DE102007055124A1 - New 7-(3-methylbut-2-en-1-yl)-2H-1,5-benzodioxepin-3(4H)-one, useful as fragrance and/or flavor material, and in e.g. shampoo, softener, detergent, pre-shave product, floor cleaner, air freshener and sunscreen cream - Google Patents

Abstract

7-(3-Methylbut-2-en-1-yl)-2H-1,5-benzodioxepin-3(4H)-one (I) is new. Independent claims are included for: (1) a mixture (III) of fragrance- and/or flavor-material comprising (I) and one or more additional fragrance- and/or flavor-materials, preferably one or more fragrance- and/or flavor-materials with a lily of the valley olfactory- and/or gustatory-notes, and/or one or more fragrance- and/or flavor-materials with an aqueous olfactory- and/or gustatory-notes; (2) the preparation of (I); (3) 4-(3-methylbut-2-en-1-yl)benzene-1,2-diol compound (II); and (4) the preparation of mixture (III), comprising mixing (I) with the components of fragrance and/or flavor-materials.

Description

The in particular, the present invention relates to the novel compound 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one, fragrance and flavoring compounds comprising this compound, corresponding perfumed products, the use of this compound as an odoriferous and / or aromatic substance as well as a method for mediating, Modifying and / or enhancing a marine, aldehydic, ozone, watery-fresh, fruity and / or floral odor and / or flavor, preferably a lily-of-the-valley odor and / or taste note.

In The perfume industry exists despite a large number already existing fragrances generally a need for new fragrances. Are z. B. marine (aqueous) fragrances since the Consumers constantly new and modern fragrances watery or with watery-fresh scents available to be asked. Fragrances with marine fragrance notes are in large quantities and innumerable variations in Perfumes, fragrance mixtures (perfume oils, Perfume oil compositions) and perfumes used for a variety of applications. Because of Consistent with growing consumer demand for new modern fragrances a constant need in the perfume industry Fragrances that produce new effects in perfumes and create new fashion trends in this way. links with watery or watery-fresh scents have always been important and coveted components in the fragrance industry. Thus, today marine fragrances come in many perfume compositions for use.

The marine odor note of numerous perfume compositions is based on 7-methyl-2H-1,5-benzodioxepin-3 (4H) -one (Calone ^1951® ), compound of formula (II).

This classic marine fragrance is used together with other 7-methyl, 7-ethyl, 7-propyl and 7-butyl substituted derivatives in US 3,517,031 described.

7-Methyl-2H-1,5-benzodioxepin-3 (4H) -one of the formula (II) can be according to US 3,517,031 by Dieckmann condensation of dimethyl 2,2 '- [(4-methyl-1,2-phenylene) bis (oxy)] diacetate and subsequent decarboxylation. There is no distinction in this specification between different 7-alkyl-substituted 2H-1,5-benzodioxepin-3 (4H) -one derivatives. These are all referred to as "watermelon ketones", which can be used in perfume compositions to achieve a fresh, green-leafy effect.

The compound 7-propyl-2H-1,5-benzodioxepin-3 (4H) -one and its use in perfume compositions is described in U.S. Pat EP 0 902 024 disclosed.

und 7-Allyl-2H-1,5-benzodioxepin-3(4H)-on der Formel (IV),

sowie 1,2-substituierten 2,3-Didehydro-1H-5,9-dioxacyclohepta[f]inden-7-onen und deren Anwendung in der Parfümerie. EP 1 136 481 deals with further 7-alkyl and 7-alkenyl derivatives of 2H-1,5-benzodioxepin-3 (4H) -one with branched and unbranched substituents, in particular 7- (3-methylbutyl) -2H-1,5- benzodioxepin-3 (4H) -one of the formula (III)

and 7-allyl-2H-1,5-benzodioxepin-3 (4H) -one of the formula (IV),

and 1,2-substituted-2,3-didehydro-1H-5,9-dioxacyclohepta [f] inden-7-ones and their use in perfumery.

EP 1 136 481 describes the synthesis of 7- (3-methylbutyl) -2H-1,5-benzodioxepin-3 (4H) -one (Verbin of the formula (III)) starting from veratrole by Friedel-Crafts acylation with isovaleric acid, Clemmensen reduction, demethylation, Williamson ether synthesis with 3-chloro-2- (chloromethyl) -prop-1-ene and oxidation to the ketone. This is loud EP 1 136 481 by an "intensive and diffuse linear marine fragrance with nuances of adoxal ^®" from. The same patent describes the preparation of 7-allyl-2H-1,5-benzodioxepin-3 (4H) -one (compound of formula (IV)), which is obtained by demethylation of eugenol, Williamson ether synthesis with bromoacetic acid methyl ester and subsequent Dieckmann condensation and decarboxylation and is described as a "linear, very intense marin-floral fragrance with nuances of ozone, watermelons and fatty aldehydes".

Perfumers often speak in general terms of these 7-substituted 2H-1,5-benzodioxepin-3 (4H) -one derivatives as "watermelon ketones", the respective compounds, however, differing very significantly with regard to individual scents and aspects ( see below.) The structure-activity relationships of various 2H-1,5-benzodioxepin-3 (4H) -one derivatives are discussed in the publication J.-M. Gaudin et al., Helv. Chim. Acta 2007, 90, 1245-1265 discussed.

For the creation of novel modern perfume compositions exists constant need for marine fragrances with special odor properties that are suitable as a basis for the composition of novel modern perfumes with complex to serve marine character. The sought after marine fragrances preferably in addition to the typical marine odor note more notes and have aspects that give them an odor character and complexity to lend. Special effects and complexity can be also with perfumes that have a varied character have during the perfume process (smell, focus odor development, after-odor) varies. Often is desired a combination of marine and floral scents, especially Lily of the Valley fragrance notes. Marine fragrances are therefore in practice often with floral, especially lily-of-the-valley fragrances combined. To the number of different fragrances in fragrance mixtures to be able to reduce, are constantly odoriferous substances sought, which have several odor notes in combination.

• – Die Mechanismen der Geruchswahrnehmung sind nicht ausreichend bekannt.
• – Die Zusammenhänge zwischen der speziellen Geruchswahrnehmung einerseits und der chemischen Struktur des zugehörigen Riechstoffs andererseits sind nicht hinreichend erforscht.
• – Häufig bewirken bereits geringfügige Änderungen am strukturellen Aufbau eines bekannten Riechstoffs starke Änderungen der sensorischen Eigenschaften und beeinträchtigen die Verträglichkeit für den menschlichen Organismus.

However, the search for suitable fragrances is made more difficult by the following facts:

• - The mechanisms of smell perception are not well known.
• - The connections between the special smell perception on the one hand and the chemical structure of the corresponding fragrance on the other hand, have not been sufficiently researched.
• Often, even minor changes in the structural makeup of a known fragrance cause significant changes in sensory properties and compromise human organism compatibility.

Of the Success of finding suitable fragrances therefore depends strongly dependent on the intuition of the seeker.

It The object of the present invention was another, new Smelling and / or flavoring with a marine odor note to find. This should preferably new and / or special odor properties (as with the marine odor note further notes and aspects), with which fragrance and / or flavoring compositions special notes and aspects can be conferred. Preferably should the odoriferous and / or aromatic substance to be released next to the marine (aqueous) Odor note a flowery, especially a lily-of-the-valley smell note exhibit. Preferably, the olfactory and / or flavoring should have a varied, z. B. varying, character. Further Preferably, the odoriferous and / or aromatic substance to be dispensed should be further advantageous properties, such as high substantivity, own and / or give odoriferous and / or flavoring mixtures can.

It It has now surprisingly been found that 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one solves this task.

One The first aspect of the present invention relates to 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one of the formula (I).

These Compound is significantly different in odor from 7-methyl-2H-1,5-benzodioxepin-3 (4H) -one (Compound of formula (II)), 7- (3-methylbutyl) -2H-1,5-benzodioxepin-3 (4H) -one (Compound of formula (III)) and 7-allyl-2H-1,5-benzodioxepin-3 (4H) -one (Compound of formula (IV)).

The odor descriptions of these compounds are according to their own experiments as follows:
7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one compound of the formula (I) according to the invention: In the onset slightly aldehydiger, ozone impression, which is too a flowery, lily of the valley-like note with ozone and slightly fruity, melon-like aspects developed. In particular, the soft, floral note in combination with the aldehydic and ozone characteristics remains dominant in the afterglow. A watery (marine) note with fresh aspects (watery-fresh) is clearly noticeable throughout the course of the fragrance.
7-Methyl-2H-1,5-benzodioxepin-3 (4H) -one (compound of the formula (II)): In all phases of the scent process, a strong, expressive watery note that hardly changes its character.
7- (3-Methylbutyl) -2H-1,5-benzodioxepin-3 (4H) -one (compound of formula (III)): Strong aldehydic note with aqueous aspects that is somewhat soapy and technical. The aldehydic, Farenal-like character dominates in all phases of the fragrance process. Flowery notes are present only to a very limited extent.
7-Allyl-2H-1,5-benzodioxepin-3 (4H) -one (compound of the formula (IV)): Aqueous note, but slightly aldehydic and not very strong in all phases of the scent process. The floral note is not very pronounced.

Surprisingly differ the previously known compounds 7-methyl-2H-1,5-benzodioxepin-3 (4H) -one (11), 7- (3-methylbutyl) -2H-1,5-benzodioxepin-3 (4H) -one (111) and 7-allyl-2H-1,5-benzodioxepin-3 (4H) -one (IV) clearly shows off odor 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one according to the invention (I), especially due to the perfumist desire and precious soft-flowering lily-of-the-valley cyclamen character the compound of the invention, the heart note the focus of the fragrance development (odor development) dominates, but also through its more complex, diversified character.

One Another aspect of the present invention relates to the use of 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one (Comp of the formula (I)) as a fragrance and / or flavoring.

Prefers is a use according to the invention for switching, Modifying and / or enhancing a marine, aldehydic, ozone, watery-fresh, fruity and / or floral Odor and / or flavor, preferably a lily-of-the-valley odor and / or taste note.

One Another aspect of the present invention relates to an odor or flavoring mixture comprising 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one and one or more other fragrances or flavorings, in particular one or more fragrances or aromas with a lily of the valley odor and / or Flavor note and / or one or more fragrance or flavoring substances with an aqueous (marine) odor and / or flavor.

In Mixtures with other fragrances or flavorings can do this 7- (3-Methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one according to the invention (I) even at low dosages the intensity of a fragrance mixture or flavoring mixture to enhance and the overall picture the odoriferous or flavoring mixture to round off the odor and the Mix to give more charisma and naturalness. In higher doses, the soft floral scent comes to Wear, accompanied by an ozone and slightly fruity note is. It is with 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one (I) achieves, in particular, effects reminiscent of lilies of the valley, and the composition features a flowery, ozone-aldehydic, marine smell on. In particular, a lily-of-the-valley odor and / or flavor of other fragrances or flavorings may so modified and / or reinforced.

Prefers is a fragrance or flavoring mixture according to the invention, comprising an amount of 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one, which is sufficient to one or more odor or taste notes selected from the group consisting of marine, aldehydic, ozone, watery-fresh, fruity and / or floral, to modify and / or reinforce. Preferably enough the amount of 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one to create a lily-of-the-valley smell or taste note to convey, modify and / or reinforce.

Preferably, a fragrance or flavoring composition according to the invention comprises an amount of 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one in the range of 0.001 to 40% by weight. %, preferably 0.01 to 25 wt .-% and in particular 0.1 to 10 wt .-%, based on the total amount of the fragrance or Aromastoffkomposition.

Usual further fragrances or flavorings with which 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one are advantageously combined in the context of an odoriferous or flavoring mixture according to the invention can, can be found z. In Steffen Arctander, Perfume and Flavor Chemicals, Self-Publishing, Montclair, NJ 1969; H. Surburg, J. Panten, Common Fragrance and Flavor Materials, 5th Edition, Wiley-VCH, Weinheim 2006 ,

In detail may be mentioned:
Extracts from natural raw materials such as essential oils, concretes, absolues, resines, resinoids, balms, tinctures such. B. amber tincture; Amyrisöl; Angelica seed oil; Angelica root oil; anise oil; Valerian oil; Basil oil; Tree moss absolute; Bay oil; Mugwort oil; Benzoeresin; Bergamot oil; Beeswax absolute; birch tar; Bitter almond oil; Savory oil; Buccoblätteröl; Cabreuvaöl; cade oil; calamus; camphor oil; Cananga oil; cardamom; Cascarillaöl; cassia; Cassie absolute; Castoreum absolute; Cedernblätteröl; cedarwood; cistus; citronella; lemon; copaiba balsam; Copaivabalsamöl; Coriander oil; costus root; Cuminöl; Cypress oil; Davanaöl; Dill herb oil; Dill seed oil; Eau de Brouts absolute; Oak moss absolute; elemi; Tarragon oil; Eucalyptus citriodora oil; eucalyptus oil; Fennel oil; Pine needle oil; galbanum; Galbanumresin; geranium; Grapefruit oil; guaiac wood; gurjun balsam; Gurdyb salsa oil, Helichrysum absolute; Helichrysumöl; Ginger oil; Iris root absolute; Orris root oil; Jasmine absolute; calamus; Chamomile oil blue; Camomile oil Roman; Carrot seed oil; Kaskarillaöl; Pine needle oil; spearmint; Seed oil; labdanum; Labdanum absolute; Labdanumresin; Lavandin absolute; lavender oil; Lavender absolute; Lavender oil; Lemongrass oil; Lovage oil; Distilled lime oil; Lime oil pressed; linaloe; Litsea cubeba oil; Bay leaf oil; Macisöl; Marjoram oil; Mandarin oil; Massoirindenöl; Mimosa absolute; Musk seed oil; musk tincture; Clary sage oil; Nutmeg oil; Myrrh absolute; Myrrh oil; myrtle; Clove leaf oil; Clove flower oil; neroli; Olibanum absolute; olibanum; Opopanaxöl; Orange blossom absolute; Orange oil; oregano; Palmarosa oil; patchouli oil; perilla oil; Peruvian balsam oil; Parsley leaf oil; Parsley seed oil; Petitgrain oil; Peppermint oil; Pepper oil; chilli; pine oil; Poleyöl; Rose absolute; Rosewood oil; Rose oil; Rosemary oil; Sage oil Dalmatian; Sage oil spanish; sandalwood; Celery seed oil; spike lavender oil; star anise; Styraxöl; tagetes; Pine needle oil; Tea-tree oil; turpentine; Thyme oil; Tolu; Tonka absolute; Tuberose absolute; Vanilla extract; Violet leaf absolute; verbena; vetiver; Juniper berry oil; Wine yeast oil; Wormwood oil; Wintergreen oil; ylang oil; hyssop oil; Civet absolute; cinnamon leaf; cinnamon bark oil; and fractions thereof or ingredients isolated therefrom;
individual fragrances from the group of hydrocarbons, such as. 3-carene; α-pinene; β-pinene; α-terpinene; γ-terpinene; ρ-cymene; bisabolene; camphene; caryophyllene; cedrene; farnesene; limonene; longifolene; myrcene; ocimene; valencene; (E, Z) -1,3,5-undecatriene;
from the group of aliphatic alcohols, such as. Hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2-methylheptanol, 2-methyl-octanol; (E) -2-hexenol; (E) - and (Z) -3-hexenol; 1-octene-3-ol; Mixture of 3,4,5,6,6-pentamethyl-3/4-hebten-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan-2-ol; (E, Z) -2,6-Nonadienol; 3,7-dimethyl-7-methoxyoctane-2-ol; 9-decenol; 10-undecenol; 4-methyl-3-decen-5-ol;
from the group of aliphatic aldehydes and their acetals such. Hexanal; heptanal; octanal; nonanal; decanal; undecanal; dodecanal; tridecanal; 2-methyloctanal; 2-methyl nonanal; (E) -2-hexenal; (Z) -4-heptenal; 2,6-dimethyl-5-heptenal; 10-undecenal; (E) -4-decenal; 2-dodecenal; 2,6,10-trimethyl-5,9-undecadienal; Heptanal diethyl; 1,1-dimethoxy-2,2,5-trimethyl-4-hexene; citronellyloxyacetaldehyde;
from the group of aliphatic ketones and their oximes such. 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;
from the group of aliphatic sulfur-containing compounds such. For example, 3-methylthiohexanol; 3-Methylthiohexylacetat; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexyl acetate; 1-menthene-8-thiol;
from the group of aliphatic nitriles such. B. 2-nonenitrile; 2-Tridecensäurenitril; 2,12-Tridecensäurenitril; 3,7-dimethyl-2,6-octadiensäurenitril; 3,7-dimethyl-6-octensäurenitril;
from the group of aliphatic carboxylic acids and their esters such. B. (E) - and (Z) -3-hexenylformate; ethylacetoacetate; isoamyl; hexyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate; (E) -2-hexenyl acetate; (E) - and (Z) -3-hexenylacetate; octyl acetate; 3-octyl acetate; 1-octen-3-yl acetate; ethyl butyrate; butyl butyrate; isoamyl; hexyl butyrate; (E) - and (Z) -3-hexenyl isobutyrate; hexyl crotonate; Ethylisovalerianat; Ethyl 2-methylpentanoate; ethylhexanoate; allyl hexanoate; ethyl heptanoate; allyl heptanoate; ethyl octanoate; Ethyl (E, Z) -2,4-decadienoate; Methyl-2-octinat; Methyl-2-noninat; Allyl-2-isoamyloxyacetat; Methyl-3,7-dimethyl-2,6-octadienoate;
from the group of acyclic terpene alcohols such. Citronellol; geraniol; nerol; linalool; Lavadulol; nerolidol; farnesol; tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl-7-octene-2-ol; 2,6-dimethyl octane-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadiene-2-ol; 2,6-dimethyl-3,5-octadiene-2-ol; 3,7-Dime thyl-4,6-octadiene-3-ol; 3,7-dimethyl-1,5,7-octatriene-3-ol; 2,6-dimethyl-2,5,7-octatien-1-ol; as well as their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates, 3-methyl-2-butenoates;
from the group of acyclic terpene aldehydes and ketones such. B. Geranial; neral; citronellal; 7-hydroxy-3,7-dimethyloctanal; 7-methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9-undecenal; geranyl acetone; and the dimethyl and diethyl acetals of geranial, neral, 7-hydroxy-3,7-dimethyloctanal;
from the group of cyclic terpene alcohols such. Menthol; isopulegol; α-terpineol; Terpinenol-4; Menthane-8-ol; Menthane-1-ol; Menthane-7-ol; borneol; soborneol; linalool; monopoly; cedrol; ambrinol; Vetyverol; guaiol; as well as their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates, 3-methyl-2-butenoates;
from the group of cyclic Terpenaldehyde and ketones such. Eg menthone; menthone; 8-mercaptomenthan-3-one; carvone; camphor; fenchon; α-ionone; β-ionone; α-n-methyl ionone; β-n-methyl ionone; α-isomethylionone; β-isomethylionone; α-Iron; α-damascone; β-Damascone; β-Damascenone; γ-damascone; δ-damascone; 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-methanonaphthalen-8 (5H) -one; nootkatone; Dihydronootkaton; α-sinensal; β-sinensal; acetylated cedarwood oil (methyl cedryl ketone);
from the group of cyclic alcohols such. For example, 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3-isocamphylcyclohexanol; 2,6,9-trimethyl- (Z2, Z5, E9) -cyclododecatrien-1-ol; 2-isobutyl-4-methyl tetrahydro-2H-pyran-4-ol;
from the group of cycloaliphatic alcohols such. B. α, 3,3-trimethylcyclohexylmethanol; 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; 2-ethyl-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;
from the group of cyclic and cycloaliphatic ethers such. Cineol; cedryl methyl ether; cyclododecyl; (Ethoxymethoxy) cyclododecane; α-Cedrenepoxid; 3a, 6,6,9a-tetramethyl-dodecahydronaphtho [2,1-b] furan; 3a-ethyl-6,6,9a-trimethyldodecahydronaphtho [2,1-b] furan; 1,5,9-trimethyl-13-oxabicyclo [10.1.0] trideca-4,8-diene; rose oxide; 2- (2,4-dimethyl-3-cyclohexen-1-yl) -5-methyl-5- (1-methylpropyl) -1,3-dioxane;
from the group of cyclic ketones such. For example, 4-tert-butylcyclohexanone; 2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclopentanone; 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) -indanon; 9-cycloheptadecen -1-one; cyclopentadecanone; cyclohexadecanone;
from the group of cycloaliphatic aldehydes such. B. 2,4-dimethyl-3-cyclohexene carbaldehyde; 2-methyl-4- (2,2,6-trimethyl-cyclohexen-1-yl) -2-butenal; 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene carbaldehyde; 4- (4-methyl-3-penten-1-yl) -3-cyclohexene carbaldehyde;
from the group of cycloaliphatic ketones such. B. 1- (3,3-dimethylcyclohexyl) -4-penten-1-one; 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-naphtalenylmethylketon; Methyl-2,6,10-trimethyl-2,5,9-cyclododecatrienylketon; tert-butyl (2,4-dimethyl-3-cyclohexen-1-yl) ketone;
from the group of esters of cyclic alcohols such. B. 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert-pentylcyclohexyl acetate; 4-tert-pentylcyclohexyl acetate; Decahydro-2-naphthyl acetate; 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-hexahydro-5- or -6-indenyl acetate; 4,7-methano-3a, 4,5,6,7,7a-hexahydro-5- or -6-indenylpropionate; 4,7-methano-3a, 4,5,6,7,7a-hexahydro-5- or -6-indenyl isobutyrate; 4,7-Methanooctahydro-5- or -6-indenyl acetate;
from the group of esters of cycloaliphatic carboxylic acids such. For example, allyl-3-cyclohexylpropionate; Allylcyclohexyloxyacetat; methyldihydrojasmonate; methyl jasmonate; Methyl-2-hexyl-3-oxocyclopentanecarboxylate; Ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate; Ethyl 2,3,6,6-tetramethyl-2-cyclohexenecarboxylate; Ethyl-2-methyl-1,3-dioxolan-2-acetate;
from the group of aromatic hydrocarbons such. Styrene and diphenylmethane;
from the group of araliphatic alcohols such. B. benzyl alcohol; 1-phenylethyl; 2-phenylethyl; 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3- (3-methylphenyl) propanol; 1,1-dimethyl-2-phenylethyl; 1,1-dimethyl-3-phenylpropanol; 1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenylpentanol; 3-methyl-5-phenylpentanol; 3-phenyl-2-propen-1-ol; 4-methoxybenzyl; 1- (4-isopropylphenyl) ethanol;
from the group of esters of araliphatic alcohols and aliphatic carboxylic acids such. B. benzyl acetate; benzylpropionate; benzyl isobutyrate; Benzylisovalerianat; 2-phenylethyl acetate; 2-phenylethyl propionate; 2-Phenylethylisobutyrat; 2-Phenylethylisovalerianat; 1-phenylethyl acetate; α-Trichlormethylbenzylacetat; α, α-Dimethylphenylethylacetat; α, α-Dimethylphenylethylbutyrat; cinnamyl; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate;
from the group of araliphatic ethers such. B. 2-phenylethyl methyl ether; 2-Phenylethylisoamylether; 2-phenylethyl-1-ethoxyethyl ether; Phenylacetaldehyde dimethylacetal; Phenylacetaldehyde diethyl; Hydratropaaldehyd dimethyl; Phenylacetaldehyde glycerinacetal; 2,4,6-trimethyl-4-phenyl-1,3-dioxane; 4,4a, 5,9b-tetrahydroindeno [1,2-d] -m-dioxin; 4,4a, 5,9b-tetrahydro-2,4-dimethylindeno [1,2-d] -m-dioxin;
from the group of aromatic and araliphatic aldehydes such. B. benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; Hydratropaaldehyd; 4-methylbenzaldehyde; 4-methylphenylacetaldehyde; 3- (4-ethylphenyl) -2,2-dimethylpropanal; 2-methyl-3- (4-isopropylphenyl) propanal; 2-methyl-3- (4-tert-butylphenyl) propanal; 3- (4-tert-butylphenyl) propanal; cinnamic aldehyde; α-Butylzimtaldehyd; α-amyl cinnamic aldehyde; α-hexyl cinnamic aldehyde; 3-methyl-5-phenylpentanal; 4-methoxybenzaldehyde; 4-Hydroxy-3-methoxybenzaldehyde; 4-hydroxy-3-ethoxybenzaldehyde; 3,4-methylenedioxybenzaldehyde; 3,4-dimethoxybenzaldehyde; 2-methyl-3- (4-methoxyphenyl) propanal; 2-methyl-3- (4-methylenedioxyphenyl) propanal;
from the group of aromatic and araliphatic ketones such. Acetophenone; 4-methylacetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone; 4- (4-hydroxyphenyl) -2-butanone; 1- (2-naphthalenyl) ethanone; benzophenone; 1,1,2,3,3,6-hexamethyl-5-indanyl methyl ketone; 6-tert-butyl-1,1-dimethyl-4-indanyl methyl ketone; 1- [2,3-dihydro-1,1,2,6-tetramethyl-3- (1-methylethyl) -1H-5-indenyl] ethanone; 8'-hexamethyl-2-acetonaphthone, 5 ', 6', 7 ', 8'-tetrahydro-3', 5 ', 5', 6 ', 8';
from the group of aromatic and araliphatic carboxylic acids and their esters such. B. benzoic acid; phenylacetic acid; methylbenzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methyl phenylacetate; ethyl phenylacetate; geranyl phenylacetate; Phenylethyl phenylacetate; methyl cinnamate; ethylcinnamate; Benzyl; Phenylethylcinnamat; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; isoamyl; hexyl salicylate; cyclohexyl; cis-3-hexenyl salicylate; benzyl; phenylethyl; Methyl-2,4-dihydroxy-3,6-dimethylbenzoate; Ethyl 3-phenylglycidate; Ethyl-3-methyl-3-phenylglycidate;
from the group of nitrogen-containing aromatic compounds such. B. 2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone; cinnamic acid; 5-phenyl-3-methyl-2-pentensäurenitril; 5-phenyl-3-methylpentansäurenitril; methyl anthranilate; Methyl N-methylanthranilate; Schiff bases of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3- (4-tert-butylphenyl) propanal or 2,4-dimethyl-3-cyclohexene carbaldehyde; 6-Isopropyl; 6-Isobutylchinolin; 6-sec-butylquinoline; indole; skatol; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine;
from the group of phenols, phenyl ethers and phenyl esters such. Eg estragole; anethole; eugenol; Eugenylmethylether; isoeugenol; Isoeugenylmethylether; thymol; carvacrol; diphenyl ether; β-naphthyl methyl ether; β-Naphthylethylether; ß-Naphthylisobutylether; 1,4-dimethoxybenzene; Eugenylacetat; 2-methoxy-4-methyl phenol; 2-ethoxy-5- (1-propenyl) phenol; p-Kresylphenylacetat;
from the group of heterocyclic compounds such. 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;
from the group of lactones such. B. 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; 1.15 pentadecanolide; cis- and trans-11-pentadecene-1,15-olide; cis and trans-12-pentadecene-1,15-olide; 1,16-hexadecanolide; 9-hexadecene-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-tridecandioat; coumarin; 2,3-dihydrocoumarin; Octahydrocoumarin.

With other marine fragrances, it is possible with the 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one (I) according to the invention to achieve further odorously interesting combinations and effects; especially in combination with Calone 1951 ^® , even more diverse sea notes (marine notes) can be created.

The the 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one according to the invention containing perfume oils (fragrance mixtures) can be in liquid form, undiluted or diluted with a solvent for Perfumes are used. Suitable solvents this is z. Ethanol, isopropanol, diethylene glycol monoethyl ether, Glycerine, propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethy citrate, Isopropyl myristate, etc.

For In some applications it is advantageous to use 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one containing perfume oils on a carrier adsorbing used for both a fine distribution the fragrances in the product as well as for a controlled Release during use ensures. Such carriers can porous inorganic materials such as light sulphate, silica gels, Zeolites, gypsum, clays, clay granules, aerated concrete etc. or organic Materials such as woods; Cellulose-based substances, sugar or plastics such as PVC, polyvinyl acetates or polyurethanes.

For For other applications it is advantageous to include 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one Perfume oils microencapsulated, spray dried, to be used as an inclusion complex or as an extrusion product and in this form the product to be perfumed add.

The Properties of such modified perfume oils in some cases by so-called "coating" with suitable materials with a view to a more targeted fragrance release further optimized, including preferably waxy plastics such z. As polyvinyl alcohol can be used.

The For example, microencapsulation of the perfume oils by the so-called coacervation method with the aid of capsule materials z. B. made of polyurethane-like substances or soft gelatin. The spray-dried perfume oils can for example, by spray drying a perfume oil containing emulsion or dispersion are prepared, wherein Starch modified starches, proteins, Dextrin and vegetable gums can be used. Inclusion complexes may, for. B. by entry of dispersions of the perfume oil and cyclodextrins or urea derivatives in a suitable solvent, e.g. As water, are produced. Extrusion products can by blending the perfume oils with a suitable one waxy fabric and by extrusion with subsequent solidification, optionally in a suitable solvent, eg. For example isopropanol, respectively.

The The invention further relates to a method for switching, amplifying and / or modifying an odor and / or flavor with a marine, aldehydic, ozone, watery-fresh, fruity and / or floral note, with a sensory effective amount of 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one or an odoriferous or flavoring mixture according to the invention as defined above, preferably in one of the preferred marked embodiments, with a product in contact brought or mixed. A preferred invention Method relates to switching, amplifying and / or Modifying a lily of the valley odor and / or taste.

• – Umsetzen von 4-(3-Methylbut-2-en-1-yl)benzol-l,2-diol zu 7-(3-Methylbut-2-en-1-yl)-2H-1,5-benzodioxepin-3(4H)-on in einem oder mehreren Schritten.

Another aspect of the present invention relates to a process for the preparation of 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one comprising:

• Reacting 4- (3-methylbut-2-en-1-yl) benzene-1,2-diol to 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin 3 (4H) -one in one or more steps.

• a) – Umsetzen von 4-(3-Methylbut-2-en-1-yl)benzol-1,2-diol mit 1,3-Dihalogenaceton in Gegenwart einer Base, oder
• b) – Umsetzen von 4-(3-Methylbut-2-en-1-yl)benzol-1,2-diol mit Bromessigsäuremethylester, und danach
• – Umsetzen des Reaktionsproduktes durch Dieckmann-Kondensation und Decarboxylierung

Preferred is a method according to the invention comprising the following steps:

• a) - reacting 4- (3-methylbut-2-en-1-yl) benzene-1,2-diol with 1,3-dihaloacetone in the presence of a base, or
• b) - reacting 4- (3-methylbut-2-en-1-yl) benzene-1,2-diol with methyl bromoacetate, and thereafter
• - Reaction of the reaction product by Dieckmann condensation and decarboxylation

The preparation of 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one can be prepared according to the preferred process alternative a) from 4- (3-methylbut-2-one en-1-yl) benzene-l, 2-diol by Williamson ether synthesis with 1,3-dihaloacetone in the presence of a base. Preference is given to 4- (3-methylbut-2-en-1-yl) benzene-1,2-diol in analogy to that in EP 1 405 851 with 1,3-dichloroacetone using sodium carbonate as the base and acetone as the solvent to give 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one (see Example 1).

The Intermediate 4- (3-methylbut-2-en-1-yl) benzene-1,2-diol may be, for example by Friedel-Cafts alkylation of pyrocatechol with 3-methylbut-2-en-1-ol in the presence of acids, such as. B. phosphoric acid, be synthesized (see Example 1). Alternatively, starting 4- (3-methylbut-2-en-1-yl) benzene-1,2-diol of 4- (3-methylbut-2-enyl) phenol through a reaction sequence of formylation and Dakin oxidation. Selective ortho-formylation the phenol is preferably carried out by reaction with paraformaldehyde, anhydrous magnesium chloride and triethylamine in tetrahydrofuran as a solvent, followed by an in situ Oxidation with hydrogen peroxide in alkaline medium, analogous to as described in Tetrahedron Letters 2005, 46, 3357-3358 Method.

alternative may be 4- (3-methylbut-2-en-1-yl) benzene-1,2-diol according to the preferred process alternative b) first with methyl bromoacetate to dimethyl 2,2 '- [[4- (3-methylbut-2-en-1-yl) -1,2-phenylene] bis (oxy)] diacetate which are converted by Dieckmann condensation and decarboxylation into 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one is (see Example 2).

The present invention, in another aspect, relates to the novel intermediate 4- (3-methylbut-2-en-1-yl) benzene-1,2-diol. The invention also relates to the use of 4- (3-methyl but-2-en-1-yl) benzene-1,2-diol to produce 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one ,

Farther The present invention relates to a perfumed product comprising 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one or a 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one according to the invention and one or more other fragrances or flavorings Smelling or flavoring mixture as defined above, preferably in a preferred embodiment as the preferred embodiments.

For the production of perfumed according to the invention Products, the inventive 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one in pure form, in solutions or in other modified forms Form to be used. Alternatively, the inventive Containing 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one Perfume oils (perfume mixtures) in concentrated Form, in solutions or in another modified form be used. Perfumed products according to the invention are z. B. Perfume Extraits, Eau de Parfum, Eau de Toilettes, Shaving waters, Eau de Colognes, Pre-shave products, Splash colognes and perfumed refreshment towels as well as acidic, alkaline and neutral cleaning agents such. B. floor cleaner, Window glass cleaner, dishwashing detergent, bath and sanitary cleaner, Scouring milk, solid and liquid toilet cleaners, powder and foam-like carpet cleaners, detergents (eg liquid or powdered detergents), laundry pre-treatment agents such as bleach, soak and stain remover, softener (Laundry softener), laundry soaps, washing tablets, Disinfectants, surface disinfectants as well Air freshener in liquid, gelatinous or on one solid carrier applied form, aerosol sprays, waxes and polishes such as furniture polishes, floor waxes, shoe polishes as well as personal care products such. B. solid and liquid Soaps, shower gels, shampoos, shaving soaps, shaving foams, Bath oils, oil-in-water, cosmetic emulsions, water-in-oil and water-in-oil-in-water type such as 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 such. Hair sprays, hair gels, Hair lotions, hair conditioners, permanent and semi-permanent Hair dyes, hair shaping agents such as cold shafts and Hair straighteners, hair lotions, hair creams and lotions, deodorants and antiperspirants such. B. underarm sprays, Roll-ons, deodorants, deodorants or decorative cosmetics.

For the production of perfumed products according to the invention, the 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one or the fragrance or flavoring mixture according to the invention is regularly combined with ingredients like for example:
Preservatives, abrasives, anti-acne agents, anti-aging agents, antibacterial agents, anti-cellulite agents, anti-dandruff agents, anti-inflammatory agents, anti-irritants, anti-irritants, antimicrobials, antioxidants, astringents, antiperspirants, antiseptics, antistatics, binders, buffers , Carrier materials, chelating agents, cell stimulants, cleansing agents, nourishing agents, depilatory agents, surface-active substances, deodorizing agents, antiperspirants, plasticizers, emulsifiers, enzymes, essential oils, fibers, film formers, fixatives, foaming agents, foam stabilizers, foaming inhibitors, foam boosters, Fungicides, gelling agents, gelling agents, hair care products, hair styling agents, hair straightening agents, moisturizers, moisturisers, moisturisers, bleaching agents, tonics, stain removers, optically brightening anti-caking agents, antisoiling agents, anti-friction agents, lubricants, moisturizers, ointments, opacifiers, plasticizers, masks, polish, brighteners, polymers, powders, proteins, lubricating agents, abrasives, silicones, skin soothing agents, skin cleansers, skin-care agents, skin-healing agents, skin-lightening agents, skin-protecting agents, skin softening agents, cooling agents, skin-cooling agents, warming agents, skin-warming agents, stabilizers, UV-absorbing agents, UV filters, detergents, fabric softeners, suspending agents, skin tanning preparations, thickeners, vitamins, Oils, waxes, fats, phospholipids, saturated fatty acids, mono- or polyunsaturated fatty acids, α-hydroxy acids, polyhydroxy fatty acids, plasticizers, dyes, color protectants, pigments, anti-corrosives, flavors, flavorings, fragrances, polyols, surfactants, electrolytes, organic Solvent or silicone derivatives.

One Another aspect of the present invention relates to the use of 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one or an odoriferous or flavoring mixture according to the invention as defined above (preferably in one of the preferred Embodiments) for increasing the substantivity a fragrance or flavoring mixture

The invention 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one (I) is characterized by a high (inherent) adhesion (substantivity), a low odor threshold, a high diffusivity and very good fixing properties. It has an extremely high self-adhesion compared to Calone 1951 ^® and is able to increase the substantivity of other fragrances or flavorings.

Especially the compound of the invention is 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one of the formula (I) therefore for use in shampoos, fabric softeners and detergents. Another aspect of the present This invention relates to the use of 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one or an odoriferous or flavoring mixture according to the invention as defined above (preferably in one of the preferred Embodiments) in a product selected from the group consisting of shampoos, fabric softeners and washing powders.

The (Eigen-) liability, also substantivity or Aufziehvermögen called, denotes the assets of a connection to adhere to a substrate, from a mostly aqueous phase on a substrate or after washing or rinse to remain on a substrate. This Effect is particularly evident on substrates such as skin, hair and textile fibers (eg cotton, wool, linen, synthetic fibers). Diffusivity is the speed with which the transmission of the fragrance by the Room is perceived. The property, as a "fixator" To be able to act (Fixateureigenschaft) means that the corresponding compound causes the adhesion of other fragrances. This can be z. B. by vapor pressure reduction or odoriferous reinforcement (eg lowering the threshold value).

• – Vermischen von 7-(3-Methylbut-2-en-1-yl)-2H-1,5-benzodioxepin-3(4H)-on mit üblichen Bestandteilen einer Riech- oder Aromastoffmischung, wobei das 7-(3-Methylbut-2-en-1-yl)-2H-1,5-benzodioxepin-3(4H)-on in einer Menge eingesetzt wird, die ausreicht, um in der Riech- oder Aromastoffkomposition eine Geruchs- oder Geschmacksnote zu vermitteln, zu modifizieren und/oder zu verstärken.

Furthermore, the following invention relates to a method for producing a fragrance or flavoring mixture, comprising the following step:

• - mixing 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one with usual constituents of a fragrance or flavoring mixture, wherein the 7- (3-methylbut -2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one is used in an amount sufficient to impart or modify an odor or flavor in the fragrance or flavoring composition and / or to reinforce.

Preferably The amount of 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one ranges a marine, aldehydic, ozone, watery-fresh, fruity and / or floral (especially lily-of-the-valley) odor and / or flavoring, to modify and / or to reinforce.

The described effects of 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one Compound of formula (I) and the particular properties of the invention Fragrance mixtures are particularly evident in the application of Comparison of the temporal change of smell to one Situation in which the compound of the invention is not used.

The The following examples illustrate the invention; unless otherwise stated, parts and percentages are by weight.

Examples:

Example 1: Preparation of 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one by reacting 4- (3-methylbut-2-en-1-yl) benzene-1,2-diol with 1,3-dichloroacetone

Example 1.1: 4- (3-Methylbut-2-en-1-yl) benzene-1,2-diol

A suspension of 50.0 g (455 mmol) pyrocatechol in 50 mL toluene is added at 50 ° C with 1.5 g of phosphoric acid. Subsequently, 35.7 g (414 mmol) of prenol are slowly added dropwise, and the reaction solution is stirred at 50 ° C for a further 3 h. After cooling to room temperature is diluted with diethyl ether and the organic phase with dist. Washed water and saturated NaHCO ₃ solution, dried over Na ₂ SO ₄ , filtered and concentrated in vacuo. The vacuum distillation of the crude product gives 21.4 g (29%) of 4- (3-methylbut-2-en-1-yl) benzene-1,2-diol as an orange oil (bp 144 ° C at 1.2 mbar). Recrystallization in cyclohexane gives the product as a colorless, crystalline solid.
¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 1.66 (s, 3H), 1.71 (s, 3H), 3.18 (d, J = 7.4 Hz, 2H), 5.25 (tsept, J = 7.4 Hz, J = 1.4 Hz, 1H), 5.88 (s _b, 2H), 6:58 (ddt, J = 8.0 Hz, J = 2.0 Hz, J = 0.7 Hz, 1H), 6.66-6.67 (m, 1H), 6.74 (d, J = 8.1 Hz, 1H).
¹³ C-NMR (100 MHz, CDCl _3): δ (ppm) = 17.7, 25.7, 33.6, 115.6, 115.7, 120.8, 123.3, 132.4, 135.2, 141.2, 143.4.

Example 1.2: 7- (3-Methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one

To a suspension of 5.6 g (53 mmol) of sodium carbonate and 670 mg (5 mmol) of potassium iodide in 40 mL of acetone is added under reflux a solution of 4.7 g (26 mmol) of 4- (3-methylbut-2-ene 1-yl) benzene-1,2-diol and 4.0 g (31 mmol) of 1,3-dichloroacetone in 10 ml of acetone are slowly added dropwise. The reaction mixture is heated under reflux for 4 h, then cooled to room temperature, filtered and the filtrate concentrated in vacuo. Purification of the crude product by silica gel chromatography (cyclohexane: ethyl acetate 15: 1) and Kugelrohr distillation yielded 1.6 g (27%) of 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one in the form of a colorless oil (bp 170 ° C at 0.2 mbar). After steaming, colorless crystals of the product are isolated.
¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 1.70 (s, 3H), 1.75 (d, J = 1.1 Hz, 3H), 3.25 (d, J = 7.4 Hz, 2H), 4.67 ( s, 2H), 4.69 (s, 2H), 5.28 (tsept, J = 7.4Hz, J = 1.5Hz, 1H), 6.75-6.79 (m, 1H), 6.79-6.82 (m, 1H), 6.90 (i.e. , J = 8.4 Hz, 1H).
¹³ C-NMR (100 MHz, CDCl _3): δ (ppm) = 17.8, 25.7, 33.4, 75.5, 75.8, 120.4, 120.7, 122.7, 123.5, 133.0, 137.8, 146.3, 148.1, 204.8.

Example 2: Preparation of 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one by Dieckmann condensation of dimethyl 2,2 '- [[4- (3-methylbut-2-en-1-yl) -1,2-phenylene] bis (oxy)] diacetate

Example 2.1: Dimethyl 2,2 '- [[4- (3-methylbut-2-en-1-yl) -1,2-phenylene] bis (oxy)] diacetate

To a solution of 3.3 g (18 mmol) of 4- (3-methylbut-2-en-1-yl) benzene-1,2-diol in 35 ml of methanol, 6.6 g of sodium methoxide solution (30% in methanol) and 5.6 g (37 mmol) of methyl bromoacetate are added dropwise, and the reaction mixture is heated under reflux for 6 h. Then again an addition of 6.6 g of sodium methoxide solution (30% in methanol) and 5.6 g (37 mmol) of methyl bromoacetate, and it is refluxed for a further 6 h. After cooling to room temperature, it is diluted with 100 ml of diethyl ether and filtered. The filtrate is concentrated in vacuo and the residue is taken up in a mixture of water, diethyl ether and saturated ammonium chloride solution (1: 1: 1). The aqueous phase is separated, washed with diethyl ether and the combined organic phases are dried over Na ₂ SO ₄ , filtered and concentrated in vacuo. Purification of the crude product by silica gel chromatography (cyclohexane: ethyl acetate 3: 1) gives 2.9 g (50%) of dimethyl 2,2 '- [[4- (3-methylbut-2-en-1-yl) -1]. 2-phenylene] bis (oxy)] diacetate in the form of a yellow oil.
¹ H-NMR (400 MHz, CDCl _3): δ (ppm) = 1.68-1.70 (m, 3H), 1.73-1.75 (m, 3H), 3.25 (d, J = 7.4 Hz, 2H), 3.78 (s , 3H), 3.79 (s, 3H), 4.69 (s, 2H), 4.71 (s, 2H), 5.27 (tsept, J = 7.4 Hz, J = 1.5 Hz, 1H), 6.69-6.71 (m, 1H) , 6.75 (ddt, J = 8.2 Hz, J = 2.0 Hz, J = 0.7 Hz, 1H), 6.81 (d, J = 8.2 Hz, 1H).
¹³ C-NMR (100 MHz, CDCl _3): δ (ppm) = 17.8, 25.7, 33.7, 52.1, 52.2, 66.7, 66.9, 115.7 (2x), 122.1, 122.9, 132.8, 136.6, 146.0, 147.9, 169.6, 169.7.

Example 2.2: 7- (3-Methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one

To a suspension of 693 mg of sodium hydride (60% in mineral oil, 17 mmol) in 20 mL of tetrahydrofuran are slowly added 2.6 g (8 mmol) of dimethyl 2,2 '- [[4- (3-methylbut-2-ene 1-yl) -1,2-phenylene] bis (oxy)] diacetate, and the reaction mixture is refluxed for 6 hours. After cooling to room temperature is hydrolyzed by the addition of 75 mL of ice water, acidified with 2 M HCl to pH = 2 and extracted with diethyl ether. The combined organic phases are dried over Na ₂ SO ₄ , filtered and concentrated in vacuo. The residue is taken up in 35 ml of ethanol, admixed with 35 ml of 2 M HCl and heated under reflux for 10 hours. After completion of the reaction is hydrolyzed with ice water and washed with diethyl ether. The combined organic phases are washed with water and saturated NaCl solution, dried over Na ₂ SO ₄ , filtered and concentrated in vacuo. There are obtained 0.5 g (27%) of 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one.

Example 3: Perfume oil composition

• DPG = Dipropylenglycol;
• ¹ Handelsname Symrise GmbH & Co. KG, Deutschland;
• ² Handelsname International Flavors & Fragrances Inc., USA;
• ³ Handelsname Givaudan AG, Schweiz;
• ⁴ Handelsname Firmenich S.A., Schweiz.

The below-described perfume oil P is used in practice for perfuming many cosmetic products. Composition: ingredients parts by weight 1. Farenal ^®1 (2,6,10-trimethyl-9-undecenal) 10% DPG 3.0 2. cis-3-hexenol 1.0 3. Leafovert ^® (cis-3-Hexenylmethylcarbonat) 2.0 4. Vertocitral ¹ (2,4-dimethyl-3-cyclohexenecarboxaldehyde) 1.0 5. Galbascone ² (1- (5,5-dimethyl-1-cyclohexen-1-yl) pent-4-en-1-one) 10% DPG 1.0 6. ^®3 Melonal (2,6-dimethyl-5-cherished-1-al) 10% DPG 1.0 7. Dihydromyrcenol 10.0 8. linalyl acetate 45.0 9. Citron oil 20.0 10. Orange oil 5.0 11. Methyl anthranilate 10% DPG 1.0 12. Aldehyde C14 so-called 1.0 13. Lilial ³ (2-methyl-3- (4-tert-butylphenyl) propanal) 20.0 14. Florhydral ³ (3- (3-isopropylphenyl) butanal) 1.0 15. Ethyllinalool 85.0 16. Dimethylbenzylcarbinyl butyrate 1.0 17th day oil 1.0 18. Damascon alpha 10% DPG 3.0 19. Rose de Mai-Base 5.0 20. Hedione ⁴ (methyldihydrojasmonate) 275.0 21. Benzyl salicylate 20.0 22. Undecavertol ³ (4-methyl-3-decene-S-ol) 1.0 23. Iraldeine gamma 6.0 24. Eugenol 10% DPG 2.0 25. Vanillin 1.0 26. Agrumex HC ¹ (2-terf-butylcyclohexylacetate) 10.0 27. Cedarwood oil 20.0 28. Iso E Super ² (2-acetyl-1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethylnaphthalene) 220.0 29 Timberol ^{® 1} (1- (2,2,6-trimethylcyclohexyl) hexan-3-ol) 10.0 30. Evernyl ³ (methyl-2,4-dihydroxy-3,6-dimethylbenzoate) 1.0 31. Ambroxide krist. ¹ (dodecahydro-3a, 6,6,9a-tetramethylnaphtho (2,1-b) furan) 8.0 32. Ethylenbrasylate 100.0 33. Globalide ^®1 (Oxacyclohexadec-11/12-ene-2-one) 35.0 34. dipropylene glycol 76.0 35. BHT Jonol 3.0 total 995.0

• DPG = dipropylene glycol;
• ¹ trade name Symrise GmbH & Co. KG, Germany;
• ² Trade name International Flavors & Fragrances Inc., USA;
• ³ trade name Givaudan AG, Switzerland;
• ⁴ Trade name Firmenich SA, Switzerland.

at Perfume oil P is a fresh-flowery Composition with lily-of-the-valley nuances and with green, fruity and citrusy aspects in the top note and a woody-musky finish Fond.

By Addition of 5.0 parts by weight of 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one results perfume oil composition K. This will the transparent fresh flowery, the lily-of-the-valley character and the slightly watery impression in the middle part and in the afterglow This perfume oil supports and intensifies. 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one (I) the present composition K also an enhanced Liability.

Example 4: Shampoo

The perfume oil composition K from Example 3, containing the inventive 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one was in a dosage of 0.5 parts by weight in a shampoo base of the following composition incorporated: ingredients parts by weight Sodium lauryl ether sulfate (eg Texapon NSO, Cognis Deutschland GmbH) 12 Cocamidopropylbetaine (eg Dehyton K, Cognis Deutschland GmbH) 2 sodium chloride 1.4 citric acid 1.3 Phenoxyethanol, methyl, ethyl, butyl and propylparaben 0.5 water 82.8 total 100

Of the pH of the resulting 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one containing shampoo base was about 6. From her were 100 mL of a 20% by weight aqueous shampoo solution produced. In this shampoo solution were 2 Haarsträhnchen washed together for 2 minutes and then Rinsed under running lukewarm water for 20 seconds. A strand of hair was wet wrapped in aluminum foil and the second strand of hair dried with a hair dryer. Both strands of hair were judged by a panel odor. Both strands of hair showed, in comparison with strands of hair, which with a comparison shampoo containing an equal proportion the basic perfume composition P from example 3 (without 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one) washed, a stronger Lily of the Valley note, the watery impression that was freshness and flowery reinforced, the overall impression as a radiant, rounded and felt more harmonious.

Example 5: Fabric softener

The perfume oil composition K from Example 3, containing the inventive 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one was in a dosage of 0.5 parts by weight in incorporated a fabric softener base of the following composition: ingredients parts by weight Quaternary ammonium methosulfate (esterquat), about 90% (eg Rewoquat WE 18, from Witco Surfactants GmbH) 5.5 Alkyldimethylbenzylammonium chloride, about 50% (eg Preventol R50, Bayer AG) 0.2 Color solution, about 1% 0.3 water 94.0 total 100

The pH of the resulting 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one fabric softener base was in the range of 2 to 3. This became a 1 wt.% Aqueous fabric softener solution prepared. Two rags were rinsed with 370 g of the 1% aqueous fabric softener solution in a Linetest machine in the softening program for 30 minutes at 20 ° C. The flaps were wrung out and then spun for 20 seconds. A rag was wet-sealed, and one hung up to dry. Subsequently, both flaps were assessed by a panel odor. Both rags in comparison with lobes, which according to a comparative fabric softener solution containing an equal proportion of the basic perfume composition P from Example 3 (without 7- (3-methylbut-2-en-1-yl) -2H-1.5 -benzodioxepin-3 (4H) -one), a stronger emphasis of the lily of the valley notes, the fresh, marine impression and the florality were enhanced, the overall impression was perceived as radiant, rounded and harmonious.

Example 6: Washing powder

The perfume oil composition K from Example 3, containing the inventive 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one was in a dosage of 0.4 parts by weight in incorporated a washing powder base of the following recipe: ingredients parts by weight Linear Na-alkylbenzenesulfonate 8.8 Ethoxylated fatty alcohol C12-18 (7 EO) 4.7 Na-soap 3.2 Defoamer DOW CORNING (R) 2-4248S POWDERED ANTIFORM, silicone oil on zeolite as carrier material 3.9 Zeolite 4A 28.3 Na carbonate 11.6 Na salt of a copolymer of acrylic and maleic acid (Sokalan CP5) 2.4 Na silicate 3.0 carboxymethylcellulose 1.2 Dequest 2066 ([[(phosphonomethyl) imino] bis [(ethylenitrilo) bis (methylene)]] tetrakisphosphonic acid, sodium salt) 2.8 Optical brightener 0.2 Na sulfate 6.5 protease 0.4 sodium perborate 22.0 TAED 1.0 total 100

From this A 1% aqueous washing powder liquor was prepared. Two rags were mixed with 370 g of the 1% aqueous Washing powder liquor (the pH of Waschpulaugeauge is significantly in the basic range) in a Linetest machine in the main wash cycle Washed at 60 ° C for 45 minutes. The rags were first Rinsed with cold water for 5 minutes, wrung out and then Thrown for 20 seconds. A rag was wet-sealed and the other hung up to dry. Subsequently Both flaps were judged by a panel odor. Both Lags showed in comparison with lobes, which with accordingly a comparative washing powder liquor containing an equal proportion the basic perfume composition P from example 3 (without 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one) had a stronger emphasis on Lily of the valley note, the fresh, marine impression and the Blumigkeit were strengthened, whereby the overall impression as radiant, rounded and harmonious was felt.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - US 3517031 [0004, 0005]
• - EP 0902024 [0006]
• - EP 1136481 [0007, 0008, 0008]
• - EP 1405851 [0036]

Cited non-patent literature

• - J.-M. Gaudin et al., Helv. Chim. Acta 2007, 90, 1245-1265 [0009]
• Steffen Arctander, Perfume and Flavor Chemicals, Self-Publishing, Montclair, NJ 1969; H. Surburg, J. Panten, Common Fragrance and Flavor Materials, 5th Edition, Wiley-VCH, Weinheim 2006 [0025]

Claims (14)

7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one. Use of 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one as a fragrance and / or flavoring. Use according to claim 2, for imparting, modifying and / or enhancing a marine, aldehydic, ozone, watery-fresh, fruity and / or floral odor and / or flavor, preferably a lily-of-the-valley odor and / or taste note. A fragrance or flavoring mixture comprising 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one and one or more other fragrances or flavorings, in particular one or more fragrances or flavorings with a lily-of-the-valley odor and / or flavor and / or one or more odoriferous or Flavorings with an aqueous odor and / or flavor. A fragrance or flavoring mixture according to claim 4, comprising an amount of 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one, which is sufficient to one or more odor or taste notes selected from the group consisting of marine, aldehydic, ozone, watery-fresh, fruity and / or floral, to modify and / or reinforce. A fragrance or flavoring mixture according to any one of claims 4-5, comprising an amount of 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one in the range of 0.001 to 40% by weight, preferably 0.01 to 25% by weight and in particular 0.1 to 10 wt .-%, based on the total amount the fragrance or aroma composition. Method for switching, amplifying and / or Modifying an odor and / or taste with a marine, aldehydes, ozone, watery-fresh, fruity and / or floral note, with a sensory effective amount of 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one or a fragrance or flavoring mixture according to any one of the claims 4 to 6 is brought into contact or mixed with a product. Process for the preparation of 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one, full: - reacting 4- (3-methylbut-2-en-1-yl) benzene-1,2-diol to give 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one in one or several steps. 4- (3-methylbut-2-en-1-yl) benzene-1,2-diol. Use of 4- (3-methylbut-2-en-1-yl) benzene-1,2-diol for the preparation of 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one. Perfumed product comprising 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one or a fragrance or flavoring mixture according to any one of the claims 4 to 6. Use of 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one or a fragrance or flavoring mixture according to any one of the claims 4 to 6 to increase the substantivity of a Smell or aroma mixture. Use of 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one or a fragrance or flavoring mixture according to any one of the claims 4 to 6 in a product selected from the group consisting from shampoos, fabric softeners and washing powders. Process for the preparation of a fragrance or flavoring mixture, with the following step: - mixing 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one with conventional ingredients of a fragrance or flavoring mixture, wherein the 7- (3-methylbut-2-en-1-yl) -2H-1,5-benzodioxepin-3 (4H) -one is used in an amount sufficient to produce in the odor or flavoring to an odor or flavor mediate, modify and / or reinforce.