EP3303315A1 - Verfahren zur herstellung cyclischer ester - Google Patents

Verfahren zur herstellung cyclischer ester

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Publication number
EP3303315A1
EP3303315A1 EP16725147.9A EP16725147A EP3303315A1 EP 3303315 A1 EP3303315 A1 EP 3303315A1 EP 16725147 A EP16725147 A EP 16725147A EP 3303315 A1 EP3303315 A1 EP 3303315A1
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EP
European Patent Office
Prior art keywords
compounds
alkyl
methyl
unbranched
compound
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.)
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EP16725147.9A
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German (de)
English (en)
French (fr)
Inventor
Wolfgang Siegel
Karin SCHEIN-ALBRECHT
Ralf Pelzer
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom

Definitions

  • the present invention relates to a process for preparing cyclic esters in the presence of at least one high-boiling metal alkoxide catalyst.
  • the invention also relates to the stereoisomers of 18-methyl-1-oxacyclooctadec-10-en-2-one and their use as an odorant and / or flavoring agent,
  • compositions containing at least one of the stereoisomers of 18-methyl-1-oxacyclooctadec-10-en-2-one and additionally a carrier material,
  • Macrocyclic compounds that have a musky odor have long been sought-after aroma chemicals in the fragrance industry. To this
  • Compounds include both macrocyclic ketones such as. Cyclopentadecanone (Exalton®) or (Z) -9-cycloheptadecen-1-one (ci-ketone) as well as macrocyclic esters or diesters such as oxacyclohexadecane-2-one (Exaltolide®) (1),
  • Oxacyloheptadecane-2-one (hexadecanolide) (2), 1,4-dioxacycloheptadecane-5,17-dione (ethylene brassylate) (3) or oxacycloheptadec-10-en-2-one (ambrettolide) (4) and other functionalized macrocycles.
  • Macrocyclic esters can be synthesized, inter alia, by cyclization of the
  • the starting materials are first converted into oligomeric or polymeric esters, which are then depolymerized at temperatures in the range of 200 to 350 ° C and low pressures below 100 mbar in the presence of typical transesterification catalysts.
  • the monomeric cyclic ester forming in equilibrium is continuously distilled off from the reaction mixture as the lowest boiling component.
  • JP 55002640 describes a process for preparing macrocyclic esters in the linear polyester obtained by the condensation of hydroxycarboxylic acids or diacids with glycols, depolymerized and cyclized in the presence of titanium alkoxide catalysts.
  • EP 1097930 describes a process for the preparation of macrocyclic lactones in which a hydroxycarboxylic ester is subjected to an intramolecular transesterification, wherein the ester group of the hydroxycarboxylic ester is an alkyl group or an alkylenoxide oligomer. It is described that this reaction proceeds particularly advantageously in the presence of an alcohol selected from aliphatic alcohols or polyalkylene oxide alcohols.
  • EP 0940396 describes a process for the preparation of lactones starting from omega-hydroxycarboxylic acids or their esters in monomeric, oligomeric or polymeric form. Among other things, it is described that high-boiling polyalkylene glycol diethers are added to the reaction medium.
  • the hydroxyl and / or carboxy fatty acids required for the polymerization and cyclization are synthetically difficult to obtain. It is known in the prior art that these can be obtained from fermentatively produced sophorolipids and can be advantageously used as starting materials for the synthesis of macrocyclic esters.
  • CH 430679 describes a process for the preparation of oxacyloheptadecan-2-one (hexadecanolide) and 16-methyl-oxacyloheptadecan-2-one from a mixture of 15- and 16-hydroxypalmitic acid.
  • the 15- or 16-hydroxypalmitic acid is obtained from sophorolipids, which are in the fermentative conversion of
  • Hydroxyfatty acid starting material sophorolipids which are formed in the fermentation of fatty acids with Candida Bombicola be used.
  • the esters can be cyclized into large lactone rings that have a musk fragrance.
  • bottom thinners Such high boiling solvents are also referred to as "bottom thinners”.
  • JP 55120581 describes a process for the preparation of macrocyclic esters by depolymerization and cyclization of linear polyesters, in which
  • Viscosity reducing additives are added to the reaction mixture.
  • Solvent / bottom thinner is used.
  • EP0260680 describes a process for preparing macrocyclic esters by the catalyzed thermal depolymerization of linear polyesters, in which an olefinic polymer, which is inert under the reaction conditions described and is in liquid form, is used as the solvent. Specifically, polyethylene is used as the olefinic polymer.
  • WO 02/16345 describes a process for preparing macrocyclic esters by the thermal cleavage of linear oligoesters in the presence of thermostable
  • EP 0739889 A1 describes a two-stage process for the preparation of macrocyclic compounds in which difunctional starting materials are used in a first step
  • oligomers obtained in this way are depolymerized in a second step in the presence of Lewis acids, the polyalkylene glycol dialkyl ethers having a molecular weight of 500-3000 Da being used as solvent or bottom thinner. Specifically described is the polycondensation of 15-
  • the catalyst used in the transesterification or depolymerization step at least partially distils off during the distillation of the monomeric Cylleiters employments and must later be laboriously separated from the product. Also critical is the selection of the solvent used as SumpfverPJner, since this may distilled under circumstances in the distillation of the monomeric cyclization with and entraining the catalyst in the bottom and / or otherwise adversely affect the activity of the catalyst.
  • the present invention has for its object to provide an improved process for the preparation of macrocyclic esters, whereby the above
  • a catalyst is to be provided which can be used advantageously for the polymerization and depolymerization and which does not distill off in the distillative removal of the monomeric cyclization product from the reaction mixture. Nevertheless, good yields can be achieved with the catalyst. That as a sump thinner in the
  • X 1 for a straight or branched C4-C3o-alkylene group or a
  • X 2 is an unbranched or branched C 1 -C 30 -alkylene group or a
  • Y is an unbranched or branched C 2 -C 10 -alkylene group
  • R 1 is hydrogen or an unbranched or branched Ci-Cio-alkyl group in which at least one compound of general formula (I la) or
  • X 1 , X 2 and R 1 have the abovementioned meanings and
  • R 2 is hydrogen or an unbranched or branched C 1 -C 30 -alkyl group, b.1) the at least one compound (I 1a) in the presence of at least one
  • Catalyst which is selected from metal alkoxides, and in the presence of at least one polyether compound (PE) having a number average
  • Reaction mixture containing at least one macrocyclic compound of the general formula (I.a), or b.2) the at least one compound (I l.b) in the presence of at least one
  • Catalyst which is selected from metal alkoxides, and in the presence of at least one polyether compound (PE) having a number average
  • a product stream enriched in the macrocyclic compounds of the general formula (Ia) or (Ib) is removed by distillation and a bottom product enriched in the polyether compound (PE) and the catalyst is obtained.
  • the stereoisomers of 18-methyl-1-oxacyclooctadec-10-en-2-one prepared by the process according to the invention ie the compounds (10Z, 18S) -18-methyl-1-oxacyclooctadec-10-ene -2-one, (10Z, 18R) -18-methyl-1-oxacyclooctadec-10-en-2-one, (10E, 18S) -18-methyl-1-oxacyclooctadec-10-ene 2-one and (10E, 18R) -18-methyl-1-oxacyclooctadec-10-en-2-one, have a musky odor.
  • the present invention relates to the compounds (10Z, 18S) -18-methyl-1-oxacyclooctadec-10-en-2-one, (1 OZ, 18R) -18-methyl-1-oxacyclooctadec-10-ene-2 on, (10E, 18S) -18-methyl-1-oxacyclooctadec-10-en-2-one and (1OE, 18R) -18-methyl-1-oxacyclooctadec-10-en-2-one. Furthermore, the present invention relates to the use of (10Z, 18S) -18-
  • the present invention relates to the use of at least one of the aforementioned compounds, as part of a composition which additionally contains a carrier material, wherein the composition is selected from detergents, laundry detergents, cleaners, cosmetic
  • Nutritional supplements fragrance dispensers, perfumes, pharmaceutical
  • the present invention relates to a fragrance composition and / or a fragrance material containing at least one of the aforementioned compounds and a carrier material.
  • the present invention relates to a method for imparting or changing a smell or taste of a composition, in which at least one of the aforementioned compounds is added to the composition in an amount which gives the composition an odor or taste or the odor or taste of the composition changed.
  • the invention comprises the following preferred embodiments:
  • X 1 is an unbranched or branched C 4 -C 30 -alkylene group or a straight-chain or branched C 4 -C 30 -alkenylene group which contains 1, 2 or 3 double bonds,
  • X 2 represents an unbranched or branched C 1 -C 30 -alkylene group or a straight-chain or branched C 2 -C 30 -alkenylene group containing 1, 2 or 3 double bonds,
  • Y is an unbranched or branched C 2 -C 10 -alkylene group and R 1 is hydrogen or an unbranched or branched C 1 -C 10 -alkylene group
  • X 1 , X 2 and R 1 have the abovementioned meanings and
  • R 2 is hydrogen or unbranched or branched
  • Catalyst selected from metal alkoxides and in the presence of at least one polyether compound (PE) having a number average molecular weight of at least 200 g / mol, to obtain a reaction mixture containing at least one macrocyclic compound of the general formula (Ia) or b.2) the at least one compound (II.b) in the presence of at least one
  • PE polyether compound having a number average molecular weight of at least 200 g / mol
  • Catalyst which is selected from metal alkoxides, and in the presence of at least one polyether compound (PE) having a number average molecular weight of at least 200 g / mol, and additionally in the presence of at least one diol HO-Y-OH, wherein Y has the abovementioned meaning to obtain a reaction mixture which contains at least one macrocyclic compound of the general formula (Ib), the reaction mixture obtained from the reaction mixture obtained in step b.1) or b.2) being reacted on the macrocyclic compounds of the general formula (Ia) or (Ib) Enriched product stream is discharged by distillation and a product enriched in the polyether compound (PE) and the catalyst bottoms product is obtained.
  • the at least one catalyst used in step b.1) or b.2) has a boiling point at 5 mbar of more than 250 ° C.
  • PE polyether compound
  • LM different solvent
  • R 1 is hydrogen or methyl
  • X 1 is an unbranched Ci2-Ci6-alkylene group or an unbranched
  • X 2 is an unbranched C 9 -C 13 -alkylene group or an unbranched C 9 -C 13 -alkenylene group which contains a double bond
  • Y is an unbranched C 2 -C 4 -alkylene group
  • R 2 is hydrogen or an unbranched C 1 -C 4 -alkyl group, where the radicals X 2 and Y together are 1 to 15 directly bridging
  • LM solvent
  • PE polyether compound
  • Product fraction is subjected to a further purification, preferably to a distillation.
  • Solvent (LM) and optionally on the polyether compound (PE) enriched fraction is returned to the reaction in step b.1) or b.2).
  • n is an integer from 3 to 250 and either one radical R 3 is hydrogen and the other radical R 3 is C 1 -C 30 -alkyl or
  • radicals R 3 are hydrogen or
  • the at least one polyether compound (PE) is selected from compounds of general formula (III) wherein
  • Z and n are as defined above and
  • R 3 is hydrogen and
  • R 3 is hydrogen
  • the other radical R 3 is hydrogen or Ci-Cio-alkyl or for
  • step b.1) or b.2) at least one metal alkoxide catalyst by reacting at least one metal compound selected from metal oxides, alkylmetal oxides, metal salts or metal alkoxides of the general formula M [0 (Ci C4-alkyl)] m , where m is 1, 2, 3 or 4, with at least one polyether compound (PE), as in
  • Embodiment 1 or 1 1 is defined.
  • metal of the production of the metal oxide used at least one metal alkoxide catalyst Alkylmetalloxids, metal salt or metal alkoxide M [0 (Ci-C 4 - alkyl)] m is selected from alkali metals, alkaline earth metals .
  • Transition metals of the 4th, 7th, 8th, 9th and 12th group and metals and / or semimetals of the 13th, 14th and 15th group of the Periodic Table of the Elements are also possible.
  • glycerol, pentaerythritol, C2-C is at least one solvent (LM) is selected from C2-Cis-alkanols, 4 -alkylene glycols and their mono- and di- (Ci-C 4 - alkyl) ethers, different from the compounds PE polyalkylene glycols and their Mono- and dialkyl ethers, aromatic hydrocarbons and
  • LM solvent
  • Provision of Compounds (II.a) or (II.b) comprise a.1) providing a C6-C22 carboxylic acid, a.2) reacting the C6-C22 carboxylic acid provided in step a.1)
  • Carboxylation in step a.2) is carried out by fermentation.
  • Nutritional supplements fragrance dispensers, perfumes, pharmaceutical
  • a method of imparting or changing a smell or taste of a composition comprising adding to the composition at least one of the compounds mentioned in embodiment 25 in an amount which imparts a smell or taste to the composition or alters the odor or taste of the composition.
  • the high-boiling catalyst does not distil off together with the macrocyclic esters.
  • the macrocyclic ester obtained according to the invention can be dispensed with.
  • the process of the invention allows the production of macrocyclic esters in good yields and purities at relatively short reaction times, d. H. in high space-time yield.
  • the process of the invention can be carried out continuously and is characterized by its simplicity and economy.
  • the catalyst used in the process according to the invention can be reused after completion of the reaction for the preparation of further macrocyclic esters or stored for a long time.
  • starting materials which are relatively easily accessible can be used.
  • Short chain feeds can easily be purchased or synthesized commercially.
  • Long-chain feedstocks can be produced relatively easily by fermentation from fatty acids.
  • isomers of 18-methyl-1 - oxacyclooctadec-10-en-2-one are characterized by advantageous organoleptic properties, in particular by a musky odor. They can therefore be advantageously used as an odor or flavoring or as part of a fragrance composition and / or a fragrance material.
  • the isomers of 18-methyl-1-oxacyclooctadec-10-en-2-one are expected to have very low toxicity as it belongs to a group of compounds that do not appear to have significant toxicity.
  • Structurally very similar macrocyclic Esters, such as oxacycloheptadec-10-en-2-one (ambrettolide), are already used as fragrances.
  • CrC 3 o-alkyl refers to unbranched alkyl groups having 1 to 30 carbon atoms or branched
  • Alkyl groups having 3 to 30 carbon atoms Preferably, "CrC 3 o-alkyl” is unbranched alkyl groups having 1 to 20 carbon atoms or branched
  • Alkyl groups with 3 to 20 carbon atoms include, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1, 2-dimethylpropyl, 1 , 1-dimethylpropyl, 2,2-dimethylpropyl,
  • n-nonadecane n-decosan and the like.
  • it is at -C 3 -alkyl unbranched Ci-Cio-alkyl or branched C 3 -Cio-alkyl, in particular unbranched Ci-C6-alkyl or branched C 3 -C 6 alkyl groups.
  • C 1 -C 30 -alkyl is unbranched C 1 -C 4 -alkyl groups, especially methyl or ethyl.
  • C 3 -alkyl includes within its definition the terms “C1-C10 alkyl”, “d-Ce-alkyl” and “CC 4 alkyl”.
  • C 1 -C 30 -alkylene refers to divalent hydrocarbon radicals having from 1 to 30 carbon atoms. The divalent hydrocarbon radicals may be unbranched or branched.
  • C 1 -C 30 -alkylene is preferably unbranched or branched C 4 -C 20 -alkylene groups, more preferably unbranched or branched C 6 -C 18 -alkylene groups, in particular unbranched C 9 -C 16 -alkylene groups.
  • the term "Ci-C3o-alkylene” includes within its definition the terms “C 4 -C 30 alkylene", “C 2 -C 8 alkylene", “C 6 -C 5 alkylene", “C 2 - Ci 6 -alkylene ", and” C9-C13-alkylene ".
  • C 2 -C 10 -alkylene refers to divalent hydrocarbon radicals having 2 to 10 carbon atoms.
  • the divalent hydrocarbon radicals may be unbranched or branched. These include, for example, 1, 2-ethylene, 1, 2-propylene, 1, 3-propylene, 1, 2-butylene, 1, 3-butylene, 1, 4-butylene, 2-methyl-1, 3-propylene, 1 , 1-dimethyl-1,2-ethylene, 1,5-pentylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 1-ethyl-1,3-propylene, 2-ethyl -1, 3-propylene,
  • 1,7-heptylene 2-methyl-1,6-hexylene, 3-methyl-1,6-hexylene, 2-ethyl-1,5-pentylene, 3-ethyl-1,5-pentylene, 2,3- Dimethyl-1, 5-pentylene, 2,4-dimethyl-1,5-pentylene,
  • C 2 -Cio-alkylene unbranched C 2 -C6- alkylene or branched C3-C6-alkylene, more preferably straight-chain C 2 -C 4 alkylene or branched C3-C4 alkylene, in particular unbranched C 2 -C 4 alkylene groups.
  • C 2 -C 30 -alkenylene are divalent hydrocarbon radicals having 2 to 30 carbon atoms, which
  • C 2 -C 30 -alkenylene is preferably unbranched or branched C 6 -C 18 -alkenylene groups having 1, 2 or 3
  • Double bonds particularly preferably unbranched C6-Ci8-alkenylene groups with 1, 2 or 3 double bonds.
  • These include, for example, 1-, 2-, 3-hexenylene, 1-, 2-, 3-heptenylene, 1-, 2-, 3-octenylene, 1-, 2-, 3-nonenylene, 1-, 2-, 3 , 4-, 5-decenylene, 1-, 2-, 3-, 4-, 5-undecenylene, 2-, 3-, 4-, 5-, 6-dodecenylene, 2,4-dodecadienylene,
  • C 2 -C 3 o-alkenylene is unbranched C 6 -C 18 -alkenylene groups having one or two double bonds, in particular unbranched C 9 -C 16 -alkenylene groups having one double bond.
  • C2-C3o-alkenylene includes within its definition the terms “C 4 -C 3 o-alkenylene", “Ci 2 -C 8 alkenylene”, “C 6 -C 5 alkenylene”, “Ci 2 -Ci 6 alkenylene "and” Cg cis alkenylene ".
  • the carbon atom can be at
  • Branching points independently of each other have an R, or an S configuration or both configurations in equal or different proportions.
  • the radical X 1 in the compounds of the general formula (Ia) has 1 to 21 ring carbon atoms and the radicals X 2 and Y in the compounds of the general formula (Ib) together have 9 to 19 ring carbon atoms.
  • the radical X 1 in the compounds of the general formula (Ia) has 12 to 18 ring carbon atoms, in particular 13 to 16 ring carbon atoms, and the radicals X 2 and Y in the compounds of the general formula (Ib) together have 10 to 17 ring carbon atoms, in particular 1 1 to 15 ring carbon atoms, on.
  • the radicals X 1 in the compounds of the general formula (Ia) has 12 to 18 ring carbon atoms, in particular 13 to 16 ring carbon atoms
  • the radicals X 2 and Y in the compounds of the general formula (Ib) together have 10 to 17 ring carbon atoms, in particular 1 1 to 15 ring carbon atoms, on.
  • R 1 is hydrogen or methyl
  • X 1 is an unbranched C 12 -C 18 -alkylene group or an unbranched C 12 -C 18 -alkenylene group containing one or two double bonds,
  • X 2 is an unbranched C6-Cis-alkylene group or an unbranched C6-C15-
  • Y is an unbranched C 2 -C 4 -alkylene group or branched C 3 -C 4 -alkylene group and
  • R 2 is hydrogen or an unbranched C 1 -C 6 -alkyl group or branched
  • R 1 is hydrogen or methyl
  • X 1 is an unbranched C 12 -C 16 -alkylene group or an unbranched C 12 -C 16 -butylene radical
  • X 2 is an unbranched C 9 -C 13 -alkylene group or an unbranched C 9 -C 13 -alkenylene group which contains a double bond
  • Y is an unbranched C 2 -C 4 -alkylene group
  • R 2 is hydrogen or an unbranched C 1 -C 4 -alkyl group, where the radicals X 2 and Y together have 1 to 15 directly bridging carbon atoms.
  • the at least one compound (II.a) or the at least one compound (II.b) provided in step a) of the process according to the invention can be either pure or as a technically available mixture containing at least one of the compounds (II.a) or (II.b) present.
  • the content of compounds (II.a) or (II.b) is generally more than 50% by weight, preferably more than 60% by weight, in particular more than 70 wt .-%, based on the total weight of the technically available mixture.
  • the compounds (II.a) or (II.b) can either be obtained commercially, synthesized or prepared by a biocatalytic method, for example by a fermentative or enzymatic method.
  • the compounds (II.a) or (II.b) are prepared from C6-C22 carboxylic acids, wherein the provision of the compounds (II.a) and (II.b) comprises the following steps:
  • step a.3) optionally the oxidation of the obtained in step a.2) omega-hydroxylated C6-C22 carboxylic acids to the corresponding omega-carboxylated C6-C22 carboxylic acids, a.4) optionally, the esterification of the omega and / or (omega) 1) -hydroxylated C 6 -C 22 -carboxylic acids from step a.2) or the carboxylated C 6 -C 22 -carboxylic acids from steps a.2) or a.3) with unbranched or branched C 1 -C 6 -alkanols.
  • the C6-C22 carboxylic acids used in step a.2) are generally commercially available or can be obtained in large quantities from readily available natural sources.
  • the reaction of the C6-C22-carboxylic acids in step a.2) is carried out biocatalytically.
  • the biocatalytic reaction in step a.2) can be carried out in different ways, for example by the use of catalytic amounts of a suitable enzyme or by a fermentative process.
  • the biocatalytic reaction in step a.2) preferably takes place via a fermentative process.
  • Candida genus such as Candida Apicola, Candida albicans, Candida bombicola, Candida magnoliae or Candida tropicanea, are used for this purpose.
  • Suitable fermentative processes are described, for example, in the Spencer et al., Canadian Journal of Chemistry, 1961, Vol. 39, pp. 846, described in detail.
  • sophorolipids In the fermentative reaction using yeast strains, the omega and / or (omega-1) -hydroxylated carboxylic acids or the (alpha, omega) -dicarboxylic acids are bound in sophorose form, i. H. as so-called sophorolipids.
  • sophorolipids which are usually present as aqueous suspension, are usually by means of suitable separation methods, for example by
  • sophorolipids For extraction of the sophorolipids are generally not or only to a very small extent miscible with water organic solvents.
  • Preferred organic solvents suitable for extracting the sophorolipids are
  • aliphatic or alicyclic hydrocarbons such as pentane, hexane, heptane, ligroin, petroleum ether or cyclohexane, halogenated aliphatic or alicyclic hydrocarbons, such as dichloromethane,
  • Hydrocarbons such as benzene, toluene or xylene, halogenated aromatic hydrocarbons such as chlorobenzene or dichlorobenzene, ethers such as methyl tert-butyl ether, diethyl ether, dibutyl ether, tetrahydrofuran, 1, 4-dioxane, 1, 2-dimethoxyethane, carboxylic acid esters such as methyl acetate or
  • Hydroxylation usually obtained a mixture of omega and (omega-l) -hydroxylated carboxylic acids, which are present in equal or different proportions can. Usually, the fermentative hydroxylation proceeds regioselectively, with one of the hydroxylation products being formed in excess.
  • hydrolysis of ester and / or ether groups as described for example in CH 430679 or DE 28341 17.
  • the hydrolysis of the sophorolipids i. H. the cleavage of the hydroxylated or carbocylated fatty acids from the sophorose, carried out under acidic conditions, using mineral acids or organic sulfonic acids.
  • mineral acids in particular sulfuric acid, for the hydrolysis of the sophorolipids.
  • the omega-hydroxylated C6-C22 carboxylic acids obtained in step a.2) can be oxidized to the corresponding (alpha, omega) dicarboxylic acids (step a.3)).
  • Suitable for this purpose are the customary processes known to the person skilled in the art for the oxidation of primary alcohols to carboxylic acids.
  • esterification catalysts customary catalysts can be used, for.
  • mineral acids such as sulfuric acid and phosphoric acid
  • organic sulfonic acids such as methanesulfonic acid and p-toluenesulfonic acid
  • Catalysts in particular titanium, tin (IV) - or zirconium compounds, such as tetraalkoxytitans, z. As tetrabutoxytitanium, and tin (IV) oxide.
  • the resulting in the reaction water can be removed by conventional means, for. B. by distillation, are removed. Preference is given to using mineral acids or organic sulfonic acids as esterification catalysts, particularly preferably mineral acids, in particular
  • the esterification catalyst is used in an effective amount, the
  • esterification (step a.4)) can take place during or after the hydrolysis of the sophorolipids carried out in step a.2).
  • the esterification is preferably carried out during the hydrolysis, the same mineral acid, in particular sulfuric acid, being used for the hydrolysis and also for the esterification.
  • the at least one compound of the general formulas (II.a) or (II.b) obtained in steps a.2), a.3) or a.4) can, after working up, be subjected to a further purification, for example a distillative purification or be used directly.
  • C6-C22 carboxylic acids are fermentatively converted into the corresponding sophorose-bound omega and / or (omega-1) -hydroxylated or omega-carboxylated C6-C22-carboxylic acids, subsequently with the addition of a mineral acid in the presence of methanol or ethanol , with the simultaneous formation of the methyl and / or ethyl ester, split off from the sophorose and the resulting crude ester, depending on the degree of purity, subjected to a distillative purification or used directly.
  • the enzymatic or fermentative (omega-I) hydroxylation can be enantioselective.
  • the compounds of general formula (II.a) prepared by enzymatic or fermentative (omega-I) hydroxylation can be used as pure R or S isomers or as R / S isomeric mixtures in which one of the enantiomers in the Excess is present.
  • Step b) of the method according to the invention includes two variants.
  • Variant b.1) of the process according to the invention relates to the reaction of at least one
  • Variant b.2 relates to the reaction of at least one compound of general formula (II.b) and additionally at least one diol HO-Y-OH, to a
  • a product stream enriched in the macrocyclic compounds of the general formula (Ia) or (Ib) is removed by distillation from the reaction mixture.
  • the catalyst used in b.1) and b.2), the at least one polyether compound (PE), the reaction conditions and the reaction procedure are identical in both variants b.1) and b.2).
  • variants b.1) and b.2) differ only in the nature of the starting materials used and the cyclization products obtained.
  • the proportion of the educt prepared in step a) in the reaction mixture of steps b.1) or b.2) is generally from 5 to 60% by weight, in particular from 10 to 50% by weight, based on the total weight of the reaction mixture at the beginning of the implementation.
  • Y in the diol HO-Y-OH represents an unbranched or branched C 2 -C 10 -alkylene group, preferably unbranched C 2 -C 6 -alkylene groups or branched C 3 -C 6 -alkylene groups, in particular unbranched C 2 -C 4 -alkylene groups. discharge:
  • Reaction mixture is discharged from the macrocyclic compounds of the general formula (I.a) or (I.b) enriched product stream by distillation.
  • the reaction mixture is separated into a product fraction enriched in the macrocyclic compounds of the general formula (I.a) or (I.b) and a bottom product enriched in the polyether compound (PE) and the catalyst.
  • Suitable devices include distillation columns, such as tray columns, with
  • Falling film evaporators Falling film evaporators, forced circulation evaporators, Sambay evaporators, etc. and
  • distillation columns and / or rotary-belt columns for the removal of the macrocyclic compounds by distillation, in particular rotary-belt columns.
  • a vapor is first withdrawn from the reaction mixture obtained in steps b.1) and b.2), which is then at least partially condensed.
  • all suitable capacitors can be used. These can be cooled with any cooling media.
  • Capacitors with air cooling and / or water cooling are preferred, with air cooling being particularly preferred.
  • at least one solvent other than the polyether compound (PE) is distilled to remove the product stream enriched in the compounds (Ia) or (Ib) to the reaction mixture obtained in step b.1) or b.2) ( LM) as entrainer, added and / or an inert gas stream introduced into the reaction mixture.
  • the solvent (LM) thus fulfills the function of an entraining agent.
  • the term "entrainer” is understood to mean an organic compound, in particular an organic solvent, which at least partially passes into the gas phase together with the compounds (I.a) and / or (I.b).
  • Suitable solvents are generally all solvents whose boiling point at 1013 mbar in the range of 95-300 ° C and at least partially pass together with the compounds (la) and / or (lb) in the gas phase, but not or only slightly with the compounds (la) and (lb) mix.
  • the at least one solvent (LM) is selected from C2-C15-
  • the at least one solvent (LM) is particularly preferably glycerol, ethylene glycol, propylene glycol or of the compounds PE
  • the at least one solvent (LM) is glycerol and
  • the at least one solvent (LM) is added over a longer period of time for the reaction.
  • the addition of the at least one solvent (LM) takes place at the beginning of the reaction or at a later time in the course of the reaction.
  • the at least one solvent (LM) is preferably metered in continuously during the entire course of the removal by distillation of the cyclization products (I.a) or (I.b).
  • the amount of solvent (LM) added depends on the total amount of the compounds used (II.a) or (II.b) and the separation of the
  • Cyclization products (l.a) or (l.b) required time It has proved to be advantageous if the amount of solvent (LM) added in the range of 0.02 to 50 g / (g (educt) * h) (gram LM per gram of starting material and hour).
  • the amount of solvent (LM) added is preferably in the range from 0.03 to 25 g / (g (educt) * h), more preferably in the range from 0.05 to 10 g / (g (educt) * h), in particular in a range of 0.1 to 5 g / (g ⁇ educt) * h).
  • the distillative removal of the product stream enriched in the compounds (1a) or (1b) can be initiated under the reaction conditions inert gas in the reaction mixture.
  • An inert gas is understood to mean a gas which, under the given process conditions, does not react with the reactants, reagents, solvents or the resulting products involved in the reaction.
  • Suitable inert gases are for. As nitrogen, helium, argon, etc.
  • nitrogen is used as the inert gas.
  • the inert gas can be passed into the gas space of the reaction zone or into the liquid reaction mixture.
  • the supply of the inert gas to the reaction zone is such that a large exchange area between the liquid Reaction mixture and the inert gas is created.
  • the introduction of the inert gas causes a stripping effect and facilitates the removal of the monomeric cyclization products from the reaction mixture.
  • the inert gas is introduced below the liquid surface into the boiling reaction mixture so that it bubbled through the reaction mixture.
  • the pressure of the inert gas must be sufficiently high to overcome the hydrostatic pressure of the reaction mixture above the inert gas feed.
  • the inert gas may be 20 to 50 cm below the surface of the liquid
  • the inert gas may be fed by any suitable means. These include z. As gassing lances or nozzles.
  • the nozzles may be provided at or near the reactor bottom.
  • the nozzles can be designed as openings of a hollow chamber surrounding the reactor. Alternatively you can
  • Diving nozzles are used with suitable supply lines.
  • Several nozzles can z. B. be arranged in the form of a wreath.
  • the nozzles may face up or down.
  • the nozzles are preferably inclined downwards.
  • the reaction mixture is mixed in order to effect an exchange of reaction mixture in the reactor region below the feed of the inert gas with reaction mixture in the reactor region above the feed of the inert gas.
  • stirrer or circulation pump are suitable.
  • a so-called gassing stirrer is used to supply the inert gas and to mix the reaction mixture.
  • Steps b.1) or b.2) The reaction of steps b.1) or b.2) proceeds in principle in two phases.
  • a first phase of the reaction the oligomerization or polymerization phase, the starting materials oligomerize predominantly to linear polyesters of different chain lengths, the macrocyclic compounds of the general formula (I.a) or (I.b), if at all, being formed only to a small extent.
  • the oligomers are depolymerized and cyclized esters. This is the monomer forming in equilibrium
  • the removal by distillation of the compounds (Ia) or (Ib) enriched takes place Product stream essentially after the reaction in step b.1) or b.2).
  • the expression "essentially after the reaction” in this context means that the distillative removal of the product stream enriched in the compounds (1 .a) or (1 .b) is started as soon as more than 70%, for example 80, 90 or 95%, the feedstocks of the general formulas (ll .a) or (ll .b) were implemented.
  • the depolymerization or cyclization phase typically begins with the removal of the equilibrium monomeric cyclic product from the reaction mixture, i. H. as soon as the removal of the monomer cyclization product by distillation is started. Since the oligomerization is usually relatively fast, the distillative discharge of the
  • Reaction in step b.1) or b.2) for example, 5, 10 or 20 minutes after the start of the reaction, carried out, if the reaction temperature and the pressure are already in the necessary range.
  • the distillative removal of the product stream enriched in the compounds (1 .a) or (1 .b) is particularly preferably carried out after the reaction in step b.1) or b.2).
  • enriched product stream are usually carried out at a temperature in the range of 150 to 350 ° C, preferably at a temperature in the range of 180 to 320 ° C and in particular at a temperature in the range of 200 to 300 ° C.
  • steps b.1) or b.2) can generally be carried out at ambient pressure or reduced pressure.
  • the reaction of steps b.1) or b.2) and the removal of the product stream enriched in the macrocyclic compounds of general formula (Ia) or (Ib) by distillation are preferably carried out under reduced pressure.
  • PE polyether compound
  • the alcohol functions may be present as free -OH groups. They are preferably polyetherols, their alcohol functions may be etherified with a (Ci-Cio) -alcohol or esterified with a (C2-Cio) carboxylic acid.
  • Suitable polyetherols may be linear or branched, preferably linear.
  • Suitable polyetherols generally have a number average molecular weight in the range of about 200 to 20,000, preferably 250 to 5000, particularly preferably 300 to 3000, on.
  • Suitable polyetherols are, for example, nonionic polymers which contain alkylene oxide repeating units. The proportion of alkylene oxide repeating units is preferably at least 30% by weight, based on the total weight of the compound.
  • Suitable polyetherols are polyalkylene glycols, such as polyethylene glycols, polypropylene glycols, polytetrahydrofurans and alkylene oxide copolymers.
  • Suitable alkylene oxides for the preparation of alkylene oxide copolymers are, for. For example, ethylene oxide, propylene oxide, epichlorohydrin, 1, 2- and 2,3-butylene oxide.
  • Suitable examples are copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and butylene oxide and copolymers of ethylene oxide, propylene oxide and at least one butylene oxide.
  • the alkylene oxide copolymers may contain randomly distributed alkylene oxide units or in copolymerized form in the form of blocks.
  • the proportion of repeating units derived from ethylene oxide is 40 to 99% by weight.
  • Particularly suitable as a polyether compound (PE) are ethylene oxide homopolymers and
  • Ethylene oxide / propylene oxide copolymers are also suitable as the polyether compound (PE) which are derived from low molecular weight C 1 -C 6 alcohols or from C 7 -C 30 -fatty alcohols and / or from low-molecular C 2 -C 6 -carboxylic acids or derived from C7-C3o fatty acids.
  • PE polyether compound
  • ether and / or ester derivatives of the polyetherols described above which are derived from low molecular weight C 1 -C 6 alcohols or from C 7 -C 30 -fatty alcohols and / or from low-molecular C 2 -C 6 -carboxylic acids or derived from C7-C3o fatty acids.
  • These include, for example, polyalkylene glycol monoalkyl ethers,
  • PE polyether compounds
  • the polyether compound (PE) is selected from compounds which are only one negligible amount, for example less than 2% or less than 1% or less than 0.5%, based on the total amount in the
  • PE polyether compound
  • LM solvent
  • the polyether compounds used according to the invention preferably have a boiling point at 5 mbar of at least 280 ° C., more preferably of at least 300 ° C., in particular of at least 350 ° C.
  • the polyether compound (PE) is selected from compounds of the general formula (III)
  • Z is independently selected from ethylene, 1, 2-propylene,
  • n is an integer from 3 to 250 and either one radical R 3 is hydrogen and the other radical R 3 is C 1 -C 30 -alkyl, preferably C 1 -C 10 -alkyl, in particular C 1 -C 6 -alkyl, or
  • one radical R 3 is hydrogen and the other radical R 3 is C 1 -C 30 -alkyl, preferably C 1 -C 10 -alkyl, in particular C 1 -C 6 -alkyl.
  • Z is preferably ethylene (homopolymers) or ethylene and 1,3-propylene
  • N is preferably an integer from 4 to 100, particularly preferably from 5 to 50, in particular from 5 to 25.
  • both R 3 stand for
  • Particularly preferred compounds of the general formula (III) are, for example, polyethylene glycols, polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol monoacetate or polyethylene glycol diacetate having an average molecular weight of from 300 to 3,000.
  • the proportion of the at least one polyether compound (PE) in the reaction mixture is generally from 25 to 95 wt .-%, preferably 40 to 90 wt .-%, in particular 50 to 85 wt .-% based on the total weight of the reaction mixture at the beginning of the reaction.
  • the at least one catalyst used in steps b.1) and b.2) is selected from metal alkoxides.
  • the at least one catalyst used in steps b.1) and b.2) is selected from Metal alkoxides which only to a negligible part, for example less than 2 wt .-% or less than 1 wt .-% or less than 0.5 wt .-%, based on the total amount of at least one in the reaction solution metal alkoxide catalyst present together with the macrocyclic
  • the at least one metal alkoxide catalyst generally has a boiling point at 5 mbar of more than 250 ° C.
  • the at least one metal alkoxide catalyst preferably has a boiling point at 5 mbar of more than 280 ° C., particularly preferably more than 300 ° C., in particular more than 350 ° C.
  • the at least one metal alkoxide catalyst used in steps b.1) or b.2) is prepared by reacting at least one metal compound selected from metal oxides, alkyl metal oxides, metal salts or metal alkoxides of the general formula M [O (C 1 -C 4 -alkyl)] m , where m is 1, 2, 3 or 4, with at least one polyether compound (PE) selected from compounds of general formula (III).
  • the metal of the metal compound used to prepare the at least one metal alkoxide catalyst is selected from alkali metals, alkaline earth metals, transition metals of the 4th, 7th, 8th, 9th and 12th groups, and metals and / or
  • the metal of the metal compound used to prepare the at least one metal alkoxide catalyst is preferably selected from among K, Na, Ca, Mg, Ti, Zr, Mn, Fe, Co, Zn, Cd, Al, Ge, Sn, Pb and Sb, in particular under K, Na, Ca, Mg, Ti, and Zn.
  • Particularly preferred metallic starting materials for the preparation of the at least one metal alkoxide catalyst are, for example, potassium hydroxide (KOH),
  • Preferred polyether compounds of general formula (III) used to prepare the at least one metal alkoxide catalyst are those defined.
  • the polyether compound used to prepare the at least one metal alkoxide catalyst will be in an excess molar excess of at least 1.5 times, preferably in an at least 2-fold molar excess, for example in a 4-fold, 15-fold or 30-fold molar excess based on the amount of metal oxide, metal hydroxide or metal alkoxide M [O (C 1 -C 5 -alkyl)] m used.
  • the preparation of the at least one metal alkoxide catalyst is generally carried out at a temperature of 50 to 250 ° C, preferably at a temperature of 80 to 220 ° C and in particular at a temperature of 100 to 200 ° C.
  • the preparation of the at least one metal alkoxide catalyst can be carried out in the absence or in the presence of an inert gas as defined above.
  • the preparation of the at least one metal alkoxide catalyst is preferably carried out with the addition of an inert gas, nitrogen preferably being used as the inert gas.
  • the preparation of the at least one metal alkoxide catalyst can generally be carried out at ambient pressure or reduced or elevated pressure. Preferably, the preparation of the at least one metal alkoxide catalyst is carried out at ambient or reduced pressure.
  • the low-boiling components formed in the preparation of the at least one metal alkoxide catalyst are removed by distillation.
  • low-boiling component refers to organic compounds which in the reaction of at least one
  • the low-boiling components are, for example, water, a C 1 -C 6 alcohol or other organic solvent
  • Components used an inert gas stream.
  • the preparation of the at least one metal alkoxide catalyst is carried out at ambient pressure, the optionally resulting, low-boiling components are removed by distillation from the reaction mixture by means of a nitrogen stream.
  • the nitrogen is passed into the gas space of the reaction zone or into the liquid reaction mixture.
  • the supply of the inert gas to the reaction zone is such that a large exchange area between the liquid
  • Reaction mixture and the inert gas is created.
  • the introduction of the inert gas causes a stripping effect and facilitates the distillative removal of the low-boiling components from the reaction mixture.
  • the preparation of the at least one metal alkoxide catalyst is preferably carried out in situ.
  • the expression "in situ” means that the preparation of the catalyst can also take place during the reaction (steps b.1) or b.2)), but before with the removal of the monomer by distillation
  • the preparation of the at least one metal alkoxide catalyst is particularly preferably carried out before the reaction of steps b.1) or b.2).
  • the preparation of the at least one metal alkoxide catalyst takes place in the absence of the starting materials (I.a), (I.b) and of the diol HO-Y-OH.
  • the amount of the metal alkoxide catalyst used in steps b.1) or b.2) is 0.1 to 50 mol%, preferably 1 to 40 mol% and in particular 3 to 30 mol%, based on the total amount of Compounds (II.a) or (II.b) in the
  • Compounds of the general formula (I.a) or (I.b) enriched product stream may contain at least part of the solvent (LM) and optionally additionally a part of the polyether compound (PE).
  • LM solvent
  • PE polyether compound
  • the fraction removed by distillation contains, on the compounds (I.a) or (I.b)
  • enriched product stream at least a portion of the solvent (LM) and optionally additionally a part of the polyether compound (PE).
  • LM solvent
  • PE polyether compound
  • Polyether compound (PE) the product stream is subjected to a separation to obtain a fraction enriched in the solvent (LM) and optionally in the polyether compound (PE) and a product fraction which contains predominantly macrocyclic compounds of the general formula (I.a) or (I.b).
  • the separation of the discharged product stream takes place in a fraction enriched in the solvent (LM) and optionally in the polyether compound (PE) and a product fraction via a process of
  • phase separation Self-segregation (phase separation), if the solvent (LM) and optionally the polyether compound (PE) with the macrocyclic compounds of the general formula (I.a) or (I.b) mix only slightly or not at all.
  • the product stream is usually passed into a phase separator (decanter), where it decomposes by mechanical settling into two phases (an LM phase, which optionally contains part of the polyether compound, and a product phase), which can be withdrawn separately. Otherwise, or in addition, it can be used to separate the discharged
  • phase separation this can be done by distillation or extractive.
  • extractive separation this is advantageously carried out using a solvent other than LM, which dissolves the macrocyclic compounds of the general formula (Ia) or (Ib) very well, but with the solvent (LM) and optionally with the polyether compound (PE ) mixes only slightly or not at all.
  • Suitable solvents other than LM are selected, for example, from aliphatic hydrocarbons, such as pentane, hexane, heptane, ligroin, petroleum ether, cyclopentane or cyclohexane, halogenated aliphatic hydrocarbons, such as dichloromethane, trichloromethane, tetrachloromethane, or 1,2-dichloroethane, aromatic hydrocarbons, such as benzene, toluene , Xylene, halogenated aromatic
  • Hydrocarbons such as chlorobenzene, dichlorobenzenes, ethers such as diethyl ether, methyl tert-butyl ether, dibutyl ether, tetrahydrofuran or dioxane, and C1-C4 alkyl nitriles such as acetonitrile or propionitrile, and the like.
  • the product fraction obtained after the separation can be subjected to further purification if necessary.
  • the further purification is preferably a distillative separation.
  • the devices mentioned in the embodiments for distillative removal are generally suitable.
  • fractional distillation of the product fraction fractional distillation is preferably carried out using distillation columns or rotary-column reactors, in particular rotary-belt columns.
  • the fraction enriched in the solvent (LM) and optionally in the polyether compound (PE) is reintroduced into the reaction in step b.1) or b.2)
  • the reaction zone may consist of a reactor or an array of multiple reactors. Several reactors are preferably connected in series.
  • the process according to the invention can be carried out batchwise or continuously.
  • the reactors can be any reactors that are used to calculate the reactors.
  • reactors are not backmixed reactors, such as tubular reactors or built-up residence time, but preferably backmixed
  • Reactors such as stirred tank, loop reactors, jet loop reactors or jet nozzle reactors suitable. However, combinations of successive backmixed reactors and non-backmixed reactors may also be used.
  • reactors can be combined in a multi-stage apparatus.
  • Such reactors are, for example, loop reactors with built-in sieve trays, cascaded tanks, tube reactors with intermediate feed or stirring columns.
  • stirred tank reactors are used.
  • the stirred tank reactors are usually made of metallic materials, with stainless steel being preferred.
  • the reaction mixture is preferably mixed intensively with the aid of a stirrer or a circulation pump.
  • the process according to the invention is carried out in a single stirred tank.
  • the process according to the invention is carried out in at least two stirred tanks, which are connected to one another in the form of a cascade.
  • Reactors are passed through the reaction mixture in succession, wherein the outlet of the first reactor to the second reactor, the outlet of the second reactor to the third reactor, etc. is supplied.
  • the cascade can z. B. 2 to 10 reactors, with 2, 3, 4 or 5 reactors are preferred. If a cascade of several reactors is used to carry out steps b.1), b.2), all reactors of a cascade can be operated at the same temperature. In general, however, it is preferable to steadily increase the temperature from the first to the last reactor of a cascade, wherein a reactor is operated at the same or higher temperature than the upstream reactor in the flow direction of the reaction mixture. Conveniently, all reactors can be operated at substantially the same pressure.
  • streams of the educts and optionally of the solvent (LM) into the reactor or, when using a reactor cascade are preferably introduced into the first reactor of the cascade, which contains the catalyst and the polyether compound (PE).
  • the residence time in the reactor or the individual reactors is determined by the volume of the reactors and the flow rate of the reactants.
  • a vapor is withdrawn which contains the monomeric cyclization product and at least part of the solvent (LM) and optionally additionally a part of the polyether compound (PE).
  • LM monomeric cyclization product
  • PE polyether compound
  • the vapor from the individual reactors of a cascade can be combined and condensed together.
  • Subunits are coupled to a capacitor. There is also the possibility to couple each reactor of the cascade with a capacitor.
  • the solvent (LM) to be recycled and the optionally recirculating polyether compound (PE) can be passed into any reactor of a cascade or split into several reactors of the cascade. However, it is preferred that the solvent (LM) to be recycled and any polyether compound (PE) to be recycled are not directed into the last reactor of the cascade.
  • the recirculating solvent (LM) and the recirculating solvent (LM) are recirculating solvent (LM) and the recirculating solvent (LM) and the recirculating solvent (LM).
  • PE optionally attributable polyether compound
  • Another object of the invention relates to macrocyclic lactones of the general formula (1 .a), which are selected from (10Z, 18S) -18-methyl-1 - oxacyclooctadec-10-en-2-one, (10Z, 18R) -18 -Methyl-1-oxacyclooctadec-10-en-2-one, (10E, 18S) -18-methyl-1-oxacyclooctadec-10-en-2-one and (10E, 18R) -18-methyl-1-oxacyclooctadec -10-en-2-one.
  • the present invention relates to both the aforementioned isomeric compounds in their pure form and mixtures thereof.
  • 18-methyl-1-oxacyclooctadec-10-en-2-one refers both to the individual aforementioned isomers of 18-methyl-1-oxacyclooctadec-10-en-2-one and to their mixtures.
  • the compounds may be present in equal proportions or one of the compounds may be present in excess.
  • one of the compounds may be present in excess.
  • one of the compounds may be present in equal proportions or one of the compounds may be present in excess.
  • the abovementioned isomers of 18-methyl-1-oxacyclooctadec-10-en-2-one can all be prepared by means of the process according to the invention and have advantageous sensory properties, in particular a pleasant odor. Specifically, the isomers of 18-methyl-1-oxacyclooctadec-10-en-2-one possess a pungent musky odor.
  • the invention also relates to the use of at least one compound selected from (10Z, 18S) -18-methyl-1-oxacyclooctadec-10-en-2-one, (10Z, 18R) -18-methyl-1 -oxacyclooctadec-10-en-2-one, (10E, 18S) -18-methyl-1 - oxacyclooctadec-10-en-2-one and (1 OE, 18R) -18-methyl-1-oxacyclooctadec-10-en-2-one, as an odor and / or flavor.
  • the ones used for this purpose are selected from (10Z, 18S) -18-methyl-1-oxacyclooctadec-10-en-2-one, (10Z, 18R) -18-methyl-1 -oxacyclooctadec-10-en-2-one, (10E, 18S) -18-methyl-1 - oxacyclooctadec-10-en-2-one and (1
  • Compounds have a purity of at least 80%, in particular of at least 90%, for example of 95% or 97%.
  • the intensity can be over one
  • Threshold determination are determined.
  • a threshold is the one
  • Concentration of a substance in the relevant gas space in which a representative sample panel just barely perceives an olfactory impression, although this no longer needs to be defined.
  • a substance class which probably belongs to the
  • very low odor thresholds belongs intense odor substance known classes, ie very low odor thresholds comprises, thiols, the threshold m 3 range is often in the ppb / are.
  • the aim of the search for new aroma chemicals is to find substances with the lowest possible odor threshold, to the lowest possible
  • Aromachemikalie mediated odor impression describe. "Beauty” and “Prägnanz” are terms that are familiar to the expert, a perfumer. Beauty usually refers to a spontaneous, positively felt, pleasant sensory impression. “Beautiful” does not have to be synonymous with “sweet.” “Beautiful” can also be the smell of musk or sandalwood.
  • “Prägnanz” usually refers to a spontaneously evoked sensory impression, which - in the same sample panel - causes a reproducible same memory of something specific.
  • a substance may have a smell that spontaneously resembles that of an "apple”: the smell would then be concise after "apple”. If this smell of apple would be very pleasant, because the smell is pronounced of a sweet, solid apple, for example, the smell would be “nice.” But the smell of a typical sour apple can also be very succinct In the example, therefore, a beautiful and pungent smell of apple, so this substance has a particularly advantageous sensor.
  • the present invention relates to the use of at least one compound selected from (10Z, 18S) -18-methyl-1-oxacyclooctadec-10-en-2-one, (1 OZ, 18R) -18-methyl-1 -oxacyclooctadec-10-en-2-one, (1OE, 18S) -18-methyl-1-oxacyclooctadec-10-en-2-one and (1OE, 18R) -18-methyl-1-oxacyclooctadec-10 -en-2-one, as part of a composition, which is typically at least one
  • Flavoring i.e. Odor and / or flavor, and in addition
  • compositions are selected, for example, from detergents, such as laundry detergents, cleansing agents, cosmetic preparations, fragrance-containing hygiene articles, such as diapers, sanitary napkins,
  • compositions for the formulation of these compositions is usually 18-methyl-1 - oxacyclooctadec-10-en-2-one, as defined above, optionally together with one or more other flavorings, to an existing preparation containing no flavoring or one or more other flavoring agents contains, admitted.
  • compositions additionally contain a carrier material consisting of a compound, a mixture of compounds or others
  • the carrier material may also be a compound or additive having appreciable sensory properties, or may be a mixture of compounds containing at least one of the isomers of 18-methyl-1-oxacyclooctadec-10-en-2-one different flavoring agent and optionally at least one other compound that does not have appreciable
  • the carrier material may be a compound, a mixture of compounds or other additives having the above-mentioned properties.
  • Suitable carrier materials include liquid or oily carrier materials and waxy or solid carrier materials.
  • Suitable liquid or oil-form carrier materials are, for example, selected from water, alcohols, such as methanol or ethanol, aliphatic diols and polyols having a melting point below 20 ° C., such as ethylene glycol, glycerol, diglycerol, propylene glycol or dipropylene glycol, cyclic siloxanes, such as Hexamethylcyclotrisiloxane or decamethylcyclopentasiloxane, vegetable oils such as fractionated coconut oil or esters of fatty alcohols having melting temperatures below 20 ° C such as tetradecyl acetate or tetradecyl lactate, and alkyl esters of fatty acids having melting temperatures below 20 ° C such as isopropyl myristate.
  • alcohols such as methanol or ethanol
  • aliphatic diols and polyols having a melting point below 20 ° C. such as ethylene glycol, glycerol, diglycerol
  • Suitable waxy or solid support materials are, for example, selected from fatty alcohols with melting temperatures above 20 ° C., such as myristyl alcohol,
  • Stearyl alcohol or cetyl alcohol polyols having melting temperatures above 20 ° C, fatty acid esters with fatty alcohols having a melting temperature of about 20 ° C, such as wool wax, beeswax, carnauba wax, candelilla wax or Japan wax, petroleum-derived waxes, such as hard paraffin, water-insoluble porous minerals, such as Silica, silicates, for example talc, microporous crystalline aluminosilicates (zeolites), clay minerals, for example bentonite, or phosphates, for example sodium tripolyphosphate, paper, cardboard, wood, textile composite or nonwovens made from natural and / or artificial fibers.
  • fatty acid esters with fatty alcohols having a melting temperature of about 20 ° C such as wool wax, beeswax, carnauba wax, candelilla wax or Japan wax
  • petroleum-derived waxes such as hard paraffin
  • water-insoluble porous minerals such as Silica, silicates,
  • Suitable support materials are, for example, also selected from water-soluble polymers, such as polyacrylic acid esters or quaternized polyvinylpyrrolidones, or water-alcohol-soluble polymers, such as special thermoplastic polyesters and polyamides.
  • the polymeric carrier material may be in various forms, e.g. In the form of a gel, a paste, as solid particles, such as microcapsules, or brittle coatings.
  • the amounts of 18-methyl-1-oxacyclooctadec-10-en-2-one in these compositions correspond to the customary commercial amounts of additives used in formulations.
  • the amount of use of 18-methyl-1-oxacyclooctadec-10-en-2-one is in the range of 0.001 to 50 wt .-%, in particular in the range of 0.01 to 20 wt .-% and specifically, in the range of 0.1 to 10 wt .-%, based on the total weight of the composition.
  • compositions in which 18-methyl-1-oxacyclooctadec-10-en-2-one as defined above is used as the odoriferous ingredient may contain further auxiliaries and / or additives such as, for example, detergents or mixtures of detergents, Thickening agents, such as polyethylene glycols having a number average molecular weight of from 400 to 20,000 Da, lubricants, binders or agglomerating agents, such as sodium silicates, dispersants, builder salts, water softeners, fillers, pigments, colorants, optical brighteners, soil carriers and the like , Furthermore, the present invention relates to a fragrance composition and / or a fragrance material containing at least one isomer of 18-methyl-1 - oxacyclooctadec-10-en-2-one, as defined above, and a carrier material.
  • auxiliaries and / or additives such as, for example, detergents or mixtures of detergents, Thickening agents, such as polyethylene glycol
  • the total concentration of 18-methyl-1-oxacyclooctadec-10-en-2-one in the fragrance composition of the present invention and / or the fragrance material of the present invention is not particularly limited. This can be adapted in a wide range to the respective purpose. As a rule, the customary market amounts of fragrance are used. Usually, the total amount of 18-methyl-1-oxacyclooctadec-10-en-2-one is in the
  • Fragrance composition according to the invention and / or the fragrance material according to the invention in the range of 0.0001 to 20 wt .-% and in particular in the range of 0.001 to 10 wt .-%.
  • Typical applications of the fragrance compositions and / or fragrance materials of the invention are detergents, fabric care products, detergents, fragrances for the human or animal body, for rooms such as kitchens, wet rooms, cars or trucks, for real or artificial plants, for clothing, for shoes and shoe inserts , for furniture, for carpets, for
  • Room humidifier for room air perfumers, for perfumes or for cosmetics such as ointments, creams, gels, shampoos, soaps or powders.
  • fragrance compositions and / or fragrance materials of the invention find application in perfume preparations for the human or animal body, for cosmetics such as ointments, creams, gels, shampoos, soaps or powders or in perfumes.
  • the invention also includes odorant combinations which contain 18-methyl-1-oxacyclo-octadec-10-en-2-one as defined above as component A and at least one further compound known as odorant or flavoring as component B, such as for example, one or more of the following compounds B1 to B1 1:
  • B7 3,7-dimethyl-trans-2,6-octadiene-1-ol (geraniol)
  • B8 2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphthalenyl methyl ketone
  • B1 1 alpha, or beta-, or delta-damascone.
  • formulations of odorous substances for example, the formulations disclosed in JP 1 1 -071312 A, paragraphs [0090] to [0092] are suitable. Also suitable are the formulations from JP 1 1 -0 35969 A, paragraphs [0039] to [0043].
  • the present invention relates to a method for imparting or changing a smell or taste of a composition
  • a method for imparting or changing a smell or taste of a composition comprising adding to the composition 18-methyl-1-oxacyclooctadec-10-en-2-one in an amount giving the composition an odor or odor Gives flavor or changes the smell or taste of the composition.
  • the required amounts of 18-methyl-1-oxacyclooctadec-10-en-2-one depend on the nature and intended use of the composition and therefore may vary widely.
  • the amounts of 18-methyl-1-oxacyclooctadec-10-en-2-one, as defined above usually in the range of 0.0001 to 50 wt .-%, in particular in the range of 0.001 to 20 wt. %, based on the total weight of the
  • EG stands for ethylene glycol
  • PEG stands for polyethylene glycol
  • Pluriol® E 600 S stands for polyethylene glycol with a number average
  • Vinegar stands for ethyl acetate
  • GC-FI .-% represents the percentage of the area of a substance peak in relation to the total area of the peaks in a gas chromatogram
  • Ti (OiPr) 4 is titanium (IV) isopropoxide
  • Ethylene glycol phase contains an additional 4.3% product.
  • Example II.2 Cyclization of 15-hydroxypentadecanoic acid methyl ester to 15-pentadecanolide
  • Ethylene glycol phase contains an additional 2.4% product.
  • Example II.3 Cyclization of 15-hydroxypentadecanoic acid methyl ester to 15-pentadecanolide 0.8 g of magnesium oxide (0.02 mol, 0.2 eq) are added to 80 g of Pluriol® E 600 S at room temperature and after heating to 120 ° C. 31, 4 g (0.1 mol) of the molten at 70 ° C. 15-Hydroxypentadecanklandrebutylesters given. It is then evacuated to 5 mbar and heated to 250 ° C within about 20 min. At 250 ° C is started with the dosage of ethylene glycol (about 20 ml / h), whereupon distilled off a mixture of pentadecanolide and ethylene glycol.
  • the distillate is single-phase and, after phase separation, 21. 1 g of pentadecanolide are obtained with a content of 97.9 wt .-%, which corresponds to a yield of 86.0%.
  • Ethylene glycol phase contains an additional 3.8% product.
  • Example 111.1 a Isolation and preparation of (omega-1) and omega-hydroxyoic acid methyl esters from fermentatively obtained sophorolipids
  • 160.8 g of an aqueous solution of sophorolipid are extracted three times with 400 ml of ethyl acetate at room temperature.
  • the combined ethyl acetate phases are concentrated to give a residue of 68.6 g.
  • the residue is dissolved in 250 g of methanol and 6.9 g of concentrated sulfuric acid are added at RT.
  • the mixture is then heated at reflux for 10 h.
  • the reaction solution is cooled and 13.8 g of potassium carbonate are added and stirred at RT for 30 min.
  • the suspension is filtered and the filtrate is concentrated.
  • the weight is 81, 6 g.
  • the product is taken up in 400 ml of ethyl acetate and 400 ml of water and extracted.
  • phase separation the aqueous phase is extracted again with 400 ml of ethyl acetate.
  • the ethyl acetate phases are combined and concentrated to give, after cooling to room temperature, a solid.
  • the weight is 31, 7 g.
  • the mass yield is 19.7%, the content of methyl hydroxyesters about 75.7 wt .-%.
  • the ratio of (omega-1) - to omega-hydroxyoic acid methyl ester is 6.4: 1.
  • Example III.1 b Cyclization of a mixture of (omega-1) - and omega-hydroxyoic acid methyl ester to (10Z) -18-methyl-1-oxacyclooctadec-10-en-2-one and (10Z) -1-oxacyclononadec-10 -en-2-one
  • Hydroxypalmitin Textremethylestern in the solid is about 45 wt .-%, which corresponds to a mass yield of HydroxypalmitinTalkremethylestern of 31, 3%.
  • the mixture of crude Hydroxypalmitin Textremethylester is fractionally distilled at 180 ° C and 3 mbar. About 81% by weight of the crude product used is obtained as the distillation effluent. The average purity is about 67 GC wt .-% or 78 GC-FI .-% (sum of both isomers), which corresponds to a mass yield of hydroxy palmitic acid methyl esters of 55%.
  • the average Isomer ratio of (omega-1) - to omega Hydroxypalmitinklaremethylester after distillation is 1, 2: 1
  • Example III.2b Cyclization of a mixture of omega and omega-1 -hydroxyhexadecanoic acid methyl ester to oxacycloheptadecan-2-o and 16-methyl-oxacyclohexadecan-2-oo
  • Transition temperature 99-1 15 ° C).
  • the yield of the distillation is 90%, the isomer ratio of 16-Methyloxacyclohexadecan-2-one and Oxacycloheptadecan-2-one about 1, 2: 1.
  • the product is a clear, colorless liquid and has a purity of 94.5 GC-FI.%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Cosmetics (AREA)
  • Detergent Compositions (AREA)
  • Coloring Foods And Improving Nutritive Qualities (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
  • Pyrane Compounds (AREA)
  • Medicinal Preparation (AREA)
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MX2018014918A (es) 2016-05-31 2019-09-05 Basf Se Esteres de tetrahidropiranilalquilo inferior y su produccion usando un compuesto de ceteno.
US11192873B2 (en) 2017-02-24 2021-12-07 Basf Se Process for the preparation of unsaturated carboxylic acids by carbonylation of allyl alcohols and their acylation products
WO2018206415A1 (en) 2017-05-06 2018-11-15 Basf Se 2,3,7-trimethyloct-6-enyl acetate and 3,7-dimethyl-2-methylene-oct-6-enyl acetate and derivatives thereof and their use as aroma chemicals
CN111499609A (zh) * 2020-04-26 2020-08-07 绵阳三香汇生物科技有限公司 一种昆仑麝香的制备方法
WO2022192443A1 (en) * 2021-03-09 2022-09-15 Blue California Macrocyclic musk lactones and uses thereof
WO2023278760A1 (en) * 2021-07-01 2023-01-05 Blue California Enrichment enhancers for taste improvement
CN113501828B (zh) * 2021-07-07 2023-02-21 上海毕得医药科技股份有限公司 2，8-二氧杂螺[4.5]癸烷-1-酮及其制备方法和应用
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DE10041198B4 (de) 2000-08-23 2004-01-15 Symrise Gmbh & Co. Kg Verfahren zur Herstellung makrocyclischer Ester

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WO2016193134A1 (de) 2016-12-08

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