Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2002-03-21
2003-06-03
Owens, Amelia (Department: 1625)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C512S012000, C560S183000
Reexamination Certificate
active
06573391
ABSTRACT:
FIELD OF THE INVENTION
The invention relates to novel 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones, and to their preparation and use in functional perfumery and in fine perfumery.
BACKGROUND OF THE INVENTION
Compounds with a musk odor are sought-after components in the fragrance industry. They are characterized both by their property of imparting radiance to perfume compositions and also by their ability to act as fixative. For this reason, musk fragrances are nowadays used in many perfume compositions.
Typical musk fragrances are characterized by a macrocyclic ring having 13 to 17 carbon atoms which carries a ketone or an ester as functional group. Moreover, macrocyclic musk fragrances which carry two functional group are also known, e.g. 1,7-dioxacycloalkan-8-ones (EP A 884,315). However, the functional groups of these molecules are distributed over both hemispheres of macrocycles. Preference is, however, given to macrocyclic compounds in which the functional groups are concentrated in one part of the molecule since, in so doing, a stronger bond to the active center of the receptor and, consequently, a lower threshold value can be expected.
Because the costs of starting materials for the preparation are sometimes high and because of the extremely high synthesis complexity, the number of macrocyclic compounds available to the perfumer for the composition of perfumes is relatively limited (K. Bauer, D. Garbe, H. Surburg, Common Fragrance and Flavor Materials, Wiley-VCH, 3
rd
Edition, 1997, 67 to 68 and 117 to 122). There is an urgent need for further macrocyclic compounds which can be prepared in an efficient synthesis from favorable starting materials and, moreover, extend the perfumer's options with their original scent properties.
The class of nature-similar macrocyclic musk fragrances will become more and more important in the future since the synthetic musk compounds of the nitroaromatic and polycyclic series are persistent and lipophilic, meaning that these compounds accumulate in aquatic food chains and fatty tissue (H. Brunn, G. Rimkus, Ernährungs-Umschau 1996, 43, 442 to 449; H. Brunn, G. Rimkus, Ernährungs-Umschau 1997, 44, 4 to 9).
SUMMARY OF THE INVENTION
It was therefore the object to extend the raw material palette available for composing perfume through novel macrocyclic musk compounds with original odiferous properties.
Furthermore, it should be possible to prepare the novel musk fragrances in a cost-effective manner.
DETAILED DESCRIPTION OF THE INVENTION
We have now found novel 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones of the formula
in which
the dashed bond is a single or E/Z double bond,
where in the case of a double bond being present in the ring, the compounds can be in the E and Z form, and
compounds with a chiral center can be either in the (R) or (S) form, or else can be present as an enantiomer mixture,
R
1
and R
2
are identical or different and are hydrogen or lower alkyl,
x is a saturated alkylene chain having 1 to 4 carbon atoms and
y is a saturated alkylene chain having 4 to 10 carbon atoms,
where saturated compounds
in which R
1
and R
2
are hydrogen and x+y=11 carbon atoms and
in which R
1
is methyl and R
2
is hydrogen and x+y=8 carbon atoms, are excluded.
Lower alkyl generally means a saturated hydrocarbon radical having 1 to 6 carbon atoms. Examples which may be mentioned are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl and isohexyl.
Preferred radicals are hydrogen, methyl and ethyl.
An alkylene chain having 1 to 4 carbon atoms generally means methylene, ethylene, propylene and butylene.
Preference is given here to: methylene, ethylene and butylene.
An alkylene chain having 4 to 10 carbon atoms generally means butylene, pentylene, hexylene, heptylene, octylene, nonylene and decylene.
Preference is given here to: butylene, octylene and nonylene.
The novel 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones according to the invention accordingly include 14- to 18-membered saturated or unsaturated, unsubstituted or lower-alkyl-substituted 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones.
Specifically, mention may be made of the following 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones:
1,4-dioxa-(E/Z)-9-cyclotetradecen-2-one
1,4-dioxacyclotetradecan-2-one
3-methyl-1,4-dioxa-(E/Z)-6-cyclopentadecen-2-one
3-methyl-1,4-dioxacyclopentadecan-2-one
1,4-dioxa-(E/Z)-6-cyclopentadecen-2-one
1,4-dioxacyclopentadecan-2-one
3-methyl-1,4-dioxa-(E/Z)-6-cyclohexadecen-2-one
3-methyl-1,4-dioxacyclohexadecan-2-one
1,4-dioxa-(E/Z)-6-cyclohexadecen-2-one
1,4-dioxacyclohexadecan-2-one
1,4-dioxa-(E/Z)-7-cyclohexadecen-2-one
1,4-dioxa (E/Z)-7-cycloheptadecen-2-one
3-methyl-1,4-dioxa-(E/Z)-7-cyclohexadecen-2-one
3-methyl-1,4-dioxa-(E/Z)-7-cycloheptadecen-2-one
3-methyl-1,4-dioxacycloheptadecan-2-one
The 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones according to the invention in which the functional groups are in close proximity to one another achieve said object in an ideal manner. As well as perfumistically interesting musk-like odor notes, they are characterized by very good adhesion, coupled with a low threshold value.
The saturated 1,4-dioxacycloalkan-2-ones, methyl-substituted in the 3 position, in particular 3-methyl-1,4-dioxacyclopentadecan-2-one and 3-methyl-1,4-dioxacyclohexadecan-2-one, have particularly attractive olfactory odor properties. They are characterized by a sweet, woody-ambergris, animalic, erogenous and thus very natural musk note. The olfactory profile of the unsaturated 3-methyl-1,4-dioxacyloalken-2-ones is very similar to that of the saturated compounds, although the intensity is lower. For comparison, the analogous 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones without methyl substitution in the 3 position have been synthesized. Surprisingly, in the case of the unsaturated 1,4-dioxacycloalken-2-ones, the erogenous and animalic aspects are pushed into the background in favor of metallic, pressing iron-like odor descriptions. The saturated 1,4-dioxacycloalkan-2-ones, by contrast, and here in particular 1,4-dioxacyclohexadecan-2-one are characterized again by a very nice natural musk-like character.
In contrast to the known 1,4-dioxacycloheptadecan-2-one and 3-methyl-1,4-dioxacyclotetradecan-2-one, the 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones according to the invention surprisingly have a very much more natural musk note, coupled with nitromusk and ambrette musk aspects.
We have found a process for the preparation of novel 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones of the formula
in which
the dashed bond is a single or E/Z double bond,
where in the case of a double bond being present in the ring, the compounds can be in the E and Z form, and
compounds with a chiral center can be either in the (R) or (S) form, or else can be present as an enantiomer mixture,
R
1
and R
2
are identical or different and are hydrogen or lower alkyl,
x is a saturated alkylene chain having 1 to 4 carbon atoms and
y is a saturated alkylene chain having 4 to 10 carbon atoms,
where saturated compounds
in which R
1
and R
2
are hydrogen and x+y=11 carbon atoms and
in which R
1
is methyl and R
2
is hydrogen and x+y=8 carbon atoms, are excluded, found,
which is characterized in that alkylcarboxylic acids or esters thereof which can be derivatized in the 2 position and are of the formula
in which
R
1
has the meaning given above, and
R
3
is OH, Cl, Br and
R
4
is OH, OMe or OEt,
are used, which, in the 1st step, are etherified, in a 2nd step are esterified and in a 3rd step the ring is closed by olefine metathesis to give the unsaturated 1,4-dioxacycloalken-2-ones, which are then optionally hydrogenated in a 4th step to give the saturated 1,4-dioxacycloalkan-2-ones.
In the 1st step, where R
3
=OH and R
4
=OMe or OEt, deprotonation is carried out with one equivalent of sodium hydride as base in tetrahydrofuran as solvent. 1.5 equivalents of the [lacuna&
Eh Marcus
Wörner Peter
Haarmann & Reimer GmbH
Pendorf & Cutliff
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