EP3968784A1 - Mélange de parfums ou d'arômes - Google Patents

Mélange de parfums ou d'arômes

Info

Publication number
EP3968784A1
EP3968784A1 EP19725698.5A EP19725698A EP3968784A1 EP 3968784 A1 EP3968784 A1 EP 3968784A1 EP 19725698 A EP19725698 A EP 19725698A EP 3968784 A1 EP3968784 A1 EP 3968784A1
Authority
EP
European Patent Office
Prior art keywords
fragrance
formula
iii
compounds
acid diester
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19725698.5A
Other languages
German (de)
English (en)
Inventor
Bernd HÖLSCHER
Vijayanand CHANDRASEKARAN
Johannes Panten
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Symrise AG
Original Assignee
Symrise AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Symrise AG filed Critical Symrise AG
Publication of EP3968784A1 publication Critical patent/EP3968784A1/fr
Pending legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/20—Synthetic spices, flavouring agents or condiments
    • A23L27/202—Aliphatic compounds
    • A23L27/2024—Aliphatic compounds having oxygen as the only hetero atom
    • A23L27/2028—Carboxy compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0007—Aliphatic compounds
    • C11B9/0015—Aliphatic compounds containing oxygen as the only heteroatom
    • C11B9/0019—Aliphatic compounds containing oxygen as the only heteroatom carbocylic acids; Salts or esters thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q13/00—Formulations or additives for perfume preparations
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/593—Dicarboxylic acid esters having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2093—Esters; Carbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/20—Synthetic spices, flavouring agents or condiments
    • A23L27/202—Aliphatic compounds
    • A23L27/2024—Aliphatic compounds having oxygen as the only hetero atom
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/20—Synthetic spices, flavouring agents or condiments
    • A23L27/29—Fruit flavours
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs

Definitions

  • the invention is in the field of fragrances and flavors and relates to fragrance or flavor mixtures with a fruity, pear-like note, a process for the production of fragrances or flavors or fragrance or flavor mixtures with a fruity, pear-like note, the use of this fragrance - Or flavoring mixtures for producing a fruity, pear-like fragrance or flavor note or for producing a fragrance mixture, perfume oils, cosmetic agents, application agents, detergents and cleaning agents, foodstuffs or animal feeds and the products made from them that contain the fragrance or flavoring mixtures.
  • fragrances or fragrances or flavors or aromas that are already present, there is still a general need for new fragrances or flavors in the perfume industry.
  • fragrances or flavors that are not only characterized by new, original fragrances, but also have additional positive secondary properties beyond their olfactory properties, such as, for example, B. higher stability and yield under certain application conditions, better adhesion, greater charisma, a lower odor threshold or better dermatological or toxicological properties, such as good biodegradability.
  • fragrances or flavors which, at a lower dosage, make the same or higher fragrance or taste contribution than comparable substances and thus lead to a lower entry into the environment (low volume - high impact), or which can be made available much cheaper with the same fragrance contribution.
  • fragrances or flavorings with complex smell or taste properties such as fruity pear-like smell or taste properties.
  • Amyl acetate which is otherwise known for its pear-like aroma, does not meet these requirements.
  • fragrances or flavors that can be produced from natural or sustainably produced raw materials, for example from vegetable raw materials or bio-based raw materials, under the aspect of environmental protection, energy and resource efficiency.
  • fragrances or flavors or fragrances or mixtures of flavors that are free of undesirable and health-impairing by-products that can arise during the synthesis of such fragrances.
  • WO 2018/114073 A1 discloses fragrances or fragrance mixtures and their uses, in particular perfume oils, cosmetic agents, application agents or detergents and cleaning agents, which contain a sensorially effective amount of (i) (E) -2-methyl-but- 2-endicarboxylic acid diethyl ester, (ii) (ZJ-2-methyl-but-2-endicarboxylic acid diethyl ester or (iii) 2-methylenebutanedicarboxylic acid diethyl ester or mixtures thereof of these compounds or mixtures of derived analogous esters.
  • the fragrances are made using a series of linear syntheses.
  • the first variant of the process for the preparation of a mono- and / or diester of mesaconic acid comprises the steps that one
  • the second variant of the process for the preparation of a mono- and / or diester of mesaconic acid comprises the steps that:
  • the second alternative production method is used as step (iv) in the first-mentioned production method.
  • the last rearrangement step is thus carried out according to the second alternative production process, as it were following steps (i) to (iii) in the first-mentioned production process.
  • halogen particularly iodine
  • the use of halogen, particularly iodine, in the isomerization requires higher amounts to complete the reaction.
  • the odorant mixture produced during the synthesis is not free from by-products. Some of these by-products are undesirable because they have an adverse effect on the fragrances.
  • the fragrance or flavor mixtures contain halogen, in particular iodine, which is used in the synthesis, in an amount which is well above the guide value of 10 ppm.
  • Iodine (HJ) also leads to discoloration of the fragrance or flavor mixtures, which are undesirable.
  • the procedure therefore requires a further process step to separate the iodine from the fragrance or flavor mixture, for example by washing the fragrance or flavor mixture with sodium disulfite.
  • halogens can attach to double bonds in fragrances or flavors.
  • the deposition leads to a change in the fragrances or flavors and thus to a worsening of the odor profile.
  • halogens can also cause skin irritation such as reddening of the skin.
  • the object of the present invention was therefore to provide fragrances and flavors or fragrance or flavor mixtures with a fruity, pear-like aroma based on renewable raw materials, preferably waste materials, and which overcome the disadvantages mentioned of the prior art , namely which can be produced on the one hand with a shorter reaction time and thus with less technical effort and at lower costs and on the other hand have a high purity, ie are free from by-products, in particular are free from halogens.
  • a first object of the invention relates to a fragrance or flavor mixture comprising a sensorially effective amount of the compounds of the general formula (I), formula (II) and formula (III):
  • the present invention also provides a process for the preparation of a compound of the general formula (I), formula (II) or formula (III) or a mixture comprising one, two or three compounds from the group consisting of compounds of the general formula (I), formula (II) and formula (III), which comprises the following steps:
  • the present invention relates to a fragrance or flavor of the general formula (I), formula (II) or formula (III) or a fragrance or flavor mixture comprising one, two or three compound (s) the group consisting of compounds of the general formula (I), formula (II) and formula (III), obtainable according to the invention Process, the process being carried out in particular without the use of halogen-containing, in particular iodine-containing, reagents.
  • the present invention relates to a method for imparting, modifying or enhancing a fruity, pear-like odor note in a fragrance mixture, a perfume oil, cosmetic agent, application agent or detergent and cleaning agent or for imparting, modifying or intensifying a fruity, Pear-like flavor note in a food, animal feed or pharmaceutical product, comprising the following steps:
  • Flavor mixture which is sufficient to produce a fruity, pear-like odor note or taste note in the finished preparation, with at least one further fragrance or flavor or a mixture of further fragrances or flavors;
  • Flavor mixture which is sufficient to produce a fruity, pear-like odor note or taste note in the finished preparation, with a perfume oil, cosmetic agent, application agent, detergent and cleaning agent, food, animal feed or pharmaceutical product.
  • Flavor mixture which comprises the compounds of the general formula (I), formula (II) and formula (III) for imparting, modifying or intensifying a fruity, pear-like odor or taste note in one
  • Fragrance mixture a perfume oil, cosmetic agent, an application agent or a washing and cleaning agent or for conveying, modifying or enhancing a fruity, pear-like taste note in a food, Animal feed or pharmaceutical product or for the production of a fragrance mixture, a perfume oil, cosmetic agent, application agent, detergent and cleaning agent, foodstuff, animal feed or pharmaceutical product.
  • the present invention relates to a fragrance mixture or a perfume oil, cosmetic agent, application agent, detergent and cleaning agent, food, animal feed or pharmaceutical product that has a sensory effective amount of the fragrance or flavor mixture according to the invention which includes compounds of general formula (I), formula (II) and formula (III).
  • Figure 1 shows schematically the process for the production of fragrances or flavors of the general formulas (I), (II) and (III) or the fragrance or flavor mixtures therefrom with a fruity, pear-like note according to the present invention in comparison with the Method of making the Fragrances or flavorings or fragrance or flavor mixtures with a fruity, pear-like note according to the prior art.
  • Figure 2 shows the 1 H-NMR spectrum (400 MHz, CDCls) of a fragrance or flavor mixture according to the invention.
  • the scale is in f1 (ppm).
  • FIG. 3 shows the 13 C-NMR spectrum (101 MHz, CDCl3) of a fragrance or flavor mixture according to the invention.
  • the scale is in f1 (ppm).
  • the present invention relates to a fragrance or flavor mixture, comprising a sensorially effective amount of the compounds of the general formula (I), formula (II) and formula (III):
  • the fragrance or flavor mixture is characterized in that it is halogen-free, in particular iodine-free.
  • the compounds of the fragrance or flavor mixture according to the invention are preferably an isomer mixture of derivatives of mesaconic acid ((E -2-methyl-but-2-endicarboxylic acid)
  • compounds of the formula (I) in particular are suitable as fruity, pear-like fragrances or flavorings and thereby fully meet the complex requirement profile described above.
  • the compounds of the formula (II) and of the formula (III) are also obtained in the fermentation process and likewise have a weakened pear-like odor or aroma.
  • the fragrance or flavoring mixtures according to the invention are equally suitable as a fragrance or fragrance on the one hand or as a flavoring or aroma on the other hand.
  • the terms “smell” and “taste” on the one hand and “fragrance mixture” and “flavor mixture” on the other hand are used equally alongside one another in the context of the present application and are therefore dependent on the intended use, namely the fragrance on the one hand or the flavoring on the other.
  • the compounds of general formula (I), formula (II) and formula (III) are compounds which are prepared from itaconic acid. Itaconic acid (C5FI6O4) is an organic dicarboxylic acid. It arises among other things in the distillation of citric acid. The technical production of itaconic acid takes place biotechnologically through the submerged fermentation of molasses (by-product of sugar production) and other substrates with strains of the fungi Aspergillus itaconicus or Aspergillus terreus. The compounds of the general formula (I), formula (II) and formula (III) can thus be produced from natural or sustainably produced raw materials.
  • a sensorially effective amount is a proportion of the compounds of the general formula (I), formula (II) and formula (III) which is sufficient to evoke a fruity, pear-like smell or taste impression.
  • This fruity, pear-like smell or taste impression is produced when at least 0.001% by weight of the compounds of the general formula (I), formula (II) and formula (III) are present in the fragrance or flavor mixture.
  • the present invention relates to a fragrance or flavor mixture containing a sensorially effective amount of the compounds of the general formula (I), formula (II) and formula (III) from the group consisting of diesters of mesaconic acid, Citraconic acid and itaconic acid.
  • R1 and / or R2 in the compounds of general formula (I), formula (II) or formula (III) each independently represent a linear or branched alkyl radical having 1 to 10 carbon atoms or a cyclic alkyl radical having 1 to 10 carbon atoms.
  • the linear radicals are particularly preferred here, in particular alkyl radicals having 1 to 4 carbon atoms.
  • branched alkyl radicals with this number of carbon atoms are preferred.
  • the radicals R1 and R2 can be identical or different.
  • the group of preferred linear alkyl radicals for R1 and / or R2 with 1 to 10 carbon atoms in the compounds of general formula (I), formula (II) or formula (III) is formed from the following radical radicals: methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-flexyl, n-heptyl, n-octyl, n-nonyl and n-decyl.
  • Preferred linear alkyl radicals are methyl, ethyl, but n-propyl, n-butyl, n-pentyl and n-flexyl are likewise suitable.
  • linear alkyl radicals are methyl, ethyl, n-propyl and n-butyl. Most preferably the alkyl radical is ethyl.
  • the group of branched alkyl radicals for R1 and / or R2 having 1 to 10 carbon atoms in the compounds of the general formula (I), formula (II) or formula (III) is formed from: isopropyl, isobutyl, sec-butyl , tert-butyl, isopentyl, tert-pentyl, iso-flexyl, tert-hexyl, iso-heptyl, iso-octyl, tert-octyl, iso-nonyl, tert-nonyl, tert-decyl and iso -Decyl.
  • Preferred branched alkyl radicals are isopropyl, isobutyl, sec-butyl and tert-
  • the group of cyclic alkyl radicals for R1 and / or R2 with 1 to 10 carbon atoms in the compounds of general formula (I), formula (II) or formula (III) is formed from: cyclopropane, cyclobutane, cyclopentane, cyclohexane, Cycloheptane and cyclooctane, cyclononane and cyclodecane.
  • Preferred cyclic alkyl radicals are cyclopentane and cyclohexane.
  • araliphatic radicals for R1 and / or R2 in the compounds of general formula (I), formula (II) or formula (III) are to be understood as alkyl radicals on which one or more hydrogen atom (s) is replaced by one aromatic radical is / are replaced.
  • the group of araliphatic radicals in the compounds of the general formulas (I), (II) or (III) is preferably formed from: toluene, 2-methylfuran, 3-methylfuran, picolines, cresols, xylenes,
  • araliphatic radicals are toluene and ethylbenzene.
  • the group of aromatic radicals for R1 and / or R2 in the compounds of the general formula (I), formula (II) or formula (III), formula (I), formula (II) or formula (III) is preferably formed from: pyrimidines, furan, thirane, benzene, naphthalene, phenol, pyridine and benzodiazepines.
  • Preferred aromatic radicals are furan and benzene.
  • radicals R1 and / or R2 in the compounds of general formula (I), formula (II) or formula (III) in the fragrance or flavor mixture described above each independently represent one C1 to C4 radical, ie in particular a methyl, Ethyl, propyl or butyl radical. These compounds are particularly easy to make and show the most impressive odor profiles.
  • the radical R1 in the compounds of the general formulas (I), (II) and (III) in the fragrance or flavor mixture described above is a methyl, ethyl, propyl, and / or butyl radical and the radical R2 in the compounds of the general formula (I), formula (II) or formula (III) in the fragrance or fragrance described above
  • Flavor mixture is a methyl radical or an ethyl radical.
  • the radical R2 in the compounds of the general formula (I), formula (II) or formula (III) in the fragrance or flavor mixture described above is a methyl, ethyl, propyl -, and butyl radical and the radical R1 in the compounds of the general formula (I), formula (II) or formula (III) in the fragrance or flavor mixture described above is a methyl radical or ethyl radical.
  • Invention are the radicals R1 and R2 in the compounds of general formula (I), formula (II) or formula (III) in the fragrance or fragrance described above
  • radicals R1 and R2 in the compounds of the general formula (I), formula (II) or formula (III) in the fragrance or flavor mixture described are each independently selected from the group which is formed by: linear or branched methyl, ethyl, propyl and butyl radicals.
  • the linear alkyl radicals and shorter branched alkyl radicals are suitable for in the
  • radicals R1 and R2 in the compounds of the general formula (I), formula (II) or formula (III) in the fragrance mixture described above are each independently methyl, ethyl, propyl - or butyl residues.
  • the radicals R1 and R2 in the compounds of the general formula (I), formula (II) and formula (III) are each identical.
  • the present invention relates to a fragrance or flavoring mixture comprising a sensorially effective amount of compounds (I), (II) and (III) from the group consisting of:
  • diesters are preferably selected from the group consisting of dimethyl ester, diethyl ester, dibutyl ester or dipropyl ester, in particular diethyl ester.
  • the compounds of general formula (I) are particularly preferred because they have a particularly intense fruity and pear quality -like smell or taste.
  • the compounds of the general formula (II) (citraconic diester) and (III) (itaconic acid diester) are usually obtained together with the mesaconic acid diester as a mixture of isomers in the preparation of the fragrance or flavor mixture, but are less intense in smell or taste than the mesaconic acid diester and therefore only have a minor influence on the overall odor or overall taste of the fragrance or flavor mixture according to the invention.
  • the present invention relates to a fragrance or flavoring mixture comprising a sensorially effective amount of compounds of the general formulas (I), (II) and (III) from the group consisting of:
  • the substance is diethyl (E -2-methylbut-2-enedioate or (EJ-2- Diethylbut-2-dicarboxylate, in which R1 and R2 in the general formula (I) represent an ethyl radical and which is represented by the formula (IV)
  • diethyl (E) -2-methylbut-2-enedioate or (EJ-2-methylbut-2-endicarboxylic acid diethyl ester and mesaconic acid diethyl ester are used synonymously.
  • the compound diethyl (E) -2-methylbut- 2-endioat is characterized by a particularly intense fruity, pear-like smell and taste.
  • Diethyl (ZJ-2-methylbut-2-enedioate or (ZJ-2-methyl-but-2-endicarboxylic acid diethyl ester (diethyl citraconate)) is particularly preferred for the compound of general formula (II) and for the compound general formula (III) of diethyl 2-methylenebutanedioate or 2-methylenebutanedicarboxylic acid diethyl ester (itaconic acid diethyl ester), which together with diethyl (E -2-methylbut-2-enedioate or mesaconic acid diethyl ester) give a preferred mixture of fragrances.
  • the aforementioned compounds of the general formula (II) O ⁇ ei ⁇ - (Z) -2-methylbut-2-enedioate and the general formula (III) diethyl 2-methylene-butanedioate are generally included the mesaconic acid diethyl ester as an isomer mixture in the preparation of the fragrance or flavor mixture, however, are less intense in smell or taste than the mesaconic acid diethyl ester and therefore have only a minor influence on the overall smell or overall taste of the fragrance or flavor mixture according to the invention.
  • fragrance or flavor mixtures or isomer mixtures which contain the compound of the formula (I) in an amount of at least 50 to 100% by weight, more preferably from 60 to 78% by weight, most preferred from 66 to 72% by weight, the compound of the formula (II) in an amount of at least 2 to 8% by weight, more preferably from 3 to 7% by weight and particularly preferably from 4 to 6% by weight .-%, and the compound of the formula (III) in an amount of at least 18 to 31% by weight, more preferably from 20 to 29% by weight and most preferably from 22 to 27% by weight have, based on the sum of the compounds of the general formulas (I), (II) and (III) or based on the total weight of the Mixture of isomers.
  • the compound of the formula (I) in relation to the sum of the two compounds of the formula (II) and the formula (III) in the fragrance or flavor mixture is 3: 1, preferably in the ratio 2.5: 1, even more preferably in a ratio of 1.5: 1.
  • These ratios also apply preferably to the compound mixture of diethyl (EJ -2-methylbut-2-enedioate or mesaconic acid diethyl ester to diethyl (ZJ-2-methylbut-2-enedioate (citraconic acid diethyl ester) and diethyl 2-methylene-butanedioate (itaconic acid di ethyl ester).
  • the ratio of the compound of the formula (I) to the compound of the formula (II) is in a range from 66: 6 to 72: 4. Particularly good sensory results are achieved in this range.
  • the proportion of the compounds of the general formulas (II) and (III) in the fragrance or flavor mixture according to the invention therefore has only a minor influence on the overall odor or overall taste of the fragrance or flavor mixture, which is determined in particular by the proportion of compound of the formula (I ) is coined.
  • a change i.e. an increase in the proportion of the compounds of the formulas (II) and (III) in relation to the compound of the formula (I) therefore also does not lead to a change, i.e. to an intensification, of the smell or taste.
  • mesaconic acid diester in particular of the mesaconic acid diethyl ester, (compound of the formula (I)
  • a higher proportion of the mesaconic acid diester, in particular of the mesaconic acid diethyl ester, (compound of the formula (I)) in the mixture according to the invention can also be achieved, for example, by concentration.
  • the fragrance or flavor mixture according to the present invention is characterized by a high degree of purity, ie that it does not contain any impurities and by-products that occur in the synthesis of the compounds of the general formula (I), formula (II) or formula (III ) arise.
  • the compounds of general formula (I), formula (II) and formula (III) have a purity of at least 98.0%, preferably a purity of 100%.
  • mesaconic acid diethyl ester has a purity of at least 98.0%, but above all a 100.0% purity.
  • a mixture of fragrances or flavorings with pure or almost pure diethyl mesaconate shows a particularly strong odor with a pear note.
  • the fragrance or flavor mixture according to the present invention comprises or consists of compounds of the general formulas (I), (II) and (III) in a sensorially effective amount.
  • a sensorially effective amount is to be understood as meaning a proportion of the compounds of the general formulas (I), (II) and formula (I) which is sufficient to produce a fruity, pear-like odor or taste impression.
  • the compounds of general formula (I), formula (II) and formula (III) are contained in the fragrance or flavor mixture in an amount of together 0.001 to 99.999% by weight, based on the total weight of the fragrance or flavor mixture.
  • the compounds of general formula (I), formula (II) and formula (III) are contained in the fragrance or flavor mixture in an amount of together 0.05 to 50% by weight, based on the total weight the fragrance or flavor mixture.
  • the compounds of the general formula (I), formula (II) and formula (III), in particular the dimethyl esters, diethyl esters, dibutyl esters or dipropyl esters are contained in the fragrance or flavor mixture in an amount of together 0.5 to 30% by weight, based on the total weight of the fragrance or flavor mixture.
  • the fragrance or flavor mixture contains diethyl (EJ-2-methylbut-2-enedioate or the mesaconic acid diethyl ester in a mixture with diethyl (ZJ-2-methylbut-2-endioate (citraconic acid diethyl ester ) and diethyl 2-methylene-butanedioate (itaconic acid diethyl ester), in a total amount of 0.001 to about 99.999% by weight, preferably in an amount of about 0.01 to about 90% by weight, preferably in an amount of about 0.05 to about 50% by weight and particularly preferably in an amount of about 0.5 to about 30% by weight.
  • diethyl (EJ-2-methylbut-2-enedioate or the mesaconic acid diethyl ester in a mixture with diethyl (ZJ-2-methylbut-2-endioate (citraconic acid diethyl ester ) and diethyl 2-methylene-butanedioate (itac
  • the fragrance or flavor mixture according to the present invention is characterized by an intense fruity, pear-like fragrance or taste and more volume, which is qualitatively and quantitatively the same as the ethyl decadienoate standard or even exceeds it, as shown in the table below 2 shows.
  • the fragrance or flavor mixture according to the present invention does not contain any halogen impurities or halogen by-products, in particular no iodine impurities or iodine by-products, since no halogen reagents, in particular no iodine, are used in their production - Reagents that are used in the method according to the prior art are used.
  • Such impurities or by-products can lead to discoloration or adversely affect the fragrances, as described in detail above in the introductory part.
  • the fragrance mixtures according to the invention are also more skin-friendly and do not cause any reddening of the skin.
  • the excellent material properties such as solubility in conventional cosmetic solvents, compatibility with other constituents, are also such Products and the toxicological harmlessness of the compounds of the general formula (I), formula (II) and formula (III) of the fragrance or flavoring mixture according to the invention should be mentioned, which underline the particular suitability for the purposes mentioned.
  • the fragrance or flavor mixture according to the invention can preferably contain one or more further (customary) active ingredients or functional ingredients, also one or more other fragrances that do not meet the criteria of the compounds of the general formulas (I), (II) and (III), which make up 100% by weight of the total in the fragrance or flavor mixture.
  • Fragrance or flavor mixtures according to the invention can be used in liquid form, undiluted or diluted with a solvent, for perfuming or flavoring.
  • a solvent for perfuming or flavoring.
  • Suitable and preferred solvents for this are in particular ethanol, glycerol, 1,2-propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate and triacetin.
  • Such fragrance or flavor mixtures contain up to 90% by weight, preferably about 5 to about 70% by weight, in particular about 10 to about 50% by weight and particularly preferably about 15 to about 25% by weight. % of the solvents mentioned.
  • the fragrances or flavoring mixtures according to the invention comprise synthetic or natural, preferably tasteless and odorless, carrier substances, in particular carrier oils, which contain the fragrances in highly concentrated form and optionally perfumery solvents and / or auxiliaries.
  • carrier oils for some applications it is also advantageous to adsorb the fragrance or flavoring mixtures according to the invention on a carrier which ensures both a fine distribution of the fragrances contained therein in the product and a controlled release during use.
  • Such carriers can be porous inorganic materials such as light sulfate, silica gels, zeolites,
  • fragrance mixture according to the invention and carrier material represents an exemplary product according to the invention.
  • the fragrance or flavor mixtures according to the invention are in microencapsulated or spray-dried form or as inclusion complexes or as extrusion products in order to be added in this form, for example, to a product to be perfumed or flavored.
  • Flavor mixtures can, for example, by the so-called coacervation process with the aid of capsule materials e.g. made of polyurethane-like substances or soft gelatine.
  • capsule materials e.g. made of polyurethane-like substances or soft gelatine.
  • Flavor compositions can be produced, for example, by spray-drying an emulsion or dispersion containing the fragrance or flavor mixture according to the invention, wherein modified starches, proteins, dextrin and vegetable gums can preferably be used as carriers.
  • Inclusion complexes can be produced, for example, by introducing dispersions of a fragrance mixture according to the invention and cyclodextrins or urea derivatives into a suitable solvent, for example water.
  • Extrusion products can be obtained by fusing a fragrance or flavoring mixture according to the invention with a suitable waxy substance and by extrusion with subsequent solidification, optionally in a suitable solvent, for example isopropanol. If necessary, the properties of fragrance or flavoring mixture preparations modified in this way can be further optimized by so-called “coating” with suitable materials with a view to a more targeted fragrance release, for which purpose waxy plastics such as polyvinyl alcohol are preferably used.
  • the fragrance or flavoring mixtures according to the invention advantageously contain at least one further fragrance or flavoring or aroma, i.e. two, three, four, five or even far more other fragrance or flavor components, or consist of the isomer mixture of the compounds of the general formula (I), formula (II) and formula (III) according to the present invention, and in particular diethyl -fE ⁇ -methylbut ⁇ -endioate, diethyl- (ZJ-2-methylbut-2-enedioate and diethyl-2-methylene-butanedioate, in a sensory effective amount with at least one further or more fragrance or flavor (s) Fragrances or flavors are not used in binary or ternary mixtures, but as a component of sophisticated, complex mixtures that can contain two, three, four, five, ten, but preferably a far higher number of fragrances or flavors, sometimes in very small quantities, In this sense, the present mixtures of the invention are also to be understood, namely as a mixture of the isomer mixture of
  • the described fragrance or flavor mixture therefore contains any number of other fragrances or flavorings selected from the group formed by: (1) hydrocarbons; (2) aliphatic alcohols; (3) aliphatic aldehydes and their acetals; (4) aliphatic ketones and their oximes; (5) aliphatic sulfur-containing compounds; (6) aliphatic nitriles; (7) esters of aliphatic carboxylic acids; (8) acyclic terpene alcohols; (9) acyclic terpene aldehydes and ketones; (10) cyclic terpene alcohols; (11) cyclic terpene aldehydes and ketones; (12) cyclic alcohols; (13) cycloaliphatic alcohols; (14) cyclic and cycloaliphatic ethers; (15) cyclic and macrocyclic ketones; (16) cycloaliphatic aldehydes; (17) cycloaliphatic ketones; (18) esters
  • fragrances or flavors are very extensive; Corresponding substances with which the compounds of the general formula (I), formula (II) and formula (III) according to the invention can be advantageously combined, can be found, for. B. in “S. Arctander, Perfume and Flavor Chemicals, Volumes I and II, Montclair, N. J., 1969, self-published “or” H. Surburg and J. Panten, Common Fragrance and Flavor Materials, 6th edition, Wiley-VCH, Weinheim, 2016 “and which are not already part of the inventive mixture of the compounds of the general formula (I), formula (II) and formula (III ) are.
  • Extracts from natural raw materials This group stands for essential oils, concretes, absolutes, resins, resinoids, balms, tinctures such as.
  • Individual fragrances can be divided into a large number of classes, namely:
  • Hydrocarbons e.g. 3-carene; a-pinene; ß-pinene; a-terpinene; g-terpinene; p-cymene; Bisabolene; Camphene; Caryophyllene; Cedren; Ferns; Limonene; Longifolene; Myrcene; Ocimen; Valencene; (E, Z) ⁇ 1, 3,5-undecatriene; Styrene; Diphenylmethane;
  • Aliphatic alcohols such as hexanol; Octanol; 3-octanol; 2,6-dimethylheptanol; 2-methyl-2-heptanol; 2-methyl-2-octanol; (E) - 2-flexenol; (E) - and (ZJ-3-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, ZJ-2,6-nonadienol; 3,7-dimethyl-7-methoxyoctan-2-ol; 9-decenol; 10-undecenol; 4-methyl-3-decen-5-ol;
  • Aliphatic aldehydes and their acetals such as e.g. Hexanal; Heptanal; Octanal; Nonanal; Decanal; Undecanal; Dodecanal; Tridecanal; 2-methyloctanal; 2-methylnonanal; (E) - 2-hexenal; (ZJ-4-heptenal; 2,6-dimethyl-5-heptenal; 10-undecenal; (E) -4-decenal; 2-dodecenal; 2,6,10-trimethyl-9-undecenal; 2,6,10 - Trimethyl-5,9-undecadienal; heptanaldiethylacetal; 1,1-dimethoxy-2,2,5-trimethyl-4-hexene; citronellyloxyacetaldehyde; 1 - (1-methoxy-propoxy) - (E, Z) -3-hexene ;
  • Aliphatic ketones and their oximes such as e.g. 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;
  • Aliphatic sulfur-containing compounds such as e.g. 3-methylthio-hexanol; 3-methylthiohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercapto hexyl butyrate; 3-acetylthiohexyl acetate; 1-menthen-8-thiol;
  • Aliphatic nitriles such as e.g. 2-nonenenitrile; 2-undecenoic acid nitrile; 2-tridecenoic acid nitrile; 3,12-tridecadienoic acid nitrile; 3,7-dimethyl-2,6-octadiene-acid nitrile;
  • Esters of aliphatic carboxylic acids such as e.g. (E) - and (Z) - 3-hexenyl formate; Ethyl acetoacetate; Isoamyl acetate; Hexyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate; ('EJ-2-hexenyl acetate; (E) - and (Z) - 3-hexenyl acetate; octyl acetate; 3-octyl acetate; 1-octen-3-ylacetate; ethyl butyrate; butyl butyrate; isoamyl butyrate; hexyl butyrate; (E) - and (ZJ -3-hexenyl isobutyrate; hexyl crotonate; ethyl isovalerate; ethyl 2-methylpentanoate; ethyl
  • Acyclic terpene aldehydes and ketones such.
  • Cyclic terpene alcohols such as. B. menthol; Isopulegol; alpha-terpineol; Terpinenol-4; Menthan-8-ol; Menthan-1-ol; Menthan-7-ol; Borneol; Isoborneol; Linalool oxide; Nopoly; Cedrol; Ambrinol; Vetiverol; Guajol; and their formates, acetates, propionates, isobutyrates, butyrates, isovalerianates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoates;
  • Cyclic terpene aldehydes and ketones such.
  • Cyclic alcohols such as, 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; Cycloaliphatic alcohols such as 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; 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-
  • Cyclic and cycloaliphatic ethers such as e.g. Cineole; Cedryl methyl ether; Cyclododecyl methyl ether; 1,1-dimethoxycyclododecane;
  • Cyclic and macrocyclic ketones such as e.g. 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) -indanone; 8-cyclohexadecen-1-one; 9-cycloheptadecen-1-one; Cyclopentadecanone;
  • Cycloaliphatic aldehydes such as e.g. 2,4-dimethyl-3-cyclohexenecarbaldehyde;
  • Cycloaliphatic ketones such as. B. 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-naphtalenyl methyl ketone; Methyl 2,6,10-trimethyl-2,5,9-cyclododecatrienyl ketone; tert-butyl- (2,4-dimethyl-3-cyclohexen-1 -yl) ketone;
  • Esters of cyclic alcohols such as e.g. 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert-pentylcyclohexyl acetate; 4-tert-pentylcyclohexyl acetate; 3,3,5-trimethylcyclohexyl acetate; Decahydro-2-naphthyl acetate; 2-cyclopentylcyclopentyl crotonate; 3-pentyl tetrahydro-2H-pyran-4-ylacetate; 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-indenyl propionate; 4,
  • Esters of cycloaliphatic alcohols such as 1-cyclohexylethyl crotonate
  • Esters of cycloaliphatic carboxylic acids such as. B. allyl 3-cyclohexyl propionate; Allylcyclohexyloxyacetate; cis and trans methyl dihydrojasmonate; cis and trans methyl jasmonate; Methyl 2-hexyl-3-oxocyclopentanecarboxylate; Ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate; Ethyl 2,3,6,6-tetramethyl-2-cyclohexene carboxylate; Ethyl 2-methyl-1,3-dioxolane-2-acetate;
  • Araliphatic alcohols such as e.g. Benzyl alcohol; 1-phenylethyl alcohol; 2-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-phenyl-propanol; 2-methyl-5-phenylpentanol; 3-methyl-5-phenylpentanol; 3-phenyl-2-propen-1-ol; 4-methoxybenzyl alcohol; 1 - (4-isopropylphenyl) ethanol;
  • Esters of araliphatic alcohols and aliphatic carboxylic acids such as, 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;
  • Araliphatic ethers such as e.g. 2-phenylethyl methyl ether; 2-phenylethyl isoamyl ether; 2-phenylethyl-1-ethoxyethyl ether;
  • Phenylacetaldehyde dimethyl acetal Phenylacetaldehyde diethyl acetal;
  • Aromatic and araliphatic aldehydes such as. B. benzaldehyde; Phenylacetaldehyde; 3-phenylpropanal; Hydratropaaldehyde; 4-methylbenzaldehyde; 4-methylphenylacetaldehyde; 3- (4-ethylphenyl) -2,2-dimethylpropanal; 2-methyl-3- (4-isopropylphenyl) propanal; 2-methyl-3- (4-tert-butylphenyl) propanal; 2-methyl-3- (4-isobutylphenyl) propanal; 3- (4-tert-butylphenyl) propanal; Cinnamaldehyde; alpha-butyl cinnamaldehyde; alpha-amylcinnamaldehyde; alpha-hexyl cinnamaldehyde; 3-methyl-5-phenylpentanal; 4-methoxybenzaldehyde; 4-hydroxy-3-
  • Aromatic and araliphatic ketones such as e.g. 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-indanyl methyl ketone; 6-tert-butyl-1,1-dimethyl-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
  • Aromatic and araliphatic carboxylic acids and their esters such as, for example, benzoic acid; Phenylacetic acid; Methyl benzoate; Ethyl benzoate; Hexyl benzoate; Benzyl benzoate; Methylphenyl acetate; Ethyl phenyl acetate; Geranyl phenyl acetate; Phenylethyl phenyl acetate; Methylcinnmat; Ethyl cinnamate; Benzyl cinnamate; Phenylethyl cinnamate; Cinnamyl cinnamate; Allyl phenoxyacetate; Methyl salicylate; Isoamyl salicylate; Hexyl salicylate; Cyclohexyl salicylate; Cis-3-hexenyl salicylate; Benzyl salicylate; Phenylethyl salicylate; Methyl 2,4-dihydroxy
  • Nitrogen-containing aromatic compounds such as e.g. 2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert-butyl acetophenone;
  • Phenols, phenyl ethers and phenyl esters such as e.g. Estragole; Anethole; Eugenol; Eugenyl methyl ether; Isoeugenol; Isoeugenyl methyl ether; Thymol; Carvacrol; Diphenyl ether; beta-naphthyl methyl ether; beta-naphthyl ethyl ether; beta-naphthyl isobutyl ether; 1,4-dimethoxybenzene; Eugenyl acetate; 2-methoxy-4-methylphenol; 2-ethoxy-5- (1-propenyl) phenol; p-cresylphenyl acetate;
  • Heterocyclic compounds such as e.g. 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;
  • Lactones such as, 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; cis- and trans-11-pentadecen-1, 15-olide; cis- and trans-12-pentadecen-1, 15-olide; 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
  • the present invention relates to a process for preparing a compound of the general formula (I), formula (II) or formula (III) or a mixture comprising one, two or three compounds from the group which consists from compounds of the general formula (I), formula (II) and formula (III), which comprises the steps:
  • step (a)) of the process according to the invention itaconic acid is esterified with an approximately equimolar amount or in excess of alcohol.
  • the reaction is acid-catalyzed, preferably using sulfuric acid or p-toluenesulfonic acid, carried out under reflux. Unreacted alcohol is then distilled off. The diester of itaconic acid is obtained.
  • the acid-catalyzed esterification step of the itaconic acid takes place according to customary process conditions known to a person skilled in the art.
  • step (b)) of the process according to the invention the isomerization of the itaconic acid diester obtained in the first step takes place under Use of an organic nitrogen-containing base to obtain one or more of the compound (s) from the group consisting of compounds of the general formula (I), formula (II) and / or formula (III) in general or to obtain one or more the compound (s) from the group consisting of diesters of mesaconic acid, citraconic acid and / or itaconic acid in particular.
  • This isomerization reaction is preferably carried out in a solvent and requires temperatures of 100 to 150 ° C. Here, too, the solvent is then removed.
  • step (b) the process for production in which a high-boiling solvent is used in step (b) is particularly preferred.
  • the high-boiling solvent preferably contains solvents having a boiling point higher than 250 ° C, more preferably higher than 300 ° C.
  • Polyalkylene glycol (PAG) -based products have proven themselves here. Such are for example Synalox® 50-B SYNALOX TM 50-xB, which are known as lubricants, and are alcoholic materials that contain oxyethylene and oxypropylene groups with a single terminal hydroxyl group with the structure: RO- [CH2- C (CH3) H0] n- [CH2CH 2 0] mH.
  • a solvent system is used as protective solvent in step (b), comprising a high-boiling solvent with a boiling point of more than 150 ° C and further comprising a co-solvent with a boiling point of between 90 ° C and 120 ° C.
  • This system increases the yield significantly, because without the protective solvent the distilled product tends to polymerize on a large scale with larger reaction vessels over the longer distillation route. It could be shown that the yield could be increased even with larger batches, or remains high if the protective solvent has a boiling point so that it can also be distilled with the product in order to prevent the product from polymerizing during the distillation.
  • the cosolvent particularly preferably has a boiling point of between 95 ° C. and 110 ° C., particularly preferably from 100 ° C to 105 ° C.
  • the protective solvent or the co-solvent can after
  • Distillation step can be separated by common methods.
  • Suitable protective solvents or co-solvents are:
  • aliphatic hydrocarbons and in particular paraffins, preferably octane, isooctane, nonane, decane, undecane or tetradecane;
  • Aromatic hydrocarbons preferably toluene, xylenes, ethylbenzene, diethylbenzene, trimethylbenzene, cumene, pseudocumene or petroleum fractions, which consist of a mixture of alkylbenzenes, in particular the fractions of the Solvesso® type;
  • chlorinated aliphatic hydrocarbons preferably 1, 1, 2-trichloroethane, pentachloroethane, 1-iodo-2-methylpropane, 1-chlorohexane or 1-chloro-2-ethylhexane;
  • chlorinated aromatic hydrocarbons preferably chlorobenzene or chlorotoluenes
  • ethers in particular aliphatic ethers, preferably butyl ether, isobutyl ether, ethylhexyl ether, 1-butoxy-2-methoxyethane, 1,1-diethoxybutane, amyl ether, isoamyl ether or dipropoxymethane;
  • aromatic ethers preferably phenylpropyl ether or mesityl oxide
  • nitrated compounds preferably nitropropane or nitrobenzene
  • aliphatic, cycloaliphatic or aromatic ketones preferably methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl n-amyl ketone, methyl isoamyl ketone, cyclohexanone, methyl cyclohexanone or diacetone alcohol.
  • a solvent system composed of the high-boiling solvent polyalkylene glycol (PAG) and the cosolvent has proven to be particularly advantageous
  • esterification ie for the preparation of the itaconic acid diester, aliphatic, araliphatic or aromatic alcohols having 1 to 10 carbon atoms or polyols having 2 to 6 hydroxyl groups, of which preferably diols, are used in step (a) of the process according to the invention.
  • methanol, ethanol or propanol are used for the esterification of the itaconic acid.
  • the use of a combination, i. a mixture of methanol, ethanol and / or propanol for esterification is also possible.
  • step (b) of the process according to the invention takes place using an organic nitrogen-containing Base instead of a catalyst.
  • the organic nitrogenous base is selected from the group consisting of TM EDA (N, N, N ', N'-tetramethylethylenediamine) (boiling point: 121 ° C), TEA (tetraethylamine) (boiling point: 89 ° C) , Dibutylamine (boiling point: 159.6 ° C), pyridine (boiling point: 115 ° C), NMP (N-methyl-2-pyrrolidone) (boiling point: 202 ° C), trioctylamine (boiling point: 365 ° C) and mixtures of the aforementioned compounds.
  • TM EDA N, N, N ', N'-tetramethylethylenediamine
  • TEA tetraethylamine
  • Dibutylamine (boiling point: 159.6 ° C)
  • pyridine boiling point: 115 ° C
  • NMP N-
  • An advantage of isomerization with an organic nitrogen-containing base is that the N-base differs well from the products, ie the compounds of the general formula (I), formula (II) or formula (III), due to different boiling points after the isomerization, can be separated.
  • the separation of the N-base from the products or the recovery of the N-base in the process according to the invention is carried out by distillation. After the distillation, the N-base can be used again in the process according to the invention.
  • the organic nitrogenous bases used in the process of the invention also have the advantage that they do not adversely affect the odor or taste profile of the products obtained.
  • the isomerization of the itaconic acid diester using TMEDA has proven to be due to its different boiling point and thus its easy separability from the compounds of the general formula (I), formula (II) or formula (III) especially turned out to be advantageous.
  • TMEDA the reaction time of the isomerization of the itaconic acid diester can also be significantly reduced and, moreover, leads to the best results with regard to the mixing ratios of the compounds of the general formulas (I), (II) and (III), as follows will be described in detail.
  • the isomerization of the itaconic acid diester in step (b) of the process according to the invention is carried out for a period of 1 to 5 hours in order to achieve optimum isomerization of the itaconic acid diester to the compounds of the general formulas (I), (II) and (III) receive.
  • the isomerization is preferably carried out for a period of 2 to 3 hours.
  • the process according to the present invention results in isomer mixtures or fragrance or flavor mixtures, in which the compound of the formula (I), in an amount of at least 50 to 100% by weight, more preferably from 60 to 78% by weight % and particularly preferably from about 66 to 72% by weight, the compound of the formula (II) is contained in an amount of at least 2 to 8% by weight, even more preferably from 3 to 7% by weight and particularly preferably from 4 to 6% by weight, and the compound of the formula (III) in an amount of at least 18 to 31% by weight, even more preferably from 20 to 29% by weight and most is preferably contained from 22 to 27 wt .-%, based on the sum of the compounds of general formula (I), formula (II) and formula (III) or based on the total weight of the isomer mixture.
  • the above-mentioned mixing ratios also apply to the compound mixtures of the particularly preferred dimethyl esters, diethyl esters, dipropyl esters or dibutyl esters, in particular the diethyl esters, mesaconic acid, citraconic acid and itaconic acid.
  • the compound of the formula (I) is 3 to 1 in relation to the sum of the two compounds of the formula (II) and the formula (III) in the fragrance or flavor mixture , preferably in a ratio of 2.5: 1, even more preferably in a ratio of 1.5: 1.
  • These relationships also apply to the Mixtures of compounds of the respective preferred dimethyl esters, diethyl esters, dipropyl esters or dibutyl esters, in particular diethyl esters, of mesaconic acid, citraconic acid and itaconic acid. Higher proportions of mesaconic acid esters produce a stronger pear odor.
  • the process according to the invention also leads to a compound of the general formula (I) or to a fragrance or flavor mixture which comprises the compound of the general formula (I), in particular the respective dimethyl esters, diethyl esters, dipropyl esters or dibutyl esters of mesaconic acid , in at least 98.0%, but above all in 100.0% purity.
  • a fragrance or flavor mixture with pure or almost pure mesaconic acid diesters, in particular mesaconic acid diethyl ester has a particularly strong odor with a pear note.
  • a preferred embodiment of the process according to the present invention also relates to a process for preparing a compound (E) -2-methylbut-2-endicarboxylic acid diester (mesaconic acid diester), (ZJ-2-methylbut-2-endicarboxylic acid diester (citraconic acid diester) or 2 -
  • Methylenebutanedicarboxylic acid diester (itaconic acid diester) or for the preparation of a mixture comprising one, two or three compounds from the group consisting of (EJ-2-methylbut-2-endicarboxylic acid diester (mesaconic acid diester), (Z) - 2-methylbut-2-endicarboxylic acid diester Citraconic diester), and 2-methylenebutanedicarboxylic acid diester (itaconic acid diester), which comprises the steps:
  • Citraconic diester or 2-methylenebutanedicarboxylic acid diester (itaconic acid diester) or a mixture comprising one, two or three compounds from the group consisting of (EJ-2-methylbut-2- endicarboxylic acid diester (mesaconic acid diester), (ZJ-2-methyl-but-2-endicarboxylic acid diester (citraconic acid diester), and 2-
  • Methylenebutanedicarboxylic acid diester (itaconic acid diester).
  • the diesters of mesaconic acid, citraconic acid and / or itaconic acid according to the general formulas (I), (II) and (III) obtained in the process described above are diethyl esters, namely diethyl- (EJ-2 -nnethylbut-2-enedioat, diethyl- (ZJ-2-methylbut-2-enedioate or diethyl-2-methylene-butanedioate or mixtures comprising one, two or three compounds from the group consisting of diethyl- (EJ-2 methylbut-2-enedioate, diethyl (ZJ-2-methylbut-2-enedioate and diethyl 2-methylene-butanedioate.
  • diethyl esters namely diethyl- (EJ-2 -nnethylbut-2-enedioat, diethyl- (ZJ-2-methylbut-2-enedioate or diethyl-2-methylene-butanedi
  • the process according to the invention results in an isomer mixture or a fragrance or flavor mixture in which diethyl (E -2-methylbut-2-enedioate or mesaconic acid diethyl ester (compound of formula (I)) in an amount of at least 50 to 100% by weight, more preferably from 60 to 78% by weight, most preferably from 66 to 72% by weight, diethyl (ZJ-2-methylbut-2-enedioate (compound of the formula (II)) is contained in an amount of at least 2 to 8% by weight, even more preferably from 3 to 7% by weight and particularly preferably from 4 to 6% by weight, and diethyl-2-methylene butanedioate (compound of formula (III)) is contained in an amount of at least 18 to 31% by weight, more preferably from 20 to 29% by weight and most preferably from 22 to 27% by weight, based on the sum of the compounds of the general formula (I), formula (II) and formula (III) or
  • the method according to the present invention is distinguished in comparison to the method according to WO 2018/114073 A1 in that there is less, i.e. comprises only two and shorter synthesis steps, i.e. the total reaction time is shorter.
  • Another advantage of the process according to the invention is that the isomerization of the itaconic acid diester without using a halogen, in particular iodine, but using an organic Nitrogen-containing base is carried out.
  • the use of an organic nitrogenous base is also not offensive to smell.
  • iodine as a catalyst in isomerizing the citraconic esters to the mesaconic esters and itaconic esters in the prior art process requires a large amount of iodine to complete the isomerization reaction. This in turn requires an additional step of purifying the resulting product in order to separate off excess iodine from the reaction mixture.
  • the use of iodine also leads to the addition of double bonds, which in turn requires subsequent dehydrohalogenation.
  • the large-scale production of the fragrance or flavor mixtures has a higher iodine content in the end product, due to the larger amounts of iodine.
  • the large-scale production of the fragrance or flavor mixture according to the invention leads to iodine-free end products. Therefore, the method according to the present invention is particularly advantageous.
  • the fragrance or flavor mixtures produced by the process according to the prior art are not free from impurities and by-products. Some of these impurities and by-products are undesirable because they have an adverse effect on the fragrances.
  • the fragrance or flavor mixtures contain halogen, in particular iodine, which is used in the synthesis.
  • Such impurities of iodine are not present in the fragrance or flavoring mixtures which are prepared by the process according to the invention, since the synthesis does not require the use of halogen, in particular iodine.
  • the method according to the present invention has the further advantage that it provides higher yields compared to the method according to WO 2018/114073 A1.
  • the yield in the process according to the invention is> 90%, preferably> 97%.
  • the yields are in the process according to WO 2018/114073 A1 at approx. 60%.
  • unreacted starting material can be used in a further synthesis process.
  • the present invention relates to fragrances of the general formula (I), formula (II) or formula (III) or a fragrance or flavor mixture comprising one, two or three compound (s) from the group , which consists of compounds of the general formula (I), formula (II) and formula (III), which are obtainable by the process according to the invention, the process being distinguished in particular by the fact that it is possible without the use of flalogen-containing, in particular iodine containing reagents.
  • a fourth aspect of the invention therefore relates to a method for imparting, modifying or enhancing a fruity, pear-like odor note in a fragrance mixture, a perfume oil, cosmetic agent, application agent or detergent and cleaning agent, or for imparting, modifying or intensifying a fruity, pear-like smell A flavor note in a food, animal feed or pharmaceutical product, comprising the following steps:
  • Flavor mixture which is sufficient to evoke a fruity, pear-like odor or taste note in the finished preparation, with at least one further fragrance or flavor or a mixture of further fragrances or flavors;
  • Flavor mixture that is sufficient to evoke a fruity, pear-like smell or taste note in the finished preparation, with a perfume oil, cosmetic agent, application agent, detergent and cleaning agent, food, animal feed or pharmaceutical product.
  • Methylenebutanedicarboxylic acid diester (itaconic acid diester). This applies in particular to the respective mixtures of the particularly preferred dimethyl esters, diethyl esters, dipropyl esters or dibutyl esters.
  • Another aspect of the invention relates to the use of a sensorially effective amount of the fragrance or flavor mixture according to the invention, comprising the compounds of the formula (I), formula (II) and formula (III) in general, or comprising diethyl (EJ- 2-methylbut-2-endioate
  • the fragrance or flavoring mixtures according to the invention are outstandingly suitable for scenting or perfuming or for flavoring products with a pear note.
  • Fragrance or flavor mixtures which generally comprise the compounds of the formula (I), formula (II) and formula (III) are considered to be preferred for this purpose. Even more preferred are fragrance or flavor mixtures of (EJ-2-methyl-but-2-endicarboxylic acid diester (mesaconic acid diester), (ZJ-2-methyl-but-2-endicarboxylic acid diester (citraconic acid diester) and 2-
  • Methylenebutanedicarboxylic acid diester (itaconic acid diester), this applies in particular to the mixtures of the respective dimethyl esters, diethyl esters, dipropyl esters or dibutyl esters of mesaconic acid, itaconic acid and itaconic acid.
  • the present invention ultimately relates to fragrance mixtures, perfume oils, cosmetic agents, application agents, detergents and cleaning agents, foods, animal feeds or pharmaceutical products which contain the fragrance or flavor mixture according to the invention in a sensorially effective amount.
  • odorant mixtures or Perfume oils are preferably those as described in detail in paragraphs [0074] to [0204] of WO 2018/114073 A1 .
  • This disclosure is incorporated into the present application in its entirety by specific reference.
  • An application agent is to be understood as meaning all agents mentioned herein that do not come under the group of perfume oils, cosmetic agents or detergents and cleaning agents.
  • the fragrance or flavor mixture according to the present invention is in amounts of 0.05 to 5% by weight, based on the fragrance mixture, the agent or the food, contain.
  • the invention therefore relates to both fragrance mixtures or puffy oils, cosmetic agents, application agents, detergents and cleaning agents, foods and animal feeds which contain the fragrance or flavoring mixture according to the invention, which contains the compounds of the general formula (I), formula (II) and formula (III) in general, or the diethyl (EJ-2-methylbut-2-enedioate or mesaconic acid diethyl ester in a mixture with diethyl (Z) -2-methylbut-2-enedioate and diethyl 2-methylene-butanedioate im Special include, contains.
  • the fragrance or flavor mixtures according to the invention are preferably combined with further constituents. Preferred further components are selected from the group consisting of:
  • Preservatives preferably the abrasives, anti-acne agents and agents for sebum reduction mentioned in US 2006/0089413, preferably the anti-aging agents mentioned in WO 2008/046791, preferably the antibacterial agents, anti-cellulite agents mentioned in WO 2005/123101
  • Antidandruff agents preferably the anti-inflammatory agents mentioned in WO 2008/046795, irritation-preventing agents, anti-irritants (anti-inflammatory, irritation-inhibiting and irritation-preventing agents), preferably the antimicrobial agents mentioned in WO 2007/042472 and US 2006/0089413, preferably the antioxidants mentioned in WO 2005/123101, preferably those mentioned in WO 2005/123101, astringents, antiseptic agents, antistatic agents, binders, buffers, carrier materials, preferably those mentioned in WO 2005/123101, chelating agents, preferably those in WO 2005/123101 mentioned, cell stimulants, cleansing agents, care agents, depilatories, surface-active agents tive substances, deodorants and
  • the fragrance or flavor mixture according to the invention composed of compounds of the general formula (I), formula (II) and formula (III), or preferably a fragrance or flavor mixture of detergents and cleaning agents containing diethyl (EJ-2-methylbut-2-enedioate, diethyl (ZJ-2-methylbut-2-enedioate and diethyl 2-methylene-butanedioate) (abbreviated as WSR agents ) within the meaning of the present invention, can be in solid form as powder, granules, tablets, etc., but also in liquid, gel or pasty form. These are preferably detergents that are suitable for both manual and machine washing, especially textiles . They can also be detergents or cleaning agents for the industrial sector or for the household sector.
  • Detergents can also be used, for example, for cleaning hard surfaces. These can for example be dishwashing agents that are used for manual or machine cleaning of dishes They can also be standard industrial or household cleaners that are used on hard surfaces such as furniture surfaces , Tiles, wall and floor coverings are cleaned. In addition to dishes, all other hard surfaces, in particular made of glass, ceramics, plastic or metal, in households and businesses can be used as hard surfaces.
  • the WSR agents can have other commercially available ingredients, such as surfactants, builders, bleaches, bleach activators, thickeners, enzymes, electrolytes, pH adjusters, dyes and fragrances, foam inhibitors, anti-redeposition agents, optical brighteners,
  • Graying inhibitors anti-crease agents, antimicrobial agents, preservatives, antioxidants, antistatic agents, UV adsorbers,
  • the fragrance mixtures or puff oils, cosmetic agents, application agents and also the detergents and cleaning agents which are made with the fragrance or flavor mixture according to the invention, comprising a sensorially effective amount of the compounds of the general formula ( I), formula (II) and formula (III) or preferably with a fragrance mixture, comprising a sensory effective amount of diethyl (E -2-methylbut-2-enedioate, diethyl (ZJ-2-methylbut-2-enedioate and diethyl) -2-methylene-butanedioate, perfumed or scented, selected from the group that consists from: Perfume extra its, eau de perfumes, eau de toilettes, aftershave lotions, eau de colognes, pre-shave products, splash colognes, perfumed
  • Refreshing tissues e.g. Floor cleaners, window glass cleaners, dishwashing detergents, bathroom and sanitary cleaners, scouring milk, solid and liquid toilet cleaners, powder and foam carpet cleaners, liquid detergents, powder detergents, laundry pretreatment agents, such as e.g. Bleaches, soaking agents and stain removers, fabric softeners, laundry soap, washing tablets, disinfectants, surface disinfectants, air fresheners in liquid, gel-like or solid carrier form, aerosol sprays, waxes and polishes, e.g.
  • tanning creams and products such as Hair sprays, hair gels, hair lotions, hair conditioners, permanent and semi-permanent hair coloring agents, hair shaping agents such as cold waves and hair straightening agents, hair lotions, hair creams and lotions, deodorants and antiperspir
  • perfume oils or compositions which contain the fragrance or flavor mixture according to the invention are selected from the group consisting of:
  • acidic, alkaline and neutral cleaning agents especially in the household sector, preferably floor cleaners, window glass cleaners, dishwashing detergents, bathroom and sanitary cleaners, scouring milk, solid and liquid toilet cleaners, powdered and foamed carpet cleaners, liquid detergents, powdery Detergents, fabric softeners, surface disinfectants, especially for hard surfaces (hard surface cleaner);
  • Body care products preferably solid and liquid soaps, shower gels, sham poos, shaving soaps, shaving foams;
  • cosmetic emulsions of the oil-in-water, water-in-oil and water-in-oil-in-water types preferably skin creams and lotions, face creams and lotions, sun protection 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, skin tanning creams and lotions, skin lightening creams and lotions;
  • Hair care products preferably hair sprays, hair gels, setting hair lotions, hair conditioners, permanent and semi-permanent hair dyes, hair lotions, hair creams and lotions;
  • Deodorants and antiperspirants preferably underarm sprays, roll-ons (preferably as an alcoholic or non-alcoholic solution, as a gel or (micro) emulsion, deodorant sticks (deodorant sticks), deodorant creams.
  • perfumed agents according to the invention are washing and cleaning agents, hygiene or care products, in particular in the field of body and hair care, cosmetics and the household.
  • the foods prepared with the flavor mixture according to the invention comprising a sensory effective amount of the compounds of the general formula (I), formula (II) and formula (III) or preferably with a flavor mixture
  • Diethyl (E -2-methylbut-2-enedioate, diethyl- (ZJ-2-methylbut-2-enedioate and diethyl 2-methylene-butanedioate are flavored, selected from the group consisting of: dairy products, beverages, sweets Food supplements, dietetic foods, food substitutes and semi-finished products,
  • Flavor mixtures comprising a sensory effective amount of the Compounds of the general formula (I), formula (II) and formula (III) or, preferably, a flavor mixture, comprising a sensory effective amount of diethyl (E -2-methylbut-2-enedioate, diethyl (ZJ-2-methylbut-2) -endioate and diethyl-2-methylene-butanedioate, can also be used in the aromatization of pharmaceutical products.
  • Preferred products are those in which the proportion of the fragrance or flavor mixture according to the invention in the product is from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight and particularly preferably from 0.25 to 3% by weight .-%, based in each case on the total weight of the perfumed or flavored end product.
  • Example 1 Determination of the iodine content of fragrance or flavor mixtures which were produced according to WO 2018/114073
  • the iodine content of the samples was determined in accordance with EN 1511, CON-PV 01187, ICP-MS.
  • Sample 1 is a 3 kg batch process.
  • sample 2 is a 50 kg batch process. The higher the batch process, the more iodine is required, which results in a higher iodine content in the end product.
  • Ethanol (2250 ml, 3% by volume) is placed in a 5 liter jacketed flask and heated to 50.degree. 2-methylenebutanoic acid (itaconic acid) (750 g, 5.76 mol, 1.0 equiv.) was then added in portions until everything dissolved. Sulfuric acid (126 ml, 0.4 equiv.) was then added dropwise and the mixture was refluxed for 5 hours.
  • 2-methylenebutanoic acid (itaconic acid) (750 g, 5.76 mol, 1.0 equiv.) was then added in portions until everything dissolved.
  • Sulfuric acid (126 ml, 0.4 equiv.) was then added dropwise and the mixture was refluxed for 5 hours.
  • Step 2 Preparation of diethyl EJ ⁇ -methylbut ⁇ -enedioate, diethyl Z) -2-methylbut-2-enedioate and diethyl 2-methylene-butanedioate
  • Example 3 Sensory evaluation of the fragrance or flavor mixture according to the invention
  • Example 4 olfactometric determination of the odor intensity of the fragrance or flavor mixture according to the invention
  • the odor threshold (ODT; odor detection threshold) of the above samples was determined using a dynamic olfactory meter with the designation T08, in which a smelling air sample is diluted with clean air. The dilution is presented to the test persons (test smells) for assessment.
  • the device is operated with synthetic air from steel cylinders or with prepared compressed air. Two gas jet pumps are operated with this clean air, the draw in the sample air directly from a sample bag.
  • the sample air is intensively mixed with the clean air in the gas jet pump. This mixture flows through a reversing valve to the individual test subject positions.
  • the volume flow of the sample air is automatically set by the control program using calibrated measuring orifices.
  • the determination of the odor concentration is the most common application.
  • the sample air is presented in increasing concentration for assessment until the odor is perceived by the test persons.
  • an answer button ("Yes, it smells") is pressed, the odor threshold concentration has been reached.
  • the measurements that are carried out with the olfactometer and with the participation of the test persons are subject to fixed standards. These olfactometric measuring methods are specified in the European standard DIN EN 13725.
  • the olfactometer T08 and the measuring method implemented with it correspond to these guidelines and make olfactometry an objective, generally recognized and proven measuring method.
  • the fragrance or flavor mixture according to the present invention has an odor threshold which is comparable to that of the ethyl decadienoate standard, but a much lower odor threshold than the fragrance or flavor mixture according to the prior art.
  • fragrance or flavoring mixtures according to the invention are therefore outstandingly suitable for scenting or flavoring. Due to the lower odor threshold, smaller dosages of the fragrance or flavor mixture are sufficient to produce a perceptible fragrance or flavoring.

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Abstract

L'invention concerne des mélanges de parfums ou d'arômes contenant (i) des diesters d'acide (E)-2-méthylbut-2-ène dicarboxylique, (ii) des diesters d'acide (Z)-2-méthylbut-2-ène dicarboxylique et (iii) des diesters d'acide 2-méthylène-butanedicarboxylique ayant une note fruitée, semblable à celle de la poire, un procédé de fabrication de ces parfums ou arômes ou de mélanges de parfums ou d'arômes, l'utilisation de mélanges de parfum ou d'arômes pour fabriquer un parfum ou un arôme fruité, semblable à une poire, ou pour fabriquer un mélange de parfum ou d'arômes ou une huile de parfum, des agents cosmétiques, des agents d'application, des détergents et des agents de nettoyage, des denrées alimentaires, des aliments pour animaux ou des produits pharmaceutiques ainsi que les produits fabriqués à partir de ceux-ci, qui contiennent des mélanges de parfum ou d'arômes en quantité efficace sur le plan sensoriel.
EP19725698.5A 2019-05-17 2019-05-17 Mélange de parfums ou d'arômes Pending EP3968784A1 (fr)

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US20030147937A1 (en) 2000-04-12 2003-08-07 Thomas Schwarz Use of compatible solutes as substances having free radical scavenging properties
SE0002960D0 (sv) 2000-08-21 2000-08-21 Eurotube Ab Engångs-smådjursfälla
DE10254872A1 (de) 2002-11-25 2004-06-03 Symrise Gmbh & Co. Kg Anthranilsäureamide und deren Derivate als kosmetische und pharmazeutische Wirkstoffe
DE102004029239A1 (de) 2004-05-03 2005-12-01 Symrise Gmbh & Co. Kg Benyliden-β-dicarbonylverbindungen als neue UV-Absorber
US9987217B2 (en) 2004-06-18 2018-06-05 Symrise Ag Blackberry extract
DE102004038485A1 (de) 2004-08-07 2006-02-23 Symrise Gmbh & Co. Kg alpha-Benzoyl-zimtsäurenitrile als neue UV-Absorber
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ATE425732T1 (de) 2004-11-22 2009-04-15 Symrise Gmbh & Co Kg Formulierungen mit ceramiden und/oder pseudoceramiden und (alpha-)bisabolol zur behandlung von hautschaden
US8241681B2 (en) 2005-10-14 2012-08-14 Symrise Ag Synergistic mixtures of bisabolol and ginger extract
DE102005056890A1 (de) 2005-11-28 2007-05-31 Institut für Umweltmedizinische Forschung gGmbH Kosmetisches Verfahren zur Beeinflussung der Melaninbildung in der Haut
WO2007110415A2 (fr) 2006-03-27 2007-10-04 Symrise Gmbh & Co. Kg Utilisation de trimères diacétyliques et formulations cosmétiques ou thérapeutiques contenant ces composés
ES2421191T3 (es) 2006-05-03 2013-08-29 Symrise Ag Antagonistas del receptor de Ah
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EP1915982A1 (fr) 2006-10-20 2008-04-30 Symrise GmbH & Co. KG Utilisation du 1,2-décanediol pour réduire la concentration du sébum et/ou pour aider à la pénétration des actives dans des régions de la peau, et des compositions cosmétiques et/ou dermatologiques comprenant du 1,2-décanediol
EP1923041A1 (fr) 2006-10-20 2008-05-21 Symrise GmbH & Co. KG Utilisation des C10-C14 alcane-diols pour la préparation d'une composition pour la prophylaxe et/ou le traitement des pellicules induites par Malassezia, ainsi que des compositions comprenant des C10-C14 alcane-diols
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CN110099990B (zh) 2016-12-21 2022-11-29 西姆莱斯股份公司 香料混合物

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