, lamp oils, joss sticks, insecticides, repellents, propellants.
Fragrance preparations according to the invention containing the compound of formula (I) or a mixture according to the invention as defined above can generally be used (e.g. in concentrated form, in solutions or in the modified form described below) for the production of e.g. perfume extracts, eaux de parfum, eaux de toilette, shaving lotions, eaux de cologne, pre-shave products, splash-Colognes and perfumed tissue wipes and the perfuming of acidic, alkaline and neutral cleaning agents, for example floor cleaners, window cleaners, dishwasher agents, bath and sanitary cleaners, scouring products, solid and liquid lavatory cleaners, powder and foam carpet cleaners, liquid detergents, powdered detergents, laundry pretreatment agents such as bleach, soaking agents and stain removers, fabric softeners, washing soaps, washing tablets, disinfectants, surface disinfectants and air fresheners in the form of liquid or gel or applied on a solid carrier, aerosol sprays, waxes and polishes such as furniture polishes, floor waxes, shoe creams and body care products, for example solid and liquid soaps, shower gels, shampoos, shaving soap, shaving foams, bath oils, cosmetic emulsions of the oil-in-water, water-in-oil and water-in-oil-in-water type, for example skin creams and lotions, face creams and lotions, sunscreen creams and lotions, after-sun creams and lotions, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, after-shave creams and lotions, tanning creams and lotions, hair care products, for example hair sprays, hair gels, fixing hair lotions, hair rinses, permanent and semi-permanent hair dyes, hair shaping agents such as cold waves and hair straightening agents, hair lotions, hair creams and lotions, deodorants and antiperspirants, for example underarm sprays, roll-ons, deodorant sticks, deodorant creams, products for decorative cosmetics, for example eyelid shadow, nail varnishes, makeup, lipsticks, mascara as well as candles, lamp oils, joss sticks, insecticides, repellents, propellants.
Preferred perfumed products according to the invention are products selected from the group consisting of washing and cleaning products, hygiene or care products, especially from the area of body and hair care, cosmetics and household products, fine fragrance (perfume), air care (especially candles), air fresheners.
The aforementioned fragrance preparations according to the invention or the fragrance preparations to be used according to the invention in the corresponding products can be used for perfuming in liquid form, undiluted or diluted with a solvent. Suitable solvents for this are e.g. ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate etc. For the explicitly named solvents, it applies that in the context of the present text, in the case of the presence of their own olfactory properties, they are to be classified exclusively as the constituent “solvent” and not the “fragrances”.
The compound of formula (I) contained in the perfumed products according to the invention, a mixture according to the invention as defined above or a fragrance preparation according to the invention as defined above can, in a preferred embodiment, be absorbed on a carrier, which ensures both a fine distribution of the fragrances in the product and controlled release during use. Said carriers can be porous inorganic materials such as light sulfate, silica gels, zeolites, gypsums, clays, clay granules, porous concrete etc. or organic materials such as wood and cellulose-based materials.
The compound of formula (I) contained in the perfumed products according to the invention, a mixture according to the invention as defined above or a fragrance preparation according to the invention as defined above can also be microencapsulated, spray-dried, as inclusion complexes or as extrusion products and can be added in this form to the product or article to be perfumed.
Optionally, the properties of the fragrance preparations modified in this way can be further optimized by so-called “coating” with suitable materials with a view to a more targeted release of fragrance, for which preferably wax-like plastics, e.g. polyvinyl alcohol, are used.
The microencapsulation of the fragrance preparations can be carried out for example by the so-called coacervation process using capsule materials, e.g. of polyurethane-like substances or soft gelatin. The spray-dried perfume oils can be produced for example by spray-drying an emulsion or dispersion containing the perfume oil, wherein modified starches, proteins, dextrin and vegetable gums can be used as carriers. Inclusion complexes can be produced for example by feeding dispersions of the fragrance preparation and cyclodextrins or urea derivatives into a suitable solvent, e.g. water. Extrusion products can be produced by melting the fragrance preparation with a suitable wax-like substance and by extrusion and subsequent solidification, optionally in a suitable solvent, e.g. isopropanol.
The fragrance preparations according to the invention can then, as already mentioned, be used in concentrated form, in solutions or in the modified form described above for the production of the corresponding perfumed articles according to the invention.
Ingredients with which the compound of formula (I) according to the invention, a mixture according to the invention as defined above or a fragrance preparation according to the invention as defined above can preferably be combined are for example: preservatives, abrasives, antiacne agents, agents against skin aging, antibacterial agents, anticellulitis agents, antidandruff agents, anti-inflammatory agents, agents for preventing irritation, agents that inhibit irritation, antimicrobial agents, antioxidants, astringents, agents inhibiting sweating, antiseptics, antistatic agents, binders, buffers, carriers, chelating agents, cell stimulants, cleaning agents, care agents, depilatory agents, surface active substances, deodorants, antiperspirants, plasticizers, emulsifiers, enzymes, essential oils, fibers, film-forming agents, fixatives, foam formers, foam stabilizers, antifoaming agents, foam boosters, fungicides, gelling agents, gel-forming agents, hair care agents, hair shaping agents, hair straightening agents, hydrating agents, moisturizers, humectants, bleaching agents, strengthening agents, stain removers, optical brighteners, impregnating agents, dirt repellents, agents that reduce friction, lubricants, moisturizing creams, ointments, opacifiers, plasticizers, covering agents, polish, gloss agents, polymers, powders, proteins, refatting agents, abrading agents, silicones, skin calming agents, skin cleansing agents, skin-care agents, skin healing agents, skin lightening agents, skin protecting agents, skin softeners, cooling agents, skin cooling agents, warming agents, skin warming agents, stabilizers, UV absorbents, UV filters, detergents, fabric softeners, suspending agents, skin tanning agents, thickeners, vitamins, oils, waxes, fats, phospholipids, saturated fatty acids, singly or multiply unsaturated fatty acids, α-hydroxy acids, polyhydroxy fatty acids, liquefiers, dyes, color protecting agents, pigments, anticorrosive agents, aromatic substances, flavoring materials, polyols, surfactants, electrolytes, organic solvents or silicone derivatives.
Mixtures such as are used in preparative organic chemistry, especially the preparations for radical addition on β-pinene known from the prior art described above, are not perfumed products in the sense of the present invention. The mixtures optionally described in the works Zhurnal Organicheskoi Khimii 1974, 10, 1153-1157, Comptes Rendus des Séances de I'Académie des Sciences, Series C: Sciences Chimiques 1967, 264, 1083-1086 or Bulletin de la Société Chimique de France 1973, 4, 1368-1372, which comprise the compound of formula (I), are not objects of the present invention and in particular are not perfumed products according to the invention.
The following mixtures or combinations are therefore preferably also not perfumed products according to the invention:

- a mixture containing the compound of formula (I) as defined above, dimethylsulfoxide and optionally (p-menthen-1-yl-7)-2-ethanol tosylate as described in Comptes Rendus des Séances de I'Académie des Sciences, Series C: Sciences Chimiques 1967, 264, 1083-1086,
- a mixture containing the compound of formula (I) as defined above, the compound of formula (IV) described in Comptes Rendus des Séances de I'Académie des Sciences, Series C: Sciences Chimiques 1967, 264, 1083-1086 (as defined there) and optionally β-pinene and optionally ethanal and optionally di-tert-butyl peroxide,
- a mixture containing the compound of formula (I) as defined above, the compound of formula (4b) described in Bulletin de la Société Chimique de France 1973, 4, 1368-1372 (as defined there) and/or the compound of formula (1b) described in Bulletin de la Société Chimique de France 1973, 4, 1368-1372 (as defined there) and optionally β-pinene and optionally ethanol and optionally di-tert-butyl peroxide and/or benzoyl peroxide,
- a mixture containing the compound of formula (I) as defined above and heptane, acetic acid, copper(II) acetate, manganese(III) acetate and/or manganese(II) acetate, the compound of formula (Ia) described in Zhurnal Organicheskoi Khimii 1974, 10, 1153-1157 (as defined there) and/or the compound of formula (IIa) described in Zhurnal Organicheskoi Khimii 1974, 10, 1153-1157 (as defined there) and/or the compound of formula (IIIa) described in Zhurnal Organicheskoi Khimii 1974, 10, 1153-1157 (as defined there) and optionally β-pinene and optionally ethanal.

A perfumed product according to the invention is preferably not a mixture containing

- the compound of formula (I) as defined above and heptane, acetic acid, manganese(III) acetate and/or manganese(II) acetate, the compound of formula (Ia) described in Zhurnal Organicheskoi Khimii 1974, 10, 1153-1157 (as defined there) and/or the compound of formula (IIa) described in Zhurnal Organicheskoi Khimii 1974, 10, 1153-1157 (as defined there) and/or the compound of formula (IIIa) described in Zhurnal Organicheskoi Khimii 1974, 10, 1153-1157 (as defined there), and optionally β-pinene and optionally ethanal
  or
- the compound of formula (I) as defined above and heptane, acetic acid, copper(II) acetate, manganese(III) acetate and/or manganese(II) acetate, and optionally β-pinene and optionally ethanal
  or
- the compound of formula (I) as defined above, optionally β-pinene and optionally ethanal and optionally di-tert-butyl peroxide
  or
- the compound of formula (I) as defined above, the compound of formula (1b) described in Bulletin de la Société Chimique de France 1973, 4, 1368-1372 (as defined there) and optionally β-pinene and optionally ethanol and optionally di-tert-butyl peroxide and/or benzoyl peroxide.

Even more preferably, a perfumed product according to the invention is not a mixture containing

Quite especially preferably, the perfumed product according to the invention is not a mixture containing the compound of formula (I) as defined above and one or more substances selected from the group consisting of heptane, acetic acid, β-pinene, ethanal, manganese salts, copper salts, compound of formula (Ia) from the publication Zhurnal Organicheskoi Khimii 1974, 10, 1153-1157 (as defined there), compound of formula (IIa) from the publication Zhurnal Organicheskoi Khimii 1974, 10, 1153-1157 (as defined there), compound of formula (IIIa) from the publication Zhurnal Organicheskoi Khimii 1974, 10, 1153-1157 (as defined there), dimethylsulfoxide, (p-menthen-1-yl-7)-2-ethanol tosylate, di-tert-butyl peroxide, benzoyl peroxide, the compound (4b) described in Bulletin de la Société Chimique de France 1973, 4, 1368-1372 (as defined there) and the compound (1b) described in Bulletin de la Société Chimique de France 1973, 4, 1368-1372 (as defined there).
A further aspect of the present invention relates to a method of imparting, intensifying and/or modifying odor notes, especially an odor note of lily of the valley. A method according to the invention of imparting, intensifying and/or modifying odor notes, especially an odor note of lily of the valley and optionally one, several or all odor notes selected from the group consisting of floral, sweet, watery, powdery and ozone-like comprising the following step:
mixing or bringing into contact

- the compound of formula (I) as defined above, or
- a mixture according to the invention as defined above, or
- a fragrance preparation according to the invention as defined above

preferably in a sensorially effective amount with a product.
With respect to preferred embodiments, the above statements apply correspondingly.
The method according to the invention described above is also suitable in the context of the production of a perfumed product according to the invention, wherein as result of the step of mixing or bringing into contact

- of the compound of formula (I) as defined above, or
- of a mixture according to the invention as defined above, or
- of a fragrance preparation according to the invention as defined above

preferably in a sensorially effective amount with a product, the perfumed product according to the invention is formed. “Product” is in this case to be understood as the totality of the ingredients of the perfumed product according to the invention with the exception of the compound of formula (I) that is used, the mixture used according to the invention or the fragrance preparation used according to the invention.
In the method according to the invention, the high substantivity of the compounds (Ia) and (Ib) according to the invention proves advantageous, since the higher the substantivity of a fragrance, the smaller is the amount of the fragrance required to be used for maintaining an odor for a specified time.
Another aspect of the present invention relates to a method of providing skin, hair, surfaces or textile fibers with an odor note, especially an odor note of lily of the valley. A method according to the invention of providing skin, hair, surfaces or textile fibers with an odor note, especially an odor note of lily of the valley comprises the following steps:

- providing a fragrance preparation comprising
  - (a) compound of formula (I) as defined above and
  - (b) one or more further fragrances, which are not a compound of formula (I)
  - wherein, in the fragrance preparation, the amount of the compound of formula (I) is sufficient to impart, to modify and/or to intensify an odor note of lily of the valley;
- applying the fragrance preparation on skin, hair and/or textile fibers.

The fragrance preparation can be a constituent of a perfumed product according to the invention, for example a body, hair or textile care product.
With respect to preferred embodiments, the above statements apply correspondingly.
The compound of formula (I) to be used as fragrance according to the invention is obtainable inter alia by radical addition of ethanal onto (+)-β-pinene. The compounds according to the invention selected from the group consisting of the compound of formula (Ia) and of the compound of formula (Ib) are obtainable inter alia by radical addition of ethanal on (+)-β-pinene or (−)-β-pinene.
Another problem to be solved by the present invention was to provide novel methods for the production of the compound of formula (I) to be used as fragrance according to the invention and the compounds according to the invention selected from the group consisting of the compound of formula (Ia).
A method according to the invention for producing the compound of formula (I) as defined above comprises the step
acid-catalyzed reaction of an acetal of formula (II) so that the compound of formula (I) is formed
wherein the group R in the acetal of formula (II) is a linear or branched, saturated or unsaturated alkyl group with 1 to 10 carbon atoms, preferably a butyl group.
The acetal of formula (II) used in the method according to the invention
wherein the group R in the acetal of formula (II) is a linear or branched, saturated or unsaturated alkyl group with 1 to 10 carbon atoms, preferably a butyl group, is novel and is also an object of the present invention. The designation “acetal of formula (II)” comprises both the individual enantiomers (acetal of formula (IIa) as defined below and acetal of formula (IIb) as defined below) and all mixtures (enantiomeric mixtures) consisting of these two compounds (in any mixture ratio). That is, statements referring to the “acetal of formula (II)” always apply to the acetal of formula (IIa) and to the acetal of formula (IIb) as well as to mixtures consisting of the acetal of formula (IIa) and the acetal of formula (IIb) in any mixture ratio.
The acetal of formula (II) can be obtained in various ways (see below), wherein the educt is in each case preferably limonene. The stereochemistry of the educt used determines the stereochemistry of the compound of formula (I) obtained. If d-(+)-limonene is used as educt, the result is the compound of formula (Ia), and if I-(−)-limonene is used as educt, the result is the compound of formula (Ib). The present invention therefore also relates to the use

- of d-(+) limonene as educt for producing the compound of formula (Ia) as defined above,
- of I-(−) limonene as educt for producing the compound of formula (Ib) as defined above, or
- of a mixture containing d-(+) limonene and I-(−) limonene as educt for producing a mixture containing the compound of formula (Ia) as defined above and the compound of formula (Ib) as defined above.

The advantage of the use according to the invention of d-(+)-limonene and/or I-(−)-limonene as educt is that they are easily accessible, i.e. commercially available, low-cost educts from renewable raw materials. By the selective use of d-(+) or I-(−)-limonene, the compound of formula (Ia) or of formula (Ib) are in each case accessible selectively.
Two synthesis routes according to the invention, which in each case lead to the compound of formula (I) starting from limonene, are described below.

(i) Synthesis Route Via Epoxidation of Hydrogenated d- or 1-limonene

The educt limonene (VI) (d-(+)-limonene and/or I-(−)-limonene) is first monohydrogenated catalytically in a manner known per se to p-menth-1-ene (formula (V)). This is epoxidized with a peracid in a manner known per se. The epoxide of formula (IV) obtained is heated in the presence of aluminum isopropylate, so that ring opening to the allyl alcohol of formula (III) takes place. By reaction of the allyl alcohol of formula (III) with an alkylvinyl ether, for example butylvinyl ether in the presence of a protic acid, for example phosphoric acid, the acetal of formula (II) is produced. Then the acetal of formula (II) is reacted with catalytic amounts of acid, for example hexanoic acid in a high-boiling solvent, for example Malotherm S via the intermediate 4-isopropyl-1-methylene-2-vinyloxy-cyclohexane to the compound of formula (I) to be used according to the invention (see below, reaction scheme (i)).
The first stage of synthesis route (i) according to the invention, the selective hydrogenation of the exocyclic double bond of limonene (formula (VIa), (VIb)), has often been described in the literature. Typical reagents for this reaction are platinum(IV) oxide, as published for example in the react J. Chem. Soc., Chem. Commun. 1994, 24, 2759-2760 or W-4 Raney nickel as published in J. Org. Chem. 1982, 10, 1824-1831. However, the use of ruthenium on carbon is easier to manage than the combustible Raney nickel and is less expensive than platinum(IV) oxide.
The epoxidation of p-menth-1-ene (formula (Va), (Vb)) is carried out with peracids such as perbenzoic acid, as undertaken for example in the work Helv. Chim. Acta 1984, 67, 1248-1253, but preferably with peracetic acid in dichloromethane, chloroform or benzene by the usual methods described in the literature, e.g. in JACS 1981, 103, 1813-1821. The solvent benzene is replaced with toluene, owing to its toxicity.
The next step is selective ring opening of the epoxide of formula (IVa), (Vlb) to the allyl alcohol of formula (IIIa), (IIIb). Various products may form in this reaction, namely the desired allyl alcohol with the exocyclic double bond and the corresponding allyl alcohol with endocyclic double bond. In the literature, lithium diisopropylamide or tert-butanolate, among others, are described as base for this reaction [Roczniki Chemii Ann. Soc. Chim. Polonorum 1976, 50, 1709-1717 and Helv. Chim. Acta 1984, 67, 1249-1253]. Disadvantages in all these methods are that relatively high equivalent amounts of base have to be used, and the sometimes difficult manageability of bases such as lithium diisopropylamide and the low selectivity and/or yield. For example, using tert-butanolate in pyridine in the conditions stated in the above literature, there is formation of a mixture of product (65%), educt (28%) and an unknown byproduct (7%).
In connection with the present invention, a method was therefore to be provided in which the allyl alcohol of formula (IIIa), (IIIb) is obtainable at high selectivity and yield starting from the epoxide of formula (IVa), (IVb). It was found, unexpectedly, that this is possible if the reaction is carried out with catalytic amounts of aluminum isopropylate in xylene, similar to the production of pinocarveol in DE 31 432 27 and methylcyclododecatri-2,5,9-en-1-ol in U.S. Pat. No. 4,853,368. By heating the epoxidation product in the presence of a catalytic amount of aluminum isopropylate, selective opening of the epoxy ring is achieved by rearrangement.
The further reaction is then carried out in two steps, as explained for example in U.S. Pat. No. 3,716,498 for the production of pinoacetaldehyde. First, by reaction of the allyl alcohol of formula (IIIa), (IIIb) with an alkylvinyl ether, for example butylvinyl ether, in the presence of a protic acid, for example phosphoric acid, the acetal of formula (IIa), (IIb) is produced. Then the acetal of formula (IIa), (IIb) is reacted, with catalytic amounts of acid, for example hexanoic acid in a high-boiling solvent, for example Malotherm S, via the intermediate 4-isopropyl-1-methylene-2-vinyloxy-cyclohexane to the compound of formula (Ia), (Ib) to be used according to the invention.
Alternatively, the intermediate 4-isopropyl-1-methylene-2-vinyloxy-cyclohexane can, as is known by a person skilled in the art, be produced selectively from the allyl alcohol of formula (IIIa) or (IIIb) and acetylene.
A method preferred according to the invention for producing the compound of formula (Ia) as above and/or the compound of formula (Ib) as defined above accordingly comprises the following steps

- providing d-(+) limonene (VIa) and/or I-(−) limonene (VIb)

- as educt
- hydrogenating of educt (VIa, VIb) provided, so that starting from
  - d-(+) limonene (VIa) the compound of formula (Va) is formed,

- - I-(−) limonene (VIb) the compound of formula (Vb) is formed,

- epoxidizing the compound (Va, Vb) formed by hydrogenation of the educt (VIa, VIb), so that starting from
  - the compound of formula (Va), the epoxide of formula (IVa) is formed,

- - the compound of formula (Vb), the epoxide of formula (IVb) is formed,

- ring opening of the epoxide (IVa, IVb) formed by epoxidation of the compound (Va, Vb), so that starting from
  - the epoxide of formula (IVa), the allyl alcohol of formula (IIIIa) is formed,

- - the epoxide of formula (IVb), the allyl alcohol of formula (IIIb) is formed,

- addition of the allyl alcohol (IIIa, IIIb) formed in the ring opening of the epoxide (IVa, IVb) onto an alkylvinyl ether, preferably butylvinyl ether, so that starting from
  - the allyl alcohol of formula (IIIa), the acetal of formula (IIa) is formed,

- - the allyl alcohol of formula (IIIb), the acetal of formula (IIb) is formed,

- acid-catalyzed reaction of the acetal (IIa, IIb) formed in the addition of the allyl alcohol (IIIa, IIIb) onto an alkylvinyl ether, preferably butylvinyl ether so that starting from
  - the acetal of formula (IIa), the compound of formula (Ia) is formed,

- - the acetal of formula (IIb), the compound of formula (Ib) formed is

(ii) Synthesis Route Via Photo-Oxidation of Hydrogenated d-(+)- or I-(−)-limonene

For this synthesis route (see reaction scheme (ii) below), limonene (formula (VIa), (VIb)) is first hydrogenated as described above to p-menth-1-ene (formula (Va), (Vb)). P-Menth-1-ene (formula (Va), (Vb)) is then submitted in a solvent, e.g. methanol, in the presence of a sensitizer, e.g. Bengal pink at room temperature to photo-oxidation and the hydroperoxides that have formed (not shown in the following scheme)) are reduced with a suitable reducing agent, e.g. sodium sulfite to the corresponding isomeric allyl alcohols (formulas (IIIa), (IIIa′), (III′a′), (IIIb), (IIIb′), (IIIb′)). Then, as described above for synthesis route (i) by reaction of the allyl alcohol of formula (IIIa), (IIIb) with an alkylvinyl ether, for example butylvinyl ether in the presence of a protic acid, for example phosphoric acid, the acetal of formula (IIa), (IIb) is produced. Then the acetal of formula (IIa), (IIb) is reacted, with catalytic amounts of acid, for example hexanoic acid in a high-boiling solvent, for example Malotherm S via the intermediate 4-isopropyl-1-methylene-2-vinyloxy-cyclohexane to the compound of formula (Ia), (Ib) to be used according to the invention.
A method based on the above reaction scheme (ii) for producing the compound of formula (Ia) as defined above and/or the compound of formula (Ib) as defined above accordingly comprises the following steps:

- providing d-(+) limonene (VIa) and/or I-(−) limonene (VIb)

- - as educt
- hydrogenating the educt (VIa, VIb) provided, so that starting from
  - d-(+) limonene (VIa), the compound of formula (Va) is formed,

- - I-(−) limonene (VIb), the compound of formula (Vb) is formed,

- photo-oxidation of the compound (Va, Vb) formed by hydrogenation of the educt (VIa, VIb) and reduction of the resultant hydroperoxides, so that starting from
  - the compound (Va), the allyl alcohol (IIIa) and its isomers (IIIa′, IIIa″) are formed

- - the compound (Vb), the allyl alcohol (IIIb) and its isomers (IIIb′, IIIb″) are formed

- addition of the allyl alcohol (IIIa, 111b) formed in the photo-oxidation of the compound (Va, Vb) onto an alkylvinyl ether, preferably butylvinyl ether, so that starting from
  - the allyl alcohol of formula (IIIa), the acetal of formula (IIa) is formed,

- - the allyl alcohol of formula (IIIb), the acetal of formula (IIb) is formed,

- acid-catalyzed reaction of the acetal (IIa, IIb) formed in the addition of the allyl alcohol (IIIa, IIIb) onto an alkylvinyl ether, preferably butylvinyl ether, so that starting from
  - the acetal of formula (IIa), the compound of formula (Ia) is formed,

- - the acetal of formula (IIb), the compound of formula (Ib) is formed

- optionally separating the compound of formula (Ia) and/or of formula (Ib) from the isomers.

Owing to the need to separate the isomeric allyl alcohols of formulas (III′) and (III″) or their byproducts, formed in the photo-oxidation and subsequent reduction, this method is somewhat less preferred according to the invention.
An alternative method according to the invention for producing the compound of formula (I) as defined above comprises the step
pyrolysis of the spirolactone of formula (VIII) (8-isopropyl-1-oxaspiro[4.5]decan-2-one) with formation of the compound of formula (I)
preferably in the presence of a cerium-containing catalyst, especially cerium(III) acetate hydrate.
8-Isopropyl-1-oxaspiro[4.5]decan-2-one is obtainable by a radical reaction of 4-isopropylcyclohexanol (formula (IX)) with methyl acrylate in the presence of di-tert-butyl peroxide. 4-Isopropylcyclohexanol (formula (IX)) is in its turn obtainable by hydrogenation of 4-isopropylphenol (formula (X)):
Production of 8-isopropyl-1-oxaspiro[4.5]decan-2-one is described in EP 0 105 157. This document does not, however, disclose the pyrolysis of said spirolactones; spirolactones are the target product of the method described in EP 0 105 157.
The document WO 2004/089861 describes the pyrolysis of a spirolactone of the general formula
wherein the group R6 is a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, in the presence of a reducing agent and a catalyst. However, WO 2004/089861 discloses neither the compound of formula (VIII) nor its pyrolysis product (I). A similar method is described in the work Helv. Chim. Acta 2004, 87, 1697-1703.
A preferred method according to the invention for production of the compound of formula (I) as defined above or the compound of formula (Ia) according to the invention as defined above and/or the compound of formula (Ib) according to the invention as defined above to be used as fragrance according to the invention comprises or consists of the following steps

- (a) providing 4-isopropyl-phenol (X) as educt

- (b) hydrogenating the educt (X) provided to 4-isopropyl-hydroxycyclohexane (IX)

- (c) reacting 4-isopropyl-hydroxycyclohexane (IX) with methyl acrylate with formation of the spirolactone of formula (VIII)

- (d) pyrolysis of the spirolactone of formula (VIII) with formation of the compound of formula (I)

- (e) optionally separating the enantiomer of formula (Ia) as defined above and/or the enantiomer of formula (Ib) as defined above.

In our own investigations it was found that the use of cerium(III) acetate hydrate coated on pumice as catalyst in the pyrolysis step (d) gives the best results. A raw yield of 28% was achieved, with a racemate as product.
A method of production of the compound of formula (Ia) according to the invention as defined above and/or of the compound of formula (Ib) according to the invention as defined above comprises the following steps or consists of the following steps

- steps (a) and (b) as described above
- after step (b), separating the cis and trans isomers (IXa, IXb)

- separate reaction of the enantiomer of formula (IXa) and/or of the enantiomer of formula (IXb) corresponding to steps (c) and (d) of the method defined above to the compound of formula (Ia) or (Ib).

PRACTICAL EXAMPLES

Example 1

Synthesis of 4-isopropylcyclohexanol (IX)

An autoclave is charged with 1 kg of 4-isopropylphenol (formula (X) as defined above), 20 g of ruthenium on charcoal and 2.5 L of ethanol. The 4-isopropylphenol is hydrogenated for 6 hours at 140° C. and a hydrogen pressure of 40 bar. After filtration and removal of the solvent, 1.04 kg of crude product is obtained at a purity of 99.8% (cis/trans isomers in 1:1 ratio, quantitative yield).

Example 2

Synthesis of 8-isopropyl-4-oxaspiro[4.5]decan-3-one (VIII)

A mixture of 768 g of 4-isopropylcyclohexanol (5.40 mol, 4.50 equiv., formula (IX) as defined above) and 1.90 g of di-tert-butyl peroxide (13.0 mmol, 0.01 equiv.) is heated to 140° C. At this temperature, a mixture of 257 g of 4-isopropylcyclohexanol (1.80 mol, 1.50 equiv.) and 103 g of methyl acrylate (1.20 mol, 1.00 equiv.) is added dropwise in the space of 6 hours. The low-boiling products that form are removed. Then 6.5 g of di-tert-butyl peroxide (44.0 mmol, 0.04 equiv.) is added, and is further stirred for 2 hours at 160° C. After cooling, 150 g of 10% sodium sulfite solution is added to the reaction mixture and stirred for 1 hour at 60° C. The phases are separated, and the organic phase is washed with 100 g water. After removal of the solvent the crude product is purified by distillation. 102 g of (3R)-3-isopropyl-6-methyl-7-oxabicyclo[4.1.0]heptane is isolated at a purity of 90% (cis/trans isomers in the ratio 40:60). This corresponds to a yield of 43% of theory. The boiling point of the final product is 90° C. at 0.1 mbar.
trans-8-isopropyl-4-oxaspiro[4.5]decan-3-one: MS: m/z (%)=196 (M⁺″ 5), 181 (6), 167 (3), 153 (10), 136 (24), 123 (23), 111 (100), 98 (30), 85 (27), 67 (16), 55 (29), 43 (31), 28 (10). ¹H NMR (400 MHz, CDCl₃): (ppm)=0.87 (d, J=6.8 Hz, 6H), 1.02-1.14 (m, 1H), 1.36-1.52 (m, 5H), 1.57-1.64 (m, 2H), 1.89-1.94 (m, 2H), 1.97 (t, J=8.3 Hz, 2H), 2.58 (t, J=8.3 Hz, 2H). ¹³C NMR (100 MHz, CDCl₃): (ppm)=20.0 (2×CH₃), 26.3 (2×CH₂), 28.7 (CH₂), 30.4 (CH₂), 32.0 (CH), 36.4 (2×CH₂), 42.6 (CH), 87.3 (c_quart), 176.7 (c_quart).
cis-8-isopropyl-4-oxaspiro[4.5]decan-3-one: MS: m/z (%)=196 (M⁺″ 3), 181 (5), 167 (3), 153 (7), 136 (19), 123 (23), 111 (100), 98 (27), 85 (25), 67 (17), 55 (28), 43 (30), 28 (10). ¹H NMR (400 MHz, CDCl₃): (ppm)=0.88 (d, J=6.8 Hz, 6H), 1.02-1.14 (m, 3H), 1.36-1.52 (m, 1H), 1.68-1.82 (m, 6H), 2.06 (t, J=8.3 Hz, 2H), 2.58 (t, J=8.3 Hz, 2H). ¹³C NMR (100 MHz, CDCl₃): (ppm)=19.8 (2×CH₃), 25.4 (2×CH₂), 28.7 (CH₂), 32.5 (CH), 34.2 (CH₂), 37.2 (2×CH₂), 43.0 (CH), 85.9 (c_quart), 177.0 (c_quart).

Example 3

Synthesis of 3-(4-isopropylcyclohexen-1-yl)propanal (I) by pyrolysis of 8-isopropyl-4-oxaspirof[4.5]decan-3-one (VIII)

Preparation of the Catalyst:
450 g water is added to a mixture of 34 g cerium(III) acetate hydrate and 87 g pumice. The mixture is stirred for 1 hour at 50° C., and then the water is removed in the rotary evaporator. The pyrolysis tube is filled with 35 g of the prepared pumice (11 cm high) and heated for 1 hour at 440° C.
Pyrolysis:
A mixture of 2 g of 8-isopropyl-4-oxaspiro[4.5]decan-3-one (93%, 9.5 mmol, formula (VIII) as defined above) and 18 g of formic acid is fed into the equipment with the catalyst described above at 440° C. and in the space of 2 hours with a nitrogen flow of 16 L/h. The pyrolysis product is captured in a cold trap, then diluted with MTBE and neutralized with saturated sodium hydrogen carbonate solution. The phases are separated, and after removal of the solvent, 1.5 g of crude product is obtained at a purity of 32%. This io corresponds to a raw yield of 28%.
Evaluation:
The NMR and MS data of the product obtained correspond to the data given in example 8.

Example 4

Synthesis of (+)-p-menth-1-ene (Va) starting from d-(+)-limonene (VIa)

A mixture of 1.5 kg d-(+)-limonene (98.7% ee, formula (VIa) as defined above), 3.0 L methanol and 4.5 g Raney nickel is hydrogenated in an autoclave at room temperature under a pressure of 50 bar. After the end of the reaction, the reaction mixture is filtered and then distilled. 1.3 kg of (+)-p-menth-1-ene (formula (Va) as defined above) is isolated at a purity of 91%. This corresponds to a yield of 78% of theory.
Boiling point: 102° C./110 mbar.—MS: m/z (%)=138 (M⁺′ 32), 123 (13), 109 (5), 95 (100), 81 (23), 68 (50), 55 (19), 53 (9), 43 (7), 41 (20), 39 (10), 27 (10). ¹H NMR (200 MHz, CDCl₃): (ppm)=0.87 (d, J=6.8 Hz, 3H), 0.89 (d, J=6.8 Hz, 3H), 1.15-1.26 (m, 2H), 1.41-1.50 (m, 1H), 1.62-1.65 (m, 3H), 1.72-1.78 (m, 2H), 1.87-2.04 (m, 3H), 5.35-5.40 (m, 1H). ¹³C NMR (50 MHz, CDCl₃): (ppm)=19.7 (CH₃), 20.0 (CH₃), 23.5 (CH₃), 26.6 (CH₂), 29.0 (CH₂), 30.9 (CH₂), 32.4 (CH), 40.1 (CH), 121.1 (CH), 133.8 (c_quart).

Example 5

Synthesis of (3R)-3-isopropyl-6-methyl-7-oxabicyclof[4.1.0]heptane (IVa)

238 g of peracetic acid (40%, 1.25 mol, 1.25 equiv.) is added dropwise to a mixture of 152 g (+)-p-menth-1-ene (91%, 1.00 mol, 1.00 equiv., formula (Va) as defined above) and 53.0 g sodium carbonate (0.50 mol, 0.50 equiv.) in 500 mL toluene at 0° C. Then the reaction mixture is heated to room temperature and stirred for 3 hours. Water is added to the reaction mixture, the organic phase is separated and stirred with a 20% solution of sodium sulfite for 2 hours at 60° C. Then the phases are separated again and the organic phase is washed twice with water. After removal of the solvent, the crude product is purified by distillation. 133 g of (3R)-3-isopropyl-6-methyl-7-oxabicyclo[4.1.0]heptane (formula (IVa) as defined above) is isolated at a purity of 96% (cis/trans isomers in the ratio approx. 1:1). This corresponds to a yield of 83% of theory. The boiling point of the final product is 102° C. at 40 mbar.
(1R, 3R, 6S)-3-Isopropyl-6-methyl-7-oxabicyclo[4.1.0]heptane: MS: m/z (%)=154 (M⁺″ 2), 139 (20), 125 (14), 111 (62), 95 (17), 83 (25), 69 (47), 55 (49), 43 (100), 27 (14). ¹H NMR (400 MHz, CDCl₃): δ (ppm)=0.83 (d, J=6.8 Hz, 6H), 0.92-1.07 (m, 1H), 1.11 (dd, J=12.4, 4.1 Hz, 1H), 1.30 (s, 3H), 1.31-1.47 (m, 3H), 1.62 (ddd, J=14.5, 12.2, 4.9 Hz, 1H), 1.95 (dddd, J=15.2, 6.0, 5.5, 2.0 Hz, 1H), 1.93 (ddd, J=14.6, 3.8, 2.4 Hz, 1H), 2.97 (d, J=5.3 Hz, 1H).—¹³C NMR (100 MHz, CDCl₃): δ (ppm)=19.4 (CH₃), 19.7 (CH₃), 22.5 (CH₂), 23.1 (CH₃), 27.9 (CH₂), 31.0 (CH₂), 32.3 (CH), 39.3 (CH), 57.8 (c_quart), 59.7 (CH).
(1S, 3R, 6R)-3-Isopropyl-6-methyl-7-oxabicyclo[4.1.0]heptane: MS: m/z (%)=154 (M⁺″ 2), 139 (18), 125 (14), 111 (57), 93 (18), 83 (29), 69 (47), 55 (54), 43 (100), 27 (15).—¹H NMR (400 MHz, CDCl₃): δ (ppm)=0.84 (d, J=6.7 Hz, 3H), 0.85 (d, J=6.7 Hz, 3H), 0.89-0.96 (m, 1H), 1.30 (s, 3H), 1.20-1.28 (m, 1H), 1.31-1.47 (m, 3H), 1.79-1.85 (m, 2H), 2.08 (ddd, J=14.6, 4.3, 2.0 Hz, 1H), 3.02 (t, J=2.1 Hz, 1H).—¹³C NMR (100 MHz, CDCl₃): δ (ppm)=19.7 (2×CH₃), 24.5 (CH₃), 24.9 (CH₂), 29.2 (CH₂), 29.3 (CH₃), 31.7 (CH), 35.1 (CH), 37.6 (c_quart), 61.0 (CH).

Example 6

Synthesis of (5R)-5-isopropyl-2-methylene cyclohexanol (IIIa)

49.0 g of aluminum isopropylate (0.24 mol, 0.10 equiv.) is carefully added dropwise to a mixture of 401 g of (3R)-3-isopropyl-6-methyl-7-oxabicyclo[4.1.0]heptane (96%, 2.48 mol, 1.00 equiv., formula (IVa) as defined above) in 1.4 L xylene. Then the reaction mixture is boiled under reflux for 4 hours. The reaction mixture is cooled to room temperature, 10% hydrochloric acid solution is added and the phases are separated. The aqueous phase is extracted with xylene and the combined organic phases are washed with water. The crude product is purified by distillation. 327 g of (5R)-5-isopropyl-2-methylene cyclohexanol (formula (IIIa) as defined above) is isolated at a purity of 71% (contains 62 g of (5R)-5-isopropyl-2-methylcyclohex-2-en-1-ol). This corresponds to a yield of 60% of theory. The boiling point of the final product is 75° C. at 25 mbar.
(1 R, 5R)-5-Isopropyl-2-methylene cyclohexanol: MS: m/z (%)=154 (M⁺″ 14), 139 (7), 121 (13), 111 (51), 97 (18), 93 (48), 82 (60), 69 (63), 55 (100), 53 (20), 41 (83), 27 (27).—¹H NMR (400 MHz, CDCl₃): δ (ppm)=0.88 (2d, J=6.8 Hz, 6H), 0.96-1.07 (m, 2H), 1.33-1.42 (m, 1H), 1.46-1.54 (m, 1H), 1.71-1.78 (m, 1H), 1.93-2.03 (m, 1H), 2.11 (dddd, J=11.8, 5.2, 2.9, 2.2 Hz, 1H), 2.42 (ddd, J=13.5, 4.2, 2.6 Hz, 1H), 4.01-4.09 (m, 1H), 4.75 (q, J=1.8 Hz, 1H), 4.91 (dd, J=1.8, 1.5 Hz, 1H).—¹³C NMR (100 MHz, CDCl₃): δ (ppm)=19.7 (CH₃), 19.9 (CH₃), 30.7 (CH₂), 32.3 (CH), 33.8 (CH₂), 40.5 (CH₂), 42.9 (CH), 72.5 (CH), 103.3 (CH₂), 152.0 (c_quart).
(1S, 5R)-5-Isopropyl-2-methylene cyclohexanol: MS: m/z (%)=154 (M⁺″ 9), 136 (7), 125 (4), 121 (18), 111 (56), 97 (18), 93 (72), 83 (61), 77 (30), 67 (64), 55 (100), 53 (23), 41 (91), 27 (39).—¹H NMR (400 MHz, CDCl₃): δ (ppm)=0.87 (d, J=6.8 Hz, 3H), 0.88 (d, J=6.8 Hz, 3H), 1.09 (tdd, J=12.7, 11.5, 4.1 Hz, 1H), 1.34 (ddd, J=13.6, 12.1, 3.1 Hz, 1H), 1.42-1.51 (m, 1H), 1.64-1.74 (m, 1H), 1.75-1.81 (m, 1H), 1.90 (ddd, J=13.6, 3.5, 2.3 Hz, 1H), 2.18 (ddd, J=13.5, 4.0, 3.5 Hz, 1H), 2.36-2.45 (m, 1H), 4.33 (t, J=3.4 Hz, 1H), 4.74 (dd, J=2.0, 0.6 Hz, 1H), 4.82 (dd, J=2.1, 1.5 Hz, 1H).—¹³C NMR (100 MHz, CDCl₃): δ (ppm)=19.7 (CH₃), 19.9 (CH₃), 30.0 (CH₂), 30.5 (CH₂), 31.9 (CH), 36.9 (CH), 37.5 (CH₂), 72.6 (CH), 109.2 (CH₂), 150.6 (c_quart).

Example 7

(4R)-2-(1-Butoxyethoxy)-4-isopropyl-1-methylene cyclohexane (IIa)

317 mg of p-toluene sulfonic acid monohydrate (1.70 mmol, 0.6 mol %.) is added in portions to a mixture of 42.9 g of (5R)-5-isopropyl-2-methylene cyclohexanol (70%, 195 mmol, 1.00 equiv., formula (IIIa) as defined above)) and 55.7 g of butylvinyl ether (556 mmol, 2.90 equiv.) at 0° C. The reaction is exothermic and the heat released is removed by means of an ice bath at 17° C. Then it is stirred for 2 hours at 0 to 10° C. MTBE is added to the reaction mixture, and it is washed three times with 5% Na₂CO₃solution and once with water. The organic phase is then separated and distilled over Na₂CO₃. 58.4 g of (4R)-2-(1-butoxyethoxy)-4-isopropyl-1-methylene cyclohexane is isolated at a purity of 71% (4 isomers in the proportions approx. 1:1:1.5:1.3). This io corresponds to a yield of 83% of theory.
MS: m/z (%)=137 (23), 101 (78), 81 (32), 67 (8), 57 (52), 45 (100), 41 (24), 29 (13).

Example 8

Synthesis of 3-[(4R)-4-isopropylcyclohexen-1-yl)propanal (Ia)

A mixture of 24 g of (4R)-2-(1-butoxyethoxy)-4-isopropyl-1-methylene cyclohexane (77%, 72 mmol, 1.00 equiv., formula (IIa) as defined above) and 2.5 g hexanoic acid (21 mmol, 0.30 equiv.) in 25 g Malotherm S is heated at 200° C. for 2 hours. During this, the low-boiling products are distilled off. Then the reaction mixture is cooled at room temperature and distilled over soda. 14.7 g of 3-[(4R)-4-isopropylcyclohexen-1-yl]-propanal (formula (Ia) as defined above) is isolated at a purity of 52% and with 96.6% ee. This corresponds to a yield of 58% of theory. Some of the product is purified on a column (cyclohexane: ethyl acetate 100:3, 3.34 g, purity 96.5%).
[α]_D ²²=+108° (c=0.07 in ethanol).—GC with chiral stationary phase (Hydrodex-b-TBADc, 25 m×0.25 mm, 40° C.−1° C./min.−180° C.): R_t=79.08 (98.3%), 79.30 (1.7%).—MS: m/z (%)=180 (M⁺″ 10), 162 (7), 147 (7), 136 (34), 119 (24), 109 (18), 93 (100), 79 (41), 67 (56), 55 (34), 41 (69), 27 (33).—¹H NMR (400 MHz, CDCl₃): δ (ppm)=0.87 (d, J=6.8 Hz, 3H), 0.88 (d, J=0.88 Hz, 3H), 1.16-1.28 (m, 2H), 1.42-1.50 (m, 1H), 1.66-1.80 (m, 2H), 1.94-2.06 (m, 3H), 2.28 (t, J=7.5 Hz, 2H), 2.49-2.54 (m, 2H), 5.39-5.43 (m, 1H), 9.75 (t, J=1.9 Hz, 1H).—¹³C NMR (100 MHz, CDCl₃): δ (ppm)=19.6 (CH₃), 19.9 (CH₃), 26.3 (CH₂), 28.8 (CH₂), 29.2 (CH₂), 29.7 (CH₂), 32.2 (CH), 40.0 (CH), 41.9 (CH₂), 121.8 (CH), 135.5 (c_quart), 202.8 (CHO).

Example 9

Fine Fragrance (Perfume Oil)


	Parts by weight

		Perfume
		oil A2
		(according
	Perfume oil A1	to the
Fragrances	(comparison)	invention)

ETHYL ACETOACETATE	4.0	4.0
HEXENOL CIS-3 10% DPG	3.0	3.0
HEXENYL ACETATE CIS-3 10% DPG	3.0	3.0
HEXENYL BENZOATE CIS-3 10% DPG	3.0	3.0
VERTOCITRAL 10% DPG	5.0	5.0
CYCLOGALBANAT ® 10% DPG	3.0	3.0
STYRALYL ACETATE 10% DPG	6.0	6.0
BERGAMOT OIL BERGAPTEN FREE FF	6.0	6.0
MANDARY OIL DIST. DECOL.	15.0	15.0
METHYL ANTHRANILATE 10% DPG	5.0	5.0
RED BERRY EXTR.	2.0	2.0
DECALACTONE GAMMA	2.0	2.0
ALLYL CAPROATE 10% DPG	5.0	5.0
PRUNELLA TYPE BASE	6.0	6.0
HELIONAL	20.0	20.0
MUGETANOL	10.0	10.0
ETHYL LINALOOL	35.0	35.0
CITRONELLOL 950	10.0	10.0
GERANIOL SUPER	3.0	3.0
ROSAPHEN ®	8.0	8.0
CITRONELLYL ACETATE EXTRA	2.0	2.0
DAMASCONE BETA 10% DPG	6.0	6.0
BENZYL ACETATE	10.0	10.0
HEDION HC/30	30.0	30.0
HEDIONE	140.0	140.0
HEXYL CINNAMIC ALDEHYDE ALPHA	30.0	30.0
LACTOJASMONE	3.0	3.0
BENZYL SALICYLATE	80.0	80.0
HEXENYL SALICYLATE CIS-3	30.0	30.0
METHYL IONONE GAMMA COEUR	3.0	3.0
CLOVE BUD OIL	1.0	1.0
VANILLIN	1.5	1.5
COUMARIN	1.0	1.0
AMBERWOOD ® F	5.0	5.0
CASHMERAN	8.0	8.0
CEDRENE	15.0	15.0
ISO E SUPER NON DISCOLORING	50.0	50.0
BRAHMANOL ®	25.0	25.0
SANDALORE	5.0	5.0
AMBROXIDE	2.0	2.0
AMBRETTOLIDE	5.0	5.0
AURELIONE ®	16.0	16.0
GLOBALIDE ®	24.0	24.0
MACROLIDE ® SUPRA	16.0	16.0
INDOLE FF 10% DPG	5.0	5.0
3-[(4R)-4-Isopropylcyclohexen-1-yl]propanal		50.0
DIPROPYLENE GLYCOL	332.5	282.5
	1000.0	1000.0

At a dosage of 6 wt % of perfume oil A1 or A2 in ethanol, the findings are as follows: By adding 3-[(4R)-4-isopropylcyclohexen-1-yl]propanal in perfume oil A2 the floral note is intensified relative to perfume oil A1 (without 3-[(4R)-4-isopropylcyclohexen-1-yl]propanal). Furthermore, 3-[(4R)-4-isopropylcyclohexen-1-yl]propanal endows the composition with perfume oil A2 more power and fullness than the composition with perfume oil A1; on the whole, addition of 3-[(4R)-4-isopropylcyclohexen-1-yl]propanal results in an odor impression reminiscent of lily of the valley.

Example 10

Body Lotion


Component	wt %	wt %

Paraffin oil	5.00	5.00
Isopropyl palmitate	5.00	5.00
Cetyl alcohol	2.00	2.00
Beeswax	2.00	2.00
Ceteareth-20	2.00	2.00
PEG-20-glyceryl stearate	1.50	1.50
Glycerol	3.00	3.00
Phenoxyethanol	0.50	—
Parabens (mixture of methyl, ethyl, propyl, butyl,	—	0.50
isobutyl paraben)
Perfume oil B1 or B2	0.50	0.50
Water	to 100	to 100

Composition of the perfume oil B1 or B2:


	Parts by weight

		Perfume oil
		B2
	Perfume oil	(according
	B1	to the
Fragrances	(comparison)	invention)

NONADIENAL TRANS, CIS-2.6 5% TEC	2.0	2.0
20% DPG
ETHYL ACETOACETATE	3.0	3.0
FARENAL ® 10% DPG	5.0	5.0
VERTOCITRAL	3.0	3.0
CYCLOGALBANAT ® 10% DPG	2.0	2.0
STYRALYL ACETATE	3.0	3.0
MELONAL ®	0.5	0.5
DIHYDROMYRCENOL	15.0	15.0
LINALYL ACETATE	20.0	20.0
LEMON OIL TERPENE FLAVOR WONF	8.0	8.0
EUCALYPTOL NATURAL. 10% DPG	0.5	0.5
HEXYL ACETATE	1.5	1.5
ISOAMYL ACETATE 10% DPG	4.0	4.0
PRENYL ACETATE 10% DPG	4.0	4.0
ALDEHYDE C14 SO-CALLED	2.0	2.0
ETHYL METHYL BUTYRATE-2	1.0	1.0
ALLYL CYCLOHEXYL PROPIONATE	2.0	2.0
ALDEHYDE C16 SO-CALLED	1.0	1.0
FRAGOLANE ®	0.5	0.5
MAJANTOL ®	25.0	25.0
LINALOOL	40.0	40.0
DIMETHYL BENZYL CARBINOL	10.0	10.0
TERPINEOL PURE	10.0	10.0
PHENIRAT ®	30.0	30.0
CITRONELLOL 950	15.0	15.0
GERANIOL 60	10.0	10.0
CITRONELLYL ACETATE EXTRA	2.0	2.0
HEDIONE	90.0	90.0
HEXYL CINNAMIC ALDEHYDE ALPHA	35.0	35.0
HEXYL SALICYLATE	160.0	160.0
METHYL OCTIN CARBONATE 10% DPG	2.0	2.0
CALONE 1951 10% DPG	1.0	1.0
GALAXOLIDE 50% IN IPM	20.0	20.0
ANETHOLE SUPRA 21.5 CELSIUS	2.0	2.0
AGRUMEX HC	15.0	15.0
ORYCLON SPECIAL	40.0	40.0
3-[(4R)-4-Isopropylcyclohexen-1-yl]propanal		15.0
DIPROPYLENE GLYCOL	415.0	400.0
	1000.0	1000.0

At a dosage of 0.5 wt % of perfume oil B1 or B2 in the body lotion, the findings are as follows: due to the proportion of 3-[(4R)-4-isopropylcyclohexen-1-yl]propanal, the body lotion containing perfume oil B2 has a stronger and more natural floral note than the body lotion that contains perfume oil B1 (without 3-[(4R)-4-isopropylcyclohexen-1-yl] propanal). Furthermore, the body lotion with perfume oil B2 displays a more cosmetic top note and a creamier bottom note than the body lotion with perfume oil B1; on the whole, addition of 3-[(4R)-4-isopropylcyclohexen-1-yl]propanal results in an odor impression reminiscent of lily of the valley.

Example 11

Fabric Softener


Material	Manufacturer	Chemical name	Function	wt %

Deionized water		Water	Solvent	72.4
Rewoquat WE 18	Evonik	Dialkylesterammonium	Cationic	16.6
	Goldschmidt	ethosulfate	surfactant
	GmbH
Mergal K9N	Honeywell	5-Chloro-2-methyl-3-	Preservative	0.10
	Austria GmbH	(2H)-isothiazolone and
		2-methyl-3-(2H)-
		isothiazolone
Dow Corning 1520	Dow Corning	Polydimethylsiloxane	Antifoaming	0.30
Antifoam	GmbH,		agent
Magnesium chloride		Magnesium chloride	Consistency	10.00
1% solution		solution	agent
Perfume Oil C1 or C2	Symrise		Perfume	0.60
			(fragrance)

Composition of perfume oil C1 or C2:


	Parts by weight

		Perfume oil
		C2
	Perfume oil	(according
	C1	to the
Fragrances	(comparison)	invention)

ALDEHYDE C10	0.5	0.5
ALDEHYDE C11 ISO	2.0	2.0
ALDEHYDE C11 UNDECYLENIC	12.0	12.0
ALDEHYDE C12 MNA	6.0	6.0
FARENAL ®	1.0	1.0
VERTOCITRAL	8.0	8.0
ALLYL AMYL GLYCOLATE	1.0	1.0
STYRALYL ACETATE	1.5	1.5
DIHYDROMYRCENOL	65.0	65.0
AGRUNITRIL	1.0	1.0
PEONILE	15.0	15.0
METHYL ANTHRANILATE	10.0	10.0
NEROLIONE 10% DPG	1.5	1.5
ROSEMARY OIL BM	7.0	7.0
SAGE OFFICINALE OIL DALM.	3.0	3.0
ISOBORNYL ACETATE	40.0	40.0
PRENYL ACETATE	0.5	0.5
ISOAMYL BUTYRATE E	0.5	0.5
ALDEHYDE C14 SO-CALLED	5.0	5.0
MANZANATE	0.5	0.5
MUGETANOL	5.0	5.0
DIMETHYL BENZYL CARBINYL	2.5	2.5
ACETATE
ROSE OXIDE D	3.0	3.0
ANTHER	0.5	0.5
PHENYLETHYL ALCOHOL	35.0	35.0
CITRONELLOL 950	15.0	15.0
GERANIOL 60	10.0	10.0
ISODAMASCON ®	2.0	2.0
ROSACETATE	35.0	35.0
CRESYL METHYL ETHER PARA	0.5	0.5
BENZYL ACETATE	20.0	20.0
HEXYL CINNAMIC ALDEHYDE ALPHA	40.0	40.0
METHYL BENZOATE	1.0	1.0
AMYL SALICYLATE N/ISO	10.0	10.0
BENZYL SALICYLATE	70.0	70.0
MYSORE ACETATE	15.0	15.0
PARMANYL ®	0.5	0.5
EUGENOL	10.0	10.0
ETHYL VANILLIN	0.5	0.5
COUMARIN	3.0	3.0
AGRUMEX HC	45.0	45.0
HERBAFLORAT	25.0	25.0
AMBERWOOD ® F	5.0	5.0
ISO E SUPER	170.0	170.0
PATCHOULI OIL DECOL.	2.5	2.5
SANDRANOL ®	10.0	10.0
ISOBUTYL QUINOLINE	1.0	1.0
EVERNYL	0.5	0.5
AMBROXIDE	1.0	1.0
GALAXOLIDE 50% IN IPM	120.0	120.0
INDOFLOR ® CRYST.	0.5	0.5
3-[(4R)-4-Isopropylcyclohexen-1-yl]propanal		60.0
DIPROPYLENE GLYCOL	220.0	160.0
	1000.0	1000.0

At a dosage of 0.6 wt % of perfume oil C1 or C2 in the fabric softener, the findings are as follows: due to the proportion of 3-[(4R)-4-isopropylcyclohexen-1-yl]propanal, the fabric softener containing perfume oil C2 has a more natural, fresher floral note than the fabric softener that contains perfume oil C1 (without 3-[(4R)-4-isopropylcyclohexen-1-yl] propanal); on the whole, addition of 3-[(4R)-4-isopropylcyclohexen-1-yl]propanal results in an odor impression reminiscent of lily of the valley.

Example 12

Soap


Material	Manufacturer	Chemical name	Function	wt %

Deionized water		Water	Solvent	2.0
Soap Base Mix	Various	Sodium	Surfactants	95.8
		tallowates/
		palmitates
Titanium dioxide	Kronos Titan	Titanium	Pigment/	1.0
	GmbH,	dioxide	Lightening
	Germany		agent
Perfume oil D1	Symrise		Perfume	1.2
or D2			(fragrance)

Composition of perfume oil D1 or D2:


	Parts by weight

		Perfume oil
		D2
	Perfume oil	(according
	D1	to the
Fragrances	(comparison)	invention)

ALDEHYDE C 8	10.0	10.0
ALDEHYDE C10	14.0	14.0
ALDEHYDE C11 UNDECYLIC	5.0	5.0
ALDEHYDE C12 MNA	4.0	4.0
ISOAMYL ALCOHOL	6.0	6.0
VERTOCITRAL	4.0	4.0
ALLYL AMYL GLYCOLATE	4.0	4.0
DIHYDROMYRCENOL	120.0	120.0
CITRAL 95	30.0	30.0
AGRUNITRIL	80.0	80.0
CITRONITRILE	40.0	40.0
CITRYLAL	4.0	4.0
ORANGE OIL TERPENES	250.0	250.0
METHYL ANTHRANILATE	1.5	1.5
TERPINEOL HEAD FRACTION	10.0	10.0
EUCALYPTOL NAT.	10.0	10.0
THYMOL CRYST	6.0	6.0
BORNYL ACETATE L CRYST.	82.5	82.5
CAMPHOR DL	20.0	20.0
JASMAPRUNAT	5.0	5.0
ALDEHYDE C14 SO-CALLED	2.0	2.0
MANZANATE	0.5	0.5
ALLYL HEPTOATE	2.5	2.5
ROSE OXIDE L	0.5	0.5
DAMASCONE ALPHA	0.5	0.5
HEDIONE	10.0	10.0
AMYL SALICYLATE N/ISO	60.0	60.0
HEXYL SALICYLATE	35.0	35.0
COUMARIN	2.5	2.5
AGRUMEX HC	30.0	30.0
ORYCLON SPECIAL	55.0	55.0
PATCHOULI OIL DECOL.	2.0	2.0
SANDRANOL ®	1.5	1.5
TONALIDE	2.0	2.0
3-[(4R)-4-Isopropylcyclohexen-1-yl]propanal		40.0
DIPROPYLENE GLYCOL	130.0	90.0
	1000.0	1000.0

At a dosage of 1.2 wt % of perfume oil D1 or D2 in the soap, the findings are as follows: due to the proportion of 3-[(4R)-4-isopropylcyclohexen-1-yl]propanal, the soap containing perfume oil D2 has a round, aldehyde note, in contrast to the soap that contains perfume oil D1 (without 3-[(4R)-4-isopropylcyclohexen-1-yl] propanal). Furthermore, the soap with perfume oil D2 radiates more naturalness and fullness than the soap with perfume oil D1; on the whole, addition of 3-[(4R)-4-isopropylcyclohexen-1-yl]propanal results in an odor impression reminiscent of lily of the valley.

Example 13

Washing Powder


Material	Manufacturer	Chemical name	Function	wt %

Sodium metasilicate	Akzo Nobel	Sodium metasilicate		48.0
pentahydrate	Chemicals,	pentahydrate
	Germany
Sodium hydrogen	Various	Sodium hydrogen	Alkali	15.0
carbonate		carbonate
Sodium percarbonate	Various	Sodium carbonate	Bleach	15.0
		peroxyhydrate
Peractive AC blue	Clariant	TAED/Na-carboxy-	Activator	5.00
	GmbH,	methylcellulose
	Germany
Genapol OA-080	Clariant	Oxoalcohol C14-15,	Non-ionic	3.00
	GmbH,	8EO	surfactant
	Germany
Texapon K12 powder	Cognis	Sodium lauryl sulfate	Anionic	7.00
	Germany	C12	surfactant
	GmbH
Tinopal CBS-X	Ciba,		Brightener	0.50
	Germany
Savinase 6.0 T, Type W	Novozymes	Protease	Enzyme	0.40
Termamyl 120 T	Novozymes	Alpha-amylase	Enzyme	0.30
Sodium sulfate	Various	Sodium sulfate	Filler	5.50
Perfume oil E1 or E2	Symrise		Perfume	0.30
			(fragrance)

Composition of perfume oil E1 or E2:


	Parts by weight

		Perfume oil
		E2
	Perfume oil	(according
	E1	to the
Fragrances	(comparison)	invention)

ALDEHYDE C 8	0.5	0.5
HEXENOL CIS-3	3.5	3.5
VERTOCITRAL	15.0	15.0
STYRALYL ACETATE	3.0	3.0
MELONAL ®	2.0	2.0
DIHYDROMYRCENOL	60.0	60.0
CITRAL 95	6.0	6.0
ORANGE OIL TERPENES	20.0	20.0
EUCALYPTUS OIL GLOBULUS 80/85%	10.0	10.0
MENTHONE L/ISOMENTHONE D 82/18	1.5	1.5
HEXYL ACETATE 10% DPG	5.0	5.0
ISOPENTYRATE	4.0	4.0
ETHYL CAPROATE	1.0	1.0
ETHYL METHYL BUTYRATE-2	6.0	6.0
LINALOOL	10.0	10.0
DIMETHYL BENZYL CARBINYL	15.0	15.0
BUTYRATE
PHENYLETHYL ALCOHOL	15.0	15.0
CITRONELLOL 950	20.0	20.0
GERANIOL 60	20.0	20.0
ISODAMASCON ®	10.0	10.0
CRESYL METHYL ETHER PARA	1.0	1.0
BENZYL ACETONE	50.0	50.0
HEXYL CINNAMIC ALDEHYDE ALPHA	60.0	60.0
DIHYDROJASMONE	1.0	1.0
METHYL BENZOATE	0.5	0.5
HEXYL SALICYLATE	10.0	10.0
LEGUMINAL	6.0	6.0
IONONE BETA	20.0	20.0
ISORALDEINE 70	45.0	45.0
EUGENOL	2.0	2.0
ACETOPHENONE 1% DPG	5.0	5.0
AGRUMEX HC	60.0	60.0
ORYCLON SPECIAL	40.0	40.0
HERBAFLORAT	10.0	10.0
HERBYL PROPIONATE	20.0	20.0
KOAVONE	20.0	20.0
VERTOFIX	40.0	40.0
ISO E SUPER	150.0	150.0
SANDRANOL ®	20.0	20.0
AMBROXIDE	2.0	2.0
3-[(4R)-4-Isopropylcyclohexen-1-yl]propanal		60.0
DIPROPYLENE GLYCOL	270.0	210.0
	1000.0	1000.0

At a dosage of 0.3 wt % of perfume oil E1 or E2 in the washing powder (powder detergent), the findings are as follows: the proportion of 3-[(4R)-4-isopropylcyclohexen-1-yl]propanal produces, in the washing powder containing perfume oil E2, an intensification of the green notes relative to the washing powder that contains perfume oil E1 (without 3-[(4R)-4-isopropylcyclohexen-1-yl]propanal). Furthermore, the composition of the washing powder with perfume oil E2 radiates altogether more freshness than the washing powder with perfume oil E1; on the whole, addition of 3-[(4R)-4-isopropylcyclohexen-1-yl]propanal results in an odor impression reminiscent of lily of the valley.

Example 14

General-Purpose Cleaner


Material	Manufacturer	Chemical name	Function	wt %

Deionized water		Water	Solvent	59.6
Mergal K9N	Troy Chemie,	5-Chloro-2-methyl-3-(2H)-	Preservative	0.1
	Seelze	isothiazolone and 2-methyl-
		3-(2H)-isothiazolone
Trisodium citrate	Various	Trisodium citrate dihydrate	Complexing	3.0
dihydrate			agent
Zetesol NL-2	Zschimmer &	Fatty alcohol C12-14-	Anionic	30.0
	Schwarz,	sulfate, sodium	surfactant
	Germany
Imbentin C/125/055	Dr. W. Kolb	Fatty alcohol C12-C15, 8EO	Non-ionic	5.0
	AG chem.		surfactant
Ethanol 96%	Various	Ethanol	Solvent	2.0
Perfume oil F1 or	Symrise		Perfume	0.3
F2			(fragrance)

Composition of perfume oil F1 or F2:


	Parts by weight

		Perfume oil
		F2
	Perfume oil	(according
	F1	to the
Fragrances	(comparison)	invention)

ALDEHYDE C10	0.5	0.5
ALCOHOL C10	6.0	6.0
HEXENOL CIS-3	1.0	1.0
LIMONENAL	4.0	4.0
VERTOCITRAL	8.0	8.0
PHENYLACETALDEHYDE 50% DPG	1.0	1.0
MINTONAT	15.5	15.5
METHYL ANTHRANILATE	1.0	1.0
HEXYL ACETATE	20.0	20.0
ALLYL HEPTOATE	1.0	1.0
LINALOOL	30.0	30.0
DIMETHYL BENZYL CARBINYL	2.0	2.0
ACETATE
PHENYLETHYL ALCOHOL	150.0	150.0
CITRONELLOL 950	130.0	130.0
GERANIOL SUPER	35.0	35.0
GERANYL ACETATE PURE	10.0	10.0
BENZYL ACETATE	55.0	55.0
HEDIONE	15.0	15.0
HEXYL CINNAMIC ALDEHYDE ALPHA	130.0	130.0
CINNAMIC ALCOHOL	6.0	6.0
ACETOPHENONE 10% DPG	1.0	1.0
JACINTHAFLOR ®	4.0	4.0
ISO E SUPER	20.0	20.0
GALAXOLIDE 50% IN IPM	35.0	35.0
INDOFLOR ® CRYST.	1.0	1.0
BHT IONOL	8.0	8.0
3-[(4R)-4-Isopropylcyclohexen-1-yl]propanal		60.0
DIPROPYLENE GLYCOL	370.0	310.0
	1000.0	1000.0

At a dosage of 0.3 wt % of perfume oil F1 or F2 in the general-purpose cleaner, the findings are as follows: the proportion of 3-[(4R)-4-isopropylcyclohexen-1-yl]propanal produces, in the general-purpose cleaner containing perfume oil F2, an intensification of the floral note relative to the general-purpose cleaner that contains perfume oil F1 (without 3-[(4R)-4-isopropylcyclohexen-1-yl]propanal). Moreover, the composition of the general-purpose cleaner with perfume oil F2 seems much creamier and fresher than that of the general-purpose cleaner with perfume oil F1; on the whole, addition of 3-[(4R)-4-isopropylcyclohexen-1-yl]propanal results in an odor impression reminiscent of lily of the valley.

Example 15

Shampoo


Material	Manufacturer	INCI Name	wt %

Deionized water		Water	71.5
Plantacare PS 10	Cognis Germany	Sodium Laureth Sulfate,	20.0
	GmbH	Lauryl Glucoside
Euperlan PK 771	Cognis Germany	Glycol Distearate, Sodium	6.0
	GmbH	Lauryl Sulfate, Cocamide
		MEA, Laureth-10
Dragocid Liquid	Symrise	Phenoxyethanol,	0.5
		Methylparaben,
		Ethylparaben,
		Butylparaben,
		Propylparaben,
		Isobutylparaben
Sodium chloride		Sodium Chloride	1.4
Citric acid		Citric Acid	0.1
monohydrate
crystalline
Perfume oil G1	Symrise	Perfume (Fragrance)	0.5
or G2

Composition of perfume oil G1 or G2:


	Parts by weight

		Perfume oil
		G2
	Perfume oil	(according
	G1	to the
Fragrances	(comparison)	invention)

FARENAL ®	3.0	3.0
FLORAZON	0.5	0.5
HEXENYL ACETATE CIS-3	3.0	3.0
VERTOCITRAL	1.0	1.0
DYNASCONE 10% DPG	2.0	2.0
CYCLOGALBANAT ®	2.0	2.0
STYRALYL ACETATE	1.5	1.5
DIHYDROMYRCENOL	6.0	6.0
OXANTHIA 50% IN TEC 10% DPG	10.0	10.0
LEMON OIL ITAL.	10.0	10.0
ORANGE OIL BRASIL	50.0	50.0
HEXYL ACETATE	2.0	2.0
ISOAMYL ACETATE	0.5	0.5
PRENYL ACETATE	0.5	0.5
ETHYL BUTYRATE 10% DPG	2.0	2.0
ALDEHYDE C14 SO-CALLED	25.0	25.0
DECALACTONE GAMMA	5.0	5.0
ETHYL METHYL BUTYRATE-2	1.0	1.0
ALLYL CAPROATE	1.5	1.5
ALLYL CYCLOHEXYL PROPIONATE	3.0	3.0
ALLYL HEPTOATE	2.5	2.5
MELOZONE	2.0	2.0
CALONE 1951	0.5	0.5
MUGETANOL	10.0	10.0
LINALOOL	25.0	25.0
DIMETHYL BENZYL CARBINYL	6.0	6.0
ACETATE
DIMETHYL BENZYL CARBINYL	4.0	4.0
BUTYRATE
PHENYLETHYL ACETATE	1.5	1.5
PHENYLETHYL ALCOHOL	15.0	15.0
CITRONELLOL 950	10.0	10.0
GERANIOL SUPER	5.0	5.0
GERANYL ACETATE PURE	15.0	15.0
ISODAMASCON ®	2.0	2.0
BENZYL ACETATE	15.0	15.0
HEDIONE	90.0	90.0
HEXYL CINNAMIC ALDEHYDE ALPHA	35.0	35.0
JASMONE CIS	0.5	0.5
BENZYL SALICYLATE	80.0	80.0
HEXENYL SALICYLATE CIS-3	30.0	30.0
ISORALDEINE 70	35.0	35.0
HERBAFLORAT	15.0	15.0
ISO E SUPER	15.0	15.0
ISOBORNYL CYCLOHEXANOL	30.0	30.0
BRAHMANOL ®	10.0	10.0
AMBROXIDE	1.5	1.5
GLOBALIDE ®	5.0	5.0
GALAXOLIDE 50% IN DPG	120.0	120.0
3-[(4R)-4-Isopropylcyclohexen-1-yl]propanal		65.0
DIPROPYLENE GLYCOL	290.0	225.0
	1000.0	1000.0

At a dosage of 0.5 wt % of perfume oil G1 or G2 in the shampoo, the findings are as follows: addition of 3-[(4R)-4-isopropylcyclohexen-1-yl]propanal intensifies, in the shampoo containing perfume oil G2, the watery-fruity character relative to the shampoo that contains perfume oil G1 (without 3-[(4R)-4-isopropylcyclohexen-1-yl]propanal). Moreover, in the shampoo with perfume oil G2, the diffusivity is increased relative to the shampoo with perfume oil G1; on the whole, addition of 3-[(4R)-4-isopropylcyclohexen-1-yl]propanal results in an odor impression reminiscent of lily of the valley.
Example 16

Shower Gel


Material	Manufacturer	INCI Name	wt %

Deionized water		Water	76.3
Plantacare PS 10	Cognis	Sodium Laureth Sulfate,	20.0
	Germany	Lauryl Glucoside
	GmbH
Dragocid liquid	Symrise	Phenoxyethanol,	0.5
		Methylparaben,
		Ethylparaben,
		Butylparaben,
		Propylparaben,
		Isobutylparaben
Sodium chloride		Sodium Chloride	1.4
Citric acid		Citric Acid	1.3
monohydrate
crystalline
Perfume oil G1 or G2	Symrise	Perfume (Fragrance)	0.5
from example 15

At a dosage of 0.5 wt % of perfume oil G1 or G2 in the shower gel, the findings are as follows: the addition of 3-[(4R)-4-isopropylcyclohexen-1-yl]propanal endows the shower gel containing perfume oil G2 with a more natural and caring note relative to the shower gel that contains perfume oil G1 (without 3-[(4R)-4-isopropylcyclohexen-1-yl]propanal); on the whole, addition of 3-[(4R)-4-isopropylcyclohexen-1-yl]propanal results in an odor impression reminiscent of lily of the valley.

Example 17

Transparent Deodorant Sticks (Formulations A and B) or Deodorant Cream Sticks (Formulations C and D)


	A	B	C	D
Component	wt %	wt %	wt %	wt %

Aluminum zirconium	25.00	20.00	25.00	20.00
tetrachlorohydrate - glycine
complex
Dimethicone (10 cst)	—	—	5.00	5.00
Cyclopentasiloxane	—	0.50	1.00	0.50
Petroleum jelly	5.00	4.70	5.00	5.00
Ozokerite	1.00	1.50	—	—
Stearyl alcohol	12.00	12.00	—	—
2-Butyloctanoic acid	0.50	—	0.50	—
Wax	—	—	1.25	1.25
PPG-14 butyl ether	9.00	9.00	—	—
Hardened rapeseed oil	—	—	5.00	5.00
Silicon dioxide	—	—	1.00	—
Farnesol	0.25	—	0.25	—
Paraffin oil	0.50	0.50	—	—
Hydrogenated castor oil (castor	3.50	3.50	—	—
wax)
Talc	4.00	4.00	—	—
Behenyl alcohol	0.20	0.20	—	—
d-Panthenyltriacetate	1.00	1.00	—	—
Preservative	q.s.	q.s.	q.s.	q.s.
Perfume oil H1 or H2	1.50	—	1.15	—
Perfume oil G2 from example 15		0.90	—	0.75
Water	to 100	to 100	to 100	to 100

Composition of perfume oil H1 or H2


	Parts by weight

		Perfume oil
		H2
	Perfume oil	(according
	H1	to the
Fragrances	(comparison)	invention)

ALDEHYDE C10	0.5	0.5
ALDEHYDE C12 MNA 10% DPG	2.0	2.0
MINTONAT	40.0	40.0
MELOZONE	0.5	0.5
VERTOCITRAL	6.0	6.0
DIHYDRO MYRCENOL	120.0	120.0
TETRAHYDRO MYRCENOL	10.0	10.0
AGRUNITRIL	1.0	1.0
ORANGE OIL BRASIL	10.0	10.0
TAMARINE TYPE BASE	10.0	10.0
HEXYL ACETATE	6.0	6.0
ALDEHYDE C14 SO-CALLED	1.0	1.0
TETRAHYDRO LINALOOL	40.0	40.0
DIMETHYL BENZYL CARBINYL	5.0	5.0
BUTYRATE
ORANGE FLOWER ETHER	5.0	5.0
PHENYLETHYL ACETATE	6.5	6.5
PHENYLETHYL ALCOHOL	15.0	15.0
GERANIOL SUPER	30.0	30.0
ROSAPHEN ®	25.0	25.0
ISODAMASCON ®	0.5	0.5
HEDIONE	300.0	300.0
UNDECAVERTOL	0.5	0.5
ALLYL IONONE	2.5	2.5
IONONE BETA	10.0	10.0
EUGENOL	4.0	4.0
ISO E SUPER	30.0	30.0
BRAHMANOL ®	2.0	2.0
AMBROXIDE	2.0	2.0
GLOBALIDE ®	12.0	12.0
GLOBANONE ®	8.0	8.0
MACROLIDE ®SUPRA	45.0	45.0
3-[(4R)-4-Isopropylcyclohexen-1-yl]propanal		50.0
DIPROPYLENE GLYCOL	300.0	250.0
	1000.0	1000.0

Example 18

Antiperspirant Roll-On


Component	wt %	wt %

Caprylyl trimethicone (SilCare TM Silicone 31 M 50)	0.30	0.30
Steareth-20 (GENAPOL TM HS 200)	3.00	3.00
Steareth-2 (GENAPOL TM HS 020)	1.50	1.50
Dicaprylyl ether (Cetiol TM OE)	2.00	2.00
Coco caprylate/caprate (Cetiol TM LC)	2.00	2.00
Glycerin	2.00	2.00
Glyceryl stearate (Cutina TM GMS)	2.00	2.00
Octyldodecanol (Eutanol TM G)	1.00	1.00
Stearyl alcohol	2.50	2.50
Aluminum chlorohydrate according to example 1	10.00	10.00
of EP 1321431
Avocado Extract Persea Gratissima	0.30	0.20
Perfume oil G2 from example 15	0.50	—
Perfume oil H2 from example 17	—	0.60
Water	to 100	to 100

Example 19

Antiperspirant Stick


Component	wt %	wt %

Phenyl trimethicone (SilCare TM Silicone 15 M 50)	13.50	13.50
Cetearyl alcohol	to 100	to 100
Cetiol CC (dicaprylyl carbonate)	13.50	13.50
Stearic acid	3.50	3.50
PEG-40-hydrogenated castor oil (Emulsogen TM HCO	4.10	4.10
040)
PEG-8 distearate (Cithrol 4 DS)	4.10	4.10
Petroleum jelly	6.90	6.90
Aluminum chlorohydrate	13.80	13.80
Aluminum Zirconium Trichlorohydrex Gly	19.50	20.00
Ethylhexylglycerin (octoxyglycerin)	0.30	0.20
4-Methyl-4-phenyl-2-pentanol (Vetikol)	0.25	0.10
Perfume oil A2 from example 9	1.00	—
Perfume oil G2 from example 15	—	0.80

Example 20

Aerosol Spray


Component	wt %	wt %	wt %

Octyldodecanol	0.50	—	0.50
Phenoxyethanol	—	—	0.30
1,2-Pentanediol	1.00	1.00	0.50
1,2-Hexanediol	0.25	0.15	0.25
1,2-Octanediol	0.25	0.25	0.25
Farnesol	—	0.25	0.15
Ethylhexylglycerin (octoxyglycerin)	0.50	0.30	0.50
Perfume oil A2 from example 9	0.80	—	0.50
Perfume oil H2 from example 17	—	1.15	0.50
Ethanol	to 100	to 100	to 100

The mixture obtained after mixing the components given in each case is filled with a propane-butane mixture (2:7) in the weight ratio 2:3 in an aerosol container.

Example 21

Hair Conditioner with UV Protection


Component	INCI Name	wt %	wt %

Lanette O	Cetearyl Alcohol	4.00	4.00
Dragoxat 89	Ethylhexyl Isononanoate	4.00	4.00
Emulsiphos	Potassium Cetyl Phosphate,	0.50	0.50
	Hydrogenated Palm Glycerides
Natrosol 250 HR	Hydroxyethylcellulose	0.25	0.25
Neo Heliopan Hydro	Phenylbenzimidazole Sulfonic Acid	2.00	2.00
L-arginine	Arginine	1.20	1.20
Benzophenone-4	Benzophenone-4	0.50	0.50
Neo Heliopan AP	Disodium Phenyl Dibenzimidazole	0.50	1.00
	Tetrasulfonate
Edeta BD	Disodium EDTA	0.05	0.05
Dragocide liquid	Phenoxyethanol (=and) Methylparaben	0.80	0.80
	(=and) Butylparaben (=and)
	Ethylparaben (=and) Propylparaben
Dow Corning 949 cationic	Amodimethicone, Cetrimonium	2.00	2.00
emulsion	Chloride, Trideceth-12
Dow Corning 5200	Laurylmethicone Copolyol	0.50	0.50
Perfume oil B2 from example	Perfume	0.95	—
10
Perfume oil H2 from example	Perfume		1.25
17
Water	Water (Aqua)	to 100	to 100

Example 22

Sunscreen Spray


Part	Raw materials	INCI Designation	wt %

A	Water, demineralized	Water (aqua)	69.50
	Glycerol	Glycerol	4.00
	1,3-Butylene glycol	Butylene Glycol	5.00
	D-panthenol	Panthenol	0.50
	Lara care A-200	Galactoarabinan	0.25
B	Baysilone oil M 10	Dimethicone	1.00
	Edeta BD	Disodium EDTA	0.10
	Copherol 1250	Tocopheryl Acetate	0.50
	Cetiol OE	Dicaprylyl Ether	3.00
	Neo Heliopan ® HMS	Homosalate	5.00
	Neo Heliopan ® AV	Ethylhexyl Methoxycinnamate	6.00
	Neo Heliopan ® 357	Butyl Methoxydibenzoylmethane	1.00
	Corapan TQ	Diethylhexylnaphthalate	2.00
	Alpha Bisabolol	Bisabolol	0.10
	Pemulen TR-2	Acrylates/C10-30 Alkyl Acrylate	0.25
		Crosspolymer
C	Phenoxyethanol	Phenoxyethanol	0.70
	Solbrol M	Methylparaben	0.20
	Solbrol P	Propylparaben	0.10
D	NAOH, 10%	Sodium Hydroxide	0.60
E	Perfume oil B2 from	Fragrance (Perfume)	0.20
	example 10

Method of production: Dissolve Lara Care A-200 in the other constituents of part A, with stirring. Weigh out all the raw materials of part B (without Pemulen) and dissolve the crystalline substances, with heating. Add and disperse the Pemulen. Add part B to part A and homogenize for 1 minute. Add parts C-E and homogenize for a further 1-2 minutes with the Ultra Turrax.

Example 23

Sunscreen Soft Cream (W/O), Sun Protection Factor (SPF) 40


Part	Raw materials	INCI designation	wt %

A	Dehymuls PGPH	Polyglyceryl-2 Dipolyhydroxy	5.00
		Stearate E
	Copherol 1250	Tocopheryl Acetate E	0.50
	Permulgin 3220	Ozokerite	0.50
	Zinc stearate	Zinc Stearate E	0.50
	Tegosoft TN	C12-15 Alkyl Benzoate E	10.00
	Neo Heliopan ®	Isoamyl-P-Methoxycinnamate E	2.00
	E1000
	Neo Heliopan ® 303	Octocrylene E	5.00
	Neo Heliopan ® MBC	4-Methylbenzylidene Camphor	3.00
	Zinc oxide neutral	Zinc Oxide E	5.00
B	Water, distilled	Water (Aqua)	to 100
	EDETA BD	Disodium EDTA	0.10
	Glycerin	Glycerin	4.00
	Phenoxyethanol	Phenoxyethanol	0.70
	Solbrol M	Methylparaben	0.20
	Solbrol P	Propylparaben	0.10
	Magnesium sulfate	Magnesium Sulfate	0.50
C	Perfume oil B2 from	Perfume (Fragrance)	0.30
	example 10

Method of production: Heat part A to approx. 85° C. Heat part B (without zinc oxide) to approx. 85° C.; add zinc oxide and disperse with the Ultra Turrax. Add B to A. Leave to cool, with stirring. Add part C and then homogenize.

Example 24

Sunscreen Milk (W/O)


Part	Raw materials	INCI Designation	wt %

A	Dehymuls PGPH	Polyglyceryl-2	3.00
		Dipolyhydroxystearate
	Beeswax 8100	Beeswax	1.00
	Monomuls 90-O-18	Glyceryl Oleate	1.00
	Zinc stearate	Zinc Stearate	1.00
	Cetiol SN	Cetearyl Isononanoate	5.00
	Cetiol OE	Dicaprylyl Ether	5.00
	Tegosoft TN	C12-15 Alkyl Benzoate	4.00
	Vitamin E	Tocopherol	0.50
	Solbrol P	Propylparaben	0.10
	Neo Heliopan ® OS	Ethylhexyl Salicylate	5.00
	Neo Heliopan ® AV	Ethylhexyl Methoxycinnamate	7.50
	Uvinul ® T150	Ethylhexyl Triazone	1.50
B	Water, distilled	Water (Aqua)	to 100
	Trilon BD	Disodium EDTA	0.10
	Glycerin	Glycerin	5.00
	Solbrol M	Methylparaben	0.20
	Phenoxyethanol	Phenoxyethanol	0.70
	Neo Heliopan ® AP	Disodium Phenyl	15.00
	10% solution, neutralized	Dibenzimidazole
	with NAOH	Tetrasulfonate
C	Perfume oil G2 from	Perfume (Fragrance)	0.25
	example 15
	Alpha bisabolol	Bisabolol	0.10

Method of production: Heat part A to approx. 85° C. Heat part B to approx. 85° C. Add B to A. Leave to cool, with stirring. Add part C and then homogenize.

Example 25

Permanent Hair Colorant

Part A—Hair coloring base:


	Raw materials	wt %

	Sodium myreth sulfate (e.g. texapon K14 S/K, Cognis)	2.80
	Linoleamidopropyl PG-dimonium chloride phosphate	1.00
	(Arlasilk Phospholipid EFA, Uniqema)
	Caprylyl/capryl glucoside (Plantacare 810 UP, Cognis)	2.00
	Sodium laureth-6 carboxylate (Akypo Soft 45 NV, Kao)	10.00
	Cetearyl alcohol	8.00
	Octyldodecanol	1.00
	Ceteareth-12	0.50
	Ceteareth-20	0.50
	KOH, 50% in water	0.70
	Toluene-2,5-diamine sulfate (oxidizing dye)	0.90
	Resorcinol	0.20
	m-Aminophenol	0.06
	4-Chlororesorcinol	0.15
	Ascorbic acid	0.10
	Sodium sulfite	0.15
	Ammonia, 25% in water	6.00
	Etidronic acid	0.20
	Polyquaternium-2 (Mirapol A15, Rhodia)	0.20
	Perfume oil G2 from example 15	0.30
	Water	65.24

Part B—Developer:


	Raw materials	wt %

	Cetostearyl alcohol	8.00
	Ceteareth-20	2.50
	Steartrimonium chloride (Dehyquart B, Cognis)	1.00
	2,6-Dicarboxypyridine	0.10
	Paraffin oil	0.30
	Etidronic acid	0.40
	Propylene glycol	0.40
	Sodium benzoate	0.04
	Hydrogen peroxide, 50% in water	12.00
	KOH, 50% in water, added to pH = 3.5	q.s.
	Water	To 100

Application: The hair coloring basis according to the invention (part A) and the developer according to the invention (part B) are stirred together in a 1:1 weight ratio and applied to the hair.

Example 26

Hair Coloring Cream for a Blonde Shade


Part	Material	Manufacturer	INCI Name	wt %

A	Oxowax	LCW, France	Cetyl alcohol,	21.00
			Oleyl alcohol,
			Cetearyl alcohol,
			Stearic acid
	Volpo CS 25	Croda GmbH,	Ceteareth25	4.00
		Germany
	Berol 175	Brenntag eurochem	Laureth-8	10.00
		GmbH, Germany
	Lanette ® E	Cognis Germany	Sodium Cetearyl	1.00
		GmbH	Sulfate
	Covaquat 16	LCW, France	Polyquaternium-6	4.00
	Water		Water (Aqua)	49.30
B	Ammonia (20%	Merk Eurolab	Ammonia	10.20
	in water)
C	Perfume oil G2	Symrise	Perfume	0.50
	from example 15

Method of Production:
Mix together Part A, B and C except Covaquat 16 and heat for 20 minutes at 80° C. Once the product is homogeneous, leave to cool. Add Covaquat 16 at 50° C. When the product begins to thicken, stop stirring. Add NH₄OH at room temperature and stir the mixture until homogeneous.

Example 27

Air Freshener Aerosol Spray, Water-Based (W/O Alcohol)


Material	Manufacturer	INCI Name	wt %

Imbentin C/125/030	Symrise	C12-15 pareth-3	0.25
Imbentin AG/100/080	Symrise	deceth-8, Ziegler alcohol	1.00
Perfume oil H2 from	Symrise	Perfume	1.25
example 17
Water, demineralized		Aqua	22.50
Propellant gas 4.2 bar			75.00

Method of production: Mix together all the raw materials in the order given.

Example 28

Liquid Air Freshener Pump-Spray


Material	Manufacturer	INCI Name	wt %

Water, demineralized		Aqua	90.70
Ethanol 96%	Symrise	Ethanol	4.00
Empilan KCL 11/90	Stockmeier	Alcohol C12-15 11EO	3.00
	Chemie GmbH
	&Co. KG
Isopropanol	Symrise	Propan-2-ol	1.00
Sodium hydrogen	Symrise	Sodium bicarbonate	0.20
carbonate p.a.
Parmetol A 26	Hoesch Julius	Mixture of 5-chloro-2-	0.10
		methyl-2H-isothiazol-3-
		one and 2-methyl-2H-
		isothiazol-3-one
Perfume oil F2 from	Symrise	Perfume	1.00
example 14

Method of production: Mix together all the raw materials in the order given. Adjust the pH.

Example 29

Deodorizing Air Freshener Pump/Wick 5% Fragrance


Part	Material	Manufacturer	INCI Name	wt %

A	Water, demineralized		Aqua	67.32
	Sequion 40 NA 32	Polygon		1.25
		Chemie
	Triethanolamine pur C	Symrise	Triethanolamine	0.30
	Rewoderm S 1333	Goldschmidt	DiNa-ricinoleamide of	2.33
		AG	MEA-sulfosuccinate
	Tego Sorb Conc. 50	Evonik	Alcohol C12-14, ethoxylated	0.50
			(2-5 EO) + Zn-ricinoleate
	Ethanol 96%	Symrise	Ethanol	20.00
B	Perfume oil E2 from example	Symrise	Perfume	5.00
	13
	Solubilizer	Symrise		3.00
C	Lactic acid	Symrise	Propanoic acid, 2-hydroxy-	0.30
			propionic acid, Lactol

Method of production: Mix together materials of Part A in the order given. Mix together materials of Part B. When Part A is clear, add Part B. Then add Part C and stir until the mixture is homogeneous.

Example 30

Candle


	Material	wt %

	Candle wax	95.00
	Perfume oil D2 from example 12	5.00

Method of production: Melt the candle wax and stir. Add the perfume oil, stir well. Cast into the desired shape.

Example 31

WC Block


Part	Material	Manufacturer	INCI Name	wt %

A	Imbentin C/125/200	Dr. W. Kolb AG	C12/15 pareth-20	4.00
	Rewomid C 212	Goldschmidt AG	Cocamide MEA	6.00
	Marlon ARL	Sasol GmbH	C10-13, ABS-Na,	42.00
			powder
B	Sodium sulfate	Symrise	Sodium sulfate	42.00
	pharm. (E514)
	Perfume oil F2 from	Symrise	Perfume	6.00
	example 14

Method of production: Melt Part A. Mix in Part B in a mixer-kneader. Form in the extruder at 35-40° C. to a WC block.

Example 32

Synthesis of 3-[(4S)-4-isopropylcyclohexen-1-yl]propanal (Ib)

The aldehyde 3-[(4S)-4-isopropylcyclohexen-1-yl]propanal (formula (Ib) as defined above) is produced starting from I-(−)-limonene (79.5% ee, formula (VIb) as defined above) similarly to the synthesis of 3-[(4R)-4-isopropylcyclohexen-1-yl] propanal (Ia) (examples 4 to 8). The product is obtained with a purity of 97% and with 78% ee.

Example 33

Substantivity

The substantivity test is a test for determining the sensory adherence of a substance on smelling strips. The fragrances to be investigated (compound of formula (Ia), compound of formula (Ib) and Lilial® as benchmark) are each applied in the form of a 10% solution in triethyl citrate (TEC) on a coded smelling strip by dipping and are assessed for intensity at specified time intervals by 15 testers. The 15 testers assess the odor intensity on a scale from 1=odorless to 9=very strong. The results (odor intensity I as a function of the time elapsed t in days d since dipping of the smelling strips) are in shown FIG. 1.
The odor intensity is assessed at the following time intervals after dipping of the smelling strips: 1 hour or less (shown in FIG. 1 as time point “0 days”); 1 day; 2 days; 3 days; 4 days; 7 days; 8 days; 9 days. To ensure that the testers are not influenced, the coded smelling strips are not arranged in a chronological order on the smelling strip stand.
The odor intensity of the compound of formula (Ia) (black filled bar) is assessed in the fresh state and for a period of up to 3 days by the testers in comparison with Lilial® (black cross-hatched bar) as stronger, and after 4 to 7 days at least comparable to Lilial®. After 9 days, a higher odor intensity of the compound of formula (Ia) compared to Lilial® is observed again.
The odor intensity of compound (Ib) (black dotted bar) is, in the fresh state, stronger than that of Lilial® (black cross-hatched bar) and after one day is comparable to Lilial®. After that, the odor intensity of the compound of formula (Ib) at first decreases more than for Lilial® and the compound of formula (Ia), but after 7 to 9 days the values are comparable or slightly higher than with Lilial®.

Claims

1. A compound selected from the group consisting of a compound of formula (Ia)

and a compound of formula (Ib)

2. A mixture, comprising a compound of formula (Ia) and a compound of formula (Ib), as defined in claim 1.

3. A mixture according to claim 2, wherein

the mass ratio of the compound of formula (Ia) to the compound of formula (Ib) is in the range from 0.01 to 99.99 and/or

the total proportion of compounds of formulas (Ia) and (Ib) is greater than 0.01 wt.

4. (canceled)

5. (canceled)

6. A fragrance preparation, comprising:

a compound of formula (I)

and

an additional fragrance that is not a compound of formula (I).

7. A fragrance preparation according to claim 6, wherein the amount of a compound of formula (Ia)

and/or a compound of formula (Ib)

is in the range from 0.0001 to 40 wt relative to the total weight of the fragrance preparation.

8. A fragrance preparation according to claim 6 comprising an additional fragrance with an odor note of lily of the valley.

9. A fragrance preparation according to claim 6, wherein

(i) the amount of the compound of formula (Ia) is sufficient to endow the fragrance preparation with an odor note of lily of the valley,

and/or

(ii) an additional fragrance of the fragrance preparation imparts an odor note of lily of the valley, wherein the amount of the compound of formula (Ia) is sufficient, in comparison with a comparative fragrance preparation of otherwise identical composition without the compound of formula (Ia), to modify and/or to intensify the odor note of lily of the valley,

and/or

(iii) the amount of the compound of formula (Ia) is sufficient to endow the fragrance preparation with an impression selected from the group consisting of natural, caring, complex and radiant

and/or

(iv) the amount of the compound of formula (Ia) is sufficient to modify and/or to intensify an impression selected from the group consisting of natural, caring, complex and radiant in comparison with a comparative fragrance preparation of otherwise identical composition without the compound of formula (Ia)

and/or

(v) the amount of the compound of formula (Ib) is sufficient to endow the fragrance preparation with an odor note of lily of the valley,

and/or

(vi) an additional fragrance of the fragrance preparation imparts an odor note of lily of the valley, wherein the amount of the compound of formula (Ib) is sufficient, in comparison with a comparative fragrance preparation of otherwise identical composition without the compound of formula (Ib), to modify and/or to intensify the odor note of lily of the valley.

10. A perfumed product comprising

a compound of formula (I) as defined in claim 1 in a sensorially effective amount.

11. A perfumed product according to claim 10, wherein the amount of a compound of formula (Ia) and/or a compound of formula (Ib) is in the range from 0.0001 to 5 wt %, relative to the total weight of the product.

12. A perfumed product according to claim 10, selected from the group consisting of washing and cleaning products, hygiene products, and care products.

13. A method for of providing skin, hair, surfaces, or textile fibers with an odor note of lily of the valley comprising applying a fragrance preparation according to claim 6 to the skin, hair, surfaces, or textile fibers.

14. A method for producing the compound of formula (I)

comprising an acid-catalyzed reaction of an acetal of formula (II),

wherein R is a linear or branched, saturated or unsaturated alkyl group with 1 to 10 carbon atoms.

15. An acetal of formula (II)

16. A method for producing a compound of formula (Ia) or a compound of formula (Ib) as defined in claim 1, or a mixture of compounds of formula (Ia) and (Ib), comprising the use

of d-(+) limonene as educt for producing the compound of formula (Ia),

of 1-(−) limonene as educt for producing the compound of formula (Ib) as, or

of a mixture containing d-(+) limonene and 1-(−) limonene as educt for producing a mixture containing the compound of formula (Ia) and the compound of formula (Ib).

17. A method for producing a compound of formula (I) as defined in claim 6 comprising pyrolysis of the spirolactone of formula (VIII) to form the compound of formula (I)

18. A method for mediating, intensifying and/or modifying an odor note of lily of the valley to a substance comprising bringing the substance into contact with a compound according to claim 1.

a compound of formula (I),

19. A method for mediating, intensifying and/or modifying an odor note of lily of the valley to a substance comprising bringing the substance into contact with a mixture according to claim 2.

20. A method for mediating, intensifying and/or modifying an odor note of lily of the valley to a substance comprising bringing the substance into contact with a fragrance preparation according to claim 6.

21. A method for mediating, intensifying and/or modifying an odor note of lily of the valley to a substance comprising bringing the substance into contact with a fragrance preparation according to claim 7.

22. A method for increasing the sub stantivity and/or the retention of a fragrance comprising combining the fragrance with a compound of formula (I) as defined in claim 6.