Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
  • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
  • C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms

Definitions

• the present invention relates to a process for the preparation of a cis-2- (2-methyl-prop-1-en-yl) -4-methyl-tetrahydropyran enriched composition comprising the catalytic hydrogenation of 2 - (2-methyl-prop-1-en-yl) -4-methylene-tetrahydropyran in the presence of hydrogen and a heterogeneous ruthenium-containing catalyst.
• Cis-2- (2-methyl-prop-1-yl) -4-methyl-tetrahydropyran is a valuable aromachemic chemical, also referred to as cis-rose oxide. It usually falls in the form of a mixture of diastereomers with the corresponding trans-configured compound with the cis-configured compound proving to be the more valuable, because better scented compound. Since the diastereomers, especially when produced on an industrial scale, are difficult to separate from one another, there is a sustainable need for production processes in which the preferred cis isomer of the rose oxide is formed as selectively as possible in high yield. J.H.P. Tyman and B.J. Willis describe in Tetrahedron Letters no. 51, 4507 -
• WO 79/00509 discloses a process for the preparation of cis-isomerically enriched mixtures of cis- and trans- (2-methyl-prop-1 -en-yl) -4-methyl-tetrahydropyran by catalytic hydrogenation of the corresponding, in the 4-position an exo-methylene-containing precursor.
• Suitable hydrogenation catalysts include Raney nickel and palladium catalysts, especially palladium on carbon.
• the isomeric enrichment is achieved by treatment of the hydrogenation product with an acidic or Lewis acidic reagent.
• the preferred Lewis acid is boron trifluoride.
• the process is characterized in that 2- (2-methyl-prop-1 -en-yl) -4-methylene-tetrahydropyran ("dehydro-red oxide") on a platinum dioxide or a platinum / carbon catalyst in the presence of a strongly acidic cation exchanger hydrogenated.
• dehydro-red oxide 2- (2-methyl-prop-1 -en-yl) -4-methylene-tetrahydropyran
• Th. Reached with an isomer content of the trans isomer of 90.5% and the cis isomers of 7%.
• WO 2009/077550 describes a process for the preparation of cis-2- (2-methyl-prop-1-en-yl) -4-methyl-tetrahydropyran, comprising the catalytic hydrogenation of 2- (2-methyl-prop-1 -en-yl) -4-methylene-tetrahydropyran in the presence of hydrogen and a heterogeneous catalyst comprising ruthenium on a carbon support and subsequent isomerization to increase the proportion of cis isomer by contacting the compounds thus obtained with a strongly acidic cation exchanger , Although this process allows the production of rose oxide with good conversions and selectivities, further improvement of catalytic hydrogenation is desirable.
• the invention therefore provides a process for the preparation of a cis-2- (2-methyl-prop-1-en-yl) -4-methyl-tetrahydropyran enriched composition comprising the catalytic hydrogenation of 2- (2-methyl-prop 1 -en-yl) -4-methylene-tetrahydropyran in the presence of hydrogen and a heterogeneous catalyst comprising ruthenium on an alumina carrier.
• rose oxide in the context of the invention refers to cis / trans mixtures of any composition as well as the pure conformational isomers.
• rose oxide furthermore refers to all enantiomers in pure form as well as racemic and optically active mixtures of the enantiomers of the rose oxide.
• the process according to the invention relates to a process for the preparation of an isomer mixture of cis-2- (2-methyl-prop-1-yl) - 4-methyl-tetrahydropyran of the formula (IIa) and trans-2- (2-methyl-prop-1 -en-yl) -4-methyl-tetrahydropyran of the formula (IIb).
• the compounds of the formulas (IIa) and (IIb) are obtained according to the invention in racemic form. Accordingly, the formulas (IIa) and (IIb) serve to illustrate the relative configuration of the two stereocenters and each represents the racemic mixtures of the respective enantiomeric pairs.
• the 2- (2-methyl-prop-1-en-yl) -4-methylene-tetrahydropyran used as the starting material can in principle be prepared in any way, and no special requirements are imposed on its nature or purity beyond the scope of what is customary for synthetic purposes.
• racemic 2- (2-methyl-prop-1-en-yl) -4-methylene-tetrahydropyran is used as represented by formula (I).
• the method according to the invention comprises, as additional, upstream process step, the provision of 2- (2-methyl-prop-1-en-yl) -4-methylene-tetrahydropyran (dehydro-redox oxide) of the formula (I) by reaction of 3-methyl-but-3-en-1-ol (isoprenol) of the formula (III) with 3-methyl-but-2-en-1-al (prenal) of the formula (IV) in a condensation reaction. Details can be found below the description of step i).
• a composition enriched in cis-2- (2-methylprop-1-en-yl) -4-methyltetrahydropyran is understood as meaning a composition which contains more than 50% by weight of cis-2- (2 -Methylprop-1-en-yl) -4-methyl-tetrahydropyran, based on the total amount of cis and trans isomers in the composition.
• the process according to the invention makes it possible to prepare cis-2- (2-methylprop-1-enyl) -4-methyltetrahydropyran-enriched compositions, which are preferably at least 70% by weight, more preferably at least 80% % By weight, in particular at least 90% by weight, of cis-2- (2-methylprop-1 -ene-yl) -4-methyltetrahydropyran, based on the total amount of cis and trans isomers in the composition, contain.
• the composition obtained by the process according to the invention preferably contains at most 30% by weight, particularly preferably at most 20% by weight, in particular at most 10% by weight, of trans-2- (2-methylprop-1-en-yl) 4-methyl-tetrahydropyran, based on the total amount of cis and trans isomers in the composition.
• the composition obtained by the process according to the invention contains 90 to 98% of cis-2- (2-methyl-prop-1 -en-yl) -4-methyl-tetrahydropyran and 2 to 10% by weight of trans.
• 2- (2-methyl-prop-1-en-yl) -4-methyl-tetrahydropyran each based on the total amount of cis and trans isomers in the composition.
• composition enriched in cis-2- (2-methylprop-1 -en-yl) -4-methyltetrahydropyran obtained by the process according to the invention preferably contains at most 10% by weight, particularly preferably at most 5% by weight. , in particular at most 2 wt .-% of different from cis- and trans-2- (2-methylprop-1-en-yl) -4-methyl-tetrahydropyran compounds.
• an alumina carrier is understood as meaning a carrier which comprises at least 50% by weight, based on the total weight of the carrier material, of aluminum oxide.
• the carrier used according to the invention may contain alumina in admixture with other carrier materials.
• Suitable further carrier materials are, for example, selected from graphite, silicon dioxide, titanium dioxide, zirconium dioxide and mixtures thereof.
• Preferred as further carrier materials are titanium dioxide and / or zirconium dioxide.
• the support preferably comprises at least 80% by weight, more preferably at least 90% by weight, in particular at least 96% by weight, based on the total weight of the support material, of aluminum oxide.
• Particularly preferred for use in the process according to the invention is a catalyst in which the alumina content of the carrier consists essentially of alpha alumina.
• the alumina content of the carrier is preferably at least 80 wt .-%, more preferably at least 90 wt .-%, in particular at least
• phase composition of the support can be determined by XRD (X-ray diffraction).
• the catalyst used according to the invention contains ruthenium as the active metal.
• the catalyst preferably contains 0.001 to 10% by weight of ruthenium, particularly preferably 0.01 to 5% by weight of ruthenium, in particular 1 to 3% by weight of ruthenium, based on the total weight of the catalyst.
• the weights relative to ruthenium and other metals are based on the weight of the metal, even if the metals are usually present in oxidic form on the support.
• the catalyst according to the invention may contain at least one further metal other than ruthenium as active metal or as promoter.
• Further active metals are preferably selected from the elements of groups 7 to 11 of the Periodic Table of the Elements.
• the catalysts of the invention may additionally contain at least one further metal, preferably selected from copper, gold, palladium, platinum, osmium, iridium, silver, rhenium and mixtures thereof.
• the catalyst preferably contains 0 to 10 wt .-%, preferably 0.001 to 5 wt .-%, especially 0.01 to 1 wt .-% of a further metal selected from copper, gold, palladium, platinum, osmium, iridium, silver, rhenium and mixtures thereof , based on the total weight of the catalyst.
• Preferred further metals are copper and / or gold.
• the catalysts may further contain another metal or several other metals as promoters.
• the promoters are preferably selected from alkali metals, alkaline earth metals, rare earth metals, titanium, manganese, molybdenum, tin and mixtures thereof. These are usually contained in an amount of 0 to 10 wt .-%, based on the total weight of the catalyst. If the catalysts contain a further metal or several further metals as promoters, these are preferably in an amount of 0.001 to 5 wt .-%, particularly preferably in an amount of 0.1 to 3 wt .-%, based on the total weight of the catalyst.
• the promoters are particularly preferably selected from lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, titanium, manganese, molybdenum, tin and mixtures thereof.
• the promoters are in particular selected from lithium, sodium, potassium, magnesium, calcium, scandium, yttrium, lanthanum, cerium, titanium, manganese, molybdenum, tin and mixtures thereof.
• the promoters are specifically selected from potassium, magnesium, lanthanum, cerium, titanium, manganese, molybdenum, tin, and mixtures thereof.
• Preferred novel catalysts comprise a) from 0.001 to 10% by weight, preferably from 1 to 3% by weight, of ruthenium, b) from 0 to 5% by weight, preferably from 0 to 3% by weight, of one or more alkaline earth metals, c) 0 to 5% by weight, preferably 0 to 3% by weight of one or more alkali metals,
• 0 to 10 wt .-% preferably 0 to 3 wt .-% of one or more rare earth metals, e) 0 to 10 wt .-%, preferably 0 to 1 wt .-% of one or more other metals selected from the group consisting of copper, gold, palladium, platinum, osmium, iridium, silver and rhenium, each based on the Total weight of the catalyst.
• the weights are based on the weight of the metal, even if the metals are usually present in oxidic form on the support.
• the active metal is ruthenium, which is generally contained in amounts of from 0.001 to 10% by weight, based on the weight of the catalyst.
• the catalyst of the invention contains 1 to 3% by weight, for example about 1, 6 wt .-%, ruthenium on alpha-alumina as a carrier and next to no further active metals and promoter metals.
• the ruthenium is present as RuÜ2.
• the catalysts according to the invention can be prepared by customary processes known to the person skilled in the art.
• the catalysts are obtained by impregnation of the support material with aqueous solutions of salts of the metals.
• Non-gold metals are usually applied to the carrier as aqueous solutions of their chlorides, oxychlorides or oxides.
• the ruthenium catalysts can be obtained, for example, by impregnation of the support material with aqueous solutions of RuC, optionally the salt of at least one further active metal and / or optionally a promoter for doping.
• the chlorides are preferably used in each case.
• the shaping of the catalyst can take place after or preferably before the impregnation of the support material.
• the catalysts of the invention can be used in powder form. Such catalysts preferably have an average particle size in a range of 10 to 200 ⁇ . Powdered catalysts are preferably suitable for use in the fluidized bed.
• the catalysts according to the invention can furthermore be used in the form of shaped catalyst bodies.
• Catalyst shaped bodies are preferably suitable for use as fixed bed catalysts.
• the shaped bodies or powders can be dried after impregnation at elevated temperatures and optionally calcined.
• the temperature during drying and / or calcination is preferably in a range from 50 to 600 ° C, particularly preferably from 100 to 400 ° C.
• the drying of the impregnated catalyst form body can continuously or batchwise, for. B. in band or Hordenöfen done.
• the drying can be carried out at atmospheric pressure or reduced pressure.
• the drying in a gas stream for. As an air stream or a stream of nitrogen, take place. In general, the drying is carried out at temperatures of 50 to 200 ° C, preferably 100 to 150 ° C.
• the calcination of the optionally previously dried catalyst is generally carried out at temperatures of 150 to 600 ° C, preferably 200 to 400 ° C.
• the calcination can be continuous or batchwise, for. B. in band or Hordenöfen performed.
• the calcination may be carried out at atmospheric or reduced pressure and / or in a gas stream, e.g. B. in an inert gas stream, oxygen-containing gas stream, or hydrogen-containing gas stream.
• Suitable inert gases are for. As nitrogen or argon.
• the oxides are formed from the chlorides, such as RuU2.
• Pretreatment with hydrogen or hydrogen-containing gases generally serves to pre-reduce / activate the hydrogenation catalyst.
• Shaping into shaped catalyst particles can be done before or after impregnation.
• Suitable shaped catalyst bodies are any desired forms, preference being given to tablets, rings, cylinders, stars, carriage wheels or spheres, particular preference being given to rings, cylinders or star strands.
• the specific surface area of the alpha alumina carrier before the metal salt deposition is generally in the range of 0.1 to 10 m 2 / g.
• Alpha-alumina can be prepared by heating gamma-alumina to temperatures in excess of 1000 ° C, preferably it is prepared. Generally calcined for 2 to 24 hours.
• the catalyst is subjected to reduction at elevated temperatures in the presence of a hydrogen-containing gas before use for the catalytic hydrogenation of 2- (2-methyl-prop-1-enyl) -4-methylene-tetrahydropyran.
• a hydrogen-containing gas is used for the reduction, which contains hydrogen mixed with at least one inert gas. Suitable inert gases are for. As nitrogen, argon or helium.
• the hydrogen content of the hydrogen-containing gas is at most 80% by volume, more preferably at most 60% by volume.
• the hydrogen content of the hydrogen-containing gas is preferably in a range from 10 to 60% by volume.
• the reduced catalyst is added immediately after reduction to an inert liquid and stored therein until it is used for hydrogenation.
• Suitable inert liquids are the solvents mentioned below which are suitable for carrying out the hydrogenation.
• water is used.
• the hydrogenation of 2- (2-methyl-prop-1-en-yl) -4-methylene-tetrahydropyran is preferably carried out at a temperature in a range from 50 to 150 ° C, more preferably from 70 to 130 ° C.
• the hydrogenation of 2- (2-methyl-prop-1-en-yl) -4-methylene-tetrahydropyran is preferably carried out at an absolute pressure in a range from 1 to 50 bar, more preferably from 1, 5 to 25 bar, in particular from 2 to 10 bar.
• the hydrogenation of 2- (2-methyl-prop-1-en-yl) -4-methylene-tetrahydropyran can be carried out in the presence of a solvent which is inert under the hydrogenation conditions.
• Suitable solvents are, for example, water, alcohols, such as methanol, ethanol, n-propanol and isopropanol, aliphatic hydrocarbons and hydrocarbon mixtures, such as hexane, petroleum ether and ligroin, cyclic ethers, such as tetrahydrofuran, etc.
• the hydrogen used for the hydrogenation can be used in pure form or, if desired, also in the form of mixtures with other, preferably inert, gases, such as nitrogen or argon. Preference is given to using hydrogen in undiluted form.
• the conversion in the hydrogenation, based on rose oxide, is preferably at least 90%, in particular at least 94%.
• the selectivity in the hydrogenation is preferably at least 91%, more preferably at least 95%. In many cases even higher selectivities of up to 96% and more can be achieved.
• separation of the catalyst used for example by filtration and optionally separation of the solvent used, preferably by distillation, to obtain a reaction mixture containing the diastereomeric compounds of the formulas (IIa) and (IIb) and optionally further impurities, undesirable secondary components or radicals may contain unreacted educt.
• a preferred embodiment of the process according to the invention is a process in which i) a 2- (2-methyl-prop-1-en-yl) -4-methylene-tetrahydropyran of the formula (I)
• step i) containing starting material which comprises subjecting the starting material provided in step i) to catalytic hydrogenation in the presence of hydrogen and a heterogeneous catalyst comprising ruthenium on an alumina support, wherein a cis-2- (2-methyl-prop-1-ene -yl) -4-methyl-tetrahydropyrane (IIa) and trans-2- (2-methyl-prop-1-enyl) -4-methyl-tetrahydropyrane (IIb)
• Iii) optionally separating the compounds (IIa) and (IIb) from the reaction mixture obtained in step ii), and iv) bringing the reaction mixture obtained in step ii) or the compounds (IIa) and (IIb) separated in step iii) into contact with a strongly acidic ion exchanger, the trans compound (IIb) at least partially being converted into the cis compound (IIa ) isomerized.
• the preparation of the starting mixture comprising 2- (2-methyl-prop-1-en-yl) -4-methylene-tetrahydropyran of the formula (I) in step i) preferably comprises the reaction of 3-methyl-but-3- en-1-ol (isoprenol) of the formula (III) with 3-methyl-but-2-en-1-al (prenal) of the formula (IV) in a condensation reaction.
• the reaction of 3-methyl-but-3-en-1-ol (isoprenol) of the formula (III) with 3-methyl-but-2-en-1-al (prenal) of the formula (IV) is preferably carried out in the presence an acid and in the presence of a water azeotrope forming solvent. Preference is given to doing so that in the above reaction of 3-methyl-but-3-en-1-ol of the formula (III) with 3-methyl-but-2-en-1-al of the formula (IV) separated water by azeotropic distillation with the solvent used from the reaction mixture. Both individual solvents forming an azeotrope with water and mixtures of various solvents can be used.
• solvents which form an azeotrope with water having a lower boiling point than the respective solvent or solvent mixture itself preferably those whose azeotropic boiling point in the range of about 60 ° C to about 120 ° C, particularly preferably is in the range of about 65 ° C to about 90 ° C.
• Preferred solvents are selected from ethanol, benzene, carbon tetrachloride, ethyl acetate, toluene, chloroform, n-heptane, cyclohexane and methylcyclohexane.
• Water azeotrope forming solvents are selected from toluene, chloroform, n-heptane, cyclohexane and methylcyclohexane.
• Very particularly preferred solvents are toluene and n-heptane.
• Especially preferred is toluene.
• the separation of the water released by the reaction by azeotropic distillation can be carried out according to methods known per se to the person skilled in the art or with the devices suitable for this purpose, for example with a water separator.
• the amount of solvent to be used in the azeotropic distillation mentioned above can be selected within a wide range and is generally governed by the chosen reaction conditions and the apparatus used for the removal of water.
• 3-Methyl-but-3-en-1-ol (III) and 3-methyl-but-2-en-1-al (IV) is preferably carried out in the presence of an acid.
• Suitable acids are both organic and inorganic acids, such as p-toluenesulfonic acid, trifluoroacetic acid or alkali hydrogen sulfates.
• the chosen acid is preferably used in catalytic amounts, usually based on the total amount of the starting materials to be reacted
• the reaction for the preparation of dehydroacetic oxide by condensation of isoprenol with prenal is usually and depending on the chosen solvent or solvent mixture and the chosen acid at temperatures in the range of about 60 ° C to 150 ° C, preferably in the range of about 70 ° C is carried out to 120 ° C and is then usually quickly, often after about 24 hours or earlier, largely completed.
• the resulting reaction mixture can be known to the person skilled in the art Process, for example, by extractive processes, optionally after neutralization of the acid used, worked up.
• the dehydroose oxide of the formula (I) obtained in this way as crude product can subsequently be further purified, for example by chromatography or preferably by (fractional) distillation, in which case the by-product usually obtained nerol oxide and other high-boiling secondary components can be separated.
• Step ii) With regard to suitable and preferred embodiments of step ii), reference is made to the previous statements on the catalytic hydrogenation of 2- (2-methyl-prop-1-yl) -4-methylene-tetrahydropyran in the presence of hydrogen and a heterogeneous catalyst comprising ruthenium on an alumina support, fully incorporated by reference.
• separation of the compounds of the formula (IIa) and (IIb) from the reaction mixture obtained according to step ii) can be carried out according to the optional process step iii) of the process according to the invention.
• the methods of substance separation such as, for example, chromatographic methods or, preferably, distillation, which are considered suitable by the person skilled in the art, are available.
• suitable distillation apparatuses include apparatuses for short-path distillation, such as, for example, thin-film evaporators, or else filled or packed columns and tray columns.
• the isomerization according to process step iv) of the process according to the invention is carried out in the presence of a strongly acid ion exchanger, d. H. a strongly acidic cation exchanger, such as Lewatit® S100, Lewatit® SP1 12, Lewatit® S1 15, Lewatit® SP1080, Lewatit® SC 102, Lewatit® SPC1 18, Lewatit® CNP 80, Lewatit® HD 5, Amberlite® IR 120, Amberlite® IR200, Amberlyst® 15, Bay. KAT. K 2431, Bay. KAT.
• a strongly acidic cation exchanger such as Lewatit® S100, Lewatit® SP1 12, Lewatit® S1 15, Lewatit® SP1080, Lewatit® SC 102, Lewatit® SPC1 18, Lewatit® CNP 80, Lewatit® HD 5, Amberlite® IR 120, Amberlite® IR200, Amberlys
• the selected strongly acidic cation exchangers can also be used in the form of mixtures of two or more different cation exchangers.
• the cation exchangers Lewatit® SP1 12 and / or Amberlyst® 15 are preferably used.
• the selected cation exchanger is used in the form of a fixed bed, via which the diastereomer mixture obtained from process step ii) or iii), as such or in the form of a solution in a suitable, inert under the reaction conditions, Solvent is passed.
• the mixture to be isomerized is preferably contacted in undiluted form with the selected, strongly acidic cation exchanger.
• the fixed bed can be designed, for example, in the form of a bed of the selected cation exchanger in a reaction tube, wherein the mixture to be isomerized is passed through the reaction tube filled in this way.
• the reactors can be operated in all operating modes or operating modes which appear suitable to the person skilled in the art, such as, for example, in the upflow mode or preferably in trickle mode, with the mixture to be isomerized being drizzled onto a bed of the selected cation exchanger.
• process step iv) is carried out continuously.
• the mixture to be isomerized containing the compounds of the formula (IIa) and (IIb) is continuously fed to the cation exchanger, for example by introduction into a reactor filled with cation exchanger and continuously from the same reaction vessel. the separated, for example by discharging the isomerized mixture from the reactor.
• the mixture of the compounds of the formulas (IIa) and (IIb) to be isomerised can also be contacted several times in succession with the selected strongly acidic cation exchanger or else with various strongly acidic cation exchangers, for example by recycling the diastereomer discharged from the fixed bed reactor as described above Enriched isomer mixture in the same reactor. It is also possible to pass through a plurality of such reactors, which, if desired, may also be filled with different cation exchangers in succession, so as to obtain the desired diastereomeric ratio as described above.
• the isomerization according to process step iv) is usually carried out at temperatures of about 0 ° C to about 100 ° C, preferably at about 20 to about 80 ° C.
• the resulting reaction mixture was then washed with 278 g of 2% NaOH solution.
• the toluene was distilled off at a pressure of 200 mbar over a 30 cm long column filled with Raschig rings.
• the conversion to Dehydrorosenoxid (DHR) was 62.7% of theory.
• the DHR was separated by distillation of nerol oxide and high boiling minor components and obtained with a purity of> 99%.
• Example 2 (according to the invention): First, according to Example 1 of WO 2007/023161, a RuO 2 catalyst was prepared on an alpha-A O 2 support. For this purpose, a powdery gamma-alumina carrier from Sasol (Puralox (R) SCCa 30/170) was first converted into alpha-A-C. The carrier consists of particles with a mean particle diameter of about 50 ⁇ m. 2000 g of Puralox (R) SCCa 30/170 were annealed at 1200 to 1300 ° C for 5 hours.
• Sasol Puralox (R) SCCa 30/170
• Example 2 (Analogous to WO 2009/077550, Example 2) A catalyst according to Example 1 of EP 0071787 was used which contains 5% by weight of Ru and 1% by weight of Fe on an activated carbon support.

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